米国のピクルス漬け床と小倉の糠床の比較
糠の存否で熟成香の化学成分はどう違うのか（米国農務省 USDA との交流から）2018年6月、米国農務省（USDA）の Truong VanDen 教授より発酵野菜関連で４名の博士研究員を紹介いただき、日本の糠床とアメリカのピクルス漬け床の観点で暫く交流した。

Suzanne はピクルス漬け床を専門とする准教授であり、非常に informational な彼女の論文を送って下さった。塩分低減策と床の床の品質劣化が記され、日本の糠床と同一問題を抱えていた。
お礼に北九州の糠の食文化の英文解説をプレゼントした。
一方、2022年7月、研究会のホームページに掲載の全ファイルが消失し、当時の英文ファイルの探索をFred にお願いした結果、記述部のみが見つかり送ってきてくれた。現在、英文版を復旧中

ピクルス漬け床1と糠床2の揮発成分（香り）の比較（参考文献は１ページ目のスライド）

ピクルス漬け床（brine)と糠床は共に水と塩を含有する。両床の主要な違いは後者が米糠を含有し、それ故、、米糠油、米糠蛋白等に起因する成分を多数含有していること。次頁の両床のエステル成分の比較はこれを明確に示している。
また、米糠油由来のオレイン酸とリノール酸に起因するラクトン（C9-lactone、ピーチの香）はピクルス漬け床には生成しない。

ピクルス漬け床（左）と糠床（右）の揮発成分(ｴｽﾃﾙ類)の比較

Volatile Compounds in Fermented Cucumber Brines 1
1

Aged Rice Bran Beds 2
2

Suzanne, J. Food Sci., 76 (1), C168-C177 (2011). From Table 3 and Table 4

M. Imai, Agric. Biol. Chem., 55 (9), 2209-2220 (1991).

[Compound Groups][Compound Groups]

Hydrocarbons, Alcohols, Aldehydes, Ketones, Acids, Estetrs, Ethers, Furans, Pyrans

Esters, Acidfs, Aldehydes, Ketones, Hydrocarbons, S,N-Compounds, Alcohols
Lactones, Phenols

1 Methyl lactate

Lactic acid fermentation

2 Ethyl lactate
3 Isoamyl lactate

乳酸と酢酸のエステル

4 Methyl acetate

Alcohol fermentation & oxidation

5 n-Propyl acetate

1,719,881
7,808,306
27,084
1,012,974
33,8836 Isoamyl acetate

Dibutyl phthalate
Imai (130 years rice bran bed)

fold
Average area

Esterschange *-3.2-1.7

1 Ethyl lactate

2.3

2 Amyl formate

6.0

3 Propyl acetate

6.0

4 Hexyl acetate

Lactic Acid Fermentation

AlcoholFermentation& Oxidation

USDA (Suzanne)Esters

5 cis-3-Hexenyl acetate
6 Octyl acetate
7 Phenethyl acetate
8 Propylphenyl acetate
9 1,3-Propanediol monoacetate
10 1,3-Propanediol diacetate

Glutamate metabolites by yeast

8 Ethyl propionate

9 2-Methyl, 3-hydroxy, 2,4,4-trimethylpentyl propanoate
10 2-Methyl, 2,2-dimethyl-1-(2-hydroxy-1-methylethyl) propylpropionate
11 trans-3-Hexenyl butanoate
12 Ethyl nitrate

57,501
81,551
281,380
185,822
42,111
4,708-1.9

11 Ethyl propionate

Glutamic acid
Metabolites
by yeast

7 Methyl propionate

12 Isobutyl propionate
13 Propyl propionate
14 Amyl propionate
15 Hexyl propionate
16 Heptyl propionate
17 2-methylbutyl propionate
18 Octyl propionate
19 Phenethyl propionate

米糠油に起因する

20 Propyl butyrate(C4 acid)

21 Propyl valerate(C5 acid)

22 Propyl 2-methylbutyrate
23 Ethyl caproate(C5 acid)(C6 acid)

24 Propyl caproate(C6 acid)

25 Ethyl caprylate(C8 acid)

26 Propyl caprylate (C8 acid)
27 Methylmyristate
28 Ethyl myristate

ricebranoil

29 Propyl myristate
30 Methyl palmitate

エステルがないbesed

31 Ethyl palmitate
32 Propyl palmitate
33 Methyl oleate
34 Ethyl oleate

esters35 Propyl oleate
36 Ethyl linoleate
37 Propyl linoleate*Changes in volatile metabolites associated with anaerobic spoilage of fermented cucumber slurry (pH 3.8, 6% NaCl)]

38 Propyl benzoate[Aromatics]

39 Dibutyl phthalate[Aromatics]*

acids contained

acids eleminated*

ppb

ppb

483

－

555
1053
－
56
－
236

－
－
58
－
41
264
83－
－
－
69－
1930
－
－
－
155－
412
54－
69－

91
－
12
119
27
192
44
126
78
794
56
1920
38

189

57

－
－

36
107
3675
173
84
286
465
49
283
336
220
423112342－10345203
165－144－－157
120175neutralization with 10% aqueous NaHCO 3 solution, followed by the extraction with diethylether

Aged Rice Bran Beds & Boiled Soup of Nuka-Daki 3
3Makinoya (Nuka-Doko, Nuka-Zuke & Nukla-Daki shop)[Compound Groups]
Esters, Acidfs, Aldehydes, Ketones, Hydrocarbons, S,N-Compounds, Alcohols

槙乃家＊の熟成糠床と糠炊き煮汁の揮発成分の比較

Lactones, Phenols

1 Ethyl acetate

Nuka-DokoNuka-DokoNuka-Daki

Nuka-DakiArea (2)EstersArea (1)

EstersArea (2)Area (1)(excess presence produces poor odor)

38,202,105

2 Ethyl propionate

11,556,674

3 Ethyl butanoate

15,710,605

4 Ethyl 2-methylbutanoate

6,089,301

5

disappeared
totally vaporized during cooking

disappeared
disappeared
Ethyl hexanoate

6 Ethyl octanoate
7 Ethyl nonanoate
8 Ethyl decanoate
9 Ethyl dodecanoate

ricebran

10 Ethyl tetradecanoate
11 Ethyl pentadecanoateoil

12 Ethyl hexadecanoate

150,210,947
24,894,496

bran

48,620,335

8,147,118
disappeared
disappeared
135,281,979

0.19

66,845,876 Ethyl pentadecanoate

8,806,026

0.13

2,933,396,4970.33

14Ethyl-9-hexadecanoate

15Ethyl heptadecanoateoil

179,555,133&

10,799,387,357 Ethyl oleate
9,379,383,181 Ethyl linoleate or Ethyl 9,12-octadecanoate

fish

58,971,918
30,999,106
3,720,382,313

0.34

3,823,327,819

0.41
0.25

18 Ethyl linoleate

937,497,489 Ethyl lenoleate

236,327,234

19 Methyl 9,12,15-octadecatrienoate

875,101,633 Ethyl 9,12,15-octadecatrienoate

263,022,187

20 Methyl hexadecanoate

bran

21 Methyl octadecenoate

oil

118,452,987 Methyl hexadecanoate
212,997,674 Methyl cis-11-eicosenoate

oil

28,629,247

based

24 n-Propyl-9-octadecenoate

371,676,861 n-Propyl-9-octadecenoate

25 n-Propyl-9,12-octadecadienoate

278,387,590 n-Propyl-9,12-octadecadienoate

26 Propyl hexadecanoate

27 Ethyl-β-(4-hydroxy-8-methoxyphenyl) propionate

204,012,158 Isopropyl linoleate
Ethyl-β-(4-hydroxy-3-methoxyphenyl) propionate

28 Ethyl 9,12,15-octadecatrienoate

19,300,034 2-Heptadecanoate[Aromatics]
29 2-Phenylethyl acetate

25,630,913

0.22

47,276,168

0.22

98,498,467

0.27

90,869,186

0.33

321,899,558

22 Methyl-cis-11-eicosenoate
23 3-Methyl-1-butyl-acetate

based

esters82,201,633
9,085,740[Aromatics]
46,399,955 2-Phenylethyl acetate

20,223,58930

Methyl 3-phenyl-2-propanoate

89,850,79431

Isopropyl-4-hydroxy benzoate

645,211,858

32

Isobutyl -4-hydroxy benzoate

75,760,752

33 Ethyl benzoate

0.26

724,667,764 Ethyl tetradecanoate
8,808,264,017 Ethyl hexadecanoate

rice

13,766,125
disappeared

Ethyl octadecanoate

17 Ethyl linoleate

rice

31,486,389 Ethyl octanoate

13

16 Ethyl oleate

disappeared

30,753,973 Ethyl benzoate

9,523,735＊波多野淳子研究会顧問

ピクルス漬け床（左）と糠床（右）のカルボン酸類の比較
USDA (Suzanne)
Acids
1 Acetic acidchange *9,802,352
230,741
106,234
55,323
136,728
81,854
721,279

2 Propanoic acid
3 Pivalic acid
4 Butanoic acid
5 2-Methyulbutanoic acid
6 Pentanoic acid
7 Hexanoic aciod

Dr. IMAI (130-years Nuka-Doko)
Acids

fold

Average area

9 Nonanoic acid
10 Decanoic acid－－－－－－－

1,079
610－－

11 Myristic acid

25
117－－

12 Palmitic acid294

1 Acetic acid

4.8

2 Propionic acid
3 Isobutyric acid

3.0acids eleminated
ppb

3,132
53,005
1,561
1,037
4,745960
1,724

4.5

4 Butyric acid
5 2-Methylbutyric acid
6 Valeric acid (Pentanoic acid)
7 Caproic acid (Hexanoic acid)375,641
501,018
52,296

8 Octanoic acidacids containedppb

8 Caprylic acid (Octanoic acid)9 Nonanoic acid
10 Lauric acid

782－

酢酸が主

プロピオン酸が主[Aromatics]

236

13 Benzoic acid

ピクルス漬け床（左）と糠床（右）のラクトン類の比較
USDA (Suzanne)
Lactones
1 Butyrolactone (C4)fold
276,487changeDr. IMAI (130-years Nuka-Doko)
Lactones

100,505

acids eleminatedppb

1 Butane-1,4-olide

182－

2 Pentane-1,4-olide

23－

3 Hexane-1,4-olide
2 5-pentyl-γ -lactone (C9)acids containedppb

4 Nonane-1,4-olide

1636

5 Decan-1,4-olide
6 2,3-Dimethyl-2-nonene-1,4-olide

126－
83

2179
－65

－

7 Undecane-1,4-olide

164

100

8 Dihydroactinidiolide

31134

9 Dodecane-1,4-olide

45

ピクルス漬け床（左）と糠床（右）のアルコール類の比較
USDA (Suzanne)
Alcohols

1 Butanolchange794,956

2 2-Methyl-2-propene-1-ol
3 2-Methyl-2-propanol

Dr. IMAI (130-years Nuka-Doko)
Alcohols

fold
Average area

C42.511,391

1 Isopropanol

850－52－

3 Butanol

76－

169－

477,300

5 2-Pentanol

223,939

11.4

6 2-Pentanol

6 3-Pentanol

81,102

2.8

5 3-Pentanol

318,459-4.5

8 3-Pentene-2-ol

C5C4

2.5

4 Pentanol

7 1-Pentene-3-ol

acids eleminatedppb

2 3-Ethoxy propanol
4 Isobutanol?

acids contained
ppb

－20－
140－

11,164C5

9 trans-2-Pentene-1-ol

22,334

10 3-Methyl-3-butene-1-ol

37,794

7 3-Methylbutane-2-ol

321－

11 2-Methyl-2-butene-1-ol

55,966

8 3-Methyl-3-butene-2-ol

37－9 2-Methylbutanol

301－

10 Amyl alcohopl

163－

11 Isoamyl alcohol
12 Hexanol(from cucumber)

13 2-Hexanol

2,564,937
49,86514 trans-3-Hexexe-1-ol
15 cis-3-Hexene-1-ol
16 trans-2-Hexene-1-ol

12 Hexanol？

184

20,351

C6335,213
31,23821,06818 2-Methyl-2-pentanol

200,446

2.5

19 Heptanol

106,479

4.7

20 2-Heptanol

299,671

22 2,4-Dimethyl-2-pentanol

393

33.4

17 2-Methyl-3-pentanol

21 cis-3-Heptene-1-ol

132

－

C7

23 2,4-Dimethyl-4-pentene-2-ol

18,911
40,57838,954

24 2,3-Dimethyl-1-pentanol

3,623

25 Octanol

63,77213 Octanol－

26 3-Octanol

19,815

14 Octane-3-ol－

42

27 2-Octanol

29,30915 1-Octene-3-ol－

117

248,344

16 trans-2-octenol－

48

15,12617 6-Methyl-5-heptene-3-ol

28 1-Octene-3-ol
29 cis-2-Octene-1-ol

C8

188.2

30 2-Methyl-2-heptanol

47,995

21 4-Methyl-2-heptanol

120,208

19 Nonanol

32 2-Methyl-2-octanol

71,67320 Linalool

291,814

21 1-(2-tetrahydrofuryl)-hexanol

33 2-Ethyl-1-hexanol
34 2-Nonanol

C919,277

36 Eucaryptol①29,202

37 4-Terpineol②4,39138 α-Terpineol②345,764③

28,20240 cis-Ocimenol

55,33941 trans-ocimenol

72,28244 4-Methylbenzenemethanol
42 Benzyl alcohol

18 2-Ethylhexanol

73

47

240

160

92－

208－－

23 trans-Nerolidol[Aromatics]
43 Phenylethyl alcohol

61－

34,66535 cis-6-Nonene-1-ol

39 Myrcenol

C8134

85

[Aromatics]
54,906?
48,41922 Phenethyl alcohol
579

2976

2395

ピクルス漬け床（左）と糠床（右）のアルデヒド類の比較
USDA (Suzanne)
Aldehydes
1 Acetaldehyde

Dr. IMAI (130-years Nuka-Doko)
Aldehydes

foldAverage area
7,442,303

change?

acids eleminatedppb

1

5 3-Methylbutanal

431,295

2

10 Hexanal

664,650

32 Nonanal

283,024

43 Pivaldehyde

146,8015

4 2-Methylbutanal

90,9406

6 trans-2-Methyl-2-butenal

29,451

7

7 2-Pentenal

175,6778

8 2,4,4-Trimethyl-2-pentenal

17,7499 trans-2-Heptenal

9 cis-2-Heptenal

540,2861011 trans-2-Octenal

317,31911

12 2,4-Heptadienal

30,513120 Furfuralacids contained
ppb

2,442,243126

86131430.1

14 Benzaldehyde

70－

ピクルス漬け床（左）と糠床（右）の炭化水素類の比較USDA (Suzanne)
Hydrocarbons

foldAverage areachange

Dr. IMAI (130-years Nuka-Doko)Hydrocarbons

acids containedppb

acids eleminatedppb

1 Pentane

45,602

1 Decane

2 Hexane

655,8162 Limonene

8.7

3 1,4-pentadiene

37,4003 Isobutylbenzene－

4 Ethylcyclobutane

472,102

4 Trimethylbenzene－

5 Cyclohexane

88,3645 Tridecane

159

6 cis-5,5-dimethyl-2-hexene

29,255

6 Tetradecane

47

7 Benzene

743,703

7 Pentadecane

8 Toluene909,2128 Hexadecane

9 m-Xylene

17,2659 Ethylbenzene

10 Cardene

64,92810 Heptadecane－

11 Naphthalene－73

12 2-Methyulnaphthalene－163

13 2,6-Dimethyulnaphthalene

－59－
324

－

41
46
49
85
57
100
104
8264

ピクルス漬け床（左）と糠床（右）のケトン類の比較
USDA(Susanne)

Dr. IMAI (130-years Nuka-Doko)

Ketones

Ketones

1 Acetone

1,363,820

2 3-methyl-2-butanone

25,302

3 3,3-dimethyl-2-butanone

32,6114 2-methyl-3-pentanone

37,274

5 2,4-dimethyl-3-pentanone

10,0996 Methyl isobutyl ketone

524,065

7 3-methyl-2-pentanone

70,287

8 1-penten-3-one

698,188

9 4,4-dimethyl-2-pentanone

144,329

10 3-hexanone

65,095

11 2-methyl-1-penten-3-one

40,62612 trans-3-penten-2-one

29,502

13 4-methyl-3-penten-2-one

8,040

14 4-methyl-2-heptanone

124,174

15 3-hydroxy-2-butanone

983,577

16 1-octen-3-one

210,558

17 6-methyl-5-hepten-2-one

112,007

18 2-hydroxy-2,4-dimethyl-3-pentanone

7,580

19 Acetophenione

42,62920 p-methylacetophenone

19,81921 4-Methyl-3-heptene-2-one?

acids contained

1 2-Butanone
2 6,10,14-Trimethylpentadecane-2-one

6.3

29.4

1367
－

acids eleminated－115