リグニン討論会
第１回ー第 63 回
発表題名、著者、キーワード、要約

Lignin Symposium
1st (1956) – 63rd (2018)
Title, author, and Keywords or Abstract

2019.09.17 改訂版

目次
はじめに ................................................................................................................................................................ iii
リグニン(化学)討論会 開催記録 ..........................................................................................................................iv
１９９４年、第３９回討論会、特別寄稿 ..................................................................................................................vi
２００５年、第５０回討論会 特別寄稿 ................................................................................................................ vii
２００５年、第５０回討論会 特別寄稿 ..................................................................................................................ix
第 1 回 (1956.11.12) 大阪、府立教育会館 .........................................................................................................1
第 2 回 (1957.11.15) 東京、紙パルプ会館 ..........................................................................................................4
第 3 回 (1958.11.04) 九州大学農学部 ...............................................................................................................8
第 4 回 (1959.11.13-14) 京大、楽友会館 .......................................................................................................... 11
第 5 回 (1960.11.19-20) 名古屋、商工会議所 ..................................................................................................16
第 6 回 (1961.11.18-19) 大阪、府立農林会館 ..................................................................................................20
第 7 回 (1962.10.04-05) 北海道大学クラーク会館 ..........................................................................................24
第 8 回 （1963.11.5-6） 松江市、島根自治会館 .................................................................................................29
第 9 回 (1964.11.11-12) 紙パルプ会館 .............................................................................................................33
第 10 回 （1965.11.8-9） 大阪科学技術センター ...............................................................................................38
第 11 回 （1966.10.31-11.1） 広島大学会館.......................................................................................................44
第 12 回 （1967.11. 1-2） 九州大学農学部 .........................................................................................................51
第 13 回 （1968.10.26-27） 名古屋大学農学部 .................................................................................................56
第 14 回 （1969.10.28-29）東京、日本化学会講堂 .............................................................................................61
第 15 回 （1970.10.8-9） 札幌市民会館 ..............................................................................................................65
第 16 回 （1971.11.4-5） 高松電機ビル ..............................................................................................................70
第 17 回 （1972.11.4-5） 京都大学農学部 ..........................................................................................................76
第 18 回 （1973.11.3-4） 九州大学農学部 .........................................................................................................80
第 19 回 （1974.10.19-20） 秋田大学教育学部 .................................................................................................86
第 20 回 （1975.10.20-21） 名古屋大学農学部 .................................................................................................92
第 21 回 （1976.10.18-19） 東京大学農学部 .....................................................................................................99
第 22 回 （1977.10.8-9） 北海道大学農学部 ...................................................................................................105
第 23 回 （1978.11.1-2） 愛媛大学農学部 ....................................................................................................... 111
第 24 回 （1979.11.1-2） 京都大学、生産開発科学研究所 ............................................................................. 118
第 25 回 （1980.10.17-18） 九州大学農学部 ...................................................................................................124
第 26 回 （1981.10.29-30） 工業技術院筑波研究センター .............................................................................130
第 27 回 （1982.10.21-22） 名古屋大学農学部 ...............................................................................................136
第 28 回 （1983.10.7-8） 北海道大学農学部 ...................................................................................................143
第 29 回 （1984.10.15-16） 東京大学農学部 ...................................................................................................149
第 30 回 （1985.11.6-7） 高知会館 ...................................................................................................................155
第 31 回 （1986.10.21-22） 京大会館 ...............................................................................................................162
第 32 回 （1987.10.20-21） 福岡リーセントホテル............................................................................................169
第 33 回 （1988.11.8-9） ホテルサンルート筑波 ..............................................................................................176
第 34 回 （1989.10.16-17） 名古屋大学農学部 ...............................................................................................183
第 35 回 （1990.10.15-16） 東京大学 山上会館.............................................................................................190
第 36 回 （1991.10.14-15） 北海道大学 学術交流会館 .................................................................................201
第 37 回 （1992.10.19-20） 京大会館 ...............................................................................................................214
第 38 回 （1993.11.15-16） 四国電力株式会社 総合研究所 .........................................................................227
第 39 回 （1994.10.12-13） 福岡リーセントホテル............................................................................................240
第 40 回 （1995.10.12-13） つくば 研究交流センター ....................................................................................255
第 41 回 （1996.10.3-4） 名古屋大学農学部 ...................................................................................................269
第 42 回 （1997.10.27-28） 北海道大学学術交流会館 ...................................................................................285i

第 43 回 （1998.10.26-27） 府中グリーンプラザ ..............................................................................................302
第 44 回 （1999.10.7-8） 岐阜大学農学部 .......................................................................................................316
第 45 回 （2000.10.26-27） 愛媛大学農学部 ...................................................................................................330
第 46 回 （2001.11.1-2） 京都大学木質科学研究所 .......................................................................................347
第 47 回 （2002.10.31-11.01） アクロス福岡国際会議場.................................................................................367
第 48 回 （2003.10.30-30） 福井工業大学芦原学舎 .......................................................................................383
第 49 回 （2004.11.18-19） 筑波大学大学会館 ...............................................................................................402
第 50 回 （2005.10.19-20） 名古屋大学 野依記念学術交流館 .....................................................................416
第 51 回 （2006.10.26-27） 北海道大学 学術交流会館 .................................................................................430
第 52 回 （2007.11.14-15） 宇都宮大学 大学会館 .........................................................................................451
第 53 回 （2008.10.30-31） 東京大学農学部 弥生講堂 .................................................................................469
第 54 回 （2009.10.29-30） 静岡県男女共同参画センター .............................................................................485
第 55 回 （2010.10.20-21） 京都大学 百週年時計台記念館 .........................................................................502
第 56 回 （2011.09.15-16） 山形大学 農学部 .................................................................................................519
第 57 回 （2012.10.17-18） アクロス福岡 国際会議場 ...................................................................................536
第 58 回 （2013.11.12-13） サンポートホール高松 ...........................................................................................550
第 59 回 （2014.09.11-12） 福井工業大学 ........................................................................................................566
第 60 回 （2015.11.05-06） つくば大学 ..............................................................................................................584
第 61 回 （2016.10.27-28） 京都大学 宇治おうばくプラザ..............................................................................603
第 62 回 （2017.10.27-28） 名古屋大学 野依記念学術交流館 .....................................................................632
第 63 回 （2018.11.1-2） 東京農工大学 グリーンホール、科学博物館 .........................................................651

ii

はじめに
リグニン討論会は 1956 年に発足しました。事務局も会長もなく、毎年世話人が交替しながら、この討論会が半世紀以上も続いて開催されてきたのは実に希有なことです。これはリグニンが、人々の科学的探究心を常に奮い立たせる魅力的な未踏峰の如き物質であるからでしょう。曾て世界のリグニン研究をリードしてきた欧米諸国の拠点の多くでは、近年の「すぐ目に見える研究成果」を求める風潮のなか、次第にその活動は寂れてきています。一方、日本では、毎年若い優秀な研究者がこの分野に参入し、厚い研究者層を形成して、樹木・木材科学分野で世界の研究をリードしつつあります。半世紀以上にわたるリグニン討論会の活動が、このことに大きく貢献していることは疑いのないことです。
高等植物は、リグニンの形成によってその大型化が可能となり、多様な進化を遂げました。そのため、リグニ
ンおよびリグニン由来の腐植物質等は地球上最多の有機物となり、炭素循環の大きなプールとして、生態系の変遷に深く関わっています。したがって、リグニンに関する知見は、樹木や作物の生産・利用のみならず、
人類生存圏の理解にとっても重要であります。しかしその化学構造さえも、天然有機化合物中最も複雑・多様であるため、未だ完全には解明されていません。いろいろな意味で未踏峰の連なる山脈のような未解明物質リ
グニンは、種々の異なる視点から異なる手法で見た断面の知見を総合することで、始めてその全貌を捉え得るものでしょう。そのため、リグニン討論会は、紙パルプ技術協会、日本木材学会、日本化学会、日本農芸化学会および繊維学会の共催、高分子学会およびバイオインダストリー協会の協賛学会となっており、異なる分野の研究者たちが、自由な討論を通してリグニンの全貌への理解を深めることを目指しています。このため、たとえ未完成の研究であっても、新しい着想や手法・技術、実験結果についての自由な討論が歓迎され、特定の学会の年次大会とは異なる性格を持っています。
リグニン討論会の講演要旨集には、その研究の最初の着想やデータが載ります。その後論文として発表されないものもあるので、貴重な文献です。審査済みの論文でなくとも、あるいは古い着想やデータでも、それがヒントになって優れた研究が触発されることは多々あります。この分野に新しく参入される研究者には、過去の講演要旨集を通覧することによって、リグニン研究の内容や手法の進歩・変遷を知り、巨大なリグニン山脈に立ち向かうための新しい戦略的発想の手掛りを得る「温故知新」の効果が期待できるかも知れません。 しかし
リグニン討論会には公式の記録を残す事務局もなく、半世紀余の間には研究者の世代交代も進んで、古い講演要旨集は散逸しようとしています。そこで第 1 回討論会以来の全講演要旨集の原本を整備し、下記の研究拠点で保存公開することになりました。
★紙パルプ技術協会★東京大学大学院農学生命科学研究科木材化学研究室（問合せ先、松本雄二）★名古屋大学大学院生命農学研究科森林化学研究室（問合せ先、福島和彦）★京都大学生存圏研究所（問合せ先、梅沢俊明）
そして約２０００件を超える研究発表内容の検索を容易にするため、和文と英文とで発表題目、研究者名と所属を記録し、キーワードを本文内容から選定し、デジタル記録として整理しました。第３５回討論会以降の要旨についてはキーワードの替わりに Abstract を記載しました。ただし重要なキーワードでも表題中に含まれる場
合は、二重記録を避けるため省略してあります。各発表番号の最初の４桁は発表年次を、次の３桁は要旨集
記載の発表番号を示しています。またリグニン討論会発足の経緯と変遷を知るための参考資料として、討論会発足の頃から深く関与して来られた３名の方々の特別寄稿を載せました。今後のリグニン研究のための参考資料として利用されることを期待しています。
この記録を整理するに当たっては、なるべく原著者を含む多くの方々にお願いし、点検・修正をして頂きました。貴重な時間を割いてご協力下さいました皆様に厚くお礼を申し上げます。なお、英文の表題、氏名，所属の誤訳・誤読、キーワードの選定などの責任はすべて編集世話人にあります。これらの記録は、原講演要旨集の検索の目的以外には、転用なさらぬ様にお願いします。さらに、誤字、脱字、その他修正を要する点などお気付きのときは、世話人宛お知らせ下さい。適時に修正版を下記の URL よりお配りして、正しい記録を皆様と共有したいと思います。
http://www.agr.nagoya-u.ac.jp/~lignin/Lignin_Symposium.pdf（2018 年のリグニン学会設立により管理移管しました）
編集世話人、名古屋大学名誉教授 寺島 典二
iii

リグニン(化学)討論会 開催記録
回

日時

開催地

講演

1

1956.11.12

0

1957.11.15
1958.11.04

大阪、府立教育会館
東京、紙パルプ会館

16

2
3

20
15

0
0

4
5

1959.11.13-14
1960.11.19-20

29
21

0
0

6
7

1961.11.18-19
1962.10.04-05

19
24

1
1

8
9

1963.11.05-06
1964.11.11-12

18
22

3
2

10
11

1965.11.08-09
1966.10.31-11.01

31
38

4
2

12
13

1967.11.01-02
1968.10.26-27

26
28

0
0

14
15

1969.10.28-29
1970.10.08-09

20
25

0
0

16
17

1971.11.04-05
1972.11.04-05

34
18

0
2

18
19

1973.11.03-04
1974.10.19-20

35
30

0
1

20
21

1975.10.20-21
1976.10.18-19

22
23

1977.10.08-09
1978.11.01-02

24
25

1979.11.01-02
1980.10.17-18

26
27

1981.10.29-30
1982,10.21-22

28
29

1983.10.07-08
1984.10.15-16

30
31

1985.11.06-07
1986.10.21-22

32
33

1987.10.20-21
1988.11.08-09

34
35

1989.10.16-17
1990.10.15-16

36
37

1991.10.14-15
1992.10.19-20

38
39

1993.11.15-16
1994.10.12-13

40
41

1995.10.12-13
1996.10.03-04

42
43

1997.10.27-28
1998.10.26-27

44
45

1999.10.07-08
2000.10.26-27

46
47

2001.11.01-02
2002.10.31-11.01

48
49

2003.10.30-31
2004.11.18-19

50

2005.10.19-20

福岡、九州大学農学部
京都、楽友会館
名古屋、商工会議所
大阪、府立農林会館
札幌、北海道大学クラーク会館
松江、自治会館
東京、紙パルプ会館
大阪、科学技術センター
広島、広島大学会館
福岡、九州大学農学部
名古屋、名古屋大学農学部
東京、日本化学会講堂
札幌、市民会館
高松、電気ビル
京都、京都大学農学部
福岡、九州大学農学部
秋田、秋他大学教育学部
名古屋、名古屋大学農学部

34
28

東京、東京大学農学部
札幌、北海道大学農学部

28
34

松山、愛媛大学農学部
京都、生産開発科学研究所
福岡、九州大学農学部
つくば、工業技術院筑波研究センター
名古屋、名古屋大学農学部
札幌、北海道大学農学部
東京、東京大学農学部
高知、高知会館
京都、京大会館
福岡、福岡リーセントホテル
つくば、ホテルサンルート筑波
名古屋、名古屋大学農学部
東京、東京大学山上会館
札幌、北海道大学学術交流会館
京都、京大会館
高松、四国電力 KK 総合研究所
福岡、福岡リーセントホテル
つくば、研究交流センター
名古屋、名古屋大学農学部
札幌、北海道大学学術交流会館
府中、府中グリーンプラザ
岐阜、岐阜大学農学部
松山、愛媛大学農学部
宇治、京都大学木質科学研究所
福岡、アクロス福岡国際会議場
福井、福井工業大学芦原学舎
つくば、筑波大学
名古屋、名古屋大学野依学術交流館

小計

iv

30
32

ポスター

特別講演

備考

会期が 2 日間となる。

2
1+総合討論 1
1+総合討論 2
1
2

32
33

1+総合討論 1
2
2

30
30

1
2

34
35

2
2

36
36

2
2

37
36

2
1

42
41

2
2

リグニン討論会に改称。

英文 Abstract を記載。

39
25

23

2
1

26
32

18
17

1
1

33
25

23
17

1
2

29
34

19
20

2
2

41
34

24
17

3
2

35
27

27
17

2
1

29

13

1 + パネル討論 １

1486

235

72

ポスター発表を開始。

計 1793

回

日時

開催地

講演

ポスター

特別講演

51
52

2006.10.26-27
2007.11.14-15

北海道大学、学術交流館

28
33

30
22

2
2

53
54

2008.10.30-31
2009.10.29-30

28
28

19
24

1
1

55
56

2010.10.20-21
2011.09.15-16

30
28

20
19

1
1

57
58

2012.10.17-18
2013.11.12-13

24
23

12

1
1

59
60

2014.09.11-12
2015.11.05-06

61
62

2016.10.27-28
2017.10.27-28

63

2018.11.1-2

宇都宮大学、大学会館
東京大学、弥生講堂
静岡県男女共同参画センター「あざれあ」
京都大学、百周年時計台記念館 国際交流ホール
山形大学農学部
福岡、アクロス福岡国際会議場
高松、サンポートホール高松
福井、福井工業大学
つくば、筑波大学
宇治、京都大学宇治おうばくプラザ
名古屋、名古屋大学野依学術交流館
小金井、東京農工大学

総計

v

22
20

1７
21
27

26
18

41
29

1 + 9＊
3

25
1819

44
560

2
100

備考

1
2
＊

ワークショップ

総計 2479

１９９４年、第３９回討論会、特別寄稿「リグニン討論会の発足の頃」
九州大学名誉教授 千手諒一
リグニン討論会も今年で 39 回を迎えると言う。「10 年ひと昔」と言います。40 年も前のことを思い出すのは、82
歳の翁には難儀なことです。かすかな記憶を頼りにべンをとってはみましたが、思い違いはお許し願います。
リグニン討論会の第一回目（昭和 31 年）は阪大工学部の八浜義和先生（故人）のお声がかりで聞かれました。
当時は日本も、経済発展の真只中でありました。大東亜戦争で、エネルギーの総てを使い果した日本も、ようやく復興の波に乗り、朝鮮事変も重なって、復興景気に湧き立っておりました。3P 景気、3 白景気（紙、砂糖、硫安）と騒がれた時代です。製紙工場も増設また増設、勿論 SP 法ですから、蒸解廃液は垂れ流しです。公害
問題は、早速田子の浦の汚染で始まりました。紙パルプ産業は四面楚歌で、私どもは肩身の狭い思いをしたものです。当時私は、九大の木材研究所で、キチン、キトサンの研究から SP 廃液中のリグニンスルホン酸のコ
ロイド滴定を始めておりました。それがご縁で、八浜先生に親しくして頂きましたが、先生は木材化学工業に深い関心を持っておられました。ある時私に、「紙パルプ工業も木材の大半を流失するようでは、真の化学工業とは言えませんね」と言われました。農学部の学生時代から、工学部の応化にコンプレックスを感じていた私には、胸に突き刺さるひと言でした。私は廃液リグニンの利用を中心とした研究を進めて、木材の完全利用と共に、SP 廃液による公害を防止せねばと思いました。早速、八浜先生を初め東大の右田信彦先生（故人）、国策パルプの三川礼氏（後に阪大工学部教授）や佐藤孝一郎氏、九大木研の北浦貞夫先生（故人）、にお願い
して、初回は阪大工学部で開くことになりました。初めの頃は、発表件数も少ないので、リグニンに関することなら何んでもよいと言うことで、パルプ蒸解のことまで発表されましたが、それでも数件で寂しいものでした。しかし回を重ねるにつれて参加者も段々増えて来ました。大学関係のみならず、工試（東京、大阪）の方々まで参加され、討論会も一段と活発になってきました。私なんか、わざわざあるマイクも使わずに口角泡を飛ばしたものです。中野さん（東大）、越島さん（大阪工試から京大木研）、林さん（立命館大）、猪狩さん（東京工試）などなど、懐かしいご仁が大勢でした。この討論会の魅力はなんと言ってもその会の雰囲気でした。参加者全員が、恰も一家族のように、心おきなく語りあえる。その喜びは他の学会では到底味あうことのできない大きな魅力でした。メンバーの各人は、年一回のこの討論会を楽しみに、日々研究に励んでいたように思います。リグニン
討論会が、39 回を数える今日もなお、旧に倍して盛大であるのも、一因がその辺にあるのかもしれませんね。
しかし時は流れて、パルプの製造法も KP 法に変わりました。廃液リグニンは、公害の元になる廃物ではありません。燃料として立派に利用されておりますから、パルプ工業も真の化学工業と言える時代になりました。リグ
ニンの利用研究も、そろそろ看板を下してもよい頃かと思っておりましたが、今回のプログラムを拝見して安堵致しました。これからはリグニンの生化学を中心に、リグニンの本質を明らかにしたいものです。リグニンのない
木材などは無理だとしても、丸太の木材をそのままシートに変えることができれば最高ですね。ナインテイ（90）、
ナインテイ（90）、ナイン（9）の収量、白色度、強度を目標とするリグニンのメカノケミカルの研究も進められている由、私は大きな期待を寄せております。リグニン討論会の進路も、時の流れと共に、大きく変わりつつあることをこの上なく嬉しく思います。皆さんの御研鑽を祈ります。

vi

２００５年、第５０回討論会 特別寄稿
「リグニン討論会の黎明」
京都大学名誉教授 越島哲夫
寺島先生の、本当に先生らしい純粋なご提案に賛同しながら、この討論会はそもそも誰が、どんな経緯で始めたのかを、先ず知りたいと思って、私なりに努力してみました。当時私は、京大木材研究所の助手をしており、大凡のことは解っているつもりでしたが、調べてみると、かなり誤っていたようです。
第 1 回の討論会は、皆さんもご承知の様に，阪大、八浜義和先生のところでした。八浜先生が日本化学会に要望書を出して“リグニン化学討論会”が発足したのには千手諒一先生〈当時九大生産科学研究所助教授〉と八浜先生の出会いが一つのきっかけになった（坂田功氏）ようです。もう一人、設立に当って外せない人は、
当時、国策パルプ〈株〉農林科学研究所の三川礼先生（のちに阪大教授）です。三川先生もその頃、八浜先生に討論会をつくることを強く要望されていたのではないかというのが私や林アキラさん（のちに立命館大教授）の推測です。その結果、八浜（阪大）、西田（九大）、右田（東大）、舘〈京大〉先生が発起人となり、リグニン化
学討論会がスタートしたようです。第 1 回討論会の開催には当時阪大助教授だった京極先生が奔走され、１６件の発表がありました。この時、企業からは国策パルプのみで、３件の発表があったのも，三川先生のリグニン
化学への情熱が現れていたようにおもえます。第１回では、当時、大御所といわれた，八浜、右田，舘、北浦、
大野（一月）各先生のほか、近藤（民），千手、三川、軒原，佐藤（孝）、石川、中野、榊原、本田（真）、京極など錚々たる名前がならんでいます。第 2 回は東大において右田-中野先生で、第 3 回は九大、第 4 回は京大で行われました。九大では、北浦-千手先生で実施され、千手先生が世話人として大変努力された（坂田功氏）と聞いています。京大では、林アキラさんが世話人を任され、この時始めて企業からの参加を呼びかけ、寄付も募った結果、発表数が増えたので会期を二日間とした（林アキラ氏）ようです。同時に懇親会も加え学生は無料としたのも第 4 回からでした。第 2 回の、東大での討論会には私、欠席したので詳しい情報は私の所になく、寺島先生から補足して頂ければ幸いです。何れにしろ創世期のころは大学を代表する大先生のほかに、実際の運営に当った世話人各位の情熱と努力がこの討論会の維持と発展の大いなる原動力となったことは記録されるべきでありましょう。
ここで私は、あまり知られていないと思われるので、もう一度三川先生について触れておきたい。先生は国策パルプ時代、昭和 26-31 年にかけ、当時有名であった三川理論を展開された。それは，X 基、Z 基、B 基となずけられた、リグニンの反応性の異なる官能基がサルファイト蒸解やクラフト蒸解でどのように挙動するか、そして脱リグニンが進行するかを示したもので、当時としては理路整然として真に興味深いものでした。私は後になってリグニンの話を直接お聞きするため三川先生を阪大にお訪ねしたことがあります。その頃“基礎木材工学”なる学生向け冊子を当時近畿大学で講義をもっていた 5 名の共著として執筆中であって、初版は昭和４８
年に出版されました。従って三川先生にお会いしたのが 45-47 年の間と思います。既にその時、八浜先生の後任として阪大にきておられ、リグニン研究から離れて半導体をご研究中ということでしたが、実に懐かしそうにリグニンの話をされました。自らを誇るでなく、また惜しむ様子もなく一人の研究者として淡々と話された雰囲
気がとても印象的でした。ただ繰り返し話された言葉は“リグニンは別れた女房のようなものだ。懐かしくもあり
忘れ難い”と。東大理学部化学科卒の、いかにも秀才らしい、しかもえらぶった所のない紳士の面影が、育ちの良さとでもいえるのでしょうか、その柔和さと共に私にとって忘れられないリグニン化学者の一人です。
黎明期を便宜上昭和 30 年代と位置ずけると、私自身にとっても一つの転換期でした。恩師のお勧めを無げに断って大学を去り，通産省（当時）の工業試験所（いまの産総研）へ移ったのが昭和 37 年で、その主たる理由が十分な研究費を使って研究室をもちたいということでした。若気の至りという所でしたが、さて試験所で何をしたかということになると、これがリグニンのグラフト重合でした。時、恰も高分子全盛時代であって京大，阪大、阪市大などの工学系では物凄いブームで、高分子化学が跋扈した世の中でした。その時、工業技術院でも放射線の平和利用のための予算がつき、高分子センターになっていた大工試にガンマ線照射室が設けられることになった訳です。予算がついたから成果を出せという話になって、リグニンを基体とするグラフト重合を行うことを決めた訳です。今にして思えば、よくもまあ、やったものだという感がします。しかし、ガンマ線を使ったリグニンのグラフト重合は一つのアイデアだったかもしれないと今ではおもうのです。何故なら，リグニンは放射線に比較的強いからです。ただし、グラフトポリマーの物性に関する知識に乏しかったのが世に出なかった最大の理由だったと思います。放射線照射研究の場合、そのものが持つＧ R 値、すなわち吸収エネルギー
100e.V.当り生成するラジカル数が大きい意味をもちます。例えばメタクリル酸メチルはこの値が 6.3、スチレン
vii

が 0.66、つまり芳香核など共鳴構造を多く持つものは放射線に強いことになります。この点から類推するとリグ
ニンはかなり放射線に強くすぐに崩壊するセルロースとは対照的です。この特性を利用しリグニン-スチレング
ラフトポリマーをつくり、特性を調べると耐磨耗性は高く，半導体的性質も併せ持つことがわかりました。用いたリグニンは淡黄色の塩酸リグニンで研究用としては木粉から容易に製造できましたが、企業用原料としては当時適当とは言えず、また、放射線を使うことは設備、その他で制限を受けることになります。それでリグニン原料としては後述するようにパルプ廃液から得られるリグノスルホン酸がよく、レドックス開始グラフト重合が有望であることがわかりました。塩酸リグニンを用いるグラフト研究は昭和 37-39 年に行ったもので、リグノスルホン酸をベースにしたメタクリル酸メチルのグラフト研究は私が京大に移った為中断したのがいささか残念ではありました。昭和 39-41 年初頭まではシラキユウスのニュ－ヨ-ク州立大学で働き、帰国後はリグニンとヘミセルロ－スの結合体、所謂 LCC の研究に移りましたので、リグニンへのグラフト研究は終了しました。リグノスルホン酸にメ
タクリル酸メチルあるいはアクリロニトリルをレドックス系，例えば過酸化水素－第 1 鉄塩を開始剤としてグラフト重合させる反応は、前者は室温付近で、後者は零度でも進行する大変面白い反応なのでグラフトポリマ－の物性を含めて、関心のある方は是非試してみる価値があると思っています。リグニン化学討論会は、後に化学系だけでなく生物系の研究者も加わってもらうため、東大での幹事会のとき中野先生らと話しあって“化学”を取り去り今のようにしたことを覚えています。このサロン的な集いが今後とも発展の原動力として存続することを願っています。

viii

２００５年、第５０回討論会 特別寄稿
「第５０回リグニン討論会を迎えて」
京都大学名誉教授（京都大学木質科学研究所）樋口隆昌
第５０回リグニン討論会を迎えるにあたり、これまで、私達のグループが岐阜大学、京都大学で進めてきた、リグニンの生合成と微生物分解研究の流れと将来への展望に就いて簡単にまとめてみました。
私は１９５０年４月、岐阜大学農学部林学科木材化学講座（川村一次教授）の助手に採用されてから一貫してリグニンの生化学的研究を続けてきました。当時、欧米（Heidelberg, Prof. K. Freudenberg; Göteborg, Prof. E.
Adler；Stockholm, Prof. H. Erdtman, Prof. E. Hägglund; Wien, Prof. K. Kratzl; Wisconsin, Prof. F.E. Brauns;
New York, Prof. F.F. Nord; Toronto, Prof. H. Hibbert 等）では理学部、工学部関係の研究者が、主としてリグニンの化学構造、木材のパルプ蒸解と関連したリグニンの化学反応機構、リグニンの化学分解反応（ニトロベン
ゼン酸化、過マンガン酸酸化、エタノリシス、アシドリシス等）が研究されていました。更に１９５６年、 A.
Björkman によって milled wood lignin が調製され、リグニンの IR, UV スペクトル、分子量、上記した分解反応と分解生成物の解明が急速に進展しました。
しかし、リグニンは、タンパク質、セルロース、デンプンなど加水分解によって定量的に構成モノマーに分解される生体高分子と異なり、上記代表的な分解法でも分解生成物の収量は 1０—４０％で、分解法によるリグニン化学構造の解明は不可能な特異な高分子である事が次第に明らかになってきました。
当時、我が国では、主としてリグニン研究に携わっておられた右田伸彦教授（東大農学部）、西田屹二教授（九大農学部）、館勇教授（京大農学部）、八浜義和教授（阪大工学部）の諸先生による協議の結果、第１回リ
グニン化学討論会が発足しました。その後、次第にリグニン研究の内要と分野が広くなり、現在のリグニン討論会に至っている。
私のリグニン研究は、そのような時期に始まりました。私は名大理学部生物学科（植物）の出身で、有機化合物の合成、反応解明、構造決定などの経験に乏しく、植物生化学の手法でリグニンの生化学的研究ができればと思っていましたので、リグニンの生合成に就いて研究を始める事にしました。その頃、八浜義和、岡部次郎：リグニン化学の最近の進歩（I）, (II). 化学の領域、南江堂、11, 1-12(1956), 12,15-31 (1956)が出版され、Freudenberg の研究室で、マッシュルーム酵素によるコニフェリルアルコールの脱水素重合で生成した、オリゴ
リグノール（グアイアシルグリセロ−ル−β−コニフェリルエ−テル、d,l-ピノレジノ−ル、デヒドロジコニフェリルアルコール）と DHP の構造研究が詳細に紹介されました。
そこで手始めに Freudenberg の方法でマッシュルームのフェノールオキシダーゼを調製して酵素的性質を調べ、コニフェリルアルコールを脱水素重合させる酵素は CO 阻害を受けないラッカーゼ（p—ジフェノールオキシダーゼ）である事を突き止め、漆ラッカーゼとも比較した結果、樹木の木化（モノリグノールの脱水素重合）に関与する酵素は、ラッカーゼより、植物に一般的に分布しているペロキシダーぜである事を明らかにする事が出来ました。この結果（Biochemical studies of lignin formation (1), (2), (3). Physiol. Plantarum 10, 356, 621,
633 (1957); Further studies on phenol oxidase related to the lignin biosynthesis. J. Biochem. 45, 515 (1958) がWien 大学の Prof. Kratzl の目にとまり、第４回国際生化学会（1958, Wien）で講演する機会を与えられたわけです。(T. Higuchi: Studies on the Biosynthesis of Lignin. pp161-188. Proc. 4th International Congress ofBiochemistry 1958)
この学会で Prof. Freudenberg, Adler, Erdtman, Nord, Neish 等、それぞれの分野の代表的な研究者の研究発表と真剣な討論に接し、強い感銘を受けました。さらに学会後、ドイツ、スェ−デンで各先生の研究室を訪問し、研究の実体を知る事が出来たのが、私の将来の研究方向を決定したように思います。
Dr. A.C. Neish（Prairie Regional Laboratory, Saskatoon, Canada）から同研究所の Dr. S. A. Brown がリグニンの生合成の研究を始めたので、一緒に研究をしませんかとお誘いをうけたのもこの学会でした。当時、岐阜大学ではアイソトープによるトレーサー実験は出来ませんでしたので、１９６０— ６２の 2 年間、Saskatoon の平原地方研究所に滞在し、14C-ラベルしたリグニン前駆物質（グルコース、シキミ酸、フェニルアラニン、ケイヒ酸、pクマール酸、カフェー酸、フェルラ酸、シナピン酸など）を小麦植物体に投与して２４時間代謝させてから、ニト
ロベンゼン酸化生成物（バニリン、シリンガアルデヒド）、エタノリシス生成物（ジケトン）の 1４C 活性を測定する方法で、モノリグノール生合成経路を解明していきました。その結果をとりまとめたのが、Dr. Brown と私によるモ
ノリグノール生合成経路で、その後、内外の研究者によりモノリグノール生合成経路の基礎として引用されて来ています。
ix

１９６８年、京都大学木材研究所に新設されたリグニン化学研究部門に招待され、島田幹夫（現京都大学名
誉教授）、中坪文明（現京都大学教授）等の協力を得てリグニン生合成に関与する酵素（OMT 等）の解明、オ
リゴリグノ−ルの合成、リグニンの微生物分解反応機構の解明等に力を入れてきました。
最近は研究法、分析法の進歩、関与する酵素の細胞内分布などが解明され、上記のモノリグノール生合成
経路にバイパスや、一部改定が加えられていますが,我々のモノリグノール生合成経路の基本は、保たれていると思っています。
私の定年退職の頃からモノリグノ−ル形成に関与する酵素の遺伝子解明が進み、最近ではポプラ、テーダ松、Zinnia、Arabidopsis などによる細胞壁合成に関する遺伝子と、その発現機構の解明（T. Higuchi, Pathways formonolignol biosynthesis via metabolic grids: coniferyl aldehyde 5-hydroxylase, a possible key enzyme inangiosperm syringyl lignin biosynthesis. Proc. Jpn. Acad., 79, 227-236. Ser B (2003) が進みつつあり、将来は利用目的と生態系に適した樹木の生産が可能になるものと考えられ、私達の研究がここまで発展してきている事を大変嬉しく思っています。
さらに私等はリグニンの微生物分解機構に就いても研究を進め、白色腐朽菌が分泌するリグニンペロキシ
ダーゼ、ラッカーゼによって、リグニン側鎖ばかりで無く芳香環も分解される機構を 13C, D, 18O で標識したオリゴリグノール、DHP を基質として D2O, 18O2 の存在下でリグニンペロキシダーゼ分解し、分解生成物の分析によってそれらの分解機構を明らかにする事が出来ました。この研究分野も現在遺伝子レベルの研究に移行していますので、将来、バイオパルピングや生態環境浄化に繋がっていくものと期待しています（T. Higuchi,
Microbial degradation of lignin : Role of lignin peroxidase, manganese peroxidase, and laccase. Proc. Jpn.
Acad., 80, 204-214. Ser B(2004).
以上、私達がこれまでやってきたリグニンの生化学的研究についての経過と感想を思い出すままに記述しました。第５０回リグニン討論会に出席され、現在第一線でリグニンの研究に携わっておられる方々に少しでも参考になれば幸いです。今後、リグニン討論会のますますの発展を祈念しております。

x

第 1 回 (1956.11.12) 大阪、府立教育会館
1956-001
亜硫酸蒸解の速度を支配する因子について
坂田 功、千手諒一
九州大学大生産研究所
Factors controlling sulfite cooking rate
Isao Sakata, Ryoichi Senju
Institute of Industrial Science, Kyusyu University
Keywords: lignin sulfonic acid, delignification, sulfonation, successive reaction
1956-002
亜硫酸蒸解におけるフエノール成分の挙動
中野準三
東京大学農学部
Behavior of phenolic components during sulfite cooking
Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Japanese red pine, Pinus densiflora, larch, Larix Kaempferi, pinosylvin, taxifolin,
vanillyl alcohol, quercetin
1956-003
落葉樹のサルファイト蒸解について
軒原栄三
国策パルプ株式会社
Sulfite cooking of larch
Eizo Nokihara
Kokusaku Pulp Co., Ltd.
Keywords: heartwood, sapwood, taxifolin,ε-galactan
1956-004
クラフト蒸解機構
三川 礼
国策パルプ株式会社
Mechanism of kraft cooking
Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: lignin, sodium sulfide, mercaptan, monosulfide, disulfide, X-group, Z-group, B-group
1956-005
リグノスルホン酸中の酸性基について（第一報）佐藤孝一
国策パルプ株式会社
Acidic groups in lignosulfonic acid (I)Koichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: sulfonic acid group, carboxylic acid group, guaiacyl-type, phenolic hydroxyl group, condensed
phenolic hydroxyl group, X-group, Z-group, B-group
1956-006
リグノスルホン酸の鞣皮性と多分子性
京極与寿郎、八浜義和
大阪大学工学部
1

Tannability and multimolecularity of lignosulfonic acidYojuro Kyogoku, Yoshikazu Hachihama
Faculty of Engineering, Osaka University
Keywords: degree of sulfonation, tannability, multimoleculurarity
1956-007
幼植物のリグニン形成について
石川久雄、高市克美、喜多川重樹、沖 妙
愛媛大学農学部
Formation of lignin in juvenile plantHisao Ishikawa, Katumi Takaiti, Sigeki Kitagawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: shikimic acid, phenylalanine, tyrosine, coniferin, syringin, coniferyl alcohol, peroxidase,mung bean, Robinia pseudoacacia,
1956-008
植物体中におけるリグニンの形成機構
樋口隆昌、川村一次
岐阜大学農学部
Formation mechanism of lignin in plant
Takayoshi Higuchi, Ichiji Kawamura
Faculty of Agriculture, Gifu University
Keywords: phenylalanine, coniferin, β-glucosidase, coniferyl alcohol, peroxidase, laccase
1956-009
リグニンの呈色機構に関する研究
右田伸彦、中野準三、平川公夫
東京大学農学部
On the mechanism of color reaction of lignin
Nobuhiko Migita, Junzo Nakano, Kimio Hirakawa
Faculty of Agriculture, the University of Tokyo
Keywords: Mäule color reaction, Cross-Bevan color reaction, phloroglucinol-hydrochloric acid color
reaction
1956-010
リグニンの呈色について
中村徳郎*１、北浦貞男*２*１
興国人絹パルプ株式会社、*２九州大学生産研究所
On the color reaction of lignin
Tokurou Nakamura*1, Sadao Kitaura*２*1
Koukoku Jinken Pulp Co. Ltd. *2 Institute of Industrial Science, Kyusyu University
Keywords: chromopholic group, coniferaldehyde, Schiff’s reagent
1956-011
リグニンの水添分解に関する研究
榊原 彰、荒木 正
林業試験場
Hydrogenolysis of lignin
Akira Sakakibara, Tadasi Araki
Forestry and Forest Product Research Institute
Keywords: hydrogenolysis, residual lignin from wood saccharification, sulfite spent liquor
1956-012
リグニンに関する研究（第 3 報）低スルホン化木紛のエタノリシスについて2

石原達夫、近藤民雄
林業試験場
Studies on lignin (III), Ethanolysis of sulfonated wood meal
Tatsuo Ishihara, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: ethanolysis, Hibbert’s ketones, guaiacylglycerol, structure moiety A by Erdtman
1956-013
リグニンの分解に関する研究（第 1 報）ニトロベンゼン酸化生成物について
田中次郎、近藤民雄
林業試験場
Studies on degradation of lignin (I), Nitrobenzene oxidation products
Jiro Tanaka, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: vanillin, paperchromatography, quantitative determination by UV absorption
1956-014
木材糖化リグニンの性状（続）岡部次郎、八浜義和
大阪大学工学部
Properties of residual lignin from wood saccharification
Jiro Okabe, Yoshikazu Hachihama
Department of Engineering, Osaka University
Keywords: nitrobenzene oxidation, Klason lignin, vanillin
1956-015
竹リグニンの研究
大野一月、三浦克己
大阪府立大学工学部
Studies on bamboo lignin
Kazuki Ono, Katsumi Miura
Department of Engineering, Osaka Prefectural University
Keywords: nitrobenzene oxidation, paper chromatography, kraft cooking
1956-016
リグニン多糖類複合体とパルプ原木の近似組成の関係
本田真一
浜松商科短期大学
Similarity in composition between pulp wood and lignin-carbohydrate complex
Shinichi Honda
Hamamatsu Commercial College
Keywords: hardwood, conifer, furfural, pentose3

第 2 回 (1957.11.15) 東京、紙パルプ会館
1957-001
幼植物のリグニン形成について（第 8 報）
石川久雄、高市克美、沖 妙
愛媛大学農学部
Formation of lignin in juvenile plant (VIII)
Hisao Ishikawa, Katsumi Takaichi, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: aromatic amino acid, tannin, shikimic acid, phenylalanine, tyrosine
1957-002
コニフェリールアルコール重合に関与するフェノールオキシダーゼについて
樋口隆昌、川村一次、井藤佳美
岐阜大学農学部
On the phenol oxidase responsible for polymerization of coniferyl alcohol
Takayoshi Higuchi, Ichiji Kawamura, Yosimi Ito
Faculty of Agriculture, Gifu University
Keywords: laccase, peroxidase, tyrosinase, dehydrogenative polymerization
1957-003
リグニンと炭水化物との化学結合に関する研究（第 5 報）小麦藁中におけるフェノールグルコサイド結合の存在について
林 晄、 館 勇
京都大学農学部
Studies on the chemical linkages between lignin and carbohydrates (V), Presence of phenylglucoside bonds inwheat straw
Akira Hayashi, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: acetylated xylolignin, dioxane lignin, UV spectra
1957-004
樹皮のリグニンについて
幡 克美、十河村男
香川大学農学部
On lignin in barkKatsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: dioxane lignin, Willstätter lignin, nitrobenzene oxidation, Pinus densiflora,
1957-005
消石灰による S.P.廃液中の L.S.の沈澱について
北浦貞男、上野雄造
九州大学農学部
On the precipitation of lignosulfonic acid by calcium hydroxide from sulfite spent liquor
Sadao Kitaura, Yuzo Ueno
Faculty of Agriculture, Kyusyu University
Keywords: carbohydrates, glucose, mannose, galactose, arabinose, xylose
1957-006
リグニンスルホン酸の沈降恒数の測定
京極与寿郎、八浜義和
大阪大学工学部
Determination of sedimentation coefficient of lignosulfonic acid4

Yoshiro Kyogoku, Yoshikazu Hachihama
Faculty of Engineering, Osaka university
Keywords: molecular weight, diffusion coefficient, sulfite spent liquor
1957-007
赤外線吸収スペクトルによるリグニンの研究
祖父江寛、福原節雄
東京大学工学部
Studies on lignin by infrared spectroscopy
Hiroshi Sobue, Setsuo Fukuhara
Faculty of Engineering, the University of Tokyo
Keywords: Brauns’s native lignin, beech, Picea jezoensis, spruce, Cryptomeria japonica, holocellulose
1957-008
リグニンのベンジルアルコール性 OH 基の新反応と考えられるチオ尿素とリグニンとの反応について
三川 礼
国策パルプ株式会社
Reaction of lignin with thiourea – A new reaction of benzyl alcoholic hydroxyl group in lignin
Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: lignin, thiourea, benzyl alcoholic hydroxyl group, X-group, Z-group
1957-009
リグニンモデル化合物の硫化に関する研究
石原達夫、近藤民雄
林業試験場
Studies on the reaction of lignin model compounds with hydrogen sulfide
Tatsuo Ishihara, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: hydrogen sulfide, benzyl alcohol, benzyl ether, thioxane
1957-010
ベンジルグループの hydrogenolysis
右田伸彦、中野準三、石津 敦
東京大学農学部
Hydrogenolysis of benzyl group
Nobuhiko Migita, Junzo Nakano, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: benzyl alcohol, benzyl ether, aromatic hydroxyl group, methanol lignin
1957-011
リグニンの臭素化について
北浦貞男、中村徳郎
九州大学農学部
On the bromination of lignin
Sadao Kitaura, Tokurou Nakamura
Faculty of Agriculture, Kyusyu University
Keywords: Abies sachaliensis, substitution reaction, lignin model compounds, native lignin
1957-012
パルプ漂白の際のリグニンの挙動について
佐藤孝一郎、海老沢きよ
国策パルプ株式会社
Behavior of lignin during bleaching of pulp
5

Koichiro Sato, Kiyo Ebisawa
Kokusaku Pulp Co., Ltd.
Keywords: bleaching, chlorination, lignosulfonic acid, hydrochlonic acid lignin, thiolignin, carbonyl group
1957-013
ハドロトロピック塩による脱リグニン
右田伸彦、中野準三
東京大学農学部
Delignification by hydrotropic salt
Nobuhiko Migita, Junzo Nakano, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: beech, sodium xylenesulfonate, semichemical pulp, dissolving kraft pulp, kraft pulp
1957-014
ハドロトロピックリグニンの酸化
万木 正、鈴木英吉
繊維工業試験所
Oxidation of hydrotropic lignin
Tadashi Yurugi, Eikichi Suzuki
Institute of Fiber Science and Technology
Keywords: beech, nitrobenzene oxidation, guaiacyl group, syringyl group.
1957-015
広葉樹リグニンのニトロベンゼン酸化生成物
田中次郎、近藤民雄
林業試験場
Nitrobenzene oxidation products from hardwood lignin
Jiro Tanaka, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: beech, condensed structure, dehydrodivanillin
1957-016
リグニンの水素添加分解物の硝酸酸化
岡部次郎*1，八浜義和*2*1
山陽パルプ，*2 阪大工
Nitric acid oxidation of hydrocracking products of lignin
Jiro Okabe*1, Yoshikazu Hachihama*2*1
Sanyo Pulp Co., Ltd., *2 Faculty of Engineering, Osaka University
Keywords: lignin, hydrogenolysis, Nitric acid oxidation, adipic acid
1957-017
鞣剤としてのリグニンスルホン酸
千手諒一
九州大学農学部
Lignin sulfonic acid as a tanning agent
Ryoichi Senju
Faculty of Agriculture, Kyusyu University
Keywords: plant tannin, adsorption of tanning agent, diffusion of tanning agent
1957-018
リグニンスルホン酸の酸化
祖父江寛、斉藤吉民
東京大学工学部
Oxidation of lignosulfonic acid6

Hiroshi Sobue, Yoshitami Saito
Faculty of Engineering, the University of Tokyo
Keywords: sulfite spent liquor, oxidation by sodium hydroxide, vanillin
1957-019
バニリンより高分子化合物の合成に関する研究
舘 勇、村上浩二
京都大学農学部
Studies on the synthesis of macromolecular compounds from vanillin
Isamu Tachi, Koji Murakami
Faculty of Agriculture, Kyoto University
Keywords: polyurethane, polyamide urethane, polyester
1957-020
6（及び 7-）-カルボキシ-2-ヒドロキシメチル-1,4-ベンゾジオキサンより生成するポリエステル繊維の製造研究
万木 正、長谷川正木
繊維工業試験場
Production of polyester fiber from 6-(or 7-)-carboxy-2-hydroxymethyl-1,4-benzodioxane
Tadashi Yurugi, Masaki Hasegawa
Institute of Fiber Science and Technology
Keywords: protocatechuic acid, epichlorohydrin7

第 3 回 (1958.11.04) 九州大学農学部
1958-001
プロトリグニンの臭素化について
中村徳郎、北浦貞男
九州大学農学部
On the bromination of protolignin
Tokurou Nakamura, Sadao Kitaura
Faculty of Agriculture, Kyusyuu University
Keywords: Abies sachaliensis, lignin model compound, dehydrogenative polymer, urushi laccase
1958-002
リグニンの生成母体の生成に関する研究
石川久雄、沖 妙
愛媛大学農学部
Studies on the biosyntheses of lignin precursors
Hisao Ishikawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: biosynthesis, shikimic acid, phenylalanine, tyrosine, gallotannin
1958-003
幼植物のリグニンについて
川村一次
岐阜大学農学部
On the lignin in juvenile plant
Ichiji Kawamura
Faculty of Agriculture, Gifu University
Keywords: Pinus Thunbergii, Robinia pseudoacacia, guaiacyl nucleus, syringyl nucleus, methoxyl content
1958-004
リグニンと炭水化物との化学結合に関する研究（第 6 報）小麦藁のジメチルホルムアミド抽出物について
林 晄、 館 勇
京都大学農学部
Studies on the chemical bond between lignin and carbohydrates (VI), Dimethylformamide extracts from wheat
straw
Akira Hayashi, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: lignin-carbohydrate complex, milled wood lignin,
1958-005
針葉樹及び広葉樹に生育した寄生木（やどりぎ）のリグニンについて
中島浩二、八浜義和、F.E. Brauns
大阪大学工学部
On the lignin of mistletoe grown on coniferous trees and broad-leaved trees
Koji Nakajima, Yoshikazu Hachihama, F.E. Brauns
Faculty of Engineering, Osaka University
Keywords: Quercus sp., Pinus ponderosa, Mistletoe pholadendron flavescens, Mäule color reaction,
thioglycolic acid lignin, ethanolysis
1958-006
Lignum Vitae 中のリグニンについて
中島浩二、八浜義和、F.E. Brauns
大阪大学工学部
On the lignin in lignum vitae
8

Koji Nakajima, Yoshikazu Hachihama, F.E. Brauns
Faculty of Engineering, Osaka University
Keywords: Guaiacum officinale, methoxyl content, Mäule color reaction
1958-007
リグニンスルホン酸の高分子化学的性状について
京極与寿郎、八浜義和
大阪大学工学部
Macromolecular properties of lignin sulfonic acid
Yoshiro Kyougoku, Yoshikazu Hachihama
Faculty of Engineering, Osaka University
Keywords: polymolecularity, ion-exchange resin chromatography
1958-008
リグニンのエステルグループ
中野準三、石津 敦、右田伸彦
東京大学農学部
Ester group in lignin
Junzo Nakano, Atsushi Ishizu, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: p-hydroxybenzoic acid, vanillic acid, syringic acid, p-coumaric acid, ferulic acid, Populus
Sieboldii, Populus Maximowiczii
1958-009
リグニンとメルカプタンの反応
石原達夫、近藤民雄
林業試験場
Reaction of mercaptan with lignin
Tatsuo Ishihara, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: hydrogen sufide, ethyl mercaptan, vanillyl alcohol, mercaptolysis
1958-010
広葉樹リグニンのアルカリ分解
田中次郎、近藤民雄
林業試験場
Degradation of hardwood lignin by sodium hydroxide
Jiro Tanaka, Tamio Kondo
Forestry and Forest Product Research Institute
Keywords: beech, sodium hydroxide, 4,4’-dihydroxy-3,3’-dimethoxystilben
1958-011
S.P.廃液のアルカリ溶液に於ける酸化について
舘 勇、浦野信清、赤嶋晋一郎、山本昭
京都大学農学部
Oxidation of sulfite spent liquor in alkaline medium
Isamu Tachi, Nobukiyo Urano, Sinichiro Akashima, Akira Yamamoto
Faculty of Agriculture, Kyoto University
Keywords: vanillin, vanillic acid, yield of vanillin
1958-012
バニリンより高分子化合物の合成に関する研究- -ヒドロキシエトキシ-バニリン酸のポリエステルの性状について舘 勇、村上浩二
9京都大学農学部
Studies on the synthesis of macromolecular compounds from vanillin- On the properties of polyester preparedfromβ-hydroxyethoxy-vanillic acid
Isamu Tachi, Koji Murakami
Faculty of Agriculture, Kyoto University
Keywords: transesterification, catalyst, infrared spectrum
1958-013
バニリン酸誘導体の合成とその高分子物質への応用
長谷川正木
繊維工業試験場
Synthesis of vanillin derivatives and their use for polymer production
Masaki Hasegawa
Institute of Fiber Science and Technology
Keywords: vanillin, vanillic acid, epichlorohydrin, hexamethylene diamine
1958-014
アルカリ性亜硫酸ソーダ蒸解について
坂田 功、千手諒一
九州大学農学部
On the alkaline sulfite cooking
Isao Sakata, Ryoichi Senjyu
Faculty of Agriculture, Kyusyu University
Keywords: Castanopsis sp., sulfonation, delignification
1958-015
未晒パルプより抽出されるリグニンの量的関係
佐藤孝一郎，三川 礼
国策パルプ株式会社Amount of lignin extracted from unbleached pulps
Koichiro Sato, Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: unbleached pulp, beating, dimethysulfoxide, extraction, lignin, lignin-carbohydrate complex

10

第 4 回 (1959.11.13-14) 京大、楽友会館
1959-001
リグニンの生合成に関する研究— ユウガオ果実の木質化に関与する酵素と有機酸の消長について
館 勇、佐藤 惺
京都大学農学部
Studies on the biosynthesis of lignin – Changes in content of enzymes and organic acids related to lignificationof kanpyo, a fruit of Lagenaria siceraria var. hispida
Isamu Tachi, Satoru Sato
Faculty of Agriculture, Kyoto University
Keywords: laccase, peroxidase, shikimic acid, quinic acid
1959-002
14
C−アイソトープに依るリグニン生合成の研究
長谷川正男＊１、樋口隆昌＊２＊１
林業試験場、＊２岐阜大学農学部
Studies on the biosynthesis of lignin using 14C-isotope
Masao Hasegawa, Takayoshi Higuchi＊１
Forestry and Forest Product Research Institute,＊２Faculty of Agriculture, Gifu University
Keywords: phenylpropane, shikimic acid, protocatechuic acid, dehydroshikimic acid
1959-003
リグニン生成母体の形成について
石川久雄、沖 妙
愛媛大学農学部
On the biosyntheses of lignin precursors
Hisao Ishikawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: Bacillus cereus, dehydroshikimic acid, protocatechuic acid, aromatic amino acids
1959-004
ミズナラ樹皮のリグニンについて
幡 克実、十河村男
香川大学農学部
On the lignin in the bark of Japanese oak (Quecus cryspura)
Katsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: dioxane lignin, hydrochloric acid lignin, UV spectra, IR spectra
1959-005
下等植物のリグニンについて（第一報）へゴ及びコフキサルノコシカケのリグニン
川村一次、樋口隆昌、近藤雅春
岐阜大学農学部
On the lignin of lower plants. I. Lignin in Cythea spinulosa and Fomea applanatus.
Ichiji Kawamura,Takayoshi Higuchi, Masaharu Kondo
Faculty of Agriculture, Gifu University
Keywords: wood rotting fungi, color reaction, Klason lignin, dioxane lignin, nitrobenzene oxidation
1959-006
リグニンと炭水化物との化学結合に関する研究
林 晄、 館 勇
京都大学農学部
Studies on the chemical linkages between lignin and carbohydrates
Faculty of Agriculture, Kyoto University
11

Akira Hayashi, Isamu Tachi
Keywords: wheat straw, lignin-carbohydrate complex, sugar composition
1959-007
酢化した木材粉とエチレンオキサイドの反応について
石川久雄、山下謙三
愛媛大学農学部
On the reaction of ethylene oxide with acetylated wood meal
Hisao Ishikawa, Kenzo Yamashita
Faculty of Agriculture, Kagawa University
Keywords: beech, hydroxyethyl lignin, hydroxyethyl cellulose, Brauns’s native lignin
1959-008
リグニンの単離及びリグニンの反応性について
福渡七郎、竹田貴美、宮崎親二郎
島根農科大学On the isolation of lignins and their reactivity
Shichiro Fukuwatari, Takami Takeda, Sinjiro Miyazaki
Shimane Agricultural University
Keywords: kraft lignin, lignosufonic acid, Purves lignin, -ray irradiated lignin
1959-009
脱リグニン反応とその過程について
福渡七郎、安田徳郎、石野荘造、柳浦千里
島根農科大学On the delignification reaction and its process
Shichiro Fukuwatari, Tokuro Yasuda, Shozo Ishino, Chisato Yagiura
Shimane Agricultural University
Keywords: chlorination, holocellulose, Tilia japonica, Pinus densiflora, Eucalyptus, Populus Sieboldii,
Quercus crispula
1959-010
リグニンスルホン酸に関する研究（第一報）
舘 勇*1、林 晄*1、小島義一＊２、東辻 健＊２*1
京都大学農学部、＊２丸菱油脂工業株式会社
Studies on the lignin sulfonic acid (I)Isamu Tachi*1, Akira Hayashi*1, Giichi Kojima＊２, Ken Higashitsuji＊２＊1
Faculty of Agriculture, Kyoto University,＊２Marubishi Oil and Fat Co. Ltd.
Keywords: sulfite waste liquor, separation by extraction, dicyclohexylamine salt
1959-011
リグニンスルホン酸に関する研究（第二報）
舘 勇*1、林 晄*1、小島義一＊２、東辻 健＊２*1
京都大学農学部、＊２丸菱油脂工業株式会社
Studies on the lignin sulfonic acid (II)Isamu Tachi*1, Akira Hayashi*1, Giichi Kojima＊２, Ken Higashitsuji＊２＊1
Faculty of Agriculture, Kyoto University,＊２Marubishi Oil and Fat Co. Ltd.
Keywords: molecular weight, melting point depression method, ethylene carbonate
1959-012
未晒パルプよりジメチルスルホオキサイド抽出した成分について
佐藤孝一郎，小林晃夫
国策パルプ株式会社
Component of dimethysulfoxide extract of unbleached pulps
12

Koichiro Sato, Akio Kobayashi
Kokusaku Pulp Co., Ltd.
Keywords: beating, extraction, lignin, lignin-carbohydrate complex
1959-013
未晒 SP より抽出したリグニンスルホン酸の分子量について
佐藤孝一郎，小林晃夫，三川 礼
国策パルプ株式会社
Molecular weight of lignin sulfonic acid extracted from unbleached sulfite pulp
Koichiro Sato, Akio Kobayashi, Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: dimethysulfoxide, extraction, lignosulfonic acid
1959-014
リグニンの物理化学的研究（第 1 報）微分容量より見たリグニンスルホン酸塩の一考察
上田静男、辻 福寿、林 晄、渡辺 昌、中井章能
京都大学農学部
Physicochemical studies on ligninc Differential capacity of lignosulfonate
Shizuo Ueda, Fukujyu Tsuji, Akira Hayashi, Akira Watanabe, Akiyoshi Nakai
Faculty of Agriculture, Kyoto University
Keywords: dropping mercury electrode, electrical double layer, surface active property
1959-015
リグニンの物理化学的研究（第 2 報）微分容量より見たリグニンスルホン酸塩の一考察
上田静男、辻 福寿、林 晄、渡辺 昌、中井章能
京都大学農学部
Physicochemical studies on lignin (I), Differential capacity of lignosulfonate
Shizuo Ueda, Fukujyu Tsuji, Akira Hayashi, Akira Watanabe, Akiyoshi Nakai
Faculty of Agriculture, Kyoto University
Keywords: electric frequency
1959-016
チオリグニンのポーラログラフイー（第 7 報〉 接触波の活性基について（I）
神田 孝、寺島典二、川上日出国
名古屋大学農学部
Polarography of lignin （VII）, On the active group of thiolignin catalytic wave (1)Takashi Kanda, Noritsugu Terashima, Hidekuni Kawakami
Faculty of Agriculture, Nagoya University
Keywords: Pinus densiflora, reduction, sodium borohydride, Raney nickel
1959-017
ニトロリグニンのポーラログラフイー
永田美之介、北尾弘一郎、舘 勇
京都大学農学部
Polarography of nitrolignin
Yoshinosuke Nagata, Kouichiro Kitao, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: m-nitrophenol, low molecular nitrocompounds
1959-018
Vanillin より高分子化合物の合成に関する研究（第４報）
村上浩二、舘 勇
京都大学農学部
Studies on the synthesis of high polymer from vanillin (IV)13

Koji Murakami, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: vanillic acid, polyamide, solubility
1959-019
リグニンとメルカプタンとの反応
石原達夫
林業試験場
Reaction of lignin and mercaptan
Tatsuo Ishihara
Forestry and Forest Product Research Institute
Keywords: mercaptolysis, ethyl mercaptan, mercaptol, lignin model compounds
1959-020
リグニンの臭素化について
中村徳郎、北浦貞夫
九州大学農学部
On the bromination of lignin
Tokurou Nakamura, Sadao Kitaura
Faculty of Agriculture, Kyusyu University
Keywords: protolignin, sodiumborohydride
1959-021
アルカリリグニンの位にカルポニル基をもつた側鎖構造について
右田伸彦、石津 敦
東京大学農学部
On the -carbonyl side chain structure in alkali lignin
Nobuhiko Migita, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: condensation, acetovanillone, propiovanillone, 3,4-dihydroxypropiovanillone
1959-022
広葉樹リグニンの分解生成物について
田中治郎
林業試験場
On the alkali degradation products of hardwood lignin
Jiro Tanaka
Forestry and Forest Product Research Institute
Keywords: beech, alkali degradation, syringyl ethane
1959-023
バニリンの酸素酸化について
舘 勇、村上浩二、阿部圭二
京都大学農学部
On the oxidation of vanillin with oxygen
Isamu Tachi, Koji Murakami, Keiji Abe
Faculty of Agriculture, Kyoto University
Keywords: oxidation with oxygen, UV absorption spectrum
1959-024
リグニンとフエノールスルホン酸の反応
中島浩二*1、八浜義和*2*1
山陽パルプ株式会社、*2 大阪大学工学部
Reaction of lignin with phenol sulfonic acid14

Koji Nakajima*1 , Yoshikazu Hachihama*2*1
Sanyo Pulp Co. Ltd, *2Faculty of Engineering, Osaka University
Keywords: Brauns’s native lignin, condensation, Japanese red pine
1959-025
高分子凝集剤によるリグニンの沈澱（第 2 報）佐々木壮吉
東京工業試験所
Precipitation of lignin by polymer flocculant (II)Sokichi Sasaki
The Government Chemical Industrial Research Institute, Tokyo
Keywords: sulfite waste liquor, dicyanodiamide, formalin, semichemical pulp waste liquor
1959-026
広葉樹リグニンスルホン酸に関する研究
京極与寿郎、位田博敏、八浜義和
大阪大学工学部
Studies on the hardwood lignin sulfonic acid
Yoshiro Kyogoku, Hirotoshi Ida, Yoshikazu Hachihama
Faculty of Engineering, Osaka University
Keywords: beech, heterogeneity, polymolecularity, nitrobenzene oxidation
1959-027
リグニンの利用に関する研究
舘 勇、林 晄、山本 昭
京都大学農学部
Studies on the utilization of lignin
Isamu Tachi, Akira Hayashi, Akira Yamamoto
Faculty of Agriculture, Kyoto University
Keywords: tanning agent, lignin sulfonic acid, oxidized lignin sulfonic acid
1959-028
リグニン及び木材に対する放射線の作用
高椋節夫、八浜義和
大阪大学工学部
Effect of radiation on lignin and wood
Setsuo Takamuku, Yashikazu Hachihama
Faculty of Engineering, Osaka University
Keywords: Japanese red pine, spruce, cobalt 60, Brauns’s native lignin, infrared spectrometry
1959-029
リグニンに対する放射線照射効果
祖父江寛，上埜武夫
日本放射線高分子研究協会
Effect of radiation on lignin
Hiroshi Sobue, Takeo Ueno
Japan Radiation Polymer Research Association
Keywords: γ-ray, irradiation, paramagnetic resonance spectroscopy, free radical

15

第 5 回 (1960.11.19-20) 名古屋、商工会議所
1960-001
リグニンの高圧水素添加分解
鹿島 覚、長田 武、田畑晴朗、渡辺 浩、久保輝雄
野口研究所
Hydrocracking of lignin
Satoru Kashima, Takeshi Nagata, Haruo Tabata, Hiroshi Watanabe, Teruo Kubo
Noguchi Institute
Keywords: liquefaction rate, p-cresol, 4-ethylphenol, pyrocatechol
1960-002
リグニンの高圧水添分解に関する研究
榊原 彰、荒木 正
林業試験場
Studies on the hydrogenolysis of lignin
Akira Sakakibara, Tadashi Araki
Forestry and Forest Product Research Institute
Keywords: phenol, cresols, catechols, xylenols, ethylphenol
1960-003
リグニンスルホン酸に関する研究（VII) 水溶液の電導度並びに拡散係数について
小島義一、中井章能、舘 勇
京都大学農学部
Studies on the lignin sulfonic acid. VII. Electric conductivity and diffusion coefficient of the aqueous solution
Giichi Kojima, Akiyosi Nakai, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: electric conductivity, diffusion coefficient, micelle formation, association
1960-004
リグニンスルホン酸に関する研究（VIII） 非水溶媒中による分別
小島義一、東辻 健、林 晄、舘 勇
京都大学農学部
Studies on the lignin sulfonic acid (VIII), Fractionation by nonaqueous solvents
Gi-ichi Kojima, Ken Azumatsuji, Akira Hayashi, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: dicyclohexylamine salt, molecular weight, fractional precipitation, molecular weight
1960-005
リグニンスルホン酸に関する研究（IX）非水溶媒中における粒度の測定
小島義一、林 晄、舘 勇
京都大学農学部
Studies on the lignin sulfonic acid (IX), Determination of particle size in nonaqueous solvents
Gi-ichi Kojima, Akira Hayashi, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: dicyclohexylamine salt, dicyclohexylamine hydrochloric acid salt, dissociation
1960-006
光散乱法によるリグニンスルホン酸塩の研究
鈴木 勇*1，京極与寿郎*2，八浜義和*2*1
国策パルプ株式会社，*2 大阪大学工学部
Studies on light scattering spectrophotometry of lignosulfonate
Isamu Suzuki*1, Yoshiro Kyogoku*2, Yoshikazu Hachihama*2*1
Kokusaku Pulp Co., Ltd., *2Osaka University, Faculty of Technology
16Keywords:

light scattering spectrophotometry, lignosulfonate, molecular weight

1960-007
リグニンの物理化学的研究（第 3 報）
上田静男、渡辺 昌、辻 福寿
京都大学化研究所
Physicochemical study of lignin (III)Shizuo Ueda, Akira Watanabe, Fukutoshi Tsuji
Institute for Chemical Research, Kyoto University
Keywords: electric conductivity, micelle formation, molecular weight
1960-008
リグニンのポーラログラフイー（第 9 報）接触波の活性基について（3）神田 孝、寺島典二、川上日出国
名古屋大学農学部
Polarography of lignin (IX) On the active group of thiolignin catalytic wave (3)Takashi Kanda, NoritsuguTerashima, Hidekuni Kawakami
Faculty of Agriculture, Gifu University
Keywords: thiolignin, sodalignin, lignin model compounds, carbonyl group
1960-009
ナギ、ラカンマキ及びイチョウ材のリグニンについて
川村一次、樋口隆昌
岐阜大学農学部
On the lignin in Podocarpus nagi, Podocarpus chinensis and Ginkgo biloba
Ichiji Kawamura, Takayoshi Higuchi
Faculty of Agriculture, Gifu University
Keywords: Mäule color reaction, nitrobenzene oxidation, milled wood lignin, UV absorption spectrum, IRabsorption spectrum
1960-010
アカマツ樹皮フエノール酸の性状
幡 克美、十河村男
香川大学農学部
Properties of phenolic acids in the bark of red pine
Katsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: ethanolysis, protocatechualdehyde, methoxyl group content
1960-011
リグニンと炭水化物との化学結合に関する研究
林 晄
立命館大学理工学部
Studies on the chemical bonds between lignin and carbohydrates
Akira Hayashi
College of Science and Engineering, Ritsumeikan University
Keywords: DMF extractives, phenol glucoside bond, uronic acid ester bond
1960-012
リグニンの単離及び反応性について（II）フエノール及びアニリンとの結合反応について
福渡七郎、渡辺 寿、安田徳郎
島根農科大学
On isolation and reactivity of lignin (II), Reaction with phenol and anilin
Hichirou Fukuwatari, Hisashi Watanabe, Tokurou Yasuda
17

Shimane University of Agriculture
Keywords: soda pulp lignin, sulfate pulp lignin, sulfuric acid lignin, -ray lignin
1960-013
グアヤコールの塩素水による塩素化について
佐藤孝一郎，小林晃夫，三川 礼
国策パルプ株式会社
Chlorination of guaiacol with aqueous chlorine solution
Koichiro Sato, Akio Kobayashi, Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: guaiacol, aqueous chlorine solution, chlorination, methoxyl group, methanol
1960-014
リグニン中のフエノール性水酸基のヒドロオキシエチル化について
石川久雄、沖 妙
愛媛大学農学部
On the hydroxyethylation of phenolic hydroxyl groups in lignin
Hisao Ishikawa, Tae Oki,
Faculty of Agriculture, Ehime University
Keywords: beech, neutral sulfite pulping, guaiacyl-syringyl lignin, UV spectrum
1960-015
芳香核カルポン酸形成に関与する酵素系について
石川久雄、沖 妙
愛媛大学農学部
On the enzymes participate in formation of aromatic carboxylic acids
Hisao Ishikawa, Tae Oki,
Faculty of Agriculture, Ehime University
Keywords: Bacillus cereus, shikimic acid, 5-dehydroshikimic acid, dehydroshikimic acid dehydrase
1960-016
リグニンの生合成に関する研究、 ユウガオ果実の木質化に関与する酵素とコニフェリルアルコールの酸化について
佐藤 惺、舘 勇
京都大学農学部
Studies on the biosynthesis of lignin. Enzymes related to lignification of kanpyo, a fruit of Lagenaria siceraria
var. hispida and oxidation of coniferyl alcohol
Akira Sato, Isamu Tachi
Faculty of Agriculture, Kyoto University
Keywords: laccase, peroxidase, dehydrogenative polymerization products (DHP)
1960-017
過酸化物によるリグニンの酸化
尾上史郎，大久保正道，池田健郎
山陽パルプ株式会社
Oxidation of lignin with peroxides.
Shiro Onoe, Masamichi Okubo, Kenro Ikeda
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, lignin, peroxide, barium peroxide, oxidation, vanillin, vanillic acid
1960-018
過マンガン酸カリ酸化分解による椈リグニンの p−ヒドロキシフエニル核の検索藤井俊太郎*1、京極与寿郎*2、八浜義和*2*1
興国人絹パルプ株式会社、*2 大阪大学工学部
18

Search of p-hydroxyphenyl nucleus in beech lignin by potassium permanganate oxidation*1
Shuntaro Fujii, *2Yojyuro Kyogoku, *2Yoshikazu Hachihama*1
Koukoku Jinken Pulp Co. Ltd, *2Faculty of Engineering, Osaka University
Keywords: p-hydroxyphenyl nucleus, paper chromatography, condensed structure
1960-019
硫化物により生成するアセトバニロン構造の起源
右田伸彦、石津 教
東京大学農学部
Origin of acetovanillone structure formed by sodium hydrosulfide cooking of wood
Nobuhiko Migita, Atsusi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: retro-aldol reaction, lignin model compounds
1960-020
リグニン加水分解物としてのコニフェリルアルコールの生成
榊原 彰、中山信子
林業試験場
Formation of coniferyl alcohol as a hydrolysis product of lignin
Akira Sakakibara, Nobuko Nakayama
Forestry and Forest Product Research Institute
Keywords: Yezo spruce, Picea jezoensis, coniferyl aldehyde, dehydrodiconiferyl alcohol
1960-021
アルカリ分解物としてのシリンギルエタン
田中治郎
林業試験場
Syringylethane as an alkaline degradation product of lignin.
Jiro Tanaka
Forestry and Forest Product Research Institute
Keywords: beech, Fagus crenata, syringylethane19

第 6 回 (1961.11.18-19) 大阪、府立農林会館
1961-001
Björkman リグニンについてJohn S．Fujii．中野準三、Bengt Rånby
ニューヨーク州立大学
Studies on the Björkman lignin
John S．Fujii, Junzo Nakano, Bengt RånbyNew York State University
Keywords: polystyrene, change of molecular weight, free-radical, toluene
1961-002
リグニンのポーラログラフイー
寺島典二、神田 孝
名古屋大学農学部
Polarography of lignin
Noritsugu Terashima, Takashi Kanda
Faculty of Agriculture, Nagoya University
Keywords: thiolignin, imine cobalt chelate compound,
1961-003
幼植物のリグニンについて（第 3 報）ニセアカシアの MWL の赤外および紫外線吸収曲線につ いて
川村一次、樋口隆昌
岐阜大学農学部
On the juvenile plant lignin (III), Infrared and ultraviolet absorption spectra of MWL from locust tree
Ichiji Kawamura, Takayoshi Higuchi
Faculty of Agriculture, Gifu University
Keywords: Mayapis, Shorea palosapis, Ginkgo, Ginkgo biloba
1961-004
リグニンの単離および単離リグニンの反応性
福渡七郎、久下 喬
島根農科大学
Isolation and reactivity of lignin
Shichiro Fukuwatari, Takashi Kuge
Shimane University of Agriculture
Keywords: soda lignin, thiolignin, sulfuric acid lignin
1961-005
クラフト蒸煮における硫化物の役割
石津 敦、右田伸彦
東京大学農学部
Role of sulfide in kraft cooking
Atsushi Ishizu, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compound, veratrylglycerol- -guaiacyl
-hydroxypropioveratrone, pH, sulfidity
1961-006
亜硫酸パルプ廃液よりリグニンを採取する方法について
久保輝雄、鹿島 寛
野口研究所
Separation of lignin from sulfite pulping black liquor
Teruo Kubo, Hiroshi Kashima
20

ether,

-(2-methoxyphenoxy)-Noguchi Institute
Keywords: lignosulfonate, concentrated black liquor
1961-007
リグニン水素添加分解生成物の分析 — モノフェノール類について
渡辺 浩、鹿島 寛
野口研究所
Analysis of lignin hydrogenolysis products, – Monophenols
Hiroshi Watanabe, Hiroshi Kashima
Noguchi Institute
Keywords: phenol, o-cresol, p-cresol, p-ethylphenol, 2,4-xylenol, p-n-propylphenol
1961-008
リグニンの水素添加分解について
尾上史郎，大久保正道，岡部次郎
山陽パルプ株式会社
Hydrocracking of lignin
Shiro Onoe, Masamichi Okubo, Jiro Okabe
Sanyo Pulp Co., Ltd.
Keywords: wood meal, hydrochloric acid lignin, sulfuric acid lignin, lignosulfonic acid, Raney-nickel
1961-009
リグニンの水素添加分解に関する研究
榊原 彰*1、阿部 勲*２*1
林業試験場、*２北海道林産試験場
Hydrogenolysis of lignin
Akira Sakakibara*1, Isao Abe*２*1
Forestry and Forest Products Research Institute, *2Hokkaido Forest Products Research Institute
Keywords: catalyst, low-boiling point phenols
1961-010
ジオキサンー水によるリグニンの加水分解（第 2 報）
榊原 彰、中山信子
林業試験場
Hydrolysis of lignin with dioxane and water
Akira Sakakibara, Nobuko Nakayama
Forestry and Forest Product Research Institute
Keywords: Klason lignin, Yezo spruce, Picea jezoencis, beech, Fagus crenata
1961-011
木材のアセチルブロマイドによる分解
田中治郎、榊原 彰
林業試験場
Degradation of wood by acetyl bromide
Jiro Tanaka, Akira Sakakibara
Forestry and Forest Products Research Institute
Keywords: syringyl ethane, beech, degradation by alkali
1961-012
木材加水分解リグニンの利用について 1. アルカリによる活性化
森 滋*1、山岸祥恭*1、半沢道郎*2、川瀬 清*2、笹谷宣志*2*1
北海道林産試験場、*2 北海道大学農学部
Utilization of wood hydrolysis lignin, I. Activation by alkali treatment
Shigeru Mori*1, Yoshiyasu Yamagishi*1, Michio Hanzawa*2, Kiyoshi Kawase*2, Takashi Sasaya*2
21

*1

Hokkaido Forest Products Research Institute, *2Faculty of Agriculture, Hokkaido University
Keywords: Betula platyphylla, acid hydrolysis lignin, phenol resin
1961-013
木材加水分解リグニンの利用について 2. 硫酸による活性炭の製造
半沢道郎、里中聖一、氏家雅男
北海道大学農学部
Utilization of wood hydrolysis lignin (II), Production of activated charcoal using sulfuric acid
Michio Hanzawa, Seiichi Satonaka, Masao Ujiie
Faculty of Agriculture, Hokkaido University
Keywords: white birch, Betula platyphylla, acid hydrolysis lignin, methylene blue
1961-014
中性亜硫酸セミケミカルパルプ廃液中のリグニンの性状並びに定量法の検討
幡 克美、十河村男
香川大学農学部
Properties and quantitative analysis of lignin in waste liquor of neutral sulfite semi-chemical pulping
Katsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: tannin, tannin sulfonic acid, lignin sulfonic acid, colloid titration method
1961-015
中性亜硫酸セミケミカルパルプ廃液のイオン交換樹脂膜透析
幡 克美、十河村男
香川大学農学部
Dialysis of waste liquor of neutral sulfite semi-chemical pulping through ion-exchange resin membranes
Katsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: lignin sulfonic acid, free inorganic salt
1961-016
リグニンスルホン酸による可溶化（I）
林 晄、舘 勇、小島義一、東辻 健、坂口 享
京都大学農学部
Solubilization by lignosulfonate (I)Akira Hayashi, Isamu Tachi, Giichi Kojima, Ken Higashitsuji, Toru Sakaguchi
Faculty of Agriculture, Kyoto University
Keywords: electric conductivity, diffusion coefficient, surface tension
1961-017
リグニンスルホン酸による可溶化（II）
林 晄、舘 勇、東辻 健、坂口 享, 小島義一
京都大学農学部
Solubilization by lignosulfonate (II)Akira Hayashi, Isamu Tachi, Takeshi Azumatsuji, Ken Higashitsuji, Giichi Kojima
Faculty of Agriculture, Kyoto University
Keywords:pinocyanol chloride, micelle formation
1961-018
重クロム酸加里によるリグニンのゲル化機構について
千手諒一、阿部 光
九州大学農学部
Gelation mechanism of lignin by potassium dichromate
Ryoichi Senjyu, Hikaru Abe
22

Faculty of Agriculture, Kyusyu University
Keywords: electric conductivity, thiolignin, cross linking
1961-019
リグニンスルホン酸の分子形態についての考察
京極与寿郎、八浜義和
大阪大学工学部
Consideration for molecular configuration of lignin sulfonic acid
Yoshiro Kyogoku, Yoshikazu Hachihama
Faculty of Engineering, Osaka University.
Keywords: molecular weight, sedimentation coefficient, viscosity
1961-020
リグニンの物理化学的研究（第 3 報）微分容量と吸着動力学
上田静男、辻 福寿、渡辺 昌
京都大学化学研究所
Physicochemical study of lignin (III), Differential capacity and adsorption dynamics
Shizuo Ueda, Fukujyu Tsuji, Akira Watanabe
Chemisrtry Institute, Kyoto University
Keywords: dropping mercury electrode1961-021
リグニンの物理化学的研究（第 4 報）リグニンスルホン酸(LSA)イオンの水銀面への吸着エネルギー
上田静男、辻 福寿、渡辺 昌
京都大学化学研究所
Physicochemical study of lignin (IV), Adsorption energy of lignin sulfonic acid ion on mercury surface
Shizuo Ueda, Fukujyu Tsuji, Akira Watanabe
Institute for Chemical Research, Kyoto University
Keywords: surface active agent, electrical double layer
1961-022
単離した塩素化リグニンスルホン酸バリウムについて
佐藤孝一郎、小林晃夫、三川 礼
国策パルプ株式会社
Properties of isolated chlorinated barium lignosulfonate
Koichiro Sato, Akio Kobayashi, Rei Mikawa
Kokusaku Pulp Co., Ltd.
Keywords: acidic groups, carboxylic group, molecular weight，potentiometric titration
特別講演
米国リグニン化学討論会に出席して
鹿島 寛
野口研究所
1961-Invited lecture:
A report on the Lignin Chemistry Symposium in USA.
Hiroshi Kashima
Noguchi Institute23

第 7 回 (1962.10.04-05) 北海道大学クラーク会館
1962-001
リグニンの単離及び単離リグニンの反応性（IV） 特にヂメチルスルフオキサイド・リグニンについて
福渡七郎、久下 喬、神保幹夫
島根農科大学
Isolation of lignin and reactivity of the isolated lignin (IV), On the dimethylsulfoxide-lignin
Shichiro Fukuwatari, Takashi Hisashita, Mikio Jinbo
Shimane University of Agriculture
Keywords: red pine, Pinus densiflora, methoxyl content, UV absorption spectrum, hydroxyl group content
1962-002
Mäule 反応の呈色機構（VI）
中野準三、右田伸彦
東京大学農学部
Mechanism of Mäule color reaction (VI)
Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo.
Keywords: biosynthetic lignin, DHP, infrared absorption spectrum
1962-003
ヂオキサンー水によるリグニンの加水分解（第 4 報）
榊原 彰、 中山信子
林業試験場
Hydrolysis of lignin by dioxane-water (IV)
Akira Sakakibara, Nobuko Nakayama
Forestry and Forest Products Research Institute
Keywords: guaiacylglycerol
1962-004
液体アンモニヤ中の金属ナトリウムによるリグニンの分解
榊原 彰, 山口 彰
林業試験場
Degradation of lignin by metallic sodium in liquid ammonia
Akira Sakakibara, Akira Yamaguchi
Forestry and Forest Products Research Institute
Keywords: Picea jezoensis, dihydroeugenol, guaiacylglycerol
1962-005
リグニンの水素化分解に関する研究
榊原 彰*1、尾田勝夫*1、阿部 勲*2*1
林業試験場、*2 北海道林産試験場
Hydrogenolysis of lignin
Akira Sakakibara*1, Masao Oda*1, Isao Abe*2*1
Forestry and Forest Products Research Institute, *2Hokkaido Forest Produvts Research Institute
Keywords: catalyst, nickel carbonyl, iron carbonyl, catechols
1962-006
リグニンのメルカプトリシスについて
石原達夫、榊原 彰
林業試験場
Mercaptolysis of lignin
Tatsuo Ishihara, Akira Sakakibara
Forestry and Forest Products Research Institute24

Keywords:

Picea jezpensis, mercaptolysis products, structure of products

1962-007
竹リグニンに関するする研究（第 2 報）ニトロベンゼン酸化による p-ヒドロキシべンズアルデヒの成因
前田信夫、五十野善四郎、大野一月
大阪府立大学農学部
Studies on the bamboo lignin (II), Origin of p-hydroxybenzaldehyde by nitrobenzene oxidation
Nobuo Maeda, Zenshiro Isono, Kazuki Ono
Faculty of Agriculture, Osaka Prefecture University
Keywords: p-hydroxyphenyl nucleus, Hibbert’s ketones, p-coumaric acid
1962-008
リグニンスルホン酸バリウムの分散性
小林晃夫，葉賀忠昭，佐藤孝一郎
国策パルプ株式会社
Dispersing ability of barium lignosulfonate
Akio Kobayashi, Tadaaki Haga, Koichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: molecular weight, sulfonic group
1962-009
リグニンスルホン酸のポーラログラフによる定量
林 晄、山条弘子*1、小島義一*2*1
立命館大学理工学部、*2 丸菱油脂株式会社
Quantitative determination of lignin sulfonic acid by polarography
Akira Hayashi*1, Hiroko Yamajyo*1, Gi-ichi Kojima*2*1
College of Science and Engineering, Ritsumeikan University, *2Marubishi Oil Chemical Co. Ltd
Keywords: methylene blue, catalytic wave
1962-010
リグニンスルホン酸のキレート作用（1）林 晄、山条弘子、羽下利勝
立命館大学理工学部
Chelating property of lignosulfonic acid (I)Akira Hayashi, Hiroko Yamajyou, Toshikatsu Hage
College of Science and Engineering, Ritsumeikan University
Keywords: polarography, ferric ion, catalytic wave
1962-011
リグニンスルホン酸のキレート作用（2）林 晄、山条弘子、扇孝三郎
立命館大学理工学部
Chelating property of lignosulfonic acid (II)Akira Hayashi, Hiroko Yamajyou, Kozaburo Ougi
College of Science and Engineering, Ritsumeikan University
Keywords: polarography, ferric ion, catalytic wave, titration curve, ionic linkage
1962-012
リグニンスルホン酸と塩素との反応
尾上史郎，大久保正道，中島浩二
山陽パルプ株式会社
Reaction of lignosulfonic acid with chlorine
Shiro Onoe, Masamichi Okubo, Koji Nakajima
Sanyo Pulp Co., Ltd.
25

Keywords:

sulfite pulp, spent liquor, lignosulfonic acid, chlorination, oxidation, substitution

1962-013
イオン交換繊維によるリグニンスルホン酸の吸着平山謙三郎，日向明，加藤正明
東洋紡績株式会社
Adsorption of lignosulfonetes with ion-exchange cellulose fiber
Kenzaburo Hirayama, Akira Hyuga, Masaaki Kato
Toyobo Co., Ltd.
Keywords: sulfite spent siquor, lignosulfonates, anion-exchange resin, ion-exchange cellulose, aminoethyl
cellulose
1962-014
腐朽材のリグニン
川瀬 清
北海道大学農学部
Lignin in rotten wood
Kiyoshi Kawase
Faculty of Agriculture, Hokkaido University
Keywords: UV spectrometric analysis
1962-015
モクマオウ及びバッカリス材のリグニンについて
川村一次、樋口隆昌
岐阜大学農学部
Studies on the lignin in Casuarina equisetifolia and Baccharis halimifolia
Takamasa Higuchi, Ichiji Kawamura
Faculty of Agriculture, Gifu University
Keywords: Mäure color reaction, Cross Bevan color reaction, IR absorption specrum, dioxane lignin
1962-016
セミケミカルパルプ廃夜中のリグニンの性状 −とくにメトキシル基について
幡 克美、十河村男
香川大学農学部
Properties of lignin in waste liquor of semi-chemical pulping, especially on the methoxyl content
Katsumi Hata, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: chestnut, beech, nitrobenzene oxidation, syringaldehyde, vanillin
1962-017
N−L 材混合チオリグニンの IR 吸収
杉松昭人，岩田秀子
国策パルプ株式会社
Infrared spectroscopy of a mixture of softwood and hardwood thiolignins
Akihito Sugimatsu, Hideko Iwata
Kokusaku Pulp Co., Ltd.
Keywords: thiolignin, softwood, hardwood, mixture ratio, infrared spectroscopy
1962-018
チオリグニンの過安息香酸分解について
鍵野豊祐、中野準三、右田伸彦
東京大学農学部
Degradation of thiolignin by perbenzoic acidToyosuke Kagino, Junzo Nakano, Nobuhiko Migita
26

Faculty of Agriculture, the University of Tokyo
Keywords: acetovanillone, acetoveratrone, propiovanillone, propioveratrone
1962-019
アルカリリグニン中のカルボニル溝造
石津 敦、仙頭 明、右田伸彦
東京大学農学部
Carbonyl structure in alkali lignin
Atsushi Ishizu, Akira Sento, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: spruce, thiolignin, soda lignin,r spectrum

1962-020
サルフエート蒸解における硫化物の役割
石津 敦、中野準三、右田伸彦
東京大学農学部
Role of sulfides in sulfate cooking
Atsushi Ishizu, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, guaiacylglycerol--guaiacyl ether
1962-021
木材加水分解リグニンの水溶性処理
中野準三、佐々木和仁、右田伸彦
東京大学農学部
Solubilization of wood hydrolysis lignin
Junzo Nakano, Kazuhito Sasaki, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: sufonation, sodium sulfite
1962-022
濃硫酸法木材加水分解リグニンの物理化学的性状について（その一）布村昭夫、阿部 勲、長谷川勇、峰村伸哉、北村維朗
北海道林業試験場
Physicochemical properties of wood hydrolysis lignin with concentrated sulfuric acid (I)Akio Nunomura, Isao Abe, Isamu Hasegawa, Nobuya Minemura, Tadao Kitamura
Hokkaido Forestry Research Institute
Keywords: white birch, Betula platypylla, methoxyl content
1962-023
リグニン樹脂に関する研究
岡田稔，後藤孝，白岩治巳，高安信義
興国人絹パルプ株式会社
Studies on lignin resin
Minoru Okada, Takashi Goto, Harumi Shiroiwa, Nobuyoshi Takayasu
Kokoku Jinken Pulp Co., Ltd.
Keywords: sulfite lignin, sulfite spent Liquor, polyamine lignin complex, lignin-phenol- formaldehyde
resin
1962-024
リグニンスルホン酸−フェノール縮合物の鞣皮性能
京極与寿郎、加藤正之、八浜義和
大阪大学工学部
Tanning property of condensation product of lignosulfonic acid and phenol
27

Yoshiro Kyougoku, Masayuki Kato, Yoshikazu Hachihama
Faculty of Engineering, Osaka University
Keywords: red pine, Pinus densiflora, waste lignin from neutral sulfite cooking, phenolic hydroxyl content
特別誇演、
木材加水分解工業の二、三の知見
保坂秀明
北海道木材化学株式会社
1962-Invited lecture:
Information concerning wood hydrolysis industry
Hideaki Hosaka
Hokkaido Wood Chemical Co. Ltd.

28

第 8 回 （1963.11.5-6） 松江市、島根自治会館
1963-001
ペルオキシダーゼによるコニフェリルアルコールの脱水素重合 1．タケノコのペルオキシダー ゼの精製と脱水素重合物の分光学的検索法
野津祐三、 中村 亘、奥貫一男
大阪大学理学部
Dehydrogenative polymerization of coniferyl alcohol by peroxidase (I), Purification of bamboo peroxidase andspectroscopic investigation of dehydrogenative polymer
Yuzo Nozu, Wataru Nakamura, Kazuo Okunuki
Faculty of Science, Osaka University
Keywords: DHP, UV spectroscopy, optimum pH
1963-002
パーオキシダーゼによるリグニン及びモデル化合物の酵素的分解
石川久雄、沖 妙
愛媛大学農学部
Enzymatic degradation of lignin and lignin model compounds by peroxidase
Hisao Ishikawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: radish, horse radish, Collybia velutipes
1963-003
アカマツ外皮リグニンスルフォン酸の性状について
十河村男、幡 克美
香川大学農学部
Properties of lignosulfonic acid from outer bark of red pine
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: nitrobenzene oxidation, molecular weight
1963-004
ポリサルフアイドリグニンの性状
中野準三、右田伸彦
東京大学農学部
Properties of lignin from polysulfide cooking liquor
Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compound, vanillyl alcohol, apocynol
1963-005
タバコリグニンの性状について
加藤邦雄＊１、中野準三＊２、右田伸彦＊２＊１
専売公社中央研究所、＊２東京大学農学部
Properties of lignin in tobacco plant
Kunio Kato*1, Junzo Nakano*2, Nobuhiko Migita*3*1
Central Research Institute, Japan Tobacco and Salt Public Corporation,*2
Faculty of Agriculture, the University of Tokyo
Keywords: milled wood lignin, elemental composition, UV absorption spectrum, IR absorption spectrum
1963-006
ササのリグニンの性質
氏家雅男
北海道大学農学部29

Properties of lignin in Sasa kurilensis
Masao Uji-ie
Faculty of Agriculture, Hokkaido University
Keywords: Sasa kurilensis, milled wood lignin, color reaction, UV absorption spectrum, IR absorption
spectrum
1963-007
木材の MWL の赤外線吸収曲線について
川村一次、樋口隆昌
岐阜大学農学部
Infrared absorption spectra of milled wood lignins
Ichiji Kawamura, Takamasa Higuchi
Faculty of Agriculture, Gifu University
Keywords: softwood, hardwood, monocotyledons, dioxane lignin
1963-008
アルカリリグニンのカルボキシル基石津 敦、中野準三、右田伸彦
東京大学農学部
Carboxyl group in alkali lignin
Atsushi Ishizu, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: protolignin, decarboxylation, Mannich reaction
特別講演
リグニンの工業的利用
野村順次
山陽パルプ株式会社
1963- Invited lecture:
Industrial utilization of lignin
Junji Nomura
Sanyo Pulp Co. Ltd.
パネル討論会、リグニンの利用開発
司会者：八浜義和（大阪大学工学部）
1963- Panel discussion: Development of lignin utilization
Moderator: Yoshikazu Hachihama, Faculty of Engineering, Osaka University
1963-009
リグニンのゲル化、特にその活性中心について
田中浩雄、千手諒一
九州大学農学部
Gelation of lignin, especially on the active center for gel formation
Hirowo Tanaka, Ryouichi Senjyu
Faculty of Agriculture, Kyushu University
Keywords: lignosulfonic acid, thiolignin, potassium dichromate, desulfonation, carboxymethylation,
methylation, chlorination
1963-010
リグニンスルフォン酸塩の分散性
小林晃夫、山川 功、葉賀忠昭、佐藤孝一郎
国策パルプ株式会社
Dispersing ability of lignosulfonate
Akio Kobayashi, Isao Yamakawa, Tada-aki Haga, Kouichiro Sato30

Kokusaku Pulp Co., Ltd.
Keywords: cement, molecular weight,
1963-011
リグニンに対する放射線グラフト共重合
越島哲夫、村木永之介
大阪工業技術試験所
Radiation–induced graft copolymerization onto lignin
Tetsuo Koshijima, Einosuke Muraki
Osaka National Research Institute.
Keywords: methyl metacrylate, styrene, vinyl acetate, cobalt 60
1963-012
糖化リグニンの溶解と IR スペクトル （リグニンの単離及び単離リグニンの反応性、V）
福渡七郎、雑賀宏昌
島根農科大学
Isolation of lignin and reactivity of the isolated lignin (V), Solubilization of wood-hydolysis lignin, and its
infrared absorption spectroscopy
Shichiro Fukuwatari, Hiromasa Saika
Shimane University of Agriculture
Keywords: sulfuric acid lignin, IR spectroscopy
1963-013
ポリサルフアイド２段蒸解におけるリグニンの挙動
宮尾再青＊１、中野準三＊２、右田伸彦＊２＊１
東洋パルプ株式会社、＊２東京大学農学部
Behavior of lignin during two-stage polysulfide cooking
Saisei Miyao*1, Junzo Nakano*2, Nobuhiko Migita*2*1
Toyo Pulp Co. Ltd., *2Faculty of Agriculture, the University of Tokyo
Keywords: Polysulfide, two-stage cooking, vanillyl alcohol.
1963-014
特別講演、リグニン化学の一動向
石川久雄
愛媛大学農学部
Invited lecture:
Trend of lignin chemistry
Hisao Ishikawa
Faculty of Agriculture, Ehime University
1963-015
土壌処理剤としてのリグニンスルフォン酸塩の研究 2．ゲル化による砂質土の処理
赤羽政亮、黒沢 彰、矢野弘子
鉄道技術研究所
Studies on lignosulfonate as a soil-stabilizer (II), Treatment of sandy soil by gelation
Masasuke Akabane, Akira Kurosawa, Hiroko Yano
Railway Technical Research Institute
Keywords: potassium dichromate, aluminum chloride, cupric chloride, ferric chloride, aging test
1963-016
土壌処理剤としてのリグニンスルフォン酸塩の研究 3．クロムリグニン及び処理土からの溶赤羽政亮、黒沢 彰、矢野弘子
鉄道技術研究所
31

脱Studies on lignosulfonate as a soil-stabilizer (III), Chrom-lignin and its leaching from treated soil
Masasuke Akabane, Akira Kurosawa, Hiroko Yano
Railway Technical Research Institute
Keywords: potassium dichromate, aluminum chloride, cupric chloride, ferric chloride, aging test
1963-017
クラフトリグニンの水素添加分解について
藤岡靖雄
日本パルプ工業株式会社
Hydrocrackinng of kraft lignin
Yasuo Fujioka
Nippon Pulp Industry Co., Ltd.
Keywords: hydrocracking, kraft lignin, oil yield, catalyst, phenols
1963-018
連続試験装置によるリグニンの水素化分解（予報）榊原 彰、宮崎 信、石原達夫、尾田勝夫、山口 章、高橋 敏
林業試験場
Continuous hydrocracking of lignin by small-scale pilot plant (Preliminary report)
Akira Sakakibara, Sin Miyazaki, Tatsuo Ishihara, Masao Oda, Akira Yamaguchi, Satoshi Takahashi
Forestry and Forest Product Research Institute特別講演
1963- Invited Lecture:
The Swedish Wood Research Center, a Brief Review of Organization and Research
J. L. Samuelsson
The Central Laboratory of the Swedish Cellulose Industry32

第 9 回 (1964.11.11-12) 紙パルプ会館
1964-001
コニフェリルアルコールの脱水素重合に関する酵素系について
中村 亘、野津祐三、奥貫一男
大阪大学理学部
Enzymes participating in dehydrogenative polymerization of coniferyl alcohol
Wataru Nakamura, Yuzo Nozu, Kazuo Okunuki
Faculty of Science, Osaka University
Keywords: peroxidase, laccase, Japanese lacquer, bamboo shoot, mushroom
1964-002
植物の組織培養中のリグニンの生合成
樋口隆昌
岐阜大学農学部
Biosynthesis of lignin during tissue culturing of plants
Takayoshi Higuchi
Facuty of Agriculture, Gifu University
Keywords: strobus pine (Pinus strobus), sequoia (Sequoia sempervirens), paulownia (Paulownia
tomentosa), syringe (Syringa pekinensis), rosa (Rosa grauca), pelargonium (Pelargonium grandiflorum), poplar(Populus nigra), 14C-phenylalanine, ethanolysis, nitrobenzene oxidation
1964-003
赤外線吸収曲線に基づくリグニンの分別と化学的性質との関係
川村一次、樋口隆昌
岐阜大学農学部
Relationship between classification of lignin based on IR absorption spectra and theirchemicalproperties

Ichiji Kawamura, Takayoshi Higuchi
Facuty of Agriculture, Gifu University
Keywords: fern plant (Pteridophyta), cycads (Cycas revoluta), ginkgo (Ginkgo biloba), ephedra(Ephedra sinica), Mäule color reaction, nitrobenzene oxidation
1964-004
リグニンのポーラログラフ的研究（第 11 報）モデル化合物の KP 蒸解とポーラログラフ的性質
寺島典二、玉生征人、神田 孝
名古屋大学農学部
Polarography of lignin, XI. Kaft cooking of lignin model compounds and their polarographic properties
Noritsugu Terashima, Masato Tamao, Takashi Kanda
Faculty of Agriculture, Nagoya University
Keywords: imine-cobalt chelate compound
1964-005
リグニン中のピノレジノール構造について
荻山紘一、近藤民雄
九州大学農学部
Pinoresinol structural units in lignin molecule
Koichi Ogiyama, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: red pine, Pinus densiflora, Cryptomeria japonica, white birch, Betula tauschii, Symplocos
lucida, alcohol lignin, nitric acid oxidation, dilactone
1964-006
低分子量リグニンスルホン酸の分離（主としてペーパークロマトグラフイによる知見）
33

田中治郎
林業試験場
Separation of low molecular lignosulfonic acid, and information obtained by paper chromatography
Jiro Tanaka
Forestry and Forest Product Research Institute
Keywords: Abies sachariensis, sulfite cooking, paper chromatography
1964-007
ブナリグニンスルホン酸に関する研究（第 1 報）
秦 邦男、中村孝一
東北パルプ株式会社
Studies on beech lignosulfonates (I)Kunio Hata, Koichi Nakamura
Tohoku Pulp Co., Ltd.
Keywords: sulfite spent liquor, barium lignosulfonate, beech, Fagus crenata
1964-008
クラフト蒸解における硫化物の役割
石津 敦、中野準三、右田伸彦
東京大学農学部
Role of sulfides in kraft cooking
Atsushi Ishizu, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: Abies sachariensis, milled wood lignin,r spectrum

1964-009
ポリスルフイドリグニンの性状＊１
中野準三、＊１右田伸彦、＊２宮尾再青＊１
東京大学農学部、＊２東洋パルプ株式会社
Characterization of lignin from polysulfide cooking liquor
Junzo Nakano, Nobuhiko Migita, Saisei Miyao*1
Faculty of Agriculture, the University of Tokyo, *2Toyo Pulp Co, Ltd.
Keywords: vanillyl alcohol, thiolignin, sulfur content
1964-010
チオリグニンとフェノールとの反応
小林晃夫、葉賀忠昭、佐藤孝一郎
国策パルプ株式会社
Reaction of thiolignin with phenol
Akio Kobayashi, Tadaaki Haga, Kouichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: thiolignin, phenol, reaction, formaldehyde
1964-011
リグニンをベースとした接着剤について
秋野精也、岩崎揮一、三輪一迪
東海パルプ株式会社
Lignin-base adhesive
Seiya Akino, Terukazu Iwasaki, Kazumichi Miwa
Tokai Pulp & Paper Co., Ltd.
Keywords: thiolignin, phenol-formaldehyde resin, resol resin, softwood black liquor
1964-012
セメントに対する亜硫酸パルプ排液の作用34町原 晃、中島浩二
山陽パルプ株式会社
Dispersing ability of sulfite spent liquor on cement slurry
Akira Machihara, Koji Nakajima
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, spent liquor, cement, dispersing effect, lignosulfonic acid, sulfonatedcarbohydrate, aldonic acid
1964-013
エゾマツ粗酢酸リグニンより得た低分子化合物および高分子化合物について
福住俊郎、芝本武夫
東京大学農学部
Low and high molecular weight compounds obtained from crude acetic acid lignin of Yezo spruce
Toshio Fukuzumi, Takeo Shibamoto
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, vanilloyl methyl ketone, vanillin, molecular weight
1964-014
リグニンの過酢酸分解について
畠山兵衛、中野準三、右田伸彦
東京大学農学部
Degradation of lignin with peracetic acid
Hyoe Hatakeyama, Jyunzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, vanillyl alcohol, veratryl alcohol
1964-015
リグニンの酸化分解に関する研究（III） 過酸化物による高収率パルプの漂白時における脱リグニンの機作について
石川久雄、沖 妙
愛媛大学農学部
Studies on the oxidative degradation of lignin (III), Delignification mechanism of peroxide bleaching of highyield pulp
Hisao Ishikawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: chemigroundwood pulp, dioxane lignin, peracetic acid
1964-016
硫酸糖化リグニンの化学「シェルモールド用材料としての基礎的知見」
宮崎安太郎＊１、勝田千昭＊１、森松久徳＊２、上ケ島慶一＊２＊１
東京教育大学農学部、＊２北海道木材化学工業株式会社
Chemistry of sulfuric acid hyrolysis lignin: Basic knowledge on the material for shell mold process
Yasutaro Miyazaki*1, Chiaki Katuta*1, Hisanori Morimatsu*2, Keiichi Jyogasima*2＊１
Faculty of Agriculture, Tokyo University of Education,＊２Hokkaido Wood Chemical Engineering Co. Ltd.
1964-0017
リグニンの水素化分解に関する研究（第 6 報）鉄カーボニルを触媒とした場合のリグニンスル ホン酸に対する各要因の検討榊原 彰＊１、田中治郎＊２、古屋信子＊２、宮崎 信＊２、石原達夫＊２、尾田勝夫＊２、山口 彰＊２、 高橋 敏 ＊ ２ 、
志水一允＊２＊１
北海道大学農学部、＊２林業試験場
Hydrogenolysis of lignin (VI), Investigation of factors affecting on reaction during hydrogenolysis of
lignosulfonic acid using iron carbonyl as a catalyst
Akira Sakakibara*1, Jiro Tanaka*2, Nobuko Furuya*2, Shin Miyazaki*2, Tatsuo Ishihara*2, Masao Oda*2, Akira
35

Yamaguchi*2, Satoshi Takahashi*2, Kazumasa Simizu*2*1Faculty of Agriculture, Hokkaido University, *2Forestry and Forest Products Research Institute
Keywords: addition of sulfur, yield of phenolic cpmpounds
1964-018
リグニンの水素化分解に関する研究（第 7 報）モデル化合物の水素化分解によって得られた 2、3 の知見
石原達夫、宮崎 信、田中治郎、尾田勝夫、山口 彰、古屋信子、高橋 敏、志水一允
林業試験場
Hydrocracking of lignin (VII), Information obtained by hydrocracking of lignin model compounds
Tatsuo Ishihara, Sin Miyazaki, Jiro Tanaka, Masao Oda, Akira Yamaguchi, Nobuko Furuya, Satoshi Takahashi,
Kazumasa Simizu
Forestry and Forest Products Research Institute
Keywords: lignin model compounds, structure of side chain
1964-019
重クロム酸リグニンのゲル化機構について（その一）林 晄*1、D.A.I.Goring*2*1
立命館大学理工学部、*2 カナダ紙パルプ研究所
Gelling mechanism of lignin by dichromate (I)Akira Hayashi*1, D.A.I. Goring*2*1
College of Science and Engineering, Ritsumeikan University, *2Pulp and Paper Research Institute of Canada
Keywords: viscosity, hydrophilicity, sulfonic acid group content, catechol group
1964-020
重クロム酸リグニンのゲル化機構について（その二）林 晄*1、D. A. I. Goring*2*1
立命館大学理工学部、*2 カナダ紙パルプ研究所
Gelation mechanism of lignin by dichromate (II)Akira Hayashi*1, D.A.I. Goring*2*1
College of Science and Engineering, Ritsumeikan University, *2Pulp and Paper Research Institute of Canada
Keywords: active group, tannin, molybdate, tungstate
1964-021
過硫酸塩によるリグニンのゲル化について
田中浩雄、千手諒一
九州大学農学部
Gelation of lignin by persulfate
Hiroo Tanaka, Ryoichi Senjyu
Faculty of Agriculture, Kyusyu University
Keywords: ammonium persulfate, lignin sulfonic acid, thiolignin
1964-022
土壌処理剤としてのリグニンスルホン酸塩の研究、第５報、カビ性試験について
赤羽政亮，河村肇，八木舜治
鉄道技術研究所
Studies on lignosulfonates for soil stabilizer (V), Result of fungus resistance test
Masasuke Akabane, Hajime Kawamura, Shunji Yagi
Railway Technical Research Institute
Keywords: soil stabilizer, chromium lignin, fungus, lignin sulfonate, gelatinizer
1964-023
特別講演： リグニンの研究に対する要望
1. 大学から民間研究機関へ
三川 礼
36

大阪大学産業科学研究所
2. 民間から国公立研究機関へ
秦 邦男
東北パルプ株式会社
Invited lecture: Requests to the research on lignin
1. From university to private research institutes.
Rei Mikawa,
Institute of Scientific and Industrial Research, Osaka University
2. From private research institutes to university.
Kunio Hata
Tohoku Pulp Co. Ltd.

37

第 10 回 （1965.11.8-9） 大阪科学技術センター
1965-001
加水分解リグニン系樹脂製造に関する研究（第 2 報）リグニンのアルカリ活性化試験
阿部 勲、窪田 実、布村昭夫、森 滋
北海道林産試験場
Preparation of plastics from wood hydrolysis lignin (II), Activation of lignin by treatment with alkali
Isao Abe, Minoru Kubota, Akio Nunomura, Shigeru Mori
Hokkaido Forest Products Research Institute
Keywords: thermosetting plastic, sulfuric acid lignin
1965-002
加水分解リグニン系樹脂製造に関する研究（第 3 報）活性化リグニンの縮合試験
阿部 勲、北村維朗、布村昭夫、森 滋
北海道林産試験場
Preparation of plastics from wood hydrolysis lignin (III) Condensation of activated lignin
Isao Abe, Minoru Kubota, Akio Nunomura, Shigeru Mori
Hokkaido Forest Products Research Institute
Keywords: thermosetting plastic, sulfuric acid lignin, phenol, formaldehyde
1965-003
リグニン樹脂のシェルモールドへの応用
広瀬正尚
日本合成化工株式会社
Application of lignin resin for shell mold
Masanao Hirose
Nihon Gosei Kako Co., Ltd.
Keywords: lignin resin, shell mold, phenylpropane radical
1965-004
チオリグニンおよびフェノール化チオリグニンとホルムアルデヒドの反応
小林晃夫，葉賀忠昭，佐藤孝一郎
国策パルプ株式会社
Reaction of thiolignin and phenolated thiolignin with formaldehyde
Akio Kobayashi, Tadaaki Haga, Kouichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: thiolignin, phenolated thiolignin, formaldehyde, reaction
1965-005
アルカリ電池中のリグニンの挙動
林 晄、名村好文、山下大二郎
立命館大学理工学部
Behavior of lignin in alkaline battery
Akira Hayashi, Yosifumi Namura, Daijiro Yamashita
College of Science and Engineering, Ritsumeikan University
Keywords: thiolignin, electrode reaction
1965-006
亜硫酸パルプ排液の粘結性について
町原 晃，岡部次郎
山陽パルプ株式会社
Adhering ability of sulfite spent liquor
Akira Machihara, Jiro Okabe
Sanyo Pulp Co., Ltd.
38

Keywords:

sulfite pulp, spent liquor, adhering ability, casting sand, lignosulfonic acid, xylose

1965-007
亜硫酸パルプ廃液の 2、3 の粉体に対する分散効果について
猪狩俶将、小川博嗣、生源寺延東京工業試験所
Dispersion ability of sulfite waste liquor to some kinds of powder material
Yoshimasa Ikari, Hirotsugu Ogawa, Susumu Shogenji
Government Chemical Industrial Research Institute, Tokyo
Keywords: calcium carbonate, calcium hydroxide, Portland cement
1965-008
亜硫酸パルプ廃液およびリグニンスルホン酸の界面活性
小山 実、生源寺延東京工業試験所
Surface activity of sulfite waste liquor and lignin sulfonic acid
Minoru Koyama, Susumu Shogenji
Government Chemical Industrial Research Institute, Tokyo
Keywords: surface tension, interfacial surface tension, solubilization capacity, emulsifying capacity,dispersion force, osmotic force, foaming power
1965-009
加水分解リグニンから製造した陰イオン交換樹脂
載 清華、中野準三、右田伸彦
東京大学農学部
Anion exchange resin prepared from wood hydrolysis lignin
Seika Tai, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: white birch (Betula platyphylla), chloromethylated lignin, quaternary ammonium-strong basic
ion-exchange resin
1965-010
リグニンの水素化分解に関する研究 (第 8 報) 再生重質油をペースト油に使用するくりかえし運転について
宮崎 信*1、石原達夫*1、尾田勝夫*1、田中治郎*1、山口 彰*1、高橋 敏*1、古屋信子*1、志水 一 允 *1 、 榊 原彰*2*1
林業試験場、*2 北海道大学農学部
Hydrogenolysis of lignin, VIII. Repeated operation using recovered heavy oil as paste oil
Shin Miyazaki*1, Tatsuo Ishihara*1, Masao Oda*1, Jiro Tanaka*1, Akira Yamaguchi*2, Satoshi Takahashi*1,
Nobuko Furuya*1, Kazumasa Simizu*1, Akira Sakakibara*2*1
Forestry and Forest Products Research Institute, *2Faculty of Agriculture, Hokkaido
University
Keywords: SP waste lignin
1965-011
リグニンの水素化分解に関する研究（第 9 報）リグニンペーストの粘度
山口 彰 *1 宮崎 信 *1 、石原達夫 *1 、尾田勝夫 *1 、田中治郎 *1 、、高橋 敏 *1 、古屋信子 *1 、志水一允 *1 、榊原彰*2*1
林業試験場、*2 北海道大学農学部
Hydrogenolysis of lignin (IX), Viscosity of lignin paste
Akira Yamaguchi*2, Shin Miyazaki*1, Tatsuo Ishihara*1, Masao Oda*1, Jiro Tanaka*1, Satoshi Takahashi*1,
Nobuko Furuya*1, Kazumasa Simizu*1, Akira Sakakibara*2*1
Forestry and Forest Products Research Institute, *2Faculty of Agriculture, Hokkaido
University
Keywords: SP waste lignin
1965-01239スチレンのリグニンへの放射線グラフト共重合における溶媒効果
村木永之介、越島哲夫
大阪工業技術試験所
Solvent effect of styrene on radiation-induced graft copolymerization onto lignin
Einosuke Muraki, Tetsuo Koshijima
Government Industrial Research Institute, Osaka
Keywords: red pine (Pinus densiflora), hydrochloric acid lignin, methylated lignin, styrene
1965-013
塩酸リグニン・スチレングラフト重合生成物の性状と官能基
越島哲夫、村木永之介
大阪工業技術試験所
Properties and functional groups of hydrochloric acid lignin-styrene graft copolymer
Tetsuo Koshijima, Einosuke Muraki
Government Industrial Research Institute, Osaka
Keywords: nitrobenzene oxidation, chlorite oxidation
1965-014
リグニンモデルのゲル化機構について
田中浩雄、千手諒一
九州大学農学部
Gelation mechanism of lignin model compounds
Hiroo Tanaka, Ryoichi Senjyu
Faculty of Agriculture, Kyusyu University
Keywords: poly-(4-hydroxy)-styrene, novolac type phenolic resin
1965-015
モデル化合物のアルカリ分解生成物より見たリグニン側鎖の構造
田中治郎
林業試験場
Side chain structure of lignin estimated by alkaline degradation of model compounds
Jiro Tanaka
Forestry and Forest Product Research Institute
Keywords: guaiacylethane
1965-016
広葉樹リグニンのアリルグリセロール-β-アリルエーテル型構造について
中野準三、何 照〓、右田伸彦
東京大学農学部
Arylglycerol--aryl ether structure in hardwood lignin
Junzo Nakano, Zhao Jun He, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: guaiacyl nucleus, syringyl nucleus, acetoguaiacone, acetosyringone
1965-017
リグニン中のピノレジノール構造について（第 2 報）
荻山紘一、近藤民雄
九州大学農学部
Pinoresinol structural units in lignin molecule (II)Koichi Ogiyama, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: ethanol lignin, acetic acid lignin, dioxane lignin, milled wood lignin
1965-01840

リグニンの色に関する研究（第 2 報）官能基がチオリグニンの色に及ぼす影響
飯山賢治、中野準三、右田伸彦
東京大学農学部
Studies on the color of lignin (II), Effect of functional groups on the color of thiolignin
Kenji Iiyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: methylated lignin, chromophore, auxochrome
1965-019
リグニンの酸・アルカり変性について
福渡七郎、瀬崎一敏
兵庫農科大学
Modification of lignin by treatment with acid and alkali
Shichiro Fukuwatari, Kazutoshi Sezaki
Hyogo University of Agriculture
Keywords: sulfuric acid lignin, solubility
1965-020
リグニンの酸化分解に関する研究（第 5 報）過酢酸による模型化合物の酸化
石川久雄、沖 妙
愛媛大学農学部
Studies on the oxidative degradation of lignin (V), Oxidation of lignin model compounds by peracetic acid
Hisao Ishikawa, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: guaiacyl methyl carbinol, vanillyl alcohol, acetovanillone, vanillin, vanillic acid
1965-021
リグニンの酸化分解に関する研究（第 6 報）過酸化物漂白によるパルプからの脱リグニンについて
石川久雄、大久保克美、沖 妙
愛媛大学農学部
Studies on the oxidative degradation of lignin (VI), Delignification of pulp by peracetic acid bleaching
Hisao Ishikawa, Katsumi Okubo, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: high yied pulp, semichemical pulp, groundwood pulp, dioxane lignin
1965-022
リグニンの過酢酸分解について（コハク酸の起源構造の追求）
畠山兵衛、中野準三、右田伸彦
東京大学農学部
Degradation of lignin by peracetic acid — Investigation of original structure from which succinic acid is derived
Hyoe Hatakeyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: Yezo spruce (Picea jezoensis), succinic acid, vanillyl alcohol, veratryl alcohol
1965-023
リグニンに対する過酢酸の作用（第２報）
坂井克己、近藤民雄
九州大学農学部
Action of peracetic acid on lignin (II)Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: red pine (Pinus densiflora), white birch (Betula platyphylla), dioxane lignin, infrared absorption
spectrum41

1965-024
MWL およびその抽出残渣リグニンの分解物における比較
榊原 彰、松倉紀男
北海道大学農学部
Comparison of degradation products from MWL and residual lignin
Akira Sakakibara, Motoo Matsukura
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce (Picea jezoensis), veratric acid, isohemipic acid, dehydrodiveratric acid
1965-025
ジオキサン-水によるリグニンの加水分解（第 5 報）モデル物質の分解およびリグニン中にお ける結合形態に対する 2、3 の考察
榊原 彰、武山浩武、諸星紀幸北海道大学農学部
Hydrolysis of lignin with dioxane and water (V), Hydrolysis of lignin model compounds and discussion of
linkage types in lignin
Akira Sakakibara, Hirotake Takeyama, Noriyuki Morohoshi
Faculty of Agriculture, Hokkaido University
Keywords: coniferyl alcohol, veratrylglycerol--guaiacyl ether, disproportionation reaction
1965-026
チオ・リグニンの反応、 (その１) スルホ・メチル化反応
品部義秋，小川昭弘
東洋パルプ株式会社
Reaction of thiolignin (I), Sulfomethylation
Yoshiaki Shinabe, Akihiro Ogawa
Toyo Pulp Co., Ltd.
Keywords: dispersing agent, thiolignin, hydrophilicity, sulfomethylation, methylol group, air-entraining
ability
1965-027
チオ・リグニンの反応、 （その２） アミノ・メチル化反応
品部義秋，小川昭弘
東洋パルプ株式会社
Reaction of thiolignin (II), Aminomethylation
Yoshiaki Shinabe, Akihiro Ogawa
Toyo Pulp Co., Ltd.
Keywords: thiolignin, asphalt emulsifier, cationic surfactant, Mannich reaction
1965-028
チオリグニンのスルホメル化について
老田 靖、中野準三、右田伸彦
東京大学農学部
Sulfomethylation of thiolignin
Yasushi Oita, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: softwood thiolignin, hardwood thiolignin, surface tension, dispersion force
1965-029
竹の維管束および柔細胞のリグニンの化学的性質
木村長治、樋口隆昌、川村一次
岐阜大学農学部
Chemical properties of lignin in vascular bundle and parenchyma of bamboo
42

Choji Kimura, Takayoshi Higuchi, Ichiji Kawamura
Faculty of Agriculture, Gifu University
Keywords: Phyllostachys pubescens, Phyllostachys reticulata, nitrobenzene oxidation, ethanolysis
1965-030
種々のリグニン中の p-ヒドロキシフェニルグリセロール-β-アリルエーテル構造
樋口隆昌、川村一次
岐阜大学農学部
p-Hydroxyphenylglycerol structures in lignin of various plants
Takayoshi Higuchi, Ichiji Kawamura
Faculty of Agriculture, Gifu University
nitrobenzene oxidation, ethanolysis, gaschromatography, Gramineae
1965-031
ペルオキシダーゼによるコニフェリルアルコールの脱水素重合
野津祐三、中村 亘、奥貫一男
大阪大学理学部
Dehydrogenative polymerization of coniferyl alcohol by peroxidase
Yuzo Nozu, Wataru Nakamura, Kazuo Okunuki
Faculty of Science, Osaka University
Keywords: laccase, molecular weight, sinapyl alcohol
1965-総合講演
A
リグニン研究の最近の動向
中野準三（東京大学農学部）
B
リグニン生合成研究の現状と問題点
樋口隆昌（岐阜大学農学部）
C
リグニンの利用と物性について林 晄（立命館大学）
D
最近のパルプ廃液処理の動向
野村順次（山陽パルプ株式会社）
1965-Plenary lectures:A
Recent trends in research of lignin
Junzo Nakano (Faculty of Agriculture, the University of Tokyo)
B
Current situation of research in lignin biosynthesis and related problems
Takayoshi Higuchi (Faculty of Agriculture, Gifu University)
CPhysical properties and utilization of lignin
Akira Hayashi (Ritsumeikan University)
D
Recent trends in pulp waste liquor treatment
Junji Nomura (Sanyo Pulp Co. Ltd.)43

第 11 回 （1966.10.31-11.1） 広島大学会館
1966-001
リグニンの色に関する研究（第 3 報）蒸煮および単離条件がチオリグニンの色に及ほす影響
飯山賢冶、中野準三、右田伸彦
東京大学農学部
Studies on the color of lignin (III), Effect of cooking and isolation conditions on the color of thiolignin
Kenji Iiyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: red pine (Pinus densiflora), beech (Fagus crenata), reflectance spectra, visible lighttransmittance, sulfur
1966-002
リグニンの色に関する研究（IV）材のシーズニングがリグノスルホン酸の色に及ぼす影響について
中野準三、飯塚堯介、右田伸彦
東京大学農学部
Studies on the color of lignin (IV), Effect of seasoning on the color of lignosulfonic acid
Junzo Nakano, Gyosuke Meshitsuka, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: Abies firma, Pinus densiflora, Fagus crenata, Betura Maximowiziana, brightness, wavelength,
excitation purity
1966-003
重金属イオンとリグニンスルホン酸の色
林 晄、三成 紘
立命館大学理工学部
Heavy metai ion and color of lignosulfonic acid
Akira Hayashi, Hiro Mitsunari
College of Science and Engineering, Ritsumeikan University
Keywords: chelation, iron, copper, nickel, cobalt, manganese, chromium, catechol group
1966-004
リグニンのオゾン分解について
畠山兵衛、外岡豊穂、中野準三、右田伸彦
東京大学農学部
Degradation of lignin by ozone
Hyoe Hatakeyama, Toyoho Tonooka, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: vanillyl alcohol, veratryl alcohol, muconic acid lactone
1966-005
リグノスルホン酸およびチオリグニンの過酢酸分解
鈴木金道＊１畠山兵衛＊２、中野準三＊２、右田伸彦＊２＊１
東北パルプ株式会社研究所、＊２東京大学農学部
Degradation of lignosulfonic acid and thiolignin by peracetic acid
Kanemichi Suzuki*1, Hyoe Hatakeyama*2, Junzo Nakano*2, Nobuhiko Migita*2*1
Institute of Tohoku Pulp Co. Ltd., *2 Faculty of Agriculture, the University of Tokyo
Keywords: carboxyl group, phenolic hydroxyl group, methoxyl group, UV absorption spectrum
1966-006
二酸化塩素漂白に関する研究（I）モデル物質の二酸化塩素酸化について
石川俊彦、住本昌之、近藤民雄
九州大学農学部
Studies on the bleaching by chlorine dioxide (I), Oxidation of model compounds by chlorine dioxide44

Toshihiko Ishikawa, Masayuki Sumimoto, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: vanillin, vanillyl alcohol, syringyl alcohol, p-quinone structure
1966-007
リグノスルホン酸ゲル化反応中の脱メチル
林 晄、名村好夫、上北忠之
立命館大学理工学部
Demethylation during gelation reaction of lignosulfonic acid
Akira Hayashi, Yoshio Namura, Tadayuki Uekita
College of Science and Engineering, Ritsumeikan University
Keywords: catechol group, dichromate, guaiacol, vanillin, vanillyl alcohol
1966-008
リグニン及びリグニンモデル物質の高分解能 NMR スぺクトル
武谷 愿、横山 晋、石井忠雄
北海道大学工学部
High resolution NMR spectroscopy of lignin and lignin model compounds
Gen Taketani, Shin Yokoyama, Tadao Ishii
Faculty of Engineering, Hokkaido University
Keywords: Abies sachalniensis, Fagus crenata, Quercus crispula, milled wood lignin, DMSO
1966-009
リグニンと炭水化物との結合について
寺島典二*1、H.I. Bolker*2*1
名古屋大学農学部、*2 カナダ紙パルプ研研究所
Linkages between lignin and carbohydrates
Noritsugu Terashima*1, Henry I. Bolker*2*1
Faculty of Agriculture, Nagoya University, *2 Pulp and Paper Research Institute of Canada
Keywords: acetal, 2,2-dimethoxypropane, 2,2-diethoxypropane, solvolysis
1966-010
リグニン中のカルボキシル基定量
福渡七郎、錦織 勇
島根大学農学部
Determination of carboxyl group in lignin
Shichiro Fukuwatari, Isamu Nishikori
Faculty of Agriculture, Shimane University
Keywords: Infrared absorption spectroscopy, potassium thiocyanate, soda-lignin, thiolignin
1966-011
稲科植物 MWL の化学的性質
樋口隆昌＊１、島田幹夫＊１、川村一次＊１、井藤佳美＊２＊１
岐阜大学農学部、＊２岐阜大学工学部
Chemical properties of milled wood lignin from gramineous plants
Takayoshi Higuchi*1, Mikio Shimada*1, Ichiji Kawamura*1, Yoshimi Itoh*2*1
Faculty of Agriculture, Gifu University,*2 Faculty of Engineering, Gifu University
Keywords: UV absorption spectroscopy, IR absorption spectroscopy, p-coumaric acid, ferulic acid, esterbond
1966-012
熱帯より温帯にわたり自然分布しているユーカリのリグニンの化学的性質について
川村一次＊１、D.E. Bland＊２＊１
岐阜大学農学部、＊２オーストラリヤ CSIRO 林産研究所
45

Chemical properties of lignin of eucalyptus distributed from tropical to temperate zone
Ichiji Kawamura*1, D.E. Bland＊２*1
Faculty of Agriculture, Gifu University, ＊２Forest Product Research Institute, CSIRO, Australia
Keywords: IR absorption spectroscopy, S/V ratio, Klason lignin, altitude effect
1966-013
樹皮リグニンの化学的牲質樋口隆昌＊１、島田幹夫＊１、川村一次＊１、井藤佳美＊２＊１
岐阜大学農学部、＊２岐阜大学工学部
Chemical properties of bark lignin
Takayoshi Higuchi*1, Mikio Shimada*1, Ichiji Kawamura*1, Yoshimi Itoh*2*1
Faculty of Agriculture, Gifu University,*2 Faculty of Engineering, Gifu University
Keywords: black pine, Pinus Thunbergii, fir, Abies firma, hemlock, Tsuga heterophylla, Alder, Alnus
japonica, beech, Fagus crenata, ethanolysis
1966-014
ダグラスファー樹皮のエタノリシス生成物
藤井ミチヒロ*1，E. F. Kurth*2*1
北越製紙，*2 オレゴン州立大
Ethanolysis products from Douglas fir bark
Michihiro Fujii*1, E. F. Kurth*2*1
Hokuetsu Paper Mills Co., Ltd.，*2Oregon State University
Keywords: Douglas fir, Pseudotsuga taxifolia, ethanolysis, Hibbert’s ketones
1966-015
ブナリグニンスルホン酸に関する研究（第２報）ブナリグニンスルホン酸分劃物のニトロベンゼン酸化
秦邦男，中村孝一
東北パルプ株式会社
Studies on beech lignosulfonates (II), Nitrobenzene oxidation of fractionated lignosulfunate portions
Kunio Hata, Koichi Nakamura
Tohoku Pulp Co., Ltd.
Keywords: beech lignosulfonates, alkaline nitrobenzene oxidation, vanillin, syringyl aldehyde,
p-hydroxybenzaldehyde
1966-016
リグニンに対するアルカリ蒸解の影響 (IX) アリルアルキル-β-アリルエーテルの開裂に関するモデル実験
中野準三、鈴木 磨、佐伯節夫、右田伸彦
東京大学農学部
Effect of alkali cooking on lignin (IX), Model experiments on cleavage of arylalkyl--aryl ether
Junzo Nakano, Migaku Suzuki, Setsuo Saheki, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: kraft cooking, sulfidity, reaction temperature, paper chromatography, UV absorption
spectroscopy
1966-017
ジオキサンー水によるリグニンの加水分解（第 6 報）
佐野嘉拓、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane and water (VI)
Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: coniferyl alcohol, isoeugenol, paper chromatography
1966-01846

プロトリグニンの水素化分解に関する研究（第 1 報）ビフエニール結合体を中心として
和田 功、太田路一、榊原 彰
北海道大学農学部
Hydrogenolysis of protolignin (I), On the biphenyl type products
Isao Wada, Michikazu Ota, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, paper chromatography, 5,5′-biphenyl compounds
1966-019
モデル化合物のアルカリ分解生成物からみたリグニン側鎖の構造（II）
田中治郎
林業試験場
Side chain structure of lignin estimated from alkaline degradation products of model compounds (II)Jiro Tanaka
Forestry and Forest Product Research Institute
Keywords: guaiacyl ethane, ferulic acid, acetoguaiacone
1966-020
リグニン中のピノレジノール構造について（第 3 報）2,3-[Bis−oxyvanillyl]-butane-diol(1,4)から dl-Pinoresinolの合成について萩山紘一、近藤民雄
九州大学農学部
Pinoresinol structure in lignin (III), Synthesis of dl-pinoresinol from 2,3-[bis−oxyvanillyl]-butane- diol(1,4)
Koichi Ogiyama, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: thin layer chromatography, symplocosigenol, epipinoresinol
1966-021
β-ナフタレンスルホン酸ホルムアルデヒド縮合体（リグニンスルホン酸塩類似物質）の薄層クロマトグラフイーによる分離ならびにそれらの分子量と分子構造について
根来健二、佐伯幸民
広島大学工学部
Separation of a condensation product of -naphthalene sulfonic acid and formaldehyde (a compound analogous
to lignin sulfonic acid) by thin layer chromatography, and its molecular weight, and chemical structure
Kenji Negoro, Yukitami Saiki
Faculty of Engineering, Hiroshima University
Keywords: Tamol NNO, Demol N, gel filtration
1966-022
稲科植物リグニンの P-ヒドロキシフエニルプロパン部の性質とその形成におけるチラーゼの役割り
樋口隆昌＊１、川村一次＊１、井藤佳美＊２＊１
岐阜大学農学部、＊２岐阜大学工学部
Properties of p-hydroxyphenylpropane moiety in gramineous plant lignin and role of tyrase in its formation
Takayoshi Higuchi*1, Ichiji Kawamura*1, Yosimi Itoh*2*1
Faculty of Agriculture, Gifu University,*2 Faculty of Engineering, Gifu University
Keywords: p-coumaric acid, p-hydroxyphenyl nucleus, phenylalanine-G-14C,tyrosine-G-14C
1966-023
タケノコ中の 5-デヒドロシキミ酸還元酵素
樋口隆昌、島田幹夫
岐阜大学農学部
5-Dehydroshikimic acid reductase in bamboo shoots
Takayoshi Higuchi, Mikio Shimada
47

Faculty of Agriculture, Gifu University
Keywords: Phyllostachys reticulata, shikimic acid pathway, NADP, EDTA
1966-024
酵素によるフエルラ酸およびシナップ酸の生成
樋口隆昌、島田幹夫
岐阜大学農学部
Formation of ferulic and sinapic acids by enzyme
Takayoshi Higuchi, Mikio Shimada
Faculty of Agriculture, Gifu University
Keywords: Phyllostachys pubescens, Phyllostachys reticulata, S-adenosylmethinine, caffeic acid,5-dehydroferulic acid
1966-025
キンイロアナタケによって腐朽されたトウヒ材から分離したリグニンについて
幡 克美＊１、F.F. Nord＊２＊１
香川大学農学部、＊２フオーダム大学
Studies on the lignin isolated from spruce wood rotted by Poria subacida B11
Katsumi Hata*1, F.F. Nord*2*1
Faculty of Agriculture, Kagawa Universty, ＊2Fordham University
Keywords: spruce, Picea jezoensis, milled wood lignin, UV absorption spectrum, IR absorption spectrum,
nitrobenzene oxidation
1966-026
リグニンの水素添加分解
大島幹義、鹿島 寛、田畑晴郎、久保輝雄、渡部 浩
野口研究所
亜硫酸パルプ廃液、脱スルホンリグニン、触媒
Hydrocracking of lignin
Mikiyoshi Oshima, Hiroshi Kajima, Haruo Tabata, Teruo Kubo, Hiroshi Watanabe
Noguchi Institute
Keywords: sulfite pulp waste liquor, desulfonated lignin, catalyst
1966-027
鉛蓄電池に対するリグニンの効果
林 晄、名村好文
立命館大学理工学部
Effect of lignin on lead storage battery
Akira Hayashi, Yoshifumi Namura
College of Science and Engineering, Ritsumeikan University
Keywords: alkaline lignin, catechol, maleic acid
1966-028
液相及び気相アルカリ蒸解黒液から単離したリグニンの性状について
岡本行雄＊１、李 宗藩＊２、中野準三＊２、右田伸彦＊２＊１
東洋パルプ株式会社、＊２東京大学農学部
Characteristics of lignins isolated from the black liquor of liquid-phase and vapor-phase alkaline cookings
Yukio Okamoto*1, Sohan Ri*2, Junzo Nakano*2, Nobuhiko Migita*2*1
Toyo Pulp Co. Ltd., *2 Faculty of Agriculture, the University of Tokyo
Keywords: alkafide pulping, kraft pulping, polysulfide pulping
1966-029
Na-S 系によるリグニンの脱メチル反応
種田健造、長谷川勇
48

北海道林産試験場
Demethylation of lignin in aqueous alkaline solution containing sulfur
Kenzo Taneda, Isamu Hasegawa
Hokkaido Forest Products Research Institute
Keywords: dimethyl sifide, acid hydrolysis lignin, conversion to resin
1966-030
亜硫酸パルプ廃液のアルカリ溶液中での挙動について
猪狩俶将、小川博嗣、生源寺延東京工業試験所
Behavior of lignin in alkaline sulfite black liquor
Yoshimasa Ikari, Hirotsugu Ogawa, Susumu Shogenji
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: calcium hydroxide, cement, conductivity titration
1966-031
粉体の分散に対するリグニンスルホン酸と糖変成物の作用
小川博嗣、猪狩俶将、生源寺延東京工業試験所
Effect of lignin sulfonic acid and metamorphic product of carbohydrates on dispersion of powder
Hirotsugu Ogawa, Yoshimasa Ikari, Susumu Shogenji
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: zinc powder, light absorption
1966-032
亜硫酸パルプ排液の熱処理による分散剤の製造について
町原 晃，岡部次郎
山陽パルプ株式会社
Preparation of dispersant by heat treatment of sulfite spent liquor
Akira Machihara, Jiro Okabe
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, spent liquor, dispersant, heat treatment, spray drying, lignosulfonic acid
1966-033
針葉樹のクラフト黒液からチオリグニンの沈澱品部義秋、西部隆文
東洋パルプ株式会社
Precipitation of thiolignin from black liquor of kraft cooking of conifer wood
Yoshiaki Shinabe, Takafumi Nishibe
Toyo Pulp Co. Ltd.
Keywords: precipitant, sulfuric acid, carbon dioxide, cohesion property
1966-034
KP 黒液およびチオリグニンの界面活性
小山 実、生源寺延東京工業試験所
Surface activity of sulfite waste liquor and lignin sulfonic acid
Minoru Koyama, Susumu Shogenji
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: surface tension, solubilization capacity, emulsifying capacity, dispersion force, osmotic force,
foaming power
1966-035
チオリグニンの熱的挙動
49

岩見田 糺，佐藤孝一郎
国策パルプ株式会社
Thermal properties of thiolignin
Tadashi Iwamida, Kouichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: thiolignin, thermal gravimetric analysis, differential thermal analysis, insolubility, oxygen
content, softening temperature
1966-036
リグニンのエポオキシ化について
戴 洋華、中野準三、右田伸彦
東京大学農学部
Epoxidation of lignin
Seika Tai, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: softwood lignin, coniferous wood lignin, epichlorohydrin, infrared spectroscopy
1966-037
フェノール化チオリグニンとヘキサメチレンテトラミンとの反応
小林晃夫，葉賀忠昭，佐藤孝一郎
国策パルプ株式会社
Reaction of phenolated thiolignin with hexamethylene tetramine
Akio Kobayashi, Tadaaki Haga, Kouichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: thiolignin, phenolated thiolignin, hexamethylene tetramine, formaldehyde
1966-038
加水分解リグニン系樹脂に関する研究（第 4 報）装置試験および製造原単位
森 滋、布村昭夫、阿部 勲、北村維郎、窪田 実、朝倉孝之、斉藤 勝
北海道林産試験場
Studies on the plastics from wood hydrolysis lignin (IV), Equipment test and production intensity
Shigeru Mori, Akio Nunomura, Isao Abe, Tadao Kitamura, Minoru Kubota, Takayuki Asakura, Masaru Saito
Hokkaido Forest Products Research Institute
Keywords: thermosetting resin, continuous activation reaction, production intensity, operation cost
1966-特別講演
A
鋳型粘結剤について
東 正十郎
広島県呉工業試験所
1966-Invited lecture: Binder for casting moldShojuro Azuma
Kure Institute of Industrial Science and Technology, Hiroshima Prefecture.
Keywords: bentnite, water glass, sodium silicate, cement, starch, drying oil, lignin binderB
最近の界面活性剤の物性研究の動向
根来健二
広島大学工学部
1966-Invited lecture: Recent trend in the research of physical property of surfactant
Kenji Negoro
Faculty of Engineering, Hiroshima University
Keywords: surface tension, surface adsorption, contact angle, cloud point50

第 12 回 （1967.11. 1-2） 九州大学農学部
1967-001
SP 排液中のリグニンスルホン酸と非リグニン有機物の粉体の分散に対する作用
小川博嗣、猪狩俶将、生源寺延東京工業試験所
要旨空白（中止）
1967-002
リグニンの過酢酸酸化生成物の性状について
石川久雄、木下良郎、沖 妙、大久保克美
愛媛大学農学部
Characteristics of peracetic acid oxidation product of lignin
Hisao Ishikawa, Yoshiro Kinoshita, Tae Oki, Katumi Okubo
Faculty of Agriculture, Ehime University
Keywords: conifer, dioxane lignin, molecular weight
1967-003
SP 排夜中のリグニンスルホン酸の分子量分布とアルカリ溶液中での挙動
猪狩俶将、小川博嗣、生源寺延東京工業試験所
Molecular weight distribution of lignin sulfonic acid from sulfite waste liquor and its behavior in alkaline
solution
Yoshimasa Ikari, Hirotsugu Ogawa, Susumu Shogenji
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: hyamine salt, quaternary ammonium salt, electric conductivity titration, cement dispersing
agent
1967-004
リグニンスルホン酸のゲル化に関する研究
秦邦男，中村孝一
東北パルプ株式会社
Studies on gelation of lignosulfonates
Kunio Hata, Koichi Nakamura
Tohoku Pulp Co., Ltd
Keywords: beech, Fagus crenata, sulfite cooking black liquor, gelation, dicyclohexylamine- n-butanol
extraction, potassium dichromate
1967-005
亜硫酸パルプ排液と重クロム酸の反応に関する 2，3 の考察
岡部次郎，町原 晃，三浦義之
山陽パルプ株式会社
Reaction of sulfite spent liquor with dichromate
Jiro Okabe, Akira Machihara, Yoshiyuki Miura
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, spent liquor, dichromate, soil stabilizer, lignosulfonic acid, gelation, chelate
1967-006
フェノール類の酸化的カップリング反応
熊野谿従、加藤 隆
東京大学工学部
Oxidative coupling reaction of phenolic compounds
Ju Kumanotani, Takashi Kato
Faculty of Engineering, the University of Tokyo
51

Keywords:

quinone quinhydron, quinone methide, radical reaction

1967-007
リグニンモデル化合物と過酢酸との反応における側鎖の影響
鈴木金道*1、畠山兵衛*2、中野準三*2、右田伸彦*2*1
東北パルプ株式会社、*2 東京大学農学部
Effect of side chain structure on the reaction of lignin model compounds with peracetic acid Kanemichi
Suzuki*1, Hyoe Hatakeyama*2, Junzo Nakano*2, Nobuhiko Migita*2*1
Tohoku pulp Co.Ltd., *2Faculty of Agriculture, the University of Tokyo.
Keywords: vanillyl alcohol, barium vanillyl sulfonate, vanillyl ethyl sulfide
1967-008
リグニンモデル化合物の過酢酸酸化分解について
沖 妙、木下良郎、石川久雄
愛媛大学農学部
Oxidation of lignin model compounds by peracetic acidTae Oki, Yosiro Kinoshita, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: vanillyl alcohol, vanillin, guaiacylglycerol, isoeugenol, Baeyer-Villiger Reaction
1967-009
プロトリグニンの水素化分解に関する研究（第 2 報）1,2-Diaryl Propane 構造を有する分解物の単離
太田路一、榊原 彰
北海道大学農学部
Hydrogenolysis of protolignin (II), Isolation of 1,2-diaryl propane type products
Michikazu Ota, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo
spruce,Picea
jezoensis,
paper
chromatography,
1,2-bis-(4-hydroxy-3methoxyphenyl)-propanol-3
1967-010
クラフトパルプの塩素による漂白について
寺島典二*1、篠田善彦*2、神田 孝*1*1名古屋大学農学部、*2 岐阜大学農学部
Bleaching of kraft pulp with chlorine
Noritsugu Terashima*1, Yoshihiko Shinoda*2, Takashi Kanda*1*1
Faculty of Agriculture, Nagoya University, *2Faculty of Agriculture, Gifu University
Keywords: vanillyl alcohol, quinhydron, stilbene, lignin-carbohydrate bond
1967-011
サルフアイト蒸解における着色構造の生成について
飯塚堯介、中野準三、右田伸彦
東京大学農学部
Formation of chromopholic structures during sulfite cooking
Gyosuke Meshitsuka, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: red pine, Pinus densiflora, birch, Betula maximowiczii, lignin sulfonic acid, combined sulfur
dioxide, catechol, hemicellulose
1967-012
リグニン中のラジカルの温度依存性
畠山兵衛、中野準三、右田伸彦
東京大学農学部
Temperature dependence of stability of radical in lignin
52

Hyoue Hatakeyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: electron spin resonance, broad line nuclear magnetic resonance, milled wood lignin, dioxane
lignin, lignin sulfonic acid
1967-013
樹皮の難溶性リグニンについて十河村男、幡 克美
香川大学農学部
Low-solubility lignin in tree bark
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: red pine, Pinus densiflora, Yezo spruce, Picea jezoensis, Acacia, Japanese oak, Quercus
crispula, Quercus serrata, chestnut, Castanea crenata, dioxane lignin
1967-014
MWL、LCC およびその抽出残渣リグニンの分解物における比較（第 2 報）
松倉紀男、榊原 彰
北海道大学農学部
Comparison of degradation products of MWL, LCC and lignin in extracted residue (II)Motoo Matsukura, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: protolignin, potassium permanganate oxidation, nitrobenzene oxidation, ethanolysis, condensed
structure
1967-015
リグニン樹脂発泡体製造に関する研究 —縮合に関する二，三の知見—
森 滋、阿部 勲、峯村伸哉、窪田 実
北海道林産試験場
Production of plastics form from lignin — Results obtained from cndensation test—
Shigeru Mori, Isao Abe, Shinya Minemura, Minoru Kubota
Hokkaido Forest Products Research Institute
Keywords: kraft lignin, formaldehyde, hydroxymethylated lignin
1967-016
チオリグニンのイソシアネート化について
戴 清華、沢登丈夫、中野準三、右田伸彦
東京大学農学部
Reaction of thiolignin with trilene diisocyanate
Seika Tai, Takeo Sawanobori, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: urethane bond, allophanate bond, m-phenylenediamine, polyethyleneglycol
1967-017
リグニンと合成高分子化合物との共縮合に関する研究 —ポリメタアクロイルクロライドと諸種水酸基とのエステル化反応内藤寿夫、福住俊郎、南 享二
東京大学農学部
Studies on the copolymerization of lignin with synthetic polymer —Esterification of several hydroxyl
compounds with polymethacryloyl chloride
Hisao Naito, Toshio Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: phenol, methoxyphenol, vanillyl alcohol, NMR spectra
1967-01853

放射線の空気中前照射によるリグニンのグラフト化
村木永之介、越島哲夫
大阪工業技術試験所
Grafting of lignin with pre-radiation in the air
Einosuke Muraki, Tetsuo Koshijima
Osaka Institute of Advanced Industrial Science and Technology
red pine, Pinus densiflora, hydrochloric acid lignin, lignin sulfonic acid, styrene
1967-019
リグニンモデル化合物のアルカリ蓄電池に対する作用
林 晄、木下恭介
立命館大学理工学部
Effect of lignin models on alkali storage battery
Akira Hayashi, Kyosuke Kinoshita
College of Science and Engineering, Ritsumeikan University
Keywords: thiolignin, catechol, guaiacol, pyrogallol, maleic acid, chelate
1967-020
亜硫酸パルプ廃液活性炭について
岸本 定吉＊１、森 見二＊２
＊１
東京教育大学農学部、＊２静岡大学農学部
Production of active carbon from sulfite waste liquor
Teikichi Kishimoto, Kenji Mori
＊１
Faculty of Agriculture, Tokyo University of Education, ＊２Faculty of Agriculture, Shizuoka University
Keywords: activation by zinc chloride, water vapor activation
1967-021
フェニルプロパン誘導体のガスクロマトグラフィ
山口 彰、宮崎 信、高橋 敏
林業試験場
Gas chromatography of phenylpropane derivatives
Akira Yamaguchi, Makoto Miyazaki, Satoshi Takahashi
Forestry and Forest Products Research Institute
Keywords: trimethylsilylether, side-chain structure, side-chain hydroxyl group
1967-022
リグニンの電子スペクトルの解析
飯山賢治、中野準三、右田伸彦
東京大学農学部
Resolution of electronic spectra of lignin
Kenji Iiyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: Yezo spruce, Picea jezoensis, milled wood lignin, lignin sulfonic acid, absorption band,
guaiacyl nucleus, syringyl nucleus
1967-023
チオリグニンのポーラログラフ的研究（第 12 報）アルカリ蒸解中におけるクアヤシル核 5 位置 換 構 造 の 生成について
玉生征人、寺島典二、神田 孝
名古屋大学農学部
Polarography of lignin (XII), Formation of substructure with substitution at 5 position of guaiacyl nucleus
during alkali pulping
Masato Tamao, Noritsugu Terashima, Takashi Kanda
Faculty of Agriculture, Nagoya University
54

Keywords: red pine, Pinus densiflora, thiolignin, polarography, alkaline cooking, guaiacyl nucleus,condensed unit
1967-024
担子菌によるリグニンの分解における芳香族化合物添加の影響
原口隆英
東京農工大学農学部
Effect of addition of aromatic compounds on the degradation of lignin by basidiomycetes
Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Pycnoporus coccineus, Yezo spruce, Picea jezoensis, benzoic acid, p-hydroxybenzoic acid,vanillic acid, ferulic acid
1967-025
木材腐朽菌の酵素によるリグニンの分解 —リグニンのアリルアルキルエーテル結合の分解
福住俊郎、南 享二
東京大学農学部
Degradation of lignin by enzyme of wood-rotting fungi, –Cleavage of arylalkyl ether bondToshio Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Yezo spruce, Picea jezoensis, Perenniporia subacida, veratrylglycerol- -guaiacyl ether, laccase
1967-026
タケノコの木化における O-メチルトランスフエラーゼの役割について
樋口隆昌、島田幹夫、大橋英雄
岐阜大学農学部
Role of O-methyltransferase in lignification of bamboo shootTakayoshi Higuchi, Mikio Shimada, Hideo Ohashi
Faculty of Agriculture, Gifu University
Keywords: Phyllostachys pubescens, Phyllostachys reticulata, caffeic acid, S-adenosylmethionine, ferulic
acid, sinapic acid
1967-027
タケノコの木化に伴う関連酵素の変動について
樋口隆昌、島田幹夫
岐阜大学農学部
Change of activity of enzymes involved in lignification of bamboo
Takayoshi Higuchi, Mikio Shimada
Faculty of Agriculture, Gifu University
Keywords: Phyllostachys pubescens, Phyllostachys reticulata, phenylalanine ammonia-lyase, peroxidase55

第 13 回 （1968.10.26-27） 名古屋大学農学部
1968-001
リグニンのメトキシル基生成に関する生化学的研究
樋口隆昌＊１、島田幹夫＊２、大橋英雄＊２＊１
京都大学木材研究所、＊２岐阜大学農学部
Biochemical study on the formation of methoxyl groups of lignin
Takayoshi Higuchi*1, Mikio Shimada*2, Hideo Ohashi*2*1
Wood Research Institute, Kyoto University, *2 Faculty of Agriculture, Gifu University
Keywords: Phyllostachys pubescens, Phyllostachys reticulata, Ginkgo biloba, Cryptomeria japonica,
Podocarpus macrophyllus, yew, Taxus cuspidate, autoradiography, O-methyltransferase
1968-002
稲科植物リグニン中の p-クマール酸のエステル結合に関する研究
樋口隆昌＊１、島田幹夫＊２、山崎 徹＊１、福塚 哲＊２＊１
京都大学木材研究所、＊２岐阜大学農学部
Studies on the p-coumaric ester bond of grass lignin
Takayoshi Higuchi*1, Mikio Shimada*2, Toru Yamasaki＊１, Tetsu Fukuzuka*2*1
Wood Research Institute, Kyoto University, *2 Faculty of Agriculture, Gifu University
Keywords: bamboo, Arundo donax, Coix, Phragmites, DHP
1968-003
木材腐朽菌によるリグニンの分解
石原達夫、宮崎 信
林業試験場
Degradation of lignin by wood-rotting fungi
Tatsuo Ishihara, Makoto Miyazaki
Forestry and Forest Product Research Institute
Keywords: Polyporus versicolor, milled wood lignin, catechol, Pseudomonas
1968-004
樹皮リグニンの定量について
十河村男、幡 克美
香川大学農学部
Determination of lignin content in bark
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: Japanese red pine, Pinus densiflora, Yezo spruce, Picea jezoensis, Quercus serrata, chestnut,
Castanea crenata, cork oak, Quercus variabilis, Klason lignin, dioxane lignin
1968-005
リグニンの親水性に関する研究
岡部次郎，工藤正邦
山陽パルプ株式会社
Studies on hydrophilicity of lignin
Jiro Okabe, Masakuni Kudo
Sanyo Pulp Co., Ltd.
Keywords: dioxane lignin, hydrophilicity, hygroscopy
1968-006
多段漂白における塩素化−アルカリ抽出（III）塩素化された DL の吸湿牲について
河内 進策、武井 斎
宮崎大学農学部
Chlorination-alkali extraction in multistage bleaching (III), Hygroscopy of chlorinated dioxane lignin
56

Shinsaku Kawachi, Hitoshi Takei
Faculty of Agriculture, Miyazaki University
Keywords: red pine, Pinus densiflora, Machilus thunbergii, dioxane lignin
1968-007
可塑剤によるリグニンの可塑化について
坂田 功、青柳祥二、千手諒一
九州大学農学部
Plasticization of lignin by plasticizer
Isao Sakata, Shoji Aoyagi, Ryoichi Senju
Faculty of Agriculture, Kyusyu University
Keywords: red pine, Pinus densiflora, dioxane lignin, thiolignin, phthalic acid ester, tributyl phosphate,softening temperature
1968-008
チオリグニンの加熱時における活性基量の変化について
岩見田 糺，佐藤孝一郎
国策パルプ株式会社
Change in the amount of reactive groups during heat treatment of thiolignin
Tadashi Iwamida, Koichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: reactive groups, alcoholic hydroxyl group, phenolic hydroxyl group, carboxyl group
1968-009
リグニンラジカルの性状について
畠山兵衛＊１、籏野 晃＊１、中野準三＊２、右田伸彦＊２＊１
アラスカパルプ株式会社、＊２東京大学農学部
Properties of radical in lignin
Hyoe Hatakeyama＊１, Akira Hatano＊１, Junzo Nakano＊２, Nobuhiko Migita＊２＊１
Alaska Pulp Co. Ltd.,＊２Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, electron spin resonance spectra, milled wood lignin, dioxane lignin,
calcium lignosulfonate, thiolignin, -ray irradiation
1968-010
リグニン分子中のピノレジノール構造について（第 5 報）酸アルカリ処理とピノレジノール構造
荻山紘一、近藤民雄
九州大学農学部
On the pinoresinol type of structural units in lignin molecule (V), Effect of acid or alkali treatment on
pinoresinol structures
Koichi Ogiyama, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: Japanese red pine, Pinus densiflora, Cryptomeria japonica, Betula Tauschii, Shorea negrosensis,
dioxane lignin, symplocosigenol
1968-011
アルカリ処理によるリグニン分子の変化 —NMR による芳香環置換度の測定について
諸星紀幸、榊原 彰
北海道大学農学部
Change in lignin molecule by alkaline treatment, — Determination of condensed type unit by NMR
spectroscopy
Noriyuki Morohoshi, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, milled wood lignin, assignment of proton signal
57

1968-012
液安中金属ナトリウムによるリグニンの分解
山口 彰、広居忠量、宮崎 信
林業試験場
Degradation of lignin with metallic sodium in liquid ammonia
Akira Yamaguchi, Tadakazu Hiroi, Makoto Miyazaki
Keywords: Yezo spruce, Picea jezoensis, milled wood lignin, lignin carbohydrate complex, paper
chromatography, gas chromatography
1968-013
プロトリグニンの水素化分解（弟 4 報）フェニルクマラン開環型分解物の単離、同定について
松倉紀男、榊原 彰
北海道大学農学部
Hydrogenolysis of protolignin. IV. Isolation and identification of open-ring-phenylcoumaran type products
Motoo Matsukura, Akira sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, thin-layer chromatography, gas chromatography,
1-(4-hydroxy-3-methoxyphenyl)-2-(2’-hydroxy-3’-methoxy-5’-propylphenyl)-propane
1968-014
ジオキサン-水によるリグニンの加水分解（第 8 報）
佐野嘉拓、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane and water (VIII)
Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: column chromatography, p-hydroxyphenylglycerol, NMR, UV absorption spectroscopy
1968-015
Björkman リグニンの酸素酸化に関する研究
渡辺貞良、林 治助、戸坂圀夫、小林昌子
北海道大学工学部
Oxidation of Björkman lignin with oxygen
Sadayoshi Watanabe, Jisuke Hayashi, Kunio Tosaka, Masako Kobayashi
Faculty of Engineering, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, functional group, hydroxyl group, carboxyl group, infraredabsorption spectroscopy
1968-016
リグニンスルホン酸の電解酸化
小川博嗣、富田由明
東京工業試験所
カルボキシル基、メトキシル基Electrolytic oxidation of lignin sulfonic acid
Hirotsugu Ogawa, Yoshiaki Tomita
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: carboxyl group, methoxyl group,
1968-017
電子スペクトルの解析によるリグニンの着色機構の検討
飯山賢治、中野準三、右田伸彦
東京大学農学部
Studies on the coloring mechanism of lignin by the electronic spectral analysis
Kenji Iiyama, Junzo Nakano, Nobuhiko Migita
58

Faculty of Agriculture, the University of Tokyo
Keywords: thiolignin, milled wood lignin, lignin model compounds, adsorption band, vanillyl alcohol,
assignment of absorption band
1968-018
リグニンに対する亜二チオン酸塩の反応機構について
細谷修二、畠山兵衝、中野準三、右田伸彦
東京大学農学部
Reaction mechanism of sodium hydrosulfite with lignin
Shuji Hosaya, Hyoe Hatakeyama, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: calcium lignosulfonate, lignin model compounds, vanillin, acetoguaiacone, isoeugenol,o-quinone
1968-019
リグニン脱メチル生成物の着色について
林 晄、上北忠之
立命館大学理工学部
Coloring of demethylated lignin
Akira Hayashi, Tadayuki Kamikita
College of Science and Engineering, Ritsumeikan University
Keywords: guaiacol, 1-cyclopentene carboxylic acid, catechol, quinhydron, quinone
1968-020
サルフアイト蒸解におけるリグニンの着色について
飯塚堯介、川上菊士、中野準三、右田伸彦
東京大学農学部
Coloring of lignin during sulfite cooking
Gyosuke Meshitsuka, Kikuo Kawakami, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: fir, Abies firma, functional group, UV absorption difference spectroscopy
1968-021
Hydrotropic cooking について
村主信彦、近藤民雄
九州大学農学部
Studies on the hydrotropic cooking
Nobuhiko Suguri, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: xylene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, benzoic acid, surface tension
1968-022
リグニンの蓄電池に及ほす効果について林 晄，木下恭介
立命館大学理工学部
Effect of addition of lignin to battery
Akira Hayashi, Kyousuke kinoshita
College of Science and Engineering, Ritsumeikan University
Keywords: polyphenol, chelating agent, catechol, resorcinol
1968-023
リグノスルホン酸塩の色におよほす重金属イオンの影響
飯塚堯介、中野準三，右田伸彦
東京大学農学部59

Effect of heavy metal ions on the color of lignosulfonate
Gyosuke Meshitsuka, Junzo Nakano, Nobuhiko Migita
Faculty of Agriculture, the University of Tokyo
Keywords: iron, copper, nickel, vanadium, manganese, chromium, visible light absorption spectra
1968-024
リグノスルホン酸類と各種金属イオンとの反応牲
猪狩俶将，横山正一郎、室井和彦
東京工業試験所
Reactivity of various metal ions with lignosulfonic acid
Yoshimasa Ikari, Shoichiro Yokoyama, Kazuhiko Muroi
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: iron, calcium, cadmium, nickel, copper, chromium, manganese, UV light absorption
spectroscopy
1968-025
亜硫酸パルプ排液と重クロム酸の反応に関する研究（第 2 報）
岡部次郎，町原 晃，三浦義之
山陽パルプ株式会社
Reaction of sulfite spent liquor with dichromate (II)Jiro Okabe, Akira Machihara, Yoshiyuki Miura
Sanyo Pulp Co., Ltd.
Keywords: soil stabilizer, lignosulfonic acid, sugar, gelation, chelate
1968-026
ポリフェノールの酸化カップリング反応
熊野谿従、加藤 隆
東京工業大学
Oxidative coupling reaction of polyphenols
Ju Kumanotani, Takashi Kato
Tokyo Institute of Technology
Keywords: urushiol, thin layer chromatography, o-quinone, nuclear magnetic resonance
1968-027
重クロム酸塩によるフェノールの酸化カップリング
田中浩雄、坂田 功、千手諒一
九州大学農学部
Oxidative coupling of phenols by potassium dichromate
Hiroo Tanaka, Isao Sakata, Ryoichi Senjyu
Faculty of Agriculture, Kyusyu University
Keywords: p-cresol, creosol, manganese
1968-028
リグニンのゲル化機構
田中浩雄、坂田 功、千手諒一
九州大学農学部
Gelation mechanism of lignin
Hiroo Tanaka, Isao Sakata, Ryoichi Senjyu
Faculty of Agriculture, Kyusyu University
Keywords: chromium, chelate, lignin sulfonic acid, polyhydroxystyrene sulfonic acid60

第 14 回 （1969.10.28-29）東京、日本化学会講堂
1969-001
アテ材リグニンの化学的特性に関する研究（第２報）
諸星紀幸、榊原 彰
北海道大学農学部
Chemical properties of of reaction wood (II)Noriyuki Morohoshi, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Abies mayriana, Fraxinus excelsissima, milled wood lignin, lignin carbohydrate complex,
potassium permanganate oxidation, ethanolysis, nitrobenzene oxidation, gas chromatography
1969-002
ジオキサンー水によるリグニンの加水分解（第 9 報）
佐野嘉柘、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane and water (IX)
Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: guaiacylglycerol, 1,2-bisguaiacylpropane1,3-diol, NMR, mass spectrometry
1969-003
AP 法廃液からのアルカリ・リグニンの性状について
香川詔士、内田 壮
関東学院大学工学部
Characteristics of alkali lignin in soda pulping waste liquor
Shoji Kagawa, So Uchida
Faculty of Engineering, Kanto Gakuin University
Keywords: larch, Larix Kaempferi, soda pulping waste liquor, hydrochloric acid lignin, differential thermal
analysis, nitrobenzene oxidation
1969-004
クラフト蒸解中におけるグアヤシル核 5 位置換型構造の生成について
玉生征人、寺島典二
名古屋大学農学部
Formation of guaiacyl nucleus with substitution at position 5 during kraft pulping
Masato Tamao, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: 14C-labeledligninmodel
compounds,
guaiacylglycerol-β-guaiacyl
guaiacylglycerol-β-guaiacyl ether-[β-14C], guaiacylglycerol-β-guaiacyl ether-[γ-14C],

ether-[α-14C],

1969-005
リグニン中のピノレジノール構造について（第 6 報）KP 蒸解とピノレジノール構造との関係
荻山紘一、谷口栄一
山形大学農学部
Pinoresinol structure in lignin (VI), Behavior of pinoresinol structure during kraft cooking
Koichi Ogiyama, Eichi Taniguchi
Faculty of Agriculture, Yamagata University
Keywords: Symplocos lucida, Pinus densiflora, Betula tauschii, symplocosin, symplocosigenol,
syringaresinol
1969-006
リグノスルホン酸塩中の共役二重結合について
飯塚堯介、中野準三
61東京大学農学部
Conjugated double bonds in lignosulfonate
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: coniferaldehyde, coniferyl alcohol, stilbene, chalcone, phenylcoumaran
1969-007
リグニン分解木材腐朽菌（未同定菌）によるアセトン・リグニンの分解生成物
福住俊郎、南 享二
東京大学農学部
Degradation products of acetone lignin by a wood-rotting fungus (unidentified white rot type)Toshio Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Yezo spruce, Picea jezoensis, jar-fermentor, hydroxymatairesinol
1969-008
カワラタケ酵素のワニリン酸に対する挙動
石原達夫、宮崎 信
林業試験場
Behavior of enzyme of Polyporus versicolor on vanillic acid
Tatsuo Ishihara, Makoto Miyazaki
Forestry and Forest Product Research Institute
Keywords: laccase, peroxidase, UV spectroscopy, IR spectroscopy, NMR
1969-009
広葉樹の葉における芳香核構造の季節的変動
田中治郎、千野広子
林業試験場
Seasonal change of aromatic structures in the leaves of hardwood
Jiro Tanaka, Hiroko Chino
Forestry and Forest Product Research Institute
Keywords: sycamore, Platanus occidentalis, nitrobenzene oxidation, formation of aldehydes
1969-010
Hydrotropic Cooking について（II）
村主信彦、近藤民雄
九州大学農学部
Hydrotropic cooking (II)Nobuhiko Suguri, Tamio kondo
Faculty of Agriculture, Kyusyu University
Keywords: sodium xylenesulfonate, sodium benzoate, gel filtration chromatography
1969-011
リグニンの水溶性化に関する研究
工藤正邦，岡部次郎
山陽パルプ株式会社
Studies on water solubilization of lignin
Masakuni Kudo, Jiro Okabe
Sanyo Pulp Co., Ltd.
Keywords: solubilization, dioxane lignin, sulfonation, hygroscopy, sulfonic group
1969-012
ゲル濾過法によるリグノスルホン酸類の分別
猪狩俶将、横山正一郎
62

東京工業試験所
Fractionation of lignosulfonic acids by gel filtration chromatography
Yoshimasa Ikari, Shoichiro Yokoyama
Tokyo Institute of Advanced Industrial Science and Technology
Keywords: molecular weight distribution, sephadex, affinity
1969-013
リグノスルホン酸とスチレンのグラフト共重合における Fe[III]イオンによる酸化の効果
村木永之介、越島哲夫
大阪工業技術試験所
Effect of oxidation with ferric ion on the copolymerization of lignosulfonic acid and styrene
Einosuke Muraki, Tetsuo Koshijima
National Industrial Research Institute of Osaka
Keywords: vanillyl sulfonic acid, graft polymer
1969-014
フエノール系高分子（リグニンモデル）の合成とその重クロム酸塩によるゲル化田中浩雄、坂田 功、千手諒一
九州大学農学部
Synthesis of phenolic polymers (lignin model) and their gelation by dichromate
Hiroo Tanaka, Isao Sakata, Ryoichi Senju
Faculty of Agriculture, Kyusyu University
Keywords: poly-4-hydroxystyrenesulfonic acid, poly-4-hydroxy-3-methoxystyrene
poly-4-hydroxy-3,5-dimethoxystyrene sulfonic acid, viscosity, molecular weight
1969-015
リグニンゲルとポリウロン酸ゲルの粘性について
石川久雄、木下良郎、大久保克美、沖 妙
愛媛大学農学部
Viscosity of lignin gel and polyuronide gel
Hisao Ishikawa, Yoshiro Kinoshita, Katsumi Okubo, Tae Oki
Faculty of Agriculture, Ehime University
Keywords: Abelmoschus manihot, alginate, lignin sulfonic acid, calcium ion
1969-016
ベラトリルスルホン酸の電解酸化
小川博嗣、戸倉保司
東京工業試験所
Electrolytic oxidation of veratryl sulfonic acid
Hiroshi Ogawa, Yasusi Tokura
National Industrial Research Institute of Tokyo
Keywords: pH, UV absorption spectra, demethylation
1969-017
チオリグニンの熱重合時における生成ガスについて
岩見田 糺
国策パルプ株式会社
Gases generated during polymerization of thiolignin by heat treatment
Tadashi Iwamida
Kokusaku Pulp Co., Ltd.
Keywords: heat treatment, polymerization, gaschromatography
1969-018
リグニンの DSC による熱解析
63

sulfonicacid,

畠山兵衛、久保田勝也
製品科学研究所
Thermal analysis of lignin by differential scanning calorimetry
Hyoe Hatakeyama, Masaya Kubota
Industrial Products Research Institute
Keywords: glass transition temperature, differential scanning calorimetry, milled wood lignin, dioxane
lignin, thiolignin, calcium lignosulfonate
1969-019
リグニンモデル化合物の過酢酸酸化分解について
沖 妙、木下良郎、石川久雄
愛媛大学農学部
Oxidative degradation of lignin model compounds by peracetic acidTae Oki, Yoshiro Kinoshita, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Baeyer-Villiger reaction, dehydrodiisoeugenol, isoeugenol, UV absorption spectroscopy
1969-020
パルプ廃液の色に関する研究（I）KP 晒廃液の色とオキシリグニン
鮫島一彦、近藤民雄
九州大学農学部
Studies on the color of pulping waste liquor (I), Color of waste liquor from kraft pulp bleaching and oxylignin
Kazuhiko Sameshima, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: Japanese red pine, Pinus densiflora, Betula Tauschii, multistage bleaching, UV absorption
spectroscopy

64

第 15 回 （1970.10.8-9） 札幌市民会館
1970-001
タケリグニンのメトキシル基生成に関する生化学的研究
島田幹夫、樋口隆昌
京都大学木材研究所
Biochemical studies on the formation of methoxyl groups in bamboo lignin
Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phyllostachys reticulata, bamboo shoot, O-methyltransferase, caffeic acid-2-14C, ferulic
acid-2-14C, S-adenosyl methionine
1970-002
タケ及びイネ科植物リグニン中の p−クマール酸エステル結合に関する研究
島田幹夫、樋口隆昌
京都大学木材研究所
Studies on the coumaric acid ester bonds in lignins of bamboo and gramineous plants
Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: dehydrogenative polymer, coniferyl alcohol, UV absorption spectra, radio-labeled p-coumaricacid, methanolysis
1970-003
コニフェリルアルコールの脱水素重合におよばすへミセルロースの影響
樋口隆昌、荻野桂作
京都大学木材研究所
Effect of hemicelluloses on dehydrogenative polymerization of coniferyl alcohol
Takayoshi Higuchi, Keisaku Ogino
Wood Research Institute, Kyoto University
Keywords: pectin, peroxidase, dehydrogenative polymer, molecular weight, UV absorption spectra
1970-004
酵素によるリグニンのエーテル結合の分解
松本 久、福住俊郎、南 享二
東京大学農学部
Cleavage of ether bonds in lignin by enzyme
Hisashi Matsumoto, Toshiro Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: wood rotting fungi, Perenniporia subacida, thin layer chromatography, gas chromatography
1970-005
放線薗の一種によるリグニンの分解
原口隆英
東京農工大学農学部
Degradation of lignin by Actinomycetes sp.
Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: potassium lignosulfonate, vanillic acid, UV absorption spectrometry, chemical oxygen demand
1970-006
ヒノキ-MWL 及び LCC の化学特性、その分子量分布について
広居忠量、宮崎 信
林業試験場
65Chemical properties of MWL and LCC of Japanese cypress, and their molecular weight distribution
Tadakazu Hiroi, Makoto Miyazaki
Forestry and Forest Products Research Institute
Keywords: Japanese cypress, Chamaecyparis obtusa, gel permeation chromatography, number averagemolecular weight, vapor pressure osmometry
1970-007
液安中の金属ナトリウムによるリグニンの分解（II）
山口 彰、宮崎 信
林業試験場
要旨なし（中止）
1970-008
サルファイト蒸解過程におけるリグニンの酸加水分解について
飯塚尭介、中野準三
東京大学農学部
Acid hydrolysis of lignin during sulfite cooking process
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: red pine, Pinus densiflora, repeating unit, lignosulfonic acid, molecular weight distribution, ge
filtration chromatography
1970-009
塩化アルミニウムによるリグノスルホン酸塩の凝集沈澱について飯塚尭介、徐道太郎、中野準三
東京大学農学部
Precipitation of lignisulfonate by coagulation with aluminum chloride
Gyosuke Meshitsuka, Michitaro Jo, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: softwood, conifer, gel filtration, pH, phenolic hydroxyl group, alcoholic hydroxyl group
1970-010
リグノスルホン酸塩とメタクリル酸メチルのフエントン試薬によるグラフト重合反応（その 1）
南正院、斉藤雅康、村木永之介、越島哲夫
大阪工業技術試験所
Graft polymerization of lignosulfonate and methyl methacrylates by Fenton’s reagent (I)Zeong-Woun Nam, Masayasu Saito, Einosuke Muraki, Tetsuo Koshijima
Osaka Institute of Advanced Industrial Science and Technology
Keywords: softwood, conifer, molecular weight, veratryl sulfonic acid p-hydroxybenzylsulfonic acid
1970-011
木材パルプのアクリルアミドグラフト重合にたいするリグニンの影響
小林晃夫＊１、W. Brown＊２、V. Stannett＊３＊１
国策パルプ株式会社、＊２Uppsala 大学、＊３North Carolina 州立大学
Influence of lignin on graft polymerization of acrylamide to wood pulp
Akio Kobayashi*1, W. Brown*2, V. Stannett*3*1
Kokusaku Pulp Co., Ltd., *2Uppsala University, *3North Carolina State University
Keywords: spruce, Picea engelmannii, KP, kraft pulp, BKP, bleached kraft pulp, DP, dissolve pulp, GP,ground wood pulp, cotton linter, electron spin resonance spectroscopy
1970-012
二、三のリグニンモデル化合物合成の試み —グアヤシルプロペン類の合成—
福住俊郎、小宅茂夫、南 享二
東京大学農学部
66

Synthesis of a few lignin model compounds, –Synthesis of guaiacyl propenesToshio Fukuzumi, Shigeo Koyake, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: guaiacyl vinyl ketone, vanilloyl acetoaldehyde, coniferyl alcohol
1970-013
次亜塩素酸ナトリウムによるリグニンモデル化合物の反応について
細谷修二、中野準三
東京大学農学部
Reaction of lignin model compounds with sodium hypochlorite
Shuji Hosaya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: pH, vanillyl alcohol, veratryl alcohol, gaschromatography
1970-014
リグニンスルホン酸の二酸化塩素による酸化 —モデル化合物の酸化反応
中村孝一、横田金吾、秦 邦男
十条製紙株式会社
Oxidation of lignosulfonates with chlorine dioxide – Oxidation of model compounds
Koichi Nakamura, Kingo Yokota, Kunio Hata,
Jyujo Pulp Co., Ltd.
Keywords: lignosulfonates, chlorine dioxide, vanillyl sulfonate, syringyl sufonate
1970-015
2-(2-Methoxy-phenoxy)-1-(4-hydroxy-3-methoxyphenyl)-ethanol の過酢酸酸化について
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Oxidation of 2-(2-methoxy-phenoxy)-1-(4-hydroxy-3-methoxyphenyl)-ethanol by peracetic acidTae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Baeyer-Villiger reaction, paper chromatography, UV absorption chromatography
1970-016
パルプ廃液の色に関する研究（II）塩素オキシリグニンの着色について
鮫島一彦、近藤民堆
九州大学農学部
Studies on the color of pulping waste liquor (II), On the color of chlorin-oxylignin
Kazuhiko Sameshima, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: Pinus densiflora, Betula Tauschii, oxylignin, pH dependence, functional groups
1970-017
ハイドロトロピツク蒸解におけるリグニンの可溶化
石川久雄、沖 妙、大久保克美
愛媛大学農学部
Solubilization of lignin during hydrotropic cooking
Hisao Ishikawa, Tae Oki, Katsumi Okubo
Faculty of Agriculture, Ehime University
Keywords: beech, Fagus crenata, sodium m-xylenesulfonate, dioxane lignin, sodium salicilate
1970-018
Hydrotropic Cooking について（III）より強力なハイドロトロピック剤へのアプローチ
山田洋三、近藤民雄
九州大学農学部
67

Hdrotropic cooking (III), Approach toward more effective hydrotropic reagent
Yozo Yamada, Tamio Kondo
Faculty of Agriculture, Kyusyu University
Keywords: sodium salycilate, sodium aminobenzene sulfonate, viscosity
1970-019
アルカリ蒸解における酸素と硫黄の役割
飯山賢治、中山忠光、中野準三
東京大学農学部
Role of oxygen and sulfur in alkaline cooking
Kenji Iiyama, Tadamitsu Nakayama, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, vanillyl alcohol, acetoguaiacone, creosol, soda cooking, kraft cooking
1970-020
リグニンの脱メチル反応について
林 晄、谷口 彰
立命館大学理工学部
Demethylation reaction of lignin
Akira Hayashi, Akira Taniguchi
College of Science and Engineering, Ritsumeikan University
Keywords: Pinus densiflora, dioxane lignin, soda cooking, o-quinone
1970-021
リグニンのメチロール化反応について
阿部 勲、窪田 実
北海道林産試験場
Introduction of methylol groups onto lignin
Isao Abe, Minoru Kubota
Hokkaido Forest Products Research Institute
Keywords: kraft lignin, formaldehyde, vanillic acid, ferulic acid, p-coumaric acid
1970-022
チオリグニンの鋳型への利用
岩見田糺、佐藤孝一郎
国策パルプ株式会社
Utilization of thiolignin for shell moldTadashi Iwamida, Kouichiro Sato
Kokusaku Pulp Co., Ltd.
Keywords: hell mold, sand, binder, phenol
1970-023
アルカリリグニンからバニリンの製造について
香川詔士、六川真佐行．堀井淑子
関東学院大学工学部
Production of vanillin from alkali lignin
Shoji Kagawa, Masayuki Mutsukawa, Toshiko Horii
Faculty of Engineering, Kanto Gakuin University
Keywords: larch, Larix Kaempferi, nitrobenzene oxidation, air oxidation, UV absorption spectroscopy
1970-024
バニリン製造における副生リグニンの性状について
品川和夫、工藤正邦
山陽パルプ株式会社68

Properties of residual lignin during production of vanillin
Kazuo Shinagawa, Masakuni Kudo
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, spent liquor, vanillin, by-product, chemical structure
1970-025
蓄電池添加剤としてのリグニンの効果
木下恭介、林 晄
立命館大学理工学部
Effect of lignin as lead-acid battery additive
Kyousuke kinoshita, Akira Hayashi
College of Science and Engineering, Ritsumeikan University
Keywords: polyphenol, novolac type phenolic resin, poly-4-hydroxy-3-methoxystyrene

69

第 16 回 （1971.11.4-5） 高松電機ビル
1971-001
植物体に投与されたフエルラ酸のデメトキシ、およびメトキシレーションに関する研究
島田幹夫、伏木秀文、樋口隆昌
京都大学木材研究所
Studies on the demethoxylation and methoxylation of ferulic acid fed to a plant
Mikio Shimada, Hidefumi Fushiki, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phyllostachys pubescens, sinapic acid, 5-hydroxyferulic acid, guaiacyl nucleus, syringyl
nucleus, hardwood, softwood
1971-002
広葉樹、および針葉樹リグニンのメトキシル基形成に関する比較生化学的研究
島田幹夫、伏木秀文、樋口隆昌
京都大学木材研究所
Comparative biochemical studies on the formation of methoxyl groups in hardwood and softwood lignins
Mikio Shimada, Hidefumi Fushiki, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phyllostachys pubescens,
Pinus Thunbergii, Ginkgo biloba, O-methyltransferase,
S-adenosylmethionine
1971-003
ポプラリグニン中のパラハイドロキシ安息香酸の生合成
寺島典二，森 勇
名古屋大学農学部
Biosynthesis of p-hydroxybenzoic acid in poplar lignin
Noritsugu Terashima and Isamu Mori
Faculty of Agriculture, Nagoya University
Keywords: Populus nigra x Populus Maximowiczii, phenylalanine ammonia-lyase, t-cinnamic acid,p-coumaric acid
1971-004
広葉樹リグニン生合成についての一考察
寺沢 実、古賀卓哉、奥山 寛、三宅基夫
帯広畜産大学
Studies on the biosynthesis of lignin in hardwood
Minoru Terasawa, Takuya Koga, Hiroshi Okuyama, Motoo Miyake
Obihiro University of Agriculture and Veterinary Medicine
Keywords: Larix Kaempferi, Magnolia obobata, p−glucocoumaryl alcohol, coniferin, syringin, cambial
sap, softwood, hardwood
1971-005
MWL, LCC の磨砕に対する挙動
広居忠量、宮崎 信
林業試験場
Behavior of MWL and LCC during milling
Tadakazu Hiroi, Makoto Miyazaki
Government Forest Experiment Station
Keywords: Chamaecyparis obtusa, glucomannan, ball mill, IR spectra, molecular weight distribution
1971-006
種子リグニンの特性
萩山紘一、畠山隆一、故 谷口栄一
70

山形大学農学部
Characteristic properties of lignin in seeds
Koichi Ogiyama, Ryuuichi Hatakeyama, the late Eiichi Taniguchi
Faculty of Agriculture, Yamagata University
Keywords: Pinus densiflora, Juglans Sieboldiana, UV spectra, IR spectra, nitrobenzene oxidation
1971-007
竹リグニンのアシドリシス (第 2 報) アシドリシス生成物の分離同定
中坪文明、棚橋光彦、樋口隆昌
京都大学木材研究所
Acidolysis of bamboo lignin (II), Isolation and identification of acidolysis products
Fumiaki Nakatsubo, Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: gel filtration, NMR, IR, p-coumaric acid, arylglycerol-β-aryl ether substructure
1971-008
竹リグニンのアシドリシス（第 3 報） アリルグリセロール-β-アリルエーテルの合成とそのアシドリシス
樋口隆昌、棚橋光彦、中坪文明
京都大学木材研究所
Acidolysis of bamboo lignin (III), Synthesis of arylglycerol-β-aryl ether and its acidolysis
Takayoshi Higuchi, Mitsuhiko Tanahashi, Fumiaki Nakatsubo
Wood Research Institute, Kyoto University
Keywords: Phyllostachys pubescens, model compounds, acidolysis in dioxane-water
1971-009
プロトリグニンの水素化分解に関する研究（第 9 報） 新 2，3 量体の単離・同定について
松倉紀男＊１、榊原 彰＊2＊１
十條製紙株式会社，＊2 北海道大学農学部
Hydrogenolysis of protolignin (IX), Isolation and identification of new dimeric and trimeric products
Motoo Matsukura＊１, Akira Sakakibara＊2,＊１
Jujo Paper Co. Ltd., ＊2Faculty of Agriculture, Hokkaido University
Keywords: NMR, jezo spruce, Picea jezoensis, paper chromatography, thin-layer chromatography,
1971-010
リグニン-炭水化物複合体に関する研究 —ジオキサン−水による加水分解物からの単離—
武山浩武、榊原 彰
北海道大学農学部
Studies on the lignin-carbohydrate complex. —Isolation from hydrolysis products with dioxane-water
Hirotake Takeyama, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Picea jezoensis, paper chromatography, thin-layer chromatography
1971-011
NMR を用いた MWL の測定
佐藤 惺、北村晃子、樋口隆昌
京都大学木材研究所
NMR analysis of MWL
Akira Sato, Teruko Kitamura, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Metasequoia glyptostroboides, Fagus crenata, Phyllostachys, molecular weight distribution
1971-012
チオリグニンの熱的性質に及ぼす分子量の影響について
岩下建二＊1、飯塚堯介＊1、畠山兵衛＊２、中野準三＊1
71

＊1

東京大学農学部、＊２製品科学研究所
Effect of molecular weight on thermal properties of thiolignin
Kenji Iwashita＊1, Gyosuke Meshitsuka＊1, Hyoe Hatakeyama＊2, Junzo Nakano＊1＊1
Faculty of Agriculture, the University of Tokyo＊２Industrial Products Research Institute
Keywords: Abies mayriana, Fagus crenata, gel filtration, differential scanning calorimetry
1971-013
リグニンモデル化合物の酸化電位について
小川博嗣
東京工業試験所
Oxidation potential of lignin model compounds
Hirotsugu Ogawa
Government Chemical Industrial Research Institute, Tokyo
Keywords: polarography, vanillin, vanillic acid, vanillyl sulfonic acid
1971-014
サルファイト蒸解におけるリグニン・糖複合体の挙動について
飯塚堯介、白銀英明、中野準三
東京大学農学部
Behavior of lignin-carbohydrate complex during sulfite cooking
Gyosuke Meshitsuka, Hideaki Shirogane, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Pinus densiflora, gel filtration, peracetic acid treatment
1971-015
サルファイト系高歩留りパルプ製造時のリグニンの挙動
岩見田 糺*1，浜田忠平*1，李 宗藩*2，中野準三*2*1
国策パルプ株式会社，*2 東京大学農学部
Behavior of lignin during sulfite chemimechanical pulping
Tadashi Iwamida*1, Tadahira Hamada*1, Sohan Ri*2, Junzo Nakano*2*1
Kokusaku Pulp Co., Ltd., *2the University of Tokyo, Faculty of Agriculture
Keywords: defibration, sulfonic acid group, middle lamella, secondary wall
1971-016
クラフト蒸解における残存および溶出リグニンの性状
飯山賢治、中野準三
東京大学農学部
Properties of dissolved and residual lignin in kraft pulp
Kenji Iiyama, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Pseudotsuga taxifolia, color of lignin, color of pulp, MWL, molecular weight distribution
1971-017
ソーダ蒸解によるリグニンの着色機構
林 晄、木下恭介、谷口 彰
立命館大学理工学部
Coloring mechanism of lignin during soda cooking
Akira Hayashi, Kyosuke Kinoshita, Akira Taniguchi
Faculty of Science and Engineering, Ritsumeikan University
Keywords: model compound, quinone, catechol, chromophoric groups
1971-018
2-(2-Methoxy-phenoxy)-1-(4-hydroxy-3-methoxyphenyl)-ethanol とそのメチル化物の過酢酸酸化について
沖 妙、大久保克美、石川久雄
72愛媛大学農学部
Peracetic acid oxidation of 2-(2-Methoxy-phenoxy)-1-(4-hydroxy-3-methoxyphenyl)–ethanol
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: TLC, NMR, IR absorption spectroscopy
1971-019
β-アリルエーテル型リグニンモデル化合物の過酢酸酸化
坂井克己＊１、黒田健一＊１、岸本定吉＊２＊１
九州大学農学部, ＊２東京教育大学農学部
Peracetic acid oxidation of -aryl ether type lignin model compounds
Kokki Sakai＊１, Ken-ichi Kuroda＊１, Sadakichi Kishimoto＊2＊１
Faculty of Agriculture, Kyushu University, ＊2Faculty of Agriculture, Tokyo University of Education
Keywords: conifer lignin, guaiacylglycerol--guaiacyl ether, gas chromatography, mass spectrometry
1971-020
酸化漂白剤によるビフエニル型リグニンモデル化合物の反応について
細谷修二、中野準三
東京大学農学部
Reaction of biphenyl type lignin model compounds with oxidative bleaching agents
Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords:
dehydrodivanillyl alcohol, dehydrodiveratryl alcohol, sodium hypochlorite, hydrogen peroxide
1971-021
高歩留パルプの漂白機構について—漂白剤添加量と白色度増加との関係
加納 直*1，細谷修二*2，中野準三*2*1
国策パルプ，*2 東京大学農学部
Mechanism of bleaching of high yield pulp – Relation between dosage of bleaching agent and increase ofbrightness
Tadashi Kano*1, Shuji Hosoya*2, Junzo Nakano*2*1
Kokusaku Pulp Co.,Ltd., *2Faculty of Agriculture, the University of Tokyo
Keywords: chemimechanical pulp, cold soda process, hydrogen peroxide, MWL
1971-022
塩素化リグニンのアルカリ抽出におよぼす熱処理の影響について（II）
河内進策
宮崎大学農学部))
Effect of thermal treatment on alkali extraction of chlorinated lignin (II)Shinsaku Kawachi
Faculty of Agriculture, Miyazaki University
Keywords: Pinus densiflora, dioxane lignin, holocellulose
1971-023
ゲルろ過法による針葉樹と広葉樹リグノスルホン酸類の比較
猪狩俶将、横山正一郎
東京工業試験所
Comparison of lignosulfonic acids prepared from softwood and hardwood by gel filtration
Government Chemical Industrial Research Institute, Tokyo
Yoshimasa Ikari, Shoichirou Yokoyama
Keywords: sephadex
1971-024
リグノスルホン酸塩とメタクリル酸メチルのフエントン試薬によるグラフト重合反応（その 2）73越島哲夫、南 正院、村木永之介
大阪工業技術試験所
Graft copolymerization of methyl methacrylate onto lignosulfonate by Fenton reagent, II.
Tetsuo Koshijima, Chongwon Nam, Einosuke Muraki,
Government Industrial Research Institute, Osaka
Keywords: barium p-hydroxybenzylsulfonate, barium vanillylsulfonate, barium veratrylsulfonate,
1971-025
金属酸化物触媒の存在下におけるリグニンスルホン酸塩のアルカリ酸化分解 —酸化銅触媒の表面特性がバニリン生成反応に及ほす影響
高橋英郎、渡辺昭雄
東京工業試験所
Alkaline oxidative degradation of lignosulfonate in presence of metal oxide catalyst, —Effect of surface
properties of copper oxide catalyst on vanillin production
Hideo Takahashi, Akio Watanabe
Government Chemical Industrial Research Institute, Tokyo
Keywords: volatile acid, oxygen consumption
1971-026
アルカリリグニンの空気酸化について
香川詔士、古梶 誠
関東学院大学工学部
Air oxidation of alkali lignin
Shoji Kagawa, Makoto Kokaji
Faculty of Engineering, Kanto Gakuin University
Keywords: Larix Kaempferi, gas chromatography
1971-027
バニリン製造における副生リグニンの性状に関する研究（第 2 報）
品川和夫，工藤正邦，岡部次郎
山陽パルプ
Properties of residual lignin during production of vanillin (II)
Kazuo Shinagawa, Masakuni Kudo, Jiro Okabe
Sanyo Pulp Co., Ltd.
Keywords: sulfite pulp, spent liquor, vanillin, by-product, lignin, molecular weight, sulfopropylation
1971-028
濃縮 SP 廃液とフエノールによる耐水性接着剤の製造に関する研究
榊原 彰、佐野嘉拓
北海道大学農学部
Preparation of water resistant adhesives from concentrated sulfite waste liquor and phenol
Akira Sakakibara, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Keywords: chest nut powder, formaldehyde
1971-029
カワラタケのラッカーゼによる MWL の分解
石原達夫、宮崎 信
林業試験場
Degradation of MWL by laccase of Polyporus versicolor
Tatsuo Ishihara, Makoto Miyazaki
Forestry and Forest Product Research Institute
Keywords: Acer palmatum Thunb, wood rotting fungi, milled wood lignin, GPC
74

1971-030
加水分解酵素によるリグニンの分解
福住俊郎、南 享二
東京大学農学部
Degradation of lignin by hydrolase
Toshio Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, Polystictus sanquineus, Perenniporia subacida, Brauns’s lignin
1971-031
放線菌によるリグニンの分解（第 2 報）
原口隆英、諸星紀幸
東京農工大学農学部
Degradation of lignin by Actinomycetes (II)Takafusa Haraguchi, Noriyuki Morohoshi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: lignosulfonic acid, gel filtration, UV absorption spectra, p-hydoxybenzoic acid, vanillic acid
1971-032
パルプ廃液の色に関する研究（II） 塩素化オキシリグニンの着色について（2）鮫島一彦、住本昌之、近藤民雄
九州大学農学部
Studies on the color of pulping waste liquor (II) Color of chlorinated oxylignin (2)Kazuhiko Sameshima, Masashi Sumimoto, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: benzoquinone, auxochrome, complex chromophore
1971-033
パルプ製造排水の凝集処理に関する研究
徐道太郎、飯塚堯介、中野準三
東京大学農学部
Treatment of pulp and paper mill wastewater by coagulation–flocculation
Michitaro Jo, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: lignosulfonate, chlorine treatment, alkali treatment, gel filtration
1971-034
パルプ廃水の清水化に関する研究 —クラフトリグニンの活性炭による吸着
壁谷 洋、藤井利郎、久保隆昌
四国工業技術試験所
Purification of pulp and paper mill wastewater – Adsorption of kraft lignin by activated carbon
Hiroshi Kabeya, Toshirou Fujii, Takamasa Kubo
Government Industrial Research Institute, Shikoku
Keywords: adsorption isotherm75

第 17 回 （1972.11.4-5） 京都大学農学部
1972-001
広葉樹材生長過程における S/V 比の変動
田中治郎、宮崎 信
林業試験場
Variation of S/V ratio during growing of hardwood
Jiro Tanaka, Makoto Miyazaki
Government Forest Experiment Station
Keywords: Platanus occidentalis, nitrobenzene oxidation
1972-002
加水分解酵素による木粉よりのリグニン分解物
福住俊郎
東京大学農学部
Degradation products from lignin in wood meal by hydolase
Toshiro Fukuzumi
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, cellulase from Trametes sanquineus, Meicelase
1972-003
南洋材リグニンの特性について（2）南洋材広葉樹の 1％−NaOH 易溶性リグニンについて
荻山紘一、安江保民
山形大学農学部
Characteristics of the tropical wood lignins (II), Lignin soluble in 1% NaOH in tropical hardwood
Koichi Ogiyama, Moritami Yasue
Faculty of Agriculture, Yamagata University
Parashorea melaanonan, Shorea rubroshorea, white lauan, red lauan, 1%NaOH-extract, polymer
1972-004
リグニンの水素化分解に関する研究（第 10 報）新二，三量体の単離について
須藤賢一、榊原 彰
北海道大学農学部
Hydrogenolysis of protolignin (X), Isolation of new dimer and trimer
Kenichi Sudo, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, TLC, 1H-NMR, UV spectroscopy
1972-005
広葉樹リグニンの加水分解物から新リグナン型化合物およびシリンギルグリセロール-β-シリンギルグリセロ
ールエーテルの単離
大森茂俊、榊原 彰
北海道大学農学部
Isolation of a new lignan-type compound and syringylglycerol-β-syringyl ether from hydrolysis products ofhardwood lignin
Shigetoshi Omori, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Fraxinus excelsissima, 1H-NMR, UV spectroscopy, IR spectroscopy, mass spectrometry
1972-006
ジオキサン-水によるリグニンの加水分解・スチルベン分解物について
佐野嘉拓、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane-water. On the stilbene type degradation products
76

Yoshihiro Sano, Akira Sakakibara,
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, MWL, 1H-NMR, UV spectroscopy, IR spectroscopy
1972-007
液安中金属ナトリウムによるリグニンの分解−III
山口 彰
林業試験場
Degradation of lignin by metallic sodium in liquid ammonia (III)Akira Yamaguchi
Government Forest Experiment Station
Keywords: Yezo spruce, Picea jezoensis, guaiacyl-1,3-propanediol, 1H-NMR,
1972-008
リグニンの分子運動におよぼす置換基の影響に関する研究
畠山兵衛
製品科学研究所
Effect of substituent group on molecular motion of lignin molecule
Hyoe Hatakeyama
Industrial Products Research Institute
Keywords: dioxane lignin, thiolignin, polystyrene, GPC
1972-009
塩素化リグニンの光化学反応による脱ハロゲン島田謹爾＊1、稲田 治＊2＊1
林業試験場, ＊2 東京農工大学農学部
Dehalogenation of chlorolignin by photochemical reaction
Kinji Shimada*1, Osamu Inada*2*1
Government Forest Experiment Station, ＊2Faculty of Agriculture, Tokyo University of Agriculture andTechnology
Keywords: Pinus densiflora, Fagus crenata, MWL, irradiation of UV light, GLC
1972-010
過酢酸酸化のさいの β−アリルエーテル型構造の拳動
坂井克己、近藤民雄
九州大学農学部
Behavior of  -aryl ether type structure in peracetic acid oxidation
Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Pinus densiflora, Betula Tauschii, MWL, acidolysis,
1972-011
特別講演、リグニン化学の進歩と今後の進路
榊原 彰
北海道大学農学部
Invited lecture: Progress and future prospects of lignin chemistry
Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: occurrence, distribution, formation, lignin in reaction wood, carbohydrates, structural model
1972-012
亜硫酸パルプ排液よりキシロースの単離加藤孝二郎，工藤正邦，岡部次郎
山陽国策パルプ
77Isolation of xylose from sulfite spent liquor
Koujiro Kato, Masakuni Kudo, Jiro Okabe
Sanyo Kokusaku Pulp Co., Ltd.
Keywords: sugar composition, pentose, hexose, extraction solvent
1972-013
リグニン中のキノイド構造
飯山賢治、中野準三
東京大学農学部
Quinoid structure in lignin
Kenji Iiyama, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, MWL, thiolignin, lignosulfonic acid, visible light absorption spectrometry,o-quinone,
1972-014
高歩留パルプの酸化および還元漂白中におけるキノン類の挙動に関する研究
細谷修二、清家孝一、中野準三
東京大学農学部
Behavior of quinones during oxidative and reductive bleaching of high yield pulp
Shuji Hosoya, Koichi Seike, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: methoxy-p-quinone, 2,6-dimethoxy-p-quinone, 2-6-dimethoxybibenzoquinone,
peroxidehydrogen

1972-015
パルプ廃液の色に関する研究（第 4 報）オキシリグニンと金属塩（2）鮫島一彦、住本昌之、近藤民雄
九州大学農学部
Studies on the color of pulp waste liquor, IV. Oxylignin and metal salt (II)Kazuhiko Sameshima, Masashi Sumimoto, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: aluminum ion, calcium ion, pH, gel filtration, lignin aluminum cpmplex
1972-016
パルプ製造排水の凝集処理に関する研究
徐道太郎、飯塚堯介、中野準三
東京大学農学部
Studies on coagulation treatment of waste liquor from pulp millMichitaro Jyo, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Pinus densiflora, sulfite pulping, chlorine treatment, ferric sulfate, aluminum sulfate, pH
1972-017
ソーダ、酸素蒸解におけるリグニンの挙動について
十河村男、幡 克美
香川大学農学部
Behavior of lignin during soda-oxygen cooking
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: Pinus densiflora, Fagus crenata, MWL, UV absorption spectroscopy, IR absorption
spectroscopy
1972-018
アミノベンゼンスルホン酸塩リグニンについて（II)78黒田健一、坂井克己、近藤民雄
九州大学農学部
On aminobenzenesulfonate lignin (II)Ken-ichi Kuroda, Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Fagus crenata, dioxane lignin, UV absorption spectroscopy, IR absorption spectroscopy
1972-019
高歩留り蒸煮木材のリファイニングにおいて剥離される中間層について
岩見田 糺*1，中野準三*2*1
山陽国策パルプ，*2 東大農
Properties of middle lamella peeling during refining of steamed wood in sulfite semichemiical process
Tadashi Iwamida*1, Junzo Nakano*2*1
Sanyo Kokusaku Pulp Co., Ltd., *2 Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, sulfite cooking, cell wall layers, electron microscope
1972-020
特別講演: Tappi Chromophores セミナーおよび酸素−アルカリ蒸解・漂白セミナーに参加して
中野準三
東京大学農学部
Invited lecture: Reports as an attendant at the Tappi Chromophore Seminar and Oxygen-Alkali Cooking,Bleaching Seminar
Junzo Nakano
Faculty of Agriculture, the University of Tokyo

79

第 18 回 （1973.11.3-4） 九州大学農学部
1973-A01
シナップ酸の還元および針葉樹におけるシリンギルリグニンの生成
中村吉紀、樋口隆昌
京都大学木材研究所
Reduction of sinapic acid and formation of syringyl lignin in conifer
Yoshiki Nakamura, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keyword:poplar, Populus spp., cherry, Prunus densiflora, red pine, Pinus densiflora, Ginkgo biloba,
acidolysis, GC-MS analysis
1973-A02
p-クマリルアルコールの脱水素重合（II）. Coumaran の Configuration
中坪文明、樋口隆昌
京都大学木材研究所
Dehydrogenative polymerization of p-coumaryl alcohol (II), Configuration of coumaran substructures
Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywordsynthesis of coumarans, 1H-NMR
1973-A03
P-ヒドロキシシンナミルアルコール類の酵素的脱水素反応によるアリルグリセロールの生成
樋口隆昌、中坪文明、池田良久
京都大学木材研究所
Formation of arylglycerol by enzymatic dehydrogenation of p-hydroxycinnamyl alcohols
Takayoshi Higuchi, Fumiaki Nakatsubo, Yoshihisa Ikeda
Wood Research Institute, Kyoto University
Keywords: synthesis of arylglycerols, 1H-NMR, laccase, peroxidase
1973-A04
プロトリグニンの水素化分解に関する研究（第 12 報）—炭素・炭素結合を有する二，三の 2 量体、3 量体の単離、同定について
須藤賢一、榊原 彰
北海道大学農学部
Hydrogenolysis of protolignin (XII), Isolation and identification of some dimmers and trimers havingcarbon-carbon bond
Kenichi Sudo, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Picea jezoensis, UV absorption spectrometry, 1H-NMR, gas chromatography-mass spectrometry
1973-A05
磨砕木粉の酵素分解（1）佐野嘉拓、榊原 彰
北海道大学農学部
Enzymatic degradation of milled wood (I)Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: hemicellulase, cellulase, nitrobenzene oxidation
1973-A06
竹 MWL アシドリシス残渣のオゾン分解
棚橋光彦、中坪文明、樋口隆昌
京都大学木材研究所
80

Ozonolysis of acidolysis residue of bamboo MWL
Mitsuhiko Tanahashi, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 1H-NMR, synthesis of phenyl coumarone compound, UV absorption spectrometry
1973-A07
ヤチダモ材の加水分解物よりリグナン型化合物の単離
大森茂俊＊１、榊原 彰＊２＊１
岩手大学農学部、＊２北海道大学農学部
Isolation of lignan type compounds from hyrolysis products of Fraxinus excelsissima
Shigetoshi Omori＊１, Akira Sakakibara＊２＊１
Faculty of Agriculture, Iwate University, ＊２Faculty of Agriculture, Hokkaido University
Keywords: 1H-NMR, column chromatography, mass spectrometry, UV absorption spectrometry, IRabsorption spectrometry, 1H-NMR
1973-A08
Björkman LCC の分別
越島哲夫、夜久富美子、田中龍太郎
大阪工業試験所
Fractionation of Björkman LCC
Tetsuo Koshijima, Fumiko Yaku, Ryutaro Tanaka
Government Industrial Research Institute, Osaka
Keywords: gel filtration, paper electrophoresis, molecular weight
1973-A09
リグニンの抗腫瘍作用
村上浩紀
九州大学農学部
Antitumor activity of lignin
Hiroki Murakami
Faculty of Agriculture, Kyushu University
Keywords: Sasa veitchii, Pinus densiflora, calcium lignosulfonate, mouse
1973-A10
南洋材リグニンの特性について(3) —Eucalyptus Calophylla の KINO 成分—
荻山紘一、安江保民
山形大学農学部
Characteristics of the tropical wood lignins (III), Kino of Eucalyptus calophylla
Koichi Ogiyama, Moritami Yasue
Faculty of Agriculture, Yamagata University
Keywords: anthocyanidine, leucoanthocyanidine, polymer
1973-A11
広巾 NMR によるリグニンの分子運動に及ぼす置換基の影響についての研究
村越 康、畠山兵衛
製品科学研究所
Studies on the effect of substituent on molecular motion of lignin by broad band NMR
Yasushi Murakoshi, Hyoe Hatakeyama
Industrial Products Research Institute
Keywords: polystyrene, model polymer, substituted styrene
1973-A12
アセトグアヤコン、イソオイゲノールおよび関連アリールエーテル類の光分解
佐分義正、善本知孝、南 享二
81東京大学農学部
Photodegradation of acetoguaiacone, isoeugenol and related arylethers
Yoshimasa Saburi, Tomotaka Yoshimoto, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, gas liquid chromatography,
1973-A13
放射性同位元素標識リグニンの反応 —リグニンを構成する各炭素の KP 蒸解中の挙動
寺島典二、荒木 広、菅沼伸夫、神田 孝
名古屋大学農学部
Radiotracer experiments on lignin reactions, — Behavior of lignin carbons during kraft cooking process
Noritsugu Terashima , Hiroshi Araki, Nobuo Suganuma, Takashi Kanda
Faculty of Agriculture, Nagoya University
Keywords: Pinus Thunbergii, radiotracer, carbon 14, gel filtration
1973-A14
放射性同位元素標識リグニンの反応 —KP 蒸解中のリグニンと炭水化物との反応—
寺島典二、菅沼伸夫、荒木 広、神田 孝
名古屋大学農学部
Radiotracer experiments on lignin reactions, — Reaction of lignin with carbohydrates during kraft cooking
process
Noritsugu Terashima , Nobuo Suganuma, Hiroshi Araki, Takashi Kanda
Faculty of Agriculture, Nagoya University
Keywords: Pinus Thunbergii, carbon 14, gel filtration, MWL, DHP, guaiacylglycerol-β-guaiacyl ether
1973-A15
リグニン及びフェノール類の着色
林 晄、木下恭介、中村卓司
立命館大学理工学部
Coloring of lignin and phenols
Akira Hayashi, Kyosuke Kinoshita, Takuji Nakamura
Faculty of Science and Engineering, Ritsumeikan University
Keywords: quinone polymer, ferric chloride, thiolignin, polarography
1973-A16
過酸化水素漂白における高歩留パルプ中のリグニンの反応に関する研究 —リグニン中間位モデル物質の反応—
細谷修二、中野準三
東京大学農学部
Reaction of lignin during bleaching of high yield pulp by hydrogen peroxide, — Reaction of intermediate lignin
model compounds
Shuji Hosaya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: model compounds, Mass spectrometry, GC-Mass, TLC, NMR spectroscopy
1973-A17
Guaiacylglycerol-β-guaiacyl ether の過酢酸酸化
沖 妙、大久保 克美、石川 久雄
愛媛大学農学部
Peracetic acid oxidation of guaiacylglycerol-β-guaiacyl ether
Tae Oki, Katsumi Okubo, Hisao Ishikawa,
Faculty of Agriculture, Ehime University
Keywords: lignin model compounds, vapor-phase oxidation, liquid phase oxidation82

1973-A18
分子量分別したリグニンスルホン酸の電解酸化について
小川博嗣
東京工業試験所
Electrolytic oxidation of lignosulfonic acids fractionated by molecular weight
Hirotsugu Ogawa
Government Chemical Industrial Research Institute, Tokyo
Keywords: oxidation potential, pH
1973-A19
リグニンのオゾン処理 —溶媒の影響—
田中 治郎
林業試験場
Ozone treatment of lignin. –Effect of solvent
Jiro Tanaka
Government Forest Experiment Station
Keywords: larch, Larix Kaempferi, red pine, Pinus densiflora, wettability test
1973-B01
過酢酸気相漂白とその特色について
大久保克美、沖 妙、石川久雄
愛媛大学農学部
Vapor phase bleaching by peracetic acid, and its special feature
Katsumi Okubo, Tae Oki, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Douglas fir, Pseudotsuga taxifolia, UKP, dioxane lignin
1973-B02
各種ベースによるホロパルプ製造
松浦洋
日本紙パルプ研究所
Holopulping process using different bases
Hiroshi Matsuura
Japan Pulp and Paper Research Institute, Inc.
Keywords: holopulp, holocellulose, chlorine dioxide, recovery process, Na-base holopulp, Mg-baseholopulp
1973-B03

中止

1973-B04
酸素・アルカリ処理によるアカマツ MWL の分解
十河 村男、幡 克美
香川大学農学部
Degradation of MWL of Japanese red pine by oxygen-alkali treatment
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: Pinus densiflora, MWL, UV spectroscopy, gel filtration
1973-B05
針葉樹クラフトパルプの酸素漂白永野正，石井彰一，宮尾再青，松井泰彦
東洋パルプ株式会社
Oxygen bleaching of softwood kraft pulp
Tadashi Nagano, Shoichi Ishi, Saisei Miyao, Yasuhiko Matsui
83

Toyo Pulp Co., Ltd
Keywords: COD, cooking spent liquor, green liquor, kappa number
1973-B06
酸素漂白について
田渕博，川島功，山田洋三
紀州製紙株式会社
On the oxygen bleaching
Horoshi Tabuchi, Isao Kawashima, Yozo Yamada
Kishu Paper Co., Ltd.
Keywords: heavy metal ion, cellulose protecting agents, brightness stability
1973-B07
パルプ工業の無公害化へのアプローチ
御田昭雄*1、平井久雄*2*1
東京工業試験所、*2 チッソエンジニアリング株式会社
Approaches to pollution free pulp industry
Akio Mita*1, Hisao Hirai*2*1
Government Chemical Industrial Research Institute, Tokyo, *2Chisso Engineering Co.Ltd.
Keywords: closed system, unit process,1973-B08
SO2＋MgSO4 蒸解廃液からの薬品の回収と活性炭の製造について
林 治助*1, 戸坂圀夫*1、伴内正樹*2*1
北海道大学工学部、*2 プロセス資材株式会社
Recovery of chemicals and production of activated carbon from waste liquor of pulping with SO2 + MgSO4
Jisuke Hayashi*1, Kunio Tosaka*1, Masaki Bannai*2*1
Faculty of Engineering, Hokkaido University, *2Process Shizai Co. Ltd.
Keywords: white birch, Betula Tauschii,
1973-B09
γ 線照射によるパルプ製造廃水の淡色化に関する研究
飯塚堯介、中野準三
東京大学農学部
Reduction of color intensity of pulp mill effluent liquor byγ-ray irradiation
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: thiolignin, lignosulfonic acid, cobalt 60, peroxide radical
1973-B10
亜硫酸系パルプ廃液中の有機物成分の分取
猪狩俶将、横山正一郎
東京工業試験所
Separation of organic components from sulfite pulp waste liquor
Yoshimasa Ikari, Shoichiro Yokoyama
Government Chemical Industrial Research Institute, Tokyo
Keywords: Yezo spruce, Picea jezoensis, Abies Mayriana, NSCP, BOD,
1973-B11
パルプ製造廃水の凝集処理に関する研究 —凝集機構について—
徐道太郎、飯塚堯介、中野準三
東京大学農学部
Studies on the coagulation treatment of pulp mill effluent liquor. –Mechanism of coagulation
Jyo Michitaro, Gyosuke Meshitsuka, Junzo Nakano.
84

Faculty of Agriculture, the University of Tokyo
Keywords: lignosulfonate, thiolignin, sulfomethyl thiolignin, zeta potential, electrokinetic potential,
aluminum ion
1973-B12
クラフトパルプ廃水のオゾン併用活性汚泥処理 —処理効率と諸パラメーターについて—
上嶋 洋、赤松 勲
四国工業技術試験所
Treatment of kraft pulp mill effluent by activated sludge combined with ozone treatment. -Efficiency andparameters of the treatment
Hiroshi Kamishima, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: BOD, COD(Mn),
1973-B13
製紙スラッジを原料とする吸着剤の製造研究 —各種スラッジの示差熱分析結果と製造条件について—
前松陸郎、曽我部隆紀、芳地全保、谷 静男
愛媛県製紙試験所
Production of adsorbent from pulp mill sludge. –Differential thermal analyses of various sludge and conditionsof preparation
Mutsuo Maematsu, Takanori Sogabe, Masayasu Hochi, Shizuo Tani
Pulp and Paper Research Institute of Ehime Prefecture.
Keywords: recycled paper sludge, straw pulp sludge,
1973-B14
クラフトパルプ廃水の石灰処理（V）—廃水中のリグニンの分子量分布の石灰処理に及ばす影響—
加藤俊作、久保隆昌、木村 裕
四国工業技術試験所
Treatment of kraft pulp mill effluent with lime (V), Effect of molecular weight distribution of lignin in theeffluent on lime treatment
Shunsaku Kato, Takamasa Kubo, Yutaka Kimura
Government Industrial Research Institute, Shikoku
Keywords: COD, TOC, gel filtration,
1973-B15
BKP 製造における工程別排水の性状およびその凝集沈澱処理
上埜武夫，守屋正夫，竹下 登
山陽国策パルプ株式会社
Properties and sedimentation treatment of effluents from kraft pulping and bleaching processes
Takeo Ueno, Masao Moriya, Noboru Takeshita
Sanyo Kokusaku Pulp Co., Ltd.
Keywords: Pseudotsuga taxifolia, COD, chromaticity, lignin, sugar, color analysis
1973-B16
パルプ廃水処理
白川精一，木村勇，川添早苗，荒牧幹男
三菱重工業株式会社
Pulp effluents treatment
Seiichi Shirakawa, Isamu Kimura, Sanae Kawazoe, Mikio Aramaki
Mitsubishi Heavy Industries, Ltd.
Keywords: sedimentation, KP, SP, SCP, fermentation spent liquor, flocculant, colloid titration

85

第 19 回 （1974.10.19-20） 秋田大学教育学部
1974-101
ヤドリギ（Viscum album）のリグニンと Oーメチル基転位酵素
黒田宏之、樋口隆昌
京都大学木材研究所
Lignin in Viscum album, and O-methyl transferase
Hiroyuki Kuroda, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: ferulic acid, sinapic acid, OMT inhibitor
1974-102
シラカンバ新生組織へのフェニールアラニン-14C（U）の取り込みとリグニン形成
三宅基夫、寺沢 実、奥山 寛
帯広畜産大学
Incorporation of phenylalanine-14C(U) into newly formed xylem tissue of Betula Tauschii and lignin formation
Motoo Miyake, Minoru Terasawa, Hiroshi Okuyama
Obihiro University of Agriculture and Veterinary Medicine
Keywords: platyophylloside, platyphylldioloside, betuloside
1974-103
ポプラリグニンのパラハイドロオキシ安息香酸の生合成
寺島典二、岡田基光、神田 孝
名古屋大学農学部
Biosynthesis of p-hydroxybenzoic acid in poplar lignin
Noritsugu Terashima, Motomitsu Okada, Takashi Kanda
Faculty of Agriculture, Nagoya University
Keywords: Populus nigra X Populus Maximowiczii, 14C-labeled precursor
1974-104
Non-Woody リグニンについて —ナシの石細胞とモモの内果皮リグニン—
黒田宏之、近藤民堆
九州大学農学部
On the non-woody lignin. –Lignins in stone cell of pear (Pyrus pyrifolia var. culta) and in endocarp of peach(Amygdalus persica)
Hiroyuki Kuroda, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: dioxane lignin, nitrobenzene oxidation, ethanolysis
1974-105
圧縮アテ材リグニンの化学構造について
安田征市、榊原 彰
北海道大学農学部
Chemical structure of lignin in compression wood
Seichi Yasuda, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Larix leptolepis, p-hydroxyphenyl nucleus, guaiacyl nucleus, MWL，NMR
1974-106
カラマツアルカリリグニンの GPC について
香川詔士、長谷川修
関東学院大学工学部
On gel permeation chromatography of alkali lignin from larch
Shoji Kagawa, Osamu Hasegawa
86

Kanto Gakuin University
Keywords: Larix leptolepis, molecular weight distribution, air oxidation of alkali lignin, IR spectrum
1974-107
プロトリグニンの水素化分解に関する研究（第 13 報）—2，3 量体の単離、同定について—
須藤賢一、榊原 彰
北海道大学農学部
Hydrgenolysis of protolignin (XIII), –Isolation and identification of dimers and trimers
Kenichi Sudo, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis, α-conidendrin, matairesinol
1974-108
液安中金属ナトリウムによるリグニンの分解 —G 核及び P 核を有する二量体の単離—
山口 彰
林業試験場
Degradation of lignin by metallic sodium in liquid ammonia, — Isolation of dimer containing G and P units—
Akira Yamaguchi
Government Forest Experiment Station
Keywoeds:
Yezo spruce, Picea jezoensis, 1H-NMR, mass spectrometry
1974-109
竹リグニンのアシドリシス残渣のオゾン分解
棚橋光彦、中坪文明、樋口隆昌
京都大学木材研究所
Ozonolysis of acidolysis residue of bamboo lignin
Mitsuhiko Tanahashi, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: lignin model compound,
1974-110
ジオキサン—水によるリグニンの加水分解
佐野嘉拓、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane-water
Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: synthesis of compounds related hydrolysis products, gel chromatography
1974-111
リグニンの加溶媒分解 (第３報) −トレーサー法による反応の検討−
可知省吾*1，荒木廣*2，寺島典二*2
日本紙パルプ研究所*1，名古屋大学農学部*2
Solvolysis of lignin (III), Examination of reaction by the radioisotope tracer techniques
Shogo Kachi*1, Hiroshi Araki*2, Noritsugu Terashima *2*1
Japan Pulp and Paper Research Institute, Inc, *2 Faculty of Agriculture、 Nagoya University
Keywords: MWL, radioisotope, carbon-14, tritium
1974-112
1,2-Diarylpropane-1,3-diols の合成
中坪文明、樋口隆昌
京都大学木材研究所
Synthesis of 1,2-diarylpropane-1,3-diols
Fumiaki Nakatsubo, Takayoshi Higuchi
87Wood Research Institute, Kyoto University
Keywords: 1H-NMR, configuration, preparative TLC
1974-113
グアヤシルグリセロール-β-グアヤシルエーテルの合成
細谷修二、中野準三
東京大学農学部
Synthesis of guaiacylglycerol-guaiacyl ether
Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: 1H-NMR, mass spectrometry
1974-114
Guaiacylglycerol-β-guaiacylether の酸素アルカリ分解
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Degradation of guaiacylglycerol-β-guaiacylether by oxygen-alkali
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: peracetic acid oxidation, thin layer chromatography, gas chromatography
1974-115
リグニン分子運動のモデルポリマーによる考察
畠山兵衝*1、木村 実*2*1
製品科学研究所, *2 東京大学農学部
Simulation of molecular motion of lignin using a model polymer
Hyoe Hatakeyama*1, Minoru Kimura*2*1
National Institute of Advanced Industrial Science and Technology, *2Faculty of Agriculture, the University ofTokyo
Keywords: TBA, torsion brade analysis, DSC, broad band NMR,
1974-116
特別講演、Past and Present Challenges in Lignin Chemistry
Conrad Schuerch
ニューヨーク州立大、米、シラキウス
Invited lecture: Past and Present Challenges of Lignin Chemistry
Conrad Schuerch
New York State University, Syracuse. USA
Keywords: Klason, Staudinger, Freudenberg, Hibbert, Erdtman, heterogeneity, macromolecule, molecularweight, cellulose, UV spectroscopy, IR spectroscopy, protolignin, milled wood lignin,biphenyl structure, phenolic hydroxyl group content, 13C-NMR, microscopy, pulping, bleaching
1974-201
酸素アルカリ蒸解におけるブナリグニンの挙動
十河村男、幡 克美
香川大学農学部
Behavior of beech lignin during oxygen-alkali cooking
Murao Sogo, Katsumi Hata
Faculty of Agriculture, Kagawa University
Keywords: Fagus crenata, MWL, UV spectroscopy, gaschromatography
1974-202
酸素アルカリ蒸解におけるリグニンの挙動
青柳哲夫、細谷修二、中野準三
88東京大学農学部
Behavior of lignin during oxygen-alkali cooking
Tetsuo Aoyagi, Syuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: apocinol, acetovanillon, gas chromatography, quinone, radical
1974-203
アルカリ酸素漂白におけるプロテクターの保護機構
林 治助*1、山田紹良*1、戸坂圀夫*1、小泉正弘*2*1
北海道大学工学部, *2 東洋パルプ株式会社
Mechanism of protection of cellulose degradation by protectors in oxygen-alkali bleaching
Jisuke Hayashi*1, Akira Yamada*1, Kunio Tosaka*1, Masahiro Koizumi*2*1
Faculty of Engineering, Hokkaido University, *2Toyo Pulp Co. Ltd.
Keywords: magnesium carbonate, glucose, xylose, reducing monosaccharide, water soluble lignin
1974-204
クラフトパルプのオゾン漂白 —針葉樹と広葉樹パルプの漂白性について
上嶋 洋、藤井利郎、赤松 勲
四国工業技術試験所
Ozone bleaching of kraft pulp. –Bleachability of softwood pulp and hardwood pulp
Hiroshi Kamishima, Toshiro Fujii, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: Japanese red pine, Pinus densiflora, beech, Fagus crenata,
1974-205
酸素アルカリ処理に関する研究（V）—酸素漂白シーケンスについて（2）—
西田友昭、坂井克己、近藤民堆
九州大学農学部
Studies on oxygen-alkali treatment (V), —Peracetic acid bleaching of kraft pulp prebleached by oxygen-alkali(2)—
Tomoaki Nishida, Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: white birch, Betula Tauschii, analysis of variance, brightness
1974-206
高収率パルプに関する研究
御田昭雄*1、山本登久男*2、勝地光雄*2、勝山敦弘*2、平井久夫*3、赤羽利昭*3*1
東京工業試験所、*2 静岡県製紙工業試験所、*3 チッソエンジニアリング
Studies on the high yield pulp
Akio Mita*1, Tokuo Yamamoto*2, Mitsuo Katsuji*2, Atsuhiro Katsuyama *2, Hisao Hirai*3, Toshiaki Akabane*3*1
Government Industrial Research Institute, Tokyo, *2Paper Research Institute of Shizuoka Prefecture, *3Chisso
Engineering Co. Ltd.
Keywords: Douglas fir, Pseudotsuga taxifolia, lauan, Shorea sp., straw, bagasse, SOX chemimechanicalpulp,
1974-207
南洋材リグニンの特性について(4)—パルプ排液の着色に及ぼす高分子ロイコアントシアニジンの影響—
荻山紘一、安江保民
山形大学農学部
Characteristics of the tropical wood lignins. IV. –Effect of high molecular leuco-anthocyanidins on coloring ofpulp waste liquor
Koichi Ogiyama, Moritami Yasue
Faculty of Agriculture, Yamagata University
Keywords: Eucalyptus calophylla, UV spectroscopy, benzoquinone
89

1974-208
SCP 廃液について（4）—廃液中の Xylan—
稲田 治、鮫島一彦、近藤民雄
九州大学農学部
On the waste liquor of SCP (IV), –Xylan in waste liquor
Osamu Inada, Kazuhiko Sameshima, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Carpinus sp. white birch, Betula Tauschii, beech, Fagus crenata, kapur, Doryobalanops, whitelauan, Pentacme sp.
1974-209
石巻地先における底質汚染の調査結果について
上柿明子、渡辺丈夫、佐藤春雄、曾根 光
宮城県公害技術センター
Report of sediment contamination survey at onshore of Ishinomaki
Akiko Kamigaki, Takeo Watanabe, Haruo Sato, Hikaru Sone
Pollution Reserch Center of Miyagi Prefecture
Keywords: pulp effluent, COD, TOC, sulfide
1974-210
秋田湾海域汚染とスス水発生について
加藤治男
秋田県水産試験場
Sea water pollution and cause of sooty water at Akita bay
Haruo Kato
Akita Fisheries Experiment station
Keywords: COD, SS, suspended substance,
1974-211

中止

1974-212
BKP 製造工程から発生する各種漂白排水の性状及びその排水処理
竹下 登，上埜武夫，守屋正夫
山陽国策パルプ株式会社
Properties and treatment of effluents from kraft pulp bleaching processes
Noboru Takeshita, Takeo Ueno, Masao Moriya
Sanyo Kokusaku Pulp Co., Ltd.
Keywords: molecular weight distribution, sedimentation process, activated sludge process
1974-213
パルプ廃液の色に関する研究 —廃液処理時の色の挙動について—
鮫島一彦、石崎貞二、住本昌之、近藤民堆
九州大学農学部
Studies on the color of pulping waste liquor, –Behavior of coloring matter during treatment of waste liquor
Kazuhiko Sameshima, Teiji Ishizaki, Masashi Sumimoto, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords:: activated carbon, dialysis, aluminum sulfate
1974-214
パルプ廃水の炭素質材料等による浄化
里中聖一
北海道大学農学部
Purification of pulp mill effluent with carbonaceous materials
90

Seichi Satonaka
Faculty of Agriculture, Hokkaido University
Keywords: activated carbon, KP, SP, NSC. bark, Japanese oak, Quercus crispula
1974-215
パルプ漂白排水中の塩素化リグニンの紫外線分解
島田謹爾
林業試験場
Degradation of chlorinated lignin in pulp bleach effluent by ultraviolet light
Kinji Shimada
Forestry and Forest Product Research Institute
Keywords: red pine, Pinus densiflora, KP, COD, gas chromatography
1974-216
γ 線照射によるパルプ製造排水の淡色化について
飯塚堯介、中野準三
東京大学農学部
Reduction of color intensity of pulp mill effluent by -ray irradiation
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: thiolignin, lignosulfonic acid, lignin model compounds, COD, active oxygen species, conjugateddouble bonds, air bubbling91

第 20 回 （1975.10.20-21） 名古屋大学農学部
1975-101
バクテリアによるリグニンモデル化合物の分解（l）
森 義博、福住俊郎，南 享二
東京大学農学部
Degradation of lignin model compounds by bacteria (I)Yoshihiro Mori, Toshiro Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas dacunhae, Pseudomonas ovalis,
Pseudomonas surfactasimilas, DHP,
1975-102
木材腐朽菌による β−エーテル化合物の分解
松本 久、福住俊郎，南 享二
東京大学農学部
Degradation of β-ether compounds by wood rotting fungi
Hisashi Matsumoto, Toshio Fukuzumi, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Perenniporia subacida, Irpex lacteus, Trametes sanquineus
1975-103
リグニン関連合成高分子の生分解
林 英一*1、畠山兵衛*2、原口隆英*1*1
東京農工大学農学部、*2 製品科学研究所
Biodegradation of synthetic polymer related to lignin
Eiichi Hayashi*1,Hyoe Hatakeyama*2, Takafusa Haraguchi*1*1Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2 Industrial Products ResearchInstitute
Keywords: poly-(p-hydroxy styrene), poly-(3-methoxy-4-hydroxy styrene), poly-(3,5-dimethoxy4-hydroxy styrene), molecular weight distribution, UV spectrometry
1975-104
白色腐朽菌ヒラタケによるリグニンの分解
広居忠量*1，K.E. Eriksson*2*1
林業試験場，*2STFI
Degradation of lignin by white rot fungus Pleurotus ostreatus
Tadakazu Hiroi*1, K.E. Eriksson*2*1
Government Forest Experiment Station, *2Swedish Pulp and Paper Research Institute
Keywords: MWL, Chamaecyparis obtuse, kraft lignin, Pinus densiflora, Ca-lignosulfonate, molecularweight distribution
1975-105
ラッカーゼによりシリンガ酸から生成した o-キノン誘導体の構造について
石原達夫、石原光朗
林業試験場
Structure of o-quinone derivatives derived from syringic acid by laccase
Tatsuo Ishihara, Mitsuro Ishihara
Government Forest Experiment Station
Keywords: Polyporus versicolor, UV spectrometry, 2,6-dimethoxy-p-benzoquinone
1975-106
木材腐朽菌によるクラフト廃液の脱色
福住俊郎、西田篤實、島崎徹郎、南 享二
92東京大学農学部
Decolorization of kraft pulp mill effluent by wood rotting fungi
Toshio Fukuzumi, Atsumi Nishida, Tetsuro Shimazaki, Kyoji Minami
Faculty of Agriculture, the University of Tokyo
Keywords: Tinctoporia sp., Trametes sp., Tryromyces sp., Pleurotus sp., Pholiota sp., Phallinus sp. UV
spectrometry, gel filtration
1975-107
南洋材リグニンの特性（5）赤ラワン、ブナ材の着色
荻山絃一、安江保民
山形大学農学部
Characteristics of the tropical wood lignins (V), –Coloration of red lauan and beech wood
Koichi Ogiyama, Moritami Yasue
Faculty of Agriculture, Yamagata University
Keywords: Shorea negrosensis, Fagus crenata, reflectance spectrum,
1975-108
ジオキサン—水によるリグニンの加水分解 —モデル化合物の加水分解—
佐野嘉拓、榊原 彰
北海道大学農学部
Hydrolysis of lignin with dioxane-water, —Hydrolysis of model compounds—
Yoshihiro Sano, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: synthesis of model compounds, NMR, mass spectrometry, thin layer chromatography
1975-109
ジオキサン—水によるプロトリグニンの加水分解 —新 3 量体の単離—大森茂俊*1、榊原 彰*2*1
岩手大学農学部、*2 北海道大学農学部
Hydrolysis of protolignin with dioxane-water, –Isolation of a new trimer—
Shigetoshi Omori*1, Akira Sakakibara*2*1
Faculty of Agriculture, Iwate University, *2Faculty of Agriculture, Hokkaido University
Keywords: Fraxinus excelsissima, IR spectroscopy, UV spectroscopy, Mass spectrometry, NMR
1975-110
広葉樹プロトリグニンの水素化分解 —２量体の単離と構造解析について
須藤賢一*1、岸 政美*2、榊原 彰*2*1
林業試験場、*2 北海道大学農学部
Hydrogenolysis of hardwood protolignin, –Isolation and structural analysis of a dimer
Kenichi Sudo*1, Masami Kishi*2, Akira Sakakibara*2*1
Forestry and Forest Product Research Institute,*2Faculty of Agriculture, Hokkaido University
Keywords: Fraxinus excelsissima,TLC, Mass spectrometry, 1H-NMR, dimethoxylariciresinol
1975-111
アテ材リグニンの水素化分解 —縮合型新２量体その他の単離
安田征市、榊原 彰
北海道大学農学部
Hydrogenolysis of lignin in compression wood. Isolation of a new condensed type dimmer and othercompounds
Seiichi Yasuda, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: larch, Larix Kaempferi, TLC, Mass spectrometry, 1H-NMR,
1975-11293

リグニンの加溶媒分解 (第５報) −トレーサー法による反応の検討 (3)−
可知省吾*1，荒木廣*2，寺島典二*2，神田孝*2*1
日本紙パルプ研究所，*2 名古屋大学農学部
Solvolysis of lignin (V), −Comparison of solvolysis lignins with other lignins by the radioisotope tracer
techniques (3) −Shogo Kachi*1, Hiroshi Araki*2 , Noritsugu Terashima *2, Takashi Kanda *2*1
Japan Pulp and Paper Research Institute, Inc，*2 Faculty of Agriculture, Nagoya University, Keywords:
solvolysis, lignin, radioisotope, carbon-14, tracer
1975-113
Björkman LCC 中のリグニンに結合する糖の結合様式
越島哲夫、夜久富美子、田中龍太郎
大阪工業技術試験所
Linkage type of sugar unit bound to lignin in Björkman LCC
Tetsuo Koshijima, Kumiko Yaku, Ryutaro Tanaka
Government Industrial Research Institute, Osaka
Keywords: DEAE Sephadex column chromatography, electrophoresis,
1975-114
シラカンバ樹皮のリグニン
三宅基夫、寺沢 実、奥山 寛
帯広畜産大学
Lignin in the bark of birch
Motoo Miyake, Minoru Terasawa, Hiroshi Okuyama
Obihiro University of Agriculture and Veterinary Medicine
Keywords: Betula Tauschii, cork tissue, nitrobenzene oxidation, suberin, pectin
1975-115
3,5−2 置換 p-ヒドロキシケイヒアルコールの脱水素重合
棚橋光彦、武内英夫、樋口隆昌
京都大学木材研究所
Dehydrogenative polymerization of 3,5-disubstituted p-hydroxycinnamyl alcohol
Mitsuhiko Tanahashi, Hideo Takeuchi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 5-iodo-coniferyl alcohol, 3,5-diiodo-p-coumaryl alcohol, sinapyl alcohol, 1H-NMR
1975-116
ヤドリギリグニンの生合成
黒田宏之、樋口隆昌
京都大学木材研究所
Biosynthesis of lignin in Viscum album
Hiroyuki Kuroda, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: O-methyl transferase, OMT, guaiacyl lignin, syringyl lignin, Celtis sinensis, MWL, 13C-NMR,
radio tracer, phenylalanine-U-14C
1975-117
傷害，病害に伴うサツマイモ、ウリ類におけるリグニン形成
瓜谷郁三、寺島典二、小島峯雄
名古屋大学農学部
Lignin formation in sweet potato and cucumber caused by injury or blight
Ikuzo Uritani, Noritsugu Terashima, Mineo Kojima
Faculty of Agriculture, Nagoya University
Keywords: sweet potato, Ipomea batatas, cucumber, Cucumis sativus, lignification, injury, blight94

1975-118
特別講演、植物病態組織でのリグニン生合成
浅田泰次、大口富三、松本勲
愛媛大学農学部
Invited lecture: Biosynthesis of lignin in diseased plant tissue
Yasuji Asada, Tomizo Ohguchi, Isao Matsumoto
Faculty of Agriculture, Ehime University
Keywords: Alternaria japonica, Peronospora parasitica, peroxidase, isoperoxidase, lignification inducer
1975-201
ユーカリ材黒液の高分子的性質
岡山隆之、大江礼三郎
東京農工大学農学部
Macromolecular properties of black liquor from eucalyptus wood
Takayuki Okayama, Reizaburo Ooe
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: kraft lignin, polyphenol, Eucalyptus marginata, gel filtration, molecular weight
1975-202
Mg ベース SCP について（4）—廃液の燃焼性と薬品回収—
周 森、住本昌之、近藤民雄
九州大学農学部
On the Mg-base SCP. IV. –Combustibility of waste liquor and recovery of chemicals
Syu Sin, Masashi Sumimoto, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: magnesium oxide, heat of combustion, semichemical pulp
1975-203
無機吸着剤によるパルプ廃液の処理
猪狩椒将*1、横山正一郎*1、村上達夫*2*1
東京工業試験所、*２富士化学工業株式会社
Treatment of pulp waste liquor with inorganic adsorbent
Yoshimasa Ikari*1, Shoichiro Yokoyama*1, Tatsuo Murakami*2*1
Government Industrial Research Institute, Tokyo，*2Fuji Chemical Co. Ltd.
Keywords: COD, BOD, TOC, gel filtration
1975-204
粘土懸濁液の粘性に与える高分子量リグニンスルホン酸の影響
小山 実
東京工業試験所
Effect of high molecular lignosulfonic acid on the viscosity of clay suspension
Minoru Koyama
Government Industrial Research Institute, Tokyo
Keywords: montmorillonite, kaolinite,
1975-205
リグニン中のフリーラジカルについて
飯塚堯介、中野準三
東京大学農学部
On the free radical in lignin
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: ESR spectrum, pH, EDTA, metal ion, reducing agents95

1975-206
KP 蒸解における炭水化物からの色
鮫島一彦、高村憲男
高知大学農学部
Color originated from carbohydrate in kraft cooking
Kazuhiko Sameshima, Norio Takamura
Faculty of Agriculture, Kochi University
Keywords: Betula Tauschii, xylan, xylose, holocellulose, UV and Visible light spectroscopy
1975-207
クラフトパルプ漂白排水中の低分子化合物について
金沢健治、細谷修二、中野準三
東京大学農学部
Low molecular weight compounds in kraft pulp bleach effluent
Kenji Kanazawa, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: thiolignin, TLC, gas chromatography, mass spectrometry
1975-208
パルプ漂白廃液中の低分子有機成分について
島田謹爾
林業試験場
Low molecular organic compounds in pulp bleach effluent
Kinji Shimada
Government Forest Experiment Station
Keywords: Japanese red pine, Pinus densiflora, BKP, GC/MS,
1975-209
高収率パルプ白色度向上について—亜塩素酸塩利用の効果—
加納 直，岩見田糺，角 祐一郎
山陽国策パルプ株式会社
Peroxide bleaching of chemimechanical pulps, – Effect of pretreatment with sodium chlorite
Tadashi Kano, Tadashi Iwamida, Yuichiro Sumi
Sanyo Kokusaku Pulp Co., Ltd.
Keywords: chemimechanical pulp, peroxide bleaching, pretreatment, sodium chlorite, brightness
1975-210
パルプのオゾン漂白におけるセルロース保護剤の効果
上嶋 洋、藤井利郎、赤松 勲
四国工業技術試験所
Effect of cellulose protector in ozone bleaching of pulp
Hiroshi Kamishima, Toshio Fujii, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: Pseudotsuga taxifolia, iron, copper, zinc, cobalt, manganese, organic protector
1975-211
酸素・アルカリ蒸解におけるリグニンの挙動について —α−カルボニル基に基づく新しい反応サイト
青柳哲夫、細谷修二、中野準三
東京大学農学部
Behavior of lignin during oxygen-alkali cooking, -New reaction site based on a-carbonyl group
Tetsuo Aoyagi, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compounds, reaction mechanism, benzyl alcohol, benzyl ether
96

1975-212
Guaiacylglycerol-β-guajacy1ether の酸素・アルカリ酸化分解
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Oxygen-alkali degradation of guaiacy1glycerol-βguajacy1ether
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: UV spectrometry, quinone, pH dependence
1975-213
亜硫酸ソーダ—酸素・アルカリ２段蒸解試験並びに蒸解時におけるリグニンの挙動について
林 忠和、幡 克美、十河村男、山崎 徹
香川大学農学部
Two stage sodium sulfite-oxygen alkali cooking test and behavior of lignin during the cooking
JongHer Lin, Katsumi Hata, Murao Sogo, Toru Yamasaki
Faculty of Agriculture, Kagawa University
Keywords: Japanese red pine, Pinus densiflora, beech, Fagus crenata, IR spectrometry
1975-214
酸素・アルカリ処理に関する研究 —廃液の濃縮過程で生ずる沈殿について—
浅野 勲、坂井克己、近藤民堆
九州大学農学部
Studies on the oxygen alkali treatment, –On the precipitant formed in the concentration process of waste liquor
Isao Asano, Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: birch, Betula tauschii, scaling problem,
1975-215
アルカリ，酸素漂白におけるプロテクターの保護機構（第３報）
山田紹良、小森重男、林 治助、戸坂圀夫
北海道大学工学部
Protection mechanism by protectors during alkali oxygen bleaching
Akira Yamada, Shigeo Komori, Jisuke Hayashi, Kunio Tosaka
Faculty of Engineering, Hokkaido University
Keywords: softwood UKP, hydroxyl radical, reducing sugar, glucose
1975-216
アルカリ-酸素蒸解に関する研究（第 3 報）ふりかけ法による稲わらからのパルプ製造について
戸坂圀夫*1、渡辺貞良*1、林 治助*1、山田邦重*2、小川文人*3*1
北海道大学工学部、*2 株式会社ほくさん、*3 王子製紙株式会社
Studies on the oxygen alkali cooking (III), Pulp production from rice straw by sprinkling process
Kunio Tosaka *1, Sadayoshi Watanabe*1, Jisuke Hayashi*1,Kunishige Yamada*2, Fumito Ogawa*3*1
Faculty of Engineering, Hokkaido University, *2Hokusan Co. Ltd., *3Oji Paper Co. Ltd
Keywords: tensile strength，burst factor, breaking length,
1975-217
非木材パルプに関する研究
御田昭雄*1、山本登久男*2、勝地光雄*2、山崎恒夫*2、勝山敦弘*2、
赤羽利昭*3、梅木一義*3*1
東京工業試験所、*2 静岡県製紙工業試験所、*3 チッソエンジニアリング株式会社
Studies on non-woody pulp
Akio Mita*1, Tokuo Yamamoto*2, Mitsuo Katsuji*2, Tsuneo Yamazaki*2, Atsuhiro Katsuyama*2, Toshiaki
97

Akabane*3, Kazuyoshi Umeki*3*1
Government Industrial Research Institute, Tokyo, 2Paper Research Institute of Shizuoka Prefecture, *3Chisso
Engineering Co. Ltd.
Keywords: straw, bagasse, silica, SOX chemimechanical pulp, tensile strength
1975-218
特別講演、これからのウッドケミカルスおよび無公害パルプ化に関する最近の海外の研究の動向
中野準三
東京大学農学部
Invited lecture:
Recent research trends in wood chemicals and pollution-free pulping in foreign countries
Junzo Nakano
Faculty of Agriculture, the University of Tokyo

98

第 21 回 （1976.10.18-19） 東京大学農学部
1976-101
成育時の光質とリグニン
田中冶郎
林業試験場
Relation between light quality and lignin structure during growth
Jiro Tanaka
Government Forest Products Research Institute
Keywords: Platanus occidentalis, environmental factor, S/V ratio, wave length,
1976-102
木材腐朽菌によるリグニンモデル化合物の代謝
西田篤実、福住俊郎
東京大学農学部
Metabolism of lignin model compounds by wood rotting fungi
Atsumi Nishida, Toshio Fukuzumi
Faculty of Agriculture, the University of Tokyo
Keywords: white-rot fungi, Trametes sp., ferulic acid, p-coumaric acid, UV spectrometry
1976-103
バクテリアによるリグニンモデル化合物の分解（III）
片山義博、福住俊郎
東京大学農学部
Degradation of lignin model compounds by bacteria (III)Yoshihiro Katayama, Toshio Fukuzumi
Faculty of Agriculture, the University of Tokyo
Keywords: Pseudomonas sp., dehydrodiconiferyl alcohol. pinoresinol, guaiacylglycerol-βconiferyl ether,
1
H-NMR, UV spectrometry
1976-104
Betulachrysoquinone hemiketal, A p-benzoquinone hemiketal type macrocyclic compound produced by
Phanerochaete chrysosporium
C.-L. Chen*1, H.-M. Chang*1, T.K. Kirk*2*1
North Carolina State University, *2Forest Products Laboratory, USDA
Keywords: Betula lutea, fungal metabolite, 1H-NMR, UV spectroscopy
1976-105
アミノベンゼンスルホン酸塩リグニンについて（V）
黒田健一*1、坂井克己*2、近藤民雄*2*1
東京教育大学農学部、*2 九州大学農学部
On aminobenzenesulfonate lignin (V)Ken-ichi Kuroda*1, Kokki Sakai*2, Tamio Kondo*2*1
Faculty of Agriculture, Tokyo University of Education, *2Faculty of Agriculture, Kyushu University
Keywords: vanillyl alcohol, sodium metanilate, 1H-NMR, UV spectroscopy, IR spectroscopy
1976-106
クラフト蒸解時のイオウの挙動 第 1 報 蒸解条件とイオウの配分
近藤隆一郎、近藤民雄
九州大学農学部
Behavior of sulfur during kraft pulping (I), The distribution of sulfur into vapor-, liquid- andduring cooking
Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
99

solid-phases

Keywords: white birch, Betula Tauschii, sulfidity, gas chromatography, methyl mercapthane, dimethyl
sulfide, dimethyl disulfide,
1976-107
ゲル浸透クロマトグラフィーによるカラマツアルカリリグニンの分子量分布測定（その 2）
香川詔士、小室益広
関東学院大学工学部
Determination of molecular weight distribution of larch alkali lignin by gel permeation chromatography (II)Shoji Kagawa, Masuhiro Komuro
College of Engineering, Kanto Gakuin University
Keywords: larch, Larix Kaempferi, mass spectrometry,
1976-108
竹リグニンのエステル構造 -Coniferyl p−Coumarate の脱水素重合中村吉紀*1、樋口隆昌*2*1
山陽国策パルプ株式会社、*2 京都大学木材研究所
Ester structure in bamboo lignin, −Dehydrogenative polymerization of coniferyl p-coumarate−
Yoshiki Nakamura*1, Takayoshi Higuchi*2*1
Sanyo-Kokusaku Pulp Co. Ltd., *2Wood Research Institute, Kyoto University
Keywords: UV spectrometry, IR spectrometry, Zutropfverfahren, Zulaufverfahren
1976-109
ネズコ材のリグニンおよびリグナン
久津木英俊、塩 徹、樋口隆昌
京都大学木材研究所
Lignin and lignan in Thuja Standishii
Hidetoshi Kutsuki, Toru Shio, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Thuja plicata, O-methyl transferase, dihydroxythujaplicatin, dihydroxythujaplicatin methyl
ether, S-adenosylmethionine-14CH3,
1976-110
ユリノキ中のレジノール型リグナン類
藤本英人、樋口隆昌
京都大学木材研究所
Resinol type lignans in Liriodendron tulipifera
Hideto Fujimoto, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: pinoresinol, medioresinol, syringaresinol, lriodendrin, TLC, 1H-NMR,
1976-111
ジオキサン・水によるリグニンの加水分解 −アルデヒド型フェニルクマラン２量体の単離青山政和、榊原 彰
北海道大学農学部
Hydrolysis of lignin in dioxane-water, −Isolation of aldehyde type phenylcoumaran dimer
Masakazu Aoyama, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Japanese oak, Quercus crispula, TLC, UV spectroscopy, IR spectroscopy, 1H-NMR,
1976-112
圧縮あて材プロトリグニンの水素化分解 — 縮合型二量体の単離
安田征市、榊原 彰
100

北海道大学農学部
Hydrogenolysis of protolignin in compression wood, −Isolation of condensed type dimers
Seiichi Yasuda, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: larch, Larix leptolepis, mass spectrometry, IR spectroscopy, 1H-NMR,
1976-113
リグニン水素化分解物の 13C−NMR による検討
武山浩武、佐藤哲夫、榊原 彰
北海道大学農学部
Examination of lignin hydrogenolysis products by 13C−NMR
Hirotake Takeyama, Tetsuo Sato, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Yezo spruce, Picea jezoensis,
1976-114
Arundo donax, Welwitschia bainessi 及び関連物質の酸化分解
安田征市*1、G. E. Miksche*2*1
北海道大学農学部、*2Lund Institute of Technology, Sweden
Oxidative degradation of Arundo donax, Welwitschia bainessi and related materials
Seiichi Yasuda*1, G. E. Miksche*2*1
Faculty of Agriculture, Hokkaido University, *2Lund Institute of Technology, Sweden
Keywords: leaf lamina, petiole, permanganate oxidation, gas chromatography,
1976-115
シリンギル核リッチリグニンの単離
山崎 徹*1、幡 克美*1、樋口隆昌*2*1
香川大学農学部、*2 京都大学木材研究所
Isolation of syringyl nucleus-rich lignin
Toru Yamasaki*1, Katsumi Hata*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: mercury acetate, mercuration, MWL, nitrobenzene oxidation,
11976-116
総合討論：リグニン化学構造
座長: 寺島典二 (名古屋大学農学部)
General discussion: Structure of lignin
Moderator: Noritsugu Terashima (Faculty of Agriculture, Nagoya University)
Keywords:
1976-201
パルプの酸素酸化反応機構 反応速度論的研究
山田紹良、戸坂圀夫、林 治助
北海道大学工学部
Reaction mechanism of oxygen oxidation of pulp, –Kinetic study
Akira Yamada, Kunio Tosaka, Jisuke Hayashi
Faculty of Engineering, Hokkaido University
Keywords: cellulose protectant, glucose, triethanolamine, magnesium sulfate, Mg-EDTA
1976-202
放射性同位元素標識リグニンの反応 −リグニンを構成する各炭素の酸素・アルカリ蒸解中の挙動（2）荒木 広、寺島典二
名古屋大学農学部
101

Radiotracer experiments on lignin reactions, —The behavior of lignin carbons in oxygen-alkali pulping process(II)
Hiroshi Araki, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: oxygen-alkali pulping, radiotracer, radioisotope, carbon 14, pine, lignin, gel filtration,
1976-203
Dihydrodehydrodiisoeugenol の酸素・アルカリ酸化
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Oxygen alkali oxidation of dihydrodehydrodiisoeugenol
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: UV spectrometry, difference spectrum, o-quinone
1976-204
非木材植物の酸化的脱リグニンについて
Tran van Ai、坂井克己、近藤民雄
九州大学農学部
On the oxidative delignification of certain non−woody plants
Tran van Ai, Kokki Sakai, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Oryza sativa, Hordeum vulgare, Phyllostachys pubescens, Saccharum officinarum, sodium
chlorite, Wise method
1976-205
クラフトパルプの酸素−オゾン漂白について
藤井利郎、上嶋 洋、赤松 勲
四国工業技術試験所
Oxygen-ozone bleaching of kraft pulp
Tosiro Fujii, Hiroshi Kamishima, Isao Akamatsu
National Industrial Research Institute of Shikoku
Keywords: Douglas fir, Pseudotsuga taxifolia, brightness, pH
1976-206
クラフトパルプのメタノール添加オゾン漂白上嶋 洋、藤井利郎、赤松 勲
四国工業試験所
Bleaching of kraft pulp by ozone with addition of methanol
Hiroshi Kamishima, Tosiro Fujii, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: cellulose protectant, brightness, breaking length, tear factor
1976-207
総合討論：酸化的脱リグニン
座長 近藤民堆 (九州大学農学部)
General discussion: Oxidative delignification
Moderator: Tamio Kondo (Faculty of Agriculture, Kyushu University)
1976-208
サルファイト系高歩留パルプの製造に関する研究 第 5 報 ディスクリファイニングによって露出する繊維表面
岩見田 糺*1，角 祐一郎*1，中野準三*2*1
山陽国策パルプ株式会社，*2 東京大学農学部102

Studies on production of sulfite chemimechanical pulps (V), Fiber surface exposed by disk-refining
Tadashi Iwamida*1, Yuichiro Sumi*1, Junzo Nakano*2
1
Sanyo Kokusaku Pulp Co., Ltd., *2 Faculty of Agriculture, the University of Tokyo,
Keywords: sulfite chemimechanical pulp, disk-refining, fiber surface, compound middle lamella, secondarywall, Abies Mayriana, Betula Tauschii, scanning electron microscopy,
1976-209
リグニンの塩素化アルカリ抽出（IX） 塩素化ジオキサンリグニン（CL）の 2，3 の物理化学的性質
河内進策
宮崎大学農学部
Chlorination of lignin followed by alkali extraction (IX), Physicochemical properties of chlorinated dioxane
ligninSinsaku Kawachi
Faculty of Agriculture, Miyazaki University
Keywords: Japanese red pine, Pinus densiflora, dioxane lignin, viscosity, heat of wetting
1976-210
アカマツ材クラフト漂白廃液中の有機成分
島田謹爾
林業試験場
Organic components in bleaching effluent of red pine kraft pulp
Kinji Shimada
Government Forest Experiment Station
Keywords: Pinus densiflora, gas chromatography, mass spectrometry, alkali-copper

dioxide oxidation,

1976-211
パルプ廃液の浄化に関する研究 —活性汚泥法による処理—
八重樫稔、三浦 清
北海道大学農学部
Studies on the purification of pulp mill effluent, —Treatment with activated sludge—
Minoru Yaegashi, Kiyoshi Miura
Faculty of Agriculture, Hokkaido University
Keywords: Betula Tauschii, Glehn’s spruce, Picea Glehnii. chromaticity, COD, BOD, TOC
1976-212
パルプスラッジから粒状活性炭の製造
品部義秋，国正秀昭
東洋パルプ株式会社
Manufacturing of granular activated carbon from pulp and paper sludge
Yoshiaki Shinabe, Hideaki Kunimasa
Toyo Pulp Co., Ltd.
Keywords: pulp and paper mills, organic sludges, granular activated carbon, adsorption, dry distillation
1976-213
紙パルプ排水水質モニタリングについての一方法
中村孝一，佐藤坦，福島正輝，秦邦男
十條製紙
A monitoring method of pulp and paper effluents
Koichi Nakamura, Taira Sato, Masateru Fukushima, Kunio Hata
Jujo Paper Co., Ltd.
Keywords: pulp and paper effluents, COD, BOD, continuous monitoring system, ultraviolet absorption
method1976-214
特別講演、紙・パルプ産業の現状と問題点
103

松井康博
十條製紙株式会社
Invited lecture:
Present state and future problems in pulp and paper industry
Yasuhiro Matsui
Jujo Paper Co. Ltd.

104

第 22 回 （1977.10.8-9） 北海道大学農学部
1977-101
DHP 合成に対する新しい試み
棚橋光彦、樋口隆昌
京都大学木材研究所
A new trial of synthesis of DHP
Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: dialysis membrane, cellulose tube, coniferyl alcohol, sinapyl alcohol, Zulaufverfahren,
Zutropfverfahren
1977-102
グワヤシルグリセロール-β-グワヤシルエーテルと糖類の反応（第 2 報）
田中憲次、中坪文明、樋口隆昌
京都大学木材研究所
Reaction of guaiacylglycerol-βguaiacyl ether and sugar (II)Kenji Tanaka, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: LCC, lignin carbohydrate complex, quinone methide, gel filtration, 1H-NMR
1977-103
コニフェリルアルコールと d-カテキンの脱水素共重合
小寺 学、棚橋光彦、樋口隆昌
京都大学木材研究所
Dehydrogenative copoymerization of coniferyl alcohol and d-catechinManabu Kodera, Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: molecular weight, UV spectroscopy, permanganate oxidation,
1977-104
リグニン生合成と側鎖飽和型フェノール成分
寺沢 実、三宅基夫
帯広畜産大学
Biosynthesis of lignin and phenolic components with saturated side chain
Minoru Terasawa, Motoo Miyake
Obihiro University of Agriculture and Veterinary Medicine
Keywords: Betula platyphylla, beturoside-14C(U), platypylloside-14C(U), phenylalanine-14C(U), radio-tracer
1977-105
アメリカデイコリグニン生合成の特異性
久津木英俊、樋口隆昌
京都大学木材研究所
Specificity in lignin biosynthesis in Erythrina crista-galli
Hidetoshi Kutsuki, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: radio-tracer, ferulic acid-2-14C, sinapic acid-2-14C, acidolysis, TLC, poplar, Pinus Thunbergii
1977-106
デヒドロジコニフェリルアルコールの微生物分解
大田雅彦*1、樋口隆昌*1、岩原章二郎*2*1
京都大学木材研究所、*２香川大学農学部
Degradation of dehydrodiconiferyl alcohol by microorganisms
Masahiko Ohta*1, Takayoshi Higuchi*1, Shojiro Iwahara*2
105

*1

Wood Research Institute, Kyoto University, *2 Faculty of Agriculture, Kagawa University
Keywords: biodegradation, Fusarium sp., phenylcoumaran substructures, 1H-NMR,
1977-107
微生物によるコニフェリルアルコール脱水素重合物（DHP）の分解について
岩原章二郎*1、桑原正章*1、樋口 隆昌*2
*1
香川大学農学部、 *２京都大学木材研究所
Degradation of dehydrogenative polymer of coniferyl alcohol (DHP) by microorganisms
Shojiro Iwahara*1, Masaaki Kuwahara*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: biodegradation, Fusarium sp., gel filtration, pinoresinol, dehydrodiconiferyl alcohol
1977-108
微生物によるリグニン関連芳香族化合物の代謝
桑原正章、岩原章二郎
香川大学農学部
Metabolism of lignin related aromatic compounds by microorganisms
Masaaki Kuwahara, Shojiro Iwahara
Faculty of Agriculture, Kagawa University
Keywords: biodegradation, Pseudomonas sp., Rhodotorula
demethoxylationsp.,

Corynebacterium

glutamicum,

1977-109
木材腐朽菌の Benzoic acids，Cinnamic acids の還元酵素、及び Ferulic acid から Vanillic acid の生成酵素系について
西田篤実、福住俊郎
東京大学農学部
Reducing enzymes of benzoic acids and cinnamic acids in wood rotting fungi, and enzyme system converting
ferulic acid to vanillic acid
Atsumi Nishida, Toshio Fukuzumi
Faculty of Agriculture, the University of Tokyo
Keywords: Trametes sp., 3,4,5-trimethoxybenzoic acid, gas chromatography
1977-110
アテ材化学成分の研究 —主として圧縮アテ材のリグニンについて—
榊原 彰*1、諸星紀幸*2、安田征市*3*1
北海道大学農学部, *2 東京農工大学農学部, *3 名古屋大学農学部
Studies on the chemical components of reaction wood. –Lignin in compression wood
Akira Sakakibara*1, Noriyuki Morohoshi*2, Seiichi Yasuda*3*1
Faculty of Agriculture, Hokkaido University, *2Faculty of Agriculture, Tokyo University of Agriculture andTechnology, *3Faculty of Agriculture, Nagoya University
Keywords: Abies sachalinensis, Larix leptolepis, Fraxinus mandshurica, lariciresinol p-coumarate,p-hydroxyphenyl unit
1977-111
Mäule 反応の呈色機構（第 8 報）
飯塚堯介、中野準三
東京大学農学部
Mechanism of Mäule color reaction (VIII)
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compound, ESR spectroscopy, visible light absorption spectroscopy chlorinatedo-quinone,
1977-112106

トレーサー法によるリグニンの諸反応の解析 —パルプ化過程におけるフェニルプロパン側鎖末端基の挙動—
荒木 広、富村洋一、寺島典二
名古屋大学農学部
Radiotracer experiments on lignin reactions, -The behaviour of phenylpropane side-chain carbons during
pulping process—
Hiroshi Araki, Yoichi Tomimura, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords; radiotracer, radioisotope, carbon 14, pine, lignin, kraft pulping, soda pulping, oxygen-alkali
pulping, gel filtration,
1977-113
三弗化硼素、フェノール系におけるリグニン及びリグニンモデル化合物の反応
船岡正光、阿部 勲
三重大学農学部
Reaction of lignin and lignin model compounds in boron trifluoride and phenol system
Masamitsu Funaoka, Isao Abe
Faculty of Agriculture, Mie University
Keywords; diphenylmethane, catechol, nucleus exchange reaction
1977-114
中性での H2O2 酸化によるリグニンの淡色化について
石川久雄、沖 妙、大久保克美
愛媛大学農学部
Lignin color reduction by H2O2 oxidation in neutral condition
Hisao Ishikawa, Tae Oki, Katsumi Okubo
Faculty of Agriculture, Ehime University
Keywords; lignosulfonic acid, thiolignin, dioxane lignin, MWL, reductive bleaching, zinc dithionite,o-quinone, p-quinone
1977-115
過酸化物および酸素・アルカリによるリグニン酸化分解の特徴
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Specificity in oxidative degradation of lignin by peroxide and oxygen alkali
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords; lignin model compounds, dioxane lignin, peracetic acid, hydrogen peroxide
1977-116
総合討論：
座長: 樋口隆昌（京都大学木材研究所）
General discussion:Moderator: Takayoshi Higuchi (Wood Research Institute, Kyoto University)
1977-201
リグニン及びリグニンモデル化合物のオゾン分解
金子英信、細谷修二、中野準三
東京大学農学部
Degradation of lignin and lignin model compounds by ozone
Hidenobu Kaneko, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords; guaiacylglycerol-β-guaiacyl ether, TLC, HPLC, 1H-NMR, 13C-NMR

107

1977-202
針葉樹リグニンモデル化合物のオゾン分解
小島康夫、三浦 清、香山 彊
北海道大学農学部
Degradation of softwood lignin model compounds by ozone
Yasuo Kojima, Kiyoshi Miura, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords; UV spectrometry, IR spectrometry, TLC, 1H-NMR, 13C-NMR
1977-203
液相法によるパルプのオゾン漂白
藤井利郎、上嶋 洋、赤松 勲
四国工業技術試験所
Ozone bleaching of pulp in liquid phaseToshiro Fujii, Hiroshi Kamishima, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords; Douglas fir, Pseudotsuga taxifolia, cellulose protectant, gas phase bleaching
1977-204
クラフトパルプのオゾン漂白におけるメタノールのセルロース保護機構に関する研究
上嶋 洋、藤井利郎、赤松 勲
四国工業技術試験所
Mechanism of protection of cellulose by methanol during ozone bleaching of kraft pulp
Hiroshi Kamishima, Toshiro Fujii, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords; Douglas fir, Pseudotsuga taxifolia, n-hexane, ethyl acetate, acetone methyl oxalate, pyridine,
methyl cellosolve
1977-205
RGP のオゾン及びアルカリによる後処理
小林 武、細川 純、久保隆昌、木村 裕
四国工業技術試験所
Posttreatment of RGP with ozone and alkali
Takeshi Kobayashi, Jun Hosokawa, Takamasa Kubo, Yutaka Kimura
Government Industrial Research Institute, Shikoku
Keywords;
1977-206
酸素・アルカリ蒸解におけるリグニンの挙動について
青柳哲夫、細谷修二、中野準三
東京大学農学部
Behavior of lignin during oxygen alkali pulping
Tetsuo Aoyagi, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords; lignin model compounds, TLC, mass spectrometry, 1H-NMR, 13C-NMR
1977-207
亜硫酸ソーダ—酸素・アルカリ蒸解について
幡 克美、林 忠和、十河村男、山崎 徹
香川大学農学部
On the sodium sulfite-oxygen/alkali pulping
Katsumi Hata, JongHer Lin, Murao Sogo, Toru Yamasaki
Faculty of Agriculture, Kagawa University
Keywords; beech, Fagus crenata, Eucalyptus sp. physical properties of NS-OA pulp
108

1977-208
クラフト蒸解におけるリグニン中へのイオウの取り込み
石野良明、近藤隆一郎、近藤民雄
九州大学農学部
Introduction of sulfur into lignin during kraft pulping
Yoshiaki Ishino, Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords; Japanese red pine, Pinus densiflora, hydrogen sulfide, sulfidation of wood, wood sulfide
1977-209
クラフト蒸解時のイオウの挙動（III）—揮発性有機イオウ化合物の生成について—
近藤隆一郎、近藤民雄
九州大学農学部
Behavior of sulfur during kraft pulping (III), On the formation of volatile organic sulfur compounds
Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords; Betula Tauschii, Pinus densiflora, dioxane lignin, lignin model compound, methyl mercaptane,
dimethyl sulfide, dimethyl disulfide, demethylation reaction
1977-210
SOX 法によるバガスのパルプ化
御田昭雄*1、佐伯 剛*2*1
東京工業試験所、*2 工学院大学
Pulping of bagasse by SOX process
Akio Mita*1, Tsuyoshi Saiki*2*1
Government Chemical Industrial Research Institute, Tokyo, *2Kogakuin University
Keywords; cooking with (Na2SO4 + SO2), soda pulping, electron microscopy
1977-211
SO2＋MgSO4 2 成分蒸解法に関する研究 「広葉樹の木材細胞壁の porous 構造と溶出リグニンの分子量特性」
鈴木 勉、戸坂圀夫、林 治助
北海道大学工学部
Studies on two component pulping with SO2＋ MgSO4. “Relation between porous structure of hardwood cellwall and molecular weight characteristics of dissolved lignin”
Tsutomu Suzuki, Kunio Tosaka, Jisuke Hayashi
Faculty of Engineering, Hokkaido University
Keywords; Betula Ermanii, pore volume, gel filtration, cell wall morphology
1977-212
マグネシャ系吸着剤を中心にした NSCP 廃水の処理
猪狩淑将*1、横山正一郎*1、板矢柳太郎*2，池田恵一*2、大熊恒雄*2、
加藤啓介*3、深川和幸*3*1
東京工業試験所、*２北曹、*３住重エンバイロ
Processing of NSCP effluent with magnesia adsorbent
Yoshimasa Ikari*1,Shoichiro Yokoyama*1,Ryutaro Itaya*2, Kei-ichi Ikeda*2, Tsuneo Okuma*2, Keisuke Kato*3,
Kazuyuki Fukagawa*3*1
Government Chemical Industrial Research Institute, Tokyo, *2Hokuso Co. Ltd., *3Sumijyu Environmental
Engineering Co. Ltd.
Keywords; COD, chromaticity, TOC, activated sludge
1977-213
109

クラフトパルプ廃水、アルカリチオリグニン、リグニンモデル物質の石灰による凝集処理
赤松 勲、上嶋 洋、藤井利郎、細川 純
四国工業技術試験所
Coagulation treatments with lime of effluent from kraft pulp mill, alkali thiolignin, and lignin model compounds
Isao Akamatsu, Hiroshi Kamishima, Toshiro Fujii, Jun Hosokawa
Government Industrial Research Institute, Shikoku
Keywords; curcumin, tin, zinc, dehydrodiisoeugenol
1977-214
総合討論：
座長: 中野準三
東京大学農学部
General discussion:Moderator: Junzo Nakano
Faculty of Agriculture, the University of Tokyo
1977-215
特別講演：
フアインケミカルスを中心としたリグニン利用の将来
岡部次郎
山陽国策パルプ株式会社
Invited lecture:
Future aspects of utilization of lignin as fine chemicals
Jiro Okabe
Sanyo-Kokusaku Pulp Co. Ltd.
Keywords: water-reducing admixtures, granulation agent for ore powder, cement detergent,110

第 23 回 （1978.11.1-2） 愛媛大学農学部
1978-101
シナップ酸形成能の高いコノテガシワ O−メチル基転位酵素について
久津木英俊、島田幹夫、樋口隆昌
京都大学木材研究所
O-Methyl transferase inThuja orientalis having high sinapic acid forming ability
Hidetoshi Kutsuki, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: substrate specificity, metal ion demand, optimum pH, Michaelis constant
1978-102
透析膜法による DHP の合成
棚橋光彦、樋口隆昌
京都大学木材研究所
Synthesis of DHP by the dialysis membrane method
Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Zulaufverfahren, Zutropfverfahren, coniferyl alcohol, sinapyl alcohol, LCC, cell wall model
1978-103
木材腐朽菌による針葉樹、広葉樹型リグニンの分解に見られるシリンギル核劣化の優先性
野口明雄*1、島田幹夫*1、樋口隆昌*1、青島清雄*2*1
京都大学木材研究所、 *２林業試験場
Preferential degradation of syringyl nucleus in decay of softwood and hardwood lignin by wood- rotting fungi
Akio Noguchi*1, Mikio Shimada*1, Takayoshi Higuchi*1, Kiyoo Aoshima*2*1
Wood Research Institute, Kyoto University,*2Forestry and Forest Products Research Institute
Keywords: Coriolus versicolor, Poria subacida, Tyromyces palustris, host specificity, radio-labeled lignin
model compounds,
1978-104
リグニン生分解への立体生化学的アプローチ：ラッカーゼのリグニン側鎖不斉構造に及ばす非立体特異的
酸化反応の意義
島田幹夫、野口明雄、樋口隆昌
京都大学木材研究所
Biostereochemical approaches to lignin biodegradation: Meaning of non-stereo specific oxidation reaction on
asymmetric side chain structure of lignin by laccase
Mikio Shimada, Akio Noguchi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Coriolus versicolor, 3H-coniferyl alcohol, 3H/14C-coniferyl alcohol, 3H/14C-DHP,
1978-105
グアヤシルグリセロール-β-コニフェリルエーテルの微生物分解（第 2 報）
片山健至、中坪文明、樋口隆昌
京都大学木材研究所
Microbial degradation of guaiacylglycerol-coniferyl ether (II)Takeshi Katayama, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Fusrium solani, TLC, 1H-NMR, UV spectrometry
1978-106
デヒドロジコニフェリールアルコールの酵素的酸化について
岩原章二郎*1、西平 強*1、城森孝仁*1、桑原正章*1、樋口隆昌*2*1
香川大学農学部, *2 京都大学木材研究所
111

Enzymatic oxidation of dehydrodiconiferyl alcohol
Shojiro Iwahara*1, Tsuyoshi Nishihira*1, Takahito Jomori*1, Masaaki Kuwahara*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: Fusarium spp. gel filtration, TLC,
1978-107
糸状菌および細菌によるリグニン関連芳香族化合物の代謝
桑原 正章、登林浩司、佐藤哲雄、岩原章二郎
香川大学農学部
Metabolism of lignin related aromatic compounds by fungi and bacteria
Masaaki Kuwahara, Koji Noboribayashi, Tetsuo Sato, Shojiro Iwahara
Faculty of Agriculture, Kagawa University
Keywords: Pseudomonas sp., Fusarium solani, Fusarium oxysporum, Phanerochaete chrysosporium,
differential respirometer,
1978-108
カラマツの phenylpropane 誘導体および関連物質
三木啓司、笹谷宜志、榊原 彰
北海道大学農学部
Phenylpropane derivatives and related compounds from Larix Kaempferi
Keiji Miki, Takashi Sasaya, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: larch, Larix Kaempferi, inner bark, UV spectroscopy, 1H-NMR,
1978-109
ジオキサン・水によるリグニンの加水分解 —ラクトン環を有する化合物の単離—青山政和、榊原 彰
北海道大学農学部
Hydrolysis of lignin by dioxane-water, –Isolation of compounds having lactone ring—
Masakazu Aoyama, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Japanese oak, Quercus crispula, IR spectroscopy, mass spectrometry, 1H-NMR,
1978-110
プロトリグニンの水素化分解に関する研究 —新 3 量体の単離—
保田智之、榊原 彰
北海道大学農学部
Studies on the hydrogenolysis of protolignin, -Isolation of a new trimer—
Yasuda Tomoyuki, Ajira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: larch, Larix Kaempferi, compression wood, matairesinol, IR spectroscopy, mass spectrometry,
1
H-NMR,
1978-111
リグニンの化学構造の不均質性に関する研究
富村洋一、横井達明、寺島典二
名古屋大学農学部
Studies on the heterogeneity of lignin structure
Yooichi Tomimura, Tatsuaki Yokoi, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: Pinus Thunbergii, Kamabuchi poplar (Populus nigra X Populus Maximowiczii), radiotracer,
3
H,14C, double labeling
1978-112
MWL より分離した LCC 中のリグニンと糖の結合様式について112

榎 章郎、有国 尚、越島哲夫
京都大学木材研究所
Linkages between lignin and carbohydrates in LCC isolated from MWL
Akio Enoki, Hisashi Arikuni, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, enzymatic degradation, Seruroshin, boron tribromide,
1978-113
β-アルコキシ脱離反応を用いたアリールグリセロール-β-アリールエーテル結合の選択的開裂
松本雄二、石津 敦、中野準三
東京大学農学部
Selective cleavage of arylglycerol-β-aryl ether bond by β-alkoxy elimination reaction
Yuji Matsumoto, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: erythro and threo isomers, 13C-NMR, mass spectrometry, TLC
1978-114
三弗化硼素・フエノール系におけるリグニンの反応 —ジフェニルメタン構造の形成について
船岡正光、阿部 勲
三重大学農学部
Reaction of lignin in borontrifluoride-phenol system. –Formation of diphenylmethane structure
Masamitsu Funaoka, Isao Abe
Faculty of Agriculture, Mie University
Keywords: Yezo spruce, Picea jezoensis, TLC, quinone methide, quinhydron, visible light absorption
spectrometry
1978-115
過マンガン酸カリ酸化分解によるリグニン化学構造の分析
諸星紀幸*1、W．G．Glasser*2
東京農工大学農学部
Analysis of lignin structure by oxidative degradation with potassium permanganate
Noriyuki Morohoshi*1, W.G. Glasser*2*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Virginia Polytechnic Institute andState University
Keywords: Loblolly pine, Pinus taeda, red alder, Alnus rubra, gel filtration, gas chromatography
1978-116
アルカリリグニンの着色構造 —バニリルアルコール縮合物の着色構造について—
安田征市、藤井和美、尹 炳虎、寺島典二
名古屋大学農学部
Chromophoric structures of alkali lignin. Chromophoric structures of condensation products from vanillyl
alcohol
Seiichi Yasuda, Kazumi Fujii, Byung-Ho Yoon, Noritsugu Terashima.
Faculty of Agriculture, Nagoya University
Keywords: 13C-enrichment, 13C-NMR, diguaiacyl methane, quinone methide,
1978-117
核共役二重結合を有する化合物の過酸化水素に対する挙動
小島康夫、香山 彊
北海道大学農学部
Behavior of aromatic compounds carrying conjugated double bonds in the reaction with hydrogen peroxide
Yasuo Kojima, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords: isoeugenol, dehydrodiisoeugenol, vanillin, o-methoxy-p-hydroquinone, mass spectrometry,113

1

H-NMR,

1978-201
高濃度オゾン水によるクラフトパルプの漂白
藤井利郎*1、上嶋 洋*1、赤松 勲*1、中山繁樹*2、難波敬典*2*1
四国工業技術試験所、*2 三菱電機株式会社
Bleaching of kraft pulp with water containing high concentration of ozone
Toshiro Fujii*1, Hiroshi Kamishima*1, Isao Akamatsu*1, Shigeki Nakayama*２, Takanori Nanba*２*1
Government Industrial Research Institute, Shikoku, *２Mitsubishi Electric Corporation
Keywords: Douglas fir, Pseudotsuga taxifolia, brightness, viscosity, pH
1978-202
高収率パルプの製造に関する研究（第 3 報）TMP のオゾン処理に及ぼすリファイニング温度の影響
久保隆昌、細川 純、小林 武、赤松 勲、木村 裕
四国工業技術試験所
Studies on the high yield pulp production (III), Effect of refining temperature on ozone treatment of TMPTakamasa Kubo, Jun Hosokawa, Takeshi Kobayashi, Isao Akamatsu, Yutaka Kimura
Government Industrial Research Institute, Shikoku
Keywords: Japanese red pine, Pinus densiflora, freeness, fiber length distribution，breaking length
1978-203
酸素酸化精製パルプのオゾン漂白について（第 2 報）
萱場 基、戸坂圀夫、林 治助
北海道大学工学部
Ozone bleaching of oxygen treated pulp (II)Motoi Kayaba, Kunio Tosaka, Jisuke Hayashi
Faculty of Engineering, Hokkaido University
Keywords: Betula Tauschii, brightness,
1978-204
チオリグニンのオゾン分解について
金子英信、細谷修二、中野準三
東京大学農学部
Degradation of thiolignin by ozone
Hidenobu Kaneko, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: ESR spectroscopy, double bond content, GPC, IR spectroscopy, 1H-NMR,
1978-205
クラフト蒸解時のイオウの挙動（IV) 揮発性有機イオウ化合物の生成について
近藤隆一郎、近藤民雄
九州大学農学部
Behavior of sulfur during kraft pulping (IV), On the formation of volatile organic sulfur compounds
Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, Pinus densiflora, labile methoxyl group, dioxane lignin
1978-206
放射線前照射チップのクラフト蒸解に関する研究
稲葉政満、飯塚堯介、中野準三
東京大学農学部
Studies on the kraft pulping of wood chips pretreated byγ-ray
Masamitsu Inaba, Gyosuke Mashitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
114

Keywords:

beech, Fagus crenata, α-hydroxylalkyl radical

1978-207
アルカリ蒸解助剤テトラヒドロアントラキノンの脱リグニン促進機構
矢口時也*1、佐藤惇夫*1、野村芳禾*1、中村正人*1、細谷修二*2、中野準三*2*1
本州製紙株式会社、*2 東京大学農学部
Promotion mechanism of delignification by alkaline cooking aids, tetrahydroanthraquinone
Tokiya Yaguchi*1, Atsuo Satoh*1, Yoshika Nomura*1, Masato Nakamura*1, Shuji Hosoya*2, Junzo Nakano*2*1
Honshu Paper Co. Ltd. *2Faculty of Agriculture, the University of Tokyo
Keywords: guaiacylglycerol-βguaiacyl ether, oxygen-free cooking, carbohydrate
1978-208
ユーカリ材の抽出成分量とパルプ収率
亀井基和*1、大江礼三郎*2*1
北越製紙株式会社、*2 東京農工大学農学部
Content of extractives and yield of pulp from eucalyptus wood
Motokazu Kamei*1, Raysaburo Oye*2*1
Hokuetsu Paper Co. Ltd., *2Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Eucalyptus calophylla, Eucalyptus diversicolor, Klason lignin
1978-209
酸素・アルカリ蒸解の蒸解要因（II）界面活性剤添加の効果
日黒貞利、近藤民雄
九州大学農学部
Cooking factor in oxygen alkali pulping (II), Effect of addition of surface active agents
Sadatoshi Meguro, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, Asplund pulp, sodium laurylbenzene sulfonate, Tween 20
1978-210
マグネファイト—酸素・Mg(OH)2 蒸解について
十河村男、幡 克美、山崎 徹
香川大学農学部
On the magnefite-O2+Mg(OH)2 pulping
Murao Sogo, Katsumi Hata, Toru Yamasaki
Faculty of Agriculture, Kagawa University
Keywords: Betula Tauschii, Eucalyptus sp., gel filtration, MWL
1978-211
非木材繊維の叩解について（第 2 報）
ラム・チ・パクチュエト*1、原 啓志*2、大江礼三郎*１*1
東京農工大学農学部、*2 三島製紙株式会社
Beating of non-woody fiber (II)Lam T. B. T*1., Keishi Hara*2, Raysabro Oye*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Mishima Paper Co., Ltd.
Keywords: Linum usitatissimum, Hibiscus cannabinus, mercury penetration, monosaccharide composition
1978-212
バガスから新聞紙パルプの調製について
御田昭雄*1、佐伯 剛*2
東京工業試験所、工学院大学
Production of newspaper pulp from bagasse
Akio Mita*1, Tsuyoshi Saiki*2*1
Government Chemical Industrial Research Institute, Tokyo, *2Kogakuin University
115

Keywords:
endurance

bleaching, brightness, breaking length, tear factor, percent Elmendorf tear factor, folding

1978-213
TMP 法によるバガスのパルプ化
西山昌史*1、松尾隆吉*1、小林良生*1、佐藤隆士*2、Naiyana Niyomwan*3*1
四国工業技術試験所、*2 日立造船株式会社、*３ASRCT
Pulping of bagasse by TMP process
Masashi Nishiyama*1, Ryukichi Matsuo*1, Yoshinari Kobayashi*1, Takashi Sato*2, Naiyana Niyomwan*3*1
Government Industrial Research Institute, Shikoku, *2Hitachi Zosen Corporation, *3ASRCT
Keywords: freeness, breaking length, tear factor,
1978-2014
KP 晒廃液中の毒性物質の分画とキャラクタリゼーション
鮫島一彦*1、B. Simson*2，C. W. Dence*2*1
高知大学農学部、*2 ニューヨーク州立大学
Fractionation and characterization of toxic substances in effluent from KP bleaching process
Kazuhiko Sameshima*1, B. Simon *2, C.W. Dence *2*1
Faculty of Agriculture, Kochi University, *2State University of New York.
Keywords: southern pine, Daphnia magna, Aspergillus fumigatus, TOC, molecular weight, VPO
1978-215
KP 蒸解廃液の活性汚泥処理と限外ロ過特性について
三浦 清、平田裕浩
北海道大学農学部
Active sludge treatment of KP waste liquor and its ultrafiltration characteristics
Kiyoshi Miura, Yasuhiro Hirata
Faculty of Agriculture, Hokkaido University
Keywords: Betula platyphylla, Picea Glehnii, BOD, COD, UV and visible light absorption,
1978-216
Mg 系吸着剤のパルプ廃液成分吸着能
猪狩俶将、横山正一郎
東京工業試験所
Adsorption capacity of Mg containing adsorbents for components in pulp mill effluent
Yoshimasa Ikari, Shoichiro Yokoyama
Government Chemical Industrial Research Institute, Tokyo
Keywords: COD, adsorption isotherm,
1978-217
活性炭吸着機構に及ぼすパルプ製造排水成分の物理化学的性状の影響
飯山賢治、中野準三
東京大学農学部
Effect of physicochemical properties of pulp mill effluent on the mechanism of adsorption by
activated carbon
Kenji Iiyama, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: softwood lignin sulfonic acid, molecular size, intrinsic viscosity, adsorption isotherm
1978-218
特別講演、高収率パルプの現状と問嘩点角祐一郎
山陽国策パルプ株式会社
Invited lecture:116

Present state and problems in high yield pulp production
Yuichiro Sumi
Sanyo-Kokusaku Pulp Co. Ltd.
Keywords: SCP, TMP, NSSC, brightness, Tampella process, SCA-Billerud process, Ebara process117

第 24 回 （1979.11.1-2） 京都大学、生産開発科学研究所
1979-101β-O-4 及びシリンガレジノール構造からなる三量体リグニンモデル化合物の合成
釜谷保志、中坪文明、樋口隆昌
京都大学木材研究所
Synthesis of a trimeric lignin model compound composed of β-O-4 and syringaresinol substructures
Yasushi Kamaya, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: stereochemistry, erythro and threo isomers, IR spectroscopy, 1H-NMR
1979-102β-O-4 及び β-1 構造からなる三量体リグニンモデル化合物の合成
難波宏彰、中坪文明、樋口隆昌
京都大学木材研究所
Synthesis of a trimeric lignin model compound composed of β-O-4 and β-1 substructures
Hiroaki Namba, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: IR spectroscopy, UV spectroscopy, 1H-NMR,
1979-103
フェニルクマラン及び β-1 構造からなる三量体リグニンモデル化合物の合成並びにリグニン
モデル化合物の合成に関するまとめ
中坪文明、樋口隆昌
京都大学木材研究所
Synthesis of trimeric lignin model compounds composed of phenylcoumaran and -1 substructures, andsummary of synthetic method for lignin model compounds
Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: IR spectroscopy, 1H-NMR, diastereomers,
1979-104
広葉樹プロトリグニンの水素化分解に関する研究 -新 2 量体（-O-4）の単離
黄 炳浩、榊原 彰
北海道大学農学部
Studies on the hydrogenolysis of hardwood protolignin. –Isolation of a new dimeric product with -O-4 linkage
Byung Ho Hwang, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Fraxinus excelsissima, TLC, UV spectrum, IR spectrum, MS spectrum, 1H-NMR,
1979-105
リグナン類の 13C−NMR スペクトル
三木啓司、笹谷宣志、榊原 彰
北海道大学農学部
13
C−NMR spectroscopy of lignans
Keiji Miki, Takashi Sasaya, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: larch, Larix Kaempferi, diastereomer, erythro and threo isomers, chemical shift
1979-106
ユウガオ及びヒョータン硬化果皮のリグニンについて
川上日出国、福田忠徳
名古屋大学農学部
On the lignin in hardened rind of Lagenaria siceraria Standley var. hispida Hara and Lagenaria siceraria
118

Standley var. gourd Hara
Hidekuni Kawakami, Tadanori Fukuda
Faculty of Agriculture, Nagoya University
Keywords: phenylalanine ammonia-lyase, nitrobenzene oxidation, permanganate oxidation, ethanolysis,
13
C-NMR, lignin structure
1979-107
出土木材リグニンの化学構造
玉井 篤、井上嘉幸、南 享二
筑波大学農林工学系
Chemical structure of lignin in excavated wood
Atsushi Tamai, Yoshiyuki Inoue, Kyoji Minami
Institute of Agricultural and Forest Engineering, University of Tsukuba
Keywords: Aesculus turbinate, MWL, permanganate oxidation, 1H-NMR, nitrobenzene oxidation
1979-108
透析膜法による LCC の合成と植物細胞壁のモデル化
棚橋光彦、樋口隆昌
京都大学木材研究所
Synthesis of LCC by dialysis membrane method and modeling of plant cell wall
Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phyllostachys pubescens, thermal softening property, hydrophobic chromatography,
1979-109
リグニン・糖結合体に関する研究（その 2）リグニン・糖結合体に及ぼす界面活性剤の効果
東 順一、高橋信義、越島哲夫
京都大学木材研究所
Studies on lignin-carbohydrate complex (II), Effect of surface active agents on lignin-carbohydrate complex
Junichi Azuma, Nobuyoshi Takahashi, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Japanese red pine, Pinus densiflora, gel filtration, non-ionic detergent, anionic detergent,cationic detergent
1979-110
二量体に相当するリグニンモデル化合物の酸化分解
沖 妙、大久保克美、石川久雄
愛媛大学農学部
Oxidative degradation of lignin model compounds corresponding to dimer
Tae Oki, Katsumi Okubo, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: guaiacylglycerol--guaiacyl
ether,
dihydrodehydrodiisoeugenol,
oxygen-alkali oxidation, alkaline H2O2 oxidation, peracetic acid oxidation

symprocosigenol,

1979-111
リグニンの主分散及びローカルモード緩和
畠山兵衛*1、中村邦雄*2、畠山立子*3*1
製品科学研究所、*2 神奈県工業試験所、*3 繊維高分子材料研究所
Main dispersion and local mode relaxation of lignin
Hyoe Hatakeyama*1, Kunio Nakamura*2, Tatsuko Hatakeyama*3*1*3
Industrial Products Research Institute, *2Industrial Research Institute of Kanagawa Prefecture,
Research
Institute for Polymers and Textiles.
Keywords: lignin related polystyrenes, MWL, GPC, broad-line NMR, DSC, glass transition temperature
1979-112
細胞間層リグニンの性状について119

趙 南爽、飯塚堯介、中野準三
東京大学農学部
On the characteristics of compound middle lamella lignin
Nam Seok Cho, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Betula Ermanii, MWL, nitrobenzene oxidation, S/V ratio,
1979-113
リグニンのオゾン分解
金子英信、細谷修二、中野準三
東京大学農学部
Degradation of lignin with ozone
Hidenobu Kaneko, Shuji Hosoya, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: dehydrodivanillyl alcohol, thiolignin, Picea jezoensis, soda lignin, TLC, 1H-NMR, 13C-NMR
1979-114
リグニンの親水性化に関する研究（2）飯塚堯介、中野準三
東京大学農学部
Studies on introducing hydrophilicity to lignin (II)Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: softwood kraft lignin, sulfonation, surface tension, metal complex formation
1979-115
クラフトリグニンの調製について — 失敗の記録から
中野準三、高塚千代子
東京大学農学部
Preparation of kraft lignin, –Problems in purification procedure
Junzo Nakano, Chiyoko Takatsuka
Faculty of Agriculture, the University of Tokyo
Keywords: methoxyl content, dioxane, freeze drying
1979-116
特別講演、Invited lecture:
Speculative pathways for the fungal metabolism of lignin substructures
T. K. Kirk
Forest Products Laboratory，Madison，U.S.A
Keywords: white-rot fungi, Phanerochaete chrysosporium, Fusarium sp.,
1979-201
針葉樹リグニンと広葉樹リグニンの担子菌による分解
広居忠量
林業試験場
Degradation of softwood lignin and hardwood lignin by Basidiomycetes
Tadakazu Hiroi
Forestry and Forest Products Research Institute
Keywords: Chamaecyparis obtuse, Betula Tauschii, Pinus densiflora,
Phanerochaete chrysosporium,
1979-202
カタウロコタケ粗酵素によるリグニンの分解
福田 滋、原口隆英、諸星紀幸
120

Fagus

crenata,

MWL,

東京農工大学農学部
Degradation of lignin by crude enzyme of Stereum flustulosum
Shigeru Fukuda, Takafusa Haraguchi, Noriyuki Morohoshi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Picea jezoensis, Ulmus davidiana, MWL, Bavendamm’s reaction, vanillic acid, ferulic acid
1979-203
Fusarium spp. によるリグニン関連芳香族化合物の側鎖の分解について
岩原章二郎*1、城森孝仁*1、一色健二*1、樋口隆昌*2
香川大学農学部, 京都大学木材研究所
Degradation of side chain of lignin related aromatic compounds by Fusarium spp.
Shojiro Iwahara*1, Takahito Jomori*1, Kenji Isshiki*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: biodegradation, 3,4-dimethoxycinnamaldehyde, 3,4-dimethoxycinnamic acid, pinoresinol, UV
spectroscopy
1979-204
リグニンの酸化分解反応（II）. H2O2 によるクラフトパルプ廃液の酸化分解処理
辰己憲司*1、寺島典二*2*1
公害資源研究所、*2 名古屋大学農学部
Oxidative degradation of lignin (II), Oxidative degradation treatment of kraft pulp mill effluent with hydrogen
peroxide
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: Pinus densiflora, Fenton reagent, hydroxyl radical, degradation by UV-H2O2, COD, TOC
1979-205
クラフト蒸解時のイオウの挙動（VI）蒸解時のメチルメルカプタンについて
近藤隆一郎、近藤民雄
九州大学農学部
Behavior of sulfur during kraft pulping (VI), Methyl mercaptan generated during cooking
Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, Pinus densiflora, volatile organic sulfur, kraft cooking
1979-206
処理木粉によるクラフト臭気成分の吸着処理
池田耕作、近藤隆一郎、近藤民雄
九州大学農学部
Adsorption treatment of kraft smell components with pretreated wood powder
Kosaku Ikeda, Ryuichiro Kondo, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, hydrogen sulfide, methyl mercaptan
1979-207
多段オゾン漂白効果の要因について
小林 武、細川 純、久保隆昌、木村 裕
四国工業技術試験所
Factors affecting multistage ozone bleaching
Takeshi Kobayashi, Jun Hosokawa, Takamasa Kubo, Yutaka Kimura
Government Industrial Research Institute, Shikoku
Keywords: ash content, resin content, brightness, viscosity,
1979-208121

パルプのオゾン漂白廃水の性状
三浦 清、佐藤礼人
北海道大学農学部
Properties of effluent from ozone bleaching of pulp
Kiyoshi Miura, Ayato Sato
Faculty of Agriculture, Hokkaido University
Keywords: Betula Tauschii, kraft pulping, ultrafiltration, UV absorption, BOD, COD
1979-209
針葉樹材 CTMP のオゾン処理
細川 純、久保隆昌、小林 武、赤松 勲
四国工業技術試験所
Ozone treament of softwood CTMP
Jun Hosokawa, Takamasa Kubo, Takeshi Kobayashi, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: Pinus densiflora, sulfur dioxide, folding endurance, breaking length, brightness
1979-210
イピルイピルの SOX 法によるパルプ化
御田昭雄*1、佐伯 剛*2*1
化学技術研究所, *2 工学院大学
Pulping of Leucaena leucocephala by SOX process
Akio Mita*1, Tsuyoshi Saiki*2*1
The Government Chemical Industrial Research Institute, Tokyo, *2Kogakuin University
Keywords: neutral sulfite semichemical pulp, kraft pulp, brightness, ring crush test
1979-211
酸素・アルカリ蒸解の蒸解要因（IV）界面活性剤による脱リグニン促進について
目黒貞利、近藤民雄
九州大学農学部
Cooking factors in oxygen alkali pulping. IV. Promotion of lignin removal by surfactant
Sadatoshi Meguro, Tamio Kondo
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, Pinus densiflora, sodium laurylbenzene sulfonate, Asplund process, dioxane
lignin
1979-212
TMP 法によるパラゴム廃材のパルプ化
久保隆昌、細川 純，小林 武、赤松 勲、小林良生
四国工業技術試験所
Pulping of Para rubber waste wood by TMP process
Takamasa Kubo, Jun Hosokawa, Takeshi Kobayashi, Isao Akamatsu, Yoshio Kobayashi
Government Industrial Research Institute, Shikoku
Keywords: Hevea brasiliensis, TMP, freeness, breaking length, tear factor, brightness
1979-213
TMP 法によるバガスパルプの漂白特性
松尾隆吉、西山昌史、小林良生
四国工業技術試験所
Bleaching characteristics of bagasse pulp produced by TMP process
Ryukichi Matsuo, Masashi Nishiyama, Yoshinari Kobayashi
Government Industrial Research Institute, Shikoku
Keywords: sugar cane, Saccharum sp, brightness,
1979-214122

活性汚泥処におけるクラフトリグニンの挙動
鮫島一彦、高村憲男、瀬戸辰彦
高知大学農学部
Behavior of kraft lignin during treatment with activated sludge
Kazuhiko Sameshima, Norio Takamura, Tatsuhiko Seto
Faculty of Agriculture, Kochi University
Keywords: Pinus densiflora, Betula Tauschii, BOD, COD, gel filtration, UV absorption spectroscopy
1979-215
パルプ蒸解廃液からの活性炭製造に関する研究 第 4 報
戸坂圀夫、鈴木英次、林治助
北海道大学工学部
Studies on the production of activated carbon from pulp waste liquor (IV)
Kunio Tosaka, Eiji Suzuki, Jisuke Hayashi
Faculty of Engineering, Hokkaido University
Keywords: Abies Mayriana, steam activation
1979-216
特別講演、リグニン利用の現状と問題点
町原 晃
山陽国策パルプ株式会社
Invited lecture: Present state and problems in utilization of lignin
Akira Machihara
Sanyo-Kokusaku Pulp Co. Ltd.
Keywords: cement dispersant, binder of ore powder, detergent123

第 25 回 （1980.10.17-18） 九州大学農学部
1980-101
1,2-ジアリールプロパン-1,3−ジオール化合物の Fusarium solani による分解
難波宏彰、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of 1,2-diarylpropane-1,3-diol compounds by Fusarium solani
Hiroaki Namba, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: mass spectrometry, 1H-NMR, UV absorption spectroscopy, phenol oxidase, aldorase
1980-102
シリンギル核を含む β-O-4 および β-5 型ジリグノールの Fusarium solani による分解
片山健至、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of β-O-4 and β-5 dilignols containing syringyl nucleus by Fusarium solani
Takeshi Katayama, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: biodegradation, syringylglycerol-β-vanillin ether, oxygenase, phenol oxidase
1980-103
Fusarium solani による d,l-シリンガレジノールの分解
釜谷保志、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of d,l-syringaresinol by Fusarium solani
Yasushi Kamaya, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: UV absorption spectroscopy, mass spectrometry, 1H-NMR, HPLC, phenol oxidase
1980-104
リグニンの微生物分解に関与する酵素系について
沖 妙、渡部広行、石川久雄
愛媛大学農学部
Enzyme systems participating in microbial degradation of lignin
Tae Oki, Hiroyuki Watanabe, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Lentinus edodes, Fagus crenata, dioxane lignin, guaiacylglycerol-β-guaiacyl ether, UV
absorption spectroscopy. gel filtration, phenol oxidase, laccase, peroxidase
1980-105
カタウロコタケ粗酵素によるリグニンの分解（第 2 報）—菌体内粗酵素によるミズナラ MWL の分解—
福田 滋、諸星紀幸、原口隆英
東京農工大学農学部
Degradation of lignin by crude enzyme of Stereum flustulosum (II), Degradation of Japanese oak MWL byintracellular crude enzyme
Shigeru Fukuda, Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: syringic acid, 2,6-dimethoxy-1,4-benzoquinone, IR spectrum
1980-106
リグニン生分解と酸化還元酵素
石原達夫
林業試験場
124

Biodegradation of lignin and oxidoreductase
Tatsuo Ishihara
Forestry and Forest Products Research Institute
Keywords: Pleurotus ostreatus, Betula Tauschii, laccase, cellobiose oxidase, redox potential，
1980-107
木材腐朽菌（カワラタケ）によるリグニンモデル化合物の代謝片山義博
筑波大学農林工学系
Metabolism of lignin model compounds by wood rotting fungi Coridus versicolor
Yoshihiro Katayama
Institute of Agricultural and Forest Engineering, University of Tsukuba
Keywords: syringaresinol, pinoresinol, UV absorption spectroscopy, 1H-NMR, 13C-NMR,
1980-108
Phanerochaete chrysosporium によるフェニルクマラン型二量体の分解機構の研究
梅澤俊明*1、中坪文明*1、樋口隆昌*1、T.K．Kirk*2*1
京都大学木材研究所、*２マジソン林産物研究所
Degradation mechanism of phenylcoumaran type dimer by Phanerochaete chrysosporium
Toshiaki Umezawa*1, Fumiaki Nakatsubo*1, Takayoshi Higuchi*1, T.K．Kirk*2*1
Wood Research Institute, Kyoto University, *2 Forest Products Laboratory，Madison，U.S.A
Keywords: 2-(4-hydroxy-3,5-dimethoxyphenyl)-3-hydroxymethyl-5-formyl-7-methoxycoumaran,
phenol oxidase
1980-109
硫酸リグニンの化学構造—アリールグリセロール-β-アリールエーテル型構造からの縮合物の化学構造—
安田征市、寺島典二、伊東 健
名古屋大学農学部
Chemical structures of sulfuric acid lignin, —Chemical structures of condensation products fromarylglycerol-β-aryl ether type structures—
Seiichi Yasuda, Noritsugu Terashima, Takeshi Ito
Faculty of Agriculture, Nagoya University
Keywords: 13C-NMR, creosol, phenylcoumaran, Hibbert’s ketone, diphenylpropane compounds
1980-110
木酢液について黒田健一
筑波大学農林工学系
On the wood vinegar
Kenichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Keywords: Pinus densiflora, dioxane lignin, nitrobenzene oxidation, permanganate oxidation, HPLC,
guaiacol, creosol, 4-ethylguaiacol
1980-111
カキシブの硬化機構
田中治郎
林業試験場
Hardening mechanism of persimmon juice
Jiro Tanaka
Forestry and Forest Products Research Institute
Keywords: UV spectroscopy, IR spectroscopy, carbonyl group125

1980-112
ビーズ状リグニン樹脂の製造に関する研究
飯塚堯介、中野準三
東京大学農学部
Studies on production of beads type resin from lignin
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: hardwood lignosulfonic acid, two-step resinification, one-step resinification
1980-113
リグニンの酸化分解（III） —H2O2 によるリグニンモデル化合物の酸化分解—
辰己憲司*1、寺島典二*2*1
公害資源研究所、*2 名古屋大学農学部
Oxidative degradation of lignin (III), Oxidative degradation of lignin model compounds with hydrogen peroxide
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: UV radiation, pH dependence, veratric acid, vanillic acid, protocatechuic acid
1980-114
リグニンのオゾン分解について
金子英信、中野準三
東京大学農学部
Degradation of lignin with ozone
Hidenobu Kaneko, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: lignin model compound, thiolignin, surface tension, dispersion effect, dispersion number,
1
H-NMR, 13C-NMR,
1980-115
クラフト蒸解廃液中の生物活性物質
重松章彦、鮫島一彦、高村憲男
高知大学農学部
Bioactive substances in kraft pulp waste liquor
Akihiko Shigematsu, Kazuhiko Sameshima, Norio Takamura
Faculty of Agriculture, Kochi University
Keywords: Pinus densiflora, Betula Tauschii, Oryzias latipes, medaka bioassay, toxicity,
1980-116
パルプ廃液中の有機塩素化合物の毒性および分解性
島田謹爾
林業試験場
Toxicity and degradability of organic chlorine compounds in pulp waste liquor
Kinji Shimada
Forestry and Forest Products Research Institute
Keywords: bioassay, Oryzias latipes, trichloroguaiacol, trichlorosyringol
1980-117
特別講演、石炭の液化と炭化
竹下健次郎
九州大学生産科学研究所
Invited lecture: Liquefaction and carbonization of coal
Kenjiro Takeshita
Kyushu University Research Institute for Production Science
Keywords: model compounds of coal, coal pitch, mesophase, microphotograph126

1980-201
不斉場におけるコニフェリルアルコールの脱水素重合
三木啓司、榊原 彰
北海道大学農学部
Dehydrogenative polymerization of coniferyl alcohol in chiral environment
Keiji Miki, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Quercus mongolica, Larix leptorepis, holocellulose, hemicellulose, gel filtration
1980-202
シナポイル CoA リガーゼの植物間分布及び性質について
久津木英俊、島田幹夫、樋口隆昌
京都大学木材研究所
Occurrence of synapoyl Co-A ligase among plants and its properties
Hidetoshi Kutsuki, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Erythrina crista-galli, feruloyl Co-A ligase, 5-hydroxyferulic acid
1980-203
広葉樹プロトリグニンの水素化分解物に関する研究黄 炳浩、榊原 彰
北海道大学農学部
Studies on the hydrogenolysis products from hardwood protolignin
Byung Ho Hwang, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Fraxinus mandshurica var. japonica, mass spectrometry, 1H-NMR, diarylpropane derivative
1980-204
カラマツアテ材リグニンの水素化分解に関する研究
小林千益、安田征市、榊原 彰
北海道大学農学部
Studies on the hydrogenolysis of lignin in compression wood of larch
Seneki Kobayashi, Seiichi Yasuda, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Larix leptolepis, phenylisochromane, diarylpropane, lignaloid, lappaol A,B,C,D
1980-205
アリールグリセロール-β-アリールエーテル型構造の選択的解裂について
松本雄二、石津 敦、中野準三
東京大学農学部
Selective cleavage of arylglycerol-β-aryl ether type structure
Yuji Matsumoto, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, γ-p-toluenesulfinyl veratrylglycerol-β-guaiacyl ether, MWL, gel filtration
1980-206
エゾマツブラウンズリグニン（BL）の性質について
高橋秀敏、青山政和、榊原 彰
北海道大学農学部
On the properties of Brauns’s lignin (BL) from Yezo spruce
Hidetoshi Takahashi, Masakazu Aoyama, Akira Sakakibara
Faculty of Agriculture, Hokkaido University127Keywords:

Picea jezoensis, lignan, western hemlock, Tsuga heterophylla, 1H-NMR, 13C-NMR

1980-207
磨砕時間を異にして段階的に単離した広葉樹 MWL の性状について
李 忠正、飯塚堯介、中野準三
東京大学農学
Characteristics of hardwood MWL isolated with different milling times
Zhong Zheng Lee, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: birch, Betula sp., cell wall layers, nitrobenzene oxidation, non-conjugated phenolic hydroxyl
group,
1980-208
へミセルロース・リグニン結合体に関する研究（その 4）—アカマツあて材 MWL 画分よりのへミセルロース・リ
グニン結合体の性質
向吉俊一郎、東 順一、越島哲夫
京都大学木材研究所
Studies on the hemicellulose-lignin complex (IV), Characteristics of hemicellulose-lignin complex obtained
from MWL fraction of red pine compression wood
Shunichiro Mukoyoshi, Junichi Azuma, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, gel filtration, methylation analysis, Smith degradation, galactose
1980-209
ユーカリ材チップの劣化
岡山隆之、蔵本 敬、屋部雅夫、大江礼三郎
東京農工大学農学部
Biodegradation of eucalyptus wood chip
Takayuki Okayama, Takashi Kuramoto, Masao Yabe, Raysabro Oye
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: thermal degradation, Klason lignin, holocellulose
1980-210
硝酸法蒸解におけるリグニンの挙動について —モデル実験—
Huynh Van Ba、石津 敦、中野準三
東京大学農学部
Behavior of lignin during nitric acid pulping, —Model experiments—
Huynh Van Ba, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: apocynol, guaiacylglycerol-β-guaiacyl ether, veratrylglycerol-β-guaiacyl ether, TLC
1980-211
クラフト蒸解における木材成分の溶出挙動と黒液成分の変化
玉生征人，炭村栄一，高橋 武，上埜武夫
山陽国策パルプ株式会社
Dissolution of wood components and change of black liquor composition during kraft cooking
Masato Tamao, Eiichi Sumimura, Takeshi Takahashi, Takeo Ueno
Sanyo Kokusaku Pulp Co., Ltd.
Keywords: lignin, carbohydrate, low molecular fraction, high molecular fraction, active alkali,
1980-212
バガスの過酸化水素アルカリ蒸解について
御田昭雄、柏原 進、河村英司
化学技術研究所
Pulping of bagasse with hydogenperoxide and alkali
128

Akio Mita, Susumu Kashiwabara, Eishi Kawamura
The Government Chemical Industrial Research Institute, Tokyo
Keywords: energy consumption, pulp yield, Kappa number, pentosan content
1980-213
KP の酸素-オゾン-過酸化水素漂白
藤井利郎、上嶋 洋、赤松 勲
四国工業技術試験所
Bleaching of KP with oxygen-ozone-hydrogen peroxide
Toshiro Fujii, Hiroshi Kamishima, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: Pseudotsuga taxifolia, viscosity, brightness
1980-214
パルプのオゾン漂白に関する研究
三浦 清、香山 彊
北海道大学農学部
Studies on the ozone bleaching of pulp
Kiyoshi Miura, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords: Abies Mayriana, SEM (scanning electron microscopy), ESR (electron spin resonancespectroscopy)
1980-215
薬液添加ＴＭＰの製造とその品質について
加地隆男，菊池春朗，河村道雄
大王製紙株式会社
Manufacturing and properties of TMP with chemicals
Takao Kaji, Shunro Kikuchi, Michio Kawamura
Daio Paper Corporation
Keywords: Picea sp., Eucalyptus, high yield pulp, resource saving, specific energy consumption, domesticpine,
1980-216
針葉樹 CTMP に関する研究 —収率差における物性と漂白性について—
小島康夫、香山 彊
北海道大学農学部
Studies on the softwood CTMP. —Relation between pulp yield and physical properties, and bleachability
Yasuo Kojima, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords: Picea Glehnii，freeness, density, printing opasity, brightness,
1980-217
総合討論、これからのリグニン研究 —若手研究者の立場から—
飯山賢治（東京大学農学部 司会）、安田征市（名古屋大学農学部）、鮫島一彦（高知大学農学部）、飯塚堯介（東京大学農学部）、中坪文明（京都大学木質科学研究所）
General discussion on “Future prospects of lignin research”, From young researchers
Moderator: Kenji Iiyama (Faculty of Agriculture, the University of Tokyo)
Seiichi Yasuda (Faculty of Agriculture, Nagoya University)
Kazuhiko Sameshima (Faculty of Agriculture, Kochi University)
Gyosuke Meshitsuka (Faculty of Agriculture, the University of Tokyo)
Fumiaki Nakatsubo (Faculty of Agriculture, Kyoto University)129

第 26 回 （1981.10.29-30） 工業技術院筑波研究センター
1981-101
Fusarium solani によるグリセロール−2−バニリン酸エーテルおよぴフェニルクマラン型二量体の分解
片山健至、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of glycerol-2-vanilic acid ether and phenylcoumaran-type dimer by Fusarium solani
Takeshi Katayama, Fumiaki Nakatubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: biodegradation, Fusarium solani , arylglycerol-β-aryl ether, phenylcoumaran
1981-102
Fusarium solani による d,l-シリンガレジノールの分解（その 2）
釜谷保志、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of d,l-syringaresinol by Fusarium solani, II.
Yasushi Kamaya, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: biodegradation, Fusarium solani, syringaresinol
1981-103
カワラタケ・ラッカーゼの分別と精製及び 2，3 の性質
村磯知採、割石博之、永井 享、諸星紀幸、原口隆英
東京農工大学農学部
Fractionation and purification of laccase from Coriolus versicolor and its properties
Chidori Muraiso, Hiroyuki Wariishi, Tooru Nagai, Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Laccase, Coriolus versicolor
1981-104
カワラタケ・ラッカーゼによるリグニンの変化（第 2 報）−BNL，MWL，LCC，残渣木粉中のリグニンの定量的変化量について−
諸星紀幸、原口隆英
東京農工大学農学部
Changes of lignin by laccase from Coriolus versicolor (II), Quantitative evaluation of changes of lignin in BNL,
MWL, LCC, residual wood meal
Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: laccase, Coriolus versicolor
1981-105
Lentinus edodes 体外酵素による guaiacylglycerol-β-guaiacyl ether の分解
沖 妙、仙波裕子、石川久雄
愛媛大学農学部
Degradation of guaiacylglycerol-β-guaiacyl ether by the extracellular enzyme of Lentinus edodes
Tae Oki, Yuko Sennami, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Lentinus edodes, guaiacylglycerol-β-guaiacyl ether
1981-106
Phanerochaete chrysosporium によるフェノール性水酸基をもつフェニルクマラン型二量体の分解
梅澤俊明、中坪文明、樋口隆昌
京都大学木材研究所
Degradation of a phenolic phenylcoumaran-type dimer by Phanerochaete chrysosporium
130

Toshiaki Umezawa, Fumiaki Nakatsubo, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: phenylcoumaran, dimer, Phanerochaete chrysosporium
1981-107
担子菌の変異株を用いたべラトリルアルコール代謝とリグニンの『生合成』的生分解に関する研究
島田幹夫*1、樋口隆昌*1、M.H. Gold*2*1
京都大学木材研究所、*2OGC
Studies on the metabolism of veratrylalcohol by the mutant of baｓidiomycete and the biosynthetic degradationof lignin
Mikio Shimada*1, Takayoshi Higuchi*1, M.H. Gold*2*1
Wood Ressearch Institute , Kyoto University, *2Oregon Graduate Center
Keywords: Biosynthetic degradation, mutant, basidiomycetes, veratryl alcohol
1981-108
キノンメチド中間体を経る LCC モデルの形成に関する研究
棚橋光彦、樋口隆昌
京都大学木材研究所
Studies on the formation of LCC model compounds through quinone methide intermediate
Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: LCC model, quinine methide, glucose, xylose
1981-109
リグニンの KMnO4 酸化分解
佐野嘉拓*1、W.G. Glasser*2
北海道大学農学部
Oxidative degradation of lignin with KMnO4
Yoshihiro Sano*1, W.G.Glasser*2*1
Faculty of Agriculture, Hokkaido University, *2Virginia Polytechnic Institute and State University
Keywords: KMnO4 oxidation, MWL
1981-110
オゾノリシスによるリグニン中の glyceraldehyde−2−aryl ether 構造の定量
松本雄二、石津 敦、中野準三
東京大学農学部
Quantitative determination of glyceraldehyde-2-aryl ether in lignin by ozonolysis
Yuji Matsumoto, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: glyceraldehydes-2-aryl ether, ozonolysis, glycerol
1981-111
広葉樹プロトリグニンの水素化分解物に関する研究 —新 2 量体の単離—
黄 柄浩、榊原 彰
北海道大学農学部
Hydrogenolysis of hardwood protolignin, -Isolation of a new dimer
Byung Ho Hwang, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: hydrogenolysis, hardwood lignin, new dimer
1981-112
クラフトパルプ中の残留りグニンの性状
山崎 岳、細谷修二、Chen C．L., Gratzl J.S., Chang H.-m．
ノースカロライナ州立大学
131

Properties of residual lignin in kraft pulp
Takeshi Yamasaki, Shuji Hosoya, C. L. Chen, J.S. Gratzl, H.-m. Chang
North Carolina State University
Keywords: residual lignin, kraft pulp, enzymatic treatment, lignin-carbohydrate linkage in pulp
1981-113
硫酸リグニンの化学構造 —アリールグリセロール-β-アリールエーテルと 72％硫酸との反応—
安田征市、寺島典二、伊東 健
名古屋大学農学部
Structures of sulfuric acid lignin,-Reactions of arylglycerol-β-aryl ether in 72% sulfuric acid
Seiichi Yasuda, Noritsugu Terashima, Takeshi Ito
Faculty of Agriculture, Nagoya University
Keywords: sulfuric acid lignin, arylglycerol-β-ary ether, acid condensation
1981-114
水分及び熱処理によるリグニン主分散の変化
矢野彰一郎、品川俊一、畠山兵衛
製品科学研究所
Changes in the main dispersion of dynamic viscoelasticity curves of lignin by water and heat treatment
Shoichiro Yano, Shunichi Shinagawa, Hyoe Hatakeyama
Industrial Products Research Institute
Keywords: Tg, polystyrene, dynamic viscoelasticity
1981-115
へミセルロース・リグニン結合体（LCC）に関する研究（その 5）−アカマツ圧縮アテ材よりの Björkman LCC の性質—
東 順一*1、向吉俊一郎*1*2、越島哲夫*1*1
京都大学木材研究所, *2 神崎製紙株式会社
Studies on lignin hemicellulose complex (LCC) (V), Characterization of Björkman LCC from red pinecompression wood
Junichi Azuma*1, Shunichiro Mukoyoshi *1*２, Tetsuo Koshijima*1*1
Wood Research Institute, Kyoto University; *２Kanzaki Paper Co. Ltd.
Keywords: Pinus densiflora, hemicellulose, GPC
1981-116
リグニン—糖結合体の性状について
飯塚堯介*1、李 忠正*1、中野準三*1、江田 茂*2*1
東京大学農学部、*2 日本専売公社中央研究所
Characterization of lignin-carbohydrate complex
Gyosuke Meshitsuka*1, Zhong Zheng Lee *1, Junzo Nakano*1, Shigeru Eda*2*1
Faculty of Agriculture, the University of Tokyo, *2 Central Research Institute, Japan Tobacco and Salt Public
Corporation
Keywords: LCC, pectinase, GPC
1981-117
特別講演、C1 化学について
阪東憲一郎
化学技術研究所
Invited Lecture ; C-1 Chemistry
Kenichiro Bando
National Chemical Laboratory for Industry
1981-201
亜塩素酸塩法及び過酢酸法によるホロセルロースの調製過程で溶出する多糖成分について132前川英一、越島哲夫
京都大学木材研究所
Dissolution of polysaccharides during the hollocellulose preparation with sodium chlorite and peracetic acid
methods
Eiichi Maekawa, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, Fagus crenata, degree of delignification, UV absorption spectroscopy
1981-202
高収率パルプを用いるカルボキシメチルセルロースの調製（II) —カルボキシメチル化リグニンの加熱処理に対する挙動—
ラム・チ・バック・チュエット、石津 敦、中野準三
東京大学農学部
Preparation of carboxymethyl cellulose from high-yield pulp (II), Behavior of carboxymethyl lignin on heating
Thi Bach Tuyet Lam, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, MWL, carboxymethyl cellulose, high-yield pulp, carboxymethyl lignin
1981-203
リグニン存在下でのセルロース質の酵素分解
夜久富美子*1、田中龍太郎*1、村木永之介*1、足立公洋*1、越島哲夫*2*1
大阪工業技術試験所、*2 京都大学木材研究所
Enzymatic hydrolysis of cellulosic materials in the presence of lignin
Fumiko Yaku*1, Ryutaro Tanaka*1, Einosuke Muraki*1, Kimihiro Adachi*1, Tetsuo Koshijima*2*1
Government Industrial Research Institute, Osaka, *2Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, vibration ball mill, roll mill, cellulase
1981-204
リグニンおよび関連物質の熱分解（第 1 報）佐々木坤彪、鈴木正人、佐方克彦、長沢武夫
日本紙パルプ研究所
Pyrolysis of lignin and related materials (I)Nobutake Sasaki, Masato Suzuki, Katsuhiko Sakata, Takeo Nagasawa
Japan Pulp ＆ Paper Research Institute, Inc.
Keywords: Fagus crenata, chlorinated compound, chlorinated lignin
1981-2054−n−アルコキシ−3−メトキシ安息香酸誘導体の液晶性
春日和行、畠山兵衛
製品科学研究所
Properties of 4-n-alkoxy-3-methoxybenzoic acid derivatives as liquid crystal
Kazuyuki Kasuga, Hyoe Hatakeyama
Industrial Products Research Institute
Keywords: vanillin, alkyl chain length, transition temperature,
1981-206
リグニンの酸化分解（IV）紫外線照射下での H2O2 とリグニンモデル化合物の芳香核との反応
辰巳憲司*1、寺島典二*1*1
公害資源研究所、*2 名古屋大学農学部
Oxidative degradation of lignin (IV), Reactions of aromatic rings of lignin model compounds with hydrogen
peroxide under UV irradiation
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: HPLC, vanillic acid, protocatechuic acid133

1981-207
木材の液化に関する研究 (I) —アルカリ-アルコール法による樹皮の液化—
須藤賢一
林業試験場
Liquefaction of wood (I), -Liquefaction of bark by alkali-alcohol system
Kenichi Sudo
Forestry and Forest Products Research Institute
Keywords: GPC, IR absorption spectroscopy, 1H-NMR
1981-208
水素化によるパルプ製造に関する研究
榊原 彰、枝重有祐、植松敏夫、武山浩武
北海道大学農学部
Hydrogenolysis pulping
Akira Sakakibara, Yusuke Edasige, Toshio Uematsu, Hirotake Takeyama
Faculty of Agriculture, Hokkaido University
Keywords: Betula platyphylla, phenol, cresols, xylenols, guaiacol
1981-209
高収率パルプに関する研究 —化学前処理とリフアイニングエネルギー—
坂井克己
九州大学農学部
Studies on high yield pulp. -Chemical pretreatment and refining energy
Kokki Sakai
Faculty of Agriculture, Kyushu University
Keywords: Pinus Thunbergii, sodium sulfite, sodium chlorite, refining energy
1981-210
CMP のリフアイニング条件について
大森隆志、坂井克己
九州大学農学部
Refining conditions of chemi-mechanical pulp
Takashi Ohmori, Kokki Sakai
Faculty of Agriculture, Kyushu University
Keywords: CGP, RGP, TMP, sodium sulfite
1981-211
ジャイアント・レウカエナ材の CTMP 法による新聞紙級パルプ
久保隆昌*1 細川 純*1、小林 武*1、赤松 勲*1、小林良生*1、Supasuri Janesuthiwechakul*2
四国工業技術試験所
Production of newspaper grade CTMP from giant leucaena
Takamasa Kubo*1, Jun Hosokawa*1, Takeshi Kobayashi*1, Isao Akamatsu*1, Yoshinari Kobayashi*1, Supasri
Janesuthiwechakul*2*1
Government Industrial Research Institute, Sikoku, *2Royal Forest Dept. Thailand
Keywords: giant leucaena, Leucaena glauca, sodium sulfite, pulp properties, refining energy
1981-212
高歩留パルプの改質 —ラジカル的スルホン化反応による TMP の改質—
大井 洋、飯塚堯介、中野準三
東京大学農学部
Improvement of high yield pulp.-Improvement of TMP by radical sulfonation
Hiroshi Ohi, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
134

Keywords:

Picea jezoensis, sodium sulfite, potassium permanganate, manganese dioxide,

1981-213
木材チップの圧縮と蒸解性
岡山隆之、木下卓麻、大江礼三郎
東京農工大学農学部
Effect of roll-pressing of wood chips on pulping
Takayuki Okayama, Takuma Kinoshita, Reisabro Oye
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Eucalyptus marginata, Pinus densiflora, roll pressing, shear, kraft pulping
1981-214
ネマガリダケのパルプ化に関する研究
戸坂圀夫*1、望月 明*1、林 治助*1、ヌエ・ニイ・ウェイ*2*1
北海道大学工学部、*2 京都大学農学部
Studies on pulping of Sasa kurilensis
Kunio Tosaka*1, Akira Mochizuki*1, Jisuke Hayashi*1, *????????*2*1
Faculty of Engineering, Hokkaido University, *2Faculty of Agriculture, Kyoto University
Keywords: Sasa kurilensis, kraft pulping, soda pulping, oxygen alkali pulping
1981-2015
酸素・アルカリ蒸解の蒸解要因 —グアヤコールの酸素酸化に及ぼす酸素担体添加の効果−
目黒貞利
九州大学農学部
Factors influencing oxygen-alkali cooking, -Effects of oxygen carrier on the oxidation of guaiacol
Sadatoshi Meguro
Faculty of Agriculture, Kyushu University
Keywords: oxygen carrier, Co-salen, Co-salpr
1981-2016
シュウ酸添加オゾン漂白におけるシュウ酸の回収と再使用
藤井利郎、上嶋 洋、赤松 勲
四国工業技術試験所
Recovery and reuse of oxalic acid from effluent of ozone bleaching with oxalic acidToshio Fujii, Hiroshi Kamishima, Isao Akamatsu
Government Industrial Research Institute, Shikoku
Keywords: Pseudotsuga taxifolia, cellulose protectant, calcium oxalate
1981-2017
特別講演、今後のリグニン化学工業の展望
秦 邦男
十條製紙株式会社中央研究所
Invited lecture ; Future prospects of industrial utilization of lignin
Kunio Hata
Central Research Institute, Jujo Paper Co. Ltd.

135

第 27 回 （1982.10.21-22） 名古屋大学農学部
1982-101
オゾノリシスを用いたリグニン側鎖構造の研究 —各種単離リグニンへの適用—
松本雄二、石津 敦、中野準三
東京大学農学部
Studies on the structure of lignin side chain by ozonolysis,-Application to various isolated ligninsYuji Matsumoto, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, MWL, erythronic acid, threonic acid, glyceraldehydes-2-aryl ether, 13C-NMR
1982-102
針葉樹リグニンへのシリンギル核の導入
飯山賢治、R．Pant、中野準三
東京大学農学部
Introduction of syringyl nuclei to softwood lignin
Kenji Iiyama, R. Pant, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, Fagus crenata, MWL, Mäule color reaction, Fremy’s salt oxidation
1982-103
スギ心材の色とリグニン
黒田宏之、島地 謙
京都大学木材研究所
Color and lignin of Japanese cedar heartwood
Hiroyuki Kuroda, Ken Shimaji
Wood Research Institute, Kyoto University
Keywords: Japanese cedar, Cryptomeria japonica, MWL, LCC, microspectroscopy, morphology
1982-104
逐次アシドリシスにより溶出するリグニンの分子構造
船岡正光、阿部 勲
三重大学農学部
Structure of lignin dissolved by stepwise acidolysis
Masamitsu Funaoka, Isao Abe
Faculty of Agriculture, Mie University
Keywords: condensed structure, nuclear exchange reaction, nitrobenzene oxidation
1982-105
リグニンおよびリグニン関連型ポリスチレン誘導体の水素結合と吸着水
畠山兵衛*1、広瀬重雄*1、中村邦雄*2、畠山立子*3*1
製品科学研究所、*2 神奈川県工業試験所，*3 繊維高分子材料研究所
Hydrogen bond and adsorbed water of lignin and lignin-like polystyrene derivatives
Hyoe Hatakeyama*1, Shigeo Hirose*1, Kunio Nakamura*2, Tatsuko Hatakeyama*3*1
Industrial Products Research Institute, *2Kanagawa Industrial Technology Center, *3Research Institute for
Polymers and Textiles
Keywords: Libocedrus decurrens, dioxane lignin, lignin-like polystyrene derivatives, thermal analysis,
glass transition temperature
1982-106
リグニン—糖間結合に対するペクチン質の寄与
飯塚堯介、中野準三
東京大学農学部
Contribution of pectic substances to lignin carbohydrate bond136

Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: birch, Betula sp., endo-pectin lyase, endo-polygalacturonase, pectin esterase, LCC
1982-107
リファイナーメカニカルパルプを用いるカルボキシメチルセルロースの調製（第 3 報） カルボキシメチル化炭
水化物の溶出に及ぼすリグニンの影響
ラム・チ・バック・チユエット、飯山賢治、石津 敦、中野準三
東京大学農学部
Preparation of carboxymethyl cellulose from refiner mechanical pulp (III), Effect of lignin on the dissolution ofcarboxymethylated carbohydrates
Thi Bach Tuyet Lam, Kenji Iiyama, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, Fagus crenata, mannan, xylan, 1H-NMR,
1982-108
針葉樹仮道管の壁形成における多糖類とリグニンの堆積高部圭司、藤田 稔、佐伯 浩、原田 浩
京都大学農学部
Deposition of polysaccharides and lignin during the cell wall formation of softwood tracheids
Keiji Takabe, Minoru Fujita, Hiroshi Saiki, Hiroshi Harada
Faculty of Agriculture, Kyoto University
Keywords: Cryptomeria japonica, UV microscopy, autoradiography, 3H-glucose,
3H-phenylalanine

14

C-glucose,

1982-109
アカマツ圧縮アテ材の脱リグニン液中に溶出してくる多糖の性賃
東 順一*1、向吉俊一郎*1*2、越島哲夫*1*1
京都大学木材研究所、*2 神崎製紙株式会社
Characterization of polysaccharides dissolving out during the delignification of red pine compression wood
Junichi Azuma*1, Mukoyoshi Shunichiro*1*2, Tetsuo Koshijima*2*1
Wood Research Institute, Kyoto University, *2Kanzaki Paper Co. Ltd.
Keywords: Pinus densiflora, LCC, sodium chlorite, galactoglucomannan
1982-110
リグニンの酸化分解（V）酸素およびヒドロキシラジカルとリグニンの芳香核との反応
辰己憲司*1、寺島典二*2*1
公害資源研究所、*2 名古屋大学農学部
Oxidative degradation of lignin (V), Reactions of lignin aromatic nuclei with oxygen and hydroxyl radical
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: UV radiation, pH dependence, vanillic acid, protocatechuic acid, gallic acid
1982-111
求核性試薬添加ソーダ蒸解
大原誠資、飯塚堯介、R．Pant、中野準三
東京大学農学部
Soda pulping with addition of nucleophilic reagentsSeiji Ohara, Gyosuke Meshitsuka, R. Pant, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: soda pulping, nucleophilic reagent, methyl mercaptan, thiophenol
1982-112
酸素・アルカリ蒸解の蒸解要因。 Co-Salen 触媒活性に及ばす蒸解因子の影響137目黒貞利、今村博之
九州大学農学部
Cooking factors influencing oxygen-alkali pulping. -Factors influencing the catalytic activity of Co-salen
Sadatoshi Meguro, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: cobalt (II) bis(salicylidene)ethylenediamine, oxidation of guaiacol,
1982-113
クレゾール・水によるパルプ化法について
榊原 彰、技重有祐、武山浩武
北海道大学農学部
Pulping with cresol and water
Akira Sakakibara, Yusuke Edashige, Hirotake Takeyama
Faculty of Agriculture, Hokkaido University
Keywords: Picea Glehnii, organosolv pulping,
1982-114
オルガノソルブパルプ化に関する研究
佐野嘉拓、榊原 彰、笹谷宜志
北海道大学農学部
Studies on organosolv pulping
Yoshihiro Sano, Akira Sakakibara, Takashi Sasaya
Faculty of Agriculture,Hokkaido University
Keywords: Quercus crispula, Betula Tauschii, Picea Glehnii, Larix Kaempferi, Abies Mayriana,
phenol, cresol,
1982-115
有機溶媒とサルファイトによるパルプ化（I） スギ SCP 蒸解におけるイソプロピルアルコール添加の効果（その1）
文 星筆、坂井克己、今村博之
九州大学農学部
Pulping with organic solvents and sulfite (I), Effects of the addition of isopropyl alcohol on SCP cooking ofJapanese cedar
Sung-Phil Mun, Kokki Sakai, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: Cryptomeria japonica, neutral sulfite, monosulfite, bisulfite, isopropyl alcohol, Japanese cedar
1982-116
広葉樹（GL 材）CTMP の強度と繊維特性
久保隆昌、細川 純、小林 武、赤松 勲
四国工業技術試験所
Strength properties and fiber characteristics of hardwood CTMP
Government Industrial Research Institute, Shikoku
Takamasa Kubo, Jun Hosokawa, Takeshi Kobayashi, Isao Akamatsu
Keywords: giant leucaena, Leucaena leucocephala, TMP,
1982-117
リグニンおよび関連物質の熱分解（第 3 報）佐々木坤彪、荒木 廣、鈴木正人、長沢武夫
日本紙パルプ研究所
Pyrolysis of lignin and related materials (III)Nobutake Sasaki, Hiroshi Araki, Masato Suzuki, Takeo Nagasawa
Japan Pulp & Paper Research Institute, Inc.
138

Keywords:

Fagus crenata, thiolignin, pyrolysis, chlorinated lignin, TG, DSC

1982-118
特別講演、木材の細胞璧の構造と形成原田 浩
京都大学農学部
Invited lecture ; Structure and formation of wood cell wall
Hiroshi Harada
Faculty of Agriculture, Kyoto University
Keywords: vascular cambium, chemical composition, cell wall layers
1982-201
大気汚染地域で見られたスギ葉中のタンニン生合成阻害について
加藤輝隆*1、加須屋実*1、鏡森定信*1、河野昭一*2
富山医科薬科大学医学部、富山大学生物学科
Inhibition of tannin biosynthesis in the leaves of Japanese cedar in the air pollutied area
Terutaka Kato*1, Minoru Kasuya*1, Sadanobu Kagamimori*1, Shoichi Kawano*2*1
Faculty of Medicine, Toyama Medical and Pharmaceutical University, *2Department of Biology, Toyama
University
Keywords: Cryptomeria japonica, glucose content, shikimic acid
1982-202
リグニン存在下でのセルロース質の酵素分解（2）夜久富美子*1、田中龍太郎*1、村木永之介*1、田中文男*2、越島哲夫*2*1
大阪工業技術試験所、*2 京都大学木材研究所
Enzymatic hydrolysis of cellulosic substance in the presence of lignin (II)Fumiko Yaku*1, Ryutaro Tanaka*1, Einosuke Muraki*1, Fumio Tanaka*2, Tetsuo Koshijima*2*1
Government Industrial Research Institute, Osaka, *2Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, Shorea negrosensis, Pentacme contorta, vibration ball mill, MWL, LCC,
1982-203
爆砕木材の特性とその酵素糖化
棚橋光彦*1、樋口隆昌*1、高田信輔*2、花井四郎*3*1
京都大学木材研究所、*2 近畿大学農学部、*3 宝酒造株式会社
Characterization of steam-exploded wood and its enzymatic hydrolysis
Mitsuhiko Tanahashi, Takayoshi Higuchi, Shinsuke Takada, Shiro Hanai*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kinki University, *3Takara Shuzo Co.
Ltd.
Keywords: Betula Tauschii, Larix Kaempferi, SEM, TEM, pulping
1982-204
Fusarium 属菌の生産するリグニン関連芳香族化合物の分解に関与する酵素系について
岩原章二郎
香川大学農学部
On the enzymes produced by Fusarium species that participate in degradation of lignin-related aromaticcompounds
Shojiro Iwahara
Faculty of Agriculture, Kagawa University
Keywords: laccase, pinoresinol, syringaresinol, UV absorption spectroscopy
1982-205
Phanerochaete chrysosporium のピリジン補酵素代謝 —リグニン分解との関連性について
桑原正章、麻田恭彦、石田 豊、河上智栄美、赤池嘉彦
香川大学農学部
139

Metabolism of pyridine coenzymes in Phanerochaete chrysosporium, –In relation to lignin degradation
Masaaki Kuwahara, Yasuhiko Asada, Yutaka Ishida, Chiemi Kawakami, Yoshihiko Akaike
Faculty of Agriculture, Kagawa University
Keywords: Aspergillus sp., radiotracer, NAD, NADP
1982-206
Guaiacylglycerol−β-guaiacyl ether の分解に関与する酵素系について
沖 妙、新本美智枝、石川久雄
愛媛大学農学部
Enzymes involved in the degradation of guaiacylglycerol-β-guaiacyl ether
Tae Oki, Michie Shinmoto, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Pinus densiflora, Phanerochaete chrysosporium, Lentinus edodes, peroxidase, laccase
1982-207
木材腐朽菌によるリグニンモデル化合物の代謝について
榎 章郎*1、田中裕美*1、高橋旨象*2、布施五郎*1*1
近畿大学農学部、*1 京都大学木材研究所
Metabolism of lignin model compounds by wood rotting fungi
Akio Enoki*1, Hiromi Tanaka*1, Munezoh Takahashi*2, Goro Fuse*1*1
Faculty of Agriculture, Kinki University, *2Wood Research Institute, Kyoto University
Keywords: white rot fungi, brown rot fungi
1982-208
Phanerochaete chrysosporium による 5-carboxyprotocatechuic acid の分解
梅澤俊明、樋口隆昌
京都大学木材研究所
Degradation of 5-carboxyprotocatechuic acid by Phanerochaete chrysosporium
Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 5,5’-dehydrodivanillic acid, phenylcoumaran
1982-209
Phanerochaete chrysosporium によるシリンガレジノールの分解
釜谷保志、樋口隆昌
京都大学木材研究所
Degradation of syringaresinol by Phanerochaete chrysosporium
Yasushi Kamaya, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 1H-NMR, 13C-NMR,
1982-210
リグニンとリグニンモデル化合物の光増感剤及びヒドロキシルラジカルによる分解
久津木英俊*1*2、M. H. Gold*2*1
京都大学木材研究所、*2 オレゴン大学院センター
Degradation of lignin and lignin model compounds by photosensitizer and hydroxyl radical
Hidetoshi Kutsuki*1*2, Michael H. Gold*2*1*2
Wood Research Institute, Kyoto University, *2Oregon Graduate Center
Keywords: Phanerochaete chrysosporium, nonphenolic lignin model compounds, singlet oxygen, 14C-DHP
1982-211
カワラタケ生育時に分泌される酵素類について
諸星紀幸、中村 剛、村磯知採、原口隆英
東京農工大学農学部
140

Characterization of enzymes secreted during the growth of Coriolus versicolor
Noriyuki Morohoshi, Tuyoshi Nakamura, Chidori Muraiso, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: tyrosinase, laccase, cellulase, pectinase, protease, gel filtration
1982-212
カワラタケラッカーゼによるリグニンの変化（第 3 報）—精製ラッカ−ゼのリグニンに対する反応性—
割石博之、藤田佳代、諸星紀幸、原口隆英
東京農工大学農学部
Changes of lignin by the treatment with laccase from Coriolus versicolor (III), Reactivity of purified laccasewith lignin
Hiroyuki Wariishi, Kayo Fujita, Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Yezo spruce, Picea jezoensis, BNL, MWL, LCC, ESR
1982-213
白腐れ菌菌体内の酸素添加酵素について
田部眞哉、野中久美雄、原口隆英
東京農工大学農学部
Characterization of intracellular oxygenation enzyme of white rot fungi
Shinya Tabe, Kumio Nonaka, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Pycnoporus coccineus, Stereum frustulosum, catechol, protocatechuic acid, vanillic acid
1982-214
Lentinus edodes の広葉樹材への作用とそのクラフトパルプ化
赤松 勲、上嶋 洋、藤井利郎、小林 武
四国工業技術試験所
Treatment of hardwood with Lentinus edodes and its kraft pulping
Isao Akamatsu, Hiroshi Kamishima, Toshiro Fujii, Takeshi Kobayashi
Government Industrial Research Institute, Shikoku
Keywords: Quercus acutissima, Quercus serrata, X-ray diffraction, cellulose crystalinity, MWL
1982-215
Erwinia carotovora を用いた発酵精練によるコウゾのパルプ化
小林良生、松尾隆吉
四国工業技術試験所
Pulping of Kozo bast by retting with Ervinia carotovora
Yoshio Kobayashi, Ryukichi Matsuo
Government Industrial Research Institute, Shikoku
Keywords: Broussonetia kazinoki × B. papyrifera, retting, Erwinia carotovora, brightness
1982-216
パルプ廃液の新しい微生物処理法へのアプローチ
鮫島一彦、高村憲男
高知大学農学部
Approach to the new microbiological treatment of pulping effluent
Kazuhiko Sameshima, Norio Takamura
Faculty of Agriculture, Kochi University
Keywords: BOD, wood rotting fungi,
1982-217
特別講演、バイオマス特にリグニン経由化学製品開発の世界的動向
鈴木 明
141

野口研究所Invited lecture: World trend of research and development of chemicals from biomass and especially from lignin
Akira Suzuki
Noguchi Institute
Keywords: hydrocracking, ethanol production,142

第 28 回 （1983.10.7-8） 北海道大学農学部
1983-101
オートラジオグラフイーからみた細胞間層と二次壁の木化
高部圭司、藤田 稔、佐伯 浩、原田 浩
京都大学農学部
Lignification of middle lamella and secondary wall investigated by autoradiography
Keiji Takabe, Minoru Fujita, Hiroshi Saiki, Hiroshi Harada
Faculty of Agriculture, Kyoto University
Keywords: Cryptomeria japonica, UV microscopy, fluorescent microscopy, 3H-phenylalanine
1983-102
細胞壁形成、とくに木化の細胞学的検討
藤田 稔、高部圭司、佐伯 浩、原田 浩
京都大学農学部
Cytological studies on cell wall formation especially on lignification
Minoru Fujita, Keiji Takabe, Hiroshi Saiki, Hiroshi Harada
Faculty of Agriculture, Kyoto University
Keywords: Populus euramericana, Cryptomeria japonica, reaction wood, microautoradiography,
1983-103
オートラジオグラフイーからみたマツ属放射柔細胞壁の木化
山本幸一*1、深沢和三*2、石田茂雄*2*1
林業試験場、*2 北海道大学農学部
Studies on lignification of ray parenchyma wall of pine by microautoradiography
Koichi Yamamoto*1, Kazumi Fukazawa*2, Shigeo Ishida*2*1
Forestry and Forest Products Research Institute, *2Faculty of Agriculture Hokkaido University
Keywords: Pinus strobes, Pinus densiflora, Pinus banksiana, 3H-phenylalanine, 14C-glucose
1983-104
カラマツ 2 次師部の厚壁細胞の木化経過
今川一志、深沢和三、石田茂雄
北海道大学農学部
Lignification process of sclerenchyma cell of larch secondary phloem
Kazushi Imagawa, Kazumi Fukazawa, Shigeo Ishida
Faculty of Agriculture, Hokkaido University
Keywords: Larix leptolepis, screleid fiber, UV microscope
1983-105
紫外及び電子顕微鏡による細胞壁中のリグニン分布の観察
広居忠量、藤井智之
林業試験場
Observation of lignin distribution across cell wall by UV microscopy and electron microscopy
Tadakazu Hiroi, Tomoyuki Fujii
Forestry and Forest Products Research Institute
Keywords: Fagus crenata, guaiacyl lignin, syringyl lignin, electron microphotography,
microphotography
1983-106
広葉樹材複合細胞間層リグニンの性状について
飯塚堯介、中野準三
東京大学農学部
Characterization of lignin in compound middle lamella of hardwood
Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
143

UVKeywords:

Betula maximowiczii, nitrobenzene oxidation, Klason lignin, condensed structure

1983-107
ソルボリシスリグニン —低分子量フラクションについて—
佐野嘉拓、遠藤博之、榊原 彰
北海道大学農学部
Solvolysis lignin. -Characterization of low molecular weight fraction
Yoshihiro Sano, Hiroyuki Endo, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Quercus crispula, p-cresol, 1H-NMR, 13C-NMR,
1983-108
硫酸リグニンの化学構造
安田征市、寺島典二、浜中 篤
名古屋大学農学部
Chemical structures of sulfuric acid lignin
Seiichi Yasuda, Noritsugu Terashima, Atsushi Hamanaka.
Faculty of Agriculture, Nagoya University
Keywords: Pinus densiflora, carbohydrates, arylglycerol-β-aryl ether, 1H-NMR, nitrobenzene oxidation,
permanganate oxidation, condensation reaction
1983-109
トリメチルクロルシラン／ヨウ化ナトリウムによるリグニン中のエーテル結合の選択的開裂
近藤哲男、飯塚堯介、中野準三
東京大学農学部
Selective cleavage of ether linkage in lignin by trimethylchlorosilane/sodium iodide
Tetsuo Kondo, Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, MWL, guaiacylglycerol-βguaiacyl ether, gel filtration chromatography
1983-110
アルカリ蒸解時のリグニンの縮合反応について —特にコニフェリルアルコールの蒸解時の役割—
近藤隆一郎*1、J.F．McCarthy*2*1
九州大学農学部、*2 ワシントン大学
Condensation reactions of lignin during alkaline pulping. -Role of coniferyl alcohol during cooking
Ryuichiro Kondo*1, J. F. McCarthy*2*1
Faculty of Agriculture, Kyushu University, *2University of Washington
Keywords: western hemlock, Thuja heterophylla, soda cooking, soda AQ cooking, kraft cooking, gelfiltration chromatography
1983-111
リグニンの酸化分解（VI） —ヒドロキシラジカルとリグニンの芳香核との反応—
辰巳憲司*1、寺島典二*2*1
公害資源研究所, *2 名古屋大学農学部
Oxidative degradation of lignin (VI), —Reaction of aromatic ring in lignin with a hydroxyl radical
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: veratric acid, UV irradiation, gas chromatography, mass spectrometry
1983-112
分子軌道法によるリグニンの反応性の検討
飯山賢治
東京大学農学部
Studies on reactivity of lignin by molecular orbital method
144

Kenji Iiyama
Faculty of Agriculture, the University of Tokyo
Keywords: biphenyl, apocynol, cooking with nucleophilic additives
1983-113
リグニン吸着水の 1H 核磁気緩和
畠山兵衝*1、岩田ひろ*1、畠山立子*2*1
製品科学研究所、*2 繊維高分子材料研究所
Proton nuclear magnetic relaxation of adsorbed water in lignin
Hyoe Hatakeyama*1, Hiro Iwata*1, Tatsuko Hatakeyama*2*1
Industrial Products Research Institute, *2Research Institute for Polymers and Textiles
Keywords: Hyderia decuurens , dioxane lignin, DSC
1983-114
リグノスルホン酸塩の吸湿と粘弾性矢野彰一郎*1、Mikael Rigdahl*2，Petter Kolseth*2，Alf de Ruvo*2*1
製品科学研究所、*2STFI (Sweden)
Moisture adsorption and viscoelasticity of lignosulfonate
Shoichiro Yano*1, Mikael Rigdahl*2，Petter Kolseth*2，Alf de Ruvo*2*1
Industrial Products Research Institute, *2STFI (Sweden)
Keywords: Picea abies, adsorption isotherm
1983-115
特別講演、Biomass の加水分解工程
小林達吉
東京教育大学名誉教授
Invited lecture ; Hydrolysis process of biomass
Tatsukichi Kobayashi
Professor emeritus, Tokyo University of Education
1983-201
カワラタケ菌体外分泌蛋白の 2 次元電気泳動
諸星紀幸、割石博之、原口隆英
東京農工大学農学部
Two dimensional electrophoresis of the proteins secreted by Coriolus versicolor
Noriyuki Morohoshi, Hiroyuki Wariishi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agricultue and Technology
Keywords: laccase, cellulase, βglucosidase, xylanase, affinity chromatography
1983-202
Guaiacylglycerol-β-guaiacyl ether の生分解に関与する酵素系について
沖 妙、新本美智枝、石川久雄
愛媛大学農学部
Studies on the enzymes involved in the biodegradation of guaiacylglycerol-βguaiacyl ether
Tae Oki, Michie Shinmoto, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Coprinus aff ellisii, Phanerochaete chrysosporium, Coriolus versicolor,
Irpex lacteus, Schizophyllum commune
1983-203
Phanerochaete chrysosporium による β−O−4 及び β−1 型二量体の分解における 18O2 の取り込み
梅澤俊明*1、樋口隆昌*1、中坪文明*2*1
京都大学木材研究所、*2 京都大学農学部
Incorporation of 18O2 during the degradation of β-O-4 and β-1 type dimers by Phanerochaete chrysosporium
145

Toshiaki Umezawa*1, Takayoshi Higuchi*1, Fumiaki Nakatsubo*2*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kyoto University
Keywords: 1H-NMR, mass spectrometry
1983-204
カンバ材リグニンの生分解
寺沢 実*1、D. Tai*2、C. L. Chen*3、H-m. Chang*3、T. K. KirK*4*1
帯広畜産大学、*2 南京林産工業学院、*3 ノースカロライナ州立大学、*4USDA 林産物研究所
Biodegradation of birch lignin
Minoru Terasawa*1, D. Tai*2, C.L. Chen*3, H-m. Chang*3, T. K. Kirk*4*1
Obihiro University of Agriculture and Veterinary Medicine, *2Nanjin University of Forest Industry, *3North
Carolina State University, *4Forest Products Laboratory Madison
Keywords: Betula platyphylla, Phanerochaete chrysosporium, degradation products
1983-205
木材の酵素による加水分解 —無機塩存在下での蒸煮・爆砕処理の効果—
須藤賢一、石井 忠、志水一允、藤井智之、長沢定男
林業試験場
Enzymatic hydrolysis of wood. -Effects of steam-explosion under the presence of inorganic salts
Kenichi Sudo, Tadashi Ishii, Kazumasa Shimizu, Tomoyuki Fujii, Sadao Nagasawa
Forestry and Forest Products Research Institute
Keywords: Betula platyphylla, Fagus crenata, Aesculus turbinate, Larix Kaempferi, aluminium chloride,ammonium chloride,
1983-206
リグニン—糖間の物理および化学的結合について
Lam Thi Bach Tuyet、飯山賢治、中野準三
東京大学農学部
Studies on the physical and chemical associations between lignin and carbohydrate
Lam Thi Bach Tuyet, Kenji Iiyama, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: refiner mechanical pulp, carboxymethylation, gel filtration, 1H-NMR,
1983-207
へミセルロース・リグニン結合体に関する研究（その 10）—バガス Björkman LCC の性質—
加藤 厚、東 順一、越島哲夫
京都大学木材研究所
Studies on hemicellulose-lignin bond (X), Characterization of bagasse Björkman LCC
Atsushi Kato, Junichi Azuma, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Saccharum sp., ferulic acid, coumaric acid, gel filtration, 13C-NMR
1983-208
Klason Lignin に残存する炭水化物について
松本雄二、寺澤一雄、石津 敦、中野準三
東京大学農学部
Studies on the carbohydrate remaining in Klason lignin
Yuji Matsumoto, Kazuo Terasawa, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, Betula sp., ozone degradation,
1983-209
白色腐朽菌のポプラチップへの作用と同菌による部分分解材の TMP 化
赤松 勲、吉原一年、上嶋 洋、藤井利郎
146四国工業技術試験所
Treatment of poplar chips with white rot fungi and production of TMP from the treated chips
Isao Akamatsu, Kazutoshi Yoshihara, Hiroshi Kamishima, Toshiro Fujii
Government Industrial Research Institute, Shikoku
Keywords: Populus sp., defibration energy, pulp properties
1983-210
前加水分解処理（アスプルンド法）残渣パルプの性質
島田謹爾、高野 勲、宇佐見国典、長沢定男、須藤賢一、志水一允
林業試験場
Characterization of prehydrolysis (Asplund) pulp
Kinji Shimada, Isao Takano, Kuninori Usami, Sadao Nagasawa, Kenichi Sudo, Kazumasa Shimizu
Forestry and Forest Products Research Institute
Keywords: Betula Tauschii, Pinus densiflora, Fagus crenata, Larix Kaempferi, chlorine, chlorine dioxide,sodium hypochlorite, strength properties
1983-211
過酸化水素—アルカリ法（PA 法）による沖縄産ギンネムのパルプ化
金沢健治*1、御田昭雄*1、柏原 進*1、原 信治*2、浅見明彦*2*1
化学技術研究所、*2 東海パルプ株式会社
Peroxide-alkali pulping (PA process) of lead tree (Leucaena leucocephala)
Kenji Kanazawa*1, Akio Mita*1, Susumu Kashiwabara*1, Shinji Hara*2, Akihiko Asami*2*1
National Chemical Laboratory for Industry, *2Tokai pulp Co. Ltd.
Keywords: bleachability, EDTA, anthraquinone
1983-212
アルカリ酸素蒸解に関する研究（第 7 報）—稲わらパルプの酸化漂白—
戸坂圀夫、林 治助
北海道大学工学部
Studies on alkali-oxygen pulping (VII), -Oxidative bleaching of rice straw pulp—
Kunio Tosaka, Jisuke Hayashi
Faculty of Engineering, Hokkaido University
Keywords: Oryza sativa, ozone bleaching, alkaline hydrogen peroxide bleaching, brightness
1983-213
ネマガリタケのソルボリシスパルプ化
中村敏也、榊原 彰
北海道大学農学部
Solvolysis pulping of Sasa kurilensis
Toshiya Nakamura, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: cresol, brightness, biomass refinery
1983-214
高歩留 SP 廃液を利用した耐水性接着剤の製造
境 一男、佐藤 裕、成田 升、下田 優
王子建材工業株式会社
Preparation of waterproof adhesives from high yield sulfite pulp effluent
Kazuo Sakai, Hiroshi Sato, Masu Narita, Suguru Shimoda
Oji Kenzai Co. Ltd.
Keywords: phenol, lauan plywood, birch plywood, larch plywood, particleboard,
1983-215
カラマツ樹皮の水酸化ナトリウム抽出物を利用した接着剤の製造147

窪田 実、平田三郎、斉藤 勝、駒沢克己、青山政和
北海道立林産試験場
Preparation of adhesives from sodium hydroxide extracts of larch bark
Minoru Kubota, Saburo Hirata, Masaru Saito, Katsumi Komazawa, Masakazu Aoyama
Hokkaido Forest Products Research Institute
Keywords: Larix Kaempferi, polyphenol,
1983-216
紙・パルプ廃液からの活性炭の製造
里中聖一、磯部泰佐、香山 彊
北海道大学農学部
Production of activated carbon from pulp and paper mill effluent
Seiichi Satonaka, Taisuke Isobe, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords: Picea Glehnii, Betula Tauschii, Quercus crispula,148

第 29 回 （1984.10.15-16） 東京大学農学部
1984-101
広葉樹複合細胞間層リグニンの性状について（第 2 報）
飯塚堯介、中野準三
東京大学農学部
Characterization of lignin in compound middle lamella of hardwood (II)Gyosuke Meshitsuka, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Betula maximowicziana, BetulaTauschii, fiber, soft xylem, permanganate oxidation,
nitrobenzene oxidation
1984-102
針葉樹プロトリグニンの芳香核縮合度について
船岡正光、阿部 勲
三重大学農学部
Degree of condensation of aromatic rings in softwood protolignin
Masamitsu Funaoka, Isao Abe
Faculty of Agriculture, Mie University
Keywords: Chamaecyparis obtuse, nuclear exchange method, condensation degree
1984-103
スギ穿孔牲害虫被害材リグニンの化学的特性
島田謹爾、西田篤実、高野 勲、宇佐美国典
林業試験場
Chemical characteristics of lignin in the wood damaged by boring insect
Kinji Shimada, Atsumi Nishida, Isao Takano, Kuninori Usami
Forestry and Forest Products Research Institute
Keywords: Anaglyptus subfasciatus, Resseliella odai, Epi-notia granitalis, permanganate oxidation
1984-104
硫酸リグニンの化学構造 — 1,2−ジアリール-1,3−プロパンジオールと硫酸との反応
安田征市，足立久美子、寺島典二、太田勝人
名古屋大学農学部
Chemical structures of sulfuric acid lignin. —Reactions of 1,2-diaryl- 1,3-propanediol with sulfuric acid
Seiichi Yasuda, Kumiko Adachi, Noritsugu Terashima, Katsuhito Oota
Faculty of Agriculture, Nagoya University
Keywords: pinoresinol,
1984-105
リグニン・ヘミセルロース結合体の簡便な調製法とその構造
東 順一*1、渡辺隆司*1*2、越島哲夫*1*1
京都大学木材研究所、*2 山陽国策パルプ株式会社
Simple preparation of lignin hemicellulose complex and its chemical structure
Junichi Azuma*1, Takashi Watanabe*1*2, Tetsuo Koshijima*1*1
Wood Research Institute, Kyoto University, *2Sanyo Kokusaku Pulp Co. Ltd.
Keywords: Pinus densiflora, Björkman LCC, ion exchange chromatography, 13C-NMR
1984-106
クラフトパルプにおけるリグニンと炭水化物の結合
磯貝 明、石津 敦、中野準三
東京大学農学部
Linkages between lignin and carbohydrate in kraft pulp
Akira Isogai, Atsushi Ishizu, Junzo Nakano
149

Faculty of Agriculture, the University of Tokyo
Keywords: gel permeation chromatography, lignin cellulose linkage, lignin hemicellulose linkage
1984-107
リグニンの酸化分解（VII）ヒドロキシラジカルによるリグニンの分解
辰巳憲司*1、寺島典二*2*1
公害資源研究所, *2 名古屋大学農学部
Oxidative degradation of lignin. VII. Degradation of lignin with a hydroxyl radical
Kenji Tatsumi*1, Noritsugu Terashima*2*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Nagoya University
Keywords: aromatic ring, UV irradiation, lignin model compounds, mass spectrometry
1984-108
好アルカリ性細菌によるリグニンモデル化合物の分解
川上日出国、近藤規子
名古屋大学農学部
Degradation of lignin model compounds by alkalophilic bacteria
Hidekuni Kawakami, Noriko Kondo
Faculty of Agriculture, Nagoya University
Keywords: -O-4 dimer, biphenyl compounds, mass spectrometry, Pseudomonas ovalis
1984-109
菌体外酵素による Guaiacylglycerol-β-guaiacyl ether の生分解
沖 妙、新本美智枝、石川久雄
愛媛大学農学部
Biodegradation of guaiacylglycerol-β-guaiacyl ether by extracellular enzyme
Tae Oki, Michie Shinmoto, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Coriolus versicolor, Irpex lacteus, Phanerochaete chrysosporium, Coprinus off ellisii, dioxane
lignin1984-110
カワラタケ菌体外酵素によるリグニンモデル化合物の分解
諸星紀幸、原口隆英
東京農工大学農学部
Degradation of lignin model compounds by the extracellular enzyme of Coriolus versicolor
Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Coriolus versicolor, laccase Ⅲ, syringylglycerol-β-(2,6-dimethoxyphenyl) ether
1984-111
α-O-4 型及び α 位にケトンを有する β-O-4 型リグノールの Fusarium solani M-13-1 による分解
片山健至*1、山田康博*1、十河村男*1、樋口隆昌*2*1
香川大学農学部、*2 京都大学木材研究所
Degradation of an α-O-4 type lignol and β-O-4 type lignol with α-ketone by Fusarium solani M-13-1.
Takeshi Katayama*1, Yasuhiro Yamada*1, Murao Sogo*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: dilignols, non-cyclic benzyl ether, trilignols, mass spectrometry, 13C-NMR,
1984-112
4-エトキシ-3-メトキシフエニルグリセロール-β-シリンガアルデヒドエーテルのカワラタケによる分解
河合真吾、梅沢俊明、樋口隆昌
京都大学木材研究所
Degradation of 4-ethoxy-3-methoxyphenylglycerol-β-syringaldehyde ether by Coriolus versicolor
150

Shingo Kawai, Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: biodegradation, lignin substructure model compound, Phanerochaete chrysosporium,
Pseudomonas putida, TLC, NMR, GC-MS,
1984-113
Phanerochaete chrysosporium による β -4 結合の開裂とアリールグリセロールの生成機構について
梅澤俊明、樋口隆昌
京都大学木材研究所
Cleavage of β -4 bond and formation of arylglycerol by Phanerochaete chrysosporium
Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 18O tracer, TLC, GC-MS
1984-114
リグニン分解へのバイオミメティックアプローチ(I) —リグニンモデル化合物の分解反応に及ぼすヘミンの触
媒効果
島田幹夫*1、波部 豪*1、樋口隆昌*1、岡本 忠*2*1
京都大学木材研究所、*2 京大化学研究所
Biomimetic approach to the degradation of lignin (I), Catalytic effect of hemin on the degradation of lignin
model compounds
Mikio Shimada*1, Tsuyoshi Habe*1, Takayoshi Higuchi*1, Tadashi Okamoto*2*1
Wood Research Institute, Kyoto University, *2Institute for Chemical Research, Kyoto University
Keywords: iron porphyrin, cytochrome, peroxidase, catalase
1984-115
リグニン分解へのバイオミメティックアプローチ（II） —リグニン分解酵素及び酵素モデル触媒による重水素
化リグニンモデル化合物の分解
波部 豪、島田幹夫、樋口隆昌
京都大学木材研究所
Biomimetic approach to the degradation of lignin (II), -Degradation of deuterated lignin model compounds bylignin degrading enzyme and enzyme model catalyst
Tsuyoshi Habe, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phanerochaete chrysosporium, hemin
1984-116
特別講演、リグニン化学構造研究の回顧榊原 彰
北海道大学農学部
Invited lecture; Retrospection on the research of lignin chemical structure
Akira Sakakibara
Faculty of Agriculture, Hokkaido University
1984-201
爆砕処理による木質系物質の利用
志水一允*1、須藤賢一*1、長沢定男*1、島田規男*2、菅原一晃*3*1
林業試験場、*2 東和化成、*3 三菱重工
Utilization of woody biomass by steam explosion
Kazumasa Shimizu*1, Kenichi Sudo*1, Sadao Nagasawa*1, *Norio Shimada*2, Kazuaki Sugawara*3*1
Forestry and Forest Products Research Institute, *2Towa-Kasei Co. Ltd., *3Mitsubishi Heavy Industries Co.
Ltd.
Keywords: Betula Tauschii, Fagus crenata, Quercus serrata, Castanopsis cuspidate, GPC
151

1984-202
A Solid state CP/MAS NMR-study of a product synthesized from lignin and sulphur
K. Levon, B. Hortling, J.J. Lindberg
ヘルシンキ大学 University of Helsinki
Keywords: sulphur lignin, poly(phenylene)sulphides, lignosulphonate, solution NMR
1984-203
リグニン関連型構造を有するコレステリルエステルの合成とその液晶牲
春日和行、畠山兵衛
製品科学研究所
Synthesis of cholesteryl ester with lignin-related structure and its characteristics as liquid crystal
Kazuyuki Kasuga, Hyoe Hatakeyama
Industrial Products Research Institute
Keywords: 4-n-alkoxybenzoic acid derivative, polarization microscope, DSC
1984-204
水-リグノスルホン酸 Na 塩混合系の DSC 及び 23Na−NMR
畠山兵衛*1、広瀬重雄*1、中村邦雄*2、畠山立子*3
製品科学研究所、神奈川県工業試験所、繊維高分子材料研究所
DSC and 23Na−NMR studies of the water-sodium lignosulphonate system
Hyoe Hatakeyama*1, Shigeo Hirose*1, Kunio Nakamura*2, Tatsuko Hatakeyama*3*1
Industrial Products Research Institute, *2Kanagawa Industrial Technology Center, *3Institute for Textiles andPolymers
Keywords: non-freezing water, freezing bound water,
1984-205
マニラ麻の Bio−RMP 化について
赤松 勲、上島 洋、藤井利郎、吉原一年
四国工業技術試験所
Preparation of bio-refiner mechanical pulp from Manila hemp
Susumu Akamatsu, Hiroshi Kamishima, Toshiro Fujii, Kazutoshi Yoshihara
Government Industrial Research Institute, Shikoku
Keywords: Bio-RMP, Manila hemp, white rot fungi, Coriolus hirstus
1984-206
ソルボリシスパルプの組織化学的研究
枝重有祐、榊原 彰
北海道大学農学部
Histochemical study of solvolysis pulp
Yusuke Edashige, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: beech, Fagus crenata, sapwood, heartwood, UV microscopy
1984-207
加溶媒分解におけるヘミセルロースの挙動
小沢修二、武山浩武、榊原 彰
北海道大学農学部
Behaviors of hemicellulose during solvolysis
Shuji Ozawa, Hirotake Takeyama, Akira Sakakibara
Faculty of Agriculture, Hokkaido University
Keywords: Betula Tauschii, cresol, GPC, 1H-NMR, 13C-NMR, MS
1984-208
有機溶媒と亜硫酸塩による脱リグニン（III）イソプロピルアルコール—亜硫酸塩セミケミカルパルプ化におけ152

る樹種特性
文 星筆、近藤隆一郎、坂井克己、今村博之
九州大学農学部
Delignification with organic solvents and bisulfite (III), Characteristics of wood species on semichemical
pulping with isopropyl alcohol and bisulfite
Sung-Phil Mung, Ryuichiro Kondo, Kokki Sakai, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: softwood, hardwood, tropical wood,
1984-209
アルカリ蒸解における針葉樹型および広葉樹型リグニンの反応性の差異
近藤隆一郎、堤 祐司、野口浩司、今村博之
九州大学農学部
Differences in reactivity between softwood and hardwood lignins during alkaline pulping
Ryuichiro Kondo, Yuji Tsutsumi, Koji Noguchi, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: kinetics, guaiacylglycerol-βguaiacyl ether, syringylglycerol-βsyringyl ether, βaryl ether
cleavage,
1984-210
Modified Kraft Pulplng. A way to decrease lignin content and improve pulp quality
Peter Sandström
STFI, Swedish Pulp and Paper Research Institute
Keywords: initial phase, bulk delignification, final phase, effective alkali
1984-211
酸素・アルカリ蒸解の蒸解要因（10）コバルト・アミノアルコール錯体の脱リグニン促進効果
目黒貞利、今村博之
九州大学農学部
Factors influencing oxygen-alkali cooking (X), Delignification enhancement by the addition of cobalt-amino
alcohol complex
Sadatoshi Meguro, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: Betula Tauschii, Co-salen, Co-triethanolamine complex,
1984-212
GP リグニンのニトロベンゼン酸化について
平島英則*1、住本昌之*2*1
片山化学工業株式会社、*2 九州大学農学部
Nitrobenzene oxidation of GP lignin
Hidenori Hirashima*1, *Masashi Sumimoto*２*1
Katayama Chemical Industries Co. Ltd, *２Faculty of Agriculture, Kyushu University
Keywords: Pinus densiflora, bleaching, brightness
1984-213
脱リグニン反応に及ぼす超音波照射の影響（第 2 報）超音波照射下におけるリグニンの挙動譚 国民、安田征市、寺島典二
名古屋大学農学部
Effect of ultrasonic irradiation on delignification reaction (II), Behavior of lignin during delignification underultrasonic irradiation
Guo-Min Tan, Seiichi Yasuda, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: Pinus densiflora, MWL, guaiacylglycerol-βguaiacyl ether, calcium hypochlorite
153

1984-214
バガスの UPAP の漂白の無塩素化について
御田昭雄、柏原 進
化学技術研究所
Nonchlorine bleaching of UPAP from bagasse
Akio Mita, Susumu Kashiwabara
National Chemical Laboratory for Industry
Keywords: AQ, AP, brightness
1984-215
晒排液中の突然変異原性に関する研究（第 1 報）各種の親核試薬による突然変異原性の解毒機構
橘 燦郎*1、J．Santodonato*2、C. W. Dence*3*1
九州大学農学部、*2 シラキユース大学、*3 ニューヨーク州立大学
Studies on the mutagenicity of bleach effluent (I), Mechanism of the detoxication of mutagenicity by
nucleophilic reagents
Sanro Tachibana*1, J. Santodonato*2, C. W. Dence*3*1
Faculty of Agriculture, Kyushu University, *2University of Syracuse, *3State University of New York
Keywords: Pinus virginiana, Pinus taeda, 2-chloropropenal, chloroacetone, chloro-o-benzoquinone,
1984-216
招待講演、
Soda-AQ／oxygen pulping process as an alternative to kraft process for production of bleached pulp fromsoftwood
Y. C. Tsai, N. H. Shin, H.−m. Chang, J. S. Gratzl
ノースカロライナ州立大学
Invited lecture;
Y. C. Tsai, N. H. Shin, H.-m. Chang, J. S. Gratzl
North Carolina State University
Keywords: viscosity, brightness,154

第 30 回 （1985.11.6-7） 高知会館
1985-101
スギ細胞壁の木化とペルオキシダーゼ活性の分布
高部圭司、原田 浩
京都大学農学部
Lignification and distribution of peroxidase activity in Japanese cedar cell wall
Keiji Takabe, Hiroshi Harada
Faculty of Agriculture, Kyoto University
Keywords: Cryptomeria japonica, osmium black, electron micrograph, lignin skeleton,
1985-102
カラマツ師部の厚壁細胞の木化（予報）今川一志、深沢和三
北海道大学農学部
Lignification of fiber sclereid in the phloem of larch (Preliminary report)
Kazushi Imagawa, Kazumi Fukazawa
Faculty of Agriculture, Hokkaido University
Keywords: Larix leptolepis, UV micrograph, lignin distribution, differentiation
1985-103
広葉樹リグニン中のグアヤシルおよびシリンギル構造の選択的標識
寺島典二*1、福島和彦*1、高部圭司*2
名古屋大学農学部、京都大学農学部
Selective radio-labeling of guaiacyl and syringyl structures in hardwood lignin
Noritsugu Terashima*1, Kazuhiko Fukushima*1, Keiji Takabe*2*1
Faculty of Agriculture, Nagoya University, *2Faculty of Agriculture, Kyoto University
Keywords: magnolia, Magnolia kobus, oxford poplar, Populus Maximowiczii X Populus belorinensis,
autoradiography, guaiacyl unit, syringyl unit, 3H-coniferin, 3H-syringin
1985-104
リグニンモデル化合物の合成とそのニトロベンゼン酸化について
季 典艶、橘 燦郎、住本昌之
九州大学農学部
Synthesis of lignin model compounds and their nitrobenzene oxidation
Dian Yan Lee, Sanro Tachibana, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Keywords: guaiacylglycerol-β-coniferyl ether, guaiacylglycerol-β-guaiacyl ether, nitrobenzene oxidation,
1
H-NMR, mass spectrometry
1985-105
硫酸リグニンの化学構造 —硫酸溶液中におけるシリンギルアルコールの反応とグアヤシルおよびシリンギ
ル核の反応性安田征市、太田勝人
名古屋大学農学部
Chemical structures of sulfuric acid lignin. —Reactions of syringyl alcohol and reactivity of guaiacyl andsyringyl nucleus in sulfuric acid
Seiichi Yasuda, Katsuhito Oota
Faculty of Agriculture, Nagoya University
Keywords: condensation, hardwood lignin, guaiacyl nucleus, syringyl nucleus, 13C-NMR
1985-106
リグニン・ヘミセルロース結合体のマイクロ波加熱
東 順一、土井美紀、越島哲夫
155京都大学木材研究所
Microwave heating of lignin hemicellulose complex
Junichi Azuma, Miki Doi, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, MWL. LCC, furfural, sugars, 13C-NMR, UV spectroscopy
1985-107
アルカリ蒸解において安定な LCC 結合について
種田英孝*1、細谷修二*2、中野準三*1*1
東京大学農学部、*2 林業試験場
LCC bond stable during alkaline cooking
Hidetaka Taneda*1, Shuji Hosoya*2, Junzo Nakano*1*1
Faculty of Agriculture, the University of Tokyo, *2Forestry and Forest Products Research Institute
Keywords: guaiacylglycerol-α-methylglucoside-β-guaiacyl ether, HPLC, 13C-NMR,
1985-108
アルカリ性処理におけるシリンギルグリセロール-β-シリンギルエーテル型モデル化合物の反応生成物について
堤 祐司、近藤隆一郎、今村博之
九州大学農学部
Reaction products from syringylglycerol-β-syringyl ether type model compounds on alkaline treatment
Yuji Tsutsumi, Ryuichiro Kondo, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: soda cooking, kraft cooking, soda-AQ cooking, HPLC,
1985-109β-O-4 型結合開裂の新反応
竹内寿一、坂井克己、文 星筆、今村博之
九州大学農学部
A new reaction for cleavage of β -4 type bonds
Jyuichi Takeuchi, Kokki Sakai, Sung-Phil Mung, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: methanol, ethanol, isopropanol, t-butyl alcohol, magnesium sulfite, lignin
1985-110
有機溶媒と亜硫酸塩による脱リグニン（V） 低分子フェノール類について
文 星筆、坂井克己、今村博之
九州大学農学部
Delignification with organic solvents and sulfite (V), On the low molecular weight phenols
Sung-Phil Mung, Kokki Sakai, Hiroyuki Imamura
Keywords: Cryptomeria japonica, magnesium sulfite, phenols, isopropyl alcohol,
1985-111
フェニルクマラン型構造のオゾン分解について
羽生直人、松本雄二、中野準三
東京大学農学部
Ozonolysis of phenylcoumaran type structure
Naoto Habu, Yuji Matsumoto, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: dicarboxylic acids, GLC, GC-MS, 1H-NMR
1985-112
ヨウ素化トリメチルシランによるリグニン・エーテル結合の選択的開裂について
飯塚堯介、近藤哲男、中野準三
156東京大学農学部
Selective cleavage of ether linkage in lignin by trimethylsilyliodide
Gyosuke Meshitsuka, Tetsuo Kondo, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Betula maximowicziana, MWL, guaiacylglycerol–β-guaiacyl ether, 1H-NMR
1985-113
蒸煮処理材酵素糖化残渣リグニンの性状について
須藤賢一、志水一允、島田謹爾、桜井孝一、藤井智之
林業試験場
Characterization of residual lignin after steaming and enzymatic hydrolysis
Kenichi Sudo, Kazumasa Shimizu, Kinji Shimada, Koichi Sakurai, Tomoyuki Fujii
Forestry and Forest Products Research Institute
Keywords: Betula platyphylla, nitrobenzene oxidation, permanganate oxidation,
1985-114
Guaiacylglycerol−β−guaiacyl ether と lignin 生分解に関与する酵素について
沖 妙、石川久雄
愛媛大学農学部
Enzymes involved in the biodegradation of guaiacylglycerol−β−guaiacyl ether and lignin
Tae Oki, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Ketwords:
Phanerochaete chrisosporium, Coprinus aff ellisii, UV spectroscopy, GPC
1985-115
リグニン分解へのバイオミメティックアプローチ（IV) —鉄・ポルフイリン錯体と一電子酸化剤によるリグニン関
連化合物の分解機構
島田幹夫*1、河波好宏*2、梅澤俊明*1、棚橋光彦*1、樋口隆昌*1、岡本 忠*3*1
京都大学木材研究所、*2 近畿大学農学部、*3 京都大学化学研究所
Biomimetic approach to the biodegrdation of lignin (IV), -Degradation mechanism of lignin related compounds
by ferriporphyrin and one electron oxidant
Mikio Shimada*1, Yoshihiro Kawanami*2, Toshiaki Umezawa*1, Mitsuhiko Tanahashi*1, Takayoshi Higuchi*1,
Tadashi Okamoto*3*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kinki University, *3Institute for Chemical
Research, Kyoto University
Keywords: active oxygen species, phenylcoumaran, heme-enzyme, t-buthylhydroperoxide, ceric
ammonium nitrate
1985-116
カワラタケ菌体外酵素によるリグニンモデル化合物の分解
諸星紀幸、中村雅哉、原口隆英
東京農工大学農学部
Degradation of lignin model compounds by extracellular enzyme of Coriolus versicolor
Noriyuki Morohoshi, Masaya Nakamura, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: laccase Ⅲ, guaiacylglycerol−β−guaiacyl ether, guaiacylglycerol−β−syringyl ether
1985-117
カワラタケラッカーゼによる β-1 型リグニンモデル化合物の分解
河合真吾*1、梅澤俊明*1、島田幹夫*1、樋口隆昌*1、小池一雄*2、西田友昭*2、諸星紀幸*3、原口隆英*3*1
京都大学木材研究所、*2 王子製紙株式会社中央研究所、*3 東京農工大学農学部
Degradation of  -1 type lignin model compounds by laccase of Coriolus versicolor
Shingo Kawai*1, Toshiaki Umezawa*1, Mikio Shimada*1 Takayoshi Higuchi*1, Kazuo Koike*2, Tomoaki
Nishida*2, Noriyuki Morohoshi*3, Takafusa Haraguchi*3
157

*1

Wood Research Institute, Kyoto University, *2Oji Paper Co. Ltd., *3 Faculty of Agriculture, Tokyo Universityof Agriculture and Technology.
Keywords: biodegradation, lignin substructure model compound, stable isotope tracer, 18O2, mass
spectrometry, 1,2-disyringylpropane-1,3-diol
1985-118
特別講演、酵母細胞壁溶解酵素とその利用
高知大学農学部
長崎 亀
Invited lecture ; Enzymes involved in the dissolution of yeast cell wall and its utilization
Susumu Nagasaki
Faculty of Agriculture, Kochi University
Keywords: β-1,3 glucanase,1985-201
Phanerochaete chrysosporium による β-O-4 二量体の分解における -アリール基の転位とCα−Cβ 開裂
梅澤俊明、樋口隆昌
京都大学木材研究所
Rearrangement of β-aryl group and Cα−Cβcleavage in the degradation of β-O-4 dimer by Phanerochaetechrysosporium
Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 2H, 13C, 18O, stable isotope tracer method, 1H-NMR, mass spectrometry
1985-202
シユードモナス属細菌 TMY1009 株の変異株による β-エーテル型モデル化合物の分解と中間代謝物の生成
安部修一、鮫島正浩、佐分義正、善本知孝
東京大学農学部
Degradation of β-O-4 type lignin model compounds and formation of intermediate metabolites by the mutant ofPseudomonas TMY1009
Shuichi Abe, Masahiro Samejima, Yoshimasa Saburi, Tomotaka Yoshimoto
Faculty of Agriculture, the University of Tokyo
Keywords: β-O-4, TLC, UV spectroscopy
1985-203
好アルカリ性細菌によるリグニンモデル化合物及びリグニンの分解
川上日出国、青井理恵、丹羽 淳
名古屋大学農学部
Degradation of lignin model compounds and lignin by alkalophilic bacteria
Hidekuni Kawakami, Rie Aoi, Makoto Niwa
Faculty of Agriculture, Nagoya University
Keywords: diarylpropane
diol,
beech,
Fagus
crenata,
1-guaiacyl-2-syringylpropane GPC

1,2-guaiacylpropane-1,3-diol,

1985-204
白色腐朽菌 Phanerochaete chrysosporium の生分解によって生成した脱脂シラカンバチップ中の低分子成分
寺沢 実*1、香山 彊*1、C.L. Chen*2，D.-S. Tai*3
北海道大学農学部、ノースカロライナ州立大学、南京林学院
Low molecular weight compounds formed in the degradation of extractive-free birch tips by a white rot fungus
Phanerochaete chrysosporium
Minoru Terasawa*1, Tsutomu Kayama*1 C.L. Chen*2, D.-S. Tai*3*1
Faculty of Agriculture, Hokkaido University, *2North Carolina State University, *3Nanjin Forestry University
Keywords: Betula platyphylla, acetophenone derivatives, ligninase158

1985-205
ミツマタ靱皮の酵素パルプ化過程におけるリグニン及びヘミセルロースの溶出挙動
田辺寛之、小林良生
四国工業技術試験所
Dissolution behavior of lignin and hemicellulose during enzymatic pulping of mitsumata (oriental paperbush)bast
Hiroyuki Tanabe, Yoshinari Kobayashi
Government Industrial Research Institute, Shikoku
Keywords: Edgeworthia chrysantha, carbohydrate composition
1985-206
菌処理マニラ麻の H2O2 添加 TMP 化
赤松 勲、上嶋 洋、吉原一年
四国工業技術試験所
Preparation of thermomechanical pulp with addition of hydrogen peroxide from fungi treated Manila hemp
Isao Akamatsu, Hiroshi Kamishima, Kazutoshi Yoshihara
Government Industrial Research Institute, Shikoku
Keywords: Coriolus hirtus, Klason lignin, holocellulose, pulp yield, pulp properties
1985-207
GP リグニン中のコニフェリルアルデヒド構造の挙動について
平嶋英則、住本昌之
九州大学農学部
Behaviors of coniferyl aldehyde structure in GP lignin
Hidenori Hirashima, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Keywords: red pine, Pinus densiflora, H2O2, NaBH4
1985-208
リグノセルロースの HF 糖化 —HF リグニンの構造
広居忠量、石井 忠
林業試験場
Saccharification of lignocellulose by HF, -Structure of HF lignin
Tadakazu Hiroi, Tadashi Ishii
Forestry and Forest Products Research Institute
Keywords: red pine, Pinus densiflora, white birch, Betula platyphylla, 13C-NMR, IR spectroscopy,
permanganate oxidation
1985-209
広葉樹材蒸煮処理効果の樹種による差
山口 彰、 志水一允、桜井孝一、藤井智之
林業試験場
Differences in the effectiveness of steaming for saccharification among wood species
Akira Yamaguchi, Kazumasa Shimizu, Koichi Sakurai, Tomoyuki Fujii
Forestry and Forest Products Research Institute
Keywords: enzymatic susceptibility, nitrobenzene oxidtion, S/V ratio, sugar composition
1985-210
リグニンの繊維化について
須藤賢一、志水一允
林業試験場
Preparation of fiber from lignin
Kenichi Sudo, Kazumasa Shimizu
Forestry and Forest Products Research Institute159

Keywords:

carbon fiber, white birch, Betula platyphylla, steaming, methanol extraction

1985-211
The Effect of Modified Lignosulphonate on Beating
Kalle Levon, Gyosuke Meshitsuka and Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: aminated lignosulphonate, mannich reaction, beating rate, freeness,
1985-212
リグニンの水素化分解 —反応温度および時間の検討—
小山 実、金沢健治、山田谷正子、杉本義一
化学技術研究所
Hydrogenolysis of lignin. -Investigation of reaction time and temperature
Makoto Koyama, Kenji Kanazawa, Masako Yamadaya, Giichi Sugimoto
National Chemical Laboratory for Industry
Keywords: thiolignin, cresol lignin, molecular weight distribution, monophenols,
1985-213
無機吸着剤に濃縮したバイオマスの熱分解
猪狩俶将*1、横山正一郎*1、井上晴彦*2*1
化学技術研究所, *2 クニミネ工業株式会社
Pyrolysis of biomass adsorbed on inorganic adsorbents
Yoshimasa Ikari*1, Shoichiro Yokoyama*1, * Haruhiko Inoue*2*1
National Chemical Laboratory for Industry, *2Kunimine Industries Co. Ltd.
Keywords: gasification, methanol synthesis, recovery of adsorbent
1985-214
ソルボリシスパルプ化による木材の脱リグニン —パルプ化条件とリグニンの性質
佐野 嘉拓、笹谷 宜志
北海道大学農学部
Delignification of wood by solvolysis pulping, -Pulping conditions and the properties of lignin
Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Keywords: beech, Fagus crenata, white birch, Betula platyphylla, cresol, solvolysis lignin
1985-215
ソルボリシスパルプ化による木材の脱リグニン —パルプ残存リグニン
枝重有祐、佐野嘉拓、笹谷宜志
北海道大学農学部
Delignification of wood by solvolysis pulping, -Residual lignin in pulp
Yusuke Edashige, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Keywords: beech, Fagus crenata, cresol, gel filtration, MWL, nitrobenzene oxidation, 1H-NMR
1985-216
クレゾールを含むヘミセルロース水溶液の精製
西山昌史、細川 純、上嶋 洋
四国工業技術試験所
Removal of cresol from aqueous hemicellulose and cresol solution
Masashi Nishiyama, Jun Hosokawa, Hiroshi Kamishima
Government Industrial Research Institute, Shikoku
Keywords: beech, Fagus crenata, solvolysis pulping, cresol, hemicellulose
1985-217
古代紙の打紙について160

大川昭典*1、増田勝彦*2*1
高知県紙業試験場、*2 東京国立文化財研究所
Beating of ancient paper
Akinori Ohkawa*1, Katsuhiko Masuda*2*1
Kochi Prefectural Pulp and Paper Experimental Station, *2National Research Institute for Cultural Properties,
Tokyo
Keywords: ancient paper, beating, breaking length
1985-218
特別講演、リグニン研究の回顧
中野準三
東京大学農学部
Invited lecture; A review of my lignin researchJunzo Nakano
Faculty of Agriculture, the University of Tokyo

161

第 31 回 （1986.10.21-22） 京大会館
1986-101
トドマツ圧縮あて材仮道管の木化
高部圭司、深沢和三
北海道大学農学部
Lignification of the tracheid of todomatsu compression wood
Keiji Takabe, Kazumi Fukazawa
Faculty of Agriculture, Hokkaido University
Keywords: Abies Mayriana, UV microscope, electron microscope, peroxidase activity
1986-102
カラマツ樹皮のフアイバースクレレイドの機械的単離とその化学成分
竹田昌文、寺沢 実、香山 彊
北海道大学農学部
Mechanical isolation and chemical components of Japanese larch fiber sclereid
Masafumi Takeda, Minoru Terasawa, Tsutomu Kayama
Faculty of Agriculture, Hokkaido University
Keywords: UV microscope, thioacidolysis, MWL,
1986-103
広葉樹新生組織中のリグニンの性状（II）
厳 泰振、飯塚堯介、石津 敦、中野準三
東京大学農学部
Characterization of lignin in differentiating xylem of hardwood (II)Tae Jin Eom, Gyosuke Meshitsuka, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: Betula maximowicziana, MWL, LCC, 1H-NMR, nitrobenzene oxidation
1986-104
アカマツリグニン・糖結合体の糖鎖とリグニンの結合位置について
渡辺隆司、海津澄子、越島哲夫
京都大学木材研究所
Bonding position between carbohydrate and lignin in red pine LCC
Takashi Watanabe, Sumiko Kaizu, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, DDQ oxidation, cellulase,
1986-105
ブナのリグニン・ヘミセルロース結合体におけるリグニンと糖の結合様式について
東 順一*1、越島哲夫*2*1
京都大学農学部、*2 京都大学木材研究所
Linkages between lignin and carbohydrate in beech lignin carbohydrate complex
Junichi Azuma*1, Tetsuo Koshijima*2*1
Faculty of Agriculture, Kyoto University, *2Wood Research Institute, Kyoto University
Keywords: Fagus crenata, DDQ oxidation, 13C-NMR,
1986-106
木材腐朽菌によるリグニンモデル配糖体の生成について
近藤隆一郎、今村博之
九州大学農学部
Formation of glycoside of lignin model compounds by wood rotting fungi
Ryuichiro Kondo, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
162

Keywords:

Polyporus versicolor, Tyromyces palustris，glucosidase, laccase

1986-107
好アルカリ性細菌による水溶性リグニンの生成
川上日出国、丹羽 淳
名古屋大学農学部
Formation of water-soluble lignin by alkalophilic bacteria
Hidekuni Kawakami, Makoto Niwa
Faculty of Agriculture, Nagoya University
Keywords: lignin degradation, wheat, Hordeum vulgare，poplar，Populus sp.,
1986-108
白色腐朽菌マイタケによる木材からの選択的脱リグニン
広居忠量、藤井智之
林業試験場
Selective delignification of wood by white rot fungus Grifora frondosa
Tadakazu Hiroi, Tomoyuki Fujii
Forestry and Forest Products Research Institute
Keywords: Betula platyphylla, microscopy, compound middle lamella, secondary wall
1986-109
α 位にケトンを有する β-O-4 型ジリグノールの Fusarium solani M-13-1 による分解と立体選択的還元（第 2報）
片山健至*1、十河村男*1、堀池満子*1、三木敬夫*1、小橋啓志*1、樋口隆昌*2*1
香川大学農学部、*2 京都大学木材研究所
Degradation and stereoselective reduction of β-O-4 dilignol with a-ketone group by Fusarium solani M-13-1(II)
Takeshi Katayama*1, Murao Sogo*1, Mitchiko Horiike*1, Takao Miki, *1 Keishi Kohashi*1, Takayoshi Higuchi*2*1
Faculty of Agriculture, Kagawa University, *2Wood Research Institute, Kyoto University
Keywords: erythro/threo ratio, 1H-NMR, syringylpropanone, UV spectroscopy
1986-110
カワラタケラッカーゼの単離とその化学的、生化学的特徴
諸星紀幸、吉武彰文、片山義博、原口隆英
東京農工大学農学部
Isolation of laccase fom Coriolus versicolor, and its chemical and biochemical characteristics
Noriyuki Morohoshi, Akifumi Yoshitake, Yoshihiro Katayama, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agiculture and Technology
Keywords: phenol oxidase, electrophoresis, crystallization, antigen
1986-111
Lignin peroxidase による β-O-4 リグニンモデル化合他の分解
三木啓司*1、Michael H. Gold*2*1
公害資源研究所、*2Oregon Graduate Center
Degradation ofβ-O-4 type lignin model compounds by lignin peroxidase
Keiji Miki*1, Michael H. Gold*2*1
National Research Institute for Pollution and Resources, *2Oregon Graduate Center
Keywords: Phanerochaete chrysosporium, cation radical, 18O tracer,
1986-112
酵素によるジオキサンリグニンの生分解
沖 妙、石川久雄
愛嬢大学農学部
Biodegradation of dioxane lignin by enzyme
163

Tae Oki, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: Phanerochaete chrysosporium, dioxane lignin, nitrobenzene oxidation
1986-113
リグニンモデル化合物分解酵素遺伝子のクローニング（I）大腸菌−Pseudomonas シャトルベクターpKT230 お
よびコスミドベクターpVK100 の受動的伝達能力を利用した分解酵素遺伝子のクローニング系の確立
片山義博*1、西川誠司*1、諸星紀幸*1、原口隆英*1、山崎眞狩*2*1
東京農工大学農学部、*2 東京大学農学部
Cloning of the genes related to the enzyme for lignin model compound degradation, I. -Constrution of thecloning system using the Escherichia coli and Pseudomonas spp. shuttle vector pKT230 and cosmid vector
pVK100 by transconjugation
Yoshihiro Katayama*1, Seiji Nishikawa*1 Noriyuki Morohoshi*1, Takafusa Haraguchi*1, Makari Yamasaki*2*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Faculty of Agriculture , theUniversity of Tokyo
Keywords: 5,5-dehydrodivanillic acid, protocatechuic acid, ferulic acid1986-114
リグニンモデル化合物分解酵素遺伝子のクローニング（II）受動的伝達能力を有する大腸菌−Pseudomonas
シャトルベクターpKT230 を用いた P. paucimobilis SYK-6 株のジーンライブラリの構築とクローニング
西川誠司*1、片山義博*1、中村雅哉*1、村山彰啓*1、諸星紀幸*1、原口隆英*1、山崎眞狩*2*1
東京農工大学農学部、*2 東京大学農学部
Cloning of the genes related to the enzyme for lignin model compound degradation (II), -Construction of genelibrary from Pseudomonas paucimobilis SYK-6 with the shuttle vector pKT230 by transconjugation
Seiji Nishikawa*1, Yoshihiro Katayama*1, Masaya Nakamura*1, Akihiro Murayama*1, Noriyuki Morohoshi*1,
Takafusa Haraguchi*1, * Makari Yamasaki*2*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Faculty of Agriculture , theUniversity of Tokyo
Keywords: Pseudomonas putida, vanillic acid, protocatechuic acid,1986-115
Ulin 材（Eusideroxylon zwageri）の耐朽性と化学成分
Wasrin Syafii、善本知孝、鮫島正浩
東京大学農学部
Durability and chemical components of Ulin (Eusideroxylon zwageri) wood
Wasrin Syafii, Tomotaka Yoshimoto, Masahiro Samejima
Faculty of Agriculture, the University of Tokyo
Keywords: Coriolus vercicolor, Tyromeces polutris, decay test, eusiderin, neolignans
1986-116
菌処理マニラ麻の H2O2 添加 TMP 化（その 2）
赤松 勲、上嶋 洋、吉原一年
四国工業技術試験所
Thermomechanical pulping of fungi treated Manila hemp by addition of H2O2 (II)Susumu Akamatsu, Hiroshi Kamishima, Kazutoshi Yoshihara
Government Industrial Research Institute, Shikoku
Keywords: Coriolus hirstus, brightness
1986-117
白色腐朽菌によるパルブ漂白排水の脱色・脱塩素
松本雄二*1、Hou-min Chang*2，T. Joyce*2, T. K. Kirk*3*1
東京大学農学部、*2 ノースカロライナ州立大学、*3 米国林産物研究所
Decoloration and dechlorination of pulp bleach effluent by white rot fungi
Yuji Matsumoto*1, Hou-min Chang*2, T. Joyce*2, T. K. Kirk*3
164

*1

Faculty of Agriculture, the University of Tokyo, *2North Carolina State University, *3Forest Products
Laboratory, USDA
Keywords: Phanerochaete chrysosporium, rotating biological contactor,
1986-118
パルプ廃液処理に関する研究（5） 廃液リグニンおよびフェノールモノマー類の担子菌類による処理性
鮫鳥一彦、谷岡俊彦、高村憲男
高知大学農学部
Studies on treatment of pulp effluent (V), Treatability of effluent lignin and phenol monomer by basidiomycetes
Kazuhiko Sameshima, Toshihiko Tanioka, Norio Takamura
Keywords: Polystictus versicolor, Pleurotus ostreatus , vanillyl alcohol, vanillin, vanillic acid1986-119
特別講演、人工チトクロム P−450 を用いる脂肪族・芳香族化合物の酸化田伏岩夫
京都大学工学部
Invited lecture ; Oxidation of aliphatic and aromatic compounds by artificial cytochrome P-450
Iwao Tabushi
Faculty of Engineering, Kyoto University
1986-201
亜硫酸ナトリウム、ホルムアルデヒドおよびキノン化合物を用いた新蒸解法
大井 洋、中野準三、石津 敦
東京大学農学部
New pulping process with sodium sulfite, formaldehyde and quinone compounds
Hiroshi Ohi, Junzo Nakano, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: yezo spruce, Picea jezoensis. beech, Fagus crenata, saghalien fir, Abies Mayriana,
1986-202
有機溶媒と亜硫酸塩による脱リグニン（VII）パルプ品質の改善について
文 星筆、坂井克己、今村博之
九州大学農学部
Delignification with organic solvents and sulfite (VII), Improvement of pulp properties
Sung-Phil Mung, Kokki Sakai, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: Pinus rigida×Pinus taeda, Betula platyphylla, isopropyl alcohol, secondary butyl alcohol
1986-203
フェノオルガノソルブパルプ化法（弟 3 報）
高橋昭博、佐野嘉拓、笹谷宜志
北海道大学農学部
Phenorganosolv pulping (III)Akihiro Takahashi, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido Univeersity
Keywords: Fagus crenata, pulping, n-propyl alcohol, phenol, cresol, pyrocatechol, dissolved lignin
1986-204
有機酸蒸解におけるリグニンの挙動
安田征市、伊藤範明
名古屋大学農学部
Behavior of lignin during pulping with organic acids
Seiichi Yasuda, Noriaki Ito
Faculty of Agriculture, Nagoya University
Keywords: solvolysis pulping, lignin model compound, acetic acid, arylglycerol-βaryl ether
165

1986-205
酢酸パルプ化における脱リグニン反応
J. L. Davis*1、中坪文明*1、村上浩二*1、R. A. Young*2*1
京都大学農学部、*2University of Wisconsin
Delignification reaction during acetic acid pulping
J. L. Davis*1, Fumiaki Nakatsubo*1, Koji Murakami*1, R. A. Young*2*1
Faculty of Agriculture, Kyoto University, *2University of Wisconsin
Keywords: guaiacylglycerol-β-guaiacyl ether, enol ether, Hibbert’s ketones
1986-206
オゾン分解によるリグニン化学構造の研究 —β-5、 β-1 型構造に由来する二塩基性酸の検索
羽生直人、松本雄二、石津 敦、中野準三
東京大学農学部
Structural study of lignin by ozonolysis. - Investigation of dicarboxylic acids derived from β-5 and β-1
structures
Naoto Habu, Yuji Matsumoto, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, the University of Tokyo
Keywords: dihydrodehydrodiconiferyl alcohol, GLC, GC-MS, 13C-NMR
1986-207
リグニンのメカノケミストリー— モデル化合物のメカノケミカル反応について
李 典艶、橘 燦郎、住本昌之
九州大学農学部
Mechanochemistry of lignin, -Mechanochemical reaction of lignin model compounds
Dian Yan Lee, Sanro Tachibana, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Keywords: coniferyl alcohol methyl ether, veratrylglycerol- -aryl ether, GLC, MS
1986-208
A study on mechanism of pyrolized lignin
Wenda Lu，Jian Li，Sheng Luo Gwei, Yu Koh ming
Northeast Forestry University, China
Keywords: Larix dahurica, dioxane lignin, DSC, IR
1986-209
針葉樹材酵素糖化のためのオゾン酸化前処理
林 徳子、細谷修二、志水一允
林業試験場
Ozonation pretreatment for the enzymatic hydrolysis of softwood
Noriko Hayashi, Shuji Hosoya, Kazumasa Shimizu
Forestry and Forest Products Research Institute
Keywords: Cryptomeria japonica, polarization microscope，cell wall morphology
1986-210
酸糖化リグニンのラジカルスルホン化
渡辺正介、飯塚堯介、石津 敦、中野準三
東京大学農学部
Radical sulphonation of acid hydrolysis lignin
Shosuke Watanabe, Gyosuke Meshitsuka, Atsushi Ishizu, Junzo Nakano
Faculty of Agriculture, The University of Tpkyo
Keywords: Betula maximowicziana, sodium sulfite, MWL, IR
1986-211
166

リグニン系高分子電解質と水との相互作用
畠山兵衛*1、岩田ひろ*2、中村邦雄*3、畠山立子*4*1
製品科学研究所、*2 日本紙パルプ研究所，*3 神奈川県工業試験所、*4 繊維高分子材料研究所
Interaction between water and polyelectrolyte derived from lignin
Hyoe Hatakeyama*1, Hiro Iwata*2, Kunio Nakamura*3, Tatsuko Hatakeyama*4*1
Industrial Products Research Institute, *2Japan Pulp & Paper Research Institute, Inc., *3Kanagawa Industrial
Technology Center, *4Institute for Textiles and Polymers
Keywords: sodium lignosulfonate, DSC, NMR, relaxation time
1986-212
リグニン分解物を原料とする耐熱性高分子
広瀬重雄*1、畠山兵衛*1、中村邦雄*2、畠山立子*3*1
製品科学研究所、*2 神奈川県工業試験所、*3 繊維高分子材料研究所
Heat resistant polymer prepared from lignin degradation productsShigeo Hirose*1, Hyoe Hatakeyama*1, Kunio Nakamura*2, Tatsuko Hatakeyama*3*1
Industrial Products Research Institute, *2Kanagawa Industrial Technology Center, *3Institute for Textiles andPolymers
Keywords: polyester, DSC, X ray analysis, Tg
1986-213
リグニンの水素化分解 —高温における反応時間の影響
小山 実、金沢健治、山田谷正子、杉本義一
化学技術研究所
Hydrogenolysis of lignin, -Effect of reaction time at high temperature
Makoto Koyama, Kenji Kanazawa, Masako Yamadaya, Giichi Sugimoto
National Chemical Laboratory for Industry
Keywords: cresol lignin, thiolignin, monophenols
1986-214
リグニン水素化分解生成物の質量分析 —分子イオンスペクトル法および MS-MS によるキャラクタリゼーシ
ョン
杉本義一、石川啓一郎、丹羽吉夫、山田谷正子、金沢健治、小山 実
化学技術研究所
Mass spectrometric analysis of hydrogenolysis products of lignin, -Molecular ion spectral analysis andcharacterization by MS-MS analysis
Giichi Sugimoto, Keiichiro Ishikawa, Yoshio Niwa, Masako Yamadaya, Kenji Kanazawa, Makoto Koyama
National Chemical Laboratory for Industry
Keywords: thiolignin, alkylphenols
1986-215
フェノール類可溶化木材からの木材用接着剤
小野拡邦、須藤賢一、唐沢仁志
林業試験場
Wood adhesives from wood liquefied by phenol
Hirokuni Ono, Kenichi Sudo, Hitoshi Karasawa
Forestry and Forest Products Research Institute
Keywords: resol formaldehyde resin, GPC, torsional blade analysis
1986-216
リグニン系炭素繊維 —紡糸用リグニンの性状について
須藤賢一、志水一允
林業試験場
Lignin derived carbon fiber, —Properties of lignin suitable for spinning
Kenichi Sudo, Kazumasa Shimizu
167

Forestry and Forest Products Research Institute
Keywords: Betula platyphylla, hydrocracking, GPC, 1H-NMR, 13C-NMR, heat treatment, SEM
1986-217
爆砕リグニンの抗変異原性（弟 2 報） —爆砕リグニン成分及び関連化合物について—
矢澤 到*1、野澤美津子*1、柿島 博*1、西島 靖*1、棚橋光彦*2、樋口隆昌*2*1
鐘紡化粧品研究所、*2 京都大学木材研究所
Antimutagenicity of steam explosion lignin (II), Steam explosion lignin and related compounds
Toru Yazawa*1, Mitsuko Nozawa*1, Hiroshi Kakishima*1, Yasushi Nishijima*1, Mitsuhiko Tanahashi*2, Takayoshi
Higuchi*2*1
Research Laboratory, Kanebo Cosmetic Inc., *2Wood Research Institute, Kyoto University
Keywords: Chamaecyparis obtuse, Betula platyphylla, Salmonella typhimurium, coniferyl alcohol,
peroxidase
1986-218
特別講演、リグニンの形成と構造の不均一牲
寺島典二
名古屋大学農学部
Invited lecture: Heterogeneity in formation and structure of lignin
Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: protolignin, condensed unit, p-hydroxyphenyl lignin, guaiacyl lignin, syringyl lignin, softwood,
hardwood, microautoradiography, cell wall layers

168

第 32 回 （1987.10.20-21） 福岡リーセントホテル
1987-101
紫外線顕微分光法による広葉樹木部構成要素の木化過程の検討
高部圭司*1、深沢和三*1、寺島典二*2、福島和彦*2*1
北海道大学農学部、*2 名古屋大学農学部
Studies on the lignification process of hardwood xylem elements by UV microscope
Keiji Takabe*1, Kazumi Fukazawa*1, Noritsugu Terashima*2, Kazuhiko Fukushima*2*1
Faculty of Agriculture, Hokkaido University, *2Faculty of Agriculture, Nagoya University
Keywords: Oxford poplar, Populus Maximowiczii×Populus berolinensis, Magnolia kobus, cell wall layers
1987-102
木部細胞分化過程における各種成分量の変化 —切片のデンシトメトリー解析を中心として—
藤田 稔、杉山由美子、佐伯 浩
京都大学農学部
Changes of the amount of chemical components during differentiation of xylem cell, - Observation of sections
by densitometry
Minoru Fujita, Yumiko Sugiyama, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Keywords: Cryptomeria japonica, Chamaecyparis obtuse, Pinus Thunbergii, Robinia pseudoacacia,
proteins, peroxidase, lignin
1987-103
西洋ワサビペルオキシターゼを用いた免疫電顕観察法のモデル実験杉山由美子、藤田 稔、佐伯 浩
京都大学農学部
Model experiment for immunoelectron microscopy by use of horseradish peroxidase
Yumiko Sugiyama, Minoru Fujita, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Keywords: Armoracia rusticana, diaminobenzidine, immunostaining, immunohistochemistry
1987-104
ミクロオートラジオグラフ法による広葉樹リグニン形成過程の可視化
福島和彦、寺島典二
名古屋大学農学部
Visualization of formation process of hardwood lignin by microautoradiography
Kazuhiko Fukushima, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: magnolia, Magnolia kobus, lilac, Syringa vulgaris, p-hydroxyphenyl lignin, guaiacyl lignin,
syringyl lignin,
1987-105
強冷摩砕法による MWL，LCC の調製について
福田忠徳、寺島典二
名古屋大学農学部
Preparation of MWL and LCC by milling under super cooling conditions
Tadanori Fukuda, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: black pine, Pinus Thunbergii, liquid nitrogen, UV spectroscopy, IR spectroscopy
1987-106
エポキシ樹脂包埋 MWL の紫外線顕微分光測光
藤井智之
169

林業試験場
UV microspectroscopic analysis of MWL embedded in epoxy resin
Tomoyuki Fujii
Forestry and Forest Products Research Institute
Keywords: beech, Fagus crenata, cell wall model，
1987-107
硫酸法によるリグニン定量における酸可溶性リグニン量の評価
前川英一、一澤泰三、越島哲夫
京都大学木材研究所
Evaluation of acid soluble lignin in sulfuric acid lignin determination
Eiichi Maekawa, Taizo Ichizawa, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Fagus crenata. Acer pictum, Pinus densiflora, Phyllostachys pubescens, Klason lignin
1987-108
リグニンモデル化合物芳香族炭素の化学シフトに及ばす置換基の影響
青山政和*1、H. Y. Hassi*2，D. Tai*3、C. L. Chen*4，J. S．Gratzl*4*1
北海道立林産試験場、*2Metsaliiton Teollisuus OY、*3 南京林業大学、*4 ノースカロライナ州立大学
Effect of substituent groups on the 13C chemical shift of the aromatic carbons of lignin model compounds
Masakazu Aoyama*1, H.Y. Hassi*2, D. Tai*3, C.L. Chen*4, J.S. Gratzl*4*1
Hokkaido Forest Products Research Institute, *2Metsaliiton Teollisuus OY, *3Nanjin Forestry University,*4
North Carolina State University
Keywords: 13C-NMR, substituent chemical shift
1987-109
微生物によるリグニン分解（第 1 報）—高活性，高選択性リグニン分解菌の探索
西田友昭、樫野由憲、三村精男、高原義昌
神戸製鋼所生物学研究所
Lignin biodegradation by wood rot fungi (I) —Screening of highly active and highly selective lignin degrading
fungi
Tomoaki Nishida, Yoshinori Kashino, Akio Mimura, Yoshimasa Takahara
Biotechnology Research Laboratory, Kobe Steel. Ltd.
Keywords: Fagus crenata, guaiacol, gallic acid, phenoloxidase activity, ligninolytic activity
1987-110
嫌気性バクテリアによるリグニンモデル化合物の分解
川上日出国、陳 巍、大宮邦雄、清水祥一
名古屋大学農学部
Degradation of lignin model compounds by anaerobic bacteria
Hidekuni Kawakami, Wei Chen, Kunio Oomiya, Shoichi Shimizu
Faculty of Agriculture, Nagoya University
Keywords: Fusobacterium varium, Enterococcus faecium, biphenyl,  -ether, phenylcoumaran
1987-111
シユードモナス属細菌 TMYl009 株から得られるリグニンモデル化合物脱水素酵素
羽生直人、鮫島正浩、佐分義正、善本知孝
東京大学農学部
Lignin model compound-dehydrogenation enzyme obtained from Pseudomonas TMY1009
Naoto Habu, Masahiro Samejima, Yoshimasa Saburi, Tomotaka Yoshimoto
Faculty of Agriculture, the University of Tokyo
Keywords: phenylcoumaran, NAD, NADH,
1987-112170

ヒイロタケによるリグニン関連芳香族化合物の分解
早川敏雄*1、原口隆英*1、樫野由憲*2*1
東京農工大学農学部、*2 神戸製鋼所
Degradation of aromatic compounds related to lignin by Pycnoporus coccineus
Toshio Hayakawa*1, Takafusa Haraguchi*2, Yoshinori Kashino*2*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Kobe Steel. Ltd.
Keywords: biodegradation, protocatechuic acid, catechol, oxygenase, GC-MS
1987-113
リグニン分解に対する酵素特性
沖 妙、石川久雄
愛媛大学農学部
Characteristics of lignin degrading enzyme
Tae Oki, Hisao Ishikawa
Faculty of Agriculture, Ehime University
Ketwords:
Phanerochaete chrysosporium, dioxane lignin, laccase, peroxidase
1987-114
Phanerochaete chrysosporium におけるリグニン分解酵素系 —Manganese peroxidase の作用機構—
割石博之、Micheal H. Gold
Oregon Graduate Center
Ligninolytic enzyme system in Phanerochaete chrysosporium, - Reaction mechanism of manganese peroxidase
Hiroyuki Wariishi, Michael H. Gold
Oregon Graduate Center
Keywords: EPR spectroscopy, 14NO-MnP, 15NO-MnP,
1987-115
Lignin peroxidase によるリグニンモデル化合物の芳香環開裂
三木啓司*1、近藤隆一郎*2、Michael H. Gold*3*1
公害資源研究所, *2 九州大学農学部、*3Oregon Graduate Center
Cleavage of aromatic rings of lignin model compounds by lignin peroxidase
Keiji Miki*1, Ryuichiro Kondo*2, Michael H. Gold*3*1
National Research Institute for Pollution and Resources, *2Faculty of Agriculture, Kyushu University, *3Oregon
Graduate Center
Keywords: 18O tracer, arylglycerol-biphenyl ether,
1987-116
フェノール類を媒介とする非フェノール性リグニンモデル化合物のカワラタケラッカーゼによる分解
河合真吾、梅澤俊明、樋口隆昌
京都大学木材研究所
Degradation of non-phenolic lignin model compounds in the presence of phenols by laccase of Coriolus
versicolor
Shingo Kawai, Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: biodegradation, lignin substructure model compound, 1,2-bis-(3,4,5-trimethoxyphenyl)propane-1,3-diol, , mediator, syringaldehyde, GC-MS
1987-117
β-O-4-β-O-4 型リグニンモデル三量体のリグニンペルオキシターゼによる分解
梅澤俊明、樋口隆昌
京都大学木材研究所
Degradation of β-O-4-β-O-4 type lignin model trimer by lignin peroxidase
Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
171

Keywords:

Phanerochaete chrysosporium, GC-MS,

1987-118
バイオミメティツクポルフイリン触媒によるリグニン芳香環モデル化合物の環開裂反応服部武文、島田幹夫、梅澤俊明、樋口隆昌
京都大学木材研究所
Ring cleavage reaction of lignin model compound by biomimetic porphyrin catalyst
Takefumi Hattori, Mikio Shimada, Toshiaki Umezawa, Takayoshi Higuchi
Wood research Institute, Kyoto University
Keywords: 3,4-dimethoxybenzylalcohol, lignin peroxidase, 18O tracer,
1987-119
特別講演、最近のタンニンの研究から
西岡五夫
九州大学薬学部
Invited lecture ; Recent advances in research on tannin
Itsuo Nishioka
Faculty of Pharmaceutical Science, Kyushu University
Keywords: Quercus salicina, Camellia sinensis, biological activity
1987-201
シュードモナス属細菌 TMY1009 株におけるリグニンモデル化合物分解酵素産生遺伝子のセルフクローニン
グ系について鮫島正浩、善本知孝
東京大学農学部
Self cloning system of the genes for the production of lignin model compounds degrading enzyme in
Pseudomonas TMY1009
Masahiro Samejima, Tomotaka Yoshimoto
Faculty of Agriculture, the University of Tokyo
Keywords: plasmid, gene library
1987-202
カワラタケ酵素遺伝子のクローニング（II）—Laccase III 糖鎖機能解析と cDNA の合成—
中村雅哉*1、吉武彰文*1、片山義博*1*2、諸星紀幸*1、原口隆英*1、*1
東京農工大学農学部, *2 神戸製鋼生物学研究所
Cloning of the genes for the enzyme of Coriolus versicolor (II) – Functional analysis of sugar chains of laccase
Ⅲ and the synthesis of cDNA
Masaya Nakamura*1, Akifumi Yoshitake*1, * Yoshihiro Katayama*2, Noriyuki Morohoshi*1, Takafusa
Haraguchi*1*1Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Biotechnology Research Laboratory,
Kobe Steel, Ltd.
Keywords: sugar chain function
1987-203
リグニンモデル化合物分解酵素遺伝子のクローニング V
西川誠司*1、片山義博*1*2、政井英二*1，諸星紀幸*1、原口隆英*1、山崎眞狩*3*1
東京農工大学農学部、*2 神戸製鋼生物学研究所、*3 東京大学農学部
Cloning of the genes for the lignin model compounds degrading enzyme (V)Seiji Nishikawa*1, Yoshihiro Katayama*2, Eiji Masai*1, Noriyuki Morohoshi*1, Takafusa Haraguchi*1, Makari
Yamasaki*3*1
Faculty of Agriculture,Tokyo University of Agriculture and Technology, *2Biotechnology Research Laboratory,
Kobe Steel Co. Ltd, *3Faculty of Agriculture, the University of Tokyo
Keywords: Pseudomonas paucimobilis, Pseudomonas putida, gene library,172

1987-204
白色腐朽薗による E 段漂白排液の脱色機構
桃原郁夫*1、渋谷往男*1、松本雄二*1、石津 敦*1、H.-m Chang*2*1
東京大学農学部、*2 ノースカロライナ州立大学
Decoloration mechanism of E stage bleach effluent by white rot fungi
Ikuo Momohara*1, Sumio Shibuya*1, Yuji Matsumoto*1, Atsushi Ishizu*1, H.-m Chang*2*1
Faculty of Agriculture, the University of Tokyo, *2North Carolina State University
Keywords: Phanerochaete chrysosporium, loblolly pine, Pinus taeda, quinone structure
1987-205
白色腐朽菌によるパルプ漂白排水の突然変異原性の変化
渋谷往男、桃原郁夫、松本雄二、石津 敦
東京大学農学部
Changes of mutagenicity of pulp bleach effluent by treatment with white rot fungi
Sumio Shibuya, Ikuo Momohara, Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Phanerochaete chrysosporium, Ames test, softwood KP
1987-206
トリメチルヨードシランによるリグニン中のエーテル結合の選択的開裂
牧野重人、飯塚堯介、石津 敦
東京大学農学部
Selective cleavage of ether linkage in lignin by trimethylsilyl iodide
Shigeto Makino, Gyosuke Meshitsuka, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Betula maximowicziana, Larix Kaempferi, Picea jezoensis, MWL, molecular weight
distribution,
1987-207
リグニンモデル 2 量体の水素化分解
小山 実、金沢健治、杉本義一、山田谷正子
化学技術研究所
Hydrogenolysis of dimeric model compounds of lignin
Makoto Koyama, Kenji Kanazawa, Gi-ichi Sugimoto, Masako Yamadaya
National Chemical Laboratory for Industry
Keywords: diphenyl ether, diphenyl methane, dibenzyl, metal catalyst
1987-208
ソルボリシスによる針葉樹材の脱リグニン
佐野嘉柘、笹谷宜志
北海道大学農学部
Delignification of softwood by solvolysis
Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Keywords: Abies Mayriana, cresol water, delignification mechanism, guaiacylglycerol-β-guaiacyl ether,veratrylglycerol-β-guaiacyl ether, 1H-NMR
1987-209
有機酸蒸解におけるリグニンの挙動 —フェニルクマランおよびジアリールプロパン構造の反応牲
安田征市
名古屋大学農学部
Behavior of lignin during cooking in organic acids, —Reactivity of phenylcoumaran and diarylpropane
structures
Seiichi Yasuda
173

Faculty of Agriculture, Nagoya University
Keywords: acetic acid cooking, phenylcoumaran, diarylpropane
1987-210
蒸煮・爆砕前処理によるアカシア類の利用
勝部和則*1、嘉手苅幸男*2、志水一允*3、藤井智之*3、須藤賢一*3、長沢定男*3*1
岩手バイオマス研究センター, *2 沖縄県林業試験所、*3 林業試験場
Utilization of Acacia by steam explosion pretreatment
Kazunori Katsube*1, Yukio Kategaru*2, Kazumasa Shimizu*3, Tomoyuki Fujii*3, Kenichi Sudo*3, Sadao
Nagasawa*3*1
Iwate Biomass Research Center, *2Okinawa Prefectural Forest Experiment Station, *3Forestry and Forest
Products Research Institute
Keywords: enzymatic hydrolysis, sugar composition, lignin structure
1987-211
爆砕処理によるリグニンの分解機構の解明（II)Myrtha Karina、棚橋光彦、樋口隆昌
京都大学木材研究所
Degradation mechanism of lignin during steam explosion treatment (II)Myrtha Karina, Mitsuhiko Tanahashi, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: guaiacylglycerol-β-guaiacyl ether, veratrylglycerol-β-guaiacyl ether, 1H-NMR, GC-MS
1987-212
未利用林産資源の酵素、微生物による変換利用(1)—前処理としてのアスプルンドパルプの製造と解析—
鮫島一彦*1、藤原新二*1、高村憲男*1、黒田健一*2
高知大学農学部、筑波大学農林工学系
Utilization of unused forest resources by conversion with enzyme and microorganism (I) -Preparation andanalysis of Asplund pulp as a pretreatment
Kazuhiko Sameshima*1, Shinji Fujiwara*1, Norio Takamura*1, Ken-ichi Kuroda*2*1
Faculty of Agriculture, Kochi University, *2 Institute of Agricultural and Forest Engineering, University ofTsukuba
Keywords: Betula platyphylla, Fagus crenata, Zelkova serrata, Cryptomeria japonica, Chamaecyparis
obtuse, Pinus densiflora, enzymatic susceptibility
1987-213
アルカリ性サルファイト・キノン蒸解におけるリグニンの挙動
大井 洋*1、石津 敦*1、中野準三*2*1
東京大学農学部、*2 福井工業大学工学部
Behavior of lignin during alkaline sulfite-quinone pulping
Hiroshi Ohi*1, Atsushi Ishizu*1, Junzo Nakano*2*1
Faculty of Agriculture, the University of Tokyo, *2Faculty of Engineering, Fukui University of Technology
Keywords: Picea jezoensis, Fagus crenata, Abies sachalinensis, gel filtration chromatography
1987-214
N 材クラフト蒸解において最終脱リグニンを阻害する多糖について
松本雄二*1、石津 敦*1、H.-m. Chang*2*1
東京大学農学部, *2 ノースカロライナ州立大学
Studies on the polysaccharides preventing final delignification in kraft pulping of softwood
Yuji Matsumoto*1, Atsushi Ishizu *1, H.-m. Chang*2*1
Faculty of Agriculture, the University of Tokyo, *2North Carolina State University
Keywords: Pinus taeda, LCC, hemicellulose-consisting sugars
1987-215
A preliminary study on paper aging caused by light174

Jian Li，Gwei Sheng Luo，Wenda Lu，Yu Koh Ming
Northeast Forestry University, China
Keywords: ESCA, FTIR, SEM
1987-216
リグノスルホン酸塩—水系のメゾフェーズ
畠山兵衛*1、広瀬重雄*1、畠山立子*2*1
製品科学研究所、*2 繊維高分子研究所
Meso phase of lignosulfonate-water system
Hyoe Hatakeyama*1, Shigeo Hirose*1, Tatsuko Hatakeyama*2*1
Industrial Products Research Institute, *2Institute for Textiles and Polymers
Keywords: DSC, 1H-NMR, polarization microscope
1987-217
リグニンから誘導される含リン型ポリウレタン
広瀬重雄*1、矢野彰一郎*1、畠山兵衛*1、畠山立子*2*1
製品科学研究所、*2 繊維高分子材料研究所
Polyurethane including phosphor derived from lignin
Shigeo Hirose*1, Shoichiro Yano*1, Hyoe Hatakeyama*1, Tatsuko Hatakeyama*2*1
Industrial Products Research Institute, *2Institute for Textiles and Polymers
Keywords: Fagus crenata, solvolysis lignin, TG, heat resistance
1987-218
フェノール化リグニンの木材接着剤への応用
小野拡邦*1、須藤賢一*1、唐沢仁志*1、姚 忻*2*1
林業試験場, *2 黒竜江省林産工業研究所
Utilization of phenolated lignin to wood adhesives
Hirokuni Ono*1, Kenichi Sudo*1, Hitoshi Karasawa*1, Yao Xin*2*1
Forestry and Forest Products Research Institute, *2Forest Products Research Institute of Heilongjiang Province
Keywords: Betula platyphylla, GPC, IR spectroscopy,
1987-219
特別講演、酸素及び過酸化物漂白におけるリグニンの挙動石川久碓
愛媛大学農学部
Invited lecture ; Reactions of lignin during oxygen and peroxide bleaching
Hisao Ishikawa
Faculty of Agriculture, Ehime University
Keywords: active oxygen species

175

第 33 回 （1988.11.8-9） ホテルサンルート筑波
1988-101
ポプラの分子育種に関する研究（1） リグニン形成能に関与するアイソペルオキシターゼの性質
諸星紀幸、西田謙吾、山田恵子、三国順子、片山義博、原口隆英
東京農工大学農学部
Molecular breeding of poplar (I), Characterization of isoperoxidase involved to lignification
Noriyuki Morohoshi, Kengo Nishida, Keiko Yamada, Junko Mikuni, Yoshihiro Katayama, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Populus euroamericana, isoelectric focusing, gel filtration chromatography
1988-102
ポプラの分子育種に関する研究（2） ポプラカルスの分化誘導と Ti プラスミド導入系の確立
片山義博、柳田恒一郎、諸星紀幸、原口隆英
Molecular breeding of poplar (II), Induction of poplar callus differentiation and establishment of Ti plasmid
introduction system
Yoshihiro Katayama, Koichiro Yanagida, Noriyuki Morohoshi, Takafusa Haraguchi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: Agrobacterium tumefacience
1988-103
イネにおけるリグニンの形成と構造
何 蘭芳、寺島典二
名古屋大学農学部
Formation and structure of lignin in rice plants
Lanfang He, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: Oryza sativa, microautoradiography, p-hydroxyphenyl lignin, guaiacyl lignin, syringyl lignin,
AQ-soda pulping
1988-104p−ヒドロキシフェニルリグニンの性質について
福島和彦、寺島典二
名古屋大学農学部
Properties of p-hydroxyphenyl lignin
Kazuhiko Fukushima, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: Pinus Thunbergii, microautoradiography, compression wood, HPLC
1988-105
LCC 生合成時における糖加水分解酵素の関与について
迫 孝、飯森武志、近藤隆一郎、今村博之
九州大学農学部
Participation of carbohydrate hydrolyzing enzyme during biosynthesis of LCC
Takashi Sako, Takeshi Iimori, Ryuichiro Kondo, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: cellobiose, β-glucosidase, transglycosylation, coniferyl alcohol, isoconiferin
1988-106
過ヨウ素酸リグニンの調製と性状
種田英孝、石津 敦
東京大学農学部
Preparation and characterization of periodate lignin
Hidetaka Taneda, Atsushi Ishizu
176

Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, Smith degradation, sugar contents,
1988-107
凍結粉砕を利用した木材酵素糖化とリグニンの抽出について
渡辺隆司、吉村直子、越島哲夫
京都大学木材研究所
Enzymatic saccharification of wood and extraction of lignin using cryomilling
Takashi Watanabe, Naoko Yoshimura, Tetsuo Koshijima
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, Fagus crenata, ball milling, SEM,
1988-108
オゾン分解によるリグニン化学構造の研究 —ピノレジノール型構造の存在の検討—
松本雄二、南 一守、石津 敦
東京大学農学部
Structural study on lignin by ozonolysis, —Investigation of the presence of pinoresinol structures—
Yuji Matsumoto, Kazumori Minami, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Fagus crenata, Picea jezoensis, Eucalyptus, MWL, 13C-NMR
1988-109
トリメチルヨードシランによるリグニン中のエーテル結合の選択的開裂
牧野重人、飯塚堯介、石津 敦
東京大学農学部
Selective cleavage of ether linkages in lignin by trimethylsilyl iodide
Shigeto Makino, Gyosuke Meshitsuka, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Picea jezoensis, MWL, molecular weight distribution
1988-110
Acetylbromide へのリグノセルロースの溶解 —反応機構とリグニンの UV スペクトル
飯山賢治*1、Adrian F. A. Wallis*2*1
東京大学農学部、*2CSIRO, Australia
Dissolution of lignocellulose in acetylbromide, -Reaction mechanism and UV spectra of lignin—
Kenji Iiyama*1, Adrian F.A. Wallis*2*1
Faculty of Agriculture, the University of Tokyo, *2CSIRO, Australia
Keywords: Pinus radiata, UV spectroscopy, lignin model compound, GPC
1988-111
酸および加熱処理過程におけるリグニンの縮合について
船岡正光、柴田真美、加古辰成、阿部 勲
三重大学生物資源学部
Condensation of lignin during acid and heat treatment
Masamitsu Funaoka, Mami Shibata, Tatsunari Kako, Isao Abe
Faculty of Bioresources, Mie University
Keywords: Picea jezoensis, Pseudotsuga taxifolia, nucleus exchange reaction, nitrobenzene oxidation
1988-112
クラフト蒸解過程における複合中間層および二次壁領域でのリグニンのフラグメンテーションと縮合
船岡正光*1、Vincent L．Chiang*2*1
三重大学生物資源学部、*2Michigan Technological University
Fragmentation and condensation of lignin in middle lamella and secondary wall during kraft cooking
Masamitsu Funaoka*1, Vincent L. Chiang*2
177

*1

Faculty of Bioresources, Mie University, *2Michigan Technological University
Keywords: Pseudotsuga taxifolia, nuclear exchange reaction, nitrobenzene oxidation, middle lamella,secondary wall
1988-113
爆砕処理によるリグニンの分解機構解明（IV）—シナピルアルコール DHP の合成と高圧水蒸気処理
棚橋光彦、Myrtha Karina、樋口隆昌
京都大学木材研究所
Degradation mechanism of lignin during steam explosion (IV), -Synthesis of sinapyl alcohol DHP and its
treatment with high pressure steam
Mitsuhiko Tanahashi, Myrtha Karina, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: 1H-NMR, 13C-NMR, GC-MS, acidolysis, syringaresinol, radical reaction
1988-114
リグニンのメカノケミストリー（IV） —フェニルクマランモデル化合物のメカノケミカル反応と其の生成物の過酸化水素反応—李典 艶、住本昌之
九州大学農学部
Mechanochemistry of lignin (IV), —Mechanochemical reaction of phenylcoumaran type model compounds,
and reaction of the products with hydrogen peroxide—
Dian Yan Lee, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Keywords: stilbene, 1H-NMR, UV spectroscopy, IR spectroscopy, mass spectrometry
1988-115
酸糖化リグニンのラジカルスルホン化
渡辺正介、飯塚堯介、石津 敦
東京大学農学部
Radical sulphonation of acid hydrolysis lignin
Masasuke Watanabe, Gyosuke Meshitsuka, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Betula maximowicziana, sodium sulphite, UV spectroscopy, GPC
1988-116
分別クラフトリグニンのガラス転移
吉田博久*1、R. Mörck、K. Kringstad*2、畠山兵衛*3*1
東京都立大学工学部、*2STFI、*3 製品科学研究所
Glass transition of fractionated kraft lignin
Hirohisa Yoshida*1, R. Mörck*2, K. Kringstad*2, Hyoe Hatakeyama*3*1
Faculty of Engineering, Tokyo Metropolitan University, *2STFI, Sweden, *3Industrial Products ResearchInstitute
Keywords: solubility parameter, polydispersity, molecular weight distribution
1988-117
ソルボリシスリグニンを原料とするポリウレタンの力学特性
中村邦雄*1、R. Mörck*２、A．Reimann*２、K. Kringstad*２、畠山兵衛*３*1
大妻女子大学、*２STFI、*３製品科学研究所
Mechanical properties of polyurethane prepared from solvolysis lignin
Kunio Nakamura*1, R. Mörck*２, A. Reimann*２, K. Kringstad*２, Hyoe Hatakeyama*３*1
Otsuma Women’s University, *２STFI, Sweden, *３Industrial Products Research Institute
Keywords: Fagus crenata, PEG
1988-118
178

特別講演、糖質の生産とその高度利用について
小林昭一
農林水産省食品総合研究所
Invited lecture ; Production of carbohydrates and their advanced utilization
Shoichi Kobayashi
National Food Research Institute, Ministry of Agriculture, Fishery and Forestry
Keywords: sucrose, chitin, fructan, starch, isomerase, maltoligosaccharide, cyclodextrin
1988-201
カルボニル化合物を助剤とする亜硫酸ソーダ・キノン蒸解
中野準三、宮崎重和、隈原文康
福井工業大学工学部
Sodium sulfite-quinone cooking with carbonyl compounds as additives
Junzo Nakano, Shigekazu Miyazaki, Fumiyasu Kumahara
Fukui University of Technology
Keywords: Pinus
densiflora,
Betulamaximowicziana,
1,4-dihydro-9,10-dihydroxyanthracene,
formaldehyde
1988-202
アルカリ性サルファイト・キノン蒸解の脱リグニン機構
大井 洋、石津 敦
東京大学農学部
Delignification mechanism of alkaline sulfite-quinone cooking
Hiroshi Ohi, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Picea
jezoensis,
Abies
sachalinensis,
1,4-dihydro-9,10-dihydroxyanthracene, cellulose,  -ether cleavage,

Fagus

crenata,

MWL,

DDA,

1988-203
ソルボリシスパルプ化に関する研究 (第４報) 蒸解溶媒と蒸解反応
岩田ひろ、可知省吾、荒木 廣、青柳哲夫
日本紙パルプ研究所
Studies on solvolysis pulping (IV), Composition of cooking solvent and cooking reaction
Hiro Iwata, Shogo Kachi, Hiroshi Araki, Tetsuo Aoyagi
Japan Pulp & Paper Research Institute, Inc.
Keywords: Fagus crenata, Pinus Thunbergii, cresol, bound solvent
1988-204
硫酸触媒による広葉樹材の常圧パルプ化（第 2 報）
島本 周、中村雅幸、佐野嘉柘
北海道大学農学部
Pulping of hardwood at atmospheric pressure with sulfuric acid as catalyst (II)Shu Shimamoto, Masayuki Nakamura, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Keywords: Betula maximowicziana, acetic acid, phenol, 1H-NMR, GPC
1988-205
未利用植物資源の PA 法（過酸化水素-アルカリ法）によるパルプ化 —パルプ工業におけるショート
サーキットはどこまで可能か—
御田昭雄
化学技術研究所
Pulping of unutilized plant resources by PA method (hydrogen peroxide-alkali), —How far the short circuit ofpulp industry could be achieved—
Akio Mita
179

National Chemical Laboratory for Industry
Keywords: used paper, recyling, non-wood pulp
1988-206
伝統的和紙製造法の化学的研究（2）—木灰の分析と木灰蒸煮処理—
鮫島一彦、藤原新二、堀江大介、高村憲男
高知大学農学部
Chemical characterization of traditional process of Japanese paper production, II. -Analysis of ash and pulping
with ashKazuhiko Sameshima, Shinji Fujiwara, Daisuke Horie, Norio Takamura
Faculty of Agriculture, Kochi University
Keywords: Edgeworthia chrysantha, Broussonetia kazinoki × B. papyrifera, Washi paper, ash
1988-特別講演
森林経営の展望熊崎 実
森林総合研究所
Invited lecture ; A perspective on forest management
Minoru Kumazaki
Forestry and Forest Products Research Institute1988-207
アラゲカワラタケの 1 核菌糸体の生理特性とリグニンの分解
吉原一年、上嶋 洋、西山昌史、赤松 勲
四国工業技術試験所
Physiological characteristics of monokariotic mycelia of Coriolus hirsutus IFO4917 and the degradation ofligninKazutoshi Yoshihara, Hiroshi Kamishima, Masashi Nishiyama, Isao Akamatsu
Government Industrial Research Institute ,Sikoku
Keywords: Populus sp., liquid culture, β-glucosidase, CMCase, xylanase, laccase
1988-208
白色腐朽菌 Phanerochaete chrysosporium のリグニンパーオキシダーゼ生産能についての遺伝的改良桑原正章、麻田恭彦、打越正延、凌 楓、木村義雄、山本澄人
香川大学農学部
Genetic improvement of lignin peroxidase productivity of white rot fungus Phanerochaete chrysosporium
Masaaki Kuwahara, Yasuhiko Asada, Masanobu Uchikoshi, Ling Feng, Yoshio Kimura, Sumito Yamamoto
Faculty of Agriculture, Kagawa University
Keywords: DNA, mutant, DEAE–Sepharose chromatography,
1988-209
好アルカリ性コリネバクテリウム。 ジリグノール分解株のプロトプラスト化及び再生
川上日出国、葛原憲康
名古屋大学農学部
Alkalophilic Corynebacterium. Protoplast formation and regeneration of the dilignol degrading strain
Hidekuni Kawakami, Noriyasu Kuzuhara
Faculty of Agriculture, Nagoya University
Keywords: lignin degradation, lignin model compound, vanillin, protoplast,
1988-210
リグニンモデル化合物分解酵素遺伝子のクローニング（VIII）—Pseudomonas paucimobilis SYK−6 のβ−エーテル結合開裂酵素—
政井英司*1，片山義博*1*2、西川誠司*1、山崎眞狩*3、諸星紀幸*1、原口隆英*1*1
東京農工大学農学部、*2 神戸製鋼生物学研究所、*3 東京大学農学部
180

Cloning of the genes for the lignin model compounds degrading enzyme. VIII. -β-Ether cleaving enzyme of
Pseudomonas paucimobilis SYK−6
Eiji Masai*1, Yoshihiro Katayama*2, Seiji Nishikawa*1, Makari Yamasaki*3, Noriyuki Morohoshi*1, Takafusa
Haraguchi*1*1Faculty of Agriculture,Tokyo University of Agriculture and Technology, *2Biotechnology Research Laboratory,
Kobe Steel, Ltd, *3Faculty of Agriculture, the University of Tokyo
Keywords: umbelliferone ether, vanillin ether,
1988-211
電気パルスによるシュードモナス属細菌への遺伝子の導入
鮫島正浩、鴨田重裕、善本知孝
東京大学農学部
Introduction of the genes to Pseudomonas by electric pulse
Masahiro Samejima, Shigehiro Kamota, Tomotaka Yoshimoto
Faculty of Agriculture, the University of Tokyo
Keywords: Pseudomonas putida, genetic transformation, plasmid
1988-212
シユードモナス属細菌 TMYl009 株による β-1 型モデル化合物の分解
羽生直人、小松徹史、鴨田重裕、鮫島正浩、善本知孝
東京大学農学部
Degradation of 1 type lignin model compounds by Pseudomonas TMY1009
Naoto Habu, Tetsushi Komatsu, Shigehiro Kamota, Masahiro Samejima, Tomotaka Yoshimoto
Faculty of Agriculture, the University of Tokyo
Keywords: erythro-1,2-bis(4-hydroxy-3-methoxyphenyl)-1,3-propanediol, HPLC
1988-213
Fusarium solani M-13-1 による β−アリールエーテル結合の開裂と α−ケトンの還元生成物の絶対配置
片山健至、大浦健二、筒井丈二、十河村男
香川大学農学部
Cleavage of a β-aryl ether linkage by Fusarium solani M-13-1 and the absolute configuration of α-ketonic
reduction products
Takeshi Katayama, Kenji Ohura, Jyoji Tsutsui, Murao Sogo
Faculty of Agriculture, Kagawa University
Keywords: glycerol-2-aryl ether, guaiacylglycerol-β-(vanillic acid) ether, UV spectroscopy, HPLC,
1
H-NMR
1988-214
カワラタケ菌体外酵素によるリグニン生分解機構の解析
飯村洋介*1、片山義博*1*2、田村利香*1、諸星紀幸*1、原口隆英*1*1
東京農工大学農学部、*2 神戸製鋼生物学研究所
Analysis of the biodegradation mechanism of lignin by extracellular enzyme of Coriolus vercicolor
Yosuke Iimura*1, Yoshihiro Katayama*1*2, Rika Tamura*1, Noriyuki Morohoshi, *1 Takafusa Haraguchi*1*1Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Biotechnology ResearchLaboratory Kobe Steel, Ltd.
Keywords: laccase Ⅲ, 13C-DHP, 14C-DHP, HPLC, 13C-NMR
1988-215
木材腐朽菌によるリグニンモデル配糖体の生成について（V）
近藤隆一郎、今村博之
九州大学農学部
Formation of lignin model glycosides by wood-rotting fungi (V)Ryuichiro Kondo, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
181

Keywords: Betula platyphylla, Tyromyces palustris, Coriolus versicolor, Phanerochaete chrysosporium,veratryl alcohol, veratraldehyde
1988-216
DHP 及びその配糖体の酵素分解
飯森武志*1、迫 孝*1、近藤隆一郎*1、今村博之*1、西田友昭*2*1
九州大学農学部、*2 神戸製鋼生物学研究所
Enzymatic degradation of DHP and its glycoside
Takeshi Iimori*1, Takashi Sako*1, Ryuichiro Kondo*1, Hiroyuki Imamura*1, Tomoaki Nishida*2*1
Faculty of Agriculture, Kyushu University, *2Biotechnology Research Laboratory, Kobe Steel, Ltd.
Keywords: Phanerochaete chrysosporium, lignin peroxidase, laccase, horse radish peroxidase
1988-217
遊離のフェノール性水酸基を持つ DHP のリグニンペルオキシダーゼによる分解
梅澤俊明、樋口隆昌
京都大学木材研究所
Degradation of DHP with free phenolic hydroxyl group by lignin peroxidase
Toshiaki Umezawa, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phanerochaete chrysosporium, phenolic OH, GC-MS, β-O-4 bond cleavage
1988-218
微生物によるリグニン分解（第 4 報）—高活性、高選択性リグニン分解菌 IZU−154 株を前処理に用いた木材
糖化プロセス—
西田友昭、中山雄之、三村精男、高原義昌
神戸製鋼所生物学研究所
Lignin biodegradation by wood rot fungi (IV) -Wood hydrolysis process using highly active and highly selective
lignin degrading fungus IZU-154—
Tomoaki Nishida, Tsuyoshi Nakayama, Akio Mimura, Yoshimasa Takahara
Biotechnology Research Laboratory, Kobe Steel Ltd.
Keywords: Fagus crenata, Coriolus versicolor, wood saccharification, enzymatic hydrolysis, Klason lignin
1988-219
機械パルプの菌体外酵素による漂白
山下民治*1、橘 燦郎*2、大島喜八郎 3、住本昌之*2*1
中越パルプ工業株式会社、*2 九州大学農学部、*3 十條製紙株式会社
Bleaching of mechanical pulp by extracellular enzyme
Tamiharu Yamashita*1, Sanro Tachibana*2, Kihachiro Ohshima*3, Masashi Sumimoto*2*1
Chuetsu Pulp & Paper Co. Ltd, *2Faculty of Agriculture, Kyushu University, *3Jujo Paper Co. Ltd.
Keywords: Phanerochaete chrysosporium, Coriolus versicolor, brightness, post color number

182

第 34 回 （1989.10.16-17） 名古屋大学農学部
1989-101
圧締試料の X 線回折法などによるミクロフイブリル配向分布の計測とリグニンの堆積
畑 茂樹、藤田 稔、佐伯 浩
京都大学農学部
Measurement of distribution of microfibril orientation and lignin deposition in the compressed sample by X ray
diffraction
Shigeki Hata, Minoru Fujita, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Keywords: Cryptomeria japonica, Chamaecyparis obtusa, UV microspectroscopy
1989-102
液体窒素下で破砕された細胞壁断片におけるリグニン分布と多様性の検討
吉永 新、藤田 稔、佐伯 浩
京都大学農学部
Distribution and diversity of lignin in cell wall pieces obtained by cryomilling in liquid nitrogen
Arata Yoshinaga, Minoru Fujita, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Keywords: Chamaecyparis obtusa, Betula maximowicziana, Quercus crispula, secondary wall, middle
lamella, UV microspectroscopy, Mäule color reaction,
1989-103
イチョウにおけるリグニンの形成と構造
福島和彦、寺島典二
名古屋大学農学部
Formation and structure of lignin in ginkgo
Kazuhiko Fukushima, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Keywords: microautoradiography, radio tracer, nitrobenzene oxidation, xylem differentiation
1989-104
草本植物リグニン中の p−hydroxyphenyl 核
飯山賢治*1、Thi Bach Tuyet Lam*2, Bruce A．Stone*2*1
東京大学農学部、*2La Trobe 大学生化学科
p−Hydroxyphenyl nucleus in herbaceous plant lignin
Kenji Iiyama*1, Thi Bach Tuyet Lam*2, Bruce A. Stone*2*1
Faculty of Agriculture, the University of Tokyo, *２Department of Biochemistry, La Trobe University, Australia
Keywords: wheat, Triticum aestivum, nitrobenzene oxidation, cinnamic acid
1989-105
イネ科植物細胞壁中の LCC 結合 —Ferulic acid bridge—
飯山賢治*1、Thi Bach Tuyet Lam*2, Bruce A．Stone*2*1
東京大学農学部、*2La Trobe 大学生化学科
LCC bonds in cell wall of Gramineous plant, –Ferulic acid bridge
Kenji Iiyama*1, Thi Bach Tuyet Lam*2, Bruce A. Stone*2*1
Faculty of Agriculture, the University of Tokyo, *２Department of Biochemistry, La Trobe University, Australia
Keywords: Triticum aestivum, wheat internode, ferulic acid, cinnamic acid, diferulic acid
1989-106
E1 リグニンの起源と性状
松本雄二、桃原郁夫、石津 敦
東京大学農学部
Origin and character of E1 lignin
183

Yuji Matsumoto, Ikuo Momohara, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: chlorine bleaching, E1 effluent, chlorinated lignin, alkaline treatment, GPC
1989-107
Cloning of bi-functional O-methyltransferase from aspen (Populus tremuloides)
Robert C．Bugos，Vincent L．Chiang, Wilbur H．Campbell
Michigan Technological University
Keywords: ion exchange chromatography, affinity chromatography,
1989-108
リグニン生合成制御に関する研究 アンチセンス法を用いたペルオキシダーゼの発現制御
刑部敬史*1、西田謙吾*1、山門幹子*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Studies on the control of lignin biosynthesis, -Regulation of peroxidase expression by antisense RNAtechnology.Keishi Osakabe*1, Kengo Nishida*1, Mikiko Yamakado*1, Yoshihiro Katayama*2, Noriyuki Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2 Cooperative Research Center,
Tokyo University of Agriculture and Technology
Keywords: Nicotiana tabacum, antisense RNA, Ti plasmid
1989-109
リグニンモデル化合物分解酵素遺伝子のクローニング(XI) βアリルエーテル結合開裂酵素遺伝子の解析
政井英司*1、片山義博*２、西川誠司*1、山崎眞狩*３、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター、*３東京大学農学部
Cloning of the gene for lignin model compounds degrading enzyme (XI), —Analysis of the gene encoding the
enzyme of βaryl ether cleavage
Eiji Masai*1, Yoshihiro Katayama*２, Seiji Nishikawa*1, Makari Yamazaki*３, Noriyuki Morohoshi*１*1
Faculty of Agriculture, Tokyo University of Agriculture, *2Cooperative Research Center, Tokyo University ofAgriculture and Technology, *３Faculty of Agriculture, the University of Tokyo
Keywords: Pseudomonas paucimobilis, Escherichia coli, umbelliferone ether
1989-110ビフェニル型リグニンモデル化合物芳香族炭素の化学シフトに及ぼす置換基の影響
青山政和*1、M．Drumond*2，C. L．Chen*2, D．Robert*3*1
北海道立林産試験場、*2 ノースカロライナ州立大学、*3C. E. N. G.
Effect of substituent groups on the chemical shift of aromatic carbons of biphenyl type lignin model compounds
Masakazu Aoyama*1, M. Drumond*2, * C.L. Chen*2, D. Robert*3*1
Hokkaido Forest Products Research Institute, *2North Carolina State University, *3Centre d’Etudes Nucléaires
de Grenoble
Keywords: 13C NMR, Picea glauca, MWL,
1989-111
アルカリ性蒸解における針葉樹リグニンと広葉樹リグニンの反応性の差異（4）—イオン化示差スペクトルを用いたシリンギルリグニンの分布—
堤 祐司、近藤隆一郎、坂井克己、今村博之
九州大学農学部
Differences in the reactivity between lignins from softwood and hardwood during alkaline cooking (IV)—Distribution of syringyl lignin by ionization difference spectroscopy
Yuji Tsutsumi, Ryuichiro Kondo, Kokki Sakai, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: Pinus densiflora, Betula platyphylla, dioxane lignin, syringyl lignin, guaiacyl lignin, GPC
1989-112
核交換法を用いたプロトリグニンの構造解析へのアプローチ184

光永 徹、船岡正光、阿部 勲
三重大学生物資源学部
Approach to the structural analysis of proto lignin by the use of nuclear exchange method
Toru Mitsunaga, Masamitsu Funaoka, Isao Abe
Faculty of Bioresources, Mie University
Keywords: Picea jezoensis, Betula maximowicziana, Phyllostachys sp., Triticum sp., nitrobenzene
oxidation
1989-113
ESR による粉砕した含水リグノセルロース中のラジカル定量と粉砕挙動の解明
壁谷 洋
四国工業技術試験所
Quantitative determination of radicals in wet milled lignocellulose by ESR and investigation of behavior during
milling
Hiroshi Kabeya
Government Industrial Research Institute, Shikoku
Keywords: TMP, cellulose powder, free radical, enzymatic hydrolysis,
1989-114
リグニンのメカノケミストリー（第 7 報）β−1 型リグニンモデル化合物のメカノケミカル反応
呉 宗華、松岡昌伸、李 典艶、住本昌之
九州大学農学部
Mechanochemistry of lignin (VII), -Mechanochemical reaction of β−1 type lignin model compounds
Zong-Hua Wu, Masanobu Matsuoka, Dian-Yan Lee, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Keywords: ceramic ball mill, vibratory ball mill, KRK type refiner, stilbene
1989-115
リグニンのラジカルスルホン化
渡辺正介、飯塚堯介、石津 敦
東京大学農学部
Radical-sulfonation of lignin
Shosuke Watanabe, Gyosuke Meshitsuka, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: sodium sulfite, oxygen, ethylguaiacol, GC-MS
1989-116
広葉樹硫酸リグニンの理化学的性質
安田征市、平野淳一
名古屋大学農学部
Physical and chemical properties of sulfuric acid lignins from hardwoods
Seiichi Yasuda, Junichi Hirano
Faculty of Agriculture, Nagoya University
Keywords: beech, Fagus crenata, MWL, Klason lignin, acid-soluble lignin, syringyl lignin, nitrobenzene
oxidation, gel filtration, 1H-NMR
1989-117
硫酸触媒による常圧酢酸パルプ化 —脱リグニン機構とリグニンの性質—
島本 周、佐野嘉拓
北海道大学農学部
Acetic acid pulping at atmospheric pressure with sulfuric acid as a catalyst, -Delignification mechanism andproperties of lignin
Shu Shimamoto, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
185

Keywords:

Betula maximowicziana, hydrogenolysis, GPC, 1H-NMR, 13C-NMR

1989-118
アルコール・バイサルファイト処理による β-O-4 結合の開裂反応について
高木孝夫、坂井克己、宮脇正一、今村博之
九州大学農学部
β-O-4 cleavage reactions during alcohol-bisulfite treatment
Takao Takagi, Kokki Sakai, Shoichi Miyawaki, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: lignin model compounds, 2-propanol, isoeugenol, eugenol
1989-特別講演
葉肉単細胞培養系における木部細胞分化機構
福田裕穂
東北大学理学部
Invited lecture ; Differentiation mechanism of xylem cells in single mesophyll cells culture
Hiroo Fukuda
Faculty of Science, Tohoku University
Keywords: Zinnia elegans, tracheary element, secondary cell wall, lignin deposition, peroxidase
1989-201
リグニンの熱分解ガスクロマトグラフィー（第一報）分解生成物組成に及ぼす無機化合物の影響
黒田健一*1、井上嘉幸*1、坂井克己*2*1
筑波大学農林工学系、*2 九州大学農学部
Pyrolysis gas chromatography of lignin (I), Effects of inorganic compounds on the composition of degradation
products
Ken-ichi Kuroda*1, Yoshiyuki Inoue*1, Kokki Sakai*2*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2Faculty of Agriculture, Kyushu
University
Keywords: Pinus densiflora, Chamaecyparis obtuse, Cryptomeria japonica,
1989-202
膨潤-溶媒和のコンビネーションによる木材成分の迅速分離 —理論および分離挙動—
船岡正光、阿部 勲
三重大学生物資源学部
Rapid separation of wood constituents by the combination of swelling and solvation. -Theory and separation
behavior
Masamitsu Funaoka, Isao Abe
Faculty of Bioresources, Mie University
Keywords: cresol, sulphric acid, temperature, wood refining
1989-203
膨潤-溶媒和法による木材成分の分離 —分離におよほす酸およびフェノール誘導体の効果—
船岡正光、深津俊輔、阿部 勲
三重大学生物資源学部
Separation of wood constituents by swelling –solvation method, —Effects of acid and phenol derivatives on
separation—
Masamitsu Funaoka, Shunsuke Fukatsu, Isao Abe
Faculty of Bioresources, Mie University
Keywords: cresol, ethylphenol, propylphenol, guaiacol, chlorophenol, GPC
1989-204
リグニンにおけるジフェニルメタン型縮合構造の生成とその解裂
船岡正光、久保村実、阿部 勲
186三重大学生物資源学部
Formation and cleavage of diphenylmethane type condensed structure in lignin
Masamitsu Funaoka, Minoru Kubomura, Isao Abe
Faculty of Bioresources, Mie University
Keywords: Picea jezoensis, Betula maximowicziana, nuclear exchange, nitrobenzene oxidation
1989-205
α−ケト β−アリールエーテル構造を有するモデル化合物の光分解
深川伸隆、石津 敦
東京大学農学部
Photolysis of α−keto, β-aryl ether type lignin model compounds
Nobutaka Fukagawa, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: β-aryl ether cleavage, coloration，high pressure mercury lamp,
1989-206
リグニンの水素化分解 —HRI の報告についての検討—
小山 実、金沢健治、小川博嗣
化学技術研究所
Hydrocracking of lignin, —Investigation of the report by HRI—
Makoto Koyama, Kenji Kanazawa, Hirotsugu Ogawa
National Chemical Laboratory for Industry
Keywords: HRI (Hydrocarbon Research Inc.) process, improved Noguchi process,1989-207
シユードモナス属細菌 TMYl009 株のジアリールプロパン型モデル化合物の Cg 脱離酵素について
岸 克行*1、羽生直人*1*2、鮫島正浩*1、善本知孝*1*1
東京大学農学部、*2 ダイセル化学株式会社
Studies on the Cg eliminating enzyme from the diaylpropane type lignin model compounds produced by
Pseudomonas sp. TMY1009
Katsuyuki Kishi*1, Naoto Habu*1*2, Masahiro Samejima*1, Tomotaka Yoshimoto*1*1
Faculty of Agriculture, the University of Tokyo, *2Daicel Chemical Industries Ltd.
Keywords: gel electrophoresis, mass spectrometry
1989-208
リグノスチルベン-α、β-ジオキシゲナーゼ I に含有される鉄と酵素活性との関連性について
鴨田重裕*1、羽生直人*1*2、鮫島正浩*1、善本知孝*1*1
東京大学農学部、*2 ダイセル化学株式会社
Relationship between iron and enzyme activities in lignostylbene-α,β-dioxigenase I
Shigehiro Kamoda*1, Naoto Habu*1*2, Masahiro Samejima*1, Tomotaka Yoshimoto*1*1
Faculty of Agriculture, the University of Tokyo, *2Daicel Chemical Industries Ltd.
Keywords: gel electrophoresis, Fe-chelater,
1989-209
バイオミメティック Mn／Co 触媒とリグニナーゼによる β-O-4 二量体の酸化分解反応
中川麻理子、島田幹夫、樋口隆昌
京都大学木材研究所
Oxidative degradation of β-O-4 type dimer by biomimetic Mn／Co catalyst and ligninase
Mariko Nakagawa, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phanerochaete chrysosporium, lignin peroxidase, total ion chromatography
1989-210
白色腐朽菌による漂白排液の脱色：モデル化合物の分解・代謝機構の検討
187

桃原郁夫、松本雄二、石津 敦
東京大学農学部
Decoloration of bleach effluent by white rot fungi: Degradation of model compounds and investigation of
metabolic mechanism
Ikuo Momohara, Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: naphthoquinone, anthraquinone, lignin peroxidase
1989-211
白色腐朽菌による漂白排水の突然変異原性の除去
渋谷征男、松本雄二、石津 敦
東京大学農学部
Removal of mutagenicity from bleach effluent by white rot fungi
Masao Shibuya, Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Keywords: Phanerochaete chrysosporium, 1,3-dichloroacetone, Ames test
1989-212
シリンギル及びビフェニール型リグニンモデル化合物芳香環のリグニンペルオキシダーゼによる開裂
服部武文、島田幹夫、樋口隆昌
京都大学木材研究所
Aromatic ring cleavage of syringyl and biphenyl type lignin model compounds by lignin peroxidase
Takefumi, Hattori, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Keywords: Phanerochaete chrysosporium, non-phenolic syringyl type compounds, 1H-NMR, GC-MS,
1989-213
カワラタケによるリグニン生分解機構の解析
飯村洋介、片山義博、田村利香、中村雅哉、諸星紀幸
東京農工大学農学部
Investigation of lignin biodegradation mechanism by Coriolus vercicolor
Yosuke Iimura, Yoshihiro Katayama, Rika Tamura, Masaya Nakamura, Noriyuki Morohoshi
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Keywords: 14C tracer, 13C tracer, 14C -DHP, 13C-DHP, GPC
1989-214
木材腐朽菌によるリグニンモデル配糖体の生成について(VII) カワラタケによるキシロース配糖体の生成機
構
迫 孝、近藤隆一郎、今村博之
九州大学農学部
Formation of lignin model glycoside by wood rotting fungi (VII), Formation mechanism of xyloside by
Coriolus vercicolor
Takashi Sako, Ryuichiro Kondo, Hiroyuki Imamura
Faculty of Agriculture, Kyushu University
Keywords: 14C tracer, 14C-glucose, 13C tracer, 13C-glucose, 13C-NMR
1989-215
木材腐朽菌によるリグニンモデル配糖体の生成について(VIII) カワラタケによるリグニン生分解おけるキシ
ロース配糖体生成の役割
追 孝、山上 陽、近藤隆一郎、今村博之
九州大学農学部
Formation of lignin model glycoside by wood rotting fungi (VIII), The role of the formation of xyloside inbiodegradation of lignin by Coriolus vercicolor
Takashi Sako, Hikari Yamagami, Ryuichiro Kondo, Hiroyuki Imamura
188

Faculty of Agriculture, Kyushu University
Keywords: Fagus crenata , 14C tracer, 14C-glucose, veratryl-β-D-xyloside, GPC
1989-216
リグニン・多糖複合体のモデル高分子 —細胞特異性の生医学材料としての応用—
小 林
*1
*2
一清 、赤池敏宏*1
名古屋大学農学部、*2 東京農工大学工学部
Macromolecular models of lignin-polysaccharide complex, —Application to cell-specific biomedical material
Kazukiyo Kobayashi*1, Toshihiro Akaike*2*1
Faculty of Agriculture, Nagoya University, *2Faculty of Engineering, Tokyo University of Agriculture andTechnology
Keywords: LCC, oligosaccharide-carrying polystyrene, oligosaccharide, hepatocytes
1989-217
水溶性リグニンの免疫活性及び抗ウイルス活性
鈴木春巳*1、飯山賢治*1、栃倉匡文*2、山崎素直*1、山本直樹*2、戸田昭三*1*1
東京大学農学部、*2 山口大学医学部
Immunological and antiviral activities of water soluble lignin
Harumi Suzuki*1, Kenji Iiyama*1, Tadafumi Tochikura*2, Sunao Yamazaki*1, Naoki Yamamoto*2, Shozo Toda*1*1
Faculty of Agriculture, the University of Tokyo, *2School of Medicine, Yamaguchi University
Keywords: Lentinus edodes, bagasse, lignosulfonate, polyanion
1989-218
リグニン樹脂接着剤の製造
佐野嘉拓、遠藤 稔、遠藤健一
北海道大学農学部
Production of lignin based adhesives
Yoshihiro Sano, Minoru Endo, Kenichi Endo
Faculty of Agriculture, Hokkaido University
Keywords: Abies sachalinensis, cresol lignin, kraft lignin, lignin-phenol resin
1989-219
光学活性基を有するリグニン関連型液晶の合成とその物性（1）春日和行*1、畠山兵衛*1、畠山立子*2*1
製品科学研究所、*2 繊維高分子材料研究所
Synthesis and properties of lignin-related liquid crystal with optically active groups (I)Kazuyuki Kasuga*1, Hyoe Hatakeyama*1 Tatsuko Hatakeyama*2*1
Industrial Products Research Institute, *2Institute for Textiles and Polymers
Keywords: DSC, X-ray diffraction, vanillic acid methyl ester
1989-特別講演
リグニンはどのように糖と結合するか
越島哲夫
京都大学木材研究所
Invited lecture ; How lignin is bonded to carbohydrate ?
Tetsuo Koshijima,
Wood Research Institute, Kyoto University
Keywords: Pinus densiflora, Björkman LCC, GPC, DDQ, 2.3-dichloro-5.6-dicyano-p-benzoquinone,

189第 35 回 （1990.10.15-16） 東京大学 山上会館
1990-101
水溶性リグニンの溶液中の挙動
渡辺正介、飯塚堯介、石津 敦
東京大学農学部
Behavior of water soluble lignin in aqueous solution
Masasuke Watanabet, Gyosuke Meshitstlka, Atsushi lshizu
Faculty of Agriculture. the University of Tokyo.
Abstract:
Behavior of water soluble lignin in ion-exchanged water in the presence of surface-active agents, such as
sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfonate(SDB), vas investigated with gel filtration
chromatography using Sepharose CL-2B. With a surface-active agent, a remrkable change in gel filtration curves of sodium
lignosulfonate (LSA). that is, shift to at low molecular weight region was observed. These results seen to indicate theaggregation of LSA molecules which carry both of hydrophilic and hydrophobic domains, and the molecular association of
LSA was thought to be attributed to the hydrophobic inter molecular interaction.
1990-102
ポリフエノール類のタンパク質吸着能について
河本晴雄、中坪文明、村上浩二
京都大学農学部
Protein--adsorption capacily of polyphenols
Haruo Kawamoto, Fumiali Nakatsubo, Kouji Murakami
Protein--adsorption capacity of polyphenols
Abstract:
Several kinds of condensed tannins were successfully synthesized and the relationships between the
structure and the protein precipitating capacity were examined. This examination revealed that the distribution pattern of thephenolic hydroxyl groups in tannin molecule, not the existence of o-dihydroxyl- phenyl groups, is important for higher
protein-precipitating capacity. Thus, these results suggest that 1ignin should also have the protein-adsorption capacity, if thephenolic hydroxyl groups are located in the appropriate positions of lignin molecule. Then, the protein-adsorption capacity ofseveral kinds of lignins was tested. Consequently, thiolignin and steam explosion lignin were found to have the higher
capacity than commercial available immobilized tannin.
1990-103
放射線照射によるリグニンの特性変化について
古屋信子、菱山正二郎、須藤賢一
森林総合研究所
Characterization of lignin from γ-ray irradiated wood
Nobuko Furuya, Shojiro Hishiyama, Ken-ichi Sudo
Forestry and Forest Products Reserch Institute
Abstract:
The chemical feature of lignin from wood irradiated by 25-100 Mrad of γ-ray irradiated was investigated.
The dioxane lignin (DL) was isolated from untreated and irradiated woods according to Pepper's method. The
yield of DL was higher compared with that of untreated wood, though it depends on the radiation dose. The yielcl of DL fromthe wood treated by 50 Mrad of irradiation dose was about 40%, whereas that from the untreated wood was 27%. The averagemolecular weight of DL from the irradiated wood increased with increasing the irradiation dose. The amounts of phenolic-OH
and methoxyl groups in DL decreased with increasing the irradiation dose. The relative amounts of C and H in DL from
γ-irradiated wood had a tendency to decrease, whereas that. of oxygen increased. The yield of nitrobenzene oxidation products
ranged from 11.9 to 18.2% depending to the irradiation dose. This shows that lignin in wood changes both decomposition andcondensation by γ-irradiation. From these results, it is indicated that lignin in wood changes in the chemical structure to someextent in mo1ecular weight, functional groups and so on.
1990-104
リグニンの水素化分解 —数種の触媒の検討—
小山 実
化学技術研究所
Hydrocracking of lignin, —Montmorillonite catalysts—
Makoto Koyama
190

National Chemical Laboratory for Industry
Abstract:
A kraft lignin (KL) and lignin model diners were hydrocracked with Fe-, Ni-. Co-, andMo-montmorillonite-S (Mo-Mtm-S) as catalysts. Yields of monophenols and benzenes from hydrocracking of
2-hydroxybiphenyl by 450 ºC, 50 minutes with Fe-Mtm-S were about 10 and 25 %, respectively. Abouthydrocracking of KL with Fe-Mtm-S, yields of monophenols were similar to, but depolymerization of KL was
more promoted than it with Fe/Alumina-S catalyst.
1990-105
リグノセルロース熱分解物を原料とするポリウレタンの熱的性質
広瀬重雄、畠山兵衛
製品科学研究所
Thermal properties of polyurethanes derived from thermal degradation products of lignocellulose Shigeo Hirose,
Hyoe Hatakeyama
Industrial Products Research Institute, Tokyo
Abstract:
A liquid and charcoal were obtained by the thermal degradation of Eucalyptus.
The liquid was distilled at 230 ºC and the solid residue was obtained. The residue was found to contain 5.8mmol/g of the hydroxyl group. Polyurethanes (PU's) were prepared from the residue, polyethylene glycol (PEG)
400 and diphenylmethane diisocyanate (MDl). Thermal degradation of PU's Was studied by thermogravimetry(TG). The effect of the addition of residue to PU,s is considered in this paper.
1990-106
ユーカリリグニンからのポリウレタンフォームの力学的性質
中村邦雄*1、畠山兵衛*2、J. Meadows*3、P.A．Williams*3、G.0．Phillips*3*1
大妻女子大学, 製品科学研究所、*3Northeast Wales InstituteMechanical properties of polyurethane foam derived from Eucalyptus lignin
Kunio Nakamura*1, Hyoe Hatakeyama*2, J. Meadows*3、P.A．Williams*3、G.0．Phillips*3*1
Otuma Women's University, *2Industrial Products Research Institute, *3Northeast Wales Institute
Abstract:
Polyurethane (PU) from Eucalyplus lignin (EL) and polyol were prepared as follows: EL
was dissolved ln polyethylene glyco1 (PEG) having a molecular Weight of 400 at 50 ºC for1 hour. PU foam was
obtained by the reaction between the polyol and diphenylmethane diisocyanate (MDl). The EL content in PU
foam and MDl/polyol ratio were varied in order to obtain different kinds of PU foam. The density of PU foam,compression strength and elasticity were measured using the weight method and a LLoyd INSTRUME:NT
T30K Mode1. Thermal properties of the PU foam prepared were measured by differential scannlng calorimetry(DSC).
1990-107
リグニン系炭素繊維の基礎物性とその応用
中嶋信之*1、横山 昭*1、須藤賢一*2、志水一允*2*1
日本カーボン株式会社、*2 森林総合研究所
Propert.ies and applications of lignin based carbon fiber
Nobuyuki Nakajima*1, Akira Yokoyama*1, Kenichi Sudo*2, Kazumasa Shimizu*2*1
Nippon Carbon Co., Ltd., *2Forestry and Forest Products Research Institute,
Abstract:
Preparation methods for lignin based carbon fiber (LCF) were investigated. Raw lignin was
extracted from steam-exploded white birch. After mild hydrocracking followed by heat treatment under reducedpressure, the lignin shoved excellent spinnability in melt-state. Crystallinity of LCF is somewhat lower than thatof another kind of carbon fiber. As to mechanical properties, LCF is classified into general purpose carbon fiber.
Tensile strength of LCF is 40-60kg/mm2. After steam activation, the specific surface area increased to
2000m2/g. The bending strength of LCF/cement composite was about 100kg/cm2 at 7vol.% fiber content.
LCF/Epoxy-resin composite showed the bending strength of 25-30kg/mm2 and about 3kg/mm2 of inter laminarstrength.
1990-108
Albizia falcata 材のリグニン・多糖結合体について
渡辺隆司*1、今村剛士*1、越島哲夫*2、Myrtha Karina*3*1
京都大学木材研究所、*2 近畿大学農学部、*3LIPI,P3FT
191

Lignin-carbohydrate complexes from Albizia falcata wood
Takashi Watanabe*1, Takeshi lmamura*1, Tetsuo Koshijima*2, Myrtha Karina*3*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture Kinki University, *3Research andDevelopment Centre for Applied Physics. Indonesian Institute of Sciences
Abstract:
Lignin-carbohydrate complexes (LCCs) were isolated from tropical hard wood of Albizia
falcata Backer by a modified Björkman method. After extraction of milled wood lignin from the hard wood,
LCCs were isolated by successive extraction of the wood residue with water and 4% aqueous NaOH. NMR andrnethylation analysis indicated that the alkali-soluble fraction was composed of glucuronoxylan-lignin complex
and that a neutral xylan chain existed in the water-soluble LCC fraction.
1990-109
Forsythia intermedia のリグナン生合成酵素について
梅澤俊明（Toshiaki Umezawa ）*1、Laurence B. Davin*2、Norman G. Lewis*2*1
Commonwealth Center for Wood Science and Technology/ *2Department ofBiochemistry, Virginia Polytec
Institute and State University
Formation of optically pure lignans by cell free extracts of Forsythia Intermedia
Toshiaki Umezawa, *1, Laurence B. Davin*2, Norman G. Lewis*2*1
Commonwealth Center for Wood Science and Technology/ *2Department ofBiochemistry, Virginia Polytec
Institute and State University
Abstract:
A crude cell-free extract from Forsythia IntermEdina catalyzes the formation of(-) -secoisolaliciresinol, and not its (+) –enantiomer, when incubated with coniferyl alcohol in the presence ofNAD(P)H and H202. This extract also catalyses the oxidation of (-)-secoisolariciresinol, but not its(+)-enantiomer, to (-)-matairesino1. This is the first report of an enzyme reaction specifically involved in the
coupling between two phenyl-propanoid monomers to afford an optically pure lignan.
1990-110
リグノール類の脱水素重合
内田洋介、寺島典二
名古屋大学農学部
Dehydrog:enative polymerization of lignols
Yousuke Uchida, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Abstract:
In order to examine the factors affecting formation of condensed structures in protolignin
macromolecule, coniferyl alcohol, p-coumaryl alcohol and sinapyl alcohol were polymerized dehydrogenatively
under different pHs and in the presence of different kinds of polysaccharides. The proportion of three main
dilignols, β-0-4, β-5, and β-βtypes, formed in the earliest stage of polymerization was affected greatly by the pH.
Under low pH and in the presence of an acidic polysaccharide, pectin, the proportion of condensed type β-5
dimer, dehydrodiconiferyl alcohol, was higher than that found under high pH and in the absence of pectin or in
the presence of less acidic hemicelluloses.
1990-111
広葉樹培養細胞のリグニン生成とペルオキシターゼアイソザイムの基質特異性について
堤 裕司、坂井克己
九州大学農学部
Lignin biosynthesis and substrate specificities of peroxidase isoenzymes with respect to syringyl and guaiacyl
structures in angiosperm tree callus cultures
Yuji Tsutsumi, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We investigated the possibility that substrate specificities of peroxidase isoenzymes can control
syringyl lignin contents in xylem tissues. Peroxidase isoenzymes from Populus callus cultures were fractionatedto three isoenzyme groups, soluble peroxidase (SPO), ionically bound peroxidase (IPO) and wall boundperoxidase (WPO). The substrate specificities of these isoenzyme groups with respect to syringyl and guaiacyl
substrates were investigated. The speclflcity of IPO to syringyl substrate was the highest, among three
peroxidase isoenzyme groups. Though the severe water stress applied to the calluses elevated both their lignin
content and peroxidase levels, the specificity to syringyl substrate and syringyl lignin content determined bynitrobenzene oxidation were decreased. The peroxidase isoenzyme groups from Cryptomeria calluses exhibited192

the lower specificity to a syringyl substrate. These results suggest that the syringyl lignin biosynthesis iscontrolled not only by the lignin monomer supply but also by the substrate specificity of peroxidase in the last
step of lignin formation, that is dehydrogenetive polymerization catalyzed by peroxidase in angiosperm xylem
tissues.
1990-112
食用担子菌の生産するフエノール酸化酵素
小藤田久義、太田朋子、松下敦史、麻田恭彦、桑原正章
香川大学農学部
Phenol oxidase and peroxidase produced by edible mushrooms
Hisayoshi Kofujita, Tomoko Ohta, Atsushi Matsushita, Yasuhiko Asada,
Masaaki Kuwahara
Faculty of Agriculture, Kagawa University,
Abstract:
Phenol oxidase and peroxidases were produced by Lentinus edodes and Pleurotus ostreatus inliquid and solid state cultures containing low or high nitrogen source. Lignin peroxidase activity was negligible
in these culture conditions. Laccase produced in the wheat bran medium by L. edodes and Mn(II)-peroxidase
produced in the glucose-peptone medium by P. ostreatus were purified to homogeneity by various
chromatography. In most properties of each enzyme, laccase of L. edodes and Mn(II)-peroxidase of P. ostreatus
were similar to that of Coriorus versicolor or Phanerochaete chrysosporium. Both of these enzymes degraded
the phenolic β-0-4 lignin substructure model compound, syringylglycerol-β-guaiacyl ether (I). The structure ofdegradation products indicated that these two enzymes catalyze alkyl-aryl cleavage of substrate I.
1990-113
木材腐朽菌による木材の水溶性化挙動について
迫 孝、近藤隆一郎、坂井克己
九州大学農学部
Water solubilization of wood by white-rot fungi during wood decaying process
Takashi Sako, Ryuichiro Kondo and Kokki Sakai
Faculty of Agriculttlre, Kyushu University
Abstract:
In previous papers, we reported that Coriolus versicolor transformed lignin model compounds
into their xylosides in various sugar media. We tried to clarify the possibility of the formation oflignin-glycosides during the biodegradation of lignin by C. versicolor in 14C-glucose and 13C-glucose media. On
the basis of the results of the incorporation of radioactivities into fungus treated lignin and the 13C-NMR
spectrum of the treated lignin, it was suggested that lignin was possibly transformed into its xylosides by C.
versicolor. To get a better understanding of biodegradation of wood by wood-rot fungi, we attempted to decay
beech wood meal with by white-rot fungi, C. versicolor and Phanerochaete chrysosporium for various period,and investigated the water soluble fraction of decayed wood meals. In C. verslcolor cultivation, the lignin
components in the water soluble fraction were seemed to be degraded severely. On the other hand, the dissolved
lignin components from wood meals decayed by P. chrysosporium were seemed to be relatively stable in theculture medium. Therefore, it was suggested that these fungi might have different catabolic system to degrade
lignin.
1990-114
ベラトリル β-D-キシロシド共存下におけるリグニンペルオキシターゼによるリグニンモデル化合物の分解
服部武文、島田幹夫、樋口隆昌
京都大学木材研究所
Degradation of a lignin model compound by lignin peroxidase in the presence of veratryl βD-xyloside
Takefumi Hattori, Mikio Shimada, Takayoshi Higuchi
Wood Research Institute, Kyoto University
Abstract:
Addition of veratryl alcohol and/or veratryl β-D-xyloside enhanced Cα-Cβ cleavage reaction ofl,2-bis(4-methoxyphenyl)propane-l,3-diol (I) which was a poorer substrate for lignin peroxidase than veratryl
alcohol. The rate of degradation (I) was greater with veratryl alcohol than with veratryl β-D-xyloside, however
veratryl β-D-xyloside was more stable than veratryl alcohol during reaction. Mixed type of competitive andnoncompetitive inhibition pattern of Lineweaver-Burk plots obtained suggests that veratryl alcohol not only
prevent lignin peroxidase from inactivation but also acts as a radical mediator.
193

1990-115
キノン型化合物のリグニンパーオキシダーゼによる分解
桃原郁夫、松本雄二、石津 敦
東京大学農学部
Degradation of a quinone model compound by lignin peroxidase
Ikuo Momohara, Yuji Matsumoto, Atsushi Ishizu
Facult,y of Agriculture, the University of Tokyo
Keywords: Phanerochaete chrysosporium, 1ignin peroxidase, superoxide anion, quinone, decolorization,veratryl alcohol
Abstract:
A quinone model compound, 2-hydroxy-1,4-naphthoquinone (HNQ), is degraded by lignin
peroxidase when veratryl alochol is present. Spectral study of this reaction system indicated that the presence of
HNQ inhibits the oxidation of veratryl alcohol by lignin peroxidase and, thus, the formation of veratraldehyde
starts only after the degradation of HNQ. Degradation rate was remarkably increased by the increase in veratryl
alcohol concentration. Degradation was partly and completely prevented by adding a OH• scavenger (mannitol)
and a O2-scavenger (Mn2+), respectively. These results suggest that active oxygen species formed in lignin
peroxidase - H2O2 - veratryl alcohol system play an important role in HNQ degradation.
1990-116
フエノール性 β-O-4 型リグニンモデル二量体のリグニンペルオキシダーゼによる分解
横田信三*1、（京大木研）梅澤俊明*2、樋口隆昌*2*1
宇都宮大学農学部、*2 京都大学木材研究所
Degradation of phenolic βO-4 lignin model dirners by lignin peroxidase
Shinsou Yokota*1, Toshiaki Umezawa*2, Takayoshi Higuchi*2*1
Faculty of Agriculture, Utsunomiya University, *2Wood Research Institute, Kyoto University
Abstract:
Degradation of three kinds of phenolic β-O-4 1ignin model dimers,1-(4-hydroxy-3methoxy-pheny1)-2-(2-methoxyphenoxy)-1,3-propanediol(I),
1-(4-hydroxy-3-methoxyphenyl)-2(2,6-dimethoxyphenoxy)-1,3-propanediol(II)and
1-(4-hydroxy-3,5-dimethoxyphenyl)-2(2-methoxy-phenoxy)-1,3-propanediol (III), by lignin peroxidase was investigated. Of these three substrates,
substrate III was degraded to the following six compounds: guaiacol (IV) , syringaldehyde (V), syringic acid(VI),
2,6-dimethoxy-p-hydroquinone(VII),
2-(2-methoxy-phenoxy)-2-propenal
(IX),
and
1-(4-hydroxy-3,5-dimethoxyphenyl)-2-(2-methoxyphenoxy)-2-propene-1-one (X). The results showed that
substrate III was degraded via alkyl-aryl cleavage, Ca-Cb cleavage, and Ca oxidation by lignin peroxidase.
1990-117
リグニンペルオキシダーゼ（LiP）系による新しいシュウ酸分解反応とその生理的意義
島田幹夫*1、馬 登波*1、樋口隆昌*1、赤松やすみ*2*１
京都大学木材研究所、*2 福井グリーンセンター
A new enzymatic decarboxylation of oxalic acid by lignin peroxidase (Lip) system and its physiological role
Mikio Shimada*1, Denbo Ma*1, Takayoshi Higuchi*1, Yasumi Akamatsu*2,*1
Wood Rsearch Institute, Kyoto Uniersity, *2General Green Center, Fukui Prefecture.
Abstract:
A new enzymatic decarboxylation of oxalic acid by lignin peroxidase (LiP) system) was
discovered. Oxidation of veratryl alcohol by LiP vas potently inhibited by oxalic acid. The inhibition analysis
clearly showed that the type of inhibition is noncompetitive. The apparent noncompetitive inhibition of LiP is
explained as such that the veratryl alcohol cation radical
intermediate formed by LiP is reduced back toveratryl alcohol by oxalic acid and consequently formation of veratraldehyde is blocked. The addition of oxalic
acid into the ligninolytic culture of Phanerochaete chrysosporium also inhibited decomposition of synthetic
lignin to CO2. The results indicate that oxalic acid as a secondary metabolite of white-rot fungi controls lignin
deconposition on one side and veratryl alcohol acts as a mediator for decomposition of oxalic acid on the other.
1990-118
特別講演: リグニンの生化学：生合成と生分解
樋口隆昌
京都大学木材研究所
Special lecture: Lignin biochemistry: Biosynthesis and biodegradation
194

Takayoshi tliguchi
Wood Research Institute, Kyoto University
Abstract:
Lignin biosynthesis via shikimate-cinnamate pathways in plants, and the biosynthetic
differences of guaiacyl- and syringyl lignins between gymnosperms and angiosperms have been elucidated bytracer experiments using 14C labeled precursors and the following enzyme reactions. The main cleavage
mechanisms of propyl side chain and aromatic ring opening of lignin model compounds and synthetic lignin(DHP) by white-rot fungi and their enzymes, lignin peroxidase and laccase have been elucidated using 2H, 13C
and 18O-labeled lignin substructure dimmers with 18O2 and H218O. Side chains and aromatic rings of thesesubstrates were cleaved via aryl cation radical and phenoxy radical intermediates, in reaction mediated only bylignin peroxidase and laccase.
1990-201
リグニンのメカノケミストリー（第 7 報）ベラトリルグリセロール-β-シリンガアルデヒドエーテルのメカノケミカル反応
呉 宗華、住本昌之
九州大学農学部
Mechanochemistry of lignin (VII), Mechanochemical reaction of veratryl-β-syringaldehyde ether
Zonghua Wu, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Abstract:
Veratrylglycerol-β-syringaldehyde ether (M) was treated with CBM, VBM and KRKrefiner to find out the mechanochemical conversion products. Under the conditions treated, about 20% of thestarting materials (M) were converted to give veratryl propan-1-on-3-ol 1, syringaldehyde 2,
2,6-dimethoxy-p-hydroquiqone 3, 2,6-dimethoxy-p-benzoquinone 4, vanillin 5 , veratrylalcohol 6.
syringaldehydeglycol ether 7 and a condensation product 8. Formation of a chromophore
2.6-dimethoxy-p-benzoquinone 4, a leucochromophore 2,6-dmethoxy-p-hydro- quinone 3 , andpara-carbonylphenols 2 and 5 should be deeply related to the color of unbleached pulp and color reversion of
bleached mechanical pulp.
1990-202
高収率パルプ製造時のリグニンの挙動 (III) p-カルボニルフエノールを有する β-O-4 型モデル化合物の合成とそのメカノケミストリー
伊藤和貴*1、橘 燦郎*2、住本昌之*1*1
九州大学農学部、 *2 愛媛大学農学部
Behaviours of lignin during production of high-yield pulp (III) - Synthesis and mechanochemical conversions of
β-O-4 lignin model compound having a para-carbonyl phenol Kazutaka Ito*1, Sanro Tachibana*2, Masashi Suninoto*1*1
Faculty of Agriculture, Kyushu University, *2Faculty of Agriculture, Ehime University
Abstract:
Trials for the improved method of synthesis of β-O-4 lignin model compounds (I)[3-methoxy-4-hydroxy-α-(2-nethoxyphenoxy)- β-hydroxypropiophenone] were made first.
The second one (II) [3,5-dinethoxy-4-hydroxy-α-(2-methoxyphenoxy)- β-hydroxypropio- phenone], however,
had to be synthesized by the relatively different method. By the Mechanical treatments of the latter modelcompound (II) as a representative of a biphenyl model (III) and a biphenyl ether model (IV) with VBM and
CBM, 2,6-dimethoxy-p-benzoquinone and others were obtained in reasonable yields.
1990-203
クラフト蒸解中難分解性リグニンの漂白過程における反応
細谷修二、島田謹爾、富村洋一
森林総合研究所
Reactions of pulping-resistant structure in lignin during bleaching
Shuji Hosoya, Kinji Shimada, Yoichi Tomimura
Forestry and Forest Products Research Institute
Abstract:
Reactions of veratrylglycerol-α-ethyl-β-guaiacyl ether (VEG) during bleaching were
investigated. This lignin model compound represents the kraft pulping-resistant and oxygen bleaching-resistant
structures in lignin. By chlorine treatment, about 3 moles of chlorine per mole of VEG were very quickly taken
up for the unfavorable chlorination reaction. Only after this chlorination reaction was observed the extensive
195demethylation reaction which leads to favorable delignification reaction. α-Ethyl ether was never cleaved bychlorine treatment. Nitrogen dioxide and chlorine dioxide were not reactive to VEG. Acetic acid containing
small amount of HCl (0.1% w/v) effectively cleaved the α-ether bond giving almost theoretical yield of ethyl
acetate. Acetic acid treatment of KP and oxygen bleached KP (KOP) resulted in large drop in kappa number (Fig.
2). As a conclusion, we propose new non-chlorine bleaching sequence: either Oxygen-Acid Treatment-Chlorine
Dioxide or Acid Treatment-Oxygen-Chlorine Dioxide.
1990-204
さらしパルプ中に検出されるダイオキシンの前駆体に関する一考察 塩素経換反応におよぼすリグニンの影響
阿部善作*1、P. Ljungquist*2、F. de Sousa*2、K. P．Kringstad*3*1
九州大学農学部、*2STFI、*3Norske Skogindustrier AS
An investigation on precursors of dioxins detected in bleached kraft pulp (Influence of lignin on chlorine
substitution reaction in chlorine water)Zensaku Abe*1, Pirre Ljungquist*2, Filipe de Sousa*2, Knut P. Kringstad*3*1
Faculty of Agriculture, Kyushu University, *2STFI,Stockholm, Sweden, *3Norske Skogindustrier AS, Honefoss,
NorwayAbstract:
The investigation was done to obtain a better understanding of the reason why the ratio of
2,3,7,8-tetrachlorodibenzofuran (TCDF) to 1,2,7,8-TCDP detected in bleached kraft pulp is almost two and of
the precursors of PCDFs. The ratios of 2,3,7,8-TCDF to 1,2,7,8-TCDF formed during the chlorination of
uncblrinated dibenzofuran without pulp in chlorine water at different reaction conditions are about one,respectively. And also the ratio with bleached pulp is one. But 2,3,7,8- TCDF was formed more than three tinesof 1,2,7,8-TCDF during the chlorination of dibenzofuran with unbleached pulp using chlorine water. These
results show that lignin of unbleached pulp oriented chlorine substitution in the chlorination using chlorinewater and that unchlorinated dibenzofuran may be a precursor of PCDFs.
1990-205
N02 前処理酸素漂白法の機構について
大井 洋、Thomas. J. McDonoughInstituteofPaper Science and Technology
Mechanism of nitrogen dioxide pretreatment for oxygen bleaching
Hiroshi Ooi, Thomas. J. McDonoughInstitute of Paper Science and Technology
Abstract:
Pretreatment of kraft pulp with nitrogen dioxde has been shown to be an effective method forboth improvement of delignification and protection of carbohydrate degradation in oxygen bleaching. However,
the mechanism of its action is not clear. The objective of this research is to learn more about the mechanism.
1990-206
硫酸触媒による広葉樹材の常圧酢酸パルプ化 —パルプ化条件の検討
佐野嘉拓、島本 周
北海道大学農学部
Abstract:
Aqueous acetic acid pulping of hardwoods at atmospheric pressure with a sulfuric acid catalyst
pulping conditions
Yoshihiro Sano and Shu Shimamoto
Faculty of Agriculture, Hokkaido University
Abstract:
Pulping of hardwoods at atmospheric pressure with 90% AcOH containing a small amount ofsulfuric acid was investigated. The hardwoods were boiled for 0.5 hours in 90% AcOH for pretreatment, andthen for 2-3 hours in 90% AcOH with 1.6-2.0% H2SO4 of wood for pulping. The hardwoods used wereclassified roughly into three groups on basis of the results of pulping. The 1st, class (birch) is pulped with easeby these procedure, the 2nd class (alder, beech, eucalyputus and poplar) with less difficulty and the 3rd class(acacia) with difficulties. Also lignin model compounds with ether were degraded under similar conditions to
the pulping of hardwoods in order to clarify the reaction mechanism of lignin. The ether compounds were
found to be reacted by the same mechanism as acetic acid pulping without H2SO4 at elevated temperatures.
1990-207196

硫酸触媒による広葉樹材の常圧パルプ化 —酢酸リグニンの樹脂接着剤への応用
中村雅幸、佐野嘉拓
北海道大学農学部
Pulping of hardwood at atmospheric pressure with sulfuric acid catalyst, –Preparation of lignin based resin
adhesives
Masayuki Nakamura, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Utilization of lignin in the substrate of phenol resins was investigated. Commercial kraft lignin
and acetic acid lignin (AWL) prepared by acetic acid pulping of birch at atmospheric pressure were used aslignin. A mixture of lignin and phenol was condensed with HCHO in aqueous methanol under alkalineconditions in order to produce phenol-type resins. When 80% of phenol was replaced by each lignin, theresulting resins met JIS for phenol-type resins. When 20% resorcinol added to the resins, the press temperature
was depressed to 100ºC. AWL and lignin model compounds were reacted with HCHO under acidic conditions inorder to yield more activated hydroxymethylated lignin. Lignin reacted under acidic conditions were found tocontain twice amounts of hydroxymethyl groups than that under alkali conditions.
1990-208
オイルパーム副産物のケミサーモメカニカルパルプ化
赤松 勲*1、上嶋 洋*1、細川 純*1、D.H.A.H．Hassan*2*1
四国工業試験所, *2 Palm Oil Research Institute of Malaysia
Chemi-thermomechanical pulp of oil palm byproducts
lsao Akamatsu, Hiroshi Kamishima, Jun Hosokawa, Datuk Haji Abdul Halim Hassan
Government Industrial Research lnstitute of Shikoku
Abstract:
With increasing demand of pulp and paper production, the new raw materials for pulp havebeen investigated with the purpose of higher utilizing of ligno-cellulosic oil palm by-products. Empty
fruit bunch frond and trunk were pulped by anthraquinone-KP and TMP process. From the yield and sheet
properties, frond was selected as the optimum raw material and CTMP process the appropriate one. The fungus
attack to frond was prevented by pretreatment with some chemicals, including alkalis, bunch ash. Plant scale
CTM-pulping showed almost the same results as the laboratory studies using the alkali pretreated fronds. The
rolled paper produced corrugating medium and corrugated boards with the satisfied strengths. The
characteristics of CTMP waste water were also studied and the biological treatability was tested.
1990-209
未利用林産資源の酵素、微生物による変換利用（2）高知県産広華樹 35 種の水蒸煮処理パルプの酵素糖化率
鮫鳥一彦*1、藤原新二*1、黒田健一*2、高村意男*1
高知大学農学部、筑波大学農林工学系
Enzymatic and microbial conversion of unused forest product resources for further utilization (II), The
susceptibility to the enzymatic saccharification of steam-cooked pulps made from thirty-five hardwoods ofKochi growth
Kazuhiko Sameshima*1, Shinji Fujiwara*1, Kenichi Kuroda*2, Norio Takamura*1*1
Faculty of Agr., Kochi University, *2Instittlte of Agricultural and Forestry Engineering, Tsukuba University
Abstract:
The Asplund pulps made from thirty-five Japanese hardwoods of Kochi growth were tested fortheir susceptibilities to the enzymatic saccharification with Trichoderna viride cellulase, ”Meicelase P-1”. Afterthe chemical analyses of both wood meals of the sample woods
and the pulps were made, the morphological features such as the fiber cell wall area and the fiber cell wall
thickness of each wood samples were measured using art image analysis system. The overall correlations
between the susceptibilities and the chemical and the morphological features showed that only the lignin
contents of both wood meals and pulps have the strongest correlations. Detailed analyses are now being
undertaken.
1990-210
微生物（IZU−154 株）によるクラフトパルプの漂白（第 2 報）
藤田弘毅*1、近藤隆一郎*1、坂井克己*1、樫野由憲*2、西田友昭*2、高原義昌*2*1
九州大学農学部、*2 神戸製鋼所
197

Biobleaching of kraft pulp by the fungus, IZU-154 (II)Koki Fujita*1, Ryuichiro Kondo*1, Kokki Sakai*1, Yoshinori Kashino*2, Tomoaki Nishida*2, Yoshimasa
Takahara*2*1
Factllty of Agriculttlre, Kyushu University, *2Biotechnology Research Lab., Kobe Steel, Ltd.,
Abstract:
The fungus, IZU-154 exhibited the high activity of brightening the beech kraft pulp. The pulp
brightness increased by 21 points to 49% by a five-day treatment associated with a corresponding decrease in
Kappa number from 20.9 to 9.3. Combined fungal (F) and chemical (CED) bleaching gave a pulp with thealmost same brightness (88%) and bleaching yield (94%) as a conventionally CEDED bleached pulp. The
FCED bleaching process could significantly reduce the use of chlorine-based chemicals and the pollution loadof waste liquors, compared to the conventional CEDED process. This is also the first report that softwood kraft
pulp was brightened by the fungal treatment; i.e. IZU-154 treatment increased the brightness of Japanese redpine (Pinus densiflora) kraft pulp by 3l point to 55.9% and decreased kappa number from 35.4 to 5.3.
1990-211
ジリグノール分解性好アルカリ性細菌のプロトプラスト融合及び融合株の性質
葛原憲康、川上日出国
名古屋大学農学部
Protoplast fusion of dilignol degradable alkalophilic bacteria and properties of the fusants
Noriyasu Kuzuhara, Hidekuni Kawakami
Faculty of Agriculture, Nagoya University
Abstract:ln order to improve lignin degrading ability of alkalophilic bacteria, intergeneric protoplast
fusion was carried out. The procedure for protoplast fusion from two strains, Corynebacterium CM-432 andAcinetobacter lwoffi CM-401 has been established. As the selective pressure of the fusants, antibiotics,
kanamycin and penicillin were used. Some promising fusants were isolated. The lignin model compounds
degrading ability and APPL generating ability of the fusants were superior to those of the parental strains.
However, the fusants have grown only on the medium of pH 8.5 and have been devoid of the adaptability forwide pH range such as parental strains.
1990-212
担子菌 Phanerochaete chrysosporium 及び Bjerkandera adusta の生産するリグニンパーオキシダーゼとその遺伝子
桑原正章、木村義雄、岡 豊則、麻田恭彦
香川大学農学部
Characterization of lignin peroxidases and its genes from basidiomycetes Phanerochaete chrysosporium and
Bjerkandera adusta
Masaaki Kuwahara, Yoshio Kimura, Toyonori Oka, Yasuhiko Asada
Faculty of Agriculture, Kagava tJniversity
Abstract:
The basidiomycetes Phanerochaete chrysosporium and Bjerkandera adusta produce multiple
extracellular glycosylated heme peroxidases called ligninases or lignin peroxidases. We have purified andcharacterized major lignin peroxidases of their enzymes. The lignin peroxidase of B. adusta exhibited close
similarity to lignin peroxidase of P. chrysosporium with respect to their basic properties. Also, lignin peroxidase
genes have been cloned from a P. chrysosporium DNA library and a B. adusta DNA library. Nucleotide
sequencing of the gene of B. adusta has revealed that the lignin peroxidase structural gene contains 1,116 bp ofprotein-encoding sequence of which 69 bp encode the signal peptide. Amino acid sequence homology between
the coding gene of B. adusta and the lignin peroxidase gene of P. chrysosporium is 61%.
1990-213
合成 DNA プローブを用いたハイブリダイゼーションによるリグノスチルベン-α,β-ジオキシケナーゼ産生遺伝
子の検出
鮫島正浩、鴨田重裕
東京大学農学部
Detection of the gene encoding lignostilbeneα,βdioxygenases by hybridization with synthetic oligonucleotide
probesMasahiro Samejina, Shigehiro Kamoda
Faculty of Agriculture, Universitv of Tokyo
198

Abstract:
Lignostilbene a, b dioxygenases (LSDs) are the key enzyme responsible for the cleavage of the
Cα-Cβdouble bonds in the metabolism of lignin related compounds by Pseudomonas sp. TMY1009 (Fig.1). To
elucidate the catalytic mechanism of LSD, detailed knowledge of the enzyme structure is required. The analysisof the gene is enable to determine the primary structure of the enzyme. In this study, to clone the gene encoding
LSDs, genomic library of Pseudomonas sp. TMY1009 was constructed with a cosmid vector and two
oligonucleotides corresponding to the partial amino acid sequences of LSD-I were synthesized. Hybridization
between the library and two probes was conducted and several positive colonies were detected (Table 1). The
recombinant cosmid (pMSH25) from one of the positive colonies were digested with several appropriate
restriction enzymes and the physical map of this cosmid was determined. Furthermore, the location of LSD gene
was analyzed by Southern hybridization (Fig.2 and 3).
1990-214
リグニンモデル化合物分解酵素遺伝子のクローニング(XV)10.5 kbp EcoRI 断片の構造および機能の解析
西川誠司*1、川合伸也*1、片山義博*2、山崎真狩*3、諸星紀幸*1*1
東京農工大学農学部, *2 東京農工大学共同研究開発センター, *3 東京大学農学部
Cloning of the genes involved in degradation of lignin model compounds (XV),
Seiji Nishikawa*1, Shinya Kawai*1, Yoshihiro Katayama*2, Makarl Yamasaki*3, Noriyuki Morohoshi*1*1
Faculty of Agriculture,Tokyo University of Agriculture and Technology, *2Cooperative Research Center, Tokyo
University of Agriculture and Technology, *3Faculty of Agriculture, University of Tokyo
Abstract:
We already reported the isolation of the 10.5 kbp EcoRI DNA restriction fragment from P.
paucimobilis SYE-6 chromosomal DNA. When this DNA fragment was inserted in the EcoRI site of vector
plasmid pKT 230, this recombinant plasmid (pVAO1) could transform the vanillic acid- negative strain P. putida
PpY1100 to vanillic acid-positive phenotype. One of the genes carried on this fragment was protocatechuate
4,5-dioxygenase gene and recerltly complete nucleotide sequence of this was determined [1]. In this study, we
showed that the location of protocatechuate 4,5-dioxygenase, 4-carboxy-2-hydroxymuconate-6-semialdehyde
dehydrogenase and 2-pyrone- 4,6-dicarboxylic acid hydrolase genes on the10.5 kbp EcoRI fragment isolated
from Pseudomonas paucimobilis SYK-6 chromosormal DNA.
[1] Noda,Y. and Nishikawa, S. et a1. J. 8acteriol., 1990, Vo1.172,No.5, 2704-2709.
1990-215
リグニンモデル化合物分解酵素遺伝子のクローニング（XVI）β-エーテラーゼ（β-アリールエーテル開裂酵素）
遺伝子の解析
政井英司*1、川合伸也*1、片山義博*2、山崎真狩*3、諸星紀幸*1*1
東京農工大学農学部,*2 東京農工大学共同研究開発センター,*２東京大学農学部
Molecular cloning and analysis of β-etherase gene of Pseudomonas paucimobilis SYK-6
Eiji Masai *1, Shinya Kawai*1, Yoshihiro Katayama*2, Makarl Yamasaki*3, Noriyuki Morohoshi*1*1
Faculty of Agriculture,Tokyo University of Agriculture and Technology,*2Cooperative Research Center, Tokyo
University of Agriculture and Technology,*2Faculty of Agriculture, the University of Tokyo
Abstract:
β-Aryl ether cleavage is essential to the biological degradation of lignin. In this study, we
succeeded in the first isolation of β-etherase gene from cosmid genonic library of Pseudomorms paucimobilis
SYK-6. 1.9kbp Sal 1 fragment encoding β-etherase was subcloned into pUC19 and pTTQ19. This gene wasexpressed in E. coli and expressed products were analyzed. Analysis of nucleotide sequence of this gene iscarrying out.
1990-216
フエニルアラニンアンモニアリアーゼとその遺伝子
黒田宏之
京都大学木材研究所
Phenylalanine ammonia-lyases and their genes
Hiroki Kuroda
Wood Research Institute, Kyoto University
Abstract:
PAL and the genes were preliminary examined before studying PAL genes from woody
plants. First, GenBank and EMBL databases were surveyed by using IDKAS for the primer design in relation to
PCR amplification of the genes. Some of the primers were successfully applied to the Hindlll digested DNA
fragment from IPBPAL(sweet potato). The PCR products cover ca. 200bp fragments localized on the high199

homologous region. Further studies are now on progress. Secondary, visualizing PAL activities, especially on
the PAGE gel, was intended by using fluorescent TLC plate. The product was not visualized on the gel, to which
crude enzyme extract was charged, but the method worked before the PAGE. The threshold concentration forthe detection was less than 0.2 mM, which is equivalent to <0.2 nmole/ml. Detecting the product on the gel may
need more sensitive another method.
1990-217
PCR を用いたフェニルアラニンアンモニアリアーゼ遺伝子の解析
山門幹子*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Phenylafanine ammonia-lyase genes isolated by PCR method
Mikjko Yamakado*1, Shinya Kawai*1. Yoshihiro Katayama*2, Noriyuki Morohoshi*1*1
Faculty of Agriculture. Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology
Abstract:
Polymerase chain reaction (PCR) is an in vitro method for the primer-directed enzymatic
amplification of specific DNA sequences. We have used this technique to isolate phenyalanine ammonia-lyase(PAL) genes. The primers corresponding to highly conserved regions of the PAL genes were used and amplified
partial genomic clones from poplar and tobacco plants. The nucleotide sequences of PCR products showing ∼78.9% similarity with those of PAL genes for bean and parsley, and 89% similarity at the deduced amino acidlevel.
1990-218
アンチセンス RNA 法によるペルオキシダーゼの発現抑制
刑部敬史*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Antisense RNA inhibion of peroxidase gene expression in trans genic tobacco
Keishi Osakahe, Shinya Kawai, Yoshbiro Katayamaa , Noriyuki Morohoshi.
*1Faclllty of Agriculture, Tokyo University of Agriculture and Technology,*2Cooperative Research Center,
Tokyo University of Agriculture and Technology
Abstract:
In order to inhibit of lignin forming peroxidase activities, we have attempted to introduce ofantisense peroxidase gene into N. tabacum. Peroxidase isoenzymes were extracted from transformants andseparated by isoelectric focusing. From the results of isoelectric focusing, dramatic changes were not observed
between isoenyme patterns of wild type and those of transformants. And we obtained 9 clones containing partsof tobacco peroxidase genes (TPOX genes) by polymerase chain reaction method. Parts of TPOX genes were
determined.
1990-219
Agrobacterium tumefaciens による樹木形質転換系の碓立
梶田真也*1、川合伸也*1、片山義博*2、諸星紀辛*1、我彦広悦*3、佐野 浩*3、秦 邦男*4
*1
東京農工大学農学部, *2 東京農工大学共同研究開発センター, *3 秋田県立農業短期大学、*4 十条製紙株式会社
Constraction of transformation system of woody plant using Agrobacterium tumefaciens
Shinya Kajita*1, Shinya Kawai*1, Yoshihiro Katayama*2, Noriyuki Morohoshi*1, Hiroetu Wabiko*3, Hiroshi
Sano*3, Kunio Hata*4*1
Faculty of Agriculture,Tokyo University of Agriculture and Technology,*2Cooperative Research Center, Tokyo
University of Agriculture and Technology,*3Akita Prefectural College of Agriculture, *4Jujo Paper Co.,LTD
Abstract:
Poplar leaf disks were inoculated with Agrobacterium tumefaciens LBA 4404 carrying adisarmd Ti plasmid vector pB1121. T-DNA of this plasmid encodes two genes, one is neomycin
phosphotransferase ll gene and the other is -glucuronidase gene. The leaf disks were then transferred to
selective medium containing kanamycin. Transformed callus were obtained within 10 days, band maintained byfortnighty subculture. These transformants stained with X-Gluc., while untransformed callus contrastively didn't.
This transformation system will contribute to the genetic engineering of woody plants.

200

第 36 回 （1991.10.14-15） 北海道大学 学術交流会館
1991-101
急速凍結置換固定法による細胞壁木化過程の観察
猪股書恵、高部圭司、佐伯 浩
京都大学農学部
Observations on lignification process of cell wall by rapid-freeze and substitution method
Fumie Inomata, Keiji Takabe, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Abstract:
Lignification process of cell wall in conifer tracheid was observed by rapid-freeze andsubstitution method. The ultrastructural images indicate that the wall materials of newly deposition form an
amorphous thin layer lining the cell wall. This layer consists of polysaccarides and much water. Subsequently
cellulose microfibrils and hemicelluloses may be assembled to form hydrophilic ordered structure. Lignified
region of the wall hardly suffers the ice crystal damage, showing that lignification cause the removal of waterfrom unlignified cell wall. In the later stage of secondary wall lignification, egg-shaped rough- and/or smooth
endoplasmic reticula appear in cytosol. They may participate in biosynthesis and/or transport of lignin precursor.
1991-102
広葉樹の生育地・管孔配列・細胞壁厚とリグニン成分
呉 晋、深沢和三、大谷 諒
北海道大学農学部
Lignin compoition in hardwoods in relation to habitat, porosity and cell wall thickness in wood
Jing Wu, Kazumi Fukazawa, Jun Ohtani
Faculty of Agriculture, Hokkaido University
Abstract:
Guaiacyl (G) and syringyl (S) lignins were detected by VIS microspectrophotometry using
Mäule color reaction test. 110 hardwood species in 94 genera and 51 families from 3 habitats of Ynnnan, China,
have been investigated. The monomer composition of lignin in a particular area of wood tissue was influenced
by the kind of cell elelents, vessel arrangement of woods, tree habitat and cell wall thickness. GS ratio amongcertain cells or tree could not be fixed by this method, but a rough estimation of it was made by the analysis
from the spectrum. The variations may suggest the evolutionary stages of tree phylogeny.
1991-103
カエデ属におけるリグニン分布の多様性
平井陽子、深沢和三、呉 晋
北海道大学農学部
Distribnion of lignins on the genus Acer
Yoko Hirai, Kazumi Fukazawa, Jing Wu
Faculty of Agriculture, Hokkaido University
Abstract:
Distribution of lignins on the genus Acer was investigated by Mäule reaction, Klason method
and nitrobenzene oxidation. The Klason lignin content ranges from 20 to 25%, but some species have very highlignin contents (28-30%). The syringaldehyde-vanillin ratio (S/V) ranges from 0.3 to 3.0. The species which has
higher lignin content has lower S/V values. All species were classified into 7 types by these results andabsorption spectra of Mäule reaction.
1991-104
タケ、ササ細胞壁中のいくつかの成分について
橘 燦郎*1、大久保克美*1、G.H.N. Towers*2*1
愛媛大学農学部、*2 ブリティシュコロンビア大学
Some phenolic components of the cell walls of bamboos (Phyllostachys edulis and Phyllostachys bambusoides
Sieb. et Zucc.) and banboo grass (Sasa kurilensis Makino et Shibata)Sanro Tachibana*1, Katsumi Ohkubo*1, G.H.N. Towers*2*1
Faculty of Agriculture, Ehine University, *2Departnent of Botany, The University of British Columbia, Canada
Abstract:
4,4'-Dihydroxytruxillic acid (DTA), a photodimer of p-coumaric acid, and 4,4'-dihydroxy3,3'-dimethoxytruxillic acid (FAD), a photodimer of ferulic acid, were identified as components of the cell wallsof stems and leaves of the bamboo (Phyllostachys edulis) and the bamboo grass (Sasa kurilensis Makino et201

Shibata). Caffei acid, sinapic acid, 5-hydroxyferulic acid as well as p-coumaric acid and ferulic acid were also
identified. The amounts were determined by peak areas using GC/MS with stearyl alcohol as an internal
standard.
Existence
of
the
two
feruloyl
esters,O-(5-feruloyl-α-Larabinofuranosyl)-(1→3)-O-β-D-xylopyranosyl-(1→4)-D-xylopyranose and 5-O-feruloyl-α-L- arabinofuranose, in the hydrolysis products of the bamboo (Phyllostachys bambusoides Sieb. et Zucc.) cell walls was
confirmed on TLC plate through comparison of the Rf values with that of authentic samples.
1991-105
へミセルロース中におけるシナピルアルコールの脱水素重合
吉田晋一、棚橋光彦、篠田善彦
岐阜大学農学部
Dehydrogenative polymerization of sinapyl alcohol in hemicelluloses solutions
Shinichi Yoshida, Mitsuhiko Tanahashi, Yoshihiko Shinoda
Faculty of Agriculture, Gifu University
Abstract:
In a plant cell wall, lignin was deposited in the matrix of polysaccharides through thelignification process. To demonstrate the effect of hemicelluloses on dehydrogenative polymerization, sinapyl
alcohol was dehydrogenated with horseradish peroxidase/H2O2 in the presence of pectin by Zulaufverfahren.
Main reaction products, which were syringylglycerol-β- sinapyl alcohol ether, syringaresinol and unknown
compound, were isolated after the acetylation by PTLC and analyzed by NMR and MS spectrometry. As aresults,
unknowncompoundidentified
1,5-di(3,5-dimethoxy-4-hydroxyphenyl)-4-hydroxymethyl-5-hydroxy-1-pentene β-γtype). This substructure
would be presented in native lignin, and generated by ionic reaction through the extended
quinone-methide-intermediate.
1991-106
リグニン—グルクロン酸間エステル結合の酸化的開裂とその定量分析への応用
今村剛士*1、渡辺隆司*1、桑原正章*1、越島哲夫*2*1
京都大学木質科学研究所、*2 近畿大学農学部
Oxidative cleavage of ester linkages between lignin and glucuronic acid and its application to their quantitative
analysisTakeshi Imamura*1, Takashi Watanabe*1, Masaaki Kuwahara*1, Tetuo Koshijima*2*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kinki University
Abstract:
Conjugated acid between 2,3-dichloro-5,6-dicyano-1,4-benzoquirnone (DDQ) and protonic acid,
which is more electrophilic than DDQ, was subjected to the oxidative cleavage of ester bonds between
alkylaromatic compounds and glucuronic acid. When DDQ-TFA conjugate was allowed to react withbenzylglucuronate, the ester bonds were quantitatively cleaved, while ethyl glucuronate was inert to the reaction
due to its high oxidation potential. Application of the selective oxidation to the determination oflignin-glucuronic acid bonds in 1ignin-carbohydrate complexes (LCCs) is reported.
1991-107
イネのリグニンの 13C による選択的標識
謝 益民、寺島典二
名古屋大学農学部
Selective 13C enrichment of rice stalk lignin
Yimin Xie, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Abstract:
Carbon-13 enrichment of a specific carbon of rice stalk lignin was carried out by administrationof coniferin-[α-13C] and 4-O-β-D-glucoferulic acid-[α-13C] to a growing rice plant. The 13C content of a side
chain -carbon of rice stalk lignin reached about 10 times of the natural abundance. ln the I3C-NMR spectra ofcellulolytic enzyme lignin and acetal lignin showed intense signals corresponding to α-carbons. The enhanced
signals provide useful information about structure of lignin and the linkages between lignin and carbohydrates
in rice plant.
1991-108
ラジオトレーサー法によるリグニン試料中の残留炭水化物量の測定
202今井貴規、寺島典二
名古屋大学農学部
Quantitative determination of the residual carbohydrate in lignin-preparations by radiotracer technique
Takanori Imai, Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Abstract:
When myo-inositol-[2-3H] was administered to a magnolia shoot, radioactivity was mainly
incorporated into xylose obtained by sulfuric acid hydrolysis of newly formed xylem, whereas, no radioactivity
was incorporated into vanillin and syringaldehyde obtained by nitrobenzene oxidation. This result indicates thatxylan was labeled selectively in the tissue, To estimate the amount of residual carbohydrate remaining in Klason
lignin, the xylan-labeled wood tissue was treated with sulfuric acid, and the radioactivity of the insoluble solid
lignin was determined. The amount of residual carbohydrate originating from xylan in Klason lignin was
estimated to be about 8 %.
1991-109
ミクロオートラジオグラフ法による樹幹先端部の木部分化とリグニン不均一形成に関する研究
福島和彦*1、寺島典二*1、高部圭司*2*1
名古屋大学農学部, *1 京都大学農学部
Heterogeneous lignification during the apical growth of magnolia shoot studied by microautoradiography
Kazuhiko Fukushima*1, Noritsugu Terashima*1, Keiji Takabe*2*1
Faculty of Agriculture, Nagoya University, *2Faculty of Agriculture. Kyoto University
Abstract:
Heterogeneous formation of lignin in the primary xylem of magnolia was visualized by
microautoradiography and UV microscopy. Protoxylem in the vascular bundle consists of some vessels withlignified spiral secondary wall and undifferentiated parenchyma whose lignification is much delayed than otherkind of cells. The cells around the primary xylem were differentiated to be thick wall cells and lignified after theformation of secondary xylem. UV spectra showed that the vessel wall lignin of primary xylem was similar tothat of secondary xylem and that pith lignin was similar to fiber secondary wall 1ignin which is syringyl-rich. It
is proposed that lignification in the elongating shoot would proceed in accordance with cell differentiation under
definite controlled manner.
1991-110
リグニン化学構造の不均一性
深川伸隆、飯塚堯介、西山正樹、石津 敦
東京大学農学部
Structural inhomogeneity of lignin
Nobutaka Fukagawa, Gyosuke Meshitsuka, Masaki Nishiyama, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Abstract:
Structural inhomogeneity of lignin was clearly demonstrated by the isolation of two distinctive
lignin fractions from birchwood periodate lignin. The first one is a predominatingly syringyl-rich, mostly β-O-4linked lignin fraction, which has a molecular weight of not lower than a milled wood lignin. The second one is alow molecular weight fraction of guaiacyl-rich and highly condensed structure.
1991-111
核交換および過ヨウ素酸酸化の併用によるリグニン芳香核構造の解析
船岡正光*1、Y.−Z．Lai*2*1
三重大学生物資源学部、*2NewYork 州立大、ESPRIStructural analysis of lignin by a combined nucleus exchange - periodate oxidation method
Masamitsu Funaoka*1, Y.-Z. Lai*2*1
Faculty of Bioresources, Mie University, *2Empire State Paper Research Institute, State University of New
York
Abstract:
The phenolic hydroxyl group is one of the most important functionalities significantly affecting
the reactivity of lignin during various modification processes. The free phenolic hydroxyl content of lignin has
been estimated by several methods such as UV and NMR spectroscopies, potentiometric titration or periodate
oxidation. However, these conventional processes give only the data on its total amount. The combined nucleus
exchange-periodate oxidation method provides the quantitative information on the distribution of phenolichydroxyl group in guaiacyl and syringyl, condensed and non-condensed, and diphenylmethane type units which203

are important as secondarily formed condensed structures. In the present paper, the theory, the procedure, and its
application to softwood and hardwood protolignins, isolated lignins and pulp residual lignins are discussed.
1991-112
TMSiI 処理によるリグニン中めエーテル結合の選択的開裂 —低分子生成物の性状
藤野謙一、飯塚堯介、石津 敦
東京大学農学部
Selective cleavage of ether bonds in lignin by trimethylsilyl iodide, - The character of the low molecular weight
products Kenichi Fujino, Gyosuke Meshitsuka, Atsushi lshizu
Faculty of Agriculture, the University of Tokyo
Abstract:
Trimethylsilyl iodide cleaves ether bonds in lignin selectively under very mild reaction
conditions. Applying this agent to gaiacylglycerol-β-guaiacyl ether as a model compoud, it has been proposedthat the cleavage reaction results from the iodination of the benzyl carbon followed by the formation of a α-β
double bond and the cleavage of the β-aryl ether bond. In this paper we applied this agent to a periodate lignin.
Some acetate derivatives of the degradatiton products were separated by TLC and analyzed by means of
GC-MS.
1991-113
1,2-ジアリール-1,3-プロパンジオールの塩酸中の挙動
岩瀬幸彦、安田征市
名古屋大学農学部
Behavior of 1, 2-diaryl-1, 3-propanediol in hydrochloric acid
Yukihiko Iwase, Seiichi Yasuda
Faculty of AgrictJlture, Nagoya University
Abstract:
1,2-Diguaiacyl-1,3-propanediol [α-l3C] , one of lignin structural models, was synthesized andthen treated in refluxing 0.2N hydrochloric acid. The 13C NMR analysis of the products strongly supported thealready proposed reaction mechanism of so-called "acidolysis'' and. at the same tine, confirmed norearrangement of a methyl group in contrast with easy rearrangement of a hydrogen atom and a phenyl nucleus.
Treatment of models in refluxing 5% hydrochloric acid afforded less low-molecular- weight compounds andmore condensation products in comparison with acidolysis. Treatment of the models in concentratedhydrochloric acid recovered the starting compounds together with condensation products
and tentative
chlorides. These results accord the fact that hydrochloric acid lignin contains less condensed structural unit thansulfuric acid lignin.
1991-114
ウド（Alaria cordata）シンナミルアルコールデヒドロゲナーゼの精製
日尾野隆*1、柴田大輔*1、梅沢俊明*2、樋口隆昌*3*1
三井植物バイオ研究所、*2 京都大学木質科学研究所、*3 日本大学農獣医学部
Isolation and characterization of cinnamyl alcohol dehydorogenase from Alaria cordata
Takashi Hibino*1, Daisuke Shibata*1, Toshiaki Umezawa*2, Takayoshi Higuchi*3*1
Mitsui Plant Biotechnology Research Institute, *2Wood Research Institute, Kyoto University,*3
College of Agriculture and Veterinary Medicine, Nihon University
Abstract:
A cinnamyl alcohel dehydrogenase (CAD) from Alaria cordata was purified about_ 2100 foldto homogeneity. The molecular weight of the enzyme was estimated by Superose 12 column to be 72,000. The
enzyme preferred cinnamaldehydes and cinnamyl alcohol as substrates. The purified protein was subjected to
BrCN cleavage and the resulting peptides were separated using reverse- phase HPLC for amino acidsequencing.
1991-115
エレクトロポレーション法によるアンチセンス PAL 遺伝子のタバコヘの導入
日尾野隆*1、伊藤恵美子*1、柴田大輔*1、樋口隆昌*２、永井伸夫*３、下坂 誠*３、岡崎光雄*３*1
三井植物バイオ研究所、*２日本大学農獣医学部、*３信州大学応用生物科学科
Phenyalanine ammonia-lyase antisense gene transfer into tobacco by electroporation
Takashi Hibino*1, Emiko ltoh*1, Daisuke Shibata*1, Takayoshi Higuchi*2, Nobuo Nagai*3,204

Makoto Shimosaka*3, Mitsuo Okazaki*3*1
Mitsui Plant Biotechnology Research Institute, *2Wood Research Institute, Kyoto University,*3
Faculty of Textile Science and Technology, Shinshu University
Abstract:
Phenylalanine ammonia-lyase (PAL) is the key enzyme in the formation of secondary
metabolites including lignjn precursors. To control the production of lignin in plant cells, we constructed
antisense genes using a PAL cDNA isolated from tobacco suspension cells. They were introduced into tobacco
protoplasts by electroporation.
1991-116
ユーカリゲノムライブラリーの作成
日尾野隆，伊藤恵美子，柴田大輔
三井植物バイオ研究所
Construction of a genomic library from Eucalyptus (E. saligna)
Takashi Hibino, Emiko Itoh, Daisuke Shibata
Mitsui Plant Biotechnology Research Institute
Abstract:
We isolated genomic DNA from callus of Eucalyptus using CTAB (cetyltrimethyl- ammonium
bromide). DNA fragments which was partially digested with Sau3Al were ligated with EMBL3. The DNAs
were packaged into phase particles to obtain a genomic library, resulting one million recombinants.
1991-117
交雑ヤマナラシの宿主・ベクタ一系の構築及びアンチセンス RNA 法によるリグニン生合成の解析
梶田真也*1、三浦 進*1、山門幹子*1、山田恵子*2、川合伸也*1、片山義博*２、秦 邦男*３、諸星紀幸*1*1
東京農工大学農学部、*２東京農工大学共同研究開発センター、*３十条製紙株式会社
Agrobacterium-mediated transformation of poplar and using antisense or sense gene fragment to study genefunction of lignin biosynthesis
Shinya Kajita*1, Susumu Miura*1, Mikiko Yamakado*1, Keiko Yamada*2, Shinya Kawai*1
Yoshihiro Kataywa*２, Kunio Hata*３, Noriyuki Morohoshi*1*1
Faculty of Agriculture, Tokyo Univercity of Agriculture and Technology, *２Cooperative Research Center,
Tokyo University of Agriculture and Technology,*3Jujo Paper Co. Ltd.
Abstract:
The long generation time of the tree means that genetic improvement by classical breeding isa slow process. Genetic engineering should be helpful in solving this problem. We have established atransformation system mediated binary vector of non-oncogenic Agrobacterium tumefaciens LBA4404 andapplied this system to a analysis of the functional relationships of genes encoding enzymes of lignin
biosynthesis pathway. So we introduced antisense and sense gene fragment into poplar hybrid clone andtobacco.
1991-118
リグニンモデル化合物分解酵素遺伝子のクローニング. XVIII. β-エーテラーゼ遺伝子の塩基配列と Cα-デヒ
ドロゲナーゼ遺伝子のクローニング
政井英司*1、窪田祥子*1、片山義博*2、川合伸也*1、山崎眞狩*3、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター、*3 東京大学農学部
Cloning of the genes involved in degradation of lignin model compounds (XVII), Sequencing of the β-etherase
gene and cloning of the Cα-dehydrogenase gene from Pseudomonas paucimobilis SYK-6
Eiji Masai*1, Sachiko Kubota*1, Yoshihiro Katayama*2, Shinya Kawai*1, Makari Yamasaki*3,
Noriyuki Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology,*3Faculty of Agriculture, the University of Tokyo
Abstract:
We have isolated Pseudomonas paucimobilis SYK-6 which could grow on various lignin
dimeric compounds as a sole carbon source. Cleavage of β-aryl ether is the most important process in the lignin
degradation because this linkage is the most abundant. We have already reported the detection of the activity of
β-etherase in a cellular membrane fraction of P.paucimobilis SYK-6. This enzyme catalyzed the unique andreductive cleavage of arylglycerol-β-aryl ether (Cαcarbonyl type). Here, we report the sequencing of the
β-etherase gene. This gene contains an open reading frame of 843bp and the molecular weight of deduced
protein is 32,070. We named this gene ligE. The polypeptide expressed in Escherichia coli transformant was
identified. In addition, we also found the Cα-dehydrogenase gene (ligD ) for which the enzyme catalyzes the205

Cα-dehydrogenation of arylglycero1-β-aryl ether (C alcohol type) in the 24kb Sal I fragment containing ligE.
1991-119
リグニンモデル化合物分解酵素遺伝子のクローニング（XIX） ビフェニル型化合物分解に関与する遺伝子の単離と解析
花城 薫*1、政井英司*1、片山義博*2、川合伸也*1、西川誠司*1*3、諸星紀幸*1*1
東京農工大学農学部, *2 東京農工大学共同研究開発センター, *3 コスモ石油株式会社
Cloning of the genes involved in degradation of lignin model compounds (XIX)
Kaoru Hanashiro*1, Eiji Masai*1, Yoshihiro Katayama*2, Shinya Kawai*1, Seiji Nishikawa*1*3, Noriyuki
Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center, Tokyo
University of Agriculture and Technology, *3Kosumo Oil Co.Ltd.
Abstract:
Pseudomonas paucimobilis could grow on various lignin dimeric compounds as a sole carbon
source. In particular, it is characteristic of this strain to degrade biphenyl compounds. We have already reported
about the metabolism of biphenyl structure in lignin. Here we tried to isolate the gene involved in degradation of
biphenyl compounds. We isolated the several mutants of P. paucimobilis SYK-6 deficient in degradation ofcompound (1) and (3). The gene which restore the wild's phenotype of mutants were isolated from cosmid
genomic library of P. paucimobilis SYK-6.
1991-120
リグノスチルベン-α,β-ジオキシゲナーゼ産生遺伝子のクローニングと発現・同定
鴨田重裕、佐分義正
東京大学農学部
Cloning, expression and identification of a lignostilbene-α β-dioxygenase gene from Pseudomonas
paucimobilis TMY1009
Shigehiro Kamoda, Yoshimasa Saburi
Faculty of Agriculture, the University of Tokyo,
Abstract:
Lignostilbene-α  -dioxygenases (LSDs) are the key enzyme responsible for the cleavage ofthe interphenyl Cα-Cβdouble bonds of stilbene type structure in the metabolism of dimeric lignin-related
compounds by Pseudomonas paucimobilis TMY1009. Though LSD is similar to meta-cleavage dioxygenase inhaving nonheme iron, LSD is a new type dioxygenase which excels those in stability. To get the knowledge ofthe primary structure, it is one aim, cloning the gene encoding LSD has been done. The BamHI-KpnI fragment(8kbp) encoding a LSD gene was ligated in pUC19 at the same restriction enzyme site. E.coli JM109 carrying
this plasmid produced LSD little. In this study, a SalI fragment (1.9kbp) was subcloned, the LSD gene on thisfragment was expressed, andthe products was identified.
1991-特別講演
リグニン化学における標識実験法
寺島典二
名古屋大学農学部
Invited lecture: Tracer method in lignin chemistry
Noritsugu Terashima
Faculty of Agriculture, Nagoya University
Abstract:
Every wood chemist encounter serious difficulties in investigating the structure and reaction oflignin in the cell wall, because lignin is a structurally inhomogeneous macromolecule and it is impossible toisolate lignin in its unaltered state, or to depolymerize lignin into monomeric or oligomeric building units
quantitatively. The nondestructive analysis of lignin labeled selectively with radioisotope or stable isotope at
specific hydrogen and/or carbon gives useful information that is not obtained by any other methods. An outline
and discussion are given of the recent advances in application of this technique to the studies on formation,
structure and reaction of lignin in the cell wall.
1991-201
カワラタケが分泌するリグニン分解酵素とタンパク分解酵素の関係について —リグニン分解性ラッカーゼ(III) の糖鎖の役割
中村雅哉*1、西田篤実*1、吉武彰文*2、片山義博*3、飯村洋介*3、諸星紀幸*3
206

*1

森林総合研究所、*2 へキストジャパン、*３東京農工大学農学部
Production of ligninolytic laccase and proteolytic enzymes in Coriolus versicolor
Masaya Nakamura*1, Atsurni Nishida*1, Akifumi Yoshitake*２, Yoshihiro KaLayama*３,
Yousnke limura*３, Noriyuki Morohoshi*３*1
Forestry and Forest Products Research Institute,*2Haechst Japan Ltd., *2Faculty of Agriculture, Tokyo
University of Agriculture and Technology
Abstract:
Ligninolytic laccase ( laccase llI ) from Coriolus versicolorr was known to be anionicglycoprotein. Structural analysis of this enzyme showed that laccase III contained at least four N-linked
carbohydrate chains. Judging from the time course changes of laccase and protease activities in the culture
fluids containing tunicamycin, these four carbohydrate chains had a protective function to maintain enzymatic
activity under proteolytic condition. In particular, high proteolytic activity was identified in nitrogen starved
culture filtrates. Partial characterization of proteases induced by nitrogen starvation stress is carrying out.
1991-202
リグニンパーオキシターゼの触媒サイクル
桃原郁夫、松本雄二、石津 敦
東京大学農学部
Catalytic cycle of lignin peroxidase
Ikuo Momohara. Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture. the University of Tokyo
Abstract:
The formation of super oxide during the lignin peroxidase (Li-P) reaction was confirmed by thereaction of super oxide with tetranitromethane (TNM). In the presence of H2O2, veratryl alcohol, Mn 2+, andTNM, trinitromethane anion was perhaps only one product by the Li-P reaction and veratraldehyde formation is
not found. The same result was obtained when the above reaction was carried out under a nitrogen atmosphere.
On the other hands, veratraldehyde was formed under the same condition as the above whenm-chloroperbenzoic acid (CPBA) was used as an oxygen donor. Oxygen consumption which was observed
during the Li-P reaction with veratryl alcohol, Mn2+, arid H2O2 was not observed in the presence of CPBA
instead of H2O2. These results strongly suggest that super oxide formation and oxygen uptake are independentof the substrate radicals.
1991-203
広葉樹培養細胞のリグニン生成とペルオキシターゼアイソザイムの基質特異性について（その 3）
堤 祐司、坂井克己
九州大学農学部
Lignin biosynthesis and substrate specificity of peroxidase isoenzymes with respect to syringyl and guaiacyl
stracture in angiosperm tree callus cultures (III)Yuji Tsutsumi, Kokki Sakai
Faculty of Agrictllture, Kyushu University
Abstract:
We have been investigating the possibility that substrate specificities of peroxidases can control
syringyl/guaiacyl ratio of lignin in xylem tissues. It was found that the syringyl specificperoxidase (SyPO) was present in the ionically bound peroxidase (IPO) group extracted from callus culture ofPopulus alba. This SyPO isoenzyme specifically catalyzed the hydrogen peroxide- oxidation of syringyl
substrates such as syringaldazine and 2,6-dimethoxyphenol but not the dehydrogenative polymerization ofconiferyl alcohol. The IPO group from a Populus alba tree also exhibited the highest specificity for syringyl
substrate among three peroxidase groups in both spring and summer. Whole peroxidase activities, especiallysyringyl oxidizing activity of IPO were decreased in summer.
1991-204
カワラタケによるリグニンモデル化合物のフェノール性水酸基のキシロース配糖化
山上 陽、近藤隆一郎、坂井克己
九州大学農学部
Xylosidation of phenolic hydroxyl group of lignin model compounds by Coriolus versicolor
Hikari Yamagami, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
In previous reports we showed that primary alcoholic hydroxyl groups of lignin model207

compounds were bioconverted into their xylosides, in glucose media that were inoculated with Coriolus
versicolor. In the present work, the xylosidation of phenolic hydroxyl group of lignin model compounds wasinvestigated. When added to a culture of C. versicolor, methyl-guaiacol (MeG), a phenolic lignin modelcompounds, was bioconverted into 2-methoxy-4-methylphenyl- -D-xyloside (MeG-Xyl). The formation of
HG-Xyl was also observed in holocellulose media. When the cultivation was performed under nitrogen
atmosphere to avoid the rapid consumption of MeG by laccase in the medium 28% of MeG was bioconverted
into MeG-Xyl for 24 hours. Therefore, it can be concluded that not only alcoholic but phenolic hydroxyl groupof lignin model compounds were transformed into their xylosides by C. versicolor. Furthermore,it was observedthat the xyloside formation activity of C. versicolor was activated by the exogenous addition of phenolic
compounds into the medium.
1991-205
バイオミメティツクフタロシアニン鉄錯体による β-O-4 型リグニンモデル化合物の酸化分解
谷原佳文*1、服部武文*1、(信大繊)白井江芳*2、島田幹夫*2*1
京都大学木質科学研究所，*2 信州大学繊維学部、The biomimetic degradation of β-O-4 lignin model dimers by t-BuOH in the presence ofoctacarboxyphthalocyaninato-iron (III) catalyst
Yoshifurmi Tanihara*1. Takefumi Hattori*1, Hirofusa Shirai*2, Mikio Shimada*1*1
Wood Research Institute, Kyoto University, *2Faculty of Textile Science and Technology. Shinshu University
Abstract:
The biomimetic degradation of a β-O-4 lignin substructure model dirmer, 4-ethoxy- 3methoxy-arylglycero1-β-vanillyl alcohol ether (I), by tert-butylhydroperoxide in the presence ofoctacarboxyphthalocyaninato-iron (III) (Fe(III)Pc) was investigated. The substrate (I) Was oxidatively degradedby catalysis of Fe(III)Pc in aqueous solution at pH 3 at room temperature. This catalyst was found to mimic alignin peroxidase (LiP) activity, yielding both C-C bond cleavage and aromatic ring opening products derived
from β-O-4 substrate (I). The β-O-4 dimer (II) formed from substrate (I) was also degraded to give C-C bondcleavage products. vanillin and 4-O-ethylvanillic acid, in alkaline solution at room temperature.
1991-206
硫酸触媒を用いた広葉樹材の常圧酢酸パルプ化 —高分子リグニンの利用研究のための多量リグニン簡
易分離法としての評価
堀崎敬史、島谷啓二、佐野嘉拓、笹谷宜志
北海道大学農学部
Pulping of hardwoods at atmospheric pressure with aqueous acetic acid containing a small amount of sulfuric
acid -Characterization of resulting acetic acid lignins as raw materials for utilization studeis of polymeric lignins
Yoshifumi Horisaki, Keiji Shimatani, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Abstract:
Acetic acid lignins (AWL) can be produced without tedious operation and in quantity from thereaction solution obtained by atmospheric pulping with aqueous acetic acid containing a small amount ofsulfuric acid. Therefore, the lignins may be used in the utilization studies of lignins with large quantities, if they
are modified less greatly during the pulping. To determine the possibility, the chemical structure of AWLs wascharacterized by the elemental analysis, analysis of functional groups by 1H-NMR and other methods, several
degradation procedures average molecular weights and so forth.
1991-207
広葉樹クラフトパルプ中のキシランとリグニンの関係
種田英孝，松倉紀男，秦邦男
十條製紙
Characterization of xylan and lignin in hardwood kraft pulp
Hidetaka Taneda, Motoo Matsukura, Kunio Hata
Jujo Paper Co., Ltd.
Keywods:
広葉樹クラフトパルプ・ヘミセルロース・キシラン・リグニン・カッパー価・未晒パルプ
hardwood kraft pulp, hemicellulose, xylan, lignin, kappa number, unbleached pulp
Abstract:
Relation between lignin and xylan in hardwood kraft pulp was investigated. From theunbleached pulp and oxygen delignified pulp, xylan ms isolated, and then lignin contents in these fractions,
xylans, extracted pulps and extraction liquors were measured by the use of Kappa number method. In the case208

of chlorine and alkali treated pulp and bleached pulp, chlorine contents of the fractions were measured insteadof the lignin contents. These results show that about half of the residual lignin in kraft pulp exists in xylan
fraction. It may suggest that the lignin should be linked with xylan chemically.
1991-208
酸素・アルカリ脱リグニン過程における炭水化物の崩壊機構（1）糖の分解に及ぼすリグニンの影響についてのモデル実験
安本光夫、松本雄二、石津 敦
東京大学農学部
Effects of lignin structure on carbohydrate degradation during oxygen bleaching
Mitsuo Yasumoto, Yuji Matsunoto. Atsushi Ishizu
Faculty ofAgriculture. The Uniyersity or Tokyo
Abstract:
Methyl β-D-glucopyranoside (MeG) was treated with oxygen under an oxygen bleachingcondition in the presence or absence of various types of lignin model compounds as well as waste liquor lignin
obtained by oxygen bleaching of pine kraft pulp. Then lignin model compounds were absent, MeG wasn't
degraded at all. ln the presence of phenolic lignin compounds without α-carbonyl group, MeG was degraded toa significant extent, which was proportional to the amount of added model compounds. Whereas the wholewaste liquor lignin didn't show any degradation effect, its high molecular weight fraction showed strong effecton the MeG degradation.
1991-209
酸素酸化パルプ化による稲わらリグニンの変化（1）陳 克利、伊藤博徳、林 治助
北海道大学工学部
Variation of rice straw lignin with NaOH-O2 pulping (I)Ke-Li Chen, Hironori ltoh、Jisuke Hayashi
Faculty of Engineering, Hokkaido Uiyersity
Abstract:
Rice straw is readily pulped by oxygen oxidation after alkali soaking. To investigate changes oflignin and polysaccharides during the gulping, waste liquors of soaking and pulping were subjected to a seriesof extraction of acid-precipitated solid (AP), acid-soluble lignin (ASL) and polysaccharides, and then wereanalyzed. Because of the existence of nitrogen in the straw, all the products contained nitrogen. Purified APfrom soaking waste liquor did not contain nitrogen, but pulped lignin still retained high content of nitrogen,nearly equal to 5 times that of the straw. It also showed that the lignin subject to oxidation was degraded to agreat extent.
1991-210
アルカリ・アルコール・アントラキノン蒸解について
阿部善作
九州大学農学部
Alkali-alcohol-anthraquinone pulping
Zensaku Abe
Faculty of Agriculture, Kyushu University
Abstract:
This investigation was carried out to obtain better understandins of alkali-alcoholanthraquinone pupling. It was compared with other pulpings ; alkali-alcohol pulping, alkali- anthraquinone
pulping, and kraft pulping. As the results were shown in Fig.1, alkali-alcohol- anthraquinone pulping can
produce unbleached pulp of the lowest lignin content at high pulp yield.
1991-211
アルコール・バイサルファイト処理によるリグニンモデル化合物の β-O-4 結合開裂反応の特徴（その 2）
宮脇正一、坂井克己
九州大学農学部
Characteristics of the β-O-4 bond cleavage reaction during an alcohol-bisulfite treatment of lignin modelcompounds (II)Shoichi Miyawak, Kokki Sakai
Factllty of Agriculture, Kyushu University
209

Abstract:
Lignin model compounds shown in Fig.1 were synthesized and subjected to alcohol- bisulfite(AB) treatment and alcohol-phosphate buffer (AP) treatment at 160ºC for 30 and 60 min. Substituents at theposition para to the β-O-4 bond in the ring a provided no large influence on yields of isoeugenol and phenols
derived from the ring B that were produced by the β-O-4 bond cleavage in the AB treatment. Recovery ofstarting materials after the AB treatment was about the same as those after the AP treatment of the sane
compounds. We now presume that the β-O-4 bonds in phenolic lignin units are cleaved homolytically during the
AB treatment. Radical intermediates formed by the homolysis may be stabilized by a rapid electron transferfrom bisulfite anions and/or bisulfite radicals.
1991-212
リグニンのメカノケミストリー（XII） （5,5’）-(β-O-4)型三量体リグニンモデル化合物の合成とそのメカノケミス
トリー伊藤和貴、住本昌之
九州大学農学部
Mechanochemistry of lignin (XII), -Synthesis and mechanochemical conversions of (5-5')-(β-O-4) type oftrimer lignin model compound
Kazutaka Itoh, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Abstract:
Trials for the improved method of synthesis of (5-5')-(β-O-4) type of trimeric lignin modelcompounds (I) and (II) were made by application of benzyltri-n-butylammonium bromide as a phase-transfer
catalyst. Mechanochemical treatments of the model compound (I) with VBM and CBM furnished a(5-5')-β-O-4) type of trimer having a para-carbonyl pheno1 (III), and a pair of oxidation products of
3-methoxy-5-substituted para-benzoquinone (IV), and 2-(2-methoxy- phenoxy)-3-hydroxypropionic acid (V),and the other product (VI).
1991-213
リグニンのメカノケミストリー（XIII） Veratrylglycerol-β-syringylaldehyde ether の反応とその機構について
呉 宗華、住本昌之
九州大学農学部
Mechanochemistryoflignin(XIII),
Mechanochemical
reductions
andmechanismsofveratrylglycerol-β-syringaldehyde ether
Wu Zonghua, Masashi Sumimoto
Faculty of Agriculture, Kyushu University
Abstract:
To clarify the mechanochemical reaction mechanisms of veratrylglycerol-β-syringaldehyde
ether (M), comparative treatments of the compound (M) were made with VBM under nitrogen or air. Treatments
under nitrogen resulted in the significant decrease in the yields of 3,5- dimethoxy-p-hydroquinone and3,5-dimethoxy-p-benzoquinone but a little increase in the yields of syringaldehyde compared to those under air.
This strongly suggested that •O2H radical is formed in the aqueous media to react with syringaldehyde moiety.
Addition of normal paraffin alcohols served as •OH radical scavengers showed that the mechanochemical
reactions were heavily retarded. The formation of adduct of phthalic hydrazide with •OH radical fully confirmed
the presence of •OH radical in the aqueous media of VBM during the treatments. Likely to those in the media ofsuper sound, the aqueous media of mechanical pulping produces •O2H, •H, and •OH radicals to convert
mainly lignin.
1991-214
Phanerochaete chrysosporium による塩素化フェノール類の代謝 (2) 塩素置換位置とフェノール性水酸 基 のメチル化の影響小野克正、桃原郁夫、松本雄二、石津 敦
東京大学農学部
Metabolism of chlorinated phenols by Phanerochaete chrysosporium
Katsumasa Ono, Ikuo Momohara, Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Abstrsct:
When chloroguaiacols were t.rented with lignin peroxidase (Li-P) in the presence of veratryl
alcohol (VA), they were oxidized easily and oxidation of VA does not proceed until the reaction ofchloroguaiaco18 was completed, indicating that VA oxidation is strongly inhibited by chloroguaiacols. On the210other hand, chloroveratrol did not show any inhibiting effect on VA oxidation and, even under a very low H2O2
concentration, spectral change was not observedin the absence of VA. These results coincide with theobservation that metabolism of chlorophenols by P. chrysosporium are prohibited by methylation reaction which
is apparently active throughout the life time of this fungus.
1991-215
リグニン分解菌（IZU−154 株）によるクラフトパルプ漂白廃液の処理
李 宣鏑*1、近藤隆一郎*1、坂井克己*1、西田友昭*2、高原義昌*2*1
九州大学農学部、*2 神戸製鋼株式会社生物研究所
Decolorization of kraft bleaching effluent by the lignin-degrading fungus IZD-154
Seen-Ho Lee*1, Ryuichiro Rondo*1, Kokki Sakai*1, Tomoaki Nishida*2, Yoshimasa Takahara*2*1
Faculty of Agriculture, Kyushu University, *2Biotechnology Research Laboratory, Kobe Steel, Co. Ltd.
Abstract:
In the previous reports, we showed that biomechanical pulping and biobleaching weresuccessfully performed by the treatment with a hyperligninolytic fungus IZU-154. In the present work, we tried
to decolorize the bleaching effluent from an alkaline-extraction stage (E1) by the fungus IZU-154. To establish
an effective color removal process, various cultivation parameters of IZU-154 and treatment conditions of E1
effluent with the fungus were investigated. Under the best conditions employed here, a treatment with IZU-154
for 24 hours in the presence of a small amount of glucose resulted in 95% reduction of color of an undiluted E1
effluent containing 7,500 color unit. On the other hand, when the effluent was treated with Phanerochaetechrysosporium and Coriolus versicolor under the same conditions, only 58% and 19% of the color were
removed after a 48-hour incubation. The elucidation of the mechanism of color reduction by the fungus
IZU-154 is now in progress.
1991-216
機械パルプの微生物処理に関する研究（VIII）光退色におよぼすカルボニル基の影響
橘 燦郎*1、神谷英伸*1、足立幸男*1、大久保克美*1、住本昌之*2
愛媛大学農学部、九州大学農学部
Studies on biological treatment of mechanical pulps (VIII)
Effect of carbonyl groups on light-induced color reversion of mechanical pulps
Sanro Tachibana*1,Hidenobu Kamitani*1,Yukio Adachi*1, Katsuni Ohkubo*1,Masashi Sumimoto*2*1
Faculty of Agriculture, Ehime University, *2Faculty of Agriculture, Kyushu University
Abstract:
The effect of carbonyl groups on light-induced color reversion of mechanical pulps was
examined. For the first time, reduction of seven model compounds containing -carbonyl group with KBH4
accompanied with or without phase transfer catalyst (PTC) was conducted to find out an effective reduction
method for the groups. The model compounds could not be reduced with KBH4 only, however, the reduction of
the model compounds with KBH4 proceeded significantly by addition of small amount of PTC. Based on the
results obtained from the model experiments, mechanical pulps were treated with KBH4 accompanied with PTC
before and after bleaching. Light-induced color reversion of bleached groundwood pulp (GP) was suppressed 33
to 44% by pretreatment of GP with KBH4 accompanied with PTC. However, in the case of thermomechanicalpulp (TMP) and pressurized groundwood pulp (PGW), the depression of the color reversion was 11 to 19%
and11to 23%, respectively, to that of the untreated pulp. It is suggested that the effect of carbonyl groups on thecolor reversion of mechanical pulps is not so high.
1991-217
リグノセルロースのリン酸エステル化によるヒドロゲル化（第 3 報）吸水性に及ぼすリグニンの影響
斉藤直人、関 一人、吉田兼之、青山政和
北海道林産試験場
Hydrogelation of lignocellulosic materials by phosphorylation (III), Effect of lignin content on the water
absorbency
Naoto Saito, Kazuto Seki, Kaneyuki Yoshida, Hasakazu Aoyama
Hokkaido Forest Products Research Institute
Abstract:
To investigate the effect of pretreatment with acidic sodium chlorite on swelling behavior ofphosphorylated lignocellulosic materials, chlorite treated wood meals containing various amounts of lignin wereprepared. In the early stage of delignification, the procedure was quite selective in removing lignin, and no
significant change in carbohydrate content was observed. Water absorbency of chlorite treated wood meals
211

followed by phosphorylation with phosphoric acid and urea rapidly increased with increasing degree ofdelignification during the first 65 %. When wood meals were treated with chlorite three times, maximum water
absorbency (141 gH2O/g) gas obtained. Degree of delignification of the treated wood meals was 65 %, and theircarboxyl group content was maximum (0.48 mmol/g). These results indicate that delignification and carboxylgroup content of wood meals play an important role in hydrogelation of the phosphorylated products.
1991-218
リグニンのヒドロキシアルキル化 （I） リグニンとグリセロールの反応
菱山正二郎*1、大原誠資*1、須藤賢一*2*1
森林総合研究所、*2 群馬女子短期大学
Hydroxyalkylation of lignin (I), Reaction of lignin with glycerol
Shojiro Hishiyama*1, Seiji Ohara*1, Kenichi Sudo*2*1
Forestry and Forest Products Research Institute, *2Gunma Womens Junior College.
Abstract:
In the case of the preparation of polyurethane from lignin, it is necessary to modify lignins to
the derivatives which possess high reactivity to isocyanates. Then in this study, we tried to introduce alcoholichydroxyl groups into lignin model compounds. Three kinds of lignin model compounds ( phenol, guaiacol,
syringol ) were treated with glycerol -monochlorohydrin. The products having alcoholic hydroxyl groups wereidentified based on the NMR and MS spectra. The reaction of these modified model compounds withisocyanates are now carried on.
1991-219
Synthesis and properties of lignin based epoxy resins
Klaus Hofmann*1, Wolfgang G．Glasser*2*1
Industrial Products Research Institute, Tsukuba, *2Virginia Polytechnic Institute and State University
Abstract:
Lignin from steam-exploded yellow poplar wood was chain-extended by hydroxypropylation of
the hydroxyl groups. Depending on the amount of propylene oxide used chain-ext:ended hydroxypropyl lignins(CEHPL) with various polyether chain lengths were obtained which had a wide range of viscoelastlc properties.
Endcapplng of the poly (propylene oxide) segments with ethylene oxide and subsequent epoxidation withepichlorohydrin yielded segmented, star-like epoxy resins. Fractionation by precipitation in aceton:hexane
solvent systems was carried out to obtain poly (propylene oxide) homopolymer free resins with different
molecular weights and narrow molecular weight distributions. Curing of these compounds with m-PDA yieldedmaterials which ranged from elastomers to rigid solids, depending on the molecular weight and the level ofchain-extension. Also their mechanical properties showed a wide variation whereby the short chain-extended,high molecular weight materials exhibited strengths and moduli in the same order as those of a commercial
DGEBA based resin.
1991-220
リグノセルロース系ポリウレタン分子複合材料の力学的性質
中村邦雄*1、畠山兵衛*2*1
大妻女子大学, *2 製品科学研究所
Molecular composites consisting of polyurethanes from lignocellulosics
Kunio Nakamura*1, Hyoe Hatakeyama*1*1
Otsuma Wonen's University, *2Industrial Products Research Institute, Tokyo
Abstract:
Solvolysis lignin and wood tar were used in the preparation of molecular composites consistingof paper and polyurethane (PU). The composites of filter paper (FP)-solvolysis lignin(SL)-diphenylmethanediisocyanate(MDI)(FP-SL-MDI),
FP-SL-polypropyleneglycol(PPG)-MDI(FP-SL-PPG-MDI), FP-wood tar (WT)-MDI (FP-WT-MDI) and FP-WT-PPG-MDl systems were prepared.
Mechanical properties of these composites were investigated by a tensile test machine. The tensile strength ofthe composites of FP-WT-MDI system increased with increasing the amount of PU/FP (g/g). The maximum
stress of the composites was five times higher than that of filter paper. It is found that PPG acts as a soft
segment in those systems.
1991-221
リグニン分解物を原料とする液晶性全芳香族ポリエーテルの合成と熱的性質
広瀬重雄*1、畠山立子*2、畠山兵衛*1
212

*1

製品科学研究所、*2 繊高研
Synthesis and thermal analysis of liquid crystalline aromatic polyethers derived from degradation products ofligninShigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*1*1
Industria] Products Research lnstit.ute, *2Research Institute for Polymers and Textiles
Abstract:
Aromatic polyethers were synthesized by the condensation of 4..4'-difluoro-3,3'dinitro-benzophenone with potassium salts of hydroquinone derivatives such as 2.5-dimethoxy- hydroquinone,
2,5-dimethylhydroquinone and hydroquinone. Average molecular weights of the obtained polyethers were in theorder of 104. Thermal properties of the polyethers were studied by thermogravimetry and differential scanningcalorimetry. Polyethers started to decompose at ca. 250 ºC and their glass transition temperatures were in therange of 140 ºC to 189 ºC. The liquid crystalline phase of p-chlorophenol solutions of polyethers was observed
using a polarizing microscope.
1991-222
バクテリアセルロース製造における炭素源としての低分子酸・アルコール類
鮫島一彦、西村高明、高村憲男
高知大学農学部
Evaluation of low molecular acids and alcohols as the carbon source for the production of bacterial cellulose
Kazuhiko Sameshina, Takaaki Nishimura, Norio Takamura
Faculty of Agriculture, Kochi University
Abstract:
Low molecular nine acids and six alcohols were evaluated as the carbon source for the
production of bacterial cellulose. A bacteria, Acetobacter xylinum ATCC 10245 under the Hestrim-Schram's
mediun system was used for the evaluation. Among alcohols, glycerol gave the best cellulose yield (152% ;based on the membrane yield from glucose) and the inositol (89%) followed. Among the acids, lactic acid savethe best yield (71%) and the pH of the culture medium increased from 6.0 to 9.2. Acetic acid gave a little
cellulose yield (11.7%) but the pH of the culture medium went up to 7.95 as in the case of lactic acid.
1991-特別講演
リグニンのメカノケミストリーとパルプ漂白
住本昌之
九州大学農学部
Mechanochemistry of lignin in pulping and its relation to pulp bleaching
Masashi Sumimoto
Department of Forest Products, Kyushu University
Abstract:
Mechanochenical treatments of various types of lignin model compounds with CAM, VBM,
and laboratory refiner disclosed that O2H, OH, and H radicals were produced in the aqueous media of
mechanical pulping, similarly to those in the aqueous media of super sound. Effective attack of such radicals toeither syringyl glycerol--guaiacyl ether or (5-5')-biphenyl type of model compound hawingα-carbinol
furnished the corresponding para-carbonyl phenol, and 3-methoxy-5- substituted p-benzoquinone, respectiyely.
Furthermore. mehanical treatnent of a 5-substituted-p- carbonyl phenol ether produced a pair of chromophore,p-benzoquinone and a leucochromophore, p-hydroquinone. Alkaline H2O2 bleaching destructs most of thechromophor but the leucochromo- phores, which are believed to be the major cause of color reversion of
bleached mechanical pulp.

213

第 37 回 （1992.10.19-20） 京大会館
1992-101
担子菌 Coriolus versicolor によるリグニン分解機構の解析
飯村洋介、川合伸也、片山義博、諸星紀幸
東京農工大学農学部
Elucidation of lignin biodegradation mechanism by basidiomycete Coriolus versicolor
Yousuke Iimura, Shinya Kawai, Yoshihiro Katayama, Noriyuki Morohoshi
Department of Applied Biological Science, Tokyo Llniversity of Agliculture and Technology
Abstract:
A white-rot basidiomycete, Coriolus versicolor secrets a number of extracellular laccases. ln
polymeric lignin metabolism by C. versicolor laccase activity was closely related to the accumulation of watersoluble intermediates. In this fungus, a multitude of laccase gene related DNA sequence was observed. We havecloned and sequenced a gene coding for the ligninolytic Laccase lIl and homologus laccases of C. versicolor.
1992-102
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（I）自然界より分難したリグニン分解菌のリグニン分解特性及び菌体外酵素活性平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi. I. Lignin-degrading characteristic and extracellular enzyme
activities of new isolates of white-rot fungi
Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyusyu University
Abstract:
We previously reported that new isolates of white-rot fungi, YK-472 and YE-624, showed muchhigher ligninolytic activity and selectivity in beech-wood lignin than typical lignin- degrading fungi,
Phanerochaete chrysosporium and Coriolus versicolor. In the present work, we investigated theirlignin-degrading characteristic and extracellular enzyme activity. The fungi YK-472 and YK-624 degraded birch
dioxane lignin and residual lignin in unbleached kraft pulp (UKP) much higher than P. chrysosporium and C.
versicolor. During fungal treatment of beech wood meals, the fungus YK-624 which degraded beech-wood
lignin, showed much higher activity of extracellular peroxidase in the medium than P. chrysosporium.
1992-103
Phanerochaete chrysosporium の生産するセロビオース脱水素酵素の性質とリグノセルロース生分解におけるその役割
鮫島正浩*1、カール・エリック L. エリックソン*2*1
東京大学農学部、*1 ジョージア大学生化学科
Cellobiose dehydrogenases from Phanerochaete chrysosprium, Enzymatic properties and functions inlignocellulose biodegradation
Msahiro Samejima*1, Karl Erik L. Eriksson*2*1
Faculty of Agriculture, Uiversity of Tokyo, *2Dernrtment of Biochemistry, Center for Biological Resources a
Recovery, University of Georgia
Abstract:
In relation to ligncellulose biodegradation by Phanerochaete chrysosporium, enzymatic
properties of cellobiose oxidase (CBO) and cellobiose : quinone oxidoreductase (CBQ), especially the
specificity of electron acceptors for these enzymes, were investigated. CBO can reduce quinones as yell as CBQin the presence of cellobiose. FAD is a common prosthetic group for both enzyme. Therefore, these reductions
are conducted by FAD. Atmospheric oxygen is a poor electron acceptor for both CBO and CBQ. In contrast,
cytochrome c is utilized as an effective electron acceptor by CBO. The pH dependence experiment and thestopped flow analysis suggest that the reduction of cytochrome c is depending on the function of heme
prosthetic group in CBO indicating that cytochrone c is a most possible electron acceptor for CBO in vivo
system. The amount of CBO in the cellulolytic culture increases in the course of the fungal growth. Therefore
all of these results suggests that CBO participates in cellulose biodegradation rather than lignin biodegradation.
On the other hand, CBQ produces in the later stage of the cellulolytic culture like as a secondary metabolite.
Therefore, CBQ has less importance in cellulose bidegradation.
1992-104214

Phanerochaete chrysosporium の芳香環開裂酵素について
西田篤実、中村雅哉、中川麻里子
森林総合研究所
Aromatic ring cleavage enzyme from Phanerochaete chrysosporium
Atsumi Nishida, Masaya Nakamura, Mariko Nakagawa
Forestry and Forest Products Research Institute
Abstract:
In an investigation of vanillic acid metabolism by Phanerochaete chrysosporium, aromatic ringcleavage enzyme is very unstable so the purification of the enzyme is very difficult. In this time, we succeededin the purification of hydoxyquinol 1,2-dioxygenase and clarified the some properties. The native molecularweight of this enzyme is 94,000 Dalton and the subunit molecular weight are 40,000 and 52,.000 Dalton (bySDS-Page). The enzyme is inactivated with Fe2+ and -SH chelator. Optimum pH is 6.0-6.5 and pH stability is
6.5-7.5 in phosphate buffer.
1992-105
マツノカタワタケによる β-O-4 型リグニンサブストラクチヤーモデル二量体の分解
横田信三*1、海野 清*1*2、梅澤俊明*3、佐藤素子*1、吉沢伸夫*1*1
宇都宮大学農学部、*1*2 巴川製紙株式会社、*3 京都大学木質科学研究所
Degradation of β-O-4 lignin substructure model dimers by Cryptoderma pini
Shiunzou Yokota*1, Kiyoshi Unno*1*2, Toshiaki Umezawa*3, Motoko Satoh*1, Nobuo Yoshizawa*1*1
Faculty of Agriculture, Utsunomiya University, *2Tomoegawa Paper Co. Ltd., *3Wood Research Institute,
Kyoto University
Abstract:
Degradationofanon-phenolic(1-(4-ethoxy-3-methoxyphenyl)-2-(2,6-di-methoxyphenoxy)-1,3-propanediol (I)) and a phenolic (1-(4-hydroxy-3-methoxy-phenyl)-2-(2,6-dimethoxyphenoxy)-1,3-propanediol (II)) β-O-4 lignin substructure model diners by the intact cells of Cryptoderma pini,and activities of lignin-degrading enzymes in the extracellular culture fluid of the fungus were investigated. In
the degradation of substrate (I) by the fungus, degradation products were formed via O-C4 cleavage andβ-etherified aromatic ring opening. On the other hand, substrate (II) was degraded via alkyl-aryl cleavage. In
addition, activities of laccase and Mn(II)- dependent peroxidase were detected in the extracellular fluid of thefungus culture.
1992-106
有機溶媒中におけるペルオキシダーゼの反応
吉田晋一*1、中尾博一*2、渡辺隆司*1，桑原正章*1、麻田恭彦*2*1
京都大学木質科学研究所、*1 香川大学農学部
Reaction of peroxidase in organic solvents
Shinichi Yoshida*1, Hirokazu Nakao*2, Takashi Watanabe*1, Masaaki Kuwahara*1, Yasuhiko Asada*2*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kagawa University
Abstract:
Horseradish peroxidase (HRP) was modified with methoxypolyethylene glycol- succinimidyl
succinate (MPSS. MW 5000) to dissolve in organic solvent. The modified HRP retained over 85% of theoriginal activity in potassium phosphate buffer, and its Km value and Vmax were about the same as those ofnative enzyme. Similarly, lignin peroxidase (LiP) was purified from culture filtrate of Phanerochaetechrysosporium, and modified with MPSS under neutral pH condition. The hydrophobically modified HRP and
LiP were soluble in benzene. Reaction of both modified peroxidases in organic solvent is reported_
1992-107
透析膜法によるシナピルアルコールの酵素的脱水素重合
小川昌士、棚橋光彦、重松幹二、篠田善彦
岐阜大学農学部
Enzymatically dehydrogenative polynerization of sinapyl alcohol by dialysis membrane method
Masashi Ogawa, Mitsuhiko Tanahashi, Mikiji Shigematsu, Yoshihiko Shinoda
Faculty of Agriculture, Gifu University
Abstract:
In a plant cell wall, a lignin was deposited in the matrix of polysaccharides through thelignification process. To prepare the closer model of a native lignin, sinapyl alcohol was polymerized withhorseradish peroxidase/H2O2 in the presence of xylan or pectin by dialysis membrane method, and theirchemical structures were investigated. As a result, the ratio of acidolysis monomers to syringaresinol was
215

determined about 20 :1 in xylan and about 10 :1 in pectin. Further, there was a little benzyl phenyl ether indehydrogenation polymer (DHP) fraction of the LCC/xylan. The degree of polymerization ofthe
DHP was decided to be twenty-five by the determination of phenolic hydroxyl group and yield of acidolysis
monomers. Dehydrogenative polymerization of monolignols by the dialysis membrane method would
sufficiently simulate the lignification process in a plant cell wall.
1992-108
抗ウイルス活性を有する水溶性腐朽バガスリグニンの化学構造
梶原淳一*1、服部武文*2，城野浩之*1、島田幹夫*2
日本ケミカルリサーチ株式会社、京都大学木質科学研究所
Characterization of antiviral water-soluble lignin from bagasse degraded by Lentinus edodes
Junichi Kajihara*1, Takefumi Hattori*2, Hiroyuki Shirono*1, Mikio Shimada*2*1
JCR Pharmaceuticals Co. Ltd., *2Wood Research Institute, Kyoto University
Abstract:
We characterized water soluble lignin (WSL) which is responsible for antiviral activity of lignin
complex (LC) extracted from bagasse degraded by Lentinus edodes. The results of potassium permanganate
oxidation show that WSL contains larger amounts of condensed type structures than MWL. However, themethoxyl content of WSL was lower than that of MWL. Thus. the new evidence is that the quantities of benzene
rings in WSL were obviously reduced, which suggests that bagasse lignin were modified to those rich in ring
opening or quinone moieties during the decay process. The hydrolysis of WSL with aqueous sodium hydroxideyielded oxalic acid and formic acid, which indicates WSL contains oxalate and formate esters possibly derived
from the aromatic-ring opening structures.
1992-109
リグニン構造単位の選択的標識に関する研究（I）
福島和彦*!、松井直之*!、鎌田 要*!、安田征市*!、寺島典二*2*!
名古屋大学農学部、*2USDA 林産物研究所
Studies on the selective radio-labeling of lignin structural units in tree xylem (I)Kazuhiko Fukushima*!, Naoyuki Matsui*!, Kaname Kamada*!, Seiichi Yasuda*! , Noritsugu Terashima*2
1
Factilty of Agriculture, agoya University, 2United States Dept. of Agriculture, Forest Products Laboratory,
U.S.A.
Abstract:
For the selective labeling of lignin structural units, monolignol glucosides are considered as
suitable precursors. However, during a long term metabolism after the administration of these labeled precursors,a certain proportion of interconversion between each units (p-hydroxy- phenyl, guaiacyl, syringyl) was often
observed. To avoid this conversion, -hydrogens labeled monolignol glucosides were employed. If theconversions occur, these -hydrogens must be released because in lignin biosynthetic pathway, it is consideredthat OMT functions for p-hydroxy cinnamic acids which has no -hydrogens. In this study, -hydrogens inmonolignol glucosides were labeled with deuteriums, and their behavior during the dehydrogenatedpolymerization was investigated using the preparing DHP. It was found the -hydrogens were stable through thereaction.
1992-110
リグニン構造単位の選択的標識に関する研究（II）
松井直之*1、福島和彦*1、、安田征市*1、寺島典二*2*!
名古屋大学農学部、*2USDA 林産物研究所
Studies on the selective radio-labeling of lignin structural units in tree xylem (II)Naoyuki Matsui*1, Kazuhiko Fukushima*1, Seiichi Yasuda*1 , Noritsugu Terashima*2*1
Factilty of Agriculture, agoya University, *2United States Dept. of Agriculture, Forest Products Laboratory,
U.S.A.
Abstract:
To achieve the selective labeling of lignin structural units, the γ-position of lignin C6-C3 units
was labeled by the administration of γ3H labeled monolignol glucosides to the plants. The newly formed lignin
was degraded to C6-C3 units by thioacidolysis, and the radioactivity of degradative products (derived fromguaiacyl, syringyl units) were measured. The perfectly selective labeling was expected, however, a considerable
proportion of interconversion was observed in the angiospermous trees administered with p-glucocoumary
lalcohol and coniferin. When syringin was administered, little conversion was observed. These suggest that newroute (or mechanism) of interconversion which does not pass the cinnamic acids exists in the lignin
216

biosynthesis.
1992-111
広葉樹樹幹先端部における木部分化とリグニン不均一形成に関する研究
福島和彦*1、高部圭司*２、寺島典二*３、安田征市*1*!
名古屋大学農学部、*２京都大学農学部、*３USDA 林産物研究所
Studies on the heterogeneous formation of lignin in the elongating shoot of Magnolia kobus
Kazuhiko Fukushima*1, Keiji Takabe*2, Noritsugu Terashima*3 and Seiichi Yasuda*1*1
Faculty of Agriculture, Nagoya University, *２Faculty of Agriculture, Kyoto University, *3United States Dept. ofAgriculture, Forest Products Laboratory, U.S.A.
Abstract:
The differences in lignification between the vessel of primary xylem and that of secondary
xylem are discussed. The vessels of primary xylem of Magnolia kobus have thickened spiral secondary wall.
This secondary wall lignifies in the early stage of shoot formation. However, the lignification of the compound
middle lamella is fairly delayed. This pattern of lignification is quite different from that of secondary xylem. In
addition, surprisingly, it was found that the vessel of primary xylem with lignified secondary wall dramaticallyelongated (approximately 3.5 fold) like a spring coil during the growth of the shoot.
1992-112
雲南省産カエデ属数種のリグニンの分布
平井陽子、深沢和三
北海道大学農学部
Distribution of lignins on the genus Acer in Yunnan
Yoko Hirai, Kazumi Fukazawa
Faculty of Agriculture, Hokkaido University
Abstract:
Distribution of lignins of 5 species on the Genus Acer in Yunnan was investigated by Mäule
reaction, ultraviolet microscopy and Klason method. Absorption spectra of Mäule reaction show that all 5
species were syringyl lignin rich in all elements.
1992-113
Forsythia sp．のリグナン生合成の初発段階を触媒する(＋)−ピノレジノールシンターゼ
片山健至*1*2，L.B. Davin*1，D.L．Bedga*1，N.G．Lewis*1*1ワシントン州立大学、*２香川大学農学部(+)-Pinoresinol synthase: The first enzymatic step committed to lignan biosynthesis in the Forsythia sp．
Takeshi Katayama*1, *2, Laurence B. Davin*1, Diana L. Bedgar*1, Norman G. Lewis*1*1
Institute of Biological Chemistry, Washington State University, *2Faculty of Agriculture, Kagawa University
Abstract:
Detailed fractionation studies have determined that in the insoluble residue from Forsythia sp (F.
suspensa and F. intermedia) there exists a coniferyl alcohol coupling enzyme which catalyzes preferential
formation of (+)-pinoresinol in the absence of cofactors. When NAD and malate were supplied, thestereoselectivity of the coupling reaction was enhanced. Sinapyl alcohol does not serve as a substrate for thisenzyme i.e. in this case stereoselective coupling does not occur. Thus, lignan biosynthesis in the Forsythia sp. is
initiated by the coupling of the two coniferyl alcohol molecules to give (+)-pinoresinol, this being the firstisolable product of stereoselective coupling.
1992-114(＋)−ピノレジノールのエナンチオ特異的還元片山健至*1*2，L.B. Davin*1，Alex Chu*1，N.G．Lewis*1*1ワシントン州立大学、*２香川大学農学部、Enantiospecific reduction of (+)-pinoresinol
Takeshi Katayama*1, *2, Laurence B. Davin*1, Alex Chu*1, Norman G. Lewis*1*1
Institute of Biological Chemistry, Washington State University, *2Faculty of Agriculture, Kagawa
University
Abstract:
Time-course experiments using Forsythia intermedia cell-free extracts, incubatedwith coniferyl alcohol in the presence of NADPH and H2O2, revealed that formation of (-)-secoiso- lariciresinol
was linear over the time period examined. But, these crude cell-free extracts also catalyzed formation of(±)-pinoresinols as the initial coupling products. The (+)-enantiomer was then selectively depleted, as a function217

of time, from the incubation mixture, with concomitant formation of (-)-secoisolariciresinol. By contrast, the(-)-antipode remained unchanged. Next, the cell-free extracts were incubated with (±) and (+)-pinoresinols.
Formation of (-)-secoisolarici- resinol from the (+)-antipode was again observed, but only required NADPH as a
cofactor.
1992-115
Lignan biogenesis： Towards elucidating ragio- and enantiospecific methylation/glucosylation transformations
beyond matairesinol
Shuji Ozawa, Laurence B. Davin, Norman G. Lewis
Institute of Biological Chemistry. Washington State University
Abstract:
Since the pathway from (+)-pinoresino[ to (-)-matairesinol in Forsythia intermedia
is characterized by highly enantioselective enzymatic conversions, it was of interest to establish whether
comparable enantioselectivity was extended into arctigenin/arctiin formation, and if the apparent
regiospecificity of methylation was controlled at this stage. But, in contrast to previous enantiosesective
enzymatic steps affording (-)-matairesinol, it was found that both (+)- and (-)-antipodes of matairesinol served
as substrates for methylation -with the naturally occurring (-)-enantiomer slightly preferred. Surprisingly, themajor enzymatic products were (+)- and (-)-isoarctigenins rather than the naturally occurring regio-isomer,(-)-arctigenin. Thus, O-methyLation of matairesinol was neither enantioselective or regiospecific. Further, only
monomethylation was observed, since no evidence for dimethyl matairesinol formation occurred. Taken together,
it is proposed that regiospecific methylation of matairesinol does not proceed to give arctigenin directly. Instead,regiospecific glucosylation is presumed to first occur to afford matairesinoside. Subsequent methylation affords
arctiin, which is converted into arctigenin via action of a β-glucosidase.
1992-116
Forsythia koreana のリグナン生合成酵素
梅澤俊明、黒田宏之、五十幡俊成、島田幹夫
京都大学木質科学研究所
Enantioselective lignan formation by cell-free extracts of Forsythia koreana
Toshiaki Umezawa, Hiroyuki Kuroda, Toshinari lsohata, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Cell-free extracts from Forsythia koreana catalyzed the formation of (-)-secoiso- lariciresinol,
as well as (-)-pinoresinol and (-)-lariciresmol. When incubated with coniferyl alcohol in the presence of
NADPH and H2O2. The extracts also catalyzed the formation of (-)-secoisolarici- resinol from (±)-lariciresinol.
The mechanisms of the enantioselective (-)-secoisolariciresinol formation are discussed.
1992-117
ウド（Aralia coradata）シンナミルアルコールデヒドロゲナーゼ cDNA の単離および解析
日尾野隆*1、柴田大輔*1、樋口隆昌*2*1
三井植物バイオ研究所、*2 日本大学農獣医学部
Isolation and characterization of a cDNA encoding cinnamyl alcohol dehydrogenase from Aralia cordata
Takashi Hibino*1, Daisuke Shibata*1, Takayoshi Higuchi*1*1
Mitsui Plant Biotechnology Reserch lnstitute, *2College of Agriculture and Veterinary Medicine, Nihon
University
Abstract:
We isolated a full-length cDNA clone encoding cinnamyl alcohol dehydrogenase (CAD;
EC1.1.1.195) from Aralia cordata by oligonucleotide-screening derived from amino acid sequence of A.
cordata CAD protein. The cDNA clone comprised a open reading frame of 1080 base pairs. The partial aminoacid sequences of peptides isolated from the purified CAD of A. cordata were found in that deduced from thecDNA nucleotide sequence. This showed the cDNA clone encodes CAD of A. cordata.
1992-118
樹木フエニルプロパノイド系生合成酵素遺伝子群の単難・解析
早川敏雄*1、大坪祐二*1、刑部祐里子*1、川合伸也*1、諸星紀幸*1、片山義博*２、秦 邦男*2
*1
東京農工大学農学部、*２東京農工大学共同研究開発センター、*３十条製紙株式会社
Isolation arid analysis of the genes encoding the enzymes for phenylpropanoids biosyrlthesis in woody plants
Toshio Hayakawa*1, Yuuji Ootsubo*1, Yuriko Osakabe*1, Shinya Kawa*1i, Yoshihiro Katayama*1, Noriyuki
218

Morohoshi*1,Kunio Hata*2*1
Faculity of Agricult,urc,Tokyo University of Agriculture and Technology, *２Cooperative Research Center,
Tokyo University of Agriculture and Technology,*2JuJo Paper. Co., LTD.
Abstract:
We use Populus kitakamiensis as a model for analysis of lignification in woody plants. For the
analysis of gene regulation in lignification process and moleculer breeding of lignin less tree, it is necessary toisolate the genes encoding enzymes for lignin biosynthesis. We isolated some phenylalanine ammonia-lyase,O-methyltransferase, and peroxidase genes from the poplar genome. And some of them were characterized.
1992-119アンチセンス RNA 法を用いた樹木の分子育種
川合伸也*1、三浦 進*1、梶田真也*1、諸星紀幸*1、片山義博*2、秦 邦男*3
*1
東京農工大学農学部、*２東京農工大学共同研究開発センター、*3 十条製紙株式会社
Molecular breeding of woody plants by using antisense RNA method
Shinya Kawai*1, Susumu Miura*1, Shinya Kajita*1,Yoshihiro Katayama*1, Noriyuki Morohoshi*1, Kunio Hata*2*1
Faculity of Agricult,urc,Tokyo University of Agriculture and Technology, *２Cooperative Research Center,
Tokyo University of Agriculture and Technology *3JuJo Paper. Co., LTD.
Abstract:
Cells of the hybrid poplar (Populus kitakamiensis) were transfomed by Agrobacteriummediated gene transfer and regenerated into plants from the transformed calli. T-DNA of plasmid DNA, pBI121,
bearing marker genes encoding beta-glucronidase (GUS) and neomycin phospho- transferase (NPTII) wereintroduced by non-oncogenic Agrobacterium tumefaciens LBA4404 using leaf disk method. The transformed
cells grew into calli on the selective medium containing kanamycin and calli regenerated into plants. The
kanamycin resistant plants were analysed by Southern blot hybridization and a fluorometric assay for GUS. All
kanamycin resistant plants had two marker genes and were confined as transformants. And sense or antisense
genes for phenylalanine ammonia-lyase or peroxidase derived from the poplar genome were introduced into the
poplar and the transfomants were regenerated into plants.
1992-120
リグニンビフエニル型化合物の分解酵素遺伝子の解析
窪田祥子*1、片山義博*2、花城 薫*1、木村尚代*1、政井英司*1、川合伸也*1、諸星紀幸*1*1
東京農工大学農学部、*２東京農工大学共同研究開発センター
Cloning of the genes involved in degradation of biphenyl structure of lignin compounds
Sachiko Kubota*1, Yoshihiro Katayama*2, Kaoru Hanashiro*1, Hisayo Kinura*1, Eiji Masai*1, Shinya Kawai*1,
Noriyuki Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology
Abstract:
Pseudomonas paucimobilis SYK-6 is able to grow on DDVA ( biphenyl structure of lignin) as asole carbon source. We have already reported that the metabolism of DDVA proceeds via intermediates,
OH-DDVA, 5-carboxyvanillate. The first step in the catabolism of DDVA by SYK-6 is the demethylation of
DDVA to OH-DDVA. In this study we report, using as a host strain for the nitrosoguanidine mutant NT1 which
was isolated for loss of the ability to use DDVA as a carbon source, we isolated the genes involved in DDVA
catabolism.
1992-121β-アリールエーテル開裂酵素遺伝子群の機能と構造
政井英司*1、窪田祥子*1，片山義博*2、川合伸也*1、山崎真狩*3，諸星紀幸*2*1
東京農工大学農学部、 *2 東京農工大学共同研究開発センター、*３東京大学農学部
Structures and functions of the genes involved in the cleavage of β-aryl ether
Eiji Masai*1, Sachiko Kubota*1, Yoshihiro Katayama*2, Shinya Kawai*1, Makari Yamasaki* ３ , Noriyuki
Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center, Tokyo
University of Agriculture and Technology,*2Faculty of Agriculture, the University of Tokyo
Abstract:
Pseudomonas paucimobilis SYK-6 is able to assimilate various types of dimeric lignin
compounds. Cleavage of arylglycerol-β-aryl ether is essential in the lignin degradation. We have alreadycharacterized the β-etherase gene (ligE). Here, we isolated and characterized the C- dehydrogenase gene (ligD).
C-dehydrogenase catalyzes the oxidation of arylglycerol-β-aryl ether and this process produces the specific219substrate for β-etherase. Homology search showed that ligD had a homology with ribitol dehydrogenase family.
Mapping and sequencing analysis indicated ligD and ligE were separated by an open reading frame encoding
another -etherase gene (ligF). β-etherase activity of ligF expressed in Escherichia coli was more than100 times
as high as that of ligE. We found that ligF was homologous to glutathione S-transferase. Drastic acceleration ofβ-etherase activity was observed in the reaction mixture including ligF by addition of glutathione.
1992-201
リグニンの熱分解ガスクロマトグラフィー（第 4 報）単難リグニンの熱分解ガスクロマトグラフィ
黒田健一*1、山口 彰*1、坂井克己*2*1
筑波大学農林工学系、*2 九州大学農学部
Analysis of lignin by pyrolysis-gas chromatography (IV), Pyrolysis-gas chromatography of sugi wood, its lignin
preparations and synthetic lignin
Kenichi Kuroda*1, Akira Yamaguchi*1, Kokki Sakai*2*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2Faculty of Agriculture, Kyushu
University
Abstract:
Curie-point pyrolysis of wood and several isolated lignins from sugi (Cryptomeria japonica D.
Don) and synthetic lignin was performed. Pyrolysis products were analyzed by GC and GC/MS. Total yields of
selected pyrolysis products were ordered as follows: wood > DHP > MWL > alcohol bisulfite lignin>HC1-lignin > DL >> KL. Py-GC of lignin gave different product distribution profiles from that of woodmeal; coniferyl alcohol was the most abundant lignin marker product in the wood pyrolysate, and a minor
product in its lignin pyrolysate. These findings showed that analytical pyrolysis data may help in achieving abetter understanding of the structural change of lignin.
1992-202
リグニンのメカノケミストリー（XVI） グアイアシルグリセロール-β-グアイアシルエーテルのメカノケミストリー
伊藤和貴、住本昌之、田中浩堆
九州大学農学部
Mechcanochemistry of lignin (XVI), Mechanochemical conversions of guaiacylglycerol-β-guaiacyl ether
Kazutaka Itoh, Masashi Sumimoto, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Mechanochernical conversions of vanillylalcohol I, α-methyl vanillylalcohol II, and guaiasylglycerol-β-guaiacyl
ether IV were investigated. Two types of conversions occurred by the treatment of compound IV with VBM.
The major reaction furnished firstly the corresponding p-carbonyl phenol 4, which afforded six products
similarly to the case of syringylglycerol-β-guaiacyl ether, but strangely included 2-methoxy-p-hydroquinone 5.
The minor reaction involved Abstraction of phenolic H atom followed by dimerization to give compound 10
which was oxidized further via compound 11 to 12.
1992-203
爆砕処理よるリグニンの分解機構の解明（VI） シリンギル型リグニンモデル化合物の水蒸気処理
M. Karina＊１＊２、上野直之＊２，棚橋光彦＊２、桑原正章＊３＊１
LIPI-PPPFT、＊２岐阜大学農学部、＊３京都大学木質科学研究所
Degradation mechanism of lignin by steam explosion (Vl), - Steam treatment of syringyl type of lignin modelcompoundM. Karina＊１＊２, Naoyuki Uenot＊２, Mitsuhiko Tanahashi＊２, Masaaki Kuwahara＊3＊１
LIPI-PPPFT,＊２Faculty of Agriculture, Gifu University,＊3Wood Research lnstitute, Kyoto University
Abstract.
ln order to explain the degradation mechanism of lignin by steam explosion, syringylglycerol-β-sinapylalcohol ether (SS) was used in the present study. This model compound was subjected to thesteam treatment, 230 ºC, 2.9 MPa for 4 min. Steam treatment of S-DHP and S-LCC was also subjected to thesteam treatment. The major degradation product obtained from steamed SS was syringaresinol. Other products
found were sinapyl alcohol, sinapaldehyde, dehydrosinapyl alcohol and syringaldehyde. On the other hand,
β-oxysinapylalcohol as the majordegradation product of acidolysis was not detected. This result suggested that the degradation mechanism oflignin by steam explosion is different from acidolysis. By the condition used. β-ether linkage of SS was cleaved
homolytically and formed sinapyl alcohol radical. These adicals were
homocoupled to give syringaresino1, and reduction of sinapyl alcohol radical formed sinapyl alcohol. The
220

results obtained from steam treated S-DHP and S-LCC were similar with that from SS. However, from steamed
S-DHP, sinapaldehyde was obtained much more than that of sinapyl alcohol. The difference in the amounts ofthe degradation products possibly due to the different oxidation levels of the C6-C3 units of the molecule. ln theSS, each phenolic unit was subjected to one- electron oxidation (the oxidation level is similar to the sinapyl
alcohol radical). In the S-DHP, to produce a polymer, one-electron oxidation occurred twice (the oxidation levelis similar to sinapyl aldehyde radical). On the other hand, from steamed S-LCC, sinapyl alcohol was produced
much higher than that of sinapaldehyde. Sinapyl alcohol radical results from the cleavage of β-ether by steam
treatment was reduced by the hemicellulose exist in S-LCC.
1992-204
機能性リグノフェノール誘導体の調製およびその特性
松江淳介、船岡正光
三重大学農学部
Preparation of functional lignophenols and their characteristics
Junsuke Matsue, Masamitsu Funaoka
Faculty of Bioresources, Mie University
Abstract:
A new conversion technique (SS Conversion Process) of protolignins and technicallignins into functional lignophenols has been developed. The characteristics of this process are as follows : 1.
Rapid conversion at room temperature. 2. No special chemicals and equipment. 3. Selective phenolation at
-positions of lignin side chains. 4. Disappearance of conjugated systems. The resulting lignophenols have highreactivity and new functions as phenolic polymers. In the present paper, the characteristics and procedure of SSconversion process are described, compared with conventional phenolation techniques.
1992-205
高度の縮合構造を有する酸リグニンの可溶性リグノスルホン酸への変換
松下泰幸、安田征市
名古屋大学農学部
Conversion of highly condensed acid lignin into water-soluble lignosulfonate
Yasuyuki Matsushita, Seiichi Y'asuda
Faculty of Agriculture, Nagoya University
Abstract:
Conversion of highly condensed sulfuric acid lignin into water-soluble lignosulfonate wasinvestigated. At first, sulfuric acid lignin was phenolized to enhence its reactivity. Two methods were tried toconvert phenolized SAL into water-soluble lignosulfonate. One was hydroxymethylation, followed by neutral
sulfite treatment, and the other was sulfomethylation with hydroxymethane sulfonate. Sulfur content introducedby the two-step procedure was higher than that by the one- step method and commercial lignosulfonates. The
two-step method gave higher molecular weight products than the one-step procedure, maybe because ofpolymerization during hydroxymethylation and sulfonation.
1992-206
カルボキシルメチル化リグニンの合成とその特性について
木村泰章，熊田直子，滝沢正博，中村昌允
ライオン株式会社、素材開発センター
Synthesis and properties of carboxymethylated lignin
Yasuaki Kimura, Naoko Kumada, Masahiro Takizawa, Masayoshi Nakamura
Advanced Materials Research Center, Lion Co., Ltd.
Abstract:
The purpose of this study is to synthesize a water-soluble dispersing agent fromwater-insoluble lignin which is obtained from softwood by acetic acid-digestion. The dispersing agent was
synthesized by carboxymethylation of the lignin with monochloroacetic acid. This carboxymethylation was
successfully performed by heterogeneous reaction of the lignin dipped into 48% NaOH-aq. andmonochloroacetic acid in 2-propanoｌ (IPA). We found this carboxymethylated lignin was easily soluble inwater and had a calcium sequestering capacity of 130mg-CaCO3/g and a dispersing power for Fe2O3 particles.
Keywords: 酢酸蒸解・リグニン・脱アセチル化リグニン・カルボキシメチル化リグニン・Ｃａイオン捕捉能・分散能、dispersing agent, acetic acid cooking, deacetylated lignin, carboxymethylated lignin, calcium ion
sequestering capacity, dispersibility
221

1992-207
リグニンを原料とするポリエステルポリウレタンの調製と熱的性質
広瀬重雄*1、小橋川健*2、畠山兵衛*1*1
製品科学研究所、*2 トロピカルテクノセンター
Preparation and thermal properties of polyester-polyurethanes derived from lignin
Shigeo Hirose*1, Ken Kobashigawa*2, Hyoe Hatakeyama*1*1lndustrial Products Research Institute, *2Tropical Technology Center Ltd..
Abstract:
Polyurethane foams (PU) could successfully be prepared by the following procedure. A mixture
consisting of a ethylene glycol (EG) solution of kraft lignin and polyester-polyol (PES, diol- typepolycaprolactone, molecular weight 550) was reacted with diphenylmethane diisocyanate (MDl) in the presenceof a small amount of water, tin catalyst and silicone surfactant. Thermal properties of PU's were studied bythermogravimetry (TG) and differential scanning calorimetry (DSC). Mechanical properties of the obtained
foams were also studied by compression test. The effect of the addition of kraft lignin to PU's is considered inthis paper.
1992-208
Synthesis and thermal properties of liquid crystalline aromatic copolyesters from phenols related to lignin
M. Acevedo, Shigeo Hirose, Hyoe Hatakeyama
Industrial Products Research Institute
Abstract:
New aromatic copolyterephtahalates combining two hydroquinones such as: methoxyhydroquinone (MHQ), 2,6-dimethoxyhydroquinone (DHQ) and 4,4’-dihydroxy-3,3’,5,5'- tetramethoxy-biphenyl(THQ), have been synthesized and characterized starting with lignin-related phenols. These copolymers showedliquid crystalline properties according to the observation by polarizing microscopy and differential scanningcalorimetry.
1992-209
中温硬化型リグニン樹脂接着剤の製造
島谷啓二、佐野嘉柘
北海道大学農学部
Preparation of medium-temperature setting lignin-based wood adhesives
Keiji Shimatani, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
The utilization of kraft lignin in the substrate of medium-temperature setting wood adhesives
was investigated. A mixture of the lignin and phenol was hydroxymethylated under alkali conditions withvarious molar ratios of formaldehyde and methanol at 80 ºC for 2 hours. Resorcinol or wattle tannin andparaformaldehyde were added to the hydroxymethylated products in order to prepare the adhesives. The
adhesives yielded high bonding strength and water resistance at hot pressing temperature of 100 ºC. The
hydroxymethylated products were analyzed by GPC,1H-NMR, 13C-NHR, HPLC and so forth.
1992-210
酢酸リグニンの繊維化
久保智史*1、浦木康光*1、佐野嘉拓*1、笹谷宜志*1、小川正人*2*1
北海道大学農学部, *2 北海道大学理学部
Preparation of lignin fiber from acetic acid lignin
Satoshi Kubo*1, Yasumitsu Uraki*1, Yoshihiro Sano*1, Takashi Sasaya*1, Masato Ogawa*2**1Flaculty of Agriculture, Hokkaido University, *2Faculty of Science,Hokkaido University
Abstract:
Acetic acid lignin (AWL) which was prepared from birch chips by atmospheric acetic acid
pulping containing H2SO4 had a melt spinnability. However the lignin fiber spun out of AWL had a roughsurface and had some micropores probably due to the elimination of low molecular weight volatile materials. In
this study, we tried heat treatment of AWL as pretreatment to solve these problems. The heat treatment at l60 ºC
reduced the amount of micropores of the surface. Consequently the treatment gave a easily spinning condition.
1992-211
硫酸触媒による常圧酢酸パルプ化 —単離リグニンの化学構造
堀崎敬史、島谷啓二、佐野嘉拓、笹谷宜志
222

北海道大学農学部
Pulping at atmospheric pressure with aqueous acetic acid containing a small amount ofsulfuric Acid. -Chemical structure of isolated lignins
Yoshifumi Horisaki, Keiji Shimatani, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Abstract:
Cellulose, hemicellulose, and lignin can be recovered quantitatively without tedious operation
by atmospheric pulping with aqueous acetic acid containing a small amount of sulfuric acid. We reported that
acetic acid lignins (AWL) with large amounts of phenolic hydroxyl groups had high reactivity, which may be
useful for the substrate of synthetic phenol polymers. To examine the chemical structure of AWLs in detail, thecontent of phenolic and aliphatic hydroxyl, carbonyl and carboxyl groups, degree of condensation and so forth
in AWLs were determined. And the effects of polysaccharides on delignification during pulping were also
examined.
1992-212
The high efficiency of cellulose poduction by Acetobacter xylinum ATCC 10245 in a new culture medium witha sulfite pulping waste fraction
Siripong Premet、鮫島一彦、高村憲男
高知大学農学部
The high efficiency of cellulose poduction by Acetobacter xylinum ATCC 10245 in a new culture medium witha sulfite pulping waste fraction.
Siripong Premet, Kazuhiko Sameshima, Noiro Takamura
Faculty of Agriculture, Kochi University
Abstract:
A new culture medium named KC medium (based on KOCHI) is a compound with a fraction of
sulfite pulping waste (commercially available), glucose, yeast extract, peptone and buffer compounds. Thisnutrient culture medium showed high efficiency for cellulose production than the standard culture medium.
Acetobacter xylinum ATCC 10245 was cultured in KC medium at static condition, and 2% glucose KC medium
gave high cellulose membrane yield (about 300%) than 2% glucose standard medium.
1992-213
クラフトパルプ残留リグニンの特性 —S-S プロセスによる評価
浜口佳織、船岡正光
三重大学農学部
Characterization of kraft pulp residual lignin by swelling-solvation process
Kaori Hamaguchi, Masamitsu Funaoka
Facult.y of Bioresources, Mie University
Abstract:
Swelling-solvation (SS) technique was applied to separate and characterize kraft pulp residual
lignins. The SS process has originally been developed for the quantitative separation of lignin with selective
structural modifications from lignocellulosics. The key point of this process is to destroy carbohydrates byconcentrated sulfuric acid under the solvation of lignin with cresol. The mass balance of residtlal ligrlins in the
SS reaction system was determined in detail, and properties of SS separated residual lignins were comparedwith those of dissolved lignins subjected to the same SS treatment. Through these data, the chemical andpolymeric characteristics of pulp residual lignins were discussed.
1992-214
リグニンの酵素分解に関する研究（III）メンブランフィルターを用いた培養系におけるクラフトパルプ残留リグ
ニンの挙動
蔵敷賢二、近藤隆一郎、坂井克己
九州大学農学部
Modification of residual lignin in unbleached kraft pulp by extracellular enzymes excreted from white-rot fungiin a cultivation system using a membrane filter
Kenji Kurashiki, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
In a previous work, we demonstrated the modification of dioxane lignin by extracellularenzymes excreted from white-rot fungi using two membrane filters of different thickness, and suggested that thedegradation of the low-molecular-weight dioxane lignin depended on the distance between the hyphae and the223lignin sample. In the present experiment, some beech unbleached kraft pulp sheets were treated in thiscultivation system. About 10% of residual lignin in kraft pulp was degraded by treatment with Phanerochaetechrysosporium or Coriolus versocolor if the thin membrane filter was used, although almostt 100% of lignin
was recovered in the thick-membrane system. The ligninolitic activities of fungus YK-624, and YK-472 whichwere isolated from decayed wood were superior to those of P. chrysosporium and C. versocolor in thethin-membrane system. Consequently, it was suggested that the degradation of the residual lignin in kraft pulp
also depended on the distance between the hyphae and the surface of kraft pulp sheet.
1992-215
リグニン分解菌によるクラフトパルプ漂白廃液の処理（IV）自然界より分離したリグニン分解菌によるクラフト
パルプ漂白廃液の脱色
李 宣鎬、近藤隆一郎、坂井克己
九州大学農学部
Decolorization of kaft bleaching effluent by lignin-degrading fungi (IV), Screening of wood-rotting fungi for
efficierlt decolorization of kraft bleaching effluent
Seon-Ho Lee, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
To find a more efficient system for the decolorization of kraft pulp bleaching (E1) effluent, wehave performed screening for high-decolorization fungi from l52 strains of isolated wood-rotting fungi. We
observed that most of the guaiacol-colorization positive fungi showed the efficient decolorization of the E1
effluent. A highly significant correlation between the decolorization of the E1 effluent and the degradation oflignin in wood was not observed for isolated wood-rotting fungi. From decay wood samples we could isolate
three fungi (MZ-227, MZ-400 and YK-624) having high decolorization activity of the E1 effluent withadditional nutrients. Moreover, the fungus KS-62 showed the excellence in the decolorization and the reductionof the UV absorbance (280 nm) of the E1 effluent without any additional nutrients.
1992-216
酸処理によるクラフトパルプの無塩素漂白
細谷修二、富村洋一、島田謹爾
森林総合研究所
Acid treatment as one stage of non-chlorine bleaching
Shuji Hosoya, Yoichi Tomimura, Kinji Shimada
Forestry and Forest Products Research Institute
Abstract:
Beech kraft pulp of a kappa number 20.5 was successfully delignified by 95 % acetic acidtreatment with a small amount of hydrochloric acid at a refluxing temperature. The degree of delignification andthe decrease in pulp viscosity highly depended on the amounts of hydrochloric acid added. The delignification
was accelerated by the addition of nitrates and the selectivity increased. Finally the kappa number below five
was achieved with the viscosity above twenty c.p.. Better result was also obtained in aqueous soluti , without
using acetic acid, by adjusting the pH with sulfuric acid and applying the alkaline extraction after acidtreatment.
1992-217
クラフトパルプの無塩素漂白.
オゾン漂白におけるパルプ粘度低下の機構
岸本崇生、中坪文明、村上浩二
京都大学農学部
Non-chlorine bleaching of kraft pulps, -Mechanism of viscosity drop in ozone bleaching
Takao Kishimoto, Fumiaki Nakatsubo, Koji Murakami
Faculty of Agriculture, Kyoto University
Abstract:
A oxygen-bleached hardwood kraft pulp was treated with ozone at low consistency in acidic
aqueous medium with sulfuric or oxalic acid and in methanol. These reaction conditions have been found to
inhibit carbohydrate degradation. Here, we considered that the viscosity drop may be caused by two reactions,direct glycosidic bond cleavage during ozone bleaching and indirect reaction caused by carbonyl groups formedby oxidation. As a result of these experiments, it is indicated that methanol inhibits the direct glycosidic bondcleavage, not oxidation, contrary to the expectation reported earlier.
224

1992-218
漂白過程で生じる有機塩素化合物の性状
新谷博幸、松本雄二、飯塚堯介、石津 敦
東京大学農学部
Nature of chlorinated organic compounds
Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka and Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo,
Abstract:
Unbleached hardwood kraft pulp, oxygen semibleached hardwood kraft pulp andunbleached softwood MCC pulp were chlorinated at various levels of chlorine ratio (0.1-0.3). The mostsignificant difference between chlorinated lignin from softwood and that from hardwood is water solubility.
Chlorolignin formed from hardwood kraft pulp is highly water soluble and, thus, considerable part of TOC (totalorganic carbon) and TOCl (total organic chlorine) are found in chlorination liquor, whereas only small part ofchlorolignin became water soluble during chlorination of softwood pulp. Chemical structure of chlorolignin inoxygen semibleached pulp was quite different from that in non-semibleached pulp, and the former lignin was
dissolved out more easily than the latter.
1992-219
リグニンペルオキシダーゼによるクロロフェノールの分解
藤井里絵、小野克正、松本雄二、石津 敦、桃原郁夫
東京大学農学部、森林総合研究所
Inhibition of lignin peroxidase oxidation of veratryl alcohol by chlorophenols
Rie Fujii, Katsumasa Ono, Ikuo Monohara, Yuji Matsumoto, Atsushi lshizu
Faculty of Agriculuture. the University of Tokyo
Abstract:
When veratryl alcohol (VA) is treated with lignin peroxidase (Lip) in the presence ofchlorophenols, the VA-oxidation is inhibited in a special manner. The inhibition period, which is difined as thetime until VA-oxidation started, was analyzed in terms of concentrations of VA and chlorophenols. In thepresence of an enough amount of VA, the inhibition period was proportional to the concentration ofchlorophenols. With the increase in the concentration of VA, the inhibition period decreased and reached aminimum value. Kinetic analyses of this reaction indicated the presence of highly reactive species which arecapable of degrading chlorophenols.
1992-220
クラフトパルプ前処理酸素漂白法の機構と新しい前処理方法の検索
大井 洋、田尻政直、岩永雄三、青柳哲夫、大内基弘
日本紙パルプ研研究所
Mechanism of pretreatment for oxygen bleaching of kraft pulp and a new pretreatment
Hiroshi Ohi, Masanao Tajiri, Yuzo lwanaga, Tetsuo Aoyagi, Motohiro Ohuchi
Japan Pulp a Paper Research Institute
Abstract:
A new pretreatment method with nitrite, acid and oxygen for oxygen bleaching was proposed
while mechanism of various pretreatments was discussed in this study. Although the pretreatment called
Samuelson's S3 process fairly improves oxygen bleaching, it requires the two-stages pretreatment. Furthermore,in its first stage, the reaction is done with gas-phase nitrogen dioxide and a pulp of high consistency. These
defects were removed for the new pretreatment method. For the improvement of oxygen bleaching, nitrite has
an important role both in the second stage of S3 process and the new method. In the new method, oxygen shouldhave an important effect on the oxidation of lignin and its activation for oxygen bleaching.
1992-特別講演 S-1
森林環境と微生物 —森林ときのこの共生
小川 真
株式会社、関西総合環境センター・生物環境研究所
Forest environment and microorganisms. Symbiosis between forest tree and mushroom
Makoto Ogawa
The General Environmental Technos Co. Ltd.
Keywords: evolution, wood rotting fungi, mycorrhiza, vesicular-arbuscular mycorrhiza,225

1992-特別講演 S-2
セルロース系材料の機能変換
京都大学化学研究所
宮本武明
Functionality conversion of cellulosic materials by chemical modifications and structural controls
Takeaki Miyamoto
Institute for Chemical Research, Kyoto University
Abstract:
Recently cellulose has been reevaluated as a functional material to meet diverse needs oftoday's society. This is mainly due to the unique reactivities and molecular characteristics of cellulose, which is
nontoxic, biodegradable, biocompatible, hydrophilic, chiral, and semi-rigid. Rather simple chemical
modifications allow the conversion of cellulose to materials of novel functions for practical use, whileconserving the cellulose characteristics mentioned above. Currently in the author's laboratory, by means ofchemical modifications and structural controls, naturally occurring polymers like cellulose and chitin areattempted to be converted from mere structural polymers to new materials with special functions. This
presentation intends to illustrate examples of cellulose modifications as broadly as possible. The topics include(i) substituents distribution control of conventional cellulose derivatives, (ii) thermoplasticization of cellulose
and its applications, (iii) thermotropic liquid crystals and LB films from cellulose, (iv) highly dielectric cellulose
derivatives, and (v) preparation and functionalization of oligosaccharides.

226

第 38 回 （1993.11.15-16） 四国電力株式会社 総合研究所
1993-101
熱分解ガスクロマトグラフィーによる広葉樹型リグニンの分析（I）アルカリ性ニトロベンゼン酸化との比較
和泉明子、黒田健一、山口 彰
筑波大学農林工学系
Analysis of hardwood lignin by pyrolysis-gas chromatography. I. Comparison of pyrolysis with alkaline
nitrobenzene oxidation using synthetic lignin
Akiko Izumi, Kenichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Several synthetic lignins (DHPs) with various syringyl/guaiacyl ratios were prepared by the
dialysis method, and Curie-point pyrolyzed at 500ºC for 4 s. The products were identified by GC/MS andestimated by GC with FID. The observed pyrolysis products were same as those from tochinoki (Aesculus
turbinata). Yields of degradation products and their S/V ratios were compared with those by alkaline
nitrobenzene oxidation.
1993-102
熱分解ガスクロマトグラフィーによる日本産針葉樹の分析
黒田健一、山口 彰
筑波大学農林工学系
Analysis of some Japanese softwoods by pyrolysis-gas chromatography
Kenichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
To find out any difference in lignins between softwood species, an analytical pyrolysis
technique, pyrolysis combined with gas chromatography (Py-GC), was applied to 16 Japanese softwoods.
Twenty-five peaks of lignin-derived monomer pyrolysis products, 21 guaiacyl and 4 p-hydroxyphenyl typeproducts, were displayed on all Py-GC traces of the softwoods pyrolyzed at 500 ºC for 4 s: no remarkable
qualitative differences, hence, were observed. However, the Py-GC traces differed quantitatively. Distribution oftrans-coniferyl alcohol in the lignin-derived products indicated that the pyrograms of Japanese softwoods
examined are grouped into three types: the alcohol distribution in the selected lignin-derived products is (a)more than 20%, (b) around 15% and (c) less than 10%.
1993-103
ユーカリ属の組織化学的方法によるリグニンの分析（I）
渡辺陽子*1、深沢和三*1、船田 良*1、浅田隆之*2、小名俊博*2*1
北海道大学農学部、*2 王子製紙株式会社林木育種研究所
Lignin analysis of Eucalyptus by histochemical methods (I )Yoko Watanabe*1, Kazumi Fukazawa*1, Ryo Funada*1, Takayuki Asada*2, Toshihiro Ona*2*1
Faculty of Agriculture, Uokkaido University, *2Oji Institute for Forest Tree Improvement
Abstract:
Lignin heterogeneity of Eucalyptus was investigated by using histochemical methods (Mäule
reaction and ultraviolet microscopy). Absorption spectra of Mäule reaction showed that all samples were
syringyl lignin rich type in all elements.
1993-104
樹木クラウンゴール細胞壁の化学構造と組織構造に関する研究
枝重有祐、富村洋一、藤井智之、石井 忠
森林総合研究所
Structural analysis of crown gall cell wall of Populus kitakamiensis
Yusuke Edashige, Yoichi Tomimura, Tomoyuki Fujii, Tadashi lshii
Forestry and Forest Products Research Institute
Abstract:
Cell wall material was isolated from crown gall tumor and sound part of Populus kitakamiensis.
Crown gall cll wall contained larger amount of lignin than the sound wd and the lignin was rich in condensed
type. There was little difference in cell wall polysaccharides between them. The main hemicellulosic
polysaccharide was 4-O-methylglucuronoxylan, which is a typical hemicellulose of hardwood. Callose, which isinduced in infected cells, was not detected in the crown gall cell wall. Microscopic observation indicated that227

crown gall was consisted of normal cells, but that rapid cell division induced by Agrobacterium tumefacience
made cambium abnormal form.
1993-105
リグニン化学構造の不均一性に関する研究 —β-O-4 構造の erythro, threo 比のリグニン存在部位による相違
松本雄二、南 一守、飯塚堯介、石津 敦
東京大学農学部
Structural heterogeneity of lignin, The ratio of erythro and threo type of arylglycerol--aryl ether structure indifferent part of cell wall
Yuji Matsunoto, Kazumori Minani, Gyosuke Meshitsuka, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Abstract:
Ozonation method was applied to investigate how erythro and threo ratio of arylglycerol-β-aryl ether structure (E/T ratio) is regulated. E/T ratio in a DHP synthesized by the stepwise addition
method (Zutropfverfahren) was 3 : 1, whereas that in a DHP synthesized by the one time addition method(Zuraufverfahren) was about 1 : 1. E/T ratio in MWLs extracted from stepwisely milled wood meal increased
with the increase in milling time, indicating that E/T ratio in secondary wall lignin is higher than that incompound middle lamella lignin. On the basis of these results, we concluded that in a endwisely polymerized
lignin (secondary wall lignin), erythro type of arylglycerol--aryl ether structure is preferentially formed, andthat in a bulk polymer type lignin (compound middle lamella lignin) threo type becomes relatively important.
1993-106
デヒドロジコニフェリルアルコールの光学分割と絶対配置の決定
平井伸博*1、宇田川裕晃*1、山室宗弘*1、加藤昌芳*1、小清水弘一*1、岡本昌彦*2*1
京都大学農学部, *1 住友化学株式会社
Optical resolution and absolute configuration of dehydrodiconiferyl alcohol
Nobuhiro Hirai*1, Hiroaki Udagawa*1, Munehiro Yamamuro*1, Masayoshi Katoh*1, Koichi Koshimizu*1,
Masahiko Okamoto*2*1
Faculty of Agriculture, Kyoto University, *2Sumitomo Chemical Co., Ltd.
Abstract:
The absolute configuration of dehydrodiconiferyl alcohol was elucidated by a chemicaldegradation. (+)-Dehydrodiconiferyl alcohol was prepared by optical resolution of the racemate with HPLC.
The value of specific rotation was +63.3º , suggesting that the natural (+)-dehydrodiconiferyl alcohol isolated
from milk thistle ([a]D +10.9º ) was not optically pure. (+)-Dehydrodiconiferyl alcohol was degradated tomethylsuccinic acid via several steps. The methylsuccinic acid was (R)-(+)- enantiomer, the optical purity ofwhich was confirmed by HPLC after derivatization. This showed that the absolute configuration of C-2 of(+)-dehydrodiconiferyl alcohol was S. Since H-2 and H-3 of dehydrodiconiferyl alcohol is trams, the absoluteconfiguration of C-3 is inevitably R. Thus (+)-dehydrodiconiferyl alcohol is 2S and 3R.
1993-107
リグニン、フミン酸の酸化還元的性質 —ESR による解析
鬼木隆幸
九州歯科大学
Redox properties of humic acid and lignin, -Electron spin resonance study
Takayuki Oniki
Kyushu Dental College
Abstract:
Electron spin resonance (ESR) spectra of humic acids and lignin were measured at pH 13.0
under argon atmosphere or after air bubbling with or without redox reagents. ESR signal intensities of humic
acids increased with elapsed time, whereas those of lignins decreased. The signals of humic acids dccreascd byoxidation with O2 or K3[Fe(CN)6] but original signals were recovered as time elapsed. The signal of lignins
increased by the oxidation. The intensities of humic acids increased by reducuon with a small amount of
Na2S2O4 but decreased with a large amount of Na2S2O4. The intensities of lignins decreased with a small
amount of Na2S2O4. Lignins were found to be a more reduced state than humic acids.
1993-108
コブシ細胞壁形成過程におけるモノリグノールグルコシドの挙動
228

松井直之*1、福島和彦*1、安田征市*1、寺島典二*2
1
名大農, 2USDA 林産物研
Behavior of monolignol glucosides during cell wall formation of magnolia
Naoyuki Matsui*1, Kazuhiko Fukushima*1, Seiiti Yasuda*1,Noritsugu Terashima*2*1
Factilty of Agriculture, agoya University, *2United States Dept. of Agriculture, Forest Products Laboratory,
U.S.A.
Abstract:
To examine the behavior of glucose residue of monolignol glucosides jn cell wall lignification,
coniferin-[Glc-6-3H, β-14C] was administered to magnolia two-years old shoot. After 3 hours or 7 days feeding,coniferin and syringin were isolated from the sap and each radioactivity was measured. The 3H-activity wasobserved not only in coniferin, but in syringin. It suggests the introduction of methoxyl group may occur in thestate of monolignol glucosides. The decrease of 3H (glucose) to 14C (lignols) in monolignol glucosides was little
at the end of 3 hours feeding, and increased corresponding to the length of feeding period. The ratio of3
H-decrease of monolignol glucosides in phloem region was larger than that in newly formed xylem region.
1993-109
Expression of brown midrib mutations on grass lignin
B. Chabbert，M.T．Tollier and B．Monties
Laboratoire de Chimie Biologique, INRA
Abstract:
Studies were conducted to characterize cell wall phenolic composition in diverse genotypes ofgrasses, including bmr6 and bmr12 sorghum lines, and bm1, bm2, bm3 maize lines and their normal
counterparts. All brown midrib genotypes contained lower lignin content and alkali-labile p-coumaric acid. The
monomer composition of lignin was differently altered according to the bm(r) gene. The occurrence of
5-hydroxyguaiacyl was shown in the alkyl aryl ether structures of bmr12 lignin of sorghum as previously
reported for bm3 maize mutants. In these plants, the non-condensed lignin structures incorporated a low
proportion of syringyl unit in contrast to the maize bm2 lignin which contained less guaiacyl moieties thannormal lignin. Furthermore, bmr6 sorghum incorporated
cinnamaldehydes units in the lignin polymer. The variations in the relative proportions of guaiacyl andsyringyl units indicated that the bm(r) mutations cause different lignin structural changes. Therefore, thephenotypically similar brown midrib plants originate from different modifications of the lignification pathway.
1993-110
ウド CAD アンチセンス遺伝子を導入したタバコの解析
日尾野隆*1、柴田大輔*1、河津 哲*2、高部圭司*3、樋口隆昌*4*1
三井植物バイオ研究所, *2 王子製紙株式会社, *3 京都大学農学部、*4 日本大学農獣医学部
Anaysis of tobacco plants with an antisense cinnamyl alcohol dehydrogenase transgene from Aralia cordata
Takashi Hibino*1, Daisuke Shibata*1, Tetsu Kawazu*2, Keiji Takabe*3, Takayoshi Higuchi*4*1
Mitsui Plant Biotechnology Research Institute, *2Kameyama Breeding Station, Oji Paper Co. Ltd., *3Faculty ofAgriculture. Kyoto University, *4Cllege of Agriculture and Veterinary Medicine, Nihon University.
Abstract:
Cinnamyl alcohol dehydrogenase (CAD) catalyzes the reduction of hydroxycinnmic aldehydes(para-coumaryl, coniferyl, and sinapyl) to the corresponding alcohols (monolignols) in lignin biosynthesis. Thus,
CAD is an important target in genetic engineering to modify lignin content or quality. We tested CAD activity insome tobacco plants carrying an antisense gene constructed with Aralia cordata CAD cDNA. CAD activity of
one of transgenic tobacco plants was decreased about 55 % in comarison with that of a normal tobacco plant.
Observation of cross-sections of shoots stained for lignin by the phloroglucinol-HCl assay provided evidence
that more aldehydes accumlate in the cell wall in the transgenic tobacco plant than in normal tobacco plants.
1993-111
シュート分化により誘導される交雑ヤマナラシおよびタバコの酸性ペルオキシダーゼアイソザイムの発現解析刑部敬史*1、松本康郎*1、小山浩和*1、川合伸也*1、片山義博*２、秦 邦男*３、諸星紀幸*1*1
東京農工大学農学部、*２東京農工大学共同研究開発センター *３日本製紙株式会社
Expression analysis of anionic peroxidases correlated with shoot forming in Nicotiana tabacum and Populus
kitakamiensis
Keishi Osakabe*1, Yasuo Matsumoto*1, Hirokazu Koyama*1, Shinya Kawai*1, Yoshihiro Katayama*2, Kunio
Hata*3, Noriyuki Morohoshi*1
229

*1

Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology, *3Nippon Paper Co., Ltd.
We have analysed the expression of peroxidase isozymes correlated with shoot forming in Nicotina tabacumand Populus kitakmniensis. Several anionic isozymes were found to express in the callus forming vegetative budor regenerating shoot but not in callus or leaf tissue. We have already isolated N. tabacum genomic peroxidase
clones (poxA1 and poxC1) and P. kitakamiensis genomic clone (prxA1). In this report, we have isolated twoother novel peroxidase clones fromP. kitakamiensis cDNA library. Using these peroxidase genes as probes, expression patterns of anionicperoxidases were examined by RNA blot analysis.
1993-112
樹木フェニルアラニンアンモニアリアーゼ遺伝子群の構造と発現の解析
刑部祐里子*1、大坪祐二*1、川合伸也*1、片山義博*２、山田恵子*1、海老沼宏安*1、秦 邦男*2、
諸星紀幸*1*1
東京農工大学農学部、*２東京農工大学共同研究開発センター、*３日本製紙株式会社
Characterization and expression of phenylalanne ammonia-lyase genes from a woody plant (Populus
kitakamiensis)
Yuriko Osakabe*1, Yuji Ohtsubo*1, Shinya Kawai*1, Yoshihiro Katayama*2, Keiko Yamada*1, Hiroyasu
Ebinuma*1, Kunio Hata*3, Noriyuki Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technofogy, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology, *3Nippon Paper Co., Ltd.
Abstract:
Six independent phenylalanine ammonia-lyase (PAL) genes were isolated from a genomic
library and a cDNA library constructed win mRNAs from the young stem tissue of a hybrid aspen, Populus
kitakamiensis. The isolated PAL clones from the cDNA library were transcribed from one gene. The
corresponding gene (pal g1) to the cDNA and four other genes were isolated from the genomic library. Most of
PAL genes consist of two exons divided with one intron. Interestingly,
pal g2a and pal g2b were isolated as one DNA fragment containing two tandemly oriented PAL genes. The
expressions of these PAL genes in stem, leaf, and callus tissues were demonstrated by RNA blot analysis using
gene-specific probes. lt was defined that pal g1 was mainly transcribed in the young stem tissue.
1993-113
リグニン生合成系に関与する OMT 酵素蛋白と遺伝子の単離
早川敏雄*1、岡村慎仁*1、川合伸也*1、片山義博*２、秦 邦男*３、諸星紀幸*1*1
東京農工大学農学部、*２東京農工大学共同研究開発センター、*３日本製紙株式会社
Purification of O-methyltransferase (OMT) involved in the lignin biosynthesis and cDNA cloning
Toshio Hayakawa*1, Shinji Okamura*1, Shinya Kawai*1, Yoshihiro Katayama*2, Kunio Hata*3, Noriyuki
Morohoshi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technofogy, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology, *3Nippon Paper Co., Ltd.
Abstract:
O-methyltransferase (OMT) is a key enzyme for deterninating aromatic ring structures in lignin.
We obtained two OMT activities from a hybrid aspen, Populus kitakamiensis, by using anion exchange
chromatography and affinity chromatography on S-adenosyl-L-homocystein- Sepharose 4B. The results ofSouthern hybridization for total DNA from P. kitakamiensis suggested that OMT was consisted of a snmall genefamily. We isolated a DNA fragment encoding OMT from a cDNA library constructed with the stem RNA and it
was very similar to OMT genes from aspen and poplar.
1993-114
Pseudomonas paucimobilis SYK−6 株のビフェニル環開裂酵素遺伝子の単離と解析
花城 薫*１、片山義博*2、笠原健秀*１、政井英司*３、川合伸也*１、山崎真狩*４、諸星紀幸*１*１
東京農工大学農学部、*２東京農工大学共同研究開発センター、*３新技技術開発事業団微生物進化プロジ
ェクト、*４東京大学農学部
Cloning and analysis of the genes of biphenyl ring fission from Pseudomonas paucimobilis SYK-6
Kaoru Hanashiro, Yoshihiro Katayama, Takehide Kasahara, Eiji Masai, Shinya Kawai, Makari Yamasaki,
Noriyuki Morohoshi*1
Faculty of Agriculture, Tokyo University of Agriculture and Technofogy, *2Cooperative Research Center,
230

Tokyo University of Agriculture and Technology, *2Microbial Evolution Project, JRDC
*４Faculty of Agriculture, The University of Tokyo
Abstract:
Pseudomonas paucimobilis SYE-6 grows on various lignin dimeric compounds as a sole carbon
souce. In particular, it is characteristic of this strain to degrade biphenyl compounds. We have already reported
about the metabolism of biphenyl structure in lignin and cloning of 15-kbp EcoR I fragment which could restore
the wild's phenotype of mutants. We explain that l5-kbp EcoR I fragment is related to degradation of biphenyl
compounds.
1993-115
リグニンビフェニル型化合物の分解酵素遺伝子群の単離と解析 （脱メチル酵素遺伝子の単離と解析）
窪田祥子*１、小尾高広*１、片山義博*２、川合伸也*１、諸星紀幸*１*１
東京農工大学農学部、*２東京農工大学共同研究開発センター
Cloning and analysis of the genes involved in degradation of biphenyl structure of lignin compounds Cloning
and analysis of the demethylase gene.
Sachiko Kubota*１, Takahiro Obi*１, Yoshihiro Katayama*2, Shinya Kawai*１,Noriyuki Morohoshi*１*1
Faculty of Agriculture, Tokyo University of Agriculture and Technofogy, *2Cooperative Research Center,
Abstract:
Pseudomonas paucimobilis SYK-6 is able to grow on DDVA and other various lignin dimericcompounds as a sole carbon source. To reveal of the specific reactions of lignin metabolism of microorganism,
we investigate the metabolism of biphenyl compound DDVA by SKY-6. We have isolated the gene coding
DDVA demethylase as a 30kb Sal I DNA fragment (plasmid clone pDM22) from Pseudomonas paucimobilis
SYK-6 chromosomal DNA. Here, we have isolated another clone which has a 6kb EcoR I fragment (plasmid
clone pLE6), which is thought to be the same of the 6kb EcoR I fragment in pDM22.
1993-116
リグニンペルオキシダーゼによるチトクロ−ム C の酸化
割石博之*1、Michael H. Gold*2*1
九州大学農学部、*2Oregon Graduate Institute
Oxidation of ferrocytochrome c by lignin peroxidase
Hiroyuki Wariishi*1, Michael H Gold*2*1
Faculty of Agriculture, Kyushu University, *2Oregon Graduate Institute of Science and Technology
Abstract:
The direct oxidation of ferrocytochrome c by lignin peroxidase (LiP) from the lignin degradingbasidiomycete, Phanerochaete chrysosporium, was demonstrated. As with cytochrome c peroxidase reactions,
LiP oxidation of ferrocytochrome c decreased as the ionic strength increased, implying the involvement ofelectrostatic interactions between the polymeric substrate and enzyme. The reaction product ferricytochrome cinhibited veratryl alcohol oxidation by LiP in a noncompetitive manner, suggesting that cytochrome c binds to
LiP at a site different from the small aromatic substrate binding site. Recent crystallographic studies show thatthe heme is buried in the LiP protein and unavailable for direct interaction with polymeric substrates, suggestingthat the electron transfer from ferrocytochrome c to LiP may occur via electron tunneling, as in the reaction ofcytochrome c peroxidase with ferrocytochrome c. This observation of the direct oxidation offerrocytochrome c by LiP may serve as a useful model for probing the mechanism of electron transfer between
the buried heme of the enzyme and polymeric substrates.
1993-117
有機溶媒中における化学修飾ペルオキシダーゼの反応
吉田晋一、渡辺隆司、本田与一、桑原正章
京都大学木質科学研究所
Reaction of chemically modified peroxidase in organic solvents
Shinichi Yoshida, Takashi Watanabe, Yoichi Honda, Masaaki Kuwahara
Wood Research Institute. Kyoto University
Abstract:
Lignin peroxidase (LiP) from Phanerochaete chrysosporium was chemically modified
with methoxypolyethylene glycol-succinimidyl succinate (MPSS). Reaction products by the native andmodified LiP in organic solvents were analyzed by g.1.c. 3,4,5-Trimethoxybenzyl alcohol (TMBA) was
oxidized by the modified LiP in benzene, While the native LiP was inactive to TMBA in the organic solvent.
Furthermore, it has been found that veratryl alcohol was more susceptible to the oxidation than TMBA in
aqueous solutions, while the reverse substrate specificity was observed in the reactions in benzene. Oxidation
231

activity of the modified LiP in benzene was 1/300 of that observed in aqueous solution.
1993-118
Phanerochaete chrysosporium の芳香環閑裂酵素について（II）
中村雅哉、西田篤実、高野麻理子
森林総合研究所
Aromatic ring cleavage enzyne from Phanerochaete chrysosporium (II)Masaya Nakamura, Atsumi Nishida, Mariko Takano
Forestry and Forest Products Research Institute
Abstract:
In the metabolic pathway for vanillic acid degradation by Phanerochaete chrysosporium, it was
shown that 1,2,4-tri-hydroxybenzen underwent aromatic ring-cleavage. However, ring-fission dioxygenase isvery unstable so the purification of this enzyme is very difficult. In this study, we succeeded in the purificationof 1,2,4-trihydroxybenzen (hydroxyquinol) 1,2-dioxygenase and clarified some enzymatic properties. The native
molecular weight of this enzyme is 94,000 Dalton and subunit molecular weight are 40,000 and 52,000 Dalton
by SDS-PAGE. In the kinetic analysis, Michaelis constant for 1.2.4-tri-hydroxybenzen equals 7μM and Vmax
equals 0.826.
1993-119
リグノスチルベン-α,β-ジオキシゲナーゼの活性と鉄の閑係（II）
鴨田重裕、佐分義正
東京大学農学部
The relation between activity and iron content of lignostilbene-α,β-dioxygenase (II)Shigehiro Kamoda, Yoshhasa Saburi
Faculty of Agriculture, the University of Tokyo
Abstract:
Lignostilbene-α,β-dioxygenase I (LSD-I), one of LSD isozymes, contained iron. Native LSD-I
was almost colorless or pale yellow at high concentration. LSD-I did not show the heme typical absorption
spectrum. LSD-I seemed to have nonheme iron. LSD-I was inactivated by H2O2, oxidizing agent, and was
activated by hydroxylamine, reducing agent, o-phenanthroline, chelating agent for ferrous ion, inhibited the
LSD reaction. Tiron, chelating agent for ferric ion, did not inhibit the LSD reaction. LSD-I inactivated by H2O2
was reactivated with ferrous ion and hydroxylamine. These results indicated that ferrous ion play the importantrole on the enzyme activity. Furthermore, linear relation was founded between the amounts of ferrous ion andactivities. The maximum amount of iron seemed to be two atoms per one molecule of LSD-I.
1993-特別講演、植物培養細胞の二次代謝機能 —シキミ酸経路由来の shikonin と berberine を例に
福井宏至
香川大学農学部
Invited Lecture: Secondary metabolism (shikonin and berberine) in cultured plant cells
Hiroshi Fukui
Faculty of Agriculture, Kagawa University
1993-201
リグニンからのポリウレタン
菱山正二郎*1、大原誠資*1、秦野恭典*1、須藤賢一*2*1
森林総合研究所、*2 群馬女子短期大学
Polyurethanes from lignin
Shojiro Hishiyama*1, Seiji Ohara*1, Yasunori Hatano*1, Kenichi Sudo*2*1
Forestry and Forest Products Research Institute, *2Gunma Womens Junior College
Abstract:
In order to prepare the polyurethane from lignin, lignin derivatives (I and II) were synthesizedfrom steam-exploded lignin using glycerol -monochlorohydrin (GMH). NMR studies show that lignin
derivative II possesses large amount of hydroxyl groups which have high reaction activity with isocyanate.
Preparation of polyurethane films was accomplished from lignin derivative II using two kinds of isocyanate,hexamethylenediisocyanate (HDI) and diphenylmethanediisocyanate (MDI). Viscoelastic properties of thesepolyurethane films were investigated.
2321993-202
リグニン樹脂接着剤の製造
島谷啓二、佐野嘉拓、笹谷宜志
北海道大学農学部
Preparation of lignin-based wood adhesives
Keiji Shimatani, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Abstract:
The utilization of kraft lignin in the substrate of wood adhesives has been investigated. A
mixture of kraft lignin and phenol (8:2) was hydroxymethylated under alkali conditions in order to produce
phenol-lignin co-polymer (WI and WS). WI was recovered in a yield of 89% from the reaction mixture.
Resorcinol terminated resins of the co-polymers (WI-R) were prepared by condensation of WI (100 parts) withresorcinol (ca 30 parts) in alkali solution at pH 11. An alkali solution of WI-R (40%solids) containing 5-10% of paraformaldehyde had a gelation time of 25 minutes at room temperature. The
gelation times varied with amounts and kinds of cross-linking reagents suggesting that wood lignins may beutilized as a readily available and inexpensive substrate for cold-setting wood adhesives.
1993-203
膨潤—溶媒和プロセスによる高反応性リグニンの合成
松原正幸、船岡正光、阿部 勲
三重大学生物資源学部
Synthesis of highlyy reactive lignins by the swelling-solvation process
Masayuki Mtsubara, Masamitsu Funaoka, Isao Abe
Faculty of Bioresources, Mie University
Abstract:
The swelling-solvation process is a method for direct conversion of protolignin into functional
lignophenol derivatives, which proceeds rapidly at room temperature. The key point of this process is to treat
lignocellulosics with concentrated acid under the solvation of lignin with phenol derivatives. The resulting
lignohenol derivatives have several distinctive properties whichconventional lignins do not have: no conjugated system, light color, high protein adsorbing capacity, etc. ln thispresentation, the processes for synthesizing lignophenol derivatives having different reactivities and functions
are discussed.
1993-204
隣接基関与反応を応用するリグノフェノール誘導体の分子構造変換
寳勝智貴、船岡正光、阿部 勲
三重大学生物資源学部
Structural conversion of lignophenol derivatives by neighbouring group participation
Tomotaka Hosho, Masamitsu Funaoka, Isao Abe
Faculty of Bioresources, Mie tJniversity
Abstract:
Lignophenol derivatives are directly derived from protolignin by the swelling-solvation process
combining the solvation of lignin with phenol derivative and the swelling and dissolution of carbohydrates byconcentrated acid. Lignophenol derivatives are not subjected to complicated structural modifications, retaining
structural characteristics of original lignin, and highly phenolic, due to the cleavage of benzyl ether linkages andthe phenolation at -positions (0.65mol/C9 in softwood, 0.90mol/C9 in hardwood). In the present work, thelignocresols were synthesized from spruce and birch by the S-S process, and their depolymerizations werecarried out by the neighbouring group participation in alkaline systems, in order to corltrol their reactivities andfunctions. Spruce lignocresol was depolymerized to Mw ca. 900 by the treatments with 2N NaOH or a mixtureof NaOH and Na2S at l70 ºC for 2 hours, while birch lignocresol to Mw ca. 600. When p-cresol was added in
the reaction system, spruce lignocresol decreased toMw ca. 600. Alkaline depolymerization mechanisms oflignophenol derivatives were discussed.
1993-205
リグノフェノール誘導体の構造とタンパク質に対するその機能
井岡浩之、関 範雄、中嶋礼子、三亀啓吾、○船岡正光、阿部 勲
三重大学生物資源学部
Affinity of lignophenol derivatives for proteins233

Hiroyuki Ioka, Norio Seki, Reiko Nakajima, Kei!o Mikame, Masamitsu Funaoka, Isao Abe
Faculty of Bioresources, Mie University
Abstract:
Lignophenol derivatives were synthesized from various lignocellulosics, using theswelling-solvation process, and their affinity for proteins was investigated. Lignophenol derivatives had muchhigher affinity for proteins, compared with conventional lignin preparations. The protein adsorbing capacities oflignophenol derivatives differed with their originating species and increased with increasing basicity of phenol
derivatives. The adsorption of protein on lignophenol derivatives rapidly took place at the initial step oftreatment, after which the amount increased gradually with time. The maximum adsorption was achieved at
isoelectric points of proteins. Proteins immobilized on lignophenol derivatives were not desorbed at any pH.
1993-206
リグニンの水素化分解 —触媒等の検討—
小山 実
物質工学工業技術研究所
Hydrocracking of lignin. -Search for catalysts and reaction conditions
Makoto Koyama
National Institute of Materials and Chemical Research
Abstract:
Hydrocracking of a kraft lignin (KL) was conducted in order to search the catalysts and reaction
conditions as the purpose to rise monophenol yield and promote the mononerization of KL. The searchedcatalysts were as follows; solid acids (smectites, aluminosilicates, Al-pillared smectites, composite metal oxides,
zeolites and titanium oxides), alumina, metal oxides and metal.
1993-特別講演、
樹木抽出成分 —フェニルプロパン誘導体—
笹谷宜志
北海道大学農学部
Invited Lecture: Wood extractives, -Phenylpropane derivatives
Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Abstract:
In numerous wood extractives, typical phenylpropane derivatives are lignans. They include
those based on the new definition, namely neolignans. This paper summarizes the chemical structures of lignans
and neolignans in larch Larix leptolepis Gord., fir Abies sachalinensis Masters, willows Chosenia arbutifolia A.
Skvortz. and Salix sachalinensis Fr. Schm. Among them, trimeric and tetrameric derivatives were involved inaddition to dimeric ones. It is presumed that there is intimate relation between lignans and Brauns' 1ignin (BL).
Also, the biological activities of lignans will be dealt with only briefly here.
1993-207
稲ワラ・ソーダ蒸解黒液リグニンの分散剤としての利用
中野準三*1、北仲由美子*1、矢田英律*1、石津 敦*2*1
福井工業大学工学部、*2 東京大学農学部
Utilization of rice straw soda lignin from pulping black liquor as dispersantJunzo Nakano*1, Yumiko Kitanaka*1, Hidenori Yada*1, Atsushi Ishizu*2*1Faculty of Engineering, Fukui Institute of Technology, *2Faculty of Agriculture, the University of Tokyo
Abstract:
Soda lignin was isolated from the pulping black liquor of rice straw, then was sulfomethylated(SWL). The dispersibility of kaolin suspension and the setting of mortar with SWL were measured in contrast
with wood lignosulfonate. The effects of dispersing additives were also tested with various carboxylic acids.
The results are summarized as follows: (1) Dispersibility with rice straw SWL is efficient for concrete
production. (2) Among the additives used here, sugar carboxylic acids are better than other carboxylic acid, andglucaric acid is superior than gluconic acid. (3) In order to simplify the sulfomethylation, lignin in black liquor
was directly sulfomethylated after the acidification with dil. sulfurous acid. The dispersibility is poor comparing
with that of purified SWL. The setting of mortar takes a long tine.
1993-208
リグニングラフトポリマーのセメント粒子への分散性と粘稠性
矢口 稔*1，大田晃*1，田中義夫*1，瓜生敏之*2
234

*1

株式会社エヌエヌビー，*2 東京大学生産研究所
The dispersibility and viscosity of lignin graft polymer to cement particles
Minoru Yaguchi*1, Akira Ohta*1, Yoshio Tanaka*1, Toshiyuki Uryu*2*1
NMB Co., Lt d. *2 Institute of Industrial Science, the University of Tokyo
Keywords: lignin graft polymer, lignosulfonates, cement particles, dispersing agent, viscosity
Abstract:
In this study, the synthesis of lignin graft polymer provides high-dispersibility and moderate
viscosity for cement particles was investigated. Acrylamide (AM) and acrylamide methylpropansulfonate(AMPS) were grafted to lignin sulfonate (LSA) for which AM provides the viscosity and AMPS provides thehigh dispersibility. Various lignin graft polymers (LGP) were evaluated dispersibility and viscosity in cement
mortar testings. It was found that LGP provided the high-dispersibility and the moderate viscosity to the cement
particles.
1993-209
常圧酢酸パルプ化
金野晴男、佐野嘉拓、笹谷宜志
北海道大学農学部
Acetic acid pulping at atmospheric pressure
Haruo Konno, Yoshihiro Sano, Takashi Sasaya
Faculty of Agriculture, Hokkaido University
Abstract:
Atmospheric pulping of commercial hardwood chips of Hokkaido in a boiling aqueous
AcOH with a small amount of sulfuric acid were carried out either in a batch system or in a mimetic
continuous-extraction system. The continuous extraction conditions used for the chips were the optimum
conditions for separating into each of the main components as quantitatively as possible. By the continuous
extraction in a boiling 95% AcOH with 0.32% sulfuric acid, the chips yielded 44.6% of screened pulp with
Klason lignin of 6.9%, 1.8% of reject, 16.9% of reducing sugars (14.1% of xylose) and 19.0% of AcOH lignin
based on o.d. chips, respectively.
1993-210
リグニンモデル化合物のオルガノソルブパルプ化処理における β-O-4 結合の開裂機構（II）—キノンメチド生
成速度に対する有機溶媒の効果
高橋一郎、坂井克己
九州大学農学部
The β-O-4 bond cleavage mechanism during organosolv pulping treatments of lignin modelcompound, I. - The effect of organic solvent on rate of quinone methide formationIchirou Takahashi, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
The β-O-4 bonds n lignin and its model compounds were cleaved to give eugenol and/or
isoeugenol during an organosolv pulping treatment with bisulfite at 160 ºC. It was found that this reaction which
proceeds via a quinone methide intermediate was seriously influenced by concentration and inductivity oforganic solvents, Consequently we presumed that the rate- determining step is an ionic reaction. In order toinvestigate the effect of solvent on rate of quinone methide formation, a lignin model compound shown in Fig. 1
was subjected to an alcohol-phosphate buffer treatment in aqueous ethanol of various concentration at relatively
low temperatures. The rate constants and activation parameters were calculated for erythro form to threo form.
The conversion rate was affected seriously by solvent concentration. This result suggests that therate-determining step of this reaction is not the β-O-4 bond cleavage process, but the quinone methide formation
process.
1993-211
パルプ漂白菌によるリグニンモデル物質の変換
飯森武志，金子令治，吉川宏，町田誠，吉岡英敏，村上邦睦
日本製紙株式会社
Transformation of lignin model compounds by pulp-bleaching fungi
Takeshi Iimori, Reiji Kaneko, Hiroshi Yoshikawa, Makoto Machida, Hidetoshi Yoshioka, Kunichika Murakami
Nippon Paper Industries Co., Ltd.
Keywords: pulp-bleaching fungus, oxygen-bleached pulp, lignin degradation fungus, enzyme activity
235

Abstract:
We have already reported a new pulp-bleaching fungus, namely SKB-1152, which could
increase the brightness of oxygen-bleached kraft pulp (OKP) to over 80%. In the present work, we investigatedthe change of three lignin model compounds (veratryl alcohol: VE, veratric aldehyde : VEA, veratric acid :VEacid) when these compounds was added to the OKP in bleaching. After incubation, culture filtrate wereanalyzed by HPLC. VE was oxidized to VEA and VEA was consumed in the treatment by SKB-1152. However,when VEA and VEacid were added, these compounds were reduced to VE respectively. Resulting, produced VE
was oxidized to VEA again and finally consumed. Further, we reported the enzyme activity in culture filtrate.
1993-212
機械パルプの微生物処理に関する研究（XI） 光退色を抑制する菌とモデル化合物との反応性について
谷口新吾、武田早苗、橘 燦郎、伊藤和貴、沖 妙
愛媛大学農学部
Studies on biological treatment of mechanical pulps (XI), Reactivity between lignin model compounds andextracellular crude enzymes solution from fungi having ability for depression of color reversion of mechanicalpulps
Shingo Taniguchi, Sanae Takeda, Sanro Tachibana, Kazutaka ltoh, Tae Oki
Faculty of Agriculture, Ehime University
Abstract:
Reactions between the lignin model compounds having functional groups for color reversion
and the crude enzymes solution from six wood-rotting fungi having ability for depression of color reversion of
mechanical pulps were examined. The model compounds used were coniferyl- aldehyde methy wther (1),-(2-methoxyphenoxy)- β-hydroxypropioguaiacone (2), and methoxy-p- quinone (3). The compound (3) wasmost reactive to the crude enzymes solution in the three compounds, the compound (1) was next to thecompound (3), and the compound (2) was less reactive. Main reaction of each compound was reductive
reactions, but some oxidative reactions was also occurred. When the compound (3) was treated with the crude
enzymes solution, main reaction was reduction of quinone to the corresponding hydroquinone and followed bymethylation of the phenolic hydroxyl group generated. Based on the results of the reactivity between the modelcompounds and the crude enzymes solution, reduction of quinone and followed by protection of the phenolichydroxyl group generated seem to contribute mainly to the depression of color reversion of mechanical pulps.
1993-213
リグニン分解菌によるクラフトパルプ漂白廃液の処理（VI）グルコノ-δ-ラクトン添加による処理性向上の機構について
李 宣鏑、近藤隆一郎、坂井克己
九州大学農学部
Decolorization of kraft bleaching effluent by lignin-degrading fungi (Vl), The mechanism of the decolorizationof E1 effluent by an addition of glucono-δ-lactone
Seon-Ho Lee, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu Uiversity
Abstract:
In a previous report, we observed that the addition of glucono- -lactone to the E1 effluent
showed great decolorization during a short treatment period. In the present study, we have attempted to clarify
the mechanism of decolorization by the addition of glucono-δ-lactone. When the aqueous solutions of glucose
and glucono-δ-lactone were treated with Coriolus versicolor, most of the glucose was consumed and the
glucono-δ-lactone was converted a part into gluconic acid remaining in the cultivation medium. The pH of theeffluent With the glucono-δ-lactone was decreased from an initial pH of 4.5 to 3.6, although the pH of theeffluent without any additives was increased gradually during fungal treatment. From the results, we assume
that the effect of the glucono-δ-lactone on the great decolorization of E1 effluent was due to the somemorphological change of the mycelium of the C. versicolor by the gradual decrease of pH.
1993-214
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（II）クラフトパルプのバイオブリーチングに及ぼす金属塩の影響平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (II)
Effects of metal salts on biological bleaching of kraft pulp.
236

Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We obtained several new isolates which showed higher ligninolytic activity and selectivity thantypical lignin-degrading fungi, Phanerochaete chrysosporium and Coriolus versicolor. In the present work, weapplied these new isolates to bleaching of the kraft pulp, and determined ligninolytic enzyme activities in thesebleaching cultures. Manganese peroxidase (MnP) was dominant in most strains which could bleach the kraft
pulp, and the higher brightness increase of fungal treated pulp was observed, the higher MnP activity was
detected in the culture. If metal ions were removed from the kraft pulp with an acid treatment, biologicalbleaching of the pulp hardly showed brightness increase, and ligninolytic enzyme activity in the culture sharply
decreased. These results suggest that metal ions in the kraft pulp played an important role in biologicalbleaching of the kraft pulp by white-rot fungi.
1993-215
リグニンの酵素分解に関する研究（IV） メンブランフィルターを用いた培養系におけるクラフトパルプの invitro ブリーチング
近藤隆一郎、蔵敷賢二、坂井克己
九州大学農学部
In vitro bleaching of haft pulp by extracellular enzymes excreted from white-rot fungi in a cultivating systemusing a membrane filter
Ryuichiro Kondo, Kenji Kurashiki, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
To clarify the role of the excreted extracellular enzymes during long-term incubation inbiobleaching with white-rot fungi, we have developed a cultivation system using a membrane filter
which can prevent the direct contact between hyphae and kraft pulp, but allows extracellular enzymes to attack
the kraft pulp. The fungus YK-624 brightened the pulp 21.4 points to 54.0%
brightness after 5-days in vitro treatment, which was significantly higher than Phanerohaete chrysosporium andCoriolus versicolor did during 7-days treatment. This results indicate that cell-free, membrane-filteredcomponents from the in vitro biobleaching system are capable ofdelignifying unbleached kraft pulp. Obvious candidates for filterable reagents capable of delignifying andbleaching kraft pulp are peroxidase and phenoloxidase proteins. Secreted manganese peroxidase activity in thefilterable components was substantial during the fungus YK-624 in vitro biobleaching. A positive correlation
between the level of manganese peroxidase and brightening of the pulp was observed.
1993-216
亜硝酸前処理を用いるクラフトパルプ酸素漂白法とその漂白機構（2） アカマツパルプの亜硝酸処理とリグニンモデル化合物の反応
大井 洋、岸野正典、山口 彰
筑波大学農林工学系
A pretreatnent with nitrous acid for oxygen bleaching of kraft pulp and its bleaching mechanism (II), Nitrousacid treatment of akamatsu pulp and reactions of lignin model compounds
Hiroshi Ohi, Masanori Kishino, Akira Yamaguchi
Institute of Agriculture and Forest Engineering, University of Tsukuba
Abstract:
To clarify the conditions of nitrous acid pretreatment for softwoods pulp, akamatsu kraft pulp
(kappa number: 26, viscosity: 3lcP) at medium consistency was treated under various conditions. Kappa numberof the pulp decreased to 13.5 under the condition of 0.3% nitrite, 4% nitric acid, 90 ºC and 3 hours. Secondly we
discussed about the bleaching mechanism based on reactions of non- phenolic lignin mdel compounds. When
1-(3,4-dimethoxyphenyl)-2-(2-methoxy-4-methylphenoxy)- propan-1-ol was treated in the nitric acid solution
without nitrite at 90 ºC, it was stable even after 3 hours, which changed into an its stereo chemical isomer. Morethan 90% of the model was recovered. On the other hands, the model was clearly decomposed when it was
treated with the nitrite and nitric acid, we identified 35% of veratraldehyde and 6% of 4-nitroveratrole from themodel. It was found that a main reaction is the cleavage of a Cα-Cβbond.
1993-217
酸処理を用いたクラフトパルプの無塩素漂白 —漂白機構—
池田 努*1、真柄謙吾*2、富村洋一*2、細谷修二*2
237

*1

筑波大学農林工学系、*2 森林総合研究所
Non-chlorine bleaching by acid rreatment of kraft pulp, -Bleaching mechanismTsutomu lkeda*1, Kengo Magara*2, Yoichi Tomimura*2, Shuji Hosoya*2*1Institute of Agricultural and Forest Engineering, University of Tsukuba, *2Forestry and Forest Products
Research Institute
Abstract:
It was reported in our previous paper that beech and red pine kraft pulp were successfully
delignified by sulfuric acid treatment. with a small amount of sodium nitrate and sodium nitrite followed bycaustic extraction. In this paper, the structure of the lignin dissolved by acid treatment or caustic extraction werecharacterized by elemental analysis UV, IR, NMR, and GPC to understand the delignification mechanism.
Carbohydrate analysis of the pulp and the bleach effluent were also performed by using liquid chromatography
to see the degradation of cellulose and hemicellulose during bleaching.
1993-218
酸素アルカリ漂白過程における多糖類の分解機構（2）—糖分解がリグニン反応に依存する系での反応選択性の向上—
安本光夫、松本雄二、石津 敦
東京大学農学部
Dependence of carbohydrate degradation on reaction of lignin during oxygen bleaching
Mitsuo Yasumoto, Yuji Matsumoto, Atsushi Ishizu
Faculty of Agriculture, the University of Tokyo
Abstract:
During oxygen bleaching, the degradation of carbohydrate depends on the reaction of lignin.
Therefore, mechanistic studies such as degradation pathway of carbohydrates, factors affecting reaction
selectivity, or protective effect of additives have to be performed in a system where carbohydrate degradation ishardly observed if lignin is absent. In our model system, methyl- -glucopyranoside (MGP) is not degradedwhen either vanillyl alcohol (VA) or oxygen is not present. Effects of oxygen pressure, magnesium to iron ratio,
and methanol addition on the reaction rateof both MGP and VA, and on the reaction selectivity between MGP and VA were examined in this model system.
Results suggested that degradation products of lignin peroxides rather than hydrogenperoxide or superoxideanion have a significant effect on the degradation of carbohydrate.
1993-219
The Contribution of high molecular lignosulfonate to the powerful bacterial cellulose production by Acetobacter
xylinum ATCC 10245
S．Premjet、大谷慶人、鮫島一彦
高知大学農学部
Abstract:
The high molecular lignosulfonate fraction and the low molecular lignosulfonate andcarbohydrate mixture fraction were obtained through gel-filtration and a 80% ethanol precipitation
method from the commercial sulfite pulping waste fraction (named CP powder). The media with high molecularlignosulfonate fraction showed better yields than those with the low molecular carbohydrate rich fractions. The
elimination of carbohydrates, cations and low molecular fraction
from the whole CP powder showed no negative effect on the powerful cellulose production. The powerfulcellulose production was also observed by the addition of commercially pure sodium lignosulfonate. The
contribution of the dispersing nature of the lignosulfonate was compared withsynthetic dispersant and natural digitonin but they showed only slight effects on cellulose production.
1993-220
微粉砕セルロースの生成に及ぼす因子
遠藤貴士、北川良一、細川 純、壁谷 洋、西山昌史
四国工業試験所
Factors for production of fine-grinding cellulose
Takashi Endo, Ryouichi Kitagawa, Jun Hosokawa, Hiroshi Kabeya, Masashi Nishiyama
Government Industrial Research Institute, Shikoku
Abstract:
Air-dried or vacuum-dried CF11 (Whatman) was ground in a vibratory ball mill under several
conditions, and then the obtained powders were characterized. In case of both air-dried and vacuum-dried CF11
at room temperature, the particle size of powders became small and the crystallinity was decreased with238

grinding time. However, the degree of polymerization was not significantly reduced. In vacuum-dried CF11, theparticle size was much smaller than in air-dried one. The particle distribution was same in both air-dried andvacuum-dried CF11 grinding at -100 ºC, and the particle size of obtained powders was small. However, thecrystallinity from air-dried CF11 was slightly decreased. Addition of organic solvents such as acetone on CF11
was effective in forming fine particles. In particular, fine particles were formed from dried CF11. For
fine-grinding of cellulose, the absorbed water significantly effects on the production of powder. The absorbed
water causes agglomeration of the particles and plasticizing of cellulose.

239

第 39 回 （1994.10.12-13） 福岡リーセントホテル
1994-101
熱分解ガスクロマトグラフィーによる広葉樹型リグニンの分析（II） 日本産広葉樹の分析
和泉明子、黒田健一、山口 彰
筑波大学農林工学系
Analysis of hardwood lignin by pyrolysis-gas chromatography (II), Analysis of Japanese hardwoods
Akiko lzumi, Kenichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Several Japanese hardwoods were analyzed by pyrolysis combined with gas chromatography(Py-GC). The yields of pyrolysis products were about half of those on nitrobenzene
oxidation. The ratios of syringyl-derived pyrolysis products to guaiacyl-derived pyrolysis products were inagreement with the ratios of the syringaldehyde yields to the vanillin yields on nitrobenzene oxidation.
1994-102
熱分解ガスクロマトグラフィーによるイネ中の桂皮酸類の分析
黒田健一*1、鈴木亜樹*2*1
筑波大学農林工学系、*2 筑波大学農林学系
Analysis of cinnamic acids in rice (Oryza sativa L.) by pyrolysis-gas chromatography
Kenichi Kuroda*1, Aki Suzuki*2*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2 Institute of Agriculture and Forest,
University of Tsukuba
Abstract:
Pyrolysis derivatisation using tetramethylammonium hydroxide (TMAH), a thermally assistedhydrolysis and methylation method, was effectively used to identify cinnamic acids in paddy rice (Oryza sativaL.). Rice and its lignin produced 4-methoxy and 3,4-dimethoxycinnamic acid methyl esters as the main products
on pyrolysis in the presence of TMAH., 3,4,5-trimethoxy- cinnamic acid methyl ester was absent. This report
describes furthermore the determination of p-coumaric and ferulic acids in rice on the basis of the yields of
4-vinylphenol and 4-vinylguaiacol produced by the conventional pyrolysis-gas chromatography method(Py-GC). The amounts of p-coumaric and ferulic acids determined by Py-GC were in good agreement withthose determined by a combination of alkaline hydrolysis and high temperature.
1994-103
Sorghum, pearl millet および maize の brown midrib mutant stem 細胞壁のリグニンおよびヒドロキシ桂皮酸
Thi Bach Tuyet Lam*1、飯山賢治*1*2、Bruce A. Stone*1*1
La Trobe 大学生化学科、*2 東京大学農学部
Lignin and hydroxycinnamic acids in walls of brown midrib mutants of sorghum，pearl millet and maize stems
Thi Bach Tuyet Lam*1, Kenji Iiyama*1*2, Bruce A．Stone*1*1
School of Biochemistry, La Trobe University, *2Faculty of Agriculture, the University of Tokyo
Abstract:
The brown-midrib (bmr) mutants have been found or induced in maize, sorghum, pearl
millet and hybrid of sorghum×sudangrass. We discussed the characteristics of stem walls of bmr mutants ofsorghum (two mutants, Sorghum bicolor), pearl millet (Pennesetum glaucumi) and maize (Zea mays) focusing
on linkage types of hydroxycinnamic acids to wall polymers and on lignin structural feature. Lignin content of
all mutants determined using acid detergent lignin (ADL) procedure was significantly lower than that of normal
counterparts, however there are no significant differences in lignin content determined by acetyl bromide
procedure between bmr and normal strains, suggesting the incomplete polymerization of lignin molecules
during lignification in bmr mutants. No etherified p-coumaric acids were found in all samples tested except on
normal strain of pearl millet, the amounts of etherified ferulic acid in bmr mutants, which probably form
ester-ether bridges between lignin and polysaccharides, were not as much as those of normal counterparts. The
low content of the bridges in bmr mutants may contribute to the high rumen digestibilities.
1994-104
小麦 straw およびクスの木から抽出したリグニンの ESR
鬼木隆幸、高浜有明夫
九州歯科大学Electron spin resonance study on lignins from wheat straw and camphor tree240

Takayuki Oniki, Umeo Takahama
Kyushu Dental College
Abstract:
Milled straw or milled wood lignins and dioxane lignins were isolated successively from wheat
straw and camphor tree. Saponification and acidolysis were used to release ester and ether linkages, respectively,
between lignins and polymetic compounds. EIectron spin resonance (ESR) spectra of the lignins isolated fromeach steps were measured at pH 13.0 or 12.5 under argon atmosphere or after air-bubbling in solutions. When
air was bubbled in solutions, milled wood lignin from camphor tree showed an ESR signal due to
4-hydroxyphenyl group, while dioxane lignin showed
ESR signals due to 3-methoxy-4-hydroxyphenyl (guaiacyl) group and 3,5-dimethoxy-4-hydroxy- phenyl(syringyl) group. Wheat straw lignin showed a guaiacyl signal and a slight amount of syringyl signal by the air
oxidation. The results confirm that lignins are polymerized with successive, sinapyl alcohol, coniferyl alcohol,and p-coumaryl alcohol when three precursors present simultaneously in a cell.
1994-105
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（IV）〜白色腐朽菌の還元能について
平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (IV), Reducing ability of white-rot fungi
Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
To clarify reduchg ability of white-rot fungi, we used 6 tetrazorium salts which were well-hown
as dehydrogenase-detectable agents. We examined the effect of various culture conditions on fungal reducing
and oxidizing activity which were detected by colorization of the tetrazorium salts and the decolorization of
Poly R-478, respectively. The highest level of reducing activity of white-rot fungi was detected in nutrient-richconditions although the decolorization of Poly R-478 was observed in nutrient-poor conditions.
1994-106
組み換え DNA によるマンガンペルオキシダーゼ変異株の作成とその諸性質
岸克行*1、Margo Kusters*1、Mary B．Mayfield*1、Taina Lundell*2、Margaret Alic*1、Michael H. Gold*1,*1
Oregon Graduate Institute, *2 Helsinki University
Homologous expression and site-directed mutagenesis of recombinant manganese peroxidase in
Phanerochaete chrysosporium
Katsuyuki Kishi*1, Margo Kusters*1, Mary B. Mayfield*1, Taina Lundell*2, Margaret Alic*1, Michael H. Gold*1*1
Dept. of Chemistry, Biochemistry and Molecular Biology, Oregon Graduate Institute of Science andTechnology, *2Dept. of Applied Chemistry and Microbiology, University of Helsinki
Abstract:
Homologous expression and site-directed mutagenesis on MnII ligands of manganeseperoxidase (MnP) in Phanerochaete chrysosporium were performed using glyceraldehyde-3- phosphate
dehydrogenase (gpd) primary metabolic promoter and polymerase chain reaction (PCR). The recombinant
proteins were expressed and secreted under primary metabolic growth conditions. The Mr and absorption
spectra of the recombinant MnP proteins were essentially identical to the wild type MnP. Steady state kinetic
values for the oxidation of MnII by recombinant wild type MnP and wild type MnP were also very similar. In
contrast, the mutation at MnII binding site resulted in markedly lower affinity and reactivity for MnII.
1994-107
リグノスチルベン-α,β-ジオキシゲナーゼアイソザイム遺伝子のクローニング
鴨田重裕、佐分義正
東京大学農学部
Cloning of a lignostilbene-α,β-dioxygenase isozyme gene from Pseudomonas paucimobilis TMY1009
Shigehiro Kamoda, Yoshimasa Saburi
Faculty of Agriculture, the University of Tokyo
Abstract:
The gene of lignostnbene-α,β-dioxygenase I (LSD-I), one of LSD isozymes, has been cloned
and expressed in E. coli. Since there has been no other gene of LSD isozyme around LSD-I gene, genomic
library was newly constructed. Detection of LSD isozyme gene was done with universal probe forα,β γsubunits,
which compose LSD isozymes. The positive clone was analyzed by southern blot hybridization. The
BamHI-HindIII 4.2kb fragment, containing LSD isozyme gene, was subcloned in pUC118. The gene wasexpressed in E. coli by the use of lac promoter. The product was purified in the purity showing single band on241

PAGE. And it was identified as LSD-III on native-PAGE and reversed-phase HPLC by comparison with LSD-I.
Furthermore the nucleotide sequence of the gene accorded with the amino acid sequences of two peptides fromdigested  subunits.
1994-108
樹木 OMT 遺伝子の構造とその発現様式の解析
早川敏雄*1、南藤和也*1、岡村慎仁*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究センター
Structures and expression analysis of O-methyltransferase genes from woody plant
Toshio Hayakawa*1, Kazuya Nantou*1, Shinji Okamura*1, Shinya Kawai, *1 Yoshihiro Katayama*2, Noriyuki
Morohoshi*1*1
Facurity of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology
Abstract:
We isolated two genes encoding O-Methyltransferase from Poplus kitakamiensis. The Genomic
clone g26 consists of four exons divided with three introns. And another clone, g25 consists of five exons
divided with four introns and it shared higher homology with OMT CDNA from P. kitakamiensis. RNA blot
analysis using gene-specific probes shows that the CDNA accumulates in young stem tissue, but g26 expresses
in young leaf. The difference of expression pattern of genes demonstrates that OMT genes are developmentally
regulated in the tissue-specific manners.
1994-109
PAL 活性の阻害は二次壁の木化にどのような影響を及ぼすのか？ ヒャクニチソウ単難葉肉細胞培養系を用いて
中島 仁、高部圭司、佐伯 浩
京都大学農学部
Inhibition of PAL activity by 2-aminoindan-2-phosphonic acid (AIP) caused the depression of lignin content of
secondary wall thickening isolated Zinnia mesophyll cell
Jin Nakashima, Keiji Takabe, Hiroshi Saiki
Faculty of Agriculture, Kyoto University
Abstract:
Isolated mesophyll cells from the first leaves of Zinnia elegans L. cv. Canary Bird can be
induced to differentiate into tracheary elements, which can give us a lot of biochemical events during the courseof secondary thickening and lignification. The influence of AIP, an inhibitor of PAL on lignin formation wasobserved under a TEM and an UV microscope. At 96 hr, the differentiation into tracheary elements had almost
finished, the secondary walls were lignified completely and showed the electron opaque material covered thefibrilar texture observed at 72 hr. These walls gave the absorption maxima about 280nm. Secondary walls
inhibited PAL activity by AIP at 100 M presented greatly different images as if they were cracked. They
showed weak UV absorption and quite different UV absorption spectra. At 54 hr of culture, coniferyl alcohol at
100 M were administered after inhibition of PAL activity by AIP, then the secondary walls were given the UV
absorption maxima as much as the secondary walls normally cultured, indicating that the secondary walls wereartificially lignified by the exogenous monolignol.
1994-110
モノリグノールグルコシドの樹幹内分布
福島和彦、田口小百合、松井直之、安田征市
名古屋大学農学部
Distribution of monolignol glucosides in tree
Kazuhiko Fukushima, Sayuri Taguchi, Naoyuki Mstsui, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
Quantitative analyses were made on monolignol glucosides in 50% EtOH extracts fromdifferent tissue fractions of Pinus thunbergii, Ginkgo biloba and Magnolia kobus in May, June and August. In
gingko and pine, coniferin existed mainly in the xylem, and the content was highest in May and lowest in
August. In magnolia, large amount of coniferin and syringin was contained even in the bark. and the content ofsyringin in August was much higher than that in other season. As the distance from tip became longer, thesyringin/coniferin ratio became higher, especially in the bark.
242

1994-111
Arctium lappa のリグナン生合成酵素
梅澤俊明、島田幹夫
京都大学木質科学研究所
Lignan synthesis by cell-free extracts of Arctium lappa
Toshiaki Umezawa, mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Cell free extracts from Arctium lappa. catalyzed the formation of secoisolariciresinol andlariciresinol, when incubated with coniferyl alcohol in the presence of NADPH and H2O2. Since A. lappa
grows very well, the plant can be used as a plant material for the study of lignan synthesizing enzymes.
1994-112(＋)-Erythro-(4,7-dihydroxy-3-methqxy-1”-allyl-3’,5’-dimethoxy)-8-O-4’-neolignan の生物変換とその変換物の抗菌活性
宮沢三雄、○笠原博幸、亀岡 弘
近畿大学理工学部
Biotransformation and antibacterial activity of(+)-erythro-(4,7-dihydroxy-3-methoxy-1”-allyI3’,5’-dimethoxy)-8-O-4'-neolignan
Mitsuo Miyazawa, Hiroyuki Kasahara, Hiromu Kameoka
Faculty of Science and Engineering, Kinki University
Abstract:
The biotransformation ofanacyclic
neolignan,(+)-erythro-(4,7-dihydroxy-3methoxy-1"-allyl-3',5'-dimethoxy)-8-O-4'-neolignan (1 ) in rat and fecal intestinal bacteria in vitro have been
investigated. The sole metabolic product which excreted to feces (>98%) and urine (<2%) was identified as(+)-(4-hydroxy-3-methoxy-1'-allyl-3',5'-dimethoxy)-8-O-4'-neolignan (2) by the spectroscopic methods.
Although rat and fecal intestinal bacteria could transform 1 to 2, several tested microbes which can oxidize
lignans and terpenoids could not transform 1. The antibacterial activities of 1 and 2 were also investigated andrevealed that both compounds showed to be antibacterial against several microbes.
1994-特別講演
フェニールプロパノイドと植物保護
谷口東二
九州大学農学部
Invited Lecture: The role of phenylpropanoids in plant protection and plant growth regulation
Eiji Taniguchi
Faculty of Agriculture, Kyushu University
Abstract:
A wide variety of phenylpropanoids, including flavonoids and tannins etc., is considered as very
important ecochemicals in the enviromental ecology. For example, the fluvic acid, producing from the plant
residues in the soil and partially from lignin-like materials, may takes a role of iron-transportation fromterrestrial to aquatic environment, where a rich biosphere is brought in by nourishing algae. In plant-parasite
relationship, a sort of flavonoids has been revealed to be the signal compound of host plant for the parasite, andsome of phytoalexins are old-known pterocarpanoids. Allelopathy is also largely caused by phenylpropanoids
and their related compouunds. From the chemo-ecological point of view, the importance of phenylpropanoids
for plant protection and regulation will be discussed by presenting two brief stories concerning with an
insecticidal neolignan of the genus Phryma and an auxin-transport inhibitor as a chalcone analog.
1994-201
常温硬化クラフトリグニン接着剤の製造に関する研究
島谷啓二*1*２、佐野嘉拓*１*１
北海道大学農学部、*２本州製紙株式会社
Preparation of kraft lignin-based cold setting adhesives
Keiji Shimatani*1, Yoshihiro Sano*2*1
Faculty of Agriculture, Hokkaido University，*2Honshu Paper Co. Ltd.
Abstract:
The utilizaion of softwood kraft lignin in one of the main substrate of cold setting woodadhesives was investigated. Kraft lignin, formaldehde-phenol-kraft lignin copolymer (LP-resin) andresorcinol-terminated LP-resin (LPR-resin) were prepared as described in the 38th Lignin Symposium243

(Takarnatsu). When 5-10% methanol were added to the LPR-resin solution with a solid content of 45%
containing small amounts of paraformaldehyde, the mixture developed the excellent strength properties forcold-setting wood adhesives. Furthermore, LP-, LPR- and resorcinol- formaldehyde-resins were characterized
by thermal analyses.
1994-202
リグニン及び糖蜜含有型ポリウレタンフォームの物性
廣瀬重雄*1、渡嘉敷唯章*2、畠山兵衛*1*1
物質研研究所, *2 トロピカルテクノセンター
Thermal and mechanical properties of polyurethanes containing lignin and saccharides
Shigeo Hirose*1, Tadaaki Tokashiki, *2 Hyoe Hatakeyama*1*1
National Institute of Materials and Chemical Research, *2Tropical Technology Center Ltd.
Abstract:
Polyurethane (PU) foams were prepared by the following procedures. An ethylene glycol (EG)solution of kraft lignin (KL) was mixed with polyethylene glycol (PEG), and then the obtained solution was
reacted with diphenylmethane diiisocyanate (MDI) in the presence of small amounts of water, silicone
surfactant and tin catalyst. PU's containing molasses (MOL) were also prepared according to the above
procedures. Thermal properties of PU's were studies by thermogravimetry (TG) and differential scanningcalorimetry (DSC). Mechanical properties were also studied by compression tests. The effect of the addition ofKL, MOL and EG to PU’s on physical properties were studied.
1994-203
末晒し酢酸パルプの化学修飾による分子会合体の調製（I） 残存リグニンをコアとする誘導体のセルフアッセ
ンブリー
橋田 光、浦木康光、佐野嘉拓
北海道大学農学部
Preparation of unbleached acetic acid pulp derivatives to form self-aggregates in water by chemical
modification (I), Self-assembly of the pulp derivatives centered around residual lignin as cores
Koh Hashida, Yasumitsu Uraki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Self-assembly or aggregation of polymer amphiphiles and hydrophobically associatingwater-soluble polymers is of great interest with respect to biological application and novel industrial importance.
In this study, the preparation of self-aggregates in water from acetic acid plup (AWP), which contained larger
amount of lignin than unbleached kraft pulp, by chemical modification was investigated to develop new
functional materials from lignocellulose. Hydroxypropyl (HP)-AWP was indicated to form the aggregates inaqueous solution by transmission electron microscopic observation. On the other hand, HP-bleached AWP andcommercial HP-cellulose were not found the phenomena. Furthermore, carboxymethyl-AWP did not also form
the aggregate. These suggested that the AWP derivatives involving hydrophilically nonionic functional groupself-assembled in water as cores of the hydrophobicaIly residual lignin.
1994-204
化学変性した工業リグニン中のフェノールカルボン酸型構造の抗菌活性
中野準三、山田まゆみ、草桶秀夫
福井工業大学工学部
Antibiotic activity of phenol carboxylic acid type structure in chemically modified industrial lignin
Junzo Nakano, Mayumi Yamada, Hideo Kusaoke
Faculty of Engineering, Fukui Institute of Technology
Abstract:(1) The antibiotic activity of phenol carboxylic acid changes with the species of microorganisms. The activity of ester is higher than that of free carboxyl group. Methoxyl group gives negative effecttoward the activity. The relative position of phenolic hydroxyl and carboxyl groups on aromatic nucleus does
not give the remarkable effect toward the activity. (2) In order to give the activity to industrial lignin, theintroduction of phenol carboxylic type structure has been tried by the use of sodium sulfide treatment andcaustic fusion. Within the limits of this experiment so far, the ethanol soluble fraction after the fractionation of
caustic fused lignin shows comparatively high antibiotic activity.
1994-205244

Phanerochaete sordida YK-624 株の産生するマンガンペルオキシダーゼによるクラフトパルプの漂白
原園幸一、近藤隆一郎、坂井克己
九州大学農学部
Bleaching of kraft pulp with manganese peroxidase secreted from Phanerochaete sordida YK-624
Koichi Harazono, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We have previously reported that bleaching of hardwood kraft pulp with isolated manganeseperoxidase (MnP) from Phanerochaete sordida YK-624 is possible. In the present study, supplementary
experiments in various conditions were carried out to improve the method of bleaching with MnP. An optimum
pH for enzyme treatment was 4.5. A maximum activity was observed when a temperature was 45ºC. In variousorganic acid buffers (50 mM and pH 4.5), malonate functioned most effectively as an Mn 3+ chelator during
bleaching of pulp with MnP. A surfactant was an important factor on enzyme bleaching. Enzyme treatmentswith H2O2-generating enzyme, glucose oxidase, had a similar effect on pulp brightness and bleachability as
those with H2O2 added directly. The pulp treated with MnP had strength properties comparable with those forunbleached hardwood kraft pulp.
1994-206
An initial evaluation of the role of lignin-carbohydrate complexes in the xylanase prebleaching of kraft pulps
Shinzo Yokota*1, Ken K.Y．Wong*2, John N．Saddler*2*1
Faculty of Agriculture, Utsunomiya University, *2Faculty of Forestry, University of British Columbia
Abstract:
The molecular weight distribution of lignin- and xylan-containing macromolecules, that havebeen isolated from kraft pplps derived from aspen and spruce, was determined using size exclusion
chromatography under highly alkaline conditions. A UV-vis monitor and a pulsed amperometric detector wereused to monitor the elution of lignin and carbohydrates, respectively. The change in molecular weight, as aresult of treatment with xylanase and acid was evaluated in order to examine the role of lignin-carbohydratecomplexes in the xylanase prebleaching of kraft pulp. The results indicated that xylanase could decrease themolecular weight distribution of the UV-absorbing material in xylan-rich fractions obtained from kraft pulp.
1994-207
クラフトパルプの着色性キシラン画分の分離と微生物分解
三亀啓吾、渡辺隆司、本田与−、桑原正章
京都大学木質科学研究所
Fractionation and microbial degradation of chromophoric xylan fractions from kraft pulp
Keigo Mikame, Takashi Watanabe, Yoichi Honda, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Unbleached kraft pulp (UKP) was degraded by a cellulase/ xylanase-bioreactor. Water-soluble
chromophoric xylan was separated from the UKP by silica gel column chromatography. The fraction wascharacterized as follows; 1) This fraction contained more than 40% of unremovable inorganic atoms including
Si, Na and S, together with non-branched xylan chain. 2) In the NMR spectrum, signals originating from
olefinic carbons and methoxyl group were below background noise, suggesting that the major chromogen in thisfraction is not a typical residual lignin. 3) The xylanase-resistant fraction was more effectively decolorized by
microflora from soils rather than selected white-rot fungi which effectively decolorize the intact unbleachedkraft pulp itself.
1994-208
酸素−アルカリ漂白過程における多糖類の分解機構（3） 酸素圧の反応選択性への影響
横山朝哉、安本光夫、松本雄二、飯塚堯介
東京大学農学部
Dependence of carbohydrate degradation on reaction of lignin during oxygen bleachjng (III), Effect of oxygenpressure on the reaction selectivity
Tomoya Yokoyama, Mitsuo Yasumoto, Yuji Matsumoto, Gyosuke Meshitsuka
Faculty of Agriculture, The University of Tokyo
Abstract:
A kinetic investigation was performed on the oxygen-alkali treatment of the mixture ofcarbohydrate model compound, methyl -D-glucopyranoside (MeG) and lignin model compound,
2,4,6-trimethylphenol (TMPh). The whole degradation pathway of TMPh was expressed by a following simple
245

formula.
-d[TMPh]/dt=k[TMPh]n [TMPh]: concentration of TMPh n: reaction order k: reaction constant
The amount of degraded MePG is dependent on the amount of degraded TMPh and expressed roughly by afoflowing simple formula.
MePG degradation (mol) = A x TMPh degradation (mol) A : reaction selectivity constant
1994-209
リグニンによるセルロースのオゾン分解促進
真柄謙吾*1、富村洋一*1、細谷修二*1、島田謹爾*1、池田 努*2*1
森林総合研究所, *2 筑波大学農林工学系
Accelerated degradation of cellulose by the presence of lignin during ozonolysis
Kengo Magara*1, Yoichi Tomimura*1, Shuji hsoya *1, Einji Shimada*1, Tsutomu lkeda*2*1
Forestry and Forest Products Research Institute, *2Institute of Agricultural and Forest Engineering. Universityof Tsukuba
Abstract:
To clarify the influence of residual lignin in the kraft pulp on the degradation of cellulose,cellobiose was treated with ozone in the presence of vanillyl alcohol. When cellobiose alone was ozonized, thecellobiose was degraded linearly with the increase in supplied ozone. When cellobiose was ozonized in thepresence of vanillyl alcohol, the coexisted vanillyl alcohol was completely consumed at the initial period ofozonolysis. As for the degradation of cellobiose, more degradation of the cellobiose was observed in thepresence of vanillyl alcohol than its absence until ozone supply reached about 6 mmol per one mol of cellobiose.
Most of the supplied ozone within this period has been consumed by the reaction with vanillyl alcohol, and theamount of ozone to attack cellobiose should be much smaller. However, the cellobiose was degraded more
readily in the presence of vanillyl alcohol than in vanillyl alcohol free condition. So that we concluded thatorganic ozonides or hydroxy radicals formed from the reaction of vanillyl alcohol and ozone accelerated thedegradation of cellobiose.
1994-210
漂白過程で生じる高分子塩素化リグニンの構造
新谷博幸、松本雄二、飯塚堯介
東京大学農学部
Structure of high molecular weight chlorolignin produced by bleaching
Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Faculty of Agriculture, the University of Tokyo
Abstract:
Three types kraft pulp (unbleached softwood kraft pulp, unbleached hardwood kraft pulp andoxygen prebleached hardwood kraft pulp) were chlorinated at various levels of chlorine ratio (0.1 - 0.3), andresidual chlorolignins in pulps were extracted in high yields with aqueous dioxane. Extracted chlorolignins weretreated by aqueous alkali under a similar condition as E1-stage of bleaching. Structural features of extracted
chlorolignins and their alkali-treated products were analyzed by 1H-NMR spectroscopy. These analytical results
revealed that chlorolignins have structures which are quite different from usual lignin structures. Namely, only
few aromatic structures are present in chlorolignins. Instead of this, chlorolignins are very rich in methyl,
methylene and methine structures.
1994-211
北海道産広葉樹の連続常圧酢酸パルプ化 —酢酸パルプの漂白について—
金野晴男、佐野嘉拓
北海道大学農学部
Acetic acid pulping of commercial hardwood chips in Hokkaido at atmospheric pressure with continuous
extraction, – Bleaching of acetic acid pulp Haruo Konno, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
To establish the bleaching methods of acetic acid pulp with non-chlorine reagents, the pulps
were prepared by extracting commercial chips of hardwood grown in Hokkaido with boiling 95% aqueous
acetic acid containing 0.32% H2SO4 continuously. The pulps were bleached in PA (peracetic acid), PA-P
(hydrogen peroxide) and O (oxygen)-PA-P sequence. The pulps were bleached at 62.9%, 77.9% and 90.2%
brightness by using 5%PA(70ºC,30min)-3%PA (70ºC, 90min), 5%PA-3%PA-P (2% pH11, 70ºC, 2h) and O(7%NaOH, 110ºC, 60min)-5%PA (70ºC, 60min)-P, respectively. The bleached pulps were characterized by246

K-values, viscosity and strength properties.
1994-212
ラジオトレーサー法によるクラフトパルプ化中のキシランの挙動の解明
今井貴規*1、安田征市*1、寺島典二*2*1名古屋大学農学部, *2USDA 林産物研究所
Behavior of xylan during kraft cooking studied by radiotracer technique
Takanori Imai*1, Seiiti Yasuda*1,Noritsugu Terashima*2*1
Factilty of Agriculture, Nagoya University, *2United States Department of Agriculture, Forest Products
Laboratory
Abstract:
To examine the behavior of xylan during kraft cooking by radiotracer method, the wood meal inwhich xylan was radio-labeled selectively by feeding myo-inositol-[2-3H] as a precursor to plant was treatedunder kraft cooking condition. Radioactivities of pulp and cooking black liquor obtained at various cooking
stages were determined. The results showed that dissolution of xylan was remarkable during heat-up period andmore than 70% of xylan was dissolved at this stage, and suggested that about 10% of the dissolved xylan was
readsorbed on pulp fiber and this part amounts to about 25% of xylan remaining in pulp.
1994-213
リグニン誘導体添加によるバクテリアセルロース膜生産性の改善
鮫島一彦、シリポン・プレムジェット、大谷慶人
高知大学農学部
Improvement of the acterial cellulose production efficiency with the addition of lignin derivatives
Kazuhiko Sameshima, Siripong Prenjet, Yoshito Ohtani
Faculty of Agriculture, Kochi University
Abstract:ln the previous papers we have demonstrated that the addition of lignosulfonate to a bacterial
cellulose medium remarkably enhanced the efficiency of the cellulose production by Acetobacter xylinum ATCC
10245. The highest cellulose membrane yield was 389% on the standard Hestrin-Schramm medium. In thispaper the effect of the addition of kraft lignin samples has been investigated. The addition of pine kraft lignin
increased the cellulose membrane yield (max. 139%) but that of birch kraft lignin affected adversely. The reason
for this phenomena might have to do with the lignin structure difference and could bc a clue to find a better
medium for the cellulose production.
1994-P101
白色腐朽菌ベッコウタケの染料脱色能及びリグニン分解能
遠藤陽子、割石博之、大賀祥治、田中浩雄
九州大学農学部
Decolorization of polymeric dye and degradation of lignin by the white-rot basidiomycete Fomitella fraxinea
Yoko Endo, Hiroyuki Wariishi, Shoji Ohga, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
Effective decolorization of polymeric dye, Poly-R by the white-rot basidiomycete Fomitellafraxinea was demonstrated under high nutrient carbon-high nutrient nitrogen (HCHN) conditions. This fungus
also exhibited the ability to oxidatively degrade either phenolic or nonphenolic lignin model compounds under
HCHN conditions. Under these conditions only laccase activity was observed, so far. The influence of theatmosphere and pH (4.5-6.5) on physiological phenomena of F. fraxinea was relatively minor compared to thoseof Phanerochaete crysosporium.
1994-P102
白色腐朽菌による色素の分解
桑原正章*1、渡辺隆司*1、井上千景*2、本田与一*1*1
京都大学木質研究所、*2 近畿大学農学部
Degradation of dyes by white-rot fungi
Masaaki Kuwahara*1, Takashi Watanabe*1, Chikage Inoue*2. Yoichi Honda*1*1
Wood Research Institute, Kyoto University, *2Faculty of Agriculture, Kinki University
Abstract:
Degradation of dyes by various basidionycetes was examined. Several fungi
Phanerochaete crysosporium, Bjerkandera adusta, Coriolus versicolor, C. hirsutus, C. consors, C. vellerus,247decolorized Azur B, Orange II, Congo red, Tropaeolin O and other dyes, which were added into Kirk's low
nitrogen medium. However, the rate of the degradation differed in fungal strains.
1994-P103
リグニン生分解に関する研究（II） —バイオブリーチング時に産生される還元系酵素について—
片桐誠之、堤 祐司、西田友昭
静岡大学農学部
Extracellular reductive enzyme produced during biobleaching of kraft pulp by white-rot fungi
Nobuyuki Katagiri, Yuji Tsutsmi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The role of reductive enzyme for the biobleaching of kraft pulp by Phanerochaete crysosporium
and Coriolus versicolor was investigated in solid-state fermentation system with low nitrogen-high carbon andhigh nitrogen high carbon media. The profiles of manganese peroxidase (MnP) and reductiye enzyme
productions during the biotbleaching were very different each other, suggesting the complementary function ofboth enzymes for the lignin degradation. Though a positive relationship between cumulative MnP activity andbrightness increase was observed, any positive correlation was not observed in case of cumulative reductive
enzyme activity. This result suggests that reductive enzyme may not be involved in the biobleaching of kraft
pulp.
1994-P104
クラフトパルプ漂白能力を持つ木材腐朽菌のスクリーニング
高野麻理子、西田篤実、中村雅哉
森林総合研究所
Screening of wood rotting fungi for kraft pulp biobleaching
Mariko Takano, Atsumi Nishida, Masaya Nakamura
Forestry and Forest Products Research Institute
Abstract:
Many studies about biobleaching processes are proceeding to develop new chlorine-freebleaching systems. But more efforts will be needed to overcome remaining problems for practical use. We
selected several wood rotting fungi for kraft pulp biobleaching using two screening methods, Poly-R
decolorization test and phenol coloradon test. 7 Fungi selected by Poly-R decolorization test show kraft pulp
biobleaching ability. After 10 days treatment, the most effective fungus was able to increase the brightness from28 to 54 and decrease kappa number from 15.7 to 6.1. 2 Fungi selected by phenol coloration test were able toincrease the brightness of oxygen-alkali bleached pulp but not unbleached kraft pulp.
1994-P105
機械パルプの光による色戻りを抑制する菌のスクリーニング
河村佳枝、伊藤和貴、沖 妙、橘 燦朗
愛媛大学農学部
Screening of fungi on depression of color reversion of mechanical pulps
Yoshie Kawamura, Kazutaka Itoh, Tae Oki, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Screaningg of fungi having depression of light-induced color reversion of mechanical pulps was
carried out by using 2,6-dichloroindophenol and methoxy-p-quinone as an indicator for estimation of ability ofdepression of the-color reversion. First, we tried tile screaning of fungi having reducing ability of
2,6-dichloroindophenol from soils in our uniiversity forest and 67 fungi were found on Czapek-Dox agar plates.
ln the second step, each 67 fungi was incubated in a liquid medium containing methoxy-p-quinone and 20 fungi
having ability of decoloration of the quinone were obtained. ln the third step, reactivity between each an
extracellular crude enzymes from the 20 fungi and methoxy-p-quinone was measured and screened fungi having
higher reactivity. By using this method, we obtained a funguds which was called 501 had higher ability for
depression of the color reversion. The fungus could be depressed 47 % of the color reversion ofthermomechanical pulps.
1994-P106
Compositional changes in compost during conventional and environmentally controlled composting and growthof Agaricus bisporus248

Kenji Iiyama*1*3, Thi Bach Tuyet Lam*1, Barry J．Macauley*2, Bruce A．Stone*1*1
Schools of Biochemistry and *2Microbiology, La Trobe University, Australia*3
Department of Forest Products, the University of Tokyo
Abstract:
Samples from conventional, “cold” and “hot” environmentally controlled composts(“cold” and “hot” EC) taken at various stages of composting and mushroom (Agaricus bisporus) growth wereanalyzed for changes in extractives, neutral sugar composition, lignin concentration, and lignin structuralfeatures. Variable amounts of extraneous inorganic solids in the form of fine sandy particles were removed by
sedimentation of the samples in a CCl4-CH2Br2 mixture. During composting, about two-thirds of the initialwall polysaccharides were consumed by compost microorganisms, and only 13-16% of the total polysaccharides
were used during mushroom production. The relative lignin content of composts as measured by acetyl bromide
procedure increased, both during composting and mushroom growth, and the chemical structure of lignin wasaltered by condensation and oxidation reactions.
1994-P107
Eucalyptus camaldulensis および E. globulus におけるリグニン S／G 比樹間内変異
小名俊博、園田哲也、柴田 勝
新王子製紙株式会社 林木育種研究所
With-in tree variation of lignin S/G ratio in Eucalyptus camaldulensis and E. globulus
Toshihiro Ona, Tetsuya Sonoda, Masaru Shibata
New Oji Institute For Forest Tree Improvement
Abstract:
With-in tree variation of lignin S/G ratio was analyzed for Eucalyptus camaldulensis and E.
globulus from Western Australia by using thioacidolysis method, as a link or quality breeding program.
Furthermore, whole-tree values of S/G ratio and suitable sampling heights were examined from the results ofeach position. As a result, the differences between species and trees were recognized.
1994-P108
クラフトパルプの亜硝酸処理における脱リグニン機構（2） —亜硝酸処理における LCC モデル化合物の反応—
岸野正典、大井 洋、黒田健一、山口 彰
筑波大学農林工学系
Mechanism of delignification during nitrous acid treatment of kraft pulp (II), Reaction of LCC modelcompound during nitrous acid treatment
Masanori Kishino, Hiroshi Ohi, Kenichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, The University of Tsukuba
Abstract:
Much attention has been paid to nitrous acid treatment of kraft pulp as one of the non-chlorine
bleaching. A nonphenolic lignin-carbohydrate complex (LCC) structure is one of the important residual lignin
structures of kraft pulp. To discuss the mechanism of delignification during nitrous acid treatment,veratrylglycerol-β-guaiacyl ether (VG) and its α-ethyl ether (VGE, as an LCC model compound) were used. The
reaction products observed at 90ºC suggested that the following reactions occur in the models: (1) cleavage of
the Cα-Cβbond, (2) acid-hydrolysis at an α-ethyl ether (in the case of the VGE experiment). Furthermore, theidentification of several unknown peaks was attempted and it is assumed that one of the unknown peaks iscorresponding to a compound with carboxylic acid.
1994-P109
ベンジルエーテル結合の選択的開裂によるクラフトパルプ残存リグニンの性状の検討
木村尚代、飯塚堯介
東京大学農学部
Characterization of residual lignin in kraft pulp by selective cleavage with pivaloyl iodide
Hisayo Kimura, Gyosuke Meshitsuka
Faculty of Agriculture, the University of Tokyo
Abstract:
In recent years, it has been claimed that chlorine bleaching produces various organic
chlorinated compounds causing enviromental problems. Therefore, the development of pollution-free bleachingis one of the most important subjects for the pulping industry. Many studies have been reported on the chemical
structures of residual lignin for the better understanding of inhibiting factors for the delignification. In thisreport, by the use of pivaloyl iodide (one of HASB reagents) for the selective cleavage of benzyl ether bonds249

under mild conditions, we tried to evaluate the contribution of benzyl ether bonds to the residual nature of lignin
in kraft pulp and to characterize the lignin fraction released from kraft pulp by this treatment.
1994-P110
熱分解ガスクロマトグラフィーによるクラフトパルプ残存リグニンの構造解析 —漂白処理における変化—
田中潤治、和泉明子、大井 洋、黒田健一、山口 彰
筑波大学農林工学系
Structural analysis of residual lignin in kraft pulp by pyrolysis-gas chromatography, —Changes of residual
lignin during chlorine bleaching—
Junji Tanaka, Akiko Izumi, Hiroshi Ohi, Kenichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, The University of Tsukuba
Abstract:
Pyrolysis-gas chromatography (Py-GC) provides useful complementary information about
lignin structures to chemical degradation methods, using small amounts of samples without any sample
pretreatment. Unbleached hardwood kraft pulp (LUKP) and oxygen-bleached hardwood kraft pulp (LOKP)
were chlorinated at various chlorine ratios (1-5% on Pulp) , and were extracted with sodium hydroxide solution.
Chlorinated kraft pulps before and after the alkali extraction were subjected to Py-GC, and structural changes oflignin in kraft pulp were studied.
1994-P111
酢酸リグニンを原料とする炭素織維の調製（3） —酢酸リグニンの溶融性—
久保智史、沢田雅博、浦木康光、佐野嘉拓
北海道大学農学部
Preparation of carbon fiber from acetic acid lignin (III), -Fusibility of acetic acid ligninSatoshi Kubo, Masahiro Sawada, Yasumitu Uraki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Thermal properties, especially fusibility, of acetic acid lignin (AWL) were investigatedby thermomechanical analysis (TMA). On the TMA measurement of fractionated birch (B)-AWL , the fractions
with less than 1,000 of molecular weight (Mw) indicated the clearly fusion state, while other fractions having
larger a than original B-AWL did not fuse. Therefore, the fusibility of B-AWL was caused by low molecularweight fractions. However, abies (A)-AWL was not fused probably due to condensation of aromatic nucleus.
These results suggest that the fusibility of AWL depends on not only acetylation of hydroxyl groups but also
molecular structures such as condensation. Furthermore, we examined the thermal properties of industrial kraft
lignin (KPL) blended with AWL. The grass-transition temperature of KPL was decreased by the addition of
AWL remarkably. These results indicate that KPL may be used as thermal molding materials by blending with asmall amount of AWL.
1994-P201
未晒し酢酸パルプの化学修飾による分子会合体の調製（II）〜ゲスト分子との相互作用〜
橋田 光、浦木康光、佐野嘉拓
北海道大学農学部
Preparation of unbleached acetic acid pulp derivatives to form self-aggregates in water by chemical
modification (II), - Interaction between pulp derivatives and guest molecules
Koh Hashida, Yasumitu Uraki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Uptake of hydrophobic fluorescence reagents as guest molecules to self-aggregatesof hydroxypropylated AWP (HP-AWP) was investigated to clarify the conjugation of the aggregates withwater-insoluble materials. HP-AWP was found to have obvious transition concentration at 1.27 mg/ml
corresponding to the critical micell concentration, and to form extremely hydrophobic regions in the aggregates,
which was suggested by both of the remarkably shift of maximum emission wavelength and the enhancement ofemission intensity. However, other derivatives having no self- assembly, HP-cellulose andcarboxymethyl-cellulose, scarcely form the hydrophobic region. This suggested that the aggregates of HP-AWP
took in the hydrophobic guest molecules in the hydrophobic regions which were probably formed by residual
lignin in HP-AWP.
1994-P202
250

フェニルクマラン型二量体の配糖体化
渡辺雄*1、棚橋光彦*1、重松幹二*1、篠田善彦*2*1
岐阜大学農学部, *2 岐阜大学連農
Glycosylation of phenylcoumaran type dimer
Yuichi Watanabe*1, Mitsuhiko Tanahashi*1, Mikiji Shigematsu*1, Yoshihiko Shinoda*2*1
Faculty of Agriculture,Gifu University, *2The United Graduate School of Agricultural Science, Gifu University
Abstract:
Phenylcoumaran glycoside was synthesized by linking the phenolic hydroxyl group of
dehydrodiconifcrylalcohol with -bromo-saccharides (glucose, galactose and xylose). The effects of theprotecting groups on the yields were invesdgated. The glucosylation yield was increased from 30.7 % to 46.8 %by changing the protecting group of glucose from acetyl to pivaloyl. In the case of pivaloyl derivatives ofgalactose and xylose, the yields were 23.40% and 68.0%, respectively. For the synthesis of this phenylcoumaran
glycoside, a new synthetic route was attempted with a phenyl- coumaran type dimer derived fromdehydrogenation of ethylferulate.
1994-P203
リグニン前駆体とへミセルロースの親和性
杉野秀明、重松幹二、棚橋光彦、（岐大連農）篠田善彦
岐阜大学農学部
Affinities between lignin precursors and hemicelluloses
Hideaki Sugino*1, Mikiji Shigematsu*1, Mitsuhiko Tanahashi*1, Yoshihiko Shinoda*2*1
Faculty of Agriculture,Gifu University, *2The United Graduate School of Agricultural Science, Gifu University
Abstract:
In plant cell wall, a lignin is deposited in the matrix of polysaccharides through the lignification
process. In this study, the binding of lignin precursors (p-coumaryl alcohol, coniferyl alcohol and sinapyl
alcohol) to hemicelluloses (from softwood and hardwood, and citrus pectin) were observed by ultrafiltration of
the mixed solutions to examine the affinities between lignin precursors and hemicelluloses. As a result, thebinding of lignin precursor to hemicellulose was observed in all pairs. It shows that the attractive interaction
exists between them.
1994-P204
ラマン散乱スペクトルによる木材と竹のリグニン解析
武井利之、加藤紀子、飯島倫明、桧垣宮都
東京農業大学農学部
Raman spectroscopic identification of wood and bamboo lignin
Tosiyuki Takei, Noriko Kato, Tomoaki Iijima, Miyato Higaki
Faculty of Agriculture, Tokyo University of Agriculture
Abstract:
Fundamental conditions to record near-infrared excited fourier-transform Raman
spectra from wood meal samples were researched. Favorable Raman spectra were obtained between 150mW to
200mW of laser power with more than 100 times scanning, The size of meal samples between 20 to 200 mesh,has not affected the spectra. Under these conditions Raman spectra were recorded from meal samples andholocellulose of Fagus crenata B.I., Cryptomeria japonica D, Don and Phyllostachys pubescens Mazel as a
typical hardwood, softwood and bamboo respectively. The Raman band intensity of F. crenata and C, japonica
were decreased by the delignification process, at the wave number of 1660 cm−1,1600 cm−1, 1460 cm−1, 1330
cm−1,1030 cm−1and 800 cm−1. In the case of P. pubescesns, extremely strong bands observed at the wave
number of 1630 and l604 cm−1, and their intensity were decreased by alkaline-treatment. By the delignification
process of P. pubescens the same bands as so F. crenata and C. japonica but 1660 cm−1, and the bands at 1630
cm−1 and 1424 cm−1 were decreased. This result indicate that these Raman bands decreased by thedelignification process were those of lignin origin. It was suggested that by recording Raman spectra from woodmeal sample, the information of native state lignin were obtained directly and easily.
1994-P205
リグニンモデルの一電子酸化服部和生、高谷政広、浜田良三、岡本 忠
近畿大学農学部
One electron oxidation of lignin models
Kazuo Hattori, Masahiro Takatani, Ryozo Hamada, Tadashi Okamoto251

Faculty of Agriculture, Kinki University
Abstract:
To study the mechanism of alkaline nitrobenzene oxidation of lignin, oxidation of some lignin
models, derivatives of cinnamic acid, was examined by using nitrobenzene or some oxidizing
agents such as CAN and MnO2. Obtained results support a mechanism of initial oxidative decarboxylation,
succeeding hydration of a side-chain double bond, and oxidation of the generated benzylic alcohol. Although
one-electron-transfer mechanism is important in the oxidation step, quinone methide intermediate is also
necessary because it accelerates hydration of the aryl- conjugated double bond under alkaline conditions.
1994-P206
ユーカリ属の組織化学的方法によるリグニン分析（III） —抽出条件の決定—
渡辺陽子*1、小島康夫*1、船田 良*1、深沢和三*1、小名俊博*2、浅田隆之*2*1
北海道大学農学部、*2 新王子製紙株式会社林木育種研究所
Lignin analysis of Eucalyptus by histochemical methods (III), —Evaluation of the methods of alkali extraction
in removing polyphenols—
Yoko Watanabe*1, Yasuo Kojima*1, Ryo Funada*1, Kazumi Fukazawa*1, Toshihiro Ona*2, Takayuki Asada*2*1
Faculty of Agriculture, Hokkaido University, *2Shin Oji Institute for Forest Tree Improvement,
Abstract:
Lignin analysis of Eucalyptus have been done by histochemical methods. However, Eucalyptus species
contain a lot of polyphenols which influence on lignin analysis and thus it is required to remove thosepolyphenols prior to analysis of lignin. In this study, the effect of polyphenols on lignin analysis byhistochemical methods were evaluated using alkali extracted samples. Specimen (cross sections and woodmeals) of two Eucalyptus species were extracted by given alkali conditions and then they were analyzed bychemical arid histochemical methods. It appeared that those alkali extractives contained guaiacyl typepolyphenols and affected considerably on lignin analysis, especially in vessel walls and ray cells, byhistochemical methods.
1994-P207
ポプラ早生樹リグニソの化学構造について —ヒドロキシ芳香族酸類のリグニンに対する結合様式
金 泳信*1、飯山賢治*1、倉橋昭夫*2、飯塚堯介*1*1
東京大学農学部、*2 東京大学北海道演習林
Strutural feature of lignin in fast-grow and native aspen woods: Linkage types of hydroxybenzoic andhydroxycinnamic acids
Youngsin Kim*1, Kenji Iiyama*1, Akio Kurahashi*2, Gyosuke Mcshitsuka*1*1
Faculty of Agriculture, the University of Tokyo, *2University Forest, the University of Tokyo
Keywords: MWL, LCC，vanillic acid, syringic acid, syringaldehyde, p-coumaric acid, ferulic acid, cellwall, GC-MS
1994-P208
交雑ヤマナラシ（Populus kitakamiensis）シンナミルアルコールデヒドロゲナーゼ（CAD）遺伝子の単離および解析
小園聖治*1、刑部敬史*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Isolation and characterisation of genes encoding cinnamyl alcohol dehydrogenase from hybrid aspen (Populus
kitakamiensis)
Shoji Oguni*1, Keisi Osakabe*1, Shinya Kawai*1, Yosihiro Katayama*2, Noriyuki Mrohosi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative Research Center,
Tokyo University of Agriculture and Technology
Abstract:
To change the quality and quantity of lignin, we isolated a partial gene encoding cinnamyl
alcohol dehydrogenase (CAD) from hybrid aspen (Populus kitakamiensis) by polymerase chain reaction (PCR)
method. The nucleotide sequence was analyzed and used as a probe of Southern and Northan analysis and
CDNA isolation. Results showed that there was a small number of genes for CAD in the genome and CAD
genes expressed in the upper and lower stem and weekly expressed in leaves. Screening of λgt 10 cDNA library,
one CAD cDNA clone (1.4 Kbp) was isolated and characterized.
1994-P209
交雑ヤマナラシ・キクカミハクヨウの茎において発現するペルオキシダーゼアイソザイム遺伝子群の発現様
252

式の解析
刑部敬史*1、小山浩和*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Mofecular cloning of anionic peroxidases from Populus kitakamiensis and Inhibition of peroxidase expression
by using antisense RNA method
Keisi Osakabe*1, Hirokazu Koyama*1, Shinya Kawai*1, Yosihiro Katayama*2, Noriyuki Mrohosi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative ResearchCenter, Tokyo University of Agriculture and Technology,
Abstract:
Agrobacterium-mediated gene transformtion and plant regeneration from transformed tissue
were established for hybrid aspen, Populus kitakamiensis (P. sieboldii X P. grandidentata). Using this system,
antisense prxA1 gene driven by prxA1 promoter that was introduced into aspen. The peroxidase activities oftransformed callus were about 2-5 ford decreased. We have already isolated three cDNAs that encode anionicpeoxidase from P. kitakamiensis. In this report, we have two genomic DNAs corresponding to the cDNAs and anovel genomic DNA that encodes anionic peroxidase. The pattern of expression of the peroxidase genes inseveral plant organs is discussed.
1994-P210
樹木フェニルアラニンアンモニアリアーゼ（PAL）の発現解析
刑部祐里子*1、北村宗子*1、川合伸也*1、片山義博*2、諸星紀幸*1*1
東京農工大学農学部、*2 東京農工大学共同研究開発センター
Characterization and expression of phenylalanine ammonia-lyase from populus kitakamiensis
Yuriko Osakabe *1, Hiroko Kitamura*1, Shinya Kawai*1, Yosihiro Katayama*2, Noriyuki Mrohosi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative ResearchCenter, Tokyo University of Agriculture and Technology,
Abstract:
In Populus kitakamiensis, the genes for phenylalanine ammonia-lyase (PAL) form a small genefamily. Southern blot analysis indicated that PAL family was consisted with at least six members. We thenisolated and characterized six PAL genes, HPAL13, pal g1, pal g2a, pal g2b, pal g3, and pal g4, from genomeof Populus kitakamiensis. Furthemore, the PAL protein was isolated from the stem tissue, and analyzed usinganion-exchange chromatography and 2-D gel electrophoresis detected by immuno blot. Results indicated that
Mr identical with PAL subunits was 75,000 and five subunits differing pl values were observed in the wholestem tissue. Results from Northern blot analysis suggested that pal g1 was expressed in the young tissues near
the shoot bud and pal g2 gene-group was mainly expressed in lower stems. Thus, the expression of each PAL
gene (orgene-class) from Populus kitakamiensis was tissue-specific and altered with the stem growth. In Populus
kitakamiensis PAL play the important roles that are classified two groups in the function of the stem.
1994-P211
カワラタケラッカーゼアイソザイムの解析
三園順子*1、飯村洋介*２、川合伸也*1、片山義博*３、諸星紀幸*1*1
東京農工大学農学部、*２通産省工業技術院資源環境技術総合研究所、*３東京農工大学共同研究開発センター
Characterization of laccase isoenzymes from Coriolus versicolor
Junko Mikuni *1, Yousuke limura,*1, Shinya Kawai*1, Yosihiro Katayama*2, Noriyuki Mrohosi*1*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Cooperative ResearchCenter, Tokyo University of Agriculture and Technology,
Abstract:
Extracellular laccase is commonly produced by wood-degrading white-rot fungi. Our previous
studies cleared the genetic and enzymic properties of Laccase III from Coriolus versicolor, and showed thisenzyme was concerned in lignin biodegradation. In order to define the inherent and physiolosical role of laccase,
we present to characterize the other laccase isoenzymes. Laccase l was little adsorbed on ion exchanger, thus it
is considered to have a weak surface charge. So this enzyme was separated by preparative electrophoresis
system, the Rotofor cell (BIO-RAD). As genetic characterization, we determined the DNA sequence of CVLG1.
1994-P212
担子菌のプロトプラスト調製および細胞融合によって誘導されたラッカーゼ欠損株の安定性
江口文陽、桧垣宮都253

東京農業大学
The stability of laccase-less mutants induced by preparation of protoplasts and cell fusion of Basidiomycetes
Fumio Eguchi, Miyato Higaki
Faculty of Agriculture. Tokyo University of Agriculture,
Abstract:
Protoplasts were prepared from the mycelia of basidionycetes; P. ostreatus, P.sajor-caju and P.
eryngii. In the regenerated mycelia from them, some mutants lacking laccase were induced. These mutants had
no decoloring activity for carminic acid and Remazol brilliant blue R, both of which are decolorized by theparent strains. Some fusion strains with no laccase activity were produced by individual electric fusion between
these laccase-less mutants or the strains with and without the laccase activit,y. These laccase-less mutants weresuccessively cultured on an agar plate and 3 mooths, growth alteration was observed in some of their mycelia.
Laccase activity of these mycelia were determined and some strains were found to have lower activities of the
enzyme than the parent strains. In order to examine the possibility that the culture conditions of mycelia havecaused this phenomenal, an investigation of changes in laccase activity of mycelia were made by the freeze
stock method at -80 ºC and under the culture conditions using a liquid or agar medium. These results indicatethat the laccase activity and the growth of mycelia were more stable for the freeze stock method.
1994-特別寄稿「リグニン討論会の発足の頃」
九州大学名誉教授 千手諒一254

第 40 回 （1995.10.12-13） つくば 研究交流センター
1995-101
樹木のフエニルプロパノイド生合成系のチトクロム P-450 遺伝子の解析
盛 有子*1、川合伸也*2、Zhan Xiang Can*2、塩川貴広*2、片山義博*1、諸星紀幸*1*1
東京農工大学大学院生物システム応用科学研究科、 *２東京農工学大農学部
Molecular cloning and heterologous expression of cytochrome P-450 from a woody plant (Populus
kitakamiensis)
Ariko Mori*1, Sinya Kawai*2, Zhan Xiang Can*2, Takahiro Shiokawa*2, Yoshihiro Katayama*1, Noriyuki
Morohoshi*1*1
Gradtnte school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
In higher plants, some cytochrome P-450 enzymes are concerned with biosynthesis ofphenylpropanoids. Cne of them, cinnamic acid 4-hydroxylase (CA4H), catalyzes the formation of
p-coumaric acid from trans-cinnamic acid. The other enzyme, ferulic acid 5-hydroxylase (FA5H), catalyzes theformation of 5-hydroxyferulic acid from ferulic acid. CA4H and FA5H provide precursors for the biosynthesisof secondary metabolites, such as lignin. CA4H gene (cyp73a, cyp73b, and cyp73c) were isolated from Populus
kitakamiensis, and have been determined the nucleotide sequences of their ORFs and promoter regions. Each ofthem has two introns. In the promoter regions of cyp73a and cyp73b, there are many cis-element-like sequencesthat ate conserved in promoters of genes involved in phenylpropanoid biosynthesis. We also isolated a CDNA
(cyp73a) from a P. kitakamiensis CDNA library constructed with mRNAs of the upper part of the stem. Ushg
this CDNA clone, we constructed CA4H expression plasmids for heterologous expression in yeast.
1995-102
樹木酸性ペルオキシターゼ遺伝子の組織特異杓発現様式の解析
手嶋克介*1、刑部敬史*２、川合伸也*２、片山義博*1、諸星紀幸*1、海老沼宏安*３*1
東京農工大学大学院生物システム応用科学研究科、 *２東京農工学大農学部、*３日本製紙株式会社中央研究所
Tissue specific expression patterns of anionic peroxidase genes from Populus kitakamiensis
Katsusuke Teshirna*1, Keishi Osakabe*2, Shinya Kawai, *2 Yoshihiro Katayama*1, Noriyuki Morohoshi*1,
Hiroyasu Ebinuma*3*1
Gradtnte school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology, *3Nippon Paper
Industries.
Abstract:
We have isolated three CDNAs (pA2a, pA2b and pA3) and four genomic DNAs (prxA1, prxA2b,
prxA3, and prxA4a) for anionic peroxidases from Populus kitakamiensis and analyzed their expression patterns
by using Northern blotting. The results suggested that the each gene is under the different regulation. prxA3aand prxA4a are the genes that encode anionic isoenzymes, which specifically express in stems. To identify theregulation of each gene, we analyzed the developmental expression of GUS activity in transgenic tobacco plants
containing the prxA3a- or prxA4a-promoter and GUS gene fusion. The GUS activity under the control of theprxA3a promoter (1.0 kbp) was histochemically deteted in xylem and phloem tissues in which lignin isvigorously synthesized. In the other hand, the prxA4a promoter (1.1kbp) had transcriptional activity only in theauxiliary bud and leaf trace. In order to determine cis-acting elements which regulate complicatedpatterns of prxA3a expression, we constracted the 5 - deleted series of the promoter fragment with GUS geneand transformed plants with them.
1995-103
酵素ラッカーゼによるコニフェリルアルコール、イソオイゲノールの重合反応
柴 忠裕、肖 玲、宮腰哲雄
明治大学理工学部
Polymerization of coniferyl alcohol and isoeugenol by laccases
Tadahiro Shiba, Xiao Ling, Tetsuo Miyakoshi
Department of Industrial Chemistry, Meiji University
Abstract:
In this paper, we wish to report dehydrogenative polymerization of isoeugenol and coniferyl
alcohol by various laccases and peroxidase. Urushi laccase oxidized isoeugenol very slowly. Dimer (1), (2a,2b),255

tetramer (3) and oligomer were produced, but no dehydrogenative polymer (DHP). Fungal laccase oxidized thesubstrate faster than urushi laccase. Peroxidase from horseradish oxidized isoeugenol even slower than thefungal laccase in the presence of hydrogen peroxide.
Compared to urushi laccase, fungal laccases oxidized coniferyl alcohol faster under the same reaction conditions.
Dehydrogenative polymer obtained enzymic reaction of coniferyl alcohol and isoeugenol have beencharacterized by NMR analysis.
1995-104
Arctium lappa によるセコイソラリシレジノールの生合成
梅澤俊明、島田幹夫
京都大学木質科学研究所
Biosynthesis of secoisolariciresinoi in Arctium lappa
Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Cell-free extracts from Arctium lappa L. cv. kobarutogokuwase catalyzed the enantio- selectiye
fortmtion of (+)-secoisolariciresinol, Then incubated with coniferyl alcohol in the presence of NADPH andH2O2. The stereochemical mechanisms sharply contrasts with that in (-)-secoisolariciresinol formation fromconiferyl alcohol by enzymes of Forsythia plants.
1995-105
リグニン化学構造の不均一性 —エーテル結合の部分的開裂によって生成する低分子量リグニン区分の性状—
大熊啓映子、飯塚堯介
東京大学農学生命科学研究科
Heterogeneity of lignin structure, —Properties of low molecular weight lignin formed by limited ether bonds
cleavage—
Keko Ohkuma, Gyosuke Meshitsuka
Graduate School of Agriculture and Agricultural Life Sciences, the University of Tokyo
Abstract:
The authors have been investigating the structural heterogeneity of lignin, in particular,
heterogeneous distribution of bonding structures and aromatic structures. ln this context, a β-O-4 rich end-wiselignin fraction was found in the low molecular weight fraction of birch periodate lignin and phenylcoumaranrich lignin fraction was found in a very low yield in the TMSiI-depolymerized fraction. In this paper, a periodate
lignin prepared from diazomethane- methylated wood meal was partially depolymerized by TMSiI and the low
molecular weight fractions extracted by dioxane/water (9/1) were characterized. It was found that the low
molecular weight fractions were rich in β-O-4 linkage and syringyl unit. This was particularly characteristic forthe acetone soluble fractions.
1995-106
リグニンの酸化過程におけるシリンギルおよびグアイアシルカルボニルラジカルの生成機構 —特異的シリ
ンギルおよびグアイアシル末端基の定量—
鬼木隆季、高浜有明夫
九州歯科大学一般教育部
Production mechanism of syrhgyl carbonyl and guaiacyt carbonyl radicals by oxidations of lignin,-Determination of syringyl and guaiacyl end-groups the bonding type of which are specificT. Oniki, U. Takahama
Kyushu Dental College
Abstract:
Electron spin resonance spectra of dioxane lignins from various plants were measured at pH l3
in the presence of oxidants. Hardwood lignin and true grass lignins showed signals due tosyringyl carbonyl and guaiacyl carbonyl radicals, and softwood lignins showed only very weak guaiacyl
carbonyl signal. These radicals were thought to be produced by oxidative C-C cleavage in lignins. The signal
intensity was found to be due to the types of linkages of end-groups.
1995-107
DHP および β-O-4 型リグニンモデル化合物の熱分解生成物
黒田健一
256

筑波大学農林工学系
Comparative study of pyrolysis products of DHP and β-O-4 lignin model compounds
Kenichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
This paper describes the contributions of the β-O-4 substructure in lignin to the pyrograms oflignocellulosic materials. Two β-O-4 type lignin model compounds, guaiacylglycerol-β- guaiacyl ether (GGG)
and guaiacylglycerol-β-coniferyl ether (GGC), were pyrolyzed at 500 ºC for 4 s. The products were comparedwith those of a dehydrogenation polymer of coniferyl alcohol (DHP). The primary products of GGG wereguaiacylvinylketone and (E)-coniferyl alcohol, together with guaiacol released by the cleavage of the β-etherbond. 4-Methylguaiacol, 4-vinylguaiacol, ioseugenol and dihydroconiferyl alcohol, the major products of DHP,
were obtained in very small levels. GGC
produced dihydroconiferyl alcohol, coniferaldehyde and (E)-coniferyl alcohol in considerable levels.
Unlike GGG, GGC contributed to the formation of guaiacol, 4-methylguaiacol, 4-vinylguaiacol andioseugenol. The pyrolysis products from the model compounds suggest that coniferyl alcohol endgroups in lignin are related to the formation of dihydroconiferyl alcohol.
1995-108
クラフトパルプの亜硝酸処理における脱リグニン機構（3）—非フェノール性 β-5 型および β-O-4 型リグニンモ
デル化合物における Cα-Cβ 結合の閲裂—
岸野正典、大井 洋、山口 彰
筑波大学農林工学系
Mechanism of delignification during nitrous acid treatment of kraft pulp (III), Cleavage of Cα-Cβbond innonphenolicβ-5 type andβ-O-4 type lignin model compounds
Masanori Kishino, Hiroshi Ohi, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, The University of Tsukuba
Abstract:
The Cα-Cβcleavage has been reported as one of the main reactions during the nitrous acidtreatment of nonphenolic β-O-4 type lignin model compounds. The mechanism of Cα-Cβcleavage wasdiscussed using a nonphenolic β-5 type lignin model compound and nonphenolic β-O-4 type lignin modelcompounds in which deuterium was substituted for Cα-hydrogen. The Cα-Cβbond in coumaran ring of
dehydrodiisoeugenol methyl ether was cleaved giving veratraldehyde in a high yield. Thus, the cleavage of the
Cα-Cβbond in the nonphenolic β-5 type lignin model compound was one of the main reactions, and it was thesame as in nonphenolic β-O-4 type lignin model compounds. Veratrylglycerol-β-guaiacyl ether which had adeuterium at the Cαposition gave veratraldehyde having deuterium. The Abstraction of hydrogen was notobserved during the nitrous acid treatment.
1995-109
塩素漂白過程における酸化反応の役割
幸田圭一、新谷博幸、松本雄二、飯塚堯介
東京大学農学部
Role of oxidation reaction in the chlorine bleaching process
Keiichi Koda, Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agriculture and Agricultural Life Science, the University of Tokyo,
Abstract:
New calculation method was proposed for the evaluation of oxidation reaction and substitution
reaction during chlorine bleaching. New calculation method proved that more than half of the chlorine wasconsumed by oxidation reaction during chlorine bleaching. As an average, about 4 electrons were abstructedfrom one lignin structural unit. This result coincides with our former results that chlorinated lignin contains only
few aromatic structures. When oxidation reaction was depressed, delignification did not proceed effectively.
1995-110
ラジオトレーサー法によるクラフトパルプ化中のペクチンおよびキシランの挙動の解明
今井貴規*1、後藤任孝*1、松村浩如*1、安田征市*1、寺島典二*2*1名古屋大学農学部、*2USDA 林産物研究所
Behavior of pectin and xylan during kraft pulping studied by radiotracer technique
Takanori Imai*1, Hideyuki Goto*1, Hiroyuki Matsumura*1, Seiichi Yasuda*1, Noritsugu Terashima*2*1
Factilty of Agriculture, agoya University, *2United States Dept. of Agriculture, Forest Products Laboratory
257

Abstract:
Pectin and xylan were labeled with l4C and 3H respectively by administration of D-glucuronicl4
acid-[6- C] and myo-inositol-[2-3H] to a growing stem of magnolia. The doubly radio-labeled wood tissue wastreated under kraft cooking conditions, and radioactivities of pulps and cooking black liquors were determinedat various stages of cooking. The results showed that xylan was dissolved rapidly during heat-up stage, whereas
pectin could not be dissolved easily at the early stage of cooking. Readsorption of xylan on pulp wasdemonstrated at the late stage, whereas that of pectin was not observed.
1995-111
アバカ・ケナフの酵素処理
上垣勇吾、伊藤和貴、沖 妙、橘 燦郎
愛媛大学農学部
Enzyme treatment of non-woody fiber, abaca and kenaf
Yuugo Uegaki, Kazutaka Itoh, Tae Oki, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Treatment of the pulps prepared from non-woody plants, abaca and kenaf with twocommercially available pectinases containing CMC-ase, xylanase and β-glucosidase was conducted toinvestigate the effect of the pulp properties on the pectinase treatment. We found that parenchyma cells in thepulps were removed by the treatment with pectinases. We also found that physical properties, water retention
value and pulp strength were improved by the treatment with pectinases.
1995-112
フェノール酸化試薬によるリグニン酸化過程における分子状酸素の役割 —モデル実験—
森下智之、松本雄二、飯塚堯介
東京大学農学部
Model experiment on the role of molecular oxygen during oxidation reaction of lignin by phenol oxidizing
reagents
Tomoyuki Morishita, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agriculture and Agricultural Life Science, the University of Tokyo
Abstract:
When vanillyl alcohol (VA) was oxidized by laccase under pressurized oxygen (3 atm), reaction
products become more hydrophilic than those obtained by the oxidation under normal pressure. 1H-NMR
analysis suggested that oxidation products of VA by Mn(III) under pressurized oxygen had a different structuralfeature from those obtained under anaerobic condition. These results revealed that oxygen can be incorporated
in the reaction of phenolic compounds with one electron oxidizing reagents. When methyl-β-D-glucopyranoside(MGP) was subjected to Mn(III) oxidation together with homovanillic acid, no active species harmful to MGP
was produced.
1995-113
常圧酢酸パルプ化に関する研究 —β-O-4 型エーテル結合の反応性—
榎 牧子、佐野嘉拓
北海道大学農学部
Acetic acid pulping of wood at atmospheric pressure. —Reactivity of β-aryl ether linkages—
Makiko Enoki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
To explain the reaction mechanism of delignification by aqueous AcOH containing a small
amount of HCl or H2SO4 (acetolysis), guaiacylglycerol-β-guaiacyl ether (GOG) andveratrylglycerol-β-guaiacyl ether (VOG) were refluxed in 70-95% AcOH with HCl or H2SO4. β-Ethers byacetolysis were cleavaged much more readily by acetolysis than acidolysis. R-GOG and R-VOG withγ-CH3
were prepared from GOG and VOG by tosylation, iodination and finally reduction. R-GOG and R-VOG
produced guaiacol and corresponding aryl acetone as main products indicating that acetolysis for protolignin
modified terminal CH2OH groups in lignin to CH3 groups is a new degradation method for the investigation on
the chemical structure of lignin.
1995-特別講演
遺伝子の世界からみた生命の不思議 —つくば高血圧マウスとつくば低血圧マウスの創作—
村上和雄
258

筑波大学応用生物化学科
Invited Lecture: Tsukuba hypertensive mice and Tsukuba hypotensive mice
Kazuo Murakami
Institute of Applied Biochemistry, University of Tsukuba
Abstract:
We have constructed the chimeric renin-angiotensin cascade in mice comprising both humanrenin and human angiotensinogen as well as the endogenous angiotensin-converting enzyme and angiotensin II
receptor by crossmating separate lines of transgenic mice carrying either the human renin or humanangiotensinogen genes. Although each single gene carrier did not develop hypertension despite the observed
normal tissue specific expression of the transgenes, dual gene strains exhibited a chronically sustained increasein blood pressure (BP). The systolic BP was 130±7 mmHg. We named the hypertensive mice as “Tsukuba
Hypertensive Mice". On the other hand, we generated angiotensinogen-deficient mice by homologous
recombination in mouse embryonic stem cells. These mice do not produce angiotensinogen in the liver, resulting
in the complete loss of plasma immunoreactive angiotensin I. The systolic blood pressure of the homozygous
mutant mice was 66.9 ± 4.1 mmHg, significantly lower than that of wild-type mice (100.4±4.4 mmHg). We
named the hypotensive mice as "Tsukuba Hypotensive Mice".
1995-201
白色腐朽菌の産生するマンガンペルオキシダーゼの諸特性について
原園幸一、近藤隆一郎、坂井克己
九州大学農学部
Comparison of properties of manganese peroxidases from some white rot fungi
Koichi Harazono, Ryuichiro Rondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
Properties of partially purified manganese peroxidases (MnPs) from liquid cultures of white rot
fungi, the fungus YK- 505, Phanerochaete sordida YK- 624 and Phanerochaete chrysosporium were compared.
Properties of MnP from P. sordida YK-624 were similar to those of MnP from P. chrysosporium, while MnPfrom YK-505 had different properties from those produced by two other fungi. MnP from YK-505 adsorbed
onto a hardwood kraft pulp. MnPs from P. sovdida YK-624 and P. chrysosporium did not significantly adsorb
onto the pulp. MnP from YK-505 was superior to MnPs from P. sordida YK-624 and P. chrysosporium instabilities against high temperature and high concentration of H2O2.
1995-202
アルカリ性木粉培地に生育する微生物が生産するフェノールオキシダーゼについて
国沢直子、近藤隆一郎、坂井克己
九州大学農学部
Characterization of phenoloxidases from new isolates which can grow on alkaline wood meal media
Naoko Kunizawe, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We found several fungi producing extracellular phenol oxidases on alkaline wood meal media.
These crude phenol oxidases had optimal pH near neutral when guaiacol was used as a substrate. These
enzymes were produced well on alkaline wood meal media, but hardly on well-known laccase-inducing media.
Active fractions were obtained by ion-exchange chromatography, and the fractions revealed several bands ofactivity at pH 4.6 and 8 on non- denaturing PAGE, but culture filtrate of Coriolus versicolor revealed active
bands only at pH 4 and 6.
1995-203
カワラタケラッカーゼアイソザイムの解析
三国順子＊１、中村雅哉＊２、川合伸也＊１、片山義博＊３、諸星紀幸＊３＊１
東京農工大学農学部、＊２森林総合研究所、＊３東京農工大学生物システム応用科学科
Characterization of laccase isoenzymes from Coriolus versicolor
Junko Mikuni*1, Masaya Nakamura*2, Shinya Kawai*1, Yosbihiro Katayama*3, Noriyuki Morohoshi*3*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *2Forestry and Forest Products
Research Institute, *3Graduate School of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology
Abstract:
Our previous studies showed laccase III concerned in lignin biodegradation, and cleared the259

properties of this enzyme genetically and enzymatically. In order to define the inherent and physiolosical role oflaccase, we present to characterize the other laccase isoenzymes. As genetic characterization, we sequenced
another laccase gene and named CVLG1, previously. In this study, the origin of Laccasc III gene and CVLG1
were confirmed by Southern hybridization. Two Pst I DNA fragments were hybridized by probe a and b,
respectively. These four fragments were analyzed.
1995-204
土壌微生物 Pseumomonas paucimobilis SYK-6 のリグニン・ビフエニル特異的脱メチル化酵素遺伝子に関する研究
東 素夫*1、笠原健秀*２、小尾高広*２、片山義博*１、川合伸也*２、諸星紀幸*１*1
東京農工大学生物システム応用科学科、*２東京農工大学農学部
Analysis of the lignin-biphenyl specific demethylase gene from Pseudomonas paucimobilis SYK-6
Motoo Higashi, Takehide Kasahara, Takahiro Obi, Yoshihiro Katayama, Shinya Kawai, Noriyuki Morohoshi*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology
Abstract;
Pseudomonas paucimobilis SYK-6 is able to grow on DDVA and other various lignin dimericcompounds as a sole carbon source. To study of the specific reactions of lignin degradation by the
microorganism, we investigate the degradation of the biphenyl compound, DDVA, by P.
paucimobilis SYK-6. In our study, we analyzed the demethylation of DDVA, which is the first step of DDVA
degradation. We isolated a deficient mutant (NT-1) for DDVA demethylation, and the 6kbp-fragment from P.
paucimobilis SYK-6 chromosomal DNA, which complemented DDVA
demethylation for NT-1. Here we report characteristics of this 6kbp-fragment.
1995-205
土壌微生物 Pseumomonas paucimobilis SYK-6 のリグニン・ビフエニル特異的環開裂酵素遺伝子の構造と機能に関する研究片山義博*1、花城 薫*1、川合伸也*2、諸星紀幸*1、江頭 崇*3、彭 学、金原和秀*4、政井英司*3、 福田雅夫
*4、矢野圭司*4*1
東京農工大学大学院生物システム応用科学科、*2 東京農工大学農学部、*3 長岡技術科学大学、 *4 新技術
事業団
Cloning and characterization of the gene encoding novel ring cleavage enzyme for lignin biphenyl compuond in
Pseumomonas paucimobilis SYK-6
Yoshiriro Katayana, Kaoru Hanashiro, Sinya Kawai, Noriyuki Morohoshi*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology, *3Nagaoka University ofTechnology, *4Research Development Cooperation.
Abstract:
The soil bacterium, Pseumomonas paucimobilis SYK-6 is able to degrade various types ofdimeric lignin compounds such as biphenyl, -aryl ether, phenylcoumaran etc. Here, we reported molecularcloning of the gene encoding ring cleavage enzyme for lignin biphenyl. The 1.5 Kbp DNA fragment which
maintained the ring cleavage activity was identified by subcloning and sequencing. An open reading frame
encoding 334 amino acid was identified which designated lig Z. The lig Z gene was expressed in E. coli and thecharacterization of this enzyme was carried out. The enzymatic activity was observed only when OHDDVA(2.2'.3-trihydroxy-3'-methoxy-5,5'-dicarboxybiphenyl) was used as substrate but not for protocatechuate,
3-methylgallic acid and 2.3-dihydroxybiphenyl.
1995-206
α 位にカルボニル基を有する難分解性 β-O-4 型リグニンモデル化合物のマンガン及びシユウ酸による分解
近藤 登、服部武文、島田幹夫
京都大学木質科学研究所
A novel MnP-mimetic breakdown of recalcitrant nonphenolic lignin model compounds with two electron
pulling groups in the presence of Mn(III) and oxalate
Noboru Kondo, Takefumi Hattori, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Nonphenolic dimeric lignin model compounds with two electron-pulling groups such as
1-(4-ethoxy-3-methoxyphenyl)-2-(4-fomyl-2-methoxyphenoxy)-1-ethanone (I) was broken down with Mn(III)260

in the presence of oxalate and dimethyl sulfoxide (DMSO), yielding the Cα-Cβbond cleavage and Cβ-etherbond cleavage products such as 4-O-ethylvanillic acid (II) and vaniliin (III), respectively. ln this case, one atomof dioxygen has been demonstrated to be incorporated into the product (II). Almost no cleavage reaction
occurred in the control systems without either Mn(III),
oxalate or DMSO. Possible mechanisms for these unprecedent degradation of lignin models are discussed.
1995-207
担子菌由来リグニン分解酵素の有機溶媒中における反応
吉田晋一、渡辺隆司、本田与一、桑原正章
京都大学木質科学研究所
Reaction of ligninolytic enzymes from basidionycete in organic solvents
Shinichi Yoshida, Takashi Watanabe, Yoichi Honda, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Oxidation of aromatic compounds by lignin peroxidase (LiP) of Phanerochaete chrysosporium
was examined in organic solvents. LiP exhibited high activity of 3.3'-dimethoxy- benzidine oxidation in several
70% aqueous solutions of water-miscible solvents including ethylene glycol, diethylene glycol,
methylcellosolve, and acetone. LiP catalyzed the oxidation of several phenolics and aromatic amine including
3,3'-dimethoxybenzidine, catechol, o-phenylenediamine and o-aminophenol in 70% aqueous ethylene glycol
solution. UV/VIS absorption analysis suggested the formation of an intermediary charge-transfer complex in thereaction in water, whereas the presence of this complex was not shown in the 70% aqueous ethylene glycol
media. Electron spin resonance (ESR) analysis demonstrated that the reaction proceeded via the cation radical of
3,3'dimethoxybenzidine both in water and 70% aqueous ethylene glycol solution.
1995-208
リグニン生分解に関する研究（IV） —針葉樹および広葉樹クラフトパルプのバイオブリーチングにおけるマンガンペルオキシダーゼとリグニン分解の関係—
片桐誠之、江原克信、堤 祐司、西田友昭
静岡大学農学部
Studies on lignin biodegradation (IV), —The relationship between manganese peroxidase and delignification on
biobleaching or softwood and hardwood kraft pulp—
Nobuyuki Katagiri, Katsunobu Ehara, Yuji Tsutsumi, Tomoaki Nishida
Faculty or Agriculture. Shizuoka University
Abstract:
The reladonship between MnP and delignification on biobleaching or softwood (SWKP) andhardwood kraft pulp (HWKP) was investigated. The treatment of SWKP and HWKP with partially purified MnPsupports that MnP can bleach SWKP and HWKP, and lignin loss of SWKP and HWKP by MnP is nearly samelevel. ln the biobleaching of HWKP, there was a linear relationship between brightness increase (lignin loss) andcumulauve activity of MnP produced by Phanerochaete chrysosporium, Trametes versicolor and lZU-l54. In thebiobleaching of SWKP, though lignin loss was same level, cumulative activity or MnP produced by
Phanerochaete chrysosporium was much less than by IZU-154. These results suggest that other enzymes may
contribute to delignification of SWKP during treatment with P. chrysosporium.
1995-209
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（VII）—クラフトパルプのバイオブリーチングにおける白色腐朽菌の還元能の役割—
平井浩文、北濱 孝、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (VII), —The role of reducing abilities of white-rot fungi
during biological bleaching of kraft pulp—
Hirofumi Hirai, Takashi Kitahama, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We examined biological bleaching of unbleached hardwood kraft pulp (UKP) with
Phanenochaete sordida YK-624 and Phlebia sp. YK-63. P. sordida YK-624 secreted oxalate during thebiological bleaching of UKP under the condition of the initial culture pH 7.0, and then the culture pH was
dropped to about 5.0. After 2days incubation, the culture pH being dropped, the brightness increase of261

fungal-treated UKP and MnP producbon were observed. Phlebia sp. YK-663 could not bleach UKP at initial
culture pH 7.0, and neither the drop of pH nor MnP production were observed. Mn 2+ ion was detected in UKPs
which were brightened by each fungus although Phlebia sp. YK-663 could not reduce manganese dioxide
present in UKP under the initial culture pH 7.0. It is expected that the ability of droppinng culture pH and
MnO2-reducing ability are necessary to delignify residual lignin in UKP, and that these abilities were related to
the reducing ability detected with tetrazolium salts.
1995-210
MnSO4 無添加系でのマンガンペルオキシダーゼによるクラフトパルプの漂白
原園幸一、近藤隆一郎、坂井克己
九州大学農学部
Bleaching of kraft pulp with manganese peroxidase without addition of MnSO4
Koichi Harazono, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
In vitro bleaching of an unbleached hardwood kraft pulp was performed with partially purified
manganese peroxidase (MnP) from the fungus Phanerochaete soldida YK-624 without the addition of MnSO4
in the presence of some organic acids. When the pulp was treated without the addition of MnSO4, the pulp
brightness increased by about 10 points in the presence of 2 mM oxalate while the brightness did not
significantly increase in the presence of 50 mM malonate, a good Mn 3+ chelator. Cxalate reduced MnO2 which
had been existed in the pulp or produced from Mn2+ by the oxidation with MnP, and supplied Mn2+ to MnPsystem. It can be concluded that bleaching of hardwood kraft pulp with MnP by the effective use of manganeseoriginally present in the pulp was possible in the presence of oxalate, a good Mn 3+ chelator and MnO2-reducing
agent.
1995-211
PEG および PEG−PPG 系リグニン／糖ベースポリウレタンの熱分析
畠山兵衛*1、伊豆田良信*1、河崎将也 *1、中野準三*1、小橋川健 *2、照屋輝一*2、廣瀬重雄 *3、
畠山立
*3
子
*1
福井工業大学工学部、*2 トロピカルテクノセンター、*3 物質研究所
Thermal analysis of polyurethanes from PEG- and PEG-PPG-/lignin and saccharide systems
Hyoe Hatakeyama*1, Yoshinobu Izuta*1, Masaya Kawasaki*1, Junzo Nakano*1, Ken Kobashigawa*2,
Kiichi Teruya*2, Shigeo Hirose*3, Tatsuko Hatakeyama*3*1
Fukui Institute of Technology, *2Tropical Technology Center Ltd., *3 National lnstitute of Materials andChemical Research
Abstract:
Polyurethane (PU) foams were prepared by the following procedures. A 50 wt% solution ofkraft lignin (KL) in polyethylene glycol 200 (PEG, m.w. 200) was mixed with PEG 200, and then the obtained
solution was reacted with diphenylmethane diiisocyanate (MDI) in the presence of small amounts of water,
silicone surfactant and tin catalyst. PU foams were also prepared using a PEG- polypropylene grycoI (PPG)
copolymer instead of PEG 200 in the above process. Furthermore, PU's containing molasses (MOL) were also
prepared according to the above procedures. The thermal properties of PU’s were studied by differential
scanning calorimetry (DSC), thermogravimetry (TG) and TG-infrared spectrometry (FTIR). The influence of
the addition of KL and MOL to PU's on thermal properties were studied.
1995-212
リン酸化によるリグノセルロースのヒドロゲル化
斉藤直人*1、青山政和*1、清水祐一*2、高井光男*3、林 治助*3*1
北海道立林産試験場、*2 苫小牧工業高等専門学校、*3 北海道大学大学院工学研究科
Hydrogelation of lignocellulosic materials by phosphorylation
Naoto Saito*1, Masakazu Aoyama*1, Yuichi Shimizu*2, Mitsuo Takai*3, Jisuke Hayashi*3*1
Hokkaido Forest Products Reserach Institute, *2Tomkomai National College of Technology, *3Graduate Schoolof Hokkaido University
Abstract:
To investigate the swelling mechanisn with crystalline and fine structures, the chlorite-treatedwoodmeal and the ramie fiber were pretreated with hydrochloric acid or sodium hydroxide and by intensive
milling. The phosphorylated product obtained from the milled ramie showed the water absorbency 17 (g H2O/g).
The treatment with HCl or NaOH being followed by phosphorylation decreased the water absorbency of the262

product prepared from the woodmeal. The phosphorylated product was identical with Cellulose I regarding the
crystalline structure. Consequently, the phosphorylation occurs on the finer structure unit such as microfibril.
The stronger hydrogen bond between microfibrils of the ramie decreases the water absorbency of the product.
1995-213
ベンジル化木材の単独発泡における含有 LCC の効果
平岡俊治*1、上田昌見*1、高見秦博*1、越島哲夫*2*1
日本化学機械製造株式会社，*2 近畿大学農学部
Effects of lignin-carbohydrate complexes on foaming of benzylated wood without adding plasticizers
Toshiharu Hiraoka*1, Masami Ueda*1, Yasuhiro Takami*1, Tetsuo Koshijima*2*1
Japan Chemical Engineering & Machinary Co. Ltd., *2Faculty of Agriculture, Kinki University
Abstract:
Researches have been done aiming to make a degradable foam from benzylated wood. As aresult we have found that it is possible to produce a expandable benzylated wood without adding any ofplasticizers or other polymers and also it is necessary for the benzylated wood to retain more than 70% of the
LCC in the original wood in order to accomplish ten to twenty times foaming. There was direct proportional
relationship between the foaming extents and LCC contents of the resin up to nine-teen times of foaming extent.
What kinds of effects of lignin have been brought on physical properties of the final products also have been
investigated.
1995-P01
モノリグノールグルコシドの樹幹内分布と季節変動
田口小百合、福島和彦、安田征市
名古屋大学農学部
Distribution and seasonal changes of monolignol gucosides in Magnolia kobus
Sayuri Taguchi, Kazuhiko Fukushima and Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
Monolignol glucosides (MLG), coniferin (CF) and syringin (SY), existed in the xylem and thebark of Magnolia kobus in different season were determined quantitatively. The proportion of SY in the bark
were much higher compared with that in the xylem. The concentration of CF was a higher value in lignifying
season. But even in a resting stage, SY content in the bark was very high. In lignifying season, MLG in the outerbark was almost syringin, on the contrary, in the cambial zone and differentiating xylem was almost coniferin. It
seems that CF existing in the xylem is related to the lignification of stem. But there is no relationship between
SY content and lignification of xylem in magnolia shoot.
1995-P02
芳香環 3 位あるいは 5 位に水酸基を導入したモノリグノールクルコシドのコブシ樹幹内での挙動
松井直之*1、福島和彦*1、安田征市*1、寺島典二*2*1名古屋大学農学部、*2USDA 林産物研究所
Bahavior of monolignol glucoside derivatives which contains hydroxyl group on aromatic ring 3- or 5-positionin magnolia shootNaoyuki Matsui*1, Kazuhiko Fukushima*1, Seiiti Yasuda*1, Noritsugu Terashima*2*1
Factilty of Agriculture, agoya University, *1United States Dept. of Agriculture, Forest Products Laboratory,
U.S.A.
Abstract:
The feeding of hydroxylated monolignol glucoside to magnolia shoot revealed that thesederivatives can be used as precursors of coniferin and syringin, and the structural conversion proceeds mostly tothe direction of the increase of methoxyl groups. The mechanism of the conversion seems to need a temporary
removal of glucose residue, in spite of our previous result [1]. By the further study using variously labeledconiferin, it became clear the conversion from coniferin to syringin is achieved at the stage of monolignols, nottheir glucoside.
1995-P03
交雑ヤマナラシ キタカミハクヨウから単離した OMT 遺伝子の解析
早川敏雄*1、吉澤たまか*1、川合伸也*1
高塚慎司*2、片山義博*2、諸星紀幸*2*1
東京農工大農、*2 東京農工大生物システム応用科学研究科
263

Analysis of genes for OMT that were isolated from a hybrid aspen, Populus kitakamiensis
Tosihio Hayakawa*1, Tamaka Yoshizawa*1, Shinya Kawa*1i, Shinji Takatsuka*2, Yoshihiro Katayama*2, Noriyuki
Morohoshi*2*1
Fuculty of Agriculture, Tokyo University or Agriculture and Technology, *2Graduate school of BASE, Tokyo
University or Agriculture and Technology
Abstract:
O-methyl transferase (OMT) plays a important role in monolignol biosynthesis. Genomic
Southern blot analysis suggested that the genes for OMT formed small gene family in Populus kitakamiensis..
We have isolated two genes, homt1 and homt3, from genome of P. kitakamiensis.. Two OMT isoenzymes havebeen isolated from stems or P. kitakamiensis. They differed from one another in substrate specificity. It is
important to clarify the relationship between the genes and isoenzymes. We attempted to express the genes in E.
coli cells and P. kitakamiensis. On the other hand, antisense gene for OMT was introduced into tobacco and thetransformants were regenerated into plants.
1995-P04
ゴマ (Sesamum indicum) のフロフラン型リグナンの生合成
片山健至、池西康晴
香川大学農学部
Biosynthesis of furofuran lignans in sesame (Sesamum indicum)
Takeshi Katayama, Yasuharu lkenishi
Faculty of Agriculture, Kagawa University
Abstract:
Sesame seeds contain furofuran lignans such as (+)-sesamin and (+)-pinoresinoI,
which are widely distributed in higher plants. To investigate biosynthesis of the furofuran lignans in sesame(Sesamum indicum), [8-14C]coniferyl alcohol was fed to excised stems of sesame and [8-14C]coniferyl alcohol
was incubated with insoluble residue from stems and capsules, upon removal of soluble enzymes, in the absenceof cofactor and in the presence of NAD-malate or aqueous Kl. Fllowing [8-14C]coniferyl alcohol administration
to excised shoots for 3 hr, radio-labeled pinoresinol was formed more in stems than in leaves. The (+)/(-) ratio
was 42-46 : 58-54. Radio-activities for sesamin and sesamolin were the same as background level. Enzymatic[8,8'-14C]pinoresinol formation with the insoluble residue was found in each incubation condition. The additionof NAD-malate enhanced the pinoresinol formation.
1995-P05
カラスザンショウ（Zanthoxylnum ailanthoides)のリグナンの生合成と立体化学
正岡 武、片山健至
香川大学農学部
Lignans biosynthesis and stereochemistry of Zanthoxylum ailanthoides
Takeshi Kasaoka, Takeshi Katayama
Faculty of Agriculture, Kagawa University
Abstract:
Adninistration of [8-14C]coniferyl alcohol to an excised shoot of Zanthoxylum ailanthoides
resulted in a conversion of pinoresinol (almost racemic), (-)-lariciresinol (71%ee), and (+)-secoisolariciresinol(56%ee). (±)-[8,8'-14C]pinoresinols was incubated for 1 hr with cell-free extracts from Z. ailanthoides in thepresence of NADPH. Both [8,8'-14C]lariciresinol and [8,8'-14C] secoisolariciresinol were detected as (+)-forms.
Time-course experiments (5, 20min, 1 hr) using the cell-free extracts [10-80% (NH4)2SO4, precipitate under
the same condition as above showed formations of lariciresinol and secoisolariciresinol were linear over thetime period, corresponding a linear depletion of pinoresinol.
1995-P06
反芻家畜の消化作用により可溶化したイネ科牧草リグニンの特性
渡辺隆司*1、近藤恒夫*2、大下友子*2、久馬 忠*2、本田与一*1、桑原正章*1*1
京都大学木質科学研究所、*2 東北農業試験所
Structural characteristics of soluble lignin fractions released by digestion in ruminant animal from forage
grasses
Takashi Watanabe*1, Tsuneo Kondo* ２ , Tomoko Ohshita* ２ , Tadashi Kyuma* ２ , Yoichi Honda*1, Masaaki
Kuwahara*1
Wood Research Institute, Kyoto University, *2Tohoku National Agricultural Experiment Station
Abstract:
Faecal soluble lignin (FSL), extracted from the faeces of sheep that received orchard grass and264

timothy, were compared with 90% dioxane-soluble lignins released by ball milling (MHL) and by subsequent
enzymatic hydrolysis (EHL) from the same grasses. FSL contained much less carbohydrate and esterified
p-coumaric and ferulic acids than MHL and EHL. Molecular weight of FSL was much smaller than those of
MHL and EHL. The molar ratio of syringaldehyde to vanillin produced by nitrobenzene-oxidation was higher
for FSL than for MHL and EHL. Results indicated that syringyl-rich lignin fragements with less phenolic acid
esters were released by digestion in sheep from the forage grasses.
1995-P07
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（VIII）—Phanerochaete sordida YK-624 株によるベラトリルアルコールの生産について—
平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (VIII), — Production of veratryl alcohol by Phanerochaete
sordida YK-624 —Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Dept. of Forest Products, Kyushu University
Abstract:
To clarify the production of veratryl alcohol (VA) by Phanerochaete sordida YK-624 under thenutrient-rich conditions, where the reduction of tetrazolium salts was induced and no lignin peroxidase activity
was detected, the pathway for VA biosynthesis was examined by the addition of cinnamic acid (Cacid) as the
precursor of VA to potato-dextrose media. (pH 7.0). Cacid was transformed to cinnamaldehyde (Cald), cinnamyl
alcohol (CA), benzaldehyde (Bald), and benzyl aJcohol (BA) by P. sordida YK-624, and no benzoate was
detected. It was suggested that the pathway for VA biosynthesis in P. sordida YK-624 differed from the pathway
proposed by Jensen et al. Phlebia sp. YK-663. which showed lower tetrazolium salts-reducing activity than P.
sordida YK-624 and hardly produced VA under ligninolytic or nutrient-rich conditions, transformed Cacid to
Cald and CA, but Bald and BA were hardly detected.
1995-P08
リグノスチルベン-α,β-ジオキシゲナーゼアイソザイム I およぴ III のキメラ酵素の基質特異性（II）
鴨田重裕、佐分義正
東京大学農学部
Substrate specificities of chimera enzymes of lignostilbene-α.β-dioxygenase isozyme I and III, (II)Shigehiro Kamoda, Yoshimasa Saburi
Faculty of Agriculttlre, the University of Tokyo
Abstract:
Pseudomonas paucimobilis TMY1009 produced at least four lignostilbene-α,β- dioxygenase(LSD) isozymes. LSD-I and -III were composed of two homogeneous α and β subunits, respectively. LSD-I
degraded 4, 2'-dihydroxy-3, 3’-dimethoxy-5-(2"-carboxyyinyl) stilbene (β-5 stilbene) very slowly. It seemed to
be specific for 4, 4'-dihydroxy-3, 3'-dimethoxystilbene (β-1 stilbene). The other hand, LSD-III degraded β-5
stilbene better than β-1 stilbene. The gene of LSD-I (lsd A) and -III (lsd B) were cloned and sequenced. These
two isozymes share 69% amino acid sequence identity, yet differ markedly with respect to their substratespecificities. Chimeric LSD consisting of either the N-terminal fragment ofαsubunit fused with the C-terminal
fragment of β subunit or the inverse pair. Chimera α158 βincludes the 158 N-terminal residues of αsubunit fusedto the complementary part of the βsubunit sequence. Chimera βl58α,β356α and α407βwere designed in the sameway. Analyses on Km and specific activities for two stilbenes indicated that chimera α158βand βl58αhave thesame substrate specificities as LSD-III (β subunit) and LSD-I (αsubunit), respectively. As concerns β356α and
α407β, no activity was detected. Further investigation is required.
1995-P09
種々の培養条件下における白色腐朽菌 Phanerochaete chrysosporium のフエニルアラニンアンモニアリアー
ゼ（PAL）活性
服部武文、島田幹夫
京都大学木質科学研究所
The detection of PAL activity in Phanerochaete chrysosporium grown in the four different cultures
Takefumi Hattori, Mikio Shimada
Wood Research Institute. Kyoto University
Abstract:
The activities of L-phenylalanine ammonia-lyase extracted from Phanerochaete chrysosporium
265which had been grown in the four different cultures (HC-LN, HC-HN, LC-MN, and LC-HN) were assayed. The
PAL activity and the concentration of veratryl alcohol in the culture fluid were greater in HC-LN culture than in
HC-HN culture. Furthermore. the PAL activities were detected in both of LC-MN and LC-HN cultures during ashort period after the mycelial growth reached the peak. However, in HC-LN culture, PAL activity was detected
before the mycelial growth peaked and maintained for another 6 days at higher level.
1995-P10
PEG に結合させたリグニンモデル化合物の白色腐朽菌及びその酵素による分解
河合真吾*1、Ken Jensen*2, Wuli Bao*2，Ken Hammel*2*1
岐阜大学農学部、*2USDA 林産物研究所
Fungal and enzymic oxidation of PEG-linked lignin model compound
Shingo Kawai*1, Kenneth A. Jensen*2, Jr., Wuli Bao*2, Kenneth E. Hammel*2*1
Facufty of Agriculture, Gifu University, *2USDA Forest Products Laboratory
Abstract:
We prepared a lignin model in which β-O-4 dimers were covalently attached to 8000
MW polyethylene glycol (PEG). The PEG-linked model was mineralized extensively in liquid medium and insolid wood cultures of the white-rot fungus Phanerochaete chrysosporium. GPC showed that P. chrysosporium
degraded the PEG-linked model by cleaving its lignin dimer substructure rather than its PEG moiety.
Cα-Cβcleavage was the major fate of the PEG-linked model after incubation with P. chrysosporium and also
after oxidation with its lignin peroxidase. The brown-rot fungus Gloeophyllum trabeum was unable to degrade
the PEG-linked model efficiently.
1995-P11
白色腐朽菌カワラタケのシュウ酸合成酵素の部分精製
三井香代子、服部武文、島田幹夫
京都大学木質科学研究所
Partial purification of glyoxylate oxidase from the white-rot basidiomycete Coriolus versicolor
Kayoko Mii, Takefumi Hattori, Mikio Shimada
Wood Research lnstitute, Kyoto University
Abstract:
The glyoxylate oxidase which catalyses oxidation of glyoxylate to form oxalate was partiallypurified from the homogenate of a white-rot basidiomycete Coriolus versicolor .The g!yoxylate oxidase waspurified by combination of (NH4)2SO4 precipitation. DEAE-Biogel A chromatography and Sephadex G-l50 gel
filtration. Three isozymes were detected by DEAE-Biogel A chromatography.
1995-P12
白色腐朽菌 Phanerochaete chrysosporium の核酸要求性変異株の単離とその相補遺伝子の取得
中村雅哉、西田篤実、高野麻理子
森林総合研究所
Isolation of uracil auxotrophic mutants from Phanerochaete chrysosporium
Masaya Nakamura, Atsumi Nishuda, Mariko Takano
Forestry and Forest Products Reserach Institute
Abstract:
Uracil auxotrophic mutants of the white-rot fungus Phanerochaete chrysosporium using a
positive screening procedure with 5-fluoro orotic acid. Mutants deficient for the orotidin-5'- phosphate
decarboxylase (pyr 4 mutants) and for the orotate phosphoribosyl transferase (pyr 2 mutants) have beencharacterized by enzyme assays. The pyr 4 gene was screened from a P. chrysosporium genomic library using
the Aspegillus nidulans pyr 4 gene as a probe. The pyr 2 gene was amplifyed from P. chrysosporium genomic
DNA by PCR using the pyr 2 specific primers.
1995-P13
クラフト蒸解条件の酸素酸化漂白への影響 —蒸解条件による酸素酸化したパルプ中残留リグニンの構造変化
陳 嘉義、清水祐一、高井光男、林 治助
北海道大学大学院工学研究科
Effect of kraft cooking conditions on effciency of oxygen delignification, -The structure characteristics ofresidual lignin in the oxygen delignified pulp
J.-Y. Chen, Yuichi Shimizu, Mitsuo Takai, Jisuke Hayashi
266

Graduate School or Engineering, Hokkaido University
1995-P14
リグニンスルホン酸添加バクテリアセルロース製造における菌株、炭素源の選択
恩地真一、大谷慶人、鮫鳥一彦
高知大学農学部
Selection of strain of Acetobacter xylinum and carbon source in cultuer medium with lignosulufonate for
production of bacterial cellulose.
Shinichi Onji, Yoshito Ohotani, Kazuhiko Sameshima
Faculty of Agriculture, Kochi Univercity
Abstract:
We have found that the cellulose yields of seven different strains of Acetobactor xylinum
increased by the addition of lignoslufonate from sulfite pulping waste 2% glucose medium. In this study, we
studied whether cellulose yield of each strain could be increased or not with different carbon source with orwithout lignosulfonte. We used Fructose, Glyserol, Saccharose, Xlose and Lactic acid as carbon source. The
results indicated that cellulose yields of each strain of A. xylinum are not always increased by the use of different
carbon source. The selections of strain and carbon source are very important to secure the cellulose yield.
1995-P15
熱分解ガスクロマトグラフィーによる広葉樹型リグニンの分析（III）—クラフト蒸解およびパルプ漂白による熱分解物の変化—和泉明子、田中潤治、大井 洋、黒田健一、山口 彰
筑波大学農林工学系
Analysis of hardwood lignin by pyrolysis-gas chromatography (III), — Changes of pyrolysis products by kraft
cooking and pulp bleaching —Akiko Izumi, Junji Tanaka, Hiroshi Ohi, Ken-ichi Kuroda, Akira Yamaguchi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Several Japanese hardwood kraft pulps were analyzed by pyrolysis combined with gas
chromatography (Py-GC). The major pyrolysis products were guaiacol, 4-methylguaiacol, 4-vinylguiaicol,
trans-isoeugenol, coniferylaldehyde, syringol, 4-methylsyringol, 4-vinylsyringol,trans-4-propenylsyrjngol, sinapaldehyde. The ratios of syringyl-derived pyrolysis products to guaiacyl-derived
pyrolysis products were decreased by kraft cooking. The yields of pyrolysis products from lignin in chlorinatedkraft pulp were small, and the chlorinated-derived pyrolysis products were rarely detected.
1995-P16
ケナフ靭皮部の酸素パルプ化敖日格勒、佐野嘉拓
北海道大学農学部
Oxygen pulping of kenaf bast
Aorigele, Yoshihiro Sano
Faculty of Agriculture , Hokkaido University
Abstract:
Oxygen pulping of kenaf bast was carried out with 10%-20% NaOH of o.d. bast at 110 ºC and 7kg/cm2 of' O2 pressure for 60-120 min. Products were separated into pulp-1 (long fiber pulp), pulp-2 (screenedpulp), fines (epidermis part) and a reaction liquor. After boiling with 50-70% AcOH, pulp-1 was further
delignified and yielded the bast pulp. Satisfactory bast pulps with much greater delignification and physicalproperties were obtained in yields of 48%-56% when bast was subjected to oxygen pulping with 15% NaOH for
60-120 min, followed by boiling in aqueous AcOH. The reaction liquor was separated into three main fractions
according to the fractional precipitate procedure and so on in order to analyze chemical properties and utilize as
raw materials for biomass conversion.
1995-P17
酢酸リグニンを原料とする炭素繊維の調製（5）—針葉樹酢酸リグニンの炭素繊維化—
久保智史、石川直哉、浦木康光、佐野嘉拓
北海道大学農学部
Preparation of carbon fiber from acetic acid lignin (V), — Preparation of carbon fiber from softwood acetin acidlignin —267

Satoshi Kubo, Naoya Ishikawa, Yasumitu Uraki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Preparation of lignin fiber as precursors for carbon fibers from softwood acetic
acid lignin (NAL) was obtained from todomatu wood ( Abies sacahlininsis) by aqueous AcOH pulping with
0.1% HCl at atmospheric pressure. NAL was infusible, though birch acetic acid lignin (BAL) was readilyfusible without any chemical modification. However, F-2 which was precipitated from waste liquor by 70%
aqueous AcOH and was obtained in a yield of 81% based on NAL, had fusibility and spinnability. Preparation oflignin fiber was achieved without thermal treatment, though thefiber had a rough surface and mechanical properties inferior to those for BAL fibers. F-2 was possible toundergo direct carbonization without thermal stabilization. Carbon fibers prepared from the lignin fibers of F-2
had worse mechanical properties compared with those for BAL fibers. The charactization of F-2 lignin fibers
and carbon fibers seemed to be improved by addition of plasticizer for F-2 to have a lower fusible temperaturefor our handmade spinning apparatus.
1995-P18
Flavan-3,4-carbonate の開環重合による高重合度縮合型タンニンの合成とその機能
米田 聡、河本晴雄、中坪文明
京都大学農学部
Synthesis of high-molecular-weight condensed tannin by cationic ring-opening polymerization offlavan-3,4-carbonate and their function
Satoshi Yoneda, Haruo Kawamoto, Fumiaki Nakatsubo
Faculty of Agriculture, Kyoto University
Abstract:
In order to obtain high-molecular-weight condensed tannin, we synthesized newly
flavan-3,4-carbonate and tried its cationic ring-opening polymerization with BF3-Et2O in CH2Cl2
at 0 ºC. The molecular-weight of polymers increased with an increase of reaction time, and the number-average
degrees of polymerization (DPn) reached 47 after 264h. The protein-precipitating capacity was found toincrease with an increase in the molecular weight of condensed tannin.

268

第 41 回 （1996.10.3-4） 名古屋大学農学部
1996-101
樹木の細胞壁リグニン生合成過程の免疫組織学的研究
増野洋子*1、早川敏雄*1、船田 良*2、川合伸也*3、諸星紀幸*1、片山義博*1*1
東京農工大学大学院 BASE, *2 北海道大大学農学部、 *3 東京農工大学農学部
Immunohistochemistry of biosynthesis of lignin in woody plants
Yoko Mashino*1, Toshio Hayakawa*1, Ryo Funada*2, Shinya Kawai*2, Noriyuki Morohoshi*1, Yoshihiro
Katayama*1*1
Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *1Hokkaido University, *3Tokyo University of Agriculture and Technology
Abstract:
As protoxylem and mataxylern of angiosperms maturate and develop, the elements withmore extensive secondary thickenings than that represented by a helix deposit the secondary wall in two stages.
First, a helical framework is built (first-order secondary wall). Then, additional secondary wall material is laid
down as sheets or strands or both between the gyres of the helix (second-order secondary wall). In this study, we
report the intergrading of tracheary elements using by immno- histochemistry. We prepared antiserum for
irnmunohistochemical analysis. Antiserums were raised against PAL, OMT, CAD, 4CL, and POX. The peptide
in the expression vector pQE (QUIAGEN, Chatsworth, CA, USA) was expressed in E. coli cells. The ability of
the antiserum to react with crude and purified protein from P. kitakamiensis was tested by Western
immunoblotting. PAL OMT, CAD, 4CL and POX were localized specifically in cells of xylem, but not observedin parenchyma.
1996-102
樹木の桂皮酸 4-水酸化酵素遺伝子の発現様式の解析
塩川貴広*1、片山義博*1、諸星紀幸*1、川合伸也*2*1
東京農工大学大学院 BASE, *2 東京農工大学農学部
Expression analysis of a cinnamic acid 4-hydroxylase gene from a hybrid aspen, Populus kitakamiensis
Takahiro Shiokawa*1, Yoshihiro Katayama*1, Noriyuki Morohoshi*1, Shinya Kawoai*2,*1Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Tokyo University of Agriculture and Technology
Abstract:
In higher plants, Cinnamic acid 4-hydroxylose (CA4H) is the second enzyme involved inphenylpropanoid biosynthesis and is a member of cytochrome P-450 superfamily. Three CA4H genes, -cyp73a,
cyp73b, Cnd cyp73c-, and a cDNA clone of cyp73a were isolated from a genomic library and a cDNA library ofa hybrid aspen; Populus kitakamiensis, ctnd were characterized. They might be interrupted by two introns,
respectively. cyp73a and cyp73b were very similar each other not only in coding regions but also in non-coding
regions. Southern blot analysis showed that four homologous genes for CA4H constructed a small gene family
in the diploid genome of P. kitakamiensis. In the promoter regions, there were many common cis-element-likesequences in phenylpropanoid biosynthesis genes. Here, we win report a tissue-specific expression manner of anaspen CA4H gene in transgeneic tobacco plants. We made a cyp73a promoter-GUS gene fused constract. It was
introduced to tobacco and aspen cells. The GUS activity in transgenic tobacco plants with the cyp73a
promoter-GUS fusion gene was mainly detected in the vasculor bundles and was strongly induced in a
non-tisssue-specific manner by wounding.
1996-103
樹木細胞壁形成におけるリグニンと糖代謝遺伝子の特徴
真壁和彦*1、西窪伸之*1、川合伸也*2、諸星紀幸*1、片山義博*1*1
東京農工大学大学院 BASE, *2 東京農工大学農学部
Characteristics of genes related to lignin and sugar metabolism in plant cell wall formation
Kazuhiko Makabe*1, Nobuyuki Nishikubo*1, Shinya Kawai*2, Noriyuki Morohoshi*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Tokyo University of Agriculture and Technology
Abstract:
Lignin biosynthesis and carbohydrate chain biosynthesis are closely related to cell wall
formation of plant. We constructed the cDNA library from the one year old stem of Populus kitakamiensis,
which showed active cell wall thickness and lignification. We isolated the cDNA fragments of Sucrose synthase,
UGPase and DAHP synthase from the cDNA library. Sucrose synthase and UGPase are related to sugar
269

metabolism, and DAHP synthase is related to shikimic
acid pathway and lignin biosynthesis. The nucleotide sequences and the deduced amino acid sequences of their
DNA fragments showed that sucrose synthase and UGase of P. kitakamiensis are similar to other higher plant.
1996-104
シナピルアルコールを用いた広葉樹細胞壁木化過程シミュレーション
伊藤岐仁、重松幹二、棚橋光彦
岐阜大学農学部
Modeling of hardwood lignification using sinapyl alcohol
Michihito Itoh, Mikiji Shigematsu, Mitsuhiko Tanahashi
Faculty of Agriculture, Gifu University
Abstract:
To be clear biosynthetic process and chemical structure of hardwood lignin, the effect ofhydrophobicity of reaction media on dehydrogenative polymerization (DHP) of sinapyl alcohol was studied byusing a horseradish peroxidase. First, to inhibit polymerization of sinapyl alcohol in wateraround the enzyme, the hydrophilic site of horseradish peroxidase was converted to be hydrophobic bymodifying with methoxypolyethlene glycol succinimidyl succinate. Sinapyl alcohol was polymerized by themodified enzyme, and the products were analyzed by 1H-NMR. Second, considering the lignification model thatsinapyl alcohol is polymerized by β-O-4 linkage to syringaresinol formed previously, syringaresinol was used as
starting radical at DHP process of sinapyl alcohol. Third, to examine the effect of hydrophobic media,
polymerization of sinapyl alcohol in polysaccharide solution or hydrophobic solvents was investigated by
1
H-NMR. Further, structure of polymerized products of Cβ-labeled sinapyl alcohol (HO-C6H2(OCH3)2-CH=C✶
H-CH2OH) was analyzed by 13C-CP/MAS.
1996-105
広葉樹の CAD 形質転換体における異常リグニンの化学的構造について
伊藤 隆*1、河合真吾*1、大橋英堆*1、樋口隆昌*2*1
岐阜大学農学部, *2 京都大学名誉教授
Chemical study on abnormal hardwood lignin with antisense cinnamyl alcohol dehydrogenase (CAD) geneTakashi Ito*1, Shingo Kawai*1, Hideo Ohashi*1, Takayoshi Higuchi*2*1
The United Graduate School of Agriculture Science, Gifu University, *2Professor emeritus of Kyoto University
Abstract:
Various DHPs derived from mixtures or coniferyl aldehyde and sinapaldehyde with coniferyland sinapyl alcohol were prepared for the model of the transgenic hardwood lignin. Fr-IR and UV analysis of
the DHP showed that sinapaldehyde and sinapyl alcohol were effectively incorporated into these DHPs.
However, GC-MS analyses of the thioacidolysis products of the DHPs showed that coniferyl aldehyde wassignificantly incorporated into the DHPs and end group via β-O-4 linkages, and the incorporation ofsinapaldehyde into the DHPs as end group was very small. Therefore, the thioacidolysis products ofsinapaldehyde were analyzed by GC-MS. The chromatogram gave a small peak of the extended product withrelatively large amount of two new components derived from sinapaldehyde.
1996-106
カラスザンシヨウにおけるリグナン生合成
片山健至、正岡 武、杉本博之、瀧井忠人、大柿 篤
香川大学農学部
Biosynthesis of lignans in Zanthoxylum ailanthoides
Takeshi Katayama, Takeshi Masaoka, Hiroyuki Sugimoto, Tadato Takii, Atsushi Ogaki
Faculty of Agriculture, Kagawa University
Abstract:
Interestingly Zanthoxylum ailanthoides have (8S,8'S)-furofran lignans such as (-)-pinoresinoland (8R,8'R)-(-)-secoisolariciresinol. It was suggested that insoluble residue from Z. ailanthoides catalyzed
enentioselective (-)-pinoresinol formation from coniferyl alcohol. Incubation of cell-free extracts from the plants
with (±)-pinoresinols in the presence of NAD(P)H resulted in the enantiospecific formation of (+)-lariciresinol,
whose configuration was identical with that of natural (-)-secoisolariciresinol. Following administration of[8-14C]coniferyl alcohol the radioactivities were incorporated in pinoresinol, lariciresinol andsecoisolariciresinol with their (8S,8'S) enantiomer preferred. Following administration of [8,8'-14C] pinoresinol,
the formation of radioactive lariciresinol and secoisolariciresinol was found again, although they were almost
racemic. These facts suggested the presence of both biosynthetic pathways to (8S,8'S) and (8R,8'R) lignans in270the plant.
1996-107
トチュウのリグナン・ネオリグナンの生合成と立体化学
片山健至、加登優樹、大柿 篤
香川大学農学部
Biosynthesis and stereochemistry of lignans and neolignans in Eucommia ulmoides
Takeshi Katayama, Yuki Kado, Atsushi Ogaki
Faculty of Agriculture, Kagawa University
Abstract:
Eucommia ulmoides contains diverse lignans and neolignans. To investjgate their biosynthesis,[8-14C]coniferyl alcohol was fed to excised young shoots, and it was incubated with cell-free extracts of theplant in the presence of H2O2 and with insoluble residue in the absence of cofactors. (+)-Pinoresinol formation
was found in preference to the (-)-form in the feeding experiment. Erythro-isomer was more than the threo one
in guaiacylglycerol- -coniferyl ether obtained both in the feeding experiment and in the assay using theinsoluble
residue.
(-)-Dehydrodiconiferylarcoholandoptically
activeerythroandthreo-guaiacylglycerol- -coniferyl ethers were formed in the assay using cell-free extracts in spite of their low
enantiomeric excess (9-14%).
1996-108
Wikstroemia sikokiana から単離されたリグナンとその生合成経路について
奥西智哉、梅澤俊明、島田幹夫
京都大学木質科学研究所
A possible biosynthetic pathway of lignans in Wikstroemia sikokiana
Tomoya Okunishi, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:[9,9-2H2OC2H3]Coniferyl alcohol, [9,9,9’,9’-2H4]pinoresinol, [9,9,9’,9’-2H4]lariciresinol and2[9,9,9’,9’- H4]]secoisolariciresinol were administered to Wikstroemia sikokiana, and incorporation of deuterium
atoms into several lignans were observed. Based on the result, a possible biosynthetic pathway of lignans in W.
sikokiana was proposed.
1996-109
Eucalyptus camaldulensis および E. globulus 各 2 個体の樹幹内変異を用いたリグニンの S／G 比とリグニン含有率の関係について
小名俊博、園田哲也、伊藤一弥、伊藤昌樹
王子製紙株式会社森林資源研究所
Relationship between lignin content and lignin S/G ratio in the same trunk sought by their within-tree variations
in Eucalyptus camaldulensis and E. globules
Toshihiro Ona, Tetsuya Sonoda, Kazuya Ito, Masaki Ito
Kameyama Research Center, Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
The relationship between extractives-free (EF) lignin content and lignin monomericcomposition as syringyl/guaiacyl (S/G) ratio by thioacidolysis was examined. This was performed in the same
trunk by their within-tree variations, which mean the investigation with the same genes, in
Eucalyptus camaldulensis and E. globules.. As results, each species had a high negative correlation between
EF-lignin content and lignin S/G ratio although the difference between species and/or individuals was observedin the trend of within-tree variations of the wood properties. The relationship between EF-lignin content andlignin S/G ratio is considered to be caused from the difference in the fiber morphology from the relationshipbetween lignin and EF-basic density which may relate to the fiber morphology.
1996-110
5-Hydroxyguaiacyl nuclei in native lignin
Kenji Iiyama*1, Satoshi Suzuki*2, Thi Bach Tuyet Lam*3*1
Asian Natural Environmental Science Center, the University of Tokyo, *2Graduate School of Agriculture andLife Science, the University of Tokyo, *3School of Biochemistry, La Trobe University
1996-111271

多糖類存在下におけるリグニンモデル物質の反応
大森茂俊*1、青山政和*2、榊原 彰*3*1
College of Environmental Science and Forestry, State University of New York, *2 北海道立林産試験場、*3 北
海道大学名誉教授
Reaction of lignin model compounds in the presence of polysaccharides
Shigetoshi Omori*1.Masakazu Aoyama*2, Akira Sakakibara*3*1
College of Environmental Science and Forestry, State University of New York, *2Hokkajdo Forest Products
Research Institute, *3Professor emeritus, Hokkaido University
Abstract:
The lignin model compounds of β-O-4 type were treated in dioxane and water (1:1) mixture at
l80ºC for 20 min with and without spruce holocellulose. A model, guaiacylglycerol-βguaiacyl ether (1) gave β-l (8), β-5 (9), β-β(10) dilignols and a trilignol (11) which are the products of recoupledradicals from homolysis of the model (1). However, when treated in the presence of holocellulose, these dimericand trimeric compounds could not be detected. The results indicate that the polysaccharides act as hydrogen
donor to stabilize the formed radicals before their coupling. The same results were also recognized in the case ofotherβ-O-4 model compounds.
1996-112
分析的熱分析によるリグニンの分析 —熱分解生成物の起源構造について—
和泉明子、黒田健一
筑波大学農林工学系
Analytical pyrolysis of lignin : origins of pyrolysis products
Akiko Izumi, Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Lignin model compounds, β-β and β-5 types, were pyrolyzed in the presence oftetramethylammonium hydroxide (TMAH) to obtain information on the lignin structure. Pinoresinol andsyringaresinol yielded full methylated products as main products. The full methylated product (M + 400) of
dehydrodiconiferyl alcohol was not observed. However, dehydrodiconiferyl alcohol showed the formation of
three methylated products, which were isomers from their mass fragment patterns (M + 370). These methylated
dimer products were also observed in the pyrolysis of hardwood type dehydrogenative polymers.
1996-113
熱分解-メチル化によるリグニンの分析：β-O-4 型構造由来の熱分解生成物
黒田健一
筑波大学農林工学系
Pyrolysis-gas chromatography analysis of lignin in the presence of tetra-methylammoniurn hydroxide: β-O-4
substructure-derived pyrolysis products
Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
To obtain pyrolysis fragments with information on the lignin structure, a dehydrogenation
polymer of coniferyl alcohol was pyrolyzed in the presence of tetramethylammonium hydroxide (TMAH) at
500 ºC for 4 s. A series of methylated products were swept on a gas chromatograph column. The products, suchas (3,4-dimethoxyphenyl) methoxyethylenes and 1-(3,4-dimethoxy- phenyl)-1,2,3-trimethoxypropanes, derived
from the β-O-4 building blocks were observed in the pyrolyzate. TMAH/pyrolysis of Japanese cedar andJapanese Douglas fir woods also produced these products. The sources of some products were explained on thebasis of the TMAH/pyrolysis results of β-O-4 type lignin model compounds. Abundances of the β-O-4 building
blocks in lignin were compared among the woods and several isolated lignins using the peak intensities of
1-(3,4- dimethoxyphenyl)-1,2,3-trimethoxypropanes. Results showed that TMAH/pyrolysis offers muchinformation on the β-O-4 1ignin building blocks than conventional pyrolysis without TMAH.
1996-114
リグニンの β-O-4 構造の化学反応牲（2）—ルイス酸触媒アセトリシスによるリグニンの β-O-4 構造の定量—
小幡雅子、中坪文明
京都大学農学部
Chemical reactivity of β-O-4 substructures in lignins, -Quantitative analysis of β-O-4 structures in lignins by
Lewis acid catalyzed acetolysis (LCA) 272

Masako Obata, Fumiaki Nakatsubo
Faculty of Agriculture, Kyoto University
Abstract:
In our recent investigation, Lewis acid catalyzed acetolysis (LCA) reaction has been shown to
be a suitable degradation method for the analysis of β-O-4 substructures in lignins, for its characteristic
reactivity and the simple experimental procedure. Here, we describe the synthesis of Hibbert's ketones in order
to identify the degradation products, and discuss some structural aspects of Eucalyptus globules MWL from its
LCA reaction products.
1996-115
機械パルプの光褪色におよぼすフェノール牲水酸基の影響
足立幸雄、伊藤和貴、坪田弘志、沖 妙、橘 燦郎
愛媛大学農学部
Effect of phenolic hydroxyl groups in mechanical pulps on depression of color reversion of mechanical pulps
Yukio Adachi, Kazutaka Itoh, Hiroshi Tsubota, Tae Oki, Sano Tachibana
Faculty of Agriculture, Ehime University
Abstract:
In order to investigate the effect of phenolic hydroxyl groups in mechanical pulps on depression
or light-induced color reversion of mechanical pulp, two types or mechanical pulp
(thermomechanical pulp : TMP, groundwood pulp : GP) were acetylated, and examined to what extent the color
reversion of the pulps was prevented by the acetylation. When about 11% of the phenolic hydroxy groups inunbleached GP and unbleached TMP were acetylated, the color reversion or the pulps were also completely
depressed. On the other hand, when about 16% and 29% of the phenolic hydroxy groups in bleached GP andbleached TMP, respectively, were acetylated, the color reversion of the pulps were completely depressed. On thebasis of these results, the phenolic hydroxyl groups in mechanical pulps seem to contribute mainly to thedepression of the color reversion of mechanical pulps.
1996-116
バクテリアセルロース製造培地における緩衝液成分およびリグニンスルホン酸の役割
島本 明、Siripong Premjet．大谷慶人、鮫島一彦
高知大学農学部
Role of buffer components and lignosulfonate in the superior medium for bacterial cellulose production
Akira Shimamoto, Siripong Premjet, Yoshito Ohtani, Kazuhiko Sameshima
Faculty of Agriculture, Kochi University
Abstract:
We have already reported bacterial cellulose membrane yield is greatly increased by theaddition of lignosulfonate to a standard cultivation medium. In this report we examined the relationship between
concentration of buffer, yield of cellulose membrane and final pH of media to clarify the role of buffer
components and lignosulfonate in the superior bacterial cellulose production medium. The results showed thatthe final pH values of media with lignosulfonate were slightly higher than those media without lignosulfonate
but the cellulose yield increases were greater. Only citric acid was probed to be the effective component for thesuperior cellulose production system with lignosulfonate.
1996-特別講演
樹木系フェノールポリマーとエコテクノロジー
阿部 勲
三重大学生物資源学部
Woody phenolpolymers and ecotechnology
Isao Abe
Faculty of Bioresources, Mie University
Abstract:
The investigations on woody phenolpolymers, namely wood lignin and some barkproanthocyanidins (condensed tannins) I participated were summarized, and the forest ecotechnology
concerning the specific species, which contained highly of condensed tannins in bark, was discussed.
1996-201
オイルパーム・フロンド爆砕パルプからのボードの調製と爆砕パルプ中のリグニンの性状
鈴木 聡*1、新谷博幸*1、朴 承栄*1、Nikhom Laemsak*1、大熊幹章*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
273

Preparation of binderless boards from steam exploded pulp of oil palm frond and structural characteristic oflignin in steam exploded pulp
Satoshi Suzuki*1, Hiroyuki Shintani*1, Seung-Young Park*1, Nikhom Laemsak*1, Motoaki Okuma*1, Kenji
Iiyama*2*1
Graduate School of Agricultural and Life Science, the University of Tokyo, *2Asian Natural Environmental
Science Center, the University of Tokyo
Abstract:
The binderless boards were prepared from steam exploded (2.0-3.0MPa, 5-10min) pulps of oilpalm frond. The strength of these boards met the requirements of the boards of JIS. To clarify the mechanism of
the bonding of the binderless boards, oil palm frond, pulp and board were analyzed by the chemical andspectrometical methods and pyrolysis-gas chromatography mass spectrometry. Björkman lignin from oil palm
frond, and this lignin was characterized by the presence of significant amount of esterified p-hydroxybenzoic
acid. Most ester bonds and β-O-4 bonds were cleaved during steam explosion process, and the other hand,
guaiacyl units were condensed greatly, as revealed by 1H and 13C-NMR spectra, Moreover, the structuraldifference of the aromatic units between 2.5MPa and 3.0MPa exploded pulp, were observed in 1H, 13C-NMR
and FTIR spectra. The ratios of syringyl derivatives to guaiacyl derivatives (S/G) from total ion pyrograms weredecreased by hot pressing. As a result of the analytical pyrolysis, 5-hydroxymethylfurfural, derived from
cellulose, was increased by the steam explosion especially 3.0MPa. Significant amount of furfural, derived from
pentosan, was detected in the pulp steam exploded under the condition of 2.5MPa, and furfural was increased
during hot pressing. These facts suggest that furfural is involved in the formation of binder together with lignin.
1996-202
蒸解黒液中のリグニンの性状に関する研究
岩瀬幸彦，種田英孝，井上敏雄
日本製紙株式会社
Studies on lignin in the kraft black liquor
Yukihiko Iwase, Hidetaka Taneda, Toshio Inoue
Nippon Paper Industries Co., Ltd.
Abstract:
We analyzed a black liquor to establish a method to determine a pulp yield. When the black
liquor was acidified to separate lignin and other wood components, it was observed that kraft cooking withanthraquinone (AQ) increased the rate of precipitated lignin to the total lignin in the black liquor.
Determinations of functional groups of precipitated lignin, "kraft lignin", and acid- soluble lignin, indicated that
AQ did not give a significant influence to a character of kraft lignin, but did much to one of acid-soluble lignin.
It would be suggested that AQ decreased the acid-solubility of lignin by preventing formation oflignin-carbohydrates-complex (LCC) containing carboxylic acids derived from carbohydrates degradation
compounds.
1996-203
酸素−アルカリ漂白過程における多糖類の分解機構（6）—過酸化物の安定性と炭水化物分解の関連について—横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Degradation mechanisms of carbohydrate during oxygen-aIkali bleaching (VI), — Relationships between
peroxide stability and carbohydra te degradation —Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
A cellulose model compound, methyl β-D-glucopyranoside (MGP), was treated with an alkalinehydrogen peroxide solution in the presence or absence of metal ions, such as iron, manganese and magnesium,and the effect of these metal ions on the degradation of MGP was examined. The results showed that the amountof degraded MGP at a certain consumption of hydrogen peroxide was strongly dependent on the metal ions. The
addition of iron did not cause more MGP degradation than the case of no metal addition, and the less MGP
degradation was observed when more magnesium was added together with iron. Contrarily, the addition ofmanganese caused only a little degradation of MGP though the rate of hydrogen peroxide degradation was very
high, and the addition of magnesium together with manganese had no positive effect on the protection of MGP.
The sole addition of magnesium had some positive effect on the protection of MGP but the complete protectionof MGP was not obtained.
274

1996-204
リグニンおよび兼モデル化合物とオゾンとの直接の反応によるヒドロキシラジカルの生成
スウェーデン王立工科大学
Martin Ragnar*1, Tord Eriksson*1, Torbjörn Reitberger*2
Formation of hydroxyl radicals from direct ozone reactions with lignin and carbohydrate model compounds —A
kinetic study
Martin Ragnar*1, Tord Eriksson*1, Torbjörn Reitberger*2*1
Department of Pulp and Paper Chemistry and Technology, Royal Institute of Technology, *2Department ofChemistry, Royal Institute of Technology, Sweden
Abstract:
オゾンがリグニンモデル化合物と反応する際には、二重結合を酸化的に解裂する通常のイ
オン的な酸化反応のほかに、一電子的にフェノールを酸化してフエノキシラジカルを生成する
ラジカル的な反応が考えられる。その時に生じるオゾンの還元生成物は酸素とヒドロキシラジカルに分解するので、オゾン漂白中の多糖類分解の原因となることを明らかにした。このラジカル的な酸化反応の反応速度は、反応の相手方であるフェノールの酸化電位と直線的な相関を示す。反応 pH が高いと反応速度は急激に増大する。
1996-205
化学パルプの高収率化と無塩素漂白に関する研究、亜硝酸処理におけるリグニンの反応
大井 洋*1、轟 英治*1、具 延*1、岸野正典*1*2*1
筑波大学農林工学系、*2 北海道立林産試験場
Pretreatment for chemical pulping and non-chlorine bleaching reactions of lignin during nitrous acid treatment
Hiroshi Ohi, Eiji Todoroki, Yan Ju, Masanori Kishino
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Nitrous acid treatment of kraft pulp has been proposed as a non-chlorine bleaching method.
This treatment is also expected to be effective as a pretreatment for kraft pulping to increase the pulp yields.
Behaviors of lignin degradation during the nitrous acid treatment were studied using beech wood meals andnonphenolic β-O-4 type lignin model compounds. The delignification during kraft pulping was accelerated by
the pretreatment. By the nitrous acid treatment, veratrylglycerol-β-syringyl ether (VS) and α-ethyl ether of VS(VSE) were distinctly degraded through cleavage of their Cα-Cβbonds giving veratraldehyde in a 51 and 47
mol% yields, respectively. Both erythro and threo of the lignin models were treated with nitric acid solution in
the absence and presence of nitrite, and the degradation behaviors were discussed.
1996-206
白色腐朽菌によるポリエチレンの生分解（I）
飯吉由佳、堤 祐司、西田友昭
静岡大学農学部
Polyethylene biodegradation by white rot fungi
Yuka Iiyoshi, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
Polyethylene (PE) biodegradation by white rot fungi, IZU-154, Phanerochaete chrysosporium,
and Trametes versocolor, was investigated. PE was effectively biodegraded under the nutritional nitrogenand/or carbon-limited culture condition, and IZU-154 showed the most significant PE biodeqadation among
three white rot fungi. The addition of manganese sulfate into nitrogen- and/or carbon-limited medium enhanced
the PE biodegradability of white rot fungi. These results suggest that manganese peroxidase (MnP) plays asignificant role in the PE biodegaradation by white rot fungi, and in vitro PE biodegradation by isolated MnPsupports this hypothesis.
1996-207
リグニン生分解に関する研究（VII) 〜バイオブリーチングにおける針葉樹クラフトパルプ残留リグニンの構
造変化〜
片桐誠之、堤 祐司、西田友昭
静岡大学農学部
Studies on lignin biodegradation (VI), Changes in the residual lignin framework in softwood kraft pulp duringbiobleaching by Phanerochaete chrysosporium and manganese peroxidase275

Nobuyuki Katagiri, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agrictllture, Shizuoka University
Abstract:
Softwood kraft pulp (SWKP) was treated with Phanerochaete chrysosporium or with its
manganese peroxidase (MnP) under both conditions of which Mn(II) was added or not, and the residual lignin
frameworks were compared among these treated pulps by the chemical analysis(nitrobenzene oxidation, acidolysis and permanganate oxidation). In the treatment of SWKP by P.
chrysosporium without Mn(II) addition, the residual lignin was degraded and selective decrease ofarylglycerol-β-aryl ether unit was observed. On the other hand, the treatment of SWKP with partially purified
MnP without Mn(II) addition revealed that MnP can not degrade the residual lignin because of lack ofmanganese in SWKP. These results suggested that enzyme(s) other than MnP may contribute to delignificationof SWKP by P. chrysosporium under manganese-insufficient condition.
1996-208
白色腐朽菌のリグニン分解に関与する酵素系に関する研究 (X) 〜Phanerochaete sordida YK−624 株の産生する NAD(P)H 依存性 Fe(III)還元酵素について〜
平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (X), NAD(P)H-dependent ferrireductase produced by
Phanerochaete sordida YK-624
Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu university
Abstract:
We have previously reported NAD(P)H-dependent reduction of manganese dioxide mediated byferrous chelate in white-rot fungus Phanerochaete sordida YK-624. In the present study, we tried to isolate
ferrireductase which would involve in the reduction or manganese dioxide by P. sordida YK-624. Ferrireductase
activity was detected in cell-free extract, and most of the ferrireductase was precipitated by the addition of
30-65% ammonium sulfate saturation. The ferrireductase was purified to homogeneity by hydrophobic, gelfiltration, and Mono Q chromatography. This enzyme was monomer protein, and pI and molecular weight were
5.1 and 35 kDa, respectively. Optimal pH for the reduction of ferric chelate by this enzyme was about 7.0. This
reductase was dependent on NADPH although cellobiose could not act as electron donor. In the kinetic analysts,
this enzyme showed higher substrate specificity for ferric chelate than Mn(III) and lignin model compounds.
1996-209
Ganoderma sp．YK505 株の産生するマンガンペルオキシターゼの諸特性とクラフトパルプ漂白牲
原園幸一、近藤隆一郎、坂井克己
九州大学農学部
Bleaching of kraft pulp with manganese peroxidase secreted from Ganoderma sp. YK-505 and properties of the
enzymeKoichi Harazono, Ryuichiro Rondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We performed in vitro bleaching of an unbleached hardwood kraft pulp (UKP) with manganeseperoxidase (MnP) from the white rot fungus Ganoderma sp. YK-505 or Phanerochaete sordida YK-624. MnPfrom Ganoderma sp. YK-505 could brighten UKP at higher temperature and concentration of H2O2 than with
MnP from P. sordida YK-624. Two MnP isoenzymes were purified from shaken culture of Ganoderma sp.
YK-505. The molecular masses of both isoenzymes were about 43 kDa. Maximum activities of both isoenzymes
were exhibited at 55ºC. Both isoenzymes had higher resistance to H2O2 and different pH dependency fromother MnPs, e.g. MnP from Phanerochaete chrysosporium and P. sordida, and maintained activities at high pH(6-8.5).
1996-210
アルカリ耐性担子菌 Phellinus sp．IS-847 株が産生するフェノールオキシダーゼについて
国澤直子、近藤隆一郎、坂井克己
九州大学農学部
Characterization of phenoloxidases from anti-alkaline basidiomycete Phellinus sp. IS-847
Naoko Kunizawa , Ryuichiro Rondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
276

Abstract:
Anti-alkaline basidiomycete Phellinus sp. IS-847 isolated from nature grew in an alkaline woodmill + buffer medium (pH 8) very well, and secreted exracellular phenol oxidases, which contained two
isoenzymes. The main isoenzyme (PhO I) was isolated and purified by using hydrophobic, gel filtration andanion exchange chromatography. This isoenzyme had molecular mass of about 60 kDa and isoelectric point of
about 6.3. The optimal pH was 6.0 when guaiacol was used as a substrate. The substrate specificities and theeffect of inhibitors were similar to the behavior of known laccases. The minor isoenzyme (PhO II) had
molecular mass of about 63 kDa and pI 4.8, and showed high activity in an alkaline region than PhO I did.
1996-211
木材腐朽菌 IO−427 株による難分解牲 β-O-4 型リグニンモデル化合物のエーテル結合開裂について
瀧下 寛、平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Cleavage of ether linkage in recalcitrant β-O-4 lignin model compound by wood-rot fungus IO-427
Hiroshi Takishita, Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agricu)ture, Kyushu University
Abstract:
The β-ether linkage is the most abundant in chemical structure of lignin, therefore, it
seems that the cleavage of this linkage is the most important process in the lignin biodegradation. From thisviewpoint, we tried to isolate fungi which can release fluorescent 4-methylumbelliferone by the cleavage of the
β-ether bond in Substrate I, which is recalcitrant β-O-4 type lignin model compound,
3-hydroxy-2-(4-methylumbelliferyl)-1-phenyl-l-propanone. By this screening method, we selected awood-rotting fungus lO-427. In the present study, we tried to determine the metabolites from Substrate I in order
to examine cleavage process of β-ether linkage. After 24 hour-incubation, Substrate l decreased by 23%, and
20% of 4-methylumbelliferone was produced. Two kinds of C6-C3 compounds were found, and they wereidentified as 2.3-dihydroxy-1-phenyl- 1-propanone, and 3-hydroxy-1-phenyl-1-propanone. These compounds
and 4-methylumbelliferone weren’t detected in the culture of Phanerochaete chrysosporium although decreaseof Substrate I was observed. It was expected that lO-427 might possess different function of the cleavage of
β-O-4 linkage from other white-rot fungi.
1996-212
木材腐朽菌による LCC の分解について (VI) DSC 分析によるリグニン—糖マトリツクスの変化の検出
辻山彰一
京都府立大学農学部
Degradation of lignin-carbohydrate complex by wood-rotting fungi (VI), Detection of changes oflignin-carbohydrate matrix by differential scanning calorimeter (DSC)
Sho-ichi Tsujiyama
Faculty of Agriculture, Kyoto Prefectural University
Abstract:
Differential scanning calorimetric (DSC) analysis was applied to the akamatsu LCC(Lignin-Carbohydrate Complex) degraded by wood-rotting fungi, a brown-rot fungus Tyromyces palustris and awhite-rot fungus Coriolus versicolor. Original LCC indicates two exothermal peaks at 440-470ºC and one
shoulder at 330ºC. Comparing with the component materials prepared fromakamatsu wood, the peak determined at 440-470ºC is considered to be due to the lignin- carbohydrate matrix.
DSC analysis of degraded LCC indicated that T. palustris degraded only the
carbohydrate portion in lignin-carbohydrate matrix and that C. versicolor decomposed the lignin
portion to form the fragments with less lignin amount.
1996-213
針葉樹の常圧プロピレングリコールパルプ化
佐野嘉拓、村田裕之、浦木康光
北海道大学農学部
Pulping of softwoods by propylene glycol system at atmospheric pressure
Yoshihiro Sano, Hiroyuki Murata, Yasumitsu Uraki
Faculty or Agriculture, Hokkaido University
Abstract:
Organosolv pulping of softwoods was investigated in polyhydric alcohols containing mineralacids at atmospheric pressure. The propylene glycol (PG) pulping with sulfuric acid gave satisfactory pulps withlittle rejects and the very low content of residual lignin, which were readily bleached. Mechanical properties of277

the pulps were comparable to those of KP. The bleached pulp has considerably high glucose and α-cellulose
contents, and high crystallinity that was further increased by simple chemical treatment. Therefore, the pulps aresuggested to be utilized as not only paper but also dissolved pulp and highly crystalline cellulose. The pulping
solvent is supplied from hydrolyzed hemicellulose, and the waste liquor including hemicellulose after removalof PG lignin can be re-used as the solvent. This suggests to reduce the cost of the pulping. Consequently, the PG
pulping is considered an alternative process to conventional chemical pulping.
1996-211
ササ稈の触媒添加蒸煮処理
津田真由美*1、関 一人*1、青山政和*1、Nam-Seok CHO*2*1
北海道立林産試験場、*2 韓国忠北大学
Acid-catalyzed steaming treatment of bamboo grass, Sasa senanensis Rehd
Mayumi Tsuda*1, Kazuto Seki*1, Masakazu Aoyama*1, Nam-Seok Cho*2*1
Hokkaido Forest Products Reserch Institute, *2Chungbuk National University, Republic of Korea
Abstract:
The effect of acid catalysts in the steaming treatment on solubilization of bamboo grass xylan
was investigated. Among catalysts used, FeCl3 and CaCl2 were efficient in solubilization of
xylo-oligosaccharides at a level of 10 mmole/kg substrate and below. When the substrate was steamed in thepresence of these catalysts at 191ºC for 10 min, xylo-oligosaccharides were obtained in a yield of 8-9% basedon the raw material. The enzymatic digestibility of residual fiber was also determined. The catalysts were foundto be effective on enhancement of the susceptibility to cellulase. Water extract of steamed bamboo grass showed
inhibitory activity to the angiotensin I -converting enzyme (ACE). The lC50 value was 0.06 mg/ml.
1996-215
水蒸気圧縮処理による樹液抽出法の開発
鈴木悦子*1*2、棚橋光彦*1、重松幹二*1*1
岐阜大学農学部、*2 ウッディテックコーポレーシヨン
Development of sap extraction method associated with the compressive molding process
Etsuko Suzuki*1*2, Mitsuhiko Tanahashi*1, Mikiji Shigematsu*1*1Faculty of Agriculture, Gifu University, *2Woody Tech Corporation, Japan
Abstract:
For the utilization method of forest resources, there is a gathering of sap for the particularpurpose excepting the use of wood itself for building materials, pulp and paper. The purpose of this study was adevelopment of sap extraction method associated with the compressive molding process of Cryptomeria
japonica D.Don. and Camaecypariss obutusa Endl. for effective utilization of wood. In analysis of wood sap
squeezed from Cryptomeria japonica during compressive molding process of raw wood with steam treatment,
four compounds were isolated from the chloroform extraction and idendfied by 1H-NMR and MS. These
compounds were coniferyl alcohol, D,L-pinoresinol, lariciresinol and dihydrodehydrodiconiferyl alcohol. On
the other hand, judging from the fact that two compounds, D,L-pinoresinol and dihydrodehydrodiconiferyl
alcohol, were isolated from the hydrolyzed water layer, high amount of lignan-glycosides was contained inoriginal sap.
From the Camaecyparis obutusa wood sap, hinokinin was isolated from the chloroform extraction and idendfied
by NMR and MS.
1996-216
リグニンを原料とするポリウレタンの熱的及び粘弾性的特性
広瀬重雄*1、伊豆田良信*2、畠山兵衛*2*1
物質研究所、*2 福井工業大学工学部
Thermal and viscoelastic properties of polyurethanes from lignin
Shigeo Hirose*1, Yoshinobu lzuta*2, Hyoe Hatakeyama*2*1
National Institute of Materials and Chemical Research, *2Fukui Institute of Technology
Abstract:
Polyurethane (PU) sheets were prepared from alcohol-solvolysis lignin (AL) and kraft lignin(KL) by the following procedures. Lignin and polyethylene glycol having a molecular weight of 400 (PEG 400)
were dissolved in tetrahydrofuran (THF). Diphenyrmethane diisocyanale (MDI) was added to the above
solution and the reaction was continued at room temperature until a prepolymer solution was obtained. The
prepolymer solution was cast on a glass plale which was placed in a desiccator. After the removal of THF, theobtained prepolymer sheet was cured at 120 ºC for24 hr. The thermal and viscoelastic properties of PU's werestudied by thermogravimetry (TG), differential scanning calorimetry (DSC). and dynamic thermomechanometry
278

(DMA). Thermal degradation temperatures (Td’s) slightly decreased with increasing lignin contents in PU's.
Glass transition temperatures increased with increasing lignin contents in PU's. A large peak was observed in atan curve at the temperature region where E' showed a sudden decrease. It is considered that this peak can be
attributed to the main chain motion of PU’s.
1996-P01
熱分解ガスクロマトグラフィーによる南洋材リグニンの分析
大井 洋、安田有紀野、和泉明子、黒田健一
筑波大学農林工学系
Analysis of lignin in tropical hardwoods by pyrolysis-gas chromatography
Hiroshi Ohi, Yukino Yasuta, Akiko Izumi, Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, the Uhiversity of Tsukuba
Abstract:
Ratios of syringyl units to guaiacyl units (S/G ratios) of lignin in tropical hardwoods were
estimated by pyrolysis-gas chromatography (Py-GC). The wood meals were extracted with benzene andsuccessively with 70% acetone/ water to remove tannins and other phenols. The observed S/G ratios were ingood agreement with syringaldehyde/vanilin (S/V) ratios obtained by nitrobenzene oxidation. Furthermore, theextracted kapur wood meals were treated with hot 1 % NaOH solution to extract lignin-like substances in a
tropical wood. Both syringyl and guaiacyl pyrolysis products were obtained from a chloroform soluble part ofthe 1 % NaOH extractives. In order to simplify a method for determination of acid-insoluble (Klason) lignin intropical hardwoods, wood samples were hydrolyzed at 121ºC, and the acid-insoluble residue was characterized
by Py-GC.
1996-P02
シリンギル基又はグアイアシル基を持った化合物の酸化によって生成するフリーラジカル
鬼木隆幸、高浜有明夫
九州歯科大学一般教育部
Free radicals produced by oxidations of compounds containing syringyl or guaiacyl groups
Takayuki Oniki, Umeo Takahama
Kyushu Dental College
Abstract:
Electron spin resonance spectra of free radicals produced by oxidations of compounds
containing syringyl or guaiacyl group were measured at pH 13.0. Syringaldehyde or 2,6-dimethoxy-phydroquinone showed an ESR signal of 2,6-dimethoxy-p-benzo-semiquinone radical by the oxidation with
H2O2. This radical was also produced by the oxidation of dioxane lignins with hexacyanoferrate (III) or H2O2.
Vanillin or methoxy-p-hydroquinone showed an ESR signal due to methoxy-p-benzosemiquinone radical by theoxidation with H2O2. A radical produced by the oxidation of methoxy-p-hydroquinone with O2 orhexacyanoferrate (III) was also observed when dioxane lignin was oxidized with O2 or hexacyanoferrate (III).
Two kinds of radicals which were observed in the oxidation of dioxane lignins were identified to be due tosyringyl and guaiacyl groups in the lignins.
1996-P03
フエノキシラジカルと酸素との反応牲
杉元倫子、森下智之、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Reactivity of phenoxyl radical with molecular oxygen
Tomoko Sugimoto, Tomoyuki Morishita, Yuji Matsumoto and Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
The possibility of the reaction between phenoxyl radical and molecular oxygen was
examined. Vanillyl alcohol (VA) or syringyl alcohol (SA) was treated with a one electron oxidizing reagent,
manganese (III), and the effect of oxygen pressure on the yield of methanol from these phenols was determined.
Methanol can be released when the radical produced at the carbon to which a methoxyl group is attachedcombines either with phenoxyl radical or with molecular oxygen. Although methanol was produced from areaction under nitrogen pressure (oxygen 0 MPa), the increased yield of methanol under increased oxygenpressure was thought to indicate the reaction between phenoxyl radical and molecular oxygen.
1996-P04279

酸素−アルカリ漂白過程における多糖類の分解機構（7）—リグニンの酸素酸化反応の速度論的特徴—
松本雄二、横山朝哉、飯塚堯介
東京大学大学院農学生命科学研究科
Degradation mechanism of carbohydrate during oxygen-alkali bleaching( VII), Kinetic behavior of lignin duringoxygen oxidation in aqueous alkali solution
Yuji Matsumoto, Tomoya Yokoyama, Gyosuke Meshitsuka
Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, the University ofTokyo
Abstract:
Isolated kraft lignin was treated with oxygen-alkali and the extent of oxygen oxidation was
evaluated on the basis of the consumption of permanganate by the kraft lignin before and after
the oxygen oxidation. One unit of kraft lignin (200 g) was found to be oxidized by 8.5 mole electron duringoxygen-alkali treatment. Kinetic analysis showed that the process of oxygen oxidation can mainly be divided
into two first order reactions. An acceleration of oxidation during the reaction, which was observed when model
phenols were treated by oxygen-alkali, was not observed.
1996-P05
Thuya 属のリグナン生合成について
杉下千洋、河合真吾、大橋英雄
岐阜大学農学部
Lignan biosynthesis of Thuja species
Kazuhiro Sugishita, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
In addition to the previously found 2-(3,5-dimethoxy-4-hydroxybenzyl)-3-(3,4methylendioxy-benzyl)-butyrolactone (4-O-demethylyatein), three lignans, secoisolariciresinol, matairesinoland dihydrodehydrodiconiferyl alcohol as minor components were confirmed in young shoots and leaves ofThuja occidentalis. Next, to investigate biosynthesis of lignans in Thuja species. [9,9-2H2,O2H3]coniferyl
alcohol was fed to excised young shoots of T. occidentalis and T. plicata.
Following metabolism for 24 hr, deuterated pinoresinol, lariciresinol and dihydrodehydrodiconiferyl alcohol
were formed in T. occidentalis young shoots. Cell-fee extracts from T. occidentalis leaves catalyzed theformation or deuterated pinoresinol, when incubated with [9,9-2H2,O2H3]coniferyl alcohol in the presence of
NADPH and H2O2.
1996-P06
植物培養細胞によるフェノール頬のグルコシル化の試み
村中俊夫、伊藤和貴、沖 妙、橘 燦郎
愛媛大学農学部
Trial for glucosylation of phenols by plant cell cultures
Toshio Muranaka, Kazutaka ltoh, Tae Oki, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Production of phenolic glucosides from three phenols, salicyl alcohol, coniferyl alcohol andconiferyl aldehyde by cell suspension cultures of Coffea arabica was tried. From the results of HPLC analysis
of each reaction product, we found that salicin, phenolic glucoside of salicyl alcohol was produced in the
maximum yield of 17.5% by the cultures of C. arabica. However, the glucosides from the two other phenols
could not be produced by the cultures of C. arabica.
1996-P07
カワラタケラッカーゼ遺伝子の解析
三国順子*1、中村雅哉*2、西田篤実*2、川合伸也*1、片山義博*3、諸星紀幸*3*1
東京農工大学農学部、*2 森林総合研究所、*3 東京農工大学大学院 BASE
Analysis of laccase genes from Coriolus versicolor
Junko Mikuni*1, Masaya Nakamura*2, Atsumi Nishida*2, Shinya Kawai*1, Yoshihiro Katayama*3, Noriyuki
Morohoshi*3*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, *1Forestry and Forest Products
Reseach Institute, *3Graduate school of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology.
Abstract:
Eight chromosomal DNA bands of Coriolus versicolor have been resolved by pulsed-field gel
280electrophoretic analysis. The estimated sizes of the chromosomal DNAs ranged from 5.6 to 2.5 megabase pairs.
Previously, we cloned and sequenced Laccase III gene (CVL3) and other laccase gene(CVLG1) of C. versicolor.
The membrane, which was transferred the separated chromosomal DNAs of C. versicolor, was hybridized withgene specific probes of CVL3 and CVLG1. It is cleared that CVL3 and CVLG1 were different chromosomal
DNAs.
1996-P08
担子菌 Coriolus versicolor（カワラタケ）のフェノールオキシダーゼ遺伝子のクローニング
飯村洋介、辰巳憲司
資源環境技術総合研究所
Cloning and sequencing of a phenoloxidase gene from the basidiomycete Coriolus versicolor
Yosuke Iimura, Kenji Tatsumi
National Institute for Resources and Environment
Abstract:
The gene (cvmnp) encoding a manganese peroxidase from Coriolus versicolor IFO 30340, alignin-degrading basidiomycete, was cloned and sequenced, and the corresponding cvmnp, cDNA was also
cloned and sequenced. The isolated gene consist of 1,397 bp, with the coding sequence being interrupted by 5
introns and flanked by an upstream region in which putative TATA and inverted CCAAT consensus sequences
could be identified at positions -81 and -162, respectively. A potential metal responce element (MRE),
xenobiotic responce element (XRE), and nitrogen regulatory consensus sequence (NIT) are recognized in the
upstream region of the gene. The mature translation product, preceed by a 26-residue signal peptide, should
consist of 339 residues.
1996-P09
白色腐朽菌 Pleurotus ostreatus のフルトラニル耐性変異株におけるコハク酸デヒドロゲナーゼ Ip サブユニット
遺伝子の解析
松山拓郎、入江俊一、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
Analysis of the genes encoding succinate dehydrogenase lp subunit from flutolanil-resistant mutant Pleurotus
ostreatus strains
Takuro Matsuyama, Toshikazu Irie, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
For development of an useful vecter system in basidiomycetes, it is desired to develop adominant genetic marker which requires no genetic background of the host strains. We have obtained several
mutant P. ostreatus strains resistant to a carboxin-derived fungicide, flutolanil, from UV irradiated basidiosporesof wild-type strains. We examined to clone a gene encoding succinate dehydrogenase iron-sulfer (Sdh lp)
subunit, Sdi, which is thought to be concerned with the flutolanil resistance, using PCR technologies. And we
tried to determine the nucleotide sequence of the gene from wild-type and mutant strains. As a result, total
sequence of wild-type Sdi has been determined, and those of mutant strains are currently being analyzed.
1996-P10
天然からのダイオキシン分解能を有する分解菌のスクリーニング
大川浩樹、平林達也、伊藤和貴、沖 妙、橘 燦郎
愛媛大学農学部
Screening of fungi having ability for degradation of dioxins
Hiroki Ohkawa, Tatuya Hirabayasi, Kazutaka ltho, Tae Oki, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
The time-course of the activities of lignin peroxidase, manganase peroxidase and laccase fromthe six fungi having ability for degradation of 2.7-Dichlorodibenzo-p-dioxin (2,7-DCDD) isolated by thescreening method was measured in connection with the degradation rate of 2,7-DCDD. Correlation between theactivity of lignin peroxidase and the degradation rate of 2.7-DCDD was observed. However, the activities ofmanganese peroxidase and laccase were not correlated to the degradation rate of 2.7-DCDD. From the results
obtained above, we tried to modify the screening method found previously.
1996-P11
白色腐朽菌 WD544 菌株による色素の分解について281

高野麻理子、西田篤実、中村雅哉
森林総合研究所
Degradation of dyes by white-rot fungus WD544 strain
Mariko Takano, Atsumi Nishida, Masaya Nakamura
Forestry and Forest Products Research Institute
Abstract:
Four dyes decolorization plates tests using RBBR, PolyR, Poly S and Azure B were conductedwith 26 wood-rotting fungi. WD544 was the only strain that decolorized all of 4 dyes on the test plates
containing High-C, Low-N medium. WD544 decolorized RBBR and Poly R not only on the H-C, L-N plates
while Poly S and Azure B were decolorized only under H-C, L-N condition. RBBR was also decolorized in bothshaken and stationary liquid cultures, but the other 3 dyes were decolorized only under static conditions.
Laccase activity was assayed during stationary cultivation but lignin peroxidase activity was rarely observed inthese cultures. Time course change in visible
spectrum of each of 4 dyes suggested that RBBR was degraded in the liquid culture and the other 3 dyes were
removed predominantly by fungal adsorption and further degraded on or in the mycelium.
1996-P12
ケナフ化学成分の総合利用 —靭皮部と本部のパルプ化—敖日格勒、佐野嘉拓、浦木康光
北海道大学農学部
Utilization of kenaf component. -Pulping of bast and woodAorigele, Yoshihiro Sano, Yasumitsu Uraki
Faculty of Agriculture, Hokkaido University
Abstract:
Oxygen pulping of kenaf bast was carried out with 150% NaOH of o.d. bast at 110ºC and 7kg/cm2 of O2 for 90 min. After boiling with 70% AcOH, bast pulps with much great delignification andsatisfactory physical properties were obtained in yields of 48%. The pulp was easily bleached at 85% brightness
by ECF bleaching. For the total utilization of kenaf stalk kenaf wood (core) and stalk (core and bast) were
pulped by solvent systems using aqueous AcOH with mineral acids at refluxing temperature and aqueous EtOH
with AcOH at l70.
1996-P13
リグニン生分解に関する研究（VIII） —マンガンペルオキシダーゼによる針葉樹クラフトパルプの濃色化—
江原克信、堤 祐司、西田友昭
静岡大学農学部
Studio a on lignin biodegradation (VIII), The darkening of softwood kraft pulp with manganese peroxidase
Katunobu Ehara, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The brightening performance of softwood haft pulp (SWKP) during manganese peroidase(MnP) treatment and the yields of alkaline nitrobenzene oxidation products from the treated pulp werecompared to clarify the mechanism of darkening of SWKP by MnP treatment. The yields of oxidation products
markedly decreased with the brightness started to decrease, and the yields kept same level after when the pulp
brightness increase thereafter. On the other hand, the yields from untreated hardwood kraft pulp (HWKP) weremuch less than that from SWKP and kept the same level during the brightness increase by MnP treatment. These
results suggest that non-condensed type lignin may he oxidatively condensed and lead to the darkening of
SWKP during MnP treatment.
1996-P14
β-O-4 型 LCC モデル化合物のリグニンペルオキシダーゼによる分解
宮田 聡、梅澤俊明、服部武文、島田幹夫
京都大学木質科学研究所
The degradation of β-O-4 type lignin carbohydrate complex model compounds by lignin peroxidase
Satoshi Miyata, Toshiaki Umezawa, Takefumi Hattori, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Nonphenolic β-O-4 type lignin carbohydrate complex model compounds (LCCs) as well as thecorresponding β-O-4 dimers were degraded by lignin peroxidase (LiP), and time course of oxidation of thesubstrates and product formation was monitored. No significant differences in the LiP catalyzed oxidation were282

observed between the LCC model compounds and the β-O-4 dimers. The result indicated that the sugar moietyof the LCC model compounds did not prevent, at least qualitatively, oxidation of the LCC model compounds by
LiP.
1996-P15
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（XI）〜クラフトパルプのバイオブリーチングにおけるパルプ中のマンガンイオンの状態変化〜
平井浩文*1、近藤隆一郎*1、坂井克己*1、鬼木隆幸*2*1
九州大学農学部、*2 九州歯科大学一般教育部
Studies on ligninolytic enzymes of white-rot fungi (XI), Change of oxidation number of manganese in kraft pulp
during biological bleaching
Hirofumi Hirai*1, Ryuichiro Kondo*1, Kokki Sakai*1, Takayuki Oniki*2*1
Department of Forest Products, Faculty of Agriculture, Kyushu university, *2Kyushu Dental College
Abstract:
The oxidation number of manganese in unbleached hardwood kraft pulp (UKP) was determinedby the electron spin resonance (ESR) method. The spectrum of Mn(II), which revearled hyperfine splitting, was
not observed, and the spectrum of dioxide could be observed. After fungal- treatment of UKP with
Phanerochaele sordida YK-624, the spectrum of Mn(II) could be detected in the UKP. It is concluded thatmanganese dioxide is dominant in UKP, and that P. sordida YK-624 reduced manganese dioxide to Mn(II)which may stimulate production and function of manganese peroxidase.
1996-P16
イネワラのセルラーゼ及びアンモニアを用いたパルプ化とパルプの性状
朴 承栄*1、飯塚堯介*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
Preparation and characterization of rice straw pulps by cellulase or ammonia treatments
Park Seung Young*1, Kenji Iiyama*2, Gyosuke Meshitsuka*1*1Graduate School of Agriculture and Life Science, the University of Tokyo, *2Asian Natural Environmental
Science Center, the University of Tokyo
Abstract:
It is expected to develop the effective utilizations of agricultural wastes, such as rice straws,
with environmentally sustainable processes. In this paper, pulping of rice straw by treatments with
polysaccharide hydrolases or alkaligenic chemicals, but not by conventional alkaline treatments, were examined.
The pulps were characterized by chemical analyses of the components, and their behaviors during laboratory
scale defibration of treated rice straws were observed by SEM-EDXA. There were no significant improvements
for defibration of rice straws by any enzyme treatments, but ammonia treatment which improved defibration andcaused considerable deliglification probably due to the cleavage of ester-linkage between lignin andpolysaccharides through ferulic acids, together with effective removal of silica from pulps. In addition we
confirmed that all of p-hydroxybenzaldehydes in an alkaline nitrobenzene oxidation products of rice straw are
produced from p-coumaric acids esterified or etherified to wall polymers, and lignin in rice straws is notcharacterized by the presence of p-hydroxyphenyl nuclei.
1996-P17
リグニン系土壌改良剤の開発（5）各種リグニンの添加と根の伸長生長
斉藤京子*1、中西友子*2、松林政仁*3、飯塚堯介*1*1
東京大学大学院農学生命科学研究料、*2 日本原子力研究所
Developmentof new lignin derivatives as soil conditioning agent (V), Growth of plants root under various soil
condition containing lignin samples
Kyoko Saito*1, Tomoko Nakmishi*2, Masahito Matsubayashi*3, Gyosuke Meshitsuka*1*1Graduate School of Agricultural and Life Sciences, the University of Tokyo*2
Faculty of Agriculture, the University of Tokyo, *3Japan Atomic Energy Research Institute
Abstract:
It is well known that aluminium ion gives seriously damages to plant growth in acid soil. We
have developed a new lignin derivative (radically sulfonated: S-1) from kraft lignin, which strongly
associates with soil and also traps Al ion. So, there is a possibility of utilization of kraft lignin as asoil conditioning agent. In this paper, the length of roots of radish (Raphanus Sativus.) were determined during
the growth on various soils containing lignin samples, and these effects on the growth of root were examined.
As a results, all lignin samples apparently removed the inhibitory effects of aluminium ion. And, S-1 may be283

more effective than LSA.

284

第 42 回 （1997.10.27-28） 北海道大学学術交流会館
1997-101
イネ培養細胞におけるヒドロキシケイ皮酸類の形成機構
福島和彦、山下耕司、加藤由佳、安田征市
名古屋大学農学部
Formation of hydroxycinnamic acids in the suspension culture of Oriza sativa
Kazuhiko Fukushima, Koji Yamashita, Yuka Kato, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
Formation of hydroxycinnamic acids in the suspension culture of Oriza sativa was investigated.
This culture was the cluster of a number of cells which did not have the secondary cell wall. It was shown
ferulic acid was deposited in the cell wall at the early stage prior to the deposition of p-coumaric acid. Feeding
experiment showed that labeled feru1ic acid was incorporated into cell wall as esterified ferulic acid selectively,
while labeled p-coumaric acid was incorporated after the major conversion to ferulic acid. It was also suggested
that considerable amount of ferulic acid fed to the culture was covalently linked at the 5 position of its aromaticring during long term incubation.
1997-102
イネ節間柔組織形成異常 mutant を用いた細胞壁形成過程の解析
西窪伸之*1、荒木智之*1、藤川 裕*1、平田 豊*2、北野英己*3、黒田健一*4、片山義博*1*1
東京農工大学大学院 BASE、*２東京農工大学農学部、*３名古屋大学農学部、*４筑波大学農林工学系
Chemical and molecular biological analysis of cell wall formation in dwarf mutant of rice plant (Fukei-71)
Nobuyuki Nishikubo*1, Tomoyuki Araki*1, Yutaka Fujikawa*1, Yutaka Hirata*2, Hidemi Kitano*3, Kenichi
Kuroda*4, Yoshihiro Katayama*1*1
Graduate school of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Tokyo University of Agriculture and Technology, *3Faculty of Agriculture, Nagoya University,*4
Institute of Agricultural and Forest Engineering, University of Tukuba
Abstract:
Recessive mutations at single locus cause the collapse of parenchyma cells in internode of Rice
plant “Fukei-7l”. This irregular parenchyma mutation was identified by gamma-ray irradiation of seed of"Fujiminori”. The mutated Rice plant "Fukei-71" show dwarf form and acuumulates lgnin- like material fromp-coumaric acid and ferulic acid in parenchyma cell. The lignin-like material may be esterified cross-link
between phenylpropanoids and polysaccharide. Furthermore existence of pathway related to ester cross-link
separate from is suggested by strong expression of PAL and OMT of lignin biosynthesis pathway in parenchyma
cell. This mutant is regarded as mutation participating in the factor that controls the cell wall formation withsingle regulation factor recessive at higher position than regulation of lignin and polysaccharide biosynthesis.
The mutation should be useful in facilitating the identification of factors that control the synthesis anddeposition of lignin and other cell wall components.
1997-103
イネ科植物リグニンにエーテル結合したヒドロキシ桂皮酸の結合位置
角谷和芽*1、飯塚堯介*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
Hydroxycinnamic acid bridges between wall polysaccharides and lignin in Gramineous plants
Kazume Kadoya*1, Gyousuke Meshitsuka*1, Kenji Iiyama*2*1
Graduate School of Agricultural and Life Sciences, The University of Tokyo, *2Environmental Science Center,the University of Tokyo,
Abstract:
The hydroxycinmmic acids, p-coumaric (PCA) and ferulic acid (FA), are esterified and/or
etherified to cell wall polymers in Gramineous plants, but of which position etherified to lignin side chain are
not clear and argued for the α- or β-positions. In this study, lignin-polysaccharide complexes (bridges between
lignin and wall polysaccharide through FA) extracted from walls of oat (Avena sativa L. ) internodes were
examined by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation followed by alkaline hydrolysis. The
quantities of hydroxycinnamic acids liberated by alkaline hydrolysis were compared between before and after
DDQ oxidation. Relatively high quantities of liberated FA and PCA after DDQ oxidation than those before
DDQ oxidation suggests that they could etherify lignin at α-position of lignin side chain.
285

1997-104
Eucalyptus camaldulensis および E. globulus の樹幹内変異を用いたリグニン含有率、リグニンのモノマー組
成比とへミセルロース組成比の関係について
小名俊博、園田哲也、伊藤一弥、柴田 勝
王子製紙株式会社森林資源研究所
Relationship of lignin content, and lignin monomeric composition and hemicellulose composition in the same
trunk sought by their within-tree variations in Eucalyptus camaldulensis and E. globules
Toshihiro Ona, Tetsuya Sonoda, Kazuya Ito, Masaru Shibata
Kameyama Research Center, Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
The relationship of extractives-free (EF) lignin content, lignin monomeric composition as
syringyl/guaiacyl (S/G) ratio by thioacidolysis, and neutral sugars constituting hemicellulose by hydrolysis withtrifluoroacetic acid was examined. This was performed in the same trunk by their within-tree variations, whichmean the investigation with the same genes, in Eucalyptus camaldulensis and E. globulus. As results, eachspecies had a high negative correlation between EF-lignin content and lignin S/G ratio although the difference
between species and/or individuals was observed in the trend of within-tree variations of the wood properties.
The relationship between EF-lignin content and lignin S/G ratio is considered to be caused from the differencein the fiber morphology from the relationship between lignin and EF-basic density which may relate to the fiber
morphology. Furthermore, the relationship between the lignin monomeric composition derived from β-O-4bonds and the hemicellulose composition is concluded to exist since common trend was observed between two
species as higher lignin S/G ratio with the increase in xylan and or with decrease in arabinogalactan (galactan).
We also discuss and suggest that the hemicellulose composition can influence on the lignin monomericcomposition.
1997-105
Eucalyptus globulus Lignin の化学的性状 —改良ニトロベンゼン酸化—
片平 類、中坪文明
京都大学大学院農学研究科
The chemical characterization of Eucalyptus globulus lignin, — Analysis by a modified nitrobenzene oxidation—
Rui Katahira, Fumiaki Nakatubo
Graduate school of Agriculture, Kyoto University
Abstract:
Recently, Eucalyptus globulus has been regarded as one of the most suitable trees for
pulping, because it can grow largely in short time and gives a high yield of pulping. It is really important to findthe reason for its high yield. Thus, we intended to investigate the chemical structure of E.globulus lignin. Here
we propose a modified nitrobenzene oxidation method, which was applied to E. globulus lignin.
1997-106
超音波照射したリグニン溶液の ESR 法による研究 —スピントラッピング法の適用—
清野晃之、吉岡亜希、藤原政司、陳 克利、恵良田知樹、田畑昌祥、高井光男
北海道大学大学院工学研究科
An electron spin resonance study of radicals produced by ultrasonic irradiation of lignin solution. An applicationof spin-trapping method
Teruyuki Seino, Aki Yoshioka, Masashi Fujiwara, Ke-Li Chen, Tomoki Erata, Masayoshi Tabata, Mituo Takai
Graduate School of Engineen.ng, Hokkaido University
Abstract:
A spin trapping technique combined with an electron spin resonance (ESR) method
was successfully applied to the lignin solution which was subjected to ultrasonic irradiation in order to trap andidentify the origin radical of the phenoxy radicals stabilized in the wood lignin. It was found, consequently, that
nitroxide radicals called spin adducts produced by the reaction of secondary carbon radicals and2,4,6-tri-tert-butylnitrosobenzenes as the spin trapping reagent were generated from the lignin dissolved indimethysulphoxide (DMSO) when the lignin solution was subjected to ultrasonic irradiation at 50 ºC. The
resulting secondary carbon radical was supposed to be created by the βbond scission in the HCβ-O-4phenolgroup called β-O-4 bond which combines the three dimentional network structure of the wood lignin. Further
the secondary carbon radical was also considered as a counter radical of the phenoxy radical stabilized in the not
only solution but also lignin solid.
286

1997-107
リグニン化学構造の不均一性（2）—エーテル結合の選択的開裂を用いたリグニンの性状の検討—
堀啓映子、飯塚堯介
東京大学大学院農学生命科学研究科
Structural heterogeneity of hardwood lignin (II), —Characterization of lignin by selective cleavage of ether
linkages—
Keko Hori, Gyosuke Meshitsuka
Graduate
Schoolof
AgriculturalandLife
Sciences,theUniversityofTokyo
Abstract:
Trimethylsilyl iodide (TMSiI) was known to cleave - and - ether bonds selectively under
mild condition. We used TMSiI to degrade high molecular weight lignin, and analyzed the newly formed low
molecular weight fractions. It was found that there are some endwise lignin fractions in methylated-periodate
lignin of birch, however it was not the case for birch MWL. Every low molecular weight fraction from MWL by
TMSiI treatment showed quite similar characteristics. An end-wise lignin fraction from periodate lignin was
confirmed to be depolymerized mainly to monomeric units by excess amount of TMSiI.
1997-108
CAD 阻害によって形質転換させた樹木中に生成する異常リグニンの化学的構造について —種々の化学分
解反応に対するシンナミルアルヂヒド構造の挙動—
伊藤 隆*1、河合真吾*1、大橋英雄*1、樋口隆昌*2*1
岐阜大学大学院連合農学研究科、*2 京都大学名誉教授
Chemical study on abnormal lignin of transgenic plants with antisense cinnamyI alcohol dehydrogenase gene,—The behavior of cinnamyl aldehyde groups for various chemical degradation reactions—Takashi Ito*1, Shingo Kawai*1,, Hideo Ohashi*1,, Takayoshi Higuchi*2*1,
The United Graduate School of Agriculture Science, Gifu University, *2Professor emeritus Kyoto University
Abstract:
Novel thioacidolysis products derived from sinapaldehyde and coniferyl aldehyde were isolated
and identified by GC-MS and 1H-NMR analyses, It is clear that the cinnamyl aldehydes were converted to manydegradation products by thioacidolysis. On the other hand, sinapaldehyde and coniferyl aldehyde were notaltered by acidolysis. The acidolysis treatment of coniferyl aldehyde DHP gave vanillin, coniferyl aldehyde andan unknown product as degradation lproducts. Coniferyl aldehyde and sinapaldehyde were effectively altered bymild alkali treatment to give vanillin and syringaldehyde, respectively.
1997-109
樹木細胞壁リグニン生合成及び糖代謝過程の免疫組織化学的研究
吉富圭織*1、増野洋子*1、西窪伸之*1、真壁和彦*1、川合伸也*2、諸星紀幸*1、片山義博*1*1
東京農工大学大学院 BASE、*２東京農工大学農学部
Immunohistochemistry of lignin biosynthesis and carbohydrate metabolism in woody plant
Kaori Yoshitomi*1, Yoko Mashino*1, Nobuyuki Nishikubo*1, Kazuhiko Makabe*1, Shinya Kawai*2, Noriyuki
Morohosi*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Tokyo University of Agriculture and Technology
Abstract:
Lignin is a major component of plant cell wall. We have investigated enzymes involved in thephenylpropanoid biosynthesis by biochemical and immunochemical methods. We prepared antiserums raise
against PAL, OMT, 4CL, CAD, POX, and investigate immunochemical localization of these enzymes. As aresult, we suggested the tissue-specific expression and relevance of each enzyme in protoxylem. We will reportlocalization of each enzyme in metaxylem tissue and propose functions of them. Carbohydrate chain
biosynthesis closely related to lignin biosynthesis in cell wall fomlation in plant. Therefor, we prepared
antiserums raise against enzymes involved in the carbohydrate chain biosynthesis and investigate
immunochemical relationship between lignin and carbohydrate chain biosynthesis.
1997-110
土壌微生物 Sphingomonas paucimobilis SYK-6 株のリグニン分解に関与するテトラヒドロ葉酸依存性脱メチル化酵素遺伝子（lig H）の構造と機能に関する研究
園木和典*1、笠原健秀*2*3、西川誠司*4、川合伸也*2、諸星紀幸*1、片山義博*1*1
東京農工大学大学院 BASE、*２東京農工大学農学部、*３日本製紙株式会社、*４コスモ総合研究所
Structure and function of tetrahydroforic acid dependent Sphingomonas paucimobilis SYK-6 gene essential to287

degradation of lignin
Tomonori Sonoki*1, Takehide Kasahara*2*3, Seiji Nishikawa*4, Shinya Kawai*2, Noriyuki Morohoshi*1, Yoshihiro
Ktayama*1*1Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Tokyo University of Agriculture and Technology, *3Cosmo research institute, *4Nippon paperindustries
Abstract:
The soil bacterium, Sphingomonas paucimobilis SYK-6 is able to degrade various types ofdimeric lignin compounds such as biphenyl, β-aryl ether, phenylcoumaran etc. In this study, we report here
about the 1.8 kbp DNA fragment essential to O-demethylation of syringic acid (SA) and vanillic acid (VA).
Sequencing analysis showed an open reading frame of 1671bp in this fragment, and this ORF has homolog toformyltetrahydrofolate synthetase. When this gene was expressed in mutant DC-49, which was deficient indemethylation of SA and VA, the enzymatic activity of VA and SA demethylation was observed. For enzymatic
activity of O-demethylation of SA and VA, lig H and tetrahydroforic acid were essential.
1997-111
担子菌における菌体外ヘム酵素合成系の解析 —外因性 5-アミノレブリン酸の菌体外酵素分泌への影響松下啓太、割石博之、田中浩雄
九州大学農学部
Effect of exogenous 5-aminolevulinic acid on fungal production of extracellular heme peroxidases
Keita Matsushita, Hiroyuki Wariishi, Hiroo Tanaka
Abstract:
Extracellular activity of heme peroxidases (LiP, MnP) was closely related to 5-aminolevulinicacid biosynthetic activity in white-rot fungi. ALA biosynthetic activity was higher in the white-rot fungi,
Coriolus versicolor and Phanerochaete chrysosporium, than that in the brown-rot fungus, Tyromyces palustris.
The effects of exogenous ALA on extracellular heme peroxidases were investigated. Exogenous addition of
ALA increased the relative amounts of free protoheme and of secreted MnP. ALA had no effect on MnP activity.
These results suggested that the rate- determining step for extracellular heme peroxidase production may not beprotein but heme biosynthesis.
1997-112
ペルオキシラジカル及びスーパーオキサイドアニオンの関与する遷移金属錯体 —電子移動系反応によるリグニンの解重合—渡辺隆司*1、Karin Koller*2、Kurt Messner*2、仲亀誠司*1、榎 牧子*1、本田与一*1、桑原正章*1*1
京都大学木質科学研究所、*2 ウィーン工科大学生物化学工学微生物研究所
Depolymerization of lignin by transition metal complex-electron transfer reactions involving peroxyl radical
and superoxide anion
Takashi Watanabe*1, Karin Koller*2, Kurt Messner*2, Seiji Nakagame*1, Makiko Enoki*1, Yoichi Honda*1,
Masaaki Kuwahara*1*1
Wood Rsearch Insdtute, Kyoto University, *2Research Institute for Biochemical Technology and Microbiology,
University of Technology, Vienna
Abstract:
In aqueous solutions, 14C-labelled synthetic lignin was intensively depolymerized with
Cu(II) ad lipid hydroperoxide model compounds at room temperature in the presence of pyridine, which is
known as a metabolite of lignin-degrading fungi. Reaction of Cu(II)/pyr with H2O2 was less effective for thelignin depolymerization, but this system enhanced the brightness of UKP frm 34.5 to 81 point. Spin trapping
experiments demonstrated that peroxyl radical is involved in the former reaction while the latter involves
superoxide anion and active oxidants other than hydroxyl radical. A wide variiety of practical application will be
developed based on the copper/coordination compound/ peroxide reactions.
1997-113
リグニンペルオキシダーゼによるべラトリルアルコールの酸化機構
桃原郁夫
森林総合研究所
Veratryl alcohol oxidation catalyzed by lignin peroxidase
Ikuo Momohara
Forestry and Forest Products Research Institute
Abstract:
Mechanism of veratryl alcohol oxidation catalyzed by lignin peroxidase was investigated.
288

Relationship between LiP inactivation and amount of veratraldehyde formation suggests that the amount ofhydrogen peroxide consumed for inactivating LiP is negligible. Reactions under single turn over conditions
suggest reaction of LiP-I with veratryl alcohol is necessary for veratraldehyde formation in the absence ofoxygen. Stopped-flow technique reveals that two veratryl alcohol molecules are involved in Lip catalytic cycle.
1997-114
Lignin Peroxidase によるリグニンの直接酸化 −DHP と LiP compound I, II の反応性の検討—
城島 透、割石博之、田中浩雄
九州大学農学部
Direct oxidation of lignin by lignin peroxidase, – Reactivity of LiP compound I, II with DHP
Toru Johjima, Hiroyuki Wariishi, Hiroo Tanaka.
Faculty of Agriculture, Kyushu University
Abstract:
Reactivity of lignin peroxidase (LiP) from Phanerochaete chrysosporium against a synthetic
lignin (DHP) were studied utilizing transient kinetic technique. A one-electron transfer from DHP to LiP
compound I (LiPI) exhibited saturation kinetics, from which the dissociation equilibrium constant for LiPI-DHP
interaction was calculated to be 350 M. Kinetic characterization of LiPI reaction with DHP strongly suggested
that LiP is capable of oxidizing DHP directly at the protein surface via a long-range electron transfer process.
1997-特別講演
地球環境とバイオマス
戸倉清一
北海道大学大学院地球環境科学研究科
Sustainability of earth environment through biotechnology
Seiichi Tokura
Graduate School of Environmental Earth Science, Hokkaido University
Abstract:
The higher quality of foods is requested due to rapid progress of human life, the more heavy
environmental pollution is caused by a tremendous amount of food, agricultural and marine wastes. Several
polysaccharides in these wastes have been studied as renewable resource due to relatively easier extraction andpurification from waste. Chitin, one of biofunctional muco- polysaccharides of natural occurrence, has been
investigated to apply for biomedical materials following to the removal of calcium and protein. Although waste
paper is recycled in paper industry, cellulosic resources are able to find out easily in agricultural or food wastes.
These cellulosic wastes were studied to reconstruct into novel polysaccharides with new functions throughbacterial cultivation. The direct filamentation of novel polysaccharide has been achieved successfully by the useof shallow culture pan which was designed to form a thinner gel on the surface of culture medium. The
filamentation was proceeded continuously with the rate of 30mm/h. The functionalization of cellulosic products
were also achieved successfully with change of carbon source in the culture medium.
1997-201
トチュウの粗酵素によるネオリグナン・リグナンのエナンチオ選択的生成
加登優樹、片山健至
香川大学農学部
Enantioselective formation of neolignans/lignans by cell-free extracts of Eucommia ulmoides
Yuki Kado, Takeshi Katayama
Faculty of Agriculture, Kagawa University
Abstract:
Formation of (+)-erythro and (-)-threo guaiacylglycerol- -coniferyl ethers was found, following
incubation of coniferyl alcohol with cell-free extracts from stems of Eucommia ulmoides young shoots in thepresence of H2O2. Enantiomeric excesses of the both diastereomers increased in a Iinear fashion for l hr. Whenthe (±)-erythro isomer was incubated as a substrate under the same conditions, it was recovered as an almost
racemate. The erythro isomer formed by the action of cell-free extracts from the leaves was an almost racemate.
Incubation of sinapyl alcohol with insoluble residues from the stems in the absence of provided cofactors gave
syringaresinol with (+)-enantiomer slightly preferred.
1997-202
Linum flavum のリグナン生合成酵素について
三亀啓吾、梅澤俊明、島田幹夫
289京都大学木質科学研究所
Lignan synthesis by cell-free extracts from L.inum flavum
Keigo Mikame, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Three lignans, (+)-pinoresinol (65% e. e.), (+)-lariciresinol (70% e. e.) and(-)-secoisolariciresinol (>99% e. e.) were isolated from Linum flavum. When [9,9-2H2,OC2H3] coniferyl alcohol
was administered to this plant, incorporation of deuterium atoms into pinoresinol, lariciresinol andsecoisolariciresinol was observed. Cell-free extracts from Linum flavum catalyzed the formation of the threelignans, when incubated with coniferyl alcohol in the presence of NADPH and H2O2. These results suggested
that the step to produce the optically pure lignan is the formation of
secoisolariciresinol from lariciresinol in L. flavum.
1997-208
ベンジル化木材樹脂の発泡性を支配する諸因子
平岡俊治、上田昌見、高見泰博、越島哲夫
日本化学機械製造株式会社
Foaming-regulating factors of benzylation reaction on wood.
Toshiharu Hiraoka, Masami Ueda, Yasuhiro Takami, Tetsuo Koshijima
Japan Chemical Engineering & Machinery Co. Ltd.
Abstract:
Foaming is one of the most interesting practical use of wood plastics. In the case of benzylated
wood resins, it becomes the biggest advantages for use of the resin that the foaming can be performed without
use of any plasticizers. The present investigations were conducted to make clear the principal production
conditions of well-foamable benzylated resin: Foaming temperature depended on the softening or flow
temperatures, and the most adequate at about 5ºC above thesoftening temperature. Ferric ion was found to catalyze the decomposition of benzylchloride and diminishedextensively the foaming extent of the benzylated wood resins. The influences of mercerization temperature were
one of the biggest factors, and the extensive foaming appeared at 20 to 46ºC. Above 50ºC, foaming decreased
less than 40% owing to liberation of lignin moiety from the LCC contained.
1997-204
リグニン含有型吸水性ポリウレタンフォームの形態的及び物理的性質
畠山兵衛*1、伊豆田良信*1、兼松幹生*1、廣瀬重雄*2、畠山立子*2*1
福井工業大学工学部、*2 物質工学工業技術研究所
Morphological and physical properties of water-sorption type polyurethane foams containing lignin
Hyoe Hatakeyama*1, Yoshinobu Izuta*1, Mikio Kanematsu*1, Sigeo Hirose*2, Tatsuko Hatakeyama*2*1
Fukui Institute of Technology, *2National Institute of Materials and Chemical Research
Abstract:
Polyurethane (PU) foams were prepared from molasses (MOL), kraft lignin (KL) and anorganosolv lignin (Alcel lignin, AL). The prepared PU foams were analyzed by differential scanning calorimetry(DSC), thermogravimetry (TG) and mechanical measurements. Using the obtained results, water-sorption type
PU foams were prepared. The prepared PU foams showed thermal degradation temperature (Td) at around 220 230 ºC. Water absorptivity (Ws) was calculated according to the following equation: Ws=(W1- Wo)/V, where Wo
is weight of dry sample (g), W1 weight of sample after water-absorption (g), V volume of dry sample (cm3). Ws
of the prepared PU foams depended on the density of sample and a maximum value was ca. 0.9. Stress/density
value (kPa/kg±·m-3) of dry sample was ca. 1.9 and ca 1.7 after water-absorption.
1997-205
リグニンベースポリカプロラクトン誘導体からのポリウレタンの調製と熱的性質
伊豆田良信*1、畠山兵衝*1、廣瀬重雄*2、畠山立子*2*1
福井工業大学工学部、*2 物質工学工業技術研究所
Preparation and thermal properties of polyurethanes derived from lignin-based PCL
Yoshinobu Izuta*1, Hyoe Hatakeyama*1, Sigeo Hirose*2, Tatsuko Hatakeyama*2*1
Fukui Institute of Technology, *2National Institute of Materials and Chemical Research
Abstract:
Polyurethane (PU) sheets were prepared from kaft (KL) and Alce1 (AL) lignin-based
polycarprolactones (PCL). The obtained lignin-based PCL's were analyzed by differential scanning calorimetry(DSC) and thermogravimetry (TG). The glass transition temperature (Tg) decreased from -10 to -60 ºC with290

increasing CL/OH ratio from 2 to 25 mol/mol. The cold-crystallization and melting were observed when CL/OH
ratio of the samples exceeds 15 mol/mol. DSC results suggest that CL molecules form crystalline structure bymolecular rearrangement occurred at around 0 ºC. Phase diagrams were established for both KL and AL
lignin-based PCL's.
1997-206
タンニン—タンパク質沈澱機構
河本晴雄*1、中坪文明*2*1
京都大学大学院エネルギー科学研究科、*2 京都大学大学院農学研究科
Tannin-protein co-precipitation mechanism
Haruo Kawamoto*1, Fumiaki Nakatsubo*2*1
Graduate School of Energy Science, Kyoto University, *2Graduate School of Agriculture, Kyoto University
Abstract:
Stoichiometric analysis of successive washing of galloylglucose (hydrolysable tannin) - protein
precipitates by aqueous solution was carried out. The following results were obtained: 1) at least two bindings,
strong and weak bindings, respectively, are included in the galloylglucose-protein bonds; 2) although maximum
number of the binding site on a protein molecule increases linearly with an increase in protein molecular weight,
content of the number of the strong binding sites (NSB) is quite different depending on the protein structure; this
explains different relative affinities of proteins for tannin; 3) stability of the precipitates is explainable by the
relationships between galloylglucose/protein molar ratio required for the precipitation and NSB.
1997-207
高分子量 procyanidin gallate の合成とその性質
米田 聡、中坪文明
京都大学大学院農学研究科
Synthesis of procyanidin gallates with high molecular weight and their function
Satoshi Yoneda, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
The preparation methods of the high-molecular-weight procyanidin gallate was developed.
These methods may be also applicable to the conversion of lignins into the functional polymer withprotein-precipitating capacity like tannins.
1997-208
炭素化非木材繊維シートの物性
大谷慶人、中島綾子、鮫島一彦
高知大学農学部
Characterization of resin-impregnated and carbonized nonwood fiber sheets
Yoshito Ohtani, Ayako Nakajima, Kazuhiko Sameshima
Faculty of Agriculture, Kochi University
Abstract:
Ten nonwood bleached chemical pulps and one softwood bleached kraft pulp were used tomake handsheets. All pulps were beaten by PFI mill and also subjected to handsheet making. Every handsheet
was impregnated with phenol resin, polymerized by heating and carbonized at 800ºC. Resulting carbonized pulp
sheets were characterized and evaluated as an electromagnetic shielding material. The sheets from bagasse,
kenaf and jute pocessed good electric wave shielding effects rather than the cupper sheet. But the magnetic
shielding effects were inferior to that of cupper sheet. The electric wave shielding effect correlates to the sheet
thickness and density.
1997-209
Ganoderma sp. YK-505 株の産生するマンガンペルオキシダーゼの安定性について
原園幸一、近藤隆一郎、坂井克己
九州大学農学部
Stability of manganese peroxidase secreted from Ganoderma sp. YK-505
Koichi Harazono, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We evaluated stabilities of manganese peroxidases (MnPs) secreted from white rot fungi,
Phanerochaete chrysosporium, Phanerochaet sordida YK-624 and Ganoderma sp. YK-505. Two MnP
291

isoenzymes (G-1 and G-2) from Ganoderma sp. YK-505 exhibited stabilities against high temperature and pH.
Change in the heme environment of MnPs from Ganoderma sp. YK-505 during incubation at high temperatureand pH was investigated by electronic absorption spectroscopy. The absorption spectra of MnPs after incubation
at high temperature or pH were similar to those of low-spin hexacoordinate ferric heme proteins, as described
previously in the report that MnP from P. chrysosporium was very susceptible to thermal inactivation due to theloss of calcium from the enzyme. The results demonstrated that the same structural changes as MnP from P.
chrysosporium occur during inactivation, resulting from the release of calcium from MnPs from Ganoderma sp.
YK-505 although inactivation of MnPs from Ganoderma sp. YK-505 occur in severer condition than that of
MnP from P. chrysosporium,
1997-210
担子菌 Bjerkandera adusta（ヤケイロタケ）の生産するマンガンペルオキシダーゼの有機溶媒中における反応
茶谷明伸*1、吉田晋一*2、本田与一*1、渡辺隆司*1、桑原正章*1*1
京都大学木質科学研究所、*2 鳥取県工業試験所
Reaction of manganese-dependent peroxidase from Bjerkandera adusta in organic solvents
Akinobu Chatani*1, Shinichi Yoshida*2, Yoichi Honda*1, Takashi Watanabe*1, Masaaki Kuwahara*1*1
Wood Research Institute, Kyoto University, *2lndustrial Research Institute of Tottori Prefecture
Abstract:
To characterize activities of manganese-dependent peroxidase (MnP) in organic media,
aromatic compounds and DHPs were oxidized with MnP from Bjerkandera adusta in water-miscible organic
solvents. ln 70% aqueous organic solvents, MnP exhibited high activities toward several phenolics and aromatic
amines such as guaiacol, 2,6-dimethoxyphenol, 3,3.-dimethoxybendizine, o-phenylenediamine andm-aminophenol. Oxidation of DHPs by MnP was also observed in aqueous organic solvents. ln 70% acetone,
guaiacyl DHP was polymerized by MnP while syrigyI DHP was depolymerized with concomitant formation of asmall amount of polymerized compounds.
1997-211
白色腐朽菌のリグニン分解に関与する酵素系に関する研究（XIII）—白色腐朽菌の産生する siderophore
様物質について—平井浩文、近藤隆一郎、坂井克己
九州大学農学部
Studies on ligninolytic enzymes of white-rot fungi (XIII), - Siderophore-like compounds produced by white-rot
fungi
Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
We primarily tried to detect and isolate siderophore-like compounds from white-rot fungus
Phanerochaet sordida YK-624. Fe(II) binding ability ms detected in 70% acetone-insoluble fraction from theliquid culture without Fe. The siderophore-like compounds were also secreted under Fe-sufficient culture. Two
compounds (compound I and II) were purified from the fraction with gel permeation chromatographies. The
molecular weight of these compounds were estimated about 3000-5000. IR spectra of these compounds showed
the presence of both peptide bonds and alcoholic hydroxyl groups. It is suggested that these compounds
selectively bound iron or cobalt. The addition of these compounds to the reaction mixture of ferrireductases
accelerated consumption of NADPH.
1997-212
白色腐朽菌 Phanerochate sordida YK-624 株より得られた突然変異体によるクラフトパルプのバイオブリーチ
ング
石村大児、近藤隆一郎、坂井克己、平井浩文
九州大学農学部
Biobleaching of kraft pulp with mutants from white-rot fungus Phanerochaete sordida YK-624
Daiji Ishimura, Hirofumi Hirai, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture. Kyushu University
Abstract:
We isolated mutant 1 and mutant 2 which have weak and strong tetrazolium salts reductive
activity, respectively from Phanerochaete sordida YK-624 by UV irradiation. When unbleached hardwood andoxygen-bleached softwood kraft pulps were treated with wild type and these mutants, mutant l made highly pulp
brightness increasing and secreted more manganese peroxidase (MnP) in the early incubation period compared292

with wild type, although mutant 2 showed the same tendency as wild type. Mutant 1 secreted MnP under lower
Mn(II) concentration, and uptook Mn(II) faster than wild type.
1997-213
The study on the 13C-NMR spectra of dissolved lignin from Na2S pretreatment kraft cooking
金 永燦*1、李 忠正*1, Diesheng Tai*1、佐渡 篤*2*1
南京林業大学、*2 東京農工大学農学部
The study on the 13C-NMR spectra of dissolved lignin from Na2S pretreatment kraft cooking.
Yongcan Jin*1, Zhongzheng Lee*1, Diesheng Tai*1, Atsushi Sawatari*2*1Nanjing Forestry University, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
Kraftban lignins from Na2S pretreatment liquor and cooking black liquor were isolated andanalyzed by 13C-NMR spectroscopy. The results were compared with those from conventional kraft cooking
with similar degree of delignification. Kraft lignin from Na2S pretreatment liquor contains less etherified
structures than that from conventional cooking. This indicates that the lignin removal during the Na2S
pretreatment is different from that in normal kraft cooking. The structure of lignin from pretreatment liquor
differs appreciably from that of lignin obtained from conventional pulping. Because of the relatively mild
condition, a large amount of terminal groups in the lignin molecule are removed one by one as peeling reactionin the Na2S pretreatment. In contrast, the fragmentation of lignin is more random in the conventional kraft
cooking.
1997-214
リグニンのオゾン酸化に伴う過酸化水素の生成
真柄謙吾*1、富村洋一*1、細谷修二*1、池田 努*2*1
森林総合研究所、*2 筑波大学農林工学系
Generation of hydrogen peroxide during the ozonation of lignin
Kengo Magara*1, Yoichi Tomimura*1, Shuji Hosoya*1, Tsutomu Ikeda*2*1
Forestry and Forest Product Research Institute, *2Tsukuba University
Abstract:
Ozone reacts with lignin through two pathways. One is ionic cyclo-addition to cleave a C3-C4
double bond. This reaction generates hydrogen peroxide as a reaction product. Another way is one-efectrontransfer from a dissociated phenolic hydroxyl group. This reaction reads to the formation of hydroxyl radicals
which cause the non-selectivity of ozone reaction. In the case of the radical reaction pathway, hydrogen
peroxide will not be produced. To investigate the contribution of these two pathways, we determined thegenerated hydrogen peroxide. When 2 mmol of veratryl alcohol was reacted with excess amount of ozone,
4.7mmol of hydrogen peroxide was detected. On the other hand, vanillyl alcohol gave only 0.7mmol ofhydrogen peroxide under the same reaction conditions. In the case of veratryl alcohol, because of the lack ofphenolic hydroxyl group, the ionic reaction pathway dominated. Although the dissociation of phenolic hydroxyl
groups is very little under neutral conditions, the radical reaction pathway dominated in the case of ozonation ofvanillyl alcohol. This is probably because the radical reaction is much faster than the ionic reaction.
1997-215
酸素脱リグニンに影響を与える要因 –溶解性有機物とリグニン量のばらつき種田英孝，飯嶋純フェルナンド
日本製紙株式会社
Effect of several factors on oxygen delignification,–Carryover and lignin contents variation in fibers Hidetaka
Taneda, Jun Fernando Iijima
Nippon Paper Industries Co., Ltd.
Abstract:
The process factors which affect the delignification in a medium consistency oxygen
delignification process were investigated. The effect of carryover to oxygen process consisted of the negative
one by the organic compounds like lignin and the positive one by residual alkali in it. After the initial reaction
with oxygen, COD and TOC values of the effluent did not change greatly. Therefore the further oxidation withoxygen did not observed. The variation of the lignin contents in each fiber showed the positive effect on thedelignification in the case of oxygen delignification. The reason for this phenomena is under investigation.
1997-216
酸素系の漂白過程における活性酸素種の反応経路と反応選択性293横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Reaction route and reaction selectivity of active oxygen species in oxygen containing bleaching processes
Tomova Yokoyama, Yuji Matsumoto, Gvosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
A cellulose model compound, methyl β-D-glucopyranoside (MGP), and/or lignin modelcompounds were subjected to a reaction in an alkaline hydrogen peroxide solution. The initial concentration of
MGP and the presence of a lignin model compound did not affect the recoveries of MGP. Recoveries of MGP
were smaller when hydrogen peroxide was stepwisely added than when hydrogen peroxide was added at once
initially. These results confirmed a competition between model compounds and hydrogen peroxide in reactingwith active oxygen species which were produced from the degradation of hydrogen peroxide itself, andsuggested that active oxygen species attacked hydrogen peroxide preferentially rather than model compounds.
The competition was observed most clearly when ferric ion was added.
1997-217
フエノキシラジカルと酸素との反応性について（2）
杉元倫子、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Reactivity of phenoxyl radical with molecular oxygen, (2)Tomoko Sugimoto, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
In order to examine the possibility of the reaction between phenoxyl radical andmolecular oxygen, syringyl alcohol (SA) was treated with a one electron oxidizing reagent, manganese (III), andthe effect of oxygen pressure on the yield of methanol from this phenol
was determined. The increased formation of methanol under increased oxygen pressure was thought to indicate
the reaction between phenoxyl radical and molecular oxygen. The yields of the starting material SA and one of
the reaction products, syringaldehyde, were constant regardless of the oxygen pressure. Post-treatment withalkali was essential for the complete formation of methanol. The reduction by NaBH4 after the sufficientalkali-treatment resulted in increased formation of methanol. This is due to the reduction of formaldehvde
formed by the coupling reactions of C1 radical.
1997-218
塩素漂白で生成した高分子有機塩素化合物の環境中での挙動（1）—熱分解ガスクロマトグラフによる分析法の確立—
幸田圭一、新谷博幸、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Environental fate of high molecular weight chloroorganics produced by chlorine bleaching (1) : Development of
a new analytical method by the use of pyrolysis gas chromatography
Keiichi Koda, Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
High molecular weight chloroorganics were extracted from chlorinated pulps by the use of
aqueous dioxane and were used as authentic samples of chloroorganics in the effluent. The extracted
chloroorganics were subjected to pyrolysis GC. The pyrogram of chloroorganics is quite different from that ofmilled wood lignin (MWL), which is assumed to be representative of the native lignin in wood. Over five
hundred of pyrolysis products were detected in the GC and their mass fragmentation patterns were stored in themass library. Interestingly, the majority of the pyrolysis products were not aromatics. By the use of the mass
library thus constructed, samples obtained from the discharged bleaching effluents were successfully analyzed.
1997-219
塩素漂白過程で環開裂した芳香核に由来する低分子化合物の検出
新谷博幸、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Liberation of low molecular weight compounds from oxidatively cleaved aromatic ring of chlorolignin
Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
294

Abstract:
Unbleached softwood kraft pulp, unbleached hardwood kraft pulp and oxygen prebleachedhardwood kraft pulp were chlorinated, and residual chlorolignin in pulps were extracted by aqueous dioxane.
When extracted chlorolignins were treated with alkali, formic acid, glycolic acid, acetic acid and carbon dioxide
were produced. These low molecular weight compounds should be liberated from the muconic acid typestructure or its delivertives which were produced by the oxidative cleavage of aromatic ring during chlorine
bleaching.
1997-P01
脱成分処理によるコルク細胞壁微細構造の変化
白井伸侍、吉永 新、藤田 稔
京都大学大学院農学研究科
Ultrastructure and histochemistry of phellem cell wall after solvent extraction and depolymerizations
Shinji Shirai, ArataYoshinaga, Minoru Fujita
Faculty of Agriculture, Kyoto University
Abstract:
Phellem, or cork tissue, of tree bark is well known to have suberized cell walls. It is acceptedthat suberin layers have polymeric suberin and soluble waxes, and that they appear as a fine lamellar structure intransmission electron microscopy. In this study, to clarify the relationship between chemical components andfine lamellar structure, removing process of cell wall components were observed in detail. Wax extracting withchloroform-methanol mixture at room temperature did not affect the lamellar structure, Whereas electrontranslucent lamellae are not observed after the extraction at 60ºC. KOH saponification for a brief time disrupted
partially the lamellar structure. Possible explanadons for these observations are discussed.
1997-P02
ニトロベンゼン酸化後のヒノキ材細胞壁の構造
大野清三、吉永 新、藤田 稔
京都大学大学院農学研究科
Structure of cell walls after nitrobenzene oxidation in Camaecyparis obtusa Endl
Seizo Ohno, Arata Yoshinaga, Minoru Fujita
Graduate School of Agriculture, Kyoto University
Abstract:
In alkaline nitrobenzene oxidation, degree of condensation in lignin has been evaluated fromtotal yields of the oxidation products. The condensed units in lignin is expected to be resistant to thenitrobenzene oxidation. To clarify delignification process, wood sections after nitrobenzene oxidation withvarious reaction time were observed under an UV microscope, a SEM, and a TEM. As a result, the major part oflignin was removed from cell walls by the oxidation. This result suggested that condensed lignins were removed
from cell walls by the cleavage of non-condensed units.
1997-P03
ニトロベンゼン酸化後の数種の広葉樹材細胞壁の構造
吉永 新、藤田 稔
京都大学大学院農学研究科
Structure of cell walls after nitrobenzene oxidation in several hardwoods
Arata Yoshinaga, Minoru Fujita
Graduate School of Agriculture, Kyoto University
Abstract:
Alkaline nitrobenzene oxidation has been used as a useful means of characterizing monomericcomposition and also degree of condensation of lignin. However, syringaldehyde / vanillin molar ratio (S/Vratio) obtained from the nitrobenzene oxidation provides information on only a part of lignin. To clarify
behavior of the whole lignin during nitrobenzene oxidation, lignin distribution in cell walls were examined on
several hardwoods after the nitrobenzene oxidation using UV microscopy and transmission electron microscopy.
As a result, in both vessel elements and wood fibers, the major part of lignin was removed from cell walls by theoxidation.
1997-P04
ラジオトレーサー法によるリグニン試料調製中のペクチンおよびキシランの挙動の解明
今井貴規、中井陽子、安田征市
名古屋大学農学部
295

Behaviors of pectin and xylan during lignin preparations studied by radiotracer technique
Takanori Imai, Youko Nakai, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
Pectin and xylan were labeled with l4C and 3H respectively by administration of D-glucuronic
14
acid-[6- C] and myo-inositol-[2-3H] to a growing stem of magnolia. The doubly radio-labeled wood meal was
subjected to preparations of Klason lignin and milled wood lignin (MWL), and the radioactivities of the various
fractions were determined to compare the behaviors of pectin and xylan during the preparations. Value of 3H/14Cof the Klason lignin was smaller than that of original wood meat, and the value of the soluble part was larger
that of the original. While, the 3H/14C value of the MWL fraction was smaller than that of the original, and thevalue of the lignin-carbohydrate-complex (LCC) fraction was near to the original value. These results indicatethat pectin and xylan behaved differently during the lignin preparations, and pectin were ready to remain in
Klason lignin and MWL compared with xylan.
1997-P05
リグニン前駆体とペルオキシダーゼの親和性と反応性
土橋英紀、伊藤岐仁、重松幹二、棚橋光彦
岐阜大学農学部
Affinities and reactivities between monolignols and peroxidase
Hidenori Tsuchihashi, Michihito ltoh, Mikiji Shigematsu, Mitsuhiko Tanahashi
Faculty of Agriculture, Gifu University
Abstract:
To clarify biosynthetic process of lignin, we studied affinities and reactivities between
monolignols (p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol and horseradish peroxidase (HRP).
Affinities and reactivities were defined as k+1/k−１ and k+2 of enzyme reaction, respectively. Affinities andreactivities between monolignols and HRP were reduced by increases number of methoxyl groups. However, thereduction of reactivity was extremely larger compared with the reduction of affinity.
1997-P06
フェノール性 β-O-4 型ジリグノール合成法の改良
置田恭子、飛鳥井雅倫、田中 愛、杉下千洋、河合真吾、大橋英雄
岐阜大学農学部
The convenient synthetic method of β-O-4 dilignols
Kyoko Okita, Masanori Asukai, Ai Tanaka, Kazuhiro Sugishita, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
Lignin substructure model compounds, especially β-O-4 dilignols, play important role forbiodegradation and structural studies of lignin. Many synthetic routes were reported, but these methods needchloric solvents which have been forbidden for environment problems, different protecting groups for thereactivity between guaiacyl and syringyl nuclei and/or strict anhydrous condition. To make up for suchdisadvantages, we tried a few modification based on method of Adler
and Eriksson. This convenient method has relatively short reaction time and high yields without strict anhydrous
conditions, chloric solvents and drastic reagents.
1997-P07
近赤外フーリエ変換ラマン分光法によるリグニン中の α およぴ γ 位のカルボニル基の定性および定量
高山 幸、割石博之、田中浩雄
九州大学農学部
FT Raman spectroscopic characterization of carbonyl groups in lignin
Miyuki Takayama, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
A near infrared fourier transform Raman (NIR-FTR) spectroscopic technique was utilized tocharacterize lignin. The ν(C=O) band, which could be a good monitoring probe to follow wood deterioration,
can be seen as an isolated sharp band with medium intensity on NIR-FTR spectra of wood. On the other hand, it
has been known to give a broad absorption with strong intensity on FTIR spectra. DHP prepared fromconiferaldehyde exhibited a band at 1620 cm-1, while DHP prepared from coniferyl alcohol did not show thisband. In NIR-FTR spectra of MWL and wood meals 1620cm-1 disappeared as reduction with NaBH4. Fromthese results, this band was assigned to γ-carbonyl band.
296

1997-P08
Cloning of novel cytochrome P450 monooxygenase in quaking aspen (Populus tremuloides)
Keishi Osakabe, Vincent L. Chiang
Plant Biotechnology Research Center, School of Forestry, Michigan Technological University
Abstract:
Using a modified mRNA differential display technique to analyze differentially expressed P450
genes in the 6th to 10th internodes that were absent in the 1st to 4th internodes of young aspen shoots, wecloned a full-length cDNA (asc6), which encodes a typical P450 of 508 amino acids. The deduced asc6 protein
sequence shows a less than 40% sequence identity with all other known plant P450s in DNA databases. Thus,
asc6 can be considered to represent a novel class of P450.
1997-P09
カワラタケ（Coriolus versicolor）菌体外粗酵素によるカテキン類の変換とその Gtase 阻害活性
西田容子、光永 徹、船岡正光
三重大学生物資源学部
Conversion of catechins by the extracellular enzymes of Coriolus versicolor and inhibitory action of converted
compounds on GTase
Yoko Nishida, Tohru Mitsunaga, Masamitsu Funaoka
Faculty of Bioresources, Mie University,
Abstract:
The chemical structures of bioconverted compounds from catechins by Coriolus versicolor andtheir inhibitory activities on glucosyltransferase (GTase), relating to the generation of dental caries are examined.
Dimeric compounds Y-2, Y-3 from (+)-catechin and trimer Y-4, dimer Y-5 from (-)-epicatechin were produced.
According to the NMR data, oxidative coupling occurred between A ring and B ring of catechins to generate a
conjugated carbonyl group in the molecules. In spite of the dimeric classes the converted compounds showed
high inhibitory activities on GTase, especially Y-3 and Y-5 were remarkable. The MM2 energy calculation ofthese compounds showed a good correlation between stretch-bend energy and GTase inhibitory activity.
Therefore, it was presumed that the planar and strained structure is one of the important factor on GTase
inhibitory action.
1997-P10
CAD 遺伝子を導入したタバコでの CAD の分布
伊藤真記*1、高部圭司*1、藤田 稔*1、佐藤 茂*2、柴田大輔*2、日尾野隆*3*1
京都大学大学院農学研究科、*2 三井植物バイオ研究所、*3 王子製紙株式会社森林資源研究所
Localization of CAD in CAD gene induced tobacco cell
Masaki Ito*1, Keiji Takabe*1, Minoru Fujita*1, Shigeru Sato*2, Daisuke Shibata*2, Takashi Hibino*3*1Graduate School of Agriculture, Kyoto University, *2 Mitsui Plant Biotechnology Research Institute,*3
Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
Considerable works has revealed the presence of enzymes involved in lignin biosynthesis, andthe biosynthetic pathway of lignin is, now, generally accepted. However, thelocalization of each enzyme in the cell, the regulation of the synthesis of each enzyme and the transporting
mechanism of lignin precursors are unresolved. Cinnamyl alcohol dehydrogenase (CAD) is the final enzyme forthe synthesis of monolignols. This enzyme catalyzes the reduction of cinnamaldehydes to their corresponding
cinnamyl alcohols. Immunocytochemistry revealed the difference of CAD distribution between the normal
tobacco cell and the CAD gene induced tobacco cell. The latter showed the remarkable increase of labelling in
cyto-sol. The labelling was also observed on the cell wall in both cells. From above results, localization and roleof CAD were discussed.
1997-P11
植物培養細胞を用いたバイオトランスフオーメーションによる有用物質の生産
坪田弘志、伊藤和貴、橘 燦郎
愛媛大学農学部
Production of useful substances by biotransformation with plant cell cultures
Hiroshi Tsubota, Kazutaka ltoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Production of pinoresinol diglucoside from pinoresinol by cell suspension cultures of Coffea
297

arabica was tried. From the results of HPLC analyses of the reaction products, we found that pinoresinol
diglucoside was produced from pinoresinol in the maximum yield of 33.6% by the culturesof C. arabica. We also found that the concentrations of the substrate added to the cultures was lower, the yieldsof the glucoside was higher. However, the yields of the glucoside was higher. However, the yields of the yieldsof the glucoside decreased with the incubation time.
1997-P12
数種の植物懸濁培養細胞を用いたフェノール性化合物のバイオトランスフオーメーション
好川 恵、光度知代、伊藤和貴、橘 燦郎
愛媛大学農学部
Biotransformation of phenol compounds by some plant cell suspension cultures
Megumi Yoshikawa, Tiyo Mitsuhara, Kazutaka ltoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Production of phenol glucosides from two phenols, 4-methoxy phenol and scopoletin by cellsuspension cultures of Coffea arabica, Nicotiana tabacum and Vinca rosea were tried. From the results of
HPLC analysis of each reaction product, we found that methylarbutin, phenolic glucoside of 4-methoxy phenol
was produced from 4-methoxy phenol in the maximum yield of 22.7 % and 15.6 % by the cell suspension
cultures of C. arabica and N. tabacum, respectively. Scopolin, glucoside of scopoletin could be produced fromscopoletin by the cell suspension cultures of V. rosea, however, the maximum yield of scopolin was 2.6 % of theadded substrate.
1997-P13
原子間力顕微鏡を用いたクラフトパルプ表面の観察 —脱リグニンが表面性状に及ぽす影響—
岡本哲明、飯塚堯介
東京大学大学院農学生命科学研究科
Observation of the surface of kraft pulp fibers by atomic force microscopy, — Influence of deligniflcation on
the character of the surface of kraft pulp fibers
Tetsuaki Okamoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
The surfaces of unbleached kraft pulp and some treated kraft pulp fibers were observed bycontact mode AFM in the air. Clear and high-resolution images of AFM of fine fibrils were obtained. The size offine fibrils was estimated to be 2-5nm according to the artifact by tip-sample convolution. Apparent swelling offine fibrils was observed in the case of Cl2-alkali treated sample probably due to the removal of lignin andhemicellulose during the treatment.
1997-P14
酸素漂白過程における共酸化現象の評価
童 国林、横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Oxygen oxidation of non-phenolic lignin units by a co-oxidation mechanism
Guolin Tong, Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Kraft lignin and isolated residual lignin from unbleached softwood kraft pulp were subjected tooxygen-alkali oxidation, and the extent of the oxidation were evaluated by permanganate consumption ofoxidized lignin. The residual lignin was much more easily oxidized by oxygen-alkali than kraft lignin. Threephases are observed during the oxidation of the isolated residual lignin. The first phase was the fastest and mostof electrons (about 5) were lost in this phase. The lost electrons during total three phases were 9 per lignin unit.
Model experiments by the use of phenolic and non-phenolic lignin model compounds confirmed that even a
non-phenolic unit can be oxidized during oxygen-alkali treatment by the co-oxidation mechanism. However, theextent of oxidation of the model system which contains equimolar amount of phenolic model and non-phenolicmodel compound was much smaller than the extent of oxidation of the isolated residual lignin.
1997-P15
生ゴミ処理スギチップのリグニン、ノルリグナンの変化とパルプ化に及ぼす影響
島田謹爾*1、加藤 厚*1、富村洋一*1、真柄謙吾*1、大原誠資*1、石原光朗*1、福田清春*2
298

*1

森林総合研究所、*2 東京農工大学農学部
Changes of lignin and norlignans of Sugi (Cryptomeria japonica) chips during the garbage treatment and theireffects on kraft pulping
Kinji Shimada*1, Atsushi Kato*1, Yoichi Tomimura*1, Kengo Magara*1, Seiji Ohara*1, Mitsuro Ishihara*1,
Kiyoharu Fukuda*2*1
Forestry and Forest Products Research Institute, *2Faculty of Agriculture, Tokyo University of Agriculture andTechnology
Abstract:
To investigate the changes of lignin and norlignans of Sugi (Cryptomeria japonica) chips
during the treatment of garbage, the alkaline-nitrobenzene oxidation products were analyzed by means of
GLC,1H and 13C-NMR spectroscopy. In addition, the effects of the changes of them on kraft pulping was also
examined. Following results were obtained. 1) The yield of total aldehydes on nitrobenzene oxidation decreasedin the treated chips. 2) The yields of the oxidation products of treated chip were higher for
p-hydroxybenzaldehyde and lower for methoxyl group than those of non-treated chip. This result implies thatthe polymerized norlignans have remained in the chip and decomposed on nitrobenzene oxidation to yield
p-hydroxybenzaldehyde. 3) In the initial stage of kraft pulping, the treated chip was well cooked and thedelignification proceeded faster than the non-treated chip. In the last stage, however, the large amounts of lignin
remained in the pulp. 4) Both the changed lignin and norlignans could not be easily removed during the pulping
process.
1997-P16
担子菌による含硫黄へテロ環化合物の変換 —基質認識および代謝応答—
一瀬博文、中溝真啓、割石博之、田中浩雄
九州大学農学部
Biotransformation of sulfur containing heterocyclic compounds by basidiomycetes, - Substrate recognition andmetabolic response
Hirofumi lchinose, Masahiro Nakamizo, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
Lignin degrading basidiomycete Coriolus versicolor was utilized to degrade sulfur containing
heterocyclic compounds which are recalcitrant compounds found in fossil resources. The transformation ofthese compounds by C, versicolor were occurred in different manner under different metabolic conditions.
Nonaromatic compounds such as 2-hydroxymethylthiophene were metabolized in primary metabolic conditions
and utilized as a sulfur source for growth. While aromatic compounds such as 2-hydroxymethylbenzothiophene
and 4-methyldibenzothiophene were metabolized as xenobiotic detoxification. It was suggested that substrate
recognition controls the metabolic response.
1997-P17
担子菌原形質膜機能解析モデルへのプロトプラストの適用
小林芳徳、割石博之、田中浩雄
九州大学農学部
Utilization of fungal protoplasts as a plasma membrane model for functional analysis
Yoshinori Kobayashi, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract;
White-rot basidiomycetes are capable of degrading lignin. The extracllular lignin degrading
enzymes catalyze the depolymerization of lignin. But a little is known about mechanism of uptake of lignin
degradation fragments. As an active plasma membrane model, we attempted to utilize protoplasts. In this study,
we analyze the reduction of quinones and uptake of lignin degradation fragment using protoplasts prepared froma brown-rot basidiomycete. 2,6-Dimethoxy- 1,4-benzoquinone and 2,5-dihydroxy-1,4-benzoquinone wereeffectively
reducedbyprotoplasts
andformed
1,4-dihydroxy-2,6-dimethoxybenzene
and1,2,4,5,-tetrahydroxybenzene, respectively. Syringaldehyde, syringic acid and protocatechuic acid was notconverted into other compounds. However, only protocatechuic acid was detected intracllularly, showing theselective permeability of fungal plasma membrane.
1997-P18
絶対嫌気性ルーメン細菌による非フェノール性ベンジルエーテルの解裂
渡辺隆司*1、梶川 博*2、工藤 博*2、近藤恒夫*3、城代 進*4、中島由美*1、本田与一*1、桑原正章*1
299

*1

京都大学木質科学研究所, *2 農林水産省畜産試験所，*3 農林水産省東北農業試験所、*4 近畿大学農学部
Cleavage of non-phenolic benzyl ether bonds by strictly anaerobic rumen bacteria
Takashi Watanabe*1, Hiroshi Kajikawa*2, Hiroshi Kudo*2, Tsuneo Kondo*3, Susumu Johdai*4, Yumi Nakajima*1,
Yoichi Honda*1, Masaaki Kuwahara*1*1
Wood Research Institute, Kyoto University, *2National Institute of Animal Industry, *3Tohoku National
Agricultural Experiment Station, *4Faculty of Agriculture, Kinki University
Abstract:
Fluorescent benzyl ether model compunds with non-phenolic unit were chemically synthesized.
The models were incubated with rumen microorganisms under anaerobic conditions in the presence and absenceof bactericidal and fungicidal antibiotics. Fluorescent spectrometry of the culture fluid showed that the
non-phenolic benzyl ethers were rapidly cleaved by strictly anaerobic rumen bacterial fraction.
1997-P19
白色腐朽菌によるポリエチレンの分解（III）
飯吉由佳、堤 祐司、西田友昭
静岡大学農学部
Polyethylene degradation by white rot fungi
Yuka Iiyoshi, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract;
We previously reported that polyethylene degradation by manganese peroxidase (MnP) required
Tween 80 or 20 and Mn(III) generated from Mn(II) in the MnP catalytic cycle but not H2O2 which isrecognised to be indispensable for the generation of Mn(III) by MnP. In this study, therefore, Mn(III) formation
by MnP without exogenous H2O2-supply was investigated. Neither Tween 80 nor Tween 20 affected on the
Mn(III) formation by MnP very much. The Mn(III) formation was slightly accelerated under oxygen atmosphere,
but was strongly restrained under nitrogen atmosphere. Addition of catalase into MnP reaction mixture todecompose endogenous H2O2 did not inhibit the Mn(III) formation. These results indicate that Mn(III)formation by MnP in polyethylene degradation is dependent on oxygen under the condition without exogenous
H2O2.
1997-P20
Differential Display 法による、カワラタケの有害化学物質分解関連遺伝子の検索
飯村洋介、辰巳憲司
工業技術院資源環境技術総合研究所
Isolation of mRNAs induced by a hazardous chemical in white-rot fungus, Coriolus versicolor, by differential
display
Yosuke Iimura, Kenji Tatsumi
Department of Hydrospheric Environmental Protection, National Institute for Resources and Environment
Abstract;
White-rot fungus Coriolus versicolor, a ligninolytic basidiomycete, has been studied because of
its ability to degrade hazardous chemicals. In this study, we searched for genes that are induced by a hazardous
chemical using the mRNA differential-display technique arid C. versicolor IFO30340 that has been exposed topentachlorophenol (PCP). Five cDNA frgments were cloned and the DNA sequences of two fragments wereanalyzed in further detail. The clones corresponded to novel genes that have not previously been identified in C.
versicolor. One of the cDNAs exhibited homology to a heat shock protein. The expression of the gene was
up-regulated in PCP-treated C.versicolor.
1997-P21
リグニン系土壌改良剤の開発（6）—改質リグニンの金属イオンとの相互作用—
斉藤京子、飯塚堯介
東京大学大学院農学生命科学研究科
Development of lignin derivatives as soil conditioning agents (6), - Interaction between modified lignins andmetal ions
Kyoko Saito, Giosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract;
Soil conditioning agents to remove toxic metal ions released in acid soil were prepared byradical-sulfonation and alkaline-oxygen treatment of kraft lignin. Interaction between modified lignins andmetal ion (Al3+) was investigated using potentiometric titration. It is well known that proton is released by300

coordination of acidic functional groups in organic compounds to metal ion. The coordination bond between
lignin and Al was estimated by the change of shape of titration curves. It was suggested that carboxyl andphenolic groups in modified lignins behave as a ligand, because formation of coordinate bond was clearlyobserved in the complex of Al and modified lignin by only alkaline-oxygen treatment.
1997-P22
Daphne odora におけるリグナン生合成について
奥西智哉、梅澤俊明、島田幹夫
京都大学木質科学研究所
Lignan biosynthesis in Daphne odora
Tomoya Okunishi, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:(-)-Pinoresinol and (+)-matairesinol were isolated from Daphne odora. These lignans were(almost) optically pure. In addition, lariciresinol, secoisolariciresinol and isolariciresinol weredetected by GC-MS. [9,9-2H2, OC2H3]Coniferyl alcohol was administered to this plant, and incorporation of
deuterium atoms into several lignans were observed. The results suggested that the step to produce opticallypure lignan is the formation of pinoresinol from coniferyl alcohol in D. odora.
1997-P23
8-O-4’型ネオリグナンの Fusarium solani M-13-1 による変換（第 2 報）
岡本茂樹、片山健至
香川大学農学部
Transformation of 8-O-4' neolignans by Fusarium solani M-13-1, II.
Shigeki Okamoto, Takeshi Katayama
Faculty of Agriculture, Kagawa University
Abstract:∆8’-4,7-Dihydroxy-3,3’-dimethoxy-8-O-4’-neolignan was prepared by incubation of intact
Fusarlium solani M-13-1 cells with (±)- ∆8’-4-hydroxy-3,3'-dimethoxy-7-oxo-8-O-4'- neolignan in the presenceof -oxo-guaiacylglycerol--vanilfin ether. The neolignan obtained was a mixture of (-)-erythro and (+)-threo
isomers, which were enantiomerically pure. Their absolute configuration were determined with the modified
Mosher's method as (7S, 8R)-(-)-erythro and (7S,8S)-(+)-threo, which would be derived from both enantiomersof the racemic substrate. This fungal reduction seems to be highly enantioselective but of low substratespecificity, indicating that this reduction could be applied to preparation of other 8-O-4' neolignans.

301

第 43 回 （1998.10.26-27） 府中グリーンプラザ
1998-101
グニンの水酸基の新しい定量法
片平 類*1、中坪文明*1、Hou-min Chang*2*1
京都大学大学院農学研究科、*2North Carolina State University
The new method for the quantitative determination of the hydroxyl groups in lignins
Rui Katahira*1, Fumiaki Nakatsubo*1, Hou-min Chang*2*1
Graduate school of Agriculture, Kyoto University, *2North Carolina State University
Abstract:
Lignins have aliphatic hydroxy groups at C-γand C-α positions on the side chain in addition tophenolic hydroxy group at C-4 position of aromatic ring. The chemical and physical properties of lignin arealmost determined by these hydroxy groups. Therefore, it is very important to determine these hydroxy groupcontents in lignins. Several methods for quantitative determination of three hydroxy groups in lignins have beenreported. Here, we propose a new method for the quantitative analysis of these three hydroxyl groups.
1998-102
酢酸リグニンの性質及び利用
藩 学軍、佐野嘉拓
北海道大学農学部
Characterization and utilization of acetic acid lignins: Methylolation of lignin and preparation of lignin-based
adhesives
Xue-Jun Pan, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Acetic acid lignins from rice straw (R-AcL), birch (B-AcL) and fir (F-AcL) were methylolatedby three routes: direct methylolation with formaldehyde, condensation with phenol formaldehyde resins andmethylolation after phenolization. By the third route, as many as 6-8% methylol groups could be introduced into
the lignins. Thermo-setting adhesive with acceptable bonding strength was made from F-AcL in a ratio of 2: 1
(lignin to phenol). Cold-setting adhesives were also prepared with satisfactory bonding quality from both F-AcL
and B-AcL in a proportion of 2 : 1 : 1.2 (lignin/phenol/resorcinol).
1998-103
ケナフ靭皮繊維からの高粘度溶解用パルプの調製法
ビブチ・B・マズンダル、程 舟、大谷慶人、鮫島一彦
高知大学農学部
Pulping method of kenaf bast fiber for high viscosity pulp
Bibhuti B. Mazumder, Chen Zhou, Yoshito Ohtani, Kazuhiko Sameshima
Faculty of Agriculture, Kochi University,
Abstract:
In order to obtain high viscosity pulp from kenaf bast, a combination of Amox pretreatment,soda pulping under normal pressure and chlorite bleaching is found the most suitable method. The pulp
viscosity did not directly correlate to the fiber length or the carbohydrate composition of kenaf bast pulp, but it
rather depends on the treatment history of the pulping.
1998-104
酸素漂白過程における酸化反応の解析
童 国林、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Quantitative analysis of oxidation reaction during oxygen-alkali bleaching
GuolinTong, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, The Unitersitv of Tokyo
Abstract:
Residual lignin and residual hemicellulose were isolated from unbleached softwood kraft pulp.
They were separately or as a mixture, subjected to alkali treatment with or without oxygen, and the change inthe permanganate consumption during the treatment was analyzed. The permanganate consumption by theisolated residual lignin decreased to about one third of the initial value by prolonged oxygen alkali treatment
whereas it changed only to a minor extent when oxygen was absent. Contrary to this, permanganate
consumption by the isolated residual hemicellulose increased significantly during the alkali treatment without
302

regard to the presence of oxygen. This result indicates that new structures, which consume permanganate, areproduced from hemicellulose even during a weak alkali treatment such as oxygen bleaching and these can not
be oxidized by oxygen. By taking those into account, the progress and the extent of the lignin oxidation duringoxygen-alkali bleaching of kraft pulp was reevaluated.
1998-105
リグニンのオゾン酸化過程で生じるラジカル反応の抑制
真柄謙吾*1、富村洋一*1、細谷修二*1、池田 努*2*1
森林総合研究所、*2 筑波大学農林工学系
Suppression of radical reaction caused during ozonation of lignin
Kengo Magara*1, Yoichi Tomimura*1, Shuji Hosoya*1, Tsutomu Ikeda*2*1
Forestry and Forest Products Research Institute, *2Tsukuba University
Abstract:
Ozone reacts with lignin through two pathways. One is an ionic reaction which generates
muconic acid derivatives and hydrogen peroxide. The other one is a radical reaction. The first step of which is
the one electron oxidation of dissociated phenolic OH and thus the radical chain reactions are initiated. To
control the initiation of radical reactions which brings about the non-selectivity of ozone reactions, ozonation
was performed at quite low pH for the purpose of suppressing the disocciation of phenolic OH. The result
showed that even at pH 0.7, the amount of hydrogen peroxide formed by the ionic reactions was 1 mmol more
for veratryl alcohol (non-phenolic) than that for vanillyl alcohol (phenolic). To explain the difference in theyield of hydrogen peroxide, we have investigated the H2O2-stabilizing effect of MeOH since a doublet amountof MeOH was formed from veratryl alcohol and MeOH is known as a radical scavenger. Furthermore, hydrogen
peroxide is also formed by the reaction of MeOH with ozone. But, both possibilities were neglected.
1998-106
リグニン立体構造の解析を目的としたオゾン分解法の定量性の検討
秋山拓也、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Investigation of lignin stereo structure by ozonation
Takuya Akiyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Ozonation method as an analytical tool of stereo-structure of lignin was reexamined by the useof a lignin model compound veratrylglycerol-β-guaiacyl ether (VG). The yield of erythronic and threonic acids
from VG was found to be 58%, which was higher than that formerly reported. Prolonged ozonation (20 min to
120 min) did not result in a significant yield loss of these products. Contrary to this, when erythronic andthreonic acid in their free acid form were subjected to ozone treatment, their recovery decreased with prolonged
reaction time. However, if the reaction mixture were reduced by sodium thiosulfate, their recovery was
improved. Erythro and threo ratio of VG determined based on the yield of ephronic acid and threonic acid wasslightly higher than the ratio determined by 1H-NMR. Reproducibility of the GC determination of the products
was quite satisfactory when ozonation products were trimethylsililated from their ammonium salts by a mixtureof HMDS and TMSCl in DMSO.
1998-特別講演 I.
The challenges and opportunities of lignin
Wolfgang G．Glasser
Virginia Polytechnic Institute and State University
Abstract:
Lignin comprises approximately 1/4 of the earth's biomass production of estimated 1010 tops per
year. In the process of pulp and paper production, approximately one ton of lignin is separated from biomass foreach two tons of paper produced. This means that approximately 100 million tons of lignin are commerciallyseparated from biomass annually worldwide. Only about one percent of that amount is actually recovered fromspent pulping liquors for commercial, non-fuel uses. Virtually all of the approximately one million tons of lignin
co-generated from pulp and paper operations in the world annually are marketed as water-soluble lignin
sulfonate derivatives (Table I). The worldwide value of this market is estimated to be $600 million per year (1).
Lignosulfonates have captured the majority of the industrial ionic surfactant markets owing to their favorable
price/performance relationship. Prominent uses are in concrete admixtures, animal feed, oil well drilling muds,
and dust control agents. Having satisfied major commodity markets, lignosulfonate producers are now focusing
on markets for specialty water-soluble polymers. Since the majority of lignin is separated from biomass in303

non-sulfonated form, as water- insoluble polymer, the potential exists for lignin to become a competitor in themarket for structural polymers, adhesives, and composites. The use of lignin in thermosets and thermoplastics
requires a significant level of understanding regarding the structure-property relationships of the polymeric
resource. This understanding concerns in particular (a) the chemistry of the basic repeat unit structure(s); (b) thenature of the intermonomer bonds; (c) the size and weight distributions of the molecular mixture; and (d)aspects of the inter/intramolecular interactions. This paper deals with a review of the current state-of-art of thequantitative analysis of lignin's chemical and molecular structure, and on techniques qualified to characterize theperformance of lignin in thermosetting resins and in melt-processed thermoplastics.
1998 特別講演 II.
リグニン利用の現状と将来展望
町原 晃
日本製紙株式会社
The current usage of lignin and its prospects
Akira Machihara
Nippon Paper Industries Co. Ltd.
Abstract:
Currently, industry utilizes lignosulfonate (obtained from sulfite liquor) and kraft lignin(extracted from kraft black liquor). Demand for lignin products are increasing in the field such as concrete
admixtures and dye dispersants. In order to enhance the usefulness of lignin, it is essential that the features oflignin should be characterized and the original properties must be improved tobe the value added products and the mass consumption. Also, it is necessary in future to solve technicalproblems, explore new applications and continually develop the values of lignin.
1998-201
Kapok 繊維の油吸着特性と繊維の化学的・組織学的性状
堀 啓映子*1、Maxima E．Flavier*2、空閑重則*1、飯山賢治*3*1
東京大学大学院農学生命科学研究科、*2 フィリピン大学化学研研究所、*3 東大アジア生物資源環境研究センター
An excellent oil absorbent, Kapok (Ceiba pentandra (L.) Gaertn.) fibre: its fibre structural and chemical
characteristics
Keko Hori*1, Maxima E. Flavier*2, shigenori Kuga*1,OKenji liyama*3*1
Graduate School of Agriculture and Life Sciences, the University of Tokyo, *2Institute of Chemistry, theUniversity of Philippines, *3ANESC, the University of Tokyo
1998-202
リグニンと古紙を原料とする成形活性炭の吸着性能
久保智史*1、浦木康光*1、佐野嘉拓*1、陳 克利*2
*1
北海道大学農学部, *2 秋田県立農業短期大学
Adsorption property of molded activated carbon prepared from lignin and waste paper
Satoshi Kubo*1, Yasumitsu Uraki*1, Yoshihiro Sano*1, Ke-Li Chen*2*1
Faculty of Agriculture, Hokkaido University, *2Akita Prefectural College of Agriculture
Abstract:
The activated carbon (AC) with sheet shape (ACS) which was a new type of molded AC was
prepared from the mixture of isolated lignins and waste news paper. The adsorption capacities of ACSs werehigher than those of commercial powdery and granulated ACs. Particularly, ACSs prepared from acetic acidlignin (AL) showed the excellent adsorption capacity: iodine 1,350 mg/g; metylene blue 225 mg/g andp-chlorophenol 1,250 mg/g, resectively. Furthermore, p-chlorophenol adsorption rate of AL-ACSs was fasterthan that of the commercially granulaced activated carbon. These results revealed that AL was an effective
material for molded activated carbon. The ratio of internal surface to external surface area of AL-ACSs from
nitrogen sorption was much higher than that of commercial powdery AC, suggesting that the excellent
adsorption capacity of AL ACS was based on development of meso- and micro-pores which acts as adsorption
sites.
1998-203
ヒドロキシプロピル化リグノセルロースの性質
半崎亜希子、浦木康光、佐野嘉拓
304北海道大学農学部
Characteristics of hydroxypropylated lignocellulose
Akiko Hanzaki, Yasumitsu Uraki, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract;
Hydrophobically associating water-soluble polymers (HAWSP) have been focused on
their unique theological properties and the functions as inclusion compounds for drugs and proteins. HAWSP
was prepared from acetic acid pulp (AWP) by hydroxypropylation. The association of hydroxypropylated AWP(HP-AWP) was found to occur in water, and even in chloroform by TEM observation and viscometricmeasurement. The interactions between HP-AWP molecules in water and in organic solvent seemed to be due tothe hydrophobic interaction of residual lignin and to hydrogen bonding of polysacchahdes, respectively.
HP-AWP was suggested to have an excellent complexation ability to low molecular-mass compounds. With
respect to the interaction with biopolymer, HP-AWP was also indicated to play a role as a stabilizer thatprevented protease (papain) from its autolysis.
1998-204
リグニン及びリグニン関連型フェノールを原料とするエポキシ樹脂の調製と熱的性質
畠山兵衛*1、吉田考範*1、谷口 誠*1、永田 茂*1、広瀬重雄*2, 畠山立子*3*1
福井工業大学工学部, *2 物質工学研究所、*3 大妻女子大学家政学部
Preparation and thermal properties of epoxy resins derived from lignin and lignin-related phenol
Hyoe Hatakeyama*1, Takanori Yoshida*1, Makoto Taniguchi*1, Shigeru Nagata*1, Shigeo Hirose*2, Tatsuko
Hatakeyama*3*1
Fukui University of Teclmology, *2National Institute of Materials and Chemical Research,*3
Otsuma Women's University
Abstract:
Epoxy prepolymers were synthesized from alcoholysis lignin (AL), and lignin-related phenols
such as p-hydroquinone and methoxy-p-hydroquinone by reaction with epichlorohydrin.
Epoxy resins were synthesized from the above prepolymers by reaction with poly(azelaic anhydride). The molar
ratios of acid anhydride groups to epoxy groups ([AA]/[EPOXY] ratios) were varied at 10/10 and 12/10. The
thermal properties of the obtained prepolymers and epoxy resins were studied by differential scanningcalorimetry (DSC), thermogravimetry (TG) and TG-Fourier transform infrared spectroscopy (FTIR). Glasstransition temperatures (Tg's) increased with increasing [AA]/[EPOXY] ratios. Thermal degradation
temperatures (Td'’S) of epoxy resins were almost constant regardless of [AA]/[EPOXY] ratios, suggesting thatthe curing of prepolymers with poly(azelaic anhydride) does not affect Td Values. The intensities of absorption
peaks at 2900 cm-1 (CH) and 1730 cm-I (C=O) in IR spectra of the evolved gases during thermal degradation
increases with increasing [AA/[EPOY] ratios.
1998-205
分子状酸素によるアルデイトール類の直接酸化
前川 巌、横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Direct oxidation of alditols by molecular oxygen
Iwao Maekawa, Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Alditols can be easily oxidized by oxygen-alkali treatment without any active oxygen
generator such as a phenolic compound. When alditol (xylitol, D-arabinitol or ribitol) was treated at 95ºC, theoxidation was quite rapid and no induction period seemed to be present until the oxidation started. However,when the reaction was carried out at 55ºC or 70ºC, the presence of induction period was clearly observed. The
induction period at these temperatures increased when a small amount of a known stabilizer of peroxides(diethylenetriaminepentamethylene-phosphonic acid, DTMPA) was added to the reaction system. Theseobservations suggest that the oxidation of alditols during oxygen-alkali treatment proceeds by an auto-oxidation
type reaction, which consists of an initiation reaction (direct reaction of alditols and molecular oxygen) and thefollowing chain oxidation type reaction. The fact that the addition of DTMPA did not result in a visualization of
induction period at 95ºC seems to indicate that the direct reaction with molecular oxygen is much more
important in the oxidation of alditols at this temperature than at lower temperature, but no direct proof for thiswas obtained.
1998-206305

リグニンの熱分解：グァイアシルグリセロールおよびコニフェリルアルコール末端基由来の熱分解生成物
黒田健一
筑波大学農林工学系
Analytical pyrolysis of lignin: pyrolysis products derived from guaiacylglycerol moieties and coniferyl
alcohol-end groups
Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Pyrolysis products of acetylated lignin model compounds and reference lignins were analyzed
to determine guaiacylglycerol moieties and coniferyl alcohol-end groups. Guaiacylglycerol-β-coniferyl ether
tetraacetateproduced
3-(4-hydroxy-3-methoxy-phenyl)propyl
acetate1,3-(4-acetyloxy-3-methoxyphenyl)-propyl acetate 2, and 3-(4-acetyloxy-3- methoxyphenyl)-prop-2-enyl acetate
3. Guaiacylglycerol-β-guaiacyl ether triacetate produced 2 and 3. These findings suggested that 1 is indicative
for coniferyl alcohol-end groups, and 2 and 3 for guaiacylglycerol moieties. Acetates of reference lignins,
synthetic lignins, Japanese cedar wood, its dioxane lignin, and Japanese Douglas fir wood, also produced 1-3.
Large differences in yields of 1-3 were observed among the acetylated lignins. Pyrolysis using acetylated
samples is effective for analyzing guaiacylglycerol moieties and coniferyl alcohol-end groups in lignins.
1998-207
熱分解ガスクロマトグラフィーによるユーカリ中のリグニンの樹幹内変異の解析
横井裕明*1、石田康行*1、大谷 肇*1、柘植 新*1、園田哲也*2、小名俊博*2*1
名古屋大学大学院工学研究科、*2 王子製紙株式会社森林資源研究所
Characterization of within-tree variation of lignin in Eucalyptus camaldulensis by pyrolysis-gas
chromatography
Hiroaki Yokoi*1, Yasuyuki Ishida*1, Hajime Ohtani*1, Shin Tsuge*1, Tetsuya Sonoda*2, Toshihiro Ona*2*1
Graduate School of Engineering, Nagoya University, *2Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
Pyrolysis-gas chromatography (Py-GC) using a vertical micro furnace pyrolyzer was applied tothe detailed estimation of “the within-tree variation” of the ratio of syringyl and guaiacyl units (S/G ratio) for
lignin in Eucalyptus camaldulensis. On the pyrogram of the Eucalyptus obtained at 450ºC, many characteristic
peaks derived from syringyl and guaiacyl units of lignin were reproducibly observed together with those from
cellulose and hemicellulose. On the basis of the intensities of these characteristic peaks, "the within-tree
variation" of the S/G ratio for lignin were estimated rapidly using g order of the powdered tree sample, and theobtained results were also discussed comparing with those obtained by the thioacidolysis method.
1998-208
コーヒー酸の酸化的二分子縮合における反応機構の考察
田崎弘之、田口大祐、鍋田憲助
帯広畜産大学生物資源学部
Reaction mechanism of oxidative bimolecular condensation of caffeic acid
Hiroyuki Tazaki, Daisuke Taguchi, Kensuke Nabeta
Department of Bioresource Science, Obihiro University of Agriculture and Veterinary Medicine
Abstract:
We examined a formation of furofuran-type lignan 2,6-exo-bis(3,4-dihydroxyphenyl)3,7-dioxabicyclo[3.3.0]octane-4,8-dione (4) from 3,4-dihydroxycinnamic acid (caffeic acid, 1) with NaIO4, as amodel of bimolecular condensation. The first step of bimolecular condensation was thought as the oxidation of 1
to highly reactive o-quinone (3). It was confirmed by NMR analysis and the reaction of 3 in MeOH with
1,2-phenylenediamine to produce phenazine derivative. Further labeling studies by using [8-13C] 1 revealed thatthe condensation occurred between 1 and 3.
1998-209
クロマツあて材リグニンの形成と構造
斉藤香織、福島和彦、安田征市
名古屋大学農学部
Formation and structure of lignin in the compression wood of Pinus thunbergii
Kaori Saito, Kazuhiko Fukushima, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
Lignin is considered to be different in coupling type of its component according to a kind of cell306

or a position of cell wall. In this study, we analyzed lignin by thioacidolysis at the level of monomer or dimer.
We prepared 50 mm-thick tangential sections (cambial zone to mature xylem) from compression or normal
wood of Pinus thunbergii, and analyzed how lignin deposit in the process of cell wall differentiation insecondary xylem. By the dimer analysis, heterogeneity of the inter units linkage in lignin was suggested.
1998-210
The behaviors of deuterium labeled monolignols and monolignol glucoside in lignin biosynthesis
陳 方、福島和彦、安田征市
名古屋大学農学部
Fang Chen, Kazuhiko Fukushima, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
To examine the different behavior of monolignol and monolignol glucoside in lignin
biosynthesis, pentadeutero[γ, γ,-D2,OMe-D3]-coniferyl alcohol and pentadeutero[γ,γ-D2, OMe-D3]-coniferin
were synthesized and fed to growing trees. The difference in patterns of incorporation of labeled precursors wasstudied by GC-MS. The results indicate that both precursors can be incorporated into lignin effectively, but thelabeled coniferyl alcohol can be incorporated into lignin more directly, resulting high proportion of 5D-labeledguaiacyl and syringyl units in newly formed xylem. On the other hand, labeled coniferin tends to beincorporated into 4D-labeled guaiacyl and syringyl units, releasing oneγ-deuterium atom due to oxidation.
1998-211
In situ hybridization 法によるリグニン生合成関連遺伝子の発現解析
島田武明*1、川合伸也*2、諸星紀幸*1*1
東京農工大学大学院生物システム応用科学、*２東京農工大学農学部
Expression analysis of lignin-biosynthesis related genes with in situ hybridization
Takeaki Shimada*1, Shinya Kawai*2, Noriyuki Morohoshi*1*1Graduate School of Bio-application and Systems Engineering, Tokyo Universityof Agriculture and Technology, *2Faculty of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
We have attempted to construct the experimental system of in situ hybridization to detect theexpression of lignin-biosynthesis related genes in, Populus kitakamiensis, hybrid aspen. In situ hybridization is
widely employed to analyze tissue-specific gene expressions in both plants and animals. With this method, theanalysis of tissue-specific gene expression can be achieved in very short tern, comparing to other methods suchas promoter-GUS assay and so on. In the this report, we used one year old stems of P. kitakamiensis anddetected the pal expression in several phloem cells locating cambial zone nearby. This result partially coincidedwith that of promoter-GUS assay which was conducted formerly. Although pal expression was detected, now ye
are thinking the signal was not intact, therefore further study is necessary to decide the strict localization of pal
mRNA and also the identification of isozymes.
1998-212
ダイオキシン分解菌 V2 からのリグニンペルオキシダーゼによるダイベンゾフランの分解
大川浩樹、伊藤和貴、橘 燦郎
愛媛大学農学部
Degradation of 2,4,8-trichlorodibenzofuran by lignin peroxidase produced by fungus V2 having ability for
degradation of dioxins
Hiroki Ohkawa, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
The time-course of the activities of lignin peroxidase (Lip) and dioxygenase from fungus V2
separated by a screening from natural world and a wood-rotting fungus Phanerochaete chrysosporium having
ability for degradation of dioxins (2,7-Dichlorodibenzo-p-dioxin) was measured in connection with thedegradation rate of 2.4.8-Trichlorodibenzofuran (2,4,8-TCDF) with two fungi. We tried to isolate Lip by fungus
V2 separated by the screening method. Three Lip fractions were purifled by DEAE-BioGel A. Three Lip
fractions ( I , II. III) degraded 10.5% to 49.7% of
2,4,8-TCDF. The maximum degradation rate of 2,4,8-TCDF was obtained by Lip fraction II-9 when the
incubation was conducted for 3 hours after addition of 0.25 mmol of 2,4.8-TCDF to the fraction. The activity of
Lip from fungus V2 was higher in the initial stage of the culture. the degradation rate of 2.4.8-TCDF was larger.
The activity of Lip from fungus V2 was decreased with the incubation time. the activity kept a constant level
after the incubation for 15 days. However, the degradation rate of 2,4.8-TCDF was increased after the307incubation for 15 days. The degradation rate of 2,4,8-TCDF was increased with the increase in the activity ofdioxigenase from fungus V2. The activity of dioxygenase from fungus V2 was higher, the degradation rate of
2,4,8-TCDF was larger. These results suggested the participation of both Lip and dioxygenase in degradation of
2.4.8-TCDF.
1998-213
白色腐朽菌のリグニン分解に関与する脂質過酸化に関する研究
榎 牧子 *1 、 片 山志歩子 *1 、 仲 亀誠司 *1 、 本 田与一 *1 、 渡 辺隆司 *1 、 桑原正章 *1 、 Karin Koller*2 、 Kurt
Messner*2*1
京都大学木質科学研究所、*2 ウィーン工科大学生物化学工学・微生物研究所
Studies on lipid peroxidation during lignin degradation by white-rot fungi
Makiko Enoki*1, Shihoko Katayama*1, Seiji Nakagame*1, Karin Koller*2, Kurt Messner*2, Yoichi ttonda*1,
Takashi Watanabe*1, Masaaki Kuwahara*1*1
Wood Research Institute, Kyoto University, *2Research Institute for Biochemical Technology andMicrobiology, University of Technology, Vienna
Abstract:
White-rot fungus Coriporiopsis subvermispora is known to decompose cell wall lignin withoutmorphological changes of wood cell walls. Since enzymes cannot penetrate inside of the wood cell walls during
this stage, this reaction must be catalyzed by low molecular mass compounds. To elucidate the selective
ligninolytic system, we focused on extracellular peroxidizable compounds such as lipid since the peroxidizable
compounds can generate active radicals inside of wood cell walls even at the site far from enzymes. Analysis ofperoxidizable compounds prduced by C. subvermispora is reported.
1998-214
化学修飾法を用いたリグニンペルオキシダーゼ基質酸化機構の解析
城島 透、割石博之、田中浩雄
九州大学農学部
Spectroscopic and kinetic characterization of chemically modified lignin peroxidase
Toru Johjima, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
To investigate a reaction mechanism, chemically modified lignin peroxidases were preparedusing N-bromosuccinimide (Lip-NBS) and 1-ethyl-3-(3-dimethylaminopropyl)-carbo- diimide with and without
2-aminoethanesulfonic acid (S- and EDC-LiP). Reactivity of LiP against veratryl alcohol (VA),
2,6-dimethoxyphenol, and ferrocytochrome c was remarkably reduced by thechemical modification. On the other hand, reactivity against 2,2’-azinobis-(3-ethylbenzthiazoline- 6-sulfonate),
KI, and ferrocyanide was almost unchanged upon the modification. This observation strongly suggests that LiP
may have two or more substrate oxidation sites. To further characterize
the mechanism, steady state kinetic parameters of modified LiPs on VA oxidation were determined, indicatingthat the NBS modification reduces all electron transfer efficiency rather than a substrate binding. The effects ofthe chemical modification on the role of VA in LiP oxidation of ferricyto- chrome c were determined. The
extents of the inhibition by the chemical modification using NBS and EDC against VA oxidation andVA-supported oxidation of ferricytochrome c were very similar, suggesting that VA binding sites may be thesame when acting as a reducing substrate and as a
cofactor during ferricytochrome c oxidation.
1998-215
デンドリティツクポルフイリンの触媒するペルオキシダーゼ型反応
山中 猛、堤晋一郎、割石博之、田中浩雄
九州大学農学部
Dendritic porphyrin designed for eatalyzing peroxidative reaction
Takeshi Yamanaka, Shinichiro Tsutsumi, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
Lignin peroxidase (LiP) oxidizes a variety of nonphenolic aromatic compounds including
chlorinated dibenzo-p-dioxins and biphenyls to their aryl cation radicals. To maximize LiP-catalyzing oxidationof those pollutants, a stable one electron oxidation activity in organic media has been expected. Using aniron-meso-tetra(4-carboxyphenyl)porphine as a core, which has higher redox potential than theiron-protoporphyrin IX, the dendritic porphyrin was synthesized to mimic LiP catalysis. The relationships308

between the size of dendron (generation 1 (G1) to G4) and LiP activity, peroxide-derived inactivation, andkinetic characteristics were examined. G4-dendritic porphyrin shows a stable one-electron oxidation activity inorganic media via a typical peroxidase catalytic cycle. The addition of imidazole derivatives improved either
LiP or peroxidase activity of G4-dendritic porphyrin.
1998-216
白色腐朽菌によるポリエチレンの分解（IV）—過酸化水素非存在下での MnP による Mn(III)の生成機構—
飯吉由佳、堤 祐司、西田友昭
静岡大学農学部
Polyethylene degradation by white-rot fungi (IV), -Formation of Mn(III) by MnP in the absence of hydrogen
peroxide
Yuka Iiyoshi, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University,
Abstract:
We have investigated the degradation of high-molecular-weight polyethylene membrane by(MnP). The previous study clearly indicated that Mn(III) formed by MnP function closely relates to thepolyethylene degradation in the absence of hydrogen peroxide. We, therefore, studied the mechanism forformation of Mn(III) by MnP without hydrogen peroxide supply during polyethylene degradation. The Mn(III)formation was completely inhibited under nitrogen atmosphere and was accelerated by addition of Mn(III) or
Mn(IV) in the reaction system. The effect of the Mn(III)-addition was also restrained under nitrogen atmosphere.
These results indicate that the reaction of oxygen, Mn(III), and MnP initiates the MnP catalytic cycle. The
peroxidation of unsaturated lipid did not participate in the formation of Mn(III) by MnP nor polyethylene
degradation in the our system.
1998-217
Phanerochaete sordida YK-624 株のマンガンペルオキシダーゼ遺伝子について
廣末慎嗣*1、平井浩文*1、渡辺吉雄*2、深津武馬*1、倉根隆一郎*1*1
NEDO 複合・工業技術院生命研究所、*2NEDO 複合・メルシヤン中央研究所
Manganese peroxidase genes from the white-rot fungus Phanerochaete sordida YK-624
Shinji Hirosue*1, Hirofumi Hirai*1, Yoshio Watanabe*2, Takema Fukatsu*1, Ryuichiro Kurane*1*1
NEDO Bioconsortia Program, National Institute of Bioscience and HumanTechnology, Agency of Industrial
Science and Technology, *2Central Research Laboratory, Mercian Corp.
Abstract:
We have cloned and sequenced the mnp genes encoding isoenzymes of manganese peroxidase(MnP) from the white-rot fungus Phanenochaete sordida YK-624 under nitrogen-limiting condition. At least
four mnp cDNAs were cloned. The predicted amino-acid sequence of these isozymes showed a high degree ofidentity each other and also highly conserved to MnP families of other white-rot fungi.
1998-218
1−HBT 存在下における非フェノール性 β-O-4 型ジリグノールのカワラタケラッカーゼによる芳香環開裂
河合真吾、中川 誠、飛鳥井雅倫、大橋英雄
岐阜大学農学部
Aromatic ring cleavage of nonphenolic β-O-4 dilignol by laccase of Coriolus versicolor in the presence of
1-HBT
Shingo Kawai, Makoto Nakagawa, Masanori Asukai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
Aromatic ring cleavage products, 1-(4-ethoxy-3-methoxyphenyl)glycerol-γ-formyl ester and1-(4-ethoxy-3-methoxyphenyl)glycerol-β,γ-cyclic carbonate, were idendfied as degradation prodcuts ofnonphenolic
β-O-4
ligninsubstructure
model
compound,
1,3-dihydroxy-2(2,6-dimethoxylphenoxy)-1-(4-ethoxy-3-methoxyphenyl)propane, by a Coriolus versicolor laccase in thepresence of 1-hydroxybenzotriazole.
1998-219
非水媒体中で機能する界面活性剤 —ラッカーゼ複合体—
岡崎信也*1、後藤雅宏*1、古崎新太郎*1、割石博之*2、田中浩雄*2*1
九州大学大学院工学研究科、*2 九州大学農学部309

Surfactant-laccase complex catalytically active in anhydrous media
Shin-ya Okazaki*1, Masahiro Goto*1, Shintaro Furusaki*1, Hiroyuki Wariishi*2, Hiroo Tanaka*2*1Graduate School of Engineering, Kyushu University, *2Faculty of Agriculture, Kyushu University
Abstract:
A surfactant-laccase complex was prepared with a nonionic surfactant utilizing water-in-oil
emulsions. The complex was easily soluble in anhydrous toluene and effectively catalyzed the oxidation ofo-PDA in such bitterly harsh environment. In contrast, lyophilized laccase hardly catalyzed the reaction process.
The preparation and reaction conditions of the complex have been optimized through studies of the effect of
aqueous pH in the W/O emulsions, surfactant concentration, enzyme concentration at preparation stage, and thenature of the organic solvents.
1998-P01
カワラタケの Hsp30 の遺伝子解析
飯村洋介、辰巳憲司
工業技術院資源環境技術総合研究所
Gene analysis of HSP30 from Coriolus versicolor
Yosuke Iimura, Kenji Tatsumi
Department of Hydrospheric and Environmental Protection, National Institute for Resources and Environment
Abstract:
White-rot fungus Coriolus velsicolor, a ligninolytic basidomycete, has been studied because of
its ability to degrade hazarous chemicals. In this study, two genomic DNAs coding for the Hsp30 were isolated
from C. versicolor. The nucleotide sequences of the two genes differ by 37 base changes within the open
reading frames resulting in 3 amino acid substitutions. Three small introns interrupt genomic DNAs. Putative
eukaryotic regulatory sequences, CAAT-box and TATA-box, are exist in the promoter regions. The regions
contain the consensus heat shock element, xenobiotics response element and metal response element sequences.
Northern blot hybridization indicate that the expression of the Hsp30 gene is constitutive at a normal
temperature and is accelerated at elevated temperature. That expression level is higher in C. versicolor cells thathas been exposed to pentachlorophenol.
1998-P02
MnP バイオブリーチングにおける Tween 80 の役割
江原克信、堤 祐司、西田友昭
静岡大学農学部
The role of Tween 80 in biobleaching with manganese peroxidase
Katsunobu Ehara, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The role of Tween 80 in biobleaching of hardwood kraft pulp (HWKP) with manganeseperoxidase (MnP) was investigated. The most increase of pulp brightness was obtained with Tween 80 among
the surfactants, Tween 80, Tween 20, and CHAPSO. The MnP activity assayed in the presence of eachsurfactant was similarly increased by approximately 1.5 times that of control (no surfactants). Tween 80 had lessstabilizing effect on MnP than other surfactants during MnP- biobleaching. Lipid peroxidation of Tween80
during MnP-biobleaching by TBA methods was not noticeable. Neither these characteristics of Tween 80 nor
delignification by the radical derived from the lipid peroxidation did not explain the most appreciable effect on
the brightness increase by Tween 80.
1998-P03
マンガンを除去した各種クラフトパルプのバイオブリーチング
石村大児、近藤隆一郎、坂井克己
九州大学農学部
Biobleaching of various kraft pulps removed manganese by EDTA
Daiji lshimura, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
When EDTA-extracted oxygen-bleached hardwood kraft pulp (EDTA-extracted LOKP) was
bleached with Phanerochaete sordida YK-624, brightness was increased without secretion of manganeseperoxidase. In order to clarify this phenomenon, various kraft pulps delignified with chlorine compounds andxylanase were treated with the fungus. When EDTA-extracted oxygen- bleached softwood kraft pulp delignified
with chlorine dioxide was treated, the brightness was not increased. When EDTA-extracted unbleached310hardwood kraft pulp delignified with chlorine and chlorine dioxide was treated, both pulps were not bleached.
Effect of xylanase on biological bleaching of EDTA-extracted LOKP was not observed. Consequently, only
EDTA-extracted LOKP was bleached.
1998-P04
シロアリによるリグニンの分解（II）—イエシロアリによる高分子リグニンの分解—
平井浩文*1、中川明子*1、渡辺吉雄*2、深津武馬*1、倉根隆一郎*1*1
NEDO 複合・工業技術院生命研究所、*2NEDO 複合・メルシヤン中央研究所
Degradation of lignin by termites (II), - Degradation of synthetic lignin by Coptotermes formosanus
Hirofumi Hirai*1, Akiko Nakagawa*1, Yoshio Watanabe*2, Takema Fukatu*1, Ryuichiro Kurane*1*1
NEDO Bioconsortia Program, National Institute of Bioscience and Human Technology,
Agency of Industrial Science and Technology,
Abstract:
We examined the degradation of lignin (DHPs) by termite Coptotermes formosanus.
For 1 week treatment by C. formosanus, DHP combined with 4-methylumbelliferone was hardly degradaed, andthe low-molecular-weight fraction of the DHP was polymerized. 13C-NMR spectrum of  -13C-DHP treated by C.
formosanus for 12 days suggests that C. formosanus unselectively degraded DHP.
1998-P05
広葉樹培養細胞のリグニン生合成における前駆体投与の影響
浜田勝義、堤 祐司、西田友昭
静岡大学農学部
The effect of lignin precursors feeding on lignin biosynthesis in Populus calluses
Katsuyoshi Hamada, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture Shizuoka University
Abstract:
Precursors of lignin, ferulic acid (FA) and sinapic acid (SA), were administered to poplar(Populus alba L.) callus cultures. FA and SA addition induces increased levels of lignin in poplar calluses.
Alkaline treatment of cell wall followed by determination of FA and SA from cell walls and alkaline
nitrobenzene oxidation suggest that administered FA is incorporated into both guaiacyl and syringyl lignins,while SA into only syringyl lignin. A marked increase in 4-Coumarate:CoA ligase (4CL) activity against FA was
not observed in the calluses cultured with FA-addition. The increased 4CL activity against SA was correlatedwith the increase in syringyl lignin composition in FA or SA administered calluses. The other class of 4CL
which utilizes SA may be induced in poplar calluses by an extraordinarily high level of FA or SA in calluses.
1998-P06
Anthriscus sylvestris のリグナンの生合成について
鈴木史朗、梅澤俊明、島田幹夫
京都大学木質科学研究所
Lignan biosynthesis in Anthriscus sylvestris Hoffm
Shiro Suzuki, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
L-[Ring-13C6]phenylalanine and [9,9-2H2, OC2H3]coniferyl alcohol were incorporated into
secoisolariciresinol and yatein in Anthriscus sylvestris Hoffm. (Umbelliferae). Furthermore, cell-free extracts
from the leaves of A. sylvestris catalyzed the enantioselective formation of (+)-lariciresinol and(+secoisolariciresinol from (±)-pinoresinols in the presence of NADPH. The enantiomeric compositions of thelignans formed by the cell-free extracts show the similarity to that in case of Forsythia enzyme preparations.
1998-P07
Linum flavum var. compactum から単離された新規ジベンジルブチロラクトンリグナンについて
三亀啓吾、梅澤俊明、島田幹夫
京都大学木質科学研究所
A new dibenzylbutyrolactone lignan from L.inum flavum var. compactum
Keigo Mikame, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
A new dibenzylbutyrolactone lignan 7, 6'-dihydroxybursehernin was isolated from the methanol
extracts of L.inum flavum var. compactum which is known to contain an antitumor lignan311

methoxypodophyllotoxin. 7, 6'-Dihydroxybursehernin was a unique dibenzylbutyrolactone lignan having 3’,4'-methylenedioxy-6'-hydroxy phenyl group.
1998-P08
ネジキにおけるシリンギルリグナン生合成の初期反応について
中川貴志、片山健至
香川大学農学部
Initial reactions in syringyl lignan biosynthesis in Lyonia ovalifolia var. elliptica
Takashi Nakagawa, Takeshi Katayama
Faculty of Agriculture, Kagawa University
Abstract:
Lyonia ovalifolia var. elliptica contains (+)-lyoniresinol (LYR) which is a syringyl andaryltetrahydronaphthalene lignan. To investigate biosynthesis of (+)-LYR and the related syringyl lignans,feeding experiments of radio-isotopically labeled precursors to excised shoots of the plant were performed. It
was found that [8-14C]sinapyl alcohol was incorporated into (+)-[14C]5,5'- dimethoxylariciresinol (DMLAR) andits glycosides, and (+)-[14C]LYR glycosides, but not into [14C]5,5'-dimethoxysecoisolariciresinol. The result
suggested that an enantiospecific reduction of syringaresjnol gave (+)-DMLAR which was then converted to(+)-LYR.
1998-P09
熱分解—質量分析（Py-MS）および多変量解析による草本類リグニンの分析
樺澤直樹、黒田健一
筑波大学農林工学系
Analysis of herbaceous lignins by pyrolysis-mass spectrometry (Py-MS) and multivariate analysis
Naoki Kabasawa, Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba,
Abstract:
Several kinds of herbaceous materials were characterized using pyrolysis-mass spectrometry(Py-MS), The mass spectral data were further analyzed by principal component analysis (PCA) and factor
analysis (FA) in order to investigate the relationships between pyrolysis products and samples. PCA clearly
showed the differences in fractions and growth stages of the samples, quantitative analysis of lignin by Py-MSand FA was examined. The results showed the correlation between acetyl bromide lignin content and factor
score of FA.
1998-P10
塩素漂白で生成した高分子有機塩素化合物の環境中での挙動（3）酸化リグニンの熱分解生成物中に見出されるアルカンタイブ構造の起源について
幸田圭一、新谷博幸、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Environmental fate of high molecular weight chloroorganics produced by chlorine bleaching (III), Origin ofalkane type structures detected in pyrolysis products from oxidized lignins
Keiichi Koda, Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Pyrolysis gas chromatographic analysis showed that alkane type structures were produced as
major pyrolysis products of oxidized lignins. Therefore, the authors assumed thesestructures might originate directly from oxidized aromatic structures of lignin when they underwent pyrolytic
decomposition. By the further study, however, we have come to the conclusion that some unknown structures(i.e. extracts from wood) extracted together with lignin from unbleached kraft pulp are the main source of thesealkane type structures. We'll also report the structural modification of extract components during bleaching, theknowledge of which is very limited.
1998-P11
FT−Raman 分光法を用いたリグニン S／G 比の非破壊的な定量
小名俊博、園田哲也、伊藤一弥、柴田 勝
王子製紙株式会社森林資源研究所
Non-destructive determination of lignin syringyl/guaiacyl monomeric composition in native wood by Fouriertransform Raman spectroscopy
312Toshihiro Ona, Tetsuya Sonoda, Kazuya lto, Masaru Shibata
Kameyama Research Center. Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
The feasibility of using FT-Raman spectroscopy for rapid non-destructive determination oflignin syringyl/guaiacyl (S/G) monomeric composition was examined using Eucalyptus camaldulensis and E.
globules, including samples of various ages and colors, which are of importance as a plantation source. The
application of 2nd derivatives transformation of Raman spectroscopic data revealed highly significant
correlations between wet chemical and Raman predicted values with correlation coefficient (r) = 0.998 andstandard error of prediction (SEP) <0.07 points in the calibration (for known samples), and r=0.935 and
SEP<0.32 points in the prediction (for unknown samples) respectively. Consequently, this non-destructive
method has proved its validity for analyzing Eucalyptus native wood meal samples, regardless of their age andcolor to determine lignin S/G monomeric composition. Using FT-Raman spectroscopy, elite tree selection basedon quality aspects for pulp and paper production can be performed.
1998-P12
マングローブ樹皮タンニンの性状
荻 陽子*1、大井 洋*1、大原誠資*2*1
筑波大学農林工学系、*2 森林総合研究所
Characteristics of tannins from the bark of Sonneratia caseoralis
Yoko Ogi*1, Hiroshi Ohi*1, Seiji Ohara*2*1
Institute of Agricultural and Forest Engineering, The University of Tsukuba, *2Forestry and Forest Products
Research Institute
Abstract:
Chemical characteristics of tannin components from the bark of Sonneratia caseoralis were
investigated. The bark contained 15.9% polyphenols, 4.2% flavanols and 4.9% tannins. From the ethyl acetate
extracts of 70% acetone aqueous extracts, gallic acid was isolated. The acetone aqueous extracts from the bark
were submitted to both pyrolysis gas chromatography and on-line methylation pyrolysis gas chromatography.
Consequently, it has been made clear that pyrogallol and 3,4,5-trimethoxybenzoic acid methyl ester were themain products of pyrolysis gas chromatography and on-line methylation pyrolysis gas chromatography,
respectively. These results indicate that the bark of S. caseoralis contains condensed tannins with more amountsof pyrogallol-type B-rings in more amounts than with catechol-type B-rings, and that hydrolysable tannins are
the main tannin components of S. caseoralis.
1998-P13
南洋材含有アントラキノン類の迅速な定量およびチーク材抽出物の蒸解助剤効果大井 洋
筑波大学農林工学系
Rapid analysis of quinones in tropical hardwoods and catalytic effects of teak extract on pulping
Hiroshi Ohi
Institute of Agricultural and Forest Engineering, The University of Tsukuba
Abstract:
Teak (Tectona grandis) wood contains 2-methyl anthraquinone (MAQ), which is an effective
catalyst for alkaline pulping woods and other lignocellulosics. Pyrolysis-gas chromatography (Py-GC) was
found to be a useful method for the rapid determination of MAQ and anthraquinone (AQ) in a very small
amount of wood, bark and other samples. Teak heartwood of wood samples from Myanmar was shown tocontain 0.47-1.10% MAQ, but not AQ. The sapwood, the bark, and other tropical hardwoods (approximately 20
species) did not contain MAQ at all. The teak wood samples were extracted with some organic solvents. The
extract contents were 7.0-9.9%, and the results from GC showed that MAQ was approximately 5% of theextract. Compared with the GC method accompanied by extraction, the Py-GC method is very useful insearching for a plant which contains anthraquinones. Genetic modification of trees to produce MAQ thatcatalyzes their own pulping is an attractive topic. The alkaline pulping of eucalyptus (Eucalyptus camaldulensis)
wood was carried out in the presence of 0.6% teak extract (0.06% as MAQ) and of 0.06% synthesized MAQ.
The teak extract had better effects on delignification.
1998-P14
酸素−アルカリ漂白過程における多糖類の分解機構（10）横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Degradation mechanisms of carbohydrate during oxygen-alkali bleaching process (X)313

Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
A cellulose model compound, methyl β-D-glucopyranoside (MGP) and a non-phenolic lignin
model
compound,3,4-dimethoxybenzyl
alcohol(veratryl
alcohol,VA)or
1-(3,4-dimethoxy-phenyl)-1,2-ethanediol (veratryl glycol, VG), were subjected to oxygen-alkali treatments with
2,4,6-trimethylphenol which was an active oxygen generator in this system.The degradation of VG was muchlarger than the degradation of VA under high pH. This indicates that the side chain part of lignin modelcompounds participates in the reaction with active oxygen species more than the aromatic part does under high
pH. Reaction selectivity was higher when VG was used as a non-phenolic lignin model compound than when
VA was used as that under high pH, but the reverse was the case under low pH.
1998-P15
免疫法によるクラフト蒸解中のグルコマンナンおよびキシランの挙動の可視化
今井貴規、左合章太郎、安田征市
名古屋大学農学部
Visualization of the behaviors of glucomannan and xylan during kraft pulping by immuno- microscopicaltechniqueTakanori Imai, Shotaro Sago, Seiichi Yasuda
School of Agricultural Sciences, Nagoya University
The distribution of glucomannan and xylan in pine wood was visualized by immune- microscopy at various
stages of kraft pulping to investigate their behaviors during the pulping. Using anti-glucomannan antibody,
secondary wall was entirely immuno-labeled in non-kraft treated wood, whereas in kraft treated wood lumenside of secondary wall was labeled preferentially. Using anti-xylan antibody, the lumen side was preferentiallyimmuno- labeled in both non-kraft treated wood and kraft treated wood. These results indicate that during kraft
pulping glucomannan and xylan were dissolved in pulping liquor in cell wall, and the hemicelluloses moved tolumen side of cell wall with diffusion of pulping liquor and were concentrated in this side, then eluted fromwood.
1998-P16
未利用プランテーションバイオマスの有効利用開発：ココナッツ・コアイアダストからの土壌改良材の調製とその性状
市川朋子*1、飯塚堯介*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物環境資源研究センター
Effective utilization of plantation waste biomass. -Soil conditioner from coconut coir dust
Tomoko Ichikawa*1, Gyosuke Mesitsuka*1, Kenji Iiyama*2
Graduate School of Agricultural and Life Sciences, the University of Tokyo, Asian Natural Environmental
Science Center, the University of Tokyo
Abstract:
There are many plantations producing latex, palm oil, coconut oil, sugar, cacao coffee beans,and so on, in tropical region. Huge quantities of waste and residue are produced during harvesting commercial
products and replanting. The most of these waste and residues are not effectively utilized yet. It is significant
important for conservation of global environmental and sustainable production of biomass to utilize thesewastes and residue. In this paper, we focused coconut coir fiber (CCF) and coir dust (CCD) to develop theireffective utilization. Chemical composition of these materials were analyzed and its structural feature werecharacterized. Both CCF and CCD were carboxymetylated to be utilized as soil conditioner. The Cm-CCF and
CM-CCD were fractionated into water-soluble and insoluble fractions and characterized their chemical feature.
Then their water absorbtivety was examined.
1998-P17
酸リグニンより可溶性アリールリグノスルホン酸および陽イオン交換樹脂の調製
浅野敦子、安田征市
名古屋大学農学部
Preparations of soluble aryllignosulfonic acid and cation exchange resin from acid lignin
Kyoko Asano, Seiichi Yasuda
School of Agricultural Sciences, Nagoya University
Abstract:
Preparations of soluble aryllignosulfonic acid and cation exchange resin from gymnosperm
314sulfuric acid lignin (Klason lignin) (SAL) were tried. Soluble aryllignosulfonic acid was prepared from SAL bysulfuric acid-catalyzed phenolation, chlorosulfonation and final alkali hydrolysis. Reaction mechanism wasconfirmed in a separate experiment with a model compound. Furthermore, cation exchange resin was preparedby a series of reactions of SAL, that is, resinification with formalin, chlorosulfonation and alkali hydrolysis. Ion
exchange capacity of it was 3.2 meq/g.

315

第 44 回 （1999.10.7-8） 岐阜大学農学部
1999-101
スギ胚へのパーティクルガン法による遺伝子導入
田仲徹称、七澤雅治、諸星紀幸
東京農工大学大学院生物システム応用科学研究科
Gene introduction into Sugi embryo with particle bombardment
TetsuyaTanaka, Masaharu Nanasawa, Noriyuki Morohoshi
Graduate School of Bio-application and Systems Engineering, Tokyo University of Agriculture and Technology
Abstract:
Lignin is one of the major components in woody plant cell wall. The quantity and quality oflignin have an influence on the pulping and the biomass utilization. In the future, their improvement will be
required for utilization of the biomass more effectively. In this study, we tried to regenerate Sugi (Cryptomeria
japonica D.Don), which is a useful conifer in Japan, and to establish a transformation system of Sugi. We
succeeded to introduce foreign genes into Sugi embryo with particle bombardment.
1999-102
細胞壁の木質化に関与する酵素の局在
高部圭司*1、伊藤真記*2、竹内美由紀*1、藤田 稔*1、片山義博*3*1
京都大学大学院農学研究科、*2 日本製紙株式会社、*3 東京農工大学大学院 BASE
Distribution of enzymes involved in lignification of cell wall
Keiji Takabe*1, Masaki Ito*2, Miyuki Takeuchi*1, Minoru Fujita*1, Yoshihiro Katayama*3*1
Graduate School of Agriculture, Kyoto University, *2Nippon Paper Industries Co. Ltd., *3Graduate School of
Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology
Abstract:
One of the most characteristic phenomena in woody plants is lignification of cell walls. Almost
all of the enzymes involved in lignification are now well known. However, much more works are needed toelucidate the localization of these enzymes in the cell, relation of enzymes to cell differentiation, and regulatory
mechanism of synthesis of these enzymes. We applied the immuno- cytochemistry by using the antibodies
against the enzymes involved in lignification, and showed the enzymes involved in biosynthesis of monolignols
are synthesized at polysomes and then are dispersed into the cytosol of the lignifying cells. Therefore,monolignols are synthesized in the cytosol and transported to the cell wall by passing through the plasma
membrane. On the contrary, the enzyme involved in dehydrogenative polymerization of monolignols is
synthesized in rough endoplasmic reticulum and transported to lignifying cell walls via the Golgi apparatus.
Finally lignification occurs in the cell walls.
1999-103
ケナフ（Hibiscus cannabinus）勒皮、コア及び根の細胞壁成分の生長にともなう変化と光合成能
Thi Bach Tuyet Lam*1、角園敏郎*2、飯山賢治*3*1
School of Biochemistry, La Trobe University, *2 森林総合研究所、*3 東京大学アジア生物資源環境研究セン
ター
Core and root of maturing kenaf (Hibiscus cannabinus).
Thi Bach Tuyet Lam*1, Toshio Sumizono*2, Kenji Iiyama*3*1
School of Biochemistry, La Trobe University, *2Forestry and Forest Products Research Institute, *3Asian
Natural Environmental Science Centre, the University of Tokyo
1999-104
リグニン化学構造の不均一牲（3）—TMSiI を用いたエンドワイズリグニンの評価—
掘啓映子、飯塚堯介
東京大学大学院農学生命科学研究科
Structural heterogeneity of hardwood lignjn (III), - Estimation of endwise lignin fraction by TMSil treatment
Keko Hori, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Endwise lignin fraction, was composed mostly of syringyl units and β-O-4 intermonomer
linkages, was found in birch periodate lignin. The endwise lignin fraction should be cleaved to monomer by
TMSiI (trimethylsilyl iodide) under a very mild condition. Sinapyl alcohol was the main peak of GC
chromatogram after TMSiI treatment for 3hr, but the yield was not very high. Syringylpropane monoiodide was316

detected by GC analysis after 72hr TMSiI treatment, but the peak was not detected after Zn treatment. The
molecular weight distribution after Zn treatment is now under investigation.
1999-105
リグニンの三次元構造の推定方法に関する考察
寺島典二
名古屋大学
Possible approaches for estimating three dimensional structure of lignin
Noritsugu Terashima
Nagoya University
Abstract:
Lignin structural models proposed in the past provide information insufficient to predict
chemical behavior of lignin in the cell wall. An advanced 3D structural model should contain information on
structural heterogeneities and macromolecular properties as follows; (I) distribution and frequencies of different
kinds of units, functional groups, inter-unit bonds, lignin-polysaccharide bonds in lignin macromolecule and in
the cell walls, (2) higher order structure and size of lignin macromolecule, and (3) 3D assembly of lignin andpolysaccharides in different morphological regions of cell walls and in different kinds of cells. Based on theinformation obtained by non-destructive analyses employing improved radio- and stable isotope tracer methods
combined with the information by electron microscopy and other various destructive analyses, a 3D model canbe proposed tentatively. For further revision of the model, improvements of the approaches to get more reliable
information especially on (3) are required.
1999-106TOF−SIMS イメージによるリグニン構造解析の試み
福島和彦*1、陳 方*1、山内一慶*1、安田征市*1、高橋元幾*2、星 孝弘*2
*1
名古屋大学大学院生命農学研究科、*2 アルバック・フアイ株式会社
Analysis of lignin structure by TOF-SIMS
Kazuhiko Fukushima*1, Fang Chen*1, Kazuchika Yamauch*1, Seiichi Yasuda*1, Motoki akahashi*2 ,Takahiro
Hoshi*2*1
Graduate School of Bioagricultural Sciences, Nagoya University, *2ULVAC-PHI. Inc.
Abstract:
The structure of lignin of tree xylem was investigated by TOF-SIMS. Pine and beech MWLs
gave some secondary ions which had guaiacyl or syringyl nuclei on TOF-SIMS analysis. Deuterium labeledmagnolia xylem fed with phenylalanine-d7 gave the image which represent the localization of deuterium on thesurface of xylem on TOF-SIMS analysis.
1999-107
リグニンの熱分解：β−5 型構造由来の熱分解生成物
黒田健一
筑波大学農林工学系
Analytical pyrolysis of lignin: pyrolysis products derived from the -5 building blocks
Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Dehydrodiconiferyl alcohol and its related compounds II-V were pyrolyzed at 500ºC for 4s.
The predominance of 4-methylguaiacol (a 27 % (mol/mol) yield from I) was observed in the monomericproducts, suggesting that in pyrolysis of lignins parts of 4-methylguaiacol are derived from the β-5 building
blocks. Pyrolysis product profile of I methylated by diazomethane showed that the products derived from theβ-5 building blocks are extensively derived from the A ring-moiety in the β-5 building blocks. Comparison of
the product yields from I with those from a Japanese cedar wood and its lignins suggested that the contributionsof the β-5 building blocks are large to the formation of 4-methylguaiacol in pyrolysis of lignins.
1999-108
過マンガン酸カリウム酸化分解の新たな触媒を用いた改良法の開発
辻 幸子*1、諸星紀幸*1、大森茂俊*2*1
東京農工大学大学院生物システム応用科学研究科、*2 ニューヨーク州立大学
A potassium permanganate oxidation method modified with new catalysis
Yukiko Tsuji*1, Noriyuki Morohoshi*1, Shigetoshi Omori*2
317

*1

Graduate School of Bio-application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Department of Paper Science and Engineering / ESPRI SUNY, Collage of Environmental Scienceand Forestry
Abstract:
Potassium permanganate oxidation of lignin is a very important method to be able to obtain
information about lignin chemical structures, and the higher the yield of degradation products is, the more
useful the method will become. Then we tried to modify the method by addition of catalysis,cetyltrimethylammonium bromide, in order to increase the yield of degradation products.
In conclusion, we got the result that the yield of degradation products of the modified method increased
10%-30% in comparison with control method.
1999-109
TIZ 分解法における α エーテル構造の反応牲片平 類、中坪文明
京都大学大学院農学研究科
The chemical reactivity of  ether structure in lignin in the TIZ degradation method
Rui Katahira, Fumiaki Nakatsubo
Graduate school of Agriculture, Kyoto University
Abstract:
Many degradation methods for β-O-4 structure reported so far are usually conducted underacidic or alkaline conditions, resulting in that unexpected secondary condensation reactions are caused.
Therefore we have previously developed the quite novel degradation method of the β-O-4 structure in lignins
without any secondary side reactions named TIZ method. But the stability of  ether structure in the degradation
reactions by TIZ method has not been recognized. In this study, weshowedby β-O-4 lignin model experimentsthat  ether structures were not cleaved by TIZ method.
1999-110
過ヨウ素酸酸化によるリグニン・多糖エーテル結合の定性的及び定量的検討
藤本文*1、飯塚堯介*1、Thi Bach Tuyet Lam*2、飯山賢治*3*1
東京大学大学院農学生命科学研究科, *2La Trobe 大学生化学科、*3 東京大学アジア生物資源環境研究センター
Qualitative and quantitative investigation of ether linkage between lignin and polysaccharide in plant cell walls
by periodate oxidation
Aya Fujimoto*1, Gyosuke Meshitsuka*1, Thi Bach Tuyet Lam*2, Kenji Iiyama*3*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2School of Biochemistry, La
Trobe University, *3Asian Natural Environmental Science Center, the University of Tokyo,
Abstract:
It is exciting to make clear the structural feature of covalent associations between lignin andwall polysaccharides, so called LCC, because of their important roles for plant physiology and effective
utilization of biomass. We are focusing to elucidate linkage positions of direct ether linkages between
phenylpropane unit of lignin and glycosidic residue, which would be most important linkages for periodate
oxidation followed by ozonolysis to remove sugar residues and phenylpropane units free from the associations,
respectively. ln this paper, we applied these procedures to cell walls of yezo spruce (Picea jezoensis Carr.) andinvestigated the optimum conditions for periodate oxidation, reduction of the residue of periodate oxidation,
mild acid hydrolysis and so on. Tetra-O-acetyl-erithritol was detected and quantified as a major product by analditol acetate analysis of residue of the periodate oxidation followed by reduction and mild acid hydrolysis,
together with tetra-O-acetyl-threitol. The result suggests that the presence of linkages between lignin and theC6-position of glucosyl residue, probably cellulose, and between lignin and the C6-position of galactosyl
residue. We have applied the procedures to cell walls of beech (Fagus crenata Blume).
1999-111
脱リグニンに伴う β-O-4 型構造のエリスロ・スレオ比の変化について
杉本倫子、秋山拓也、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Change in E/T ratio ofβ-O-4 structure during delignification reaction
Tomoko Sugimoto, Takuya Akiyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultura1 and Life Sciences, the University of Tokyo
Abstract:
By the ozonation method, erythro and threo (E/T) ratio of arylglycerol-β-aryl ether (β-O-4)
318

structure can be obtained as a ratio between two ozonation products, erythronic and threonic acids. It was
confirmed that the ozonation method can be successfully applied to a lignin remaining in partially delignified
samples if degraded lignin is well washed out from the sample. This method was applied to an analysis of thechange in E/T ratio in the residual lignin after wood meal was stepwisely delignified. When delignified by alkali
cooking, not only the total yield of erythronic acid and threonic acid per lignin but also the E/T ratio decreased
significantly with the progress of delignification. In contrast to this, when delignified by NaClO 2 treatment, nosignificant change was observed in E/T ratio. It is likely that a part of lignin with higher content of β-O-4structure was rich in erythro type and was preferentially removed by alkali cooking, and , the part of lignin withlow content of β-O-4 structure was relatively poor in erythro type and resistant to alkali cooking. These results
coincide well not only with the generally accepted delignification mechanism during alkaline pulping but alsowith our previous hypothetical proposal that the E/T ratio of secondary wall lignin is higher than that ofcompound middle lamella lignin. On the other hand, when delignified by NaClO2, the delignification seems toproceed almost homogeneously regardless of the content of β-O-4 structure and its E/T ratio. It is wellunderstood from its reaction mechanism to oxidize lignin.
1999-112
バングラデシュ産アカシア・カテチュ心材抽出物の化学組成
アブル・カラム・アザド、荻山紘一
山形大学農学部
The chemical constituents of Bengal catechu (Acacia catechu)-heartwood extractives
Abul Kalam Azad, Koichi Ogiyama
Faculty of Agriculture, Yamagata University
Keywords: (+)-catechin, NMR spectrometry, PTLC. GC-MS
Abstract:
Acacia catechu に属するベンガル・カテチュの水抽出物は，ベテルの葉（地方名パン）のスパイスとしてチューインガムに昔から用いられている．この樹木の赤色心材の主化学成分は，バング
ラデシュではカテチュと呼ばれている．心材のメタノール抽出物（収量 8.64%）の TLC 分析は，この部分に 9個のフェノール性化合物が存在することを示した．この抽出物の主ポリフェノール化合物は，（＋）-カテキンで，メタノール抽出物の約 3.33%を占めていた．その母液から新規な化合物が単離された．それは（＋）-カテキンと同じ A 環と B 環を持ち，七員ヘテロ環状の C 環を有していた．その収量は，メタノール抽出物の約 0.053%であった。
1999-113
ゴボウ（Arctium lappa)におけるセコイソラリシレジノール生成の立体化学的選択性について
鈴木史朗、梅澤俊明、島田幹夫
京都大学木質科学研究所
Stereochemical selectivity of secoisolariciresinol formation in Arctium lappa L.
Shiro Suzuki, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
The difference in stereochemistry of secoisolariciresinol formation between petioles andripening seeds of Arctium lappa L. was further investigated using the cell-free extracts. Both cell- free extracts
from ripening seeds and petioles catalyzed the formation of (-)-secoisolariciresinol from (±)pinoresinols and(±)lariciresinols, but with different enantiomeric compositions of the product. However, we previously reported
the enantioselectiveformation of (+)secoisolariciresinol from coniferyl alcohol using cell-free extracts from thepetioles. These results indicate that stereochemistry of lignan biosynthesis in A. lappa is very complicated anddiverse.
1999-特別講演、I.
植物の外部環境検知能力と形づくりについて
野方文雄
岐阜大学工学部
Cell-based sensing system for external stimuli and an adaptive modeling process in plant
Fumio Nogata
Department of Mechanical and Systems Engineering, Gifu University
Abstract:
Examining some biological load carriers such as plant and tree stems, animal bones and other319

biological hard tissues, we see that their geometry changes under loading to match mainly stress- or
strain-dependent requirements. For example, the interior structure of a bone exhibits all optimized shape withrespect to the principal stress directions and the shear stress magnitude in the body. This indicates that the bone
is managed by a self-optimizing system with sensing mechanisms (e.g., piezoelectric and/or streaming potential
effect of bone) that detect external mechanical stimuli to control the modeling/remodeling of the skeletal system.
Thus, it can be inferred that the shape and ingenious construction of biological hard tissues are the result of acontinuous process of intelligent optimization. The goals of this work are to gain an understanding of theprinciples of design and processes found in biological tissues and to apply these findings toward developing new,intelligent, superior material concepts by using and/or modifying those models which are found in livingorganisms. We begin by presenting bamboo as a typical example of the ingenious construction, depending on
mechanical stresses/strains conditions, and a cell based sensing system for external stimuli as well as an
adaptive modeling process in plant.
1999-特別講演、II.
リグニン生分解研究から派生したシュウ酸合成酵素研究への新局面。—木質資源の育成と保護に関わる菌
類の役割—
島田幹夫
京都大学木質科学研究所
A new aspect of oxalic acid producing enzyme research derived from lignin biodegradation research, —Roles offungi in production and preservation of woods
Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Retrospective viewpoints of lignin biodegradation research are described focusing on
development of the first biomimetic example of heme enzyme (LiP and MnP) model catalysts for the one
electron oxidation of lignin and bleaching of unbleached kraft pulps. A new aspect of oxalic acid involved inligninolytic systems in white-rot fungi is discussed in relation to a possible role of the glyoxylate cycle which
may commonly occur in a wide variety of saprophytic, symbiotic, and edible mushrooms.
1999-201
耐塩牲白色腐朽菌に関する研究（I）高塩濃度条件下で生育する菌株の探索
李 シン、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
Study on hypersaline-tolerant white-rot-fungi. (I). Screening of lignin-degrading fungi at hypersaline
Li Xin, Ryuichiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
In order to characterize marine fungi, which have high lignin-degrading ability at salineconditions, several marine fungi were screened from 28 fungus strains isolated from mushrooms and driftwood
samples from the mangrove stands in Okinawa, Japan. The decolorization ability, delignification activity ofwood meals and biobleaching property were evaluated and then a strain MG-60, was selected as a prosperous
marine fungus that had tolerance to hypersaline.
1999-202
白色腐朽菌 Ceriporiopsis subvermispora の生産する新規ジカルボン酸
榎 牧子、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
A novel dicarboxylic acid produced by white-rot fungus Ceriporiopsis subvermispora
Makiko Enoki, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Novel fluorescent dicarboxylic acids, 1-heptadecene-2,3-dicarboxylic, 1,7-nonadecadiene 2,3dicarboxylic and 1-nonadecene-2,3-dicarboxylic acids were isolated from wood meal cultures of white-rot
fungus Ceriporiopsis subvermispora. These three compounds are itaconic acid derivatives having different
aliphatic chain. The amount of these amphiphilic dicarboxylic acids increased with incubation time, suggestingthat production of these dicarboxylic acids is related to lignin biodegradation.
1999-203320

マンガンペルオキシダーゼによる非フエノール性リグニンモデル化合物の分解
鬼束愛子、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
Degradation of non-phenolic lignin model compounds by manganese peroxidase
Aiko Onitsuka, Ryuitiro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University,
Abstract:
We previously reported that isolated manganese peroxidase (MnP) from white rot fungus
Phanerochaete sordida YK-624 cleaved -ether bond of 3-hydoroxy-2-(4-methyl- umbelliferone)1-phenylpropanone. The system required MnP, malonate, Tween 20 and MnSO4 but not hydrogen peroxide. In
this study, we tried to degrade nonphenolic lignin model compounds having -carbonyl or -hydroxyl group by
MnP from P. sordida YK-624. Model compounds having -carbonyl group were degraded by MnP system (MnP,
malonate, Tween 20. and MnSO4), however. model compounds having -hydroxyl group were not degraded atall. The reaction mechanism will be discussed.
1999-204
白色腐朽菌 Pleurotus ostreatus により生産される MnP アイソザイムの生産調節について
上辻久敏、河 考哲、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
The effect of culture condition on the production of manganese peroxidase by white-rot fungi Pleurotus
ostreatus
Hisatoshi Kamitsuji, Ha Hyo-cheol, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Manganese peroxidase (MnP) was secreted by Pleurotus ostreatus in liquid stationary
culture. Two different MnP isozymes were produced in glucose/yeast-extract medium (GY) andpeptone/glucose/yeast-extract medium (PGY). The isoelectric points of MnP produced in GY medium(MnP-GY) and PGY medium (MnP-PGY) were found to be 3.70 and 3.95, respectively. The molecular massesof both isozymes were 42 kDa. N-terminal amino acid sequences of MnP-PGY was found to be identical to thatof MnP 3. It was also similar to that of MnP which was produced in the sawdust culture.
1999-205
白色腐朽菌ヒラタケにおける組換えマンガンペルオキシダーゼ発現系の開発
入江俊一、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
Homologous expression of recombinant manganese peroxidase gene in Pleurotus ostreatus
Toshikazu Irie, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
The genomic and cDNA fragments encoding Pleurotus ostreatus. MnP3 were cloned andanalyzed. From sequencing analysis, it was demonstrated that P. ostreaus MnP3 has a property specific for bothof manganese peroxidase and lignin peroxidase from Phanerochaete chrysosporium. The coding sequence was
fused with promoter and terminator sequence of P. ostreatus sdi1 encoding succinate dehydrogenase iron-sulfur
protein subunit. The recombinant constructs were introduced into wild-type P. ostreatus strain via
DNA-mediated transformation. Transformants which express higher MnP activity than wild type were isolated.
One of the recombinants obtained by mating between two monokaryotic transformants, TMG9-C1 has shown
several times higher MnP activity than the wild-type control in the early stage of liquid culture of the mycelium.
Predominant transcription of the recombinant mnp3 at the 6th day was demonstrated by a competitive RT-PCR
experiment.
1999-206
シロアリ腸内から単離した放線菌の産生するペルオキシダーゼについて
原園幸一*1、渡辺吉雄*2、深津武馬*1、倉根隆一郎*1*1
工業技術院生命工学工業技術研究所、*2 メルシヤン中央研究所
Peroxidase produced by Streptomyces eurythermus isolated from guts of lower termites, Coptotermes
formosanus
Koichi Harazono*1, Yoshio Watanabe*2, Takema Fukatsu*1, Ryuichiro Kurane*1*1
Bioconsortia Program, National Institute of Bioscience and Human Technology, Agency of321

Industrial Science and Technology, *2Central Research Laboratory, Mercian Corp.
Abstract:
The production of peroxidase by actinomycete, Streptomyces eurythermus CA2 isolated fromguts of lower termites, Coptotermes formosanus was studied in shaken liquid culture.
The addition of 5-aminolevulinic acid increased peroxidase activity in culture of S. eurythermus CA2.
Peroxidase activity in culture of S. eurythermus CA2 was dependent on H2O2 and was inhibited with potassium
cyanide and ethylene glycol bis(-aminoethyl ether) N,N,N’,N’-tetraacetic acid (EGTA). Four peroxidase
isozymes from concentrated culture filtrate were detected by nondenaturing polyacrylamide gel electrophoresis(PAGE) and activity staining with L-3,4-dihydroxyphenylalanine as the substrate. The molecular mass of main
peroxidase isozyme P2 was about 53 kDa.
1999-207
白色腐朽菌の液体培養系による飛灰中ダイオキシン類の分解
好光正豪*1、近藤隆一郎*1、坂井克己*1、水海吉太郎*2*1
九州大学農学部、*2 有限会社微創研
Degradation of dioxins in fly ash treated in the liquid culture of white rot fungi
Masahide Yoshimitsu, Ryuichiro Kondo, Kokki Sakail, Yoshitaro Suimi
Faculty of Agriculture, Kyusyu University
Abstract:
Seventy two strains of fungi were screened for the growth in the liquid medium mixed with fly
ash. White rot fungus MZ-340 was selected, because it grew well in the medium mixed with fly ash, anddegraded 2,7-dichlorodibenzo-p-dioxin extensively. In this study, we demonstrated the degradation ofpolychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/DFs) in fly ash by the liquid
culture of the fungus. PCDDs/DFs content, 52.0 ng-TEQ/g, in the fry ash were reduced to l 8.6 ng-TEQ/g bytreatment with the fungus MZ-340 for 2 weeks.
1999-208
ラッカーゼおよびマンガンペルオキシダーゼによる内分泌撹乱物質の除去
羽田 崇*1、堤 祐司*1、西田友昭*1、和田敏明*2*1
静岡大学農学部、*2 東京都林産試験場
Removal of endocrine disrupters by laccase and manganese peroxidase
Thkashi Haneda*1, Yuji Tsutsumi*1, Tomoaki Nishida*1, Toshiaki Wada*2*1
Faculty of Agriculture, Shizuoka University, *2Tokyo Metropolitan Forestry Experiment Station
Abstract:
Endocrine disrupters, such as bisphenol A (BPA) and nonylphenol (NP), may modify natural
endocrine function and so affect human health and wildlife. In this study, therefore, we tried to remove the
estrogenic activity of BPA wd NP with partially purified laccase and manganese peroxidase (MnP). BPA and NP
were removed by both enzyme treatments in 60 min, which was mainly due to polymerization. We alsomeasured the estrogenic activity of-BPA or NP before and after enzyme treatments by using yeast two-hybrid
system. More than 95% of estrogenic activity of BPA and NP disappeared after 12h-treatment with both
enzymes. These findings indicate that the treatment of BFA and NP with laccae and MnP is effective in removal
and disappearance of estrogenic activity of them.
1999-209
リグニン分解酵素系によるパルプ繊維の改質 —MnP 処理が DIP パルプ繊維に及ばす影響—
土川圭一*1、近藤隆一郎*2、坂井克己*2*1
特殊製紙株式会社、*2 九州大学農学部
Application of ligninolytic enzymes to modification of pulp fibers. -Effects of MnP treatment on DIP
Keiichi Tsuchikawa*1, Ryuichiro Rondo*2, Kokki Sakai*2*1
Tokushu Paper MFG Co. Ltd, *2Faculty of Agriculture, Kyushu University
Abstract:
The application of MnP treatment to DIP was examined. The ISO brightness of the DIP
decreased slightly by MnP treatment, however, it was recovered with the combination of H2O2 bleaching. The
residual fluorescence intensity in DIP was decreased by MnP treatment. Physical properties of DIP was
improved by Map treatment, and also Map treatment enhanced the effect of PAM addition on physical strengthof the pulp.
1999-210
溶媒循環プロセスによる HBS パルプ化（1）—針葉樹材の脱リグニン322

梶本純子、衣笠わか子、佐野嘉拓
北海道大学大学院農学研究科
HBS pulping with solvent-recycling process. (I). -Delignification of softwood.
Junko Kagimoto, Wakako Kinugasa, Yoshihiro Sano
Graduate school of Agriculture, Hokkaido University
Abstract:
In order to develop a new pulping process with non-pollution and saving energy, softwood was
subjected to delignification with high boiling-pint solvents (HBS) with and without acetic add. Todomatsu,
ezomatsu, karamatsu and sugi were easily delignified under conditions with 60-80% HBS such as
butanediol-1,4 at 220ºC for 1-3 h with and without acetic acid. However, acetic add promoted the delignification
reaction. Pulp was washed with the same solvent or acetone, and then water. The water washing was poured intoa mixture of the reaction liquor and solvent washing to precipitate water insolubles such as lignin and sugar
modified products. A mixture of solvent andsugars recovered by evaporation of the water from water solubles could be reused more than 5 times as apulping solvent for the new pulping procedure without hitch.
1999-211
硝酸と亜硝酸塩を添如した有機溶媒水媒体における広葉樹リグニンの分解挙動
大井 洋
筑波大学農林工学系
Behavior of hardwood lignin decomposition in organic solvent-water media with nitrite and nitric acid
Hiroshi Ohi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Ethanol-water pulping has been proposed as one of organosolve pulping methods. Acid
catalysts were investigated for improving the pulping conditions, but nitric acid is not studied yet. Nitric acid
pulping is conducted at much lower temperatures than the ethanol-water pulping. The effects of nitrite and nitricacid on the pulping using ethanol-water media are not clear. It has been shown that at the dosage of 40% nitricacid and 90ºC, the lignin decomposition was facilitated when a very small amount of catalytic nitrite was added.
In addition, the pH of the media was increased by the consumption of nitric acid. In this study, behavior oflignin decomposition in such media is further discussed using an isolated lignin and wood chips.
1999-212
塩素漂白過程で生成するクロロホルムの可能生成量について
幸田圭一、新谷博幸、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Formation potential of chloroform during chlorine bleaching of kraft pulp
Keiichi Koda, Hiroyuki Shintani, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
Chlomform produced during chlorine bleaching of kraft pulp was quantitatively analyzed by
GC-MS (SIM mode). The amount of chloroform that can potentially be formed was also estimated. Chlorination
and alkali treatment of pulp and/or effluent was performed in a gas tight reaction vessel in order to determine
chloroform as accurately as possible. The result suggested that by subjecting both chlorinated pulp andchlorination effluent to alkali treatment, chloroform precursors were quantitatively estimated. Even though
hypochlorite addition is the major source of chloroform formation, chloroform formation during both C-and
E-stages should properly be evaluated.
1999-213
マルチング中の剪定枝チップ細胞壁成分の変化
小野 芳*1、市川朋子*1、渡辺達三*2、飯山賢治*3*1
東京大学大学院農学生命科学研究科、*2 東京大学大学院新領域、*3 東京大学アジア生物資源環境研究センター
Compositional changes of wood chips during mulching
Kaori Ono*1, Tomoko Ichikawa*1, Satomi Watanabe*2, Kenji Iiyama*3*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Graduate School of Frontier
Science, the University of Tokyo, *3Asian Natural Environmental Science Center, the University of Tokyo
Abstract:
Huge quantities of pruned branches are produced from planted trees at urban area. Recently,
323

they are utilized in the shape of wood chips as compost and mulch. In this paper, sequential changes in woodchip mulch were examined by using sugi (Cryptomeria japonica) and keyaki (Zelcova serrata). Changes inchemical composition were also investigated for wood chips buried at the bottom and the surface of mulch
system. It was shown that Z. serrata, an Angiosperm wood, was modified biologically faster than C. japonica, aGymnosperm wood, and compositional changes in mulch buried in the bottom was more significant than that at
surface. The relative content of lignin increased significantly in Z. serrata mulch, and condensation of lignin
made progress during mulching.
1999-214
リグニン系土壌改良剤による植物の AL 生育障害の改善
斎藤京子、飯塚堯介
東京大学大学院農学生命科学研究科
Improvement of growth inhibition of plant by AL using soil conditioning agent from lignin
Kyoko Saito, Gyosuke Meshitsuka
Graduate School of Agriculture and Life Sciences, The Umiversity of Tokyo
Abstract:
Aluminum ion (AL) is one of the main reasons of toxicity to plant growth in acid soil. AL iseluted from soil matrix below pH 4.5 and inhibits elongation of plant root. We modified krait lignin byalkaline-oxygen treatment and obtained humin-like materials rich in acidic groups, especially carboxylic acidgroup. Modified kraft lignins were expected to form complex with AL, which has been confirmed by pH
titration. In this study, the effect of pH and the formation of AL-lignin complex on grow of radish root were
examined. It was found that toxicity of AL dissolved in the culture solution was effectively removed by thepresence of enough amount of a modified lignin.
1999-215
両親媒牲リグニン誘導体と蛋白質の相互作用
西田光邦、浦木康光、佐野嘉拓
北海道大学大学院農学研究科
Interaction of amphiphilic lignin derivative with protein
Mitsukuni Nishida, Yasumitsu Uraki, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
Acetic acid ligmin (AL) prepared by the atmospheric acetic acid pulping of birch
was reacted with polyethylene glycol diglycidyl ether (PE) under alkaline conditions to yield an amphiphilic AL
derivative (PE-AL). PE-AL was suggested to have a similar structure to the rigid Binstein's sphere in aqueous
solution, and to shrink as increasing in the concentration probably due to the hydrophobic interaction of AL
domains by viscometric study. PE-AL was found to form the complex with bovine serum albumin as model
protein for about one week at 4ºC by the measurements of size-exclusion chromatography and circulardichroism. Furthermore, the decrease in lipase activity in aqueous 20% ethanol was repressed by PE-AL. Thus,
PE-AL seems to contribute to preserve the activity of enzyme.
1999-216
リグニンベースポリカプロラクトン誘導体の TG・FTIR
畠山兵衛*1、吉田孝範*1、伊豆田良信*1、廣瀬重雄*2、畠山立子*3*1
福井工業大学工学部、*2 工業技術院物質研究所、*3 大妻女子大学家政学部
TG-FTIR of lignin-based polycaprolactone derivatives
Hyoe Hatakeyama*1, Takanori Yoshida*1, Yoshinobu Izuta*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3*1
Fukui Institute of Technology, *2National Institute of Materials and Chemical Research, *30tsuma Women's
University
Abstract:
Lignin-based polycaprolactone derivatives (LigPCL) were prepared from kraft lignin (KL) andan organosolv lignin (Alcel lignin, AL). The gases evolved by thermaldegradation of LigPCL were analyzed bysimultaneous thermogravimetry (TG) and Fourier-transformed infrared spectrometry (TG-FTIR). The amountsof thermal degradation products having characteristic functional groups changed according to the length of PCL
chains in the LigPCLs.
1999-P01
広葉樹シリンギルリグニンの生成機構
324

山内一慶、福島和彦、斉藤香織、安田征市
名古屋大学大学院生命農学研究科
Biosynthesis of syringyl lignin in angiosperm
Kazuchika Yamauchi, Kazuhiko Fukushima, Kaori Saito, Seiichi Yasuda
Faculty of Agriculture, Nagoya University
Abstract:
4-Coumarate:CoA ligase (4CL) activity for sinapic acid has not been detected in many
dicotyledonous plants. In order to investigate the existence of the pathway (sinapic acid to sinapoyl-CoA), we
perform the tracer experiment. Sinapic acid, both two methoxyl groups were labled by deuteriums, wassynthesized and fed to various angiospermous wood. If the pathway (sinapic acid to sinapoyl-CoA) exists, twolabled methoxyl groups should be intrduced to lignin.
1999-P02
広葉樹分化中木部細胞における O-メチルトランスフエラーゼの局在
竹内美由紀*1、高雄圭司*1、藤田 稔*1、片山義博*2*1
京都大学大学院農学研究科、*2 東京農工大学大学院 BASE
Localization of OMT in differentiating xylem cells of hard wood
Miyuki Takeuchi*1, Keiji Takabe*1, Minoru Fujita*1, Yoshihiro Katayama*2*1
Graduate School of Agriculture, Kyoto University, *2Graduate School of Bio-Applications and Systems
Engineering, Tokyo University of Agriculture and Technology
Abstract:
Considerable works has revealed the presence of enzymes involved in lignin biosynthesis, andthe biosynthetic pathway of lignin is, now, generally accepted. However, thelocalization of each enzyme in cell is still open to discussion. O-Methyl transferase (OMT) catalyzes reactions
from caffeic acid to ferulic acid or from 5-hydroxyferulic acid to sinapic acid. We produced rabbit anti-OMT
antibody by using a fusion protein of a part of OMT and histidine as an antigen. Immunocytochemistry revealed
localization of OMT at differentiating xylem cells of populus and eucalyptus. Labelings of OMT was notobserved on any organelles but on cytosol.
1999-P03
シナピルアルコールの酵素的脱水素重合に対するコニフェリルアルコール混合の影響
小林孝行*1、鈴木正史*1、重松幹二*1、棚橋光彦*1、小名俊博*2*1
岐阜大学農学部、*2 王子製紙株式会社森林資源研究所
Effect of the mixing of coniferyl alcohol on the enzymatic dehydrogenative polymerization of sinapyl alcohol
Takayuki Kobayashi*1, Masashi Suzuki*1, Mikiji Shigematsu*1, Mitsuhiko Tanahashi*1, Toshihiro Ona*2*1
Faculty of Agriculture, Gifu Universty, *2Forestry Research Institute, Oji Paper Co. Ltd.
Abstract:
Sinapyl alcohol reacts very slowly by horseradish peroxidase (HRP) comparing with othermonolignols, but it reacts so fast by addition of guaiacyl or p-hydroxyphenyl compound. Some phenolicmaterials were used to investigate the influence of their functional groups on the HRP reaction. Further, theposibility of the radical transportation was investigated by two-layer system in which sinapyl alcohol was
separated from HRP by ultra filter. From the results, we proved that some phenolic materials play a roll as aradical mediator.
1999-P04
分子軌道法による種々の溶媒中でのリグニン前駆体のコンフオメーション解析
重松幹二、小林孝行、棚橋光彦
岐阜大学農学部
Molecular orbital analysis on the conformations of monolignols dissolved in various solvents
Mikiji Shigematsu, Takayuki Kobayashi, Mitsuhiko Tanahashi
Faculty of Agriculture, Gifu University
Abstract:
Solvent effect on the optimum conformations of monolignols was computer-simulatedby MOPAC97 program including PM3 and COSMO methods. In the cases of guaiacol and coniferyl alcohol, theBoltzman's probability of hydrogen bond between phenolic hydroxyl and methoxyl groups was decreased byincrease of the dielectric constant of solvent, for example, 96% in gas phase, 86% in benzene, 48% in pyridine
and 36% in water. In the cases of 2,6-dimethoxyphenol and sinapyl alcohol, the 60% of phenol hydrogenoriented to either of two methoxyl oxygens in gas phase, but less than 30% in water.
325

1999-P05
リグニンの NMR におけるシフト試薬の効果
関口俊司、新谷博幸、飯塚堯介
東京大学大学院農学生命科学研究科
The effect of shift reagents on NMR spectra of lignin
Syunji Sekiguchi, Hiroyuki Shintani, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
The shift reagents have been applied for the separation of overlapped peaks in NMR spectra. ln
this paper, the effect of Eu-FOD and Pr-FOD, which are common shift reagents, on NMR spectra of lignin wasinvestigated. Signals in 1H-NMR spectra of acetylated MWL (milled wood lignin) were broadened by theaddition of those shift reagents, and the resolution of spectra became even worse. The main reason for this resultmust be the difficult complex formation caused by the bulkiness of lignin molecule. Further modifications ofconditions (ex. solvent, temperature, kind of derivatization) are needed for the effective application of shift
reagents on NMR spectrometry of lignin.
1999-P06
セプターパヤ細胞壁の成分とタンニンの特徴
鶴田暁史*1、大井 洋*1、大原誠資*2*1
筑波大学農林工学系、*2 森林総合研究所
Characteristics of cell wall components and tannins from the wood of Pseudosindora palustris
Akifumi Tsuruta*1, Hiroshi Ohi*1, Seiji Ohara*1*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2 Forestry and Forest Products
Research Institute
Abstract:
Pseudosindora palustris wood contained 18.9% of polyphenols and 23.6% of acid insoluble
lignin. From acetone-water (7:3) extracts of he wood fisetinidol and fisetinidol-(4α→8)- catechin were isolated
after separation by column chromatography. 13C-NMR spectra indicated that polymers from the acetone-water
extracts were prpanthocyanldin polymers which mainly consisted of profisetinidin. On-line methylation
pyrolysis-gas chromatography gave 3, 4-dimethoxytoluene from die B ring, 1, 3-dimethoxybenzene from the A
ring, and a pyrolysis product which was assumed to be 1-(2-methoxyethyl)-2, 4, 6-trimethoxybenzene. It has
been made clear that the proantho- cyanidin polymers consist of profisetinidin units including a small number ofprocyanidin units.
1999-P07
チヤボヒバ（Chamaecyparis obtusa cv. Breviramea)から単離された新規リグナンについて
高久尚裕、奥西智哉、三亀啓吾、鈴木史朗、梅澤俊明、島田幹夫
京都大学木質科学研究所
A new lignan from Chamaecyparis obtusa cv. Breviramea
Naohiro Takaku, Tomoya Okunishi, Keigo Mikame, Shiro Suzuki, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
A new lignan, which is an isomer of actifolin named isoactifolin, and three known lignans,dihydrosesamin, piperitol, and sesamin, were isolated from the methanol extracts of leaves of Chamaecyparis
obtusa cv. Breviramea.
1999-P08
ニオイヒバリグナンの検索とそれらリグナン類の生合成について
榎本慎一、河合真吾、大橋英雄
岐阜大学農学部
Isolation and identification of Thuja occidentalis lignans and their biosyntheses
Shin-ichi Enomoto, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
Five lignans, (8R, 8'R)-(-)-yatein, dihydroxythujaplicatin methyl ether, thujastandin, lariciresino,
pinoresinol were isolated from Thuja occidentalis xylem, besides the previously identified seven lignans. Chiral
HPLC analysis of yatein indicated that the compound was optically pure. The presence of secoisolariciresinol
was also identified by GC-MS analysis of the extract of T. occidentalis xylem. Feeding experiments of [9, 9-2H2,
OC2H3]coniferyl alcohol and [7, 7-2H2, 3'326

OC2H3] secoisolariciresinol into T. occidentalis young shoots resulted that two molecules of coniferyl alcohol
were incorporated into pinoresinol and lariciresinol, and secoisolariciresinol was incorporated into lariciresinol.
1999-P09
数種の培養細胞を用いたリグナン、ポドフイロトキシンのバイオトランスフオーメーションによるリナン配糖体の調製の試み内藤隆行、伊藤和貴、橘 燦郎
愛媛大学農学部
Trial for preparation of podophyllotoxin glucoside by biotransformation of podophyllotoxin by use of someplant cell cultures
Takayuki Naito, Kazutaka Ito, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Production of podophyllotoxin glucoside by biotransformation of podophyllotoxin by use ofcell suspension cultures of Gardenia jasminoides, Nicotiana tabacum and Datura innoxia was tried. From theresults of HPLC analysis of each reaction product, we found that podophyllotoxin glucoside was produced by
the cultures of D. innoxia in the maximum yield of 4.6%. However, the glucoside could not be produced by thecultures of G. jasminoides and N. tabacum.
1999-P10
Mn(II)酸化能を有する微生物に関する研究
西中亜紀子、堤 祐司、西田友昭
静岡大学農学部
Studies on Mn( II )-oxidizing microorganisms
Akiko Nishinaka, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
Screening of microorganisms which can oxidize Mn(II) to Mn(III) was attempted. One of suchmicroorganism from literatures, Leptothrix discophora SS-1(SS-1), was examined its potential of Mn(III)formation from Mn(II). The prepared crude enzyme from SS-1 could oxidize Mn(II) to MnOx and effectively
convert Mn(II) to Mn(III) in the presence of pyrophosphate as a chelator of Mn(III). Also, 336 of positivebacterial colonies were isolated from the samples collected from Taguchi mine, Japan, by their ability of MnOx
formation from Mn(II) on the plate. Twenty-six colonies were further selected from 336 and their ability ofMn(III) formation is in progress.
1999-P11
白色腐朽菌が産生するマンガンペルオキシダーゼ活性化物質について
扇 剛士、鬼束愛子、近藤隆一郎、坂井克己
九州大学農学部
Production of extracellular manganese peroxidase activity-stimulating substances by white rot fungi
Takeshi Ougi, Aiko Onitsuka, Ryuichiro Rondo, Kokki Sakai
Faculty of Agriculture, Kyusyu University
Abstract:
Manganese peroxidase (MnP) is an extracellular heme protein produced by wood-rotting andlitter-degrading basidiomycetes especially during secondary metabolism. MnP catalyzes the H2O2-dependentoxidation of phenolic lignin structures. We had interest in producing of extracellular MnP activity-stimulating
substances by white rot fungi. Phanerochaete sordida YK-624 and P. chrysosporium were cultivated in theliquid medium, and extracellular low molecular-weight substances were prepared. Addition of extracellular
substances, which is equivalent amounts of Mn to MnSO4, to the MnP reaction mixture increased the MnPactivity comparing with MnP-MnSO4 system. Addition of Kirk medium instead of MnSO4 to the reaction
mixture did not increase the MnP activity. These results suggest that white rot fungi night produce extracellular
MnP activity- stimulating substances.
1999-P12（発表中止）

1999-P13
白色腐朽菌 MZ-340 株の 18SrDNA による系統学的分類
須原弘登、近藤隆一郎、坂井克己、白石 進
327九州大学大学院生物資源環境科学研究科
Taxonomy of the white rot fungus MZ-340 using 18SrDNA
Hiroto Suhara, Ryuichiro Kondo, Kokki Sakai, Susumu Shiraishi
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) havebeen a public concern for several decades because of their strong toxicity. We have suggested that one white rot
fungus, tentatively named strain MZ-340, collected from natural forest in Japan, can degrade PCDDs and
PCDFs. To identify the classification of the strain MZ-340, nucleotide sequences of the small subunit ribosomal
RNA gene were examined. The strain MZ-340 was closely related to Phanerochaete chrysosporium or Phlebia
radiata when searched with “DDBJ BRAST search”. Subsequently phylogenetic relationship of strain MZ-340
was investigated by ''Phylip package” using our sequences and data on “GenBank”. Based on our current data,strain MZ-340 could be classified as family of Corticiaceae including genus of Phanerochaete and Phlebia.
1999-P14
白色腐朽菌によるダイオキシン類の in vitro 分解 (III) 〜MZ-340 株産生酵素の基質特異牲について〜
森智夫、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
In vitro degradation of dioxins by white rot fungi (III), 〜Substrate specificity of extracellular enzyme from thefungus MZ-340〜
Toshio Mori, Ryuichro Kondo, Kokki Sakai
Faculty of Agriculture, Kyushu University
Absreact:
The white rot fungus strain MZ-340 was screened as the strain having dioxins- degrading ability.
We have previously reported that culture filtrate from the strain MZ-340 can degrade
2,7-dichlorodibenzo-p-dioxin and 2,8-dichrlorodibenzofuran. The purpose of present study was to examine
whether biarylic compounds such as dioxins or dioxin like compounds can be degraded by the culture filtratefrom the strain MZ-340. 2,7 dichlorodibenzo-p-dioxin, 2,8-dichloro- dibenzofuran and 4,4’-dichlorobiphenyl
were reacted with the filtrate, although non-chlorinated compounds, dibenzo-p-dioxin, dibenzofuran andbiphenyl were not. Probably, chlorine-substitution will be important in this enzymatic reaction.
1999-P15
担子菌におけるケミカルストレス応答タンパク質の検索
森下大史、一瀬博文、栗原宏征、割石博之、田中浩雄
九州大学農学部
Search for the new proteins from the basidiomycetes
Hiroshi Morishita, Hirofumi Ichinose, Hiroyuki Kurihara, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
To investigate the mechanism of substrate recognition and metabolic response, 2-dimensional
protein electrophoresis and differential display techniques were utilized. The cell free extracts prepared fromfungal hyphae in the presence of the chemical stress were compared with those from non-stressed cell. Dioxins,biphenyls, and dibenzothiophenes were utilized as a chemical stress, since their metabolic pathways were atleast partially elucidated. The addition of these compounds resulted in the appearance of new proteins and theexpression of specific genes.
1999-P16
木材腐朽菌によるケナフパルプの漂白
大前陽子、大谷慶人、鮫島一彦
高知大学農学部
Biobleaching of kenaf bast pulp by wood rot fungi
Yoko Ohmae, Yoshito Ohtani, Kazuhiko Smeshima
Faculty of Agriculture, Kochi University
Abstract:
Biobleadhing of kenaf bast pulp was tried using some wood-rot fungi screened andisolated from the field and typical ones; Pleurotus ostreatus and Phanerochaete chrysosporium.
Each fungus precultured in Kirk medium was inoculated upon kenaf bast pulp and incubated statically at 29ºC.
The mest effective fungus was OM5-1 screened in our laboratory. It has an ability to increase pulp brightness 2
tines larger and to decrease kappa number 1.5 tines larger than P. chrysosporium. It also showed higher initial328

Mn peroxidase activity than P. chrysosporium.
1999-P17
溶媒再循環プロセスによる HBS パルプ化（2）—広葉樹材および草本類の脱リグニン—
ワヒュ・エコ・ウイドド、佐野嘉拓
北海道大学大学院農学研究科
HBS pulping with solvent-reycling process (2), —Delignification of hardwood and annual plants—
Wahju Eko Widodo, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
In order to develop a new pulping process with non-pollution and saving energy, hardwood(birch and commercial E. globulus) and annual plants (kenaf, palm oil wastes, rice and wheat straws, andbagasse) were subjected to delignification by HBS pulping prpocess with high boiling-point solvents (HBS)
with and without acetic add. They were significantly delignified at 200ºC for 3 h without acetic acid and for 2 hwith 5-10% AcOH of the solvent. The RHBSs removed only lignin from pulping waste liquors were possible toreuse several times as pulping solvent.
1999-P18
常圧酢酸パルプ化 —パルプ廃液から得られる糖成分の考察
久保田康恵、佐野嘉拓
北海道大学大学院農学研究科
Atmospheric acetic acid pulping, -Carbohydrate in water solubles fractionated from waste liquor
Yasue Kubota, Yoshihiro Sano
Faculty of Agriculture, Hokkaido University
Abstract:
Atmospheric acetic acid pulping (AcOH pulping) is one of the organosolv pulping aimed at
total utiliziation of biomass. Birch, todomatsu and rice and wheat straws were fractionated into pulp, lignin andwater solubles by the pulping. Each water solubles were obtained in yields of 20-30% of raw material andcontained monosaccharides (sugars,40-50% of water solubles) and colored substances. The sugars were easily
purified with carbon-celite, following by conversion to alditols by catalytic hydrogenolysis with Raney Nickel.
The alditols purified by ion-exchange resin were analyzed.
1999-P19
自己会合牲ヒドロキシプロピルリグノセルロース誘導体の溶液挙動
半崎亜希子*1、浦木康光*1、佐野裏拓*1、浦川 宏*2、安永秀計*2、梶原莞爾*2*1
北海道大学大学院農学研究科、*2 京都工芸繊維大学工芸学部
Solution property of self-assembled hydroxypropylated lignocellulose derivative
Akiko Hanzaki*1, Yasumitsu Uraki*1, Yoshihiro Sano*1, Hiroshi Urakawa*2, Hidekazu Yasunaga*2, Kanji
Kajiwara*2*1
Graduate School of Agriculture, Hokkaido University, *2Faculty of Engineering and Design, Kyoto Institute ofTechnology
Abstract:
Solution behavior of hydroxypropylated (HP) lignocellulose that was prepared from acetic acid
pulp was investigated by the small angle X-ray scattering (SAXS) and the measurement of lower criticalsolution temperature (LCST) to clarify the self-assembly. Kratky plot of SAXS indicated that HP-lignocellulose
was a rod-like polymer both in water and tetrahydrofuran as well as commercially HP-cellulose (HPC). The
cross-sectional radium of gyration was found to increase with the increase in residual lignin content by Guinierplot. LCST of HP-lignocellulose was approximately 36ºC, while HPC had LCST above 39ºC. These results
suggest that the residual lignin in the self-assembled HP-lignocellulose remarkably affected polymer structure
and phase separation in the solution.

329

第 45 回 （2000.10.26-27） 愛媛大学農学部
2000-101
広葉樹シリンギルリグニンの生成機構
山内一慶*1、福島和彦*1、安田征市*1、浜田勝義*2、堤祐司*2*1
名古屋大学大学院生命農学研究科, *2 静岡大学農学部
The biosynthetic mechanism of syringyl lignin in angioperm
Kazuchika Yamauch*1, Kazuhiko Fukushima*1, sehchi Yasuda*1, Katsuyoshi Hamada*2, Yuji Tsutsumi*2*1
Grduate School of Bioagicultural Sciences, Nagoya University, *2Facul[y of Agriculture, Shizuoka University
Abstract:
There is a great interest in the question whether sinapic acid is the true precursor of syringyl
lignin or not, because the activity of 4-coumarate:CoA ligase (4CL) for sinapic acid was not detected in many
angiosperms. We synthesized labeled sinapic acid-[2OMe-d6,β-d] and [2OMe-d6,β-13C], and administered into
angiosperms (Nerium indicum Mill. and Robinia pseudoacacia L.). The newly formed xylem of administeredwoods was analyzed by DFRC method. Labeled sinapic acid was incorporated into the syringyl lignin
accompanied by all labels. Our results suggested the existence of the pathway from sinapic acid to sinapy1
alcohol via sinapoyl CoA.
2000-102
コニフェリルアルコールの脱水素重合中に生成するシリンギル核
斉藤香織*1、安田征市*1、小名俊博*2、福島和彦*1
1
名大院生命農, 2 王製紙㈱森林資源研究所
Syringyl units generated during the polymerization of coniferyl alcohol
Kaori Saito1*1, Seiichi Yasuda*1, Toshihiro Ona*2, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, *1Forestry Research Institute, Oji Paper Co.
Ltd.
Syringyl (S) and p-hydroxyphenyl (H) units were detected in addition to guaiacyl (G) unit in thioacidolysis
products of the DHP prepared from only coniferyl alcohol by peroxidase- H202 system. We established theappropriate condition for the formation of S and H units during the polymerization of coniferyl alcohol. We also
prepared DHPs from methoxyl-d-labeled coniferyl alcohol to clarify the mechanism for the formation of S andH units, but we could not prove the transference of methoxyl groups.
2000-103
シリンギルリグニン生合成におけるシナップ酸と 4-Coumarate: Coenzyme A Ligase の役割
浜田勝義*1、宮武亜樹子*1、福島和彦*2、堤 祐司*1、西田友昭*1*1
静岡大学農学部、*2 名古屋大学大学院生命農学研究科
The role of sinapic acid and 4-coumarate: coenzyme A ligase in syringyl lignin biosynthesis
Katsuyoshi Hamada*1, Akiko Miyatake*1, Kazuhiko Fukushima*2, Yuji Tsutsumi*1, Tomoaki Nishida*1*1
Faculty of Agriculture, Shizuoka University, *2Graduate School of Bioagricultural Sciences, Nagoya
University
Abstract:
We investigated the involvement of sinapic acid (SA) and 4-coumarate: Coenzyme A ligase(4CL) in syringyl lignin biosynthesis. Deuterated ferulic acid (FA) [3-OD3,β-D] and SA [3,5OCD3,β-D] were administered to poplar (Populus alba L.) callus cultures as precursors of lignin. The
thioacidolysis analyses of the administered calluses showed that the deuterated SA was not converted toguaiacyl and syringyl lignins, while SA administration clearly increased syringyl lignin content in the callus.
4CL activity against SA was not observed in the homogenized cell, crude enzyme, and microsome preparations
by an enzyme assay using 14C-labeled SA. The results suggest that SA is not a precursor of syringyl lignin per sebut induces or enhances syringyl lignin biosynthesis in the callus.
2000-104
ヒャクニチソウ管状要素分化過程における細包外リグニン前駆体の存在とリグニン化への影響
細川麻美*1、鈷木史朗*2、梅沢俊明*2、佐藤 康*1*1
愛媛大学理学部、*2 京都大学木質科学研究所、
Existance of extracellular lignin precursors and their effects on lignification during tracheary element
differentiation of Zinnia
Mami Hosokawa*1, Shiro Suzuki*2, Toshiaki Umezawa*2, Yasushi Sato*1
330

Faculty of Science, Ehime University, Wood Research Institute, Kyoto University
Abstract:
We investigated how and whence monolignols are supplied to tracheary elements (TEs)undergone programmed cell death using an experimental system of TE differentiation from isolated Zinnia
mesophyll cells. Alternations of culture condition indicated that monolignols were supplied to TEs throughmedium. Analyses by HPLC and GC-MS showed that coniferyl alcohol were mainly accumulated in cultured
medium. The concentration of coniferyl alcohol peaked at the beginning of secondary wall thickening,
decreased during secondary wall thickening, then increased again. These results indicated that lignification of
TEs progressed by supply of monolignols from not only TEs themselves but also surrounding xylem
parenchyma-like cells.
2000-105
アスパラガス培養細胞の産生する cis-ヒノキレジノールの生合成機構こついて
鈴木史朗、梅澤俊明、島田幹夫
京都大学木質科学研究所
The biosynthesis of cis-hinokiresinol produced by cultured cells of Asparagus officinalis L.
Shiro Suzuki, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
The biosynthesis of a norlignan, cis-hinokiresinol, was studied by feeding of labelled
compounds into cultured cells of Asparagus officinalis L. treated with fungal elicitor. The SIM-MS analysis
showed that two 13C atoms were incorporated into a single molecule of cis-hinokiresinol when
[7-13C1]cinnamate and [8-13C1]cinnamate were administered individually to the cells, while only one 13C atom
originated from [9-13C1]cinnamate was incorporated into the compound. The NMR analysis of cis-hinokiresinol
produced by the cells fed with [9-13C1]cinnamate revealed the incorporation of a single 13C atom into the
9-position of cis-hinokiresinol. The cells administered with 4-[8-13C1, ring-13C6]coumarate produced
cis-[13C14]hinokiresinol. These results unequivocally indicated for the first time that cis-hinokiresinol wasformed by the coupling of two phenylpropanoid monomer units with the loss of one carbon of the 9-position of
the monomer.
2000-106
Sphingomonas paucimobilis SYK-6 株のリグニン代謝に関わる脱メチル化酵素機能の多様性と遺伝子配置
園木和典、大塚祐一郎彰 学、政井英司、福田雅夫、片山義博
東京農工大学大学院 BASE、長岡技術大学工学部
An enzymatic diversity involved in the O demethylation of lignin metabolism and the gene arrangement in
Sphingomonas paucimobilis SYK-6
Tomonori Sonoki, Yuichiro Otuka, Xue Peng, Eiji Masai, Masao Fukuda, Yoshihiro Katayama*1
Graduate school of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, Nagaoka University of Technology
Abstract:
Sphingomonas paucimobilis SYK-6, a bacterium that can grow on 5,5’-dehydrodivanillic acid
(DDVA) as a sole carbon source, and call also grow on several dimeric model compounds of lignin. This meansthat this bacterium has various enzyme systems for getting energy from poor degrading compounds such as
lignin. S. paucimobilis SYK-6 has the O demethylation systems upon three kinds of substrates; DDVA,
syringate, and vanillate. We succeeded in detecting enzyme activity and moleular cloning involved in DDVA
spedcific O demethylation and syringate and vanillate specific O demethylation. The biochemical analysis of O
demethylation systems revealed that the O demethylation system of DDVA was oxygenase system and that ofsringate and vanillate was tetrahydrofolate dependent methyltransferase system. In the genome of SYK-6, thebiphenyl specific O demethylase gene and dioxygenase involved in ring fission located in the neighborhood.
2000-107
担子菌におけるダイオキシンストレス応答遺伝子
栗原宏征、割石博之、田中浩雄
九州大学大学院生物資源環境科学研究科
Dioxin stress responsible genes from lignin-degrading basidiomycete
Hiroyuki Kurihara, Hiroyuki Wariishi, Hiroo Tanaka
Graduate School of Bioresources and Bioenvironmental Sciences, Kyushu University
Abstract:
To survey the enzymes and genes involved in fungal degradation of dioxin derivatives, the331effect of exogenous dibenzo-p-dioxin on extracellular enzyme activities and gene transcription were studied.
Lignin peroxidase activity in the culture medium of white-rot fungus Phanerochaete chrysosporium increased
upon the addition of dibenzo-p-dioxin, strongly suggesting the involvement of LiP in the oxidation of thiscompound. A series of dioxin stress responsible genes were detected using a differential display RT-PCR
technique. Several cDNAs of those responsible genes (FDD-1 to -6) were further characterized. The full length
cDNA of FDD-1 was determined and sequenced, indicating that its deduced amino acid sequence showed a highhomology to that of quinone oxidoreductase. The expression of this gene was confirmed when dibenzo-p-dioxin
and catecol were added but not when dibenzofuran was added. The protein encoded by FDD-1 might play animportant role in the reduction of LiP-derived quinone products to the corresponding phenolic compounds forfurther metabolism.
2000-108
担子菌類の汚染物質分解遺伝子を導入した植物の分子育種と持続的環境修復に関する研究
池田成一郎*1、園木和典*1、飯付洋介*2、早川敏夫*3、金原和秀*3、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 工業技術院資源環境技術総合研究所、*3JR 総合技術研究所
Studies on molecular breeding of plants with fungal ability degrades of environmental pollutants and continuous
remediation
Seiichiro Ikeda*1, Tomonori Sonoki*1, Yosuke Iimura*2, Toshio Hayakawa*3, Kazuhide Kinbara*3, Sinya Kajita*1,
Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2National Institute for Resources and Environment, *3Railway Technical Research Institute.
Abstract:
Plants offer many advantages over bacteria as agents for bioremediation; however, they
typically lack the degradative capabilities of specially selected bacterial strains. Innate biodegradative abilitiesof plants are less impressive than those of adapted bacteria and fungi, but these disadvantages are balanced by
the large amounts of plant biomass that can easily be sustained in the field. Transgenic plants expressing
microbial degradative enzymes could combine the advantages of both systems. To investigate this possibility,
we generated transgenic plants expressing Manganese Peroxidase(MnP), an enzyme derived from Coliolus
versicolor. In comparison with control, transgenic callus showed high MnP activity.
2000-109
リグニンの -aryl ether 結合の特異的開裂機能を有する新規糸状菌 2BW-1 株の機能及び酵素学的研究
大塚裕一郎、園木和典、片山義博
東京農工大学大学院 BASE
Detection and characterization of new fungous enzyme catalyzing cleavage of guaiacylglycerol-β- aryl etherbond
Yuichiro Ohtsuka, Tomonori Sonoki , Yoshihiro Katayama*1
Graduate school of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology
Abstract:
Fungus lignin degradation has studied to upspecific degradation from the viewpoint of lignin.
The specific degradation of low molecular lignin has been studied in soil bacterium while that of high molecularlignin isn’t yet detected. We forcused in the fungi world that have special extracellular deqvqge fmdnleavage
function. In this report, we succeeded isolation the fungus, 2BW-1 strain, that has specifical β-aryl ether cleavge
function. This function was observed at the extracellular fraction. In this fraction, theeguaiacylglycerol-β-O-guaiacyl (GOG) was converted into the guaiacylglycerol. It is the new fungus specificallignin degrading function.
2000-110
耐塩牲白色腐朽菌に関する研究（III）：耐塩牲白色腐朽菌 MG-60 株が産生する MnP の特性
李 シン、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
Studies on hypersaline-tolerant white-rot fungi. (III). Characterization of manganese peroxidase from a marine
fungus MG-60
Xin LI, Ryuichiro Kondo, Kokki Sakai
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
Characterization of MnPs secreted by a fungus, MG-60 that was incubated at 0% and 3% sea
salts concentrations, was reported and the purified MnPs were represented as MnP-0 and MnP-3, respectively, in332

this paper. The MnPs were highly tolerant to sea salts and NaCl. The optimum pH and temperature of MnP-0
was 4 and 65ºC, respectively, while, for MnP-3, optimum pH was 3 and optimum temperature was 60ºC.
2000-111
マンガンペルオキシダーゼ活性に影響を及ぼす担子菌菌体外物質について
扇 剛士、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
The extracellular manganese peroxidase activity-stimulating substances produced by basidiomycetes
Takeshi Ougi, Ryuichiro Kondo, Kokki Sakai
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
Manganese peroxidase (MnP) is an extracellular heme protein produced by wood-rotting andlitter-degrading basidiomycetes especilly during secondary metabolism. MnP catatyzes the H2O2-dependentoxidation of phenolic lignin structures. We have focused in extracellular MnP activity-stimulating substances
produced by white rot fungi. The best-studied lignin-degrading fungus, Phanerochaete chrysosporiumum wascultivated in the liquid medium, and extracellular MnP activity-stimulating substances were prepared. Additionof extracellular substances increased the MnP activity comparing with MnP-MnSO4 system even in succinate
buffer. GPC analyses show thepossibility that extracellular substances have absorption at 280nm.
2000-112
ラッカーゼ・1-HBT 系による非フェノール性 β-O-4 型リグニンモデル化合物の分解機構の解析
中川 誠、河合真吾、大橋英雄
岐阜大学農学部
Degradation mechanism of non-phenolic β-O-4 ligmin model compound by laccase-1-HBT system
Makoto Nakagawa, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
In the previous work, we demonstrated that Trametes versicolor laccase catalyzed not onlyCα-Cβcleavage, C oxidation and β-ether cleavage but also aromatic ring cleavage of a non-phenolic β-O-4lignin model dimer, 1,3-dihydroxy-2-(2,6-dimethoxyphenoxy)-1-(4-ethoxy-3- methoxyphenyl)propane (i), in
the present of 1-HBT. This paper reports the incorporation experiments of 18O from H218O and 18O2 into thedegradation products of substrate (i) catalyzed by laccase-1-HBT system. Furthermore, the degradation
mechanisms for non-phenolic β-O-4 lignin model dimer by this system are discussed.
2000-113
白色腐朽菌 Ceriporiopsis subvermispora によるポリイソプレノイドの分解
佐藤 伸、榎 牧子、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
Degradation of polyisoprenoids by white rot fungus Ceriporiopsis subvermispora
Shin Sato, Makiko Enoki, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Vulcanized natural rubber sheet was intensively degraded on wood meal cultures by aselective white rot fungus, Ceriporiopsis subvermispora, while Dichomitus squalens was not able to decompose
the rubber sheet under the same culture condition. C. subvermispora also decomposed synthetic polyisoprenoids,
styrene-butadiene rubber (SBR) and ethylene-propylene rubber (EP) in addition to natural polyisoprene isolated
from natural rubber latex on wood cultures. Structural changes of the fungal treated polyisoprenoids wereanalyzed.
2000-114
MnP-脂質過酸化複合系による多環式芳香属炭化水素類の酸化松浦好高*1、長野和種*2、堤 祐司*1、西田友昭*1*1
静岡大学農学部、*2 名古屋大学大学院生命農学研究科
Oxidation of polycyclic aromatic hydrocarbons by MnP-lipid peroxidation system
Yositaka Matsuura*1, Kazutane Nagano*2, Yuji Tsutsumi*1, Tomoaki Nishida*1*1
Faculty of Agriculture, Shizuoka University, *2Graduate School of Bioagricultural Sciences, Nagoya
University333Abstract:
We investigate the reaction mechanisms in the oxidation of polycyclic aromatic hydrocarbons
by a MnP-mediated lipid peroxidation system. In the system containing 100 mU/ml of MnP, linoleic acid was
rapidly consumed and produced active radical species to react with anthraene (AT), consequently a decrease of
AT followed to almost a pseudo-first order reaction. The oxidation rates of linoleic acid and AT were not largely
affected by the reduction of MnP concentration down to 25 mU/ml in the system. A reaction with very low MnPconcentration (2.5 mU/ml) in the system suggests that the MnP-mediated lipid peroxidation to produce active
radical species is composed of at least two reactions: the first step is very fast and probably the formation ofperoxidized-lipid as intermediates, and the next is the formation of active radical species from intermediates.
2000-115
ペルオキシダーゼ活性を抑制した組換え樹木のリグニン構造
諸星紀幸*1、李 亜紅*1、並木理卓*1 西窪伸之*1、梶田真也*1、辻 幸子*２
*1
東京農工大学大学院 BASE,、*2 名古屋大学大学院生命農学研究科
Lignin chemical structure of transgenic poplar controlling the peroxidase activity
Noriyuki Morohoshi*1, Li Yahong*1, Ritaku Namiki*1, Nobuyuki Nishikubo*1, Shinnya Kajita*1, Yukiko Tsuji*2*1
Graduate School of Bio-application and Systems engineering, Tokyo University of Agriculture andTeclmology, *2Grduate School of Bioagicultural Sciences, Nagoya University
Abstract:
The objective of our research was to form a super tree using new biotechnological and genetic
engineering techniques. The primary aim was to produce a tree with a lower lignin content by controlling lignin
biosynthesis genes using antisense RNA. The isolation and sequencing of prxA3a involved in lignification fromhybrid aspen (Populus kitakamiensis) was achieved. The transgenic poplars had lower total peroxidase activity
compared with that of the control. After peroxidase isozyme analysis by the isoelectric focusing, it was clearthat a peroxidase band (pI 3.8) disappeared in the transgenic plants. The lignin content in transgenic plants
decreased 20-50% compared with control parts when the potassium permanganate oxidation method was used.
A characteristic of the lignin chemical structure in transformants are to have more syringyl units, beta-O-4
structures and condensed units. The decrease of syringyl units and lignin contents in the primary xylem tissue oftransformant (POX27) were also observed by the ultraviolet microscopy.
2000-116
酸化的脱リグニン過程での-O-4 型側鎖構造の変化について
杉本倫子、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Change in side-chain of β-O-4 structure during oxidative degradation of lignin
Tomoko Sugimoto, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School ofAgricultural and Life Sciences, the University of Tokyo
Abstract:
By the ozonation method, erythro and threo (E/T) ratio of arylglycerol-β-aryl ether (β-O-4)
structure can be obtained as a ratio between two ozonation products, erythronic and threonic acids. Previously,
when wood samples were delignified by NaClO2 treatment, no significant change was observed in E/T ratio of
residual lignin. In order to confirm the reason for this, MWL was treated with NaClO2, and changes inside-chain part (β-O-4 structure) of lignin were observed by ozonation method. NaClO2 treated MWL showedalmost the same E/T ratio as starting MWL, indicating that delignification reaction proceeded homogeneously
during NaClO2 treatment. When MWL was reduced by NaBH4, the yield of both acids increased. This increaseis due to the reduction of β-O-4 structure that possessesα-carbonyl structure, but since the reduction of NaBH4
was stereo-preferential, the increase in threonic acid was greater than erythronic acid. When thisNaBH4-reduced MWL (red-MWL) was treated with NaClO2, the yields of both acid decreased but notsignificantly. Probably, oxidatively cleaved aromatics during NaCO2 treatment can still give erythronic andthreonic acids by ozonation if they carry β-O-4 structure. But when NaBH4 reduction was conducted after
NaClO2 treatment, the yield of ozonation product decreased significantly. The reason for this is probably thatthe reduction of cleaved aromatics would change these structures into structure that could not produce erythonicand threonic acids by ozonation method. These NaClO2 treatments of red-MWL were conducted in aerobic andanaerobic atmosphere, but no significant difference was observed between these two. At least in this reaction
condition, the presence of oxygen does not affect the NaClO2 treatment of (red-)MWL.
2000-117
リグニン中の β-O-4 型側鎖構造の光学活性に関する研究
秋山拓也*1、松本雄二*1、飯塚堯介*1、石津 敦*1、真柄謙吾*2
334

*1

東京大学大学院農学生命科学研究科、*2 森林総合研究所
Studies on the optical activities of β-O-4 structure in lignin by ozonation method
Takuya Akiyama*1, Yuji Matsumoto*1, Gyosuke Meshitsuka*1, Kengo Magara*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Forestry and Forest Products
Research Institute
Abstract:
Erythronic acid and threonic acid were obtained from corresponding erythro and threo forms ofarylglycerol-β-aryl ether structure in lignin by ozonation of Birch wood meal. These acids
obtained from lignin keep the stereo structure of side-chain part of β-O-4 ether structure. Erythronic andthreonic acids were separated by HPLC and were collected, respectively. The fraction of erythronic acid was
subjected to HPLC analysis, and the optical activity was measured by on-line optical rotation detector. The
optical activity of threonic acid was also measured. It was confirmed that both erythro and threo forms ofarylglycerol-β-guaiacyl ether structure consist of two enamtiomers. It was strongly suggested that the erythro
forms of arylglycerol-β-guaiacyl ether structure is optically inactive (enantiomer excess (e.e.)< 3.5%). As to
threonic acid, because of the incompleteness of purification, maximum e.e. was rather high but was still lessthan 10%.
2000-118
熱分解ガスクロマトグラフィーによるシンナムアルデヒドを含むモノリグノール比の解析
園田哲也*1、小名俊博*1、横井裕明*2、石田康行*2、大谷 肇*2、柘植 新*2
王子製紙株式会社森林資源研究所、名古屋大学大学院工学研究科
Characterization of monolignol ratio including cinnamaldehydes by pyrolysis-gas chromatography.
Tetsuya Sonoda*1, Toshihiro Ona*1, Hiroaki Yokoi, *2 Yasuyuki Ishida*2, Hajime Ohtani*2, Shin Tsuge*2*1
Forestry Research institute, Oji Paper Co. Ltd., *2 Grduate School of Engineering, Nagoya University
Abstract:
It is difficult to determine cinnamaldehyde components in lignin accurately by pyrolysis- gas
chromatography (Py-GC) because the secondary formation of cinnamaldehydes are considered to occur fromthe cinnamyl alcohol components in lignin during pyrolysis. In this work, we examined the compositional
analysis of monolignols including cinnamaldehydes in various DHPs and woods using pre-acetylation before
Py-GC in order to prevent the secondary formation of cinnamaldehydes during pyrolysis. On the basis of thecharacteristics peaks on the pyrograms, the monolignol ratios in various DHPs determined with taking
cinnamaldehydes into consideration were in excellent agreement with those in the DHP preparation.
2000-119
反応熱脱着ガスクロマトグラフィーによる木材中の抽出成分の迅速分析
横井裕明*1、中瀬敬二*1、後藤邦佳*1、石田康行*1、大谷 肇*1、柘植 新*1、園田哲也*2、小名俊博*2*1
名古屋大学大学院工学研究科、*2 王子製紙株式会社森林資源研究所
Rapid characterization of wood extractives by reactive thermal desorption-gas chromatography
Hiroaki Yokoi*1, Takahito Nakase*1, Kuniyoshi Goto*1, Yasuyuki Ishida*1, Hajime Ohtani*1, Shin Tsuge*1,
Tetsuya Sonoda*2, Toshihiro Ona*2*1
Grduate School of Engineering, Nagoya University, *2Forestry Research institute, Oji Paper Co. Ltd.
Abstract:
A novel rapid method to characterize wood extractives was developed on the basis of reactive
thermal desorption-gas chromatograhy (RTD-GC) in the presence of an organic alkali,
tetramethy1ammonium acetate ((CH3)4N+OCOCH3−;TMAAc). The reactive thermal desorption at 200ºC using
TMAAc allowed highly sensitive detection of wood extractives such as fatty acids, steroids and phenols in
Eucalyptus camaldulensis as their methyl derivatives on the resulting pyrograms without using any cumbersome
pretreatments such as solvent extraction. The distribution of fatty acids in extractives was able to estimate by
RTD-GC using powdered wood samples as received with relative standard deviations of around 5%. The
observed result was in good agreement with that determined using acetone solubles.
2000-特別講演
今後の植物の遺伝子組み換え
林 秀則
愛媛大学理学部
Invited Lecture: Future aspects in genetic engineering of plants
Hidenori Hayashi
Department of Chemistry, Ehime University
335

Abstract:
Gene engineering of stress tolerance in plants is powerful technique which would be helpful toimprove the crop productivity and to recover the damaged environment. So far target genes suitable for thispurpose have been searched from a variety of organisms and used for plant transformation. In addition to thesepreexisting gene, more potential genes would be available if we understand the molecular mechanism of eachgene product and design proteins having enhanced function by molecular engineering. In this lecture, I will
demonstrate an example of gene engineering to enhance the salt tolerance in plant with the gene for synthesis of
a compatible solute as well as our approach in the molecular engineering of proteins responsible for heavy metal
tolerance in cyanobacteria.
2000-201
MWL 抽出残渣からのリグニンの溶出挙動
廣沢修一、中坪文明
京都大学大学院農学研究科
The behavior of extraction of lignin from wood meal after extraction of milled wood lignin
Shuichi Hirosawa, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
At present, milled wood lignin (MWL) is mainly used to investigate chemical structure of lignin.
But the MWL is not representative of the total lignin component. Therefore, elucidation of chemical structure oflignin in the wood meal after extraction of the MWL (WMEM) is important. In this study, lignin in the WMEM
was fractionated by extractions with solvents for polysaccharides (hemicellulose, cellulose). Alkali extraction
was carried out for the purpose of extraction of hemicellulose and lignin. Then, cellulose and lignin was
extracted with LiCl/N, N-dimethylacetamide (DMAc). Determination of lignin contents, nitrobenzene oxidationand sugar analyses were carried out to elucidate behaviors of polysaccharides and lignin during extractions.
2000-202
非フェノール牲 α-O-アルキル β-O-4 型シリンギルリグニンモデルのエリスロ・スレオ体の NMR と酸加水分解
過程の速度論的解析
岸野正典*1、大井 洋*2、大原誠資*3*1
北海道立林産試験場、*2 筑波大学農林工学系、*3 森林総合研究所
NMR of erythro and threo forms of nonphenolic α-O-alkyl β-O-4 type syringyl lignin model and kinetics oftheir acid hydrolysis
Masanori Kishino, Hiroshi Ohi, Seiji Ohara
Hokkaido Forest Products Research Institute, Institute of Agricultural and Forest Engineering, University ofTsukuba, Forestry and Forest Products Research Institute
Abstract:
NMR chemical shifts of erythro and threo forms of α-ethyl ether derivatives ofveratrylglycerol-β-syringyl
ether
(VSE:
3-(3,4-dimethoxyphenyl)-2-(2,6-dimethoxyphenoxy)3-ethoxypropan-1-ol) were assigned on the basis of the kinetics for acid hydrolysis of each diastereomer of VSE
intothediastereomers
mixtureofveratrylglycerol-β-syringyl
ether
(VS:
1-(3,4-dimethoxyphenyl)-2-(2,6-dimethoxyphenoxy)propane-1,3-diol). One VSE diastereomer eluted earlier by
HPLC and the other diastereomer were named VSE1 and VSE2, respectively. The value of z1 defined as a molar
ratio (VS threo to VSE1) at which VSE1 gave VS threo during the acid hydrolysis was found to be 1.000. The
value of z2 for VSE2 giving VS erythro isomer of VS was 0.841. This indicates that VSE1 is the erythro form ofVSE. In addition, coupling constants (J) for both VSE1 (erythro VSE) and VSE2 (threo VSE) were 7.0Hz,
although those for erythro and threo forms of VS were 3.7 Hz and 7.5Hz, respectively. This indicates that
conformations of VSE are changed by introduction of α-ethyl group into VS.
2000-203
遺伝子組換えタバコから得られる木部組織のパルプ蒸解生性
梶田真也*1、石藤雅俊*2、原 晋一*2、川端治彦*2、諸星紀幸*1*1
東京農工大学大学院 BASE、*2 三菱製紙株式会社、
Pulping characteristics of xylem materials from transgenic tobacco phnts
Shinya Kajita, Masatoshi Ishifuji, Shin-ich Hara, Haruhiko Kawabata, Noriyuki Morohoshi
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Mitsubishi Paper Mills Limited,
Abstract:
4-Coumarate:CoA ligase (4CL) is a phenylpropanoid biosynthetic enzyme that converts336

hydroxycinnamic acids into corresponding CoA esters. Recently, we produced transgenic tobacco plants with achimeric gene for 4CL. The activity of 4CL and lignin content in the plants were depressed by effect of theintroduced gene. In this Study, we found that tobacco chips, the xylem
materials from the transgenic plants, was delignified more extensively than those from controls in Kraft pulping
process. This result indicates that genetic engineering of lignin biosynthesis with modulation of 4CL activity isan efficient tool for production of new wood materials.
2000-204
HBS パルプ化-RHBS の脱リグニン促進効果
梶本純子、佐野嘉拓
北海道大学大学院農学研究科
HBS pulping. -Acceleration effect of RHBS on delignification
Junko Kajimoto, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
HBS pulping with saving-energy and non-pollution was investigated using aqueous solvents(HBS) with boiling point of about 200ºC. Todomatsu and birch chips were satisfactorily pulped with the pulping
process. RHBS recovered only high molecular-weight lignin from spent liquors were reused several times as apulping solvent, though it consisted of sugars, modified sugars, low molecular-weight lignin and so forth as
minor components in addition of a main material HBS. RHBS was a more excellent pulping solvent than pure
HBS. The accelerated effect of RHBS on the delignification resulted from aldoses existed in RHBS. Bothdelignification with HBS and RHBS obeyed two pseudo first-order kinetics, bulk and final phases, respectively.
The rate constant of the bulk phase with RHBS was about 1.5 times that with HBS. We name the delignificationoflignin with aldoses " aldosolysis ". When heated with aqueous neutral solvent at temperatures of above 200ºC,
the depolymerization of lignin takes place by homolysis, though it is accelerated by aldosolysis.
2000-205
HBS パルプ化 —β-O-4 モデル化合物の反応（2） —岸本崇生、佐野嘉拓
北海道大学大学院農学研究科
HBS pulping. - Reaction of β-O-4 type lignin model compounds, (2)Takao Kishimoto, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
We have been proposed that phenolic β-aryl ethers in lignins are cleaved homolitically via theformation of quinone methide intermediates under HBS (high-boiling solvent) pulping conditions. In order toconfirm the delignification mechanism, a phenolic β-O-4 type lignin model compound,guaiacylglycerol-β-guaiacyl ether (GG) was treated with 70 wt % aq 1,4-butanediol solution at 180 ºC. Thirteencompounds including 4 monomers, 6 dimers, 2 trimers and 1 tetramer were isolated from the reaction products.
Most of those oligomeric products were generated by recombination of phenoxy radicals formed by homolysisof the β-aryl ether. These results support that phenolic β-O-4 linkages in lignin are cleaved by radical
mechanism under HBS pulping conditions.
2000-206
リグニン芳香核の酸化的開裂に伴う構造変化 —生成する低分子カルボン酸類の起源構造—
角田靖典、新谷博幸、飯塚堯介
東京大学大学院農学生命科学研究科
Structural changes of lignin at oxidative degradation of aromatic rings, -Origin of low molecular weight
carboxylic acids
Yasunori Tsunoda, Hiroyuki Shintani, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Hardwood kraft lignin was treated with alkaline oxygen (1 mol/L NaOH, 0.3 MPa, 70ªC, 8hours) in H2O, H2O-D2O (1:1) and D2O. 13C-NMR spectra of these three samples indicated the production ofmany kinds of low molecular weight compounds, especially a lot of carboxylic acids, and introduction of
deuterium atoms to their compounds, although quantitative evaluation of each compound or tructure was notaccomplished. When alkaline oxygen treated samples in H2O were heated in D2O/NaOD at 70ºC for 8 hours,
further structural change of some compounds were indicated by 13C-NMR.
337

2000-207
酸処理・過酸化水素漂白を用いるクラフトパルプの低二酸化塩素添加・無塩素漂白大井 洋
筑波大学農林工学系
Non-chlorine bleaching of kraft pulp with small addition of chlorine dioxide using acid treatment and peroxide
beaching
Hiroshi Ohi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Non-chlorine bleaching of hardwood kraft pulp (LUKP) with a small addition of chlorine
dioxide was investigated. Acid (A) treatment conducted at pH2-2.5 and 40-80ºC for 30-120min was proposed as
the pre-treatment of peroxide (P) beaching. By the A treatment, manganese could be reduced and removed
significantly. Kappa numbers of pulp were decreased slightly by the A treatment. The P bleaching at 105ºC
could be improved by stabilization of manganese (II) in pulp. Dioxins and coplanar PCBs from LOKP bleachingwith a very large excess of chlorine dioxide were determined. Formation of 2,3,7,8-TCDD and PCBs was at alittle higher level than the minimum level, but 2,3,7.8-TCDF was distinctly determined. A possibility that an
excess of chlorine dioxide may cause TCDFs formation was shown. Then, the sequences using the A-P
bleaching and a small addition of chlorine dioxide were developed; O-A-P-D, O-A-P-D-P2, A-P-A-P-D,
A-P-D-P2-D, A-P-H-D-P2, and O-A-P-A-P2, A-P-A-P for totally chlorine free bleaching of LUKP.
2000-208
リグニンの脱水素重合反応に対する分子軌道法によるコンピュータシミュレーション
重松幹二、小林孝行、杉野哲也、棚橋光彦
岐阜大学農学部
Computer simulation by molecular orbital calculation on the dehydrogenative polymerization of lignin
Mikiji Shigematsu, Takayuki Kobayashi, Tetsuya Sugino, Mitsuhiko Tanahashi
Faculty of Agriculture, Gufu University
Abstract:
Solvent effect on the dehyrogenative polymerization of lignin was computer-simulated bysemi-empirical molecular orbital calculation, MOPAC2000. The simulation was divided into three stages andanalyzed; 1) one electron oxidation of monolignols catalyzed by horseradish peroxidase (HRP) analyzed by
HOMO energy level, 2) spin density and atomic charge of reactable atoms, 3) transition state and activation
enthalpy at radical coupling reaction. All the results of these simulations qualitatively agreed with theexperimental results about solvent effect, i.e., the activity of HRP to monolignols, and the increased formationof β-O-4 linkage in a nonpolar solvent.
2000-209
分子軌道討算によるフェノール化合物のホルムアルデヒドとの反応牲予測
光永 徹*1、Anthony H. Conner*2, Charles G. Hill Jr*3.
*1
三重大学生物資源学部、*2USDA-Forest Service, Forest Products Laboratory、*3College of Engineering,
University of Wisconsin
Predicting the reaction of formaldehyde with phenols by molecular orbital computation
Tohru Mitsunaga*1, Anthony H. Conner*2, Charles G. Hill, Jr*3
*1
Faculty of Bioresources, Mie University, *2USDA-Forest Service, Forest Products Laboratory, *3Department ofChemical Engineering, College of Engineering, University of Wisconsin
Abstract:
Computational chemistry has been used to study the relationship between the reactivity of anumber of phenolic compounds with formaldehyde in an aqueous, alkaline system, and charges calculated forreactive sites on the aromatic ring of the phenolic compound. Atomic- charges foreach phenolic compound were
calculated by ab initio methods at the RHF/6-31+G level of theory using the ChelpG method. Reaction rate
constants were determined from measurements of the concentrations of the phenolic compounds andformaldehyde as functions of time. The charge per reactive site was estimated by summing the charges at all thereactive sites on the phenolic ring and dividing by the number of reactive sites. A strong correlation wasobserved between the reactivity per reactive site and the average charge per reactive site.
2000-210
超臨界メタノールによる木質系バイオマスの化学変換 —針葉樹と広葉樹の比較—338

南 英治、大貫英範、坂 志朗
京都大学大学院エネルギー科学研究科
Chemical conversion of woody biomass in supercritical methanol. -Comparisons between softwood andhardwood
Eiji Minami, Hidenori Onuki, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
The supercritical methanol biomass conversion system with batch-type reaction vessel wasapplied to study the chemical conversion of sugi (Cryptomeria japonica) and buna (Fagus crenata) woods touseful chemicals. As a result, more than 90% of sugi and buna woods were decomposed and liquefied inmethanol for 30min supercritical treatment at 350ºC-43MPa. In addition, buna wood was easier to be liquefied
in methanol than sugi at 270ºC-27MPa. It was further indicated for the methanol-insoluble residues thatobserved differences are mainly originated from intrinsic ones in lignin structure between softwood andhardwood.
2000-211
亜臨界水及び超臨界水による木材の化学変換 —リグニンの分解—
江原克信、坂 志朗
京都大学大学院エネルギー科学研究科
Chemical conversion of wood by subcritical or supercritical water, -Degradation of lignin
Katsunobu Ehara, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Chemical conversion of buna wood (Fagus crenata Blume) was made in subcritical andsupercritical water (>22.1MPa, >374ºC) to study liquefaction mechanism of wood. The treated wood was
fractionated into the water-soluble portion, methanol-soluble portion, and methanol-insoluble residues. In thisstudy, a characterization or the lignin was forcused on the methanol-soluble portion. The obtained
methanol-soluble porrtion showed to be rich in lignin and more oxidative with more phenolic hydroxyl groups
than milled wood lignin (MWL). The alkaline nitrotxnzene oxidation abalyses of the lignin in methanol-soluble
and methanol-insoluble portions exhibited a decrease or oxidation products under supercritical water treatment.
These observations suggested that a preferential degradation of the ether linkages of lignin ocurred insupercritical water.
2000-212
スギ樹皮のポリエチレングリコール・バイサルファイト法による液化
上野智子、耿 興蓮、芦谷竜矢、親泊政二三、坂井克己
九州大学大学院生物資源環境科学研究科
Liquefaction of sugi (Cryptomeria japonica D. Don) bark by Polyethyleneglycol-bisulfite method
Tomoko Ueno, Xinglian Geng, Tatsuya Ashitani, Masafumi Oyadomari, Kokki Sakai
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
Polyethyleneglycol-bisulfite treatment was applied to the liquefaction of inner and outer barksof sugi. The optimal temperature of the treatment was 250ºC. The longer liquefaction time resulted in the higher
solubilization of inner bark. In the case of outer bark, condensation of lignin and/or tannin appeared to occur
during treatments for 60min and longer. The concentration of aqueous sodium bisulfite solution exhibited no
influence on solubilization of inner bark. Higher solubilization of outer bark was obtained in higher
concentration of the bisulfite solution. This
result suggests that sodium bisulfite caused sulfonation of lignin and condensed tannin which are contained inlarger amounts in outer bark than in inner bark.
2000-213
含糖型ポリウレタンの熱的および機械的性質に対するリグニン添加の影響
畠山兵衛*1、浅野育洋*1、廣瀬重雄*2、畠山立子*3*1
福井工業大学工学部、*2 工業技術院物質研究所、*3 大妻女子大学家政学部
Influence of lignin on thermal and mechanical prtoperties of polyurthanes containing saccharides Hyoe
Hatakeyama*1, Y Asano*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3*1
Fukui Institute of Technology, *2National Institute of Materials and Chemical Research, *30tsuma Women's
University339

Abstract:
Polyurethane (PU) foams with various lignin and saccharides contents were prepared bychanging the ratio between kraft lignin (KL) and molasses (ML) contents in polyethylene glycol (Mw=ca.200).
Thermal and mechanical properties of the above polyurethanes (PU's) were investigated by differential scanningcalorimetry (DSC), thermogravimetry (TG), simultaneous TG and Fourier-transformed infrared spectrometry(TG-FTIR) and mechanical measurements. Glass transition temperatures (T g’s) of the PU's decreased withincreasing KL/ML ratio. However, thermal degradation temperatures (T d's) increased with increasing KL/ML
ratio. The amount of thermal degradation products having characteristic functional groups changed according to
the temperature.
2000-214
相分離システムによる草本系リグノフェノール誘導体の誘導
関 範雄*1、伊藤国億*1*2、船岡正光*2*1
岐阜県生活技術研究所、CREST,JST、*2 三重大学生物資源学部、CREST,JST
Synthesis of lignophenol derivatives from herbaceous lignocellulosics through phase-separation system
Norio Seki*1, Kuniyasu Itoh*1*2, Masamitsu Funaoka*2*1
Gifu Prefectural Human Life Technology Research Institute, *2Faculty of Bioresources, Mie University
Abstract:
Lignophnol derivatives were synthesized from various herbaceous lingocellulosics, using
phase-separation system that was composed of phenol derivatives and concentrated acid, and theircharacteristics were investigated. Their yields were higher with mild concentrated acid treatment during thissystem, compared with that of softwood. Although lignophenol derivatives from herbs had similar basic
characteristics to that from woods, some characteristics of which slightly differed with their originating species
and woods. These differences would be due to the difference in the network structure of native lignin, thedistribution and quantity of ether linkages, and the degree of condensation.
2000-215
両親媒性物質に親和性を示す酢酸リグニンヒドロゲルの調製
西田光邦、浦木康光、佐野嘉拓
北海道大学大学院農学研究科
Preparation of acedc acid lignin hydrogel with affinity for amphiphilies
Mitsukuni Nishida, Yasmitsu Uraki, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
Acetic acid lignin (AL) prepared by the atmospheric acetic acid pulping of birch was found toform hydrogel by the reaction with polyethylene glycol diglycidyl eher(PE) as a cross-linker under alkalineconditions. In this study, the gelation time and the adsorption ability of the gel to cationic surfactants were
investigated to clarify the properties of novel lignin gels. The gel formation depended on amounts of glycidylgroup in PE and reaction temperatures. AL hydrogel remarkably adsorbed cationic surfactants with long alkyl
chains, but the surfactants with the short chain was not adsorbed. This result suggests that the adsorption was
mainly caused from hydrophobic interaction between AL domain of gel and alkyl chain of surfactant.
2000-特別講演
リグニン研究とケナフ栽培利用研究の接点について
鮫島一彦
高知大学農学部
Invited Lecture: About the overlapping points of lignin research and kenaf cultivation and utilization research
Kazuhiko Sameshima,
Faculty of Agriculture, Kochi University
Abstract:
Kenaf (Hibiscus cannabinus , in some case a variety of Hibiscus sabdariffa is included) is afiber plant which is traditionally used for making rope, bag and other fiber products. It is now, however, widely
recognized that kenaf could be one of the possible plants to fight to realize a new fiber production andutilization system for the future in may places in the world. After the industrial revolution wood has beenrecognized as a fiber plant and used for pulp and paper making and other purposes for large-scale production. It
is still true but other fiber plant like kenaf should be utilized as a supplemental fiber for many purposes. Because
the population increases, environmental problems and other modern problems could be solved in part by using
kenaf as useful plant for human being. Lignin research has been mostly concentrated on wood utilization, but
the methods will be adopted to kenaf research and development. It grows fast and have low lignin and silica
340

content, and it might be easier for lignin researchers to find useful methods for kenaf versatile utilization.
2000-P01
リグニンモデル化合物を用いた超臨界メタノールでのリグニンの反応牲
辻野潤一郎、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Reactivity of lignin in supercritical methanol studied with some lignin model compounds
Junichiro Tsujino, Harui Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Behaviors of lignin in supercritical methanol were studied by using lignin model compounds.
As a result, both guaiacyl and syringyl types of aromatic rings and biphenyl type structures were very stable
under supercritical condition of methanol. However, β-ether linkage in the phenolic β-O-4 model compound wascleaved rapidly into guaiacol and coniferyl alcohol which was further converted to its γ-methyl ether.
Non-phenolic β-O-4 model compound was, on the other hand, converted initially into its α-methyl ether andfurther degraded to produce guaiacol. Such a continuous decomposition can suggest that the supercriticalmethanol treatment is very effective to depolymerize lignin into the lower molecular products. These lines ofevidence imply that new phenolic residues of lignin are continuously formed and decomposed repeatedly insupercriticalmethanol mainly by the cleavage of the dominant β-ether structure in lignin.
2000-P02
非塩素漂白過程における α-カルボニル型リグニン構造の挙動 I. 重水素ラベルとニトロベンゼン酸化 を 組
み合わせた定量法
友田生織、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Formation and degradation of α-carbonyl structure in lignin during chlorine free bleaching, I. Method toestimate the α-carbonyl content in lignin remaining in pulp
Iori Tomoda, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
It is generally assumed that α-carbonyl structure is one of the key structures which govern thereactivity of lignin towards non-chlorine bleaching. We developed a method to evaluate the content of
α-carbonyl structure in residual lignin without isolating the lignin from the pulp. This method is based on afinding that a deuterium atom introduced to α-position by a NaBD4 reduction of α-carbonyl structure could be
retained in aldehyde when nitrobenzene oxidation was applied under mild condition. Under the modified
reaction condition of nitrobenzene oxidation, the retention of α-D in a model compound was about 70%.
2000-P03
GC 法こよるメトキシル基の定量法の再評価（2）—漂白パルプのリグニンメトキシル基の定量—
後藤仁志*1、幸田圭一*2、松本雄二*1、飯塚堯介*1*1
東京大学大学院農学生命科学研究科、*2 北海道大学大学院農学研究科
Determination of methoxyl content with GC method.(2). -Determination of lignin methoxyl content in bleachedpulp
Hitoshi Goto*1, Keiichi Koda*2, Yuji Matsumoto*1, Gyosuke Meshitsuka*1*1Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Graduate School of Agriculture,
Hokkaido University
Abstract:
Several types of lignin model compounds were subjected to HI treatment under various
conditions and the yield of methyl iodide was determined. Methyl iodide formation from a compound withelectron donating group was faster than that with electron withdrawing group. Not only the iodide concentration
but also the acid concentration significantly affected the formation rate of methyl iodide. All these results
seemed to be explained well by a hypothesis that the protonation to the oxygen atom of methoxyl group plays adecisive role in the cleavage of this group by HL The ability of carbohydrate as Lewis base to consume acidcould partly explain the interfering effect of the carbohydrate on the methyl iodide formation from a modelcompound, which could be explained also by a consumption of iodide by carbohydrates.
2000-P04341

木材炭化に伴う抽出成分の構造変化
渡辺泰高*1、光永 徹*1、中原光一*2*1
三重大学生物資源学部、*2 サントリー株式会社基礎研究所
Structural changes of extractives by carbonization of wood
Yasutaka Watanabe*1, Tohru Mitsunaga*1, Koichi Nakahara*2*1
Faculty of Bioresources, Mie University, *2 Institute for Fundamental Research, Suntory Ltd.,
Abstract:
Constitutional analysis of the components extracted with 60% aqueous ethanol from thecarbonized or heated (180ºC) white oak (Quercus alba L.) wood were investigated. The yield of the extractives
from carbonized or heated wood was almost the same with untreated wood, but the color of the solution fromtreated wood showed light brown and its color became dark brown as the function of time. Gallic acid, syringic
acid, vanillic acid, vanillin, syringaldehyde and ellagic acid were contained in the extractives of wood with andwithout carbonization. On the other hand, the yields of these compounds from carbonized wood meal were
1.6-6.3 times of untreated meal. In addition, 5-hydroxymethylfurfural and sinapaldehyde were formed fromtreated wood and wood meal.
2000-P05
フェノール牲 β-O-4 型リグニンモデル化合物の熱分解
堀越 直、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Thermal degradation of phenolic β-O-4 lignin model compounds
Sunao Horigoshi, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Effects of Cαand C structures on the cleavage of the β-ether during thermal degradation oflignin were studied by the reactivity of four phenolic β-O-4 lignin model compounds under atmosphericnitrogen at 400ºC for 1 min. As a result, the reactivity varied greatly with the Cα and Cγstructures (Cγ: CH2OH>> CH3, Cα: C=O >> CH2OH≅CH3). Mechanism of thermal degradation of the β-ether is discussed with theseresults; Cγ-OH plays an important role in the β-ether cleavage, while neighboring group participation of Cα-OH
and a quinonemethide intermediate formed by elimination of this hydroxyl group are not important in themechanism.
2000-P06
水蒸気圧縮処理による樹液抽出法の開発（II）
棚橋光彦*1、鈴木正史*1、神谷 恵*1、志智千賀子*1、小林孝行*1、京盛健一*2*1
岐阜大学農学部、*2 岐阜大学工学部
Development of a sap extraction method associated with the compressive molding process, (II)
Mitsuhiko Tanahashi*1, Masashi Suzuki*1, Megumi Kamiya*1, Chikako Shicchi*1, Takayuki Kobayashi*1,
Ken-ichi Kyomori*2*1
Faculty of Agriculture, Gifu University, *2Faculty of Engineering, Gifu University
Abstract:
We have developed a compressive molding process, which converts thinnings or the growth of
miscellaneous hardwood species to useful materials. However, sap is disposed of together with wastewater inthis process. In this study, utilization of the sap for new industrial materials was investigated. Composition
analysis of the sap from white birch, detected the presence of sinapylalcohol and coniferylalcohol. In anotherstudy, 5-hydroxymethylfurfural was identified from leaves of Japanese cedar. These compounds will be useful
as industrial materials. Furthermore revised settings in the apparatus could yield hydrocarbon compounds which
are useful as liquid fuels.
2000-P07
ケナフ靭皮繊維のパルプ化温度に関する研究
金森季一、ビブチ・B・マズンダル、大谷慶人、鮫島一彦
高知大学農学部
Studies on kenaf bast pulping temperature
K. Kanamori, B. B. Mazumder, Y. Ohtani and K. Samesima
Faculty of Agriculture, Kochi University
Abstract:
The relationship between viscosity and cooking temperature in kenaf bast soda-pulping, at
100ºC, 120ºC, 140ºC was examined. The bleaching after soda-pulping was also tried. Kenaf variety of342

Zhejiang-1 grown in Kochi was used as bast sample. The soda-pulping was made after ammonium oxalate
pretreatment. Sodium hypochlorite and chlorine dioxide were used for bleaching experiment. Yield, Kapper
number, viscosity, and brightness were measured. Kappa number didn't decrease much at 100ºC and 120ºC but
started to decrease at 140ºC. In contrast viscosity decreased proportionally to cooking temperature increase. In
bleaching, sodium hypochlorite showed maximum brightness, but that of chlorine dioxide increased
proportionally to the dosage.
2000-P08
HBS パルプ化 —回転式オートクレーブによるシラカンバのパルプ化
長岡秀明、梶本純子、佐野嘉拓
北海道大学大学院農学研究科
HBS pulping-pulping of birchwood by rotating autoclave
Hideaki Nagaoka, Junko Kajimoto, Yoshihiro Sano.
Graduate School of Agriculture, Hokkaido University
Abstract:
HBS pulping of birch wood with PG in a rotating autoclave was carried out at 200ºC,
for 1 to 2 h. Pulping spent liquors were separated into lignin and RPG. RPG consisted of low molecular lignin
products, ugars and modified sugar products in addition to PG as a main material. The results on the yields ofpulp, pulp residual lignin (KL) and lignin showed that PG and RPG were good pulping solvents corresponding
to butanediols (BDOL) and RBDOL, though RPG and RBDOL were better solvents tha PG and BDOL. The
strength properties of PG pulp were inferior to those ofcorresponding kraft pulp, but comparable to those of BDOL and other organosolv pulps.
2000-P09
常圧酢酸法によるバイオマス成分の効率的総合利用
佐野嘉拓、中野潤也、久保田康恵、浦木康光
北海道大学大学院農学研究科
Total utilization of biomass with efficiency with atmospheric acetic acid process.- Separation of birch
components using a large-scale extractor
Yoshihiro Sano, Jyunya Nakano, Yasue Kubota, Yasumitsu Uraki
Graduate School of Agriculture, Hokkaido University
Abstract:
Birch was separated into wood, outer bark and inner bark fractions. Ten kg of chips preparedfrom the wood fraction was refluxed with 90% AcOH containing a small amount of H 2SO4 for 1-3 h by use of
all extractor of 100L capacity to be divided into pulp, lignin and water solubles. Xylose was isolated andpurified from the water solubles to convert to xylitol. The outer bark faction (3.4 kg) was refluxed with absolute
AcOH by the same extractor to extract betulin.
2000-P10
樹皮のグリコール—バイサルファイト法による液化反応の解析
芦谷竜矢、上野智子、坂井克己
九州大学大学院生物資源環境科学研究科
Reaction of liquefaction of bark by glycol-bisulfite method
Tatsuya Ashitani, Tomoko Ueno, Kokki Sakai
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
Liquefaction of bark by glycol-bisulfite method was analyzed. Especially, conversion ofpolyphenolic components under the liquefaction condition was examined. Catechin as tannin monomer andquebracho tannin were treated with ethylene glycol and aqueous sodium bisulfite at
250ºC. The products were extracted by water and ethyl acetate. Catechol was detected as a common product by
GC-MS analysis of the ethyl acetate soluble parts obtained from the treatment of catechin and quebracho tannin.
From IR spectra, it was assumed that solvent-insoluble precipitate was polymerization products of low molecule
phenolic compounds like catechol.
2000-P11
酢酸リグニン-古紙混合物の押し出し成形と活性炭化
浦木康光、岡野祥平、久保智史、佐野嘉拓、
北海道大学大学院農学研究科
343

Extrusion molding of a mixture of acetic acid lignin and waste paper, and its conversion to activated carbon
moldings
Yasumitsu Uraki, Shohei Okano, Satoshi Kubo, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
An aim of study is to prepare activated carbon (AC) moldings, such as pellet and sheet, fromthe mixture of acetic acid lignin and waste newspaper continuously. The continuous molding of the mixture
even with 10% of the infusible newspaper was carried out by extrusion molding using single screw extruder
equipped with mono hole nozzle in a diameter of 3 mm and T-die as dice for preparing long pellet and sheet,respectively. Such moldings were converted to AC moldings by steam activation. The sheet prepared by the
extruder required longer activation time than that by thermal compression method to produce the AC with morethan 900 m2/g of specific surface area.
2000-P12
免疫法によるスギ心材成分の標識 3. 抗アガサレジノール血清の認識選択性
長崎剛士*1、安田征市*1、今井貴規*1、高橋孝悦*2*1名古屋大学大学院生命農学研究科, *2 山形大学農学部
Immunolabeling of heartwood extractives in Cryptomeria japonica. 3. Recognition selectivity ofanti-agatharesinol serum
Takeshi Nagasaki*1, Seiichi Yasuda*1, Takanori Imai*1, Koetsu Takahashi*2*1Graduate School of Bioagricultural Sciences, Nagoya University, *2School of Agriculture, Yamagata
University
Abstract:
Recognition selectivity of the previously prepared anti-agatharesinol serum was examined bycompetitive inhibition-ELISA using various kinds of wood extractives as competitors. The antiserum had thehighest reactivity with agatharesinol among the used extractives. The antiserum was able to differentiate
between norlignans according to slight differences in their chemical structures, and reactivities of the extractives
other than norlignan were much lower. Competitive inhibition-ELISA using agatharesinol derivatives as well as
various norlignans indicated that the antiserum required 1,3-bis-(p-hydroxyphenyl)-propene structural unit ofagatharesinol for the antigen-antibody reaction and that hydroxylation pattern on one aromatic ring (referred to''B ring'') influenced seriously the reactivity.
2000-P13
ペルオキシダーゼアイソザイムの基質認識の差異とシリンギルリグニン生合成における役割
青山 渉、松村茂起、堤 祐司、西田友昭
静岡大学農学部
Substrate utilization toward monolignols of peroxidase isoenzymes and their involvement in syringyl lignin
biosynthesis
Wataru Aoyama, Shigeki Matsumura, Yuji Tsutsumi, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
A peroxidase, SyPO, isolated from the cell walls of poplar callus culture is capable to utilize
sinapyl alcohol as substrate most effectively in plant isoperoxidases. In this paper, we compared the ability of
SyPO in oxidation and polymerization of sinapyl alcohol to other peroxidases, such as horseradish peroxidase(HRP) and the other isoperoxidase, GPO-2, that was also isolated from the cell walls of poplar callus culture.
The results showed that the two peroxidases, HRP and GPO-2 could also oxidize sinapyl alcohol in the presenceof coniferyl alcohol, however, these peroxidases could not produce a dehydrogenative polymer from sinapyl
alcohol and its oligomer compared to that SyPO could do. The surface plasmon resonance analysis suggests that
only SyPO can bind to the oligomer of sinapyl alcohol.
2000-P14
担子菌によるジフェニルエーテル化合物の分解機構
平塚宣博、割石博之、田中浩雄
九州大学大学院生物資源環境科学研究科
Fungal degradation of diphenyl ether derivatives
Nobuhiro Hiratsuka, Hiroyuki Wariishi, Hiroo Tanaka
Graduate School of Bioresources and Bioenvironmental Sciences, Kyushu University
Abstract:
A series of diphenyl ether compounds were effectively degraded by the white-rot fungus,344

Coriolus versicolor. 4-Chlorodiphenyl ether was degraded to produce 4-chlorophenol via the intermediate
formation of 4-chloro-4'-hydroxydiphenyl ether. Diphenyl ether was also hydroxylated to form
4-hydroxydiphenyl ether which was further metabolized. Piperonyl butoxide, a typical inhibitor for cytochrome
P450, effectively inhibited the hydroxylation of diphenyl ethers. The quantitative recovery of the starting
substrates was also confirmed in the presence of piperonyl butoxide, strongly suggesting that the initial step of
the metabolic pathways might be the hydroxylation reaction. On the other hand, 4-amino- and
4-hydroxydiphenyl ethers were oxidized by extracellular phenoloxidases.
2000-P15
18SrDNA による有用白色腐朽菌株の同定
須原弘登*1、近藤隆一郎*1、坂井克己*1、前川二太郎*2*1
九州大学大学院生物資源環境科学研究科、*2㈶菌蕈研究所
Identification of valuable white rot fungi by 18SrDNA sequences
Hiroto Suhara*1, Ryuichiro Kondo*1, Kokki Sakai*1, Nitaro Maekawa*2*1
Graduate School of Bioresourse and Bioenvironmental Sciences, Kyushu University, *2The Tottori
Mycological Institute
Abstract:
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) havebeen a public concern for several decades because of their strong toxicity. We have suggested one white rot
fungus, strain MZ-34O, collected from-natural forest in Japan, is able to degrade highly-chlorinated PCDDs and
PCDFs. We did not have enough information except that it belongs to white rot fungus. Therefore nucreotide
sequences of the small subunit ribosomal RNA gene were used to identify strain MZ-340. Strain MZ-340 was
suggested to belong to genus Ceriporia with DNA analysis data. Subsequently, morphological observation wasdone. The observation also supported that strain MZ-34O belongs to genus Ceriporia.
2000-P16
遺伝子組み換え微生物バイオリアクターを用いたリグニン芳香核構造からの新規ポリアミド型機能性高分子
材料の生産
片山義博*1、西川誠司*2、政井英司*1、福田雅夫*3、重原淳孝*4*1
東京農工大学大学院 BASE、*2 株式会社コスモ総合研究所、*3 長岡技術科学大学工学部、*4 東京農工大
学工学部
The production of the new polyamide type polymer materials from lignin aromatic structure using generecombination of microorganism
Yoshihiro Katayama*1, Seiji Nishikawa*2, Eiji Masai*1, Masao Fukuda*3, Atsutaka Shigehara*4*1
Graduate School of Bio-Appications and System Engineering, Tokyo University of Agriculture & Technology,*2
Cbsmo Research Instjtute, *3Department of Bioengineering, Nagaoka University of Technology, *4Faculty ofTechnology, Tokyo University of Agriculture and Technology
Abstract:
We are currently investigating biotransformation process based on the catabolism of various
dimeric lignin compounds by Sphingomonas pausimobilis SYK-6, which proceed via protocatechuate meta
cleavage pathway. 2-pyrone-4,6-dicarboxylic acid (PDC) is a characteristic intermediate of the protocatechuatemeta cleavage pathway. We have prepared the mutant with defective in PDC hydrolase by gene replacement
technique ( lig I), by which we have succeeded in producing the PDC in the high yield (ca. 90%) from thelow-molecular weight lignin mixture. Since PDC has the unique molecular structure and the polymer made from
PDC is expected to have the new function as optical material, we prepared new polyamide type polymer by theinterfacial polymerization reaction with hexamethylene diamine.
2000-P17
白色腐朽菌 Phanerochaete sordida YK-624 株における ferrireductase 産生について
伊藤敬訓、平井浩文、西田友昭
静岡大学農学部
Production of ferrireductases by white-rot fungus Phanerochaete sordida YK-624
Takanori Itoh, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
We examined the production of ferrireductase by white-rot fungus Phanerochaete sordida
YK-624. High level of ferrireductase activity was observed in nitrogen-sufficient culture compared withnitrogen-limited culture. Ferrireductase was produced under the culture containing Fe, although it was345well-known that fcrrireductase by yeast was produced only in Fe-deficient culture. The addition of Mn(IV) tothe culture induced the production of both manganese peroxidase and ferrireductase as same level as the
addition of Mn(II) did. These result suggest that ferrireductase plays an important role in the reduction ofMn(IV) to Mn(II).
2000-P18
ユリノキの組織培養によるシリンガレジノールの生成
山地裕二、原 敬治、伊藤和貴、橘 燦郎
愛媛大学農学部
Formation of syringaresinol in Liriodendron tulipifera by callus cultures
Yuji Yamaji, Takaharu Hara, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Calli were induced from the leaves of young trees of Yurinoki, Liriodendron tulipifera, on
Gamborg's B5 medium supplemented with 2,4-diclllorophenoxyacetic acid and kinetin, and subcultured on thesame medium. High-performance liquid chromatographic analysis of the extractives of calli revealed that thecalli produced syringaresinol.
2000-P19
天然からスクリーニングした菌によるダイオキシン類のバイオレメデイエーション
清田幸徳、児山友彦、伊藤和貴、橘 燦郎
愛媛大学農学部
Bioremediation of dioxins by selected fungi from natural world
Yukinori Kiyota, Tomohiko Koyama, Kazutaka Ito, Sanrou Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Bioremediation of dioxins (PCDD/Fs) contaminated in a paddy soil by fungus PL1 selected bya screening method from the natural world was conducted. The fungus degraded about 90% of the dioxins in thesoil when 7% of the fungus was added to the soil and incubated for 30 days. The degradation rate of PCDD/Fs
increased with increase in added amount of the fungus. On thecontrary, the value of toxicity equivalency quantity (TEQ) in the treated soils deceased with increase in added
amount of the fungus because of degradation of PCDD/Fs. Furthermore, thedegradation rate of PCDD/Fs in the soil by the bioremediation was improved by addition of a surfactant. The
results suggest that bioremediation of dioxins contaminated soils by selected fungi by a screening method is
possible.
2000-P20
ダイオキシン分解能を有する菌による焼却灰中のダイオキシン類の分解
古賀道房、伊藤和貴、橘 燦郎
愛媛大学農学部
Degradation of dioxins in incinerated ashes by some fungi having ability for degradation of dioxins
Michifusa Koga, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Microbial degradation of octachlorodibenzo-p-dioxin (OCDD) by three fungi (Coprinus sp.,
Pycnoporus sp. and Lyophyllum sp.) having ability for degradation of dioxins selected by a screening methodfrom the natural world was conducted in a liquid medium. The three fungi degraded from about 35% to 45% of
OCDD for 30 days. And bioremediation of dioxins (PCDD/Fs) in an incinerated ash by three fungi selected by
the screening method was conducted in a solid medium. The three fungi degraded from about 40% to 50% of
PCDD/Fs. The results suggest that purification of PCDD/Fs in incinerated ashes by the bioremediation with theselected fungi is possible.

346

第 46 回 （2001.11.1-2） 京都大学木質科学研究所
2001-101
TIZ 法によるリグニン—糖モデル化合物（DHP−Sugar）の分解
片平 類、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
The degradation of DHP-sugar model compound by the TIZ method
Rui Katahira, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Graduate school of Agriculture, Kyoto University
Abstract:
TIZ method is an useful method to cleavage β-O-4 bond in lignin quantitatively without any
secondary condensation reaction. And in this method, most of α-structure of lignin can be maintained. In thisstudy, at first TIZ method was modified. TIZ method requires three reaction steps (Tosylation, Iodination and Zn
treatment). It was found that iodination and Zn treatment could be carried out in one pot. Second, the modified
TIZ method was applied to the degradation of DHP- sugar and Loblolly pine MWL. In the degradation products,
compound 5 R2 : Ac) was not found. But, the hydrogenation of the products gave compound 6 R3: H). It
suggested that most of α-structure of β-O-4 structure parts in lignin were substituted.
2001-102
樹幹内における β−O−4 型側鎖立体構造の不均一性
秋山拓也、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Heterogeneities of erythro and threo forms of β-O-4 structures in lignin
Takuya Akiyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
The ratio of erythro and threo forms of β-O-4 structures (E/T ratio) and methoxyl group content
in tension wood parts of yellow poplar were higher than those in normal wood parts. The distribution of erythro
and threo forms of β-O-4 structures is not homogeneous, and is in fairly good agreement with that of syringyl
and guaiacyl units. It was indicated that the methoxyl group is one of the factors which affects thediastereoface-differentiating water addition to quinone methides.
2001-103
GC 法によるメトキシル基の定量法の再評価（3）−メトキシル基解裂反応の機構の解析と共存する炭水化物の影響−
後藤仁志*1、幸田圭一*1*2、松本雄二*1、飯塚尭介*1*1
東京大学大学院農学生命科学研究科、*1 北海道大学大学院農学研究科
Determination of methoxyl content with GC method. (3). -Analysis of the reaction mechanism of methoxyl
cleavage and the effect of co-existing carbohydrate
Hitoshi Goto*1, Keijchi Koda*1*2, Yuji Matsumoto*1, Gyosuke Meshitsuka*1*1Graduate School of Agricultural and Life Sciences. the University of Tokyo, *2Graduate School of Agriculture,
Hokkaido University
Abstract:
Reaction mechanism and possible interfering effects caused by the presence of carbohydrates
for the methoxyl determination by hydroiodic acid were investigated. The formation rate of methyl iodide fromcarbohydrates was quantitatively analyzed. and it was suggested that methyl iodide could arise fromcarbohydrate even when the carbohydrates did not contain a direct precursor for methyl iodide. It was also
confirmed that the presence of carbohydrates depress the formation rate of methyl iodide from lignin methoxylgroup. Therefore. the presence of carbohydrates could result both in overestimation and underestimation of
methoxyl group depending on the amount of carbohydrates. Hammett plot of substituent effect of side-chain
part on the methyl iodide formation suggested SN2cA reaction mechanism for guaiacyl models but no clear
relation was observed for syringyl models.
2001-104
TOF-SIMS によるリグニン構造解析
福島和彦*1、山内一慶*1、斉藤香織*1、辻 幸子*1、安田征市*1、高橋元幾*2、星 孝弘*2
*1
名古屋大学大学院生命農学研究科、*2 アルバック・フアイ株式会
Analysis of lignin structures by TOF-SIMS
347

Kazuhiko Fukushima*1, Kazuchika Yamauch*1, Kaori Saito*1, Yukiko Tsuji*1, Seiichi Yasuda*1, Motoki
Takahashi*2 and Takahiro Hoshi*2*1Graduate School of Bioagricultural Sciences, Nagoya University, *2ULVAC-PHI. Inc., Japan
Abstract:
The structure of lignin was investigated by TOF-SIMS. Pine milled wood lignin (MWL) gavesome secondary ions which seemed to correspond to guaiacyl lignin fragments. In this study, these secondary
ions could be attributed to the typical guaiacyl fragments by labeling experiment of DHP. Deuterium labeled
DHP prepared from coniferyl alcohol-[-D,D, -OCD3] was subjected to TOF-SIMS analysis. In addition to two
major peaks of C6-C1 structures, some secondary ions with C6-C3 structures were also found in the mass spectraof MWL and DHP.
2001-105
熱分解マススペクトロメトリーによるリグニンの分析（II）：腐朽過程における化学構造の差異
中川明子、砂原 寛、黒田健一
筑波大学農林工学系
Analysis of lignin by pyrolysis-mass spectrometry, (II). Difference of chemical structure during the decaying
process
Akiko Nakagawa-izumi, Hiroshi Sunahara, Ken-ichi Kuroda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Sugi woods were decayed by brown-rot fungi (Fomitopsis palustris) and white-rot fungi(Trametes versicolor). The minute samples(<1pg) from the surface and inner parts of the decayed woods were
pyrolyzed at 500ºC for 4s. The products were immediately to a mass-spectrometer and ionized at 20eV. The MS
spectra were analyzed by the principal components analysis (PCA). Py-MS and PCA showed (1) the differencesin the samples obtained from the surface ant inner parts and (2) the differences rotting process by brown-rot
fungi and white-rot fungi.
2001-106
反応熱脱着ガスクロマトグラフィーによる木材中のフェノール性抽出成分の解析
横井裕明*1、後藤邦佳*1、石田康行*1、大谷 肇*1、柘植 新*1、園田哲也*2、小名俊博*2*2
名古屋大学大学院工学研究科、*2 王子製紙株式会社森林資源研究所
Characterization of phenolic wood extractives by reactive thermal desorption-gas chromatography
Hiroaki Yokoi*1, Kuniyoshi Goto*1, Yasuyuki Ishida*1, Hajime Ohtani*1, Shin Tsuge*1, Tetsuya Sonoda*2,
Toshihiro Ona*2*1
Graduate School of Engineering, Nagoya University, *2Forestry Research Institute, Oji Paper Co. Ltd.,
Abstract:
Reactive thermal desorption-gas chromatography (RTD-GC) in the presence of organic alkali
was applied to the rapid characterization of phenolic extractives in Euca!yplus samples. By the use of
tetramethylammonium acetate (TMAAc) as the organic alkali the methyl derivatives of the phenolic acids were
expectedly observed on the chromatogram formed through RTD. However, they were concluded to be formed
from the extractives together from partial pyrolysis of lignin. This fact suggested that the accurate determinationof the phenolic extractives were difficult. Thereupon by using tetrabutylammonium hydroxide (TBAH), thephenolic acids in the extractives without methoxyl group were converted into their perbutyl derivatives, whichwere clearly discriminated from lignin or the extractives with methoxyl group. Based on the peak intensities ofthe perbutylated phenolic acids observed on the chromatograms, the contents of the phenolic extractives without
methoxyl group were rapidly estimated without using any cumbersome pretreatments of samples such as solvent
extraction.
2001-107
Keynote: Monolignol biosynthesis in trees：Recent findings and paths for the future
Vincent L. Chiang
Michigan Technological University
Abstract:
We have discovered novel genes that regulate syringyl monolignol biosynthesis in angiosperms
and demonstrated that the diversion of guaiacyl monolignol intermediates into syringyl types takes place at
coniferaldehyde mediated by coniferaldehyde 5-hydroxylase (CAld5H) , 5-hydroxyconiferaldehyde
O-methyltransferase (AldOMT) and sinapyl alcohol dehydrogenase (SAD). These discoveries together with ourearly demonstration that monolignol pathway 4- coumarate: coenzyme A ligase (Pt4CL1) controls lignin
accumulation provided us clues to simultaneously increasing lignin S/G ratio and reducing lignin content intrees by concurrent manipulation of the expression of genes encoding these enzymes. New insights derived from348

these discoveries to genetic engineering of syringyl lignin in conifers will also be discussed.
2001-108
樹木ポプラにおけるリグニン合成量の遺伝子工学的調節
熊谷大地、川合伸也
東京農工大学農学部
Regulation of lignin synthesis by genetic manipulation from Populus kitakamiensis
Daichi Kumagai, Shinya Kawai
Faculty of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
It was reported that tabacco LIM protein bound to Pal-box which was a cis-acting element forgene expression involved in phenylpropanoid biosynthesis. Thus we have cloned and sequenced a cDNA clone,
named klim, from young leaves of Populus kitakamiensis. The deduced amino acid sequence showed a highidentity to other plant LIM proteins which had zinc finger motifs. We also cloned the 5'-flanking region of klim
from genomic DNA by inversed PCR. We found several zinc finger binding motifs in 1,094 bp of the 5'-flanking
region. This motif also exsisted in the 5'-nontranslational region of klim cDNA. It suggested that LIM protein
might regulate itself.
2001-109
ペルオキシダーゼ過剰発現による除草剤耐性付加
田村 健、寺尾 俊、柳崎 真輝、高橋順子、川合伸也
東京農工大学農学部
Plant peroxidase over-production in tobacco induces herbicide-tolerance
Takeshi Tamura, Shun Terao, Masaki Yanazaki, Yoriko Takahashi, Shinya Kawai
Faculty of Agriculture, Tokvo University of Agriculture and Technology
Abstract:
The aspen gene, prxA3a, encoding an anionic peroxidase, was over-expressed in transgenic
tobacco plants. This gene had been isolated from Populus kitakamiensis and characterized that it contributed tolignin-biosynthesis. Peroxidase expression cassette was under the control of CaMV35S promoter. Thesetransgenic plants increased herbicide-tolerance against paraquat, DCMU and atrazin, in leafdisk assay, without
the accumulation of lignin. Such resistant plants also had more SOD activities than those of wild-type plants.
These indicated that the over-expression of prxA3a induced plants the protection from oxidative damage causedby paraquat and DCMU.
2001-P01
高粘度ケナフ靭皮パルプの製造に関する研究（2）シュウ酸アンモニウム前処理とパルプ品質の関係
渡辺大輔、大谷慶人、鮫島一彦
高知大学農学部
Studies on production of high viscosity kenaf bast pulp. (2). Relationship between ammonium oxalate
pretreatment and pulp quality
Daisuke Watanabe, Yoshito Ohtani, Kazuhiko Sameshima
Faculty of Agriculture, Kochi University
Abstract:
To confirm the importance of ammonium oxalate (Amox) pretreatment before the pulping at
normal pressure, the soda pulpings with or without Amox pretreatment were compared. Whole kenaf stem washarvested, and debarked by hand, and air dried. Amox pretreatment was carried out on the bast of 10cm in 0.5%
Amox. Soda pulping was performed in 10,15,20,25% NaOH for I hour. The yield of soda kenaf bast pulp
without Amox pretreatment was higher than that of Amox pretreated one. This indicates that there exist somematerial which can be removed by the Amox pretreatment but not in the soda cooking. Viscosity was higher inAmox treated pulp in low NaOH concentrations. Pectin in soda pulp with the Smox pretreatment was about halfof that in the pulp without Amox pretreatment. It was confirmed that Amox pretreatment is important if a pulp
with lower impurities is required, but high viscosity pulp can be produced without Amox pretreatment although
the level of viscosity is a little lower.
2001-P02
クラフトパルプの二酸化塩素漂白におけるダイオキシン類の生成機構
大井 洋*1、細谷修二*2、真柄謙吾*2*1
筑波大学農林工学系、*2 森林総合研究所
349

Mechanism of dioxins formation during chlorine dioxide bleaching of kraft pulp
Hiroshi Ohi*1, Shuji Hosoya*2, Kengo Magara*2*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2Forestry and Forest Products
Research Institute
Abstract:
Kraft pulp and sulfite pulp bleaching mills using chlorine, chlorine dioxide (D) and otherchlorinated compounds are under surveillance of the dioxins regulation. The bleaching mills are regarded as"notified establishments" which should pollute water quality. According to it, a limit for emissions of dioxins
and PCBs to environmental water from the mills is less than 10pg-TEQWHO1998/L. The limit should beconsidered ten times as that of environmental water quality (1pg-TEQ/L). One of questions is that water
qualities of process sewers in chlorine dioxide bleaching (ECF) mills are less than the environmental water
quality (1pg-TEQ/L), or not. Objectives of this study are to clarify the dioxins level of ECF mill sewers and toknow more about mechanism of dioxins formation during chlorine dioxide bleaching of oxygen-delignified
hardwood kraft pulp (LOKP) on a basis of the analysis revel for the environmental water quality. Laboratory
bleaching was carried out using a mill LOKP(kappa number 9.8), chlorine dioxide from a mill R8 generator anddrink water in a laboratory high-share mixer. Active chlorine factors were in the range of 0.14-1.14. The total
TEQs are less than 15ppq for the D treated and D and alkali-extracted (E) pulps and less than 0.0057pg-TEQ/L
for the D and E spent liquors. ln both cases, 2,3,7,8-TCDD and TCDF were not detected.
2001-P03
アルカリ系蒸解過程におけるリグニン側鎖構造の変化
永谷宏幸、杉元倫子、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Change of lignin side-chain structure during soda- and kraft-pulping
Hiroyuki Nagatani, Tomoko Sugimoto, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Glyceric acid was obtained as a predominant product by ozonation of both kraft pulp residual
lignin and dissolved lignin. The yield ratio between glyceric acid and tetronic acids(erythronic and threonic) becomes higher with the progress of delignification. Quantitative analysis of the yieldof those ozonation products suggested that glyceric acid originates from certain structure(s) which originallypresent in wood lignin, although structures modified during pulping reaction could also contribute to theformation of this acid.
2001-P04
パルプ残存リグニンの単離とその性状に関する研究 —過ヨウ素酸塩前処理を用いたパルプ残存リグニンの単離—
相見 光、飯塚堯介
東京大学大学院農学生命科学研究科
Isolation of residual lignin from unbleached hardwood kraft pulp by a pretreatment with mild periodate
treatment
Hikaru Aimi, Yuji Matsumoto, Gyosuke Meshitstika
Graduate School of Agricultural and Life Sciences, the University of Tokyo,
Abstract:
lt is very important to elucidate the structural feature of residual 1ignin to understand the reason
why it is not removed from pulp during cooking. In order to isolate the residual lignin from pulp, two methods
are, at the present, widely used: that is, acidolytic treatment and enzymatic treatment. In this study, weinvestigated the isolation method of residual lignin by a mild periodate
pretreatment. By this treatment, the rings of sugar units in pulp will be opened and the sugar chains will havemore flexible conditions. We expect to obtain the residual lignin at higher yield by the subsequent extraction of
the treated pulps. When the diazomethane treated pulp was mildly treated with periodate and was extracted withaqueous akali in the presence of NaBH4, about 73% of residual lignin was found to be removed from the pulp.
This fact may indicate that the major part of he residual lignin is entrapped in the carbohydrate matrix of pulp.
2001-P05
白色腐朽菌によるケナフおよびシラカバパルプの漂白特性の比較
大前陽子、大谷慶人、鮫島一彦
高知大学農学部
350

Bleaching. effects of kenaf and shirakaba pulps by white rot fungi
Yoko Ohmae, Yoshito Ohtani, Kazuhiko Sameshima
Faculty of Agriculture, Kochi University
Abstract:
Soda-Anthraquinone (AQ) and kraft pulps from kenaf bark, core, or shirakaba were
bio-bleached by four white rot fungi, two of them were obtained from the fields and the others were
Phanerochaete chrysosporium and Pleurotus ostreatus. Bleachabilities, such as brightness, kappa number,viscosity of the pulps were investigated in connection with laccase, manganese peroxidase, and lignin
peroxiidase activities of each fungus. Bleachability of kenaf core pulp was similar to that of shirakaba pulp, but
far from that of kenaf bark pulp. Relationship between bleachability and enzymatic activity was quite dependent
upon not only the fungi but also the pulps.
2001-P06
蒸煮・爆砕処理を用いた建築廃材中のリグニンの挙動
前田めぐみ*1、樋口暁浩*1、佐藤雅俊*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センターCharacterization inlignin in waste boards during steam-explosion treatment
Megumi Maeda*1, Akihiro Higuchi*1, Masatoshi Sato*1, Kenji Iiyama*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Asia Natural Environmental
Science Center, the University of Tokyo
Abstract:
It was tried to produce binderless board from waste woody materials used in construction using
steam explosion procedure. Properties of lignin treated with steam explosion process under various conditions
were investigated by chemical analyses and scanning electron microscopy. Hemicellulose was decomposed at
higher pressure of steam explosion, and significant amounts of lignin was dissolved in exhaust liquor of steam
explosion. S/V ratio of alkaline nitrobenzene oxidation products of lignin in steam explosion pulps was almost
constant under conditions used in this study. Mechanical strength of binderless board from steam exploded pulp
was also discussed.
2001-P07
酸加水分解リグニンより機能性物質調製の試み（その 2）
田村敬史、安田征市
名古屋大学大学院生命農学研究科
Preparation of functional materials from gynnosperm acid hydrolysis lignin, (2)Takashi Tamura, Seiichi Yasuda
Graduate School of Bioagricultural Sciences, Nagoya University,
Abstract:
The chemical conversion of sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis
lignin into functional materials was investigated. SAL has lower reactivity owing mainly to the high rate ofcondensed structures and then was phenolized (P-SAL) for its activation. In order to prepare surface-active
agents having monosaccharide and carboxyhydroxymethy1 (-CH(OH)COOH) group from P-SAL, phenolized
lignin model compounds were treated with xylose in 72% sulfuric acid and glyoxylic acid in alkaline media.
The yields of a C-xyloside and products with carboxyhydroxymethyl group were <5% and 75% respectively.
The preparation of a surface-active agent with carboxy- hydroxymethyl group from P-SAL is attempted.
2001-P08
PEG・バイサルファイト法により液化したスギ樹皮由来ポリウレタンフィルムの調製
芦谷竜矢*1、上野智子*2、栗本康司*3、坂井克己*1*1
九州大学大学院生物資源環境科学研究科、*2 福岡女子大学人間環境学科、*3 秋田県立大学木材高度加工研究所
Polyurethane film prepared from liquefied sugi bark by PEG-bisulfite method
Tatsuya Ashitani*1, Tomoko Ueno*2, Yasushi Kurimoto*3, Kokki Sakai*1*1Graduate School of Bioresource and Bioenviromental Sciences, Kyushu University, *2Fukuoka Women’s
University, Institute of Wood Technology, *3 Akita Prefectural University
Abstract:
Sugi (Cryptomeria japonica D. Don) bark was liquefied using PEG-400 and sodium bisulfite at
250ºC. Polyurethane (PU) films were prepared by a solution casting technique after co-polymerization of theobtained liquefied bark and polymeric methylene diphenylene diisocyanate (PMDI) in dichloromethane.
Thermal and mechanical properties of the PU films were investigated by thermo gravimetric analysis (TGA),
351

dynamic mechanical thermal analysis (DMTA) and mechanical measurements. Tensile strengths of the PU films
prepared from liquefied sugi bark were 0.2-70 MPa at [NCO]/[OH] ratio = 0.25-1.25. It was suggested fromresults of DMTA and TGA that components in liquefied bark acted as cross linking agents.
2001-P09
木材及び腐朽材によるクロム(III)および銅(II)の吸着
オスカー・ビコベンス*1*2、ヤニス・グラビテイス*1、飯山賢治*2
ラトビア国立木材科学研究所、東京大学アジア生物資源環境研究センター
Sorption of chromium（III）and copper（II）on wood and biologically decayed wood
Oskars Bikovens*1*2, Janis Gravitis*1, Kenji Iiyama*2*1
Latvian State Institute of Wood Chemistry, *2Asian Natural Environmental Science Center，the University ofTokyo
2001-P10
リグニンペルオキシダーゼの電気化学的解析
親泊政二三*1、割石博之*2、田中浩雄*2、篠原寛明*3*1
九州大学大学院生物資源環境科学研究科, *2 九州大学大学院農学研究院, *3 岡山大学工学部
Electrochemical analysis of lignin peroxidase
Masafumi Oyadomari*1, Hiroyuki Wariishi*2, Hiroo Tanaka*2, Hiroaki Shinohara*3*1Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Faculty of Agriculture,
Kyushu University, *3Faculty of Engineering, Okayama University
Abstract:
The redox potential of lignin peroxidase (LiP) was measured by a cyclic voltammetry technique.
The pyrolytic graphite electrode coated with LiP-embedded tributylmethyl phophonium chloride membrane wasutilized. Quasi-reversible electron transfer between LiP and the electrode surface was observed. The redox
potential between ferric and ferrous LiP exhibited pH-dependency, indicating that the reductive half-reaction of
the LiP occurred as; ferric LiP + 1e- + H+ →ferrous LiP.
2001-P11
Phanerochaete crassa WD1694 菌株由来のマンガンペルオキシターゼの精製
高野麻理子、中村雅哉、関谷 敦、山口宗義、西田篤実
森林総合研究所
Purification of manganese peroxidase from Phanerochaete crassa WD1694
Mariko Takano, Masaya Nakamura, Atsushi Sekiya, Muneyoshi Yamaguti, Atsumi Nishida
Forestry and Forest Products Research Institute,
Abstract:
Four manganese peroxidase isozymes were purified from the culture fluid of Phanerochaete
crassa WD1694. The culture filtrate was subjected to DEAE-Sepharose chromatography and DEAE-Toyopearl
FPLC, and eluted as a single peak of manganese peroxidase activity. The sample showed a single band at amolecular weight of approximatey 50,000 on SDS- PAGE. The same sample was separated as four bands which
had the pI value of 4.50, 4.52, 4.62, and 4.65 on isoelectric phocusing, and all four bands were stained bymanganese peroxidase active staining. These results showed that Phanerochaete crassa WD1694 produced fourmanganese peroxidase isozymes which have same molecular weight and different pI values described above.
2001-P12
選択的白色腐朽菌 Celiporiopsis subvermispora の菌体外フリーラジカル反応 —NDA による鉄酸化還元の阻害と電荷移動錯体形成
榎 牧子*1*2、本田与一*1、渡辺隆司*1、桑原正章*1*1
京都大学木質科学研究所、*2 理化学研究所
Extracellular free radical reactions of selective white-rot fungus, Celiporiopsis subvermispora- Inhibition
effects on iron redox reactions and formation of charge transfer complexes.
Makiko Enoki, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
A selective white-rot fungus, Celiporiopsis subvermispora is able to decompose lignin without
intensive damage of cellulose accompanied by lipid peroxidation. Recently we reported production of threenovel lipid-related itaconic acid derivatives by this fungus. Among of them, 1-nonadecene-2,3-dicarboxylic acid
(NDA) was analyzed in this report. Electron transfer reactions of Fe(II) and Fe(III) were inhibited by NDA.
352

NDA formed charge transfer complexes with a quinoid compound originating from phenolic compounds inaqueous solutions. These phenomena suggest that NDA stabilizes Fe(II) and Fe(III) and interacts with oxidation
products from phenolic compounds during wood decay by C. subvermispora.
2001-P13
白色腐朽菌による土壌中ダイオキシン類の処理の試み —土壌成分の分解への影響について—
好光正豪*1、近藤隆一郎*1、坂井克己*1、東房健一*2*1
九州大学大学院生物資源環境科学研究科、*2 財団法人九州環境管理協会
Attempt to treat dioxins in soils by white rot fungi. -Influence of soil components on degradation of dioxins
Masahide Yoshimits*1, Ryuichiro Kondo*1, Kokki Sakai*1, Kenichi Tobo*2*1
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University, *2Kyushu Envirornental
Evaluation Association
Abstract:
We demonstrated that polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDDs/DFs) in toluene extracts of the soil were degraded by a white rot fungus Celiporia sp. MZ-340.
Degradation of a mixture of PCDDs/DFs extracted from the soil by the white rot fungus was examined in a
low-nitrogen Kirk medium. The toxic equivalence quantity (TEQ) of the extracts of the soil reduced from 19.0
to 12.4 ng-TEQ/flask, and that of the soil extracts, from which polar organic compounds had been removed bysilica gel, reduced from 10.0 to 2.4 ng-TEQ/flask by the treatment for 10 days with the white rot fungus.
2001-P14
白色腐朽菌の有する ferrireductase システムを用いた in vitro 系での二酸化マンガン還元
伊藤敬訓、平井浩文、西田友昭
静岡大学農学部
In vitro reduction of manganese dioxide by ferrireductase system in white-rot fungi
Takanori ltoh, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
In vitro reduction of manganese dioxide by ferrireductase system in white-rot fungi wasinvestigated. The reduction of manganese dioxide by Fe(II)-iron binding compound complex, which occurs at
extracellular region of the fungi, was dependent on pH, and Fe(Il)-iron binding compound complex was a goodelectron donor for the reduction of manganese dioxide compared with Fe(lI) itself. Fe(III)-iron binding
compound complex was the best substrate for NADPH-dependent ferrireductase than other ferric chelate. These
results suggest that ferrireductase system, including NADPH-dependent ferrireductase and Fe(III)-iron binding
compound, is involved in the reduction of manganese dioxide by white-rot fungi.
2001-P15
熱分解におけるリグニン中の各結合様式の反応性
堀越 直、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Reactivity of lignin substructures in pyrolysis of lignin
Sunao Horigoshi, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Reactivity of lignin in pyrolysis was studied at 400ºC focusing on depolymerization,polymerization, carbonization and gasification reactions by using α-O-4,β-O-4,β-1 and biphenyl types ofdimeric lignin model compounds. As a result, the following results were obtained. ① Reactivity for
depolymerization varies significantly depending on the model compound structure: α-O-4, phenolic β-O-4 >non-phenolic β-O-4, non-phenolic β-1 > phenolic β-1, biphenyl types of model compounds. ② Carbonization
occurs from almost structures via very reactive intermediate without leaving polymerization products soluble in
THF. ③ Gasification is not important at 400ºC.
2001-P16
フェノール性 β−O−4 型構造の熱分解開裂における α-及び γ-位の水酸基の役割
河本晴雄、堀越 直、坂 志朗
京都大学大学院エネルギー科学研究科
Role of Cα- and Cγ-hydroxyl groups on pyrolytic cleavage of phenolic β-O-4 type of structure
Haruo Kawamoto, Sunao Horigoshi, Shiro Saka
353

Graduate School of Energy Science, Kyoto University
Abstract:
Role of Cα- and Cγ-hydroxyl groups on pyrolytic cleavage of phenolic β-O-4 type of structure
was investigated by using a series of dimeric lignin model compounds with regiospecifically deoxygenatedstructures or regiospecifically methylated structures. As a result, it is revealed that hydrogen bonding between
these hydroxyl groups plays an important role in β-ether cleavage, and that this effect is only effective inphenolic structure. These results indicate that conformation of the phenolic β type of structure is important in
the mechanism of the β-ether cleavage.
2001-P17
エレクトロポーレーションによるヒラタケの形質転換
馬上 学、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
Genetic transformation of Pleurotus ostreatus using electroporation
Manabu Moue, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
Pleurotus ostreatus is one of the white rot basidiomycetes researched to utilize for biobleaching,bioremediation and catalysis of difficult chemical transformation. In order to elucidate the degrading mechanismof lignin by P. ostreatus, it is important to introduce genetic engineering techniques which permit us molecular
genetic analysis, such as overexpression of ligninolytic enzymes. In our laboratory, drug resistant marker gene
CbxR and transformation system have been developed in this fungus. However, many genetic manipulations,such as gene targeting and functional cloning, are not available if the transformation efficiency is low. We
examined transformation of P. ostreatus by electroporation aiming at high transformation efficiency.
2001-P18
担子菌のプロテオームデイフアレンシヤルディスプレー解析 —培地成分の発現タンパク質への影響—
中村朋史*1、一瀬博文*1、割石博之*2、田中浩雄*2*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究院
Proteome differential display analysis of basidiomycetes
Tomofumi Nakamura, Hirofumi Ichinose, Hiroyuki Wariishi, Hiroo Tanaka
Faculty of Agriculture, Kyushu University
Abstract:
The white-rot basidiomycete, Coriolus versicolor, metabolizes a series of sulfur- containing
heterocyclic compounds found in fossil fuels as impurities. In our previous study, certain thiophene and sulfide
compounds were degraded by C. versicolor more effectively under sulfur- limiting culture conditions,suggesting that the fungus utilizes sulfur compounds as a sulfur sourcefor growth. To better understand a metabolic system for sulfur compounds and to search for proteins related tothe desulfurization, proteome differential display analysis was performed.
2001-P19
ラッカーゼ／1-HBT 系による β-O-4 型リグニンモデル化合物の新規 β-エーテル開裂反応について
岩月正人、中川 誠、稲垣真澄、浜辺鮎佳、河合真吾、大橋英雄
岐阜大学農学部
New β-ether cleavage reaction of β-O-4 lignin model compounds by laccase/1-HBT system
Masato Iwatsuki, Makoto Nakagawa, Masumi Inagaki, Ayuka Hamabe, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
We have studied that the degradation mechanism of non-phenolic β-O-4 lignin modelcompounds by laccase/1-HBT system. In the previous work, we proposed new mechanisms for the formation ofCα-Cβ cleavage product via benzylic radical. In this study, we further investigated the incorporation
experiments of 18O from 18O2 into the degradation products of substrate (1) and (2) catalyzed by laccase/1-HBT
system respectively. The results suggest that a novel β-ether cleavage reaction is caused by laccase/1-HBT
system.
2001-P20
植物細胞壁成分の安定炭素同位体比に関する研究
上平雄也、谷川一樹、福島和彦、安田征市
名古屋大学大学院生命農学研究科
354

Stable carbon isotope ratios of some plant cell wall components
Yuya Kamihira, Kazuki Tanigawa, Kazuhiko Fukushima, Seiichi Yasuda
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
Stable carbon isotope ratios (δ13C) of some plant cell wall components were determined by anisotope ratio mass spectrometer (IRMS). The carbon of sugarcane (C4 plant) was isotopically heavier than thatof pine and popular (C3 Plants) significantly, and the carbon of the Klason lignins from all the species wereabout 2.6-3.7 ‰ lighter than that of the -celluloses. These results showed the same tendency as the previous
reports1) 2). Although δ13C of components of each tissue in sugarcane were also determined, the reproducibility
was not enough. Further precise measurements are needed to make differences between the tissues clear.
2001-P21
コニフェリルアルコールの脱水素重合中に生成するシリンギル核
斉藤香織*1、安田征市*1、小名俊博*2、福島和彦*1
名古屋大学大学院生命農学研究科、２王子製紙㈱森林資源研
Syringyl units generated during the polymerization of coniferyl alcohol
Kaori Saito*1, Seiichi Yasuda*1, Toshihiro Ona*2 and Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, *2Forestry Research Institute, Oji Paper Co.
Ltd.
Abstract:
Syringyl (S) and p-hydroxyphenyl (H) units were detected in addition to guaiacy1 (G) unit inthioacidolysis products obtained from the DHP prepared from only coniferyl alcohol using a peroxidase-H202
System. To determine the DHP at the dimer level, we analyzed thioacidolysis products of the DHP and detected
dimers of G-G, S-G, S-S and H-G types.
2001-P22
カプール（Dryobalanops spp.）心材の抗う蝕活性成分の検索
三原理江、光永 徹
三重大学生物資源学部
Anti-dental caries active compounds of kapur (Dryobalanops spp.) heart wood extracts
Rie Mihara, Tohru Mitsunaga
Faculty of Bioresources, Mie University
Abstract:
The inhibitory effects of 22 species of wood extracts on the glucosyltransferase (GTase) activity
were investigated. Kapur (Dryobalanops spp.) heart wood extracts showed inhibited
GTase activity more effectively than any other species. The results obtained by the Folin-Denis method for thedetermination of total phenol contents, vanillin-HCl method to determine flavanol contents and protein
adsorption by using BSA suggested that the active fractions contained hydrolyzable tannin like component. The
main components which inhibit GTase activity in kapur were probably ellagitannins, because a large amount ofellagic acid was released by acid hydrolysis. Furthermore, these components exhibited antioxidative activity in a
rabbit erythrocyte membrane ghost system.
2001-P23
分子軌道計算を用いたポリフェノールの反応性の解析 —フラボノイド類の付加縮合反応速度と分子軌道計
算値との相関性—渡辺泰高、光永 徹
三重大学生物資源学部
Reactivities of polyphenols with formaldehyde by Molecular Orbital Computation. —Correlation additionalcondensation rates of flavanoids and the parameters calculated by molecular orbital method
Yasutaka Watanabe, Tohru Mitsunaga
Faculty of Bioresources, Mie University
Abstract:
Molecular Orbital Computation for flavonoids, (+)-catechin and taxifolin, has been used to
study the relationshjp between the calculated electrostatic charges at the carbons existed Highest Occupied
Molecular Orbital (HOMO) and the reaction rate of hydroxymethylation with formaldehyde. Electrostatic
charges (q) of several kinds of flavonoids were calculated by semi- empirical methods at the AM1 and PM3 andab initio methods at RHF/3-21G level of theory. The rate (k) of flavonoids consumption were determined by
HPLC. When q were plotted against logarithm of k in these flavonoids, phenol, resorcinol and phloroglucinl,
high correlation (R2=0.92) was obtained.
355

2001-P24
マタイレジノールの 5 位水酸化過程に関する考察
大須賀優夫、鈴木視番、木原智仁、榎本慎一、河合真吾、大橋英雄、小山博之、原 徹夫
岐阜大学農学部
5-Hydroxylation of matairesinol in syringyl lignan biosynthesis
Masao Osuka, Mitsuru Suzuki, Tomonori Kihara, Shin-ichi Enomoto, Shingo Kawai, Hideo Ohasi, Hiroyuki
Koyama, Tetsuo Hara
Faculty of Agriculture, Gifu University
Abstract:
We have studied on the biosynthesis of syringyl lignans in Thuja species. In the previous work,
we suggested that matairesinol is the possible intermediate on the biosynthetic pathway of syringyl lignans. In
this study, we report the feeding experiment of [7, 7-2H2, 3'-OC2H3]matairesinol into T. occidentalis young shoot.
The results indicated for the first time that matairesinol was converted into thujaplicatin. Last of all, we show apreliminary experiment for the detection of matairesinol 5-hydroxylase gene.
2001-110
ペルオキシダーゼ遺伝子を抑制した形質転換ポプラの化学的・組織化学的解析
李 並紅、太田祥弘、梶田真也、諸星紀幸
東京農工大学大学院 BASE
Characterization of transgenic aspens inhibited by a peroxidase gene
Yahong Li, Nobuyuki Nishikubo, Shinya Kajita, Noriyuki Morohoshi
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology
Abstract:
To study the down-regulation of specific peroxidase involved in lignin biosynthesis and its
correlation with lignification, an anionic peroxidase gene, prxA3a was transferred into its original
host, hybrid aspen P. kitakamiensis (P. sieboldii X P. gradidentata) under the control of the original
promoter of prxA3a. Twelve transformed lines were regenerated and confirmed by PCR and Southern blotting.
Enzyme assay showed that both total peroxidase activity and prxA3a specific activity were decreased in mosttransgenic lines as compared to control plant. In addition, difference in lignin content and structure wasobserved between transformants and control aspen. Furthermore, histochemical analysis revealed thatsuppressed lignification in the secondary xylem was the result of down-regulated peroxidase expression. These
results indicated that it was achievable to develop genetically improved woody plant.
2001-111
担子菌カワラタケの環境汚染物質分解酵素遺伝子（mnp,lac）を導入した植物の分子育種と持続的環境修復に関する研究（2）池田成一郎*1、園木和典*1、飯村洋介*2、早川敏夫*3、金原和秀*3、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 産業技術総合研究所、*3JR 総合技術研究所
Studies on molecular breeding of plants with ability of MnP, Lac derived from Coliorus versicolor degrade
environmental pollutants and continuous remediation
Seiichiro Ikeda*1, Tomonori Sonoki*1, Yosuke Iimura*2, Toshio Hayakawa*3, Kazuhide Kinbara*3, Shinya
Kajita*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2National Institute of Advanced Industrial Science and Technology, *3Railway Technical ResearchInstitute
Abstract:
Remediation methods for environmental pollutants such as physical & chemical treatment andbioremediation have been experimentally tested. However, these methods have someproblems; these are impractical in view of cost efficiency of hazardous chemicals accumulated at
low levels in the environment or becomes labored as the area of contamination expands. Meanwhile, plant callbe grown independently taking nourishment from the sun, water, and inorganic ions, and can be cultivatedextensively by controlling seeds. Because of this, plants have attracted attention as a method for long-lasting
environmental decontamination. And, we have attempted to degrading hazardous chemicals directly usingtransgenic plants into which Mn-Peroxidase gene and Laccase gene for degrading hazardous chemicals derived
from Coliorus versicolor is transfered. If a plant capable of exerting the effect of these enzyme could be
prepared, it would be very useful for degrading and removing hazardous chemicals in the environment.
356

2001-112
微生物の物質変換機能の導入による、植物のフェニルプロパノイド合成系の制御
補永文子*1、梶田真也*1、園木和典*1、上杉幹子*1、政井英司*2、原田恭*2、福田雅夫*2、諸星紀幸*1、片山義博*1*1
東京農工大学大学院 BASE、*2 長岡技術科学大学
Manipulation of phenylpropanoid-biosynthetic pathway by genetic engineering with bacterial genes
Fumiko Honaga*1, Shinya Kajita*1, Tomonori Sonoki*1, Mikiko Uesugi*1, Eiji Masai*2, Kyo Harada*2, Masao
Fukuda*2, Noriyuki Morohoshi*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, *2Nagaoka University of Technology
Abstract:
Hydroxycinnamoyl-CoA esters are intermediates of phenylpropanoid biosynthetic pathway andcan be precursors of many secondary metabolic compounds such as flavonoids, stilbenes and lignin. A bacterial
gene FerB isolated from Sphingomonas paucimobilis SYK-6 encodes feruloyl-CoA hydratase/lyase. This
enzyme can catalyze the reaction step for conversion from hydroxycinnamoyl-CoAs to correspondinghydroxybenzaldehydes. We tried to express this gene in tobacco and hybrid aspen plants by genetic engineeringin aim to biosynthesize beneficial phenolic compounds in vivo. The transgenic plants showed activities to
produce hydroxybenzaldehydes.
2001-113
ペルオキシダーゼアイソザイムの基質認識とシリンギルリグニン生合成の役割
佐々木慎弥*1、堤 祐司*1、西田友昭*1、光永 徹*2*1
静岡大学農学部、*2 三重大学生物資源学部
Substrate utilization toward monolignols of peroxidase isoenzymes and their involvement in syringyl lignin
biosynthesis
Shinya Sasaki, Yuji Tsutsumi, Tomoaki Nishida, Thoru Mitsunaga
Faculty of Agriculture, Shizuoka University, Faculty of Bioresource, Mie University
Abstract:
A peroxidase, SyPO, isolated from the cell wall of poplar (Populus alba L.) callus culture iscapable to utilize sinapyl alcohol (Salc) as substrate most effectively in plant isoperoxidases. SyPO polymerized
sinapyl alcohol-oligomer (Salc-oligomer) and sinapyl alcohol, producing a polymer of greater molecular weight.
In contrast, horseradish peroxidase (HRP), which is specific to coniferyl alcohol (Calc), produced sinapyl
alcohol diners, rather than catalyzing polymerization. Adding coniferyl alcohol as a radical mediator in the
HRP-mediated reaction did not result in Salc-oligomer polymerization.
2001-114
シナップ酸に活性を有する 4-coumarate：coenzyme A ligase の検索
浜田勝義*1、堤 祐司*1、西田友昭*1、山内一慶*2、福島和彦*2*1
静岡大学農学部、*2 名古屋大学大学院生命農学研究科
Screening of 4-coumarate: coenzyme A ligase utilizing sinapic acid as substrate
Katsuyoshi Hamada, Yuji Tsutsumi, Tomoaki Nishida, Kazuchika Yamauchi, Kazuhiko Fukushima
Faculty of Agriculture Shizuoka University, Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
The conversion of sinapic acid to sinapoyl CoA was confirmed by an enzyme assay using
14
C-labeled sinapic acid and crude enzyme preparation from Robinia pseudoacacia L.. This and previous results
indicate that R. pseudoacacia has a biosynthetic pathway for sinapyl alcohol via sinapic acid. Fractionation of
the crude enzyme using a Mono Q column resulted into the resolution of two 4CL isoformes. The molecularweight of the one major 4CL fraction was estimated to be ca. 64kD by SDS-PAGE followed by the treatment
with 4CL-specific antiserum. This partially purified 4CL showed high activity with p-coumaric acid but very
low with sinapic acid and ferulic acid. Isolation of the 4CL isozyme active against sinapic acid in R.
pseudoacacia is ongoing.
2001-115
特別講演
茶の香気生成機構の研究から植物グリコシダーゼ研究の新展開へ
坂田完三
京都大学化学研究所
357

Invited Lecture: New research developments of plant glycosidases from studies on molecular basis of aroma
formation during tea manufacturing
Kanzo Sakata
Institute for Chemical Research, Kyoto University,
Abstract:
We have clarified the molecular mechanism of floral tea aroma formation during tea
manufacturing. Floral aroma such as geraniol, linalool, etc. are present mainly as β-primeveroside(6-O-β-D-xylopyranosyl-β-D-glucopyranosides in fresh tea leaves), which are hydrolyzed by a disaccharide
specific glycosidase, β-primevrerosidase, to aglycons (aroma compounds) and primeverose. The glycosidase
shows a very high substrate specificity to β-primeverosides. Gene cloning of the glycosidase shows very highhomology in its amino acid alignment to that of amygdalin hydrolase (57 %). We also have succeeded insynthesis of new type of glycosidase inhibitors (glycosyl amidines), which can be easily synthesized from eachsugar without protecting hydroxy groups. Each glycosyl amidine shows very high selective and competitive
inhibitory activity against its corresponding glycosyl hydrolase. A successful application for affinity
chromatography is shown.
2001-116
特別講演
リグノセルロースの利用 —現状と将来
畠山兵衛
福井工業大学工学部
Invited Lecture: Utilization of lignocellulosics, —Present and future
Hyoe Hatakeyama
Faculty of Engineering, Fukui University of Technology
Abstract:
This paper reviews liquid crystals, high performance polymers and environmentally compatible
polymers that have been derived from saccharides and phenolic compounds. Liquid crystals were synthesizedfrom 4-hydroxylphenyl, guaiacyl and syringyl derivatives which are obtainable from lignin. Polymers such as
polyurethanes containing saccharide and lignin structures were also synthesized. Polycaprolactone derivatives
were synthesized from lignin, cellulose and cellulose acetate. Thermal and mechanical properties of the abovesaccharide- and lignin- derivatives were studied by differential scanning calorimetry, thermogravimetry,
thermogravimetric infrared spectroscopy (TG-FTIR) and mechanical measurements.
2001-201
Anthricus sylvestris におけるシリンギル型リグナン生合成経路について
榊原紀和、鈴木史朗、梅澤俊明、島田幹夫
京都大学木質科学研究所
Syringyl type lignan biosynthesis in Anthriscus sylvestris
Norikazu Sakakibara, Shiro Suzuki, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
Feedirq experiments with Anthriscus sylvestris have indicated that thujaplicatin, 5methylthujaplicatin, 4, 5-dimethylthujaplicatin are good precursos of the syringyl type lignan yatein.
Furthermore, Anthriscus sylvestris cell-free extracts catalyzed O-methylation of several lignans including
thujaplicatin and 5-methylthujaplicatin.
2001-202
熱帯産イネ科飼料植物の消化性と細胞壁化学構造
樋口暁浩*1、飯山賢治*２*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
Structural feature of indigestible wall components of tropical forage grasses
Akihiro Higuchi*1, Kenji Iiyama*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Asia Natural Environmental
Science Center, the University of Tokyo
Abstract:
Setaria grass (Setaria sphacelata (Schmach.) Stapf & Hubbard ex M.B. Moss) and Guinea grass(Panicum maximum Jacq.) as tropical forage grass were investigated for the relation- ship between cell wall
structure and their digestibilities. In vitro cell wall digestibility (IVCWD) was highly correlated withhydroxycinnamic acid content, especially indigested hydroxycinnamic acid content. This result suggests that358

indigestible cell wall contain high amount of covalent association between lignin and wall polysaccharides(LCC) through hydroxycinnamic acids. Generally, parenchyma cell in grass stems was easily digested. However,Setaria and Guinea grasses have indigestable parenchyma.
2001-203
カカオ（Theobroma cacao L.）種皮の導管及び非導管組織中のポリフェノールの差異
Byung−Yeoup Chung*1、飯山賢治*２*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
Differences in accumulated polyphenolic compounds between vascular bundles and non-vascular bundles of
Cacao（Theobroma cacao L．）hull
Byung−Yeoup Chung*1, Kenji Iiyama *２*1
Graduate School of Agricultural and Life Sciences，the University of Tokyo, *2Asian Natural Environmental
Science Center，the University of Tokyo
2001-204
ラット尿中に存在する DHP 由来のファイトエストロジェン
長野和種*1、福島和彦*1、安田征市*1、堀尾文彦*1、Augustin Scalbert*2*1名古屋大学大学院生命農学研究科、*2INRA-Clermont-Ferrand
Phytoestrogens found in the urine of a rat after oral administration of DHP
Kazutane Nagano*1, Kazuhiko Fukushima*1, Seiichi Yasuda*1, Fumihiko Horio*1,Augustin Scarbert**1
Graduate School of Bioagricultural Sciences, Nagoya University, *2INRA, Saint-Genes- Champanelle, France
Abstract:
Two groups of hormone-like diphenolic phytoestrogens, lignans and isoflavonoids, are exist in
human body fluids, and have gained increasing interest because of their possible cancer protective properties.
The phytoestrogenic lignans are called mammalian lignans. The two major mammalian lignans, enterodiol andenterolactone, are thought to be the products of colonic bacterial metabolism of the plant precursors
secoisolariciresinol and matairesinol. However little is known about, the biotransformation of these compounds.
And the possibility that lignin in the dietary fiber might be converted into mammalian lignans has been
considered. In order to clarify whether lignin is biotransformed to mammalian lignans, lignin model compound,
DHP prepared by endwise polymerization of coniferyl alcohol was administrated to the female Wistar rat andthe urine was analyzed by GC-MS. Enterodiol and enterolactone were detected, which were not detected in thecontrol urine. This is sufficient to show the possibility that DHP could be converted into mammalian lignans.
2001-205
無機系粒子分散型ポリウレタン系ジオコンポジットの機械的性質
馬渕将人、畠山兵衛
福井工業大学工学部
Mechanical properties of geocomposites of the polyurethane system containing lignin
Masato Mabuchi, Hyoe Hatakeyama
Fukui University of Technology
Abstract:
Polyurethane (PU) geocomposites were prepared from a mixture of lignin, polyethylene glycol(PEG) (Mw=ca.200) and silicic sand. The content of lignin in PEG was changed from 0 to 90%. Mechanicalproperties of the above PU geocomposites were investigated by mechanical measurements. In the kraft lignin(KL)-PEG200-polyphenyl polyethylene polyisocyanate (MDI) system and in the lignosulfonate(LS)-PEG200-MDI system, the permeation distance of PU into silicic sand increased with increasing lignin
contents. However, a maximum stress of the PU geocomposites decreased with increasing lignin contents.
2001-206
リグノスルホン酸含有硬質ポリウレタンフォームの調製と物性
浅野育洋*1、畠山兵衛*1、畠山立子*2*1
福井工業大学工学部, *2 大妻女大学家政学部
Preparation and properties of lignosulfonate-based rigid polyurethane foams
Y. Asano*1, Hyoe Hatakeyama*1, Tatsuko Hatakeyama*2*1
Fukui University of Technology, *2Otsuma Women's University
Abstract:
Rigid polyurethane (PU) foams were prepared from lignosulfonate (LS) dissolved in diethylene
glycol (DEG), triethylene glycol (TEG) or polyethylene glycol (Mw=200:PEG200) by the reaction with359

polyphenyl polymethylene polyisocyanate (MDI). Thermal and mechanical properties of the above
polyurethanes (PU's) were investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), andcompression tests. Glass transition temperatures (Tg's) of the PU's from the LS-PEG200-MDI system increasedslightly with increasing LS content. However, Tg's of the PU's from the LS-DEG-MDI system did not show
obvious change with increasing LS content.
2001-207
リグニンを原料とするエステル系エポキシ樹脂の合成と熱的性質
廣瀬重雄*1、畠山兵衛*２*1
産業技術総合研究所、*２福井工業大学工学部
Synthesis and thermal properties of ester-epoxy resins from lignin
Shigeo Hirose*1, Hyoe Hatakeyama*2*1
Research Institute of Materials and Chemical Process, AIST, *２ Fukui University of Technology
Abstract:
Alcoholysis lignin (AL) was dissolved in ethylene glycol and the obtained mixture was reactedwith succinic anhydride to form a mixture of ester-carboxylic acid derivatives (AL-polyacid, ALPA). Ethylene
glycol-polyacid (EGPA) was also prepared from ethylene glycol. The obtained mixture of ester carboxylic acidderivatives was reacted with ethylene glycol diglycidyl ether in the presence of catalytic amount ofdimethylbenzylamine to form ester-epoxy resins. The curing reaction was analyzed by Ozawa's method using
differential scanning calorimetry (DSC). The activation energy (E) of curing reaction in the initial step was
found to be ca. 83 kJ/mol. The molar ratios of epoxy groups to carboxylic acid groups ([EPOjN]/[AA] ratios,
mol/mol) were varied from 0.8 to 1.3. The contents of ALPA in the mixture of ALPA and EGPA (ALPA content)
were also varied from 0 to 100 %. Thermal properties of epoxy resins were studied by DSC andthermogravimetry (TG). Glass transition temperatures (T g's) of epoxy resins showed a maximum value of -11.5ºC when [EPOXY]/[AA] ratio was 1.1. Tg's increased with increasing ALPA contents suggesting that lignin acts
as a hard segment in epoxy resin networks. Thermal degradation temperatures (T d's) of epoxy resins slightly
decreased with increasing ALPA contents.
2001-208
アルカリ性酸素処理に伴うリグニンの赤外吸収スペクトルの変化
矢田 実、角田靖典、新谷博幸、飯塚堯介
東京大学大学院農学生命科学研究科
The changes in infrared spectra of lignin by alkaline oxygen treatment
Minoru Yada, Yasunori Tsunoda, Hiroyuki Shintani, Gyosuke Meshitsuka
Graduated School of Agricultural and Life Science, The University of Tokyo
Abstract:
Various oxidizing agents were applied for bleaching sequence of kraft pulp. Oxygen
delignification under alkaline condition which is employed by many plants is important process for pulp
bleaching. Structural changes of lignin during oxygen delignification stage are, however, not clarified yet indetail. In this study, softwood and hardwood kraft lignins were treated with alkaline oxygen (1M NaOH,
0.3MPa, 70ºC) for 0.5-8.5 hours, and the reaction solutions were analyzed by IR spectroscopy with ATR(Attenuated Total Reflection) methods. The changes in spectra depending on reaction time indicated that
aromatic rings with high reactivities to oxygen were almost cleaved until 2.5 hours of reaction, while increase ofabsorbance due to carboxyl group continued to 8.5 hours of reaction. Spectral changes were observed when pHof the reaction solution of softwood kraft lignin treated for 3.0 hours was increased from 9.4 to 12.2, whichshould be caused by the difference of degree of dissociation of phenolic hydroxyl groups.
2001-209
酸素漂白過程におけるフェノール類の酸化反応速度
横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Model studies on kinetics of phenol oxidation during oxygen bleaching
Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Several phenolic compounds were subjected to oxygen-alkali treatment, and their degradations
were analyzed in detail by applying a novel formula_ This formula was established by two considerations. One
was that the degradation of phenolic compounds should be expressed by the sum of two reactions; one of which360

is caused by molecular oxygen and the other by active oxygen species. The other consideration was that thedegradation of phenolic compounds should be written by a pseudo-first-order reaction in which the rate constantkobs(t) is dependent on reaction time. By arrangements, kobs(t) was shown as a hyperbola. The contribution ofactive oxygen species to the degradation of phenolic compounds is visualized by illustrating kobs(t). The higher
the temperature is, the more active oxygen species contribute to the degradation of phenolic compounds. The
extrapolation of kobs(t) to the beginning of the reaction gave an initial pseudo-first- order reaction rate constantkobs((initial). The reaction between phenolic compounds and molecular oxygen without any influence of active
oxygen species can be elucidated by using kobs((initial). As expected, kobs((initial) is dependent on functionalgroups, which indicates that their electronic effect on the aromaticπelectron system provides the reaction rate ofphenolic compounds with molecular oxygen.
2001-210
非塩素系漂白過程における α−カルボニル型リグニン構造の挙動 II．定量法の確立とそのパルプ残存リグニンへの適用
友田生織、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Formation and degradation of α-carbonyl structure in lignin during chlorine free bleaching, II. Method toestimate the α-carbonyl content in lignin remaining in pulp
Iori Tomoda, Yuji Matsumoto, Gyosuke Meshitsuka
Graduated School of Agricultural and Life Science, the University of Tokyo
Abstract: When guaiacylglycerol-β-guaiacyl ether carrying deuterium at α-methin position (GG-D) was
subjected to nitrobenzene oxidation under the usual reaction condition, the retention of deuterium in the formyl
group of the reaction product (vanillin) was quite low because of the D-H exchange during the reaction. The
D-H exchange could be suppressed by employing LiOH or Ba(OH)2 as an alkali during nitrobenzene oxidation.
This finding was applied to the semi-quantitative analytical method of lignin α-carbonyl structure, which
consists of successive NaBD4 reduction of α-carbonyl structure and nitrobenzene oxidation. Experiments using
α-carbonyl enriched MWL (DDQ treated MWIJ) and its H2O2 treatment product revealed that the increase andthe decrease of α-carbonyl structure in lignin could be successfully analyzed by this method.
2001-211
酸処理・過酸化水素漂白を用いるクラフトパルプの無塩素漂白
大井 洋、池田 努
筑波大学農林工学系
Non-chlorine bleaching of kraft pulp using acid and hydrogen peroxide
Hiroshi Ohi, Tsutomu Ikeda
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Chlorine dioxide is most popular chemical to convert the bleaching from chlorine system to
ECF system. But usually over three times chlorine dioxide need to get the same result that of chlorine system.
We discussed about decreasing chlorine dioxide during ECF and non-chlorine bleaching using acid, ozone andhydrogen peroxide. Kappa number 9.4 LKOP contained hexeneuronic acid that was equivalent to kappa number
2.3. After acid treatment and ozone bleaching kappa number decreased to 2.9. But about 26% hexeneuronic acidthat was equivalent to kappa number 0.6 still existed in pulp.
2001-212
On-line Kappa number determination in sulfite pulping by visible spectroscopic measurements on spent liquor
Yimin Xie，Wenhao Shen, Huanbin Liu
South China University of Technology
Abstract:
This paper presents a method of on-line measurement of Kappa number with visible
spectroscopy during batch sulfite cooking. It was discovered that the absorption of the spent liquorfrom Masson's pine in 460-580nm wave range resulted mainly from lignin-sulfonate with high molecular weight(MW>30KD) and that Kappa number maintained a linear relationship with the absorbency of the spent liquor
within the wave range. Mathematical models of on-line Kappa number determination with visible light of
460-580nm wavelength were developed by chemometrics for batch sulfite cooking. These models had highlearning and prediction precision. Their relative errors were less than 1.5 Kappa number.
2001-213
361

HBS パルプ化 —溶媒の安定性とパルプの漂白性
佐野嘉柘、オリギル、梶本純子
北海道大学大学院農学研究科
HBS pulping- sabilization of solvents and bleachability of HBS pulp
Yoshihiro Sano, Aorigele and Junko Kajimoto
Graduate School of Agriculture, Hokkaido University
Abstract:
We has reported in the earlier work of this series that not only hardwood and nonwood, but
softwood can be pulped at elevated temperatures and low pressure by HBS pulping process using low-volatilesolvents (HBS) with the boiling pint of about 200ªC. One HBS introduced into pulp
process has to be recovered quantitatively from spent liquors to be used repeatedly as pulping solvents, so thestability of HBS to heat was investigated. Also, in order to prepare complete- bleached pulp for paper-grade,functional cellulose and biopolymers, the bleachability of HBS pulps
was studied. The results showed that the pulps were easily bleached by ECF sequence and TI of each pulp was
improved significantly by bleaching.
2001-214
HBS パルプ化 —リグニンの理化学的性質
長岡秀明、佐野嘉柘
北海道大学大学院農学研究科
HBS pulping. -Physical and chemical properties of lignin
Hideaki Nagaoka, Yoshihiro Sano.
Graduate School of Agriculture, Hokkaido University
Abstract:
HBS pulping of birch wood with PG in a rotating autoclave was carried out. Spent liquors wereseparated into lignin and RPG. RPG consisted of low molecular lignin products, sugars and modified sugar
products in addition to PG as a main material. The results on the yields of pulp, pulp residual lignin (KL) andlignin showed that PG and RPG were good pulping solvents corresponding to butanediols (BDOL) and RBDOL,
though RPG and RBDOL were better solvents than PG and BDOL. Ligmins prepared by HBS pulping with
RPG in a rotating autoclave have lower molecular weight, a lower amount of methoxyl groups and a higher
amount of phenolic hydroxyl groups than those with PG.
2001-215
酢酸パルプの機能化（2） —パルプ化・漂白および誘導体化を酢酸中で行うシステムの構築—
佐藤大典、辻 洋路、浦木康光、岸本崇生、佐野嘉柘
北海道大学大学院農学研究科
Functionalization of acetic acid pulp, (2) -Construction of the successive system from pulping to derivatization
performed in acetic acid
Hironori Sato, Hiromichi Tsuji, Yasumitsu Uraki, Takao Kishimoto, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
To explore the further application of acetic acid pulp (AP) in addition to the use as chemical
pulp, we investigated the production system of cellulose acetate (CA) from wood by the successive treatment ofacetic acid pulping, TCF bleaching and acetylation, which were performed in acetic acid. AP with Kappa
number 30 and ISO brightness 16 was bleached by ozone (Z) to Z-AP with 1.9 and 48, respectively, and then by
the following peracetic acid (Pa) to Z-Pa-AP with 0.6 and 66. The resulting bleached AP could be derivatized to
CA with degree of substitution of 2.54 and high solubility in acetone by the conventional acetylation.
2001-216
メソ多孔体へ固定化したマンガンペルオキシダーゼによるバイオパルプ漂白システム
梶野 勉、杉山英彦、浅見 修、高橋治雄
株式会社豊田中央研究所
New pulp biobleaching system involving manganese peroxidase immobilized in a silica support with controlled
pore sizes
Tsutomu Kajino, Hidehiko Sugiyama, Osamu Asami, Haruo Takahashi
Toyota Central R & D Labratories, Inc.
Abstract:
Attempts have been made to use manganese peroxidase (MnP) for chlorine-free pulp
biobleaching, but they have not been commercially viable because of the enzyme's low stability. We developed a362

new pulp biobleaching method involving mesoporous material-immobilized manganese peroxidase from
Phanerochaete chrysosporium. MnP immobilized in FSM, a folded-sheet mesoporous material whose pore sizeis nearly the same as the diameter of the enzyme, had the highest thermal stability and tolerance to H2O2. We
constructed a thermally discontinuous two-stage reactor system, in which the enzyme (39ºC)and pulp-bleaching(70ºC)reactions were performed separately. After seven cycles of MnP-treatment and alkaline extraction, thebrightness of the pulp increased to about 85% within 6h.
2001-217
マンガンペルオキシダーゼを用いたアゾ系反応性染料の脱色
原園幸一*1、渡辺吉雄*2、深津武馬*1*1
産業技術総合研究所、*2 メルシヤン㈱生資研究所
Decolorization of azo reactive dye by manganese peroxidase system
Koichi Harazono*1, Yoshio Watanabe*2, Takema Fukatsu*1*1
National Institute of Advanced Industrial Science and Technology (AlST), *2Bioresource Laboratories,
Mercian Corporation
Abstract:
We investigated the decolorization of azo reactive dye, Reactive Red 120 by white rot fungus
Phanerochaete sordida YK-624 and its enzyme. The dye (200 mg/l) was decolorized 90.6% by P. sordida
YK-624 in a medium containing 3% malt extract for 7 days. Manganese peroxidase (MnP) activity was detectedduring decolorization by the fungus. By methylation with H2SO4 and methanol, linoleic acid methyl ester was
also detected from the mycelium. The dye was treated with MnP purified from P. sordida YK-624. The dye wasdecolored by MnP system in the presence of Mn2+ and Tween 80. These results suggest that P. sordida YK-624
and MnP have potential applications for the cleanup of textile mill effluents.
2001-218
Production and purification of laccase from white rot fungus Lentites sp. NP21
Chartchai Khanongnuch*1，Nittaya Wanphrut*1, Saisamorn Lumyong*1，Yoichi Hond*2，Masaaki Kuwahara*2,
Takashi Watanabe*2*1
Faculty of Agro-industry, Chiang Mai University, *2Wood Research Institute, Kyoto University
Abstract:
The laccase was produced by the thermotolerant wood rotting fungus isolated from tropical rain
forest in northern Thailand, Lenzites sp. NP21, on solid state fermentation containing the rubber wood chips as anutrient source. The laccase production was 2.94 units/gram substrate. Addition of 4% (w/v) peptone solution
increased the enzyme production yield up to 5.69 units/gram substrate and addition of 150 M of CuSO4
increased the enzyme produced to 9.43 units/gram substrate. The laccase was purified to the homogeneity using
the DEAE-cellulose column chromatography, ultrafiltration and gel filtration on Sephadex G-100 column. The
enzyme was purified 893 folds with 49.8% of recovery yield. The optimal pH of enzyme was found at pH 4.0
and the maximum stability, after incubation for 24 hours at various pH, was found from pH 3.5-5.0. The enzyme
showed the thermal stability up to 45ºC and decreased continuously at the higher temperature. The half-life ofheat inactivation at 55ºC and 60ºC were 130 and 70 min, respectively. The enzyme was inactivated completely
with 1 mM Hg+2 ion. Further research on characterization of the purified laccase is in progress.
2001-219
白色腐朽菌 Phanerochaete sordida YK−624 株の産生するペルオキシダーゼによるリグニンモデル化合物の分解
杉浦むつみ、平井浩文、西田友昭
静岡大学農学部
Degradation of lignin model compound by peroxidase produced by white-rot fungus Phanerochaete sordida
YK-624
Mutsumi Sugiura, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The peroxidase which involves in the degradation of nonphenolic β-O-4 lignin modelcompound by white-rot fungus Phanerochaete sordida YK-624 was purified to homogeneity by Mono Q andSuperdex 75 chromatographies. The peroxidase was monomeric heme protein, and the molecular weight was
about 50 kDa. The study of degradation of nonphenolic β-O-4 lignin model compound by the peroxidase
showed that the Cα-Cβcleavage dominantly occurs, and that very small amount of degradation products, which
are originated from -oxidation, β-O-4 bond cleavage and B-ring cleavage, are detected. These oxidative
degradation of nonphenolic model were obtained by lignin peroxidase (LiP) from P. chrysosporium, however,363

more effective degradation was observed with the peroxidase of P. sordida YK-624 compared with the LiP.
2001-220
非フェノール性リグニン β-aryl ether 結合の特異的開裂活性を持つ糸状菌の新規細胞外分泌酵素の検出とその分解機能の解析
大塚祐一郎*1、園木和典*1、中村雅哉*2、梶田真也*1、片山義博*1
東京農工大学大学院 BASE、森林総合研究所
Detetiion and isolation of new fungus that cleave the β-aryl ether linkage of high molecular lignin by using thehigh sensitive assay system
Yuichiro Otsuka*1, Tomonori Sonoki*1, Masaya Nakamura*2, Shinya Kawai*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Forestry and Forest Products Research Institute
Abstract:
Cleavage of the arylglycerol-β-aryl eher linkage is the most important process in the biologicaldegradation of lignin. The bacterial β-etheras was already described and was tightly associated with the cellular
membrane. This function is not able to cleave β-aryl ether linkage in the high molecule lignin, because thisenzyme does not secret to extracellular space. In our previous study, the fungal β-aryl ether cleavage enzyme
was also described and required the p-hydroxyl group and Ca alcohol structure. In this study, we tried the searchof the fungi that cleave the β-aryl
ethler linkage of non-phenolic structure by extracellular function. We succeeded to isolation the fungus,
2T6-6-strain that has β-aryl ether cleavage function for non-phnolic lignin model compounds.
2001-221
耐塩性白色腐朽菌に関する研究（IV）耐塩性白色腐朽菌 MG-60 株による MnP 産生の海塩添加による促進効果について李 シン、近藤隆一郎、坂井克己
九州大学大学院生物資源環境科学研究科
Study on hypersaline-tolerant white-rot-fungi, (IV). A study on the stimulation of sea salts on MnP production
by the salt-tolerant white rot fungus Phlebia sp. MG-60
Xin Li, Ryuichiro Kondo, Kokki Sakai.
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University
Abstract:
A white rot marine isolate, Phlebia sp. MG-60, secreted manganese peroxidase (MnP) under
different sea salt incubation conditions, and its MnP production was strongly enhanced by the added sea salts
into incubation media. In this paper, we demonstrate how and why sea salts enhanced the MnP production by
Phlebia sp. MG-60, and the results pointed out that the combination of NaCl and Ca2+ enhanced MnPproduction as strongly as sea salts.
2001-222
選択的白色腐朽菌 Ceriporiopsis subvermispora の菌体外フリーラジカル反応 —NDA による水酸化ラジ
カル生成反応の抑制
寺西紘子、榎 牧子、本田与一、渡辺隆司、桑原正章
京都大学木質科学研究所
Extracellular free radical reactions of selective white-rot fungus, Ceriporiopsis subvermispora—Suppression of hydroxyl radical generation by NDA
Hiroko Teranishi, Makiko Enoki, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University
Abstract:
A selective lignin-degrading fungus, Ceriporiopsis subvermispora is able to decompose lignin
without morphorogical changes of wood cell walls. Since lignolytic enzymes are too big to penetrate inside ofplant cell walls, this fungus decomposes lignin at a site far from enzymes using low molecular mass metabolites.
In the wood decaying process, it is expected that the fungus suppresses hydroxyl radical generation to prevent
depolymerization of cellulose. In this paper, we report that hydroxyl radical generation by Fenton reaction issuppressed by a novel metabolite of C.
subvermispora, 1-nonadecene-2, 3-dicarboxylic acid (NDA).
2001-223
ラッカーゼ-メデイエーター系によるポリエチレンとナイロンの分解364

藤澤幹仁、平井浩文、西田友昭
静岡大学農学部
Degradation of polyethylene and nylon in laccase-mediator system
Mikihito Fujisawa, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
We investigated whether the laccase-mediator system (LMS) with 1-hydroxybenzo- triazole(HBT) as a mediator could degrade high-molecular-weight polyethylene and nylon-66 membranes. The LMS
markedly reduced the elongation and tensile strength of these membranes. After 3 days of treatment with the
LMS, the Mw of polyethylene decreased from 242,000 to 28,300, and that of nylon-66 Mw from 79,300 to
14,700. The LMS also decreased the polydispersity (Mw/Mn) of polyethylene and nylon-66. Furthermore, these
reductions in elongation, tensile strength, and molecular weight were accompanied by morphologicaldisintegration of the polyethylene and nylon-66 membranes. These results strongly suggest that the LMS with
HBT can effectively degrade polyethylene and nylon-66.
2001-224
クラフトパルプ ECF 漂白排水中のダイオキシン類発生レベル
中俣恵一*1、大井 洋*2*1
北越製紙株式会社、*2 筑波大学農林工学系
Dioxins level of kraft pulp ECF bleaching mill sewers
Keiichi Nakamata, Hiroshi Ohi
Hokuetsu Paper Mills, Ltd., Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
In accordance with the new legislation on dioxin abatement put into effect in Japan in January
2000, kraft and sulfite pulp bleaching mills with chlorine and chlorinated compounds are specified as dioxin
generation sources, and since then such pulp mills are subject to restriction of this code. With this code, theconcentration of dioxins and coplanar PCBs are restricted below
1 pg-TEQWHO1998/L for the river waterand below 10pg-TEQ/L for the effluents from the mills. Under the circumstances above, the Hokuetsu Paper
Niigata mill converted in April 2000 its conventional bleaching line with the annual production of 200,000
ADMT into an ECF process following the new ECF bleaching line with the annual production of 400,000
ADMT started up in 1998.
2001-225
ダイオキシン分解微生物の新規アツセイ基質によるスクリーニング
中村雅哉*1、菱山正次郎*1、大塚祐一郎*2、小林 崇*2、片山義博*2*1
森林総合研究所、*2 東京農工大学大学院 BASE
Screening of dioxin degrading microorganisms by new assay substrate
Masaya Nakamura*1, Shojiro Hishiyama*1, Yuichiro Otsuka*1, Takashi Kobayashi*2, Yoshihiro Katayama*2*1
Forestry and Forest Products Research Institute, *2Graduate School Bio-application and System Engineering,Tokyo University of Agriculture and Technology
Abstract:
A new method to facilitate rapid and sensitive screening of dioxin degrading microorganisms
was developed. The dioxin-like substrates were synthesized with the conjugation of chlorobenzene andfluorescence substrates. Microorganisms including fungi and bacteria are cultivated in liquid culture containing
these dioxin-like substrates. Fluorescence based on the cleavage of the dioxin ring of the dioxin-like substrates
was measured. The method is especially useful for screening for powerful dioxin degrading strains in naturalenvironments. It eliminates the need for special equipments and laborious analysis which are used for theradiolabeled dioxin. In this study, the new assay method has been used to screen our stock fungi.
2001-226
数種のダイオキシン分解菌を用いた PCB 分解の試み
三好進祐、木村圭助、伊藤和貴、橋 燦郎
愛媛大学農学部
Biodegradation of polychlorinated biphenyls by some microorganisms having ability for degradation of dioxins
Shinsuke Miyoshi, Keisuke Kimura, Kazutaka Ito, Sanrou Tachibana
Faculty of Agriculture, Ehime University
Abstract:
To obtain the basic information for purification of polychlorinated biphenyl (PCBs) bybioremediation, microbial degradation of PCB was conducted. Microbial degradation of two kinds of PCBs,
365

4-chlorobiphenyl (4CB) and 3,3',4,4'-tetrachlorobiphenyl (TCB) was conducted by the three microorganisms,
two white-rot fungi (PL1 and 267) and a bacteria screened from the nature,
respectively, in a liquid medium. The two fungi degraded about 90% and 70% of 4CB and TCB, respectively,
for 30 days. On the contrary, the bacteria degraded about 20% of TCB were degraded by manganese peroxidase(MnP) and mediator complex system for 24 hours.
2001-227
白色腐朽菌 Phlebia lindtneri による dibenzo-p-dioxin および dibenzofuran の分解
森 智夫、近藤隆一郎
九州大学大学院生物資源環境科学研究科
Degradation of dibenzo-p-dioxin and dibenzofuran by the white-rot fungus, Phlebia lindtneri
Toshio Mori, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University
Abstract:
Dibenzo-p-dionxin (DD) and dibenzofuran (DF) was rapidly degraded in lignolytic cultures of
the white-rot fungus Phlebia lindtneri. Although DF was oxidized to 2- and other position hydroxylateddibenzofuran, the amounts of these metabolites were too little (< 1 %). 2-hydroxy- dibenzofuran (2-OH-DF)
was rapidly decreased over 50 times than DD and DF. Significant inhibition of DD and DF degradation wasobserved in incubation with the cytochrome P-450 inhibitor 1-amino- benzotriazole. In this fact, we concluded
that DD and DF were oxidized to hydroxy derivatives by the cytochrome P450, and hydroxy derivatives will bedegraded by the further oxidation by the extracellular laccase and /or peroxidase.

366

第 47 回 （2002.10.31-11.01） アクロス福岡国際会議場
2002-101
単離過程におけるリグニン構造の変化とその要因について
藤本 文、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Stereo preferential degradation of β-O-4 structure during the process of MWL isolation
Aya Fujimoto, Yuji Matstmoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Beech (Fagus crenata Blume) wood meal was milled for 40 to 120 hr with/without toluene byvibratory ball mill to prepare the milled woods, from which the MWLs were isolated by Björkman's method.
The derived milled wood and MWL samples were subjected to the ozonation to investigate the changes in E/Tratio and the content of β-O-4 structure. As the milling effect proceeds, both the E/T ratio and β-O-4 content of
the milled wood decreased suggesting that the erythro β-O-4 structures is more frequently degraded than the
threo one during the milling. This indicates that the stereo preferential degradation of lignin proceeds during
milling. On the other hand, E/T ratio of MWL increased with the progress of milling but was always lower thanthat of milled wood from which MWL was extracted. MWL seems to be extracted easily from a region with low
E/T ratio arid, with the progress of milling, lignins in regions with higher E/T ratio gradually become
extractable.
2002-102
MWL 抽出残渣から得た水溶性多糖類に含まれるリグニンの構造
相見 光、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Structure of small lignin fragment retained in water soluble polysaccharide extracted from MWL isolation
residue
Hikaru Aimi, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Water soluble polysaccharide (WS) was extracted from finely divided softwood residues after
extraction of MWL. WS contains only 5.3% of lignin. In a gel filtration curve of WS, lignin was found together
with sugars at higher molecular weight part. After treatment of WS with carbohydrate degrading enzyme, theapparent molecular weight of both lignin and sugars decreased significantly. Contrary to this, mild alkaline
treatment of WS resulted in the significant decrease of the apparent molecular weight of lignin while that ofsugars were almost unchanged. These results may indicate that lignin in WS is present as small fragments
attached to polysaccharide chain.
2002-103
MWL 抽出残達への TIZ 法適用の試み
廣澤修一、高野俊幸、中坪文明
京都大学大学院農学研究科
Attempts to application of TIZ degradation method to wood meal after extraction of MWL
Shuichi Hirosawa, Toshiyuki Takano, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
Tosylation of wood meal after extraction of MWL (WMEM) was investigated for TIZ
degradation analysis. The degree of tosylation was evaluated by FT-IR. The WMEM was tosylated underconventional TsCl / Pyridine condition, but only small amount of Tosyl group was introduced into the WMEM.
Then, the WMEM was divided into three fractions, Cellulose-Lignin fraction (CL),
Hemicellulose-Lignin fraction (HCL), Insoluble-Lignin fraction (IL). Each fraction was highly tosylated underappropriate reaction conditions. Thus, TIZ degradation method may be applied to elucidate total lignin structure
in wood.
2002-104
リグニンの β-O-4 結合の生成に対するコンピュータシミュレーシヨン
重松幹二、小林孝行、田口大安、棚橋光彦
岐阜大学農学部
367

Computer simulation on the formation of β-O-4 linkage of lignin
Mikiji Shigematsu, Takayuki Kobayashi, Hiroyasu Taguchi, Mitsuhiko Tanahashi
Faculty of Agriculture, Gifu University
Abstract:
Dehydrogenative polymerization of monolignols was computer-simulated with semi- empiricalmolecular orbital calculation, MOPAC2002. The reactivity was predicted by activation enthalpy at the transition
state with the assumption of a kinetic control. In radical coupling stage, it was predicted that the production ratioof β-O-4 coupling was low compared with those of β-β, β- and 5-5 couplings, however, it was increased in
non-polar solvent. In the reaction of water to α-carbon of β-O-4 quinonemethide, it was predicted that threo
form was predominant. However, the reactivity depended on the charge of hydroxyl group and the molecularsize of nucleophile.
2002-105
熱分解—TMS 化によるリグニンの分析：けい皮アルコール末端基分析への応用
黒田健一、中川明子
筑波大学農林工学系
Pyrolysis-trimethylsilylation of lignin: a sensitive and easy method for analysis of cinnamyl alcohol-end groups
Ken-ichi Kuroda, Akiko Nakagawa-izumi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Pyrolysis in the presence of N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA),
pyrolysis-trimethylsilylation, was proposed as a new method for analysis of cinnamyl alcohol-end
groups in lignin. It preferentially provided large levels of trimethylsilyl (TMS) derivatized cinnamyl alcohols
such as coniferyl alcohol diTMS ether (1). This method was sensitive to the formed cinnamyl alcohols
compared to the conventional pyrolysis and pyrolysis-methylation methods. Pyrolysis-trimethylsilylation of adiazomethane-methylated Japanese cedar (Cryptomeria japonica) wood gave two coniferyl alcohol TMS ethers,
1 in 1.3% yield stemming from coniferyl alcohol-end groups and 3 (OMe instead of the phenolic TMS ether of1) stemming from the guaiacylglycerol moieties involved in β-O-4 subunits. The results indicated thatpyrolysis-trimethylsilylation conveniently provides information on cinnamyl alcohol-end groups when applied
to diazomethane- methylated lignins.
2002-106
電子スピン共鳴法によるリグニンの活性酸素消去機能の評価
藤加珠子，野田博行
生物ラジカル研究所
Evaluation of the active oxygen scavenging activity of lignin using an electron spin resonance method
Kazuko Toh, Hiroyuki Noda
Institute of Life Support Technology
Abstract:
The superoxide scavenging activity of water solution of lignin extracted from Quercus
acutissima (KLW) and rice bran (RLW) was evaluated by employing an electron spin resonance cpmbined withthe superoxide dismutase addition method. It was found that both samples had superoxide scavenging activity(LLW = 600Unit/g, RLW = 1000Unit/g) with small inhibition rate for superoxide generation in
hypoxanthin-xanthine oxidase system (less than 26%).
2002-107
湖沼堆積物のリグニン由来物質
上平雄也*1*2、福島和彦*1、安田征市*1、寺井久慈*3、大田啓一*4*1
名大院生命農、*2 永大産業（株）、*3 中部大応用生物、*4 名大地球水循環研究センー
Lignin-derived matters in surface sediments of Japanese lakes
Yuya Kamihira*1*2,Kazuhiko Fukushima*1, Seiichi Yasuda*1, Hisashi Tera*3 and Keiichi Ohta*4*1Graduate School of Bioagicultural Sciences, Nagoya University, *2Eidai Co., Ltd., *3The college of Bioscienceand Biotechnology, Chubu University, *4Hydrospheric Atmospheric Research Center, Nagoya University
Abstract:
Lignin derived matters were detected by degradative methods chemically from the surface
sediments of three kinds of lake, Biwa, Seto-Taisho and Fukami, located in Japan. Monomers of lignin
fragments obtained by CuO oxidation and thioacidolysis were quantified by GC. Dimers obtained bydesulphulation of thioacidolysis products were analyzed by GC-MS. In all samples, biphenyl (5-5') structures
were dominant among the dimerer compounds derived from lignin.
368

2002-108
維管束および木繊維における多糖—リグニン結合の定性的・定量的考察
勝亦京子、廣川朋子、飯山賢治
東京大学アジア生物資源環境研究センター
Covalent associations between lignin and polysaccharides in vascular bundle and fiber of plant
Kyoko S. Katsumata, Tomoko Hirokawa, Kenji Iiyama
Asian Natural Environmental Science Center, the University of Tokyo
Abstract:
In this study, structural evidences of each type of cell wall were discussed on the view-point ofcovalent associations between lignin and polysaccharides, which were evaluated qualitatively and quantitatively
with carboxymethylation followed by water extraction for vascular bundle, fiber and compound middle lamella
separated from some plants. Chemical composition ofvascular bundles and fibers, and secondary walls and compound middle lamella of plants and structural featureof Björknan lignin isolated from their walls were also investigated. Role of covalent associations between lignin
and polysaccharides in different types of cell walls was discussed for subsistence and effective utilization ofplants on the basis of these results.
2002-109
ペルオキシダーゼ／H2O2 によるモノリグノール類酸化速度に対する 3，5 位置換基の影響
小林孝行*1、田口大安*2、重松幹二*2、棚橋光彦*2*1
岐阜大学大学院連合農学研究科、 *2 岐阜大学農学部
The effect of 3,5-substituents on oxidation rates of monolignols by peroxidase/H2O2 as oxidant
Takayuki Kobayashi*1 Hiroyasu Taguchi*2, Mikiji Shigematsu*2, Mitsuhiko Tanahashi*2*1
The United Graduate School of Agricultural Science, Gifu University, *2Faculty of Agriculture, Gifu
University
Abstract:
It is thought that one-electron oxidation of Monolignols is mainly catalyzed by peroxidase/H2O2
in lignification in the cell wall. To elucidate the process of lignification in the all wall, it is important to clarify
the mechanism of one-oxidation of monolignol by peroxidase/H2O2. In this study, to investigate the differenceof the reactivity of monolignols in terns of 3,5-substituents, the order listed as to oxidation rates of monolignols
and 3,5-subsdtuted monolignols with Horseradish Peroxidase (HRP) /H2O2 as oxidant and the order listed as tooxidation potential of them, which were measured with cyclic voltammetry, were compared.
2002-110
白色腐朽薗 Phanerochaete sordida YK−624 株の産生するペルオキシダーゼについて(II)平井浩文、森田英弘、杉浦むつみ、西田友昭
静岡大学農学部
Peroxidases produced by white-rot fungus Phanerochaete sordida YK−624 (II)
Hirofumi Hirai, Hidehiko Morita, Mutsumi Sugiura, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The hhhitor for peroxidases produced by Phanerochaete sordida YK−624 was investigated. The
inhibitor, of which the molecular weight was less than 10 kDa, was purified by gel permeation chromatography.
The inhibitor inhibited the oxidation of verahyl alcohol (VA) by YK-PO1, YK-PO2 and lignin peroxidase,
although the inhibitor did not affect on he reactions of manganese peroxidase and horseradish peroxidase (HRP).
In the spectral analysis, compound I of YK-PO2 changed to the native state of YK-PO2 by the addition of theinhibitor, although compound I of HRP did to compound II. On the other hand, little change of compound I of
YK-PO2 to native state was observed by the addition of the inhibitor. The inhibitor inhibited VA oxidation by
YK-PO1 in an uncompetitive manner.
2002-111
リグニンペルオキシダーゼの酸化反応機構：電気化学的特性からの考察
親泊政二三*1、篠原寛明*2、割石博之*3、田中浩雄*3*1
九州大学大学院生物資源環境科学研究科, *2 岡山大学工学部、*3 九州大学大学院農学研究院）
Redox mechanism of lignin peroxidase: Electrochemical characterization
Masafumi Oyadomari*1, Hiroaki Shinohara*2, Hiroyuki Wariishi*3, Hiroo Tanaka*3*1Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Faculty of369

Engineering, Okayama University, *3Faculty of Agriculture, Kyushu University,
Abstract:
Electrochemical analysis of lignin peroxidase (LiP) was performed using a pyrolytic graphite
electrode coated with peroxidase-embedded tributylmethyl phosphonium chloride membrane. The formal redox
potential for the ferric/ferrous couples of LiP was found to be -126 mV (vs. SHE), which was comparable withthat of manganese peroxidase and horseradish peroxidase pKa values for the distal His in peroxidases were
calculated using the Nernst equation, to be 5.8 for LiP, 4.7 for MnP, and 3.8 for HRP. A high pKa value of the
distal His might be crucial for LiP compound II to uptake a proton from the solvent. Therefore, LiP is able tocomplete its catalytic cycle during the oxidation non-proton-donating substrates with a low pH optimum.
2002-112
白色腐朽薗 Pleurotus ostreatus により生産される MnP アイソザイムの発現調節について
上辻久敏*1、本田与一*1、波辺隆司*1、桑原正章*2*1
京都大学木質科学研究所, *２秋田県立大学木材高度加工研究所
The analysis of expression on the production of manganese peroxidase by white-rot fungi Pleurotus ostreatus
Hisatoshi Kamitsuji, Yoichi Honda, Takashi Watanabe, Masaaki Kuwahara
Wood Research Institute, Kyoto University, Akita Prefectural University
Abstract:
Manganese peroxidase (MnP) was secreted by Pleurotus ostreatus in liquid stationary culture.
Two different MnP isozymes were produced in glucose/Yeast-extract medium (GY) andpeptone/glucose/yeast-extract medium (PGY). The isoelectric points of MnP produced in GY medium(MnP-GY) and PGY medium (MnP-PGY) were found to be 3.70 and 3.95, respectively. The molecular massesof both isozymes were 42 kDa. N-terminal amino acid sequences of MnP-PGY was found to be identical to thatof MnP 3. It was also similar to that of MnP which was produced in the sawdust culture. To better understand a
MnP isozyme production system for medium content, RT-PCR analysis was performed.
2002-113
カワラタケの遺伝子導入系の確立
仁田由美*1*2、（森総研）宮崎安将*3、中村雅哉*3、飯村洋介*4、宍戸和夫*5、（農工大院 BASE）梶田真也*2、諸星紀幸*2*1
株式会社コシダテック、*2 農工大院 BASE、*3 森林総合研究所、*4 産業技術総合研究所、*5 東京工業大学生
命工学科
Development of transformation system in Coriolus versicolor
Yumi Nitta*1*2, Yasumasa Miyazaki*3, Masaya Nakamura*3, Yosuke Iimura*4, Kazui Shishido*5, Shinya Kajita*2,
Noriyuki morohoshi*2*1
Koshida Co Ltd., *2Graduate school of Bio-Application and Systems Engineering, Tokyo University ofAgriculture and Technology, *3Forestry and Forest Products Research Institute, *4National Institute of Advanced
Industrial Science and Technology, *5Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology
Abstract:
Since white rot fungi have a system for the degradation of lignin and various types of persistentorganic polutants (POPs), it has been proposed that these fungi are useful for bioremediationand bioconversionof them. A white-rot basidiomycete, Coriolus versicolor, secrete laccase abd the enzyme contribute to degrade
lignin and POPs. In this study, we tried to establish the transformation system in order to over-produce gene of
enzyme such as laccase in C. versicolor. We constracted pT7GPDHPT vector containing promotor ofglyceraldehydes-3-phosphate dehydrogenase (gpd) gene from C. versicolor with hygromycin B resistance geneas marker gene. This plasmid vector was integrated into genome of C. versicolor ard resultant transformations
could be selected on medium including hygromycin B.
2002-114
メソ多孔体による酵素の超安定化と無塩素パルプ漂白への応用
杉山英彦，梶野勉，高橋治雄
株式会社豊田中央研究所
Enzyme stabilization in mesoporous material and its application for TCF pulp bleaching
Hidehiko Sugiyama, Tsutomu Kajino, Haruo Takahashi
Toyota Central R & D Laboratories, Inc.
Abstract:
Enzymes were adsorbed on the silica mesoporous materials and their stabilities were studied.
Both the surface character and size matching between pore sizes and the molecular diameters of enzyme were
important in achieving a high stability. Manganese peroxidase (MnP) immobilized in mesoporous material,
370

whose pore size just matched the diameter of the enzyme, showed the best stability and high H2O2 tolerance. We
constructed a thermally discontinuous two stage reactor system (TSRS), in which the enzyme and pulp
bleaching reactions were separately performed. After treatment of pulp with TSRS, the brightness of pulp
increased to about 85% within 6hr.
2002-115
特別講演：
非水媒体中における酸化還元酵素の機能発現とその応用
後藤雅宏
九州大学大学院工学研究院、科技団さきがけ 21
Invited Lecture: Catalytic activatiom of peroxidase in nonaqueous media and its novel application
Masahiro Goto
Department of Applied Chemistry, Kyushu University
Abstract:
Activatiion of peroxidase in an organic solvent by reversed micell or surfactant coating method
was investigated. Lyophilized LIP from an optimized aqueous solution exhibited no enzymatic activity in any
organic solvents examined in his study; however, LIP was catalytically active by being entrapped in the AOT
reversed micellar solution. LIP activity in the reversed micelle was enhanced by optimizing either preparation or
oparation conditions such as water and pH in water pools of the reversed micelle, and the raction temperature.
The degradation reaction of several environmental pollutants was attempted using LP hosted in the reversed
micelle.
2002-116
特別講演:
リグニンの加溶媒分解 —ホモリシス、クレゾリシス、アルドソリシス、アセトソリシス
佐野嘉拓
北海道大学大学院農学研究科
Invited Lecture: Solvolysis of lignin, - Homolysis, cresolysis, acetosolysis and aldosolysis
Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
Depolymerization and solubilization of lignin by solvolysis are of primary importance forindustrial processes of wood proceeded by heating at different pH such as pulping processes as well as for
fundamental lignin chemistry. We have been studying the mild hydrolysis of lignin with 50% aqueous dioxane
at 180ºC for 20 min for the chemical structure of lignin, and solvent pulping processes, solvolysis pulping with
50% aqueous cresol, atmospheric AcOH pulping with a small amount of mineral acid and HBS pulping withaqueous high-boiling alcoholic solvent for the fractionation of lignocelluloses. Also the reaction mechanisms fortheir processes have been studied using lignin model compounds. This paper reviews the reaction mechanismsof lignin by solvolysis processes in hot neutral, weakly acidic and weakly alkaline solutions.
2002-201
酸加水分解リグニンの陰イオン交換樹脂への変換
松下泰幸、安田征市
名古屋大学大学院生命農学研究科
Preparation of anion-exchange resins from acid hydrolysis lignin
Yasuyuki Matsushita and Seiichi Yasuda
Graduate School of Bioagricultural Sciences, Nagoya University. Nagoya
Abstract:
One of the key points in developing saccharification process is to find effective ways to utilize
acid lignin. The authors investigated the chemical conversion into anion-exchange resins of phenolized acidlignin (P-SAL), prepared from acid lignin by phenolation with sulfuric acid catalyst, by two methods. The
restricted resinification of P-SAL followed by Mannich reaction to yield a weakly basic anion-exchange resinwith 2.4 meq/g ion exchange capacity. Another method is the reaction of resinified P-SAL withglycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with 2.1 meq/g ion
exchange capacity.
2002-202
リグニン系ポリウレタン複合材料の力学物性に及ぼす充填材形状の影響
371

船橋正弘*1、廣瀬重雄*1、畠山立子*2、畠山兵衛*3*1
産業技術総合研究所、*2 大妻女大学家政学部、*3 福井工業大学工学部
Effect of filter shape on mechanical properties of lignin-based polyurethane composites
Masahiro Funabashi*1, Shigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*3*1
National Institute of Advanced Industrial Science and Technology, *2Otsuma Women's University,*3
Fukui University of Technology
Abstract:
Polyurethane (PU) composites were prepared using a lignin polyol (KLP, a mixture of kraft
lignin and polyethylene glycol, Mw=200) diphenylmethane diisocyanate (MDI) and fillers. Wood meal andcoffee grounds were used as fillers. The mixture of KLP and fillers was reacted with MDI by adding anadequate amount of acetone as a solvent. Mechanical properties of composite samples were determined bycompression tests. Master curves of the relationships between the specific values of mechanical properties andthe apparent volume ratio, determined as the ratio of the apparent volume of filters to the reciprocal values of
the apparent density of the samples, were obtained.
2002-203
リグノスルフォン酸ソーダのナノレベル構造と熱的性質
畠山兵衛*1、角野浩崇*1、善定和博*1 畠山立子*2*1
福井工業大学工学部、*2 大妻女大学家政学部
Nanoscale morphology and thermal properties of sodium lignosulfonate
Hyoe Hatakeyama*1, T. Sumino*1, Kazuhiro Zenjyo*1, Tatsuko Hatakeyama*2*1
Fukui University of Technology, *2Otsuma Women's University
Abstract:
Sodium lignosulfonate (NaLS) has been examined using differential scanning calorimetry(DSC) and tapping mode atomic force microscopy (AFM). NaLS from aqueous solutions was deposited onto
freshly cleaved mica surfaces and then air-dried. AFM images of NaLS showed clear network structure at theconcentration of 10 pg/ml. DSC was carried out at the scanning rate of 10ºC/min from -150ºC to 200ºC. Glasstransition was observed for a dry sample. However, glass transition, cold crystallization and melting of water
were observed for wet samples.
2002-204
非塩素系漂白過程における α-カルボニル型リグニン構造の挙動（III）： パルプ残存リグニン中の α-カルボニ
ル型リグニン構造の挙動
友田生織、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Formation and degradation of α-carbonyl structure in lignin during chlorine free bleaching, (III)Formation and degradation of α-carbonyl structure in lignin remaining in pulp
Iori Tomoda, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
We have already proposed a new method to evaluate the content of -carbonyl structure in
residual lignin without isolating the lignin from the pulp. In this report, we applied thismethod to MWL and soft wood oxygen-bleached kraft pulp (NOKP) , and the changes in the content of
α-carbonyl structure during alkali and alkali hydrogen peroxide treatment were evaluated. In MWL experiment,
hydrogen peroxide treatment under pH13 was very effective to reduce the α-carbonyl content, but pH10 was not
as effective as pH13. The results of hydrogen peroxide treatment of NOKP suggested that hydrogen peroxide
bleaching is a process in which the formation and degradation of α-carbonyl structure take place at the sametime.
2002-205
広葉樹クラフトパルプのオゾン・過酸化水素を用いる無塩素漂白
池田 努、大井 洋
筑波大学農林工学系
Non-chlorine bleaching of hardwood kraft pup with ozone and hydrogen peroxide
Tsutomu Ikeda, Hiroshi Ohi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Acid treatment was developed for non-chlorine bleaching with ozone and hydrogen peroxide. Medium
consistency ozone bleaching of hard wood oxygen delignified kraft pup required higher ozone charge than high372

consistency ozone bleaching did to bleach al a given brightness. Although, high consistency ozone bleaching
could not keep a viscosity at an acceptable level, medium consistency ozone bleaching could keep it.
Hexeneuronic acid could be removed by both acid treatment and ozone bleaching. Then, a bleaching sequencewith acid treatment and ozone bleaching could decrease the ozone charge and improve bleaching selectivity.
2002-206
酸性条件下におけるリグニンの反応機構：アシドリシス条件下におけるリグニン構造の変質に関する分析
坂口智一、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Rcaction mechanism of lignin under acidic conditions. Analysis of structural modification of lignin during
acidolysis
Tomokazu sakaguchi, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Acidolysis by the use of hydrochloric acid has been widely applied to the analysis of chemical
structure of lignin (analytical acidolysis), and to the isolation of lignin (preparative acidolysis). Compared withanalytical acidolysis, preparative acidolysis employs milder condition. It is considered that preparative
acidolysis gives less chemical changes of lignin than analytical acidolysis. In this work, wood meal and milledwood lignin (MWL) were treated under several acidolysis conditions and structural modification caused by acidtreatment was quantitatively analyzed by ozonation method. Not only the solubilized part but also the solid part(precipitates for MWL and residual lignin for wood meal) were analyzed.
2002-207
Kinetic and mechanism of the degradation of non-phenolic lignin model compounds under aerobic
polyoxometalate (POM) bleaching conditions
Tomoya Yokoyama*1, John F．Kadla*1, Hou-min Chang*1, Ira A. Weinstock*2, Richard S．Reiner*2*1
Department of Wood and Paper Science, North Carolina State University, *2 USDA Forest Service, Forest
Products Laboratory
Abstract:
A non-phenolic lignin model compound, 1, 2 and 4, was reacted with polyoxometalate(POM) under anaerobic bleaching conditions, and the kinetic and mechanism were investigated. A syringyl type,1, was degraded slower than a guaiacy1 type, 2, although the activation energy of 1 is a little lower than 2.
Instead, the frequency factor of 1 is considerably smaller than 2, suggesting that steric factor controls the rate of
the reaction between POM and model compound, and dominates over electronic property of its aromatic ring.
The significance of steric factor was confirmed by the reaction using 4 that has an ethoxyl group instead of amethoxyl group. The degradation of 4 was slower than 1, giving a lower activation energy and a much smallerfrequency factor. A kinetic isotope effect was observed when the -deuterated compound of 1 and 2 was
subjected to the reaction. It is suggested that the rate-determining step of the reaction between POM andnon-phenolic models is the Abstraction of the benzylic hydrogen. Further kinetic and mechanism will be
discussed in the presentation.
2002-208
Structural characteristics of lignin in humified materials
Oskars Bikovens*1*2, Janis Gravitis*2, Kenji Iiyama*1*1
Asian Natural Environmental Science Center, the University of Tokyo, *2Latvian State Institute of Wood
Chemistry
Abstract:
The behavior of lignocellulosic material during humification was investigated using grasscompost. Lignin of grass compost prepared by the Björkman's method suggested that lignin macromolecules
were modified even after short time composting. Soluble fraction of composted grasses gave the same productswith lignin by alkaline nitrobenzene oxidation and by ozonation, and also by methoxyl group determination.
These results suggested that some portion of lignin macromolecules were biologically modified to be dissolvedin water by introduction of hydrophilic groups such as carboxyl groups, which could play same role as soil
humic matters.
2002-209
β-O-4 型側鎖の立体構造を規定する要因の解明 --樹種間における β-O-4 型側鎖立体構造の分布-秋山拓也*1、松本雄二*1、飯塚堯介*1、Deded S. Nawawi*2*1
東京大学大学院農学生命科学研究科、*2Bogor Agricultural University373

Distribution of diastereomeric forms of β-O-4 structures among different wood species
Takuya Akiyama*1, Yuji Matsumoto*1, Gyosuke Meshitsuka*1, Deded S Nawawi*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Dept. of Forest ProductsTechnology, Bogor Agricultural University
Abstract:
The erythro/thero ratios of β-O-4 structures were investigated by the ozonation analysis forabout 20 species including both softwood and hardwood. The erythro/threo ratio exhibited wide variation
among species, about 1.0 for softwood and 1.5-3.5 for hardwood. The correlation between erythro/thero ratiosof β-O-4 structures and the methoxyl group contents were clearly observed among the species. lt was confirmedthat there is the relationship between the erythro/thero ratio and syringyl/guaiacyl ratio among different species,
suggesting that the aromatic ring type is one of the factors which control the formation of diastereomeric formsof β-O-4 structures during lignin biosynthesis.
2002-210
熱帯モンスーン気候と温帯における樹木主要成分の生分解過程の定量的・定性的考察
小野 芳*1、目黒あい*2、Maria F．A. Navera*3、武内和彦*1、飯山賢治*4*1
東京大学大学院農学生命科学研究科、*2 東京大学大学院新領域、*3 フィリッピン大学、*4 東京大学アジア
生物資源環境研究センター
Qualitative and quantitative discussions for biodegradation of wood components in the tropical monsoon area
and in the temperate area
Kaori Ono*1, Ai Meguro*2, Maria F. A. Navera*3, Kazuhiko Takeuchii*1, Kenji Iiyama*4*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Graduate School of Frontier
Sciences, the University of Tokyo, *3University of the Philippines, *4Asian Natural Environmental Science
Center, the University of Tokyo
Abstract:
Urban green spaces should be promoted in tropical monsoon area such as in the Philippines,
where their effects on mitigation of urban climate would be expected to be greater than those in temperate area.
Huge amounts of plant residues produced under high plant productivity should be utilized as resources. This
study discusses the process of biodegradation of plant remains into soil organic matter for their utilization.
Quantitative and qualitative analyses were carried out to discuss changes in biomass weight, lignin weight(Klason lignin and acid soluble lignin), aromatic composition of lignin and neutral sugar composition of majorurban trees in the Philippines during biodegradation. The results were compared with those carried out in Japan.
2002-211
落葉のマルチング過程におけるリグニン量の変化
金 貞福*1、渡辺達三*2、飯山賢治*3、秋山拓也*1、松本雄二*1*1
東京大学大学院農学生命科学研究科、*2 東京大学大学院新領域、*3 東京大学アジア生物資源環境研究センター
Changes in lignin content of leaf litters during mulching
ZhenFu Jin*1, Satomi Watanabe*2, Kenji liyama*3, Takuya Akiyama*1, Yuji Matsumoto*1*1
Graduate School of Agriculture and Life Science, the University of Tokyo, *2Asian Natural Environmental
Science Center, the University of Tokyo, *3 Graduate School of Frontier Science, the University of Tokyo,
Abstract:
Alkaline nitrobenzene oxidation procedure, ozonation method and methoxyl content
determination have been applied to the decomposing leaf litters during mulching to investigate the properties oflignin and to approximately estimate lignin content as assumed lignin content during mulching. Assumed lignin
content based on methoxyl content of Klason residue was much lower (3.9 to 10.0%) than that of Klason
residue (37.1 to 46.7%). Absolute amount of assumed lignin somewhat decreased during mulching, while thestructure of lignin remaining in leaf litters alter mulching was not quite different from its original structure.
2002-212
ケイヒ酸／モノリグノール経路のメタボローム解析に用いる重水素標識モノリグノールの合成
榊原紀和、梅澤俊明、島田幹夫
京都大学木質科学研究所
Syntheses of deuterium-labelled monolignols for metabolome analysis of the cinnamate/monolignol pathway
Norikazu Sakakibara, Toshiaki Umezawa, Mikio Shimada
Wood Research Institute, Kyoto University
Abstract:
In the postgenomic era, much attention has been focused on the overall understanding of the374metabolism of the cinnamate/monolignol pathway in relation to lignin, lignan and norlignan biosynthesis.
Recently, transcriptome and proteome analysis of the pathway has been reported. On the other hand,metabolome analysis has not been yet applied to the pathway, because of the lack of an appropriate methodology.
Herein, we have synthesized deuterium-labelled monolignols, which can be used for internal standards of stable
isotope dilution method-guided metabolome analysis of the cinnamate/monolignol pathway.
2002-213
新生木部におけるリグニン前駆物質配糖体の挙動
辻 幸子、安田征市、福島和彦
名古屋大学大学院生命農学研究科
On the behaviors of gluasides of lignin precursors in the differentiating xylem
Yukiko Tsuji, Seiichi Yasuda and Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
To clarify the mechanism of storage and supply of monoligno1 in the metabolism of lignin, theroles and behaviors of coniferin and coniferyl aldehyde glucoside in lignin biosynthesis were examined bytracer experiments using labeled precursors. The microautoradiography showed coniferyl aldehyde glucoside
was incorporated into lignin with almost similar pattern to the case of coniferin. The results of lignin chemical
analysis, DFRC/GC-MS ensured that coniferyl aldehyde glucoside was metabolized as monolignol precursor.
Coniferin might be incorporated into lignin through the complex pathway with oxidative step that is
independent of coniferin/-glucosidase system.
2002-214
イネをモデルとした植物細胞壁形成過程に関する研究（1）—イネ科植物細胞壁成分の生合成制御に関する研究—
間瀬浩平*1、佐藤かんな*1、中野仁美*1、西窪伸之*1、北野英己*2、梶田真也*1、片山義博*1*1
東京農工大学大学院生物システム応用科学研究科、*2 名古屋大学大学院生命農学研究科
Studies on genetic regulation of cell wall formation in rice plant (1) —The research on biosynthesis control ofcell wall component in the Gramineae plant
Kohei Mase*1, Kanna Sato*1, Yoshimi Nakano*1, Nobuyuki Nishikubo*1, Hidemi Kitano*2, Shinya Kajita*1,
Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Graduate school of Bioagricultural Sciences, Nagoya University
Abstract:
It is obvious that genes involved in lignin biosynthesis have to be coordinately regulated in
response to developmental and environmental cues. So, we think that the elucidation of regulation mechanismsof such genes is effective for the acquisition of useful characteristics such as environmental adaptation andblocking of the ingress of pathogens and increase in the biomass resource. The rice plant in which genome
analysis advances is very useful in order to understand these regulation mechanisms using the genetic andmolecularbiological technique. In this study, as a part of program characterizing the biosynthetic regulation ofplant cell wall component, we examined the polysaccharide-linked hydroxycinnamoyl esters biosynthetic
pathway and its molecular mechanism of genetic regulation in rice plant using rice one gene recessive mutant.
2002-215
イネをモデルとした植物細胞壁形成過程に関する研究（2）—イネ細胞壁成分の生合成制御遺伝子のマップ
ベースクローニングと新しい 2 次壁形成異常を持つイネの解析—
佐藤かんな*1、間瀬浩平*1、北野英己*2、梶田真也*1、片山義博*1*1
東京農工大学大学院生物システム応用科学研究科、*2 名古屋大学大学院生命農学研究科
Studies on genetic regulation of cell wall formation in rice plant, (2) —Map based cloning of biosynthesis
control gene of cell wall component and analysis of novel secondary cell wall mutant
Kanna Sato, Kohei Mase, Hidemi Kitano, Shinya Kajita, Yoshihiro Katayama
Graduate School of Bio-Applicadons and System Engineering, Tokyo University of Agriculture and Technology,
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
The plant cell walls are composed of a complex mixture of phenolic component, carbohydrates
and proteins. To date, the structure and biosynthesis of major cell wall components, lignin and cellulose havebeen clarified, but the co-ordinate regulations of individual steps in end biosynthetic pathway and different
pathways through cell wall establishment remain unclear. To understand these co-ordinate regulations, we375

perform map based cloning of d50 gene which induces abnormal parenchyma cell walls in Fukei71 as shown inprevious presentation. In addition, using histochemical and cheical methods, we analyze a novel rice mutant ofalterations in the thick secondary cell wall formation.
2002-216
白色腐朽菌のバイオレメディエーション環境下でのモニタリング
須原弘登*1、大黒千映子*1、近藤隆一郎*2*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究院
Monitoring of white-rot fungus during bioremediation
Hiroto Suhara, Chieko Daikoku, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University
Abstract:
Bioremediation is a low-cost treatment alternative for the cleanup of dioxin- contaminatedenvironment, when pollution spread broad-ranging. An interesting fungus was isolated from white rotten woodof a broadleaf tree from Kyushu island, in Japan, named strain MZ-340. This isoiate has ability to degrade
dioxin. We have tried to use this strain for bioremediation of dioxin- contaminated environment on site. Hence,
we have to develop a PCR-based assay to detect strain MZ-340 reliably on bioremediation site. We successfully
monitored the strain MZ-340 on site. The relationship between the population of the fungus and the effect ofbioremediation by this fungus will be discussed.
2002-217
ペルオキシダーゼ及び遷移金属反応を開始系とするリピッドペルオキシデーションによる加硫・未加硫イソプ
レンゴムの分解佐藤 伸*1、本田与一*1、渡辺隆司*1、桑原正章*2*1
京都大学木質科学研究所, *2 秋田県立大学木材高度加工研究所
Degradation of vulcanized and non-vulcanized isoprene rubbers by lipid peroxidation initiated with peroxidases
and transition metals
Shin Sato*1, Yoichi Honda*1, Takashi Watanabe*1, Masaaki Kuwahara*2*1
Wood Research Institute, Kyoto University, *2Institute of Wood Technology, Akita Prefectural University
Abstract:
Degradation of vulcanized and non-vulcanized synthetic polyisoprene (IR) by lipid peroxidation
initiated with peroxidases and transition metals was analyzed by CHCl3-extraction,
gel permeation chromatography. and double-shot pyrolysis GC-MS (DS-Py-GCMS). Non- vulcanized IR was
depolymerized intensively by the free radicals from unsaturated fatty acids produced by manganese peroxidase(MnP), Mn(III) chelate, and the Fenton reagent (FR). Partial depolymerization was observed in lipid
peroxidation with horseradish peroxidase (HRP) and laccase/mediator. Distinct degradation was not observed in
the reactions with lipoxygenase (LOX). In these reaction systems, the depolymerization of polyisoprene
depended on the presence of peroxidizable lipids. Degradation of vulcanized IR sheets was observed in the lipid
peroxidation initiated by FR. Reactions by MnP and Mn(III) chelate in sodium oxalate buffer also degraded therubbers. The reaction system by FR degraded the vulcanized rubber sheet intensively as 80 % of the rubbercomponent was solubilized with CHCl3. By the DS-Py-GCMS analysis of CHCl3 extracts, low molecular massfragments, isoprene, 1,4-dimethyl-4-vinylcyclohexene, 1-methyl-5-(1-methyl- ethenyl)-cyclohexene andlimonene were identified. These results indicate that control of free radical chain reactions of lipids by enzymes
and transition metals is a key to degrade the recalcitrant vulcanized rubber products.
2002-218
リグニン分解酵素による Irgarol の分解
小川直人*1、平井浩文*1、西田友昭*1、岡村秀雄*2*1
静岡大学農学部、*2 神戸商船大学
Degradation of Irgarol by ligninolytic enzymes
Naoto Ogawa, Hideo Okamura, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University, Kobe University of Mercantile Marine
Abstract:
2-Methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (Irgarol 1051), which is a newly
developed herbicidal additive for use in copper-based antifouling paints, was treated with partially purified MnPand laccase. The HPLC data showed that lrgarol 1051 disappears by 36-37% after a 24-h treatment with both
enzymes and two peaks suspected the transformation products of Irgarol 1051 are newly formed by thetreatment.
One
of
the
transformation
products
was
identified
to
be
376

2-methylthio-4-tert-butylamino-6-amino-s-triaxine (M1) by comparing its retention time and mass spectrumwith those of an authentic compound using GC-MS. This suggests that N-dealkylation occurs at thecyclopropylamino group of Irgarol 1051 resulting in metabolite M1. Toxicities of Irgarol 1051 and M1 were
evaluated by the growth inhibition tests using alga (Selenastrum capricornutum) and duckweeds (Lemna gibba
and L. minor). M1 showed the toxicity about 10 times lower than that of Irgarol 1051 for all the aquatic plant
species tested, indicating that the treatment with ligninolytic enzyme is effective in detoxification of Irgarol1051.
2002-219
木材腐朽担子菌による Polych1orinated Naphthalenes の分解
北野史朗*1、森 智夫*1、近藤隆一郎*２*1
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院
Degradation of poychlorinated naphthalenes by wood decaying fungi
Shirou Kitano*1, Toshio Mori*1, Ryuichiro Kondo*2*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University
Abstract:
The transformation of polychlorinated naphthalenes (PCNs) has been studied using six strainsof wood decaying fungi. In one of these strains, Phlebia lindtneri GB-1027degraded 2-chloronaphthalene (2CN)
immediately. The initial metabolites were detected by gas chromatography-mass spectrometry. The
hydroxylation of substrates was initially observed during degradation of 2CN. Significant inhibition of
degradation of 2CN was observed in incubation with cytochrome P-450 monooxygenase inhibitors,
1-aminobenzotriazole and piperonyl butoxide. These experiments with cytochrome P-450 monooxygenase
inhibitors, and formation of the mono- hydroxylated metabolites suggested that P. lindtneri initially degraded
2CN by monooxygenases oxidation system.
2002-220
白色腐朽菌 Phlebia lindtneri による塩素化 dibenzo-p-dioxin および dibenzofuran の酸化
森 智夫、近藤隆一郎
九州大学大学院生物資源環境科学研究科
Oxidation of chlorinated dibenzo-p-doxin and dibenzofuran by white-rot fungus; Phlebia lindtneri
Toshio Mori, Ryuichiro Kondo
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University
Abstract:
The actions of white-rot fungus on two chlorinated aromatic compounds, known to be persistentenvironmental
contaminants,
werestudied.
Twoboth-ring
chlorinateddioxin-models,
2,7-dichlorodibenzo-p-doxin (2,7-diCDD) and 2,8-dichlorodibenzouran (2,8-diCDF), were metabolized bywhite-rot fungus Phlebia lindtneri. 2,7-DiCDD was disappeared linearly in he culture of P. lindtneri, after a 20
day incubation period, only 45 % remained in die culture. One of metabolites each produced by P. lindtneri
from a 5-day incubated culture with 2,7-diCDD or 2,8-diCDF was identified by gas chromatography-mass
spectrometry. P. lindtneri was shown to metabolize 2,7-diCDD and 2,8-diCDF to a hydroxy-diCDD and ahydroxy diCDF, respectively.
2002-P01
微生物相互作用による白色腐朽菌の酵素生産
原園幸一*1、渡辺吉雄*2、中村和憲*1*1
産業技術総合研究所、*2 メルシヤン生資研
Induction of ligninolytic enzyme production in white-rot fungi by antagonistic microorganisms
Koichi Harazono*1, Yoshio Watanabe*2, Kazunori Nakamura*1*1
National Institute of Advanced Industrial Science and Technology (AlST), *2Bioresource Laboratories,
Mercian Corporation
Abstract:
We investigated enzyme production in white-rot fungi by antagonistic microorganisms. Fungi
often produce the phenoloxidase enzyme laccase during interactions with other organisms. By pairings ofwhite-rot fungi Trametes versicolor or Lentinus edodes, and antagonistic organism Trichoderma
longibrachiatum on malt extract agar, laccase activity was mainly detected on the region in contact with both
fungi. On the other hands, manganese peroxidase (MnP) activity was detected on the region in contact with T.
longibrachiatum in the case of white-rot fungus Phanerochaete sordida.
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2002-P02
白色腐朽菌 Phanerochaete sordida YK−624 株の産生するペルオキシダーゼについて(III）
杉浦むつみ、森田英弘、平井浩文、西田友昭
静岡大学農学部
Peroxidases produced by white-rot fungus Phanerochaete sordida YK-624 (III)
Mutsumi Sugiura, Hidehiro Morita, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
The characteristics of two peroxidase isozymes (YK-PO1, YK-PO2), produced by
Phanerochaete sordida YK-624 were investigated. The substrate specificities of lignin peroxidase from P.
chrysosporium (Pc-LiP), YK-PO1, and YK-PO2 for monomeric lignin model compounds were not differ. On theother hand, dimeric β-O-4 lignin model compound was more efficiently consumed by YK-POl and YK-PO2
than by Pc-LiP. Moreover, YK-PO1 had a higher specificity for sinapyl alcohol oligomer than did YK-PO2 andPc-LiP, though the specific activity of veratryl alcohol (VA) oxidation was the lowest with YK-PO1. YK-PO1
showed high tolerance to hydrogen peroxide compared with YK-PO2 and Pc-LiP. It is thought that low
reactability of YK-PO1 with hydrogen peroxide affects on VA oxidation by YK-PO1.
2002-P03
非フエノール性 β-O-4 型リグニンモデル化合物の酸化電位とラッカーゼ／1−HBT 系による酸化力との相関
岩月正人、山本明日香、中川 誠、稲垣真澄、重松幹二、河合真吾、大橋英雄
岐阜大学農学部
The correlation between the oxidation potentials of non-phenolic β-O-4 lignin model compounds and theoxidation abilities of laccase/1-HBT system
Masato Iwatsuki, Asuka Yamamoto, Makoto Nakagawa, Masumi Inagaki, Mikiji Shigematsu, Shingo Kawai,
Hideo Ohashi.
Faculty of Agriculture, Gifu University
Abstract:
We have studied on the degradation of non-phenolic β-O-4 lignin model compounds bylaccase/1-HBT system. In this Study, we investigated the oxidation potentials and HOMO energies of
non-phenolic β-O-4 lignin model compounds (1)-(7). These results suggest that the oxidation ability oflaccase/1-HBT system correlates with their oxidation potentials and HOMO energies.
2002-P04
スジチヤダイゴケ（Cyathus stercoreus）による非フ工ノール性リグニンモデル化合物の分解とリグニン分解酵素稲垣真澄、大畑直人、河合真吾、大橋英雄
岐阜大学農学部
Dqadadon of non-phenolic lignin model compound by Cyathus stercoreus and its lignin degrading enzymes
Masumi Inagaki, Naoto Ohata, Shingo Kawai, Hideo Ohashi
Faculty of Agriculture, Gifu University
Abstract:
The white rot fungus Cyathus stercoreus degraded a non-phenolic β-O-4 lignin modelcompound, 1,3-dihyroxy-2-(2,6-dimethoxyphenoxy)-1-(4-ethoxy-3-methoxyphenyl) propane [I] , in Tien andKirk medium. The fungus catalyzed the β-ether cleavage and the aromatic ring cleavage of substrate I.
Furthermore, the enzyme activities of extracellular fluid of C. stercoreus were investigated_
2002-P05
白色腐朽菌によるダイオキシン汚染土壊のバイオレメディエーションにおける土壌成分の影響
城村真衣*1、近藤隆一郎*2*1
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院
Effect of soil components on bioremediation of dioxin-polluted soil by white-rot fungi
Mai Jomura, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University
Abstract:
A white-rot fungus, Ceriporia sp. MZ-340 is able to degrade polychlorinated dibenzo-p- dioxins
and polychlorinated dibenzofurans. However, dioxins in soils are hardly degraded by the fungus. In order toclarify inhibitory effect of soil components on the degradation of dioxins by the fungus, glass beads and soil
were used as carriers for dioxins. As model compounds for dioxins, 2,7-dichlorodibenzo-p-dioxin (DCDD) or
octachlorodibenzo-p-dioxin (OCDD) were added to the glass beads or soil, and treated with the fungus.
378

Although both DCDD and OCDD added on glass beads were degraded extensively, the degradation of both
DCDD and OCDD added on soil was inhibited completely. Furthermore, toluene extracts of soil was suggested
to affect inhibitively on the degradation of DCDD.
2002-P06
Polych1orinated Biphenyls (PCBs）の酵素による分解の試み
三好進祐、伊藤和貴、橘 燦郎
愛媛大学農学部
Biodegradation of polychlorinated biphenyl by enzymes from fungus having ability for degradation of dioxins
Shinsuke Miyoshi, Kazutaka Ito, Sanrou Tachibana
Faculty of Agriculture, Ehime University
Abstract:
To obtain the basic information for purification of polychlorinated biphenyls (PCBs) bybioremediation, degradation of PCBs by crude enzymes from fungus PL1 having ability for degradation ofdioxins was tried in this research. Two kind of PCBs, 4-Chlorobiphenyl (4CB) and 3,3',4,4'-Tetrachlorobiphenyl(TCB) were used as substrates. About 74% and 13% of 4CB and TCB were degraded by the crude enzymes
from fungus PL1 in a liquid medium for 24 hours, respectively. And furthermore, about 33% and 26% of 4CB
and TCB in a soils were degraded by the crude enzymes from fungus PL1 for 30 days, respectively. From theresults obtained here, it was found that PCBs could be degraded by crude enzymes from fungus having ability
for degradation of dioxins.
2002-P07
白色腐朽菌ミノタケが分泌する新規リグニンペルオキシダーゼの触媒特性
三木佑太*1、割石博之*2、田中浩雄*2*1
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院
Characterization of novel lignin peroxidase from the white-rot basidiomysete Trametes cervina
Yuta Miki, Hiroyuki Wariishi, Hiroo Tanaka.
Faculty of Agriculture, Kyushu University
Abstract:
Among several white-rot basidiomycetes examined, Trametes cervina was found to show
relatively higher lignin peroxidase (LiP) activity in the extracellular medium. Utilizing DEAE Sepharoe FF,
Sephadex G-100, and Mono Q, LiP from T. cervina (TcLiP) was purified. TcLiP was obtained as a major bandwith Mr of 37 kDa but with a minor band on SDS-PAGE analysis. Further study revealed that the minor band
was derived from a contamination of MnP. However, the contamination was minimal; thus, steady-state kinetic
and spectroscopic analyses could be achieved. Electron absorption spectrum of TcLiP shows a typicalcharacteristics for a hexa- coordinate high spin ferric iron state of the heme.
2002-P08
担子菌の示す細胞応答機構の解析：外因性有機化合物が引き起こす種々の応答反応
一瀬博文*1*３、栗原宏征*1*４、平塚宜博*1、志水元亨*1、中村朋史*1*５、三浦大典*1、湯田直樹*1、
割石博之*2、田中浩雄*2
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院, *３九州大学大学院工学研究院、*４
東京大学大学院工学研究科、*５財務省印刷局
Fungal cellular responses against exogenous chemicals
Hirofumi Ichinose*1* ３ , Hiroyuki Kurihara*1* ４ , Nobuhiro Hiratsuka*1, Motoyuki Shimizu*1, Tomofumi
Nakamura*1*5, Daisuke Miura*1, Naoki Yuda*1, Hiroyuki Wariishi*2, Hiroo Tanaka*2*1Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University, *3Graduate School of Engineering, Kyushu University, *4Graduate School ofEngineering, Tokyo University, *5Printing Bureau, Ministry of Finance
Abstract:
Extracellular ligninolytic enzymes are thought to be involved in the initial attack on polymericlignin and aromatic pollutants via the one-electron oxidation mechanism, resulting in the formation of a varietyof aromatic and quinoid fragments which are further metabolized intracellularly. Therefore, basidiomycetes
seem to have highly regulated and specific intracellular metabolic systems for each fragment. However, a fungal
cellular response mechanism against chemical compounds has not been well studied. In this study, the fungal
responses occurred against the addition of a wide variety of chemicals to fungal cells were analyzed usingtranscriptomic, proteomic, and metabolomic techniques.
379

2002-P09
8-O-4’型シリンギルネオリグナンのジアステレマーの立体化学とトチュウにおけるそれらの生合成
ラウリツト ナタヤ，片山健至、石川貴美子，栗田陽輔．鈴木利貞
香川大学農学部
Stereochemistry of 8-O-4' syringyl neolignans and their biosynthesis in Eucommia ulmoides
Nattaya Lourith, Takeshi Katayama, Kimiko Ishikawa, Yousuke Kurita, Toshisada Suzuki
Faculty of Agriculture, Kagawa University
Abstract:
8-O-4' type neolignans, syringylglycerol-8-O-4'-(sinapyl alcohol) ether (SGSE) andguaiacylglycerol-8-O-4'-(sinapyl alcohol) ether (GGSE) were synthesized. Their erythro and threo isomers wereseparated and identified by means of NMR. To understand their biosynthesis in Eucommia ulmoides, feeding
experiments of a labeled precursor, [8-14C]sinapyl alcohol, to excised shoots were undertaken. It was found thatthe radioactivity was incorporated into SGSE (and its glucoside) in the stems and the leaves, and that the present
incorporation into erythro isomer was more than that into threo isomer.
2002-P10
クラフトパルプの漂白過程で生成する高分子成分の生分解挙動
幸田圭一
北海道大学大学院農学研究科
Biodegrdation of high-molecular-weight compounds produced by kraft pulp bleaching process
Keiichi Koda
Graduate School of Agriculture, Hokkaido University
Biodegradation behavior of high molecular portion of kraft pulp bleach effluent containing substantial amountof organochlorine was investigated. Chlorine-based bleach liquor containing microorganisms was subjected todialysis cultivation to trace low-molecular –weight degradation products (MW<1000), some of which may
cause environmental impact. A few degradation products were successively detected as intermediary metabolites
by HPLC equipped with UV detector (270nm).
It was observed that abou 50 % of organically bound chlorine in the fraction was removed during the incubation
period of three months.
2002-P11
ケナフ靭皮の中間温度での蒸解
吉永新司、鮫島一彦
高知大学農学部
Pulping or kenaf bast fiber at moderate temperature
Faculty of Agriculture, Kochi University
Abstract:
lt was already shown that it is possible to make a high viscosity kenaf bast pulp by normalpressure soda pulping although the residual lignin is still at high level. To realize a commercial pulping to makehigh viscosity (strength) pulp, it is needed to reduce the lignin content and the lordof bleaching even if some reduction of viscosity occur. A moderate temperature pulping was examined here to
reduce the residual lignin content of unbleached pulp. At 140ºC, the pretreatment of ammonium oxalate was noteffective to the delignification, but viscosity was kept comparatively at high level. The addition ofanthraquinone and the extension of keeping time at 140ºC was proved to be effective. The viscosity was 62 cp
and the Kappa number was 39.
2002-P12
シラカンバ常圧酢酸パルプの無塩素漂白（2）辻 洋路、岸本崇生、浦木康光、佐野嘉拓
北海道大学大学院農学研究科
Non-chlorine bleaching of atmospheric acetic acid pulp from Betula platyphylla var. japonica Hara, (2)Hiromichi Tsuji, Takao Kishimoto, Yasumitsu Uraki, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstrct: Atmospheric acetic acid pulp from Japanese white birch wood was treated with non-chlorine bleaching
agents such as oxygen (O), ozone (Z) and chlorine dioxide (D). In the previous investigation we showed that thepulp was fully bleached with multi-stage bleaching in DEDED or ZZZEpD sequence. In order to decrease theamount of ozone or chlorine dioxide, oxygen bleaching was performed in this investigation. Deacetylation of380the pulp prior to oxygen bleaching was essential. Bleachability of the pulp was improved by EO treatments, andbrightness reached 86-87% ISO in EOZED sequence. However, paper strength of the pulp was inferior to that in
DEDED or ZZZEpD sequence. Further investigations were necessary to optimize oxygen bleaching stage.
2002-P13
HBS パルプ化におけるリグニンの構造変化 —NMR による解析（2）—植木飛鳥、岸本崇生、佐野嘉拓
北海道大学大学院農学研究科
Structural changes in lignin during HBS pulping. -NMR Analysis, (2)Asuka Ueki, Takao Kishimoto, Yoshihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
Structural changes in lignin during HBS pulping were investigated by quantitative 13C-NMR
and HMQC spectra. The content of phenolic hydroxyl groups in MWL increased significantly, which nay be
attributed to hydrolysis of α-O-4 bonds and homolytic cleavage of phenolic β-aryl ether. The decrease in thecontent of β-O-4 structures and introduction of 1,4-butanediol into α-position of β-O-4 moiety were confirmed.
The β-5 and ββ substructures were relatively resistant to HBS pulping conditions, but β-1 may not. The signals
corresponding to Hibbert's ketones were not observed, which suggests that acidolysis is not importantdegradation pathway in HBS pulping.
2002-P14
アルカリ性酸素脱リグニン段排液リグニンの土壌改良剤としての性状
王 東香、勝亦京子、飯塚堯介
東京大学大学院農学生命科学研究科
Characterization of lignin fragments in alkaline-oxygen stage waste liquor as soil conditioning agent
Dongxiang Wang、 Kyoko Katsumata, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
2002-P15
酸可溶性リグニンのクロロホルム可溶成分
宮脇 慈、松下泰幸、安田征市
名古屋大学大学院生命農学研究科
Chloroform soluble components of acid soluble lignin
Shigeru Miyawaki, Yasuyuki Matsushita and Seiichi Yasuda
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
To elucidate the formation and chemical structures of chloroform soluble materials in acidsoluble lignin (ASL), lignin model compounds of arylglycero1-β-aryl ethers with guaiacyl ( I ) and syringyl (II)nuclei were treated by the KIason procedure. Model compound I gave only insoluble polymerized condensation
product, while II gave insoluble polymerized product and chloroform soluble low molecular weight products,
which were dissolved in 3% sulfuric acid.
2002-P16
リグニンと新聞古紙を原料とする成形活性炭ボードの作成
根本純司、浦木康光、佐野嘉拓
北海道大学大学院農学研究科
Preparation of activated carbon boards from a mixture of lignin and waste newspaper
Junji Nemoto, Yasumitsu Uraki, Yohihiro Sano
Graduate School of Agriculture, Hokkaido University
Abstract:
Activated carbon boards (ACB) were prepared from mixture of hardwood acetic acidlignin (HAL) and waste newspaper. The mixture was molded to precursory boards by thermal press, and thenconverted to ACB by carbonization and steam activation. The ACB prepared from the precursory boards with
20% HAL molded under the conditions of 130ºC and 6 MPa showed the most excellent adsorption properties
and flexural strength among the ACB tested. The adsorption ability and flexural strength of ACB were
deteriorated with the increase in the board thickness. The laminated ACB with 3 layers showed better adsorption
property than that of mono layer ACB with the corresponding thickness.
381

2002-P17
リグニンの構造および反応研究のための 13C-標識 NMR 示差スペクトル分析法
寺島典二
名古屋大学名誉教授
Carbon 13-NMR spectrometry measuring difference between spectra of 13C- enriched and unenriched lignins.
—An effective tool for analysis of structure and reactions
Noritsugu Terashima
Professor emeritus, Nagoya University
Abstract:
Lignin is a structurally heterogeneous polymer formed by an irreversible random
polymerization of several kinds of monolignol radicals. Therefore, it is impossible to degrade
ligninquantitatively into monomeric or oligomeric units, and degradation loses information on heterogeneity.
Accordingly, destructive analyses can provide limited information on the chemical structure of lignin
macromolecule. Nondestructive analyses by 13C-NMR difference spectrometry between spectra of specifically
13
C-enriched lignin and unenriched lignin can provide definite information not only on the structure of lignin
macromolecule but also on the structural change during various reactions that is hardly obtained by any otherconventional destructive analyses. Information on the structural heterogeneity can also be obtained by
combination of this technique with pulse labeling and anatomical separation techniques.

382

第 48 回 （2003.10.30-30） 福井工業大学芦原学舎
2003-101
TOF-SIMS によるリグニン構造の解析
斉藤香織*1、高森ひとみ*2、岸本崇生*2、安田征市*1、福島和彦*1*1
名古屋大学大学院生命農学研究科, *2 北海道大学大学院農学研究科
Analysis of lignin structures by TOF-SIMS
Kaori Saito*1, Hitomi Takamori*2, Takao Kishimoto*2, Seiichi Yasuda*1, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, *2Graduate School of Agriculture, Hokkaido
University
Abstract:
Lignin model compounds were investigated using time-of-flight secondary ion mass
spectrometry (TOF-SIMS) to study the relationship between the chemical structure and the secondary ion
spectra. The formation mechanism of two prominent fragment ions (m/z 137 and 151), each of which has a
CG-CI Structure With a guaiacyl nuclei, was deduced by using deuterium labeling of specific positions ofconiferyl alcohol. We also examined 8-O-4', 8-1’, 5-5', 8-5' and 8-8' types of dimers, showing dominant C6-C1
ions originated from specific inter-unit bonds in lignin.
2003-102
近赤外分光計測による植物葉リグニンの定量
高橋俊守*1、安岡善文*1、飯山賢治*2*1
東京大学生産技術研究所、*2 東京大学アジア生物資源環境研究センター
Estimation of lignin content in fallen leaves using near-infra-red spectroscopy
Toshimori Takahashi*1, Yoshifumi Yasuoka*1, Kenji Iiyama*2*1
Institute of Industrial Science, the University of Tokyo, *2 Asia Natural Environmental Science Center, theUniversity of Tokyo
Abstract:
It is important to develop the measuring method of organic matter in conjunction with carbon
circulation or global warming. Near-infra-red (NIR) spectroscopy may be an effective method to estimate
contents of organic matter such as lignin. Lignin contents of fallen leaves were determined using various
analytical procedures. In laboratory, NIR spectra were recorded for each sample of leaves on ground. The
correlation coefficient between NIR spectra and lignin content varied with analytical procedures used todetermine lignin content and plant species. The combination of plant species and analytical method should beconsidered to develop a suitable regression model using NIR spectroscopy.
2003-103
光による熱帯産材の変色とそれらのスペクトルの特徴
岸野正典*1、中野隆人*2*1
北海道立林産試験場、*2 島根大学総合理工学部
Photo-induced color changes of some tropical woods and their spectral features
Masanori Kishino*1, Takato Nakano*2*1
Hokkaido Forest Products Research Institute, *2 Interdisciplinary Faculty of Science and Engineering, Shimane
University
Abstract:
Although for bangkirai (Shorea spp.), jahhra (Eucalyptus marginata) and robusta (E. robusta),
both a* (shify to red) and b* (yellowing) decreased with increased exposure time up to 600 h, for auri
(Acacia auriculiformis), cumaru (Amnurana acreana), ipe-high (Tabebuia spp. with relative high speciflc
gravity), ipe-low (with relative low specific gravity), keruing (Dipterocarpus spp.), b* increased with
exposure up to 50 h, and decreased above 50 h. Further information on thecorrelation between the above color changes and their spectral features such as diffuse reflectance Fouriertransform infrared (DRIFT) and ultraviolet-visible (UV-Vis.) spectra are given at the presentation.
2003-104
マカンバ MWL 抽出残渣から得た水溶性多糖類に含まれるリグニンの構造
相見 光、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Structure of small lignin fragment retained in water soluble polysaccharide extracted from birch MWL isolation
residue383

Hikaru Aimi, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
To investigate the structural feature of lignin existing nearby the lignin-carbohydrate linkages,
water soluble fraction with low lignin content was prepared from the residual Birch wood meal after the
extraction of MWL. Gel filtration behavior before and after treatment with polysaccharide degrading enzyme
revealed that this fraction was composed of relatively high molecular weight polysaccharide to which small
lignin fragments were linked. Structural analysis of lignin in this fraction revealed that it is rich in syringyl
nuclei with non-condensed type structures and have different character in condensed type one.
2003-105
アシドリシス条件下におけるリグニン構造の変質に関する分析（2）
坂口智一、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Analysis of structural modification of lignin during acidolysis (2)Tomokazu Sakaguchi, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
In the last lignin symposium, we reported that about 25% of β-O-4 structure was lost underpreparative acidolysis condition (0.1M HCl in dioxane-water, reflux for 2h), and that α-condensed structure was
not detected even under 5% sulfuric acid treatment by ozonation analysis. In this work, Hibbert's ketone typeside-chain structure of acidolysis MWL was quantitatively analysed by NaBH4 reduction followed by ozonation.
In this result, it was indicated that about 45% of β-O-4 structure was lost during analytical acidolysis (0.2M
HC1, reflux for 4h) and about 40% of lost β-O-4 structure was converted into C6-C3 type Hibbert's ketone
structure. However, C6-C3 type Hibbert's ketone structure was not detected when H2SO4 was used as catalyst.
2003-106
花弁道管部におけるトラケアリー・エレメントの形成とリグニンの化学構造
勝亦京子*1、飯山賢治*１、江前敏晴*２*1
東京大学アジア生物資源環境研究センター、*２東京大学大学院農学生命科学研究科
Genesis of tracheary element and chemical structure of lignin at vessel of flower petal
Kyoko S. Katsumata*1, Kenji Iiyama*1, Toshiharu Enomae*2*1
Asian Natural Environmental Science Center, the University of Tokyo, *2Graduate School of Agricultural andLife Sciences, the University of Tokyo
Abstract:
It is hardly recognized the presence of lignin in flower pedals. But frower pedals have to besupplied water through vessels, which may be quite different from "normal vessels" in other tissues of plant.
Vessels of flower pedals are characterized by quick formation and significantly short life span. The vessels
would be excellent specimens to investigate the formation of secondary walls in plants. Morphology of vesselsof flower pedals of 14 popular species were observed by light and scanning electron microscopies, and foundtracheary element structures from all of specimens. In addition, chemical composition of secondary walls ofcamellia (Camellia reticulata Lindl.) was analyzed and structural feature of Björkman lignin isolated fromcamellia was investigated. Lignin was significantly rich in p-hydroxyphenyl nuclei and condensed structure,
which could characterize as initial stage of lignin biosynthesis.
2003-107
樹木の防御反応としてのリグニン生合成について
堀啓映子*1、谷田貝光克*1、山田利博*2*1
東京大学大学院農学生命科学研究科、*2 東京大学大学院農学生命科学研究科付属演習林
Lignin biosynthesis for defense responses against fungus
Keko Hori*1, Mitsuyoshi Yatagai*1, Toshihiro Yamada*2*1Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Experimental Station at Tanashi,
University Forests, the University of Tokyo
Abstract:
Mass mortality of oaks is caused by the infection of a fungus Raffaelea quercivora, vectored byambrosia beetle Platipus quercivorus. Reaction zone barrier (RZB) was observed near the discolored part in theinfected wood. Lignin content of RZB was higher than the other part, and S/V ratio was lower. Guaiacyl typeand condensed type lignin was synthesized for the defense response against fungus in the reaction zone barrier.

384

2003-108
イネをモデルとした植物細胞壁形成過程に関する研究（3）−イネ科植物細胞壁成分の生合成制御に関する研究−
中野仁美*1、間瀬浩平*1、佐藤かんな*1、北野英己*2、梶田真也*1、片山義博*1*1
東京農工大学大学院生物システム応用科学研究科、*2 名古屋大学大学院生命農学研究科
Studies for genetic regulation of cell wall formation in rice plant (3)- The research on biosynthesis control ofcell wall component in the Gramineae plant
Yoshimi Nakano*1, Kohei Mase*1, Kanna Sato*1, Hidemi Kitano*2, Shinya Kajita*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and System Engineering, Tokyo University of Agriculture andTechnology, *2Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
The series of genes involved in the biosynthesis of lignin and polysaccharide-linked
hydroxycinnamoyl esters, which compose plant cell walls, have to be coordinately regulated in order to respondand adapt to environmental stresses during plant growth process. The rice plant that genome analysis makeadvance is very useful in understanding these regulation mechanisms using the genetic and molecular biological
technique. In this study, as a part of program characterizing the biosynthetic regulation of plant cell wallcomponent, we examined the polysaccharide-linked hydroxycinnamoyl esters biosynthetic pathway and its
molecular mechanism of genetic regulation in rice plant with rice one gene recessive mutant.
2003-109
ラッカーゼ反応系における 1-Hydroxybenzotriazole の役割
柴田浩志*1、平井浩文*1、西田友昭*1、大西正健*2*1
静岡大学農学部，*2 京都府立大学大学院農学研究科
The role of 1-hydroxybenzotriazole in laccase reaction system
Hiroshi Shibata*1, Hirofumi Hirai*1, Tomoaki Initia*1, Masatake Ohnishi*2*1
Faculty of Agriculture Shizuoka University, *2Graduate School of Agriculture, The Prefecture University of
Kyoto
Abstract:
We investigated the role of 1-hydroxybenzotriazole (HBT) in laccase (Lac) reaction system. No
metabolites which were produced from a non-phenolic β-O-4 lignin model compound in Lac/HBT system was
detected in artificial HBT radical system, although the artificial HBT radical degraded the model compound. In
the kinetics studies, HBT was not a competitive inhibitor for Lac, and the inhibition pattern was changed by theaddition of HBT. On the other hand, HBT was an uncompetitive inhibitor for horseradish peroxidase (HRP).
Moreover, ferrocytochrome c was competitively oxidized by Lac/HBT system. These results suggest that HBTmight be involved in the formation of ES complex, but not a radical mediator.
2003-110
ポプラ分化中木部におけるラッカーゼの局在
竹内美由紀、高部圭司、藤田 稔
京都大学大学院農学研究科
Localization of laccase in differentiating xylem of poplar
Miyuki Takeuchi, Keiji Takabe, Minoru Fujita
Graduate School of Agriculture, Kyoto University
Abstract:
Laccases and peroxidases are thought to be the candidates for dehydrogenative polymerizationof monolignols, however their differences have not been clarified. We have, therefore, investigated the
localization of these two enzymes in poplar trees using immunocytochemistry to reveal the possible difference
between laccases and peroxidases in their localization and perhaps the role in lignification. For immunolabelingof laccase, antibodies were raised against the peptides
synthesized according to the amino acid sequences of laccase. The labeling of laccase was observed in the cell
walls of secondary wall forming fibers and vessels, especially in compound middle lamella and in outer layer of
secondary wall. In parenchyma cells, intensive labeling was seen in the innermost layer of cell wall.
2003-111
リグニン生合成の抑制による飼料消化性の向上
久保賢太郎、川合伸也
東京農工大学農学部
Down regulation of cinnamoyl-CoA reductase(CCR) induces increase of cell wall digestibility in rice (Oryza
385sativa)
Kentaro Kubo, Shinya Kawai
Faculty of Agriculture, Tokyo University of Agriculture &Technology
Abstract:
Cinnamoyl-CoA reductase(CCR) is the first enzyme to the lignin-specific biosynthesis. Inverted
repeats constructs of the DNA encoding CCR of Oryza sativa have been introduced into rice plants. Some CCR
down-regulated plants displayed phenotype like Brownn midrib mutants. Histochemical analysis was performedon the transformants. The internodes from them, in contrast to wild type, indicated weaker red staining whentreated with phloroglucinol-HCl. This suggested reduction in aldehydes and/or lignin contents. Little difference
was detected between wild type and transformants with the Mäule reagent.
2003-112
超高感度蛍光アツセイシステムにより見出されたリグニンの β−aryl ether 結合を特異的に切断する糸状菌の分解機能とその多様性
大塚祐一郎*1、中村雅哉*2、菱山正二郎*2、梶田信也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 森林総合研究所
Detection, characterization and its diversity of new fungus that cleave the -aryl ether linkage of high molecularlignin by using the high sensitive assay system
Yuichiro Otsuka*1, Masaya Nakamura*2, Shoujiro Hishiyama*2, Shinya Kajita*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Forestry and Forest Products Research Institute
Abstract:
Cleavage of the arylglycerol-β-aryl ether linkage is the most important process in the biologicaldegradation of lignin. The bacterial β-etherase was already described and was tightly associated with the cellular
membrane. This function is not able to clave β-aryl ether linkage in the high molecule lignin, because thisenzyme does not secret to exbacellular space. In this time, we aimed to detect and isolate of the fungi catalyzing
cleavage of β-aryl ether linkage of high molecular lignin in the soil fungi. We screened and isolated the several
fungi, named 2BW-1, f5053,2T6-6,FA1 and FC5 by using GOU, GOUbz and DHP-GOU as the high sensitive
assay system. Resulting
analysis of 18srDNA, we determined that these fungi belong to Ascomycetes and it suggest that various fungi
affect to degrade the phenolic compounds of plant involving lignin in nature.
2003-113
リグナン生合成の系統分類的多様性
梅澤俊明
京都大学木質科学研究所
Phylogenetic aspects of lignan biosynthesis
Toshiaki Umezawa
Wood Research Institute, Kyoto University
Abstract:
The chemical structures of lignans vary substantially in basic carbon frameworks, as do theiroxidation levels and substitution patterns. In this review, the phylogenetic distribution of plants producing 66
typical lignans with a variety of chemical structures are listed based on a data base search. The distribution iscorrelated with the possible biosynthetic pathways of the lignans and discussed from evolutionary aspects.
2003-114
アベマキ及びイチョウ外樹皮におけるスベリン芳香族部分の予想前駆体と外樹皮のメタノリシス分解生成物の比較
鈴木利貞、滝野修平、泉 大輔、片山健至
香川大学農学部
Predicted precursors of the aromatic domain of suberin and methanolysis products of two kinds of outer bark:comparison between Quercus variabilis and Ginkgo biloba
Toshisada Suzuki, Shuhei Takino, Daisuke Izumi, Takeshi Katayama
Faculty of Agriculture, Kagawa University
Abstract:
p-Hydroxycinnamic acid esters, as predicted precursors of the aromatic domain of suberin, in
two kinds of bark of Quercus variabilis and Ginkgo biloba were analyzed. The esters were specifically present
in both of the outer bark. Dehydrogenative polymerizations of butyl ferulate and butyl caffeate were carried out
as a model system. The polymerization of butyl ferulate gave dimers of β-O-4’, β-5', dihydronaphthalene,386

naphthalene and β-β’symmetry types. The polymerization of butyl caffeate afforded dimers of β-6' anddihydronaphtharene types. Extractive free powders obtained from the two kinds of bark were treated bymethanolysis. Feruloyloxy fatty acid esters and methyl ferulate were isolated from both of the decomposition
products.
2003-115
特別講演:
樹木心材成分の生理活性と生成坂井克己
九州大学大学院生物資源環境科学研究科
Invited Lecture: Bioactivity and production of heartwood components
Kokki Sakai
Faculty of Agriculture, Kyushu University
Abstract:
Here I review our works on anti-tyrosinase activity of the Artocarpus incisus heartwood andsteroid 5-reductase inhibitory of resveratrol oligomers isolated from Shorea spp. heartwood. Contribution of
the 2,4-dihydroxyphenyl structure to the anti-tyrosinase activity is noted. Dehydrogenative polymerization of
resveratrol yielded 5-reductase inhibitory oligomers. ln addition, I deal with our studies on hinokitiol(-thujaplicin), a heartwood constituent of Cupressaceae species exhibiting a variety of bioactivities. Its
production by Cupressus lusitanica cell cultures, signal transduction after elicitation, and biosynthetic pathway
has been studied.
2003-116
特別講演:
自然に学ぶ高分子合成の現状
蒲池幹治
福井工業大学工学部
Invited Lecture: Development in nature-inspired polymer synthesis
Mikiharu Kamachi
Fukui University of Technology
Abstract:
Molecular design in polymer synthesis has been inspired by fine functions of natural polymers.
Remarkable advance has been made in artificial control of molecular weight in chain- growth polymerization,
preparation a helical polymers, application of enzymes to polymer synthesis, and matrix polymerization due tosupra molecules. In this lecture, living radical polymerization, asymmetric polymerization, enzymatic
polymerization, and preparation of tubular polymer from cyclodextrin are mentioned.
2003-201-O-4 結合からなる規則性人工リグニンポリマーの化学合成
岸本崇生、浦木康光、生方 信
北海道大学大学院農学研究科
Synthetic lignin polymer composed of β-O-4 structure
Takao Kishimoto, Yasumitsu Uraki, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
The β-O-4 structure is one of the most important substructures in lignin. In this investigation,highly regulated synthetic lignin polymers composed of β-O-4 structure were prepared from simple aromaticcompounds as starting materials by a solution polymerization method. Acetophenone derivatives werebrominated and polymerized in the presence of K2CO3. The polymer was converted to synthetic lignin polymer
composed of β-O-4 structure. The polymer was soluble in usual lignin solvents such as 1,4-dioxane and DMSO.
Molecular weight of acetate derivatives of the polymer was determined by GPC analysis.
2003-202β-O-4 型リグニンオリゴマーの簡便な合成法の検討
片平 類、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Facile synthetic method for β-O-4 type lignin oligomers
Rui Katahira, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
387

Graduate School of Agriculture, Kyoto University
Abstract:
A novel synthetic method for obtaining lignin oligomers that are composed of only the β-O-4structure was investigated. This method consists of two reaction steps: the continuous nucleophilic addtion
oligomerization of butoxycarbonylmethyl vanillin (1) and subsequent reduction of the oligomeric β-hydroxyl
ester. In the first step, the oligomeric β-hydroxyl ester (2) was obtained in 90% yield; the repeating units of theseoligomers were joined exclusively by β-O-4 linkages. The number-average degree of polymerization of 2 was
calculated to be about 7.2 (Mw/Mn=1.36). In the second step, the oligomeric β-hydroxyl ester (2) was treatedwith LiAlH4 to give product 3 in 73% yield. On the basis of NMR, MALDI-TOP-MS, and GPC analysis of theacetate of 3, it was indicated that compound 3 is an oligomeric lignin related compound containing only β-O-4interunit linkage.
2003-203
熱帯泥炭湿地環境中有機物の性状と土壌有機物形成過程
金 貞福、勝亦京子、飯山賢治
東京大学アジア生物資源環境研究センター
Chemical characterization of peat organic materials
Zhenfu JIN, S. Kyoko Katsumata, Kenji Iiyama
Asian Natural Environmental Science Center, the University of Tokyo
Abstract:
A series of structural features of the three main humic fractions, namely humic acid,
fulvic acid and humin from different depths of peat profile in Narathiwat Province, southern Thailand wereisolated and analyzed. Humin and humic acid contained similar amount of total carbon and nitrogen in acidinsoluble fractions of humin and humic acid. Ash free acid insoluble fractions in humin ranged from 76.4% to86.2% of original peat samples and there was no significant difference among different peat profiles. Contentsof methoxyl groups and total yield of alkaline nitrobenzene oxidation products were significantly lower thanthose of fresh wood specimens. Those values increased with depth of sampling and the amount of water
extractives, the content of acid soluble lignin and the ratio of acid to aldehyde of alkaline nitrohenzene oxidation
products showed the same trend.
2003-204
ケナフ茎芯加溶媒分解物から繊維強化型ポリウレタン
執行 薫*1、堀 成人*1、竹村彰夫*1、小野拡邦*1、飯山賢治*2*1
東京大学大学院農学生命科学研究科、*2 東京大学アジア生物資源環境研究センター
Fiber reinforced polyurethane film prepared from solvolysis product of Kenaf (Hibiscus cannabinus L.) core
Kaoru Shigyo*1, Naruhito Hori*1, Akio Takemura*1, Hirokuni Ono*1, Kenji Iiyama*2*1
Graduated School of Agricultural and Life Sciences, the University of Tokyo, *2Asian Natural Environmental
Science Center, the University of Tokyo
Abstract:
Solvolysis of Kenaf (Hibiscus cannabinus L.) core with polyethylene glycol (PEG) is studied toacquire plant-biomass-derived polyols from which polyurethane products are prepared. Conventional study toobtain alternative oil resources from the biomass has focused on the solubilization as much as possible. In thiswork, the solvolysis is carried out to the extent of that the cellulose fiber remains in the solvolyzed crude.
Polyurethane products prepared from this crude would be reinforced with the residual fiber. This report deals
with 1) optimization of solvolysis condition suited to the above idea, 2) mechanical properties of thepolyurethane films prepared from the solvolyzed.
2003-205
Development of effective utilization of rice waste−byproducts
Maxima E．Flavier*1*2，Kyoko S．Katsumata*1, Kenji Iiyama*1*1
東京大学アジア生物資源環境研究センター, *2 Institute of Chemistry,University of Philippines.
Development of effective utilization of rice waste-byproducts.
Maxima E．Flavier*1*2，Kyoko S．Katsumata*1, Kenji Iiyama*1
Asian Natural Environmental Science Center, the University of Tokyo, Institute of Chemistry, University of thePhilippines Los Banos
Abstract:
This study involved the chemical and structural characterization of 80% aqueous
ethanol-extracted samples of rice hull, straw and bran including amylase-treated and roasted bran. Neutral sugarcomposition, uronic acids, C:N ratio, lignin by acetyl bromide, hydroxycinnamic acids and nitrobenzene
388

oxidation products were determined.
2003-206
リグニン分解のシステム解析を目指した Phanerochaete chrysosporium のゲノム解析
割石博之*1、志水元亨*2、平塚宣博*2、湯田直樹*2、松崎芙美子*2、廣瀬宣子*2、野中大輔*2*1
九州大学大学院農学研究院、*2 九州大学大学院生物資源環境科学研究科
Functional genomic studies on Phanerochaete chrysosporium for systematic determination of lignin degradation
mechanisms
Hiroyuki Wariishi, Motoyuki Shimizu, Nobuhiro Hiratsuka, Naoki Yuda, Fumiko Matsuzaki, Noriko Hirose,
Daisuke Nonaka
Faculty of Agriculture, Kyushu University
Abstract:
To better understand mechanisms involved in fungal ability to degrade lignin and a wide varietyof aromatic compounds, systemic analysis on cellular mechanisms is believed to be projected. Functional
genomics seems to be a starting point for such studies. In the present study, recent situations for fungal genomic
research will be briefly summarized. Furthermore, our recent data on genome annotation of Phanerochaele
chrysosporium will also be discussed.
2003-207
耐塩性白色腐朽菌 MG-60 株の産生するマンガンペルオキシダーゼの発現特性（2）大黒千映子*1、須原弘登*2、堤 祐司*3、近藤隆一郎*3*1
九州大学大学院生物資源環境科学研究科、*2 有明工業高等専門学校、*3 九州大学大学院農学研究院
Characterization and expression of manganese peroxidase produced by halotolerant white-rot fungus Phlebia sp.
Mg-60 (2)
Chieko Daikoku*1, Hiroto Suhara*2, Yuji Tsutsumi, *3 Ryuichiro Kondo*3*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Ariake National
College of Technology, *3Faculty of Agriculture, Kyushu University
Abstract:
Phlebia sp.MG-60 is a ligninolytic basidiomycete isolated from mangrove stands based on its
lignin degradative ability. This fungus can grow and exhibit high lignin degrading ability under the culture
condition with high salt concentration. In this study, we investigated the production of manganese peroxidase(MnP) by MG-60. When MG-60 was grown in the medium containing 3% sea salts, it showed higher MnP
activity than that in the medium without sea salts. MG-60 produced different MnP isoenzymes under theconditions with or without sea salts, and two partial cDNAs encoding MnP isoenzymes were cloned andsequenced. Investigation of the expression of these MnP mRNA levels under different sea salts conditions is
now undergoing.
2003-208
白色腐朽菌 Ceriporiopsis subvermispora の菌体外代謝物 ceriporic acid B の物理化学的性質
大橋康典、寺西紘子、渡辺崇人、本田与一、渡辺隆司
京都大学木質科学研究所
Physico-chemical properties of ceriporic acid B, an extracellular product by Ceriporiopsis subvermispora
Yasunori Ohashi, Hiroko Teranishi, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Wood Research Institute, Kyoto University
Abstract:
Ceriporiopsis subvermispora produces alk(en)yl itaconates (ceriporic acids). In the present
study, physico-chemical properties of ceriporic acid B were examined. The acid dissociation constants, pKa1 andpKa2 of ceriporic acid B determined in H2O/EtOH (1:1, v/v) by pH titration were 4.5 and 8.2, lower than thoseof itaconic acid (3.6 and 5.0). This result suggests that carboxylic structures were stabilized by a long side chainof ceriporic acid B. Ceriporic acid B strongly inhibited reduction of Fe(III) by L-cysteine. The inhibitory effects
were suppressed by chelators such as NTA and EGTA. These results suggest that ceriporic acid B coordinates toFe(III) and decreases reactivity of Fe(III) with the reductant.
2003-209
白色腐朽菌およびその酵素によるポリアクリル酸の分解
桐原朋子、平井浩文、西田友昭
静岡大学農学部
Biodegradation of polyacrylic acid by white rot fungi and ligninolytic enzymes
389

Tomoko Kirihara, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
Super absorbent polymer (SAP), which is a crosslinked polymer of polyacrylic acid (PAA), wassolubilized by treatments with white rot fungi and ligninolytic enzymes, manganese peroxidase (MnP) andlaccase (Lac), and water-soluble PAAs were detected as metabolites. White rot fungi also degraded PAA and thedecrease of Mw of PAA was enhanced under LN culture without glucose. Furthermore, the degradation of PAA
by MnP and Lac was observed. These results suggest that white rot fungi and ligninolytic enzymes can degrade
PAA and have potential applications to decrease environmental levels of water-soluble polymers.
2003-210
白色腐朽薗の産生する酵素による塩素化芳香族化合物の脱塩素について
若月亜希子、平井浩文、西田友昭
静岡大学農学部
Dechlorination of polychlorinated aromatic compounds by enzymes from white-rot fungi
Akiko Wakatsuki, Hirofumi Hirai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
Ligninolytic enzymes from white-rot fungi, manganese peroxidase (MnP), laccase (Lac), andlignin peroxidase (LiP), were used in an attempt to treat methoxychlor (MC), a chemical widely used as apesticide and an environmental contaminant. MC was converted into methoxychlor olefin (MCO) and
4,4'-dimethoxybenzophenone by MnP or laccase treatment. These results indicate that ligninolytic enzymes
from white-rot fungi can catalyze the oxidative dechlorination of MC. The culture fluids from various white-rot
fungi decreased 2,4,8-trichlorodibenzofuran (TCDF) by 20-40% after a 24-h treatment. Most of TCDF wasdechlorinated and polymerized by the culture fluids. In fact, the dechlorinase was separated withanion-exchange chromatography from the culture fluid inoculated with P. sordida YK-624. These results
suggest that white-rot fungi secrete hydrolytic dechlorinase, and that the dechlorinase eliminates Cl ion fromTCDF and inserts hydroxyl group to TCDF, and that the metabolites which contain hydroxyl group would beoxidized by phenol oxidase, and then polymerized.
2003-211
新規塩素化ダイオキシン分解微生物の分解機能に関する研究（II）
中村雅哉*1、菱山正二郎*1、大塚祐一郎*2、片山義博*2、保科定頼*3*1
森林総合研究所、*2 東京農工大学大学院 BASE、*3 慈恵医科大学
Screening and functional analysis of chlorinated dibenzo-p-dioxin degrading microorganisms by dioxin-likeassay substrate
Masaya Nakamur*1a, Shojiro Hishiyarna*1, Yuichiro Otsuka*2, Yoshihiro Katayama*2, Sadayori Hoshina*3*1
Forestry and Forest Products Research Institute, *2Graduate School of Bio-application and System Engineering,Tokyo University of Agriculture and Technology, *3Jikei University School of Medicine
Abstract:
We developed a fluorometric assay method for rapid and sensitive evaluation of dioxin
degrading capacity by microorganisms. The dioxin-like substrates for fluorometric assay of dioxin degrading
microorganisms were synthesized with the conjugation of chlorobenzenes and fluorescence substrate. Cleavageof the ether bridge in these assay substrates would yield the highly fluorescent products. Bacillus midousuji
SB2B-J2 was isolated from the compost in Osaka by professor Hoshina. The isolated bacterium could degrade
chlorinated dibenzo-p-dioxins in the fly ash. The capability of this bacterium for dioxin degradation was
analyzed by using the dioxin-like assay substrates biochemically. During incubation of the bacterium with theassay substrates, fluorescence based on the cleavage of the dioxin ring was detected. The activity for thecleavage of the ether bridge in dioxin ring was detected in a membrane fraction of cell free extract from B.
midousuji SH2B-J2.
2003-212
白色腐朽菌によるダイオキシン汚染土壌の処理
平林徹也*１、迫田江美乃*１、城村真衣*１、近藤隆一郎*２*１
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院
Treatment of polychlorinated dioxin-polluted soil by white-rot fungi
Tetsuya Hirabayashi*１, Emino Sakoda*１, Mai Jomura*１, Ryuichiro Kondo*２*１
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *２Graduate School of390

Agriculture, Kyushu University
Abstract:
When dioxin-polluted soil was treated by Ceriporia lacerate MZ-340, no decrease of dioxin,
contents of octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF), was observed. However,when dioxin-polluted soil pretreated with HCl was treated by the fungus, the decrease of OCDD and OCDF
contents was observed. This result indicated that characteristics of soil components (organic and inorganic state)
may affect the degradation activity of the fungus. To establish bioremediation technology to treat
dioxin-polluted sludge under sea, 2,7-dichlorodibenzo- p-dioxin (2,7-DCDD) was treated by white-rot fungi
under hypersaline condition. The halotolerant white-rot fungus, Phlebia sp. MG-60 was observed to have an
ability to degrade 2,7-DCDD under hypersaline condition.
2003-213
多糖加水分解酵素による MWL 抽出残渣の分解挙動 〜Cellu1ose-Lignin fraction について〜
吉野寛之、廣澤修一、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
The behavior of degradation of wood meal after extraction of the MWL by carbohydrate-degrading enzymes-Analysis of cellulose-lignin fraction
Hiroyuki Furuno, Shuichi Hirosawa, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
Cellulase and xylanase were used to investigate the structure of Cellulose-Lignin fraction (CL),which was extracted from wood meal after extraction of the MWL with LiCl/ DMAc. The peaks in the elution
curves of CL from UV detector, which was derived from lignin containing component, was almost
corresponding to the peaks in the curves of CL from RI detector, which was due to all components. In the both
enzyme treatments, the behaviors of main peaks from UV detector were similar to that of main peaks from RI
detector. They indicated that lignin was connected sugar component.
2003-214
リグニンの熱分解機構 —生成物の高分子化について—
中村健史、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Polymerization mechanism of lignin during pyrolysis
Takeshi Nakamura, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
A series of lignin model compounds were pyrolyzed at 250ºC for 2 h to investigate thepolymerization mechanism of lignin. Two types of the mechanisms were suggested to be involvedin the polymerization; one is via radical intermediates formed by dehydrogenation of phenolic hydroxyl group
and Cα-hydrogen, and the other is via quinone methide-type intermediates. At 250ºC, the latter quinone methidemechanism was dominant and phenolic unit had much higher reactivity than the corresponding non-phenolic
one. Furthermore, Cβin vinylguaiacol was found to have higher reactivity than the aromatic ring in their
nucleophilic attack to the quinone methide-type of intermediate.
2003-215
熱分解−トリメチルシリル化による広葉樹リグニンの分析
黒田健一、中川明子
筑波大学農林工学系
Analysis of hardwood lignins by pyrolysis-trimethylsilylation
Ken-ichi Kuroda, Akiko Nakagawa-izumi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Pyrolysis of softwood lignins in the presence of N,O-bis(trimethyl-silyl)trifluoro- acetamide(pyrolysis-trimethylsilylation, BSTFA/Py) provides coniferyl alcohol and aldehyde trimethylsilyl (TMS) ethers
stemming from both terminal phenylglycerol moieties and cinnamyl end-groups. To deep the BSTFA/Py
chemistry of lignin, this method was applied to hardwood lignins. The results with syringyl dehydrogenative
polymers and a tochinoki milled wood lignin showed that BSTFA/Py provides sinapyl alcohol and aldehyde
TMS ethers, with high sensitivity. The yield ratios of sinapyl to coniferyl alcohol TMS ethers (SA/CA) were
determined with hardwood type lignins. Most of the lignins showed good correlation between the SA/CA ratios
and the yield ratios of syringaldehyde to vanillin (S/V) by nitrobenzene oxidation. Kenaf bast and some391

hardwood lignins showed rather lower SA/CA ratios than expected from their S/V ratios.
2003-216
シダおよびコケ植物に存在するリグニンの分析的熱分解法による解析
中川明子*1、松本定*2、樋口正信*2、石井 忠*3、黒田健一*1*1
筑波大学農林工学系、*2 国立科学縛物館、*3 森林総合研究所
Characterization of fern (Pteridophytes) and moss (Bryophytes) in situ lignins by analytical pyrolysis
Akiko Nakngawa-izumi*1, Sadamu Matsumoto*2, Masanobu Higuchi*2, Tadashi Ishii, *3 Ken-ichi Kuroda*1*1Institute of Agricultural and Forest Engineering, University of Tsukuba, *2The National Science Museum,*3
Forestry and Forest Products Research Institute
Abstract:
Nine ferns and 10 mosses were analyzed by pyrolysis-trimethylsilylation (TMS-Py) andpyrolysis-mass spectrometry (Py-MS). In TMS-Py, coniferyl alcohol derivative (CA) was detected from an ferns
samples, and sinapyl alcohol derivative (SA) was detected only from Iwahiba (Selaginella tamariscina).
Iwahiba, Haiboragoke (Crepidomanes birmanicum) and Matsubaran (Psilotum mudum) provided the CA peak
distinctly. In Py-MS of these ferns, ions derived from lignin were detected. In TMS-Py of mosses, a trace
amount of CA was detected from Aohaigoke (Rhynchostegium riparioides), Futoryuubigoke (Hylocomium
brevirostre) and Kumonosugoke (Pallavicinia longispina). Oomizugoke provided trace amounts of CA and SA.
2003-217
種々のアルカリ条件下でのパルプ処理における過酸化水素の役割
友田生織、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
The role of hydrogen peroxide during pulp treatment under several alkali conditions
Iori Tomoda, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract: Hydrogen peroxide bleaching is important in non-chlorine bleaching. However, there are many
unknown parts in the role of hydrogen peroxide during pulp bleaching. We have shown increase of vanillin yieldthat was produced by nitrobenzene oxidation, after hydrogen peroxide treatment ofoxygen bleached kraft pulp. We applied kappa number method to hydrogen peroxide treated pulps
and treatment liquors to analyze lignin and other permanganate consuming compounds. The data show thathydrogen peroxide has at least two different roles. Ionized/non-ionized hydrogen peroxide can remove pulp
kappa number. Ionized hydrogen peroxide has another hidden role that is against alkali-promoted creation of
permanganate consuming substances.
2003-218
Comparison of different treatment sequences of kenaf bast fiber for high viscosity pulp
Sherif Keshk*1, Wiwin Suwinarti*2，Kazuhiko Sameshima*2*1
Ain-Shams University, *2 Faculty of Agriculture, Kochi University
Abstract:
This paper explores the production of high viscosity pulp from kenaf bast by using threedifferent treatment sequences (A, B and C). The chemical compositions (cellulose, hemicellulose and lignin
contents) and viscosity from these treatments were determined. Yield and kappa number of sample B are thehighest one, while sample A shows the highest viscosity or degree of polymerization rather than those from B
and C samples. Furthermore, the pulp extracted from these treatments was investigated by vibration
spectroscopy and the structure differences found were validated by X-ray diffractometry. The FT-IR spectra of
all pulp samples reveal the same chain conformation but different in mean hydrogen bonding, relative ether
linkage and crystallinity index. From X-ray diffractograms of extracted pulp, the crystallinity index percentages
for A, B and C samples were 77.0, 73.4 and 75.0 that confirm the FT-IR results.
2003-219
広葉樹材のポリサルフアイド・アントラキノン添加等温蒸解の最適方法
横山朝哉*1、大井 洋*1、中俣恵一*2*1
筑波大学農林工学系、*2 北越製紙株式会社技術開発部
The most suitable method of polysulfide-anthraquinone isothermal cooking of hardwood
Tomoya Yokoyama*1, Hiroshi Ohi*1, Keiichi Nakamata*2*1
Institute of Agricultural and Forest Engineering, University of Tsukuba, *2Technical and Development Division,392

Hokuetsu Paper Mills, Ltd.
Abstract:
The improvement of pulp yield using a hardwood raw material, Acacia mearnsii, wassuccessful in the optimization of isothermal cooking (ITC) parameters. The addition of both polysulfide (PS)and anthraquinone (AQ) gave an about 4.5-5% higher yield at kappa number of about 17. The highest yield was
obtained when 70% of total active alkali and 100% of both PS and AQ were added at the beginning, andconsecutively, the black liquor was exchanged with fresh white liquor containing the remaining 30% of total
active alkali just after cooking temperature reached 135ºC. A mill scale trial was conducted to examine theeffect of PS and AQ in a practical pulp mill. Pulp samples were collected from a continuous cooking digester
not only when the PS-AQ ITC was operating but also when the simple kraft cooking was operating. Kappa
number, xylose to glucose ratio, brightness and viscosity of pulps were compared between the PS-AQ ITC andwith the simple kraft cooking.
2003-220
クラフトパルプ漂白工場のクロロホルムに関する環境観点からの評価
中俣恵一*1、本永洋一*2、大井 洋*3*1
北越製紙株式会社技術開発部、*2 北越製紙株式会社新潟工場、*3 筑波大学農林工学系
Evaluation of chloroform formed in processes of a kraft pulp bleaching mill from the environmental aspect
Keiichi Nakamata*1*2, Youichi Motoe*1*2, Hiroshi Ohi*3*1**2
Hokuetsu Paper Mills, Ltd., *3Institute of Agricultural & Forest Engineering, University of Tsukuba
In the mill scale investigation, it was clarified that the chloroform formation in chlorine bleaching of hardwood
oxygen-delignified kraft pulp (LOKP) was approximated 170 g/ pulp ton, approximated 90% of which wasdischarged to bleaching effluents, and that chloroform in the effluents was un- degradable in the activatedsludge treatment. More than 97% of the chloroform was discharged to the air by volatilization. It is suggested
that chloroform formation in Japanese LOKP bleachingmills can be decreased to l6-42 t per one year for 8000000 t of pulp production by chorine dioxide (ECF)
bleaching.
2003-221
天然から選抜した白色腐朽菌を用いた数種の環境ホルモンのバイオレメディエーション
木村圭助、松尾保洋、小堀敦子、鷹見純子、伊藤和貴、橘 燦郎
愛媛大学農学部
Bioremediation of environmental hormones by white-rot fungi screened from the nature
Keisuke Kimura, Yasuhiro Matsuo, Atsuko Kobori, Junko Takami, Kazutaka Ito, Sanrou Tachibana
Faculty of Agriculture, Ehime University
Abstract:
To obtain the basic information for purification of environmental hormones by bioremediation
with screened fungi from the nature, degradation of two kinds of environmental hormones by fungus PL1
having ability for degradation of dioxins and with a crude enzyme from the fungus PL1 was tried in thisresearch. p,p’-DDT and Lindane were used as substrates. About 72% and 64% of of p,p'-DDT and Lindane weredegraded by the fungus in a liquid medium for 30 days, respectively. Furthermore, about 75% and 51% of
p,p'-DDT and Lindane were degraded with the crude enzymes from the fungus in a liquid medium for 48 hours,
respectively. From the results obtained here, it is suggested that bioremediation of environmental hormones likep,p'-DDT and Lindane by screened fungi from the nature is possible.
2003-P01
キノコ子実体フエノール性物質に関する研究萱 祐絵*1、福島和彦*1、安田征市*1、松井直之*2、平山秀樹*3、重本 桂*3*1
名古屋大学大学院生命農学研究科、*2 森林総合研究所、*3 日本生薬株式会社
Phenolic constituents in the mushroom fruit bodies
Sachie Kaya*1, Kazuhiko Fukushima*1, Seiichi Yasuda*1, Naoyuki Matsui*2, Hideki Hirayama*3, Katsura
Shigemoto*3*1
Graduate School of Bioagricultural Sciences. Nagoya University, Nagoya, *2Forestry and Forest Products
Research Institute, *3Nihon-Syoyaku Co. Ltd.
Abstract:
Thioacidolysis and alkaline nitrobenzene oxidation showed that typical lignin structures were
not contained in the mushroom fruit bodies of Phellinus linteus and Agaricus brazei and the sclerotium oflnonotus obliqqus. Vanillic and syringic acids were detected in the products of alkaline hydrolysis of lnonotus
obliqqus, but could not be obtained from the other mushrooms. The antioxidant activities of ethanol extracts393

from mushrooms and sclerotium were measured by the inhibition of lipid peroxidation (ferric thiocyanate) and
1,1-diphenyt-2-picrylhydrazyl (DPPH) radical scavenging methods. The extract of Phellinus linteus had highactivity as DPPH scavenger. and the extracts except for Agaricus brazei had high activities on ferric thiocyanate
method.
2003-P02
細胞壁中における高分子リグニン形成過程の電顕観察
寺島典二*1、粟野達也*2、高部圭司*3*1
名古屋大学、*2SLU．Sweden、*3 京都大学大学院農学研究科
Formation of macromolecular lignin in the cell wall as observed by electron microscope
Noritsugu Terashima*1, Tatsuya Awano*2 and Keiji Takabe*3*1
Professor Emeritus, Nagoya University, *2Umea Plant Science Centre, Dept. of Forest Genetics and Plant
Physiology, SLU, Sweden, *3Graduate School of Agriculture, Kyoto University
Abstract:
In the lignifying process of xylem cell walls, macromolecular lignin is formed bypolymerization of monolignols on the pectic substances, hemicelluloses and cellulose microfibrils that havedeposited prior to the start of lignification. Observation of lignifying primary and secondary walls of tracheid of
ginkgo by electron microscope gave images that macromolecular lignin or lignin- hemicellulose complexes areformed as modules of similar size surrounding the cellulose microfibrils. This suggests that the starting points ofpolymerization of lignols are distributed along the cellulose microfibri1s at almost regular intervals, 19-26 nm
in the outer layer of secondary wall (S1) and 15-18 nm in the middle layer of secondary wall (S2).
2003-P03
Eucommia ulmoides Oliv.における 8-O-4’ネオリグナン類の生合成と立体化学：コニフェリルアルコールとシナ
ピルアルコールとの交叉カップリング
ラウリット ナタヤ、片山健至，鈴木利貞
香川大学農学部
Biosynthesis and stereochemistry of 8-O-4’ neolignans in Eucommia ulmoides Oliv.: cross coupling of coniferyl
alcohol and sinapyl alcohol
Nattaya Lourith, Takeshi Katayama, Toshisada Suzuki
Abstract:
Four 8-O-4' neolignans. guaiacylglycerol-8-O-4'-(coniferyl alcohol) ether (GGCE);
guaiacylglycerol-8-O-4'-(sinapyl alcohol) ether (GGSE), syringylglycero-8-O-4’-(sinapyl alcohol) ether (SGSE)
and syringylglycerol-8-O-4'-(coniferyl alcohol) ether (SGCE) were synthesized. Their diastereomers wereseparated and elucidated by means of NMR and C7-Hs of threo isomers have larger coupling constant than thoseof erythro isomer. To examine their biosynthesis, feeding experiments of p-[8-14C]hydroxycinnamic acid and a
mixture of [8-14C]comiferyl alcohol (CA) and [8-14C]sinapyl alcohol (SA) into young shoots of E. ulmoides
were undertaken. The [14C]GGCE incorporated from the former precursor was found as aglycone from stems
with the erythro/threo ratio, 1: 1. Its glucosides from the mixed precursors were also found in stems and leaves.
Incubation of a mixture of [8-14C]CA and [8-14C]SA with cell-free extracts from E. ulmoides showed theformation of not only [14C]GGCE but also [14C]GGSE.
2003-P04
白色腐朽菌ミノタケ由来リグニンペルオキシダーゼの反応特性 —P. chrysosporium 由来 LiP H8 との特性比
較—
三木佑太*1、割石博之*2*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究院
Characterization of lignin peroxidase from the white-rot basidiomycete Trametes cervina -Comparison with
LiPH8 from Phanerochaete chrysosporium
Yuta Miki, Hiroyuki Wariishi
Faculty of Agriculture, Kyushu University
Abstract:
A possible site of veratryl alcohol (VA) oxidation in lignin peroxidase of Trametes cervina(TcLiP) was investigated. Reactivities of N-Bromosuccinimide (NBS) modified TcLiP and LiPH8 of
Phanerochaete chrysosporium against VA were determined. VA oxidation activity of NBS-LiPH8 decreased
with NBS concentration-dependent manner. On the other hand, the activity of TcLiP was not interfered by the
NBS modification. Thus, the VA oxidation site of TcLiP is most likely other amino acid residue than Trp. From
3-D modeling of TcLiP, His170 is the candidate for VA oxidation site.
394

2003-P05
白色腐朽担子菌による Polychlorinated biphenyls の分解
北野史郎*1、森 智夫*1、近藤隆一郎*2*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究院
Degradation of polychlorinated biphenyls by white-rot fungi
Shiro Kitano, Toshio Mori, Ryuichiro Kondo
Graduate School of Agriculture, Kyushu University
Abstract:
We have demonstrated that white-rot fungus, Phlebia lindtneri has abilities to oxidize many
xenobiotic compounds, such as polyaromatic hydrocarbons and dioxins. And, we have screened white-rot fungi
for the degradation ability of 4,4'-dichlorobiphenyl (4,4'-DCB). As a result the strain MZ-142 was selected fromtwenty strains. In this study, the degradation of bipheny1 (BPE) and 4,4'-DCB by Phlebia lindtneri and thestrain MZ-142 was examined and the mechanisms
involved in initial hydroxylation were characterized. One of the metabolites, 2-hydroxy-4,4'- dichlorobiphenyl
from 4,4'-DCB was identified in the culture of the both fungi during 9-day incubation. When BPE and 4,4'-DCB
were treated by the strain MZ-142, the decrease of 4,4'-DCB(50%) was much higher than that of BPE (25%) in the culture of potato dextrose medium. Two kinds ofmetabolites, 2-hydroxy-4,4'-dichlorobiphenyl and 3-hydroxy-3,4'-dichlorobiphenyl were identified from
4,4'-DCB by the strain MZ-142. The quantity of each products was drastically dependent on the culture medium
conditions. Based on these results, the specific pathway for the introduction of hydroxyl group into 4,4'-DCB by
the strain MZ-142 was proposed.
2003-P06
14
C−コニフェリンを用いたヒヤクニチソウ管状要素におけるリグニンの標識
梶田真也*1、辻 幸子*2、福島和彦*2、諸星紀幸*1、片山義博*1、Alain M. Boudet*3*1
東京農工大学大学院 BASE、*2 名古屋大学大学院生命農学研究科、*3UPS−CNRS, France
Radiolabeling of lignin in secondary cell wall of Zinnia tracheary elements
Shinya Kajita*1, Yukiko Tsuji*2, Kazuhiko Fukushima*2, Noriyuki Morohoshi*1, Yoshihiro Katayama*1, Alain M.
Boudet*3*1
Graduate school of Bio-Application and Systems Engineering, Tokyo University of Agriculture andTechnology, *2 Grduate School of Bioagicultural Sciences, Nagoya University, *3UMR CNRS, France
Abstract:
In order to identify the protein(s) that play important roles in inhibition and/or proceeding of
lignin polymerization in secondary wall, novel experimental system have been constructed with tracheary
elements (TEs) of Zinnia elegans. In this system, lignin in the secondary wall of the Zinnia TEs can be labeledwith 14C that derived from administered coniferin-[beta-14C]. The incorporated radioactivity can be estimatedafter thin layer chromatographic separation of thioacidolysis main monomers that recovered from 14C-labeledlignin in TEs. This experimental system is useful for quantitative analysis of lignin and lignification with a small
amount of cell walls.
2003-P07
キタカミハクヨウ ferulate-5-hydroxylase 遺伝子の解析
中田陽子、村上義彦、川合伸也
東京農工大学農学部
Cloning and characterization of ferulate-5-hydroxylase gene from Populus kitakamiensis
Yoko Nakata, Yoshihiko Murakami, Shinya Kawai
Graduate School of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
Ferulate 5-hydroxylase (FA5H) belongs to the family of cytochrome P450-dependentmono-oxygenases. We isolated FA5H cDNA from hybrid aspen, Populus kitakamiensis, it was very similar tothat of Populus trichocalpa. We prepared microsomal fraction from the transformed yeast harboring FA5H
expression vector, and measured its FA5H enzyme activity. Further, we constructed expression vector for fusedprotein of FA5H and NADPH-cytochrome P450 oxidoreductase to increase FA5H activity.
2003-P08
赤色酵母由来 PAL 遺伝子を用いた新規薬剤耐性植物の作出
丸山 亮、織茂良和、赤松智隆、川合伸也
395

東京農工大学農学部
Molecular breeding of a novel herbicide resistant plant by using phenylalanine ammonia-lyase gene from
Rodotorula rubla
Ryo Maruyama, Kazuyoshi Orimo, Tomotaka Akamatsu, Shinya Kawai
Graduate School of Agriculture, Tokyo University of Agriculture and Technology
Abstract:
Phenylalanine ammonia-lyase (PAL) is a key enzyme in the secondary metabolism of higher
plants. Genes encoding PAL have been identified in yeasts and plants. Amino acid sequences between plant
PALs and yeast PALs have low homology and their sensitivity to aminooxy compounds, inhibitors of PAL, arevery different. Yeast PALs are less sensitive. We cloned a PAL gene from Rodotorula rubla (RRPAL) andconstructed expression vector for fused protein in E. coli. Further, we introduced the gene into tobacco plants.
Heterogeneous expressed fused protein in E. coli had PAL activity and RRPAL gene were transcribed intransgenic tobacco plants.
2003-P09
ニセアカシア４CL 遺伝子の単離と機能解析
西口朋子*1、西田友昭*2、堤 祐司*3、近藤隆一郎*3*1
九州大学大学院生物資源環境科学研究科、*2 静岡大学農学部、*3 九州大学大学院農学研究院
4-Coumarate : CoA ligase in Robinia pseudoacacia: cDNA structures
Tomoko Nishiguchi*1, Tomoaki Nishida*2, Yuji Tsutsumi*3, Ryuichiro Kondo*3*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Faculty of Agriculture,
Shizuoka University, *3 Graduate School of Agriculture, Kyushu University
Abstract:
4-Coumarate CoA ligase (4CL) is a key enzyme in general phenylpropanoid pathway and isbelieved to catalyze the activation of 4-hydroxy cinnamate analogues, however, studies indicated that most of
4CL isoenzymes are not active for sinapate. On the other hand, we reported that 4CL isoenzyme in Robinia
pseudoacacia utilized sinapate as substrate. In this study, three 4CL cDNAs were isolated from R. pseudoacacia
and deduced amino acid sequencess were compared to Gm4CL1 which has a catalytic activity for sinapate. A
differential pattern of transcription of each Robinia 4CL gene in various organs was also investigated.
2003-P10
ダイオキシン分解菌から抽出した粗酵素による Polych1orinated Biphenyls（PCB）の分解
松尾保洋、三好進祐、木村圭助、伊藤和貴、橘 燦郎
愛媛大学農学部
Biodegradation of polychlorinated biphenyls with a crude enzyme from fungi having ability for degradation ofdioxins
Yasuhiro Matsuo, Shinsuke Miyoshi, Keisuke Kimura, Kazutaka Ito, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Degradations of 3,3',4,4'-tetrachlorobiphenyl(TCB) with a crude enzyme from fungus PL1 was
conducted in this research to obtain basic information for purification of polychlorinated biphenyls bybioremediation with fungi screened from the nature. About 20% of TCB was degraded for 72 hours with animmobilized crude enzyme from fungus PL1 in a liquid medium. Furthermore, about 60% of TCB was degradedfor 30 days with the immobilized crude enzyme from the fungus in a soil. From the results obtained here, it issuggested that bioremediation of polychlorinated biphenyls by screened fungi from the nature is possible.
2003-P11
アメリカヤマナラシにおけるシナピルアルコールデヒドロゲナーゼ（SAD）の免疫局在
西原 猛、大室義人、高部圭司、藤田 稔
京都大学大学院農学研究科
Immunolocalization of sinapyl alcohol dehydrogenase (SAD) in Populus tremuloides
Takeshi Nishihara, Yoshihito Omuro, Keiji Takabe, Minoru Fujita
Graduate School of Agriculture, Kyoto University
Abstract:
To study biosynthesis of monolignols, it is necessary to know how expression and function of
enzymes that ale involved in the cinnamic acid pathway are regulated. Sinapyl alcohol dehydrogenase (SAD)
has been reported to catalyze the reductive reaction specifically from sinapaldehyde to sinapyl alcohol. We
therefore tried to investigate the distribution of SAD in quaking aspen (Populus tremuloides) byimmunolabeling. The labeling was mainly observed on cytosol of the differentiating xylem cells. It indicates396

that sinapyl alcohol, which is the last product of monolignol, is synthesized in cytosol.
2003-P12
HBS パルプ化におけるリグニンモデル化合物の反応（2）高森ひとみ、岸本崇生、浦木康光、生方 信
北海道大学大学院農学研究科
Reaction of lignin model compounds during high-boiling solvent pulping (2)Hitomi Takamori,Takao Kishimoto,Yastmitu Uraki, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
Reaction of β-β, β-5 and β-I types of dimeric lignin model compounds were studied in 70wt%
aq 1,4-butanediol solution at 180ºC to investigate the delignification mechanism under HBS (high-boilingsolvent) pulping conditions. Reaction products were separated by TLC, and analyzed by HPLC, GPC and NMR.
As a result, β-βand β-5 type of lignin model compounds was stable, while β-1 type is unstable and converted
into stilbene. These results are in agreement with those of lignin sample.
2003-P13
HBS パルプ化におけるリグニンの構造変化 −チオアシドリシス及び NMR による解析（2）−植木飛鳥*1、斉藤香織*2、福島和彦*2、岸本崇生*1、浦木康光*1、生方 信*1*1
北海道大学大学院農学研究科、*2 名古屋大学大学院生命農学研究科、
Structural changes in lignin during HBS pulping -Thioacidolysis and NMR analysis (2) Asuka Ueki*1, Kaori Saito*2, Kazuhiko Fukushima*2, Takao Kishimoto*1, Yasumitsu Uraki*1, Makoto Ubukata*1*1
Graduate School of Agriculture, Hokkaido University, *2Graduate School of Bioagricultural Science, Nagoya
University
Abstract:
Structural changes in lignin during high-boiling solvent (HBS) pulping were investigated bythioacidolysis and HMQC spectra. The decrease in the content of β-O-4 structures was confirmed bythioacidolysis. Introduction of 1,4-butanediol into -position of β-O-4 moiety was observed by HMQC spectra.
The reactivity of syringyl type β-O-4 structure was slightly higher than that of guaiacyl type structure. The
higher reactivity of syringyl type was also observed with β-1 structure. The β-1 substructure was unstable under
HBS pulping conditions. Formation of stilbene structure was obvious in HMQC spectra.
2003-P14
広葉樹クラフトパルプのキシロース・グルコース比による収率予測（2）児安 崇、横山朝哉、大井 洋
筑波大学農林工学系
Prediction of pulp yields using xylose/glucose ratios of hardwood kraft pulp (2)Takashi Koyasu, Tomoya Yokoyama, Hiroshi Ohi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
Alkali pulps were acid-hydrolyzed according to TAPPI method T249 cm-85 using 3ml
of 72% sulfuric acid for 0.3g of pulp. However, it was shown that the hydrolysis is insufficient. The method was
modified by the use of 6ml of 72% sulfuric acid for 0.3g of pulp and the prolonged reaction time; 2.5 hr for the
primary hydrolysis. After the modified hydrolysis, the xylose ratios to glucose were obtained by gas
chromatography of the alditol acetates and high performance liquid chromatography of the aldoses.
Carbohydrates analysis of hardwood alkali pulps was applied to prediction of pulp yields obtained by modified
polysulfide-anthraquinone pulping.
2003-P15
直接導入法による DHP の質量分析
黒田健一、中川明子
筑波大学農林工学系
Mass spectrometry of dehydrogenation polymer of coniferyl alcohol with a direct sample inlet
Ken-ichi Kuroda and Akiko Nakagawa-jzumi
Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
A 25% tetramethylammonium hydroxide (TMAH) methanolic solution containing a bulk
dehydrogenation polymer of coniferyl alcohol (DHP) was introduced into a mass spectrometer with a direct
injection probe. Mass analysis employed a rate of 40ºC/m, probe temperature 50 to 400ºC, and a 70eV397

ionization voltage. The mass spectrum, time integrated over scans 526-556 (225-235ºC), showed a highabundance of the m/z 181 base ion of 1-(3,4-dimethoxyphenyl)-1,2,3-trimethoxy- propane (2) stemming fromguaiacylglycerol moieties involved in -aryl ether linkages, and a low abundance of the m/z 386 ion, themolecular ion of pinoresinol dimethyl ether (4), and the m/z 370 ion, the TMAH thermochemolysis product 3 ofdehydrodiconiferyl alcohol, were observed. The mass
spectrum, time integrated over scans 602-639 (250-264ºC), showed a high abundance of the m/z 181 and 370
ions. The m/z 181 ion was observed ranging scans 180 from 1000 (110-370ºC). The 208 m/z molecular ion ofconiferyl alcohol dimethyl ether (1) was observed in the spectrum integrated over scans 180-660 (110-270ºC).
The mass spectrum, time integrated over scans 180-1000 (110-370ºC), was similar to the 315ºC pyrolysis mass
spectrum of the DHP. TMAH thermochemolysis-gas chromatography (-mass spectrometry) of the DHP revealed
GC(-MS) signals corresponding to 1-4.
2003-P16
TMSiI によるリグニン β-O-4 の開裂機構の検討 —13C-標識 NMR 示差スペクトル分析法を用いて堀啓映子*1、新谷博幸*1、飯塚堯介*1、寺島典二*2*1
東京大学大学院農学生命科学研究科、*２名古屋大学
Studies on β-O-4 cleavage by TMSiI treatment: using for 13C-enriched differential NMR spectroscopy
Keko Hori*1, Hiroyuki Shintani*1, Gyosuke Meshitsuka*1, Noritsugu Terashima*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Professor emeritus, Nagoya
University
Abstract:
Trimethylsilyl iodide (TMSiI) is known to cleave β-ether bonds selectively under very mild
reaction condition. But side reactions, such as iodination and polymerization, were occurred by long timetreatment. 13C-enriched and unenriched DHPs were synthesized and their differential NMR spectra were
measured before and after TMSil treatment in NMR tube. The differential NMR spectra showed some changes
indicating decreased amount of β-O-4, coniferyl alcohol and coniferaldehyde structures and appearance of one
signal after TMSil treatment. However, total peak area was also decreased after TMSiI treatment, probably
because of the precipitation of reaction products by water addition for stopping the reaction. Water addition
might cause some side reactions.
2003-P17
単離過程におけるリグニン構造の変化とその要因について —磨砕処理の影響—
藤本 文、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Changes of lignin structures during the process of MWL isolation
Aya Fujimoto, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Milled wood lignin (MWL) is a lignin sample that reflects the characters of protolignin in wood,
although it is well recognized that MWL represents only a part of protolignin and it can never be free fromstructural modification during its isolation procedure. The structures of MWL are featured by such artificial
changes and native differences, in addition to general characteristics as lignin. In this paper, we aimed to
distinguish the nature of lignin after milling from its original nature by the use of alkaline nitrobenzene
oxidation method and determination of methoxyl groups in order to understand the essential characters of MWL
and lignin in wood and milled wood. From the results of S/V ratios and the yields of main oxidation products byalkaline nitrobenzene oxidation, it was suggested that the nucleic structural differences in crude MWLs mightreflect mainly the native differences in lignin.
2003-P18
アルカリ性酸素脱リグニン段排液リグニンの土壌改良剤としての性状
王東香、勝亦京子、飯塚堯介
東京大学大学院農学生命科学研究科
Characterization of lignin fractions in alkaline-oxygen stage waste liquor as soil conditioning agent
Dongxang Wang, Kyoko S. Katsumata, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo,
Abstract:
In most of the worlds tropical areas where soil is acidic, Al toxicity is a serious problem which
limits the productivity of crop plants. The possibility of utilizing lignin fragments from alkaline oxygen398

delignification stage waste liquor generated from paper mill as soil conditioning agent was studied. Alkaline
oxygen delignification stage waste liquor was subjected to Gel Filtrationn Chromatography (GFC) andseparated into four fractions (F1, F2, F3, and F4). Then, these four fractions were used for plant experiment. The
results indicated lignin fragments are capable of alleviating the toxicity of Al, providing improved performanceof radish root growth. Each fraction showed different performance on removing the Al toxicity, and so thereason for their different behaviors on Al toxicity was also studied.
2003-P19
スギおよぴブナの超臨界水処理により得られるリグニン由来物質の GC−MS 分析
江原克信、高田大士、坂 志朗
京都大学大学院エネルギー科学研究科
Gas chromatographic and mass spectrometric (GC-MS) analysis of lignin-derived products from Cryptomeria
japonica and Fagus crenata as treated in supercritical water
Katsunobu Ehara, Daishi Takada, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Softwood (Cryptomeria japonic) and hardwood (Fagus crenata) were treated in supercriticalwater (380ºC, 100MPa) for 8 seconds. The treated woods were fractionated to the water-soluble portion,
methanol-soluble portion and methanol-insoluble residues. For the methanol- soluble portion which mainly
consists of lignin-derived products, GPC and GC-MS analyses were made to clarify the molecular weight
distribution and to identify monomeric products, respectively. GPC analysis revealed that the methanol-soluble
portion contains monomeric and some oligomeric products. Nineteen guaiacyl compounds in methanol-soluble
portion from softwood, and 15 syringyl compounds in methanol-soluble portion from hardwood were identified
by GC-MS analysis. These observations suggested that the lignin-derived products are useful products for
substituting the chemicals from fossil resources.
2003-P20
中性抄紙における硫酸リグニン由来のロジンサイズ定着剤の調製とその評価
松下泰幸、岩月亜佑子、安田征市
名古屋大学大学院生命農学研究科
Preparation and evaluation of retention aids for rosin sizes from sulfuric acid lignin in neutral papermaking
condition
Yasuyuki Matsushita, Ayuko Iwatsuki and Seiichi Yasuda
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
Cationic polymers as the retention aids for rosin sizes in neutral papermaking were preparedfrom sulfuric acid lignin (SAL), one type of acid lignin. To convert SAL to the cationic polymer (MP-SAL),
SAL was phenolated followed by the Mannich reaction to introduce the amino groups. In the MP-SAL single
system, MP-SAL exhibited high sizing effectiveness in neutral papermaking with the rosin emulsion size.
However, MP-SAL showed no sizing effectiveness when soap rosin size was used. In the alum-MP-SAL dual
system, alum and MP-SAL, synergistically enhanced the sizing effectiveness in the rosin emulsion sizing at
neutral pH.
2003-P21ヒドロキシプロピル化未漂白パルプより調製したゲルの膨潤挙動
井村 健、浦木康光、岸本崇生、生方 信
北海道大学大学院農学研究科
Swelling behavior of hydroxypropylated unbleached pulp gels
Takeshi Imura, Yasumitu Uraki, Takao Kishimoto, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
Urethane- and epoxy-types of gels were prepared from hydroxypropylated unbleached acetic
acid pulps (HP-AP' s) using hexamethylen diisocianate (HDl) and ethyleneglycol diglycidyl ether (ED) as
cross-linkers. The residual lignin content influenced thermoresponse of the gels; the volume-transition
temperature of the gel upon heating was lowered by the lignin. The epoxy-type gel from HP-softwood AP
showed the volume transition at 38ºC, suggesting its possibility as a support in the drug delivery system. In
addition, all the gels showed very unique swelling behavior in aqueous solution of cationic surfactants.
Although the mechanism have not been clarified yet, the behavior seems to contribute to explore novel
utilization of the gels.
399

2003-P22
リグニンゲルの膨潤と応用
臼倉ゆり子*1、浦木康光*1、岸本崇生*1、生方 信*1、平沖敏文*2、福島和彦*3*1
北海道大学大学院農学研究科、*2 北海道大学大学院工学研究科、*3 名古屋大学大学院生命農学研究科
Swelling mechanism and application of lignin gel
Yuriko Usukura*1, Yasumitsu Uraki*1, Takao Kishimoto*1, Makoto Ubukata*1, Toshifumi Hiraoki*2, Kazuhiko
Fukushima*3*1
Graduate School of Agriculture, Hokkaido University, *2Graduate School of Engineering, Hokkaido University,*3
Graduate School of Bioagricultural Science, Nagoya University
Abstract:
Lignin-gel was prepared from acetic acid lignin (AL) with polyethylene glycol diglycidyl ether(PE) at a high lignin concentration. This lignin gel was found to swell in aqueous organic solvents. The mobilityof the solvated solvent was evaluated from the spin-spin lattice relaxation time (T2) using NMR to clarify theswelling mechanism. T2 of the solvents decreased with increasing the gel swelling degree. In particular, thistendency of the organic solvent was remarkable. This result suggests that the adsorption of solvent molecules
onto gel polymer chain reduces the mobility of the solvent. As one of the applications of lignin gel, we
attempted to utilize it as a membrane for solvent separation by pervaporation. As a result, ethanol selectively
permeated at the low ethanol concentration, but the selectivity changes at the high concentration.
2003-P23
リグノスルホン酸塩系ポリウレタンゲルの調製と物性
伊藤孝志*1、畠山兵衛*1、畠山立子*2*1
福井工業大学工学部、*2 大妻女子大学
DSC and AFM studies on sodium lignosulfonate-based PU hydrogels
Takashi Itoh*1, Hyoe Hatakeyama*1, Tatsuko Hatakeyama*2*1
Fukui University of Technology, *2Otsuma Women’s University
Abstract:
Sodium lignosulfonate (LS)-based polyurethane (PU) hydrogels were prepared from LS andhexamethylene diisocyanate (HDI) derivatives. Water content (Wc) of the obtained PU hydrogels was less than
3.0 g g-1 and NCO/OH ratio was varied from 0.2 to 0.6 mol mol-1. Phase transitions of LS and PU hydrogels
were measured by differential scanning calorimetry PSC). From DSC curves, glass transition temperature (T g),
melting peak at low temperature (Tml) and melting peak at high temperature (Tmh) were observed. It was also
confirmed that there were three kinds of water, non-freezing water, freezing bound water, and freezing water.
2003-P24
アルコリシスリグニン、エチレングリコール及びグリセリンのエステル—カルボン酸誘導体を原料とするエポキシ樹脂の合成とその熱的性質
廣瀬重雄*1、畠山兵衛*２*1
産業技術総合研究所、*２福井工業大学工学部
Synthesis and thermal properties of epoxy resins from ester-carboxylic acid derivatives of alcoholysis lignin,
ethylene glycol and glycerin
Shigeo Hirose*1, Hyoe Hatakeyama*2*1
Research Institute of Materials and Chemical Process, AlST, *2 Fukui University of Technology
Abstract:
Alcoholysis lignin (AL) was dissolved in ethylene glycol (EG) and the obtained mixture wasreacted with succinic anhydride to form a mixture of ester-carboxylic acid derivatives (AL-EG polyacid,
ALEGPA). Glycerin-polyacid (ALGLYPA) was also prepared from AL and glycerin. The mixture of ALEGPA
and ALGLYPA was reacted with ethylene glycol diglycidyl ether in the presence of catalytic amount ofdimethylbenzylamine to form epoxy resins. The molar ratio of epoxy groups to carboxylic acid groups([EPOXY]/[AA] ratios, mol/mol) was maintained at 1.1. The contents of ALGLYPA in the mixture of ALEGPA
and ALGLYPA (ALGLYPA content) were varied from 0 to 100 %. Thermal properties of epoxy resins werestudied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Glass transition temperatures(Tg's) of epoxy resins increased with increasing ALGLYPA contents suggesting that glycerin structure acts as a
hard segment in epoxy resin networks. Thermal decomposition temperatures (T d'S) of epoxy resins were almost
constant regardless of ALGLYPA contents.
2003-P25
400

クラフトリグニン及びリグノスルホン酸塩系木粉分散型ポリウレタン複合材料の熱的・機械的性質
栗本幹久*1、藤井博知*1、畠山兵衛*1、畠山立子*2*1
福井工業大学工学部、*2 大妻女子大学
Thermal and mechanical properties of PU composites containing wood powder with sodium lignosulfonate andkraft lignin
M. Kurimoto*1, Hyoe Hatakeyama*1, Tatsuko Hatakeyama*2*1
Fukui University of Technology, *2Otsuma Women’s University
Abstract:
Polyurethape (PU) composites were prepared from ground wood mixed with a kraft
lignin (KL)-polyol solution and sodium lignosulfonate (LS)-polyol solution consisting of KL or LS dissolved inpolyethylene glycol (PEG-200) triethylene glycol (TEG) and diethylene glycol (DEG). Mechanical and thermal
properties of the above composites were studied. Thermal properties of the prepared PU composites werestudied by thermogravimetry (TG). Sample weight for TG was ca. 7mg. Mechanical properties of PU
composites were studied by compression tests, according to the Japanese Industrial Standard (JIS) A 1408 at
room temperature.
2003-P26
無機粒子分散型クラフトリグニン系ポリウレタンの調製と物性
松村博司*1、畠山兵衝*1、畠山立子*2*1
福井工業大学工学部、*2 大妻女子大学
Mechanical properties of kraft lignin-based PU foams containing inorganic fillers
Hiroshi Matsumura*1, Hyoe Hatakeyama*1, Tatsuko Hatakeyama*2*1
Fukui University of Technology, *2Otsuma Women’s University
Abstract:
Rigid polyurethane (PU) foams were prepared from kraft lignin (KL) which was dissolved in
diethylene glycol (DEG), triethylene glycol (TEG) or polyethylene glycol (molecular weight 200: PEG200).
The obtained solution containing filler was reacted with isocyanate in the presence of small amounts of silicone
surfactant, catalyst and water. Mechanical properties of these polyurethanes (PU's) were studied by compression
tests. It was found that compression strength and compression elasticity of KLPU show maximum values at a
certain filler content from 10 to 40%. Compression strength decreased with increasing molecular weight of
ethylene glycol.
2003-P27
植物性廃棄物に由来するリグニンの油脂に対する参加防止効果
藤加珠子，野田博行
生物ラジカル研究所
Antioxidant effect of lignin obtained from botanical wastes
Kazuko Toh, Hiroyuki Noda
Institute for Life Support Technology
Abstract:
Antioxidant effect of lignin and lignophenol, which were prepared from botanical wastes, wasinvestigated. As the botanical wastes, used tea leaves (green tea), peanut husk, rice bran, and wood meal wereused. The antioxidant effect was evaluated on the basis of the changes in peroxide value by auto-oxidation oflinoleic acid. It was found that all samples showed high antioxidant effect. Especially, a lignophenol from tea
leaves had the highest activity. In comparison with commercially available antioxidants, the antioxidant effect of
the lignophenol from tea leaves was higher than that, of vitamin E, but lower than those of t-butylhydroxyanisol(=BHA) and ferulic acid.

401

第 49 回 （2004.11.18-19） 筑波大学大学会館
2004-101
表面プラズモン共鳴を用いたモノリグノール類とヘミセルロースの相互作用解析
浦木康光、中村 淳、岸本崇生、生方 信
北海道大学大学院農学研究科
Investigation on interaction between monolignols and hemicellulose using surface plasmon resonanceYasumitsu Uraki, Atsushi Nakamura, Takao Kishimoto, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
Interactions of monolignol (coniferyl alcohol) or its glucoside (coniferin) with xylan wasinvestigated by the surface plasmon resonance (BiacoreTM) to clarify the transportation of lignin
precursor from cytoplasm in the lignification process. Xylan isolated from birch was oxidized with periodate to
generate aldehyde group, and then the resulting xylan was immobilized onto carboxymethyl (CM)-dextran as asupport of sensor chip by the reductive amination to give a ligand on the sensor chip. The adsorption capacity ofthe oxidized xylan to coniferin was much larger than that of its glucoside. It is proposed that coniferyl alcohol
would be supplied from cytoplasm for lignification but not its glucoside.
2004-102
広葉樹放射組織におけるリグニン化学構造の特性について
近藤憲哉、秋山拓也、、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Structure of lignin in ray parenchyma obtained by a direct sampling without chemical treatment
Kenya Kondo, Takuya Akiyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Science, the University of Tokyo
Abstract:'Ray' and 'ray-free' fractions were separated from heartwood of Platanus orientalis by direct
cutting on naked eyes. Klason lignin content was higher in 'ray' and lower in 'ray-free' fraction. Diastereomerratio of β-O-4 structure obtained by ozonation method (E/T ratio) and ratio of aromatic ring type obtained bynitrobenzene oxidation (S/V ratio) were also higher in 'ray' and lower in 'ray-free' fraction. These tendencies
were the same as those in sapwood. However, both S/V and E/T ratios obtained for whole wood of heartwood
didn't exhibit the intermediate values of 'ray' and 'ray-free' fraction of heartwood. Although this result can't be
explained at this moment, it was implied that alcohol-benzene extractives could affect significantly the results ofnitrobenzene oxidation and ozonation. When all values of E/T ratio obtained in this experiment were plottedagainst those of SN ratio, they were correlated well each other, which confirmed the recent finding by Akiyama
et al.
2004-103
高分子鋳型存在下でのコニフェリルアルコールの酵素重合
中村力也*1、松下泰幸*1、福島和彦*1、梅本和彦*2、臼杵有光*2*1名古屋大学大学院生命農学研究科, *2 豊田中研
Enzymatic polymerization of coniferyl alcohol in the presence of polymer templates
Rikiya Nakamura*1, Yasuyuki Matsusita*1, Kazuhiko Fukushima*1, Kazuhiko Umemoto*1, Arimitsu Usuki*2*1
Graduated School of Bioagriculutual Sciences, Nagoya University, *2Toyota Central R & D Laboratries
Abstract:
Dehydrogenative polymerisate (DHP) of coniferyl alcohol, a main monomer of lignin, wasprepared by the use of horseradish peroxidase/H2O2 system in the presence of polymer templates, e.g.,poly(ethylene glycol), cellulose, xylan, and cyclodextrins (CDs). DHP was characterized by 1H NMR and size
exclusion chromatography. The chemical bonds ratio (β-O-4': β-5': β-β') was calculated by using the signal of 1H
NMR of acetylated DHP. Addition of xylan and α-CD led to the increase of β-5' and β-O-4' structure,
respectively. This result indicated that chemical structure of DHP was regulated by the additions of xylan andα-CD in the reaction medium.
2004-104
細胞壁中における高分子リグニン形成過程の電顕観察 III. イチョウの Purves リグニンの観察
寺島典二*1、吉田正人*2*1
名古屋大学、*2 名古屋大学大学院生命農学研究科
Formation of macromolecular lignin in the cell wall as observed by electron microscopy III, Observation of402

Purves lignin prepared from differentiating xylem of Ginkgo biloba
Noritsugu Terashima*1,Masato Yoshida*1*1
Professor emeritus, Nagoya University, *2Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
In the lignifying cell wall, lignin is formed as beads-like modules of lignin-hemicellulose
complexes surrounding cellulose microfibrils as observed by FE-SEM. It was assumed that fusion of themodules in a final stage of cell wall lignification form a super high-molecular lignin-hemicellulose complex.
Purves lignin was isolated from the differentiating ginkgo xylem by selective removal of polysaccharides by
periodate oxidation. The lignin retained morphological features of tracheids even if it is isolated from the woodin which phenolic hydroxyl groups of lignin were protected by methylation from undesirable modification
during periodate oxidation. The results support the assumed ultrastructural assembly of the cell wall polymers inginkgo tracheids.
2004-105
イソコニフェリン化学合成法の改良とその脱水兼重合
飛松裕基，細谷隆史，上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
lmprovement of chemical synthesis of isoconiferin and its dehydrogenative polymerization
Yuki Tobimatsu, Takashi Hosoya, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
To obtain highly polymerized DHP (Dehydrogenation polymer) by an introduction ofhydrophilic glucose unit to monolignol, isoconiferin was successively prepared by the use of imidate method
and polymerized by Peroxidase/ Hydrogen peroxide. The polymerization of isoconiferin proceeded in acompletely homogeneous way and the resulting polymer was water-soluble. The molecular weight ofisoconiferin-DHP depended on monomer addition times, concentrations of monomer and most strongly onamounts of peroxidase, while the molecular weight of coniferyl alcohol-DHP had no dependence on the amountof Peroxidase. As the results, maximum DP of isoconiferin-DHP was 31, while that of comiferyl alcohol was 15.
2004-106
β-O-4 型規則性人工リグニンポリマーの合成（2）岸本崇生．浦木康光，生方 信
北海道大学大学院農学研究科
Synthesis of artificial lignin polymer composed of β-O-4 structure
Takao Kishimoto, Yasumitsu Uraki, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
The β-O-4 structure is one of the most important substructures in lignin. We are working on thesynthesis of lignin polymers composed of only β-O-4 structure from simple aromatic compounds as starting
materials by a solution polymerization method. New monomer was selected and polymerized in the presence ofalkali. The obtained polymeric material was analyzed by 1H- and 13C-NMR spectroscopy, which suggests thatthe polymer has a regular structure. Molecular weight of the polymer will be determined by GPC analysis.
2004-107
ポプラペルオキシダーゼ遺伝子の単離とそれらのストレス誘導発現解析
森永紗也佳*1、佐々木慎弥*1、楠城時彦*2、篠原健司*2、堤 裕司*3、近藤隆一郎*3*1
九州大学大学院生物資源環境科学研究科、*2 森林総合研究所、*3 九州大学大学院農学研究院
Isolation and expression analysis of peroxidase genes in poplar under stress treatments
Sayaka Morinaga*1, Shinya Saaki*1, Tokihiko Nanjo*2, Kenji Shinohara*2, Yuji Tsutsumi*3, Ryuichiro Kondo*3*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Forestry and Forest
Products Research Institute, *3Graduate School of Agriculture, Kyushu University
Abstract:
In higher plants, the peroxidase (PO) activity is generally upregulated by environmental stresses.
However, PO comprise a multigene family, and therefore the most of physiological functions of isoenzynes have
yet been unclear. In this Study, we analyzed the gene expression of some POs from poplar, a model tree. ESTs
generated from the stress-treated leaves of Populus nigra were subjected to the screeming of poplar PO clones,
and 198 PO candidates were isolated. Of the 198 candidates, we selected 11 PO clones. A cationic PO clone wasabundantly expressed in the poplar stress-related ESTs (104/198), suggesting its stress inducibility. In fact, it
was confirmed to be induced by environmental stress treatnents such as dry, cold, heat, and H 2O2 by northern403

analysis. The exhaustive expression analysis of other PO genes and additional 17 PO clones isolated from theleaf, shoot, and xylem of P. alba with respect to the stress-induction is now undergoing.
2004-108
ＬＩＭ様転写因子の発現抑制による低リグニン樹木の開発
河岡明義，渡邊恵子，南藤和也，海老沼宏安
日本製紙株式会社森林科学研究所
Production and characterization of lignin-reduced woody plants by suppression of LIM transcription factor
Akiyoshi Kawaoka, Keiko Watanabe, Kazuya Nanto, Hiroyasu Ebinuma
Nippon Paper Industries Co., Ltd.
Abstract:
Lignins are phenolic polymers that are embedded in the cell walls of specialized plant cells. Our
research purpose is to produce woody plants with low level of lignin for environmental and economical benefitsof pulp production. Previously, we identified a cDNA encoding transcription factor from tobacco (Nicotiana
tabacum), namely Nt1im1 that regulates the gene expression involved in lignin biosynthesis. The antisense
Nt1im1construct was introduced into Eucalyptus camaldulensis that is one of the most important hardwood forafforestration. The transgenic Eucalyptus grown in the greenhouse showed 5% reduction of lignin content and
5% increase of holocellulose content.
2004-109
リグナンの位置選択的メチル化を触媒する新規 O-メチルトランスフエラーゼ
梅澤俊明*1、Laigeng Li*2、鈴木史朗*1*2、榊原紀和*1、中坪朋文*1、Vincent L. Chang*2*1
京都大学生存圏研究所、*2 ノースカロライナ州立大学
A novel O-methyltransferase catalyzing a regioselective methylation of lignan
Toshiaki Umezawa*1, Laigeng Li*2, Shiro Suzuki*1*2, Norikazu Sakakibara*1, Tomoyuki Nakatsubo*1, Vincent L.
Chiang*2*1
Research Institute for Sustainable Humanosphere, Kyoto University, *2 North Carolina State University
Abstract:
In spite of frequent occurrence of methoxyl groups in lignan molecules, little is known about
O-methyltransferases (OMTs) involoved in lignan O-methylation. The present study reports the isolation of anovel safflower (Carthamus tinctorius) gene encoding a lignan O-methyltransferase which catalyzes
regioselective methylation of matairesinol giving rise to arctigenin, but not isoarctigenin. A recombinant proteinof the enzyme, matairesinol O-methyltransferase (CtMROMT),
expressed in E. coli, exhibited the regioselectivity, like the plant protein, while the recombinmt CtMROMT did
not catalyze O-methylation of hydroxymonolignols and cinnamates, suggesting that the OMT is a novel type ofplant OMT specific to lignan methylation.
2004-110
トチュウ粗酵素によってコニフェリルアルコールから生じる(＋)-エリトロ-及び(−)-トレオ-グアイアシルグリセロ
ール−β−コニフェリルエーテルの絶対立体配置とその新奇な立体選択的生成機構の提案
片山健至、田渕ゆかり、鈴木利貞
香川大学農学部
Absolute configuration of (+)erythro- and (-)-threo-guaiacylglycerol-β-coniferyl ethers formed by the
incubation of coniferyl alcohol wit cell-free extracts of Eucommia ulmoides and their novel stereoselective
formation
Thkeshi Katayama, Yukari Tabuchi, Toshisda Suzuki
Faculty of Agriculture, Kagawa University
Abstract:
Incubation of coniferyl alcohol wit cell-free extracts of Eucommia ulmoides in die presence ofhydrogen peroxide gave (+)erythro- and (-)-threo-guaiacylglycerol-β-oniferyl ethers (GGCE), and the erythro
isomer was formed more than the threo isomer. Absolute configuration of (+)erythro, (-)erythro, (+)-threo, and(-)-threo GGCE was determined as (7R, 8S), (7S, 8R), (7S, 8S), and (7R, 8R), respectively, by Mosher's method.
Quanbtative analysis of the four stereoisomers, (7R, 8S)-(+) erythro-, (7S, 8R)- (-)erythro-, (7S, 8S)-(+)-threo-,and (7R, 8R)-(-)-threo-GGCE, showed that their percentages were 44.45%, 25.55%, 5.25%, and 24.75%,
respectively. We found for die first time an enzyme activity that catalyzes the stereoselective addition of waterto (8R)-quinonemethide giving (7R, 8S)- (+)-erythro-GGCE. Non-enzymatic addition of water to the(8S)-quinonamethide gave (7S, 8R)-(-)erythro- and (7R, 8R)-(-)threo-GGCE in the almost same ratio.
404

2004-111
Evolution of lignin —Structural characteristics of polyphenolic components of bryophytes pteridophytes andspermatophytes
Zenfu Jin*1，Yuji Matumoto*1，Takeshi Tange*1，Kenji Iiyama*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Tokyo University of Agriculture
Abstract:
Polyphenolic components of several species of bryophytes and pteridophytes, which have been
gifted by Dr. T. Ishii, Forestry and Forest Products Research Institute and Dr. M, Higuchi, National Science
Museum, were examined by the yield of residues after Klason treatment. an alkaline nitrobenzene oxidation foraromatic composition, analytical ozonolysis to investigate the presence of β-O-4 intermonomer linkages andmethoxyl content. Syringyl unit was detected in alkaline nitrobenzene oxidation products of Selaginella
tamariscina (Beauv.) Spring and molar ratio of syringyl to guaiacyl nuclei (S/V ratio) was 2.31. Björkman
lignins were prepared from S. tamariscina and Polystichum polyblepharum after extraction with 80% EtOH
followed by water to investigate structural characteristics of lignins. The presence of syringyl unit as the major
component of lignin in S. tamariscina, but not in P. polyblepharum, was also supported by 1H NMR and FTIR
spectroscopies,
and confirmed by acidolysis and ozonation, that syringyl unit of S. tamariscina lignin is involved in β-O-4linkages. The low content of methoxyl group and low total yield of alkaline nitrobenzene oxidation products andozonation products suggest that Klason residue is not represent real lignin of
S. tamariscina and P. polyblepharum.
2004-１12β-O-4 型構造の側鎖の立体構造を規定する要因（その 2）—erythro/threo 比と S/V 比の相関—
秋山拓也*1、後藤仁志*1、松本雄二*1、飯塚堯介*1、Deded S. Nawawi*2, Wasrin Syafii*2*1
東京大学院農学生命科学研究科、*2Bogor Agricultural University
A factor determining the diastereomeric forms of β-O-4 structures -Relationships between erythro/threo ratio
and syringyl/guaiacyl ratio among different wood species
Takuya Akiyama*1, Hitoshi Goto*1, Yuji Matsumoto*1, Gyosuke Meshitsuka*1, Deded S Nawawi*2, Wasrin
Syafii*2*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Bogor Agricultural University
Abstract:
Twenty-one wood species containing softwoods and hardwoods were subjected to nitrobenzene
oxidation. The S/V ratio obtained was widely varied depending on wood species (0 to 6.1). The erythro/(erythro+ threo) ratios of β-O-4 structures were strongly correlated with the S/(S+V) ratios (R2 = 0.99), as well as withthe previously reported methoxyl group content in lignin (R2 = 0.83). It was suggested that syringyl/guaiacyl
composition is one of the factors which control the proportion of erythro and threo forms of β-O-4 structuresduring the process of lignin formation. By nitrobenzene oxidation, a variation in the content of biphenyl type(5-5 linkage type) structure was also investigated based on divanillin yield.
2004-特別講演
リグニン科学の新たな展開 —リグニン科学者に求められている課題—
飯山賢治
東京農業大学、東京大学アジア生物資源環境研究センター
Let's advance a fresh lignin science: Assignments asked for lignin scientists
Kenji Iiyama
Tokyo University of Agriculture and the University of Tokyo
Abstract:
The most abundant organic compound on the earth is "Lignin", but not cellulose, because lignin
resists strongly against mineralization by the activities of microorganisms. Presence of lignin, therefore, plays akey part in global carbon circulation, global environment and accumulation of fossil resources. In addition, theterm of lignin is discussed widely in various disciplines such as agricultural science, botany, environmental
science, ecology, animal husbandry, pharmacy, oceanography, archaeology, and so on. Lignin scientists arelooked forward to advancing such disciplines. The assignments asked for lignin scientists are discussed.
2004-201
Phanerochaete crassa WD1694 菌の菌糸先端部のペルオキシダーゼ活性の定量高野麻理子、安部 久、林 徳子
森林総合研究所
405

Extracellular peroxidase activity at the apical tip of Phanerochaete crassa WD1694
Mariko Takano, Hisashi Abe, Noriko Hayashi
Forestry and Forest Products Research Institute
Abstract:
Extracellular peroxidase activity of Phanerochaete crassa WD1694 was visualized by staining
with a peroxidase substrate, 3,3'-5,5'-Tetramethylbenzidine precipitate. The staining occurred directly on andalong the apical tip of the mycelium. Visible spectra and absorbance of the staining at the apical tip was
analyzed by microspectrophotometry, and catalytic velocity was calculated. The maximum catalytic velocity
was estimated 1135 M/min. The result clearly showed that the catalytic velocity of the extracellular peroxidase
reaction at the apical tip of P. crassa WD1694 was much higher than that reported on MnP and Lip of
Phanerochaete chrysosporium that caused the depolymerization of lignin in vitro.
2004-20213
C シアン配位型ペルオキシダーゼの NMR 解析 —過酸化水素との反応における活性部位アミノ酸残基の役割—
野中大輔*1、親泊政二三*2、藤井 浩*3、割石博之*4*1
九州大学大学院生物資源環境科学研究科、*2 科学技術振興機構、*3 大学共同利用機関法人自然科学研究機構岡崎統合バイオサイエンスセンター、*4 九州大学大学院農学研究院
NMR Analysis of 13C15N-ligated lignin peroxidase and manganese peroxidase - Role of active-site amino acids
in hydrogen peroxide activation
Daisuke Nonaka*1, Masafumi Oyadomari*2, Hiroshi Fujii*3, Hiroyuki Wariishi*4*1Graduate School of Bioresource and Bioenvironmental Sciences. Kyushu University, *2Japan Science andTechnology Agency, *3lnstjtute for Molecular Science and Center for lntegrative Bioscience. *4National
Institutes of Natural Science, Faculty of Agriculture, Kyushu University
Abstract:
To investigate the heme environment of lignin peroxidase and manganese peroxidasefrom Phanerochaete chrysosporium, 13C- and 15N-NMR spectroscopjc techniques were utilized. 13C-NMR
signals of cyanide bound to the heme iron of LiP and MnP (-3860 ppm and -3863 ppm , respectively) indicatedthat electron push effect from axial ligands of both enzymes were much lower than that of common peroxidases,
e.g. horseradish peroxidase. On the other hand, 15N-NMR analysis of these enzymes revealed that the electron
pull effect of both enzymes were strong as observed in other peroxidases. These results indicated that LiP and
MnP were shown to share unique features, significantly weak electron push effect but with strong pull effect,
which may explain slower rates of compound I formation for either LiP or MnP.
2004-203
Phanerochaete chrysosporium におけるパスウェイクロストーク
割石博之*1,三浦大典*2、志水元亨*2*1
九州大学大学院農学研究院、*2 九州大学大学院生物資源環境科学研究科
Pathway crosstalk involved in lignin degradation system of Phanerochaete chrysosporium
Hiroyuki Wariishi, Daisuke Miura, Motoyuki Shimizu
Faculty of Agriculture, Kyushu University
Abstract:
A proteomic analysis for surveying heme-binding proteins produced by the white-rot
basidiomycete Phanerochaete chrysosporium was performed utilizing a biotinylated heme- streptavidin beads
system. Mitochondrial citrate synthase (CS) and glyceraldehyde 3-phosphate dehydrogenase (GAPDH) wereidentified as a heme binding protein. CS was shown to possess a Cys-Pro motif, a well-known heme responsive
motif, in its amino acid sequences. A homology modeling via MOE using the crystal structure of citrate synthasefrom pig as a template revealed the existence of the Cys-Pro motif on the surface of the protein. A genomic
analysis revealed that 5Aminolevulinic acid synthase (ALAS) also possesses the Cys-Pro motif. These data, combined with ourprevious data showing the involvement of CS, GAPDH, and ALAS in the metabolic control of carbon flux andredox regulation, strongly suggested that the existence of a unique pathway crosstalk between the glycolysis,
TCA cycle, and heme biosynthetic pathway. This pathway crosstalk is thought necessary for optimizing fungal
lignin degradation system.
2004-204
多糖加水分解酵素による MWL 抽出残渣の分解挙動(II) —特にキシラナーゼ処理について—
吉野寛之、上高原浩、高野俊幸、中坪文明
406京都大学大学院農学研究科
The behavior of degradation of wood meal after extraction of the MWL by carbohydrate-degrading enzymes (II)-Structural analysis by xylanase
Hiroyuki Furuno, Hiroshi Kamitakahara, Toshiyuki Tbkano, Fumiaki Nakatsubo
Graduate school of Agriculture, Kyoto University
Abstract:
The xylanase treatment of Cellulose-Lignin fracdon (CL), which was extracted from MWL
extracted residue with LiCl/ DMAc, was carried out. From neutral sugar and lignin analyses data, it was foundthat xylanase sohbilized approximately 75% of xylose and 41% of lignin CL. From GPC data, it was found thatthe molecular weight of the solubilized lignin was much lower than MWL. These indicated that no less than
40% of lignin in CL, with a low molecular weight, formed xylan-lignin complex. The solubilized lignin
apparently had the native structure derived from LCC.
2004-205
酸素アルカリ処理におけるクラフトリグニンの酸素消費量の測定
今井愛子、友日生織、松本雄二，飯塚堯介
東京大学院農学生命科学研究科
Accurate measurement of oxygen consumption during oxygen-alkali treatment of kraft lignin and lignin modelcompounds
Aiko Imai, Iori Tomoda, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
During oxygen-alkali bleaching, the progress of lignin oxidation is believed to govern thedelignification. However there seems to be no clear relationships established between the oxidation reaction anddelignification. In order to directly analyze the progress of lignin oxidation, we designed a measuring device bywhich oxygen consumption can be precisely followed based on the accurate measurement of oxygen supply tothe reactor. By use of this device, oxygen consumption of isolated softwood kraft lignin and several lignin
model compounds was measured under 0.80 MPa of oxygen pressure at 95ºC. The results were that one
aromatic ring consumed about 3 oxygen molecules. Although non-phenolic lignin model compound didn't
consume any oxygen, results obtained for kraft lignin suggested that non-phenolic unit as well as phenolic unit
in lignin consumed oxygen during oxygen-alkali treatment.
2004-205
化学パルプの温和なアルカリ処理による過マンガン酸カリウム消費物質の生成
友田生織、童国林、松本雄二、飯塚堯介
東京大学院農学生命科学研究科
Formation of permanganate consuming substances by mild alkali treatment of chemical pulp
Iori Tomoda. Guolin Tong, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Permanganate consuming structures were produced from kraft pulp by mild alkali treatment. Its
formation was suppressed when hydrogen peroxide was present during the reaction. In order to fully understandthe role of hydrogen peroxide, pulp was treated by alkali in the presence or absence of hydrogen peroxide under
different pH and the permanganate consumption of both pulp and reaction liquor were analyzed. As roles ofhydrogen peroxide, (i) destruction of permanganate consuming structures, (ii) suppression of the formation of
permanganate consuming structures, and (iii) prohibition of incorporation of permanganate consuming
structures into pulp were suggested.
2004-207
リグニンの嫌気条件下での微生物変性 —シロアリ原腸を通過したリグニンの性状—勝亦京子*1、堀啓映子*1、飯山賢治*2*1
東京大学院農学生命科学研究科、*2 東京農業大学
Changes in structural feature of lignin by microorganism under anaerobic condition -Property of lignin afterdigestion by termite
Kyoko S. Katsumata*1. Keko Hori*1, Kenji Iiyama*2*1
Graduate School of Agricultural and Life Science, the University of Tokyo, *2Tokyo University of Agriculture
Abstract:
Behavior of biodegradation (biomodification) of plant cell wall components under aerobic
condition is well documented, but not enough for especially lignin under anaerobic system. Biomodification of407

lignin is greatly due to the activities of peroxidase group, it is not clear yet the behavior of peroxidases underanaerobic condition. Digestion of woody materials by termites is the typical anaerobic modification of plant cellwall components together with digestion of forages in rumen of ruminants. Changes in chemical feature oflignin by microorganism under anaerobic condition were investigated by the comparison of cell wallcomponents of wood before and after digestion by termite. Wood of Ilang-Ilang (Ilang-Ilang C. dadloyl) andApitong (Dipterocarpus grandiflorua) and excrements of termites which feed each wood were collected from
University of the Philippines. Los Baňos. Björkman lignin of each samples were isolated. There were no
significant differences on 1H-NMR spectra between acetylated Björkman lignin from excrements and original
woods. Methoxyl contents of Björkman lignins from excrements of termite were also similar to those of original
wood. Small differences for only contents of aliphatic hydroxyl and conjugated phenolic hydroxyl group weredetected.
2004-208
リグニンエーテル構造の熱分解開裂機構
河本晴雄、中村健史、坂 志朗
京都大学大学院エネルギー科学研究科
Mechanism of the pyrolytic cleavage of ether structures in lignin
Haruo Kawamoto, Takeshi Nakamura, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Mechanism of the pyrolytic cleavage of α- and β-ether structures in ligmin was studied with
α-ether types of dimeric and α, β-diether types of trimeric model compounds having differently substituted
Cα-phenyl ether groups. As a result, phenolic and non-phenolic α-ether structures were cleaved in ionic andhomolytic (radical) mechanisms, respectively, in dimers. In trimers, additional β-ether groups did not change themechanism of the α-ether cleavage of the non- phenolic trimers, wheras the ionic mechanism was changed toradical in the phenolic trimers. The latter results are reasonably explained with the formation of radical species
through homolytic cleavage of the β-ether structure, although the pyrolytic cleavage of the phenolic α-ether
structures in the phenolic trimers is initiated with the ionic mechanism.
2004-209
木材の光劣化（II） —光照射によるスギ材表面のリグニン構造変化—
砂原 寛*1、中川明子*2、富田文一郎*2、黒田健一*3*1
ケミプロ化成株式会社、*2 筑波大学大学院生命環境科学研究科、*3 九州大学大学院農学研究院
Photodegradation of wood (2) -Change of lignin structure of Cryptomeria japonica D. Don by UV irradiation
Hiroshi Sunahara*1, Akiko Nakagawa*2, Bunichiro Tomita*2, Ken-ichi Kuroda*3*1
Chemipro Lasei Kaisha Ltd., *2Graduate School of Life and Environmental Sciences, University of Tsukuba,*3
Department of Forest and Forest Products Science, Faculty of Agriculture, Kyushu
University
Abstract:
When lumber is left for out side for long time, the color of the lumber's surface is changed,
yellow to white-brown and the surface was cracking. These are due to the participation of photo degradation oflignin by UV irradiation. We then started to the study of photo degradation of lignin. The results suggested thatlignin is degraded early time (acceleration by UV irradiation for 1 to 5 hours). A decrease in β-O-4 subunits wasfound by pyrolysis gas chromatography.
2004-210
リグニン含有フエノール樹脂の表面特性
松下泰幸、和田沙織、福島和彦
名古屋大学大学院生命農学研究科
Surface characteristics of phenol resins contained lignin
Yasuyuki Matsushita, Saori Wada and Kazuhiko Fukushima
Grauate School of Bioagricultural Sciences, Nagoya University
Abstract:
The surface characteristics of phenol-formaldehyde (PF) resin with lignosulfonate and kraft
lignin were determined by contact angle measurement and inverse gas chromatography (IGC). In the contact
angle measurement, the three-liquid method was utilized to determine the Lifshitz- van der Waals components(LW), electron-acceptor parameter (+), and electron- donor parameter (s-) of the prepared resins andcalculation of the acid-base component of the work of adhesion between water and the resins. The result of IGC
408

showed the same LW trends obtained from the contact angle measurement.
2004-211
セルロース微粒子充填クラフトリグニン系エポキシ樹脂複合材料の製造
船橋正弘
産業技術総合研究所
Preparation of composites of kraft-lignin based epoxy resin filled with cellulose particle
Masahiro Funabashi
National Institute of Advanced Industrial Science and Technology (AIST).
Abstract:
A mixture of ester-carboxylic acid derivatives (KLPA) was obtained by reaction of an ethylene
glycol solution of Kraft 1ignin (KL) and succinic anhydride in the presence of a catalytic amount ofdimethylbenzylamine at 80 ºC. Composite samples were prepared by a reaction of the mixture of KLPA andcellulose particles with ethylene glycol diglycidyl ether (EGDGE) at 70 ºC. Cellulose contents ranged from 0 to
60 wt%. The above mixtures were molded into sheets at 130 ºC for 5 hours. The mechanical properties of thesamples were investigated by tensile tests using plate type specimens.
2004-212
断熱材用リグニンベースポリウレタンフォームの熱的機械的性質
畠山兵衝*1、松村博司*1、廣瀬重雄*2、畠山立子*3*1
福井工業大学工学部、*2 産業技術総合研究所、*3 大妻女子大学
Thermal and mechanical properties of lignin-based rigid polyurethane foams for insulation
Hyoe Hatakeyama*1, Hiroshi Matsumura*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3*1
Fukui University of Teclmology, *2National Institute of Advanced Industrial Science and Technology, *30tsuma
Women's University
Abstract:
Rigid polymethane (PU) foams for insulation were prepared from various kinds of lignins suchas kraft lignin (KL), sodium lignosulfonate (LS), solvolysis lignin (SL) and alcoholysis lignin (AL). Thermal
and mechanical properties of the above polyurethane foams (PU's) were investigated by differential scanningcalorimetry (DSC), thermogravimetry (TG), and compression tests. It was found that glass transition
emperatures (Tg's), thermal degradation temperatures (Td'S) and mechanical properties of the PU's were notprominently dependent on kinds of lignin and that all of the above lignin-based PU's are available for insulation.
From the viewpoints of practical utilization, KL- and LS-based PU's were compared in this study.
2004-213
リピッドペルオキシデーションにおけるリグニン分解のラジカル反応化学的考察 —カーボンセンターラジカルについて
大橋康典．渡邉崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Radical chemistry of lipid peroxidation for lignin degradation: On the roles of carbon-centered radicals
Yasunori Ohashi, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University
Abstract:
In 1999, Kapich et al. reported that peroxyl radicals produced by thermal decomposition of azo
compounds degraded a non-phenolic lignin model compound. However, there was no direct evidence showingthat carbon-centered radicals were responsible for the degradation. In the present study, mechanisms for the
non-phenolic β-O-4 lignin model degradation by carbon-centered radicals from azo compounds were
investigated. The results suggested that carbon-centered radicals are able to degrade the model compound by amechanism different from that for peroxyl radicals.
2004-214
カワラタケによるフタル酸ジブチルの分解とそれに関与する酵素
山田喜彦、平井浩文、河合真吾、西田友昭
静岡大学農学部
Degradation of di-n-butyl phthalate by white rot fungus Trametes versicolor and its related enzyme
Yoshihiko Yamada, Hirofumi Hirai, Shingo Kawai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
Di-n-butyl phthalate (DBP) is widely used in a variety of industrial applications as a plasticizer,
and is suspected of having estrogenic (endocrine- disrupting) activity, mutagenicity, teratogenicity, and409

carcinogenicity. In this study, therefore, we attempted the degradation of DBP by white rot fungus Trametes
versicolor. DBP decreased by 85% and 95% after 2 days and 3 days of fungal treatment, respectively, and DBP
was converted into mono-n-butyl phthalate (MBP) and an unidentified product. Although no appreciable
decrease of DBP was obtained by manganese peroxidase and laccase, the cell-free extract prepared from themycelium of T. versicolor decreased DBP and converted DBP into MBP. This result indicated that the
intracellular enzyme(s) produced by white rot fungus is involved in DBP degradation.
2004-215
白色腐朽担子菌とその菌体外酵素による異常プリオンタンパクの分解
岩村 翼*1、山口 同*1、堤 祐司*1、松浦裕一*2、毛利資郎*2、近藤隆一郎*1*1
九州大学大学院農学研究院、*2 九州大学大学院医学研究院
Biodegradation of protease-resistant prion protein by white-rot fungi and their ligninolytic enzymes
Tsubasa Iwanura*1, Atsumu Yanaguchi*1, Yuji Tsutsumi, *1 Yuichi Mat8suura*2, Shirou Mohri*2, Ryuichiro
Kondo*1*1
Graduate School of Agriculture, Kyushu University, *2Graduate School of Medical Sciences, Kyushu
University
Abstract:
Protease Resistant Prion Protein (PrPRes) is cause substance of bovine spongiform
encephalopathy (BSE) and other diseases. PrPRes can not be degraded either by proteases or usual chemicaltreatments. Thus, validated method for the decontamination of PrPRes is urgently required. Recently, white-rot
fungi have received worldwide attention for bioremediation because of their abilities for the degradation anddetoxification of environmental pollutants, such as dioxins and chlorophenols. In this study, PrP Res was treatedby 14 white-rot fungi and 1 brown-rot fungus. The PrPRes was completely degraded by 8 white-rot fungi, and allthese fungi produced manganese peroxidase (MnP) during the treatment. The crude extracellular enzyme alsodegraded PrPRes in the condition containing Mn( II ) and H2O2. These results support that MnP is a key enzyme
for PrPRes degradation.
2004-P01
LCC の両親媒的性質
臼倉ゆり子、植木飛鳥、浦木康光、岸本崇生、生方 信
北海道大学大学院農学研究科
Amphiphilic characteristics of LCC
Yuriko Usukura, Asuka Ueki, Yasumitsu Uraki, Takao Kishimoto, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
Lignin-Carbohydrate Complex (LCC) was isolated from wood meal residue with DMSO after
extraction of milled wood lignin (MWL). Transmission electron micrographs after negative staining indicatedthat LCC formed self-aggregates in water with diameters in the range of nano-meter. The aggregates revealed tohave strong hydrophobic domains by the fluorometric study of their complexes with fluorescent reagents as
indicators for hydrophobicity. The surface pressure (π)-area (A) isotherms of LCC also indicated self-assembly
and the possibihty of formation of LB film.
2004-P02
リグニン・炭水化物結合体の単離（IV)アカマツ材からの単離
池田 努、杉元倫子、田中良平、真柄謙吾、加藤 厚、細谷修二
森林総合研究所
Isolation of lignin-carbohydrate complexes. (IV). Application to red pine wood
Tsutomu Ikeda,Tomoko Sugimoto, Ryohei Tanaka, Kengo Magara, Atsushi Kato, Shuji Hosoya
Forestry and Forest Products Research Institute
Abstract:
Ozonation followed by acid hydrolysis was applied to red pine wood meal to isolate thebenzylic ether type lignin-carbohydrate bonds (LCC bonds). The yield of the acidic fraction which contained
LCC products was increased by extending ozonation and using weak anion exchange resin for anion exchange
chromatography. There were many products in the acidic fraction with similar retention time on GC
chromatogram after trimethylsilylation. Therefore, the identification of the products was difficult. It was
improved by applying acetylation instead of trimethylsilylation. Some peaks on GC chromatogram of thesamples from red pine wood showed the same retention time and the similar mass fragment pattern comparedwith the authentic compounds from LCC model compounds. These results suggested that benzylic ether type
LCC bonds existed in red pine wood.
410

2004-P03
ケナフの成熟段階と部位の違いによる化学成分の変化
金光笵*1、中川明子*1、大井 洋*1、黒田健一*2*1
筑波大学大学院生命環境科学研究科、*2 九州大学大学院農学研究院
Difference of chemical components of Hibiscus cannabinus bast and core between various maturation steps
Guang-Fan Jin*1, Akiko Nakagawa*1, Hiroshi Ohi*1, Ken-ichi Kuroda*2*1Graduate School of Life and Environmental Sciences, University of Tsukuba, *2Faculty of Agriculture, Kyushu
University
Abstract:
Hibiscus cannabinus plant grown in the Agricultural and Forestry Research Center at the
University of Tsukuba were separated into three parts (up, middle and bottom), and their bast and core parts
were subjected to lignin and carbohydrates analyses. The middle and bottom parts of the bast were treated undersoda-anthraquinone pulping and totally chlorine-free bleaching conditions, and the results were compared withthose from Acacia mearnsii.
2004-P04
SEC-UV-MALS 法を用いた針葉樹クラフトパルプの特性解析
柳澤正弘、磯貝 明
東京大学大学院農学生命科学研究科
SEC-UV-MALS analysis of softwood kraft pulp
Masahiro Yanagisawa, Akira Isogai
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Various cellulose and pulp samples including softwood kraft pulp (SKP) were dissolved in 8%
lithium chloride/1,3-dimethyI-2-imidazolidinone (LiCl/DMI) and 8% LiCl/N,N-dimethylacetamide(LiCl/DMAc), and the obtained solutions were analyzed by size-exclusion chromatography equipped withultraviolet and multi-angle light scattering detectors (SEC-UV-MALS). The conformation analysis using 1%
LiCI/DMI as an eluent revealed that some compact structures consisting of cellulose, hemicellulose and lignin
are present in the high MM part of SKP/LiCl/DMI. This structure was not broken by bleaching or removal oflignin, while it was susceptible to acid treatments and -1,4-mannanase treatments. Thus, glucomannan seems to
be a key component of the structure.
2004-P05
分轄添加型ラボ蒸解装置を用いたキノン蒸解法の検討
田中潤治
川崎化成工業株式会社
Studies on quinone cooking using laboratory cooking equipment applied to modified cooking processes
Junji Tanaka
Kawasaki Kasei Chemicals Co., Ltd
Abstract:
Quinone has been used as a cooking additive in many KP mills. This paper shows how quinone
is applied to recent modified cooking processes. In order to make conditions of laboratory test similar to theones of a real digester, we developed a small scale digester in which addition and extraction of cooking liquors
are possible. Using this equipment, the following results became clear.
1. Addition of quinone at the top of digester is most effective. The effect of quinone is decreased if it is added
after the start of cooking. 2. The amount of extracted SAG (solution-type quinone) from a digester
accompanying the extraction of black liquor is very small. But the large amount of AQ (slurry-type quinone) is
extracted under the lower concentration of active alkali.
2004-P06
摩砕によるリグニン構造の変化について
藤本 文*1、松本雄二*1、Hou-min Chang*2、飯塚堯介*1*1
東京大学大学院農学生命科学研究科、*2North Calorina state University
Changes of lignin structures caused by milling
Aya Fuiimoto*1, Yuji Matsumoto*1, Hou-min Chang*2, Gyosuke Meshitsuka*1*1Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2North Carolina State University
Abstract:
In this paper, we tried to investigate the effect of milling on the structural change of lignin under411

various milling conditions. Milled woods prepared under different conditions were analyzed by ozonation
method 4). Both the content of β-O-4 structure and the diastereomer ratio (erythro / erythro + threo) decreased
with the progress of milling. It was found that lignin undergoes the same degree of structural change whenwoods were milled to the same extent regardless of the difference of milling condition.
2004-P07
リグニン構造論におけるオゾン分解法の最近の展開
松本雄二
東京大学大学院農学生命科学研究科
Recent contribution of ozonation method to structural analysis of lignin
Yuji Matsumoto
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Recent development of ozonation method and its contribution to lignin chemistry is reviewed.
The presence of simple relationships between stereo structure of β-O-41inkage and aromatic ring type has beensuggested. This relationship seems to be valid not only to woods but also to lower plant. Stereo preferential
reactions of lignin during many kinds of chemical and mechanical treatments were detected by ozonation
analysis.
2004-P08
腸内細菌に対するリグニンの影響
藤加珠子、野田博行
生物ラジカル研究所
Effect of lignin on the growth of enterobacteria
Kazuko Toh, Hiroyuki Noda
Institute for Life Support Technology
Abstract:
Several kinds of enterobacteria were cultured with the medium containing lignin that had been
derived from rice bran. Lignin was metabolized by Escherichia coli and Staphylococcus epidermidis. In themedium with lignin, the growth of Lactobacillus acidophilus and Streptococcus intermedius was augmented. On
the other hand, the growth of other enterobacteria such as
Escherichia coli was supressed.
2004-P09
脱水素重合時におけるシンナミルアルコール類と 4-クロロアニリンとの反応
蓮見実理恵*1、中川明子*1、富田文一郎*1、黒田健一*2*1
筑波大学大学院生命環境科学研究科、*2 九州大学大学院農学研究院
Structural elucidation of chloroaniline-lignin matrix by pyrolysis-gas chromatography with on-line methylation
Mirie Hasumi*1, Akiko Nakagawa-izumi*1, Bun-ichiro Tomita*1, Ken-ichi Kuroda*2*1Graduate School of Life and Environmental Sciences, University of Tsukuba, *2Graduate Schools of
Agriculture, Kyushu University,
Abstract:
Agrochemicals containing organochlorine compounds remain in soil. These compounds areincorporated into lignin and humic acid. In order to clarify the fate of organochlorine compounds, bulk guaiacyland syringyl dehydrogenative polymers (DHPS) were prepared in the presence and absence of 4-chloroaniline,
and analyzed with on-line methylation pyrolysis gas chromatography/ mass spectrometry using
tetramethylammonium hydroxide (TMAH), TMAH-Py- GC/MS. In TMAH-Py-GC/MS of coniferyl
alcohol-DHP incorporating chloroaniline, (4-chloro- phenyl)-[1-(3,4- dimethoxyphenyl)-2,3-dimethoxypropyl]
amine was detected as a pyrolysis product; a similar syringyl product was obtained from TMAH-Py-GC/MS ofsinapyl alcohol/chloro -aniline-DHP. In TMAH-Py-GC/MS of DHPs incorporating chloroaniline, the amountsof β-O-4 substructure- derived products, erythro/threo-1-(3,4-dimethoxyphenyl)-1,2,3-tri-methoxy- propane
and 1-(3,4,5- trimethoxyphenyl)-1,2,3-trimethoxypropane, were greatly decreased compared to those from
DHPs without chloroaniline. The pyrolysis results directly proved that the incorporation of 4-chloroaniline into
the Cα-position of arylglycerol-β-guaiacyl ether substructures.
2004-P10
スギリグニンの熱分解における各種単位構造の役割
河本晴雄、中村健史、坂 志朗
412京都大学大学院エネルギー科学研究科
Role of substructure in pyrolysis of Japanese cedar lignin
Haruo Kawamoto, Takeshi Nakamura, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
To elucidate the pyrolysis behavior of lignin in wood, pyrolysis behavior of milled wood lignin(MWL) isolated from Japanese cedar (Cryptomeria japonica) was studied at 200-400ºC in nitrogen. As a result,condensation preferentially occured at 200-300ºC rather than depolymerization, substantial depolymerization
started at 300-350ºC, and carbonization started at 350-400Qc. Methylation of the OH groups stabilized the
MWL sample for condensation as indicated by raising the condensation temperature by 50-100ºC, while themethylation did not change the reactivities of depolymerization and carbonization. With the results of dimericmodel compounds, role of the substructure in lignin in these pyrolysis behaviors is also discussed. These results
will give useful suggestions for controlling the product selectivity, low molecular weight substances vs. char,from lignin in wood.
2004-P11
リグノフエノールエポキシ樹脂の合成と物性
八木雅史、梶山幹夫、富田文一郎
筑波大学大学院生命環境科学研究科
Synthesis and properties of lignophenol/epoxy resins
Masashi Yagi, Mikio Kajiyama, Bunichiro Tomita
Graduate School of Life and Environmental Sciences, University of Tsukuba
Abstract:
Lignophenol/epoxy resins were prepared from lignophenols (LP), epoxy compounds (E), andtriethylene tetramine. They were prepared at various weight ratios of LP and E, LP/E, and various molar ratios
of N-H and epoxy group, [NH]/[Epoxy]. N,N-dimethylformamide (DMF) solubility and the viscoelastic
properties of cured resins were investigated. The solubility of DMF increased with increasing LP/E ratios. The
resins with LP/E=1/1 and [NH]/[Epoxy]=0.5 had the highest peak temperature of loss modulus. The breadth of
the temperature-modulus curve in the transition region was estimated quantitatively according to the Kwei's
equation which indicates the, steepness of the dispersion curve.
2004-P12
アカマツ硫酸リグニンのレゾルシノール化
今井将徳、松下泰幸、今井貴規、福島和彦
名古屋大学大学院生命農学研究科
Resorcinolization of red pine sulfuric acid lignin
Masanori Imai, Yasuyuki Matsushita, Takanori Imai, and Kazuhiko, Fukusima
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
To enhance the reactivity and the solubility of sulfuric acid ligmin (SAL), treatments withresorcinol in the presence of 72% sulfuric acid catalyst were performed. When resorcinol concentration was
sufficiently high, resorcinolized sulfuric acid lignin with higher solubility to organic solvent was obtained.
Compared with phenolization of SAL, larger amount of acid soluble fraction of reaction product was yielded.
But molecule weight of resorcinolized product was larger than that of phenolized one. This may be interpreted
that decomposed SAL was re-polymerized during the resorcinolized reaction.
2004-P13
ヒラタケにおける多機能型ペルオキシダーゼ MnP2 組換え遺伝子の発現
月原多佳久、本田与一、渡邉崇人、渡辺隆司
京都大学生存圏研究所
Expression of recombinant versatile peroxidase MnP2 in Pleurotus ostreatus
Takahisa Tsukihara, Yoichi Honda, Takahito Watanabe, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University
Abstract:
Pleurotus ostreatus secrets an unique peroxidase, MnP2 predominantly in low nitrogencondition. MnP2 can oxidize not only Mn2+ but also non-phenolic and high-molecular weight compounds
directly [1]. To express MnP2, we made expression plasmid containing the coding sequence of mnp2 between P.
ostreatus sdi1 promoter and terminator sequences and introduced the plasmid to P. ostreatus. We isolated 33
transformants containing the recombinant mnp2 sequence. Through screenings for elevated decolorizing activity
413

of Poly R-478, one of the recombinants, TM2-10 was selected. On a synthetic medium containing 15 mM
ammonium oxalate, specific expression of rMnP2 by TM2-10, but not wild-type control, was demonstrated withanion- exchange chromatography.
2004-P14
白色腐朽菌 Ceriporiopsis subvermispora の産生するジカルボン酸 ceriporic acid B アナログの合成と機能解析
菅 祥彦、大橋康典、渡邉崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Synthesis and functional analysis of dicarboxylic acid, ceriporic acid B produced by a white rot fungus
Ceriporiopsis subvermispora
Yoshihiko Kan, Yasunori Ohashi, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University
Abstract:
Previously, we reported that 1-nonadecene-2, 3-dicarboxylic acid (ceriporic acid B,
NDA) inhibited production of •OH by the Fenton reaction. The present research aimed at elucidating effects of
the alkyl side chain of this metabolite on iron redox reactions and the Fenton reaction. To discuss on the
structure-function relationship, we synthesized 1-undecene-2, 3-dicaroboxylic acid (UDA), an analogue of
ceriporic acid B. Using UDA, NDA and itaconic acid, we analyzed surfactant activities, suppression of Fe 3+
redox reaction and inhibition of •OH production. As a result, we found that UDA suppressed •OH production by
the Fenton reaction less effectively than NDA. No inhibitory effects were found for itacomic acid. These results
indicate that chain length of the alkyl side chain is a key factor for controlling iron redox reactions andinhibition of •OH production by the Fenton reaction.
2004-P15
担子菌カワラタケの遺伝子組換えによるラッカーゼの高生産梶田真也*1、宮崎安将*2、中村雅哉*2、片山義博*1、飯村洋介*３*1
東京農工大学大学院 BASE、*2 森林総合研究所、*３産業技術総合研究所
Overproduction of recombinant laccase using a homologous expression system in Coriolus versicolor
Shinya Kajita*1, Yasumasa Miyazaki*2, Masaya Nakamura*2, Yoshihiro Katayama*1, Yosuke Iimura*3*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Forestry and Forest Products Research Institute, *3National Institute of Advanced Industrial
Science and Technology
Abstract:
One of the major extracellular enzymes of the white-rot fungus Coriolus versicolor is laccase,which is involved in the degradation of lignin. We constructed a homologous system for the expression of agene for laccase III in C. versicolor using a chimeric laccase gene driven by the promoter of a gene forglyceraldehyde-3-phosphate dehydrogenase from this fungus. We transformed C. versicolor successfully byintroducing both a gene for hygromycin B phosphotrans- ferase and the chimeric laccase gene. We examined
one of the transformants that had the highest laccase activity and found that its activity was significantly higher
than that of the wild type.
2004-P16
マンガンペルオキシダーゼによる変異原性物質の分解と無毒化
待井芳晴、平井浩文、河合真吾、西田友昭
静岡大学農学部
Degradation and detoxification of mutagen by manganese peroxidase
Yoshiharu Machii, Hirofumi Hirai, Shingo Kawai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
3-Tert-butyl-4-hydroxyanisole (BHA), which is a phenolic compound widely used as anantioxidant for foods and cosmetics, displays both mutagemic and estrogenic activities. Therefore, weinvestigated whether manganese peroxidase (MnP) can degrade and remove the mutagenic activity. BHA
completely disappeared in the reaction mixture after a 24-h treatment with MnP, and the mutagenic activity of
BHA was also completely removed. These results indicate that the MnP is effective in degradation anddetoxification of BHA. The GC-MS analyses indicated that the major metabolite of BHA is
2,2'-dihydroxy-5,5'-dimethoxy-3,3'-di-tart-butylbiphenyl (M1).
414

2004-P17
白色腐朽担子菌による塩素化ダイオキシン類の分解特異性*1
亀井一郎、*２近藤隆一郎*1
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院
Specificity for the degradation of polychlorinated dioxins by white-rot fungi
Ichiro Kamei*1, Ryuichiro Kondo*2*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University
Abstract:
The model compounds of polychlorinated dibenzo-p-dioxins (PCDDs), 2,7-dichloro-,
2,3,7-trichloro, 1,2,6,7-, I,2,8,9-, 1,3,6,8-tetrachlorodibenzo-p-dioxin and the model compounds ofpolychlorinated dibenzofuran, 2,8-dichloro, 2,4,8-trichlorodibenzofuran were used as substrate for degradation
experiment by white-rot fungi Phlebia lindtneri, and Phlebia brevispora. In the cultures treated with P. lindtneri,
the degradation rate of 1,2,6,7-tetraCDD was higher than that of 2,3,7- triCDD, and no degradation of
1,3,6,8-tetraCDD was observed. These results indicate that the degradation of PCDDs depend more strongly
chlorinated position than the number of chlorinated substituents. Degradation rate of polychlorinateddibenzofuran was lower than that of polychlorinated dibenzo-p-dioxin. On the other hand,
1,3,6,8-tetrachlorodibenzo-p-dioxin, 2,8- dichloro, and 2,4,8-trichlorodibenzofuran were degraded by P.
brevispora. Monohydroxylated and monomethoxylated compounds were detected as metabolite from thecultures treated with P. brevispora.

415

第 50 回 （2005.10.19-20） 名古屋大学 野依記念学術交流館
2005-101
マツ木部組織における過ヨウ素酸リグニンの ToF-SIMS 測定
斉藤香織*1、寺島典二*2、加藤俊之*3、福島和彦*1
１
名古屋大学大学院生命農学研究科、２名古屋、３名古屋大学全学技術センター
Investigation of periodate lignin from Pinus thunbergii xylem using ToF-SIMS
Kaori Saito*1, Noritsugu Terashima*2, Toshiyuki Kato*3, and Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, *22-61 0 Uedayama, Tenpaku, Nagoya,*3
TechnicaI Center, Nagoya University
Abstract:
Periodate lignin structures of the differentiating xylem of normal and compression wood of pine
were investigated using time-of-fright secondary ion mass spectrometry (ToF-SIMS). In a previous study, themorphological features of lignin have shown to be retained after the removal of polysaccharides by periodate
oxidation. Xylem tissue samples were pre-methylated with CH2N2 to protect free-phenolic groups in lignin fromundesirable oxidative modification, and then were treated with periodate. The spectra of compression wood
treated with periodate showed both the ions derived from units having free-phenolic groups and the ions derived
from lignin units having a methylated phenolic hydroxyl group at m/z 165 for guaiacyl and at m/z 135 forp-hydroxyphenyl units. Comparison of the ToF-SIMS spectra of untreated, CH2N2-treated, andCH2N2-periodate- treated samples gave a good explanation for the behavior of periodate oxidation observed inintact xylem tissues of wood.
2005-10213
C 標識テトラメチルアンモニウムヒドロキシドを用いた熱分解—メチル化によるリグニンの分析
黒田健一*1、中川明子*2、T. R. Filley*3*1
九州大学大学院農学研究院、*2 筑波大学大学院生命環境科学研究科、*3Purdue University
１3
C-Labeled tetramethylammonium hydroxide (TMAH) thermochemolysis of lignin
Ken-ichi Kuroda*1, Akiko Nakagawa-izumi*2, Timothy R. Filley*3*1Graduate School of Agriculture, Kyushu University, *2Graduate School of Life and Environmental Sciences,
University of Tsukuba, *3Department of Earth and Atmospheric Sciences, Purdue University
Abstract:
A bulk dehydrogenation polymer of coniferyl alcohol (G-DHP) and a Japanese ceder wood
were methylated with diazomethane and subjected to 13C-labeled tetramethylammonium hydroxide(13C-TMAH) thermochemolysis (315ºC/4s). Products having diazomethane- and analytically-added methylgroups were transferred to GC/MS. MS data of the products showed that (1 ) veratrylaldehyde (2),,3,4-trimethoxystyrene (5) extensively stemmed from nonphenolic -aryl ether subunits, and1-(3 ,4-dimethoxyphenyl)-1,2,3-trimethoxypropane (7) stemmed from both phenolic and nonphenolic -aryl
ether subunits, (2) the DHP had phenolic guaiacylglycerol moieties involved in -aryl ether linkages in a larger
abundance than nonphenolic ones, in contrast to the wood lignin, (3) coniferyl alcohol dimethyl ether (6)observed in the DHP pyrogram stemmed from 4-O-etherified coniferyl alcohol and 6 produced from the wood
stemmed from both 4-O- and C-O-etherified corliferyl alcohols in roughly equal amounts, (4) pinoresinol
dimethyl ether (11) showed the M+ ions both at m/z 387 and m/z 388 in a roughly 1:2 signal intensity ratio,suggesting that 1/3 β-β subunits are present at the terminal of the DHP network, and (4) stilbenes 8-10 showed
the molecular ion at m/z 373, suggesting that these stem from terminal -5 subunits.
2005-103
酸性条件下におけるリグニン β-O-4 結合解裂機構の再評価（１）
横山朝哉、松本雄二、飯塚堯介
東京大学大学院農学生命科学研究科
Reinvestigation of the mechanism of lignin β-O-4 bond cleavage under acidic conditions (1) -Experiments using
C6-C2 model compounds
Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
Acidolysis of lignin containing materials has widely been applied as a method for
isolation as well as structural analysis of lignin. The most important chemical reaction in these methods is thecleavage of β-O-4 bond in lignin. Although the mechanism of the cleavage has been postulated, it seems not to
be rationale when the known phenomenon, the rate of the cleavage is dependent on the concentration and kind416

of acid, is taken into consideration. The objective of this research is to propose a more rationale mechanism forthe cleavage of lignin β-O-4 bond in acidolysis and to examine its kinetic in detail. To avoid complexities of thereaction caused by the presence of γ-hydroxymethyl group, a C6-C2 model compound was used in this paper.
The model was subjected to an acidolysis under various conditions and its degradation and kinetic were
thoroughly examined.
2005-104
モノリグノール配糖体の HRP 触媒脱水素重合
飛松裕基、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
HRP catalyzed dehydrogenative polymerization of monolignol glucosides
Yuki Tobimatsu, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Graduate School of Agriculture, Kyoto University
Abstract:
High yields synthesis of (E)-isoconiferin, (E)-triandrin and (E)-isosyringin, which had ahydrophilic D-glucose unit on their  positions of the respective monolignols, were established and their HRP
catalyzed polymerizations in homogeneous systems were conducted. Under optimum conditions, isoconiferin
and triandrin gave polymers with DPn = 42-47 in high yields,
while the DPn of conventional DHPs were around 10. But the polymerization of isosyringin gavea polymer in ony 28% yield and the DPn of the polymer was in the same range with that of DHP from sinapyl
alcohol. The copolymerization of isosyringin and isoconiferin, however, gave a copolymer with DPn = 27 in
80% yield.
2005-105
形質転換樹木リグニンの迅速分析 −透過型近赤外分光法の応用−
山田竜彦*1*2、Ting-Feng Yeh*1、Hou-min Chang*1、John F. Kadla*3、Laigeng Li*1、Vincent L Chiang*2*1
ノースカロライナ州立大学, *2 森林総合研究所、*3 ブリティッシュコロンビア大学
Rapid analysis of transgenic tree lignin, Application of transmittance near infrared spectroscopy
Tatsuhiko Yamada*1*2, Ting-Feng Yeh*1, Hou-min Chang, *1 John F. Kadla*3, Laigeng Li*1, Vincent L Chiang*1*1
North Carolina State University, *2Forestry and Forest Products Research Institute, *3University of British
Columbia
Abstract:
Our extensive functional genomic research on lignin biosynthesis has produced highly
improved transgenic trees. To efficiently monitor and control the properties of the transgenic products a rapid
mini scale analytical method is required. Transmittance near infrared (NIR) spectroscopy was chosen as a rapid
lignin analysis tool. Pellets were prepared from 75 mg of wood meal and directly scanned. Very strong
correlations were obtained between the conventional wet chemistry results and the NIR data for lignin content
and S/G ratio. The results indicate that transmittance NIR is a powerful tool for determining and screening thechemical properties of transgenic trees.
2005-106
酸素処理過程におけるリグニン構造変化の赤外分光法による解析（４）−酸素処理に抵抗性を示すフェノール類の生成について−
矢田実、飯塚堯介
東京大学大学院農学生命科学研究科
Infrared study of structural changes of lignin during oxygen treatment : part 4. Generation of resistant phenolic
structure to oxygen treatment
Minoru Yada, Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
For the fundamental study of oxygen delignification of kraft pulp, structural changes of kraft
lignin during alkaline oxygen treatment was studied. At the early phase of the treatment, not only the generationof muconate substructure but the generation of some resistant phenolic substructures toward the treatment weresuggested from the measurement of UV-VIS spectra at various pH. Furthermore formation of carbonyl groups
was indicated by the time series analysis of infrared ATR spectra. Correlation analysis between this carbonylband and other infrared bands under pH perturbation indicated that a part of carbonyl groups should be
conjugated with phenolic substructure. In addition, the time series analysis of 1H-NMR indicated that changes ofthe structural circumstance of a methoxyl group were occurred by the modification of a side chain part of lignin
417

structure. These three results could be explained by the generation of a phenolic substructure conjugated with acarbonyl group, and o-vanillin type phenolic structure formed by the olefinic side chain cleavage of op-stilbene moiety can be a possible structure. Here, a stilbene structure should be generated from a phenolic
phenylcoumaran moiety as the result of kraft cooking.
2005-107
美唄泥炭湿地からの水溶性有機物の分析
勝亦京子、Zhenfu Jin、堀啓映子、飯山賢治
東京大学大学院農学生命科学研究科
Chemical feature of dissolved organic matter from Bibai swamp
Kyoko S. Katsumata, Zhenfu Jim, Keeko Hori, Kenji Iiyama
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Water passed through peat swamp colored in brown to dark brown by dissolving organic
matters (DOM). When the DOM in water now in ocean, such DOM could form chelates with metal ions inocean water. The chelates would be insoluble in ocean water, and accumulate at the ocean bed as sediments.
Lignin, which is significantly resist to biological decomposition, is the major component of DOM, has highability of chelate formation. The behavior of water-soluble lignin is significantly important factor for global
carbon circulation, but quite limited information is available. We started to investigate to make clear chemical
structure of water-soluble lignin under natural condition and reaction under global system. The DOM wasisolated from water at Bibai peat swamp in Hokkaido, the chemical feature of the DOM was analysed using
some wet and spectrometric analyses. The major component of DOM would be highly modified lignin by
activities of microorganisms.
2005-108
Characteristics of bast and core lignins of kenaf (Hibiscus cannabinus) and mulberry (Morus bombycis)
Zhenfu Jin、Kenji Iiyama
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Structural characteristics of bark and core lignins from kenaf (Hibiscus cannabinus), paper
mulberry (Broussonetia kazinoki) and mulberry (Morus bombycis) were examined. All of bark fractions gave
lower Klason lignin contents than those of core fractions. Kenaf bark exhibited significantly high S/V molar
ratio. High ratio of elythro- to threo-form (E/T ratio) of β-O-4 structure in lignin o kenaf bark was confirmed byboth ozonation and 1H-NMR analysis. Lignin structure of kenaf bark was comparable to core lignin while paper
mulberry and mulberry bark exhibited quite different lignin characteristics comparing to core lignin.
2005-109
Feasibility of branch of young Acacia mangium Willd as raw material for pulp and paper manufacture
Ridwan Yahya*1*2, Takuya Akiyama*2、Gyosuke Meshitsuka*2, Yuji Matsumoto*2*1
Bengkulu University, *2Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
To examine the feasibility of branch of Acacia mangium with diameter less than 8 cm as a raw
material for pulp production, we carried out a systematic fundamental study. Those branches are usually left on
the ground as logging wastes in a plantation. Based on their chemical composition and fiber dimensions, weconcluded that the quality of branches of A. mangium is as good as its trunks as raw materials for pulp and paper
production. It was also suggested that yield and qualities of pulps might not be spoiled significantly even if
branches with bark are subjected to pulping with trunks.
2005-110Ozone bleaching for the low-kappa- number kraft pulp of wheat straw
Miaomiao Cao*1, Guolin Tong*1, Guoxin Xue*1*2*1Nanjing Forestry University, *2Zhejiang University of Science and Technology
Abstract:
This study has investigated the ozone bleaching for low-kappa-number kraft pulp of wheat
straw, and the low-kappa- number kraft pulp was produced by the one stage extended delignification technology.
Results showed 86.9% (SBD) brightness of bleached pulp could be achieved and the viscosity of the pulp could
be S51ml/g after the AZEYP bleaching sequences. Lignin is the natural protector to carbohydrate. The Ozone
delignification is important and benefit for TCF bleaching.
2005-111
418

Synthesis and properties of cationic lignin surfactant
Yiqin Yang, Guolin Tong, Zhongzheng Li
College of Chemical Engineering, Nanjing Forestry University
Abstract:
Cationic lignin surfactant was synthesized by reacting kraft lignin with quaternary ammonium
salt cationic 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTMAC). The effects of CHPTMAC
dosage, NaOH dosage, reaction temperature and reaction time on the surface activity, nitrogen content andsolubility of cationic lignin surfactants were studied. The results indicated the suitable synthesis conditions ofcationic lignin surfactant were as follows: the dosage of quaternary ammonium salt (CHPTMAC) was 4 mol/kg
lignin, the molar ratio of NaOH to quaternary ammonium salt agent was 1.3, reaction temperature was 50ºC andreaction time was 4 h. Synthesized cationic lignin surfactant had good solubility under different pH value, thehighest nitrogen content was 2.57% and the lowest surface tension of them was reached 42.7 mN/m.
Keywords: kraft lignin, quaternary ammonium salt, cationic lignin surfactant, nitrogen content, surfactivity.
2005-112
リグニンを含有するヒドロキシプロピルセルロースゲルの熱的性質とゲスト分子との相互作用
浦木康光、井村健、岸本崇生、生方信
北海道大学大学院農学研究科
Thermal property of hydroxypropylcellulose bearing lignin gel and its interaction with guest molecules
Yasumitsu Uraki, Takeshi lmura, Takao Kishimoto, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
Hydroxypropylcellulose bearing lignin (HPC-L) was prepared from unbleached acetic
acid pulp of Todo-fir. The pulp derivative was converted to hydrogel with ethyleneglycol diglycidyl- ether as acrosslinker. The resultant gel showed exothermic peak in differential scanning calorimetry, of which temperature
was consistent with that of gel shrinking. The temperature was elevated by adsorption of ionized dye. Thus, thethermal property was altered by the interaction with guest molecules. In addition, the gel showed different
swelling behaviors upon interaction with ionic and nonionic surfactants.
2005-113
HBS パルプ化の実証試験—リグニン利用の可能性—
生方信*1、植木飛鳥*1、三橋進也*1、岸本崇生*1、浦木康光*1、藤田進一郎*2*1
北海道大学大学院農学研究科, *2 北海道大学大学院工学研究科
Verification test of HBS-pulping: Possibility of lignin utilization
Makoto Ubukata*1, Asuka Ueki*1, Shinya Mitsuhashi*1, Yasumitsu Uraki*1, Shinichiro Fujita*2*1
Gradtlate School of Agriculture, Hokkaido University, *2Gradtlate School of Engineering, Hokkaido University
Abstract:
Y. Sano et al. developed the HBS-pulping method that could operate even on a small scale at anative locality of woody biomass. We undertook a verification test of this method including HBS pulping ofsoftwood and agricultural husks, preparation of monosaccharide by pre-hydrolysis, enzymatic saccharization of
HBS pulp, quality of silica contained in agricultural husks, preparation of fiberboard, appliation of HBS lignin
to medical field, feasibility study and conceptual design of HBS- pulping process. In this symposium, we report
the results of the verification test of HBS pulping from the point of view of lignin utilization.
2005-114
酢酸リグニン/合成ポリマー複合体の調製と分子間相互作用の評価
寺本好邦、田中紀子、遠藤貴士
産業技術総合研究所
Preparation and characterization of intermolecular interaction of organosolv lignin, acetate / synthetic polymer
composites
Yoshikuni Teramoto, Noriko Tanaka, Takashi Endo
National Institute of Advanced Industrial Science and Technology
Abstract:
Binary blends and pseudo complexes of organosolv lignin, acetate (OSL-Ac) with poly(N-vinyl
pyrrolidone) were prepared, respectively, by casting from mixed polymer solution in N,N-dimethylformaide as
good solvent and by spontaneous co-precipitation from solutions in tetrahydrofuran as comparatively poor
solvent. Fourier transform inbred meastwements revealed
the presence of rather stronger hydrogen-bonding interactions between hydroxyls of OSL-Ac and carbonyls of
N-vinyl pyrrolidone units for the complexes than those for the blends. Thermal transition data obtained by419

differential scanning calorimetory suggested that the blends are miscible,
whereas, for the complexes, a high frequency of interactions combined OSL-Ac with PVP intimately in thecomplexes to reduce the mobilities of the individual polymer chains.
2005-115
リグニンベースのポリイオンコンプレックスの調製と機能開拓
長谷川大輔*1、寺本好邦*2、西尾嘉之*1*1
京都大学大学院農学研究科、*2 産業技術総合研究所
Preparation and functionalization of lignin-based poly-ion complex
Daisuke Hasegawa*1, Yoshikmi Teramoto*2, Yoshiyuki Nishio*1*1Graduate School of Agriculture, Kyoto University, *2National Institute of Advanced Industrial Science andTechnology
Abstract:
Poly-ion complexes of anionic lignosulfonic acid (LSA) with cationic poly(2-vinyl pyridine) orpoly(4-vinyl pyridine) were prepared by spontaneous precipitation from solutions in dimethyl sulfoxide or
diluted hydrochloric acid. Fourier transform infrared measurenent8 for the complexes revealed the presence ofstrong ionic interactions between sulfonic anion of LSA and pyridimium cation of vinylpyridine (VPy) polymer.
The emergence of the strong interaction was supported by striking elevation of glass transition temperature indifferential scanning calorimetry
measurements. Subsequently, thin-layered coating of lignin on VPy polymer films was conducted successfully
to vary their surface property, as evidenced through visualization of the LSA component by atomic force
microscopy.
2005-116
リグニンベース木質粒子分散型ポリウレタン複合体パネルの調製と物性
畠山兵衛*1、南保貴士*1、廣瀬重雄*2、畠山立子*3*1
福井工業大学工学部、*2 産業技術総合研究所、*3 リグノセルリサーチ
Preparation and mechanical properties of wood panel with lignin-based polyurethane composites
Hyoe Hatakeyama*1, Takashi Nanbo*1, Shigeo Hirose*2, Tatsuko Hatakcyama*3*1
Fukui University of Technology, *2National Institute of Advanced Industrial Science and Technology*3
Lignocell Rcscarch Co.
Abstract:
Wood panels with kraft lignin (KL)-based polyurethane (PU) compsites were prepared using
three kinds of ethylene glycols, such as diethylene glycol, triethylene glycol or polyethylene glycol. Wood
powder and coffee residue were used as fillers. Filler content (=filler/polyol, g/g) in KL polyol was varied from50 to 100 %. Apparent density and mechanical properties of wood panels with the above PU composites were
investigated as functions of filler contents and molecular mass of ethylene glycol. Flexural strength calibrated
with apparent density was correlated with filler content. For the panel with PU composites filled with wood
powder, the optimum point was observed at around filler content 70 to 80 %. Modulus of elasticity ranged from
3 to 6 GPa, suggested that panels obtained in this study are sufficiently strong for practical applications.
2005-特別講演
リグニン化学構造の不均一性
飯塚 堯介
東京大学大学院農学生命科学研究科
Structural heterogeneity of lignin
Gyosuke Meshitsuka
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract:
Structural heterogeneity seems to be a key to understand the real structure of lignin and to
discuss how lignin is deposited in the course of cell wall formation. Structure of lignin is believed to be nothomogeneous in wood, but to be different dependent on the tissues of wood fiber, vessel and ray cell, on the cellwall layers of middle lamella, primary wall and secondary wall, and even in a lignin molecule. In order tocharacterize a lignin in a particular layer of cell wall, the fractionation of disintegrated wood and the separationof differentiating xylem were introduced. By these methods, structural characteristics of lignin in the compound
middle lamella were obtained. It is well known that Milled Wood Lignin (MWL) does not represent whole
lignin in wood but is originated from the compound middle lamella at least in the case of hardwood MWL
obtained at the early stage of milling. Ozonation is truly epoc-making for the structural analysis of lignin, by
420

which stereostructural characteristics of lignin side chain part were obtained, and β-O-4 structure in lignin wasfor the first tine confirmed to be in a racemic form and optically inactive. It is also important to note thatsyringaldehyde ratio by alkaline nitrobenzene oxidation and erythronic acid ratio by ozonation are in a linear
relationship. Development of new and controlled degradation methods and advanced microscopic technologies
may open a new stage for the study of the structural heterogeneity of lignin.
2005-201
イネをモデルとした植物細胞壁形成過程に関する研究 ‐糖代謝系とシキミ酸経路、フェニルプロパノイド経路との共役、及びその遺伝子発現制御機構‐
中野仁美*1、佐藤かんな*1、間瀬浩平*1、半智史*2 、西窪伸之*1*3、北野秀己*4、船田 良*2、
梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 農工大院農学教育部、*3 理化学研究所植物科学研究センター、*4
名古屋大学生物機能開発利用研究センター
Study for the process of cell wall formation in rice plant. - Conjugation and regulation of gene expressions
among three metabolic pathways, carbohydrate metabolism, shikimate pathway and phenylpropanoid pathway
Yoshimi Nakano*1, Kanna Sato*1, Kohei Mase*1, Satoshi Nakaba*2,Nobuyuki Nishikubo*1*3, Hidemi Kitano*4,
Ryo Funada*2, Shinya Kajita*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Graduate School of Agriculture, Tokyo University of Agriculture and Technology, *3RIKEN Plant
Science Center, *4Bioscience wd Biotechnology Center, Nagoya University
Abstract:
Plant cell walls contain polysaccharides-linked hydroxycinnamoyl ethers (PHEs) which consistof the ester-linkages between hydroxycinnamic acid derivatives such as ferulic acid (PA), p-coumaric acid(pCA) and cell wall matrix polysaccharides. Those hydroxycinnamic acids, in the Gramineae, mainly compose
the ester linkages mainly with arabinoxylan or slightly with xyloglucan. They also compose ether-linkages withcell wall lignin units to form covalent ester-ether bridges between polysaccharides and lignins. A novel ricedwarf mutant Fukei 71 is found ectopically accumulating PHEs in the cell walls of internode pith parenchyma.
We have pursued molecular and genetic analyses with Fukei 71 in order to clear PHEs biosynthesis in rice.
2005-202
イネをモデルとした植物細胞壁形成過程に関する研究 -Glycosylphosphatidylinositol-anchored protein はイ
ネの細胞壁高次構造形成にどのように関わるのか？
鈴木瑠*1、武内佐知*1、佐藤かんな*1、半智史*２、北野英己*３、船田良*２、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 農工大院農学教育部、*３名古屋大学生物機能開発利用研究センター
Study of plant cell wall formation in Oryza sativa L. -How does glycosylphosphatidylinositol -anchored protein
relate to cell wall conformation in rice plant (Oryza saliva L.)
Ryu Suzuki*1, Sachi Takenouchi*1, Kanna Sato*1, Satoshi Nakaba*2, Hidemi Kitano*3, Ryo Funada*2, Shinya
Kajita*1, Yoshihiro Katayama*1*1
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Graduate school of Agriculture, Tokyo University of Agriculture and Technology, *3Bioscienceand Biotechnology Center, Nagoya University
Abstract:
The advances in microscopy, molecular biology and genomics converged to make work easierfor biologists to study the mechanism and process of cell wall conformation. Many biologists used Arabidopsis
thatiana as a model plant to study cell wall conformation, and they revealed there are many genes involved inplant cell wall conformation. But few knowledge came out about detailed mechanism and process of wall
formation. In this study, we used brittle culm mutant called cwa1, recessive mutant rice plant (Oryza sativa L.),to obtain new information about plant cell wall conformation which are not revealed in Arabidopsis study.
2005-203
ゴマの機能性リグナン，特にセサミノールの生合成について
片山健至*1、小堀里恵*1、鈴木利貞*1、並木満夫*2、田代亨*3*1
香川大学農学部、*2 おいしさの科学研究所、*3 千葉大学園芸学部
Biosynthesis of functional lignans, particularly sesaminol, in Sesamum indicum seeds
Takeshi Katayama*1, Rie Kobori*1, Toshisada Suzuki*1, Mitsuo Namiki*2, Toru Tashiro*3*1
Faculty of Agriculture, Kagawa University, *2 Institute of Oishisa Science, *3Faculty of Horticulture, Chiba
University421

Abstract:
To clarify biosynthesis of sesaminol, one of the strongest antioxidant lignans in sesame seeds,
feeding experiments of L-[U-14C]phenylalanine (Phe) were carried out. A solution of
L-[U-14C]Phe (10mM, 20 l) was injected into unripe capsules of 11 week-old (after seeding) intact Sesamum
indicum plants cultivated in pots and then the plants were cultivated for a week at 26ºC. The order of the percent
incorporation of the radioactivity into the sesame lignans is as follows: sesamin > sesamolin > sesaminol ≥pinoresinol > 7-episesaminol. It was found for the first time that the radioactivity was clearly incorporated into
free sesaminol and 7-episesaminol in the seeds in a 100 : 8-9 ratio, but not into those in the pods. The percent
incorporation into sesamin, sesamolin, and (+)-pinoresinol, in the seeds was 5-38 times larger than that in thepods.
2005-204
MROMT に相同性の高い新規フラボノイド OMT について
中坪朋文*1、Laigeng Li*2、Vincent L. Chiang*2、服部武文*1、梅澤俊明*1*1
京都大学生存圏研究所、*2 ノースカロライナ州立大学
A novel flavonoid O-methyltransferase having a high sequence similarity to MROMT
Tomoyuki Nakatsubo*1, Laigeng Li*２, Vincent L. Chiang*２, Takefumi Hattori*1, Toshiaki Umezawa*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, *２College of Natural Resources, North
Carolina State University
Abstract:
Carthamus tinctorius maturing seeds produce various secondary metabolites such as lignans,lignin, flavonoids, and serotonin amides of cinnamates. Recently, Umezawa et al. reported the cloning of thenovel gene encoding lignan O-methyltransferase (matairesinol O-methyltransferase, CtMROMT) using
C.tinctorius maturing seeds. In addition, they cloned a cDNA which shows a high sequence similarity to
CtMROMT named CtMROMTlike. The present study identified the function of CtMROMTlike. Thus, therecombinant CtMROMTlike, expressed in E. coli, did not catalyze O-methylation of matairesinol, but catalyzed
O-methylation of a flavonoid, apigenin, indicating clearly that CtMROMTlike was flavonoid
O-methyltransferase (FOMT), but not MROMT.
2005-205
Arabidopsis thaliana の細胞分裂機構を用いた樹木資源の生産制御に関する研究
松井紀子*1、武内 佐知*1、西窪伸之*1*２、半智史*３、船田良*３、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*２理化学研究所植物科学研究センター、 *３農工大院農学教育部、Researchon production control of woody resources with cell division mechanisms of Arabidopsis thatiana
Noriko Matsui, Sachi Takenouchi, Nobuyuki Nishikubo, Satoshi Nakaba, Ryo Funada, Shinya Kajita, Yoshihiro
Katayama*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, *2Plant Science Center, RIKEN, *3Graduate School of Agriculture, Tokyo University of Agriculture
and Technology
Abstract:
The mechanisms by which plants modulate their growth rate in response to environmental anddevelopmental conditions are unknown, but are presumed to involve specialized regions meristems where cells
division is concentrated. In plant, as in other eukaryotes, the cell cycle consists of four different
phases-G1(gap1),S(DNA synthesis), G2(gap2),and M(mitosis) phases.
The G1/S transition generally represents the principal point of commitment to cell division. Many of thecomponents of the cell cycle core machinery regulating the G1/S transition in plant have been recently identified.
In this study, we examined regulation cell division in vascular cambium with G1/S related genes, AtE2F, AtDP,
AtCycD.
2005-206
植物ペルオキシダーゼの生理機能解明に向けたプロテオミクス
佐々木慎弥*1、江藤佑*2、志水元亨*３，割石博之*３、堤祐司*3、近藤隆一郎*３*1
九州大学大学院生物資源環境科学研究科、*２九州大学農学部、*３九州大学大学院農学研究院
Proteomic studies for physiological function of plant peroxidases
Shinya Sasaki*1, Yu Eto*2, Motoyuki Shimizu *3, Hiroyuki Wariishi *3, Yuji Tsutsumi *3, Ryuichiro Kondo *3*1Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Faculty of Agriculture,
Kyushu University, *3Graduate School of Agriculture, Kyushu University
Abstract:
Higher plants possess a large set of the classical plant peroxidases. These peroxidases are422

thought to participate in a wide rage of physiological functions. However, the most of them have been unclear.
Using proteomic analysis, we surveyed the localization of plant peroxidase in various organs in Populus alba L.
Peroxidase isoenzymes were extracted from the various organs and fractionated by a Concanavallin A Sepharosecolumn. Approximately 20 protein spots were detected by the two-dimensional electrophoresis gels. Someanionic peroxidase isoenzymes were identified via the PMF analysis. One of the anionic peroxidases would be
xylem and inner bark specific peroxidase.
2005-207
Phanerochaete crassa WD1694 の菌体外スライムと菌体外ペルオキシダーゼ活性染色について
高野麻理子、林 徳子
森林総合研究所
Slime of Phanerochaete crassa WD 1694 and its relationship to extracellular peroxidase activity staining
Mariko Takano, Noriko Hayashi
Forestry and Forest Products Research Institute
Abstract:
Distribution of slime of the white-rot fungi Phanerochaete crassa WD1694 was studied by amicroscope with phloxine B coloration and phase contrast technique. The slime was occurred inside of eachmycelial pellets grown in the shaken culture containing unbleached kraft pulp. Hyphal tips that caused
extracellular peroxidase staining did not had slime around the hyphae. Besides the strong coloration of
extracellular peroxidase staining at the hyphal tips and on the hyphae protruding from mycelial pellets, thestaining also occurred on the hyphae inside of the mycelial pellets and in slime among the hyphae. The results
suggested that the localization of extracellular peroxidase staining on the mycelium was mainly due to thegeneration of oxidant at the hyphal tips and on the hyphae, and was also caused by fungal slime that might keep
the generated oxodants.
2005-208
MnP による異常プリオンタンパク β−シート構造の分解
岩村翼*1、堤祐司*2、近藤隆一郎*2、松浦裕一*3、毛利資郎*3*1
九州大学大学院生物資源環境科学研究科、*２九州大学大学院農学研究院、*３九州大学大学院医学研究院
Degradation of β-sheet structure of protease-resistant prion protein by MnPTsubasa Iwamura, Yuji Tsutsumi, Ryuichiro Kondo, Yuichi Matsuura, Shirou Mohri*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2 Graduate School of
Agriculture, Kyushu University, *3Graduate School of Medical Science, Kyushu University
Abstract:
Protease Resistant Prion Protein (PrPRes) is a causual substance of bovine spongiform
encephalopathy (BSE) and other prion diseases. PrPRes has a high content of β-sheet structure, and can not be
degraded either by proteases or usual chemical treatments. Thus, convincing method for the decontamination of
PrPRes is urgently required. We reported that PrPRes was completely degraded by 8 white-rot fungi and it's crude
extracellular enzyme. In this study, we assessed the PrPRes infectious after the treatment by white-rot fungi.
When PrPRes was treated with Ceriporia lacerata MZ-340, intracerebral bioassay showed virtually no infectivity.
In addition, keratin that has a high content of β-sheet structure as well as PrPRes was also completely degradedby purified MnP from C. lacerata MZ-340. These results support that MnP produced by C. lacerata MZ-340
can degrade β-sheet structure.
2005-209
土壌浄化を指向した白色腐朽菌のスクリーニング
天野智絵、平井浩文、河合真吾、西田友昭
静岡大学農学部
Screening of white rot fungi aiming for soil remediation
Chie Amano, Hirofumi Hirai, Shingo Kawai, Tomoaki Nisida
Faculty of Agriculture, Shizuoka University
Abstract:
White rot fungus, tentatively named AG-200, which extensively degrades white birch (Betula
platyphylla var japonica) wood-lignin was isolated by using hardwood kraft pulp and agar medium containing
guaiacol. The partial sequencing data of 18S ribosomal DNA and the shape of fruit body suggested that thefungus AG-200 belongs to Amauroderma sp.. Great interest is currently being expressed in white rot fungi andtheir ligninolytic enzymes due to recognized potential for degrading and detoxifying recalcitrant environmental423

pollutants such as dioxins. For practical application of white rot fungus to soil remediation, it is important thatthe fungus is resistant to contamination by autochthonous microorganisms in soil. Thus, we investigatedwhether AG-200 can degrade wood-lignin under highly acidic condition (pH 2.5) in which the grow of
autochthonous microorganisms such as bacteria is inhibited. AG-200 had over 50% Klason lignin loss for 4
weeks of incubation under acidic and natural (pH 6) conditions, while the ligninolytic activities of
Phanerochaete sordida YK-624 and IZU-154 were influenced by pH and markedly decreased under acidic
condition. Therefore, it might be possible to use the acid-resistant fungus AG-200 for bioremediation of soil
contaminated with aromatic compounds. Practical application of AG-200 to soil remediation should be thesubject of a forthcoming study.
2005-210
リグニン分解酵素による 4-tert-オクチルフェノールのエストロゲン様活性除去
玉川祐基、平井浩文、河合真吾、西田友昭
静岡大学農学部
Removal of estrogenic activity of 4-tert-octylphenol by ligninolytic enzymes
Yuuki Tamagawa, Hirofumi Hirai, Shingo Kawai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka Universityan
Abstract:
4-tert-Octylphenol (4-TOP) is widely used in a variety of industrial and residential applications,and is suspected of having estrogenic (endocrine-disrupting) activity. Thus, 4-TOP was treated with the white
rot fungi, Phanerochaete sordida YK-624 and Trametes versicolor, under ligninolytic condition with
low-nitrogen and high-carbon culture medium. 4-TOP decreased by over 90% within 6 days of treatments withthe two fungi and the activities of ligninolytic enzymes, manganese peroxidase (MnP) and laccase, weredetected during treatment, which suggested that the disappearance of 4-TOP is related to ligninolytic enzymes
produced extracellularly by white rot fungi. Therefore, 4-TOP was treated with MnP and laccase prepared fromthe culture of white rot fungi. Using the yeast two-hybrid assay system, it was confirmed that both enzymatic
treatments completely removed the estrogenic activity of 4-TOP after 2 h. This result strongly suggests thatligninolytic enzymes are effective in removing the estrogenic activity of 4-TOP.
2005-211
白色腐朽菌 Phlebia brevispora による PCB の代謝変換
亀井一郎*1、其木茂則*2、原口浩一*3、近藤隆一郎*4*1
九州大学大学院生物資源環境科学研究科、*2 麻布大学環境保健学部、*3 第一薬科大学、*4 九州大学大学
院農学研究科
Fungal metabolism of polychlorinated biphenyls by white rot fungus Phlebia brevispora
Ichiro Kamei*1, Sigenori Sonoki*2, Koichi Haraguchi*3, Ryuichiro Kondo*4*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2College ofEnvironmental Health, Azabu University,*3Daiichi College of Pharmaceutical Science,*1Graduate School of
Agriculture, Kyushu University
Abstract:
The degradation of individual PCB congeners in the culture of Phanerochaete sordida,
Phlebia acerina, and Phlebia brevispora are examined. These fungi showed the different traits of degradation ofeach compounds. P. sordida showed any degradation of tested PCBs. P. acerina showed the degradation of
3,3',4,4'-tetraCB, although more chlorinated PCBs were not degraded. On the other hand, in addition to3,3',4,4'-tetraCB (#77), 2,3,3',4,4'-pentaCB (#105), 2,3',4,4',5-pentaCB (#118), 3,3',4,4',5-pentaCB (#126), and
2,3',4,4',5,5'-hexaCB (#167) were degraded by P. brevispora. By GC/MS analysis, methoxylated anddechlorinated metabolites were detected from the culture with these compounds. This is the first report on thebiotransformation of toxic coplanar PCBs by fungal strains.
2005-212
木材腐朽菌による PVA フィルムの分解
魯風*1、近藤隆一郎*2、二階堂祐子*3、岡 桂子*3、檜垣達彦*3*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究科、*3 クラレ くらしき研究所
Biodegradation of PVA film by wood-rotting fungiFeng Lu*1, Ryuichiro Kondo*2. Yuko Nikaido*3, Keiko Oka*3, Tatsuhiko Higaki*3*1Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University, *3Kurashiki Research Laboratories, Kuraray Co. Ltd.
424

Abstract:
A polyvinyl alcohol (PVA) film is used for the packing for food and fats, because it isindissoluble in water. Degradation efficiency of solid polymer is important in the viewpoint of material recycle.
The screening of wood-rotting fungi for the biodegradation of PVA film was examined. Although no white-rot
fungi degraded PVA film, one fungus in Gloeophyllum genus, G. trabeum degraded PVA film extensively. The
clarification of the degradation mechanism of PVA film by this fungus is now on progress.
2005-213
白色腐朽菌から抽出した酵素による Polychlorinated biphenyls (PCBs) 分解の試み
松尾保洋、藤井啓太、伊藤和貴、橘燦郎
愛媛大学農学部
Study on degradation of polychlorinated biphenyls with an enzymes from white rot fungi
Yasuhiro Matsuo, Keita Fujii, Kazutaka Ito, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Degradation of 3,3',4,4'-Tetrachlorobiphenyl (TCB) with crude enzymes from PL1 and the
enzymes isolated from the crude enzymes was investigated_ About 40% of TCB was degraded by the crude
enzynes in 48 hours in a liquid medium. Manganese peoxidase (MnP), Lignin peroxidase, Laccase and1,2-Dioxygenase were isolated from the crude ezymes by ion-exchange and gel filtration chromatography. By
the degradation of TCB with the isolated MnP in the liquid medium, about 7% of TCB was degraded in 24
hours. On the contrary, about 2% of TCB was degraded when the degradation of TCB with the immobilized
MnP was conducted for 24 hours in the liquid medium. From the results obtained here, it is suggested that MnPin the crude enzymes might not play an important role on the initial stage of degradation of TCB. Furthermore, adegradation pathway of TCB with the crude enzymes was proposed by confirmation of the intermediates.
2005 パネルディスカッション「リグニン研究の過去・現在・未来」
パネリスト：京都大学名誉教授 越島哲夫、名古屋大学名誉教授 寺島典二、京都大学名誉教授 樋口隆昌、
北海道大学大学院農学研究科 浦木康光、九州大学大学院農学研究院
堤祐司、 東京大学大学院農学生命科学研究科 横山朝哉
コーディネーター：名古屋大学大学院生命農学研究科 福島和彦
2005-P01
爆砕発酵処理バガスの抗酸化能と抗酸化性物質
大原誠資*1、橋田光*1、柏木豊*2、藤野哲也*3、稲福直*3、稲福盛雄*3*１
森林総合研究所、*２食品総合研究所、*3 琉球バイオリソース開発株式会社
Antioxidant activity of steam-exploded, fermented bagasse and related antioxidant substances
Seiji Ohara*1, Koh Hashida*1, Yutaka Kashiwagi*2, Tetsuya Fujino*3, Naoshi Inafuku*3, Seiyu Inafuku*3*1
Forestry and Forest Products Research Institute, *2National Food Research Institute, *3Ryukyu Bio-Resource
Development Co. Ltd.
Abstract:
We have been studying for utilization of bagasse as foodstuffs. In this study, it has been foundthat steam explosion of bagasse followed by fermentation is an effective pretreatment not only on the formationof xylooligosaccharides, but also on increase in antioxidant activity. In addition, we examined steam explosion
products of bagasse to elucidate the reaction mechanism causing the improvement of antioxidant activity. We
concluded the following. 1) Antioxidant activity of steam- exploded bagasse is attributed to low molecularweight polyphenols formed during steam explosion. 2) Ferulic acid shows high antioxidant activity, while
p-hydroxycinnamic acid and p-hydroxybenzoic acid don't. Ferulic acid is regarded as one of the compounds
responsible for antioxidant activity of steam-exploded bagasse.
2005-P02
ニセアカシアのシリンギルリグニン生合成経路の探索
植田幸恵*1、中坪朋文*２、梅澤俊明*２、堤祐司*３、近藤隆一郎*３*1
九州大学大学院生物資源環境科学研究科、京都大学生存圏研究所、*2 九州大学大学院農学研究科、
Search of syringyl lignin biosynthesis in black locust (Robinia pseudoacacia)
Yukie Ueda*1, Tomoyuki Nakatsubo*2, Toshiaki Umezawa*2, Yuji Tsutsumi*3, Ryuichirou Kondo*3*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Research Institute for
Sustainable Humanosphere, Kyoto University, *3Graduate School of Agriculture, Kyushu University
425

Abstract:
It was reported that administered sinapate was incorporated into syringyl lignin of Robinia
pseudoacacia and that 4CL isoenzyme in Robinia utilized sinapate unlike other plant 4CLs. These findings areindicative of an alternative route of syringyl lignin biosynthesis where sinapyl alcohol is biosynthesized passing
through sinapate and sinapoyl CoA. We therefore examined 4CL, ALDH, F5H, and COMT enzyme reaction inlignifying xylem of Robinia to investigate the biosynthetic pathways of syringyl lignin in Robinia. All the
enzymes possess a larger substrate preferences toward syringyl substrates compared to the enzymes in otherplant species ever reported. This result is an evidence for the presence of biosynthetic route of syringyl lignin
via sinapate.
2005-P03
MWL 抽出残さ木粉に存在するリグニンの性状
藤本文*1、高山雅人*1、松本雄二*1、飯塚堯介*1、Hou-min Chang*2*1
東京大学大学院農学生命科学研究科、*2 ノースカロライナ州立大学
Characteristics of lignin structures in MWL isolation residue (MWLR)
Aya Fujimoto*1, Masato Takayama*1, Yuji Matsumoto*1, Hou-min Chang*2, Gyosuke Meshitsuka*1*1Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Department of Wood and Paper
Science, North Carolina State University
Abstract:
Beech (Fagus crenata Blume) milled woods were extracted with dioxane/water (96 : 4, v/v).
The extracts were separated by centrifugation and the insoluble fraction was obtained as MWL isolation residue(MWLR). In this paper, the characterization of lignin in MWLR was tried out. The characteristics of lignin
structures in MWLR were analyzed by the ozonation method and alkaline nitrobenzene oxidation method. The
erythro and syringyl ratios of MWLRs were similar to or slightly higher than those of the corresponding milledwoods and always higher than those of corresponding MWLs. These results and the lower erythro ratio of
MWLR than the original wood meal indicated that lignin in MWLR was never free from structural changes
during milling.
2005-P04
β-O-4 型人工リグニンポリマーの合成 (4) —モノマー合成ルートの短縮—
岸本崇生、浦木康光、生方信
北海道大学大学院農学研究科
Synthesis of β-O-4 type artificial lignin polymer (4) - Improved synthetic methods for monomer
Takao Kishimoto, Yasumitsu Uraki, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
The β-O-4 structure is one of the most important substructures in lignin. The first polymericlignin mimic composed of only β-O-4 structure (DPw = 19.5-30.6) has been synthesized in our laboratory. In
this investigation the synthetic method for the monomer was improved, where the starting material was changed
from vanillin to acetovanillone.
2005-P05
DHP 調製における因子の検討
灰咲裕規*1、芦谷竜矢*2、藤田弘毅*2、中川明子*3 、黒田健一*2*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究院、*3 筑波大学大学院生命環境科学研究科
Effect of DHP preparation factors on the chemical structures
Hironori Haisaki*1, Tastuya Ashitani*2, Koki Fujita*2, Akiko Nakagawa*3, Kenichi Kuroda*2*1Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University, *3Institute of Agricultural and Forest Engineering, University of Tsukuba
Abstract:
DHP is made from p-hydroxycinnamyl alcohol by enzymatic polymerization, and it is used as amodel compound for natural lignin. However the reaction conditions (pH, substrate additive rate, enzyme
activity and so on) depend on each work and few people reported reproductivity of DHP preparation about yieldand linkages. In this study, bulk DHP is enzymatically prepared from coniferyl alcohol under various pH
conditions, and the chemical structures were examined by nuclear magnetic resonance ( 13C-NMR) and pyrolysis
gas-chromatography (Py-GC/FID). DHP prepared under low pH condition has higher abundance of β-O-4linkage, and that of -O-4 linkage was lower.
426

2005-P06
表面プラズモン共鳴を用いたモノリグノール類とヘミセルロースの相互作用（III）
中村淳、浦木康光、岸本崇生、生方信
北海道大学大学院農学研究科
Investigation on interaction between monolignols and hemicelluloses using surface plasmon resonance (III)Atsushi Nakamura, Yasumitsu Uraki, Takao Kishimoto, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University
Abstract:
To clarify lignin biosynthesis, we investigated on the interactions of hemicelluloses (xylan andglucomannan) with monolignols (coniferyl alcohol and sinapyl alcohol) and its glucosides (coniferin andsiryngin), and horseradish peroxidase by using surface plasmon resonance. The adsorption capacities of theoxidized hemicelluloses to monolignols were much larger than those to their glucosides. The interaction seems
to be due to the hydrophobic interaction. The adsorption of HRP to xylan was likely to be specific, and its
amount was larger than that to glucomannan. lt is suggested from these results that substrate of lignin
biopolymerization is supplied as monolignols from cytoplasm, and polymerized in xylan matrix.
2005-P07
リグニン前駆物質と多糖の相互作用に関する研究
藤加珠子、湯口宜明
産業技術総合研究所
Study on interaction of lignin precursor substances and polysaccharide
Kazuko Toh, Yoshiaki Yuguchi
National Institute of Advanced Industrial Science and Technology
Abstract:
Xyloglucan is a kind of hemicellulose, and exists in the cell wall or seed in the higher plants.
We investigated that xyloglucan aqueous solution took place gelation by addition of precursors of lignin as
coniferyl alcohol or sinapyl alcohol. Coniferyl alcohol needed for the formation of hydrogel was very low
concentration of 0.75wt% with 0.5wt% xyloglucan at 5ºC. The change in the line shape of the ESR spectrum
was also observed during the sol-gel transition of these mixtures.
2005-P08
白色腐朽菌 Phanerochaete sordida YK-624 株の産生する新規リグニンペルオキシダーゼによる塩素化芳香族化合物の分解
平井浩文、政氏恵理、高橋昭裕、河合真吾、西田友昭
静岡大学農学部
Degradation of polychlorinated aromatic compounds by novel lignin peroxidase from white-rot fungus
Phanerochaete sordida YK-624
Hirofumi Hirai, Eri Masauji, Akihiro Takahashi, Shingo Kawai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University
Abstract:
We tried to degrade various polychlorinated aromatic compounds by novel lignin peroxidase(YK-LiP) from Phanerochaete sordida YK-624. YK-LiP degraded 2,4,8-trichlorodibenzo- furan and
2,7-dichlorodibenzo-p-dioxin although LiP (Pc-LiP) from P. chrysosporium could not degrade these dioxins,
and the degradation rate of methoxychlor by YK-LiP was greater than that by Pc-LiP. Moreover, YK-LiP
degraded polychlorinated phenols more effectively than Pc-LiP. 2,4,6-Trichlorophenol (TCP) was converted to
2,6-dichloro-1,4-benzoquinone by YK-LiP. On the other hand, 2,6-dichloro-1,4-benzoquinone was not detectedin MnP reaction mixture although thedegradation of TCP by MnP was almost the same as that by YK-LiP.
2005-P09
白色腐朽菌から抽出した粗酵素によるダイオキシンの分解
佐々木良輝、伊藤和貴、橘燦郎
愛媛大学農学部
Biodegradation of dioxins with a crude enzyme from white-rot fungi
Yoshiteru Sasaki, Kazutaka Ito, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
To obtain the basic information for bioremediation of dioxin-contaminated soil by a crude
enzyme from white-rot fungi, biodegradation of 2,4, 8-Trichlorodibenzofuran (2,4,8-TrCDF) was investigated.
427

By biodegradation of 2,4,8-TrCDF with a crude enzyme from fungus PL1 in a liquid medium, about 50% of
2,4,8-TrCDF was degraded in 72 hours. Furthermore, the enzyme degraded about 20% of 2,4,8-TrCDF in soil
when the slurry phase biodegradation was conducted for 72 hours. These results suggest that bioremediation ofdioxin-contaminated soil by a crude enzyme from white-rot fungi is possible.
2005-P10
白色腐朽担子菌の系統解析とダイオキシン分解性
渡邊昌司*1、亀井一郎*1、近藤隆一郎*２*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究科
Phylogenic analysis and characterization of degrading dioxin for white-rot fungi
Masashi Watanabe*1, Ichiro Kamei*1, Ryuichirou Kondo*2*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University
Abstract:
In our previous study, we found that some Phlebia genera species were capable of degrading 2,
7-dichlorodibenzo-p-dioxin (2,7-diCDD) as model dioxin compound. In the present paper, we focused on newly
42 Phlebia strains and screened them. As a result, only Phlebia lindtneri and Phlebia acerina could degrade
2,7-diCDD. In addition, most strains which belong to these three species were capable of degrading 2,7-diCDD.
Therefore, we suggest that the ability of degrading chlorinated dioxin is conserved in the particular species of
Phlebia genera.
2005-P11
白色腐朽菌による塩素系芳香族化合物の分解における 菌体内・菌体外酵素の役割について
丸吉美幸*1、亀井一郎*1、近藤隆一郎*２*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究科
Roles of intracellular and extracellular enzymes in degradation of chlorinated aromatic compounds by white rot
fungi
Miyuki Maruyoshi*1, Ichiro Kamei*1, Ryuichiro Kondo*2*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University
Abstract:
Various white rot fungi (Phanerochaete, Phlebia, Pleurotus and Trametes sp.) were used indegradation experiment of 4,4'-dichlorobiphenyl (4,4'-DCB), 2,7-dichlordibenzo-p-dioxin (2.7-DCDD),
1,3,6.8-tetraCDD and dichlorodiphenyltrichloroethane (DDT). Although DDT and 4.4'-DCB were degradated
by most fungi, dioxins were effectively degradated by only Phlebia species, Decolorization of poly R 478 which
was thought to involve with ligninolytic enzyme was compared with degradation of pollutants. Decolorization
rate seemed to correlate with degradation of DDT, but not dioxins. Furthermore, piperonyl butoxide (inhibitor of
cytochrome P450) inhibited degradation of 2,7-DCDD, but not DDT. These results indicate that degradation
mechanisms of dioxins and DDT were different.
2005-P12
白色腐朽菌によるダイオキシン汚染土壌の処理
原田和寿*1、亀井一郎*1、近藤隆一郎*２*1
九州大学大学院生物資源環境科学研究科、*2 九州大学大学院農学研究科
Biodegradation of polychlorinated dioxin-polluted soil by white-rot fungi
Kazuhisa Harada*1, Ichiro Kamei*1, Ryuichiro Kondo*2*1
Graduate School of Boiresources and Bioenvironmental Sciences, Kyushu University, *2Graduate School of
Agriculture, Kyushu University
Abstract:
1,3.6,8-tetrachlorodibenzo-p-dioxin (1,3,6,8-tetraCDD) is a main contaminant of contaminatedpaddy soil. Therefore, the removal of 1,3.6,8-tetraCDD is the key component of decontamination. Recently, we
showed that 1,3,6,8-tetraCDD was transformed by Phlebia brevispora, and 2-methoxy-1,3,6,8-tetraCDD and
3.5-dichlorocatechol were detected as metabolites1). In this study, we attempted the degradation of
2.7-dichlorodibenzo-p-dioxin (2,7-diCDD) and 1,3,6,8-tetraCDD in soil. Forty six% of 1,3,6,8-tetraCDD in
artificially contaminated soil were degraded by the treatment with P. brevispora for 14 days. And also, we
identified the metabolites from 2,7-diCDD and 1.3,6,8-tetraCDD in artificially contaminated soil by treatment
with P. brevispora.
2005-P13428

アンモニウム残基を有するリグニン誘導体とクレーを原料とする複合体の調製
廣瀬重雄*1、畠山兵衛*2*1
産業技術総合研究所、*2 福井工業大学工学部
Preparation of composites consisting of lignin derivative with ammonium residue and clay
Shigeo Hirose*1, Hyoe Hatakeyama*2*1
Research Institute for Innovation in Sustainable Chemistry, *2Fukui University of Technology
Abstract:
Kraft lignin was allowed to react with glycidyltrimethylammonium chloride inpolyethylene glycol 400 (molecular weight 400) in the presence of catalytic amount of dimethylbenzylamine at
100 ºC for 12 h. The obtained reaction product was mixed with montmorillonite at room temperature. The
obtained composites were allowed to stand for 1 day at 60 ºC. The composites were studied by Fourier transfer
infrared spectroscopy (FTIR). The thermal properties of the composites were also studied by differential
scanning calorimetry (DSC) and thermogravimetry (TG).

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第 51 回 （2006.10.26-27） 北海道大学 学術交流会館
2006-101
高分子リグニン酸化能力を有するペルオキシダーゼアイソザイム CWPO−C の機能解析
佐々木慎弥、野中大輔、割石博之、埴祐司、近藤隆一郎
九州大学大学院農学研究院
The rote of the Tyr on the protein surface of cationic cell-wall-peroxidase
Shinya Sasaki, Daisuke Nonaka, Hiroyuki Wariishi, Yuji Tsutsumi, Ryuichiro Kondo
Facculty of Agriculture, Kyushu University, 6-10-1, Fukuoka, 812-8581, Japan
Abstract：
A unique peroxidase isoenzyme, cationic cell-wall-peroxidase (CWPO-C), from poplar callus
oxidizes sinapyl alcohol, ferrocytochrome c and synthetic lignin polymers, unlike other plant peroxidases. Here,the catalytic mechanism of CWPO-C was investigated using chemical modification and homology modeling.
Tyr modification of CWPO-C strongly suppressed its oxidation activities toward syringaldazine and 2,6-DMP
by 90%, and also suppressed its guaiacol oxidation activity to a Iesser extent. Ferrocytochrome c was notoxidized by TNM-modified CWPO-C. These resu[ts strongly suggest that Tyr residues in CWPO-C mediate its
oxidation of syringyl compounds and high-molecular-weight substrates. Homology modeling indicated thatTyr-177 and Tyr-74 werelocated at the protein surface of CWPO-C and near the heme. These results suggest that Tyr residue on theprotein surface is a key player in CWPO-C for its wide substrate oxidation spectrum.
2006-102
Characterization of Carthamus tinctorius cinnamyl alcohol dehydrogenases
Safendrri Komara Ragamustari*1,Tomoyuki Nakatsubo*1, Naoko Shiraiwa*1,
Shiro Suzuki*2, Takefumi Hattoril*1, Toshiaki Umezawa*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan*2
Institute of Sustainability Science, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract:
Characterization of three genes encoding cinnamyl alcohol dehydrogenase in Carthamus
tinctorius was carried out. Gas chromatography-mass spectrometry based enzyme analysis and substrate level
enzyme kinetics show that two Carthamus tinctorius cinnamyl alcohol dehydrogenases (CtCADs), named
CtCAD1 and CtCAD2, respectively, have a slightly different kinetic character. Lineweaver-Burk kinetic
analysis shows that CtCADl and CtCAD2 have almost the same catalytic activity towards coniferaldehyde andsinapaldehyde. Inhibition assay of CtCAD1 shows that the reduction of coniferyaldehyde is inhibited by thepresence of sinapaldehyde. In contrast, inhibition assay of CtCAD2 showed inhibition of both coniferaldehyde
and sinapaldehyde reduction. The results show that CtCAD1 and CtCAD2 play an important role in theformation of both syringyl and guaiacyl monolignols. The characterization of another CtCAD (CtCAD3) iscurrently underway.
2006-103
イネをモデルとした植物細胞壁形成過程に関する研究 —Glosylphosphatidylinositol はイネの細胞壁高次構
造形成にどのように関わるのか？−2
鈴木瑠*1、伊藤幸子*1、佐藤かんな*2、半智史*3、北野英己*2、船良*3、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 名古屋大学大学院 BBC、*3 東京農工大学大学院農学研究科
Study of plant cell wall formation in Oryza sativa L. — How does glosylphosphatidylinositol-anchoredprotein relate to cell wall conformation in rice plant (Oryza satiba L.)?-2
Ryu Suzuki＊１, Sachiko Ito＊１, Kanna Sato＊2, Satoshi Nakaba＊3,Hidemi Kitano＊2, Ryo Funda＊3 ,Sinya Kajita＊１,
Yoshihiro Katayam＊１＊１Graduate school of Bio-Applications ad Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan＊2
Graduate school of Agriculture, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509,
Japan＊3
Bioscience and Biotechnology Center, Nagoya University, Chikusaku, Nagoya, 464-8601 Japan
Abstract:
There are many studies about cell wall formation using mutant. However, most of them areabout biosynthesis of main cell wall component such as cellulose, hemicellulose, and lignin. Few information
obtained about detailed mechanism and process of wall conformation. In this study, we used brittle culm mutant
called 'cwa1', recessive mutant rice plant (Oryaza sativa L.). Cwal has defective in plant mechanical strength.
430

But there is a little distinction of amount of cell wall components. And it's revealed that cwa1 has defective cellwall thickness, and distribution of wal1 components by histological analysis. So cwa1 is predicted that it has
defective in cell wall conformation after cell wall components are biosynthesized. By analyzing cwa1 and its'
defective gene, BC1, we can discuss about mechanism and process of cell wall conformation in monnocot..
2006-104
ポプラにおける細胞膜を介したモノリグノール輸送メカニズム河合亮*1、高部圭司*1、藤田稔*1、間藤徹*1、研士反伸和*2、矢崎一史*2*1
京都大学大学院農学研究科、*2 京都大学生存圏研究所
Mechanism of monolignol transportation through plasma membrane in poplar
Ryo Kawai*1, Keiji Takabe*1, Minoru Fujita*1, Toru Matoh*2, Nobukazu Shitan*2, Kazufumi Yazaki*2*1Graduate School of Agriculture, Kyoto University, Kyoto 606-8502, Japan, *2Research Institute for Sustainable
Humanosphere, Kyoto University, Gokasho, Uji 611-0011, Japan
Abstract:
The lignin biosynthesis consists of three parts, that is, biosynthesis, transportation, andpolymerization of monolignols. Recent investigation shows that the enzymes, involved in conversion of the last
step of monolignol biosynthesis, localize in cyto-sol. Therefore, monolignols probably exist in cytosol. They
may be transported from cyto-sol to cell wall via plasma membrane and then polymerized within the cell wall.
In this study, we analyzed the mechanism of monolignol transportation in lignifying tissues. The
characterization of monolignol transport using microsomal fractions containing membrane vesicles showed that
uptake of coniferin was stimulated by Mg/ATP, while that of coniferyl alcohol, sinapyl alcohol and syringin
were little regardless of presence of ATP. Coniferin uptake was strongly inhibited with NH4 +, while vanadate,
which was commonly used to inhibit ATP-binding cassette (ABC) transporters, had no effect. This suggests thatconiferin uptake
into membrane vesicles depends on the electrochemical gradient of H+ across them.
2006-105
リグナン生合成経路におけるメチレンジオキシブリツジ形成と配糖化反応
小埜栄一郎*1、中井正晃*2、福井祐子*2、富森菜美乃*2、水谷正子*1、佐竹炎 *3、斉藤雅之*1、中尾正宏*1、田中隆治*3、勝田真澄*4、梅津俊明*5、田中良和*1*1
サントリー（株）先進コア技術研研究所、*２サントリー（株）健康科学研究所、*３（財）サントリー生有研、*４（独）作物研究所、*５京都大学生存圏研究所
Methylenedioxy bridge formation and glucosylation in lignan biosynthesis
Eiichiro Ono*1, Masaaki Nakai*2, Yuko Fukui*2, Namino Tomimori*2, Masako Fukuchi-Mizutani*1, Honoo
Satake*3, Masayuki Saito*1, Masahiro Nakao*1, Takaharu Tanaka*3, Masumi Katsuta*4, Toshiaki Umezawa*5,
Yoshikazu Tanaka*1*1Institute for Advanced Core Technology, Suntoy Ltd., Mishima, Osaka 618-8503, Japan, *2Institute for
Healthcare Science, Suntory Ltd., *3Suntory Institute for Bioorganic Research, *4Department ofField Crop Research National Institute of Crop Science, *5Institute for Sustainable Humanosphere Kyoto
University
Abstract:(+)-Sesamin, a furofuran class lignan, is widespread in vascular plants and represented by
Sesamum spp. (+)-Sesamin has been of rapidly growing interest because of its beneficial biological effects in
mammals, but its biosynthesis and physiological roles in plants remains to be clarified. It is speculated to besynthesized from (+)-pinoresinol via (+)-piperitol by formation of two methylnedioxy bridges mediated by two
distinct Sesamum indicum cytochrome P450 proteins. Here we report a novel S. indicum P450, CYP81Q1 thatalone catalyzes (+)-sesamin biosynthesis from (+)-pinoresinol via (+)-piperitol by forming two methylenedioxy
bridges. The CYP81Q1 gene expression profile was temporally consistent with the accumulation pattern of(+)-sesamin during seed development. The CYP81Q1-GFP chimera protein was co-localized with anendoplasmic
reticulum (ER) targethg chimera protein, indicative that (+)-sesamin biosynthesis occurs on the ER cytoplasmic
surface. Moreover, we isolated two CYP81Q1 homologs from other Sesamum spp. S. radiatum CYP81Q2
showed the dual (+)-piperitol/(+)-sesamin synthetic activity. CYP81Q2 as well as CYP81Q1, therefore
corresponds to an (+)-piperitol/(+)-sesamin synthase (PSS) in lignan biosynthesis. In contrast, S. alatum
CYP81Q3 showed no activity, in accord with (+)-sesamin being deficient in S. alatum. Our findings not only
provide new insight into lignan biosynthesis but also
unravel a novel mode of cytochrome P450 action.
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2006-106
分化中木部における細胞壁成分の ToF−SIMS イメージング
斉藤香織、今井貴規、松下泰幸、福島和彦
名古屋大学大学院生命農学研究科
ToF-SIMS imaging of constituents in plant cell walls of differentiating xylem
Kaori Saito, Takanori Imai, Yasuyuki Matsushita and Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601
Abstract:
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to visualize the
distribution of lignin and polysaccharides in the differentiating xylem of Pinus thunbergii. A recent study using
ToF-SIMS showed that lignin polymers can be characterized by specific secondary cations with a guaiacyl ringat m/z 137 and 151. In this study, the specific monomeric ions of cellulose and xylan were also identified.
ToF-SIMS imaging analysis showed that the image of deposition of cellulose and xylan disappeared after thatthe image of deposition of lignin started in
the differentiating xylem.
2006-107
リグニン β−O−4 構造の細胞壁における絶対量と細胞壁「木質化」との関係
東京大学大学院農学生命科学研究科
中村裕貴、秋山拓也、Deded S．Nawawi、近藤憲哉、松本雄二
Absolute Amounts of β-O-4 structures in wood and non-wood cell walls
Hirotaka Nakamura, Takuya Akiyama, Deded S.Nawawi, Kenya Kondo, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
All higher vascular plants, whether they are wood species or not, contain lignin in the cell walls,
but wood cell walls are much harder and stronger than non-wood cell walls such as leaves and grasses. The
important key factor for cell walls to be hard and have enough strength is still unknown. The purpose of thisinvestigation is to understand the difference between wood cell wall and non-wood cell wall such as of leaves
and grasses from viewpoints of lignin structure and its content. As a measure to distinguish wood cell walls andnon-wood cell walls, we examined the absolute amount of arylglycerol-β-aryl ether (β-O-4) structure in cellwall, not in lignin, by ozonation method. It seems that a critical level is present for the amount of β-O-4structures in wood cell wall and this level gradually increased depending on the syringyl ratio. Interestingly, thisamount found for all the leaves and most of the grass stems was lower than this critical level. We will
hypothetically propose the importance of the absolute amount of β-O-4 structure in cell wall, not in lignin, todistinguish wood cell and non-wood cell.
2006-108
モノリグノール配糖体の HRP 触媒脱水素重合 Part 2．
飛松裕基、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
HRP catalyzed dehyrogenative polymerizations of monolignol glucosides. Part 2.
Yuki Tobimatsu, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture. Kyoto University. Sakyo-ku, Kyoto
606-8502, Japan
Abstract:
Dehydrogenative polymerizations of monolignol βD-glucosides (isoconiferin, 1a;isosyringin, 1b; triandrin, 1c) using horseradish peroxidase (HRP)/ H202 as catalyst were carried out, resulting in
the formations of water-soluble lignin-like polymers (DHPs): poly (1a)-(1c), The degrees of polymerization(DPs) of poly (1a) and poly (1c) were much higher than those of conventional DHPs, whereas DP of poly (1c)was low. Cyclic voltammetry analyses showed that the monomer 1b had a lower oxidation potential thanmonomer 1a and 1b. HRP-catalyzed initial reaction rates ofmonomer 1b, however, was extremely low and in the same range as that of sinapyl alcohol, while the oxidation
rates of monomer 1a and 1c were significantly higher than those of corresponding monolignols. These results
indicated that HRP had low specificity to monomer 1b as well as to sinapyl alcohol and did not catalyze theformation of highly polymerized poly (1b) even in a homogeneous reaction system. Structural analyses
confirmed that poly (1a)-(1c) were lignin-like polymers containing D-glucose units attached to the lignin
sidechains.
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2006-109
高速フローESR 法を用いたリグニンモデル化合物に対するラジカル種の反応性に関する研究
大橋康典、宇野由紀子、渡遽崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Studies on reactivity of radical species with lignin model compounds using a rapid flow-ESR method
Yasunori Ohashi, Yukiko Uno, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Laboratory of Biomass Conversion, Research Institute for Sustainable Humanosphere, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
Abstract:
It has been discussed that non-phenolic lignin model compounds (LMCs) are degraded byradical reactions. In the reactions with free radicals, it is suggested that extraction of electron or hydrogen atomfrom the LMCs are induced by the radicals. However, there has been no direct spectroscopic evidence
demonstrating the production of initial radical intermediates from the LMCs by the free-radical-mediateddegradation. Furthermore, it was not shown which radical species can degrade the LMCs. In the present study,
we tried to detect the radicals derived from the LMCs produced by the reactions with alkoxyl, peroxyl, hydroxyl
and hydroperoxyl radicals using a rapid flow-ESR method. The results suggested that peroxyl and hydroperoxyl
radicals have no reactivity with the LMCs. On the other hand, hydroxyl radicals extract a hydrogen atom fromthe a position of veratryl alcohol (VA), a simplest monomeric LMC used. ESR spectrum of this radical wasquite different from the radical produced by one electron extraction with Ce4+.
2006-110
耐塩性白色腐朽菌 Phlebia sp．MG60 の産生するマンガンペルオキシダーゼの発現解析
亀井一郎*1、大黒千映子*2、堤祐司*2、近藤隆一郎*2*1
九州大学 VBL、*2 九州大学大学院農学研究院
Expressional analysis of manganese peroxidases from saline-tolerant white rot fungus, Phlebia sp. MG60
Ichiro Kamei*1, Chieko Daikoku*2, Yuji TsuTsumi*2, Ryuichiro Rondo*2*1
VBL, Kyushu University, *2Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka
812-8581, Japan
Abstract:
Expression pattern of manganese peroxidases (MnPs) which were produced by saline- tolerant
white rot fungus, Phlebia sp. MG-60, was analyzed. When MG-60 was cultured in the Kirk medium containing
3% sea salts (salt medium), higher activity of MnPs was produced than that in the normal Kirk medium (0% sea
salts). SDS-PAGE analysis demonstrated that two MnP isoenzymes were de novo synthesized during the culturein the salts medium. Three MnP encoding genes (MG-mnp1, MG-mnp2, and MG-mnp3) were isolated and thesetranscriptions in the Kirk medium with and without 2% NaCl were determined by real-time PCR technique.
MG-mnp2, and MG-mnp3 were highly expressed in the medium with NaCl.
2006-111
アカシアクラフトパルプのバイオブリーチングに向けた白色腐朽菌のスクリーニング
アフリダ*1、玉井 裕*2、大崎 満*1*1*２
北海道大学大学院農学研究科
Screening of white rot fungi and their potential application in biobleaching of acacia kraft pulp
Afrida*1, Yutaka Tamai*2, Mitsuru Osaki*1*1
Laboratory of Plant Nutrition, *2Laboratory of Forest Resource Biology, Graduate School of Agriculture,
Hokkaido University, N-9, W-9, Kita-ku, Sapporo 060-8589, Japan
Abstract:
To study the biobleaching to Acacia kraft pulp, over 600 strains of white rot fungi werecollected from various natural sources such as fruiting bodies, rotten woods and trap piles atvarious locations in Indonesia such as West Java, Central Kalimantan, South Kalimantan, Jambi and North
Sumatra. We succeeded to screen five strains of white rot fungi for application in Acacia kraft pulp bleaching.
2006-112
担子菌におけるヘム生合成の特異的制御機構
三浦大典*1、志水元亨*2、割石博之*3*1
九州大学大 VBL、*2 九州大学大学院農学研究院、*3 九州大学大学院農学研究院・KBAC
Molecular mechanisms involved in the regulation of heme biosynthesis in Phanerochaete chrysosporium
Daisuke Miura, Moyoyuki Shimizu, Hiroyuki Wariishi
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*1

Venture Business Laboratory, *2Faculty of Agriculture, *3Bio-Architecture Center, Kyushu University, Fukuoka,
Japan
Abstract:
Addition of exogenous aromatic compounds to Phanerochaete chrysosporium resulted in an
immediate metabolic shift from a short-cut TCA/glyoxylate bicycle system into a general TCA cycle, which inturn resulted in the activation of the heme biosynthetic pathway branched at succiny1-CoA. On the other hand, afree heme is highly toxic to the cell. To reveal regulatory mechanisms involved in fungal heme biosynthesis, acomprehensive analysis for surveying heme- binding proteins produced by P. chrysosporium was performed.
Biotinylated heme- streptavidin beads system was utilized for separating intracellular heme-binding proteins.
From an SDS-PAGE separation and MALDI/TOF-MS analysis on peptide mass fingerprinting of these proteins,
mitochondrial citrate synthase (PcCS) and glycelaldehyde 3-phosphate dehydrogenase (PcGAPDH) wereidentified as putative heme-binding proteins. Recombinant PcCS and PcGAPDH were expressed as active forms
in E. coli for further kinetic and spectroscopic characterization. Either PcCS or PcGAPDH was inhibited with aphysiological concentration of hemin. Inhibitory mechanism was further characterized for PcCS using ahomology modeling technique. These observations were the first evidence for a direct interaction of a heme
molecule to metabolic enzymes to control a metabolic flux in the fungus.
2006-113
The oxidation of polyphenols by extracelullar peroxidase from suspension cultured cells of liverwort
Heteroscyphus planus
Leily Tjandrawaskitasari*1, Rie Hata*1 , Takashi Ohsasa*2, Hanami Chiba*2, Makoto Hashimoto*2, Kosaku
Takahashi*1, Kensuke Nabeta*1*1
Laboratory of Bioorganic Chemistry, Division of Applied Bioscience, Research Faculty of Agriculture,
Hokkaido University, *2Department of Agriculture and Life Science, Obihiro University ofAgriculture and Veterinary Medicine
Abstract:
Suspension cultured cells of liverwort, Heteroscyphus planus excreted peroxidase in the culture
medium. The peroxidase activities were inducted by co-incubation of phenols such as p-cresol,
2,6-dimethoxyphenol, bisphenol-A (BPA) and lignin model compound (LMC, guaiacylglycerol-guaiacyl
ether). We observed the oxidation of BPA and LMC in the cultured cells of the liverwort. BPA was mainly
polymerized to higher molecular compounds, while was partly
biodegraded to small molecular compounds. The biodegraded compounds were identified as
4-isopropenyl and p-hydroxyacetophenone. The process to form these compounds was examined using
deuterated-BPA. LMC was degraded to guaiacol, vanillin, coniferyl alcohol and ferulic acid, while a dimmer of
LMC, 1,1'-(4,4'-dihydroxy-3,3'-dimethoxy-5,5'-biphenylene)-bis [8-(2''-methoxy- phenoxy)-7,9-propanediol]
was also detected.
2006-特別講演 I
Invited Lecture, I
Biotechnology based wood quality research program for forest biorefinery
H-m. Chang*1, R. Sederoff*2, B. Li*2 , B. Goldfarb*2, J. F. Kadla*3 , V. L. Chiang*1*2*1
Dept. of Wood and Paper Science, *2Dept. of Forestry, College of Natural Resources, North Carolina State
University, Raleigh, NC 27695-8005, USA, *3University of British Columbia, Vancouver, B.C. V6T IZ4,
CanadaIntroduction: The Southern U.S. is the major supplier of industrial wood and wood products to the world.
North Carolina State University, in collaboration with industry and governmental agencies, has been
undertaking an intensive breeding program for loblolly pine during the past fifty year, resulting in great increasein growth, straightness, wood density and disease resistance. In anticipation of ever increased demand for woodin the future, increasingly intensive plantation forestry is being used for wood supply. Great increases in the
productivity of pine plantations in the southern US have been achieved due to genetic and silvicultural
improvements in recent years. However, increased growth rates have resulted in trees with more juvenile wood,
many properties of which are quite different from those of mature wood. We thus focus our efforts for the
production of rapid growing short rotation juvenile loblolly pine with improved wood properties. To achieve thisgoal, we have been integrating research on wood properties, tree breeding, propagation and genomics during thepast 8 years. Two approaches have been taken to achieve this goal: selection of the desired traits from thegenetically controlled natural variations in target properties and improvement through genetic profiling of thedesired properties. On the other hand, recent sharp increase in the price of oil has greatly stimulated greatinterest in biofuel production. Several barriers still exist in converting lignocellulosic feed stock to biofuel.
434

During the past two years, we have been undertaking study to overcome some of the barriers by lowering lignin
content and increase syringylpropane to guaiacylpropane ratio (S/G) using transgenic approach. In thispresentation, we attempt to briefly describe our efforts and summarize the results in these two areas of research.
2006-201
リグニンの立体化学と微生物代謝機能に関する研究（I） −guaiacylglycerol-β-gaiacylether（GGE）の立体化
学−
菱山正二郎*1、中村雅哉*1、大塚祐一郎*1、大原誠資*1、政井英司*2、片山義博*3*1
森林総合研究所、*2 長岡技術科学大学・生物、*3 東京農工大学大学院
Studies on stereochemistry of lignin and microbial metabolic functions - Stereochemistry of lignin andmicrobial metabolic functions -Stereochemistry of guaiacylglycerol-βguaiacyl ether (GGE)Shojiro Hishiyama*1, Masaya Nakamura*1, Yuichiro Otsuka*1, Seiji Ohara*1, Eiji Masai*2
Yoshihiro Katayama*3*1
Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan,*2
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan,*1
Gradurate School of Bio-Applications and Systems Engineering, Tokyo
University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Abstract:
Four stereoisomers of guaiacylglycerol-β-guaiacyl ether (GGE:1), which is important substrate
for understanding the relationship between microbial metabolic functions and stereochemistry of lignin, weresynthesized with enantiopure form. And two stereoisomers of α-(2-methoxyphenyl)- β-hydroxypropiophenone(MPHPV:2), which is important intermediate located in metabolic pathway of GGE microbial degradation, werealso synthesized.
2006-202
リグニンの立体化学と微生物代謝機能に関する研究（II） 一バクテリアの立体選択的グルタチオン−S−トラン
スフエラーゼによる β-アリールエーテル開裂機構−
政井英司*1、市村篤史*1、宮内啓介*1、福田雅夫*1、菱山正二郎*2、中村雅哉*2、片山義博*3*1
長岡技術大学・生物機能工学、*2 森林総合研研究所、*3 東京農工大学大学院 BASE
Studies on stereochemistry of lignin and microbial metabolic functions (II): Cleavage of the aryl ether
linkage catalyzed by bacterial enantioselective glutathione S-transferases
Eiji Masai*1, Atsushi Ichimura*1, Keisuke Miyauchi*1, Shojiro Hishiyama*2, Masaya Nakamura*2, Yoshihiro
Katayama*3, Masao Fukuda*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, *2Forestry andForest Products Research Institute, Tsukuba, Ibaraki, 305-8687, *3Graduate school of Bio-Applications andSystems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Abstract:
Cleavage of the β-aryl ether linkage is the most important process in lignin degradation. In aprevious study, we isolated the β-aryl ether degradation operon, ligDFEG, of Sphingomonas paucimobilis
SYK-6. The ligD gene encodes Ca-dehydrogenase, which oxidizes guaiacylglycerol-β-guaiacyl ether (GGE) toa-(2-methoxyphenoxy)- β-hydroxypropiovanillone (MPHPV). The ligE, ligF, and ligG genes showed similarity
with glutathione S-transferases but only the gene products of ligE and ligF exhibited the β-etherase activity. In
this study, we determined the actual roles of three GST genes. MPHPV was transformed by LigE and LigF to
guaiacol and α-glutathionyl-β-hydroxy- propiovanillone (GS-HPV), suggesting that LigE and LigF catalyze thenucleophilic attack of glutathione on the carbon atom at the β position of MPHPV. HPLC-circular dichroism
analysis indicated that LigE and LigF each attacked a different enantiomer of the racemic MPHPV preparation.
LigG catalyzed the elimination of glutathione from GS-HPV generated by the action of LigF. Disruption of ligE,
ligF, and ligG in SYK-6 showed that ligF is essential to the degradation of one of the MPHPV enantiomers. The
alternative activities which metabolize the substrates of LigE and LigG are present in this strain.
2006-203
超臨界・亜臨界水条件での嘲 Björkman リグニンおよび微生物変性リグニンの反応
金貞福*1*2、勝亦京子*1、飯山賢治*3*1
東京大学大学院農学生命科学研究科、*２現：中国浙江林業大学化学工程、*３東京大学アジア生物資源環
境研究センター
Reaction of Björkman lignin and biologically modified lignin under supercritical and sub-critical watercondition
435

Zhenfu Jin*1*2, Kyoko S. Katsumata*1, Kenji Iiyama*3*1
Graduate School of Agricultural & Life Sciences, the University of Tokyo, *2Department of Chemical
Engineering, Zhejiang Forestry University, China, *3Asian Natural Environmental Science Center, theUniversity of Tokyo
Abstract:
Behavior of dissolved organic matters (DOM) in water, which was isolated from peatswamp water and characterised as biologically modifled lignin, under condition at deep sea would be quite
important for global carbon circulation. Reaction of DOM under supercritical water condition (650K, 22.4MPa)
was investigated together with those of Björknan lignins isolated from Abies firma and Fagus crenata.
Demethylation reaction was predominant, and major products were catechol derivatives.
2006-204
フェノール性 β−エーテル型２量体モデル化合物の熱分解開裂機構に及ぼす Cγ−水酸基の影響
河本晴雄、料理谷 正和、坂 志朗
京都大学大学院エネルギー科学専攻科
Influence of Cγ-hydroxyl group on the mechanism of pyrolytic β-ether cleavage of phenolic model dimers
Haruo Kawamoto, Masakazu Ryoritani, Shiro Saka
Graduate School of Energy Science, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
We already reported that elimination of the Cγ-OH group substantially inhibited the pyrolytic
cleavage of the -ether bond of phenolic model dimers. The temperatures where model dimmers became
reactive in 1 min pyrolysis were different between Cγ-OH type (250ºC) and Cγ-deoxy type (400ºC). Theseprevious findings indicate that cleavage mechanisms are different between these model dimers. In this paper,
these cleavage mechanisms are discussed. Reactivity of the Cγ-deoxy type was very dependent on the pyrolysis
conditions. Cγ-deoxy type was stable even at 400ºC under the conditions which made the volatilization of low
molecular weight (MW) products from the heated zone easy. On the other hand, the Cγ-deoxy type wascompletely decomposed at 400ºC and even reactive at 300ºC when model compound in a closed ampoule washeated in muffle furnace. These results indicate that radical chain reaction occurs in pyrolysis of the Cγ-deoxy
type. To confirm this, influence of tetralin (a radical scavenger) was investigated for Cγ-deoxy and Cγ-OH typesof model dimers. As a result, addition of tetralin substantially reduced the pyrolytic cleavage reactivity of theC-deoxy type, whereas the reactivity of the Cγ-OH type was not influenced by tetralin. Furthermore,reactivities of variously p-substituted model dimers (Cγ-deoxy type) in sufficient amount of tetralin increased
positively related to the order of ABDE of the substituent groups. These results suggest the radical chain
mechanism starting from the direct homolytic Cβ-O bond cleavage for the Cγ-deoxy type, although the β-etherbond of the Cγ-OH type is cleaved through quinonemethide formation (an ionic reaction) at much lower
temperature of 250ºC. The role of the Cγ-OH group is also proposed as stabilizing effect of the transition state inquinonemethide formation by hydrogen bonds between Cα- and Cγ-OH groups. Under pyrolysis conditions,such intramolecular stabilization may play an important role in promoting the ionic type of reaction.
2006-205
酸素漂白条件下における活性酸素種による糖の被攻撃部位の特定（1）〜アノマ一位についての検討〜
小西史子、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Specification of the site of carbohydrate attacked by active oxygen species under oxygen bleaching conditions(1) - Examination on the anomeric position Fumiko Konishi, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 1 13-8657, Japan
Abstract:
lt has still been the serious problem that oxygen delignification is accompanied by
the depolymerization of carbohydrates. It is important to know the degradation mechanism of carbohydrates toprotect them under oxygen bleaching conditions. In this study, the relative reactivity of active oxygen species(AOS) toward two carbohydrate model compounds, methyl α-D-glucopyranoside (MGPα) and methyl
β-D-glucopyranoside (MGPβ), was examined under practical oxygen bleaching conditions, where AOS were insitu generated by subjecting a phenolic compound, 2,4,6-trimethylphenol, to the oxygen oxidation. It was also
examined whether or not the anomeric position is attacked by AOS by using a model compound, methyl
β-D-[1-d]-gluco- pyranoside (MGPβ[1-d]). As the degradation of MGPβwas greater than MGPαat pH 13.5, it issuggested that the stereo configurational difference in their anomeric positions has an influence on theirreactions with AOS. And the result that the reactivity of AOS toward MGPβwas higher than that toward436

MGPβ[1-d], suggests a possible occurrence of the attack on the anomeric position.
2006-206
生命科学と有機材料科学を基盤としたリグニンの新しい高度利用に関する研究（I）
大塚祐一郎*1、中村雅哉*1、大原誠資*1、重原淳孝*2、梶田真也*2、片山義博*2、政井英司*3、福田雅夫*3*1
森林総合研究所、 *2 東京農工大学大学院 BASE、*3 長岡技術科学大学
Studies on the novel advanced utilization system of lignin based on the life science and organic material
chemistry (I)Yuichiro Otsuka*1, Masaya Nakamura*1, Seiji Ohara*1, Kiyotaka Shigehara*2, Shinya Kajita*2, Yoshihiro
Katayama*2, Eiji Masai*3, Masao Fukuda*3*1
Forestry and Forest Products Research Insutitute, Ibaraki, Japan, *2Graduate School of Bio-Applications andSystems-Engineering, Tokyo University of Agriculture and Technology, Tokyo, Japan, *3Nagaoka University ofTechnology, Niigata, Japan
Abstract:
Sphingomonas paucimobilis SYK-6, which can degrade various low molecular weightcompounds derived from plant polyphenols such as lignin, lignan, and tannin, metabolizes these substances via
2-pyrone-4,6-dicarboxylic acid (PDC). We focused on this metabolic intermediate as a potential raw material for
novel biopolymers. We cloned the ligAB and ligC genes of SYK-6, which respectively encode protocatechuate
4,5-dioxygenase and4-carboxy-2-hydroxymuconate-6-semi- aldehyde dehydrogenase, into a broad host-range
plasmid vector, pKT230MC. The resulting plasmid, pDVABC, was introduced into the PpY1100 strain of
Pseudomonas putida, and we found that PDC could be stably produced from protocatechuate and accumulated.
In addition, we examined the efficiency of production of PDC from protocatechuate on a 5-L scale in a
LB-medium containing 100 mM glucose, and determined that PDC was stably produced from protocatechuate
to yield 10g/L or more.
2006-207
生命科学と有機材料科学を基盤としたリグニンの新しい高度利用に関する研究（II）
近藤晋*１、大塚博之*１、重原淳孝*１、梶田真也*１、片山義博*１、政井英司*２、福田雅夫*２、大塚祐一郎*３、中村雅哉*３、大原誠資*３*１
東京農工大学大学院 BASE、 *２長岡技術科学大学、*３森林総合研究所
Studies on the novel advanced utilization system of lignin based on the life science and organic material
chemistry (II)Susumu Rondo*１, Hiroyuki Otsuka*１, Kiyotaka Shigehara*１, Shinya Kajita*１, Yoshihiro Katayama*１, Eiji
Masai*２, Masao Fukuda*２, Yuichiro Otsuka*3, Masaya Nakamura*3, Seiji Ohara*3*１Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei Tokyo,184-8588, Japan, *2Department of Bioengineering, Nagaoka University ofTechnology, Nagaoka Niigata,940-2188,Japan, *3Forestry and Forest Products Research Institute,1 Matsunosato
Tsukuba, Ibaraki, 305-8687,Japan
Abstract:
2-Pyrane-4,6-dicarboxylic acid (PDC) is an intermediate metabolite of Sphingomonas
paucimobilis SYK-6 which can degrade and assimilate low molecular lignin. PDC can be used as polymer
materials. We decided to product PDC using genetic engineering. For practical use, we tried to product PDC
from various kinds of low molecular lignin in large scale. We finally product PDC in 5L scale from vanillin,
vanillate, syringate and p-hydroxybenzoate which were provided from chemical treatment of lignin. In addition,
we tried to product PDC from terephthalate which can obtain easily and cheaply. And now, we can product PDC
from 10g/l of terephthalate. It helps to develop PDC application.
2006-208
リグノスルホン酸系硬質ポリウレタンフォームの発泡速度制御と熱的・機械的性質
畠山兵衛*1、塵垣亜耶*1、畠山立子*2*1
福井工業大学工学部、*2 リグノセルリサーチ
Effect of reaction rate on thermal and mechanical properties of sodium lingnosulufonate-based polyurethane
foams
Hyoe Hatakeyama*1, Aya Hirogaki*1, Tatsuko Hatakeyama*2*1
Fukni University of Teclmology, 3-6-1, Gakuen, Fukui 910-8505, *2Lignocell Research, 2-6-16, Mejirodai,
Bunkyo-ku, Tokyo 112-0015
Abstract:
Sodium ligninosulfonate (NaLS)-based polyurethane (PU) foams were prepared using three437

kinds of ethylene glycols, such as diethylene glyco1, triethylene glycol or polyethylene glycol.
Two kinds of NaLS, weak acid based NaLS(WA) and weak alkaline based NaLS (WB), were used in order tocontrol the foaming reaction. Stirring time, cream time and rise time were used as an index of foaming reaction.
Mixing time was defined as a time interval from adding MDI to detect evolved heat under stirring, cream time
as a time interval from termination of stirring to starting of foaming, and rise time as a time interval fromstarting to completion of foaming. The above reaction times increased with increasing the amount of NaLS
(WA) content in polyols. Apparent density, compression strength and compression modulus of PU foams
linearly increased with reaction times. At the same time, the molecular mass of ethylene glycols markedly
affects the molecular motion of PU foams. It was found that mechanical and thermal properties of PU foams arecontrollable through foaming reaction rate.
2006-209
リグニンスルホン酸塩を原料とするエステル型エポキシ樹脂の合成と熱的性質
贋瀬重雄*１、相楽壮志*１、畠山立子*２、畠山兵衛*３*１
産業技術総合研究所・環境化学、*２リグノセルリサーチ、*３福井工業大学工学部
Synthesis and thermal properties of epoxy resins from ligninsulfonate
Shigeo Hirose*１, Soshi Sagara*１, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*3*１
Research Institute for Innovation in Sustainable Chemistry, AIST, Central 5, 1-1-4, Higashi, Tsukuba, Ibaraki
305-8565, Japan, *2Lignocel Research Ltd., 2-6-16 Mejirodai, Bunkyo-ku, Tokyo 112-0015, Japan, *3Fukui
University ofTeclmology, 3-6- I Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Sodium ligninsulfonate (LS) was dissolved in ethylene glyco1 (EG) and the obtained mixture
was allowed to react with succinic anhydride to form a mixture of ester-carboxylic acid derivatives (LS-EG
polyacid, LSEGPA). EG-polyacid (EGPA) was also prepared from EG. The mixture of LSEGPA and EGPA wasreacted with ethylene glycol diglycidyl ether in the presence of catalytic amount of dimethylbenzylamine toform epoxy resins. The molar ratio of epoxy groups tocarboxylic acid groups ([EPOXY]/[AA] ratios, mol/mol) was maintained at 1.1. The contents of LSEGPA in the
mixture of LSEGPA and EGPA (LSEGPA content) were varied from 0 to 100 %. Thermal properties of epoxy
resins were studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Glass transition
temperatures (Tg's) of epoxy resins increased with increasing LSEGPA contents suggesting that lignin acts as a
hard segment in epoxy resin networks. Thermal decomposition temperatures (Td's) of epoxy resins were almost
constant regardless of
LSEGPA contents.
2006-210
リグノスルフォン酸をベースとしたポリカプロラクトン誘導体の物性と生分解性について
島田 幹夫、山下寿々佳、大西 徹、畠山 兵衛
福井工業大学工学部
Effect of biodegradation on thermal and spectroscopic properties of lignosulfonate-based polycaprolactone
derivatives
Mikio Shimada, Szuka Yamashita, Toru 0mishi, Hyoe Hatakeyama
Fukui University of Technology, 3-6- 1, Gakuen, Fukui, 910-8505
Abstract:
Lignosulfonate-based poly caprolactone (L-PCL) specimens were subjected to biodegradationin the field. Spectroscopic and thermal properties of the recovered samples were analyzed with FTIR and DSC.
The results suggested that ester moieties in L-PCL were more rapidly degraded than lignin moieties. The
alternative experiment with MODA (Micobial Oxidative Degradation Analyzer) recently developed indicatedthat sucrose linked with PCL was decomposed to CO2 much faster than L-PCL and cellulose.
2006-211
環状カーボネート／グリコール系加溶媒分解で得られるリグニンの化学構造と熟特性
久保智史、山田竜彦、橋田光
森林総合研究所
Chemical structure and thermal properties of the Llgnin fraction prepared by the solvolysis using cycliccarbonate/glycol systems
Satosih Kubo, Tatsuhiko Yamada, Koh Hashida
Forestry and Forest Products Research Institute,1 Matsunosato, Department of Biomass Chemistry Tsukuba,438

305-8687 Japan
Abstract:
A new solvolysis system is being proposed for the bioconversion of lignocellulosics to valuable
chemicals and materials in FFPRl. Using the solvolysis systems of cyclic carbonates/glycoI, our system canconvert lignocellulose into levulinates with high conversion rates, and moldable lignin
fraction, During this process, glycol chains that have high thermal mobility are introduced into the lignin
molecules by the reaction with both of cyclic carbonates and glycols. With extent of reaction period, average
length of ethylene glycol chain is extended, and GPC average molecular weight is increased. The amount of
introduced glycol chain can be estimated by quantitative 13C-NMR with relaxation reagent, UV andthermogravimetric analysis.
2006-212
オルガノソルブリグニン（アセテート）／セルロース親和性ポリマー複合体の分子間相互作用の評価と木材・紙用速乾性接着剤としての応用
寺本好邦、田中紀子、堺真奈美、遠藤黄土
産業技術総合研究所バイオマス研究センター
Interaction in organosolv lignin and its acetate with synthetic polymers comprising vinyl pyrrolidone unit
Yoshikuni Teramoto, Noriko Tanaka, Manami Sakai, Takashi Endo
National Institute of Advanced Industrial Science and Teclmology (AIST), Biomass Technology ResearchCenter (BTRC), Kure 737-0197, Japan
Abstract：
Binary blends and pseudo complexes of organosolv lignin (OSL) and acetylated OSL withpoly(N-vinyl pyrrolidone) (PVP) and poly(N-vinyl pymolidone-co-vinyl acetate) (PVPVAc) were prepared,
respectively, by casting from mixed polymer solution in NN-dimethylformaide as good solvent and by
spontaneous co-precipitation &om solutions in tetrahydrofuran as comparatively poor solvent. Miscibility andintermolecular interaction of the blends were investigated by means of DSC and FT-IR. FT-IR spectra revealed
the presence of hydrogen-bonding interactions between hydroxyl groups of OSL and carbonyl groups of N-vinyl
pyrrolidone units. Thermal transition data obtained in the DSC analysis clarified that the blends of the twopolymers exhibited decidedly a single and composition-dependant Tg between the Tgs of the individualcomponents. This observation demonstrates that the blend system is miscible. The existences of both thehydroxyl group in OSL and VP unit in vinyl polymers were essential for the emergence of miscibility and theformation of pseudo-complexes.
2006-213
針葉樹パルプ製造とバイオエネルギー生産における国産カラマツ材の有効利用
高橋史帆，中川明子，金光氾，大井洋
筑波大学大学院生命環境科学研究科
Effective utilization of Japanese Larix leptolepis wood for production of softwood pulp and bio-energy
Shiho Takahashi, Akiko Nakagawa-izumi, Guang-fan Jin, Hiroshi Ohi
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8572 Japan
Abstract:
Eighty seven percent of the afforestation area in Japan is coniferous forest. For the effective
production of pulp and bio-energy, the kraft and soda pulp yieldsof Japanese major planted softwoods (Larix
leptolepis, Pinus densiflora, Cryptomeria japonica) were investigated, and compared those of imported
hardwoods (Acacia, Eucalyptus). The softwood pulp yields at a kraft pulp mill were estimated by a method
based on the ratios of mannose to glucose from pulps. The organic elements components in the black liquors
were estimated for their utilization as bio-energy.
2006-214
リグニンによる転写因子 NF− B の活性化の抑制
三橋進也、岸本崇生、浦木康光、生方信
北海道大学大学院農学研究科
Lignin suppresses NF- B activation in 293-T cells
Shinya Mitsuhashi, Takao Kishimoto, Yasumitsu Uraki, Makoto Ubukata
Research Faculty of Agriculture, Hokkaido University
Abstract:
Transcription factor NF-kB controls cell functions such as apoptosis, inflammation, the immune
response, cell growth, differentiation, and chronic infection with human immunodeficiency virus type 1(HIV-1).
Activation of NF- B by external stimuli such as tumor necrosis factor α(TNFα) and its binding to long terminal439

repeat (LTR) of HIV-1 triggers the initiation of transcription of viral genes. In this study, we use several lignins
to show that lignins inhibit expression of NF- B and LTR(HIV-1) reporter genes. Low molecular weightlignins (800>) were more effective rather than high molecular weight lignins. Furthermore, we exhibit that a β-5lignin model compound shows stronger inhibitory activity than β-O-4 lignin model compounds. These results
suggest that low molecular weight lignins (dimmer or trimer?) suppress HIV-1 replication and NF- B
activation, and that lignin could be lead-compound for medical drugs.
2006-215
酢酸リグニンの工業利用に関する研究
宮田直紀*1、荻野晋一*1、浦木康光*2、生方信*2*1
関西ペイント株式会社、*２北海道大学大学院農学研究科
A study for industrial utilization of acetic acid lignin
Naonori Miyata*1, Sinichi Ogino*1, Yasumitsu Uraki*2, Makoto Ubukata*2*1
Kansai Paint Co., Ltd., Hiratsuka 254-8562, Japan, *2Graduate School ofAgriculture, Hokkaido University,
Sapporo 060-8589, Japan
Abstract:
Attempts were made to utilize palm oil residues with acetic acid pulping process underatmospheric pressure. Empty fruit bunch, herein after called EFB, of the oil palm was digested into pulp andacetic acid lignin, herein after called AL, through the process, since lignin reacted with and dissolved into acetic
acid. Oil palm AL showed heat fusion characteristic and dissolved into organic solvents such as acetone and etc,
as same manner as other ALs taken from ordinary woods. Board-shaped moldings were prepared from the pulp
and the AL from EFB by proper pressurizing at around 170 degree C. Bending strength of the moldings was
easily controlled by varying molding pressure and/or temperature or composition ratio between the pulp and theAL. Another attempt was made to prove termites repellent or termiticide of the AL. Cedar chips treated withdiluted AL showed certain repellency and termiticide effect to suggest a new usage of the AL.
2006-特別講演 II
人工土壌マトリックスとしてのオガ屑 −リグニンの存在と意義一
寺沢 実
北海道大学大学院農学研究科、環境資源学部門、森林資源科学分野、森林化学研究室
Invited Lecture, II
Sawdust as an artificial soil matrix for bioconversion of biomass wastes into multifunctional recyclables Significance of the existence of lignin in sawdustMinoru Terazawa
Research Group of Forest Resources Science, Environmental Resources Division, Graduate School of
Agriculture, Hokkaido University, Sapporo 060-8589, Japan
Abstract:
Biomass wastes such as garbage (food oriented wastes), excreta, and livestock manure are
effectively bio-converted into multifunctional recyclables in the GADE (garbage automatic
decomposer-extinguisher), BT (bio-toilet, dry toilet or composting toilet), and LMF (livestock manure fixer)
systems, respectively, using sawdust as an artificial soil matrix in the systems. Mushroom cultivation beds,
anti-fire fiberboard, nutrition containing planting pots, pellets, packing materials, etc. are the multi-functional
recyclables. High porosity of sawdust is the main function of sawdust, offering the high air retention andmoderate water retention. High surface ratio of sawdust contributes the effective evaporation of water from thesawdust matrix. These characteristics keep the matrix aerobic conditions. Aerobic biodegradation of the organic
matters in the wastes is essential for the odorless operation of the systems. High bacterial tolerance and highabrasion tolerance are caused from the existence of lignin in the matrix. Because of the existence of lignin,sawdust can be used for long period as the artificial soil matrix. Practical uses of sawdust will be introduced.
2006-P01
リグニンの α 位水酸基の生成と脱離に関する分子軌道解析
伊藤直人*1、正本博士*1、重松幹二*1、岸本崇生*2*1
福岡大学工学部、*2 北海道大学大学院農学研究科
Molecular orbital analysis on the formation and cleavage of α-hydroxyl group in lignin
Naoto Ito*1, Hiroshi Masamoto*1, Mikiji Shigematsu*1, Takao Kishimoto*2*1
Faculty of Engineering, Fukuoka University, Fukuoka 814-0180, Japan, *2Graduate School of Agriculture,
Hokkaido University, Sapporo 060-8589, Japan440

Abstract:
To investigate the formation of α-hydroxyl group in lignin, the β-O-4 lignin model compounds
were analyzed with an ab initio molecular orbital calculation using RB3LYP/6-31G* method. The optimum
conformations were varied with the existence of methoxyl groups in B-ring. The electrostatic charges at
α-carbon were negative value and similar in neutral quinonemethides. For cationic enol radicals of guaiacyl andsyringyl models, the electrostatic charge at α-carbon transferred to positive value by protonation of ketone inquinonemethides. Also the HOMO-LUMO gaps were independent with the methoxyl groups but muchdecreased with protonation.
2006-P02
レジノール構造の生成に関する分子軌道解析
高口良輔，正本博士，重松幹二
福岡大学工学部
Molecular orbital analysis on the formation of resinol structure
Ryosuke Kouguchi，Hiroshi Masamoto, Mikiji Sbigematsu
Faculty of Engineering，Fukuoka University, Fukuoka 814−0180, Japan
Abstract:
The reaction mecbanism in radical couplingr eaction of lignin was analyzed with a molecularorbital calculation．The cbarge density, the electrostatic potential and the spin density of monolignol radicals
were determined with UB3LYP/6-31G* basis set．For the simulation in acid solution，the spin density at C8 wasincreased by protonation of O4．The transition states during radical coupling reaction were determined withsemi-empirical molecular orbital calculation by using UPM3．The simulation on the reaction of cationic andneutral radicals of sinapyl alcohol demonstrated that β-O coupling dominantly produced compared witb β-βcoupling. This computational result agrees with the experimental result that the production of β-O dimer
increases in acid solution．
2006-P03
木材抽出成分の着色に関する計算化学シミュレーション
宮脇圭司、正本博士、重松幹二
福岡大学工学部
Computer-chemical simulation on the coloration of woody extractives
Keiji Miyawaki, Hiroshi Masamoto, Mikiji Shigematsu
Faculty of Engineering, Fukuoka University, Fukuoka 814-0180, Japan
Abstract:
To predict the color change of norlignans, UV/VIS spectra were simulated with the molecularorbital energies determined by an ab initio molecular orbital calculation (RB3LYP/6-31G*). Obtained spectra
well expressed the coloration of sequirin-C involving the oxidation with enzyme, air or alkaline treatment;sequirin-C is the main component causing the blacking of sugi (Cryptomeria japonica) heartwood. We believe
this simulation technique is useful for the prediction of UV/VIS spectrum of unknown or unpurified substances,and the chase of intermediates in various reaction pathways.
2006-P04
計算化学によるタンニン吸着機構の解析
荒木孝文*1、正本博士*1、重松幹二*1、光永徹*2
福岡大学工学部、岐阜大応生
Computer-chemical analysis on the adsorption mechanism of tannin
Takafumi Araki*1, Hiroshi Masamoto*1, Mikiji Shigematsu*1, Tohru Mitsunaga*2*1
Faculty of Engineering, Fukuoka University, Fukuoka 814-0180, Japan, *2Faculty of Applied Biological
Science, Gifu University, Gifu 501-1193, Japan
Abstract:
The conformation, the dipole and the electrostatic potential of proanthocyanidins up to hexamer
were computed with a semi-empirical molecular orbital calculation (RPM3). In the case of (4α-8)-catechins, thedipole increased with the degree of polymerization. This tendency was parallel to the experimental result in the
precipitation of protein by fractionated bark tannin. For other proanthocyanidins, the dipoles of (4α-6)-catechinsand (4β-8)-epicatechins were decreased at odd and even values, respectively, of the degree of polymerization.
2006-P05
リグニンの熱分解：β-O-4 構造単位由来の生成物441

黒田健一*1，岸本崇生*2，中川明子*3，芦谷竜矢*4，藤田弘毅*1*1
九州大学大学院農学研究院、*2 北海道大学大学院農学研究科、*3 筑波大学大学院生命環境科学研究科、*4
秋田県立大学
Pyrolysis of lignin: Products stemming from β-O-4 subunits
Ken-ichi Kuroda*1, Takao Kishimoto*2, Akiko Nakagawa-izumi*3, Tatsuya Ashitami*4, Koki Fujita*1*1
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University, 6-10-1
Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan, *2Graduate School of Agriculture, Hokkaido University,
Sapporo, 060-85 89, Japa, *3Graduate School of Life and Environmental Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8572, Japan, *4Institute of Wood Technology, Akita Prefectural University, 11-1, Kaieizaka,
Noshiro, Akita 016-0876, Japan
Abstract:
Sources of pyrolysis products of lignin were investigated in conventional pyrolysis and in
pyrolysis in the presence of tetramethylammonium hydroxide (TMAH) (TMAH thermochemolysis). To know
the contribution of β-O-4 subunits to the pyrograms of lignins, a polymer (I, DPn 15.8), connected only by
β-O-4 linkages, was subjected to both conventional pyrolysis (500ºC/4s) and TMAH thermochemolysis(315ºC/4s). Products were monitored by gas chromatography/mass spectrometry and compared with those of
guaiacylglycerol-β-guaiacyl erther (II) and lignins (bulk dehydrogenation polymer of coniferyl alcohol andJapanese cedar wood lignin). I produced most of monomeric products observed in conventional pyrolysis and
TMAH thermochemolysis. The results
show that β-O-4 subunits make a large contribution to the lignin pyrograms obtained in conventional pyrolysis
and TMAH thermochemolysis.
2006-P06
白色腐朽担子菌による PCB 代謝に関与するメチルトランスフエラーゼ
岸本雅樹、亀井一郎、近藤隆一郎
九州大学大学院農学研究院
Methyltransferase involved in PCB metabolism by white-rot fungi
Masaki Kishimoto, Ichiro Kamei, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
Polychlorinated biphenyls (PCBs) are recalcitrant pollutants. Degradation experiment of model
PCB compound, 4,4'-dichlorobipheny1 (4,4'-DCB) and its metabolites by white-rot fungus, Phlebia brevispora
TMIC33929, which is capable of degrading a part of coplanar PCBs was carried out. The metabolic pathway of
4,4'-DCB was elucidated by the identification of metabolites upon addition of 4,4'-DCB and its metabolic
intermediates. These results suggested the metabolic pathway was branched two pathways, a methylation
pathway and a ring cleavage pathway, via initial metabolite, 3-hydroxy-4,4'-DCB. Of two pathways, themethylation pathway was predominantly compared to the ring cleavage pathway, and 3-methoxy-4,4'-DCB was
decreased slowly. The conversion of 3-hydroxy-4,4'-DCB into 3-methoxy-4,4'-DCB was shown to occur by O
methylation of 3-hydroxy-4,4'-DCB in a reaction catalyzed by S-adenosyl-L-methionine dependent
O-methyltransferase.
2006-P07
白色腐朽菌からの微生物製剤作成の試み
佐々木良輝、古山健太、伊藤和貴、橘燦郎
愛媛大学農学部
Attempts to make a microbial preparation from a white-rot fungus
Yoshiteru Sasaki, Kenta Furuyama, Kazutaka Itoh, Sanro Tachibana
Department of Applied Bioscience, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime
790-8566, Japan
Abstract:
In the present study, microbial preparation used several porous materials (zeolite, charcoal
coated with ceramics, and wood) as basic materials were tried to prepare for bioremediation ofdioxin-contaminated soil with white-rot fungi. The microbial preparations were made by adsorption of fungal
biomass on the surface of porous materials. Furthermore, the microbial preparations were entrapped withcalcium alginate gel. And the preparations were estimated by thedecolonization ability on the agar plate impregnated with the dye as well as degradation rate of
2,4,8-Trichlorodibenzofuran (2,4,8-TCDF) in the soil. The degradation rate of 2,4,8-TCDF in the soil was only
10% for 30 days when the treatment with non-entrapped microbial preparation (zeolite) was conducted for 30
days. In contrast, 20% of 2,4,8-TCDF was degraded when the treatment with442

entrapped microbial preparations (zeolite and charcoal) was conducted for 30 days. These results suggest thatbioremediation of dioxin-contaminated soil by microbial preparations made from white-rot fungi is possible.
2006-P08
ダイオキシン分解菌からの酵素を用いた酵素製剤作成の試み
藤井啓太，橘 燦郎，栗田紘希，柚本 聡，伊藤和貴
愛媛大学農学部
Attempts to make an enzyme preparation by crude enzyme from fungus capable of dioxins
Keita Fujii, Sanro Tachibana, Kouki Kurita, Satoshi Somamoto, Kazutaka Ito
Department of Applied Bioscience, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime
790-8566, Japan
Abstract:
Environmental pollution caused by endocrine disrupting chemicals (envirornental hormones)
such as DDT [1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane] has become a major social problem. Therefore,
several methods of dealing with environmental pollution have been proposed. Bioremediation withmicroorganisms or enzymes from the microorganisms is considered a most effective method of dealing withwidespread pollution involving a low concentration of pollutant. In the present report, biodegradation ofenvironmental
hormones[DDT,
2,4,8-TCDF(2,4,8-trichlorodibenzofuran)andTCB(3,3’,4,4’-tetrachlorobiphenyl)] in water with a double capsule (an enzyme preparation) prepared from crude
enzyme from fungi capable of dioxins, HBT(1-hydroxybenzo- triazole) and so on was conducted. The result
showed that DDT, 2,4,8-TCDF and TCB could be degraded for 72 hours by the treatment. The rates ofdegradation were 50, 15 and 30%, respectively. In addition, environmental hormones (DDT, TCB) in soil werealso degraded by the treatment.
2006-P09
ゴマの機能性リグナンの生合成、特にセサミノール配糖体等について
鈴木利貞*1、片山健至*1、大野素未*1、小堀里恵*1、並木満夫*2、田代 亨*3*1
香川大学農学部、*2 おいしさの科学研究所、*3 千葉大学園芸学部
Biosynthesis of functional lignans, particularly sesaminol glycosides, in Sesamum indicum seeds
Toshisada Suzuki*1,Takeshi Katayama*1,Motomi Olmo*1,Rie Kobori*1,Mitsuo Namiki*2, Toru Tashiro*3*1
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, *2Institute of Oishisa
Science, 2217-44 Hayashi, Takamatsu, Kagawa 761-0301, *3Faculty of Horticulture, Chiba University, 648
Matsudo, Chiba 271-8510
Abstract:
Sesame seeds contain phenolic and antioxidant lignans such as sesaminol and pinoresinol, as
well as sesamin and sesamolin. However, biosynthesis of the sesame lignans, particularly sesaminol andsesaminol glycosides was not clarified. In this study, feeding experiments of L-[U-14C]phenylalanine (Phe) werecarried out. A solution of L-[U-14C]Phe (10 mM, 20 ml) was injected into unripe capsules of 11 week-old intact
plants (Sesame indicum var. Mie-dai No.1 and S. indicum var. Chinese 36), and the plants were cultivated for aweek at 26ºC. The radioactivity wasincorporated into free sesaminol and sesaminol triglucoside and sesaminol diglucoside. The percent
incorporation into sesaminol and sesaminol glycosides in seeds was eight times larger than that in the pods. In
addition, the radioactivity was incorporated into 7-carbonyl type lignan glycoside in seeds
2006-P10
新規白色腐朽菌 Phellinus sp. SKM2102 株の脂肪酸不飽和化酵素遺伝子の単離・解析
吉田太郎、矢野健太、津田冴子、渡遽崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Characterization of fatty acid desaturase genes from a white-rot fungus, Phellinus sp. SKM2102
Taro Yoshida, Kenta Yano, Saeko Tsuda, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Laboratory of Biomass conversion, Research Institute for Sustainable Humanosphere, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
Abstract:
A new white-rot fungus, Phellinus sp. SKM2102, exhibits high pretreatment effects for
enzymatic saccharification of wood similar to those of a selective lignin-degrading fungus, Ceriporiopsis
subvermispora. However, profiles of their metabolites, such as fatty acids, are different, reflecting thedifferences of the gene expression involved in the fatty acid metabolism of these strains. We focus on the fatty
acid metabolism, especially the biosynthesis of unsaturated fatty acids because unsaturated fatty acids are theprecursors of lipid peroxidation in the selective lignin degradation by C. subvermispora. In order to investigate443

the unsaturation of fatty acids, we have already cloned fatty acid desaturase genes from C. subvermispora. In
this report, we cloned fatty acid desaturase genes from SKM2102 by PCR-based method.
2006-P11
フエルラ酸ステアリルの酵素触媒二次元重合
坂本昌平、上高原 浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Enzyme-catalyzed two-dimensional polymerization of stearylferulate
Shohei Sakamoto, Hiroshi Kamitakahara, Toshiyuki Takano, Fmiaki Nakatsubo
Graduate School of Agriculture, Kyoto University, Kyoto 606-8502, Japan
Abstract:
Two-dimensional polymerizadon is a novel approach which can bring improved control ofmonomer reactivity and orientation in the resulting polymer compared to the polymer by conventional method.
A good p-A isotherm of Stearylferulate (FA18) was obtained on phosphate buffer (pH=6.5) as well as on
ultrapure water, so FA18 was spread at an air-water interface on buffer solution, and polymerized withhorseradish peroxidase (HRP) and H2O2 in dark. From the results of UV spectroscopic analysis, it wassuggested that the two-dimensional polymerization afforded the polymer with different bond pattern from thatof the conventional polymer.
2006-P12
リグニンモデル化合物の電気化学的酸化
白石 匠、上高原 浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Electrooxidation of lignin model compounds
Takumi Shiraishi, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku
Kyoto, 606-8502, Japan
Abstract:
The anodic oxidation of a lignin model compound, 1-(4'-ethoxy-3'-methoxyphenyl) ethanol(1G) was investigated to introduce carbnyl group at a-position. Cyclic voltammetric measurements of 1G andother 1-phneyl ethanol derivatives, 1-(4'-ethoxy-3',5'-dimethoxyphenyl) ethanol (1S) and 1-(4'-ehoKyPhen9)ethanol (1 P), were performed to determine their redox potentials and compare electronic properties ofnonphenolic G S, P substructures in lignins. The compound 1G was oxidized by bulk electrolysis in acetonitrile.
In electrolysis without base, various side reactions occurred, and a-carbonyl product was obtained in low yield.
Whereas, electrolysis with base or H2O gave α-carbonyl derivative (2G) in high yield. The proposed
electrooxidation mechanism of 1G is likely guideline for α-carbonyl introduction to neutral lignin structures.
2006-P13
植物細胞壁木化過程のシュミレーション、—ポリエチレングリコールを用いたシリンギルグリセロールーβーシ
ナピルアルコールエーテルの合成—
小路裕美*1、小林孝行*1、棚橋光彦*1、重松幹二*2*1
岐阜大学大学院農学研究科、*２福岡大学工学部
Simulation of plant cell wall lignification process - Dehydrogenative syringylglycerol-β-sinapyl alcohol ether inthe presence of polyethylene glycolHiromi Koji*1, Takayuki Kobayashi*1, Mitsuhiko Tanahashi*1, Mikiji Shigematsu*2*1
Laboratory of Biomass Conversion, Graduate School of Agriculture, Gifu University, 1-1Yanagido, 501-1193
Gifu, Japan, *2Faculty of Engineering, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku,
Fukuoka 814-0180, Japan
Abstract:
DHPs (dehydrogenative polymer of monolignols, artifical lignins) have been used as modelcompounds to clarify the chemical structure and the formation mechanism of lignins in plant cell walls. DHP of
the sinapyl alcohol is remarkably different from lignin in the hardwood cell wall. For example, syringaresinol isformed mainly from the sinapyl alcohol with a small amount of β-O-4 type on using the mixed method
polymerization. Also, in relating to the drop-wised method polymerization, lower molecular weight S-DHP
including mainly β-βtype linkage are formed. It is therefore important to examine the polymerization conditionof DHP for clarifying the biosynthesis mechanism of lignin in cell wall. We have succeeded to synthesize lignin
containing a large amount of β-O-4 unit under the hydrophobic condition using the polysaccharide gel. In thepaper, enzymatic dehydrogenative polymerization of sinapyl alcohol is tried under the hydrophobic condition444

using polyethylene glycol (PEG).
2006-P14
広葉樹硫酸リグニンのフェノール化に関する研究
松下泰幸、佐野仁美、今井絡徳、今井貴規、福島和彦
名古屋大学大学院生命農学研究科
Study of phenolization of hardwood sulfuric acid lignin
Yasuyuki Matsushita, Hitomi Sano, Masanori Imai, Takanori Imai, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-860l Japan
Abstract:
To study the behavior of hardwood sulfuric acid lignin (SAL) during phenolization, we
compared the product yield, average molecular weight, methoxy content, and reactions of simple modelcompounds with those of softwood SAL, focusing on the difference between syringyl and guaiacyl units. The
beech SAL reacted with phenol more readily than red pine SAL and yielded a greater soluble fraction ofphenolized SAL. To investigate the difference in the phenolization activity of the syringyl and guaiacyl units inbeech lignin, we prepared syringyl-nucleus-rich sulfuric acid lignin (S-rich-SAL) and guaiacyl-nucleus-richsulfuric acid lignin (G-rich-SAL) from beech, which were subjected to phenolization. The results suggest thatthe syringyl unit in SAL had greater phenolization activity and its phenolized products were more soluble inacidic aqueous medium and introduced less phenol than the guaiacyl unit to solubilize. The study using modelcompounds also showed that the syringyl unit had higher phenolization reactivity than the guaiacyl unit.
2006-P15
リグノクレゾールを利用した環境適合型接着剤の開発
原田征*1、石垣友三*1、小田三都郎*1、秋田重人*1、平野幸治*1、福田博行*1、水野恭介*2、岡部洋治*2*1
名古屋市工業研究所、*2 東洋樹脂株式会社
Development of environmental-friendly lignocresol-based adhesive
Masaki Harada*1, Yuzo Ishigaki*1, Mitsuo Od*1, Shigendo Akita*1, Koji Hirano*1, Hiroyuki Fukuda*1, Kyosuke
Mizuno*2, Yoji Okabe*2*1
Nagoya Municipal Industrial Research Institetute, 3-4-41 Rokuban, Atsuta-ku, Nagoya 456-0058, Japan,*2
Toyo Jushi Co., 450, Hayashiazanohara, Komaki, Aichi 485-0805, Japan
Abstract:
Biodegradable lignin-derivatives are gathering attention as a possible source for polymer
materials. Lignocresol (LC) is produced through reactive extraction with p-cresol from lignin- containing wood,and is considered to be biomass-derived polyol since it has a number of phenolic and alcoholic hydroxyl groups.
In this study, a polyurethane based adhesive was prepared from a ternary mixture of LC / polyethylene glycol(PEG) / Lysine triisocyanate (LTI) (2-Isocyanatethyl- 2,6-diisocyanatecaproate), and was applied for thebonding of wood. Satisfactory tensile share strength of over 10 MPa was obtained with the adhesive, indicatinga promising use of LC as an ingredient of environmentally-friendly adhesives.
2006-P16
白色腐朽菌 Phanerochaete sordida YK-624 株の産生する菌体外ペプチド様物質の機能特性
平井浩文，森田英弘，河合真吾，西田友昭
静岡大学農学部
Functional characterization of peptide-like compound produced by white-rot fungus Phanerochaete sordida
YK-624
Hirofumi Hirai, Hidehiro Morita, Shingo Kawai, Tomoaki Nishida
Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
White-rot fungus Phanerochaete sordida YK-624 produced a compound (YK-S) which
inhibited the veratryl alcohol (VA) oxidation by novel lignin peroxidase (YK-LiP1) from this fungus. YK-S,
which was produced under shaking culture, was purified to homogeneity by anion-exchange chromatography
and gel permeation chromatography. By MALDI TOF-MS analysis, the molecular mass of YK-S was 1.822 Da,
and YK-S contained 560 Da of peptide. Inhibitory effect of YK-S on VA oxidation by YK-LiP1 was investigatedby Lineweaver-Burke plot in order to analyze the reaction mechanism of YK-S with YK-LiP1. YK-S inhibited
VA oxidation by YK-LiP1 in a noncompetitive manner, and Ki Value of YK-S for YK-LiP1 was 103 mM.
Moreover, the inactivation of YK-LiP1 by hydrogen peroxide was repressed under the presence of YK-S. These
results strongly suggest that the role of YK-S is same as that of VA which functions as the substrate of Lip fromP. chrysosporium.
445

2006-P17
バクテリアによるリグニン由来化合物代謝に関与する新規脱メチルシステム
阿部友邦*1、佐々木光雪*1、宮内啓介*1、政井英司*1、福田雅夫*1、片山義博*2*1
長岡技術科学大学・生物機能工学、*2 東京農工大学大学院 BASE
A novel tetrahydrofolate-dependent O-demethylation system in lignin metabolism by bacteria
Tomokuni Abe*1, Miyuki Sasaki*1, Keisuke Miyauchi*1, Yoshihiro Katayama*2, Eiji Masai*1, Masao Fukuda*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, *2Graduate
School of Bio Applications and Systems Engineering, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588, Japan
Abstract:
The catabolism of vanillate and syringate by bacteria is an important process of the
microbial lignin degradation. In Sphingomonas paucimobilis SYK-6, vanillate and syringate are converted into
protocatechuate (PCA) and 3-O-methylgallate (3MGA), respectively, byO-demethylases. In this study, we isolated the ligM gene that conferred on Escherichia coli the activity required
for the conversion of vanillate and 3MGA to PCA and gallate, respectively, with similar specific activities. The
LigM catalyzes the transfer of the methyl moiety of vanillate to tetrahydrofolate (H4folate), thereby forming
PCA and 5-methyl-H4folate. We demonstrated that PCA is not a growth substrate for SYK-6 cells, but we also
showed that this strain is able to grow well on PCA in the presence of methionine. This finding suggested thatthe 5-methyl-H4folate generated by the O demethylation of vanillate is essential for methionine biosynthesis.
Downstream of ligM, two ORFs, which showed similarity with 5,10-methylene-H4folate reductase gene (metF)
and
10-formyl-H4folate synthetase gene (ligH), were identified, and these genes were found to constitute an operon.
These results indicated that the O demethylation of vanillate and the C1 metabolism are simultaneously
regulated in SYK-6. In conclusion, the O demethylation of vanillate catalyzed by LigM is important for SYK-6
cells, not only as a degradation step for vanillate, but also to supply the 5-methyl-H4folate required formethionine biosynthesis.
2006-P18
バクテリアによるシリンガ酸代謝に関与するジオキシゲナーゼシステム
笠井大輔*1、政井英司*1、宮内啓介*1、福田雅夫*1、片山義博*２*1
長岡技術科学大学・生物機能工学、*2 東京農工大学大学院 BASE
The ring cleavage dioxygenase system involved in the syringate catabolic pathways in Sphingomonas
paucimobilis SYK-6
Daistike Kasai*1, Eiji Masai*1, Keisuke Miyauchi*1, Yoshihiro Katayama*2, Masao Ftikuda*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, *2Graduate
School of Bio-Applications and Systems Engineering, Tokyo Univwsiy of Agriculture and Technology, Koganei,
Tokyo 184-8588, Japan
Abstract:
Sphingomonas paucimobilis SYK-6 converts vanillate and syringate, which are intermediate
metabolites of lignin, to protochatechuate (PCA) and 3-O-methylgallate (3MGA), respectively. Previous studies
have indicated that PCA is further degraded by the reaction catalyzed by PCA 4,5-dioxygenase (LigAB) in PCA
4,5-cleavage pathway. In order to determine die ring cleavage pathways for syringate metabolism, we isolated
and characterized the ring cleavage dioxygenase genes, desZ and desB, which confer the 3MGA and gallate
degradation activities on Escherichia coli, respectively. Based on the analysis of enzymatic properties of thesegene products and various SYK-6 mutants lacking die genes involved in the syringate degradation, we
concluded that (i) all three-ring cleavage dioxygenases are involved in syringate catabolism, (ii) DesB and
LigAB are involved in the degradation of gallate, and (iii) the pathway involving DesB plays an especially
important role in the growth of SYK-6 on syringate.
2006-P19
樹木の細胞分裂制御に関する研究
松井紀子*1、本村莱荊子 *1、半智史*2、西窪仲之*3、篠崎祐介*4、佐藤かんな*5 、北野英己*5、船田良*2、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*２東京農工大学大学院農学研究科、*３理化学研究所植物科学研究センター、*４
名古屋大学大学院生命農学研究科、*５名古屋大学・生物機能開発利用研究センター
Research on cell division control of woody plant
Noriko Matsui*1, Mariko Motomura*1, Satoshi Nakaba*2, Nobuyuki Nishikubo*3, Yusuke Shinozaki*4, Kanna
446

Sato*5, Hidemi Kitano*5, Ryo Funada*2, Shinya Kajita*1, Yoshihiro Katayama*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan, *2Graduate school of Agriculture, Tokyo University ofAgriculture and Technology, Fuchu, Tokyo, 183-8509, Japan, *3RIKEN Plant Science center, Yokohama,
Kanagawa, 230-0045, Japan, *4Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, Aichi,
464-8601, Japan, *5Bioscience and Bioteclmology Center, Nagoya University, Nagoya, Aichi, 464-8601, Japan
Abstract:
As the largest storage organ in woody plants, it is of economic significance because most forest
products are derived from the stem and help alleviate global warming by sequestering and storing carbons inlong-term storage. Thickening of stem occurs as a result of growth and differentiation of secondary tissues
produced by the vascular cambium. Therefore, control of cell division in vascular cambium leads to theimprovement of woody resource production. In this study, we generated transgenic tobacco and poplar
overexpressing CycD, E2F and DP-core cell cycle related genes and examined their influences for cell division,
cell expansion, cell wall biosynthesis and lignification in secondary xylem. Moreover, as another approach of
the cell division control, we try to solve the mechanism of an increase of the number of cells by suppression ofgenes. Here, we screened and analyzed a rice mutant that has many cells though growth normally.
2006-P20
シキミ酸経路を経由したグルコースからの 2H-pyran-2-one--4,6-dicarboxylicacid（PDC）生産系の開発
西野由香里*1、田村真統*1、大塚博之*1、近藤晋*1、政井英司*2、片山義博*1、梶田真也*1
東京農工大学大学院 BASE、長岡技術科学大学・生物機能工学
Biological conversion of glucose to 2H-pyran-2-one-4,6-dicarboxylic acid (PDC) by the bypassed shikimate
pathways
Yukari Nishino*1, Masatsugu Tamura*1, Hiroyuki Otsuka*1, Susumu Kondo*1, Eiji Masai*2, Yoshihiro
Katayama*1, Shinya Kajita*1*1
Graduate school of Bio-Applications and Systems Engineering, *2Tokyo University ofAgriculture andTechnology, Koganei, Tokyo 184-8588, Japan, *2Nagaoka University ofTechnology, Nagaoka, Niigata 940-2188,
Japan
Abstract:
PDC, 2H-pyran-2-one-4,6-diarboxylic acid, is one of metabolic intermediates in Sphingomonas
paucimobilis SYK-6 that is a degrader of lignin-derived compounds. This compound has been alsocharacterized as a raw material for synthetic polymers such as polyester and polyamide. In the previous study,
we have already constructed the system on which PDC was efficiently converted from the aromatic compounds
such as vanillic acid and vanillin in the recombinant microorganisms. In order to develop alternative system for
PDC production, we try to produce the compound from glucose, which is one of low-cost sugars expected to beconverted from abundant cellulose wastes and biomass crops. In the present study, we constructed two types ofrecombinant bacteria with the bypasses in their own shikimate pathways. By HPLC analysis, a trace amount of
PDC that derived from glucose could be detected in the culture medium of the recombinant bacterium with ubiC,
pobA and LigABC. Our result suggests that the bypassed shikimate pathway provide an alternative option for
PDC production.
2006-P21
カワラタケ由来のラッカーゼ遺伝子を導入した組換え植物に見られる雄性不稔の解析
中村雄己*1、園木和典*2、飯村洋介*2、片山義博*1、梶田真也*1
東京農工大学大学院 BASE、産業技術総合研究所
Analysis of male sterility in the transgenic plants with the chimeric gene construct derived from the Trametes
versicolor laccase gene
Yuki Nakamura*1, Tomonori Sonoki*2, Yosuke Iimura*2, Yoshihiro Katayama*1, Shinya Kajita*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, *2National (nstitute of Advanced fndustrial Science and Technology,
Tsukuba, Ibaraki 305-8569, Japan
Abstract:
Laccase that require O2 as secondary substrate can oxidize phenolic compounds. In the previous
work, we have isolated a laccase cDNA, CVL3, from Trametes versicolor cDNA pool and generated transgenic
tobacco plants in which a chimeric laccase gene was expressed under the control of cauliflower 35S promoter
elements. Some of the transgenic plants overexpressing the gene could secret recombinant laccase protein fromtheir roots. The secretory laccase activity in the plants was responsible for the transformation of phenolic
compounds such as pentachlorophenol. Flowers of four transgenic lines, FL4, FL9, FL20 and FL22 with highly
laccase activity exhibited mate sterile due to inhibition of anther maturation and dehiscence. Levels of laccase447

activity in the anthers of these four transgenic plants have reached by over 6-fold increase as compared to that inwild-type plant. These results indicate that the laccase protein may play some physiological roles in antherdevelopment.
2006-P22
オゾン酸化を用いたリグニン系土壌改良剤の開発 II −オゾン酸化リグニンの酸化の程度と Al 毒性除去能との関係についての研究
相見 光、大村 知士、加藤 珠央、中原 知子、志水一允
日本大学生物資源科学部
Development of lignin soil conditioning agent by ozone treatment II. -Studies on relationship between degree ofoxidation and reduction of aluminum toxicity for ozone treated lignin
Hikaru Aimi, Satoshi Ohmura, Tamao Katoh, Tomoko Nakahara, Kazumasa Shimizu
Laboratory of Biomass Sciences, Department of Forest Sciences and Resources, College of Bioresource
Sciences, the Nihon University,1866 Kameino, Fujisawa, Kanagawa, 252-8510, Japan
Abstract:
Relationship between degree of oxidation for oxidized lignin and its ability for the reduction ofaluminum toxicity was examined in this study. The oxidized lignin samples were prepared by ozone or alkaline
oxygen treatments. Degrees of oxidation for these samples were evaluated by permanganate consumption andmethoxyl content after saponification. The lignin treated with ozone for 4h lost about 85% of methoxyl group,
but the lignins treated by alkaline oxygen lost only about 4-14% of it. Both of them were, however, effective for
reduction of aluminum toxicity. These facts were also confirmed by IR analysis. These results suggest that otherfactors, such as water-solubility or difference of reaction mechanism between ozone and alkaline oxygen, aremore important than degree of oxidation for reduction of aluminum toxicity.
2006-P23
酸性下におけるリグニン β-O-4 結合開裂勝構の再評価（３） 一 C6-C3 リグニンモデル合物を用いた解析一
伊藤宏昭、横山朝哉、松本雄二
束京大学大学院農学生命科学研究科
Reevaluation of the mechanism for ale cleavage of lignin β-O-4 bond under acidic conditions (3) -Experiments
using a C6-C3 model compound Hiroaki Ito, Tomoya Yokoyama, Yuji Matstmoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
Acidolysis of lignin is a method used for structural analysis and isolation of liignin. The
main reaction during acidolysis is the clavage of β-O-4 bond. According to the mechanism proposed by
Lundquist et al., die rate-determining step of the reaction is the Abstraction of the β-proton from a benzyl cation
substructure, resulting in the formation of an enol ether type substructure. Although other reports show diedependence of the cleavage rate on the kind of acid used, it is impossible to explain die dependence based on themechanism proposed. Therefore, it is necessary to reinvestigate the reaction mechanism of acidolysis andanalyze its kinetic. A dimeric non-phenolic lignin model compound, veratrylglycerol-β-guaiacyl ether (VG), wastreated with HBr in 82% aqueous dioxane. It was found that the elimination of γ-position as formaldehyde does
not occur in the system. This result is contrast with the known fact that die elimination of formaldehyde isoccurred when HCl is used as a catalyst. It is suggested that HBr is more suitable than HCl as a catalyst of
acidolysis.
2006-P24
熱帯産樹アテ材のリグニン化学構造
Deded S．Nawawi、Wasrin Syafii、秋山拓也、松本雄二、飯塚尭介
東京大学大学院農学生命科学研究科
Chemical tructure of lignin in reaction wood of tropical species
Deded S. Nawawi, Wasrin Syafii, Takuya Akiyama, Yuji Matsumoto, Gyosuke Meshitsuka
Wood Chemistry Laboratory, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
Reaction woods were obtained from leaning wood stems or branches of several tropical woodspecies and the relationships between the type of reaction wood and lignin characteristics was surveyed. As
lignin characteristics, stereo structure of β-O-4 linkage (erythro ratio), aromatic ring type (syringyl ratio),448

Klason lignin yield and acid soluble lignin content were determined. Tentatively, the relationships could beclassified into 4 types. In all types, erythro ratio changed with clear tendency from the reaction wood part toopposite wood part, but the direction of the change was dependent on the type. In G-S lignin (guaiacyl-syringyl
lignin) erythro ratio was highly correlated with syringyl ratio, and in G-lignin, it was correlated withp-hydroxyphenyl content.
2006-P26
アルカリ及びアルカリ酸素処理において α-カルボニル基の存在が及ぼすリグニン分解反応への影響
今井愛子、横山朝哉、松本雄二、飯塚尭介
東京大学大学院農学生命科学研究科
Effects of the presence of α-carbonyl group on the degradation reactions of lignin during anaerobic and aerobic
alkaline treatments
Aiko Imai, Tomoya Yokoyama, Yuji Matsumoto, Gyosuke Meshitsuka
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
It is well known that the presence of α-carbonyl group in lignin has a significant effect on its
reactivity toward various chemical reactions. However in most of the researches, the effect has been studied
when α-carbonyl group is located at the lignin phenylpropane unit where the target reactions are occurred(located at A-ring). In this study, the effect of α-carbonyl group on the reactions occurred under anaerobic andaerobic alkaline conditions was examined when the group is located at the unit next to that where the reactions
are operative (located at B-ring) using a dimeric lignin model compound, guaiacylglycerol-β-ethylvanillin ether(GE). A significant amount of ethylvanillin was obtained in the nitrogen-alkali treatment of GE. This result
indicates that the presence of α-carbonyl group at the B-ring surprisingly accelerates the alkali promoted β-O-4bond cleavage. A large amount of vanillin was obtained in the oxygen-alkali treatment of GE. This is quite
contrast to the result observed when an analogous model compound of GE without the α-carbonyl group wastreated under the same conditions. These phenomena indicate that the rate of the Cα-Cβbond cleavage exceedsthat of the aromatic ring scission. It is suggested that the presence of α-carbonyl group at the B-ring changes thereaction site of lignin where oxygen oxidation is occurred.
2006-P27
ケナフリグニンの化学構造について
中川明子*1、土居修一*1、黒田健一*2*1
筑波大学大学院生命環境科学研究科、*2 九州大学大学院農学研究院
Chemical structures of kenaf (Hibiscus cannabinus) lignin
Akiko Nakagawa-izumi*1, Ken-ichi Kuroda*2, shuichi Doi*1*1
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8572
Japan, *2Deparbnent of Forest and Forest Products Sciences, Faculty of Agriculture,
Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
Kenaf (Hibiscus cannabinus), variety Everlglades, bast native and isolated lignins were
subjected to analytical pyrolysis to confirm unusual structures of kenaf lignin. Pyrolysis results showed that the
kenaf sample employed in the present study contains no comiferyl and sinapyl alcohols with an acetyl group at
the γ-position, and it has a paucity of 5-hydroxyguaiacyl units because the small abundance of
3-methoxycatechols was present in the pyrolyzates.
2006-P28
ケナフ靭皮クラフトパルプの酸素漂白特性
金光苑，中川明子，大井洋
筑波大学大学院生命環境科学研究科
Characteristic of kenaf bast kraft pulp for oxygen bleaching
Guang-fan Jin, Akiko Nakagawa-izumi, Hiroshi Ohi
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8572 Japan
Abstract:
Kraft cooking efficiency of bast of Hibiscus cannabinus (kenaf) was compared with that of
Acacia mearnsii and Eucalyptus spp. Although the lignin content of the bast was lower than that of A. mearnsii
wood, the selectivity of delignification of the bast was not better than that of the hardwoods. The bast contained
more uronic acids than the hardwoods. Then, it consumed more alkali during kraft cooking and did not show
better delignification selectivity. However, the bast pulp was easily oxygen-bleached at a small alkali charge,449

resulting in a low kappa number.
2006-P29
リグニンの温度変調型 DSC 分析
久保智史*1、山田竜彦*1、橋田光*1、浦木康光*2、John F．Kadla*3*1
森林総合研究所、*2 北海道大学大学院農学研究科、*3 ブリティッシュコロンビア大学
Temperature modulated DSC analysis of isolated lignin
Satoshi Kubo*1, Tatsuhiko Yamad*1, Koh Hashida*1, Yasumitsu Uraki*2, John F. Kadla*3*1
Department of Biomass Chemistry, Forestry and Forest Products Research Institute, Tsukuba, 305-8687 Japan,*2
Graduate School of Agriculture, Hokkaido University, Sapporo, 060-8589 Japan*3
Depanment of Wood Science, University of British Columbia, Vancouver, B.C., V6T IZ4 Canada
Abstract:
DSC is commonly used to examine the thermal properties of lignin preparations. However, inmany of the lignin preparations a large enthalpic relaxation peak overlaps the glass transition, Tg, region in the
DSC curve, which makes it difficult to identify the Tg. This is typically addressed by applying a pre-heat
treatment (first scan) to remove this endothermic peak. However, lignin preparations have thermosetting
properties as well as thermo-plasticity; the chemical structure of lignin changes during the heat treatment. To
avoid this problem, temperature modulated DSC (TMDSC) was examined for thermal analysis of lignin
preparation. By use of TMDSC, an enthalpic relaxation peak can be removed from total heat flow, and Tg oflignin preparation can be clearly seen without pre-treatment, In conventional DSC run, Tg temperature of lignin
preparations were only slightly increased by repeating heat treatment. However, Tg temperature measured in
2nd heating run is remarkably higher than in 1st heating. This indicates that pre-heat treatment of DSC run
affects the Tg of the lignin preparation.
2006-P30
β−O−4 型人工リグニンポリマーの合成とその性質 −シリンギルタイプの合成−
岸本崇生、浦木康光、生方信
北海道大学大学院農学研究科
Synthesis of βO-4 type artificial lignin polymers and their properties - Synthesis of syringyl type lignin
polymer Takao Kishimoto, Yasumitsu Uraki, Makoto Ubukata
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589
Abstract:
The β-O-4 structure is one of the most important substructures in lignin. Guaiacyl type artificial
lignin polymer composed of only β-O-4 structure has been synthesized in our laboratory. In this investigation
syringyl type monomer was treated with potassium carbonate and reduced with sodium borohydride to yield apolymer. The polymer was acetylated and fully analyzed by NMR spectroscopy.
2006-P31
オルガノソルブリグニンアルキルエステル／ポリ（ε-カブロラクトン）環境適合型ブレンドの相構造評価
寺本好邦*1，李承桓*2，田中紀子*1，堺真奈美*1，遠藤貴士*1*1
産業技術総合研究所バイオマス研究センター、*２テネシー州立大学
Phase structure of biodegradable poly(ε-caprolactone) with organosolv lignin alkyl esters
Yoshikuni Teramoto*1, Seung-Hwan Lee*2, Noriko Tanaka*1, Manami Saka*1, Takashi Endo*1*1
National Institute of Advanced Industrial Science and Technology (AIST), Biomass Technology ResearchCenter (BTRC), Kure 737-0197, Japan, *2Forest Products Center, The University of Tennessee, Knoxville, TN37996, USA
Abstract:
Organosolv lignin (OSL) alkyl esters (carbon number, 2-5) were synthesized by ahomogeneous reaction with different acyl anhydrides/4-dimethylamino pyridine in pyridine solution. The
miscibility of the esterified OSLs with poly(ε-caprolactone) (PCL) was investigated, mainly through thermal
analysis by differential scanning calorimetry (DSC). DSC analysis revealed that a polymer pair OSL
butyrate/PCL and valerate/PCL showed a compatibility. Atomic force microscopy also indicated that noremarkable phase separation occurred in these two blends.

450

第 52 回 （2007.11.14-15） 宇都宮大学 大学会館
2007-101
ゼラチン層を形成しない広葉樹あて材におけるリグニン分布
平岩季子、石栗 太、飯塚和也、横田信三、吉澤伸夫
宇都宮大学農学部
Lignin distribution in tension wood cell walls without gelatinous layer
Tokiko Hiraiwa, Futoshi Ishiguri, Kazuya Iizuka, Shinso Yokota, Nobuo Yoshizawa
Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
The present study investigated affects of inclination angle on reaction wood formationin three angiosperm species (Paulownia tomentosa, Liriodendron tuliplfera, and Osmanthus fragrans) which do
not form typical gelatinous fibers. These sample trees were inclined artificially at angle of 30, 50, 70 degrees
from the vertical. The amount of lignins was decreased by tension wood formation in the intercellular layer andwood fiber walls. It was found that inclination angle affects the amount of syringyl unit in lignins.
2007-102
ToF−SIMS による広葉樹木部におけるリグニン分布の解析
斉藤香織*1、渡遽陽子*2、勝山さやか*1、松下泰幸*1 、今井貴規*1、船田良*3、小池孝良*4、深澤和三*4、福島和彦*1*1
名古屋大学大学院生命農学研究科、*2 北海道大学 FSC、*3 東京農工大学大学院農学研究科、 *4 北海道大学大学院農学研究科
Lignin distribution in the cell walls of angiosperm xylem determined by ToF-SIMS
Kaori Saito*1, Yoko Watanabe*2, Sayaka Katsuyama*1, Yasuyuki Matsushita*1, Takanori Imai*1, Ryo Funada*3,
Takayoshi Koike*4, Kazumi Fukazawa*4, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, *2Field Science Center for
Northern Biosphere, Hokkaido University, Sapporo 060-0809, *3Inslitute of Symbiotic Science and Technology,
Tokyo University of Agriculture and Technology, Fuchu, 183-8509, *4Graduate School of Agriculture, Hokkaido
University, Sapporo 060-8589
Abstract:
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate theheterogeneous distribution of guaiacyl and syringyl lignin in the transverse section of the xylem of Acer
micranthum. The lignin distribution was visualized by ToF-SIMS direct mapping of secondary ions withguaiacyl or syringyl rings at m/z 137 and m/z 167, respectively. The result supports the previous observation
obtained by Mäule color reaction that the vessels are rich in guaiacyl lignin and the fibers are rich in syringyl
lignin.
2007-103
ポプラペルオキシダーゼの遺伝子およびタンパク構造の多様性
江藤祐*1、重松幹二*2、堤祐司*1、近藤隆一郎*1*1
九州大学大学院農学研究院、*2 福岡大学工学部
Structural diversity of poplar peroxidases
Yu Eto*1, Mikiji Shigematsu*2, yuji Tsutsumi*1, Ryuichiro Kondo*1*1
Faculty of Agriculture, Kyushu University, Fukuoka, 812-8581, Japan, *2Department of Chemical Engineering,
Fukuoka University, Fukuoka, 814-0180, Japan
Plant peroxidases form a numerous multigenic family in higher plants. We have surveyed peroxidase genes in
the Populus trjchocarpa database and found at least 79 sequences encode complete peroxidase protein withmanual anotation, and diversity of peroxidase isoenzymes was investigated from genome structure and aminoacid sequences. The coding sequence of the majority of the peroxidase genes are disrupted by three introns. The
genes excluding this structure bring some light on the evolutionary steps encountered during the diversificationof poplar peroxidase genes. Within the protein structure of 79 putative peroxidases, observed changes of highly
conserved residue may cause significant change in enzyme kinetics and functions, and this observation suggest
the diversification of plant peroxidases.
2007-104
改変型植物酸性 peroxidase の酵母での発現と精製
吉中喬慈，平道哲理，川合伸也
451

東京農工大学大学院農学研究院
Heterogeneous expression and purification of modified plant peroxidase
T. Yoshinaka, T. Hiramichi, Shinya Kawai
The Graduate School of Agriculture, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509
Abstract:
PrxA3a is an anionic peroxidase from hybrid aspen. A gene, prxA3a, was fused with sequenceof His-tag. The construct was inserted into the downstream of FLAG sequence in a yeast expression vector,
YEpFLAG. Active peroxidase was secreted into the medium. The secreted peroxidase was purified byNi-column. The peroxidase might be highly glycosylated. Other modified peroxidase is also analyzed.
2007-105
リグニン生合成を抑制した飼料用・エタノール変換用イネの分子育種
志波朋美、久保賢太郎、川合伸也
東京農工大学農学府
Down regulation of cinnamyl alcohol dehydrogenase (CAD) induces increase of cell wall digestibility in rice
(Oryza sativa)
Tomomi Shiba, Kentaro Kubo, Shinya Kawai
Faculty of Agriculture, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo
183-8509, Japan
Abstract:
Cinnamyl alcohol dehydrogenase (CAD) is the enzyme of the lignin-specific biosynthesis.
Inverted repeats constructs of the DNA encoding CAD of Oryza sativa have been introduced into rice plants.
CAD down-regulated plants did not displayed any abnormal phenotype compared with a wild type. Lignin
content and cell wall digestibility measurement was performed on the transformants. Lignin content was not
reduced, but cell wall digestibility increased. This suggested CAD down-regulation induced change in lignin
composition. As a result, increasing of cell wall digestibility without weakening plant structure is realized.
2007-106
モノリグノール配糖体によるシリンギル型 DHP の生成挙動の解析
飛松裕基，上高原浩，高野俊幸，中坪文明
京都大学大学院農学研究科
In-situ UV spectroscopic study on the horseradish peroxidase-catalyzed polymerizations of monolignol
glycosides
Yuki Tobimatsu, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University,
Sakyo-ku, Kyoto 606-8502, Japan
Abstract:
Horseradish peroxidase catalyzed homopolymerizations of syringyl-type (S-type) glycoside 1Sand copolymerizations of 1S with guaiacyl-type (G-type) glycoside 1G were monitored by in situ UVspectroscopy. In the former, new absorption peak at 325 nm (A325) from S-type quinone methide intermediates(S-QM) increased rapidly within 30 min, and then disappeared gradually, suggesting that the reactivities of the
S-QM are significantly low. In the latter, the addition of 1G promoted both of the increase and the following
decrease of A325, suggesting that 1G acts not only as a radical mediator but also as a nucleophile for the S-QM
during the copolymerizations.
2007-107
担子菌のラッカーゼ遺伝子を導入した組換え植物が示す雄性不稔の解析
Zannatul Nasrin*1、園木和典*2、飯村洋介*12、片山義博*1、梶田真也*1*1
東京農工大学大学院 BASE、*2 産業技術総合研究所
Analysis of male sterility in transgenic plants with the chimeric gene for fungal laccase
Zannatuf Nasrin*1, Tomonori Sonoki*2, Yosuke limura*2, Yoshihiro Katayama*1, Shinya Kajita*1*1
Graduate Schoof of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan. *2National Jnstitute of Advanced Industrial Science andTechnology, Tsukuba, Ibaraki 305-8569, Japan
2007-108
イネをモデル植物とした細胞壁形成過程に関する研究 −Glycosylphosphatidylinositol-anchored protein はイ
ネの細胞壁高次構造形成にどのように関わるのか？（3）ー452伊藤幸子*1、鈴木瑠*1、佐藤かんな*2、半智史*3、北野英己*2、船由良*3、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 名古屋大学大学院 BBC *3 東京農工大学大学院農学研究院
Study of plant cell wall formation in Oryza sativa L. -How does glycosylphosphatidylinositol- anchored protein
relate fo cell wall conformation in rice plant (Oryza sativa L.) ? (3)Sachiko Ito*1, Ryu Suzuki*1, Kanna Sato*2, Satoshi Nakaba*3, Hidemi Kitano*2, Ryo Funada*3, Shinya Kajita*1,
Yosihiro Katayama*1*1
Graduate School of Bio-Appplication and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan. *2Bioscience and Biotechnology Center, Nagoya University,
Chikusa-ku, Nagoya 464-8601, Japan, *3Graduate School of Agriculture, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan
Abstract:
To understand the mechanism that regulate the high-order conformation of plant cell wall, amutant defective in stem strength had been isolated and characterized. A rice mutant cell wall architecture 1(cwa1) exhibits the systemic brittle-culm phenotype with indistinguishable morphology from wild-type plant.
Whereas abnormal depositions that contain much phenols were found at secondary cell wall in cortical fiber
regions of cwa1. Thus cwa1 is likely to be defective in control of cell wall architecture but not in biosynthesis ofcell wall. We suggest that defective protein of cwa1;BC1 work as a scaffold for precise localization of each cellwall components.
2007-109
ヤマモモ抽出成分ミリカノールの生合成、 –p−クマール酸および p-ヒドロキシフェニルプロパン酸の投与とその取り込み–
仲田京祐、河合真吾、西田友昭
静岡大学農学部
Myricanol biosynthesis in Myrica rubra - Feeding experiments of p-coumaric acid andp-hydroxyphenylpropanoic acid Kyosuke Nakata, Shingo Kawai, Tomoaki Nishida
Department of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka University, 836
0hya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
Diarylheptanoids are one of the major wood extractives and have C6-C7-C6 carbon skeleton.
However, there is little evidence about the biosynthetic pathways for diarylheptanoids. We have investigated thebiosynthesis of cyclic diarylheptanoid myricanol, which is the major extractive in Myrica rubra, and previously
reported in vivo feeding experiments using [β, γ-13C2]-p-coumaric acid. The results indicated that the
involvement of two molecules of p-coumaric acid for myricanol biosynthesis in M. rubra. In the present study,
we reports that the assignments of the incorporated
positions of [β, γ-13C2]-p-coumaric acid into myricanol with 13C-NMR studies. Furthermore, to clarify whether
13p-hydroxyphenylpropanoic
acid
is
a
precursor
formyricanol
biosynthesis,
C-labeledp-hydroxyphenylpropanoic acid was prepared and administrated into M. rubra. The results reveal that[γ-13C]-p-hydroxyphenylpropanoic acid is incorporated into myricanol.
2007-110Isolation of Anthriscus sylvestris O-methyltransferase cDNAs
Safendrri Komara Ragamustari*1, Shiro Suzuki*1, Yu Kitamura*1, Masaomi Yamamura*1, Eiichiro Ono*2,
Takefumi Hattori*1, Toshiaki Umezawa*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto, 611-0011, Japan*2
Institute for Healthcare Science, Suntory, 1-1-1 Wakayamadai, Shimamoto-cho, Mishima, Osaka 618-8503,
Japan
Abstract:
In order to further understand the role of O-methyltransferases (OMTs) in podophyllotoxin
biosynthesis, we have isolated 7 OMT cDNAs from an Anthriscus sylvestris cDNA library. The isolation using
digoxigenin (DIG) labeled probes resulted in 62 positives and further
screening narrowed them down into 7 cDNA clones. Phylogenetic analysis showed that the 7 cDNA clones havehigh identity towards their respective probes. Among the isolated clones, we are particularly interested in clone#50 due to its close phylogenetic relationship with AEOMT. The clone is predicted to encode an AEOMT-likeprotein, which has a similar role in plant metabolism. Expression and characterization of the 7 clones are
currently underway.
2007-111
453

白色腐朽菌 Phanerochaete sordida YK-624 株の形質転換系構築及び新規リグニンペルオキシダーゼの発現杉浦立樹*1、平井浩文*1、西田友昭*1、山岸賢治*2、木村俊之*2*1
静岡大学農学部、*2 東北農業研究センター
Homologues expression of novel lignin peroxidases in Phanerochaete sordida YK-624
Tatsuki Sugiura*1, Hirofumi Hirai*1, Tomoaki Nishida*1, Kenji Yamagishi*2, Toshiyuki Kimura*2*1
Faculty ofAgriculture, Shizuoka University, Shizuoka 422-8529, Japan, *2National Agricultural ResearchCenter for the Tohoku Region, National Agriculture and Food Research Organization, Fukushima 960-2156,
Japan
Abstract]
In our previous reports, the gene transformation system of white-rot fungus Phanerochaete
sordida YK-624 has been developed, and we have cloned two cDNAs (ylpA and ylpB) and two genomic DNAs(g-ylpA and g-ylpB) encoding YK-Lips which are novel lignin peroxidases from this fungus. In the present study,
we tried homologues expression of YK-Lips. The glyceraldehyde-3-phosphate dehydrogenase (GPD) promoter
was used to drive the expression of g-ylpA or g-ylpB, and plasmids (pGPD-g-ylpA and pGPD-g-ylpB) wereconstructed. Transformants were screened for YK-Lip activity in the liquid cultures (1.2 mM ammonium tartrate,
pH 4.5), and A-11 and B-3 were selected as transformants which were high YK-Lips-expressing strains.
Recombinant YK-Lips were secreted in active form by these transformants after 4 days of growth, whereas
endogenous YK-Lips genes were not expressed in manganese-deficient liquid culture (40 mM ammonium
tartrate, pH 6.5).
2007-112
シキミ酸経路を経由したグルコースからの 2-pyrone4, 6-dicarboxylicacid の発酵生産
中島正博*1、西野由香里*2、田村真統*2、間瀬浩平*3、政井英司*4、大塚裕一郎*5、中村雅哉*5、大原誠資 *5、
片山義博*2、梶田真也*2*1
東京農工大学大学院農学研究院、*2 東京農工大学大学院 BASE、*3 豊田自動織機株式会社、 *4 長岡技術科学大学・生物機能工学、*5 森林総合研究所
Biological conversion of glucose to 2-pyrone-4, 6-dicarboxylic acid by the bypassed shikimate pathways
Masahiro Nakajima*1, Yukari Nishino*2, Masatsugu Tamura*2, Kohei Mase*3, Eiji Masai*4, Yuichiro Otsuka*5,
Masaya Nakamura*5, Seiji Ohara*5, Yoshihiro Katayama*2, Shinya Kajita*2*1
Faculty of Agriculture, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509, Japan,*2
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan, *3Toyota Industries Corporation, Kariya, Aichi 448-8671, Japan,*4
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan,*5
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
PDC, 2-pyrone-4, 6-dicarboxylic acid, is one of metabolic intermediates in Sphingomonas
paucimobilis SYK-6 that is a degrader of lignin-derived compounds. PDC has been characterized as a material
for synthetic polymers. In the previous study, we have already constructed the system on which PDC was
efficiently converted from vanillic acid and vanillin. In order to develop alternative system for PDC production,
we try to produce it from glucose, which is one of low-cost sugars expected to be converted from abundant
cellulose wastes and biomass crops. In the present study, we generated six types of recombinant bacteria. PDC
could be produced from glucose by all of the bacteria analyzed. Especially, the recombinant bacteria with qutC
could produce PDC at high concentration than those with ubiC and pobA. Our results suggest that qutC is usefulgene for the fermentative production of PDC.
2007-113
Biodegradation of chrysene in a soil by fungi screened from nature
Tony Hadibarata, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Polyporus sp. S133, a fungus collected from soil, was selected for its ability to grow on anddegrade chrysene as a sole carbon source. The effect of adding several concentrations of tween 80 to increasedegradation rate of chrysene was studied. Maximal degradation (86%) was obtained when Polyporus sp. S133
was incubated in a soil supplemented with 0.50% of tween 80. The mechanism for degradation of chrysene withthe fungus through identification of the intermediates was found. Several enzymes (manganese peroxidase,
lignin peroxidase, laccase, 1,2-dioxygenase and 2,3-dioxygenase) produced by Polyporus sp. S133 weredetected in the culture. The highest enzyme activity was shown by 1,2-dioxygenase after 20 days of cultivation(237.5 UI-1). Those ligninolytic and dioxygenase enzymes played an important role to oxidize chrysene.
454

2007-114
Degradation of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) by brown rot fungus Fomitopsis pinicola
Faculty of Agriculture, Kyushu University
Adi Setyo Purnomo, Ichiro Kamei and Ryuichiro Kondo
Abstract:
Fomitopsis pinicola showed high ability to degrade DDT in PDB medium. To investigate theinvolvement of Fenton reaction, mineral salt medium with or without FeSO4 was used. F. pinicola showed
higher ability to degrade DDT in medium without FeSO4 than that in medium with FeSO4 either in vivo or invitro experiment. It indicates that the extracellular iron-dependent reaction was not involved in DDT
degradation by F. pinicola. DDD (1,1-dichloro-2,2-bis(4- chlorophenyl) ethane) was detected as metabolic
product from DDT degradation. The transformation of DDT to DDD by F. pinicola might be involved
extracellular enzymatic reaction.
2007-115
耐塩性白色腐朽菌 Phlebia sp．MG60 におけるペルオキシダーゼ転写制御
亀井一郎*1、大黒千映子*2、堤祐司*2、近藤隆一郎*2*1
九州大学 VBL、*九州大学大学院農学研究院
Transcriptional regulation of manganese peroxidases from saline–tolerant white rot fungus, Phlebia sp. MG60
Ichiro Kamei*1, Chieko Daikoku*2, Yuji Tsutsumi*2, Ryuichiro Kondo*2*1
Venture Business Laboratory, *2Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku,
Fukuoka 812-8581, Japan
Abstract:
The expression pattern of manganese peroxidases (MnPs) in nitrogen-limited cultures ofsaline-tolerant fungus, Phlebia sp. MG-60, is differentially regulated under a hyper-saline condition at thetranscriptional level. When MG-60 was cultured in the nitrogen limited medium containing 3% sea salts(LN-SSM), higher activity of MnPs was observed than that in the normal medium (LNM). SDS-PAGE analysis
demonstrated that two MnP isoenzymes were de DOVO synthesized during the culture in LN-SSM. Three MnPencoding genes (MG-mnp1, MG-mnp2, and MG-mnp3) were isolated by RT-PCR and RACE-PCR techniques,
and identification of each MnP protein was achieved by peptide mass fingerprinting (PMF) analysis of thetryptic fragments of each MnP isoenzyme observed on SDS-PAGE. Two MnP isoenzymes that were mainly
observed in LN-SSM were encoded by MG-mnp2 and MG-mnp3. Real-time PCR analysis revealed that
MG-mnp2 and MG-mnp3 were highly transcribed in LN-SSM, and the transcription was induced 48 h after the
addition of 2% NaCl. The induction of MnP production and gene transcription by saline was well correlated in
the presence of Mn2+. However, in the absence of Mn2+ there is no clear correlation between mnp transcription
and MnP activity, suggesting the existence of a post-transcriptional regulation by Mn2+.
2007-116
Phanerochaete chrysosporium のリグニン分解能を支える代謝制御機構
割石博之*1*2*3、石川真梨子*4、志水元亨*1、寺本寛*4，三浦大典*3、国武宣道*4、中村朋史*4、一瀬博文*1*1
九州大学大学院農学研究院、*2 九州大学バイオアーキテクチャーセンター、*3 九州大学先端融合医療レドックスナビ研究拠点、*4 九州大学大学院生物資源環境科学府
Systems biology of lignin biodegradation
Hiroytlki Wariishi*1*2*3, Mariko Ishikawa*4, Motoyuki Shimizu*1, Hiroshi Teramoto*4, Daisuke Miura*3,
Nohmichi Kunitake*4, Tomofumi Nakamtlra*4, Hirofumi Ichinose*1*1
Faculty of Agriculture, *2Bio-Architecture Center, *3Innovalive Center for Medical Redox Navigation,*4
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University, Fukuoka 812- 8581,
Japan
Abstract:
Effect of exogenous vanillin on a cellular system in Phanerochaete chrysosporium wasinvestigated utilizing integrative OMICS. Addition of vanillin caused an immediate flux shift at the TCA cycle,
initiating a production of succinyl CoA. Transcriptomic data obtained from a 50-mer oligoDNA microarraysystem combined with proteomic data clearly indicated the activation of the heme biosynthetic pathway
branched at succinyl CoA. Up-regulation of extracellular peroxidases and several cytochrome P450s was also
observed. Addition of vanillin also brought about a down- regulation of extracellular oxalate dehydrogenase andintracellular formate dehydrogenase and an up-regulation of enzymes in mannitol cycle, suggesting the presenceof unique regulation system for energy production in the fungus. These metabolic shifts seem to be required for
optimizing its ligninolytic system.
2007-117455

フリーラジカルによるリグニンモデル化合物の反応部位に関する研究
大橋康典、渡遽崇人、本田与一、渡辺隆司
Study on reactive position of lignin model compounds with free radicals
Yasunori Ohashi, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Laboratory of Biomass Conversion, Research Institute for Sustainable Humanosphere, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
Abstract:
A white rot fungus, Ceriporiopsis subvermispora degrades lignin by radical reactions of low
molecular mass metabolites at a site far from enzymes. As a possible ligninolytic system by the fungus, in situ
radical reactions have been proposed. In the degradation of non-phenolic lignin model compounds (LMCs) by
free radicals, it was proposed that the reaction was initiated by hydrogen Abstraction from the benzyl position of
LMCs. However, no concrete evidence has been presented. In the present study LMCs were reacted with
tert-butoxyl radical generated by UV-photolysis of di-tert-butyl peroxide, and radical intermediates from the
LMCs were analyzed by ESR. Reactivity of free radicals with the LMCs was also analyzed using ab initio MO
calculation.
2007-特別講演 I
ブラシノステロイド研究の始まりと現在の進展
横田孝雄
帝京大学理工学部バイオサイエンス学科
2007-201
リグニン熱分解物の気相における二次熱分解反応
細谷隆史、河本晴雄、坂 志朗
京都大学大学院エネルギー科学専攻科
Secondary reactions of lignin-derived pyrolysis vapor
Takashi Hosoya, Haruo Kawamoto, Shiro Saka
Departnent of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
Secondary reaction of lignin-derived primary tar (guaiacols with various side-chain) in vapor
phase was studied with milled wood lignin (from Japanese cedar: Cryptomeria japonica) and various modelcompounds (conditions: N2/600 ºC/ 50-120 s). The benzene-ring and side-chain structures were found to change
in the following pathways: benzene-ring: guaiacyl- → catechol-, o-cresol (2-methylphenol)- and phenol-types,
side-chain: >C=C<, -CHO and >C=O → -H and saturated alkyl chain types. Secondary carbonization was also
observed during these structural changes of the tar components, especially disappearing the -OCH3 groups.
These results indicate that the secondary carbonization is closely related to the formation of phenoxy and methyl
radicals through the O-CH3 bond homolysis. This is also supported by the experimental fact that only the modelcompounds with aromatic -OCH3 formed secondary char.
2007-202
リグニン β−エーテル構造の熱分解ラジカル連鎖開裂反応渡辺敏弘，河本晴雄，坂 志朗
京都大学大学院エネルギー科学専攻科
Radical chain mechanisms in pyrolytic β-ether cleavage suggested from the products of lignin model dimers
and trimer
Toshihiro Watanabe, Haruo Kawamoto, Shiro Saka
Departnent of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
Pyrolysis of lignin model dimers (phenolic and nonphenolic β-ether type) and trimer(nonphenolicα, β-ether type) in a closed ample (N2) at 400ºC for 2min gave Cα=O and isoeugenol (Cα=Cβ)types products as the β-ether-cleavaged products. Formation of these products indicates that radical chain
reactions proceed through H-Abstraction of the Cα-H and phenolic-OH.
2007-203
全細胞壁の溶液 NMR 法によるイチョウのプロトリグニンの 13C 標識２D−NMR 示差スペクトル分析
寺島典二*1、秋山拓也*2、John Ralph*2
456

*1

名古屋大学、*２DFRC, USA
2D-NMR difference spectra between specifically 13C-enriched and unenriched ginkgo protolignin bysolution-state whole-cell wall NMR
Noritsugu Terashima*1 , Takuya Akiyama* *, John Ralph* **1Prof. Emeritus, Nagoya University, 2-610 Uedayama, Tenpaku, Nagoya, 468-0001 Japan, *2US Dairy Forage
Research Center, USDA-Agricultural Research Service, Madison, WI 53706-1108 USA
Abstract:
Coniferins specifically 13C-enriched at side chain carbons and unenriched coniferin wereadministered to growing stems of ginkgo. The whole newly formed xylems containing 13C-enriched andunenriched lignins were milled and dissolved in a mixture of N-methylimidazole and DMSO, then acetylated.
Solution-state 2D-NMR (HSQC) spectra of the dissolved whole xylem cell walls were determined in highresolution. Determination of difference spectra between the spectra of whole cell walls containing 13C-enriched
and unenriched lignins afforded simplified 2D spectra in which all signals were assigned exclusively to thespecifically enriched carbons. The present novel NMR technique provides a useful nondestructive tool for
elucidation of the structure and behavior of entire lignin in the cell wall (protolignin) not only in ginkgo but also
in most common conifers.
2007-204
構造を制御した人工リグニンの化学合成
岸本崇生*1、浦木康光*2、生方信*2*1
富山県立大学工学部、*2 北海道大学大学院農学研究科
Synthesis of β-O-4 type artificial lignin polymers
Takao Kishimoto*1, Yasumitsu Uraki*2, Makoto Ubukata*2*1
Faculty of Engineering, Toyama Prefectural University, Imizu-shi, Toyama 939-0398, Japan
4
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan
Abstract:
The β-O-4 structure is one of the most important substructures in lignin. Artificial lignin
polymer composed of only β-O-4 structure has been synthesized in our laboratory. Brominated acetophenone
derivatives were treated with potassium carbonate and reduced with sodium borohydride to yield polymers. The
polymers were acetylated and fully analyzed by NMR spectroscopy. The spectra of guaiacyl-type homopolymer
and guaiacyl/syringyl-type heteropolymer with three-carbon side chain were well consistent with β-O-4
substructure in milled wood lignin from Japanese tdo fir wood and Japanese white birch wood, respectively.
2007-205β-O−4 結合定量法としてのチオアシドリシス法の評価、−β-O-4 型人工リグニンポリマーの反応の定量性から−
金津香枝*1、浦木康光*2、生方信*2、岸本崇生*3*1*2
北海道大学大学院農学研究科、*3 富山県立大学工学部
Thioacidolysis as quantitative determination of β-O-4 bond -Quantifiability of the reaction of β-O-4 typeartificial lignin polymerYoshie Kanazawa*1,Uraki yasumitu*1,Ubukata Makoto*1,Takao Kishimoto*2*1
Graduate School of Agriculture, Hokkaido University,Sapporo 060-8589, Japan*2
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan*3
Faculty of Engineering,Toyama Prefectural University, Toyama 939-0398, Japan
Abstract:
Thioacidolysis is a method for quantitative determination of β-O-4 bond in lignin. We
established the synthetic route to artificial lignin polymer comprised of only β-O-4 linkage. In this study, weevaluated thioacidolysis reactivity to β-O-4 bond by using this lignin polymer. The monomer yield for theartificial lignin polymer was less than 100% (about 70%) under the conventional thioacidolysis conditions,whereas approximately 100% yield for the dimer model compound under the same conditions. No enhancementof monomer yield was observed, by prolonging reaction time. These results suggest that thioacidolysis was not a
stoichiometrical decomposition method for β-O-4 macromolecule.
2007-206
リグニンおよび微生物変性水可溶リグニンの超臨界水・亜臨界水条件下での反応：原油生成機構
Zhenfu Jin*1、勝亦京子*1*2、飯山賢治*3*1
東京大学大学院農学生命科学研究科、*3 東京大学アジア生物資源環境研究センター
Reaction of lignin and biologically modified lignin under supercritical and subcritical water conditions:
457

Presumptive production mechanism of petroleum
Zhenfu Jin*1*2, Kyoko S. Katsumata*1, Kenji liyama*3*1
Graduate School of Agricultural and Life Sciences, the University of Tokyo, *2Present address: Department ofEngineering, Zhejiang Forestry University, China, *3Japan International Research Center for Agricultural
Sciences, the University of Tokyo
Abstract:
The annual discharge of dissolved organic mater (DOM) and particulate organic matter (POM)from rivers to ocean is estimated as ∼0.4 x 109 ton, which are primarily composed of biologically modified
remains of terrestrial vegetation. The DOM in the ocean could form insoluble sediments by chelating with metal
ions and considered to be precursor of kerogen. Kerogen is defined as the sedimentary organic matter generating
petroleum, which is an insoluble matter, in contrast petroleum soluble in usual organic solvents. Reaction ofmodel compounds, Björkman lignins and DOM were examined under supercritical water condition to confirm
the formation mechanism of petroleum at deep sea, where is subcritical condition. It was confirmed thatdemethylation and demethoxylation reactions were the major reactions of lignins and DOM. These reactions
also were confirmed by phenol, guaiacol and 2,6-dimethoxyphenol (syringol) as model compounds.
2007-207
ハード酸とソフト塩基の組み合わせによるリグニンエーテル結合の新規開裂方法の検討
湯川邦彦、幸田圭一、小島康夫
北海道大学大学院農学研究科
A novel ethereal bond cleavage of lignin interunit linkage by a combination of hard acid and soft baseKunihiko Yukawa*1, Keiichi Koda*2, Yasuo Kojima*2*1
Graduate School of Agriculture, Hokkaido University, Kita 9, Nishi 9, Kita-ku, Sapporo, 060-8589 Hokkaido,
Japan, *2Research Faculty ofAgriculture, Hokkaido University, Kita 9, Nishi 9, Kita-ku, Sapporo, 060-8589
Hokkaido, Japan
Abstract:
Ethereal bond cleavage of wood meal, isolated lignin, and lignin model compound(guaiacylglycerol--guaiacyl ether) by aluminium (III) iodide, known as a hard Lewis acid as well as a soft
nucleophile, were investigated to explore a new procedure to delignify woody preparations effectively underrelatively mild reaction conditions. The lignin model compound was successfully degraded even when treated atroom temperature for 4.5 hours, suggesting AlI3 can cleave ethereal bond of lignin structural units under somemild reaction conditions. Enhanced delignification of wood meal by AlI3 treatment at refluxing temperature wasalso observed, but optimized conditions were yet to be established.
2007-208
炭水化物のアノマ一位に対する活性酸素種の反応性の評価
小西史子、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Evaluation of the reactivity of active oxygen species toward the anomeric position of carbohydrate
Fumiko Konishi, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
The reactivity of active oxygen species (AOS) toward two different anomeric types ofcarbohydrate was examined using methyl α-D-glucopyranoside (MGPα) and methyl β-D-gluco- pyranoside(MGPβ). In this study, AOS were in situ generated by subjecting a phenolic compound, 2,4,6-trimethylphenol(TMPh), to the oxygen oxidation. As the degradation of MGPβwas greater than MGPα, it was suggested that thestereo configurational difference in their anomeric positions has an influence on their reactions with AOS. It wasalso examined whether or not the anomeric position is certainly attacked by AOS subjecting TMPh, MGP, andmethyl β-D-[1-d]-gluco- pyranoside (MGPβ[1-d]) to the oxygen oxidation. The result obtained by the GC-MS
analysis showed that the degradation of MGPβ[1-d] is slower than MGPβsuggesting a possible occurrence ofthe certain Abstraction of the anomeric hydrogen.
2007-209
酸性下におけるリグニン β-O-4 結合開裂機構の再評価 (4) 一酸の種類の影響について一伊藤宏昭、横山朝哉、松本雄二
束京大学大学完農学生命科学研究科
Reevaluation of the mechanism for the cleavage of lignin β-O-4 bond under acidic conditions (4)458—On the effect of kind of acid—
Hiroaki Ito, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
A dimeric non-phenolic lignin model compound, veratrylglycerol-β-guaiacyl ether (VG), wastreated with HBr in 82% aqueous dioxane. It was found that the elimination of γ-position as formaldehyde does
not occur in the system. Because the C6-C3 type enol ether afforded from VG by the water elimination was notdetected at all, it could not be clarified whether or not the enol ether is produced during die VG acidolysis. The
results obtained by the use of VG with the deuterium at the β-position (VGbD) indicated that the Abstraction ofthe β-proton from the benzyl cation structure resulting in the formation of the C6-C3 type enol ether (referred toreaction (I) in the following) probably relates to the rate-determining step in the disappearance of VG. However,
because the difference in die β-O-4 bond cleavage rate between kind of acids cannot be explained from the rate
difference in die reaction (I), there seems to be another step with a similar rate to the reaction (I), where kind ofacids affects its rate.
2007-210
国産針葉樹材アルカリパルプのへキセンウロン酸含有量と無塩素漂白特性
高橋史帆，中川明子，金光箔，大井洋
筑波大学大学院生命環境科学研究科
Hexenuronic acid contents of various alkali pulps from Japanese softwood and their non-chlorine bleaching
response
Shiho Takahashi, Akiko Nakagawa-izumi, Guang-fan Jin, Hiroshi Ohi
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba. Ibaraki 305-8572 Japan
Abstract:
We estimated hexenuronic acid (HexA) contents and lignin contents of various alkali pulps
given by kraft, kraft-anthraquinone (kraft-AQ), and polysulfide-anthraquinone (PS-AQ) cookings based onsome cooking factors such as cooking time, active alkali charge, AQ charge, and sulfur charge. HexA contentsof PS-AQ and kraft-AQ pulps with kappa number 25 at H-factor 1200 from Japanese softwood were higher thanthat of the conventional kraft pulp. Various alkali pulps were bleached using the O-A-Z-E-Ep sequence. We
discussed that their non-chlorine bleaching response from the standpoint of brightness and residual HexA
contents.
211
南アフリカ産ユーカリ材のクラフト・アントラキノン蒸解および無塩素漂白特性
本間光子*1，中川明子*1，大井 洋*1，中俣恵一*2*１
筑波大学大学院生命環境科学研究科、*２北越製紙株式会社
Characteristics of various eucalyptus woods from South Africa for kraft-AQ cooking and TCF bleaching
Mitsuko Honma*1, Akiko Nakagawa-izumi*1, Hiroshi Ohi*1, Keiichi Nakamata*2*1
Graduate School of Life and Environmental Sciences, University of Tsukuba,1-1-1, Tennodai, Tsukuba,
305-8572 Ibaraki, Japan. *2Technical & Development Division, Hokuetsu Paper Mills, Ltd., 3-2-2 Hongoku-cho,
Nihonbashi, Chuo-ku,103-0021 Tokyo, Japan
Abstract:
Eucalyptus nitens, E. grandis, E. smithii and E. macarthurii woods grown in South Africa,
which have been used in Japanese pulp mills, were investigated to clarify their characteristics forkraft-anthraquinone (AQ) cooking and totally chlorine-free (TCF) bleaching. They had various densities from0.477 to 0.751 g/cm3. Lower lignin contents on original wood resulted in higher pulp yields. Higher ratios ofsyringaldehyde to vanillin by alkaline nitrobenzene oxidation of lignin brought higher brightness after cooking.
After oxygen bleaching, the kappa number decrease of E. grandis pulp was quite low because of its highhexenuronic acid content which contributed kappa number. Pulp sheet were made under neutral conditions after
TCF bleaching and the accelerated yellowing tests were performed. Each pulp showed little brightness reversion,and there are no clear relationship between the hexenuronic acid (HexA) contents and the brightness reversion.
All TCF bleached pulps except E. grandis showed high brightness around 85% ISO and E. smithii is the highest(86.7% ISO).
2007-212
アルカリ処理オゾン酸化リグニンのアルミニウム毒性除去能についての研究
相見 光、大村 知士、加藤 珠央、中原 知子、志水一允
日本大学生物資源科学部
459

Studies on elimination of aluminum toxicity with modified kraft lignin
Hikaru Aimi, Satoshi Ohmura, Tamao Katoh, Tomoko Nakahara, Kazumasa Shimizu
Laboratory of Biomass Sciences, Department of Forest Sciences and Resources, College of Bioresource
Sciences, the Nihon University, 1866 Kameino, Fujisawa, Kanagawa, 252-8510, Japan
Abstract:
Ozone treated kraft lignins were subjected to alkaline treatment and the effect of these modified
kraft lignins on elimination of aluminum toxicity was assayed by planting experiment. Modified kraft ligninswith ozone followed by alkaline treatments were more effective on elimination of aluminum toxicity andacceleration of root growth than that with only ozone. It is, furthermore, observed that the kraft lignin which
was subjected to alkaline treatment was also effective on elimination of aluminum toxicity and acceleration ofroot growth in this experiment. This fact suggests that kraft lignin itself has chemical structure which is effective
on above favorable effects.
2007-213
リグノスルフォン酸塩一糖蜜系木質充填型バイオコンポジットの熱的・機械的性質
畠山兵衛*1、大菅忠秀*1、島田幹夫*1、広瀬重雄*2、畠山立子*3*1
福井工業大学工学部、*2 産業技術総合研究所、*3 リグノセルリサーチ
Thermal and mechanical properties of sodium lignosulfonate and molasses-based polyurethane biocomposites
Hyoe Hatakeyama*1, Tadahide Ohsuga*1, Mikio Shimada*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3*1
Fukui University of Technology, 3-6-1, Gakuen, Fukui 910-8505, *2AIST, 1-1-1, Higashi, Tsukuba, 305-8565,*3
Lignocell Research, 2-6-16, Mejirodai, Bunkyo-ku, Tokyo 112-0015
Abstract:
Molasses ( ML ) is obtained as a by-product of the sugar industry. Sodium lignosulfonate (LS)is obtained as a by-product of the pulping industry. ML polyol (MLD) and LS polyo1 (LSD) are obtained bydissolving ML and LS in diethyleneglycol (DEG). In this study, MLD and LSD were reacted withpoly(phenylene methylene) polyisocyanate MDI) that was used for the preparation of molasses- andlignin-based polyurethane (PU) composites using wood meal as fillers. In the above biocomposites, wood meal
contents were changed from 50 to 90 %. MLD and LSD mixing ratios were changed as follows, 0:100, 20:80,
40:60, 50:50, 60:40, 80:20, 100:0. Apparent density, compression and thermal properties of the PU composites
were examined. Apparent density and compression strength showed the optimum point at MLD and LSD themixing ratio 60:40. Thermal degradations (Td) of composites were observed as two steps, low temperature side(Td1) and high temperature side of thermal degradation (Td2). The Td1 at ca. 290ºC is attributed to thedegradation of MLPU and LSPU matrix. The Td2 observed at 310-360ºC is attributed to the degradation of wood
meal. It was found that mechanical and thermal properties of composites are controllable through reaction
conditions.
2007-214
リグニンスルホン酸塩を原料とする飽和及び不飽和エステル型エポキシ樹脂の合成と熱的性質
広瀬重雄*1、畠山立子*２、畠山兵衛*３*1福井工業大学工学部、産業技術総合研究所、*２リグノセルリサーチ、*３福井工業大学工学部
Synthesis and thermal properties of epoxy resins with saturated and unsaturated ester chains fromligninsulfonate salt
Shigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*3*1
Research Institute for Innovation in Sustainable Chemistry, AIST, Central 5,1-1-4 Higashi, Tsukuba, Ibaraki
305-8565, Japan, *2Lignocel Research Ltd., 2-6-16 Mejirodai, Bunkyo-ku, Tokyo 112-0015, Japan, *3Fukui
University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Sodium ligninsulfonate (LS) was dissolved in ethylene glycol (EG) and the obtained mixture
was allowed to react with succinic anhydride to form a mixture of ester-carboxylic acid derivatives (LS-EG
polyacid, LSEGPA). EG-polyacid (EGPA) was also prepared from EG. The mixture of LSEGPA and EGPA wasreacted with ethylene glycol diglycidyl ether in the presence of catalytic amount of dimethylbenzylamine toform epoxy resins. The molar ratio of epoxy groups to carboxylic acid groups ([EPOXY]/[AA] ratios, mol/mol)
was maintained at 1.1. The contents of LSEGPA in the mixture of LSEGPA and EGPA (LSEGPA content) werevaried from 0 to 100%. A mixture of ester-carboxylic acid derivatives (LS-EGM polyacid, LSEGMPA) and
EGM-polyacid (EGMPA) were also synthesized using maleic anhydride. Thermal properties of epoxy resins
were studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Glass transition
temperatures (Tg's) of epoxy resins increased with increasing LSEGPA and LSEGMPA contents suggesting thatlignin acts as a hard segment in epoxy resin networks. Thermal decomposition temperatures (Td's) of epoxy
resins were almost constant regardless of LSEGPA and LSEGMPA contents.
460

2007-215
オルガノソルブリグニンアルキルエステル／ポリ（ 一カプロラクトン）相溶ブレンドの相構造評価と結晶化挙動
寺本好邦 李承桓，遠藤貴土
産業技術総合研究所バイオマス研究センター
Phase structure and crystallization behavior of biodegradable blends of poly( -caprolactone) with organosolv
lignin alkyl esters
Yoshikuni Teramoto, Seung-Hwan Lee, Takashi Endo
National Institute of Advanced Industrial Science and Technology (AIST), Biomass Technology ResearchCenter (BTRC), 2-2-2, Hirosuehiro, Kure, Hiroshima, 737-0197, Japan
Abstract:
Organosolv lignin (OSL) alkyl esters (carbon number, 2-5) were synthesized by a homogeneous
reaction with different acyl anhydrides/4-dimethylamino pyridine in pyridine solution. The miscibility of theesterified OSLs with poly( -caprolactone) (PCL) was investigated, mainly through the evaluation of the glasstransition temperature (Tg) using differential scanning calorimetry (DSC). DSC analysis revealed that the blendsof OSL esters with n=3-5 with PCL showed a composition-dependent shift in Tg. Therefore, the blend systems
can be regarded as miscible ones in a scale of T g-detection, usually assumed to be less than a couple of tens ofnanometers. Atomic force microscopy also indicated that no remarkable phase separation occurred in theseblends. On the other hand, it was noted that the crystallinity of PCL vanished for PCL-rich compositions of themiscible pairs. This observation also supports that the blends show the higher degree of miscibility with PCL. In
order to obtain further details of the crystalline development, isothermal crystallization experiments wereconducted by means of polarized optical microscopy.
2007-216
イオン液体への木材の溶解性とリグニンモデル化合物の安定性
久保智史*1、橋田 光*1、細谷修二*1、眞柄謙吾*1、山田竜彦*1*2、岸野正典*3、大野弘幸*4*1
森林総合研究所、*1 農林水産省農林水産技術会議事務局、*３北海道林産試験場、*４東京農工大学大学院
共生科学技術研究院
Solubility of wood and stability of lignin model compounds in ionic liquid
Satoshi Kubo*1, Tatsuhiko Yamada*1*2,Koh Hashida*1, Shuji Hosoya*1, Kengo Magara*1, Masanori Kishino*3,
Hiroyuki Ohno*4*1
Department of Biomass Chemistry, Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan,*2Agriculture, Forestry and Fisheries Research Council, Tokyo, Japan, *3Wood Utilization Division, Hokkaido
Forest Products Research Institute, Asahikawa, Hokkaido, *4Department of Biotechnology, Tokyo University ofAgriculture and Technology, Koganei, Japan,
Abstract:
Structure stability of lignin model compounds in ionic liquids was studied to develop the novel
isolation methods of lignin and LCC from wood. Four imidazolium based ionic liquids, and two phenolic lignin
model compounds, Guaiacy1glycerol-β-guaiacyl ether and its α- ethoxy model compound, were examined inthis study. Under the temperature condition of 120 ºC, cellulose component in wood meal were decrystalized bymore than 48 hs treatment. However, lignin model compounds were gradually decomposed under thistemperature condition with extending the processing time. Depending on the ionic liquid used, more than 40%
of loaded model compound were decomposed for 48 hs treatment. Under the lower temperature condition (100ºC), those model compounds were relatively stable. Decomposition degree after 48 hs treatment was less than
20% in chlorinated ionic liquid, 1-Butyl-3-methylimidazolium and 1-Allyl-3-methylimidazolium chloride,
although significant decomposition was estimated in other ionic liquids.
2007-特別講演 II
熱分解ガスクロマトグラフィーによるリグニンの分析黒田 健一
九州大学大学院農学研究院
Invited Lecture, II: Analysis of lignin by pyrolysis-gas chromatography
Ken-ichi Kuroda
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University, 6-10-1,
Higashi-ku, Hakozaki, Fukuoka 812-8581, Japan
Abstract:
Emergence of analytical pyrolysis combined with modern instruments such as gas
461

chromatography and/or mass spectrometry has provided new possibilities to analyze the lignin owing to its highsensitivity, lesser sample-preparation steps and a short analysis time. Under controlled pyrolysis conditions,lignin is reproducibly broken to give products retaining structural attributes. This paper examines several recent
advances in analytical pyrolysis. Selected aspects are exemplified using original results.
2007-P01
イネ稈及び葉鞘の組織構造とリグニン分布
三瓶広幸、平岩季子、石栗 太、飯塚和也、横田信三、吉澤伸夫
Anatomy and lignin distribution of stem and leaf tissues in Oryza sativa
Hiroyuki Sanpe, Tokiko Hiraiwa, Futoshi Ishiguri, Kazuya Iizuka, Shinso Yokota, Nobuo Yoshizawa
Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
For utilization of biomass resources, anatomy and lignin distribution of stem and leaf tissues in
Oryza sativa, which is one of the popular crops in Japan, were investigated. Tracheid wall and vessel walls invascular bundles in cortex and parenchyma tissues showed pinkish color after
Wiesner reaction. Spectrophotometry analysis showed a distinct absorption peak around 570 nm inthese walls after Wiesner reaction, suggesting that substances with coniferyl aldehyde structure exist in thesetissues. On the other hand, fiber walls in cortex were weakly stained with Wiesner reagent and did not show any
distinct peak in visible-light absorption microspectra. These results
indicate that the amount and type of lignin in cell walls of O. sativa vary among cell types.
2007-P02
Lignin deposition and peroxidase activity in Japanese birch plantlets (Tohoku) infected with lnonotus obliquus
IO-U1 strain
Md. Mahabubur Rahman*1*2, Futoshi Ishiguri*2, Yuya Takashima*2, Mariko Satoh*2, Mustafa Abul Kalam Azad*2,
Kazuya Iizuka*2, Nobuo Yoshizawa*2, Shinso Yokota*2*1
United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology, Fuchu,
Tokyo 183-8509, Japan, *2Faculty of Agriculture, Utsunomiya University, Utsunomiya 321- 8505, Japan
Abstract:
Histochemical studies were undertaken on defensive reactions of Betula platyphylla var.
japonica Tohoku clone after infection with Inonotus obliquus IO-U1 strain. As a defensive reaction, phenolics
deposition was found rapidly within 2 hrs of infection and reached extensive by 10 days. The peroxidase
activities were observed in phenolics-deposited cell walls. Cell walls of vessels and wood fibers were rich inlignin at the infection site in 10 days of treatment. These histochemical changes are considered to occur as
defense reactions in the infected Tohoku birch plantlets.
2007-P03
モノリグノール類の電解重合
関口卓也、松下泰幸、今井貴規、福島和彦
名古屋大学大学院生命農学研究科
Electropolymerization of monolignols
Takuya Sekiguchi, Yasuyuki Matsushita, Takanori Imai, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract:
We carried out anodic oxidation of monolignols, especially coniferyl alcohol, by galvano-static(constant-current) method. Using dichloromethane/methanol as a mixed solvent, a yellow filmy product was
deposited on Pt anode during the electrolysis reaction. Although the yield of this electropolymerized productwas very low, thioacidolysis analysis suggests that it has high β-O-4 linkage content. Probably, theelectropolymerization of monolignols could produce the characteristic polymer that we have not obtained fromconventional DHP preparation method.
2007-P04
リグニン重合機構の解明 −モノリグノールのラジカル重合の可能性−
鈴木啓介*1、浦木康光*2、生方 信*2*1
北海道大学大学院生命科学院、*2 北海道大学大学院農学研究科
Elucidation of the lignin polymerization mechanism -Possibility of radical polymerization of monolignolKeisuke Suzuki*1, Yasumitsu Uraki*2, Makoto Ubukata*2*1
Graduate School of Life Science, Hokkaido University, Sapporo 060-8589, Japan. *2Research Faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan.
462

Abstract:
We investigated possibility of radical polymerization of coniferyl alcohol as a monolignol. The
monolignol was found to be polymerized under the solution polymerization conditions with and without
initiators. The resultant polymeric materials contain aliphatic alcohols having only a few double bonds. These
results suggest that the polymer was formed by radical polymerization together with dehydration.
2007-P05
ポプラペルオキシダーゼアイソザイム CWPO−C の機能解析
清永裕子*1，佐々木慎弥*1、堤 祐司*2，近藤隆一郎*2*1
九州大学大学院生物資源環境科学府、*2 九州大学大学院農学研究院
Function of cationic cell-wall-peroxidase (CWPO-C) from poplar
Yuko Kiyonaga*1, Shinya Sasaki*1, Yuji Tsutsumi*2, Ryuichiro Kondo*2*1
Graduate School of Bioresource and Bioenvironmental Sciences, *2Faculty of Agriculture, Kyushu University,
Fukuoka, 812-8581, Japan
Abstract:
A unique peroxidase isoenzyme, cationic cell-wall-peroxidase (CWPO-C), from poplar oxidizes
sinapyl alcohol, ferrocytochrome c and synthetic lignin polymers, unlike other plant peroxidase. Recently,
catalytic mechanism of CWPO-C was investigated using chemical modification and homology modeling. It wassuggested that Tyr residues on the protein surface, such as Tyr-177 and Tyr-74, are considered to be important
for the oxidation activities of CWPO-C with a wide range of substrates. In this study, we focused on CWPO-C
homolog genes of Arabidopsis thaliana, and these T-DNA mutant lines were analyzed. The point-mutatedrecombinant CWPO-C was also generated to determine the oxidation sites of CWPO-C.
2007-P06
ポプラ分化中木部における 4−coumarate:CoA ligase 免疫局在山下恭平、高部圭司、藤田稔
京都大学大学院農学研究科
Immunolocalization of 4CL in differentiating xylem of poplar
Kyohei Yamashita, Keiji Takabe, Minoru Fujita
Laboratory of Tree Cell Biology, Division of Forest and Biomaterials Science, Graduate School of Agriculture,
Kyoto University, Kitashirakawaoiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan
Abstract:
Anti-4-coumarate:CoA ligase (4CL) antiserum were raised using artificially synthesizedpeptides. They were injected several times into mouse, and then the mouse anti-4CL serum was obtained.
Specificity of the anti-serum was confirmed by western blotting and immunoprecipitation techniques.
Immunolocalization of 4CL was observed in differentiating xylem cells of Populus sieboldii X P. grandidentata.
2007-P07
Stereochemistry on the formation of syringylglycerol-8-O-4'-(sinapyl alcohol) ether from sinapyl alcohol withenzyme preparations of Eucommia ulmoides
Md. Shameul Alam, Takeshi Katayama, Toshisada Suzuki
Faculty of Agriculture, Kagawa University, Miki-cho, Kagawa 761-0795
Abstracts:
Incubation of a soluble enzyme preparation with [8-14C]sinapyl alcohol (SA) in the presence of14
H2O2 gave [ C]syringylglycerol-8-O-4'-(sinapyl alcohol) ether (SGSE). The erythro isomer was more favoredthan the threo isomer with 63.2 percentage of diastereomeric excess (%d.e.) at 30min and 26.7% d.e. at 60min, respectively. The erythro and threo isomers at 60min were levorotatory
with 47.4% and 21.6% enantiomeric excess (% e.e.), respectively. Incubation of an insoluble enzyme
preparation with [8-14C]SA also gave [14C]SGSE. The erythro isomer was more favored than threo isomer with
60.8% d.e. at 2min and 11.4% d.e. at 60min, respectively. At 60min(+)-erythro and (-)-threo isomers were formed with 24.8 and l4.6 enantiomeric excess (% e.e.), respectively.
Interestingly, the soluble preparation catalyzed the formation of (-)-erythro SGSE, whereas the insoluble
preparation did (+)-erythro SGSE.
2007-P08
カテキン類の熱変性に対する計算化学解析
徳満圭祐*1、石井 圭*1、正本博士*1、重松幹二*1、光永 徹*2
福岡大学工学部、岐阜大学応用生物科学部

463

Computor chemistry analysis of thermal transformation of carechins
Keisuke Tokumitsu*1, Kei Ishii*1, Hiroshi Masamoto*1, Mikiji Shigematsu*1, Tohru Mitsunaga*2*1
Faculty of Engineering, Fukuoka University, Fukuoka 814-0180, JAPAN, *2Faculty of Applied Biological
Science, Gifu University, Gifu 501-1193, JAPAN
Abstract:(+)-Catechin transforms to (+)-epicatechin at high temperature, and they reach tothermodynamically equilibrium state expressible with the equilibrium constant, K. This report deals with theequilibrium constants calculated by several methods of computer chemistry, K Calc, and the comparison of themto experimental value, KExpt. The KCalc by a molecular orbital calculation (RB3LYP/6-31G*) designatedqualitatively agreement with KExp. Which denotes superior of (+)-catechin to (+)-epicatechin and decreases withtemperature. However, KCalc quantitatively disagrees with KExpt.
2007-P09
高圧水蒸気蒸留による桐材成分の抽出
金原弥生、西谷耕三、棚橋光彦
岐阜大学大学院連合農学研究科
Extraction of constituents from paulownia wood by high-pressure steam distillation
Yayoi Kimpara, Kouzou Yoshitani, Mitsuhiko Tanahashi
Laboratory of Biomass Conversion, United Graduate School of Agriculture, Gifu University, Gifu 501-1193,
Japan
Abstract:
Paulownia (Pauloumia tomentosa) wood contains sesamin and paulownin which have arepellent action against insects. In this study, steam distillation of paulownia wood was conducted at two
different pressures (1.5 and 2.1MPa) and the distilled oil was analyzed by GC-MS. During high-pressure
steaming for paulownia wood, sesamin and paulownin were epimerized. The combined yield based on the drywood weight under 2.1MPa of sesamin and episesamin was 0.098%, and that of paulownin and epipaulownin
was 0.82%. Meanwhile, those of total extraction with alcohol-benzene refluxed for 24 hr were 0.49% and 1.1%,
respectively.
2007-P10
白色腐朽菌 Phanerochaete crassa WD1694 由来のグリオキサールオキシダーゼの生産と精製
高野麻理子、中村雅哉、山口宗義、渋谷源
森林総合研究所
Production and purification of glyoxal oxidase from a white-rot fungus Phanerochaete crassa WD1694
Mariko Takano, Masaya Nakamura, Muneyoshi Yamaguchi, Hajime Shibuya
Forestry and Forest Products Research Institute, Matsunosato 1, Tsukuba 305-8687
Abstract:
As a preliminary step to analyze localization mechanism of peroxidase reaction at
hyphal tips of P. crassa WD1694, production and purification of glyoxal oxidase from P. crassa WD1694 wasstudied. The maximum activity of glyoxal oxidase was produced in cultures containing 100 mg/l MnSO 4 and
0.05% Tween 80 on day 4 of growth. The harvested culture was filtrated, concentrated, and further purified with
DEAE-Sepharose. The purified GLOX was detected as a single band by the analysis of SDS-PAGE.
2007-P11
フラクトメータを用いた腐朽測定値とリグニン分解過程の相互関係
松本かほる、石栗太、飯塚和也、横田信三、吉澤伸夫
森林総合研究所
Relationship between compression strength of decayed wood measured by Fractometer and lignin degradation
process
Kahoru Matsumoto, Futoshi Ishiguri, Kazuya Iizuka, Shinso Yokota, Nobuo Yoshizawa
Faculity of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
To obtain basic knowledge for detecting the degree of wood decay using Fractometer,
relationship between compression strength of decayed wood measured by Fractometer and lignin degradation
process was investigated. Sapwood cores of Cryptomeria japonica, Prunus jamasakura,and Magnolia obovata were decayed for 60 days by a brown-rot fungus (Coriolellus palustri, FFPRI 0507), a
white-rot fungus (Coriolus versicolor, FFPRI 1030), and a soft-rot fungus (Chaetomium globosum, NBRC
6347). When C. japonica and P jamasakura cores were decayed, compression strength of each core wasdecreased. These results suggest that degree of decay in wood can be evaluated using compression strength464

measured by Fractometer.
2007-P12
Sphingomonas paucimobilis SYK-6 株の β-アリールエーテル代謝に関与する 4 種の脱水素酵素の機能と立体選択性
政井英司*1、森内英輝*1、佐藤裕介*1、福田雅夫*1、菱山正二郎*2、中村雅哉*2、片山義博*3*1
長岡技術科学大学・生物機能工学、*2 森林総合研究所、*3 東京農工大学大学院 BASE
Stereoselectivity and roles of four distinct guaiacylglycerol-b-guaiacyl ether dehydrogenases from
Sphingomonas paucimobilis SYK-6
Eiji Masai*1, Hideki Moriuchi*1, Yusuke Sato*1, Shojiro Hishiyama*2, Masaya Nakamura*2, Yoshihiro
Katayama*3, Masao Fukuda*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188,*2
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki 305-8687, *3Graduate School of
Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo
184-8588, Japan
Abstract:
Degradation of arylglycerol-β-aryl ether is the most important process of bacterial lignin
catabolism. S. paucimobilis SYK-6 oxidizes guaiacylglycerol-β-guaiacyl ether (GGE) toα-(2-methoxyphenoxy)- β-hydroxypropiovanillone (MPHPV), and then the ether linkage of MPHPV is cleaved
to generate α-glutathionyl-β-hydroxypropiovanillone and guaiacol. We have characterized enantioselective
glutathione S-transferases, which are involved in the ether cleavage of different enantiomers of MPHPV. In thisstudy, we found that three GGE dehydrogenases of SYK-6 are involved in the transformation of GGE into
MPHPV. LigD1 is essential for the transformation of(αR, βS)-GGE and (αR,βR)-GGE. Both LigD2 and LigD4 participate in the conversion of(αS,βR)-GGE and (αS,βS)-GGE.
2007-P13
Sphingomonas paucimobilis SYK-6 株のプロトカテク酸ジオキシゲナーゼが関与する 3-O-メチルガリック酸解裂経路
笠井大輔*1、政井英司*1、福田雅夫*1、片山義博*2*1
長岡技術科学大学・生物工学、 *2 東京農工大学大学院 BASE
Degradation of 3-O-methylgallate in Sphingomonas paucimobilis SYK-6 by pathways involving
protocatechuate 4,5-dioxygenase
Daisuke Kasai*1, Eiji Masai*1, Yoshihiro Katayama*2, Masa. Fukuda*2*1
Deparhnent of Bioengineering, Nagaoka Universiy of Technology, Nagaoka, Niigata, 940-2188, *2Graduate
School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588, Japan
Abstract:
Sphingomonas paucbnobilis SYK-6 converts vanillate and syringate to protocatechuate (PCA)
and 3-O-methylgallate (3MGA), respectively. 3MGA is metabolized via multiple pathways involving 3MGA
3,4-dioxygenase, PCA 4,5-dioxygenase (LigAB), and gallate dioxygenase. In this study, we investigated the roleof LigAB in syringate metabolism. The reaction product of 3MGA catalyzed by His-tagged LigAB was
identified
as4-caboxy-2-hydroxy-6methoxy-6-oxohexa-2,4dienoate(CHMOD)and
2-pyrone-4,6-dicarboxylate (PDC), indicating that 3MGA is transformed to CHMOD and PDC by the reaction
catalyzed by LigAB. Mutant analysis revealed hat die 3MGA catabolic pathways involving LigAB arefunctional in SYK-6.
2007-P14
リグニン下流代謝系プロトカテク酸 4，5-解裂経路遺伝子群の転写制御機横上村直史*1、高村一寛*1、原啓文*1、政井英司*1、福田雅夫*1、片山義博*2*1
長岡技術科学大学・生物工学、 *2 東京農工大学大学院 BASE
Transcriptional regulation of the genes involved in the protocatechuate 4,5-cleavage pathway
Naofumi Kamimura*1, Kazuhiro Takamura*1, Hirofumi Hara*1, Yoshihiro Katayama*2, Eiji Masai*1, Masao
Fukuda*1*1
Deparhnent of Bioengineering, Nagaoka Universiy of Technology, Nagaoka, Niigata, 940-2188, *2Graduate
School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588, Japan
465

Abstract:
The protocatechuate (PCA) 4,5-cleavage pathway is the essential metabolic route for lignin
catabolism in Sphingomonas paucimobilis SYK-6. Here we examined the operon structure of the PCA
4,5-cleavage pathway genes and investigated the transcriptional regulation of the genes.
Reverse transcription-PCR analysis indicated that the PCA 4,5-cleavage pathway genes of SYK-6 consist of
three transcriptional units, including the ligK-orf1-ligI-lsdA operon, theligJ-ligA-ligB-ligC operon, and the monocistronic ligR. Transcription of ligK and ligJ operons are directly
up-regulated by LigR, and this transcriptional activation requires PCA as an inducer.
2007-P15
リグニンモデル化合物の電気化学的酸化（2）、 − 1-phenylethanol 誘導体の酸化反応−
白石 匠、上高原 浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Electrooxidation of lignin model compounds (2) - Oxidation of 1-phenylethanol derivatives -.
Takumi Shiraishi, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
The Chemistry of Biomaterials, Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto
University, Sakyo-ku, Kyoto, 606-8502, Japan
Abstract:
The anodic oxidation of 1-phenylethanol derivatives, 1-(4'-ethoxy-3'methoxyphenyl) ethanol(1G), 1-(4'-ethoxy-3', 5'-dimethoxyphenyl) ethanol (1S) and 1-(4'-ethoxyphenyl) ethano1 (1 P) were
investigated for the application to the pretreatment of kraft pulping. The oxidation with
2,6-lutidine, gave the corresponding a-carbonyl derivatives (4-O-ethylacetovanilone : 2G,
4-O-ethylacetosyringone : 2S, 4-ethoxyacetophenone : 2P) in 40-70%. The electrooxidation mechanism of
1-phnylethanols is also proposed.
2007-P16
非木質試料におけるリグニン定量値の評価
中村裕貴，秋山拓也，Zhenfu Jin，Deded S．Nawawi，横山朝哉，松本雄二
東京大学大学院農学生命科学研究科
Evaluation of lignin content in non-wood plants
Hirotaka Nakamura, Takuya Akiyama, Zhenfu Jin, Deded S. Nawawi, Tomoya Yokoyama, Yuji Matsumoto
Wood Chemistry Laboratory, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
To evaluate the lignin content in non-wood cell walls, leaves and grass stems of various
vascular plants were subjected to different kind of wet chemical analyses and these results were compared withthe apparent lignin content obtained by Klason procedure. As a method of wet chemical analysis, nitrobenzene
oxidation and ozonation were applied. Infrared spectroscopy was also used to estimate the amount of aromatic
structures. The comparison of apparent lignin content and the yields of specific degradation products obtainedby wet chemical methods suggested that the Klason procedure cannot give the correct lignin content in the caseof non-wood cell walls. The amount of aromatic structures estimated by FT-IR was correlated very well with theyield of nitrobenzene oxidation products, which strongly supported the idea that lignin content in non-wood cell
walls can be more reasonably expressed by the yields of these specific degradation products rather than Klason
procedure.
2007-P17
リグニンの熱分解による機能性炭素への物質変換
肥留川孝治、木島正志
筑波大学大学院数理物質科学研究科
Conversion of lignin to functional carbon materials by pyrolysis
Takaharu Hirukawa, Masashi Kijima
Institute of Materials Science, Graduate School of Pure and Applied Sciences, University ofTsukuba
Abstract:
It is attempted that nano-structured and porous carbon materials were synthesized by pyrolysis
of lignin. Under anaerobic conditions of a slow heating rate, lignin (alkaline) was converted to a porous
carbonaceous material showing 738 m2/g of BET surface area. Under the same heating conditions, afreeze-dried reverse micelle of lignin converted to a high porous carbonaceous material showing 1003 m2/g ofsurface area.
466

2007-P18
β-5 型リグニンモデル化合物の熱分解− メチル化
黒田健一*1、中川明子*2、芦谷竜矢*3、藤田弘毅*1*1
九州大学大学院農学研究院、*2 筑波大学大学院生命環境科学研究科、*3 山形大学農学部
Tetramethylammonium hydroxide (TMAH) thermochemolysis of lignin: Behavior of β5-type lignin modelcompounds
Ken-ichi Kuroda*1, Akiko Nakagawa*2, Tatsuya Ashitani*3, Koki Fujita*1*1
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University, 6-10-1
Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan, *2Graduate School of Life and Environmental Sciences,
University of Tsukuba, 1-1-1, Tennodai, Tsukuba, lbaraki 305-8572, Japan*3
Faculty of Agriculture, Yamagata University, 1-23 Wakaba, Tsuruoka, Yamagata 997-8555, Japan
Abstract:
Phenolic 2-arylcoumarans 1-6 were subjected to tetramethylammonium hydroxide (TMAH)
thermochemolysis (500 ºC/4 s) to investigate reactions occurring in lignin specifically under these conditions.
Products were monitored by gas chromatography/mass spectrometry (GC/MS). GC/MS signals corresponding
to dimers overwhelmed all GC/MS traces. (2-Phenyl-2,3-don-3-yl) methan-1-ols (1 and 6) predominantly gave
2,3,3',4'-tetramethoxystilbenes
involving
in
a
loss
of
the
γ-CH2OH
substituent.
3-Methyl-2-phenyl-2,3-dihydrobenzofurans
(2-5)
gave
a
mixtureof
1-(3,4-dimethoxyphenyl)-2-(2,3-dimethoxyphenyl)-1-methoxypropans and 2,3,3’,4’- tetramethoxy-stilbenes
having the γ-methyl group. Side chains –CH=CHCH2OH and -COOH on ring B were simply methylated to
produce the corresponding methyl ether and ester, respectively. A –CH=CHCH3 Side chain was preserved intact,
whereas a –CH=CHCHO side chain changed to a -CHO side chain. This was confirmed by isolating
5-formyl-2,3,3',4'-tetramethoxystilbene as an off-line TMAH thermo- chemolysis product from3-[2-(4-hydroxy-3-methoxyphenyl)-3- hydroxymethyl-7-methoxy-2, 3- dihydrobenzofuran-5-yl] propenal.
2007-P19
DSC で検出されるリグニンのガラス転移温度に対する加熱前処理の影響一 針英樹と広葉樹の違いおよびメトキシ基量の影響
山田竜彦*1*2、久保智史*1、橋田 光*1、John F. Kadla*3、Hou-min Chang*4, Vincent Chang*4*1
森林総合研究所、*2 農林水産省農林水産技術会議事務局、*3 ブリティッシュコロンビア大学、*4 ノースカロラ
イナ州立大学
Effects of DSC pre-heat treatment on the glass-transition temperature of lignin -Difference between softwoodand hardwood lignin, and effect of methoxy contents
Satoshi Kubo*1, Tatsuhiko Yamada*1*2, Koh Hashida*1, John F. Kadla*3, Hou-min Chang*4, Vincent Chiang*4*1
Forestry and Forest Products Research Institute, Tsukuba, Japan, *2Agriculture, Forestry and Fisheries
Research Council, Tokyo, Japan, *3The University of British Columbia, Vancouver, B.C., Canada, *4North
Carolina State University, Raleigh, NC, USA
Abstract:
In the DSC analysis of lignin, thermal treatment "pre-heat treatment" is usually required toremove thermal history before measurement. However, glass transition temperature of softwood kraft lignin was
significantly affected by this pre-heat treatment. By contrast, such Tg increase was not observed for hardwood
kraft lignin. Typical structural difference between softwood and hardwood lignin can be found in the aromaticring structure. Therefore, DSC analysis was also performed for various lignins which have different S/G.
However, clear correlation could not be detected between S/G and Tg increases. S/G would be not solo factor tosuch Tg increase of lignin.
2007-P20
リグニンを基盤とした新規ポリマーの創製
井上宗亮、松下泰幸、今井貴規、福島和彦
名古屋大学大学院生命農学研究科
Development of novel polymer based on lignin
Sosuke Inoue, Yasuyuki Matsushita, Takanori Imai, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601
Abstract:
In Japan, lignosulfonate is mainly used for water reducing agent of cement and dye dispersant.
In order to expand in application, we tried to produce a novel polymer based on the lignosulfonate. We obtained
ion-conducting polymers from sodium lignosulfonate by substitution of sodium ion to imidazole compound. The
467

polymers showed higher conductivity with longer the side chain of imidazole compound. Purification of sodium
lignosulfonate led low ion conductivity. It is suggested that impurity contained in the sodium lignosulfonate,such as sugars, induced the ion conductivity.
2007-P21
イオン性相互作用によるリグノスルホン酸の生体関連物質吸着能長谷川大輔*1、寺本好邦*2、西尾嘉之*1*1
京都大学大学院農学研究科、*2 産業技術総合研究所バイオマス研究センター
Functionalization of lignosulfonic acid: Its adsorption property to catch bio-related substances by ionicinteractions
Daisuke Hasegawa*1, Yoshikuni Teramoto*2, Yoshiyuki Nishio*1*1Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, *2National Institute ofAdvanced Industrial Science and Technology (AIST), Biomass Technology Research Center, 2-2-2, Hirosuehiro,
Kure, Hiroshima, 737-0197, Japan
Abstract:
Poly-ion complexes of anionic lignosulfonic acid (LSA) with cationic poly(L-lysine) (PLL)
were prepared by spontaneous precipitation from mixed aqueous solutions adjusted at different pHs. Fouriertransform infrared (FTIR) measurements and elementary analysis for the complexes revealed the presence ofstrong ionic interactions between the sulfonic anion of LSA and the -aminocation of PLL. Circular dichroism
measurements revealed that an -helix conformation of PLL changed to a random coil conformation when thecomplexes were formed. An adsorption property of LSA to catch nicotine compounds was also examined by
FTIR measurements and highperformance liquid chromatography.
2007-P22
高圧水蒸気蒸留による竹からのチロシンの効率的な抽出
烏日郷*1・道家真一*2・村手宏隆*2・棚橋光彦*1*2*1
岐阜大学農学部、*2 岐阜大学工学部
Development of the efficient extraction of tyrosine from grown bamboo shoot by high-pressure steam
distillation
Wurina*1, Shinichi Doke*2, Hirotaka Murate*2, Mitsuhiko Tanahashi*1*2*1
Faculty of Agriculture, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan, *2Faculty of Engineering, Gifu
University, 1-1 Yanagido, Gifu 501-1193, Japan
Abstract:
It was confirmed that large quantities of tyrosine is contained in grown bamboo shoot by solidstate CPMAS 13C-NMR analysis. Because of its chemical structure, tyrosine is not distillable with common
steam distillation method. Therefore, a new high-pressure steam distillation method was evaluated for efficient
extraction of tyrosine from bamboo shoot. From the distilled essential oil of madake bamboo shoot, 4-hydroxy
styrene and 3-methoxy-4-styrene derivatives were isolated and identified.

468

第 53 回 （2008.10.30-31） 東京大学農学部 弥生講堂
2008-101
イネのケイヒ酸モノリグノール経路遺伝子の検索と遺伝子発現解析
山本直樹*1、鈴木史朗*2、村上真也*1、坂本正弘*3、服部武文*1、梅澤俊明*1*2*1
京都大学生存圏研究所、*２京都大学生存圏研究所基盤ユニット、*３京都大学大学院農学研究科
Computational identification and expression analysis of monolignol biosynthesis pathway genes in rice
Naoki Yamamoto*1, Shiro Suzuki*2, Shinya Murakami*1, Masahiro Sakamoto*3, Takefumi Hattori*1,
Toshiaki Umezawa*1*2*1
Research Institute for Sustainable Humanosphere, Kyoto university. Gokasho, Uji, Kyoto 611-0011, Japan,*2
Institute of Sustainability Science, Kyoto university. Gokasho, Uji, Kyoto 611-0011, Japan, *3Faculty/Graduate
School of Agriculture, Kyoto university, Kitashirakawa Oiwakecho, Sakyo-ku, Kyoto, Kyoto 606-8502, Japan..
Abstract:
It is still unknown which gene set works in monolignol biosynthesis in rice. Here, wesurveyed computationally the genes encoding enzymes of the cinnamate/monolignol pathway in allrice protein sequences. Expression analysis of the rice genes showed diversification of the qualitative andquantitative expression patterns among the gene family members. The most part of
the genes were classified into 5 groups with the organ-specific expression pattern using Self
Organizing Maps method. The fact that all the groups have plural enzyme genes of the monolignol
biosynthesis pathway implies role and responsibility of the gene sets for monolignol synthesis in each organ.
2008-102
TDNA 挿入変異体を用いたシロイヌナズナ 4CL 遺伝子の機能解析
吉村奈穂、佐藤かんな、片山義博、梶田真也
東京農工大学大学院 BASE
The functional analysis of 4-coumarate:CoA ligase genes in Arabidopsis thaliana by using T-DNA tagged
mutants
Naho Yoshimura, Kanna Sato, Yoshihiro Katayama, Shinya Kajita
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan
Abstract:
4-Coumarate:CoA ligase is one of key enzymes in biosynthesis of monolignols in many plants.
Arabidopsis thaliana has five 4CL genes (At4CL1-At4CL5) in its genome. To understand thefunction of the genes for 4CL in the lignin biosynthesis, the phenotypes of two T-DNA inserted
mutants (At4cl1/At4cl1 and At4cl2/At4cl2) were analyzed in this study. We have measured 4CL
activity of the mutants with crude enzymes from their stems. The activities of At4cl1/At4cl1 andAt4cl2/At4cl2 lines were 12.5% and 43.7% of that in control line, respectively. As the results of lignin specificstaining, decrease in lignin content and composition of syringyl residue in At4cl1/At4cl1 line were revealed,
whereas those in At4cl2/At4cl2 line were nearly identical to the control plant. The mutant and control lines
showed similar development pattern except for a At4cl1/At4cl1 line, SALK142526, which exhibited dwarf
phenotype. These results suggest that At4CL1 plays crucial roles in lignin biosynthesis in A. thaliana.
2008-103
改変型植物酸性 peroxidase の酵母での発現と精製（2）吉中喬慈、川合伸也
東京農工大学大学院
Heterogeneous expression and purification of modified plant peroxidase (2)Kyoji Yoshinaka, Shinya Kawai
Faculty of Agriculture, Tokyo University of Agriculture and Technology, 3-5-8, Saiwai-cho, Fuchu, Tokyo
183-8509, Japan
Abstract:
Lignin peroxidase of Phanerochaete chrysosporium can oxidize the environmental pollutants
and lignin by assuming Trp-171 near the surface of the protein to be a catalyst site. CWPO-C that is a kind of
poplar peroxidases can oxidize sinapyl alcohol, and is presumed that Tyr-74 arid Tyr-177 exposed to the surfaceof the protein are the catalyst sites. We introduced the mutations into prxA3a, a POX gene of Populus
kitakamiensis, changed the amino acid residues at thecorresponding positions to Trp and Tyr residues, and examined the changes in the substrate specificities.
469

2008-104
選択的リグニン分解菌が産生する菌体外脂質関連代謝物の構造解析
西村裕志、村山京子、渡連崇人、本田与−、渡辺隆司
京都大学生存圏研究所
Structural analyses of extracellular lipid-related metabolites produced by a selective lignin degrading fungus
Hiroshi Nishimura, Kyoko Murayama, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Laboratory of Biomass Conversion, Research Institute for Sustainable Humanosphere (RISH), Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan.
Abstract:
Wood-rot fungus, Ceriporiopsis subvermispora can degrade lignin without intensive damage ofcellulose. We have been focusing on extracellular metabolites participating in the selective ligninolysis, andcharacterized a series of unique metabolites, ceriporic acids. Important function of ceriporic acid is inhibition ofcellulose degradation by hydroxyl radicals (HO・) produced by the Fenton reaction system. Here, we investigate
extracellular lipid-related metabolites using liquid chromatography, mass spectrometry and nuclear magnetic
resonance spectrometry. New metabolites including a series of ceriporic acids were found and analyzed.
2008-105
抗炎症剤であるジクロフェナクおよびメフェナム酸の白色腐朽菌による毒性除去
畑 貴之*1、河合真吾*1、西田友昭*1、岡村秀雄*2*1
静岡大学農学部、 *2 神戸大学大学院海事科学研究科
Removal of toxicities of anti-inflammatory drugs, diclofenac and mefenamic acid, by white rot fungus
Phanerochaete sordida YK-624
Takayuki Hata*1, Shingo Kawai*1, Tomoaki Nishida*1, Hideo Okamura*2*1
Department of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka University, 836
Ohya, Suruga-ku, Shizuoka 422-8529, Japan, *2Faculty of Maritime Sciences, Kobe University Graduate schoolof Maritime Sciences, 5-1-1 Fukaeminamicho, Higashinada-ku, Kobe 658-0022, Japan
Abstract:
At present, there is an increasing concern on the presence of pharmaceutical compounds in theenvironment mainly due to their potential risk to the aquatic environment. In this study, diclofenac (Dic) andmefenamic acid (Mef), which are used widely as non-steroidal anti- inflammatory drugs and are ubiquitously
found in the water sample, were treated with white rot fungus Phanerochaete sordida YK-624 under ligninolytic
condition with low-nitrogen and high- carbon culture medium. After 6 days of fungal treatment, Dic completely
disappeared and Met decreased by about 90%. During the treatment of Dic, two major metabolites,
4’-hydroxydiclofenac
and 5-hydroxydiclofenac, were found in the cultures. On the other hand, a major metabolite of Mef was
3'-hydroxymefenamic acid. Toxicities of Dic and Mef before and after fungal treatment were evaluated by acutelethal toxicity test using freshwater crustacean Thamnocephalus platyurus. The profiles for removal of toxicities
of Dic and Mef and decrease in concentrations of both drugs during
treatment were very similar. These results suggested that hydroxylation of Dic and Mef is mainly involved indetoxification of these drugs.
2008-106
冬虫夏草（Cordyceps）菌による多環式芳香族炭化水素および塩素化ダイオキシン分解の試み
久野祐功*1、渡辺昌司*1、亀井一郎*1*2、近藤隆一郎*3*1
九九州大学大学院生物資源環境科学府、*2 福岡大学工学部、*3 九州大学農学研究院
Attempts to degrade polycyclic aromatic hydrocarbons (PAHS) and chlorinated dioxins by Cordyceps species
Tasuku Kuno, Ichiro Kamei, Masashi Watanabe, Ryuichiro Kondo
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University, 6-10-1,
Hako2aki, Higashi-ku, Fukuoka, 812-8581, Japan
Abstract:
Degradation experiments of chlorinated dioxins using Cordyceps species were carried out. As
chlorinated dioxins, 2,7-dichloro-, 2,3,7-trichloro, 1,3,6,8-, 1,3,7,8-, and 1,3,7,9-tetrachloro- dibenzo-p-dioxin
and 2,4,8-trichhrodibenzofuran were used. Cordyceps brongniartii and Cordyceps militaris, were selected basedon the ability of 2,7-dichlorodibenzo-p-dioxin (2,7-diCDD) degradation. 2,7-DCDD, 2,3,7-triCDD and
2,4,8-triCDF were biotransformed to hydroxyl compounds by C.militaris. PAHs were degraded rapidly in
medium containing chitin or chitosan by C. militaris and C. brongniartii. Phenanrhrene and pyrene werecompletely disappeared in these medium. In addition, benzo [a] pyrene and indeno [1,2,3-c,d] pyrene also weredegraded extensively.
470

2008-107
Biodegradation of phenanthrene, an aromatic hydrocarbon by Polyporus sp. S133 in liquid medium
Tony Hadibarata, Sanro Tachibana, Kazutaka Itoh
Department of Applied Bioscience, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime
790-8566, Japan
Abstract:
The effect of adding several concentrations of tween 80 and agitation rate to increasedegradation rate of phenanthrene by using Polyporus sp. S133 collected from contaminated soil was studied. A
maximal degradation rate (92%) was obtained when Polyporus sp. S133 was cultured underagitation of 120 rpm for 30 days, as compared to just 44% degradation in non-agitated cultures. The
degradation rate increased as the amount of tween 80 added increased. The rate in agitated cultures
was about 2 times that in non-agitated cultures. The mechanism for degradation of phenanthrenewith the fungus through identification of the metabolites was found.
2008-108
微生物機能を用いた植物バイオマス資源（リグニン）の新規ポリマー原料への変換技術と新しい機能性材料の製造 III岡村祐里子*1、大塚博之*1、間瀬浩平*1、阿部友邦*1、笠井大輔*2、政井英司*2、福田雅夫*2、大塚祐一郎*3、
中村雅哉*3、大原誠資*3、重原淳孝*4、佐藤かんな*1、梶田真也*1、片山義博*1*1
東京農工大学大学院 BASE、*2 長岡技術科学大学・生物機能工学、*3 森林総合研究所、*4 東京農工大学工学府
Studies of technology that converts plant biomass (lignin) into new polymer materials using bacterial function
and products novel functionality materials, III
Yuriko Okamura*1, Hiroyuki Otsuka*1, Kohei Mase*1, Tomokuni Abe*1, Daisuke Kasai*2, Eiji Masai*2,
Masao Fukuda*2, Yuichiro Otsuka*3, Masaya Nakamura*3, Seiji Ohara*3, Kiyotaka Shigehara*4, Kanna Sato*1,
Shinya Kajita*1, Yoshihiro Katayama*1*1
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei Tokyo, 184-8588, Japan, *2Department of BioEngineering, Nagaoka University ofTechnology, Nagaoka Niigata, 940-2188, Japan, *3Forestry and Forest Products Research Institute, Matsunosato
Tsukuba Ibaraki, 305-8687, Japan, *4Graduate School of Technology, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan
Abstract:
Sphingomonas paucimobilis SYK-6 is able to grow on various lignin-derived biaryls, and2-pyrone-4,6-dicarboxylic acid (PDC), an intermediate of these compounds, can be used as the polymer
materials. In a previous study, we built a bioreactor to produce PDC with genetic technique, and succeeded in
producing PDC from protocatechuate, vanillin, vanillate, and p-hydroxybenzoate. In this study, we examined thefeasibility of industrial PDC production by using lignosulfonic acid, one of the actual lignin resolvent. The
existence of resolvent of lignosulfonic acid did not inhibit PDC production from 5 g/L vanillin. This result raise
the possibility of industrial PDC production built into the paper-forming process.
2008-109
単離リグニンの両親媒性化とその機能評価
本間春海*1、浦木康光*1、久保智史*2、山田竜彦*2、松下泰幸*3、福島和彦*3*1
北海道大学大学院農学研究科、*2 森林総合研究所、*3 名古屋大学大学院生命農学研究科
Conversion of lignin to amphiphilic compounds and their characterization
Harumi Homma*1, Satoshi Kubo*2, Tatsuhiko Yamada*2, Yasuyuki Matsushita*3, Kazuhiko Fukushima*3,
Yasumitsu Uraki*4*1Graduate School ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan, *2Department of Biomass
Chemistry, Forestry and Forest Products Research Institute, Tsukuba 305-8687, Japan,*3
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan,*1
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan
Abstract:
The acetic acid lignin (AL) was converted to an amphiphilic polymer by derivatization of AL
with several polyethylene glycol diglycidylethers (PEGDE) to make use of them as a nonionic surfactant. The
derivatives revealed significant surface activity, such as reduction of water surface tension and critical micelleconcentrations (CMC), although both PEGDE and PEG showed very weak. The surface activity of AL
derivativewasimprovedbythereactionwithmonoepoxide
compound,ethoxy-(2-hydroxy)-propoxy-polyethylene glycol glycidylether (PEGGE). The hydrophile-lipophile balance
471

(HLB) suggested these derivatives were suitable to use as emulsifiers and detergents. In addition, thesederivatives were found to have higher biodegradability than lignin. Consequently, these derivatives arepromising as environmentally-friendly surfactants.
2008-110バイオエタノール生産副産物加水分解リグニンを原料とするポリウレタンの調製と物性
畠山兵衛*1，辻本泰人*1、廣瀬重雄*2、畠山立子*3*1
福井工業大学・工学部、*2 産業技術総合研究所、*3 リグノセルリサーチ
Preparation and properties of polyurethane derived from hydrolysis lignin obtained as byproduct of bioethanol
Hyoe Hatakeyama*1, T. Ohsuga*1, M. Shimada*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3*1
Fukni University of Technology, 3-6-1, Gakuen, Fukui 910-8505, AIST, 1-1-4 Higashi, Tsukuba, 305-8565,
Lignocell Research, 73-8, Yatsumata, Fukui 910-3558
Abstract:
Polyurethane (PU) foams were prepared using hydrolysis lignin (HL) obtained as a by-productof bioethanol industry. Four kinds of HL's from Russia and New Zealand were utilized. Sodium lignosulfonate(LS) obtained as a by-product of the pulping industry was also used as a reference. HL and LS polyols wereobtained by dissolving HL and LS in diethyleneglycol (DEG) andpolyethyleneglycol (PEG200). In this study, PU foams were obtained by reacting the above polyols withpoly(phenylene methylene) polyisocyanate (MDI) using a small amount of water as foaming reagent. Apparent
density of PU foams was in a range from 0.04 to 0.08 g/cm3. Compression strength (δ10) was in a range from
0.1 to 0.4MPa. Thermal degradation was ca. 300 ºC and mass residue at 500 ºC was ca. 35 %. Glass transition
temperature (Tg) of PU foams from DEG was ca. 100 ºC regardless of kinds of lignin. In contrast, Tg of PU
foams from PEG was ca. 50 ºC. Thermal conductivity was ca. 0.03 W/mK which indicates that PU foams show
excellent insulation effect. It is concluded that PU foams derived from HL can be applicable for housingmaterials as an insulator.
2008-111
リグニンスルホン酸塩、エチレングリコール及びグリセリンを原料とするエポキシ樹脂の合成と熱的性質
廣瀬重雄*１、畠山立子*２、畠山兵衛*３*１
産業技術総合研究所、*２リグノセルリサーチ、*３福井工業大学工学部、Synthesis and thermal properties of epoxy resins from ligninsulfonate, ethylene glyco1 and glycerol
Shigeo Hirose*１, Tatsuko Hatakeyama*１, Hyoe Hatakeyama*3*１
Research Institute for Immovation in Sustainable Chemistry, AIST, Central 5, 1-1-4 Higashi, Tsukuba, Ibaraki
305-8565, Japan, *2Lignocel Research Ltd., Yatsumata, Fukui 9 1 0-3558, Japan,*3
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Sodium ligninsulfonate (LS) was dissolved in glycerol (GLY) and the obtained mixture
was allowed to react with succinic anhydride to form a mixture of ester-carboxylic acid derivatives(LS-GLY polyacid, LSGLYPA). LS-ethylene glycol (EG)-polyacid (LSEGPA) was also prepared from
EG. The mixture of LSGLYPA and LSEGPA was reacted with glycerol diglycidyl ether (GLYDGE) in thepresence of catalytic amount of dimethylbenzy1amine to form epoxy resins. The molar ratio of epoxy groups tocarboxylic acid groups ([EPOXY]/[AA] ratio, mol/mol) was maintained at 1.1. The
contents of LSGLYPA in the mixture of LSGLYPA and LSEGPA (LSEGPA content) were varied from0 to 100 %. Thermal properties of epoxy resins were studied by differential scanning calorimetry (DSC) andthermogravimetry (TG). Glass transition temperatures (Tg's) of epoxy resins increased with increasing
LSGLYPA contents suggesting that glycerol act as a cross-linking forming agent in epoxy resin networks.
Thermal decomposition temperatures (Td's) of epoxy resins were almost constant regardless of LSGLYPA
contents.
2008-特別講演
有機合成化学的アプローチによる木質バイオマス成分研究 一木材の総合研究と総合利用一
中坪文明
京都大学大学院農学研究科
Studies on the woody biomass constituents by organic synthetic approach -Toward total utilization of woody
biomass by interdisciplinary researchFumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto
472606-8502, Japan
Abstract:
Studies on the woody biomass constituents by organic synthetic approach toward total
utilization of woody biomass by interdisciplinary research are reported: general synthetic method for oligo- andpolylignols and novel selective cleavage method for β-O-4 in the lignin chemistry; chemical synthesis ofcellulose and its extended research to the preparation and characterization of Langmuir-Blogett films, cellulosic
photocurrent generation thin films in the cellulose chemistry, and syntheses of hydrolysable and condensed
tannins and their properties in tannin chemistry.
2008-201
クラフトーアントラキノン蒸解におけるアントラキノン浸透処理の効果
田中潤治*1、大井 洋*2、横山朝哉*3、松本雄二*3*1
川崎化成工業株式会社技術研究所、*2 筑波大学生命環境科学研究科、*3 東京大学農学生命科学研究科
Effects of anthraquinone compounds impregnation in kraft cooking
Junji Tanaka*1*3, Hiroshi Ohi*2, Tomoya Yokoyama*3, Yuji Matsumoto*3*1
Kawasaki Kasei Chemicals Ltd., *2Graduate School of Life and Environmental Sciences, University ofTsukuba, *3Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
In order to increase the pulp yield by anthraquinone compounds, it is very important toimpregnate anthraquinone compounds efficiently into wood chips. In this report, the effect of impregnation
treatment before kraft cooking process was investigated using the laboratory cooking equipments. By measuring
9,10-anthraquinone in the liquor after the impregnation treatment, the impregnation conditions (temperature,time, active alkali charge, and liquor/wood ratio) were optimized. By the employment of the optimized
impregnation condition, the pulp yield was improved by about 0.4% when compared at kappa 16.
2008-202
Analysis of lignin by the use of whole wood solution consisting of DMSO-LiCl
Zhiguo Wang, Tomoya Yokoyama, Yuji Matsumoto
Department of Biomaterials Sciences, Graduate School of Agricultural and Life Sciences, The University ofTokyo
Abstract:
The whole lignin in wood was analyzed by the use of whole wood solution consisting
DMSO/LiCl. The wood solution formed gel after standing one day at room temperature. Concentration ofmilled wood required for gel formation was dependent on the milling time. The gram absorptivity of lignin at
280nm was obtained by the use of this whole wood solution. The 1H-NMR spectrum of whole wood solution
clearly shows the lignin aromatic part without any interfering overlapping peak. This is the first time to obtain
information of aromatic part in whole lignin directly
without any kind of isolation treatment.
2008-203
イオン液体処理過程における木材成分の溶出挙動とリグニンの変化
蓮見愛*1、中川明子*1、大井洋*1、岸野正典*2*1
筑波大学大学院生命環境科学研究科、*2 北海道立林産試験場
Structural change of lignin during a process of wood components dissolution into ionic liquid
Ai Hasumi*1, Akiko Nakagawa-izumi*1, Masanori Kishino*2, Hiroshi Ohi*1*1
Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba,
Ibaraki 305-8572, Japan, *2Hokkaido Forest Products Research Institute, 1-10 Nishikagura, Asahikawa,
Hokkaido 071-0198, Japan
Abstract:
Wood meals of Abies sachalinensis and three eucalyptus were treated with one of the ionicliquids: 1-n-buthyl-3-methylimidazolium chloride ([bmim]Cl). The contents of lignin and carbohydrates in theinsoluble fractions were determined. The insoluble fractions were applied to analytical pyrolysis for lignin
characterization. The results showed that cellulose dissolved significantly during the [bmim]Cl treatment. The
pyrograms of insoluble fraction were quite similar to that of untreated wood. Moreover, the amount of βO-4linkage in lignin were slightly decreased by this treatment. Therefore, it showed that chemical characteristics oflignin were hardly changed by the [bmim]Cl treatment.
2008-204
イオン液休中での βO-4 型リグニンモデル化合物の反応性
久保智史、山田竜彦、橋田光、菱山正二郎、眞柄謙吾、細谷修二
473

森林総合研究所
Reactivity of β-O-4 type ligmin model compounds in ionic liquids
Satoshi Kubo, Tatsuhiko Yamada, Koh Hashida, Shojiro Hishiyama, Kengo Magara, Shuji Hosoya
Forestry and Forest Products Research Institute. 1 Matsunosato, Tsukuba, Ibaraki
Abstract:
Structural stabilities and reactivity of lignin in ionic liquids (ILs) have been examined using
lignin model conpounds. Threo type guaiacylglycerol-β-guaiacyl ether (T-GG) was decomposed similarly to [Z]isomer of enol-ether, [Z]-3-(4-hydroxy-3-methoxyphenyl)-2- (2-methoxyphenoxy)-2-propenol (Z-EE), as
erythroGG (E-GG), although decomposition rates of E-GG were faster than TLGG. Hardwood type β-O-4lignin model compounds, threo-guaiacyl- glycerol-βsyringyl ether (T-GS) was decomposed rather faster thansoftwood type β-O-4 lignin model compounds, and nonphenolic model compounds were relatively stable in ILs.
These results could be comparable with the structural stability of β-O-4 type lignin model compounds inalkaline conditions, although the reaction mechanisms in ionic liquids have not been elucidated.
2008-205
イオン液体中での木材の反応挙動 一針葉樹と広葉樹の比較−
中村篤史*1、宮藤久士*1、坂志朗*1、植田文雄*2、森みどり*2*1
京都大学大学院エネルギー科学専攻科、*2 トヨタ自動車株式会社
Reaction behavior of wood in an ionic liquid -Comparisons between softwood and hardwoodAtsushi Nakamura*1, Hisashi Miyafuji*1, Shiro Saka*1, Fumio Ueda*2, Midori Mori*2*1
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan, *2Vehicle Engineering Group, Toyota Motor
Corporation, 1, Toyota-cho, Toyota, Aichi, 471-8572, Japan
Abstract:
Reaction behavior of western red cedar (Thuja plicata) and beech (Fagus crenata) as treated inan ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) which can dissolve cellulose wasinvestigated. Much residue after [C2mim][Cl] treatment can be obtained from western red cedar, compared tobeech. Lignin content in the residues from western red cedar is higher than in that from beech. It is also foundthat the degradation of lignin occurs by the cleavage of the ether linkage with [C2mim] [Cl] treatment.
2008-206β-エーテル型リグニン 2 主体モデル化合物の熱分解における同位体効果
渡辺敏弘，河本晴雄，坂 志朗
京都大学大学院エネルギー科学専攻科
Kinetic isotope effects in pyrolysis of lignin β-ether model dimers
Toshihiro Watanabe, Haruo Kawamoto, Shiro Saka
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyoku, Kyoto, 606-8501, Japan
Abstract:
From the comparison of the reactivities and the pyrolysis products of lignin β-ether- typedimers between an open-top and a closed ampoule reactors, We have proposed some radical chain reactions
starting from the H-Abstraction reactions. In this paper, kinetic isotope effects observed in the deuterated dimers
are described. Based on the results, possibilities of radical chain reactions in lignin pyrolysis are discussed.
2008-207
木材ガス化におけるセルロースーリグニン間の相互作用
細谷隆史，河本晴雄，坂 志朗
京都大学大学院エネルギー科学専攻科
Interactions between cellulose- and lignin-derived pyrolysis products in gasification
Takashi Hosoya, Haruo Kawamoto, Shiro Saka
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyoku, Kyoto, 606-8501, Japan
Abstract:
Interactions between cellulose- and lignin-derived pyrolysis products were studied undergasification conditions (N2/600ºC/40-80s). A dual-space closed ampoule reactor was used to eliminate thesolid-phase interactions, and careful comparison of the resulting data with those of the pyrolysis of the mixed
samples gave some insights into the solid - and vapor-phase interactions separately. As a result, significant
interactions were observed which include acceleration of the gasification of cellulose-derived volatiles and theformation of methane and catechols from lignin. These influences are explained with a proposed mechanism, in474

which the cellulose-derived volatiles act as H-donors while the lignin-derived volatiles (radicals) as
H-acceptors.
2008-208
13
C 標識テトラメチルアンモニウムヒドロキシドを用いた熱分解−メチル化法によるリグニン中の β-O-4 型構造
およびシンナミルアルコール末端基の検討
中川明子*1、TimotbyR．Filley*2、黒田健一*3*1
筑波大学大学院生命環境科学研究科、*2Purdue 大学、*3 九州大学大学院農学研究院
Chamcterization of βO-4 and cinnamyl alcohol end units in lignin by 13C-labeled TMAH thermochemolysis
Akiko Nakagawa-izumi*1, Timothy R. Filley*2, Ken-ichi Kuroda*3*1Graduate School of Life and Environmental Sciences, University of Tsukuba, Tennoudai,
Tsukuba, Ibaraki, 305-8572, Japan, *2Department of Earth and Atmospheric Sciences, Purdue University, 550
Stadium Mall Drive, West Lafayette, Indiana 47907, USA, *3Department of Forest and Forest Products Sciences,
Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
To estimate the origins of pyrolysis-methylation products from lignin, 13C-labeled
tetramethylammonium hydroxide (13C-TMAH) thermochemolysis was applied to lignins pre-methylated withdiazomethane. Products were monitored by gas chromatography/mass spectrometry. The number of 13C atom
incorporated in the products showed that in guaiacyl synthetic lignin (DHP) coniferyl alcohol end units arepresent in a 7/3 of 4-O-/γ-O-etherified forms, while in Japanese cedar wood they are present in roughly 6/4 ratio.
In both lignins, guaiacylglycerol moieties involving in β-O-4 linkage provided the same amount of
1-(3,4-dimethoxyphenyl)-1,2,3- trimethoxypropane consisting of two isomers (erythro- and threo-forms) fromend units and core units. Although G-DHP provided many dimer products, the cedar provided those in a trace
amount.
2008-209
リグニンモデル化合物の間接電解酸化反応
白石匠、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Indirect electrooxidation of lignin model compounds
Takumi Shiraishi, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku. Kyoto,606-8502, Japan
Abstract:
Indirect electrooxidation of lignin model compounds using N-hydroxyphthalimide (NHPI) as an
mediator was studied to introduce carbonyl group at -position. Monomeric lignin models,
1-(4'-ethoxy-3'-methoxyphenyl)ethanol (1G), 1-(4'-ethoxy-3',5'-dimethoxyphenyl)ethanol (1S) were oxidized tothe corresponding carbonyl compounds (2G, 2S) in high yields (over 90%) and high current efficiencies (ca.
90%).
In
the
indirect
electrooxidationofdimeric
ligninmodel(4-ethoxy3-methoxyphenylglycerol-β-guaiacylether(3)),α-carbonyldimer(3-hydroxy-1-(4-ethoxy-3methoxyphenyl)-2-(2-methoxyphenoxy)-propan-1-one (4)) was formed, while 4-O-ethylvanillin was formed in
the direct oxidation. These results suggest that NHPI-mediated indirect electrooxidation is an effective method
for α-carbonyl introduction to natural lignin structures.
2008-210
モノリグノール配糖体によるシリンギル型 DHP の生成挙動の解析（II）−pH の影響−
飛松裕基、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Mechanistic study of the dehydrogenative polymerization using -glycosylated monolignols, II-The effect of pH on the formation of syringyl dehydrogenation polymers
Yuki Tobimatsu, Hiroshi Kamitakahara, Toshiyuki Thkano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto
606-8502, Japan
Abstract:
Horseradish peroxidase (HRP)-catalyzed polymerization of syringyl-type monolignol glycoside(iso-S) was carried out in homogeneous aqueous media of different acidity and was monitored by UV
spectroscopic and GPC techniques, in order to determine the effect of pH on the formation of syringyl
dehydrogenation polymers (S-DHPs). It was found that at lower pH, the S-type quinone methide intermediates
475

(S-QM) were quenched more rapidly to result in more efficient formation of S-DHP. The results for thepolymerization of S-alc also support this view. Structural analyses on the S-DHPs demonstrated that the reactionof S-QM with water was promoted at low pH, indicating its higher reactivity than that in neutral media.
2008-211
TOF-SIMS によるリグニン S／G 比顕微分析法の開発
斉藤香織*1、渡連陽子*2、岸本崇生*3、家田真理子*1、勝山さやか*1、松下泰幸*1、今井貴規*1、船田良*4、*5*5*1
小池孝良 、深澤和三 、福島和彦*1
名古屋大学大学院生命農学研究科、*2 北海道大学北方生物圏フイールド科学センター、*3 富山大学工学部、*4 東京農工大学大学院農学研究院、*5 北海道大学大学院農学研究科
The syringyl/guaiacyl (S/G) ratio of lignin estimated by TOF-SIMS
Kaori Saito*1, Yoko Watanabe*2, Takao Kishimoto*3, Mariko Ieda*1, Sayaka Katsuyama*1, Yasuyuki Matsushita*1,
Takanori Imai*1, Ryo Funada*4, Takayoshi Koike*5, Kazumi Fukazawa*5, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, *2Field Science Center for
Northern Biosphere, Hokkaido University, Sapporo 060-0809, *3Faculty of Engineering, Toyama Prefectural
University, Imizu 939-0398, *4Institute of Symbiotic Science and Technology, Tokyo University of Agriculture
and Technology, Fuchu,183-8509, *5Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589
Abstract:
The syringyl/guaiacyl (S/G) ratios were estimated by time-of-fright secondary ion mass
spectrometry (TOF-SIMS) using lignin model compounds and the transverse section of the xylem of Acer
micranthum. The result showed that the value of S/G ratios detected by TOF-SIMS and the molar S/G ratios
were similar in the spectra of 8-O-4’ polymers. In other hands, the S/G ratios calculated in the spectra ofmonomer and dimer model compounds were much higher than the molar S/G ratios. This result suggests that theestimation of S/G ratio by TOF-SIMS is reliable in lignin polymers. Further experiments were needed toestimate the reliability of S/G ratio calculated in TOF-SIMS spectra.
2008-212
リグニン中の枝分かれ構造の探索 - 非フェノール性ダイベンゾダイオキソシン構造の 1H−および 13CNMR 化
学シフトの特徴 秋山拓也*1、John Ralph*1*2*1
US DFRC, *2Univ. Wisconsin
Characteristics in 1H- and 13C-NMR chemical shifts of non-phenolic dibenzodioxocin model compounds as
branch-points in lignin
Takuya Akiyama*1, John Ralph*1*2*1
US Dairy Forage Research Center, USDA-ARS, Dairy Forage Research Center, 1925 Linden Drive West,
Madison, WI 53706, USA, *2University of Wisconsin-Madison, Department of Biochemistry, Enzyme Institute,1710 University Ave., Madison, WI 53726, USA
Abstract:
Non-phenolic dibenzodioxocin compounds modelling the 4-O-β-ethers that would be generated
following radical coupling with a monolignol were synthesized to explore branch-points in lignin. NMR
measurements on acetylated models revealed that the aromatic carbons (C1) attached to the side chain of adibenzodioxocin had significantly different chemical shifts between phenolic and non-phenolic models ( δ∼3.6ppm) while the other side chain proton and carbon shifts (α- and β-positions) were similar. It is suggested thatphenolic and non-phenolic dibenzodioxocin models can be distinguished from each other by NMR, particularly
via long-range correlation (HMBC) NMR experiments.
2008-213
オイルパーム材のバイオエタノール製造原料としての特性
村井宏輔*1、内田隆一郎*1、大久保篤史*1、近藤隆一郎*2*1
九州大学大学院生物資源環境科学府、*2 九州大学大学院農学研究院
The characterization of oil palm trunk as a material of bio-ethanol production
Kousuke Murai*1, Ryuichiro Uchida*1, Atsusi Okubo*1, Ryuichiro Kondo*2
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University,
6-10-1 Hakozaki, Higashi-ku, Fukuoka, 812-8581 Japan
Abstract:
Using some samples cut out vertically and radially from 25 years old Elaeis guineensis (oilpalm) trunks, chemical composition was determined. As a result, as higher and innerer the oil palm trunk, themore hot water extractable glucose were observed. The hot water extractable glucose, fructose and sucrose
476contents of oil palm trunk were roughly estimated as 63, 13 and 11 kg, respectively. Estimated ethanol
production per cultivated area was 7.4 kL/ha. The ethanol yields of fermentation of sugar liquors from oil palm
wood meals by Zymomonas mobilis were almost same as that from glucose solution, so it would appear that
there was no fermentation inhibitor in oil palm wood meal.
2008-214
高圧下におけるツヤ酸の水蒸気蒸留とその化学転換
浅井淳子、道家真一、中村宣夫、橋本敬、西谷耕三、棚橋光彦
岐阜大学大学院応用生物科学研究科
Result of the steam distillation and the chemical changes of thujic acid under high-pressure
Junko Asai, Shinichi Doke, Nobuo Nakamura, Takashi Hashimoto, Kouzou Yoshitani, Mitsuhiko Tanahashi
Graduate School of Applied Biological Sciences, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan
Abstract:
Thujic acid, knows as antibacterial substance, is a component of the essential oil
extracted
from Western Red Ceder (Thuja plicata). Since the structure of thujic acid is unstable, it is expected to undergochemical transformation easily. Therefore, the chemical transformations of thujic acid under high-pressure
steam condition and under UV radiation were observed. By high- pressure steam treatment, thujic acid wastransformed into cumin acid and m-cumin acid under acidic condition, while novel compound was produced
under basic condition. Furthermore, thujic acid transformed into novel compounds by UV radiation.
2008-215
樹皮の酵素糖化における新規前処理技術の開発
松下泰幸*1、山内一慶*1、小林哲夫*1、加藤雅士*1、古城敦*2、浅田隆之*2、福島和彦*1*1
名古屋大学大学院生命農学研究科、*2 王子製紙株式会社
Development of novel pretreatment for enzymatic saccharification of bark
Yasuyuki Matsushita*1, Kazuchika Yamauchi*1, Tetsuo Kobayashi*1, Masashi Kato*1, Atsushi Furuzyo*2,
Takayuki Asada*2, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan*2
Oji Paper Co., Ltd., 1-10-6 Shinonome, Koto-ku, Tokyo, 135-8558, Japan
Abstract:
In this study, saccharification of bark by enzyme hydrolysis was investigated. To enhance the
enzyme accessibility to the polysaccharides in the cell wall, such as cellulose and holocellulose, hydrothermal
pretreatment with carbon dioxide was conducted. The results of the enzyme hydrolysis showed that themonosaccharide yield using pretreated bark reached 36%, whereas that using non-pretreatment sample wasabout 10%. More than 95% of the generated monosaccharide was glucose. This results suggested that thesecondary wall which main component is cellulose hydrolyzed effectively by enzyme. The yield of glucose on
the basis of a-cellulose reaches about 80%.
2008-216
ユーカリ樹皮のリグニン分布と酵素糖化性
高部圭司 *1、吉永 新*1、粟野達也 *1、福島和彦*2、松下泰幸 *2、山内一慶*2、小林哲夫 *2、加藤雅士*2、古城敦*3、浅田隆之*3*1
京都大学大学院農学研究科、*2 名古屋大学大学院生命農学研究科、*3 王子製紙株式会社
Lignin distribution influences enzyme succharification of bark in Eucalyptus
Keiji Takabe*1, Arata Yoshinaga*1, Tatsuya Awano*1, Kazuhiko Fuknshima*2, Yasuyuki
Matsushita*2, Kazuchika Yamauchi*2*3, Tetsuo Kobayashi*2, Masashi Kato*2, Atsushi Furujo*4, Takayuki Asada*5*1Graduate School of Agriculture, Kyoto University, Kyoto 606-8502, *2Graduate School of Bioagricultural
Sciences, Nagoya University, Nagoya 464-8501. *3Graduate School of Energy Science, Kyoto University, Kyoto
606-8501. *4Oji Paper Co., Ltd., Research & Development Division, Tokyo 135-8558. *5Oji Paper Co., Ltd.,
Albany Forestry Research Centre, Albany, WA6331, Australia
Abstract:
Inner bark of Eucalyptus is composed of sieve tube member, companion cell, phloem
parenchyma cell, phloem ray parenchyma cell and phloem fiber. Phloem fiber has a thick secondary wall inwhich syringyl lignin is accumulated. After the inner bark is exposed to the acidified hot water with CO 2 at 200
degree Celsius, Primary wall of parenchyma cell shows highly swollen structure andsecondary wall of phloem fiber has many clefts with a several nanometer width. These cell walls arecompletely degraded by the treatment with enzymes contained cellulase, xylanase, pectinase andamylase.
477

2008-217
Gmelina arborea と Swietenia macrophylla の樹皮から新規フェニルプロパノイド関連成分の単離同定とそれらの抗酸化活性Syamsul Falah、鈴木利貞、片山健至
香川大学農学部
Chemical constituents from Gmelina arborea and Swietenia macrophylla bark and their antioxidant activity
Syamsul Falah, Toshisada Suzuki, Takeshi Katayama
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan
Abstract:
A new phenylethanoid glycoside,(-)-p-hydroxyphenylethyl[5’’’-O-(3,4-dimethoxy- cinnamoyl)β-D-apiofuranosyl(1’’’→6')]- β-D-glucopyranoside, was isolated from Gmelina arborea bark together withtyrosol, (+)-balanophonin, gmelinol, 2,6-dimethoxy-p-benzoquinone, and 3,4,5- trimethoxyphenol. The
3,4,5-trimethoxyphenol exhibited a moderate antioxidant activity. From Swietenia macropkylla bark, a new
phenylpropanoid-substituted
catechin,namely,swietemacrophyllanin[(2R*,3S*,7"R*)-catechin-8,7"-7,2"-epoxy-(methyl 4",5"-dihydroxyphenyl- propanoate)] was isolated together
with catechin and epicatechin. The swietemacrophyllanin had strong antioxidant activity.
2008-P0１
担子菌のラッカーゼ遺伝子を導入した組換え植物における雄性不稔の解析
Zannatul Nasrin*1，吉川海郷*1、園木和典*2、飯村洋介*3、佐藤かんな*1、片山義博*1、梶田真也*1*1
東京農工大学大学院 BASE、*2 弘前大学農業生物科学部、*3 産業技術総合研究所
Analysis of male sterility in transgenic plants with the chimeric gene for fungal laccase
Zannatul Nasrin*1, Misato Yoshikawa*1, Tomonori Sonoki*2, Yosuke Iimura*3, Kanna Sato*1, Yoshihiro
Katayama*1, Shinya Kajita*1*1
BASE, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan, *2Faculty ofAgriculture and Life Science, Hirosaki University. Hirosaki, Aomori 036-8561, Japan, *3National Institute ofAdvanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8569, Japan
Abstract:
Transgenic tobacco plants with the chimeric gene for fungal laccase exhibited mate sterility
without any influence of pollen viability. Frequencies of the male sterility in the plants depended on the laccase
activities in their anther tissues. Since lignification in endothecium of the anther tissue is essential for normal
dehiscence of the organ to distribute pollen grains, we analyzed lignin characteristics in the tissue. Results from
histochemical and wet chemical analyses indicate that lignin contents in the transgenic tissues are unchanged.
By contrast, abnormal deposition of flavonoid in epidermis layer of the transgenic anther was revealed byvanillin staining of the anthers. These results suggest that laccase expression does not affect the lignin
biosynthesis but does flavonoid deposition in the transgenic anthers.
2008-P02
カバノアナタケ菌 IO・U1 株に感染した 2 種類のシラカンバ幼植物体クローンにおけるフェノール性化合物の沈着とペルオキシダーゼ活性
高島有哉*1、Md. Mababubur Rahman*1*2、鈴木美帆*3、石栗太*3、飯塚和也*3、吉澤伸夫*3、
横田信三
*3
*1

東京農工大学大学院農学研究院、*2 京都大学生存圏研究所、*3 宇都宮大学農学部、Phenolics deposition and peroxidase activity in two types of Japanese birch plantlet clones infected with
Inonotus obliquus IO-U1 strain
Yuya Takashima*1, Md. Mahabubur Rahman*1*2, Miho Suzuki*3, Futoshi Ishiguri*3, Kazuya Iizuka*3, Nobuo
Yoshizawa*3, Shinzo Yokota*3*1
United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology, Fuchu,
183-8509, Japan, *2Current affiliation: Research Institute for Sustainable Humanosphere, Kyoto University, Uji,
Kyoto 611-0011, Japan, *3Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
Two types of Japanese birch clone (Tohoku and No.8) plantlets were used in order to investigate
the time-course changes of phenolics deposition and peroxidase activity in Japanese birch (Betula platyphyllavar. japonica) plantlets infected with Inonotus obliquus which causes a canker-rot disease of birch tree. In intact
and wounded plantlets after 12 hrs of treatments, phenolics deposition was not detected in the both clones. On
the other hand, in infected both clones, phenolics deposition was observed in the vessels, wood fibers, andparenchyma cells. In the case of Tohoku clone, peroxidase activity was detected near the infection site after 2478

hrs of inoculation, in the vessel cells after 4 hrs, and in the sclerenchyma cells after 30 days.
2008-P03
高活性リグニン分解菌 Phanerochaete sordida YK−624 株における新規リグニンペルオキシダーゼ高発現株の特性
杉浦立樹*1、山岸賢治*2、平井浩文*3*1
静岡大学創造科学技術大学院、*2 東北農業研究センター、*3 静岡大学農学部
Properties of novel lignin peroxidase-high expression transformants from Phanerochaete sordida YK-624
Tatsuki Sugiura*1, Kenji Yamagishi*2, Hirofumi Hirai*3*1
Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan,*2
National Agricultural Research Center for the Tohoku Region, National Agriculture and Food Research
Organization, Fukushima 960-2156, Japan, *3Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529,
Japan
Abstract:
In our previous reports, we have cloned YK-LiP1 and YK-LiP2 encoding genes (ylpB and ylpA,
respectively) from Phanenchaete sondida YK-624, and constructed homologous expression transformants
introducing these genomic DNAs which were regulated by GPD promoter. In the present study, we investigatedligninolytic properties of these transformants, A-11 (ylpA transformant) and B-3 (ylpB transformant). Thesetransformants A-11 and B-3 showed higher ligninolytic activity than wild type P. sordida YK-624. Moreover,high glucose conversion was observed in the enzymatic saccharification of wood meal which was inoculatedwith A-11 or B-3, compared with wild type P. sordida YK-624. These results suggest that high expression of
YK-Lip genes improve ligninolytic activity and selectivity of P. sordida YK-624.
2008-P04
白色腐朽菌の菌体外ペルオキシダーゼ反応の局在化について
高野麻理子、中村雅哉、山口宗義
森林総合研究所
Localized extracellular peroxidase reaction of a white-rot fungus Phanerochaete crassa WD1694
Mariko Takano, Masaya Nakamura, Muneyoshi Yamaguchi
Forestry and Forest Products Research Institute, Matsunosato 1, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
Distribution of extracellular peroxidase reaction of a white-rot fungus Phanerochaete crassa
WD1694 was visualized by peroxidase activity staining. The results showed that the extracellular peroxidase
reaction of P. crassa WD1694 occurred only on the fungal bodies and not in the culture fluids. Further studies
about the extracellular peroxidase reaction on the fungal bodies of P. crassa WD1694 revealed the occurrence ofintense peroxidase reaction at the hyphal tips that lacked fungal slime. Manganese peroxidase and glyoxal
oxidase were determined as major enzymes that worked in the peroxidase reaction at the hyphal tips. The
significance of the extracellular peroxidase reaction at the hyphal tips on the ligninolytic mechanism ofwhite-rot fungi was discussed.
2008-P05
The pretreatment of corn stover by wood-rotting fungi for the production of bio-ethanol
Ziqing Gao, Ryuichiro Rondo
Faculty of Agriculture, Kyushu University, Fukuoka, 812-8581, Japan
Abstract:
40 strains of wood-rotting fungi (33 strains of white-rot fungi and 7 strains of brown-rot fungi)
were screened for the pretreatment of bio-ethanol production made of corn stover. Cellulase was used forcellulose saccharification from corn stover pretreated by wood-rotting fungi to test the efficiency of
pretreatment. As a result, B-2 a strain of brown-rot fungus was selected for corn stover pretreatment. We
determine the composition in corn stover pretreated by B-2 fungus. Although the lignin content increased to28.3% (control: 25.7%), the glucose yield in cellulose saccharification in corn stover pretreated by B-2 wasincreased by 150%.
2008-P06
糖質結合モジュール（CBM−CFP）融合タンパクを用いた木材酵素糖化前処理物の解析
川久保武*1、親泊政二三*1、渡連崇人*1、本田与一*1、渡辺隆司*1、苅田修一*2*1
京都大学生存圏研究所、*2 三重大学大学院生物資源学研究科
Surface analysis of wood biomass pretreated for enzymatic saccharification by carbohydrate binding module
479

(CBM)-cyan fluorescent protein (CFP) complexes
Takeshi Kawakubo*1, IMasafumi Oyadomari*1, Takahito Watanabe*1, Yoichi Honda*1, Syuichi Karita*2, Takashi
Watanabe*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan,*2
Graduate School of Bioresource, Mie University, 1577 Kurima-Machiyacho, Tsu, 514-8507, Japan
Abstract:
Carbohydrate binding modules (CBMs) are noncatalytic substrate binding domains ofcellulolytic enzymes. Here we used fluorescent labeled recombinant CBMs specific for crystalline cellulose(CBM3) and non-crystalline cellulose (CBM28) to analyze the complex surfaces of wood tissues pretreated bychemical, thermal and physical methods. Linear correlation between enzymatic saccharification yield and theadsorption of the two CBM-CFP complexes was obtained for the chemically delignified wood. Adsorption of
the two CBM-CFP complexes to the physically disrupted wood was much lower than that of the chemicallydelignified wood. Fluorescent microscopy revealed that CBM-CFP complexes adsorbed preferentially on
fibrillated wood tissues but direct adsorption of CBM-CFP complexes on the surface of delignified wood fibers
were observed. Thus thequantitative fluorometric method clarified the linear dependency of saccharification yield on exposure ofcellulose surfaces in delignified wood.
2008-P07
難揮発性化合物の高圧水蒸気蒸留
中村宣夫、浅井淳子、橋本敬、金原弥生、西谷耕三、棚橋光彦
岐阜大学大学院連合農学研究科
High-pressure steam distillation of nonvolatile compounds
Nobuo Nakamura, Junko Asai, Takashi Hashimoto, Yayoi Kimpara, Kouzou Yoshitani, Mitsuhiko Tanahashi
Graduate School of Agriculture, Gifu University, 1-1 Yanagido, 501-1193 Gifu, Japan
Abstract:
It has been reported that High-pressure steam distillation method allowed distillation of highboiling compounds and nonvolatile compounds which are considered difficult to be distilled. With using thismethod, thujic acid and hinokitiol were successfully distilled from Thuja plicata at the condition of 1.6MPa,
200ºC. The aim of this study is to estimate the availability of high-pressure steam distillation method byobserving the distillation behavior of model compounds for further application of this method. In this study,
curcumin, known as nonvolatile compound, was chosen as model compound. Curcumin was distilled nearly
1000% within 20mins at the condition of 1.6MPa, 200ºC.
2008-P08
オルガノソルブリグニンアルキルエステル／ポリ（e 一カプロラクトン）ブレンドの均一混合スケールの評価
寺本好邦*1、李承桓*2，遠藤貴土*2，西尾嘉之*1*1
京都大学大学院農学研究科、*2 産業技術総合研究所
Evaluation of size of heterogeneity in blends of poly(e-caprolactone) with organosolv lignin alkyl esters
Yoshikuni Teramoto*1, Seung-Hwan Lee*2, Takashi Endo*2, Yoshiyuki Nishio*1*1
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku,
Kyoto 606-8502, Japan*2
Nalional Institute of Advanced Industrial Science and Technology (AIST), Biomass Technology ResearchCenter (BTRC), 2-2-2, Hirosuehiro, Kure, Hiroshima 737-0197, Japan
Abstract:
Organosolv lignin (OSL) alkyl esters (carbon number n, 2-5) were synthesized by ahomogeneous reaction with different acyl anhydrides/4-dimethylamino pyridine in pyridine solution. The
miscibility of the esterified OSLs with poly(e-caprolactone) (PCL) has been investigated previously, mainly
through the evaluation of the glass transition temperature (Tg) using differential scanning calorimetry (DSC).
DSC analysis has revealed that the blends of OSL esters with n = 3-5 with PCL showed acomposition-dependent shift in Tg. Therefore, the blend systems can be regarded as miscible ones in a scale ofTg-detection, usually assumed to be less than a couple of tens of manometers. To ascertain the state of
miscibility of the blends precisely, they were investigated by using dynamic mechanical analysis (DMA) andsolid-state 13C CP/MAS NMR. A detailed estimation of the Tg by DMA revealed that the blends with n = 3-5
shows a single Tg, which varies with composition. Taking into account the T1pH estimated by solid-state NMR, it
was suggested that the miscible combinations mix on a scale between ca. 5 and 15 nm.
2008-P09
リグニンの表面特性に関する研究480糟谷絵理、福島和彦、今井貴規、松下泰幸
名古屋大学大学院生命農学研究科
Study on surface properties of lignins
Eri Kasuya, Kazuhiko Fukushima, Takanori Imai, Yasuyuki Matsushita
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract:
Lignin chemical structures are known to differ between species, tissues, and regions. The
structural heterogeneity of lignin seems to affect its characteristics, and the investigation of such relationship is
significant for better utilization of lignin. In present study, the surface properties of lignins were evaluated byinverse gas chromatography (IGC). To compare interspecific difference,
we used a-cellulose coated with milled wood lignin (MWL) prepared from Pinus densiflora (Red pine) andFagus crenata (Beech) as sample. By these methods, we determined Lifshitz-van der Waals component of thesurface free energy (γsLW) of each lignin samples.
2008-P10
イオン液体 1−n-ブチル-3-メチルイミダゾリウムクロライドを用いて処理されたトドマツ（Abies sachalinensis）木粉の化学的特徴 〜リグニンと糖の関係に関する考察〜
岸野正典*1、岸本崇生*2、久保智史*3、山田竜彦*3、折橋健*1、槍山亮*1*1
北海道林産試験場、*2 富山県立大学、*3 森林総合研究所
Chemical characteristics of Abies sachalinensis sawdust treated with an ionic liquid,
1-n-butyl-3-methyl-imidazolium chloride. Discussion on relationship between lignin and carbohydrate
Masanori Kishino*1, Takao Kishimoto*2, satoshi Kubo*3, Tatsuhiko Yamada*3, Ken Orihashi*1, Ryo Hiyama*1*1
Hokkaido Forest Products Research Institute, Asahikawa, Hokkaido, Japan, *2Faculty of Engineering, Toyama
Prefectural University, Imizu, Toyama, Japan, *3Forestry and Forest Products Research Institute, Tsukuba,
Ibaraki, Japan
Abstract:
We investigated chemical characteristics of the insoluble fraction obtained by treatment ofAbies sachalinensis sawdust with 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) as one of the ionicliquids (ILs) at 100 and 120ºC for periods ranging from 2 to 24h. Galactose contents in the insoluble fraction
increase with as lignin contents increase, whereas other monosaccharide contents except for xylose tend to
decrease. These results suggest the existence of lignin bonded closely to galactose in hemicellulose as astructure of lignin-carbohydrate complex (LCC) in Abies sachalinensis sawdust.
2008-P11
アカシアファイバーのイオン液体 1-n-ブチル-3-メチルイミダゾリウムクロライドへの溶解挙動
谷口僚*1、中川明子*1、大井洋*1、岸野正典*2*1
筑波大学大学院生命環境科学研究科、*2 北海道立林産試験場
Dissolution behavior of acacia fiber in 1-n-butyl-3-methylimidazolium chloride as an ionic liquid
Ryo Taniguchi*1, Akiko Nakagawa-izumi*1, Masanori Kishino*2, Hiroshi Ohi*1*1
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8572
Japan, *2Hokkaido Forest Products Research Institute, Hokkaido, 071-0198 Japan
Abstract:
To make the selectively dissolving condition of cellulose in wood components during thedissolution in 1-n-buyl-3-methylimidazolium chloride ([bmim]Cl) clear, Acacia mangium fiber, milled fiber andwood meal were heated in [bmim]Cl. After the treatment for 24 hours at 100ºC, the yield of residue from milled
fiber, fiber and wood meal were 71, 84 and 88%, respectively. The residue from milled fiber treated with[bmim]Cl decreased with increasing temperature and time. In addition, glucose, which is hydrolyzed by the
carbohydrate analysis from, wood materials treated with [bmim]Cl decreased rapidly, although their acidinsoluble parts increased. The result indicates that the dissolution rate of carbohydrates such as cellulose inwood components is faster than that of lignin.
2008-P12
リグニン分析法のエーテル結合開裂能の評価 一 β-O-4 型人工リグニンポリマーの分解性−
金澤香枝*1、幸田圭一*1、浦木康光*1、岸本崇生*2*1
北海道大学大学院農学研究科、*2 富山県立大学
Quantifiability of ether bond cleavage of lignin analysis method -Degradability of β−O-4 type artificial lignin
polymerYoshie Kanazawa*1, Keiichi Koda*2, Yasumitus Urak*2i,Takao Kishimoto*3
481

*1

Graduate School of Agriculture,Hokkaido University,Sapporo 060-85 89, Japan, *2Research Faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan, *3Faculty of Engineering,Toyama Prefectural
University, Toyama 939-0398, Japan
Abstract:
Thioacidolysis and nitrobenzene oxidation are methods for analyzing lignin structure bycleavage of aryl ether linkages in lignin. However, the reaction efficiencies of the cleavage to polymericmaterials are not clear yet. In this study, we evaluated thioacidolysis and nitrobenzene oxidation reactivity tocleavage of aryl ether linkages, β-O-4 linkage in particular, by using the artificial lignin polymer, which wascomprised of only β-O-4 linkage. The yields of monomeric product by thioacidolysis and nitrobenzene
oxidation under the conventional conditions were about 70% and 50%, respectively. These results reveal thatthese methods incomplete decompose β-O-4 macromolecule.
2008-P13
β-O-4 結合の新規な選択的開裂法 一 β-phenoxy sulfone elimination method（β-PSE 法）一
安藤大将、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
New selective stepwise cleavage method for the β-O-4 linkages —β-phenoxy sulfone elimination method—
Daisuke Ando, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto,606-8502, Japan
Abstract:
We develop the new selective stepwise cleavage method for the β-O-4 linkages with aquantitative yield carried out under the mild reaction conditions without any side reactions. This degradation
method involves basically three reaction steps: 1) Nucloephilic substitution of the γ-primary or α-secondaryhydroxyl group in the β-O-4 structure with inodorous alkylthiol such as C12H25SH, 2) Oxidation of the thioether
to sulfone, and finally 3) β-Elimination of β-phenoxy sulfone under the mild alkaline conditions, i.e.,
0.1N-NaOH to produce α, β-unsaturated sulfone with spontaneous β-O-4 bond cleavage. This method may be
useful especially for die elucidation of LCC-structures.
2008-P14
t-BuOK/t-BuOH 系におけるリグニン β-O-4 結合の挙動
竹野甲子夫、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Behavior of lignin β-O-4 bond in t-BuOK/t-BuOH system
Kineo Takeno, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Graduate School of Agricultural and Life Sciences, the University of Tokyo,
1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
We have focused on t-BuOK as a base and investigated the efficiency of the t-BuOK/ t-BuOH
system to cleave β-O-4 bond in lignin under mild conditions (0.5 mol/l t-BuOK/t-BuOH, 30ºC) using lignin
model compounds, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxy- phenyl)propane-1,3- diol (VG) and2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol (V'G). The results showed that the β-O-4 bonds of VG
and V'G are certainly cleaved and 2-methoxyphenol is quantitatively detected from both compounds. This is
surprising because much severer conditions (ca. 2 mol/l NaOH, >150ºC) are commonly required to cleave thesebonds in aqueous media. The degradation of both compounds was approximated to pseudo-first-order rateequations, and the rate constants of VG and V’G were 0.0022 and 0.0015 min-1, respectively, which shows thefaster degradation of VG than V'G and suggests the contribution of the g-position of VG to this cleavage
reaction. However, wood meal was not delignified well and relatively large amounts of carbohydrates were
removed when it was treated in the t-BuOK/t-BuOH system at the elevated temperature. This result suggeststhat delignification is not controlled only by potential ability to cleave chemical bonds between lignin subunits
but by various topochemical factors.
2008-P15
非木質組織のリグニン定量
戸田守一、中村裕貴、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科木材化学研究室
Determination of lignin content in non-wood tissues and plants
Morikazu Toda, Yuki Nakamura, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Graduate School of Agricultural and Life Sciences, the University of Tokyo,482

1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
It has been presumed that Klason method overestimates the lignin content of non-wood tissues
or plants, but a method to determine the “true'' lignin content of these samples has not been established yet. Our
previous studies showed that wood and non-wood are reasonably distinguished by the yields of specific lignin
degradation products obtained by nitrobenzene oxidation and ozonation analysis but not by their Klason lignin
contents. The yields of these degradation products from non-woods were always lower than a certain level
although their Klason lignin content is sometimes extremely high. On the other hand, woods always gave higher
values than this certain level. These results suggested that Klason residue obtained from non-woods containlarge amount of non-lignin substances. However, one possibility was still remaining; that is the lignin structureof non-wood plants or tissues is rich in condensed type so that these specific degradation products can be given
only in small yields. If we can “count” the number of aromatics contained in the Klason residue, we can verify
this possibility. For this purpose, we developed a method based on IR
absorption and applied to Klason residues of both wood and non-wood samples. It was successfully shown thatthe number of aromatics in the Klason residue from non-wood was very low compared with that of woods, andit was corresponding well to the low yield of lignin degradation products from non-wood samples. Further
research is conducted to elucidate what are included as non-lignin substances in the Klason residue of non-woodsamples.
2008-P16
カシノナガキクイムシによる病傷害を受けたコナラ辺材のリグニン構造
山ぎし崇之、横山朝哉、山田利博、松本雄二
東京大学大学院農学生命科学研究科
Structure of lignin in the sapwood of Qurecus serrata Thunb. infected by Platypus Quercivora
Takayuki Yamagishi, Tomoya Yokoyama, Toshihiro Yamada, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of
Agricultural and Life Sciences, the University of Tokyo, Tokyo, Japan
Abstract:
When the sapwood of Quercus serrata is wounded by an insect of Platypus Quercivora, thearea surrounding the wounded part is infected by a symbiotic fungi of this insect, Raffaerea quercivora, which
results in a discoloration of this area. As a defense response of the tree, polymeric substances are secreted at theboundary of this discolored area and normal area. Because these substances are positive to phloroglucinol-HCl
colorization reaction, these are often called "lignin-like compounds". In order to analyze the any change caused
in lignin structure of discolored area, we prepared samples along several lines that extended to different
directions from the center of discolored area, and the change of structure and amount of lignin along these lines
were examined. If we can find a clear tendency from the center to outer part beyond the difference of direction,
it is reasonably assumed that the change corresponds to the discoloration. According to this strategy, about 20
samples were prepared from different parts in one discolored area, and, Klason lignin determination,
nitrobenzene oxidation and ozonation analysis were performed. Even though the difference was not large, aclear tendency was found in the change of Klason lignin content, SN ratio or the total yield of aromatic
aldehydes obtained by nitrobenzene oxidation along the lines beyond the difference of direction. We are now
looking into in more detail how these difference were created based on the hypothesis that these were initiatedby fungal infection.
2008-P17
アカマツ木粉の熱分解生成物の分析〜回収留分の定量的検討と熱分解残漆の分析〜
錦織香、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Quantitative analysis of pyrolysis products derived from red pine wood meal "iquid products and pyrolysis
residue"
Kaoru Nishikior, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of
Agricultural & Life Sciences, the University of Tokyo, 1-1-1, Yayoi, Bunkyo-ku, Tokyo, 113-8657 Japan
Abstract:
Red Pine wood meals were pyrolysed by tube type kiln under various conditions andquantitative analysis by GC was performed on the main 18 compounds in the fraction recovered as a liquid
pyrolyzate. These determined compounds accounted for only about 10% of all liquid pyrolysate.
Determination of water in this fraction by 1H-NMR suggested that 60% of the fraction was water.
483

2008-P18
泥炭を通過した水中に存在するリグニンの研究勝亦京子*1、松本雄二*1、金貞福*2、飯山賢治*3*1
東京大学大学院農学生命科学研究科、*2 浙江林業大学、*3 国際農林水産業研究センター3
Lignin in dissolved organic matter obtained from peat swamp water
Kyoko S. Katsumata*1, Yuji Matsumoto*1, Zhenfu Jin*2, Kenji Iiyama*3*1
Graduate School of Agricultural and Life Sciences. the University of Tokyo, 1-1-1 Yayoi. Bunkyo-ku,
113-8657 Tokyo, Japan, *2Zhejiang Forestry University, China, *3Japan International Research Center for
Agricultural Sciences
Abstract:
It is well known that lignin is highly resistant against biological attack. Some part of
biologically modified lignin in peat would be expected to dissolve in water. In this study, dissolved organic
matters (DOM) isolated from water soaked out of Ishikari (Japan) and To Daeng (Thailand) peat swamps were
investigated. Well-defined lignin structural features, e.g., products of alkaline
nitrobenzene oxidation, methoxyl group, and resonance signals for β-O-4 linkage around 6 ppm in
1
H-NMR spectrum, were hardly detected in DOM. Successive treatment consisting of diazomethane
methylation and saponincation suggested that DOM has 0.09-0.14 mol/C mol of acidic hydroxyl groups, among
which 0.05-0.08 mol/C mol were unstable to alkali when methylated. Average molecular weight of DOM was at
MW 1,600. It was considered that lower part of molecular weight of peat in which much of hydrophillicfunctional group was introduced by biological modification, was dissolved into water. In 1H-NMR spectrum of
DOM obtained from Ishikari showed weak but clear peak attributable to aromatic proton.
2008-P19
Spectral study on reaction mechanism of etherification of rice straw
Yu Huang, Linshan Wang, Ying Xing
Department of Chemistry, Northeastern University, China
Abstract:
Etherification of rice straw with epoxy chloropropane was carried out at 120ºC for 1-8h intoluene with NaOH as a base. The extent of etherification was estimated by the use of weight percent gain
(WPG) as an indication. FT-IR spectroscopy were used to investigate the changes in composition and structureof rice straw that had been subjected to pretreatment and epoxy chloropropane modification. WPG of epoxy
chloropropane modified rice straw increased with reaction time. The increase was first significant with theprogress of reaction time, and the increment became slight after 5h. FT-IR analyses of epoxy chloropropane
modified rice straws agreed with the well established reaction mechanism of epoxy chloropropane. Namely, two-OH groups of rice straw were replaced by two ether links in the former three steps, and one -OH group
generated in propane chain derived from epoxy chloropropane in the fourth step.

484

第 54 回 （2009.10.29-30） 静岡県男女共同参画センター
2009-101
改変型植物酸性 Peroxidase の酵母での発現と精製(3)吉中喬慈、川合伸也
東京農工大学大学院農学府
Heterogeneous expression and purification of modified plant peroxidase (3)Kyoji Yoshinaka, Shinya Kawai
Tokyo University of Agriculture and Technology
Abstract:
Lignin peroxidase of Phanerochaete chrysosporium can oxidize the many environmental
pollutants and lignin by assuming Trp-171 near the surface of the enzyme of the catalytic site. CWPO-C that is
one of popular POXs can oxidize sinapyl alcohol polymers, and is presumed that Tyr-177 and Tyr-74 exposed tothe surface of the enzyme are the catalytic sites. Moreover, the surrounding amino-acid residues of the catalytic
sites influenced the specificity of substrates. We introduced the mutations into prxA3a, a POX gene of Populus
kitakamiensis, to change the corresponding amino acid residues at the positions to Trp residue of Lignin
Peroxidase and Tyr residues of CWPO-C and to change the surrounding amino acid residues of the catalytic
sites, and examined the changes in the substrate specificities.
2009-102
タバコ・ポプラにおける細胞分裂マーカーcycB pro.:GUS を利用した維管束形成層の細胞分裂
評価
藤井武郎*1、古市孝行*1、松井紀子*1、佐藤かんな*1、梶田真也*1、片山義博*1、西窪伸之*2*1
東京農工大学大学院生物システム応用科学府、*２理化学研究所植物科学センター
Analyze of cell division on vascular cambium with the marker cycBpro.:GUS in tobacco and poplar
Takeo Fujii*1, Takayuki Furuichi*1, Noriko Matsui*1, Kanna Sato*1, Yoshihiro Katayama*1, Nobuyuki Nishikubo*
２*1

Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, 2-24-16 naka-cho, Koganei-city, Tokyo, 184-8588, Japan, *2RIKEN Plant Science Center, 1-7-22
Suehiro-cho, Tsurumi-ku, Yokohama City, Kanagawa, 230-0045, Japan
Abstract:
The researches about components of cell wall have been investigated with model plants, forexample Arabidopsis thaliana or Oryza sativa. To keep plant biomass sustainably in 21st century, we indicatethat the research should be approached with woody plant. Woody plant has vascular cambium, and show
thickening growth and a lot of biomass accumulation. We indicated the regulation of cell division on vascularcambium effects beneficial change about plant biomass production. Therefore, we approached analysis aboutcell number, cell differentiation, and cell wall formation in vascular cambium. In this work, we have madetransgenic tobacco and poplar. First, it is overexpressed cell cycle G1/S phase regulated factor, cycD2, E2F, DP,
and E2F/DP, and the cambium was enlarged In Only cycD2 transgenic plant. Second, we approached with cell
division marker cycB1：３pro.:GUS to check cell cycle regulation. As a result, the activity was not secondary
meristem we targeted, but primary meristem.
2009-103
イネをモデルとした植物細胞壁形成過程に関する研究 （４） -Glycosyl-phosphatidylinsitol- anchored protein
はイネの細胞壁高次構造形成にどのように関わるのか ? –伊藤幸子*1、片山義博*1、佐藤かんな*1、鈴木 瑠*1、半 智史*2、船田 良*2、梶田真也*1、北野英己*3*1
東京農工大学大学院生物システム応用科学府、*２東京農工大学大学院農学府、*３名古屋大学生物機能
開発利用研究センター
Study of plant cell wall formation in Oryza sativa L. (4) –How does glycosylphosphatidyl- inositol-anchoredprotein relate to cell wall conformation in rice plant (Oryza sativa L.)? –Sachiko Ito*1, Yoshihiro Katayama*1, Kanna Sato*1, Ryu Suzuki*1,Satoshi Nakaba*2, Ryo Funada*2, Shinya
Kajita*1, Hidemi Kitano*3*1Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan, *2Graduate school of Agriculture, Tokyo University ofAgriculture and Technology, Fuchu, Tokyo, 183-8509, Japan, *3Bioscience and Biotechnology Center, Nagoya
University, Chikusa-ku, Nagoya 464-8601, Japan
Abstract:
Previously, we succeeded in isolating a novel mutant cwa1, bc1 allele of japonica species of485rice, which was likely to be loss-of-function mutations of AtCOBL4 ortholog encoding a putative
glycosylphosphatidylinositol (GPI)-anchored COBRA family protein and unable to synthesize normal
secondary walls. The novel rice mutant cwa1 has lost a regulation of deposition and assembly of cell wallmaterials to form the architecture of the even pattern of thickening secondary cell wall in the sclerenchymatous
cells of rice internodes. So far, the primary function of AtCOBRA is hypothesized to be orienting cellulose
microfibrils, presumably through some sort of interaction with the AtCesA complex and microtubules. One
hypothesized way of ahieving this is through the putative carbohydrate binding module (CBM) present on the
AtCOB protein. In rice genome, the BC1 gene encodes a plant-specific GPI-anchored COBRA family proteinwith a putative CBM. In this study, by 3-amino acid substitution in the putative CBM, we examine the functionof putative CBM in cell wall formation process through binding to cell wall matrix carbohydrate.
2009-104
イネ CAD 遺伝子変異体 gh2 の稲わらの糖化効率
村上真也*1、服部武文*1、向井まい*1、宮尾安藝雄*2、池 正和*3、鈴木史朗*4、徳安 健*3、廣近洋彦 *2、坂本
正弘*5、梅澤俊明*1*4*1
京都大学生存圏研究所、*2 農業生物資源研究所、*3 食品総合研究所、*4 京都大学生存基盤科学研究ユニ
ット、*5 京都大学大学院農学研究科地域環境科学専攻
Saccharification degree of lingo-cellulose in rice straw of a cinnamyl alcohol dehydrogenase mutant, gh2
Shinya Murakami*1, Takefumi Hattori*1, Mai Mukai*1, Akio Miyao*2, Masakazu Ike*3, Shiro Suzuki*4, Ken
Tokuyasu*3, Hirohiko Hirochika*2, Masahiro Sakamoto*5, Toshiaki Umezawa*1*4*1
Research Institute for Sustainable Humano sphere, Kyoto University. Uji, Kyoto 611-0011, *2National Instituteof Agrobiological Science. 2-1-2 Kannondai, Tsukuba, Ibaraki 305-8602*3
National Food Research Institute. 2-1-12 Kannondai, Tsukuba, Ibaraki 305-8642, *4Institute of Sustainability
Science, Kyoto University. Uji, Kyoto 611-0011, *5Graduate School of Agriculture, Kyoto University. Sakyo-ku,
Kyoto 606-8502
Abstract:
We are attempting the alteration of the cinnamate/monolignol pathway to improve bioethanol
production from rice straw. In this study, we focused on cinnamyl alcohol dehydrogenase (CAD). CADs are the
enzymes that reduce the p-hydroxycinnamaldehydes to the corresponding alcohols. The brown midrib 1 mutant
of maize is known to have low activity of CAD and used as forage crop because of its high digestivity. We
found a rice mutant having retrotransposon insertion in a CAD gene. It had lower lignin content in all tissues
compared to those of control plants. We investigated the enzymatic saccharification of the plants and foundhigher degree in the mutant.
2009-105
ゴマの抗酸化リグナンであるセサミノールの生合成経路
藤原利彦*1、小山晴菜*1、小幡昌代*1、塩手直樹*1、川原夏美*1、鈴木利貞*1、片山健至*1、並木満夫*2、田代亨*3*1
香川大学農学部、*2 名古屋大学農学部 （名大名誉教授）、*3 千葉大学園芸学部
Biosynthesis of sesaminol, an antioxidant lignan in Sesamum indicum seeds
Toshihiko Fujiwara*1, Haruna Koyama*1, Masayo Obata*1, Naoki Shiote*1, Natsumi Kawahara*1,
Toshisada Suzuki*1, Takeshi Katayama*1, Mitsuo Namiki*2, Toru Tashiro*3.
*1
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, *2Faculty ofAgriculture, Nagoya University, Furou-cho, Chikusa, Nagoya, Aichi 464-8601, *3Faculty of Horticulture, Chiba
University, 648 Matsudo, Chiba 271-8510
Abstract:
Sesame seeds contain sesaminol, a phenolic and antioxidant lignan, with sesamin and sesamolin.
However, biosynthetic pathway to sesaminol peculiar to the sesame seeds was unknown. To clarify thebiosynthetic pathway to sesaminol and the related sesame lignans, isolation and identification of sesaminol,
minor sesame lignans, and lignan glycosides from the sesame seeds, and enzymatic formation of sesaminol werecarried out. Pinoresinol, piperitol, sesamolinol, 7-episesaminol, and sesamolinol diglucoside were isolated andidentified together with sesaminol and sesaminol triglucoside. It was suggested that incubation of sesamin witha microsome fraction from the sesame seeds gave sesaminol.
2009-106
Phanerochaete chrysosporium のリグニン分解酵素発現におけるカルモデュリン阻害剤の影響
阪本鷹行・北浦博法・南 正彦・上田暁生・鈴木一実・入江俊一
486滋賀県立大学大学院 環境科学研究科
Effect of calmodulin inhibitors on the production of ligninolytic enzymes in Phanerochaete chrysosporium
Takaiku Sakamoto, Hironori Kitaura, Masahiko Minami, Akio Ueda, Kazumi Suzuki and Toshikazu Irie
Department of Environmental Science, The University of Shiga Prefecture
Abstract:
Our previous study revealed that the calmodulin (CaM) gene was upregulated during initiationof lignin peroxidases (LiPs) and manganese peroxidases (MnPs) production in Phanerochaete chrysosporium.
In this study, we investigated effects of CaM inhibitors, trifluoperazine (TFP), W-7 and W-5 on the enzymes
production in P. chrysosporium to confirm the role and involvement of CaM in the enzyme expression. Whenthe chemicals were added into reaction mixtures including the crude enzymes, W-7 and W-5 didn't influence the
enzyme activities, but, unexpectedly, TFP specifically inhibited LiP reaction. When 100 7M of W-7 was added
into the fungal culture within 72 h of the culture start, the enzyme expression was inhibited. Using a contrast
medicine, W-5 instead of W-7, about 50% of the enzyme activities were still observed, which indicates that the
inhibition mechanism of W-7 was interaction with CaM. Real time RT-PCR analysis revealed that 12 genes of
LiPs and MnPs were transcribed parallel with the enzyme activities under the culture condition and the all genes
were inhibited by W-7 at transcription level.
2009-107
土壌から単離した菌類によるクリセンの分解
アセップ ヒダヤット、伊藤和貴、橘 燦郎
愛媛大学農学部
Degradation of chrysene by a fungus isolated from soil
Asep Hidayat, Kazutaka Itoh, Sanro Tachibana
Department of Applied Bioscience, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime
790-8566, Japan
Abstract:
Chrysene, a polycyclic aromatic hydrocarbon (PAH), is an important class of environmental
pollutants because it has been found to have a variety of toxic, mutagenic, and resist biodegradation. The
degradation of chrysene in a liquid medium by a fungus isolated form soil is studied. A single strain fungus wasfound for the best ability to degrade chrysene in an agar medium. This fungus, Fusarium sp. F092, was tested todegrade chrysene in both saline and non-saline conditions. Effects of surfactant concentration and agitatedculture were also conducted to improve the fungus ability for degradation of chrysene. Salinity level of sea
water (35o/oo) had no significant effect on the degradation of chrysene in both on solid and liquid media. The
degradation of chrysene in a liquid medium had improved 1.5 folds when the culture agitated at 120 rpm.
Several non- ligninolytic enzymes secreted by a fungus were detected in a liquid medium. The highest activityof 1,2- dioxigenase reached 203.5 Ul-1 on 30 days and 29.7 Ul-1 for 2,3-dioxygenase on 40 days. These results
show that Fusarium sp. F092 is a potential fungus for bioremediation.
2009-108
白色腐朽菌 Phlebia 属菌による有機塩素系農薬の処理
肖 鵬飛*1、森 智夫*2、近藤隆一郎*2*1
九州大学大学院生物資源環境科学府、*2 九州大学大学院農学研究院
Biodegradation of organochlorine pesticides by white rot fungi, Phlebia genus
Pengfei Xiao, Toshio Mori, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
The organochlorine pesticides, dieldrin and heptachlor were used as substrate for degradation
experiment by 20 white rot fungi belonging to Phlebia genus. Phlebia acanthosystis, Phlebia brevispora andPhlebia aurea were selected based on the degradation ability of dieldrin. Dieldrin was biotransformed tohydroxyl dieldrin and several unidentified metabolites by Phlebia acanthosystis, Phlebia brevispora andPhlebia aurea. Heptachlor was degraded rapidly by almost all of white rot fungi belonging to Phlebia genus.
The degradation rate of heptachlor was higher than that of dieldrin. Heptachlor epoxide, 1-hydroxychlordene
and 1-hydroxy-2,3-epoxychlordene were detected as metabolites from the cultures treated by most of Phlebia
fungi.
2009-109
DDT degradation potential of mushroom waste medium
Adi Setyo Purnomo, Ichiro Kamei, Toshio Mori and Ryuichiro Kondo
Faculty of Agriculture, Kyushu University, Fukuoka, 812-8581, Japan
487

Abstract:
Pleurotus ostreatus (Hiratake) had high ability to degrade and mineralize DDT (1,1,1-trichloro
2,2 bis (4-chlorophenyl) ethane) in potato dextrose broth (PDB) medium. P. ostretaus also degraded DDT in
solid medium higher than Gloeophyllum trabeum and Phanerochaete chrysosporium. P. ostreatus medium
before and after mushroom production (waste medium) were used and compared. DDT was degraded 23% and
31% during 4 weeks incubation by P. ostreatus medium before and after mushroom production, respectively.
Mineralization of 14C-DDT was also investigated. 14C-DDT was mineralized 3.2% and 3.4% during 4 weeks
incubation by P. ostreatus medium before and after mushroom production, respectively. It indicated that waste
medium was more effective to degrade DDT. For application purposes, degradation potential in artificial
DDT-contaminated soil was also investigated. The waste medium of P. ostretus degraded DDT 40% and 60%
during 4 weeks incubation in sterile and un-sterile soils, respectively. DDD (1,1-dichloro-2,2 bis(4-chlorophenyl) ethane) was detected in un-sterile soil, indicated involvement of soil microorganisms.
14
C-DDT was mineralized 3.0% and 4.1% in sterile and un-sterile soil, respectively. These results indicated thatmushroom waste medium of P. ostreatus is the potential nature source which can be used for bioremediation of
DDT.
2009-110
イオン液体 1-n-ブチル-3-メチルイミダゾリウムクロライドに対する木材構成成分の反応性
谷口 僚*1、蓮見 愛*1、中川明子*1、大井 洋*1、岸野正典*2
筑波大学大学院生命環境科学研究科、北海道立林産試験場
Reactivity of wood components against an ionic liquid 1-n-butyl-3-methylimudazolium chloride
Ryo Taniguchi*1, Ai Hasumi*1, Akiko Nakagawa-izumi*1, Hiroshi Ohi*1, Masanori Kishino*2*1
Graduate School of Life and Environmental Sciences, University of Tsukuba, *2Hokkaido forest Products
Research Institute)
Abstract:
Japanese red pine (Pinus densiflora) and Japanese beech (Fagus crenata) woods were treatedwith one of ionic liquids: 1-n-butyl-3-methylimidazolium chloride. P. densiflora dissolved more rapidly
compared to F. crenata, but its tendency was reversed at the end of treatment for 24 hours. After the treatment at
120ºC for 72 hours, approximately 70% of glucan in Acacia mangium fibers was denatured. Although cellulose
was dissolved by the treatment at 120ºC for 24 hours, the residue of A. mangium fibers kept containing alignin-carbohydrate complex (LCC). The structure of LCC was estimated a complex of βO-4 type structuralelement and xylan. We synthesized an LCC model compound with veratrylglycerol-syringyl ether andmethyl--D- xylopyranoside to clarify the stability of LCC during the ionic liquid treatment.
2009-111
イオン液体/DMSO 混合溶媒系に於けるリグニンモデル化合物の分解挙動
久保智史、山田竜彦、橋田 光、菱山正二郎、細谷修二
独立行政法人森林総合研究所
Decomposition of a β-O-4 type lignin model compound in the mixed solvent system of ionic liquid and DMSO
Satoshi Kubo, Tatsuhiko Yamada, Koh Hashida, Shojiro Hishiyama, Shuji Hosoya
Forestry and Forest Products Research Institute
Abstract:
Structural stabilities of phenolic β-O-4 lignin model compounds in the mixed solvent system ofionic liquid and DMSO (IL/DMSO) were examined. Decomposition rate of the model compound,
threo-guaiacylglycerol-beta-guaiacyl ether (T-GG), in IL was not significantly affected by the incorporating of
90% of DMSO. However, decomposition of T-GG became gradually slow, if more than 95% of DMSO wasincorporated to IL. Enol-ether, one of the primary decomposition products of GG, was also detected in the T-GG
decomposition in the IL/DMSO, even in the mixed solvent having very low content of IL(IL/DMSO=0.25/99.75 w/w), although EE was not formed in the pure DMSO. This result suggested that
decomposition mechanism of T-GG in pure DMSO was different from that in IL/DMSO.
2009-112
アルカリ処理オゾン酸化クラフトリグニンとアルミニウムとの錯体形成
相見 光*1、栗本康司*1、山内 繁*1、田原 恒*2*1
秋田県立大学木材高度加工研究所、*2 独立行政法人森林総合研究所
Formation of a complex with aluminum by ozone-treated kraft lignins and their low molecular weight fragments
Hikaru Aimi*1, Ko Tahara*2, Yasuji Kurimoto*1, Shigeru Yamauchi*1*1
Institute of Wood Technology, Akita Prefectural University, 11-1 Kaieisaka, Noshiro, Akita 016-0876, Japan,
488

*2

Department of Molecular and Cell Biology, Forestry and Forest Products Research Institute, 1 Matsunosato,
Tsukuba, Ibaraki 305-8687, Japan
Abstract:
The formation of a complex with aluminum by low molecular weight compounds andsaponified ozone-treated kraft lignins was evaluated based on the decrease in pH of their solutions on the
addition of 0.1 M AlCl3. Decreases in pH were observed with the solutions containing compounds having
adjacent carboxyl groups (oxalic acid), carboxyl/alcoholic hydroxyl groups (glycolic acid), carboxyl/formyl
groups (glyoxylic acid), and phenolic hydroxyl groups (protocatechuic acid) on the addition of 0.1 M AlCl 3. The
malonic and phthalic acids, having two carboxyl groups, were also effective. These results show that thecompounds were effective in forming complexes with aluminum. This finding corresponds to the fact thataluminum toxicity is reduced by formation of a complex with aluminum, except in phthalic acid. The chemical
structures stated above in ozone-treated kraft lignins contribute, at least partly, to the complex with aluminum.
The pH of solutions containing saponified ozone-treated kraft lignins and alkaline-treated kraft lignin decreased
more than that without modified kraft lignins on the addition of 0.1 M AlCl3, showing that they were effective informing a complex with aluminum.
2009-特別講演
木材腐朽菌の新たな機能を求めて 一 環境浄化と健康増進 一
近藤隆一郎
九州大学大学院農学研究院
Invited Lecture: New functions of wood-rotting fungi -Bioremediation and functional foodRyuichiro Rondo
Faculty of Agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Environmental pollutants are a serious concern worldwide because of the hazards they pose to
the health of humans and animals. One method that has become increasingly popular for decontamination of theenvironment has been bioremediation. One of the early reports indicated that lignin-degrading white-rot fungi,
as exemplified by Phanerochaete chrysosporium, can degrade an extremely diverse group of environmental
pollutants. For thousands of years, mushrooms have been known as a source of medicine. In East Asia, thefruiting body of the fungus Ganoderma lucidum has been used for centuries. In this presentation, new functionsof wood-rotting fungi, bioremediation and functional food, will be discussed.
2009-201
非木質組織のリグニン定量
戸田守一、中村裕貴、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
On the determination of lignin content in non-wood tissues and plants
Morikazu Toda, Hirotaka Nakamura, Tomoya Yokoyama, Yuji Matsumoto
Wood Chemistry Laboratory, Graduate School of Agricultural and Life Sciences, the University of Tokyo, Japan
Abstract:
In previous studies it was clarified that as Klason residue of non-woody tissues contain definite
amounts non-lignin substances, Klason method overestimates the lignin content of non-wood tissues or plants.
To see the effect of various kind of extraction to lignin measurement, 9 kinds of extractions were carried toginkgo leaf and zelkova leaf. After pre-extraction, amounts of lignin measured by Klason method and acetyl
bromide method were lower than those of non-extracted samples in most case. But it is not sure whether we canuse these extractions to other species.
2009-202
アシドリシスにおいて酸の種類が及ぼすリグニン β-O-4 結合開裂機構への影響について
今井貴章、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Effect of kind of acid on the mechanism of the β-O-4 bond cleavage during acidolysis
Takaaki Imai, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo
Abstract:
In the acidolyses of veratrylglycerol- -guaiacyl ether (VG) using HBr, guauachol (G) was
quantitatively produced on the disappearance of VG, but the formation of a Hibbert’s ketone,
1-hydroxy-3-(3,4-dimethoxyphenyl)propan-2-one (HK), started after certain lag time and was not quantitative.
489

In the HCl system, both G and HK were quantitatively produced. In the H2SO4 system, another Hibbert’s
ketone, 3,4-dimethoxyphenylacetaldehyde (HK’), was fairly produced with the quantitative formation of G, but
only trace amount of HK was detected. By the addition of KBr to the HBr system, the disappearance rate of VG
was not affected, but the formation of HK as well as G became quantitative. The addition of KCl to the HBrsystem did not affect the disappearance rate of VG, but the difference in the formation rates between G and HK
become smaller than that in the HBr system without KCl. The addition KBr to the HCl system enhances thedisappearance rate of VG and formation rate of G. Consequently, the formation rate of HK was slower than G in
this case. In all these cases, the formation of G was almost quantitative, but the reaction rate and probably thereaction mechanisms themselves are greatly affected by the kind and amount of counter anion of the acid.
2009-203
レーザー脱離イオン化法によるリグニンの質量分析
吉岡康一*1、安東大介*1、西村裕志*1、岸本崇生*2、渡邉崇人*1、本田与一*1、渡辺隆司*1*1
京都大学生存圏研究所、*2 富山県立大学工学部
Mass spectrometry of lignin by laser desorption/ionization
Koichi Yoshioka*1, Daisuke Ando*1, Hiroshi Nishimura*1, Takao Kishimoto*2, Takahito Watanabe*1, Yoichi
Honda*1, Takashi Watanabe*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, *2Faculty of Engineering, Toyama
Prefectural University
Abstract:
Synthetic and natural lignins were analyzed by matrix-assisted laser desorption/ionization
time-of-flight mass spectrometry (MALDI-TOF MS) and a matrix free-LDI- MS method, named nano-assisted
laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOF MS). In the analysis of MALDI with
2,5-dihydroxybenzoic acid as a matrix, peaks originating from various lignin samples, such as, dehydrataion
polymer (DHP), β-O-4 type artificial lignin and MWL (milled wood lignin) were detected with highreproducibility. MALDI mass spectra of β-O-4 type artificial lignin were obtained in a high molecular weightarea (over m/z 5,000). Close similarity was found between NALDI-MS and MALDI-MS of the lignins. The soft
LDI method is useful for the structural analysis of lignin.
2009-204
p-ハイドロキシフェニル核をビフェニル骨格に有する新規ジベンゾジオキソシン構造
秋山拓也*1、Hoon Kim*2、Richard A. Dixon*3、John Ralph*2*1
東京大学大学院農学生命科学研究科、*２ウイスコンシン大学生化学部、 *３サミュエルロバーツノーブル財団植物生物学部門
Novel dibenzodioxocin structures involving p-hydroxyphenyl units on their biphenyl units
Takuya Akiyama*1, Hoon Kim*2, Richard A. Dixon*3, John Ralph*2*1
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1Yayoi, Bunkyo, Tokyo
113-8657, John Ralph*2University of Wisconsin-Madison, Department of Biochemistry, Enzyme Institute, 1710
University Ave., Madison, WI 53726, USA, John Ralph, *3Plant Biology Division, Samuel Roberts Noble
Foundation, Ardomore, OK73401, USA
Abstract:
Cross-coupling of monolignols with biphenyl compounds consisting of p-hydroxyphenyl (H)and/or guaiacyl (G) moieties, using Ag2O, formed dibenzodioxocins. HH-, GH-, and GG-biphenyl types ofdibenzodioxocins were found HSQC spectra of H-enriched lignins isolated from C3H deficient alfalfa. Of thethree types, the GH-biphenyl type was a major structure. When a GH-biphenyl unit is etherified by
4-O-coupling with another monomer only a single regioisomer is observed – that in which the G-unit isetherified. The other regioisomer β-O-4-linked on the H unit was not found either in the lignin or in the
cross-coupling products.
2009-205
マイクロ波増感触媒反応を利用したバイオリファイナリーシステムの開発
大橋康典、内藤喜之、渡邊崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Development of biorefinery system using microwave-sensitized catalytic reaction system
Yasunori Ohashi, Yoshiyuki Naito, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 6110011, Japan
Abstract:
Recently, increase in oil price caused by fossil fuel depletion and global warming by use of the490

fuel become serious problem. Therefore bioethanol production from wood, which is the most abundant biomass
and distributed worldwide will be developed as an alternative energy resource. Usually sugars obtained frombiomass were utilized effectively as resource of many chemicals and polymers. On the other hand, lignin, thesecond abundant natural polymer has often been burned or discarded without use for chemical resources.
Therefore we stated to develop environmentally- benign lignobiorefinery system using microwave-sensitizedcatalytic reactions.
2009-206
半流通型加圧熱水処理におけるブナリグニンの挙動
山内一慶、Natthanon Phaiboonsilpa、河本晴雄、坂志朗
京都大学大学院エネルギー科学研究科
The behavior of lignin in Japanese beech as treated by semi-flow hot-compressed water
Kazuchika Yamauchi, Natthanon Phaiboonsilpa, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Yoshida-honmachi. Sakyo-ku, Kyoto 606-8501, Japan
Abstract:
Japanese beech (Fagus crenata) wood was treated by two-step semi-flow hot-compressed water(the first step: 230ºC/10MPa/15min and the second step: 270ºC/10MPa/ 15min). To study a behavior of lignin
during the treatment, water-soluble portion and residue were fractionated and Klason lignin, acid-soluble lignin
and alkaline nitrobenzene oxidation products were determined. As a result, about 17wt% on wood basis (64wt%
on lignin basis) was found as lignin in water-soluble portion at the first step, while about 4wt% (13wt% on
lignin basis) at the second step. In the residue, at the end of the second stage, only 3% of lignin (11wt% on
lignin basis) was found. Interestingly, the lignin structures in these fractions were different.
2009-207
スギの半流通型２段階加圧熱水処理におけるスギリグニンの分解
ナッタノン パイブーンスウィルパ、山内一慶、河本晴雄、坂志朗
京都大学大学院エネルギー科学研究科
Decomposition of lignin in two-step semi-flow hot-compressed water treatment of Japanese cedar
Natthanon Phaiboonsilpa, Kazuchika Yamauchi, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Yoshida-honmachi. Sakyo-ku, Kyoto 606-8501, Japan
Abstract:
Japanese cedar (Cryptomeria japonica) was treated by two-step semi-flow hot-compressedwater (230ºC/10MPa/15min and 280ºC/10MPa/30min), and fractionated into water-soluble portion, precipitatesand hot-compressed water-insoluble residue. The water-soluble portion was then extracted by ethyl acetate toobtain ethyl acetate-soluble portion. For the obtained ethyl acetate-soluble portion and precipitates, consisting
mainly of lignin-derived products, gel permeation chromatography (GPC) and gas chromatographic-mass
spectrometric (GC-MS) analyses were conducted. As a result, GPC analysis revealed that the ethyl
acetate-soluble portion contained lignin-derived monomeric, oligomeric and polymeric products, while theproducts with relatively higher molecular weight were found in the precipitates. GC-MS analysis of the ethyl
acetate-soluble portion, on the other hand, elucidated that β-O-4 ether linkage of lignin as well as Cβ/Cγ andCα/Cβ linkages in the propyl sidechain of the C6-C3 units could be cleaved under the condition of
hot-compressed water treatment. In addition, the alkaline nitrobenzene oxidation analysis showed a decrease inoxidation products of the hot-compressed water-insoluble residue. This observation clearly confirmed that thecleavage of the ether linkage of lignin was preferably taken place in the present hot-compressed water treatment.
2009-208
木材熱分解における針葉樹、広葉樹リグンの挙動
モハメド・アスマディ, 河本晴雄, 坂 志朗
京都大学大学院エネルギー科学研究科
Pyrolysis behaviors of softwood and hardwood lignins in wood pyrolysis
Mohd Asmadi, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Yoshida-honmachi. Sakyo-ku, Kyoto 606-8501, Japan
Abstract:
Pyrolysis behaviors of Japanese cedar (Cryptomeria japonica, a softwood) and Japanese beech(Fagus crenata, a hardwood) milled wood lignins were studied with thermogravimetry (TG) and pyrolysis in an
ampoule reactor (N2/600ºC/40-600s). Guaiacol and syringol were also used to understand the behaviors of theguaiacyl- and syringyl-types of aromatic rings in lignin, respectively. As a result, the following results wereobtained; 1) DTG peak temperature: lower in beech, corresponding to the low-temperature shoulders of cedar
and beech wood samples, 2) devolatilization efficiency: beech > cedar, 3) coke formation: beech > cedar, 4) tar
491

composition: similar after long heating time. Some of these features are explained with the different pyrolysis
behaviors of guaiacol and syringol.
2009-209
Relationships between hemicellulose composition and lignin structure in hardwoods
Yu Huang*1*1, Linshan Wang*2, Yuesheng Chao*2, Deded Sarip Nawawi*3, Takuya Akiyama*1, Tomoya
Yokoyama*1, Yuji Matsumoto*1*1
Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, the University ofTokyo, *2School of Sciences, Northeastern University, China, *3Bogor Agricultural University, Indonesia
Abstract:
The composition and the absolute amount of neutral sugars were determined for 48 hardwood
species (including 17 hardwoods of genus Acacia, 14 hardwoods of genus Eucalyptus and l7 hardwoods ofdifferent other genus) by aldito1-acetate method, and their relationships to the syringyl ratio (S/(S+V)) of lignin,
which was determined by nitrobenzene oxidation, was investigated. It was suggested that it is hemicellulose but
not cellulose that changes with certain tendency in the conjugation with the change of lignin structure. The
relationships between syringyl ratio and characteristic peak area ratios of aromatic ring in IR spectrum were alsostudied.
2009-210
炭水化物 C-2 位に対する活性酸素種の反応性の評価
中川明彦、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科生物材料科学専攻木材化学研究室
Evaluation of the reactivity of active oxygen species toward the C-2 position of carbohydrate
Akihiko Nakagawa, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo
Abstract:
The reactivity of active oxygen speices (AOS) toward carbon-hydrogen bonds at the C-2
positions of carbohydrate was examined using methyl β-D-glucopyranoside (MGP), methyl
β-D-mannopyranoside (MMPβ), and methyl β-D-(2-2H)glucopyranoside (MGPβ-2D). In this study, AOS werein situ generated by subjecting phenolic compounds, 2,4,6-trimethylphenol (TMPh) and
4-hydroxy3-methoxybenzyl alcohol (vanillyl alcohol, VA), to the oxygen oxidation. MMPβ was degraded
greater than MGPβwhen they were treated together in the presence of each phenolic compound, which suggeststhat the stereo configurational difference in their C-2 positions has a certain effect on their reactions with AOS.
The degradations of the carbohydrate model compounds
seemed to be slightly but clearly dependent on kind of AOS origin. In the absence of the phenolic compounds,
MMPβwas degraded slightly in the oxygen alkaline treatment although MGPβ was stable in the same system,suggesting that the stereo configuration at the C-2 position has an influence on the lability to oxygen oxidation.
2009-211
Dissolution of ethylenediamine pretreated high kappa pulp in LiCl/DMSO
Zhiguo Wang, Tomoya Yokoyama, Yuji Matsumoto
Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, The University ofTokyo
Abstract:
Various hardwood and softwood chemical pulps, including those with relatively high lignin
content (up to ca.10.5%), were completely dissolved without milling in LiCl/DMSO after a pretreatment with
ethylenediamine (EDA). Because the milling of the sample is not required, degradation of cell wall components
caused by milling does not take place. After the EDA pretreatment, the crystallinity of pulps were found to be
kept as high as the corresponding original pulps although the crystal structure was changed. It is the first timethat transparent solutions of underivatized pulps with high lignin content were obtained in a simple organic
solvent system. Formation of pulp-EDA complex with proper EDA ratio seems to be critical for the dissolution
in LiCl/DMSO. The NMR spectrum of EDA treated pulp solution provided good resolution even though the DPof cellulose in the pulp is very high.
2009-212
ポリサルファイド蒸解と修正蒸解の最適な組み合わせに関する検討
渡部啓吾*1、清水正裕*1、黒須一博*1、南里泰徳*1*2、大井 洋*3*1
日本製紙株式会社技術研究所、*2 株式会社日本紙パルプ研究所、*3 筑波大学大学院生命環境科学研究492

科Application of new cooking system using highly concentrated polysulfide to modified cooking with multicharges of cooking liquor
Keigo Watanabe*1, Masahiro Shimizu*1, Kazuhiro Kurosu*1, Yasunori Nanri*1*2, Hiroshi Ohi*3*1
Nippon Paper Industries Co., LTD, 5-21-1 Oji, Kita-ku, Tokyo, Japan, *2Japan Pulp and Paper ResearchInstitute, Inc., *3Graduate School of Life and Environmental Science, University of Tsukuba, 1-1-1, Tennoudai,
Tsukuba, Ibaraki, Japan
Abstract:
Polysulflde cooking is one of the most efficient technologies to increase pulp yields. The
polysulfide has to be produced from white liquor (WL) to keep the Na + and S2- balance in the WL recovery
cycle. When we try applying the polysulfide to iso-thermal cooking (ITC), not only NaOH but also Na2S at astart of the cooking are diluted by sequential charges of cooking liquor. Therefore, a new electrolysis method of
WL has been developed to produce the polysulfide efficiently. In this study, the combinatorial use of ITC andpolysulfide cooking were evaluated, expecting a process in which the mill scale pilot electrolyzers were
installed.
2009-213
硫酸リグニンを原料としたポリエステルの合成
松下泰幸*1、猪又豊生*1、高木康雄*2、長谷川達也*3、福島和彦*1
名古屋大学大学院生命農学研究科、*2 名古屋市工業研究所、*3 名古屋大学エコトピア科学研究所
Synthesis of polyester using sulfuric acid lignin
Yasuyuki Matsushita*1, Toyoki Inomata*1, Yasuo Takagi*2, Tatsuya Hasegawa*3, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
464-8601, *2Nagoya municipal Industrial Research Institute, 3-4-41 Rokuban, Atsuta-ku, Nagoya 456-0058,*3
EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601
Abstract:
In this study, polyesters were synthesized using sulfuric acid lignin. First, sulfuric acid lignin
was converted into water-soluble polymer (HSAL) by hydrothermal reaction under alkali condition. H-SAL wasintroduced carboxyl group during the hydrothermal reaction and the acid-type HSAL (-COOH) could be
dissolved into ε-caprolactone. The polyesters were synthesized using the acid-type H-SAL andε-caprolactonewith varying ratio of them. The prepared polyesters with high H-SAL content exhibited the swellability inorganic solvent. The thermal properties of the prepared polyesters were measured by DSC. From the results, anendothermal peak, which corresponds to the crystalline fusion of the polycaprolactone (PLA) segment was
shifted at lower temperature and the area was smaller with increase the H-SAL content in the polymer.
2009-214
リグノスルホン酸/ピロリドン環含有ポリマー複合体の調製と吸着機能材料としての応用
仲西雄亮、寺本好邦、西尾嘉之
京都大学大学院農学研究科
Preparation of lignosulfonic acid/polymer containing pyrrolidone rings and application to absorbents
Yusuke Nakanishi, Yoshikuni Teramoto, and Yoshiyuki Nishio
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa
Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan
Abstract：
In order to utilize lignosulfonic acid (LSA) as absorbents of bio-related substances,
LSA-containing composites were prepared by (a) immersion of polyvinylpolypyrrolidone or cellulose acetate(CA)/poly(N-vinyl pyrrolidone) (PVP) complex in a LSA solution and (b) re-precipitation from a solution of
CA/PVP/LSA mixture. Chemical compositions of the products were successfully determined by FT-IR
measurements. LSA was effectively incorporated into the composites via hydrogen bonding withvinylpyrrolidone unit. An adsorption property of the composites to catch nicotine was evaluated with Freundlichand Langmuir models, revealed the occurrence of a strong interaction between LSA and nicotine especially inthe composites prepared by (a).
2009-215
リグニンスルホン酸塩及び芳香族エポキシ化合物を原料とするエポキシ樹脂の合成と熱的性質
贋瀬重雄*1、畠山立子*2、畠山兵衛*3*1
産業技術総合研究所・環境化学、*2 リグノセルリサーチ、*3 福井工業大学工学部
Synthesis and thermal properties of epoxy resins derived from sodium ligninsulfonate and aromatic epoxy
493

compound
Shigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*3*1
Research Institute for Innovation in Sustainable Chemistry' AIST, Central 5, 1-1-4 Higashi, Tsukuba, Ibaraki
305-8565, Japan, *2Lignocel Research Ltd., Fukui-City, Fukui , 910-3558 Japan, *3Fukui University ofTechnology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Sodium ligninsulfonate (LS) was dissolved in ethylene glycol (EG) and the obtained mixture
was allowed to react with succinic anhydride in order to obtain a mixture of ester-carboxylic acid derivatives(LSEG polyacid, LSEGPA). EGPA was also synthesized from EG. LSEGPA was allowed to react with phthalicacid diglycidyl ester (PhADGE) in the presence of a catalytic amount of dimethylbenzylamine to form epoxy
resins. The molar ratio of epoxy groups to carboxylic acid groups ([EPOXY]/[ACID] ratios, mol/mol) was
maintained at 1.0. The contents of LSEGPA in the mixture of LSEGPA and EGPA (LSEGPA content) werevaried from 0 to 100 %. Thermal properties of epoxy resins were studied by differential scanning calorimetry(DSC) and thermogravimetry (TG). Glass transition temperatures (Tg's) of epoxy resins increased withincreasing LSEGPA contents, suggesting that lignin acts as a hard segment in epoxy resin polymer networks.
Thermal decomposition temperatures (Td's) of epoxy resins were almost constant regardless of LSEGPA
contents.
2009-216
リグニン由来エポキシ樹脂の合成とその応用
香川博之*1、岡部義昭*1、中村嘉利*2、佐々木千鶴*2、高橋昭雄*3*1
日立製作所材料研究所、*2 徳島大院ソシオテクノサインス研究部、*3 横浜国立大大学院工学研究院
Synthesis of lignin-derived epoxy resin and its application
Hiroyuki Kagawa*1, Yoshiaki Okabe*1, Yoshitoshi Nakamura*2, Chizuru Sasaki*2, Akio Takahashi*3*1
Material Research Laboratory, Hitachi, Ltd., *2Department of Biological Science and Technology Institute ofTechnology and Science, The University of Tokushima Graduate School, *3Department of Advanced Materials
Chemistry. Yokohama National University
Abstract:
We have tried to apply epoxy resin derived from woody lignin to copper-clad laminates andprinted-circuit boards. Lignin (L) and lignophenol (LP), which was lignin derivatives extracted by phenol fromwood, were successfully converted to organic-solvent-soluble epoxidized-lignin (EL) andepoxidized-lignophenol (ELP) by using tetramethyl ammonium hydroxide. EL and ELP as epoxy resins, L and
LP as hardeners were applied to copper-clad laminates. Glass transition temperatures of lignin-derived epoxy
resin hardeners were over 200 degrees C, and higher than those of commercially available epoxy resin hardeners
that were derived from oil. The properties of copper-clad laminates using lignin-derived epoxy resin hardeners
were almost the same as those of commercially available laminates.
2009-P01
豪雪地帯に生育する樹木の根元曲がり材の主成分について
小林慧、唐田信吾、芦谷竜矢、高橋孝悦
山形大学農学部
Chemical composition of basal bending wood in heavy snowfall region
Kei Kobayashi, Shingo Karata,Tatsuya Ashitani,Kouetsu Takahashi
Faculty of Agriculture, Yamagata University,
Abstract:
Basal bending of trees was formed by snow pressure in the snowfall region. We analyzed
chemical composition of normal and basal bending Sugi (Cryptomeria japonica D.Don) wood. As a result,lignin contents of basal bending wood were higher than normal wood, holocellurose contents of normal wood
were higher than basal bending wood. In eccentric thickening growth part of basal bending wood, range oflignin and holocellulose contents were similar to normal wood. It was suggested that the basal bending part,
except compression wood, was normal type growth.
2009-P02
ハンゲショウにおける 9,9’-デオキシ型ネオリグナンおよびリグナンの立体化学と生合成
牧野啓輔、片山健至,、鈴木利貞
香川大学農学部
Stereochemistry and biosynthesis of 9,9’-deoxy-neolignans/lignans by Saururus chainensis
Keisuke Makino, Takeshi Katayama, Toshisada Suzuki
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan
494

Abstract:9, 9’-Deoxy-lignans/neolignans have been isolated and identified in mainly Myristicaceae or
Lauraceae plants. However, their biosynthesis is unknown. The present report describes stereochemistry andbiosynthesis of Δ8’-4,7-dihydroxy-3,3’-dimethoxy-8-O-4’-neolignan, whose erythro and threo isomers are
named as Machilins C and D, respectively, in Saururus chainensis, that is, (1) dehydrogenative polymerizationof isoeugenol with horseradish peroxidase and H2O2 (erythro : threo = 16 : 84), (2) isolation of the9,9’-deoxy-8-O-4’ neolignans from the root of S. chainensis (4 : 96), (3) dehydrogenative polymerization of
isoeugenol with a cell-free extract from S. chainensis and H2O2 (14 : 86). The diastereomeric ratios of the9,9’-deoxy-8-O-4’-neolignan are shown in parentheses. A peroxidase activity in S. chainensis gave Machilin C
and Machilin D, but the ratio of the latter to the former is the same as the case in horseradish peroxidase (1).
However, the ratio in the neolignan from the plant (3) is larger than the above ratios in (1) and (2). Therefore,
the presence of a specific Machilin D synthase was suggested.
2009-P03
シラカンバ No. 8 幼植物体におけるカバノアナタケ菌 IO-U1 株感染部位縦断面でのフェノール性化合物の堆積及びペルオキシダーゼ活性の経時変化
鈴木美帆*1、高島有哉*2、石栗 太*1、飯塚和也*1、吉澤伸夫*1、横田信三*1*1
宇都宮大学農学部、*2 東京農工大学大学院農学研究院
Time-course changes in accumulation of phenolic compounds and peroxidase activity in the longitudinal
sections from Betula platyphylla var. japonica No. 8 plantlets infected with Inonotus obliquus IO-U1 strain
Miho Suzuki*1, Yuya Takashim*2a, Futoshi Ishiguri*1, Kazuya Iizuka*1, Nobuo Yoshizawa*1, Shinzo Yokota*1*1
Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Tochigi, Japan, *2United Graduate
School of Agricultural Science, Toku¥yo University of Agriculture and Technology, Fuchu 183-8509, Japan
Abstract:
It is well known that Inonotus obliquus is a fungas causing canker disease of birch trees.
Purpose of this study is to clarify the defense mechanisms of Betula platyphylla plantlets against infection with I.
obliquus. Time-course changes in accumulation of phenolic compounds and peroxidase activity were observedin the longitudinal sections from birch plantlets. The accumulation of phenolic compounds and peroxidase
activity were found in both wounded and infected plantlets, especially they were prominent in the infected
plantlets. In the infected plantlets, the accumulation of phenolic compounds and peroxidase activity wereobserved in the vessels located above and below the infected portion. These results suggest that phenolic
compounds might be polymerized by the peroxidases, forming barrier to protect the vessels from invasion of thefungal hyphae.
2009-P04
木材腐朽担子菌におけるシトクロム P450 分子種の多様性
井手正迪*1、一瀬博文*2、割石博之*2*1
九州大学大学院生物資源環境科学府森林資源科学部門生物資源化学分野、*2 九州大学大学院農学研究院森林資源科学部門生物資源化学分野
The diversity of cytochrome P450 of wood-rotting basidiomycetes
Masamichi Ide*1, Hirofumi Ichinose*２, Hiroyuki Wariishi*２*1Graduate School of Bioresource and Bioenvironmental Sciences, Department of Forest and Forest Products
Sciences, Kyushu University; *２Faculty of Agriculture, Department of Forest and Forest Products Sciences,
Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
We explored the molecular diversity of cytochrome P450 (P450) in the brown-rot fungus Postia
placenta using bioinformatic and experimental approaches. Based upon bioinformatic survey, 325 putativecoding sequences of cytochrome P450s were discovered from the genome database. To facillitate molecularand functional diversities of P. placenta P450s (PpCYPs), we attempted to isolate and characterize cDNAs using
RT-PCR. To date, we confirmed the gene expression of 157 PpCYPs and cloned 123 PpCYPs as full-length
cDNAs encoding a mature open reading frame. In addition, phylogenetic analysis was done suggesting thatwhite-rot and brown-rot basidiomycetes have been developed through vigorous evolution of P450s to meet theirunique metabolic diversities.
2009-P05
高活性リグニン分解菌 Phanerochaete sordida YK-624 株リグニン分解関連酵素遺伝子のクローニング及び発現解析
三隅健太*1、杉浦立樹*2、山口真也*1、平井浩文*1
495

*1

静岡大学農学部、*2 静岡大学創造科学技術大学院
Cloning and transcriptional analysis of genes which are involved in the lignin degradation by Phanerochaete
sordida YK-624
Kenta Misumi*1, Tatsuki Sugiura*2, Shinya Yamaguchi*1,Hirofumi Hirai*1*1
Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan. *2Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
Genes of 5-aminolevulinic acid synthase (ALAS) and 1,4-benzoquinone reductase (BQR) werecloned from hyper lignin-degrading fungus Phanerochaete sordida YK-624. ALAS gene from P. sordida
YK-624 (PsALAS) showed highest identity (93.0%) with ALAS from Phanerochaete chrysosporium ME-446.
BQR gene from P. sordida YK-624 (PsBQR) showed highest identity (93.1%) with the predicted BQR cording
gene in genomic sequence of P. chrysosporium RP78 which has been named as e_gwh2.5.446.1. The expressionof PsALAS showed significant correlation with the production of ligninolytic peroxidases such as manganeseperoxidase and lignin peroxidase. The expression of PsBQR was strongly induced by the addition of vanillin.
2009-P06
The enhancement of cellulose saccharification in corn stover by pretreatment with brown-rot fungi
Ziqing Gao, Ryuichiro Kondo
Department of Forest and Forest Products Sciences, Faculty of Agriculture, Kyushu University, 6-10-1
Hakozaki, 812-8581, Japan
Abstract:
Gloeophyllum trabeum KU-41 was chosen for corn stover pretreatment for bio-ethanol
production. Alditol acetate method was used to determine the changes of sugar content in corn stover pretreatedby G. trabeum KU-41. The content of xylan has been decreased by 25% in comparison to the control. For
cellulose crystallinity determination by X-ray diffraction, the crystallinity in corn stover pretreated didn`tchange significantly compared to the control. The activity of xylanase secreted by G. trabeum KU-41 was muchhigher than that of other G. trabeum strains. Xylan was degraded and hemicellulose might be disentangled
during the pretreatment
2009-P07
パラコッカス属細菌による黒液リグニンの分解と分解産物の定性
平田真寛*1、高木博子*1、本田宗央*1、松下泰幸*2、福島和彦*2*1
イビデン株式会社、*2 名古屋大学大学院生命農学研究科
Biodegradation of black liquror lignin and identification of degradation products by Paracoccus.sp.
Masahiro Hirata*1, Hiroko takagi*1, Munetaka Honda*1, Yasuyuki Matusita*2, Kazuhiko Fukushima*2*1
IBIDEN Co.,Ltd, *2Graduate School of Bioagricultural Science, Nagoya University, Nagoya 464-8601, Japan
Abstract:
In this study, we isolated a lignin degradation bacterium from IBIDEN activated sludge. The
bacterium was identified as Paracoccus species by the 16s rDNA genetic analysis. Paracoccus sp. was degraded
black liquor lignin to some products with a liquid shaking culture for 7 days at 30℃. Low molecular aromaticcompounds such as salicylic acid, 2,3-dihydroxybenzoic and 3,4-dihydroxybenzoic acid were detected in abacterium treated sample with GC/MS. In our results, there is a possibility of efficiency biotechnology refineryof black liquor lignin by bacteria.
2009-P08
白色腐朽菌由来の粗酵素を用いたアゾ染料の分解
大森元樹、伊藤和貴、橘 燦郎
愛媛大学農学部
Degradation of azo dyes with a crude enzyme from white rot fungi
Motoki Omori, Kazutaka Itoh, Sanro Tachibana
Department of Applied Bioscience, Faculty of Agriculture, Ehime University
3-5-7 Tarumi, Matsuyama, Ehime 790-8566, Japan
Abstract:
To purify effluents from textile industries and so forth, degradation of three azo dyes, Reactive
Red 4 (RR4), Reactive Black 5 (RB5) and Reactive Green 19 (RG19) by a crude enzyme from a white-rot
fungus, PL1 was conducted. Degradation rate of the dyes by the enzyme was about 10 to 20%. To enhance thedegradation rate, effects of pH, hydrogen peroxide and manganese sulfate concentrations, and mediators on
degradation of the dyes were investigated. Using the optimum reaction conditions found, degradation of thedyes by the enzyme was further conducted. It was found that 90 to 95% of each dye could be degraded forwithin 24 hours by the enzyme.
496

2009-P09
白色腐朽菌由来の酵素による 1-ニトロピレンの分解
木村 萌、河合真吾、西田友昭
静岡大学農学部
Degradation of 1-nitropyrene by enzymes from white rot fungi
Megumi Kimura, Shingo Kawai, Tomoaki Nishida
Department of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka University
Abstract：
Nitropolycyclic aromatic hydrocarbons (NPAHs) are a widely distributed class ofenvironmental contaminants which can be formed in the atmosphere by reaction of nitrogen oxides withpolycyclic aromatic hydrocarbons. In the present study, 1-nitropyrene, one of NPAHs was treated with each two
ligninolytic enzymes, laccase (Lac) and manganese peroxidase (MnP) prepared from the culture of white rot
fungi. The Lac-HBT (1-hydroxybenzotriazole) system in the presence of Tween 80 decreased 1-nitropyrene by
30% after 24 h of treatment, however, Lac-HBT system in the presence of Tween 20 did it only by 10%. On theother hand, MnP in the presence of Tween 80 (MnP-Tween 80) decreased 1-nitropyrene by 50% after 24 h oftreatment. These results indicate that, among the three enzymatic treatments, MnP-Tween 80 is most effective inremoving 1-nitropyrene.
2009-P10
Separation of wood cell components by the use of two dissolving procedures, "ball-milling and dsdsolution in
LiCl/DMSO" and "EDA-treatment and dissolution in LiCl/DMSO"
Zhiguo Wang, Tomoya Yokoyama, Yuji Matsumoto
Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, the University ofTokyo
Abstract:
The different fractions of wood cell components were separated by the dissolution of woodmeal in lithium chloride/dimethyl sulfoxide (LiCl/DMSO). By putting milling pretreated wood meal in to
DMSO containing different amount of LiCl, series of soluble fractions and residual fractions can be obtained.
The lignin in the residual fractions has always higher syringyl ratio (S/(S+V)) and higher yield of nitrobenzene
oxidation products (S+V) than that of corresponding soluble fractions. However, lignin in the soluble fractions,which was separated from ethylenediamine (EDA) pretreated wood meals had more non-condensed type thanresidual fractions. Both the yield of S+V and the ratio of S/(S+V) of soluble fraction from EDA pretreated wood
were higher than those of residual fraction. Characteristic carbohydrates found in the most difficult parts to bedissolved in milling pretreated wood meals were hemicelluloses rather than cellulose. Contrary, the weightration of xylose was relatively higher in soluble fraction than residual part separated from EDA pretreated woodmeals.
2009-P11
フリーラジカルによるリグニンモデル化合物の反応部位に関する研究(2)大橋康典、渡邊崇人、本田与一、渡辺隆司
京都大学生存圏研究所
Study on reactive position of lignin model compounds with free radicals (2)Yasunori Ohashi, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
Abstract:
A white rot fungus, Ceriporiopsis subvermispora degrades lignin by radical reactions of low
molecular mass metabolites at a site far from enzymes. As a possible ligninolytic system by the fungus, in situ
radical reactions have been proposed. Our previous experiments clearly indicate that carbon-centered (CR) andalkoxyl (AR) radicals degrade non-phenolic lignin model compounds (LMCs) through hydrogen Abstraction at
benzyl position of LMC, but peroxyl radical (PR) does not. Furthermore, direct detection of free radicals using
ESR support this reactivity of AR with LMCs. In the present study reactivity and LMC degradation mechanismof CR produced from azo-compounds was analyzed by UV-ESR method.
2009-P12
tert-ブトキシドを塩基とする反応系における β-O-4 結合開裂機構の検討
竹野甲子夫、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
497

Investigation into the mechanism of the βO-4 bond cleavage in a reaction system using tert-butoxide as a baseKineo Takeno, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Graduate School of Agricultural and Life Sciences, the University of Tokyo,
1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
The β-O-4 bond cleavage of dimeric non-phenolic lignin model compounds,
2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol(2),2-(2-methoxyphenoxy)-1-(3,4dimethoxyphenyl)ethanone (3), and 1-methoxy-2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl) ethane (4) was
examined in a potassium tert-butoxide/tert-butanol (KOtBu/tBuOH) system. The β-O-4 bonds of (2) and (3)cleaved in 0.5 mol/l KOtBu at 30ºC, which were much milder than those in general alkaline based pulping
processes. The disappearance of (3) was much faster than (2), which was similar to the results in aqueous NaOH
system reported by Gierer. An oxidized product, 3,4-dimethoxybenzoic acid (6), was detected, which is acharacteristic in this reaction system. The β-O-4 bond of (4) did not cleave in the same system, indicating thatthe initial reaction of (2) is the dissociation of the α-hydroxy group induced by -OtBu.
2009-P13
ヨウ化アルミニウム（III）試薬によるリグニン高分子モデル化合物の低分子化
幸田圭一*1、岸本崇生*2、塩澤洋介*3、浦木康光*3*1
北海道大学大学院農学研究院、*2 富山県立大工学部、*3 北海道大学大学院農学院
Depolymerization of a lignin polymer model compound with aluminium iodide (III)Keiichi Koda*1, Takao Kishimoto*2, Yosuke Shiozawa*3, Yasumitsu Uraki*3*1
Research Faculty of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, Hokkaido 060-8589,
Japan, *2Faculty of Engineering, Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama 939-0398,
Japan, *3Graduate School of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, Hokkaido
060-8589, Japan
Abstract:
Aluminium iodide (III), an effective reagent for cleavage of low-molecular-weight alkyl-aryl
ethers, was used to observe if it was able to cleave and depolymerize a lignin polymer model compoundconsisting of guaiacyl units exclusively with β-O-4 linkages. The AlI3 reagent degraded the lignin polymer
model compound to give some low-molecular-weight compounds, one of which was increasing in peak intensity(in total ion chromatogram) with increasing AlI3 Charge ratio and reaction time. The reagent, however, did notcleave all the β-O-4 linkages of the lignin polymer
model compound as it did those of a lignin dimer model compound.
2009-P14
スギ針葉中のリグニン −DFRC 法による分析の試み−
松井直之、大平辰朗
森林総合研究所 樹木抽出成分研究室
Detection of lignin in sugi leaves —An attempt of DFRC analysis—
Naoyuki Matsui, Tatsuro Ohira
Forestry and Forest Products Research Institute, Wood Extractives Lab., Matsunosato 1, Tsukuba, 305-8687
Japan
Abstract:
Many questions are left in lignins of tree leaves and needles, beginning with in their occurrence,
structure and functions. The Klason method often gives excessive results because of insoluble contaminants. In
this study, DFRC (Derivatization Followed by Reductive Cleavage) method, that can degradate the arylether
structure in lignin selectively, was employed to sugi (Cryptomeria japonica) leaves. This method gave thelignin-specific C6-C3 degradation products from sugi leaves, that show the existence of lignin in leaves.
2009-P15
-O-4 結合の新規な選択的開裂法:PSE 法の検討(1) −開裂条件の最適化−
安藤大将、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Studies on new selective cleavage method for β-O-4 linkages of lignin (β-PSE method) (1)—Optimization of mild alkali cleavage reaction condition—
Daisuke Ando, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Guraduate School of Agriculture, Kyoto University, Sakyo-ku,
Kyoto, 606-8502, Japan
498

Abstract:
New selective β-O-4 cleavage method (named β-PSE method) which consisted of four reactions
has been proposed. In this study, the final reaction (dilute alkali cleavage) of G-type lignin dimer wasinvestigated to determine its optimum conditions. The yield of degradation product reached a peak after 1∼3 hand decreased, and it was significantly affected by reaction temperature. As a result, the yield was maximum inthe conditions (NaOH concentration:0.03N, temperature:25℃, reaction time:1.5h). The cleavage reaction of
S-type and P-type lignin dimmers in the same conditions also gave the degradation product in high yield.
2009-P16
MWL 抽出残渣の分画と分析 — Hemicellulose-Lignin fraction (HCL) のキャラクタリゼーション—
宮川泰幸、竹本央記、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Fractionation and analysis of wood meal after extraction of MWL —Characterization of Hemicellulose-Lignin
fraction (HCL) —Yasuyuki Miyagawa, Ooki Takemoto, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Forest and Biomaterials Science, Graduate school of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502,
Japan
Abstract:
Wood meal after extraction of MWL and the following extraction with LiCl/DMAc was
extracted with 3M NaOH solution to get Hemicellulose-Lignin fraction (HCL). HCL was composed of much
hemicellulose and lignin in it. But the presence of Lignin-Carbohydrate Complex (LCC) bonds was unclear by
the combination method of enzymatic treatment and GPC analysis. Then, HCL was further acetylated andextracted with chloroform to afford Xylan-Lignin fraction (XL). XL had much xylan and lignin, andlignin-xylan bonds strongly suggested by the above combination method. Accordingly, XL may be a usefulfraction for the LCC bonds analysis.
2009-P17
リグニンモデル化合物の間接電解酸化反応(2) —mediator の検討—
白石 匠、上高原浩,、高野俊幸、中坪文明
京都大学大学院農学研究科
Indirect electrooxidation of lignin model compounds (2) —mediated by 1-hydroxybenztriazole, violuric acidand 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate)—
Takumi Shiraishi, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku. Kyoto,606-8502, Japan
Abstract:
Indirect electrooxidation of lignin model compound, 1-(4’-ethoxy-3’-methoxy- phenyl)ethanol(1G) using laccase mediators, such as 1-hydroxybenztroazole (HOBT) , violuric acid (VLA),
2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), was investigated to introduce
carbonyl group at a-position. The yields of the corresponding carbonyl compound 2G were about 50 % (HOBTor VLA mediated) and 20% (ABTS mediated). They are useful mediators for the indirect electrooxidation ofnatural lignin, although yields of 2G by these mediators were lower than that by N-hydroxyphthalimide (NHPI).
2009-P18
木材の酵素糖化におけるイオン液体前処理の効果
宮田賢二、宮藤久士、坂 志朗
京都大学大学院エネルギー科学研究科
Pretreatment with ionic liquids for enzymatic saccharification of wood
Kenji Miyata, Hisashi Miyafuji, Shiro Saka
Graduate School of Energy Science, Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
Pretreatment with ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) or
1-butyl-3-methylimidazolium acetate ([C4mim][Ac]) was studied for producing glucose from Japanese beech
by enzymatic hydrolysis. Beech wood was easily liquefied by [C4mim][Ac] treatment than [C2mim][Cl]treatment. Decrystallization of cellulose in wood was significant by [C4mim][Ac] treatment. Wood componentsliquefied in ionic liquids were recovered by adding water to the ionic liquids. By enzymatic saccharification
with cellulase for these recovered wood components, it was found that ionic liquids pretreatment was effective
to enhance glucose productivity. It was also clarified that much glucose yields can be attained by the
pretreatment with [C4mim][Ac], compared to that with [C2mim][Cl].
499

2009-P19
イオン液体中での非フェノール性 β-O-4 型リグニンモデル化合物の反応挙動
橋田 光、久保智史、山田竜彦、菱山正二郎、細谷修二
森林総合研究所
Reaction behaviors of non-phenolic β-O-4 type lignin model compounds in ionic liquids
Koh Hashida, Satoshi Kubo, Tatsuhiko Yamada, Shojiro Hishiyama, Shuji Hosoya
Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
Reaction behaviors of non-phenolic β-O-4 type lignin model compounds in ionic liquids havebeen examined. In ionic liquids at 150ºC, guaiacyl type model compounds, erythro (E) and threo (T) form
veratrylglycerol-β-guaiacyl ethers (VG), were decomposed slower than corresponding phenolic modelcompounds, gaiacylglycerol-β-guaiacyl ethers (GG). In the ionic liquid of 1-Butyl-3-methylimidazolium
chloride, E-VG was decomposed faster than T-VG. By contrast, significant differences in the decomposition
rates were not observed in 1-Ethyl-3-methyl- imidazolium acetate. Syringyl type non-phenolic model compoundof T-veratrylglycerol-beta- syringyl ether was decomposed slower than VGs. This result would be related withthe difference in the decomposition rate appeared between softwood and hardwood in an ionic liquid.
2009-P20
両親媒性リグニンの調製及びセメント分散剤としての評価
本間春海*1、久保智史*2、山田竜彦*2、幸田圭一*3、松下泰幸*4、福島和彦*4、浦木康光*3*1
北海道大学大学院農学院、、*2 森林総合研究所、*３北海道大学大学院農学研究院、*4 名古屋大学大学院
生命農学研究科
Preparation of amphiphilic lignin derivatives and evaluation of their viability as cement dispersant
Harumi Homma*1, Satoshi Kubo*2, Tatsuhiko Yamada*2, Keiichi Koda*3, Yasuyuki Matsushita*４, Kazuhiko
Fukushima*4, Yasumitsu Uraki*3*1Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, *2Department of Biomass
Chemistry, Forestry and Forest Products Research Institute, Tsukuba, 305-8687, Japan*3
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, *4Graduate School of
Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract:
Several polyethylene glycols were introduced to isolated lignins to prepare amphiphilic lignin
derivatives. Among them, a lignin derivative with dodecyloxy-polyethylene glycol glycidyl ether (DAEO)
showed as high surface activity as a commercially available surfactant. To use those derivatives as cement
dispersants, the dispersibility was evaluated. Although LS is actually used as a dispersant of cement, most lignin
derivatives showed much better dispersibilities than LS. In addition, the dispersibility of LS was dramatically
improved by the reaction with a small amount of DAEO. Thus, this study demonstrated that the amphiphilic
lignin derivatives in this study were useful for cement dispersants.
2009-P21
リグニン／PEO ポリマーブレンドの熱流動特性
久保智史*1、木口実*1、山田竜彦*1、堀沢栄*２、辻知宏*２、本間春海*3、浦木康光*3、John Kadla*4*1
森林総合研究所、*2 高知工科大学、*３北海道大学大学院農学研究科、*４University of Britisｈ Columbia
Thermal fluidity of the polymer blend of lignin and PEO
Satoshi Kubo*1, Makoto Kiguchi*1, Tatsuhiko Yamada*1, Sakae Horisawa*2, Tomohiro Tsuji*2 ,Harumi Homma*3,
Yasumitsu Uraki*3, John Kadla*4*1
Department of Biomass Chemistry, Forestry and Forest Products Research Institute. 1 Matsunosato Tsukuba,
Ibaraki, *2Kochi University of Engineering, *3Research Faculty of Agriculture, Hokkaido University, Sapporo
060-8589, Japan, *4University of Britisｈ Columbia
Abstract:
Thermal viscous behavior of the blends of alcohol lignin (AL) and PEO were examined using
thermo-mechanical analysis (TMA) and capillary viscometer. Both of the initiation temperature of the thermal
flow and thermal viscosity of AL was decreased by the blending with PEO. However,by contraries, that temperature and thermal viscosity was increased by the incorporation of excess
amount of PEO. Those thermal behaviors are good agreement with the changes in the thermal
formability of AL/PEO blend, such as thermal spinning temperature.
2009-P22500

バイオディーゼル燃料生産副産物グリセリンと工業リグニン由来原料からのポリウレタン誘導体の調製と物性
辻本泰人*1、鹿瀬重雄*2、畠山立子*3、島田幹夫*1、畠山兵衛*1*1
福井工業大学工学部、*2 産業技術総合研究所、*3 リグノセルリサーチ
Preparation and properties of polyurethane foams derived from industrial lignins and crude gycerin from BDF
industry
Yasuto Tsujimoto*1, Shigeo Hirose*2, Tatsuko Hatakeyama*3, Mikio Shimada*1, Hyoe Hatakeyama*1*1
Fukui University of Technology, 3-6-1, Gakuen, Fukui 910-8505, *2AIST, 1-1-4Higashi, Tsukuba, 305-8565,*3
Lignocell Research, 73-8, Yatsumata, Fukui 910-3558
Abstract:
Polyurethane (PU) foams were prepared using crude glycerin (CG) obtained as a by-product of
the biodiesel fuel (BDF) industry and lignosulfonate (LS) obtained as a by-product of the pulping industry. LS
and CG were dissolved in polyethyleneglyco1 (PEG), and two kinds of polyols LSP and CGP were prepared.
CG content was varied 0, 5, 10, 15, 20 % in polyols. The above polyols were reacted with poly(phenylene
methylene) polyisocyanate (MDI). Water was used as afoaming reagent. Apparent density of PU foams was in a range from 0.09 to 0.07 g cm-3. Compression strength(σ10) was in a range from 0.31 to 0.51 MPa. Scanning electron micrographs of the prepared PU foams were
examined.
2009-P23
木質系バイオマス糖化残漆を主成分とする低炭素型プラスチック充填材の製造に関する研究
松永興哲*1、坂西欣也*1、西本徹郎*2、平田雅章*2*1
産業技術総合研究所、*2 株式会社ジュオン
Research on the production of plastic filler by utilization of fermentation residue obtained from thewood-derived bio-ethanol production process
Kotetsu Matsunaga*1, Kinya Sakanishi*1, Tetsuro Nishimoto*2, Masayuki Hirata*2*1
National Institute of Advansed Industrial Science and Technology (AIST), AIST Chugoku, Suehiro 2-2-2, Hiro,Kure, Hiroshima 737-0197, Japan, *2JUON CO. Ltd., 1-28-7, Gion, Asaminami-ku, Hiroshima, 731-0138, Japan
Abstract:
In the production procedure of ethanol from woody biomass, about 60-80 wt% of fermentation
residue is produced on the base of wood feedstock. We produced the neat biomass- derived synthesized resin
complex from the mixed feedstock of the fermentation residue obtained from the wood-derived bio-ethanol
production process with glycerol and poly-lactic acid. In the evaluation of the biomass-derived synthesized resin
complex as plastic filler, its blending with
poly-propylene resin exhibited the better dispersion compatibility and processing performance compared tothose produced from the crude saccharification residue. In addition, the melting viscosity of the complex resin
was not affected so much by its addition, keeping the stable processing performance, while the addition of thecrude residue considerably increased the viscosity.
2009-P24
リグニンからの紫外線吸収剤の開発
内藤喜之*1、大橋康典*1、吉岡康一*1、渡辺崇人*1、本田与一*1、渡辺隆司*1、菅原智*2、小池謙造*2
京都大学生存圏研究所、花王株式会社
Development of ultraviolet absorbers from lignin
Yoshiyuki Naito*1, Yasunori Ohashi*1, Koichi Yoshioka*1, Takahito Watanabe*1, Yoichi Honda*1, Takashi
Watanabe*1, Satoshi Sugawara*2, Kenzo Koike*2*1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan,*2
Kao Corporation, 2-1-3 Bunka, Sumidaku, Tokyo 131-8501, Japan
Abstract:
Currently, ultraviolet absorbers are becoming popular due to cosmetic and medical purposes.
Exposure of skins to ultraviolet rays from the sun causes damage of the skins. Excessive exposure induces skincancer and aging. Although the demand for UV absorbers with high safety and minimum environmental impact
is becoming increasing, most of the organic UV absorbers currently available are synthetic compounds frompetroleum. Therefore, we started the research to develop UV absorbers &om natural aromatic polymer, lignin.
By extensive screening of degradation products from lignin, we found the products having high absorbance in
UV A and UV B regions.

501

第 55 回 （2010.10.20-21） 京都大学 百週年時計台記念館
2010-101
イネ節間の細胞壁成分合成が異常になる d50 変異体の解析と D50 遺伝子の同定
佐藤かんな*1、中野仁美*1、西窪伸之*2、田村克徳*3、半 智史*4、船田良*4、梶田真也*1、
芦苅基行
*5
*5
*6
、北野英己 、片山義博*1
東京農工大学大学院 BASE、*2 王子製紙株式会社、*3 九州沖縄農研究センター、*4 東京農工大学大学院農学研究院、*5 名古屋大学大学院 BBC, *6 日本大学生物資源学部
Histochemical analysis of rice d50 mutant internodes exhibiting abnormal synthesis of cell wall materials andisolation of D50 gene
Kanna Sato*1, Yoshimi Nakano*1, Nobuyuki Nishikubo*2, Katsunori Tamura*3, Satoshi Nakaba*4, Ryo Funada*4,
Shinya Kajita*1, Motoyuki Ashikari*5, Hidemi Kitano*5, Yoshihiro Katayama*6*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan, *2Forestry Research Institute, Oji Paper
Company Limited, 24-9 Nobono-cho, Kameyama, Mie 519-0212, Japan, *3National Agricultural ResearchCenter for Kyushu Okinawa Region, 496 Izumi, Chikugo, Fukuoka, 833-0041, Japan, *4Graduate School of
Agriculture, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8538, Japan, *5Bioscience andBioteclmology Center, Nagoya University, Furo-cho, Nagoya, Aichi 464-8601, Japan. *6College of Bioresource
Sciences, Nihon University, 1866 Kameino, Fujisawa, Kanagawa 252-0880, Japan
Abstract:
Previously, we reported that parenchyma cells in the elongated internodes of Fukei 71 (d50mutant) ectopically deposit grass-specific cell wall material, polysaccharide-linked hydroxy- cinnamoyl esters.
Through map-based cloning, we revealed that the D50 encodes putative inositol polyphosphate 5-phosphatase,which may be involved in phosphoinositide signaling pathways required for many essential cellular functions
including cytoskeleton organization, endocytosis and vesicular trafficking in eukaryotes. Further analyses of d50
phenotype revealed that the d50 mutation induced abnormally oriented cell division, ectopic deposition of cellwall pectins and thick actin bundles in the parenchyma cells of the intercalary meristem.
2010-102
Sphingobium sp．SYK−6 株由来の ligD 遺伝子を発現する遺伝子組換え植物の作出と解析
石川靖之*1、大浦良*1、辻幸子 *1、上杉幹子*1、佐藤かんな*1、片山義博 *2、原啓文 *3、菱山正二郎*4、政井英
司*5、梶田真也*1*1
東京農工大学大学院 BASE、*２日本大学生物資源学部、*３岡山理科大学工学部、*４森林総合研究所、*５長岡技術科学大学工学部
Generation and analysis of transgenic plants with ligD gene isolated from Sphingobium sp. SYK-6
Yasuyuki Ishikawa*1, Ryo Oura*1, Yukiko Tsuji*1, Mikiko Uesugi*1, Kanna Sato*1, Yoshihiro Katayama*2,
Hirofumi Hara*3, Shojiro Hishiyama*4, Eiji Masai*5, Shinya Kajita*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, *2College of Bioresource Sciences, Nihon University, Kanagawa,
252-0880, Japan, *3Department of Biomedical Engineering, Okayama University of Science, Okayama
700-0005, Japan, *4Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan, *5Department of
Bioengineering, Nagaoka University of Technology, Niigata 940-2188, Japan
Abstract:
Sphingobium sp. SYK-6 can catabolite various types of phenolic compounds including
monolignols, their precursors and lignin dimers. Several genes involved in the catabolism of these compounds
have been isolated from this strain in our previous studies. For modification of lignin biosynthesis in plant cell,
we focus on ligD gene, which encodes Cα dehydrogenase for first step of cleavage of ether bond in compoundswith β-O-4 bond. After optimization of codon usage of the gene for efficient expression, we introduced amodified ligD gene into tobacco BY-2 cells and Arabidopsis plants. Characterization of the transgenic cells andplants will be discussed.
2010-103
高機能性微生物による木質バイオリファイナリー 〜Phanerochaete sordida YK−624 株におけるリグニン分解
性ペルオキシダーゼと 5−アミノレプリン酸シンターゼの関係〜
三隅健太*1、渡辺裕也*1、平井浩文*1、河岸洋和*1*2、亀井一郎*3、森智夫*4、近藤隆一郎*4*1
静岡大学農学部、*2 静岡大学創造科学技術大学院、*3 宮崎大学農学部、*4 九州大学大学院農学研究院
Woody biorefinery with functional microorganisms. — Relationship between ligninolytic peroxidases and502

5-aminolevulinic acid synthase in Phanerochaete sordida YK-624 —Kenta Misumi*1, Yuya Watanabe*1, Hirofumi Hirai*1, Hirokazu Kawagishi*1*2, Ichiro Kame*3i, Toshio Mori*4,
Ryuichiro Kondo*4*1
Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, *2Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan, *3Faculty of Agriculture, University of Miyazaki,
Miyazaki 889-2192, Japan, *4Faculty of Agriculture, Kyushu University, University, Fukuoka 812-8581, Japan
Abstract:
To overproduce ligninolytic peroxidases (manganese peroxidase (MnP) and novel lignin
peroxidase) in Phanerochaete sordida YK-624, the gene of 5-aminolevulinic acid synthase (ALAS), aas, isinvolved in the production of 5-aminolevulinic acid which is the rate-limiting step in the biosynthesis of heme,
was cloned. The deduced amino acid sequence of aas showed highest identity (93.0%) with ALAS from P.
chrysosporium ME-446. The promoter of glyceraldehyde-3- phosphate dehydrogenase (GPD) gene cloned from
P. sordida YK-624 was used to drive the expression of aas. The expression vector was transformed into a P.
sordida YK-624 uracil auxotrophic mutant, UV-64. Three transformants showed high MnP activities comparedwith control transformants into which only ura5 was introduced.
2010-104
高機能性微生物による木質バイオリファイナリー 〜新規リグニン分解特異的プロモーターを用いた超高活性リグニン分解菌の分子育種〜
杉浦立樹*1、三隅健太*2、渡辺裕也*2、平井浩文*2、河岸洋和*1*2、亀井一郎*3 、森智夫*4、
近藤隆
*4
一郎
*1
静岡大学創造科学技術大学院、*2 静岡大学農学部、*3 宮崎大学農学部、*4 九州大学大学院農学研究院
Woody biorefinery with functional microorganis. Molecular breeding of superior lignin-degrading fungi usingnovel ligninolytic condition-specific promoter
Tatsuki Sugiura*1, Kenta Misumi*2, Yuya Watanabe*2, Hirofumi Hirai*2, Hirokazu Kawagishi*1*2, Ichiro Kamei*3,
Toshio Mori*4, Ryuichiro Kondo*4*1
Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan, *2Faculty ofAgriculture, Shizuoka University, Shizuoka 422-8529, Japan, *3Faculty of Agriculture, University of Miyazaki,
Miyazaki 889-2192, Japan, *4Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan
Abstract:
BUNA2 is one of high produced proteins from hyper lignin-degrading fungus Phanerochaete
sordida YK-624 under wood-rotting condition. In the transcriptional analysis, the gene of BUNA2 (bee2) was
stably and strongly transcribed during 20 days cultivation in beach wood meals. A promoter region of bee2
(bee2 promoter) was cloned using TAIL PCR and inverse PCR method. The obtained promoter was used todrive the expression of Lip gene (ylpA) or MnP gene (mnp4), and these plasmids (pBUNA2pro-ylpA andpBUNA2pro-mnp4) were constructed. Protoplasts of UV-64 were mixed with DNA solution containing
pBUNA2pro-ylpA, pBUNA2pro- mnp4 and pPsURA5, and co-transformed by PEG method. With the same
method, DNA solution containing pBUNA2pro-ylpA and pPsURA5, and pBUNA2pro-mnp4 and pPsURA5
were co-transformed respectively. We obtained 17 of ylpA & mnp4-introducing clones, 9 of ylpA- introducing
clones, and 14 of mnp4-introducing clones.
2010-105
高機能性微生物による木質バイオリファイナリー 〜新規糖化酵素産生微生物の探索〜
亀井一郎*1、森智夫*2、平井浩文*3、目黒貞利*1、近藤隆一郎*2*1
宮崎大学農学部、*2 九州大学大学院農学研究院、*3 静岡大学農学部
Woody biorefinery with functional microorganisms—Screening of functional saccharification
enzyme-producing microorganisms—
Ichiro Kamei*1, Toshio Mori*2, Hirofumi Hirai*3, Sadatoshi Meguro*1, Ryuichiro Kondo*2*1
Faculty of Agriculture, University of Miyazaki, *2Faculty of Agriculture, Graduate School of Kyushu
University, *3Faculty of Agriculture, Shizuoka University,
Abstract:
To isolate functional saccharification enzyme-producing bacteria, a decayed wood-pulp
perfusion system was developed and applied. An enrichment culture in decayed wood-pulp perfusion system
contained at least ten bacteria after two month perfusion and then two strains (E814-1 and E814-2) were isolated
as cellulase-producing microorganisms. Among them, strain E814-2 was identified as Paenibacillus sp. using
16S rDNA sequencing and this strain closely related to Paenibacillus curdlanolyticus which was reported
recently as multienzyme complex (cellulosome)- producing bacteria. This result indicates that pulp perfusion
system is a useful method for isolate saccharification enzyme-producing bacteria. Additionally, to identify
potential enzymes from nonculturable microbes, metagenomic libraries were constructed from several503

lignocellulose-rich environments. Around 7.5 kbp eDNAs were successfully cloned and applied to plate assay
for screening.
2010-106
リグニン分解酵素による医薬品類の除去
新館秀章、畑貴之、河合真吾、西田友昭
静岡大学農学部
Elimination of pharmaceutically active compounds by ligninolytic enzymes
Hideaki Shintate, Takayuki Hata, Shingo Kawai, Tomoaki Nishida
Department of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka
University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
Carbamazepine (CBZP) is used as an antiepileptic drug and is highly persistent. In this study,
CBZP was treated with manganese peroxidase (MnP), laccase and the laccase-mediator system with
1-hydroxybenzotriazole (HBT). The laccase-HBT system is most effective in eliminating CBZP among the three
enzymatic treatments. A single treatment with laccase and HBT eliminated CBZP by about 22% after 24 h, andrepeated treatments with laccase and HBT, which were added to the reaction mixture every 8 h, helped eliminate
about 60% of CBZP after 48 h. This suggests that repeated treatment is effective in eliminating CBZP. Mass
spectrometricanalysesdemonstrated
that
twodegradation
products
of
CBZP,10,11-dihydro-10,11-epoxycarbamazepine and 9(10H)-acridone, were formed via repeated treatment withlaccase and HBT. Furthermore, theanti-inflammatory drug indomethacin (IMC) was also treated with MnP, laccase and the laccase- HBT system.
MnP and the laccase-HBT system almost completely eliminated IMC after 4 h of treatment, suggesting thatthese two enzymatic treatments are effective in eliminating IMC.
2010-107
Bioremediation of DDT by Pleurotus ostreatus spent mushroom waste: involvement of ligninolytic enzymes
and application in historically contaminated soil
Adi Setyo Purnomo*1*2, Toshio Mori*1, Eri Takata*1, Kazuhiro Takagi*3, Yuji Tsutsumi*1, Ryuichiro Kondo*1*1
Department of Agro-environmental Sciences, Faculty of Agriculture, Kyushu University, *2Department ofChemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Sepuluh Nopember, Indonesia.
*3
National Institute for Agro-environmental Sciences.
Abstract:
In our previous work, spent mushroom waste (SMW) of Pleurotus ostreatus (Hiratake) was
shown to have high ability to degrade and mineralize DDT (1,1,1-Trichloro-2,2-bis(4-chloro- phenyl)ethane) inartificially contaminated soil. In present study, SMW of Hiratake was applied to thehistorically contaminated soil which collected from pesticide manufacturing site in Japan. DDT
concentration in the historically contaminated soil is 0.4 mmol/g dry weight of soil. After 28 days
incubation, approximately 70% of DDT was degraded compared with autoclave-killed control.
Degradation mechanisms especially involvement of ligninolytic enzymes were investigated. SMWof Hiratake has 0.26, 1.90, and 0.13 mmol/min/ml of laccase, MnP, and LiP activities, respectively.
High MnP activity suggested MnP seems a key enzyme for degradation of DDT. DDT was treatedwith purified MnP, and DDD (1,1-dichloro-2,2-bis-(4-chlorophenyl) ethane) and DBP(4,4-dichlorobenzophenone) were detected as metabolic products.
2010-108
白色腐朽菌 Phlebia 属菌によるクロルデンの処理
肖 鵬飛*1*2、森 智夫*3、近藤隆一郎*3*1
九州大学大学院生物資源環境科学府、*２東北林業大学、*3 九州大学大学院農学研究院
Biodegradation of chlordane by white rot fungi, Phlebia genus
Pengfei Xiao*1*2, Toshio Mori*3, Ryuichiro Kondo*3*1
Graduate School of Bioresource and Bioenvironmental Sciences, Kyushu University, 6-10-1 Hakozaki,
Higashi-ku, Fukuoka 812-8581, Japan, *2College of Forestry, Northeast Forestry University, Harbin 150040,
China, *3Graduate School of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581,
Japan,
Abstract:
The organochlorine pesticide, chlordane was used as the substrate for degradation experimentwith the white rot fungi Phlebia lindtneri, Phlebia brevispora and Phlebia aurea, which are capable ofdegrading dieldrin, heptachror and heptachlor epoxide. Pure culture of fungi with chlordane (0.25mmol/flask)504

showed that over 50% of chlordane disappeared in Kirk (LN) medium and PDB medium after 42-day
incubation period. Chlordane was biotransformed to heptachlor, heptachlor epoxide, dichlorochlordene,
oxychrordane and several hydroxylated metabolites, which have not been reported as bacterial metabolite.
1-aminobenzotrjazole and piperonyl butoxide strongly inhibited the degradation of chlordane and concomitant
accumulation of metabolites, indicating cytochrome P450 mediated metabolism.
2010-109
C heavy oil degradation in sea water liquid medium by Fusarium sp. F092
Asep Hidayat, Kazutaka ltoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Oil contamination have became serious problem in environmental generated via several
accident on production. Experiments were carried out to evaluate the ability of Fusarium sp. F092 to degrade C
heavy oil on sea water liquid medium. The strain F092 grew 0.41 cm/day on potato glucose (PG) agar medium
containing C heavy oil. C heavy oil used in our experiment contained 44% of aliphatic, 31% of aromatic, 8% of
nitrogen, sulfur and oxygen (NSO) and 17% of asphaltene. At 60 days incubation, degradation of C heavy oil bystrain F092 fungus was obtained at the level 77% on those aliphatic and aromatic fractions, and 56 % of total
petroleum hydrocarbon (TPH) degradation. The effect of manganese (Mn) addition, could increase 20% of TPH
degradation, those are 75% of (NSO) and 31% of asphaltene. The highest activity of manganese peroxidase andlaccase reached at 69 UI-1 and 49 UI-1 on 20 days, while 1,2- and 2,3-dioxygenase showed the highest level after
20 days.
2010-110
Degradation of 2,4,8-Trichlorodibenzofuran by fungi selected from nature
Ajeng Arum Sari, Kazutaka ltoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
Dioxin can be serious problem for environmental because of its strong toxicity andmutagenicity. White rot fungi are well known for their outstanding ability to produce extracellularoxidative enzymes, which are involved in the degradation of either lignin than a wide range of pollutants
include dioxins. Fungus U97 screened from nature had ability to degrade 2,4,8-TCDF by
43%, on 15 days and 61%, on 30 days, respectively. The maximum enzyme activity of strain U97
during 2,4,8-TCDF degradation was 1,2-dioxygenase (262.8 UI-1) and Lip (93.6 UI-1). Carbon
source, surfactant and agitation have no negative effect on the growth of U97 during biodegradationof 2,4,8-TCDF on 15 and 30 days. The finding suggest that U97 can metabolize 2,4,8-TCDF to 3,5dichlorosalicylic acid.
2010-111
白色腐朽菌由来の酵素および酵素製剤を用いたアゾ染料の分解
大森元樹、伊藤和貴、橘 燦郎
愛媛大学農学部
Degradation of azo dyes with a crude enzyme and immobilized enzyme from white rot fungi
Motoki Omori, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University
Abstract:
To purify effluents from textile industry, food industry and so forth, degradation of three kindsof azo dyes, Reactive Red (RR4), Reactive Black 5 (RB5) and Reactive Green 19 (RG19) was conducted byusing a crude enzyme and immobilized enzyme from a white rot fungus, PL1. Degradation rate of the dyes by
the crude enzyme in liquid medium was about 20 to 87 %. However, the degradation rate was increased to about
90 to 95% by addition of Tween 80. On the contrary, degradation rate of the dyes by the immobilized enzyme(double capsule) in the medium was about 80 to 93%. To conduct the degradation of the dyes using bioreactor
packed with the double capsule, effects of flow rate on degradation of the dyes were investigated. It was foundthat the degradation rate was increased when the flow rate became faster, or the treatment time got longer. The
maximum degradation rate of RG19 was 95% when the treatment was conducted for 48 hours at 7.0/min.
2010-112
シロイヌナズナ T87 培養細胞のリグニン分析
山村正臣*1、和田将平*1、榊原和紀*1*2、中坪朋文*1、鈴木史朗*1*3、服部武文*1、竹田みぎわ*４、桜井望*４、鈴木秀幸*4、柴田大輔*4、梅澤俊明*1*3
505

*1

京都大学生存圏研究所、*2 徳島文理大学、*３京大生存基盤科学研究ユニット、*4 かずさ DNA 研究所
Lignin analyses of Arabidopsis thaliana T87 cells
Masaomi Yamamura*1, Shohei Wada*1, Kazunori Sakakibara*1*2, Tomoyuki Nakatsubo*1, Shiro Suzuki*1*4,
Takefumi Hattori*1, Migiwa Takeda*4, Nozomu Sakurai*4, Hideyuki Suzuki*4, Daisuke Shibata*4, Toshiaki
Umezawal*1*3*1Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011,*2
Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, Sanuki, Kagawa
769-2193, *3Institute of Sustainability Science, Kyoto University, Uji, Kyoto 611-0011, *4Kazusa DNA ResearchInstitute, Kisarazu, Chiba 292-0818
Abstract:
Arabidopsis thaliana is the most widely used model plant in the area of plant bioscience sector.
T87 is one of the typical lines of A. thaliana cultured cells. This cell line has various advantages in the researchof plant metabolism, as well as intact A. thaliana plants. However, nothing is known about the lignins of T87
cells. In this study, we characterized lignins of T87 cells using six lignin analytical methods,
phloroglucino1-hydrochloric acid staining, thioacidolysis, nitrobenzene oxidation, alkaline hydrolysis, andKlason and acetyl bromide methods. These analyses clearly showed that lignins of T87 cells are composed of
guaiacyl and p-hydroxyphenyl units, and are quite different from lignin found in the A. thaliana inflorescencestem, which are composed of guaiacyl and syringyl units.
2010-113
The finding and characterization of hindered LCC by the fractionation of wood cell wall components using
LiCl/DMSO system
Zhiguo Wang, Takuya Akiyama, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, Tokyo, Japan
Abstract:
The fractionation of wood cell wall components was achieved by the application of the
LiCl/DMSO solvent system developed in our previous study. Various soluble and insoluble fractions wereprepared from beech milled wood by extractions with DMSO containing different amounts of lithium chloride(LiCl) for the study of lignin-carbohydrate complex (LCC). Nitrobenzene oxidation (NO) analyses
demonstrated that the lignin in the soluble fractions always has lower yields of NO products consisting ofsyringaldehyde + syringic acid (S) and vanillin + vanillic acid (V). The syringyl ratios, S/(S+V), were also
lower than in insoluble fractions. Accordingly, lignins with lower syringyl ratios are better soluble than thosewith higher ones. The former is typical in primary wall and the latter in secondary wall. Solubilization of glucan
is significantly dependent on the LiCl concentration in DMSO. In the absence of LiCl, only about 6% of glucan
was found in the soluble fraction, but about 40% of lignin and xylan were solubilized. The additional 40% of
lignin and xylan became soluble together with glucan solubilization by the addition of LiCl up to 3%
concentration. However, a fraction amounting to 13% (based on the whole wood) is still remained as a residue
under these conditions. Glucan solubilization could not be the reason for this observation as ball-milledcellulose is soluble in 3% LiCl/DMSO. Probably, strong interactions between lignin and carbohydrates prevent
solubilization of this fraction, which is denominated here as "hindered LCC", that has never been isolated andanalyzed in previous studies. The "hindered LCC" contains non-condensed-type lignin and featured by strong
interactions between lignin, hemicelluloses, and cellulose. On the other hand, Björkman LCC, which is obtained
when LiCl concentration is O%, is rich in condensed-type lignin and characterized by interactions between
lignin and hemicelluloses.
2010-114
Relationships between hemicellulose composition and lignin structure of LCC fractions
Yu Huang*1*2, Zhiguo Wang*1, Linshan Wang*2, Yuesheng Chao*2, Takuya Akiyam*1a, Tomoya Yokoyama*1, Yuji
Matsumoto*1*1
Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, the University ofTokyo, *2School of Sciences, Northeastem University, China
Abstract:
New fractionation method of wood cell wall components was applied to selected wood species(beech and red pine). Finely ground wood meal was first extracted by aq dioxane and DMSO to obtain
conventional Björkman lignin and LCC. The residue was then subjected to successive extraction by DMSO withincreasing content of LiC1 (0.5 to 3.0%). Relationships between lignin structure and carbohydrates in obtained
fractions were examined. Syringyl ratio of soluble fractions was always lower than that obtained forcorresponding insoluble fractions. It was confirmed that MWL represents very specific part of whole lignin.
With the increase of LiCl concentration of the extraction solvent, the lignin content and weight ratio of506

hemicellulose in sugars decreased, and weight ratio of cellulose in sugars increased.
2010-115
高 CO２下で生育した樹木の細胞壁構成成分の評価
白河 学*1、斎藤香織*1、渡辺陽子*2、渡辺 誠*3、船田 良*3、小池孝良*2、福島和彦*1
名古屋大学大学院生命農学研究科、北海道大学大学院農学研究科、東京農工大学大学院共生科学技術研究院
Evaluation of wood cell wall component growing under elevated CO2
Manabu Shirakawa*1, Kaori Saito*1, Yoko Watanabe*2, Makoto Watanabe*2, Ryo Funada*3, Takayoshi Koike*2,
Kazuhiko Fukushima*1*1
Graduate School of bioagricultural Science, Nagoya University, Nagoya, 464-8601, *2Graduate School of
Agriculture, Hokkaido University, Sapporo 060-8589, *3Institute of Symbiotic Science and Technology, Tokyo
University of Agriculture and Technology, Fuchu, 183-8509
Abstract:
Chemical characterization of the wood which was grown under free air CO2 enrichment (FACE)
was investigated. We focused on lignin to detect the effect of increasing atmospheric concentration of CO 2 towood material. We characterized lignin using the acetylbromide method for lignin content and the thioacidolysis
to examine the syringyl/guaiacyl (S/G) monomer ratios. The results show no significant difference between
FACE and control samples, which indicates elevated CO2 environment would not induce the change of lignin
content, S/G monomer ratios.
2010-116
木質バイオマスリファイナリーのための高分解能質量分析法の開発
吉岡康一*1、岸本崇生*2、渡連崇人*1、本田与一*1、渡辺隆司*1*1
京都大学生存圏研究所、*2 富山県立大学工学部
Development of high-resolution mass spectrometry for woody biomass refinery
Koichi Yoshioka*1, Takao Kishimoto*2, Takahito Watanabe*1, Yoichi Honda*1, Takashi Watanabe*1*1
Research Institute for Sustainable Humanosphere, Kyoto Universiy, Gokasho, Uji, Kyoto 611-0011, Japan,
Faculty of Engineering, *2 Toyama Prefectural University, Imizu 939-0398, Japan
Abstract:
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI- TOFMS) gives direct structural information in a wide range of molecular mass regions. However, reports on the
structural analysis of lignin by MALDI-TOF MS are still limited. In this study, milled wood lignin (MWL) fromJapanese ceder, Fagus crenata and Eucalyptus globulus wood were analyzed MALDI-TOF MS. The mass
spectrometry provided peaks of the lignin including those characteristic to βO-4 linkage, a major linkage
among monomeric units in lignin. The mass spectrometry is useful for woody biomass refinery, especially forstructure-based utilization of lignin.
2010-117
HSQC NMR analysis of bamboo lignin and bamboo cell walls
Qu Chen, Takao Kishimoto, Shinjiro Ogita, Masahiro Hamada, Noriyuki Nakajima
Bioorganic Chemistry Lab, Department of Biotechnology, Toyama Prefectural University, 5180 Kurokawa,Imizu, Toyama, Japan
Abstract:
In situ acetylated mature and immature hachiku bamboo (Phyllostachys nigra Munro var.
Henonis) cell walls were characterized by 1H-13C correlation heteronuclear single quantum coherence (HSQC)
NMR spectroscopy. The lignins from mature and immature bamboo were also isolated in order to assign thelignin fraction. The HSQC spectrum of immature bamboo lignin and plant cell walls can help studying thelignification of bamboo.
2010-特別講演
リグニン利用の現状と将来展望
西盛嘉人
日本製紙ケミカル株式会社開発研究所
The current industrial applications of the lignin and its prospect
Yoshito Nishimori
Research and Development Laboratory, Nippon Paper Chemicals Co. Ltd., 2-8-1, Iidamachi, Iwakuni,
Yamagichi 740-0003 Japan
507

Abstract:
Commercial lignin is produced as a co-product of the pulp industry. Lignins are products ofKraft and Sulfite pulping process. The Kraft lignin is mainly used as a fuel through a recovery boiler. On theother hand, the lignosulfonate generated from the Sulfite pulping process is used as a concrete admixture, binderand for other applications due to its dispersing, binding, complexing and emulsifying properties. This
presentation will introduce the current industrial applications of the lignin. Furthermore, new possible
applications such as a raw material for bio-refineries are discussed as well.
2010-201
リグニンモデル化合物の間接電解酸化反応（3） —β-O-4 モデルオリゴマーの NHPI 間接電解—
白石 匠、上高原 浩、高野 俊幸、中坪 文明
京都大学大学院農学研究科
Indirect electrooxidation of lignin model compounds (3) — NHPI-mediated indirect electrooxidation of -O-4
model oligomers —Takumi Shiraishi, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University,
Sakyo-ku. Kyoto, 606-8502, Japan
Abstract:
Indirect electrooxidation of β-O-4 type oligomeric lignin model compound using
N-hydroxyphthalimide PHPI) as an mediator was studied to introduce carbonyl group at α-position. It wassuggested from the NMR data of the electrolysis products that carbonyl group was introduced to α-position of
the oligomer in 68-84% yield. These results suggest that NHPI-mediated indirect electrooxidation is an effective
method for α-carbonylation of natural lignin structures.
2010-202
イオン液体中でのリグニンモデルおよびリグニンの構造変化
久保智史、橋田光、山田竜彦、菱山正二郎、細谷修二
森林総合研究所
Structure changes of lignin model compounds and lignin preparations in ionic liquids
Satoshi Kubo, Koh Hashida, Tatsuhiko Yamada, Shojiro Hishiyama, Shuji Hosoya
Department of biomass chemistry, Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba,
Ibaraki, Japan
Abstract:
To examine the structure changes of lignin in ionic liquids (IL), MWL was treated with IL under
the heat conditions. After IL treatments, some portions of MWL were recovered as water soluble fractions. In
FT-IR analysis, the band assigned to conjugated carbonyl groups, which was clearly detected for original MWL,
were dramatically decreased by the IL treatment. 1H-NMR estimated the differences in the side-chain structures
between the water insoluble fractions and original MWL. In this presentation, we will discuss the structurechanges of lignin preparations in ILs by comparing them with those of lignin model compounds.
2010-203
活性酸素種との反応における非フェノール性リグニンモデル化合物のベラトリル芳香環と側鎖水酸基の位置の影響について大村知士、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Effect of veratryl aromatic ring and location of side chain hydroxyl group on the reaction of non-phenolic lignin
model compounds with active oxygen species
Satoshi Ohmura, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo
Abstract:
Each of a non-phenolic β-O-4 type dimeric lignin model compound, 2-(3,5-difluorophenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (VDF), or a β-O-4 type model compound,
2-(3,5-difluorophenoxy)propane-1,3-diol or 3-(3,5-difluorophenoxy)propane-1,2-diol, was subjected to anoxygen alkaline treatment in the presence or absence of a generator of active oxygen species (AOS),
4-hydroxy-3-methoxybenzyl alcohol (VA). AOS are generated by the reaction of VA with oxygen. The
incorporation of 3,5-difluorophenoxyl group in the structure of the model compounds is to detect
3,5-difluorophenol (DFPh) when DFPh is liberated from the model compound during the treatment. It wassuggested that AOS attack the side chain of VDF and non-phenolic 3,5-difluoro- phenoxyl group in VDF is508

converted to DFPh, a phenolic compound. The effect of existences of veratryl aromatic ring, benzyl hydroxyl
group, and secondary hydroxyl group on the reaction of the model compounds with AOS is also discussed.
2010-204
過酸化水素−アルカリ処理におけるシリンギルおよびグアイアシルリグニンモデル化合物の分解の比較
石川裕剛、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Comparison of the degradation of syringyl and guaiacyl type lignin model compounds in alkaline hydrogen
peroxide treatment
Yugo Ishikawa, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
Non-phenolic lignin model compounds, 1-(3,4-dimethoxyphenyl)ethane-1,2-diol (G),
1-(3,4,5-trimethoxypheny1)ethane-1,2-diol (S),1,2-dimethoxybenzene (G'), and 1,2,3-trimethoxy- benzene (S'),
were reacted with hydroxyl (HO•) and oxyl anion (O•–) radicals, which were generated by the decomposition ofhydrogen peroxide under alkaline conditions bH 12.0, 70Qc). The degradation of G was not very different fromthat of S, which suggests that the difference in the aromatic structure does not have significant influence on thereaction. The degradation of G' was clearly greater than that of S' but much smaller than those of G and S. These
results suggest that the side chains of G and S are predominantly attacked by O•– (and HO•) and that highelectron density of aromatic ring interferes with the reaction with O•– (and HO•).
2010-205
半流通型２段階加圧熱水処理によるブナ由来水可溶性リグニンの分析
山内一慶、河本晴雄、坂 志朗
京都大学大学院エネルギー科学専攻科
Characterization of water-soluble lignin-derived products from Japanese beech as treated by semi-flow two-step
hot-compressed water
Kazuchika Yamauchi, Haruo Kawamoto, Shiro Saka
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
Japanese beech was treated by two-step semi-flow hot-compressed water (1st stage:
230ºC/10MPa/15min, 2nd stage: 270ºC/10MPa/15min). Interestingly, 34.4% of lignin was recovered in thewater-soluble portion at the 1st stage. In order to characterize lignin-derived products, the water-soluble portion
at the 1st stage was extracted with ethyl acetate, and ethyl acetate layer and water layer were separated. UVabsorption which is characteristic of aromatic ring was detected in both the water layer and the ethyl acetate
layer. Some mono-saccharides were detected from the ethyl acetate layer after hydrolysis. These results may besuggested that some lignin-derived products at the lst stage were related with saccharides from hemicelluloses,
it is likely lignin- carbohydrate complex (LCC).
2010-206
リグニン熱分解中間体としてのカテコール、ピロガロール、クレゾール、キシレノール類の熱分解反応
モハメド・アスマディ、河本晴雄、坂 志朗
京都大学大学院エネルギー科学専攻科
Pyrolysis reactions of catechols, pyrogallols, cresolS and xylenols as lignin pyrolySis intermediates
Mohd Asmadi, Haruo Kawamoto, Shiro Saka
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University,
Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
Abstract:
Secondary reactions of lignin pyrolysis intermediates were studied with a closed ampoule
reactor under N2 at 600ºC for 40-600 s. Two types of the intermediates were used; catechols and pyrogallols as
products of O-CH3 homolysis pathway; cresols and xylenols as those of OCH3 rearrangement pathway. As aresult, it was found that additional OH and CH3 (especially OH) on phenol increase the reactivity, althoughphenol was fairly stable under the present conditions. Accordingly, O-CH3 homolysis products especiallysyringyl-characteristic pyrogallols were more effectively converted into the gaseous products, mainly CO, evenat short heating time as 120 s. On the other hand, the OCH3 rearrangement products were comparatively stableand formed CH4 and H2 with coke at longer heating time as 600 s. Selective demethylation at the o- andp-position to phenolic OH was also observed in cresols, xylenols and trimethylphenol. A two step mechanism509

was proposed for this demethylation, which include radical coupling of H and C-centered radicals (o- or
p-position) formed from the phenoxy radical intermediates and the following C-CH3 homolysis. This isconfirmed with the calculated BDEs (-60 kcal/mol) of the C-CH3 bonds in the coupling products. Based onthese results of intermediates pyrolysis, pyrolysis reactions of guaiacol and syringol are discussed.
2010-207
アルカリ処理クラフトリグニンのアルミニウムとの錯体形成能およびその毒性除去能に対するフェノール性水酸基の寄与に関する研究
相見 光*1、栗本康司*1、山内 繁*1、池田 努*2、眞柄謙吾*2*1
秋田県立大学木材高度加工研究所、*2 森林総合研究所
Studies on contribution of phenolic hydroxyl groups in kraft lignin to complexation with aluminum andreducing its toxicity
Hikaru Aimi*1, Yasuji Kurimoto*1, Shigeru Yamauchi*1, Tsutomu Ikeda*2, Kengo Magara*2*1
Institute of Wood Teclmology, Akita Prefectural University, 11-1 Kaieisaka, Noshiro, Akita 016-0876, Japan,*2
Department of Biomass Chemistry, Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba,
Ibaraki 305-8687, Japan
Abstract:
Contribution of phenolic hydroxyl groups, including catechol type structures, in alkalinetreated kraft lignin to forming complex with aluminum and reducing its toxicity was examined in this study. The
soda-cooked lignin, which was shown to be effective in reducing aluminum toxicity and forming aluminumcomplex, was also used. The results obtained in this study indicate that contribution of catechol structures inalkaline-treated kraft lignin and soda-cooked lignin to forming complex with aluminum was insignificant.
Phenolic hydroxyl groups in alkaline-treated kraft lignin may contribute indirectly to forming complex withaluminum and reducing its toxicity by increasing its water solubility.
2010-208
Effect of residual lignin in alkali pulps on enzymatic hydrolysis of cellulose
Yi Zhang, Shiho Takahashi, Hiroshi Ohi, Keiichi Nakamata
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Japan, Technical &Development Division, Hokuetsu Paper Mills, Ltd., Japan
Abstract:
Alkaline sulfite-anthraquinone (AS-AQ) cooking was applied to the pretreatment for enzymatichydrolysis of cellulose of Japanese larch (Larix leptolepis) heartwood. We changed the ratio of Na2SO3 in thecooking liquors, and found that the 40% ratio of Na2SO3 at chips cooking had the capability of acquiring a highpulp yield and the lowest lignin content compared to others. During the hydrolysis of AS-AQ pulps, the content
of glucose hydrolyzed in the enzymatic hydrolysate of a pulp containing a small amount of lignin was higher
than that of a pulp containing a large amount of lignin at any cellulase charges (Filter paper cellulase unit: FPU).
We determined the enzyme adsorption to the pulps by pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS).
2010-209
セルロースの芳香族ヒドロキシ酸エステルにおける熱的特性と液晶性
石井大輔、中川瑞己、林久夫
龍谷大学理工学部
Thermal and liquid crystalline properties of cellulosic aromatic hydroxyl acid esters
Daisuke Ishii, Mizuki Nakagawa, Hisao Hayashi
Faculty of Science and Technology, Ryukoku University, 1-5 Yokotani, Seta Oe-cho, Otsu-shi, Shiga 520-2194,
Japan
Abstract:
Liquid crystalline properties of esterification products of cellulose and gallic acid were
investigated. Cellulose gallate formed liquid crystalline mesophase on heating between 220 and 230ºC. As agallic acid molecule possesses three hydroxyl and one carboxyl groups, polycondensed
gallic acids as side chain of cellulose can form hyperbranched structure. The thermotropic liquid crystallinity ofcellulose gallate is attributed to the hyperbranching nature of poly(gallate) side chains that can interrupt theinteraction between cellulosic backbones.
2010-210
リグノスルホン酸／ポリビニルアルコール複合ゲルの調製とキャラクタリゼーション
仲西雄亮，寺本好邦，西尾嘉之
510京都大学大学院農学研究科
Preparation and characterization of lignosulfonic acid/poly (vinyl alcohol) composite hydrogel
Yusuke Nakanishi, Yoshikuni Teramoto, Yoshiyuki Nishio
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa
Oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan
Abstract:
Previously, we have prepared lignosulfonic acid (LSA)/poly(vinyl alcohol) (PVA) compositehydrogels via cross-linking with glutaraldehyde (GA) in aqueous solution. In the present study, to avoid elutionof the LSA component in aqueous media and increase the LSA content, LSA/PVA composite hydrogels wereprepared via blend films cast from their mixed aqueous solutions. Cross-linking moiety was introduced into theblend films by thermal treatment and/or reaction with GA. The retentivity of LSA in aqueous media was
improved by formations of hydrogen bonding and sulfonate ester between LSA and PVA, both of which were
corroborated by FT-IR measurement. The salt-splitting capacity and activity of the sulfo groups of LSA for thecomposite gel samples were found to reach ∼0.7 mmol/g-gel and ∼47 %, respectively.
2010-211
リグニンのエポキシ成形材料への応用検討
香川博之*1、岡部義昭*1、中村嘉利*2、佐々木千鶴*2*1
日立製作所材料研研究所、*2 徳島大学大学院ソシオテクノサインス研究部
Possible application of lignin derivatives to molding compounds
Hiroyuki Kagawa*1, Yoshiaki Okabe*1, Yoshitoshi Nakamura*2, Chizuru Sasaki*2*1
Material Research Laboratory, Hitachi, Ltd. 7-1-1 0mika-cho, Hitachi-shi, Ibaraki-ken, 319-1292, Japan, *2
Department of Biological Science and Technology, Institute of Technology and Science, The University ofTokushima Graduate School, 2-1 Minamijosanjima-cho, Tokushima-shi, Tokushima-ken,770-8501, Japan
Abstract:
A more sustainable society by promoting global production that reduces the environmental
burden of a product throughout its life cycle is required. We are currently researching the use of woody biomass,
particularly the application of woody lignin to the epoxy resin widely used in modern electric and electronicequipment. We have investigated the use of lignin derivatives as molding materials. Melt viscosities of molding
compounds containing lignin derivatives as hardening
agents were higher than that of a commercially-available molding compound. However, other mechanical andelectrical properties of hardened compounds were comparable to those of the hardened commercially-available
molding compound. We have successfully applied the molding compound containing lignin to mold a stator of a
prototype of motor. Results suggest that woody lignin has great potential for application to electric devices.
2010-212
アシル化リグニンを原料とするエポキシ樹脂の合成と熱的性質
廣瀬重雄*1、畠山立子*2、畠山兵衛*3*1
産業技術総合研究所、*2 リグノセルリサーチ、*3 福井工業大学工学部
Synthesis and thermal properties of epoxy resins derived from acetylated alcoholysis lignin
Shigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*3*1
Research Institute for Innovation in Sustainable Chemistry, AIST, Central 5, 1-1-4 Higashi, Tsukuba, Ibaraki
305-8565, Japan, *2Lignocel Research Ltd., Fukui-City, Fukui, 910-3558 Japan, *3Fukui UniversityofTechnology, 3-6-1 Gakuen, Fukui-City' Fukui 910-8505, Japan
Abstract:
Acetylated alcoholysis lignin (AcAL) was allowed to react with bisphenol A diglycidyl ether(BPADGE) in the presence of a catalytic amount of phosphorous compound. The molar ratio of epoxy groups toacetoxyl groups ([EPOXY]/[PhOAc] ratios, mol/mol) was varied from 0.9 to 1.2. The chemical structure of theobtained epoxy resins was detemined by FT-infrared spectra of epoxy resins. Thermal properties of epoxy resins
were studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Glass transition
temperatures (Tg's) of epoxy resins showed a maximum value at 1.1 of [EPOXY]/[PhOAc] ratio. The activationenergy (E) of curing reaction was determined by the integral method using values of reaction heats which wereobtained by heating samples at various heating rates. The obtained value of E was ca. 90-210 kJ/mol. Thermal
decomposition temperatures (Td's) of epoxy resins were almost constant regardless of [EPOXY]/[PhOAc] ratios,
while the residue at 500 ºC (MR500) Of epoxy resins showed a maximum value at of 1.0 of [EPOXY]/[PhOAc]
ratio.
2010-213
両親媒性リグニン誘導体の利活用
511

本間春海*1*2、及川千括*2、幸田圭一*2、平井卓郎*2、浦木康光*2、山田竜彦*3*1
ドーコン株式会社、*2 北海道大学大学院農学研究科、*3 森林総合研究所
Utilization of amphiphilic lignin derivatives
Harumi Homma*1*2, Chihiro Oikawa*2, Keiichi Koda*2, Takuro Hirai*2, Tatsuhiko Yamada*3, Yasumitsu Uraki*2*1Docon Co., Ltd,, Sapporo 004-8585, Japan, *2Research Faculty of Agriculture, Hokkaido University, Sapporo
060-8589, Japan, *3Department of Biomass Chemistry' Forestry and Forest Products Research Institute, Tsukuba
305-8687, Japan
Abstract:
Three types of polyethylene glycol (PEG) derivatives with epoxy group, PEGDE, EPEG and
DAEO, were reacted with several isolated lignins to prepare amphiphilic lignin derivatives. The relationships
between surface activities of the lignin derivatives and dispersibility or efficiency of cellulase activity
enhancement were investigated to make use of the lignin derivatives as cement
dispersants and cellulase-aid agents, DAEO-Lignin showed the highest surface activity, followed by
EPEG-Lignin and PEGDE-Lignin. These lignin derivatives improved the enzymatic saccharification yield ofunbleached pulp. This effect of lignin derivatives is closely related to their surface activities. On the other hand,
EPEG lignin had the highest dispersibility. This effect of cement dispersibility did not simply obey the surface
activity.
2010-P01
高機能性微生物による木質バイオリファイナリー 〜高活性リグニン分解菌 Phanerochaete sordida YK-624
株のリグニン分解時に産生されるタンパク質のプロテオーム解析〜
八木澤俊倫*1、杉浦立樹*2、平井浩文*1、河岸洋和*1*2、亀井一郎*3、森 智夫*4、近藤隆一郎*4*1
静岡大学農学部、*2 静岡大学大学院創造科学院、*3 宮崎大学農学部、*4 九州大学大学院農学研究院
Woody biorefinery with functional microorganisms — Proteomic analysis of proteins produced by hyper
lignin-degrading fungus Phanerochaete sordida YK-624 under the ligninolytic condition—
Toshimichi Yagisawa*1, Tatsuki Sugiura*2, Hirofumi Hirai*1, Hirokazu Kawagishi*1*2, Ichiro Kamei*3, Toshio
Mori*4, Ryuichiro Kondo*4*1
Faculty ofAgriculture, Shizuoka University, Shizuoka 422-8529, Japan, *2Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan, *3Faculty of Agriculture, University of Miyazaki,
Miyazaki 889-2192, Japan, *4Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan
Abstract:
Proteomic analyses of proteins produced by hyper lignin-degrading fungus Phanerochaete
sordida YK-624 under differential ligninolytic condition were carried out. In the fungal-treated unbleachedhardwood kraft pulp (under low lignin content condition), some ligninolytic enzymes were mainly detected. On
the other hand, catalase, glutathione S-transferase, 1,4-benzo- quinone reductase, enolase,mannose-6-phosphatase, and D-xylose reductase, including ligninolytic enzymes, were detected in thefungal-treated beech wood meals (under high lignin content condition). These results suggest that secreted
proteins were different by lignin content of the culture, and that multiple metabolic pathways were activatedunder high lignin content condition.
2010-P02
高機能性微生物による木質バイオリファイナリー
森 智夫*1、亀井一郎*2、平井浩文*3、近藤隆一郎*1*1
九州大学大学院農学研究院、*2 宮崎大学農学部、*3 静岡大学農学部
Woody biorefinery with functional microorganisms
Toshio Mori*1, Ichiro Kamei*2, Hirofumi Hirai*3, Ryuichiro Kondo*1*1
Faculty of Agriculture, Graduate School of Kyushu University, *2Faculty of Agriculture, Miyazaki University,*3
Faculty of Agriculture, Shizuoka University,
Abstract:
Biorefinery process is environmental friendly and low-energy cost technology. Ethanol can bealso biorefined from lignocellulosic material. There are two big problems on the biorefinery of woody materials
for ethanol fermentable sugar. First is low-efficiency of biological treatment for lignin removal. Second,
enzymatic saccharification process is less efficiency and its cost is quite expensive comparing with chemical
process. Our final goal is the establishment of biorefinary process that can obtain fermentable sugars fromwoody material, especially from cedar wood. We are constructing functional organism that is capable toeffective lignin-removal from wood, and screening of environmental microorganisms that produce functional
glycosidases.
2010-P03
512

パラコツカス属細菌によるリグニンの分解
松下泰幸*1、平田真寛*2、高木博子*2、本田宗央*2、福島和彦*1*1
名古屋大学大学院生命農学研究科、*2 イビデン株式会社
Biodegradation of lignin by Paracoccus sp.
Yasuyuki Matsushita*1, Masahiro Hirata*2, Hiroko Takagi*2 Munechika Honda*2, Kazuhiko Fukushima*1*1
Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601,*2
IBIDEN Co., Ltd, Aoyanagi-cho 300, Ogaki, Gifu, 503-8503
Abstract:
In this study, DHPs were subjected to the degradation by Paracoccus. sp. and the degradation
products were investigated. After the degradation, the molecular weight of DHP was decreased and somephenolic compounds, such as salicylic acid, 2,3-dihydroxybenzoic acid, vanillin and vanillic acid were produced.
When the 13C-[α]-labeled DHP was degraded, 13C-[α]-labeled vanillin and vanillic acid were yielded. Salicylic
acid and 2,3-dihydroxybenzoic acid were also produced, however they were not labeled. These four compounds
were not yielded when the culture was occurred with glycerin as a sole carbon source. Thus it can be concluded
that salicylic acid and2,3-dihydroxybenzoic acid were also produced from DHP.
2010-P04
カワラタケの産生する天然型ラッカーゼメディエータ
萩原通子、宮崎恵、鈴木綾乃、臼井明由美、林佳美、河合真吾、西田友昭
静岡大学農学部
Natural laccase mediator from the culture fluid of Trametes versicolor
Michiko Hagiwara, Megumi Miyazaki, Ayano Suzuki, Ayumi Usui, Yoshimi Hayashi, Shingo Kawai, Tomoaki
NishidaDeparment of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka University, 836
0hya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
To elucidate the presence of natural laccase mediator, we searched for components in theculture fluid of laccase-producing medium of Trametes versicolor. Anthracene, which is not oxidized by laccase
alone, was used for the assay of the ability of laccase mediator. An active fraction was obtained from the ethyl
acetate extracts by repeated chromatography, ant it was analyzed by GC-MS. It is revealed thatp-hydroxybenzoic acid (HBA) was contained in the fraction. Then, to clarify the mediator ability of HBA, theoxidations of anthracene, reactive black 5 and nonphenolic βO-4 lignin substructure model compound bylaccase-HBA couple were conducted. The results demonstrated that all substrates were extensively decreased bythis treatment.
2010-P05
アイソザイム分析及び NALDI-TOF-MS 分析によるカバノアナタケ菌 IO−U1 株に感染したシラカンパ No. 8
幼植物体の防御応答の解明
鈴木美帆、鈴木 拡、高島有哉、石栗 太、飯塚和也、吉澤伸夫、横田信三
宇都宮大学農学部
Clarifying defence responses in Japanese birch No.8 plantlets infected with Inonotus obliquus IO-U1 strain byanalyses of peroxidase isozyme and NALDI-TOF-MS
Miho Suzuki, Hiromu Suzuki, Yuya Takashima, Futoshi Ishiguri, Kazuya Iizuka, Nobuo Yoshizawa, Sinzo
YokotaFaculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
It has been found that lignin and phenolic compounds accumulate, and peroxidase activity
appears in Japanese birch plantlets immediately after the infection with Inonotus obliquus. In this study,
invasion of the fungal hypha into tissues of the plantlets was observed by a scanning electron microscope. After
10 and 30 days of infection, invasion of the fungal hypha into vessels and wood fibers were observed in theplantlets. These results suggest that lignin and phenolic compounds were accumulated to protect the plantlets
from invasion of the fungal hypha. Analyses of peroxidase isozyme and Nano-Assisted Laser Desorption /Ionization (NALDI) –TOF-MS are currently under way.
2010-P06
ポプラ引張あて材細胞壁の木化過程
吉永 新*1、楠元大志*1、Françoise Raulans*2、Gilles Pilate*2、高部圭司*1
513

*1

京都大学大学院農学研究科、*2 フランス国立農業研究所（lNRA）オルレアン
Lignification process of lignified cell wall layers in poplar tension wood
Arata Yoshinaga*1, Hiroshi Kusumoyo*1, Françoise Laurans*2, Gilles Pilate*2, Keiji Takabe*1*1Graduate School of Agriculture, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto
606-8502 Japan, *2Forest Tree Improvement, Genetics and Physiology Research Unit, lNRA-Orléans, 2163
Avenue de la Pomme de Pin, CS40001 Ardon, 45075, Orléans Cedex 2, France
Abstract:
Lignification process of delignified cell wall layers namely, S1, S2 and compound middle
lamella in poplar tension wood fibers was examined by UV microscopy and TEM. Formation process of G layer
was compared to clarify that these lignified cell wall layers finish lignification before G layers are deposited orthat lignification of these layers progresses during G layer formation. As a result, the UV absorption and also
contrast in potassium permanganate staining in TEM in these lignified cell wall layers increased during G layer
formation. This result suggests that lignification of these layers progresses during G layer formation.
2010-P07
MWL 抽出残渣の分画と分析（II） — Xylan-Lignin fraction (XL) のキャラクタリゼーション —宮川泰幸、上高原浩、高野俊幸、中坪文明
京都大学大学院農学研究科
Fractionation and analysis of wood meal after extraction of MWL ( II ) —Characterization of Xylan-Lignin
fraction (XL)—
Yasuyuki Miyagawa, Hiroshi Kamitakahara, Toshiyuki Takano, Fumiaki Nakatsubo
Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502,
Japan
Abstract:
Xylan-lignin fraction (XL), which was prepared by several fractionation steps from wood meal
after extraction of MWL, was characterized by conventional analytical methods. XL was found to be mainlycomposed by syringyl lignin with βO-4 structure and xylan. Furthermore, XL was fractionated withdioxane/water (9:1) to give a soluble fraction (named DL) and a insoluble fraction (DLR). The former and thelatter are mainly composed by syringyl lignin with βO-4 structure and xylan, respectively. DLR is one ofpromising fractions for elucidation of LCC-bonds.
2010-P08
ケイ素吸収欠乏イネ突然変異体 lsi1 におけるリグニン分析
山畑 梓*1、鈴木利貞*1、片山健至*1、武田 真*2*1
香川大学農学部、*2 岡山大学資源植物研究所
Analysis of the lignin in a silicon uptake-deficient mutant lsi1 of rice
Azusa Yamahata, Toshisada Suzuki, Takeshi Katayama, Shin Taketa*1
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, *2Institute of Plant
Science and Resources, Okayama University, 2-20-1 Chuo, Kurashiki, Okayama 710-0046
Abstract:
A rice mutant lsi1 accumulates less silicon in the shoots than a wild type rice (cv. Oochikara).
The mutant lsi1 and the wild type were planted in seedling cases, lignin contents in leaf and stem tissues were
determined with Klason method. Lignin contents in leaves and stems of lsi1 were higher than those of the wild
type. Lignin contents in leaves and stems of lsi1 planted in silicon addition soil (Si+) were lower than those incontrol soil (Si-). While cellulose contents in leaves and stems of lsi1 were slightly higher than those of the wild
type. These results suggested that silicon accumulation in rice might have a negative influence on the depositionof lignin and cellulose, and formation of the secondary cell walls, and thus it affected mechanical strength ofrice.
2010-P09
DFRC 法による針葉樹の葉リグニンの検出
松井直之、大平辰朗
森林総合研究所
Detection of leaf lignin in Japanese gymnosperms by DFRC analysis
Naoyuki Matsui, Tatsuro Ohira
Forestry and Forest Products Research Institute , Wood Extractives Lab. Matsunosato 1, Tsukuba, 305-8687
Japan
Abstract:
A small amount of guaiacyl lignin was detected in sugi leaf by DFRC analysis in our previous514

report. In this study, the analysis was subjected to major Japanese gymnospermous leaves, hinoki, pine andginkgo. Pine needle gave relatively much lignin degradates, in contrast, hinoki and ginkgo leaves gave only
trace amount. Therefore, there is no lignin with arylether interunit linkages in hinoki and ginkgo leaves. This
result shows the obvious difference in leaf-lignin distribution in gymnospermous species. The existence ofwell-developed cambial tissues is anticipated for the depositing site of lignin in rigid leaf, and pine and sugi
leaves seem to have these characteristics.
2010-P10
ハンゲショウにおける 9,9’-デオキシネオリグナン・リグナンの生合成の検討
牧野啓輔，博田健二，片山健至，鈴木利貞
香川大学農学部
Investigation of biosynthesis of 9,9'-deoxy-neolignans/lignans by Saururus chinensis
Keisuke Makino, Kenji Denda, Takeshi Katayama, Toshisada Suzuki
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan
Abstract:
9,9'-Deoxy-lignans/neolignans have been isolated from mainly Myristicaceae, Lauraceae, andPiperaceae plants. However, their biosynthesis is unknown. The present report describes stereochemistry andbiosynthesis of D7'-4,7-dihydroxy-3,3'-dimethoxy-8-O-4'- neolignane, whose erythro and threo isomers are
named as Machilin C and D, respectively, in Saururus chinensis (Saururaceae). (1) The neolignans wereprepared by dehydrogenative
polymerization of isoeugenol with horseradish peroxidase and H2O2. The diastereomeric ratio was erythro :threo =16 : 84. (2) The neolignans were isolated from the underground parts of S. chinensis. The diastereomericratio was 0 : 100 and the enantiomeric ratio was (+) : (-) = 2 : 98. To determine the enantiomeric ratio of thepreferred diastereomer (Machilin D), its terminal double bond was saturated by catalytic reduction withpalladium carbon and chiral HPLC of the resulting dihydro- Machilih D was done. (3) Dehydrogenative
polymerization of isoeugenol with a cell-free extract from S. chinensis in the presence of H2O2 gave theneolignans in the diastereomeric ratio of 14 : 86. However, this Machilin D was racemate. Furthermore,
Sauchinon, a 9,9'-deoxy-lignan whose benzene ring lost its aromaticity was isolated from S. chinensis. A
proposed biosynthetic pathway
Sauchinon will be discussed.
2010-P11
-1 型リグニン二量体モデル化合物の簡便な合成法
菱山正二郎*1、大塚祐一郎*1、中村雅哉*1、加藤厚*1、片山義博*2、原啓文*3、政井英司*4、梶田真也*5*1
森林総合研究所、*２日本大学生物資源学部、*３岡山理科大学、*４長岡技術大学、*５東京農工大学大学院
BASE
Efficient short step synthesis of -1 lignin model compound
Shojiro Hishiyama*1, Yuichiro Otsuka*1, Masaya Nakamura*1, Atsushi Kato*1, Yoshihiro Katayama*２, Hirofumi
Hara*3, Eiji Masai*4, Shinya Kajita*5*1
Forestry and Forest Products Research Institute, 1 Matsunosato Tsukuba, Ibaraki 305-8687, Japan, *2College of
Bioresource Science, Nihon University, Kanagawa 252-0880, Japan, *3Department of Biomedical Engineering,
Okayama University of Science, 1-1 Ridaicho, Okayama
700-0005, Japan, *4Department of Bioengineering, Nagaoka University of Technology, Kamitomioka, Nagaoka,
Niigata 940-2188, Japan, *5Graduate school of Bio-Applications and Systems Ihgineering, Tokyo University ofAgriculture and Technology, Koganei, Tokyo 184-8588, Japan
Abstract:
Efficient short step synthesis of 1,2-Bis(4-hydroxy-3-methoxyphenyl)-1,3-propanediol [β-1lignin model compound] has been achieved. The key step in the synthesis is hydroboration of
2,3-bis-(4-acetoxy-3-methoxyphenyl) acrylic acid obtained from perkin reaction of vanillin andhomovanillic acid. In this strategy, only threo forms of desired compound is produced. The efficient conversion
process of threo form into erythro form has also been discussed.
2010-P12
ジリグノールの酵素的脱水素重合
橋ヶ谷尚大、松下泰幸、今井貴規、福島和彦
名古屋大学大学院生命農学研究科
Enzymatic dehydrogenative polymerization of dilignols
515

Shota Hashigaya, Yasuyuki Matsushita, Takanori Imai, Kazuhiko Fukushima
Guraduate School of Bioagricultual Sciences, Nagoya University, Nagoya 464-8601
Abstract:
To analyze the reaction kinetics of the dilignols in lignin biosynthesis, we tried enzymatic
dehydrogenative polymerization of pinoresinol as a typical dilignol. LC/MS/MS analysis indicated that there
were pinoresinol dimers in the reaction mixture. This results suggested that there was a possibility of thepolymerization between dilignols each other in vivo. Reaction kinetics of coniferyl alcohol was compared withthat of pinoresinol.
2010-P13
tert-ブトキシドによる-O-4 結合開裂反応における溶媒の影響
竹野甲子夫、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Effects of the solvents on the reaction of the -O-4 bond cleavage using tert-butoxide
Kineo Takeno, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, the University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
The -O-4 bond cleavage of a dimeric non-phenolic lignin model compound,
2-(2-methoyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol (2), was examined in systems using potassium
tert-butoxide (KOtBu)/THF and KOtBu/1,4-dioxane. The  -O-4 bond of (2) was cleaved in both systems at
30ºC and the rates were much greater than those in KOtBu/tBuOH and
KOtBu/DMSO systems, which had been reported in our previous paper. A characteristic reaction product
1,2-dimethoxybenzene (6), was detected in both systems. (6) was probably produced from
4-acetyl-1,2-dimethoxybenzene (4), a primary degradation product of the  -O-4 bond cleavage of (2).
2010-P14
Absolute configurations of erythro- and threo-syringylglycerol-8-O-4'-(sinapyl alcohol) ethers, dilignols as wellas 8-O-4' neolignans
Md. Shameul Alam, Toshisada Suzuki, Takeshi Katayama
Faculty of Agriculture, Kagawa University, Miki-cho, Kagawa 761-0795
Abstract:
To clarify the stereochemical mechanism of the optically active syringylglycerol8-O-4'-(sinapyl alcohol) ethers (SGSE) formation by the incubation of sinapyl alcohol (SA) with enzyme
preparations of Eucommia ulmoides, absolute configuration of four stereoisomers, (+)-erythro-, (-)-erythro,(+)-threo-, and (-)-threo isomers, of SGSEs that contain a chiral secondary benzyl alcohol were determined as(7R, 8S), (7S, 8R), (7S, 8S) and (7R, 8R),respectively, by Mosher’s method [1H NMR analysis oftri-(R)-(+)-a-methoxy-a-trifluoromethylphenylacetate (MTPA) esters of SGSEs] with our related empirical rules.
Four stereoisomers of SGSEs were obtained by dehydrogenations of SA with FeCl 3 followed by reversed phase
HPLC and chiral HPLC.
2010-P15
ヨウ化アルミニウム処理によるクラフトリグニンの構造変化
塩澤洋介*1、幸田圭一*2、浦木康光*2、岸本崇生*3*1
北海道大学大学院農学研究院、*2 北海道大学大学院農学研究科、*3 富山県立大学エ学部
Structural changes in kraft lignin by aluminium iodide (III) treatment
Yosuke Shiozawa*1, Keiichi Koda*2, Yasumitsu Uraki*2, Takao Kishimoto*3*1
Graduate School of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, Hokkaido 060-8589,
Japan, *2Research Faculty of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, Hokkaido
060-8589, Japan, *3Faculty of Engineering, Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama
939-0398, Japan
Abstract:
We have been trying to develop a new method to modify technical lignin chemically, aiming at
fabricating a novel biomass-based polymer with functionality in terms of biorefinery. In this study, kraft lignin,
an important technical lignin, was subjected to a treatment with AlI3, an effective ether-cleaving reagent under amild reaction condition, to give lower mass compounds with higher hydroxyl content. As in the case of a lignin
polymer model compound in a separate experiment, the AlI3 reagent was found to degrade KL and increasehydroxyl group significantly, depending on the reaction condition.
2010-P16
516

フェルラ酸・グリコール酸共重合体の合成および特性解析
河村奈々絵、前田拓希、福井宙、石井大輔、林久夫
龍谷大学理工学部
Synthesis and characterization of poly(ferulic acid-co-glicolic acid)
Nanae Kawamura, Hiroki Maeda, Hiroshi Fukui, Daisuke Ishii, Hisao Hayashi
Faculty of Science and Technology, Ryukoku University, 1-5 Yokotani, Seta Oe-cho, Otsu, Shiga 520-2194,
Japan
Abstract:
Copolymerization of ferulic and glicolic acids were performed to obtain heat-resistantliquid crystal polyester. It was revealed that poly(ferulic acid-co-glicolic acid) obtained after a reflux in acetic
anhydride/sodium acetate at 160ºC for 18 h formed liquid crystalline mesophase between 162 and 213ºC, inspite of its low molecular weight comprising three ferulic and two glycol units.
2010-P17
カフェ酸をモノマーとする多分岐型ポリエステルの合成及び構造解析
前田拓希，石井大輔，林久夫
龍谷大学理工学部
Synthesis and structural analysis of poly(caffeic acid)
Hiroki Maeda, Daisuke Ishii, Hisao Hayashi
Department of Materials Chemistry, Graduate School of Science and Technology, Ryukoku University, 1-5
Yokotani, Seta Oe-cho, Otsu-shi, Shiga 520-2194, Japan
Abstract:
Caffeic acid, a cinnamic acid derivative provided from lignin, can be polymerized to form
multi-branched polyester, because caffeic acid has two phenolic hydroxyl groups and one carboxyl group. In
this study, synthesis and characterization of poly(caffeic acid) (PCA) were performed. The polymerization was
performed in a two-step process. First, caffeic acid was acetylated using acetic anhydride and sodium acetate
under a reflux in 160 ºC. Then a polycondensation was performed at 160 ºC under a vacuum. The product was
analyzed by using FT-IR, NMR, GPC, MALDI-TOF-MS, DSC and hot stage-equipped polarizing microscope.
It was revealed that PCA obtained after polycondensation has a melting point at about 180 ºC and forms
anisotropic phase under molten state in response to external mechanical field.
2010-P18
4 級アミン型リグノフェノールによる貴金属の回収
Parajuli Durga、広田耕一、瀬古典明
独立行政法人日本原子力研究開発機構
Recovery of precious metals using quaternary amine type lignophenol
Durga Parajuli, Koichi Hirota, Noriaki Seko
Quantum Beam Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma, 370-1292, Japan.
Abstract:
Quaternary amine type derivative of lignophenol (TMA-CLP) was prepared by electron beamirradiation followed by chemical treatment with trimethylamine. The adsorbent was tested for its adsorption
behavior for a number of metal ions and found to exhibit selectivity for Au(III), Pd(II), and Pt(IV) in 0.5 to 5.0
M hydrochloric acid medium. From the adsorption isotherm study, the maximum loading capacity of TMA-CLP
for Au(III), Pd(II), and Pt(IV) was evaluated as 4.3, 0.74, and 1.3 mol/kg of the dry adsorbent, respectively.
2010-P19
電子ビームによる高機能性リグノフェノール吸着剤の開発
広田耕一、Parajuli Durga、瀬古典明
独立行政法人日本原子力研究開発機構
Development of high functional lignophenol sorbent using electron beam
Koichi Hirota, Durga Parajuli, Noriaki Seko
Quantum Beam Directorate, Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma, 370-1292, Japan.
Abstract:
Wood derived lignin has been modified with ethylenediamine after electron beam irradiation. Its
performance for the recovery of precious metals has been studied and the results are compared with that ofchemically modified derivative. Electron beam induced modification yielded better performing sorbent.
Electron beam is a good tool for synthesis of high functional bio-sorbent.
2010-P20517

糖化残渣からのリグニン抽出とその性状評価
伊藤一志*1、星井弘道*1、伊藤新*1、高橋武彦*1、小林淳一*1、遠田幸生*2、郷地元博*3*1
秋田県立大学、*2 秋田県産業技術総合研究センター、*3 中央化工機商事株式会社
Extract of lignin from saccharification residue and estimation of chemical nature of the lignin
Kazushi Ito*1, Hiromichi Hoshii*1, Arata Ito*1, Takahiko Takahashi*1, Junichi Kobayashi*1, Yukio Enda*2,
Motohiro Gochi*3*1
Akita Prefectural University. 84-4 Tsuchiya-ebinokuti, Yurihonjo, Akita 015-0055, Japan, *2Akita Researchand Development Center. 4-11 Sanuki-araya, Akita 010-1623, Japan, *3Chuo Kakohki Shoji Co., Ltd. 3-6 Kanda
Nishiki Chiyoda, Tokyo 101-0054, Japan
Abstract:
One of the important issues in bio-ethanol production from woody biomass is the effective
usage of saccharification residue. The saccharification residue includes lignin, which is contained a variety offunctional groups. It is possible to apply the lignin as raw martial for chemical agents and plastics, thus there isa need for an effective extraction technique of lignin from the saccharification residue. In this study,saccharification residue was applied to the extraction technique that was reported in previous study. This report
explained that the lignin was extracted from saccharification residue.

518

第 56 回 （2011.09.15-16） 山形大学 農学部
2011-101
β-1 型スピロジエノン構造に関する研究：シリンギル型同モデル化合物と広葉樹リグニンの NMR 化学シフト
値の比較
秋山拓也*1、菊地淳*2、横山朝哉*1、松本雄二*1*1
東京大学大学院農学生命科学研究科、*2 理化学研究所植物科学研究センター
Study on spirodienone structures with β-1 linkage: NMR chemical shifts of the syringyl type model and thecorresponding signals on the HSQC spectrum of hardwood lignin
Takuya Akiyama*1, Jun Kikuchi*2, Tomoya Yokoyama*1 and Yuji Matsumoto*1*1
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo, Tokyo
113-8657, *2RIKEN Plant Science Center, 1-7-22, Suehiro, Tsurumi, Yokohama, Kanagawa 230-0045
Abstract:
A novel lignin model compound of syringyl type spirodienone structures (β-1/α-O-α′) was
obtained by oxidative coupling of sinapyl alcohol γ-acetate with 1-(4-hydroxy-3,5-dimethoxyphenyl) ethanol.
The 1H and 13C NMR chemical shifts of the acetylated model compound were compared with the signals on the
HSQC spectrum of acetylated avicenia lignin (MWL). The 1H and 13C chemical shifts of signals from α, β, andγ-positions in one side chain part of the model were in well agreement with the candidate correlation signals of
spirodienone structures on the HSQC spectrum of the acetylated MWL.
2011-102
Dissolution of ball-milled plant cell walls in ionic liquid systems for HSQC NMR analysis
Chen Qu, Takao Kishimoto, Masahiro Hamada, Noriyuki Nakajima
Bioorganic Chemistry Lab, Department of Biotechnology, Toyama Prefectural University
5180, Japan
Abstract:
Several ionic liquids with and without co-solvent were used to find milder conditions than thosereported so far for complete dissolution of ball-milled plant cell walls in ionic liquids. Among the ionic liquids
tested, 1-ally-3-methylimidazolium chloride ([Amim]Cl) was the most effective ionic liquid for our purposes.
Some co-solvents such as N,N-dimethyacetamide (DMAc) and pyridine were found to be quite effective toincrease the solubility of the cell walls. The milled fir wood prepared by ball-milling for 8 h was dissolved
completely in [Amim]Cl–DMAc (2:1, w/w) and [Amim]Cl–pyridine (1:1, w/w) even at room temperature(30ºC). 1H–13C correlation HSQC NMR experiments were successfully conducted with the in situ acetylated
fir wood. The differences between the two solvent systems were discussed based on the spectra.
2011-103
木質バイオマスの定量・微細構造解析のための HSQC/HMBC NMR 法の開発
西村裕志*1、小澤佑*1、岡村英保*1、佐々木碧*2、片平正人*1、渡辺隆司*2*1
京都大学 エネルギー理工学研究所 生体エネルギー研究分野 *2 京都大学 生存圏研究所 バイオマス変
換分野
Developments for quantitative and microstructural analyses of woody biomass using HSQC/HMBC NMR
Hiroshi Nishimura*1, Yu Kozawa*1, Hideyasu Okamura*1, Midori Sasaki*2, Masato Katahira*1, Takashi
Watanabe*2*1
Laboratory of Bioenergy, Institute of Advanced Energy (IAE), Kyoto University, Kyoto 611-0011, Japan.
*2
Laboratory of Biomass Conversion, Research Institute for Sustainable Humanosphere (RISH), Kyoto
University, Kyoto 611-0011, Japan
Abstract:
Woody biomass is a heterogeneous material and its microstructure is not yet fully understood.
Here, we developed an analytical method of intact and biodegraded wood using solution state NMR without any
chemical treatment. Wood pieces were milled in mild conditions and dissolved in DMSO-d6. Optimization ofanalytical parameters gave high resolution and quantitative HSQC spectra. NMR signals of lignin
microstructures were well distinguished and assigned by HMBC correlations. We applied this method tobiodegraded wood by white rot fungus and demonstrate a decrease of lignin contents.
2011-104
バイオリファイナリーのためのリグニンの MALDI-FT-ICR MS
吉岡康一, 渡邊崇人, 本田与一, 渡辺隆司
京都大学生存圏研究所
519

MALDI-FT-ICR MS of lignin for biorefinery
Koichi Yoshioka, Takahito Watanabe, Yoichi Honda, Takashi Watanabe
Research Institute for Sustainable Humanosphere, Kyoto University, Kyoto 611-0011, Japan
Abstract:
Mass spectrometry by MALDI ionization gives direct structural information in a wide range ofmolecular mass regions. However, reports on mass spectrometry of lignin by MALDI ionization are still limited.
Our group has analyzed isolated and synthetic lignin using MALDI-MS. In this study, the milled wood from
Eucalyptus globulus was analyzed with ultra-high resolution mass spectrometry with Fourier-transform ion
cyclotron resonance mass spectrometer (FT-ICR MS). The mass spectrometry provided the peaks originatingfrom the inter linkages of lignin and hexoses. The mass spectrometry is useful for wood biomass refinery,especially for structure-based utilization of lignin.
2011-105
ToF-SIMS を用いたリグニン構造の解析
井岡昂介、 松下泰幸、 今井貴規、 斉藤香織、 福島和彦
名古屋大学大学院生命農学研究科
Analysis of lignin structure using ToF-SIMS
Kousuke Ioka, Yasuyuki Matsushita, Takanori Imai, Kaori Saito, and Kazuhiko Fukushima
Graduate School of Bioagricultural Science, Nagoya University, Nagoya, 464-8601
Abstract:
From the experiments using model compounds, when lignin is analyzed by ToF-SIMS, thecommon interunit linkages without 5-5’linkage are cleaved and the characteristic secondary ions of lignin are
generated. In previous study, the characteristic secondary ions at m/z 137 and 151 are produced from thephenylcoumaran type lignin model compound by ToF-SIMS. But it is still not clear which aromatic ring
generates these ions and whether the β-5’ linkage is cleaved by ToF-SIMS. In this study, the phenylcoumaran
type lignin model compound and its deuterium-labelled compound were synthesized and analyzed by ToF-SIMS.
From the result, the β-5’ linkage seems not to be cleaved by ToF-SIMS.
2011-106
IR-SNOM による木質組織の分析
山㟁崇之、松本雄二
東京大学大学院農学生命科学研究科生物材料科学専攻木材化学研究室
IR-SNOM analysis of wood tissue
Takayuki Yamagishi, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, Tokyo, 113-8657, Japan
Abstract:
IR-SNOM (Infrared-Scanning near-field optical microspectrometer) is potentially capable ofobtaining IR spectra from a microscopic area of submicron order. After the wood fiber of Quercus serrata wasmanually isolated, it was put on the KBr tablet and subjected to IR-SNOM analysis. We succeeded in obtaining
a good near-field IR spectrum by omitting the scattering light derived from surrounding tissue. The absorbancepeak at around 835cm-1 in near-field IR spectrum from wood fiber was stronger than the corresponding peak in
the usual IR spectrum obtained from wood powder. Considering that the spectrum obtained from wood powder
by usual FT-IR reflects the average spectrum of whole sample, peaks characteristic in near-field IR spectrum
may indicate the specific feature of the observed sample.
2011-107
木材の熱分解生成物の定量的検討 ～過ヨウ素酸処理木粉の熱分解生成物とリグニン含有率の関係～
錦織香*1、勝亦京子、秋山拓也、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科生物材料科学専攻木材化学研究室 *1 現在：Biomaterial in Tokyo
Quantitative analysis of pyrolysis products of Wood material -Relation with pyrolysates of periodate treatedwood material and Lignin contentsKaoru Nishikiori*1, Kyoko Katsumata, Takuya Akiyama, Tomoya Yokoyama, Yuji Matsumoto
Department of Biomaterials Sciences, Graduate School of Agricultural and Life Sciences, The University ofTokyo, Tokyo, 113-8657, Japan*1
Present address: Biomaterial in Tokyo
Abstract:
In order to understand the effect of lignin on the formation of pyrolysis products, wood meals
520with increased lignin content prepared by periodate pre-treatment were subjectd to pyrolysis by the us of tube
type kiln. Lignin content of prepared samples were 45.1% (by 4days periodate treatment) and 67.6% (by 7days
periodate treatment) in addition to 26.2% of un-treated wood meal. The contribution of lignin to the formationof pyrolysis residue was made clear. Interestingly, the increase of lignin content by periodate treatment did not
result in the increase of the total yield of aromatic type low molecular pyrolisates. Results obtained here as wellas those obtained in our former experiment by the use of chlorite pre-treatment suggested that the formation ofpyrolisates is affected not only by the amount of lignin but also by the chemical changes caused during thepretreatment.
2011-108
コニフェリルアルコール及びシナピルアルコールの熱分解反応特性とリグニン熱分解における役割小竹毅郎，
河本晴雄，坂 志朗
京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻
Pyrolytic reactivities of coniferyl alcohol and sinapyl alcoholand their roles in lignin pyrolysis
Takeo Kotake, Haruo Kawamoto, Shiro Saka
Department of Socio-Environmental Energy Science, Graduate School of Energy Science,
Kyoto University, Kyoto 606-8501, Japan
Abstract:
Pyrolytic β-ether cleavage of dimers gives coniferyl alcohol and sinapyl alcohol, while theiryields reported from the isolated lignins are not significant. To clarify this contradiction, pyrolytic reactivities ofconiferyl alcohol and sinapyl alcohol were studied under N2/200-350˚C/5min. As a result, evaporation ofconiferyl alcohol was competed with some pyrolytic reactions to form condensation products and Cγ-oxidation(coniferyl aldehyde) and Cγ-reducition (isoeugenol) products at 250-350˚C, where β-ether linkages in dimers
are reported to be cleaved. Roe of coniferyl alcohol as a pyrolysis intermediate of lignin was also discussed by
the yield (coniferyl alcohol + coniferyl aldehyde + isoeugenol) from sugi (Cryptomeria japonica) wood and
MWL. The yields were only less than 1.5 wt% under neat conditions, while the yields increased by 1.3 to 4.5
times along with the yields of dimer/trimer fractions in 1,3-diphenoxybenzene which suppressed thecondensation reactivity of coniferyl alcohol.
2011-109
リグニンの β-O-4 結合新規選択的開裂法(γ-TTSA 法)の検討(2)—DHP への適用—
安藤大将*1、西村裕志*2、片平正人*2、高野俊幸*1、中坪文明*3、矢野浩之*3*1
京都大学大学院農学研究科 *2 京都大学エネルギー理工学研究所 *3 京都大学生存圏研究所
Studies on the selective cleavage method for β-O-4 linkages of lignins (γ-TTSA method)(2)–Application to lignin model polymer (DHP)–
Daisuke Ando*1, Hiroshi Nishimura*2, Masato Katahira*2, Toshiyuki Takano*1, Fumiaki Nakatsubo*3 , Hiroyuki
Yano*3*1
Division of Forest ＆ Biomaterials Science, Guraduate School of Agriculture, Kyoto University, Kyoto,606-8502, Japan, *2Institute of Advanced Energy, Kyoto University, Gokasho, Kyoto, 611-0011, Japan,*3
Reserch Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Kyoto, 611-0011, Japan
Abstract:
Application of γ-TTSA method (consisted of four reactions; tosylation, thioetherification,
sulfonation, alkali-treatment), which has been proposed as new selective β-O-4 cleavage method, to lignin
model polymer (DHP) with various linkages such as β-5, β-β and β-O-4 was investigated. FT-IR and 1H-NMR
spectra of the four products suggested that the former three reactions proceeded in DHP as well as in β-O-4
model dimer. HSQC-NMR spectrum of the final product after the alkali-cleavage revealed that β-O-4 linkages
were selectively cleaved with the reaction of other linkages such as β-5 and β-β in the last reaction.
2011-110
活性酸素種による糖の水素引き抜き反応における速度論的同位体効果の解析
中川明彦、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Analysis of kinetic isotope effect in hydrogen Abstraction from carbohydrate by active oxygen species
Akihiko Nakagawa, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, Tokyo 113-8657, Japan
Abstract:
In our previous studies, a clear kinetic isotope effect was observed when a pair of a521

carbohydrate model compound, methyl β-D-glucopyranoside (MGP), and its deuterated compound at theanomeric or C-2 position, methyl β-D-(1-2H)glucopyranoside or methyl β-D-(2-2H) glucopyranoside,
respectively, were reacted with active oxygen species (AOS) generated by reactions of O2 with a phenolic
compound, 2,4,6-trimethylphenol (TMPh), under oxygen delignification conditions. This result indicates that
the AOS Abstract the hydrogens connected to the anomeric and C-2 positions of MGP. Contrarily, no clear
kinetic isotope effect was observed when AOS were generated by reactions of O2 with another phenolic
compound, 4-hydroxy-3- methoxybenzyl alcohol (vanillyl alcohol, VA), and hence, the Abstraction of thehydrogens could not be confirmed in this case. In this study, a pair of MGP and its completely deuterated
compound at all the positions, (2H3)methyl β-D-(1,2,3,4,5,6,6-2H7)glucopyranoside, was reacted with AOS
generated from TMPh or VA under oxygen delignification conditions to examine whether a clear kinetic isotope
effect is always observed when AOS Abstract one of the hydrogens from the C-H bonds in MGP. A clear
kinetic isotope effect was observed in each system of the AOS generators, which shows that AOS generated
both from TMPh and VA certainly Abstract the hydrogens from the C-H bonds in MGP. We further discuss on
the appearance of kinetic isotope effect in the following text.
2011-111
アルカリ蒸解過程におけるリグニン β-O-4 結合開裂の速度論的検討（２） —芳香核構造および側鎖立体構
造の影響—
清水智子、横山朝哉、秋山拓也、松本雄二
東京大学大学院農学生命科学研究科
Kinetic analysis of the β-O-4 bond cleavage of lignin during alkaline cooking process (2)Effect of aromatic structure and stereo structure of side chain.
Satoko Shimizu, Tomoya Yokoyama, Takuya Akiyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 113-8657, Japan.
Abstract:
In this study, it was examined how the aromatic structure and the stereo structure of side chainof non-phenolic β-O-4 type unit in lignin control the rate of the β-O-4 bond cleavage during alkaline cooking
using
the
erythroandthreo
isomersof
non-phenolicmodel
compounds,
2-(methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol(VG),
2-(2,6-dimethoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (VS), and 2-(methoxyphenoxy)-1-(3,4,5-trimethoxy- phenyl)
propane-1,3-diol (SG). The disappearances of all the compounds used were well approximated topseudo-first-order reactions. The rate constants (k) of the erythro isomers of all the compounds were about 4times as large as those of the corresponding threo isomers. The both isomers of VS disappeared much faster thanthose of VG. On the other hand, SG degraded only slightly faster than VG in any case. These results suggest thatthe effect of the substitution of syringyl nucleus for guaiacyl nucleus on the rate of the β-O-4 bond cleavage
appears more strongly when syringyl nucleus exists as the cleaving phenoxyl ether than when it is present as the
carbon framework. Number of peaks observed in the HPLC chromatograms was larger when the mixtures
obtained from the threo isomers of all the compounds were analyzed than when those from the corresponding
erythro isomers were analyzed. This suggests that the mechanism of the β-O-4 bond cleavage of threo isomer is
not completely the same with that of erythro counterpart.
2011-112
Effects of DMSO/LiCl dissolution on the structural characteristics of rice straw lignin
Wenjuan Wu*1*2, Zhiguo Wang*1*2, Yongcan Jin*1*2, Yuji Matsumoto*1*1
Grtaduate School of Agricultural and Life Sciences, The University of Tokyo, 113-8657, Japan*2
Department of Paper Science and Technology, Nanjing Forestry University, China
Abstract:
Four samples of rice straw (stem only, stem with knot, leaf including sheath, whole straw) were
subjected to the dissolution in DMSO/LiCl after the planetary ball milling pretreatment. Regenerated materials
from the DMSO/LiCl solution or suspension were treated by cellulolytic enzymes. The samples were almost
completely dissolved in DMSO/LiCl by 1 h ball milling. The chemical nature of the regenerated materials andtheir residue after the enzymatic hydrolysis were analyzed and the accessibility of this rice straw to the
enzymatic hydrolysis was evaluated.
2011-113
One electron oxidation of wood and carbohydrates
Ulla Westermark*1, Anna Pantze*1, Olov Karlsson*1
522

*1

Wood Material Science, Campus Skellefteå, Luleå University of Technology, S-931 87 Skellefteå, Sweden,
Present address: Hörnåkersvägen 45, SE-18365 Täby, Sweden
Abstract:
One electron oxidation of lignocellulosic materials can give a material with self bonding
properties on further pressing and heating. Similar oxidation gives wet strength properties to paper after shortheating. One electron oxidation of lignocelluloses materials are complicated reactions and both oxidized lignin
and carbohydrates can contribute to the bonding ability. This paper present results pointing to that oxidized
carbohydrates of the dialdehyde type plays an important role in the bonding.
*1

2011-114
酸性サルファイトパルプ残留リグニンがパルプの酵素糖化挙動に及ぼす影響
谷藤渓詩*1，張翼*1，髙橋史帆*2，大井洋*1，中俣恵一*3*1
筑波大学大学院生命環境科学研究科, *2 ニューブランズウィック州立大学，カナダ*3
北越紀州製紙株式会社 技術開発部
Effect of residual lignin in acid sulfite pulp on behavior of enzymatic saccharification of pulp
Keishi Tanifuji*1, Zhang Yi *1, Shiho Takahashi*2, Hiroshi Ohi*1 , Keiichi Nakamata*3*1
Graduate School of Life and Environmental Sciences, University of Tsukuba, 305-8572, Japan*2
Department of Chemical Engineering, University of New Brunswick, Canada, *3Technical and Development
Division, Hokuetsu Kishu Paper Co., Ltd.
Abstract:
The lignin contents of pulp with enzyme impregnated and amounts of the enzyme in pulp wereanalyzed by the acetyl bromide method and the K number method to establish a method for estimating amountsof enzyme adsorbed to residual lignin in the enzyme-treated pulps. The estimation is very important to develop ahighly efficient enzyme-hydrolysis of ligno-cellulosics materials for bio-ethanol production. When lignin
analysis was conducted by the acetyl bromide method, the apparent lignin content of pulp with impregnation of
12.7 FPU of enzyme per one gram of pulp was about 9%, which was only 1% point higher than the lignin
content of pulp (7.9%). The apparent K numbers of pulp increased with the amounts of enzyme impregnated inpulp. However, the apparent K numbers of the pulp residues decreased during the enzymatic treatment of pulps.
The residual lignin of the pulps, which were less soluble in water, partly liberated from the pulps during the
enzymatic treatment. In addition, a part of reducing sugars in the hydrolysate must consume the permanganateof the K number method. It is still difficult to establish it, and therefore the both methods are discussed incomparison with the pyrolysis-gas chromatography/ mass spectrometry (Py-GC/MS) method.
2011-115
Sulfurous acid treatment of wood
Yan Shi, Tomoya Yokoyama, Yuji Matsumoto
Graduate School of Agricultural and Life Sciences, The University of Tokyo, 113-8657, Japan
Abstract:
From the wood bio-refinery's point of view, now, sulfurous acid treatment is still attractive
because not only lignin is effectively removed but also hemicelluloses can be hydrolyzed to monosaccharides
during the treatment. So in this work, first, in order to understand the basic behavior of hemicelluloses during
the dilute acid treatment, hydrolysis of Radiata Pine (RP) with dilute hydrochloric acid, sulfuric acid andsulfurous acid was conducted. Main concern was whether or not it is possible to convert as much hemicelluloses
as possible into monosaccharides while depressing the further degradation of produced monosaccharides andcellulose degradation. Under the condition examined, the highest yield of each monosaccharide fromhemicelluloses were as follows: mannose 87%, xylose 96%, galactose 85%, and, arabinose 98%. Second, inorder to know degradation of monosaccharide in these acids, model degradation experiment was conducted. The
results showed that, compared with that in HCl and in H2SO4, degradation of each monosaccharide in sulfurous
acid hardly changes significantly with increase of acid concentration. In a word, sulfurous acid treatment seems
to be of benefit to bio-refinery from hemicellulose.
2011-116
リグニン性状の水蒸気爆砕条件依存性
香川博之*1、岡部義昭*1、佐々木千鶴*2、中村嘉利*2*1(株)日立製作所日立研究所電子材料研究部、*2 徳島大学大学院ソシオテクノサイエンス研究部ライフシス
テム部門
Effect of the steam-explosion conditions on cedar-lignin properties
Hiroyuki Kagawa*1, Yoshiaki Okabe*1, Chizuru Sasaki*２, Yoshitoshi Nakamura*２
523

*1

Hitachi Research Laboratory, Hitachi, Ltd., Hitachi, 319-1292 Japan, *２Department of Life System, Institute ofTechnology and Science, The University of Tokushima, Tokushima, 770-8506, Japan
Abstract:
It is required that a more sustainable society is realized by promoting global production that
reduces the environmental burden of a product throughout its life cycle. We are currently researching the use ofwoody biomass, particularly the application of woody lignin to the epoxy resin widely used in modern electricand electronic equipment. It is preferable that the lignin has homogeneous properties when we apply it toelectric and electronic devices. We have investigated the variability and dependence of lignin properties on
steam-explosion conditions. The molecular weight of lignin after steam-explosion process decreased by setting
the steam pressure higher and the steam time longer. However, the hydroxyl equivalent of the lignin increased
under those conditions. There was less variability in the properties of the lignin obtained by steam- explosion,that is, the steam-explosion method is the manufacturing system which can produce the lignin that havehomogenous properties.
2011-117
バイオエタノール製造副産リグニンを利用したコンクリート用化学混和剤の製造
山田竜彦*1、久保智史*1、中嶋（浅野）勇*2、浦木康光*3*1
森林総合研究所、*2 農業・食品産業技術総合研究機構農村工学研究所、*3 北海道大学大学院
Production of concrete chemical admixture based on byproduct lignin of the woody bio-ethanol process
Tatsuhiko Yamada*1, Satoshi Kbo*1, Isamu Nakajima-Asano*2, Yasumitsu Uraki*3
1
Forestry and Forest Products Research Institute, Tsukuba, 305-8687, Japan, 2National Institute for RuralEngineering, NARO, Tsukuba, 305-8609, Japan, 3Graduate School of Agriculture, Hokkaido University,
Sapporo 060-8589, Japan
Abstract:
Bio-ethanol production using soft wood resources is an important national challenging issue
related to the nation resource sufficiency due to the accumulating soft wood biomass in Japan. FFPRI is
producing woody bio-ethanol from Japanese cedar wood in a pilot research plant on the enzyme saccharification
method following the soda cooking. In the pilot process, lignin is separated into a soda solution that is so called
black liquor. We are trying to find an applicable method of producing highly value added materials using
by-product lignin, because producing highly value added by-products could very much accelerate theforthcoming commercial production of woody bio-ethanol. A simple method to produce amphiphilic lignins thatis highly valued added functional material was studied using glycidylethers on the single reaction step in theblack liquor. Concrete admixtures such as water reducing agent were produced by purifying the reacted
amphiphilic lignin mixture. The performance of the produced concrete admixture as water reducing agent was 3
times higher than widely used commercial product. The admixture had enough quality on the concrete mortar
strength test. The admixture showed sufficient performance of concrete air entraining agent as well.
2011-118
バイオディーゼル燃料用植物の有効成分の探索
江藤恭子*1，松田友佳*1，平田千恵*1，鈴木利貞*1，片山健至*1，Tanachai Pankasemusk*2*1
香川大学農学部、*2 チェンマイ大学農学部
Investigation of effective ingredients from a plant for biodiesel fuel production
Kyoko Eto*1, Yuka Matsuda*1, Chie Hirata*1, Toshisada Suzuki*1, Takeshi Katayama*1,
Tanachai Pankasemusk*2*1
Faculty of Aguriculture, Kagawa University, Kagawa 761-0795, Japan, *2Faculty of Aguriculture, Chiang Mai
University, Chiang Mai 50200, Thailand
Abstract:
Jatropha curcas L. is, native to tropical Latin America, an oil-bearing shrub widely harvested intropical and sub-tropical regions throughout Africa and Asia. The plant is resistant to drought and diseases andcan grow on wastelands or barrens. The seed contain about 30% oil with a fatty acid composition similar to thatof palm oil. The seed oil contains toxic compounds for humans and its nutritional utilizations are impossible.
For these reasons this non-edible oil from J. curcas is favored for biodiesel fuel production. Although irritantphorbol esters were isolated from J. curcas, the other chemical constituents of J. curcas were not fully
understood. In the study, we found antioxidant activity of some extracts from the defatted seed residue of J.
curcas. From the active extracts, one lignan and two neolignans with catechol moieties were isolated andidentified. Antioxidant activity of those compounds was also found.
2011-特別講演
リグニン研究・教育五十年、「意気に感ず」
524

荻山紘一
山形大学名誉教授
Outlook of my study and education about woods for fifty years" Heart to heart"
Koichi Ogiyama
Professor Emeritus of Yamagata University
Abstract:
My study of wood and forest from chemical viewpoint of components have been for
ca.50-years. I am now going to outline several studies briefly and discuss with some criticisms and many
renections. Main subjects are as follows, 1) Lignin structure and reaction on the nitric acid oxidation, 2)
Manufacturing cellulosic pulp by non-aqueous solvent system, 3) Chemosystematic investigation of Sugi
(Cryptomerla japonica) on the basis of heartwood or foliage extractives (diterpene, wax and phenols), 4)
Chemosystematic investigation of Japanese Percimmon, Kaki (Diospyros kaki) on the basis of isozyme
pheno-types, 5) Physiologically active compounds; plant hormones in sugi foliage, 6) Biologically active
compounds of extractives of domestic wood species (Pinus densiflora, Cryptomeria japonica, Taxodium
disticum etc.), 7) Biologically active compounds of tropical heartwood extractives (Dalbergia latifolia,
Artocarpus heterophylla, Macherium pedicellatum etc.). From viewpoint of forest chemistry, importance ofsense about the fate of tree components will be pointed out to maintain the sound forest.
2011-201
バクテリアにおけるリグニン由来ビフェニル化合物の脱メチルシステム
鈴木一也*1、並木仁宏*1、上村直史*1、大塚祐一郎*2、中村雅哉*2、笠井大輔*1、片山義博*3、福田雅夫*1、政井英司*1*1
長岡技術科学大学・生物、*2 森林総合研究所、*3 日本大学・生物資源科学部
Characterization of the O demethylation system essential for the catabolism of
a lignin-derived biphenyl compound in Sphingobium sp. strain SYK-6
Kazuya Suzuki*1, Masahiro Namiki*1, Naofumi Kamimura*1, Yuichiro Otsuka*2, Masaya Nakamura*2, Daisuke
Kasai*1, Yoshihiro Katayama*3, Masao Fukuda*1, Eiji Masai*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, 940-2188, *2Forestry and Forest
Products Research Institute, Tsukuba, 305-8687, *3College of Bioresource Science, Nihon University, Fujisawa,
252-0880, Japan
Abstract:
Sphingobium sp. strain SYK-6, a bacterial degrader of various lignin-derived biaryls andmonoaryls, is able to grow on 5,5'-dehydrodivanillate (DDVA). In a previous study, ligX, which shows thesimilarity with the oxygenase component gene (vanA) of vanillate demethylase of Pseudomonas putida, wasisolated as the gene involved in the O demethylation of DDVA. However, genes for electron transfer
components have not yet been identified. From the genome sequence of SYK-6, we found two ferredoxin genes
and two ferredoxin reductase genes as the candidate genes for electron transfer components. Disruption of eachgene indicated that SS1C_Con002_0548 (ferredoxin) and SS1C_Con009_0377 (ferredoxin reductase) were
essential for the growth of SYK-6 on DDVA. A mixture of crude enzymes containing the gene products of ligX,
SS1C_Con002_0548, and SS1C_Con009_0377 produced in Escherichia coli catalyzed the O demethylation of
DDVA in the presence of NADH. It was concluded that the DDVA O-demethylase system consists of an
oxygenase component, a ferredoxin, and a ferredoxin reductase.
2011-202
Biodegradation of heptachlor and its metabolites in contaminated soil by white-rot fungi
Adi Setyo Purnomo*1*2, Pengfei Xiao*1, Toshio Mori*1, Ryuichiro Kondo*1*1
Department of Agro-environmental Sciences, Faculty of Agriculture,Kyushu University, 812-8581, Japan,*2
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Sepuluh
Nopember.
Abstract:
The ability of white-rot fungi (WRF) to degrade heptachlor and heptachlor epoxide has been
investigated. During 14 days incubation, heptachlor was transformed completely to chlordene,
heptachlor epoxide and 1-hydoxychlordene by Pleurotus ostreatus (hiratake) in PDB and Kirk'shigh nitrogen (HN) media, indicating hiratake has better ability rather than Phlebia fungi. For
application purpose, spent mushroom waste (SMW) of hiratake and/or fungal substrates of Phlebia
was used. After 28 days incubation, approximately 89% and 100% of heptachlor was eliminated byhiratake SMW and P. acanthocystis fungal substrate. Chlordene, heptachlor epoxide and1-hydoxychlordene were detected as metabolites from hiratake SMW while only heptachlor
epoxide was detected from P. acanthocystis fungal substrate. Since hiratake SMW can degrade525heptachlor and heptachlor epoxide, hiratake SMW was applied to treat heptachlor in artificiallycontaminated soil. Approximately 89% and 92% of heptachlor was eliminated in sterilized (SL) andun-sterilized (USL) soils, respectively. Furthermore, approximately 23% of heptachlor epoxide waseliminated in SL soil. This study demonstrates that hiratake SMW was applicable for degradation of heptachlor
and its resistant metabolite, heptachlor epoxide, in contaminated soil.
2011-203
Degradation of aliphatic hydrocarbons in three types of crude oil by Fusarium sp. F092 in sea water liquidmediumAsep Hidayat, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University, 790-8566, Japan
Abstract:
The capabilities of Fusarium sp. F092 to degrade the aliphatic fraction in comparison of three
types of crude oil in sea water liquid cultures were examined. The results showed that Fusarium sp. F092 having
the ability to degrade the aliphatic fraction in crude oil contaminating a liquid culture with artificial sea water(35o/oo). The aliphatic fraction was large in crude oil type-3 than crude oil type-1 or type-2 and the otherfractions comprised less than 31% of the total. Crude oil type-1, type-2 and type-3 contained C13 to C31, C13
to C27 and C12 to C20, respectively. F092 showed the best performance to break down the aliphatic fraction in
crude oil type-3 (98%) and type-2 (72%) and type-1 (49%) after 60 days at an initial concentration of 1000 mg
L-1. Furthermore, almost all the aliphatic compounds (Up to C31) in the crude oil were degraded by F092
which preferred short and long chain hydrocarbons. Incubation of crude oil at concentration of 15000 mg L-1
degraded less than 40% of the aliphatic fraction of all crude oils tested.
2011-204
高機能性微生物による木質バイオリファイナリー、 ～新規リグニン分解特異的プロモーターに関する研究～
大野正人*1、杉浦立樹*2、平井浩文*1、河岸洋和*1*2、山岸賢治*3、亀井一郎*4、
森智夫*5、近藤隆一郎*5*1
静岡大学農学部、*2 静岡大学創造科学技術大学院、*3 独立行政法人農業・食品産業技術総合研究機構東北農業研究センター、*4 宮崎大学農学部、*5 九州大学大学院農学研究院
Woody biorefinery with functional microorganisms
Masato Ohno*1, Tatsuki Sugiura*2, Hirofumi Hirai*1, Hirokazu Kawagishi*1*2, Kenji Yamagihsi*3, Ichiro Kamei*4,
Toshio Mori*5, Ryuichiro Kondo*5*1
Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, *2Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan, *3National Agricultural Research Center for the
Tohoku Region, National Agriculture and Food Research Organization, Fukushima 960-2156, Japan, *4Facultyof Agriculture, University of Miyazaki, Miyazaki 889-2192, Japan, *5Faculty of Agriculture, Kyushu University,
Fukuoka 812-8581, Japan
Abstract:
In our previous reports, we identified protein (BUNA2) as a strong and sharp spot from hyper
lignin-degrading fungus Phanerochaete sordida YK-624 under wood-rotting condition by two-dimensional gel
electrophoresis, and BUNA2 gene (bee2) and a promoter region of bee2 were cloned by several PCR series.
Moreover, bee2 promoter was used to drive the expression of manganese peroxidase gene (mnp4) in P. sordida
YK-624, and most of transformants showed higher ligninolytic activity and selectively than wild type. BUNA 2
was classified as oxidoredutases containing Zn-binding site. bee2 was induced by the addition of vanillin,
Mn(II), bisphenol A, and veratryl alcohol. Recently, we constructed the various EGFP-expression plasmids
which were regulated by various-length bee2 promoter in order to determine actual promoter region of bee2 andto modify the promoter.
2011-205
高機能性微生物による木質バイオリファイナリー、 ～白色腐朽菌 Phlebia sp. MG-60 株によるセルロースの直接エタノール発酵～
亀井一郎*1、廣田佳幸*1、目黒貞*1、平井浩文*2、山岸賢治*3、森智夫*4、近藤隆一郎*4*1
宮崎大学農学部、*2 静岡大学農学部、*3 農業・食品産業技術総合研究機構東北農業研究センター、*4 九州大学大学院農学研究院
Woody biorefinery with functional microorganisms ～Direct ethanol production from cellulosic materials bywhite-rot fungus Phlebia sp. MG-60～
Ichiro Kamei*1, Yoshiyuki Hirota*1, Sadatoshi Meguro*1, Hirofumi Hirai*2, Kenji Yamagishi*3, Toshio Mori*4,526

Ryuichiro Kondo*5*1
Faculty of Agriculture, University of Miyazaki, Miyazaki 889-2192, Japan, *2Faculty of Agriculture, Shizuoka
University, Shizuoka 422-8529, Japan, *3National Agricultural Research Center for Tohoku Region, Fukushima,960-2156, Japan, *4Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan
Abstract:
Twelve strains of basidiomycetes were applied for ethanol fermentation. Silicon rubber plug
was used to block the aeration for keeping semi-aerobic condition in flasks. When glucose was used as carbon
source, Phlebia sp. MG-60 showed the high productivity of ethanol (over 70% of theoretical conversion rate).
When Phlebia sp. MG-60 was cultured with in 20 g/l microcrystalline cellulose, 2.8 g/l ethanol, 25.3% of
theoretical maximum was detected after 480 h incubation. When silico plug was used for keeping aerobic
condition, there was no production of ethanol in the culture with glucose or cellulose. Hexoses; glucose,mannose, galactose and fructose were well assimilated by Phlebia sp. MG-60. In the case of pentoses, there wasno production of ethanol from arabinose, however, good fermentability of xylose by Phlebia sp. MG-60 was
observed. When Phlebia sp. MG-60 was cultured with in 20 g/l unbleached hardwood kraft pulp (UHKP),
64.3% and 70.3% ethanol of theoretical maximum were detected after 240 h and 480 h incubation respectively.
When Phlebia sp. MG-60 was cultured with in 20 g/l softwood kraft pulp (USKP), 19.4% and 42.4% ethanol oftheoretical maximum were detected after 240 h and 480 h incubation respectively. These results indicated thatethanol production is occurred simultaneously with hydrolysis of cellulose.
2011-206
高機能性微生物による木質バイオリファイナリー
～メタゲノムライブラリからの木材分解酵素獲得の試み～
森智夫*1、平井浩文*2、山岸賢治*3、亀井一郎*4、近藤隆一郎*1*1
九州大学大学院農学研究、*2 静岡大学農学部、*3 農業・食品産業技術総合研究機構東北農業研究センタ
ー、*4 宮崎大学農学部
Developments of wood biorefinery techniques with functional microorganisms, Functional screening of novel
wood-degrading enzymes genes from metagenome libraries derived from soils
Toshio Mori*1, Hirofumi Hirai*2, Kenji Yamagishi*3, Ichiro Kamei*4, Ryuichiro Kondo*1*1
Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan, *2Faculty of Agriculture, Shizuoka
University, Shizuoka 422-8529, Japan, *3National Agricultural Research Center for Tohoku Region, National
Agriculture and Food Research Organization, Fukushima, 960-2156, Japan, *4Faculty of Agriculture, Universityof Miyazaki, Miyazaki 889-2192, Japan
Abstract:
Several metagenomic libraries were constructed from soils via short-term enrichment culture.
The cultures for accumulation contained avicel, kraft pulp or cedar wood powder as carbon source and thecultures were incubated for a week. Bacterial cells were collected by centrifugation, and whole genomes wereextracted. Partial digested (using Sau3AI) genomes were ligated into pUC19 plasmid, and then transformed into
Escherichia coli DH5  chemical competent cells. Recombinant cells were spread on LB agar medium
containing RBBR-stained CMC. After incubation, CMCase-positive clones appeared with clear halo against
blue culture color. DNA sequence analysis of the transformed inserts revealed that the sequence contained novel
CMCase.
2011-207
高分子リグニン酸化能をもつ CWPO-C における基質酸化部位の同定
重藤 潤*1、伊藤義隆*2、堤 祐司*1、近藤隆一郎*1*1
九州大学 大学院 農学研究院、*2 九州大学 大学院 生物資源環境科学府
Oxidation mechanism of cationic cell-wall-bound peroxidase (CWPO-C) toward lignin model compounds
Jun Shigeto, Yoshitaka Itoh, Yuji Tsutsumi, Ryuichiro Kondo
Department of Forest and Forest Products Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka,
812-8581 Japan
Abstract:
Cationic cell-wall-bound peroxidase (CWPO-C) has the capability to oxidize sinapyl alcohol,
ferrocytochrome c, and synthetic lignin polymers, unlike most peroxidases. It is extrapolated that the oxidationsite is located on CWPO-C protein surface and homology modeling and chemically modified CWPO-C studies
suggest Tyr-74 and/or Tyr-177 are possible participants in the catalytic site. The present study clarifies theimportance of these tyrosine residues for substrate oxidation using recombinant CWPO-C and recombinantmutant CWPO-C with phenylalanine substitution(s) for tyrosine. Our results indicated that Tyr-74 and Tyr-177,
instead of heme pocket, take a central role in the oxidation of guaiacol, 2,6-dimethoxyphenol andsyringaldazine.
527

2011-208
シロイヌナズナ CWPO-C ホモログのダブルノックアウト変異体解析
伊藤義隆*1、重藤 潤*2、堤 祐司*2、近藤隆一郎*2*1
九州大学大学院 生物資源環境科学府、*2 九州大学大学院 農学研究院
Function analysis of cationic cell-wall-bound peroxidase (CWPO-C) homolog double-knockout mutants on
Lignin in Arabidopsis thaliana
Yoshitaka Itoh, Jun Shigeto, Yuji Tsutsumi, Ryuichiro Kondo
Faculty of Agriculture, Kyushu University, 6-10-1, Fukuoka, 812-8581, Japan
Abstract:
Cationic cell-wall-bound peroxidase (CWPO-C) oxidizes sinapyl alcohol and synthetic lignin
polymer,and Tyr-74 and -177 located on the protein surface are possible substrate oxidation sites for highmolecular weight substrates. These characteristics imply that CWPO-C is related to lignification. ThreeCWPO-C homolog genes among 73 Arabidopsis peroxidases are also suggested to be involved in lignificationby the analyses of Arabidopsis T-DNA insertion mutants. These results suggest that the Tyr located on theprotein surface of peroxidase may play an important role in lignification. In this study, Arabidopsis double
knockout mutants, in which CWPO-C homolog genes were ablated, were generated to clarify the function of
three peroxidases in lignification. Also, protein structures of all Arabidopsis peroxidases were constructed byhomology modeling, and possible substrate oxidation site locates on protein surface were analyzed in silico.
2011-209
Sphingobium sp. SYK-6 株由来の ligD 遺伝子を発現する組換え植物の解析
辻 幸子*1，石川靖之*1，高橋理恵*1，佐藤かんな*1，片山義博*3，原 啓文*4
菱山正二郎*5，政井英司*2，梶田真也*1*1
東京農工大学大学院生物システム応用科学府、*2 長岡技術科学大学工学部生物系、*3 日本大学生物資源科学部森林資源科学科、*4 岡山理科大学工学部生体医工学科、*5 森林総合研究所バイオマス化学研究
領域
Characterization of transgenic plants with ligD gene isolated from Sphingobium sp. SYK-6
Yukiko Tsuji*1, Yasuyuki Ishikawa*1, Rie Takahashi*1, Kanna Sato*1, Yoshihiro Katayama*3, Hirofumi Hara*4,
Shojiro Hishiyama*5, Eiji Masai*2, Shinya Kajita*1*1
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, *2Department of Bioengineering, Nagaoka University of Technology,
Niigata 940-2188, Japan, *3College of Bioresource Sciences, Nihon University, Kanagawa 252-0880, Japan,*4
Department of Biomedical Engineering, Okayama University of Science, Okayama 700-0005, Japan,*5
Department of Biomass Chemistry, Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan
Abstract:
Sphingobium sp. SYK-6, a gram-negative bacterium, can utilize various monomeric anddimeric aromatic compounds, which appeared in lignin biosynthetic pathway, such as cinnamic acids,
cinnamaldehydes and β-O-4 dimers. In our previous studies, some genes involved in degradation of thesecompounds were isolated from the bacterium and characterized. One of them, ligD gene encoding
Cαdehydrogenase catalyzes the first step of cleavage reactions for ether bond of β-O-4 dimers. This enzyme
oxidizes alcohol to carbonyl group at benzyl (Cα) position of the dimers. It has been known that the presence ofcarbonyl group at the benzyl position of aryl propane units in lignin speeds up the rate of cleavage of beta-aryl
ether linkages during kraft pulping condition (Gierer et al., 1980; Gierer and Noren, 1982). Thus, we introduced
the ligD gene into plant genome and try to generate transgenic plants whose lignin can be easy to remove fromhollocellulose fraction under the alkaline pulping condition. The enhanced cleavage of beta-aryl ether linkages
which are the most common bonds in lignin structure might contribute not only to pulp and paper industries but
also to bioethanol production from lignocellulose materials. Characteristics of the transgenic Arabidopsis plants
will be discussed as a preliminary step toward the molecular engineering of lignin.
2011-210
イネにおけるシリンギルリグニン生合成経路の解明
小柴太一*1、廣瀬孝江*1、向井まい*1、山村正臣*1、坂本正弘*2、鈴木史朗*1、服部武文*1、

梅澤俊明

*1*3
*1

京都大学生存圏研究所、*2 京都大学大学院農学研究科地域環境科学専攻、*3 京都大学生存基盤科学研
究ユニット
Elucidation of syringyl lignin biosynthetic pathway in rice plant
528

Taichi Koshiba*1, Norie Hirose*1, Mai Mukai*1, Masaomi Yamamura*1, Masahiro Sakamoto*2, Shiro Suzuki*1,
Takefumi Hattori*1 and Toshiaki Umezawa*1*3*1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan,*2
Division of Environmental Science & Technology, Graduate School of Agriculture, Kyoto University.
606-8502, Japan, *3Institute of Sustainability Science, Kyoto University, Kyoto, 611-0011, Japan.
Abstract:
We have analyzed the physiological function of putative rice (Oryza sativa) caffeic acidO-methyltransferase 3 (OsCOMT3). Recombinant COMT3 catalyzed the 5-methylation of 5-hydroxyferulate(5-HFA) and 5-hydroxyconiferylaldehyde (5-HCAld) as substrates, and the methylation of 5-HFA was inhibitedby 5-HCAld. The rice plant which was down-regulated in expression of COMT3 exhibited a weakened staining
with Wiesner reagent in the walls of vascular bundle cells and sclerenchyma tissue compared to wild-type plant.
Lignin content of the transgenic shoot was decreased, and syringyl lignin content of those was reduced up to
87% than that of wild-type. These data indicate that the physiological function of COMT3 is to catalyze the5-methylation in the biosynthetic pathway of syringyl lignin, and suggest that the biosynthetic pathway ofsyringyl lignin in rice is similar to those in dicotyledonous plants.
2011-P01
シラカシモデル林における土壌形成過程での有機物の挙動
勝亦京子*1、田中裕也*1、宮崎毅*2、松本雄二*1*1
木材化学研究室、*2 環境地水学研究室・東京大学大学院農学生命科学研究科
Changes of organic substances at Quercus myrsinaefolia forests during soil formation
Kyoko S. Katsumata*1, Yuya Tanaka*1, Tsuyoshi Miyazaki*2, Yuji Matsumoto*1*1
Laboratory of Wood Chemistry, Graduate School of Agricultural and Life Sciences, the University of Tokyo,*2
Laboratory of Soil Physics and Soil Hydrology, Graduate School of Agricultural and Life Sciences, theUniversity of Tokyo, 113-8657, Japan
Abstract:
Lignin is considered to play an important role in the fixation of organic carbon on the earth. On
the other hand, it is difficult to trace quantitatively the behavior of lignin during soil formation. In this study,changes of organic substances during soil formation were investigated in terms of organic carbon content,
extractability by various solvents and yield of Klason residue.
Samples (living plant, litter and soil) were collected at Quercus myrsinaefolia forests at the University of Tokyo
Tanashi Forest. Total organic carbon (TOC) of living wood and litter were among 43–47%. TOC of soils were
14-4% and was in a range of carbon (C) contents of Japanese forest soil. Any soil did not contain inorganiccarbon. This means that C content is equal to TOC in Tanashi forest soil. Amounts of organic matter were
estimated by assuming that the carbon content of organic matter was 50%. Yields of extractives on estimatedorganic matter were 10–38%, 3–11% and 1-3% in living wood, litter and soil, respectively. It was apparent thatorganic matter turns into hardly extractable materials during soil formation.
2011-P02
Chemical components of eccentric grown wood of teakGanis Lukmandaru
Department of Forest Product Technology, Faculty of Forestry, Universitas Gadjah Mada, 55281, Indonesia
Abstract:
Chemical components of minimum and maximum ring width in the outer heartwood of
eccentric grown teak (Tectona grandis) were compared. The woods were sampled from 10 leaning trees ofthinning activities. The values of chemical components of eccentric wood were in the range of normal teakwoods. T-test analysis showed that no significant differences in extractive, ash, pentosan, and acid soluble lignin
content levels. However, the difference was found in Klason lignin content, which the woods with maximum
ring width showed higher values than those of minimum ring width.
2011-P03
植物の進化に伴うリグニン構造の多様化に関する考察
寺島 典二
名古屋大学 (名誉教授)
Speculations on the diversification of lignin structure during the evolution of plant
Noritsugu Terashima
Nagoya University (Emeritus Professor)
Present address: 2-610 Uedayama, Tenpaku, Nagoya 468-0001, Japan
Abstract:
Diversification of lignin structure occurred during evolution of plant, from p-hydroxyphenyl
529

(H)-guaiacyl (G) lignin to syringyl (S)-G lignin. About 400 million years ago, the first vascular plants appearedon the earth. The vascular bundle performed various functions, conduction of aqueous material, mechanicalsupport of plant, and defense against injuries and microbial attack by formation of supra- molecular complex
composed of lignin and polysaccharides. Pteridophyta and gymnosperms were the first dominant vascular plant,
but change of environment on the earth resulted in evolution of angiosperms, in which multifunctional tracheid
differentiated to conduction- specialized vessel and support-specialized fiber. The strong defense function
arising from the frequent condensed structures in H-G lignin in gymnosperms was weakened to moderate
defense by less condensed S-G lignin in angiosperms. Adequate defense by S-G lignin and quick biodegradation
after the plant death provided suitable environment for frequent alternation of generation and faster evolution toadapt environmental change on the earth.
2011-P04
針葉樹仮道管壁複合中間層におけるリグニン-多糖類-超分子複合体の形成に関する考察
寺島典二*1*4、福島和彦*2、吉田正人*3、Ulla Westermark*1*5*1
STFI(Swedish Pulp and Paper Research Institute), *2 名古屋大学大学院農学研究科森林化学研究室, *3 名古屋大学大学院農学研究科生物材料物理学研究室, *4 現在：自宅（468-0001,名古屋市天白区植田山 2-610）,*5
Present address: Hörnåkers vägen 45, Täby, Sweden
Speculations on the formation of supramolecular complex of lignin and polysaccharides in the compound
middle lamella region of softwood tracheid
Noritsugu Terashima*1*4, Kazuhiko Fukushima*2, Masato Yoshida*3, Ulla Westermark*1*5*1
STFI(Swedish Pulp and Paper research Institute), *2Laboratory of Forest Chemistry, School of Bioagricultural
Science, Nagoya University, Nagoya 464-8601,Japan, *3Laboratory of Bio-material Physics, School of
Bio-agricultural Science, Nagoya University, Nagoya 464-8601,Japan, *4Present address: 2-610 Uedayama,
Tenpaku, Nagoya 468-0001,Japan, *5Present address: Hörnåkers vägen 45, Täby, Sweden
Abstract:
Supramolecular structure of lignins in compound middle lamella (CML) and secondary wall(SW) of softwood tracheid differs partly due to higher content of condensed structures (5-5´-biphenyl,
dibenzodioxocin and 4-O-5´-diphenyl ether) in CML lignin than in SW lignin. In an early stage of cell wall
formation, random networks made up of cellulose microfibril, xyloglucan and pectin are formed in CML. A
large number of globular p-hydroxyphenyl-guaiacyl lignin grow on the network. The growing ends of folded
chain molecules are on the surface of the globules, and successive addition of monolignols by β-O-4 and β-5linkages are prevailed. When the space on the polysaccharide network is almost filled up, insufficient space forfurther monolignol addition causes frequent bonding between two growing ends by 5-5´ or 4-O-5´ linkages. The
circadian rhythm of cell activity may accelerate closer contact of the globules, and supply of one monolignol
after the 5-5´ bonding to form dibenzodioxocin structure.
2011-P05
広葉樹の葉リグニンの DFRC 法による検出（１）松井直之、大平辰朗（独）森林総合研究所バイオマス化学研究領域
Detection of broad-leaf lignin in angiosperms by DFRC analysis (1)Naoyuki Matsui, Tatsuro Ohira
Forestry and Forest Products Research Institute, Wood Extractives Lab. Matsunosato 1, Tsukuba, 305-8687
Japan
Abstract:
The DFRC analysis gives C6-C3 type degradation products from arylether linkages of lignin.
Therefore this method can be used to detect lignin specifically from plant tissues, excluding other(poly)phenolic substances. To investigate the lignin composition in broad-leaves of angiosperms, DFRC
analysis was employed. Many leaves gave both guaiacyl- and syringyl-type degradation products, whichindicates the broad leaf lignin has common structural elements with xylem lignin of the same tree. However,results were not always the same among species and tissues. Syringyl / guaiacyl ratio of DFRC products of leaf
lignin was apparently lower than that of xylem lignin. The leaves of persimmon and cherry gave only trace
amount of degradation products. These results show the heterogeneous distribution of leaf lignin inangiospermous trees.
2011-P06
ニトロベンゼン酸化法によるリグニンのビフェニル型構造の定量的検討
玉井あかり、秋山拓也、松本雄二
530東京大学大学院 農学生命科学研究科
Quantitative evaluation of biphenyl type structures in lignin by nitrobenzene oxidation method
Akari Tamai, Takuya Akiyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657, Japan
Abstract:
Japanese cedar wood meals were subjected to alkaline nitrobenzene oxidation at different
reaction temperatureand for different period to investigate the yields of dehydrodivanillin,
dehydrovanillinvanillic acid and dehydrodivanillic acid that are considered to be the products from biphenyl
type structures (5-5 linkage type) in lignin. On the basis of the total yield of the products obtained in the
optimized reaction condition, 170 ºC for 2 hours, it was suggested that at least 5.2 % of phenylpropane units inthe cedar lignin were involved in 5–5 linkage type structures.
2011-P07
パーム油由来のグリセリンを利用したポリウレタン複合材料及びエポキシ樹脂の熱的・機械的性質
廣瀬重雄*1、畠山立子*2、畠山兵衛*2*1福井工業大学・工、*2 リグノセルリサーチ(株)Thermal and mechanical properties of polyurethane composites and epoxy resins derived from glycerol frompalm oil
Shigeo Hirose*1, Tatsuko Hatakeyama*2, Hyoe Hatakeyama*2*1
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan, *2Lignocel Research Co.
Ltd., 391-5 Ofunato, Tsukuba, Ibaraki 300-1267, Japan
Abstract:
Polyurethane composites were prepared using industrial by-products such as lignin (LS)obtained in pulping process, molasses (ML) obtained in sugar production process, crude glycerol (CG) obtainedin bio-diesel fuel production process, cellulose and empty fruit bunches (EFB) of oil palm. Sodium
lignosulfonate (LS) , ML and CG were dissolved in polyethylene glycol 200 (PEG), and each of the above
solutions, LSP, MLP and CGP were obtained. Cellulose powder with different particle size and EFB powder
were mixed with the mixture of the above polyols, and then the obtained mixtures were allowed to react withpoly(phenylelnemethlylene)polyisocyanate (MDI) under a pressure of 20 MPa for 1 h, and then at 120 oC, for 2
h. The mechanical properties were studied by bending tests. The bending strength (σ) was almost constantregardless of MLP contents (MLP content, % = WMLP/ WMPL + WLSP). Maximum value of σmax was 23 MPa
when fiber length was 28μm at MLP content of 80%, while σmin was 11 MPa when fiber length was 37 μm at
MLP content of 50 %. The bending modulus E values also showed the similar tendency to those of σ values.
Crude glycerol and pure glycerol were allowed to react with succinic anhydride, respectively. When theobtained poly acid derivatives of crude glycerol (CGPA) and GPA were allowed to react with glycerol diglycidyl
ether (GDGE), the weight contents of CGPA {WCGPA/(WCGPA+WGPA)} were change from 0 to 100 %. The glasstransition temperatures were almost constant regardless of CGPA contents in epoxy resins.
2011-P08
工業リグニンを用いた新規セメント分散剤の開発
麻生知裕*1*2、幸田圭一*１*2、浦木康光*１*2、久保智史*3、山田竜彦*3、中嶋勇*4*１*2
北海道大学大学院農学研究科、*3 森林総合研究所、*4 農業・食品産業技術総合研究機構農村工学研究所
Preparation of novel lignin-based cement dispersants from technical lignin
Tomohiro Aso*1, Keiichi Koda*2, Yasumitsu Uraki2, Satoshi Kubo3, Tatsuhiko Yamada3 and Isamu Nakajima4*１
Graduate School of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, 060-8589
Hokkaido,Japan, *2Research Faculty of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo,
060-8589 Hokkaido, Japan, *３Department of Biomass Chemistry, Forest and Forest Products Research Institute,
1 Matsunosato, Tsukuba, 305-8687 Ibaraki, Japan,* ４ National Institute for Rural Engineering, National
Agriculture and Food Research Organization, 2-1-6 Kannondai, Tsukuba, 305-8609 Ibaraki, Japan
Abstract:
We have developed amphiphilic lignin derivatives from technical lignin by the reaction withpoly(ethylene glycol) derivatives. They obviously showed considerable surface activity. The utility ofamphiphilic lignin derivatives were evaluated in terms of their dispersion capacity, as a cement admixture.
Amphiphilic lignin derivatives (EPEG) prepared with monoepoxylated poly(ethylene glycol) gave higher
dispersity to cement than lignosulfonate (LS), a commercially available lignin, at room temperature and 6oC.
The cured cement mixed with amphiphilic lignin derivatives at both temperatures also revealed almost the same531

or slightly higher bending strength than those with LS and without lignin-based additive. In conclusion,
EPEG-based amphiphilic lignin derivatives were proven to be a promising cement admixture that would beavailable even in the wintertime.
2011-P09
リグニン誘導体を用いた天然型有機系紫外線吸収剤
三亀啓吾*1、大橋康典*1、片平律子*2、小澤佑*3、片平正人*3、渡邊崇人*1、本田与一*1、菅原智*4、小池謙造*4，
渡辺隆司*1*1
京都大学生存圏研究所、*2 大阪大学蛋白質研究所、*3 京都大学エネルギー理工学研究所、*4 花王株式会
社
Natural organic ultraviolet absorbers from lignin derivatives
Keigo Mikame*1, Yasunori Ohashi*1, Ritsuko Katahira*２, Yu Kozawa*３, Masato Katahira*３, Takahito Watanabe*１,
Yoichi Honda*1, Satoshi Sugawara*４, Kenzo Koike*４, Takashi Watanabe*1*1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan. *２
Institute for Protein Research, Osaka University, Yamadaoka, Suita-shi, Osaka 565-0871, Japan. *３Institute ofAdvanced Energy, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
*４
Kao Corporation, 2-1-3 Bunka, Sumida-ku, Tokyo 131-8501, Japan.
Abstract:
Currently, ultraviolet (UV) absorbers are becoming popular due to cosmetic and medical
purposes. Exposure of skins to UV rays from the sun causes damage of the skins. Excessive exposure inducesskin cancer and aging. Although the demand for UV absorbers with high safety and minimum environmental
impacts is becoming increasing, most of the organic UV absorbers currently available are synthetic compounds
from petroleum. Therefore, we started the research to develop UV absorbers from natural organic compounds.
Natural aromatic polymer, lignin retain the potential to produce strong UV absorbers by oxidative degradation.
By extensive screening of degradation products from lignin, we found the products having high absorbance in
UV-A and UV-B regions.
2011-P10
フェルラ酸およびカフェ酸をモノマーとするポリエステルの高分子量化
石井大輔，前田拓希，河村奈々絵，林久夫
龍谷大学理工学部物質化学科
Molecular weight enhancement of polyesters from ferulic or caffeic acids
Daisuke Ishii, Hiroki Maeda, Nanae Kawamura, Hisao Hayashi
Department of Materials Chemistry, Faculty of Science and technology, Ryukoku University,
Shiga 520-2194, Japan
Abstract:
Enhancement of molecular weight was attempted for polyesters prepared from ferulic (FA) or
caffeic (CA) acids, both of which are lignin-related aromatic hydroxyl acids. Polymerization of these acids was
performed by ester exchange reaction in sodium acetate/acetic anhydride system followed by polycondensation
at different temperatures and reaction time under reduced pressures. Molecular weight (MW) of poly(caffeicacid) (PCA) as estimated by GPC (relative to polyetyrene standard) increased up to 1.0×10 6 bypolycondensation at 160 ºC for 16 h. On the other hand, MW of poly(ferulic acid-co-glycolic acid) (PFG)
increased only up to 8.0×103 after polycondensation at 180 ºC for 26 h. These polyesters showed different
thermal behaviors: PCA formed liquid crystalline (LC) phase under shear upon heating to 140-170 ºC; PFG
polymerized with the FA feed ratio of 30% spontaneously formed LC phase above 130 ºC.
2011-P11
ポリビニルアルコールとの微視的複合化によるリグノスルホン酸のゲル化と機能発現
仲西雄亮，寺本好邦，西尾嘉之
京都大学大学院農学研究科森林科学専攻
Composite gel formation and functionalization of lignosulfonic acid via microcompositions with poly(vinyl
alcohol)
Yusuke Nakanishi, Yoshikuni Teramoto, and Yoshiyuki Nishio
Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University
Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-8502, Japan
Abstract:
Utilization of isolated lignins as a solid material is constrained by poor film formability andinsufficient moldability due to their low molecular weight and molecular structure. In the present study, we532

prepared lignosulfonic acid (LSA)/poly(vinyl alcohol) (PVA) composite hydrogels. Cross-linking moiety was
introduced by thermal treatment or reaction with glutaraldehyde. By thermal cross-linking, an elution of LSA in
aqueous media could be prevented by formations of hydrogen bonding and sulfonate ester between LSA and
PVA, both of which were corroborated by FT-IR measurement. The thermal-treated composite hydrogels
demonstrated a sustained-release behavior of nicotine in normal saline solution. On the other hand,
pre-interlinking of LSA was performed using poly(ethylene glycol) diglycidyl ether as a linking agent, in orderto improve the LSA content for the LSA/PVA composite hydrogel prepared via chemical cross-linking inaqueous media. Thereupon, the incorporation of linked-LSA achieved much improvement of water retentivity
for the composite hydrogels, where the maximum retentivity of distilled water was > 500 times its own weight.
2011-P12
アルカリリグニンのアルミニウム毒性除去能に関する研究 ―擬似酸性土壌を用いた系での検討―
相見 光*1、栗本康司*2、山内 繁*2、池田 努*3、眞柄謙吾*3*1
東京大学大学院農学生命科学研究科木材化学研究室、*2 秋田県立大学木材高度加工研究所*3
森林総合研究所木材化学研究室
Studies on the ability of alkali lignin to reduce aluminum toxicity assayed using acidic soils
Hikaru Aimi*1, Yasuji Kurimoto*2, Shigeru Yamauchi*2, Tsutomu Ikeda*3, Kengo Magara*3*1
Wood Chemistry Laboratory, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan,*2
Institute of Wood Technology, Akita Prefectural University, Akita 016-0876, Japan,*3
Department of Biomass Chemistry, Forestry and Forest Products Research Institute, 1 Tsukuba, 305-8687,
Japan
Abstract:
The ability of alkali lignin to reduce aluminum toxicity was assayed by plant growth tests using
acidic soils. Acidic soils used in this study were prepared by adding aluminum chloride or hydrochloric acid to
Akadama soil (loamy soil). Root elongations of radish were suppressed in these acidic soils, and addition ofalkali lignin to these soils did not have any effect on recovery. This result indicates that alkali lignin was noteffective at reducing aluminum toxicity when these acidic soils were employed. Preliminary experiment using
saponified ozone-treated kraft lignin indicates that improvement of the ability of alkali lignin may need to
become effective at reduce aluminum toxicity in these soils.
2011-P13
直パルス通電加熱による木質バイオマスの急速熱分解生成物
本間千晶*1、畑 俊充*2、大橋康典*2*3、渡辺隆司*2*1
北海道立総合研究機構林産試験場、*2 京都大学生存圏研究所、*3 現 ハリマ化成株式会社
Products from fast pyrolysis of wood biomass by pulse current heating
Sensho Honma*1, Toshimitsu Hata*2, Yasunori Ohashi*3, Takashi Watanabe*3*1
Hokkaido Research Organization Forest Products Research Institute 1-10 Nishikagura, Asahikawa,
Hokkaido, 071-0198, Japan, *2Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho,
Uji City, Kyoto, 611-0011, Japan, *3present address: Harima Chemicals Incorporated, Kakogawa Plant andCentral Research Laboratory, 671-4 Mizuashi, Noguchi-cho, Kakogawa, Hyogo 675-0019, Japan
Abstract:
Fast pyrolysis of wood biomass with pulse current heating in order to get useful co-products
from bio-oil and to know the pyrolysis conditions on bio-oil compositions and properties and functions ofco-products were examined. The maximum yield of bio-oil was shown at around 500℃. The relationships
between the reaction temperature and mass balance, the chemical structure and bio-oil compositions, theorganics and ammonia adsorbed on char were discussed. It was suggested about the potential of the catalyst on
the yields and properties of the products from fast pyrolysis.
2011-P14
バクテリア由来ピノレジノール変換酵素遺伝子の単離と機能解析
福原優樹*1、上村直史*1、中島正博*2、菱山正二郎*3、笠 大輔*1、原 啓文*4、
片山義博*5、福田雅夫*1、梶田真也*2、政井英司*1*1
長岡技術科学大学・生物、*2 東京農工大学大学院・生物システム応用科学府、*3
森林総合研究所、*4 岡山理科大学・生体医工学科、*5 日本大学・生物資源科学部
Isolation and Characterization of the Pinoresinol Reductase Gene of Sphingobium sp. Strain SYK-6
Yuki Fukuhara*1, Naofumi Kamimura*1, Masahiro Nakajima*2, Shojiro Hishiyama*3, Daisuke Kasai*1, Hirofumi
533

Hara*4, Yoshihiro Katayama*5, Masao Fukuda*1, Shinya Kajita*2, Eiji Masai*1*1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188,*2
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, *3Forestry and Forest Products Research Institute, Tsukuba, Ibaraki
305-8687, *4Department of Biomedical Engineering, Okayama University of Science, Kita-ku, Okayama
700-0005, *5College of Bioresource Science, Nihon University, Fujisawa, Kanagawa 252-0880, Japan
Abstract:
Our group aims to control the lignin biosynthesis in plants by using lignin catabolic genes frombacteria. In this study, we isolated and characterized an enzyme gene involved in the transformation of
pinoresinol (8-8 dimer) from Sphingobium sp. SYK-6. A cosmid clone which conferred the pinoresinoltransformation activity to a host strain Pseudomonas putida was isolated. In the 3.5-kb SalI fragment of thecosmid, we found a 948-bp open reading frame (pinZ) which has 21% identity with pinoresinol reductase of
Arabidopsis thaliana. Purified His-tag fused PinZ produced in Escherichia coli completely converted a racemic
mixture of pinoresinol into lariciresinol and secoisolariciresinol in the presence of NADPH. These results
indicated that pinZ encodes pinoresinol reductase. Disruption of pinZ in SYK-6 demonstrated that this gene isessential for the transformation of pinoresinol.
2011-P15
Sphingobium sp. SYK-6 株から単離されたピノレジノール変換酵素
遺伝子 pinZ を発現する組換え植物の解析
田村尚之*1，中島正博*1，辻 幸子*1，福原優樹*2，上村直史*2，佐藤かんな*1, 片山義博*3，原 啓文*4，菱山正二郎*5，政井英司*2，梶田真也*1*1
東京農工大学大学院生物システム応用科学府、*2 長岡技術科学大学工学部生物系、*3 日本大学 生物資源科学部森林資源科学科、*4 岡山理科大学工学部生体医工学科、*5 森林総合研究所バイオマス化学研究
領域
Analysis of transgenic plants with the bacterial gene for pinoresinol reductase, pinZ, which has been isolated
from Sphingobium sp. SYK-6
Masayuki Tamura*1, Masahiro Nakajima*1, Yukiko Tsuji*1, Yuuki Fukuhara*2, Naoto Kamimura*2
Kanna Sato*1, Yoshihiro Katayama*3, Hirohumi Hara*4, Syoujiro Hishiyama*5, Eiji Masai*2,Shinya Kajita*1*1
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo, 184-8588 Japan, *2Department of BioEngineering, Nagaoka University of Technology,
Niigata, 940-2188, Japan, *3Department of Forest Science and Resources, Nihon University Collage of
Biosource Sciences Kanagawa, 252-8510, Japan, *4Department of Biomedical Engineering, Okayama
University of Science, Okayama, 700-0005, Japan, *5Forestry and Forest Products Research Institute, Ibaraki,305-8687, Japan
Abstract:
We try to modify lignan and lignin biosyntheses in transgenic plants by expression of various
types of bacterial genes for catabolism of aromatic compounds. This study focused on one of the genes, pinZ,
which encodes pinoresinol reductase that catalyzes the conversion of pinoresinol to lariciresinol. To overexpress
the gene efficiency in transgenic plants, we modified codon usage of endogenous pinZ gene and constructed an
expression vector with the resultant cDNA sequence. Generation of transgenic BY-2 cells and Arabidopsis
thaliana plants have been performed by traditional Agrobacterium mediated transformation procedures.
Appropriate level of PinZ activity as it is in recombinant Escherichia coli could be detected in crude enzymes
prepared from both of the transgenic lines.
2011-P116
Quercus 属外樹皮におけるスベリン芳香族部分の化学構造と生合成
伊藤彰伸、松本匠哉、中林亮太、鈴木利貞、片山健至
香川大学農学部
Chemical structure and biosynthesis of poly phenolic domain of suberin in outre bark of Quercus family
Akinobu Ito, Takuya Matsumoto, Ryota Nakabayashi, Toshisada Suzuki, Takeshi Katayama
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795
Abstract:
Suberin is one of the main components in outer bark of woody plants, wound healing tissue ofhigher plants and periderm of underground organs. The insoluble biopolymer is composed of poly aliphatic
domain and poly phenolic domain. Although the structure and composition of the poly aliphatic domain were
well investigated, those of the poly phenolic domain were unclear. In this study, a β-O-4’ enol ether dimer ofmethyl ferulate and its derivatives were isolated from methanolysis products of extractive free outer bark of534

Quercus suber and Q. variabilis. Dehydrogenative polymerization of feruloyloxy hexadecanoic acid withhorseradish peroxidase and H2O2 was carried out as a suberin model system. A 5-O-4’ diaryl ether type dimerof the substrate and its derivatives were isolated together with a β-5’ dimer. These results suggest thatferuloyloxy fatty acid derivatives are dehydrogenetively polymerized by a peroxidase to give β-O-4’ enol ether
structures with β-5’, 5-O-4’ and the other coupling structures, which would form the poly phenolic domain ofsuberin in the outer bark of Quercus family. Dehydrogenative polymerization of feruloyloxy hexadecanoic acidwith Q. variabilis bark crude enzyme is being examined.
2011-P17
シロイヌナズナ T-DNA 挿入変異体を用いたリグニン前駆物質輸送体の絞り込み
津山濯*1、高部圭司*1、尾形善之*2*1
京都大学大学院農学研究科、*2 理化学研究所植物科学研究センター
Seeking the candidates of lignin transporter using Arabidopsis T-DNA tagged mutants
Taku Tsuyama*1, Keiji Takabe*1, Yoshiyuki Ogata*2*1
Graduate School of Agriculture, Kyoto University, Kyoto, 606-8502, Japan, *2RIKEN Plant Science Center,
Yokohama, Kanagawa, 230-0045, Japan,
Abstract:
Lignin biosynthesis proceeds in three steps; biosynthesis, transport, and polymerization oflignin precursors. Though many researches have elucidated the biosynthesis and the polymerization of lignin
precursors, their transport mechanism has not been investigated except coniferin transport into vacuole. To
identify the transporter of lignin precursor, we selected candidates of transporter genes in Arabidopsis thaliana
by co-expression analysis. Mature stems of T-DNA tagged mutants of candidate genes were harvested andanalyzed their lignin distribution. A T-DNA mutant showed weak Mäule color reaction in iterfascicular fiber.
Although lignin content of the mutant was not different from Col-0, S/V ratio was decreased. The candidate oftransporter gene may be involved in transport of S lignin precursors.
2011-P18
サリチル酸投与によってシラカンバ幼植物体に誘導される植物免疫に係わるペルオキシダーゼの解析
鈴木 拡, 石栗 太, 飯塚和也, 吉澤伸夫, 横田信三
宇都宮大学農学部
Analysis of plant-immunity-related peroxidases induced in Japanese birch plantlets by administration ofsalicylic acid
Hiromu Suzuki, Futoshi Ishiguri, Kazuya Iizuka, Nobuo Yoshizawa, Shinso Yokota
Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan
Abstract:
Salicylic acid (SA) is known to induce immunity in plants against pathogens through systemicacquired resistance. The present study investigated localization of peroxidase induced in Japanese birch plantlets
by administration of SA. Histochemical observation of peroxidase revealed that SA induced peroxidases withhigher activity in the wider area around the administered site compared to the controls, suggesting the
involvement of these peroxidases in plant immunity. Proteomic analysis was also performed using protein
samples prepared from the plantlets treated with SA. As the results, malate dehydrogenase and arginase weredetected and identified as the proteins specific to SA treatment.
2011-P19
ファイトアレキシン生産時の Cupressus lusitanica 培養細胞のリグニン生成
柴田久美子、Ransika De Alwis、藤田弘毅
九州大学大学院農学研究院
Lignin formation at phytoalexin producing Cupressus lusitanica cultured cell
Kumiko Shibata, Ransika De Alwis, Koki Fujita
Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan
Abstract:
The lignin formation with water stress, mechanical stress, elicitor stress on Cupressus lusitanica
cultured cell was investigated. By analysis of acidolysis and pyrolysis method on the cells at the incubation timesame as phytoalexin production (up to 5 days), only the trace amount of lignin degradation products weredetected. No significant change of lignin content was observed on Klason lignin content. Therefore, the cells
would response at first for protection from elicitor stress in short time (several days) with low molecular weightphytoalexin such like β-thujaplicin. And then at later phase, lignin formation was completed in the cell wall
against various stresses including water stress, mechanical stress and so on.
535

第 57 回 （2012.10.17-18） アクロス福岡 国際会議場
2012-101
二段階半流通型加圧熱水処理不溶残渣のリグニン
鈴木信義、高田昌嗣、山内一慶、坂 志朗
京都大学大学院エネルギー科学研究科
Lignin in the residues as treated by two-step semi-flow hot-compressed waterNobuyoshi Suzuki, Masatsugu Takada, Kazuchika Yamauchi, Shiro Saka
Graduate School of Energy Science, Kyoto University, Japan
Abstract:
Japanese cedar (Cryptomeria japonica) and Japanese beech (Fagus crenata) were treated with
two-step semi-flow hot-compressed water. The first stage was conducted at 230ºC/10 MPa for 15min and thesecond stage at 270ºC/10MPa for 15mim. The residues at the first and second stages of Japanese cedar
contained 59.7 and 43.1wt% of the original lignin, while these of Japanese beech 50.8 and 23.2wt%,
respectively. As hot-compressed water treatment proceeds for the first and second stages, the cell wall wasdestructed for both species. However, the cell wall of the beech was remarkably destructed, compared withcedar, and in the residue of the second stage, only the middle lamella region remained for beech. On the other
hand, for the cedar, the cell wall was not so destructed and its structure was comparatively retained. From theseobservations and the yield of alkaline nitrobenzene oxidation products, the fiber cell wall of the beech encrustedwith syringyl lignin would be more likely to be composed of non-condensed type of lignin, while middle
lamella and its cell corner region encrusted with guaiacyl lignin would be largely composed of condensed typeof lignin. In the case of cedar, however, the middle lamella region remained even at the end of the second stage,
thus must have mainly condensed type lignin. In addition, compared with the beech, the cell wall portion of thecedar must have more condensed type of lignin. Such a difference suggests that the topochemical difference inlignin exists in the residues as treated by hot-compressed water.
Keywords: hot-compressed water, topochemistry, lignin distribution, TEM, UV microscope
2012-102
バイオディーゼル燃料用植物ジャトロファから抗酸化活性を有するカテコール型リグナン・ネオリグナンの単離
江藤恭子*1，小池 悠*1，鈴木利貞*1，片山健至*1，Tanachai Pankasemsuk*2*1
香川大学農学部，*2 チェンマイ大学農学部
Isolation of antioxidant catechol lignan/neolignans from Jatropha curcas, a shrub for biodiesel fuel production
Kyoko Eto*1, Yu Koike*1, Toshisada Suzuk*1, Takeshi Katayama*1, Tanachai Pankasemsuk*2*1
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan*2
Faculty of Agriculture, Chiang Mai University, Chiang Mai 50200, Thailand
Abstract:
The ethyl acetate soluble fraction of the methanol extract obtained from the defatted seed
residue of Jatropha curcas had the same potent antioxidant activities as Trolox. From the antioxidant fraction acatechol-type furofuran lignan, (+)-3,3’-bisdemethylpinoresinol; five catechol-type 1,4-benzodioxane
neolignans, (-)-isoamericanol A, (+)-americanol A, 9’-O-methylisoamericanol A, 9’-O-methylamericanol A, andisoamericanin A; and two catechol-type sesquineolignans with furofuran and 1,4-benzodioxane moieties,
isoprincepin and princepin were isolated and identified. Potent antioxidant activities of these eight compounds
were also confirmed. The ethyl acetate soluble fraction of the methanol extract was found to be more effective
than α-tocopherol by the tests for preventing oxidation of commercial salad oil and Jatropha oil and thebiodiesel fuels (BDF) derived from the two oils.
2012-103
リグニン性状とリグニン硬化エポキシ樹脂特性の相関
香川博之*１、岡部義昭*１、佐々木 千鶴*2、中村 嘉利*2
*１(株)日立製作所日立研究所有機材料研究部*2
徳島大学大学院ソシオテクノサイエンス研究部ライフシステム部門
Correlation between lignin properties and properties of epoxy resin hardened by lignin
Hiroyuki Kagawa*１, Yoshiaki Okabe*１, Chizuru Sasaki*2, Yoshitoshi Nakamura*2*１
Hitachi Research Laboratory, Hitachi, Ltd.,
7-1-1 Omika-cho, Hitachi-shi, Ibaraki-ken, 319-1292 JAPAN
536

*2

Department of Life System, Institute of Technology and Science, The University of Tokushima, 2-1
Minamijosanjima-cho, Tokushima-shi, Tokushima- ken, 770-8506 JAPAN
Abstract:
We are currently researching the use of woody biomass, particularly the application of lignin
extracted from steam-exploded woody biomass to epoxy resin, which is widely used in modern electric andelectronic equipment. We have already reported that the weight-average molecular weight (Mw) of lignin after
the steam explosion process decreased by setting a higher steam pressure and a longer process time, however,
the hydroxyl equivalent of the lignin increased under those conditions. We report that the correlation between
lignin properties and properties of epoxy resin hardened by lignin. Epoxy resins hardened by lignin withdifferent Mw showed approximately the same glass transition temperatures (Tg), implying that the crosslink
density of hardened resin is not much different in this range of Mw. We also prepared epoxy molding
compounds using lignin as a hardener. Steam-explosion conditions of cedar chips were explored, and themolding compounds with lower water absorption were obtained for longer steam time, reflecting the propertiesof lignin.
Mechanical and electrical properties of molding compounds were independent of thesteam-explosion conditions.
Keywords: steam explosion, epoxy, resin, crosslink, mechanical property.
2012-104
グリコールエーテル系溶剤中での酸分解によるスギ木粉からのリグニン抽出および抽出リグニンのサーモト
ロック液晶性ポリエステル化
石井大輔*１，山崎昌男*2, 山太郎*１，井林賢太*１，白井伸明*3，松本正*3，中沖隆彦*１，林久夫*１*１
龍谷大学理工学部物質化学科，*2 桜宮化学株式会社，*3 滋賀県東北部工業技術センター
Lignin extraction from Sugi (Cryptomeria japonica D. Don) woodmeal by acid-catalyzed solvolysis inglycolethers and preparation of thermotropic liquid crystalline polyester from the glycolether lignin
Daisuke Ishii* １ , Masao Yamazaki*2, Ryotaro Yamamoto* １ , Kenta Ibayashi* １ , Nobuaki Shirai*3, Tadashi
Matsumoto*3, Takahiko Nakaoki*１, Hisao Hayashi*１*1
Department of Materials Chemistry, Faculty of Science and Technology, Ryukoku University, Otsu, Shiga
520-2194, Japan, *2Sakuranomiya Chemical, Co. Ltd., Moriyama, Shiga 524-0044, Japan,*3
Northeastern Industrial Research Center of Shiga Prefecture, Nagahama, Shiga 526-0024, Japan
Abstract:
Extraction of Lignin from Sugi (Cryptomeria japonica D. Don) by acid-catalyzed solvolysis inglycolethers at 160 C for 2 h has been performed. The glycol lignin, obtained by concentrating the soluble
fraction in glycolethers, showed good solubility to acetone, 2-butanone and chloroform. Furthermore, it was
found that the glycol lignin contains considerable amount of hydtoxyl groups (0.677 mmol OH / g ). Preparationof polyesters by esterification of the glycol lignin and diacid chlorides (adipoyl chloride, sebacoyl chloride, andterephthaloyl dichloride) was performed in acetone. The polyesters, obtained as the insoluble fraction in acetone,
showed melting transitions at 70 C and 190-210 C. The multiple melting transition implies that the glycol
lignin polyester has the thermotropic liquid crystalline nature, which was shown by polarized optical
microscopy.
Keywords: solvolysis lignin, glycolethers, sulfonic acid, liquifaction, liquid crystalline polyesters
2012 特別講演
バイオエタノール製造で副生するリグニンの有効利用
坂西欣也*1、松永興哲*1、井上宏之*1、スヤント*2*1
産業技術総合研究所、 *2 インドネシア BPPT
Utilization of lignin coproduced in the bio-ethanol production process
Kinya Sakanishi*1, Kotetsu Matsunaga*1, H2iroyuki Inoue*1, Suyanto**1
National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8568, Japan,*2
Agency for the Assessment and Application of Technology, Indonesia
Abstract:
Lignocellulosic biomass resources, such as wood wastes and oil palm trunks(OPT), areexpected to be feedstock for recovering lignin derivatives during 2 nd-generation bioethanol production process.
In the present study, OPT were thermally extracted with ethyleneglycol and phenol/ ethyleneglycol mixed
solvent. The soluble fraction includes mainly lignin derived fraction (LDF), which exhibited the good plasticity
and thermal stability. The plasticized fractions were processed to prepare green composites (biomass-derived
carbon fibers and biomass plastics).
Keywords: lignocellulosic biomass, oil palm trunks, solvent extraction, ethanol fermentation, lignin
537

2012-201
MWL 抽出残渣からの LCC 解析用フラクションの探索 (2) ：2 次元 NMR による分析
宮川泰幸、上高原浩、高野俊幸
京都大学大学院農学研究科
Fractionation of extracted residue of MWL for LCC analysis (2)Yasuyuki Miyagawa, Hiroshi Kamitakahara, Toshiyuki Takano
Division of Forest & Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku. Kyoto,606-8502, Japan
Abstract:
The residual wood meal left after milled wood lignin (MWL) isolation (MWR) was fractionatedseveral times to afford xylan-lignin fraction (X-L). X-L was extracted with lignin solvent 1, 4-dioxane/water (9:1, v/v) to give a soluble fraction (X-L-Fraction-1 (XL-F1)) and an insoluble fraction (XL-F1-residue).
XL-F1-residue was further extracted with xylan solvent (DMSO) to afford a soluble fraction (X-L-Fraction-2(XL-F2)) with 43.0% yield based on XL-F1-residue. XL-F2 was mainly composed of xylan and some amountof lignin, and according to the 2D NMR analysis, it is suggested the existence of phenyl glycoside type LC
linkages in XL-F2.
Keywords: Eucalyptus globulus; milled wood lignin (MWL); lignin-carbohydrate complex (LCC); gelpermeation chromatograph5y (GPC); hetero-nuclear single quantum coherence (HSQC)
2012-20213
C 標識法と高分解能NMR を組み合わせたリグニンの構造解析
今村良教*1、西村裕志*2,*5、寺島典二*3、松下泰幸*1、青木 弾*1、片平正人 5*4*5、福島和彦*1*1
名古屋大学大学院生命農学研究科、*2 京都大学生存圏研究所、*3 名古屋大学名誉教授、*4 都大学エネル
ギー理工学研究所、*5JST・CREST
Structural analysis of lignin by a specific13C-enrichment technique combined with high resolution solution state
NMR
Yoshinori imamura*1, Hiroshi Nishimura*2*5 ,Noritsugu Terashima*3, Yasuyuki Matsushita*1, Dan Aoki*1,Masato
Katahira*4*5, Kazuhiko Fukushima*1*1
Graduate School of bioagricultural Science, Nagoya University, Nagoya 464-8601, Japan, *2Research institutefor Sustainable Humanosphere, Kyoto University, Uji 611-0011, Japan, *3Emeritus professor, Nagoya University,
Nagoya 464-8601, Japan, *1Institute of Advanced Energy (IAE), Kyoto University, Uji 611-0011, Japan, *5JST・
CRST
Abstract:
In order to analyze lignin structures, a technique of specific 13C-enrichment of cell wall lignin
combined with nondestructive analysis of the whole cell wall material by high-resolution 2D-NMR (HSQC) in
solution-state has been developed. Additional technique of making difference NMR spectrum between 13C-enriched lignin and unenriched lignin provided a simpler spectrum arising exclusively from the 13C -enrichedcarbon. From the signal intensity of the simplified difference HSQC spectrum between13Cα-enriched andunenriched lignins, quantitative determination was made on the frequencies of major inter-unit bonds, andconiferyl alcohol, coniferaldehyde end groups.
2012-203
MALDI-FT-ICR MS/MS による単離リグニンの精密構造解析
吉岡 康一*1、丸本 真輔*1、渡辺 隆司*1, *2*1
京都大学生存圏研究所、*2JST, CREST
Structural analysis of the isolated lignin by MALDI-FT-ICR MS/MS
Koichi Yoshioka*1, *2, Shinsuke Marumoto*1, Takashi Watanabe*1, *2*1Research Institute for Sustainable Humanosphere (RISH), Kyoto University, Gokasho, Uji, Kyoto 611-0011,
Japan. *2CREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
Abstract:
MALDI-MS gives direct structural information in a wide range of molecular weight regions.
However, Abstract: structural analysis of lignin by MALDI-MS is still limited. Our group has analyzed
isolated and synthetic lignin using MALDI-TOF and Fourier-transform ion cyclotron resonance (FT-ICR) MS.
In this study, structure of the lignin isolated from Eucalyptus globulus and Fagus crenata was analyzed by
MALDI-FT-ICR MS/MS. Comparative analyses of the mass spectra between the isolated lignin and synthetic
lignin model compounds demonstrated existence of oligomeric structures including β-β and β-O-4 linkages.
Keywords: interunit linkage, network structure, β-O-4 linkage, syringaresinol,
Eucalyptus globulus, Fagus crenata538

2012-204
Lignin released from spruce wood during hot-water extraction
Ivan Sumerskiy, Andrey Pranovich, Bjarne Holmbom, Stefan Willför
Process Chemistry Centre, Laboratory of Wood and Paper Chemistry, Åbo Akademi University, FI-20500
Turku/Åbo, Finland.
Abstract.
Ground spruce sapwood was extracted with pressurized hot water in an accelerated solvent
extractor (ASE) at 170 ºC during 20, 60 and 100 min. Dissolved aromatic substances in water extracts wereisolated by sorption on XAD-7 resin and fractionated into lignin, oligomeric aromatic substances (OAS) andinsoluble-in-methanol compounds (IMC). The extracted and separated fractions as well as the ground wood
before and after extraction were analyzed by classical wet chemistry (Derivatization Followed by Reductive
Cleavage (DFRC), Klason lignin and content of extractive substances) and instrumental physico-chemical
methods (GC, RP-HPLC and SEC, and NMR, FT-IR, UV and mass spectrometry). The yield of dissolved lignin
slightly increased during the hot-water extraction. Simultaneously, the proportion of lignin in extracted total
dissolve solids decreased to about the half. The physico-chemical characteristics of isolated lignins wereconsiderably different compared to spruce MWL. The extracted lignin had a notably lower molar mass than
MWL. During hot-water extraction the number of hydroxyl and especially carboxylic groups in lignins
increased and the lignins became more condensed.
2012-205
アセチルブロミド法によるリグニン含有量の定量におけるタケパルプ中のキシラン含有量の影響(II) フルフラール生成量の検討
中川明子、張翼、大井洋
筑波大学大学院 生命環境科学研究科
Effect of xylan content in alkali bamboo pulp on determination of lignin content by acetyl bromide method (II)–Examination of furfural production Akiko Nakagawa-izumi, Yi Zhang, Hiroshi Ohi
Graduate School of Life and Environmental Sciences, University of Tsukuba
Abstract:
The xylan in hardwood pulp affects the acetyl bromide method due to UV absorption of the
product. The maximum production of furfural from xylose in the acetyl bromide treatment was 8.5 %. During
room temperature treatment, furfural decreased slightly, but UV absorbance of the resulting solution at 280nm
increased. On the other hand, in this treatment with heating, furfural decreased remarkably but those of UV
absorbance increased slightly. It shows that xylan produces furfural and it promptly changes to product which
has UV absorption.
2012-206
リグニン β-O-4 結合新規選択的開裂法(γ-TTSA 法)の検討(4)-天然リグニンへの適用安藤大将*1、西村裕志*2*3、 片平正人*３、高野俊幸*1、矢野浩之*２、中坪文明*２*1
京都大学大学院農学研究科、*２京都大学エネルギー理工学研究所、*３京都大学生存圏研究所
Studies on the selective cleavage method for β-O-4 linkages of lignins (γ-TTSA method) (4) -Application tonatural ligninDaisuke Ando*1, Hiroshi Nishimura*２*３, Masato Katahira*２, Toshiyuki Takano*1, Hiroyuki Yano*3, Fumiaki
Nakatsubo*3*1
Guraduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan*2
Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan*3
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan
Abstract:
Application of γ-TTSA method (consisted of four reactions; tosylation, thioetherification,
sulfonation, alkali-treatment), which has been proposed as new selective β-O-4 cleavage method, to Milled
Wood Lignin (MWL) from Eucalyptus globulus. HSQC-NMR spectra of the four reaction products suggested
that the four reactions proceeded in MWL as well as in lignin model compounds. Especially, HSQC-NMR
spectrum of the final product revealed that β-O-4 linkages were selectively cleaved with the retention of β-βlinkages in the last reaction.
Keywords: Cleavage of β-O-4 linkage, β-Elimination, Eucalyptus globulus, HSQC-NMR, LCC, Milled
Wood Lignin
2012-207
539

TEMPO をメディエーターに用いたリグニンモデル化合物の電解酸化
三波 由実*1、白石 匠*2、高野 俊幸*1、上高原 浩*1*1
京都大学大学院農学研究科、*2 京都大学生存圏研究所
TEMPO-mediated electro-oxidation of lignin model compounds
Yumi Sannami*1, Takumi Shiraishi*2, Toshiyuki Takano*1, Hiroshi Kamitakahara*1*1
Division of Forest & Biomaterials Science, Graduate School of Agriculture,
Kyoto University, Sakyo-ku. Kyoto, 606-8502, Japan, *2Research Institute for Sustainable Humanosphere,
Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
Abstract:
The TEMPO-mediated electro-oxidation of monomeric lignin model compound 1G(1-(4’-ethoxy-3’-methoxyphenyl) ethanol) in 70% CH3CN-H2O and 10% dioxane-carbonate buffer afforded thecorresponding Cα-carbonyl compound 2G in high yields, suggesting that the oxidation of Cα-hydroxyl groupproceeded efficiently. On the other hand, in the TEMPO-mediated oxidation of dimeric compound 3G(4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether) in 70% CH3CN-H2O, most of starting material 3G wasrecovered, whereas in that of compound 3G in 10% dioxane-carbonate buffer, the corresponding Cγ-carbonylcompound 7G was obtained as a main product in moderate yield, suggesting that the oxidation of Cγ-hydroxyl
group proceeded efficiently. As the result, it was found that the TEMPO-mediated electro-oxidation was
significantly influenced by the solvent used.
Keyword: 2,2,6,6-tetramethylpiperidine-N-oxyl, electrolysis, mediator, lignin , Cα-carbonylation
2012-208
広葉樹リグニン熱分解における低分子シリンゴール類/グアイアコール類の生成挙動
小竹毅郎、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Formation behaviors of monomeric syringols/guaiacols in pyrolysis of hardwood lignin
Takeo Kotake, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University
Abstract:
Hardwood lignin gives monomeric syringols/guaiacols with various side-chains at 300-350°C,
while their pyrolytic formation mechanisms are not well-known. To clarify it, pyrolytic reactivities of sinapyl
alcohol (SA) and coniferyl alcohol (CA) were compared first under the condition of N2/200-350ºC/5min. As aresult, pyrolytic products from SA were similar to those from CA, which suggests similar reactions occurringfor both compounds. Influences of the addition of a solvent (1,3-diphenoxybenzene) and an H-donor(1,2,3,10b-tetrahydrofluoranthene) on the reactivities of SA and CA suggested that the decomposition reactivityof SA dramatically increaseat 350ºC where radical intermediates play important roles. This characteristic feature reduced the monomericsyringols yields significantly at 350ºC under neat condition and in solution from SA and buna milled wood
lignin (MWL). The addition of the H-donor increased the monomeric syringols yields greatly, which is
explained by the stabilization effect on the intermediate radicals. On the other hand, the monomeric syringols
yields from buna wood at 350ºC were much higher from those of buna MWL and sugi (MWL/wood) even
without the addition the H-donor. These results indicate that the buna wood pyrolysis at 350ºC produces someH-donors for stabilization of the intermediate radicals from buna lignin.
Keywords: lignin, pyrolysis, mechanism, sinapyl alcohol, monomer formation
2012-209
亜硫酸を用いた前加水分解化学パルプ化法
石 岩、横山朝哉、秋山拓也、松本雄二
東京大学大学院農学生命科学研究科
Prehydrolysis chemical pulping by the use of sulforous acid
Shi Yan, Tomoya Yokoyama, Takuya Akiyama, Yuji Matsumoto
Wood Chemistry Laboratory, Department of Biomaterials Sciences,
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
For the total utilization of wood polysaccharides, suitable combination of prehydrolysis stage
and chemical pulping (delignification) stage was surveyed., Condition of prehydrolysis by the use ofhydrochloric acid, sulfuric acid or sulfurous acid was adjusted so that majority of hemicellulose could beobtained as monosaccharides. Prehydrolysis residue was subjected to chemical pulping under various codition.
Pulping of prehydrolysis residues obtained by hydrochloric acid or sulfuric acid were rather difficult under any
540conditions examined. On the other hand prehydrolysis residue obtained by sulfurous acid were found to beeasily delignified by simple alkali cooking and give pulp in rather high yield (42% based on the original wood)with rather high purity as cellulose (about 92%). Monosaccharide yield from hemicellulose during prehydrolysis
stage was close to 90%.
2012-210
Biodegradation behavior of petroleum hydrocarbons by Pestalotiopsis sp. NG007
Dede Heri Yuli Yanto, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime 790-8566, Japan
Abstract:
The biodegradation of three different petroleum hydrocarbon samples, namely, heavy oil A,
heavy oil C and asphalt by Pestalotiopsis sp. NG007 was examined under ligninolytic condition at pH 4.5 orunder saline condition at pH 8.2. Pestalotiopsis sp. NG007 exhibited high activity for the biodegradation of all
three petroleum hydrocarbon samples. However, the biodegradability was found to be highly dependent on thetype of petroleum hydrocarbons and the environmental condition. The degree of biodegradation of petroleumhydrocarbon components differed according to the petroleum hydrocarbons, the aliphatic fraction being more
susceptible to biodegradation than the aromatic, resin, and asphaltene fraction in all petroleum hydrocarbon
samples. The extent of biodegradation by Pestalotiopsis sp. NG007 was found to be in the order of heavy oil A> heavy oil C > asphalt; the petroleum hydrocarbons with higher composition of aliphatic fraction being more
susceptible to biodegradation. Regarding to environmental condition, aliphatic and aromatic fraction waspreferentially degraded under saline condition at pH 8.2, particularly in asphalt, led to higher biodegradation
rate compared with under ligninolytic condition at pH 4.5. The study shows that the dynamic ratio of aliphatic
to other constituents in petroleum hydrocarbons affects the biodegradation behavior by Pestalotiopsis sp.
NG007.
Keywords: biodegradation, heavy oil, asphalt, hydrocarbon, Pestalotiopsis sp., ligninolytic enzymes.
2012-2011
Enhancement of ligninolytic systems for degradation of DDT by Trametes versicolor U97 pre-grown in oil palm
empty fruit bunch
Ajeng Arum Sari*1, Kazutaka Itoh*2, Sanro Tachibana*2*1
The United Graduate School of Agricultural Sciences, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime
790-8566, Japan,*2Department of Applied Bioscience, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi,
Matsuyama, Ehime 790-8566, Japan
Abstract:
Oil palm empty fruit bunch (EFB) as agricultural waste is potentially used for pre-grown sourceof white-rot fungi (WRF) since it contains lignin, cellulose and hemicellulose. Enzyme activity secreted by
WRF mainly depends on its additives such as metals and veratryl alcohol. This study aims to investigate theability of EFB as pre-grown source of Trametes versicolor U97 to degrade DDT in liquid medium and soil
including addition of several additives e.g. CuSO4, MnSO4, and veratryl alcohol in soil. DDT in water, malt
extract liquid medium, and soil was degraded 68%, 75%, and 54% during 30 d incubation period, respectively.
Addition of CuSO4 even in low concentration and MnSO4 in high concentration have negative effect for DDT
degradation. Furthermore, 0.5 mM of veratryl alcohol was optimum concentration to obtain the maximum
degradation. Addition of EDTA as lignin peroxidase (LiP) inhibitor could reduce degradation of DDT, revealed
lignin peroxidase plays a role in degradation of DDT.
Keywords: biodegradation, DDT, oil palm empty fruit bunch, Trametes versicolor U97, lignin peroxidase.
2012-212
Degradation of 2,4,8-trichlorodibenzofuran, a polychlorinated dibenzofurans, by Cerrena sp. F0607
Asep Hidayat, Kazutaka Itoh, Sanro Tachibana
Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime 790-8566, Japan
Abstract:
Cerrena sp. F0607 was chosen as fungus degrader and degradation of
2,4,8-trichlorodibenzofuras (2,4,8-TCDF) was investigated. The degradation of 2,4,8-TCDF was above 40%
after 30 day, the degradation per-unit biomass increased during the incubation period, and glucose consumption
increased rapidly when 2,4,8-TCDF was present in the culture. It was evidence that fungus oxidized
2,4,8-TCDF as an alternative source of energy and carbon. The increasing of glucose consumption stimulated
the growth of fungi that will couple to the degradation of 2,4,8-TCDF. The ligninolytic enzymes were detected
and tent to increase their activity in the presence of 2,4,8-TCDF, especially laccase, manganese peroxidase(MnP) and lignin peroxidase (LiP). The addition of various additives, such as MnSO 4, CdSO4, CuSO4,
1-Hydroxybenzotriazole (HBT), NaN3, AgNO3, and Piperonyl Butoxide (PB) was investigated. The result541

showed that there were variation on both degradation and enzymatic activities. Through a Partial Least Squareanalysis, it could be clearly concluded that laccase has a role in the degradation of 2,4,8-TCDF. Whereas
cytochrome P-450 monooxygenase could not be excluded from the degradation of 2,4,8-TCDF, since PB
showed inhibition of the degradation without disturbing fungal growth.
Keywords: biodegradation, 2,4,8-TCDF, Cerrena sp., ligninolytic enzymes, oxygenase.
2012-213
高活性リグニン分解菌 Phanerochaete sordida YK-624 株における glyoxal oxidase 遺伝子高発現によるリグ
ニン分解特性の改善
山田祐人*1、平井浩文*2、河岸洋和*1*2*1
静岡大学農学部、*2 静岡大学創造科学技術大学院
Improvement of ligninolytic properties by high expression of glyoxal oxidase gene in hyper lignin-degrading
fungus Phanerochaete sordida YK-624
Yuto Yamada*1, Hirofumi Hirai*1, Hirokazu Kawagishi*1*2*1
Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan*2
Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529,
Japan
Abstract:
Glyoxal oxidase (GLOX) is a radical copper oxidase that catalyzes the oxidation of aldehydes
to carboxylic acids coupled to the dioxygen reduction to H2O2. GLOX is a source of theextracellular H2O2 that is required for the oxidations catalyzed by the ligninolytic peroxidases.
In the present study, GLOX gene (glx) of Phanerochaete chrysosporium was cloned, and thepromoter of bee2 cloned from P. sordida YK-624 was used to drive the expression of glx. The
expression vector was transformed into a P. sordida YK-624 uracil auxotrophic mutant UV-64,
and 16 clones were obtained as glx-introducing transformants. These transformants showed
higher GLOX activities than wild type of P. sordida YK-624 and control transformants into
which only marker plasmid was introduced although manganese peroxidase activities of thesetransformants were hardly different from those of wild type and control transformants.
Moreover, these transformants showed higher ligninolytic activity than wild type and control
transformants. These results suggest that ligninolytic properties of white-rot fungi can be
improved by high expression of glx.
2012-214
大腸菌によるポルフィリンの生産と、そのリグニン分解
岸川明日香*1、福留裕文*2、福留留美*2、石橋徹*2、近藤隆一郎*3*1
九州大学大学院生物資源環境学府、*２シキソンパワー株式会社、*３九州大学大学院農学研究院
Efficient production of porphyrin by Escherichia coli and lignin degradation by coproporphyrin
Asuka Kishikawa*1, Hirofumi Fukutome*2, Rumi Fukutome*2, Toru Ishibashi*2, Ryuichiro Kondo*3*1
Department of Agro-environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences,
Kyushu University, Fukuoka 812-8581, Japan,*2SIXONPOWER Co., Ltd.
*3
Department of Agro-environmental Sciences, Faculty of Agriculture, Kyushu University, Fukuoka 812-8581,
Japan
Abstract:
Escherichia coli carrying a deletion of ypjD gene produced red pigment, when it is cultivated inminimal A culture medium. This pigment was purified and analyzed by LC/MS, GC/MS, 1H NMR, 13C NMR,
and NOESY, and it was assumed to be coproporphyrin(Ⅲ). In order to find a new way to use coproporphyrin,
we tried to degrade lignin by photosensitization reaction of coproporphyrin. The absorbance of alkali lignin at
280 nm decreased after photo irradiation at 368 nm with coproporphyrin(Ⅰ).
Keywords: Coproporphyrin, Escherichia coli, Lignin degradation, Photosensitizer, Photo irradiation
2012-215
糸状菌ラッカーゼの至適 pH および速度パラメーターに及ぼす緩衝液中のアミノ基の影響
池田 隆造*1、平 修*2、近藤 隆一郎*3、後藤 秀幸*1
*1
石川県立大学大学院生物資源環境科学研究科、*2 北陸先端科学技術大学院大学マテリアルサイエンス研
究科、*3 九州大学大学院農学研究院環境農学部門サスティナブル資源科学講座
Effects of amino group in buffer systems on optimal pH and kinetic parameters of fungal laccase
Ryuzoh Ikeda*1, Shu Taira*2, Ryuichiro Kondo*3, Hideyuki Goto*1
542

*1

Graduate School of Bioresources and Environmental Science, Ishikawa Prefectural University, 1-308
Suematsu, Nonoichi, Ishikawa 921-8836, Japan; *2School of Material Science, Japan Advanced Institute of
Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan; *3Department of Agro-Environmental
Sciences, Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract:
We found that the optimal pH of fungal laccase from the white rot fungus Pycnoporus
cinnabarinus varies with buffer systems used in the enzyme reaction. Buffer systems containing amino group(glycine and aspartic acid, tris, and ammonium) caused the optimal pH shifting to alkaline side by 1.5 pH unit
for ABTS and by 1.0 pH unit for DMP. There occurred an increase of Km and a decrease of kcat for ABTS and adecrease of Km and kcat for DMP in aspartate and tris-acetate buffer system containing amino group. Protonatedamino group in the buffer systems seems to affect the optimal pH and kinetic parameters for the laccase.
Keywords: fungal laccase, optimal pH shifting, substrate specificity, substrate binding site, carboxylic acid2012-216
アオモリヒバのリグナン生合成に関与する O-メチルトランスフェラーゼ遺伝子の取得
鈴木綾乃*1、萩原迪子*1、米田夕子*1、河合真吾*1、西田友昭*1、サフェンドリ・コマラ・ラガムスタリ *2、鈴木史朗*2、梅澤俊明*2*1
静岡大学農学部、*２京都大学生存圏研究所
Isolation of Thujopsis dolabrata var. hondai O-metyltransferase involved in the biosynthesis of lignans
Ayano Suzuki*1, Michiko Hagiwara*1, Yuko Yoneda*1, Shingo Kawai*1, Tomoaki Nishida*1, Safendrri Komara
Ragamustari*2, Shiro Suzuki*2, Toshiaki Umezawa*2*1
Department of Environment and Forest Resources Science, Faculty of Agriculture, Shizuoka University, 836
Ohya, Suruga-ku, Shizuoka 422-8529, Japan,*2Research Institute for Sustainable Humanosphere, Kyoto
University, Uji, Kyoto 611-0011, Japan
Abstract:
Thujopsis dolabrata var. hondai (Aomori-hiba, Hinoki-asunaro) is one of the useful woods inJapan. Moreover, it is known that T. dolabrata var. hondai biosynthesizes anti-cancer lignans, such as
deoxypodophyllotoxin, β-peltatin and so on. These lignans have 3,4,5-trimethoxylphenyl nuclei, but theseoxidative modifications are not present in gymnosperm lignin. Comprehensive genetic analysis by a next
generation sequencer is one of the most effective approaches to identify the whole expressed genes in aparticular sample, which can help identify the genes involved in the methoxyl substitutions. The aim of thisstudy is to isolate cDNAs which encode enzymes involved in the biosynthesis, especially O-methyltransferases(OMTs). As a result, we isolated six OMT genes, TdOMT 1 to TdOMT 6. Currently, we are conducting theheterologous expression of these genes.
Keywords: O-methyltransferase; syringyl lignans; biosynthesis; heterologous expression; Thujopsis
dolabrata var. hondai
2012-217
O-Methyltransferases involved in lignan biosynthesis in Anthriscus sylvestris
Safendrri Komara Ragamustari*1*2, Takefumi Hattori*1*3 , Eiichiro Ono*4, Shiro Suzuki*1, Masaomi Yamamura*1,
and Toshiaki Umezawa*1*2*1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
*2
Institute of Sustainability Science, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan*3
Institute of Socio-Arts and Sciences, The University of Tokushima, Tokushima, 1-1, Minamijosanjima-cho,
Tokushima 770-8502, Japan, *4Institute for Plant Science, Suntory Business Expert Ltd. 1-1-1 Wakayamadai,
Shimamoto, Mishima, Osaka 618-8503, Japan
Abstract:
We report the isolation and characterization of two plant O-methyltransferases (OMTs)
involved in lignan biosynthesis in Anthtriscus sylvestris. The recombinant OMTs were overexpressed in E. coli
expression systems and were tested for activity using a number of substrates. Both OMTs showed exclusive
regio-specific activity towards dibenzylbutyrolactone lignans. AsOMT50 converted matairesinol into arctigenin,
while AsOMT116 converted thujaplicatin into 5-methylthujaplicatin, and were thus renamed AsMROMT andAsTJOMT, respectively. In a phylogenetic tree generated from an alignment of plant OMT amino acidsequences, AsMROMT and AsTJOMT are located in a clade dominated by plant flavonoid and lignan OMTs.
AsMROMT is closely related to the Carthamus tinctorius matairesinol OMT (CtMROMT). Gas
Chromatography-Mass Spectrometry (GCMS)-based analysis of recombinant AsMROMT and AsTJOMT
assays towards their respective substrates show that the two OMTs have comparable kinetic attributes withpreviously characterized plant OMTs, having kcat/Km values of 0.0143 μM-1 min-1 and 0.0763 μM-1 min-1,
respectively. Gene expression of the OMTs in different organs show that AsTJOMT has highest expression543

levels in rhizomes, which is in line with previous reports indicating high amount of lignan in the mentioned
organ. As for AsMROMT, we were unable to observe detectable amounts of its expression in the organs that we
tested. To our knowledge, this is the first report of the isolation and characterization of plant OMTs involved inlignan biosynthesis in A. sylvestris.
2012-218
Fluorescence-tagged monolignols for delineating plant cell wall lignification
Yuki Tobimatsu*1, Armin Wagner*2, Lloyd Donaldson*2, Prajakta Mitra*3, Dominique Loque*3, Oana Dima*4,
Claudiu Niculaes*4, Wout Boerjan*4, Jeong Im Kim*5, Nickolas Anderson*5, Clint Chapple*5, John H. Grabber*6,
John Ralph*1*7*1
University of Wisconsin-Madison, Department of Biochemistry, USA, *2Scion, Biotransformation Group,
New Zealand, *3Joint BioEnergy Institute (JBEI), Lawrence Berkley National Laboratory, USA,
*4
VIB, Ghent University, Department of Plant System Biology, Belgium, *5Purdue University, Department ofBiochemistry, USA, *6US Department of Agriculture, Dairy Forage Research Center, USA. *7US Department ofEnergy, Great Lakes Bioenergy Center (GLBRC), USA
Abstract:
Fluorescence-tagged monolignols, p-hydroxycinnamyl alcohols γ-linked to fluorogenic dyes
such as aminocoumarin, nitrobenzofuran, or styrylpyridinium derivatives were synthesized and tested as
photoprobes for in vitro and in vivo studies of cell wall lignification. To illustrate the use of the probes foranalysis of monolignol-protein interactions, the complexation of each coumarin-tagged monolignol withhorseradish apoperoxidase was monitored by Förster resonance energy transfer (FRET). In addition, to test an
imaging approach, fluorescence-tagged monolignols were fed into various plant cell systems and the
localization of incorporated probes was readily visualized by fluorescence microscopy.
Keywords: enzyme-substrate complex; fluorescence probes; Förster (fluorescence) resonance energy
transfer (FRET); in vivo imaging; monolignol conjugate synthesis; peroxidase
2012-219
Quercus 属の外樹皮におけるスベリン芳香族部分の化学構造と酵素的生成伊藤彰伸，松本匠哉，鈴木利貞，片山健至
香川大学農学部
Chemical structure and enzymatic formation of aromatic domain of suberin in outer bark of Quercus spp.
Akinobu Ito, Takuya Matsumoto, Toshisada Suzuki, Takeshi Katayama,
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan
Abstract:
To clarify chemical structure of aromatic domain of suberin in outer bark of Quercus spp., basic
methanolysis of the outer bark of Quercus suber, namely cork, with sodium methoxide was performed. Fromthe methanolysis products previously an α=β－O－4’ enol ether dimers of methyl ferulate had been isolated andidentified, and furthermore the other α=β－O－4’ enol ether dimer of a ferulate derivatives was isolated in thisstudy. This ferulate-derivative moiety is presumed to be ω-feruloyloxy(long-chain fatty acids) methyl ester
whose the long-chain fatty acids were a mixture of the monologues. A dimeric ferulate bonding toω-hydroxy(long-chain fatty acids) was isolated for the first time as a methanolysis product, and is considered to
be derived from the bonding sites between the aliphatic and aromatic domains. Isolation of a β-5’ benzofuran
dimer of methyl ferulate was also suggested. A biosynthetic approach, dehydrogenative dimerization of
16-(feruloyloxy)-hexadecanoic acid with cell-free extracts of Q. variabilis bark in the presence of hydrogen
peroxide was carried out in order to support the elucidation of the chemical structure. Formation of a 4-O-5’
diaryl ether type dimer of the substrate was found for the first time.
Keywords: Cork, Quercus suber, Quercus variabilis, ferulic acid, 16-(feruloyloxy)-hexadecanoic acid2012-220
改変型植物酸性 peroxidase の酵母での発現と精製(4)吉中喬慈、川合伸也
東京農工大学大学院
Heterogeneous expression and purification of modified plant peroxidase (4)Kyouji Yoshinaka, Shinya Kawai
Tokyo University of Agriculture and Technology, Japan
Abstract:
Most of plant peroxidases can oxidize coniferyl alcohol efficiently, but not sinapyl alcohol. On
the other hand, a few of plant peroxidases were reported to use sinapyl alcohol as preferred substrates. It issugested that they have the additional active sites in the other positions than the heme pocket in the active site.
544

We tried to introduce the additional catalytic sites of these peroxidases to PrxA3a, an anionic peroxidase of
hybrid aspen, Populus kitakamiensis, for substrate specificity modifications and for certifications of the surface
amino acid residue hypothesis. As a result, PrxA3a A165W and PrxA3a F77Y, PrxA3a F77Y A165W raised theoxidizing ability of cytochrome c which cannot enter into the heme pocket. Furthermore, PrxA3a F77Y, PrxA3a
F77Y A165W, and PrxA3a F77Y L182Y gained sinapyl alcohol polymerizing activity. We analyzed shifts ofSoret band absorption by H2O2 treatment. The responses to the H2O2 of Soret band absorption differed in
mutated PrxA3a enzymes and wild type. Therefore, it is thought that electron transfer is occurred between heme
and mutated amino acid residues.
2012-P01
カンバ類癌腫病菌カバノアナタケ IO-U1 株生菌体による非フェノール性-O-4 型リグニンモデル二量体の分解機構
土屋 慧, 石栗 太, 飯塚和也, 吉澤伸, 横田信三
宇都宮大学農学部森林科学科
Degradation mechanisms of a non-phenolic -O-4 lignin model dimer by intact cells of birch canker-rot fungus
Inonotus obliquus IO-U1 strain
Satoshi Tsuchiya, Futoshi Ishiguri, Kazuya Iizuka, Nobuo Yoshizawa, Shinso Yokota
Department of Forest Science, Faculty of Agriculture, Utsunomiya University, 350 Mine-machi, Utsunomiya
321-8505, Japan
Abstract:
The present study investigated the degradation mechanisms of a non-phenolic -O-4 lignin
model dimer, 1-(4-ethoxy-3-methoxyphenyl)-2-(2,6-dimethoxyphenoxy)-1,3-propanediol, by intact cells of
birch canker-rot fungus Inonotus obliquus IO-U1 strain. In addition, extracellular ligninolytic enzyme activitiesof the fungus were assayed with culture liquid based on the modified Basal III medium. The degradation
products by -O-4 bond cleavage and by cleavage of C-etherified aromatic ring were detected by GC-MS
analysis of the metabolites from the lignin model dimer. The activities of laccase, Mn(II)-dependent peroxidase,and lignin peroxidase were detected as ligninolytic enzymes in the fungal culture liquid. It was suggested that
-O-4 bond cleavage and cleavage of C-etherified aromatic ring of the lignin model dimer might haveoccurred by laccase and unidentified mediators from the fungus, because laccase activity was the highest in theculture liquid.
Keywords: canker-rot fungus, forest pathology, Inonotus obliquus, lignin biodegradation, ligninolytic
enzyme2012-P02
イオン液体溶媒系に溶解した植物細胞壁の分子量分布
曲琛, 岸本崇生, 濱田昌弘, 中島範行
富山県立大学工学部生物工学科
Molecular weight distributions of plant cell walls recovered from verious ionic liquid systems
QU Chen, KISHIMOTO Takao, HAMADA Masahiro, NAKAJIMA Noriyuki
Bioorganic chemistry Lab, Department of Biotechnology, Toyama Prefectural University
Abstract:
A method for NMR analysis of entire plant cell walls without isolating their components wasrecently developed in our laboratory. The method consists of ball-milling of cell walls, dissolution in ionicliquids, in situ acetylation, and recovery of acetylated materials. However, dissolution in ionic liquids withrelatively long ball-milling times may cause partial degradation of wood components. In order to clarify thesepoints, molecular weight distributions of acetylated plant cell walls recovered from different ionic liquid
systems were examined by gel permeation chromatography (GPC). The results showed that the molecularweight of the acetylated cell-walls recovered from 1-allyl-3-methylimidazolium chloride ([Amim]Cl) at 30ºC–
80ºC and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) at 100ºC for 2 h were comparable to or a little
higher than that of N-methylimidazole (NMI)/DMSO system.
Keywords： molecular mass, SEC, size exclusion chromatography, lignin, cellulose
2012-P03
アセチル化リグニンを原料とする水酸基を持たないエポキシ樹脂硬化物の合成と熱的性質
廣瀬重雄*1、川崎淳貴*1、島田幹夫*1、畠山立子*2、畠山兵衛*2
1福井工業大学・工、*2 リグノセルリサーチ(株)545Thermal properties of cured epoxy resins without hydroxyl groups derived from O-acetyl lignin
Shigeo Hirose*1, Junki Kawasaki*1, Mikio Shimada*1, Tatsuko Hatakeyama*2 and Hyoe Hatakeyama*2*1
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan,*2Lignocel Research Co.
Ltd., 73-8 Yatsumata, Fukui 910-3558, Japan
Abstract:
Cured epoxy resins without hydroxyl groups were prepared using O-acetylalcoholysis lignin(AcAL). AcAL, Bisphenol A diglycidyl ether (BPADGE) and a catalytic amount of 2-ehtyl-4-methylimidazole(2E4MI) were dissolved in tetrahydrofuran (THF), and then THF was removed under a reduced pressure. The
obtained reaction mixtures having various [EPOXY]/[PhOAc] mole ratios ranging from 0.8 to 1.2 were cured at
150 oC for 5 hr. Thermal properties of the obtained cured epoxy resins were studied by differential scanningcalorimetry (DSC) and thermogravimetry (TG). The glass transition temperatures (Tg’s) showed a maximum atthe [EPOXY]/[PhOAc] mole ratio of 1.0. The thermal decomposition temperatures (Td’s) and mass residues at
500 oC were almost constant regardless of [EPOXY]/[PhOAc] ratios. It was found that 2E4MI acts as aneffective catalyst for the curing reaction between PhOAc groups of AcAL and epoxy groups of BPADGE.
Keywords; O-acetyl lignin, cured peoxy resins, sysnthesis, thermal properties.
2012-P04
土壌炭素固定能評価のための植物リターの安定炭素同位体比分析におけるリグニンの影響
山田竜彦*1、林 徳子*1、世良 耕一郎*2、酒井正治*1*1
森林総合研究所、*2 岩手医科大学
Effect of lignin to stable carbon isotopic analysis of plant litter for the evaluation of soil organic matteraccumulation
Tatsuhiko Yamada*1, Noriko Hayashi*1, Kouichiro Sera*2, Masaharu Sakai*1*1
FFPRI. Tsukuba Japan, *2Iwate Medical University, Morioka Japan
Abstract:
Stable carbon isotopic analysis of plant litter provides important information for the evaluationof soil organic matter accumulation. The carbon isotope ratio of 13C/12C (δ13C) shows around -14‰ and around-28‰ on the C4 plants and C3 plants, respectively. We have reported that the isotope ratio of soils under the C3
and C4 plants shows convergence to around -24‰ with the depth of the soil increasing. Fresh leafs of the C4
and C3 plants were corrected and the each leave samples were separated in 4 kinds of extractive fractions andKlason lignin fraction. The isotope ratio data of all Klason lignin fraction showed not much difference with thatof original plant leafs. The data didn’t support of the hypothesis of the leaf lignin that might be a difficult todegrade in soil was the main reason of the carbon isotope ratio convergence with the soil depth.
Keywords: soil analysis, carbon isotope, plant litter, leaf lignin
2012-P05
レジノール型モデル化合物の高圧水蒸気蒸留条件と構造変化の検討
鎌田将利、葭谷耕三、棚橋光彦
岐阜大学大学院 応用生物科学研究科
Examine of condition of high-pressure steam distillation and structural change of resinol model compounds
Masatoshi Kamada, Kouzou Yoshitani, Mitsuhiko Tanahashi
Graduate School of Applied Biologycal Sciences, Gifu University, Gifu 501-1193, Japan
Abstract:
For determination of high-pressure steam-distillation condition of resinol type compounds fromwood, some resinol and dilactone type model compounds such as sesamin, pinoresinol, syringaresinol,
dehydrodiferulic acid and dehydrodisinamic acid were synthesized and submitted to the high-pressure
steam-distillation at 110℃ to 180℃ with a newly constructed apparatus. Sesamin was distilled at 150℃ but
pinoresinol and syringaresinol were not distilled under these conditions. Moreover, when these compounds were
heated, these compounds partially changed to each epimers. By contrast dehydrodiferulic acid anddehydrodisinamic acid were not distilled. But 1.4-diphenolic butadiene derivative was distilled by high-pressure
steam-distillation. 1.4-Diphenolic butadiene derivative that is degradation product was obtained bydecarboxylation of dehydrodiferulic acid and dehydrodisinamic acid.
Keywords: furofuran, furolacton, resinol, ferulic acid, vanillin
2012-P06
リグニンを原料としたポリエステルの調製
磯崎友史*1、石崎光輝*2、幸田圭一*1、山田竜彦*3、浦木康光*1*1
北大院農、*2 北大農、*3 森林総研
546

Preparation of polyester derived from lignin
Tomofumi Isozaki*1, Koki Ishizaki*2, Keiichi Koda*3, Tatsuhiko Yamada*4, Yasumitsu Uraki*3*1Graduate School of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, 060-8589 Hokkaido,
Japan. *2Faculty of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, 060-8589 Hokkaido,
Japan. *3Resarch Faculty of Agriculture, Hokkaido University, Kita 9 Nishi 9, Kita-ku, Sapporo, 060-8589
Hokkaido, Japan. *4Department of Biomass Chemistry, Forest and Forest Products Research Institute, 1
Matsunosato, Tsukuba, 305-8687 Ibaraki, Japan
Abstract:
We prepared lignin-based fibrous polyester, by using technical lignin and carboxylic chloride.
Kraft lignin (KL) and soda lignin (SL) were used as a technical lignin, while terephthaloyl chloride (TC) wasused as a carboxylic chloride. Polyethylene glycol (PEG) 400 and PEG-lignin, an isolated linin recovered fromsolvolysis process of cedar wood chip with PEG400, were also used to improve mechanical strength of theresulting products. KL- and SL-based polyesters were too fragile to measure the tensile strength, but addition of
PEG 400 to SL, and introduction of PEG to lignin showed a little improvement of the tensile strength and leadto thinner diameters of polyester fiber.
Keywords: kraft lignin, soda lignin, PEG-lignin, polyester, tensile strength,
2012-P07
高圧水蒸気蒸留による針葉樹材成分の抽出
伊藤優作、棚橋光彦、葭谷耕三
岐阜大学大学院 応用生物科学研究科
Extraction of constituents from soft wood by high-pressure steam distillation
Yusaku Ito, Mitsuhiko Tanahashi, Kouzou Yoshitani
Graduate School of Applied Biologycal Sciences, Gifu University, Gifu 501-1193, Japan
Abstract:
Newly developed high-pressure steam distillation was conducted for Thujopsis dorabrate woodchips by stepwise increasing steam-temperature at 120, 140, 160, 180, and 200℃. Thujopsene was mainly
distilled at 120 and 140℃,on the other hand ferrginol was mainly distilled at 160 and 180℃and somedegradation products from lignin or polysaccharide such as vanillin and 5-hydroxymethylfurfural were distilled
at 200℃.
Keywords: high-pressure steam, steam distillation, extract, soft wood, biomass
2012-P08
Sphingobium sp. SYK-6 株の dehydrodiconiferyl alcohol 代謝系遺伝子の単離と解析
高橋 健司*1、上村 直史*1、笠井 大輔*1、菱山 正二郎*2、原 啓文*3、片山 義博*4、福田 雅夫*1、梶田 真也*5、政井 英司*1
*1
長岡技術科学大学・生物、*1 森林総合研究所、*3 岡山理科大学・生体医工学科、*4
日本大学・生物資源科学部、*5 東京農工大学大学院・生物システム応用科学府
Characterization of the dehydrodiconiferyl alcohol catabolic genes in Sphingobium sp. strain SYK-6
Kenji Takahashi*1, Naofumi Kamimura*1, Daisuke Kasai*1, Shojiro Hishiyama*2, Hirofumi Hara*3, Yoshihiro
Katayama*4, Masao Fukuda*1, Shinya Kajita*5, Eiji Masai*5*1
Department of Bioengineering, Nagaoka University of Technology, Kamitomioka, Nagaoka, Niigata 940-2188,
Japan, *2Forestry and Forest Products Research Institute, Tsukuba, Ibaraki 305-8687, Japan, *3Department of
Biomedical Engineering, Okayama University of Science, Kita-ku, Okayama 700-0005, Japan, *4College of
Bioresource Sciences, Nihon University, Fujisawa, Kanagawa 252-0880, Japan, *5Graduate School of
Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo
184-8588, Japan
Abstract:
A bacterial catabolic pathway of a phenylcoumaran-type compound, dehydrodiconiferyl alcohol(DCA), was proposed by Habu et al. in 1988. In that pathway, the first step was the oxidation of the alcoholgroup at the γ-position of the B-ring side chain of DCA into the carboxyl group. The resultant product was
degraded to 5-formylferulate and vanillin through the release of γ-carbon and the cleavage of Cα-Cβ linkage of
the A-ring side chain. In this study, we isolated and characterized a part of the DCA catabolic genes of
Sphingobium sp. strain SYK-6. Three alcohol dehydrogenase (ADH) genes, which conferred the DCA oxidation
activity on a host strain, were isolated. In a previous study, we isolated three aldehyde dehydrogenase (ALDH)
genes from SYK-6, which showed oxidation activities toward a broad range of aromatic aldehydes. All these
ALDH gene products oxidized DCA-L into DCA-C. These results suggest that multiple ADH and ALDH genes
are involved in the conversion of DCA into DCA-C. Identification of the metabolites of DCA-C suggests that547

DCA-C was oxidized to DCA-CL, and then DCA-CL was converted to DCA-S via DCA-CC. The enzyme
activity to convert DCA-C into DCA-CL was inducible, and did not require any cofactor.
Keywords: dilignol, -5, biodegradation, microorganism
2012-P09
ヤマモモおよびオオバヤシャブシの環状ジアリールヘプタノイド生合成遺伝子の検索
笠井美波、鈴木綾乃、斉藤太一、米田夕子、河合真吾、西田友昭
静岡大学農学部
Isolation of cyclic diarylheptanoid synthase genes from Myrica rubra and Alnus sieboldiana
Minami Kasai, Ayano Suzuki, Taichi Saito, Yuko Yoneda, Shingo Kawai, Tomoaki Nishida
Department of Environment and Forest Resources Science, Faculty of Agriculture,Shizuoka University, 836
Ohya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
We have investigated the biosynthesis of a cyclic diarylheptanoid myricanol in Myrica rubra by
feeding experiments using 13C-labeled cinnamic acid derivatives. On the other hand, we isolated cyclic
diarylheptanoids from Alnus sieboldiana, which have -glucosidase inhibitory activity. In the present study, toidentify the cyclic diarylheptanoid synthases of M. rubra and A. sieboldiana, their total RNAs were isolated
from young shoots, and analyzed by a next generation sequencer. EST sequences having 70~80% homolog withchalcone synthase (CHS) super family were selected. 5’- and 3’- RACE PCRs were performed using the EST
sequences and cDNAs synthesized from total RNAs of M. rubra and A. sieboldiana.
Keywords: cyclic diarylheptanoids; biosynthesis; transcriptome; Myrica rubra; Alnus sieboldiana
2012-P10
グリコールエーテル系溶剤中での酸分解によりスギ木粉から抽出したリグニンの沈殿分別と特性化
井林賢太*1，山本涼太郎*1，石井大輔*1，山崎昌男*2，白井伸明*3，松本正*3，中沖隆彦*1，林久夫*1*1
龍谷大学理工学部物質化学科，*2 桜宮化学株式会社，*3 滋賀県東北部工業技術センター
Precipitation fractionation and characterization of lignin from sugi (Cryptomeria japonica D. Don) extracted byacid-catalyzed solvolysis in glycolethers
Daisuke Ishii*1, Masao Yamazaki*2, Ryotaro Yamamoto*1, Kenta Ibayashi*1, Nobuaki Shirai*3, Tadashi
Matsumoto*3, Takahiko Nakaoki*1, Hisao Hayashi*1*1
Department of Materials Chemistry, Faculty of Science and Technology, Ryukoku University, Otsu, Shiga
520-2194, Japan. *2Sakuranomiya Chemical, Co. Ltd., Moriyama, Shiga 524-0044, Japan.
*3
Northeastern Industrial Research Center of Shiga Prefecture, Nagahama, Shiga 526-0024, Japan
Abstract:
Extraction of lignin from sugi woodmeal was performed by solvolysis in mixed glycolethers towhich p-toluenesulfonic acid was added as catalyst. The solvolysis was performed under reflux at 160 C for 2 h.
Lignin was obtained by concentrating the liquified fraction at 110 C for 4 h under vacuum. Structural analysisof the obtained lignin was performed by FT-IR, 1H- and 13C-NMR. Furthermore, in order to recover the lignin as
solid, precipitation fractionation of the liquified lignin was attempted.
Keywords: solvolysis lignin, glycolethers, sulfonic acid, liquifaction, precipitation fractionation
2012-P11
広葉樹ユリノキあて材の樹幹内におけるリグニンおよび多糖類の偏在性
秋山拓也、松本雄二
東京大学大学院農学生命科学研究科
Uneven distribution of lignin, cellulose and hemicellulose in the tension wood stem of yellow poplar(Liriodendron tulipifera)
Takuya Akiyama, and Yuji Matsumoto
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo, Tokyo
113-8657.
Abstract:
Neutral sugar analysis was applied to wood meal taken from various sapwood positions in thetension wood stem of yellow poplar (Liriodendron tulipifera), and the results were compared with those oflignin analyses previously reported. The yield of glucose was higher along the periphery of the stem toward thetension wood part. In contrast, the yields of xylose and mannose were lower in this direction. A high positive
correlation was observed between mannose yield and Klason lignin content (R2 = 0.92). The xylose yield was
also correlated with the methoxyl content of the Klason residue (R2 = 0.93) and the erythro/threo ratio of -O-4
structures (R2 = 0.95).
548

Keywords:

reaction wood, mannan, xylan, lignin content, arylglycerol--aryl ether

2012-P12
深海沈木から単離したバクテリアの分類学的位置と芳香族モノマー代謝
大田ゆかり、西真郎、芳賀拓真、坪内泰志、丸山正、長谷川良一、秦田勇二（独）海洋研究開発機構 (JAMSTEC)
Phylogenetic analysis of culturable bacteria from deep-sea sunken wood and their aromatic compounds
metabolism
Yukari Ohta, Shinro Nishi, Takuma Haga, Taishi Tsubouchi, Tadashi Maruyama, Ryoichi Hasegawa, Yuji
HatadaJapan Agency of Marine-Earth Science and Technology (JAMSTEC), 2-15 Natsushima-cho Yokosuka
237-0061, Japan
Abstract:
Functional screenings of culturable bacteria isolated from sunken wood collected from the deepsea revealed the existence of capable of metabolizing lignin-related aromatic compounds. The isolates wereclassified into diverse phyla, including Firmicutes, Actinobacteria, Bacteroidetes, and Proteobacteria.
Twenty-one unique 16S rRNA gene sequences were detected including marine lineage isolates. The metabolitesof the isolates were analyzed using liquid chromatography/mass spectrometry (LC/MS) or gas
chromatography/mass spectrometry (GC/MS). Most of the representative isolates non-oxidatively
decarboxylated the substrates to produce the corresponding aromatic vinyl monomers, which are used as feedstocks for bio-based plastics production. Oxidative metabolism of the lignin-related compounds for assimilation
was frequently observed. Our study showed that the deep-sea environment contains an abundance of
microorganisms capable of both non-oxidative and oxidative bioconversion of lignin-derived aromaticcompounds. The ability for bioconversion of aromatic compounds found in this study will facilitate thedevelopment of future biotechnological applications.
Keywords: aromatic compounds, bioconversion, deep-sea bacteria, phenolic acid, vinyl monomer

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第 58 回 （2013.11.12-13） サンポートホール高松
2013-101
イネ brown-midrib 変異体の解析
小柴太一１）、村上真也１）、向井まい１）、服部武文１、２）、宮尾安藝雄３）、廣近洋彦３）、鈴木史朗１）、坂本正弘４）、
梅澤俊明１、５）１）京都大学生存圏研究所、２）徳島大学大学院 SAS、３）農業生物資源研究所、４）京都大学大学院農学研究科、５）京都大学生存基盤科学研究ユニット
Characterization of brown-midrib mutant in rice plant
Taichi Koshiba1), Shinya Murakami1), Mai Mukai1), Takefumi Hattori1,2), Akio Miyao3), Hirohiko Hirochika3),
Shiro Suzuki1), Masahiro Sakamoto4), and Toshiaki Umezawa1,5)
1)
Research Institute for Sustainable Humanosphere, Kyoto Univ., Japan, 2) Institute of Socio-Arts and Sciences,
The University of Tokushima, Japan, 3) National Institute of Agrobiological Science, Japan, 4) Graduate Schoolof Agriculture, Kyoto University, Japan,
5)Institute of Sustainability Science, Kyoto University, Japan
Abstract:
Several brown midrib (bm) mutants have so far been isolated from the C4 grasses, maize,sorghum and pearl millet, but have not been detected in C3 grasses including rice (Oryza sativa). In the present
study we characterized the cad2 (cinnamyl alcohol dehydrogenase 2) null mutant isolated from retrotransposon
Tos17 insertion lines of Oryza sativa L. ssp. japonica cv. Nipponbare. This mutant exhibited brown-coloredmidribs in addition to hulls and internodes, clearly indicating both bm and gold hull and internode (gh)phenotypes. The enzymatic saccharification efficiency in the culm of cad2 null mutant was increased by 16.1%
than that of the control plants. The lignin content of the cad2 null mutant was 14.6% lower than that of thecontrol plants. Thioacidolysis of the cad2 null mutant indicated the presence of cinnamaldehyde structures in
the lignin. Taken together, our results show that deficiency of OsCAD2 causes the bm phenotype in addition togh, and that the coloration is probably due to the accumulation of cinnamaldehyde-related structures in thelignin. Additionally, this cad2 null mutant was useful to silage purposes and biofuel production.
Keywords: lignin, rice, cinnamyl alcohol dehydrogenase, brown midrib, mutant
2013-102
リグニン・多糖複合体分解酵素の植物体での発現黛 康悦、川合 伸也
東京農工大学連合農学研究科
Expression of lignin-carbohydrate complex degrading enzyme in the plant
Yasuyoshi Mayuzumi, Shinya Kawai,
United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology
Abstract:
We aim to increase the industrial values of crops by improvement of the digestibility of theforage crop and conversion rate to saccharification from biomass. We have been challenging to modify thelignin content and structures, by suppression of the genes for the lignin biosynthetic pathway or expression oflignin degradation enzymes. In this research, we tried to reduce the linkages between lignin and carbohydrate byintroduction of a lignin-carbohydrate-complex decomposition enzyme gene to tobacco plants. CcEST1 is anesterase of a white-rot-fungus, Coprinopsis cinerea. This enzyme can decompose bonds between the lignin andpolysaccharide. CcEST1 has feruloylesterase activity and acetyltransesterase activity. We altered the gene toeffectively secrete to the plant extracellular space and induced to tobacco plants. The esterase activities of thetransformed plants were higher than that of the wild type plant.
Keywords: lignin, Nicotiana tabacum, Coprinopsis cinerea, esterase, Agrabacterium tumefaciens,degrading enzyme, lignocarbohydrate complex, prxA3a
2013-103
リグニンを高分子化する植物ペルオキシダーゼの酸化能
重藤 潤、堤 祐司
九州大学大学院農学研究院
Oxidation ability of plant peroxidases contributing to lignin formation
Jun Shigeto, Yuji Tsutsumi
Department of Forest and Forest Products Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka,
812-8581 Japan550

Abstract:
The final step of lignin biosynthesis, which is catalyzed by a plant peroxidase, is the oxidative
coupling of the monolignols to growing lignin polymers. Cationic cell-wall-bound peroxidase (CWPO-C) from
poplar callus is a unique enzyme that has oxidative activity for both monolignols and synthetic lignin polymers.
We previously identified that three putative CWPO-C homologues (AtPrx2, AtPrx25 and AtPrx71) were related
to lignin biosynthesis in Arabidopsis by the analysis of the knockout mutants. In this study, we showed thatrecombinant proteins of AtPrx2, AtPrx25 and AtPrx71 have high oxidation activity for syringyl compound.
Moreover, assays with ferrocytochrome c showed that AtPrx2, AtPrx25 and AtPrx71 had high molecularcompound oxidation activity unlike AtPrx53 that is representative plant peroxidase. These results suggest thatsuch a property which can oxidize syringyl compounds and high molecular compounds is indispensable as alignin polymerization enzyme in vascular plants.
Keywords: plant peroxidase, lignin polymerization, Arabidopsis thaliana
2013-104
リグニンの形成過程に関する研究
高千智、橋ヶ谷尚大、松下泰幸、青木弾、福島和彦
名古屋大学大学院生命農学研究科
Studies on formation process of lignin
Chisato Ko, Shota Hashigaya, Yasuyuki Matsushita, Dan Aoki, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract:
After the dehydrogenative polymerization of coniferyl alcohol and its dimer model compounds(β-O-4, β-5, and β-β) using horseradish peroxidase, we analyzed the time courses of substrate amounts and thereaction products by LC-MS/MS. The consumption rate of coniferyl alcohol was far higher than that of the
dimers and there were difference among the consumption rates of the three dimers. From the results of cyclic
voltammogram, the consumption rate was not correlated with the radical oxidation potential. There were somedifferences on the consumption rates of the dimers between in the sole system and mixed system. We detectedthat coniferyl alcohol tetramers, hexamers, and octamers were formed during the polymerization reaction of the
dimers. It was confirmed that major bonding patterns between the dimers were 5-5´ and 4-O-5´ by analysis ofdehydrogenative polymerization products of [5-D] coniferyl alcohol dimers.
Keywords: monolignol, oligolignol, radical coupling, reaction rate, bonding type2013-10513C 標識法を用いたイネリグニンの構造解析
田村涼馬 1)、今村良教 1)、西村裕志 2)、寺島典二 3)、松下泰幸 1)、北野英己 4)、青木弾 1)、片平正人 5)、福島和彦 1)
1)
名古屋大学大学院生命農学研究科、 2)京都大学生存圏研究所、 3)名古屋大学名誉教授、 4)生物機能開発
研究センター、5)京都大学エネルギー理工学研究所
Structural analysis of rice plant lignin by 13C-enrichment technique
Ryoma Tamura1), Yoshinori Imamura1), Hiroshi Nishimura2), Noritsugu Terashima3), Yasuyuki Matsushita1),
Hidemi Kitano4), Dan Aoki1), Masato Katahira5), Kazuhiko Fukushima1)
1)
Graduate School of Bioagricultural Science, Nagoya University, Nagoya 464-8601, Japan 2)Research Institutefor Sustainable Humanosphere, Kyoto University, Uji 611-0011, Japan 3)Emeritus professor, Nagoya University,
Nagoya 464-8601, Japan 4)Bioscience and Biotechnology Center, Nagoya University, Nagoya 464-8601, Japan
5)Institute of Advanced Energy(IAE), Kyoto University, Uji 611-0011, Japan,
Abstract:
In order to analyze lignin structures, a technique have been developed using specific13
C-enrichment of the Cα of the phenylpropanoid unit by feeding coniferin-[α-13C] and syringin -[α-13C] to rice
plant. After milling of the extractive-free sample followed by acetylation for dissolving the sample in CDCl 3,
high-resolution two dimensional (2D) 13C-1H correlation HSQC (hetero-nuclear single quantum coherence)
spectrum of the whole cell wall material was recorded in the solution-state. Making difference NMR spectrum
between the 13C-enriched lignin and unenriched lignin provided a simple spectrum arising exclusively from the13
C-enriched carbons. From the simplified difference HSQC spectrum, quantitative determination was made on
the frequencies of major inter-unit bonds involving Cα. To investigate the incorporation of the 13C-enrichedmonolignol administrated as monolignol glucosides, stable carbon isotope compositions on the rice plant stems
and leaves were determined by measuring δ13C.
Keywords: lignin, rice plant , 13C-enrichment, High-Resolution NMR, δ13C
2013-106551

スピロジエノン構造に関する研究：同モデル化合物の酸処理によるジアリールプロパン構造の生成秋山拓也１）、２）、松本雄二１）、
１）
東京大学大学院農学生命科学研究科、２）科学技術振興機構 さきがけ
Study on spirodienone structures in lignin: the formation of diarylpropane structure from spiriodienone modelcompound by acid treatment
Takuya Akiyama1), 2) and Yuji Matsumoto1)
1)
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo, Tokyo
113-8657, Japan 2) JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
Abstract:
A model compound for spirodienone structures in lignin was treated with acetic acid orhydrochloric acid at room temperature (27ºC). While the model compound was stable in deuteroacetic acid
(CD3COOD), it disappeared within 3 hours by 0.1M duterochloric acid (DCl) treatment in dioxane-water(dioxane-d8:D2O, 80:20, v/v). As an acidolysis product, a diarylpropane was formed in over 80% yield.
Keywords: -1 linkage, spirodienone, diarylpropane, acidolysis, NMR,
2013-107
Eucalyptus globulus MWL 抽出残渣中の phenyl glycoside 型 LCC の構造解析
宮川泰幸、水上貴仁、上高原浩、高野俊幸
京都大学大学院農学研究科
Structural analysis of phenyl glycoside type LCC of Eucalyptus globulus in residues left after MWL isolation
Yasuyuki Miyagawa, Takahito Mizukami, Hiroshi Kamitakahara and Toshiyuki Takano
Division of Forest & Biomaterial Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto,606-8502, Japan
Abstract:
Several monolignol glycosides, including coniferyl alcohol, sinapyl alcohol and p-coumarylalcohol, bearing different sugar moieties were synthesized to obtain fundamental NMR data for the structural
analysis of phenyl glycoside type lignin-carbohydrate complex (LCC). The correlations observed for the C1β-H1βbonds of the sugar moieties in the HSQC spectra of the monolignol β-glycosides varied and were in the range of
δC/δH 97-105/4.7-5.2 ppm. The correlations of syringin and the sinapyl alcohol β-xyloside appeared in theneighborhood of that of phenyl glycoside type lignin-carbohydrate (LC) linkage in the HSQC NMR spectrum of
the fraction from the residues of Eucalyptus globulus left after MWL isolation. Suggesting that phenyl glycosidetype LC linkages in the residues might be the glycosidic bonds between syringyl lignin and cellulose or xylan.
Keywords: lignin-carbohydrate complex (LCC), phenyl glycoside, monolignol glycoside, HSQC NMR,
Eucalyptus globulus
2013-108
リグニン β-O-4 結合新規選択的開裂法(γ-TTSA 法)(6)-粗 MWL 分解物の分画および構造解析安藤大将１）、西村裕志２）、片平正人３）、矢野浩之２）、高野俊幸１）、中坪文明２）
１）
京都大学大学院農学研究科、２）京都大学生存圏研究所、３）京都大学エネルギー理工学研究所
Studies on the selective cleavage method for β-O-4 linkages of lignins (γ-TTSA method)(6) – the fractionationand the structure analysis of the degradation products of crude MWL by γ-TTSA method –Daisuke Ando1), Hiroshi Nishimura2), Masato Katahira3), Hiroyuki Yano2), Toshiyuki Takano1) and Fumiaki
Nakatsubo2)
1)
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan 2)Research Institute for
Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan
3)
Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan
Abstract:
The γ-TTSA method (consisted of four reactions; tosylation, thioetherification, sulfonation,
alkali-treatment), which has been proposed as new selective β-O-4 cleavage method, was applied to crude
Milled Wood Lignin (cMWL1) from Eucalyptus globulus. As a consequence, the lignin in the cMWL1 wasselectively degraded as expected, to get the degradation product (cMWL5). The cMWL5 was further
fractionated with the extraction of Et2O, EtOAc, THF to get the four fractions (cMWL5-1~ cMWL5-4).
HSQC-NMR spectra of the four degradation products suggested that cMWL5-1 consists low molecular lignin
degradation products and cMWL5-2~cMWL5-4 were new LCC fractions. Especially, cMWL5-4 is aninteresting LCC fraction in that xylan accounts for a large percentage differently from the others.
Keywords: crude MWL, γ-TTSA method, LCC, selective cleavage of β-O-4 linkage
2013-109552

緑液前処理条件下における β-O-4 型非フェノール性リグニンモデル化合物の反応
谷峰 1),2)、横山朝哉 1)、秋山拓也 1)、金 永燦 2)、松本雄二 1)
1)
東京大学大学院農学生命科学研究科生物材料科学専攻木材化学研究室
南京林業大学、中国江蘇省南京市龙蟠路 159 号
Reaction of nonphenolic β-O-4 type lignin model compound under green liquor pretreatment conditions
Feng Gu1),2), Tomoya Yokoyama1), Takuya Akiyama1), Yongcan Jin2), and Yuji Matsumoto1)
1)
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural andLife Sciences, The University of Tokyo, 2)Jiangsu Provincial Key Laboratory of Pulp and Paper Science andTechnology, Nanjing Forestry University, Nanjing 210037, China
Abstract:
Green liquor (GL, from Kraft pulp mill) pretreatment showed a great potential in efficient andselective removal of lignin from lignocellulose. The mechanisms of delignification in GL pretreatment shouldneed to be investigated. In this study, a nonphenolic β-O-4 type lignin model compound was synthesized andcooked with various liquors including GL to investigate the reactions of nonphenolic β-O-4 lignin moiety under
GL pretreatment conditions. The results showed that the nonphenolic β-O-4 bond of VG is broken under the GL
cooking conditions. Either of the Na2CO3 or NaSH solution caused the cleavage of β-O-4 bond only slowly,
although the former solution resulted in the disappearance of VG more rapidly than the latter. The Na 2CO3
solution mixed with NaSH not only enhanced the β-O-4 bond cleavage significantly but also changed reaction
products obtained, showing that reactions occurred in this mixed solution are different from those in the Na 2CO3or NaSH solution. These results suggest that there is a synergistic effect between CO32- and HS- on the β-O-4bond cleavage during GL cooking, although the reaction mechanism is not clear.
Keywords: Alkali, Carbonate, Green liquor, Hydrosulfide, Pulping
2)

2013-110
半流通型加圧熱水処理によるスギリグニン分解物の MALDI-TOF/MS 分析
高田 昌嗣、山内 一慶、坂 志朗
京都大学大学院エネルギー科学研究科
MALDI-TOF/MS analysis of lignin-derived products from Japanese cedar as treated by semi-flow
hot-compressed water
Masatsugu Takada, Kazuchika Yamauchi, Shiro Saka
Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan
Abstract:
By MALDI-TOF/MS analysis of lignin-derived products from Japanese cedar (Cryptomeria
japonica) as treated by semi-flow hot-compressed water (230℃/10MPa/15min), the decomposition behavior oflignin was discussed. As a result, several molecular weight intervals of 178 were observed in fractions collectedduring the increasing temperature up to 230℃, whereas more molecular weight intervals of 196 were in
fractions under constant temperature of 230℃. The former interval of 178 may be derived from β-β or β-5linkage, while the latter 196 from β-O-4 linkage. Therefore, during the increasing temperatures, thelignin-derived products in water-soluble portion would be more composed of condensed type linkages, whereas
those during the constant temperature more of ether type linkages. From these lines of evidence, it was
speculated that, during the increasing temperatures, condensed type-rich lignin-derived products were eluted in
hot-compressed water due to the cleavage of ether linkage, whereas after reaching at 230℃, some micropores
have occurred in the cell wall due to hemicellulose decomposition during the increasing temperature, someclusters of the rather large lignin molecules were eluted, and its lignin structure must be originated from thenatural lignin itself, thus more of the ether type of linkages of lignin. These results indicate that
MALDI-TOF/MS is a powerful tool for analysis of lignin-derived products.
Keywords: water-soluble lignin, bulk delignification, GC-MS, DFRC method, condensed type lignin
2013-111
側鎖からの水素引抜によるリグニンの熱分解ラジカル連鎖 β-エーテル開裂機構の検討
松田佳子、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Lignin radical chain β-ether-cleavage reactions through Abstraction of hydrogen from the side chain
Keiko Matsuda, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Sakyo-ku. Kyoto, 606-8501, Japan
Abstract:
Pyrolytic radical chain cleavage mechanisms of lignin-β-ether linkages were studied with the553

β-ether type lignin model dimers which were deuterated at the Cα-, Cβ- and Cγ- positions, respevtively. The
isotope effects on their reactivities were studied under the pyrolysis conditions (N2/350℃/2min in the presenceof Japanese ceder wood as a radical source). The reactivitiy was not reduced by deuteration at the Cα- orCβ-position. On the other hand, the reactivity of the Cγ- deuterated dimer decreased significantly. Since thebond dissociation energy (BDE) of the Cγ-H bond are rather higher than that of Cα-H bond, these results
suggest that the accessibility of radicals to the hydrogen atom is more important than the BDE of C-H bond.
This proposal is supported by the stereoelectronic factor required for the hydrogen Abstraction; liner interaction
between radical and H-C bond is required. Formation mechanisms of the Cα=Cβ and vinyl ether/ Cβ···types of
products are also discussed based on the deuterium retention in these products, which were measured with their
1
H NMR analysis. The Cα=Cβ type product is suggested to be formed through Abstraction of hydrogen from theCγ. As for vinyl ether and its hydrolysis product (Cβ···type product), it was found that the deuterium retention
data are not adequate for determination of their formation mechanisms, since the keto-enol ether-type
tautomerization occurring during pyrolysis would eliminate the deuterium atom from the Cα- and Cγ- positions.
Keywords: radical chain reaction, pyrolysis, ether cleavage, deuteration, isotope effect2013-112
工業リグニンを原料とするポリカプロラクトン誘導体の合成と熱的性質
畠山兵衛 1*、大菅忠秀 1、畠山立子２、１福井工業大学・工、*２リグノセルリサーチ
Preparation and thermal properties of industrial lignin based polycaprolactone derivatives
Hyoe Hatakeyama1*, Tadahide Ohsuga1 and Tatsuko Hatakeyama2
1
Fukui University of Technology, Fukui 901-8505, Japan, *2Lignocel Research Co. Ltd., Tsukuba, Ibaraki
300-1267, Japan
Abstract:
Based on two kinds of industrial lignin, such as hydrolysis (HL) and sodium lignosufonate (LS),polycaprolactone (PCL) derivatives were prepared via ring opening polymerization using hydroxyl group oflignin as a reaction site. By controlling the mass of -caprolactone, molecular mass of PCL side chain wasvaried from 1.1x103 to 1.1x104. Conversion rate of polymerization was ca. 100 %. Thermal properties of thelignin-PCL polymers were measured by differential scanning calorimetry and thermogravimetry. Mechanicaltests were also carried out. Glass transition was observed at around -70 to -60 oC and melting temperature wasfound at around 50 oC depending on molecular mass of PCL. Crystallinity calculated from enthalpy of melting
was 37-42%. Decomposition temperature was 370 to 400 oC. Breaking strength increased with increasing
molecular mass of PCL.
Keywords: hydrolysis lignin, sodium lignosulfonate, -caprolactone, glass transition, melting temperature
2013-特別講演、リグニン研究から始まった環境に優しい高圧水蒸気による森林資源の総合利用技術-- 爆砕処理、圧縮成
形加工、3 次元深絞り加工、バインダーレスバード、高圧水蒸気蒸留 –棚橋 光彦
飛騨産業株式会社 キツツキ森の研究所
2013- Invited lecture:
Total utilization technique of forest resources by ecop process with high-pressure steam beginning fromresearch for lignins – Steam explosion, compression molding, three dimensional deep-drawing,binderless-boads, high-pressure steam-distraction
Mitsuhiko Tanahashi
Woodpecker Forest Research Center, Hida-sangyo Co. Ltd., Japan
Abstract:
Starting from lignin chemistry such as synthesis of lignin model compounds, elucidation ofchemical structure of lignin and dehydrogenative polymerization of monolignols, eco-friendly total utilization
wood techniques using high pressure steam were developed. I had researched the reaction mechanism of woodcomponents and the separation of main degradation products from wood and these effective utilization such as
bioethanol and cattle feed from woods by steam explosion technique. In this study, I found that cellulose
crystalline structure transformed from Ⅰαto Ⅰβ by high-pressure steam-treatment. Taking advantage of thisfinding, the compressive molding method with high-pressure steam has been developed in our laboratory, as an
ecological method to make products from sawdust, leaves and branches, which arise from wood-basedindustries as waste. By this method, logs can be transformed into squares, and sawdust, leaves or branches into
biomass boards. Square timber will widely be used as building materials, and biomass board to be used for weed
suppressers or spreading materials on the sidewalk. For example, the board made by this method already has
554been used at many places, e.g., walking paths in Kenrokuen Garden. In addition, much essential oil mainly
terpenoids can also be obtained through this process. It was found that the essential oil contained furfural and
5-hydroxymethyl-2-furfural, which are byproducts from saccharides and hemicelluloses with high temperature
steaming. Furthermore a new apparatus was developed by combining a high pressure distillator with thecompressive molding apparatus. With this apparatus, the distillation of higher boiling compounds such as
sesqui-terpenoids and di-terpenoids, linans such as magnolol and sesamine and some degradation producte fromlignin such as syringaresinols which are hardly distilled with 100 ºC steam was made possible. In the case ofoperations at several saturated steam pressures (0.4-1.6 MPa) for 60 min, the yields of these compounds
increased with steam pressure within the limits of this experiment.
Keywords: high-pressure steam treatment, transformation of cellulose Iα to Iβ, compression molding,permanent fixation, flexible wood, high-pressure steam-distillation2013-201
針葉樹アルカリ蒸解黒液粉末のＰＥＧ処理による炭素繊維原料用リグニン誘導体
山田竜彦 1,2)、尹 國珍 2)、髙橋史帆 1)、細谷修二 1)、久保智史 1)、Olov Karlsson1,3)、浦木康光 4)１）
森林総合研究所、２）筑波大生命環境、３）ルレオ工科大、４）北海道大学大学院農学研究院
Lignin derivatives by alkaline-PEG treatment of softwood black liquor powder for preparing carbon fiber
precursor
Tatsuhiko YAMADA 1,2), Kukjin YOON 2), Shiho TAKAHASHI 1), Shuji HOSOYA 1),
Satoshi KUBO 1), Olov KARLSSON 1, 3), Yasumitsu URAKI 4)
1)
Forestry and Forest Products Research Institute, Japan, 2) Faculty of Life and Environmental Sciences,
University of Tsukuba, Japan, 3) Luleå University of Technology, Sweden, 4) Graduate School of Agriculture,
Hokkaido University, Japan
Abstract:
Thermal melt spinning is a major industrial process to produce commercial carbon fiber
precursor. To prepare lignin based carbon fiber precursor following the commercial process, lignin shouldmelt in heating without bringing thermo degradation. It is reported that some hardwood lignin melts at elevatedtemperature, however, softwood lignin such as softwood soda-anthraquinone (AQ) lignin does not show thermal
melting property. To prepare softwood lignin based carbon fiber, lignin should be modified to improve its
thermal properties. We found a new simple process to prepare lignin derivatives that have adequate thermal
melting property. In the process, black liquor powder was directly modified by PEGs in alkaline condition. In
this paper, the properties of the alkaline PEG treated lignin were discussed.
Keywords: carbon fiber, PEG, softwood lignin, softening temperature, dried black liquor powder
2013-202
オルガノソルブリグニンを原料とする電気二重層キャパシタ用電極の調製
Xiangyu You 1), 幸田圭一 1)、山田竜彦 2), 浦木康光 1)1）
北海道大学大学院農学研究院, 2)森林総合研究所
Preparation of electrode for electric double layer capacitor from organosolv lignin
Xiangyu You1), Keiichi Koda2), Tatsuhiko Yamada3), and Yasumitsu Uraki2)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan., 2) Research Faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan., 3) Division of Biomass Chemistry, Forestry andForest Products Research Institute, Tsukuba 305-8687, Japan.
Abstract:
An electric double layer capacitor (EDLC) was successfully prepared from electrospun
organosolv lignin fibers. This preparation was carried out by the following process. The electrospun fibers wereconverted to activated carbon fibers (ACFs) by thermostabilization followed by carbonization and steam
activation. The ACFs were suspended together with conductive carbon black (5%) in aqueous
carboxymethyl-cellulose solution, and then this suspension was spread on a thin Al foil. The foil and paper as aseparator was immersed in triethylmethylammonium tetrafluoroborate/ propylene carbonate solution as anorganic electrolyte. Finally, these materials were assembled in a measurement cell. This EDLC showed
electrostatic capacitance of 142 F/g and impedance of 12 .
Keywords: electric double layer capacitor (EDLC), electrospinning, electrode, acetic acid lignin (AL),carbon fibers (CFs)
2013-203
両親媒性サゴヤシリグニンを用いたサゴヤシ廃棄物の酵素糖化
Ina Winarni, 幸田圭一、浦木康光
555北海道大学大学院農学研究院
Enzymatic saccharification of sago palm waste with amphipathic sago-lignin derivatives
Ina Winarni1), Keiichi Koda2), and Yasumitsu Uraki2)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan. 2) Research Faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan.
Abstract:
The effect of amphipathic sago-lignin derivatives as a cellulase-aid agent on enzymaticsaccharification of pulps from sago palm waste, disposed after starch extraction, was evaluated, in terms ofsaccharification efficiency and remaining cellulase activity. This saccharification was repeated (1 st to 4th run),using cellulase purified by ultrafiltration after each run. Without additive, glucose yield was dramaticallydecreased by repeated use of cellulase. However, it was found that glucose yield and cellulase activity
maintained at a higher level by the addition of the amphipathic lignin derivatives.
Keywords: sago palm waste, saccharification, cellulolytic enzyme, critical micelle concentration,hydrophobic interaction
2013-204
酸素漂白過程における炭水化物の被攻撃部位の特定
中川明彦、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科生物材料科学専攻木材化学研究室
Specification of carbohydrate substructure attacked by active oxygen species in oxygen bleaching process
Akihiko Nakagawa, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo
Abstract:
In this study, a clear kinetic isotope effect was observed when a pair of carbohydrate modelcompounds, methyl β-D-glucopyranoside (MGP) and its deuterated compound at the C-3 or C-4 position,
methyl β-D-(3-2H)glucopyranoside or methyl β-D-(4-2H)glucopyranoside, respectively, was reacted with active
oxygen species (AOS) generated by reactions of O2 with a phenolic compound, 2,4,6-trimethylphenol (TMPh),under oxygen bleaching conditions. However, no clear kinetic isotope effect was observed when a pair of MGP
and its deuterated compound labeled at the C-5 or C-6 position, methyl β-D-(5-2H)glucopyranoside or methyl
β-D-(6,6’-2H)glucopyranoside, respectively, was reacted with the AOS under the oxygen bleaching conditions.
These results may suggest that the AOS Abstract the C-3 and C-4 hydrogens more frequently than they
Abstract the C-5 and C-6 hydrogens. It may further be suggested that the C-2 hydrogen is Abstracted by the
AOS more easily than the other hydrogens.
Keyword:cellulose, pulp, active oxygen species, lignin, oxygen delignification2013-205
アブラヤシ空果房の効率的糖化のための前処理への蒸解漂白法の適用
オクタヴィアニ コイリア、谷藤渓詩、大井 洋
筑波大学大学院生命環境科学研究科〒305-8572 茨城県つくば市天王台 1-1-1
Application of pulping and bleaching method to pretreatment of empty fruit bunch for effective enzymaticsaccharification
Khoiria Oktaviani, Keishi Tanifuji, Hiroshi Ohi
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki,305-8572, Japan.
Abstract:
This study aimed to develop pretreatment process of oil palm empty fruit bunch (EFB) for
effective enzymatic saccharification by applying wood cooking and pulp bleaching method. Firstly, EFB fibers
were subjected to prehydrolysis/ soda-anthraquinone (AQ) cooking and prehydrolysis/ acid sulfite cooking, andsubsequently oxygen bleaching to compare the lignin contents and pulp yields between of EFB pulps preparedby different cooking methods. Secondly, the enzymatic saccharification rates of EFB pulps prepared by
prehydrolysis/ acid sulfite and prehydrolysis/ soda-AQ cookings were compared. By enzymatic saccharification,
the amount of glucose liberated from acid sulfite pulp was lower than that of soda-AQ pulp. However, theoxygen bleaching treatment significantly increased the glucose liberation by enzyme from EFB acid sulfite pulp.
Keywords: pretreatment, delignification, soda-AQ cooking, acid sulfite cooking, enzymatic saccharification2013-206
556

針葉樹材からのセルロース精製および酵素糖化前処理としての 1-ethyl-3-methylimidazolium acetate 処理法の検討
荒川拓哉 1)、岸野正典 2)、中川明子 1)、大井洋 1)
1)
筑波大学大学院生命環境科学研究科、2)（地独）北海道立総合研究機構林産試験場
Treatment with 1-ethyl-3-methylimidazolium acetate as refining method of cellulose from softwood andpre-treatment for enzymatic saccharification
Takuya Arakawa1), Masanori Kishino2), Akiko Nakagawa-izumi1), Hiroshi Ohi1)
1) University of Tsukuba, Graduate School of Life and Environmental Sciences, 2) Hokkaido Research
Organization, Forest Products Research Institute
Abstractionic liquid treatment with 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) was studied as cellulose
production method and pre-treatment for enzymatic saccharification of Japanese softwood. A part of cellulose,
hemicellulose and lignin in wood were dissolved by [Emim]Ac treatment from wood meals of Cryptomeria
Japonica. After dissolution, some parts of these components were collected as regenerated cellulose and theother parts remain dissolved as oligomer in filtrate. The regenerated cellulose and [Emim]Ac treated wood
sample which collected as residue contained [Emim]Ac even after washing with dimethyl sulfoxide. The yieldof glucose liberated from regenerated cellulose by enzymatic saccharification was higher than that of filter paper.
The residue contained lignin little less than non-treated wood sample, however the glucose yield was 51.1% andit was much higher than that of non-treated wood sample. Moreover, the yield of glucose liberated from residue
was increased to 90.1% after decreasing the amount of contained [Emim]Ac from 25.1% to 3.9% by washingwith water. These results indicated that [Emim]Ac treated samples can be applied to enzymatic saccharification
without separating regenerated cellulose and residue.
Keywords: 1-ethyl-3-methylimidazolium acetate, enzymatic saccharification, Cryptomeria Japonica,
Py-GC/MS2013-207
ESI-FT-ICR MS によるリグノセルロース骨格構造モデルとセルラーゼとの複合体形成解析
吉岡 康一 1,2), 高田 理江 1,3) 渡辺 隆司 1, 2)1) 京都大学生存圏研究所, 2) CREST, 3) JSPS
Analysis of complex formation between lignocellulose model compounds and cellulase by ESI-FT-ICR MS
Koichi Yoshioka1, 2), Rie Takada1, 3), Takashi Watanabe1, 2)
1)Research Institute for Sustainable Humanosphere (RISH), Kyoto University, Gokasho, Uji, Kyoto 611-0011,
Japan, 2)Core Research Evolutional Science and Technology, Japan Science and Technology Agency, 4-1-8
Honcho, Kawaguchi, Saitama 332-0012, Japan, 3)Japan Society for the Promotion of Science, Kojimachi
Business Center Building, 5-3-1 Kojimachi, Chiyoda-ku, Tokyo 102-0083, Japan
Abstract:
In enzymatic hydrolysis of woody biomass by cellulase, inhibition of hydrolytic activity byadsorption between insoluble lignocellulose and cellulase has been widely known, but interaction between low
molecular mass lignin degradation products and cellulolytic enzymes are not well understood. We analysed
adsorption of cellulase on lignin dimer model compounds or cellooligosaccharides by ultra-high resolution mass
spectrometry. Complex formation of endoglucanase or CjCBM28 with lignin dimer model compounds wasobserved as well as that with cellooligosaccharides. Not only stoichiometric but also multiple intermolecularinteractions between cellulase component and lignin model compounds were demonstrated by the mass spectra.
Keywords: cellulase, inhibitor, ligninocellulose, complex formation, ESI-FT-ICR MS
2013-208
ピルビン酸デカルボキシラーゼ遺伝子高発現による白色腐朽菌におけるアルコール発酵能改善
平林翔 1), 平井浩文 1, 2), 河岸洋和 1, 2, 3)
1)
静岡大学大学院農学研究科、2)静岡大学グリーン科学技術研究所、3)静岡大学創造科学技術大学院
Improvement of alcohol fermentation ability by overexpression of pyruvate decarboxylase gene inwhite-rot-fungi
Sho Hirabayashi1), Hirofumi Hirai 1, 2), Hirokazu Kawagishi 1, 2, 3)
1)
Graduate School of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2)Research Institute of Green
3)
Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan,
Graduate School of Scienceand Technology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
To produce ethanol effectively from woody biomass by hyper lignin-degrading fungus
Phanerochaete sordida YK-624, the gene of pyruvate decarboxylase (pdc) which is a key enzyme in alcohol557

fermentation, was cloned. The promoter of glyceraldehyde-3-phosphate dehydrogenase gene cloned from P.
sordida YK-624 was used to drive the expression of pdc. The expression vector was transformed into a P.
sordida YK-624 uracil auxotrophic mutant, UV-64. Thirteen of 16 transforamants showed higher production of
ethanol than wild type. The strain GP7, which showed the highest production of ethanol among alltransformants, indicated higher PDC activity and transcription of pdc. These results suggest that theoverexpression of pdc is effective for the improvement of alcohol fermentation in white-rot fungi.
Keywords: white-rot fungi, molecular breeding, pyruvate decarboxylase, alcohol fermentation,
Phanerochaete sordida YK-624
2013-209
非フェノール性リグニンモデル化合物の分解を触媒するカワラタケ培養物由来のラッカーゼメディエーター
河合真吾 1)、松永 幸 2)、宮崎 恵 2)、平下晴可 1)、米田夕子 1)、西田友昭 1)
1) 静岡大学大学院農学研究科、2) 静岡大学農学部
Degradation of a nonphenolic lignin model compound catalyzed by laccase in the presence of mediators isolated
from the cultures of Trametes versicolor
Shingo Kawai 1), Miyuki Matsunaga 2), Megumi Miyazaki 2), Haruka Hirashita 1), Yuko Yoneda 1) and Tomoaki
Nishida 1)
1)
Graduate School of Agriculture, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan, 2)
Faculty of Agriculture, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
Laccase (EC 1.10.3.2) is widely found in white-rot fungi and catalyzes one-electron oxidationof phenolic substances to form many oxidation products via phenoxy radicals. In the presence of appropriatecompounds (mediators), laccase degrades nonphenolic lignin model compounds that are resistant to degradation
by laccase alone. has been reported. However, there are few report for the identification of natural laccase
mediators.
In this report, we searched the natural laccase mediators in the extacellular culture fluid of Trametes versicolor
for laccase production and in the whole-culture pf beech wood incubated with T. versicolor. The results
indicated that laccase in the presence of the low molecular phenols isolated from these cultures of T. versicolor
could catalyzed the degradation of a nonphenolic β-O-4 lignin model dimer via the Cα-oxidation, β-ether
cleavage and aromatic ring cleavage. The degradation mechanisms are very similar to those forlaccase/1-hydroybenzotriazole system and lignin peroxidase.
Keyword:laccase, natural mediator, p-hydroxybenzoic acid, vanyllyl alcohol, nonphenolic β-O-4 lignin
model dimer,
2013-210
高活性リグニン分解菌 Phanerochaete sordida YK-624 株によるビスフェノール A の分解機構の解明
王 剣橋 1)、山本 陽太郎 2)、山本 涼子 3)、徳元 俊伸 1)、轟 泰司 2, 4)、平井 浩文 2, 4)、河岸 洋和 1,2,4)
1)
静岡大学創造科学技術大学院、2)静岡大学農学研究科、3)静岡大学農学部、4)静岡大学グリーン科学技術研究所
Metabolism of bisphenol A by hyper lignin-degrading fungus Phanerochaete sordida YK-624
Jianqiao Wang1), Yotaro Yamamoto2), Ryoko Yamamoto3), Toshinobu Tokumoto1),
Yasushi Todoroki2, 4), Hirofumi Hirai2, 4), Hirokazu Kawagishi1, 2, 4)
1)
Graduate School of Science and Technology, Shizuoka University, Shizuoka, Japan, 2) Graduate School of
Agriculture, Shizuoka University, Shizuoka, Japan, 3)Faculty of Agriculture, Shizuoka University, Shizuoka,
Japan, 4) Research Institute of Green Science and Technology, Shizuoka University, Shizuoka, Japan
Abstract:
A (BPA) is one of the representative compounds of the endocrine disrupting compounds groupand the highest volume chemicals produced worldwide. As a result, BPA is often detected in many soil andwater environments. We demonstrated the metabolism of BPA from liquid cultures inoculated with hyper
lignin-degrading fungus Phanerochaete sordida YK-624. Both ligninolytic and non-ligninolytic condition, BPA
were effectively decreased and metabolites were detected by ESI-MS and NMR analysis. Under the ligninolytic
condition, BPA is oxidized to BPA phenoxy radicals by ligninolytic enzymes and then dimerized at
extracellular region. On the other hand, BPA is firstly monooxygenated to hydroxy-BPA by cytochrome P450,
and then methylated by P. sordida YK-624 under the non-ligninolytic condition.
Keywords: Phanerochaete sordida YK-624; bsphenol A; estrogenic activity; metabolic pathway
2013-211
Aliphatic biotransformation and crude oil biodegradation by Pestalotiopsis sp.
558

Dede Heri Yuli Yanto1), Kazutaka Itoh2), Sanro Tachibana2)
1)
The United Graduate School of Agricultural Sciences, Ehime University, 3-5-7 Tarumi Matsuyama, Ehime
790-8566 Japan, 2) Department of Applied Bioscience, Faculty of Agriculture, Ehime University 3-5-7 Tarumi,
Matsuyama, Ehime, 790-8566 Japan.
Abstract:
In this study, the ability of Pestalotiopsis sp. NG007 to degrade and transform aliphatic mixture
and its importance to biodegradation of crude oils was investigated in liquid medium. During the biodegradationof an aliphatic mixture (n-decane, n-undecane, n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane,n-octadecane, n-nonadecane, n-eicosane and pristane), fifteen metabolites were detected. The presence of fatty
alcohols, fatty aldehydes, and fatty acids (mono- and di-carboxylic acid) as intermediate products showed that
NG007 can degrade and transform aliphatic fractions not only via mono- or di-terminal oxidation, but also via
sub-terminal and alkyl peroxide oxidation. In co-culture with Polyporus sp. S133 (basidiomycetes fungus), theenhancement of crude oil biodegradation occurred via accelerated biodegradation of aliphatic and aromatic
fraction. Addition of piperonyl butoxide or AgNO3 inhibited biodegradation by 81-99%, which revealed theimportant role of P450 monoxygenases and/or dioxygenases in the initial degradation of the aliphatic andaromatic fractions in petroleum hydrocarbons.
Keywords: aliphatic, biodegradation, crude oil, monooxygenase, Pestalotiopsis sp.
2013-P01
特異的な広葉樹あて材形成とリグニン分布の関係
相蘇春菜、石栗 太、飯塚和也、横田信三
宇都宮大学農学部
Relationship between specific reaction wood formation and lignin distribution in angiosperms
Haruna Aiso, Futoshi Ishiguri, Kazuya Iizuka, Shinso Yokota
Faculty of Agriculture, Utsunomiya University, Utsunomiya, 321-8505 Japan
Abstract:
Lignin distribution of reaction woods in Sarcandra glabra and Gardenia jasminoides were
investigated to clarify the relationship between specific reaction wood formation and lignin distribution inangiosperm species. Based on the results of absorbance measured by visible-light microspectroscopy after
Wiesner and Mäule color reactions in normal wood, secondary wall of tracheid in S. glabra and wood fiber in G.
jasminoides were suggested to be mainly composed of guaiacyl lignin, and both guaiacyl and syringyl lignin,
respectively. On the lower side of inclined stems in both species, increase in guaiacyl lignin was foundcompared with normal wood and upper side of inclined stems. Based on the results, it is considered that increasein guaiacyl lignin may be an important factor for the species which form reaction wood on the lower side of
inclined stems in angiosperms.
Keywords: vessel-less angiosperms, Wiesner color reaction, Mäule color reaction, reaction wood
2013-P02
カ バノ ア ナ タケ 菌 IO-U1 株に 感 染 したシ ラ カン バ 幼植 物体 No.8 に 発 現 す るペ ルオ キシ ダー ゼ の
MALDI/TOF/MS イメージング
宮内 優 1)、吉永 新 2)、上高原 浩 2)、高島有哉 1)、石栗 太 1)、飯塚和也 1)、横田信三 1)1)
宇都宮大学農学部、2)京都大学大学院農学研究科
MALDI/TOF/MS imaging analysis of peroxidase expressed specifically in the Japanese birch plantlet No.8
infected with Inonotus obliquus strain IO-U1
Yu Miyauchi1), Arata Yoshinaga ２), Hiroshi Kamitakahara2), Yuya Takashima1), Futoshi Ishiguri1), Kazuya
Iizuka1), Shinso Yokota1)
1)
Faculty of Agriculture, Utsunomiya University, Utsunomiya 321-8505, Japan, 2)Graduate School of
Agriculture, Kyoto University, Kyoto, 606-8502 Japan
Abstract:
The present study aimed at clarifying the roles of the peroxidases, which were specifically
expressed in the Japanese birch plantlet No.8 infected with Inonotus obliquus strain IO-U1, in the basic
resistance mechanisms of the plantlet against the fungus. The specific peroxidases expressed by the fungal
infection were isolated by isoelectric focusing and analyzed by MALDI/TOF/MS. The distribution of thespecific peroxidases in the plantlet was investigated by using the obtained mass spectra and MALDI/TOF/MS
imaging. The obtained results indicated that the peroxidases expressed specifically by injury and fungal
infection distribute mostly in xylem, especially the peroxidases by fungal infection distribute in the specific partof xylem.
Keywords: basal resistance, canker-rot fungus, isozyme, mass spectrometry, tree pathology
559

2013-P03
セルロースミクロフィブリルゲルを用いた人工木化の試み
阿部賢太郎１），安藤大将２），矢野浩之 1）
１）京都大学生存圏研究所，２）京都大学大学院農学研究科
Cellulose microfibril-based scaffold for artificial lignification
Kentaro Abe1), Daisuke Ando２), Hiroyuki Yano1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Japan, 2) Graduate School of Agriculture,
Kyoto University, Japan
Abstract:
The aim of the present study was to evaluate a cellulose microfibril based-hydrogel as a
scaffold for artificial lignification. The cellulose microfibril aggregates isolated from softwood had a uniform
width of approx. 15 nm and lengths over several micrometers. The hydrogel was prepared from the microfibril
suspension through sodium hydroxide treatment and it had a layered structure of microfibril network and its
appearance was essentially the same as that of the primary wall of wood cells before lignification. We attempted
to synthesize DHPs on the surface and inside of the gel a by step-by-step reaction of the gel saturated withconiferyl alcohol and horseradish peroxidase in a H2O2 solution. As the lignification step was repeated, the colorof the gels gradually changed from translucent white to light brownish white and the volume was increased with
the increase in the number of polymerization times. This study confirmed that it is possible to deposit DHP
lignins in cellulose microfibril-based gels.
Keywords: lignification; cellulose microfibril; scaffold; hydrogel
2013-P04
β-O-4 型オリゴリグノールの合成研究
岸本崇生、板倉圭佑、濱田昌弘、中島範行
富山県立大学工学部、（兼）生物工学研究センター
Synthetic study on O-4 type oligolignols
Takao Kishimoto, Keisuke Itakura, Masahiro Hamada, Noriyuki Nakajima
Faculty of Engineering, Toyama Prefectural University, Imizu, Japan 939-0398
Abstract:
Artificial lignin polymers with  -O-4 linkages have been synthesized in our laboratory. In thisstudy two synthetic strategies: convergent and linear syntheses were evaluated for the synthesis of  -O-4 typeoligolignols with distinct degree of polymerization. A key reaction step was Williamson ether formation, which
includes nucleophilic substitution under basic conditions. Effect of several bases and protective groups were
investigated and a trimer was synthesized by the linear synthetic strategy.
Keywords: oligomeric model compound, dimer, tetramer, oligomer
2013-P05
β-O-4 構造を有する phenyl glycoside 型 LCC モデル化合物の合成
水上貴仁, 宮川泰幸, 上高原浩, 高野俊幸
京都大学大学院農学研究科
Synthesis of dilignol β-glycosides with β-O-4 structures
Takahito Mizukami, Yasuyuki Miyagawa, Hiroshi Kamitakahara, Toshiyuki Takano
Division of Forest & Biomaterials Science, Guraduate School of Agriculture, Kyoto University,
Sakyo-ku. Kyoto, 606-8502 Japan
Abstract:
To get fundamental HSQC NMR data for phenyl glycoside type LCC analyses, the syntheses ofdilignol β-glycosides having β-O-4 structure which is the most common structure in lignin were performed.
Guaiacylglycerol-β-guaiacyl ether (1Ge) was per-acetylated with Ac2O / pyridine to give compound 2Ge(99.7%). The compound was treated with hydrazine in THF to afford compound 3Ge (74.0%). The
glycosylation of compound 3Ge with compound 4 in the presence of BF3-Et2O in dry CH2Cl2 afforded only
β-glycoside 6Ge (97.3%). Deacylation of compound 6Ge with NaOMe / MeOH gave target material 8Ge(72.3%). The synthetic method for compound 8Ge was applied to the syntheses of other β-glycosides. The
correlations derived from C1-H1 of sugar moieties of β-glycosides are different from existing ones and present
in the region approx. δC / δH 100-104 / 4.8-4.9 ppm where supposedly signals derived from phenyl glycoside LC
linkage would appear.
Keywords: lignin-carbohydrate complex (LCC), 2D-NMR, phenyl glycoside, dilignol β-glycoside, β-O-4structure560

2013-P06
TEMPO によるリグニンの電解酸化の検討
三波 由実 上高原 浩 高野 俊幸
京都大学大学院農学研究科
TEMPO-mediated electro-oxidation of lignin model compounds
Yumi Sannami, Hiroshi Kamitakahara, Toshiyuki Takano
Division of Forest & Biomaterials Science, Graduate School of Agriculture,
Kyoto University, Sakyo-ku. Kyoto, 606-8502 Japan
Abstract:
The TEMPO and its derivatives-mediated electro-oxidation of lignin were investigated. The
electrolysis of dimeric lignin model compound 1G (4-ethoxy-3-methoxyphenylgltcerol-β-guaiacyl ether) in
acetonitrile-water afforded the corresponding Cα-carbonyl compound 2G. On the other hand, the electro
oxidation of 1G with TEMPO in 10% dioxane-buffer afforded the corresponding Cγ-carboxyl compound 3G inhigh yield. In both systems, the yields of the oxidative products by the electrolysis with 4-acetoamide-TEMPO
were higher than those with TEMPO.
Keyword:2,2,6,6-tetramethylpiperidine-N-oxyl, 4-AcNH-TEMPO, electrolysis, mediator, lignin
2013-P07
エレクトロスピニング法によるリグニン／セルロースナノクリスタル
複合ナノファイバー合成と炭素化の検討
吾郷万里子 1,2), 川本俊樹 1，佐藤一石 1)，Orlando J. Rojas2)
1)
徳島文理大学理工学部, 2)North Carolina State University
Electrospun lignin based nanofibers reinforced with cellulose nanocrystal and carbonization
Mariko Ago1), Toshiki Kawamoto1, Kazuishi Sato1), Orlando J. Roja2),
1)
Toshikuma Bunri Unibersity Faculty of Science and Engineering, Japan, 2)North Carolina State University,
USA
Abstract:
Lignin-based fibers were produced by electrospinning aqueous dispersions of lignin, poly(vinyl
alcohol) (PVA), and cellulose nanocrystals (CNC’s). Dispersion properties including viscosity, electricalconductivity, and surface tension were examined and correlated to the electro-spinnability and resulting
morphology of the composite fibers. The influence of CNC’s on the thermal properties of themulti-component materials was investigated by using thermal gravimetric analysisand differential scanningcalorimetry The thermal stability of the system was observed to increase owing to a strong interaction of thelignin-PVA matrix with the dispersed CNCs, mainly via hydrogen bonding as observed in Fourier transform
infrared spectroscopy experiments. Heat treatment on the lignin electrospun fibers was carried out by using of
nitrogen atmosphere at various temperatures, followed by carbonization at 1000 oC. Carbonized fibers were
evaluated using SEM, WAXD, and Raman spectroscopy.
Keywords: electrpspinning, cellulose nanocrystal, composite, thermal mechanical property, carbon fiber
2013-P08
リグニンおよびテルペン由来成分を原料とするエステル系エポキシ樹脂の合成と熱的性質
廣瀬重雄、越田浩史
福井工業大学工学部
Synthesis and thermal properties of epoxy resins derived from lignin and terpene-based component
Shigeo Hirose and Hiroshi Koshida
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Epoxy resins were prepared using alcoholysis lignin (AL) and terpene-based component. AL
was dissolved in the same amount of glycerol (GLY). The obtained solution was allowed to react with succinic
anhydride in order to synthesize the mixture ester-acid derivatives of AL and glycerol (ALGLYPA). A
ester-acid derivative of GLY (GLYPA) was synthesized from GLY. When the obtained ALGLYPA andGLYPA were allowed to react with 1,3-bis(3,4-epoxycyclohexenyl9-p-menthane (BECHM), the weightcontents of ALGLYPA {WALGLYPA/(WALGLYPA+WGLYPA)} were change from 0 to 100 %. [EPOXY]/[ACID]
mole ratio was maintained at 1.0. Thermal properties of the obtained cured epoxy resins were studied bydifferential scanning calorimetry (DSC) and thermogravimetry (TG). The glass transition temperatures (Tg’s)
increased and reached a constant value when ALGLYPA contents were increased. The thermal decomposition
temperatures (Td’s) and mass residues at 500 oC were almost constant regardless of ALGLYPA contents.
Keywords:l ignin, glycerol, terpene, epoxy resins, thermal properties561

2013-P09
各種木質リグニンを硬化剤に用いたエポキシ樹脂硬化物の特性
香川博之１）、岡部義昭１）、佐々木 千鶴２）、中村 嘉利２）
１）(株)日立製作所日立研究所、２）徳島大学大学院ソシオテクノサイエンス研究部
Properties of epoxy resins hardened by woody lignins
Hiroyuki Kagawa1, Yoshiaki Okabe1, Chizuru Sasaki2, Yoshitoshi Nakamura2
1
Hitachi Research Laboratory, Hitachi, Ltd., 7-1-1 Omika-cho, Hitachi-shi, Ibaraki-ken, 319-1292 JAPAN,
2
Department of Life System, Institute of Technology and Science, The University of Tokushima, 2-1
Minamijosanjima-cho, Tokushima-shi, Tokushima- ken, 770-8506 Japan
Abstract:
We are currently researching the application of lignin extracted from steam-exploded woody
biomass to epoxy resins, which is widely used as an insulating material in modern electric and electronicequipment. We have already reported the correlation between lignin properties and properties of epoxy resin
hardened by lignin obtained from softwood. Here, we report the lignin properties from hardwoods andproperties of hardened epoxy resin by hardwood lignin. The molecular weight of lignin extracted from
hardwood decreased with higher steam pressure and longer processing time as does that of lignin extracted fromsoftwood. The glass transition temperature of lignin-hardened epoxy resin depended on the crosslink density of
the hardened resin as does that of conventional epoxy resin; however, the crosslink density differed depending
on wood species. Of the four woods tested, the crosslink density of lignin extracted from Eucalyptus globulus
was the highest, those of Quercus acutissima and Phyllostachys heterocycla were next, and that of Cryptomeria
japonica was the lowest.
Keywords:
explosion, hardwood, molecular weight, epoxy resin, crosslink density

2013-P10
リグナン生合成に関与するフェニルクマランベンジルエーテルレダクターゼ遺伝子の解析諾恩達古拉（ノンダグラ）1)、辻幸子 1)、上村直史 2)、政井英司 2)、梶田真也 1)
1)
東京農工大学大学院 生物システム応用科学府
2)
長岡技術科学大学 工学部生物系
Analysis of a gene for phenylcoumaran benzylic ether reductase involved in lignan biosynthesis
Dagula nuoen1), Yukiko Tsuji1), Naofumi Kamimura2), Eiji Masai2), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, 184-8588 Tokyo, Japan, 2)Department of Bioengineering, Nagaoka University of Technology,940-2188 Niigata, Japan
Abstract:
Phenylcoumaran benzylic ether reductase (PCBER) is one of key enzymes for biosynthesis of
8-5’-linked lignan in seed, pollen, and vascular tissue. This enzyme catalyzes the NADPH-dependent reductionof dehydrodiconiferyl alcohol to give isodihydrodehydrodiconiferyl alcohol. It has been characterized in someplant species, such as Forsythia intermedia, Pinus taeda and Populus trichocarpa. Based on its sequencesimilarity, an Arabidopsis gene (At4g39230) is predicted to be a member of PCBER family. However, nobiochemical evidences for the function of the encoded polypeptide was presented so far. In order to reveal therole of the gene in plant growth and development, we characterized catalytic function of the recombinant
polypeptide and phenotypes of mutants in which the gene was inactivated through a T-DNA insertion. Ourpresent results suggest that it encodes PCBER of A. thaliana.
Keywords: lignin, neolignan, phenylpropanoid, secondary metabolite, wood formation2013-P11
バクテリア由来ヒドロキシ桂皮酸類 4-O-メチルトランスフェラーゼ遺伝子の探索小林 巽１）、○上村 直史１）、菱山 正二郎２）、笠井 大輔１）、福田 雅夫１）、菊地 淳３）、梶田 真也４）、政井 英
司１）
１）
長岡技術科学大学・生物、２）森林総合研究所、３）理化学研究所・植物科学
研究センター、４）東京農工大学大学院・生物システム応用科学府
Genome mining for hydroxycinnamic acid derivatives 4-O-methyltransferase encoding sequences
Yuduru Kobayashi1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1),
Masao Fukuda1), Jun Kikuchi3), Shinya Kajita4), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata
562

2)

Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, 3) Riken Plant Science Center, Tsurumi-ku
Yokohama, Kanagawa, 4) Graduate School of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology, Koganei, Tokyo, Japan
Abstract:
This work aims to control the lignin biosynthesis in plants using bacterial genes for the
structural modification of intermediate metabolites in the monolignol biosynthetic pathway. In this study, we
focused on O-methyltransferases (OMT), which catalyze O methylation of the para-hydroxyl group (4-OH) ofhydroxycinnamic acid derivatives. Putative OMT genes derived from seven different bacteria were selectedfrom the NCBI microbial genome database. These genes and Synechocystis OMT gene (slr0095) weresynthesized with codon optimization for expression in Escherichia coli. Six gene products, including slr0095,
were produced as soluble enzyme in E. coli, and purified by metal affinity chromatography. Finally we observedthat three OMTs in addition to slr0095 catalyzed the 4-O-methylation of caffeic acid.
Keywords: biomass, metabolic engineering, caffeoyl-CoA, feruloyl-CoA, ferulic acid2013-P12
細菌におけるリグニン由来芳香族化合物の取り込み遺伝子
森 光佑１）、上村 直史１）、原 啓文２）、笠井 大輔１）、福田 雅夫１）、政井 英司１）
１）長岡技術科学大学・生物、２）Malaysia-Japan Int’l. Inst. Tech.
Bacterial transporters for lignin-derived aromatic compounds
Kosuke Mori,1) Naofumi Kamimura,1) Hirofumi Hara,2) Daisuke Kasai,1)Masao Fukuda,1) Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology,
Nagaoka, Niigata, 940-2188 Japan, 2) Department of Environmental and Green Technology, Malaysia-Japan
International Institute of Technology, 54100 Kuala Lumpur, Malaysia
Abstract:
Sphingobiu sp. strain SYK-6 is capable of growing on various lignin-derived aromaticcompounds. The SYK-6 catabolic genes involved in the degradation of lignin-derived biaryls including
5,5-dehydrodivanillate (DDVA), and lignin-derived monoaryls have been characterized, however, the uptake
systems for lignin-derived aromatics remain unknown. In this study, we focused on the transporters for DDVA,
vanillate, syringate, and ferulate. DNA microarray analysis revealed that the transcriptions of six genes, which
probably encode major facilitator superfamily (MFS) transporters, were induced during the incubation withthese substrates. These six genes and two other genes homologous to pcaK of Pseudomonas putida PRS2000,
were disrupted in SYK-6 to determine their roles in the uptake of lignin-derived aromatics. As a result, dvxK
mutant lost the ability to grow on DDVA but retained the ability to grow on other substrates. The deduced
amino acid sequence of dvxK showed 21.6-25.7% identities with VanK of Acinetobacter sp. ADP1, PcaK of P.
putida PRS2000, and BenK of Corynebacterium glutamicum RES167. These results strongly suggested that
dvxK encodes an MFS transporter for DDVA in SYK-6.
Keywords: aromatic acid/H+ symporter, ATP-binding cassette transporter, tripartite tricarboxylatetransporter, genome mining, biomass
2013-P13
バクテリア由来コニフェリルアルデヒド二重結合還元酵素遺伝子の探索
荒木 拓馬１）、上村 直史１）、菱山 正二郎２）、笠井 大輔１）、福田 雅夫１）、菊地 淳３）、梶田 真也４）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）理化学研究所・植物科学
研究センター、４）東京農工大学大学院・生物システム応用科学府
Genome mining for coniferyl aldehyde double bond reductase encoding sequences
Takuma Araki1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1),
Masao Fukuda1), Jun Kikuchi3), Shinya Kajita4), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata
2)
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, 3) Riken Plant Science Center, Tsurumi-ku
Yokohama, Kanagawa, 4) Graduate School of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology, Koganei, Tokyo, Japan
Abstract:
This work aims to control the lignin biosynthesis in plants using bacterial genes for the
structural modification of intermediate metabolites in the monolignol biosynthetic pathway. In this study, we
focused on alkenal double bond reductases (DBR), which catalyze the reduction of the C-C-double bond of
coniferyl aldehyde. Putative DBR genes derived from six different bacteria were selected from the NCBI
563

microbial genome database. These genes and the Arabidopsis thaliana DBR gene (At5g16970) weresynthesized with codon optimization for expression in Escherichia coli. Four gene products, including
At5g16970, were produced as soluble enzymes in E. coli, and purified by metal affinity chromatography.
Finally we found that DBR of Parvibaculum lavamentivorans had a similar level of activity to that found in the
product of At5g16970.
Keywords: biomass, metabolic engineering, -proteobacteria, cinnamaldehyde, coniferyl alcohol
2013-P14
ジアリールプロパン型リグニン由来化合物代謝系遺伝子の単離と機能解析
南保 美姫１）、高橋 健司１）、上村 直史１）、菱山 正二郎２）、笠井 大輔１）、梶田 真也３）、
片山 義博４）、福田 雅夫１）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）東京農工大学大学院・生物システム応用科学府、４）日本大学・生物資源科学部
Isolation and characterization of catabolic genes for a diarylpropane-type lignin-derived compound
Miki Nambo1), Kenji Takahashi1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1),Shinya Kajita3),
Yoshihiro Katayama4), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology,
Nagaoka, Niigata 940-2188, Japan, 2)Forestry and Forest Products Research Institute, Tsukuba, Ibaraki
305-8687, Japan, 3) Graduate School of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology, Koganei, Tokyo 184-8588, Japan, 4)College of Bioresource Sciences, Nihon
University, Fujisawa, Kanagawa, 230-0045 Japan
Abstract:
Bacterialcatabolicpathwayofadiarylpropane-type
compound,
1,2-bis(4-hydroxy-3-methoxyphenyl)-propane-1,3-diol (HMPPD), has been reported only in Sphingomonas
paucimobilis TMY1009, and an HMPPD-converting enzyme was purified from this strain. However, its
reaction mechanism and the enzyme gene remain unknown. In this study, we investigated the HMPPD
catabolism by a lignin-derived compound degrader, Sphingobium sp. strain SYK-6. HMPPD was degraded byboth cells extracts prepared from SYK-6 cells grown in the presence and the absence of HMPPD, and vanillin
and vanillate were observed as intermediate metabolites. These results suggested that the HMPPD-converting
enzyme gene is constitutively expressed. Furthermore, the addition of cofactor was not required for thisconversion. To isolate the HMPPD-converting enzyme gene, a gene library of SYK-6 was screened. Subcloning
experiments suggested that the gene product of aprA, which belongs to the GMC oxidoreductase family, is an
HMPPD-converting enzyme.
Keywords: biomass, biodegradation, stilbene, C-elimination, C-dehydroxylation2013-P15
Sphingobium sp. SYK-6 株の dehydrodiconiferyl alcohol 代謝系に関わる
側鎖酸化酵素遺伝子の単離と解析
高橋 健司１）、廣瀬 優作１）、上村 直史１）、菱山 正二郎２）、原 啓文３）、笠井 大輔１）、
片山 義博４）、福田 雅夫１）、梶田 真也５）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）Malaysia-Japan Int’l. Inst. Tech.、４）
日本大学・生物資源科学部、５）東京農工大学大学院・生物システム応用科学府
Isolation and characterization of the genes involved in the side-chain oxidation of dehydrodiconiferyl alcohol in
Sphingobium sp. strain SYK-6
Kenji Takahashi1), Yusaku Hirose1), Naofumi Kamimura1), Shojiro Hishiyama2), Hirofumi Hara3), Daisuke
Kasai1), Yoshihiro Katayama4), Masao Fukuda1), Shinya Kajita5), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology,
Nagaoka, Niigata 940-2188, Japan, 2) Forestry and Forest Products Research Institute, Tsukuba, Ibaraki
305-8687, Japan, 3) Department of Environmental and Green Technology Malaysia-Japan International Instituteof Technology, 54100 Kuala Lumpur, Malaysia, 4) College of Bioresource Sciences, Nihon University, Fujisawa,
Kanagawa 230-0045, Japan, 5) Graduate School of Bio-Applications and Systems Engineering, Tokyo
University of Agriculture and Technology, Koganei, Tokyo, 184-8588 Japan
Abstract:
The objective of this study is to identify and characterize all the Sphingobium sp. SYK-6 genes
involved in the catabolism of a phenylcoumaran-type compound, dehydrodiconiferyl alcohol (DCA). It was
proposed that SYK-6 cells degrade DCA to vanillin and 5-formylferulate through six-step reactions. We
reported the isolation of the genes for the first two steps, and it was suggested that multiple alcohol564

dehydrogenase and aldehyde dehydrogenase genes contributed to the oxidation of DCA to DCA-C. In this study,
we isolated and characterized the genes involved in the conversion of DCA-C. Based on the fact that the
enzyme activity to convert DCA-C into DCA-CL was inducible, and this activity required FAD, the SYK-6oxidoreductase genes specifically induced in the cells grown in the presence of DCA were investigated by DNA
microarray analysis. As a result, phcC and phcD, which belong to the GMC oxidoreductase family, were found.
Disruption of phcC and phcD in SYK-6 resulted in a decreased conversion rate of DCA-C, therefore, thesegenes appeared to play important roles in the degradation of DCA-C. phcC and phcD were expressed in
Escherichia coli, and conversions of DCA-C into DCA-CL by these gene products were confirmed.
Keywords: biomass, dilignols, 8-5 dimer, bacteria, biodegradation2013-P16
Biodegradation of petroleum crude oil by Microphorus sp. SM04
Ade Andriani1), Kazutaka Itoh2), Sanro Tachibana2)
1)
The United Graduate School of Agricultural Sciences, Ehime University, 3-5-7 Tarumi Matsuyama, Ehime
790-8566 Japan, 2) Department of Applied Bioscience, Faculty of Agriculture, Ehime University 3-5-7 Tarumi,
Matsuyama, Ehime, 790-8566 Japan.
Abstract:
Preliminary screening using Remazol briliant blue R (RBBR) was conducted to obtain potential
ligninolytic fungi in crude oil degrading. Among 82 fungi screened from nature, 12 fungi showed ability todecolorize RBBR from blue to orange color. For screening experiment, two different types of petroleum oil
were used, namely heavy oil A (HOA) and heavy oil C (HOC), with two concentration (1000 and 15000 ppm).
5 Fungi (S03, S04, SM04, SM27, SM46) could grow well, both in HOC and HOA containing agar medium.
Then the ablity of five fungi to degrade HOC was examined in liquid medium. In this experiment, HOC withconcentration 1000 ppm was used as pollutant compounds. HOC contain aliphatic (37.5%), aromatic (36.6%),
NSO (15.2%), and asphalthene fraction (10.7%). Among all fungi, isolate SM04 showed highest degradation of
HOC. The degradation of aliphatic, aromatic, NSO, asphalthene fraction, and TPH by SM04 are 36.8, 22.7, 26.5,
18.2, 28.16% (15 days) and 76.4, 55.9, 46,2, 28.9, 59.3% (30 days), respectively. While TPH degradation of
S03, S04, SM27, SM46 in 30 days are 37, 42, 32, 28%, respectively. Ligninolytic enzymes such as Laccase andmangan peroksidase were detected during incubation by SM04. Based on molecular identification, S03, S04,
SM04, SM27, SM46 were identified as Trametes versicolor S03, Ganoderma gibbosum S04, Microporus
subaffinis SM04, Bjerkandera adusta SM27, and Bjerkandera adusta SM46.
Keywords: Petroleum crude oil, biodegradation, ligninolytic enzymes, white rot fungi, Microporus sp.
2013-P17
ジャトロファ種子の搾油カス由来のカテコール型リグナン･ネオリグナンについて
鈴木利貞，片山健至
香川大学農学部
Catechol-type lignan/neolignans isolated from the defatted seed residue of Jatropha
Toshisada Suzuki and Takeshi Katayama
Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa 761-0795, Japan
Abstract:
Jatropha (Jatropha curcus) is a shrub for biodiesel fuel production. From the defatted seed
residue of Jatropha, eight antioxidative lignan/neolignans which have catechol rings were isolated. Theirstructures, stereochemistry, and biosynthesis are discussed as compared with those of products by enzymaticand non-enzymatic dehydrogenation of caffeyl alcohol.
Keywords: Jatropha curcus, biodiesel fuel; antioxidant, caffeyl alcohol, 3,3’-bisdemethylpinoresinol565

第 59 回 （2014.09.11-12） 福井工業大学
201４-101
リグニン生合成中間体としてのモノリグノールグルコシド
寺島典二 1)、高千智 2)、松下泰幸 2)、Ulla Westermark3)
1)
名古屋大学名誉教授, 2)名古屋大学生命農学研究科、3) STFI, Stockholm, Sweden
Monolignol glucosides as intermediate compounds in lignin biosynthesis
Noritsugu Terashima1), Chisato Ko2), Yasuyuki Matsushita2), Ulla Westermark3)
1)
Emeritus Professor, Nagoya University, (Present address: 2-610, Uedayama, Tenpaku, Nagoya 468-0001
Japan), 2) Graduate School of Bioagricultural Science, Nagoya University, 3) STFI (Innventia), Stockholm,
SwedenAbstract:
A large amount of monolignol glucosides (p-glucocoumaryl alcohol, coniferin, syringin) arefound in lignifying soft xylem near cambium, and they disappear with the progress of lignification. Recently, it
became a matter of debate whether those monolignol glucosides are the real intermediates to form
macromolecular lignin or only a storage form of monolignol out of the main biosyntheic pathway. The
exclusion of monolignol glucosides from the main pathway is derived from the wrong explanation of incorrect
experimental procedures and too simple explanation of experimental result for flexible biological phenomena“lignification”. In this paper, we reconfirmed the most basic pathway of lignin biosynthesis starting fromL-phenylalanine to lignin via monolignol glucosides, and proposed a hypothetical scenario for 3D assembly
process of cellulose, hemicellulose and lignin in the lignifying cell wall. Advantages of monolignol glucosides
as the intermediates in formation of macromolecular lignin are summarized as follows: (1) They are watersoluble and so stable in oxidative environment that they are suitable for delivery to lignifying site through thepreformed thick polysaccharide gel. (2) β-D-Glucosidase specific to a specific glucoside can control formationof designed lignin supra- molecule according to the time, place and occasion (TPO). (3) Storage in large amount,often in crystalline form as an big metabolic pool, is advantageous for formation of a massive architecture in
TPO, e.g. postmortem lignification, late wood formation etc. (4) Slow turnover of monolignol glucoside,
namely slow fixation of ultrastructure in secondary wall (responsible for stem strength) supplied from the large
metabolic pool is advantageous for maintaining the stem in proper positions (reaction wood). (5) It isadvantageous also for plant that slow lignification in the secondary wall causes gradual ejection of water bywhich Ca++ and enzymes are transfered toward lumen side, and finally they are recovered for nitrogen economy.
Keywords: metabolic pool, cell wall architecture, Ginkgo, Magnolia,
201４-102
生体直交型反応を活用したリグニンのメタボリックラベルと蛍光標識
飛松裕基１）, ３）、Dorien Van de Wouwer２）、有賀哲１）、Eric Allen３）、Robert Kumpf２）、Bartel Vanholme２）、上高
原浩１）、高野俊幸１）、Wout Boerjan２）、John Ralph３）
１）
京都大学大学院農学研究科、 ２） Department of Plant Systems Biology, VIB, and Department of Plant
Biotechnology and Bioinformatics, Ghent University, Belgium、３）Department of Biochemistry, University of
Wisconsin, Madison and the US Department of Energy’s Great Lakes Bioenergy Research Center (GLBRC),USA
A bioorthogonal chemistry strategy for visualization of cell wall lignification
Yuki Tobimatsu1), 3), Dorien Van de Wouwer2), Satoshi Aruga1), Eric Allen3), Robert Kumpf2), Bartel
Vanholme2), Hiroshi Kamitakahara1), Toshiyuki Takano1), Wout Boerjan2), John Ralph3)
1)
Graduate School of Agriculture, Kyoto University, Japan, 2) Department of Plant Systems Biology, VIB, andDepartment of Plant Biotechnology and Bioinformatics, Ghent University, Belgium
3)
Department of Biochemistry, University of Wisconsin, Madison and the US Department of Energy’s Great
Lakes Bioenergy Research Center (GLBRC), USA
Abstrct: Bioorthogonal click chemistry was commissioned to visualize the plant cell wall lignification process invivo. This approach uses synthetic monolignol mimics tagged with chemical reporters (azide and alkyne groups)that can be metabolically incorporated into lignins in live plants, and subsequently derivatized via in vivo click
reactions, i.e., copper-assisted azide-alkyne cycloadditions or “copper-free” strain-promoted azide-alkyne
cycloadditions.
Keywords: Arabidopsis thaliana; cell wall; fluorescence microscopy; in vivo imaging; lignin biosynthesis.
2014-103566

ミズナラ落葉の冬季生分解過程におけるリグニンの挙動
幸田圭一 1)、川口 新 2), 3)、宮本敏澄 1)、浦木康光 1)１）
北海道大学 大学院農学研究院、２）北海道大学 大学院農学院、３）リンナイ〔株〕
Qualitative and quantitative monitoring of lignin in leaf litter of Japanese oak tree (Quercus mongolica var.
grosseserrata) during the biodegradation process in winterKeiichi Koda1), Arata Kawaguchi2), 3), Toshizumi Miyamoto1), Yasumitsu Uraki1)
1)
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 2) Graduate School of
Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 3) Rinnai Co., Nagoya 454-0802, Japan
Abstract:
An improved method to monitor lignin in leaf litter has been proposed, with a combination of
two methods to determine methoxy group and alkaline nitrobenzene oxidation products. Our results provided
additional evidence that conventional methods for lignin determination, such as Klason and acetyl bromide
methods, gave an overestimated value of lignin content, as repeatedly indicated in earlier studies. Next, theauthors tried to monitor the changes in lignin in leaf litter qualitatively and quantitatively during its
biodegradation process including wintertime, using our combined method. It was confirmed that while leaf litter
was decomposed progressively under snow cover during wintertime, lignin in leaf litter was also degradedaccordingly, indicating leaf lignin-degrading microbes were active in soil organic matter at around 0 oC.
Contrary to the previous observation, lignin content of leaf litter was steadily and gradually decreased in thecourse of time, to a comparable degree as the other leaf components. This result suggests foliage lignin is not asrecalcitrant as has been supposed. Interestingly, condensed lignin structures, supposedly less biodegradable thannon-condensed structures of lignin, were also decreased to a comparable degree.
Keywords: foliage lignin, leaf litter, carbon cycle, biodegradation, Japanese oak (Quercus mongolica var.
grosseserrata)
2014-104
樹木の葉から得られるクラーソン残渣のメトキシル基の分析
戸田守一、秋山拓也、横山朝哉、松本雄二
東京大学大学院 農学生命科学研究科
Methoxyl analysis of Klason residue of tree leaves
Morikazu Toda, Takuya Akiyama, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences,Graduate School of Agricultural and life
Sciences, The University of Tokyo
Abstract:
In previous studies, it was strongly suggested that Klason method overestimates the lignin
content of non-wood tissues or plants due to the inclusion of non-lignin substances in Klason residue and that no
pre-extraction method could remove these non-lignin substances selectively. In this study the behavior of
methoxyl group in leaf samples during extraction was examined.
Amount of methoxyl group in Klason residue of leaf samples were extremely lower than that of woodsamples.
By various kind of pre-extraction, the amount of methoxyl group in Klason residue of leaves was found to
decrease when it was expressed as non-extracted sample basis value. This result indicated that a part ofsubstances which contains methoxyl group and participates in the formation of Klason residue can be removedby these pre-extraction. Amount of methoxyl group found in nitrobenzene oxidation products was also
examined for leaf samples before and after various pre-extraction. In case of wood sample, the amount ofmethoxyl group found in nitrobenzene oxidation products should be lower than that found in Klason residue andshould not change significantly by pre-extraction. However, the amount of methoxyl group found innitrobenzene oxidation products decreased by pre-extraction almost proportionally to that found in Klason
residue.
Keywords: leaf, Klason residue, methoxyl group, extraction
2014-105
樹種間におけるビフェニル型構造量の多様性
後藤晴加、玉井あかり、秋山拓也、松本雄二
東京大学大学院 農学生命科学研究科
Variety of the content of biphenyl structures among different wood species
Haruka Goto, Akari Tamai, Takuya Akiyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657, Japan
567

Abstract:
Although biphenyl structure is important structural unit as a candidate of branch-points of lignin,
limited information is available for the content of biphenyl structures. In this study, 21 kinds of wood meals
including 6 softwood and 15 hardwood species were analyzed by alkaline nitrobenzene oxidation method toinvestigate the variety of the content of biphenyl structures among different wood species. In the case of thesoftwoods, the total yields of biphenyl products varied within a narrow range (0.030-0.035 mol/200 g lignin), in
which the yield was slightly lower in a species having a lower methoxyl content of lignin. In contrast, the total
yields of biphenyl products ranged widely among hardwood species (0.0012-0.023 mol/200 g lignin). The
hardwood species having a higher syringyl/guaiacyl ratio exhibited a lower biphenyl products yield, and a lower
yield ratio of biphenyl products to all the guaiacyl type degradation products. The latter tendency implies that,during lignin polymerization, the frequency of 5-5 coupling reaction between guaiacyl units was not constant,but lowered by cross-coupling reaction between syringyl and guaiacyl units when syringyl content is higher.
Keywords: lignin biosynthesis, divanillin, 5-5 linkage, gymnosperm, angiosperm
2014-106
クラフトパルプの過硫酸処理における残留リグニンの分解挙動
劉 強 1)、アンドリ タウフィック リザルディン 1, 2)、大井 洋 1)
1)
筑波大学大学院 生命環境科学研究科、2)インドネシア産業省 紙パルプセンター
Behavior of residual lignin during peroxymonosulfuric acid treatment of kraft pulp
Qiang Liu1), Andri Taufick Rizaluddin1, 2), Hiroshi Ohi1)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan
2)
Center for Pulp and Paper, Ministry of Industry, Indonesia
Abstract:
Conversion of chlorine process into Elemental chlorine-free (ECF) bleaching is known to beefficient for reducing the amount of organic chlorine compound in effluent to significant extent. However,biodegradability of the organic chlorine compound in mill effluent should be more improved because mills still
release organochlorine substances. ECF bleaching is still discharging organochlorine substances, especiallychloroform by volatilization. On the other hand, total chlorine-free (TCF) bleaching is a process that eliminates
possibility of organochlorine compound formation in bleaching process. Peroxymonosulfuric acid (MPS) has
been identified as one of promising alternative chemicals for delignification of wood and bleaching. It is capable
to oxidize and solubilize lignin and also to decompose hexenuronic acid (HexA), which is one of thecompounds resulting in pulp yellowing. MPS also can be produced on industry scale with high stability andsuccessfully installed in mills as a conversion of acid washing stage of ECF bleaching. MPS treatment was
conducted with 10% pulp consistency at pH 3 and 70ºC for 70 min. The application of MPS indicated that pulp
brightness
increasedto84-86%ISO
with
0.1-0.5%
MPS
dosagebythe
Oxygen-MPS-Ozone-Extraction-Peroxide bleaching. In this study, we investigated effects of the application of
MPS on decrease of HexA and kappa number, and on decomposition behaviors of vanilliyl alcohol and syringyl
alcohol and other lignin model compounds.
Keywords: pulp bleaching, peracid, viscosity, Acacia, dissolving pulp
2014-107
オイルパーム幹のアルカリ/グリセリン蒸解によるパルプとリグニンの特性
佐治薫 1)、橋田光 2)、戸川英二 2)、久保智史 2)、田中良平 2),3)、佐藤雅俊 1)
１）
東京大学大学院農学生命科学研究科、 ２）森林総合研究所バイオマス化学研究領域、 ３）インドネシア工業省バンダルランプン工業研究・標準化センター
Characterization of pulp and lignin prepared from oil palm trunk by the alkaline/glycerol pulping
Kaoru Saji1), Koh Hashida2), Eiji Togawa2), Satoshi Kubo2), Ryohei Tanaka2), 3),Masatoshi Sato1)
1)
Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo
113-8657, Japan, 2)Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687,
Japan, 3)Balai Riset dan Standardisasi Industri Bandar Lampung, JL. By Pass Soekarno-Hatta, Km. 1 Rajabasa,
Bandar Lampung 35144, Indonesia
Abstract:
The oil palm tree has widely planted for the production of edible oil in South East Asian
countries such as Indonesia and Malaysia. In those countries, large amount of oil palm waste is constantly
produced due to its plantation cycle. For the effective utilization of these waste biomass as a raw material of
biomass energy and material productions, oil palm trunk was cooked in alkaline/glycerol, which could be
produced as by-products of biodiesel production, to separate it into the components, carbohydrate and lignin. In
the alkaline/glycerol process, lignin was effectively removed in comparison with alkaline cooking process. Pulp
yield in the alkaline/glycerol process was also higher than that in the alkaline cooking process. The
568

alkaline/glycerol process would be a good method for component separation of the oil palm trunk.
Keywords: oil palm trunk, alkaline/glycerol, pulp, hemicellulose, lignin
2014-108
リグノセルロース酵素糖化に及ぼす試料加熱前処理の効果
小柴太一１）、向井まい１）、服部武文１,２）、鈴木史朗１）、坂本正弘３）、梅澤俊明１,４）
1）
京大生存研、２）徳島大院 SAS、３）京大院農学研究科、４）京大生存基盤科学研究ユニット
Drying temperature on rice straw affects the enzymatic saccharification efficiency
Taichi Koshiba1), Mai Mukai1), Takefumi Hattori1, 2), Shiro Suzuki1), Masahiro Sakamoto3), and Toshiaki
Umezawa1, 4)
1)Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan
2)
Institute of Socio-Arts and Sciences, The University of Tokushima, 1-1 Minamijosanjima-cho, Tokushima
770-8502, Japan, 3) Graduate School of Agriculture, Kyoto University, Kitashirakawa-oiwakecho, Sakyo-ku,
Kyoto 606-8502, Japan, 4) Institute of Sustainability Science, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract:
In order to use lignocellulose for polysaccharide, the pretreatment of plant materials is required.
Usually, the pretreatment of plant materials after harvesting is drying, grinding and powdering. The effects ofgrinding on saccharification efficiency have been studied intensively. However, the first step of pretreatment,
namely drying has not been noted. In this study, we estimated the effect of drying temperature on enzymatic
saccarifiation efficiency. After harvesting of rice (Oryza sativa), rice straws were dried at 27˚C, 50˚C and 70˚Cduring 31, 5 and 4 days, respectively. The enzymatic saccharification efficiency was 45.1, 45.6 and 41.6%,
respectively under each temperature. Obviously, the efficiency of pretreatment under 70˚C drying was
decreased. It is well known that many polymers change their shape with temperature rising. The glass transition
point of lignin is 60 - 70˚C under a high water content condition. Our results strongly suggested that the highdrying temperature caused plasticization of lignin and extra encrustation of cellulose microfibrils by lignins,which resulted in decreasing of accessibility of hydrolyzing enzymes to cellulose.
Keywords: rice straw, drying temperature, lignin, lignocellulose, saccharification
2014-109
ソフト水熱プロセスによるきのこ廃培地中の水／アセトニトリル可溶性低分子の挙動
大田ゆかり１）、宮本徹２、３）、黒澤佳奈子１）、坪内泰志１）、佐藤玲央奈１）、秦田勇二１）
1)
海洋研究開発機構 (JAMSTEC)、２）東北大院医、３）前田製作所
Behaviors of the water/acetonitrile-soluble low-molecular-weight compounds in the soft-hydrothermal
processing of the waste culture media of edible mushrooms
Yukari Ohta1), Toru Miyamoto2, 3), Kanako Kurosawa1), Taishi Tsubouchi1), Reona Sato1), Yuji Hatada1)
1)Japan Agency for Marine-Earth Science and Technology (JAMSTEC), 2) Graduate School of Medicine,
Tohoku University, 3) Maeda Seisakusho, Co., Ltd.
Abstract:
Lignin is a potential sustainable resource of non-petroleum natural aromatic chemicals. The
waste culture media of the edible mushroom are the plausible candidates as raw materials containing partiallydegraded lignin. Recently, we succeeded the microbial production of the aromatic monomer of phenyl-propane
structure from the waste culture media of the edible mushroom, Hypsizygus marmoreus, Bunashimeji. The yield
was elevated after the pretreatment by the soft-hydrothermal processing of the starting raw materials. In thisstudy, we traced the water/acetonitrile-soluble low-molecular weight compounds during the pretreatment using
the LCMS analysis. Multivariate statistical analysis revealed the behavior of aromatic monomers which wereconsumed along with the growth of H. marmoreus and regenerated by the soft-hydrothermal processing. The
LCMS analysis coupled with the chemometrics procedures was a robust tool to summarize and visualize thecomplex components of the bioresources.
Keywords; bacteria, beta-O-4, biorefinery, enzyme, principal component analysis
2014-110
スギ炭化物及びそのアセチル化処理試料に吸着したセシウムイオンの可視化
山㟁崇之、栗本康司、山内 繁
秋田県立大学木材高度加工研究所
Visualization of the cesium ions adsorbed onto Japanese cedar charcoals and their acetylated samples
Takayuki Yamagishi, Yasuji Kurimoto, Shigeru Yamauchi
Institute of Wood Technology, Akita Prefectural University,11-1 Kaieisaka, Noshiro 016-0876
569

Abstract:
To visualize the distribution of cesuim ions (Cs+) adsorb onto Japanese cedar charcoals
carbonized at 300oC, 500oC, and 700oC under N2 flow, respectively, Scanning electron microscopy and Energy
dispersive X-ray (SEM-EDX) analysis was applied to these samples. After soaking in saturated aqueous CsCl
solution, these samples were embedded in Technovit 7100 to make a thin section (1 m) for the observations of
Cs+ by SEM-EDX analysis. As a result of the Cs+ observations, Cs+ adsorb onto the all samples could be seen
with a sufficient contrast. Each charcoal sample treated by acetylation was also prepared in the same procedure.
However, Cs+ on these samples could not be seen with a sufficient contrast. It was suggested the possibilities
that the protection of alcoholic hydroxyl groups and phenolic hydroxyl groups on these charcoal surfaces could
affect the Cs+ adsorption involved in the ion-exchange sites of these groups, and that the Cs+ adsorption
involved in the Wan der Waals force and ion-exchange sites of carboxylic groups might be affected by the sterichindrance of acetyl groups introduced on the charcoal surface. Since introduction of acetyl groups on the
charcoal surface apparently affected the Cs+ adsorption, ester structure of introduced acetyl groups wereassumed to be less interaction with the Cs+.
Key word:line analysis, torrefaction, microtome, functional group, compound middle lamella
2014-111
リグニンの精製によるリグニン硬化エポキシ樹脂の高 Tg 化
香川博之１）、岡部義昭１）、佐々木 千鶴２）、中村 嘉利２）
１）(株)日立製作所日立研究所、２）徳島大学大学院ソシオテクノサイエンス研究部
Improvement of the glass transition temperature of epoxy resin hardened by steam-exploded lignin
Hiroyuki Kagawa1), Yoshiaki Okabe1), Chizuru Sasaki2), Yoshitoshi Nakamura2)
1)
Hitachi Research Laboratory, Hitachi, Ltd., 7-1-1 Omika-cho, Hitachi-shi, Ibaraki-ken, 319-1292 JAPAN,
2)
Department of Life System, Institute of Technology and Science, The University of Tokushima, 2-1
Minamijosanjima-cho, Tokushima-shi, Tokushima- ken, 770-8506 Japan
Abstract:
We are currently researching the application of lignin extracted from steam-exploded woody
biomass to epoxy resins, which is widely used as an insulating material in modern electric and electronicequipment. We have already reported that the glass transition temperatures of hardened epoxy resin containing
lignin were higher than those of commercially available epoxy resins, and that the electric and heat resistanceproperties of epoxy resins hardened with steam-exploded lignins are equivalent to those of conventional epoxy
resin.. Here, we report improvement of the glass transition temperature of epoxy resin hardened bysteam-exploded lignin. The decomposition temperature of steam-exploded lignin could be improved by
reducing low-molecular-weight compounds contained in the steam-exploded lignin. The glass transition
temperature of epoxy resin hardened by steam-exploded lignin was also improved by refinement ofsteam-exploded lignin or wood feedstock prior to the steam explosion. On the other hand, the decomposition
temperature of epoxy resins hardened by steam-exploded lignins was not improved by the refinement. It wassuggested that the thermal decomposition of hardened epoxy resin is primary caused by the decomposition oflignin.
Keywords: steam explosion, glass transition temperature, epoxy resin, heat resistance2014-112
スギ加溶媒分解リグニンを用いた新規ポリエステルフィルムの調製とその応用
久保田惇１）、磯崎友史 1）、山田竜彦 2)、幸田圭一 3)、浦木康光 3)１）
北海道大学大学院農学院、２）森林総合研究所、３)北海道大学大学院農学研究院
Preparation and application of a new polyester film from cedar-organosolv lignin
Atsushi Kubota1), Tomofumi Isozaki1), Tatsuhiko Yamada2), Keiichi Koda3), Yasumitsu Uraki3)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 2) Department of Biomass
Chemistry, Forestry and Forest Products Research Institute, Tsukuba 305- 8687, Japan,
3)
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan
Abstract:
A new polyester film based on the melt-polymerization of softwood organosolv lignin was
fabricated by hot pressing, with varying molar charge ratio of maleic anhydride to hydroxy group of the lignin.
This organosolv lignin was directly isolated by a solvolysis of cedar chips with polyethylene glycol 400(PEG400) and a small amount of sulfuric acid as a catalyst, and showed a thermal fusibility. At a certain charge
ratio of 6.6/3.4, tensile strength and young modulus were shown to be the maximum values of 45.6 MPa, and
2.4 GPa, respectively. Moreover, we assembled an electric double layer capacitor (EDLC) containing this film
as a separator, to investigate the application of this polyester film. Although the resulting EDLC didn’t show agood performance when the polyester film was used without further modification, formation of pores on the570

film improved the electrochemical property of EDLC; the specific capacitance reached nearly 80 % of the one
with a commercial cellulose separator. These results indicate this lignin-based polyester film can be utilized as aseparator material for the EDLC.
Keywords: organosolv lignin, melt polymerization, EDLC separator
2014-113
リグニン系活性炭素繊維を原料とする電気二重層キャパシタ用電極の開発
游 翔宇 1)、段 軍磊 1)、幸田圭一 2)、山田竜彦 3)、浦木康光 2)1)
北海道大学 大学院農学院、2)北海道大学 大学院農学研究院、3)森林総合研究所
Development of electrode for electric double layer capacitor from lignin-based activated carbon fibers
Xiangyu You1), Duan Jinlei1), Keiichi Koda2), Tatsuhiko Yamada3), Yasumitsu Uraki2)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 2) Research faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan, 3) Biomass Division, Forestry and Forest Products
Research Institute, Tsukuba 305-8687, Japan
Abstract:
In the lignin symposium last year, we reported to prepare activated carbon fibers (ACF) from
hardwood acetic acid lignin and to assemble electric double layer capacitor (EDLC) with the ACF and organic
electrolyte together with conductive carbon black. In this study, such EDLCs were prepared from two kinds ofisolated softwood (Japanese cedar) lignins, soda (SL)-lignin and PEG-lignin, via electrospinning. Although we
expected that thin fibers prepared by electrospinning would be easily converted to ACF with very large surface
area, electrospun SL-lignin fibers were converted to ACF with lower BET surface area than the ACFs fromother types of lignin fibers which were thicker. Due to this fact, EDLC assembled with the SL-lignin-based ACF
had inferior electrochemical performance to the EDLCs with ACFs from other lignin-based ACF. On the other
hand, EDLC with PEG-lignin-based ACF showed moderate electrostatic capacitance, and noticeably low chargetransfer resistance. In this symposium, we will further discuss the relationship between electrostatic capacitanceof EDLC and pore structure of ACF.
Keywords: cedar, electrode for electric double layer capacitor, electrospinning, PEG-lignin, soda-lignin,
2014-特別講演
触媒の発見から実用化まで、～クリーン酸化、テルペンやセルロースの変換、砂の資源化～
佐藤一彦（独）産業技術総合研究所 触媒化学融合研究センター
Green oxidation with hydrogen peroxide
Kazuhiko Sato
National Institute of Advanced Industrial Science and Technology (AIST), Central 5-2, 1-1-1 Higashi, Tsukuba,
Ibaraki 305-8565, Japan
Abstract:
Oxidation is a core technology for converting petroleum-based materials to useful chemicals ofa higher oxidation state. Aqueous hydrogen peroxide (H2O2) is an ideal oxidant, because the atom efficiency is
excellent and water is theoretically the sole co-product. However, H2O2 can be a clean oxidant only if it isused in a controlled manner without organic solvents and other toxic compounds. Thus, the discovery of an
efficient catalyst and the choice of reaction conditions are the keys to realizing an ideal oxidation procedure.
In this context, we developed various oxidation reactions with aqueous H2O2 under organic solvent- andhalide-free conditions.
Keywords: catalyst, cellulose, organosilicon, insulating resin, levulinic acid2014-201
-O-4 型リグニンモデルオリゴマーの合成研究
板倉圭佑、岸本崇生、濱田昌弘、中島範行
富山県立大学工学部
Synthetic study on  -O-4 type lignin model oligomer
Keisuke Itakura, Takao Kishimoto, Masahiro Hamada, Noriyuki Nakajima
Faculty of Engineering, Toyama Prefectural University, Imizu, Japan 939-0398
Abstract:
Artificial lignin polymers with  -O-4 linkages have been synthesized in our laboratory. In thisstudy two synthetic strategies: convergent and linear syntheses were evaluated for the synthesis of  -O-4 typelignin model oligomer with distinct degree of polymerization. A key reaction step was Williamson ether
formation, which includes nucleophilic substitution under basic conditions. Effect of several bases and571

protective groups were investigated and a tetramer was synthesized by the linear synthetic strategy.
Keywords: Synthesis, -O-4, tetramer, trimer, dimer
2014-202
酸性条件下におけるベンジルカチオンの生成挙動
塩谷俊直、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Formation behavior of benzyl cation of lignin model compounds under acidic conditions
Toshinao Shioya, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo,1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8675, Japan
Abstract:
In this study, it was examined how the difference between p-hydroxyphenyl (H), guaiacyl (G),and syringyl (S) or between phenolic (P) and non-phenolic (N) nuclei controls the formation rate of benzyl
cation under acidic conditions using model compounds, 2-(4-hydroxy- benzyloxy)ethanol (HP),
2-(4-methoxybenzyloxy)ethanol(HN),
2-(4-hydroxy-3methoxybenzyloxy)
ethanol(GP),
2-(3,4-dimethoxybenzyloxy)ethanol (GN), 2-(4-hydroxy-3,5-dimethoxybenzyloxy) ethanol (SP), and2-(3,4,5-trimethoxybenzyloxy)ethanol (SN). The disappearances of all the model compounds were wellapproximated to pseudo-first-order reactions. The pseudo-first- order reaction rate constants of the modelcompounds with H, G, and S nuclei were in the order of: H > G > S. On the other hand, the P type modelcompounds disappeared much faster than the N type model compounds. These results suggest that benzyl cationis generated most rapidly from H nucleus and most slowly from S nucleus and that P type nucleus affords
benzyl cation much more rapidly than N type nucleus.
Keywords: wood, acidolysis, carbo cation, carbenium ion
2014-203
非フェノール性 β-エーテル型リグニン二量体モデル化合物の熱分解反応機構 －側鎖水酸基に起因するレト
ロアルドール反応－
松田佳子、福留 明日香、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Pyrolysis mechanism of a non-phenolic β-ether type lignin model dimer －Retro-aldol reactions occurring at
the side-chain－
Keiko Matsuda, Asuka Fukutome, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Sakyo-ku. Kyoto, 606-8501 Japan
Abstract:
Influence of the Cγ-OH group on the pyrolytic reactivity of non-phenolic -ether type lignin
model dimer was studied in ampoules under the condition of N2/350℃/2min. Although the Cγ-deoxy typedimer became reactive only in the presence of wood flour as a radical source, the Cγ-OH type dimer degradedeven without the addition of any radical sources. Furthermore, the pyrolysis products were very different
depending on the Cγ-structure; the major products from the Cγ-deoxy type had C3 side-chains, while theproducts from the Cγ-OH type contained shorter C1 and C2 side-chains. Based on these results, two types ofretro-aldol reactions were suggested for the pyrolysis of the Cγ-OH type dimer. These reactions are discussedwith the side-chain conversions and depolymerization of natural lignins during pyrolysis. The results of thetheoretical investigations indicated an interesting feature of these retro-aldol reactions; the reactivity is very
different depending on the stereochemistry of the side-chain, i.e., erythro and threo types.
Keyword:pyrolysis, retro-aldol reaction, depolymerization, stereochemistry, theoretical investigation
2014-204
２次元 NMR による天然試料のフェニルグリコシド型 LCC の化学構造解析
宮川泰幸 1)、飛松裕基 1)、水上貴仁 1)、John Ralph2)、上高原浩 1)、高野俊幸 1)
1)
京都大学大学院農学研究科、2)Department of Biochemistry, University of Wisconsin, Madison and the US
Department of Energy’s Great Lakes Bioenergy Research Center (GLBRC), USA
2D NMR analysis of lignin-carbohydrate complex (LCC) in Eucalyptus globulus
Yasuyuki Miyagawa1), Yuki Tobimatsu1), Takahito Mizukami1), John Ralph2), Hiroshi Kamitakahara1),
Toshiyuki Takano1)
1)
Graduate School of Agriculture, Kyoto University, Kyoto, Japan, 2)Department of Biochemistry, University of
Wisconsin, Madison and the US Department of Energy’s Great Lakes Bioenergy Research Center (GLBRC),
572

USA
Abstract:
The Eucalyptus globulus wood meal was separated into 12 fractions via multi-step solvent
extractions, and the distributions and structures of lignins and carbohydrates in the each fractions were profiledusing 2D NMR techniques. Our NMR data suggest that lignins mainly composed of syringyl β–O–4 units aretightly associated with xylans in Eucalyptus wood cell walls. A newly constructed, NMR database based onsynthetic model for phenyl glycoside type lignin-carbohydrate linkages were applied to delineate
lignin-carbohydrate complex (LCC) possibly present in Eucalyptus wood cell walls.
Keywords: lignin-carbohydrate complex (LCC), xylan, phenyl glycoside, Eucalyptus globulus, HSQC
NMR
2014-205
ジヒドロコニフェリルアルコールの脱水素重合とその結合様式
河合真吾 1)、志賀昭裕 2)、米田夕子 1)、西田友昭 1)
1)
静岡大学大学院農学研究科、2)静岡大学農学部
Dehydrogenative polymerization of dihydroconiferyl alcohol and its chemical sturucture
Shingo Kawai 1), Akihiro Shiga 2), Yuko Yoneda 1) and Tomoaki Nishida 1)
1)
Graduate School of Agriculture, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka, 422-8529, Japan,2)
Faculty of Agriculture, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka, 422-8529, Japan
Abstract:Cβ-radical mesomeric hybrid of the phenoxy radical of coniferyl alcohol is the most importantintermediate during the dehydrogenatiive polymerization of lignin, because Cβ-radical is involved in theformation of β-O-4, β-5 and β-β substructures of lignin macromolecules. When coniferyl alcohol is reductively
converted to dihydroconiferyl alcohol without the side chain double bond, the generation of Cβ radical becomes
impossible, and it is expected that lignin biosynthesis greatly changes. In this study, we performed an in vitro
polymerization of dihydroconiferyl alcohol (DC-DHP). DC-DHP exhibited lower degree of polymerization thanconiferyl alcohol DHP and considerable amount of dihydroconiferyl alcohol oligmers was formed. Frthermore,
it was revealed that the major compound of the oligmeric fraction was a dimer having 4-O-5 linkage.
Keywords: dihydroconiferyl alcohol, lignin biosynthesis, double bond reductase, lignin substructure
2014-206
細菌のピノレジノール還元酵素遺伝子を用いた植物の芳香族化合物代謝の改変
田村 尚之 1)、辻 幸子 1)、上村 直史 2)、岡澤 敦司 3)、菊地 淳 4)、菱山 正二郎 5)政2)
1)
井 英司 、梶田 真也
1)
東京農工大学大学院 生物システム応用科学府、2)長岡技術科学大学 生物系
3)
大阪府立大学大学院 生命環境科学研究科、4)理化学研究所 資源環境科学研究センター
5)
森林総合研究所 バイオマス化学研究領域
Metabolic engineering of plant phenolic compounds by heterologous expression of a gene for pinoresinol
reductase in transgenic plants
Masayuki Tamura1), Yukiko Tsuji1), Naofumi Kamimura2), Atsushi Okazawa3), Jun Kikuchi4), Shojiro
Hishiyama5), Eiji Masai2), Shinya Kajita1)
1)
Tokyo University of Agriculture and Technology, Tokyo, Japan. 2) Nagaoka Institute of Technology, Niigata,Japan. 3) Osaka Prefecture University, Osaka, Japan. 4) RIKEN Center for Sustainable Resource Science, RIKEN,
Kanagawa, Japan. 5) Forestry and Forest Products Research Institute, Ibaraki, Japan
Abstract:
Pinoresinol reductase and pinoresinol/lariciresinol reductase play important roles in an earlystep of lignan biosynthesis in plants. The activities of both enzymes have also been detected in bacteria. In thisstudy, pinZ, which was first isolated as a gene for bacterial pinoresinol reductase, was constitutively expressedin Arabidopsis thaliana with and without apoplast-targeting sequence (ATS) under the control of thecauliflower mosaic virus 35S promoter. Higher reductive activity toward pinoresinol was detected in the
resultant transgenic plants but not in wild-type plants. The activity was higher in the transgenic plants harboring
the transgene attached without ATS than that with ATS. Principal component analysis of data from untargeted
metabolome analyses of tissue extracts of the wild-type and two independent transgenic lines with pinZ without
ATS indicate that pinZ expression caused dynamic metabolic changes in stems, but not in roots and leaves.
Amounts of pinoresinol and its glucoside form in soluble extracts of the tissues were markedly reduced in thetransgenic plant with highest PinZ activity, whereas the amounts of glucoside form of secoisolariciresinol
increased. Our findings indicate that overexpression of pinZ induces change in lignan compositions and has amajor effect not only on lignan biosynthesis but also on biosynthesis of other primary and secondary573

metabolites. Structural analysis of lignin in the transgenic plans is now in progress.
Keyword:gene expression, secondary metabolite, transgenic plant
2014-207
Sphingobium 属細菌の dehydrodiconiferyl alcohol 代謝系遺伝子の単離と機能解析
高橋 健司１）、上村 直史１）、菱山 正二郎 2）、原 啓文 3）、笠井 大輔１）、片山 義博 4）、福田 雅夫１）、梶田 真
也 5）、政井 英司 1）１）
長岡技術科学大学・生物、２）森林総合研究所、３）MJIIT, Univ. Tech., Malaysia、４）日本大学・生物資源科学
部、５）東京農工大学大学院・生物システム応用科学府
Isolation and characterization of dehydrodiconiferyl alcohol catabolism genes in Sphingobium sp. strain SYK-6
Kenji Takahashi1), Naofumi Kamimura1), Shojiro Hishiyama2), Hirofumi Hara3), Daisuke Kasai1), Yoshihiro
Katayama4), Masao Fukuda1), Shinya Kajita5), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan,
2)
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan,3)Department of Environmental
Engineering and Green Technology, Malaysia-Japan International Institute of Technology, Universiti Teknologi
Malaysia, Kuala Lumpur, Malaysia, 4)College of Bioresource Sciences, Nihon University, Fujisawa, Kanagawa,Japan, 5)Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo, Japan
Absract:
The objective of this study was to identify and characterize the Sphingobium sp. SYK-6 genes
involved in the catabolism of a phenylcoumaran-type compound, dehydrodiconiferyl alcohol (DCA). In SYK-6
cells, the alcohol group at the -carbon of the B-ring side chain of DCA was oxidized to the carboxyl group to
generate DCA-C. The resulting DCA-C was converted to DCA-CC by the oxidations of the alcohol group at the
-carbon of the A-ring side chain of DCA-C. DCA-CC was degraded to 5-formylferulate and vanillin throughthe release of -carbon and the cleavage of the C-C linkage of the A-ring side chain. In the first two steps, themultiple genes encoding alcohol dehydrogenases and aldehyde dehydrogenases were identified as possibly
being involved in the conversion processes. The phcC and phcD genes, which belong to the GMC
oxidoreductases, were identified as candidate genes responsible for the oxidation of DCA-C. Disruption of phcCand phcD in SYK-6 resulted in a decrease in the rate of DCA-C conversion, indicating that these genes play
important roles in the degradation of DCA-C. Conversion of DCA-C by the gene products of phcC and phcD
was confirmed using recombinant proteins produced in Escherichia coli and SYK-6.
Keywords: dilignol, β-5, biodegradation, catabolic pathway
2014-208
高活性リグニン分解菌 Phanerochaete sordida YK-624 株のリグニン分解過程におけるトランスクリプトーム解析
王 剣橋 1)、鈴木 智大 2)、河岸 洋和 1, 2, 3)、平井 浩文 1, 2)
1)
静岡大学大学院農学研究科、2)静岡大学グリーン科学技術研究所、3)静岡大学創造科学技術大学院
Transcriptome analysis in lignin degradation process by hyper lignin-degrading fungus Phanerochaete sordida
YK-624
Jianqiao Wang1), Tomohiro Suzuki2), Hirokazu Kawagishi1, 2, 3), Hirofumi Hirai1, 2)
1)Graduate School of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2)Research Institute of Green
Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan,
3)
Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
The mechanism of lignin biodegradation by white-rot fungi has been extensively studied.
However, the whole process is still unknown. In particular, it is interesting that why the white-rot fungus
Phanerochaete sordida YK-624 indicates high lignin-degrading activity. In order to identify genes which are
involved in lignin biodegradation by P. sordida YK-624, we analyzed the differential gene expression of P.
sordida YK-624 under the ligninolytic and non-ligninolytic conditions by next generation sequencing. Total
RNA was extracted from the wood (ligninolytic) and holocellulose (non-ligninolytic) medium. After theconstruction of cDNA library, short read sequence data (300 bp read length) were obtained using MiSeq. We
obtained high-quality read sequences by removing regions with low quality scores in fastq files (quality scores <30). The high-quality short reads from samples were assembled into unigenes (contigs, a non-redundantsequence set) by program Trinity. To detect genes showing different gene expression levels, we investigatedexpression levels by FPKM (Fragments Per Kilobase of exon per Million mapped reads) measurement.
Biological functions of differential unigenes were predicted by BLAST, Gene Ontology and KEGG pathway574

analyses. As the results of the differential gene expression analysis, manganese peroxidase and glyoxal oxidase
which were related to lignin biodegradation were upregulated under the ligninolytic condition. On the other
hand, some genes such as oligopeptide transporters which have not been previously reported in lignin
biodegradation were also upregulated under the ligninolytic condition.
Keywords: Phanerochaete sordida YK-624; lignin biodegradation; differential gene expression; Miseq
2014-209
Biodegradation of polycyclic aromatic hydrocarbons mixture by Pestalotiopsis sp.
Dede Heri Yuli Yanto1), Kazutaka Itoh2), Sanro Tachibana2)
1)
The United Graduate School of Agricultural Sciences, Ehime University, 3-5-7 Tarumi Matsuyama, Ehime
790-8566 Japan, 2)Department of Applied Bioscience, Faculty of Agriculture, Ehime University 3-5-7 Tarumi,
Matsuyama, Ehime, 790-8566 Japan.
Abstract:
The ability of Pestalotiopsis sp. NG007 to degrade and transform PAHs was examined using
four PAHs: acenaphthene (ACE), anthracene (ANT), chrysene (CHRY), and benzo[a]pyrene (BaP) in liquidmedium. The experiments were conducted in different pH (3 – 12) and salinities (0 – 10%). The results showedthat the biodegradation of PAHs mixture was dependent to pH and salinities. All the PAHs showed a maximum
degradation at pH 3 and salinities 2–2.5%. The maximum removal for ACE, ANT, CHRY, and BaP were 100%,91%, 76%, and 68%, respectively. In general, the biodegradation capacity decreased with the increasing of ringnumber in PAHs. Analysis of metabolites using GC-MS showed at least 11 compounds were detected. Strain
NG007 degraded ACE via the formation of 1-acenaphthenol (I), acenaphthenon (II) and naphthalic anhydride(III). The presence of anthraquinone (IV) in the culture can be identified as a metabolite from ANT degradation.
In addition, the presence of 1-hydroxy-2-naphthoic acid (V) may indicate the metabolism of CHRY and BaP.
Other compounds such as gentisic acid (VI), mandelic acid (VII), phthalic acid (VIII), cathecol (IX),
benzaldehyde (X), and benzoic acid (XI) indicated that the biodegradation of the major metabolites into small
compounds was occurred. This study demonstrated that strain NG007 can degrade all the PAHs in the mixture
and may consider to have the potential for degradation of PAHs in contaminated environments.
Keywords: biodegradation, ligninolytic enzymes, PAHs, Pestalotiopsis sp., saline
2014-P01
芳香核 1 位 13C 標識コニフェリルアルコールの新規合成方法の検討
伊藤郁、松下泰幸、青木弾、福島和彦
名古屋大学大学院生命農学研究科
Investigation of new synthesis approach of coniferyl alcohol-[ring-1-13C]
Kaori Ito, Yasuyuki Matsushita, Dan Aoki, Kazuhiko Fukushima
Graduate School of bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract:
It is difficult to isolate lignin without modification because of its complexity, nonuniformity,
and conjunctive bonding to other substances. In order to analyze lignin structure, a technique of specific13
C-enrichment of cell wall lignin prepared by administration of 13C-labeled monolignol glucosides combinedwith NMR has been employed. In recent studies, labeling of side chain-α, -β, and-γ, and of ring-3, -4, and -5 ofthe lignin precursors have been succeeded. 13C labeled monolignol at ring-1 was also prepared in the previous
research. However, the yield was very low, so a new method of synthesis of monolignol-[ring-1-13C] is required
for lignin structure analysis. In this study, we investigated the new synthesis approach of coniferyl
alcohol-[ring-1-13C].
Keywords: coniferyl alcohol, 2D-NMR, 13C-labeling, synthesis route, lignin
2014-P02
α-Keto / β−O−4 構造を有する phenyl glycoside 型 LCC モデル化合物の合成
水上貴仁, 宮川泰幸, 飛松裕基, 上高原浩, 高野俊幸
京都大学大学院農学研究科
Synthesis of dilignol β-glycosides with α-keto / β−O−4 structures
Takahito Mizukami, Yasuyuki Miyagawa, Yuki Tobimatsu, Hiroshi Kamitakahara, Toshiyuki Takano
Division of Forest & Biomaterials Science, Guraduate School of Agriculture, Kyoto University,
Sakyo-ku. Kyoto, 606-8502, Japan
Abstract:
A series of α-keto / β-O-4 dilignol β-D-glycosides were synthesized as model for phenyl
glycoside type lignin-carbohydrate (LC) linkages possibly present in plant cell wall. α-Ketoguaiacylglycerol-β-guaiacyl ether derivative (1G) was acetylated to give compound 2G (94.5%). The compound575

2G was treated with 5% Pt/C catalytic reduction to afford compound 3G (61.8%). The glycosylation ofcompound 3G with compound 4 by imidate method afforded only β-D-glycoside 6G (64.7%). Deacylation ofcompound 6G with NaOMe / MeOH gave target compound 8G (43.5%). The synthetic method for compound
8G was applied to the syntheses of other β-D-glycosides. The fully assigned NMR spectra of guaiacyl andsyringyl α-keto / β-O-4 dilignol β-D-glycosides and β-D-xylosides provided useful database information forpeak assignment and authentication that could be readily implemented for the analysis of LC linkages in plant
cell walls using high resolution NMR techniques.
Keywords: lignin-carbohydrate complex (LCC), 2D HSQC NMR, phenyl glycoside, dilignol, α-ketodilignol, β-O-4 dilignol
2014-P03
Laser microdissection を用いたポプラ木部の成長輪内におけるリグニン解析
和田卓、藤田弘毅、堤祐司
九州大学大学院 農学研究院
Lignin analysis in growth ring of Populus alba xylem using Laser microdissection
Suguru Wada, Koki Fujita, Yuji Tsutsumi
Faculty of Agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Lignification is a cell wall fortifying process, which occurs in xylem tisssue before programmed
cell death (PCD). It was reported that some genes related in monolignol biosynthesis were expressed in ray
parenchyma cells in the lignified area. It was also observed that CWPO-C that is capable of lignin
polymerization located in the cell corners of the mature fiber cells. These results suggest that lignification stillproceeds in the fiber cells after their programmed cell death. Acetocarmine staining of nuclei and fragments of
DNA was not observed in the cells within the area between the 20th or 30th cells from cambial and the pith,suggesting the fiber cells in this area were already suffered from PCD. The pyrolysis product and S/G ratio
derived from β-O-4 linked lignin in the dissected samples of Populus alba xylem using laser micro dissection
were determined by Py-GC-MS. The increase of pyrolysis production and decrease of S/G ratio along with theradial direction within a growth ring suggest that lignification in the fiber cells may continue even after PCD
with the assistance of ray parenchyma cells.
Keywords: acetocarmine, biosynthesis, lignification, laser microdissection, pyrolysis-GC-MS,
2014-P04
A. thaliana を用いたモノリグノール輸送に関わる輸送体の探索
武内 真奈美、堤 祐司
九州大学大学院 農学研究院
Screening of monolignol transport protein in A. thaliana
Manami Takeuchi, Yuji Tsutsumi
Graduate school of agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Monolignols are synthesized in the cytosol and transported to the cell wall to biosynthesize
linign. It was reported that one of ATP-binding cassette (ABC) proteins, AtABCG29, is involved in thetransportation of p-coumaryl alcohol, however, there have been no report on other monolignols for guaiacyl andsyringyl lignin, which are major constitute units of angiosperm lignin. In this study, 9 genes including ABC
proteins were selected as monoligol transport candidates among the genes those expressions were largely
changed during the tracheary element differentiation of Arabidopsis cell culture, and T-DNA insert mutants ofthese genes were subjected to lignin analyses. There were no difference in both lignin content and S/G ratio
between wild type and each knockout mutant. The expression analysis of each gene in the several organs did notshow specificity in the stem unlike ABCG29. These results suggest that the candidate genes may not be involved
in monolignol transportation in the Arabidopsis stem.
Keywords: ABC protein, Arabidopsis thaliana, lignification, monolignol transporter, tracheary element
2014-P05
リグニンのビフェニル型分岐構造の探索: モデル実験と NMR(HMBC)測定条件の検討
阿部 雄一郎、秋山 拓也、松本 雄二
東京大学大学院農学生命科学研究科
Exploring biphenyl-type branch-points in lignin; model experiments and the examination of NMR (HMBC)
measurement condition
576

Yuichiro Abe, Takuya Akiyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo,1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
For the purpose of exploring non-phenolic dibenzodioxocin (5–5/4–O–β, DBDOX) structures
as a candidate of branch-points in lignin, measurement condition of a long-range 13C–1H correlation NMR(HMBC) experiment was examined using acetylated pine MWL (CDCl 3). Although Hα/C1 correlation peak ofphenolic DBDOX was detected under the conditions of 71-111 ms long range coupling delays, that of
non-phenolic DBDOX was not found in the present study. As a model experiment, a coupling reaction using
peroxidase and hydrogen peroxide system was examined if or not phenolic DBDOX model compound couples
with coniferyl alcohol (CA). While a substantial amount of G-GG–type DBDOX model remained after one day,
S-GG–type DBDOX model almost disappeared in a shorter reaction time.
Keywords: 5-5 linkage, biphenyl structure, soft wood, milled wood lignin, 2D NMR
2014-P06
アルカリ蒸解過程におけるリグニン β-O-4 結合開裂の速度論的検討（３）清水智子、Pattaraporn Posoknistakul、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Kinetic analysis of the β-O-4 bond cleavage of lignin during alkaline cooking process (3)Satoko Shimizu, Pattaraporn Posoknistakul, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo,1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
It was quantitatively investigated how the structural differences between p-hydroxyphenyl,
guaiacyl and syringyl aromatic nuclei and between the erythro and threo isomers in the side chain part of β-O-4bond affect the rate of the β-O-4 bond cleavage. As model compounds, dimeric C6-C2 type non-phenolic β-O-4
types were used, and the obtained results were compared with those of the C6-C3 type analogues, which wereobtained in our previous studies. The effect of the presence of γ-hydroxymethyl group on the β-O-4 bondcleavage rate can be examined by comparing the C6-C3 and C6-C2 type model compounds. In most cases, thedisappearance rate was in the order of: C6-C3 erythro compounds > C6-C2 compounds > C6-C3 threo compounds,
when their aromatic nuclei are the identical. The presence of a syringyl nucleus enhanced the β-O-4 bondcleavage rate in the reaction of not only the C6-C3 but also C6-C2 type model compounds. These results may
suggest that steric factor resulting from the presence of syringyl nucleus affects the cleavage rate even when
γ-hydroxymethyl group is absent.
Keywords: alkaline hydrolysis, alkyl-aryl ether, cooking, configuration, kraft pulping, wood delignification
2014-P07
NMR および LC/MS/MS によるバガス中リグニンの構造解析と GPC によるバガス中セルロースの平均重合度分析
竹本紀之１）、木南冴子１）、崎山庸子１）、秋山毅１）、小杉剛史２）１）（株）東レリサーチセンター、２）東レテクノ（株）
Structural analysis of lignin in bagasse by NMR and LC/MS/MS, and analysis of the number-average degree ofpolymerization of the cellulose in bagasse by GPC
Noriyuki Takemoto1), Saeko Kinami1), Yoko Sakiyama1), Tsuyoshi Akiyama1) ,Takeshi kosugi2)
1)
Toray Research Center, Inc., Otsu, Shiga 520-8567, Japan. 2)Toray Techno Co. Ltd., Otsu, Shiga 520-8558,
Japan.
Abstract:
The structure of cellulose and lignin in bagasse were determined by NMR, and it was confirmedthat aromatic carbon derived from lignin and aliphatic carbon derived from hemicellulose existed. The structureof compounds in extracted solution detected by LC/MS/MS were estimated as a degradation products of lignin.
The number-average degree of polymerization in cellulose derived from bagasse were evaluated by modified
BCA method and GPC-MALS, and those results showed correlation each other. Because the modified BCA
method can obtain analysis results more quickly than GPC-MALS, it is possible to use it as the screening
measurement of the number-average degree of polymerization.
Keywords: CP/MAS, dipolar dephasing, multivariate statistics
2014-P08
糖化残渣中のリグニンの特性に及ぼす糖化前処理の影響
577

柳下立夫、関根伸浩、井上誠一、
産業技術総合研究所 バイオマスリファイナリー研究センター
Effects of pretreatments of saccharification on characteristics of lignin in saccarification residue
Tatsuo Yagishita, Nobuhiro Sekine and Seiichi Inoue
Biomass Refinery Research Center, National Institute of Advanced Industrial Science and Technology,
Higashi-Hiroshima, Hiroshima, 739-0046, Japan
Abstract:
Lignin residues produced from saccharification with hydrothermal-mechanochemical
pretreatment were analyzed by alkaline nitrobenzene oxidation. The sum of vanillin and syringaldehyde
detected by alkaline nitrobenzene oxidation treatment decreased with the hydrothermal reaction time of morethan 2 hours. Lignin extracted from re-hydrothermal treated saccharification residue has high ratio of
syringaldehyde content against vanillin.
Keywords: saccharification reidue, alkaline nitrobenzene oxidation, hydrothermal-mechanochemical
pretreatment, autoclave, hydrothermal reaction time
2014-P09
脱メチル化リグニンの構造分析および性質評価
澤村 かおり 飛松 裕基 上高原 浩 高野 俊幸
京都大学大学院農学研究科
Synthesis, structure, and antioxidant activity of demethylated lignins
Kaori Sawamura, Yuki Tobimatsu, Hiroshi Kamitakahara,and Toshiyuki Takano
Graduate School of Agriculture, Kyoto University, Sakyo-ku. Kyoto, 606-8502, Japan
Abstract:
In an attempt to upgrade lignins by augmenting phenolic hydroxyl groups, synthetic lignin(DHP) was treated by demethylation reagents such as 1-dodecanethiol and iodocyclohexane. We found that
iodocyclohexane more effectively increased free phenolic hydroxyl groups in DHP than 1-dodecanethiol. Bothof the reagents cleaved the side chain linkages prior to demethylation of aromatic methoxyl groups. DPPH
radical scavenging activity of the demethylated DHP appeared to be improved as its phenolic hydroxyl content
increased.
Keywords: lignin, demethylation, 1-dodecanethiol, iodocyclohexane, antioxidant activity
2014-P10
針葉樹ソーダ蒸解黒液粉末のアルカリ PEG 処理による
熱溶融性リグニン誘導体の調製
尹 國珍 1)、髙橋史帆 2)、Thi Thi Nge2)、Olov Karlsson2), 3)、中川明子 1)、大井 洋 1)、山田竜彦 1), 2)
1)
筑波大生命環境、2)森林総合研究所、3)ルレオ工科大
Preparation of thermal melting lignin derivatives in the alkaline PEG treatment from dried black liquor powderof softwood soda cooking
Kukjin YOON1), Shiho TAKAHASHI2), Thi Thi NGE2), Olov KARLSSON2), 3), Akiko NAKAGAWA-IZUMI1),
Hiroshi OHI1), Tatsuhiko YAMADA1), 2)
1)
Faculty of Life and Environmental Sciences, University of Tsukuba, Japan, 2)Forestry and Forest Products
Research Institute, Japan, 3)Luleå University of Technology, Sweden
Abstract:
Softwood soda lignin does not have thermal melting property. To improve the thermal propertyof softwood soda lignin, we have invented a new method of lignin modification using dried black liquor powder
and polyethylene glycol (PEG). In the process, the black liquor powder of the soda cooking of softwood was
directly cooked with PEG in alkaline condition to produce PEG modified lignin derivatives (alkaline PEG
treatment). The dried black liquor powder which was prepared by a spray dryer was dissolved into PEG withheating at 120ºC or 160ºC under atmospheric pressure. The modified lignin derivatives (alkaline PEG treatedlignin) were precipitated and filtrated out. The collected alkaline PEG treated lignin showed thermal melting
property. The chemical analysis data suggested that the number of possible reaction site on lignin with PEG waslimited at the treatment of 120ºC. On the other hand, the higher introduction of PEG at the 160ºC of the reaction
suggested that the number of the reaction site on the lignin was newly produced by the reaction at 160ºC.
Keywords: thermal melting property; alkaline PEG treatment; softwood soda lignin; dried black liquor
powder.
2014-P11
木材腐朽菌によるリグニン分解過程の解析
578

西村裕志１）、酒井洋尚２）、片平正人２）、渡辺隆司１）１）
京都大学生存圏研究所、２）京都大学エネルギー理工学研究所
Analysis of lignin biodegradation by wood-rotting fungi
Hiroshi Nishimura1), Hironao Sakai2), Masato Katahira2), Takashi Watanabe1)
1)
Research Institute for Sustainable Humanosphere (RISH), Kyoto University, Japan, 2)Institute of Advanced
Energy, Kyoto University, Japan
Abstract:
Wood biomass is promising resource to produce energy and various chemicals. In nature,
wood-rotting fungi is a major player for decompose wood biomass. We have developed several techniques tostudy wood biodegradation using nuclear magnetic resonance spectroscopy and mass spectroscopy. Selective
degradation of either cellulose or lignin depending on a kind of fungi used was successfully detected. A key
metabolite for a selective degradation has also been detected with the assist of 13C labeling.
Keywords: basidiomycete, NMR, MS, white-rot fungi, lignocellulose
2014-P12
リグニン分解酵素による硝酸ミコナゾールの分解と毒性除去
井上聡、米田夕子、河合真吾、西田友昭
静大院農
Degradation and detoxification of miconazole nitrate by ligninolytic enzymes
Satoshi Inoue, Yuko Yoneda, Shingo Kawai, and Tomoaki Nishida
Graduate School of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
During the last decade, the occurrence and fate of residual pharmaceuticals in wastewater
treatment and the environment has attracted increasing interest due to the potential adverse environmental andhuman health effects. Miconazole nitrate (MCZ) is an imidazole fungicide used for treatment of fungal
infections of the skin and vaginal, and is also active against a series of gram-positive bacteria including Bacillus
subtilis. In this study, MCZ was treated with laccase, the laccase-mediator system with 1-hydroxybenzotriazole,
manganese peroxidase (MnP), and the MnP-dependent lipid peroxidation system with Tween 80 containing
unsaturated fatty acid. The MnP-Tween 80 system was most effective in eliminating MCZ among the four
enzymatic treatments, with MCZ concentration being reduced by about 70 and 88% after 8 and 24 h oftreatment, respectively. Furthermore, this system caused the complete loss of growth inhibition of MCZ against
B. subtilis after 24 h.
Keywords: miconazole; elimination; manganese peroxidase; unsaturated fatty acids; lipid peroxidation
2014-P13
高活性リグニン分解菌 Phanerochaete sordida YK-624 株における RNAi 技術の構築
隅谷友紀 1)、河岸洋和 1, 2, 3)、平井浩文 1, 2)
1)
静岡大学大学院農学研究科、 2)静岡大学グリーン科学技術研究所、3)静岡大学創造科学技術大学院
Gene silencing in hyper lignin-degrading fungus Phanerochaete sordida YK-624 by RNA interference
Tomoki Sumiya1), Hirokazu Kawagishi 1, 2, 3), Hirofumi Hirai 1, 2)
1)Graduate School of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2)Research Institute of Green
Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan, 3)Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
The gene of pyruvate decarboxylase (pdc) is a key enzyme in alcohol fermentation. However,lactate dehydrogenase completes with PDC for pyruvate in the lactate production. To produce lactate effectively
from woody biomass by hyper lignin-degrading fungus Phanerochaete sordida YK-624, the pdc was silenced
by RNA interference (RNAi). The plasmid constructed for gene silencing contained a transcriptional unit for
hairpin RNA expression. The silencing vector was transformed into a P. sordida YK-624 uracil auxotrophic
mutant, UV-64. When cultivated in fermentation broth for 4 days, 21 of 25 transformants showed lower
production of ethanol than control transformant. These results indicated that the silencing of pdc is effective forthe inhibiton of alcohol fermentation in white-rot fungi.
Keywords: white-rot fungi, biorefinery, alcohol fermentation, RNA interference
2014-P14
Sphingobium sp. SYK-6 株由来の ligD 遺伝子を導入した組換えポプラの解析
國枝愛海１）、辻幸子１）、上杉幹子１）、上村直史２）、菱山正二郎３）、政井英司２）、梶田真也１）１）
東京農工大学大学院生物システム応用科学府、２）長岡技術科学大学工学部生物系
579

３）

森林総合研究所バイオマス科学研究領域
Characterization of transgenic poplar with ligD gene isolated from Sphingobium sp. SYK-6
Ami Kunieda1), Yukiko Tsuji2), Mikiko Uesugi1), Naoto Kamimura2), Shojiro Hishiyama3), Eiji Masai2), Shinya
Kajita1)
1)
Graduate school of Bio-Applications and Systems Engineering,Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, 2) Department of Bioengineering, Nagaoka University of Technology,
Niigata 940-2188, Japan, 3) Department of biomass Chemistry, Forest and Forest Products Research Institute,
Ibarali 305-8687, Japan
Abstract:
Sphingobium sp. SYK-6, one of gram-negative bacteria, has various enzymes which catalyze
the degradation of lignin-related biaryls and monoaryls. One of them, Cα-dehydrogenase, ‘LigD’, can catalyze
the first step of cleavage reactions for ether bonds of β-aryl ether unit which are most abundant bonds in lignin.
LigD oxidizes hydroxyl group at benzyl (Cα) position of the dimmers to carbonyl group. It has been known thatthe presence of carbonyl group at the benzyl position of aryl propane units can greatly improve the efficiency ofcleavage of beta-aryl ether linkages during kraft pulping. We introduced the ligD gene into plant genome and try
to generate transgenic plants whose lignin can be easily to cleave and remove from cell wall fraction underalkali conditions. The enhanced cleavage of β-aryl ether linkages might enable to improve the efficiency not
only of pulp and paper production but also of other biorefinery processes. In this study, we generated the ligDtransgenic poplars and characterization of them will be discussed.
Keywords: SYK-6, LigD, α-keto-β-aryl ether, poplar, biomass pretreatment
2014-P15
遺伝子組換えシロイヌナズナが生産する細菌由来酵素 LigD の局在性の解析
橋本彩希、臼井貴紀 1)、辻幸子 1)、上村直史 2)、菱山正二郎 3)、政井英司 2)、梶田真也 1)
1)
東京農工大学大学院生物システム応用科学府、2)長岡技術科学大学工学部生物系 3)、森林総合研究所バイオマス化学研究領域
Imunohistochemical analyses of transgenic Arabidpsis plants, which produce the bacterial enzyme LigD.
Saki Hashimoto1), Takaki Usui1), Yukiko Tsuji1), Naofumi Kamimura2), Shojiro Hishiyama3)
Eiji Masai2), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, 2)Department of Bioengineering, Nagaoka University of Technology,
Niigata 940-2188, Japan, 3)Department of Biomass Chemistry, Forestry and Forest Products Research Institute,
Ibaraki 305-8687, Japan
Abstract:
Bacterial Cα dehydrogenase, which is encoded by ligD, catalyzes the first step of cleavage
reactions for ether bond of β-O-4-type dimers. This enzyme oxidizes α-hydroxyl group of the dimers to
α-carbonyl group. It has been known that the presence of carbonyl group at the benzyl position of β-aryl ether
units in lignin greatly speeds up the rate of cleavage of the ether linkage during kraft pulping condition. Hence,
we introduced the ligD gene into plant genome and try to generate transgenic plants contributed not only to pulp
and paper industries but also to efficient biorefinery process. We designed two gene constructs for ligD
expression in plants under the control of a constitutive promoter. For apoplastic and cytosolic localizations of
the LigD protein, ligD was expressed with and without an apoplast-targeting signal, respectively. In this study,
to test whether LigD with the ATS works as expected, we analyzed LigD localization in transgenic Arabidopsis
by immunohistochemical analysis and western blotting.
Keywords: dimer, localization, apoplast, immunohistochemical
2014-P16
細菌のリグニン由来芳香族化合物の取り込みに関与する major facilitator superfamily トランスポーター
森 光佑１）、上村 直史１）、原 啓文２）、笠井 大輔１）、福田 雅夫１）、政井 英司１）１）
長岡技術科学大学・生物、２）MJIIT, Univ. Tech., Malaysia
Bacterial major facilitator superfamily transporters for lignin-derived aromatic compounds
Kosuke Mori1), Naofumi Kamimura1), Hirofumi Hara2), Daisuke Kasai1),
Masao Fukuda1) and Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan,
2)
Department of Environmental Engineering and Green Technology, Malaysia-Japan International Institute ofTechnology, Universiti Teknologi Malaysia, 54100 Kuala Lumpur, Malaysia
Abstract:
Sphingobium sp. strain SYK-6 is capable of utilizing various lignin-derived aromatic biaryls
and monoaryls, and the catabolic genes for these compounds have been characterized. However, the uptake
580

systems for lignin-derived aromatic compounds remained unknown. In this study, we focused on thetransporters for protocatechuate (PCA), vanillate, syringate, and ferulate. DNA microarray analyses revealed
that the transcriptions of five genes, which probably encode major facilitator superfamily (MFS) transporters,
were induced during the incubation of SYK-6 cells on the above-mentioned substrates. These five genes andfour other genes homologous to a vanillate transporter gene, vanK, of Acinetobacter sp. strain ADP1, were
disrupted in SYK-6 to determine their roles in the uptake of lignin-derived aromatics. As a result, the growth ofa pcaK mutant on PCA was delayed compared to that of SYK-6. On the other hand, the pcaK mutant grewnormally on other substrates. The rate of PCA uptake was significantly decreased in the pcaK mutant. These
results indicate that pcaK encodes an MFS transporter for PCA.
Keywoeds:
aromatic acid/H+ symporter, sequence alignment, complementation assay, Carbon-14, liquid
scintillation counter
2014-P17
バクテリア由来コニフェリルアルデヒド二重結合還元酵素の改良渡辺 眞悟１）、荒木 拓馬１）、上村 直史１）、菱山 正二郎２）、笠井 大輔１）、福田 雅夫１）、菊地 淳３）、梶田 真
也４）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）理化学研究所・植物科学研究センター、４）東京農工大学
大学院・生物システム応用科学府
Improvement of catalytic properties of coniferyl aldehyde double bond reductase
Shingo Watanabe,1 Takuma Araki,1 Naofumi Kamimura,1 Shojiro Hishiyama,2 Daisuke Kasai,1Masao Fukuda,1 Jun Kikuchi,3 Shinya Kajita,4 and Eiji Masai1
1
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, 2Forestry and Forest
Products Research Institute, Tsukuba, Ibaraki, 3Riken Plant Science Center, Tsurumi-ku Yokohama, Kanagawa,4
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo, Japan
Abstract:
This work aims to control the lignin biosynthesis in plants by using bacterial genes responsible
for the structural modification of intermediate metabolites in the monolignol biosynthetic pathway. In a previous
study, we focused on alkenal double bond reductases (DBR), which catalyze the reduction of the C-C-doublebond of coniferyl aldehyde (CALD). We found that DBR of Parvibaculum lavamentivorans (PlDBR) showed ahigher Vmax for the conversion of CALD compared to that of Arabidopsis thaliana (AtDBR), whereas theactivities of PlDBR were lower than those of AtDBR in the range of low substrate concentration (< 100 M). In
this study, we intended to improve the conversion ability of PlDBR toward CALD. Based on thethree-dimensional structure of AtDBR, it was suggested that amino acid residues located in the substratebinding pocket are slightly different between both enzymes. These amino acids of PlDBR were substituted tothose of AtDBR, and then the kinetic parameters of mutated PlDBRs to convert CALD were estimated. As aresult, a V268I-G269Y mutant showed a 3.5-fold lower Km value than that of the wild type, indicating an
improved substrate affinity, even though the Vmax was decreased 0.6-fold over the wild-type value.
Keywords: coniferyl alcohol, biofuel, genome database, site-directed mutagenesis, pretreatment,
dehydrogenase2014-P18
Sphingobium sp. SYK-6 株におけるアセトバニロン代謝経路の同定
樋口 雄大 1)、菖蒲田 透 1)、上村 直史 1)、原 啓文 2)、笠井 大輔 1)、片山 義博 3)、
福田 雅夫 1)、政井 英司 1)
１）
長岡技科大・生物、２）MJIIT, Univ. Tech., Malaysia、３）日大・生資科
Identification of the acetovanillone catabolism pathway in Sphingobium sp. strain SYK-6
Yudai Higuchi1), Toru Shobuda1), Naofumi Kamimura1), Hirofumi Hara2), Daisuke Kasai1), Yoshihiro
Katayama3), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan,
2)
Department of Environmental Engineering and Green Technology, Malaysia-Japan International Institute ofTechnology, Universiti Teknologi Malaysia, 54100 Kuala Lumpur, Malaysia
3)College of Bioresource Sciences, Nihon University, Fujisawa, Kanagawa 230-0045, Japan
Abstract:
Catabolism of arylglycerol--aryl ether is the most important process in bacterial lignin
catabolism. In a degrader of lignin-derived aromatic compounds, Sphingobium sp. strain SYK-6,
guaiacylglycerol--guaiacyl ether is degraded to vanilloyl acetic acid (VAA) in a five-step reaction. VAA is581

assumed to be non-enzymatically decarboxylated to produce acetovanillone (AV), and the resulting AV is
finally catabolized to vanillate. However, the catabolic pathway of AV to vanillate has not yet been determined.
In this study, we characterized the catabolic pathway of AV and identified the catabolism genes. LC-MS
analysis showed that VAA was accumulated during the growth of SYK-6 on AV. This result suggests that AV
was converted into VAA by carboxylation. The acvABCDEF genes specifically induced in the presence of AV
were identified as candidate genes responsible for the conversion of AV. Disruption of each of these genes in
SYK-6 resulted in a loss of the ability to grow on AV. In addition, the growth on AV of mutants of ferA andferB involved in the ferulic acid catabolism were significantly delayed compared to that of the wild type. All
these results suggest that acvABCDEF, ferA, and ferB are involved in the catabolism of AV in SYK-6.
Keywords: biomass, bacteria, carboxylase, acetovanillone, ferulic acid2014-P19
Sphingobium sp. SYK-6 株におけるバニリン酸・シリンガ酸代謝系遺伝子の転写制御機構
荒木 拓馬、梅田 周佑、上村 直史、笠井 大輔、福田 雅夫、政井 英司
長岡技術科学大学・生物
Transcriptional regulation of the vanillate and syringate catabolism genes in Sphingobium sp. strain SYK-6
Takuma Araki, Shusuke Umeda, Naofumi Kamimura, Daisuke Kasai, Masao Fukuda, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract:
Sphingobium sp. strain SYK-6 degrades lignin-derived biaryls via vanillate (VA) and syringate(SA). In this study, we focused on the transcriptional regulation of the VA and SA catabolism genes, including
ligM, desA, and desB. To date, it is known that ligM, desA, and desB are negatively regulated by DesR, a
MarR-type transcriptional regulator. In order to identify the inducer molecules for the expression of ligM, desA,and desB, the transcriptions of these genes in SYK-6 and a desA ligM double mutant (DDAM), which is unable
to catabolize VA, SA, and 3-O-methylgallate (3MGA), were evaluated by quantitative RT-PCR. When
incubating DDAM with VA, SA, or 3MGA, the transcriptional levels of ligM, desA, and desB in DDAM were
almost the same as those of the wild type. These results suggest that VA, SA, and 3MGA are inducers of ligM,
desA, and desB. Gel shift assays showed that purified DesR bound to the promoter regions of ligM and desB,
each of which contains a similar inverted repeat. However, the binding of DesR to the desA promoter region
was not observed. Mutations in the inverted repeat in the desB promoter region resulted in a reduction of thebinding of DesR, suggesting the importance of the inverted repeat for the DesR binding. The binding of DesR to
the ligM and desB promoter regions was inhibited by the addition of VA. This result suggests that VA acts as aneffector of DesR.
Keywords: biomass, guaiacyl lignin, syringyl lignin, bacteria, transcriptional regulation
2014-P20
Benzo[a]pyrene biodegradation by a newly isolated white rot fungus from nature in soil
Ade Andriani, Kazutaka Itoh, Sanro Tachibana
Department of Applied Bioscience, Faculty of Agriculture, Ehime University 3-5-7 Tarumi, Matsuyama, Ehime,
790-8566 Japan
Abstract:
Benzo[a]pyrene (BaP) has been observed to accumulate in marine organisms and plants
which could indirectly cause human exposure through food consumption. Bioremediation using white rot fungi
is one of the promising method to remove BaP in environment because they can produce extracellularligninolytic enzymes (Laccase, Mangan Peroxidase, and Lignin Peroxidase) that can degrade many xenobiotic
compunds such as BaP. The effect of several pre-grown such as rice straw, wood meal, pulp, kapok, and liquid
culture medium was investigated in the degradation of BaP in soil. The fungus could grow in all pre-growntreatment in different cell growth rate. The fungus could cover the surface and bottom part of soil in 7 days
incubation. The highest degradation in soil occured in treatment using rice straw as pre-grown, could reach
34.5% in 15 days and 63.2% in 30 days. The degradation varied according to different pregrown media in therange 43.2%-63.2% in 30 days. Ligninolytic enzymes such as laccase. MnP and LiP were detected during
incubation. In rice straw treatment, detected laccase, MnP and LiP in order were 63.9 U/L, 11.4 U/L and 38.8
U/L in 15 days. In 30 days, there was MnP decreasing into 1 U/L but enhancement of LiP more than 2 fold, 53.3
U/L. Characteristics of pre-grown biomass such as cellulose, hemicellulose and lignin content seems influence
enzyme activity produced by fungus SM46.
Keywords: biodegradation, ligninolytic enzymes, benzo[a]pyrene, fungus SM46
2014-P21582

縮合型タンニンを硬化剤とするエポキシ樹脂の合成と熱的性質
長房孝樹、中村成孝、廣瀬重雄
福井工業大学工学部
Synthesis and thermal properties of epoxy resins derived from tannin
Takaki Nagafusa, Yoshitaka Nakamura and Shigeo Hirose
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Epoxy resins were prepared using a fraction of tannin with a relatively low average molecularweight. Tannin, glycerol diglycidyl ether and 2-ethyl-4-methylimidazole (2E4MI) were dissolved in ethanol.
Ethanol was removed under a reduce pressure. The obtained mixtures were cured at 130 oC for 5 h. The[EPOXY]/[PhOH] mole ratios were varied from 0.8 to 1.2. Thermal properties of the obtained cured epoxy
resins were studied by differential scanning calorimetry (DSC). The glass transition temperatures (Tg’s) showeda maximum value when [EPOXY]/[PhOH] mole ratio was 1.0. The above result suggests that cross-linking
densities of the cured epoxy resins become highest when [EPOXY]/[PhOH] mole ratio was 1.0.
Keywords: epoxy resins, tannin, synthesis, thermal properties583

第 60 回 （2015.11.05-06） つくば大学
2015-101
木化に関わるキシランの機能解明
李強 1)、小川真由 1)、幸田圭一 2)、浦木康光 2)、吉永新 3)、高部圭一 3)1)
北海道大学 大学院農学院、2)北海道大学 大学院農学研究院、3)京都大学 大学院農学研究科
Clarification of xylan function in lignification
Qiang Li1), Mayu Ogawa1), Keiichi Koda2), Yasumitsu Uraki2), Arata Yoshinaga3), Keiji Takabe3)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 2) Research Faculty ofAgriculture, Hokkaido University, Sapporo 060-8589, Japan, 3) Graduate School of Agriculture, Kyoto
University, Kyoto 606-8502, Japan
Abstract:
In this study, clarification of xylan function concerning lignification was attempted by using awood cell wall model mimicking the cell wall formation process. As a result, xylan was found to induce
coniferyl alcohol as one of monolignols into inside of the film, and act as a scaffold to form dehydrogenation
polymer (DHP). From an analysis of the DHP deposited cellulosic films, xylan was also found to regulate thelignin structure.
Keywords: artificial wood cell wall, immunolabeling, scaffold, SEM-EDXA, xylan,
2015-102
免疫賦活作用を持つ大麦穀皮由来リグニン・多糖結合体の発見
辻亮平 1)、小泉英樹 1)、青木弾 2)、渡辺雄太 1),3)、松下泰幸 2)、福島和彦 2)、藤原大介 1)1)
キリン株式会社基盤技術研究所、2) 名古屋大学大学院生命農学研究科、3) キリン株式会社綜合飲料分析
センター
Identification of immune-stimulatory lignin-carbohydrate derived from barley husk
Ryohei Tsuji1), Hideki Koizumi1), Dan Aoki2), Yuta Watanabe1),3),Yasuyuki Matsushita2), Kazuhiko Fukushima2),
Daisuke Fujiwara1)
1)
2)
Central Laboratories for Key Technologies, KIRIN Co. Ltd., Yokohama, 236-0004, Japan,
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, 464-8601, Japan,
3)
Integrated Beverage Analysis Center, KIRIN Co. Ltd., Yokohama, 230-8628, Japan
Abstract:
Barley husks are produced as by-products of the malting and brewing industry. In order todevelop novel applications of barley husks, biological activities were explored regarding withimmune-stimulatory activities. Four lignin-containing fractions were tested using bone-marrow derived
dendritic cells (BM-DCs). As a result, LREL and PEL were shown to strongly activate BM-DCs via TLR4. We
also examined with the relationship between the immune-stimulatory activity and chemical features of LREL,
such as lignin amount, distinguishing composition of neutral sugars and intermolecular ester bonds. In addition,in vivo experiments revealed that systemic and mucosal immune systems were significantly activated by LREL
administration. Taken together, LREL have shown to be a strong immune-stimulator derived from edible plants.
Keywords: barley husks, lignin-carbohydrate, BM-DCs, immune-stimulatory, TLR4
2015-103
ディリジェント様タンパク質の新たな機能の提案： ダイズの莢のねじれへの関わりについて
片山 健至 1), 船附 秀行 2), 鈴木 雅也 3), 廣瀬 亜矢 4), 稲葉 大貴 3), 山田 哲也 5), 羽鹿 牧太 5), 小松 邦
彦 4), 佐山 貴司 6), 石本 政男 6), 藤野 介延 3),1)
香川大・農, 2)農研機構・近中四農研, 3)北大・院農, 4)農研機構・北農研, 5)農研機構・作物研, 6)生物研,
Suggestion about a new function of a dirigent-like protein: Relationship to the twist of soybean pods
Takeshi Katayama1), Hideyuki Funatsuki2), Masaya Suzuki3), Aya Hirose4), Hiroki Inaba3), Tetsuya Yamada5),
Makita Hajika5), Kunihiko Komatsu4), Takashi Sayama6), Masao Ishimoto6), Kaien Fujino3)
1)
Faculty of Agriculture, Kagawa University, Miki-cho, Kagawa 761-0795, Japan; 2) NARO (National
Agricultural Research Organization) Western Region Agricultural Research Center, Nishifukatsu-cho,
Fukuyama 721-8514, Japan, 3) Graduate School of Agriculture, Hokkaido University, Kita-ku, Sapporo
060-8589, Japan, 4) NARO Hokkaido Agricultural Research Center, Toyohira-ku, Sapporo 062-8555, Japan, 5)
NARO Institute of Crop Science, Kannondai, Tsukuba 305-8518, Japan, 6) National Institute of Agrobiological
Sciences, Kannondai, Tsukuba 305-8602, Japan
Abstract:
Pod dehiscence (shattering) is the critical step for seed dispersal in wild plant species, but is amajor cause of yield loss in legumes and crucifers crops. However, little is known about the genetic basis of the584

shattering resistance in those crops. Here, we performed a map-based cloning of a major quantitative trait locus
controlling pod dehiscence in soybean [Glycine max Merr. (L.)]. Fine-mapping and complementation test
revealed that the gene encodes a dirigent-like protein, which effects stereoselective bimolecular phenoxy radical
coupling, designated as Pdh1. The gene was defected with a premature stop codon in shattering-resistantcultivars. The functional Pdh1 gene was specifically expressed in pod walls. Comparison of near-isogenic lines
indicated that Pdh1 regulate torsion of dried pod walls, which functions as force to dehisce binding of pod walls.
These findings provide useful information for plant breeding and point to a new biological role for the dirigent
proteins.
2015-104
シナピルアルコール γ‐アセテートの酸化銀による酸化カップリング
岸本崇生、板倉圭佑、濱田昌弘、中島範行
富山県立大学工学部（兼）生物工学研究センター
Oxidative coupling of sinapyl -acetate by silver oxide
Takao Kishimoto, Nana Takahashi, Masahiro Hamada, Noriyuki Nakajima
Faculty of Engineering and Biotechnology Research Center, Toyama Prefectural University, Imizu, Japan
939-0398.
Abstract:
Biomimetic oxidations of sinapyl alcohol and sinapyl acetate were carried out with Ag2O tobetter understand the high frequency of β-O-4 structures in highly acylated natural lignins. The major products
from the Ag2O oxidation of sinapyl alcohol were sinapyl aldehyde (14% yield), β-O-4-coupled dimer (32%yield) and β-β-coupled dimer (3% yield). In contrast, the Ag2O oxidation of sinapyl acetate produced
β-O-4-coupled dimer in 66% yield. Oligomeric products with predominantly β-O-4 structures were also
obtained in 18% yield. The yield of the β-O-4-coupled products from sinapyl acetate was much higher than thatfrom sinapyl alcohol. Computational calculations based on density functional theory showed that the negative
charge at Cβ was significantly reduced by the γ-acetyl group. The computational calculations suggest that the
Coulombic repulsion between Cβ and O4 in sinapyl acetate radicals was significantly reduced by the γ-acetylgroup, contributing to the preferential formation of β-O-4 structures from sinapyl acetate. These findings will
advance our knowledge in biosynthesis of lignin.
Keywords: monolignol, peroxidase, lignin biosynthesis, acetylated lignin, kenaf
2015-105
二酸化マンガンによるリグニンモデル化合物の酸化反応
秋穂知、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Oxidation of lignin model compounds by manganese dioxide
Satoru Akiho, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo
Abstract:
Manganese dioxide (MnO2) is a potentially recyclable oxidant. In this study, oxidation reactionof a non-phenolic lignin model compound, veratryl alcohol (I), 2-(2-methoxyphenoxy)1-(3,4-dimethoxy-phenyl)propane-1,3-diol(II),or
2-(4-hydroxymethyl-2-methoxyphenoxy)-1(3,4-dimethoxyphenyl)- propane-1,3-diol (III), by MnO2 was examined in detail. The disappearance ofcompound I became faster with increasing proton concentration of the system, and was relatively accelerated
with the progress of the reaction when compared with a pseudo- first-order reaction. Veratraldehyde is the major
reaction product of compound I, and the yield was about 80% based on the amount of reacted compound I.
Veratraldehyde was also obtained as a major reaction product in the oxidation of compound II, which indicatesthat the Cα-Cβ bond is cleaved. This result suggests that MnO2 oxidation can potentially depolymerize lignin.
On the other hand, any reaction products resulting from a C-C bond cleavage was not detected in the oxidationof compound III. The presence of the benzyl hydroxymethyl group must have greatly affected the reactivity.
Keyword:manganese dioxide oxidation, permanganate, kappa number, delignification, benzyl alcohol
2015-106
リグニン β-O-4 結合のアルカリ開裂反応における分解生成物の検討
清水智子、Pattaraporn Posoknistakul、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
585

Study on degradation products in the alkaline cleavage reaction of lignin β-O-4 linkage
Satoko Shimizu, Pattaraporn Posoknistakul, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract: Based on the mechanism of the non-phenolic β-O-4 bond cleavage in alkali medium, alkali
cooking of a C6-C2 type non-phenolic β-O-4 model compound was expected to give a non-phenolic aromaticcompound with the 1,2-ethanediol side-chain as the predominant degradation product derived from the main
carbon skeleton as well as a phenolic compound liberated from the β-O-4 ether linkage. However, thepredominant formation of the former compound was observed only when the model compound contained
syringyl nuclei in the main carbon skeleton as the 3,4,5-trimethoxyphenyl nuclei. When the model compoundcontaining guaiacyl nuclei in the main carbon skeleton was cooked in alkali, the former compound was only oneof the four major degradation products derived from the main carbon skeleton. These were identified as
1-(3,4-dimethoxyphenyl)ethane-1,2-diol, the aimed compound, veratraldehyde, vanillin, and acetoveratrone.
The yields of these four degradation products were different when the type of another aromatic nuclei
participating in the β-O-4 ether linkage was different.
Keywords: alkali pulping, delignification, aromatic ring structure, degradation products
2015-107
Stereo-preferential degradation of the erythro and threo isomers of β-O-4 type lignin model compounds underoxygen delignification conditions
Pattaraporn Posoknistakul, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, Tokyo, Japan
Abstract:
The erythro (E) or threo (T) isomer of a dimeric non-phenolic β-O-4 type lignin modelcompound,2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol(1),2-(4-hydroxymethyl-2-methoxy-phenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol(2),or2-(4-methoxymethyl-2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (3), was reacted withactive oxygen species (AOS) under oxygen delignification conditions to observe the stereo-preferential attack of
AOS on the E or T isomer. AOS were generated in situ by the reaction of O2 with a co-existing phenolic
compound, 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol, Valc system) or 2,4,6-trimethylphenol(TMPh system). When the compound 1 or 3 was reacted in Valc system, the degradation of T isomer was
greater than that of E isomer, while compound 2 shows the reverse stereo-preference. On the other hand, when
the compound 1 was reacted in TMPh system, 1 isomer was degraded faster than T isomer. was observed. These
results could rationally been explained by the following assumptions. Compound 1E or 3E has the negatively
charged α-alkoxide owing to the relatively acidic α-hydroxy group, and consequently, is not frequently attacked
by the negatively charged AOS, oxyl anion radical, in Valc system. On the other hand, because the neutral
peroxyl radical is a main AOS in TMPh system, the negatively charged side-chain of compound 1E or 3E canbe attacked. In compound 2, the presence of the more easily ionizable benzyl hydroxymethyl group may
suppress the ionization of the α-hydroxy group of 2E, and hence the reaction of the main carbon skeleton with
the negatively charged oxyl anion radical may not be interfered with.
Keyword:
Alkyl-aryl ether, bleaching, diastereomers, pulp, oxidation
2015-108
砕木パルプのアセチル化 —アセチル基の導入量と導入位置の関係—
安藤大将、中坪文明、矢野浩之
京都大学 生存圏研究所
Acetylation of ground pulp –the quantity and the position of acetyl groupsDaisuke Ando, Fumiaki Nakatsubo, Hiroyuki Yano
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract:
In acetylation of ground pulp(GP), the position of Acetyl groups was researched. Sevendifferent AcGPs (DS=0.19,0.29,0.59,0.74,1.04,1.11,1.19) were prepared and analyzed with HSQC-NMR.
Acetylation was proceeded in the order of primary hydroxyl groups of polysaccharide and lignin, secondaryhydroxyl groups of polysaccharide, and hydroxyl groups at α-position of lignin. Then, the thermal stability of
the AcGPs was analyzed with TGA. The 1%loss temperatures of AcGPs were higher than GP. Especially, it was
found that acetylation of primary hydroxyl groups and hydroxyl groups at α-position of lignin improved thethermal stability.
586

2015-109
高活性リグニン分解菌 Phanerochaete sordida YK-624 株と自然界由来細菌の共培養系の構築
森 智夫 1)、河岸洋和 1,2,3)、平井浩文 1,2)
1)
静岡大学農学部応用生物化学科、2) 静岡大学グリーン科学技術研究所、 3) 静岡大学創造科学技術大学
院
Construction of co-culture system of hyper lignin-degrading fungus Phanerochaete sordida YK-624 with thenaturally derived bacteria that indicated the higher ligninolytic activity
Toshio Mori1), Hirokazu Kawagishi1,2,3), Hirofumi Hirai1,2)
1)
Faculty of Agriculture, 2) Research Institute of Green Science and Technology, 3) Graduate School of Scienceand Technology, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan
Abstract:
To investigate the interaction between wood rot fungi and bacteria in nature wood decay, we
tried to construct a wood rot fungal-bacterial coexisting culture system showing higher wood degrading ability.
Fungal cultures on beech wood meal of Phanerochaete sordida YK-624 were buried in soils for 1 to 5 weeks.
The resulting cultures have been contaminated by soil bacteria. Subcultures of contaminated-cultures to the
newly wood meal have shown higher wood degrading rate than P. sordida YK-624. The contents of residual
wood components of each subcultures were different. Therefore, it is suggested that the coexisting bacteria
affected wood degradation mechanisms of wood-rotting fungus P. sordida YK-624. Moreover, the results ofbacterial ribosomal intergenic sequence analysis showed progression of bacterial diversity change andstabilization by repeating subcultivation.
Keywords: white-rot fungi, wood rot, co-culture, interaction
2015-110
担子菌を用いた木質バイオリファイナリーの新展開 －白色腐朽菌による水素発酵－
有本 美沙 1)、森 智夫 1)、河岸 洋和 1, 2, 3)、平井 浩文 1, 2)
1)
静岡大学農学部、2) 静岡大学グリーン科学技術研究所、3) 静岡大学創造科学技術大学院
New development on woody biorefinery with basidiomycete - Hydrogen fermentation by white-rot fungiMisa Arimoto1), Toshio Mori1), Hirokazu Kawagishi1, 2, 3), Hirofumi Hirai1, 2)
1)Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2) Research Institute of Green
Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan, 3) Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
Hydrogen is potential alternative pollution-free energy carrier. In nature, hydrogen is producedby microorganisms either in the process of nitrogen fixation, fermentative processes or by photosynthetic
microorganisms under certain conditions. It is known that fermentative hydrogen production by anaerobic
bacteria, for example, Clostridium and Enterobacter. Although we confirmed the presence of hydrogenase-likegene sequence in many wood rotting fungi, there are no repodescribed on hydrogen production by wood-rotting
fungi. In the present study, we investigated the possibility of hydrogen production by wood-rotting fungi. We
selected 3 hydrogen-production fungi from 26 wood-rotting fungi isolated from decay woods, and confirmedthat they were white-rot fungi. Quantitative determination of hydrogen production by these white-rot fungi was
performed by using gas chromatography. As a result, Trametes versicolor K-41 showed the highest hydrogenproducing ability, and we expected that the expression of hydrogenase gene in T. versicolor K-41 was involvedin the hydrogen production. Furthermore, it was indicated that T. versicolor K-41 could produce the hydrogenfrom Japanese cedar wood meal. This is the first report of hydrogen production from wood biomass by white-rot
fungus.
Keywords: wood-rot fungi ; hydrogen fermentation ; hydrogenase gene ; Trametes versicolor K-41
2015-111
シロイヌナズナゲノムに存在するフェニルクマランベンジルエーテルレダクターゼ遺伝子の機能解析
諾恩達古拉(ノンダグラ)1)、上村直史 2)、森哲哉 3)、中林亮 3)、辻幸子 1),5)、菱山正二郎 4)、斉藤和季 3)、政井英司 2)、梶田真也 1)
1)
東京農工大学大学院生物システム応用科学府、2)長岡技術科学大学大学院工学研究科、3)理化学研究所
環 境 資 源 科 学 研 究 セ ン タ ー 、 4) 森 林 総 合 研 究 所 、 5) 現 Department of Biochemistry, University of
Wisconsin-Madison
Expression and functional analyses of a putative phenylcoumaran benzylic ether reductase in Arabidopsis
thaliana
587

Nuoendagula1), Naofumi Kamimura2), Tetsuya Mori3), Ryo Nakabayashi3), Yukiko Tsuji1, 5) Shojiro Hishiyama4),
Kazuki Saito3), Eiji Masai2), Shinya Kajita1)
1)
BASE, Tokyo University of Agriculture and Technology, Tokyo 184-8588, Japan, 2) Department of
Bioengineering, Nagaoka University of Technology, Niigata 940-2188, Japan, 3) Center for Sustainable
Resource Science, RIKEN, Kanagawa 230-0045, Japan, 4) Forestry and Forest Products Research Institute,
Ibaraki 305-8687, Japan, 5) Present address: Department of Biochemistry, University of Wisconsin-Madison,
USA
Abstract:
Phenylcoumaran benzylic ether reductase (PCBER) is thought to be an enzyme crucial in thebiosynthesis of 8–5′-linked neolignans and have been characterized in several plant species. Interestingly, in
poplar, expression of PCBER is strongly correlated with active xylem formation. In this study, we cloned cDNAand the 5′-untranslated region of a PCBER candidate gene (At4g39230, designated as AtPCBER1) from
Arabidopsis thaliana. Expression analyses of AtPCBER1 indicate that expression is induced by wounding and isexpressed in most of tissues, including flower, stem, leaf, and root. Catalytic analysis of recombinant
AtPCBER1 suggests that the protein can reduce not only the 8–5′-linked neolignan, dehydrodiconiferyl alcohol,
apparently but also 8–8′ linked lignans, pinoresinol, and lariciresinol with lower activities. Untargeted
metabolomics analysis of transgenic plants in which the target gene was up- or down-regulated indicates nohsignificant effects of AtPCBER1 gene regulation on plant growth and development, however, levels of somesecondary metabolites, including lignans, flavonoids, and glucosinolates, differ between
wild-type and transgenic plants. Taken together, our findings indicate that AtPCBER1 encodes a polypeptide
with PCBER activity and has a critical role in the biosynthesis of secondary metabolites in A. thaliana.
Keywords: Arabidopsis thaliana, Dehydrodiconiferyl alcohol, Lignan, Metabolome
2015-112
フェルラ酸 5-ヒドロキシラーゼ OsF5H1 の発現制御によるイネリグニンの構造改変
武田ゆり１）、小柴太一 1)、２）、飛松裕基１）、山村正臣１）、服部武文１）、３）、坂本正弘４）、高野俊幸４）、鈴木史朗１）、梅澤俊明１）、５）
１）
京都大学生存圏研究所、２）（株）アースノート（現所属）、３）徳島大学大学院 SAS（現所属）、４）京都大学大学
院農学研究科、５）京都大学生存基盤科学研究ユニット
Structural modification of lignin in Oryza sativa by regulation of ferulate 5-hydroxylase (OsF5H1) expression
Yuri Takeda1), Taichi Koshiba1), 2), Yuki Tobimatsu1), Masaomi Yamamura1), Takefumi Hattori1), 3), Masahiro
Sakamoto4), Toshiyuki Takano4), Shiro Suzuki1), Toshiaki Umezawa1), 5), 1Research Institute for Sustainable
Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan, 2Present address: EARTHNOTE Co., Ltd.,Kunigami-gun, Okinawa 904-1303, Japan, 3Present address: Institute of Socio-Arts and Sciences, Tokushima
University, 1-1 Minamijosanjima-cho, Tokushima 770-8502, Japan, 4Graduate School of Agriculture, Kyoto
University, Sakyo-ku, Kyoto 606-8502, Japan,
5Institute of Sustainability Science, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract:
Lignin aromatic composition, i.e., syringyl (S) and guaiacyl (G) unit ratio, greatly affects theusability and processability of lignocellulosic biomass. In this study, we attempted to control S/G lignin unit
ratio in rice (Oryza sativa), a model plant of grasses, by manipulation of a gene encoding ferulate 5-hydroxylase(F5H; a.k.a, coniferaldehyde 5-hydroxylase, CAld5H). Based on protein sequence and gene expression data
analysis, we identified a candidate gene (OsF5H1) for the primary F5H involved in S lignin biosynthesis in rice.
Accordingly, we produced transgenic plants in which OsF5H1 is down- or up-regulated, and demonstrated that
their lignins are considerably enriched in either S or G lignin units as determined by a series of chemical andspectroscopic analyses. We contemplate that manipulation of F5H genes could be a promising strategy to
improve the utilization of grass lignocelluloses.
Keywords: lignin, rice, ferulate 5-hydroxylase, S/G ratio, metabolic engineering
2015-113
バクテリア由来 Cα-デヒドロゲナーゼの発現による細胞壁中でのリグニンの構造改変
今村真子 1)、橋本彩希 1)、國枝愛海 1)、辻幸子 2)、上杉幹子 1)、Ruben Vanholme 3)、飛松裕基 4)、石川靖之 1)、
Clifton E. Foster 5)、上村直史 6)、菱山正二郎 7)、篠阿弥宇 8)、原啓文 9)、佐藤かんな 1)、Paula Oyarce 3)、Geert
Goeminne 3)、Kris Morreel 3)、菊地淳 8)、高野俊幸 10)、福田雅夫 6)、片山義博 11)、Wout Boerjan 3)、John Ralph2)、政井英司 6)、梶田真也 1)
1)
東京農工大学大学院 生物システム応用科学府、2) University of Wisconsin-Madison、3)Vlaams Instituutvoor Biotechnologie、4)京都大学 生存圏研究所、5)Michigan State University、6)長岡技術科学大学大学院588

工学研究科、7)森林総合研究所、8)理化学研究所 環境資源研究センター、9)Universiti Teknologi Malaysia、
10)
京都大学大学院 農学研究科、11)日本大学 生物資源科学部
Structural modification of lignin in the cell wall by the use of bacterial Cα-dehydrogenase
Mako Imamura 1), Saki Hashimoto 1), Ami Kunieda 1), Yukiko Tsuji 2), Mikiko Uesugi 1), Ruben Vanholme 3),
Yuki Tobimatsu 4), Yasuyuki Ishikawa 1), Clifton E. Foster 5), Naofumi Kamimura 6), Shojiro Hishiyama 7),
Amiu Shino 8), Hirofumi Hara 9), Kanna Sato 1), Paula Oyarce 3), Geert Goeminne 3), Kris Morreel 3), Jun
Kikuchi 8), Toshiyuki Takano 10), Masao Fukuda 6), Yoshihiro Katayama 11), Wout Boerjan 3), John Ralph 2), Eiji
Masai 6), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering Tokyo University of Agriculture andTechnology, Tokyo, Japan, 2) Department of Biochemistry, University of Wisconsin, Madison, USA,3)
Department of Plant Systems Biology, Ghent, Belgium, 4) Research Institute for Sustainable Humanosphere,
Kyoto University, Kyoto, Japan, 5) Michigan State University, East Lansing, USA,
6)
Department of Bioengineering, Nagaoka University of Technology, Niigata, Japan, 7) Forestry and Forest
Products Research Institute, Ibaraki, Japan, 8) RIKEN Center for Sustainable Resource Science, RIKEN,
Kanagawa, Japan, 9) Malaysia-Japan International Institute of Technology, Universiti Teknologi Malaysia,
Kuala Lumpur, Malaysia, 10) Graduate school of Agriculture, Kyoto University, Kyoto, Japan,11) College of
Bioresource Sciences, Nihon University, Kanagawa, Japan
Abstract:
Sphingobium sp. strain SYK-6 can utilize various monomeric and dimeric aromatic compounds,
which appeared in lignin biosynthetic pathway. In our previous study, some genes involved in degradation ofthese compounds were isolated from this strain. One of them, ligD gene, encodes Cα-dehydrogenase for firststep of cleavage of ether bond in compounds with β-O-4 bond. It has been known that the presence of carbonylgroup at the benzyl position of β-O-4 interunits in lignin accelerates up the rate of cleavage of the bond during
alkaline and acidic conditions. Thus, we introduced the ligD genes into plant genome and try to generatetransgenic plants. Characteristics of the transgenic Arabidopsis, Populus and Eucalyptus plants will be discussed
in the present study.
Keywords: Sphingobium sp. strain SYK-6, Cα-dehydrogenase, 1H-13C HSQC analysis, apoplast-targeting
signal (ATS)2015 特別講演、I.
リグニンの微生物分解片山 義博
日本大学 生物資源科学部
Ivited Lecture, I : Microbial degradation of Lignin
Yoshihiro Katayama
College of Bioresource Sciencies, Nihon University
Kanagawa, Japan
Abstract:
In microbial degradation process in nature, bacteria play a main role in the mineralization ofvarious types of lignin-derived aromatic compounds. Sphingobium sp strain SYK-6 grows on a lignin-related
biphenyl compounds, 5,5’-dehydrodivanillate (DDVA), as sole carbon and energy sources and also degrades
various types of lignin-derived biaryls, including β-aryl ether, pionresinol, phenylcoumaran and diarylpropan
together with DDVA. These versatile degradation activities toward various types of lignin-related compounds
reflect the presence of a wide variety of enzyme systems in this bacterium. We have been investigated the
enzyme and gene systems for β-aryl ether cleavage by two enantioselective enzymes (LigE, F), two types ofO-dimethylation for DDVA by mono-oxygenase (LigX) and for vanillate and syringate by methyl-transferase
linked with C1-metabolism (LigM), two types of aromatic ring cleavage for biphenyl derived from
DDVA(LigZ) and for protocatechuate and 3-methylgallate derived from vanillate and syringate, respectively(LigA,B). For applications, we focused on the metabolic intermediate, 2-pyrone-4.6-dicarboxylic acid (PDC) as
a potential raw material for variuous novel bio-based polymers. We established the preparation protocol of a
PDC, on a large scale from lignin using transformed bacterium by combination with chemical reaction as
pretreatment of high molecular lignin decomposition. PDC a chemically stable metabolic intermediate of lignin,
was utilized to prepare polyesters. PDC polyesters and PDC epoxides exhibited strong adhering properties
against metals and glass with tenaciously adhering to their surface
Keywords: Glutathione S-transferase, Lignin biphenyl ring cleavage, Lignin biphenyl O-demethylation,
Tetrahydrofolate-dependent O-demethylation, PDC-based polymer, PDC-based Adhesive
2015-201589

オゾン処理が針葉樹ソーダリグニン系のコンクリート用化学混和剤の性能に与える効果
高橋史帆 1)、森本和正 2)、浦木康光 3)、山田竜彦 1)
1)
森林総合研究所、2)株式会社日本触媒、3)北海道大学大学院農学研究院
Effect of ozone treatment on performance of softwood soda lignin based concrete chemical admixture
Shiho Takahashi1), Masakazu Morimoto2), Yasumitsu Uraki3), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, Japan, 2)Nippon Shokubai Co., Ltd., Japan, 3)Graduate Schoolof Agriculture, Hokkaido University, Japan
Abstract:
We have developed a water reducing admixture for concrete based on softwood soda lignin
modified with polyethylene glycol (PEG) chain. In this study, ozone treatment of soda lignin and lignin-PEG
derivatives was conducted in order to introduce carboxyl group which can be responsible for adsorpting tosurface of cement particles for developing a high performance of lignin based water reducing admixture. Ozone
treatment of soda lignin increased the number of free type of carboxyl group and improved mortar fluidity. The
lignin-PEG derivatives having various amount of PEG moiety (50 and 90 mol of ethylene oxide repeating unit)
were prepared and applied to ozone treatment as well. Ozone treated lignin-PEG derivatives showed better
performance as water reducing admixture than untreated samples. This effect should be due to introducing
carboxyl group which work as adsorpting site to cement particles.
Keywords: soda lignin, Japanese cedar, polyethylene glycol, ozone treatment, concrete chemical admixture
2015-202
数種の単離リグニンからの電気二重層用電極の調製
Xiangyu You 1)、Junlei Duan1)、幸田圭一 2)、浦木康光 2)、山田竜彦 3)、久保智史 3)1）
北海道大学大学院農学院、2）北海道大学大学院農学研究院、3）森林総合研究所
Preparation of electric double layer capacitor electrode from several kinds of isolated lignins
Xiangyu You1), Junlei Duan1), Keiichi Koda2), Yasumitsu Uraki2), Tatsuhiko Yamada3), Satoshi Kubo3)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo, 060 -8589, Japan, 2)Research Faculty ofAgriculture, Hokkaido University, Sapporo, 060-8589, Japan, 3)Division of Biomass Chemistry, Forestry andForest Products Research Institute, Tsukuba, 305-8687, Japan
Abstract:
In this study, fabrication of electric double layer capacitor (EDLC) electrode was attempted byusing polyethylene glycol-lignin (PEGL) and soda-lignin (SL) derived from cedar wood. By direct
melt-electrospinning of PEGL, fibers with 23 μm in diameter were prepared. Much finer fibers (3.6 μm) wereobtained by melt-electrospinning of 70% PEGL in dimethyl formamide (DMF) solution. Although
dry-electrospinning of SL alone in an alkaline aqueous solution was impossible, dry-electrospinning of a
mixture of SL and polyethylene glycol (Mw=500,000) was possible to give thin SL fibers with the diameter of
0.85 μm. These fibers were converted to activated carbon fibers (ACFs) by stabilization, carbonization andsteam-activation as the EDLC electrode materials. By using these carbonaceous materials, PEGL-ACF electrodeshowed an impedance of 1.6 Ω and a specific capacitance of 92.6 F g-1 at a scan rate of 1 A g-1, and SL-ACF
electrode showed 4.5 Ω and 55.6 F g-1, respectively.
Keywords: dry-electrospinning, electric double layer capacitor, melt-electrospinning, polyethylene glycol
lignin, soda lignin
2015-203
リグニン由来の新規難燃材料の開発
平野大輔、松下泰幸、青木弾、福島和彦
名古屋大学大学院生命農学研究科
Development of novel flame retardant from by-product lignin in pulping process
Daisuke Hirano, Yasuyuki Matsushita, Dan Aoki, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract:
Nitrogen-phosphorus-alkyldiol modified Lignin (NPDL) was prepared from kraft lignin. The
procedure was introduction of 3-amino-1,2,4-triazole into kraft lignin and phosphorylation using phosphoryl
chloride followed by introduction of 8-octanediol. NPDL and poly(lactic acid)-NPDL composite (PLA-NPDL)
were investigated thermal stability and flame retardancy. NPDL exhibited char-forming ability with retaining
44.9 wt% mass at 500 ºC in atmosphere. PLA-NPDL composite was achieved V-2 class in UL-94 test. The charlayer was formed on NPDL surface in simplified combustion test. Moreover, NPDL did not drip flaming
particles. NPDL exhibited high flame retardancy with growing intumescent char layer.
Keywords: industrial lignin, functionalization, resinification, additive, biorefinery590

2015-204
ブナの亜臨界フェノール及び亜臨界水による脱リグニンの比較
髙田昌嗣、田中佳樹、南英治、坂志朗
京都大学大学院エネルギー科学研究科
Comparative study of delignification from Japanese beech as treated by subcritical phenol and subcritical water
Masatsugu Takada, Yoshiki Tanaka, Eiji Minami, Shiro Saka
Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan
Abstract:
The difference in delignification behaviors of Japanese beech (Fagus crenata) was discussed astreated by subcritical phenol (230oC/1.2MPa) and subcritical water (230oC/2.9MPa). As a result, in subcriticalphenol, more than 90 wt% of lignin was decomposed and removed, while in subcritical water, around half of
lignin was removed with the other half remaining as insoluble residue. Through the ultraviolet (UV)
microscopic observations, lignin in cell walls was found to be decomposed extensively in both treatments due
perhaps to ether-linkages rich in cell wall lignin. However, lignin in middle lamella revealed resistance tosubcritical water, but not to subcritical phenol. Such a difference would imply that the lignin is phenolated andsimultaneously decomposed in subcritical phenol. The phenolated lignin would, thus, become solvated withphenol. Consequently, lignin in middle lamella, even being rich in condensed-type linkages, would be moreliquefied by subcritical phenol, compared to subcritical water.
Keywords: Topochemistry, Japanese beech, Subcritical phenol, Subcritical water, Microscopy
2015-205
リグニン熱分解における芳香核構造の変換機構 ―同位体ラベルによる検討―
成田和央、河本晴雄、坂 志朗
京都大学大学院エネルギー科学研究科
Conversion mechanisms of aromatic nuclei during lignin pyrolysis – An approach from isotope labeling –Kazuo Narita, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Japan
Abstract:
Structures of lignin aromatic nuclei dramatically change at > 400-450ºC, where the methoxylgroups become reactive. In this study, conversion mechanisms of the aromatic nuclei during pyrolysis werestudied from the reactivity and 13C/deuterium (D) incorporation data with 13C and D labeled guaiacols as modelcompounds.
Keywords: lignin, pyrolysis, polyaromatization, methoxyl group, isotope labeling2015-206
イオン液体処理におけるＭＷＬの分解挙動の解析
小川清太朗１）、山本康平１）、溝口晃平１）、吉岡康一１）、宮藤久士１）、
大野弘幸２）、山田竜彦３）１）
京都府立大学大学院生命環境科学研究科、２）東京農工大学工学研究院、
３）
森林総合研究所
Ultrastructural and Topochemical Aspects of Wood Cell Walls Treated with Ionic Liquid
Shintaro Ogawa1), Kohei Yamamoto1), Kohei Mizoguchi1), Koichi Yoshioka1), Hisashi Miyafuji1), Hiroyuki
Ohno2), Tatsuhiko Yamada3)
1)
Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, 1-5 Hangi-cho,
Shimogamo, Sakyo-ku, Kyoto 606-8522, Japan, 2) Graduate School of Engineering, Tokyo University ofAgriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan, 3) Forestry and Forest
Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
We investigated for the reaction behavior of milled wood lignin (MWL) obtained fromJapanese cedar (Cryptomeria japonica) and Japanese beech (Fagus crenata) in an ionic liquid,1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which is known that it can liquefy wood and dissolve
cellulose. Both MWLs easily dissolved in [C2mim][Cl] heated at 120℃ by oil bath and microwave irradiation.
After 96h treatment with [C2mim][Cl], MWLs were slightly depolymerized. Few amount of low molecularweight compounds such as vanillin and coniferylaldehyde were produced from MWL. Moreover, the reaction
behavior of MWL in 1-ethyl-3-methylimidazolium aminoacetate ([C2mim]Gly) and tetrabutylammoniumhydroxide 30-hydrate ([NBu4]OH) were also studied. [C2mim]Gly and [NBu4]OH can dissolve MWL during
heat treatment. The solubilized MWL in these ionic liquids were depolymerized much faster than that in591

[C2mim][Cl].
Keywords:

Ionic liquid, Milled wood lignin, Reaction, Depolymerization

2015-207
イオン液体を移動相とする HPLC： イオン液体でバイオマスから抽出したリグニン・多糖類の分子量分布測定黒田浩介 1), 2), 3)、高橋憲司 3)、大野弘幸 1) ,2)*
1)
東農工大院工 東京都小金井市中町２丁目２４−１６ 工学部生命工学科, 2)イオン液体研究拠点 東京都
小金井市中町２丁目２４−１６ 工学部生命工学科, 3)金沢大院理工 石川県金沢市角間町 理工研究域自然システム学系
Molecular weight distributions of polysaccharides and lignin extracted from plant biomass with a polar ionicliquid analyzed without a derivatization process
Kosuke Kuroda1), 2), 3), Kenji Takahashi3), Hiroyuki Ohno1) ,2)*
1)
Graduate school of Engineering, Tokyo University of Agriculture and Technology, 2-24-16, Koganei, Tokyo,
Japan, 2)Functional Ionic Liquid Laboratories, Tokyo University of Agriculture and Technology, 2-24-16,
Koganei, Tokyo, Japan, 3)Graduate School of Natural Science and Technology, Kanazawa University,
Kakumamachi, Kanazawa, Japan, *ohnoh@cc.tuat.ac.jp
Abstract;
Lignin and polysaccharides, extracted from biomass with ionic liquids, were directly analyzed
with high performance liquid chromatography with the aid of ionic liquid as an eluent(HPILC). Lignin andpolysaccharides and were clearly detected independently with the use of both a refractive index detector and UV
detector. The present HPILC method has potential to rapidly and easily analyze molecular weight distributionsof lignin and polysaccharides extracted from plants.
Keywords: molecular weight distribution, HPLC, GPC, ionic liquid, lignin-carbohydrate complex
2015-特別講演、II.
Invited Lecture II: Designer ligninsJohn Ralph,1,2* Fachuang Lu,1,2 Hoon Kim,1,2 Steven D. Karlen,2 Matt Regner,1,2 Dharshana Padmakshan,2
Rebecca Smith,1,2 Yuki Tobimatsu,1,2,* Wu Lan,1,2 Jorge Rencoret,2,† Kate E. Helmich,1,2 Sally A. Ralph,3 John C.
Sedbrook,2,4 Curtis G. Wilkerson,5 Philip J. Harris,6 Armin Wagner,7 John H. Grabber,8 Ronald D. Hatfield,8Jane Marita,8 Yukiko Tsuji,1,9 Shinya Kajita,9 Yaseen Mottiar,10 Shawn D. Mansfield,2,10 and others!
1
Dept. Biochemistry and/or Dept. Biological Systems Engineering, U. Wisconsin, Madison, WI, USA.
2
DOE Great Lakes Bioenergy Research Center, Madison, WI and East Lansing, MI, USA. 3U.S. Forest Products
Lab., Madison, WI, USA. 4School of Biological Sciences, Illinois State U., Normal, IL, USA.
5
Depts. Plant Biology, Biochemistry & Molecular Biology, Michigan State U., East Lansing, MI, USA.
6
School of Biological Sciences, U. Auckland, NZ. 7Scion, Rotorua, NZ. 8U.S. Dairy Forage Research Center,
USDA-ARS, Madison, WI, USA. 9Graduate School of Bio-Applications and Systems Engineering, Tokyo U.
Agriculture and Technology, Nakacho, Koganei, Tokyo, Japan. 10Dept. Wood Science, U. British Columbia,
Vancouver, BC, Canada. *Currently: Research Institute for Sustainable Humanosphere, Kyoto University,
Gokasho, Uji, Kyoto, Japan. †Currently: Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS),
Seville, Spain.
Abstract:
As lignin is a polymer formed from its monomer radicals by purely chemical radical coupling
reactions, the breadth of options for ‘designing’ the composition and structure of lignins is unparalleled. Beyond
simply manipulating the relative levels of the traditional monolignols, new phenolic monomers can be
introduced into the polymer, subject solely to the plant’s ability to produce and transport them to the wall andtheir chemical compatibility with the components and (cross-)coupling reactions that typify lignification. Recent
examples of this metabolic plasticity include demonstrating the introduction of hardwood-type lignins into softwoods to improve pulping performance, and the identification of plants producing lignins composed almost
entirely of hydroxycinnamaldehydes, opening up new and unique derivatization and modification opportunities.
Tissues containing 100% levels of caffeyl or 5-hydroxyconiferyl alcohol-derived lignin polymers have been
discovered. These two catechol-type monolignol analogs produce almost homogeneous (single-structured)linear lignin chains upon polymerization, again creating opportunities for valuable new uses for lignin.
Moreover, lignins have now been successfully ‘redesigned’ to contain readily chemically cleavable ester bondsin the polymer backbone, facilitating improved industrial processing – for example, chemical pulping, orpretreatment options for the saccharification of wall polysaccharides to sugars for liquid biofuels production.
Inspired by Nature’s incorporation of the non-lignin-pathway flavonoid, tricin, into monocot lignins, researchers
can now also contemplate plants in which the lignins incorporate valuable components that can be subsequently592

retrieved from the ‘waste’ streams. We suspect that we are now entering a reinvigoration period for lignin
research aimed at its manipulation for improved utilization, and suggest that the title ‘designer lignins’ used here
is not overly hyperbolic!
Keywords: Lignification, metabolic plasticity, monolignol, gene misregulation, engineering, pulping.
2015-P01
広葉樹の葉リグニンの DFRC 法による検出（２）松井直之、大平辰朗（研）森林総合研究所 バイオマス化学研究領域
Detection of broad-leaf lignin in angiosperms by DFRC analysis (2)Naoyuki Matsui and Tatsuro Ohira
Forestry and Forest Products Research Institute, Wood Extractives Lab., 305-8687, Japan
Email: naomat@ffpri.affrc.go.jp
Abstract:
The DFRC (Derivatization Followed by Reductive Cleavage) analysis can be used to detect
lignin specifically from plant tissues, since it gives C6-C3 type degradation products by the cleavage ofarylether linkages of lignin, excluding other (poly)phenolic substances. In this study, the process of lignin
deposition in the course of leaf growth was investigated by DFRC analysis. The increase of lignin in leaves ofFagus, Magnolia and Cercidiphyllum was observed from late April to mid May. Localization of lignin in majorleaf vein was not clear, but there was heterogeneity in the lignin composition between major leaf veins and otherleaf tissues. Vein lignin showed clearly low S/G ratio.
Keywords: lignin, leaf, DFRC method, vein
2015-P02
合成モノリグノールプローブを活用した細胞壁リグニンの蛍光生体標識有賀哲１）、飛松裕基２）、鈴木史朗２）、Eric Allen３）、John Ralph３）、上高原浩１）、梅澤俊明２）、

高野俊幸

１）
１）

京大院農、２）京大生存研、３）ウィスコンシン大バイオケミストリー
Visualization of Cell Wall Liginification Using Synthetic Monolignol Probes
Satoshi Aruga1), Yuki Tobimatsu2), Shiro Suzuki2), Eric Allen3), John Ralph3), Hiroshi Kamitakahara1), Toshiaki
Umezawa2), Toshiyuki Takano1)
1)
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan, 2)Research Institute for
Sustainable Humanosphere, Kyoto University, Gokasho, Uji, 611-0011, Japan,
3)
Department of Biochemistry, University of Wisconsin-Madison and the US Department of Energy’s Great
Lakes Bioenergy Research Center (GLBRC), Madison, WI, 53726, USA
Abstract:
Techniques to visualize cell wall lignification processes directly in vivo are considerably limited
mainly because lignins are not amenable to being genetically tagged for visualization. To overcome this, wehave developed a series of synthetic monolignol analogues imbued with chemical reporters (e.g., azides andalkynes) that can be selectively incorporated into lignin-producing cell walls and subsequently derivatized via
bioorthogonal reactions (e.g., click chemistry) for fluorescent labeling. Herein, using Arabidopsis live plantsystems, we have further explored the use of azide- and alkyne-tagged monolignol probes and various
fluorescent dyes for in vivo fluorescent imaging of cell wall lignins via copper-assisted or copper-free click
reactions.
Keywords: Arabidopsis thaliana; azide-alkyne cycloaddition reaction; fluorescence microscopy; in vivo
imaging; lignin biosynthesis
2015-P03
β–1 型構造に関する研究：塩酸処理による MWL の NMR スペクトル変化
秋山拓也１）、２）、松本雄二１）、
1)
東京大学大学院農学生命科学研究科、２）科学技術振興機構 さきがけ
Study on β–1 structures in lignin:
NMR spectral changes of MWL during hydrochloric acid treatment
Takuya Akiyama1), 2) and Yuji Matsumoto1)
1)
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo, Tokyo
113-8657, Japan, 2)JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
Abstract:
Hardwood lignin (MWL) was treated with 0.1M hydrochloric acid in dioxane-water (80:20,
593

v/v) at 50ºC. After the acid treatment, candidate NMR signals for spirodienone structures (β–1) almost
disappeared from the HSQC spectrum of the MWL. In contrast, a NMR signal for the β-position ofdiarylpropane structures became detectable in the course of the acid treatment.
Keywords: acidolysis, milled wood lignin, β-1 linkage, guaiacyl-syringyl, avicennia
2015-P04
バイオマス生産現場への導入を目指した改質リグニン製造用ベンチプラント
山田竜彦、髙田依里、髙橋史帆、池田努、ネー ティティ
国立研究開発法人 森林総合研究所
Local type of bio-refinery plant development to produce functional lignin derivatives
Tatsuhiko YAMADA, Eri TAKATA, Shiho TAKAHASHI, Tsutomu IKEDA, Thi Thi NGE
Forestry and Forest Products Research Institute, Japan
Abstract:
Recently, FFPRI lignin research has been upgraded by a large scale national research programof Strategic Innovation promotion Program (SIP) under the direction of Council of Science Technology andInnovation, Cabinet Office, Government of Japan. To start this new lignin program, 22 organizations (5national laboratories, 9 universities and 8 private companies) participated and launched a new research
consortium called “SIP-Lignin”. In the SIP-Lignin project, acid catalyzed solvolysis of wood meal with PEG(PEG solvolysis) was selected as a main biorefinery process. Since PEG is a not toxic high boiling point
solvent, the PEG solvolysis reactor can be operated under atmospheric pressure without using pressure
equipment. This simple operability brought a concept of introducing a small scale rural area biorefinery
system based on the PEG solvolysis. A bench scale plant has been introduced to demonstrate the concept witha stable PEG lignin production.
Keywords: solvolysis, PEG, bench scale plant, bio-refinery, SIP-Lignin
2015-P05
酸加溶媒分解による改質リグニン製造工程からの薬液の回収と再利用
髙田依里 1)、ネー ティティ 1)、髙橋史帆 1)、大橋康典 2)、山田竜彦 1)
1)
森林総合研究所、2)ハリマ化成株式会社
Recovery and reuse of the solvolysis reagent in the acidic solvolysis system of the glycol lignin production
Eri Takata1), Thi Thi Nge1), Shiho Takahashi1), Yasunori Ohashi2), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan, 2) Harima Chemicals, Inc., Saitama
340-0003, Japan
Abstract:
The acidic solvolysis of softwood with a glycol solvent, such as polyethylene glycol (PEG), is
considered to be an attractive way to produce a valuable lignin with thermal fusibility. In order to industrialize
this process, a solvolysis reagent need to be recovered and reused. In this study, the recovered PEG200 was
prepared by removing water from the waste liquor of the acidic solvolysis system of the glycol lignin production,and then was used in the acidic solvolysis reaction of softwood. The recovered PEG200 worked as a solvolysis
media and produced the glycol lignin with thermal fusibility. Thermomechanical analysis of the glycol lignin in
2.0 h of the reaction showed that both of fresh and the recovered PEG200 displayed two inflection points, whichwere assigned to the glass transition point (Tg) and the thermal softening point (Ts).
Keywords:
softwood

recycle of solvolysis reagent, acidic solvolysis, glycol lignin, polyethylene glycol (PEG),

2015-P06
Thermal flow behavior of isolated softwood lignin derivatives depending on polyethylene glycol (PEG) chain
length using as a solvolysis medium
Thi Thi Nge, Shiho Takahashi, Eri Takata, Tsutomu Ikeda, Tatsuhiko Yamada
Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
The acid catalyzed solvolysis of softwood Japanese cedar was performed using liquid
polyethylene glycol (PEG) with different PEG chain length as solvolysis medium. The physical and thermal
properties of isolated PEG-lignin derivatives obtained from PEG solvolysis medium (PEG200, PEG400,
PEG600) with substantial amount of acid catalyst concentration (0.3 to 0.7% w/w% of PEG) were theninvestigated by UV spectrophotometer, size exclusion chromatography, and various thermal analyzers including
TMA, TGA, CFT (Capillary Flow Tester Rheometer). It was noted that an efficient separation of PEG-lignin
fraction and lignocellulosic pulp fraction can be performed with this single step solvolysis process. A
594

comprehensive thermal flow profile of PEG-lignin derivatives was deduced from combination of thermal
analyses results.
Keywords: acid catalyzed solvolysis, polyethylene glycol (PEG), thermal flow behavior, capillary flow
tester rheometer (CFT), thermomechanical analyzer (TMA)
2015-P07
Characterization of lignin in residual pulp fraction obtained from polyethylene glycol solvolysis of softwood
Japanese cedar by pyrolysis gas chromatography mass spectrometry
Yin Ying H’ng1), Akiko Nakagawa-izumi1), Thi Thi Nge2), Eri Takata2), Tatsuhiko Yamada 2)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan
2)
Forestry and Forest Products Research Institute, Japan
Abstract:
The acid catalyzed solvolysis of softwood Japanese cedar was carried out using polyethylene
glycol (PEG) as a solvolysis reagent in the presence of a very small amount of sulfuric acid (H 2SO4) to isolate
lignin fraction. The lignin remained in the residual pulp fraction obtained from solvolysis process were thenanalyzed by the pyrolysis gas chromatography mass spectrometry (Py-GC/MS) in comparison with a starting
material of Japanese cedar. In order to estimate the lignin contents in residual pulp fraction, a calibration line
was developed based on Py-GC/MS results of residue with various lignin contents, which were first determined
by Klason and UV method. It was noted that the lignin contents (Klason lignin and acid soluble lignin) was ingood agreement with that measured by Py-GC/MS.
2015-P08
リグニンと粘土鉱物を用いた耐熱ガスバリアフィルムの開発
石井 亮、鈴木麻実、金子大貴、中村考志、棚池修、蛯名武雄、吉田肇、吉田学
国立研究開発法人 産業技術総合研究所
Ryo Ishii, Asami Suzuki, Hiroki Kaneko, Takashi Nakamura, Osamu Tanaike, Takeo Ebina, Hajime Yoshida,
Manabu Yoshida
National Institute of Advanced Industrial Science and Technology (AIST), 4-2-1, Nigatake, Sendai, 983-8551,
Japan)
Abstract:
我々は、粘土鉱物を主体とした耐熱ガスバリアフィルムの開発を行っている。当該バリアフィ
ルムは粘土を主成分としているため、その強度が弱く、有機バインダーを使用することにより膜の形態を保持している。さらに、そのバインダーの特性はフィルムの耐熱性やバリア性に影響を及ぼすことが分かっており、バインダーの選択はフィルムの性能向上に重要な要素となっている。今回、有機バインダーとして熱的な安定性が期待されるリグニンに注目し、リグニンと粘土鉱物を用いた耐熱ガスバリアフィルムを試作し、その評価を行ったので報告する。
2015-P09
改質リグニンに反応性基導入による硬化
山下俊 1)、松山直人 1)、中村考志 2)、石井亮 2)、蛯名武雄 2)
1)
東京工科大学工学部応用化学科、2)産業技術総合研究所東北センター化学プロセス研究部門
Thermal Curing of a Glycol Lignin by the Introduction of Reactive Groups
Takashi Yamashita1), Naoto Matsuyama1), Takashi Nakamura2), Ryo Ishii2), Takeo Ebina2),
1)
Department of Applied Chemistry, Faculty of Engineering, Tokyo University of Technology,1404-1 Katakura, Hachioji, Tokyo 192-0982, Japan, 2)Research Institute for Chemical Process Technology,
National Institute of Advanced Industrial Science and Technology（AIST）, 4-2-1 Nigatake, Miyagino-ku, Sendai,
Miyagi 983-8551, Japan
Abstract:
Hybrid materials composed of clay and glycol lignin make flexible films with high gas-barrier
ability, high resistance against electric discharge, and thermal stability. In order to improve the mechanicalproperties of those hybrid materials introduction of reactive groups on the glycol lignin was investigated toperform thermal curing of the films. Phenolic hydroxyl groups and the hydroxyl groups of ethylene glycol
chains on the glycol lignin were determined as 1.89mmol/g and 2.35mmol/g, respectively based on theacetylation method. Then several functional groups such as diisocyanates, dianhydrides, chlorides, epoxides
and so on were introduced on the active hydroxyl moieties to harden the materials. Among them introductionof (di)anhydrides was especially effective to the fabrication process due to water-solubility of the modified
glycol lignin and reactivity towards to poycarbodiimides. This work was supported by SIP-Lignin project,"Technologies for creating next-generation agriculture forestry and fisheries" Cross-ministerial Strategic595

Innovation Promotion Program (SIP), Council for Science Technology and Innovation (CSTI).
Keywords: glycol lignin, hybrid film, clay, curing
2015-P10
アルカリ PEG 処理による針葉樹ソーダリグニンの改質と特性解明
尹 國珍 1)、髙橋史帆 2)、ネー ティティ 2)、中川明子 1)、大井 洋 1)、山田竜彦 1), 2),
1)
筑波大生命環境、2)森林総合研究所
Improvement and characterization of softwood soda Lignin in the alkaline PEG treatment
Kukjin YOON1), Shiho TAKAHASHI2), Thi Thi NGE2), Akiko NAKAGAWA-IZUMI1),
Hiroshi OHI1), Tatsuhiko YAMADA1), 2)
1)
Faculty of Life and Environmental Sciences, University of Tsukuba, Japan
2)
Forestry and Forest Products Research Institute, Japan
Abstract:
To develop applications for technical lignins, it is important to develop modification methods toenhance lignin properties for high-end value-added products. We prepared lignin derivatives by using dried
black liquor powder with polyethylene glycol (PEG). In the process, the black liquor powder of the soda
cooking of softwood was directly cooked with PEG in alkaline condition to produce PEG modified lignin
derivatives (alkaline PEG treatment). The lignin derivatives showed thermal melting property. To elucidate thebehavior of lignin in this treatment, we carried out the alkaline PEG treatment using the purified soda-AQ lignin
as model compound. In this paper, the molecular weight of alkaline PEG-treated lignin and evaluation ofthermal melting property will be discussed.
Keywords: softwood soda-AQ lignin, polyethylene glycol, alkaline PEG treatment, thermal melting
property, black liquor
2015-P11
シリンギル構造を有するビフェノールを硬化剤とするエポキシ樹脂硬化物の合成と熱的性質
廣瀬重雄、酒元佑輔、菅森義彦
福井工大・工Synthesis and thermal properties of epoxy resins derived from biphenol having syringyl groups
Shigeo Hirose, Yusuke Sakamoto, Yoshihiko Sugamori
Fukui University of Technology, 3-6-1 Gakuen, Fukui-City, Fukui 901-8505, Japan
Abstract:
Epoxy resins were prepared by curing with 4,4’-dihydroxy-3,3’5,5’-tetramethoxybiphenyl(DHTMB) and 4,4’-dihydroxybiphenyl (DHB) in the presence of 2-ethyl-4-methylimidazole (2E4MI). The
mixture of ethylene glycol diglycidyl ether (EGDGE) and trimethyrol propane triglycidyl ether (TMPTGE)
were allowed to react with the above biphnols at 120 oC, in order to obtain prepolymers. The obtained
prepolymers were cured by heating from 20 to 200 oC in vessels using a differential scanning calorimeter (DSC).
The [EPOXY]/[PhOH] mole ratio was maintained at 1.0. Thermal properties of the obtained cured epoxy resins
were studied by DSC. The glass transition temperatures (Tg’s) of cured epoxy resins with DHTMB was 46.4 oC
and that of DHB was 38.8 oC. The above result suggests that methoxyl groups in DHTMB units restricts themain chain motion of cured epoxy polymer networks
Keywords: biphenol, syringyl groups, epoxy resins, synthesis, thermal properties
2015-P12
tetra-n-butylphosphonium hydroxide を用いた針葉樹リグニンの抽出山田肇 1)、宮藤久士 2)、大野弘幸 3)、山田竜彦 1)
1)
森林総合研究所、2)京都府立大、3)東京農工大
Extraction of softwood lignin using a tetra-n-butylphosphonium hydroxide
Hajime YAMADA1), Hisashi MIYAFUJI2), Hiroyuki OHNO3), Tatsuhiko YAMADA1)
1)
Forestry and Forest Products Research Institute, Japan, 2)Kyoto Prefectural University, Japan
3)
Tokyo University of Agriculture and Technology, Japan
Abstract:
Tetra-n-butylphosphonium hydroxide ([P4,4,4,4]OH) is a kind of ionic liquids. [P4,4,4,4]OH candissolve micro crystalline cellulose and hardwood biomass at ambient temperature, even when it contains
30~70% of water. In this study, the dissolving properties of softwood lignin in an aqueous solution of[P4,4,4,4]OH were studied. Cedar wood meal and 40% [P4,4,4,4]OH aqueous solution were mixed in a glass tube
and treated at 121 ºC and 2 atm in an ordinary autoclave. As the treatment time increased, the residue content
596decreased to 68.7%, 49.4%, and 37.0% after 1, 5, and 20 h, respectively. Lignin was found to dissolve fasterthan holocellulose, and 3.0% of the residue after the 20-h autoclave treatment consisted of lignin. In that residue,
glucose was the main constituent monosaccharide (96.3%). The dissolved lignin content in the [P4,4,4,4]OH
solution could be determined by UV analysis. The lignin absorption coefficients can be proposed as 39.5 L/g/cm,
calculated from the lignin elution amount and the 280nm UV absorbance. Phenolic hydroxyl group of the
dissolved lignin were 0.43-0.49 mol/unit lignin, indicating that the treatment time did not affect the phenolichydroxyl content.
Keywords: ionic liquid, TBPH, cedar, dissolution, autoclave
2015-P-13
イオン液体処理木材の組織形態および化学成分変化のトポケミストリー
神林徹１）、宮藤久士１）、大野弘幸２）、山田竜彦３）１）
京都府立大学大学院生命環境科学研究科、２）東京農工大学工学研究院、３）森林総合研究所
Ultrastructural and topochemical aspects of wood cell walls treated with ionic liquid
Toru Kanbayashi1), Hisashi Miyafuji1), Hiroyuki Ohno2), Tatsuhiko Yamada3)
1)
Graduate School of Life and Environmental Sciences, Kyoto Prefectural University,
1-5 Hangi-cho, Shimogamo, Sakyo-ku, Kyoto 606-8522, Japan, 2)Graduate School of Engineering, Tokyo
University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan, 3)Forestry andForest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
We have studied the morphological and chemical changes in cell walls of Japanese beech(Fagus crenata) after treatment with the ionic liquid, 1-ethylpyridinium bromide ([EtPy][Br]), which prefer toreact with lignin to cellulose. The cell walls of wood fibers in both earlywood and latewood were significantly
swelled after [EtPy][Br] treatment. In addition, lignin in compound middle lamella and cell corner have highresistance to degradation by [EtPy][Br] compared with that in secondary wall.
Keywords: ionic liquid, liquefaction, microscopy, morphology, topochemistry2015-P14
有機分子触媒能を持つイオン液体を用いたリグニンの誘導体化
高見澤勇太、覚知亮平、遠藤 太佳嗣、仁宮一章、高橋憲司
金沢大学 理工研究域
Synthesis of lignin derivatives by using organocatalyst in ionic liquid
Yuta Takamizawa, Ryouhei Kakuchi, Takatsugu Endo, Kazuaki Ninomiya, Kenji Takahashi
Institute of Science and Engineering, Kanazawa University, Japan
Abstract:
Lignin is a major component of biomass, abundant in nature and the resource for aromaticcompounds. Therefore, converting lignin into a useful substance is one of the most important processes inbiorefinery. However, lignin has not been employed as a chemical resource because lignin shows structuralcomplexity, poor reactivity and solubility in organic solvents. We focus on ionic liquid as solvent to realize
facile reaction of lignin. Ionic liquid featuring basic anion such as 1-Ethyl-3-methylimidazolium acetate(EmimOAc) generates N-heterocyclic carbenes (NHCs) and works as organocatalyst 1). In this study, lignin was
modified by using EmimOAc as solvent and catalyst to transform raw lignins into acetylated lignin.
Keyword:ionic liquid, organocatalyst, carbenes, transesterification, hydroxyls
2015-P15
Effect of activated carbon on impurities removal of recycled [Emim]Ac (1-Ethyl-3-Methyl- imidazolium
Acetate) for enzymatic saccharification
Hamidah Umi1), YinYing H’ng1), Akiko Nakagawa-izumi1), Masanori Kishino2)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan, 2)Forest Products
Research Institute, Hokkaido Research Organization, Japan
Abstractionic liquids pretreatment with [Emim]Ac (1-ethyl-3-methylimidazolium acetate) was carried out for
enzymatic saccharification to produce glucose from cellulose in Japanese softwood, Cryptomeria japonica.
Recycling process of [Emim]Ac was conducted by mixing the activated carbon into filtrate which containing[Emim]Ac to remove impurities from filtrate. Visually, activated carbon treatment could successfully eliminate
the black color of recycled [Emim]Ac, whereas n-hexane & ethanol treatment could not. After the enzymaticsaccharification of wood meal treated with [Emim]Ac, the yield of liberated glucose was 10.8% for therecycling with activated carbon, slightly higher than without the activated carbon treatment (9.4%). However,this value was still lower than using fresh [Emim]Ac which could produce 36.2 % of glucose.
597

2015-P16
海洋性 Novosphingobium 属細菌に由来するリグニンモデル 2 量体 β-O-4 結合開裂酵素群の酵素学的解析
大田ゆかり１）、黒澤佳奈子１）永田崇２）、片平正人２）、西村裕志３）、渡辺隆司３）、長谷川良一１）、
秦田勇二
１）
、
1)
海洋研究開発機構、2)京都大学エネルギー理工学研究所、 ３）京都大学生存圏研究所
Kinetic study of the β-O-4 cleaving enzymes of a marine Novosphingobium
Yukari Ohta1), Kanako Kurosawa1), Takashi Nagata2), Masato Katahira2), Hiroshi Nishimura3), Takashi
Watanabe3) Ryoichi Hasegawa1), Yuji Hatada1)
1)Japan Agency for Marine-Earth Science and Technology (JAMSTEC), 2-15 Natsushima, Yokosuka, Kanagawa,Japan, 2)Institute of Advanced Energy, Kyoto University, Japan, 3)Research Institute for Sustainable
Humanosphere (RISH), Kyoto University, Japan
Abstract:
Bacterial enzymatic cascade for β-O-4 reductive cleavage in lignin model dimers consists ofshort-chain dehydrogenase/reductases (SDRs), β-etherases and β-glutathione thioetherases (glutathione lyase).
We previously isolated a marine Novosphingobium from a sunken wood, detected β-O-4 cleavage activity anddetermined the responsible genes for the activity. In this study, we conducted kinetic study of the enzymes tounderstand fundamental properties of the enzymes. Furthermore, a structural model of a SDR was constructed to
discuss the structure-function relationship of the enzyme belonging SDR super family which holds versatileactivities.
Keywords; marine Novosphingobium, β-O-4 reductive cleavage, short-chain, dehydrogenase/reductase,β-etherases, β-glutathione thioetherase, glutathione lyase
2015-P17
リグニンモデル 2 量体中 β-O-4 結合を開裂する海洋性 Novosphingobium 属細菌のゲノムおよびトランスクリ
プトーム解析
西 真郎、黒澤佳奈子、小林樹和、坪内泰志、秦田勇二、大田ゆかり
海洋研究開発機構
Genome and transcriptome analyses of a marine Novosphingobium capable of cleaving the β-O-4 linkage in thelignin model dimer
Shinro Nishi, Kanako Kurosawa, Kiwa Kobayashi, Taishi Tsubouchi, Yuji Hatada, Yukari Ohta
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Japan
Abstract:
We previously isolated a marine Novosphingobium from a sunken wood and detected β-O-4cleavage activity of the isolate. In this study, we carried out genome and transcriptome analyses to understandthe environmental response to lignin related substances of the strain. The genomic analysis revealed themetabolic system of lignin related substances including guaiacylglycerol-β-guaiacyl ether (GGGE). In addition,
we confirmed that GGGE metabolizing genes were arranged in a cluster in the genome of the strain. The
homologs were detected from several microorganisms belonging diverse and phylogenetically distant clades
within Sphingomonadaceae family. The transcriptome analysis revealed that expression of the genes related toassimilation of aromatic compounds and drug-resistance such as multi drug transporter increased when culturing
this strain in the presence of GGGE.
Keywords: marine Novosphingobiu, genome and transcriptome analyses, guaiacylglycerol-β- guaiacyl ether,
metabolic system
2015-P18
リグニンモデル 2 量体中 β-O-4 結合を開裂する海洋性 Novosphingobium 属細菌のゲノムおよびトランスクリ
プトーム解析
西 真郎、黒澤佳奈子、小林樹和、坪内泰志、秦田勇二、大田ゆかり
海洋研究開発機構
Genome and transcriptome analyses of a marine Novosphingobium capable of cleaving the β-O-4 linkage in thelignin model dimer
Shinro Nishi, Kanako Kurosawa, Kiwa Kobayashi, Taishi Tsubouchi, Yuji Hatada, Yukari Ohta
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), JAPAN
Abstract：
We previously isolated a marine Novosphingobium from a sunken wood and detected β-O-4cleavage activity of the isolate. In this study, we carried out genome and transcriptome analyses to understandthe environmental response to lignin related substances of the strain. The genomic analysis revealed the598metabolic system of lignin related substances including guaiacylglycerol-β-guaiacyl ether (GGGE). In addition,
we confirmed that GGGE metabolizing genes were arranged in a cluster in the genome of the strain. The
homologs were detected from several microorganisms belonging diverse and phylogenetically distant clades
within Sphingomonadaceae family. The transcriptome analysis revealed that expression of the genes related toassimilation of aromatic compounds and drug-resistance such as multi drug transporter increased when culturing
this strain in the presence of GGGE.
Keywords: marine Novosphingobiu, genome and transcriptome analyses, guaiacylglycerol-β- guaiacyl
ether, metabolic system
2015-P19
Sphingobium sp. SYK-6 株におけるフェニルクマラン型化合物代謝に関与する
新規デカルボキシラーゼ遺伝子の解明
三宅 恭平１）、高橋 健司１）、上村 直史１）、菱山 正二郎２）、笠井 大輔１）、梶田 真也３）、片山 義博４）、福田雅夫１）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）東京農工大学大学院・生物システム応用科学府、４）日本大学・生物資源科学
Identification and characterization of novel decarboxylase genes involved in the catabolism of
dehydrodiconiferyl alcohol in Sphingobium sp. strain SYK-6
Kyohei Miyake1), Kenji Takahashi1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1), Shinya
Kajita3), Yoshihiro Katayama4), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan,
2)
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan, 3) Graduate School of
Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo,
Japan, 4) College of Bioresource Sciences, Nihon University, Fujisawa, Kanagawa, Japan
Abstract:
Sphingobium sp. strain SYK-6 is able to utilize various lignin-derived biaryls including aphenylcoumaran-type compound, dehydrodiconiferyl alcohol (DCA). In the SYK-6 cells, the alcohol group of
the B-ring side chain of DCA is initially oxidized to the carboxyl group to generate DCA-C. DCA-C is thenconverted to DCA-CC by the oxidations of the alcohol group of the A-ring side chain of DCA-C. DCA-CC isfurther degraded to 5-formylferulate and vanillin through the decarboxylation of the A-ring side chain and thefollowing interphenyl cleavage between C and C. In this study, we isolated and characterized decarboxylase
genes for the conversion of DCA-CC. The phcF, phcG, and phcH genes, which conferred the DCA-CC
decarboxylation activity on Escherichia coli, were isolated from the genomic library of SYK-6. These genes
exhibited no significant similarity with known decarboxylases. Mutant analyses indicated that phcF and phcG
have dominant roles for the conversion of DCA-CC. phcF and phcG were expressed in E. coli, and the resultant
gene products were purified by Ni-affinity chromatography. Purified PhcF and PhcG catalyzed thedecarboxylation of DCA-CC with activities of 70.9 U/mg and 36.7 U/mg, respectively. In addition, PhcF and
PhcG appear to have different stereospcecificity toward DCA-CC enantiomers.
Keywords: dimer, biodegradation, bacteria, racemic, stilbene
2015-P20
Sphingobium sp. SYK-6 株のジアリールプロパン型リグニン由来化合物代謝に関わる立体選択的変換酵素
小林将大１）、南保 美姫１）、上村 直史１）、菱山 正二郎２）、笠井 大輔１）、福田 雅夫１）、政井 英司１) 1）長岡技術科学大学・生物、２）森林総合研究所
Elucidation of the stereospecific catabolic pathway of a diarylpropane-type biaryl in Sphingobium sp. stain
SYK-6
Shota Kobayashi1), Miki Nambo1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1), Masao Fukuda1),
Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan,
2)
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan
Abstract:
Sphingobium sp. strain SYK-6 is a degrader of lignin-derived biaryls, including β-aryl ether,diarylpropane, biphenyl, and phenylcoumaran. To date, a bacterial catabolic pathway of a diarylpropane-type
compound, 1,2-bis(4-hydroxy-3-methoxyphenyl)-propane-1,3-diol (HMPPD), has been investigated only in
Pseudomonas paucimobilis TMY1009. In this strain, HMPPD was subjected to Cγ-deformylation accompanied
by dehydroxylation at the Cα position, resulting in the production of a stilbene-type compound. However, its599

reaction mechanism and the enzyme gene still remain unknown. In this study, we identified the
HMPPD-converting enzyme genes of SYK-6 to fully characterize the catabolic pathway of HMPPD. In order tocharacterize the initial step of HMPPD degradation, the cofactor requirement in converting HMPPD wasinvestigated. A conversion of HMPPD was observed only when NAD+ was present, and the keto form of
HMPPD (HMPPD-keto) was observed as the reaction product. Based on this result, we predicted the
involvement of the Cα-dehydrogenase genes (ligD, ligL, and ligN), which are responsible for the catabolism of
β-aryl ether, in the oxidation of HMPPD. The ligD ligL ligN triple mutant lost most of its ability to convert
HMPPD, whereas this mutant was able to degrade HMPPD-keto. These results strongly suggest that HMPPD is
catabolized via HMPPD-keto in SYK-6, and the Cα-dehydrogenase genes are indeed involved in thisconversion. Enzyme analyses suggest that LigL and ligN converted the same stereoisomer of threo-HMPPD,
while LigD converted the other stereoisomer.
Keywords: biodegradation, enantiomer, β-1 linkage, spirodienone, dimer
2015-P21
Sphingobium sp. SYK-6 株における-アリールエーテル代謝中間体の代謝経路及び酵素遺伝子の解明
樋口 雄大１）、竹浪 寛樹１）、青木 翔吾１）、上村 直史 1)、菱山 正二郎２）、笠井 大輔１）、片山 義博３）、福田雅夫１）、政井 英司１）１）
長岡技術科学大学・生物、２）森林総合研究所、３）日本大学・生物資源科学
Investigation of the downstream pathway of the β-aryl ether catabolism in Sphingobium sp. strain SYK-6
Yudai Higuchi1), Hiroki Takenami1), Shogo Aoki1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1),
Yoshihiro Katayama3), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan,
2)
Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan, 3) College of Bioresource Sciences,
Nihon University, Fujisawa, Kanagawa, Japan
Abstract:
In Sphingobium sp. SYK-6, a degrader of lignin-derived aromatic compounds,
guaiacylglycerol-β-guaiacyl ether (GGE) is initially degraded to β-hydroxypropiovanillone (HPV) through thecleavage of the β-ether linkage. The resulting HPV is then oxidized to vanilloyl acetic acid (VAA) via vanilloyl
acetaldehyde (VAL), and further catabolized through vanillate. In this study, we clarified the catabolic pathwayof HPV and identified the genes involved in this pathway. The hpvZ gene, which conferred the HPV conversion
activity on Sphingomonas sanguinis IAM12578 was isolated from the gene library of SYK-6. Mutant analyses
and enzymatic characterization of the gene product demonstrated that hpvZ encodes a glucose-methanol-choline(GMC) oxidoreductase family protein essential for the conversion of HPV to VAL. In order to identify genes
responsible for the conversion of VAL, putative 23 aldehyde dehydrogenase (ALDH) genes in SYK-6 wereexpressed in E. coli. The enzyme activity of these ALDH in the conversion of VAL was examined, and seven
ALDHs demonstrated significant activity. Analyses of the conversion of VAA by cell extracts of SYK-6 in thepresence of coenzymes suggest that VAA is degraded to vanillate through the formation of the coenzyme A ester
of VAA.
Keywords: acetovanillone, Cγ oxidation, coenzyme A transferase, biodegradation, bacteria
2015-P22
バクテリアにおけるリグニン由来化合物の外膜輸送システム
藤田 雅也、森 光佑、上村 直史、笠井 大輔、福田 雅夫、政井 英司
長岡技術科学大学・生物
Bacterial outer membrane transport system for lignin-derived aromatic compounds
Masaya Fujita, Kosuke Mori, Naofumi Kamimura, Daisuke Kasai, Masao Fukuda, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract:
Sphingobium sp. strain SYK-6 is an alpha proteobacterium capable of utilizing various types oflignin-derived dimeric and monomeric compounds. To date, the catabolic enzyme genes for lignin-derived
aromatics in SYK-6 have been extensively investigated. However, their uptake systems in bacteria are largely
unknown. In this study, we focused on the uptake of lignin-derived aromatics across the outer membrane in
SYK-6. DNA microarray analysis showed that the transcription of the tbtA gene proximal to the5,5-dehydrodivanillate (DDVA) catabolic gene cluster was specifically induced in the SYK-6 cells when grownin the presence of DDVA. Based on the amino acid sequence similarity, tbtA appears to encode a
TonB-dependent receptor (TBDR). Disruption of tbtA in SYK-6 resulted in a growth deficiency on DDVA.
Since outer-membrane localized TBDR is known to transport siderophore and vitamin B12 using proton motive
600

force in consort with inner-membrane localized TonB-ExbB-ExbD complex, TBDR and the TonB complex
appear to be involved in the outer-membrane transport of DDVA. In the SYK-6 genome, three tonB genes were
found, and each of these genes was inactivated to examine their roles. As a result, the growth of a tonB2 mutant
on DDVA, vanillate, and syringate were significantly retarded. These results may suggest that the TonB
complex-TBDR system is involved in the outer-membrane transport of lignin-derived aromatic compounds in
SYK-6.
Keyword:Gram-negative bacteria, transporter, biphenyl, iron, proton motive-force
2015-P23
シロイヌナズナペルオキシダーゼ、AtPrx2, 25, 71 の発現解析による機能推定鎌田 政諒 1)、大平 香織 1)、重藤 潤 2)、堤 祐司 2)
1)
九州大学大学院 生物資源環境科学府、2)九州大学大学院 農学研究院
Expression analysis of lignification-related Arabidopsis peroxidase, AtPrx2, 25, 71
Masaaki Kamada1), Kaori Ohira1), Jun Shigeto2) and Yuji Tsutsumi2)
1)
Graduate school of bioresource and bioenvironmental sciences, Kyushu University, Fukuoka, Japan, 2)Graduate
school of agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Arabidopsis peroxidase, AtPrx2, 25, 71, has been identified to be lignification-related plant
peroxidase (Prx). The analysis measuring oxidative activity for guaiacyl type substrate, syringyl type substrate
and polymer substrate showed that these three Prxs had different oxidizing property each other, and AtPrx71 hadvery similar oxidative property to CWPO-C. The property difference of lignin-polymerize-Prx may cause theinhomogeneity of lignin. In this study, we performed expression analysis using transformants introduced
-glucuronidase gene to investigate the functions of these Prxs, including lignification. The gene expression
pattern varied by individual Prxs, and AtPrx71 expression pattern was similar to that of CWPO-C. These results
suggest that three AtPrxs have different functions in lignification and/or differentiation, and AtPrx71 is the best
functional homologue with CWPO-C among three AtPrxs.
Keywords: Arabidopsis peroxidase, oxidative property, lignification, promotor analysis, differentiation,
2015-P24
エタノール発酵性白色腐朽菌 Phlebia sp. MG-60 株のエタノール発酵メカニズムの解析
王 剣橋 1)、瀧上 翔子 1)、鈴木 智大 2)、亀井 一郎 3)、森 智夫 1)、河岸 洋和 1, 4, 5)、平井 浩文 1, 4)
1)
静岡大学農学部、2)宇都宮大学バイオサイエンス教育研究センター、 3)宮崎大学農学部、4)静岡大学グリーン科学技術研究所、5)静岡大学創造科学技術大学院
Analysis of ethanol fermentation mechanism in ethanol fermentative white-rot fungus Phlebia sp. MG-60
Jianqiao Wang1), Shoko Takigami1), Tomohiro Suzuki2), Ichiro Kamei3), Toshio Mori1), Hirokazu Kawagishi1, 4, 5),
Hirofumi Hirai1, 4)
1)Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2)Center for Bioscience Research and
Education, Utsunomiya University, Utsunomiya 321-8505, Japan, 3)Faculty of Agriculture, University ofMiyazaki, Miyazaki 889-2192, Japan, 4)Research Institute of Green Science and Technology, Shizuoka
University, Shizuoka 422-8529, Japan, 5)Graduate School of Science and Technology, Shizuoka University,
Shizuoka 422-8529, Japan
Abstract:
White-rot fungus Phlebia sp. MG-60 shows higher ethanol production from several cellulosic
materials containing lignin. In order to identify genes which are involved in ethanol production by Phlebia sp.
MG-60, we analyzed the differential gene expression of Phlebia sp. MG-60 under the fermenting andnon-fermenting conditions by next generation sequencing. As the results of the differential gene expression
analysis, the genes which are involved in glucose uptake and metabolism, pyruvate metabolism, and ethanol
synthesis were upregulated under the fermenting condition. To validate the reliability of expression profiles
obtained using MiSeq, we selected four genes with higher expression levels under fermenting condition forreal-time PCR (qRT-PCR) analysis. The results obtained from the qRT-PCR analysis were consistent with datafrom MiSeq.
Keywords: Phlebia sp. MG-60; ethanol fermentation mechanism; differential gene expression; Miseq
2015-P25
Preparation of dissolving pulp from sugarcane bagass by prehydrolysis and soda-AQ cooking method
Lilik Tri Mulyantara1,2), Andri T. Rizaluddin1), Agusta S. Putra1), Roni Maryana1), and Hiroshi Ohi1)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, 2)Center of AgriculturalEngineering Research and Dev., Ministry of Agriculture of Indonesia
601

Abstract:
Sugarcane (Saccharum officinarum) bagasse was used to produce dissolving pulp withcombination of pre-hydrolysis followed by soda-anthraquinone (AQ) cooking and totally chlorine-free (TCF)
bleaching. The TCF bleaching sequence composed of oxygen (O), peroxymonosulfuric acid (Psa), and extraction
with peroxide (Ep) stages. The addition of MgSO4 was intended to maintain of pulp viscosities. Some results
showed that the TCF sequence with Mg2+ addition obtained a higher viscosity than without Mg2+ application.
However, Mg2+ had no positive effect on pulp brightness.
2015-P26
Properties of fibers prepared from oil palm empty fruit bunch for use as corrugating medium
Harsono1,2), Lilik Tri Mulyantara1,2), Andri Taufik Rizaludin1), Hiroshi Ohi1) , Nakamata Keiichi3), 1)Graduate
School of Life and Environmental Sciences, University of Tsukuba, Japan. 2)Center of Agricultural Engineering
Research and Development, Ministry of Agriculture of Indonesia. 3)Technical and Development Division,
Hokuetsu Paper Mills,Ltd, Tokyo, Japan.
Abstract:
This research was aimed at improving the utilization of waste generated by the palm oil
industry by identifying the conditions needed to make fibers suitable for products such as paperboard from theempty fruit bunch (EFB) of oil palm (Elaeis guineensis). For this, the chemical pretreatment conditions needed
to mechanically produce a pulp for paperboard were studied, as well as the effects of varying these conditions
on the fiber properties. The optimum conditions to achieve the highest paper strength were found to be a NaOH
dosage of 2 %, pretreatment time of 2 h at 121 ºC and refiner disk-clearance of 0.10 mm. The tensile index andtear index in this conditions are 19.7 kN.m/kg and 8.8 mN-m2/g, respectively, similar with a pulp preparedfrom an old corrugated fiberboard box, and on the basis of this was considered acceptable for use in corrugating
medium.
Keywords: oil palm empty fruit bunch, mechanical pulp, paperboard, fiber classification, tensile index
2015-P27
Structural alterations of lignin and carbohydrates of bamboo stems during prehydrolysis alkaline sulfite cooking
Roni Maryana1), Guangfan Jin2), Yangfan Lou1,2) and Hiroshi Ohi1)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan, 2) Zhejiang University of
Science and Technology, China
Abstract:
This study is aimed to investigate effects of prehydrolysis prior to alkaline sulfite cooking
process on alterations of lignin and carbohydrate of bamboo (Phyllostachys pubescens). Prehydrolysis was
performed at 150˚C for 1 to 3 h. The residue was then subjected to alkaline sulfite (AS)-anthraquinone (AQ)
cooking with 30% active alkali (AA) dosage at 150˚C for 4 h. Syringil to guaiacyl ratio (S/V ratio) by CuOoxidation method of raw material was 1.9, with the total aldehydes yield 33.9%, and then its decreased to 0.35
after prehydrolysis for 3 hours and cooking. Prehydrolysis followed by AS-AQ cooking can enhance anincrement of cellulose content, and decrements of hemicellulose, lignin and HexA contents. It is shown thatlignin S/V ratio was decreased by prolonged prehydrolysis time.

602

第 61 回 （2016.10.27-28） 京都大学 宇治おうばくプラザ
2016-101
大型イネ科バイオマス植物のリグノセルロース性状比較解析
宮本託志 1)、林晃大 1)、山村正臣 1)、飛松裕基 1)、鈴木史朗 1)、高田理江 1)、児嶋美穂 2)、高部圭司 2)、梅澤俊
明 1), 3)1)
京都大学生存圏研究所、2) 京都大学大学院農学研究科、3) 京都大学研究連携基盤グローバル生存基盤展開ユニットComparative analysis of lignocellulose characteristics in large-sized gramineous plants
Takuji Miyamoto1), Akihiro Hayashi1), Masaomi Yamamura1), Yuki Tobimatsu1), Shiro Suzuki1), Rie Takada1),
Miho Kojima2), Keiji Takabe2), Toshiaki Umezawa1), 3)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan,
2)
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, 3)Research Unit forDevelopment of Global Sustainability
Abstract:
Large-sized gramineous plants are expected as potent biomass feedstocks for productions of
biofuels and various biomass-derived materials especially because of their high biomass productivity. In thisstudy, to gain insight into the relationship between cell wall structures and utilization characteristics ofgramineous biomass, we comparatively characterized fractionated tissues of Erianthus, Sorghum, and sugarcane,in terms of their lignocellulose structures and enzymatic saccharification efficiency. 2D NMR and a series ofcell-wall chemical analyses revealed tissues specific assembly of wall polysaccharides and different types oflignin polymers. Enzymatic saccharification efficiency was negatively correlated with lignin content for
Sorghum and sugarcane tissues but not for the tissues from Erianthus. Our data suggest that lignin content is not
the only factor affecting the enzymatic saccharification efficiency of gramineous biomass.
Keywords: lignification, monocot, bioethanol, biorefinery, bioresource,
2016-102
選択的 13Ｃ標識法と固体ＮＭＲ測定によるリグニンの構造解析
松下泰幸 1)、野村健太 1)、寺島典二 2)、青木弾 1)、光田隼 1)、西村裕志 3)、渡辺隆司 3)、片平正人 4)、福島和彦
1)1）

名大院生命農、2）名大名誉教授、3）京大生存圏、4）京大エネルギー理工
Structural analysis of lignin by a selective 13C labeling technique combined with solid-state 13C NMR
Yasuyuki Matsushita1), Kenta Nomura1), Noritsugu Terashima2), Dan Aoki1), Hayato Mitsuda1), Hiroshi
Nishimura3), Takashi Watanabe3), Masato Katahira4), and Kazuhiko Fukushima1)
1)
Graduate School of Bioagricultural Sciences, Nagoya University, 2) Emeritus professor, Nagoya University, 3)
Research institute for Sustainable Humanosphere, Kyoto University, 4) Institute of Advanced Energy, Kyoto
University
Abstract:
Lignin is one of the main components of wood cell walls, which has a highly complicatedstructure biosynthesized by radical coupling of monolignols. To elucidate the lignin structure, selective
13
C-enriched lignin was produced by an administration of the selective 13C-labeled precursor to wood andanalyzed by solid-state 13C-NMR. In this study, we synthesized [ring 5-13C] coniferin and fed to Ginkgo biloba.
The lignin was obtained by a ball milling followed by enzyme treatment. From the difference NMR spectrum
made by subtraction of the spectrum of the un-enriched enzyme lignin from that of the 13C-enriched enzyme
lignin, quantitative determination was made on the frequencies of major inter-unit bonds. From the result, thefrequency of the uncondensed structure was about 30%, which was lower than the previously reported values. It
should be owing to the cleavage of β-O-4 bond during the ball milling.
Keywords: solid-state 13C-NMR, 13C-labeled coniferin, thioacidolysis, quantitative determination,
uncondensed structure, ball milling
2016-103
β–1 型構造に関する研究：3 量体モデル化合物の NMR データに基づく広葉樹リグニン中のスピロジエノン構造の同定
秋山拓也、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Study on β–1 structures in lignin: Identification of spirodienone structure in hardwood lignin based on the NMR
data of its trimeric model compound603

Takuya Akiyama, Tomoya Yokoyama and Yuji Matsumoto
The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo, Tokyo
113-8657.
Abstract:
A trimeric lignin model compound for spirodienone structures (β–1/α–O–α′) was prepared byoxidative coupling of sinapyl alcohol γ-acetate with a phenolic β–O–4 dimer model. The 1H and 13C NMR
chemical shifts of the spirodienone compound were compared in an acetate form with the candidate signals forspirodienone structures observed on the HSQC spectrum of acetylated hardwood lignin (MWL). The chemical
shifts of the signals from the lignin were in good agreement with those of the model at α, β, and γ-positions in
one side-chain part, α′ and β′-positions in another side-chain part, and 2′ and 6′-positions in the dienone moiety.
Keywords: milled wood lignin, guaiacyl-syringyl, avicennia, diarylpropane, radical coupling
2016-104
モノリグノール配糖体の脱水素重合によるフェニルグリコシド型 LCC 形成の可能性
宮川泰幸 1)、飛松裕基 1),2)、上高原浩 1)、高野俊幸 1)
1)
京都大学 大学院農学研究科、2) 京都大学 生存圏研究所
Possibility of phenyglycoside-type LCC formation by dehydrogenative polymerization using monolignol
glycoside
Yasuyuki Miyagawa1), Yuki Tobimastu1),2), Hiroshi Kamitakahara1), Toshiyuki Takano1)
1)
Graduate School of Agriculture, Kyoto University, Japan, 2) Research Institute for Sustainable Humanosphere,
Kyoto University, Japan
Abstract:
HRP-catalyzed dehydrogenative polymerization of coniferyl alcohol in the presence ofconiferin afforded the corresponding dehydrogenation polymer (CG-DHP-1) in 104 % yield. HSQC-NMR
spectrum of CG-DHP-1 showed that coniferin was non-enzymatically incorporated into lignins via nucleophilic
addition to quinomethide intermediates. On the other hand, HRP/ β-glucosidase-catalyzed dehydrogenative
polymerization of coniferin afforded the corresponding dehydrogenation polymer (CG-DHP-2) in 84 % yield.
HSQC-NMR spectrum of CG-DHP-2 showed not only that coniferin was directly incorporated into lignins, butalso that coniferin was incorporated into lignins via isoconiferin which is produced from coniferin bytransglycosylation.
Keywords: coniferin, isoconiferin, lignin carbohydrate complex, phenyl glycoside, syringin
2016-105
マイクロダイセクション：
ポプラ 1 年輪内のリグニン単位間結合変化の解析
和田卓 1）、藤田弘毅 2）、堤祐司 2）1）九州大学大学院 生物環境資源科学府、2）九州大学大学院 農学研究院
Microdissection : The analysis of lignin internal linkage changing in the growth ring of Populus alba
Suguru Wada1）, Koki Fujita2）, Yuji Tsutsumi2）
1）
Graduate school of bioresource and bioenvironmental sciences, Kyushu University, Fukuoka, Japan, 2）Facultyof Agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Lignification is known to occur in xylem tissue before programmed cell death (PCD). Recently,
it is suggested that lignification still proceeds after PCD in some reports, and our previous study also indicatedthe similar results; the yields of pyrolysis products and S/G ratio, which derived from β-O-4 linked lignin
determined by laser micro dissection (LMD) and pyrolysis-GC-MS (Py-GC-MS), increased and decreased,
respectively, along with the radial direction within a growth ring in which the xylem fiber cells were alreadysuffered from PCD. In order to understand more detailed lignification process, in this study we analyzed β-β,β-1, β-5 internal linkage in lignin using LMD and Py-GC-MS. First, we examined detection limit of Py-GC-MS
for these dimeric pyrolysis products from the dissected samples prepared by LMD. The minimum requirementof the dissected area was 0.3 mm2 in. Then, the abundances of β-β, β-1, β-5 subunits in wood meal preparedfrom old poplar stem, lignified fiber cells and unlignified fiber cells in a year-old P. alba stem were compared.
β-1 subunit was found in a young stem but not in wood meal, which indicate that β-1 is formed at an early stage
in differentiation of xylem fiber cells.
Keywords: laser micro dissection, Py-GC-MS, lignin dimer, xylem, fiber
2016-106
シロイヌナズナ植物体および培養細胞を用いたリグニンモノマー輸送候補 遺伝子の発現解析
604

武内真奈美 1)、毛笠貴博 2)、堤祐司 3)1)
九州大学大学院 生物資源環境科学府、2)九州大学 農学部、3)九州大学大学院 農学研究院
Expression analysis of lignin monomer transporter candidate genes in Arabidopsis plant and cell culture
Manami Takeuchi1)、Takahiro Kegasa2)、Yuji Tsutsumi3)
1)
Graduate school of bioresource and bioenvironmental sciences, Kyushu University, Fukuoka, Japan, 2)Facultyof agriculture, Kyushu University, 3)Graduate school of agriculture, Kyushu University, Fukuoka, Japan
Abstract:
Monolignol transport from the cytosol to the cell wall is essential step for lignification becausemonolignols are synthesized in the cytosol and polymerized in the apoplast. Previously, some studies suggested
that ATP-binding cassette (ABC) transporters have potential to transport monolignol across the plasma
membrane in Arabidopsis thaliana, thus screening of monolignol transporter among ABC transporters wereattempted in this study. In the first screening, ten ABC transporters that are conserved in only vascular plant, A.
thaliana but not in non-vascular plant, Physcomitrella patens were selected. Parallel screening was made by themonitoring of the gene expression with real-time PCR using tracheary element induction system of the A.
thaliana cell culture. The expression profile of selected candidate transporter genes in each plant organ was
analyzed with real-time PCR using A. thaliana intact plants. Positive correlation between monolignol synthesis
genes and the five selected transporter genes suggested that these transporters may be related to lignin
biosynthesis.
Keywords: Arabidopsis thaliana, monolignol, extracellular transport, ATP-binding cassette transporter,
real-time PCR
2016-107
改変型植物酸性 peroxidase の酵母での発現と精製(5)小山 翔、高安 真未、平野 智哉、川合 伸也
東京農工大学大学院、東京農工大学 植物工学研究室
Heterogeneous expression and purification of modified plant peroxidase (5)Sho Koyama, Mami Takayasu, Tomoya Hirano, Shinya Kawai
Department of Applied Biological Chemistry, Tokyo University of Agriculture and Technology, Tokyo, Japan
Abstract:
Most of plant peroxidases can oxidize coniferyl alcohol efficiently, but not sinapyl alcohol. On
the other hand, a few of plant peroxidases were reported to use sinapyl alcohol as preferred substrates. They
were guessed to have the additional active sites in the other positions than the heme pocket in the active site. We
tried to introduce the additional catalytic sites of these peroxidases to PrxA3a, an anionic peroxidase of hybrid
aspen, Populus X kitakamiensis, for substrate specificity modifications and for certifications of the surface
amino acid residue hypothesis. As a result, PrxA3a A165W and PrxA3a F77Y, PrxA3a F77Y A165W raised theoxidizing activity of cytochrome c which cannot enter into the heme pocket. Furthermore, PrxA3a F77Y,
PrxA3a F77Y A165W, and PrxA3a F77Y L182Y gained sinapyl alcohol polymerizing activity. We analyzed
shifts of Soret band absorption by H2O2 treatment. The responses to the H2O2 of Soret band absorption differedin mutated PrxA3a enzymes and wild type. Therefore, it is thought that electron transfer is occurred between
heme and mutated amino acid residues. The gel filtration analysis showed that PrxA3a AW and PrxA3a FYAW
could polymerize sinapyl alcohol efficiently.
Keyword:lignin, PrxA3a, soret band, HPLC, sinapyl alcohol
2016-108
リグニン・多糖複合体分解酵素の植物体での発現(２)黛 康悦、丸山 亮、川合 伸也、
東京農工大学 連合農学研究科、Expression of a lignin-carbohydrate complex degrading enzyme in plants (2)Yasuyoshi Mayuzumi, Ryo Maruyama, Shinya Kawai,
United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology
Abstract:
We aim to increase the industrial values of crops by improvement of the digestibility of theforage crop and conversion rate to saccharification from biomass. We have been challenging to modify thelignin content and structures, by suppression of the genes for the lignin biosynthetic pathway or expression oflignin degradation enzymes. In this research, we tried to reduce the linkages between lignin and carbohydrate byintroduction of a lignin-carbohydrate-complex decomposition enzyme gene to rice plants. CcEST1 is an esterase
and CcAbf62A is an arabinofuranosidase of a white-rot-fungus, Coprinopsis cinerea. These enzymes can cut
bonds between the lignin and polysaccharide. CcEST1 has feruloylesterase and acetyltransesterase activities.
605

CcAbf62A has activity for arabinoxylan, one of hemicelluroses. We altered the genes to effectively secrete to
the plant extracellular space and induced to rice plants. We checked introduction of each gene by PCR. There
were no seriously changes in the phenotypes of CcEST1 introduced rice plants. But, one CcAbf62A introduced
rice plant represented dwarf and abnormal tillering phenotypes.
Keywords: lignin, Oryza sativa, Coprinopsis cinerea, esterase, arabinofuranosidase, Agrobacterium
tumefaciens, degrading enzyme, lignocarbohydrate complex, prxA3a
2016-109
リグニン含量が極端に異なるハイブリッドユーカリ系統の遺伝子発現解析
河岡明義 1）、新屋智祟 1）、岩田英治 1)、中浜克彦 1)、福田雄二郎 1)、林和典 2)、南藤和也 1)、Antonio C. Rosa2)
１）
日本製紙 アグリ・バイオ研究所 ２）AMCEL 研究部
Transcriptome Analysis of Hybrid Eucalyptus with Contrasting Lignin Content
Akiyoshi Kawaoka1), Tomotaka Shinya1), Eiji Iwata1), Katsuhiko Nakahama1),
Yujiroh Fukuda1), Kazunori Hayashi2), Kazuya Nanto1) and Antonio C. Rosa2)
1 )Agri-Biotechnology Research Laboratory, Nippon Paper Industries Co., Ltd. 5-21-1 Oji, Kita-ku,Tokyo,
114-0002, Japan, 2) Forest Research Division, Amapa Frorestal e Celulose S.A. Rua Claudio Lucio Menteiro,
S/N, Santana, Amapa, 68925-000, Brazil
Abstract:
Eucalyptus is one of the most important commercial temperate hardwoods for the pulp andpaper industries because of its fast growth and good pulp production characteristics. In this study, we comparedtranscript levels involved in secondary cell wall synthesis related genes to find out DNA markers. First, wemeasured Klason lignin content of 918 hybrid Eucalyptus (Eucalyptus urophylla x E. grandis) trees by
Near-Infrared spectra. These trees were composed of 20.2–35.5% of Klason lignin content with normal
distribution. Among them, we selected two genotypes that have contrast lignin content for further analysis.
AM063 and AM380 had 20.2 and 35.5% of Klason lignin content, respectively. The correlation between wood
properties and transcript levels of wood formation-related genes was investigated by RNA-seq. No significant
differences of transcript levels of ten cellulose synthase and four sucrose synthase genes were observed in both
genotypes. AM063 exhibited higher transcript levels of UDP-glucose pyrophosphorylase and xyloglucan
endotransglucosylase than those in AM380. Most monolignol biosynthesis-related isozyme genes showedsignificantly higher transcript levels in AM380. Higher transcript levels of the genes encoding NAC, WRKY,
AP2/ERF, and HD transcription factors in AM380 were observed. We also found increased transcription ofseveral MYB and LIM domain transcription factors in AM380 as compared to AM063. These results show thatgenes related to monolignol biosynthesis may regulate the wood composition.
Keywords: hybrid Eucalyptus, lignin, cellulose, hemicellulose, RNA-seq
2016-110
二次細胞壁形成で発現する遺伝子の網羅的機能解析と木質バイオマス改変技術の開発
遠藤暁詩、福田裕穂
東京大学大学院理学系研究科
A comprehensive functional analysis of secondary cell wall formation-associated genes and its application forgenetic engineering of woody biomass utilization
Satoshi Endo, Hiroo Fukuda
Graduate School of Science, The University of Tokyo, Tokyo 113-0033, Japan
Abstract:
This study aims (1) to identify more key players regulating secondary cell wall (SCW)
formation, and (2) to develop genetic tools for engineering SCWs. We have prepared hundreds of Arabidopsis
homozygous lines expressing more than 50 genes of our interest at the very early stage of SCW formation.
While most lines grew like wild-type, their woody tissue samples showed different levels of susceptibility to an
enzymatic degradation under a very mild pretreatment condition. Some lines showing the high enzymatic
digestibility had modified xylan or lignin.
Keywords: 101 genes project, xylem-specific overexpression screen, hot compressed water pretreatment
2016-111
ヘミセルロースの合成阻害による細胞壁成分への影響
真嶋雄二郎１）、加藤あすか１）、中沢威人１）、本田与一１）、山村正臣２）、
飛松裕基２）、梅澤俊明２,３）、坂本正弘１）
１）
京大院農学研究科、２）京大生存研、３）京大生存基盤科学研究ユニット
606

The effect of the inhibition of hemicellulose synthesis on cell wall composition
Yuujiro Majima1), Asuka Kato1), Takehito Nakazawa1), Yoichi Honda1), Masaomi Yamamura2), Yuki Tobimatsu2),
Toshiaki Umezawa2,3), and Masahiro Sakamoto1)
1)
Graduate School of Agriculture, Kyoto University, Kitashirakawa-oiwakecho, Sakyo-ku, Kyoto 606-8502
Japan, 2) Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan, 3)
Institute of Sustainability Science, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract:
To elucidate the role of hemicellulose in plant cell wall, its synthesis was inhibited by RNAi
method. In our study, target gene is UDP-glucuronic acid decarboxylase (UDP-xylose synthase, UXS) whichconverts UDP-xylose from UDP-glucuronic acid. In rice (Oryza sativa), the genes for UXS are consisted as amulti gene family with five clones. During elongation period of rice, the expression level of UXS3 was the mostabundant among UXS gene family. To suppress this gene, UXS3-RNAi vector was constructed and introduced
into rice. Almost transgenic rice (UXS3-RNAi) strains were dwarfing compared to wild type, and they showedsterility. The expression of UXS3 in transgenic rice was inhibited. Interestingly, PAL and 4CL involved in lignin
biosynthesis were also inhibited in proportion to the UXS3 expression level. The composition of cell wall was
analyzed to show the decrease of xylose and therefore hemicellulose, in contrast cellulose content was increased.
As expected in the expression of lignin biosynthesis genes, the lignin content was also reduced. This wasderived from decrease of xylose, arabinose and ferulic acid binding to lignin. Therefore, it showed thepossibility to regulate lignin biosynthesis by UXS3 regulation.
Keywords: rice, UDP-glucuronic acid decarboxylase, PAL, 4CL, cellulose
2016-112
順遺伝学アプローチを起点とした、リグニン分解酵素活性およびリグニン生分解に重要な新たな因子の探索
中沢威人 1)、小寺里奈 1)、西村裕志 2)、坂本正弘 1)、渡辺隆司 2)、本田与一 1)1)
京都大学大学院農学研究科, 2)京都大学生存圏研究所
Forward genetics study in the white-rot agaricomycete Pleurotus ostreatus suggested unidentified factors areimportant in the ligninolytic system
Takehito Nakazawa1), Rina Kodera1), Hiroshi Nishimura2), Masahiro Sakamoto1), Takashi Watanabe2), Yoichi
Honda1)
1)
Graduate School of Agriculture, Kyoto University, 2)Research Institute for Sustainable Humanosphere, Kyoto
University
Abstract:
White-rot fungi play an important role in global carbon cycle because they are the only known
organism that biodegrade wood lignin. Lignin peroxydases (LiPs), manganese peroxidases (MnPs) and versatile
peroxidases (VPs) are considered to be key players in the ligninolytic system. However, there may remain
unidentified factor(s) important in the ligninolytic system. Classical genetics or forward genetics, isolation ofmutants followed by identification of the gene responsible for a mutant phenotype, is a straightforward strategy
to identify such factor(s). We successfully identified three genes important in decolorization of dyes, modelcompounds to examine the ligninolytic activity in the white-rot fungus Pleurotus ostreatus. Examination of theeffects of the mutations on gene expression, enzyme activity and wood lignin biodegradation suggested acomplicated mechanisms underlying the ligninolytic system.
Keywords: white rot, fungal genetics, peroxisome, RNA-seq, transcriptional regulation
2016-201
リグノセルロースバイオリファイナリーのためのリグニン・ペプチド間相互作用解析
山口亜佐子 1,4)、末富高志 1)、大城理志 1,4)、徳永有希 1)、西村裕志 1,4)、永田崇 2,4)、真嶋司 2,4)、
片平正人 2,4)、磯﨑勝弘 3,4)、高谷光 3,4)、中村正治 3,4)、渡辺隆司 1,4)
1)
京都大学生存圏研究所、2) 京都大学エネルギー理工学研究所、3) 京都大学化学研究所
4)
CREST, JST
Analysis of interaction between lignin and peptides for lignocellulosic biorefinery
Asako Yamaguchi1,4), Takashi Suetomi1), Satoshi Oshiro1,4), Yuki Tokunaga1), Hiroshi Nishimura1,4), Takashi
Nagata2,4), Tsukasa Mashima2,4), Masato Katahira2,4), Katsuhiro Isozaki3,4), Hikaru Takaya3,4),
Masaharu Nakamura3,4), Takashi Watanabe1,4), 1)Research Institute for Sustainable Humanosphere, Kyoto
University, 2)Institute of Advanced Energy, Kyoto University, 3)Institute for Chemical Research, Kyoto
University, 4)CREST, JST
Abstract:
Highly selective degradation of lignin is pivotal for lignocellulosic biorefinery. However, few
studies have examined natural and synthetic molecular components recognizing the heterogeneous aromatic607

polymer. We identified lignin-binding 12-mer peptides using a phage display technique. The selected peptides
were found to possess a characteristic sequence and exhibit structure-dependent high-affinity binding to thelignin isolated from softwood and hardwood. To characterize the key amino acid residues in the lignin-binding
peptides, a peptide designated as C416 and its single-residue substituted peptides were subjected to the binding
analysis with MWL from softwood and hardwood.
Keywords: peptide, lignin, phage display, SPR, MWL
2016-202
高活性リグニン分解菌 Phanerochaete sordida YK-624 株によるネオニコチノイド系殺虫剤の分解及び無毒化
田中佑典 1)、王剣橋 1)、長井薫 2)、森智夫 1)、河岸洋和 1, 3, 4)、平井浩文 1, 3)
1)
静大農、2)甲子園大栄養、3)静大グリーン研、4)静大創造院
Degradation and detoxification of the neonicotinoid insecticides by the white-rot fungus Phanerochaete sordida
YK-624
Yusuke Tanaka 1), Jianqiao Wang 1), Kaoru Nagai 2), Toshio Mori 1),
Hirokazu Kawagishi 1, 3, 4), Hirofumi Hirai 1, 3)
1)Faculty of Agriculture, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan,
2)
Department of Nutrition, Kohshien University, 10-1 Momijigaoka, Takarazuka 665-0006, Japan,
3)
Research Institute of Green Science and Technology, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka
422-8529, Japan, 4) Graduate School of Science and Technology, Shizuoka University, 836 Ohya, Suruga-ku,
Shizuoka 422-8529, Japan
Abstract:
Clothianidin (CLO) and nitenpyram (NIT) are the family of the neonicotinoid pesticides, whichhave been widely used over the last two decades. However, its toxicity for insects and neurological toxicity forhumans are serious problems. Here, the degradations of CLO and NIT by the white-rot fungus Phanerochaete
sordida YK-624 were examined in nitrogen-limited liquid medium. After incubation for 20 days at 30 °C, 37%
of CLO was degraded in the cultures. In contrast, after incubation for 5 days at 30 °C, 100% of NIT was
degraded in the same cultures. High-resolution ESI-MS and NMR analyses of the culture supernatant metabolite
identified N-(2-chlorothiazol- 5-yl-methyl) -N’-methylurea (TZMU) as a metabolite of CLO degradation.
Similarly, We identified (E)-N-((6-chloropyridin-3yl) methyl)-N-ethyl-N’-hydroxyacetimidamide (CPMHA) as
a metabolite of NIT degradation. The addition of cytochrome P450 inhibitors to the culture medium caused the
reduction of CLO degradation by P. sordida YK-624. The viability of the neuronal cell line Neuro2a by theeffects of CLO and TZMU demonstrated that P. sordida YK-624 effectively degrades CLO into a metabolitethat lacks neurotoxicity.
Keyword:Phanerochaete sordida YK-624; clothianidin; nitenpyram; bioremediation
2016-203
ブナ木粉中リグニンの酵素的分解反応最適化の試み
池田拡平 1)、森智夫 1)、河岸洋和 1), 2), 3)、平井浩文 1), 2)
1)
静岡大学農学部、2)静岡大学グリーン科学技術研究所、3)静岡大学創造科学技術大学院
Optimization of enzymatic lignin degradation in beech woods by manganese peroxidase
Kohei Ikeda 1), Toshio Mori 1), Hirokazu Kawagishi 1, 2, 3), Hirofumi Hirai 1, 2)
1)Faculty of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan, 2) Research Institute of Green Scienceand Technology, Shizuoka University, Shizuoka 422-8529, Japan, 3) Graduate School of Science and Technology,
Shizuoka University, Shizuoka 422-8529, Japan
Abstract:
Woody biomass is the most abundant biomass, and it is expected the utilization as biorefinery
feedstock. However, lignin which is a recalcitrant aromatic polymer contained in wood, and prevents thebreakdown of cellulose and hemicellulose. In this study, we attempt to optimize the enzymatic system that
degrades lignin in beech wood by manganese peroxidase (MnP) from Phanerochaete sordida YK-624. At first,
we investigated the effect of the combination of the radical mediators in the enzymatic delignification reaction.
Although some of combinations have not improved the lignin degradation, many of radical mediatorcombination have been improved lignin degradation. In addition, lignin degradation rate was further improvedby the addition of cellulases. Therefore, it is suggested that the simultaneous saccharification and delignification
reaction is much effective for the enzymatic delignification.
Keywords: Phanerochaete sordida YK-624, manganese peroxidase, lignin degradation, radical mediator,
saccharification
2016-204
608

ルテニウム錯体結合型アミノ酸触媒を用いるリグニンおよびモデル化合物の酸化的分解
吉田亮太１）２）、磯﨑勝弘１）２）、横井友哉１）２）、渡辺隆司３）５）、西村裕志３）５）、片平正人４）５）、近藤敬子４）５）、高谷
光１）２）５）、中村正治１）２）
１）
京都大学化学研究所、２）京都大学大学院工学研究科物質エネルギー化学専攻、
３）
京都大学生存圏研究所、４）京都大学エネルギー理工学研究所、５）CREST, JST
Ruthenium complex-bound amino acid-catalyzed oxidative degradation of lignin and model compounds
Ryota Yoshida1) 2), Katsuhiro Isozaki1) 2), Tomoya Yokoi1) 2), Takashi Watanabe3) 5), Hiroshi Nishimura3) 5),
Masato Katahira4) 5), Keiko Kondo4) 5), Hikaru Takaya1) 2) 5), Masaharu Nakamura1) 2)
1)
Institute for Chemical Research, Kyoto Univ., Gokasho, Uji, Kyoto 611-0011, Japan, 2) Department of Energyand Hydrocarbon Chemistry, Faculty of Engineering, Kyoto Univ., Nishikyo- ku, Kyoto 615-8530, Japan, 3)
Research Institute for Sustainable Humanosphere, Kyoto Univ., Gokasho, Uji, Kyoto 611-0011, Japan, 4)
Institute of Advanced Energy, Kyoto Univ., Gokasho, Uji, Kyoto 611-0011, Japan, 5) CREST, JST
Abstract:
An efficient oxidative degradation of lignin into useful aromatic compounds has beendeveloped by using H2O2 as a terminal oxidant and in the presence of a catalytic amount of ruthenium
complex-bound amino acid 1. Model compounds of the lignin substructures, such as benzyl alcohols,
methoxybenzenes, and β-O-4 dimer models can be oxidized under the degradation conditions to give thecorresponding 1,4-benzoquinones, phenols, aromatic aldehydes, and aromatic ketones. The oxidative
degradation of milled wood lignin (MWL) and wood powder obtained from Japanese cedar gives
2-methoxy-1,4-benzoquinone selectively, demonstrating the efficiency of ruthenium complex-bound amino acidcatalyst 1.
Keywords: Ruthenium catalysis, Metalated amino acid, Oxidation, Aromatic biorefinery, 2D NMR
2016-205
フェノール性水酸基をメチル化した木粉のマイクロ波ソルボリシスにより得られるリグニンオリゴマーの構造解析
齋藤香織 1)、海寳篤志 2)、酒井亮 2)、牧村裕 1)、西村裕志 1)、渡辺隆司 1)
1)
京都大学生存圏研究所、2)日本化薬株式会社
Structural analysis of lignin oligomers released by microwave solvolysis of wood obtained after methylation offree phenolic hydroxyl groups
Kaori Saito1), Atsushi Kaiho2), Ryo Sakai2), Yutaka Makimura1), Hiroshi Nishimura1), Takashi Watanabe1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611–0011, Japan,
2)
Nippon Kayaku Co., Ltd, Chiyoda-ku, Tokyo 100-0005, Japan
Abstract:
An acid-catalyzed toluene-methanol solvolysis method can release lignin oligomers from wood.
In this study, phenolic end groups in lignin were selectively methylated to investigate how the phenolic units
influence on release of lignin oligomers during solvolysis. Thioacidolysis analysis of TMS-CH2N2 methylated
wood sample showed that about 17% of guaiacyl units corresponded to terminal units with free phenolic groups.
Thioacidlysis and subsequent Raney nickel desulfuration showed that lignin dimeric compounds derived fromterminal units with free phenolic groups were detected only for β-1 and β-5 linkages, not for 5-5, β-β, and 4-O-5
bonds. In particular, the relative abundances of the β-O-4-linked β-1 dimers derived from phenolic terminal
units were significantly higher than those of β-5 linkages. This result may relate the fact that the β-1 dimers are
more easily detected during solvolysis compared to the other linkage types.
Keywords: lignin, interunit linkages, thioacidolysis, trimethylsilyl diazomethane, solvolysis.
2016-206
リグニン結合性有機物担持前加水分解による天然リグニンの構造制御
畠 智之，野中 寛
三重大学大学院生物資源学研究科
Structural control of native lignin during prehydrolysis by sorption of a lignin-binding organic compound
Tomoyuki Hata, Hiroshi Nonaka
Graduate school of Bioresources, Mie university, Japan
Abstract:
Prehydrolysis using dilute acid was conducted for wood meal sorped with p-cresol. The residue
was treated in sodium hydroxide solution at 170 ºC. After acidification of black liquor, dioxane-soluble andether-insoluble lignin was recovered. FT-IR spectrum of the lignin indicated that p-cresol was grafted to native
lignin during dilute acid prehydrolysis. An aromatic dimer with phenyl coumaran-type structure was also
recovered, indicating that cleavage of β-O-4 linkages occurred in alkaline condition by nucleophilic attack of609

p-cresol grafted to α-carbon of native lignin. The sorption of p-cresol could be an effective method to control thelignin structure during prehydrolysis.
Keywords: dilute acid, prehydrolysis, wood, p-cresol, functional lignin
2016-207
第四級アンモニウム塩を反応媒体としたリグニンの高選択的分解
細谷隆史 1)、山本康平 1)、溝口晃平 1)、吉岡康一 1)、宮藤久士 1)、大野弘幸 2)、山田竜彦 3)1)
京府大院生環、2)東京農工大院工、3)森林総研
Selective conversion of lignin with quaternary ammonium salts as a reaction medium
Takashi Hosoya1), Kohei Yamamoto1), Kohei Mizoguchi1), Koichi Yoshioka1), Hisashi Miyafuji1), Hiroyuki
Ohno2), Tatsuhiko Yamada3)
1)
Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan, 2)Graduate Schoolof Engineering, Tokyo University of Agriculture and Technology, Japan, 3)Forestry and Forest Products
Research Institute, Japan
Abstract:
Lignins such as milled wood lignin, sodium lignosulfonate, and soda lignin and Japanese cedar(Cryptomeria japonica) wood flour, were degraded in tetrabutylammonium hydroxide 30-hydrate,
NBu4OH·30H2O, at 120 oC. The degradation for 72 h gave vanillin with surprisingly high yields, e.g. themilled wood lignin gave vanillin with 11.5 wt%. Degradation in an aqueous NaOH solution with the same OH concentration resulted in much less vanillin yield, which strongly suggests that the NBu 4+ cation was
responsible for the high yield of vanillin. Discussion on the mechanisms in the effects of the NBu 4+ cation wasmade on the basis of further model experiments and pulping mechanisms reported previously.
Keywords: degradation, quaternary ammonium, vanillin, alkali
2016-208
Stereo-preferential degradation of the erythro and threo isomers of β-O-4 type lignin model compounds underhydrogen peroxide bleaching conditions and its relation to the type of major degradation products
Pattaraporn Posoknistakul, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, Tokyo, Japan
Abstract:
The erythro (E) or threo (T) isomer of a dimeric non-phenolic β-O-4-type lignin modelcompound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (E isomer or T isomer,
respectively), was individually reacted with hydroxyl and/or oxyl anion radicals generated by the decompositionof hydrogen peroxide under a condition similar to hydrogen peroxide bleaching to observe the stereo-preferenceof these radicals toward the E or T isomer. The stereo-preference of oxyl anion radical was intrinsically the E
isomer, but conversely the T isomer in the reaction at a high pH where the α-hydroxy group of the E isomer was
hypothesized to dissociate. This dissociation generates the electrostatic repulsion between negatively charged
oxyl anion radical and the side-chain of the E isomer. Hydroxyl radical had almost no stereo-preference,probably owing to its high reactivity to the aromatic nucleus. As the major degradation products, veratraldehyde
and veratric acid were obtained with relatively high yields at high pH levels.
Keywords: delignification, diastereomer, pulp, bleaching, alkyl-aryl ether
2016-209
熱分解温度を考慮したグアイアコールからのコーク、多環式芳香族化合物及びその他芳香族化合物の生成
機構
河本晴雄、成田和央、坂 志朗
京都大学大学院エネルギー科学研究科
Temperature-dependent conversion mechanisms of guaiacol into coke, polycyclic aromatic hydrocarbons, andother aromatic compounds
Haruo Kawamoto, Kazuo Narita, Shiro Saka
Graduate School of Energy Science, Kyoto University, Japan,
Abstract:
Guaiacol and its alkyl-substituted derivatives are the important intermediates during lignin
pyrolysis, which degraded further into coke (solid carbonized products), polycyclic aromatic hydrocarbons(PAHs) and other aromatic compounds including cresols, catechols, benzene and toluene along with thenoncondensable gases. In this paper, formation and degradation behaviors of 23 compounds during pyrolysis of
guaiacol were investigated under nitrogen in the temperature range 300-600 ºC. Some compounds were
pyrolyzed independently to understand their roles in the product formation. Based on these results, lignin
610

conversion mechanisms during pyrolysis are discussed in terms of the temperature effects. These results would
provide insights into the useful bio-chemicals production from lignin and mitigation of tar trouble in wood
gasification.
Keywords: lignin, pyrolysis, polycyclic aromatic hydrocarbon, methoxyl group, mechanism
2016 特別講演
超・亜臨界流体技術によるリグノセルロースのトポ化学
坂 志朗
京都大学大学院エネルギー科学研究科
Invited lecture: Topochemistry of lignocellulosics by supercritical/subcritical/fluid technologies
Shiro Saka
Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan
Abstract：
Global warming and depletion of fossil fuels are recently causing many problems. Under such asituation, a special attention has been paid to lignocellulosics for useful energy and chemicals. Therefore, in thisstudy, evolution and biodiversity of various biomass species were first introduced so as to discuss topochemistryof lignocellulosics. In addition, the behaviors of lignocellulosic decomposition were evaluated for biobasedenergy and chemicals as treated by supercritical/subcritical fluid technologies, focusing on topochemistry oflignin.
Keywords: chemical composition, biosynthesis, wood cell wall, softwood, hardwood, solvolysis
2016-210
木材の熱安定性に及ぼすリグニンの影響
モハメド・アスマディ 1, 2)、 河本晴雄 1)、 坂 志朗 1)
1)
京都大学大学院エネルギー科学研究科, 2)マレーシア工科大学化学エネルギー工学科
Influence of lignin on wood thermal stability
Mohd Asmadi1, 2), Haruo Kawamoto1), Shiro Saka1)
1)
Graduate School of Energy Science, Kyoto University, Japan, 2)Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Malaysia
Abstract:
Heterogeneous layered structure of wood cell wall, which consists of assembling cellulose
microfibrils covered by the hemicellulose-lignin matrix, is expected to influence the thermal stability of woodconsisting polymers. In this study, thermal stabilities of Japanese beech (a hardwood) and Japanese cedar (asoftwood) were compared with those of their holocellulose, milled wood lignin (MWL) and hemicellulose
fractions by using thermogravimetry (TG) (N2/ 10 C/min). As a result, the derivative of TG (DTG) peaks andshoulders of wood samples were shifted to the lower temperature regions for holocelluloses, where the peak andshoulder temperatures were rather close to those of cellulose (Avicel PH-101) and the isolated hemicelluloses,
respectively. Thus, lignin would stabilize hemicellulose and cellulose in wood cell wall against thermal
degradation. Interestingly, DTG shoulder temperatures of wood and demineralized wood samples were very
close to those of MWL + 2%KOAc (a model of metal uronate in xylan) and MWL, respectively. These results
lead to an interesting hypothesis: hemicellulose in wood cell wall becomes reactive when lignin thermal
degradation (depolymerization) occurs, since hemicellulose is stabilized by covering with lignin polymers.
Keywords: pyrolysis, thermal stability, hardwood, softwood, stabilization effect of lignin
2016-211
リグニンアナログの溶液中における構造
重冨顕吾 1）、山本陽子 2）、幸田圭一 1）、岸本崇生 3）、浦木康光 1）1）
北海道大学大学院農学研究院、2）北海道大学大学院農学院、3）富山県立大工学部
Structure of lignin analogues in solution
Kengo Shigetomi1), Yoko Yamamoto2), Keiichi Koda1), Takao Kishimoto3), Yasumitsu Uraki1)
1)
Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 2)Graduate School of
Agriculture, Hokkaido University, Sapporo 060-8589, Japan, 3)Toyama Prefectural University, Imizu 939-0398,
Japan
Abstract:
Size exclusion chromatography with a detector of multi-angle laser light scattering was
attempted for lignin analogues, polymeric lignin model exclusively comprised of β-O-4’ linkages andamphipathic lignin derivatives to investigate their structures in solution. The lignin model compound exhibited asimilar swelling behavior in chloroform to that of polystyrene. The lignin derivatives formed self-aggregates in611

chloroform, and the aggregates had more compact structure than polystyrene with the same molecular mass.
Keywords: SEC-MALS, lignin structure, Mark-Houwink-Sakurada equation, light scattering
2016-212
木材の物性研究からみえるリグニン
三好由華 1)、神代圭輔 2)、古田裕三 2)
１）
森林総合研究所、２）京都府立大学大学院 生命環境科学研究科
Lignin from the view of wood physics researches
Yuka Miyoshi1), Keisuke Kojiro2), Yuzo Furuta2)
1)
Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan, 2)Graduate
School of Life and Environmental Sciences, Kyoto Prefectural University,
1-5 Hangi-cho, Shimogamo, Sakyo-ku, Kyoto 606-8522, Japan
Abstract:
We have obtained many interesting results about lignin by various measurements of physicalproperties such as viscoelastic properties, thermal characteristics, and adsorption characteristics. And, it wasconsidered how molecular state of lignin was present in cell wall or what kinds of role was played by lignin inwood based on these results. The followings are some of the information. Thermal softening temperatures andapparent activation energy of lignin in water-swollen wood were different among Japanese hardwood, tropical
hardwood and coniferous wood, and these were decreased with decrease in the amount of lignin or crosslinking
density, and these were also changed by drying history or cooling speed after heating. In addition, the value of
micro pores with a pore size of several Å based on lignin was decreased and the specific heat was changed
significantly by heat treatment. In this debating society, these information would be explained together, andpresence state and role of lignin in wood be comprehensively discussed.
Keywords: wood physics, viscoelastic property, thermal characteristics, adsorption characteristics,
crosslinking density
2016-213
リグニンを原料とするタンデム型電気２重層キャパシタ用電極の開発
Xiangyu You 1)、幸田圭一 2)、浦木康光 2)1）北海道大学 大学院農学院、2）北海道大学 大学院農学研究院
Development of electrodes for internal tandem electric double layer capacitors (IT-EDLCs) derived from lignin
Xiangyu You1), Keiichi Koda2), Yasumitsu Uraki2)
1)
Graduate School of Agriculture, Hokkaido University, Sapporo, 060 -8589, Japan, 2)Research Faculty ofAgriculture, Hokkaido University, Sapporo, 060-8589, Japan
Abstract:
To fabricate electric double layer capacitors (EDLCs) with a wide potential window and a highenergy density in an EDLC package, electrodes derived from lignin based activated carbon fibers (ACFs) wereinternally laminated and connected in series, in parallel, or in a series/parallel combination, which are named asinternal tandem (IT) EDLCs in this article. As expected, the potential window was expanded by the seriesconnection, and the capacitance was increased by the parallel connection. The energy density in theparallel-connected EDLC was remarkably increased by 66% (16.6 Wh kg-1) compared with that of a single cell
type EDLC. The EDLC with the combination connection showed both advantages.
Keywords: electric double layer capacitor (EDLC), energy density, power density, functionalization,
value-added material
2016-214
PEG・バイサルファイト法によるタケリグニン液化物から調製したポリウレタンフォームの特性評価
河野 陽平 1、段 梦弘 2、藤田 弘毅 1、堤 祐司 1
1)
九州大学大学院 農学研究院、2)九州大学大学院 生物資源環境科学府
Characterisation of polyurethane foam prepared from liquefied bamboo-lignin by PEG-bisulfite method
Yohei Kawano1, Menghong Duan2, Koki Fujita1 and Yuji Tsutsumi1
1)
Department of Agro-environmental Sciences, Kyushu University, 2)Graduate School of Bio-resource andBioenvironmental Sciences, Kyushu University, 812-8581, Fukuoka, Japan
Abstract:
Liquefaction of bamboo was performed by polyethylene glycol (PEG)-bisulfite method. A
retention rate of lignin in liquefied bamboo was depended on treatment temperature and reaction times.
Additionally, polyurethane foam, prepared from the liquefied bamboo, was showed high storage elastic modulus
than control sample of PEG using solid viscoelasticity measurement. This PEG-bisulfite liquefaction can be one612

of plausible method for the biorefinery of bamboo and bamboo lignin.
Keyword：lignin, bamboo biorefinery, polyurethane foam, PEG-bisulfite method, viscous elasticity
2016-P01
広葉樹の葉リグニンの DFRC 法による検出（３）松井直之、大平辰朗（研）森林総合研究所 森林資源化学研究領域
Detection of broad-leaf lignin in angiosperms by DFRC analysis (3)Naoyuki Matsui and Tatsuro Ohira
Forestry and Forest Products Research Institute, Wood Extractives Lab., 305-8687, Japan
Abstract:
The DFRC (Derivatization Followed by Reductive Cleavage) analysis can be used to detect
lignin specifically from tree leaves, since it gives C6-C3 type degradation products by the cleavage ofarylether linkages of lignin, excluding other (poly)phenolic substances. In this study, the distribution of lignin in
beech leaf was investigated in detail to find out the heterogeneity in lignin composition. Leaf vein separated
from beech leaf contained lignin with low S/G ratio, and other blade tissue had apparently syringyl-rich lignin.
The hypothesis that these syringyl lignin in leaf tissue has some defensive roles against light stress was deniedby the results of increased S-lignin in leaves under weaker light condition.
Keywords: leaf lignin, DFRC method, vein, stress defense
2016-P02
Tetra-n-butylphosphonium hydroxide を用いた新規リグニン定量法の開発
山田肇 1)、山下香菜 1)、宮藤久士 2)、大野弘幸 3)、山田竜彦 1)
1)
森林総合研究所、2)京都府立大、3)東京農工大
A novel lignin quantitative analysis using tetra-n-butylphosphonium hydroxide
Hajime Yamada1), Kana Yamashita1), Hisashi Miyafuji2), Hiroyuki Ohno3), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, Japan, 2)Kyoto Prefectural University, Japan,
3)
Tokyo University of Agriculture and Technology, Japan
Abstract:
Tetra-n-butylphosphonium hydroxide (TBPH, [P4,4,4,4]OH) is a kind of ionic liquids, and known
to have the whole wood dissolution ability. In this study, TBPH was introduced to determine lignin content incedar wood. An analytical procedure of the TBPH method was developed, and its practical reliability wasinvestigated. A series of compression cedar wood meal and 60% TBPH aqueous with peroxide were mixed in a
glass tube and treated in an autoclave for 3 h at 121 ºC. After the treatment, solution was diluted with alkaline
water-methanol mixture, and precipitation of carbohydrates was removed by centrifugation. 280nm UV
absorptions of the TBPH solution was measured, and lignin contents were calculated with the lignin coefficient26.7 l g-1 cm-1. Lignin contents determined by the TBPH method showed good correlation (R2=0.78) with thoseby the Klason method. This correlation factor was nearly the same level as that of the acetyl bromide method(R2=0.71). In total, the TBPH method could be a novel lignin quantitative analysis with good reliability, safety,
and time & labor efficiency.
Keywords: ionic liquid, TBPH method, Klason method, acetyl bromide method, multi-sample analysis
2016-P03
天然リグニン中の β—β（レジノール）構造の結合様式
安藤大将、中坪文明、矢野浩之
京都大学 生存圏研究所
The bonding sites to β-β substructure in natural lignin
Daisuke Ando, Fumiaki Nakatsubo, Hiroyuki Yano
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract:
A β-β substructure accounts for about 10 % of lignin. In biosynthesis, the β-β substructure isformed only from the coupling of monolignols at the β-position, then in this case, lignin polymerization fromthis structure continue to two directions by further couplings. Then, in our previous research, it was reported thatthe β-β substructure played an important role in the bonding sites between lignin and xylan. It is considered thatthe information about the β-β substructure in lignin molecules is important for the elucidation of lignin chemical
structures such as LCC. In this study, the natural lignin was degraded and the obtained degradation products
were analyzed by LC-MS for considering whether the β-β substructure is in the molecule or at end of themolecule. In the degradation of lignin, the β-β substructure remained because β-O-4 linkages in MWL were613

selectively cleaved by the γ-TTSA method. When the degradation products were monitored with mass
chromatograms for m/z 419 and m/z 573, syringaresinol and syringaresinol monotosylate,derived from the β-β
substructure in MWL, were found. This result shows that the β-β substructure in natural lignin exists not only inthe molecule but also at the end of the molecule.
Keywords: β-β substructure, LC-MS, MWL, syringaresinol
2016-P04
トウモロコシ穂軸の各形態部位の構造解析
髙田昌嗣、鈕鋭、南英治、坂志朗
京都大学大学院エネルギー科学研究科
Structural analyses of three morphological regions of corn (Zea mays) cob
Masatsugu Takada, Rui Niu, Eiji Minami, Shiro Saka
Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan
Abstract:
Corn (Zea mays) cob is composed of three morphological regions: chaff, woody ring and pith.
In this study, the cell wall components in these morphological regions were characterized. It was found that thechemical compositions in three regions were relatively similar, and that hemicellulose was the main component
and the lignin contents were in a range between 15 and 20%. Through the alkaline nitrobenzene oxidation
analysis, lignin in all regions was composed of guaiacyl, syringyl and p-hydroxyphenyl lignins, while theirratios were different. Furthermore, the amounts of ferulic acid and p-coumaric acid, which associate with cornlignin, are different between three regions. Accordingly, it seems that there are some differences in the lignin
structure among three morphological regions.
Keywords: cinnamic acids; corn cob; hemicellulose; alkaline nitrobenzene oxidation; morphologicalregions
2016-P05
高等植物の光屈性反応における光照射側組織での成長抑制メカニズム
都築 萌 1)、Nudtanicha Chaithongsri1）、繁森 英幸 2）、山田 小須弥 2)
1)
筑波大・院・生命環境、2)筑波大・生命環境系
Regulation of phototropic response in the early stage by blue light-mediated growth inhibitors
Megumi Tsuzuki1), Nudtanicha Chaithongsri1), Hideyuki Shigemori2), Kosumi Yamada2)
1)
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan, 2) Faculty of Life andEnvironmental Sciences, University of Tsukuba, Japan
Abstract:
The growing shoot of plant seedlings always bend towards the light source. This phenomenon is
known as phototropism. This mechanism has been believed as the result of light-mediated lateral redistributionof auxin (Cholodny-Went theory). On the other hand, the second model which is generated by light-mediatedgrowth inhibition has also been proposed in the early stage of phototropism (Bruinsma-Hasegawa theory). In
this research, we examined the inhibitory mechanism of shoot growth regulated by light-induced growth
inhibitors in pea and maize seedlings. The activity of inhibitors against the auxin-induced shoot elongation andthe induction of cell-wall stiffness will be discussed.
Keywords: auxin antagonist; cell-wall stiffness; lignin accumulation; maize, pea; phototropism
2016-P06
二次壁肥厚を促進するイネ転写因子 OsSWN1 を過剰発現するシロイヌナズナ cad-c/cad-d 二重変異体の解析諾恩達古拉(ノンダグラ)1)、坂本真吾 2)、光田展隆 2)、梶田真也 1)
1)
東京農工大学大学院 BASE、2)産業技術総合研究所 生物プロセス研究部門
Analysis of Arabidopsis cad-c / cad-d double mutant overexpressing the rice transcription factor OsSWN1 thatenhances secondary cell wall thickening
Nuoendagula1), Shingo Sakamoto2), Nobutaka Mitsuda2), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, 2) Bioproduction Research Institute, National Institute of Advanced
Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8566, Japan
Abstract:
Second-generation biofuels and biomaterials produced from non-food lignocellulose biomass
are seen as a good prospect, and rapidly increasing concern due to the depletion of petroleum resources andrelated environmental issues. Typically, most of the lignocellulosic biomass is comprised of cellulose,614

hemicellulose and lignin. Cellulose and hemicellulose are major structural components of plant cell wall andassumed to be converted for biofuels and biomaterials. Whereas, lignin is complex polymer and cross-links withcellulose and hemicellulose. Effectively removal of lignin is considered as the crucial step for preparing ofcellulosic ethanol from lignocellulosic biomass. NAC Secondary wall Thickening factors (NST) can effectively
enhance the secondary cell wall formation. Previous study inferred that except for the vascular vessels, thesecondary wall thickenings are quelled by knockout of the two genes NST1 and NST3 in Arabidopsis [1].
OsSWN1 in rice is the orthologue of the NSTs in Arabidopsis. Overexpression of OsSWN1 in nst1 nst3 double
mutant of Arabidopsis driven by the NST3 promoter showed that, secondary wall thickenings are observed inpith cells and also in interfascicular fibers of inflorescence stems [2]. When OsSWN1 gene overexpressing in
poplar plants, secondary wall thickenings are significantly facilitated compared to wild type plants [3]. In thisstudy, for further application, we analyzed the Arabidopsis cad-c / cad-d double mutant overexpressing
OsSWN1.
Keywords: Arabidopsis thaliana; secondary cell wall; lignin; OsSWN1
2016-P07
種子散布能力に関する果実二型をもつ海岸植物クサトベラ, —成熟段階ごとの果実形態の比較—
栄村奈緒子 1)、内貴章世 2)、梶田忠 2)、工藤洋 1)
１）
京都大学生態学研究センター、２）琉球大学熱帯生物圏研究センター
Abstruct:
Scaevola taccada is a coastal shrub species. This species has an unique characteristic thathaving two morphs of fruits adapted to two distinct dispersal modes. (1) C-morph fruits have pulp and corklayer and are dispersed by water and frugivorous birds and (2) NC-morph fruits have only pulp layer and are
dispersed only by birds. This cork layer of C-morph fruit consists mainly of lignin. In order to identify thecritical fruit developmental times of C-and NC-morph fruit, the developmental time of lignin deposition of thecork layer was studied by staining lignin with phloroglucinol-HCl solution and was observed with lightmicroscope.
Keywords: fruit; dimorphism; lignin; seed dispersal
2016-P08
CRISPR/Cas9 システムを用いたコニフェルアルデヒド 5-ヒドロキシラーゼ機能欠損イネの作出
武田ゆり 1)、鈴木史朗 1)、飛松裕基 1)、山村正臣 1)、坂本正弘 2)、刑部敬史 3)、梅澤俊明 1)
1)
京都大学生存圏研究所、2)京都大学大学院農学研究科、3)徳島大生物資源産業学部
Generation of a loss-of function mutant of CONIFERALDEHYDE 5-HYDROXYLASE gene in Oryza sativa
using the CRISPR/Cas9 system
Yuri Takeda1), Shiro Suzuki1), Yuki Tobimatsu1), Masaomi Yamamura1), Masahiro Sakamoto2), Keishi Osakabe3),
Toshiaki Umezawa1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan,
2)
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan, 3)Faculty of Bioscienceand Bioindustry, Tokushima University, Kuramoto-cho, Tokushima 770-8503, Japan
Abstract:
Aromatic composition of lignin greatly affects usability of lignocellulosic biomass andtherefore has been one of the primary targets of cell wall engineering studies. We previously reported that
RNAi-mediated down-regulation of a rice gene encoding CAld5H (OsCAld5H1) leads augmentation of G lignin
units in rice cell walls. As G-rich lignins display higher calorific values than that of S-rich lignins, increase of G
lignin units may contribute to enhancing combustion properties of biomass. On another front, the CRISPR/Cas9
genome-editing system has proven to be a powerful tool for efficient targeted mutagenesis. In this study, we
attempted to generate OsCAld5H1 knock-out mutant rice using the CRISPR/Cas9 system. Three single guide
RNAs (sgRNAs) were designed to target distinct sites of OsCAld5H1, and incorporated into the Cas9-sgRNA
expression vector. After Agrobacterium-mediated transformation, we obtained rice T0 generation with
anticipated mutations. The majority of the T0 genotype, however, were chimeric or heterozygous for
OsCAld5H1 mutation. Plants homozygous for OsCAld5H1 mutation were then successfully isolated from T 1
generation plants.
Keywords: lignin; Oryza sativa; coniferaldehyde 5-hydroxylase; ferulate 5-hydroxylase; CRISPR/Cas9
system2016-P09
Transcriptional analysis of poplar CWPO-C in different cell types and organs
Diego Yoshikay1), Kaori Ohira1), Jun Shigeto2), Yuji Tsutsumi2)
615

1)

Forest Chemistry and Biochemistry, Kyushu University, Fukuoka, Japan, 2)Department of Forest and Forest
Products Sciences, Kyushu University, Fukuoka, Japan
Abstract:
Cationic cell-wall-bound peroxidase (CWPO-C), a class III peroxidase in Populus alba, hasbeen considered to play a role in the lignification process. In order to promote better understanding about
CWPO-C functions, detailed expression analysis of this peroxidase using laser microdissection and expression
quantification tools were performed. It was shown that cells did not express CWPO-C in cambium, but it did incortex cells. Also CWPO-C expression was observed in apical meristem to some extent, thus indicating to be
involved in growth and cell elongation; suggesting a new aspect to the role of CWPO-C.
Keywords: poplar; peroxidase; laser microdissection; gene expression; GUS reporter gene2016-P10
ゼロから創製する新しい木質の開発
坂本真吾、光田展隆
産業技術総合研究所 生物プロセス研究部門
New wood production in plant without wood formation
Shingo Sakamoto, Nobutaka Mitsuda
Bioproduction Research Institute, National Institute of Advances Industrial Science and Technology (AIST),Japan
Abstract:
Plant cell wall, especially lignocellulose enriched in secondary cell wall, provides physicalrigity and also has a large potential as a resource for the next-generation biofuel and biomaterials. However, its
recalcitrance hampers the industrial use and therefore, the development of inovative technogy to improve it isdesired. In this study, we expressed chimeric activators and chimeric repressors of ca. 300 transcription factors
in Arabidopsis nst1-1 nst3-1 double mutant, which lacks secondary cell walls in fiber cells, under the control of
the NST3 promoter. Some resultant transgenic plants reconstituted different cell wall from wild-type secondarycell wall like the striated cell wall similar to vessel element, abnormally and heavily lignified cell wall, andlignin-less cell wall in interfascicular fiber cells. Expression pattern of secondary wall associated genes andmonosaccharide composition in these reconstituted lines were different from those of wild type even in the casewhen the reconstituted secondary cell wall looked similar to that in wild type, suggesting that these cell walls
are reconstituted differently from wild type through partial activation of regulatory network of secondary cellwall formation. Using some factors identified in this screening, we successfully established the strategy toreinforce wood formation, that to produce easily-extractable cellulose, and that to produce cell wall without
crystalline-cellulose. This study demonstrates that our approach is powerful to identify the novel transcription
factors which regulates cell wall formation and also provides the potential tool to produce artificial tailor-madecell walls with novel traits for the biofuel and biomaterial production.
Keywords: Artificial cell wall; nst1 nst3 double mutant; transcription factor; wood reinforcement.
2016-P11
Contribution of host lignin on haustorium induction and host defence against obligate parasitic plant Striga
hermonthica and facultative parasitic plant Phtheirospermum japonicum
Songkui Cui1,2), Yuki Tobimatsu3), Yuri Takeda3), Toshiaki Umezawa3), Simon Saucet2), Ken Shirasu2), Satoko
Yoshida1,2)
1)
NAIST BioScience, 8916-5 Takayama cho, Ikoma city, Nara Prefecture, 630-0192 Japan, 2)RIKEN CSRS,Japan, 3)Kyoto Univ, Japan
Abstract:
As one of major constitutes of secondary cell wall, lignins provide plants with physical strengthand rigidity for maintaining proper structure and physiology. Meanwhile, lignins from host plants are alsochemical targets for parasitic plants to find and attack host through formation of a specialized organ, named
haustorium. The aim of this study is to understand to what extent host lignin compounds contribute to theformation of haustorium as well as host resistance against different parasitic plants. As a material, we used afacultative root parasite P. japonicum and obligate root parasite S. hermonthica. First, haustorium induction
assay was performed by treating parasitic plants with monolignols, quinones and flavonoids. For both parasitic
plants, H type monolignols are inactive whereas S type monolignols are active haustorium inducer. Interestingly,
ferulic acid, which belongs to G type monolignol is active only in S. hermonthica. In addition, a flavonoid
aglycon, peonidin induces haustorium only in S. hermonthica. These suggest that S. hermonthica has a broader
spectrum of chemicals for haustorium formation. In parallel, host plants (Nipponbare rice) with altered ratio of
G and S lignin composition were generated by genetic modification of F5H gene, which encodes
ferulate-5-hydroxylase, a cytochrome P450-dependent monooxygenase (P450). These transgenic rice plants616

were tested for haustorium induction and host susceptibility/resistance assay in order to address the importanceof G and S lignin composition in host plants with regard to host defense against parasitic plants. The reductionin S lignin in rice host resulted in decreased induction of haustoria in P. japonicum, and increased S lignin
induced more haustoria. On the other hand, altered ratio of S and G lignin did not exhibit any difference of thehaustorium induction against S. hermonthica. Unexpectedly, changed ratio of G and S lignin caused host plants
more susceptible to S. hermonthica at the later stage of infection. In general, we found a consistency between invitro and in vivo haustorium induction. Our study demonstrates a similar but yet parasite-specific perception oflignin compounds as haustorium inducer and highlight the importance of host lignin for parasitic plant infection.
Keywords: parasitic plant; haustorium; Striga; Phtheirospermum; host defense; lignin; cell wall
2016-P12
代謝工学的改変によるケイ皮酸モノリグノール経路の進化過程の考察
古畑美帆 1，杉山結郁 1，岡澤敦司 1，西浜竜一 2，山岡尚平 2，河内孝之 2，太田大策 1
1
大阪府立大学大学院生命環境科学研究科，2 京都大学大学院生命科学研究科
Metabolic redesign of the cinnamate/monolignol pathway in Marchantia polymorpha by transgene expressionof CYP98A3, CYP84A1, and hydroxycinnamoyl CoA transferase from Arabidopsis.
Miho Furuhata1, Yui Sugiama1, Atushi Okazawa1, Ryuich Nishihama2, Shohei Yamaoka2, Takayuki Kohchi2,
Daisaku Ohta1
1
Graduate School of Life and Environmental Sciences, Osaka Prefecture University, 2Laboratory of Plant
Molecular Biology, Graduate School of Biostudies, Kyoto University
Abstract:
Comparison of genome sequences of Marchantia, Physcomtrella, and Arabidopsis revealed thepresence of several key genes in the upstream part of cinnamate/monolignol pathway in the moss. Those include
the cytochromes P450, cinnamate 4-hydroxylase (CYP73A) and p-coumarate 3’-hydroxylase (C3’H, CYP98A),
and hydroxycinnamoyl CoA:shikimate/quinate hydroxycinnamoyl transferase (HCT) ， while anotherdownstream key enzyme CYP84A (F5H, ferulate 5-hydroxylase) is missing. We have expressed recombinant
CYP98A (PpCYP98A) and HCT (PpHCT) from Physcomitrella patens and found that PpHCT catalyzes thehigher plant type reaction with shikimate and quinate as the substrates. However, PpCYP98A failed to exhibit
the C3’H activity with the PpHCT reaction products (e.g., p-coumaroyl shikimate). These results suggested thatthe endogenous substrates of the moss HCTs are different from those of the higher plant HCTs and that the moss
CYP98A may assume unidentified roles aside from cinnamate/monolignol pathway. In other words, theevolution of the lignin biosynthesis could be understood, at least in part, through the speciation of CYP98A
enzymes to be capable of C3’H reaction. If this was actually the case, transgene expression of the higher C3’H,
F5H, and HCT from higher plants should have crucial impact on the moss metabolism stemming fromphenylpropanoids. Here, we report the generation and characterization of transgenic M. polymorpha expressing
Arabidopsis CYP98A3 (C3’H), HCT, and CYP84A1 (F5H) in different combinations.
Keywords: cinnamate/monolignol pathway, moss, evolution, cytochrome P450, metabolic redesign
2016-P13
フェニルプロペン香気成分の生合成に関わるモノリグノールアセチル化酵素遺伝子の単離と機能解析
肥塚崇男１）、鈴木史朗２）、飛松裕基２）、宮本託志２）、梅澤俊明２）、松井健二１）
１）
山口大学大学院創成科学研究科、２）京都大学生存圏研究所
Isolation and characterization of monolignol acetyltransferase genes capable of biosynthesizing volatile
phenylpropenes
Takao Koeduka1), Shiro Suzuki2), Yuki Tobimatsu2), Takuji Miyamoto2), Toshiaki Umezawa2), Kenji Matsui1)
1)
Graduate School of Sciences and Technology for Innovation, Yamaguchi University,1677-1 Yoshida,
Yamaguchi-shi, Yamaguchi 753-8515, Japan, 2)Research Institute for Sustainable Humanosphere, Kyoto
University, Gokasho, Uji, Kyoto, 611-0011, Japan
Abstract:
Acetyl monolignols are key precursors for small molecular volatile phenylpropenes andmacromolecular lignin in some plant species. Despite many previous investigations on the
cinnamate/monolignol pathway, there are few reports regarding the isolation of monolignol acetyltransferases
and the metabolic engineering of monolignol acetylation in plants. In this study, we searched monolignol
acetyltransferase genes in a phenylpropene-producing plant, dill (Anethum graveolens). In addition, we
overexpressed petunia (Petunia hybrida) coniferyl alcohol acetyltransferase (PhCFAT) with or without petunia
eugenol synthase (PhEGS) in hybrid aspen. We found two candidate monolignol acetyltransferase genes in dill
EST databases. The expression of a candidate gene was correlated with the accumulation of dillphenylproepenes, myristicin and dillapiole. In leaves of the aspen plants overexpressing PhCFAT and PhEGS,
617

the amounts of eugenol and its glycoside increased up to 7-fold and up to 22-fold higher compared to wild type.
Acetylated monolignol units were also significantly increased in the xylem of transgenics.
Keywords: phenylalanine, aromatic compound, herb, antifungal activities, phenylpropenes
2016-P14
Sphingobium sp. SYK-6 株のシリンギル型リグニン由来化合物代謝に関わるアルデヒドデヒドロゲナーゼ遺伝子の同定と機能解析
上村 直史 1)、後藤 隆之 1)、高橋 健司 1)、山本 裕子 1)、笠井 大輔 1)、大塚 祐一郎 2)、中村 雅哉 2)、片山義博 3)、福田 雅夫 1)、政井 英司 1)１）
長岡技術科学大学・生物、２）森林総合研究所、３）日本大学・生物資源科学
Identification and characterization of the aldehyde dehydrogenase genes crucial for the syringyl lignin
catabolism in Sphingobium sp. strain SYK-6
Naofumi Kamimura1), Takayuki Goto1), Kenji Takahashi1), Yuko Yamamoto1), Daisuke Kasai1), Yuichiro
Otsuka2), Masaya Nakamura2), Yoshihiro Katayama3), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan, 2)Forestry andForest Products Research Institute, Tsukuba, Ibaraki, Japan, 3)College of Bioresource Sciences, Nihon
University, Fujisawa, Kanagawa, Japan
Abstract:
Sphingobium sp. strain SYK-6 is capable of catabolizing various lignin-derived aromatics withguaiacyl and syringyl nuclei via vanillin (VN) and syringaldehyde (SN), respectively. An aldehyde
dehydrogenase (ALDH) gene, ligV, essential for the conversion of VN was previously isolated from SYK-6, andgenetically characterized. In this study, we aimed to identify the ALDH gene responsible for the conversion of
SN from the 23 ALDH genes in SYK-6. All of these ALDH genes were expressed in Escherichia coli, and we
found that nine gene products including LigV exhibited SN oxidation activity. Among these genes, SLG_28320(desV) and ligV were transcribed in significantly higher levels in a constitutive fashion in SYK-6 cells.
Disruption of desV in SYK-6 cells resulted in significant decreases in the ability to grow on and convert SN.
The Kcat/Km value of purified DesV measured for SN was 730-fold higher than that of LigV. These results
clearly demonstrate that desV plays a main role in the conversion of SN in SYK-6.
Keywords: bacteria, benzaldehyde, genome, biorefinery, microbial lignin valorization
2016-P15
Sphingobium 属細菌のフェニルクマラン型化合物代謝に関与する lignostilbene α,β-dioxygenase 遺伝子の同定と機能解析
廣瀬 優作１）、高橋 健司１）、上村 直史１）、菱山 正二郎 2）、笠井 大輔１）、片山 義博 3）、福田 雅夫１）、政井英司 1）
１）
長岡技術科学大学・生物、２）森林総合研究所、３）日本大学・生物資源科学
Isolation and characterization of the lignostilbene ,-dioxygenase genes involved in the catabolism of
dehydrodiconiferyl alcohol in Sphingobium sp. strain SYK-6
Yusaku Hirose1), Kenji Takahashi1), Naofumi Kamimura1), Shojiro Hishiyama2), Daisuke Kasai1), Yoshihiro
Katayama3), Masao Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan, 2)Forestry andForest Products Research Institute, Tsukuba, Ibaraki, Japan, 3)College of Bioresource Sciences, Nihon
University, Fujisawa, Kanagawa, Japan
Abstract:
The objective of this study is to identify and characterize all the Sphingobium sp. SYK-6 genes
involved in the catabolism of a phenylcoumaran-type compound, dehydrodiconiferyl alcohol (DCA). In SYK-6
cells, the alcohol groups at the γ-carbon of the B-ring and A-ring side chains of DCA were oxidized in asequential order to the carboxyl groups to generate DCA-CC. DCA-CC was decarboxylated to produce DCA-S,
followed by the production of 5-formylferulate and vanillin by the cleavage of the Cα-Cβ double bond of the
A-ring side chain of DCA-S. In a previous study, we isolated and characterized the genes involved in theconversion of DCA into DCA-CC. In this study, we investigated the genes responsible for the conversion of
DCA-S. Previously, four lignostilbene α,β-dioxygenases (LSD) were reported as enzymes capable of converting
DCA-S in Sphingomonas paucimobilis TMY1009. Here, we found eight LSD genes in the SYK-6 genome.
Disruption of these genes in SYK-6 suggested that three lsd genes, lsdB, lsdD, and lsdE, play important roles inthe degradation of DCA-S. These genes were expressed in E. coli and Pseudomonas putida, and the resultant
gene products were purified by Ni-affinity chromatography. While LsdD converted DCA-S into vanillin and
5-formylferulate, LsdB and LsdE showed almost no activity toward DCA-S. These results may suggest that618

LsdB and LsdE function as a heterodimer.
Keywords: dilignol, β-5, biodegradation, catabolic pathway
2016-P16
Sphingobium sp. SYK-6 株における acetovanillone 変換酵素遺伝子群の機能と転写制御
竹浪 寛樹 1)、樋口 雄大 1)、上村 直史 1)、笠井 大輔 1)、片山 義博 2)、福田 雅夫 1)、政井 英司 1)
１）
長岡技科大・生物、２）日大・生資科
Characterization of the acetovanillone catabolic genes and their transcriptional regulation in Sphingobium sp.
strain SYK-6
Hiroki Takenami1), Yudai Higuchi1), Naofumi Kamimura1), Daisuke Kasai1), Yoshihiro Katayama2), Masao
Fukuda1), Eiji Masai1)
1)
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan, 2)
College of Bioresource Sciences, Nihon University, Fujisawa, Kanagawa 230-0045, Japan
Abstract:
In Sphingobium sp. SYK-6 cells, guaiacylglycerol-β-guaiacyl ether (GGE) is catabolized tovanilloyl acetic acid (VAA). It has been suggested that VAA was converted to vanillate through reactions that
require coenzyme A. On the other hand, it is known that VAA is transformed to acetovanillone (AV) by
nonenzymatic decarboxylation. Recently, we found that SYK-6 degraded AV via VAA, and the acvABCDEF
genes, which respectively encode similar proteins of phenyl phosphate synthase 1, phenyl phosphate synthase 2,
biotin carboxyl carrier protein, biotin carboxylase, carboxyltransferase, and sugar phosphatase of the HAD
superfamily, were involved in the carboxylation of AV. In this study, we aimed to characterize the AV
decarboxylase and the transcriptional regulation of the acv genes. Each acv mutant was incubated with AV, andtheir abilities to convert AV were examined. This experiment indicated that acvA, acvB, acvC, acvD, and acvE
except acvF were essential for the conversion of AV in SYK-6. Due to the presence of acvR, which encodes an
AraC-type transcriptional regulator, just upstream of acvA, AcvR seemed to regulate the transcription of
acvABCDEF. Disruption of acvR in SYK-6 resulted in deficiencies in the growth on and the conversion of AV,
suggesting that AcvR positively regulates the acvABCDEF transcription.
Keywords: bacteria, carboxylation, acetovanillone
2016-P17
海底下嫌気性微生物群集のリグニン関連モノマー代謝
大田 ゆかり、前田 亜鈴悠、黒澤 佳奈子、市川 淳子、田角 栄二、井町 寛之、稲垣 史生
国立研究開発法人海洋研究開発機構
The metabolism of a lignin-related aromatic monomer by the anaerobic microbial community enriched fromcoal-bed below the seafloor
Yukari Ohta, Allyn H. Maeda, Kanako Kurosawa, Junko Ichikawa Eiji Tasumi, Hiroyuki Imachi, Fumio Inagaki
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Japan
Abstract:
An enriched methanogenic community from ~2-km-deep coal-bed samples below the seafloor
in the Pacific Ocean off Japan was examined for the metabolism of a lignin-related aromatic monomer,
syringaldehyde, under an anaerobic condition. Syringaldehyde was converted into syring acid, and then into
5-hydroxy vanillic acid and gallic acid. Bacterial and archaeal community analyses showed the dominance ofbacterium belonging to the three phyla, Firmicutes (class Clostridia), Cloloflexi (class Anaerolineae), andEuryarchaeota (class Methanobacteria, i.e. methanogenic archaea). This study will lead to a future
understanding for unknown microbial metabolic networks for lignin-derived aromatic compounds under theseafloor.
Keywords: anaerobic degradation, Clostridia, Cloloflexi, aromatic monomer, methanogenic community,
sub-seafloor,
2016-P18
海洋性細菌に由来するリグニン β-O-4 還元開裂酵素 GST4 の解析
嶋根康弘 1)、前田亜鈴悠 1)、塩谷美夏 1)、黒澤佳奈子 1)、市川淳子 1)、布浦拓郎 1)、山置佑大 2)、永田崇 2)、
片平正人 2)、高谷光 3)、吉田亮太 3)、中村正治 3)、渡辺隆司 4)、大田ゆかり 1)
1)
海洋研究開発機構、2)京都大学エネルギー理工学研究所、3)京都大学化学研究所、4)京都大学生存圏研究
所
Analysis of β-O-4 cleaving enzyme, GST4, from the marine bacterium, Novosphingobium sp. MBES04
619

Yasuhiro Shimane1), Allyn H Maeda1), Mika Shioya1), Kanako Kurosawa1), Jyunko Ichikawa1),
Takuro Nunoura1), Yudai Yamaoki2), Takashi Nagata2), Masato Katahira2), Hikaru Takaya3),
Ryota Yoshida3), Masaharu Nakamura3), Takashi Watanabe4), Yukari Ohta1)
1)Japan Agency for Marine-Earth Science and Technology, Japan, 2)Institute of Advanced Energy, Kyoto
University, Japan, 3)Institute for Chemical Research, Kyoto University, Japan, 4)Research Institute for
Sustainable Humanosphere, Kyoto University, Japan
Abstract:
The deep-sea marine bacterium, Novosphingobium sp. MBES04, isolated from a sunken wood
was capable of metabolizing the stereoisomers of β-O-4 lignin dimers into the respective monomers by
combination of multiple enzymes. GST4 is a glutathione-dependent β-etherase, and one of the key enzymes in
the pathway which selectively catalyzes reductive cleavage of β-O-4 aryl-ether bonds in lignin. In this study, we
compared the substrate binding mechanisms of GST4 with its homologues of LigF from Sphingobium sp. strain
SYK-6 and LigF-NA from Novosphingobium aromaticivorans. Substrate specificity analysis revealed that
GST4 is capable to accept a wide range of substrates compared to the others. Calculation of energy forintermolecularinteraction
betweenthethreemolecules(GST4,
glutathioneandα-(2-methoxyphenoxy)-β-hydroxypropiovanillone (MPHPV)) suggested the substrate recognition of GST4 wasdetermined by two different key rules of electrostatic interaction for glutathione and dispersion interaction for
MPHPV.
Keywords: lignin, Novosphingobium, glutathione-dependent β-etherase, FMO
2016-P19
海洋環境からの Guaiacylglycerol-β-guaiacyl ether - Cα 位酸化酵素の探索
前田 亜鈴悠、西 真郎、坪内 泰志、大田 ゆかり
国立研究開発法人海洋研究開発機構
Screening of guaiacylglycerol-β-guaiacyl ether – Cα-dehydrogenases from marine environment
Allyn H. Maeda, Shinro Nishi, Taishi Tsubouchi, Yukari Ohta
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Japan
Abstract:
A bacterial enzymatic cascade for β-O-4 reductive cleavage in lignin model dimers consists ofCα-dehydrogenases belonging to short-chain dehydrogenase/reductase (SDR) superfamily, β-etherases andglutathione-S-transferase (GST) superfamily, β-glutathione thioetherases (glutathione lyases). In this study,functional screenings of culturable bacteria isolated from sediments obtained from Kagoshima Bay revealed theexistence of a bacterium with oxidative activity for hydroxyl moiety at Cα (benzyl) position of
guaiacylglycerol-β-guaiacyl ether (GGGE). We conducted genome sequencing of the positive isolate designatedas strain YG1 to identify responsible genes of the activity. Two genes encoding Cα-dehydrogenases wereidentified using recombinantly expressed proteins.
Keywords: β-O-4 reductive cleavage, a marine bacterium, guaiacylglycerol-β-guaiacyl ether (GGGE),
Sphingobium sp., short-chain dehydrogenase/reductase (SDR)
2016-P20
リグノセルロース分解に関わる木材腐朽菌が産する酸化酵素の異種発現および構造活性相関解析
林孟宜 1,2)、近藤敬子 1)、永田崇 1, 2)、片平正人 1, 2)、
１）
京大・エネルギー理工学研究所、２）京大・エネルギー科学研究科
Heterologous expression and structure-activity relationship analysis of the oxidative enzymes from wood rotting
fungi that are involved in lignocellulose degradation
Meng-I Lin1,2), Keiko Kondo2), Takashi Nagata1,2), Masato Katahira1,2)
1)Institute of Advanced Energy, Kyoto University, Japan, 2)Graduate School of Energy Science, Kyoto University,
Japan
Abstract:
Fungi and their enzymes have been expected to provide milder means to extract lignin. Byutilizing fungal enzymes and their functionally improved variants, more efficient use of lignocellulose may beachieved. We have selected several different ligninolytic enzymes registered in Joint Genome Institute (JGI)
database and undertaken heterologous expression in E. coli. Three enzymes have been successfully expressedand purified in high yield with high stability and activity. The relationships between lignocellulose degradationand structure of these enzymes are under investigation. Our preliminary data shows that these three enzymes
have different activity property.
Keywords: lignocellulose; wood rotting fungi; ligninolytic enzyme; heterologous expression
2016-P21620

バイオマス細胞壁分解とオリゴ糖生成の促進に資する放線菌フェルラ酸エステラーゼ
裏地美杉, 万 クン, 畑中唯史
岡山県農林水産総合センター生物科学研究所
Streptomyces feruloyl esterase promotes enzymatic degradation of biomass and production of oligosaccharides
Misugi Uraji1), Kun Wan1), Tadashi Hatanaka1)
1)Institute for Biological Sciences, Okayama Prefectural Technology Center for Agriculture, Forestry, andFisheries, 7549-1 Yoshikawa, Kibi-chuo, Okayama 716-1241, Japan
Abstract:
Feruloyl esterase (FAE) is useful to produce a ferulic acid from plant cell walls of agricultural
biomass. Moreover, the FAE is one of important enzymes for degradation of plant cell walls in the process of
biofuel production. In this study, we investigated an enhanced effect of Streptomyces FAEs (R18 and R43) to an
enzymatic production of oligosaccharides and glucose from biomasses by carbohydrate-hydrolases, such as
Streptomyces xylanase/cellobiosidase STX-I, Streptomyces α-L-arabinofuranosidase STX-IV and a commercial
cellulase. By combining STX-I, STX-IV with R18 or R43, the contents of tri- to hexa-oligosaccharides thatconsist of hexose were increased from defatted rice bran and sugarcane bagasse. On the other hand, that of adi-oligosaccharide that consist of pentose was detected from corncob and sugarcane bagasse, and thedi-oligosaccharide from corncob was obviously increased by the combination with FAEs. A combination ofcommercial cellulase with R18 or R43 increased glucose production from corn bran and corncob but did notenhance that from defatted rice bran and sugarcane bagasse. These results suggest that Streptomyces FAEs effecton cell wall degradation accompanying oligosaccharides and glucose production, and the recipe of enzymes isimportant for production of functional materials from various agricultural biomasses.
Keywords: cinnamic acid, feruloyl esterase, saccharification, biomass, Streptomyces
2016-P22
NMR study on lignocellulose degradation by Coptotermes formosanus Shiraki
Didi Tarmadi1,2), Yuki Tobimatsu1), Masaomi Yamamura1), Takuji Miyamoto1), Toshiaki Umezawa1), Tsuyoshi
Yoshimura1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Japan, 2)Research Center for
Biomaterials, Indonesian Institute of Sciences, Bogor, Indonesia
Abstract:
Termites are effective in decomposing lignocellulose. Although degradation of polysaccharides
components has been extensively studied, lignin degradation in lignocellulose digestion by termite yet remains
unclear. In the present study, we applied modern NMR techniques to study lignocellulose degradation by alower termite Coptotermes formosanus Shiraki with emphasis on the fate of lignin polymers. Softwood(Japanese cedar), hardwood (Japanese beech), and grass (rice) cell walls were fed to C. formosanus, andlignocellulosic structures of faeces and original dietary cell walls were comparatively characterized using 2D
NMR techniques as well as various chemical methods. Our NMR and chemical analysis confirmed thatpolysaccharides were preferentially decomposed over lignins in digestion of all the three types of cell wallmaterials. However, it appeared that syringyl lignins were slightly depleted over guaiacyl lignins in digestion of
beech cell walls. It was also clearly observed that guaiacyl lignins as well as tricin flavonoid units were depleted
preferentially in digestion of rice cell walls. Distributions of major lignin inter-monomeric linkages wereslightly affected but overall similar between faeces and original cell walls. Our data suggest that C. formosanus
digestive system indeed removes part of lignin polymers along with polysaccharides upon lignocellulose
degradation but most likely has little ability to exert major impact on the major lignin linkage types such as β–
O–4, β–5, and β–β linkages.
Keywords: biodegradation, Coptotermes formosanus Shiraki, lignocellulose, NMR, termite digestivesystem2016-P23
ラッカーゼ-メディエーター処理によるタイロシンの分解と毒性除去
安藤亜季１）、米田夕子１）、西田友昭２）、河合真吾１）１）
静岡大院総合科学技術研究科農学専攻、２）静岡大名誉教授
Degradation and detoxification of tylosin by laccase-mediator system
Aki Ando1), Yuko Yoneda1), Tomoaki Nishida2), Shingo Kawai1)
1)Graduate School of Integrated Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan,
2)
Professor emeritus, Shizuoka University, Japan
Abstract:
The adverse effect from the residual of pharmaceuticals and personal care products (PPCPs) in
the wastewater on human health and the environment has become a matter of concern. Tylosin, a macrolide621

antibiotic, is used widely as a drug to treat infections for domestic animals, and it is found often as it is inseveral rivers and lakes all over the world. Considering the influences of tylosin to aquatic organisms, effective
techniques to remove and/or to decompose it from wastewater have been demanded. To degrade and to detoxifytylosin, the treatments by laccese and laccase-mediator system with 1-hydroxybenzotriazole were examined.
After treatment by laccase-mediator system, tylosin was not detected in the treatment solution, and the growth
inhibitions against Pseudokirchneriella subcapitata and Bacills subtilis of the treatment solution were reduced
significantly.
Keywords: ligninolytic enzyme, white rot fungi, bioremediation, laccase-mediator, PPCPs
2016-P24
13
C NMR 法による二量体モデル化合物分解機構の解析
中村亮太、米田夕子、河合真吾
静岡大学大学院総合科学技術研究科農学専攻
Degradation mechanism analysis of dimeric model compound using 13C NMR
Ryota Nakamura, Yuko Yoneda, Shingo Kawai
Graduate School of Integrated Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan
13
Abstract:
C Labeled lignin dimeric model compound, a guaiacyl unit linked to a syringyl one by β-O-4bond, was synthesized, and treated by laccase/1-hydroxybenzotriazole. Following the process of laccasegenerated reaction by 13C NMR, the oxidation at benzylic position and the cleavage of CαCβ bond of dimericmodel compound were observed. Veratric acid was determined as a reaction product, although it was not seen in
the laccase-generated reaction solution of the oxidized dimeric model compound product as a substrate.
Keywords: dimeric model, 13C NMR, laccase, bond cleavage, oxidation
2016-P25
Evaluations of antiviral activities of phenolic compounds in wood and bamboo vinegar toward production oflignin-derived bioactive compounds
Ruibo Li1), Ryo Narita1,2), Shinsuke Marumoto1,3), Hiroshi Nishimura1), Mitsuyoshi Yatagai4), Takashi Fujita2),
Takashi Watanabe1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, 2)Institute for Virus Research, Kyoto
University, 3)Joint Research Center, Kinki University, 4)Emeritus Professor of Tokyo University
Abstract:
Wood and bamboo vinegar (WBV), also called pyroligenous acid (PA), are made from smoke
generated during the process of wood charcoal production. Over 200 compounds have been found in wood andbamboo vinegars, which belong to different classes of organic compounds, aldehydes, ketones, alcohols, organic
acids, esters, derivatives of furan and pyran, phenolics, hydrocarbons, and nitrogen compounds. Anti-oxidation,
anti-inflammation, and anti-microbial activities of PAs have attracted more and more attentions in the recent
years1-2). It was suggested that phenolic compounds were responsible for anti-oxidation and anti-microbialactivities. Viruses threaten human’s health and cause huge economic loss. Therefore, it is urgent to find simple
and economic methods to control the outbreaks of virus. In our previous work, we found that bamboo vinegar(BV) from moso bamboo inhibited EMCV replication significantly. Phenol was identified as a major antiviralcompound in BV. In addition, acetic acid, which is the most abundant component in BV, showed synergistic
effects with phenol on the antiviral activities3). In wood and bamboo PAs, versatile phenolic compounds are
involved but their antiviral activities are not well studied. Therefore, this research aimed at elucidating antiviral
activities of phenol derivatives involved in wood and bamboo PAs.
Keywords: phenolic compounds, antivirus, wood and bamboo vinegar, pyroligneous acid, picornavirus;
2016-P26
Isoamericanol A from Jatropha curcas seed extract shows anti-cancer activity on human breast cancer cell
MCF-7 by induction of G2/M stage cell cycle arrest with prolonged treatment and disruption of regular spindle
formation with short-term treatment.
Ayako Katagi1), Li Sui1), Kazuyo Kamitori1), Toshisada Suzuki2), Takeshi Katayama2), Akram Hossain1), Chisato
Noguchi1), Youyi Dong1), Fuminori Yamaguchi1), Masaaki Tokuda1)
1)Faculty of Medicine, Kagawa University, Miki-cho, Kagawa 761-0793, Japan, 2)Faculty of Agriculture,
Kagawa University, Miki-cho, Kagawa 761-0795, Japan
Abstract:
Our study reports on the anti-carcinogenicity of isoamericanol A (IAA) as Jatropha curcas seedextract. The results showed that IAA is capable of inhibiting cell proliferation in a dose-dependent manner on
the human cancer cell lines of MCF-7, MDA-MB231, HuH-7, and HeLa. The molecular mechanisms of622

prolonged 25µg/ml IAA treatment on MCF-7 were initially investigated with DNA-microarray analysis, flow
cytometry, TUNEL assay, Western blot, and quantitative real-time PCR. The results showed increased
expression of BTG2 (B-cell translocation gene 2, p<0.05), p21 (p21WAF1/CIPI, p<0.05), and GADD45A (growtharrest and DNA-damage-inducible, alpha, p<0.001), in addition to decreased expression of CDK1
(cyclin-dependent kinase 1, p<0.05) and cyclins B1 (p<0.001) and B2 (p<0.001). These expressional changes
indicate an inhibition of the cyclin B/CDK1 complex, the major activator of G2/M cell cycle progression,
hindering further cancer cell growth. Later, we used immunofluorescence staining of aurora B kinase, α-tubulin,
and the chromosome to test the effects of short-term IAA treatment on MCF-7. In comparison to the prolonged
IAA treatments, we discovered that the short-term treatment impaired cell division by inducing irregular spindle
forms. These findings suggest IAA could have the potential to halt cancer cell growth by at least two distinct
mechanisms: G2/M cell cycle arrest and improper cell division.
Keywords: Neolignan; BTG2; p21WAF1/CIPI; GADD45A; CDK1/cyclin B; mitosis
2016-P27
生物代謝による化学変換のためのリグニンの高温高圧水処理
佐野凜作 1)、島田五百里 1)、福長博 1)、高橋伸英 1)、 二階堂満 2)、上村直史 3)、
政井英司 3) 、長田光正 1)
１）
信州大・繊維、２）一関高専・物化工、３）長岡技科大・生物
High-temperature liquid water treatment of lignin for chemical conversion through microbial catabolism
Rinsaku Sano1), Iori Shimada1), Hiroshi Fukunaga1), Nobuhide Takahashi1), Mitsuru Nikaido2), Kamimura
Naofumi3), Eiji Masai3), Mitsumasa Osada1)
1)Department of Chemistry and Materials, Faculty of Textile Science and Technology, Shinshu University,2)
Department of Chemical Engineering, National Institute of Technology, Ichinoseki College, 3)Department of
Bioengineering, Nagaoka University of Technology
Abstract:
Lignin was treated by high-temperature liquid water using a semi-batch type reactor (218～290ºC, 25 MPa, 3.0 g/min). The ethyl acetate-soluble products were analyzed by size exclusion chromatography(SEC) and gas chromatographic-mass spectrometric (GC-MS). As a result, lignin was degraded to low moleculeweight products and was converted to phenolic compounds for microbial catabolism.
Keywords: hydrothermal, supercritical water, hot compressed water, SYK-6, vanillin
2016-P28
S 核、G/S 核 β-O-4 型オリゴマーの合成とその NHPI 間接電解酸化
平野 義貴 1)、飛松 裕基 2)、上高原 浩 1)、高野 俊幸 1)
1)
京大院農、2)京大生存研
Synthesis and NHPI-mediated indirect electrochemical oxidation of S and G/S type β-O-4 model oligomer
Yoshitaka Hirano1), Yuki Tobimatsu2), Hiroshi Kamitakahara1), and Toshiyuki Takano1)
1)
Graduate School of Agriculture, Kyoto University, Japan. 2)Research Institute for Sustainable Humanosphere,
Kyoto University, Japan
Abstract:
Syringyl and guaiacyl/syringyl type β-O-4 model oligomers were newly synthesized (yields:
69.2, 78.9%, DPn = 5.90, 5.32 on 1 g scale) and electrochemically oxidized in the presence of a redox mediator,
N-hydroxyphthalimide (NHPI). Our NMR and GPC data suggested that α-positions of β-O-4 structure in both S
and G/S-type oligomers were efficiently and selectively oxidized to the carbonyl group. Next, as a preliminary
experiment for the subsequent reductive cleavage of α-keto-β-O-4 ether bond by electrochemistry, α-keto-β-O-4
type dimeric model compound was subjected to direct electrochemical reduction. We identified propiophenone
derivative and guaiacol as the electrolysis products. This supports our contention that α-keto-β-O-4 ether bond
could be reductively cleaved via direct electrolysis.
Keywords: β-O-4 linkage, Cα carbonylation, hardwood, lignin model compound, aryl ketone
2016-P29
第四級アルキルアンモニウムヒドロキシドを用いたリグニン分解におけるアンモニウムカチオンの役割
溝口晃平 1)、細谷隆史 1)、吉岡康一 1)、宮藤久士 1)、梅澤俊明 2)、大野弘幸 3)、山田竜彦 4)1)
京府大院生環、2)京大生存研、3)東京農工大院工、4)森林総研
Role of ammonium cations in degradation of lignin with quaternary alkyl ammonium hydroxides
Kohei Mizoguchi1), Takashi Hosoya1), Koichi Yoshioka1), Hisashi Miyafuji 1), Toshiaki Umezawa2), Hiroyuki
Ohno3), Tatsuhiko Yamada4)
623

1)

Graduate School of Life and Environmental Sciences, Kyoto prefectural University, Japan, 2)Research Institutefor Sustainable Humansphere, Kyoto university, Japan, 3)Graduate School of Engineering, Tokyo University ofAgriculture and Technology, Japan, 4)Forestry and Forest Products Research Institute, Japan
Abstract:
In alkaline degradation of lignin, selectivity of the degradation toward low MW compounds,
especially vanillin, is considerably improved by the presence of the tetrabutyl ammonium cation. In thispresentation, we examined degradation of a non-phenolic β-O-4 type model compound in aqueous solutions ofquaternary ammonium hydroxides having C1-C6 alkyl chains and NaOH. Selectivity toward vanillin became
higher by the change of the cation from Na+ to NMe4+. Elongation of the alkyl chain from C1 to C6 madefurther improvements with similar performance being exhibited by the C3-C6 cations. Quantum chemical
calculations on the ammonium cations indicated that the selectivity toward vanillin was inverse proportional tothe positive charge localized on the methyl end of the cations, that hydrophobicity of the ammonium cation
plays important roles in determination of the selectivity.
Keywords: degradation, quaternary ammonium, alkali, model compounds
2016-P30
テトラブチルアンモニウムヒドロキシド 30 水和物を用いたリグニン分解における各種添加剤の影響
山本康平 1)、細谷隆史 1)、吉岡康一 1)、宮藤久士 1)、大野弘幸 2)、山田竜彦 3)1)
京府大院生環、2)東京農工大院工、3)森林総研
Influence of additives on degradation of lignin with tetrabutylammonium hydroxide-30H2O
Kohei Yamamoto1), Takashi Hosoya1), Koichi Yoshioka1), Hisashi Miyafuji1), Hiroyuki Ohno2), Tatsuhiko
Yamada3)
1)
Graduate School of Life and Environmental Sciences, Kyoto prefectural University, Japan,
2)
Graduate School of Engineering Department, Tokyo University of Agriculture and Technology, Japan,
3)
Forestry and Forest Products Research Institute, Japan
Abstract:
In tetrabutylammonium hydroxide-30H2O (NBu4OH·30H2O), lignin is degraded selectively into
low MW compounds, especially vanillin. This study addresses influence of several additives on the degradationof soda lignin in NBu4OH·30H2O. Two types of additives were tested: oxidants such as PyClCrO3, PyFCrO3,
NBu4ReO4, NPr4RuO4, NBu4ClO4, (NBu4)2SO4, (NBu4)2Cr2O7 and nitrobenzene, and a H-donor,
2,4-dihydronaphthalene (tetraline). The oxidants greatly accelerated the degradation, but scarcely affected the
maximum vanillin yield, suggesting that the property of NBu 4OH·30H2O advantageous for vanillin production
was not exploited in the presence of the oxidants. On the other hand, tetraline considerably increased vanillinyield without affecting the reaction time necessary to achieve the maximum vanillin yield. This suggests that theeffect of NBu4OH·30H2O as a selectivity enhancer of vanillin was maintained in the presence of tetraline andthe H-donor suppresses radical-induced side reactions.
Keywords: degradation, vanillin, oxidants, H-donors, tetrabutylammonium hydroxide2016-P31
Copper complex-peroxide reaction producing vanillin from lignin in woody biomass accelerated by microwave
Chen Qu1,3), Keigo Ito1,3), Tomohiko Mitani1,3), Keiichiro Kashimura 2,3), Takashi Watanabe1,3)
1)Research Institute for Sustainable Humanosphere, Kyoto University, 2)Information Technology Section,
General Education Division, College of Engineering, Chubu University, 3)Crest, JST
Abstract:
Vanillin and vanillic acid are degradation products from lignin and attract a great deal of interest
as key components for synthesizing thermostable biopolymers. We investigated production of vanillin andvanillic acid from woody biomass, and found a microwave-accelerated copper-peroxide reaction producing
these monomers in a high yield from woody biomass. In order to understand the mechanism for the microwave
effect, the reaction was applied to lignin β-O-4 dimer model compounds, and the degradation products wereanalyzed comparatively using microwave irradiation and conventional heating.
Keywords: lignin, microwave, vanillin
2016-P32
疎水性アルコールを用いた植物バイオマスの効率的な成分分離法の開発
寺村浩 1)、佐々木建吾 1)、白井智量 2)、川口秀夫 1)、荻野千秋 3)、菊地淳 2)、佐塚隆志 4)、近藤昭彦 1,3)
1)神大院・イノベ、2)理研・CSRS、3)神大・工、4) 名大・生物セ
Analysis of effect of alcohol addition to dilute acid pretreatment
Hiroshi Teramura 1), Kengo sasaki1), Tomokazu shirai2), Hideo Kawaguchi1), Chiaki Ogino3), Jun Kikuchi2),
Takashi Sazuka4), Akihiko Kondo1,2)
624

1)

Graduate school of Science, technology, and Innovation, Kobe University, 1-1 Rokkodai, Nada, Kobe
657-8501, Japan, 2)RIKEN Biomass Engineering Program, Suehiro-cho, Tsurumi-ku, Yokohama, Kanagawa,Japan, 3)Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University,
Rokkodaicho, Nada-ku, Kobe, Hyogo, Japan, 4)Bioscience and Biotechnology Center, Nagoya University, Furo,
Chikusa, Nagoya 464-8601, Japan
Abstract:
Utilization of bioresource is important to reduce dependence on oil and greenhouse gas
emissions. Lignocellulosic biomass is a renewable resource and mainly composed of cellulose, hemicellulose
and lignin. Because lignocellulosic biomass has such complex structure, bioethanol production process requires
pretreatment and enzymatic hydrolysis to liberate sugars for microbial fermentation. Especially, lignin was
known as inhibitor of enzymatic hydrolysis. Therefore, removing lignin is important for realization of efficientbiorefinery process. Previous study reported that alcohol pretreatment can remove lignin efficiently. But, alcohol
pretreatment requires large amount of alcohol (30-50%). Because high amount of alcohol increase cost ofbiorefinery process, reduction in alcohol usage is required. In this study, small amount (12.5%) of six kinds ofalcohol was added to dilute sulfuric acid pretreatment, and effect of alcohol for pretreatment was analyzed.
Keywords: organosolv pretreatment, fractionation, 1-butanol, lignin, cellulose
2016-P33
木材中の多糖/リグニンの混在スケールの評価
勝永毅１），葭谷耕三２），寺本好邦２）
１）
岐阜大学大学院応用生物科学研究科応用生命科学専攻，２）岐阜大学応用生物科学部応用生命科学課程
Estimation of mixing scale for polysaccharide/lignin in wood.
Nobuki Katsu1), Kozo Yoshitani2), Yoshikuni Teramoto2)
1)
Graduate school of Applied Biological Sciences, Gifu University, Gifu 501-1193, Japan, 2)Faculty of Applied
Biological Sciences, Gifu University, Gifu 501-1193, Japan
Abstract:
Cellulose, hemicellulose, and lignin are the major components of wood. In general, distribution
states of cellulose microfibril and lignin may significantly affect material and processing properties of wood.
However, there is no standard measure to evaluate the deposition states. In the present study, we prepared thewood powders with the different polysaccharide/lignin ratios by ball milling and successive enzymatichydrolysis, aiming to estimate the mixing states by adopting the procedures established for polymer blends. In
this report, glass transition behavior of lignin component surrounding polysaccharide in hinoki-cypress woodflour (WF) was investigated using differential scanning calorimetry (DSC). The results revealed a systematiccomposition-dependent shift in the glass transition temperature (Tg) for the lignin component. The components
in the WF can thus be regarded as in an intimate mixing state on a Tg -detection scale (20–30 nm).
Keywords: wood powder, glass transition, thermal analysis, enzymatic hydrolysis, segment motion
2016-P34
樹木細胞壁モデルを用いた木化の物理的寄与に関する研究
夏目知明、阿部賢太郎、矢野浩之
京都大学生存圏研究所
Studies on the physical contributions of lignification using wood cell wall models
Tomoaki Natsume, Kentaro Abe, Hiroyuki Yano
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasyo, Uji, Kyoto, 611-0011, Japan
Abstract:
We used cellulose nanofiber hydrogels as a plant cell wall model and deposited artificial lignin
models. This process was reproduction of lignification. Then the hydrogels made by such method were
immersed in ethanol including coniferyl alcohol, peroxidase and H2O2. Dehydrogenation polymer (DHP) weresynthesized in gels after evaporating ethanol under reduced pressure. As a result, it was confirmed that DHPs
increased compression strength of gels. However, it was suggested that DHPs did not affect compression
strength when amounts of DHPs was more than 20 % of cellulose.
Keywords: artificial lignification, cellulose nanofiber, dehydrogenation polymer, compression strength
2016-P35
改質リグニン製造システムにおけるリサイクル薬液のキャラクタリゼーション
髙田依里 1)、池田努 1)、ネーティティ 1)、髙橋史帆 1)、周霖 2)、山本麻衣子 2)、谷口勇希 2)、大橋康典 2)、山田竜
彦 1)
1)
森林総合研究所、2)ハリマ化成株式会社
625

Characterization of the recovered PEG from the acid-catalyzed solvolysis system of the glycol lignin production
Eri Takata1), Tsutomu Ikeda1), Thi Thi Nge1), Shiho Takahashi1), Lin Zhou2), Maiko Yamamoto2), Yuki
Taniguchi2), Yasunori Ohashi2), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan, 2)Harima Chemicals, Inc., Saitama
340-0003, Japan
Abstract:
The acid-catalyzed solvolysis system of Japanese cedar using a glycol solvent as a solvolysis
medium is being developed to produce a glycol solvent-modified lignin (glycol lignin) having thermal fusibility.
A glycol solvent used as a solvolysis medium is recovered by removal of water from the supernatant ofsolvolysis liquor after glycol lignin precipitation, and reused in next production line. In this study, the solvolysis
medium, polyethylene glycol (PEG), was recovered under several different recovery conditions andcharacterized by size exclusion chromatography, brookfield viscometer and moisture analyzer in order todevelop a recycle system of a solvolysis medium. The molecular weight of the recovered PEG obtained from theimproved recovery process was almost same as that of fresh PEG, whereas the viscosity of the recovered PEG
was 1.4-fold higher than fresh PEG. It was found that the recovered PEG also showed a similar solvolysis
reactivity to that of fresh PEG.
Keywords: acid-catalyzed solvolysis, glycol lignin, polyethylene glycol (PEG), solvent recovery, softwood
2016-P36
分析的熱分解法による酸加溶媒分解スギリグニンの構造解析
中川明子 1)、H'ng Yinying1)、京極未憂 1)、Nge Thi Thi2)、高田依里 2)、山田竜彦 1,2)
1)
筑波大学生命環境系、2)森林総合研究所
Structural characterization of polyethylene glycol solvolysis lignin prepared from Japanese cedar by analyticalpyrolysis
Akiko Nakagawa-izumi1), Yin Ying H’ng1), Miyu Kyogoku1), Thi Thi Nge2), Eri Takata2), Tatsuhiko Yamada 1,2)
1)Faculty of Life and Environmental Sciences, University of Tsukuba, Japan, 2)Forestry and Forest Products
Research Institute, Japan
Abstract:
The acid catalyzed solvolysis of Japanese cedar was carried out using polyethylene glycol(PEG) as a solvolysis reagent in the presence of a very small amount of sulfuric acid (H 2SO4) to isolate lignin
fraction (PEG-lignin). PEG lignin were analyzed by the pyrolysis gas chromatography mass spectrometry(Py-GC/MS). A few pyrolysis products which were observed from PEG-Pulp and Japanese cedar were notobserved from PEG-lignin. It suggests that β-O-4 linkage is minor structure of PEG-lignin. PEG content
determined by PyGC/MS were 6.6-10.3%.
Keywords: PEG-lignin, pyrolysis gas chromatography/mass spectrometry, PEG content
2016-P37
pH-induced sequential fractionation and characterization of glycol lignin produced by acid-catalyzed
polyethylene glycol (PEG) solvolysis of softwoodThi Thi Nge1), Eri Takata1), Shiho Takahashi1), Tsutomu Ikeda1), Tatsuhiko Yamada1)
Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract:
pH-induced sequential fractionation of alkali diluted solvolysis liquor obtained fromacid-catalyzed PEG solvolysis of softwood meal was conducted to produce glycol lignin (GL) with different
molecular weight and thermal flow properties. It was found that the larger molecular weight fraction (F1) was
obtained at basic pH (pH8) and decreased gradually (F2> F3>F4) to acidic pH (pH2) at all PEG solvolysis
systems. The solid GL fraction of >60% was collected at the first stage fractionation at pH8 in PEG200
solvolysis process, whereas the similar amount of solid GL fraction of >25% was obtained at pH8 (F1), pH6.5(F2), and pH4.5 (F3) in PEG600 solvolysis process. As a result, the thermal flow property and thermal stabilityof GL fractions varied accordingly.
Keywords: glycol lignin, polyethylene glycol (PEG), acid-catalyzed solvolysis, fractionation, thermal flow
behavior
2016-P38
アセチル化アルコリシスリグニン及びこれを硬化剤とするエポキシ樹脂硬化物の合成と熱的性質
廣瀬重雄、佐藤彰芳、小島和樹、野坂佳秀
福井工業大学環境生命化学科
Synthesis and thermal properties of acylated lignin and epoxy resi cured with acylated lignin
Shigeo Hirose, Akiyoshi Sato, Kazuki Kojima, Yoshihide Nosaka
626

Department of Environmental and Biological Chemistry, Fukui University of Technology, Japan
Abstract:
Cured epoxy resins were prepared using acetylated alcoholysis lignin (AcAL). AcAL wassynthesized by a reaction of AL with isopropenyl acetate in the presence of catalytic amount of
p-toluenesulfonic acid. Bisphenol A diglycidyl ether (BPADGE) and a catalytic amount of
2-ethyl-4-methylimidazole (2E4MI) were dissolved in tetrahydrofuran (THF), and then THF was removed
under a reduced pressure. The obtained reaction mixtures having a [EPOXY]/[PhOAc] mole ratio of 1.0 was
cured at 180 oC for 5 hr. Thermal properties of the obtained cured epoxy resins were studied by differential
scanning calorimetry (DSC) and thermogravimetry (TG). It was found that AcAL can be synthesized using
isopropenyl acetate and that the curing reaction between PhOAc groups of AcAL and epoxy groups of BPADGE
occurs under the appropriate curing conditions.
Keywords: epoxy resins, acetylated lignin, synthesis, thermal properties
2016-P39
脱メチル化リグニンの調製と機能性評価（その２）小林 勅三 1)、飛松 裕基 2)、上高原 浩 1)、高野 俊幸 1)
1)
京都大学 大学院農学研究科、 2)京都大学 生存圏研究所
Demethylation of G/S and S-type dehydrogenation polymers (G/S, S-DHP)
Tokimitsu Kobayashi1), Yuki Tobimatsu2), Hiroshi Kamitakahara1), Toshiyuki Takano1)
1)
Graduate School of Agriculture, Kyoto University, Sakyo-ku. Kyoto, 606-8502, Japan, 2)Research Institute for
Sustainable Humanosphere, Kyoto University, Uji. Kyoto, 611-0011 Japan
Abstract:
To upgrade lignin, demethylation of guaiacyl and syringyl-type dehydrogenation polymers(G/S-, S-DHP) with iodocyclohexane were carried out. HSQC NMR spectra of the demethylated DHPs provedthat demethylation proceed smoothly. The result was supported by Phenolic-OH content of demethylated DHPs.
Demethylated S-DHP had higher iron adsorption and Bovine Serum Albumin (BSA) adsorption abilities thandemethylated G/S-DHP, although it had similar DPPH radical scavaning ability to demethylated G/SDHP.
Keywords: lignin, tannin, iodocyclohexane, demethylation, HSQC NMR
2016-P40
木質バイオマスの分子構造変換によるブロックコポリマーの調製とナノ粒子化
三木健太郎，上高原浩，吉永新，飛松裕基，高野俊幸
京都大学大学院 農学研究科
Lignin based-block copolymer and its nano particles from woody biomass
Kentaro Miki, Hiroshi Kamitakahara, Arata Yoshinaga, Yuki Tobimatsu, Toshiyuki Takano
Graduate School of Agriculture, Kyoto University, Kyoto, Japan
Abstract:
Sawdust from Japanese Larch (Larix leptolepis) was methylated or acetylated, and subsequently
fractionated by solvent extraction. Methylated and acetylated fractions were azido- or alkyne-functionalized via
Lewis acid catalyzed depolymerization. Cellulose and lignin-based block copolymers were synthesized via
Huisgen 1,3-dipolar cycloaddition between methylated and acetylated fractions, followed by the removal ofacetyl groups. Chloroform solutions of the block copolymers were spray dried to afford their nano particles.
Keywords: organic Qdot, tetrabutylammonium fluoride trihydrate, 1-ethyl-3-methylimidazolium acetate,
benzyl methyl ether, hemicellulose
2016-P41
変性草本系リグニンを用いた高性能フェノール樹脂
木村 肇１）、大塚 恵子１）、米川 盛生１）、松本 明博１）、谷口 勇希２）、山本 麻衣子２）、周 霖２）、大橋 康典２）
１）
地方独立行政法人大阪市立工業研究所 有機材料研究部, ２）ハリマ化成株式会社
High performance phenolic resin based on modified herbaceous lignin
Hajime Kimura1), Keiko Ohtsuka1), Morio Yonekawa1), Akihiro Matsumoto1), Yuki Taniguchi2), Maiko
Yamamoto2), Lin Zhou2), Yasunori Ohashi2)
1)
Osaka Municipal Technical Research Institute, Organic Materials Research Division, Osaka 536-8553, Japan,
2)
Harima Chemicals, Inc., Saitama 340-0003, Japan
Abstract:
In this study, we intended to develop the high performance phenolic resin based on natural
herbaceous lignin and revealed the characteristics. Generally, though natural lignin is added simply to phenolic
resins, for reactivity with the thermal fluidity of lignin is low, modification by lignin does not proceedsufficiently. Therefore, modified herbaceous lignin which was reactive to phenolic resins was prepared and the627

properties of the phenolic resin based on modified herbaceous lignin were investigated. The properties of thephenolic resin with modified herbaceous lignin were estimated by heat resistance, mechanical property,
electrical insulation and water resistance and compared to the phenolic resin with usual herbaceous lignin orwithout lignin. As a result, it was revealed that the phenolic resin with modified herbaceous lignin showed goodheat resistance, mechanical property and electrical insulation.
Keywords: lignin, herbaceous, phenolic resin, benzoxazine, heat resistance2016 ワークショップ－企画講演：リグニンの最新像と関連分野との連携－
第一部：NMR 法で見えてきたリグニンの最新像（W1〜W３)
2016-W1
解析法の概要と樹木リグニンの化学構造的特徴
秋山拓也
東京大学大学院農学生命科学研究科
Structural characteristics of softwood and hardwood lignins and their analytical methods
Takuya Akiyama
The University of Tokyo, Graduate School of Agricultural and Life Sciences,1-1-1 Yayoi, Bunkyo, Tokyo
113-8657.
Abstract:
The developments of NMR spectroscopy and the lignin NMR database have provided new
insights in the field of lignin chemistry filed. Dibenzodioxocins and spirodineones, those are the structural units
relatively newly proposed in softwood and hardwood lignins, can be seen on 1H-13C 2D NMR spectra of lignin.
As well as NMR methods, chemical degradation methods also play important roles on the structural elucidationof lignins since they have some advantages over the NMR methods, and vice versa. Structural characteristics ofsoftwood and hardwood lignins and their analytical methods will be shortly introduced in this presentation.
Keywords: β–O–4, resinol, phenylcoumaran, β–1, biphenyl
2016-W2
多様性と可変性：草本リグニン、種皮リグニン、組換え植物リグニン
飛松裕基
京都大学生存圏研究所
Lignin diversity and flexibility: lignins in grasses, seedcoats, and transgenic plants
Yuki Tobimatsu
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract:
Extensive studies on the structure of lignin using advanced NMR techniques have revealed thesubstantial diversity and flexibility of the polymer’s assembly in nature. It is becoming increasingly evident thatthe structure and biosynthesis of grass lignins are substantially different from those of hardwood/softwood
lignins; besides typical monolignols in hardwoods and softwoods, i.e., coniferyl and sinapyl alcohols, grass
lignins uniquely incorporate γ-p-coumaroylated monolignols as well as a flavonoid tricin upon lignification.
Recently discovered catechyl-type lignins derived from caffeyl and 5-hydroxyconiferyl alcohols in dicot andmonocot seedcoats exemplify the flexible – but yet substantially organized – manner in which different lignin
monomers are generated for lignification in different tissues/cells. Such flexibility of lignification is further
illustrated by numerous examples of lignins in transgenics and mutants that incorporate various “unusual” lignin
monomers that have arisen as a consequence of disruptions in the monolignol biosynthetic pathway.
Keywords: Gramineae, Poaceae, benozodioxane, CAD, CCR, CCoAOMT, COMT
2016-W3
リグニン—多糖複合体の解析と定量２次元 NMR 法
西村裕志
京都大学生存圏研究所
Analysis of lignin–carbohydrate complex and 2D–NMR for quantification
Hiroshi Nishimura
Res. Inst. for Sustainable Humanosphere (RISH), Kyoto Univ., Japan
Abstract:
Recent advances in NMR analysis give a better understanding of lignocellulose structures
including lignin-carbohydrate complex (LCC), a key component connecting hydrophilic and hydrophobic
macromolecules in plant cell walls. Several types of covalent linkages between lignin and hemicelluloses have628

been reported. These include  ether,  ester, γ ester, phenyl glycoside, and acetal bonds. 2D-NMR is a
powerful tool to unveil the structure of LCCs, but it was difficult to obtain direct evidence for the LC linkages
by NMR due to their very low frequency in cell walls. We concentrated LC linkages by enzymaticsaccharification and adsorption chromatography, and the LCC fragments obtained were analyzed by long-range
correlation NMR such as 1H–13C HMBC and HSQC-TOCSY in addition to HSQC. We also developed a newquantitative 2D-NMR named TAF (tolerant of any factors) which is tolerant of any factors such as variation inmolecular size, the 1JCH values, the presence of homonuclear 1H–1H couplings, and imperfections in NMR
pulses.
Keywords: lignin-carbohydrate linkage, LCC, benzyl ether, quantitative NMR, Q-HSQC
2016 ワークショップ －企画講演：リグニンの最新像と関連分野との連携－
第ニ部：関連分野からの話題提供(W4〜W6)
2016-W4
カスパリー線の機能と形成
神谷岳洋
東京大学大学院農学生命科学研究科 応用生命化学専攻 植物栄養・肥料学研究室
Function and formation of Casparian strip
Takehiro Kamiya
Laboratory of Plant Nutrition and Fertilizers, Department of Applied Biological Chemistry,
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
The Casparian strip (CS) is a lignin-based cell wall modification deposited in the anticlinal wallof root endodermal cells. The CS prevents apoplastic flow of water and solute into the vascular system, making
possible selective nutrient loading by transporters at the endodermis. However, molecular mechanisms of CS
formation and its function in solute transport are unclear as no gene had been identified until recently. Throughthe analysis of mutants that have defects in nutrient transports, we have identified genes required for CS
formation. One of the mutant has mutation in a transcription factor, MYB36. MYB36 directly upregulates
expression of genes important for the correct formation of the CS domain and the localization of the CS
biosynthetic machinery. The other mutant, low-calcium sensitive 2 (lcs2), has been identified as a mutant whose
growth was inhibited under low Ca condition. lcs2 has mutation in a novel gene with unknown domain. lcs2 has
defect in CS formation and showed altered localization of CASP1, a gene required for correct localization of CS
biosynthetic machinery, suggesting that lcs2 is required for the correct localization of CASP1. Recently, throughthe analysis of these mutant, we reveal that defect of CS as a apoplastic barrier is complemented by suberin, aglycerolipid polymer. Our findings suggest the presence of the mechanisms for the coordinated formation oflignin and suberin.
Keywords: Casparian strip, cell wall, apoplast, suberin
2016-W5
リグニン由来含芳香族化合物群を利用した新規樹脂素材開発
阿部英喜
理化学研究所 環境資源科学研究センター バイオプラスチック研究チーム
Development of novel polymeric materials utilizing aromatic chemicals from lignin
Hideki Abe
Bioplastic Research Team, RIKEN Center for Sustainable Resource Science, Japan
Abstract:
By using vanillin derivatives, the syntheses of aromatic polyesters, polyurethanes, andpolyamides were carried out. Taking account of decomposition temperature of monomeric compounds, thepolymerization conditions were optimized. As a result, the polyesters containing vanillin derivatives wereobtained at high molecular weights (Mw>50,000). The obtained polyester had a melting temperature over 190ºC and could be molded as a film specimen. When the drawing treatment was applied for the polyester films, thestretched films showed excellent mechanical properties as 120 MPa of tensile strength and 4.3 GPa of Young’s
modulus. Furthermore, we succeeded in syntheses of novel polyurethanes from vanillin derivative andlysine-based diisocyanate. The polyurethanes from monomeric vanillin derivative as a sole diol component
became to be hard resins with glass transition temperature around 70 ºC, whereas a mixing of alkanediol withvanillin derivative yielded soft polyurethane resins with elongation break over 500 %. The obtained
polyurethanes were amorphous polymers and revealed very transparent characteristics as total lighttransmittance of over 90%. When the dimeric monomer of vanillin derivatives was used as a diol component,629

the obtained polyurethane became to be semi-crystalline polymer and had a melting temperature of 162 ºC and a
glass transition temperature of 102 ºC. Thus we found that the thermal stability of polyurethanes could be
improved by the imparting the symmetric structure to monomeric units. We also embarked on the synthesis ofnovel bio-based aromatic acrylic resins from cinnamate derivatives. The organic acids such as super strong acids
catalyzed the group transfer polymerization of cinnamate derivatives at a C-C double bond to give thecorresponding polymer molecules. Under the optimized conditions, the reaction yielded polymers of cinnamate
derivatives with relative high molecular weights (Mw>30,000). The obtained polymers had higher glasstransition temperature of 165 ºC, and the values were comparable to that of common petrochemical engineering
plastic of polycarbonate.
Keywords: vanillin derivatives, aromatic polyesters, aromatic polyurethanes, cinnamate derivatives,
aromatic acrylic resins
2016-W6
国産草本繊維質を用いた糖質プラットホーム構築に向けた技術開発～現状と新たな挑戦～
徳安 健 1)、池 正和 1)、山岸賢治 1)、折笠貴寛 2)
１）
農業・食品産業技術総合研究機構 食品研究部門、２）岩手大学農学部
Current situation and new challenges of technology development for the sugar platform using domestic fibrous
feedstocks
Ken Tokuyasu1), Masakazu Ike1), Kenji Yamagishi1), and Takahiro Orikasa2)
1)
Food Research Institute, National Agriculture and Food Research Organization, Japan, 2)Faculty of Agriculture,
Iwate University, Japan
Abstract:
Sugar platform for lignocellulosic feedstock is highly expected as an environmentally-friendly
process for production of fuels or chemicals, leading us to sustainable co-existence and co-prosperity of a new
bio-business with rural agriculture/forestry. Recently we developed a “simple” sugar production system fordomestic herbaceous biomass in Japan (rice straw and cellulosic energy crops as main feedstock) with an alkali
pretreatment, termed the CaCCO (Calcium Capturing by Carbonation) process. In this paper, the simplicity of
the CaCCO process as well as its improvement for various applications in rural areas is presented.
Keywords: sugar platform, CaCCO (Calcium Capturing by Carbonation) process, herbaceous feed stock,
pretreatment, bioeconomy.
2016 ワークショップ －リグニン科学の基礎講座－(W7〜W9)
2016-W7
細胞壁の木化
高部圭司
京都大学 大学院農学研究科 森林科学専攻
Lignification of cell wall
Keiji Takabe
Division of Forest and Biomaterials Sciences, Graduate School of Agriculture, Kyoto University, Sakyo, Kyoto,606-8502 JAPAN
Abstract:
Lignification starts at cell corner middle lamellae when the secondary wall formation starts, andthen proceeds to compound middle lamellae. Lignification of secondary wall starts at the outer portion, andproceeds toward the lumen lagging behind the cell wall thickening. Non-lignified secondary cell wall showsparallelly oriented cellulose microfibrils with many cross-linkings composed of hemicelluloses. When thelignification proceeds, many globular structures appear along the microfibrils. Monolignols are synthesized in
the cell, transported toward the cell wall, and polymerized within the cell wall. Detailed process is discussed.
Keywords: basic course, cell wall, differentiating xylem, lignification, monolignol
2016-W8
リグニンとは －化学構造と単離リグニン－
河本晴雄
京都大学大学院エネルギー科学研究科
What is lignin? －Chemical structure and isolated lignins－Haruo Kawamoto
Graduate School of Energy Science, Kyoto University, Japan
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Abstract:
Lignin is an aromatic substance which comprises approximately 15-35% of the components ofwood and other lignocellulosics. In this course, chemical structures of lignins, which vary depending on thetaxonomical group, are introduced in terms of the composition of biosynthetic monomers and their radicals
formation followed by radical coupling reactions. Types of lignin preparation method and characteristic featuresof isolated lignins are also briefly explained.
Keywords: basic course, chemical structure, linkage type, lignin preparations
2016-W9
リグニンの化学分析法
高野 俊幸
京都大学 大学院農学研究科
Chemical analysis of lignin
Toshiyuki TAKANO
Graduate School of Agriculture, Kyoto University, Japan
Abstract:
Lignin-content determination
Klason method, Acetyl bromide method, Thioglycol lignin method, Kappa number test
Lignin chemical structure analysis
IR method, NMR method, Alkaline-nitrobenzene oxidation method, Thioacidolysis method, DFRC method andso on
Keywords::basic course, characterization, content, qualitative analysis, quantitative analysis, spectral analysis

631

第 62 回 （2017.10.27-28） 名古屋大学 野依記念学術交流館
207-101
木化に及ぼすヘミセルロースの影響
古川貴大 1)、吉永新 2)、高部圭司 2)、松尾朱実 3)、玉井裕 4)、幸田圭一 4)、浦木康光 4)1)北海道大学大学院農学院 2)京都大学大学院農学研究科
3)北海道大学農学部 4)北海道大学大学院農学研究科
Effect of hemicelluloses on lignification
Takahiro Furukawa1), Arata Yoshinaga2), Keiji Takabe2), Akemi Matsuo3),
Yutaka Tamai4), Keiichi Koda4), Yasumitsu Uraki4)
Graduate School of Agriculture, Hokkaido University, Sapporo, 060-8589, Japan
Graduate School of Agriculture, Kyoto University, Kyoto, 606-8502, Japan
School of Agriculture, Hokkaido University, Sapporo, 060-8589, Japan
Research Faculty of Agriculture, Hokkaido University, Sapporo, 060-8589, Japan
Abstract: We have already examined xylan functions on the formation of dehydrogenation polymer (DHP)
using artificial wood cell wall1). As results, xylan can introduce coniferyl alcohol as a monolignol into cellulose,and enhances the frequency of aryl ether linkage in DHP. In this study, we investigated glucomannan function as
another typical hemicellulose through the same experiment as that for elucidation of xylan function.
Glucomannan was adsorbed on bacterial cellulose film (BC) in much larger amount than xylan did. However,
only trace of DHP deposition inside glucomannan-deposited BC film was determined by acetyl bromide method.
Therefore, it is likely that glucomannan does not have similar functions on DHP formation to those of xylan.
Keyword: dehydrogenation polymer (DHP), glucomannan, xylan, wood cell wall, lignification
2017-102
Stereo-preferential formation of p-hydroxyphenyl-type β-O-4 structures from the quinone methides
Xuhai Zhu, Takuya Akiyama, Tomoya Yokoyama, Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences,
Graduate School of Agricultural and Life Science, The University of Tokyo, Tokyo, Japan
Abstract: A model experiment mimicking the erythro/threo (E/T) ratio determining-step for the formation of
p-hydroxyphenyl-type β-O-4 structure during lignin biosynthesis was performed to investigate the effect of
aromatic ring type on the E/T ratio. Four types of quinone methides (QM) were synthesized from corresponding
β-O-4 dimer models carrying p-hydroxyphenyl (H)-and/or guaiacyl (G)-units [HH-, GH-, HG- and GG-typemodels (ex. GH-type: guaiacylglycerol-β-p-hydroxyphenyl ether)]. The water addition to the QMs was
examined in different buffer conditions (pH 3-7). The threo-preferential formation was observed, but theerythro-preferential formation assumed based on the previous study of compression wood was not found in any
QMs under any pH conditions. The E/T ratio of the β-O-4 dimers tended to be lower at a higher pH condition.
At any pH, the threo-selectivity was always higher in the order of HH-＞GH-＞HG-＞GG-type of QM,
indicating that threo-preferential formation was enhanced by the presence of H unit either as QM moiety or as
etherified aromatic ring.
Keywords: quinone methide; β-O-4 structure; p-hydroxyphenyl; erythro/threo ratio; softwood lignin.
2017-103
植物細胞壁の木化におけるモノリグノールグルコシドの挙動と役割— Glycone 部（Glucose）の役割・命運について—
寺島典二 1)、松下泰幸 2)、橋浦雅 2)、八神祐絵 2)、青木弾 2)、福島和彦 2)
1) 名古屋大学名誉教授、2) 名古屋大学大学院生命農学研究科
Behavior and role of monolignol glucosides in lignifying plant cell walls— Role and fate of glycone moiety (glucose) —Noritsugu Terashima1), Yasuyuki Matsushita2), Masashi Hashiura2),
Sachie Yagami2), Dan Aoki2) and Kazuhiko Fukushima2)
1)
Emeritus professor, Nagoya University, Nagoya 464-8601, Japan
2)
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract: Monolignol glucosides are intermediate compounds in lignin biosynthesis. In the lignifying cell wall,monolignol glucosides are hydrolyzed by β-D-glucosidase into aglycone moiety, monolignols;
p-hydroxycinnamyl alcohol, coniferyl alcohol and sinapyl alcohol, and glycone moiety, D-glucose (Glc). The
632

aglycone moiety, monolignols are known to polymerize in the previously deposited polysaccharides gel to form
macromolecular lignin-polysaccharides complexes. On the other hand, fate of the liberated D-glucose is not yet
known. In this work, coniferins 13C-enriched at aglycone and glycone moieties, coniferin-[side chain-13Cα] andconiferin-[Glc-13C6] respectively, were administered to growing shoots of Ginkgo biloba, and fate of the
Glc-[13C6] was traced in comparison with the fate of coniferyl alcohol-[side chain-13Cα]. The side chain
13
Cα-enriched coniferyl alcohol moiety incorporated into lignin at expected level, around 4-5 % of the total
lignin, due to dilution by the large flow of original lignin formation in the cell wall. On the other hand, a part ofthe liberated glycone moiety, Glc-[13C6], was incorporated into cell wall polysaccharides. Some part is supposed
to be utilized for production of active oxygen species necessary for polymerization of monolignols, and somepart for modification of polysaccharide structure in the later formation stage of lignin-polysaccharide complexes
in the cell wall.
Keywords: 13C-tracer method, δ13C, alditol acetate, glucuronic acid, xylan
2017-104
イネにおける p-クマロイル-CoA モノリグノールトランスフェラーゼの酵素機能解析ならびに機能欠損変異株の作出と性状解析
田中拓人 1)、鈴木史朗 1)、武田ゆり 1)、山村正臣 1)、刑部敬史 2)、飛松裕基 1)、梅澤俊明 1,3)
1) 京大生存研、2) 京大院農、3) 徳島大生物資源産業、4) 京大生存基盤展開
Functional analysis of Oryza sativa p-coumaroyl CoA:monolignol transferases and characterization of theknock-out mutants
Takuto Tanaka1), Shiro Suzuki1), Yuri Takeda1), Masaomi Yamamura1),
Keishi Osakabe2), Yuki Tobimatsu1), Toshiaki Umezawa1,3)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan
2)
Faculty of Bioscience and Bioindustry, Tokushima University, Kuramoto-cho, Tokushima 770-8503, Japan
3)
Research Unit for Global Sustainability Studies, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
Abstract: Grass lignins are uniquely γ-acylated by p-coumaroyl residues which arise from the polymerizationof γ-p-coumaroylated monolignols upon lignification. Currently, however, little is yet known regarding thebiological origin, functions as well as any potential impacts on the biomass properties of such lignin
γ-acylations in grass. Here, we describe our attempt to generate rice mutants deficient in
p-coumaroyl-CoA:monolignol transferase (PMT) genes involved in the biosynthesis of γ-p-coumaroylatedmonolignols in rice. We identified two rice PMT candidates displaying the anticipated monolignol acylation
activity in vitro. We then generated rice mutants deficient in the two PMT genes using CRISPR/Cas9-mediatedtargeted mutagenesis, and subjected their cell wall tissues to an in-depth structural analysis using 2D NMR.
KeywordLignin, Bio-refinery, Oryza sativa , p-Coumaroyl-CoA:monolignol transferase, CRISPR/Cas9 system
2017-105
Altered cell wall structure and improved biomass digestibility in tricin-truncated rice mutant deficient in flavone
synthase II
Pui Ying Lam1,2), Yuki Tobimatsu2), Yuri Takeda2), Shiro Suzuki2), Masaomi Yamamura2), Toshiaki
Umezawa2,3), Clive Lo1)
1)
School of Biological Sciences, The University of Hong Kong, Hong Kong, China
2)
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
3)
Research Unit for Development of Global Sustainability Studies, Kyoto University, Japan
Abstract: A wide range of grass species utilize tricin flavone as a natural lignin monomer. However, thebiosynthetic origin of tricin-bound lignin as well as the impacts of its manipulation on cell wall structures andproperties remain poorly understood. This study addresses in-depth cell wall analysis on a tricin-trancated ricemutant deficient in a flavone synthase II (FNSII). A series of cell wall structural analyses using chemical and
NMR methods demonstrated that the mutant produces lignins being completely devoid of tricin andincorporating naringenin as a novel flavonoid component. The mutant was further revealed to display enhanced
enzymatic saccharification efficiency. Overall, we contemplate that manipulation of tricin biosynthetic pathway
could be an alternative strategy for improving cell wall digestibility in grass crops.
Keywords
Lignin, Oryza sativa, Flavone synthase II, Tricin, Enzymatic saccharification
2017-106633

選択的 13C 標識法と固体 NMR を用いた HG-DHP の構造解析
橋浦雅 1)、野村健太 1)、松下泰幸 1)、寺島典二 2)、青木弾 1)、福島和彦 1)
1) 名古屋大学大学院生命農学研究科 2) 名古屋大学名誉教授
Structural analysis of HG-DHP by 13C-enrichment technique and solid-state NMR
Masashi Hashiura1), Kenta Nomura1), Yasuyuki Matsushita1), Noritsugu Terashima2),
Dan Aoki1), Kazuhiko Fukushima1)
1) Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
2) Emeritus Professor, Nagoya University, Nagoya 464-8601, Japan
Abstract: In order to analyze lignin structures, 13C-enriched HG-DHP made from the selective 13C-enriched
p-glucocoumaryl alcohol and unenriched coniferin was analyzed by solid-state 13C CP/MAS NMR and two
dimensional (2D) 13C-1H correlation HETCOR. Making difference NMR spectra between the 13C-enrihed
HG-DHP and unenriched HG-DHP provide simple spectra from the specific 13C-enriched carbons. From thesimplified differential spectra and HETCOR spectra of HG-DHP, we assigned the C3 and C5 chemical shift oflignin major structures involved in p-hydroxyphenyl unit (H unit), respectively.
Keywords: selective 13C-enrichment, solid-state NMR, p-hydroxyphenyl unit (H unit), DHP
2017-107
分子運動性解析による多糖/リグニンのナノスコピックな共存形態の評価
勝永毅 1)，葭谷耕三 2)，寺本好邦 2,3)
1) 岐阜大学大学院応用生物科学研究科応用生命科学専攻，
2) 岐阜大学応用生物科学部応用生命科学課程
3 ) 岐阜大学生命の鎖統合研究センター（G-CHAIN）
Evaluation of nanoscopic coexistence states of polysaccharide/lignin in lignocellulosic biomass by molecularmobility
Nobuki Katsu1), Kouzou Yoshitani2), Yoshikuni Teramoto2), 3)
1)
Graduate school of Applied Biological Sciences, Gifu University, Gifu 501-1193, Japan
2)
Faculty of Applied Biological Sciences, Gifu University, Gifu 501-1193, Japan
3)
Center for Highly Advanced Integration of Nano and Life Sciences (G-CHAIN), Gifu University, Gifu
501-1193, Japan
Abstract: Cellulose, hemicellulose, and lignin are the major components of wood. Information on these
coexistence states in nanoscale is essential for promoting the effective use of wood and wood polymers. We
aimed to evaluate nanoscopic average compactness of polysaccharide/lignin by differential scanning calorimetry(DSC) analysis and proton spin-lattice relaxation times in the rotating frame (T1ρH) by solid state NMR. The
DSC thermograms showed a systematic composition-dependent shift in the glass transition temperature (Tg) forthe lignin component. The components in both samples can thus be regarded as in an intimate mixing state ona Tg-detection scale (20–30 nm). We also investigated the dependence of proton spin-lattice relaxation times
in the rotating frame (T1ρH) measured by solid-state NMR on the polysaccharide/lignin ratios and species. As aconsequence, the enzymatically hydrolyzed samples showed an increase in the T1ρH value for the lignin
component.
Keywords: Wood flour, Glass transition, solid-state NMR, Ball-milling, Enzymatic hydrolysis
2017-108
塩基性下におけるリグニン β-O-4 結合開裂反応に及ぼすカウンターカチオンの影響
加藤 唯真、秋山 拓也、横山 朝哉、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Effect of counter cation on the lignin β-O-4 bond cleavage under basic conditions
Yuishin Kato, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract: The erythro isomer of a non-phenolic β-O-4 lignin model compound, veratrylglycerol-β-guaiacyl
ether (VG-e), was reacted in a H2O solution, aqueous methanol solution, aqueous ethanol solution, or aqueous
1,4-dioxane solution containing LiOH, NaOH, or CsOH as a base under pulping conditions to examine theeffect of the counter cations on the pulping reactions. The disappearance rate of VG-e was in the order of: CsOH
> NaOH > LiOH, which presumes that Li+ interacts with HO¯ and suppresses the action of HO¯ mostsignificantly. A major reaction product, the erythro isomer of veratrylglycerol, was obtained with the highest
634

yield, when CsOH was employed in each solvent system. This result suggests that the nucleophilicity of HO¯ issensitive to strength of the interaction between a counter anion and HO¯.
Keywords.
Alkyl-aryl ether, Alkali, Cooking, Wood
2017-109
リグニンの分子構造変化に伴う材色の変化
山本雅信 1)、諾恩達古拉 1)、高田直樹 2)、小山朗夫 3)、奥泉久人 4)、上杉幹子 1)、梶田真也 1)
1)
東京農工大学大学院生物システム応用科学府、2)森林総合研究所 森林バイオ研究センター
3)
元 農業生物資源研究所、4)農業・食品産業技術総合研究機構 遺伝資源センター
The relationship between structural change of lignin and color characteristic of woods
Masanobu Yamamoto1), Nuoendagula1), Naoki Takata2), Akio Koyama3), Hisato Okuizumi4)
Mikiko Uesugi1), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan, 2)Forest Bio-Research Center, Forestry and Forest Products ResearchInstitute, Ibaraki 319-1301, Japan, 3)National Institute of Agrobiological Sciences, Japan (previous affiliation),
4)
Genetic Resources Center, National Agriculture and Food Research Organization, Ibaraki 305-8602, Japan
Abstract: Lignin is the main component of secondary cell walls in land plants. Occasionally, structural changesof the lignin are accompanied with a change in color of woods. Woods deposited in some of the mutants andtransgenic plants with modified the lignin structures have different colors compared to wild-type plants,suggesting the color of woods is the one of good indicators for the lignin structural change. In this study, wecharacterize the structure of the lignin deposited in red-colored woods in a mulberry mutant we have recently
recognized. The results from staining assay and monomeric composition analysis of the lignin in addition to thatfrom lignin content analysis of the mutant will be presented.
Keywords: cinnamyl alcohol dehydrogenase, derivatization followed by reductive cleavage procedure,
thioacidolysis
2017-201
Kinetic studies of the two fungal glutathione-dependent enzymes and their potential roles in the intracellulardetoxification and wood-derived compound metabolism
Wan Hasnidah Wan Osman1), Meng-I Lin1), Keiko Kondo2),
Takashi Nagata1, 2), Masato Katahira1, 2)
1)Graduate School of Energy Science, Kyoto University, Japan
2)
Institute of Advanced Energy, Kyoto University, Japan
Abstract: Lignin, one of the wood components, is becoming important as a raw material when sustainablebio-refinery is concerned. However, it is highly complex and recalcitrant, thereby undervalued andunderdeveloped. Wood decaying fungi have developed a complex enzymatic system and possess intracellular
networks to deal with potential recalcitrant organic compounds. Glutathione-dependent enzymes are
multifunctional and capable of catalyzing the detoxification reactions, tempting us to think that some of them, if
not all, might be involved in wood-derived compound metabolism. In this study, we developed Escherichia coli
expression systems for two fungal glutathione-dependent enzymes, individually, and successfully purified using
affinity and size exclusion column chromatographies. Three model substrates were used to determine theactivities involved in the intracellular detoxification. For wood-derived compound metabolism, three fluorescentcompounds have been used to examine etherase and esterase activities. Our data strongly suggest that these two
enzymes have distinct roles in both the fungal detoxification system and wood compound metabolism.
Keywords: fungi, glutathione-dependent enzymes, detoxification, metabolism
2017-202
白色腐朽菌ヒラタケにおける GH10・GH11 の機能喪失がリグニン分解に及ぼす影響について
湯村直樹 1)、中沢威人 1)、大沼広宜 2)、泉津弘佑 3)、入江俊一 3)、福田泰久 4)白坂憲章 4)、坂本正弘 1)、本田与一 1)
1)京都大学大学院農学研究科 2)近畿大学大学院農学研究科
3)滋賀県立大学環境科学部 4)近畿大学農学部
Effects of targeted disruption of genes encoding GH10 and GH11 on lignin degradation in the white-rot fungus
Pleurotus ostreatus635

Naoki YUMURA1), Takehito NAKAZAWA1), Hiroki ONUMA2), Kosuke IZUMITSU3), Toshikazu IRIE3),
Yasuhisa FUKUTA4), Norifumi SHIRASAKA4), Masahiro SAKAMOTO1), Yoichi HONDA1)
Graduate School of Agriculture, Kyoto University,
Graduate School of Agriculture, Kindai University,
Faculty of Environmental Science, the University of Shiga Prefecture
Faculty of Agriculture, Kindai University
Abstract: White-rot fungi efficiently degrade wood lignin, and its mechanism remains to be elucidated. Lignin
and carbohydrates form complex structures in wood. It was reported that a covalent linkage exists between
lignin and hemicellulose via glucurono acid in beech wood, which suggests degradation of lignin can beaffected by xylan. Various transcriptome and secretome studies were conducted in white-rot fungi, and it was
shown that CAZys but not so many ligninolytic enzymes were responsive to lignocellulosic substrates. In thisstudy, we examined the effects of targeted disruption of genes encoding GH10 and GH11 on lignin degradationin the white-rot fungus Pleurotus ostreatus, which intriguingly revealed that targeted disruption of one of GH11
genes decreased ability to degrade lignin in beech sawdust.
Keywords: Pleurotus ostreatus, targeted gene disruption, heterologous expression, xylanase, lignin
degradation,
2017-203
キノコによる木質リグニン分解と有性形態形成との間に、関係性はあるのか？
中沢威人 1)、堀井雅人 1)、森本亮太 1)、辻祥子 2)、西村裕志 2)、小寺里奈 1)、坂本正弘 1)、
渡辺隆司 2)、本田与一 1)
京都大学大学院農学研究科 2)京都大学生存圏研究所
Do the regulation mechanisms of wood lignin biodegradation coordinate with those of sexual development ?
Takehito NAKAZAWA1), Masato HORII1), Ryota MORIMOTO1), Shoko TSUJI2),
Hiroshi NISHIMURA2), Rina KODERA1), Masahiro SAKAMOTO1), Takashi WATANABE2),
Yoichi HONDA1)
1)
Graduate School of Agriculture, Kyoto University
2)
Research Institute for Sustainable Humanosphere, Kyoto University
Abstract: Most wood decaying fungi belong to agaricomycetes, which are characterized by their dramatic
morphological differentiation, fruiting development or mushroom formation. Fruit bodies are relatively large
multicellular structures formed during sexual reproduction. Among wood decaying fungi, white-rot fungi play
an important role in the global carbon cycle because they the species that almost exclusively degrade plant cellwall lignin in nature. Some previous studies suggested that there are some correlations/coordination between
sexual reproduction and ligninolysis in some white rot fungi. It was recently shown that mutations that causesignificant defects in the ligninolytic activity also cause defects in fruiting initiation in Pleurotus ostreatus. In
this study, we investigated this hypothesis by extensive molecular genetics and genomic studies.
Keywords: white rot, fruiting development, mushroom, gene regulation
2017-204
マンガンペルオキシダーゼ/複合メディエーター系によるリグニン分解機構の解析
池田拡平 1)、栫拓巳 2)、堤祐司 3)、森智夫 1)、河岸洋和 1, 4, 5)、平井浩文 1, 4)1) 静岡大学農学部、2) 九州大学農学部、3) 九州大学大学院農学研究院、
4) 静岡大学グリーン科学技術研究所、5) 静岡大学創造科学技術大学院
Analysis of lignin degradation mechanism by manganese peroxidase / complex mediator system
Kohei Ikeda 1), Takumi Kakoi 2), Yuji Tsutsumi 3), Toshio Mori 1), Hirokazu Kawagishi 1, 4, 5), Hirofumi Hirai 1, 4)
1)Faculty of Agriculture, Shizuoka University, Japan
2)
Faculty of Agriculture, Kyusyu University, Japan
3)
Faculty of Agriculture, Graduate School of Kyusyu University, Japan
4)
Research Institute of Green Science and Technology, Shizuoka University, Japan
5)
Graduate School of Science and Technology, Shizuoka University, Japan
Abstract: In this study, we attempted to construct the method of effective enzymatic delignification withmanganese peroxidase (MnP) from beech wood. Ball mill treatment of wood meal was increased delignification
efficiency of MnP/multi radical mediators reaction system, lignin degradation was reached at 10.6% for 48 hour
reaction. And sequential enzymatic delignification slightly increased lignin degradation ratio to 13.5%. Because
lignin degradation was reached sufficient level for structural analysis, at first alkaline-nitrobenzene oxidation
was performed. By comparison for raw beech wood meal, recoveries of syringaldehyde and vanillin from636

enzymatic delignified wood were roughly 20% reduced. This result suggested that MnP/multi mediators system
oxidized the non-condensed structure selectively, regardless to syringyl and guaiacyl type structure.
Keywords: Phanerochaete sordida YK-624, manganese peroxidase, lignin degradation, radical mediator,
alkali nitrobenzene oxidation
2017-205
イオン液体触媒を利用したリグノセルロース系バイオマスのエステル交換反応におけるリグニン水酸基の反応性鈴木栞 1)、廣瀬大祐 2)、高橋憲司 2)1) 金沢大学大学院自然科学研究科、2) 金沢大学理工研究域
Transesterification Reaction of lignocellulosic Biomass using Ionic Liquid Catalyst: Reactivity of Hydroxyl
Groups of Lignin
Shiori Suzuki1) , Daisuke Hirose2) , Kenji Takahashi2)
1) Graduation School of Natural Science and Technology, Kanazawa University,
2) Institute of Science and Engineering, Kanazawa University,
Kakuma-machi, Kanazawa-shi, Ishikawa 920-1192, Japan
Abstract: Polysaccharide acetate and lignin acetate were simultaneously synthesized from lignocellulosic
biomass via transesterification with isopropenyl acetate (IPA) as an ester donor in an ionic liquid,1-ethyl-3-methylimidazolium acetate (EmimOAc), which has both lignocellulose-dissolution andorganocatalytic abilities. Efficient homogeneous reactions of bagasse were successfully proceeded under mild
conditions without any additional acid catalysts and corrosive reagents, and a successive separation ofpolysaccharide acetate and lignin acetate was achieved with by taking a difference of solubility in methanol.
Acetylation ratio of the polysaccharide acetate and lignin acetate obtained at 80ºC for 30 min were 83% and71%, respectively. Detail analysis of reaction rates by quantitative 31P NMR method1) revealed that lower
reactivity of phenolic OH in lignin than alcoholic OH in the case of transesterification using the EmimOAc
catalyst.
Keywords: Lignocellulose, Organocatalyst, Acetylation, Chemical modification, Homogeneous reaction
2017-206
テトラブチルアンモニウムヒドロキシドを反応媒体としたリグニンの化学変換
細谷隆史 1)、溝口晃平 1)、山本康平 1)、前田美咲 1)、
吉村沙樹子 1)、宮藤久士 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Lignin Conversion with Tetrabutylammonium Hydroxide as a Reaction Medium
Takashi HOSOYA1), Kohei MIZOGUCHI1), Kohei YAMAMOTO1), Misaki MAEDA1),
Sakiko YOSHIMURA1), Hisashi MIYAFUJI1), Tatsuhiko YAMADA2)
1)
Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
2)
Forestry and Forest Products Research Institute, Japan
Abstract: Aerobic oxidation of various types of lignin in tetrabutylammonium hydroxide (TBAH) produces
vanillin and its related phenols with high selectivity. This study addresses degradation of Japanese cedar(Cryptomeria japonica) wood flour in a 1.25 M TBAH solution with the O2 and OH− concentrations beingenhanced by introduction of O2 and NaOH addition to the system. The TBAH treatment of the wood gave
vanillin, vanillin acid, and acetoguaiacone with 23.0, 1.2, and 1.9 wt% yields based on the Kason lignin amount,which were comparable to those obtained with the alkaline nitrobenzene (AN) oxidation. Our further
investigation with lignin model compounds revealed that β-O-4 and β-5 linkages formed vanillin in the TBAH
treatment whereas the AN oxidation produced vanillin only from β-O-4 linkage. This strongly suggests thatmechanisms in the vanillin formation are significantly different between the TBAH treatment and AN oxidation.
Keywords: Vanillin, Quaternary ammonium, Oxidation, Alkali, Mechanism
2017-207
リグニンフェノール性末端の構造解析と酸触媒ソルボリシスにおける反応性：スギとユーカリの比較
齋藤香織 1)、酒井亮 2)、牧村裕 1)、西村裕志 1)、渡辺隆司 1)
1) 京都大学生存圏研究所、2)日本化薬株式会社
Reactivity of free phenolic end units in lignin during acid-catalyzed solvolysis: comparison of Cryptomeria
japonica and Eucalyptus globulus
637

Kaori Saito1), Ryo Sakai2), Yutaka Makimura1), Hiroshi Nishimura1),
and Takashi Watanabe1)
1)
Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611–0011, Japan
2)
Nippon Kayaku Co., Ltd, Chiyoda-ku, Tokyo 100-0005, Japan
Abstract: Free phenolic groups in lignin were selectively methylated to investigate how the phenolic terminal
and non-phenolic units are released via the β-O-4 cleavage during the toluene-methanol microwave solvolysis.
Thioacidolysis of the methylated woods of C. japonica and E. globulus showed that the relative proportions of
the G units derived from the phenolic end units are higher than those of S units. The result of the acid-catalyzed
toluene-methanol solvolysis of the methylated wood showed that the preferential release of the C6-C2
monomeric degradation products from the phenolic units are observed only in G units, whereas the S monomers
were released mainly from the non-phenolic ether-linked units in lignin. The reactivity of the phenolic units
during solvolysis was shown to be different between softwood G lignin and hardwood SG lignin.
Keywords: guaiacyl, syringyl, phenolic hydroxyl groups, thioacidolysis, solvolysis.
2017-208
PEG・バイサルファイト法タケ液化物を用いたエレクトロスピニング処理によるカーボンファイバーの調製
河野 陽平 1、福永 史 2、藤田 弘毅 1、堤 祐司 1
1) 九州大学大学院 農学研究院、2) 九州大学 農学部
Preparation of carbon fiber by electrospinning using liquefied bamboo from PEG-bisulfite method
Yohei Kawano1, Fumiya Fukunaga2, Koki Fujita1 and Yuji Tsutsumi1
1)
Department of Agro-environmental Sciences, Kyushu University, 812-8581, Fukuoka, Japan
2)
Faculty of Agriculture, Kyushu University, 812-8581, Fukuoka, Japan
Abstract: Liquefaction of whole bamboo and bamboo-lignin had been successfully performed by
PEG-bisulfite method. We tried production of carbon fiber (CF) from liquefied bamboo with cellulose acetate orcellulose triacetate by electrospinning and carbonization treatment. The CF products were analyzed with fieldemission-type scanning electron microscopy (FE-SEM) and Raman spectrometry. FE-SEM micrographs showed
the fibrous structures with average diameters ca. 30 nm from cellulose triacetate and liquefied bamboo-lignin
cooked at 200°C for 60 min. As the results of Raman spectrometry, this CF indicated the highest degree ofgraphite among the other samples. This PEG-bisulfite liquefaction can be used for preparation of the CF frombamboo and bamboo lignin.
Keywords: Bamboo-lignin, PEG-bisulfite method, Carbon fiber, Biorefinery and Electrospinning2017-209
中山間地域導入型ＰＥＧ改質リグニン製造システムの開発
山田竜彦 1, 4)、髙橋史帆 1)、ネーティティ 1)、髙田依里 1)、池田努 1)、大橋康典 2)、
松下泰幸 3)、青木 弾 3)、福島和彦 3)、中川明子 4)、飛松裕基 5)、山村正臣 5)、梅澤俊明 5)
1)森林総合研究所、2)ハリマ化成株式会社、3)名古屋大学、4) 筑波大学生命環境系、5)京都大学生存圏研
究所
Polyethylene Glycol Lignin Derivatives (Glycol Lignin) Production System for the Operation in a Rural Area ofJapan
Tatsuhiko Yamada1,4), Shiho Takahashi1), Thi Thi Nge1), Eri Takata1), Tsutomu Ikeda1),
Yasunori Ohashi2), Yasuyuki Matsushita3), Dan Aoki3), Kazuhiko Fukushima3),
Akiko Nakagawa-Izumi4), Yuki Tobimatsu5), Masaomi Yamamura5), Toshiaki Umezawa5)
1)
Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan
2)
Harima Chemicals, Inc. Japan
3)
Nagoya University, Japan
4)
University of Tsukuba, Japan
5)
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: Acid catalyzed solvolysis of Japanese cedar wood was performed using polyethylene glycol (PEG)
as a solvolysis reagent. Since PEG is a high boiling point solvent, the PEG solvolysis reactor can be operated
under atmospheric pressure without using pressure equipment. This simple and safe operability brought a
concept of introducing a small scale rural area biorefinery system to produce PEG modified lignin derivatives(glycol lignin). Since physical properties of the glycol lignin were very improved, various functional glycol
lignin based products such as heat resistant films, activated carbon fiber and FRPs were developed. A benchscale pilot plant was constructed to demonstrate stable glycol lignin production funded by a national research
program of Strategic Innovation promotion Program (SIP). In this paper, performance of the pilot scale plant638

and the characterization of the glycol lignin were discussed.
Keywords: Solvolysis, PEG, Pilot plant, Bio-refinery, Glycol lignin
2017-P01
ゲノム編集技術を用いた抑制型転写因子欠損によるリグニン増強イネの作出
高田理江 1)、宮本託志 1)、鈴木史朗 1)、飛松裕基 1)、山村正臣 1)、坂本正弘 2)、刑部敬史 3)、梅澤俊明 1), 4)1) 京都大学生存圏研究所、2) 京都大学大学院農学研究科、3) 徳島大生物資源産業学部、
4)京都大学グローバル生存基盤展開ユニット
Molecular-breeding of lignin-enriched rice by knockout of transcription factor genes associated withdown-regulation of lignin biosynthesis using a genome editing technique
Rie Takada1), Takuji Miyamoto1), Shiro Suzuki1), Yuki Tobimatsu1), Masaomi Yamamura1),
Masahiro Sakamoto2), Keishi Osakabe3), Toshiaki Umezawa1), 4)
1) Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto 611-0011, Japan
2) Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
3) Faculty of Bioscience and Bioindustry, Tokushima University, Kuramoto-cho, Tokushima 770-8503, Japan
4) Research Unit for Development of Global Sustainability, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract: Large-sized gramineous (Poaceae) plants such as Sorghum and Erianthus show higher biomass
productivity and environment-adaptive capacity than tree species, and have received much attention assustainable feedstock. On the other hand, the content of lignin, which is a major component of plant cell-walls,
is generally lower in gramineous species than in woods. Lignin has a promising market potential as chemicals to
produce valuable materials, and could increase the heating value of biomass, because it has much larger heating
values than polysacchadides. Therefore, increasing lignin content is a positive strategy to upgrade biomass
utilization. In this study, we attempted to increase lignin content of rice (Oryza sativa) by knockout of the genesthat encode transcription factors (TFs) which act as repressors for the lignin biosynthesis. First, we selected
putative repressor-type TFs (MYB and WRKY) lignin biosynthesis in previous reports and obtained theirhomologous sequences in Oryza sativa. Then, using the CRISPR/Cas9 system, targeted mutagenesis in the firstexon of each target gene was carried out. We could find several rice lines displaying increased lignin content ingenerated transformant populations.
Keywords: Lignin, Oryza sativa, MYB, WRKY, CRISPR/Cas9 system
2017-P02
-アリールエーテル代謝中間体のグルタチオン脱離に関与する glutathione S-transferase
佐藤大輔、樋口雄大、上村直史、政井英司
長岡技術科学大学・生物
Glutathione S-transferases involved in the removal of glutathione from intermediate metabolites ofarylglycerol--aryl ether
Daisuke Sato, Yudai Higuchi, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: Sphingobium sp. strain SYK-6 is able to utilize various lignin-derived biaryls including β-aryl
ether-type biaryls as the sole source of carbon and energy. In the SYK-6 cells, four stereoisomers of a β-aryl
ether-type biaryl, guaiacylglycerol-β-guaiacyl ether are converted into two enantiomers of
α-glutathionyl-β-hydroxypropiovanillone (GS-HPV) via stereospecific Cα oxidation and ether cleavage. It waspreviously thought that (βR)-GS-HPV was converted into HPV only by the reaction catalyzed by a glutathione
S-transferase (GST), LigG. However, the GST genes actually involved in the conversion of both GS-HPV
enantiomers in SYK-6 had not yet been identified. In this study, we identified and characterized the GST genes
responsible for the conversion of GS-HPV enantiomers. Four GST genes found in SYK-6 were expressed in E.
coli, and the ability of the gene products to convert both (βR)-GS-HPV and (βS)-GS-HPV was examined. As aresult, the gene products of ligG and ligQ converted both enantiomers into HPV. Characterization of SYK-6
mutants of ligG and ligQ showed that both genes were not only involved in the conversion of (βR)-GS-HPV and(βS)-GS-HPV, but also played major roles in their conversion.
Keywords: bacteria, β-O-4 linkage, glutathione S-transferase biodegradation
2017-P03
Streptomyces sp. SirexAA-E 株由来のジオキシゲナーゼを発現する組換えポプラの解析639

新海陽介 1)、諾恩達古拉 1)、上杉幹子 1)、上村直史 2)、政井英司 2)、梶田真也 1)
1)
東京農工大学大学院生物システム応用科学府 2)長岡技術科学大学大学院工学研究科
Analysis of transgenic hybrid aspen harboring dioxygenase derived from Streptmyces sp. Strain SirexAA-E
Yosuke Shinkai1), Noendagula1), Mikiko Uesugi1), Naofumi Kamimura2), Eiji Masai2), Shinya Kajita1)
1)
Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture andTechnology, Tokyo 184－8588, Japan
2)
Graduate School of Engineering, Nagaoka University of Technology, Niigata 940-2188, Japan
Abstract: Plant biomass is focused as carbon neutral resources in today, when it is concerned of depletion offossil fuel. Woody biomass is account for large percentage of plant biomass focused as ingredient of biofuelsand biomaterials. Secondary cell wall of plants is main part of woody biomass, which is composed of cellulose,
hemicellulose and lignin. Cellulose and hemicellulose are easily converted to biofuels and biomaterials.
Whereas, lignin is complex polymer and cross-links with cellulose and hemicellulose. Accordingly, efficient
removal of lignin is needed for effective utilization of woody biomass as raw materials for fuels and chemicals.
By the use of genetic engineering, we try to generate the novel biomass with the lignin which is easy to remove.
In this study, we analyzed the transgenic hybrid aspen harboring a gene for a ring cleavage dioxygenase (RCD)derived from Streptmyces sp. strain SirexAA-E change in lignin content and its molecular structure.
Keywords: Hybrid aspen, Genetic engineering, Strain SirexAA-E, Dioxygenase, Lignin
2017-P04
ゲノム編集技術を用いたコニフェルアルデヒド 5-ヒドロキシラーゼ及び p-クマロイルエステル 3-ヒドロキシラー
ゼ機能欠損イネの作出と性状解析
武田ゆり 1)、鈴木史朗 1)、飛松裕基 1)、山村正臣 1)、坂本正弘 2)、刑部敬史 3)、梅澤俊明 1)
1) 京大生存研、2) 京大院農、3) 徳島大生物資源産業、4) 京大生存基盤展開
Characterization of loss-of function mutants of rice CONIFERALDEHYDE 5-HYDROXYLASE andp-COUMAROYL ESTER 3-HYDROXYLASE genes
generated using genome-editing system
Yuri Takeda1), Shiro Suzuki1), Yuki Tobimatsu1), Masaomi Yamamura1), Masahiro Sakamoto2), Keishi Osakabe3),
Toshiaki Umezawa1,4)
1
Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
2
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
3
Faculty of Bioscience and Bioindustry, Tokushima University, Kuramoto-cho, Tokushima 770-8503, Japan
4
Research Unit for Global Sustainability Studies, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
Abstract: Aromatic composition of lignin greatly affects usability of lignocellulosic biomass and therefore has
been one of the primary targets of cell wall engineering studies. We previously demonstrated that regulations ofrice genes encoding CAld5H (OsCAld5H1) and C3′H (OsC3H1) are effective to modulate lignin aromaticcomposition in rice. Here, we generated OsCAld5H1- and OsC3H1-deficient knock-out mutants using the
CRISPR/Cas9-mediated targeted mutagenesis. We obtained various rice T0 lines with small deletions or
insertions in the targeted OsCAld5H1 and OsC3H1 genomic regions that result frame shift or truncation of theproteins. We then isolated T1 plants with high mutation efficiency and subjected their mature cell wall tissues fora series of structural analyses using chemical and NMR spectroscopic methods.
Keywords: lignin, Oryza sativa, coniferaldehyde 5-hydroxylase, p-coumaroyl ester 3-hydroxylase,
CRISPR/Cas9 system
2017-P05(Z)-ヒノキレジノール合成酵素 β サブユニットの X 線結晶構造解析
東篤志 1、坂直樹 2、鈴木史朗 1、山村正臣 1、石水毅 3、三上文三 2、梅澤俊明 1,4
1
京大・生存研、2 京大院・農学、3 立命館大・生命科学、4 京大・生存基盤展開
X-ray crystallographic analysis of (Z)-hinokiresinol synthase β subunit
Atsushi Azuma 1, Naoki Saka 2, Shiro Suzuki 1, Masaomi Yamamura 1, Takeshi Ishimizu 3,
Bunzo Mikami 2, Toshiaki Umezawa 1, 4
1Research Institute for Sustainable Humanosphere, Kyoto University, Gokesho, Uji, Kyoto, Japan
611-0011
2
Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, Japan 606-8502
3
Graduate School of Life Sciences, Ritsumeikan University, Nojihigashi, Kusatsu, Shiga, Japan
525-8577640

4Research Unit for Development of Global Sustainability, Kyoto University, Gokesho, Uji, Kyoto, Japan
611-0011
Abstract: Hinokiresinols, ones of norlignans with the simplest structure, have (Z)- and (E)- isomers1). Both (Z)and (E)-hinokiresinols are formed from p-coumaryl p-coumarate enzymatically without any cofactors2, 3).
Previously, (Z)-hinokiresinol synthase, produced in Asparagus officinalis, was suggested to be composed of two
distinct subunits, HRSα and HRSβ. Interestingly, recombinant HRSα or HRSβ can catalyze the formation of(E)-hinokiresinol while the mixture of both recombinant subunits produces (Z)-hinokiresinol with >99%(+)-enantiomer excess4). To clarify this unique molecular mechanisms, elucidation of the structures of two
subunits with X-ray crystallographic analysis is essential. In this study, the crystal structure of HRSβ was solved,
and suggested that HRSβ formed a dimeric structure in the crystals. Furthermore, the crystal structure of HRSβ
in complex with a ligand showed the probable location of the active site in HRSβ.
Keywords: norlignan, Asparagus officinalis, hinokiresinol, (E)-hinokiresinol synthase, X-ray crystallography
2017-P06
形態観察と遺伝子発現解析によるクサトベラの果実二型の比較
栄村奈緒子 1)、内貴章世 2)、梶田忠 2)、吉永新 3)、高部圭司 3)、本庄三恵 1)、工藤洋 1)１）京大生態研、２）琉大熱生研、３）京大院農Comparative analyses of morphology and transcriptome between dimorphic fruits of Scaevola taccada
Naoko Emura1), Akiyo Naiki2), Tadashi Kajita2), Arata Yoshinaga3),
Keiji Takabe3), Mie N Honjo1), Hiroshi Kudoh1)
Center of Ecological Research, Kyoto University, Japan
Tropical Biosphere Research Center, Ryukyu University, Japan
Graduate School of Agriculture, Kyoto University, Japan
Abstruct: Scaevola taccada (Asterales: Goodeniaceae) is a common coastal shrub throughout subtropical andtropical regions. Fruit dimorphism (genetically determined two types of fruit morphology), i.e., cork- andpulp-morphs, has been reported, and the mesocarp of fruit tissue is lignified in the former morph (Emura et al.
2014). The two morphs differ in seed dispersal ability and habitat preference (Emura et al. 2014). To understandthe morphological difference and genetic basis, we conducted the following comparative studies. We comparedfruit anatomy and lignin deposition between the morphs using optical and ultraviolet microscopy. Gene
expressions in fruit tissues were investigated by RNA-seq, and we found distinctive expression levels in theseries of lignin-synthesis genes between the two morphs.
Keywords: fruit, morphology, RNA-seq
2017-P07
シロイヌナズナにおけるリグニン構造改変遺伝子の探索
徳江洋介 1),2)、坂本真吾 2)、上村直史 1)、梶田真也 3)、政井英司 1)、光田展隆 2)1) 長岡技術科学大学大学院 工学研究科 生物機能工学専攻
2) 産業技術総合研究所 生物プロセス研究部門
3) 東京農工大学大学院 生物システム応用科学府 生物機能システム科学専攻
Search for lignin structure modified genes in Arabidopsis thaliana
Yosuke Tokue1),2), Shingo Sakamoto2), Naofumi Kamimura1), Shinya Kajita3), Eiji Masai1), Nobutaka Mitsuda2)
1) Department of Bioengineering, Nagaoka University of Technology, Japan2) Bioproduction Research Institute, National Institute of Advances Industrial Science and Technology (AIST),Japan
3) Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Japan
Abstract: Plant cell wall, especially lignocellulose enriched in secondary cell wall, provides physical rigidity
for plant normal growth and also has a large potential as a resource to produce next-generation biofuel andbiomaterials. However, its recalcitrance hampers the industrial use and therefore, the development of innovativetechnology to improve it is desired. This proof-of-concept study established the screening method for
identification of lignin modification enzyme genes under the control of the poplar C4H promoter, whichfunctioned in the lignified cells and tissues in Arabidopsis thaliana. Some resultant transgenic plants showed thechange of lignin staining with phloroglucinol-HCl and/or KnMO4-HCl and high glucose productivity from cellwall residue by cellulase. These results indicated that this approach is powerful tool to identify the gene which
improves cell wall quality by modifying lignin structure.
Keywords: Arabidopsis thaliana, lignin modification, C4H promoter, glucose productivity
641

2017-P08
酸化銀によるシナピル p-クマレートの酸化カップリング
山下綾菜、岸本崇生、濱田昌弘、中島範行、占部大介
富山県立大学工学部生物工学科
Oxidative Coupling of Sinapyl p-Coumarate by Using Ag2O
Ayana Yamashita, Takao Kishimoto, Masahiro Hamada, Noriyuki Nakajima, Daisuke Urabe
Department of Biotechnology, Faculty of Engineering, Toyama Prefectural University
Abstract: Among the interunit linkages in lignin, a β-O-4 bond is one of the most important bonds. The
frequency of the β-O-4 bond is about 50-60% in wood lignins. In contrast, it is reported that the frequency
reaches more than 80% in some herbaceous plant such as kenaf and abaca. The γ-position of these lignins arehighly acylated with acetic acid and p-coumaric acid. It is thought that the γ-acylated monolignols may couple
to form the β-O-4 bond more frequently than non-acylated monolignols. In this study, the oxidative coupling of
sinapyl p-coumarate was carried out with Ag2O to better understand the high frequency of the β-O-4 bond inacylated lignins.
Keywords: sinapyl alcohol, monolignol, β-ether, silver oxide, HMBC NMR
2017-P09
リグニン形成初期におけるモノリグノール二量体の脱水素重合
馬場大輔、平出秀人、松下泰幸、青木弾、吉田正人、福島和彦
名古屋大学大学院生命農学研究科
Dehydrogenation polymerization of monolignol dimer in the first of forming lignin
Daisuke Baba, Hideto Hiraide, Yasuyuki Matsushita, Dan Aoki, Masato Yoshida, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Japan
Abstract: It is believed that polymerization of lignin proceeds by continuous coupling of free radicals ofmonolignol which is the precursor of lignin. Many studies have investigated biosynthesis of monolignol, but it
is still unclear. In our previous study, the polymerization of monolignol dimers using horseradish peroxidase(HRP) was investigated, because HRP is available and the one of the most accessible enzymes. However, it isunclear whether HRP can apply to lignin formation in actual trees. In this study, we exracted enzymes fromChamaecyparis obtusa , and carried out enzymatic dehydrogenation polymerization with the extracted enzymes.
The results obtained were compared with that of the previous study using HRP, and biosynthetic process oflignin inside the actual tree was investigated.
Keyword: dilignol, dehydrogenation polymerization, Chamaecyparis obtuse, erythro/threo, radical coupling2017-P10
原子間力顕微鏡による単離リグニン孤立分子の直接観察
宮森雄大 1)，勝永毅 2)，葭谷耕三 1)，寺本好邦 1)
岐阜大学応用生物科学部応用生命科学課程
岐阜大学大学院応用生物科学研究科応用生命科学専攻
Observation of isolated lignin single molecule by atomic force microscopy
Yuta Miyamori1)，Nobuki Katsu2), Kouzou Yoshitani1)，Yoshikuni Teramoto1,3)
Faculty of Applied Biological Sciences, Gifu University, Gifu 501-1193, Japan
Graduate School of Applied Biological Science, Gifu University, Gifu 501-1193, Japan
Center for Highly Advanced Integration of Nano and Life Sciences (G-CHAIN),
Gifu University, Gifu 501-1193, Japan
Abstract: Lignin is a natural polymeric compound with complicated and random structures. Many studies
have elucidated the structures of lignin by means of chemical analysis and NMR, while these are the average
ones. Microscopic and direct visualization of the molecular structure of lignin is a challenging task. In thisstudy, we explore polymers miscible with isolated lignin and subject the blend system to atomic force
microscopy (AFM) in order to observe the lignin structure. Visualization of molecular shape of macroscopic
lignin will give us new insights into the structural studies of lignin.
Key word: blend, single molecule, visualization, DSC,
2017-P11
アルカリ性下におけるリグニンのキノンメチド構造生成に及ぼす芳香核構造および側鎖構造の影響642

山内 富由、河本 理、秋山 拓也、横山 朝哉、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Effect of the type of aromatic nucleus and side-chain structure on the formation of quinone methide structure inlignin under alkaline conditions
Fuyu Yamauchi, Osamu Kawamoto, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences,
Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan
Abstract: Although quinone methide (QM) is an important intermediate in various reactions of lignin, theformation and reactions of QM have not yet been examined well. The purpose of this study is to examine theeffect of the type of aromatic nucleus and side-chain structure on the formation of QM, employing simple lignin
model compounds. Regarding the type of the aromatic nuclei, the formation rate of QM was in the order of themodel compounds consisting of: syringyl nucleus > guaiacyl nucleus > p-hydroxyphenyl nucleus. This result
suggests that the methoxy group(s) located at the meta- of the benzyl carbon promotes the formation of QM.
This tendency was exactly the reverse of the formation rate of the benzyl cation structure (a conjugate base ofOM) under acidic conditions. Regarding the influence of the side chain structure, it was suggested that themodel compound with the secondary benzyl carbon is more favorable for the formation of QM than those withthe primary benzyl carbons.
Keywords: inductive effect, electron withdrawing, conjugation, alkene
2017-P12
Sphingobium sp. SYK-6 株における 5-5’型リグニン二量体化合物代謝系遺伝子の転写制御機構
新沼 皐、荒木 拓馬、上村 直史、政井 英司
長岡技術科学大学・生物
Transcriptional regulation of the catabolic genes of a 5-5’-type lignin-derived biaryl compound in Sphingobium
sp. strain SYK-6
Ko Niinuma, Takuma Araki, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: Sphingobium sp. SYK-6 degrades various lignin-derived biaryls and monoaryls. A 5-5’-typelignin-derived biaryl compound, 5,5’-dehydrodivanillate (DDVA), is catabolized by SYK-6 via vanillate after O
demethylation, aromatic ring cleavage, side chain cleavage, and decarboxylation. In the DDVA catabolic genes
of SYK-6, the transporter genes (tbtA and ddvK) and the catabolic enzyme genes (ligZ, ligY, and ligXa) form agene cluster. The ddvR gene which encodes a MarR-type transcriptional regulator is located in this cluster. The
objective of this study was to elucidate the transcriptional regulation of the DDVA catabolic genes. Reverse
transcription (RT)-PCR analysis showed that the DDVA catabolic gene cluster consists of three operons,
including the ligXa operon, the ddvR operon, and the tbtA operon which contains ddvK, ligZ, and ligY.
Quantitative RT-PCR analysis using SYK-6 and ddvR mutant cells revealed that the transcriptions of the ligXa
and tbtA operons were negatively regulated by DdvR, and DDVA was identified as an inducer. On the other
hand, the ddvR operon was constitutively expressed.
Keywords: 5-5’ linkage, biphenyl, biodegradation, bacteria, repressor
2017-P13
テトラブチルアンモニウムヒドロキシド中における β-O-4 型リグニンモデル化合物の分解挙動
山本康平 1)、細谷隆史 1)、宮藤久士 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Degradation of β-O-4 Type Lignin Model Compounds in Tetrabutylammonium Hydroxide Solution
Kohei YAMAMOTO1), Takashi HOSOYA1), Hisashi MIYAFUJI1), Tatsuhiko YAMADA2)
1) Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
2) Forestry and Forest Products Research Institute, Japan
Abstract: In tetrabutylammonium hydroxide (TBAH) lignin is degraded selectively into low molecular weightcompounds, especially vanillin. This study addresses degradation of phenolic and non-phenolic β-O-4 typelignin model compounds in 1.25 M TBAH and NaOH solutions, focusing on differences in reaction behaviors ofthe models and several intermediates between TBAH and NaOH. In the phenolic model, vanillin was produced
via aerobic oxidation of an enol ether intermediate. The Bu4N+ cation stabilized the intermediate, resulting insuppressed formation of vanillin from the phenolic model in TBAH. The non-phenolic model gave
veratraldehyde (precursor of vanillin) though two steps: β-ether cleavage of the model to veratryl glycerolintermediate, followed by the aerobic oxidation of the glycerol side chain. In TBAH, both steps were greatly643

enhanced, so that the model gave vanillin in much higher yield in TBAH than in NaOH.
Keywords: degradation, vanillin, tetrabutylammonium hydroxide, model compound, alkali
2017-P14
水熱処理による種々リグノセルロースのリグニン分解挙動
髙田昌嗣、南英治、河本晴雄、坂志朗
京都大学大学院エネルギー科学研究科
Decomposition behaviors of lignin in lignocellulosics by hydrothermal treatment
Masatsugu Takada, Eiji Minami, Haruo Kawamoto, Shiro Saka
Graduate School of Energy Science, Kyoto University, Kyoto 606-8501, Japan
Abstract: The decomposition behaviors of lignin in various lignocellulosics as treated by hot-compressedwater (230°C/10 MPa/15 min) were compared. As a result, the delignification from monocotyledons such as
nipa (Nypa fruticans) frond, rice (Oryza sativa) straw and corn (Zea mays) cob was more extensive than thatfrom woods such as Japanese cedar (Cryptomeria japonca) and Japanese beech (Fagus crenata). From GPC
analysis, it was found that lignin in water-soluble portion from monocotyledons was relatively higher in its
molecular weight compared to that from woods. In the water-soluble portion from monocotyledons, phenolicacids were retrieved with a high yield.
Keywords: Cinnamic acids; Delignification; Hydrothermal treatment; Lignin; Lignocellullosics
2017-P15
テトラブチルアンモニウムイオン存在下におけるスギリグニンの酸素による低分子化前田美咲 1)、細谷隆史 1)、吉岡康一 1)、宮藤久士 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Aerobic Oxidation of Japanese Cedar Lignin in the Presence of Tetrabutylammonium Ion
Misaki MAEDA1), Takashi HOSOYA1), Koichi YOSHIOKA1), Hisashi MIYAFUJI1),
Tatsuhiko YAMADA2)
1)
Graduate School of life and Environmental sciences, Kyoto prefectural University, Japan
2)
Forestry and Forest Products Research institute, Japan
Abstract: Aerobic oxidation of lignin in tetrabuthylammonium hydroxide (TBAH) solution gives vanillin andvanillic acid with high selectivity. This study presents TBAH degradation of Japanese cedar (Cryptomeria
japonica) under O2 compressed at 1.0 MPa. The TBAH degradation with the addition of NaOH under thecompressed O2 gave vanillin and vanillic acid with 8.6 and 1.5 wt% yields, which were significantly improved
from those obtained under non-compressed O2. The compressed oxygen was also effective for reduction ofrequired reaction temperature and time.
Keywords
Vanillin, Quaternary ammonium, Oxidation, Alkali, Compressed O2
2017-P16
金属塩を用いたリグニンの新規中性加水分解システムの構築
徐 烺、秋山 拓也、横山 朝哉、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Establishment of a novel neutral hydrolysis system for lignin using metal salts
Lang Xu, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract: A neutral H2O solution containing LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr, or KI was employed
to examine whether or not the cations and/or anions consisting of these salts can induce a reaction of the erythro
isomer of veratrylglycerol-β-guaiacyl ether (VG-E) at 160°C. The pH of most solutions was not exactly neutral,
which would affect the obtained results. The isomerization to the threo isomer was observed in all the solutions
except the LiI solution, where the pH was slightly alkaline (≈10). In the LiI solution, reactions other than theisomerization occurred most significantly. Veratraldehyde was detected as the only major degradation product.
Keywords: Alkyl-aryl ether, β-O-4 bond, Pulp, Wood
2017-P17
酸加溶媒分解スギリグニン中の糖由来変性物の解析644

京極未憂 1)、中川明子 1)、ネーティティ 2)、高田依里 2)、山田竜彦 1,2)
1)筑波大学生命環境系 2)森林総合研究所
Characterization of denatured carbohydrate in the polyethylene glycol solvolysis lignin prepared from Japanese
cedar
Miyu Kyogoku1), Akiko Nakagawa1), Thi Thi Nge2), Eri Takata2), Tatsuhiko Yamada1, 2)
1) Faculty of Life and Environmental Sciences, University of Tsukuba
2) Forestry and Forest Product Research Institute, Japan
Abstract: The process of acid-catalyzed PEG solvolysis of Japanese cedar to produce PEG-lignin has being
developed at FFPRI in order to promote an effective utilization of woody biomass. Because of the introductionof PEG onto lignin side-chains, the PEG-lignin possess thermal fusible property. In our previous study, somefuran structural pyrolysis compounds were detected in PEG-lignin pyrogram, which indicated that PEG-lignin
contained a trace amount of furan based polymer. It was suggested that carbohydrate was denatured into furan
based polymer. In order to confirm that hypothesis, a model experiment of PEG solvolysis of glucose, xylose,
and holocellulose of Japanese cedar was conducted and investigated the generation of denatured carbohydrates
by Py-GC/MS. Some furan structural pyrolysis compounds were detected in pyrogram of residues from model
samples. The results indicated that the furan based polymer detected in PEG-lignin are generated fromcarbohydrate components of wood through solvolysis process as denatured carbohydrate.
Keywords: solvolysis, PEG-lignin, Pyrolysis Gas chromatography/Mass spectrometry, carbohydrate, furan
based polymer
2017-P18
Phanerochaete sordida YK-624 株が有する Mn トランスポーター遺伝子の機能解析
永井 優樹 1)、森 智夫 1)、河岸 洋和 1, 2, 3)、平井 浩文 1, 2)1) 静岡大学農学部、2) 静岡大学グリーン科学技術研究所、3) 静岡大学創造科学技術大学院
Functional analysis of Mn transporter gene possessed by Phanerochaete sordida YK-624
Yuki Nagai 1), Toshio Mori 1), Hirokazu Kawagishi 1, 2, 3), Hirofumi Hirai 1, 2)
1)Faculty of Agriculture, Shizuoka University, 2) Research Institute of Green Science and Technology, 3)
Graduate School of Science and Technology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract: A homologue gene of natural resistance-associated macrophage protein (Nramp) family transporter
smf2 was identified in white rot fungus Phanerochaete sordida YK-624. Relative expression level of thehomologue, named PsMnt, were roughly same in the cultures containing 0 to 1000 µM Mn(II), nontoxic
concentration to growth of the fungus. In PsMnt homologous overexpressed mutant, cellular Mn accumulationand the exhibited manganese peroxidase (MnP) activity were significantly increased in the 4-day culture
containing10 µM Mn(II). In comparison of wild type strain, MnP activity of the overexpressed mutants werelargely increased in lower Mn concentration (specifically 15-20 times higher at 1µM Mn(II) and 7-8 times at 10µM). Although there was no difference in MnP activity secreted during beech wood decay between overexpress
and control strains, slight but significant higher activity was observed in overexpressed strain on cedar woodmeal medium than control. From these results, it was suggested that the PsMnt is a high-affinity Mn transporter
involved in cellular Mn accumulation in Mn deficient condition. This is the first report about smf2 homologue inwood rot fungi.
Keywords: Phanerochaete sordida YK-624; Mn transporter; Manganese peroxidase2017-P19
アルカリ系蒸解により分離されたリグニンの低分子化－ 硫酸-過酸化水素処理と再生二酸化マンガン処理－
勝亦京子、 清水智子、秋山拓也、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Depolymerization of lignin isolated from alkali-AQ cooking liquor - H2O2 /H2SO4 treatment and in situ
generated MnO2 treatmentKyoko S. Katsumata, Satoko Shimizu, Takuya Akiyama, Tomoya Yokoyama and Yuji Matsumoto
Laboratory of wood chemistry, Department of Biomaterial Sciences,
Graduate School of Agricultural and Life Sciences, the University of Tokyo
Abstract: The lignin obtained from the alkali-AQ cooking liquor was subjected to H2O2 /H2SO4 treatment or
manganese dioxide treatment to reduce the molecular weight. Although the polymerization of lignin wasobserved to occur by acid treatment, the molecular weight of the treated lignin became smaller with the increase645

of the hydrogen peroxide concentration during the H2O2 /H2SO4 treatment. Within the treatment condition
examined, the longer reaction time and higher reaction temperature resulted in the lower molecular weight under
the same hydrogen peroxide concentration. In case of MnO2 treatment, because the solubility in THF of theacetylated derivative of the treated lignin was low, the amount of MnO2 treated lignin detected by GPC was only
half of the original lignin. The molecular weight of this detected part of the MnO2-treated lignin was clearlylower than that of untreated lignin.
Keywords: Sugi lignin, Alkali-AQ cooking, H2O2 /H2SO4 treatment, MnO2 treatment, GPC
2017-P20
タンデムダイマー化したリグニン親和性ペプチドの結合解析とペプチド配列を担持した酵素によるリグニン分解
大城 理志１）、山口 亜佐子１,２）、渡辺 隆司１）１）京都大学生存圏研究所、２）現 大阪府立大学大学院理学系研究科
Binding analysis of tandem dimer of lignin-binding peptide and lignin degradation by the peptide-bearing
enzymeSatoshi Oshiro1), Asako Yamaguchi1,2) and Takashi Watanabe1)
1) Research Institute for Sustainable Humanosphere, Kyoto University, Japan
2) Present address: Graduate School of Science, Osaka Prefecture University, Japan
Abstract: For the establishment of lignocellulose biorefinery system through production of biofuels andaromatic chemicals from lignocellulosic biomass, highly selective lignin degradation is required. We recently
discovered a lignin-binding 12-mer peptide by the phage display technique. The peptide is a potential novel tool
improving affinity of (bio)catalysts to the substrate lignin. In this study, we improved the affinity of the peptide
to lignin by 10 times through tandem dimerization of the two lignin-binding peptide sequences. The tandem
dimer peptide changed its conformation on addition of lignin to recognize the structural differences in the lignin
from softwood and hardwood. In addition, we comparatively analyzed the properties of oxidative enzyme
bearing the tandem dimer peptide.
Keywords: Lignin binding peptide, FTIR, conformation change, lignin degrading enzyme
2017-P21
ヒト腸内細菌 Blautia producta ATCC27340 におけるリグナン O-デメチラーゼの探索
久留菜美 1）、鈴木史朗 1）、内海龍太郎 2）、梅澤俊明 1, 3）1）京都大・生存研、2）近畿大・農・バイオ、3）京都大・生存基盤展開
Search of a lignan O-demethylase from a human intestinal bacterium,
Blautia producta ATCC27340
Nami HISADOME1), Shiro SUZUKI1), Ryutaro UTSUMI2), Toshiaki UMEZAWA1, 3).
1)
Research Institute for Sustainable Humanosphere, Kyoto University
2)
Department of Advanced Bioscience, Faulty of Agriculture, Kindai University
3)
Research Unit for Development of Global Sustainability, Kyoto University, Japan
Abstract: A lignan glycoside, secoisolariciresinol diglucoside (SDG), is one of the most abundant dietary
lignans. After oral administration of SDG, SDG is converted into the mammalian lignans, enterodiol (ED) andenterolactone (EL), by human intestinal bacteria. The mammalian lignans are lignan-type phytoestrogens andcontribute the reduction of risk of breast cancer in females. Elucidation of the formation mechanism for
mammalian lignans could be useful for further reduction of risk of breast cancer. In addition, theO-demethylation and dehydoxylation of aromatic rings in mammalian lignan formation attract a great attention
because these reactions are essential for eliminating methoxyl substitutions in aromatic monomers or oligomers
derived from depolymerized lignin in lignin biorefineries. To date, few human intestinal bacterial species
including Eubacterium limosum and Blautia producta, have been known to catalyze O-demethylation, and very
recently a tetrahydrofolate-dependent secoisolariciresinol (SIR) O-demethylase has been identified in E.
limosum ZL-II. Thus far, however, any O-demethylase has not been identified in other bacteria. To get more
information of O-demethylation mechanisms in mammalian lignan biosynthesis, we aim at identifying a lignan
O-demethylase in B. producta ATCC27340.
Keywords: tetrahydrofolate-dependent O-demethylase, mammalian lignan, human intestinal bacteria, Blautia
producta, anaerobic condition
2017-P22
Sphingombium sp. YG1 由来 guaiacylglycerol-β-guaiacyl ether - Cα 位酸化酵素の酵素学的解析と利用646

前田 亜鈴悠 1)、宋 晶 1)、西 真郎 1)、黒澤 佳奈子 1)、市川 淳子 1)、
塩谷 美夏 1)、山置 佑大 2)、永田 崇 2)、片平 正人 2)、山田 美紗登 3)、
西村 裕志 3)、渡辺 隆司 3)、大田 ゆかり 1)
1
国立研究開発法人海洋研究開発機構、2 京都大学エネルギー理工学研究所、
3
京都大学生存圏研究所
Enzymatic characterization and application of guaiacylglycerol-β-guaiacyl ether – Cα-dehydrogenases from
Sphingobium sp. YG1Allyn H. Maeda1), Jing Song1), Shinro Nishi1), Kanako Kurosawa1), Junko Ichikawa1),
Mika Shioya1), Yudai Yamaoki2), Takashi Nagata2), Masato Katahira2), Misato Yamada3),
Hiroshi Nishimura3), Takashi Watanabe3), Yukari Ohta1)
Japan Agency for Marine-Earth Science and Technology (JAMSTEC), JAPAN
Abstract: A bacterial enzymatic cascade for β-O-4 reductive cleavage in lignin model dimers consists ofCα-dehydrogenases belonging to short-chain dehydrogenase/reductase (SDR) superfamily, β-etherases andβ-glutathione thioetherases (glutathione lyases) belonging to glutathione-S-transferase (GST) superfamily. In
this study, enzymatic characterization of a recently identified Cα-dehydrogenase from Sphingobium sp. YG1
isolated from Kagoshima Bay was conducted. The recombinantly-expressed enzyme showed higher activity forhydroxyl moiety at Cα (benzyl) position of guaiacylglycerol-β-guaiacyl ether (GGGE) than the other reported
homologous enzymes. The enzyme could act on a lignin fraction extracted from hard wood (Eucalyptus
globulus), indicating future applications as a tool for lignin enzymatic conversion.
Keywords; β-O-4 linkage, enzymatic cleavage, Cα-dehydrogenase, short-chain dehydrogenase/reductase,
Sphingobium
2017-P23
フラグメント分子軌道法を活用したリグニン β-O-4 還元開裂酵素の機能改変
嶋根康弘 1)、黒澤佳奈子 1)、市川淳子 1)、前田亜鈴悠 1)、布浦拓郎 1)、山置佑大 2)、永田崇 2)、片平正人 2)、
高谷光 3)、吉田亮太 3)、中村正治 3)、磯崎勝弘 3)、渡辺隆司 4)、大田ゆかり 1)
1) 海洋研究開発機構、2) 京都大学エネルギー理工学研究所、
3) 京都大学化学研究所、4) 京都大学生存圏研究所
Analysis of β-O-4 cleaving enzyme, GST4, from the marine bacterium, Novosphingobium sp. MBES04
Yasuhiro Shimane1), Kanako Kurosawa1), Junko Ichikawa1), Allyn H. Maeda1),
Takuro Nunoura1), Yudai Yamaoki2), Takashi Nagata2), Masato Katahira2), Hikaru Takaya3),
Ryota Yoshida3), Masaharu Nakamura3), Katsuhiro Isozaki3), Takashi Watanabe4), Yukari Ohta1)
1)Japan Agency for Marine-Earth Science and Technology, Japan
2)
Institute of Advanced Energy, Kyoto University, Japan
3)
Institute for Chemical Research, Kyoto University, Japan
4)
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract
The marine bacterium, Novosphingobium sp. MBES04, isolated from a sunken wood was capable ofmetabolizing the stereoisomers of β-O-4 lignin dimers into the respective monomers (phenylpropane units) by
combination of five enzymes. A GST4 is a glutathione-dependent β-etherase, and one of the key enzymes in thepathway which selectively catalyzes reductive cleavage of β-O-4 aryl-ether bonds in lignin. In this study, we
tried to improve the activity of GST4 by computational assisted molecular designing using the fragment
molecular orbital (FMO) method so that the enzyme can convert lignin more efficiently. Mutational studies
demonstrated that single or double amino acid substitution mutants, GLY117ALA and HIS39GLN_GLY117ASP
showed considerable improvement in their specific activities.
Keywords: Lignin, Novosphingobium, GST, fragment molecular orbital method, FMO
2017-P24
リグニンの t-ブチル化による自己縮合反応制御
白木 裕也 1)、野中 寛 1)
1)三重大学大学院生物資源学研究科 資源循環学専攻
t-Butylation of lignin for preventing the self-condensation
Yuya Shiraki1) and Hiroshi Nonaka1)
1) Graduate School of Bioresources, Mie University, Mie, 514-8507, Japan
Abstract: Hinoki wood meal was treated with concentrated sulfuric acid prepared with t-butyl alcohol and647

95 % sulfuric acid to prevent self-condensation reaction of lignin. The reaction mixture was diluted, boiled andthe acid insoluble fraction was recovered. The yield of the acid insoluble fraction was higher than that simply
treated with 72 % sulfuric acid and the FT-IR spectrum demonstrated remarkable absorption of methyl groups.
The solubility of the acid insoluble fraction in various organic solvents was significantly increased by additionof t-butyl alcohol. TMA curves showed that it has thermal fluidity. These results suggest that the
self-condensation of lignin was successfully prevented by t-butylation of the lignin.
Keywords: t-butyl alcohol, concentrated sulfuric acid, self-condensation, solubility, fluidity
2017-P25
改質リグニン製造システムへの薬液再生プロセスの導入
髙田依里 1)、池田努 1)、ネーティティ 1)、髙橋史帆 1)、高山遼太郎 2)、
谷口勇希 2)、山本麻衣子 2)、大橋康典 2)、山田竜彦 1)
1) 森林総合研究所、2) ハリマ化成株式会社
Development of solvent regeneration process in the PEG solvolysis system for glycol lignin production
Eri Takata1), Tsutomu Ikeda1), Thi Thi Nge1), Shiho Takahashi1), Ryotaro Takayama2),
Yuki Taniguchi2), Maiko Yamamoto2), Yasunori Ohashi2), Tatsuhiko Yamada1)
1) Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan
2) Harima Chemicals, Inc., Saitama 340-0003, Japan
Abstract: The acid-catalyzed solvolysis system of Japanese cedar using a glycol solvent is being developed to
produce glycol modified lignin derivatives (glycol lignin). To decrease operational costs, a glycol solvent used
as a solvolysis liquor need to be recovered and reused. In this study, the solvolysis liquor, polyethylene glycol(PEG), was recovered by removal of water from the supernatant of solvolysis liquor after glycol lignin
precipitation, and the recovered PEG was reused in next production line. A diluted acid hydrolysis treatment
was conducted to the recovered PEG in order to activate the reactivity of the PEG. The amount of the terminalhydroxyl groups of the recovered PEG was increased by the hydrolysis treatment. The reactivity came back to
the level of fresh PEG by the regeneration process of the hydrolysis.
Keywords: Acid-catalyzed solvolysis; Glycol lignin; Polyethylene glycol (PEG); Solvent regeneration;
Softwood
2017-P26
テトラブチルアンモニウムヒドロキシドを用いたバニリン生産における生成物の分離精製法の開発
溝口晃平 1)、前田美咲 1)、細谷隆史 1)、宮藤久士 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Separation of Vanillin from the Reaction Mixture Formed in Degradation of Lignin in Tetrabuthylammonium
Hydroxide solution
Kohei MIZOGUCHI1), Misaki MAEDA1), Takashi HOSOYA1), Koichi YOSHIOKA1),
Hisashi MIYAFUJI 1), Tatsuhiko YAMADA2),
1) Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
2) Forestry and Forest Products Research Institute, Japan
Abstract: Aerobic oxidation tetrabutylammonium hydroxide (TBAH) gives vanillin with high selectivity. For
industrial application of the TBAH method, development of vanillin isolation techniques is indispensable. To
this end, this study addresses extraction of vanillin from the alkaline solution obtained after the TBAH treatment
of Japanese cedar (Cryptomeria japonica) by EtOAc. Our investigation clarified that vanillin was efficiently
extracted with EtOAc regardless of the acidification process by HCl aq. before the extraction. The direct
extraction of vanillin from the alkaline solution was feasible probably because of decrease in pH of the solution
by the AcOH formation from EtOAc by OH- and the ion pair formation between the vanillin anion and the
Bu4N+ cation.
Keywords: vanillin isolation, extraction, alkaline solution, EtOAc, ion pair formation
2017-P27
テトラブチルアンモニウムヒドロキシド中における β-5 型構造からのバニリン生成
吉村沙樹子 1)、細谷隆史 1)、宮藤久士 1)、山田竜彦 2)1) 京府立生環、2)森林総研
Vanillin Production from a β-5 Type Lignin Model Compound in Tetrabutylammonium Hydroxide-30H2O
Sakiko YOSHIMURA1), Takashi HOSOYA1), Hisashi MIYAFUJI1), Tatsuhiko YAMADA2)
648

1)

Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
Forestry and Forest Products Research institute, Japan
Abstract: Degradation of lignin in the presence of tetrabutylammonium hydroxide (TBAH) and oxygen gives
vanillin and its related compounds with high selectivity. This study presents degradation behavior of β-5 type
and β-O-4 type lignin model compounds in their TBAH treatment and alkaline nitrobenzene (AN) oxidation. In
the TBAH treatment vanillin was produced both from the β-5 and β-O-4 models with moderate yields of 59.9
and 40.3 mol%, respectively. In the AN oxidation, although the β-O-4 model gave vanillin with very high yieldof 91.2 mol%, the β-5 model did not yield vanillin, at all. These results suggest that lignin polymers produce
vanillin from β-5 and β-O-4 structures in the TBAH treatment, whereas only β-O-4 structures are subjected tovanillin formation in the AN oxidation.
Keywords: vanillin, β-5 linkage, model compound, alkaline nitrobenzene oxidation, tetrabutylammmoniumhydroxide,2)

2017-P28
イオン液体中でのマイクロ波照射によるスギ木粉からのメチルグリコシドの合成
斉藤真冬、岸本崇生、濱田昌弘、中島範行、占部大介
富山県立大学工学部
Synthesis of methyl glycoside from Japanese cedar (Cryptomeria japonica) in ionic liquid under microwave
irradiation
Mafuyu Saito, Takao Kishimoto, Masahiro Hamada, Noriyuki Nakajima, Daisuke Urabe
Faculty of Engineering, Toyama Prefectural University, Toyama 939-0398, Japan
Abstract: Conversion of a lignocellulosic biomass into useful substances has attracted increasing attention inrecent years. In this study, acid-catalysed conversion of cellulose to methyl glucoside was investigated by using
microwave reactor and ionic liquid as a solvent. Microcrystalline cellulose (Avicel) was reacted with acetyl
chloride (AcCl)-MeOH in 1-allyl-3-methylimidazolium chloride ([Amim]Cl)/N-methyl-2-pyrrolidone (NMP).
By oil bath heating, methyl α, β-D-glucopyranoside was generated in 43% yield. In contrast, MW heating
resulted in 71% yield. The yield decreased to only 6% by MW heating when MeOH was used as a solvent
instead of [Amim]Cl/NMP treatment. The results showed that the combined use of MW heating and ionic liquid
effectively improved the conversion of Avicel to methyl glucopyranoside. Conversion of Japanese cedar into
methyl glycoside was also conducted under the same conditions.
Keywords: biorefinery, ball-milled wood, acid-catalyst, microwave, ionic liquid
2017-P29
Effect of starting wood meal type on properties of glycol lignin produced by acid-catalyzed polyethylene glycol(PEG) solvolysis
Thi Thi Nge1), Shiho Takahashi1), Eri Takata1), Tsutomu Ikeda1), Yuki Tobimatsu2), Masaomi Yamamura2),
Toshiaki Umezawa2), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687
2)
Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: In this work, three types of sugi wood meal were used as starting material to isolate PEG-substituted
lignin, namely glycol lignin (GL) by acid-catalyzed polyethylene glycol (PEG) solvolysis process. The effect ofsugi wood meal type, especially the meal size on the properties of lignin products, such as lignin contents,
molecular weight, structural and thermal behavior were then investigated.
Keywords: glycol lignin, polyethylene glycol (PEG) solvolysis, wood meal size, 2D NMR, TMA
2017-SP1
細胞壁の木化
高部圭司
京都大学大学院農学研究科
Lignification of cell wall
Keiji TAKABE
Graduate School of Agriculture, Kyoto University, Kyoto 606-8502, Japan
Abstract: Lignification starts at cell corner middle lamella when the secondary wall formation starts, and thenproceeds toward compound middle lamella. Lignification of secondary wall starts at cell corner region of outerS1 layer, proceeds toward outer S1 layer, and then centripetally lagging behind cell wall thickening.
Monolignols are synthesized by the catalytic reactions of enzymes localized in the cyto-sol and on the649

membrane of cell organelle during secondary wall formation. They are transported toward the cell wall by somemechanism, and polymerized to form globular structures of lignin.
Keywords: lignification, lignin, middle lamella, monolignol, secondary wall
2017-SP2
木部道管二次細胞壁のリグニン沈着の制御メカニズム出村拓１）、大谷美沙都１）
１）奈良先端科学技術大学院大学・バイオサイエンス研究科
Regulatory mechanisms underlying lignin deposition on secondary cell walls of xylem vessels
Taku Demura1), Misato Ohtani1)
1)
Graduate School of Biological Sciences, Nara Institute of Science and Technology, Ikoma, Nara 630-0192,
Japan
Abstract: We previously established the in vitro systems for vessel cell differentiation, which include
lignification of secondary cell walls (SCWs). The transcriptome analyses with the culture systems identified anumber of genes related to lignification of SCWs and the regulation of vessel cell differentiation. Detailed
analysis of these genes revealed the mechanisms of SCW lignification. For example, it was found that lignin
deposition in SCWs is not dependent on cellulose patterning. Also, two previously uncharacterized DOF
transcription factors are found to have a suppressive function on the lignin deposition in Arabidopsis stem
vasculature. We will discuss about such the knowledge on SCW lignification revealed through the in vitro
systems.
Keywords: DOF transcription factor; in vitro culture system; secondary cell wall; VNS transcription factor;
xylem vessel
2017-SP3
陸上植物の進化と木化のバイオメカニックス
山本浩之 1)
名古屋大学大学院生命農学研究科
Biomechanics of evolution of wood in terrestrial plant
Hiroyuki Yamamoto1)
Laboratory of Biomaterial Physics, Graduate School of Bioagricultural Sciences,
Nagoya University, Chikusa, Nagoya 464-8601, Japan
Abstract: In this presentation, physical meanings of secondary xylem formation and its development are
discussed from the viewpoint of evolutionary strategy of terrestrial plant. We start our discussion frommechanical implication of occurrence of vascular bundle tissue and eustele stem in ancient plant. And our
discussion focuses on the growth stress generation as a new technique for surviving the race of forest trees for
growing mammoth.
Keywords: plant history, paleobotany, secondary xylem, growth stress, eustele650

第 63 回 （2018.11.1-2） 東京農工大学 グリーンホール、科学博物館
2018-101
中性付近におけるハロゲン化アルカリ金属を用いた新規脱リグニン系の検討
徐 烺、秋山 拓也、○横山 朝哉、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Establishment of a novel delignification system using alkali metal halides under circumneutral pH conditions
Lang Xu, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract: A neutral H2O solution containing LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr, or KI was treated at
160°C to examine whether or not these salts induce a reaction of veratrylglycerol-β-guaiacyl ether (VG). The
pHs of most of these solutions were not exactly neutral, and dependent on the type of the salts. The erythro
isomer of VG (VG-e) isomerized to the threo isomer (VG-t) in all the solutions except for the LiI solution,
where the pH was relatively higher (≈10) than those in the other solutions. It was confirmed that VG-e
isomerizes in the solutions with the pHs lower than 10, which suggests that the benzyl cation generates from
VG-e and hence VG-e can possibly undergo the acidolytic reaction route. To quench the possible acidolytic
reaction route, the same solutions of VG-t except for those of the K salts were treated after the pHs werearranged to be slightly higher than 10. It was confirmed that the LiI and NaI solutions induce the degradation of
VG-t without isomerizing to VG-e (LiI > NaI), which was contrast to the LiCl, LiBr, NaCl, and NaBr solutions.
Veratraldehyde and guaiacol were detected as reaction products.
Keywords: Alkyl-aryl ether; β-O-4 bond; Lithium iodide; Sodium iodide
2018-102
Investigation on the Cleavage Reaction of the β-O-4 Bond in Lignin Caused by tert-Butoxide
Xu Zeng1), Tomoya Yokoyama1), Takuya Akiyama1) and Yuji Matsumoto1)1). Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural andLife Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan.
Abstract: The erythro or threo isomer of the C6-C3-type non-phenolic β-O-4 lignin model compound,veratrylglycerol-β-guaiacyl ether (IIIe or IIIt, respectively), was reacted in a DMSO solution containing
potassium tert-butoxide with a concentration of 0.5 mol/L at 30°C. These reaction conditions were much milder
than those employed in a common alkaline pulping process. The results were compared with those obtained in
our previous study where the corresponding C6-C2-type compound, veratrylglycol-β-guaiacyl ether (II), wastreated under the identical conditions.
The disappearance rates were in the order of: compound IIIe >> compound IIIt > compound II, which is notaccordance with those observed in a common alkaline pulping process using NaOH under elevated temperature(compound IIIe > compound II > compound IIIt). This result suggests that the γ-hydroxy group participates inthe disappearance reaction of compound IIIe as well as compound IIIt. Because guaiacol (2-methoxyphenol)
was not quantitatively liberated accompanying the disappearance of compound IIIe or IIIt in contrast to thereaction of compound II, not only the β-O-4 bond cleavage but also some other reactions contribute to thedisappearance of compound IIIe or IIIt.
Keywords: potassium tert-butoxide, non-phenolic, γ-hydroxymethyl group, β-O-4 bond, cleavage.
2018-103
ソーダ蒸解過程における C6-C1 型リグニンモデル化合物の縮合反応に関する定量的研究〇小松聡浩、秋山拓也、横山朝哉、松本雄二
東京大学大学院農学生命科学研究科
Quantitative Study on Condensation Reaction of C6-C1 type Lignin Model Compounds under Soda Cooking
Process
Toshihiro Komatsu, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan
Abstract: Condensation reaction of lignin was quantitatively examined under common soda cooking
conditions using simple C6-C1-type lignin model compounds, vanillyl alcohol (A) and creosol (B). A
condensation product was isolated and identified by several NMR analyses to be dimer AB consisting of the
α-5-type interunit linkage. The yield of dimer AB was 10% or 50% based on the initial mole amount ofcompound A, when the ratio of the initial concentrations of compounds A and B was 1/1 or 1/5, respectively.
651

Chromatographic analyses suggested the formation of the other condensation product, which is not fully
identified yet but was also detected in the reaction using only compound A, which indicates that compound A
undergoes the self-condensation. Interestingly, in the reaction using only compound A, vanillin (C) andcompound B were detected. Although their yields were not very high, the formation of these compounds
suggests that the quinone methide primarily derived from compound A can oxidize compound A to generate twocompounds: compound B as the reduction product of quinone methide, and, compound C as the oxidation
product of compound A. Such a redox reaction of quinone methide may play a certain role in the alkalinedelignification process.
Keywords: soda cooking, quinone methide, condensation reaction
2018-104
天然系メディエーターによるリグニン電解酸化の検討○中健一郎 1），飛松裕基 2），上高原浩 1）, 高野俊幸 1）
1）京大院農, 2）京大生存研
Lignin oxidation by electrolytic mediator system with natural mediators〇Kenichiro Naka1）, Yuki Tobimatsu2）,
Hiroshi Kamitakahara1）,Toshiyuki Takano1）
1）Graduate School of Agriculture, Kyoto University, Japan
2）Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: It is well-known that lignin degradation products (phenolic compounds with low molecular weight)
participate to the lignin microbial degradation as mediators in nature. Therefore, the lignin degradation products
are also promising candidates for the mediators in lignin degradation by electrolytic mediator system (EMS). In
this study, guaiacyl-type artificial lignin (G-DHP) oxidation by EMS with methyl syringate (MS),acetosyringone (AS), syringaldehyde (SA) as natural mediators were investigated. It was found that the natural
mediators showed higher lignin oxidation abilities than the artificial mediators which we have investigated suchas NHPI, ABTS and so on, and that C -oxidation of G-DHP proceeded preferentially.
Keywords: DHP, Electro-oxidation, EMS, Lignin, Mediator2018-105
Analysis of microwave effects cleaving covalent bonds of lignin substructures by copper oxide-peroxide
reaction〇 Chen Qu1), Keigo Ito1), Isamu Katusyama1), Tomohiko Mitani1), Kashimura Keiichiro2), Takashi
Watanabe1)
1)
RISH, Kyoto University
2)
Information Technology Section, General Education Division, College of Engineering, Chubu
University
Abstract: Microwave irradiation promoted production of vanillin and vanillic acid from woody biomass by thereaction with CuO and H2O2 under an alkaline medium. In this study we analyzed if microwave directly
accelerates degradation of phenolic (erythro) and non-phenolic (erythro) -O-4 lignin dimer model compounds
under the conditions of the same temperature profile, stirring speed and reaction vessel with those of
conventional heating using an oil bath. The main reaction products were vanillin, vanillic acid, veratraldehyde,veratric acid, guaiacol and dicarboxylic acids including fumaric acid, maleic acid, malic acid, malonic acid andsuccinic acid. Profiles of the microwave accelerating effects are reported.
Keywords: copper oxide, microwave, peroxide2018-106
水素供与体を含む芳香族溶媒中での木材リグニンの熱分解○ワン・ジャキ、 河本晴雄
京都大学大学院エネルギー科学研究科
Pyrolytic degradation of lignin in wood in the presence of hydrogen donor and aromatic solvent○Jiaqi Wang, Haruo Kawamoto
Graduate School of Energy Science, Kyoto University, Japan
Abstract: Hydrogen donor and aromatic solvent are expected to stabilize lignin primary pyrolysis products
against secondary polymerization during lignin pyrolysis by inhibiting the radical coupling and condensation via
quinone methide (QM) intermediate, respectively. In this study, cedar wood was pyrolyzed in the presence of652

1,2,3,10b-tretrahydrofluoranthene (H-donor) and 1,3-diphenoxybenzene (DPB, aromatic solvent) under theconditions of 350 ℃/N2/5 min. The pyrolysis mixture was extracted with a binary mixture of H2O/EtOAc,
followed by the extraction of the EtOAc-soluble portion with n-hexane after evaporation. This procedure wasfound to be effective for separation of the carbohydrate- (H2O-layer) and lignin-derived(EtOAc-layer-hexane-insoluble) products from the H-donor and solvent, by analyzing these fractions with 1H
NMR and GPC. The GC/MS analysis of the hexane-soluble fraction (H-donor and solvent) indicated that the
H-donor could be utilized during pyrolysis. With this pyrolysis method, most of the lignin in cedar wood wasconverted mainly into the oligomers, which were soluble in CHCl3, although the yield was only quite low in theconventional cedar wood pyrolysis. These lignin-derived products can be utilized for further conversion, aiming
at the aromatic chemical production.
Keywords: Pyrolysis, aromatic solvent, H-donor, separation, aromatic chemical
2018-107
酵素的脱水素重合におけるβ-5 位ジリグノールの挙動解析〇大藪悠登、松下泰幸、青木弾、福島和彦
名古屋大学生命農学研究科
Behavior analysis of β-5 dilignol in enzymatic dehydrogenative polymerization
Yuto Oyabu, Yasuyuki Matsushita, Dan Aoki, Kazuhiko Fukushima
Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
Abstract: Lignin is one of the major components of the plant cell wall. The biosynthesis of lignin is started
from the formation of dimers by radical coupling of two monolignols. Then, the dimers are subjected to further
radical coupling with monolignols or dimers to form oligomaers. In the case of β-5 dimer, it is thought that thephenolic hydroxyl group or 5-position of aromatic ring of ring A were participated in the radical coupling, butthere is a possibility that β position of ring B is involved in the reaction.
The purpose of this research is to investigate the reaction of β-5 dimer in the radical coupling. We synthesized
the 13C labeled β-5 dimer at the β-position of the ring B (I) through 8-step reactions using vanillin as a starting
material. And then we prepared DHPs from I and the unlabeled analogue (II) as a substrate, respectively. The
DHPs were analyzed by HSQC NMR. It was observed that the peak intensity was increased at three regions in
the HSQC spectrum of DHP made of I by compared with that of II. This results indicated that β-position of thering B was participated in the radical coupling reactions.
Keywords:β-5 dimer, DHP, HSQC NMR, selective 13C-enrichment
2018-108
SEC-MALLS を用いたクラフトリグニンおよび関連化合物の分子量測定
王 林萍 1)、重富顕吾 2)、幸田圭一 2)、○浦木康光 2)1) 北海道大学 大学院農学院, 2) 北海道大学 大学院農学研究院
Molar mass measurement of kraft lignins and their related compounds with SEC-MALLS
Linping Wang1), Kengo Shigetomi2), Keiichi Koda2), Yasumitsu Uraki2)
1) Graduate School of Agriculture, Hokkaido University, Sapporo 060-8589, Japan
2) Research Faculty of Agriculture, Hokkaido University, Sapporo 060-8589, Japan
Abstract: Molar masses of acetylated softwood and hardwood kraft lignins and linear polymeric lignin models,
which consisted only of β-O-4 interunitary linkage, were measured on a size-exclusion chromatographyequipped with multi-angle laser light scattering detector at 785 nm of incident laser wavelength. Both acetylated
kraft lignins indicated much larger (more than 5 times) molar mass than authentic polystyrene standards at any
retention time. However, polymeric lignin models showed similar molar masses to the polystyrene standards.
This difference in molar mass between acetylated kraft lignins and acetylated lignin models must be attributed
to the branched structure of kraft lignins.
Keywords: Absolute molar mass, Mark-Houwink-Sakurada equation, Intrinsic viscosity, Hydrodynamic radius,
Self-fluorescence
2018-109
Assembly of electric double layer capacitor with electrode made from lignin and ionic liquid as an electrolyte○ Nutthira Pakkang1), Keiichi Koda2), Yasumitsu Uraki2)
1) Graduate School of Agriculture, Hokkaido University, Sapporo, 060-8589, Japan
2) Research Faculty of Agriculture, Hokkaido University, Sapporo, 060-8589, Japan
Abstract: Our research group has already reported preparation of electrode material for electric double layer653

capacitor (EDLC) from several isolated lignins through electrospinning, carbonization and steam activation.
Such EDLC was assembled with lignin-based electrode and organic electrolyte, triethylmethylammonium
tetrafluoroborate/propylene carbonate solution (TEMABF4/PC). In this study, to improve an energy density of
EDLC, an ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4), was attempted to be used as
the electrolyte, which could expand the operation voltage window due to its electric stability at higher voltage.
However, the ionic liquid was larger in molecular size than the organic electrolyte. Therefore, a main objectiveof this study was to develop lignin-based electrode material with suitable pores for the size of EMIBF4.
A target electrode was obtained from a polymer blend of hardwood kraft lignin (HKL) and polyethylene glycol(PEG) at different ratios as starting materials, which was electrospun followed by thermostabilization,
carbonization and steam activation. When PEG ratio was increased to 5%, the resultant carbonaceous electrode
had larger BET specific surface area and average pore size compared to those of the electrode prepared with 1%
PEG blend. As a result, EDLC with the electrode from 5% PEG blend showed 65 Wh/kg of energy density,
which is 1.5–fold that of the EDLC we reported previously.
Keywords: Electric double-layer capacitor (EDLC), Hardwood kraft lignin, Hexamine, Ionic liquid Electrolyte
2018-110
中山間地域導入型ＰＥＧ改質リグニン製造システムの生産性〇山田竜彦 1,3)、髙橋史帆 1)、ネーティティ 1)、髙田依里 1)、池田努 1)、大橋康典 1)、松下泰幸 2)、青木 弾
2)、福島和彦 2)、中川明子 3)、飛松裕基 4)、山村正臣 4)、梅澤俊明 4)1)森林総合研究所、2)名古屋大学、3) 筑波大学生命環境系、4)京都大学生存圏研究所
Productivity of the Japan Rural Area Type of the PEG Lignin Derivative (Glycol Lignin) Production System
Tatsuhiko Yamada1,3), Shiho Takahashi1), Thi Thi Nge1), Eri Takata1), Tsutomu Ikeda1), Yasunori Ohashi1),
Yasuyuki Matsushita2), Dan Aoki2), Kazuhiko Fukushima2), Akiko Nakagawa-Izumi3), Yuki Tobimatsu4),
Masaomi Yamamura4), Toshiaki Umezawa4)
1) Forestry and Forest Products Research Institute, Ibaraki 305-8687, Japan
2) Nagoya University, Japan
3) University of Tsukuba, Japan
4) Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: Acid catalyzed solvolysis of Japanese cedar wood was performed using polyethylene glycol (PEG)
as a solvolysis reagent. A bench scale pilot plant was constructed to demonstrate stable PEG modified lignin
derivatives (glycol lignin) production funded by a national research program of Strategic Innovation promotion
Program (SIP). In this paper, performance of the pilot scale plant was discussed. The total process efficiency
analysis showed that the solid-liquid separation process of glycol lignin preparation was the most electric energy
consuming process. To improve the efficiency of the filtration, flocculation of the glycol lignin particle waspromoted by a heating treatment of the glycol lignin suspension. As the total result, the amount of electricity
consumption was reduced to a one-third in the solid-liquid separation process of glycol lignin preparation.
Keywords: Solvolysis, PEG, Bio-refinery, Glycol lignin, Japanese cedar
2018-111
テトテトラブチルアンモニウムヒドロキシドを反応媒体とした各種リグニン試料からのバニリン生産○宮藤久士 1)、溝口晃平 1)、山本康平 1)、前田美咲 1)、吉村沙樹子 1)、岡本大輝 1)、細谷隆史 1)、吉岡康
一 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Vanillin Production from Several Lignin Samples with Tetrabutylammonium Hydroxide as a Reaction Medium
Hisashi MIYAFUJI1), Kohei MIZOGUCHI1), Kohei YAMAMOTO1), Misaki MAEDA1), Sakiko
YOSHIMURA1), Daiki OKAMOTO1), Takashi HOSOYA1), Koichi YOSHIOKA1), Tatsuhiko YAMADA2)
1) Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
2) Forestry and Forest Products Research Institute, Japan
Abstract: Aerobic oxidation of lignin in tetrabutylammonium hydroxide (TBAH) produces vanillin and its
related phenols with high selectivity. This study addresses vanillin production from several types of lignin suchas PEG-modified glycol lignin from Japanese cedar (Cryptomeria japonica) and sodium lignosulfonate in a
TBAH-based reaction solution, as compared with the results previously reported for natural lignin in Japanesecedar. The aerobic oxidation (120 oC/air) of the PEG-modified glycol lignin and sodium lignosulfonate (14 mg)
as well as the cedar wood in the TBAH-based solution (2.0 mL) resulted in significantly higher vanillin yieldthan those in a simple alkaline (NaOH) solution, regardless of the presence of the -sulfo group. We also
performed vanillin production from the PEG-modified glycol lignin in a larger reaction system (100 g of654

sample/1.0 L of the reaction solution) under pressurized O2 (0.7-2.5 MPa). In spite of the increased reaction
scale, high vanillin yield (6.4 wt%) was maintained, compared to the vanillin yield (7.0 wt%) obtained in theabove 14 mg/2.0 mL scale.
Keywords: Vanillin, Tetrabutylammonium hydroxide, Oxidation, Alkali, PEG-modified glycol lignin
2018-112
Effect of pretreatment on catalytic depolymerization of lignin in ionic liquid-solvent mixture
Xiuhui Wang, Yuta Yamamoto, Thanh Tung Nguyen, Eika W. Qian
Graduate School of Bio-Applications and Systems Engineering, Tokyo university of Agriculture and Technology,
Japan
Abstract: Pyridinium-based and imidazolium-based ionic liquids with different anions were synthesized andtested for the dissolution and subsequent extraction of lignin. Among used ionic liquids, pyridinium-based ionicliquids showed higher dissolution capacity than imidazolium-based ionic liquids at 80 ℃. Through extractionof lignin from alkali lignin-[Apy]Cl solution with different antisolvents, the results indicate that water andacetonitrile were promising ones and 97.3% recovery of lignin gotten from red pine. Furthermore, a continuous
flow fixed-bed reaction system was developed to study the catalytic depolymerization of lignin at a lowtemperature using ZrO2/SO42− as the catalyst, and lignin-[Apy]Cl solution as the feedstock. Due to thepretreatment by [Apy]Cl, lignin was more readily decomposed in the reactor at low temperature. As expected,
the phenolic compounds were the primary compounds observed in the identified compounds at 210 °C.
Keywords: ionic liquid; lignin; lignocellulose; pretreatment; catalytic depolymerization
2018-113t-ブチルアルコールを用いた硫酸リグニンの熱可塑性制御○ 白木 裕也，野中 寛
三重大学大学院生物資源学研究科 資源循環学専攻
Control of thermoplasticity of sulfuric acid lignin using t-butyl alcohol
Yuya Shiraki and Hiroshi Nonaka
Graduate School of Bioresources, Mie University, Mie, 514-8507, Japan
Abstract: Saccharification of woody biomass with concentrated sulfuric acid has been studied for a long time
to obtain monosaccharides. The monosaccharides can be converted to bioethanol and other chemicals by
fermentation. In this process, lignin is obtained in a high yield, as we call “sulfuric acid lignin” or “Klason
lignin”. It is very difficult to utilize this lignin because of poor solubility to organic solvents and thermal
fusibility. In this work, t-butyl alcohol was added in the process. t-Butyl cation is expected to be created fromt-butyl alcohol in acidic conditions and the self-condensation could be prevented by t-butylation of C6 positionin lignin. Hinoki wood meal, water, t-butyl alcohol, and 95 % sulfuric acid were mixed and reacted in different
ratios to control the thermoplasticity of sulfuric acid lignin. The reaction mixture was stirred at mainly 40 °C orother temperatures until it becomes creamy. Then, the reaction mixture was diluted, boiled and the acidinsoluble fraction was recovered. Thermomechanical analysis showed that the treatment with a larger amount of
t-butyl alcohol improved thermoplasticity of lignin. Reaction temperature accelerated the reaction rate, however,
hardly effected on the thermoplasticity. As the reaction time was extended, apparent yield of lignin wasincreased with improved thermoplasticity. Isobutylene-based polymer was formed from t-butyl alcohol during
longer reaction time and may have worked as a plasticizer.
Keywords: saccharification, concentrated sulfuric acid, t-butyl alcohol, self-condensation, thermoplasticity
2018-114
Synthetic studies of arabinoxylans – a lignin-hemicellulose junction in plant cell walls
Mads H. Clausen
Center for Nanomedicine and Theranostics, Department of Chemistry, Technical University of Denmark,
Kemitorvet 207, DK-2800 Kgs. Lyngby, Denmark; +45 4525 2131, mhc@kemi.dtu.dk
Abstract: Plant cell walls are structurally complex and contain a large number of diverse carbohydrate
polymers, glycoproteins, polyesters and the complex polyphenol lignin. These plant materials are a highly
valuable bio-resource and the focus of food, energy and health research. We are interested in studying theinterplay of plant cell wall carbohydrates with proteins such as enzymes, cell surface lectins, and antibodies. We
are studying the junctions between different components of the wall, such as carbohydrates–polyesters andlignin–hemicellulose. However, detailed molecular level investigations of such interactions are hampered by theheterogeneity and diversity of the polymers of interest. To circumvent this, we target well-defined655

oligosaccharides with representative structures that can be used for characterizing protein-carbohydrate binding
and the interactions between glycans and other polymers in the wall. The presentation will highlight chemical
syntheses of hemicellulose oligosaccharides from the group and some perspectives on current and future studies
of carbohydrate functions in the cell wall.
Keywords: cell wall, hemicellulose, oligosaccharides
2018-115
Investigating cell cooperation during lignification
Henrik Serk1, Delphine Ménard12, Edouard Pesquet12
1. Umeå Plant Science Centre (UPSC), Department of Plant Physiology,Umeå University, 901 87 Umeå, Sweden
2. Department of Ecology, Environment and Plant Sciences (DEEP), Svante Arrhenius väg 20A, Stockholm
University, 160 91 Stockholm, Sweden
Abstract: The amounts and compositions of lignin deposited in plant cell walls vary spatially between species,
tissues, cell-types and cell wall layers as well as temporally during the differentiation of cell-types anddevelopment of tissues. Among the lignified cell-types, tracheary elements (TEs) are dead cells that accumulate
large amounts of lignin in their secondary cell walls to conduct the hydro-mineral sap throughout the plant body.
To maintain their vascular function during plant growth, dead TEs gradually reinforce their secondary cell wallswith the addition of lignin. Using inducible cell suspension cultures and whole plants, the molecular and cellularmechanisms regulating the post-mortem lignification of TEs were investigated. This unique process allowing
the adaptation of TE conductive properties is due to (i) the presence of phenoloxidases (laccases and/or
peroxidases) in distinct cell wall layers, together with (ii) the cooperative supply of different lignin
mono/oligomers produced by surrounding cells.
Keywords: post-mortem lignification, tracheary elements, zinnia
2018-116
バクテリアにおけるリグニン由来芳香族化合物の取り込みシステム
森 光佑、藤田 雅也、新沼 皐、上村 直史、◯政井 英司
長岡技術科学大学・生物
Bacterial inner and outer membrane transport systems for a lignin-derived aromatic compound
Kosuke Mori, Masaya Fujita, Koh Niinuma, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: In order to efficiently convert lignin-derived aromatic compounds into value-added chemicals, thecomplete elucidation of the uptake systems for lignin-derived aromatics is essential. In this study, we identified
and characterized the inner and outer membrane transporters of 5,5’-dehydrodivanillate (DDVA) in
Sphingobium sp. SYK-6. Among the SYK-6 mutants of 67 putative major facilitator superfamily transporter
genes, we found that a ddvK mutant lost its ability to grow on DDVA. The ddvK mutant was unable to uptake
DDVA, and ddvK conferred the capacity to uptake DDVA on a host strain Sphingobium japonicum UT26S.
These results clearly indicate that ddvK encodes the DDVA inner membrane transporter. Overexpression of
ddvK in an SYK-6 mutant of the 2-pyrone-4,6-dicarboxylate hydrolase gene increased growth rate in DDVA
and the amount of DDVA converted and PDC produced after 48 h by 1.35 and 1.34-fold, respectively. In general,
outer membrane transport of aromatic compounds is achieved by utilizing passive transporters such as porins
and substrate-specific channels. In the SYK-6 genome, there is only one porin gene which may be involved inaromatic uptake, and substrate-specific channel genes were not found. In contrast, there are 74 TonB-dependent
receptor (TBDR) genes which are known to encode active outer membrane transporters of Fe3+ siderophore andvitamin B12. DNA microarray analysis revealed that the transcription of a TBDR gene designated tbtA was
specifically induced during the growth of SYK-6 on DDVA. The growth of a tbtA mutant on DDVA wassignificantly retarded, and its conversion rate of DDVA was also reduced. Furthermore, the uptake of DDVA by
the tbtA mutant was significantly diminished. All these results indicate that tbtA is involved in the outermembrane transport of DDVA.
Keywords: Gram-negative bacteria, biphenyl, uptake system, inner membrane transporter, outer membranetransporter
2018-201
フェノール酸化活性を誘導する白色腐朽菌−細菌間相互作用の解析〇松村 真輝 1)、森 智夫 2)、河岸 洋和 2, 3, 4)、平井 浩文 2, 3)
6561) 静岡大学大学院総合科学技術研究科、2) 静岡大学農学部、
3) 静岡大学グリーン科学技術研究所、4) 静岡大学創造科学技術大学院
Induction of phenol oxidative activity resulted from interaction between white rot fungus and bacteria
Masaki Matsumura 1), Toshio Mori 2), Hirokazu Kawagishi 2, 3, 4), Hirofumi Hirai 2, 3)
1) Graduate School of Agriculture, Shizuoka University, 2) Faculty of Agriculture, Shizuoka University, 3)
Research Institute of Green Science and Technology, Shizuoka University, 4) Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract: To elucidate the mechanism for improvement of ligninolytic activity of Phanerochaete sordida infungal-bacterial consortia retaining broad range of bacterial diversity, we experimented the several cultivation
methods to simplify the bacterial diversity. On wood-agar medium containing guaiacol, fungal-bacterial
consortia culture showed unusual coloration pattern resulted from phenol oxidation which was never seen in P.
sordida single culture. On wood-agar medium containing guaiacol, fungal-bacterial consortia culture showed
unusual coloration pattern resulted from phenol oxidation which was never seen in P. sordida single culture. And
the consortia expressed phenol oxidation on PDA although P. sordida did not show phenol oxidative activity on
PDA. Manganese peroxidase and laccase were involved in this phenol oxidation. The result of hyphal-bacterial
attachment assay was dramatically reduced bacterial diversity in the consortia, and indicated that this promotionof phenol oxidation was caused by hyphal-adhesive bacteria. Now, we are trying to disclose the bacteria straininteracting to P. sordida and the relationship between the ligninolytic activity and this promotion of phenol
oxidation.
Keywords: white rot fungi, microbial consortia, fungal-bacterial interaction, phenol oxidation, manganeseperoxidase
2018-202
白色腐朽菌による木質バイオマスからの好気的水素産生に関する生化学的研究○髙橋 沙綾 1), 森 智夫 2), 河岸 洋和 2,3,4), 平井 浩文 2,3)
1) 静岡大学大学院総合科学技術研究科、2) 静岡大学農学部、
3) 静岡大学グリーン科学技術研究所、4) 静岡大学創造科学技術大学院
Biochemical studies on aerobic hydrogen production from woody biomass by white-rot fungi
Saaya Takahashi1), Toshio Mori2), Hirokazu Kawagishi2,3,4), Hirofumi Hirai2,3)1) Graduate School of Agriculture, Shizuoka University, 2) Faculty of Agriculture, Shizuoka University, 3)
Research Institute of Green Science and Technology, Shizuoka University, 4) Graduate School of Science andTechnology, Shizuoka University, Shizuoka 422-8529, Japan
Abstract: We investigated for hydrogen production activities of 108 fungi obtained from decay wood,consequently slight but clear hydrogen production were observed from decaying wood meal cultures with
Phanerochaete spp. and Trametes spp. fungi. By heterologous expression of putative hydrogenase genes from P.
sordida and T. versicolor in Escherichia coli, these gene products showed hydrogen evolution activity. T.
versicolor could produce hydrogen under aerobic condition, and it was suggested that this hydrogen evolution
was catalyzed by fungal hydrogenase which accepts electrons from the formate dehydrogenase reaction by
several experiments using with calcium carbonate. Discover of aerobic hydrogen production and hydrogenase
activity of aerobic fungi are completely new findings in microbiology.
Keywords: white-rot fungi、aerobic hydrogen production、hydrogenase、formate dehydrogenase
2018-203
Phanerochaete chrysosporium によるアセタミプリド分解機構及び細菌共培養による分解促進機構の解明〇大野 遥 1)、一瀬 博文 2)、森 智夫 3)、河岸 洋和 3, 4, 5)、平井 浩文 3, 4)1) 静岡大学大学院総合科学技術研究科、2) 九州大学大学院農学研究院
3) 静岡大学農学部、4) 静岡大学グリーン科学技術研究所、5) 静岡大学創造科学技術大学院
Elucidation of the degradation mechanism of acetamiprid by Phanerochaete chrysosporium and its improvement
effect by co-cultivation with bacteria
Haruka Ono1), Hirofumi Ichinose2), Toshio Mori3), Hirokazu Kawagishi3, 4, 5), Hirofumi Hirai3, 4)1) Graduate School of Agriculture, Shizuoka University, Shizuoka 422-8529, Japan 2) Graduate School of
Agriculture, Kyusyu University, Fukuoka, 812-8581, Japan, 3) Faculty of Agriculture, Shizuoka University, 4)Research Institute of Green Science and Technology, Shizuoka University, 5) Graduate School of Science andTechnology, Shizuoka University
Abstract: Acetamiprid (ACE) is a member of the neonicotinoid insecticides, which have been widely used657

worldwide over the last two decades. However, their hazardousness, neurotoxicity to human and the potential
toxicity to nontarget insect such as honeybees, is pointed out. Therefore, the ACE degradation potential of thewhite-rot fungus Phanerochaete chrysosporium was investigated. After incubation for 21 days at 30 ºC, P.
chrysosporium degraded 32.1% of ACE in nutrient rich liquid culture. In addition, we identified a cytochrome
P450 isozyme involved in ACE degradation by heterologous expression of CYPs cDNA derived from P.
chrysosporium in yeast. Moreover, the promotion of ACE degradation of P. chrysosporium by co-cultivation
system with bacteria isolated from nature environment was attempted. As a result, co-cultures with several
bacteria that have no ACE degradation activity in pure culture showed higher ACE degradation (32.4-78.6%)
than P. chrysosporium pure culture. Furthermore, almost all of these co-cultures were accumulated one of ACE
degradation products resulting from the CYP reaction. Therefore, it was suggested that the bacteria showing
higher ACE degradation in co-culture improved the CYP activity of P. chrysosporium to promote higher ACE
degradation.
Keywords: Phanerochaete chrysosporium, neonicotinoid, bioremediation, co-culture, bacteria
2018-204
真菌グルクロン酸エステラーゼ(FGEs)－リグニン･多糖結合体分解酵素－の系統解析および白色腐朽菌の二つの FGE の発現と活性解析◯林孟宜 1,2)、檜山明穂 2)、近藤敬子 1)、坂井勇太 2)、永田崇 1, 2)、片平正人 1, 2)１）京大・エネルギー理工学研究所、２）京大・エネルギー科学研究科
Classification of a fungal glucuronoyl esterases (FGEs), lignin-carbohydrate complex (LCC) degradation
enzymes, and expression/characterization of two novel FGEs of white rot fungi
Meng-I Lin1,2), Akiho Hiyama2), Keiko Kondo1), Yuta Sakai2),Takashi Nagata1,2),
and Masato Katahira1,2)
1) Institute of Advanced Energy, Kyoto University, Japan
2) Graduate School of Energy Science, Kyoto University, Japan
Abstract: In woody biomass, lignin is linked to hemicellulose by covalent bonds such as ester, ether, andphenyl-glycoside bonds to form lignin-carbohydrate complex (LCC). Fungal glucuronoyl esterases (FGEs)
catalyze cleavage of the ester bond connecting a lignin alcohol to the xylan-bound 4-O-methyl-D-glucuronic
acid of glucuronoxylans. Thus, FGEs have potential for woody biomass utilization. In this study, we built aphylogenetic tree from almost four hundred putative FGEs and defined six main clades. The putative FGEs
belonging to one of the clades were found to have higher theoretical isoelectric points than those in the otherfive clades. To gain a molecular insight into the putative FGEs in the uncharacterized clades, we expressed two
FGEs originated from Ceriporiopsis subvermispora (CsGE) and Pleurotus eryngii (PeGE) using Pichia pastoris.
Both CsGE and PeGE exhibit esterase activity, the activity of PeGE being highest among reported FGEs. PeGE
was found to exhibit high tolerance toward various reagents, which are often used to dissolve woody-biomass
extracts and/or degrading enzymes; this finding may make PeGE a potentially more applicable enzyme for
utilization of wood biomass.
Keywords: Glucuronoyl esterase; Fungi; Lignin-carbohydrate complex; Benzyl glucuronic acid2018-205
リグニン芳香核組成を改変した組換えイネ株のバイオマス利用特性解析○武田ゆり 1)、飛松裕基 1)、山村正臣 1)、高野俊幸 2)、坂本正弘 2)、梅澤俊明 1,3)
1) 京大生存研、2) 京大院農、3) 京大生存基盤展開
Comparative characterization of lignocellulose usability of transgenic rice plants altered in lignin composition○Yuri Takeda1), Yuki Tobimatsu1), Masaomi Yamamura1), Toshiyuki Takano2),
Masahiro Sakamoto2), Toshiaki Umezawa1,3)
1 Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
2 Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
3 Research Unit for Development of Global Sustainability, Kyoto University, Gokasho, Uji, Kyoto 611-0011,
Japan
Abstract: Aromatic composition of lignins has been considered to be an important structural trait that affects
the physico-chemical properties of lignocellulosic biomass. However, our knowledge regarding the relationshipbetween the lignin aromatic composition and biomass utilization characteristics is still considerably limited
especially in monocotyledonous grass species despite their potential as biomass feedstocks. Here, we used ourrecently generated transgenic rice with distinct lignin monomer composition, i.e., guaiacyl (G)/syringyl(S)/p-hydroxyphenyl (H) aromatic unit ratio, to investigate the effect of altered lignin composition on their658

biomass saccharification efficiency and heating value. The H-lignin-enriched transgenic rice showedsignificantly enhanced biomass saccharification efficiency without any pretreatment or with alkali and acidpretreatments, whereas the S-lignin-enriched transgenic rice showed further enhanced saccharification
efficiency when using liquid hot water pretreatment. While no significant differences in the biomass heating
values between the transgenic rice materials tested, analysis of synthetic lignins comprising only G, S or H units
suggested that increasing H or G units may be beneficial to increase the heating value of biomass.
Keywords: Oryza sativa, Coniferaldehyde 5-hydroxylase, p-Coumaroyl ester 3-hydroxylase, Enzymaticsaccharification, Heating value
2018-206
-O-4 還元的開裂産物-hydroxypropiovanillone のバクテリアにおける代謝経路
樋口 雄大 1)、青木 翔吾 1)、高橋 健司 1)、◯上村 直史 1)、菱山 正二郎 2)、片山 義博 3)、政井 英司 1)1) 長岡技術科学大学・生物、2) 森林総研、3) 日本大学・生資科
Bacterial catabolism of -hydroxypropiovanillone produced by the -O-4 reductive cleavage
Yudai Higuchi1), Shogo Aoki1), Kenji Takahashi1), Naofumi Kamimura1),
Shojiro Hishiyama2), Yoshihiro Katayama3), Eiji Masai1)
1) Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
2) Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan
3) College of Bioresource Sciences, Nihon University, Fujisawa, Kanagawa, Japan
Abstract: The -O-4 cleavage is a crucial step in lignin biodegradation. A bacterial -O-4 cleavage pathway
and catabolic genes have been most elucidated in Sphingobium sp. strain SYK-6. In this strain, four
stereoisomers of -O-4 type biaryls, guaiacylglycerol--guaiacyl ether (GGE), are stereospecifically degraded
into achiral -hydroxypropiovanillone (HPV) by the -etherase enzyme system. To date, a similar system for-O-4 reductive cleavage has been found in several bacteria and most recently in fungi, however there is noreport for the HPV catabolism. In this study, we determined the HPV and HPS (a syringyl-type HPV analog)
catabolic pathway in SYK-6 and characterized the genes involved in part of the pathway. In SYK-6 cells, HPV
was subjected to two steps of oxidation and converted into vanilloyl acetic acid (VAA) via vanilloyl
acetaldehyde (VAL), and the resultant VAA was further catabolized via vanillate. HPS was also degraded by thesame pathway. A gene encoding glucose-methanol-choline oxidoreductase family enzyme, SLG_12830 (hpvZ),
was isolated as an essential gene for conversion of HPV and HPS from genomic library screening. The
localization of HpvZ in SYK-6 was determined to be both the cytoplasm and membrane. For the oxidation of
HPV, HpvZ showed ability to use ubiquinone derivatives as electron acceptors. Among 23 aldehyde
dehydrogenases (ALDH) of SYK-6, thirteen enzymes were able to oxidize VAL into VAA. Mutant analyses
suggested that multiple ALDH genes, including SLG_20400, involved in the oxidation of VAL.
Keywords: Gram-negative bacteria, -aryl ether, phenylpropane, coniferyl alcohol, ubiquinone,
2018-207
人工的な細胞壁再構築系でリグニンの効果を見る
中田未友希 1)、坂本真吾 1)、金子康子 2)、〇光田展隆 1)1) 産業技術総合研究所 生物プロセス研究部門 2) 埼玉大学大学院理工学研究科
Evaluating the contribution of lignin to the cell wall properties by using a system to reconstitute artificial cellwall in planta
Miyuki Nakata1), Shingo Sakamoto1), Yasuko Kaneko2), Nobutaka Mitsuda1)
1) Bioproduction Research Institute, National Institute of Advances Industrial Science and Technology (AIST),Japan
2) Graduate school of Science and Technology, Saitama University, Japan
Abstract: Contribution of lignin to the cell wall properties is not necessarily well described due to lack ofmutant which doesn’t have any lignin in secondary cell walls. Because lignin is inevitable for vascular vessels tokeep water inside and its biosynthesis is tightly coregulated in vascular vessels and fiber cells, it is difficult toobtain the mutant mentioned above which could grow relatively normal. We found before Arabidopsis double
mutant of NST1 and NST3 which doesn’t have any secondary cell walls in stem fiber cells (Mitsuda et al.,2007). We aimed to isolate new transcription factor genes which could reconstitute a part of or entire secondarycell walls in this mutant by screening many transcription factor genes (Sakamoto and Mitsuda 2015). We finallyfound that ClassIIId and IIIe ERF transcription factors can produce thick unusual cell walls which don’t have
any lignin in the mutant fiber cells when they are expressed under the control of NST3 promoter which is659

specifically active in fiber cells (Sakamoto et al., 2018). The accumulated cell walls are very similar to primarycell walls in terms of monosaccharide composition and gene expression profile (Sakamoto et al., 2018). We thenadditionally expressed MYB58 transcription factor in the fiber cells of the transgenic lines and succeeded todeposit lignin on the accumulated primary cell wall-like cell walls. By observing the fiber cells with electron
microscope and testing stem mechanical properties, we now demonstrated that lignin confers mechanicalstrength to the cell walls in cell-order level and in tissue-order level.
Keywords: lignin, mechanical property, plant cell wall, transcription factor
2018-208
植物細胞壁におけるリグニンエンジニアリングのための新規酵素遺伝子の探索
徳江洋介 1),2)、〇坂本真吾 2)、上村直史 1)、政井英司 1)、梶田真也 3)、光田展隆 2)1) 長岡技術科学大学大学院 工学研究科 生物機能工学専攻
2) 産業技術総合研究所 生物プロセス研究部門
3) 東京農工大学大学院 生物システム応用科学府 生物機能システム科学専攻
Exploring of useful enzymatic genes for lignin engineering
Yosuke Tokue1),2), Shingo Sakamoto2), Naofumi Kamimura1), Eiji Masai1), Shinya Kajita3), Nobutaka
Mitsuda2)
1) Department of Bioengineering, Nagaoka University of Technology, Japan2) Bioproduction Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),Japan
3) Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Japan
Abstract: Lignins are aromatic polymers which are largely present in secondary cell wall and provides plantcritical roles such as physical force in supporting tissue and hydrophobicity in vascular tissues. However, its
recalcitrance hampers the industrial use for the production of biofuel and biomaterials and therefore, lignin
engineering has potential to improve the processing efficiency of these production. We screened ca. 50
transgenic plants which expressed various enzyme genes, products of which convert metabolites of monolignol
biosynthetic pathways, under the control of a Populus Kitakamiensis C4H promoter and identified sometransgenic plants showed apparent abnormalities in xylem fibers and vessels by Wiesner and Mäule staining. We
further analyzed to their cell wall characteristics of those transgenic plants. One of them showed 2-hold higher
saccharification efficiency by cellulose treatment than wild-type plant while monosaccharide amount andcomposition in it were almost comparable to those in wild-type. Furthermore, H monomer ratio in cell wall of
the transgenic plants is 50 times higher than that in wild-type. These results indicated that this approach is
powerful tool to identify the gene which improves cell wall digestibility by modifying lignin structure.
Keywords: lignin engineering, molecular breeding, plant cell wall
2018-209
リグニン生合成抑制型転写因子 OsMYB108 変異イネの解析◯宮本託志 1)、高田理江 1)、飛松裕基 1)、武田ゆり 1)、鈴木史朗 1)、山村正臣 1)、
刑部敬史 2)、刑部祐里子 2)、坂本正弘 3)、梅澤俊明 1), 4)1) 京都大学生存圏研究所、2) 徳島大学生物資源産業学部、2) 京都大学大学院農学研究科、4) 京都大学研究連携基盤グローバル生存基盤展開ユニット
Characterization of transgenic rice with disrupted function of OsMYB108, a transcriptional repressor in lignin
biosynthesis
Takuji Miyamoto1), Rie Takada1), Yuki Tobimatsu1), Yuri Takeda1), Shiro Suzuki1), Masaomi Yamamura1),
Keishi Osakabe2), Yuriko Osakabe2), Masahiro Sakamoto3), Toshiaki Umezawa1), 4)
1) Research Institute for Sustainable Humanosphere, Kyoto University, Uji, Kyoto, Japan
2) Faculty of Bioscience and Bioindustry, Tokushima University, Tokushima-city, Tokushima, Japan
3) Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, Japan
4) Research Unit for Development of Global Sustainability, Kyoto University, Uji, Kyoto, Japan
Abstract: Grass biomass crops, such as Erianthus spp. and Sorghum spp., which typically show higher
lignocellulosic biomass productivity than trees, represent potent biomass feedstocks for producing biofuels andvarious biomass-derived materials. Lignins, a major component of lignocellulose, have a positive impact on thebiomass heating value, and also represent a viable source of aromatic chemicals. Thus, breeding approaches toenrich lignins in grass biomass crops can be beneficial for establishing a cost-effective biorefinery processes. In
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this study, we generated lignin-enriched rice (Oryza sativa) transgenic lines through the CRISPR/Cas9-mediatedtargeted mutation of OsMYB108, a transcriptional repressor gene involved in lignin biosynthesis, and closely
characterized their lignocellulose structure by chemical and NMR analyses.
Keywords: Genome editing; Heating value; Molecular breeding; Mutagenesis; Transcription factor
招待講演
Designing Lignins for the BiorefineryJohn Ralph,1,2* Yanding Li,1,2 Hoon Kim,1,2 Fachuang Lu,1,2 Steven D. Karlen,2 Matt Regner,1,2 Dharshana
Padmakshan,2 Rebecca Smith,1,2 Yuki Tobimatsu,1,2,* Wu Lan,1,2,3 José Carlos del Río,4 Jorge Rencoret,1,4
Li Shuai,1,3 Jeremy Luterbacher,3 Fang Chen,5 Richard Dixon,e Ruben Vanholme,6 Wout Boerjan,6 Ali
Hussain Motagamwala,1,2 James Dumesic,1,2 Shengfei Zhou,1,3 Troy Runge,1,2 Shinya Kajita,7 Yaseen
Mottiar,2,8 Shawn D. Mansfield,2,8 and others!
1
U. Wisconsin, Madison, WI, USA.
2
DOE Great Lakes Bioenergy Research Center, Madison, WI.
3
École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland.
4
Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Seville, Spain.
5
University of North Texas, Denton, TX, USA.
6
Ghent University, and VIB Center for Plant Systems Biology, Ghent, Belgium
7Tokyo U. Agriculture and Technology, Nakacho, Koganei, Tokyo, Japan.
8
U. British Columbia, Vancouver, BC, Canada.
*
Currently: Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto,
Japan.
Abstract: Lignin is crucial to plant growth and development but is problematic due to its major impediment tobiomass utilization in various processes. It is, however, increasingly recognized that valorizing lignin is essential
for sustainably and profitably converting biomass to valuable products. Researchers are now able to contemplate
altering lignins for improved utilization in a biorefinery and ponder what constitutes an ‘ideal lignin’ forprocessing and conversion.
As lignin is a polymer formed from its monomer radicals by purely chemical radical coupling react¬ions, thebreadth of options for ‘designing’ the com¬position and structure of lignins is unparalleled. Beyond simply
manipulating the relative levels of the traditional monolignols, new phenolic monomers can be introduced into
the polymer, subject solely to the plant’s ability to produce and transport them to the wall and their chemicalcompatibility with the com¬ponents and (cross-) coupling reactions that typify lignification. Recent examples ofthis metabolic plasticity include demonstrating the introduction of hardwood-type lignins into soft¬woods toimprove pulping performance, and the identification of plants producing lignins composed almost entirely ofhy¬droxy¬cinnamaldehydes, opening up new and unique derivatization and modification op¬por¬tun¬ities.
Tissues containing 100% levels of caffeyl or 5-hydroxy¬coniferyl alcohol-derived lignin polymers have been
discovered. These two catechol-type monolignol analogs produce almost homo¬geneous (single-structured)linear lignin chains upon poly¬mer-ization, again creating opportunities for valuable new uses for lignin. The
recently discovered catechyl lignin (C-lignin), which is essentially a benzodioxane homopolymer, might
represent an ideal lignin for lignin valorization. We discovered that C-lignin is highly acid resistant and is able
to maintain its native structure after harsh acidic treatments. Its hydrogenolysis resulted in the cleavage of all
benzodioxane structures to cleanly produce catechyl-type monomers in essentially quantitative yield. Lignins
have also now been suc¬cess¬fully ‘redesigned’ to contain readily chemically cleav¬able ester bonds in thepolymer backbone, facilitating improved industrial processing – for example, chem¬ical pulping, orpretreatment options for the sacc¬har-ification of wall polysaccharides to sugars for liquid biofuels production.
Inspired by Nature’s incor¬poration of the non-lignin-pathway flavonoid, tricin, into monocot lignins,researchers can now also con¬template plants in which the lignins incorporate valuable components that can be
subsequently retrieved from the ‘waste’ streams. We suspect that we are now entering a reinvig-oration period
for lignin research aimed at its manip¬ulation for improved utilization.
Keywords: Lignification, metabolic plasticity, monolignol, gene misregulation, engineering, pulping, C-lignin
特別講演-O-4 構造を中心としたリグニン化学構造の多様性と規則性、および、それらの化学的反応性との関係
松本雄二
東大大学院農学生命科学研究科木材化学研究室
Variety and regularity of lignin chemical structure, especially of -O-4 structure, and, the relationships between
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the chemical reactivity
Yuji Matsumoto
Wood Chemistry Laboratory, Graduate School of Agricultural and Life Sciences,
The University of Tokyo
Abstract: Hardwood lignins and softwood lignins are different by the presence of syringyl type aromatic nuclei
in the former. In addition, there are wide varieties in the lignin characteristics (structure and amount) depending
on wood species, environment of growing site, portion in the wood, portion in the cell wall, and so on. However,clear tendencies are also observed in the variety of lignin characteristics by taking the syringyl/guaiacyl ratio as
an index. We have shown that the lignin chemical structure has a significant effect on the chemical reactivity
such as delignification during chemical pulping. In this report, I review the recent achievements of mylaboratory about the quantitative relationships between lignin structure and reactivity.
Keywords: molecular structure, reactivity
2018-P01
SEC/MS および分取 SEC/MALDI-TOFMS によるリグニンの分子量測定法
竹本紀之、秋山毅、田口嘉彦，佐藤瑠璃（株）東レリサーチセンター
Molecular weight determination of lignin by SEC/MS and preparative SEC/MALDI-TOFMSNoriyuki Takemoto, Tsuyoshi Akiyama, Yoshihiko Taguchi, Ruri Sato
Toray Research Center, Inc., Otsu-City, Shiga 520-8567, Japan.
Abstract: To analyze the molecular weight of lignin, the conventional SEC/RI analysis had the problem thatthe results fluctuate greatly due to the difference in mobile phase and column. In order to establish a molecularweight determination method by SEC/MS, mobile phase conditions suitable for MS ionization were studied. As
a result, it was confirmed that SEC/MS has low molecular weight components with molecular weight of about
2400, and that of preparative SEC/MALDI-TOFMS has high molecular weight components with molecularweights of up to 30000, almost coincide with calibration curves based on polystyrene (PSt) .
The results of this research were obtained from NEDO (New Energy and Industrial Technology Development
Organization) outsourcing projects.
Keywords: Cedar, Eucalyptus, GPC, CAD, UV
2018-P02
熱機械分析によるリグニンの軟化温度測定○平野孝行、大田玲奈、北川雅士、畠幹生、大川朋寛、高井良浩
東レリサーチセンター
Softening temperature of lignin by thermomechanical analysis○Takayuki Hirano, Rena Ota, Masashi Kitagawa, Mikio Hata, Tomohiro Okawa, Yoshihiro Takai
Toray Research Center, Shiga, 520-8567, Japan
Abstract: We investigated the measurement condition of softening temperature of the lignin by the TMA
method using commercial organosolv lignin. As a result, the sample formed using a press machine could
measure change in dimensions with softening. Based on an investigated result, we measured that the softening
temperature of hardwood lignin and softwood lignin. The softening temperature of hardwood lignin andsoftwood lignin were approximately 170℃ and 140℃, respectively. The softening behavior accorded with thesample appearance change by the real-view type thermal analysis result. In addition, at 7 mass% of moisture
content, the difference was not recognized to softening temperature with the hardwood lignin, the softwood
lignin either.
Keywords: Cedar, Eucalyptus, TMA, Softening temperature, moisture
2018-P03
初期熱分解生成物の低減を目指したコルクの加熱脱着 GC/MS 分析
常定 健、國藤勝士、児子英之
岡山県工業技術センター
Thermal desorption-GC-MS analysis of cork: aiming to reduce the amount of initial pyrolysis products
Takeshi Tsunesada, Katsushi Kunitou, Hideyuki Nigo
Industrial Technology Center of Okayama Prefecture, Okayama, Japan
Abstract: Cork was analyzed to reduce the amount of initial pyrolysis products by thermal desorption-GC-MS.
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Assuming that acetic acid, which occurs due to the hydrolysis of acetyl group existing in cork, causes a decline
in heat resistance, we pretreated cork to hydrolyze acetyl group in alkaline solutions. Specifically, cork particles
were heated at 50˚C for 16 hours in the water where there were calcium hydroxide, magnesium hydroxide,
aluminium hydroxide excessively. It was found from the experimental results that vanillin and furfural as wellas acetic acid decrease by alkaline pretreatments.
Keywords: cork, thermal desorption-GC-MS, acetic acid, hemicellulose, degradation mechanisms
2018-P04
選択的 13C 標識法を用いたリグニンの構造解析‐INADEQUATE 測定による検討‐○尾崎泰斗、松下泰幸、青木弾、福島和彦
名古屋大学大学院生命農学研究科
Structural analysis of lignin by 13C-enrichment technique -Investigation by INADEQUATE measurementYasuto Ozaki, Yasuyuki Matsushita, Dan Aoki, Kazuhiko Fukushima
Graduate School of Bioagricultural Science, Nagoya University, Japan
Abstract: Among the interunit linkages in lignin, investigation of β-5, β-β, and 5-5 linkages is very importantfor effective utilization of lignin because their bonds are very strong. In this study, we focused on the carbon at
β-position and analyzed their structure by NMR measurement in an INADEQUATE mode. This method is
powerful for the analysis because it can measure 13C-13C linkage directly. However, there is few report toanalyze the structure of lignin using the INADEQUATE mode because of low presence ratio of 13C resulting in
low sensitivity. In this study, selective 13C enriched DHP at β-position was synthesized and measured by the
INADEQUATE mode to analyze the structure of lignin related to β-carbon.
Keywords: NMR, INADEQUATE mode, DHP, selective 13C-enrichment technique, β-carbon
2018-P05
13CO2 投与によるイチョウリグニン芳香核構造の解析○宮田苑加 1)、青木弾 1)、松下泰幸 1)、竹内美由紀 2)、福島和彦 1)
1) 名古屋大学大学院生命農学研究科 2) 東京大学大学院農学生命科学研究科
Analysis of lignin aromatic structures in Ginkgo biloba by 13CO2 administration
Sonoka Miyata1), Dan Aoki1), Yasuyuki Matsushita1), Miyuki Takeuchi2), Kazuhiko Fukushima1)
1) Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya 464-8601, Japan
2) Graduate School of Agricultural and Life Sciences, Tokyo University, Tokyo 113-8657, Japan
Abstract: Lignin is one of the major plant cell wall polymers. Despite extensive investigation, the structure isnot completely understood. In order to elucidate the lignin structure, 13C-enriched lignin was produced by anadministration of 13CO2 to Ginkgo biloba wood under airtight condition and analyzed by a high lateral
resolution secondary ion mass spectrometry (NanoSIMS) and 13C-NMR measurements. As a result of
NanoSIMS, the 13C ratio was up to 60 % in the xylem cell wall. As for solution-state 13C-NMR spectrum, we
assigned the major lignin aromatic carbons and quantified their frequencies.
Keywords: structural analysis, 13CO2 administration, NanoSIMS, solution-state NMR, quantitative
determination
2018-P06
分析的熱分解法による酸加溶媒分解スギリグニンの組成分析〇京極未憂 1)、中川明子 1)、ネーティティ 2)、髙田依里 2)、山田竜彦 1,2)
1)筑波大学、2)森林総合研究所
Chemical composition analysis of polyethylene glycol (PEG) solvolysis lignin by pyrolysis gas chromatography· mass spectrometry (Py - GC / MS)
Miyu Kyogoku1), Akiko Nakagawa-izumi1), Thi Thi Nge2), Eri Takata2), Tatsuhiko Yamada1, 2)
1) University of Tsukuba, 2) Forestry and Forest Product Research Institute, Japan
Abstract: The process of acid-catalyzed PEG solvolysis of Japanese cedar to produce polyethylene glycol(PEG) solvolysis lignin (glycol lignin) has being developed at FFPRI in order to promote an effective utilizationof woody biomass. It was revealed that glycol lignin included ether-bonded PEGs as well as carbohydrate
derived furan-based polymer. However, the furan-based polymer has not been analyzed quantitatively. In thisstudy, Py-GC/MS analysis was conducted to evaluate the content of bonded PEG and furan-based polymer ofglycol lignin.
Keywords: solvolysis, lignin, pyrolysis, PEG, furan663

2018-P07
針葉樹単離リグニンの分子量分画とビフェニル型構造の分布○羽田尚希１）、秋山拓也１）、横山朝哉１）、松本雄二１）１）東京大学大学院農学生命科学研究科
Fractionated Softwood MWLs Depending on the Solubility in Dioxane, and Their Molecular Weight
Distribution and Biphenyl Contents
Naoki Hada1), Takuya Akiyama1), Tomoya Yokoyama1), and Yuji Matsumoto1)
1) The University of Tokyo, Graduate School of Agricultural and Life Sciences, 1-1-1 Yayoi, Bunkyo-ku, Tokyo,113-8657, Japan
Abstract: Japanese red pine milled wood lignin (MWL) was fractionated based on the difference in thesolubility in 1,4-dioxane containing different proportion of diethyl ether. Obtained six fractions were subjected
to size exclusion chromatography and alkaline nitrobenzene oxidation to investigate the relationship between
the molecular weight distribution and the composition of inter-unit linkage, i.e. non-condensed type, β-5 typeand biphenyl type.
Keywords: 5-5 linkage, lignin, alkaline nitrobenzene oxidation, divanillin, gymnosperm
2018-P08
種々の褐色腐朽菌で腐朽させた木材の化学的特性〇近藤里沙子 1)、堀川祥生 1)、半 智史 1)、安藤恵介 1)、吉田 誠 1)
1) 東京農工大Chemical properties of wood samples decayed by brown-rot species
Risako Kondo1), Yoshiki Horikawa1), Satoshi Nakaba1), Keisuke Ando1), Makoto Yoshida1)
1) Tokyo University of Agriculture and Technology, Japan
Abstract: Brown-rot fungi are at least distributed into the four orders of Boletales, Dacrymycetes,
Gloeophyllales, and Polyporales. Therefore, we hypothesized that there are differences in wood degradationmanner among brown-rot fungi which belong to different evolutionary groups. To obtain the knowledge on thediversity of wood degradation manner in brown-rot fungi, structural features of wood samples, which weredecayed by four different brown-rot fungi, were investigated with FT-IR.
Keywords: brown-rot fungi, wood decay, lignin, polysaccharide, FT-IR
2018-P09
Characterization of heat treated glycol lignins produced by acid-catalyzed polyethylene glycol (PEG) solvolysis
Thi Thi Nge1), Mariko Ago1), Shiho Takahashi1), Eri Takata1), Yasunori Ohashi1), Tsutomu Ikeda1), Masaomi
Yamamura2), Yuki Tobimatsu2), Toshiaki Umezawa2), Tatsuhiko Yamada1)1)Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba, Ibaraki 305-8687
2)Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto 611-0011
Abstract: In this study, three types of polyethylene glycol (PEG400)-modified glycol lignin, GL400L,
GL400M, and GL400S samples were subjected to heat treatment from 100ºC to 160ºC in constant temperatureoven for 1 h and the effect of heat treatment temperature on properties of the resultant GL samples were
investigated, including thermal analyses (glass transition temperature, Tg, thermal flow temperature, Tf,
decomposition starting temperature, Tdst), molecular (Mw, and Mn), and structural (thioacidolysis analysis and
ATR-FTIR) analyses. Overall, there are small changes on thermal behavior and structural properties of the heat
treated GL samples, which in turn depend on the molecular mass of the respective control GL sample and thesource wood meal size from which control GL sample was produced.
Keywords: glycol lignin, polyethylene glycol (PEG) solvolysis, wood meal size, heat treatment
2018-P10
改質リグニンを用いた柔軟性エポキシ樹脂の合成と物性評価〇小野健太 1)、棚池修 1)、石井亮 1)、中村考志 1)、敷中一洋 1)、蛯名武雄 1)、ネーティティ 2)、山田竜彦 2)
1)産業技術総合研究所 化学プロセス研究部門、2)森林総合研究所
Fabrication and properties of Flexible Epoxy Resin using Glycol Lignin from Softwood
Kenta Ono1), Osamu Tanaike1), Ryo Ishii1), Takashi Nakamura1), Kazuhiro Shikinaka1), Takeo Ebina1), Thi
Thi Nge2), Tatsuhiko Yamada2)
1) National Institute of Advanced Industrial Science and Technology 4-2-1 Nigatake Miyagino-ku, Sendai,664

Miyagi 983-8551, Japan
2) Forestry and Forest Products Research Institute 1 Matsunosato, Tsukuba, Ibaraki 305-8687, Japan
Abstract: An epoxy resin with high lignin content has been successfully prepared by mixing and thermal
curing of Glycol Lignin and an aliphatic epoxy material, polyethylene glycol diglicidyl ether (PEGDGE),
without using additional solvent. Mechanical properties of the resins with different lignin contents were
evaluated, and it was found that the resins had good flexibilities and elasticities dependent on the Glycol Lignin
content. Mechanism of the curing reaction was also discussed through the chemical equivalent weight between
Glycol Lignin and PEGDGE.
Keywords: glycol lignin, softwood, polyethylene glycol, epoxy resin, curing reaction
2018-P11
テトラブチルアンモニウムヒドロキシド中での PEG 改質リグニンからのバニリン生産における温度および圧力の影響○岡本大輝 1)、細谷隆史 1)、吉岡康一 1)、宮藤久士 1)、山田竜彦 2)1) 京府大院生環、2) 森林総研
Effects of Temperature and Pressure on Vanillin Production from PEG-modified Glycol Lignin in
Tetrabutylammonium Hydroxide
Daiki OKAMOTO1), Takashi HOSOYA1), Koichi YOSHIOKA1),
Hisashi MIYAFUJI1), Tatsuhiko YAMADA2)
1) Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
2) Forestry and Forest Products Research Institute, Japan
Abstract: Aerobic oxidation of lignin in tetrabutylammonium hydroxide (TBAH) produces vanillin and its
related phenols with high selectivity. We performed vanillin production from PEG-modified glycol lignin in alarger scale reaction system (100 g of sample/1.0 L of the reaction solution) under pressurized O2 (0.7-2.5 MPa)at temperatures of 80-120 oC. Under the optimum conditions (120 oC/2.5 MPa/1.0 h) vanillin was obtained in
6.1 wt% yield, which was comparable to that (7.0 wt%) obtained in our previous small scale (14 mg ofsample/2.0 mL of the reaction solution) experiment.
Keywords: PEG-modified glycol lignin, oxidation, vanillin, tetrabutylammonium hydroxide, larger scale
reaction
2018-P12
イオン液体前処理と酵素糖化により得られる残渣リグニンの特性評価○仁宮一章 1)、江口真央 2)、杉野雄規 2)、柘植陽太 1)、髙橋憲司 2)1) 金沢大学 新学術創成研究機構、2) 金沢大学大学院 自然科学研究科
Oxidative depolymerization potential of biorefinery lignin obtained by ionic liquid pretreatment and subsequent
enzymatic saccharification of biomass
Kazuaki Ninomiya1), Mao Eguchi2), Yuki Sugino2), Yota Tsuge1), Kenji Takahashi2)
1) Institute for Frontier Science Initiative, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan
2) Faculty of Natural System, Institute of Science and Engineering, Kanazawa University, Kakuma-machi,
Kanazawa 920-1192, Japan
Abstract: This study compared the oxidative depolymerization potential between ionic liquid(IL)-pretreated/enzyme lignin, diluted acid (DA)-pretreated/enzyme lignin, and soda lignin of eucalyptus, bymeans of alkaline nitrobenzene oxidation which depolymerize lignin into phenolic aldehydes such as vanillin
and syringaldehyde. Here, the IL-pretreated/enzyme lignin was prepared by 1-ethyl-3-methylimidazolium
acetate pretreatment and subsequent enzymatic saccharification. Upon the oxidative depolymerization of lignin
sample by alkaline nitrobenzene oxidation, total yield of vanillin and syringaldehyde was 36.6% for untreatedcontrol eucalyptus. In contrast, the yield was enhanced upto 48.0% for IL-pretreated/enzyme lignin. As for thesoda lignin prepared by alkali cooking, the yield was 29.0%. As for the DA-pretreated/enzyme lignin preparedby DA pretreatment and subsequent enzymatic saccharification, the yield was 39.5%. Therefore, it was foundthat the IL-pretreated/enzyme lignin showed the highest yield of phenolic aldehydes (vanillin andsyringaldehyde) via alkaline oxidation, namely, highest oxidative depolymerization potential among the lignin
tested.
Keywords:Ionic liquid, Pretreatment, Enzymatic residue lignin, Oxidative depolymerization, Phenolicaldehydes.
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2018-P13
有機水酸化物水溶液に溶解した木粉成分の酸添加による分画○ 秋葉 隆 1)、大野弘幸 1,2)、中村暢文 1,2)
1) 東京農工大学大学院工学府生命工学専攻 2) 東京農工大学大学院工学研究院
Addition of acids to organic hydroxide aqueous solution
for the fractionation of woody biomass
Takashi Akiba1), Hiroyuki Ohno1), Nobuhumi Nakamura1)
1) Department of Biotechnology and Life science, Tokyo University of Agriculture and Technology, Japan 2)
Graduate School of Engineering, Tokyo University of Agriculture and Technology, Japan
Abstract: Lignocellulosic biomass is the most abundant renewable resource on the earth. The main
components of lignocellulosic biomass are cellulose, hemicellulose, and lignin. We have previously reported
several ionic liquids for the efficient dissolution of these valuable components, and also proposed that
tetrabutylphosphonium hydroxide (TBPH) aqueous solution as a novel solvent of woody biomass under mild
condition. In this study, fractionation of woody biomass dissolved in TBPH aqueous solution was examined.
Neutralization of TBPH aqueous solution with acids yields mixture of phosphonium type ionic liquids and water,
and the mixture was expected to dissolve only lignin fraction.
Keywords: Organic hydroxide aqueous solution, ionic liquids, fractionation, neutralization,
2018-P14
鉄触媒を用いる木質リグニンの酸化分解反応〇 社納貴文１），２），高谷光１），２），中谷祐也１），３），武田佳彦４），伊藤正人５），中村正治１），２）
１）京都大学化学研究所，２）京都大学大学院工学研究科，３）京都大学工学部，
４）株式会社リガク，５）九州大学先導物質化学研究所
Iron-Catalyzed Oxidative Depolymerization of Lignin
Takafumi Shanoh1),2) ， Hikaru Takaya1),2) ， Yuuya Nakatani1),3) ， Yoshihiro Takeda4) ， Masato Ito5) ，Masaharu Nakamura1),2)
1)Institute for Chemical Research, Kyoto University, Japan, 2)Department of Energy and Hydrocarbon
Chemistry, Graduate School of Engineering, Kyoto University, Japan,
3)Faculty of Engineering, Kyoto University, Japan, 4)Rigaku Corporation, Tokyo, Japan,5)Institute for Materials Chemistry and Engineering, Kyushu University, Japan
Abstract: An iron complex bearing bis(trifluoromethanesulfonyl)amido ligands showed high catalytic activity
for oxidative degradation of lignin dimer models and depolymerization of soda lignin. An X-ray micro CT
analysis has revealed that the iron complex-catalyzed decomposition of the wood tissues proceeds at the surfaceof tracheids and at the pit borders, where efficient and direct contact of the iron catalyst and oxidant promotes
the depolymerization of lignin incorporated in the secondary wall.
Keywords: degradation, oxidation, iron catalyst, β-O-4, 3D imaging
2018-P15
リグノスルホン酸の酸糖化触媒としての特性〇 菱山正二郎１）、久保智史 1）、橋田光 1）、池田努 1）、眞柄謙吾 2）
１）国立研究開発法人森林研究・整備機構 森林総合研究所 森林資源化学研究領域、 ２）国立研究開発法人森林研究・整備機構 森林総合研究所 研究ディレクター
Lignosulfonic Acid as Catalysis for Acid Saccharification
Shojiro Hishiyama1), Satoshi Kubo1), Koh Hashida1), Tutomu Ikeda1), Kengo Magara2)
1)
Department of Forest Resource Chemistry, Forestry and Forest Products Research Institute, Forest
Research and Management Organization, 2) Principal Research Director (Woody Biomass), Forestry and Forest
Products Research Institute, Forest Research and Management Organization
Abstract: Lignosulfonic acid, which is the most available industrial lignin produced from sufite pulping
process, was verified as saccharification catalysis of woody biomass. Saccharification rate of birch wood was
faster than that of Sugi wood. More than 40% (w/w) of birch wood was decomposed by saccharification using
lignosulfonic acid at 150 °C for 6 h. By contrast, decomposition of Sugi wood meal was ~30% under the same
saccharification conditions. In our previous study for acid saccharification of disaccharide, Xylobiose wasreadily hydrolyzed by lignosulfonic acid in compare with cellobiose. Therefore, observed difference in thesaccharification rate would be related to the differerences in the mono-sugar compositions between birch and666

sugi woods.
Keywords: Lignosulfonic acid, Acid catalyst, Acid hydrolysis
2018-P16
量子化学計算を用いたアルカリ性ニトロベンゼン酸化における分子機構の解明○細谷隆史、宮藤久士
京都府立大学大学院生命環境科学研究科
Quantum Chemical Study on Mechanisms in Alkaline Nitrobenzene Oxidation〇Takashi HOSOYA, Hisashi MIYAFUJI
Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Japan
Abstract: Molecular mechanisms in alkaline nitrobenzene oxidation (AN oxidation) of lignin – in spite of its
importance in lignin chemistry – have not been fully clarified yet. This study carried out DFT(M06-2X)-levelcalculations for degradation of p-hydroxyphenyl type trans-enol ether EE with nitrobenzene, where EE wasformed through alkaline degradation of phenolic -O-4 structures and considered to be a major intermediate in
the AN oxidation of phenolic -O-4 structure. Our computational results suggested that two-electron oxidationof EE occurred though electrophilic attack of nitrobenzene on the -positon of the EE’s side chain. Pathways
involving complexation between the phenolic OH of EE and nitrobenzene were not likely as such complexes
were not optimized as stable structures.
Keywords: Alkaline nitrobenzene oxidation, quantum chemical calculation, density functional theory (DFT),
vanillin, mechanisms
2018-P17
過酸化水素漂白反応を用いたリグニン由来の芳香族アルデヒドおよび芳香族酸生成最適条件の探究（東京大学大学院農学生命科学研究科）酒井達志、秋山拓也、横山朝哉、松本雄二
Study on the optimal conditions to generate lignin-derived aromatic aldehyde and acid under hydrogen peroxide
bleaching conditions
Tatsuyuki Sakai, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences,
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract:
A non-phenolic β-O-4-type lignin model compound, veratrylglycerol-β-guaiacyl ether (VG), wastreated with stepwisely-added H2O2 under alkaline H2O2 bleaching conditions. The purpose of this treatment
was to develop optimal reaction conditions to produce lignin-derived aromatic aldehydes and acids from
non-phenolic lignin units by the use of active oxygen species produced by the self-decomposition of H2O2.
The examined reaction parameters were alkaline concentration, temperature, number of addition times of H2O2,
amount of FeCl3 as a catalyst, and ratio of FeCl3 to MgCl2. Higher alkali concentration resulted in higher yieldof aimed products and higher VG consumption under the condition examined. The effects of FeCl3 and MgCl2
addition were clearly shown and their doses and ratio significantly affected the yield of aimed compounds and
VG consumption.
Keywords: Lignin; Veratraldehyde; Veratric acid; hydrogen peroxide bleaching
2018-P18
リグニンのアシドリシスにおけるフェノール性水酸基の重要性○叶 巧巧、横山 朝哉、秋山 拓也、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Significance of Phenolic Hydroxy Group in Lignin Acidolysis
Qiao-qiao Ye, Tomoya Yokoyama, Takuya Akiyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life
Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract:
The most common C6-C3-type phenolic β-O-4 lignin model compound,guaiacylglycerol-β-guaiacyl ether (I), was acidolyzed in an aqueous 82% 1,4-dioxane mainly using HCl, HBr or
H2SO4 as an acid. The results were compared with those of the corresponding non-phenolic analogue,
veratrylglycerol-β-guaiacyl ether (IV), obtained in our previous study to discuss the effect of the presence of thephenolic hydroxy group on the acidolysis reaction. Phenolic compound I was acidolyzed much more rapidly
than non-phenolic compound IV in accordance with previous knowledge on the acidolysis. It was surprising, on
the other hand, that the reaction route of phenolic compound I is not the same as that of non-phenolic compound667

IV. Fairly amounts of the primary C6-C3-type Hibbert’s ketone and its isomer were detected in the acidolysis ofphenolic compound I using H2SO4, although in the same acidolysis of non-phenolic compound IV the major
reaction product was exclusively the non-phenolic C6-C2-type Hibbert’s monomer afforded by the liberation ofthe γ-hydroxymethyl group as formaldehyde. It was thus confirmed that the presence of the phenolic hydroxygroup affects not only the rate but also mechanism of the acidolysis. The same comparisons were also
performed using C6-C2-type phenolic and non-phenolic β-O-4 lignin model compounds.
Keywords: alkyl aryl ether, hydrobromic acid, hydrochloric acid, sulfuric acid2018-P19
アルカリ性下におけるリグニンのキノンメチド構造生成に及ぼす芳香核構造の影響〇山内 富由、河本 理、秋山 拓也、横山 朝哉、松本 雄二
東京大学大学院農学生命科学研究科 生物材料科学専攻 木材化学研究室
Effect of the type of aromatic nucleus on the formation of quinone methide structure in lignin under alkalineconditions
Fuyu Yamauchi, Osamu Kawamoto, Takuya Akiyama, Tomoya Yokoyama, and Yuji Matsumoto
Laboratory of Wood Chemistry, Department of Biomaterial Sciences,
Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan
Abstract: The purpose of this study is to examine the effect of the type of aromatic nucleus on the formation
rate of quinone methide (QM) under alkaline pulping conditions by employing simple phenolic C6-C1-type
compounds (methyl ether of p-hydroxybenzyl alcohol derivatives) carrying one or two functional groups at themeta- of the benzyl position. The formation rate of QM was in the order of the compounds carrying: di-CH3 >di-OCH3 (syringyl) > CH3 > OCH3 (guaiacyl) > none (p-hydroxyphenyl) > F > Cl. It was possible to consider
that the electron donating or withdrawing effects of the functional groups promote or suppress the formation of
QM, respectively. Because these effects of the functional groups are known to similarly promote or suppress
oxygen oxidation of corresponding phenol derivatives under alkaline conditions, other simple C6-C1-type
compounds analogous to the above were subjected to an oxygen oxidation and the order of their disappearance
rates were compared with the above observed formation rate of QM. The oxidation rate was in the order of:
di-OCH3 (syringyl) > di-CH3 > OCH3 (guaiacyl) > CH3 > none (p-hydroxyphenyl) > Cl. This order was
similar to that of the formation rate of QM, except that the OCH3 group promotes the oxygen oxidation morethan the CH3 group.
Keywords: methoxy group, substituent, electron donating ability, π electron system, oxygen-alkali
2018-P20
非天然型コニフェリンの合成と性質○前田晴香 1)、津山濯 2)、高部圭司 1)、上高原浩 1)、高野俊幸 1)
1)京大院農、2)宮崎大農
Synthesis and property of coniferin enantiomer
Haruka Maeda1), Taku Tsuyama2), Keiji Takabe1), Hiroshi Kamitakahara1), Toshiyuki Takano1)
1) Graduate School of Agriculture, Kyoto University, Japan
2) Faculty of Agriculture, Miyazaki University, Japan
Abstract: Coniferin enantiomer which is composed of L-glucose and coniferyl alcohol was synthesized by theconventional method. Coniferin enantiomer was not degradated by β-glucosidase, differing natural coniferin.
Coniferin enantiomer showed the law membrane permeability. The result suggest glucose moiety of coniferin is
important to the membrane permeability.
Keywords: coniferin, monolignol, lignin, enzyme, L-glucose
2018-P21
フェニルグリコシド型 LCC（リグニンー多糖複合体）解析用モデル化合物の合成〇櫻井沙也佳 1)、水上貴仁 1)、飛松裕基 2)、上高原浩 1)、高野俊幸 1)
１）京大院農、２）京大生存研
Preparation of new phenyl glycoside-type LCC model compounds for NMR analysis of native LCC
Sayaka Sakurai1), Takahito Mizukami1), Yuki Tobimatsu2), Hiroshi Kamitakahara1),
Toshiyuki Takano1)
1)Graduate School of Agriculture, Kyoto University, Japan
2)Research Institute for Sustainable Humanosphere, Kyoto University, Japan
668

Abstract: New phenyl glycoside type LCC model compound (β-5 type dilignol glycoside 6) was preparedfrom β-5 type dilignol 1 by the four reaction steps (acetylation, selective deacetylation, glycosyration,
deacylation). The key reaction in the synthetic route was glycosyration. Glycosyration between β-5 dilignol
derivative 3 and glycocyl imidate 4 afforded β-glucoside exclusively. The synthetic method for compound 6 wasapplied to the syntheses of other LCC model compounds. The fully assigned NMR spectra of guaiacyl dilignol
β-D-glycosides provided useful database information for the analysis of LC linkages in plant cell walls using
high resolution NMR techniques.
Keywords: 2D-NMR, dilignol β-glycoside, hetero-nuclear single quantum coherence (HSQC),
lignin-carbohydrate complex (LCC), phenyl glycoside
2018-P22
PEG-HRP を用いた有機溶媒中でのコニフェリルアルコールの脱水素重合○山下綾菜、岸本崇生、濱田昌弘、中島範行、占部大介
富山県立大学工学部生物工学科
Dehydrogenative Polymerization of Coniferyl Alcohol in Organic Solvents with PEG-HRP
Ayana Yamashita, Takao Kishimoto, Masahiro Hamada, Noriyuki Nakajima, Daisuke Urabe
Department of Biotechnology, Faculty of Engineering, Toyama Prefectural University
Abstract: Among the interunit linkages in lignin, a -O-4 bond is one of the most important bonds. The
frequency of the -O-4 bond is about 50-60% in wood lignins. Whereas the frequency of the -O-4 is low in an
artificial lignin which is obtained by the dehydrogenative polymerization of monolignols in buffer solution. Thismay be partly attributed to the fact that the environment of lignin biosynthesis is more hydrophobic than thebuffer solution because of the presence of hemicellulose in the cell wall. In this study, the dehydrogenative
polymerization of coniferyl alcohol was conducted in aq. EtOH with HRP or PEG-HRP to better understand theeffect of hydrophobic environment on lignin biosynthesis.
Keywords: hydrophobicity, polyethylene glycol, DHP, HSQC, GPC
2018-P23
ケナフコアから血圧抑制および抗糖化成分の検出〇 山内 一慶
トヨタ紡織株式会社 新領域開拓部
Detection of lignin-derived components which have blood pressure suppression and antiglycation from Kenafcore
Kazuchika YAMAUCHINew Field Pioneering Division, TOYOTA BOSHOKU CORPORATION
Abstract: Kenaf core was hydrolyzed with water or 1 to 3 % of hydrogen peroxide solution. Obtainedwater-soluble compounds were estimated with antihypertensive effect and anti-glycation effect on collagen.
Interestingly, both of effects were detected in all water soluble components from Kenaf core hydrolysis withwater or hydrogen peroxide solution. These components contained some lignin-decomposed products. This
study is suggested that a new lignin application which is a utilization of lignin-derived products as a functional
component.
Keywords: lignocellulose decomposition, hydrogen peroxide, functional components, blood pressure
suppressant, anti-glycation component
2018-P24
マイクロ波反応を用いたサトウキビバガスからの抗ウイルス活性物質の生産○木村智洋 1），李瑞波 1）、應田涼太 1）,2）、西村裕志 1）、藤田尚志 2）、渡辺隆司 1）
1）京都大学・生存圏研究所、2）京都大学・ウイルス・再生医科学研究所
Production of Antiviral Compounds from Sugarcane Bagasse by Microwave Reactions
Chihiro Kimura1), Ruibo Li1), Ryota Ouda1),2), Hiroshi Nishimura1), Takashi Fujita2),
Takashi Watanabe1)
1) Research Institute for Sustainable Humanosphere, Kyoto University, Japan
2) Institute for Frontier Life and Medical Sciences, Kyoto University, Japan
Abstract: The process of converting lignocellulose into high value-added compounds as well as platformchemicals and fuels is strongly required for establishment of biorefinery. Sugarcane bagasse is one of the mostabundant lignocellulosic agricultural residues, and promising feedstock for biofuels and chemicals. Our669

objective in the present study is production of antiviral compounds from sugarcane bagasse. Bagasse wasdecomposed by microwave reaction in several polar solvents with catalysis, and the degradation products werefractionated using several organic solvents. Antiviral activities against encephalomyocarditis virus (EMCV) of
each fraction were evaluated by real-time polymerase chain reaction. The chemical structure of antiviralcompounds was analyzed by pyrolysis-GCMS and NMR. The results suggested that the antiviral compounds arecomposed of polysaccharide and lignin and that the antiviral compounds directly inhibited the EMCV
replication.
Keywords: Sugarcane bagasse, Microwave degradation, Antiviral agent, Lignin
2018-P25
リグニンだけを炭素源とした cis,cis-ムコン酸生産に効果的な培養要素の同定
阿久津 美歩 1,3)、杉田 晴佳 1,3)、上村 直史 2,3)、政井 英司 2,3)、園木 和典 1,3)
1)弘前大・農生、2)長岡技大院・生物、3)JST-ALCA
Identification of effective factors for sugar-free cis, cis-muconic acid production from lignin-related phenols
Miho Akutsu1,3), Haruka Sugita1,3), Naohumi Kamimura2,3), Eiji Masai2,3), Tomonori Sonoki1,3)
1)Agriculture and Life Science, Hirosaki University, Japan 2) Department of Bioengineering, Nagaoka
University of Technology, Japan 3) JST-ALCA
Abstract: cis,cis-muconic acid (ccMA) is a platform chemical for polymer synthesis and thus bio-based ccMA
production from carbohydrate such as glucose has been reported. In this study, we developed a new bacterial
strain capable of producing ccMA from lignin-derived phenols, in which no carbohydrates were required for thesource of carbon and energy. The engineered Pseudomonas putida strain could grow not only on vanillate or
4-hydroxybenzoate but also lignin extracts from Japanese Cedar, and produced ccMA without consuming sugar.
Through this work, we revealed dissolved oxygen is an effective parameter in regulating ccMA yield andidentified proper supply of nitrogen in addition to carbon source is necessary to maintain ccMA production in
fed-batch culture mode.
Keywords: Softwood lignin, cis,cis-muconic acid, metabolic engineering, bio-based chemical, lignocellulosic
biomass utilization
2018-P26
NMR 法によるリグニン-セルラーゼ糖質結合モジュール間吸着の解析〇 德永有希 1)、永田崇 2)、近藤敬子 2)、片平正人 2)、渡辺隆司 1)
1) 京都大学生存圏研究所、2) 京都大学エネルギー理工学研究所
Binding Analysis between Lignin and Carbohydrate Binding Module of Cellulase by NMR
Yuki Tokunaga 1), Takashi Nagata 2), Keiko Kondo 2), Masato Katahira 2), Takashi Watanabe 1).
1) Research Institute for Sustainable Humanosphere, Kyoto University, Japan.
2) Institute of Advanced Energy, Kyoto University, Japan.
Abstract: Enzymatic saccharification of lignocellulosic biomass is expected to produce green chemicals.
Industrially, a cellulolytic system including cellobiohydrolase I (Cel7A) from Trichoderma reesei has been
widely used. Cel7A consists of catalytic domain and carbohydrate binding module 1 (TrCBM1) connected withhighly glycosylated linker. TrCBM1 plays a role to enhance activity of Cel7A by bringing the catalytic domain
in close to the cellulose. However, TrCBM1 has affinity to lignin, in addition to cellulose, and the resultant
non-productive binding to lignin decreases efficiency of the saccharification. To date, the interaction mechanism
between TrCBM1 and lignin has not been clearly understood. In this study, we analyzed interaction site of
TrCBM1 with lignin at amino acid resolution using NMR. Binding site of TrCBM1 was analyzed by 1H-15N
SOFAST-HMQC NMR with incremental titration of cellohexaose and milled wood lignin (MWL) fromJapanese cedar and Eucalyptus globulus. The mechanism of the non-productive binding was discussed based on
the binding analysis.
Keywords: Carbohydrate binding module, NMR, Cellulase, Chemical shift perturbation
2018-P27
褐色腐朽の観点からのリグニンが保持する第二鉄還元能の考察○田丸 慶明１）、吉田 誠１）、Barry Goodell２）
１）東京農工大学農学部
２）Department of Microbiology, University of Massachusetts Amherst
Iron-reducing capacity of lignin and the implication on the relationship with brown-rot mechanism
670

Yoshiaki Tamaru1), Makoto Yoshida1) and Barry Goodell２)1) Department of Environmental and Natural Resource Science, Tokyo University of Agriculture andTechnology, Tokyo 183-8509, Japan
2) Department of Microbiology, 102 Morrill Science Center, IV-N 639 North Pleasant Street University of
Massachusetts Amherst, MA 01003
Abstract: Brown-rot fungi are one of the groups of wood decay fungi, and the fungi are able to deconstructwood cell wall efficiently with modification of lignin structure although the genes encoding lignin-degrading
peroxidases were lost on the genome of the fungi. As the mechanism of brown-rot wood decay,chelator-mediated Fenton (CMF) reaction (Fe2+ + H2O2 → Fe3+ + OH¬– + ・OH) is commonly accepted.
The reaction generates multitude of hydroxyl radicals that are able to rapidly attack wood cell wall components.
In this mechanism, ferric iron that is stable state in natural environment in wood is reduced by phenolic
compounds that are expected to be secreted by brown-rot fungi. On the other hand, lignin also possesses
plentiful amount of phenolic structure, and the structure may have relationship with the iron-reducing system of
CMF reaction. In the present study, iron-reducing capacities of artificially synthesized and isolated lignins andlignocellulosic materials were investigated.
Keywords: Brown-rot, Fenton reaction, Iron reduction, Electron transfer from lignin
2018-P28
白色腐朽菌ヒラタケにおける vp2, vp3 遺伝子の単独および二重破壊が木粉中のリグニン分解に及ぼす影響◯坂知奈美 1)、中沢威人 1)、山田美紗登 2)、西村裕志 2)、竹中敦紀 1)、渡辺隆司 2)、坂本正弘 1)、本田与一 1)
1)京都大学大学院農学研究科、2)京都大学生存圏研究所
Effects of single or double disruptions of vp2 and vp3 genes on wood lignin degradation in the white-rot fungus
Pleurotus ostreatus
Chinami SAKA1), Takehito NAKAZAWA1), Misato YAMADA2), Hiroshi NISHIMURA2),
Atsuki TAKENAKA2), Takashi WATANABE2), Masahiro SAKAMOTO1), Yoichi HONDA1)
1)
Graduate School of Agriculture, Kyoto University,
2)
Research Institute for Sustainable Humanosphere, Kyoto University
Abstract: White-rot fungi efficiently degrade high molecular-weight lignin in natural condition. It is generally
thought that white-rot fungi secrete lignin-modifying enzymes, such as manganese peruoxidases (MnPs) andversatile peruoxidases (VPs), and they trigger oxidative degradation of wood lignin. However, it has not been
examined whether these enzymes are involved in wood lignin degradation yet. In this study, we examined
effects of targeted disruptions of Pleurotus ostreatus vp2 and vp3, which are predominantly expressed at thetranscription level, on beechwood sawdust medium. It was shown that vp2 and vp3 disruptions do not decrease
the lignin degradation quantitively. RNA-seq and quantitative RT-PCR analyses showed that transcript
accumulation of mnp1, mnp2, and mnp6 increases in vp2/vp3 double disruptants. HSQC analysis suggested
oxidation of G nuclear allele position increased in the double disruptants. Based on these results, it wassuggested that a transcriptional regulation mechanism exists to compensate expression of mnp genes in case of a
deficiency of vp genes in Pleurotus ostreatus.
Keywords: Pleurotus ostreatus, targeted gene disruption, lignin-modifying enzymes, lignin degradation,transcriptional regulation mechanism
2018-P29
白色腐朽菌ヒラタケにおける xyn10 および xyn11 遺伝子の破壊が稲わら中のリグニン分解に与える影響〇湯村直樹 1)、中沢威人 1)、呉紅麗 1)、坂本正弘 1)、本田与一 1)
1)京都大学大学院農学研究科
Effects of xyn10 and xyn11 disruptions on lignin degradation by the white-rot fungus Pleurotus ostreatus on ricestraw medium
Naoki YUMURA1), Takehito NAKAZAWA1), Hongli WU1),
Masahiro SAKAMOTO1), Yoichi HONDA1)
1)
Graduate School of Agriculture, Kyoto University,
Abstract: Lignin and arabinoxylan are generally linked via hydroxycinnamic acids such as ferulic acid in cellwall of grasses, which led us to examine the effects of targeted disruption of xylanase genes on lignin
degradation by the white-rot fungus Pleurotus ostreatus when grown on a rice straw medium. In this study, we
newly obtained some triple-gene disruptants among xyn10 (xyn10a, b, c) and xyn11 (xyn11a, b) through671

crossing single- and double disruptants that had been created in our previous study. We then examined theability of each disruptant to degrade lignin and xylan present in rice straw. It was shown that ligninolytic andxylolytic activities of some triple-gene disruptants obtained in this study were lower than those of the parental
strain, 20bf3. These results suggest that defects in xylan degradation way cause decrease in lignin degradation
when P. ostreatus is grown on the rice straw medium.
Keywords: Pleurotus ostreatus, rice straw, xylanase, lignin degradation, gene disruption
2018-P30
白色腐朽菌ヒラタケにおけるリグニン分解不全変異株の原因変異遺伝子 gat1 及び hirA の同定○森本亮太、中沢威人、坂本正弘、本田与一
京都大学大学院農学研究科
Ligninolysis deficiency is caused by mutations in gat1 and hirA genes in the white-rot fungus Pleurotus
ostreatus
Ryota MORIMOTO, Takehito NAKAZAWA, Masahiro SAKAMOTO, Yoichi HONDA
Graduate School of Agriculture, Kyoto University
Abstract: In nature, white-rot fungi efficiently degrade high molecular-weight lignin in wood biomass. It is
generally thought that the lignin degradation is triggered by fungal secreted enzymes such as manganeseperoxidase (MnPs) and versatile peroxidases (VPs). However, the whole mechanisms underlying the lignin
degradation remain to be elucidated. To identify new factors important in wood lignin degradation by thewhite-rot fungus Pleurotus ostreatus, we have introduced an efficient forward genetics approach. In this work, it
was revealed that mutations in gat1 and hirA genes, which encode a putative Agaricomycete-specificDNA-binding transcription factor and a putative component of HIR complex involved in nucleosome assembly,
respectively, decrease the ligninolytic activity when grown on a beechwood sawdust medium. RNA-seq analysis
showed that patterns of transcript accumulation of vp/mnp genes in gat1 and hirA strains were different fromthose in other mutant strains defective in ligninolysis obtained in our previous studies.
Keywords: forward genetics, gene disruption, lignin degradation, manganese peroxidase, RNA-seq
2018-P31
Brevibacillus を宿主とした交雑ヤマナラシ由来酸性ペルオキシダーゼの効率的分泌生産○平野 智哉 1)、大友 まひろ 1)、味木 智子 2)、甲斐 遼太 2)、川合 伸也 1, 2)1) 東京農工大学大学院農学研究科、2) 東京農工大学農学部応用生物科学科
Heterogeneous secretion of plant peroxidase from hybrid aspen in Brevibacillus
Tomoya Hirano, Mahiro Otomo, Ryota Kai, Satoko Amaki, Shinya Kawai
Tokyo University of Agriculture and Technology, Japan
Abstract: Most of plant peroxidases can oxidize coniferyl alcohol efficiently, but not sinapyl alcohol. On theother hand, a few plant peroxidases were reported to catalyze sinapyl alcohol as preferred substrate. They aresuggested to have the additional active sites on the protein surface different from the heme pocket in the activesite.
We tried to add the surface alternative catalytic sites of these peroxidases to PrxA3a, an anionic peroxidase of
hybrid aspen, Populus X kitakamiensis, for substrate specificity modifications and for certifications of thesurface amino acid residue catalyst hypothesis.
We already have succeeded heterologous expression of prxA3a in Saccharomyces cerevisiae and secretion of
PrxA3a as the glycosylated form to the culture medium. To crystallize PrxA3a produced in S. cerevisiae, thedeglycosylation procedure is necessary, in which the recovery yield is wrong. Then, we tried to express PrxA3a
in bacteria those can’t add polysaccharide chains to secretory proteins. But Escherichia coli has low ability tosecret proteins and most produced secretory proteins accumulate as inclusion bodies. To gain active proteinsfrom inclusion bodies, the procedures of denaturing and refolding are important. Brevibacillus is one genus ofgram positive bacteria. It can efficiently secret active proteins as non-glycosylated forms. This unique property
is considered to contribute for functional analysis and elucidation of the sugar chain role in the monolignol
polymerization reaction. Secreted PrxA3a in Brevibacillus was active, and we are characterizing the secreted
enzyme.
Keywords: Peroxidase; lignin; sinapyl alcohol; phytoremediation
2018-P32
Novosphingobium sp. MBES04 株のリグニン関連物質存在下におけるトランスクリプトーム解析〇大田ゆかり 1)，石井俊一 1)，嶋根康弘 1)，黒澤佳奈子 1)，市川淳子 1)，小林樹和 1)山田美紗登 2)，西村672

裕志 2)，渡辺隆司 2)
1)国立研究開発法人海洋研究開発機構(JAMSTEC)，2)京都大学生存圏研究所
Transcriptome analysis of Novosphingobium sp. MBES04 in response to lignin related compounds
Yukari Ohta1), Shun'ichi Ishii1), Yasuhiro Shimane1), Kanako Kurosawa1), Junko Ichikawa1),
Kiwa Kobayashi1), Misato Yamada2), Hiroshi Nishimura2), Takashi Watanabe2)1)Japan Agency for Marine-Earth Science and Technology (JAMSTEC) Japan,2)Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: Bacterial enzymes for β-O-4 reductive cleavage in lignin model are expected to be new tools of
lignin valorization. However, high production cost for the enzymes and cofactors is a hurdle to practicalprocessing of lignin preparations utilized as renewable materials. Biological lignin processing using bacterial
cells are a potential alternative to the enzymatic processing. Novosphingobium sp. MBES04 is capable ofreductive cleavage of β-O-4 linkages in some lignin breakdown materials. In order to understand metabolic
pathway of this microbe for lignin processing, we here conducted transcriptomic analysis in the presence oflignin-related compounds; guaiacylglycerol-β-guaiacyl ether (GGGE), vanillin and lignin fraction extracted
from hard wood (Eucalyptus globulus). We detected genes which were specifically induced in response to thesecompounds.
Keywords: Lignin, Novosphingobium, β-O-4 reductive cleavage, metabolic pathway, transcriptome
2018-P33
バクテリア細胞外膜におけるリグニン由来化合物取り込みメカニズムの解明◯藤田 雅也、森 光佑、上村 直史、政井 英司
長岡技術科学大学・生物
Elucidation of the outer membrane transport of lignin-derived aromatic compounds in Sphingobium sp. SYK-6
Masaya Fujita, Kosuke Mori, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: Bacterial catabolic systems for low-molecular-weight aromatic compounds derived from lignin havebeen intensively investigated in Sphingobium sp. SYK-6. To date, over 40 catabolic enzyme genes have been
isolated and functionally characterized. However, the uptake systems for these lignin-derived aromatics,
specifically, their outer membrane transport remains unknown. In this study, based on the presence of a large
number of homologous genes, we focused on the TonB-dependent receptor (TBDR) genes, which are generally
known as outer membrane transporters of Fe3+ siderophore and vitamin B12. We found that the transcription of
tbtA, one of the TBDR genes of SYK-6, was specifically induced in cells grown with 5,5'-dehydrodivanillate(DDVA). A tbtA mutant significantly decreased its capacity to grow on, convert, and uptake DDVA. Cellular
localization analysis indicated that TbtA is present in the outer membrane of SYK-6. The N-terminal TonB box
of TBDRs which is known to interact with the C-terminal domain of TonB is conserved in TbtA. Introduction of
mutations into the TonB box of TbtA significantly affected the growth of SYK-6 on DDVA, DDVA conversion,and DDVA uptake. Based on these observations, we concluded that TbtA plays an essential role in the DDVA
uptake across the outer membrane.
Keywords: Gram-negative bacteria, outer membrane transporter, TonB, biphenyl
2018-P34
Sphingobium sp. SYK-6 株における-1 型リグニン由来化合物の立体選択的な代謝システム◯前川 滉大 1)、小林 将大 1)、樋口 雄大 1)、上村 直史 1)、菱山 正二郎 2)、政井 英司 1)
1)長岡技術科学大学・生物、 2)森林総研
Stereoselective catabolism of -1 type lignin-derived aromatic isomersin Sphingobium sp. strain SYK-6
Kodai Maekawa1), Shota Kobayashi1), Yudai Higuchi1), Naofumi Kamimura1), Shojiro Hishiyama2), Eiji
Masai1)
1) Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
2) Forestry and Forest Products Research Institute, Tsukuba, Ibaraki, Japan
Abstract: Sphingobium sp. strain SYK-6 is able to utilize various lignin-derived biaryls as the sole source ofcarbon and energy. A 1 type biaryl, 1,2-bis(4-hydroxy-3-methoxyphenyl)-propane-1,3-diol (HMPPD)
consists of two diastereomers, threo and erythro, each of which has enantiomers (threo, HMPPD I and II;
erythro, HMPPD III and IV). In SYK-6 cells, HMPPD I and II (threo form) are initially oxidized at C position
to produce HMPPD-keto I and II, respectively. The C-dehydrogenase genes (ligD, ligL, and ligN) responsible
for the catabolism of -O-4 type biaryls were suggested to be involved in the oxidation of HMPPD I and IIIn673

this study, we examined the role of C-dehydrogenases in the catabolism of HMPPD, and the catabolic pathwayof HMPPD was partially determined. Among seven C-dehydrogenases, LigD, LigO, and SLG_12640
converted HMPPD I into HMPPD-keto I, while LigL and LigN transformed HMPPD II into HMPPD-keto II.
Characterization of mutants of C-dehydrogenase genes showed that multiple genes (ligD, ligO, SLG_12640)
are involved in the oxidation of HMPPD I while ligL has a predominant role in HMPPD II oxidation.
Interestingly, SLG_12640 exhibited an ability to reduce HMPPD-keto II into HMPPD IV in the presence of
NADPH. Furthermore, an SYK-6 cell extract was able to degrade HMPPD IV via vanillin without passing
through HMPPD-keto as an intermediate. These results suggest that the conversion of threo-HMPPD toerythro-HMPPD through oxidation of HMPPD and reduction of the resultant HMPPD-keto is essential todegrade threo-HMPPD.
Keywords: bacteria, diarylpropane, C -dehydrogenase biodegradation
2018-P35
Sphingobium sp. SYK-6 株におけるリグニン・ビフェニル化合物代謝系遺伝子群の転写制御システム◯新沼 皐、荒木 拓馬、上村 直史、政井 英司
長岡技術科学大学・生物
Transcriptional regulation of the catabolic genes of a lignin-derived biphenyl compound in Sphingobium sp.
strain SYK-6
Koh Niinuma, Takuma Araki, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: Sphingobium sp. strain SYK-6 is a bacterium which is able to degrade various lignin-derived biaryls
and monoaryls. The SYK-6 catabolic system is useful in converting these lignin-derived aromatics intovalue-added chemicals. To date, although a number of genes involved in the catabolism of lignin-derived biaryls
including 5,5’-dehydrodivanillate (DDVA) have been identified and characterized, their transcriptional
regulations remain largely unknown. In the SYK-6 genome, the genes responsible for the DDVA catabolism
such as the transporter genes (tbtA and ddvK) and the catabolic enzyme genes (ligZ, ligY, and ligXa) form agene cluster. These genes appeared to be regulated by ddvR, which encodes a MarR-type transcriptional
regulator and located just upstream of ligXa. In this study, we investigated the transcriptional regulation of the
DDVA catabolic genes. RT-PCR analysis showed that the DDVA catabolic gene cluster consists of threeoperons: the ligXa operon, the ddvR operon, and the tbtA operon containing tbtA, ddvK, ligZ, and ligY.
qRT-PCR analysis using SYK-6 cells and ddvR mutant cells revealed that the transcriptions of the ligXa andtbtA operons were negatively regulated by DdvR. Electrophoretic mobility shift assay demonstrated that DdvR
bound to the promoter regions of ligXa and tbtA, and DDVA functioned as an effector molecule of DdvR. In
addition, the inverted repeat sequences found on the promoter regions of the ligXa and tbtA operons played an
important role in the DNA binding of DdvR.
Keywords: 5-5 linkage, biphenyl, bacteria, catabolism, transcriptional regulation
2018-P36
Sphingobium sp. SYK-6 株におけるリグニン由来芳香族化合物の内膜 transporter の探索◯永吉 昂太、森 光佑、上村 直史、政井 英司
長岡技術科学大学・生物
Exploration of the genes responsible for inner membrane transport of lignin-derived aromatic compounds in
Sphingobium sp. SYK-6
Kota Nagayoshi, Kosuke Mori, Naofumi Kamimura, Eiji Masai
Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan
Abstract: Various enzyme genes necessary for the catabolism of lignin-derived aromatic compounds have been
identified and characterized in Sphingobium sp. strain SYK-6. However, little is known about the bacterial
uptake of lignin-derived aromatic compounds. The transport of aromatic acids is known to be mediated by thearomatic acid/H+ symporter (AAHS) family, one of the major facilitator superfamily transporters. In the SYK-6
genome, there are 16 putative AAHS genes, and one of these genes pcaK was found to encode a major
protocatechuate transporter which has a capacity to uptake vanillate. In this study, in order to clarify whether the
16 putative AAHS genes of SYK-6 are involved in the uptake of lignin-derived aromatic compounds, mutants ofall the AAHS genes and multiple mutants of seven AAHS genes with pcaK were created. Analysis of thesemutants suggest that PcaK partially participates in the uptake of vanillate, syringate, and 4-hydroxybenzoate.
However, the contribution of other AAHS genes to the uptake of these compounds appears to be minimal.
Keywords: bacteria, transporter , proton motive force, monomer674

2018-P37
イネの GUX, XAT – RNAi 抑制株の作成と細胞壁構成成分の解析〇 長谷川 智彦、中沢 威人、本田 与一、坂本 正弘
京都大学大学院農学研究科
Making of GUX, XAT – RNAi Transformants of Rice and Analysis of Components of Plant Cell Wall〇Tomohiko Hasegawa, Takehito Nakazawa, Yoichi Honda, Masahiro Sakamoto
Graduate School of Agriculture, Division of Environmental Science and Technology,
Kyoto University
Abstract: In our previous research, we produced transformants, which repressed the gene related tohemicellulose synthesis, and analyzed their gene expression and plant cell wall components to understand thefunction of hemicellulose in plant cell wall. Then, we found that both hemicellulose and lignin synthesis related
genes were repressed at the same time in transformants, and this result suggested that hemcellulose and lignin
biosynthesis are closely related in plant cell wall synthesis.
To elucidate this relationship in detail, we selected two genes, gluclonic acid transferase （GUX） and xylan
arabinose transferase (XAT), and produced each gene knockdown-transformant (T0). T0 stocks had distorted or
curved leaves character. On this research, we will report the content of sugar (glucose, xylose, and arabinose),
ferulic acid, and lignin of cell wall of the transformant.
Keywords: gluclonic acid transferase （GUX）, xylan arabinose transferase (XAT), RNAi, hemicellulose,lignin2018-P38
ヒノキ圧縮あて材細胞壁においてラッカーゼのｐ-クマリルアルコール取込み能力を可視化する〇平出秀人 1）、飛松裕基 2）、吉永新 1）、高部圭司 1）
1）京大院農 2）京大生存研
Visualization of p-coumaryl alcohol incorporation by laccase at the compression wood cell walls in Japanesecypress.
〇Hideto Hiraide1), Yuki Tobimatsu2), Arata Yoshinaga1), Keiji Takabe1)
1) Graduate School of Agriculture, Kyoto University, Japan.
2) Research Institute for Sustainable Humanosphere, Kyoto University, Japan
Abstract: Compression wood lignin includes p-hydroxyphenyl (H) unit, and it is believed that this unit isaccumulated in the “S2L” [1], which is highly lignified region localized in the outer portion of S2 layer. In
Japanese cypress (Chamaecyparis obtusa), a compression-wood-specific laccase (CoLac1) is localized in S2L[2], suggesting this enzyme may selectively oxidize H unit precursor, p-coumaryl alcohol. In this study, we
visualized incorporation abilities of p-coumaryl and coniferyl alcohols at the lignifying cell walls using
fluorescently-labeled monolignols [3]. In addition, we compared these results with those obtained in the supplyof H2O2, to examine whether laccase or peroxidase is the main enzyme for monolignol polymerization. Whenthe labeled coniferyl alcohol was fed to differentiating compression wood section in the removal of H2O2, thefluorescence signal was high at lignifying S1 and inner portion of S2, but low at S2L. While the fluorescencesignal of the labeled p-coumaryl alcohol was high at lignifying S2L, but low at the other layers. Moreover, thelabeled p-coumaryl alcohol was hardly incorporated into the normal wood cell walls during secondary wall
formation. These results suggest accumulation of H unit may be caused by a p-coumaryl-alcohol-specificlaccase expressed during S2L formation. Besides, the incorporation of these monolignols in compression andnormal wood cell walls, were not enhanced by supply of H2O2 while reduced by conversion of dissolved O2 to
H2O2. Therefore, in Japanese cypress, not peroxidase but laccase seems to be mainly responsible forlignification of the secondary wall.
Keywords: reaction wood, secondary cell wall , oxidative polymerization, guaiacyl unit
2018-P39
Altered lignin structures and improved cell wall digestibility of rice mutants deficient in tricin biosynthesis
genes◯Pui Ying Lam1), Yuki Tobimatsu1), Toshiaki Umezawa1,2), Clive Lo3)
1)Research Institute for Sustainable Humanosphere, Kyoto University, Japan
2)Research Unit for Development of Global Sustainability Studies, Kyoto University, Japan
3)School of Biological Sciences, The University of Hong Kong, Hong Kong, China
675

Abstract: Many grass species naturally incorporate flavonoid tricin into cell wall lignins. However, how suchlignin-integrated tricin functions in planta and also how it affects the usability of grass biomass remain largely
unknown. To address these issues, we isolated tricin-truncated rice mutants and analyzed their cell walls withemphasis on lignin structure and cell wall digestibility. Through chemical, histochemical and 2D NMR analyses,
we demonstrated that rice mutants deficient in OsFNSII and OsCAldOMT1 comprised lignins largely depleted
in tricin units. In addition, the osfnsII mutant appeared to heterologously incorporate naringenin as a novel
lignin monomer. On the other hand, oscaldomt1 mutant was additionally depleted in syringyl lignin units,suggesting that OsCAldOMT1 is a bifunctional OMT involved in both the tricin and syringyl lignin biosynthetic
pathways. These two mutants were further shown to display improved cell wall digestibility.
Keywords: Enzymatic saccharification, Flavone synthase II, Poaceae, 5-Hydroxyconiferaldehyde
O-methyltransferase, Nuclear magnetic resonance2018-P40
Sphingobium sp. SYK-6 株由来 Cα-dehydrogenase とマウス由来 Cx43 を共発現する組換えポプラの解析○竹下涼 1)、Lutfar Rahman 1)、今村真子 1)、諾恩達古拉 1)、上杉幹子 1)、
上村直史 2)、政井英司 2)、梶田真也 1)
1⁾東京農工大学大学院生物システム応用科学府 2)長岡技術科学大学大学院工学研究所
Analysis of transgenic hybrid poplar coexpressing Cα-dehydrogenase derived from Sphingobium sp. strain
SYK-6 and mouse Cx43
Ryo Takeshita1), Lutfar Rahman1), Mako Imamura1), Noendagula1), Mikiko Uesugi1),
Naofumi Kamimura2), Eiji Masai2), Shinya Kajita1)
1) Graduate School of Bio-Applications and Systems Engineering, Tokyo University ofAgriculture and Technology, Tokyo 184-8588, Japan
2) Graduate School of Engineering, Nagaoka University of Technology, Niigata 940-2188, Japan
Abstract: As global warming becomes a problem, plant biomass having carbon neutral characteristic attracts
attention as resources with less environmental burden. Plant biomass is a raw material such as bioethanol, but a
lot of cost is required to remove lignin for the production. Therefore, it aims to reduce cost of plant biomass
processing by improving degradability and separability of lignin by changing its structure by genetic
engineering. Bacterial strain Sphingobium sp. SYK-6 which can utilize lignin-derived aromatic compounds as acarbon source have LigD, an enzyme involved in the degradation of a dimeric compound containing a β-O-4
type bond. It oxidizes a hydroxy group at Cα position to a keto group using NAD+as a coenzyme. It is expectedthat β-O-4 bond with a keto group is increased by the expression and lignin degradability is enhanced underalkaline conditions. In this study, we co-expressed a mouse NAD+ transporter, connexin, in the transgenic
poplar with LigD for increase of NAD+ concentration in the cell wall and analyzed its lignin structure.
Keywords: SYK-6, LigD, Cx43, poplar, genetic engineering
2018-P41
モノリグノール生合成中間体の変換酵素遺伝子を利用したリグニンエンジニアリング〇徳江洋介 1),2)、坂本真吾 2)、上村直史 1)、梶田真也 3)、政井英司 1)、光田展隆 2)1) 長岡技術科学大学・生物、2) 産業技術総合研究所・生物プロセス
3) 東京農工大学大学院・生物システム
Lignin engineering using enzyme genes for the conversion of monolignol biosynthetic intermediates
Yosuke Tokue1),2), Shingo Sakamoto2), Naofumi Kamimura1), Shinya Kajita3), Eiji Masai1),
Nobutaka Mitsuda2)
1) Department of Bioengineering, Nagaoka University of Technology, Nagaoka, Niigata, Japan2) Bioproduction Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Ibaraki, Japan
3) Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture andTechnology, Fuchu, Tokyo, Japan
Abstract: Lignin plays various critical roles in plant such as mechanical strength whereas it is a major obstacle
to the lignocellulosic biomass utilization due to its recalcitrance. Lignin engineering is a promising strategy to
reduce the biomass recalcitrance. Previously, we created transgenic plants using 47 expression constructs
harboring various enzyme genes, products of which convert metabolites of monolignol biosynthetic pathways,
under the control of a xylem preferential promoter derived from hybrid aspen. Transgenic plants harboring
genes encoding coniferaldehyde dehydrogenase (calB), feruloyl-CoA 6'-hydroxylase (F6H1), andhydroxycinnamoyl-CoA hydratase/lyase (couA) showed apparent abnormalities in Wiesner and Mäule staining
676

patterns. In this study, we further characterized these promising transgenic plants. An irregular xylem phenotype
with collapsed vessels was observed in the CouA transgenic line. Lignin content and enzymatic saccharification
efficiency tended to decreased and increased (30% 60% higher than wild type) respectively in all three lines,
while they showed no marked changes in the total sugar content and monosaccharide composition.
Keywords: Arabidopsis thaliana, lignin modification, glucose productivity, monolignol biosynthetic
intermediate2018-P42
Pseudomonas fluorescens AN103 株由来のヒドロキシシンナモイル CoA ヒドラターゼリアーゼ（HCHL）遺伝子を導入したポプラの解析諾恩達古拉 1)、青柳伸之介 1)、那布其 1)、辻幸子 1)、上杉幹子 1)、Edouard Pesquet2)、
John Ralph3), 4)、梶田真也 1)
1) 東京農工大学大学院 生物システム応用科学府
2) Arrhenius laboratories, Department of Ecology, Environment and Plant Sciences, Stockholm University,
10691 Stockholm, Sweden
3) US Department of Energy, Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, Universityof Wisconsin, Madison, Wisconsin 53726, USA
4) Department of Biochemistry, University of Wisconsin, Madison, Wisconsin 53706, USA
Analysis of transgenic poplar harboring the hydroxycinnamoyl-CoA hydratase-lyase (HCHL) gene derived from
Pseudomonas fluorescens AN103
Nuoendagula1), Shinnosuke Aoyagi1), Nabuqi1), Yukiko Tsuji1), Mikiko Uesugi1),
Edouard Pesquet2), John Ralph3), 4), Shinya Kajita1)
1) Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan
2) Arrhenius laboratories, Department of Ecology, Environment and Plant Sciences, Stockholm University,
10691 Stockholm, Sweden
3) US Department of Energy, Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, Universityof Wisconsin, Madison, Wisconsin 53726, USA
4) Department of Biochemistry, University of Wisconsin, Madison, Wisconsin 53706, USA
Abstract: Lignocellulosic biomass, which is mainly composed of cellulose, hemicellulose, lignin. It is acarbon-positive, renewable, and sustainable resource, representing an ideal alternative to fossil resources.
However, the use of lignocellulosic biomass is restricted by lignin due to its intertwined structural properties.
Generally, lignin limits enzymatic accessibility and reduces hydrolysis efficiency of lignocellulose. It isbiosynthesized under an unique pathway with various enzymes and phenolic lignin monomers are exported
from cytoplasm to cell wall. Random oxidative polymerization of the monomers occurs in the cell wall. In thisstudy, we produced and analyzed several transgenic poplars harboring the gene encoding thehydroxycinnamoyl-CoA hydratase-lyase (HCHL) for depletion of the intermediate of hydroxycinnamoyl-CoAin the lignin biosynthetic pathway. Resultant transgenic plants exhibited abnormal growth with brown-coloredwood. We characterized their lignin contents, distribution, and monomeric compositions as well as thedigestibility of the cell wall.
Keywords: chain shortening enzyme, lignin recalcitrance, transgenic plant
2018-P43
Parvibaclum lavametivorans DS-1 株由来の PlDBR 遺伝子を導入した組換えポプラの解析○胡石 1)、諾恩達古拉 1)、美麗 1)、山本雅信 1)、平山晴加 2)、秋山拓也 2)、渡辺眞悟 3)
上村直史 3)、政井英司 3)、John Ralph4)、梶田真也 1)
1)東京農工大学、2)東京大学、3)長岡技術大学、4)ウィスコンシン大学
Analysis of transgenic poplar transformed with PlDBR derived from Parvibaclum lavametivorans DS-1
Shi Hu 1), Nuoendagula1), Li Mei 1), Masanobu Yamamoto1), Haruka Hirayama2), Takuya Akiyama2),
Shingo Watanabe3), Naohumi Uemura3), Eishi Masai3), John Ralph4), Shinya Kajita1)
1) Tokyo University of Agriculture and Technology, Koganei Tokyo,184-8588, japan
2) The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, japan
3) Nagaoka University of Technology, Nagaoka Niigata,940-2188, Japan
4) University of Wisconsin, Madison 1552 University Avenue Madison, WI53726-4084
Abstract: The bond formed through the carbon of β-position is important for determine the chemical and677

physical properties of lignin. Double bond reductase (DBR) is an enzyme that catalyzes the reaction of reducing
the double bond of the side chain of coniferyl aldehyde (CALD) which is a precursor of monolignol. In thisstudy, we focused on a DBR which was derived from Parvibaclum lavametivorans DS-1(PlDBR). In order toinvestigate the impact of PlDBR expression to the structural changes of lignin in transgenic plants. We had
surveyed the lignin content and syringyl/guaiacyl (S/G) ratios of lignin in transgenic poplar.
Keywords: PlDBR, poplar, structural changes, transgenic plant
2018-P44
二次壁肥厚を促進するイネ転写因子 OsNST2 を過剰発現する CAD 発現抑制ポプラの解析
那布其 1)、諾恩達古拉 1)、吴色吉日胡 1)、大迫侑貴 1)、高田直樹 2)、坂本真吾 3)
Edouard Pesquet4)、谷口亨 2)、光田展隆 3)、梶田真也 1)
1)東京農工大学大学院 BASE、2)森林総合研究所 森林バイオ研究センター
3)産業技術総合研究所 生物プロセス研究部門
4)Arrhenius laboratories, Stockholm University
Promoting secondary wall deposition by overexpressing the rice transcription factor OsNST2 in
CAD-downregulated transgenic poplar
Nabuqi1), Nuoendagula1), Sejirihu Wu1), Yuki Osako1), Naoki Takata2), Shingo Sakamoto3), Edouard
Pesquet4), Toru Taniguchi2), Nobutaka Mitsuda3), Shinya Kajita1)
1) Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture andTechnology, Tokyo 184-8588, Japan
2) Forest Bio-Research Center, Forestry and Forest Products Research Institute, Forest Research andManagement Organization, Hitachi, Ibaraki 319-1301, Japan3) Bioproduction Research Institute, National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Ibaraki 305-8566, Japan
4) Arrhenius laboratories, Department of Ecology, Environment and Plant Sciences, Stockholm University,
10691 Stockholm, Sweden
Abstract: It is well known that, NAC Secondary wall Thickening factors (NST) could effectively enhance thesecondary cell wall formation in plant. Overexpression of OsNST2 which is a rice ortholog gene of Arabidopsis
NST in nst1 nst3 double mutant of Arabidopsis under the control of NST3 promoter leads to an increase inamount of secondary wall [1]. On the other hand, downregulation of cinnamyl alcohol dehydrogenase (CAD)
expression in both Arabidopsis and poplar were effective in enhancing the saccharification yield [2][3].
Therefore, in this study, we introduced the NST3promoter::OsNST2 construct into CAD-downregulated poplar
for increasing the deposition of secondary cell wall with higher saccharification efficiency. Weights of fresh anddry woods prepared from transgenic stems, cell wall width of fibers, lignin content and composition of thewoods as well as enzymatic digestibility of cell wall residues were analyzed.
Keywords: Transcription factor OsNST2, Secondary cell wall, Lignin

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