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1 2022 ᖺᗘ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩1.1 2022 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩ᥦฟ≧ἣ(๭ᙜⅬᩘ 30,000 Ⅼ௨ୗ) ··········· 11.2 2022 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩(๭ᙜⅬᩘ 30,000 Ⅼ㉸)·························· 92 2022 ᖺᗘィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩ ······· 481
3 ࣮ࣘࢨⓎ⾲ㄽᩥ
3.1 ࣮ࣘࢨㄽᩥ୍ぴ················································································ 504
3.2 ࣉࣟࢪ࢙ࢡࢺูㄽᩥูๅᥦฟ≧ἣ························································ 539㻝㻚䚷㻞㻜㻞㻞ᖺᗘ㻌◊✲ㄢ㢟䛚䜘䜃฼⏝ሗ࿌᭩ࠉᖺᗘ◊✲ㄢ㢟ࡢ࠺ࡕࠊ๭ᙜⅬᩘⅬ௨ୗࡢࣉࣟࢪ࢙ࢡࢺ࡟㛵ࡋ࡚ࡣ㡯࡟◊✲ㄢ㢟ྡࡢ୍ぴ࡜ࡋ࡚
グ㍕ࡋࡲࡋࡓࠋࡲࡓ๭ᙜⅬᩘⅬࢆ㉸࠼ࡿࡢࣉࣟࢪ࢙ࢡࢺ࡟㛵ࡋ࡚ࡣᥦฟࡉࢀࡓ฼⏝ሗ࿌᭩ࡢ඲ᩥࢆ㡯࡟ᥖ㍕ࡋࡲࡋࡓࠋ

㻝㻚㻝㻌㻌㻞㻜㻞㻞ᖺᗘ㻌◊✲ㄢ㢟୍ぴ䛸฼⏝ሗ࿌᭩ᥦฟ≧ἣ㻌㻔๭ᙜⅬᩘ㻌㻟㻜㻘㻜㻜㻜Ⅼ௨ୗ㻕ࠑศᏊ⛉Ꮫࠒ᪋タ฼⏝ $
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Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FD

ศගἲ࡜ศᏊືຊᏛィ⟬㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ⏕య㛵㐃ศᏊࡢືⓗ
ᵓ㐀ゎᯒ

బ㈡኱
⌮ᕤ

ᾏ㔝㞞ྖ


 㸭 

ศᏊ㛫㟁Ꮚ⛣ືࢆక࠺໬Ꮫ཯ᛂ࡜
ศᏊ㛫┦஫స⏝ࡢ◊✲

⚄ዉᕝ኱
⌮

⏣௰஧ᮁ


 㸭 

Ỉ࿴ࣇ࢙ࣀ࣮ࣝ࢝ࢳ࢜ࣥ࡟࠾ࡅࡿᚤどⓗỈ⣲⤖ྜᵓ㐀㸸」⎔ᵓ㐀ࡢ
᥈⣴

໭㔛኱
⌮

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

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ᩘ⣡ᗈဢ 㸭 

GࡲࡓࡣG㔠ᒓࢆྵࡴከ᰾㔠ᒓ㘒యࡢ㟁Ꮚ≧ែ

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ᾏ⪁ཎᫀᘯ


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࢖࢜ࣥ✀࡟ᑐࡍࡿ㧗ศゎ⬟᣺ືᅇ㌿ศග࡟ࡼࡿศᏊ㛫┦஫స⏝ࡢ◊
✲

໭㔛኱
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Ỉ℩㈼ኴ


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⸆≀࠶ࡿ࠸ࡣ⏕⌮άᛶ≀㉁࡜኱⎔≧໬ྜ≀࡜ࡢ┦஫స⏝ゎᯒ

⚟ᒸ኱
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ụ⏣ᾈே
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పศᏊ㠀ᬗ㉁᭷ᶵ༙ᑟయⷧ⭷୰ࡢᐁ⬟ᇶ㓄ྥホ౯࡟㛵ࡍࡿィ⟬ᒣᙧ኱㝔᭷ᶵᮦᩱࢩࢫࢸ࣒

ᶓᒣ኱㍜ 㸭 

➨୍ཎ⌮ィ⟬࡟ࡼࡿࣉࣛࢬ࣐ࢻࣛ
࢖࢚ࢵࢳࣥࢢࡢᒁᡤⓗ⎔ቃኚ໬࡟ࡼࡿࣇ࣮ࣟࣟ࢝࣎ࣥ⭷ࡢㄏ㟁⭷࡟࠾ࡅࡿᛶ㉁ኚ໬ࡢண

ᶓ὾ᅜ኱㝔ᕤ

5DHELJHU+DQQHV 㸭 

ᚤ⣽ᵓ㐀ࢆㄆ㆑ࡍࡿ㉸ศᏊ」ྜ⣔ࡢᵓ⠏࡜ᵓ㐀ゎᯒ

᪂₲኱㝔
⮬↛⛉Ꮫ

ᒾᮏࠉၨ


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࢔࣑ࣀ㓟ࢩࢵࣇሷᇶ㔠ᒓ㘒యࡢ❧యᵓ㐀࡜㟁Ꮚᵓ㐀

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ࣔࢹࣝ⁐⼥ሷ࠿ࡽ࡞ࡿ⁐፹ࡢ┦㛵㛵ᩘࢆṇ☜࡟ồࡵࡿ᪉ἲㄽࡢ㛤Ⓨ

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ᐑ⏣❳ᙪ


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ᡤᒓ

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 㸭 

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ࡧࡑࡢ㞟ྜయࡢィ⟬໬Ꮫⓗ᳨ウ

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ࢩࣙࣥ⏘ᴗᢏ⾡⥲ྜ◊✲ᡤᓲࠉ㝯ᇶ 㸭 

㓄఩Ꮚಖㆤ㈗㔠ᒓࢡࣛࢫࢱ࣮ࡢ୕
㔜㡯ᛶ࡟㛵ࡍࡿィ⟬⛉Ꮫⓗ◊✲

❧ᩍ኱
⌮

୕஭ṇ᫂


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

 㸭 

㔠ᒓ࢝ࣝ࣎ࢽࣝ໬ྜ≀ࡢ;$6ࢫ࣌ࢡ
ࢺࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱㝔᪂㡿ᇦ๰ᡂ⛉Ꮫబࠎᮌᓅᙪ 㸭 

ࢡࣛࢫࢱ࣮」ྜయࡢᵓ㐀࡜཯ᛂᛶ

㇏⏣ᕤᴗ኱
ᕤ

ᕷᶫṇᙪ


 㸭 

㑄⛣⣔ิ࢖࢜ࣥࢆྵࡴ໬ྜ≀ࡢ཯ᛂไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

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

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

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ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿศᏊ
㞟ྜయࡢ◊✲

ྡྂᒇᩥ⌮኱ᮏከ୍ᙪ 㸭 

⦰ྜከ⎔ⰾ㤶᪘໬ྜ≀࡟ᇶ࡙ࡃ᭷
ᶵⓎගᮦᩱࡢ㛤Ⓨ

ᮾி㎰ᕤ኱㝔ᕤ୰㔝ᖾྖ 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ࣌ࣉࢳࢻᙧᡂ
㐣⛬ࡢゎ᫂

᪩኱
ᅜ㝿ᩍ㣴

✄ⴥ▱ኈ


 㸭 

ศᏊ㓄ิ࡟ࡼࡗ࡚ไᚚࡉࢀࡓ᭷ᶵ
࣍࢘⣲㘒యࡢⓎⰍᶵᵓࡢゎ᫂

ྡᕤ኱㝔
ᕤ

ᑠ㔝ඞᙪ


 㸭 

ග໬Ꮫ཯ᛂࡢไᚚ࡜ᛂ⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㔞Ꮚ⛉Ꮫᢏ⾡
◊✲㛤Ⓨᶵᵓ

㯮ᓮࠉㆡ 㸭 

GE

GF

GF

GJ

GM

GX

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HN

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࡜ࡍࡿ᪂᭷ᶵ཯ᛂࡢ㛤Ⓨ

ࢆᇶ┙

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ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

ID

⏕యศᏊ࠾ࡼࡧ⁐፹ࡢᵓ㐀ᶵ⬟┦
㛵ࡢゎ᫂

❧࿨㤋኱
⏕࿨⛉Ꮫ

㧘ᶫ༟ஓ


 㸭 

࢚ࢿࣝࢠ࣮ኚ᥮ศᏊゐ፹ࡢศᏊᵓ
㐀࣭㟁Ꮚ≧ែ࡜཯ᛂᛶࡢ┦㛵ࡢゎ᫂ᒣཱྀᮾி⌮⛉኱Ꮫᕤኴ⏣㞝኱ 㸭 

⌮ㄽィ⟬࡟ࡼࡿ㓟໬≀ᅛᐃ໬࢟ࣛ
ࣝ7E㘒యࡢ⾲㠃ᵓ㐀ゎ᫂

ྡ኱㝔
⌮

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ࣇࢵ⣲໬࣎ࣛࢱ࢔ࣥࢺࣛ࢔ࢭࣥ࢔
ࢽ࢜ࣥࡢ㟁Ꮚⓗ≉ᛶࡀ㓄఩㔜ྜ࡟
ཬࡰࡍᙳ㡪

ᗈ኱㝔
ඛ㐍⌮ᕤ

⏣୰ࠉு


 㸭 

ཎᏊ᰾ࡢ㔞Ꮚຠᯝࢆ⪃៖ࡋࡓ⌮ㄽィ⟬ᡭἲ࡟ࡼࡿỈ⣲⤖ྜ⣔ࡢゎᯒ

ᒱ㜧኱
ᕤ

Ᏹ⏣ᕝኴ㑻


 㸭 

➨୍ཎ⌮ィ⟬ᡭἲ࡟ᇶ࡙ࡃࢼࣀ㟁Ꮚᮦᩱࡢࣉࣟࢭࢫᶵ⬟ไᚚ࡟㛵ࡍ
ࡿ◊✲

ᓥ᰿኱
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ᙳᓥ༤அ


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㛵すᏛ㝔኱
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

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

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

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ᕤ

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

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$O2⾲㠃ୖ࡟࠾ࡅࡿⅣ⣲⭷ࡢᡂ㛗㐣⛬࡟㛵ࡍࡿ◊✲

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

4,$1*<8( 㸭 

ගቑឤ๣฼⏝࡟ྥࡅࡓⓎගᛶࢭ࣒ࣜ࢘㘒యࡢ㛤Ⓨ

ᮾி⌮⛉኱
⌮

಴ᣢᝆ㍜


 㸭 

ࣇࣛࢵࢺࣂࣥࢻࢆ᭷ࡍࡿ᭷ᶵศᏊ
㔠ᒓࣁ࢖ࣈࣜࢵࢻ⣔࡟࠾ࡅࡿ㧗㉸ఏᑟࡢ⌮ㄽ

᪂₲኱㝔
⮬↛⛉Ꮫ

㛵ᕝ༟ஓ


 㸭 

࣍ࢫࣇ࢕ࣥಖㆤ$Xࢡࣛࢫࢱ࣮ࡢ
࢟ࣕࣜ࢔ࢲ࢖ࢼ࣑ࢡࢫ࡟୚࠼ࡿ㓄
఩Ꮚຠᯝ

㛵すᏛ㝔኱
⌮ᕤ

Ụཱྀ኱ᆅ


 㸭 

ྂ඾࠾ࡼࡧ㔞Ꮚࢩ࣑࣮ࣗࣞࢱࢆ⏝࠸ࡓ㔞Ꮚ໬Ꮫィ⟬ᮾ኱࢞ࣈࣜᩘ≀㐃ᦠᏱᐂ◊✲ᶵᵓᒣᓮ㞞ே 㸭 

JK

JK

JK

JK

JK

JK

JK

JL

JL

JL

JL

JL

JL

JL

JM

-7-

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬



‫ۑ‬

‫ۑ‬

௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

JM

&࢝ࣝ࣋ࣀ࢖ࢻ໬Ꮫ✀ࡢ⌮ㄽ࠾ࡼࡧᐇ㦂࡟ᇶ࡙ࡃィ⟬໬Ꮫⓗゎ᫂

໭኱㝔
⌮

ᒸᮏ࿴⣫


 㸭 

࢔ࢽࣜࣥศᏊࡢศග≉ᛶ࡟ᑐࡍࡿ
⁐፹ຠᯝࡢ◊✲

஑ᕞ኱㝔
⌮

኱ᶫ࿴ᙪ


 㸭 

JM

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

ᡤෆ
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DK

ᶵ⬟ᛶ㛤ẆศᏊᮦᩱࡢᵓ㐀̿≀ᛶ̿㟁Ꮚ≧ែ┦㛵ࡢゎ᫂㘒య≀ᛶඛ➃ⓗࢥࣄ࣮ࣞࣥࢺ᣺ືศග࡟ࡼ
ࡿᶵ⬟ᛶ」㞧ศᏊࡢ㉸㧗㏿ᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫࡢほ ࡜ゎ᫂

DK

DK

DL

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ⲡᮏဴ㑻 㸭 

༠ዌศᏊࢩࢫࢸ࣒
◊✲ࢭࣥࢱ࣮

಴ᣢࠉග 㸭 ᪂つ㧗ศᏊᢸᣢග㓟໬㑏ඖゐ፹ࡢ
๰〇

㘒యゐ፹

ዟᮧៅኴ㑻


 㸭 ῝ᒙᏛ⩦࡟ࡼࡿ࢟ࣛࣝࡽࡏࢇᵓ㐀ࡢᕥྑ࢝࢘ࣥࢺ

༠ዌศᏊࢩࢫࢸ࣒
◊✲ࢭࣥࢱ࣮ᒣᮏᾈྐ 㸭 

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ࠑᇶ♏⏕≀Ꮫࠒ᪋タ฼⏝ $
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

TF

ᢠ⏕≀㉁⪏ᛶศᏊ࣓࢝ࢽࢬ࣒ࡢ⌮
ㄽⓗ◊✲

ᇛすᅜ㝿大
⸆

㢠㈡㊰჆


 㸭 

࢔ࣝࢶࣁ࢖࣐࣮⑓ࡢ἞⒪⸆ࢆ┠ⓗ࡜ࡋࡓ࢔࣑ࣟ࢖ࢻșศゎάᛶࢆ᭷ࡍࡿ࣌ࣉࢳࢻࡢ≉ᛶホ౯࡜ᢞ୚ἲ
࡟㛵ࡍࡿ◊✲

ᮾ໭኱
⸆

ᖭᕝ♸㈨


 㸭 

TF

-8-

㸦࣓ࣥࣂ࣮ᩘ㸧‫ۑ‬‫ۑ‬㻝㻚㻞㻌㻌㻞㻜㻞㻞ᖺᗘ㻌◊✲ㄢ㢟୍ぴ䛸฼⏝ሗ࿌᭩䚷㻔๭ᙜⅬᩘ㻌㻟㻜㻘㻜㻜㻜Ⅼ㉸㻕ࠑศᏊ⛉Ꮫࠒ᪋タ฼⏝ $
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

JD

㧗࿘ᮇඖ⣲ࢆᇶ┙࡜ࡍࡿࣞࢻࢵࢡ
ࢫάᛶ᭷ᶵゐ፹ࡢ᥈⣴

ྡᕤ኱㝔
ᕤ

㧗ᮌᖾ἞


 㸭 

࣐࢖ࢡࣟࣇ࣮ࣟ཯ᛂሙࢆ⏝࠸࡚๰〇ࡉࢀࡿ‽Ᏻᐃ㉸ศᏊᵓ㐀ࡢゎᯒி㒔ᗓ኱㝔⏕࿨⎔ቃ⛉Ꮫ

἟⏣᐀඾ 㸭 

➨୍ิ㑄⛣㔠ᒓゐ፹ࡢගᛂ⟅࡟㛵ࡍࡿ⌮ㄽ໬Ꮫⓗ᳨ド

໭኱㝔
⸆

ᑠᓥṇᐶ


 㸭 

')7ィ⟬࡟ࡼࡿ」ᩘࡢ㔠ᒓ✀࠿ࡽ࡞ࡿከ᰾㔠ᒓ㘒యࡢ㟁Ꮚᵓ㐀ࡢゎ᫂

ᒱ㜧኱
ᕤ

᳜ᮧ୍ᗈ


 㸭 ᪂つ⏕≀άᛶ≀㉁ࡢタィ࣭ྜᡂ࣭
ᶵ⬟ホ౯

஑኱㝔
⸆

ᖹ஭ࠉ๛


 㸭 

࢔࣮ࣞࣥ㢮ࡢ࢔ࢲ࣐ࣥࢱࣥ⦰⎔཯ᛂࡢ཯ᛂᶵᵓゎ᫂࠾ࡼࡧ᪂ወȧඹᙺ⣔ศᏊࡢᵓ㐀≀ᛶゎ᫂ྡ኱ࢺࣛࣥࢫࣇ࢛࣮࣐ࢸ࢕ࣈ
⏕࿨ศᏊ◊✲ᡤඵᮌளᶞᏊ 㸭 

༙ྜ⌮ⓗᡭἲ࡟ࡼࡾᵓ⠏ࡉࢀࡓ୺㙐ᵓ㐀࡟ࡼࡿேᕤࢱࣥࣃࢡ㉁タィ

ྡ኱㝔
᝟ሗ

బஂ㛫⯟ஓ


 㸭 

')7ィ⟬ࢆ⏝࠸ࡓ᪂つ&̿+άᛶ໬཯ᛂࡢᶵᵓ◊✲

ྡ኱㝔
๰⸆⛉Ꮫ

ᖹᏊ┤ὒ


 㸭 

%HQ]HQH&+㸲YDQGHU:DDOV㘒య࡟࠾ࡅࡿḟඖࣔࢹ࣏ࣝࢸࣥࢩࣕࣝ
ィ⟬࡜ศᏊ㛫᣺ືἼ᮰ほ

ᮾᕤ኱
⌮

୰ᮧ㞞᫂


 㸭 

୙ᩧቑᖜࢆక࠺ගᏛάᛶྵ❅⣲㸶ဨ⎔ࡢྜᡂ◊✲

㜰኱⏘ᴗ⛉Ꮫ◊✲ᡤ⁪⃝ࠉᚸ 㸭 

JE

JF

JG

JH

JJ

JJ

JK

JK

JL

㸦࣓ࣥࣂ࣮ᩘ㸧





















᪋タ฼⏝ %
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FF

⏕యศᏊࡢᶵ⬟Ⓨ⌧཯ᛂ࡟㛵ࡍࡿ
⌮ㄽⓗ◊✲

༓ⴥ኱㝔
⸆

ᫍ㔝ᛅḟ


 㸭 ゐ፹ศᏊ⣔࠾ࡼࡧ⏕యศᏊ⣔ࡢ㔞Ꮚ໬Ꮫ࡜཯ᛂືຊᏛ໭኱ゐ፹⛉Ꮫ◊✲ᡤ㛗㇂ᕝ῟ஓ 㸭 

FF

-9-

㸦࣓ࣥࣂ࣮ᩘ㸧௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FF

ᣑᙇ࢔ࣥࢧࣥࣈࣝἲ࡟ࡼࡿศᏊࢩ
࣑࣮ࣗࣞࢩࣙࣥ

ྡ኱㝔
⌮

ᒸᮏ♸ᖾ


 㸭 

㹢㟁Ꮚ」ྜ⣔ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊ཯ᛂ㐣⛬࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ி኱ゐ፹࣭㟁ụඖ⣲ᡓ␎
ࣘࢽࢵࢺ

ᴬࠉⱱዲ


 㸭 

㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡿືⓗ≀ᛶ㔞ࡢ⌮ㄽⓗ◊✲

㜰኱㝔
ᇶ♏ᕤ

໭Ἑᗣ㝯


 㸭 

ᒁᡤ≀⌮㔞ࢆ⏝࠸ࡓ࢖࢜ࣥ࡜ࢫࣆ
ࣥࡢࢲ࢖ࢼ࣑ࢡࢫゎᯒ

ி኱㝔
ᕤ

℩Ἴ኱ᅵ


 㸭 

㧗཯ᛂᛶࡢࢪ࣎ࣛࣥ  ࡜$O࢔ࢽ࢜ࣥࡢᛶ㉁ࡢゎ᫂࠾ࡼࡧ࣓ࢱࣥࡢ&+⤖ྜάᛶ໬࡬ྥࡅࡓᆒ୍⣔ゐ፹タ
ィ

ྡ኱㝔
ᕤ

ᒣୗࠉㄔ


 㸭 

㔠ᒓ⺮ⓑ㉁ࡢ㟁Ꮚᵓ㐀ไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥᕷ኱㝔
᝟ሗ⛉Ꮫ

㮚㔝ࠉඃ


 㸭 

⏕యศᏊࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮
ㄽⓗ◊✲

ᗈᓥ኱㝔
ඛ㐍⌮ᕤ

㉥℩ࠉ኱


 㸭 

ṑ㌴≧୧ぶ፹ᛶศᏊ *6$ ࡢ⇕ຊᏛⓗᏳᐃᛶཬࡧⓎගࢫ࣌ࢡࢺࣝ࡟ᑐ
ࡍࡿ⁐ᾮຠᯝࡢ⌮ㄽⓗ◊✲ᶓ὾ᕷ኱㝔⏕࿨ࢼࣀࢩࢫࢸ࣒

❧ᕝோ඾ 㸭 

⚄ᡞ኱ศᏊࣇ࢛ࢺࢧ࢖࢚ࣥࢫ
◊✲ࢭࣥࢱ࣮

ᐩỌᆂ௓ 㸭 

㔞ᏊຊᏛ 40 ศᏊຊᏛ 00 ἲ࡜ศᏊືຊᏛィ⟬࡟ࡼࡿࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲ࡢ཯ᛂᶵᵓゎᯒ㛗὾ࣂ࢖࢜኱
ࣂ࢖࢜ࢧ࢖࢚ࣥࢫ

୰ᮧࠉ༟ 㸭 

㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀㔞Ꮚ໬Ꮫ◊✲༠఍୰㎷ࠉ༤ 㸭 

ேᕤගྜᡂ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ◊
✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ⲡ㛫ࠉோ


 㸭 

⏕యศᏊ」㞧⣔ࡢ඲ཎᏊ࣭⢒ど໬ࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲⚄ᡞ኱㝔ࢩࢫࢸ࣒᝟ሗ

⏣୰ᡂ඾ 㸭 

ࣇࣛࢢ࣓ࣥࢺ㟁Ꮚ≧ែ⌮ㄽࢆᇶ࡜ࡋࡓ኱つᶍ➨୍ཎ⌮ศᏊࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ࡜㟁Ꮚ≧ែ࢖ࣥࣇ࢛࣐
ࢸ࢕ࢡࢫ࡟ࡼࡿᶵ⬟ᮦᩱࡢ⇕ຊᏛ࣭ග≀ᛶࡢ㎿㏿タィ

୰ኸ኱
⌮ᕤ

᳃ࠉᐶᩄ


 㸭 

⁐ᾮ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࡢィ⟬໬Ꮫ

ᮾ໭኱㝔
⌮

᳃⏣᫂ᘯ


 㸭 

FG

FG

FI

FI

FJ

FJ

FK

FL

FN

FN

FO

FP

FP

FQ

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ
࠿ࡽ⣸እ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝ
ゎᯒ

- 10 -

㸦࣓ࣥࣂ࣮ᩘ㸧































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FQ

ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ࡜᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋ
ࡓⰾ㤶᪘໬ྜ≀ࡢタィ

ᮾ኱㝔
ᕤ

㔝ᓮிᏊ


 㸭 

ከ⎔ⰾ㤶᪘ศᏊ㸦3$+V㸧ࡢỈ࿴ᵓ㐀ࡢ㉥እศග࡟ࡼࡿ◊✲

࠾Ⲕ኱
ᇶᖿ◊✲㝔

ᐑᓮ඘ᙪ


 㸭 

➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫ࡜ඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽࡢከゅⓗᒎ㛤

໭኱㝔
⌮

Ṋḟᚭஓ


 㸭 

ศᏊືຊᏛཬࡧ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ⏕య㧗ศᏊ࠾ࡼࡧᶵ⬟ᮦᩱࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ◊✲

ᶓ὾ᅜ኱㝔
ᕤ

ୖ⏣୍⩏


 㸭 

㔞Ꮚ໬Ꮫ࡜⤫ィຊᏛ࡟ᇶ࡙ࡃ」㞧
໬Ꮫ⣔ࡢ⌮ㄽⓗ◊✲

ி኱㝔
ᕤ

బ⸨ၨᩥ


 㸭 

㑅ᢥⓗ཯ᛂ࡟࠾ࡅࡿ⁐፹ຠᯝ࡜཯
ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽ◊✲㧗▱኱㝔⥲ྜே㛫⮬↛⛉Ꮫ㔠㔝኱ຓ 㸭 

࣊ࣟࢼ࣑ࢻ㢮ࡢᢠ┿⳦స⏝࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡢࡓࡵࡢィ⟬ศᏊタィ
ᢏ⾡ࡢ㛤Ⓨ

໭㝣኱
⸆

㰻⸨኱᫂


 㸭 

ᵓ㐀ከ⢾ᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ᐑᓮ኱ᕤ‫‮‬஭ᩄᩥ
 㸭 

඲ཎᏊศᏊືຊᏛィ⟬ࡢ㧗ศᏊ◊
✲࡬ࡢᒎ㛤

ᮾ኱㝔
᪂㡿ᇦ๰ᡂ⛉Ꮫᒸᓮࠉ㐍 㸭 

ࢼࣀไ㝈✵㛫࡟࠾ࡅࡿ⁐፹࿴࡜ື
ែࡢゎᯒ

ᚨᓥ኱㝔
♫఍⏘ᴗ⌮ᕤ

ྜྷ⏣ࠉ೺ 㸭 

ගྜᡂ㓟⣲Ⓨ⏕୰ᚰ&D0Q2ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែ࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㜰኱ࢼࣀࢧ࢖࢚ࣥࢫ
ᩍ⫱◊✲ࢭࣥࢱ࣮

ᒣཱྀࠉ඙ 㸭 

୕ḟඖࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀ᛶ

኱㜰ᗓ኱㝔
⌮

ὠ␃ᓮ㝧኱


 㸭 

ࢼࣀⅣ⣲࣭࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮
ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊✲

㟁㏻኱㝔
᝟ሗ⌮ᕤ

ᒣ໭ెᏹ


 㸭 

୕⬮ᕮ≧ศᏊࡢจ㞟ㄏ㉳Ⓨග࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊✲

༓ⴥ኱
ᕤ

ᒣᮏ඾ྐ


 㸭 

࣓࢝ࣞ࢜ࣥࣔࢹࣝ࡟ࡼࡿࢱࣥࣃࢡ
㉁ᵓ㐀㌿⛣ࢆ࡜ࡶ࡞࠺ᶵ⬟Ⓨ⌧ᶵᵓࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮
ࣉゎᯒ

ྡ኱㝔
ᕤ

ᑎ⏣ᬛᶞ


 㸭 

⏕యศᏊ࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟
ࡢ⌮ㄽィ⟬

ி኱㝔
⌮

ᯘࠉ㔜ᙪ


 㸭 

FR

FU

FW

FY

FY

FZ

FZ

FZ

F[

F]

GE

GF

GI

GJ

GK

- 11 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

GK

⺮ⓑ㉁࡟ࡼࡿ'1$ຍỈศゎ࡟࠾ࡅࡿ
⁐፹ࡢᙺ๭

஑ᕤ኱㝔
᝟ሗᕤ

ධబṇᖾ


 㸭 

Ỉࠊịࠊࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞ
ࢺࡢᵓ㐀┦㌿⛣ࡢ⌮ㄽ◊✲ᒸᒣ኱␗ศ㔝ᇶ♏⛉Ꮫ
◊✲ᡤ

ᯇᮏṇ࿴


 㸭 

㔞ᏊศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔
17&KHP࡟ࡼࡿࢼࣀࢧ࢖ࢬศᏊࡢศ
Ꮚᶵ⬟ࡢゎ࣭᫂タィ⌮໬Ꮫ◊✲ᡤ୰ᔱ㝯ே 㸭 

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫ
ࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᶓ὾ᕷ኱㝔
⏕࿨་⛉Ꮫ

᳃ḟࠉᆂ


 㸭 

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ
࣮ࣟࢳ

㛵すᏛ㝔኱
⏕࿨⎔ቃ

ຍ⸨ᫀᏊ


 㸭 

⣽⳦ឤᰁࡢ௜╔ᅉᏊࡢ⢾㙐ㄆ㆑࡟㛵ࡍࡿ⌮ㄽ◊✲

໭㔛኱
୍⯡ᩍ⫱

⬟Ⓩࠉ㤶


 㸭 

㌾;⥺ග⛉Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥ኱㝔
⌮

㧗ᶫࠉಟ


 㸭 ி኱ゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬᒣୗ᫭୍ 㸭 

ศᏊ㌶㐨ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂ࠾ࡼ
ࡧ᭷ᶵศᏊᵓ㐀ࡢタィ࡜ゎᯒ

ᮾ኱㝔
⸆

኱࿴⏣ᬛᙪ


 㸭 

㒊఩㑅ᢥⓗ⇕ὶゎᯒ࡟ࡼࡿࢱࣥࣃ
ࢡ㉁ศᏊᶵ⬟ࡢ᥈⣴

ྡ኱㝔
⌮

ೖࠉ๛ஂ


 㸭 

ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࡢᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭ศᏊ㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝ

㟼ᒸ኱
ᕤ

㫽ᒃࠉ⫕


 㸭 ᶵ⬟ᛶࢯࣇࢺ࣐ࢸࣜ࢔ࣝࡢ඲ཎᏊ
ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

໭㔛኱
⌮

Ώ㎶ࠉ㇦


 㸭 

ࢼࣀ࣐ࢸࣜ࢔ࣝཬࡧ⏕యศᏊࡢᶵ
⬟࣭≀ᛶ࣭཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ
◊✲

᪩኱
ඛ㐍⌮ᕤ

୰஭ᾈᕭ


 㸭 

᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫឤᰁ㜼ᐖࡢศᏊᶵᵓࡢゎ᫂

㔠ἑ኱
⌮ᕤ

ᕝ୍ཱྀ᭸


 㸭 

ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽ
ⓗゎ᫂

Ⲉᇛ኱㝔
⌮ᕤ

᳃ࠉ⪷἞


 㸭 

ᶵ⬟ᛶ᭷ᶵᮦᩱࡢ㟁Ꮚ≀ᛶゎᯒ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

୕㔜኱㝔
ᕤ

ఀ⸨ᙲᾈ


GL

GM

GN

GT

GV

GX

GZ

G[

HH

HP

HP

HS

HT

HV

HW

࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉Ꮫ

- 12 -

㸦࣓ࣥࣂ࣮ᩘ㸧






























 㸭 ௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

HY

ከඖ⣲ࢡࣛࢫࢱ࣮ࡢ㉥እゎ㞳ศගࡢࡓࡵࡢ㉥እࢫ࣌ࢡࢺࣝࡢண

ᮾ኱㝔
⥲ྜᩥ໬

ᕤ⸨ࠉ⪽


 㸭 

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ
໬Ꮫィ⟬

ᮾி㒔኱㝔
⌮

Ἴ⏣㞞ᙪ


 㸭 

ḟୡ௦࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝ♫఍ࡢᇶ♏࡜࡞ࡿ༙ᑟయ⤯⦕య⏺㠃ࡢ➨୍ཎ⌮ィ⟬࡟ࡼࡿ◊✲

ྡ኱
ᮍ᮶ᮦᩱ࣭
ࢩࢫࢸ࣒◊✲ᡤⓑ▼㈼஧
 㸭 

⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟

ᮾᕤ኱
⏕࿨⌮ᕤ

໭ᑿᙲᮁ


 㸭 

➨୍ཎ⌮ィ⟬ᡭἲ࡟ࡼࡿ༙ᑟయࢼ
ࣀᵓ㐀࠾ࡼࡧཎᏊᒙ≀㉁ࡢᙧᡂ࡜
ᶵ⬟࡟㛵ࡍࡿ◊✲

୕㔜኱㝔
ᕤ

⛅ᒣࠉ஽


 㸭 

⌮ㄽィ⟬࡟ࡼࡿゐ፹ᶵ⬟ࡢゎ᫂

ᮾ㑥኱
⸆

ᆏ⏣ࠉ೺


 㸭 

ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᗄఱᵓ㐀ࠊ཯ᛂᛶ࠾ࡼࡧ⾪✺᩿㠃✚ࡢィ⟬

ᮾ໭኱㝔
⌮

኱ୗ៞ḟ㑻


 㸭 

⺮ⓑ㉁ࡢᶵ⬟Ⓨ⌧࡜ᵓ㐀࡟㛵ࡍࡿ
⌮ㄽⓗ◊✲

ி㒔ᗓ኱㝔
⏕࿨⎔ቃ⛉Ꮫ

ࣜࣥࢺࢗࣝ࢜ࢺ
ṇ⨾ศᏊ㐠ື࡟㉳ᅉࡍࡿືⓗศᏊ㛫┦஫స⏝ࢆά⏝ࡋࡓᾮᬗࡢᶵ⬟㛤Ⓨ

㜰኱㝔
ᇶ♏ᕤ

ෆ⏣ᖾ᫂


 㸭 

ศᏊᛶᑟ㟁࣭☢ᛶᮦᩱ࡟㛵ࡍࡿ⌮
ㄽⓗ◊✲

ி኱㝔
⌮

୰㔝⩏᫂


 㸭 

ࢯࣇࢺ࣐ࢱ࣮⣔࡟࠾ࡅࡿ㐜࠸ࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ◊✲

㜰኱㝔
ᇶ♏ᕤ

㔠ࠉ㗰


 㸭 

᭷ᶵศᏊ࡟࠾ࡅࡿග໬Ꮫ㐣⛬ࡢ⌮
ㄽⓗ◊✲

ᘯ๓኱㝔
⌮ᕤ

ᒣᓮ⚈ᖹ


 㸭 

ࢩࢢࢼࣝఏ㐩ࢆไᚚࡍࡿᕧ኱ࢱࣥ
ࣃࢡ㉁」ྜయࡢศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ࡟ࡼࡿືⓗไᚚᶵᵓゎ
᫂

㏆␥኱
ඛ➃ᢏ⾡
⥲ྜ◊✲ᡤ

⡿⃝ᗣ⁠


 㸭 

㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ࡑࡢ཯ᛂ
ᛶ

ᮾ኱㝔
⌮

ᑠᏳ႐୍㑻


 㸭 

ኳ↛⣸እ⥺㜵ᚚ≀㉁࣐࢖ࢥࢫ࣏ࣜ
ࣥᵝ࢔࣑ࣀ㓟ࡢ㧗㏿⬺ບ㉳ᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ᒣཱྀᮾி⌮⛉኱⸆␊ᒣࠉඔ 㸭 

➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟ࡼࡿỈࡢኚゅ᣺ື⦆࿴ࢲ
࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲

ᐩᒣ኱㝔
⌮ᕤ

▼ᒣ㐩ஓ


 㸭 

HZ

H[

H]

H]

ID

IE

IF

IF

IF

IF

IG

IG

IG

IH

IJ

- 13 -

㸦࣓ࣥࣂ࣮ᩘ㸧














 㸭 


















௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IJ

ග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵ⛣ື࣓࢝
ࢽࢬ࣒

᪥ᮏዪᏊ኱
⌮

ᮧᒸࠉᱻ


 㸭 

᣺㟁┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮బ⸨ࠉᚭ 㸭 

୙ᆒ୍⏺㠃⣔࡟࠾ࡅࡿ㟼ⓗ࠾ࡼࡧືⓗ≀ᛶࡢ⌮ㄽⓗ◊✲

៞᠕኱
⌮ᕤ

⏿୰⨾✑


 㸭 

Ỉࡢ㍺㏦ಀᩘ࡟ᑐࡍࡿᵓ㐀つ๎ᛶࡢᐤ୚࡜┦஫స⏝ࣔࢹࣝࡢ㛵ಀ

᪂₲኱
⌮

኱㫽⠊࿴


 㸭 

࣎࢘ࣝᆺඹᙺ໬ྜ≀ࡢ≀ᛶㄪᰝࠊ࠾ࡼࡧ㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢάᛶ
ホ౯◊✲

㜰኱㝔
ᕤ

Ḉ஭ⱥ༤


 㸭 

᪂ወࢼࣀ࣮࣭࢝࣎ࣥඹᙺࣛࢲ࣮ศ
Ꮚ⩌๰ฟ࡟ྥࡅࡓྜ⌮ⓗ࡞ศᏊ࣭཯ᛂ࣭ᶵ⬟ࢹࢨ࢖ࣥ

ྡ኱㝔
⌮

ఀ⸨ⱥே


 㸭 (OHFWURQLFWUDSSLQJDQGVXUIDFHSURWRQDWLRQLQ7L2
QDQRVWUXFWXUHVᮾᕤ኱⌮*HUJHO\-XKDV] 㸭 

ࣛࢪ࢝ࣝ࢝ࢳ࢜ࣥᛶ᭷ᶵ㔠ᒓศᏊ࣡࢖࣮ࣖ࡜ࢫ࢖ࢵࢳࡢ㛤Ⓨᮾᕤ኱໬Ꮫ⏕࿨⛉Ꮫ◊✲ᡤ⏣୰⿱ஓ 㸭 

ከᶵ⬟㓄఩Ꮚࢆࡶࡘ㔠ᒓ㘒యࡢᵓ㐀࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲⌮໬Ꮫ◊✲ᡤ

ὸᏊኊ⨾ 㸭 

ィ⟬ศᏊศගᏛ㸸ศᏊࡢᵓ㐀࠾ࡼࡧ཯ᛂ࡟㛵ࡍࡿィ⟬໬Ꮫ

࠾Ⲕ኱
⌮

ᖹ㔝ᜏኵ


 㸭 

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ὸᕝ኱ᶞ


 㸭 

ࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨ἲ࡟ࡼࡿ),9ࣉࣟࢸ࢔࣮ࢮ࡜+,9ࣉࣟࢸ࢔࣮ࢮ
㜼ᐖ๣ࡢ┦஫స⏝ゎᯒ

⟃Ἴ኱㝔
ᩘ⌮≀㉁

ᯇ஭ࠉ஽


 㸭 

ᾮయࡢ⤫ィຊᏛ⌮ㄽ࡟ࡼࡿ⏕యศᏊࡢᶵ⬟ゎᯒ

஑ᕞ኱㝔
⌮

ྜྷ⏣⣖⏕


 㸭 

Ⲵ㟁ȧ㟁Ꮚ⣔ࡢタィ࣭ྜᡂࢆᇶ㍈࡜ࡋࡓ㉸ศᏊ㞟ྜయࡢ๰〇

❧࿨㤋኱
⏕࿨⛉Ꮫ

๓⏣኱ග


 㸭 

Ꮫ㝿ⓗ◊✲ࡢࡓࡵࡢẼ┦୰ཎᏊ࣭ศᏊ㟁Ꮚບ㉳≧ែ⢭ᐦ㔞Ꮚ໬Ꮫィ
⟬

ᮾὒ኱
⌮ᕤ

⏣௦ᇶ៞


 㸭 

ࢱࣥࣃࢡ㉁࡟⤖ྜࡍࡿேᕤ࢜ࣜࢦ
࢔࣑ࢻࡢ࢖ࣥࢩࣜࢥタィ

ᮾ኱㝔
ᕤ

᳃ᮏ῟ᖹ


 㸭 

IJ

IJ

IJ

IK

IK

IK

IL

IL

IL

IM

IM

IN

IN

IO

IP

Ẽ┦࢖࢜ࣥࡢ
✲

ᗘィ

࡟㛵ࡍࡿ◊

- 14 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IP

')7ศᏊືຊᏛィ⟬ࢆ⏝࠸ࡓ⁐⼥ሷ୰ࡢᨺᑕᛶᗫᲠ≀ࡢ⁐ゎᗘホ౯

ᮾ໭኱㝔
ᕤ

᏷ᡞ༤⣖


 㸭 

༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢᵓ㐀ไᚚྜᡂ࡟ྥࡅࡓศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱㝔
ᕤ

୸ᒣⱱኵ


 㸭 

ࢪࢢࣜࢥ࣮ࣝ࢔࣑ࢻ⣔᭷ᶵ㓄఩Ꮚ࡟ࡼࡿࣛࣥࢱࣀ࢖ࢻ㸭࣐࢖ࢼ࣮࢔
ࢡࢳࣀ࢖ࢻ࢖࢜ࣥࡢ㑅ᢥⓗᢳฟ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥ኱㝔
ඛ㐍⌮ᕤ

஭ཱྀెဢ


 㸭 

࢟ࣀࣜࣥ㦵᱁ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ
◊✲

໭㔛኱
⌮

⚄㇂ᫀᏹ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿග໬Ꮫ⣔ϩࡢᵓ㐀࣭཯ᛂᶵᵓゎᯒ

ྡ኱㝔
⌮

㔝ཱྀࠉᕦ


 㸭 

᭷ᶵ࢖ࣜࢪ࣒࣏࢘ࣝࣇ࢕ࣜࣥ㘒య࡟ࡼࡿ㉥Ⰽග࢔ࣥࢣ࣮ࢪࣥࢢ཯ᛂ
ࡢ㛤Ⓨᮾ኱⏕⏘ᢏ⾡◊✲ᡤᮧ⏣ࠉ្ 㸭 

⌮ㄽィ⟬ࢆ฼⏝ࡋࡓ᭷ᶵ༙ᑟయᮦ
ᩱࡢ㛤Ⓨ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

ⰼᮧோႹ


 㸭 

ィ⟬໬Ꮫࢆ⏝࠸ࡓゐ፹ࡢ⌮ㄽタィ࠾ࡼࡧ᭷ᶵᮦᩱࡢⓎග≀ᛶ࡜ศᏊ
㐠ືࡢゎᯒ

໭኱㝔
ᕤ

ఀ⸨ࠉ⫕


 㸭 

ศᏊືຊᏛ࡜➨୍ཎ⌮ィ⟬ࢆ⏝࠸ࡓ᭷ᶵ⤖ᬗ࠾ࡼࡧᾮయࡢ⇕≀ᛶ࠾ࡼࡧ⇕㟁ຠᯝࡢィ⟬⛉Ꮫⓗ◊✲

໭኱㝔
ᕤ

ᓥ⏣ᩄᏹ


 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ⭷ࢱࣥࣃࢡ㉁ࡢᵓ㐀ࠊᶵ⬟ࠊࢲ࢖ࢼ࣑ࢡࢫゎᯒᮾ኱㝔㎰Ꮫ⏕࿨⛉Ꮫ

⠛⏣ᜨᏊ 㸭 ᭤ࡆኚᙧ࡟㛵ࡍࡿᾮᬗᏳᐃᛶࡢศ
ᏊືຊᏛ࡟ࡼࡿ◊✲ᮾி㎰ᕤ኱㝔ᕤᆏᮏ㐨᫛ 㸭 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ࡙ࡃศᏊࣔ
ࢲࣜࢸ࢕ࡢ⌮ゎ࣭ไᚚ࣭タィ

ᮾ኱㝔
ᕤ

㯮⏣኱♸


 㸭 

཯ᛂ⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝

໭኱㝔
⌮

๓⏣ࠉ⌮


 㸭 

G㑄⛣㔠ᒓ࠿ࡽ࡞ࡿᆒ୍⣔ཬࡧ୙ᆒ୍⣔ゐ፹࡟ࡼࡿ&2㑏ඖ཯ᛂᶵᵓ
ࡢㄪᰝ஑኱
,t&1(5ఀໃᕝ⨾✑ 㸭 ᐇ㦂࡜ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂᶵᵓゎ
ᯒ

ᮾ኱㝔
⸆

⁪⏣ࠉⰋ


 㸭 

ගᅇ᚟㓝⣲࡟ࡼࡿගᛂ⟅ᶵᵓࡢゎ
᫂

㜰኱㝔
ᇶ♏ᕤ

ᒣඖ῟ᖹ


 㸭 

IQ

IQ

IQ

IQ

IR

IR

IT

IT

IU

IU

IU

IU

IU

IV

IV

- 15 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IV

᪂つ㧗ᶵ⬟ᛶࡢ୙ᩧゐ፹◊✲࡜࣋࢖ࢬ᭱㐺໬࣭ᶵᲔᏛ⩦࡬ࡢ㐺⏝

ྡᕤ኱
ᕤ

୰ᮧಟ୍


 㸭 

㓟໬≀⤖ᬗ࠾ࡼࡧ⼥య࡟࠾ࡅࡿᵓ
㐀⦆࿴ࢆ㥑ືຊ࡜ࡋࡓ୙つ๎㘒యᵓ㐀ࡢ⮬Ⓨⓗᙧᡂ㐣⛬ࡢゎᯒ

㜰኱㝔
ᕤ

㕥ᮌ㈼⣖


 㸭 

ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂

ྡ኱㝔
ᕤ

㕥ᮌ῟ᕧ


 㸭 &RPSXWDWLRQDO,QYHVWLJDWLRQRI&RORVVDO'LHOHFWULF
3HUPLWWLYLW\0DWHULDOVDQG&KHPLFDO%RQGLQJ)HDWXUHVRI
7UDQVLWLRQ0HWDO'LR[LGHVྡ኱ᮍ᮶♫఍๰㐀ᶵᵓ

3UDGHHS
9DUDGZDM


IW

IW

IW

IX

IX

IX

IY

IZ

IZ

I[

I[

I\

I\

I\

I\

஬᰾㕲ࢡࣛࢫࢱ࣮ࡢ㟁Ꮚ≧ែ࡜཯ᛂᛶࡢ⌮ㄽゎᯒྡ኱㸦࣓ࣥࣂ࣮ᩘ㸧







 㸭 
ࢺࣛࣥࢫࣇ࢛࣮࣐ࢸ࢕ࣈ
⏕࿨ศᏊ◊✲ᡤᰗ஭ࠉẎ 㸭 

⢓ᗘࡢᇶᮏࢭࣝࢧ࢖ࢬຠᯝࢆࡶ㋃
ࡲ࠼ࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ࡟ࡼࡿᕧ኱ศᏊࡢὶయຊᏛ༙ᚄ
࡜Ỉ࿴ࡢ㛵ಀ

஑኱㝔
⌮

⛅ᒣࠉⰋ


 㸭 

ศᏊ㔠ᒓ㘒య࠾ࡼࡧከ᰾ࢡࣛࢫ
ࢱ࣮ࡢ⢭ᐦไᚚ࡜㟁Ꮚ≧ែࡢゎ᫂

ᮾ໭኱㝔
⌮

㛗⏣ᾈ୍


 㸭 ᪂つྜᡂ཯ᛂࠊ᪂ᶵ⬟ࡢ๰ฟࢆᚿ
ྥࡋࡓ⌮ㄽ໬Ꮫⓗ◊✲

ᮾ㎰኱
⏕࿨⛉Ꮫ

ᩧ⸨❳⏨


 㸭 

ࢼࣀ࣮࢝࣎ࣥ࡜᭷ᶵ≀ࢆ⏝࠸ࡓᶵ⬟ᮦᩱࡢィ⟬໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ㧗ᗘ᝟ሗ⛉Ꮫᢏ⾡
◊✲ᶵᵓ

ᡭᓥṇ࿃


 㸭 

ྵ࣊ࢸࣟ㠀ᖹ㠃ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢᵓ㐀࠾ࡼࡧᛶ㉁

᪩኱
⌮ᕤ

ຍ⸨೺ኴ


 㸭 

Ẽ┦ศᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ศᏊ㛫┦஫స⏝ࡢ⌮ㄽⓗゎᯒ࡜࣮ࣞࢨ࣮ศග◊✲

ᮾ໭኱㝔
⌮

ᯇ⏣Ḡஅ


 㸭 

ᕤᴗཎᩱࢆ฼⏝ࡋࡓ⢭ᐦ໬Ꮫኚ᥮
཯ᛂࡢ㛤Ⓨ

㜰኱㝔
ᕤ

ᫍᮏ㝧୍


 㸭 

⏕యศᏊ⮬ᕫ㞟ྜ⣔ࡢศᏊࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ

ᒸᒣ኱
␗ศ㔝ᇶ♏⛉Ꮫ
◊✲ᡤ

⠛⏣ࠉ΅


 㸭 

ᶵ⬟ᛶศᏊ㞟ྜయࡢศᏊືຊᏛ◊✲㸸ぶỈᛶ⏺㠃࡟࠾ࡅࡿỈศᏊࡢ
ᶵ⬟ゎᯒ

රᗜ┴኱㝔
᝟ሗ⛉Ꮫ

▼஭Ⰻᶞ


 㸭 ࢖࢜ࣥ ศᏊ ㄆ㆑࡟࠾ࡅࡿᚤどⓗỈ࿴ຠᯝ࡜ ᗘຠᯝࡢゎ᫂ᮾᕤ኱⛉Ꮫᢏ⾡๰ᡂ◊✲㝔ᖹ⏣ᆂ♸ 㸭 

࢖࢜ࣥᛶⰍ⣲ࢆྵࡴ᪂つȧ㟁Ꮚ⣔ࡢྜᡂ࡜㓄ิไᚚ

ᒣᙧ኱㝔᭷ᶵᮦᩱࢩࢫࢸ࣒

ᒣ㛛㝠ᖹ 㸭 

- 16 -

























௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

I\

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ㓄ྥᶞ⬡ᮦᩱࡢ⇕ఏᑟ≉ᛶゎᯒ

ᮾᕤ኱
≀㉁⌮ᕤ

ྂᒇ⚽ᓠ


 㸭 

ḟඖ࡜㸱ḟඖࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿
ࡽ᫂ࡽ࠿࡟ࡍࡿࢱࣥࣃࢡ㉁ࡢจ㞟

஑⏘኱
⌮ᕤ

ᮎᯇᏳ⏤⨾


 㸭 

ᰁⰍయࡢ᪂つࣔࢹࣝ㛤Ⓨ࡜✀ࠎࡢศᏊࡢཎᏊ㛫ຊ㢧ᚤ㙾ീࡢ⌮ㄽィ⟬㔠ἑ኱ࢼࣀ⏕࿨⛉Ꮫ◊✲ᡤⅣ❤ாྖ 㸭 

࢟ࣛࣝࢼࣇࢱࣞࣥᅄ㔞యⰍ⣲ࡢບ
㉳≧ែᵓ㐀

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

㧗▼࿴ே


 㸭 

'LVUXSWLRQPHFKDQLVPRIWKH
7R[RSODVPDJRQGLLSDUDVLWRSKRURXVYDFXROHE\
,5*%

㜰኱
ච␿Ꮫࣇࣟࣥࢸ࢕࢔
◊✲ࢭࣥࢱ࣮

)ORULV-DQ
YDQ(HUGHQᨺᑕᛶቯኚࡸ㟁☢Ἴ┦஫స⏝࡟ࡼࡿ⏕యศᏊࡢᵓ㐀ኚ໬

᰾⼥ྜ⛉Ꮫ◊✲ᡤ࣊ࣜ࢝ࣝ◊✲㒊୰ᮧᾈ❶ 㸭 

$J⨨᥮ࢮ࢜ࣛ࢖ࢺ;࡟࠾ࡅࡿࣉࣟࣃ
ࣥࣉࣟࣆࣞࣥศ㞳࣓࢝ࢽࢬ࣒ࡢゎ᫂ಙᕞ኱ඛ㗦ᮦᩱ◊✲ᡤ⏣୰⚽ᶞ 㸭 

㔠ᒓ㓟໬≀ࢡࣛࢫࢱ࣮ࢆ฼⏝ࡋࡓศᏊ≧」ྜయࡢタィ࡜ᶵ⬟㛤ᣅ

ᮾ኱㝔
ᕤ

㕥ᮌᗣ௓


 㸭 

6+ࢻ࣓࢖ࣥ࡜ࣜࣥ㓟໬࣌ࣉࢳࢻࡢ
⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ゎᯒ་⸆ᇶ┙࣭೺ᗣ࣭
ᰤ㣴◊✲ᡤ

ᮤࠉ⚽ᰤ


 㸭 

పศᏊࢆㄆ㆑࣭άᛶ໬ࡍࡿ᪂つ㘒య࡟㛵ࡍࡿ◊✲

ᮾி㟁ᶵ኱
ᕤ

ᒣᮏဴஓ


 㸭 

㧗㟁఩㕲◲㯤ࢱࣥࣃࢡ㉁ࡢάᛶ୰
ᚰࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟ࡘ࠸࡚ࡢ⌮
ㄽⓗゎᯒ

⟃Ἴ኱
ィ⟬⛉Ꮫ◊✲
ࢭࣥࢱ࣮

ᇼࠉඃኴ


 㸭 

᪂ࡋ࠸἞⒪ἲࡢ☜❧ࢆ┠ᣦࡋࡓ᪂
つゐ፹ࡢ㛤Ⓨ

ᮾ኱㝔
⸆

୕ࢶ἟἞ಙ


 㸭 

⁐ᾮෆ࠾ࡼࡧ⏕యศᏊෆ࡛㉳ࡇࡿ໬Ꮫ཯ᛂ࡜ᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽⓗゎ᫂஑኱ඛᑟ≀㉁໬Ꮫ◊✲ᡤ᳃ࠉಇᩥ 㸭 

⏺㠃άᛶ๣จ㞟ᣲືࡢ⌮ㄽࣔࢹࣜࣥࢢᒸᒣ኱␗ศ㔝ᇶ♏⛉Ꮫ
◊✲ᡤ

⏥㈡◊୍㑻


 㸭 

㧗ศᏊ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࡢࡓࡵ
ࡢศᏊືຊᏛィ⟬࡟ࡼࡿ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜㧗ᶵ⬟ᛶ㧗ศᏊࡢ᥈⣴⤫ィᩘ⌮◊✲ᡤᯘࠉ៞ᾈ 㸭 

࣐ࣝࢳࢻ࣓࢖ࣥࢱࣥࣃࢡ㉁ࡢศᏊ
ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᶵ⬟ゎᯒ㔞Ꮚ⛉Ꮫᢏ⾡
◊✲㛤Ⓨᶵᵓ

I]

I]

I]

I]

I]

I]

JD

JD

JD

JF

JF

JF

JF

JG

JG

- 17 -

㸦࣓ࣥࣂ࣮ᩘ㸧

⏣ཱྀ┿ᙪ









 㸭 





















 㸭 ௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

JG

ࢢࣝࢱ࣑ࢻ㉸ศᏊࢼࣀᵓ㐀యࡢᶵ
⬟Ⓨ⌧࡟࠾ࡅࡿᐁ⬟ᇶ㓄ྥᵓ㐀ࡢ
ゎᯒ

⇃ᮏ኱㝔
ඛ➃⛉Ꮫ

᱓ཎࠉ✨


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ᭷ᶵศᏊゐ፹
ࡢ⢭ᐦタィ

ᮾ໭኱㝔
⌮

ᑎ⏣┾ᾈ


 㸭 

⌮ㄽィ⟬ࢆ฼⏝ࡋࡓࣛࢪ࣓࢝ࣝ࢝
ࣀࣇ࢛࢔ࡢゎᯒ࠾ࡼࡧ᪂つศᏊ㦵
᱁ࡢ㛤Ⓨ

ᮾᕤ኱
≀㉁⌮ᕤ

ᮡ⏣ࠉ୍


 㸭 

࣊ࢸࣟࣛࢪ࢝ࣝ࠿ࡽ࡞ࡿ᪂ወࣇ࢛
ࢺࢡ࣑ࣟࢵࢡศᏊࡢ๰〇࡜ගᶵ⬟ศᏊࡢບ㉳≧ែ᥈⣴

❧࿨㤋኱
⏕࿨⛉Ꮫ

ᑠᯘὒ୍


 㸭 

㑄⛣㔠ᒓゐ፹࠾ࡼࡧ᭷ᶵゐ፹ࢆ⏝࠸ࡓ୙㣬࿴⤖ྜ࡬ࡢ௜ຍ཯ᛂ࡟࠾
ࡅࡿ఩⨨࠾ࡼࡧ❧య㑅ᢥᛶࡢゎ᫂

㜰኱㝔
ᕤ

ඤ⋢ᣅஓ


 㸭 

ேᕤຊㄏ㉳཯ᛂἲࢆά⏝ࡋࡓ࣊ࢸࣟඖ⣲ྵ᭷᪂཯ᛂ๣࡜᪂つ෇೫ගⓎගᮦᩱࡢ㛤Ⓨ໭኱໬Ꮫ཯ᛂ๰ᡂᣐⅬ㛗⏣⿱ஓ 㸭 

㟁Ẽ໬Ꮫⓗ࡟Ⓨ⏕ࡉࡏࡓάᛶ✀ࡢ཯ᛂ࡟࠾ࡅࡿ཯ᛂᶵᵓ࡜཯ᛂ㑅ᢥᛶࡢ⌮ㄽ໬Ꮫⓗ⪃ᐹ

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

ග⸨⪔୍


 㸭 ศᏊࡢᵓ㐀ࠊ(65ࢫ࣌ࢡࢺࣝࡢィ⟬

ᮾ໭኱㝔
⌮

ዟὠ㈼୍


 㸭 ୧ぶ፹ᛶศᏊ㞟ྜయ࡬ࡢ≀㉁㍺㏦
ᶵᵓࡢゎ᫂ி㒔ᕤⱁ⧄⥔኱
ᮦᩱ໬Ꮫ

Ỉཱྀ᭸Ꮚ


 㸭 

㧗ศᏊ◚ቯ࡟㛵ࡍࡿศᏊࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ

ྡ኱㝔
ᕤ

⸨ᮏ࿴ኈ


 㸭 

&17࡬ࡢ࢔ࣝ࢝ࣥΰྜ⁐፹࠿ࡽࡢ㛗㙐㑅ᢥⓗ྾ⶶ࡜ࡑࡢ⌮ゎ

៞᠕኱
⌮ᕤ

༓ⴥᩥ㔝


 㸭 

㜰኱ᚤ⏕≀⑓◊✲ᡤᚎࠉᏊᬸ 㸭 

ィ⟬໬Ꮫ࡟ࡼࡿ᭷ᶵゐ፹ཬࡧ᭷ᶵ
㔠ᒓゐ፹ࢆ⏝࠸ࡓ᪂つ཯ᛂࡢᶵᵓ
ゎ᫂

ᒸᒣ኱
⮬↛⛉Ꮫ

ᒣᓮࠉ㈼


 㸭 

Ⅳ⣲㸫࣊ࢸࣟཎᏊ⤖ྜࡢษ᩿࠾ࡼ
ࡧᙧᡂࢆక࠺㦵᱁㌿఩཯ᛂࡢィ⟬໬Ꮫ࡟ࡼࡿᶵᵓゎ᫂

㜰኱㝔
⸆

㮵ཪႛᖹ


 㸭 ᪂つ࢟ࣛࣝศᏊࡢ࢟ࣟࣉࢸ࢕࢝ࣝ
≉ᛶࡢ⌮ㄽィ⟬

㜰኱㝔
ᕤ

▼๭ᩥᓫ


 㸭 

㠀ᴟᛶị୰ࡢᙅ࠸┦஫స⏝,㸸&2
&2ịୖࡢ+ཎᏊࡢᣲື

ᮾ኱㝔
⌮

┦ᕝ♸⌮


 㸭 

JG

JG

JH

JH

JI

JI

JI

JI

JI

JI

JJ

JJ

JJ

JK

JL

$QWLERG\$QWLJHQFRPSOH[
SUHGLFWLRQRSWLPL]HGE\$OSKD)ROG- 18 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

JM

ࢱࣥࣃࢡ㉁51$」ྜయ⣔ࡢ඲ཎᏊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲᪩኱⌮ᕤࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DD

จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ
࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ」㞧⣔ࡢ㔞Ꮚ≧ែ⌮ㄽࡢ㛤Ⓨ࡜୙ᆒ୍⣔ゐ፹࠾ࡼࡧගᶵ⬟ࢩࢫࢸ࣒⣔࡬ࡢᛂ⏝௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧὾⏣㐨᫛

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 


ᡤෆ

DG

DG

DI

DI

DI

DJ

DJ

DK

DK

DL

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ᩧ⸨┿ྖ 㸭 

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮Ụཎṇ༤ 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿࢱࣥࣃࢡ㉁ࡢจ㞟࡜จ㞟㜼ᐖ⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮

ዟᮧஂኈ 㸭 

ศᏊືຊᏛィ⟬࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᾮయࡢศᏊ㛫┦஫స⏝ࡢ◊✲

ගศᏊ⛉Ꮫ

㛗ᆏᑗᡂ


 㸭 

ィ⟬ᶵ࠾ࡼࡧ⏕໬Ꮫᐇ㦂࡟ࡼࡿࢱ
ࣥࣃࢡ㉁ศᏊࢹࢨ࢖ࣥ

⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮

ྂ㈡ಙᗣ
 㸭 

ศᏊືຊᏛィ⟬࡟ࡼࡿᢠయࡢศᏊ
ෆࢿࢵࢺ࣮࣡ࢡࡢ᥈ᰝ

⏕࿨࣭㘒యศᏊ⛉Ꮫ㇂୰෪Ꮚ 㸭 

⏕యศᏊ࣐ࢩࣥ࡟࠾ࡅࡿ࣐ࣝࢳࢫ
ࢣ࣮ࣝ࡞ᶵ⬟Ⓨ⌧ࢲ࢖ࢼ࣑ࢡࢫࡢ
ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮

ᒸᓮᆂ୍ 㸭 

ศᏊ⣔࣭จ⦰⣔࡟࠾ࡅࡿ☢ᛶ࠾ࡼࡧࣇ࢛ࣀࣥ≀ᛶࡢ➨୍ཎ⌮ィ⟬⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ༡㇂ⱥ⨾ 㸭 

ḟඖȧඹᙺᵓ㐀యࡢ๰ᡂ⏕࿨࣭㘒యศᏊ⛉Ꮫ℩ᕝὈ▱ 㸭 

㧗㇂ࠉග 㸭 $GULDQ-8UEDQ 㸭 

㑄⛣㔠ᒓ㘒యゐ፹ࢆ⏝࠸ࡿ᭷ᶵ཯
ᛂࡢ཯ᛂᶵᵓ◊✲ගศᏊ⛉Ꮫ

6HDUFKIRUVDGGOHSRLQWVLQWKH
V\QDQWLSHULSODQDULVRPHULVP
RIWULDU\ODUR\OELODWULHQDEFRQDWRQLFNHO,,༠ዌศᏊࢩࢫࢸ࣒
◊✲ࢭࣥࢱ࣮

- 19 -























ࠑᇶ♏⏕≀Ꮫࠒ᪋タ฼⏝ %
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

TF

Șࢳ࣮ࣗࣈࣜࣥ&ᮎ➃㡿ᇦࡢ⩻ヂᚋಟ㣭ࡀᚤᑠ⟶ᵓ㐀㞟ᅋ࡟୚࠼ࡿᙳ
㡪ࡢศᏊࢲ࢖ࢼ࣑ࢡࢫゎᯒಙᕞ኱㎰௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᱵ⃝බ஧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 
ࠑ⏕⌮Ꮫࠒ᪋タ฼⏝ %
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

ND

࢖࢜ࣥࢳࣕࢿࣝࡢ࢖࢜ࣥ㑅ᢥᛶᶵᵓࡢゎᯒࡢࡓࡵࡢศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ

࿴ḷᒣ┴❧་኱
⸆ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

LD

ḟඖ05,࡟ࡼࡿ⬻ࡢᶵ⬟ཬࡧᵓ㐀
ゎᯒ

ᚰ⌮⏕⌮Ꮫ

ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⬻ᶵ⬟⏬ീゎᯒ⏕యᶵ⬟᝟ሗゎᯒᐊ௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ධỤඞ㞞

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 


ᡤෆ

LD

- 20 -

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧⚟Ọ㞞႐ 㸭 ㏆ῧ῟୍
 㸭 











    

        

$ %





#&


*,3S,30:/61P-B &  7R %! 

@8 $&K0L2;J  HG

(8Q.D9$&.

0C>N<O."$'A)?4

$&+I(5FE #'$$Q8M= "!200)!, 3=)97  #`k /;;#P JNy34 #Nh b

Te

Te

S

  z`|)' 3 OOJ{ 9+';'-&>#  rm

N
Me

POxT

J   v¡%   AE   $#W
di|  e!

PTH
PAzT

)'   1/2#12/%-&#(!*#-'%,+-*%#2*%0 /;;@aUJ KXR  /;=2%7'-&>C4?;#{h 
Osq ")' 5/>*8;6.3 
e! 9+';'-&>;$,g#D0:-;(=:1GFuJ^x_#[ ]U YN #IYNMFVQL ! 3 #IYN
0:-;'-&>}p QL  !4  3 
j Z QL#  E ;$,g ~!

 l



<1.(,wgSoE [ Hf'-&>N  TG\^BctZB    5 
/;;Pn<1.(,wg[#|,-<>Hf'-&>N  TG\B   5









- 21 -)'   
-/")1!* -& /!$)#!*
#!1)-,0.%#)%0

Calculation of metastable supramolecular structures createdin a microflow field-¯µ {ÜsÓÀÝ

1

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5 M F @ ­ ²  g l b R k o @ 0 L    ))'"!( (*#%$)%& $+#&%'& +'!$  N¬uA7?.¤<B  ÍuDC7?4</;Dq@.XlfoÕ AQi_ 3\joXC!
ÔÄ7<  Íu3.Ï}]_bPS`pN
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uC>1?.  mdlDËÁN¦7.
ÞÖuDªÑD NÈB=</ªÑE}¢~É«A  NÅ7?Ìw7</;DÃ©.Xlfo!
Õ AQi_ 3}×»rv´8L5ACIK.g
lbRko³3 )%()" 7< tu3 "-/  '&%
ªÑA7?JM</6JC.qanplNc    ( #  . *  $ )n\o8LA (#!&& ()" 7< tu3 + ,ªÑCBL5A3§J2AB=<Ü Ý/B.5M
J  ËÁDÃ©E.!( XeV\lI  XeV\lDÃ©A I»Ø7.
¨ËÁÃ©D 36M?1L/
2|F<E (1) Kanzaki C.; Numata, M. Chem. Lett. 52, 37 (2023).
(2) Kanzaki C.; Yoneda, H.; Nomura, S.; Maeda T.; Numata, M. RSC Adv. 12, 30670 (2022).

- 22 -

➨୍ิ㑄⛣㔠ᒓゐ፹ࡢගᛂ⟅࡟㛵ࡍࡿ⌮ㄽ໬Ꮫⓗ᳨ド
Theoretical investigation of photoinduced transformations catalyzed byfirst row transition metals‫ۑ‬ᑠᓥṇᐶࠊྜྷ㔝㐩ᙪࠊ෠⏣Ọᕼࠊຍ⸨ె⨾ࠊ⬥ᕝᣅᕭ㸦໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧1◊✲┠ⓗ➨୍ิ㑄⛣㔠ᒓࡣ㧗࠸ᣢ⥆ྍ⬟ᛶ࡜≉␗࡞཯ᛂᛶࢆ᭷ࡍࡿⅬ࡛᭷ᶵྜᡂ໬Ꮫࡢゐ፹࡜ࡋ࡚᭷ᮃ࡛࠶ࡿࠋ୍

᪉࡛ࡇࢀࡽࡢ㔠ᒓࢆゐ፹࡜ࡍࡿග཯ᛂࡢሗ࿌ࡣᮍࡔᑡ࡞ࡃࠊࡑࡢཎᅉࡢ୍ࡘ࡟཯ᛂᶵᵓ࡟㛵ࡍࡿ▱ぢࡀ㝈ࡽࢀ࡚࠸ࡿࡇ࡜ࡀᣲࡆࡽࢀࡿࠋᡃࠎࡣᡃࠎࡢࢢ࣮ࣝࣉ࡛ᐇ㦂໬Ꮫⓗ࡟Ⓨぢࡋࡓ➨୍ิ㑄⛣㔠ᒓゐ፹ࢆ⏝࠸ࡿග཯ᛂ࡟ࡘ࠸࡚ࠊ⌮ㄽ໬Ꮫࢆ⏝࠸ࡓ཯ᛂᶵᵓゎ᫂࡟ྲྀࡾ⤌ࢇࡔࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
㕲ゐ፹࡜ගゐ፹ࡢ༠ാࢆ⏝࠸ࡓ 2+2+2 ⎔໬௜ຍ཯ᛂ࡟ࡘ࠸࡚ࠊ᝿ᐃ཯ᛂᶵᵓࡢጇᙜᛶࢆ DFT㸦GRRM17 ࢆ౑⏝㸧࠾ࡼࡧ SAC-CI㸦Gaussian16 ࢆ౑⏝㸧ࢆ⏝࠸᳨࡚ドࡋࡓࠋࡲࡓࢥࣂࣝࢺゐ፹࡜ගゐ፹ࡢ༠ാ࡟ࡼࡿ㟁Ꮚ
୙㊊࢔ࣝࢣࣥࡢ㔜Ỉ⣲໬཯ᛂ࡟㛵ࡍࡿ཯ᛂᶵᵓ࡟ࡘ࠸࡚ࠊDFT ࢆ⏝࠸᳨࡚ドࡋࡓࠋ3◊✲ᡂᯝ㕲ゐ፹ࢆ⏝࠸ࡓ⎔໬௜ຍ཯ᛂ࡟ࡘ࠸࡚ࠊ࢚ࢿࣝࢠ࣮⛣ື࡟ࡼࡾ⇕ⓗ࡟ᅔ㞴࡞⣲཯ᛂࡀຍ㏿ࡉࢀࡿ࡜࠸࠺▱ぢࡀᚓࡽࢀࡓࠋࡇࡢᡂᯝ࡟ࡘ࠸࡚ࡣ㸯௳ࡢㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋࡲࡓࢥࣂࣝࢺゐ፹ࢆ⏝࠸ࡓ㔜Ỉ⣲ཎᏊ⛣ືᆺ཯ᛂ࡟ࡘ࠸࡚ࠊ㑄⛣≧ែࡢᑟฟࡸ୰㛫యࡢ NBO ゎᯒࢆ⏝࠸ࡿࡇ࡜࡛ࠊࣛࢪ࢝ࣝⓗ࡟㐍⾜ࡍࡿ࡜࠸࠺཯ᛂᶵᵓ
௬ㄝࡢጇᙜᛶࢆᨭᣢࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋࡇࡢᡂᯝ࡟ࡘ࠸࡚ࡣ㸰௳ࡢᏛ఍Ⓨ⾲࡜㸯௳ࡢㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ࠕۻ‬ග㓟໬㑏ඖゐ፹/ࢥࣂࣝࢺゐ፹ࡢ༠ാ࡟ࡼࡿ D2O ࢆ㔜Ỉ⣲※࡜ࡋࡓ DAT 㔜Ỉ⣲໬཯ᛂࠖࠐ㕥ᮌᬗᙪ 1ࠊட஭ᐋ἞ 1ࠊΎ㔝భ௓ 1ࠊᒣཱྀඃ෤ 1ࠊྜྷ㔝㐩ᙪ 1,2ࠊᑠᓥṇᐶ 1ࠊᯇỌⱱᶞ 1,2 㸦1 ໭኱㝔

⸆ࠊ2 GI-CoRE㸧➨ 12 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2022 2022 ᖺ 10 ᭶ ࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ࣏ࢫࢱ࣮Ⓨ⾲‫ࠕۻ‬ග㓟໬㑏ඖゐ፹/ࢥࣂࣝࢺゐ፹ࡢ༠ാ࡟ࡼࡿ D2O ࢆ㔜Ỉ⣲※࡜ࡋࡓ DAT 㔜Ỉ⣲໬཯ᛂࠖࠐ㕥ᮌᬗᙪ 1ࠊட஭ᐋ἞ 1ࠊΎ㔝భ௓ 1ࠊᒣཱྀඃ෤ 1ࠊྜྷ㔝㐩ᙪ 1,2ࠊᑠᓥṇᐶ 1ࠊᯇỌⱱᶞ 1,2 㸦1 ໭኱㝔
⸆ࠊ2 GI-CoRE㸧➨ 48 ᅇ཯ᛂ࡜ྜᡂࡢ㐍Ṍࢩ࣏ࣥࢪ࣒࢘ 2022 ᖺ 11 ᭶ ༓ⴥᕷẸ఍㤋 ࣏ࢫࢱ࣮Ⓨ⾲

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫“ۻ‬Iron/Photosensitizer Hybrid System Enables the Synthesis of Polyaryl-Substituted Azafluoranthenes”
Y. Kato, T. Yoshino, M. Gao, J. Hasegawa, M. Kojima, S. Matsunaga J. Am. Chem. Soc. 2022, 144, 18450-18458.
‫“ۻ‬Photocatalytic Deuterium Atom Transfer Deuteration of Electron-Deficient Alkenes with High Functional Group

Tolerance”
A. Suzuki, Y. Kamei, Y. Seino, Y. Yamaguchi, T. Yoshino, M. Kojima, S. Matsunaga Angew. Chem. Int. Ed. 2022,
e202214433.

- 23 -

')7 ィ⟬࡟ࡼࡿ」ᩘࡢ㔠ᒓ✀࠿ࡽ࡞ࡿከ᰾㔠ᒓ㘒యࡢ㟁Ꮚᵓ㐀ࡢゎ᫂
')7&DOFXODWLRQRI(OHFWURQLF6WUXFWXUHVIRU+HWHURPHWDOOLF0XOWLQXFOHDU&RPSOH[HV‫ۑ‬᳜ᮧ ୍ᗈࠊ㧗᳃ ᩔᚿ㸦ᒱ㜧኱Ꮫ㸧 ◊✲┠ⓗⓑ㔠࡜ࣟࢪ࣒࢘ࡢ㛫࡟␗✀㔠ᒓ⤖ྜࢆࡶࡘ」᰾㘒యࡢ>3W5K /  ; <@Qࡢྜᡂ࡟ᡂຌࡋ࡚࠸ࡿࠋኚ࠼ࡽࢀࡿ
㓄఩Ꮚࡣ /ࠊ;ࠊ< ࡢ  ࠿ᡤ࠶ࡾࠊ㓄఩Ꮚ࡟ࡼࡗ࡚㓟໬㑏ඖ㟁఩ࡀ␗࡞ࡾࠊሙྜ࡟ࡼࡗ࡚ࡣ୙ᑐ㟁Ꮚࢆࡶࡘࡇ
࡜ࡀᐇ㦂ⓗ࡟ࢃ࠿ࡗ࡚࠸ࡿࠋ≉࡟ࠊ>3W5K SLDP &O 1+ 33K@ SLDP SLYDODPLGDWH ࡣࠊ>0&O@í㸦0 3W3G㸧
࡜ΰྜࡍࡿ࡜ࠊ5Kí3Wí0í3Wí5K ࡜୍ḟඖ≧஬᰾㘒య࡜࡞ࡾࠊࡑࡢ⏕ᡂ㐣⛬࡟࠾࠸࡚ࠊ྾཰ࢫ࣌ࢡࢺࣝࡀ  ẁ㝵࡛㛗Ἴ㛗ഃ࡬ࢩࣇࢺࡍࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡇࢀࡽࡢ୍ḟඖ≧ከ᰾㔠ᒓ㘒యࡢ㟁Ꮚᵓ㐀࡜྾཰ࡢᖐᒓࢆࠊ
ཝᐦ࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣᐇ㦂ⓗ࡟㝈⏺ࡀ࠶ࡾࠊᚓࡽࢀࡓྛࠎࡢ⤖ᬗᵓ㐀ࢆࡶ࡜࡟ࠊ')7 ィ⟬࡟ࡼࡾ㟁Ꮚ㌶
㐨ࢆ᫂ࡽ࠿࡟ࡋࠊ7'')7 ィ⟬࡛㟁Ꮚ྾཰ᖏࢆぢ✚ࡶࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ༢⤖ᬗ ; ⥺ᵓ㐀ゎᯒࡢ⤖ᯝࢆࡶ࡜࡟ࠊ⤖ᬗᵓ㐀࡜㔠ᒓ㛫㊥㞳࡜㓄఩⤖ྜ㊥㞳ࢆྠࡌ࡟ࡋࡓࣔࢹࣝࢆึᮇᵓ
㐀࡟ࠊ*DXVVLDQ ࢆ⏝࠸࡚ࠊ%/<3* GS /$1/'= ࡛ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ ◊✲ᡂᯝ
')7 ィ⟬࠿ࡽࠊ>3W5K SLDP &O 1+ 33K@ࡢ /802 ࡣࠊⓑ㔠࡜ࣟࢪ࣒࢘ࡢ Gz ㌶㐨ࡢ㔜࡞ࡾ࡟ࡼࡿ ı ᛶ㌶
㐨࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ7'')7 ィ⟬࠿ࡽࠊQP ࡢ྾཰ࡣࠊྠᵝ࡟ ı ᛶ㌶㐨࡛࠶ࡿ +202í ࠿ࡽ/802 ࡬ࡢ㑄⛣࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ>3W5K SLDP &O 1+ 33K@࡟>3W&O@íࢆຍ࠼ࡿ࡜ࠊ QP ࡬ࠊࡉࡽ࡟ຍ࠼ࡿ࡜  QP ࡬㛗Ἴ㛗ࢩࣇࢺࡍࡿࠋ5Kí3Wí3W ࡜୪ࢇࡔ୕᰾㘒యࢆࣔࢹࣝ࡟ィ⟬ࡍࡿ࡜ࠊ/802 ࡜+202í ࡟ ı ᛶ㌶㐨ࡀ☜ㄆ࡛ࡁࠊQP ࡢ྾཰ࡀ୧㛫ࡢ㑄⛣࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ5Kí3Wí3Wí3Wí5K
࡜୪ࢇࡔ஬᰾㘒యࢆࣔࢹࣝ࡟ࠊ QP ࡢ྾཰ࡀࠊı ᛶ㌶㐨ࡢ +202 ࡜ /802 ࡢ㑄⛣࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟
ࡋࡓࠋࡇࢀࡽࡣࠊ0  3G ࡛ࡶྠᵝ࡛࠶ࡾࠊ㔠ᒓ᰾ᩘࡀቑ࠼ࡿ࡟ࡘࢀࠊGz ㌶㐨⏤᮶ࡢ⿕༨᭷㌶㐨ࡀ୙Ᏻᐃ໬
ࡋࠊ㛗Ἴ㛗ࢩࣇࢺࡍࡿࡇ࡜࡜ࠊ㏲ḟⓗ࡟㔠ᒓ᰾ᩘࡀቑ࠼࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬.8HPXUD+6KLPRIXVDsubmitted for the publication‫ ۻ‬.8HPXUD<,NHGD$7DNDPRUL77DNH\DPD6,ZDWVXNLChem. Eur. J.29H‫ ۻ‬.8HPXUD<6XJL\DPDInorg. Chem. Commun.142 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

- 24 -

ࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢ㓄ᗙゎᯒ࡜ࣛࢪ࢝ࣝ௜ຍ཯ᛂࡢ㑄⛣≧ែィ⟬
&RQIRUPDWLRQDODQDO\VLVRIJO\FRV\OUDGLFDODQGWUDQVLWLRQVWDWH
FDOFXODWLRQRIUDGLFDODGGLWLRQ‫ۑ‬ᐤ❧ 㯞⍆ࠊ୕ᾆ ኱ᚿࠊᖹ஭ ๛㸦஑ᕞ኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧

1◊✲┠ⓗ᭱㏆ᡃࠎࡢ◊✲ᐊ࡛ࡣࠊ↓ಖㆤࢢࣜࢥࢩࣝࢫࣝࣇ࢕ࢿ࣮ࢺࢆ฼⏝ࡋࡓࠊ↓ಖㆤࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢ Gieseࣛࢪ࢝ࣝ௜ຍ཯ᛂ࡟ࡼࡿ α 㑅ᢥⓗ࡞ Csp3 ࢢࣜࢥࢩࣝ໬཯ᛂࢆ㛤Ⓨࡋࡓࠋᮏ཯ᛂࡢ❧య㑅ᢥᛶ࡜ࢢࣜࢥࢩࣝࣛ
ࢪ࢝ࣝ୰㛫యࡢ❧య㓄ᗙࠊ࠾ࡼࡧ㑄⛣≧ែ࡟࠾ࡅࡿ⢾ࡢ❧య㓄ᗙࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊࢢࣜࢥࢩࣝ
ࣛࢪ࢝ࣝࡢ㓄ᗙゎᯒ࠾ࡼࡧ㑄⛣≧ែ᥈⣴ࢆᮏ◊✲ࡢ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢ㓄ᗙ᥈⣴࠾ࡼࡧ Giese ࣛࢪ࢝ࣝ௜ຍ཯ᛂࡢ㑄⛣≧ែ᥈⣴ࡣ௨ୗࡢᡭἲ࡛ィ⟬ࡋࡓࠋࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢ㓄ᗙ᥈⣴㸸Spartan 2 (MMFF)ᵓ㐀᭱㐺໬ࠊ࢚ࢿࣝࢠ࣮ィ⟬㸸Gaussian 16 (m062x/6-311G(d,p))㑄⛣≧ែィ⟬㸸Reaction Plus (B3LYP/6-31G(d,p)࡞࡝)ࠊGaussian 16 (m062x/6-311G(d,p))3◊✲ᡂᯝ↓ಖㆤࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢ⥙⨶ⓗ࡞㓄ᗙゎᯒ࡟ࡼࡾࠊ᭱ࡶᏳᐃ࡞㓄ᗙࡣ 4C1 㓄ᗙ࡛࠶ࡾࠊ⥆࠸࡚ 1C4 (+0.6

kcal/mol), OS2 (+1.7 kcal/mol), 1S5 (+2.8 kcal/mol), 1S3 (+2.9 kcal/mol), B2,5 (+3.9 kcal/mol), BO,3 (+3.9 kcal/mol), B1,4(+5.0 kcal/mol), 2SO (+5.6 kcal/mol), 5S1 (+6.0 kcal/mol)࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋᚓࡓࢢࣜࢥࢩࣝࣛࢪ࢝ࣝࡢᵓ㐀ࢆᇶ࡟ࠊࡑࢀࡒࢀࡢ㓄ᗙ࡟ᑐࡍࡿ࣓ࢳࣝ࢔ࢡ࣮ࣜࣞࢺࡢ α-࠾ࡼࡧ β-ࣛࢪ࢝ࣝ௜ຍ཯ᛂࡢ㑄⛣≧ែࢆ Reaction
Plus ࡛᥈⣴ࡋࡓࠋ4C1 㓄ᗙࡢࢢࣜࢥࢩࣝࣛࢪ࢝ࣝ࠿ࡽ α ௜ຍయࢆ୚࠼ࡿ㑄⛣≧ែࡀ+8.7 kcal/mol ࡛࠶ࡾࠊ4C1
㓄ᗙ࠿ࡽ β ௜ຍయࢆ୚࠼ࡿ㑄⛣≧ែ(+14.4 kcal/mol)ࡼࡾࡶᴟࡵ࡚᭷฼࡛࠶ࡗࡓࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊ1C4 ࠾ࡼࡧ
1

S5 㓄ᗙ࠿ࡽ β ௜ຍయࢆ୚࠼ࡿ

㑄⛣≧ែࡣ+11.1 kcal/mol ࠾ࡼࡧ+11.8 kcal/mol ࡛࠶ࡾࠊ4C1 㓄ᗙࡢࡑࢀࡼࡾࡶ᭷฼࡛࠶ࡿࡇ
࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ◊✲ᡂᯝ࡟㛵㐃ࡍࡿ◊✲ࢆࠊಟኈ 1 ᖺ୕ᾆ኱ᚿࡀ᪥ᮏ⸆Ꮫ఍ᖺ఍࡟ཱྀ࡚㢌Ⓨ⾲ࡋࡓࠋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
⌧ᅾࠊ௨ୖࡢ◊✲ᡂᯝࢆྵࡴ཯ᛂ㛤Ⓨㄽᩥࢆ Chemical Communications ㄅ㸦Royal Chemical Society ♫㸧࡟ᢞ✏୰࡛࠶ࡿࠋ

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1.

Hisayasu Ishibashi, Takehisa Maekawa, Akiko Yagi, Kenichiro Itami “Synthesis of a Catenane from [9]Cycloparaphenylene and 2,2′-Bipyridine Macrocycle”
19th International Symposium on Novel Aromatic Compounds (ISNA), P232, Warsaw, Poland (Online),
2022/07/03 (Poster)2.

Hiroki Shudo, Motonobu Kuwayama, Masafumi Shimasaki, Taishi Nishihara, Youhei Takeda, Nobuhiko Mitoma,
Takuya Kuwabara, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami“Synthesis and Properties of Polyfluorocycloparaphenylenes”
19th International Symposium on Novel Aromatic Compounds (ISNA), P237, Warsaw, Poland (Online),
2022/07/03 (Poster)- 27 -

3. Hideya Kono, Yuanming Li, Akiko Yagi, Kenichiro Itami
Synthesis and Size-dependent Properties of Methylene-bridged [n]Cycloparaphenylenes
ISNA-19, PP-219, Online, 2022/06/03–2022/06/08 (poster)
4. Takaku Yoshihara, Akiko Yagi, Kenichiro Itami“An Adamantane-annulation of Arenes”
19th International Symposium on Novel Aromatic Compounds (ISNA), Warsaw, Poland (Online),
2022/07/03(Poster)
5. Daiki Imoto, Hiroki Shudo, Akiko Yagi, Kenichiro Itami“Host-guest Chemistry of Perfluorocycloparaphenylenes”
19th International Symposium on Novel Aromatic Compounds (ISNA), P255, Warsaw, Poland (Online),
2022/07/03 (Poster)
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2022 Q GTR ?:", P-409, 62Kty cLSC5, Wu, 2023 Q 01 ` 16 ]¢56T£
13. f_jH#<;XtG*bgx!)U“Synthesis and properties of novel heteroatom-containing carbon nanorings”
2022 Q GTR ?:", P-308, 62Kty cLSC5, Wu, 2023 Q 01 ` 16 ]¢56T£
14. vh Sl, Manuel Rondelli, -N ), *b gx, ! )U“Synthesis of Catenane from [9]Cycloparaphenylene and 2,2′-Bipyridine Macrocycle”
2022 Q GTR ?:", P-125, 62Kty cLSC5, Wu, 2023 Q 01 ` 16 ]¢56T£- 28 -

15. ;X tG, *b gx, ! )U“Synthesis and Properties of Thiophene belts”
2022 Q GTR ?:", P-108, 62Kty cLSC5, Wu, 2023 Q 01 ` 16 ] (56T)
16. Yoshifumi Toyama, Takaku Yoshihara, Akiko Yagi, Kenichiro Itami
Synthesis of molecular diamond 38 =miy ?T, P-32, +2;EOT:yM*P, 2022 Q 09 ` 29 ] (56T)
17. ;XtG*bgx!)U8/D-SGP=m É 32 =rwiyÅÇ", 1A08, >ÚCP5FN, 2022 Q 09 ` 20 ] (1)18. Hideya Kono Atsushi UsamiHiroki Shudo Kazuma AmaikeAkiko YagiKenichiro Itami¥¢A[%'Ó¶/x8?BGP=m 32 =rwiyÅÇ", 2P045, >ÚCP5FN , 2022 Q 09 ` 21 ] (56T)
19. Takaku Yoshihara, Akiko Yagi, Kenichiro Itami
Synthesis and Properties Adamantane-anulated Arenes
 32 =rwiyÅÇ", 1P081, >ÚCP5FN , 2022 Q 09 ` 20 ] (56T)
20. Daiki Imoto, Hiroki Shudo, Akiko Yagi, Kenichiro Itami
Host-guest Chemistry of Perfluorocycloparaphenylene
 32 =rwiyÅÇ", 2P124, >ÚCP5FN , 2022 Q 09 ` 22 ] (56T)
21. Atsushi Usami, Hideya Kono, Hiroki Shudo, Akiko Yagi, Kazuma Amaike, Kenichiro Itami
Functionalization of Methylene-bridged [6]Cycloparaphenylene by Spodoptera litura 9 = ITbM/GTR S

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22. 5/}¡*b gx, ! )UAn Adamantane-annulation of Arenes
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1.  Hiroki Shudo, Motonobu Kuwayama, Yasutomo Segawa, Akiko Yagi, Kenichiro Itami"Half-substituted fluorocycloparaphenylenes with high symmetry: Synthesis, properties and derivatization todensely substituted carbon nanorings"
ChemRxiv 2023 DOI:10.26434/chemrxiv-2023-zsvnt
2.  Nobushige Kai, Hideya Kono, Akiko Yagi,* Kenichiro Itami*"Synthesis and properties of methylene-bridged [6]cyclo-2,6-naphthylene"
Synlett 2023, 18, in press. DOI: 10.1055/a-2009-8219
3.  Shusei Fujiki, Kazuma Amaike, Akiko Yagi,* and Kenichiro Itami*“Synthesis, properties, and material hybridization of bare aromatic polymers enabled by dendrimer support”
Nature Communications 2022, 13, 5358. DOI: 10.1038/s41467-022-33100-7
4.  Hiroki Shudo, Motonobu Kuwayama, Masafumi Shimasaki, Taishi Nishihara, Youhei Takeda, NobuhikoMitoma, Takuya Kuwabara, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami“Perfluorocycloparaphenylenes”
Nature Commun. 2022, 13, 3713.
5.  Hiroki Sato, Rie Suizu, Tomoki Kato, Akiko Yagi, Yasutomo Segawa, Kunio Awaga, Kenichiro Itami“N-doped Nonalternant Aromatic Belt via a Six-fold Annulative Double N-Arylation”
Chem. Sci. 2022, 13, 9947-9951.

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◊✲᪉ἲࠊィ⟬᪉ἲィ⟬⛉Ꮫⓗ࡟ศᏊ㛫࣏ࢸࣥࢩࣕࣝࢆண
1.

ࡍࡿࡓࡵ࡟௨ୗࡢࡼ࠺࡞ᡭἲࢆᐇ᪋ࡋࡓ㸬ᵝࠎ࡞ศᏊ㓄ྥ࡟ᑐࡋ࡚㸪Gaussian16 ࢆ⏝࠸࡚ CCSD(T)/augcc-pVTZ ࡛ࣞ࣋ࣝ 1 Ⅼ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓ㸬෇⟄ᗙᶆ+Euler ゅᗙᶆ⣔࡛ᐃ⩏ࡉࢀࡿᅗ 1 ࡢᗙᶆ⣔(ܴ, ߶஺ , ߩ, ߱஻ )ࢆ⏝࠸࡚㸪Tab.1 ࡟♧ࡍ 525 ⅬࡢศᏊ㓄ྥࢢࣜࢵࢻ࡟ᑐࡋ࡚ィ⟬ࢆᐇ᪋ࡋࡓ㸬ࡇࡢ࢚ࢿࣝࢠ࣮ィ⟬ࡢࡓࡵ࡟ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ࣜࢯ࣮ࢫࢆ฼⏝ࡋࡓ㸬
⾲ 1.1 Ⅼ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࢢࣜࢵࢻ
ኚᩘ

ࢢࣜࢵࢻ

ܴ

3.40, 3.55, 3.70, 3.85, 4.00 Ⴒߩ

0, 0.3, 0.6 Ⴒ߶஺

0, 120, 240 deg.

ߠ஻30, 60, 90 deg.

߯஻45, 75, 105, 135 deg.

ᅗ 1. ෇ ⟄ ᗙ ᶆ +Euler ゅ ᗙ ᶆ ⣔(ܴ, ߶஺ , ߩ, ߱஻ )㸬

2.

ィ⟬ࡋࡓ࢚ࢿࣝࢠ࣮Ⅼ࡟ᑐࡋ࡚㸪ࣔࢹ࣏ࣝࢸࣥࢩ࡛ࣕࣝ᭱ᑠ
஧஌ࣇ࢕ࢵࢸ࢕ࣥࢢࡍࡿࡇ࡜࡛࣏ࢸࣥࢩࣕࣝ᭤㠃ࢆỴᐃࡋࡓ㸬- 33 -

3◊✲ᡂᯝᡭ㡰 1 ࡛ ab initio ィ⟬ࢆ⾜࠸㸪ᡭ㡰 2 ࡛ࡑࢀࡽࡢィ⟬Ⅼࢆゎᯒⓗ࡞㛵ᩘ࡛ࣇ࢕ࢵࢺࡍࡿࡇ࡜࡛ᚓࡽࢀࡓ࣏

ࢸࣥࢩࣕࣝࡢ 2 ḟඖ᩿㠃ࢆᅗ 2 ࡟♧ࡍ㸬ᅗ 2(a)ࡣ࣋ࣥࢮࣥ㠃ୖ࡟࠶ࡿ࣓ࢱࣥࡢෆ㒊ᅇ㌿࣏ࢸࣥࢩࣕࣝࢆ⾲ࡋ࡚࠾ࡾ㸪100 cm-1 ⛬ᗘࡢప࠸ෆ㒊ᅇ㌿㞀ቨࡀィ⟬ࡉࢀࡓ㸬ẚ㍑࡜ࡋ࡚࣓ࢱࣥࡢᅇ㌿ᐃᩘࡣ B = 5.241 cm-1 ࡛࠶ࡾ㸪⮬⏤࡞࣓ࢱࣥᅇ㌿Ꮚ࡛ࡣ 2B ~ 10 cm-1, 6B ~ 30 cm-1 ࡟࢚ࢿࣝࢠ࣮‽఩ࢆࡶࡘ㸬ᅇ㌿㞀ቨࡀ࢚ࢿࣝࢠ࣮‽఩࡜ࢥࣥࣃࣛࣈ࡛ࣝ࠶ࡿࡓࡵ࡟㸪࣓ࢱࣥෆ㒊ᅇ㌿≧ែࡣࢺࣥࢿࣝศ⿣ࢆ⏕ࡌ㠀ᖖ࡟」㞧࡞࢚ࢿࣝࢠ࣮ᵓ㐀ࢆ᭷ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀࡓ㸬ᅗ 2(b)ࡣ࣓ࢱࣥ㔜ᚰ㐠ືࢆ⾲ࡍ࣏ࢸࣥࢩ᩿ࣕࣝ㠃ࢆ⾲ࡋ࡚࠸ࡿ㸬୰ኸ࡟኱ࡁ࡞
ᴟᑠ್ࢆᣢࡘࡇ࡜ࡣ㸪࣓ࢱࣥࡀ࣋ࣥࢮࣥ㠃ୖ࡟᮰⦡ࡉࢀ࡚࠸ࡿ࡜⌮ゎࡍࡿࡇ࡜ࡀ࡛ࡁࡿ㸬௒ᅇࡢゎᯒ࡟ࡼࡗ࡚ศᏊ㛫࣏ࢸࣥࢩࣕࣝࡀᐃ㔞ⓗ࡟Ỵᐃࡉࢀ㸪ᅗ 2 ࡢ 2 ࡘࡢࢢࣛࣇ࠿ࡽ(i)࣓ࢱࣥࡣ୺࡟࣋
ࣥࢮࣥ㠃ୖ࡟఩⨨ࡋ㸪(ii)ࡸࡸ㜼ᐖࡉࢀ࡞ࡀࡽ࣓ࢱࣥࡀෆ㒊ᅇ㌿ࡋ࡚࠸ࡿ㸪࡜࠸࠺ศᏊ㐠ືᥥീࡀᚓࡽࢀࡓ㸬ᅗ 2. ィ⟬ࡉࢀࡓ 6 ḟඖ࣏ࢸࣥࢩࣕࣝࡢ 2 ḟඖ᩿㠃㸬(a)࣓ࢱࣥࡢෆ㒊ᅇ㌿࡟㛵ࡍࡿ᩿㠃ᅗ (b)࣓ࢱࣥ㔜ᚰ㐠ືࢆ⾲ࡍ᩿㠃ᅗ㸬

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1. ‫ۻ‬బࠎᮌᚭ, ୰ᮧ㞞᫂, ኱ᓥᗣ⿱, ࠕ࣋ࣥࢮࣥ㸫࣓ࢱࣥ van der Waals 㘒య࡟࠾ࡅࡿ 6 ḟඖࣔࢹ࣏ࣝࢸࣥࢩ
ࣕࣝィ⟬࡜ศᏊ㛫᣺ືἼ᮰ほࠖ㸪➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍㸪2022 ᖺ 9 ᭶, ᶓ὾

2. ‫ۻ‬బࠎᮌᚭ, ୰ᮧ㞞᫂, ኱ᓥᗣ⿱, ࠕBenzene-methane ศᏊ㘒యࡢ 6 ḟඖࣔࢹࣝゎᯒ࡜⣸እ࣮ࣞࢨ࣮ศගࠖ,᪥ᮏศගᏛ఍ᖺḟㅮ₇఍, 2022 ᖺ 10 ᭶, ᮾி㸬
3. ‫ۻ‬బࠎᮌᚭ, ୰ᮧ㞞᫂, ኱ᓥᗣ⿱,ࠕBenzene-methane ศᏊ㘒య࡟࠾ࡅࡿ 6 ḟඖࣔࢹ࣏ࣝࢸࣥࢩࣕࣝィ⟬࡜ศᏊ㛫᣺ືศගࠖ
㸪➨ 22 ᅇศᏊศග◊✲఍㸪2022 ᖺ 11 ᭶㸪ᮾி㸬
4. ˔ Toru Sasaki, Masaaki Nakamura, Yasuhiro Ohshima, “Six-dimensional model calculations and wave-packet
observation of intermolecular vibration in the benzene–CH4 van der Waals complex”, Kick-off International
Symposium of JSPS Core-to-Core Program on “Molecular Recognition Mechanism between Flexible Molecules”,
Sep. 2022, poster presentation at Tokyo.
5. ˔ Toru Sasaki, Masaaki Nakamura, Yasuhiro Ohshima, “SIX-DIMENSIONAL MODEL ANALYSIS AND
INTERMOLECULAR VIBRATIONAL SPECTROSCOPY OF BENZENE-METHANE vdW COMPLEX”, 76th
International Symposium on Molecular Spectroscopy, Jun. 2023, oral presentation at Illinois.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

࡞ࡋ- 34 -

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ࡑࡇ࡛ࡲࡎࡣࠊࣔࢹࣝ໬ྜ≀ $ ࡢࣛࢭ࣑໬ࢆᢚไࡋ࡚⏕ᡂ≀ ' ࢆ୚࠼ࡿ཯ᛂᶵᵓ࡜୙ᩧቑᖜࡢ㘽୰㛫యࡢᣦ- 35 -

㔪ࢆᚓࡿࡓࡵ࡟ࠊண᝿୰㛫య % ࠿ࡽࡢ༠ዌⓗ⎔ᣑ኱཯ᛂࣉࣟࢭࢫࢆ୰ᚰ࡟ ')7 ィ⟬࡟ࡼࡾゎᯒࡋࡓࠋࡇࢀࡲ
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ィ⟬ࡢ⤖ᯝࡣ཮⏕࢖࢜ࣥ୰㛫య & ࡢ⣔୰࡛ࡢ⏕ᡂࡀᙉࡃ♧၀ࡉࢀࡓࠋ⏕ᡂ≀ ' ࢆ୚࠼ࡿ཯ᛂᶵᵓ࡜ࡋ࡚⤖ྜࡢ㛤⿣࡜ᙧᡂࡀ༠ዌⓗ࡟㐍⾜ࡍࡿ㑄⛣≧ែ 76& ࢆ⤒࡚࠸ࡿࡇ࡜ࡀᡴデࡉࢀࡓࡶࡢࡢࠊᐊ ࡟࡚㐍⾜ࡍࡿᮏ཯ᛂ࡜ࡋ࡚ࡣィ⟬࡛ᑟ࠿ࢀࡓ㑄⛣≧ែࡢ࢚ࢿࣝࢠ࣮ࡣ㧗ࡃࠊ௒ᚋᇶᗏ㛵ᩘࢆࡉࡽ࡟኱ࡁࡃࡋ࡚᭱㐺໬ࢆࡍࡿᚲせࡀ࠶ࡿࠋ

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࡞ࡋ- 36 -

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ࡋࠊ㧗ศゎ⬟ࡢࢱࣥࣃࢡ㉁⤖ᬗࢆᚓࡿࡇ࡜ࡣࠊ᫬࡟ᅔ㞴࡞సᴗ࡜࡞ࡿࠋ◲㓟࢔ࣥࣔࢽ࣒࢘ $6  ࡣࠊࢱࣥࣃ
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ࣥ 3$1  ࡜࢟ࢺࢧࢼ࣮ࢮࢆ $6 ࣮࣋ࢫࡢỿẊ๣࡟ࡼࡗ࡚⤖ᬗ໬ࡉࡏࡓࠋỿẊ๣⁐ᾮ࡟ࡣࠊࢺࣞࣁ࣮ࣟࢫ࡜ ȘȘȘࢺࣜ  2ș'ࢢࣝࢥࣆࣛࣀࢩࣝ  ࢚ࢳࣝ࢜࢟ࢩ ࢥࣛࣥ )DFDGH7(*  ࡀࡑࢀࡒࢀྵࡲࢀ࡚࠸
ࡿࠋ࡝ࡕࡽࡢ⤖ᬗࡶ௨๓ࡢ◊✲࡛ᚓࡽࢀࡓ⤖ᬗࡼࡾࡶࠊ㧗࠸ศゎ⬟ࡢᅇᢡീࢆ♧ࡋࡓࠋࢢࣜ࢝ࣥࡢ᭷↓ࡢ᮲௳࡟࠾࠸࡚ࠊ」ᩘࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊࢱࣥࣃࢡ㉁࡜ࢢࣜ࢝ࣥࡢ┦஫స⏝ࢆཎᏊࢫࢣ࣮ࣝ
࡛⌮ゎࡍࡿࠋࡉࡽ࡟ࢢࣜ࢝ࣥࢱࣥࣃࢡ㉁」ྜయࡢ❧యᵓ㐀ࡢࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸࡚῝࠸▱ぢࢆᚓࡿࠋ
ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊ$0%(5 ࢆ౑⏝ࡋࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ㌶㊧࠿ࡽᖹᆒ஧஌೫ᕪ 506' ᅇ㌿༙ᚄ 5J ᗘᅉᏊࢆồࡵᵓ㐀ࡢ㓄ᗙᏳᐃᛶࢆホ౯ࡋࡓࠋ୺ᡂศศᯒ 3&$  ࢆ⏝࠸࡚⺮ⓑ㉁ᵓ㐀ࡢ❧య㓄ᗙࡢኚ໬ࢆㄪ࡭ࡓࠋࡲࡓࠊ003%6$ ἲࢆ⏝࠸࡚ࠊࢱࣥࣃࢡ㉁࡜ࢢࣜ࢝ࣥࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓࠋḟ࡟ࠊࢱࣥࣃࢡ㉁࿘㎶ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࡢᙧ≧ࢆㄪ࡭ࠊࢢࣜ࢝ࣥࡢศᕸ࡜ẚ㍑ࡋࡓࠋẚ㍑࡛ࡣࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࡀࢱࣥࣃࢡ㉁⾲㠃ࡢࢢࣜ࢝ࣥࡢዲࡲࡋ࠸⤖ྜ㒊఩࡜┦㛵ࡍࡿ࠿࡝࠺࠿ࢆㄪ࡭ࡓࠋࡲࡓࠊ$6 ⁐ᾮ࡟ࢢࣜ࢝ࣥࢆῧຍࡋ࡚ᚓࡽࢀࡓ⤖ᬗᵓ㐀ࢆࢱࣥࣃࢡ㉁ࢹ࣮ࢱࣂࣥࢡ 3'%  ࢆ㏻ࡌ࡚ㄪᰝࡋࠊࢢࣜ࢝ࣥ࡜ࢱࣥࣃࢡ
㉁⤖ᬗᡂ㛗࡜ࡢ㛵㐃ᛶࢆ⤫ィⓗ࡟ホ౯ࡋࡓࠋ



◊✲ᡂᯝ
ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊࢱࣥࣃࢡ㉁⾲㠃ୖࡢࢢࣜ࢝ࣥ࡟ࡘ࠸࡚ࠊ࠸ࡃࡘ࠿ࡢ⤖ྜ࣏࣮ࢬࡀほᐹࡉࢀࡓࠋ஧஌ᖹᆒᖹ᪉᰿೫ᕪ࡜ᅇ㌿༙ᚄࡣࢢࣜ࢝ࣥ⤖ྜࡢᏳᐃᛶࢆ♧ࡋࡓࠋࢢࣜ࢝ࣥࢆྵࡴィ⟬ࣔࢹࣝ࡜ྵ
ࡲ࡞࠸ィ⟬ࣔࢹࣝࡢ

ᗘᅉᏊࡢẚ㍑࡟ࡼࡾࠊ᥋ゐ㡿ᇦ࡛ࡢࢱࣥࣃࢡ㉁❧య㓄ᗙࡢ㐪࠸ࡀ☜ㄆࡉࢀࡓࠋࡉࡽ࡟

ࢩ࣑࣮ࣗࣞࢩࣙࣥ㌶㊧ࡢ୺ᡂศศᯒࡣࢢ̺ࣜ࢝ࣥ⺮ⓑ㉁」ྜయࡢ᭷ព࡟ࢥࣥࣃࢡࢺ࡞㐠ືࢆ♧၀ࡋࡓࠋ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬࠿ࡽࡣࠊ୺࡟␯Ỉᛶ┦஫స⏝ࡀࢱࣥࣃࢡ㉁࡜ࢢࣜ࢝ࣥࡢ」ྜయࢆᏳᐃ໬ࡍࡿࡇ࡜ࢆ♧ࡋࡓࠋࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊࢱࣥࣃࢡ㉁࿘㎶ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝ࡜ࢢࣜ࢝ࣥ⤖ྜ࡜ࡢ㛵ಀࢆヲࡋࡃㄪ࡭ࡓࠋ

- 37 -

ྑᅗ࡟♧ࡍࡼ࠺࡟ࠊ࡯࡜ࢇ࡝ࡢࢢࣜ࢝ࣥ⤖ྜ㒊఩ࡣ㟼㟁࣏ࢸࣥࢩࣕࣝࡢṇ࡜㈇ࡢ㡿ᇦࡢቃ⏺㡿ᇦ࡟࠶ࡾࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࡢ⤯ᑐ್ࡣప࠸㡿ᇦ࡛࠶ࡗࡓࠋቃ⏺㡿ᇦࡣ⤖ᬗࡢศᏊ඘ሸ࡟࠾ࡅࡿ⺮ⓑ㉁㛫ࡢ᥋ゐ㒊఩࡜୍⮴ࡋ࡚࠸ࡓࠋࡉࡽ࡟ࠊࢱࣥࣃࢡ㉁ࢹ࣮ࢱࣂࣥࢡ࠿ࡽ
$6 ⁐ᾮ୰࡟ࢢࣜ࢝ࣥࢆῧຍࡋ࡚ᚓࡽࢀࡿ⤖ᬗᵓ㐀ࢆ᥈⣴ࡋࡓࠋ௚ࡢᚑ᮶ࡢ໬Ꮫ≀㉁࡜ẚ㍑ࡋ࡚ࠊࢱࣥࣃࢡ㉁ࡢ⤖ᬗ໬᮲௳࡛ࡣࢢࣜ࢝ࣥࡢྵ᭷࡟㛵ࡍࡿ᝟ሗࡣ
ࡲࡔ㝈ࡽࢀ࡚࠸ࡓࠋῧຍ≀ࡣࠊࢱࣥࣃࢡ㉁ࡢᏳᐃᛶࢆ
㧗ࡵࠊ⾲㠃ࡢᰂ㌾ᛶࢆపୗࡉࡏࠊࢱࣥࣃࢡ㉁࡜ࢱࣥࣃ
ࢡ㉁ࡢ఍ྜࢆࢧ࣏࣮ࢺࡍࡿ࡜࠸࠺ࢱࣥࣃࢡ㉁ࡢ⤖ᬗ໬ࡢ࣓ࣜࢵࢺࡀ࠶ࡿ࡜᥎ᐹࡉࢀࡿࠋ

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- 38 -

ゐ፹ศᏊ⣔࠾ࡼࡧ⏕యศᏊ⣔ࡢ㔞Ꮚ໬Ꮫ࡜཯ᛂືຊᏛ
Quantum Chemistry and Reaction Dynamic of
Catalytic and Biological Systemsࠐ㛗㇂ᕝ῟ஓ㸪㣤⏣ ೺஧㸪㧗 ᩄ㸪Manussada Ratanasak㸪
Sarinya Hadsadee㸪ⓑ⏨ᕝ㈗ྐ㸪ᐑᕝ ⩧㸪኱ᇛ ᾏ㸪༓ⴥ ༟⣫㸪ᖹ℩ࡦࡢࡁ㸪㇂⏣㒊 Ꮥᩥ㸪➉஭ ኱㍜㸦໭ᾏ㐨኱Ꮫゐ፹⛉Ꮫ◊✲ᡤ㸪ᮾி኱ᏛᕤᏛ⣔◊✲⛉㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࣉࣟࢪ࢙ࢡࢺ࡟ࡼࡾᐇ᪋ࡋࡓ◊✲ࡢ୰࠿ࡽḟࡢࢸ࣮࣐࡟ࡘ࠸࡚ࠊࡑࡢ⤖ᯝࢆሗ࿌ࡍࡿࠋ
(1.1) Ḟ㝗ࢆ᭷ࡍࡿ❅໬࣍࢘⣲ࢼࣀࢩ࣮ࢺୖࡢ NiCo ゐ፹࡟ࡼࡿ࣓ࢱࣥࢻࣛ࢖ࣜࣇ࢛࣮࣑ࣥࢢ
(1.2) ᱁Ꮚࡦࡎࡳࡢᑟධ࡟ࡼࡿ Ru ⾲㠃࡟࠾ࡅࡿ CO ゎ㞳཯ᛂࡢไᚚ
(1.3) ཯ᛂ≀ࡢ㓄఩࡟ࡼࡾไᚚࡉࢀࡿ཯ᛂ⤒㊰㸸Ni 㘒యゐ፹࡟ࡼࡿ࣋ࣥࢰࣇࣛࣥྜᡂ཯ᛂ
(1.4) ୙ᩧ⬺Ỉ⎔໬཯ᛂࢆゐ፹ࡍࡿ Ru ゐ፹ࡢ཯ᛂᶵᵓ࡟㛵ࡍࡿ◊✲(1.5) ୙ᆒ୍࡞ᅛᾮ㟁Ẽ஧㔜ᒙ⏺㠃ࡢ⌮ㄽⓗ◊✲(1.6) Alchemical perturbation DFT ࢆ⏝࠸ࡓᶵ⬟ᛶศᏊࡢタィἲ࡟㛵ࡍࡿ◊✲(1.7) BPh3 ゐ፹࡟ࡼࡿ࢔࣑ࣥ㢮ࡢ N-࣓ࢳࣝ໬཯ᛂࡢ࣓࢝ࢽࢬ࣒࡟㛵ࡍࡿ◊✲

2◊✲᪉ἲࠊィ⟬᪉ἲ(2.1) (1.1)ࡢ◊✲࡟ࡣ Vasp ࢆ౑⏝ࡋࡓ.
(2.2) (1.2)ࡢ◊✲࡟ࡣ GPAW ࢆ౑⏝ࡋࡓ.
(2.3) (1.3)ࡢ◊✲࡟ࡣ Gaussian, AFIR ࢆ౑⏝ࡋࡓ.
(2.3) (1.4)࠾ࡼࡧ(1.7)ࡢ◊✲࡟ࡣ Gaussian ࢆ౑⏝ࡋࡓ.
(2.5) (1.5)ࡢ◊✲࡟ࡣ SALMON ࢆ౑⏝ࡋࡓ.
(2.6) (1.6)ࡢ◊✲࡟ࡣ◊✲ᐊ࡛㛤Ⓨࡋࡓࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓ.

3◊✲ᡂᯝ(3.1) Ḟ㝗ࢆ᭷ࡍࡿ❅໬࣍࢘⣲ࢼࣀࢩ࣮ࢺୖࡢ NiCo ゐ፹࡟ࡼࡿ࣓ࢱࣥࢻࣛ࢖ࣜࣇ࢛࣮࣑ࣥࢢ
ୖᾏ኱Ꮫࡢ Zhang Dengsong ࡽࡣ㸪Ḟ㝗ࡀ࠶ࡿභ᪉ᬗ❅໬࣍࢘⣲㸦h-BN㸧࡟ᢸᣢࡋࡓ NiCo ⢏Ꮚࢆ๰ᡂࡋ㸪࣓ࢱࣥࡢࢻࣛ࢖ࣜࣇ࢛࣮࣑ࣥࢢ࡟ᛂ⏝ࡋ㸪ࢥ࣮ࢡᯒฟ࡟ࡼࡿຎ໬ࢆᢚไࡍࡿࡇ࡜࡟ᡂຌࡋࡓ㸬ᮏ◊✲࡛ࡣ⌮ㄽィ⟬ࢆ⏝࠸࡚㸪Ḟ㝗ࡢ✀㢮ࡀ⾲㠃ࡢ㟁Ꮚᵓ㐀࡟ᙉ࠸ᙳ㡪ࢆཬࡰࡋ㸪❅⣲Ḟ㝗ࡣ㟁Ꮚࢻࢼ࣮㸪࣍࢘⣲Ḟ㝗ࡣ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮࡟࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬ࡲࡓ㸪ࡇࡢ h-BN ࡟ᢸᣢࡉࢀࡓ NiCo ゐ፹࡟ࡼࡿ CH4 ࡜ CO2
ࡢ཯ᛂάᛶ࡟኱ࡁࡃᙳ㡪ࡍࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 1㸧ࠋᮏ◊✲ᡂᯝࡣᅜ㝿ඹⴭㄽᩥ࡜ࡋ࡚㸪CCS Chemistry ㄅ࡟࡚Ⓨ⾲ࡋࡓ㸬

(3.2) ᱁Ꮚࡦࡎࡳࡢᑟධ࡟ࡼࡿ Ru ⾲㠃࡟࠾ࡅࡿ CO ゎ㞳཯ᛂࡢไᚚ
୙ᆒ୍⣔ゐ፹స⏝࡟࠾ࡅࡿ᱁Ꮚࡦࡎࡳࡢᙳ㡪ࢆ⌮ゎࡍࡿࡓࡵ࡟㸪ࣇ࢕ࢵࢩ࣮࣭ࣕࢺࣟࣉࢩࣗ཯ᛂ࡟⏝࠸ࡽࢀࡿ Ru ゐ፹࡟ࡘ࠸࡚㸪➼᪉ᛶ࠾ࡼࡧ␗᪉ᛶࡦࡎࡳࡀ CO ゎ㞳άᛶ࡟ཬࡰࡍᙳ㡪ࢆ⌮ㄽィ⟬࡟ࡼࡾ᳨ウࡋࡓ㸬- 39 -

ࡦࡎࡳࢆᑟධࡍࡿ࡜ CO ࡢ྾╔࢚ࢿࣝࢠ࣮ࡀኚ໬ࡍࡿࡀ㸪࡯࡜ࢇ࡝ࡢሙྜ㸪CO ゎ㞳ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡣ
Brønsted-Evans-Polyani㸦BEP)ࡢ㛵ಀ࡟ᚑࡗ࡚྾╔࢚ࢿࣝࢠ࣮࡜ẚ౛㛵ಀࢆ♧ࡋࡓ㸬ࡋ࠿ࡋ㸪Ru(1015)⾲㠃ࡣ
BEP ๎࡜␗࡞ࡿᣲືࢆ♧ࡍࡇ࡜ࡀぢฟࡉࢀ㸦ᅗ 2㸧㸪₯ᅾⓗ࡟᪂ࡋ࠸཯ᛂ⤒㊰ࡀᏑᅾࡋ࠺ࡿࡇ࡜ࢆ♧ࡋࡓᮏ◊✲ᡂᯝࡣ J. Phys. Chem. C ㄅ࡟࡚Ⓨ⾲ࡋࡓࠋᅗ 1. Catalytic activity of the BN supported Ni cluster,
NiCo cluster and Co cluster.

ᅗ 2. An example of the breakdown of BEP
principle in Ru(1015) under lattice strain.

(3.3) ཯ᛂ≀ࡢ㓄఩࡟ࡼࡾไᚚࡉࢀࡿ཯ᛂ⤒㊰㸸Ni 㘒యゐ፹࡟ࡼࡿ࣋ࣥࢰࣇࣛࣥྜᡂ཯ᛂ㸦ᅗ㸱㸧་⸆ရ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࡿ 2,3-஧⨨᥮࣋ࣥࢰࣇࣛࣥࢆ㸪ศᏊෆ C-O ⤖ྜάᛶ໬ࢆ௓ࡋ࡚ Ni 㘒య࡟ࡼࡾຠ
⋡ⓗ࡟ྜᡂࡍࡿ཯ᛂ࡟ࡘ࠸࡚㸪ᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT㸧ィ⟬ࢆ⏝࠸࡚཯ᛂ⤒㊰ࢆ᳨ウࡋࡓ㸬཯ᛂ㏿ᗘࢆỴᐃࡍࡿࢫࢸࢵࣉࡣ㸪⏕ᡂ≀ࡢ㑏ඖ⬺㞳࡛࠶ࡿࡀ㸪཯ᛂ≀ࡢ Ni 㘒య࡬ࡢ㓄఩࡟ࡼࡾ㸪⏕ᡂ≀ࡢ⇕ຊᏛⓗᏳᐃᛶࡀྥୖࡍࡿࡔࡅ࡛࡞ࡃ㸪ゐ፹ࢧ࢖ࢡࣝࡢ཯ᛂ⤒㊰ࢆỴᐃࡍࡿ࡜࠸࠺⤖ᯝࡀᚓࡽࢀࡓ㸬ࡇࡢ⤖ᯝࡣ㸪࢜ࣞࣇ࢕ࣥ
ࡸ࢔ࣝ࢟ࣥࡢῧຍ࡟ࡼࡗ࡚ C-C ࢝ࢵࣉࣜࣥࢢ⏕ᡂ≀ࡢ㑏ඖⓗ⬺㞳ࡀಁ㐍ࡉࢀࡿ஦ᐇ࡜㛵㐃ࡋ࡚࠾ࡾ㸪ᇶ㉁ࡢ
⮬ᕫゐ፹ຠᯝ࡜ࡋ࡚ㄆ㆑ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ㸬ᮏ◊✲ᡂᯝࡣ Organometallics ㄅ࡟࡚බ⾲ࡋࡓ㸬

ᅗ 3. Substrate-assisted reductive elimination
determining the catalytic cycle of the Ni-catalyzed 2,
3-disubstituted benzofuran Synthesis.

ᅗ 4. Asymmetric dehydrative cyclization of allyl
alcohol to cyclic ether using chiral Brønsted
acid/CpRu(II) hybrid catalysts.

(3.4) ୙ᩧ⬺Ỉ⎔໬཯ᛂࢆゐ፹ࡍࡿ Ru ゐ፹ࡢ཯ᛂᶵᵓ࡟㛵ࡍࡿ◊✲㸦ᅗ㸲㸧࢟ࣛࣝࣆࣜࢪࣥ࢝ࣝ࣎ࣥ㓟ࢆ㓄఩Ꮚ࡜ࡍࡿ Ru 㘒యࡣ㸪࢔ࣜࣝ࢔ࣝࢥ࣮ࣝࢆ⎔≧࢚࣮ࢸࣝ࡬࡜୙ᩧ⬺Ỉ⎔໬ࡍࡿ㸬ࡑࡢ཯ᛂᶵᵓ࡜࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢ㉳※ࢆ DFT ィ⟬࡟ᇶ࡙ࡁ◊✲ࡋࡓ㸬ᚊ㏿ẁ㝵ࡣ⬺Ỉⓗ࡞Ȫ-࢔ࣜࣝᙧᡂ㐣⛬࡛࠶ࡾ㸪ィ⟬ࡉࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡣᐇ㦂ࢹ࣮ࢱ࡜ࡼࡃ୍⮴ࡋࡓ㸬Ȫ-࢔ࣜࣝ୰㛫యࢆ⤒⏤ࡋ࡚୺⏕ᡂ≀࡟⮳ࡿ㐣⛬ࡣ㸪Ỉ⣲⤖ྜ࡜ࣁࣟࢤࣥ⤖ྜࡢ୧᪉࡟ࡼࡗ࡚ಁ㐍ࡉࢀࡿ㸬ࡉࡽ࡟ࠊࣁࣟࢤࣥ࡟౫Ꮡࡍࡿ

- 40 -

άᛶ໬ࢠࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚ࡶᐇ㝿ࡢ཯ᛂᛶࢆ෌⌧ࡋࡓ㸬ࡇࡢࣁࣟࢤࣥഴྥࡢ㉳※ࡣࠊ࢚ࢿࣝࢠ࣮
ศゎゎᯒ࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡉࢀࡓ㸬ࡇࡢ◊✲ᡂᯝࡣ J. Org. Chem.ㄅ࡟࡚Ⓨ⾲ࡋࡓࠋ(3.5) ୙ᆒ୍࡞ᅛᾮ㟁Ẽ஧㔜ᒙ⏺㠃ࡢ⌮ㄽⓗ◊✲㟁ᅽࡢ࠿࠿ࡗࡓᅛᾮ⏺㠃࡟ᙧᡂࡉࢀࡿ㟁Ẽ஧㔜ᒙ࡟ࡘ࠸࡚㸪㟁ụࡸ㟁Ẽศゎ࡬ࡢ⯆࿡࠿ࡽᗈࡃ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓ㸬㏆ᖺ࡛ࡣ㸪ᢸᣢ㔠ᒓࢼࣀ⢏Ꮚ࡞࡝࡜㟁ゎ㉁⁐ᾮ࠿ࡽ࡞ࡿ୙ᆒ୍⣔ࡢ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿ㸬ࡑࡇ࡛ᡃࠎࡣ㸪୙ᆒ୍࡞ᅛᾮ㟁Ẽ஧㔜ᒙ⏺㠃࡟ࡘ࠸࡚ࡢཎᏊࣞ࣋ࣝࡢ▱ぢࢆᚓࡿࡓࡵ࡟㸪㉸୪ิ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛ SALMON ࡜ᾮయࡢ⤫ィຊᏛ⌮ㄽ(3D-RISM ἲ)ࢆ⤌ࡳྜࢃࡏࡓᡭἲࢆ㛤Ⓨࡋࡓ㸬㛤Ⓨࡋࡓᡭἲࢆ⏝࠸࡚㸪㟁ᅽࢆ࠿ࡅࡓࢢࣛࣇ࢓࢖ࢺᢸᣢⓑ㔠ࢼࣀࢡࣛࢫࢱ࣮࡜ KCl Ỉ⁐ᾮ⏺㠃ࡢィ⟬ࢆ⾜ࡗࡓ㸬ࡑࡢ⤖ᯝ㸪ཎᏊࣞ࣋ࣝࡢヲ⣽࡟ࡼࡗ࡚㟁Ẽ஧㔜ᒙࡢ≉ᛶࡀỴᐃ࡙ࡅࡽࢀ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ
ࡓ㸦ᅗ㸳㸧㸬ࡇࡢᡂᯝࡣ J. Phys. Chem. C ㄅ࡟࡚Ⓨ⾲ࡋࡓࠋᅗ 5. The density distribution of
Cl− near the Pt13/graphite electrodesurface.

(3.6) Alchemical perturbation DFT ࢆ⏝࠸ࡓᶵ⬟ᛶศᏊࡢタィἲ࡟㛵ࡍࡿ◊✲㸦ᅗ㸴㸧ೃ⿵࡜࡞ࡿศᏊࡀᏑᅾࡍࡿ໬Ꮫ✵㛫࡟࠾࠸࡚ࠊᡤᮃࡢᶵ⬟ᛶࢆᣢࡘศᏊࢆ᥈⣴ࡍࡿศᏊタィἲࢆ◊✲ࡋ࡚࠸ࡿࠋ᥈⣴㐣⛬࡛ศᏊᵓ㐀ࡢᏳᐃᛶࢆ⪃៖ࡍࡿࡇ࡜ࡣࠊ⌧ᐇⓗ࡞ศᏊࢆタィࡍࡿୖ࡛ᴟࡵ࡚㔜せ࡛࠶ࡿࠋࡇࡇ࡛ࡣࠊTXDQWXPDOFKHP\ ࡟ᇶ࡙ࡁࠊศᏊᵓ㐀ࡢᏳᐃᛶࢆ᫂♧ⓗ࡟⪃៖ࡋ࡞ࡀࡽ໬Ꮫ✵㛫ࢆ᥈⣴ࡋࠊᶵ⬟ᛶศᏊࢆタィࡍࡿ᪉ἲࢆᥦ᱌ࡋࡓࠋᮏ◊✲࡛ࡣࠊࣈ࣮ࣝࢺࣇ࢛࣮ࢫࢫࢡ࣮ࣜࢽࣥࢢ
ࢆ⾜࠺ࡇ࡜࡞ࡃࠊᖹ⾮ᵓ㐀࡟࠾ࡅࡿᶵ⬟ᛶศᏊ࡜ࡑࡢ┠ⓗ࡜ࡍࡿᡤᮃࡢ≉ᛶࢆ㏫タィⓗ࡟ྠ᫬࡟ண

ࡍࡿࡇ࡜ࢆྍ⬟࡟ࡍࡿࡶࡢ࡛࠶

ࡿࠋᮏᡭἲࡣࠊ %)&2  &+1+ ࠊ ✀㢮ࡢ %1 ࢻ࣮ࣉ࣋ࣥࢮ
ࣥㄏᑟయࠊ ✀㢮ࡢ %1 ࢻ࣮ࣉࣇ࢙ࢼࣥࢫࣞࣥㄏᑟయ࡜࠸࠺
ᵝࠎ࡞໬Ꮫ✵㛫࡟࠾࠸࡚ࠊ┠ⓗࡢཎᏊ໬࢚ࢿࣝࢠ࣮࡜㟁Ꮚ࢚ࢿࣝࢠ
࣮ࢆᣢࡘศᏊࢆᚓࡿࡇ࡜࡛ࡑࡢ㐺⏝ᛶࢆド࡛᫂ࡁࡓࠋᮏ◊✲ࡢᡂᯝࡣ㸪-3K\V&KHP/HWWHUV ㄅ࡟࠾࠸࡚Ⓨ⾲ࡋࡓࠋᅗ 6 . Molecular design method for
obtaining a functional molecule bymolecular optimization in a given
chemical space.

(3.7) BPh3 ゐ፹࡟ࡼࡿ࢔࣑ࣥ㢮ࡢ N-࣓ࢳࣝ໬཯ᛂࡢ࣓࢝ࢽࢬ࣒࡟㛵ࡍࡿ◊✲
BPh3 ࡣࠊCO2 ࡜ PhSiH3 ࡢᏑᅾୗࠊ2 ⣭࢔࣑ࣥࡢ N-࣓ࢳࣝ໬ࢆゐ፹ࡍࡿࠋࡇࢀࡽࡢ཯ᛂࡣ↓⁐፹᮲௳ୗࠊ30
ࠥ40Υ࡟࡚㐍⾜ࡍࡿࠋ୍᪉ࠊB(C6F5)3 ࡣ࡯࡜ࢇ࡝άᛶࢆ♧ࡉ࡞࠸ࠋ11B NMR ࢫ࣌ࢡࢺࣝࡣ[HBPh3]-ࡢ⏕ᡂࢆ♧
၀ࡋࡓࠋBPh3 ゐ፹ࢆ⏝࠸ࡓ N-࣓ࢳࣝ࢔ࢽࣜࣥࡢ CO2 ࡜ PhSiH3 ࡟ࡼࡿ N-࣓ࢳࣝ໬཯ᛂ࡟ࡘ࠸࡚ࠊDFT ィ⟬ࢆ⏝࠸࡚ヲ⣽࡞ᶵᵓࢆ᳨ウࡋࡓࠋBPh3 ࡣ 2 ࡘࡢᇶ㉁㸦N-࣓ࢳࣝ࢔ࢽࣜࣥ࡜ CO2㸧ࡢ཮ᛶ࢖࢜ࣥᛶ࢝ࣝࣂ࣓࣮ࢺ
࡬ࡢኚ᥮ࢆಁ㐍ࡋࠊ3 ᡂศ✀[Ph(Me)(H)N+CO2-͐BPh3]ࢆ୚࠼ࡿࠋࡇࡢ࢝ࣝࣂ࣓࣮ࢺ࡜ BPh3 ࡣࡑࢀࡒࢀồ᰾๣࡜ࣝ࢖ࢫ㓟࡜ࡋ࡚ാࡁࠊPhSiH3 ࢆάᛶ໬ࡋ࡚[HBPh3]-ࢆ⏕ᡂࡋࠊ࢔ࢽࣜࣥࡢ N-࣓ࢳࣝ໬࡟୙ྍḞ࡞ࢩࣜࣝࢠ
㓟ࡸࣅࢫ㸦ࢩࣜࣝ㸧࢔ࢭࢱࣝ࡞࡝ࡢ஧㓟໬Ⅳ⣲⏤᮶ࡢ୺せ✀࡟࡞ࡿࠋDFT ィ⟬࡛ࡣࠊ[HBPh3]-✀ࡢ⏕ᡂ࡟Ỉࡀ㛵ࢃࡿ௚ࡢ࣓࢝ࢽࢬ࣒ࡶ♧၀ࡋࡓࠋ◊✲ᡂᯝࡣ㸪Chem. Eur. J. ࡟࡚බ⾲ࡋ㸪hot paper ࡟㑅ࡤࢀࡓࠋ- 41 -

4ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1)

Pt17 Nanocluster Electrocatalysts: Preparation and Origin of High Oxygen Reduction Reaction Activity
T. Kawawaki, Y. Mitomi, N. Nishi, R. Kurosaki, K. Oiwa, T. Tanaka, H. Hirase, S. Miyajima, Y. Niihori, D. J. Osborn, T.
Koitaya, G. F. Metha, T. Yokoyama, K. Iida, Y. Negishi
Nanoscale, accepted, DOI: 10.1039/D3NR01152F(2) ‫ۻ‬First-Principles Study on Unidirectional Proton Transfer on Anatase TiO2 (101) Surface Induced by External Electric Fields
T. Chiba, K. Iida, S. Furukawa, J. Hasegawa
Phys. Chem. Chem. Phys., 25, 9454-9460 (2023), DOI: 10.1039/D3CP00577A(3) ‫ۻ‬Bulky magnesium(II) and sodium(I) bisphenoxide catalysts for chemoselective transesterification of methyl (meth)acrylates
X. Zhao, M. Ratanasak, K. Kon, J. Hasegawa, K. Ishihara
Chem. Sci., 14, 566-572 (2023), DOI: 10.1039/D2SC05413B(4) ‫ ۻ‬Substrate-Assisted Reductive Elimination Determining the Catalytic Cycle: Theoretical Study on the Ni-Catalyzed
2,3-Disubstituted Benzofurans Synthesis via C–O Bond Activation [Selected as Supplementary Cover]
R. Miyazaki, K. Iida, S. Ohno, T. Matsuzaki, T. Suzuki, M. Arisawa, J. Hasegawa
Organometallics, 41(23), 3455-3794 (2022), DOI: 10.1021/acs.organomet.2c00419(5) Unravelling the anomalous coking-resistance over boron nitride supported Ni catalysts for dry reforming of methane
J. Deng, M. Gao, J. Hasegawa, X. Zhang, A. Wang, A. Chen, D. Zhang
CCS Chemistry, 1-14 (2022), DOI: 10.31635/ccschem.022.202202342(6) ‫ۻ‬Iron/Photosensitizer Hybrid System Enables the Synthesis of Polyaryl-Substituted Azafluoranthenes
Y. Kato, T. Yoshino, M. Gao, J. Hasegawa, M. Kojima, S. Matsunaga
J. Am. Chem. Soc., 144, 18450–18458 (2022), DOI: 10.1021/jacs.2c06993(7) ‫ۻ‬Asymmetric Dehydrative Cyclization of Allyl Alcohol to Cyclic Ether Using Chiral Brønsted Acid/CpRu(II) Hybrid
Catalysts: DFT Study of the Origin of Enantioselectivity [Selected as Supplementary Cover]
M. Ratanasak, S. Tanaka, M. Kitamura, J. Hasegawa
J. Org. Chem., 87, 13062–13072 (2022), DOI: 10.1021/acs.joc.2c01576(8) Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane[Selected as Inside Front Cover as a hot paper]
M. Ratanasak, T. Murata, T. Adachi, J. Hasegawa, T. Ema
Chem. Eur. J., e202202210 (2022), DOI: 10.1002/chem.202202210(9) ‫ۻ‬Exploration of Chemical Space for Designing Functional Molecules Accounting for Geometric Stability [Selected as
Supplementary cover]T. Shiraogawa, J. Hasegawa
J. Phys. Chem. Lett., 13, 8620–8627 (2022), DOI: 10.1021/acs.jpclett.2c02355(10) ‫ۻ‬Reaction Mechanism of Deoxydehydration by Ceria-Supported Monomeric Rhenium Catalysts: A Computational Study
R. Hosaka, D. Asada, J. Cao, M. Tamura, Y. Nakagawa, K. Tomishige, J. Hasegawa, A. Nakayama
J. Phys. Chem. C, 126, 11566-11573 (2022), DOI: 10.1021/acs.jpcc.2c02944(11) ‫ۻ‬Identifying substrate-dependent chemical bonding nature at molecule/metal interfaces using vibrational sum frequency
generation spectroscopy and theoretical calculations
B. Wang, M. Ito, M. Gao, H. Noguchi, K. Uosaki, T. Taketsugu
J. Phys. Chem. C, 126, 11298-11309 (2022), DOI: 10.1021/acs.jpcc.2c01608(12) ‫ۻ‬Atomic-Scale Picture of the Electric Double Layer around a Heterogeneous Solid-Liquid Interface Based on 3D-RISM-SCF
TheoryK. IidaJ. Phys. Chem. C, 126, 9466-9474 (2022), DOI: 10.1021/acs.jpcc.2c00872(13) ‫ۻ‬Revisiting Activity Tuning using Lattice Strain: CO Decomposition in Terrace Ru(0001) and Stepped Ru(1015) Surfaces[Selected as Supplementary cover]
D. De Chavez, J. Hasegawa
J. Phys. Chem. C., 126, 9324-9333 (2022), DOI: 10.1021/acs.jpcc.2c00902(14) MD Studies of Methanol Confined in the Metal-Organic Framework MOF MIL-88B-Cl
S. Siwaipram, P. A. Bopp, J.C. Soetens, J. Hasegawa, R. Schmid, S. Bureekaew
J. Mol. Liq., 359, 119252 (2022), DOI: 10.1016/j.molliq.2022.119252(15) ‫ۻ‬Unraveling the promotional effects of NiCo catalysts over defective boron nitride nanosheets in dry reforming of methane
S. Kuboon, J. Deng, M. Gao, K. Faungnawakij, J. Hasegawa, X. Zhang, L. Shi, D. Zhang
Catal. Today, 402, 283-291 (2022), DOI: 10.1016/j.cattod.2022.04.031(16) Exploring the Reaction Mechanism of Heterobimetallic Nickel-Alkali Catalysts for Ethylene Polymerization:
Secondary-Metal-Ligand Cooperative Catalysis
P. Apilardmongkol, M. Ratanasak, J. Hasegawa, V. Parasuk.
ChemCatChem, 14, e202200028 (2022), DOI: 10.1002/cctc.202200028(17) ‫ۻ‬Role of Hydration in Photoexcited Electron Transfer between a Gold Nanocluster and a Water Molecule
K. IidaJ. Phys. Chem. C, 126, 7492-7499 (2022), DOI: 10.1021/acs.jpcc.1c10756(18) Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines ornitrogen-containing aromatics
T. Murata, M. Hiyoshi, S. Maekawa, Y. Saiki, M. Ratanasak, J. Hasegawa, T. Ema
Green Chemistry, 24, 2385-2390 (2022), DOI: 10.1039/D1GC04599G(19) Doubly linked chiral phenanthrene oligomers for homogeneously π-extended helicenes with large effective conjugation length
Y. Nakakuki, T. Hirose, H. Sotome, M. Gao, D. Shimizu, R. Li, J. Hasegawa, H. Miyasaka, K. Matsuda
Nat. Commun., 13, 1475 (10 pages) (2022), DOI: 10.1038/s41467-022-29108-8(20) ‫ۻ‬C-H Bond Activation Mechanism by a Pd(II)-(μ-O)-Au(0) Structure Unique to Heterogeneous Catalysts
D. Takei, T. Yatabe, T. Yabe, R. Miyazaki, J. Hasegawa, K. Yamaguchi
JACS Au., 2, 394-406 (2022), DOI: 10.1021/jacsau.1c00433(21) ‫ۻ‬Photoinduced Copper-Catalyzed Asymmetric Acylation of Allylic Phosphates with Acylsilanes [Selected as back cover]
Y. Ueda, Y. Masuda, T. Iwai, K. Imaeda, H. Takeuchi, K. Ueno, M. Gao, J. Hasegawa, M. Sawamura
J. Am. Chem. Soc., 144, 2218-2224 (2022), DOI: 10.1021/jacs.1c11526,- 42 -

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ôÜ=iHi[fĘ;ƈĳ7"Ĥ'1999 ×'ƈĳg\eAsøÁÃĘ(ĉĬÐĈChem. Phys. Lett. 314, 141 (1999)))(Żī(ÇĀ(2'´ƌĵ'Ù¤969Ģĳĵ&ĹŁĚ;ũŲ"ë) 2000 ×'ƈĳôÜ=iHi[fĘ(¾Ēg\eAsøĘg\eA
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QAXVAfĘ¾ĒğìĘ(kśŮ(ÄÛ'ê96(kŸ(îĘƈĳ'k(7;(ēÐĈJ. Chem. Phys. 130, 214105 (2009))ĈĮŭ)ŠĴű(ð7İ0;p¯ƒ$"ƇōŎĮŭ;Œ7ŵ"ăŴ#)57ÕÙƉÁĽÃJ_bgjJci(¯ƒ'Sj^;ô¿"*ŠĴű,(ŞţÁ(URCiFJ_bgjJci'ëƈĳg\eAsøH

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gjJci57ÌÁ(Ō¨Śĭ?WfDj(ŧņĘ3÷čĂ'9/#)p'¥Ã'¹!
ÁJ_bgjJci;š"×ÈÚĖƊùĘ(DFT)4ÝŌ¨ŴzÈÚĖƊùĘ(DFTB)#ƄÁČ;£79ôÜ=iHi[fĘ(ƈĳ'3ê ë(üĘ(Ĥä)Ćďŷ$"ĤÄ(3(;ī7ýĸ(ÅƕŌČ'«udiP`&Ćďŷ6J_bgjJci;À28$'- 43 -

85&ƃ0)kƟ ƜĹŁêČ
Ĉ×Ú(p&êČƘlÑ6J. Comput. Chem. 44, 1604-1609 (2023)ƙ;vn'Ŷ-8Žyèº;Â"Þê"

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8³Ɲ'(ƞ(a)(ďŷ;ĕų8(b)³ 1. HDAC1(a)$ HDAC2(b)(ł|ďŷ(ĕų.$<%7&Þ;"8$8/³ƞ')ƋÆ KTT-1 (ďŷ;ĺ³ 2.

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ôÜ=iHi[fĘ(k#8ëĦŚ'ƈĳg\eAsøHi\fÁÃĘƘĉĬ- 44 -

ÍÐĈJ. Chem. Phys. 113, 6042-6051 (2000)ƙ;ŞţÁ(OjGRTƁŉÁ,(URCiF'ŻīîĘƘÌqĬoÐĈJ. Comput. Chem. 32, 2810-2821 (2011)ƙ'¹!ÁÃJ_bgjJci;Åš(J_bgjJciŌČ6â69ƋÆ(Ɓŉ,(Ō¨'Ɗ8Ö¶]SiJaf;³Ɵ'ĺ

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  Molecular Simulation 2022: Past, Present, and Future, Celebrating 80th Birthday of Michael L.
KleinƘóßůĝƙErice, Sicily, Italy, June 25-29, 2022.

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  The 10th Conference of the Asia Pacific Association of Theoretical and Computational Chemists(APATCC-10)ƘKeynoteƙQuy Nhon, Vietnam, February 19-23, 2023.

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J. Phys. Chem. B 126, 10646-10661 (2022).

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4. lÑwşƗƅćěĬþnſÐĈ- 46 -

ÁJ. Comput. Chem. 44, 1604-1609 (2023).

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࠸ࡿࠋGẆࡣᡂศࡢ㌶㐨ࢆᣢࡘࡓࡵࠊ⤖ྜᛶࠊ཯⤖ྜᛶ㌶㐨࡜࡜ࡶ࡟ࠊ⤖ྜ࡟㛵୚ࡋ࡞࠸㠀⤖ྜᛶG㌶㐨
ࡀᏑᅾࡋࠊࡑࡢ⤖ᯝࠊGG ㌶㐨࢚ࢿࣝࢠ࣮ᕪࡀᑠࡉࡃ࡞ࡿ࡜ゝ࠺≉ᚩࡀ࠶ࡿࠋࡇࡢࡓࡵࠊከᵝ࡞ཎᏊ౯≧ែࠊ㓟໬ᩘࠊࢫࣆࣥ≧ែࢆ࡜ࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿࠋࡑࡢࡼ࠺࡟ከᵝ࡞㟁Ꮚ≧ែࢆᣢࡕᚓࡿ㑄⛣㔠ᒓඖ⣲࡜᭷ᶵᐁ⬟ᇶࠊ㧗࿘ᮇ඾ᆺඖ⣲ࡸ඾ᆺ㔠ᒓඖ⣲໬Ꮫ✀࡞࡝ࢆྠ᫬࡟ྵࡴG 㟁Ꮚ」ྜ⣔ࡣࠊከᵝ࡛ᰂ㌾࡞㟁Ꮚ≧ែࢆྲྀࡿࡇ࡜ࡀྍ⬟࡛ࠊࡑࡢ⤖ᯝࠊG㟁Ꮚ」ྜ⣔ࡣከᵝ࡞ᵓ㐀ࠊ⤖ྜࠊศᏊ≀ᛶࠊ཯ᛂᛶࢆ♧ࡍࠋᚑࡗ࡚ࠊG㟁Ꮚ」ྜ⣔ࡣศᏊᛶゐ፹ࠊᅛయゐ፹ࠊ㔠ᒓ㓝⣲ࠊኴ㝧㟁ụࡢቑឤ๣ࠊ᭷ᶵ(/ ࡢⓎග⣲ᏊࠊศᏊ☢▼࡞࡝࡜ࡋ࡚ࠊ
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ࡍࡿࡇ࡜ࡣࠊ⌮ㄽ໬Ꮫ࣭ィ⟬໬Ꮫศ㔝ࡢ୰ᚰㄢ㢟ࡢ୍ࡘ࡜ࡶゝ࠼ࡿࠋ

㟁Ꮚ」ྜ⣔ࡢ㟁Ꮚ≧ែࡣᨃ⦰㏥⣔࡛࠶ࡿࡇ࡜ࡶከࡃࠊࡲࡓࠊ⁐፹ຠᯝࡸ⤖ᬗຠᯝࡀ኱ࡁ࠸ࡇ࡜࠿ࡽࠊ࿘

ᅖࡢຠᯝࢆྲྀࡾ㎸ࢇࡔୖ࡛ࠊ኱つᶍ࡞㧗⢭ᗘ㟁Ꮚ≧ែィ⟬ࢆ⾜࠺ᚲせࡀ࠶ࡿࠋᚑࡗ࡚ࠊ᪂ࡋ࠸⌮ㄽィ⟬ἲࡶᚲせ࡜ࡉࢀࠊྠ᫬࡟ィ⟬⤖ᯝࡢṇࡋ࠸ゎᯒἲࡶᚲせ୙ྍḞ࡛࠶ࡿࠋ໬Ꮫ⤖ྜࡸ཯ᛂ㐣⛬࡟ᑐࡍࡿ᪂ࡋ࠸どⅬࠊ᪂ࡋ࠸ᴫᛕࡶᚲせ࡜ࡉࢀࡿሙྜࡶከ࠸ࠋᐇ㝿ࠊ᭱㏆ὀ┠ࡉࢀ࡚࠸ࡿ㔠ᒓᚤ⢏Ꮚࡸ㔠ᒓࢡࣛࢫࢱ࣮ࠊ㔠ᒓ㘒యࡢ㞟ྜయ࡛࠶ࡿ02) PHWDORUJDQLFIUDPHZRUN ࠊ⤖ᬗ࡛࠶ࡾ࡞ࡀࡽᵓ㐀ኚ໬ࡸᶵ⬟ࡢእ㒊่⃭ኚ໬ࢆ♧ࡍࢯࣇࢺࢡࣜࢫࢱࣝ࡟ࡣࠊࡇࢀࡲ࡛ࡢศᏊ⛉Ꮫⓗ⌮ゎࢆ㉸࠼ࡿࡶࡢࡀከࡃࠊᇶ♏࠾ࡼࡧᛂ⏝ศ㔝࡛ G 㟁Ꮚ」ྜ⣔ࡣศᏊ⛉Ꮫ◊✲ࠊ⌮ㄽ໬Ꮫ㺃ィ⟬໬Ꮫ◊✲ࡢ㔜せ࡞◊✲ᑐ㇟࡛࠶ࡿࠋ
ᡃࠎࡣࠊࡇࢀࡲ࡛㑄⛣㔠ᒓඖ⣲ࡸ㧗࿘ᮇ඾ᆺඖ⣲ࢆ࠿ࡂᡂศ࡜ࡍࡿ」ྜ㟁Ꮚ⣔ࡢ㟁Ꮚ≧ែ⌮ㄽ◊✲ࢆ⾜࠸ࠊከᵝ࡞ᵓ㐀ࡸࡇࢀࡲ࡛ࡢ⪃࠼᪉࡛ࡣㄝ࡛᫂ࡁ࡞࠸᪂ࡋ࠸ᵓ㐀ࠊ໬Ꮫ⤖ྜࠊከᵝ࡞໬Ꮫ཯ᛂᛶࠊ᭷⏝࡞ゐ፹స⏝ࢆ㟁Ꮚ≧ែ࡟ᇶ࡙࠸࡚ゎ᫂ࡋࠊ⌮ㄽⓗண࡟ࡶᡂຌࡋ࡚ࡁࡓࠋ ᖺᗘࡣࠊ L  㘒యゐ፹ࠊ᭷ᶵ㔠ᒓ໬Ꮫ཯ᛂ㛵ಀࡢ◊✲࡜ࡋ࡚ࠊ࢖ࣜࢪ࣒࢘ ,,, 㘒య࡟ࡼࡿVS &+ ⤖ྜࡢᐁ⬟ᇶᑟධ཯ᛂࡢ཯ᛂᶵᵓ࡜ゐ፹άᛶࢆᨭ
㓄ࡍࡿᅉᏊࡢゎ᫂ࠊ1L  㘒య࡟ࡼࡿ࢔࣑ࣥࡢ1+ V⤖ྜάᛶ໬཯ᛂࡢ཯ᛂᶵᵓ࡜㧗άᛶ㘒యࡢ⌮ㄽணࠊ LL 

㔠ᒓ㘒యࡢᵓ㐀࡜⤖ྜ࡟㛵ࡍࡿ◊✲࡛ࡣࠊ3G ࡢ  ᰾ࢡࣛࢫࢱ࣮㘒యࡢᵓ㐀࡜Ᏻᐃᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࠊLLL 㔠ᒓゐ፹㛵ಀ࡛ࡣࠊ1L  㠃࡛ࡢ&X$J$Xࡢ༢୍ཎᏊゐ፹࠾ࡼࡧ&X  㠃࡛ࡢ1L3G3W༢୍ཎᏊゐ፹ࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲ࠊ LY  ᅛయゐ፹཯ᛂ㛵ಀ࡛ࡣࠊࢡ࣒ࣟࢆ୺ᡂศ࡜ࡍࡿࢫࣆࢿࣝᆺ㓟໬≀0&U2
ࡢ&XGRSLQJ ࡟ࡼࡿゐ፹άᛶࡢྥୖ࡟㛵ࡍࡿ⌮ㄽண࡜ᐇ㦂ⓗ᳨ドࢆ⾜ࡗࡓࠋ⣬㠃ࡢ㒔ྜୖࠊ୍㒊ࢆ㝖࠸࡚ࠊ௨ୗ࡟ᴫせࢆ㏙࡭ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㑄⛣㔠ᒓ㘒యࡸࡑࡢゐ፹཯ᛂࡢ⌮ㄽⓗ◊✲࡛ࡣࠊDFTἲ࡟ࡼࡾᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮ኚ໬ࢆDFT,- 47 -

MP2 to MP4(SDQ), CCSD(T)ἲ᳨࡛ウࡋࡓࠋDFT ィ⟬࡟ࡣ B3PW91-D3 ࠶ࡿ࠸ࡣZB97XD ஺᥮┦㛵ỗ㛵ᩘ࡞࡝ࢆ⏝࠸ࡓࠋ㑄⛣㔠ᒓඖ⣲ࡢෆẆ㟁Ꮚࡣ Hay-Wadt ࡶࡋࡃࡣ Stuttgart-Dresden-Bonn ࡢ᭷ຠෆẆ࣏ࢸࣥࢩࣕࣝ
(ECP)࡛⨨ࡁ᥮࠼ࠊཎᏊ౯㟁Ꮚ࡟ࡣ split-valence ᆺࡶࡋࡃࡣ triple-zeta ᆺᇶᗏ㛵ᩘࢆ⏝࠸ࡓࠋࡲࡓࠊ㓄఩Ꮚ࡟ࡣᵓ㐀᭱㐺໬ィ⟬࡟ 6-31G(d)ࠊ࢚ࢿࣝࢠ࣮ኚ໬ࡸ㟁Ꮚ≧ែࡢホ౯࡟ࡣ 6-311G(d), cc-pVDZ, cc-pVTZ ᇶᗏ࡞࡝ࢆ
౑⏝ࡋࡓࠋ᭱ప㝈ࠊ཯ᛂ࡟┤᥋㛵ಀࡍࡿཎᏊࡸ㔠ᒓ࡟┦஫స⏝ࡍࡿཎᏊ࡟ࡣ d ศᴟ㛵ᩘࢆࠊ㔠ᒓ࡟ࡣ㹤ศᴟ㛵ᩘࢆຍ࠼ࡓࠋᵓ㐀᭱㐺໬࡜ DFT ィ⟬࡟ࡣࠊ୺࡟ࠊGaussian09 ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋNi㸦111㸧࠾ࡼࡧ Cu(111)㠃࡛ࡢ༢୍ཎᏊศᩓ⾲㠃࠾ࡼࡧ㔠ᒓ㓟໬≀⾲㠃ࡢ⌮ㄽⓗ◊✲࡛ࡣᖹ㠃Ἴᇶᗏ࡜ PBE ỗ㛵ᩘࢆ⏝࠸࡚ࠊ࿘ᮇቃ
⏺᮲௳ୗ࡛ࡢ DFT ィ⟬ࢆ⾜ࡗࡓࠋィ⟬࡟ࡣ VASP ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋ

3㸬◊✲ᡂᯝ
3.1 ࢔࣑ࣝࢼ࣋ࣥࢮࣥࢆ㓄఩Ꮚ࡜ࡍࡿ࢖ࣜࢪ࣒࢘(III)㘒య࡟ࡼࡿ࢔ࣝ࢟ࣝ࢔࣑ࣥࡢ C-H ⤖ྜࡢゐ፹ⓗ࣎ࣜࣝ໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸sp3 C-H ⤖ྜ࡬ࡢᐁ⬟ᇶᑟධ཯ᛂࡣ࢔ࣝ࢝ࣥ࡞࡝ࡢ฼⏝࡟㛵㐃ࡋࠊ㘒యゐ፹໬Ꮫศ㔝࡛ᣮᡓⓗ◊✲ㄢ㢟࡜ࡋ࡚άⓎ࡞◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࠋࡑࢀࡽࡢ୰࡛࢖ࣜࢪ࣒࢘㘒యࢆ⏝࠸ࡓ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬཯ᛂࡣከࡃࡢᡂຌ౛ࡀሗ࿌ࡉࢀࠊᛂ⏝࡟㏆࠸࡜ᮇᚅࡉࢀ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞࢔ࣝ࢟ࣝᇶࡢ
ᐁ⬟ᇶ໬࡛ࡣ఩⨨㑅ᢥᛶࡢไᚚࡀ㔜せ࡛࠶ࡿࠋࡇࢀࡲ࡛ࡢ࢖ࣜࢪ࣒࢘(III)ࣇ࢙ࢼࣥࢺࣟࣜࣥ㘒య࡟ࡼࡿ࣎ࣜࣝ໬཯ᛂ࡛ࡣࠊ࢔ࣝ࢟ࣝ࢔࣑ࣥࡢ
ș఩ࡢ sp3 C-H ⤖ྜ࡛࣎ࣜࣝ໬཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟ࡶሗ࿌ࡉࢀ㸪ᡃࠎࡶ⌮ㄽィ⟬࠿ࡽࡑࡢ⌮⏤ࢆゎ᫂ࡋ࡚ࡁࡓࠋࡋ࠿ࡋࠊȘ఩ࡢ sp3
C-H ⤖ྜࡢ࣎ࣜࣝ໬ࡣሗ࿌౛ࡀ↓࠿ࡗࡓࠋ᭱㏆ࠊ

Scheme 1. Ir(III) aluminabenzen 㘒య࡟ࡼࡿ sp3 CH ⤖ྜࡢᒣୗࡽ㸦ྡ኱㸧ࡣࠊᙼࡽࡀྜᡂࡋࡓ࢔࣑ࣝࢼ࣋

࣎ࣜࣝ໬཯ᛂࡢྍ⬟࡞཯ᛂᶵᵓ

ࣥࢮࣥࢆ㓄఩Ꮚ࡟⏝࠸ࡿࡇ࡜࡟ࡼࡾ࢔
ࣝ࢟ࣝ࢔࣑ࣥࡢȘ఩ࡢ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬࡟ᡂຌࡋࡓࠋ࢔࣑ࣝࢼ࣋ࣥࢮࣥࡢ
㓄఩Ꮚ࡜ࡋ࡚ࡢ≉ᛶࡀࡇࡢࡼ࠺࡞఩⨨㑅ᢥᛶࡢ┦㐪ࢆྍ⬟࡟ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡀࠊ⌮⏤ࡣ᫂ࡽ࠿࡛࡞࠿ࡗࡓࠋ
ᡃࠎࡣ௨๓࠿ࡽ࢖ࣜࢪ࣒࢘㘒య࡟ࡼࡿ
C-H ⤖ྜࡢ࣎ࣜࣝ໬཯ᛂࡢ⌮ㄽⓗ᳨ウࢆ

Scheme 2. Ir(III) aluminabenzen 㘒య࡟ࡼࡿ᭷ᶵ࢔࣑ࣥࡢ sp3 CH⾜࠸ࠊ཯ᛂᶵᵓ࡜఩⨨㑅ᢥᛶ࡞࡝ࢆゎ᫂⤖ྜࡢ࣎ࣜࣝ໬཯ᛂࡢ཯ᛂᶵᵓ

ࡋ࡚ࡁࡓࠋࡇࢀࡲ࡛ࡣ࢖ࣜࢪ࣒࢘ࡀࣇ࢙ࢼࣥࢺࣟࣜࣥ㓄఩Ꮚࢆᣢࡘሙྜࡣ Scheme 1A ࡟♧ࡍ Ir(III)-Ir(V)ࢧ࢖
ࢡ࡛ࣝࠊᔞ㧗࠸㓄఩Ꮚࢆᣢࡘሙྜࡣ Scheme 1 ࡢ(B)࡟♧ࡍ Ir(I)㸫Ir(III)ࢧ࢖ࢡ࡛ࣝ཯ᛂࡀ㐍⾜ࡍࡿ࡜⪃࠼ࡽࢀ࡚ࡁࡓࠋ࢔࣑ࣝࢼ࣋ࣥࢮࣥ㓄఩Ꮚࡢሙྜࠊ࢚ࢳࣝ࢔࣑ࣥࡢș఩ࡢ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬ࡣ Scheme 1A ࡟♧ࡍ Ir(III)-Ir(V)ࢧ࢖ࢡ࡛ࣝ㐍⾜ࡍࡿࡀࠊȘ఩ࡢ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬ࡣ Ir(III)-Ir(V)ࢧ࢖ࢡࣝࠊIr(I)-Ir(III)ࢧ࢖
ࢡࣝ࠸ࡎࢀ࡛ࡶ࡞ࡃࠊScheme 2 ࡟♧ࡍࡼ࠺࡟ࠊȘ఩ࡢ H ཎᏊࡀࣄࢻࣜࢻ࡜ࡋ࡚ Ir ࡟⛣ືࡋ࡚⏕ᡂࡍࡿᑐ࢖࢜
ࣥ୰㛫యࢆ⤒࡚㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡲ࡛࡟↓࠸཯ᛂᶵᵓ࡛࠶ࡿࠋ⏕ᡂࡋࡓ CH2=CHNR2 ୰- 48 -

㛫యࡀ Ir-Bpin ⤖ྜ࡟ᤄධࡋ࡚ࠊȘ఩ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬ࡀ㐩ᡂࡉࢀࡿࠋࡇࡢ⤒㊰ࡣࠊȘ఩ࡢ C-H ⤖ྜࡣ࢔࣑ࣝࢼ࣋ࣥࢮࣥ࡜ࡢ❧య཯Ⓨ࡜⏕ᡂࡍࡿ࢔ࢽ࢜ࣥ⏕ࡢ Ir ࣄࢻࣜࢻ㘒యࡀ࢔࣑ࣝࢼ࣋ࣥࢮࣥ࡟ࡼࡾᏳᐃ໬ࡉ
ࢀࡿࡓࡵ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ㸦R-L Jheng, S.Sakaki, ACS. Cat. 2022, 12, 4880㸧
3.2 1L  㠃࡛ࡢ &X$J$X ࡢ༢୍ཎᏊゐ፹࠾ࡼࡧ &X  㠃࡛ࡢ 1L3G3W ༢୍ཎᏊゐ፹ࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲㸸⮬ື㌴ゐ࡟ࡣⓑ㔠᪘ඖ⣲ࡀ౑⏝ࡉࢀ࡚࠸ࡿࡀࠊ㈨※ಖ඲ࠊάᛶྥୖࠊప౯᱁໬࡞࡝ࡢ┠ⓗ࡛ࠊ㈨※ⓗ࡟ၥ㢟ࡀᑠࡉ࠸ Ni ࡸ Cu ࢆẕయ࡜ࡋࠊࡑࢀࡽ࡟㈗㔠ᒓࢆ㧗ศᩓࡉࡏࡓ༢୍ཎᏊゐ፹ࡀ⯆࿡ࢆ㞟ࡵ࡚࠸ࡿࠋࡋ࠿ࡋࠊ࡝ࡢࡼ࠺࡞⤌ࡳྜࢃࡏ࡛༢୍ཎᏊྜ㔠࡜࡞ࡿࡢ࠿ࠊ┦ศ㞳ྜ㔠࡟࡞ࡿࡢ࠿ࠊ࡝ࡢࡼ࠺࡟⾲㠃㟁Ꮚ≧ែࡀᦤືࢆཷࡅࡿࡢ࠿ࠊ࡞࡝ࡢ▱ぢࡣஈࡋ࠸ࠋࡲ
ࡓࠊ༢୍ཎᏊศᩓྜ㔠ࡢ㟁Ꮚ≧ែࡣᇶ♏໬Ꮫⓗ࡟ࡶ⯆࿡῝࠸ࠋᮏ◊✲࡛ࡣ NO ゎ㞳྾╔άᛶࢆᣢࡘ Ni(111)
࠾ࡼࡧ Cu(111)⾲㠃࡟ 11 ᪘ඖ⣲ࡸⓑ㔠᪘ඖ⣲ࢆᢸᣢࡋࡓ⾲㠃ࡢྜ㔠ࡢᵓ㐀࡜㟁Ꮚ≧ែࢆ DFT ィ⟬࠿ࡽ᳨ウ

Scheme 3. Schematic presentation of single atom
alloy and phase separated alloy.

ࡋࡓࠋScheme 3 ࡟♧ࡍࡼ࠺࡟ࠊᵝࠎ࡞఩⨨࡟Ꮩ❧ཎᏊࡸࢡࣛࢫࢱ࣮ࢆ㓄⨨ࡋࠊ࡝ࡕࡽࡀᏳᐃ࡛࠶ࡿ࠿ࠊPBE ỗ㛵ᩘࢆ౑⏝ࡋࡓ࿘ᮇቃ⏺᮲௳ DFT ィ⟬᳨࡛ウࡋࡓࠋ⤖ᯝࢆ
Scheme 4 ࡟ࡲ࡜ࡵࡓࡀࠊNi(111)㠃࡛ࡣ Au ཎᏊࡣ༢୍ཎᏊ⾲㠃(SAA)ࢆᙧᡂࡋࠊCu ཎᏊࡣ┦ศ㞳⾲㠃(SAA)ࢆᙧᡂࡍࡿࠋ
Ag ࡣ⃰ᗘࡀప࠸ሙྜࡣ SAA ࢆࠊ⃰ᗘࡀ㧗࠸ሙྜࡣ PSA ࢆᙧᡂࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ୍᪉ࠊCu(111)㠃࡟ᑐࡋ࡚ࡣ Pd, Pt

Scheme 4. Single atom alloy (SAA)࠶ࡿ࠸ࡣ
phase separated alloy (PSA)ࢆྲྀࡿ⤌ࡳྜࢃࡏࡢ࠸ࡎࢀࡶࡀ SAA ࢆᙧᡂࡍࡿࡀࠊNi ࡣ㧗⃰ᗘ࡛ PSA ࢆࠊప⃰ᗘ࡛ࡣ SAA ࢆᙧᡂࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡽࡢഴྥࡣࠊẕయ࡜࡞ࡿ Ni(111)࠾ࡼࡧ
Cu(111)ࡀྜ㔠࡜࡞ࡗࡓሙྜࡢṍࡳ࢚ࢿࣝࢠ
࣮ࠊࡑࢀࡽࡢ⾲㠃࠿ࡽᩘཎᏊࢆྲྀࡾཤࡿ୙Ᏻ
ᐃ໬࢚ࢿࣝࢠ࣮ࠊࡑࡢࡼ࠺࡟ᙧᡂࡉࢀࡓ✵Ꮝ࡟༢୍ཎᏊࡶࡋࡃࡣࢡࣛࢫࢱ࣮ࢆධࢀ㎸ࡴࡇ࡜࡟࡞ࡿᏳᐃ໬࢚ࢿࣝࢠ࣮࡟ࡼࡾỴᐃࡉࢀ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊFigure 1(a) PSA࡟♧ࡍࡼ࠺࡟ࠊࢤࢫࢺ㔠ᒓཎᏊࡣ Ni(111)࠾ࡼ

Figure 1. ࢤࢫࢺ㔠ᒓཎᏊࡢ Bader charge ࡜㔠ᒓྜ㔠ࡢࣇ࢙ࡧ Cu(111)⾲㠃࡛ࢃࡎ࠿࡟࣐࢖ࢼࢫࡢ㟁Ⲵࢆ࣑ࣝ‽఩(b) SAA

ᣢࡕࠊNi(111), Cu(111)࠿ࡽࢤࢫࢺཎᏊ࡬ࡢ㟁Ⲵ⛣ືࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࠊࡑࡢࡓࡵࠊࢤࢫࢺཎᏊࡢᢸᣢ㔞ࡀቑ࠼ࡿ࡟ᚑ࠸ࠊࣇ࢙࣑ࣝ‽఩ࡀ࢚ࢿࣝࢠ࣮పୗࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࠊྜ㔠࡛ࡣ NO ゎ㞳ࡀᢚไࡉࢀࡿࡀࠊCO2 ࠾ࡼࡧ N2 ⏕ᡂࡣಁ㐍ࡉࢀࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋNi(111)ࡣ NO-CO ཯ᛂ࡛ࡣኻάࡍࡿࡀࠊCu ࡸ
Au ࢆᢸᣢࡍࡿ࡜ኻάࡀᢚไࡉࢀࡿ࡜࠸࠺ᐇ㦂⤖ᯝࢆࢧ࣏࣮ࢺࡍࡿ㟁Ꮚ≧ែࡢኚ໬࡛࠶ࡿࠋ
㸦J. Yin, M. Ehara, S.
Sakaki, Phys. Chem. Chem. Phys. 24, 10420-10438 (2022)㸧.
3㸬3ࢫࣆࢿࣝᆺ㓟໬≀ 0&U2㸦0 =QRU0J㸧ࡢ &XGRSLQJ ࡟ࡼࡿゐ፹άᛶࡢྥୖ࡟㛵ࡍࡿ⌮ㄽண࡜ᐇ㦂ⓗ᳨ド ࢡ࣒ࣟࡢ」ྜ㓟໬≀࡛࠶ࡿࢫࣆࢿࣝ 0&U2 ࡣⓑ㔠᪘ඖ⣲ࢆ౑⏝ࡋ࡞࠸⮬ື㌴୕ඖゐ፹࡜ࡋ࡚᭱㏆- 49 -

ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋࡑࡢ⾲㠃ࡢ 0 ཎᏊࢆ㐺ษ࡞ඖ⣲࡟⨨ࡁ᥮࠼ࡿࡇ࡜࡟ࡼࡾࠊ⾲㠃㟁Ꮚ≧ែࡀไᚚ࡛ࡁࠊゐ፹άᛶࢆྥୖࡉࡏࡿࡇ࡜ࡀྍ⬟࡜ᮇᚅࡉࢀࡿࠋࡑࡇ࡛ࠊ0&U2 ࡢ⾲㠃ࡢ =Q ࠶ࡿ࠸ࡣ 0J ཎᏊࢆ &X ࡛⨨᥮ࡋࡓࢫࣆࢿࣝ㓟໬≀ࡢࣔࢹࣝࢆ 6FKHPH  ࡟♧ࡍࡼ࠺࡟ᵓ⠏ࡋࠊ&X ಟ㣭ࢫࣆࢿࣝ㓟໬≀࡟ࡼࡿ &2 㓟໬཯ᛂࢆ')7 ィ⟬᳨࡛ウࡋࡓࠋ0 ࢆ⨨᥮ࡋࡓ &X ࡣෆ㒊࡛࡞ࡃࠊ⾲㠃࡟Ꮡᅾࡍࡿࡇ࡜ࠊࡑࢀࡣ⤖ᬗࡢṍࡳ࢚ࢿࣝࢠ࣮
ࡀ⾲㠃⨨᥮ࡢሙྜ࡟ᑠࡉ࠸ࡓࡵ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡉࡽ࡟ࠊ)LJXUH ࡟♧ࡍࡼ࠺࡟ࠊ0 =Q ࡢሙྜࡶࠊ
0 0J ࡢሙྜࡶࠊ&X ࡟⨨᥮ࡉࢀࡿ࡜➨㸯ẁ㝵ࡢ &2 㓟໬཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀࠊ๓⪅࡛ࡣ H9 ࠿ࡽH9 ࡟ࠊᚋ⪅࡛ࡣ H9 ࠿ࡽ  H9 ࡟పୗࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ➨୍ẁ㝵ࡢ &2 㓟໬ࡣࠊ0DUVYDQ

Scheme 5. All possible elementary
steps in Pt-catalyzed O2 reduction
reaction.UHYHOHQ ᶵᵓ࡛㐍⾜ࡍࡿࡇ࡜ࠊࡑࡢ㝿

Figure 2. Energy changes in CO oxidation by Cu-modified spinel oxide
M2Cr2O4 (M = Zn or Mg)

࡟ࠊ0 ࡀ =Q ࡸࠕ0J ࡢሙྜࠊ⾲㠃㓟⣲ཎᏊࡢ 0 ࡜ࡢ⤖ྜࡀᙉ࠸ࡓࡵ࡟άᛶ໬࢚ࢿࣝࢠ࣮ࡀ㧗ࡃ࡞ࡿࡀࠊ0 ࡀ &X ࡟⨨᥮ࡉࢀࡿ࡜ࠊ⾲㠃㓟⣲ཎᏊࡢ⤖ྜࡀᙅࡃ࡞ࡾࠊ&2 㓟໬ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀపୗࡍࡿࡓࡵ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᐇ㝿࡟ࠊ⸃ᦶࢢ࣮ࣝ
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- 52 -¤Åᒁᡤ≀⌮㔞ࢆ⏝࠸ࡓ࢖࢜ࣥ࡜ࢫࣆࣥࡢࢲ࢖ࢼ࣑ࢡࢫゎᯒ
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⛉㸧


◊✲┠ⓗ
ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙࠸࡚ᐃᘧ໬ࡉࢀࡓᒁᡤ≀⌮㔞࡟ࡼࡾࡼࡿཎᏊ࣭ศᏊ࡟ᑐࡍࡿ໬Ꮫ࣭≀⌮ࡢ⌧㇟ࠊ≉࡟ࢲ࢖ࢼ࣑ࢡࢫࢆグ㏙ࡍࡿ⌮ㄽ࡟ᑐࡍࡿ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋሙࡢ㔞Ꮚㄽࡣ┦ᑐᛶ⌮ㄽ࡜ᩚྜࡍࡿ㔞Ꮚㄽࡢᯟ⤌ࡳ࡛࠶ࡾࠊᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ㐣ཤ࡟㔞ᏊຊᏛ࡟ᇶ࡙ࡁゎᯒࡀ⾜ࢃࢀⓎᒎࡋ࡚ࡁࡓ஦㇟ࡢ⌮ゎࢆሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡁ෌⪃ࡋࠊ㔞Ꮚ໬Ꮫศ㔝࡟᪂ࡓ࡞Ⓨᒎⓗ⌮ゎࢆྲྀࡾ㎸ࡴ◊✲ࢆ᥎㐍ࡋ࡚࠸ࡿࠋᮏᖺᗘࡢ◊✲࡛ࡣࠊ࢖࢜ࣥࡢࢲ࢖ࢼ࣑ࢡࢫࢆᒁᡤⓗ࡞໬Ꮫ࣏ࢸࣥࢩࣕࣝ࡟ᇶ࡙ࡁグ㏙ࡍࡿ⌮ㄽⓗ◊✲࡜ࠊ㟁Ẽఏᑟ࡟࠾ࡅࡿࢫࣆࣥ
ศᴟࡢⓎ⏕ࡢ⌮ㄽⓗ◊✲ࠊ≉࡟ࢫࣆࣥ ࡜㟁ὶࡢ㛵ಀࡘ࠸࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ࢖࢜ࣥࢲ࢖ࢼ࣑ࢡࢫࡢ◊✲࡛ࡣᒁᡤⓗ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢィ⟬ᡭἲ࡜ࡋ࡚ࠊ᭱ప✵㌶㐨ࡢィ⟬ࢆ฼⏝ࡋࡓ᪂ࡓ࡞㏆ఝᡭἲࢆ⪃᱌ࡋࡓࠋࡇࡢ㏆ఝᡭἲࡀ᪤᭷⏝࡛࠶ࡿࡇ࡜ࢆ᳨ドࡍࡿࡓࡵ࡟ Pt ࢡࣛࢫࢱ࣮࡬ࡢỈ⣲ศᏊ྾╔⌧㇟࡜ࢥࣟࢿࣥ࡬ࡢࣜࢳ࣒࢘ཎᏊ྾╔⌧㇟࡟࠾࠸࡚ࠊᒁᡤⓗ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡀṇࡋࡃ྾╔఩⨨ࢆணゝ࡛ࡁࡿ࠿ࢆ◊✲ࡋࡓࠋࡇࡢ◊✲࡟ࡣ Gaussian ࢆ⏝࠸࡚㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋᒁᡤ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢィ⟬࡟ࡣ QEDynamics (https://github.com/mfukudaQED/QEDalpha) ࢆ⏝࠸ࡓࠋ㟁Ẽఏᑟ࡟࠾ࡅࡿࢫࣆࣥศᴟࡢ◊✲࡟࠾࠸࡚ࡣࠊࢫࣆࣥ

࡜㟁ὶࡢ㛫࡟⥺ᙧ㛵ಀࢆணゝࡋ࡚࠾ࡾࠊࡇࡢ⥺ᙧ㛵ಀࡢ᳨ドࢆ⾜ࡗࡓࠋ ḟඖⓗᵓ㐀ࢆᣢࡘࡇ࡜࠿ࡽ࣊ࣜࢭࣥࢆ◊✲ᑐ㇟࡜ࡋࠊࡑࡢ୧➃࡟Ⅳ⣲ࢆ㟁ᴟ࡜ࡋ࡚ࡘ࡞ࡆࡓࣔࢹࣝࢆ᥇⏝ࡋࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲ࡟ࡼࡾ㟁Ẽఏᑟ≧ែࡢἼື㛵ᩘࢆィ⟬ࡋࡓࠋᵝࠎ࡞ࣂ࢖࢔ࢫ㟁ᅽ࡟ᑐࡋ࡚ࠊࢫࣆࣥ

࡜㟁ὶࡢศᕸࢆィ⟬ࡋࠊࢫࣆࣥ

࡜㟁ὶࡢ㛫ࡢ⥺ᙧ㛵ಀࢆ᳨ドࡍࡿࠋࡇࡢ㟁Ꮚ≧ែィ⟬࡟ࡣ OpenMX ࢆ⏝࠸ࠊࡑࡢἼື㛵ᩘ࠿ࡽࢫࣆࣥ ࢆィ⟬ࡍࡿ㝿ࡣ QEDynamics ࢆ⏝࠸ࡓࠋ



◊✲ᡂᯝ
ᒁᡤⓗ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ᪂ࡓ࡞㏆ఝᡭἲࡢ᳨ド࡜ࡋ࡚ࠊ᪂ࡓ࡞㏆ఝᡭἲࡀ Pt ࢡࣛࢫࢱ࣮ୖ࡬ࡢṇࡋ࠸Ỉ⣲྾╔఩⨨ࢆணゝࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋᐇ㝿ࡢ྾╔఩⨨ࡢணゝ࡜ࡋ࡚ࡣᗈ࠸⠊ᅖ࡛ࡢணゝ࡜࠸࠺ᙧ࡛࠶ࡗࡓ
ࡢ࡛ࠊ᭦࡞ࡿ᳨ド࡜ࡋ࡚ࢥࣟࢿࣥ࡬ࡢࣜࢳ࣒࢘ཎᏊ྾╔⌧㇟ࡶ◊✲ࡋࡓࠋࢥࣟࢿࣥୖࡢᑐ⛠ᛶ࠿ࡽ༊ูࡉࢀ
ࡿ top, bridge, hollow ࡢ඲࡚ࡢ྾╔఩⨨ࢆẚ㍑᳨ウࡋࠊࡘࡁࡸࡍ࠸㡰␒ࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿ᪉ἲࢆ⪃᱌ࡋࡓࠋ྾╔࢚ࢿࣝࢠ࣮ࡀ㧗ࡃ㔜せ࡛࡞࠸྾╔఩⨨ࡢ㡰␒࡛ࡣṇࡋࡃணゝ࡛ࡁ࡞࠸ࡇ࡜ࡶ࠶ࡗࡓࡀࠊ㔜せ࡞྾╔఩⨨ࡢ㡰␒ࡣ㐺ษ࡟ணゝ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋᒁᡤⓗ໬Ꮫ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡞࠸᪤Ꮡࡢ᪉ἲ࡛ࡣ྾╔఩⨨ẖ࡟ཎᏊࢆ⨨࠸ࡓ≧ែィ⟬ࢆ⾜࠺ࡀࠊᮏ᪉ἲ࡛ࡣ྾╔ཎᏊ↓ࡋࡢࣔࢹࣝࡢィ⟬ࡔࡅ࠿ࡽ྾╔఩⨨ࡢணゝࡀྍ⬟࡛࠶ࡾࠊ᱁ẁ࡟పࢥࢫࢺ࡛࠶ࡿࠋ
㟁Ẽఏᑟ࡟࠾ࡅࡿࢫࣆࣥ

࡜㟁ὶࡢ㛫ࡢ⥺ᙧ㛵ಀࡢᐇド◊✲࡛ࡣࠊ࣋ࢡࢺ࡛ࣝ࠶ࡿࢫࣆࣥ

࡜ࠊ࣋ࢡࢺࣝ

࡛࠶ࡿ㟁ὶࡢ㛫ࡢࢸࣥࢯࣝࢆ௓ࡋࡓ⥺ᙧ㛵ಀࡢ☜ㄆ᪉ἲࡢ᳨ウ࠿ࡽጞࡵࠊࢸࣥࢯࣝࡢ  ᡂศࡢ஧஌ㄗᕪࢆ᭱
ᑠ࡜ࡍࡿࡼ࠺࡟⥺ᙧ㛵ಀࢆᐃࡵࡿ᪉ἲࢆ⪃᱌ࡋࡓࠋࡑࡢ᪉ἲ࡟ᇶ࡙࠸࡚ࠊⅣ⣲㟁ᴟࢆᣢࡘ࣊ࣜࢭࣥࣔࢹࣝ࡟

- 53 -

ᑐࡋ࡚㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲ࡟ࡼࡾ  ㏻ࡾࡢࣂ࢖࢔ࢫ㟁ᅽ࡟ᑐࡋ࡚㟁Ẽఏᑟ≧ែࡢィ⟬ࢆ⾜࠸ࠊࢫࣆࣥ ࡜㟁ὶᐦᗘࡢศᕸࢆィ⟬ࡋࡓࠋࡑࢀ࡟ᇶ࡙ࡁ⥺ᙧ㛵ಀࢆ⾲ࡍࢸࣥࢯࣝࢆỴᐃࡋࠊࡑࡢྛⅬྛⅬ࡛ࡢㄗᕪࢆィ⟬ࡋࡓࡀࠊࡑࡢㄗᕪࡣࢸࣥࢯࣝࡢྛᡂศࡢ್ࡼࡾࡶ㠀ᖖ࡟ᑠࡉ࠸ࡶࡢ࡛࠶ࡾࠊࡇࡢ⥺ᙧ㛵ಀࡀ㧗࠸⢭ᗘ࡛ᡂ❧ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡍࡇ࡜ࡀ࡛ࡁࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] Naoya Kuroda, Ayaki Sunaga, and Masato Senami, (Oral), “Enhancement of the parity-violating energy difference inelectronic excited states of chiral molecules”, The 8th Quantum Science (QS) symposium -The Main Symposium of
ICCMSE 2022, 2022/10/26-29, Galaxy Hotel, Crete, Greece and online.
[2] ℩Ἴ ኱ᅵ, (ᣍᚅㅮ₇, ཱྀ㢌), “Electron chirality in chiral molecule and homochirality in nature”,
ィ⟬࢔ࢫࢺࣟࣂ࢖࢜ࣟࢪ࣮2022, 2022/11/10-11, ⟃Ἴ⤎Ꮫィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮[3] 㯮⏣ ┤ஓ㸪◁㈡ ᙬග㸪℩Ἴ ኱ᅵ, “㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪࡢ㟁Ꮚບ㉳࡟ࡼࡿቑ኱-࢝࢖ࣛࣝศᏊࡢᵓ
㐀࡟ᑐࡍࡿ౫Ꮡᛶ- ”, ➨ 24 ᅇ⌮ㄽ໬Ꮫウㄽ఍, 2022/5 ᭶ 17-20, 㔠ἑၟᕤ఍㆟ᡤ
[4] ⏣୰ ᾏᩯ㸪℩Ἴ ኱ᅵ, “᭱ప✵㌶㐨ࢆ⏝࠸ࡓᒁᡤ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ㏆ఝᡭἲ”, ➨ 24 ᅇ⌮ㄽ໬Ꮫウㄽ఍,
2022/5 ᭶ 17-20, 㔠ἑၟᕤ఍㆟ᡤ
[5] Naoya Kuroda, “Enhancement of the parity-violating energy difference of chiral molecules by electronic excitation”,
RCNP ◊✲఍ ࠕ୰ᛶᏊ࡜ཎᏊ࡛᥈ࡿᇶ♏≀⌮ࠖ 2022/8/12-13, ࢜ࣥࣛ࢖ࣥ
[6] 㯮⏣ ┤ஓ, ◁㈡ᙬග, ℩Ἴ ኱ᅵ, “CHFClBr ศᏊ࡟࠾ࡅࡿࣃࣜࢸ࢕◚ࢀ࡟㉳ᅉࡋࡓ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪࡢ㟁Ꮚບ㉳࡟ࡼࡿቑ኱”, ᪥ᮏ≀⌮Ꮫ఍ 2022 ᖺ⛅Ꮨ኱఍, 2022/9/12-15, ᮾிᕤᴗ኱Ꮫ(኱ᒸᒣ࢟ࣕࣥࣃࢫ).
[7] ⏣୰ ᾏᩯ㸪℩Ἴ ኱ᅵ, “᭱ప✵㌶㐨ࢆ⏝࠸ࡓᒁᡤ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ㏆ఝᡭἲ”, ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍
2022 ᶓ὾, 2022/9/19-22, ៞᠕⩏ሿ኱Ꮫ ▮ୖ࢟ࣕࣥࣃࢫ.
[8] 㯮⏣ ┤ஓ㸪◁㈡ ᙬග㸪℩Ἴ ኱ᅵ, “CHFClBr ศᏊࡢ㟁Ꮚບ㉳≧ែ࡟࠾ࡅࡿ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪቑ
኱ຠᯝࡢ┦ᑐㄽⓗ EOM-CC ἲ࡟ࡼࡿⓎぢ”, ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍ 2022 ᶓ὾, 2022/9/19-22, ៞᠕⩏ሿ኱Ꮫ▮ୖ࢟ࣕࣥࣃࢫ.
[9] Naoya Kuroda,͆(QKDQFHPHQWRIWKHSDULW\YLRODWLQJHQHUJ\GLIIHUHQFHRIFKLUDOPROHFXOHVE\EUHDNLQJWKH
FDQFHOODWLRQDPRQJRUELWDOVGXHWRHOHFWURQH[FLWDWLRQ͇, The 14th International Workshop on Fundamental Physics Using
Atoms (FPUA2022), 2022/11/24-25, ஑ᕞ኱Ꮫ[10] 㯮⏣ ┤ஓ㸪◁㈡ ᙬග㸪℩Ἴ ኱ᅵ,͆┦ᑐㄽⓗ EOM-CC ἲࢆ⏝࠸ࡓ CHFClBr ศᏊࡢ㟁Ꮚບ㉳≧ែィ⟬:ࣃࣜࢸ࢕ࢆ◚ࡿ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪࡢቑ኱͇, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ 2022, 2023/1/1617, ࢜ࣥࣛ࢖ࣥ
[11] 㯮⏣ ┤ஓ㸪◁㈡ ᙬග㸪℩Ἴ ኱ᅵ,͆CHFClBr ศᏊ࡟࠾ࡅࡿࣃࣜࢸ࢕ࢆ◚ࡿ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪ
ࡢ㟁Ꮚບ㉳࡟ࡼࡿቑ኱͇, ➨ 18 ᅇி㒔኱Ꮫ⚟஭ㅬ୍グᛕ◊✲ࢭࣥࢱ࣮ࢩ࣏ࣥࢪ࣒࢘, 2023/2/10, ி㒔኱Ꮫ⚟஭ㅬ୍グᛕ◊✲䝉䞁䝍䞊[12] 㯮⏣ ┤ஓ㸪℩Ἴ ኱ᅵ,͆㟁Ꮚບ㉳࡟ࡼࡿ㙾ീ␗ᛶయศᏊ୰ࡢ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡢቑ኱͇, ᪥ᮏ≀⌮Ꮫ఍
2023 ᖺ᫓Ꮨ኱఍, 2023/3/22-25, ࢜ࣥࣛ࢖ࣥ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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- 54 -

*(4) Al
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



(#

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Elucidating properties of reactive diborane(4)s and Al anion species,and design of homogeneous catalyst toward C-H activation of methane #%

$&

 
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&-5RSÕ &)( W:-MF· $O -D1V 6P, m%'-SLDSÔaz,(  ÔaØb &)( W->LV=Vß,(À 3&3 HV8X,U Øb Ây-S2V»´jº,( W:-MF· $O -D1VÕwjm%'-9S-SMD/N® &)(  ¥Ç`Z 5 ÆÝ,«°©¨¯;KX;ÓpY(1)"¬  :-MF· $O -D1V%'p $O6F k¶pj|®Ûz¨ÉmÁ §½È    6-D:VrHV8X5K Øb,Ây0?TV &2

&-5RSÕÅbp (·uiÁ §½È    :-MF· $O -D1V%'p $O6P$O ØbÉÁ §½ 
  À´·2SJVHV8XÔaz,(×Øb%(-S2VÂy¨»´jm §½
  :-MF· $O -D1V%'p-9S-SMD/N®¶p mÁ È¯[  "¶ÍBX=,eGaussian 16 %' 2 ÍÐj,¼[B3LYP/LanL2DZ (for Sc)/6-31+G(d) (forothers), DFT-D3BJ]p+2
[Úb%

Ñ­¡&34¢(m·u,ª¦OBS³(2’-4’),£ÍÐj,¼))mµÊ0ES4X,#[B97XD/Def2-TZVP (for Sc, Al)/6-31G(d) (for others), PCM(SMD, benzene))

 
Ì Al -D1V 1 , ClSc(thf)2(NiPr2)2 m( )!vsc Al–Sc k¶p,Øb 2¢( ,¿[Scheme 1(a)]!2 ,JV<V[ Ph2CHBr m

*JV<V 2 d Al lz _h 3 GU7Vj-S3S¤-S3Su
(42 Öj 4¢¢(  &m Al–Sc ¶p t±Ù¾Q:2SÎ¼( ¸o®~Þ,¼$Q:2Sm(nºq})«° 2 Ûz¡- 55 -

%

2

& 3,4

¢(m,Á(# DFT Ã²,¼

! DFT Ã²%' 2 IUVA.-ËÏ,ÁHOMO \ Al ·+´lz2fÛzHOMO-1 \ Al–Sc k¶p
LUMO %

LUMO+2 \ Al lz%Sc lz*ËÏ ¶p) £,-p*ËÏ(ª¦) )&ËÏÉ vs Al–Y Øb$3 & Al–Sc Øb 2 JV<V%

Ph2CHBr (b)mOBSuÉ,Ã²( &)m, Scheme 1(b)!#! 2’
Ph2CHBr ,´lz
-MFu

Scheme 1. (a) Synthesis and reaction of Al–Sc complex 2, (b) DFT-based reaction mechanism(a)thf NiPr2
thf
Sc
thf
Cl
thf i
Ph
Ph
K
NiPr2
N Pr2 Ph2CHBr
0.5 Al
+ 0.5
Al Sc
Al
Al
Al
62%
C
H
Ph
Ph
6 6
K
thf
NiPr2
3
4
Dip
2
1
(50%)
(74%)
N
Al =
Al
N
Dip
Ph2HC
Br
NMe2 BrCHPh2
NMe2
Al Sc thf
Al Sc
thf
N
NMe2
2’
5’ Me2Sc Ôa(f Sc Y

C 6H 6

Al lz#%ÔaAl Òa -1,2shiftof thf(& 2 Ö© Ph2CHBr

6’ Al lzÔa

N

Al =

Al Br
10’

Al
N

Al
4

H
Al

H

Al

Al

NMe2 thf
Sc
NMe2
11’
12’ Me2N NMe2

thf

Sc

thf

CHPh2
BrCHPh2
Br
NMe2 thf
N Sc
Sc (NMe2)2
thf
Me2
Br 7’
CHPh2

Al

Br CHPh29’Ph

8’, gz C–C ¶p¢m/  4 fUO-SLV 10’, (6’Ph

D1V Ph2CH Òa,(  Al–Sc¶p !)(f Al–C ¶p, 6’, 

Al

H

Al
+

14’
Al
thf

"2’JV<VÔa,  11’, gz

H
15’

Al Br

Sc

Me2N NMe2
13’

Br
Sc

6’

3’ +

Me2N NMe2

Me2N
Me2N

CHPh2
Br CHPh2
8’

H

Al

Al
thf

H Sc

Br

Me2N NMe2
14’

Br
Sc

Sc
Br

NMe2
NMe2

 Al lz $JV<V´,( 5-KV=:0DSÔaz,( 12’, ( '1 Al $ Sc S;Õ ¨£JV<V,(j$¿(  nº(& 4 a´ 2S-D1V 10’m( 2 © C–Al ¶p ¢& '1

:-SMD/NjJV<V 3’ ¢( %4 ¢ Al $%(-S3S-SMD/N
6’¢ ) GU7Vj-S3S$ 2 '11V. nº'3¢JV<V Al $_h¢KV=:0D0S-D1V 10’m 2 '11V
. nº+Al  Sc¨m0 ( ¿&)=m Î¼  &  !







| §½ª¦
1.

Feng, G.; Chan, K. L.; Lin, Z.; Yamashita, M., J. Am. Chem. Soc. 2022, 144, 22662-22668.

2.

Kurumada, S.; Yamashita, M., J. Am. Chem. Soc. 2022, 144, 4327-4332.

3.

Sonoda, T.; Kanamori, M.; Endo, K.; Miwa, K.; Kurumada, S.; Suzuki, K.; Yamashita, M.; Shibahara, F., Isr. J.

Chem. 2022, 62, e202200038.
4.

Takegasa, S.; Lee, M. M.; Tokuhiro, K.; Nakano, R.; Yamashita, M., Chem. Eur. J. 2022, 28, e202201870.

5.

Zhong, R.-L.; Suzuki, K.; Yamashita, M.; Sakaki, S., ACS Catal. 2022, 12, 4880-4897.

6.

Kaneiwa, T.; Yamada, K.; Nakano, R.; Yamashita, M., ChemPlusChem 2023, 88, e202200380.

7.

Nakano, R.; Yamanashi, R.; Yamashita, M., Chem. Eur. J. 2023, 29, e202203280.

8.

Uno, N.; Nakano, R.; Yamashita, M., ACS Catal. 2023, 6956-6965.

- 56 -

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࢔ࢡࢳࣥࡢຍỈศゎ཯ᛂ⤒㊰᥈⣴*DXVVLDQ ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ 21,20 ἲࢆ⏝࠸࡚ࠊάᛶ㒊఩ࢆ 40 ࡛ࣞ࣋ࣝࠊࡑࢀ௨እࡢ㒊఩ࢆ 00 ࡛ࣞ࣋ࣝྲྀࡾᢅ࠸ࠊ$73 ࡜ỈศᏊ࠿ࡽ࡞ࡿጞ≧ែ࠿ࡽ $'3 ࡜ࣜࣥ㓟 3L ࡢ⤊≧ែ࡟⮳ࡿࡲ࡛ࡢ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰ࡢ᥈⣴ࢆ⾜ࡗࡓࠋ40 㡿ᇦࡣ 0;* G ࠾ࡼࡧ %/<3* G ࡛ࠊ00 㡿ᇦ࡟ࡣ $PEHUII ຊሙࢆࡑࢀࡒࢀ᥇⏝ࡋࡓࠋ



◊✲ᡂᯝ


࣒࣊⺮ⓑ㉁࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎᯒ& 11 䛻䜘䜛┦㛵ゎᯒ䛷䛿䚸䜎䛪 2% 25 2%25 䛻䛴䛔䛶  䝷䝧䝹䛷䛾䜽䝷䝇ศ㢮䜢⾜䛳䛯䚹ண್䛸ほ ್䛾

┦㛵ಀᩘ䜢ゎᯒ䛧䛯䛸䛣䜝䚸 ᅇ஺ᕪ᳨ド䛾ᖹᆒ್䛸䛧䛶  䛸䛔䛖㧗䛔⢭ᗘ䛜ᚓ䜙䜜䚸䝫䜿䝑䝖ᵓ㐀䛸䝍䞁䝟䜽㉁ᶵ
⬟䛸䛾┦㛵䛜♧၀䛥䜜䛯䚹ΰྠ⾜ิ䛾⤖ᯝ䛛䜙䚸༢୍ᶵ⬟䛾䝍䞁䝟䜽㉁䛻䛴䛔䛶䛿㧗⢭ᗘ䛻ண䛷஧㔜ᶵ⬟䠄2%25䠅䛾ண䛜䛷䛝䛶䛔䜛୍᪉䛿㞴䛧䛔䛣䛸䛜䜟䛛䛳䛯䚹ධຊ䝕䞊䝍䛾᝟ሗ䜢㒊ศⓗ䛻๐䛳䛯ゎᯒ䜘䜚ᶵ⬟䛾ண䛻䛿䝫䜿䝑䝖⾲㠃䜘䜚䜒䝍䞁䝟䜽㉁ෆ㒊䛾᝟ሗ䛜㔜せ䛷䛒䜛䛣䛸䛜♧၀䛥䜜䛯䚹䛥䜙䛻 2%252%25(7 䛻ᑐ䛩䜛  䝷䝧䝹䛷䛾䜽䝷䝇ศ㢮䜢⾜䛳䛯䛸䛣䜝䚸 ᅇ஺ᕪ᳨ド䛾ᖹᆒ್䛸䛧䛶  䛸䛔䛖㧗䛔⢭ᗘ䛜ᚓ䜙䜜䛯䚹2% 䛸 25 䜎䛯䛿 (7䛾ศ㢮⢭ᗘ䛿㧗䛟䚸 䝷䝧䝹ศ㢮䛛䜙䛾⢭ᗘ䛾పୗ䛿୺䛻 25 䛸 (7 䛾ㄗศ㢮䛻䜘䜛䜒䛾䛰䛳䛯䚹䜎䛯䚸⺮ⓑ㉁䛾䜻䝱
䝡䝔䜱ᵓ㐀䠄✵Ὕ㒊ศ䛾ᵓ㐀䠅䛾ẚ㍑䛛䜙䚸ྠ୍䛾ᶵ⬟䜢ᣢ䛴䝍䞁䝟䜽㉁䛷䜒䜻䝱䝡䝔䜱ᵓ㐀䛻䛿䜀䜙䛴䛝䛜䛒䜛䛣䛸䛜♧䛥䜜䛯䚹ᮏ◊✲䛷ᵓ⠏䛧䛯 &11 䝰䝕䝹䛷䛿䚸䜻䝱䝡䝔䜱ᵓ㐀䛾㢮ఝᛶ䛰䛡䛷䛺䛟䚸䝍䞁䝟䜽㉁ᶵ⬟䛻┦㛵䛩䜛ᵓ㐀ⓗ䛺≉ᚩ䜢ᢳฟ䛧䛶䛔䜛ྍ⬟ᛶ䛜䛒䜛䠄㏆⸨ࡽ Biomolecules2023䠅䚹

3QRU ࡢ཯ᛂάᛶࡢゎᯒ࢔ࢡࢳࣥ୰࡛ࡢ $73 ຍỈศゎ⤒㊰ࢆ⣔⤫ⓗ࡟᥈⣴ࡋࡓ⤖ᯝࠊࡲࡎ $73 ࡢ࣐࢞ࣥ఩࠿ࡽ࣓ࢱࣇ࢛ࢫࣇ࢙࢖ࢺ
32± ࡀゎ㞳ࡋࡓ୰㛫యࢆ୚࠼ࡓᚋ࡛ࠊ㏆఩ࡢỈศᏊ : ࡀࣉࣟࢺࣥ⛣ື࡜༠ዌࡋ࡞ࡀࡽ 32±ࢆồ᰾ᨷᧁࡋ࡚ࣜࣥ㓟ࢆ⏕ᡂࡍࡿࠊGLVVRFLDWLYH࡞཯ᛂ⤒㊰ࡀぢฟࡉࢀࡓࠋᚊ㏿ẁ㝵ࡣồ᰾ᨷᧁࡢẁ㝵࡛࠶ࡾࠊࡑࡢ࢚ࢿࣝ
ࢠ࣮㞀ቨࡣຍỈศゎ㏿཯ᛂ㏿ᗘࡢᐇ್࡜▩┪ࡋ࡞࠸ࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡉࡽ࡟ࠊ$73 ࡢ 32 ⤖ྜ㛤⿣࡟ඛ⾜ࡋ࡚ : ࡟ࡼࡿồ᰾ᨷᧁࡸࠊ: ࠿ࡽࡢࣉࣟࢺࣥ⬺㞳ࡀඛ⾜ࡍࡿDVVRFLDWLYH࡞཯ᛂ⤒㊰࡟ࡘ࠸࡚ࡶ᳨ウࡋ
ࡓࡀࠊGLVVRFLDWLYH࡞⤒㊰ࡼࡾࡶ࢚ࢿࣝࢠ࣮ⓗ࡟୙฼࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋຍ࠼࡚ࠊỗ㛵ᩘࡢ㐪࠸ࡸ 40㡿ᇦࡢࢧ࢖ࢬ࡟ᑐࡋ࡚࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡀᐃᛶⓗ࡟ኚືࡋ࡞࠸ࡇ࡜࠿ࡽࠊᮏ◊✲࡛ぢฟࡉࢀࡓ཯ᛂ⤒㊰ࡣࣟࣂࢫࢺ࡞ࡶࡢ࡛࠶ࡿ࡜⤖ㄽ࡙ࡅࡓ㸦වᯇࡽ Proc. Natl. Acad. Sci. U.S.A.2022H㸧
ࠋ



Ⓨ⾲ᐇ⦼


ཱྀ㢌Ⓨ⾲㸦ࢭࣥࢱ࣮฼⏝࡟ࡼࡿࡶࡢ඲  ௳࠺ࡕᣍᚅㅮ₇  ௳㸧‫ۻ‬㮚㔝ࡽ WK$VLDQ%LRORJLFDO,QRUJDQLF&KHPLVWU\&RQIHUHQFHࠊᣍᚅㅮ₇࡞࡝
࣏ࢫࢱ࣮Ⓨ⾲㸦ࢭࣥࢱ࣮฼⏝࡟ࡼࡿࡶࡢ඲  ௳㸧‫ۻ‬௰ྜྷࠊ㮚㔝ࡽ ➨  ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࣏ࢫࢱ࣮Ⓨ⾲࡞࡝ฟ∧ᐇ⦼㸦ㄽᩥ඲  ௳㸧‫ۻ‬㏆⸨ࡽ Biomolecules2023ࠊմවᯇࡽ Proc. Natl. Acad. Sci. U.S.A.2022H ࡞࡝- 58 -

⏕యศᏊࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXGLHVRQ6WUXFWXUHVDQG)XQFWLRQVRI%LRORJLFDO0ROHFXOHV‫ۑ‬㉥℩ ኱ࠊ┦⏣ ⨾◁Ꮚࠊᆏ᐀ ࿴᫂㸦ᗈᓥ኱Ꮫ㸧ࠊᏳ ᡂ㙠㸦ᮾி኱Ꮫ㸧



◊✲┠ⓗ
⏕⌮άᛶศᏊࡸ⏕యศᏊࡢᵓ㐀ࡢ≉ᚩࡸ཯ᛂࡢ࣓࢝ࢽࢬ࣒㸪ࡲࡓ㸪ࡑࢀࡽ࡬ࡢ⁐፹ࡸ࿘ࡾࡢศᏊ࠿ࡽࡢᙳ

㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸪୺࡟㔞Ꮚ໬Ꮫィ⟬㸪ศᏊືຊᏛἲࢆ⏝࠸ࡓ◊✲ࢆ㐍ࡵࡓ㸬ᮏᖺᗘࡢ୺
࡞◊✲ෆᐜࡣḟࡢ஧ࡘ࡛࠶ࡿ㸬
1.1 ⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤Ⓨ

NMR ศගἲࡣ⏕య㧗ศᏊࡸኳ↛᭷ᶵ໬ྜ≀ࡢᵓ㐀ỴᐃཬࡧศᏊ㛫┦஫స⏝ࡢゎ᫂࡟᭱ࡶ᭷ຊ࡞
୍ࡘ࡛࠶ࡾ㸪NMR ໬Ꮫࢩࣇࢺࡢᐃ㔞ⓗண
ࡍࢀࡤ㸪ᐇ

ᐃἲࡢ

ࡣ᭷⏝࡛࠶ࡿ㸬⌧௦࡛ࡣ୍⯡ⓗ࡞㔞Ꮚ໬Ꮫィ⟬ࣃࢵࢣ࣮ࢪࢆ฼⏝್࡜ẚ㍑࡛ࡁࡿ⢭ᗘ࡛ᑐ㇟ศᏊࡢ NMR 㐽ⶸᐃᩘࢆィ⟬࡛ࡁࡿ㸬ࡋ࠿ࡋ㸪⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ

NMR 㐽ⶸᐃᩘࢆ㸪⁐㉁࿘ࡾࡢ⁐፹ศᏊࢆ࠶ࡽࢃ࡟ྲྀࡾධࢀ࡚ከࡃࡢ⁐፹࿴ᵓ㐀࡟ᑐࡋ࡚ィ⟬ࡍࡿࡢࡣ㸪ィ⟬ࢥࢫࢺࡀẚ㍑ⓗ኱ࡁ࠸㸬ࡑࡇ࡛㸪ᶵᲔᏛ⩦ࢆ⏝࠸࡚ィ⟬ࢥࢫࢺࡢప࠸ NMR 㐽ⶸᐃᩘணࣔࢹࣝࢆసᡂࡍࡿ

ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬
1.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂RNA ᖸ΅ (RNAi)ࡣ㸪siRNA ࡜࿧ࡤࢀࡿ▷࠸஧ᮏ㙐 RNA ࡀ㑇ఏᏊⓎ⌧ᢚไຠᯝࢆ♧ࡍ⌧㇟࡛࠶ࡿ㸬siRNA
ࡣ Argnaute (AGO)ࢱࣥࣃࢡ㉁࡜」ྜయࢆᙧᡂࡍࡿ࡜஧ᮏ㙐ࡀゎࡅ㸪AGO ୖ࡟࢞࢖ࢻ㙐ࡔࡅࡀṧࡿ㸬ࡑࡢ࢞࢖ࢻ㙐ࡀ┦⿵ⓗ࡞㓄ิࢆࡶࡘᶆⓗ mRNA ࡜ᑐྜࡋ㸪ᶆⓗ mRNA ࢆษ᩿ࡍࡿࡇ࡜࡛㑇ఏᏊⓎ⌧ࢆᢚไࡍࡿ㸬RNAi࡛ࡣ㸪ᮏ᮶ᶆⓗ࡛ࡣ࡞࠸ mRNA ࡢⓎ⌧ࢆᢚไࡍࡿ࢜ࣇࢱ࣮ࢤࢵࢺຠᯝࡀゎỴࡍ࡭ࡁၥ㢟࡛࠶ࡿ㸬࢞࢖ࢻ㙐ࡢ≉ᐃࡢ఩⨨ࡢࢾࢡࣞ࢜ࢳࢻࡢ࣮ࣜ࣎ࢫࢆ໬Ꮫಟ㣭ࡍࡿࡇ࡜࡛㸪఩⨨≉␗ⓗ࡟άᛶ࡟ᙳ㡪ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡾ㸪RNAi άᛶࢆಖࡗࡓࡲࡲ࢜ࣇࢱ࣮ࢤࢵࢺຠᯝࢆῶᙅࡉࡏࡿྍ⬟ᛶࡀ♧၀ࡉࢀ࡚࠸ࡿ㸬ࡑࡇ࡛㸪㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾ㸪࢞࢖ࢻ㙐࡬ࡢ໬Ꮫಟ㣭ࡢຠᯝࡢస⏝ᶵᵓࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 ⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤Ⓨ⁐፹࿴ᵓ㐀ࢆࢧࣥࣉࣜࣥࢢࡍࡿࡓࡵ࡟㸪NAMD ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋ࡚࣓ࢱࣀ࣮ࣝỈ⁐ᾮࡢศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ㸬MD ࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽ࣓ࢱࣀ࣮ࣝศᏊ࡜ࡑࡢ㏆ഐࡢศᏊࢆᢤࡁฟࡋࡓ㸬ᚓࡽࢀࡓࢡࣛࢫࢱ࣮ᵓ㐀࡟ࡘ࠸࡚㸪B3LYP/aug-cc-pVDZ ࡛ࣞ࣋ࣝ GIAO ἲࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜࠸ NMR 㐽ⶸᐃᩘࢆồࡵࡓ㸬ᶆⓗ࡛࠶ࡿ࣓ࢱࣀ࣮ࣝศᏊࡔࡅ࡛ࡶ NMR 㐽ⶸᐃᩘࡢィ⟬ࢆ⾜࠸㸪࿘ࡾࡢ⁐፹ศᏊ࠿ࡽࡢᙳ㡪࡟ࡼࡿ NMR 㐽ⶸᐃᩘࡢࢩࣇࢺ㔞ࢆồࡵࡓ㸬NMR 㐽ⶸᐃᩘࡢィ⟬࡟ࡣ Gaussian 16 ࢆ⏝࠸ࡓ㸬
NMR 㐽ⶸᐃᩘண

ࣔࢹࣝࡣ㸪࿘ࡾࡢศᏊ࠿ࡽࡢᙳ㡪࡟ࡼࡿ㐽ⶸᐃᩘࡢࢩࣇࢺ㔞ࢆ┠ⓗኚᩘ࡜ࡋ࡚㸪⁐㉁ศ

Ꮚ࡜⁐፹ 1 ศᏊࡢᗙᶆࢆධຊ࡜ࡍࡿ 2 య㡯࡜⁐㉁ศᏊ࡜⁐፹ 2 ศᏊࡢᗙᶆࢆධຊ࡜ࡍࡿࡢ 3 య㡯ࡢฟຊࡢ࿴
࡛ணࡍࡿࣔࢹࣝ࡜ࡋࡓ㸬2 య㡯࡜ 3 య㡯ࢆࡑࢀࡒࢀࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࡛⾲⌧ࡋ㸪DFT ィ⟬ࡢ⤖ᯝࢆᩍᖌࢹ࣮ࢱ࡜ࡋ࡚Ꮫ⩦ࢆ⾜ࡗࡓ㸬ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࡣ PyTorch ࢆ฼⏝ࡋ࡚ᐇ⿦ࡋࡓ㸬- 59 -

2.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂
AGO ࢱࣥࣃࢡ㉁࡜ siRNA ࡢ࢞࢖ࢻ㙐࡜ࡢ」ྜయ࡟ᑐࡍࡿ⨨᥮ᇶࡢᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟㸪⤖ᬗᵓ㐀࠿ࡽࢱ
ࣥࣃࢡ㉁ഃ㙐࡜࢜ࣜࢦࢾࢡࣞ࢜ࢳࢻࢆᢤࡁฟࡋࡓࣔࢹࣝ⣔ࢆᵓ⠏ࡋࡓ㸬ࡑࡢࣔࢹࣝ⣔ࢆ ȦB97X-D/6-31G(d)ࣞ
࡛࣋ࣝࢱࣥࣃࢡ㉁ࡢ CĮ ཎᏊࢆᅛᐃࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࡞ࡗࡓ㸪ࡲࡓ㸪࠸ࡎࢀ࠿ࡢࢾࢡࣞ࢜ࢳࢻࡢ࣮ࣜ࣎ࢫࡢ
2¶఩ࡢ±OH ࡟⨨᥮ᇶࢆᑟධࡋ࡚ྠᵝ࡟ᵓ㐀᭱㐺໬ࢆ⾜࡞ࡗࡓ㸬ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ Gaussian 16 ࢆ⏝࠸ࡓ㸬



◊✲ᡂᯝ

3.1 ⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤ⓎMD ࡢࢺࣛࢪ࢙ࢡࢺࣜ−࠿ࡽᢤࡁฟࡋࡓ࣓ࢱࣀ࣮ࣝ 1 ศᏊ࡜⁐፹ỈศᏊ࠿ࡽ࡞ࡿࢡࣛࢫࢱ࣮19774 ᵓ㐀࡟ࡘ࠸࡚㸪ᗙᶆࢹ࣮ࢱ࡜ィ⟬ࡋࡓ NMR 㐽ⶸᐃᩘࡢࢩࣇࢺ㔞ࡢ⤌ࢆᏛ⩦ࢹ࣮ࢱ࡜ホ౯ࢹ࣮ࢱ࡟ศ๭ࡋ㸪ணࣝࢆᏛ⩦ࡉࡏࡓ㸬ホ౯ࢹ࣮ࢱ࡟ᑐࡍࡿண

ࣔࢹࣔࢹࣝࡢᖹᆒ⤯ᑐ್ㄗᕪࡣ 0.43 ppm ࡜࡞ࡗࡓ㸬ࣔࢹࣝࢆゎᯒࡍࡿ࡜㸪㐽ⶸᐃᩘࡢࢩࣇࢺ㔞ࡣ 2 య㡯ࡀᨭ㓄ⓗ࡛࠶ࡾ㸪࣓ࢱࣀ࣮ࣝศᏊ࡜Ỉ⣲⤖ྜ࡛ࡁࡿ఩⨨࡟࠶ࡿ⁐፹ศᏊࡢ㡯ࡀ኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ண⢭ᗘࡢྥୖ࡜࡜ࡶ࡟㸪࣓ࢱࣀ࣮ࣝࡀ 2 ศᏊ௨ୖᏑᅾࡍࡿࢡࣛ

ࢫࢱ࣮ᵓ㐀࡬ࡢᑐᛂ࡛ࡁࡿࡼ࠺࡟ࣔࢹࣝࡢᣑᙇࢆ㐍ࡵ࡚࠸ࡿ㸬
3.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂
AGO ࢱࣥࣃࢡ㉁࡜ siRNA ࡢ」ྜయࡢࣔࢹࣝ⣔࡟ࡘ࠸࡚㸪siRNA ࡢ࢞࢖ࢻ㙐ࡢࢾࢡࣞ࢜ࢳࢻࡢ 2¶఩ࡀ↓⨨
᥮ࡢ±OH య࠾ࡼࡧ 2 ␒┠࠿ࡽ 8 ␒┠ࡲ࡛ࡢࢾࢡࣞ࢜ࢳࢻࡢ࠸ࡎࢀ࠿ࢆ±OMe㸪±NHCHO ࡞࡝࡟⨨᥮ࡋࡓ⨨᥮యࢆᵓ㐀᭱㐺໬ࡋᵓ㐀ࢆẚ㍑ࡋࡓ࡜ࡇࢁ㸪⨨᥮ᇶࡢ఩⨨≉␗ⓗ࡟ siRNA ࡢሷᇶࡢ㓄ྥࡀኚ໬ࡋ㸪ᐇ㦂ࡢ఩⨨≉␗ᛶ࡜▩┪ࡋ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓ㸬⨨᥮ᇶᑟධ࡟ࡼࡿሷᇶࡢ㓄ྥኚ໬ࡀᶆⓗ mRNA ࡜ࡢᑐྜࢆ㜼ᐖࡋ RNAiάᛶ࡟ᙳ㡪ࢆཬࡰࡍࡇ࡜ࡀ⪃࠼ࡽࢀࡿ㸬

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Yoshiaki Kobayashi, Daiki Fukuhara, Dai Akase, Misako Aida, Kumiko Ui-Tei㸪The siRNA seed region is divided
into two functionally different domains in RNA interference in response to 2'-OMe modifications㸪➨ 23 ᅇ᪥ᮏ
RNA Ꮫ఍ᖺ఍㸦2022 ᖺ 7 ᭶㸪ி㒔㸧‫[ۻ‬2] Ᏻᡂ㙠㸪ᑠᯘⰾ᫂㸪㔝ᮧᾈᖹ㸪ᮌᮧᗣ᫂㸪㜿㒊ὒ㸪㉥℩኱㸪┦⏣⨾◁Ꮚ㸪⛬ஂ⨾Ꮚ㸪2'-formamide ಟ㣭ࢆ seed 㡿ᇦ࡟ࡶࡘ siRNA ࡣሷᇶࡢྥࡁࢆኚ࠼ࡿࡇ࡜࡛ off-target ຠᯝࢆῶᙅࡉࡏࡿ㸪᪥ᮏ᰾㓟་⸆Ꮫ఍➨ 7 ᅇᖺ఍㸦2022 ᖺ 7 ᭶㸪ᮾி㸧‫[ۻ‬3] Seongjin An, Yoshiaki Kobayashi, Kohei Nomura, Yasuaki Kimura, Hiroshi Abe, Dai Akase, Misako Aida,
Kumiko Ui-Tei㸪Prediction of Structural Change of siRNA by 2'-formamide, a Newly-synthesized Chemical
Modification, via Density Functional Theory㸪CBI Ꮫ఍ 2022 ᖺ኱఍㸦2022 ᖺ 10 ᭶㸪ᮾி㸧‫[ۻ‬4] Seongjin An, Yoshiaki Kobayashi, Kohei Nomura, Yasuaki Kimura, Hiroshi Abe, Dai Akase, Misako Aida,
Kumiko Ui-Tei㸪The 2'-formamide modification in the siRNA seed region reduces off-target effects by two
different mechanisms㸪➨ 45 ᅇ᪥ᮏศᏊ⏕≀Ꮫ఍ᖺ఍㸦2022 ᖺ 12 ᭶㸪༓ⴥ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 60 -

ṑ㌴≧୧ぶ፹ᛶศᏊ(GSA)ࡢ⇕ຊᏛⓗᏳᐃᛶཬࡧⓎගࢫ࣌ࢡࢺࣝ࡟ᑐࡍࡿ⁐ᾮຠᯝࡢ⌮ㄽⓗ◊✲
Theoretical and computational study on substitution effect for thermal
stability and emission spectra of GSA‫❧ۑ‬ᕝ ோ඾ࠊᓥᓮ ᬛᐇࠊ໭ ᖾᾏࠊᑠᯘ ⌮ࠊᆏୖ ᘯ㍤ࠊᮧ⏣ ⴌࠊྜྷ⏣ ኱㍜㸦ᶓ὾ᕷ❧኱Ꮫ㸧1◊✲┠ⓗ ᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣᮾி኱Ꮫࡢᖹᒸᩍᤵ࡜ඹྠ
࡛ࠊṑ㌴≧୧ぶ፹ᛶศᏊ(GSA)ࡀỈ୰࡛ᙧᡂࡍࡿ
⟽ᆺ 6 㔞య࡛࠶ࡿࢼࣀ࣮࢟ࣗࣈࡢ◊✲ࢆ⾜ࡗ࡚࠸ࡿ(Fig. 1)ࠋᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡢᵓ㐀ࡣⅬ⩌
S6 ࡟ᖐᒓࡉࢀࠊศᏊ࡟ྵࡲࢀࡿ 3 ࡘࡢ࣓ࢳࣝᇶࡀ
ჶࡳྜࡗࡓࠕ໭ᴟࠖཬࡧࠕ༡ᴟࠖ࡜ࠊࣆࣜࢪࢽ࢘
࣒࢝ࢳ࢜ࣥཬࡧࣇ࢙ࢽࣝᇶ࠶ࡿ࠸ࡣࣆࣜࢪࣝᇶࡀ
ᙧᡂࡍࡿࠕtriple ȧ-stackingࠖࡀ୪ࡪࠕ㉥㐨ࠖ࡜࠸

Fig. 1. Monomer and nanocube of GSA. The substitution࠺ࠊ≉ᚩⓗ࡞ᵓ㐀ࢆ᭷ࡍࠋᙜࢢ࣮ࣝࣉ࡛ࡣศᏊື

group denoted by R is methyl group or deuterium and X isຊᏛࡢᡭἲࢆ⏝࠸ࠊࡇࢀࡲ࡛࡟ GSA ࡀࢡࣟࣟ࣍ࣝ

CH or N.

࣒୰࡛ࡣ 4 㔞యࢆᙧᡂࡍࡿࡇ࡜ࡸࠊࢼࣀ࣮࢟ࣗࣈ
ࡀࢤࢫࢺศᏊࢆྲྀࡾ㎸ࡴࡇ࡜ࡢ෌⌧࡟ᡂຌࡋࡓࠋࢤࢫࢺศᏊࡢໟ᥋㐣⛬ࡣࠊࢤࢫࢺศᏊࡀࣚ࢘໬≀࢖࢜ࣥࡢሙྜ࡟㝈ࡿࡀࠊศᏊㄽⓗゎ᫂࡟ࡶᡂຌࡋࠊ᫖ᖺᗘࡣໟᦤ㐣⛬࡟࠾ࡅࡿࢼࣀ࣮࢟ࣗࣈࡢኚᙧ࡜࡜ࡶ࡟ゎᯒࢆ⾜ࡗࡓࠋGSA ࡀᙧᡂࡍࡿࢼࣀ࣮࢟ࣗࣈࡣ GSA ࡢᵓ㐀ࢆ໬Ꮫⓗ࡟ಟ㣭ࡍࡿࡇ࡜࡟ࡼࡾࠊ⇕ⓗᏳᐃᛶࡸࢤࢫࢺศ
Ꮚࡢໟ᥋㏿ᗘࢆไᚚࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿ[1,2]ࠋࡲࡓࠊࢤࢫࢺศᏊࢆໟᦤࡋࡓࢼࣀ࣮࢟ࣗࣈࡣయ✚ࡸ⺯ගࢫ࣌ࢡࢺࣝ࡜࠸ࡗࡓ≀ᛶࡀࡶ࡜ࡢࢼࣀ࣮࢟ࣗࣈ࠿ࡽኚ໬ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟☜ㄆࡉࢀ࡚࠸ࡿ[3]ࠋ
 ᮏᖺᗘࡣ GSA ࢼࣀ࣮࢟ࣗࣈࡢ⇕ຊᏛⓗᏳᐃᛶࡢホ౯࡜ GSA ࣔࣀ࣐࣮ࡢ⁐ᾮෆ࡛ࡢ⺯ගἼ㛗ࡢィ⟬ࢆ⾜ࡗࡓࡀࠊࡇࡇ࡛ࡣ⣬㠃ࡢ㒔ྜୖ⺯ගἼ㛗ࡢᡂᯝࡢࡳࢆ♧ࡍࠋⓎගࢫ࣌ࢡࢺࣝࡣࢼࣀ࣮࢟ࣗࣈࢆᵓᡂࡍࡿࣔࣀ࣐
࣮ࡢᵓ㐀࡟౫Ꮡࡍࡿࡔࡅ࡛࡞ࡃࠊࢼࣀ࣮࢟ࣗࣈࢆᵓᡂࡋ࡚࠸ࡿ࠿ྰ࠿࡟ࡼࡾኚ໬ࡍࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋ
≉࡟ࣆࣜࢪࣝᇶࢆᣢࡘ GSA ࣔࣀ࣐࣮ࡢࢫ࣌ࢡࢺࣝ࡟ࡣ኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࡀぢࡽࢀࡿࡇ࡜ࡀᐇ㦂ⓗ࡟ุ᫂ࡋ࡚࠸ࡿࠋᡃࠎࡣࢫࢺ࣮ࢡࢫࢩࣇࢺࡢ㉳※ࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡓࡵ࡟ࠊࡇࢀࡲ࡛࡟ GSA ࣔࣀ࣐࣮ࡢⓎගࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗ࡚ࡁࡓࠋ࡜ࡇࢁࡀࠊィ⟬ࡋࡓⓎගࢫ࣌ࢡࢺࣝࡸኻά⤒㊰ࡣࢫࢺ࣮ࢡࢫࢩࣇࢺࢆ෌
⌧ࡏࡎࠊᐇ㦂ࡢⓎගࢫ࣌ࢡࢺࣝࢆㄝ᫂ࡍࡿ࡟ࡣ⮳ࡽ࡞࠿ࡗࡓࠋ ḟ࡟ᡃࠎࡣ GSA ࡀ࣓ࢱࣀ࣮ࣝ୰࡟࠾࠸࡚ࡶ 2 㔞యࢆᙧᡂࡍࡿࡇ࡜ࢆ௬ᐃࡋࡓࠋᐇ㦂ⓗ࡟ GSA ศᏊࡢ࣓ࢱ
ࣀ࣮ࣝ⁐ᾮࡣᕼ࡛ⷧ࠶ࡾࠊGSA ࡀỈ୰࡛ࢼࣀ࣮࢟ࣗࣈࢆᵓᡂࡋ࣓ࢱࣀ࣮ࣝ୰࡛ࡣᙧᡂࡋ࡞࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟
࡞ࡗ࡚࠸ࡿࠋࡋ࠿ࡋࣔࣀ࣐࣮࡜ࢼࣀ࣮࢟ࣗࣈࡢ㛫࡟ࡣ 2~5 㔞యࡢᵓ㐀ࢆ᝿ᐃࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡾࠊ≉࡟ 2㔞య࡟ࡘ࠸࡚ࡣ⤫ィⓗ࡟Ꮡᅾࡍࡿࡢ࡛ࡣ࡞࠸࠿࡜௬ᐃࡋࡓࠋ≉࡟ࠊGSA ศᏊࡣ࢝ࢳ࢜ࣥ㒊ศࢆᣢࡗ࡚࠾ࡾࠊ
ศᏊෆ㟁Ⲵ⛣ືࡋࡓඛ࡟┦␗࡞ࡿ GSA ศᏊࡢ࢝ࢳ࢜ࣥ㒊ศࡀ᥋㏆ࡍࡿࡇ࡜࡟ࡼࡾࠊ㟁Ꮚࡀṇ㟁Ⲵ࡛Ᏻᐃ໬ࡉ

- 61 -

ࢀࡿ࡜⪃࠼ࡽࢀࡿࠋᇶᗏ≧ែࡼࡾࡶບ㉳≧ែࡀࡼࡾᏳᐃ໬ࡉࢀࢀࡤࢫࢺ࣮ࢡࢫࢩࣇࢺࡀ⏕ࡌࡿࠋGSA ࡣ」ᩘ
ࡢⰾ㤶᪘⎔࠿ࡽ࡞ࡿศᏊ࡛࠶ࡾࠊບ㉳≧ែ࡟࠾࠸࡚ࡣࣘࢽࢵࢺ㛫࡛ศᏊෆ㟁Ⲵ⛣ືࡀ㉳ࡇࡿࠋࡑࡇ࡛ GSA ศᏊࡢࢻࢼ࣮㒊ศ࡜࢔ࢡࢭࣉࢱ㒊ศࢆࡑࢀࡒࢀࣔࢹࣝ໬ࡋࠊ㟁Ꮚᩘࢆኚ᭦ࡋ࡚࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࡇ࡜࡛ᨃ
ఝⓗ࡟㟁Ꮚບ㉳≧ែࢆィ⟬ࡋࡓࠋࡇࡢィ⟬࡟࠾࠸࡚࢔ࢡࢭࣉࢱ㒊ศ࡟┦␗࡞ࡿ GSA ศᏊࡢ࢝ࢳ࢜ࣥ㒊ศ㸦ࡢࣔࢹࣝ㸧ࢆ᥋㏆ࡉࡏࡿ࡜㟁Ꮚບ㉳࢚ࢿࣝࢠ࣮ࡀኚ໬ࡋࠊࢫࢺ࣮ࢡࢫࢩࣇࢺࡀⓎ⏕ࡍࡿࡇ࡜ࢆ preliminary ࡞⤖ᯝ࡛ࡣ࠶ࡿࡀ☜ㄆ࡛ࡁࡓࠋࡋ࠿ࡋࡇࡢィ⟬ࡣⓎගࣆ࣮ࢡࢆᐇ㦂࡜ྜࢃࡏࡿࡓࡵ࡟ࡣ⁐ᾮࢆ⪃៖ࡍࡿࡇ࡜ࡀᚲ
せ࡛࠶ࡿ୍᪉ࠊ⁐፹ຠᯝࢆ⪃៖ࡍࡿࡇ࡜࡟ࡼࡾ⌮ㄽィ⟬࡛ࡣࢲ࢖࣐࣮ࡢᙧᡂࡀ྾⇕ⓗ࡟࡞ࡿၥ㢟ࡀ࠶ࡗࡓࠋ
ᙜึࡢணᐃ࡛ࡣ㐃⥆ㄏ㟁యࣔࢹࣝࡢ౑⏝ࢆ␲࠸ࠊ⁐ᾮศᏊࢆࢧࣥࣉࣜࣥࢢࡋࡓୖ࡛ Our own N-layered
integrated molecular orbital and molecular mechanics(ONIOM)ἲࢆ⏝࠸⁐ᾮࢆ explicit ࡟ᢅ࠺ࡇ࡜࡛ၥ㢟ࢆゎỴࡍࡿࡇ࡜ࢆ᳨ウࡋ࡚࠸ࡓࠋࡋ࠿ࡋᡃࠎࡣࠊᮏ◊✲ࡢ⣔ࡀሷ࡛࠶ࡾ࢝࢘ࣥࢱ࣮࢔ࢽ࢜ࣥࡀᏑᅾࡍࡿࡇ࡜࡟Ẽࡀࡘ࠸ࡓࠋࢡ࣮ࣟࣥຊ࡟ࡼࡿᏳᐃ໬ࢆཷࡅࡽࢀࡿࡓࡵࠊ࢝࢘ࣥࢱ࣮࢔ࢽ࢜ࣥࡀ GSA ࡢࣔࣀ࣐࣮ࡢ㏆ࡃ࡟Ꮡᅾࡍࡿ
ࡇ࡜ࡣ 2 㔞యᙧᡂࡼࡾࡶ㉳ࡇࡾࡸࡍ࠸࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊィ⟬‽ഛཬࡧᮏィ⟬࡟᫬㛫ࢆせࡍࡿ ONIOM
࡟ࡼࡿィ⟬ࢆ⾜࠺๓࡟࢝࢘ࣥࢱ࣮࢔ࢽ࢜ࣥࡢඹᏑୗ࡛ࡢບ㉳≧ែࡢィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࡣィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ᶵୖ࡛ Gaussian16 Revision C02Nࢆ⏝࠸࡚⾜ࡗࡓࠋィ⟬࡟࠾࠸࡚ࡣᐇ㦂ⓗ࡟኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࢆ
♧ࡋࡓࣆࣜࢪࣥᆺࢆ⏝࠸ࠊィ⟬ࢆ⡆༢࡟ࡍࡿࡓࡵ࡟ࣇ࢙ࢽࣝᇶ࡟⤖ྜࡋࡓ࣓ࢳࣝᇶࢆỈ⣲ཎᏊ࡛⨨᥮ࡋࡓࣔࢹࣝࢆ⏝࠸ࡓ (Fig. 2)ࠋFig. 2 ࡟♧ࡍᵓ㐀࡟ࡘ࠸࡚㟁Ꮚᇶᗏ≧ែ S0 ཬࡧ➨ 1 㟁Ꮚບ㉳≧ែ S1 ࡟࠾ࡅࡿᵓ㐀᭱㐺໬ࢆᐦᗘỗ㛵ᩘ⌮ㄽཬࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ⌮ㄽ࡟ࡼࡾ⾜ࡗࡓࠋᐦᗘỗ㛵ᩘ࡟ࡣ S0 ≧ែཬࡧ S1 ≧ែࡢ࠸ࡎࢀࡢィ⟬࡟࠾࠸࡚ࡶN+N+

ωB97X-D ࢆ⏝࠸ࡓࠋࣚ࢘⣲ཎᏊࡢᇶᗏ㛵ᩘ࡜ᨃ࣏ࢸࣥࢩࣕࣝ࡟ࡣ
LanL2DZࠊࡑࡢ௚ࡢཎᏊ࡟ᑐࡍࡿᇶᗏ㛵ᩘ࡟ࡣ MIDI!ࢆ⏝࠸ࡓࠋSCRF

Fig. 2. The calculated model molecule.

ἲࢆ⏝࠸࡚࣓ࢱࣀ࣮ࣝ⁐፹ࢆ⪃៖ࡋࡓࠋᚓࡽࢀࡓ S0 ཬࡧ S1 ࡢ᭱Ᏻᐃᵓ㐀࡟࠾࠸࡚ࡑࢀࡒࢀᇶᗏ㛵ᩘࢆ jorge-ADZP ࡟ኚ᭦ࡋ࡚ᐦᗘỗ㛵ᩘ⌮ㄽཬࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ 1 Ⅼィ⟬ࢆ෌ᗘ⾜࠸ࠊࡑࢀࡒࢀࡢᵓ㐀࡟࠾ࡅࡿ S0 ≧ែ࡜ S1 ≧ែࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࢆồࡵࡓࠋᐦᗘỗ㛵ᩘࡣ ωB97X-D ࢆᘬࡁ⥆ࡁ⏝࠸ࠊ࣓ࢱࣀ࣮ࣝ⁐፹ࡢຠᯝࡣ SCRF
ἲࢆ⏝࠸࡚⪃៖ࡋࡓࠋS0 ≧ែࡢ᭱Ᏻᐃᵓ㐀࡟࠾ࡅࡿ S0 ≧ែ࡜ S1 ≧ែࡢ࢚ࢿࣝࢠ࣮ᕪ࠿ࡽ྾཰Ἴ㛗ࠊS1 ≧ែࡢ᭱Ᏻᐃᵓ㐀࡟࠾ࡅࡿ S0 ≧ែ࡜ S1 ≧ែࡢ࢚ࢿࣝࢠ࣮ᕪ࠿ࡽ⺯ගἼ㛗ࢆィ⟬ࡋࡓࠋ3◊✲ᡂᯝࣚ࢘໬≀࢖࢜ࣥࢆ GSA ࣔࣀ࣐࣮࡜ඹᏑࡉࡏࡿࡇ࡜࡟ࡼࡾ኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࡢᐃᛶⓗ࡞෌⌧࡟ᡂຌ

ࡋࡓࠋS1 ≧ែ࡟ࡣᏳᐃᵓ㐀ࡀᏑᅾࡋ S0 ≧ែ࠿ࡽᆶ┤ບ㉳ࡉࡏࡓ࡜ࡁࡢᵓ㐀ࡼࡾ 6.4 kcal/mol Ᏻᐃ࡛࠶ࡗࡓࠋ
ᚓࡽࢀࡓ྾ගἼ㛗(S0 ࡢᏳᐃᵓ㐀࡛ࡢᆶ┤ບ㉳࢚ࢿࣝࢠ࣮)ࡣ 302 nmࠊⓎගἼ㛗(S1 ࡢᏳᐃᵓ㐀࡛ࡢᆶ┤ບ㉳࢚ࢿࣝࢠ࣮)ࡣ 477 nm ࡛࠶ࡗࡓࠋᚓࡽࢀࡓ⤖ᯝ࡟ࡘ࠸࡚ࡣࢫࢺ࣮ࢡࢫࢩࣇࢺࡢ኱ࡁࡉཬࡧⓎගᙉᗘࡢほⅬ࠿ࡽᐇ㦂ࡢ◊✲ࢢ࣮ࣝࣉ࡜᳨ウࡋࠊⓎගཬࡧࢫࢺ࣮ࢡࢫࢩࣇࢺࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣᚓࡽࢀࡓィ⟬⤖ᯝࢆ㋃ࡲ
࠼࡚⪃ᐹࢆ㐍ࡵ࡚࠸ࡿẁ㝵࡛࠶ࡾࠊ2023 ᖺᗘࡢㄽᩥᢞ✏ࢆ┠ᣦࡋ࡚࠸ࡿࠋ
࠙ཧ⪃ᩥ⊩ࠚ

- 62 -

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4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
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ᮧ⏣ⴌ࣭㝞ᘯ⇝࣭ᑠᯘ⌮࣭ᓥᓮᬛᐇ࣭ᖹᒸ⚽୍࣭❧ᕝோ඾, ࠕ⮬ᕫ㞟ྜᛶࢼࣀ࣮࢟ࣗࣈࡢᏳᐃ໬࡜ศᏊ
ෆໟ࣓࢝ࢽࢬ࣒ࡢ⌮ㄽⓗ◊✲ࠖ, ➨ 24 ᅇ⌮ㄽ໬Ꮫウㄽ఍, 2P06, ▼ᕝ㸦ᑐ㠃㸧ཬࡧ࢜ࣥࣛ࢖ࣥ, 2022 ᖺ
5 ᭶㸦࢜ࣥࣛ࢖࡛ࣥࡢ࣏ࢫࢱ࣮Ⓨ⾲㸧

2.

ᮧ⏣ⴌ࣭ᑠᯘ⌮࣭ᖹᒸ⚽୍࣭ᓥᓮᬛᐇ࣭❧ᕝோ඾, ࠕṑ㌴≧୧ぶ፹ᛶศᏊࡢ⮬ᕫ㞟ྜయ࡟࠾ࡅࡿ࣓ࢳࣝ
ᇶࡢຠᯝࡢ⌮ㄽⓗゎᯒࠖ, ᪥ᮏ໬Ꮫ఍➨ 103 ᫓Ꮨᖺ఍㸦2023㸧, K606-1pm-02, ༓ⴥ, 2023 ᖺ 3 ᭶ 㸦ཱྀ㢌Ⓨ⾲㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

Sota Funaki, Tokuhisa Kawawaki, Tomoshige Okada, Kana Takemae, Sakiat Hossain, Yoshiki Niihori, Takumi
Naitou, Makito Takagi, Tomomi Shimazaki, Soichi Kikkawa, Seiji Yamazoe, Masanori Tachikawa, Yuichi
Negishi, "Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel
nanocluster", Nanoscale, 15, 5201-5208 (2023). DOI: 10.1039/D2NR06952K

2.

‫ ۻ‬Miku Furushima, Makito Takagi, Daisuke Yoshida, Yukiumi Kita, Tomomi Shimazaki, and Masanori
Tachikawa, "Theoretical investigations of positron affinities and their structure-dependent properties of carbon
dioxide clusters (CO2)n (n = 1-5)", Phys. Chem. Chem. Phys., 25, 625-632 (2023). DOI: 10.1039/d2cp03788b

3.

‫ۻ‬Moe Murata, Takuya Koide, Osamu Kobayashi, Shuichi Hiraoka, Tomomi Shimazaki, Masanori Tachikawa,"Molecular Dynamics Study on the Structure-Property Relationship of Self-Assembled Gear-Shaped Amphiphile
Molecules

with/without

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J.

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127,

328-334(2023).

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4.

Takumi Naito, Yukiumi Kita, Tomomi Shimazaki, and Masanori Tachikawa, "Decomposition analysis on the
excitation behaviors of thiazolothiazole (TTz)-based dyes via the time-dependent dielectric density functional
theory approach", RSC advances, 12, 34685-34693 (2022). DOI: 10.1039/d2ra06454e

5.

‫ۻ‬Daisuke Yoshida, Yukiumi Kita, Tomomi Shimazaki, and Masanori Tachikawa, "A comprehensive theoretical
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6.

Tomomi Shimazaki and Masanori Tachikawa, "Theoretical study of the effect of nonlocal short-range exchange
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7.

‫ۻ‬Taro Udagawa, Amane Kinoshita, Kazuaki Kuwahata, and Masanori Tachikawa, "A path integral molecular
dynamics study on the NH4+ rotation in NH4+ XH2 (X = Be or Mg) dihydrogen bond systems", Phys. Chem.
Chem. Phys., 24, 17295-17302 (2022). DOI: 10.1039/d2cp01999j

8.

Takatsugu Wakahara, Kahori Nagaoka, Chika Hirata, Kun'ichi Miyazawa, Kazuko Fujii, Yoshitaka Matsushita,- 63 -

Osamu Ito, Makito Takagi, Tomomi Shimazaki, Masanori Tachikawa, Yoshiki Wada, Shinjiro Yagyu, Yubin Liu,
Yoshiyuki Nakajima, Kazuhito Tsukagoshi, "Fullerene C70/porphyrin hybrid nanoarchitectures: single-cocrystal
nanoribbons with ambipolar charge transport properties", RSC advances, 12, 19548-19553 (2022). DOI:
10.1039/d2ra02669d
9.

‫ۻ‬Taro Udagawa, Ikumi Hattori, Yusuke Kanematsu, Takayoshi Ishimoto, and Masanori Tachikawa, "Nuclear
quantum effect and H/D isotope effect in excited state intramolecular proton transfer and electron-induced
intramolecular proton transfer reactions in 8-hydroxyquinoline", Int. J. Quant. Chem., 122, e26962 (12 pages)(2022). DOI: 10.1002/qua.26962

10. ‫ۻ‬Hikaru Tanaka, Kazuaki Kuwahata, Masanori Tachikawa, and Taro Udagawa, "Low-Barrier Hydrogen BondinFujikurin

A-D:

A

Computational

Study",

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7,14244-14251(2022).

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Intelligence and Simplified Chemical Interactions to Explore Active Ligands for Cyclin-Dependent Kinase 2",
ACS omega, 7, 10372-10381 (2022). DOI: 10.1021/acsomega.1c06976
12. ‫ۻ‬Kiriko Ishii, Tomomi Shimazaki, Masanori Tachikawa, and Yukiumi Kita, "Theoretical Study of the Isotopeand Homologue Effects on Nuclear Magnetic Shielding in Water and Hydrogen Sulfide Molecules", Chem. Lett.,
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Chem., 1208, 113542 (2022). DOI: 10.1016/j.comptc.2021.113542
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dissociation of the second bound state of positronium hydride", Phys. Rev. A, 105, 012814 (2022). DOI:
10.1103/PhysRevA.105.012814
15. Kazuaki Kuwahata and Masanori Tachikawa, "Atomic mass dependence of the nuclear quantum effect inNH4+(H2O)", Chem. Phys., 553, 111381 (2022). DOI: 10.1016/j.chemphys.2021.111381
16. ‫ۻ‬Yuka Kimura, Yusuke Kanematsu, Hiroki Sakagami, David S Rivera Rocabado, Tomomi Shimazaki, Masanori
Tachikawa, and Takayoshi Ishimoto, "Hydrogen/Deuterium Transfer from Anisole to Methoxy Radicals: A
Theoretical Study of a Deuterium-Labeled Drug Model", J. Phys. Chem. A, 126, 155-163 (2022). DOI:
10.1021/acs.jpca.1c08514
17. Dorra Mahdaoui, Chika Hirata, Kahori Nagaoka, Kun'ichi Miyazawa, Kazuko Fujii, Toshihiro Ando, Manef
Abderrabba, Osamu Ito, Makito Takagi, Takayoshi Ishimoto, Masanori Tachikawa, Shinjiro Yagyu, Yubin Liu,
Yoshiyuki Nakajima, Yoshihiro Nemoto, Kazuhito Tsukagoshi, and Takatsugu Wakahara, "Ambipolar to unipolar
irreversible switching in nanosheet transistors: the role of ferrocene in fullerene/ferrocene nanosheets", J. Mater.
Chem. C, 10, 3770-3774 (2022). DOI: 10.1039/D1TC05545C
18. ‫ ۻ‬Kiriko Ishii, Tomomi Shimazaki, Masanori Tachikawa, and Yukiumi Kita, "Development of anharmonic
vibrational structure theory using backflow transformation", Chem. Phys. Lett., 787, 139263 (2022). DOI:
10.1016/j.cplett.2021.139263- 64 -

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ࠿ࡽ⣸እ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝゎᯒ
6SHFWUDO$QDO\VLVRI&RQGHQVHG0DWWHUVLQWKH)UHTXHQF\5DQJHIURP
7+]WR89ᐩỌ ᆂ௓ࠊᙇ ᓠࠊ⸨஭ ᝆ⏕ࠊ㧗ᮏ ࿴ஓࠊ/RX6HUDILQ/R]DGD㸦⚄ᡞ኱ᏛศᏊࣇ࢛ࢺ
ࢧ࢖࢚ࣥࢫ◊✲ࢭࣥࢱ࣮ࠊ⚄ᡞ኱Ꮫ⌮Ꮫ◊✲⛉㸧 ◊✲┠ⓗࢸࣛ࣊ࣝࢶᖏ㸦7+] FP㸧࠿ࡽ⣸እ㡿ᇦ㸦aQP㸧࡟࠾ࡅࡿ࿘ἼᩘᖏࡣࠊศᏊ⣔ࡢศᏊෆ࠾ࡼࡧ
ศᏊ㛫᣺ື࣮ࣔࢻࠊ࠾ࡼࡧ㟁Ꮚ㑄⛣࡟┦ᙜࡋࠊỈ⣲⤖ྜᛶᾮయࡸ⁐ᾮࠊࡲࡓࢱࣥࣃࢡ㉁ࠊศᏊෆ㟁Ⲵ⛣ື➼ࡢ」㞧ศᏊ⣔࡟࠾ࡅࡿືⓗᣲືࡸᒁᡤᵓ㐀ࠊศᏊ㛫ࡢ┦஫స⏝ࠊ㟁Ꮚ≧ែࠊ㟁Ꮚᵓ㐀➼ࢆ⌮ゎࡍࡿ࠺࠼࡛㔜せ࡞࿘Ἴᩘᖏ࡛࠶ࡿࠋ⏦ㄳ⪅ࡢࢢ࣮ࣝࣉ࡛ࡣࠊ᫬㛫㡿ᇦࢸࣛ࣊ࣝࢶศගࡸ᫬㛫ศゎࢸࣛ࣊ࣝࢶศගࠊࡲࡓ ḟඖ᣺ືศගࠊ࣓࢞࣊ࣝࢶ࠿ࡽ㐲㉥እ㡿ᇦ࡟ࢃࡓࡿᗈᖏᇦㄏ㟁ศගࠊࣇ࢙࣒ࢺ⛊࣏ࣥࣉ㸫ࣉ࣮ࣟࣈศගࠊ᫬
㛫ศゎ⺯ගศග

ᐃ➼ࢆ⏝࠸࡚ࠊࡇࢀࡽࡢ」㞧ศᏊ⣔࡟㛵ࡍࡿศගᏛⓗ࡞◊✲ࢆ᥎㐍ࡋ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡛ࡣࠊࡇࢀࡽࡢᐇ㦂⤖ᯝ࠿ࡽᐃ㔞ⓗ࡞᝟ሗࢆᚓࡿࡓࡵ࡟ࠊ኱ᆺィ⟬ᶵࢆ⏝࠸ࡓ⢭ᐦィ⟬ࢆ⾜࠺ࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ
&1㸬ศᏊෆ㟁Ⲵ⛣ື⣔ࡢ㟁Ꮚ≧ែࡢィ⟬*DXVVLDQ ࢆ⏝࠸࡚ࠊ㏻ᖖࡢᡭ㡰࡛ࠊࢩࢡࣟ࣊࢟ࢧࣥࠊࢸࢺࣛࣄࢻࣟࣇࣛࣥ㸦7+)㸧ࠊ࢔ ࢭ ࢺ ࢽ ࢺ ࣜ ࣝ ୰ ࡟ ࠾ ࡅ ࡿ ELV GLPHWK\ODPLQR  F\DQRSKHQ\O FDUED]ROH

1%$1&&ࠊᅗ  ཬࡧ %$&㸦ᅗ 㸧ࡢ㟁Ꮚ≧ែࢆ✚ศ᪉⛬ᘧ⾲ᘧ໬ศᴟ㐃⥆యࣔࢹ࡛ࣝィ⟬ࡋࡓࠋ

0H 1

 ᇶᗏ≧ែ㸦6㸧࡟ࡘ࠸࡚ &$0%/<3 GS ࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬

10H ᣺ືᩘゎᯒ࡟ࡼࡗ࡚ప᣺ື࣮ࣔࢻ࡜⹫᣺ືࡢ᭷↓ࢆ☜ㄆ ࡑࡢᖹ⾮ᵓ㐀ࢆᅛᐃࡋࡓࡲࡲ୍㔜㡯ບ㉳≧ែ㸦66 㸧࡟ࡘ࠸࡚ &$0%/<3 GS ୍࡛ࣞ࣋ࣝⅬ࢚ࢿࣝࢠ࣮ィ⟬ ྛ㟁Ꮚ㑄⛣࡟࠾࠸࡚᭱኱ᐤ୚ࢆ♧ࡍศᏊ㌶㐨ࡢ⤌ࢆ *DXVV9LHZ ࡛⾲♧ ࢥ࢖ࣝࢢࣟࣅ࣮ࣗࣝ㌿⛣ࡢศᏊㄽⓗゎ㔘ࡢ☜❧ᅗ 㸬%$1&&㸦ୖ㸧࡜%$&㸦ୗ㸧ࡢศᏊᵓ㐀ࠋᮏ◊✲࡛ࡣ ᗘᛂ⟅ᛶ㧗ศᏊ࡛࠶ࡿ࣏ࣜ NNࢪ࢚ࢳࣝ࢔ࢡࣜࣝ࢔࣑ࢻ㸦3G($ࠊᅗ 㸧ࡢ┦㌿⛣⌧㇟ࢆ᳨ウࡋࡓࠋỈ⁐ᾮ୰࡟࠾࠸࡚ࠊ⣙  . ࡼࡾࡶప ࡛ࡣศᏊ㙐ࡀఙࡧࡓࢥ࢖ࣝ≧ែ࡟࡞ࡾࠊ㧗 ࡛ࡣศᏊ㙐ࡀจ⦰ࡋࡓࢢࣟࣅ࣮ࣗࣝ≧ែ࡟࡞ࡿࠋࡇࢀࡣࢥ࢖ࣝࢢࣟࣅ࣮ࣗࣝ㸦&*㸧㌿⛣࡜࿧ࡤࢀ࡚࠸ࡿࠋྠᵝࡢᛶ㉁ࢆ♧ࡍࡶࡢ࡜ࡋ࡚࣏ࣜ N࢖ࢯࣉࣟࣆࣝ࢔ࢡࣜࣝ࢔࣑ࢻ㸦31L3$㸧ࡶࡲࡓㄪ࡭
ࡽࢀࠊศᏊෆỈ⣲⤖ྜࡢᙧᡂࡀ㔜せ࡞ᙺ๭ࢆᢸࡗ࡚࠸ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ3G($ ࡢࡼ࠺࡟ศᏊෆỈ⣲⤖ྜࢆ᭷ࡉ࡞࠸ሙྜࡢ &*㌿⛣࡟࠾ࡅࡿศᏊࢲ࢖ࢼ࣑ࢡࢫࡣ࡯࡜ࢇ࡝᳨ウࡉࢀ࡚࠸࡞࠸ࠋ

ࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ 3G($ ࡢ &* ㌿⛣ࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡓࡵࠊ



*URPDFV㸦YHUVLRQ㸧ࢆ⏝࠸࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⾜ࡗࡓࠋࡲࡓࠊẚ㍑࡜ࡋ࡚ 3G($ ࡢ༢㔞య༢఩࡟┦ᙜࡍࡿࢪ࢚ࢳࣝ

- 65 -ᅗ 㸬ᗘᛂ⟅ᛶ㧗ศᏊࡢศᏊᵓ㐀ࠋࣉࣟࣆ࢜ࣥ࢔࣑ࢻ㸦G(3㸧࡟ࡘ࠸࡚ࡶྠᵝࡢィ⟬ࢆ⾜࠸ࠊ⾲㠃Ỉࡢࢲ࢖ࢼ࣑ࢡࢫࢆ᳨ウࡋࡓࠋຊሙ࡜ࡋ࡚ 23/6
$$ ࢆ฼⏝ࡋࠊ&* ㌿⛣ࡢ ᗘࢆṇ☜࡟⾲⌧ࡍࡿࡓࡵ࡟ 7,33,FH ࣔࢹࣝࢆ⏝࠸ࡓࠋ3G($ ࡜ࡋ࡚༢㔞యࡀ ಶ㐃⤖ࡋࡓࡶࡢࢆ⏝ពࡋࠊ❧యつ๎ᛶࢆ DWDFWLF ࡞ࡶࡢ࡜ࡋࡓ㸦PHVRG\DGa㸧ࠋNPT ᮲௳ୗ࡛ QV ࡢᵓ㐀ᖹ⾮໬ࢆ⾜࠸ࠊࡑࡢᚋ  QV ࡢࢹ࣮ࢱࢆ  IV 㛫㝸࡛グ㘓ࡋࡓࡶࡢࢆゎᯒ࡟౑⏝ࡋࡓࠋ ᗘࡣ  . ࠿ࡽ . ࡲ࡛ . ࡎࡘኚ໬ࡉࡏࡓࠋࡲࡓࠊ⤫ィᖹᆒࢆ⪃៖ࡋ࡚ึᮇ㓄⨨ࡀ␗࡞ࡿ  ࡘࡢࢺࣛࢪ࢙ࢡࢺࣜࢆグ㘓ࡋࡓࠋ༢㔞యࡸ⣧Ỉࡢィ⟬࡛ࡣ QV ࡢࢹ࣮ࢱࢆᖹ⾮໬ࡢᚋ࡟ IV ้ࡳ࡛グ㘓ࡋࡓࠋ ◊✲ᡂᯝ
㸬ศᏊෆ㟁Ⲵ⛣ື⣔ࡢ㟁Ꮚ≧ែࡢィ⟬
%$1&& ࡜ %$& ࡢ྾཰ࢫ࣌ࢡࢺࣝࡢ⁐፹౫Ꮡᛶࢆ

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$FHWRQLWULOH㻌ᅗ  ࡟♧ࡍࠋ%$& ࡟ẚ࡭ࠊ%$1&& ࡣ QP ௜㏆
ࡢࣂࣥࢻᙉᗘࡀᙉࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋᙜ
ึࠊࡇࡢ %$1&& ࡢࣂࣥࢻࡣ %$& ࡢ㟁Ꮚ㑄⛣ࡢᙉᗘࡀఱࡽ࠿ࡢ⌮⏤࡟ࡼࡾᙉࡃ࡞ࡗࡓࡶࡢ࡜ࡋ࡚ゎ㔘ࡋ࡚࠸ࡓࠋࡍ࡞ࢃࡕࠊᒁᡤບ㉳≧ែ㸦ORFDOO\
H[FLWHGVWDWH/( ≧ែ㸧࡬ࡢࣂࣥࢻ࡛࠶ࡿ࡜⪃࠼࡚ᅗ 㸬%$1&&㸦ᐇ㊶㸧࡜ %$&㸦◚⥺㸧ࡢ྾཰ࢫ࣌ࢡ

࠸ࡓࠋィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊᅗ  ࡟♧ࡍ㑄⛣࢚ࢿࢺࣝࡢ⁐፹౫Ꮡᛶࠋ

ࣝࢠ࣮ࠊἼື㛵ᩘࡢኚ໬ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࠊ
%$1&& ࡢ QP ࡢࣂࣥࢻࡣࠊ/( ࣂࣥࢻ࡟㟁Ⲵ⛣ືࣂࣥࢻ㸦FKDUJHWUDQVIHUEDQG&7 ࣂࣥࢻ㸧࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ⁐፹ࡢㄏ㟁⋡ࢆࢩࢡࣟ࣊
࢟ࢧࣥࡢࡑࢀ࠿ࡽ࢔ࢭࢺࢽࢺࣜࣝࡢࡑࢀ࡟ኚ໬ࡉࡏ࡚ࡶࡇࡢ &7 ࣂࣥࢻࡣ࡯࡜ࢇ࡝ࡑࡢ㑄⛣࢚ࢿࣝࢠ࣮࡟ኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ୍⯡࡟ࠊ&7 ࣂࣥࢻࡣ⁐፹ࡢㄏ㟁⋡࡟኱ࡁࡃ౫Ꮡࡍࡿࡓࡵࠊ࡞ࡐࡑࡢࡼ࠺࡞ࡇ࡜ࡀ࠾ࡇࡿࡢ࠿ࠊࡑࡢᚤどⓗ࡞ཎᅉ࡟⯆࿡ࢆࡶࡗࡓࠋ྾཰ࢫ࣌ࢡࢺࣝࠊ⺯ගࢫ࣌ࢡࢺࣝࡢ⁐፹౫ᏑᛶࢆࠊศᏊෆࡢ෌㓄ྥ࢚ࢿࣝࢠ࣮㸦OLQWUD㸧ࠊ⁐፹ࡢ෌㓄ྥ࢚ࢿࣝࢠ࣮㸦OVROY㸧ࠊࡲࡓ 6 ≧ែ࡜ &7 ≧ែࡢ࢚ࢿࣝࢠ࣮ᕪ㸦'E㸧ࢆ⏝࠸࡚ゎ㔘ࡋࡓ࡜
ࡇࢁࠊ%$1&& ࡛ࡣOVROY ࡜'E ࡀ⁐፹ࡢᴟᛶ࡟౫Ꮡࡍࡿࡀࠊ6 ࠿ࡽࡢᆶ┤㑄⛣࡟ࡼࡿ )UDQFN&RQGRQ ≧ែ࡛ࡣࠊࡇࡢ஧ࡘࡢኚ໬ࡀ┦ẅࡋ࠶ࡗ࡚ࠊࡑࡢ
ᅗ 㸬%$1&&㸦ᕥ㸧࡜ %$&ࡓࡵ⁐፹౫Ꮡᛶࢆ♧ࡉ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

㸦ྑ㸧ࡢ㟁Ꮚ≧ែࡢ㑄⛣࡜ ࢥ࢖ࣝࢢࣟࣅ࣮ࣗࣝ㌿⛣ࡢศᏊㄽⓗゎ㔘ࡢ☜❧&* ㌿⛣ࡢ㐍⾜ࡣ 3G($ ࡢᅇ㌿༙ᚄࡢ ᗘኚ໬࡟ࡼࡗ࡚≉ᚩ࡙ࡅࡽࢀࠊᅗ ࡟ࡑࡢᖹᆒ್ࢆ♧ࡍࠋ㌿⛣Ἴື㛵ᩘࡢኚ໬ࡢᵝᏊࠋᗘࡣ . ࡜ぢ✚ࡶࡽࢀࠊᮏィ⟬ࡣ༑ศ࡟ᐇ ࢆ෌⌧ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋḟ࡟ࠊ&* ㌿⛣ࢆࡶࡓࡽࡍศᏊࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸࡚㆟ㄽࡍࡿࠋඛ⾜◊✲࡟࠾࠸࡚ࠊ31L3$ ࡢ &* ㌿⛣࡛ࡣศᏊෆỈ⣲⤖ྜࡢᙧᡂࡢ௚࡟ࠊഃ㙐ࡢⅣ໬Ỉ⣲ᇶྠኈࡢ᥋ゐࡶࡲࡓ㔜せ࡞ᙺ๭ࢆᯝࡓࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ⬺Ỉ࿴࡜㛵㐃ࡍࡿࡇࡢⅣ໬Ỉ⣲ᇶࡢ᥋ゐ࡟㛵ࡋࠊ୺㙐㦵᱁ࡢ᤬ࡌࢀ࡜⤖ࡧ௜ࡅࡿࡓࡵ࡟᥋ゐࡋ࡚࠸ࡿഃ
㙐ࡢ༢㔞య༢఩㛫ࡢᩘ࡛ศ㢮ࡋࡓࠋලయⓗ࡟ࡣࠊn㸦n «㸧␒┠ࡢ༢㔞య఩⨨࡜ nk ␒┠ࡢ఩⨨ࡢഃ㙐࡛᥋ゐࡍࡿ࡜ࡁࠊk ࡀ  ௨ୗࡢ᫬࡜  ௨ୖࡢ᫬࡛ሙྜศࡅࢆ⾜ࡗࡓࠋഃ㙐ࡢ࣓ࢳࣝᇶࡢ & ཎᏊ㛫ࡢ㊥㞳ࡀ - 66 -Ⴒ ௨ୗࡢ᫬࡟᥋ゐࡋ࡚࠸ࡿ࡜ࡳ࡞ࡋࠊሙྜศࡅࡋ࡞࠸᫬࡜ࡋࡓ᫬ࡢ⤖ᯝࢆᅗ  ࡟♧ࡍࠋᅗ  ࡜ྠᵝ࡞ኚ໬ࡀぢࡽࢀࡓࡢࡣ k ࡀ  ௨ୖࡢ࡜ࡁ
࡛࠶ࡾࠊk ࡀ  ௨ୗࡢ࡜ࡁࡣᗘኚ໬ࡀぢࡽࢀ࡞࠿ࡗࡓࠋẚ㍑ⓗ㏆࠸఩⨨࡛᥋ゐࡋ࡚࠸ࡿࡶࡢࡣ㦵᱁ࡢ᤬ࡌࢀࡀㄏᑟࡉࢀࡎࠊ࡯ࡰ┤⥺ᵓ㐀࡟࡞ࡿࡓࡵࢢࣟࣅ࣮ࣗࣝ≧ែ࡬ࡢ㑄⛣࡟ࡣ࡯࡜ࢇ࡝ᙳ㡪ࢆཬࡰࡉ࡞

࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊ࣓ࢳࣝᇶ࿘ࡾࡢỈ࿴Ỉࡢಶᩘ࡜࢝ࣝ࣎ࢽࣝᅗ 㸬ᅇ㌿༙ᚄࡢ

㸦&2㸧ᇶ࿘ࡾࡢỈ࿴Ỉࡢ ᗘኚ໬ࢆᅗ  ࡟♧ࡍࠋᮏ◊✲࡛ࡣ࣓ࢳࣝ

ᗘ౫Ꮡᛶࠋ࢚࣮ࣛ

ࣂ࣮ࡣᶆ‽೫ᕪࢆព࿡ࡍࡿࠋ

ᇶ࿘ࡾࡢ᪉ࡀ ᗘ࡟ᑐࡋ࡚ᩄឤ࡟ኚ໬ࡍࡿࡇ࡜࠿ࡽࠊ&* ㌿⛣ࡣⅣ໬Ỉ⣲ᇶࡢ⬺Ỉ࿴ࡀ㐍⾜ࡋࡓࡢࡕ࡟㐲㊥㞳㛫ࡢ␯Ỉᛶᇶࡢ᥋ゐ࡟ࡼࡗᅗ 㸬Ⅳ໬Ỉ⣲ᇶࡢ᥋ゐᩘࠋሙྜศࡅ↓ࡋࡢሙྜࠊ࠾ࡼࡧ k ࡀ  ௨ୗࡢ᫬࡜  ௨ୖࡢ᫬ࡢ⤖ᯝࠋ࡚㦵᱁ࡢ᤬ࡌࢀࡀⓎ⏕ࡍࡿࡇ࡜࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋศᏊ㛫Ỉ⣲⤖ྜࡢῶᑡ࡟ࡼࡿ &2 ᇶ࿘㎶ࡢ⬺Ỉ࿴ࡣ &* ㌿⛣ࡢ⤖ᯝ࡜ࡋ࡚⏕ࡌࡓ࡜⪃࠼ࡽࢀࡿࠋ ḟ࡟ࠊỈ࿴Ỉࡢࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸᳨࡚ウࡍࡿࠋࡇࡇ࡛ࡣࠊᐇ㦂ⓗ࡟ࡋࡤࡋࡤ㆟ㄽࡉࢀࡿ &2 ఙ⦰᣺ື࡟ᙳ㡪ࢆཬࡰࡍࠊศᏊ㛫Ỉ⣲⤖ྜࡋࡓỈศᏊࡢᅇ㌿㐠ື࡟ࡘ࠸࡚㆟ㄽࡍࡿࠋỈศᏊࡢᅇ㌿⦆࿴㐣⛬ࡣ௨ୗࡢ┦㛵㛵ᩘ࠿ࡽィ⟬ࡋࡓࠋ

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C t

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P >P   P t @  h  . ᅗ 㸬㸦ୖ㸧&2 ᇶ࿘ࡾࠊ㸦ୗ㸧Ⅳ໬Ỉ

ࡇࡇ࡛ࠊP x ࡣࣝࢪࣕࣥࢻࣝከ㡯ᘧࡢ➨஧ᘧ࡛࠶ࡾࠊP t ࡣ᫬้ t࡟࠾ࡅࡿỈࡢ཮ᴟᏊࡢ༢఩࣋ࢡࢺࣝࠊh t ࡣỈ⣲⤖ྜࡢᙧᡂ࣭
㛤⿣ࢆ♧ࡍ㛵ᩘ࡛࠶ࡾࠊᙧᡂࡋ࡚࠸ࡿ࡜ࡁࡣ ࠊࡑࢀ௨እࡣ ࡜࡞ࡿ㛵ᩘ࡛࠶ࡿࠋ. ࡟࠾ࡅࡿィ⟬⤖ᯝࢆᅗ  ࡟♧ࡍࠋᣦᩘ㛵ᩘ࡟ࡼࡿࣇ࢕ࢵࢸ࢕ࣥࢢࢆ⾜ࡗࡓ⤖ᯝࠊ඲࡚ࡢ⣔࡟࠾࠸࡚ SV ⛬ᗘࡢỈศᏊࡢࣛ࢖ࣈ࣮ࣞࢩࣙࣥ㐠ື࡟⏤᮶ࡍࡿῶ⾶ࡀほ ࡉࢀࡓࠋḟ࡟㐜࠸ῶ⾶࡜ࡋ࡚ࠊ⣧Ỉ࡛ࡣ  SVࠊG(3⣲ᇶ࿘ࡾࡢỈ࿴Ỉࡢ ᗘኚ໬ࠋ
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࡛ࡣ  SVࠊ3G($ ࡛ࡣ  SV ࡢ᫬ᐃᩘࡀᚓࡽࢀࡓࠋ⣧Ỉ࡜
G(3 ࡛ࡢᕪ␗ࡣศᏊ㛫Ỉ⣲⤖ྜᙉᗘ࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࠊᅗ 㸬Ỉ࿴Ỉࡢᅇ㌿⦆࿴㐣⛬ࠋ

G(3 ࡜ 3G($ ࡢᕪࡣ㌿⛣࡟క࠺᤼㝖య✚ࡢኚ໬࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ 3G($ ࡛ࡣ SV ࡢῶ⾶ࢆ♧ࡋࡓࠋᅗ  ࡟♧ࡍࡼ࠺࡟ࢥ࢖ࣝ≧ែ࡟࠾࠸࡚ࡶⅣ໬Ỉ⣲ᇶࡢ᥋ゐࡣᏑᅾࡋࠊ୺㙐ࡢ➃࡛ࡣᒁᡤⓗ࡟จ⦰ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋࡋࡓࡀࡗ࡚ࠊࡑࡢࡼ࠺࡞Ỉ࿴Ỉࡣഃ㙐ࡸ୺㙐࡟ࡼࡗ࡚㛢ࡌ㎸ࡵࡽࢀࠊⅣ⣲㦵᱁ࡢ㠀ᖖ࡟㐜࠸᤟ࡌࢀ㐠ືࡀỈࡢᅇ㌿㐠ື࡟ᙳ㡪ࢆཬࡰࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ

- 67 -

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L-DEX ࡜ L-2-CPA ࡜ࡢ」ྜయࡢ㔞ᏊຊᏛ㸦QM㸧/ศᏊຊᏛ㸦MM㸧ィ⟬࡟ࡘ࠸࡚ࠊᇶ㉁࡛࠶ࡿ L-2-CPA ࡸ཯ᛂ࡟㛵୚ࡍࡿゐ፹Ỉ࡜ࠊࡑࡢ࿘㎶ 5 Å ࡟Ꮡᅾࡍࡿ 10 ࢔࣑ࣀ㓟ࡲࡓࡣ 17 ࢔࣑ࣀ㓟㸦Asp10ࠊArg41ࠊLys151ࠊ
Tyr157ࠊAsp180 ࡞࡝ࢆྵࡴ㸧ࡢഃ㙐㒊ศࡢྜィ 114 ཎᏊࡲࡓࡣ 200 ཎᏊࡢ⣔ࢆ QM 㡿ᇦ࡟ᣦᐃࡋࠊࡑࢀ௨
እࢆ MM 㡿ᇦ࡜ࡋ࡚ Gaussian09 ࡢ Our own N-layered Integrated molecular Orbital and Molecular mechanics(ONIOM)ἲ࡟ࡼࡾ㑄⛣≧ែ㸦TS㸧ᵓ㐀᥈⣴ࠊ᣺ືᩘゎᯒࠊ཯ᛂ⤒㊰㏣㊧㸦IRC㸧ࡢィ⟬ࢆ⾜ࡗ࡚ࠊTS ᵓ㐀ࠊ཯ᛂ๓ᵓ㐀ࠊ཯ᛂᚋᵓ㐀ࢆỴᐃࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋTS ᵓ㐀᥈⣴࡟ࡘ࠸࡚ࡣࠊNudged Elastic
Band㸦NEB㸧ἲ࡟ࡼࡾ TS ᵓ㐀ࡸ཯ᛂ⤒㊰ࢆ⮬ື᥈⣴ࡍࡿࢯࣇࢺ࢙࢘࢔ Reaction Plus Pro2㸦HPC ࢩࢫࢸ࣒ࢬ㸧ࢆ౑⏝ࡋࡓࠋQM 㡿ᇦࡣࠊ㠀⤒㦂ⓗ࡞ᡭἲࡢ୍✀࡛࠶ࡿ DFT ࡢ࠺ࡕࠊZB97X-D/6-31G (d)ࢆ౑⏝ࡋࡓࠋMM 㡿ᇦ࡟ࡣ AMBER ຊሙࢆ⏝࠸ࡓࠋ㸱 ◊✲ᡂᯝ
ࡇࢀࡲ࡛ࡢィ⟬⤖ᯝ࡛ࡣࠊQM 㡿ᇦࢆ 185 ཎᏊࠊQM ィ⟬ࢆZB97X-D/6-31G (d)࡛ࣞ࣋ࣝィ⟬ࡋࡓ࡜ࡁ࡟ࠊ
άᛶ໬࢚ࢿࣝࢠ࣮ࡀ 29.43 kcal/mol ࡜࡞ࡗࡓࠋ2022 ᖺᗘࡣࡇࢀࡲ࡛ࡢ⣔࡟άᛶ࡟㔜せࡔ࡜ᛮࢃࢀࡿ Tyr157
ࡢഃ㙐㒊ศࢆ QM 㡿ᇦ࡟ຍ࠼࡚ࠊྠᵝࡢィ⟬࠿ࡽάᛶ໬࢚ࢿࣝࢠ࣮ࡢࡼࡾᑠࡉ࠸཯ᛂ⤒㊰ࡀぢࡘ࠿ࡿࡇ࡜ࢆ
ᮇᚅࡋ࡚ィ⟬ࢆヨࡳࡓࡶࡢࡢࠊ⹫ࡢ᣺ືࡀ 1 ࡘࡢ TS ᵓ㐀ࡀᚓࡽࢀࡎࠊ◊✲ࡢ㐍ᒎࡣぢࡽࢀ࡞࠿ࡗࡓࠋ

㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ㸳 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬Nakamura, T., Sasaki, S., Wang, X.F., and Kitao, O. J.Phys. D: Appl. Phys. , 55, 504001.
‫ ۻ‬Zheng, T., Liu, Y., Li, Y., Yang, L., Ren, H., Wang, X.F., Fujii, R., Kitao, O., Nakamura, T. and Sasaki,
S. Appl. Surface Sci. , 619, 156570.

- 69 -

㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀Innovations in computational quantum science and large-scale simulation science‫ۑ‬୰㎷ ༤ࠊ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴㸦㔞Ꮚ໬Ꮫ◊✲༠఍㸧◊✲┠ⓗᮏ◊✲ㄢ㢟࡟ㄢࡏࡽࢀࡓ᭱㔜せ࡞◊✲౑࿨࣭┠ⓗࡣࠊࠕࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎἲࡢᒎ㛤࡜ࡑࡢᐇ⏝໬࡛ࠖ࠶ࡿࠋ ᖺ࡟◊✲௦⾲⪅࡟ࡼࡾⓎ⾲ࡉࢀࡓࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࡟ゎࡃ㔞Ꮚ໬Ꮫ⌮ㄽ࡛࠶ࡿ⮬⏤᏶ဨ㛵ᩘ⌮ㄽ)UHH&RPSOHWH(OHPHQW RU&RPSOHPHQW 7KHRU\ Phys. Rev. Lett.93  ࡟ᇶ࡙ࡁ◊✲ࢆᒎ㛤ࡋ࡚ࡁࡓࡀࠊࡇࡢ⌮ㄽࡢᙉᅛ࡞ṇ☜ࡉ࡜ᰂ㌾ᛶࡣࡇࢀࡲ࡛ࡢ◊✲࡟ࡼࡗ࡚ࡲࡍࡲࡍ᫂ࡽ
࠿࡟࡞ࡾࠊࡑࡢ᭷⏝ᛶࡀ㧗ࡲࡾࡘࡘ࠶ࡿࠋ ᖺᗘࡣࠊࡇࡢ⌮ㄽࢆ᭦࡟㐍໬࣭Ⓨᒎࡉࡏࠊࠕṇ☜࡛ࠖ࠶ࡾ࡞ࡀ
ࡽࠕᐜ᫆ࠖࠕᏳᐃࠖ࠿ࡘࠕ㧗㏿ࠖ࡟ཎᏊ࣭ศᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢゎࢆồࡵࡽࢀࡿࡼ࠺࡟㛤Ⓨࢆ㐍ࡵ࡚ࡁࡓࠋ ᖺᗘࡣࠊィ⟬ᶵࢭࣥࢱ࣮ࡢࢩࢫࢸ࣒ࡢๅ᪂᫬ᮇ࡜㔜࡞ࡗ࡚࠾ࡾィ⟬ࢆ୰᩿ࡍࡿ᫬ᮇࡶ࠶ࡗࡓ
ࡀࠊࡑࡢ㛫ࡣ⌮ㄽయ⣔ࡢ☜❧࡜ᐇ⏝໬ࣇ࢙࣮ࢬ࡟⛣⾜ࡍࡿࡓࡵᗄࡘ࠿ࡢ㔜せ࡞᪉ἲࢆⓎᒎࡉࡏࡿࡇ࡜ࡀ࡛ࡁࠊ
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ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ⢭ᐦィ⟬ࡸ໬Ꮫ཯ᛂ࡞࡝ࠊᵝࠎ࡞ศ㔝ࡢᵝࠎ࡞⣔ࢆᑐ㇟࡟⪃࠼࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊ
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ࡶ࠺୍᪉ࡢࢸ࣮࣐࡛࠶ࡿ 6$&&, ἲࡢ⌮ㄽⓗᒎ㛤࡜ᛂ⏝࡟࠾࠸࡚ࡣࠊෆẆ࢖࢜ࣥ໬࠾ࡼࡧෆẆບ㉳ࡢ⌧㇟࡟ᛂ⏝ࡋᐇ㦂ᐙ࡜ࡢඹྠ◊✲ࡶ㐍ࡵࡓࡀࠊᮏ✏࡛ࡣ๭ឡࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ᭱㏆ࡢ⌮ㄽࡢ㐍ᒎࡢ୰࡛ࠊ ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ࡼࡿཎᏊ࣭ศᏊࡢ㟁Ꮚᵓ㐀⌮ㄽࡢᵓ⠏ J. Chem. Phys.149    ṇࡋ࠸ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࡢᑟධ J. Chem. Phys.156    ᒁᡤࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ἲ /RFDO 6FKU|GLQJHU (TXDWLRQ /6(  ἲ ࡢࢧࣥࣉࣜࣥࢢἲࡢ⌮ㄽ໬ Chem.
Phys. Lett.806    ᬑ㏻ࡢ✚ศࡢࡳ࡛ྍ⬟࡞ )& ኚศ⌮ㄽ)&sijWKHRU\ ࡢᐇ⏝ⓗᒎ㛤 Phys. Rev. A101    ᕧ኱ศᏊࡢィ⟬ࢆྍ⬟࡟ࡍࡿ ,QWHU([FKDQJH i([J  ⌮ㄽࡢᒎ㛤 J. Chem. Phys.142   QRQ%2 ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎἲࡢ୍⯡ศᏊ࡬ࡢᒎ㛤 J. Chem. Phys.139   ࡞࡝ࡣ≉࡟㔜せ࡛࠶ࡾࠊࡇࢀࡽࡢ⌮ㄽ࡜ࣉࣟࢢ࣒ࣛ㛤Ⓨ࡟ὀຊࡋࡓࠋ௨ୗࠊࡇࢀࡽࢆ⡆༢࡟ㄝ᫂ࡍࡿࠋ
໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ: ໬Ꮫ⪅ࡢ໬Ꮫᴫᛕ ศᏊᵓ㐀ᘧࡸ໬Ꮫ཯ᛂᘧ ࡜ᑐᛂࡋࠊཎᏊ࠿ࡽศᏊࡢἼື㛵ᩘࢆᵓ⠏ࡍࡿࠋ≉࡟ࠊࠕཎᏊࡢ㔞Ꮚ≧ែ࠿ࡽศᏊࡢ㔞Ꮚ≧ែࠖࢆᵓ⠏ࡍࡿ࡜࠸࠺ᴫᛕࡀ㔜せ࡛࠶ࡾࠊ%ULOORXLQ ᐃ⌮ࡢඖ࡟໬Ꮫᘧࡔࡅ࡛ࡣ⾲ࡏ࡞࠸㔞Ꮚⓗ࡞ࢥࣥࢭࣉࢺࡀᑟධࡉࢀࡿࠋᵓ⠏ࡉࢀࡿἼື㛵ᩘࡣࠊ໬Ꮫࡢᮏ㉁࡛࠶
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- 70 -࡞࠸ ࢝ࢫࣉ᮲௳ࢆ‶ࡓࡍ ࡇ࡜ࠊղ⾪✺ࡢ࡞࠸㡿ᇦ࡛ࡣ 6FDOHG ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡀඖࡢࢩ࣮ࣗࣞࢹ
࢕࣮ࣥ࢞᪉⛬ᘧ࡟₞㏆ࡍࡿࡇ࡜ࠊ࡜࠸࠺  ᮲௳ࢆ‶ࡓࡍṇࡋ࠸㛵ᩘࢆᑟධࡋࡓ ³FRUUHFW´㛵ᩘ࡜࿧ࡪ ࠋ᰾㟁Ꮚ⾪✺࡟ᑐᛂࡍࡿ giA 㛵ᩘ࡜㟁Ꮚ㟁Ꮚ⾪✺࡟ᑐᛂࡍࡿ gij 㛵ᩘࡀ࠶ࡾࠊ ᖺᗘࡣ≉࡟ giA 㛵ᩘࡢᛶ㉁ࢆㄪ࡭࡚
Ἴື㛵ᩘࡢᛶ㉁ࢆ㧗ࡵࠊࡼࡾຠ⋡ⓗ࡟ H[DFW ゎ࡬ࡢ཰᮰ࢆ㏿ࡵࡿ᪉ἲࢆ◊✲ࡋࡓࠋᒁᡤࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ἲࡢࢧࣥࣉࣜࣥࢢἲ: 㔞Ꮚࣔࣥࢸ࢝ࣝࣟἲ࡞࡝ࢧࣥࣉࣜࣥࢢἲࢆ࣮࣋ࢫ࡜ࡍࡿ࡯
࡜ࢇ࡝ࡢ㔞Ꮚ໬Ꮫࡢ᪉ἲ࡛ࡣ࣓ࢺ࣏ࣟࣜࢫࢩ࣑࣮ࣗࣞࢩࣙࣥἲࡀ⏝࠸ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊỴᐃㄽⓗ࡞ຊᏛ࡛࠶ࡿ㔞ᏊຊᏛࡢ⌮ㄽయ⣔࡟࠾࠸࡚ࡣࠊ⣔ࡢἼື㛵ᩘࢆ඲࡚ࡢᒁᡤⅬ࡟࠾࠸࡚ṇ☜࡟཯ᫎࡍࡿ ORFDOVDPSOLQJἲࢆᇶ♏࡜ࡍ࡭ࡁ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ᡃࠎࡣ୍⯡ⓗ࡟▱ࡽࢀ࡚࠸ࡓ┤᥋ἲ ㏫ኚ᥮ἲ ࢆ⚾ࡓࡕࡢἼື㛵ᩘ࡟ᛂ⏝ࡋࠊ'LUHFW/RFDO6DPSOLQJ '/6 ἲࢆᥦ᱌ࡋࡓࠋࡇࡢ᪉ἲࡣࠊ⌮ㄽ࡟ἢ࠺⌮ᛶⓗ࡞ࢧࣥࣉࣜࣥࢢⅬࡢ⏕ᡂἲ࡛࠶ࡾࠊUDQGRPQHVV HUURU ࢆ㑊ࡅࠊᏳᐃ࡛⢭ᐦ࡞ィ⟬ࢆྍ⬟࡟ࡍࡿࠋ⮬⏤᏶ဨ㛵ᩘ⌮ㄽࡢࡼ࠺࡞ H[DFW ࣞ࣋ࣝࡢ⌮ㄽィ⟬࡟ࡣࠊࡸࡣࡾࠊỴᐃㄽ࡟≉᭷ࡢ UDWLRQDO ࡞ࢧࣥࣉࣜࣥࢢἲࡀᚲせ࡛࠶ࡾࠊᮏἲࡣࡑࡢ┠ⓗ࡟࠿࡞࠺ࡶࡢ࡛ࠊ᭷⏝࡛࠶ࡿࠋ
FC sij ኚศἲ: ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ࣞ࣋ࣝࡢ H[DFW ゎࡢ㏣ồ࡜ే⾜ࡋ࡚ࠊኚศἲ࡟ᇶ࡙ࡁẚ㍑ⓗᑠࡉ࡞ィ⟬ࢥࢫࢺ࡛໬Ꮫⓗ࡞◊✲࡬ࡢᛂ⏝࡟ྥ࠸࡚࠸ࡿ )& sij ἲࡶ㛤Ⓨࡋࡓࠋࡇࡢ᪉ἲࡣࠊJ 㛵ᩘ࡟࠾ࡅࡿ rij 㡯ࢆ

sij

rij 

ri   rj    xi x j  yi y j  zi z j ࡟⨨ࡁ᥮࠼ࡿࡇ࡜࡛ࠊ 㟁Ꮚ  㟁Ꮚ✚ศࡢࡳ࡛ࡢኚศィ⟬ࢆྍ⬟࡟ࡍࡿࠋࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢ⤯ᑐゎ H[DFW ゎ ࡬ࡢ཰᮰ࡣ㐜࠸ࡀࠊ┦ᑐⓗ࡞ᕪ࡛㆟ㄽࡍࡿࡇ࡜ࡢ࡛ࡁࡿ໬
Ꮫ⌧㇟ࡢ◊✲ ໬Ꮫ཯ᛂ ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ ບ㉳࢚ࢿࣝࢠ࣮࡞࡝ ࡬᭷⏝࡟ᒎ㛤ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
iExg ⌮ㄽ: 㟁Ꮚࡢ཯ᑐ⛠໬ࡣ୍⯡࡟኱ࡁ࡞ィ⟬㈇Ⲵ࡟࡞ࡿࡀࠊ㟁Ꮚ㞼ࡀ஫࠸࡟ゐࢀࡿࡇ࡜ࡶ࡞࠸࡯࡝㐲ࡃ㞳ࢀࡓ  ࡘࡢ㟁Ꮚᑐ࡛ࡣࡑࡶࡑࡶ㟁Ꮚࡢ஺᥮ࡣᚲせ࡛ࡣ࡞ࡃࠊ㐲࠸ཎᏊ㛫ࡢ୙せ࡞㟁Ꮚ཯஺᥮ࢆ᤼㝖ࡍࡿi([J ⌮ㄽࢆᥦ᱌ࡋࡓࠋࡇࡢ⌮ㄽ࡟❧ࡘ࡜ࠊィ⟬ࡀ᰿ᮏⓗ࡟ຍ㏿ࡉࢀ O N ⌮ㄽࡀᐇ⌧ྍ⬟࡛࠶ࡾࠊH[DFW ࡛࠶ࡾ࡞ࡀࡽᕧ኱⣔ࡢィ⟬ࢆᐇ⏝໬ࡍࡿ᪉ἲㄽ࣭࢔ࣝࢦࣜࢬ࣒㛤Ⓨࢆ㐍ࡵ࡚࠸ࡿࠋ
non-BO ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢゎἲ: ཎᏊ࣭ศᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡣࠊᮏ᮶ཎᏊ᰾ࡢ㐠ືࡶ㔞Ꮚ໬ࡉࢀࡿ QRQ%RUQ2SSHQKHLPHU QRQ%2  ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡛࠶ࡿࠋᡃࠎࡣࠊ໬Ꮫࣇ࢛࣮࣑ࣗ
ࣛ⌮ㄽࡢᒁᡤⓗᥥീࡀ QRQ%2 ィ⟬࡛ࡶ≉࡟㔜せ࡛࠶ࡿࡇ࡜࡟Ẽ࡙ࡁࠊࡲࡓ✚ศᅔ㞴࡞ၥ㢟ࢆゎỴࡍࡿ /6(ἲ࡜ඹ࡟ࠊࠕ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᇶ࡙ࡃ QRQ%2 )&/6( ⌮ㄽࠖࢆ㛤Ⓨࡋࡓࠋࡇࢀ࡟ࡼࡗ࡚ࠊ୍⯡ศᏊࡢ
QRQ%2 ィ⟬ࢆ㐙⾜ࡋࠊᚑ᮶ࡢ %2 ㏆ఝࡢ໬Ꮫࢆ㉸࠼ࡓ᪂ࡓ࡞ᒎ㛤࡟⧅ࡆࡓ࠸࡜⪃࠼࡚࠸ࡿࠋ
௨ୗࡢ◊✲ᡂᯝࡣࠊୖグ⌮ㄽ࣭᪉ἲㄽࢆᛂ⏝ࡋࡓ⤖ᯝ࡛࠶ࡿࠋ ᖺᗘࡣࠊ᪂ࡋ࠸⌮ㄽࡸ᪉ἲㄽࡢ㛤Ⓨ࡜ࡑࡢ☜❧ࡀ୺┠ⓗ࡛࠶ࡗࡓࡓࡵࠊ⡆༢࡞ཎᏊ࣭ศᏊ࡛ࡢ᳨ドࡀከ࠿ࡗࡓࡀࠊ௒ᚋࡣࡇࢀࢆᇶ♏࡟ࡼࡾ୍⯡ⓗ࡞ཎᏊ࣭ศᏊࢆᑐ㇟࡟ᐇ⏝໬ࡋ࡚࠸ࡃࡇ࡜ࢆ⪃࠼࡚࠸ࡿࠋ

◊✲ᡂᯝ          

3.1. ṇࡋ࠸ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࡢᑟධ      
6FDOHG ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡜ࡋ࡚ᑟධࡉ ⾲ 1.&RUUHFW ᆺ JL$JLM 㛵ᩘࢆ⏝࠸ࡓ /L ཎᏊࡢィ⟬ )&/6( ἲ ࢀࡓ J 㛵ᩘ࡟࠾࠸࡚ࠊ᰾㟁Ꮚ㛫ࡢ giA 㛵ᩘ࡜㟁Ꮚ㟁Ꮚ㛫ࡢ gij 㛵ᩘࡢ୧⪅ඹ࡟´FRUUHFW´࡞᮲௳ࢆ‶ࡓࡍࢫࢣ࣮ࣜࣥࢢ㛵ᩘࢆᑟධࡋࡓࠋ⾲   ࡣࠊJ 㛵ᩘ࡜ࡋ࡚ H[S ᆺ g

  H[S J r ࢆ⏝࠸ࡓ࡜ࡁ ࡢ /L ཎ Ꮚ  %H ཎ Ꮚ ࡢ ཰ ᮰ 㐣 ⛬ ࢆ ♧ ࡋ ࡚ ࠸

2UGHUnM+VTXDUHHUURU(QHUJ\ DX 

ǻE NFDOPRO 









               ࡿࠋ´FRUUHFW´- 71 -

ࡢ giA gij 㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡛Ἴື㛵ᩘࡢᛶ㉁ࢆ㧗 ⾲ 2.&RUUHFW ᆺ J J 㛵ᩘࢆ⏝࠸ࡓ %H ཎᏊࡢィ⟬ )&/6( ἲ 
L$ LMࡵࠊᚑ᮶ࡢ riArij 㡯ࡼࡾࡶ H[DFW ゎ࡬ࡢ཰᮰ࢆ኱ࡁ 2UGHUn M+VTXDUHHUURU (QHUJ\ DX  ǻE NFDOPRO 
ࡃ㏿ࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ





   /L ཎᏊ࡛ࡣ )& ⌮ㄽࡢ RUGHUn  ḟඖ M  ࡛ࠊ





   +VTXDUHHUURU ࡀ ǻE ṇ☜࡞࢚ࢿࣝࢠ࣮ࡢ





   





   ぢ✚ࡶࡾ࡜ࡢᕪ NFDOPRO ࡀᚓࡽࢀࡓࠋ

%H ཎᏊ࡛ࡶ n  M  ࡛ +VTXDUHHUURU ࡀ ǻE NFDOPRO ࡀᚓࡽࢀࠊ⤯ᑐゎ࡛ࢫ࣌ࢡࢺࣝ
⢭ᗘ௨ୖࡢ㠀ᖖ࡟㧗⢭ᗘ࡞ゎࡀᚓࡽࢀࡓࠋ≉࡟ࠊ 㟁Ꮚ㡯ࡢ giA 㛵ᩘࡣึᮇ㛵ᩘ࡟ᅾࡿ 6ODWHU ㌶㐨࡜ࡶᐦ᥋࡟
㛵㐃ࡋࠊࡉࡽ࡟ຠ⋡ⓗ࡟ H[DFW ゎ࡬ࡢ཰᮰ࢆຍ㏿ࡍࡿࡇ࡜ࡢ࡛ࡁࡿྍ⬟ᛶࡶᣢࡗ࡚࠸ࡿࠋ⌧ᅾࠊ୍⯡ⓗ࡞ཎᏊ
ศᏊ࡛ giAgij 㛵ᩘࢆ࣋ࢫࢺ࡞᪉ἲ࡛ྲྀࡾᢅ࠺᪉ἲࢆ㏣ồࡋ࡚࠸ࡿࠋ
3.2. ṇ☜࡞Ἴື㛵ᩘ࡜≀⌮㔞࣭ࣉࣟࣃࢸ࢕ࡢィ⟬)& ⌮ㄽࡣࠊἼື㛵ᩘࡀ H[DFW ࡟཰᮰ࡍࡿࡇ࡜ࢆಖドࡋ࡚࠸ࡿࡓࡵࠊࡑࡢἼື㛵ᩘ࠿ࡽồࡵࡓ࢚ࢿࣝࢠ࣮௨
እࡢ≀⌮㔞ࡸࣉࣟࣃࢸ࢕ࡶ㧗⢭ᗘ࡞ゎࡀᚓࡽࢀࡿࠋࡑࡢ୰࡛ࡶࠊH[DFW ࣞ࣋ࣝࡢἼື㛵ᩘ࡛࡞࠸࡜⢭ᐦ࡟ồࡵࡽࢀ࡞࠸㔞࡜ࡋ࡚ࠊཎᏊ᰾ୖࡢࢫࣆࣥᐦᗘࡸ࢝ࢫࣉ್࡞࡝ࡀ࠶ࡿࠋ๓⪅ࡣࠊ㉸ᚤ⣽ᵓ㐀ᐃᩘ K\SHUILQHVSOLWWLQJ
FRQVWDQW ࡜㛵㐃ࡍࡿ≀⌮㔞࡛࠶ࡾࠊ(65 ἲࡢᐇ㦂࡛ࡶ SRSXODU ࡛ࠊ◊✲௦⾲⪅࡟ࡣ≉࡟࡞ࡌࡳ῝࠸ᐇ㦂್࡛࠶ࡿࠋ⌮ㄽィ⟬࡛ࡣࠊĮ ࢫࣆࣥ࡜ ȕ ࢫࣆࣥࡢ㟁Ꮚᐦᗘࡢᕪ࡜ࡋ࡚ồࡵࡿࡀࠊࡑࡢᕪࡢ FDQFHODWLRQ ࡢ᱆௨ୖࡢ⢭ᗘࡢ࠶ࡿ㧗⢭ᗘἼື㛵ᩘ࡛࡞࠸࡜࠸ࡅ࡞࠸ࠋᚋ⪅ࡣࠊ FXVS> w\  wr  \ @r  ࡜ࡋ࡚ᐃ⩏ࡉࢀࡿ㔞࡛࠶ࡿࠋ

⾲ 3./L ཎᏊࡢᵝࠎ࡞≀⌮㔞࣭ࣉࣟࣃࢸ࢕ࡢィ⟬
2UGHUnM

2

S state(QHUJ\ DX ǻE
NFDOPRO 





㟁Ꮚᐦᗘ
ཎᏊ᰾ 

ࢫࣆࣥᐦᗘ
࢝ࢫࣉ್
㟁Ꮚᐦᗘ
࢝ࢫࣉ್
ཎᏊ᰾ 
᰾㟁Ꮚ⾪✺  㟁Ꮚ㟁Ꮚ⾪✺  㟁Ꮚ㟁Ꮚ⾪✺ 















    

0.2    





   

0.2    





   

0.2    





    

0.23         

0.231         

0.2313         

0.2313      

  



5HI 'UDNH Dᐇ㦂 ([DFW 
2 oP state



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E

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 



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

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    -0.0    





   -0.0    





   -0.017    





    -0.017         -0.017         -0.017         -0.017    

5HI 'UDNH D



  

  ᐇ㦂 ([DFW 

F







D/0:DQJ=&<DQ+;4LDRDQG*:)'UDNHPhys. Rev. A85   E3.XVFKDQG+7DXE3K\V5HY  F.&%URJ7*(FNDQG+:LHGHU3K\V5HY  +:LHGHUDQG7*(FNLELG

- 72 -

ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎࡢ‶ࡓࡍ࡭ࡁᚲせ᮲௳ࡢ  ࡘ࡛࠶ࡿ࢝ࢫࣉ᮲௳࠿ࡽࠊ\ ࡀ H[DFW ࡛࠶ࢀࡤࠊ᰾㟁Ꮚ࢝ࢫࣉࡢሙྜ= ཎᏊ᰾ࡢ㟁Ⲵ  㟁Ꮚ㟁Ꮚ࢝ࢫࣉࡢሙྜ VLQJOHW ࢝ࢫࣉࡢሙྜ ࡜࡞ࡿࡇ࡜
ࡀศ࠿ࡗ࡚࠾ࡾࠊἼື㛵ᩘࡢ´ṇ☜ࡉ´ࢆ⾲ࡍᣦᶆࡢ㸯ࡘ࡛࠶ࡿࠋ*DXVV ᆺ㛵ᩘࢆ⏝࠸ࡿ࡜ࠊࡑࡢᚤศࡣཎⅬ࡛ ࡛࠶ࡿࡓࡵ࢝ࢫࣉ᮲௳ࢆ‶ࡓࡋᚓ࡞࠸ࠋ౛࠼ࡤࠊ([SOLFLWO\&RUUHODWHG*DXVVLDQ (&* ἲࡣᑠࡉ࡞⣔࡛㧗⢭ᗘ࡞࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚࠸ࡿࡀࠊH[DFW ゎ࡜ࡋ࡚ࡢࡇࡢᚲせ᮲௳ࢆ඲ࡃ‶ࡓࡋᚓ࡞࠸ࠋ⾲  ࡣࠊ/L ཎᏊ࡛ )&⌮ㄽࡢኚศ∧࡛ィ⟬ࡋࡓࠊཎᏊ᰾࡟࠾ࡅࡿ㟁Ꮚᐦᗘ ࢫࣆࣥᐦᗘ ࢝ࢫࣉ್ࠊ㟁Ꮚ⾪✺࡟࠾ࡅࡿ㟁Ꮚᐦᗘ࡜࢝
ࢫࣉ್ࢆࡲ࡜ࡵࡓࠋRUGHU ࢆୖࡆࡿ࡜ࠊ࢚ࢿࣝࢠ࣮ࡔࡅ࡛࡞ࡃࡇࢀࡽࡢ≀⌮㔞࣭ࣉࣟࣃࢸ࢕ࡶṇ☜࡞್࡟཰᮰
ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ≉࡟ࠊ6 ≧ែࡢࢫࣆࣥᐦᗘࡣࠊ)& ⌮ㄽ್ ࡟ᑐࡋ࡚ᐇ㦂್ ࡛࠶ࡾࠊ㠀ᖖ࡟Ⰻ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࠋᐇ㦂ࡣ  ᖺࡢㄽᩥ࡛࠶ࡿࡀࠊࡇࡇࡲ࡛ᐇ㦂ࡢ⢭ᗘࡶⰋࡃ್ࡀ୍⮴ࡋ࡚࠸ࡿࡇ࡜ࡣ㦫ࡁ࡛࠶ࡗࡓࠋᚑ᮶ࡢ )XOO &, ἲ➼࡛ࡣࠊࡏ࠸ࡐ࠸   ᱆⛬ᗘࡋ࠿ྜࢃࡎࠊ)& ⌮ㄽࡢゎࡢಙ㢗ᛶࡀᨵࡵ࡚☜࠿ࡵࡽࢀࡓࠋ

3.3. ໬Ꮫ཯ᛂ◊✲ࡢᇶ♏: ┿࡟ṇ☜࡞࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡢィ⟬ ❶࡛㏙࡭ࡓࡼ࠺࡟ࠊ'LUHFW/RFDO6DPSOLQJ '/6 ἲࡣ

䘂: Exptl. (RK࣓ࢺ࣏ࣟࣜࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡎ㔞Ꮚⓗ࡞Ỵᐃㄽⓗ࡞ࢧࣥࣉࣜࣥࢢ⏕ᡂࢆྍ⬟࡜ࡍࡿࡶࡢ࡛࠶ࡾࠊ࣏ࢸࣥ

㽢: FC

21Ȉg+

g

b3Ȉg+

A1Ȉu+ ᐇ㦂RKR䛸᏶඲䛻୍⮴ࡿࠋᡃࠎࡣࠊࡇࡢ᪉ἲࢆᗄࡘ࠿ࡢ⡆༢࡞ศᏊ࡟ᛂ⏝ࡋࠊ⤯ᑐゎ ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢゎ ࡜ࡋ࡚ṇ☜࡞࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆ⌮ㄽⓗ࡟ᐇ⌧ࡋ࡚ࡁࡓࠋ

B1Ȇu

13Ȇg

ࢩ࣮ࣕࣝ࢝ࣈࡢィ⟬࡟࠾࠸࡚ࡶࣛࣥࢲ࣒࡞ࢧࣥࣉࣜࣥࢢ
౫Ꮡᛶࢆᢚ࠼⁥ࡽ࠿࡞グ㏙ࢆᚓࡿୖ࡛ࡶ㠀ᖖ࡟᭷⏝࡛࠶

11Ȇ

13Ȇu

a3Ȉu+

exact䛺䝎䜲䝘䝭䜽䝇◊✲䜈ǻ(NFDOPRO

Li2 ศᏊ J. Chem. Phys. 157   : ᫖ᖺᗘሗ࿌

X1Ȉg+᭩࡛᪤࡟ሗ࿌ࡋࡓࡀࠊ㔜せ࡞ᡂᯝ࡛࠶ࡾ -&3 ㄽᩥ࡜ࡋ࡚
ࡶฟ∧ࡉࢀࡓࡓࡵࠊࡑࡢ࣏࢖ࣥࢺࡔࡅࡇࡇ࡛ࡶ㏙࡭࡚⨨
ࡃࠋ/L ศᏊ࡛ࡣࠊ9DOHQFH ᇶᗏ࣭ບ㉳≧ែ࡟ᑐࡋ࡚ࠊ)& ⌮ㄽࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡣᐇ㦂࠿ࡽồࡵࡽࢀࡓ 5\GEHUJ

ᅗ 1. /L ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ ᐇ㦂 5.5 ࣏ࢸࣥࢩࣕࣝ࡜ẚ㍑.OHLQ5HHV 5.5 ࣏ࢸࣥࢩࣕࣝ࡜⤖ྜ㡿ᇦ࠿ࡽゎ㞳ࡲ࡛᏶඲୍⮴ࡍࡿ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡢィ⟬࡟ᡂຌࡋࡓᅗ  ࠋ୍㔜㡯 ୕㔜㡯ࡢࡑࢀࡒࢀṇ☜࡞࣮࢝ࣈࡀᚓࡽࢀ࡚࠾ࡾࠊ౛࠼ࡤࡇࢀ࡟ࢫࣆࣥ㌶㐨┦஫స⏝࡞࡝ࢆྵࡵࢀࡤࠊ␗࡞ࡿࢫࣆࣥ≧ែ㛫ࡢ㑄⛣ࢆక࠺ H[DFW ࡞ࢲ࢖ࢼ࣑ࢡࢫ◊✲➼࡬⧅ࡆࡽࢀࡿࠋ
H4 ศᏊ Chem. Phys. Lett. 815   : Ỉ⣲ࡣᏱᐂࡢ≀㉁⤌ᡂࡢ  ๭௨ୖࢆ༨ࡵࡿࡇ࡜࠿ࡽࠊᏱᐂࡢ
໬Ꮫ཯ᛂ࡟࠾࠸࡚᭱ࡶ୰ᚰⓗ࡞ᙺ๭ࢆᯝࡓࡍࠋࡑࡋ࡚ࠊ++++࡞࡝ࡢỈ⣲ࢡࣛࢫࢱ࣮ࡣࠊᏱᐂࡢ໬Ꮫ
཯ᛂࡢ㉳Ⅼ࡛࠶ࡾࠊࡲࡓࠊᫍ㛫ሻ⾲㠃࡛ࡢỈ⣲໬ 㑏ඖ཯ᛂ ࡢᮦᩱ࡟ࡶ࡞ࡿࠋ+ ࡸ +ࡣࠊᵝࠎ࡞ᐇ㦂࣭⌮ㄽ◊✲ࡀ࠶ࡾࠊࡑࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩࣕࣝ᭤㠃ࡶ㧗⢭ᗘ࡟⌮ゎࡉࢀ࡚࠸ࡿࡀࠊ+ ௨ୖࡢỈ⣲ࢡࣛࢫࢱ࣮࡛ࡣᮍࡔ㧗⢭ᗘ࡞⌮ㄽ◊✲ࡀᑡ࡞࠸ࠋᮏィ⟬ᶵ฼⏝࡛ࡣࠊࣔࢹࣝᵓ㐀ࡢ + ࡢ࣏ࢸࣥࢩࣕࣝ᭤㠃ࢆ H[DFW ⌮ㄽ࡟ࡼࡗ࡚ィ⟬ࡋࡓࠋ+ ࡣࠊ༢⣧࡞  㟁Ꮚ⣔ࡔࡀ㟼ⓗ㟁Ꮚ┦㛵ࡀᙉ࠸ࡓࡵࠊ㔞Ꮚ໬Ꮫ࡛⌮ㄽࢆ᳨ドࡍࡿ࣋ࣥࢳ࣐࣮ࢡ࡜ࡋ࡚ࡶࡼࡃ⏝࠸ࡽࢀ࡚࠸ࡿࠋ᫖ᖺᗘࡢሗ࿌࡛ࡣࠊᚑ᮶ࡢ )XOO &, ἲ࡛ࡣ㠀ᖖ࡟኱ࡁ࡞ᇶᗏ㛵ᩘ
&9% ࢆ౑ࡗ࡚ࡶ )& ⌮ㄽ࡟ࡼࡿ H[DFW ࡞⤖ᯝ࡜ࡣᕪࡀ࠶ࡾࠊࡲࡓ༢ཧ↷⌮ㄽࡢ &&6' ἲ࡛ࡣᐃᛶⓗ࡟ࡶṇࡋࡃ࡞࠸ࡇ࡜ࢆ♧ࡋࡓࠋᅗ  ࡣࠊ+ ศᏊࢆ㛗᪉ᙧࡢ 5[5\ ࢆኚ໬ࡉࡏࡓࣔࢹࣝ⣔࡛ࡢࠊ)& ⌮ㄽ࡟ࡼࡿᇶᗏ࣭
ບ㉳≧ែࡢ  ḟඖ࣏ࢸࣥࢩࣕࣝ㠃ࢆ♧ࡋ࡚࠸ࡿࠋᇶᗏ≧ែ ᅗ  ᕥ ࡢ࣏ࢸࣥࢩࣕࣝ㠃࡛ࡣࠊ ࡘࡢ + ཎᏊ࠿- 73 -ࡽ  ࡘࡢ + ศᏊࡀ⏕ᡂࡍࡿ㐣⛬ࡀぢࡽࢀࡿࠋ➨୍ບ㉳≧ែ ᅗ  ୰ ࡛ࡣࠊ+ ศᏊ࡜ࡋ࡚ࡢ᭱Ᏻᐃ࡞ᵓ㐀ࡀᏑᅾࡍࡿࡇ࡜ࡀศ࠿ࡿࠋࡲࡓࠊ➨஧ບ㉳≧ែ ᅗ  ྑ ࡛ࡣࠊᑐ⛠ᛶࡀᔂࢀࡓ㛗᪉ᙧᆺࡢ + ศᏊࡀ‽Ᏻᐃ࡟Ꮡᅾࡍࡿࡇ࡜ࢆ⾲ࡋ࡚࠸ࡿࡀࠊ࣏ࢸࣥࢩࣕࣝࡢᙧ࠿ࡽ + ศᏊ࡬ࡢゎ㞳࡬⧅ࡀࡿࡇ࡜ࡀศ࠿ࡿࠋࡇࡢࡼ࠺࡟ࠊບ
㉳≧ែࡢ࣏ࢸࣥࢩࣕࣝ㠃ࡶṇ☜࡟⌮ゎࡍࡿࡇ࡜ࡶ㔜せ࡛࠶ࡾࠊගບ㉳࡟ࡼࡗ࡚Ᏻᐃ໬ࡍࡿࣉࣟࢭࢫ࡞࡝ࠊண
᝿እࡢ཯ᛂ⣲㐣⛬ࡀᏑᅾࡍࡿྍ⬟ᛶࡶ࠶ࡿࠋ
H2 + H2+&

3㽢H(1s) + H(2s)4㽢H(1s)4㽢H(1s)+'Ry+%

Energyscale(a.u.)

Energyscale(a.u.)

Energyscale(a.u.)

Ry (a.u.)Rx

Ry (a.u.)

Ry (a.u.)+$

Dissociation
path to H2

H4 (square)

H4 ((rectangular)

H2 + H2Rx (a.u.)

Rx (a.u.)

Rx (a.u.)ᅗ 2.+ ศᏊࣔࢹࣝᵓ㐀ࡢ࣏ࢸࣥࢩࣕࣝ㠃 ᕥ ᇶᗏ≧ែ ୰ኸ ➨୍ບ㉳≧ែ ྑ ➨஧ບ㉳≧ែ
3.4. ໬Ꮫ◊✲࡬ࡢ᭷⏝࡞ᒎ㛤: FC sij ኚศἲࡢᛂ⏝C2 ศᏊࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ࡜໬Ꮫ⤖ྜㄽ: & ศᏊࡣࠊ᭷ᶵ໬Ꮫࡢ᭱ࡶᇶ♏ⓗ࡞஧ཎᏊศᏊ࡛࠶ࡿࡀࠊ&ཎᏊࡢ㔞Ꮚ≧ែࡢከᵝᛶ࡟㉳ᅉࡋࠊ≉࡟ࡑࡢ && ⤖ྜࡢ໬Ꮫ⤖ྜㄽࡣᮍࡔ࡟㆟ㄽࡢᑾࡁ࡞࠸ᑐ㇟࡛࠶ࡿࠋᡃࠎ
ࡣࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽࢆඖ࡟ & ཎ
MCSCF &
Extrapolation

FC sijᏊࡢ඲࡚ࡢ  ࡘࡢ 9DOHQFH ≧ែ࠿ࡽ &ศᏊࡢἼື㛵ᩘࢆᵓ⠏ࡋࠊ)& sij ἲ࡟ࡼ
ࡗ࡚ & ཎᏊࡢ 3 VS ≧ែ࡟ゎ㞳ࡍࡿ ͸͛1ɇg+͸1ȴg͸1Ʌu͸y1ɇg+ࡘࡢᇶᗏ࣭ບ㉳≧ែ ;ȈJ$ȆX %ǻJ%¶ȈJ ࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆィ⟬ࡋ--- ͛1ɇg+--- 1ȴg--- 1Ʌu--- y1ɇg+ࡓࠋᅗ  ᕥ ࡟ )& sij ἲ࡛ィ⟬ࡋࡓ࣮࢝ࣈࠊᅗ  ྑ ࡟⌮ㄽィ⟬࡟ࡼࡿ⌧≧ࡢ࣋ࢫࢺ࡞࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ࡜⪃࠼ࡽ࠼

ᅗ 3.& ศᏊࡢ ;ȈJ$ȆX%ǻJ%¶ȈJ≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ

࡚࠸ࡿ 5XHGHQEHUJ ࡽ࡟ࡼࡿ 0&6&) ᕥ )&sij ἲ ྑ 5XHGHQEHUJ ࡽ࡟ࡼࡿ 0&6&)H[WUDSRODWLRQ

H[WUDSRODWLRQ ἲ࡟ࡼࡿ࣏ࢸࣥࢩ࣮ࣕࣝ࢝

-75.259ࣈ ࢆ♧ࡋࡓ - 6 %RVFKHQ ' 7KHLV .

-75.309⤖ᯝࡣࠊRUGHU n  ࣞ࣋ࣝࡢ⡆༢࡞ィ⟬࡟ࡶ㛵ࢃࡽࡎࠊᐃ㔞ⓗ࡟ 5XHGHQEHUJ ࡽࡢ⤖ᯝ࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋᅗ  ࡣࠊ)&sij ἲࡢ࣮࢝ࣈࢆ⤯ᑐ࢚ࢿࣝࢠ࣮ࢆࢩࣇ

FC sij-75.359
Energy (a.u.)

Chem. Acc. 133   ࠋ)&sij ἲࡢ-75.309

FC sij-75.359
Energy (a.u.)

5XHGHQEHUJ DQG 7 / :LQGXV Theor.

-75.259-75.409-75.459-75.509-75.559-75.409-75.459-75.509RKR-75.559RKR-75.609-75.659
0.0

1.0

X1Ȉg+

2.0
3.0
R (ύ)

4.0

A1Ȇu

-75.609-75.659

5.0

0.0

1.0

2.0
3.0
R (ύ)

ࢺࡋࡓᚋ࡟ᐇ㦂 5.5 ࣏ࢸࣥࢩ࣮ࣕࣝ࢝

ᅗ 4.& ศᏊࡢ ;ȈJ$ȆX ≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ

ࣈࢆ㔜ࡡྜࢃࡏࡓᅗࢆ♧ࡋ࡚࠾ࡾࠊ஫࠸

ᐇ㦂 5.5 ࣏ࢸࣥࢩࣕࣝ࡜ẚ㍑

࡟㠀ᖖ࡟ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋᐇ㦂࡛ࡣ- 74 -

4.0

5.0

;ȈJ$ȆX ≧ែࡢᖹ⾮఩⨨㏆ഐࡋ࠿ᚓࡽࢀ࡚࠸࡞࠸ࡀࠊ⌮ㄽィ⟬࡛࠶ࡿ )& sij ἲ࡛ࡣᖹ⾮఩⨨࠿ࡽゎ㞳ࡲ࡛ṇࡋࡃồࡲࡗ࡚࠸ࡿࠋ&& ⤖ྜࡢ QDWXUH ࡟ࡘ࠸࡚ࠊ ᖺ࡟ 6KDLN ࡽࡣȪ⤖ྜ ࡘࡢȧ⤖ྜLQYHUWHG Ȫ⤖ྜࡢ⣧⢋࡞  㔜⤖ྜࢆᥦၐࡋࡓࡀ 66KDLN''DQRYLFK::X36X+65]HSDDQG3&+LEHUW\Nature Chem.
4   ࠊ)UHQNLQJ ࡽࡣ &+ ศᏊ ඾ᆺⓗ࡞  㔜⤖ྜࢆᣢࡘ ࡜ẚ㍑ࡋ࡚ࡶ & ศᏊࡢ⤖ྜ㊥㞳ࡣ㛗ࡍࡂࡿࡋຊࡢᐃᩘࡣᑠࡉࡍࡂࡿࡓࡵࠊࡇࡢ 6KDLN ࡢㄽᩥ࡟Req = 1.242 Ⴒ (Exptl.)ࢥ࣓ࣥࢺࡋࡓ *)UHQNLQJDQG0+HUPDQQChem. Eur.

ศᏊࡢἼື㛵ᩘࢆゎᯒࡋࠊ⤖ྜ㛫㊥㞳 R ࡟ᑐࡋ࡚ྛ
㓄⨨ࡢ DPSOLWXGH ࢆㄪ࡭ࡓ ᅗ  ࠋᇶᗏ≧ែ ;ȈJ≧

Ɏ0 amplitude

J.22   ࠋᡃࠎࡣࠊ)&sij ἲ࡛ᚓࡽࢀࡓ &

1.0

 

y1ɇg+

0.8
0.59650.6

0.53690.4

ែ ࡟ࡘ࠸࡚ࡣࠊゎ㞳≧ែࡣ & ཎᏊࡢ 3 V S ≧ែ࡛

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0.0

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C(s2p2,1)-C(s2p2,1)C(s2p2,1)-C(s2p2,2)C(s2p2,1)-C(sp3,1)C(s2p2,1)-C(sp3,2)C(s2p2,2)-C(s2p2,2)C(s2p2,2)-C(sp3,1)C(s2p2,2)-C(sp3,2)
C(sp3,1)-C(sp3,1)
C(sp3,1)-C(sp3,2)
C(sp3,2)-C(sp3,2)C-(s2p3,1)-C+(s2p,1)
C-(s2p3,1)-C+(sp2,2)C-(s2p3,1)-C+(sp2,1)
C-(s2p3,2)-C+(s2p,1)
C-(s2p3,2)-C+(sp2,1)
C-(s2p3,2)-C+(sp2,2)C-(sp4,1)-C+(s2p,1)C-(sp4,1)-C+(sp2,1)
C-(sp4,1)-C+(sp2,2)C-(sp4,2)-C+(s2p,1)C-(sp4,2)-C+(sp2,1)
C-(sp4,2)-C+(sp2,2)

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C(s2p2,1)-C(s2p2,1)C(s2p2,1)-C(s2p2,2)C(s2p2,1)-C(sp3,1)C(s2p2,1)-C(sp3,2)C(s2p2,2)-C(s2p2,2)C(s2p2,2)-C(sp3,1)C(s2p2,2)-C(sp3,2)
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C(sp3,1)-C(sp3,2)
C(sp3,2)-C(sp3,2)C-(s2p3,1)-C+(s2p,1)
C-(s2p3,1)-C+(sp2,2)C-(s2p3,1)-C+(sp2,1)
C-(s2p3,2)-C+(s2p,1)
C-(s2p3,2)-C+(sp2,1)
C-(s2p3,2)-C+(sp2,2)C-(sp4,1)-C+(s2p,1)C-(sp4,1)-C+(sp2,1)
C-(sp4,1)-C+(sp2,2)C-(sp4,2)-C+(s2p,1)C-(sp4,2)-C+(sp2,1)
C-(sp4,2)-C+(sp2,2)

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1-1 ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ GABAA ཷᐜయࡢసືᶵᵓࡢゎ᫂GABAA ཷᐜయࡣ୰ᯡ⚄⤒⣔࡟࠾࠸࡚ᢚไᛶࡢാࡁࢆࡍࡿሷ໬≀࢖࢜ࣥࢳࣕࢿ࡛ࣝ࠶ࡾ㸪඲㌟㯞㓉࡟㛵ࢃࡿཷᐜయ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ⚄⤒ఏ㐩≀㉁ GABA ࡜඲㌟㯞㓉⸆ࡀ⤖ྜࡍࡿࡇ࡜࡟ࡼࡾ㸪ཷᐜయࡢࢧࣈࣘ
ࢽࢵࢺ㛫࡛༠ㄪⓗ࡞ᵓ㐀ኚ໬ࡀ㉳ࡇࡾ㸪࢖࢜ࣥࢳࣕࢿࣝࡀ㛤ཱྀࡍࡿࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪඲㌟㯞㓉⸆ࡀཷᐜయ࡟స⏝ࡍࡿࡇ࡜࡟ࡼࡾ࢖࢜ࣥࢳࣕࢿࣝࡀ㛤ཱྀࡍࡿศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ1-2 ⩻ヂఙ㛗㐣⛬࡟࠾ࡅࡿࣜ࣎ࢯ࣮࣒࡜ tRNA ࡢ⤖ྜᶵᵓࡢゎ᫂ࣜ࣎ࢯ࣮࣒ࡣ⣽⬊࡟࠾࠸࡚ࢱࣥࣃࢡ㉁ྜᡂࢆࡘ࠿ࡉ࡝ࡿᕧ኱࡞ࢱࣥࣃࢡ㉁࣭RNA 」ྜయ࡛࠶ࡿࠋ⩻ヂఙ㛗ẁ㝵࡟࠾࠸࡚ࡣ㸪ࢱࣥࣃࢡ㉁ࡢྜᡂ࡟ᚲせ࡞࢔࣑ࣀ㓟ࢆ tRNA ࡀࣜ࣎ࢯ࣮࣒࡟㐠ᦙࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡾ㸪ࡇࡢ tRNA ࡢ㐠ᦙࡣఙ㛗ᅉᏊ࡜ࡼࡤࢀࡿࢱࣥࣃࢡ㉁࡟፹௓ࡉࢀࡿࠋࡑࡇ࡛ᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪ఙ㛗ẁ㝵࡟࠾ࡅࡿࣜ࣎ࢯ࣮࣒࡜ EF-Tu࣭tRNA 」ྜయࡢ఍ྜ࣭ゎ㞳㐣⛬ࡢศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ

2-1 ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ GABAA ཷᐜయࡢసືᶵᵓࡢゎ᫂ࢡࣛ࢖࢜㟁Ꮚ㢧ᚤ㙾ἲ࡟ࡼࡾᚓࡽࢀࡓࣄࢺ GABAA ཷᐜయ(pdb id: 6x40)࡟ࡘ࠸࡚඲ཎᏊศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋཷᐜయᵓ㐀࡟ࡘ࠸࡚⬡㉁஧㔜⭷࡜Ỉ⁐፹࡟ᇙࡵ㎸ࢇࡔ⣔ࢆ⏝ពࡋࡓࠋGABAA ཷᐜయࡢཎᏊᩘࡣ⣙ 28,000 ࡜࡞ࡾ㸪⁐፹࡞࡝ࢆྵࡵࡓ඲ཎᏊᩘࡣ⣙ 250,000 ࡛࠶ࡗࡓࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓ⣔࡟ᑐࡋ࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ GROMACS ࡟ࡼࡾᐇ⾜ࡋࡓࠋࢱࣥࣃࢡ㉁࡞࡝ࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝ
ࢠ࣮㛵ᩘ࡜ࡋ࡚ࡣ CHARMM36m ࢆ౑⏝ࡋࡓࠋཷᐜయ࡟࠾ࡅࡿ඲㌟㯞㓉⸆⤖ྜ࡟క࠺ᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡍ
ࡿࡓࡵ࡟㸪100 ns ࡢィ⟬ࢆ 6 ᅇᐇ⾜ࡋࡓࠋ
2-2 ⩻ヂఙ㛗㐣⛬࡟࠾ࡅࡿࣜ࣎ࢯ࣮࣒࡜ tRNA ࡢ⤖ྜᶵᵓࡢゎ᫂ࣜ࣎ࢯ࣮࣒」ྜయ࡜ࡋ࡚ࣜ࣎ࢯ࣮࣒ᑠࢧࣈࣘࢽࢵࢺ࣭኱ࢧࣈࣘࢽࢵࢺ㸪messenger RNA (mRNA)1 ศᏊ㸪transfer RNA (tRNA)2 ศᏊ࠾ࡼࡧ EF-Tu࣭tRNA 」ྜయࢆᑐ㇟࡜ࡋࡓࠋࡇࢀࡽࡢᵓ㐀ࢆ⢒ど໬ࣔࢹࣝ MARTINI࡛ᢅࡗࡓࠋMARTINI ࣔࢹࣝ࡟ࡼࡾ⢒ど໬ࡉࢀࡓࣜ࣎ࢯ࣮࣒ࡣ⣙ 45,000 ⢏Ꮚ࡛࠶ࡗࡓࠋࡲࡓ⁐፹࡞࡝ࢆྵࡵ
ࡓ඲⢏Ꮚᩘࡣ⣙ 270,000 ࡜࡞ࡗࡓࠋศᏊືຊᏛィ⟬ࡣ GROMACS ࡟ࡼࡾᐇ⾜ࡋࡓࠋࣜ࣎ࢯ࣮࣒࡜ EF-Tu࣭tRNA」ྜయࡢ⤖ྜࡢヲ⣽ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟㸪ึᮇᵓ㐀࠿ࡽ 1 ȝs ࡢ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ 14 ᅇ
ᐇ⾜ࡋࡓࠋࣜ࣎ࢯ࣮࣒࠿ࡽ EF-Tu࣭tRNA 」ྜయࡀゎ㞳ࡍࡿ⤒㊰ࢆ⏕ᡂࡋ㸪EF-Tu࣭tRNA 」ྜయゎ㞳ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆィ⟬ࡋࡓࠋ- 78 -

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◊✲ᡂᯝ

3-1

඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ GABAA ཷᐜయࡢసືᶵᵓࡢゎ᫂඲㌟㯞㓉⸆ࡀ GABAA ཷᐜయ࡟⤖ྜࡍࡿ࡜㸪඲㌟㯞㓉⸆ࡢ⤖ྜ㒊఩ཬࡧ 9’ࢤ࣮ࢺ㏆ഐ㸦࢖࢜ࣥࢳࣕࢿࣝࡢ
ࢤ࣮ࢺ㒊ศ㸧࡟࠾࠸࡚ᵓ㐀ࡢኚ໬ࢆぢࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ 1(a)㸧ࠋ≉࡟඲㌟㯞㓉⸆ࡢ⤖ྜ࡟క࠸㸪9’ࢤ࣮ࢺ࡟Ꮡᅾࡍࡿ࢔࣑ࣀ㓟ഃ㙐ࡢ஧㠃ゅࡀኚ໬ࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸦ᅗ 1(b)㸧
ࠋ࢖࢜ࣥࢳࣕࢿࣝࢆᵓᡂࡍࡿ 9’ࢤ࣮ࢺṧᇶ࿘㎶ࡢᵓ㐀ኚ໬࡟ࡼࡾཷᐜయࡢ኱ࡁ࡞ᵓ㐀ኚ໬࡟ࡘ࡞ࡀࡾ㸪඲㌟㯞㓉⸆ࡀ࢖࢜ࣥࡢ㏱㐣ᛶࢆไᚚࡋ࡚࠸ࡿ
ྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ
3-2⩻ヂఙ㛗㐣⛬࡟࠾ࡅࡿࣜ࣎ࢯ࣮࣒࡜ tRNA ࡢ⤖ྜᶵᵓࡢゎ᫂ᅗ 2(a)࡟♧ࡍ⣔࡟࠾࠸࡚࣓ࢱࢲ࢖ࢼ࣑ࢡࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓ⤖ᯝ㸪tRNA ࡢゎ㞳࡟క࠺⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ 2(b)㸧
ࠋࡇࡇ࡛ࡣ tRNA ࡀ㐺ษ࡞ࢥࢻ࣭ࣥ࢔ࣥࢳࢥࢻࣥ࣌࢔ࢆᙧᡂࡋ࡚࠸
ࡿሙྜ㸦ᅗ 2(b)㉥⥺㸧࡜ࡑ࠺࡛࡞࠸ሙྜ㸦ᅗ 2(b)㟷⥺㸧ࢆẚ㍑ࡋ࡚࠸ࡿࠋࡇࡢ⤖ᯝ࠿ࡽ㸪㐺ษ࡞ࢥࢻ࣭ࣥ࢔ࣥ
ࢳࢥࢻࣥ࣌࢔ࢆᙧᡂࡋ࡚࠸ࡿሙྜࡣ tRNA ࡜ࣜ࣎ࢯ࣮࣒ࡢ⤖ྜࡣᏳᐃ࡛࠶ࡾ㸪ࡑࢀࡽࡢゎ㞳ࡣ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟୙฼࡛࠶ࡿࡇ࡜ࢆ♧ࡍࡇ࡜ࡀ࡛ࡁࡓࠋ   

ᅗ 1. ඲㌟㯞㓉⸆⤖ྜ࡟క࠺ GABAA ཷᐜయࡢᵓ㐀ᅗ 2. ⩻ヂఙ㛗㐣⛬࡟࠾ࡅࡿࣜ࣎ࢯ࣮࣒ࠋ(a) ࢩ࣑࣮ࣗࣞࢩࣙ

ኚ໬ࠋ(a) 9’ࢤ࣮ࢺᵓ㐀ࡢ᫬㛫Ⓨᒎ࠾ࡼࡧ (b) ᑐᛂࣥ⣔ࡢᵓ㐀࠾ࡼࡧ (b) tRNA ゎ㞳㐣⛬࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠࡍࡿഃ㙐ᵓ㐀ࡢኚ໬ࠋ࣮ᆅᙧࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
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㟁Ꮚ≧ែィ⟬࡟ࡼࡿ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ⁐ᾮ⏺㠃ࡢ㛵ࢃࡿ⌧㇟ࡣࠊ⇕ຊᏛࠊ㟁Ẽ໬ᏛࡸศගᏛ࡟ᇶ࡙ࡃほࡀ࡞ࡉࢀ࡚ࡁࡓࡀࠊᐇ㦂࡛ࡣ⁐ᾮ⏺㠃ࡢศᏊࢆ㑅ᢥⓗ࡟࡜ࡽ࠼࡚ほࡍࡿࡇ࡜ࡀ㞴ࡋࡃࠊ࣑ࢡ࡛ࣟ⢭ᐦ࡞ゎ᫂࡟ࡣ⌮ㄽィ⟬࡜ࡢ༠ຊࡀ࡜ࡾࢃࡅᚲせ࡜ࡉࢀࡿࠋᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ⁐ᾮ⏺㠃ࡢศᏊࢆᤊ࠼ࡿᩘᑡ࡞࠸
᭷ຊ࡞ᐇ㦂ᡭἲ࡛࠶ࡿ⏺㠃࿴࿘ἼⓎ⏕ศගࡢ⌮ㄽィ⟬ᡭἲࢆ⾜࠸ࠊࡑࢀ࡟ᇶ࡙ࡃࡑࡢᛂ⏝ࢆ㐍ࡵ࡚ࡁࡓࠋᮏ
ᖺᗘ࡟ࡣ⏺㠃ศගࡢィ⟬ᡭἲ࡟࠾࠸࡚ᚑ᮶ぢ㏨ࡉࢀ࡚ࡁࡓቃ⏺᮲௳ࡢᙳ㡪ࢆ⣔⤫ⓗ࡟᳨ウࡋ࡚᫂ࡽ࠿࡜ࡋ࡚ࠊ
ṇࡋ࠸ቃ⏺᮲௳ࡢྲྀࡾ᪉ࢆ୚࠼ࡓࠋࡲࡓࠊ᣺ືᕪࢫ࣌ࢡࢺࣝィ⟬ࡢຠ⋡ࢆ᫖ᖺᗘࡲ࡛ࡼࡾࡶ๻ⓗ࡟ᨵၿࡍࡿ
࢔ࣝࢦࣜࢬ࣒ࢆᐇ⿦ࡋ࡚ᐇ⏝໬ࡋࡓࠋࡲࡓࠊᐇ㦂ࢢ࣮ࣝࣉࢆඹྠ࡛㟁ゎ㉁Ỉ⁐ᾮࡢ࣐ࣛࣥศගࡢᕪࢫ࣌ࢡࢺ
ࣝࢆゎᯒࡋࠊ㟁ゎ㉁Ỉ⁐ᾮෆ࡛ࡢ࢖࢜ࣥ࣌࢔≧ែࢆ▱ࡿࡇ࡜ࡀ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ⏺㠃㠀⥺ᙧศගࡢィ⟬ࡣࠊᡃࠎࡢ㛤Ⓨࡋࡓ㟁Ꮚศᴟࣔࢹࣝ࡟ᇶ࡙ࡃศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ࠶ࡾࠊ

᫬ࠎ้ࠎ࡛ࡢ⏺㠃⣔ࡢศᴟࢆィ⟬ࡍࡿ 0' ࣉࣟࢢ࣒ࣛ &DOQRV ࡢ㛤Ⓨࢆᮏࢢ࣮ࣝࣉ࡛㐍ࡵࡘࡘࠊࡑࢀࢆ⏝࠸ࡓ◊✲ࢆ㐙⾜ࡋ࡚ࡁࡓࠋ௨ୗ࡟㏙࡭ࡿ᣺ືᕪࢫ࣌ࢡࢺࣝィ⟬ࡶ &DOQRV ࡢࣉࣛࢵࢺࣇ࢛࣮࣒ୖ࡛ᐇ⿦ࢆ⾜ࡗࡓࠋ
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 ࿴࿘Ἴศගィ⟬࡟࠾ࡅࡿቃ⏺ၥ㢟ࡢゎỴ>@ ᮏࢢ࣮ࣝࣉࡣࠊ⏺㠃࿴࿘Ἴศගࡢ᣺ືࢫ࣌ࢡࢺࣝࢆ᫬㛫┦㛵㛵ᩘ࡟ᇶ࡙࠸࡚ィ⟬ࡍࡿ⌮ㄽᡭἲࢆᥦ᱌ࡋࠊ
ࡑࡢᛂ⏝ࢆ㐍ࡵ࡚ࡁࡓࠋࡑࡢ㝿࡟⏺㠃ࢆᢅ࠺ 0' ィ⟬࡛ࡣࠊ࿘ᮇቃ⏺᮲௳ࡢࡶ࡜࡛ 0' ࢭࣝෆ࡟ࢫࣛࣈᙧ≧ࡢ⣔ࢆ⏝ពࡋ࡚ࠊࢫࣛࣈࡢ୧㠃࡟⏕ࡌࡿ⏺㠃ࡢಙྕࢆูࠎ࡟ࢧࣥࣉࣜࣥࢢࡋ࡚ィ⟬ࡍࡿࠋࢫࣛࣈࡢ୰ኸ㒊ศࡣࣂࣝࢡ࡜࡞ࡾࠊ⏺㠃ศගࡢࢩࢢࢼࣝࢆⓎ⏕ࡋ࡞࠸ࠋࡲࡓ༑ศ࡟ศᏊ㛫ࡢ㊥㞳ࡀ㞳ࢀࡓሙྜ࡟ࡶࠊࡑࡢ㛫࡛┦㛵㛵ᩘ࡬ࡢᐤ୚ࡣᾘ࠼ࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ᐇ㝿ࡢィ⟬࡛ࡣࠊᐤ୚ࡀᏑᅾࡋ࡞࠸ࢧࣥࣉࣜࣥࢢ㡿ᇦࢆ㐺ᐅไ㝈ࡍࡿࡇ࡜࡛ࠊ┦㛵㛵ᩘࡢࢧࣥࣉࣜࣥࢢࡀ࡞ࡉࢀࡿࠋࡑࡢ㝿ࡢቃ⏺᮲௳ࡣࠊࢩࢢࢼࣝࡢᏑᅾࡋ࡞࠸㡿ᇦ࡟࠾࠿ࢀࡿࡓࡵࠊࡑࡢヲ⣽ࡣ⤖ᯝ࡟ࡣᙳ㡪ࡋ࡞࠸ࡣࡎ࡜⪃࠼ࡽࢀࠊ༑ศ࡟వ⿱ࢆࡶࡗ࡚࡜ࡿ㝈ࡾࠊࡑࡢᙳ㡪ࡣ࠶ࡲࡾὀ┠ࡉࢀ࡞࠸࡛࠸ࡓࠋࡋ࠿ࡋᮏ◊✲࡛ࡣࠊࣂࣝࢡ୰ࡢቃ⏺᮲௳ࡢྲྀࡾ᪉ࡀ 0' ィ⟬࡟୚࠼ࡿࡉࡲࡊ
ࡲ࡞ᙳ㡪ࢆ᫂ࡽ࠿࡜ࡋࠊࡑࡢṇࡋ࠸ቃ⏺᮲௳ࡢྲྀࡾ᪉ࡢᣦ㔪ࢆ☜❧ࡋࡓࠋ࡜ࡾࢃࡅࠊቃ⏺᮲௳࡟ᑐࡋ࡚཮ᴟ
Ꮚ࡜ศᴟ⋡ࡢࢧࣥࣉࣜࣥࢢࢆ➼౯࡟ᢅ࠺ࡇ࡜ࡀṇࡋ࠸ቃ⏺࡟࡜ࡗ࡚ᚲせ࡛ࠊࡑࢀࡀ◚ࢀࡿ࡜ࡁ࡟ DUWLIDFW ࡀ- 84 -

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ࢀࢆゎỴࡍࡿ࡟ࡣᅄ㔜ᴟࡢᐤ୚ࡶṇࡋࡃィ⟬࡟ྲྀࡾ㎸ࡴᚲせࡀ࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡜ࡋࡓࠋ
>@7+LUDQRDQG $0RULWDJ. Chem. Phys.156   ᣺ືᕪࢫ࣌ࢡࢺࣝࡢ⌮ㄽ㛤Ⓨࡢ㐍ᒎ>@ศගゎᯒࡢᐇ㦂࡛ࡣ  ࡘࡢഹ࠿࡟␗࡞ࡿ⣔ࡢࢫ࣌ࢡࢺࣝࡢᕪࢆࡳࡿࡇ࡜࡛ࠊほ ࡍࡿᑐ㇟࡬ࡢឤᗘ࡜㑅ᢥᛶࢆ㧗ࡵࡿᕤኵࡀࡋࡤࡋࡤ⏝࠸ࡽࢀࡿࠋࡋ࠿ࡋ 0' ィ⟬࡟ࡼࡿゎᯒ࡛ࠊ ࡘࡢ␗࡞ࡿ⣔ࡢ㛫ࡢᚤᑠ࡞ᕪࢆồࡵࡿ࡟ࡣࠊࡑࢀࡒࢀࡢࢫ࣌ࢡࢺࣝࡢ⤫ィㄗᕪࢆᴟࡵ࡚Ⰻࡃࡍࡿࡇ࡜ࡀᚲせ᮲௳࡜࡞ࡾࠊᐇ㝿ࡢィ⟬ࢆ㐙⾜ࡍࡿࡢࡣᴟࡵ࡚ィ⟬ࢥࢫࢺࡢ࠿࠿ࡿၥ㢟࡛࠶ࡗࡓࠋࡑࡇ࡛ᮏࢢ࣮ࣝࣉ࡛ࡣࠊ ࡘࡢࢫ࣌ࢡࢺࣝࢆồࡵ࡚ᕪࢆ࡜
ࡿࡢ࡛ࡣ࡞ࡃࠊᚤᑠ࡞᣺ືᕪࢫ࣌ࢡࢺࣝ⮬యࢆ┤᥋࡟ 0' ィ⟬࡛ồࡵ࡚ゎᯒࡍࡿ⌮ㄽⓗ࡞ᡭἲࢆ㛤Ⓨࡋ࡚ࡁࡓࠋࡇࢀࡣࣂࢵࢡࢢࣛ࢘ࣥࢻࡢᙳ㡪ࢆึࡵ࠿ࡽ㝖ࡃࡇ࡜࡛ࠊ༢࡞ࡿ  ࡘࡢࢫ࣌ࢡࢺࣝࡢᕪࡢィ⟬ࡼࡾࡶᅽಽ
ⓗ࡟཰᮰ࢆ᪩ࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ௒ᖺᗘ࡟ࡣࡑࡢ⌮ㄽ࡟ᑐࡋ࡚᪂ࡓ࡞࢔ࣝࢦࣜࢬ࣒ࢆᐇ⿦ࡍࡿࡇ࡜࡟ࡼࡾࠊ
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ࢺࣝࢆ⌮ㄽィ⟬࡛ゎᯒࡍࡿࡇ࡜࡛ࠊỈ⁐ᾮ୰ࡢ࢖࢜ࣥᑐ≧ែ࡟ࡘ࠸࡚࣑ࢡࣟ࡞᝟ሗࢆᚓࡽࢀࡿࡇ࡜ࢆ♧ࡋࡓࠋ
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ຌ‫Ͳڂݜ‬ͺ”εέϫϘϱνζΦόϱۜ଒ࡪରͶΓΖۜ଒ഓҒࢢ‫ڢ‬ಉద݃߻઀இൕԢ͹֋൅”͕Γ;”༙‫ؽ‬υώ΢ηΝࢨ޴ͪ͢๗ߵଔԿ߻෼͹અ‫”ܯ‬Νߨ͏Ήͤɽ࠹शదͶͺ৿‫و‬ৰഖɼ๗ߵଔԿ߻෼͹અ‫ܯ‬ɼ͕Γ;ൕԢ‫ؽ‬ߑ͹մ໎΃͹எ‫ݡ‬Νಚͱɼࣰࡏ͹ৰഖ߻੔ɼυώ΢ηԢ༽Ͷൕӫͦ͠ɼ৿‫ؽو‬೵Ν࣍ͯયҢۜ଒ৰഖ͕Γ;๗ߵଔԿ߻෼͹߻੔Ν໪ࢨ͢Ήͤɽ
1-1.ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨգ‫ڊ‬Ͷըʓͺɼۜ଒ഓҒࢢ‫ڢ‬ಉద H–H ݃߻઀இΝ伶ͳͪ͢ C–C ݃߻͹୦ਭોԿൕԢ(J. Am. Chem. Soc. 2013,
135, 18726.)ΏɾC–O ݃߻͹Յਭો෾մൕԢ(Nat. Commun. 2015, 6, 6296.)Νๅࠄ͢Ήͪ͢ɽΉͪҲ๏Ͳɾۛ೧ըʓͺɼεέϫϘϱνζΦόϱ΢ϨζΤϞࡪରͳ୺Կਭોͳ͹ൕԢΝୣ੔͢Ήͪ͢ɽ
ʤFigure 1, J. Am. Chem.
Soc. 2021, 143, 12999–13004.ʥ
ɽਦͶࣖͤ௪ΕɼDFT ‫ࢋܯ‬ͶΓΕઅ‫ͪ͢ܯ‬ΦφΫεΩϩϚωϩ‫خ‬஖‫׷‬εέϫϘϱνζΦόϱഓҒࢢΝ࣍ͯ΢ϨζΤϞϐχϨχࡪର 1 ͳωφϫϟνϱΝൕԢͦͪ͠ͳ͞ΘɼϐχϫΫεεέ
ϫϘϱνζΦωϩωφϫϟοϩ΢ϨζΤϞࡪର 2 ΝಚΖ͞ͳͶ੔ޯ͢Ήͪ͢ɽ͞͹ൕԢͺɼۜ଒஦ৼ͹࢐ԿΝ൒͏͵͗Δ C–H ݃߻Ν෈‫ۋ‬౵Ͷ઀இͤΖͳ͏͑ɼॊཔஎΔΗΖ C–H ݃߻‫׈‬੓Կ๑ͳͺҡ͵Ζ‫Ͳࣞܙ‬਒ߨ
ͤΖ͞ͳ͗Κ͖ΕΉͪ͢ɽ

Figure ̏. εέϫϘϱνζΦόϱ΢ϨζΤϞࡪରͶΓΖ C–H ݃߻͹෈‫ۋ‬౵࢐Կద෉ՅൕԢ
ຌ‫Ͳڂݜ‬ͺɾۜ଒ഓҒࢢ‫ڢ‬ಉࡠ༽Ν઴ब‫غ‬યҢۜ଒ࡪର΃ఴ֋͢ɾͨΗΔ͹ৰഖൕԢ͹֋൅Ν໪ࢨ͢Ήͪ͢ɽεέϫϘϱνζΦόϱഓҒࢢ৏͹஖‫خ׷‬ɾۜ଒ɾࢩ࣍ഓҒࢢ͹ૌΊ߻Κͦ͗݃߻઀இ‫׈‬੓Ͷଲ͢ͱʹ͹Γ͑ͶӪ‫ڻ‬Ν༫͓Ζ͖ɾDFT ‫ࢋܯ‬Ͷ‫͚Ͱخ‬༩଎Νߨ͑͞ͳͲ‫ڂݜ‬ΝՅଐͦ͠Ήͪ͢ɽ- 88 -

1-2. ᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ
Ru ϛϨϒϨζϩࡪରͺࢀ॑ߴ MLCT ྯًয়ସͶ༟པͤΖޭָಝ੓͗ಝ௅ద͵෾ࢢͲͤɽ͞͹ࡪରͶଠ͹ഓҒ෨ҒΝઅ͜Ζͳɼͨ͹ޭָಝ੓ͺഓҒͶΓͮͱ௒੖ͤΖ͞ͳ͗Ͳ͘Ήͤɽຌ‫Ͳڂݜ‬ͺɼ1,1,2,2-τφϧϒϧμϨϩΦτϱɼLet ͳͨ͹ϩτωΤϞࡪର Ru(bpy)2Let ͠ΔͶɼ
RuPd ್֫ࡪର Ru(bpy)2LetPdCl2 ͹߻੔Νߨ͏ɼͨ͹ޭ‫ڏ‬ಊͶ‫ࡱߡͱؖ͢‬Νߨ͏Ήͪ͢ɽ)LJXUHH/HW ΝഓҒࢢͳͤΖ 5X ୱ֫ࡪର 5XES\/HWʤ੪ʥͳ 5X3G ್֫ࡪର 5XES\/HW3G&Oʤᒷʥ
2◊✲᪉ἲࠊィ⟬᪉ἲεέϫϘϱνζΦόϱۜ଒ࡪରͶΓΖۜ଒ഓҒࢢ‫ڢ‬ಉద݃߻઀இൕԢ͹֋൅‫Ͳڂݜ‬ͺɼGaussian 16 ϕϫήϧϞΝ༽͏ͱɼM06/def2-TZVP Ν࢘ͮͱ‫خ‬ఊয়ସɼયҢয়ସɼIRC ‫ࢋܯ‬Νߨ͏Ήͪ͢ɽ༙‫ؽ‬υώ΢ηΝࢨ޴ͪ͢๗ߵଔԿ߻෼͹અ‫ܯ‬͹‫Ͳڂݜ‬ͺɼGaussian 09 ϕϫήϧϞΝ༽͏ͱɼM06/sdd (for Metals) 6-31G(d,p)(forothers)Ν࢘ͮͱ‫خ‬ఊয়ସ͹‫ࢋܯ‬ɼTD-DFT ͶΓΖ UV ηϘέφϩ͹ਬ଎Νߨ͏Ήͪ͢ɽ3◊✲ᡂᯝ
3.1 ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤ⓎΉͥɼըʓͺɼεέϫϘϱνζΦόϱώψζΤϞࡪର 3 ͹߻੔ΝࢾΊΉͪ͢

(Organometallics 2023, 42, 865–870. )ɽୱ݃ধ X તߑଆմੵͶΓΕɼ͞͹ࡪର͹εέϫϘϱν
ζΦόϱഓҒࢢ͹ CʻO ݃߻͗৵ௗͪ͢͞ͳ͖Δɼۜ଒͖ΔεέϫϘϱνζΦόϱഓҒࢢ΃͹‫͏ک‬ుࢢҢಊ͗ࣖࠨ͠ΗΉͪ͢ɽΉͪɼDFT ‫ࢋܯ‬ͶΓͮͱɼώψζΤϞࡪର̑̑͹ HOMO-1
Ͷ͕͏ͱώψζΤϞ͖Δ CʻO ݃߻͹ൕ݃߻੓ٌಕͶుࢢ͗Ңಊ͢ͱ͏Ζ͞ͳΝ໎Δ͖Ͷ͢Ήͪ͢(Figure 3)ɽ͞Ηͺ෈҈ఈ͵ఁ‫ࢢݬ‬ՃώψζΤϞΝుࢢ‫ٽ‬Ӏ੓͹ഓҒࢢ͗҈ఈԿͦ͠ͱ͏Ζ͞ͳΝࣖ͢ɼࠕ‫ޛ‬΍Ӏ͘କ͘઴ब‫غ‬યҢۜ଒ࡪରͶΓΖ݃߻઀இൕԢ͹֋൅Ν਒ΌͱΉ͏ΕΉͤɽ

Figure 3. εέϫϘϱνζΦόϱώψζΤϞࡪର৏Ͳ͹ుࢢҢಊ

- 89 -

᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィΉͥըʓͺɼୱ֫ࡪରͳ್֫ࡪରͶ͕͜Ζ‫ޭٷ‬ɼ൅ޭ଎ఈ͖Δɼޭ‫ڏ‬ಊ͹մ໎ΝࢾΊΉͪ͢ɽͨ͹݃Վɼྈं͹‫ޭٷ‬ηϘέφϩ͗ࠇࣇ͢ͱ͏ΖͶ΍‫ؖ‬ΚΔͥɼ್֫ࡪରͶ͕͏ͱ͹Ίɼ600 nm ෉ۛ͹‫ౕ͗کޭܮ‬ஸ͚͢‫ݰ‬ਲ͢ͱ͏Ζ͞ͳ͗Κ͖ΕΉͪ͢(Figure 4 ࠪ)ɽ͠ΔͶ DFT ‫͖ࢋܯ‬Δୱ֫ࡪର͹ LUMO ͺ bpy ϤωρφͶ
‫ࡑۃ‬Կ͢ͱ͏ΖҲ๏Ͳɼ್֫ࡪରͶ͕͜Ζ LUMO ͺ bpy ͳ Let Ͷඉ‫ࡑۃ‬Կ͢ͱ͏Ζ͞ͳΝ͍͘Δ͖Ͷ͢Ήͪ͢(Figure 4 ࠪ)ɽ͞͹‫ڏ‬ಊͺɼRu ͖Δ Pd ΃͹ްིద͵ΦϋϩάʖҢಊΝཬ෉͜Ζ݃ՎͲ͍Εɼ͞ΗͺՏ‫ڰ‬ഓҒࢢ Let ͗ϧζΩϩΠωΨϱΝखΕͰΔ͏͞ͳͶًҾͤΖͳߡ͓ͱ͏Ήͤɽࠕ‫ޛ‬ͺޭଁ‫ͱ͢ͳࡐ״‬͹Ԣ༽Ν‫غ‬ଶ͢ͱɼ֦झ଎ఈɼ‫ࢋܯ‬ΝߨͮͱΉ͏ΕΉͤɽ

Figure 4. Let ΝഓҒࢢͳͤΖࡪର͹ LUMO ͹ుࢢߑଆʤࠪʥͳ൅ޭηϘέφϩʤӊʥ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ʀPolymers containing ester and ketone groups in chains: synthesis and their biodegradability. Haobo Yuan, Kohei
Takahashi, Shinya Hahashi, Chifeng Li, Kazuya Yamaguchi, Miwa Suzuki, Kenichi Kasuya, Kyoko Nozaki, ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ K301-3pm-03 (޳ಆ)ʀPt ୴࣍ WO3−ZrO2 ৰഖΝ༽͏ͪΦητϩ͖ΔΠϩΩϱ΃͹߶ްི͵Յਭો෾մൕԢ ࢃ㟔 ༓ߵཀྵʀKang
Yuanʀۜ ༦ܾʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22–25
ೖ K305-4am-03 (޳ಆ)˔Synthesis and Reactivities of Cyclopentadienone Group 5 Metal Complexes. ౨ ୕໷ʀ೉ຌ बฑʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ K404-2am-03 (޳ಆ)˔ζϚϨϩΩϩϗό΢χ͹߻੔ͳζϚϨϩΩϩϗϱ౵Ճରͳ͢ͱ͹੓࣯ ᖄ୫ ༒‫س‬ʀ೉ຌ बฑʀ໼࡜ ‫ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ K603-3am-02 (޳ಆ)˔ϩ΢η࢐੓ओഓҒΠωΨϱ͹֋൅͕Γ;Ғ஖મ୔ద C-H ‫ׯ‬೵‫خ‬Կ΃͹Ԣ༽ ᤊେ ྕʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ښ‬ࢢ ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ K502-3pm-02 (޳ಆ)˔΢ϨζΤϞৰഖΝ༽͏ͪζϙϩϞΠϝχͳζΠϝϱ΃͹મ୔దਭોԿ෾մͶΓΖϛϨΤϪΠधࢹ͹ίϝΩϩϨγ΢έϩ ௱৪ Ҳٍʀ಼౽ ௜धʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీ
ΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ K404-4am-04 (޳ಆ)˔φϨη(ϑΠϨʖϩζ΢ϩ)ϫζΤϞ(III)࢐/΢ϨζΤϞ(III)࢐ࡪର͹߻੔ɾߑଆ͕Γ;ޭ෼੓ ‫ ݬ‬ਜ਼ٕʀ኏Ԯ
༐ࢢʀ‫ن޻ ࡜آ‬ʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22
t25 ೖ K504-3am-13 (޳ಆ)˔΢ϨζΤϞৰഖͶΓΖΤϪΠྪ͹ϙϩϞΠϝχͳΠϝϱ΃͹ਭોԿ෾մͶ͕͜ΖഓҒࢢ͹ްՎ͹մ໎ ಼- 90 -౽ ௜धʀ௱৪ Ҳٍʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ
2023 ೧ 3 ݆ 22t25 ೖ K502-2vn-14 (޳ಆ)˔PN ഓҒࢢΝ༙ͤΖϜϱΪϱࡪର͹߻੔ͳΩϩϚωϩԿ߻෼͹ਭોԿൕԢ΃͹Ԣ༽ ᜌ౽ ਖ಺ʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023 ೧ 3 ݆ 22t25 ೖ
K504-2vn-06 (޳ಆ)ʀϤΤϫϒΤϞࡪର͗ഖղͤΖΠιφϓΥόϱ͹ՅΠϩαʖϩ෾մͶ͕͜Ζ୺ો-୺ો݃߻͹઀இ ็‫࣑ ڋ‬‫س‬ʀঘ‫ ݬ‬૘Ҳ࿗ʀ೉ຌ बฑʀ໼࡜ ‫ ࢢښ‬ೖຌԿָճ୊ 103 ॡ‫ل‬೧ճ ౨‫ښ‬ཀྵՌ୉ָ໼ీΫϡϱϏη એཁ 2023
೧ 3 ݆ 22t25 ೖ K705-3am-05 (޳ಆ)˔Heterolytic oxidative addition of group 13/14 element–hydrogen bonds by cyclopentadienone iridium complexes.
Takuya Higashi, Shuhei Kusumoto, Kyoko Nozaki, 15th CaRLa Winter School 2023 German-American Institute,
Heidelberg, Germany, 2023/03/19–24 (Poster).
˔ϑηʤΩϩϚζϙηϙϧϱʥ͹߻੔ͳఱ‫ݫܗ‬ો΃͹ഓҒ‫ڏ‬ಊ ᜌ౽ ᠵʀ೉ຌ बฑʀ໼࡜ ‫ ࢢښ‬୊ 49 յ༙‫ؽ‬ఱ‫ݫܗ‬ોԿָ౾࿨ճ ෍ࢃ୉ָࠉీߪಌ‫ָ;ٶ‬ਫ਼ճ‫ ؙ‬෍ࢃ 2022 ೧ 12 ݆ 8t10 ೖ PB-078 (ϛηνʖ)˔ϙηϓΡϱϒϫϨχഓҒࢢΝ༙ͤΖ΢ϨζΤϞৰഖͶΓΖΤϪΠྪ͹ϙϩϞΠϝχͳΠϝϱϖ͹મ୔దਭોԿ෾մ ௱৪ Ҳٍʀ಼౽ ௜धʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ ࢢښ‬୊ 12 յ CSJ ԿָϓΥην 2022 νϭʖϙʖϩ઩ຉ౨‫ ښ‬2022 ೧ 10 ݆ 18t20 ೖ P1-062 (ϛηνʖ)
ʀAu/CeO2 ͶΓΖ߻੔Ϊη஦Ͳ͹Πϩυϐχમ୔దؒ‫ͳݫ‬νϱυϞൕԢ΃͹Ԣ༽ പࢃ ߔଢ࿢ʀۜ ༦ܾʀ໼࡜ ‫ ࢢښ‬୊ 12 յ CSJ ԿָϓΥην 2022 νϭʖϙʖϩ઩ຉ ౨‫ ښ‬2022 ೧ 10 ݆ 18t20 ೖ P2-044 (ϛηνʖ)˔Atom Swapping on Aromatic Rings: Conversion from Phosphinine Pincer Metal Complexes to Metallabenzenes byO2 Oxidation. ਜ਼ీ ߔҲ࿗ʀ೉ຌ बฑʀ໼࡜ ‫ࡪ ࢢښ‬ରԿָճ୊ 72 յ౾࿨ճ ۟य୉ָґ౐ΫϡϱϏη ෳ
Ԯ 2022 ೧ 9 ݆ 26-28 ೖ 2D-02 (޳ಆ)ʀAu/CeO2 ͶΓΖ߻੔Ϊη஦Ͳ͹Πϩυϐχમ୔దؒ‫ͳݫ‬νϱυϞൕԢ΃͹Ԣ༽ പࢃ ߔଢ࿢ʀۜ ༦ܾʀ໼࡜ ‫ ࢢښ‬୊ 130 յৰഖ౾࿨ճ ෍ࢃ୉ָ‫ޔ‬ෳΫϡϱϏη ෍ࢃ 2022 ೧ 9 ݆ 20t22 ೖ 1I01 (޳ಆ)
˔1,1,2,2-τφϧϒϧμϨϩΦτϱΝ伶ͳͤΖ Ru ࡪର͹ޭ‫ڏ‬ಊ ෤੕ ༦୉ʀ໼࡜ ‫ ࢢښ‬୊ 32 յ‫ؽ༙ેخ‬Կָ౾࿨ճ ‫౐ښ‬Ϗϩηϕϧδ ‫ ౐ښ‬2022 ೧ 9 ݆ 20t22 ೖ 2P116 (ϛηνʖ)˔ϙΤો್஖‫׷‬Ωϩϗϱ͹൅ਫ਼ͳ؏଎ ᖄ୫ ༒‫س‬ʀ೉ຌ बฑʀ໼࡜ ‫ ࢢښ‬୊ 32 յ‫ؽ༙ેخ‬Կָ౾࿨ճ ‫౐ښ‬Ϗϩηϕϧδ ‫ ౐ښ‬2022 ೧ 9 ݆ 20t22 ೖ 2A07 (޳ಆ)˔΢ϨζΤϞৰഖͶΓΖΤϪΠྪમ୔ద͵ϙϩϞΠϝχͳΠϝϱϖ͹ਭોԿ෾մ ௱৪ Ҳٍʀ಼౽ ௜धʀ‫آ‬㟔 ޻‫ن‬ʀ໼࡜ ‫ ࢢښ‬୊ 68 յ༙‫ۜؽ‬଒Կָ౾࿨ճ ౨‫ۂ޽ښ‬୉ָ୉ԮࢃΫϡϱϏη ౨‫ ښ‬2022 ೧ 9 ݆ 6t8 ೖ
PA-06 (ϛηνʖ)˔εέϫϘϱνζΦόϱ΢ϨζΤϞࡪରͶΓΖۜ଒tഓҒࢢ‫ڢ‬ಉద 13 ଔ/14 ଔ‫ݫ‬ોtਭો݃߻͹઀இൕԢ ౨୕໷ʀ೉ຌ बฑʀ໼࡜ ‫ ࢢښ‬୊ 68 յ༙‫ۜؽ‬଒Կָ౾࿨ճ ౨‫ۂ޽ښ‬୉ָ୉ԮࢃΫϡϱϏη ౨‫ ښ‬2022 ೧ 9
݆ 6t8 ೖ O3-07 (޳ಆ)ϛϨίφϱ͹ Baeyer-Villiger ࢐ԿͶΓΖΦητϩ‫༙؜خ‬ϛϨϜʖ͹߻੔ͳͨ͹෾մ੓͹඲Ճ ߶‫ߪ ڰ‬ฑʀᦶߔഀʀྜྷ ৽໷ʀྵ໨ ඔ࿪ʀബ୫ ݊Ҳʀ໼࡜ ‫ ࢢښ‬୊ 71 յ߶෾ࢢԿָ౾࿨ճ ๼քಕ୉ָࡵຊΫϡϱϏη ๼
քಕ 2022 ೧ 9 ݆ 5t7 ೖ 3E06 (޳ಆ)
˔1,1,2,2-τφϧϒϧμϨϩΦτϱΝ伶ͳͤΖ Ru ࡪର͹ޭ‫ڏ‬ಊ ෤੕ ༦୉ʀ໼࡜ ‫ ࢢښ‬୊ 33 յഓҒԿ߻෼͹ޭԿָ౾࿨ճ Ψϱϧ΢ϱ 2022 ೧ 8 ݆ 5t7 ೖ P-49 (ϛηνʖ)- 91 -

ʀϟνϨϱ࢐ΠϩϝωΤϞ୴࣍പۜৰഖͶΓΖ CtO ݃߻͹મ୔దՅਭો෾մൕԢ ۜ ༦ܾʀ݆ଞ ཨॻʀᦶ߃ʀ૮‫࢚݊ ݬ‬ʀࢀӞ ୉धʀࣣ‫ ރ‬ఫ໷ʀ໼࡜ ‫ ࢢښ‬୊ 129 յৰഖ౾࿨ճ ‫౐ښ‬୉ָ٤ీΫϡϱϏη ‫ ౐ښ‬2022
೧ 3 ݆ 28t30 ೖ 2A04 (޳ಆ)

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ʀHydrogen-induced formation of surface acid sites on Pt/Al(PO3)3 enables remarkably efficient hydrogenolysis of C−O
bonds in alcohols and ethers
K. Oshida, K. Yuan, Y. Yamazaki, R. Tsukimura, X. Jin, K. Nozaki
ChemRxiv 2023 (preprint) 10.26434/chemrxiv-2023-vjn0d
ʀNickel-Catalyzed Selective Incorporation of Isolated In-Chain Carbonyls into Ethylene/Carbon Monoxide Copolymer
Using Metal Carbonyls as a Carbonyl Source
G. Yonezaki, F. Seidel, K. Takahashi, K. Nozaki
Bull. Chem. Soc. Jpn. in press. 10.1246/bcsj.20230073
˔Cyclopentadienone Vanadium(I) Complex; Synthesis, Red-Ox Activity and Application to Catalytic Transfer
Hydrogenation
T. Higashi, S. Kusumoto, K. Nozaki
Organometallics 2023, 42, 865–870. 10.1021/acs.organomet.3c00135
˔Structure and Reactivity of Ag(I) Complexes Bearing Tridentate Phosphinine Ligands
K. Masada, S. Kusumoto, K. Nozaki
Organometallics 2023, 42, 971–981. 10.1021/acs.organomet.3c00143
˔Chemoselectivity Change in Catalytic Hydrogenolysis: Ureas to Formamides and Amines
T. Iwasaki, K. Tsuge, N. Naito, K. Nozaki
ChemRxiv 2023 (preprint) 10.26434/chemrxiv-2023-z49zw
ʀMultifunctional WO3−ZrO2-supported Platinum Catalyst for Remarkably Efficient Hydrogenolysis of Esters to
AlkanesK. Yuan, Y. Yamazaki, X. Jin, K. Nozaki
J. Am. Chem. Soc. 2023, 145, 3454–3461. 10.1021/jacs.2c11145 Featured on the supplementary cover.
ʀChain Transfer Approach for Terminal Functionalization of Alternating Copolymerization of CO2 and Epoxide by
Using Active Methylene Compounds as Chain Transfer Agents
H. Nagae, S. Akebi, S. Matsushiro, K. Sakamoto, T. Iwasaki, K. Nozaki, K. Mashima
Macromolecules 2022, 55, 9066–9073. 10.1021/acs.macromol.2c01761
˔TEMPO as a Hydrogen Atom Transfer Catalyst for Aerobic Dehydrogenation of Activated Alkanes to Alkenes
T. Ito, F. Seidel, X. Jin, K. Nozaki
J. Org. Chem. 2022, 87, 12733–12740. 10.1021/acs.joc.2c01302 Selected as Most Read Articles in September 2022.
˔Electron in a cube: Synthesis and characterization of perfluorocubane as an electron acceptor
M. Sugiyama, M. Akiyama, Y. Yonezawa, K. Komaguchi, M. Higashi, K. Nozaki, T. Okazoe
Science 2022, 377, 756–759. 10.1126/science.abq0516
˔Pincer-Supported Perfluororhodacyclopentanes: High Nucleophilicity of M–CF Bond
S. Hayashi, T. Murayama, S. Kusumoto, K. Nozaki- 92 -

Angew. Chem. Int. Ed. 2022, 61, e202207760. 10.1002/anie.202207760
ʀMechanistic Insight into Rh-Catalyzed C(sp2)–O Bond Cleavage Applied to Cross-Coupling Reaction of Benzofuranswith Aryl Grignard Reagents
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ACS Catal. 2022, 12, 7936–7949. 10.1021/acscatal.2c01974
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˔Incorporation of CO2-derived Bicyclic Lactone into Conventional Vinyl Polymers
M. Hill, S. Tang, K. Masada, Y. Hirooka, K. Nozaki
Macromolecules 2022, 55, 3311–3316. 10.1021/acs.macromol.1c02503- 93 -

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ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲㸦PAHs㸧࡜⁐፹ศᏊ࡜ࡢ┦஫స⏝ࡣࠊ໬Ꮫⓗ࠾ࡼࡧ⏕≀ᏛⓗศᏊㄆ㆑㐣⛬࡟࠾࠸࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋ≉࡟ࠊPAHs ࡣ㝹▼ࠊᙟᫍࡢ⾲㠃࡜࠸ࡗࡓᫍ㛫ሻ⾲㠃࡟ᬑ㐢ⓗ࡟ぢࡽࢀࡿ᭷ᶵᡂศ
ࡢ୍ࡘ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᫍ㛫ሻ⾲㠃࡟࠾ࡅࡿᏱᐂ⥺↷ᑕ࡟ࡼࡿ PAHs ࡢගศゎ࡟ࡼࡗ࡚⏕ࡌࡿ཯
ᛂࡣࠊPAHs ࡢỈ⣲໬࡟ࡼࡿ㑏ඖࡸࠊࢣࢺࣥࡸ࢔ࣝࢥ࣮ࣝ࡞࡝ከᵝ࡞᭷ᶵ≀ࢆ⏕ᡂࡍࡿࡓࡵࠊᆅ⌫ୖࡢ᭷ᶵ≀ࡢ㉳※࡜ࡋ࡚ࡶ㠀ᖖ࡟㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ
ࡇࢀࡽᫍ㛫ሻࡢ⾲㠃⎔ቃࡣởࢀࡓ㞷ࡔࡿࡲ࡜⪃࠼ࡽࢀ࡚࠾ࡾࠊPAHs ࡣ⾲㠃࡟Ꮡᅾࡍࡿịࡸ㒊ศⓗ࡟⼥ゎࡋࡓỈ࡜ࡢ┦஫స⏝ࢆᣢࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡓࡵࠊPAHs ࡢỈ࿴ᵓ㐀ࠊ࠾ࡼࡧ⇕࡟ࡼࡿࡑࡢኚ໬ࡣࠊ
PAHs ࡢ཯ᛂᶵᵓࢆ⌮ゎࡍࡿࡓࡵࡢᇶᮏ࡜࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋࠊࡇࢀࡲ࡛ PAHs̺Ỉࡢ┦஫స⏝ࡢᐇ㦂ⓗ◊✲ࡣࠊᐇ㦂ⓗ࡞ࡶࡢࡔࡅ࡛࡞ࡃࠊィ⟬໬Ꮫ࡟ࡼࡿࡶࡢࡍࡽᴟࡵ࡚㝈ࡽࢀ࡚࠸ࡿࠋ≉࡟ࠊỈ࿴ᵓ㐀ࡢືⓗኚ໬࡟㛵ࡋ࡚ࡣ࡯࡜ࢇ࡝◊✲ࡀ⾜ࢃࢀ࡚࠸࡞࠸ࠋ
ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ㉸㡢㏿ࢪ࢙ࢵࢺ୰࡟⏕ᡂࡉࡏࡓẼ┦࣋ࣥࢮࣥỈ࿴ࢡࣛࢫࢱ࣮ࡢ᣺㟁ບ㉳࡟క࠺᣺ື࢚
ࢿࣝࢠ࣮࡟ࡼࡿỈ࿴ᵓ㐀ࡢኚ໬ࢆ㉥እศග࡟ࡼࡾほࡋࡓࠋ᭱ࡶᇶᮏⓗ࡞ⰾ㤶᪘ศᏊ࡛࠶ࡿ࣋ࣥࢮࣥỈ࿴ࢡࣛࢫࢱ࣮㸦Bz±(H2O)n㸧࡟࠾࠸࡚ࡣࠊỈศᏊࡣ⮬ᕫ㞟ྜࡋ࡚ᑠࡉ࡞ịࢆ⏕ᡂࡋࠊ࣋ࣥࢮࣥศᏊࡣࡑࡢእഃ࡟Ỉ࿴ᵓ㐀࡟࠶ࡲࡾᙳ㡪ࢆ୚࠼ࡎ࡟௜ຍࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿ[1]ࠋS1 ≧ែࡢ᣺ື‽఩ࡢ㑅ᢥⓗບ㉳ࢆ⏝࠸ࠊỈࢡࣛࢫࢱ࣮㒊ศࡢᵓ㐀ኚ໬ࡢ࢚ࢿࣝࢠ࣮౫Ꮡᛶࢆᵝࠎ࡞୙Ᏻᐃ␗ᛶయࡢ㉥እࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࠿ࡽ
᳨ウࡋࡓࠋ



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Gaussian 16㸦CAM-B3LYP/aug-cc-pVTZ with GD3BJ dispersion㸧ࢆ⏝࠸࡚ࠊࢡࣛࢫࢱ࣮ࡢ㟁Ꮚᇶᗏ࣭ບ㉳≧ែ࡟࠾ࡅࡿᵓ㐀᭱㐺໬ࠊ㉥እࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓࠋ⤖ᯝࢆᐇ㦂㉥እࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊほࡉࢀࡓࢡࣛࢫࢱ࣮ࡢỈ࿴ᵓ㐀ࡢኚ໬ࢆ᳨ウࡋࡓࠋ



◊✲ᡂᯝ
ᅗ 1 (A±C)࡟᣺ື‽఩ࢆኚ࠼࡞ࡀࡽ

ᐃࡋࡓ Bz±(H2O)8 ࡢ S1 ≧ែࡢ㉥እࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋࡇࡢࢡࣛࢫࢱ

࣮࡛ࡣࠊỈࡣᅗ 1 (D)࡟♧ࡋࡓ D2d ᆺࡢᑐ⛠ᛶࡢ㧗࠸❧᪉యᵓ㐀ࢆᣢࡘ[1]ࠋࡑࡢࡓࡵࠊᐇ

ࡢ S1 00 ‽఩࡟࠾ࡅࡿ IR ࢫ࣌ࢡࢺࣝ㸦ᅗ 1 (A)㸧ࡣࠊẚ㍑ⓗ༢⣧࡞ᙧ≧ࢆ♧ࡋ࡚࠸ࡿࠋ㉥እࢫ࣌ࢡࢺࣝࡣࠊ3 㓄఩ࡢỈ⣲⤖ྜࢆᣢࡘỈศᏊ㸦AADࠊADD㸧࠿ࡽᵓᡂࡉࢀࠊࡑࢀࡽࡢỈ⣲⤖ྜ OH ఙ⦰᣺ືࡀࡼࡃศ㞳ࡋ࡚⌧ࢀ࡚࠸ࡿࠋࡇࢀࡽ
࡟ຍ࠼ࠊ3700 cmí1 ࡟ free OH ఙ⦰᣺ືࠊ࠾ࡼࡧ 3640 cmí1 ࡟࣋ࣥࢮࣥ⎔࡜ࡢ OH-ʌ ⤖ྜ࡟ࡼࡿࣂࣥࢻࡀほࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ≉ᚩࡣ D2d ᆺᵓ㐀ࡢ⌮ㄽࢫ࣌ࢡࢺࣝ㸦ᅗ 1 (D)㸧࡜ࡶࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ
㧗࠸᣺ື࢚ࢿࣝࢠ࣮‽఩࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝ㸦ᅗ 1 (B, C)㸧࡛ࡣࠊ00 ‽఩࡛ࡣศ⿣ࡋ࡚࠸ࡓࣂࣥࢻࡀࣈ࣮ࣟ

- 94 -

ࢻࢽࣥࢢࡋࠊ≉ᚩࡀࡣࡗࡁࡾࡋ࡞ࡃ࡞ࡿࠋࡋ࠿
ࡋࠊAADࠊADDࠊOH-ʌࠊfree ࡢ 4 ✀㢮ࡢ OH ఙ⦰᣺ື࠿ࡽᵓᡂࡉࢀࡿࡇ࡜ࡣኚࢃࡽ࡞࠸ࠋࡇࡢ
⤖ᯝࡣࠊỈ࿴ᵓ㐀࡟ࡣ኱ࡁ࡞ኚ໬ࡣ࡞ࡃࠊࣈࣟ
࣮ࢻࢽࣥࢢࡣ᣺ື࢚ࢿࣝࢠ࣮ࡢቑຍ࡟క࠺࣍ࢵ
ࢺࣂࣥࢻࡢቑຍ࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࠋ
ᐇ㝿ࠊ⌮ㄽ㉥እࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿ࡜ࠊ␗
࡞ࡿ❧᪉యỈࢡࣛࢫࢱ࣮㸦ᅗ 1 (E)㸧ࡸᾮయᵝࡢᵓ㐀㸦ᅗ 1 (F)㸧ࡢ⌮ㄽࢫ࣌ࢡࢺࣝࡣࠊ3300 cmí1
௜㏆࡟ẚ㍑ⓗᙉ࠸ࣂࣥࢻࡢฟ⌧ࢆண᝿ࡋ࡚࠸ࡿ
࡟ࡶ࠿࠿ࢃࡽࡎࠊᐇ

ࢫ࣌ࢡࢺࣝ࡟ࡣ㢧ⴭ࡞ቑຍࡀぢࡽࢀ࡞࠸ࠋࡇࢀࡣࠊD2d ᆺࡢ❧᪉యᵓ㐀ࡢᏳᐃᛶࡀᴟࡵ࡚㧗࠸ࡓࡵࠊᵓ㐀ኚ໬ࡀ㉳ࡇࡾ࡟ࡃ࠸ࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ᣺ື࢚ࢿࣝࢠ࣮
ࡣ IVR ࡟ࡼࡾࢡࣛࢫࢱ࣮඲య࡟ศ㓄ࡉࢀࡿࡓࡵࠊࡍ࡭࡚ࡀỈ࿴ᵓ㐀ࡢኚ໬࡟฼⏝ࡉࢀࡿࢃࡅ
࡛ࡣ࡞ࡃࠊ௒ᅇࡢບ㉳࢚ࢿࣝࢠ࣮࡛ࡣỈ࿴ᵓ㐀ࡢኚ໬࡟ࡣ༑ศ࡛ࡣ࡞࠿ࡗࡓ࡜⪃࠼ࡽࢀࡿࠋ
Reference[1] C. J. Gruenloh et al., J. Chem. Phys. 109, 6601 ᅗ 1. Comparison of IR spectra of the benzene±(H2O)8 cluster at(1998).

various vibrational levels in the S1 state (A±C) with theoretical IR
spectra of some stable isomers (D±F) obtained at the CAM-



B3LYP/aug-cc-pVTZ with GD3BJ dispersion level of theory. TheⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

theoretical spectra were scaled by 0.98.

‫ ‮ ۑ ۻ‬Ữ  ⣸ 㡢 ࠊࠕ ㉁ 㔞 ศ ᯒ 㜈 ࢖ ࢜ ࣥ ໬ ᳨ ฟ ㉥ እ ศ ග ࡟ ࡼ ࡿ ᣺ ື ‽ ఩ 㑅 ᢥ ⓗ ᵓ 㐀 Ỵ ᐃ ࡢ ヨ ࡳ -4Aminobenzonitrile-Ar ࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ໬ㄏ㉳ Ar ⛣ື࡬ࡢ㐺⏝-ࠖࠊ➨ 16 ᅇⱝᡭ◊✲⪅࡟ࡼࡿඛ➃ⓗ࣮ࣞࢨ࣮ศගࢩ࣏ࣥࢪ࣒࢘ࠊᮾிᕤᴗ኱Ꮫࡍࡎ࠿ࡅྎ࢟ࣕࣥࣃࢫࠊ2022 ᖺ 12 ᭶ 16 ᪥‫‮ۑۻ‬Ữ ⣸㡢ࠊ୰ᓥ ᲍ࠎ㤶ࠊᐑ㷂 ඘ᙪࠊ
ࠕMATI-IR ศගἲ࡟ࡼࡿ 4 ࢔࣑ࣀ࣋ࣥࢰࢽࢺࣜࣝ-Ar ࢡࣛࢫ
ࢱ࣮ࡢ Ar ཎᏊ⛣ື཯ᛂࡢほࠖࠊ4P006ࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍‫ۑۻ‬୰ᓥ ᲍ࠎ㤶ࠊᐑ㷂 ඘ᙪࠊࠕ࣋ࣥࢮࣥỈ࿴ࢡࣛࢫࢱ࣮ࡢ㉥እศගἲ࡟ࡼࡿ࢚ࢿࣝࢠ࣮㑅ᢥⓗ࡟ຍ⇕ࡋࡓịࡢᵓ㐀ほࠖࠊ➨ 17 ᅇศᏊ⛉Ꮫウㄽ఍‫‮ۑۻ‬Ữ ⣸㡢ࠊ୰ᓥ ᲍ࠎ㤶ࠊᐑ㷂 ඘ᙪࠊ
ࠕ4-Aminobenzonitrile+±Ar1 ࢡࣛࢫࢱ࣮࢝ࢳ࢜ࣥ࡟᪊ࡅࡿ Ar ཎᏊ ʌĺH ⛣ື㞀ቨࡢᐇ㦂ⓗỴᐃࠖࠊ➨ 17 ᅇศᏊ⛉Ꮫウㄽ఍ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬R. Matsuno, O. Dopfer, M. Fujii, and M. Miyazaki, “Hydration rearrangement in the 4-aminobenzonitrile–(H2O)2cluster induced by photoionization: The effect of solvent-solvent interactions”, Chem. Eur. J. in press. DOI:
10.1002/chem.202301128- 95 -

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ග໬Ꮫ㐣⛬ࡢཎ⌮࣭ࢲ࢖ࢼ࣑ࢡࢫࡢゎ᫂ࠊ≀ᛶࡢணࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ◊✲ࢆᒎ㛤ࡋ࡚࠸ࡿࠋ௧࿴  ᖺᗘࡣ≉࡟ࠊ  ; ⥺ࢆࢺ࣮ࣜ࢞࡜ࡍࡿ 6L ࣇࢱࣟࢩ࢔ࢽࣥⰍ⣲࠿ࡽࡢ㍈㓄఩Ꮚษ᩿཯ᛂ࣓࢝ࢽࢬ࣒
ࡢゎ᫂ࠊ   IV ㌾ ; ⥺྾཰ศග࡜ࡢ㐃ᦠ࡟ࡼࡿ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥࡢ㛤⎔㐣⛬ࡢ◊✲ࠊ   ᫬㛫౫Ꮡ
+DUWUHH)RFN%RJROLXERY +)% ἲ࡟ࡼࡿ㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾ㎸ࢇࡔศᏊࡢບ㉳≧ែィ⟬ࠊ࡞࡝ࢆᐇ᪋ࡋࡓࠋ
◊✲᪉ἲࠊィ⟬᪉ἲ ࡛ࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊ8Ȧ%;' DXJ FFS9'= ࡛ࣞ࣋ࣝ㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓ㸦DXJ

ࡣ 1 ࡜ 2 ཎᏊ࡟ࡢࡳ⏝࠸ࡓ㸧ࠋ,()3&0 ἲ࡟ࡼࡾỈ⁐፹ຠᯝࢆ⪃៖ࡋࡓࠋ*LEEV ࢚ࢿࣝࢠ࣮ࡢィ⟬ࡣ *RRGYLEHVࣉࣟࢢ࣒ࣛ⏝࠸࡚ T55+2 ㏆ఝࡢࡶ࡜࡛ィ⟬ࡋࡓࠋ  ࡛ࡣࠊ㟁Ꮚ≧ែィ⟬ࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚%/<3'FFS9'= ࡛ࣞ࣋ࣝࠊ,5& ィ⟬ࡣ *550 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ '6$),5 ἲࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋෆẆບ㉳ࢫ࣌ࢡࢺࣝࡢィ⟬ࡣࠊ%++/<3FFS&9'= ࡛ࣞ࣋ࣝ 7DPP'DQFRII ㏆ఝࢆ⏝࠸ࡓ 7'')7 ィ⟬࡟ࡼࡾ⾜ࡗࡓࠋ ࡣࠊ*$0(66 ࣉࣟࢢ࣒ࣛࢆඖ࡟⊂⮬࡟ᐇ⿦ࡋࡓ +)% ཬࡧᐇ᫬㛫Ⓨᒎ᫬㛫౫Ꮡἲࡢࢥ࣮ࢻࢆ฼⏝ࡋ࡚㛤Ⓨ
ࡋࡓࠋ




◊✲ᡂᯝ

  ; ⥺ࢆࢺ࣮ࣜ࢞࡜ࡍࡿ 6L ࣇࢱࣟࢩ࢔ࢽࣥ㸦6L3F㸧Ⰽ⣲࠿ࡽࡢ㍈㓄఩Ꮚษ᩿࣓࢝ࢽࢬ࣒ࡢゎ᫂ ᪂ࡓ࡞ࡀࢇ἞⒪ἲ࡜ࡋ࡚㏆ᖺὀ┠ࡉࢀ࡚࠸ࡿ㏆㉥እ⥺ගච␿⒪ἲ㸦1,53,7㸧࡛ࡣࠊ6L ࣇࢱࣟࢩ࢔ࢽࣥⰍ⣲,5 ࢆᢠయ࡟⤖ྜࡉࡏࡓ⸆๣ࡀ⏝࠸ࡽࢀࡿࠋࡑࡢග໬Ꮫ཯ᛂࡢศᏊⓗ࣓࢝ࢽࢬ࣒ࡣࠊ໭኱⸆Ꮫ◊✲㝔ࡢᑠᕝࢢ࣮ࣝࣉ࡜ᡃࠎࡢඹྠ◊✲࡟ࡼࡾࠊ1,5 ࡟ࡼࡾ⏕ᡂࡋࡓ ,5 ࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥࡢຍỈศゎ࡟ࡼࡿ㍈㓄఩- 96 -

Ꮚษ᩿ࡀ㉳Ⅼ࡜࡞ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡋ࠿ࡋࠊ1,5 ࡣ⏕య㏱㐣ᛶࡀప࠸ࡓࡵࠊ◳ ; ⥺ࡢ↷ᑕ࡟ࡼࡾ཯ᛂ
ࡀ㛤ጞࡉࢀࡿ⸆๣࡟ࡼࡿ⏕య῝㒊ࡀࢇ࡬ࡢ㐺⏝ࢆ┠ᣦࡋ࡚࠸ࡿࠋᐇ㝿࡟ᵝࠎ࡞㍈㓄఩Ꮚࢆᣢࡘ 6L3F ࢆྵࡴ⁐ᾮ࡟ప㓟⣲᮲௳ୗ࡛ ; ⥺ࢆ↷ᑕࡋࡓ࡜ࡇࢁࠊỈ࿴㟁Ꮚ㸦HíDT㸧࡜ࡢ཯ᛂ࡟ࡼࡗ࡚㍈㓄఩Ꮚษ᩿཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࠊࣛࢪ࢝ࣝ㐃㙐཯ᛂࡀ㉳ࡇࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࢀࡽࡢᐇ㦂஦ᐇࢆィ⟬࡛☜ㄆࡍࡿ࡜࡜ࡶ࡟ࠊ཯ᛂ࣓
࢝ࢽࢬ࣒ࡢゎ᫂ࢆィ⟬໬Ꮫⓗ࡟⾜ࡗࡓࠋ ࡲࡎࠊ㟁Ꮚ⛣ື཯ᛂࡢ ǻG ್ࢆィ⟬ࡋࡓ࡜ࡇࢁ㸦⾲ 㸧ࠊ཯ᛂࡣ඲࡚Ⓨ࢚ࣝࢦࣥⓗ࡛࠶ࡾࠊ⏕ᡂ≀࠿ࡽ཯ᛂ≀࡟ࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥࡀ⛣ືࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊ཯ᛂ๓ࡢ
6L3F ࡢᆶ┤㟁Ꮚぶ࿴ຊ㸦9($㸧ࢆィ⟬ࡋࡓ࡜ࡇࢁ㸦⾲ 㸧ࠊỈ࿴㟁ᏊࡢỈ୰࡛ࡢ᮰⦡࢚ࢿࣝ
ࢠ࣮ࡢᐇ㦂್㸦᭱᪂ࡢሗ࿌࡛ࡣaH9㸧࡜㠀ᖖ࡟㏆࠸್ࢆྲྀࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇ
ࡢሙྜࠊỈ࿴㟁Ꮚࡣඹ㬆ຠᯝ࡟ࡼࡾ཯ᛂ≀ࡢ┤᥋㑏ඖࢆಁ㐍ࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ㍈㓄఩Ꮚࡢ㐪࠸࡟ࡼࡿ཯ᛂᛶࡢ┦㐪ࡣ⾲  6L3F ศゎ⏕ᡂ≀࢔ࢽ࢜ࣥ࠿ࡽᮍ཯ᛂࡢ୰ᛶ 6L3F ࡬ࡢ㟁Ꮚ⛣ື཯ᛂࡢ ǻG ್>N-PRO@㸦.ࠊ Ẽᅽ㸧
5HDFWLRQ; 26L0H5

; 2&+5í

6L3F 2+ ; 6L3F;

±±

6L3F 2+ í6L3F;

±±

í±

 ±

6L3F 2+  6L3F 2+ ;

⾲ 6L3F ໬ྜ≀ࡢᆶ┤㟁Ꮚぶ࿴ຊ㸦9($㸧>H9@
5HDFWLRQ; 26L0H5

; 2&+5

6L3F;ମ6L3F;í



6L3F 2+ ;ମ6L3F 2+ ;í



1,5 ග࡟ࡼࡿࡶࡢ࡜ఝ࡚࠸ࡿࡓࡵࠊ㍈㓄఩Ꮚษ᩿཯ᛂࡢ࣓࢝ࢽࢬ࣒⮬㌟ࡣ 1,5 ࡢሙྜ࡜ྠࡌ࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ
  IV ㌾ ; ⥺྾཰ศග࡜ࡢ㐃ᦠ࡟ࡼࡿ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥࡢ㛤⎔㐣⛬ࡢ◊✲ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㸦&+'㸧ࡢࡼ࠺࡞ࣜࣥࢢ≧ศᏊࡢ㛤⎔཯ᛂࡸࡑࡢ㏫㐣⛬࡛࠶ࡿ㛢⎔཯ᛂࡣࠊ᭷ᶵ
ྜᡂ໬Ꮫࡸ⏕యෆ཯ᛂ࡞࡝ᖜᗈ࠸ศ㔝࡛⌧ࢀࡿࠋ཯ᛂ᪉ྥ࡟ࡣྠ᪕㐣⛬࡜㏫᪕㐣⛬ࡢ஧㏻ࡾࡀ࠶ࡿࡀࠊ⨨᥮ᇶࢆᣢࡘሙྜ࡟ࡣࡇࡢ㐣⛬࡟ࡼࡾ⏕ᡂ≀ࡀኚࢃࡿࡓࡵࠊᐇ㦂᮲௳ୗ࡛ࡢ཯ᛂ㐣⛬ࢆணゝ࡛ࡁࡿࡇ࡜ࡀ㔜せ࡜࡞ࡿࠋࡇࡢࡼ࠺࡞⬡⎔ᘧ཯ᛂࡢ❧య໬Ꮫࡣࠊ
:RRGZDUG+RIIPDQQ
㸦:+㸧๎ࠊࡘࡲࡾ㌶㐨
ᑐ⛠ᛶࡢಖᏑ࡛ㄝ᫂ࡉ
ࢀࡿࠋ:+ ๎ࡀᡂࡾ❧ࡘࡇ࡜ࡣࠊ⏕ᡂ≀ࡢᵓ㐀࠿ࡽ᳨ドࡉࢀ࡚ࡁࡓ
ࡀࠊ཯ᛂࡣ㉸㧗㏿࡛㐍⾜ࡍࡿࡓࡵࠊ཯ᛂ୰ࡢ
㌶㐨ᑐ⛠ᛶࡢ᫬㛫Ⓨᒎ࡟ࡘ࠸࡚ࡣ᫂ࡽ࠿࡟ࡉ
ࢀ࡚ࡇ࡞࠿ࡗࡓࠋᡃࠎ
ࡣࠊ໭኱ᕤᏛ◊✲㝔ࡢ㛵ᕝࡽ࡜ࡢඹྠ◊✲࡟ᅗ 7'')7 ィ⟬࡟ࡼࡿ &+' ࣌ࣜ⎔≧཯ᛂࡢྠ᪕㐣⛬࡜㏫᪕㐣⛬ࡢ ; ⥺㐣Ώ྾཰ࢫ࣌ࢡࢺࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ

- 97 -

ࡼࡾࠊࣇ࢙࣒ࢺ⛊㌾ ; ⥺㐣Ώ྾཰ศගἲ࡜㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚ࠊ&+' ࡢ ࣊࢟ࢧࢺ࢚ࣜࣥ࡬ࡢ␗ᛶ໬
཯ᛂ㸦࣌ࣜ⎔≧཯ᛂ㸧ࡢ㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
ᅗ  D ࡜ E ࡟ '6$),5 ィ⟬࡟ࡼࡾồࡵࡽࢀࡓ &+' ࡢ࣌ࣜ⎔≧཯ᛂ࡟࠾ࡅࡿྠ᪕㐣⛬࡜㏫᪕㐣⛬ࡢ ,5& ࡟ἢࡗࡓ┦ᑐ࢚ࢿࣝࢠ࣮ࢆ♧ࡍࠋ㏫᪕㐣⛬ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡣྠ᪕㐣⛬ࡢࡶࡢࡼࡾࡶ H9 ௨ୖపࡃࠊ⇕ⓗ࡟ࡣ :+ ๎࡜ྠᵝ࡟㏫᪕㐣⛬࡛཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋࡇࡢ ,5& ୖࡢᵓ㐀࡟ᑐࡋ࡚ෆẆບ㉳ࡢ7'')7 ィ⟬ࢆ⾜࠸ࠊ; ⥺㐣Ώ྾཰ࢫ࣌ࢡࢺࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ⤖ᯝࢆᅗ  F ࡜ G ࡟♧ࡍࠋ㏫᪕㐣⛬ࡢ⤒㊰࡛ࡣ྾཰ࡣ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿ୍᪉ࠊྠ᪕㐣⛬࡛ࡣప࢚ࢿࣝࢠ࣮ࢩࣇࢺࡋ࡚࠸ࡿࠋᐇ㦂࡟ࡼࡾᚓࡽࢀࡓࣇ࢙࣒ࢺ⛊㌾ ; ⥺㐣Ώ྾཰ࢫ࣌ࢡࢺࣝࡣ᫬㛫ࡢ⤒㐣࡜࡜ࡶ࡟㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿࡇ࡜࠿ࡽࠊ:+๎ࡢ♧ࡍ࡜࠾ࡾ㏫᪕㐣⛬ࢆ⤒⏤ࡋ࡚㛤⎔ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟☜࠿ࡵࡽࢀࡓࠋ

᫬㛫౫Ꮡ +DUWUHH)RFN%RJROLXERY ἲ࡟ࡼࡿ㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾ㎸ࢇࡔศᏊࡢບ㉳≧ែィ⟬㟼ⓗ㟁Ꮚ┦㛵ࡣࣇࣟࣥࢸ࢕࢔㌶㐨࿘㎶ࡢᨃ⦰㏥࡟క࠺㟁Ꮚ┦㛵࡛࠶ࡾࠊ⤖ྜゎ㞳㐣⛬ࡸ㑄⛣㔠ᒓࢆྵࡴ⣔࡞࡝࡛ࡣᮏ㉁ⓗ࡟㔜せ࡜࡞ࡿࠋࡲࡓࠊ㟁Ꮚບ㉳≧ែ࡟࠾ࡅࡿ㟼ⓗ㟁Ꮚ┦㛵ࡢྲྀࡾᢅ࠸ࡣࠊᇶᗏ≧ែࡼࡾࡶࡉ
ࡽ࡟ᅔ㞴࡜࡞ࡿࠋᚑ᮶ࠊ㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾ㎸ࡴィ⟬ᡭἲ࡜ࡋ࡚ࡣከ㓄⨨Ἴື㛵ᩘ࡟ᇶ࡙࠸ࡓ᏶඲άᛶ✵㛫
㸦&$6㸧6&) ࡞࡝ࡀ୍⯡ⓗ࡛࠶ࡗࡓࠋࡋ࠿ࡋࠊάᛶ✵㛫ࡢ኱ࡁࡉ࡟కࡗ࡚ィ⟬ࢥࢫࢺࡀᣦᩘ㛵ᩘⓗ࡟ቑ኱ࡋ࡚ࡋࡲ࠺ࡓࡵࠊ㐺ษ࡞άᛶ✵㛫ࡢ㑅ᢥࡀᅔ㞴࡛࠶ࡗࡓࠋᑠࡉ࡞
ィ⟬ࢥࢫࢺ࡛㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾ㎸ࡴᡭἲࡢ୍ࡘ࡟D+DUWUHH±)RFN±%RJROLXERY +)% ἲࡀ࠶ࡿࠋ+)% ἲࡣ஧㟁ᏊἼື㛵ᩘ㸦ࢪ࢙࣑ࢼࣝ㸧࡟ᇶ࡙ࡃἼື㛵ᩘ⌮ㄽ࡜῝࠸㛵ಀࡀ࠶ࡾࠊ
⢏Ꮚ㛫ࡢ┦஫స⏝ࢆ᭷ຠⓗ࡟ྵࢇࡔ‽⢏Ꮚᥥീࢆ⏝࠸ࡿࡇ࡜࡛ࠊ
༢୍ࡢ‽⢏Ꮚ㓄⨨㛵ᩘࢆ⏝࠸࡚㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾ㎸ࡴࠋ+)%ἲࢆບ㉳≧ែィ⟬࡟ᣑᙇࡍࡿࡓࡵࠊᐇ᫬㛫Ⓨᒎ᫬㛫౫Ꮡ
㸦577'㸧ἲ࡜⤌ࡳྜࢃࡏࡓ 577'+)% ἲࢆࡲࡎᥦ᱌ࡋࡓࠋࡋ
࠿ࡋࠊࡇࡢ᪉ἲ࡛ࡣ᫬㛫Ⓨᒎ࡟కࡗ࡚㟁Ꮚᩘࡀኚືࡋ࡚ࡋࡲ࠺
ၥ㢟ࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡑࡇ࡛ࠊྛ᫬้ࡢ +)% 㟁Ꮚᐦᗘ⾜
ิࢆᑐゅ࡟ࡍࡿṇ‽ᇶᗏ㸦&E㸧ࢆ᫬㛫Ⓨᒎࡉࡏࡿࡇ࡜࡟ࡼࡾ㟁Ꮚᩘࢆ୍ᐃ࡟ࡍࡿ &E7'+)% ἲࢆ฼⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊ㟼ⓗ㟁EᏊ┦㛵ࢆᑠࡉ࡞ィ⟬ࢥࢫࢺ࡛⡆౽࡟ྲྀࡾ㎸ࡵࡿບ㉳≧ែィ⟬ἲࡢᐇ⌧ࢆ┠ᣦࡋࡓࠋ
⤖ྜ㊥㞳ࢆ c ࡟ఙࡤࡋࡓỈ⣲ศᏊ࡟ᑐࡋ࡚ &E7'+)% ィ⟬ࢆᐇ⾜ࡋ࡚ບ㉳ࢫ࣌ࢡࢺࣝࢆᚓࡓ࡜ࡇࢁࠊIXOO&, ࡟࠾ࡼࡑᑐ
ᛂࡍࡿࡶࡢࡀᚓࡽࢀࡓࠋḟ࡟ +) ṇ‽㌶㐨࡟ᇶ࡙ࡃゎᯒࢆ⾜ࡗࡓ㸦ᅗ 㸧ࠋ+) ᇶᗏ≧ែ࡛ࡣ༨᭷ࡉࢀ࡚࠸࡞࠸  ␒ࡢṇ‽㌶㐨
࡞࡝࠿ࡽࡢບ㉳ࡢᐤ୚ࡀぢࡽࢀࡿࡇ࡜࠿ࡽࠊ7'+)% ἲ࡛ࡣ㟼ⓗ㟁Ꮚ┦㛵ࢆྲྀࡾධࢀࡓບ㉳≧ែࡢィ⟬ࡀ࡛ࡁ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ᅗ + r++ c ࡢ &E7'+)% ィࡿࠋ⟬ࡢ +) ㌶㐨ゎᯒࠋ D ṇ‽㌶㐨࡜+)% ࡟࠾ࡅࡿ༨᭷ᩘࠊ E ṇ‽㌶㐨㛫
ࡢ㑄⛣ࡢᐤ୚

- 98 -

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')7 ィ⟬࡟ࡼࡿ /% ⭷ಟ㣭 6Q2΃㟁ᴟ⾲㠃ࡢ㟁Ꮚ≉ᛶࡢ◊✲The study of electronic properties of LB modified SnO2 electrodesurfaces using density functional theory calculations.
˕৏ీ季 Ҳٝʤԥශࠅཱི୉ָ୉ָӅ޽ָ‫ڂݜ‬Ӆʥ1◊✲┠ⓗࠊෆᐜ
᭷ᶵⷧ⭷ᆺࡢኴ㝧㟁ụࡣᰂ㌾ᛶࡸపࢥࢫࢺ࡛࠶ࡿࡇ࡜࠿ࡽⓎ㟁ຠ⋡ࡢྥୖ࡟ྥࡅࡓ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋᶓ὾ᅜ❧኱ᏛᕤᏛ◊✲㝔㏕ᮧ຾◊✲ᐊ࡛ࡣࠊ࢔ࣀ࣮ࢻ㟁ᴟ⾲㠃ࡢ௙஦㛵ᩘࢆไᚚࡍࡿࡇ࡜࡛ኴ
㝧㟁ụࢹࣂ࢖ࢫࡢᛶ⬟ࢆྥୖࡉࡏࡿ◊✲ࢆᐇ㦂࡜ィ⟬ࡢ୧㠃࠿ࡽ㐍ࡵ࡚࠸ࡿࠋᡃࠎࡣ ')7 ィ⟬ࢆ⏝࠸࡚
㏱᫂ᑟ㟁ᛶ≀㉁࡛࠶ࡿ SnO΃࡟ Langmuir-Blogett(LB)⭷ࢆಟ㣭ࡋࠊ௙஦㛵ᩘ࡟ᑐࡍࡿᙳ㡪ࡸ㟁Ꮚ≉ᛶࡢኚ໬࡟ࡘ࠸࡚ࡢィ⟬࡟ࡼࡿඹྠ◊✲ࢆ㛤ጞࡋࡓࠋ

2◊✲᪉ἲ࣭ィ⟬᪉ἲᮏ ◊✲࡛ࡣ SnO΃࡜஧ ✀㢮ࡢ LB ⭷ ࡟㛵 ࡋ࡚

QuantumEspresso ࢆ⏝࠸ࡓ DFT ィ⟬ࢆ⾜࠸ࠊ௙஦㛵ᩘࡢኚ໬ࢆィ⟬ࡋࡓࠋLB ⭷࡟ࡣ PFECA(Partially
Fluorinated Ether Carboxylic Acid)࡜࢔ࣛ࢟ࢪࣥ㓟ࢆ⏝࠸ࡓࠋSnO΃ࡢࢫࣛࣈࣔࢹࣝࢆసᡂࡋࠊᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࡢࡕ SnO΃⾲㠃࡟ LB ⭷ࢆಟ㣭ࡉࡏࡓࣔࢹࣝࡢ

Fig. 1 3)(&$PRGLILHG6Q2⒬ VXUIDFH

సᡂཬࡧ௙஦㛵ᩘኚ໬ࡢィ⟬ࢆ⾜ࡗࡓࠋFig1 ࡟୍౛࡜ࡋ
࡚ PFECA ࡛⾲㠃ࢆಟ㣭ࡋࡓ LB ⭷ಟ㣭 SnO΃ࢫࣛࣈࣔࢹࣝࢆ♧ࡍࠋLB ⭷ಟ㣭㠃ࡼࡾ῝࠸ࢫࣛࣈᒙ㸦㯤Ⰽ୸㒊ศ㸧࡟ࡘ࠸࡚ࡣࠊィ⟬ࢥࢫࢺᢚ࠼ࡿࡓࡵ࡟ᅛᐃࡋࡓ≧ែ࡛ィ⟬ࢆᐇ⾜ࡋࡓࠋ3◊✲ᡂᯝ௙஦㛵ᩘᕪࡣࢫࣛࣈࡢࡳࡢഃ࡜ಟ㣭⾲㠃ഃࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮࡜ࡢᕪ࠿ࡽồࡵࡓࠋPFECA ࡢሙྜ ΔWF=-0.3534eV ࡛࠶ࡾࠊ࢔ࣛ࢟ࢪࣥ㓟ࡢሙྜࡣ ΔWF=+0.292219eV ࡜࡞ࡗࡓࠋᐇ㦂࡛ࡣ PFECA ࡣ௙஦㛵ᩘࢆྥୖࡉࡏࠊ࢔ࣛ࢟ࢪࣥ㓟ࡣ࡯࡜ࢇ࡝ኚ໬ࢆཬࡰࡉ࡞࠸ࡇ࡜࠿ࡽィ⟬࡜ࡢ୍⮴ࡣⰋࡃ࡞࠸ࠋィ⟬ࡢ⤖ᯝࡣ PFECA ࡟ࣇࢵ⣲ཎᏊࡀከ࠸ࡓࡵࠊ㟁Ꮚ྾ᘬᛶࡀ㧗ࡃࠊ㟁ᏊࡢᏑᅾᐦᗘ☜⋡ࡀ㧗ࡃ࡞ࡗࡓࡇ࡜࡛࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡀୗࡀࡗ࡚ࡋࡲࡗ࡚࠸ࡿࡶࡢ࡜ᛮࢃࢀࡿࡀࠊᮍࡔࣔࢹࣝࢆ᳨ウࡋ࡚࠸ࡿึᮇࡢ⤖ᯝ࡛࠶ࡾࠊ௒ᚋ LB ⭷ಟ㣭఩⨨ࡢᙳ㡪ࡸࢫࣛࣈࣔࢹࣝࡢ኱ࡁࡉ࡞࡝ࠊィ⟬⤖ᯝ࡟ཬࡰࡍᙳ㡪࡟ࡘ࠸࡚ࡉࡽ࡟᳨ウࢆ㐍ࡵࡓ࠸ࠋ

4 Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(1)

մ" Photochemical Reaction of Ketoprofen with Proteinogenic Amino 2 Acids " Wataru Kashihara, Mio
Shinoda, Kiyoka Tsuchiya, Tasuku Isozaki, Batsaikhan Mijiddorj, Kazuyoshi Ueda, and Tadashi
Suzuki, J. Phys. Chem. B, 126, 2098-2107 (2022). doi: https://doi.org/10.1021/acs.jpcb.1c10108 .

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Theoretical studies on complex chemical system
based on quantum chemistry and statistical mechanics
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ࢩ࢔ࣀࣅࢽࣝయࡣ 2 ఩௜ຍయ 2 ࡜ 3 ఩௜ຍయ 3 ࡢΰྜ≀࡛࠶ࡾ㸦Scheme 1㸧㸪ࡑࡢ⏕ᡂẚࡣ❅⣲ୖࡢ⨨᥮ᇶࡸ཯ᛂ࡟⏝࠸ࡓ⁐፹✀࡟ࡼࡗ࡚኱ࡁࡃኚ໬ࡍࡿࠋᮏ◊✲ㄢ㢟࡛ࡣ㸪❅⣲ୖࡢ⨨᥮ࡸ⁐፹✀ࡢ㐪࠸࡟ࡼࡿ㓄ྥᛶࡸ཯ᛂᶵᵓ࡟ࡘ࠸࡚㸪ᐇ㦂ཬࡧ⌮ㄽィ⟬ࡢ୧ᡭἲࢆ⏝࠸࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ
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ᐇ㦂ࡢ⤖ᯝ㸪N ୖࡢ⨨᥮ᇶࡀࣇ࢙ࢽࣝᇶࡢሙྜ㸪⨨᥮ᇶࡀỈ⣲ࡸ࣓ࢳࣝᇶࡢ࡜ࡁࡼࡾࡶ཯ᛂ㏿ᗘࡀ㠀ᖖ࡟㐜ࡃ࡞ࡿࡇ࡜ࡸ㸪࠸ࡎࢀࡢ⁐፹୰࡛ࡶ 2 ఩⨨᥮యࡀඃඛࡋ࡚⏕ᡂࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢ཯ᛂ࡟ࡘ࠸࡚㸪- 105 -

ศᏊ㌶㐨ィ⟬࡟ࡼࡾึᮇ㘒యࡸ཯ᛂ୰㛫య㸪㑄⛣≧ែࢆࡑࢀࡒࢀồࡵ࡚࢚ࢿࣝࢠ࣮ࢲ࢖ࣖࢢ࣒ࣛࢆసᡂࡋࡓ
࡜ࡇࢁ㸪N ୖࡢ⨨᥮ᇶࡀỈ⣲ࡸ࣓ࢳࣝᇶࡢ࡜ࡁ࡜ẚ㍑ࡋ࡚㸪TCNE ࡀồ㟁Ꮚ௜ຍࡋ࡞ࡀࡽỈ⣲㌿఩ࡍࡿẁ㝵ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ㧗࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓᵓ㐀ゎᯒ࡟ࡼࡾ㸪཯ᛂึᮇẁ㝵࡛ TCNE ࡜ࣇ࢙ࢽࣝᇶࡢ㛫࡟❧య཯Ⓨࡀ㉳ࡇࡿࡇ࡜࡟ࡼࡾ㸪άᛶ໬࢚ࢿࣝࢠ࣮ࢆᢲࡋୖࡆ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ

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[1] ‫ۻ‬U. Masamoto, Y. Yoshinaga, A. Yamamoto, H. Saigo, I. Kaji, D. Kaneno, 25th IUPAC Conference on PhysicalOrganic Chemistry, July 14, 2022, Hiroshima, Japan[2] ‫ۻ‬ᫀᮏ㯇㸪ྜྷỌ᭷భ㸪㔠㔝኱ຓ㸪᪥ᮏ໬Ꮫ఍➨ 102 ᅇ᫓Ꮨᖺ఍㸪2023㸪㔝⏣[3] ‫ۻ‬ὸ㔝┿Ᏺ㸪ᑠᖹᜏ㟹㸪㔠㔝኱ຓ㸪᪥ᮏ໬Ꮫ఍➨ 102 ᅇ᫓Ꮨᖺ఍㸪2023㸪㔝⏣[4] ‫ۻ‬ᑠᕝ΅ኴ㑻㸪ୖᮧ┿㸪᳃⏣⳹⳯㸪㔠㔝኱ຓ㸪᪥ᮏ໬Ꮫ఍➨ 102 ᅇ᫓Ꮨᖺ఍㸪2023㸪㔝⏣[5] ‫ۻ‬㣕㮚⤢Ꮚ㸪బࠎᮌ⩏❶㸪㧗ᶫ኱✵㸪᭷⃝బ⧊㸪㇂ᾴኴ㸪㔠㔝኱ຓ㸪᪥ᮏ໬Ꮫ఍➨ 102 ᅇ᫓Ꮨᖺ఍㸪2023㸪㔝⏣[6] ‫ۻ‬ᫀᮏ㯇㸪ྜྷỌ᭷భ㸪㔠㔝኱ຓ㸪㧗▱໬Ꮫ఍ࢩ࣏ࣥࢪ࣒࢘ 2022㸪㧗▱[7] ‫ۻ‬㣕㮚⤢Ꮚ㸪బࠎᮌ⩏❶㸪㧗ᶫ኱✵㸪᭷⃝బ⧊㸪㔠㔝኱ຓ㸪㧗▱໬Ꮫ఍ࢩ࣏ࣥࢪ࣒࢘ 2022㸪㧗▱[8] ‫ۻ‬⍠ᮾ᫂᪥㤶㸪㛵ோᮃ㸪㔠㔝኱ຓ㸪Ἴከ㔝ៅᝅ㸪Ώ㎶ⱱ㸪ோᏊ㝧㍜㸪㧗▱໬Ꮫ఍ࢩ࣏ࣥࢪ࣒࢘ 2022㸪㧗
▱[9] ‫ۻ‬ᫀᮏ㯇㸪ྜྷỌ᭷భ㸪㔠㔝኱ຓ㸪➨ 32 ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸪2022 ᖺ 9 ᭶ 20-22 ᪥㸪ி㒔[10] ‫ۻ‬ᫀᮏ㯇㸪㔠㔝኱ຓ㸪2022 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2022 ᖺ 9 ᭶ 4 ᪥㸪㧗▱[11] ‫ۻ‬㣕㮚⤢Ꮚ㸪㔠㔝኱ຓ㸪2022 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2022 ᖺ 9 ᭶ 3 ᪥㸪㧗▱[12] ‫ۻ‬ᑠᕝ΅ኴ㑻㸪㔠㔝኱ຓ㸪2022 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2022 ᖺ 9 ᭶ 3 ᪥㸪㧗▱[13] ‫ۻ‬ὸ㔝┿Ᏺ㸪㔠㔝኱ຓ㸪2022 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2022 ᖺ 9 ᭶ 3 ᪥㸪㧗▱ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬Inoue, K.; Kawakami, R.; Murakami, M.; Nakayama, T.; Yamamoto, S.; Inoue, K.; Tsuda, T.; Sayama, K.;
Imamura, T.; Kaneno, D.; Hadano, S.; Watanabe, S.; Niko, Y., J. Mater. Chem. B, 2022, 10, 1641.

- 106 -

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ἲࡢ㐺⏝⠊ᅖࢆ㉸࠼ࡓィ⟬࡟ᑐࡋ࡚ࠊ࣐ࣝࢳࢫࢣ࣮ࣝࣔࢹࣝࡢ 4000 ἲࢆ᥇⏝ࡋࠊ㧗⢭ᗘࡢࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ⤖ᯝࢆᚓࡓࠋຊሙࣃ࣓࣮ࣛࢱࡣ $PEHU ࣛ࢖ࣈࣛࣜ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ */<&$0㸦⢾㙐㸧࠾ࡼࡧII6%㸦ࢱࣥࣃࢡ㉁㸧ࢆ᥇⏝ࡋࠊᐇ⿦ࡉࢀ࡞࠸ྛ✀ࣜ࢞ࣥࢻศᏊ࡟ᑐࡍࡿຊሙࣃ࣓࣮ࣛࢱ࡟ࡘ࠸࡚ࡣ⊂⮬࡟㛤Ⓨࡋࡓࠋࣃ࣓࣮ࣛࢱ㛤Ⓨࡸ 0' ィ⟬࡛ᚓࡽࢀࡓᵓ㐀࡟ᑐࡍࡿ㟁Ꮚ≀ᛶࡢゎᯒ࡟ࡣࠊ*DXVVLDQ  ࢆ฼⏝ࡋࡓࠋࢱࣥࣃࢡ㉁ࡸከ⢾㢮⤖ᬗᵓ㐀ࡢึᮇᵓ㐀ࡣࠊබ㛤ࡉࢀ࡚࠸ࡿ⤖ᬗᵓ㐀ࢹ࣮ࢱࡼࡾᵓ⠏ࡋࡓࠋ㸬◊✲ᡂᯝ
㸫㸬ᵓ㐀ከ⢾㢮⤖ᬗᮦᩱࡢᣑᙇ࢔ࣥࢧࣥࣈࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ᮏ◊✲ᐊ࡛Ỵᐃࡋࡓ࢟ࢺࢧࣥʊሷ໬ள㖄」ྜయ⤖ᬗᵓ㐀㸦ᅗ㸧ࢆᇶ࡟ࠊᵓ⠏ࡋࡓ⤖ᬗࣔࢹࣝࢆࢩ࣑ࣗ
࣮ࣞࢩࣙࣥᑐ㇟࡜ࡋࡓࠋࡇࢀࡼࡾ⤖ᬗෆ㒊࡟࠾ࡅࡿỈศᏊࡢ㓄⨨ࡸሷ໬ள㖄ศᏊࡢᣑᩓᣲືࢆゎᯒࡋࡓ>@ࠋD0'ィ⟬ἲ࡟ࡼࡾỈ࿴⎔ቃ࡟࠶ࡿ」ྜయ⤖ᬗෆ㒊࡟ỈศᏊࢆᣑᩓࡉࡏࡓ⤖ᯝࠊࢢࣝࢥࢧ࣑ࣥṧᇶ࠶- 112 -

ࡓࡾ⣙ศᏊࡢỈศᏊࡀ㓄⨨ࡋࠊ࠿ࡘ᫂☜࡟ᵓ㐀໬ࡋࡓỈศᏊࡢศᕸ
ࢆ☜ㄆࡋࡓ㸦ᅗ㸧ࠋ௨๓ࡢ⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡗ࡚ሷ໬ள㖄ศᏊࡣ఩࢔࣑ࣀᇶ࡜㓄఩ࡏࡎ࡟ࠊᑓࡽ఩Ỉ㓟ᇶࡀள㖄ཎᏊ࡟㓄఩ࡍࡿ㘒యᵓ㐀ࡀᥦ᱌ࡉࢀࡓࡀࠊ௒ᅇࠊࡑࡢ㘒య࡟ỈศᏊࡀࡉࡽ࡟㓄఩ࡍࡿሷ⣲ཎᏊࢆྵࡵ࡚㓄఩࡟ࡼࡿ㘒యᵓ㐀ࡀ♧၀ࡉࢀࡓࠋḟ࡟ࠊ60'ィ⟬ἲࢆ㐺⏝ࡋࠊሷ໬ள㖄ศᏊࡀศᏊ㙐㍈࡟ἢࡗ࡚⛣ືࡍࡿ㝿ࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࠊࡲࡓࡣ30)㸦3RWHQWLDORI0HDQ)RUFH㸧ࢆồࡵࡓࠋ⤖ᬗෆ㒊ࡢỈศᏊ࡜ࡢ᥋ゐ࡟ࡼࡗ࡚ᢠຊࡀ⏕ࡌࡓ⤖ᯝࠊሷ໬ள㖄ศᏊࡢᅗ䠍㻚㻌 䜻䝖䝃䞁㻙ሷ໬ள㖄」ྜయ
䛾⤖ᬗᵓ㐀䠄㼍㼎 ᢞᙳ㠃䠅㻌⛣ື࡟కࡗ࡚30)್ࡣቑຍࡋ⥆ࡅࠊ⧄⥔࿘ᮇ࡟┦ᙜࡍࡿ⛣ື㊥㞳㸦⣙ QP㸧࡟ᑐࡋ NFDOPRO௨ୖ࡟㐩ࡋࡓࠋࡑࡢ㛫ࠊ఩࢔࣑ࣀᇶࢆྵ
ࡴ⢾ṧᇶᴟᛶᇶ࡜ࡢ┦஫స⏝࡟ࡼࡾࢃࡎ࠿Ⓨ⇕ࣆ࣮ࢡࡀ⏕ࡌࡓࠋ
3㸫2㸬ከ⢾ㄏᑟయࡀ♧ࡍ࢟ࣛࣝㄆ㆑⌧㇟ᮏ◊✲ࡣࠊከ⢾㢮ㄏᑟయࢆ࢟ࣛࣝࢭࣞࢡࢱ࣮࡜ࡋࡓ࣒࢟ࣛࣝ࢝ࣛ
඘ሸ๣ࡀ♧ࡍ࢟ࣛࣝศ㞳࣓࢝ࢽࢬ࣒ࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡓࡵࠊଡ
౸ྪ༢಍ରන໚৏Ͷ͕͜Ζझʓ͹Ϋϧϩ෾ࢢ͹෾཯‫ڏ‬ಊ͹εϝϣϪ
ʖφΝࢾΊͪɽ૤ଫ෾ࢢಊྙָ‫ࢋܯ‬๑ʤ60'ʥΝన༽͢ɼ༙‫ݸ‬ௗ͹ιϩϫʖη༢಍ର෾ࢢ࠱͕Γ;Πϝϫʖη༢಍ରΝഓ஖ͪ͢ΫϧϩιϪένʖϠυϩ৏ͲϠυϩΫϧϩ෾ࢢΝҢಊͦ͠ɼޭָҡ੓ର෾ᅗ䠎㻚㻌 䜻䝖䝃䞁㻙ሷ໬ள㖄」ྜయ
⤖ᬗᵓ㐀୰䛻䛚䛡䜛ỈศᏊ䛾➼ᐦᗘ⾲㠃䠄䝞䝹䜽ᐦᗘ䛾䠏ಸ㡿ᇦ䛷㉥䠖㓟⣲ཎᏊ䚸ⓑ䠖Ỉ⣲ཎᏊ䠅㻌ࢢؔͲ૮‫༽ࡠޕ‬͹รԿΝ඲Ճͪ͢ɽྫ࿪̒೧ౕͶɼҐԾͶࣖͤ̒झϠυϩΫϧϩ෾ࢢΝઅఈ͢ɼ͞ΗΉͲҲ๏௪ߨͲ͍ͮͪΫϧϩ෾ࢢ͹Ңಊ༹ࣞΝɼΫϧϩιϪένʖϠυϩྈ୼Νԡ෰ͦ͠ɼҲఈ͹෾ࢢ࠱ௗΝ࣍ͯϠυϩΝ༽͏ͱҢಊ‫཯ړ‬Ν೜қͶ௒ઇͲ͘ΖΓ͑Ͷ෾཯εϝϣϪʖεϥϱ๏๑Νրྒྷͪ͢ɽ
ࡍ࡛࡟ၟရ໬ࡉࢀࡓ࢟ࣛࣝࢭࣞࢡࢱ࣮࡛࠶ࡿ✀ࡢࢭ࣮ࣝࣟࢫㄏᑟయࠊFHOOXORVH WULV GLPHWK\OSKHQ\O
FDUEDPDWH  &7'3&  ࡜FHOOXORVHWULV PHWK\OEHQ]RDWH  &70% ࠊ࢔࣑࣮ࣟࢫㄏᑟయDP\ORVH WULV GLPHWK\O
SKHQ\OFDUEDPDWH  $'03& ࢆᑐ㇟࡜ࡋ࡚ࠊScheme 1࡟♧ࡍࣔࢹࣝ࢟ࣛࣝศᏊ㸦7U|JHU VEDVH  ࠊNN GLSKHQ\OF\FORSURSDQHGLFDUER[DPLGH  ࠊ GLPHWK\OELSKHQRO  ࠊWULIOXRURSKHQ\OHWKDQRO  㸧ࢆタᐃࡋࡓࠋ
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6FKHPH✀ࡢࢭ࣮ࣝࣟࢫㄏᑟయศᏊ㙐ᮏࢆࢩ࣮ࢺ≧ࠊ࢔࣑࣮ࣟࢫㄏᑟయศᏊ㙐ᮏࢆᅄゅᰕ≧࡟㓄⨨ࡋࠊ࢟ࣛࣝࢭࣞࢡࢱ࣮ࣔࢹࣝ࡜ࡋࡓ㸦ᅗ㸧ࠋࢩ࣮ࢺ୰ኸ㒊ࡲࡓࡣᅄゅᰕࡢ୰ᚰ㒊࡟ἢࡗ࡚࢟ࣛ࢟ࣛࣝศᏊࢆࢭࣞ
ࢡࢱ࣮ࣔࢹࣝ୧➃㛫࡛ ᚟ࡉࡏࠊ࢟ࣛࣝศᏊ࡜࢟ࣛࣝࢭࣞࢡࢱ࣮ࣔࢹࣝ⾲㠃㛫ࡢ┦஫స⏝ࢆồࡵࡓࠋ ᚟
ᅇᩘࡣ㸰ᅇ࡜ࡋࠊ⊂❧ࡋࡓ60'ィ⟬ࢆᅇ⧞ࡾ㏉ࡋࠊồࡵࡓ┦஫స⏝ศᕸࢆ୧࢚ࢼࣥࢳ࣐࣮࢜㛫࡛ẚ㍑ࡋ
ࡓࠋ᭱㐺࡞ࢩ࣑࣮ࣗࣞࢩࣙࣥ᮲௳ࡼࡾồࡵࡓ୧࢚ࢼࣥࢳ࣐࣮࢜ࡀ♧ࡍศ㞳ࣆ࣮ࢡࡢศ㞳ᗘ㸦R㸧
㸦ᅗཧ↷㸧
ࢆ⾲࡟ẚ㍑ࡍࡿࠋ&7'3&ࡀ࢟ࣛࣝศᏊ࡟ᑐࡋ࡚ẚ㍑ⓗࠊⰋዲ࡞ศ㞳⤖ᯝࢆ୚࠼ࡓࡀࠊᐇ㝿ࡢ࢟ࣛࣝ࢝
࣒ࣛ࡟ࡼࡿศ㞳࣮ࣔࢻ࡜ẚ㍑ࡍࡿ࡜༑ศ࡞ศ㞳ᗘࡀᚓࡽࢀࡓ࡜ࡣゝ࠼࡞࠸ࠋ௒ᚋࠊࡉࡽ࡟ከࡃࡢ ࢟ࣛࣝศᏊ࡟ᑐࡋ࡚ࠊᏳᐃ࡞ศ㞳ᣲືࢆ♧ࡍࢩ࣑࣮ࣗࣞࢩࣙࣥィ⟬ᡭẁ࡜ィ⟬᮲௳ࡢᨵⰋࡀᚲせ࡛࠶ࡿࠋ

- 113 -

ᅗ䠏㻚㻌 ᮏ◊✲䛷⏝䛔䛯䜻䝷䝹䝉䝺䜽䝍䞊䝰䝕䝹䠄ᕥ䠖㻯㼀㻰㻼㻯䚸ྑ䠖㻭㻹㻰㻼㻯䠅㻌ᅗ䠐㻚㻌 ศ㞳ᗘ 㻾 䛸ศ㞳ಀᩘ Į 䛾ᐃ⩏㻌⾲䠍㻚㻌 䜻䝷䝹ศ㞳䝅䝭䝳䝺䞊䝅䝵䞁䛻䜘䛳䛶ぢ✚䜒䜙䜜䛯ศ㞳ᗘ 㻾㻌

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ࡿ⤖ᬗᛶᇶ㉁ࡢㄆ㆑࡜ࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ๤㞳ࢆ⤒ࡿศゎᶵᵓࡢศᏊㄽⓗ࡞ゎ᫂ࡣࠊࢭ࣮ࣝࣛࢮ◊✲ࡢᇶ♏࣭ᛂ⏝㠃࡟࠾࠸࡚㔜せ࡞᝟ሗ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㧗άᛶࢭࣟࣅ࢜ࣄࢻ࣮ࣟࣛࢮ࡜ࡋ࡚ከࡃࡢ◊✲ࡀሗ࿌ࡉࢀ࡚ࡁࡓTrichoderma reesei ⏤᮶ࢭ࣮ࣝࣛࢮ㸦&HO$㸧ࢆᵓᡂࡋࠊ⤖ᬗᛶࢭ࣮ࣝࣟࢫᇶ㉁ㄆ㆑⬟ࢆᣢࡘ⢾㉁⤖ྜᛶࣔࢪ࣮ࣗࣝ &%0  ࡟ࡘ࠸࡚ゎᯒࡋࡓࠋ

 3'%ࢹ࣮ࢱ࣮࣋ࢫࡼࡾධᡭࡋࡓ࣐ࣥࣀࢩࣝ໬&HO$ &%0㸦0:.㸧ࢆࠊᮏࡢࢭ࣮ࣝࣟࢫศᏊ㙐
㸦'3 㸧࡛ᵓᡂࡉࢀࡿኳ↛,ȕᆺ   ⤖ᬗ㠃ࣔࢹࣝୖ࡟&%0ࢆ㓄⨨ࡉࡏࡓ」ྜయ⤖ᬗࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࡑࡢ㝿ࠊࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ㠀㑏ඖᮎ➃࠿ࡽ㑏ඖᮎ➃᪉ྥ࡟ᑐࡋ࡚ࠊ&%0ࡀྠࡌ᪉ྥ࡜࡞ࡿ㓄⨨㸦SDUDOOHOࠊ
3㸧࡜㏫᪉ྥ࡜࡞ࡿ㓄⨨㸦DQWLSDUDOOHOࠊ$3㸧ࢆタᐃࡋࡓ㸦ᅗ㸧ࠋࡇࢀࡽ」ྜయࣔࢹࣝ࡟ࡘ࠸࡚ࠊ&%0୰ᚰཎᏊ࡟୍ᐃࡢእຊࢆ༳ຍࡋ࡚&%0ࢆ⛣ືࡉࡏࡿ60'ィ⟬ࢆ㐺⏝ࡋࠊ&%0ࡢ⛣ື࡟క࠺30)್ࢆồࡵࡓࠋ &%0 ࡢ⛣ື࡟క࠸ 30) ኚ໬᭤⥺ࡣቑຍࡍࡿ୍᪉࡛ࠊࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ⧄⥔࿘ᮇ㸦⣙ QP㸧ࡢ㛫㝸࡛ᴟᑠⅬࡀ⏕ࡌࡓࠋ&%0 ࡢᚋ㐍⛣ື࡟ẚ࡭࡚๓㐍⛣ືࡀࡼࡾᑡ࡞࠸ 30) ቑຍ࡜࡞ࡗࡓࠋࡉࡽ࡟ࠊ$3㓄⨨࡟࠶ࡿ &%0 ࡢ๓㐍⛣ືࡢ 30) ቑຍࡀ᭱ࡶᑡ࡞ࡃࠊ⧄
⥔࿘ᮇࡢ⛣ື࠶ࡓࡾ⣙ NFDOPRO ࡜࡞ࡗࡓࠋ$3 㓄⨨ &%0ࡢ๓㐍᪉ྥࡣࠊ&HO$ ඲యࡀ♧ࡍ㓝⣲ศゎࡢࣉࣟࢭࢵࢩࣥࢢ
᪉ྥ࡜୍⮴ࡋࡓࠋࡇࡢ⤖ᯝࡣࠊ&%0 ࡀࢭ࣮ࣝࣟࢫ␯Ỉᛶ⤖ᬗ㠃ࢆㄆ㆑ࡍࡿࡔࡅ࡛࡞ࡃࠊ&HO$ ඲యࡢ⛣ື᪉ྥ࡟ᑐࡋ࡚
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- 114 -

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1.1 㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ≀㉁㍺㏦ࡢゎ᫂㧗ศᏊ㟁ゎ㉁⭷࡞࡝ࡢ୙ᆒ୍⣔࡟࠾ࡅࡿᑠศᏊࡢ㍺㏦ࢆゎ᫂ࡍࡿᡭἲࢆ㛤Ⓨࡍࡿࠋ㧗ศᏊ㟁ゎ㉁⭷࡞࡝ࡢ㧗ศᏊࡢྵỈ≀ࡣࠊ㧗ศᏊ࡜ᾮయ࡜ࡀධࡾ஘ࢀࡓ୙ᆒ୍⣔ࢆᙧᡂࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞ྵỈ≀ෆ㒊࡛ࡢᑠศᏊࡢ㐠ືࡣࠊᣑᩓⓗ࡛࠶ࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋᣑᩓⓗ࡞≀㉁㍺㏦ࡣࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ࡟ࡼࡾグ㏙࡛ࡁࡿࠋࡇࢀࡽࡢ஧ࡘࡢ≀⌮㔞ࢆ✵㛫ࡢྛⅬ࡛ồࡵࡿࡇ࡜࡛ࠊᑠศᏊࡢ㍺㏦ࡢ㥑ືຊ࡜㥑ືຊ࡟ᑐࡍࡿ᢬ᢠࢆ㧗ศᏊෆ㒊ࡢྛⅬ࡛ホ౯࡛ࡁࡿࠋࡇࡢ᝟ሗࢆ฼⏝ࡋ࡚ࠊ≀㉁㍺㏦ࡢ⤒㊰࡞࡝ࡢヲ⣽ࢆศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࠋࡉࡽ࡟ࠊ⢒ど໬ࢲ࢖ࢼ࣑ࢡࢫࢆࣔࣥࢸ࢝ࣝࣟἲ࡞࡝࡟ࡼࡾゎࡃࡇ࡜࡛ࠊ඲ཎᏊ
ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ᫬㛫ࢆ㉸࠼ࡓ㛗᫬㛫ࡢࢲ࢖ࢼ࣑ࢡࢫࢆண

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1.2 ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢศゎᶵᵓࡢゎ᫂ᮏ◊✲ࡣࠊ࣒࣮ࣥࢩࣙࢵࢺᆺ◊✲㛤Ⓨࣉࣟࢪ࢙ࢡࢺࠕ㠀ྍ㣗ᛶࣂ࢖࣐࢜ࢫࢆཎᩱ࡜ࡋࡓᾏὒศゎྍ⬟࡞࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢ◊✲㛤Ⓨࠖࡢࡶ࡜ࠊィ⟬⛉Ꮫࡢ❧ሙ࠿ࡽㄢ㢟ࢆゎỴࡍࡿࠋ⎔ቃ࡟ඃࡋ࠸࡜ࡉࢀࡿ᪂つ࡞ࣂ࢖࣐࢜ࢫ⏤᮶ࡢ㧗ศᏊᮦᩱࡸ⏕ศゎᛶ࣏࣐࣮ࣜࡀ㛤Ⓨࡉࢀࠊᐇ⏝໬ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ
ᅵተ࡜ᾏὒࡢ୧᪉࡛⏕ศゎᛶࢆ♧ࡍ࣏࣐࣮ࣜᮦᩱ࡛ᐇ⏝໬ࡉࢀ࡚࠸ࡿࡶࡢࡣᴟࡵ࡚ᑡ࡞࠸ࠋࡲࡓ⏕ศゎᛶ࣏࣐࣮ࣜࡣ⮬↛⎔ቃୗ࡛ຎ໬ࡀ㐍ࡳࡸࡍ࠸Ⅼ࡛⪏ஂᛶ࡟ຎࡾࠊᶵᲔ≉ᛶࡶ༑ศ࡛࡞࠸ࡓࡵࠊ⏝㏵ࡀ㝈ࡽࢀᗈ⠊ᅖ࡞ศ㔝࡛ࡢ฼⏝ࡀ㐍ࢇ࡛࠸࡞࠸ࠋࡍ࡞ࢃࡕࠊ㧗ศᏊࡢ⏕ศゎᛶ࡜⪏ஂᛶ࣭ᙉ㠌ᛶࡣ඾ᆺⓗ࡞ࢺ࣮ࣞࢻ࢜ࣇ
ࡢ㛵ಀ࡟࠶ࡿࠋࡇࡢࡼ࠺࡞ࢺ࣮ࣞࢻ࢜ࣇ㛵ಀࢆᡴ◚ࡍࡿࡓࡵ࡟ࠊ㧗ศᏊࡢศゎ࡟࣐ࣝࢳࣟࢵࢡᶵᵓ̿ศゎࡢ㝿࡟ࠊ」ᩘࡢ่⃭㸦ග࣭⇕࣭Ỉ࣭࢖࢜ࣥ࡞࡝㸧ࢆྠ᫬࡟ᚲせ࡜ࡍࡿࣟࢵࢡᶵᵓ̿ࢆᑟධࡍࡿࠋ౑⏝᫬࡟ࡣศゎࢆᢚ࠼࡚ࢱࣇࢿࢫࢆಖࡗ࡚ຎ໬ࢆ㜵ࡄࡇ࡜࡛ᐇ⏝ᛶࢆ☜ಖࡍࡿࠋ௚᪉ࠊ⎔ቃ୰࡟ㄗࡗ࡚ᣑᩓࡋࡓሙྜ࡟ࡣ㏿ࡸ࠿࡞ศゎࡀྍ⬟࡜࡞ࡿࠋࡋࡓࡀࡗ࡚ࠊḟୡ௦ࡢࣂ࢖࣏࣐࣮࢜ࣜ࡜ࡋ࡚㠀ᖖ࡟᭷ᮃ࡛࠶ࡿࠋ
ࡑࡇ࡛ࠊ㧗ศᏊࡢศゎ཯ᛂ࡟㛵ࡍࡿ᪂つᴫᛕࢆᵓ⠏ࡋࠊ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢᮦᩱタィᣦ㔪ࢆ☜❧ࡍࡿࠋಙ㢗ᛶࡢ㧗࠸ศゎࢩࢫࢸ࣒ࡢタィ࡟ࡣࠊ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢศゎᶵᵓࡢゎ᫂࡟ຍ࠼࡚ࠊ⏕ศゎᛶࡸ࣐ࣝࢳࣟࢵࢡᶵ⬟ࡢ௜ຍ࡟ࡼࡾ᪂ࡓ࡟せồࡉࢀࡿࢱࣇࢿࢫ໬ࢆࡣ࠿ࡿྜ⌮ⓗタィᢏ⾡ࡢ☜❧ࡶ୙ྍḞ࡛࠶ࡿࠋᮏᖺᗘࡣࠊග࣭⇕࣭ග࡞࡝እ㒊࠿ࡽ」ᩘࡢ่⃭࡟ࡼࡾᾏὒ࡞࡝ࡢ⎔ቃ࡟࠾࠸࡚㏿ࡸ࠿࡟ศゎࡍࡿࠕ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࠖ࡟࠾ࡅࡿ㟁Ꮚ࠶ࡿ࠸ࡣศᏊ࡛ࣞ࣋ࣝࡢศゎ཯ᛂࡢᶵᵓゎ᫂ࢆ┠ᣦࡍࠋ

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2.1 㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ≀㉁㍺㏦ࡢゎ᫂㧗ศᏊ㟁ゎ㉁⭷ QDILRQ  ࡟࠾ࡅࡿ఩⨨࡟౫Ꮡࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ࡜ᣑᩓಀᩘࡣࠊ๓ᖺᗘࡲ࡛࡟ィ⟬῭ࡳ࡛࠶ࡿࠋࡇࢀࡽࡢ᝟ሗ࡟ᇶ࡙࠸࡚ࠊỈ⣲࣭㓟⣲ศᏊࡢ኱ᇦⓗᣑᩓࢆືⓗࣔࣥࢸ࢝ࣝࣟ (DMC) ἲ࡟ࡼࡾヲࡋࡃゎᯒࡋࡓࠋࡇࡢࣔࣥࢸ࢝ࣝࣟィ⟬⮬㌟ࡢィ⟬㈇Ⲵࡣ㍍ࡃࠊᩘ୓ಶࡢᣑᩓࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ㌶㊧ࡀᐜ᫆࡟ィ⟬࡛ࡁࡿࠋࡋࡓࡀࡗ࡚ࠊ㛗᫬㛫ࡢ⌧㇟ࢆ⤫ィⓗ࡟㧗࠸⢭ᗘ࡛ᚓࡽࢀࡓࠋࡇࢀࡽ㌶㊧ࡢゎᯒ࠿ࡽࠊ㍺㏦
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2.2 ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢศゎᶵᵓࡢゎ᫂ࢱࣥࢢࢫࢸ࣭ࣥࣂࢼࢪ࣒࢘࠿ࡽ࡞ࡿ㔠ᒓࢡࣛࢫࢱ࣮ගゐ፹࠾ࡼࡧ࣏࣐࣮ࣜࣔࢹࣝศᏊࡢ㟁Ꮚ≧ែࢆィ⟬ࡋࡓࠋࢯࣇࢺ࢙࢘࢔ࡣࠊ*DXVVLDQ ࠾ࡼࡧ 25&$ ࢆ᥇⏝ࡋࡓࠋィ⟬ᡭἲࡣࠊᐦᗘỗ㛵ᩘἲ࡛࠶ࡿࠋࡲࡎࠊ㔠ᒓゐ፹࠾ࡼࡧ࣏࣐࣮ࣜศᏊࢆ༢⊂࡛ィ⟬ࡋࠊ㓟໬㑏ඖ཯ᛂ㸦Ỉ⣲ᘬࡁᢤࡁ࣭㟁Ꮚ⛣ື㸧ࡢ཯ᛂ⇕ࢆணࡋࡓࠋྜࢃࡏ࡚ࠊỈ⣲ᘬࡁᢤࡁ཯ᛂ࡟࠾ࡅࡿゐ፹࠾ࡼࡧ࣏࣐࣮ࣜ㙐ࡢ཯ᛂࢧ࢖ࢺࡢྠᐃࢆ࠾ࡇ࡞ࡗࡓࠋ
ゐ፹࣏࣐࣮̽ࣜศᏊࡢ」ྜయࡢ཯ᛂゎᯒࢆ࠾ࡇ࡞ࡗࡓࠋ᭱ప୕㔜㡯ບ㉳≧ែࢆ௬ᐃࡋࡓࠋỈ⣲ᘬࡁᢤࡁ཯ᛂ
ࡢ཯ᛂ≀ 5 ࣭㑄⛣≧ែ࣭⏕ᡂ≀ 3  ࢆ㏻ᖖࡢᵓ㐀᭱㐺໬ィ⟬࡟ࡼࡾỴᐃࡋࡓࠋỈ⣲ᘬࡁᢤࡁᚋ࡟㉳ࡇࡾ࠺ࡿ཯ᛂࡢ඲యീࡣ୙࡛᫂࠶ࡿࡀࠊ᭱⤊⏕ᡂ≀࡜ᛮࢃࢀࡿᵓ㐀 3  ࢆᚓࡓࠋࡑࡇ࡛ 3 ࡜ 3 ࢆ➃Ⅼ࡜ࡋ࡚
Nudged Elastic Band (NEB) ἲࢆ㐺⏝ࡋࠊ཯ᛂ⤒㊰ࡢ᥈⣴࡜㏵୰ࡢ㟁Ꮚ≧ែࡢኚ໬࡟ࡘ࠸࡚ゎᯒࡋࡓࠋ࣐ࣝࢳࣟࢵࢡ཯ᛂᶵᵓ࡛ࡣࠊගゐ፹ࡢ㓟໬཯ᛂ࡟ࡼࡾࠊῧຍࡋࡓ࢖࢜ࣥࡢࣛࢪ࢝ࣝ໬ࡀ᝿ᐃࡉࢀࡿࠋࡑࡇ
࡛ࠊྛ✀࢖࢜ࣥ㸦ࣁࣟࢤࣥ໬≀࢖࣭࢜ࣥ◲㓟Ỉ⣲࢖࣭࢜ࣥ◲㓟࢖࢜ࣥ㸧ࡢ࢖࢜ࣥ໬࣏ࢸࢩࣕࣝ࠾ࡼࡧゐ፹̽࢖࢜ࣥࡢ」ྜయࡢィ⟬ࢆ࠾ࡇ࡞ࡗࡓࠋᐇ㦂࡛ほࡉࢀ࡚࠸ࡿ࢖࢜ࣥ✀࡟ࡼࡿ཯ᛂᛶࡢ㐪࠸ࢆࠊ࢖࢜ࣥ໬࣏ࢸࣥ

ࢩࣕࣝ࡜」ྜయࡢࢫࣆࣥᐦᗘศᕸ࠿ࡽ⪃ᐹࡋࡓࠋ

2.3 0HFKDQLFDOSURSHUWLHVRIELRGHJUDGDEOHSRO\ODFWLFDFLG:HUDQWKH0'VLPXODWLRQXVLQJWKHPRGLILHGYHUVLRQRI*520$&6DQG02'</$66LQFH)HEUXDU\ZHKDYH
FDUULHGRXWDVHULHVRIWHVWVWRHVWLPDWHWKHFRPSXWDWLRQDOHIILFLHQF\RIWKH&38VLPSOHPHQWHGDIWHUPDLQWHQDQFH)RU
02'</$6XVLQJWKHGLIIHUHQWQXPEHURIQRGHVYDU\LQJIURPDQGWKHFDOFXODWLRQHIILFLHQF\LV
DQGVHFVWHSUHVSHFWLYHO\$WWKHVDPHWLPHWKHHIILFLHQF\ZDVQRWUHSURGXFLEOHHYHQXVLQJWKHVDPHQXPEHU
RIQRGHV:HIRXQGDVLPLODUWHQGHQF\XVLQJRXUPRGLILHG*520$&6DQGWKHSUHLQVWDOOHGRQHSURYLGHGE\WKH,06
7KHHIILFLHQF\YDULHVIURPWRKRXUVQVXVLQJWKHVL[WHHQQRGHV7RVDYHFRPSXWDWLRQDOFRVWVZHGHDOWZLWKWKH
*520$&6UXQVWKURXJKWULDODQGHUURUWRNHHSWKHHIILFLHQF\IDVWHUWKDQKRXUVQV

- 117 -

◊✲ᡂᯝ3.1 㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ≀㉁㍺㏦ࡢゎ᫂఩⨨౫Ꮡࡢᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ࢆᣢࡘ୍⢏ᏊᣑᩓᛶศᏊ㐠ື࡟⢒ど໬ࡍࡿࡇ࡜࡛ࠊ␗✀⣔࡟࠾ࡅࡿศᏊࡢ㛗㊥㞳࣭㛗᫬㛫ࡢ኱ᇦⓗ࡞㍺㏦⌧㇟ࢆㄪ࡭ࡓࠋࡲࡎࠊ᪂ࡋ࠸ࣔࣥࢸ࢝ࣝࣟ㑄⛣☜⋡ࢆᑟධࡋࡓࠋࡇࡢ
ᡭἲࡣࠊ఩⨨౫Ꮡࡢᣑᩓಀᩘ࡜࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࢆᣢࡘᣑᩓ᪉⛬ᘧࢆ⤫ィⓗ࡟‶ࡓࡍ㌶㐨ࢆ⏕ᡂ࡛ࡁࡿࠋ☜⋡ศᕸࡢ᫬㛫Ⓨᒎࡸᖹᆒึᅇ㏻㐣᫬㛫ࢆィ⟬ࡋࠊ㌶㐨ࢆᣑᩓ᪉⛬ᘧࡢᩘ್ゎ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊⰋ࠸
୍⮴ࢆ♧ࡋࡓࠋࡲࡓࠊࡇࡢ᪉ἲࡣከ⢏Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟ࡶ㐺⏝ྍ⬟࡛࠶ࡿࠋ⇞ᩱ㟁ụࡢ㟁ゎ㉁⭷ࡢ୙ᆒ୍ᵓ㐀࡛ࡢỈ⣲ศᏊࡢ኱ᇦⓗ࡞ᣑᩓ࡟ࡘ࠸࡚ࠊᮏᡭἲࢆ㐺⏝ࡋࡓࠋỈ⣲ศᏊࡢ
3 ḟඖ఩⨨౫Ꮡ⮬⏤࢚ࢿࣝࢠ࣮࡜ᣑᩓᐃᩘࢆ⏝࠸࡚ࠊୖ㏙ࡢ '0& ィ⟬ࢆ࠾ࡇ࡞ࡗࡓࠋ㛤Ⓨࡋࡓ '0& ἲࡢ㛗ᡤࡣࠊ኱ᇦⓗ࡞ᣑᩓᐃᩘࢆྵࡴ㛗᫬㛫ࢫࢣ࣮࡛ࣝࡢỈ⣲ࡢᣑᩓࢲ࢖ࢼ࣑ࢡࢫࡢホ౯ࡀྍ⬟࡞Ⅼ࡛࠶ࡿࠋィ⟬ࡉࢀࡓ኱ᇦⓗ࡞ᣑᩓᐃᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮࡟ᇶ࡙ࡁࠊ⁐ゎ̽ᣑᩓࣔࢹࣝ࡟ࡼࡾỈ⣲ศᏊࡢ㏱㐣ᛶࢆ᥎ᐃࡋࡓࠋ
ࡇࡢ᥎ᐃ್ࡣࠊሗ࿌ࡉࢀ࡚࠸ࡿᐇ㦂ࢹ࣮ࢱ࡜ࡼࡃ୍⮴ࡋࠊᮏᡭἲࡢጇᙜᛶࡀ♧ࡉࢀࡓࠋ㌶㊧ࡢゎᯒ࠿ࡽࠊỈ⣲ศᏊࡢ୺࡞㏱㐣⤒㊰ࡣ࣏࣐࣮ࣜ┦࡜ቃ⏺㠃┦࡟࠶ࡿ୍᪉ࠊỈ┦ࡣ㍺㏦࡟↓ど࡛ࡁ࡞࠸ᐤ୚ࢆࡋ࡚࠸ࡿྍ⬟ᛶࢆ♧ࡋࡓࠋ

3.2 ࣐ࣝࢳࣟࢵࢡᆺࣂ࢖࣏࣐࣮࢜ࣜࡢศゎᶵᵓࡢゎ᫂࢖࢜ࣥ࡟ࡼࡿ࣐ࣝࢳࣟࢵࢡᆺศゎ཯ᛂࡢไᚚ࡛ࡣࠊ $  ගゐ፹༢⊂࡛ศゎ཯ᛂࢆ࠾ࡇࡉ࡞࠸ࡇ࡜ࠊ࠾ࡼࡧ%  ࢖࢜ࣥῧຍ࡟ࡼࡾࡣࡌࡵ࡚ศゎ཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀせồࡉࢀࡿࠋࡲࡎࠊゐ፹༢⊂ࡢሙྜࡢ཯ᛂᶵᵓࡢゎ᫂ࢆ┠ᣦࡋࡓࠋᐇ㦂࡛ࡣ࣏࣐࣮ࣜࡢศᏊ㔞ࡢኚ໬࠿ࡽࠊศゎ཯ᛂࡣ㉳ࡁ࡞࠸࡜⤖ㄽ࡙ࡅࡽࢀ࡚࠸ࡿࠋ
୍᪉ࠊᑠࡉ࡞᭷ᶵศᏊࡢᐇ㦂࡛ࡣࠊ㓟໬཯ᛂ࡟ࡼࡿࢣࢺࣥࡢ⏕ᡂࡀ☜ㄆࡉࢀ࡚࠸ࡿࠋゐ፹±࣏࣐࣮ࣜ」ྜయࡢィ⟬⤖ᯝ࠿ࡽࠊỈ⣲ᘬࡁᢤࡁ཯
ᛂ 5ĺ3  ࡜Ⅳ⣲±㓟⣲⤖ྜ 3ĺ3  ࡢ⏕ᡂ཯ᛂࡢ㸰ẁ㝵཯ᛂࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ๓⪅ࡣࠊ཯ᛂ㞀ቨࡀపࡃࠊỈ⣲ཎᏊࡢࢺࣥࢿࣝຠᯝࡶ
ྜࢃࡏࡿ࡜ࠊᐇ㉁ⓗ࡞㞀ቨࡣ࡞࠸࡜⪃࠼ࡽࢀࡿࠋࡑࡢࡓࡵࠊ㏿ࡸ࠿࡟Ỉᅗ 1.

⣲⛣ື཯ᛂࡀ㉳ࡇࡿ࡜᝿ᐃࡉࢀࡿࠋᚋ⪅ࡣࡲࡔィ⟬㏵୰࡛࠶ࡿࡀࠊ཯

ゐ፹࣏࣐࣮̽ࣜ」ྜయࡢ
཯ᛂ⤒㊰ (P1 Ѝ P2)

ᛂ㞀ቨࡀప࠸⤒㊰ࡢᏑᅾࡀ☜ㄆࡉࢀࡓ㸦ᅗ 㸧ࠋࡋࡓࡀࡗ࡚ࠊ᭱⤊⏕ᡂ≀ 3  ࡬⮳ࡿྍ⬟ᛶࡀ㧗࠸ࠋ3 ࡢᏑᅾ࡜せồ㡯┠ $  ࡟ᩚྜᛶࡀ࠶ࡿ࠿ࡣ⌧᫬Ⅼ࡛ࡣ᫂ࡽ࠿࡛ࡣ࡞࠸ࠋ௒
ᚋࠊỈ⣲ᘬࡁᢤࡁ཯ᛂࡢࢧ࢖ࢺ౫Ꮡᛶࡸ 3 ࢆฟⓎⅬ࡜ࡍࡿ཯ᛂ⤒㊰࡟ࡘ࠸࡚ゎᯒࡍࡿணᐃ࡛࠶ࡿࠋ㔠ᒓゐ፹̽㝜࢖࢜ࣥࡢ」ྜయ࡟࠾ࡅࡿࠊࢫࣆࣥᐦᗘศᕸࢆィ⟬ࡋࡓࠋ
ᅗ 2 ࡣࠊሷ໬≀࢖࢜ࣥࡢィ⟬౛࡛࠶ࡿࠋሷ⣲ཎᏊୖ࡟ࢫࣆࣥࡀᒁᅾࡋ
࡚࠾ࡾࠊሷ⣲ࣛࢪ࢝ࣝ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟⏕ᡂࡋࡓࣛࢪ࢝ࣝ✀ࡀࠊ࣏࣐࣮ࣜ㙐ࢆᨷᧁࡋศゎ཯ᛂࡀ㐍⾜ࡍࡿ࡜ᛮࢃࢀࠊ
ィ⟬⤖ᯝࡣせồ㡯┠ (B) ࡜▩┪ࡋ࡞࠸ࠋྠᵝࡢィ⟬ࢆ௚ࡢࣁࣟࢤࣥ໬
≀࢖࢜ࣥࡸ◲㓟Ỉ⣲࢖࢜ࣥ࡟ࡘ࠸࡚ࡶ⾜ࡗࡓ࡜ࡇࢁࠊᐇ㦂ࡢഴྥࢆᐃ
ᛶⓗ࡟ㄝ࡛᫂ࡁࡓࠋ௒ᚋࠊࣛࢪ࢝ࣝ✀࡟ࡼࡿỈ⣲ᘬࡁᢤࡁ࡟ࡼࡾ࣏ࣜ
࣐࣮ࡢศゎࡀ㉳ࡇࡿ࠿࡝࠺࠿ィ⟬ࢆࡍࡍࡵࡿணᐃ࡛࠶ࡿࠋ

- 118 -

ᅗ 2.

ゐ፹̽ሷ໬≀࢖࢜ࣥ」ྜ
యࡢࢫࣆࣥᐦᗘศᕸ

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1.

‫ۻ‬Ọ஭ဴ㑻࣭ᒸᓮ㐍ࠊ㧗ศᏊ㟁ゎ㉁⭷୰࡛⏕ࡌࡿ࢞ࢫࡢ㍺㏦࡟㛵ࡍࡿ኱つᶍศᏊືຊᏛィ⟬࡜ືⓗࣔࣥࢸ࢝ࣝࣟἲ࡟ࡼࡿ◊✲㸦ཱྀ㢌Ⓨ⾲㸧ࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍㸦ᶓ὾㸧ࠊ2022.

2.

‫ۻ‬Ọ஭ဴ㑻࣭ᒸᓮ㐍ࠊ㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ࢞ࢫ㍺㏦ࡢศᏊືຊᏛィ⟬࡜᪂つ࡞ືⓗࣔࣥࢸ࢝ࣝࣟ
ἲ࡟ࡼࡿ◊✲㸦ཱྀ㢌Ⓨ⾲㸧ࠊ➨ 44 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘㸦㮵ඣᓥ㸧
ࠊ2022.

3.

㤿ሙᘅᾏ࣭Ọ஭ဴ㑻࣭ᾆ㔝ㄹ࣭ᒸᓮ㐍ࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᾮయࡢ⮬ᕫᣑᩓಀᩘ࣭⢓ᛶಀᩘࡢணᛶࡢホ౯㸦࣏ࢫࢱ࣮Ⓨ⾲㸧ࠊ➨ 36 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᮾி㸧ࠊ2022.

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[1] T. Horikawa, R. Yuasa, K. Yoshida, D.D. Do, Carbon, 183, 380 (2021).
[2] N. Noguchi, T. Yonezawa, Y. Yokoi, T. Tokunaga, T. Moriwaki, Y. Ikemoto, H. Okamura, J. Phys. Chem. C, 125,
189 (2021).
[3] G. Fuseya, S. Takeya, A. Hachikubo, RCS Adv., 10, 17473 (2020).

 (%
ÜÜÝKen Yoshida: Adsorption and Film-Formation of Corrosion-Protective Aliphatic Amines on Metal Surface in
Hot Water, 1st International Solvothermal and Hydrothermal Association Seminar, Online, Apr. 2022 [Invited].
ÜÝÝN§ < : ,½¨JÎ½¨M©Wmº%tÃ¨)X&ÉJ6*;C
04J¹, FC04I1 ± 35 c­c3I

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Ìµq¹gWma«8&Öm£,¤p`O%/+! 2022, PS12, 2022 y 9 .

ÜÝSaki Kurohama, Naoki Noguchi and Hidekazu Okamura: Interaction between host framework and methane
molecule in methane hydrate phase up to 40 GPa, International Workshop on Infrared Microscopy and Spectroscopy with- 122 -

Accelerator Based Sources (WIRMS 2022), Hiroshima, Oct. 2022.
ÜÝNaoki Noguchi, Chisaki Teraoka, Shiraishi Yui, Kurohama Saki, Yokoi Yuu and Hidekazu Okamura : Dynamics
and amorphization of methane hydrates at high pressures and low temperatures, International Workshop on Infrared
Microscopy and Spectroscopy with Accelerator Based Sources (WIRMS 2022), Hiroshima, Oct. 2022.
ÜÝKen Yoshida: Formation Mechanism and Microscopic Structure of Corrosion Protective Coating for Steam

Piping by Film-Forming Amine, International Association for the Properties of Water and Steam Annual Meeting
2022, Rotorua, New Zealand, Dec. 2022 [Invited].
Ü!Ý

[µy, Ö ,  b, À&, ÖL  : D5I>*:HK9MD5INÌ, ± 63 cÛVÅ1, 2022 y 12 .

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cÛVÅ1, 2022 y 12 .
ÜÜÝKen Yoshida: Structure, Formation Mechanism, and Reaction of Film-Forming Amines for Anticorrosion
Protection for Steam Piping, The 9th International Discussion Meeting on Relaxations in Complex Systems, Chiba, Japan,
Aug. 2023 [Invited].

%
ÜÜÝIuchi Hirotoshi and Toshihide Horikawa : Influence of resorcinol-formaldehyde resin on the formation of alkalititanate fibers, Ceramics International, Vol. 48, No. 4, 5704-5713, 2022.
Ü Ý Ý Haruka Yoshioka, Ken Yoshida, Naoki Noguchi, Tomoyuki Ueki, Kei-ichiro Murai, Kazuya
Watanabe and Masaru Nakahara: Microscopic Structure and Binding Mechanism of the Corrosion-Protective Film of
Oleylpropanediamine on Copper in Hot Water, The Journal of Physical Chemistry C, Vol.126, No.14, 6436-6447, 2022.
ÜßÝToshihide Horikawa, Miku Okamoto, Ayaka Kuroki, and Ken Yoshida: Significant role of counterion forlead() ion adsorption on carbon pore surface, Carbon, Vol.196, 575-588, 2022.
ÜÝHirotomo Nishihara, Hong-Wei Zhao, Kazuya Kanamaru, Keita Nomura, Mao Ohwada, Masashi Ito, Li-Xiang
Li, Bai-Gang An, Toshihide Horikawa and Takashi Kyotani : Adsorption properties of templated nanoporous carbons
consisting of 1-2 graphene layers, Carbon Reports, Vol.1, No.3, 123-135, 2022.
Ü  Ý Tomáš Zelenka, Toshihide Horikawa and D.D. Do: Artifacts and Misinterpretations in Gas Physisorption
Measurements and Characterization of Porous Solids, Advances in Colloid and Interface Science, Vol.311, 102831, 2023.
ÜÝHidekazu Okamura, Takashi Mizokawa, Katsuaki Miki, Yuta Matsui, Naoki Noguchi, Naoyuki Katayama,
Hiroshi Sawa, Minoru Nohara, Yangfan Lu, Hidenori Takagi, Yuka Ikemoto and Taro Moriwaki : Pressure suppressionof the excitonic insulator state in Ta2NiSe5 observed by optical conductivity, Physical Review B, Vol.107, 045141-1045141-7, 2023.
ÜÝ Ken Yoshida, Ayato Doi, Haruka Yoshioka, Tomohiro Hirano and Masaru Nakahara Nuclear Magnetic

Resonance Analysis of Hydrothermal Reactions of Ethyl- and Octylamine in Sub- and Supercritical Water,7KH-RXUQDO
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ࡼࡾ 36,, ࡟㛵ࡍࡿ◊✲࡟࠾࠸࡚ࠊ౛࠼ࡤඹྠ◊✲⪅ࡢỿࡽࡸࠊ᭱㏆ࡢ %HUNHOH\ /%/  ࢢ࣮ࣝࣉ࡟ࡼࡿ㧗ศゎ⬟ ;)(/ ᐇ㦂࡟ࡼࡿ 6 ᵓ㐀࠿ࡽ 6 ≧ែࡢ཯ᛂᶵᵓࡢゎ᫂ࡢࡓࡵࡢᵓ㐀ⓗᇶ┙ࡀゎ᫂ࡉࢀࡘࡘ࠶ࡾࠊỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡ࡟ࡼࡿỈศᏊࡸࣉࣟࢺࣥࡢ⛣ື࡜཯ᛂ㐣⛬ࡢ㐍⾜࡜ࡢ㛵㐃ࡶ㔜せ࡜࡞ࡗ࡚࠸ࡿࠋࡉࡽ࡟ࠊ᭱
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ᵓ㐀ࡸ࢔࣑ࣀ㓟⨨᥮࡟ࡼࡿᵓ㐀ኚ໬࡞࡝࡟㛵ࡍࡿ▱ぢࡀᚓࡽࢀࡿࡼ࠺࡟࡞ࡾࠊ2(& ࡟࠾ࡅࡿỈศゎ཯ᛂ࡟ᚲせ࡞Ỉᤄධ⤒㊰ࠊࣉࣟࢺࣥᨺฟ⤒㊰࡞࡝ࡢ≉ᐃࡶྍ⬟࡟࡞ࡗ࡚ࡁ࡚࠾ࡾࠊᐇ㦂ⓗ࡟ࡣ᪂ࡓ࡞ẁ㝵࡟ධࡾࡘࡘ
࠶ࡿࠋ୍᪉ࠊ⏦ㄳ⪅ࡽࡣ &D0Q2 ࢡࣛࢫࢱ࣮ࡀ⌮ㄽⓗ࡟ࡣ㟁Ꮚ┦㛵ຠᯝࡀ㔜せ࡛࠶ࡿࡇ࡜ࡼࡾࠊゐ፹ᶵ⬟ࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚ࡑࡢ㟁Ꮚ࣭ࢫࣆࣥ≧ែࡢゎ᫂ࢆ⾜࡞ࡗ࡚ࡁࡓࠋᚑࡗ࡚ࠊ36,, ࡢ㓟⣲Ⓨ⏕ゐ፹ࢧ࢖ࢺ 2(& ࡣᙉ┦㛵㟁Ꮚ⣔ 6&(6 &D0Q2 ࢡࣛࢫࢱ࣮ࡀ 36,, ࡢ⺮ⓑሙ࡟㛢ࡌ㎸ࡵࡽࢀࡓศᏊࢩࢫࢸ࣒࡛࠶ࡿ࡜ࡢどⅬࢆᙉㄪࡋ࡚ࡁࡓࠋୖグࡢࡼ࠺࡟ ;)(/ ࡜᭱㏆ࡢࢡࣛ࢖࢜㟁㢧ᐇ㦂ࡢ㐍Ṍ࡟ࡼࡾࠊศᏊࢩࢫࢸ࣒ᵓ㐀ࡢᵓ㐀ࡀゎ᫂ࡉࢀ࡚᮶ࡓࡢ࡛ࡑࡢᶵ⬟ࡢゎ᫂ࡢࡓࡵ࡟ 4000 ィ⟬࡟ᇶ࡙࠸࡚ 7KHRUHWLFDO0XWDWLRQ ࡶど㔝࡟ධࡗ࡚ࡁ
ࡓ࡜ゝࡗ࡚ࡶ㐣ゝ࡛ࡣ࡞࠸ࠋ⏦ㄳ⪅ࡽࡣࡇࡢࡼ࠺࡞どⅬ࡛ 2(& ࡟࠾ࡅࡿỈศゎ཯ᛂᶵᵓࡢ㟁Ꮚ࣭ཎᏊ࣭ศᏊ࣭
ศᏊࢩࢫࢸ࣒࡛ࡢゎ᫂ࢆ┠ᣦࡋ⣔⤫ⓗ࡟ィ⟬ᶵᐇ㦂ࢆᐇ⾜ࡋ࡚ࡁࡓࠋ⌧ᅾࡲ࡛ࡢ◊✲⤖ᯝࢆ ;)(/ ᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿ࡜ࠊᑐ⛠ᛶࡢ◚ࢀࡓ %URNHQ6\PPHWU\%6  ᐦᗘỗ㛵ᩘ +')7  ࢆ⏝࠸ࡓᡭἲࡣ 40 ᭱኱  ཎᏊ 00 ィ⟬ࡣᵓ㐀᭱㐺໬࡟㛵ࡋ࡚ࡣ༑ศಙ㢗࡛ࡁࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡿࠋࡉࡽ࡟ࠊ(65 ࡢᐇ㦂⤖ᯝ➼࠿ࡽ㏆ఝᑕᙳࢫࣆࣥ $3 ἲࢆ౑ࡗࡓ᭷ຠ஺᥮✚ศࡢィ⟬ࡸཝᐦᑐゅ໬ࢆ౑ࡗࡓࢫࣆࣥ≧ែࡢྫྷ࿡࡟㛵ࡋ࡚ࡶ +)ᡂศࡢㄪᩚ࡟ࡼࡾ %6+')7 ࡀ᭷ຠᡭẁ࡜ࡋ࡚Ⓨ᥹ࡉࢀࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡿࠋ ᖺᗘࡣࠊ;)(/(35%6
')7 ィ⟬ࡢ㐃⤖࡟ࡼࡾᚓࡽࢀࡓ✀ࠎࡢᡂᯝࡀ ,VROREDO DQG ,VRVSLQ ࡜࠸࠺໬Ꮫࡢᇶᮏᴫᛕࡢᇶ࡟⤫୍ⓗ࡟⌮ゎ࡛ࡁࡿࡇ࡜ࢆሗ࿌ࡋࠊ%6 ἲ࡟ࡼࡿ㌶㐨࠾ࡼࡧࢫࣆࣥ⮬⏤ᗘࡢᐃᛶⓗᙺ๭ࢆゎ᫂ࡋࡓࠋ୍᪉ࠊ%6')7 ࡟ࡼࡿᵓ㐀᭱㐺໬࡟㛵ࡋ࡚ࡣ ;)(/ ᐇ㦂࡜ࡢẚ㍑᳨ウ࡟ࡼࡾၥ㢟ࡀ࡞࠸ࡀࠊ࢚ࢿࣝࢠ࣮ィ⟬࡟㛵ࡋ࡚ࡣὀព῝࠸᳨

- 124 -ウࡀᚲ㡲࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ.RN ࢧ࢖ࢡࣝࡢྛ≧ែ࡛⏕ᡂྍ⬟࡛࠶ࡿ୰㛫యࡢ┦ᑐ࢚ࢿࣝࢠ࣮ࡢゎ᫂࡟㛵ࡋ࡚ࡣ %6 +')7  ἲ࡟ྵࡲࢀࡿ +) ᡂศࡢ๭ྜ Z  ࡟ᩄឤ࡞ሙྜࡀ࠶ࡾࠊFRXSOHGFOXVWHU &&  ἲ࡞࡝ࡢ㧗⢭ᗘィ⟬⤖ᯝ࡜ࡢẚ㍑᳨ウ࡟ᇶ࡙ࡁ᭷ຠ࡞ Z ್ࢆ᳨ウࡋ࡚࠾ࡃ஦ࡀᚲせ୙ྍḞ࡛࠶ࡗࡓࠋࡑࡇ࡛ࠊ⏦ㄳ⪅ࡽ
ࡣ '/312&& ἲࢆィ⟬ྍ⬟࡞ẚ㍑ⓗᑠࡉ࠸ &D0Q2 㘒య࡟㐺⏝ࡋࠊ%6')7 ィ⟬⤖ᯝ࡜ẚ㍑᳨ウࡋ  ᖺᗘ࡟⥆ࡁ㟁Ꮚ┦㛵ຠᯝࡢ㔜せᛶࢆᐇドࡋ࡚ࡁࡓࠋ≉࡟ +) ᡂศࡢ๭ྜ࡟ᩄឤ࡛࠶ࡗࡓ 6 ≧ែࡢ୰㛫య㛫ࡢ┦ᑐᏳᐃᛶ࡟ࡘ࠸࡚ +) ᡂศࡢ๭ྜࢆኚ࠼ࡓἼື㛵ᩘࢆ '/312&& ἲࡢ࢖ࢽࢩࣕࣝ࡟ࡑࢀࡒࢀ⏝࠸ࡿࡇ࡜࡛࢖
ࢽࢩࣕࣝ࡟ࡼࡽ࡞࠸⤖ᯝࡀᚓࡽࢀࠊ㧗⢭ᗘィ⟬ࡢ᭷ຠᛶࡢ㧗ࡉࡀఛ࠼ࡓࠋࡲࡓᑠつᶍ࡞⣔࡟࠾࠸࡚ && ἲ࡜'/312&& ἲࡢ㔠ᒓཎᏊ࡬ࡢ㐺⏝ྍ⬟ᛶࢆ᳨ウࡋከ᰾㘒య࡬ࡢᒎ㛤ࢆ᳨ドࡋࡓࠋࡋ࠿ࡋࠊୖグࡢࡼ࠺࡟ 36,,ࡢᶵ⬟Ⓨ⌧ࡢゎ᫂࡟ࡣ⺮ⓑሙࡸỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢຠᯝࢆ⪃៖ࡍࡿࡇ࡜ࡀᚲ㡲࡛࠶ࡿࠋ᭱㏆ %HUNHOH\ ࡽࡢࢢ࣮ࣝࣉ࡛ࡣ  ᖺࡢ 6 ࡢሗ࿌࡟ຍ࠼ࡿᙧ࡛Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡸỈศᏊࡢືࡁࡸ⤒㊰࡟ࡘ࠸࡚ࡶゝཬࢆࡋ࡚࠸ࡿ +XVVHLQHWDO1DW&RPPXQ ࠋ᭱᪂ࡢỿࡽࡢᐇ㦂⤖ᯝ࡛ࡶศゎ⬟ࡢྥୖ࡟ࡼࡾࣉࣟࢺࣥࡢື
ࡁࡶᚎࠎ࡟᫂ࡽ࠿࡜࡞ࡗ࡚࠸ࡿࠋᚑࡗ࡚ࡇࢀࡽࡢᐇ㦂⤖ᯝ࡟ᇶ࡙࠸࡚཯ᛂ㐣⛬ࡢゎ᫂࡟㔜せ࡞Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆ௓ࡋࡓỈᤄධ㐣⛬ࡸࣉࣟࢺࣥ⛣ືࡢ⌮ㄽ◊✲ࡀ㔜せ࡟࡞ࡗ࡚ࡁࡓࠋᐇ㝿ࠊ⏦ㄳ⪅ࡽࡢ⤖ᯝ࡟࠾࠸࡚ࡶỈ⣲⛣ືࡢ &D0Q2 ࢥ࢔࡟ᑐࡍࡿᏳᐃᛶ࡬ࡢᐤ୚ࡣ  ᖺ࡟ሗ࿌ࡋࡓ 6 ≧ែࡔࡅ࡛࡞ࡃ 6 ≧ែ࡟࠾࠸࡚ࡶ☜ㄆࡉࢀ࡚࠸ࡿࠋ୍᪉࡛ࠊỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢ㔜せᛶࢆ㚷ࡳẚ㍑ⓗ኱ࡁ࠸⣔ ⣙  ཎᏊ⣔  ࡛ 6≧ែ࡟࠾࠸࡚ +')7 ἲ࡜ '/312&& ἲ࡜ࢆẚ㍑ࡋࡓ࡜ࡇࢁᑠࡉ࠸ࣔࢹࣝ࡟࠾࠸࡚ぢࡽࢀࡓഴྥ࡜␗࡞ࡾ
&D0Q2 ࢥ࢔ 2 ཎᏊ࡟ࣉࣟࢺࣥࡀ⤖ྜࡋࡓᵓ㐀ࡀ㠀ᖖ࡟୙Ᏻᐃ࡜࡞ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡼ࠺࡞どⅬ࠿ࡽࠊ ᖺᗘ࠿ࡽ⥅⥆ࡋ࡚࠸ࡿከ㝵ᒙ㐃⤖ィ⟬ࠊ40 '/312&& 40 %6')7 00 ࡞࡝ࢆ᭱㏆ࡢᐇ㦂⤖ᯝ࡟ᇶ࡙ࡁᐇ⾜ࡍࡿࡇ࡜ࡀᚲ㡲ࡢ≧ἣ࡛࠶ࡿࠋ ᖺᗘࡣ &D0Q2 㘒యࢥ࢔ࡢ࿘ࡾࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡
ࢡࡸሷ⣲ཎᏊ࡟ࡼࡿࣉࣟࢺࣥࡢືࡁ࡟ࡶ╔┠ࡋ᫖ᖺᗘࡼࡾ᳨ウࢆ⥆ࡅ࡚࠸ࡿ⺮ⓑሙࢆ⪃៖ࡋࡓࡉࡽ࡟኱ࡁ࡞⣔ࡢ  ࠿ࡽ  ཎᏊ⣔ࡢከ㝵ᒙ㐃⤖ィ⟬ࢆᮏ᱁ⓗ࡟ᐇ⾜ࡋࠊᵓ㐀࡜࢚ࢿࣝࢠ࣮ࡢ୧㠃࠿ࡽಙ㢗࡛ࡁࡿ⤖ᯝࢆᚓࡿࡇ࡜ࢆィ⏬ࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊ ᖺᗘ࠿ࡽࡣ ;)(/ ᐇ㦂ࡔࡅ࡛࡞ࡃࢡࣛ࢖࢜㟁㢧ᐇ㦂ࡢ⤖ᯝࡶཧ⪃࡟ࡋ࡚ࠊ36,, ࡟࠾ࡅࡿ 2(& ࡢከ㝵ᒙ㐃⤖ィ⟬࡟ࡼࡾ⺮ⓑሙ࡜ᙉࡃ㐃⤖ࡋࡓࣂ࢖࢜ 6&(6 &D0Q2  ࢩࢫࢸ࣒ࡢゐ፹ᶵ⬟ࡢᮏ㉁ࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ
2011 ᖺ࡟ሗ࿌ࡉࢀࡓᱵྡࡽࡢ S1 ≧ែࡢ㧗ゎീᗘ XRD ᵓ㐀(PDB ID: 3WU2)ࡸ 2019 ᖺ࡟ሗ࿌ࡉࢀࡓⳢࡽࡢ

S3 ≧ែࡢ SFX XFEL ᵓ㐀(PDB ID: 6JLL)ࢆ⏝࠸ &D0Q2 ࢡࣛࢫࢱ࣮ࡢ O(4)ࠊO(5)ࠊO(6)ཎᏊཬࡧ Mn4 ཎᏊ࡟㓄఩ࡋ࡚࠸ࡿ W2ࠊW1 ศᏊࡢࣉࣟࢺࣥ໬≧ែࢆኚ໬ࡉࡏࡓ S1 ≧ែ࠿ࡽ S3 ≧ែࡢᵓ㐀ࢆసᡂࡋࡓࠋྛᵓ㐀࡟ᑐࡋ࡚ࡢᵓ㐀᭱㐺໬ࡣ NWChem ࢆ⏝࠸ࠊQM ィ⟬ࢆᐇ⾜ࡋࡓࠋᵓ㐀᭱㐺໬ࡢᡭἲ࡟ࡣ UB3LYP ࡲࡓࡣ B3LYP
ࡢ HF ᡂศࢆ 30%࡟ኚ໬ࡉࡏࡓỗ㛵ᩘ࡟ Grimme ࡢ D2 ࢱ࢖ࣉࡢศᩓ⿵ṇࢆຍ࠼ࡓࡶࡢࢆ⏝࠸ࠊᇶᗏ㛵ᩘ࡟ࡣ
all-electron ࡢᇶᗏ࡛࠶ࡿ Def2-TZVP ࢆ⏝࠸ࡓ(⣙ 2300 ᇶᗏ)ࠋࡲࡓ⎔ቃຠᯝࢆ COSMO (ㄏ㟁⋡ ε = 10.0) ࡟ࡼࡾྲྀࡾධࢀࡓࠋࡲࡓࠊࣔࢹࣝᵓ㐀ࡢ᳨ドࡍࡿࡓࡵ࡟᭱ᑠࣔࢹࣝ࡟➨ 2 ᒙࡢ㓄఩Ꮚ࡟┦ᙜࡍࡿ࢔࣑ࣀ㓟(Val185,
Asp61, His337, Arg354, Tyr161)ࢆຍ࠼ࡓ semi-large ࣔࢹࣝࠊGly62, Asn87, Ser167, Ser169 ࡶຍ࠼ࡓ large ࣔࢹࣝࢆసᡂࡋ UB3LYP-D3 ࡢᡭἲ࡛᭱㐺໬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘ࡟ࡣࢥ࢔ࡢᵓ㐀࡟ࡣ Def2-TZVP ࡢᇶᗏࢆࠊsemilargeࠊlarge ࣔࢹ࡛ࣝ᪂ࡓ࡟ຍ࠼ࡓ㓄఩Ꮚ࡟ࡣ Def2-SVP ᇶᗏࡢ 2 ᒙࡢᇶᗏ㛵ᩘࢆ⏝࠸(semi-large ࣔࢹ࡛ࣝ⣙4000 ᇶᗏࠊlarge ࣔࢹ࡛ࣝ⣙ 5000 ᇶᗏ)ࠊ⎔ቃຠᯝࢆ COSMO ࡟ࡼࡾྲྀࡾධࢀࡓࠋ᭱㐺໬࡟ࡣྛᵓ㐀࡟ࡘ࠸࡚ࠊ
⣙ 100 ࢧ࢖ࢡࣝ⛬ᗘࡢ཯᚟ࡀᚲせ࡜࡞ࡾࠊ406Rh-2 (࣓ࣥࢸࢼࣥࢫ๓) ࢆ୪ิ౑⏝ࡍࡿࡇ࡜࡟ࡼࡾ㧗㏿࡞ィ⟬ࡀྍ⬟࡛࠶ࡗࡓࠋ

- 125 -

┦ᑐ࢚ࢿࣝࢠ࣮ࡢẚ㍑ࡢࡓࡵ HDFT ࡜ DLPNO-CC ࡢᡭἲࢆ⏝࠸ࠊ᭱㧗ࢫࣆࣥ≧ែ (S1 ≧ែࡣ S = 15/2ࠊS2≧ែࡣ S = 14/2ࠊS3 ≧ែ S = 13/2ࠊPeroxo ࣔࢹࣝࡢࡳ S = 15/2) ࡟ᑐࡋ࡚ᇶᗏ㛵ᩘ࡟ࡣ Def2-TZVPP ࢆ⏝࠸࡚ィ⟬ࢆ⾜࠸ (᭱ᑠࣔࢹ࡛ࣝ⣙ 2500 ᇶᗏࠊsemi-large ࣔࢹ࡛ࣝ 5000 ᇶᗏ)ࠊ⎔ቃຠᯝ࡟ࡣ COSMO ࡲࡓࡣ CPCMࢆ⏝࠸ࡓࠋHDFT ࡟ࡣ B3LYP ࡜ࡑࡢ Hartree-Fock ᡂศࢆኚ໬ࡉࡏࡓỗ㛵ᩘࢆ⏝࠸ࠊẚ㍑ࡢࡓࡵ B3LYP-D3 ࡜double-HDFT ࡛࠶ࡿ B2PLYP ࢆ⏝࠸ࡓࠋDLPNO-CC ࡢィ⟬࡟ࡣ DLPNO-CCSD ἲ࡜ DLPNO-CCSD(T0)ἲࢆࡑ
ࢀࡒࢀ PNO ࡢ㜈್ࡢ᮲௳ࢆኚ໬(Normal ࡜ Tight)ࡉࡏホ౯ࡋࡓࠋࡲࡓࠊྛ≧ែ࡟ࡘ࠸࡚୰㛫ࢫࣆࣥ≧ែࢆ DFT(B3LYP) ࡛ồࡵࠊࣁ࢖ࢮࣥ࣋ࣝࢡࢫࣆࣥࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ࠊ☢Ẽⓗᛶ㉁ࡢゎᯒࢆ⾜ࡗࡓࠋDFT ࡢィ⟬࡟ࡣ NWChem ࠾ࡼࡧ NTChem ࢆ⏝࠸ࠊDLPNO-CC ἲ࡟ࡣ ORCA4 ࡜ ORCA5 ࡢࣉࣟࢢ࣒ࣛࢆࡑࢀࡒࢀ OpenMPI
3, OpenMPI 4 ࡟ࡼࡾ 1 ࣀ࣮ࢻෆ࡛୪ิฎ⌮ࡉࡏࡿࡼ࠺࡟ࡋ࡚౑⏝ࡋࡓࠋDLPNO-CC ィ⟬࡟ࡣከᩘࡢ࣓ࣔࣜ࡜
ࢫࢡࣛࢵࢳࣇ࢓࢖ࣝࡢ㧗㏿࡞ㄞࡳ᭩ࡁࡀᚲせ࡜࡞ࡿࡓࡵࠊศᏊ◊ࡢ work 㡿ᇦ࡟࠾ࡅࡿ㧗㏿࡞࢔ࢡࢭࢫ࡜኱ᐜ
㔞ࡢ࣓ࣔࣜࢆ✚ࢇࡔ 110Rh-1 (࣓ࣥࢸࢼࣥࢫ๓) ࡢ౑⏝࡟ࡼࡾຠ⋡ࡢⰋ࠸ィ⟬ࡀྍ⬟࡛࠶ࡗࡓࠋ࣓ࣥࢸࢼࣥࢫ
ᚋࡣィ⟬ᶵࢩࢫࢸ࣒ࡢᵓᡂࡸ CPU ࡀኚ໬ࡋࡓࡇ࡜ࡶ࠶ࡾ ORCA ࢆ㉮ࡽࡏࡿࡓࡵࡢ OpenMPI ࡸ NWChem ࢆ⮬๓࡛ࢲ࣮࢘ࣥࣟࢻࡋ࡚ࡁࡓ Intel OneAPI ࡟ࡼࡾ෌ࢥࣥࣃ࢖ࣝࢆ⾜࠸ࠊ࣓ࣥࢸࢼࣥࢫ௨๓ࡢ⤖ᯝ࡜ᩚྜᛶࡢ
࠶ࡿ⤖ᯝࡀᚓࡽࢀࡿ࠿᳨ドࢆ⾜ࡗࡓࠋ



◊✲ᡂᯝ
ࡇࢀࡲ࡛ࡢ &D0Q2 ࢡࣛࢫࢱ࣮࿘ࡾࡢ࢔࣑ࣀ㓟ṧᇶ࡜ỈศᏊࡢࡳ࡟╔┠ࡋࡓ᭱ᑠࣔࢹࣝࢆ⏝࠸ࡓ⤖ᯝ࡟ࡼ

ࡾࠊDLPNO-CC ἲ࡞࡝ࢆ౑ࡗࡓືⓗ㟁Ꮚ┦㛵ࡢ㔜せᛶ࡜㐺⏝ྍ⬟ᛶࡀุ᫂ࡋࠊ᭱ᑠࣔࢹࣝ࡟➨ 2 ᒙࡢ㓄఩Ꮚ࡟┦ᙜࡍࡿ࢔࣑ࣀ㓟(Val185, Asp61, His337, Arg354, Tyr161)ࢆຍ࠼ࡓ semi-large ࣔࢹࣝ࡟ࡼࡿ S1 ≧ែࡢ⤖ᯝࡀ኱ࡁࡃ␗࡞ࡿഴྥࢆ୚࠼ࡓࡇ࡜࠿ࡽࠊᮏᖺᗘࡣ S0 ≧ែ࠿ࡽ S3 ≧ែࡲ࡛ࡢ semi-large ࣔࢹࣝࢆ⏝࠸ࡓ᭱㐺໬ᵓ㐀ࡸ DFT ࡜ DLPNO-CC ἲࢆ⏝࠸ࡓ┦ᑐᏳᐃᛶࡢィ⟬ࢆ⾜࠸ࠊBSDFT ࡟ࡼࡿ㟁Ꮚ࣭ࢫࣆࣥᵓ㐀ࡢゎᯒࢆ⾜ࡗࡓࠋ௒ᅇᚓࡽࢀࡓᵓ㐀ࡢ⤖ᯝ࡜ࠊ௨๓ࡢ Large-scale QM/MM ࡢ⤖ᯝ (Shoji et al., Adv. Quant. Chem. (2015))ࠊ
2011 ᖺࡢỿࠊ⚄㇂ࡽࡢ⤖ᯝ(Umena et al., Nature 2011)ࡸ㏆ᖺࡢ XFEL ࡢ⤖ᯝࢆẚ㍑ࡋࠊỈࡢὶධ⤒㊰࡜ࣉࣟࢺࣥᨺฟ⤒㊰ࢆᢸ࠺ỈศᏊ࡜ Cl ࢔ࢽ࢜ࣥ࡞࡝࠿ࡽ࡞ࡿỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢゎᯒࢆ⾜ࡗࡓ (Yamaguchi et al.,Coord. Chem. Rev. 2022, ᡂᯝㄽᩥ[2])ࠋࡲࡓࠊS3 ≧ែࡢ semi-large ࣔࢹࣝࢆ⏝࠸ࡓ DLPNO-CCSD(T0)ィ⟬࡟ࡼࡿ┦ᑐᏳᐃᛶࡢ⤖ᯝࠊ௨๓ࡢ QM/MM ࡢ⤖ᯝ࡜ Gernot Renger ࡽࡢ kinetics ࡟㛵ࡍࡿᐇ㦂࠿ࡽࠊ⊂⮬ࡢ᥎⟬ᘧࢆࡶ࡜࡟ S3 ≧ែ࡛ྍ⬟࡞୰㛫యࡢᵓ㐀࡜ S3 ≧ែ࡟࠾ࡅࡿ Multi-intermediate ࣔࢹࣝࡢྍ⬟ᛶ࡟ࡘ࠸࡚ࡢ㆟ㄽࢆ⾜ࡗࡓ (Yamaguchi et al., Chem. Phys. Lett. 2022, ᡂᯝㄽᩥ[3]ࠊIsobe et al., J Phys Chem. B 2022, ᡂᯝㄽᩥ[4])ࠋ
ᮏᖺᗘࡢሗ࿌᭩࡛ࡣࠊࡇࡢ⤖ᯝ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋࡲࡓࠊ300 ཎᏊ⣔ࡢ large ࣔࢹ࡛ࣝࡢィ⟬ࢆ S1 ≧ែ࠿ࡽ S3≧ែ࡟ࡘ࠸࡚⾜࠸ࠊsemi-large ࣔࢹࣝ࡜ᵓ㐀ⓗ࡟ࡣ኱ࡁ࡞ᕪ␗ࡀ⏕ࡌ࡞࠸ࡇ࡜ࡀุ᫂ࡋᏛ఍Ⓨ⾲ࢆ⾜ࡗࡓࠋ2022 ᖺᗘࡢᚋ༙ (⤊┙) ࡟࠾࠸࡚ࡣィ⟬ᶵࢩࢫࢸ࣒ࡢ᭦᪂ࡢࡓࡵィ⟬ᶵࢩࢫࢸ࣒ࡢᵓᡂࡸ CPU ࡀኚ໬ࡋࡓࡇ
࡜ࡶ࠶ࡾࠊ࣓ࣥࢸࢼࣥࢫ௨๓ࡢ⤖ᯝ࡜ᩚྜᛶࡢ࠶ࡿ⤖ᯝࡀᚓࡽࢀࡿ࠿᳨ドࢆ⾜ࡗࡓࠋࡲࡓࠊ2023 ᖺᗘ௨㝆ࡶ⥅⥆ࡋ࡚⾜࠺ணᐃࡢィ⟬࡟࠾࠸࡚ᚲせ࡜࡞ࡿࠊS2 ࠿ࡽ S3 ≧ែࠊS3 ࠿ࡽ S0 ≧ែ࡬ࡢ㑄⛣࡟క࠺ỈศᏊᤄධ⤒㊰ࡸࣉࣟࢺࣥᨺฟ⤒㊰࡟ࡘ࠸࡚ࡢィ⟬ࣔࢹࣝᵓ⠏ࡢࡓࡵ࡟ࠊQM ィ⟬⤖ᯝࠊQM/MM ィ⟬⤖ᯝࠊ2011 ᖺ࡟ሗ࿌ࡉࢀࡓᱵྡࡽࡢ S1 ≧ែࡢ㧗ゎീᗘ XRD ᵓ㐀ࠊ2019 ᖺ࡟ሗ࿌ࡉࢀࡓⳢࡽࡢ S3 ≧ែࡢ SFX XFEL ᵓ㐀ࡸ㏆ᖺࡢ Berkeley ࡢ XFEL ࡢᵓ㐀ࢆẚ㍑ࡋࠊ࣓ࣥࢸࢼࣥࢫ๓࡟⾜ࡗࡓ large model (⣙ 300 ཎᏊ⣔) ࡢ⤖ᯝࢆࡶ࡜࡜ࡋ࡚ࠊI) ỈศᏊᤄධ⤒㊰ࡢゎᯒࡢࡓࡵ O1 ཎᏊ࿘ࡾࡢỈศᏊ W10 ࢆྵࡴỈศᏊࡢ 5 ဨ⎔࡜࿘ࡾࡢ࢔࣑ࣀ㓟ṧᇶࢆྵࡴ Water Inlet Path (WIP) ࣔࢹࣝ(⣙ 400 ཎᏊ⣔)ࠊII) ࣉࣟࢺࣥᨺฟ⤒㊰ࡢ୍ࡘ࡛࠶ࡿ Cl1 ཎᏊ࿘ࡾࡢ࢔࣑
ࣀ㓟ṧᇶ࡜ỈศᏊࢆྵࡴ Channel D ࣔࢹࣝ(⣙ 400 ཎᏊ)࡜ III) WIP ࠿ࡽ Channel D ࢆྵࡳỈศᏊᤄධ⤒㊰ࡸࣉ

- 126 -

ࣟࢺࣥᨺฟ⤒㊰ࢆ⪃៖ࡍࡿࡓࡵࡢ⣔(⣙ 500 ཎᏊ)ࡢᵓ⠏ࢆ⾜ࡗࡓ (ᅗ 1 ཧ↷)ࠋᵓ⠏ࡋࡓࣔࢹࣝ࡟ᑐࡋ࡚᪂ࡋ
࠸ィ⟬ᶵࢩࢫࢸ࣒࡟࠾࠸࡚ᵓ㐀᭱㐺໬ィ⟬୰࡟୙ලྜࡀ⏕ࡌ࡞࠸࠿ࠊ࣓ࣔࣜ୙㊊ࡢၥ㢟ࡀ㉳ࡁ࡞࠸࠿࡞࡝ࡢ
☜ㄆࢆ⾜ࡗࡓࠋᅗ 1.

HR XRD ᐇ㦂࡟ࡼࡾゎ᫂ࡉࢀ㸪Large-scale QM(380 atom)/MM ィ⟬࡟ࡼࡾ⢭ᐦ໬ࡉࢀࡓ OEC ࡟࠾ࡅࡿ CaMn4O5 ࢡࣛࢫࢱ࣮࿘㎶ࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡᵓ㐀࡜ᵓᡂỈศᏊࡢỗ⏝ྡࠋ

S3 ≧ែࡢ semi-large ࣔࢹࣝ(227 ཎᏊ)ࢆ⏝࠸ࡓ⤖ᯝ࡜ large ࣔࢹࣝ࡜࡛ࡣ CaMn4O6 㦵᱁࡟኱ࡁ࡞ᕪࡣ࡞ࡃࠊ
SFX ࡟ࡼࡿᐇ㦂⤖ᯝ 6XJDHWDO6FLHQFH ࡢẚ㍑ࢆࡍࡿ࡜ Oxyl ᵓ㐀࡜ࢥࣥࢩࢫࢸࣥࢺ࡞⤖ᯝ࡜࡞ࡗ࡚࠸ࡿ
ࡓࡵࠊSFX ࡢ⤖ᯝࡢゎ㔘࡟౑࠼ࡿࡇ࡜ࡀศ࠿ࡿࠋDLPNO-CCSD(T0)ィ⟬࡛ࡣ open-cubane ᆺࡢ hydroxide(S3abca(R)-OH) ୰㛫యࡢ᪉ࡀ R[\O 6DEFD 5 R[\O  ୰㛫యࡼࡾᏳᐃ࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋⳢࡽࡢ 6);;)(/ ᐇ㦂⤖ᯝ 6XJDHWDO6FLHQFH ࡜ᩚྜࡋ࡞࠸⤖ᯝ࡜࡞ࡗࡓࡀࠊVHPLODUJH ࣔࢹ࡛ࣝࡣ༑ศ࡞࢚ࢿࣝࢠ࣮ࡢぢ✚ࡶࡾࡀ㞴ࡋࡃࡉࡽ࡟኱ࡁ࡞⺮ⓑሙࢆྵࢇࡔࣔࢹࣝ࠿ 4000 ࣞ࣋ࣝࡢィ⟬࡟ࡼࡿ☜ㄆࡶᚲせ࡜࡞ࡿࠋ6); ࡢᐇ㦂⤖ᯝࡣᐊ≧ែ࡛ࡢᵓ㐀ࢆゎ᫂ࡋ࡚࠸ࡿࡢ࡛ࠊ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬⤖ᯝ࡟ࡼࡿ┦ᑐᏳᐃᛶࡢ᳨ウࡶᚲせ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊK\GUR[LGH ୰㛫యࡢᇶᗏࢫࣆࣥ≧ែ 6  ࡸ SURMHFWLRQIDFWRUV ࡞࡝ࡣపࡢ (35 ᐇ㦂⤖ᯝ࡜Ⰻࡃᩚྜࡍࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡿࠋ୍᪉ࠊR[\O ୰㛫యࡣ᭱㧗ࢫࣆࣥ㓄⨨ 6   ࡟┦ᙜࡍࡿࡢ࡛ (35 ࡛ᤊ࠼ࡽࢀ࡞࠸ྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࡸᐊ

࡛ࡣ (35 ᐇ㦂ࡀᅔ㞴࡛࠶ࡿࡓࡵࠊᐊ

6); ᐇ㦂⤖ᯝ࡜ప(35 ᐇ㦂⤖ᯝࢆ┤᥋ᑐᛂࡉࡏࡿࡇ࡜ࡣ㞴ࡋ࠸ࠋࡲࡓࠊึᮇࡢ ;$6 ࡸ (;$)6 ࡢ◊✲࡛ࡣ 6 ≧ែࡢ౯㟁Ꮚ≧ែࡣ  2ᵓ㐀࡜ᖐᒓࡉࢀ࡚࠸ࡓࡀࠊ᭱㏆ࡢ (;$)6 ᐇ㦂࡛ࡣ  ࡢ౯㟁Ꮚ≧ែ࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞
ࡀࡽࠊR[\O ᵓ㐀ࡢ 2  2  ࢧ࢖ࢺࡢ ȕ ࢫࣆࣥᐦᗘࡣࢫࣆࣥศᴟ࡟ࡼࡿࡶࡢ࡛࠶ࡿࡢ࡛ࠊ0Q ࢧ࢖ࢺࡢᙧᘧⓗ࡞ࢫࣆࣥ≧ែࡢ  ౯ࡢ≧ែࡣ  ౯ࡢ≧ែ࡜ࡢΰྜ≧ែ࡜⪃࠼ࡿࡇ࡜ࡀ࡛ࡁࡿࡓࡵࠊ㟁Ⲵࡢ⮬⏤ᗘ࠿ࡽุ᩿ࡍࡿ
࡜ࠊ6DEFD 5 R[\O ୰㛫యࡢ๭ྜࡣᐊ

࡛ࡶᑠࡉ࠸ྍ⬟ᛶࡀฟ࡚ࡃࡿࠋࡑࡇ࡛ࠊ6 ≧ែ࡟ࡘ࠸࡚ K\GUR[LGH ࣔࢹࣝ࡜ R[\O ࣔࢹࣝ࡜ࡢ஧୰㛫యࣔࢹࣝ࡟ᇶ࡙ࡁྛᵓ㐀ࡢᐊ࡛ࡢ๭ྜࢆ᥎⟬ࡋ࡚ࡳࡿࡇ࡜ࢆヨࡳࡓࠋ.HUQ ࡽ࡟ࡼࡿ 6);;)(/ ᵓ㐀 .HUQHWDO1DWXUH  ࡢศゎ⬟ࡣ⣙ c ࡞ࡢ࡛ࠊc ௨ୖࡢ㛗ࡉ࡟࡞ࡿ 0Q0Q ㊥㞳࡟ࡣ 0Q ୖࡢ㟁Ꮚᐦᗘࡀከ࠸ࡇ࡜ࡶ࠶ࡾᐇ㦂ㄗᕪࡣẚ㍑ⓗᑡ࡞࠸࡜⪃࠼ࡽࢀࡿࠋ ୍᪉ࠊ0Q2 ㊥㞳ࡣ㓟⣲ࡢ㟁Ꮚᐦᗘࡣ 0Q ࡟ẚ㍑ࡋ࡚ᑠࡉ࠸ࡢ࡛ศ㞳ࡋࡓࣆ࣮ࢡ࡜ࡋ࡚ほ- 127 -

ࡉࢀࡎᐇ㦂ㄗᕪࡀྵࡲࢀ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋᚑࡗ࡚ࠊMn3- Mn4 ㊥㞳ࢆ᥎⟬࡟౑⏝ࡍࡿ࡜ࡍࢀࡤࠊ

ᐃࡉࢀࡓ Mn3- Mn4 ㊥㞳ࡣ S3 ≧ែࡢ஧୰㛫యࣔࢹࣝࡢ⠊ᅖ࡛ hydroxide ࡢᵓ㐀࡜ oxyl ᵓ㐀࡟ᑐᛂࡍࡿ Mn4-Mn3 ㊥㞳ࡢ㔜ࡡྜࢃࡏ࡛⾲⌧ࡉࢀࡿࠋR(Mn4-Mn3)obs. = p R(Mn4-Mn3)OH(DFT) + (1-p) R(Mn4-Mn3)Oxyl(DFT)(1)ࡇࡇ࡛ࠊp ࡣΰྜಀᩘ࡛࠶ࡾ hydroxideࠊoxyl ᵓ㐀ࡢ DFT ࡟ࡼࡿ᭱㐺໬ࡋࡓ Mn3- Mn4 ㊥㞳ࡣࡑࢀࡒࢀ 2.75ࠊ
2.83 Å ࡛࠶ࡿࠋKern ࡽ࡟ࡼࡿ SFX XFEL ᐇ㦂࡟ࡼࡿ Mn3- Mn4 ㊥㞳ࡣ A ࠾ࡼࡧ a ࣔࣀ࣐࣮ࡢᖹᆒ್ࢆ࡜ࢀࡤ
2.77 Å ࡛࠶ࡿࡢ࡛(1)ᘧ࠿ࡽ p ࡢ್ࡣ 0.75 (p ×100%) ࡜᥎⟬ࡉࢀࡿࠋBerkeley ࢢ࣮ࣝࣉࡢ᭱᪂ࡢ⤖ᯝ (Ibrahim
et al., PNAS 2020, Hussein et al., Nat. Commun. 2022) ࠿ࡽࡣ p ࡢ್ࡣ 0.9 (90%) ~ 1.0 (100%)࡟࡞ࡿࠋࡇࡢࡼ࠺
࡟ࠊᐇ㦂ㄗᕪࡀᑡ࡞࠸࡜௬ᐃࡋࡓ Mn3-Mn4 ㊥㞳࠿ࡽ᥎⟬ࡍࡿ࡜ Berkeley ࢢ࣮ࣝࣉࡢ SFX XFEL ᵓ㐀ࡣᐊ≧ែ࡛ࡶ hydroxide ᵓ㐀ࡢ๭ྜࡀከ࠸࡜࠸࠼ࡿࠋ0Q2  ㊥㞳࡟ࡘ࠸࡚ࡣࠊ')7 ࡟ࡼࡿ⤖ᯝ࡛ࡣ R[\O ᵓ㐀࡛ࡣ c ࡛࠶ࡿࡀࠊ.HUQ ࡽ࡟ࡼࡿ 6); ;)(/ ᐇ㦂ࡢ 6 ≧ែ࡛ࡢᐇ᰾㘒య࡛ほ್ࡣ  c ࡛࠶ࡿࡢ࡛ࠊᩘከࡃࡢ 0Q ከࡉࢀ࡚࠸ࡿ 0Q ,9 2±㊥㞳 ac ࡟ẚ㍑ࡋ࡚㛗ࡍࡂࡿࡼ࠺࡟ᛮࢃࢀࡿࠋᚑࡗ࡚ࠊ0Q2 ㊥㞳ࡣ 0Q ཎᏊࡸ 2  ཎᏊࡢ㓟໬≧ែ࡟ࡼࡾኚ໬ࡍࡿࡇ࡜ࡀศ࠿ࡿࠋࡲࡓࠊMn3-Mn4 ㊥㞳ࡶ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢ࢟ࣗࣂࣥᵓ㐀ࡀ㛤࠸ࡓሙྜ࡜㛢ࡌࡓሙྜ࡛ࡶኚ໬ࡍࡿࠋᚑࡗ࡚ࡇࢀࡽࡢࣃ࣓࣮ࣛࢱࡀ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆゎ㔘ࡍࡿࡓࡵ࡟ࡣ≉࡟㔜せ࡜࡞ࡿࠋ&D0Q2 ࢡࣛࢫࢱ࣮ࡢᐇ

್࡜ 4000 ィ⟬࡟ࡼࡿ 0Q0Q ㊥㞳ࢆ⏝࠸ࡿࡇ࡜࡛ 0Q2  ㊥㞳ࢆ᥎⟬ࡍࡿ⤒㦂ᘧࡣ
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K\GUR[LGH ᵓ㐀࡛ cࠊR[\O ᵓ㐀࡛±c ࡢ࡛ࠊ')7 ࡟ࡼࡿ K\GUR[LGH ࡜ R[\O ࡢΰྜࡋࡓᘧ  ࡀ 0Q2 ㊥㞳ࡢ⤖ᯝࢆ 2  2  㛫㊥㞳ࡢぢ✚ࡶࡾ࡟ࡶ༑ศ౑⏝࡛ࡁࡿࡇ࡜ࡀศ࠿ࡿࠋ6);;)(/ ᵓ㐀ࡢ Mn3-Mn4 ㊥㞳ࢆ
0Q2  ㊥㞳ࢆᘧ  ࡟ࡼࡾぢ✚ࡶࡿࡓࡵ࡟⏝࠸ࡿ࡜ࠊ(1)ᘧồࡵࡓ p ್ࢆ⏝࠸࡚ࠊMn4-O(5)ཬࡧ O(5)-O(6)㊥㞳ࡶྠᵝ࡟᥎⟬ྍ⬟࡜࡞ࡿࠋR(Mn4-O(5))obs = pR(Mn4-O(5))S3abca(R)-OHglu + (1-p) R(Mn4-O(5))S3abca(R)-oxyl(4a)R(O(5)-O(6))obs = pR(O(5)-O(6))S3abca(R)-OHglu + (1-p) R(O(5)-O(6))S3abca(R)-oxyl(4b)(4b)ᘧ࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟ࠊ᥎⟬ࡉࢀࡓ O(5)-O(6)㊥㞳ࡣ 2.4~2.5 Å ࡟ఙࡧࡿࡇ࡜࡟࡞ࡾࠊBerkeley ࢢ࣮ࣝࣉࡢ
SFX XFEL ᵓ㐀࡛ồࡵࡽࢀࡓ O(5)-O(6)㊥㞳(2.1 Å)ࡼࡾࡶ㛗ࡃ࡞ࡿࠋᚑࡗ࡚ࠊ(4)ᘧ࡛ࡣ Berkeley ࡢᵓ㐀࡛ OX ࡜

- 128 -

⾲⌧ࡉࢀ࡚࠸ࡿᤄධᇶࡣ OH (Mn-hydroxide)࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋୖグࡢ⤖ᯝࡣ A ࡜ a ࣔࣀ࣐࣮ࡢᖹᆒ್ࢆ᥇
⏝ࡋ࡚᥎⟬ࡋࡓ⤖ᯝ࡛࠶ࡿࡀࠊಶู࡟ホ౯ࡋࡓሙྜ࡟ࡣ Kean ࡽࡢ⤖ᯝ࡛ࡣ A ࣔࣀ࣐࣮࡛ࡣ 100% hydroxideᵓ㐀࡟ࠊa ࣔࣀ࣐࣮࡛ࡣ 100% Oxyl ᵓ㐀࡟ྠᐃࡉࢀࡓࠋࡇࡢࡼ࠺࡟ࠊBerkeley ࢢ࣮ࣝࣉࡢ PSII ࡢ⤖ᬗᵓ㐀ゎ
ᯒ࡛ࡣ S3 ≧ែࡢ୰㛫యࡢᵓ㐀ࡀ A ࡜ a ࡢࣔࣀ࣐࣮࡛␗࡞ࡗ࡚࠸ࡿࠋ୍᪉ࠊᒸᒣ኱Ꮫࢢ࣮ࣝࣉࡢ SFX XFEL ᵓ㐀࡛ࡣ Aࠊa ࣔࣀ࣐࣮࡜ࡶ࡟ Oxyl ᵓ㐀࡟ྠᐃࡉࢀࡓࠋ⾲ 1.

᥎⟬ᘧ࡟ࡼࡾぢ✚ࡶࡗࡓ S3 ≧ែࡢᵓ㐀ࣃ࣓࣮ࣛࢱ

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㈹ ග໬Ꮫ⣔ ,, ࡟࠾ࡅࡿ㓟⣲Ⓨ⏕୰ᚰࡢ 6 ≧ែ࡛ࡢ୰㛫యᵓ㐀ࡢ ')7 ࡜ && ἲ࡟ࡼࡿゎᯒ ᐑᕝ᫭୍ ᕝୖ㈗㈨ ᗉྖග⏨ ☾㒊 ᐶ ᒣཱྀ ඙ 㔜⏣⫱↷ 㔞Ꮚ⏕࿨⛉Ꮫ఍ ➨  ᅇ኱఍  ᖺ  ᭶  ᪥㹼 ᪥ ⚄ᡞ኱Ꮫⓒᖺグᛕ㤋භ⏥࣮࣍ࣝ ཱྀ㢌 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
★>@5HODWLYHHQHUJLHVDPRQJ6LQWHUPHGLDWHVLQWKHSKRWRV\VWHP,,UHYHDOHGE\'/312FRXSOHGFOXVWHUDQGK\EULG

')7FDOFXODWLRQV3RVVLEOHSDWKZD\VRIZDWHULQVHUWLRQLQWKH6WR6WUDQVLWLRQ.0L\DJDZD06KRML+,VREH7
.DZDNDPL71DNDMLPDDQG.<DPDJXFKL&KHP3K\V/HWW  '2,MFSOHWW ★>@ *HRPHWULF HOHFWURQLF DQG VSLQ VWUXFWXUHV RI WKH &D0Q 2 FDWDO\VW IRU ZDWHU R[LGDWLRQ LQ R[\JHQHYROYLQJSKRWRV\VWHP ,, ,QWHUSOD\ EHWZHHQ H[SHULPHQWV DQG WKHRUHWLFDO FRPSXWDWLRQV .<DPDJXFKL 0 6KRML + ,VREH .
0L\DJDZD06XJD)$NLWDDQG-56KHQ&RRUG&KHP5HY  '2,MFFU
★>@ (OXFLGDWLRQ RI D PXOWLSOH 6 LQWHUPHGLDWHV PRGHO IRU ZDWHU R[LGDWLRQ LQ WKH R[\JHQ HYROYLQJ FRPSOH[ RI
SKRWRV\VWHP,,&DOFLXPDVVLVWHGFRQFHUWHG22ERQGIRUPDWLRQ.<DPDJXFKL.0L\DJDZD06KRML+,VREHDQG

- 130 -

7.DZDNDPL&KHP3K\V/HWW  '2,MFSOHWW ★>@5ROHVRIWKH)OH[LEOH3ULPDU\&RRUGLQDWLRQ6SKHUHRIWKH0Q&D2[&OXVWHU:KDW$UHWKH,PPHGLDWH'HFD\3URGXFWVRIWKH66WDWH"+,VREH06KRML76X]XNL-56KHQDQG.<DPDJXFKL-3K\V&KHP%
 '2,DFVMSFEF
>@ ໬Ꮫ཯ᛂ࡟࠾ࡅࡿᑐ⛠ᛶࡢ◚ࢀࡢ⌮ㄽ㸦㸧㸸ගྜᡂỈศゎ཯ᛂ୰㛫యࡢ⤖ྜࢡࣛࢫࢱ࣮ '/312
&RXSOHG&OXVWHU && 6' 7 ィ⟬ ᒣཱྀ ඙ ᐑᕝ᫭୍ ᗉྖග⏨ ☾㒊 ᐶ ᕝୖ㈗㈨ ୰ᔱ㝯ே ㇏⏣◊✲ሗ࿌   

- 131 -

୕ḟඖࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀ᛶ
6WUXFWXUHDQG3URSHUWLHVRI7KUHHGLPHQVLRQDOS&RQMXJDWHG0ROHFXOHV‫ۑ‬ὠ␃㷂 㝧኱㸦኱㜰බ❧኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧1◊✲┠ⓗ࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥࡣࠊ஬ဨ⎔࡜භဨ⎔ࡀ⦰⎔ࡋࠊ⎔⦰ྜ఩࡟ࣜࣥཎᏊࢆ᭷ࡍࡿ໬ྜ≀࡛࠶ࡿࠋᡃࠎࡣࠊ

ࡑࡢㄏᑟయ࡜ࡋ࡚ึࡵ࡚ࡢ౛࡜࡞ࡿࢪ࣋ࣥࢰ[b,e]࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ 1 ࡢྜᡂ࡟ᡂຌࡋࠊࡑࡢ‴᭤ᵓ㐀࡜ศᏊ඲య࡬ࡢSඹᙺᣑᙇࢆ᫂ࡽ࠿࡟ࡋࡓ &KHP&RPPXQ2019 ࠋ᭱㏆ࠊ࢜࢟ࢩࢻయ 1a ࡢ␗ᛶయ࡛࠶ࡿࢪ࣋
ࣥࢰ[b,g]࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ 2 ࠾ࡼࡧ୕✀㢮ࡢࢼࣇࢱࣞࣥ⦰⎔࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ 3a-c ࡢྜᡂ࡟ࡶᡂຌࡋࠊ
ᇶ♏≀ᛶࡢᐃࢆᐇ᪋ࡋࡓ(◊✲ᡂᯝ࡟グ㍕)ࠋᮏ◊✲࡛ࡣࠊ࣋ࣥࢮࣥ⎔ࡢ⦰⎔ᩘ࡜఩⨨ࡢ㐪࠸࡟ࡼࡿඹᙺᣑᙇ

ຠᯝࡸ≀ᛶ࡬ࡢᙳ㡪ࠊ࣍ࢫࣇ࢕ࣥ
ࢻࣜࢪࣥ㦵᱁ࡢⰾ㤶᪘ᛶ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ⌮ㄽィ⟬ࢆᐇ᪋ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ ࢆ฼⏝ࡋࡓࠋ%/<3* G ࣞ࣋ࣝࢆᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓᵓ㐀࡟ࡘ ࠸ ࡚ ࡣ ࠊ ᣺ ື ᩘ ィ ⟬ ࢆ ⾜ ࠺ ࡇ ࡜ ࡛ Ᏻ ᐃ ᵓ 㐀 ࡛ ࠶ ࡿ ࡇ ࡜ ࢆ ☜ ㄆ ࡋ ࡓ ࠋ 7'')7 ィ ⟬ ࡟ ࡘ ࠸ ࡚ ࡣ ࠊ
B3LYP/6-311+G(2d,p) (PCM = CH2Cl2)ࢆ౑⏝ࡋࠊ1,&6 ࡢ⟬ฟ࡟ࡣ *,$2%/<3J GS ࣞ࣋ࣝࢆ౑⏝ࡋࡓࠋ



3

◊✲ᡂᯝ
໬ྜ≀ 2, 3a-c ࡢࢪࢡ࣓ࣟࣟࢱࣥ୰࡛ࡢ⣸



1a

2

3a

3b

3c

ȜPD[QP











İ

 

 

 

 

 

D(R[9 









D(UHG9 í

í

í

í

í

ࡉࢀࠊ໬ྜ≀ 1a (397 nm, H = 3410)࡜

1,&6  %E

+4.09

+3.92

+4.92

+3.91

+5.28ࡢ㐪࠸ࡀぢࡽࢀࡓ(Table 1)ࠋࡲࡓࠊ࢔ࢭࢺࢽ

1,&6  &E+4.25

+3.57

+4.71

+3.77

+4.70እྍど྾཰ࢫ࣌ࢡࢺ࡛ࣝࡣࠊ380 (H, 2870),
434 (1110), 399 (7200), 437 nm (1220) ࡟྾཰ࡀほࢺࣜࣝ୰࡛ CVᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊ㓟໬ഃ࣭㑏ඖഃࡢ࠸ࡎࢀࡶ㠀ྍ㏫࡞㓟໬Ἴ࠾ࡼࡧ
㑏ඖἼࡀほTable 1. ໬ྜ≀ 1a 23a-c ࡢග≀ᛶࢹ࣮ࢱD YV)F)FE  ஬ဨ⎔% ࠾ࡼࡧභဨ⎔ & ࡢ 1,&6  ್ ࡉࢀࡓࠋ㓟໬㟁఩ࡣ㧗࠸᪉࠿ࡽ㡰࡟ 2!1a!3b!3a!3cࠊ㑏ඖഃ࡛ࡣࠊ3a!3c!1a§2§3b ࡛࠶ࡾࠊ࣋ࣥࢮࣥ⎔ࡢ⦰⎔ᩘ࡜఩⨨ࡢ㐪࠸࡟ࡼࡗ࡚㐪࠸ࡀぢࡽࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
໬ྜ≀ 1a23a-c ࡢ࢚ࢿࣝࢠ࣮‽఩࠾ࡼࡧศᏊ㌶㐨ࢆ )LJXUH ࡟♧ࡍࠋ+202 ࡣࠊ࠸ࡎࢀࡶศᏊ඲య࡟ᗈࡀࡗࡓ ʌ ᛶࡢ㌶㐨ࢆ᭷ࡋ࡚࠸ࡿࠋ໬ྜ≀ 2 ࡛ࡣࠊࣜࣥཎᏊࢆྵࡴභဨ⎔ & ࡢ஧㔜⤖ྜࡢᐤ୚ࡀᑠࡉ࠸ࡓࡵ࡟
ศᏊ඲యࡢඹᙺ⣔ࡀᑠࡉࡃ࡞ࡾࠊ௚ࡢ࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ࡜ẚ㍑ࡋ࡚ +202 ࡀపࡃ࡞ࡗ࡚࠸ࡓࠋࢼࣇࢱࣞࣥ
⦰⎔ㄏᑟయ 3a-c ࡟࠾࠸࡚ࡣࠊ࠸ࡎࢀࡢሙྜࡶ 1a ࡼࡾ +202 ࡀ㧗ࡃࠊ3b3a3c ࡢ㡰࡟ୖ᪼ࡋ࡚࠸ࡓࠋࢼࣇࢱ
࡛ࣞࣥࡣ &í& ⤖ྜࡢ࡯࠺ࡀ &í& ⤖ྜࡼࡾࡶ஧㔜⤖ྜᛶࡀ㧗ࡃࠊࢼࣇࢱࣞࣥ⮬㌟ࡢ +202 ࡢᐤ୚ࡀ኱ࡁ
࠸ࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

- 132 -

Figure 1. ໬ྜ≀ 1a23a-c ࡢ࢚ࢿࣝࢠ࣮‽఩࠾ࡼࡧศᏊ㌶㐨/802 ࡟࠾࠸࡚ࡶࠊ+202 ࡜ྠᵝ࡟ศᏊ඲య࡟ᗈࡀࡗࡓ ʌ ᛶࡢ㌶㐨࡛࠶ࡾࠊ㟁Ꮚồᘬᛶࡢ 3 2 㒊఩ࡢᐤ୚ࡀ኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ໬ྜ≀ 1a ࡟ᑐࡋ࡚⦰⎔ࡉࡏࡓ࣋ࣥࢮࣥ⎔࡜ࡢ㌶㐨┦஫స⏝࡟╔┠ࡍࡿ࡜ࠊ໬ྜ
≀ 3a ࡜ 3c ࡛ࡣ㌶㐨ࡢ㔜࡞ࡾࡀᏑᅾࡍࡿࡢ࡟ᑐࡋ ⥳ࡢ▮༳࡛グ㍕ ࠊ໬ྜ≀ 3b ࡛ࡣ⠇ࢆ⏕ࡌ࡚࠸ࡓࠋࡑࡢࡓ
ࡵࠊ/802 ࡣ 1a ࡜ẚ㍑ࡋ࡚໬ྜ≀ 3a 3c ࡛ࡣపୗࡋࠊ3b ࡛ࡣୖ᪼ࡋࡓࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ+202 /802ࡢ࢚ࢿࣝࢠ࣮‽఩ࡣࠊ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝ࠾ࡼࡧ &9ᐃ࡟࠾ࡅࡿᐇ㦂⤖ᯝࢆ෌⌧ࡋ࡚࠸ࡓࠋ

࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ࡟࠾ࡅࡿ஬ဨ⎔ % ࡜භဨ⎔ & ࡢ 1,&6  ࢆ⟬ฟࡋࡓ࡜ࡇࢁࠊ࠸ࡎࢀࡶṇࡢ್ࢆ♧ࡋࠊᙅ࠸཯ⰾ㤶᪘ᛶࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ 7DEOH  ࠋ⎔ % ࡢ್ࡣ࣍ࢫ࣮࣍ࣝ࢜࢟ࢩࢻ  ࠾ࡼࡧ࣋ࣥ
ࢰ>E@࣍ࢫ࣮࣍ࣝ࢜࢟ࢩࢻ  ࡼࡾࡶቑຍࡋ࡚࠸ࡓࠋ໬ྜ≀ 3a ࡜ 3c ࡢ 1,&6 ್ࡣࠊ௚࡜ẚ㍑ࡋ࡚኱ࡁࡃ࡞
ࡗ࡚࠾ࡾࠊ࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥ࡟⦰⎔ࡋࡓࢼࣇࢱࣞࣥ⎔ࡢ஧㔜⤖ྜᛶ࡟ࡼࡿᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

4Ⓨ⾲࠾ࡼࡧฟ∧ᐇ⦼‫ ۻ‬ὠ␃ᓮ 㝧኱ࠊ⏣ཎ ⣪ዉࠊ୰ᮧ ㄔࠊᯇᮏ ၨୡࠊ⚄ᕝ ᠇ࠊࠕSᣑᙇ࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥㄏᑟయࡢྜᡂ࡜ᛶ
㉁ࠖࠊ➨  ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍ࠊி㒔ࣃࣝࢫࣉࣛࢨࠊ ᖺ  ᭶ࠊ$‫ ۻ‬ὠ␃ᓮ 㝧኱ࠊᾆ 㔛⳹Ꮚࠊ⚄ᕝ ᠇ࠕ␗࡞ࡿ㓄఩ᵝᘧࢆ࡜ࡿࣅࢫ ࢪ࣍ࢫࣇ࢙ࣥ ࣃࣛࢪ࣒࢘ ,, 㘒యࠖࠊ➨ ᅇ᭷ᶵ㔠ᒓ໬Ꮫウㄽ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ ᖺ  ᭶ࠊ3&‫ ۻ‬ᓊᮏ ┿⌮⾰, ὠ␃ᓮ 㝧኱, ⚄ᕝ ᠇ࠕ㔠 , ゐ፹ࢆ⏝࠸ࡓศᏊෆࣄࢻࣟ࢔࣮ࣜࣝ໬཯ᛂ࡟ࡼࡿ࣍ࢫࣇ࢙ࣆࣥ
ㄏᑟయࡢྜᡂࠖࠊ➨  ᅇ᭷ᶵ඾ᆺඖ⣲໬Ꮫウㄽ఍ࠊᐩᒣ኱Ꮫࠊ ᖺ  ᭶ࠊ2% ‫ ۻ‬୰ᮧ ㄔ, ὠ␃ᓮ 㝧኱, ⚄ᕝ ᠇ࠕࢡࣟࣟ⨨᥮ࢪ࣋ࣥࢰ࣍ࢫࣇ࢕ࣥࢻࣜࢪࣥࡢኚ᥮཯ᛂࠖࠊ➨  ᅇ᭷ᶵ඾ᆺඖ⣲໬Ꮫウㄽ఍ࠊᐩᒣ኱Ꮫࠊ ᖺ  ᭶ࠊ3%‫ ۻ‬$ 7VXUXVDNL 6 7DKDUD 0 1DNDPXUD + 0DWVXPRWR . .DPLNDZD ³6\QWKHVLV 6WUXFWXUHV DQG 3URSHUWLHV RI

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ࢼࣀⅣ⣲࣭࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊✲
4XDQWXP&KHPLFDO6WXG\RQ5HDFWLRQ'\QDPLFVRI1DQRFDUERQV$PLQR$FLGVDQG&OXVWHUV‫ۑ‬ᒣ໭ ెᏹࠊ㧗ᶫ ᾴࠊᒣཱྀ ៞࿃㸦㟁Ẽ㏻ಙ኱Ꮫ㸧◊✲┠ⓗᮏ◊✲ࡢ┠ⓗࡣࠊ(1) ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲㸦PAH㸧࡜࢔࣑ࣀ㓟ࡢ࣌ࢽࣥࢢ࢖࢜ࣥ໬཯ᛂ㸦He* + M Ѝ He +M + e-㸧ࡢ཯ᛂືຊᏛࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࠊ(2) ᯫᶫᵓ㐀ࢆᣢࡘࣃࣛࢩࢡࣟࣇ࢓ࣥ㢮ࡸࠊSඹᙺ⣔࡞࡝ࡢᙉ࠸
࣐ࣛࣥᙉᗘࡢ㉳※ࢆศᏊ㌶㐨ࢆ౑ࡗ࡚♧ࡍࡇ࡜ࠊ(3) ࢔࣑ࣀ㓟ࡢ㟁Ꮚᵓ㐀ࢆィ⟬ࡋࠊศᏊෆᅇ㌿࣏ࢸࣥࢩࣕࣝ
࡟ᑐࡍࡿỈ⣲⤖ྜ࡜࢚ࣥࢺࣟࣆ࣮ࡢᐤ୚ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࠊ(4) ࣛࣥࢱࣀ࢖ࢻ࡟ศᏊࡀ྾╔ࡋࡓࢡࣛࢫࢱ
࣮࡟ࡘ࠸࡚㉁㔞ศᯒᐇ㦂࡜ᑐẚࡋ࡞ࡀࡽᵓ㐀Ỵᐃ࡜ࢡࣛࢫࢱ࣮ෆ཯ᛂࡢ⤒㊰ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛࠶ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ(1) ࡟ࡘ࠸࡚ࡣࠊGaussian 16 ࡜⮬సࡢࣉࣟࢢ࣒ࣛࢆ⏝࠸ࠊ࣋ࣥࢮࣥ࡜ࢺ࢚ࣝࣥࡢ࣒࣊ࣜ࢘ບ㉳ཎᏊ He*(23S)࡜ࡢ┦஫స⏝ࢆ 3 ḟඖ᱁ᏊⅬୖ࡛ィ⟬ࡋࠊศᏊ㓄ྥࢆつᐃࡋࡓ≧ែ࡛ྂ඾ࢺࣛࢪ࢙ࢡࢺࣜィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࢥࢫࢺࡢၥ㢟࡛ He*࡜➼౯እẆ࡛࠶ࡿ Li ࢆ⏝࠸ศᏊ࡜ࡢ┦஫స⏝࢚ࢿࣝࢠ࣮ࢆ MP2 ࡛ࣞ࣋ࣝ Counterpoiseἲࢆ౑ࡗ࡚ィ⟬ࡋࡓࠋ(2)࡟ࡘ࠸࡚ࡣࠊ࣐ࣛࣥᙉᗘࢆィ⟬ࡍࡿࡓࡵࠊ㟁ሙᏑᅾୗ࡛ࡢ཮ᴟᏊ⾜ิࢆ Gaussian 16࡛ィ⟬ࡋࡓࠋ (3),(4) ࡟ࡘ࠸࡚ࡣࠊLa+ࡸ Cu+࡟࢔ࢭࢺࣥࡸ࢔ࢡࣜࣟࢽࢺࣜࣝࡀ 2㹼4 ศᏊ㓄఩ࡋࡓࢡࣛࢫࢱ࣮
࢖࢜ࣥࡢᏳᐃᵓ㐀࡜཯ᛂ⤒㊰᥈⣴ࢆ GRRM ࣉࣟࢢ࣒࡛ࣛィ⟬ࡋࡓࠋ



◊✲ᡂᯝ
(1) ࡟ࡘ࠸࡚ࠊ࣋ࣥࢮࣥ࡜ࢺ࢚ࣝࣥࡢࢩ࣮ࢻศᏊ⥺୰ࡢศᏊ㓄ྥࡀ೫ࡗ࡚࠸ࡿࡇ࡜ࢆ♧ࡍᐇ㦂⤖ᯝࡀᚓࡽࢀࡓ[1]ࠋࡑࡇ࡛ࠊ࣋ࣥࢮࣥࡢ㓄ྥࢆᅛᐃࡋ࡚ࢺࣛࢪ࢙ࢡࢺࣜィ⟬ࢆ⾜࠸ࠊS㌶㐨㸦V㌶㐨㸧ࡢ࢖࢜ࣥ໬᩿㠃✚ࡀ㠃እ㸦㠃ෆ㸧᪉ྥ࠿ࡽࡢ᥋㏆࡛ࡣ኱ࡁࡃ࡞ࡿࡇ࡜ࢆぢฟࡋࡓ[2]ࠋࡋ࠿ࡋ㸪ୖグࡢᐇ㦂஦ᐇࡣࢡࣛࢫࢱ࣮⏕ᡂ࡟ࡼࡿࡶࡢ࡛࠶ࡿྍ⬟ᛶࡀุ᫂ࡋࡓࠋࡑࡇ࡛ࢡࣛࢫࢱ࣮ࡢィ⟬ࢆࡉࡽ࡟⾜࠸ࠊᐇ㦂᮲௳ࢆ᭱㐺໬ࡋ࡞ࡀࡽ
඲ㇺࢆゎ᫂ࡋࡘࡘ࠶ࡿࠋ(2)࡛ࡣࠊᯫᶫᆺⅣ໬Ỉ⣲ࡸ࢟ࣀ࢖ࢻࡢSඹᙺ⣔ࡢᇶ‽᣺ື࡛ㄏ㉳ࡉࢀࡿ཮ᴟᏊ࣮࣓ࣔ
ࣥࢺࢆ㟁ሙᏑᅾୗ࡛ゎᯒࡋࠊศᏊ㌶㐨ࡢᐤ୚ࡢ≉ᛶࢆ≉␗್ศゎ࡛ゎᯒࡋࡓ[3]ࠋ(3),(4)࡛ࡣࠊࡑࢀࡒࢀ࢔࣑ࣀ
㓟ࡢ࣌ࢽࣥࢢ㟁Ꮚࢫ࣌ࢡࢺࣝ࡜ࢡࣛࢫࢱ࣮ෆ཯ᛂ࡟㛵ࡍࡿㄽᩥࢆྲྀࡾࡲ࡜ࡵ࡚࠸ࡿࠋ



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[1] 㧗ᶫ㸪ΎỈ㸪ᒣ໭㸪㧗ឤᗘ࣌ࢽࣥࢢ㟁Ꮚศග࡟ࡼࡿ㉸㡢㏿ศᏊ⥺୰ࡢ࢔ࣝ࢟ࣝ࣋ࣥࢮࣥࡢ㓄ྥศᕸࡢ◊✲㸪᪥ᮏ໬Ꮫ఍➨ 103 ᫓Ꮨᖺ఍㸪K205-2pm㸬‫[ۻ‬2] ᮏྜྷ㸪㧗ᶫ㸪ᒣ໭㸪ࢩ࣮ࢻศᏊ⥺୰ࡢ࣋ࣥࢮࣥࡢ㓄ྥ࡟╔┠ࡋࡓ࣌ࢽࣥࢢ࢖࢜ࣥ໬཯ᛂࡢྂ඾ࢺࣛࢪ࢙ࢡࢺࣜィ⟬㸪᪥໬➨ 103 ᫓Ꮨᖺ఍㸪P1-2am-06㸬‫[ۻ‬3] ᒣཱྀ㸪ᒣ໭㸪㠀ᖹ㠃ࢼࣀⅣ⣲ࡢ࣐ࣛࣥᙉᗘ࡜㟁Ꮚບ㉳≧ែࡢ≉␗್ศゎ࡟ࡼࡿゎᯒ㸪᪥໬➨ 103 ᫓Ꮨᖺ఍㸪3DP㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] Y. Shigekawa, Y. Kasamatsu, Y. Yamakita, Y. Yasuda, E. Watanabe, N. Kondo, H. Haba, A. Shinohara, Nucl. Inst.
Methods Phys. Res. A, 976, 164207 (2020). 10.1016/j.nima.2020.164207 ‫[ۻ‬2] Y. Ishiguro, Y. Yamakita, and N. Hayashi,
Chem. Phys. Lett., 754, 137653 (2020). 10.1016/j.cplett.2020.137653- 134 -

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ࡁࡓࠋࡋ࠿ࡋࠊィ⟬㔞ࡢไ⣙࠿ࡽࠊࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡿᵓ㐀ࡣ᪤▱ࡢᵓ㐀࡝࠺ࡋࢆ┤⥺ⓗ࡟⤖ࡪ⤒㊰ࡢ㏆ഐ࡟㝈ᐃࡉࢀ࡚࠸ࡿࠋ
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㐀ኚ໬ࡢ༠ྠᛶࢆ⪃៖ࡋࡓ⢒ど໬ࣔࢹࣝࢆ㛤Ⓨࡍࡿࠋ஧ḟᵓ㐀ኚ໬ࠊ኱つᶍࢻ࣓࢖ࣥ㐠ືࠊ」ྜయᵓ㐀ࡢᅄḟᵓ㐀ኚ໬࡜࠸ࡗࡓከᵝ࡞ᵓ㐀㌿⛣ࢆ♧ࡍࢱࣥࣃࢡ㉁ࡢᐇ㦂஦ᐇࢆཧ↷ࡋ࡞ࡀࡽࠊࡇࢀࡽࡢࢱࣥࣃࢡ㉁࡟୍
⯡ⓗ࡟㐺⏝࡛ࡁࡿ⤫୍ⓗ࡞ࣔࢹࣝࢆᵓ⠏ࡋࠊࡇࢀࢆ⏝࠸ࡓ኱ᇦⓗ࡞ࣛࣥࢻࢫࢣ࣮ࣉࡢィ⟬࡟ࡼࡾࠊᵓ㐀㌿⛣ࡢ☜⋡ⓗᥥീࢆ☜❧ࡍࡿࠋࢃࢀࢃࢀࡣ㐣ཤ࡟ࠊ┦஫స⏝㒊఩ࡢ࠶࠸ࡔࡢ༠ྠⓗ࡞ᒁᡤᵓ㐀ኚ໬ࢆ⾲⌧ࡋࡓ࣓࢝ࣞ࢜ࣥࣔࢹࣝࢆᥦၐࡋࡓ (Terada et al., J. Phys. Chem. B 117, 12864-12877 (2013))ࠋࡇࡢࣔࢹࣝࡣࠊࢱࣥࣃࢡ㉁ࡢᵓ㐀㌿⛣๓ᚋࡢ஧ࡘ
ࡢ❧యᵓ㐀࡟ᇶ࡙࠸࡚ࠊ኱ᇦⓗ࡞ࣛࣥࢻࢫࢣ࣮ࣉࢆ⏕ᡂ࡛ࡁࡿ⢒ど໬ࣔࢹ࡛ࣝ࠶ࡾࠊ౛࡜ࡋ࡚ DHFR ࡢᵓ㐀㌿⛣࣓࢝ࢽࢬ࣒ࡢゎᯒࡀ࠾ࡇ࡞ࢃࢀࡓࠋࡋ࠿ࡋࠊ୍⯡ࡢࢱࣥࣃࢡ㉁࡟ࡘ࠸࡚ᵓ㐀㌿⛣⤒㊰ࢆṇ☜࡟グ㏙ࡍࡿࡓࡵ࡟ࠊ༠ྠⓗ࡞ᒁᡤᵓ㐀ኚ໬ࢆ࡝ࡢࡼ࠺࡟ࣔࢹࣝ໬ࡍࢀࡤࡼ࠸ࡢ࠿࡟ࡘ࠸࡚ࡣࠊ༑ศ࡞᳨ウࡀ࠾ࡇ࡞ࢃࢀ
࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲ࡣࠊࡼࡾከࡃࡢࢱࣥࣃࢡ㉁࡟㛵ࡍࡿᐇ㦂஦ᐇ࡟ࡶ࡜࡙ࡃ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡢ㐺⏝⠊ᅖࡢᣑ኱࡜ᅄḟᵓ㐀ኚ໬࡬ࡢᣑᙇ࡟ࡼࡾࠊከᵝ࡞ࢱࣥࣃࢡ㉁ࡢᵓ㐀㌿⛣࣓࢝ࢽࢬ࣒ࢆ࢔࣑ࣀ㓟ṧᇶࣞ࣋ࣝࡢศゎ⬟࡛ணゝ࡛ࡁࡿ⤫୍ⓗ࡞ࣔࢹࣝࢆᵓ⠏ࡋࠊ኱ᇦⓗࣛࣥࢻࢫࢣ࣮ࣉࢆィ⟬ࡍࡿࡇ࡜࡟ࡼࡾᵓ㐀㌿⛣ࡢ☜⋡ⓗᥥീࢆ☜❧ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣࠊࢱࣥࣃࢡ㉁ࢆ࢔࣑ࣀ㓟ṧᇶࣞ࣋ࣝࡢ⢒ど໬ࣔࢹ࡛ࣝ⾲⌧ࡍࡿࠋࡍ࡞ࢃࡕࠊX ⥺⤖ᬗゎᯒࡲࡓࡣ NMR ࡟ࡼࡿ❧యᵓ㐀ࢆ⏝࠸࡚ࠊ࢔࣑ࣀ㓟ṧᇶ 1 ಶࢆ୍ࡘࡢ㉁Ⅼ࡜ࡋ࡚⢒ど໬ࡍࡿࠋࡑࡋ࡚ࠊ⢒ど໬⢏Ꮚ㛫ࡢ┦஫స⏝࡜ࡋ࡚ࠊ2 ࡘࡢ❧యᵓ㐀ࢆᏳᐃ࡟ࡍࡿ 2 ✀㢮ࡢ┦஫స⏝ࡢ࠶࠸ࡔ࡛㐃⥆ⓗ࡟ษࡾ᭰ࢃࡿ࣓࢝ࣞ
࢜ࣥࣔࢹࣝࢆ᥇⏝ࡍࡿࠋ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡣලయⓗ࡟ࡣࠊ⤖ྜゅ࣏ࢸࣥࢩ࣭ࣕࣝ஧㠃ゅ࣏ࢸࣥࢩ࣭ࣕࣝࢥࣥ

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ࢱࢡࢺ࣏ࢸࣥࢩࣕࣝࡢ 3 ✀㢮ࡢ࣏ࢸࣥࢩࣕࣝࡢྜィ࡛⾲ࡉࢀࡿࡀࠊ┦஫స⏝⢏Ꮚࡢ࿘ᅖ⎔ቃࡀ 2 ࡘࡢᵓ㐀࡟࠾ࡅࡿ࿘ᅖ⎔ቃࡢ࡝ࡕࡽ࡟ࡼࡾ㏆࠸࠿ࢆ⾲ࡍ⎔ቃኚᩘࡢኚ໬࡟ᛂࡌ࡚ࠊ2 ࡘࡢ❧యᵓ㐀ࡢ࠺ࡕࡢ࠸ࡎࢀ࠿୍᪉࡟࠾ࡅࡿ್࡛᭱Ᏻᐃ࡜࡞ࡿࡼ࠺࡞ 2 ✀㢮ࡢ㛵ᩘᙧࡢ࠶࠸ࡔ࡛ࠊྛ┦஫స⏝ࡢ㛵ᩘᙧࡀ㐃⥆ⓗ࡟ኚ໬ࡍࡿࡼ
࠺࡟ᐃ⩏ࡉࢀ࡚࠸ࡿࠋ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡢ᭱ึࡢㄽᩥ (Terada etal., J. Phys. Chem. B 117, 12864-12877 (2013)) ࡢ࠶࡜ࠊࡇࡢࣔࢹࣝ
ࡢᵝࠎ࡞㒊ศ࡟ᑐࡋ࡚ᨵⰋࢆ⾜ࡗ࡚ࡁ࡚࠸ࡿࡀࠊࡲࡔ᳨ウࡢవᆅࡀከࡃṧࡉࢀ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࠊࡇࡢࣔࢹࣝࢆ⏝࠸࡚⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮
ࣉゎᯒࢆ⾜࠺ࡓࡵ࡟ࠊᇶᮏⓗ࡟ࡣࣛࣥࢪࣗࣂࣥືຊᏛἲࢆ⏝࠸࡚ᅗ 㸸࣓࢝ࣞ࢜ࣥࣔࢹࣝࡢᴫᛕᅗࠋᒁ

࠸ࡿࠋࡲࡓࠊ୍㒊ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ㧗࠸ሙྜ࡟ࡘ࠸࡚ࡣࠊ

ᡤᵓ㐀ኚ໬࡟㐃ືࡋ࡚┦஫స⏝ࡢᏳ࣐ࣝࢳ࢝ࣀࢽ࢝ࣝἲࢆ⏝࠸࡚࠸ࡿࡀࠊࣛࣥࢪࣗࣂࣥືຊᏛἲ࡜࠺

ᐃ㓄⨨ࡀኚ໬ࡍࡿࠋ

ࡲࡃ⤌ࡳྜࢃࡏࡿࡇ࡜ࡀ㞴ࡋࡃࠊࣔࣥࢸ࢝ࣝࣟἲࡢ࣒࣮ࣦࢭࢵࢺ
ࡢ⏕ᡂ᪉ἲ࡜ࡋ࡚ࡈࡃ▷࠸ศᏊືຊᏛィ⟬ࢆ⾜࠺ࣁ࢖ࣈࣜࢵࢻࣔࣥࢸ࢝ࣝࣟἲࢆᐇ⿦ࡋ౑⏝ࡋ࡚࠸ࡿࠋ
௨ୖࡢᮏ◊✲ࡢィ⟬ࡣࡍ࡭࡚ࠊ᪤Ꮡࡢࢯࣇࢺ࢙࢘࢔ࢆ⏝࠸ࡿࡢ࡛ࡣ࡞ࡃࠊ◊✲ᐊ⊂⮬࡛ᵓ⠏ࡋࡓࢯࣇࢺ࢘
࢙࢔ࢆ⏝࠸࡚⾜ࡗ࡚࠸ࡿࠋ౑⏝ゝㄒࡣ୺࡟ Fortran 77 ࡛࠶ࡿࠋ



◊✲ᡂᯝ
㸯㸬ࢻ࣓࢖ࣥ㐠ືࢆ࡜ࡶ࡞࠺࢔ࣟࢫࢸࣜࢵࢡ㌿⛣ࢆ㉳ࡇࡍ࣐ࣝࢳࢧࣈࣘࢽࢵࢺࢱࣥࣃࢡ㉁࡛࠶
ࡿ࢔ࢹࢽࣝ㓟࢟ࢼ࣮ࢮࢆᑐ㇟࡟ࡋࡓィ⟬࡛ࡣࠊ㐣ཤࡢ◊✲࡟࠾࠸࡚ᐊ
⛣࡜࡟࠾ࡅࡿ 2 ≧ែⓗ࡞ᵓ㐀㌿ᗘୖ᪼࡟క࠺࢔ࣥࣇ࢛࣮ࣝࢹ࢕ࣥࢢ㌿⛣ࡢ୧᪉ࢆ⾲⌧ࡍࡿࡇ࡜࡟ᡂຌࡋ࡚࠸ࡓࡀࠊᐇ㦂࡛ࡣ௚ࡢࢻ࣓࢖ࣥ࡜ẚ࡭࡚୙Ᏻᐃ࡛࠶ࡿ࡜ࡉࢀ࡚
࠸ࡿ LID ࢻ࣓࢖ࣥࡀࣔࢹࣝィ⟬࡛ࡣ௚ࡢࢻ࣓࢖
ࣥ࡜ẚ࡭࡚Ᏻᐃ࡟࡞ࡗ࡚࠸ࡿ࡜࠸࠺ၥ㢟ࡀ࠶ࡗࡓࡓࡵࠊࡇࡢⅬࢆᨵⰋࡍࡿ◊✲ࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣ࢔࣑ࣀ㓟ṧᇶࡢࢥࣥࢱࢡࢺ࣐ࢵࣉࡢᐃ⩏ࡢᅗ 2㸸ṧᇶ㛫┦஫స⏝ࡢᙉࡉ࡟ Miyazawa-Jernigan ࣏ࢸࡋ࠿ࡓࡢኚ᭦࡜㸪ṧᇶ㛫ࡢ┦஫స⏝ࡢᙉࡉࢆࣥࢩࣕࣝ࡟ࡼࡿᙉᙅࢆࡘࡅࡓሙྜࡢ࢔ࢹࢽࣝ㓟࢟ࢼ࣮

Miyazawa-Jernigan ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚࢔࣑ࣀ

ࢮࡢྛṧᇶࡢ࿘㎶ࡢࣇ࢛࣮ࣝࢹ࢕ࣥࢢࡢ⛬ᗘࠋᶓ㍈ࡣ㓟ࡢ✀㢮ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡗ࡚ኚ໬ࡉࡏࡿኚ᭦

ṧᇶ␒ྕࠋኚᛶ

ࡢ஧ࡘࢆヨࡋࡓ࡜ࡇࢁࠊᚋ⪅ࡢᨵኚ࡟ࡼࡗ࡚ LID࣓࣮ࢱ࣮࡟ࡼࡗ࡚ᵓ㐀✵㛫඲యࢆኳ↛≧ែࠊ㑄⛣≧ែࠊࢻ࣓࢖ࣥࡀኚᛶ≧ែ࡛᭱ࡶ୙Ᏻᐃ࡛࠶ࡿ࡜࠸࠺

ኚᛶ≧ែࡢ 3 ࡘ࡟ศࡅࡓ࡜ࡁࡢྛ≧ែ࡟࠾ࡅࡿᖹᆒ್

ᐇ㦂⤖ᯝࢆ෌⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋLID ࢻ࣓࢖ࣥࢆࡑࢀࡒࢀ⥳ࠊ࢜ࣞࣥࢪࠊ㟷࡛ࣉࣟࢵࢺࡋ࡚࠸ࡿࠋ㑄ࡀ௚ࡢࢻ࣓࢖ࣥ࡜ẚ࡭࡚ぶỈᛶࡀ㧗࠸ࡇ࡜ࢆࣔ

⛣≧ែ࠾ࡼࡧኚᛶ≧ែ࡟࠾࠸࡚ࠊLID ࢻ࣓࢖ࣥ࡜ COREࢹࣝ࡟཯ᫎࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡓ⤖ᯝ࡜⪃࠼ࡽࢀࢻ࣓࢖ࣥࡢ୍㒊ࡀ୙Ᏻᐃ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ

- 138 -

ᗘ࡟࠾ࡅࡿᵓ㐀㌿⛣ࡢ࣮࢜ࢲ࣮ࣃࣛ

ࡿࠋ௒ᚋࡢㄢ㢟ࡣࠊࡇࡢ࢔࣑ࣀ㓟ࡢ✀㢮࡟ࡼࡗ࡚┦஫స⏝ࡢᙉࡉࡀኚࢃࡿࣔࢹࣝࢆ⏝࠸࡚ࠊᐊ࡟࠾ࡅࡿ 2≧ែⓗ࡞ᵓ㐀㌿⛣ࡀ෌⌧࡛ࡁࡿࡇ࡜ࢆ☜ㄆࡍࡿ࡜࡜ࡶ࡟ࠊࣜ࢞ࣥࢻࡀᏑᅾࡍࡿ᮲௳࡟࠾ࡅࡿ 2 ≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡢ㧗ࡉࡢኚ໬࠿ࡽィ⟬ࡉࢀࡿᵓ㐀㌿⛣ࡢ㏿ᗘࡢᗘ౫Ꮡᛶࡀ㓝⣲άᛶ㏿ᗘࡢᗘ౫Ꮡᛶ࡜୍⮴ࡍࡿ࠿࡝࠺࠿ࢆ☜ㄆࡋࠊࣔࢹࣝࡢጇᙜᛶࢆ᳨ドࡍࡿࡇ࡜࡛࠶ࡿࠋ
㸰㸬஧ḟᵓ㐀ࡀ猕ࡁࡃ␗࡞ࡿᵓ㐀ࡢ㛫࡛ᵓ㐀㌿⛣ࡍࡿ࣓ࢱࣔࣝࣇ࢕ࢵࢡࢱࣥࣃࢡ㉁ࡢ୍ࡘ࡜ࡋ࡚▱ࡽࢀ࡚
࠸ࡿ XCL1 ࢆᑐ㇟࡟ࡋࡓ◊✲࡛ࡣࠊᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀẚ㍑ⓗ㧗࠸ࡇ࡜ࡀண᝿ࡉࢀࡿࡓࡵࠊ࣐
ࣝࢳ࢝ࣀࢽ࢝ࣝࢧࣥࣉࣜࣥࢢࢆ⏝࠸࡚ 2 ≧ែⓗ࡞ᵓ㐀㌿⛣ࢆ෌⌧ࡋࡓࠋXCL1 ࡟㛵ࡍࡿඛ獻◊✲࡛⾜ࢃࢀࡓᐇ㦂࠿ࡽࠊᵓ㐀㌿⛣㏿ᗘ࡜࢔ࣥࣇ࢛࣮ࣝࢻ㏿ᗘࡀ࡯ࡰྠࡌ್ࢆࡶࡘࡇ࡜࠿ࡽࠊXCL1 ࡢᵓ㐀㌿⛣ࡣ࢔ࣥࣇ࢛
࣮ࣝࢻ≧ែࢆ⤒⏤ࡍࡿᚲせࡀ࠶ࡿ࡜࠸࠺᥎ㄽࡀ࡞ࡉࢀ
࡚࠸ࡓࡀࠊࣔࢹࣝィ⟬࡟ࡼࡿ 2 ḟඖࡢ⮬⏤࢚ࢿࣝࢠ࣮
ࣛࣥࢻࢫࢣ࣮ࣉゎᯒ࠿ࡽࠊ࢔ࣥࣇ࢛࣮ࣝࢻ≧ែࢆ⤒⏤ࡏࡎ࡟ᵓ㐀㌿⛣ࡍࡿ⤒㊰ࡀᏑᅾࡍࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋࡲࡓ XCL1 ࡣࢪࢫࣝࣇ࢕ࢻ⤖ྜࢆ୍ࡘࡶࡘࡀࠊࢪ
ࢫࣝࣇ࢕ࢻ⤖ྜࡀ࡞࠸ሙྜࡢィ⟬⤖ᯝ࡜ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢẚ㍑࠿ࡽࠊࢪࢫࣝࣇ࢕ࢻ⤖ྜࡀ࠶ࡿࡇ࡜࡛ᵓ㐀㌿⛣ࡢ獳⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ㧗ࡃ࡞ࡗ࡚࠾ࡾࠊࢪࢫࣝࣇ࢕ࢻ⤖ྜࡀ࡞ࡅࢀࡤᵓ㐀ࡢศᕸࡀࡼ

ᅗ 3㸸ᐊ࡟࠾࠸࡚ィ⟬ࡉࢀࡓࢪࢫࣝࣇ࢕ࢻ⤖ྜࡀ࠶ࡿሙྜࡢ XCL1 ࡢᵓ㐀㌿⛣ࡢ 2 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࠋ⦪㍈ࡣ Ltn10ࠊᶓ㍈ࡣ
Ltn40 ᵓ㐀࡜ࡢ㢮ఝᛶࢆ࠶ࡽࢃࡍ࣮࢜ࢲ࣮ࣃ࣓ࣛ
࣮ࢱ࣮ࠋࡾᗈ⠊ᅖ࡟ᗈࡀࡿ࡜࠸࠺ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡓࡔࡋࠊ⌧᫬Ⅼ࡛ࡣࣔࢹࣝࡢࣃ࣓࣮ࣛࢱㄪᩚࡀ୙༑ศ࡛࠶ࡿࡓ
ࡵࠊLtn10 ࠾ࡼࡧ Ltn40 ࡜ࡼࡤࢀࡿ஧ࡘࡢᵓ㐀ࡢ࠺ࡕ Ltn40 ࡀከࡃᏑᅾࡍࡿ⤖ᯝ࡜࡞ࡗ࡚࠾ࡾࠊࡇࢀࡣ஧ࡘࡢ
ᵓ㐀ࡀ࡯ࡰ➼ࡋ࠸☜⋡࡛Ꮡᅾࡍࡿ⌧ᐇ࡜୍⮴ࡋ࡚࠸࡞࠸ࠋࡲࡓࠊᮏ◊✲ࡢࣔࢹࣝィ⟬ࡣ༢㔞యࡢィ⟬࡟࡜࡝ࡲࡗ࡚࠾ࡾࠊLtn40 ࡢᵓ㐀࡟࠾࠸࡚஧㔞యࢆᙧᡂࡍࡿ஦ᐇࢆ⾲⌧࡛ࡁ࡚࠸࡞࠸ࠋࡇࢀࡽࡢⅬࢆᨵⰋࡍࡿࡇ࡜ࡀ
௒ᚋࡢㄢ㢟࡛࠶ࡿࠋ

ᅗ 4㸸ᐊ࡟࠾࠸࡚ィ⟬ࡉࢀࡓࢪࢫࣝࣇ࢕ࢻ⤖ྜࡀ࠶ࡿሙྜ㸦ᕥ㸧࠾ࡼࡧ࡞࠸ሙྜ㸦ྑ㸧ࡢ XCL1 ࡢᵓ㐀㌿⛣ࡢ 1 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࠋ

- 139 -

㸱㸬ᅄḟᵓ㐀ኚ໬ࢆ࡜ࡶ࡞࠺࢔ࣟࢫࢸࣜࢵࢡ㌿⛣ࢆ㉳ࡇࡍ࣐ࣝࢳࢧࣈࣘࢽࢵࢺࢱࣥࣃࢡ㉁࡛࠶ࡿ࣊ࣔࢢࣟ
ࣅࣥࢆᑐ㇟࡟ࡋࡓィ⟬࡛ࡣࠊ㓟⣲⤖ྜ᭤⥺ࡀ S Ꮠᆺ࡟࡞ࡿ≧ἣࢆ෌⌧ࡍࡿࡓࡵࡢ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡢᨵⰋࢆ
㐍ࡵࡓࠋᙜึࡢࣔࢹ࡛ࣝࡣ T ≧ែ࡜ R ≧ែࡢ㛫ࡢ 2 ≧ែ㌿⛣ࡀࡳࡽࢀࠊ㓟⣲⃰ᗘࡀୖࡀࡿ࡟ࡘࢀ࡚ R ≧ែࡀࡼࡾᏳᐃ࡟࡞ࡗ࡚࠸ࡃࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࡶࡢࡢࠊ㓟⣲⤖ྜ᭤⥺ࡣ S Ꮠᆺ࡛ࡣ࡞ࡃ཮᭤⥺࡜࡞ࡗࡓࠋࡇࡢཎᅉ
ࢆㄪ࡭ࡓ⤖ᯝ࡜ࡋ࡚ࠊࢱࣥࣃࢡ㉁ࡢᵓ㐀඲యࡢ T ≧ែ࡜ R ≧ែࡢ㛫࡛㓟⣲⤖ྜ㒊఩࿘㎶ࡢᵓ㐀࡟኱ࡁ࡞ᕪ
ࡀ⏕ࡌ࡚࠸࡞࠸ࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࡢ≧ἣࢆᨵၿࡍࡿࡓࡵࠊ㓟⣲⤖ྜ㒊఩࿘㎶ࡢ⢏Ꮚ࡜ࡑࡢ࿘㎶࡛ࡣࡓࡽࡃ࣏ࢸࣥࢩࣕࣝࡢᖜࢆᑠࡉࡃࡍࡿ࡜࡜ࡶ࡟ࠊ㓟⣲⤖ྜ㒊఩࿘㎶ࡢ⢏Ꮚ㛫㊥㞳ࡢࡎࢀࡢチᐜ⠊ᅖࢆ⊃ࡃࡋ࡚ࠊ෌ᗘࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ࠾ࡇ࡞ࡗࡓ࡜ࡇࢁࠊ
ࢱࣥࣃࢡ㉁ࡢᵓ㐀඲యࡢ T ≧ែ࡜ R ≧ែࡢ㛫࡛㓟⣲⤖ྜ㒊఩࿘㎶ࡢᵓ㐀࡟ᕪࡀ⏕ࡌ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡇࡢኚ᭦࡟࡜ࡶ࡞ࡗ࡚㓟⣲ࡀᏑᅾࡋ࡞࠸
᮲௳࡛ࡶ T ≧ែࡼࡾࡶ R ≧ែࡢ᪉ࡀᏳᐃ࡜࡞ࡗࡓ
ࡓࡵࠊT ≧ែ࡜ R ≧ែࡢᏳᐃᛶࡢࣂࣛࣥࢫࡢㄪᩚࡀᚲせ࡜࡞ࡗࡓࡀࠊ᫬㛫ⓗไ⣙࠿ࡽ T ≧ែࡢ᪉ࡀᏳᐃ࡞᮲௳࡛ࡢィ⟬ࢆ⾜࠺ࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ௒
ᚋࡣᘬࡁ⥆ࡁ T ≧ែ࡜ R ≧ែࡢᏳᐃᛶࡢࣂࣛࣥࢫ
ࢆㄪᩚࡍࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࡲࡓࠊᅄ㔞యᵓ㐀ࢆᅗ 5㸸࣊ࣔࢢࣟࣅࣥࡢᵓ㐀㌿⛣ࡢ T ≧ែ࡜ R ≧ែ࡟஫࠸࡟ࡘ࡞ࡂ࡜ࡵࡿ࢔ࣥࣈ࣏ࣞࣛࢸࣥࢩࣕࣝࢆᑟ

࠾ࡅࡿ⢏Ꮚࡈ࡜ࡢ࿘ᅖ⎔ቃࡢ R ᵓ㐀࡬ࡢ㏆ࡉࠋᶓ㍈ධࡋࡓ࣐ࣝࢳ࢝ࣀࢽ࢝ࣝࢧࣥࣉࣜࣥࢢࢆᐇ⿦ࡍࡿ

ࡣ⢏Ꮚ␒ྕ࡛࠶ࡾࠊ㯮࠸⥺࡛༊ษࡽࢀࡓ 6 ࡘࡢ㡿ᇦࡇ࡜࡛ᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ㧗࠸ሙྜࡀᕥ࠿ࡽ㡰࡟Ș1 ࢧࣈࣘࢽࢵࢺࠊș1 ࢧࣈࣘࢽࢵࢺࠊ

࡛ࡶ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡀྍ⬟࡜࡞ࡿࡓࡵࠊ࣏ࢸ

Ș2 ࢧࣈࣘࢽࢵࢺࠊș2 ࢧࣈࣘࢽࢵࢺࠊ࣒࣊ࠊ࣒࣊ࡢ

ࣥࢩࣕࣝࡢᖜࢆᑠࡉࡃࡋࡓࡾ⢏Ꮚ㛫㊥㞳ࡢࡎࢀࡢ୧ഃࡢࣄࢫࢳࢪࣥṧᇶࡢഃ㙐ࡢ⢏Ꮚ࡟ᑐᛂࡋ࡚࠸

チᐜ⠊ᅖࢆ⊃ࡃࡋࡓࡾࡍࡿኚ᭦ࢆ㓟⣲⤖ྜ㒊఩࿘ࡿࠋᵓ㐀㌿⛣ࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮࡟ࡼࡾᐃ⩏ࡉ㎶࡟㝈ᐃࡏࡎศᏊ඲య࡟㐺⏝ࡍࡿࡇ࡜࡛ࠊ㓟⣲⤖ࢀࡓ T ≧ែ࡜ R ≧ែ࡟࠾ࡅࡿ್ࢆࡑࢀࡒࢀ㟷Ⰽ࡜㉥ྜࡢᙳ㡪ࢆࡼࡾ㗦ᩄ࡟཯ᫎࡋࡓᅄḟᵓ㐀㌿⛣ࡢ෌Ⰽࡢᢡࢀ⥺࡛⾲ࡍ࡜࡜ࡶ࡟ࠊ㓟⣲⤖ྜ㒊఩࿘㎶ࡢ⢏⌧ࢆ┠ᣦࡍࡇ࡜ࡶ௒ᚋࡢᒎ㛤࡜ࡋ࡚⪃࠼ࡽࢀࡿࠋ

Ꮚ࡟୸ࢆ௜ࡅ࡚࠶ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫ ⏣ྜྷۻ‬ᶞ⏕, ᑎ⏣ ᬛᶞ, "Testing cooperativity of chameleon model by sigmoidal oxygen binding curve ofhemoglobin", ➨ 60 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ภ㤋࢔࣮ࣜࢼ࣭ภ㤋ᕷẸ఍㤋 (2022 ᖺ 9 ᭶)(2) ᑿ⏣ 㥴ኴ, ᑎ⏣ ᬛᶞ, "Construction of six-state model of muscle contraction with switched free energy
landscapes and power stroke", ➨ 60 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ภ㤋࢔࣮ࣜࢼ࣭ภ㤋ᕷẸ఍㤋 (2022 ᖺ 9 ᭶)ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫ۻ‬Tomoki P. Terada, Qing-Miao Nie, Masaki Sasai, "A landscape-based view on the stepping movement of myosin

VI", Journal of Physical Chemistry B 126(38), 7262-7270 (2022).

- 140 -

⏕యศᏊ࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟ࡢ⌮ㄽィ⟬ 
7KHRUHWLFDOFDOFXODWLRQVRIPROHFXODUIXQFWLRQVRIELRPROHFXOHVDQG
PROHFXODUDVVHPEOLHV ‫ۑ‬ᯘ㔜ᙪࠊ಴㔜భ㍤ࠊ኱ሙඃ⏕ࠊᒣᮏ⿱⏕ࠊ໭ᮧ┤኱ࠊᯇᒣ⥤ኟࠊすᑿ᐀୍㑻ࠊ㮵಴ၨྐࠊୖ⏣ዲᶵࠊᵽ㔝೺ኴ㑻ࠊᏳᮾᬛ኱ࠊᚚ௦ᕝඞ㍤ࠊྜྷ⏣ᣅᾏࠊỤᑼᬛ᳃ࠊὠᮧᑗᘺ
㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧

1.1.

◊✲┠ⓗ
ኳ↛ගྜᡂ⣔ II㸦PSII㸧ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

36,, ࡢ㓟⣲Ⓨ⏕୰ᚰ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮㘒య࡟ᑐࡋࠊ40005:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ཯ᛂᶵᵓࢆゎ᫂ࡍࡿࠋᮏ◊✲࡛ࡣࠊ㓟⣲ศᏊⓎ⏕ࢧ࢖ࢡࣝࡢ 6 ཬࡧ 6 ≧ែࢆゎᯒࡋࡓࠋࡇ
ࢀࡽࡢ≧ែࡣ 2 ศᏊࡀ⏕ᡂࡍࡿ᭱ࡶ㔜せ࡞≧ែ࡛࠶ࡿࠋ
1.2.

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ࢔ࢽ࢜ࣥࢳࣕࢿࣝ *W$5& ࡢගάᛶ໬࡟ࡼࡿ࢖࢜ࣥࢳࣕࢿࣝᙧᡂ࡞࡝ࡢ࢖࢜ࣥ㍺㏦ࡢศᏊᶵᵓࢆ 0' ཬࡧ
40005:)(6&) ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡋࠊࡼࡾᐇ⏝ⓗ࡞ග㑇ఏᏛࢶ࣮ࣝࡢタィࢆ┠ᣦࡍࠋ
1.3.

࢖ࢡ࢜ࣜࣥⓎගࢱࣥࣃࢡ㉁ࡢⓎගไᚚศᏊᶵᵓࡢ⌮ㄽⓗゎᯒⓎගࢱࣥࣃࢡ㉁࢖ࢡ࢜ࣜࣥࡢ໬ᏛⓎග㓝⣲཯ᛂ࡜ࡑࡢ &D ࢖࢜ࣥ⤖ྜ࡟ࡼࡿไᚚࡢศᏊᶵᵓࢆ 0' ཬࡧ
4000 5:)(6&) ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⏝࠸࡚᫂ࡽ࠿࡟ࡍࡿࠋᮏ◊✲࡛ࡣࠊ&D㠀⤖ྜ≧ែ࡟࠾ࡅࡿⓎග཯ᛂᢚไᶵᵓ࡟㛵ࡍࡿゎᯒࢆ⾜ࡗࡓࠋ
1.4.

ඹ᭷⤖ྜᆺ㜼ᐖ๣ศᏊ⤖ྜ࡟㛵ࡍࡿ⌮ㄽⓗゎᯒ(*)5 ࢟ࢼ࣮ࢮࢱࣥࣃࢡ㉁㜼ᐖ๣࡛࠶ࡿ 2VLPHUWLQLE ࡸ 6$56&R9 ឤᰁࡢ⤒ཱྀ⸆࡛࠶ࡿ 1LUPDWUHOYLU ࢆྵࡴඹ᭷⤖ྜ㒊఩࡞࡝ࡀ␗࡞ࡿ」ᩘࡢඹ᭷⤖ྜᆺ㜼ᐖ๣ศᏊ⤖ྜ࡟ᑐࡋ࡚ࠊ0' ཬࡧ 4000 5:)(6&)
ἲࢆ⏝࠸࡚ඹ᭷⤖ྜᙧᡂ㐣⛬ࢆゎᯒࡍࡿࡇ࡜࡟ࡼࡾࠊ㜼ᐖࡢศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࠋ
1.5.

Prestin ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁ࡢ Cl- ࢖࢜ࣥ⤖ྜࡢゎᯒ⫈ぬ࡟࠾࠸࡚⣽⬊⭷㟁఩ࢆ⣽⬊ఙᙇࡢຊᏛⓗ࢚ࢿࣝࢠ࣮࡟ኚ᥮ࡍࡿ SUHVWLQ ࣮ࣔࢱ࣮ࡢ &O ࢖࢜ࣥࡢ⤖ྜ࡟㛵ࡋ࡚ࠊ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒࢆ⾜ࡗࡓࠋ1.6.

ࢮࣟ☢ሙศ⿣᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸ࡓ㟁Ꮚࢫࣆࣥඹ㬆ᐇ㦂ࡢゎᯒศᏊࡢ㟁Ꮚࢫࣆࣥ⮬⏤ᗘࢆ฼⏝ࡋࡓᶵ⬟࡟㛵ࡋ࡚ࠊ୍㐃ࡢ࣏ࣝࣇ࢕ࣜࣥㄏᑟయ࡟ࡘ࠸࡚┦ᑐㄽຠᯝࢆᵝࠎ࡞⌮ㄽ࡛ࣞ࣋ࣝྵࡵࡓ㔞Ꮚ໬Ꮫィ⟬ࡢẚ㍑᳨ウࡋࠊࡉࡽ࡟⌧㇟ㄽⓗ࡞ࣁ࣑ࣝࢺࢽ࢔࡛ࣥ࠶ࡿࢮࣟ᫬ሙศ⿣᭷ຠ
ࣁ࣑ࣝࢺࢽ࢔ࣥ࡬ࡢᑕᙳࢆ⾜࠺ࠋ㧗⢭ᗘ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾ⟬ฟࡉࢀࡓࢮࣟ☢ሙศ⿣᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥ࡜
㟁Ꮚࢫࣆࣥඹ㬆ᐇ㦂࡜ࡢ┦⿵ゎᯒ࡟ࡼࡾ⌮ㄽⓗ࡞ᇶ┙ࢆᵓ⠏ࡍࡿࠋ
1.7.

ᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࢆ⏝࠸ࡓከ᰾㔠ᒓ㘒య༢ศᏊ☢▼ࡢ⌮ㄽⓗゎᯒᮏ◊✲࡛ࡣࢥࣂࣝࢺ࣭ࢽࢵࢣ࣭ࣝ㕲࢖࢜ࣥࡢከ᰾㘒యࢆᑐ㇟࡟ࠊ㛤Ⓨࡋࡓᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࢆᇶ┙࡜ࡋࡓ㔞Ꮚ໬Ꮫィ⟬ᡭἲ࡟ࡼࡾࢫࣆࣥ᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࡢィ⟬ࡋࠊከ᰾㔠ᒓ㘒య༢ศᏊ☢▼ࡢ⌮ㄽⓗゎᯒࢆ⾜࠺ࠋ≉࡟ ' ࢸࣥࢯࣝࡢᅛ᭷್࠿ࡽᐃࡵࡽࢀࡿ ' ್ࡢ➢ྕ࡜኱ࡁࡉࡣ༢ศᏊ☢▼࡜ࡋ࡚ࡢࡕᛶ⬟࡟┤⤖ࡋ࡚࠾ࡾࡇࢀࢆቑ኱ࡉࡏࡿࡼ࠺࡞ᅉᏊࢆ≉ᐃࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ

- 141 -

ᗘ㞀ቨࡢ㧗ࡉࠊࡍ࡞ࢃ

1.8.

⾜ิ✚≧ែἼ᮰ࢲ࢖ࢼ࣑ࢡࢫࢆ⏝࠸ࡓ᣺ື࢚ࢿࣝࢠ࣮⦆࿴㐣⛬ࡢ⌮ㄽⓗゎᯒᮏ◊✲࡛ࡣ㛤Ⓨࡋࡓ⾜ิ✚≧ែᆺࡢἼື㛵ᩘࢆཎᏊ᰾ࡢἼື㛵ᩘ࡜ࡋ࡚⏝࠸ࡿࡇ࡜࡛኱つᶍ⮬⏤ᗘࡢ㔞ᏊἼ᮰ࢲ࢖ࢼ࣑ࢡࢫࢆᐇ⌧ࡍࡿࠋȧඹᙺศᏊࡀ୍ḟඖ᪉ྥ࡟ࢫࢱࢵࢡࡋࡓศᏊ㞟ྜయࡸỈศᏊ࡞࡝ࡢศᏊࢡࣛࢫ
ࢱ୰ࡢ࢚ࢿࣝࢠ࣮⛣ື࣭⦆࿴㐣⛬ࢆᑐ㇟࡟ࠊᐇ㝿ࡢศᏊᵓ㐀ࢆධຊ࡜ࡍࡿ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚⌧ᐇศᏊࡢከ≧ែከయ࣏ࢸࣥࢩࣕࣝࢆィ⟬ࡋࠊࡑࡢୖ࡛ࡢ㔞ᏊἼ᮰ࢲ࢖ࢼ࣑ࢡࢫィ⟬ࢆᐇ⌧ࡍࡿࠋ



2.1.

◊✲᪉ἲࠊィ⟬᪉ἲኳ↛ගྜᡂ⣔ II(PSII)ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

6 ࠾ࡼࡧ 6 ≧ែࡢ␗࡞ࡿࣉࣟࢺࣥ໬≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆࠊ4000 5:)(6&) ἲࢆ⏝࠸࡚Ỵᐃࡋࡓࠋ0' ⣔ࡣ a ཎᏊࢆྵࡳࠊࡲࡓ 40 ⣔ࡣa ཎᏊ࡛ᇶᗏ㛵ᩘࡣ a ࡛࠶ࡿࠋィ⟬ࡣ
4000 ࢖ࣥࢱ࣮ࣇ࢙࣮ࢫࢆ⤌ࡳ㎸ࢇࡔ *$0(66 ࠾ࡼࡧ $PEHU ࢆ⏝࠸࡚⾜ࡗࡓࠋ2.2.

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ

*W$&5 ࡟㛵ࡋ࡚ࠊ୰㛫యᵓ㐀ࣔࢹࣝࠊཬࡧኚ␗యࡢࣔࢹࣝࢆᵓ⠏ࡋࠊ4000 5:)(6&) ⮬⏤࢚ࢿࣝࢠ࣮
ᵓ㐀᭱㐺໬࡟ࡼࡾᵓ㐀ࡢ⢭ᐦ໬ࢆ⾜ࡗࡓࠋࡲࡓࠊ0' ἲࢆ⏝࠸ࡓ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊሷ⣲࢖࢜ࣥ⛣ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆィ⟬ࡋࡓࠋ*W$&5 ࡢ 0' ⣔ࡣa ཎᏊ⣔࡛࠶ࡾࠊィ⟬ࡣ $PEHU ࢆ⏝࠸ࡓࠋ
2.3.

࢖ࢡ࢜ࣜࣥⓎගࢱࣥࣃࢡ㉁ࡢⓎගไᚚศᏊᶵᵓࡢ⌮ㄽⓗゎᯒࡇࢀࡲ࡛࡟ᚓࡽࢀ࡚࠸ࡿ UHVWLQJ ≧ែࡢ 40005:)(6&) ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀࠿ࡽࠊ཯ᛂไᚚ࡟㛵୚ࡍࡿ࡜ᛮࢃࢀࡿ㏆ഐࣄࢫࢳࢪࣥഃ㙐࡬ࡢࣉࣟࢺࣥ⛣ື཯ᛂࠊཬࡧ GLR[HWDQRQH ⏕ᡂ཯ᛂ࡟㛵ࡋ࡚ 4000
5:)(6&) ἲཬࡧ %$5 ἲࢆ⏝࠸ࡓ཯ᛂ⤒㊰ࡢỴᐃ࡜཯ᛂ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡢィ⟬ࢆ⾜࠺ࠋ0'ࢩ࣑࣮ࣗࣞࢩࣙࣥ⣔ࡣ a ཎᏊ⣔࡛࠶ࡾࠊィ⟬ࡣ $PEHU ࢆ⏝࠸࡚⾜ࡗࡓࠋ2.4.

ඹ᭷⤖ྜᆺ㜼ᐖ๣ศᏊ⤖ྜ࡟㛵ࡍࡿ⌮ㄽⓗゎᯒ(*)5 ࢟ࢼ࣮ࢮࢱࣥࣃࢡ㉁࡟ᑐࡋ࡚ࡣ  ಶࡢ㜼ᐖ๣ࠊ6$56&R9 0SUR ࡟ᑐࡋ࡚ࡣ  ಶࡢ␗࡞ࡿ㜼ᐖ๣࡟ᑐࡋ࡚ࠊ⤖ྜ๓≧ែࠊ⤖ྜᚋ≧ែࠊཬࡧ୰㛫≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆ 40005:)(6&) ἲࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ⣔ࡣࠊࡑࢀࡒࢀ a ཎᏊ⣔࡛ࠊ$PEHU ࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ
2.5.

Prestin ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁ࡢ Cl- ࢖࢜ࣥ⤖ྜࡢゎᯒ

3UHVWLQ ࡢ⭷㈏㏻ࢻ࣓࢖ࣥࢆ 323& ⬡㉁஧㔜⭷࡟ᇙࡵࡓ⣔࡟ᑐࡋ࡚ࠊ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ⣔ࡣ  ཎᏊ⣔࡛࠶ࡾࠊ1$0' ཬࡧ $0%(5 ࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ2.6.

ࢮࣟ☢ሙศ⿣᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸ࡓ㟁Ꮚࢫࣆࣥඹ㬆ᐇ㦂ࡢゎᯒࢫࣆࣥ㌶㐨┦஫స⏝࡟ࡼࡿ୍㔜㡯≧ែ࡜୕㔜㡯≧ែ㛫ࡢࢫࣆࣥ⚗ไ㑄⛣ࡢぢ✚ࡶࡾࢆࠊ᫬㛫౫Ꮡࢩࣗࣞࢹ࢕
࣮ࣥ࢞᪉⛬ᘧ࡟ᑐࡍࡿᦤືㄽ࠿ࡽᑟ࠿ࢀࡿࣇ࢙࣑ࣝ㯤㔠ᚊࢆࣇ࣮࢚ࣜኚ᥮࡟ࡼࡾ᫬㛫౫Ꮡᙧᘧ࡟ࡋࡓ⾲ᘧࢆ⏝࠸࡚⾜࠺ࠋᑐ㇟࡜ࡍࡿᖹ㠃ȧ㌶㐨㛫ࡢȧȧ ບ㉳ࡣࡑࡢᑐ⛠ᛶ࠿ࡽᖹ㠃ෆ㍈᪉ྥࡢࢫࣆࣥᡂศ࡟ࡘ࠸࡚ࢫ
ࣆࣥ㌶㐨┦஫స⏝ࢆṇࡋࡃぢ✚ࡶࡿࡓࡵ࡟ࠊᵓ㐀ኚ఩ࡢᦤື㡯࡟ࡘ࠸࡚ࡢ࣊ࣝࢶ࣋ࣝࢢ̽ࢸ࣮ࣛຠᯝࢆྵࡵ
ࡿࠋィ⟬࡟ࡣ㔞Ꮚ໬Ꮫࢯࣇࢺ 25&$ ࡜㛤Ⓨࡋࡓ LQKRXVH ࡢ㔞Ꮚ໬Ꮫィ⟬ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡍࡿࠋ
2.7.

ᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࢆ⏝࠸ࡓከ᰾㔠ᒓ㘒య༢ศᏊ☢▼ࡢ⌮ㄽⓗゎᯒゎᯒᑐ㇟࡜ࡍࡿࢥࣂࣝࢺ࣭ࢽࢵࢣ࣭ࣝ㕲࢖࢜ࣥ࡜ཧ↷ศᏊ࡜ࡋ࡚࣐ࣥ࢞ࣥ࢖࢜ࣥࢆ㸯ࠥ㸲ಶ᭷ࡍࡿከ᰾㔠ᒓ㘒య࡟ࡘ࠸࡚ィ⟬ࢆ⾜࠺ࠋ༢ศᏊ☢▼࡜ࡋ࡚ࡢᛶ⬟ࠊࡍ࡞ࢃࡕ

ᗘ㞀ቨࡢ㧗ࡉࢆᐃࡵࡿ ' ࢸࣥࢯࣝࡢィ⟬࡟ࡶࢫࣆࣥ㌶㐨┦஫స⏝ࢆᦤື࡜ࡋ࡚ᢅ࠺ᨃ⦰㏥ᦤືㄽ࡟ᇶ࡙ࡃᡭἲ࡜ࠊࣁ࣑ࣝࢺࢽ࢔ࣥ࡟ྵࡵ࡚ኚศ᭱㐺໬- 142 -

ࡍࡿᡭἲࢆᐇ⾜ࡍࡿࠋィ⟬࡟ࡣ㛤Ⓨࡋࡓ LQKRXVH ࡢ㔞Ꮚ໬Ꮫィ⟬ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡍࡿࠋ
2.8.

⾜ิ✚≧ែἼ᮰ࢲ࢖ࢼ࣑ࢡࢫࢆ⏝࠸ࡓ᣺ື࢚ࢿࣝࢠ࣮⦆࿴㐣⛬ࡢ⌮ㄽⓗゎᯒⅣ⣲ȧඹᙺศᏊࡸศᏊࢡࣛࢫࢱࡢ᣺ື࢚ࢿࣝࢠ࣮෌㓄ศࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࡓࡵከయ࣏ࢸࣥࢩࣕࣝୖ
࡛ࡢ኱⮬⏤ᗘࡢ㔞ᏊἼ᮰ࢲ࢖ࢼ࣑ࢡࢫィ⟬ࢆ⾜࠺ࠋ㛤Ⓨࡋࡓࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊኚศཎ⌮࡟ᇶ࡙ࡁ⾜ิ✚≧ែࡢἼື㛵ᩘࡢ᫬㛫Ⓨᒎࢆィ⟬ࡍࡿࠋ࢚ࢿࣝࢠ࣮ࢧࣥࣉࣜࣥࢢィ⟬࡟ࡣ㔞Ꮚ໬Ꮫࢯࣇࢺ *DXVVLDQ ࡸ
25&$ ࢆ⏝࠸ࠊከయ࣏ࢸࣥࢩࣕࣝࡢసᡂ࡟ࡣ LQKRXVH ࡢ᰾Ἴ᮰ࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡿࠋ



3.1.

◊✲ᡂᯝ
ኳ↛ගྜᡂ⣔ II(PSII)ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

6 ཬࡧ 6 ≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆᚓࡓࠋ6 ≧ែ࡟㛵ࡋ࡚ࡣࠊ」ᩘࡢࣉࣟࢺࣥ໬≧ែ࡟ᑐࡋ࡚ࠊ
6 ≧ែࡢ๓㥑≧ែ࡟ᑐᛂࡍࡿࣉࣟࢺࣥࡀ  ಶ⬺㞳ࡋࡓ≧ែࡢ᭱Ᏻᐃᵓ㐀ࢆỴᐃࡋࡓࠋ6 ≧ែ࡟㛵ࡋ࡚ࡣࠊ
0Q ࡜ 0Q ࡢ㛫ࡢ஧ࡘࡢ㓟⣲ཎᏊࡀ SHUR[LGHࠊVXSHUR[LGHࠊཬࡧ㓟⣲ศᏊ࡜࡞ࡗࡓ≧ែࢆỴᐃࡋࡓࠋ
3.2.

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ'1 ࡟࠾࠸࡚ *OX ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែࡣࠊኳ↛ᆺࡢᬯ≧ែࡢᵓ㐀ࢆ⥔ᣢࡋ࡚࠾ࡾࠊᐇ㦂࡜
FRQVLVWHQW ࡛࠶ࡗࡓࠋࡲࡓࠊ'1 ࡢ *OX ࡀ⬺ࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែࡣࠊ኱ࡁ࡞ᵓ㐀ኚ໬ࡀほࡉࢀ࡚࠸ࡿࠋࡉࡽ࡟ࠊ(4 ཬࡧ (4'1 ኚ␗య࡟࠾࠸࡚ࡶࠊ㢧ⴭ࡞ᵓ㐀ኚ໬ࡀぢࡽࢀࡓࠋࡲࡓࠊኳ↛ᆺࡢගάᛶ໬୰㛫≧ែ࡟ᑐࡋ࡚ሷ⣲࢖࢜ࣥ㏱㐣ࡢ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ&O ࡀ㠀ᖖ࡟ᙉࡃ⤖ྜࡋ࢖࢜ࣥ㏱㐣ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ㠀ᖖ࡟኱ࡁࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
3.3.

࢖ࢡ࢜ࣜࣥⓎගࢱࣥࣃࢡ㉁ࡢⓎගไᚚศᏊᶵᵓࡢ⌮ㄽⓗゎᯒ

5HVWLQJ VWDWH ࡢ㐣㓟໬Ỉ⣲ᇶ࠿ࡽ㏆ഐࡢࣄࢫࢳࢪࣥഃ㙐࡬ࡢࣉࣟࢺࣥ⛣ື⤒㊰ࢆ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬࡛ồࡵࠊ%$5 ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊࣉࣟࢺࣥ⛣ືࡣ኱ࡁࡃ྾⇕ⓗ࡛࠶ࡾࠊࣉࣟࢺ
ࣥ⛣ືࡣᢚไࡉࢀ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊࣉࣟࢺࣥ⛣ື࡜┦㛵ࡋ࡚Ⓨග཯ᛂ୰㛫య࡛࠶ࡿ GLR[HWDQRQH
ࡀ⏕ᡂࡍࡿ཯ᛂ⤒㊰ࡶゎᯒࡋࡓ࡜ࡇࢁࠊ཯ᛂ࢚ࢿࣝࢠ࣮ࡣ኱ࡁࡃ྾⇕ⓗ࡛࠶ࡗࡓࠋᚑࡗ࡚ࠊUHVWLQJVWDWH ࡛ࡣⓎග཯ᛂ㛤ጞࡀᙉࡃᢚไࡉࢀ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
3.4.

ඹ᭷⤖ྜᆺ㜼ᐖ๣ศᏊ⤖ྜ࡟㛵ࡍࡿ⌮ㄽⓗゎᯒ(*)5 ࢟ࢼ࣮ࢮࢱࣥࣃࢡ㉁ࡢඹ᭷⤖ྜᆺ㜼ᐖ๣࡟㛵ࡋ࡚ࡣࠊ཯ᛂࡢጞ≧ែࠊ⤊≧ែࠊཬࡧ࢚ࣀ࣮ࣝᆺ୰㛫≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ࡀ᏶஢ࡋࡓࠋࡲࡓࠊ6$56&R90SUR ࡟㛵ࡋ࡚ࡣࠊ ಶࡢ㜼ᐖ๣ศᏊ࡟ᑐࡋ
࡚཯ᛂࡢጞ≧ែ࠾ࡼࡧ⤊≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ࡀ᏶஢ࡋࡓࠋ
3.5.

Prestin ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁ࡢ Cl- ࢖࢜ࣥ⤖ྜࡢゎᯒ

&O ࢖࢜ࣥࢆ⤖ྜ㒊఩࡟ᣊ᮰ࡋࡓึᮇᵓ㐀࠿ࡽ  ᮏࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ PV ィ⟬ࡋࡓ㸦ィ PV㸧ࠋࡑࡢ⤖ᯝࠊከࡃࡢࢺࣛࢪ࢙ࢡࢺ࡛ࣜ &O ⤖ྜࡀಖᣢࡉࢀࡓࠋࡲࡓ &O ࡀゎ㞳ࡋࡓࢺࣛࢪ࢙ࢡࢺࣜ࡟㛵ࡋ࡚ࡶ」ᩘࡢ
ࢺࣛࢪ࢙ࢡࢺ࡛ࣜ෌⤖ྜࢆほ
3.6.

ࡋࡓࠋᚑࡗ࡚ࠊ&O ࢖࢜ࣥࡣᏳᐃࡋ࡚⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

ࢮࣟ☢ሙศ⿣᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸ࡓ㟁Ꮚࢫࣆࣥඹ㬆ᐇ㦂ࡢゎᯒᮏ◊✲࡛ᑐ㇟࡜ࡍࡿᖹ㠃ȧ㌶㐨㛫ࡢȧȧ ບ㉳ࡢࢫࣆࣥ㌶㐨┦஫స⏝ࢆṇࡋࡃぢ✚ࡶࡿࡓࡵ࡟ࠊᖹ⾮ᵓ㐀࡟࠾ࡅࡿ್ࢆ⏝࠸ࡓ࠸ࢃࡺࡿࢥࣥࢻࣥ㏆ఝ࡟ຍ࠼࡚ᵓ㐀ኚ఩࡜ࢫࣆࣥ㌶㐨┦஫స⏝ࡢ㸰ࡘࡢᦤື㡯࡟ࡘ࠸࡚ࡢ࣊ࣝࢶ࣋ࣝࢢ̽ࢸ࣮ࣛຠᯝࢆྵࡵࡓィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ⤖ᯝ࠿ࡽ୕㔜㡯ບ㉳≧ែࡢ㸱ࡘࡢࢫࣆࣥ๪‽఩ࡑࢀࡒࢀ࡟ᑐࡋ࡚ಶู࡟୍㔜㡯ບ㉳≧ែ࠿ࡽࡢ㡯㛫஺ᕪࡢ㑄⛣㏿ᗘᐃᩘࢆண
3.7.

ᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࢆ⏝࠸ࡓከ᰾㔠ᒓ㘒య༢ศᏊ☢▼ࡢ⌮ㄽⓗゎᯒ- 143 -

ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

ᑐ㇟࡜ࡍࡿࢥࣂࣝࢺ࣭ࢽࢵࢣࣝࡢࢫࣆࣥከ㔜㡯ࡢ㛤Ẇᇶᗏ≧ែ࡟࠾࠸࡚ࠊ' ࢸࣥࢯࣝࢆ㠀┦ᑐㄽⓗ࡞ከཧ↷Ἴື㛵ᩘࢆィ⟬ࡋࡓᚋ࡟ࢫࣆࣥ㌶㐨┦஫స⏝ࢆᦤື࡜ࡋ࡚⪃៖ࡋࡓᨃ⦰㏥ᦤືㄽ࡟ᇶ࡙ࡁィ⟬࠿ࡽ⟬ฟࡋࡓࠋࡲࡓྠ᫬࡟ࠊࢫࣆࣥ㌶㐨┦஫స⏝ࢆࣁ࣑ࣝࢺࢽ࢔ࣥ࡟ྵࡵ࡚ኚศ᭱㐺໬ࡍࡿࡇ࡜࡛┦ᑐㄽⓗ࡞Ἴື㛵ᩘࢆ┤᥋ồࡵࠊᨃ⦰㏥ᦤືㄽࡢ᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࡢᇶᗏ࡟ຍ࠼ࡿ㠀┦ᑐㄽⓗ࡞ᅛ᭷≧ែࢆቑࡸࡍࡇ࡜࡟ࡼࡾ
୧⪅ࡢᕪࡣᑠࡉࡃ࡞ࡗ࡚࠸ࡃࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋ
3.8.

⾜ิ✚≧ែἼ᮰ࢲ࢖ࢼ࣑ࢡࢫࢆ⏝࠸ࡓ᣺ື࢚ࢿࣝࢠ࣮⦆࿴㐣⛬ࡢ⌮ㄽⓗゎᯒ㛤Ⓨࡋࡓ LQKRXVH ࡢ᰾Ἴ᮰ࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊࢹ࢕ࣛࢵࢡ࣭ࣇࣞࣥࢣࣝኚศཎ⌮࡟ᇶ࡙ࡁ⾜ิ✚≧ែࡢἼື㛵ᩘࡢ᫬㛫Ⓨᒎࢆィ⟬ࡋࡓࠋィ⟬ᶵࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ⏝࠸࡚᰾᣺ືࣁ࣑ࣝࢺࢽ࢔ࣥࡢ
እሙ࣏ࢸࣥࢩࣕࣝ࡜ࡋ࡚㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ᰾ࡢከయ࣏ࢸࣥࢩࣕࣝࢆ⟬ฟࡋࡓࠋᐇ㦂࠿ࡽᚓࡽࢀࡿ᫬㛫ศゎࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑᳨ウ࠿ࡽ⌧㇟ࡢ⌮ゎࡍࡿࡓࡵ࡟ࠊィ⟬ࡋࡓ᰾Ἴ᮰ࡢ㌶㊧࡟ᑐࡋ࡚ゎᯒࡋࡓ࠸ཎᏊ᰾ࡢ
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⺮ⓑ㉁࡟ࡼࡿ DNA ຍỈศゎ࡟࠾ࡅࡿ⁐፹ࡢᙺ๭The role of solvent in DNA hydrolysis with a protein‫୕ۑ‬ᯇ⨾㤶ࠊᯇ⏣ᾴኴ㑻ࠊ኱す฿ࠊධబṇᖾ㸦஑ᕞᕤᴗ኱Ꮫ᝟ሗᕤᏛ◊✲㝔㸧1◊✲┠ⓗ⺮ⓑ㉁࡟ࡼࡿ DNA ຍỈศゎ࡟࠾ࡅࡿ⁐፹ࡢᙺ๭ࢆ᥈ࡿࡓࡵࠊ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚཯ᛂ㐣⛬ࠊ≉࡟㑄⛣≧ែ࡟࠾ࡅࡿ཯ᛂ㒊఩ࡢ❧యᵓ㐀ࡢྍど໬࡜ゎᯒࢆ⾜࠺ࡇ࡜ࢆ┠ᶆ࡜ࡋࡓࠋࡲࡓࠊSTCSB [1]࡟㔞Ꮚ໬Ꮫィ⟬ᶵ⬟ࢆ㏣ຍࡋࡓࠋI ᆺࡢไ㝈㓝⣲࡛࠶ࡿ EcoRV ࡢ DNA ษ᩿཯ᛂࢆᡃࠎࡢ◊✲ᐊ࡛ࡣ◊✲ࡋ࡚ࡁࡓ[2,3]ࠋᙜ◊✲ᐊࡢ኱すࡣ DNA ษ᩿๓ࡢ EcoRV̽DNA 」ྜయࡢ X ⥺⤖ᬗᵓ㐀ࢆᇶ࡟ QM/MM MD ィ⟬ࢆ⾜ࡗࡓ[2,3]ࠋᙜ◊✲ᐊࡢ୕ᯇࡢ QM/MM MD ࡟ࡼࡿ DNA ษ᩿཯ᛂ࡟࠾ࡅࡿཎᏊ఩⨨ࡢື⏬సᡂ࡟ࡼࡾࠊ཯ᛂ࡟㛵ಀࡍࡿࣉࣟ
ࢺࣥ⛣ືࡢᵝᏊࡀࢃ࠿ࡗ࡚ࡁࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲไ㝈㓝⣲ EcoRV ࡣ II ᆺࡢไ㝈㓝⣲࡛࠶ࡾࠊDNA ຍỈศゎ࡟஧౯ࡢ㔠ᒓ࢖࢜ࣥ Mg2+ ࢖࢜ࣥࢆᚲせ࡜ࡍࡿ.

࣍ࣔࢲ࢖࣐࣮(subunit A ࡜ B ࠿ࡽᡂࡿ)࡛࠶ࡿ EcoRV ࡣࠊࡑࢀࡒࢀࡢࢧࣈࣘࢽࢵࢺࡀ DNA ࡢ 2 㔜ࡽࡏࢇࡢ㸯ᮏࡎࡘࡢࢾࢡࣞ࢜ࢳࢻ࡜⤖ྜࡍࡿ. ᡃࠎࡢ◊✲ᐊ࡛ࡣࡇࢀࡲ࡛࡟ࠊ㔞Ꮚ໬Ꮫィ⟬(QM/MM metadynamics)ࢆ
⾜࠺ࡇ࡜࡛ DNA ษ᩿ࡢ㸰ࡘࡢ཯ᛂ⤒㊰ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ[2-3]. 1 ࡘࡣ associative reaction path ࡛࠶ࡾࠊồ᰾๣ࡢỈศᏊࡲࡓࡣỈ㓟໬≀࢖࢜ࣥࡀ scissile ࣜࣥ㓟ᇶࡢࣜࣥཎᏊ࡟࢔ࢱࢵࢡࡍࡿ཯ᛂ⤒㊰࡟┦ᙜࡍࡿ. ࡶ࠺ 1
ࡘࡣ dissociative reaction path ࡛࠶ࡾ scissile bond ࡢ㛗ࡉࡀඛ࡟኱ࡁࡃ࡞ࡾᚋ࠿ࡽồ᰾๣ࡢỈศᏊࡲࡓࡣỈ㓟໬≀࢖࢜ࣥࡀ scissile ࣜࣥ㓟ᇶࡢࣜࣥཎᏊ࡟࢔ࢱࢵࢡࡍࡿ཯ᛂ࡛࠶ࡿ. ௒ᅇࡢ◊✲࡛ࡣࠊsubunit A ࡜ B ࡢ
dissociative reaction path ࡜ associative reaction path ࡢྜィ 4 ࡘࡢࢣ࣮ࢫ࡟ࡘ࠸࡚ࠊศᏊࢢࣛࣇ࢕ࢵࢡࢫࢆ⏝࠸ࡓື⏬ࢆసᡂࡋẚ㍑ࡍࡿࡇ࡜࡛཯ᛂ⤒㊰࡟࠾ࡅࡿලయⓗ࡞ࣉࣟࢺࣥ⛣ືࢆゎᯒࡋࡓ. ྍど໬࡟ࡣศᏊࢢࣛࣇ
࢕ࢡࢫࢯࣇࢺ࢙࢘࢔ UCSF Chimera ࢆ౑⏝ࡋࠊ཯ᛂ㒊఩࡛ࡢཎᏊ㛫⤖ྜࡣཎᏊ㛫㊥㞳࡟ᇶ࡙ࡁ⾲♧/㠀⾲♧ࢆ⾜࠺ᶵ⬟ࢆ㏣ຍࡍࡿ◊✲ᐊ⮬సࢶ࣮ࣝࢆ⏝࠸ࡓ.

3◊✲ᡂᯝ㔞Ꮚ໬Ꮫィ⟬࡟ࡣࠊX ⥺⤖ᬗᵓ㐀 1rvb ࢆฟⓎᵓ㐀࡟ࡋࡓྂ඾ⓗ࡞ศᏊືຊᏛ࡟ࡼࡾᚓࡽࢀࡓ཯ᛂ๓㥑యࡢᵓ㐀[2]ࢆ⏝࠸࡚࠸ࡿࠋࡑࡢࡓࡵࠊᵓ㐀 1rvb ࡛ࡳࡽࢀࡓ㸰ࡘࡢࢧࣈࣘࢽࢵࢺࡢᵓ㐀ࡢ㐪࠸ࡀ཯ᫎࡉࢀ࡚࠸ࡿࠋ
EcoRV ࡜ DNA ࡢ┦ᑐ఩⨨ࡀ Mg2+ ࢖࢜ࣥࡀᏑᅾࡋ࡞࠸ሙྜࡢ」ྜయࡢ X ⥺⤖ᬗᵓ㐀(1rva)࡜࡯ࡰኚࢃࡽ࡞࠸
subunit A ࡛ࡣࠊdissociative reaction path ࡀ୺࡞⤒㊰࡜⪃࠼ࡽࢀࡿ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࡀᚓࡽࢀࡓ. ୍᪉ࠊ
EcoRV ࡜ DNA ࡢ┦ᑐ఩⨨࡟࠾࠸࡚ scissile ࣜࣥ㓟ᇶࡀ Ile91 ௜㏆(site I)ࡢ Mg2+ ࢖࢜ࣥ࡜ࡼࡾ㏆࡙࠸ࡓᵓ㐀ࢆᣢࡘ subunit B ࡛ࡣࠊdissociative reaction path ࡜ associative reaction path ࡢ཮᪉ࡀ཯ᛂ⤒㊰࡜ࡋ࡚༑ศ࡜ࡾ࠺ࡿ
⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࢆᚓ࡚࠸ࡿ. 㸰ࡘࡢ཯ᛂᗙᶆ࡟ࡣࠊồ᰾๣ࡢỈศᏊࡢ㓟⣲ཎᏊ࡜ scissile ࣜࣥ㓟ᇶࡢࣜࣥཎᏊ࡜ࡢ㊥㞳(RC1)࡜ scissile bond ࡢ㛗ࡉ(RC2)ࢆ⏝࠸ࡓ. QM/MM ࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆྍど໬ࡍࡿࡇ࡜࡛
཯ᛂ୰࡟࡝ࡢࡼ࠺࡟ࣉࣟࢺࣥࡀ⛣ືࡋ࡚࠸ࡿ࠿ࢆほᐹࡋࡓࠋࡑࡢ⤖ᯝࠊࣉࣟࢺࣥ⛣ື㏵୰ࡢᏙ❧ࡋࡓࣉࣟࢺ
ࣥࡢ⾲♧ࡶྍ⬟࡟࡞ࡗࡓ. ⣬㠃ࡢ㒔ྜ࠿ࡽࠊࡲࡎࠊ4 ࡘࡢ path ࡢ࠺ࡕ subunit B ࡢ dissociative reraction pathࡢ⤖ᯝࡢࡳලయⓗ࡟♧ࡍ. Subunit B, dissociative reaction path ࡣḟࡢࡼ࠺࡟࡞ࡗ࡚࠸ࡓ. Step 1: ཯ᛂጞ≧ែ㹰

- 145 -

ࡘࡲࡾຍỈศゎ๓࡛ࡣࠊLys92, Asp90 ࡣ㟁㞳≧ែࠊᇶ㉁࡜ồ᰾๣ࡢ㸰ࡘࡀỈศᏊࡢ≧ែ (RC1=3.0Å,RC2=1.6Å).
Step 2: scissile bond ࡢษ᩿ࡀ⾜ࢃࢀࡿ. Step 3: Lys92 ࠿ࡽ Asp90 ࡬ࣉࣟࢺࣥࡀ⛣ືࡋࠊLys92 ࡜ Asp90 ࡢ୧᪉ࡀ㟁Ẽⓗ࡟୰ᛶ≧ែ࡟࡞ࡿ (RC1=3.0Å,RC2=2.2Å, ᅗ 1 top). Step 4: ồ᰾๣ࡢỈศᏊࡢࣉࣟࢺࣥࡀ Lys92 ࡬⛣
ືࡍࡿ (RC1=2.4Å, RC2=2.7Å, ᅗ 1 bottom). Step 5: ồ᰾๣ࡢỈศᏊࡀ scissile ࣜࣥ㓟ᇶࡢࣜࣥཎᏊ࡜⤖ྜࡍࡿ(RC1=1.8Å, RC2=2.7Å). Step 6: ᇶ㉁ࡢỈศᏊࡢࣉࣟࢺࣥࡀ DNA ࡢ 6 ṧᇶ┠ࡢࢳ࣑ࣥࡢ O3̓ ࡟⛣ືࡋࠊ

Lys92 ࡢࣉࣟࢺࣥࡀᇶ㉁ࡢỈศᏊࡢỈ㓟໬≀࢖࢜ࣥ࡬⛣ືࡍࡿ (RC1=1.8Å, RC2=2.7Å).
ࡉࡽ࡟ 4 ࡘࡢ path ࡢẚ㍑࠿ࡽࡣ௨ୗࡢࡇ࡜ࡀࢃ࠿ࡗࡓࠋLys92 ࡀồ᰾๣ࡢỈศᏊࡢࣉࣟࢺࣥࢆዣ࠺࡟ࡣഃ
㙐ࡀ㟁Ẽⓗ࡟୰ᛶ࡛࠶ࡿᚲせࡀ࠶ࡿࡀࠊ4 ࡘࡢࡍ࡭࡚ࡢ path ࡟ࡘ࠸࡚ Lys92 ࠿ࡽ Asp90 ࡬┤᥋ࣉࣟࢺࣥࡀ⛣ືࡋ୧ṧᇶࡀ㟁㞳≧ែ࠿ࡽ㟁Ẽⓗ࡟୰ᛶ࡟࡞ࡿࡇ࡜ࡀ཯ᛂࡢ᭱ึࡢẁ㝵࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ┤᥋ほᐹ࡛ࡁࡓ.
⥆࠸࡚㉳ࡇࡿࠊscissile ࣜࣥ㓟ᇶࡢ P, O1, ࡑࡋ࡚ O2 ࡀ࡯ࡰ୍ᖹ㠃࡟࡞ࡿ scissile ࣜࣥ㓟ᇶࡢࠕ཯㌿ࠖࡣࠊ⮬⏤࢚ࢿࣝࢠ࣮ࡢᴟ኱࡟ࡣ࡞ࡗ࡚࠸ࡿࡀࠊ1 ࡘࡢ path (subunit A ࡢ dissociative reaction path) ௨እࡣ᭱኱(཯ᛂࡢᚊ㏿)࡟࡞ࡗ࡚࠸࡞࠿ࡗࡓ. ཯㌿࡟ࡣ࿘ࡾࡢゐ፹ṧᇶࡸ⁐፹ศᏊࡢᐤ୚ࡀ኱ࡁ࠸ྍ⬟ᛶࡀ♧ࡉࢀࡓ. ࡲࡓࠊồ᰾๣ࡢỈศᏊ࠿ࡽࣉࣟࢺࣥࢆዣ࠸Ỉ㓟໬≀࢖࢜ࣥ࡟ࡍࡿሷࡢᙺ๭ࢆ Lys92 ࡀᣢࡗ࡚࠸ࡿࡇ࡜ࡀࠊsubunit Aࡢ associative reaction path ࢆ㝖ࡃ 3 ࡘ path ࡛ほᐹࡉࢀࡓ[3]. ồ᰾๣ࡢỈศᏊࡀࣉࣟࢺࣥࢆኻࡗ࡚Ỉ㓟໬≀࢖࢜ࣥ࡟࡞ࡿ㐣⛬࡛⮬⏤࢚ࢿࣝࢠ࣮ࡢᴟ኱(཯ᛂࡢᚊ㏿)࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ subunit A ࡜ B ࡢ dissociative
reaction path ࡛ඹ㏻ࡋ࡚࠸ࡓ. Subunit B ࡢ associative reaction path ࡣỈ㓟໬≀࢖࢜ࣥ࡟࡞ࡗࡓᚋࠊ┤᥋ scissileࣜࣥ㓟ᇶࡢ P ࡟⤖ྜࡍࡿࡇ࡜ࡀ⮬⏤࢚ࢿࣝࢠ࣮ࡢᴟ኱࡟࡞ࡗ࡚࠸ࡓ. ࡑࡢᚋࡢࣉࣟࢺࣥ⛣ືࠊ≉࡟ᇶ㉁ࡀỈ㓟໬≀࢖࢜ࣥ࠿ࡽࣉࣟࢺࣥࢆᚓ࡚ỈศᏊ࡟ᡠࡿࡓࡵࡢ⛣ື࡟࠾࠸࡚ࠊ
subunit A ࡟ࡘ࠸࡚ࡣ Asp90 ࡀࣉࣟࢺ࣮ࣥࣜࣞࡢᙺ๭ࢆᯝࡓࡋ࡚࠸ࡓ.
Subunit B ࡢ㸰ࡘࡢ path ࡛ࡣ Lys92 ࡀồ᰾๣ࡢỈ࠿ࡽࣉࣟࢺࣥࢆዣ࠺
ሷࡢᙺ๭ࢆࡋ࡚࠸ࡓ. ୍᪉ࠊsubunit A ࡢ㸰ࡘࡢ path ࡛ࡣࠊồ᰾๣ࡣỈศᏊࡢࡲࡲ P ࡟࢔ࢱࢵࢡࡋࠊྠ᫬࡟ Asp90 ࡀồ᰾๣ࡢࣉࣟࢺࣥࢆཷࡅ
ྲྀࡗ࡚࠸ࡿ. ࡲࡓࠊsubunit A ࡢ 2 ࡘࡢ path ࡛ࡣࠊsubunit B ࡜ྠࡌࡼ࠺
࡟⮬⏤࢚ࢿࣝࢠ࣮ࡀ᭱኱࡟࡞ࡿ㝿࡟ồ᰾๣ࡀ Lys92 ࡟ࣉࣟࢺࣥࢆዣࢃࢀ
Ỉ㓟໬≀࢖࢜ࣥ࡞ࡿ. ⮬⏤࢚ࢿࣝࢠ࣮ࡀ᭱኱࡟࡞ࡗࡓᚋ࡟ồ᰾๣ࡀࣉࣟ
ࢺࣥࢆ෌ᗘཷࡅྲྀࡾỈศᏊ࡟ᡠࡿࡇ࡜࡛ࣉࣟࢺࣥࢆ Asp90 ࡟Ώࡍࡇ࡜ࡀ
࡛ࡁࡿ࡜⪃࠼ࡿࡇ࡜࡛ 4 ࡘࡢ path ࡀ⤫୍ⓗ࡟ㄝ࡛᫂ࡁࡿ.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃⓎ⾲ணᐃ:ICBP2023, 2023 ᖺ 8 ᭶ 14 ᪥̽17 ᪥, ࢯ࢘ࣝ, 㡑ᅜ.

Ⓨ⾲ணᐃ: ➨ 45 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘, 2023 ᖺ 10 ᭶ 18 ᪥̽20 ᪥, ᒣᙧᕷ.

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ࡵ㸪ࡇࡢࡼ࠺࡞ཎᏊࡢᑟධࡣ㞴ࡋ࠸࡜ண᝿ࡉࢀࡿ㸬ᮏ◊✲࡛ࡣ㸪ࡇࡢཎᏊᑟධࢆᐇ⌧ࡍࡿྜᡂἲࡢ㛤Ⓨࡢࡓࡵ㸪཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬' ศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ 17&KHP ࡢ 5&&6 ࢧ࣮ࣂ࡛ࡢᩚഛ
௒ᖺᗘࡣࢩࢫࢸ࣒ࡢ᭦᪂࡟࠶ࢃࡏ㸪᪂⎔ቃ࡛ࡢ 17&KHP ࡢࣅࣝࢻࡸࢸࢫࢺࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬- 151 -

◊✲᪉ἲࠊィ⟬᪉ἲ$ ⤖ྜࢡࣛࢫࢱ࣮⌮ㄽࡢ㛤Ⓨ஧㔜༨᭷ᑐ⤖ྜࢡࣛࢫࢱ࣮ S&&'  ⌮ㄽࡣ㟼ⓗ㟁Ꮚ┦㛵ࢆグ㏙ࡍࡿୖ࡛ඃࢀࡓᛶ⬟ࢆᣢࡘ࡜࠸࠺ሗ࿌ࡀ࠶
ࡿ㸬ࡑࡇ࡛ᡃࠎࡣ༢ບ㉳ࢆྵࡴࡼ࠺࡟ᨵⰋࡋ㸪ືⓗ㟁Ꮚ┦㛵ࢆ ) ἲ࡟ࡼࡾ㝧࡟ᢅ࠺⤖ྜࢡࣛࢫࢱ࣮ἲ
S&&6')  ࢆ㛤Ⓨࡋࡓ㸬ࡲࡓ㸪S&&6') ἲ࡛ࡣ㸪㧗⢭ᗘィ⟬ࡢࡓࡵࡢືⓗ┦㛵ࡀࡲࡔ༑ศ࡟グ㏙ࡉࢀ࡞࠸㸬ࡑࡇ࡛㸪ࢫࣆࣥ㐺ᛂࢆ⏝࠸ࡓ᪂ࡓ࡞࢔ࣉ࣮ࣟࢳ࡛࠶ࡿ &&6') ἲࡶ㛤Ⓨࡋࡓ㸬ࡇࢀࡽࡢ᪉ἲࢆᡃࠎࡢ
㛤Ⓨࡋ࡚࠸ࡿࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡋࡓ㸬% ኱つᶍࢡࣛࢫࢱ࣮ศᏊࡢ 03 ィ⟬࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨᡃࠎࡀ㛤Ⓨࡋࡓ 5($/JR ࡟ࡼࡾィ⟬ࢆ⾜ࡗࡓ㸬5($/JR ࡣ㸪 ḟࡢ 0¡OOHU±3OHVVHW ᦤື⌮ㄽ㸦03㸧ࢆ⏝࠸ࡓ኱つᶍศᏊࢡࣛࢫࢱ࣮ࡢ࢚ࢿࣝࢠ࣮໙㓄ࢆ㧗㏿࠿ࡘຠ⋡ⓗ࡟ホ౯ࡍࡿࣇࣛࢢ࣓ࣥࢺ࣮࣋ࢫࡢ࢔ࣝࢦࣜࢬ࣒
࡛࠶ࡿ㸬ࡇࡢ᪉ἲࡢᮏ㉁ࡣ㸪+DUWUHH±)RFN +)  ᡂศ࡜┦㛵ᡂศࡢ᥎ᐃࢆศ㞳ࡍࡿࡇ࡜࡛࠶ࡿ㸬+) ࢚ࢿࣝࢠ࣮
࡜໙㓄ࡣ᏶඲ィ⟬ࢆ⾜࠺ࡇ࡜࡛ᚓࡽࢀࡿ㸬ྛࣔࣀ࣐࣮ࡢ┦㛵࢚ࢿࣝࢠ࣮໙㓄ࡣ㸪ࡑࢀࢆ୰ᚰ࡜ࡋࡓࣇࣛࢢ࣓
ࣥࢺࡢ㏆ഐࢆ㏆ఝࡍࡿࡇ࡜࡛ᚓࡽࢀࡿ㸬& .HJJLQ ᆺ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺࡢྜᡂ⤒㊰࡟㛵ࡍࡿ◊✲ձ࢟ࣕࢵࣉ㒊ࡀḞᦆࡋࡓ .HJJLQ ᆺ 327>:2+@í࡬ࡢࣉࣟࢺࣥ࡜ࡢ࢖࢜ࣥ஺᥮࡟ࡼࡿ࣊ࢸࣟཎᏊࡢᑟධ
཯ᛂ࡜ղ࢟ࣕࢵࣉ㒊㝖ཤ࣭ᙧᡂ࡟㛵ࢃࡿ .HJJLQ ᆺ 327 ࡢ࢟ࣕࢵࣉᙧᡂ཯ᛂ࡟ࡘ࠸࡚㸪ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙࠸ࡓ➨୍ཎ⌮ィ⟬࡟ࡼࡾ㸪཯ᛂ⤒㊰ࢆ᥈⣴ࡋࡓ㸬཯ᛂձ࡛ࡣ࣊ࢸࣟཎᏊ ; &X㸪&G㸪=Q㸪,Q㸪6Q㸪
6L㸪3࡜ࡍࡿ⣔ࢆ㸪཯ᛂղ࡛ࡣ ; 3࡜ࡋ㸪ࣄࢻࣟ࢟ࢩᇶᑐࡢ཯ᛂ࡟ࡼࡿ⬺Ỉ⦰ྜ࡜ࡋ࡚୕㔞యࡀ୍ẁ࡛⦰ྜࡍࡿ⣔ >3:2+@í 㸩 >:2+@ ĺ >3:2@í 㸩 +2 ࡜୕ࡘࡢ༢㔞యࡀ㏲ḟ୕ẁ࡛⦰ྜࡍࡿ⣔>3:2+@í 㸩 >:2+@ ĺ >3:2@í 㸩 +2 ࢆィ⟬ᑐ㇟࡜ࡋࡓ㸬⁐፹ࡢຠᯝࢆㄪ࡭ࡿࡓࡵ㸪&2602
ἲࢆ⏝࠸࡚ẚㄏ㟁⋡ İ 㸪㸪 ࡛ࡢィ⟬ࡶ⾜ࡗࡓ㸬ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ 17&KHP ࢆ⏝࠸㸪཯ᛂ⤒㊰᥈⣴
ࡣ 1XGJHG(ODVWLF%DQG 1(%  ἲ࡟ࡼࡾ⾜ࡗࡓ㸬ィ⟬ࣞ࣋ࣝࡣ Ȧ%;'GHI693 ࡜ࡋ㸪:㸪&G㸪,Q㸪6Q ࡟ࡣ┦ᑐㄽຠᯝࡀ⧊ࡾ㎸ࡲࢀࡓ᭷ຠෆẆ࣏ࢸࣥࢩࣕࣝࢆ౑⏝ࡋࡓ㸬' ศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ 17&KHP ࡢ 5&&6 ࢧ࣮ࣂ࡛ࡢᩚഛ
ࡇࢀࡲ࡛ࡢ 5&&6 ࢩࢫࢸ࣒࡛ࡣ ,QWHO ࢥࣥࣃ࢖࡛ࣛ 17&KHP ࢆࣅࣝࢻࡋ࡚࠸ࡓࡀ㸪᭦᪂࡟ࡼࡾィ⟬ࣀ࣮ࢻ
ࡢ &38 ࡀ $0' (3<& ࡟ኚ᭦ࡉࢀ㸪᪂ࡓ࡞ࢥࣥࣃ࢖ࣛ࠾ࡼࡧࣛ࢖ࣈ࣮ࣛࣜࡀ฼⏝ྍ⬟࡟࡞ࡗࡓ㸬ࡑࡇ࡛㸪ୗグࡢ⤌ࡳྜࢃࡏ࡛ࣅࣝࢻࡋ㸪ࡲࡓᑠศᏊࡢィ⟬ࢆ⾜࠺ࡇ࡜࡛ṇᖖ࡟ືసࡋ࡚࠸ࡿ࠿☜ㄆࡋࡓ㸬&&&;;)&*&&  *&& $2&&  03, 09$3,&+  2SHQ03,  %/$6/$3$&. 2SHQ%/$6 
$2&/




◊✲ᡂᯝ

$ ⤖ྜࢡࣛࢫࢱ࣮⌮ㄽࡢ㛤Ⓨ
S&&6') ἲ࡟ࡼࡾ㸪᏶඲࡞஧㔜ບ㉳₇⟬Ꮚࢆ⏝࠸ࡓᶆ‽ⓗ࡞᪉ἲ㸦&&6')㸧࡟ẚ࡭ィ⟬つᶍࢆ኱ᖜ࡟
๐ῶ࡛ࡁ㸪S&&' ἲ࡟ẚ࡭ືⓗ┦㛵ࡢグ㏙ࢆᨵၿࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸬&&6') ἲ࡛ࡣ㸪஧㔜ບ㉳࡟ࢫࣆࣥ㐺ᛂࡋࡓ୍㔜㡯᣺ᖜࢆ⏝࠸ࡿ㸬୕㔜㡯஧㔜㡯ບ㉳ࡣᚑ᮶ἲ࡛ࡣ↓どࡉࢀ㸪㝧࡞┦㛵ἲ࡛ࡣᨃఝⓗ࡞஧㔜㡯ບ㉳࡜ࡋ࡚ᐇ⿦ࡋࡓ㸬ࡇࢀ࡟ࡼࡗ࡚㸪᏶඲࡞ &&6' ἲ࡛ࡣᙉ┦㛵⣔ࡢ㠀≀⌮ⓗ࡞⤖ᯝ࡟ࡘ࡞ࡀࡿ୍㔜㡯࡜୕㔜- 152 -

㡯ࡢ஧㔜㡯ບ㉳ࡢ࢝ࢵࣉࣜࣥࢢࢆ㝖ཤࡋ㸪୕㔜㡯஧㔜ບ㉳ࡢືⓗ┦㛵ࢆ㐺ษ࡟グ㏙࡛ࡁࡿࡼ࠺࡟࡞ࡗࡓ㸬ᅗ  ࡟♧ࡍ㏻ࡾ᭷ᮃ࡞⤖ᯝࡀᚓࡽࢀ࡚࠾ࡾ㸪࣋ࣥࢳ࣐࣮ࢡィ⟬࡞ࡽࡧ࡟໬Ꮫ࡬ࡢᛂ⏝࡟ྥࡅ‽ഛ୰࡛࠶ࡿ㸬% ኱つᶍࢡࣛࢫࢱ࣮ศᏊࡢ 03 ィ⟬࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ⣙  ಶࡢᇶᗏ㛵ᩘࢆྵࡴ &+  ࡜ +2  ࢆྵࡴᵝࠎ࡞኱つᶍศᏊࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚㸪5($/JR ࡢ⢭ᗘ࡜᭷ຠᛶࢆ᳨ドࡋࡓ࡜ࡇࢁ㸪ຠ⋡࡜⢭ᗘࡢ㠃࡛㠀ᖖ࡟᭷ຠ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗᅗ 1 ࡢ FFS97= ᇶᗏࡢ࣏ࢸࣥ

ࡓ㸬5($OJR ࡢ≉➹ࡍ࡭ࡁ฼Ⅼࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿ㸸  03 ἲࡢࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺㸬ᙧᘧⓗ࡞ࢫࢣ࣮ࣜࣥࢢࡀඞ᭹ࡉࢀࡿ㸬   ࢹ࢕ࢫࢡ㸪࣓ࣔࣜ㸪ィ⟬᫬㛫ࡀ኱ᖜ࡟๐ῶࡉࢀࡿ㸬   ୪ิ⎔ቃ࡟᭱㐺㸬   ኱つᶍศᏊࢡࣛࢫࢱ࣮ࡢィ⟬ࡀྍ⬟㸬  ࠶ࡽࡺࡿ࣏ࢫࢺ
+) ἲ࡟ᐜ᫆࡟㐺ᛂ࡛ࡁࡿ㸬   㡰ᛂ≉ᛶ㸸ᇶᗏ㛵ᩘ㸪⌮ㄽࣞ࣋ࣝ㸪ࣂࢵࢡ࢚ࣥࢻࡢ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛ
ࡢไ⣙ࡀ࡞࠸㸬& .HJJLQ ᆺ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺࡢྜᡂ⤒㊰࡟㛵ࡍࡿ◊✲཯ᛂձࢆㄪ࡭ࡓ࡜ࡇࢁ㸪࠸ࡎࢀࡢሙྜࡶ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ㸬⤒㊰ࡢ࢚ࢿࣝࢠ࣮ࢲ࢖
࢔ࢢ࣒ࣛࡢᙧࡣ࣊ࢸࣟཎᏊࡢ✀㢮࡜┿✵ୗ İ  ࠿⁐፹Ꮡᅾ᮲௳ୗ İ 㸪㸪 ࡢ㐪࠸࡟ࡼࡗ࡚␗࡞ࡿ
ࡀ㸪⁐፹Ꮡᅾ᮲௳ୗࡢ᪉ࡀ┿✵ୗࡼࡾ཯ᛂࡣࡼࡾⓎ⇕ⓗ࡟㐍ࡳ㸪࠸ࡎࢀࡢ⣔࡟࠾࠸࡚ࡶࡑࡢ࢚ࢿࣝࢠ࣮㞀ቨࡣ  N- PROí ௨ୗ࡛࠶ࡗࡓ㸬ㄏ㟁⋡ᑟධ࡟ࡼࡿኚ໬ࡣ౯ᩘࡢ኱ࡁ࡞ ;  3࡛≉࡟㢧ⴭ࡛࠶ࡗࡓ ᅗ  ᕥ 㸬⤒㊰࡟ἢࡗࡓᵓ㐀ࡢኚ໬ࢆ☜ㄆࡍࡿ࡜㸪㦵᱁ࡢ㓟⣲࡜࣊ࢸࣟཎᏊࡣ㟼㟁ⓗ࡞┦஫స⏝ࡢࡓࡵ㸪.HJJLQ ᆺ㦵᱁ࡢ㓄⨨࠿ࡽእࢀࡓ࢚ࢿࣝࢠ࣮ࡢ㧗࠸ᵓ㐀ࢆ⤒⏤ࡋ࡚ኚ໬ࡍࡿഴྥࡀ࠶ࡿ㸬ㄏ㟁⋡ࡢᑟධࡣ㸪ࡇࡢ┦஫స⏝ࢆ⦆࿴ࡋ㸪Ᏻᐃ࡞ᵓ㐀࡬ࡢ⛣⾜ࢆ㉳ࡇࡾࡸࡍࡃࡍࡿ࡜⪃࠼ࡽࢀࡿ㸬཯ᛂղ࡟ࡘ࠸࡚ࡶ㸪୕㔞యࡢ⦰ྜ࡜༢㔞య
ࡢ㏲ḟ୕ẁ࡛ࡢ⦰ྜࡢ୧᪉࡛᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ㸬ࡑࡢ⤖ᯝ࡟ᇶ࡙ࡃ࡜㸪ㄏ㟁⋡ࢆ㑅࡭ࡤ୕㔞యࡢ⦰ྜࡢ᪉ࡀ༢㔞యࡢ㏲ḟ୕ẁ࡛ࡢ⦰ྜࡼࡾ࢚ࢿࣝࢠ࣮ⓗ࡟᭷฼࡟㐍ࡴࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࡑࡋ࡚ࡑࢀࡣ༢㔞యࡢ⤖ྜ㓄⨨ࡢ⮬⏤ᗘࡢ㧗ࡉ࡟ࡼࡿࡶࡢ࡜ぢཷࡅࡽࢀ㸪࢚ࢿࣝࢠ࣮ⓗ࡟୙Ᏻᐃ࡞ᵓ㐀ࢆ⤒⏤ࡋ࡚཯ᛂࡀ㐍⾜ࡍࡿሙྜࡀከ࠿ࡗࡓ㸬ࡲࡓ㸪ࡇࢀࡽࡢ⦰ྜ཯ᛂ࡛ࡣ㸪ࣄࢻࣟ࢟ࢩᇶᑐ㛫ࡢᙉ࠸⤖ྜࡀᚲせ࡛཯ᛂձ࡜␗࡞ࡾ㸪┿✵ୗ࡛ࡢ཯ᛂࡣᚲࡎࡋࡶ୙฼࡛ࡣ࡞࠿ࡗࡓ㸬ࡑࡋ࡚୕㔞యࡢ⦰ྜ཯ᛂࡢ࢚ࢿࣝࢠ࣮㞀ቨࡢ್ࡣ」㞧࡞ㄏ㟁⋡౫Ꮡᛶࢆ♧ࡋࡓ㸦ᅗ  ྑ㸧㸬ࡇࢀࡣ㸪ࡇࡢ⣔࡛ࡣ⬺Ỉ⦰ྜࡢ㝿࡟ࣉࣟࢺࣥࡢཷࡅΏࡋ࡟㛵ࢃࡿࢧ࢖ࢺࡀከࡃ㸪㛵ࢃࡿࢧ࢖ࢺࡢ㐪࠸࡟ࡼࡾ୕㔞యࡢ࢖࢜ࣥ໬≧ែࡢ࢚ࢿࣝࢠ࣮ⓗᏳᐃᗘࡀ⁐፹ࡢㄏ㟁⋡࡟ࡼࡗ࡚␗࡞ࡿᙳ㡪ࢆཷࡅࡿࡓࡵ࡜⪃࠼ࡽࢀࡿ㸬


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H    

Ǽ(N-PRO±Ǽ(N-PRO±



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

   









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H 


3DWKOHQJWK%RKUDPXò

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3DWKOHQJWK%RKUDPXòᅗ  ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛ ᕥ ձ ; 3 㸪ྑ ղ WULPHU - 153 -

' ศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ 17&KHP ࡢ 5&&6 ࢧ࣮ࣂ࡛ࡢᩚഛ
᪂ࡋ࠸⎔ቃ࡛ 17&KHP ࢆࣅࣝࢻࡋࡓࡀ㸪17&KHP ࡢᶆ‽ࢸࢫࢺࢭࢵࢺ࡛ࡣ᪂つࡢၥ㢟ࡣぢࡘ࠿ࡽ࡞࠿ࡗࡓ㸬%)ၸࡢ୍Ⅼィ⟬ 0;GHI693  ࢆ 17&KHPVHLDO ∧࡛⾜ࡗࡓ࡜ࡇࢁ㸪ࢥࣥࣃ࢖ࣛ㸪%/$6/$3$&. ࣛ࢖ࣈ࣮࡛ࣛࣜ࠶ࡲࡾᕪࡣぢࡽࢀ࡞࠿ࡗࡓࡀ㸪*18㸪2SHQ%/$6 ࡀ᭱㏿࡛࠶ࡗࡓ㸬ࡑࡇ࡛㸪*18㸪2SHQ%/$6 ࡛
03, ᐇ⿦ࢆኚ࠼࡚ 1 ࡢ୍Ⅼィ⟬ 3%(GHI4=93  ࢆ⾜ࡗࡓ࡜ࡇࢁ㸪09$3,&+ ࡣ 2SHQ03, ࡟ẚ࡭࡚㢧ⴭ࡟㐜࠸ VYVV  ࡇ࡜ࡀุ᫂ࡋࡓ㸬௒ᚋ㸪᪂ 5&&6 ࡛᭱᪂ࡢ 17&KHP ࢆබ㛤ࡍࡿணᐃ࡛࠶ࡿ㸬 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
z:'DZVRQWK-/(6&:RUNVKRS*LURQGHz: 'DZVRQ &KDOOHQJHV DQG$GYDQFHV LQ 6ROYLQJ (LJHQSUREOHPV IRU (OHFWURQLF6WUXFWXUH 7KHRU\ /DXVDQQH
zմ▼ୖ ᛌ ኱ሜ ฼⾜ ୰ᔱ 㝯ே ᯞ ࿴⏨㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍㸪㛗㔝㸪
z:'DZVRQࠕ࣏ࢫࢺࠕᐩᓅࠖୡ௦ࡢィ⟬≀㉁⛉Ꮫࡢᒎᮃࠖຮᙉ఍zỤཱྀ ኱ᆅ㸪ᕝᔱ ⱥభ㸪୰ᔱ 㝯ே 㸪⋢஭ ᑦⓏ㸪 ᖺග໬Ꮫウㄽ఍㸪ி㒔㸪

z:'DZVRQ36,.&RQIHUHQFH/DXVDQQH

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
z%&KDQ:'DZVRQ71DNDMLPD-3K\V&KHP$±   z0=%UHOD<'LGRYHWV0%RF]DU+6DWR71DNDMLPD0-:yMFLN&KHP3K\V/HWW   z

0=DFFDULD/*HQRYHVH:'DZVRQ9&ULVWLJOLR71DNDMLPD:-RKQVRQ0)DU]DQ%0RPHQL31$6
1H[XVSJDF  z0 =DFFDULD: 'DZVRQ '5 .LVK 0 5HYHUEHUL 0 & % GL 3DWWL 0 'RPLQ9 &ULVWLJOLR % &KDQ /
'HOODILRUD)*DEHO71DNDMLPD/*HQRYHVH%0RPHQL6FL5HS   z1,QRXH71DNDMLPD-&KHP3K\V  zմ.+LUDR71DNDMLPD%&KDQ+-/HH-&KHP3K\V  z1,QRXH71DNDMLPD-&RPSXW&KHP±  zմ▼ୖ ᛌ㸪኱ሜ ฼⾜㸪୰ᔱ 㝯ே㸪ᯞ ࿴⏨㸪-&RPSXW&KHP-SQ±   

- 154 -

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ
0XOWLFRS\DQGPXOWLVFDOHVLPXODWLRQRIELRPROHFXOHV‫ۑ‬᳃ḟ ᆂ㸦኱㜰බ❧኱࣭⌮㸧



◊✲┠ⓗ
◊✲௦⾲⪅ࡣࡇࢀࡲ࡛࡟ࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࡢィ⟬⬟ຊࢆ᭱኱㝈࡟ά⏝ࡋ⏕య㧗ศᏊࡢ❧యᵓ㐀ᙧᡂ࣭ᶵ⬟Ⓨ⌧࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ㧗⢭ᗘ࠿ࡘຠ⋡ⓗ࡟⾜࠺ࡇ࡜ࡢ࡛ࡁࡿ᪂つ࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ࡜ࠊࡇࢀࢆᐇ⿦
ࡍࡿࣉࣛࢵࢺࣇ࢛࣮࣒࡜࡞ࡿ࣐ࣝࢳࢥࣆ࣮࣭࣐ࣝࢳࢫࢣ࣮ࣝศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢙࢘࢔ࠕP2libࠖࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࠋࡲࡓࠊࡑࡢ࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜ࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠ⤒㊰᥈⣴ἲ㸦ࢫࢺࣜࣥࢢἲ㸧࡜ᵓ㐀᥈⣴ἲ㸦MSES ἲ㸧ࡢ◊✲㛤Ⓨࢆ⾜ࡗࡓࠋ௒ᖺᗘࡢ◊✲࡛ࡣࠊMSES ἲࡢᛂ⏝◊✲࡜ࡋ࡚ࠊLinear 䝆䝴䝡䜻䝏䞁/HOIL-1L NZF 」ྜయ䛾」ྜయᙧᡂ䝅䝭䝳䝺䞊䝅䝵䞁䚸ཬ䜃䚸ᰂ㌾䛺䝸䞁䜹䞊䛷⤖䜀䜜䛯 Linear 䝆䝴䝡䜻䝏䞁༢య䛾⥙⨶ⓗᵓ㐀᥈⣴䛻ྲྀ䜚⤌䜣䛰䚹ඹྠ◊✲䜢⾜䛳䛶䛔䜛ி㒔኱Ꮫ⌮Ꮫ◊✲⛉䞉᮵ᑿඛ⏕䛜㏆ᖺ䚸㔠ᒓ䜲䜸䞁㓄఩䜢⏝䛔䛯⁐ᾮ NMR 䛻䜘䜚䝗䝯䜲䞁㛫䛾㊥㞳䛰䛡䛷䛺䛟䝗䝯䜲䞁䛾㓄ྥ䜒᳨ฟྍ⬟䛺ゎᯒᡭἲ䜢ᥦ᱌䛧䛶䛚䜚䚸ᮏ◊✲䛾┠ⓗ䛿䚸䛭䜜䜙䛾ᐇ㦂䝕䞊䝍䛸ᑐẚ䛧䛺䛜䜙ศᏊືຊᏛ䠄MD䠅䝅䝭䝳䝺䞊䝅䝵䞁䛾⤖ᯝ䜢᳨ド䛧䛴䛴䚸䝫䝸䝴䝡䜻䝏䞁㙐䛜䝍䞊䝀䝑䝖䝍䞁䝟䜽㉁䜢≉␗ⓗ䛻ㄆ㆑䛩䜛ᵓ㐀ᇶ┙䜢᫂䜙䛛䛻䛩䜛䛣䛸䛸䛧䛯䚹◊✲᪉ἲࠊィ⟬᪉ἲࢩ࣑࣮ࣗࣞࢩࣙࣥࡢึᮇࣔࢹࣝ࡜ࡋ࡚ࡣࠊLinear 䝆䝴䝡䜻䝏䞁䛸 HOIL-1L NZF 䛾」ྜయ⤖ᬗᵓ㐀(PDB䠖3b0a,

chain CD)ࢆ⏝࠸ࡓࠋAMBER ff14SB ࡢຊሙࢆ⏝࠸ࠊNZF ࢻ࣓࢖ࣥ࡟ྵࡲࢀࡿ Zinc finger ࡟ࡣ ZAFF ຊሙࢆ㐺
⏝ࡋࡓࠋMSES ἲࡢィ⟬ࡣࠊࢩࢫࢸ࣒࡟࢖ࣥࢫࢺ࣮ࣝࡉࢀ࡚࠸ࡿศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢙࢘࢔ AMBER࡜⮬๓ࡢࢫࢡࣜࣉࢺ࡟ࡼࡾ⾜ࡗࡓࠋMSES ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊࢱࣥࣃࢡ㉁ࡢ㓄⨨ࡀẚ㍑ⓗ⮬⏤࡟㐠ືࡍࡿࡼ࠺࡞⢒ど໬ࣔࢹࣝຊሙࢆᵓ⠏ࡍࡿᚲせࡀ࠶ࡿࡀࠊᮏ◊✲࡛ࡣࠊ」ྜయᵓ㐀ࢆ᭱Ᏻᐃ࡜ࡋ㑄⛣ⓗ࡟࿘㎶ࢆࡶ༑ศ࡟ືࡅࡿࡼ࠺࡟⢒ど໬ຊሙࣃ࣓ࣛࢱࢆỴᐃࡋࡓࠋࡑࡢ⢒ど໬ࣔࢹࣝ࡜඲ཎᏊࣔࢹࣝࢆ࢝ࢵࣉࣝࡉࡏࡿ
ࡇ࡜࡟ࡼࡾᗈ⠊࡞ࢧࣥࣉࣜࣥࢢࢆᐇ⌧ࡋࡘࡘࠊࣁ࣑ࣝࢺࣥࣞࣉࣜ࢝஺᥮ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊ࢝ࢵࣉࣜࣥࢢࡢ
࡞࠸ࠊ඲ཎᏊຊሙࡢࡳ࡛ࡢᵓ㐀࢔ࣥࢧࣥࣈࣝ࡟᥋⥆ࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿࠋᮏㄢ㢟࡛ࡣࠊ12 ಶࡢࣞࣉࣜ࢝ࢆ
⏝࠸ 400 ns ࡢࣁ࣑ࣝࢺࢽ࢔ࣥࣞࣉࣜ࢝஺᥮ MSES ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ༑ศ࡞ᵓ㐀ࢧࣥࣉࣜࣥࢢࢆᐇ᪋ࡋࡓࠋ
Linear ࢪࣘࣅ࢟ࢳࣥ༢యࡢᵓ㐀ࢧࣥࣉࣜࣥࢢ࡛ࡣࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࡢึᮇࣔࢹࣝ࡜ࡋ࡚ୖグࣔࢹࣝ࠿ࡽ
NZF ࢻ࣓࢖ࣥࢆ㝖࠸ࡓᵓ㐀ࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࢪࣘࣅ࢟ࢳࣥ༢య࡛ࡣࠊ᭱Ᏻᐃ࡜࡞ࡿᵓ㐀ࡀ᝿ᐃ࡛ࡁࡎ⢒ど໬ຊሙࡢసᡂࡀ㞴ࡋ࠸ࡓࡵࠊᵓ㐀᥈⣴࡟ࡣ gREST ἲࢆ㐺⏝ࡋࡓࠋgREST ࡢィ⟬ࡣࠊࢩࢫࢸ࣒࡟࢖ࣥࢫࢺ࣮ࣝ
ࡉࢀ࡚࠸ࡿศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢙࢘࢔ GENESIS ࢆ⏝࠸ࡓࠋ㟼㟁┦஫స⏝࡟ࡼࡾࣘࣅ࢟ࢳࣥ㛫ࡢ㓄⨨ࡀᅛᐃࡉࢀࡀࡕ࡛࠶ࡿࡇ࡜ࢆ⪃៖ࡋࠊࣘࣅ࢟ࢳࣥࡢ㓟ᛶ࣭ሷᇶᛶṧᇶࡢศᏊ㛫┦஫స⏝࡟ࡘ࠸࡚ࡢ

ᗘࢆኚ࠼ࡓࣁ࣑ࣝࢺࢽ࢔ࣥࣞࣉࣜ࢝஺᥮ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆࠊ8 ಶࡢࣞࣉࣜ࢝ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋᮏㄢ㢟࡛ࡣࠊ
NMR ᐇ㦂࡜ࡢᑐᛂࢆぢࡿࡓࡵࠊWild Type ࡔࡅ࡛࡞ࡃ Distal ࣘࣅ࢟ࢳࣥࡢ G75A/G76A ኚ␗య࡟ᑐࡋ࡚ࡶྠ
ᵝࡢィ⟬ࢆᐇ᪋ࡋࡓࠋ༑ศ࡞ᵓ㐀᥈⣴ࡢࡓࡵࠊ2 ࡘࡢࣔࢹࣝ⣔࡛ࡑࢀࡒࢀ 1 Psࠊィ 16Ps ࡢ኱つᶍ MD ィ⟬ࢆᐇ⾜ࡋࠊᚓࡽࢀࡓᵓ㐀࢔ࣥࢧࣥࣈࣝࡢゎᯒࢆ⾜ࡗࡓࠋ- 155 -

◊✲ᡂᯝLinear 䝆䝴䝡䜻䝏䞁/HOIL-1L NZF 」ྜయ䛾◊✲䛷䛿䚸⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡀ」ྜయࢆ୰ᚰ࡜ࡋࡓᖜᗈ࠸ࣇࣛ

ࢵࢺ࡞ࣛࣥࢻࢫࢣ࣮ࣉ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓ㸦ୖᅗ㸧ࠋ1=) ࡀ୺࡟ GLVWDO ࣘࣅ࢟ࢳࣥ࡟⤖ྜࡍࡿࡇ࡜ࠊࡲࡓࠊ୧
᪉ࡢࣘࣅ࢟ࢳࣥ࡜ࢥࣥࢱࢡࢺࡋࡓᵓ㐀࡛ࡶ⠊ᅖࡣ㝈ᐃࡉࢀࡎᗈ⠊࡟ືࡁ࠺ࡿࡇ࡜࠿ࡽࠊࢪࣘࣅ࢟ࢳ࡛ࣥつᐃࡉࢀࡓ  ಶࡢࣘࣅ࢟ࢳ࡛ࣥ 1=) ࡀࢲ࢖ࢼ࣑ࢵࢡ࡟ㄆ㆑ࡉࢀࡿศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

⁐ᾮ୰࡟࠾ࡅࡿࢪࣘࣅ࢟ࢳࣥ㙐ࡢᵓ㐀ᦂࡽࡂࡢ◊✲࡛ࡣࠊNMR ࡛ࡢᐇ㦂ࡀᐇ᪋ࡉࢀࡓ Linear ࢪࣘࣅ࢟ࢳ
ࣥ࡜࣮ࣜࣥ࢝㒊఩ࢆ⨨᥮ࡋࡓ G75/76A ኚ␗య࡟ࡘ࠸࡚ࠊgREST ࡟ࡼࡾ⁐ᾮ୰࡛ࡢᵓ㐀᥈⣴ࢆᐇ᪋ࡋࡓࠋࡑࡢ
⤖ᯝࠊPDB ࡛ぢฟࡉࢀࡿከᵝ࡞⤖ᬗᵓ㐀ࡍ࡭࡚ࢆໟᣓࡍࡿࡼ࠺࡞ᗈ⠊࡞ᵓ㐀࢔ࣥࢧࣥࣈࣝࢆࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ࡟ࡼࡾ⏕ᡂࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ୗᅗ㸧ࠋ௒ᚋࡢ◊✲࡛ࡣࠊᖖ☢ᛶ NMR ࢫ࣌ࢡࢺࣝࢆᚓࡽࢀࡓᵓ㐀࢔ࣥࢧࣥࣈࣝ࠿ࡽ┤᥋ィ⟬ࡋࠊᐇ㦂࡜ࡢᑐᛂࢆྫྷ࿡ࡍࡿࠋࡲࡓࠊࣘࣅ࢟ࢳࣥ㙐ࡢࡼ࠺࡞ᰂ㌾ᛶ࡟ᐩࢇࡔࢱࣥࣃࢡ㉁࡟
ᑐࡍࡿᵓ㐀᥈⣴ἲࡢᨵⰋࢆ┠ᣦࡍࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
1.

᳃ḟᆂࠕ㔜ࡳ௜ࡁ࢔ࣥࢧࣥࣈࣝἲ࡜⏕యศᏊ࡬ࡢᛂ⏝ࠖ➨ 3 ᅇ⏕యศᏊࢩ࣑࣮ࣗࣞࢩ࣭ࣙࣥࣔ
ࢹࣜࣥࢢ◊✲఍ࠊภ㤋ࠊ2022 ᖺ 10 ᭶ 1 ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

Kei Moritsugu, Akinori Kidera, Toru Ekimoto and Mitsunori Ikeguchi, “Binding and unbinding pathways of

peptide substrate on SARS-CoV-2 3CL protease”, Journal of Chemical Information and Modeling. 2023, 63,240-250- 156 -

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ࣮ࣟࢳ
7KHRUHWLFDODSSURDFKRQHOHFWURQLFVWDWHVRIOXPLQHVFHQWPHWDOFRPSOH[HVDQGWKHLUDVVHPEOHGV\VWHPV‫ۑ‬ຍ⸨ ᫀᏊ 㸪బࠎᮌ ࡇࡢ 㸪∾㔝 ♸௓ 㸪㰻⸨ ኱ᑗ 㸪ྜྷ⏣ ᑗᕫ 㸪ᑠᯘ ཌᚿ 㸦 㛵すᏛ㝔኱Ꮫ⏕࿨⎔ቃᏛ㒊ࠊ ໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲㝔㸧◊✲┠ⓗࠊෆᐜ
Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧࢡࣛࢫࢱ࣮ࡣࠊ᭷ᶵ (/ ⣲Ꮚࡸࢭࣥࢧ࣮࡞࡝ࡢᮦᩱ࡜ࡋ࡚ࡶ⯆࿡῝ࡃࠊάⓎ࡞◊✲ࡀᒎ㛤ࡉࢀ࡚࠸ࡿࠋ㧗ຠ⋡࡞Ⓨගᛶ㔠ᒓ㘒య㛤Ⓨࡢࡓࡵ࡟ࡣࠊ㔞Ꮚ཰⋡ࠊⓎගᑑ࿨ࠊⓎග࢚ࢿࣝࢠ࣮ࠊගᏳ
ᐃᛶ➼ࢆไᚚࡍࡿせᅉࢆゎ᫂ࡋࡓศᏊタィࡀᚲせ࡛࠶ࡿࠋࡑࡇ࡛ᮏᥦ᱌࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢᵓ㐀ࡸ㟁Ꮚ≧ែࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ᑐ㇟࡜ࡍࡿ㘒యࡣࠊᮏ◊✲ࢢ࣮ࣝࣉ࡛㛤ⓎࡋࡓⓎගᛶⓑ㔠 ,, 㘒యࡸ㖡 , 㘒య➼࡛࠶ࡿࠋึࡵ࡟ࠊึᮇ

ᵓ㐀ࡢᵓ⠏ࡣࠊ; ⥺ᵓ㐀ゎᯒ࡟ࡼࡾỴᐃࡋࡓᗙᶆࢆ⏝࠸࡚⾜࠸ࠊࡇࢀࢆᚲせ࡟ᛂࡌ࡚ᐦᗘỗ㛵ᩘἲ ')7 ࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࡍࡿ࡜࡜ࡶ࡟ᇶᗏ≧ែࢆィ⟬ࡋࡓࠋḟ࡟ࠊ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ 7'')7 ࢆ⏝࠸࡚ࠊᆶ┤ບ㉳≧ែࢆィ⟬ࡋࡓࠋࡇࢀ࡟ࡼࡾప࠸ࣞ࣋ࣝࡢບ㉳≧ែࡢ᝟ሗࢆᚓࠊ୺せ࡞ບ㉳≧ែ࡟ࡘ࠸࡚ࡣ᭱㐺໬ࢆ⾜ࡗࡓࠋᇶᗏ≧ែ࡜ບ㉳≧ែࡢヲ⣽࡞グ㏙ࢆ㏻ࡌ࡚྾཰࠾ࡼࡧⓎගࢫ࣌ࢡࢺࣝࡢゎ᫂ࢆ⾜࠸ࠊ㧗Ⓨගࡸ࣮࢝ࣛ
ࢳ࣮ࣗࢽࣥࢢࢆᐇ⌧ࡍࡿࡓࡵࡢศᏊᵓ㐀ணࢆ⾜࠸ࠊᐇ㦂໬Ꮫࡢࣇ࢕࣮ࢻࣂࢵࢡ࡟฼⏝ࡋࡓࠋ')7 ࠾ࡼࡧ 7'

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 ࢡ࣑ࣟࢵࢡࢺ࣑ࣜ࣎ࣝࢿࢵࢭࣥࢫࢆ♧ࡍᙉⓎගᛶⓑ㔠 ,, 㘒యᙜ◊✲ᐊ࡛ࡣࠊຊᏛ่⃭࡛Ⓨගࡍࡿ㸦ࢺ࣑ࣜ࣎ࣝࢿࢵࢭࣥ
ࢫ㸧࡜࡜ࡶ࡟ྍ㏫ⓗ࡟ⓎගⰍࢆኚ໬ࡉࡏࡿࠕࢡ࣑ࣟࢵࢡࢺࣜ
࣑࣎ࣝࢿࢵࢭࣥࢫࠖࢆ♧ࡍⓑ㔠 ,, 㘒య⤖ᬗࢆ㛤Ⓨࡋࡓ㸦ྑᅗ㸧ࠋࡑࡇ࡛ࠊࡇࡢⓑ㔠 ,, 㘒య㸦ྑᅗ㸧࡟ࡘ࠸࡚⌮ㄽィ⟬࠿ࡽࡑࡢⓎග≉ᛶࡢヲ⣽ࢆ᳨ウࡋࡓࠋ≉࡟ࠊࡇࡢⓑ㔠 ,, 㘒యࡢⓎගࡣ⤖ᬗ୰࡛ࡢ㔠ᒓ㛫┦஫స⏝࡟⏤᮶ࡋࡓ 00/&7 㑄⛣࡟ᖐᒓࡉࢀࡿࡇ࡜ࡀศග໬Ꮫ

ᐃ࡟ࡼࡾุ᫂ࡋ࡚࠸ࡓࡓࡵࠊ

⌮ㄽィ⟬࡟ࡼࡗ࡚ヲ⣽࡞᳨ドࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ☜࠿࡟ィ⟬࡟ࡼࡗ࡚ồࡵࡽࢀࡓ +202 ࡣ㔠ᒓ㛫࡟㠀ᒁᅾ໬ࡋ࡚࠾ࡾࠊ/802 ࡣ㓄఩Ꮚୖ࡟ᒁᅾ໬ࡋ࡚࠸ࡓࡓࡵࠊࡇ
ࡢ㑄⛣ࡀ 00/&7 㑄⛣࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊࡑࡢ +202/802 ࢠࣕࢵࣉࡣ㓄఩Ꮚୖ࡟ᑟධࡋࡓ
⨨᥮ᇶࡢᔞ㧗ࡉ࡟ࡼࡗ࡚⣔⤫ⓗ࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡶ☜ㄆ࡛ࡁࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊຊᏛ่⃭ࢆ᳨ฟࡍࡿࢭ
ࣥࢧ࣮ࢆ㛤Ⓨࡍࡿࡓࡵࡢ㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ
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 ᙎᛶኚᙧࢆ♧ࡍᙉⓎගᛶⓑ㔠 ,, 㘒యᙜ◊✲ᐊ࡛ࡣࠊ㔠ᒓ㛫┦஫స⏝࡟⏤᮶ࡍࡿ
00/&7 Ⓨගࢆ♧ࡍ࡜࡜ࡶ࡟ࠊ⤖ᬗ࡛࠶ࡾ࡞ࡀࡽ㈇Ⲵࢆ࠿ࡅ࡚ࡶᢡࢀࡎ࡟ᙎᛶኚᙧࢆ♧ࡍⓑ㔠 ,, 㘒య⤖ᬗࢆ㛤Ⓨࡋࡓ㸦ྑᅗ㸧ࠋࡑࡇ࡛ࠊࡇࡢ㘒య⤖ᬗ࡟ࡘ࠸࡚ࠊࡑࡢⓎග⏤᮶ࡢ᳨ド࠾ࡼࡧศᏊ㛫┦஫స⏝࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊィ⟬࡟ࡼࡗ࡚ồࡵࡽࢀࡓ +202 ࡣ㔠ᒓ㛫࡟㠀ᒁᅾ໬ࡋ࡚࠾ࡾࠊ/802ࡣ㓄఩Ꮚୖ࡟ᒁᅾ໬ࡋ࡚࠸ࡓࡓࡵࠊⓎග⏤᮶ࡀ 00/&7 㑄⛣࡛࠶ࡿࡇ࡜ࡀ᳨ドࡉࢀࡓࠋࡲࡓࠊศᏊ㛫┦஫స⏝࡟╔┠ࡍࡿ࡜ࠊࡇࡢ㘒యࡣ㔪≧⤖ᬗࡢ㛗㍈᪉ྥ࡟ᑐࡋ࡚ࡣࣁࣟࢤࣥ㛫┦஫స⏝࡞࡝ࡢ  N- PRO ௨ୗࡢᙅ࠸┦஫స⏝࡛㐃⤖ࡉࢀࡓࢪࢢࢨࢢ㙐ᵓ㐀ࢆ࡜ࡗ࡚࠸ࡓࡢ࡟ᑐࡋࠊ▷㍈᪉ྥ࡟ࡣ ʌʌ ࢫࢱࢵ࢟ࣥࢢ࡟⏤᮶ࡍࡿ
N-PRO ⛬ᗘࡢẚ㍑ⓗᙉ࠸┦஫స⏝ࡀほࡉࢀࡓࠋࡇࡢࡇ࡜࠿ࡽࠊࡇࡢᴟࡵ࡚␗᪉ⓗ࡞┦஫స⏝࠾ࡼࡧࢪࢢࢨࢢ㙐ᵓ㐀ࡀᙎᛶኚᙧࢆྍ⬟࡜ࡋ࡚࠸ࡿ࡜♧၀ࡉࢀࡓࠋᮏᡂᯝࡣຊᏛⓗ࡟ࣇࣞ࢟ࢩࣈࣝ࡞ගᶵ⬟ᮦᩱࢆタィࡍࡿ࠺࠼࡛㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ

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࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋගຎ໬ࡉࡏࡿග※࡜ࡋ࡚/('ࣛࣥࣉ࡟ࡼࡿⓑⰍගࢆศගࡏࡎ࡟⏝࠸ࡓࠋ࣏ࣜ࢖࣑ࢻ⭷࡟࠶ࡽ࠿ࡌࡵ ̽ ᫬㛫ࡲ࡛↷ᑕࡋගຎ໬ࡉࡏࡓヨᩱࢆసᡂࡋࠊࡑࢀࡽ࡟ᑐࡋ;$6ࢫ࣌ࢡࢺࣝࢆྲྀᚓࡋࡓࠋ
ᅗ㸯࡟㓟⣲.➃ࡢ;$6ࢆ♧ࡍࠋ᫬㛫௨ୖࡢග↷ᑕ࡟ࡼࡾࠊ&1⤖ྜษ᩿࡟ࡼࡾ㓟໬ࡉࢀࡓ⏕ᡂ≀⏤᮶ࡢH9ࡢࣆ࣮ࢡࡢࣈ࣮ࣟࢻࢽࣥࢢࡀぢࡽࢀࡿࠋࡲࡓᐦᗘỗ㛵ᩘἲ࡟ࡼࡿ⌮ㄽィ⟬࡟ࡼࡾࠊศᏊᵓ㐀࡜ࡋ࡚ࣆ࣓ࣟࣜ
ࢵࢺ㓟஧↓Ỉ≀̓࢜࢟ࢩࢪ࢔ࢽࣜࣥ 30'$2'$ ᆺࡢ࣏ࣜ࢖࣑ࢻࢆ௬ᐃࡋࠊࣔࣀ࣐࣮ࣔࢹࣝ࠾ࡼࡧ᝿ᐃࡉ
ࢀࡿゎ㞳⏕ᡂ≀ࣔࢹࣝࢆ⏝࠸࡚;$6ࢫ࣌ࢡࢺࣝࢆ⟬ฟࡋࡓࠋỈ࡟ࡼࡿ⤖ྜษ᩿ࣔࢹࣝࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊ
H9௜㏆ࡢࣈ࣮ࣟࢻࢽࣥࢢࢆㄝ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

Intensity (arb. units)

PMDA-ODA+(H2O)2

PMDA-ODA+H2O
PMDA-ODA

530

535

540

545

Photon energy (eV)  ᅗ  㸦ᕥ㸧࣏ࣜ࢖࣑ࢻ⭷ࡢ 2.HGJH;$6 ࢫ࣌ࢡࢺࣝࠋ
㸦ྑ㸧

550

555




  ᾮ⁲ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ㻌ࣂࣝࢡỈࡣᚤどⓗ࡟୙ᆒ୍࡟࡞ࡗ࡚࠾ࡾࠊỈࡢ≧ែ࡟㏆࠸´+LJK 'HQVLW\ /LTXLG +'/ ´࡜ࠊịࡢ≧ែ࡟㏆
࠸´/RZ'HQVLW\/LTXLG /'/ ´ࡢ஧≧ែࡀᏑᅾࡍࡿࡇ࡜ࡀ㌾ ; ⥺Ⓨගศගἲ ;(6 ࡞࡝࡟ࡼࡿඛ➃ィᢏ⾡࡟ࡼࡾ᫂ࡽ࠿࡟ࡉࢀࡘࡘ࠶ࡿࠋḟࡢࢫࢸࢵࣉ࡜ࡋ࡚ࠊỈ࡜≀㉁࡜ࡢΰྜ࡟ࡼࡿỈࡢᶵ⬟Ⓨ⌧ᶵᵓࢆ᥈ࡿࡇ࡜࡛࠶

- 160 -

ࡿࠋᮏ◊✲࡛ࡣỈࡢ⏺㠃ࡢᵓ㐀ࢆ᥈ࡿࡇ࡜࡟╔┠ࡋࠊࣂࣝࢡ࡜⏺㠃ࡢ୧᪉ྵࡴᩘ QP ⛬ᗘࡢᾮ⁲ࢆᑐ㇟࡜ࡋ
ࡓࠋ㐣෭༷㡿ᇦࡢ . ࠿ࡽᾮయࡢỈ࡛࠶ࡿ . ࡲ࡛ศᏊືຊᏛ 0' ィ⟬ࢆ⾜࠸ࠊᾮ⁲ࢆᵓᡂࡍࡿỈศᏊࡢᵓ㐀ࡸ≧ែ࡟ࡘ࠸࡚ㄪᰝࡋࡓࠋ ỈศᏊᩘࢆ      ࡜ࡋࠊ ࡜  ỈศᏊࡣ  . ࠿ࡽ  . ࡲ࡛  . ࡈ࡜࡟ᗘࢆୖ᪼ࡉࡏࠊ ỈศᏊࡣ . ࡜ . ࡢࡳィ⟬ࢆ⾜ࡗࡓࠋ197 ࢔ࣥࢧࣥࣈ࡛ࣝ IV ࡈ࡜࡟ィ QV ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋ0' ィ⟬ࡣ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢯࣇࢺ࢙࢘࢔ࣃࢵࢣ࣮ࢪ *520$&6
7,33 Ỉࣔࢹࣝࢆ⏝࠸ࡓࠋᮏ◊✲࡛ࡣ  ࡘࡢᒁᡤᵓ㐀ᅉᏊ /6,7HWUDKHGUDOLW\Jၺ]HWD ࢆᾮ⁲ࠊ. ࡢࣂࣝࢡỈ࡟㐺⏝ࡋࡓࠋ ᅗ㸱࡟ 7HWUDKHGUDOLW\ ࡢᾮ⁲ࢧ࢖ࢬ౫Ꮡᛶࠊ

ᗘ౫Ꮡᛶࢆ♧ࡍࠋ7HWUDKHGUDOLW\ ࡢ  ௨ୗࡢ್ࢆࡶࡘࡶࡢࡣỈศᏊࡀᾮ⁲ࡢ⾲㠃࡟఩⨨ࡋ࡚࠾ࡾࠊࡍ࡞ࢃࡕ⏺㠃ࡢỈ࡟ᑐᛂࡍࡿࠋࡲࡓ

ᗘࡀୖ᪼ࡍࡿ࡟ࡘࢀ࡚  ௜㏆ࡢࣆ࣮ࢡ࡟ຍ࠼  ௜㏆࡟ࡶࣆ࣮ࢡࡀฟ⌧ࡍࡿࠋࡇࢀࡽࡣ /'/ +'/ ≧ែ࡟ᑐᛂࡍࡿࡶࡢ࡜ゎ㔘࡛ࡁࡿࠋࡲࡓ
ᗘࡀୖ᪼ࡍࡿ࡟ࡘࢀ࡚ /6, ࡢᑠࡉ࡞್ࢆࡶࡘỈศᏊࡢ๭ྜࡀቑຍࡋ࡚࠸ࡃࡇ࡜ࡀࢃ࠿ࡗࡓࠋᑠࡉ࡞ /6, ್ࢆࡶࡘỈศᏊࡣࢡࣛࢫࢱ࣮ࢆᙧᡂࡋ࡙ࡽ࠸ࠊࡍ࡞ࢃࡕ +'/ ≧ែࢆ࡜ࡿഴྥ࡟࠶ࡿ࡜࠸࠺ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸
ࡿࠋࡋࡓࡀࡗ࡚

ᗘࡢୖ᪼࡟ࡼࡾỈศᏊࡢ≧ែࡀ /'/ ࠿ࡽ +'/ ࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࢆ⾲ࡋ࡚࠸ࡿࠋ௨ୖࡼ

ࡾࠊỈࡢᒁᡤᵓ㐀ᅉᏊ࡟ࡼࡾᾮ⁲ᵓ㐀ࡢヲ⣽ࢆ㆟ㄽࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ    ᅗ㸱 ᾮ⁲࠾ࡼࡧ . ࡢỈ࡟ᑐࡍࡿ WHWUDKHGUDOLW\ࠋ ᕥ   . ࡟࠾ࡅࡿᾮ⁲ࡢࢧ࢖ࢬ౫Ꮡᛶࠋ ྑ  ศᏊᾮ⁲ࡢ ᗘ౫Ꮡᛶࠋ


㸱㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
㧗ᶫ㸪ศᏊ⛉Ꮫウㄽ఍㸪 ᖺ  ᭶㸪ᶓ὾㧗ᶫࡽ㸪ᨺᑕග⛉Ꮫྜྠࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪ⲡὠ㧗ᶫ㸪,:35,;6 ᖺ  ᭶㸪ⶶ⋤㸲㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
5)XMLWDet alColloids and Surfaces A: Physicochemical and Engineering Aspects634 SDJHV   ‫ۻ‬/*03HWWHUVVRQet alJ. Non-Crystalline Solids: X14 SDJHV   ‫ۻ‬27DNDKDVKLet alPhys. Rev. Lett.128   SDJHV   ‫ۻ‬5<DPDPXUDet alJ. Phys. Chem. B126    - 161 -

࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉Ꮫ&RPSXWDWLRQDO6FLHQFHIRU(QHUJ\&RQYHUVLRQ0DWHULDOV‫ۑ‬ᒣୗ᫭୍㸪㔠Ꮚṇᚨ㸦ᶓ὾ᕷ❧኱Ꮫ⏕࿨ࢼࣀࢩࢫࢸ࣒⛉Ꮫ◊✲⛉㸧◊✲┠ⓗࠊෆᐜ
ᆅ⌫ᬮ໬࡟ຍ࠼ࠊཎⓎ஦ᨾ࡟క࠺࢚ࢿࣝࢠ࣮༴ᶵᅇ㑊࡟ྥࡅ࡚ࠊኴ㝧ග࢚ࢿࣝࢠ࣮ࡢ฼⏝ᣑ኱ࡣᛴົ࡛

࠶ࡿࠋࡑࡢ࢝ࢠࢆᥱࡿᢏ⾡ࢆ͆┦⏺㠃࡟࠾ࡅࡿ⣲㐣⛬͇ࡢほⅬ࠿ࡽ࡜ࡽ࠼ࠊྛᢏ⾡࡛ồࡵࡽࢀࡿ┦⏺㠃⣲㐣⛬ࡢไᚚ࡜᭱㐺໬࡟ࡘ࠸࡚ࠊィ⟬⛉Ꮫⓗ◊✲࡟ࡼࡾ᳨ウࡍࡿࠋ┦⏺㠃࡟࠾ࡅࡿ⣲㐣⛬ࡢᇶᮏᴫᛕ࡜ࡋ࡚࢚࢟
ࢩࢺ࣭ࣥࢲ࢖ࢼ࣑ࢡࢫࠊ࢟ࣕࣜ࢔⛣ືࠊࣂࣥࢻ࣭࢚ࣥࢪࢽ࢔ࣜࣥࢢࠊ⾲㠃ゐ፹཯ᛂ࡟ὀ┠ࡋࠊ㟁Ꮚᵓ㐀ㄽ࣭཯ᛂㄽ࡟ᇶ࡙࠸ࡓศᏊㄽࠊࡉࡽ࡟㉸㧗㏿ィ⟬࡟ᇶ࡙ࡃィ⟬໬Ꮫ࡜ᶵᲔᏛ⩦ࢆ⼥ྜࡋࠊ㧗ຠ⋡࢚ࢿ࣮ࣝኚ᥮࡟
ྥࡅࡓ┦⏺㠃࡟࠾ࡅࡿ⣲㐣⛬ࡢᶵᵓゎ᫂ࠊࡉࡽ࡟᪂つ㧗ຠ⋡࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢ᥈⣴ࠊタィࢆ┠ⓗ࡜ࡍࡿࠋලయⓗ࡟ࡣࠊග࢚ࢿࣝࢠ࣮ኚ᥮ᢏ⾡࡜ࡋ࡚ኴ㝧㟁ụ࡜ගゐ፹ࢆྲྀࡾୖࡆࠊ
ࠕ࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉Ꮫࠖࢆ᥎㐍ࡋࡓࠋ௧࿴㸲ᖺᗘࡣ㸯㸧㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚບ㉳≧ែ࡜ࠊ㸰㸧*H ࢔ࣟ࢖໬ 6Q ࣌ࣟࣈࢫ࢝
࢖ࢺ &V6Q[*H\, ࡢᙧᡂ࢚ࢿࣝࢠ࣮࡜ࣂࣥࢻࢠࣕࢵࣉ࡟ࡘ࠸࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚບ㉳≧ែ❧᪉ᬗ ✵㛫⩌ 3P P ࡢ㓟໬ࢱࣥࢢࢫࢸࣥᵓ㐀ࢆ⏝࠸࡚㸪㟁Ꮚ≧ែ㸪ࣇ࢛ࣀࣥศᩓ㸪㟁Ꮚࣇ࢛ࣀࣥ࢝ࢵࣉ
ࣜࣥࢢィ⟬ࢆࡋࡓ㸬ࣈࣜࣝ࢔ࣥࢰ࣮ࣥࡢ✚ศ࡟ࡘ࠸࡚㸪ᵓ㐀⦆࿴࣭ࣇ࢛ࣀࣥィ⟬ࡣ  ࡢ k Ⅼࢢࣜࢵࢻ࡛⾜࠸㸪3'26࣭ࣂࣥࢻᵓ㐀ࡣ  ࡢ k Ⅼࢢࣜࢵࢻ࡛⾜ࡗࡓ㸬ࣇ࢛ࣀࣥィ⟬ࡣ  ࡢ T Ⅼࢢࣜࢵࢻ࡛⾜ࡗࡓ㸬᭷ຠ㉁㔞ࡣ㸪ࢫࣆࣥ㌶㐨┦஫స⏝ࢆ⪃៖ࡋ࡚ィ⟬ࡋࡓ㸬㟁Ꮚບ㉳≧ែᵓ㐀ࡢィ⟬ࡣ㸪༢ᩳᬗ 3QP P ࡢ  ࢫ࣮ࡢᵓ㐀ࢆ      ಸࡍࡿࡇ࡜࡛ᚓࡽࢀࡓᵓ㐀ࢆ฼⏝ࡋ࡚⾜ࡗࡓ㸦ࡇࢀࡣ㸪❧᪉ᬗ 3P
ࣃ࣮ࢭࣝ࡟┦ᙜࡍࡿ㸪 ཎᏊ⣔㸧㸬ບ㉳≧ែィ⟬࡜ࡋ࡚㸪9%0 ࡢ㟁Ꮚࡀ &%0 ࡟ບ㉳ࡉࢀࡿບ㉳≧ែࡢタᐃࡣ㸪FRQVWUDLQHGRFFXSDWLRQ')7 ἲ࡟ࡼࡗ࡚⾲⌧ࡋࡓ㸬ࣈࣜࣝ࢔ࣥࢰ࣮ࣥࡢ✚ศࡣ㸪ǻⅬࡢࡳࡢ k Ⅼ࡛⾜ࡗࡓ㸬ࣂࣥࢻᒎ㛤ࡣ㸪%DQG83EHWD ࢯࣇࢺ࢙࢘࢔ࢆ⏝࠸࡚⾜ࡗࡓ㸬ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬࡟ࡣ㸪
4XDQWXP (635(662  ࡜ <DPER  ࢆ౑⏝ࡋࡓ㸬஺᥮┦㛵ỗ㛵ᩘ࡜ࡋ࡚㸪**$3%( ỗ㛵ᩘࢆ⏝࠸ࡓ㸬ᨃ࣏ࢸࣥࢩࣕࣝ࡜ࡋ࡚ࡣ㸪᭱㐺໬ࡋࡓࣀ࣒ࣝಖᏑ 9DQGHUELOW ᨃ࣏ࢸࣥࢩࣕࣝࢆ౑⏝ࡋࡓ㸬᏶඲┦ᑐㄽⓗᨃ࣏ࢸࣥࢩࣕࣝࡣ㸪᭷ຠ㉁㔞ࡢィ⟬࡟ࡢࡳ౑⏝ࡋ㸪௚ࡣࢫ࣮࢝ࣛ┦ᑐㄽⓗᨃ࣏ࢸࣥࢩࣕࣝࢆ౑⏝ࡋࡓ㸬ᖹ㠃Ἴᇶᗏ࡜㟁Ⲵᐦᗘࡢ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣࡑࢀࡒࢀ 5\ ࡜ 5\ ࡜ࡋࡓ㸬 *H ࢔ࣟ࢖໬ 6Q ࣌ࣟࣈࢫ࢝࢖ࢺ &V6Q[*H\, ࡢᙧᡂ࢚ࢿࣝࢠ࣮࡜ࣂࣥࢻࢠࣕࢵࣉ
*H ࢔ࣟ࢖໬ 6Q ࣌ࣟࣈࢫ࢝࢖ࢺ &V6Q[*H\, ࢆᐦᗘỗ㛵ᩘἲ࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ィ⟬ࡋࡓ㸬➨୍ཎ⌮ィ⟬ࣃࢵࢣ࣮ࢪ࡜ࡋ࡚ 9$63 ࢆ⏝࠸࡚㸪ᖹ㠃Ἴࡢ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ H9㸪஺᥮┦㛵ỗ㛵ᩘ
࡜ࡋ࡚ 3%( ỗ㛵ᩘ㸪ࣈࣜࣝ࢔ࣥࢰ࣮ࣥࡢ✚ศࡣ  k ⅬIXࡢ᮲௳࡛ィ⟬ࢆ⾜ࡗࡓ㸬ᵓ㐀࡟ࡘ࠸࡚ࡣ㸰ࣃࢱ࣮ࣥࡢࣂ࢚࣮ࣜࢩࣙࣥࢆసᡂࡋࡓ㸬(1) ❧᪉ᬗ ✵㛫⩌ 3P
P P ࡢ &V6Q, ࡢ  ಸࡘࡲࡾ  ಸࡢࢫ࣮ࣃ࣮
ࢭࣝࢆసᡂࡋ㸪୍㒊ࡢ 6Q ཎᏊࢆ *H ཎᏊ࡟⨨᥮ࡋࡓ㸬ࡲࡓ㸪% ࢧ࢖ࢺ 6Q *H ࡢࢧ࢖ࢺ ࡟✵Ꮝࡀ⏕ࡌࡿྍ⬟- 162 -ᛶ ࢆ ⪃ ៖ ࡋ ࡓ 㸬 &V6Q, &V6Q*H, &V6Q, &V6Q*H, &V6Q*H, &V6Q, &V*H,
&V6Q*H, &V*H, &V6Q*H, &V6Q*H, &V*H, ࡣ⥙⨶ⓗ࡟඲࡚సᡂࡋ඲  ᵓ㐀࡛࠶ࡗࡓ㸬ࡲࡓ㸪6Q*H ࡀ  ࡢ &V6Q*H, ࡣ 6Q ࡜ *H ࢆ஺஫ࡲࡓࡣ㠃ୖ࡟㓄⨨ࡍࡿ࡜࠸࠺ᑐ⛠ᛶࡢ㧗࠸ᵓ㐀ࢆస ᡂ ࡋ 㸪 ࡇࡇ ࠿ ࡽ 6Q*H ཎ Ꮚ ࢆ ୍ࡘ ⨨ ᥮ ࡶ ࡋࡃ ࡣ ๐ 㝖 ࡍࡿ ࡇ ࡜ ࡛ 㸪&V6Q*H, &V6Q*H,
&V6Q*H, &V6Q*H, ࡢ඲  ᵓ㐀ࢆసᡂࡋࡓ㸬   ḟ࡟సᡂࡋࡓࡢࡣḞ㝗ࢆྵࡲ࡞࠸ᵓ㐀࡛࠶ࡿ㸬❧᪉ᬗ ✵㛫⩌ 3P P ࡢ &V6Q, ࡢ  ಸࡘࡲࡾ  ಸࡢࢫ࣮ࣃ࣮ࢭࣝࢆసᡂࡋ㸪୍㒊ࡢ 6Q ཎᏊࢆ *H ཎᏊ࡟⨨᥮ࡋ㸪ྲྀࡾ࠺ࡿ඲࡚ࡢᵓ㐀ࢆ⥙⨶ࡋࡓ &V6Q[*H[,  㓄⨨ࢆᑐ㇟࡜ࡋࡓ㸬ࡓࡔࡋ㸪ࡇࡢࡲࡲᵓ㐀᭱㐺໬ࡋ࡚ࡋࡲ࠺࡜㸪❧᪉ᬗࡀᏳᐃ࡛࠶ࡿ࡜ࡣ㝈ࡽ࡞࠸ࡢ࡟ࡶ㛵ࢃࡽࡎ㸪୍㒊ࡢᑐ⛠ᛶࢆಖᏑࡋ࡚ࡋࡲ࠺ࡓࡵ㸪ཎᏊࡢ఩⨨ࢆࣛࣥࢲ࣒࡟ࡎࡽࡋᑐ⛠ᛶࢆ᏶඲࡟ᔂࡋࡓᵓ㐀ࢆྛ㓄⨨࡟ࡘ࠸࡚  ࡘ‽ഛࡋ㸪ࡘࡲࡾ   ᵓ㐀ࢆィ⟬ࡋࡓ㸬ᵓ㐀᭱㐺໬࡛ࡣ㸪ཎᏊࡢ఩⨨ࡔࡅ࡛࡞ࡃࢭࣝࡢᙧࡸయ✚ࡶ᭱㐺໬ࡋࡓ㸬ྠ୍ཎᏊ㓄⨨ࡢ  ࡘࡢᵓ㐀࡛᭱ࡶ࢚ࢿࣝࢠ࣮ࡢᏳᐃ࡞ᵓ㐀࡟╔┠ࡋࡓ㸬



◊✲ᡂᯝ



㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚບ㉳≧ែ

:2 ࡣ㸪ᐊ ࡛ࡣ༢ᩳᬗ 3Q ࡛࠶ࡿࡀ㸪༢ᩳᬗ 3Q ࡛ࡢ㟁Ꮚࣇ࢛ࣀࣥ࢝ࢵࣉࣜࣥࢢィ⟬ࡣ㠀ᖖ࡟ࢥࢫࢺࡀ࠿࠿ࡿࡓࡵ㸪❧᪉ᬗ 3P P ࡢᵓ㐀ࢆ౑⏝ࡋࡓ㸬ࡣࡌࡵ࡟㸪㟁Ꮚ≧ែ࡟ࡘ࠸࡚ゎᯒࡋࡓ㸬❧᪉ᬗ 3P
P P࡛
ࡢࣂࣥࢻࢠࣕࢵࣉࡣ 62& ࡞ࡋ࡛ H9㸪62& ࠶ࡾ࡛ H9 ࡛࠶ࡗࡓ㸬ẚ㍑ࡢࡓࡵ㸪༢ᩳᬗ 3Q ࡢࣂࣥࢻࢠࣕࢵࣉࢆィ⟬ࡋ㸪62& ࡞ࡋ࡛ H9㸪62& ࠶ࡾ࡛ H9 ࢆᚓࡓ㸬ࡇࡢࣂࣥࢻࢠࣕࢵࣉࡣ㸪༢ᩳᬗ 3Qࡢᐇ㦂ⓗ࡞ࣂࣥࢻࢠࣕࢵࣉ 㹼H9 ࡼࡾᑠࡉ࠿ࡗࡓࡀ㸪3%( ỗ㛵ᩘ࡟ࡼࡿࣂࣥࢻࢠࣕࢵࣉࡢ㐣ᑠホ౯࡜㸪༢ᩳᬗ 3Q ࡼࡾ❧᪉ᬗ 3P P ࡢ᪉ࡀ኱ࡁ࠸ࡇ࡜ࡀཎᅉࡔ࡜⪃࠼ࡽࢀࡿ㸬ࡋ࠿ࡋ㸪༢ᩳᬗ 3Q ࡢࣂࣥࢻᵓ㐀ࢆ❧᪉ᬗ 3P
P P ࡟ᒎ㛤ࡍࡿ࡜㸪ࣂࣥࢻᵓ㐀࡟ࡣ࡯࡜ࢇ࡝㐪࠸ࡣぢࡽࢀ࡞࠿ࡗࡓ㸬᭷ຠ㉁㔞ࡣ 9% ࡛ࡣẚ㍑ⓗ኱ࡁ࡞್࡛ 㹼㸪&% ࡛ࡣẚ㍑ⓗᑠࡉ࠸್࡛ 㹼 ࡛࠶ࡗࡓ㸬ບ㉳≧ែࡢᵓ㐀࡟ࡘ࠸࡚ࠊFRQVWUDLQHG RFFXSDWLRQ ')7 ἲ࡟ࡼࡾ 9%0 ࡢ㟁Ꮚࡀᮍ༨᭷࡜ࡋ㸪&%0 ࡟㟁Ꮚࢆ༨᭷ࡉࡏࡿࡼ࠺࡟㌶㐨ࡢ༨᭷ᩘࢆไ⣙ࡋィ⟬ࢆ⾜ࡗࡓ㸬ࡇࡢᡭἲ࡛ࡣ㸪඲࢚ࢿࣝࢠ࣮ࡀ᫂☜࡟ᐃ⩏ࡉࢀ࡚࠸ࡿࡓࡵ㸪ࢩࢫࢸ࣒ࡢᵓ㐀ࢆ᭱㐺໬ࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸬ᇶᗏ≧ែ࡛ᵓ㐀᭱㐺໬ࡋࡓᵓ㐀ࢆ 67㸪ບ㉳≧ែ࡛ᵓ㐀᭱㐺໬ࡋࡓᵓ㐀ࢆ 67 ࡜ࡍࡿ㸬67 ࡢບ㉳≧ែ࡜ᇶᗏ≧ែࡢ㟁Ⲵᐦᗘࢆẚ㍑ࡍࡿ࡜㸪:2 㠃ࡢ 2 S ཎᏊࡢ୍ࡘࡢ㟁Ꮚࡀ : G ࡟ບ㉳ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬67 ࡢ &% ࡜ 9% ࡢ㟁Ⲵᐦᗘࡣ㸪࡝ࡕࡽࡶ⤖ᬗ඲య࡟ ḟඖⓗ࡟ᗈࡀࡗ࡚࠸ࡓ㸬ࡇࢀࡣ㸪ບ㉳≧ែ࡛ࡢᵓ㐀ኚ໬࡟ࡼࡾ㸪&%0 ࡜ 9%0 ࡢ㟁Ꮚ≧ែࡀྛ⾲㠃࡟ศ㞳ࡉࢀࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿ㸬67 ࠿ࡽ 67 ࡬ࡢཎᏊࡢኚ఩ࢆほᐹࡍࡿ࡜㸪: ཎᏊࡀບ㉳≧ែ࡛ 2 ཎᏊࡢ᪉ྥ
࡟ኚ఩ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬: ཎᏊࡢኚ఩ࡣ㸪ࢪࢢࢨࢢ :2:2 㙐ࡢࢪࢢࢨࢢࢆῶᑡࡉࡏࡿ᪉ྥ࡟⛣ືࡋࡓ㸬ບ㉳≧ែࡢᵓ㐀ኚ໬࡟ࡼࡾ㸪ඖࠎ࡯ࡰ➼㊥㞳ࡔࡗࡓ  ␒┠࡜  ␒┠ࡢ㏆ഐࡢ :2 ⤖ྜࡣ∦ഃࡀ▷ࡃ㸪཯ᑐഃࡀ㛗ࡃ࡞ࡗࡓࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ྠᵝ࡟㸪67 ࡢ㟁Ꮚບ㉳≧ែ࡛ຊࡀຍ࠼ࡽࢀࡓ᪉ྥ࡟ኚ఩ࡋࡓᵓ㐀ࡢ :2ཎᏊ㛫ࡢ㊥㞳ࢆィ⟬ࡍࡿ࡜㸪๓ࡢሙྜ࡜ࡣ␗࡞ࡾ㸪 ␒┠ࡢ㏆ഐࡢ :2 ⤖ྜࡀ㛗ࡃ࡞ࡾ㸪 ␒┠࡜  ␒┠ࡢ㏆ഐࡢ :2 ⤖ྜࡀ▷ࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࡘࡲࡾ㸪㟁Ꮚࡀບ㉳≧ែ࡟࠶ࡿึࡵ࡜㸪ᵓ㐀ࡀບ㉳≧ែࡢᵓᡂ࡛᭱⤊ⓗ࡟Ᏻᐃࡍࡿ࡜ࡁ࡟㸪ཎᏊࡀཷࡅࡿຊࡢ᪉ྥࡀ␗࡞ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿ㸬67 ࡢບ㉳≧ែ࡛ཎᏊ࡟㐺⏝ࡉࢀࡿຊࢆほᐹࡍࡿ࡜㸪: ཎᏊࡶ 2 ཎᏊࡢ᪉ྥ࡟ኚ఩ࡍࡿഴྥࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ບ㉳≧ែ࡛ࡢ୕ᩳ
ᬗ 3 ࡬ࡢኚ఩ࡶྠࡌ᪉ྥࢆ♧ࡋ࡚࠸ࡿࡓࡵ㸪: ཎᏊࡣ 2 ཎᏊࡢ᪉ྥ࡟⛣ືࡋ⥆ࡅࡿ࡜⪃࠼ࡽࢀࡿ㸬୍᪉㸪
2 ཎᏊࡣ : ཎᏊࡢ᪉ྥ࡟ኚ఩ࡋࡼ࠺࡜ࡍࡿࡀ㸪㏵୰࠿ࡽ௚ࡢ᪉ྥ࡟⛣ືࡍࡿࡼ࠺࡛࠶ࡿ㸬ḟ࡟㸪67 ࡜ 67

- 163 -

ࡢࣂࣥࢻᵓ㐀ࢆ❧᪉ᬗ 3P
P P ࡢࣂࣥࢻᵓ㐀࡟ᒎ㛤ࡋ㸪❧᪉ᬗ 3P
P P ࡢࣂࣥࢻᅗ࡜ẚ㍑ࡍࡿ࡜㸪኱ࡁ࡞ኚ໬ࡣ
࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡉࡽ࡟㸪9%0 ࡜ &%0 㛫ࡢ཮ᴟᏊ⾜ิせ⣲ࡢ⤯ᑐ್ࡣ㸪67 ࡜ 67 ࡢ୧᪉࡛࡯ࡰࢮࣟ
ࡔࡗࡓ㸬ࡇࢀࡽࡢ஦ᐇ࠿ࡽ㸪❧᪉ᬗ 3P P ࡛ࡣ㛫᥋ࢠࣕࢵࣉࡔࡗࡓࡶࡢࡀ㸪67 ࡜ 67 ࡛ࡶࡑࡢࡲࡲ⥔ᣢࡉࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ㸬ࡇࢀࡽࡢ⤖ᯝ࡜ $VDNXUD ࡽࡢ◊✲࠾ࡼࡧ .RLGH ࡽࡢ :/, ࢚ࢵࢪ᫬㛫ศゎ ; ⥺྾཰ศගἲࡢ⤖ᯝ࠿ࡽ㸪ගບ㉳࠿ࡽ SV ࡲ࡛ࡢ㛫࡟┤᪉ᬗࡢᒁᡤᵓ㐀ࢆᣢࡘࢧ࢖ࢺࡢẚ⋡ࡀቑຍࡋ㸪ࡑࡋ࡚ࠊ
SV ᚋ࡟ࡣࠊඖࡢ༢ᩳᬗᵓ㐀࡬ࡢᚎࠎ࡞ᅇᖐࢆほᐹࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ㸬

*H ࢔ࣟ࢖໬ 6Q ࣌ࣟࣈࢫ࢝࢖ࢺ &V6Q[*H\, ࡢᙧᡂ࢚ࢿࣝࢠ࣮࡜ࣂࣥࢻࢠࣕࢵࣉ

❧᪉ᬗ࠿ࡽసᡂࡋࡓᵓ㐀(1)࡟ࡘ࠸࡚ࠊ3'26 ࢆ☜ㄆࡍࡿ࡜㸪࡝ࡢᵓ㐀ࡶ౯㟁Ꮚᖏ 9% ࡀ , S 㸪ఏᑟయ &%ࡀ 6Q S ࡜ *H S ࡛ᵓᡂࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࣂࣥࢻᵓ㐀ࢆ☜ㄆࡍࡿ࡜㸪&%0 ࡜ 9%0 ࡀ㸦ࢫ࣮ࣃ࣮ࢭ
ࣝ࡟࠾ࡅࡿ㸧ǻⅬୖ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࡑࡇ࡛㸪඲࡚ࡢᵓ㐀࡟ࡘ࠸࡚ *H ⨨᥮ࡸ 6Q ✵Ꮝ࡟ࡼࡿࣂࣥࢻࢠ
ࣕࢵࣉࡢኚ໬ࢆぢ✚ࡶࡿࡓࡵ࡟ǻⅬࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࢆィ⟬ࡋࡓ㸬ࡲࡎ㸪Ḟ㝗ࢆྵࢇࡔᵓ㐀ࡣ඲࡚ࣂࣥ
ࢻࢠࣕࢵࣉࡀ  ࡛㔠ᒓᵝ࡜࡞ࡗࡓ㸬Ḟ㝗ࢆྵࡲ࡞࠸ᵓ㐀࡟ࡘ࠸࡚ࡣ㸪6Q ࡢࡳ *H ࡢࡳ ࡢᵓ㐀࠿ࡽ㸪ᑡࡋ࡛ࡶ*H 6Q ࡀΰࡌࡿ࡜㸪ࣂࣥࢻࢠࣕࢵࣉࡀ⦰ᑠࡋࡓ㸬ࡋ࠿ࡋ㸪6Q*H ࡀ  ௜㏆ࡣࣂࣥࢻࢠࣕࢵࣉࡀᣑ኱ࡋࡓ㸬௒ᅇࡢ⤖ᯝ࡛ࡣ㸪ᑐ⛠ᛶࡀⰋ࠸࡯࡝ࣂࣥࢻࢠࣕࢵࣉࡀ㧗࠸ഴྥ࡟࠶ࡗࡓ㸬ḟ࡟ྛ⤌ᡂ࡟ࡘ࠸࡚࢚ࢿࣝࢠ࣮ⓗ࡟᭱ࡶᏳᐃ࡞ᵓ㐀ࢆㄪ࡭ࡿ࡜㸪&V6Q*H, ࢆ㝖࠸࡚ 6Q*H ࢆᖹ㠃࡟஺஫࡟㓄⨨ࡋࡓᵓ㐀ࡼࡾࡶ㸪1D&O ࡢᵝ࡞஫࠸㐪࠸࡟ࡋࡓᵓ㐀ࡢ᪉ࡀᏳᐃ࡛࠶ࡗࡓ㸬ࡇࢀࡽࡢᏳᐃ࡞ᵓ㐀ࡢ⏕ᡂ࢚ࢿࣝࢠ࣮ࢆඖ࡟㸪Ḟ㝗ᙧᡂ࢚ࢿࣝ
ࢠ࣮ࢆィ⟬ࡋࡓ㸬Ḟ㝗✀ ' ' 6Q*H ࡢ㟁Ⲵࡣ  ࡜ࡋ࡚ィ⟬ࢆ⾜ࡗࡓ㸬ࡑࡢ⤖ᯝ㸪&V6Q, &V6Q*H, &V*H, ࡣ 6Q Ḟ㝗㸪&V*H,  &V6Q*H,  &V6Q*H, ࡣ *H Ḟ㝗㸪&V6Q*H,&V6Q*H,
&V6Q*H, ࡣ 6Q Ḟ㝗࣭*H Ḟ㝗୧᪉ࡢḞ㝗ᙧᡂ࢚ࢿࣝࢠ࣮ࡀᚓࡽࢀࡓ㸬6Q Ḟ㝗ࡣ 㹼H9㸪*H Ḟ㝗ࡣ  㹼 H9 ࡢḞ㝗ᙧᡂ࢚ࢿࣝࢠ࣮࡛㸪㟁Ⲵ  ࡢ 6Q*H Ḟ㝗ࡣ࢚ࢿࣝࢠ࣮ⓗ࡟୙Ᏻᐃ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗ
ࡓ㸬ḟ࡟㸪᱁Ꮚᐃᩘࡢኚ໬ࢆ☜ㄆࡋࡓ㸬ࡲࡎ㸪᱁Ꮚᐃᩘ D E F ࡟ࡘ࠸࡚㸪6Q ࠿ࡽ *H ࡟࡞ࡿ࡟ࡘࢀ࡚᱁Ꮚᐃ
ᩘࡀᚎࠎ࡟ᑠࡉࡃ࡞ࡗ࡚࠸ࡃࡇ࡜ࡀ☜ㄆ࡛ࡁ㸪ࡇࢀࡣ 6Q ࡜ *H ࡢ࢖༙࢜ࣥᚄࡢ኱ࡁࡉࡢ㐪࠸ࢆ཯ᫎࡋ࡚࠸ࡿ
ࡢࡔ࡜⪃࠼ࡽࢀࡿ㸬❧᪉ᬗ࡜࠸࠺ᑐ⛠ᛶࡢ✵㛫⩌ࢆᔂࡋࡓᵓ
㐀࠿ࡽᵓ㐀᭱㐺໬ࡋ࡚ᚓࡽࢀࡓᵓ㐀  ࡟ࡘ࠸࡚㸪ࡲࡎ㸪6Q ࡜ *H ࡀ  ࡢ &V6Q*H,࡛ࡣ㸪ࡇࢀࡲ࡛ 6Q ࡜ *H ࢆ஺஫࡟㓄⨨ࡋࡓ❧᪉ᬗࡢ 1D&O ᆺࡀᏳᐃ࡛࠶ࡗࡓࡀ㸪ྠᵝࡢ
1D&O ᆺ࡛ࡶ㸪❧᪉ᬗ࡜࠸࠺᮲௳ࢆእࡋࡓ᪉
ࡀᏳᐃ࡛࠶ࡗࡓ㸬ࡲࡓ㸪1D&O ᆺࡼࡾࡶᑐ⛠ᛶࡢప࠸ 6Q ࡸ *H ࡀྠ✀ྠኈ୍࡛㒊࡜࡞ࡾྜࡗࡓᵓ㐀ࡢ᪉ࡀᏳᐃࡔࡗࡓ㸬ࡇࢀࡣ㸪6Q
࡜ *H ࡀ᏶඲࡟ΰࡊࡾྜࡗ࡚࠸ࡿࡼࡾࡶ 6Q
ࡸ *H 㛫୍࡛㒊ࢻ࣓࢖ࣥࢆࡘࡃࡗࡓ᪉ࡀᏳ
ᐃ໬ࡍࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿ㸬ᅗࡢ࡜࠾ࡾ 6Q*H ࡢ๭ྜ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ࡢኚ໬࡜ࡋ࡚ࡣ㸪&V6Q, ࡜ &V*H, ࡢ࢚ࢿࣝࢠ࣮ࢆᇶ‽࡜ࡋ࡚ィ⟬ࡍࡿ࡜㸪&V6Q, ࡼࡾࡶ *H ࢆ༙ศ௨ୗࡢ๭ྜ࡛ྵࢇࡔᵓ㐀ࡢ᪉ &V6Q[*H[, [Ӎ ࡀᏳᐃ࡛࠶ࡾ㸪᭱ࡶᏳᐃ࡞
ࡢࡣ 6Q ࢆ *H ࡟  㸣⨨᥮ࡋࡓᵓ㐀࡛࠶ࡗࡓ㸬ḟ࡟ྠ୍⤌ᡂࡢ 6Q*H ࡢ㓄⨨࡜ึᮇᵓ㐀ࡢཎᏊ఩⨨ࡢࣛࣥ- 164 -

ࢲ࣒ᛶࡢ࡝ࡕࡽࡀ࡝ࡢ⛬ᗘࡢᙳ㡪ࢆ୚࠼ࡿࡢ࠿☜ㄆࡍࡿࡓࡵ࡟㸪ࡑࢀࡒࢀᶆ‽೫ᕪࢆィ⟬ࡋࡓ㸬ࡑࡢ⤖ᯝ㸪㓄⨨࡟ࡼࡿ࢚ࢿࣝࢠ࣮ࡢᶆ‽೫ᕪࡣ  PH9IX࡛㸪ึᮇཎᏊ఩⨨ࡢࣛࣥࢲ࣒ᛶ࡟ᑐࡍࡿᶆ‽೫ᕪࡣ 
PH9IX࡛࠶ࡾࠊࡇࢀࡽࡣ࡜࡚ࡶᑠࡉ࠸ࡢ࡛㸪㓄⨨ࡸึᮇࡢཎᏊ఩⨨ࡣ඲࢚ࢿࣝࢠ࣮࡟࠾࠸࡚኱ࡁ࡞ၥ㢟࡟࡞ࡽ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓ㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

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- 165 -

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(a)
N
R1

1

OH

H+
R1

N

R1

R2

R2

H 2O

R2

N

R1

1

OH
R2

SO2F2 (gas), Et3N
CH2Cl2

R1
N

F

H2 O

R2
4
Detected in GC-MS (EI)
- 166 -

OR2
32(b) Fokin et al (Chem. Eur. J. 2020)
N

R1
N
H

R1
N
H

O
R2
3

(c)

N

F
N S F
Et
F

Et

DAST

O

Et
F
F S N H
O Et
N

HF

R2

R1

O

R2

O

2

F

4

R2

6  $"#&@(87&<,;

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F

7
R1
N

F

R2

R1

6
R1 N

R2

R1 N

F
Et
F S N
O Et
N

R1 1 R2

F
N S O
Et
F
F
5

Et

OH

%!

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N

OH
CH3

Fluorinating Reagent(1.5 eq.)
Solvent (1.0 mL)
20℃, 20 min

H
N
O
3a

1a (0.5 mmol)
6 ?.>D)K- 167 -

CH3

%



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Entry
Fluorinating reagent

D)JB2++
Solvent

Yield of 3a (%)

1

DAST

CH2Cl2

47

2
3

DAST
DAST

CHCl3
1,2-Dichloroethane

41
41

4
5
6

DAST
DAST
DAST

THF
1,4-Dioxane
Et2O

97
91

7

DAST

1,2-Dimethoxyethane

88
92

8
9
10

DAST
DAST
DAST

acetone
AcOEt
DMF

86
91
92

11
12
13
14

DAST
DAST
DAST
DAST

DMSO
MeCN
Pyridine
THF (2.0 eq.) in CH2Cl2

80
86
26

15

DAST

THF: CH2 Cl2 = 1: 1

66
91

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N

2a

C

+
O

THF

THF

9.0 kcal/mol

O


N

C

2a -THF complex- 168 -

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- 171 -

Molecular Mechanism of Protein Function Studied by Site-Selective
Heat Current Analysis, , T. WANG, *, "/, , +., 

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[1] T. Yamato, et al. “Computational study on the thermal conductivity of a protein”, J. Phys. Chem. B 126, 3029
(2022); [2] T. Wang, et al. “Site-selective heat current analysis of α-helical protein with linear-homopolymer-likemodel”, J. Chem. Phys. (in press)- 172 -

ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࡢᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭
ศᏊ㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝ
Structures, Dynamics, Intermolecular Interactions, and Vibrational
Spectra of Liquids, Biomolecules, and Related Molecular Systems‫ۑ‬㫽ᒃ ⫕㸪໭ᮧຬྜྷ㸪㓇஭Ꮥᚫ㸪㉥⃝᭸㤶㸪✄⏕ႛ௓㸪㕥ᮌ೺௓㸦㟼ᒸ኱࣭ᕤ㸧ᗎᮏࣉࣟࢪ࢙ࢡࢺ࡛ࡣ㸪ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࢆᑐ㇟࡟㸪ᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭ศᏊ㛫┦஫స⏝࡟ࡲࡘࢃࡿ⌮ㄽⓗㅖၥ㢟ࡢ࠺ࡕ㸪≉࡟㸦ᗈ⩏ࡢ㸧᣺ືࢫ࣌ࢡࢺࣝ࡟㛵ಀࡋࡓࡶࡢ࡟ࡘ࠸࡚㸪ศᏊືຊᏛἲ࣭
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௧࿴㸲ᖺᗘ࡟ࡣ㸪௨ୗ࡟♧ࡍ◊✲ࢆ⾜ࡗࡓࠋỈ⁐ᾮ୰ࡢ◪㓟࢖࢜ࣥࡢᑐ⛠ᛶ◚ࢀ࡟࠾ࡅࡿศᏊ㛫㟼㟁┦஫స⏝ࡢᙺ๭ࡢゎᯒ◪㓟࢖࢜ࣥࡣᏙ❧≧ែ࡟࠾࠸࡚ 'K ᑐ⛠࡛࠶ࡾ㸪㸱ࡘࡢ 1̽2 ఙ⦰᣺ື࣮ࣔࢻࡢ࠺ࡕᑐ⛠ఙ⦰௨እࡢ㸰ࡘ㸦㠀ᑐ⛠ఙ⦰㸧ࡣ⦰㔜ࡋ࡚࠸ࡿࡀ㸪Ỉ⁐ᾮ୰࡛ࡣ FP ⛬ᗘࡢࣂࣥࢻศ⿣ࡀほࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ㸪ࡇࢀࡣᑐ⛠ᛶ◚ࢀࡢຠᯝ࡟ࡼࡿࡶࡢ࡜ㄆ㆑ࡉࢀ࡚࠸ࡿࠋỈ࡜ࡢ఍ྜయࢆᑐ㇟࡜ࡋࡓ㔞Ꮚ໬Ꮫィ⟬ࡸ㸪Ỉ⁐ᾮࢆᑐ㇟࡜ࡋࡓ 4000 ィ⟬࡟ࡼࡾ㸪ࡇࡢࣂࣥࢻศ⿣ࡀᐃᛶⓗ࡟෌⌧ࡉࢀࡿࡇ࡜ࡣ᪤࡟♧ࡉࢀ࡚࠸ࡿࡀ㸪࣓࢝ࢽ
ࢬ࣒ࡢヲ⣽࡟ᑐࡍࡿ⌮ゎࡣ༑ศ࡛ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣ㸪 12± +2  ࡞࡝఍ྜయࢆᑐ㇟࡜ࡋࡓィ⟬࡜ゎᯒ࡟ࡼࡾ㸪Ỉ࿴࡟ࡼࡿᵓ㐀࡜᣺ື࣮ࣔࢻࡢኚ໬࡟ᑐࡋ࡚㟼㟁┦஫స⏝ࣔࢹࣝࡀ࡝ࡢ⛬ᗘᡂ❧ࡍࡿ࠿ࢆ᳨ウࡍࡿ࡜࡜ࡶ࡟㸪ࡇࢀࢆỈ⁐ᾮ⣔ࡢྂ඾ 0' ࡜⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾ㸪ᐇࡢࣂࣥࢻศ⿣ࡀ෌⌧ྍ⬟࡛࠶ࡿ࠿࡝࠺࠿ࢆ᳨ウࡋࡓࠋ
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࡟ࡼࡾ㸪1±2 ᑐ⛠࣭㠀ᑐ⛠ఙ⦰᣺ືࣂࣥࢻࡢ᫬㛫㡿ᇦࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࡇ࡜ࡀ࡛ࡁࡿࠋࡑࡢ⤖ᯝ㸪㠀ᑐ⛠ఙ⦰ࡢࣂࣥࢻศ⿣࡜ࡋ࡚ aFP ࡜࠸࠺ィ⟬್ࡀᚓࡽࢀ㸪ᐇ aFP  ࡜Ⰻ࠸୍⮴ࢆ♧ࡋࡓࠋィ⟬ࣉ

ࣟࢭࢫࢆ㎺ࡿ࡜㸪㟼㟁⎔ቃࡢ㠀ᑐ⛠ᛶ࡜ࡋ࡚auEKe ࡟ᑐᛂࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
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- 173 -

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[1] Y. Kawashima, T. Hamachi, A. Yamauchi, K. Nishimura, Y. Nakashima, S. Fujiwara, N. Kimizuka, T. Ryu, T.
Tamura, M. Saigo, K. Onda, S. Sato, Y. Kobori, K. Tateishi, T. Uesaka, G. Watanabe*, K. Miyata*, and N. Yanai“Singlet fission as a polarized spin generator for biological nuclear hyperpolarization” Nat. Commun. 14, 1056
(2023). (GLWRUV¶+LJKOLJKW
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luminescence of rotaxane mechanophores by varying the stopper size”, J. Mater. Chem. C 11, 3949 (2023). )URQW

&RYHUDQG+273DSHU
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[4] H. Nishikawa*, K. Sano, S. Kurihara, G. Watanabe, A. Nihonyanagi, B. Dhara, and Fumito Araoka*, “Nanoclustering mediates phase transitions in a diastereomerically-stabilized ferroelectric nematic system”, Commun.
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- 178 -

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Rev. B. 01 ࠶ࡿ࠸ࡣ Rev. C 01, ORCA ࢆ⏝࠸ࡓࠋィ⟬ࡣ୺࡟ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ₇⟬ࢧ࣮ࣂ࣮࠾ࡼࡧᙜ◊✲ᐊࡢࢥࣥࣆ࣮ࣗࢱୖ࡛⾜ࡗࡓࠋࡉࡽ࡟ࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝(NCI)ࡢ
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࠾࠸࡚ࠊࡶࡗ࡜ࡶ┤ᡖⓗ࡞᪉ἲ࡜ࡋ࡚㔜せどࡉࢀ࡚ࡁ࡚࠸ࡿࠋᙜ◊✲ᐊ࡛ࡣࠊ኱㜰኱ᏛࡢⲔ㇂┤ேᩍᤵࡀ㛤Ⓨࡋࡓ N-8-࢔࣑ࣀ࢟ࣀࣜࢽࣝ࣋ࣥࢬ࢔࣑ࢻㄏᑟయࢆ㓄ྥᇶ࡜ࡋ࡚⏝࠸ࡓࠊ࣐ࣞ࢖࣑ࢻࡢ C-H ࢔ࣝࢣࢽࣝ໬཯
ᛂ㸦Org. Lett. 2017, 19, 4544−4547㸧ࡢゎᯒࢆࡲࡎ⾜ࡗࡓࠋࡇࡢ཯ᛂ࡛ࡣࠊⰾ㤶᪘࢔࣑ࢻࡢ࢜ࣝࢺ఩ࡢࡳ࡟ CH ࢔ࣝ࢟ࣝ໬ࡀ㉳ࡁࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 1a㸧[1]ࠋⰾ㤶᪘㒊఩ࡢ㔜Ỉ⣲ࣛ࣋ࣝ࡟ࡼࡿྠ఩యຠᯝࡢᐇ㦂࡟ࡼࡿ࡜ࠊᅗ㸯a ࡟♧ࡋࡓ཯ᛂ࡛ࡣࠊ᭱ึࡢ C-H ⤖ྜάᛶ໬ࡢẁ㝵ࡣྍ㏫ⓗ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡉࡽ࡟ࠊ
㓄ྥᇶࢆ N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ㸧࣋ࣥࢬ࢔࣑ࢻㄏᑟయ࡟ኚ࠼ࡓሙྜࠊ㓟໬ⓗ C-H ࢔ࣝࢣࢽࣝ໬/⎔໬཯ᛂࡀྠ᫬࡟㉳ࡁ࡚ࢫࣆࣟ⎔⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࠊDFT ィ⟬࡜ྠ᫬࡟Ꮫ⾡ㄅㄽᩥ࡟ሗ࿌ࡋࡓ㸦ᅗ1b㸧ࠋᮏ◊✲ㄢ㢟࡛ࡣࠊ᫖ᖺᗘ㸦2021 ᖺᗘ㸧ࡢሗ࿌᭩࡟ࠊᏛ⾡ㄅㄽᩥ࡜ࡋ࡚ฟ∧ࡋࡓ N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽ
ࣝ㸧࣋ࣥࢬ࢔࣑ࢻㄏᑟయࡢ཯ᛂࡢᡂᯝࡀ♧ࡉࢀ࡚࠸࡞࠸ࡇ࡜࠿ࡽࠊᮏᖺᗘ࡟ࠊࢫࣆࣟ⎔໬཯ᛂ࡜୪࡭࡚ሗ࿌ࡍࡿࠋ(a) N-8-࢔࣑ࣀ࢟ࣀࣜࢽࣝ࣋ࣥࢬ࢔࣑ࢻㄏᑟయࢆ㓄ྥᇶ࡜ࡋ࡚⏝࠸ࡓࠊDFT ィ⟬࡟ࡼࡿ࣐ࣞ࢖࣑ࢻࡢ C-H ࢔ࣝࢣࢽࣝ໬཯ᛂ࡟ࡘ࠸࡚ࡲࡎሗ࿌ࡍࡿࠋM06/def2-TZVP/SMD+W+cc ࡛ࣞ࣋ࣝࡢ᳨ウࢆ⾜ࡗࡓࠋ- 187 -

ᅗ㸯. ࣟࢪ࣒࢘(I)ゐ፹ࢆ⏝࠸ࡓ࣐ࣞࣥ࢖࣑ࢻࡢ㓟໬ⓗ C-H ࢔ࣝࢣࢽࣝ໬཯ᛂ

ࡲࡎࠊRh(I)(OAc)(COD)࡟ࠊN-8-࢔࣑ࣀ࢟ࣀࣜࢽࣝ࣋ࣥࢬ࢔࣑ࢻࡀ㓄఩ࡋࡓࡢࡕࠊN-8-࢔࣑ࣀ࢟ࣀࣜࢽࣝ࣋ࣥ
ࢬ࢔࣑ࢻࡢ NH ࡀ⬺ࣉࣟࢺࣥ໬ࡋ࡚ࠊ㓑㓟ࡢ⬺㞳ࢆక࠸ࠊINT-2 ࡀ⏕ᡂࡍࡿࠋࡑࡢࡢࡕࠊ㓟໬ⓗ௜ຍࡀ㉳ࡁ࡚ࠊ࣐ࣞ࢖࣑ࢻࡀ Rh ࡟ȧ㓄఩ࡋࡓࡢࡕࠊ࣐ࣞ࢖࣑ࢻࡢ C=C ⤖ྜ࡬ࡢ C-Rh ⤖ྜࡢᤄධࡀ㉳ࡁࠊRh(III)୰ᚰ࡟ࣉࣟ
ࢺࣥ໬ࡋࡓ࣐ࣞ࢖࣑ࢻࡀ⤖ྜࡋࡓ㘒యࡀ⏕ᡂࡍࡿࠋࡇࡢ཯ᛂ࡛ࡣࠊ㓄఩Ꮚ㛫Ỉ⣲⛣ື (LLHT)ࡢ⤒㊰ࡢ᪉ࡀࠊ㓟໬ⓗ௜ຍ࡟ẚ࡭࡚୙฼࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ࡜࡜ࡶ࡟ࠊenergy span model ゎᯒ࡟ࡼࡾゐ፹ࡢ
turnover ࢆỴࡵࡿẁ㝵ࡀࠊ㓟໬ⓗ௜ຍ࡛࠶ࡿࡇ࡜ࡶࢃ࠿ࡗࡓࠋⰾ㤶᪘ C-Rh ⤖ྜ㛤⿣ࢆక࠺㑏ඖⓗ⬺㞳࡜ⰾ㤶᪘Ⅳ⣲ࡢ࢔ࣝ࢟ࢽࣝ໬ࢆ⤒࡚ࠊ᭱⤊⏕ᡂ≀(FP)࡟⮳ࡿࠋ(b) N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ㸧࣋ࣥࢬ࢔࣑ࢻㄏᑟయࢆ㓄ྥᇶ࡜ࡋ࡚⏝࠸ࡓࠊDFT ィ⟬࡟ࡼࡿ࣐ࣞ࢖࣑ࢻࡢ CH ࢔ࣝࢣࢽࣝ໬཯ᛂ࡟ࡘ࠸࡚ࡶࠊDFT ィ⟬ࢆ⾜ࡗࡓࠋRh (COD)(OPiv) ࡢ N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ)࣋ࣥ

ࢬ࢔࣑ࢻ (ᅗ㸰ࠊINT-0) ࡬ࡢ㓄఩࡟ࡼࡗ࡚㛤ጞࡉࢀࠊRh(I) 」ྜయ (INT-1) ࢆᙧᡂࡍࡿࠋ S ཎᏊࡣ Rh
୰ᚰ (Rh−S = 2.40 Å) ࡟㓄఩ࡍࡿࡀࠊࣆࣂ࣮ࣞࢺࡢ O ཎᏊࡢ 1 ࡘࡀỈ⣲⤖ྜࢆ௓ࡋ࡚࢔࣑ࢻᇶࡢ H࡜┦஫స⏝ࡋࠊ௚ࡢ O ཎᏊ࡜ Rh(I) ࡜ࡢ㛫ࡢ⤖ྜࡀ┦஫స⏝ࡍࡿࠋ (Rh−O = 2.08 Å) ࡀ⥔ᣢࡉࢀࡿࠋ
ゐ፹ࡢ㓄఩࡟⥆࠸࡚ࠊ120 kJ/mol ࡢάᛶ໬࢚ࢿࣝࢠ࣮࡛ N-H ࡀ⬺ࣉࣟࢺࣥ໬ࡉࢀ (TS-1)ࠊRh(I) 㘒య࠿ࡽࣆࣂࣝ㓟 (PivOH) ࡀゎ㞳ࡍࡿ(INT-2)ࠋ
N-H ⬺ࣉࣟࢺࣥ໬ᚋࡢ C-H άᛶ໬ࢫࢸࢵࣉ࡛ࡣࠊ㓟໬ⓗ௜ຍ/㌿⛣ᤄධ (OA/MI㸸⤒㊰ A) ࡜㓄఩Ꮚ㛫Ỉ⣲⛣ື (LLHT:⤒㊰ B) ࡢ 2 ࡘࡢྍ⬟࡞཯ᛂ⤒㊰ࢆ⪃៖ࡋࡓࠋ๓⪅ࡢ᪉ࡀᚋ⪅ࡢ⤒㊰ࡼࡾࡶ᭷฼࡛
࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ㓟໬ⓗ௜ຍࡢᚋࠊ࣐ࣞ࢖࣑ࢻࡣ Rh(III)-」ྜయ(INT-4A)࡟㓄఩ࡋࠊS ཎᏊࡣྠ᫬࡟
Rh(III)࠿ࡽゎ㞳ࡍࡿࠋ2 ␒┠ࡢ࣐ࣞ࢖࣑ࢻࡀ INT-5A ࡢ Rh ୰ᚰ࡟㓄఩ࡋࡓࡢࡕࠊ㌿⛣ᤄධࡲࡓࡣ㓄఩Ꮚ㛫Ỉ⣲⛣ືࡢᚋࠊRh(III)㘒య࡟㓄఩ࡍࡿࠋ
TS-4A 㑄⛣≧ែࢫࢸࢵࣉ࡟ࡼࡾࠊⰾ㤶᪘࢔࣑ࢻࡢ࣐ࣞ࢖࣑ࢻ࡜ࣇ࢙ࢽࣝᇶࡢ㛫࡛ 72 kJ/mol ࡢάᛶ໬࢚
ࢿࣝࢠ࣮࡛ C-C ⤖ྜࡀ⏕ᡂࡍࡿ(TS-4AࠊCOD ࡞ࡋ)ࠋ(N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ)࣋ࣥࢬ࢔࣑ࢻ࠿ࡽࡢ᭱⤊⏕ᡂ≀(࢖ࢯ࢖ࣥࢻࣟࣥࢫࣆࣟࢫࢡࢩࣥ࢖࣑ࢻ)ࡢᙧ
ᡂ࡟ࡘ࠸࡚ࠊ࠸ࡃࡘ࠿ࡢ௦᭰⤒㊰ࡶ⪃៖ࡋࡓࠋC-N ⤖ྜᙧᡂ๓㥑య࡛ࡶ࠶ࡿ Rh 」ྜయ INT-8 ࡬ࡢ PivOH
ࡢ෌㓄఩㸦INT-9C㸧ࢆྵࡴ⤒㊰ࡶ᳨ウࡋࡓࠋ඲య࡜ࡋ࡚ࠊRh-COD ゐ፹ࡢᏑᅾୗ࡛ࡣ TS-6A ࢆ௓ࡋࡓ⤒㊰ A ࡛ࡢ C-N ⤖ྜᙧᡂࢫࢸࢵࣉࡀዲࡲࡋ࠸࡜⤖ㄽ࡙ࡅࡓࠋC-N ⤖ྜᙧᡂ(TS-6A㸧ࢫࢸࢵࣉ࡟⥆࠸࡚ࠊ- 188 -

PivOH ࡢ෌㓄఩(INT-10A)࠾ࡼࡧ࣐ࣞ࢖࣑ࢻࡢș఩Ⅳ⣲ࡢࣉࣟࢺࣥ໬(TS-7A)ࡀࠊ98 kJ/mol ࡢάᛶ໬࢚ࢿ
ࣝࢠ࣮࡛㐍⾜ࡍࡿࠋEnergy span model ゎᯒ࡟ࡼࡾゐ፹ࡢ turnover ࢆỴࡵࡿẁ㝵ࡀࠊ㓟໬ⓗ௜ຍ࠾ࡼࡧᤄ
ධ࡛࠶ࡿࡇ࡜ࡶࢃ࠿ࡗࡓࠋ(N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ)࣋ࣥࢬ࢔࣑ࢻࡢࣇ࢙ࢽࣝᇶࡢ㔜Ỉ⣲⨨᥮ࡋࡓ㏿ᗘྠ఩యຠᯝࡢᐇ㦂࡛ࠊkH/kD = 2.5 ࡛࠶ࡿࡇ࡜࡜୍⮴ࡍࡿࠋTS-7C ࡜ TS-7D ࡟࠾ࡅࡿ KIE㸦ࡑࢀࡒࢀ 1.02,
0.97㸧ࡣᐇ㦂್ࡼࡾࡶᅽಽⓗ࡟ᑠࡉࡃࠊTS-2B ࢆ⤒⏤ࡍࡿ࡜ 9.3 ࡜ᐇ㦂್ࡼࡾࡶ኱ࡁࡃ࡞ࡿࠋ

ᅗ 2.

N-(2-࣓ࢳࣝࢳ࢜)ࣇ࢙ࢽࣝ㸧࣋ࣥࢬ࢔࣑ࢻㄏᑟయࢆ㓄ྥᇶ࡜ࡋ࡚⏝࠸ࡓࠊDFT ィ⟬࡟ࡼࡿ࣐ࣞࣥ࢖࣑

- 189 -

ࢻࡢ C-H ࢔ࣝࢣࢽࣝ໬཯ᛂࡢ࢚ࢿࣝࢠ࣮ኚ໬(M06/def2-TZVP/SMD+W+cc ࣞ࣋ࣝ)


4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Seiji Mori, Chien-Tien Chen, Combined DFT and experimental studies on the importance of noncovalent interactions

in vanadium-catalyzed oxidative trifluoromethylation reactions of olefins, WATOC 2020, July 3-8, 2022, Vancouver,
Canada (invited lecture)‫ۻ‬ΎỈ㞝ோࠊChien-Tien Chenࠊ᳃ ⪷἞ࠊ࢟ࣛࣝ࡞ࣂࢼࢪࣝゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥࡢ࢚ࢼࣥࢳ࢜㑅ᢥⓗ 1,2-࢜࢟ࢩࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែࡢ┦஫స⏝࢚ࢿࣝࢠ࣮ศ๭ゎᯒࠊࢩ࣏ࣥࢪ࢘
࣒ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2022ࠖ
ࠊ2022 ᖺ 9 ᭶ 18 ᪥ࠊᶓ὾
‫ྜྷۻ‬ඖ ⌮ỤࠊAttila TaborosiࠊQiyuan Heࠊ㜿㔝 ຬ௓ࠊⲔ㇂ ┤ேࠊ᳃ ⪷἞ࠊࣃࣛࢪ࣒࢘ゐ፹ࢆ⏝࠸ࡓ࣐ࣞ࢖࣑ࢻࡢ[3+2]⎔໬௜ຍ཯ᛂ࡟࠾ࡅࡿ 2-࣓ࢳࣝ࣋ࣥࢬ࢔࣑ࢻ㢮ࡢ❅⣲ୖࡢ㓄ྥᇶຠᯝ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࠊࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2022ࠖ
ࠊ2022 ᖺ 9 ᭶ 18 ᪥ࠊᶓ὾‫ྜྷۻ‬ඖ⌮ỤࠊAttila TaborosiࠊQiyuan Heࠊ㜿㔝ຬ௓ࠊⲔ㇂┤ேࠊ᳃⪷἞ࠊࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ>@⎔໬௜ຍ཯ᛂࢆྵࡴ࣋ࣥࢪࣝཬࡧ࣓ࢱⅣ⣲Ỉ⣲⤖ྜάᛶ໬཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࠊ㘒య໬Ꮫ఍➨  ᅇウㄽ఍ࠊ ᖺ  ᭶  ᪥ࠊ⚟ᒸࠋ‫⋹ ✚✑ۻ‬᪊, ᕝᓥ ᜤᖹ, すཎ ᗣᖌ, ᳃ ⪷἞ࠊࢽࢵࢣࣝゐ፹࡟ࡼࡿ⬺࢝ࣝ࣎ࢽࣝ໬ࢆྵࡴሷ໬࢔ࢩࣝࡢࢩ
࢔ࣀ໬཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࠊ㘒య໬Ꮫ఍➨ 72 ᅇウㄽ఍ࠊ2022 ᖺ 9 ᭶ 26-28 ᪥ࠊ⚟ᒸ.
‫ۻ‬Takahide Yamaguchi, Attila Taborosi, Wood Kathleen, Whitten Andrew, Seiji Mori, Takamitsu Kohzuma, Tuning of
the Cu Site Properties and Protein Stability by the Noncovalent Interacntions in Second Coordination Sphere of
Pseudaozurin, 10th Asian Biological Inorganic Chemistry (AsBIC10), Nov. 28 - Dec. 3, 2022, Kobe

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1]‫ۻ‬Attila Taborosi, Qiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori, Reaction Path Determination of Rhodium(I)Catalyzed C–H Alkylation of N-8-Aminoquinolinyl Aromatic Amides with Maleimides, J. Org. Chem. 2022, 87, 737–743.
[2]‫ۻ‬Yuki Yamakawa, Takashi Ikuta, Hiroki Hayashi, Keigo Hashimoto, Ryoma Fujii, Kyohei Kawashima, Seiji Mori,
Tatsuya Uchida, and Tsutomu Katsuki, Iridium(III)-Catalyzed Asymmetric Site-Selective Carbene C–H Insertion during
Late-Stage Transformation, J. Org. Chem. 2022, 87, 6769-6780.
[3]‫ۻ‬Yuto Shima, Takashi Suzuki, Hitoshi Abe, Tatsuo Yajima, Seiji Mori, Yuichi Shimazaki, Non-Innocent Redox
Behavior of CuII-S-Dimethylaminophenolate Complexes: Formation and Characterization of the CuI-Phenoxyl Radical
Species, Chem. Commun., 2022, 58, 6401-6404.
[4]‫ۻ‬A. Taborosi, Q. He, Y. Ano, N. Chatani, S. Mori, Reaction Path Determination of Rhodium(I)-Catalyzed C–H
Alkylation of N-8-Aminoquinolinyl Aromatic Amides with Maleimides, J. Org. Chem. 2022, 87, 737-743.
[5]‫ۻ‬T. Takeyama, T. Suzuki, M. Kikuchi, M. Kobayashi, H. Oshita, K. Kawashima, S. Mori, H. Abe, N. Hoshino, S.
Iwatsuki, Y. Shimazaki, Solid State Characterization of One̺and Two̺Electron Oxidized CuII-salen Complexes withpara-Substituents: Geometric Structure̺Magnetic Property Relationship, Eur. J. Inorg. Chem. 2021, 39, 4133-4145.

- 190 -

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3UHGLFWLRQRILQIUDUHGVSHFWUDRIPXOWLHOHPHQWFOXVWHUVIRULQIUDUHGSKRWRGLVVRFLDWLRQVSHFWURVFRS\‫ۑ‬ᕤ⸨ ⪽ࠊỌ⏣ ฼᫂ࠊᒣཱྀ 㞞ே㸦ᮾி኱Ꮫ㸧◊✲┠ⓗ㔠ᒓࢡࣛࢫࢱ࣮ୖ࡛ࡢゐ፹཯ᛂࡢ཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ᪼

⬺㞳ᐇ㦂ࠊ㉥እゎ㞳ศගᐇ㦂࡞࡝ࡢᐇ㦂࡜㔞Ꮚ໬Ꮫィ⟬ࢆే⏝ࡋ࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ௒ᮇࡣ୺࡟ &D0Q2ࢡࣛࢫࢱ࣮ࠊ,Un12m
ࢡࣛࢫࢱ࣮࡞࡝ࢆᑐ㇟࡜ࡋ࡚ィ⟬ࢆ࠾ࡇ࡞ࡗࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㔠ᒓࢡࣛࢫࢱ࣮࡜⿕ゐ፹ศᏊࡢ」ྜయࡢᵓ㐀ࢆỴᐃࡍࡿࡓࡵ࡟ࠊ㉥እゎ㞳ศගᐇ㦂࡛㉥እࢫ࣌ࢡࢺࣝࢆ

ᐃࡋࠊ*DXVVLDQ ࢆ౑⏝ࡋࡓ㔞Ꮚ໬Ꮫィ⟬㸦')7 ィ⟬㸪%/<3 ࡞࡝㸧࡟ࡼࡗ࡚ண
ࣥ࡜ẚ㍑ࡍࡿࡇ࡜࡛ᵓ㐀ࡢỴᐃࢆ࠾ࡇ࡞ࡗࡓࠋࡑࡢ࡯࠿࡟ࠊẼ┦᪼⿕ゐ፹ศᏊࡢ」ྜయ࠿ࡽࡢศᏊ⬺㞳ࡢࡉࢀࡓࢫ࣌ࢡࢺࣝࣃࢱ࣮

⬺㞳ᐇ㦂࡛ᚓࡽࢀࡓ㔠ᒓࢡࣛࢫࢱ࣮࡜

ᗘ౫Ꮡᛶࢆㄝ᫂ࡍࡿࡓࡵ࡟ࠊ཯ᛂ࡟㛵ࢃࡿ୰㛫యࡸ㑄⛣≧ែࡢᵓ㐀᭱㐺໬ࢆ࠾ࡇ࡞ࡗࡓࠋ



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ᡂᯝࡢ୍౛࡜ࡋ࡚ &D0Q2ࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚グ㍕ࡍࡿࠋ㉥እゎ㞳ศග࡟ࡼࡾ &D0Q2࡟ +2 ࡀ྾╔ࡍࡿ࡜ +2 ࡀゎ㞳ࡋ஧ࡘࡢ 2+ ᇶࢆᣢࡘᵓ㐀ࡀ⏕ࡌࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡇࡢ⌮⏤ࢆ▱ࡿࡓࡵ࡟ &D0Q2ୖ࡛ࡢ +2 ࡸ + ཎᏊࠊ2+ ᇶࡢ⛣ືࡢ୰㛫యࡸ㑄⛣≧ែࢆィ⟬ࡋࡓࠋࡇࢀࡲ࡛ࡢᐇ㦂࡜ィ⟬ࡢ⤖ᯝࢆࡲ࡜ࡵ
ࡿ࡜ࠊ&D0Q2࡟ +2 ࡀ௜╔ࡍࡿ࡜ +2 ࡣࢡࣛࢫࢱ࣮ୖࢆᐜ᫆࡟⛣ືࡋ࡚ゎ㞳ࡢ⤒㊰ࡢධཱྀ࡟⮳ࡿࠋḟ࡟ࠊ+2 ࡣ  H9 ࡢ㑄⛣≧ែࢆ㉸࠼࡚ゎ㞳ࡋ + ཎᏊࢆ &D0Q2ࡢ 2 ཎᏊ࡟୚࠼࡚஧ࡘࡢ 2+ ᇶࢆ⏕ᡂࡍࡿࠋࡑࡢᚋࠊ㦵᱁㒊ศࡢᵓ㐀⦆࿴ࢆ⤒࡚᭱Ᏻᐃ࡞ゎ㞳྾╔ᵓ㐀࡟⮳ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸦ฟ∧ᐇ⦼ 㸧ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
཭⃝㸪࿘㸪ᕤ⸨㸪Ọ⏣㸪ᐑᓥ㸪┿⯪㸪ࠕ㉥እගゎ㞳ศගἲ࡟ࡼࡿẼ┦ⓑ㔠ࢡࣛࢫࢱ࣮ୖࡢỈ⣲࣭㓟⣲྾╔ᙧែࡢ◊✲ࠖ㸪➨  ᅇศᏊ⛉Ꮫウㄽ఍  ཭⃝㸪࿘㸪ᕤ⸨㸪Ọ⏣㸪ᐑᓥ㸪┿⯪㸪ࠕ㉥እගゎ㞳ศගἲ࡟ࡼࡿẼ┦ⓑ㔠㓟໬≀ࢡࣛࢫࢱ࣮࡜Ỉ⣲ࡢ཯ᛂࠖ㸪᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬0<DPDJXFKL<=KDQJ29/XVKFKLNRYD-0%DNNHU)0DIXQp³12%RQG&OHDYDJHRQ*DV3KDVH,Un&OXVWHUV,QYHVWLJDWHGE\,QIUDUHG0XOWLSOH3KRWRQ'LVVRFLDWLRQ6SHFWURVFRS\´-3K\V&KHP$±   ‫ۻ‬7=KRX0 $EH<=KDQJ6.XGRK)0DIXQp ³'LVVRFLDWLYH $GVRUSWLRQRI:DWHURQ&D0Q2&DWLRQLF
&OXVWHUV´-3K\V&KHP$±  - 192 -

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫィ⟬
Quantum-Chemical Calculation for Ground and Excited Electronic
States and Molecular Properties of Molecules Containing Heavy
Elements○Ἴ⏣ 㞞ᙪࠊ୰㇂ ┤㍤ࠊ㜿㒊✨㔛ࠊከ⏣ ᐓࠊ∵ᑿ ஧㑻ࠊబ⸨ ᭷ử␃ࠊྜྷ⏣ ⋹He Nanࠊ㔝ᐑ ᾏ㡢ࠊᒾᐊ ᑑ⨾ᯝࠊᮌᮧ ⿱ኴࠊ኱㇂ ඃኴ㑻ࠊKuduva R. Vigneshࠊቑ⏣ᗣேࠊ⣒஭㐶ࠊᑠᯘᯝࠊỤ่ᣅဢࠊᑠ℩ᮧ⚈᫂ࠊ୰㇂ᮃᾏࠊୖ⏣ᯝ✑㸦ᮾி㒔❧኱Ꮫࠊᗈᓥ኱ᏛࠊዉⰋዪᏊ኱Ꮫ㸧㸯 ◊✲┠ⓗࠊෆᐜ┦ᑐㄽࢆ⪃៖ࡋࡓ㟁Ꮚ≧ែࡢ㧗⢭ᗘ࣭኱つᶍィ⟬ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨཬࡧࠊࡑࢀࡽ࡟㛵㐃ࡍࡿୗ㏙ࡢ◊✲ࢸ࣮࣐ࢆ㐍ࡵࡓࠋ
࣐ࣥ࢞ࣥ࢜࢟ࢯ࣏ࣝࣇ࢕ࣜࣥࢆゐ፹࡜ࡋࡓ࢜ࣞࣇ࢕ࣥࡢ࢚࣏࢟ࢩ໬཯ᛂࡢゎᯒ㔠ᒓ 105 ໬Ꮫࢩࣇࢺࡢ 1DWXUDO3HUWXUEDWLRQ2UELWDO 132 ࡟ࡼࡿゎᯒ㟁ᅽ༳ຍ࡟ࡼࡿศᏊෆ &7 ≧ែ࡟࠾ࡅࡿ㟼ⓗ㟁Ꮚ┦㛵ຠᯝ㔜ඖ⣲ྠ఩యศู࡟࠾ࡅࡿ᰾ࡢయ✚ຠᯝࡢ⌮ㄽ◊✲࢔ࢡࢳࣀ࢖ࢻ໬ྜ≀ࡢ㟁Ꮚ≧ែゎ᫂ࡢࡓࡵࡢ㧗⢭ᗘ࣭┦ᑐㄽィ⟬ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ㸬ከ᰾㔠ᒓ㘒యࢆ⏝࠸ࡓගゐ፹཯ᛂࡢ཯ᛂ⤒㊰᥈ᰝ㸬ࢳࢱࣥ㘒యࠊࣂࢼࢪ࣒࢘㘒యࠊ࠾ࡼࡧࢽ࢜ࣈ㘒య࡟ࡼࡿ㔜ྜ཯ᛂࡢゎᯒ㸬1L ,, ࢟ࣀࣀ࢖ࢻ㘒యࡢ࣋࢖࣏ࢡ࣑ࣟࢬ࣒⌧㇟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㸬ᫍ㛫ị⾲㠃࡟࠾ࡅࡿ໬Ꮫ㐍໬࡟㛵ࡍࡿ➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲࢸ࣮࣐㸯㹼㸱࡟ࡘ࠸࡚ࡣ HONDOࠊGAMESSࠊNWChem ࢆ࣮࣋ࢫ࡟ᨵⰋࡋࡓᮏ◊✲ᐊࡢࣉࣟࢢ࣒ࣛࠊࢸ࣮
࣐㸲ࠊ 㸳࡟ࡘ࠸࡚ࡣ DIRACࠊ Gaussianࠊཬࡧࠊ⮬సࡢࣉࣟࢢ࣒ࣛࠊࡑࡢ௚ࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡣ Gaussian09ࠊ
Gaussian16ࠊADFࠊMOLCAS ࢆ㐺ᐅ࡟฼⏝ࡋ࡚◊✲ࢆ⾜ࡗࡓࠋ㸱 ◊✲ᡂᯝ
ୖグ◊✲࡟ᑐࡋࠊ୺࡟ 2020 ᖺᗘ࡟◊✲㐍ᤖࡀ࠶ࡗࡓࢸ࣮࣐ 2ࠊ6ࠊ8ࠊ9 ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
ࢸ࣮࣐ 2 ࡛ࡣࠊ✀ࠎࡢ Se ໬ྜ≀ࡢ Se-NMR ໬Ꮫࢩࣇࢺࢆ⣔⤫ⓗ࡟ẚ㍑࣭ゎᯒࡋࡓࠋィ⟬᪉ἲࡣ ZORADFT ἲ࡛࠶ࡾࠊỗ㛵ᩘࡣ B3LYP ࢆ⏝࠸ࡓࠋゎᯒࡢⅭ࡟ࠊ᪂ࡓ࡟㛤Ⓨࡋࡓ⮬↛ᦤື㌶㐨㸦NPO㸧ࢆ⏝࠸ࡓࠋᅗ㸯ࡣィ⟬⤖ᯝ࡛࠶ࡿ Se-NMR ໬Ꮫࢩࣇࢺ࡜ 4p ཬࡧ 3d ㌶㐨ࡢ㟁Ꮚ population ࡜ࡢ┦㛵ࢆ♧ࡋࡓࠋSe ཎᏊࡢ㟁Ꮚ㓄⨨ࡣ[Ar](3d)10(2s)2(4p)4(4d)0 ࡛࠶ࡿࠋࡑࡢⅭࠊ4p-population ࡜ Se-NMR ໬Ꮫࢩࣇࢺࡣࠊ
ࠋ୍᪉ࠊ4d ㌶(4p)6 ࡢ㏆ഐ࡛ࡣⰋ࠸┦㛵ࢆ♧ࡋࠊ4p-population ࡀ㸰㹼㸲࡛ࡣ┦㛵ࡀ୙᫂░࠶ࡿ㸦ᅗ㸯ᕥ㸧㐨࡛ࡣ┦㛵ࡣ࠶ࡿࡶࡢࡢᐤ୚ࡣᚤᑠ࡛࠶ࡿ㸦ᅗ㸯ྑ㸧ࠋ᭦࡟ゎᯒࢆ㐍ࡵࡿࡓࡵ࡟⮬↛ᦤື㌶㐨(NPO)ࢆ⏝࠸ࡓࠋࡇࡇ࡛ NPO ࢆ⡆༢࡟ㄝ᫂ࡍࡿࠋ☢ሙࡢᦤື B ࡟ࡼࡿ㸯ḟࡢ≀ᛶȪࡣࠊࢭࣟḟ㌶㐨࡜㸯ḟᦤື㌶
1

1

㐨\ i ࢆ౑ࡗ࡚ḟᘧࡢࡼ࠺࡟᭩ࡅࡿࠋࡲࡓࠊ㸯ḟᦤື㌶㐨ࡢ㌶㐨ಀᩘࢆ U ji ࡜ࡍࡿ࡜ḟᘧ⩌ࢆᚓࡿࠋ V- 193 -

ࡣࣘࢽࢱ࣮ࣜኚ᥮⾜ิ࡛࠶ࡿࠋ

V

occ

¦ \i
i

Cˆ o1

0

Vˆ \ i1§U 1 ·
C o0 C v 0 ¨ oo1 ¸ ,© U vo ¹

C o1,
Cˆ o0 Cˆ v 0

C o1 C v1 Voo ,§V c V c ·C o0 C v 0 ¨ oo ov ¸ ,   Cˆ o1© Vvoc Vvvc ¹§V c† V c† · § U 1 ·Cˆ o0 Cˆ v 0 ¨ oo† vo† ¸ ¨ oo1 ¸Voo .
©Vovc Vvvc ¹© U vo ¹

≉␗್ศゎࢆᐇ᪋ࡍࡿ࡜≉␗್ /oo ࢆᚓࡿࠋࡇࡢ࡜ࡁࡢ Cˆ o0 Cˆ v 0 ࡀ NPO ࡛࠶ࡾࠊᑡᩘࡢ NPO ࣌࢔̿ࡢᐤ୚࡛≀ᛶȪࡀ⾲⌧࡛ࡁࡿࠋ§Vooc† Vvoc† · § U oo1 ·¨ † † ¸ ¨ 1 ¸Voo
©Vovc Vvvc ¹© U vo ¹

§ /oo ·
¨ O ¸,©
¹/oodiag O1 , O2 ,   , ONocc ,V

occ¦i \ˆi00Vˆ \ˆ i  Nocc Oi

Se(CH3)2 ࡢ Se ᰾☢Ẽ㐽ⶸᐃᩘࢆ༨᭷㌶㐨㸫㠀༨᭷㌶㐨ࡢ࣌࢔̿ࡢᐤ୚࡟ศゎࡋࡓࠋṇ‽㌶㐨࡛ࡣᐤ୚
ࡀከࡃࡢ㌶㐨࣌࢔̿࡟ศᩓࡋ࡚࠸ࡓࡀࠊ⮬↛ᦤື㌶㐨(NPO)࡛ࡣࠊ㸯࣌࢔̿ࡢᐤ୚ࡀ 85%௨ୖ࡜࡞ࡾࠊ
໬Ꮫࢩࣇࢺࡢゎᯒࡀᐜ᫆࡟࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋ

ᅗ㸯㸬Se-NMR ໬Ꮫࢩࣇࢺ࡜ 4p,4d 㟁Ꮚ࣏ࣆ࣮ࣗࣞࢩࣙࣥ࡜ࡢ┦㛵ᅗ㸰㸬Se ☢Ẽ㐽ⶸࡢ㌶㐨
࣌࢔̿ࡈ࡜ࡢᐤ୚

ࢸ࣮࣐ 6 ࡛ࡣࠊ2 ᰾㔠ᒓ㘒య (Ru-Pd, Ir-Pd) ࢆゐ፹࡟⏝࠸ࡓࢫࢳࣞࣥ㔜ྜࡢගゐ፹཯ᛂᶵᵓࡢゎ᫂࡟ྥࡅ࡚ࠊᐦᗘỗ㛵ᩘἲࢆ⏝࠸ࡓ⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡇࢀࡽࡢ 2 ᰾㔠ᒓゐ፹࡟ࡼࡿ㐣ཤࡢᐇ㦂࡛ࡣࠊྍどග↷ᑕୗ࡟࠾࠸࡚࣏ࣜࢫࢳࣞࣥ㔜ྜࡢ཯ᛂᛶࡀቑຍࡋ࡚࠸ࡓࠋ≉࡟ࢼࣇࢳࣝ⨨᥮ᇶࡀᑟධࡉࢀࡓࣇ࢙ࢽ
ࣝ㓄఩Ꮚࡢ㓄఩ࡋࡓ Ir-Pd1 㘒య ( ᅗ 3 ᕥ (f) ) ࡟ᑐࡋ࡚཯ᛂᛶࡀቑ኱ࡋࡓࡀࠊ㢮ఝࡢ␗ᛶయ࡛࠶ࡿ IrPd2㸦ᅗ 3 ᕥ (g㸧)࡛ࡣࢼࣇࢳࣝ௜ຍ࡟ࡼࡿ཯ᛂᛶࡢቑ኱ࡀぢࡽࢀ࡞࠿ࡗࡓࠋ⨨᥮ᇶຠᯝࡀ࡝ࡢࡼ࠺࡟཯
ᛂάᛶࢆྥୖࡍࡿࡢ࠿ࢆㄪ࡭ࡿࡓࡵ࡟ࠊࡇࢀࡽࡢゐ፹㘒యࡢບ㉳≧ែࡢᨺᑕᑑ࿨ࢆᮏ◊✲࡛⌮ㄽィ⟬ࡋࡓ࡜ࡇࢁࠊIr-Pd1 ゐ፹ࡀ᭱ࡶ㛗࠸ᑑ࿨ࢆ♧ࡋࡓࠋࡇࡢ⤖ᯝࡣࠊ࣏ࣜࢫࢳࣞࣥ㔜ྜࡢ཯ᛂᛶࡢഴྥ࠾ࡼࡧࠊ┤᥋ ᐃࡋࡓບ㉳ᑑ࿨ࡢᐇ㦂⤖ᯝ࡜ࡶ୍⮴ࡋ࡚࠸ࡿࠋග໬Ꮫ཯ᛂ࡛࠶ࡿࡓࡵບ㉳≧ែࡀ཯ᛂ࡟㛵୚ࡋ࡚࠾ࡾࠊບ㉳≧ែࡢᏳᐃᛶ㸦㸻㛗࠸ᑑ࿨㸧ࡀࠊ཯ᛂᛶࢆ㧗ࡵ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ࡞ࡐᑑ࿨ࡀ㛗࠸࠿࡜࠸࠺࡜ࠊIr-Pd1 ࡛ࡣ HOMO-LUMO ࢠࣕࢵࣉࡀ᭱ࡶᑠࡉࡃ(ᅗ㸱ྑ)ࠊࢼࣇࢳࣝ㓄఩Ꮚ࡜ࣇ࢙ࢽࣝ㓄఩Ꮚࡢ㛫ࡢȧ*㸫ȧ*┦஫స⏝࡟ࡼࡗ࡚ HOMO ࡀ୙Ᏻᐃ໬ࡋࡓ࠿ࡽ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࡇࡢ HOMOLUMO ࢠࣕࢵࣉࡢᑠࡉࡉࡣࠊIr ࡜ Pd 㛫ࡢᯫᶫ㓄఩Ꮚ࡬ࡢ㔠ᒓ࠿ࡽ㓄఩Ꮚ࡬ࡢ㟁Ⲵ⛣ືࢆಁ㐍ࡋࠊ཯ᛂ୰ᚰ࡛࠶ࡿ Pd ࡢ㟁Ⲵ࡟ࡶᙳ㡪ࢆཬࡰࡍ࡜⪃࠼ࡽࢀࡿࠋ
ࡉࡽ࡟ࢫࢳࣞࣥ 2 㔞యࡀᙧᡂࡍࡿ㐣⛬࡟ࡘ࠸࡚ࠊ⇕ⓗ⤒㊰ࡸບ㉳≧ែࢆ⤒⏤ࡋࡓ཯ᛂ⤒㊰࡟ࡘ࠸࡚ࠊ
3 ࣃࢱ࣮ࣥ⌮ㄽィ⟬࡛ồࡵࡓࠋ3 㔜㡯ບ㉳≧ែࡢᏳᐃᵓ㐀ࡀࠊ⇕ⓗ⤒㊰࡛ᚓࡽࢀࡿ㑄⛣≧ែ࡜࢚ࢿࣝࢠ

- 194 -

࣮ⓗ࡟ࡶศᏊᵓ㐀ⓗ࡟ࡶ㢮ఝⅬࡀ࠶ࡗࡓࡓࡵࠊගບ㉳ࡋ࡚ 3 㔜㡯≧ែ࡟ᵓ㐀⦆࿴ࡋࡓᚋࠊࢫࣆࣥ㌿᥮ࡋࠊ
ࡑࡢࡲࡲ TS ࡟㏆࠸ᵓ㐀ࢆ⤒࡚⏕ᡂ≀࡟฿㐩ࡍࡿ⤒㊰ࡀ࠶ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ

ᅗ㸱. 7 ✀ࡢ 2 ᰾㔠ᒓ㘒యගゐ፹࡜㌶㐨࢚ࢿࣝࢠ࣮ᅗ

ࢸ࣮࣐ 8 ࡛ࡣࠊ㛵すᏛ㝔኱࣭ຍ⸨ඛ⏕ࠊ㇏ᶫᢏ⛉኱࣭ᚋ⸨ඛ⏕ࠊࢥࣥࣇࣞࢵࢡࢫ♫࣭୰ᒣ༤ኈࡽ࡜ඹ
ྠࡋ࡚ࠊ࣋࢖࣏ࢡ࣑ࣟࢬ࣒⌧㇟ࢆ♧ࡍ Ni(II)࢟ࣀࣀ࢖ࢻ㘒యࡢ⤖ᬗᵓ㐀ண ࠊ࠾ࡼࡧ྾཰࢚ࢿࣝࢠ࣮ኚ
໬ࡢศᏊㄽⓗ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ⾜ࡗࡓࠋᮏᖺᗘࡣࠊ୰ᒣ༤ኈ࡜ඹྠࡋ࡚ᚓࡽࢀࡓィ 20 ✀ࡢᅄ㓄఩ Ni 㘒యࡢೃ⿵⤖ᬗᵓ㐀࡟ࡘ࠸࡚ࠊVASP ࢆ฼⏝ࡋ࡚ DFT ἲ࡟ࡼࡿᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮Ᏻᐃᛶࠊ࠾ࡼࡧᐇ㦂ࡢ⢊ᮎ X ⥺ࢫ࣌ࢡࢺࣝ
࡜ࡢẚ㍑ࢆ⾜࠺ࡇ࡜࡛ࠊጇᙜ࡞⤖ᬗᵓ㐀ࢆ⌮ㄽⓗ࡟ண ࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡲࡓࠊᐇ㦂ⓗ࡟ࡍ࡛࡟ᵓ
㐀ࡀỴᐃࡉࢀ࡚࠸ࡿ࣓ࢱࣀ࣮ࣝศᏊ྾╔ᚋࡢභ㓄఩ Ni 㘒య࡜࠶ࢃࡏ࡚ࠊ⤖ᬗ୰ࡢ྾཰ࢫ࣌ࢡࢺࣝࢆㄏ
㟁㛵ᩘ࠿ࡽィ⟬ࡋࠊ࣓ࢱࣀ࣮ࣝศᏊࡢ྾╔๓ᚋ࡟࠾ࡅࡿ྾཰ࢫ࣌ࢡࢺࣝኚ໬ࢆᑡ࡞ࡃ࡜ࡶᐃᛶⓗ࡟ṇࡋࡃ෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ㸦ᅗ 4㸧ࠋ

ᅗ 4. Ni(II)࢟ࣀࣀ࢖ࢻ㘒యࡢ⤖ᬗᵓ㐀ண 㸦ᕥ㸧࡜྾཰ࢫ࣌ࢡࢺࣝィ⟬㸦ྑ㸧≧ែᐦᗘ࡜ࣂࣥࢻᵓ㐀ࡢゎᯒ࠿ࡽࠊᅄ㓄఩ Ni 㘒య࡛ࡣࠊ⤖ᬗ୰࡛ศᏊ㠃ࡀ㔜࡞ࡿࡇ࡜࡛ȧࢫࢱࢵ࢟ࣥࢢ┦஫స⏝ࡀ a ㍈᪉ྥ࡟⧅ࡀࡗ࡚࠾ࡾࠊNi ࡢ 3d ㌶㐨࡜࢟ࣀࣀ࢖ࢻࡢȧ㌶㐨࠿ࡽ࡞ࡿࣂࣥࢻࡀᙧᡂࡉ
ࢀࡿࡇ࡜࡛ࠊບ㉳࢚ࢿࣝࢠ࣮ࡀప࢚ࢿࣝࢠ࣮ഃ࡟኱ࡁࡃࢩࣇࢺࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢࡼ࠺࡞
ȧࢫࢱࢵ࢟ࣥࢢ┦஫స⏝࡟ࡼࡗ࡚ᙧᡂࡉࢀࡿࣂࣥࢻᵓ㐀ࡣࠊගᏛ≉ᛶࢆ᭷ࡍࡿ㘒యศᏊࡢศᏊ⤖ᬗ࡛ࡣࡋࡤࡋࡤぢࡽࢀࡿࡀࠊᮏ◊✲ࡢ⤖ᯝࡣࠊࡇ࠺ࡋࡓࣂࣥࢻᵓ㐀ࡀᶵ⬟࡟┤᥋ᙳ㡪ࢆ୚࠼ࡿ㠀ᖖ࡟≉␗࡞⣔࡛࠶ࡾࠊศᏊ⤖ᬗࡢගᶵ⬟ไᚚ࡟᪂ࡓ࡞ྍ⬟ᛶࢆ୚࠼ࡿࡶࡢ࡛࠶ࡿࠋ

- 195 -

ࢸ࣮࣐ 9 ࡛ࡣࠊᫍ㛫✵㛫࡟࠾ࡅࡿ໬Ꮫ㐍໬࡟ࡘ࠸࡚ࠊ᪂₲኱࣭ୗすඛ⏕ࠊ⟃Ἴ኱࣭ྂᐙඛ⏕࡜ඹྠࡋ࡚ཎᏊ࣭ศᏊࡢị⾲㠃࡬ࡢ྾╔ࠊ࠾ࡼࡧᣑᩓ㐣⛬ࡢ⣔⤫ⓗ࡞ࣃ࣓࣮ࣛࢱண ࢆ⾜ࡗ࡚࠸ࡿࠋࡇࢀࡲ࡛ࡢ
◊✲࡛ࡣࠊCࠊNࠊO ࡞࡝ࡢ 2P ࣈࣟࢵࢡඖ⣲࡟ࡘ࠸࡚ࠊỈࢡࣛࢫࢱ࣮ࣔࢹࣝࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡾࠊࡑࡢ྾╔࢚ࢿࣝࢠ࣮ࢆ⣔⤫ⓗ࡟ண ࡍࡿࡇ࡜࡟ᡂຌࡋ࡚࠸ࡿࠋ
ᮏᖺᗘࡣࠊᏱᐂ✵㛫࡟࠾ࡅࡿືែࡀ୙᫂࡞ 3P ࣈࣟࢵࢡඖ⣲࡟ࡘ࠸࡚ྠᵝࡢ᳨ウࢆ⾜࠸ࠊP ཎᏊࡀ N
ཎᏊ࡜ྠᵝ࡟ị⾲㠃࡬≀⌮྾╔ࡍࡿࡇ࡜ࠊS ཎᏊࡀ O ཎᏊ࡜ྠᵝ࡟≀⌮྾╔࡜໬Ꮫ྾╔ࡢ୧᪉ࡢᛶ㉁ࢆ♧ࡍࡇ࡜ࠊ࠾ࡼࡧ Cl ཎᏊࡀ⾲㠃ࡢỈศᏊ࡜୍㒊཯ᛂࡋ࡚ HCl ࡀ⏕ᡂࡍࡿࢣ࣮ࢫࡀ࠶ࡿࡇ࡜ࠊࢆ᫂ࡽ
࠿࡟ࡋࡓࠋP ཎᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࡢィ⟬್ࡣ⣙ 900K ࡜ࠊN ཎᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࡢィ⟬್࡛࠶ࡿ⣙400K ࡜ẚ㍑ࡋ࡚ࡶ኱ࡁࡃࠊP ཎᏊࡢ⾲㠃ᣑᩓࡣ N ཎᏊ࡟ẚ࡭ࡿ࡜㐜࠸࡜ண᝿ࡉࢀࠊị⾲㠃࡛ PH3 ศᏊࡀ⏕ᡂࡍࡿྍ⬟ᛶࡀ㧗࠸ࠋࡲࡓࠊCl ཎᏊࡢ⤖ᯝࡣࠊᏱᐂ✵㛫࡛ほ ࡉࢀࡿ HCl ࡢ࢔ࣂࣥࢲࣥࢫࡀண᝿
ࡉࢀࡿࡼࡾࡶ኱ࡁ࠸ࡇ࡜࡬ࡢ 1 ࡘ࡜⟅࠼࡜࡞ࡾᚓࡿ⯆࿡῝࠸⤖ᯝ࡛࠶ࡿࠋ

㸲 Ⓨ⾲ᐇ⦼
㔝ᐑᾏ㡢 HW DOࠊ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸭኱㇂ඃኴ㑻 HW DOࠊ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭Ἴ⏣㞞ᙪࠊ3XUH $QG $SSOLHG &KHPLVWU\,QWHUQDWLRQDO&RQIHUHQFH㸦3$&&21㸧ࠊ ᖺ  ᭶  ᪥ ᭶  ᪥㸭୰㇂┤㍤ࠊ㔞Ꮚ໬Ꮫ᥈⣴◊✲ᡤࢩ࣏ࣥࢪ࣒࢘ ࠊ ᖺ  ᭶  ᪥㸭+H 1DQ HW DOࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶ ᪥ ᪥㸭኱㇂ඃኴ㑻HWDOࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸭㔝ᐑᾏ㡢HWDOࠊ
㘒య໬Ꮫ఍➨  ᅇウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸭ᕝ㷂ឡ⌮ et al.ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍⛅Ꮨᖺ
఍ࠊ2022 ᖺ 11 ᭶ 25 ᪥-27 ᪥㸭୰㇂┤㍤ࠊ➨ 12 ᅇ㔞Ꮚ໬Ꮫࢫࢡ࣮ࣝࠊ2022 ᖺ 12 ᭶ 6 ᪥-8 ᪥㸭Ἴ⏣㞞ᙪࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ 2022ࠊ2023 ᖺ 1 ᭶ 16 ᪥-17 ᪥㸭ᒾᐊ ᑑ⨾ᯝ et al.ࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2022 ᖺ 9 ᭶ 19 ᪥-22 ᪥㸭ྜྷ⏣⋹ et al.ࠊ᪥ᮏᨺᑕ໬Ꮫ఍➨ 66 ᅇウㄽ఍(2022)ࠊ2022 ᖺ
9 ᭶ 15 ᪥㹼17 ᪥㸭㜿㒊✨㔛 ᪥ᮏᨺᑕ໬Ꮫ఍➨ 66 ᅇウㄽ఍(2022)ࠊ2022 ᖺ 9 ᭶ 15 ᪥㹼17 ᪥㸭㔝⏣⣫ᖹ et al. 2022 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍ᗈᓥ኱఍, 2022 ᖺ 11 ᭶ 12 ᪥㹼13 ᪥㸭ቑ⏣ᗣே et al. 2022ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍ᗈᓥ኱఍, 2022 ᖺ 11 ᭶ 12 ᪥㹼13 ᪥㸭㧘ᒣඃᕼ et al. ➨ 20 ᅇྠ఩య⛉Ꮫ◊✲఍ 2023 ᖺ 3 ᭶ 10 ᪥㸭బ⸨᭷ử␃ et al. ➨ 20 ᅇྠ఩య⛉Ꮫ◊✲఍ 2023 ᖺ 3 ᭶ 10 ᪥㸭బ⸨᭷ử
␃ et al. 2022 㔜ඖ⣲໬Ꮫ◊✲఍, 2023 ᖺ 3 ᭶ 20 ᪥㹼21 ᪥㸭ᡞ⏣ᬛ῵ et al. 2022 㔜ඖ⣲໬Ꮫ◊✲఍, 2023 ᖺ 3 ᭶ 20 ᪥㹼21 ᪥㸭ቑ⏣ ᗣே et al. 2022 㔜ඖ⣲໬Ꮫ◊✲఍, 2023 ᖺ 3 ᭶ 20 ᪥㹼21 ᪥
㸭M. Abe et al. 13th International Conference on Relativistic Effects in Heavy-Element Chemistry and Physics,
26th-30th Sep. 2022, Italy㸭M. Abe et al., Searches for Electric Dipole Moments: From Theory to Experiment, 2ndMarch 2023, Nagoya.

5

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

◊✲┠ⓗ
㏆ᮍ᮶࡟ᚲせ࡜࡞ࡿ㟁⏺ຠᯝᆺࢺࣛࣥࢪࢫࢱ㸦MOSFET㸧ࡸḟୡ௦᣺ືⓎ㟁⣲Ꮚ࡟ᑐࡍࡿタィᣦ㔪ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ᥦ᱌ࡍࡿࡇ࡜ࢆ㏻ࡋ࡚ࠊḟୡ௦࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝ♫఍ᐇ⌧ࡢࡓࡵࡢᇶ♏࡜࡞ࡿ༙ᑟయ/⤯⦕య⏺㠃࡟ᑐࡍࡿཎᏊ࣭ࣞ࣋ࣝ㟁Ꮚࣞ࣋ࣝࡢ▱ぢࢆ⋓ᚓࡍࡿࡇ࡜ࡀᮏ◊✲ㄢ㢟ࡢ┠ⓗ࡛࠶ࡿࠋ⌧ᅾࡢ௦⾲ⓗ࡞༙ᑟయࢹࣂ࢖ࢫࡣ MOSFET ࡛࠶ࡿࠋࡲࡓḟୡ௦᣺ືⓎ㟁⣲Ꮚ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞ
ࢡࣞࢵࢺࡣ Si/SiO2 ⏺㠃ࢆࡑࡢᵓᡂせ⣲࡜ࡋ࡚࠸ࡿࠋࡑࡢࡓࡵࡇࢀࡽࡢ༙ᑟయ/⤯⦕య⏺㠃ࡢရ㉁ࡀࡇࢀࡽࡢ
ࢹࣂ࢖ࢫࡢᛶ⬟ࢆᕥྑࡍࡿࠋ᭱㏆࡛ࡣࠊࣃ࣮࣡ࢹࣂ࢖ࢫ⏝ࡢ GaN/㓟໬≀⏺㠃ࢆ⏝࠸ࡓ MOSFET ࡀ࣮࢝࣎ࣥ
ࢽ࣮ࣗࢺࣛࣝ♫఍ࡢᐇ⌧ࡢࡓࡵ࡟኱ࡁ࡞ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋGaN-MOSFET ⏝ࡢࢤ࣮ࢺ⤯⦕⭷࡜ࡋ࡚ೃ⿵࡟ᣲ
ࡀࡗ࡚࠸ࡿࡢࡀ SiO2 ࡜ Al2O3 ࡛࠶ࡿࠋᮏ◊✲࡛ࡣ GaN/SiO2 ࡜ GaN/Al2O3 ⏺㠃ࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆ➨୍ཎ⌮ィ⟬࡛᫂ࡽ࠿࡟ࡍࡿࠋ≉࡟᭱㏆ GaN-MOSFET ࡢᐇ⏝໬ࡢ㝿࡟ၥ㢟࡜࡞ࡗ࡚࠸ࡿ౯㟁Ꮚᖏ௜㏆ࡢ⏺㠃‽఩ࡢཎᏊ࣭ࣞ࣋ࣝ㟁Ꮚࣞ࣋ࣝࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡋࠊࡇࡢ౯㟁Ꮚᖏ௜㏆ࡢ⏺㠃‽఩ࢆ㝖ཤࡍࡿࡓࡵࡢฎ᪉⟢ࢆᥦ᱌ࡋࠊḟୡ௦࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝ♫఍ࡢᇶ♏ࢆᙧసࡿࠋࡲࡓࠊSi/SiO2 ⏺㠃ࡣ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࣞࢵࢺ
ࢆ⏝࠸ࡓḟୡ௦᣺ືⓎ㟁⣲Ꮚ࡟࠾࠸࡚᭱ࡶᇶᮏ࡜࡞ࡿ⏺㠃࡛࠶ࡿࠋ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࡣ༙Ọஂⓗ࡟㈇㟁Ⲵࢆ⵳✚ࡍࡿᮦᩱ࡛ SiO2 ࡟ K ཎᏊࢆΰධࡍࡿࡇ࡜࡟ࡼࡗ࡚ᐇ⌧ࡉࢀࡿࡀ㈇㟁Ⲵ⵳✚ࡢ≀⌮ⓗ㉳※ࡣ඲ࡃࢃ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲ㄢ㢟࡛ࡣ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࡀ㈇㟁Ⲵࢆ⵳✚ࡍࡿཎᏊ࣭ࣞ࣋ࣝ㟁Ꮚࣞ࣋ࣝࡢᶵᵓࢆ᫂ࡽ࠿࡟ࡋࠊ᣺ືⓎ㟁⣲Ꮚࡢᛶ⬟ྥୖࡢฎ᪉⟢ࢆᥦ᱌ࡍࡿࠋ
௨ୖࡢ◊✲࡟ࡼࡗ࡚ࠊ㏆ᮍ᮶࡟ᚲせ࡜࡞ࡿ༙ᑟయ MOSFET ࡸ᣺ືⓎ㟁⣲Ꮚ࡟ᑐࡍࡿタィᣦ㔪ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ᥦ᱌ࡍࡿࡇ࡜ࢆ㏻ࡋ࡚ࠊḟୡ௦࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝ♫఍ᐇ⌧ࡢࡓࡵࡢ▱ぢࢆ⋓ᚓࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲձ  GaN-MOSFET ⏝ࡢ GaN/SiO2 ⏺㠃࡜ GaN/Al2O3 ⏺㠃ࡢ◊✲᪉ἲ࡜ィ⟬᪉ἲ
GaN-MOSFET ⏝ࡢ GaN/SiO2 ⏺㠃࡜ GaN/Al2O3 ⏺㠃ࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟
ࡍࡿࠋලయⓗ࡟ࡣ GaN/SiO2 ཬࡧ GaN/Al2O3 ⏺㠃ࢆࣔࢹࣝ໬ࡋࡓ 500 ཎᏊ⛬ᗘࡢ༢఩⬊ࢆ⏝ពࡋࠊSiO2 ཬࡧ
Al2O3 ⤯⦕⭷ࢆ࣓ࣝࢺࢡ࢚ࣥࢳἲ࡛࢔ࣔࣝࣇ࢓ࢫ໬ࡍࡿࠋලయⓗ࡟ࡣ⤯⦕⭷ࢆ 5000K ࡛࣓ࣝࢺࡉࡏࡓᚋࠊ
50K/psࠥ100K/ps ࡛෭༷ࡍࡿࠋSiO2 ࡣ 50K/ps ࡛ࠊAl2O3 ࡣ 100K/ps ࡛෭༷ィ⟬ࢆ⾜࠺ࠋࡇ࠺ࡋ࡚ᚓࡽࢀࡓ
GaN/a-SiO2 ཬࡧ GaN/a-Al2O3 ࡢ⏺㠃ࣔࢹࣝࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆゎᯒࡍࡿࠋ≉࡟ὀຊࡍࡿࡢࡣ GaNMOSFET ࢆᐇ⏝໬ࡍࡿ㝿ࡢࢿࢵࢡ࡟࡞ࡗ࡚࠸ࡿ౯㟁Ꮚᖏ௜㏆ࡢ⏺㠃‽఩࡛࠶ࡿࠋᡃࠎࡣ⏺㠃௜㏆ࡢ Ga-O-Si⤖ྜࡸ Ga-O-Al ⤖ྜ୰ࡢ O ཎᏊࡢ lone pair ࡀḞ㝗‽఩ࡢ㉳※࡜࡞ࡿឤゐࢆᚓ࡚࠸ࡿࡀࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ࡑࡢཎᏊ࣭ࣞ࣋ࣝ㟁Ꮚࣞ࣋ࣝࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ➨୍ཎ⌮ィ⟬ࢯࣇࢺ࡜ࡋ࡚ VASP ࢆ⏝࠸࡚⾜࠺ࠋ- 197 -

ղ

᣺ືⓎ㟁⣲Ꮚ⏝ࡢ Si/SiO2 ⏺㠃ࡢ◊✲᪉ἲ࡜ィ⟬᪉ἲ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࢆ⏝࠸ࡓḟୡ௦᣺ືⓎ㟁⣲Ꮚ⏝ࡢ Si/SiO2 ⏺㠃ࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡍࡿࠋලయⓗ࡟ࡣࠊSi/SiO2 ⏺㠃ࢆࣔࢹࣝ໬ࡋࡓ 500 ཎᏊ⛬ᗘࡢ༢఩⬊ࢆ⏝ពࡋࠊK ཎᏊࢆྵࡴ SiO2 ⤯⦕⭷ࢆ࣓ࣝࢺࢡ࢚ࣥࢳἲ࡛࢔ࣔࣝࣇ࢓ࢫ໬ࡍࡿࠋ⤯⦕⭷ࢆ 5000K ࡢ㧗࡛࣓ࣝࢺࡉࡏࡓᚋࠊ50K/ps ࡛෭༷ࡍࡿࠋࡇ࠺ࡋ࡚ᚓࡽࢀࡓ Si/a-SiO2 ࡢ⏺㠃ࣔࢹࣝࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆゎᯒࡍࡿࠋ➨୍ཎ⌮ィ⟬ࢯࣇࢺ࡜ࡋ࡚ VASP ࢆ⏝࠸࡚⾜࠺ࠋ



◊✲ᡂᯝ

ձ

GaN-MOSFET ⏝ࡢ GaN/SiO2 ⏺㠃ࡢ◊✲ᡂᯝ๓⠇࡛ㄝ᫂ࡋࡓ࣓ࣝࢺࢡ࢚ࣥࢳἲࡢィ⟬ࡢ⤖ᯝࠊᚓࡽࢀࡓ

GaN/a-SiO2 ࡢ⏺㠃ᵓ㐀ࢆᅗ㸯࡟♧ࡍࠋ⏺㠃ࡣࠊGaN ⾲㠃ࡢ Ga ཎᏊࡀ඲࡚ O ཎᏊ࡜⤖ྜࡋࡓᵓ㐀ࢆᙧᡂࡋ࡚࠾ࡾࠊࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡣⓎ⏕ࡋ࡞࠿ࡗࡓࠋ⏺㠃ࡢ Ga-O ⤖ྜ࡟ࡣ 3 ࡘࡢࢱ࢖ࣉ
ࡀ࠶ࡾࠊࡑࢀࡒࢀ⤖ྜཎᏊࡢᩘ࡜✀㢮࡟㐪࠸ࡀ࠶ࡿࠋ㸯ࡘ┠ࡣࠊO ཎᏊࡀ SiࠊGa ࡜⤖ྜࡋࡓ 2 㓄఩ᵓ㐀㸦ᅗ 1(a)㸧
ࠋ2 ࡘ┠ࡣࠊOཎᏊࡀ SiࠊSiࠊGa ࡜⤖ྜࡋࡓ 3 㓄఩ᵓ㐀㸦ᅗ㸯(b)㸧ࠋ3 ࡘ┠ࡣࠊᅗ㸯:ᚓࡽࢀࡓ GaN/a-SiO2 ࡢ⏺㠃ᵓ㐀O ཎᏊࡀ SiࠊGaࠊGa ࡜⤖ྜࡋࡓ 3 㓄఩ᵓ㐀㸦ᅗ 1(c)㸧࡛࠶ࡿࠋḟ࡟ࠊ⏺㠃ࡢ 3 ✀㢮ࡢ Ga-O ⤖ྜ(ᅗ㸯(a),(b),(c)) ࡟ᑐࡋ࡚ࠊྛཎᏊࡢ౯㟁Ꮚᩘ࠿ࡽࡑࢀࡒࢀࡢ⤖ྜ࣎ࣥࢻ࡟ྵࡲࢀࡿ㟁Ꮚᩘࢆ࢝࢘ࣥࢺࡋࡓࠋྛཎᏊࡢ౯㟁ᏊᩘࡣࠊGa㸸3
ಶ(4s24p1)ࠊSi㸸4 ಶ(3s23p2)ࠊO㸸6 ಶ(2s22p4)
࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊ4 㓄఩ࡢ Ga ࡜ Si ࡣ 1࣎ࣥࢻᙜࡓࡾࡑࢀࡒࢀ 3/4 ಶ࡜ 1 ಶࡢ㟁Ꮚࢆ౪⤥ࡍࡿࠋࡇࢀࡣࠊ୍᪉࡛ࠊ2 㓄఩ࡢ O ཎᏊᅗ㸰: ⏺㠃 Ga-O ⤖ྜࡢ⤖ྜ㟁Ꮚࡢᩘ࡜࢚ࣞࢡࢺࣟࣥ࢝࢘ࣥ
ࢸ࢕ࣥࢢࣔࢹࣝ

࡟ࡣ 2 ⤌ࡢ lonepairࠊ3 㓄఩ࡢ O ཎᏊ࡟ࡣ 1⤌ࡢ lonepair ࡀᏑᅾࡍࡿࡓࡵࠊ1 ࣎ࣥࢻᙜࡓࡾ࡛ 2 㓄
఩ࡢ O ཎᏊࡣ 1 ಶࠊ3 㓄఩ࡢ O ཎᏊࡣ 4/3 ಶࡢ㟁Ꮚ

SiO2

ࢆ౪⤥ࡍࡿࠋ㸯ࡘࡢ⤖ྜ࣎ࣥࢻࡣ 2 ಶࡢ㟁Ꮚ࡛᏶඲࡟༨᭷ࡉࢀࡿ࡜⪃࠼ࡿ࡜ࠊᅗ㸯(a)ࡢᵓ㐀࡛ࡣ㟁Ꮚࡀ
1/4 ಶ୙㊊ࠊᅗ㸯(b)ࡢᵓ㐀࡛ࡣ㟁Ꮚࡀ 3/4 ಶ㐣๫ࠊ
ᅗ㸯(c)ࡢᵓ㐀࡛ࡣ㟁Ꮚࡀ 1/2 ಶ㐣๫࡛࠶ࡿ(ᅗ㸰)ࠋ

VBM

GaN

ࡋ࠿ࡋࠊࡇࢀࡽࡢ㟁Ꮚࡢ㐣୙㊊ࢆ⏺㠃඲య࡛ྜィࡍࡿ࡜ࠊ⥡㯇࡟ᡴࡕᾘࡋ࠶࠸୎ᗘࢮࣟ࡟࡞ࡿࠋࡘࡲࡾࠊ
㟁Ꮚࡢవࡗࡓ⤖ྜ࣎ࣥࢻ࠿ࡽ㟁Ꮚࡢ୙㊊ࡋࡓ⤖ྜ࣎ᅗ㸱:ᛴᓧ࡞ GaN/a-SiO2 ⏺㠃ࡢ≧ែᐦᗘࠋࣥࢻ࡟㟁Ⲵ⛣ືࡀ㉳ࡇࡿࡇ࡜࡛඲࡚ࡢ⤖ྜ࣎ࣥࢻࡀ᏶඲࡟༨᭷ࡉࢀࡿᵓ㐀࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊ1 ࡘ 1 ࡘࡢ⤖ྜࡔࡅ࡛ࡣ㟁Ꮚⓗ࡟୙Ᏻᐃ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡀࠊ⏺㠃඲య࡜ࡋ࡚㟁Ꮚⓗ࡟Ᏻᐃ࡞ᵓ㐀ࡀᙧᡂࡋ࡚࠸ࡿ࡜
⪃࠼ࡽࢀࡿࠋ

- 198 -

᭱ᚋ࡟ࠊGaN/a-SiO2 ⏺㠃ࣔࢹࣝࡢ㟁Ꮚ≧ែࢆࣂࣥࢻࢠࣕࢵࣉࡀ෌⌧ࡉࢀࡿࡇ࡜࡛▱ࡽࢀ࡚࠸ࡿ HSE ἲ࡛ゎᯒࡋࡓࠋᅗ㸱 ࡟ GaN ࡜ SiO2 ࡟ศゎࡋࡓ≧ែᐦᗘᅗࢆ♧ࡍࠋࡇࡢᅗ࠿ࡽࠊGaN ࡢࣂࣥࢻࢠࣕࢵࣉෆ࡟ࡣḞ㝗‽఩ࡣᏑᅾࡋ࡞࠸ࠋࡇࡢࡇ࡜ࡣᛴᓧ࡞ GaN/a-SiO2 ⏺㠃ࢆᙧᡂ࡛ࡁࢀࡤࠊ࣮࣍ࣝࢺࣛࢵࣉࡢ࡞࠸⌮᝿ⓗ࡞⏺
㠃ࡀᚓࡽࢀࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

ճ

᣺ືⓎ㟁⣲Ꮚ⏝ࡢ Si/SiO2 ⏺㠃ࡢ◊✲࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࢆ⏝࠸ࡓ᣺ືⓎ㟁⣲Ꮚࡣࠊ࢝ࣜ

ᩓ‫܇‬࣒࢘ཎᏊࢆ SiO2 ࡟ᑟධࡍࡿ࡜ SiO2 ࡀ㈇࡟ᖏ㟁ࡋ࡚࢚ࣞࢡࢺࣞࢵ
ࢺ࡜࡞ࡿ⌧㇟ࢆ⏝࠸ࡓ᣺ືⓎ㟁⣲Ꮚ࡛࠶ࡿࠋ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞ

.

ஜႸỉ
6L2ኽӳỉแˮࢡࢺࣞࢵࢺ㈇㟁Ⲵ⵳✚ࡢ≀⌮ⓗ㉳※ࡣ SiO5 ᵓ㐀࡛࠶ࡿࡇ࡜ࢆ
ᡃࠎࡀᮏ◊✲࡛ⓎぢࡋࡓࠋSiO5 ᵓ㐀ࡀᙧᡂࡉࢀࡿせᅉࡣ࢔ࣝ࢝ࣜ
㔠ᒓ࡛࠶ࡿ࣒࢝ࣜ࢘ཎᏊ࠿ࡽ౪⤥ࡉࢀࡿ㟁Ꮚ࡟ࡼࡗ࡚㏻ᖖ㸲㓄఩ࡢ Si ཎᏊࡀࡶ࠺୍ࡘࡢ㓟⣲࡜⤖ྜࢆసࡾ SiO5 ᵓ㐀࡜࡞ࡾ㈇㟁

2ᢅй᪸؏

2ɧឱ᪸؏

Ⲵࢆࢺࣛࢵࣉࡍࡿࠋࡇࡢ᫬ࠊ㓟⣲㐣๫㡿ᇦࡢ SiO5 ᵓ㐀ࡀᙧᡂࡉࢀ
ࡿ࡜ࠊࡑࢀ࡜ྠ᫬࡟㓟⣲୙㊊㡿ᇦࡢ Si-Si ⤖ྜࡀᙧᡂࡉࢀࡿ㸦ᅗ㸲㸧ࠋࡇࡢ Si-Si ⤖ྜࡀษ᩿ࡉࢀࡿ࡜ Si ࢲࣥࢢࣜࣥࢢ࣎ࣥࢻ࠿ࡽ㟁Ꮚࡀ⬺㞳ࡋᒁᡤⓗ࡟ṇ㟁Ⲵࡢ≧ែ࡟࡞ࡿࡓࡵࠊSiO5 ᵓ㐀ࡢ㈇㟁Ⲵࢆᡴࡕᾘࡋ࡚ࠊ⣔඲య࡜ࡋ࡚ࡣ୰ᛶ࡟࡞ࡗ࡚ࡋࡲ࠺ࠋࡇࡢࡼ࠺࡟
㓟⣲୙㊊㡿ᇦࡢ Si-Si ࣎ࣥࢻࡀᏑᅾࡍࡿ࡜࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡ

ᅗ㸲㸸SiO2 ࡟࣒࢝ࣜ࢘ཎᏊࢆᑟධࡍࡿࡇ
࡜࡛ᙧᡂࡉࢀࡿ SiO5 ᵓ㐀࡜ Si-Si ⤖ྜࠋࢺࣞࢵࢺࡀຎ໬ࡋ࡚▷ᑑ࿨࡟࡞ࡗ࡚ࡋࡲ࠺ࠋ
ࡑࡇ࡛ࠊ࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࡢಙ
㢗ᛶࢆ㧗ࡵࡿ᪉⟇࡜ࡋ࡚㏣㓟໬ࢆ⌮ㄽⓗ࡟᳨ウࡋࡓࠋィ⟬ࡣ࣒࢝ࣜ࢘࡜ྠ᫬࡟㐣๫㓟⣲ࡶྠ᫬࡟ᑟධࡋ࡚࣓ࣝࢺࢡ࢚ࣥࢳἲ࡛࢝ࣜ
࣒࢘࡜㐣๫㓟⣲ࢆྵࡴ a-SiO2 ࢆᙧᡂࡋࡓࠋࡑ
ࡢ⤖ᯝࠊSi-Si ࣎ࣥࢻࡣᙧᡂࡉࢀࡎ࣒࢝ࣜ࢘ཎ

ᅗ㸳㸸(a)㏣㓟໬๓࡜(b)㏣㓟໬ᚋࡢᙧᡂ࢚ࢿࣝࢠ࣮ࠋ

Ꮚࡢ௚ࡣ SiO5 ᵓ㐀࡜㏻ᖖࡢ SiO4 ᵓ㐀࡜࡞ࡗࡓࠋ࣒࢝ࣜ࢘ࢆ㝖ཤࡍࡿ࡜⣔ࡣ㈇࡟ᖏ㟁ࡋ㸳࡟♧ࡍࠋࡇࡢᅗ࠿ࡽࢃ࠿ࡿࡼ࠺࡟ࠊ㏣㓟໬๓ࡣ୰ᛶ≧ែࡀᏳᐃ࡞㡿ᇦࡀᗈࡃᏑᅾࡋࡓ

㏣㓟໬࠶ࡾ㟼㟁࣏ࢸࣥࢩࣕࣝ
ࣝ 9

ࡓࠋ㏣㓟໬๓ᚋࡢ⣔ࡢᙧᡂ࢚ࢿࣝࢠ࣮ࢆᅗ

㏣㓟໬࡞ࡋࡢ࡟ᑐࡋࠊ㏣㓟໬ᚋࡣ SiO2 ࡢࣇ࢙࣑ࣝࣞ࣋
ࣝࡢṤ࡝ࡢ㡿ᇦ࡛㈇㟁Ⲵ≧ែࡀᏳᐃ࡜࡞ࡿ᫬㛫㛫 KRXUᅗ㸴㸸㏣㓟໬ࡢ๓ᚋ࡛ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࡢ⤒᫬ኚ໬ࡢ┦㐪ࡇ࡜ࡀࢃ࠿ࡿࠋᐇ㝿ᐇ㦂࡟ࡼࡗ࡚㏣㓟໬ࡢຠᯝࢆ☜ㄆࡋࡓ࡜ࡇࢁᅗ㸴ࡢࡼ࠺࡟㏣㓟໬࡟ࡼࡗ࡚࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࡢᑑ࿨ࡀᘏࡧࡿࡇ࡜ࡀࢃ
࠿ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊィ⟬⛉Ꮫ࡟ࡼࡗ࡚࣒࢝ࣜ࢘࢖࢚࢜ࣥࣞࢡࢺࣞࢵࢺࢆ⏝࠸ࡓ᣺ືⓎ㟁⣲Ꮚࡢಙ㢗ᛶᢏ⾡ࢆඛᑟࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ

- 199 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1) 㸦‫ۻ‬㸧኱⏿៞グࠊὙᖹᫀ᫭ࠊ▼㯮ᕦ┿ࠊ୕ᒇ⿱ᖾࠊᖺྜྷὒࠊⰪ⏣Ὀࠊᶫཱྀཎࠊⓑ▼㈼஧ࠊ
ࠕ࣒࢝ࣜ࢘࢖࢜
࢚ࣥࣞࢡࢺࣞࢵࢺෆ࡛ࡢỈ⣲ཎᏊࡢᣑᩓ⤒㊰ࠖࠊ➨ 83 ᅇᛂ⏝≀⌮Ꮫ఍⛅Ꮨㅮ₇఍ࠊ21a-A304-3ࠊᮾ໭኱
Ꮫࠊ2022 ᖺ 9 ᭶ 20 ᪥㹼23 ᪥ࠋ(2) 㸦‫ۻ‬㸧ⓑ▼㈼஧ࠊᢲᒣ῟ࠊࠕィ⟬⛉Ꮫ࡛ぢࡿ࣡࢖ࢻࢠࣕࢵࣉ༙ᑟయ MOSFET ⏺㠃ࠖࠊ➨ 83 ᅇᛂ⏝≀⌮Ꮫ఍⛅Ꮨㅮ₇఍ࠊ21p-M206-6ࠊᮾ໭኱Ꮫࠊ2022 ᖺ 9 ᭶ 20 ᪥㹼23 ᪥ࠋฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) 㸦 ‫ ۻ‬㸧 K. Chokawa, K. Shiraishi, and A. Oshiyama, “Atomic and electronic structures of interfaces between
amorphous (Al2O3) 1-x (SiO2) x and GaN polar surfaces revealed by first-principles simulated annealing technique”,
J. Appl. Phys. 133, 065301, (2023).
(2) 㸦‫ۻ‬㸧Y. Ohata, M. Araidai, Y. Shibata, G. Hashiguchi, and K. Shiraishi, “Effect of carbon atoms on the reliabilityof potassium-ion electrets used in vibration-powered generators”, Jpn. J. Appl. Phys., 61, SH1013 (2022).
(3) 㸦‫ۻ‬㸧Y. Ohata, T. Nakanishi, K. Chokawa, M. Araidai, T. Ishiguro, H. Mitsuya, H. Toshiyoshi, Y. Shibata, G.
Hashiguchi, and K. Shiraishi, “Improvement of the reliability of potassium-ion electrets thorough an additionaloxidation process”, Appl. Phys. Lett., 121, 243903 (2022).
(4) 㸦‫ۻ‬㸧Y Ohata, M Araidai, T Ishiguro, H Mitsuya, H Toshiyoshi, Y Shibata, G. Hashiguchi, and K. Shiraishi, “Effectof hydrogen atoms on potassium-ion electrets used in vibration-powered generators”, Mater. Sci. in Semi. Process.
157, 107306 (2023).

- 200 -

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$1() Tatsuro Nishikino, Norihiro Takekawa, Duy Phuoc Tran, Jun-ichi Kishikawa, Mika Hirose, Sakura Onoe, Seiji
Kojima, Michio Homma, Akio Kitao, Takayuki Kato, Katsumi Imada, Structure of MotA, a flagellar stator protein, fromhyperthermophile, Biochemical and Biophysical Research Communications 631, 78 (2022)() Tohru Minamino, Miki Kinoshita, Yumi Inoue, Akio Kitao, Keiichi Namba, Conserved GYXLI motif of FlhA is
involved in dynamic domain motions of FlhA required for flagellar protein export, Microbiology Spectrum 10, e01110(2022)() Duy Phuoc Tran, Yuta Taira, Takumi Ogawa, Ryoga Misu, Yoshiki Miyazawa, Akio Kitao, Inhibition of thehexamerization of SARS-CoV-2 endoribonuclease and modeling of RNA structures bound to the hexamer, Scientific
Reports 12, 1 (2022)() Satoshi Yamashita, Misao Mizuno, Kazuhiro Takemura, Akio Kitao, Yasuhisa Mizutani, Dependence of Vibrational
Energy Transfer on Distance in a Four-Helix Bundle Protein: Equidistant Increments with the Periodicity of α Helices,
The Journal of Physical Chemistry B 126, 3283 (2022)() Mohamed Marzouk Sobeh, Akio Kitao, Dissociation Pathways of the p53 DNA Binding Domain from DNA andCritical Roles of Key Residues Elucidated by dPaCS-MD/MSM, Journal of Chemical Information and Modeling 62, 1294
(2022)- 204 -

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࢚࣮ࣥࢸࣝ࡟ࡼࡿ㔠ᒓ࢖࢜ࣥㄆ㆑ࡢ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊCryo-IM-MS ࢆ⏝࠸࡚㔠ᒓ࢖࢜ࣥ࡜ࢡ
࢚࣮ࣛ࢘ࣥࢸࣝ࠿ࡽ࡞ࡿ࣍ࢫࢺ-ࢤࢫࢺ໬ྜ≀ࡢᵓ㐀ࢆ◊✲ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲK+ ࡜ ࢡ ࣛ ࢘ ࣥ ࢚ ࣮ ࢸ ࣝ ࡢ 1 ✀ ࡛ ࠶ ࡿ dibenzo-24-crown-8 (DB24C8) ࠿ ࡽ ࡞ ࡿ ࣍ ࢫ ࢺ ࢤ ࢫ ࢺ ໬ ྜ ≀K+(DB24C8)ࡢሙྜࠊMMFF94s ຊሙ࡟ࡼࡿ㓄ᗙ᥈⣴ィ⟬ࢆ CONFLEX 8 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚⾜࠸ࠊ541 ಶࡢࢥࣥࣇ࢛࣐࣮ࢆᚓࡓࠋᚓࡽࢀࡓࢥࣥࣇ࢛࣐࣮ࡢ࠺ࡕ࢚ࢿࣝࢠ࣮ࡀᏳᐃ࡞ 20 ಶ࡟ࡘ࠸࡚ࠊࡉࡽ࡟ᵓ㐀᭱㐺໬ࢆ⾜࠸Ᏻᐃᵓ㐀ࢆồࡵࡓ㸦ィ⟬ࣞ࣋ࣝ M05-2X/6-311++G(d,p)ࠊࣉࣟࢢ࣒ࣛ Gaussian 16㸧ࠋࡇࡢ 20 ಶࡢᏳᐃᵓ㐀࡟
ࡘ࠸࡚ࠊMOBCAL ࣉࣟࢢ࣒ࣛࡢࢺࣛࢪ࢙ࢡࢺࣜἲࢆ⏝࠸࡚ྛᗘ࡟࠾ࡅࡿ He ཎᏊ࡜ࡢ CCS ࢆồࡵࡓ㸬◊✲ᡂᯝCryo-IM-MS ࡜ 㔞 Ꮚ ໬ Ꮫ ィ ⟬ ࡟ ࡼ ࡾ Ỵ ᐃ ࡉ ࢀ ࡓ+

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8 ಶࡢ㓟⣲ཎᏊࢆྵࡴࢡ࢚࣮ࣛ࢘ࣥࢸࣝ࡟ࡼࡾ❧యⓗ࡟ྲྀࡾᅖࡲࢀࡓໟ᥋㘒యࢆᙧᡂࡋ࡚࠸ࡿࠋ㘒యෆࡢ 2 ಶࡢ࣋ࣥࢮࣥ⎔㛫ࡢ㊥㞳ࡣࠊRbz-bz = 3.8 Å ࡛࠶ࡾࠊ2 ಶࡢ࣋ࣥࢮࣥ⎔ࡀ࡯ࡰᖹ⾜࡟୪ࢇ࡛࠸ࡿࠋ୍᪉ࠊK+ ࡜㘒ᙧᡂࡋ࡚࠸࡞࠸
DB24C8 ࡢ᭱Ᏻᐃᵓ㐀ࢆ㔞Ꮚ໬Ꮫィ⟬࡛ồࡵࡓ࡜ࡇࢁࠊᖹ㠃࡟㏆࠸ᵓ㐀ࢆ࡜ࡾ 2 ಶࡢ࣋ࣥࢮࣥ⎔ࡣ㐲ࡃ㞳ࢀ࡚࠸ࡓ
㸦Rbz-bz = 14 Å㸧ࠋࡼࡗ࡚ࠊ࣍ࢫࢺศᏊ࡛࠶ࡿ DB24C8 ࡣඖࠎ
K+ࢆྲྀࡾ㎸ࡳࡸࡍ࠸ᵓ㐀ࢆᣢࡗ࡚࠸ࡿࡢ࡛ࡣ࡞ࡃࠊK+࡜㘒ᙧᡂࡋ࡞ࡀࡽࡑࡢᵓ㐀ࢆኚᙧࡉࡏ࡚Ᏻᐃ໬ࡍࡿࡇ࡜ࡀࢃ࠿ᅗ   㔞 Ꮚ ໬ Ꮫ ィ ⟬ ࡛ ᚓ ࡽ ࢀ ࡓࡗࡓࠋࡇࡢᵓ㐀ኚᙧࡢ⌧㇟ࡣࠊ㓝⣲཯ᛂ࡟࠾࠸࡚ᇶ㉁ศᏊࡀ

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࢔࣑ࣀᏳᜥ㤶㓟࡟࠾ࡅࡿศᏊෆࣉࣟࢺࣥ⛣ືࡢ◊✲ࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2A15 (ཱྀ㢌)‫ۑۻ‬୰ᓥ ඃᩯࠊỌ⏣ ฼᫂ࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠊⓑ㔠㓟໬≀ࢡࣛࢫࢱ࣮ṇ࢖࢜ࣥࡢ୍㓟໬❅⣲࡜ࡢ཯ᛂࡢ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿほࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ1P054 (࣏ࢫࢱ࣮)‫ۑۻ‬He Xiࠊ⨾㰺ὠ ᩥ඾ࠊ኱ୗ ៞ḟ㑻ࠊConformations of dibenzo-24-crown-8 complex with diverse metal ionsstudied by cryogenic ion mobility-mass spectrometryࠊ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ1P002 (࣏ࢫࢱ࣮)‫ࠐۻ‬኱ୗ ៞ḟ㑻ࠊబ⸨ Ⰻுࠊ㧗ᓮ భஓࠊ⨾㰺ὠ ᩥ඾ࠊ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸ࡓࣉࣟࢺࣥ௜ຍศᏊ
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⺮ⓑ㉁ࡢᶵ⬟Ⓨ⌧࡜ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on the relation between the functional expression and thestructure in protein‫ࢺ࢜ࣝࢗࢺࣥࣜۑ‬ṇ⨾ࠊ୰ᮧ⨾⩚ (ி㒔ᗓ❧኱Ꮫ኱Ꮫ㝔⏕࿨⎔ቃ⛉Ꮫ◊✲⛉)1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࢱࣥࣃࢡ㉁ࡢᵓ㐀ኚ໬࡜ᶵ⬟ࡢኚ໬࡟ࡘ࠸࡚ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

62' ࡢ༢㔞య໬࡟࠾ࡅࡿ㟼㟁࣮ࣝࣉࡢᵓ㐀ኚ໬࡜㟁Ⲵศᕸࡢᙳ㡪SOD㸦superoxide dismutase㸧ࡢ୍ࡘ࡛࠶ࡿ SOD1 ࡣ⣽⬊ෆ࡟Ꮡᅾࡋ࡚࠾ࡾࠊᐙ᪘ᛶ➽ⴎ⦰ᛶഃ⣴◳໬⑕
(FALS: Familial Amyotrophic Lateral Sclerosis㸧࡞࡝ࡢ⚄⤒⑌ᝈ࡜㛵ಀࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣᇶ㉁࡛࠶ࡿࢫ࣮ࣃ
࣮࢜࢟ࢧ࢖ࢻ࢔ࢽ࢜ࣥࣛࢪ࢝ࣝ㹍2-ࡢάᛶ㒊఩࡬ࡢ᥋㏆࡟ᑐࡍࡿ༢㔞య໬ࡢᙳ㡪࡟ࡘ࠸࡚≉࡟㟼㟁࣮ࣝࣉࡢᵓ㐀ኚ໬ࡸ㟁Ⲵศᕸࡢኚ໬࡟╔┠ࡋ࡚㹋㹂ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ 40 ィ⟬ࢆ⏝࠸ࡓ◊✲ࢆ⾜ࡗࡓࠋĮ+\GUR[\VWHURLG'HK\GURJHQDVH㸦Į+6'㸧ࡢ⿵ᅉᏊ⤖ྜ࡟ࡼࡿ㈇ࡢ༠ྠᛶ࡜⿵ᅉᏊ≉␗ᛶࡢゎ᫂
3αHSD ࡣෆᅉᛶ⚄⤒ࢫࢸࣟ࢖ࢻࡢྜᡂ࡟ᚲせ࡞㓝⣲࡛⣽⳦࠿ࡽࣄࢺࡲ࡛ከࡃࡢ⏕࿨య୰࡛ാ࠸࡚࠸ࡿࠋ
ᅵᎹࡼࡾศ㞳ࡉࢀࡓ Pseudomonas sp. B-0831 ᰴ⏤᮶ࡢ 3ȘHSD㸦Ps3aHSD㸧ࡣ㸪⮫ᗋデ᩿⏝㓝⣲࡜ࡋ࡚⫹Ồ㓟ᐃ࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋPs3aHSD ࡜┦ྠᛶࡢ㧗࠸ Comamonas testosterone ⏤᮶ࡢ 3ȘHSD㸦Ct3aHSD㸧࡜ࡣ␗࡞ࡾࠊ⿵ᅉᏊ⤖ྜ࡟ࡼࡿ㈇ࡢ༠ྠᛶࢆ♧ࡋ⿵ᅉᏊ NADH ࡢࡳ࡞ࡽࡎ NADPH ࡟ࡶάᛶࢆ♧ࡍࠋࡇࢀࡽࡢάᛶࠊ
⿵ᅉᏊ౫Ꮡᛶࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ᣦࡋ Ps3aHSD ࡜ Ct3aHSD ࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࡓ⤖ᯝࠊ୧⪅࡜
ࡶ࡟ 2 㔞య໬ࡸ⿵ᅉᏊ⤖ྜ࡟ࡼࡗ࡚ࡑࢀࡒࢀࡢᇶ㉁⤖ྜ㒊఩ࡢᏳᐃᛶࡀኚ໬ࡍࡿࡀࠊᏳᐃ໬ࡢ᪉ྥᛶࡀ␗࡞
ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᅇࡣ≉࡟ apo యࡢᇶ㉁⤖ྜ࣮ࣝࣉࡢᦂࡽࡂ࡟╔┠ࡋࡓࣔࢹࣝ໬ࢆ⾜࠸㹋D ィ⟬࡟ࡼࡿ
Ps3aHSD ࡟࠾ࡅࡿ⿵ᅉᏊ⤖ྜ࡟ࡼࡿ㈇ࡢ༠ྠᛶࡢ⪃ᐹࢆヨࡳࡓࠋ ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮࡢᇶ㉁≉␗ᛶ࡜ศᏊㄆ㆑ᶵᵓࡢゎ᫂࡟ྥࡅࡓ◊✲ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛࠶ࡿࢽ࣮ࣗࣟࣉࢩࣥࡣࠊ኱⬻㎶⦕⣔࡛Ⓨ⌧ࡉࢀࠊࡇࡢࢱࣥࣃࢡ㉁ࡢᶵ⬟㞀ᐖࡣ⢭⚄⑌ᝈࡢཎᅉ࡜࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࢽ࣮ࣗࣟࣉࢩࣥࡢศᏊㄆ㆑ᶵᵓࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞
ࡗ࡚࠸࡞࠸ࠋࡇࢀࡲ࡛ᐇ㦂ࠊィ⟬ඹ࡟ษ᩿㒊఩ࡢ๓᪉ࡢ࢔࣑ࣀ㓟ṧᇶࡢࡳ࡟ࡘ࠸࡚ᇶ㉁≉␗ᛶࡢỴᐃᅉᏊ࡜ࡢ㛵㐃ᛶࢆ᳨ウࡋ࡚ࡁࡓࡀࠊ௒ᅇࡣᚋ᪉࡟ᣑᙇࡋࡓࣔࢹࣝࢆ⏝࠸ᇶ㉁≉␗ᛶᅉᏊࡢỴᐃࢆヨࡳࡓࠋࡲࡓࠊࡇ
ࢀࡽࡢ࢔࣑ࣀ㓟ṧᇶࡢ⬻ෆ࡟࠾ࡅࡿศᕸ࡟ࡘ࠸࡚ࠊࢹ࣮ࢱ࣮࣋ࢫ࡜㐃⤖ࡍࡿࡇ࡜࡛᥈⣴ࢆヨࡳࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
SOD1ࠊ3ȘHSDࠊneuropsin ࡢึᮇᵓ㐀࡟ࡣ㹖⥺⤖ᬗᵓ㐀ࡸ NMR ᵓ㐀ࢆ⏝࠸ࡓࠋࢽ࣮ࣗࣟࣉࢩࣥ-࣌ࣉࢳ

ࢻ」ྜయࣔࢹࣝࡢึᮇᵓ㐀ࡣ sievgene ࢆ⏝࠸ࡓࢻࢵ࢟ࣥࢢ࡟ࡼࡿࣔࢹࣝ໬ࢆ⾜ࡗࡓࠋMD ィ⟬࡟ Gromacs ࢆ
⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

62' ࡢ༢㔞య໬࡟࠾ࡅࡿ㟼㟁࣮ࣝࣉࡢᵓ㐀ኚ໬࡜㟁Ⲵศᕸࡢᙳ㡪
SOD1 ࡣ Cu ࡜ Zn ཎᏊࡀ཯ᛂάᛶࢧ࢖ࢺࡢᗏ࡟Ꮡᅾࡋ࡚࠾ࡾࠊࡑࡢୖ㒊࡟ࡣ▷࠸Ș࣊ࣜࢵࢡࢫࢆྵࡴ㟼- 211 -

㟁࣮ࣝࣉ࡜࿧ࡤࢀࡿ㒊఩ࡀᏑᅾࡋ㈇㟁Ⲵࢆ᭷ࡍࡿᇶ㉁ࢆ࣏ࢣࢵࢺࡢᗏ࡟࠶ࡿ Cu ࡬࡜ㄏᑟࡍࡿࠋ௒ᅇࡣ≉࡟㟼㟁࣮ࣝࣉࡢ unfolding ࢆྵࡴᇶ㉁⤖ྜ㒊఩࿘㎶ࡢᵓ㐀ኚ໬ࡣᇶ㉁⤖ྜ࣏ࢣࢵࢺ࿘㎶ࡢ㟁Ⲵศᕸࢆኚ໬ࡉࡏࡿࡇ
࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㟼㟁࣮ࣝࣉࡢᵓ㐀ኚ໬࡜ᇶ㉁ࡢ࣏ࢣࢵࢺ࡬ࡢ᥋㏆ࡢ㐜ᘏࡢ㛵㐃ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚ウ୰࡛࠶ࡿࠋĮ+\GUR[\VWHURLG'HK\GURJHQDVH㸦㸦Į+6'㸧ࡢ⿵ᅉᏊ⤖ྜ࡟ࡼࡿ㈇ࡢ༠ྠᛶ࡜⿵ᅉᏊ≉␗ᛶࡢゎ᫂
1 ศᏊ┦ᙜࡢᇶ㉁ࡢῧຍ࡟ࡼࡗ࡚ Ps3aHSD ࡛ࡣ CD ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ loop-helix 㑄⛣ࡀほᐹࡉࢀ࡚࠸
ࡿࡇ࡜࠿ࡽࠊholo య࡟࠾࠸࡚ᇶ㉁⤖ྜ࡟ࡼࡗ࡚ loop-helix 㑄⛣ࡀᘬࡁ㉳ࡇࡉࢀࡿ࡜ᥦ᱌ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊ⇕ຊᏛⓗ◊✲ࡸ⤖ᬗᵓ㐀ゎᯒࡢ⤖ᯝࡼࡾ apo య࡟࠾࠸࡚ᇶ㉁⤖ྜ࣮ࣝࣉࡢࣇࣞ࢟ࢩࣅࣜࢸ࢕࣮ࡢቑຍࡀ♧၀ࡉࢀ࡚࠾ࡾࠊᇶ㉁⤖ྜ࡟ᑐࡍࡿ 2 㔞య࡟࠾ࡅࡿ㈇ࡢ༠ྠᛶࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋ௒ᅇࡣ apo యࡢ࣮ࣝࣉᵓ㐀࡟╔┠ࡋࠊsteered MD ࢆ⏝࠸ࡿࡇ࡜࡛ 3 ࡘࡢࣔࢹࣝࢆ⏕ᡂࡋࠊᇶ㉁⤖ྜ࡟ࡼࡿ࣮ࣝࣉᵓ㐀࡜ࡑࡢᦂࡽࡂ࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ2 㔞య඲య࡜ࡋ࡚ᇶ㉁⤖ྜ࣮ࣝࣉ࡟࠾ࡅࡿ loop-helix 㑄⛣ࡀほᐹࡉࢀࡓࡀࠊapo య࡟࠾ࡅࡿᇶ㉁⤖ྜ࣮ࣝࣉࡢࣇࣞ࢟ࢩࣅࣜࢸ࢕࣮ࡢቑຍࡣほᐹࡉࢀ࡞࠿ࡗࡓࠋ⌧ᅾࠊapo-holo2 㔞యࣔࢹࣝࡢ㠀ᑐ⛠ᛶ࡜㈇ࡢ༠ྠᛶ࡟㛵ࡍࡿ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

 ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮࡢᇶ㉁≉␗ᛶ࡜ศᏊㄆ㆑ᶵᵓࡢゎ᫂࡟ྥࡅࡓ◊✲ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛ࡣᇶ㉁ࡢษ᩿㒊఩ࡢ๓᪉࡟࠶ࡿ࢔࣑ࣀ㓟ṧᇶࡢ㔜せᛶ࡟ࡘ࠸࡚㆟ㄽࡉࢀࡿࡇ࡜ࡀ
ከ࠸ࠋษ᩿㒊఩ࡢ๓᪉㸱ࡘࡢ࢔࣑ࣀ㓟ṧᇶ࠿ࡽ࡞ࡿᑠࡉ࡞࣌ࣉࢳࢻࣔࢹࣝࢆ⏝࠸࡚ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸㏿ᗘㄽⓗᐇ㦂⤖ᯝ࡜ࡢẚ㍑ࢆ⾜ࡗࡓ⤖ᯝࠊ⤖ྜぶ࿴ᛶࠊゐ፹ 3 ṧᇶࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࠊ࢜࢟ࢩ࢔ࢽ
࣮࢜ࣥ࣍ࣝࡢᙧᡂࠊᇶ㉁ࡢ㓄ྥᛶࡀᇶ㉁≉␗ᛶࡢỴᐃᅉᏊ࡛࠶ࡿ࡜⤖ㄽ࡙ࡅࡓࠋࡇࢀࡽࡢỴᐃᅉᏊࢆࣃ࣓ࣛ
࣮ࢱ࡜ࡋ࡚ࠊࡇࢀࡲ࡛⪃៖ࡉࢀ࡞࠿ࡗࡓษ᩿㒊఩ࡢᚋ᪉ࡢ࢔࣑ࣀ㓟ṧᇶࡢ㓄ิ࡟ࡘ࠸࡚ࡶ᳨ウࢆ⾜ࡗࡓ⤖ᯝࠊ≉␗ⓗᇶ㉁ࡢ୍ࡘ࡛࠶ࡿ neuregulin-1 ࡢษ᩿㒊఩ࡢ≉␗ᛶ࡟ࡘ࠸࡚ᐇ㦂ⓗ࡟ᚓࡽࢀ࡚࠸ࡿ⤖ᯝࢆㄝ࡛᫂ࡁࡿ
ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊ⬻ෆ࡛Ⓨ⌧ࡋ࡚࠸ࡿࢱࣥࣃࢡ㉁࡟ࡘ࠸࡚ࢹ࣮ࢱ࣮࣋ࢫ࡜㐃⤖ࡍࡿࡇ࡜࡟ࡼࡾ
neuregulin-1 ࡢษ᩿㒊఩ࡢ㓄ิࡢ≉␗ᛶࡶࡲࡓ᫂ࡽ࠿࡜࡞ࡗࡓࠋ⌧ᅾࡣ㔠ᒓࡸ⢾㙐ಟ㣭ࡢᇶ㉁⤖ྜ≉␗ᛶ࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸᳨࡚ウ୰࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬SOD1 ࡬ࡢᇶ㉁᥋㏆࡟ᑐࡍࡿ㟼㟁࣮ࣝࣉ࡜ Arg143 ࡢᙺ๭ࠊ୰ᮧ⨾⩚ࠊ⚟すᛌᩥࠊࣜࣥࢺࢗࣝ࢜ࢺࣘࣁࠊ
ࣜࣥࢺࢗࣝ࢜ࢺṇ⨾(2022:⏕≀≀⌮Ꮫ఍ 2022 ᖺ఍ ภ㤋)‫ۻ‬MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ㸱Ș̺ࣄࢻࣟ࢟ࢩࢫࢸࣟ࢖ࢻ⬺Ỉ⣲㓝⣲ࡢᵓ㐀ኚ໬ࠊኳᕝ⸅ࠊ㕥ᮌ኱ᶞࠊࣜࣥࢺࢗࣝ࢜ࢺࣘࣁࠊࣜࣥࢺࢗࣝ࢜ࢺṇ⨾(2022:⏕≀≀⌮Ꮫ఍ 2022 ᖺ఍ ภ㤋)‫ ࢮ࣮࢔ࢸࣟࣉࣥࣜࢭۻ‬Neuropsin ࡢᇶ㉁≉␗ᛶࡢỴᐃᅉᏊ࡟㛵ࡍࡿ㹋㹂◊✲ࠊࣜࣥࢺࢗࣝ࢜ࢺṇ⨾ࠊᇼᒸὒኴࠊ㜿㒊ගᑗࠊ⚟すᛌᩥࠊࣜࣥࢺࢗࣝ࢜ࢺࣘࣁࠊ⏣ᮧⱥ⣖(2022:⏕≀≀⌮Ꮫ఍ 2022 ᖺ఍ ภ㤋)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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Biophysics and Physicobiology19H  ‫ۻ‬6XEVWUDWHVSHFLILFLW\RIQHXURSVLQLQYHVWLJDWHGE\0'VWXG\FRPELQHGZLWKGDWDEDVHRIJHQHH[SUHVVLRQRYHUEUDLQ
0/LQWXOXRWR0$EH<+RULRND<)XNXQLVKL+7DPXUD-0/LQWXOXRWR ᢞ✏‽ഛ୰- 212 -

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ᬡ㔞ࠊ▮㔝

ளᐇ

㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉໬Ꮫᑓᨷࠊி㒔኱Ꮫ⎔ቃᏳ඲ಖ೺ᶵᵓ㸧◊✲┠ⓗࣉࣟࢺࣥඹᙺ㟁Ꮚ⛣ື㸦Proton-coupled electron transfer (PCET)㸧ࡣࠊ≉࡟⏕໬Ꮫࡸゐ፹໬Ꮫࡢศ㔝࡛ᗈࡃ◊✲ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ◊✲ศ㔝࡛ࡣࠊ㓟໬㑏ඖάᛶ࡞㓄఩Ꮚࢆ᭷ࡍࡿ㔠ᒓ㘒యࡀ୍⩼ࢆᢸࡗ࡚࠸ࡿࡀࠊȧᖹ㠃ᵓ㐀ࢆᣢࡘ㔠ᒓ㘒యࡣᮍ㛤ᣅ࡞ࡲࡲ࡛࠶ࡿࠋ௒ᅇࡣࠊ㓟໬㑏ඖάᛶ࡞㓄఩Ꮚࢆ᭷ࡍࡿȧᖹ㠃ࢽࢵࢣࣝ㘒య Ni(itsq)2 ࢆᐇ㦂࡜⌮ㄽࡢ୧㠃࠿ࡽ᳨ウࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT㸧ࠊ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ⌮ㄽ㸦TD-DFT㸧࡟ࡼࡿ⌮ㄽⓗゎᯒࡣࠊB3LYP ỗ㛵ᩘ࡜ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊCࠊHࠊNࠊS ࡟ᑐࡋ࡚ 6-31++G(d,p)ࠊNi ࡟ࡘ࠸࡚ LanL2DZ ࢆ⤌ࡳྜࢃࡏ࡚⾜ࡗࡓࠋ඲࡚ࡢィ⟬ࡣࠊGaussian 09 ࣉࣟࢢ࣒࡛ࣛᐇ⾜ࡋࡓࠋ◊✲ᡂᯝ㓟໬㑏ඖάᛶ࡞㓄఩Ꮚࢆ᭷ࡋࠊ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮࡛࠶ࡿ Ni(itsq)2 ࡟ࡘ࠸࡚ࠊB3LYP ἲ࡟ࡼࡾ⌮ㄽⓗゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊNi(itsq)2 ࡢ LUMO ࡣ୺࡟㓄఩Ꮚୖ࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊNi(itsq)2ࠊ[Ni(itsq)(itsq+H)]+ࠊ
[Ni(itsq+H)2]2+ࡢࡼ࠺࡟ࣉࣟࢺࣥ໬ࡀ㉳ࡇࡿ࡜ࠊLUMO ࡢ࢚ࢿࣝࢠ࣮ࡀኚ໬

Ni(itsq)2

ࡍࡿ࡜ྠ᫬࡟ࠊLUMO ࡟ᑐࡍࡿ࣋ࣥࢮࣥ⎔ࡢᐤ୚ࡀⴭࡋࡃῶᑡࡍࡿࡇ࡜ࡀ
ศ࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࠊNi(itsq)2 ࡢ㑏ඖ࡟㛵㐃ࡍࡿ PCET ᣲື࡟⯆࿡ࡀᣢࡓࢀࡿࠋ
Ni(itsq)2 ࡢ☢໬⋡ࡢᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊᐊ

࡛ࡢ χT ್ࡣࠊ0.034 emu Kímol ࡜ࠊS = 1 ࡢࢫࣆࣥࠊࡲࡓࡣࠊ2 ಶࡢ S = 1/2 ࢫࣆࣥ࡟ᑐࡍࡿ⌮ㄽ್ࡼ

[Ni(dcpdt)2]2−

ࡾࡶࡣࡿ࠿࡟ᑠࡉ࡞್ࢆ♧ࡋࡓࠋB3LYP ἲ࡟ࡼࡾศᏊෆࡢ☢Ẽⓗ┦஫స⏝ࡢ኱ࡁࡉࢆぢ✚ࡶࡗࡓ࡜ࡇࢁࠊJ =í0.17 eV ࡢ཯ᙉ☢ᛶ┦஫స⏝ࡀാ࠸࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
Ni(itsq)2 ࡣࠊ࢔ࢭࢺࢽࢺࣜࣝ୰࡛㏆㉥እ㡿ᇦ㸦808 nm㸧࡟ᙉ࠸྾཰ࢆ♧ࡍࠋTD-DFT ィ⟬࡟ࡼࡿ⌮ㄽⓗゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊNi(itsq)2 ࡛ࡣ 801.3 nm ࡟ HOMO ࠿ࡽ LUMO ࡬ࡢ㑄⛣࡟ᑐᛂࡍࡿᙉ࠸྾཰ࡀᏑᅾࡋࠊ2 ࡘࡢ㓄఩Ꮚ㸦itsqí㸧ࡢ㛫ࡢ㟁Ⲵ⛣ື㸦//&7㸧࡟ᖐᒓࡉࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࣉࣟࢺࣥ໬ࡀࠊNi(itsq)2 ࡢ㟁Ꮚ≧ែ࡟ཬࡰࡍᙳ㡪ࢆ᳨ウࡍࡿࡓࡵࠊNi(itsq)2 ࡢ࢔ࢭࢺࢽࢺࣜࣝ⁐ᾮ࡟ࣅࢫ(ࢺࣜࣇ࣓ࣝ࢜ࣟࢱࣥࢫࣝ࣍ࢽࣝ)࢔࣑ࣥ
㸦HTf2N㸧ࢆῧຍࡋࡓ࡜ࡇࢁࠊHTf2N ࡢῧຍ㔞ࡀቑ࠼ࡿ࡟ᚑ࠸ࠊ808 nm ࡢ྾཰ᖏࡢᙉᗘࡀᑠࡉࡃ࡞ࡾࠊ1.54 ᙜ㔞௨ୖ࡛ࡣ᏶඲࡟ᾘኻࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࡢࡇ࡜ࡣࠊTD-DFT ィ⟬࠿ࡽࡶᨭᣢࡉࢀࡓࠋ
HTf2N ࢆῧຍࡋࠊCV ἲ࡟ࡼࡾ㓟໬㑏ඖ㟁఩ࢆᐃࡋࡓ࡜ࡇࢁࠊNi(itsq)2 ࡟࠾ࡅࡿ➨ 1 㑏ඖ㟁఩ࡢࢩࣇࢺ㔞

㸦63 mV㸧ࡣࠊ㓟໬㑏ඖ୙άᛶ࡞㓄఩Ꮚࢆ᭷ࡍࡿ[Ni(dcpdt)2]2−ࡢ➨ 1 㓟໬㟁఩ࡢࢩࣇࢺ㔞㸦29 mV㸧ࡢ⣙ 2 ಸ- 215 -

࡛࠶ࡗࡓࠋB3LYP ἲ࡟ࡼࡿ⌮ㄽⓗゎᯒ࡛ࡣࠊࣉࣟࢺࣥ໬࡟ࡼࡿ Ni(itsq)2 ࡢ LUMO ࡢᏳᐃ໬࢚ࢿࣝࢠ࣮㸦4.2
eV㸧ࡀࠊ[Ni(dcpdt)2]2−ࡢ HOMO ࡢᏳᐃ໬࢚ࢿࣝࢠ࣮㸦3.2 eV㸧ࡼࡾࡶ኱ࡁ࠸ࡇ࡜ࡀ♧ࡉࢀ࡚࠾ࡾࠊᐇ㦂⤖ᯝࢆᨭᣢࡋ࡚࠸ࡿࠋ
௨ୖࡢ⤖ᯝࡣࠊ㓟໬㑏ඖάᛶ࡞㓄఩Ꮚࢆ㐺ษ࡟タィࡍࡿࡇ࡜࡛ࠊ㓟໬㑏ඖ≉ᛶࡔࡅ࡛࡞ࡃࠊࣝ࢖ࢫ㓟ᛶ࣭ሷᇶᛶ≉ᛶࡶไᚚ࡛ࡁࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡲࡓࠊ㓟໬㑏ඖάᛶ࡞㓄఩Ꮚࢆᣢࡘȧᖹ㠃ᆺ㔠ᒓ㘒యࡣࠊ᪂つPCET ᆺᮦᩱࡢ㛤Ⓨ࡟ࡘ࡞ࡀࡿࡇ࡜ࡀᮇᚅࡉࢀࡿ㸦ฟ∧ᐇ⦼[1]㸧
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ࢫග␗ᛶ໬ࢆ㉳ࡇࡉ࡞࠸ࠋ୍᪉ࠊ࢖ࣥࢹ࢕ࢦࡣ 1+ ᇶ࡜ &2 ᇶࡢ㛫࡛ศᏊෆỈ⣲⤖ྜࢆᙧᡂࡋ࡚࠸ࡿࡀࠊࡇ
ࡢ 1+ ᇶࢆ௚ࡢཎᏊࡲࡓࡣཎᏊᅋ࡛⨨ࡁ᥮࠼ࡓศᏊ࡛ࡣග␗ᛶ໬ࡀ㉳ࡇࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡇࡢ཯ᛂᛶ
ࡢ㐪࠸࡟ࡣศᏊෆỈ⣲⤖ྜࡢ᭷↓ࡀᙳ㡪ࡍࡿ࡜⪃࠼ࡽࢀࡿࡶࡢࡢࠊ㐪࠸ࢆ⏕ࡌࡉࡏࡿලయⓗ࡞ᶵᵓࡣศ࠿ࡗ
࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ࢖ࣥࢹ࢕ࢦ࡜ࡑࡢ⨨᥮యࡢࢩࢫ̺ࢺࣛࣥࢫග␗ᛶ໬࡟ࡘ࠸࡚࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ
࣮ィ⟬ࢆ⾜࠸ࠊࡑࡢ⤖ᯝ࡟ᇶ࡙࠸࡚཯ᛂᛶࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ≉࡟ࠊ1+ ᇶࢆ◲㯤ཎᏊ࡛⨨ࡁ᥮࠼ࡓࢳ࢜࢖ࣥࢹ࢕ࢦࡢග␗ᛶ໬࡟ࡘ࠸࡚࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ィ⟬ࢆ⾜࠸ࠊ࢖ࣥࢹ࢕ࢦ࡜ࡢ┦㐪
Ⅼࢆ᳨ウࡍࡿࠋ
㸦㸰㸧ࢢࣝࢥ࣮ࢫ࡜ࡑࡢ஧㔞య࡟࠾ࡅࡿ 2+ ⤖ྜࡢගゎ㞳⢾㢮ࡣⓎⰍᅋࢆᣢࡓ࡞࠸ࡓࡵ࡟྾཰࣭Ⓨගࢫ࣌ࢡࢺࣝࡢほࡀᅔ㞴࡛࠶ࡾࠊࡑࡢග໬Ꮫⓗᣲື࡟ࡘ࠸࡚ࡣ

Ṥ࡝ศ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊࢢࣝࢥ࣮ࢫ㸦ȕࢢࣝࢥ࣮ࢫ㸧ࠊ୪ࡧ࡟  ಶࡢࢢࣝࢥ࣮ࢫศᏊࡀ⬺Ỉ⦰ྜࡋࡓ஧㔞య㸦஧⢾㸧࡛࠶ࡿࢭࣟࣅ࣮࢜ࢫࢆィ⟬ᑐ㇟࡟㑅ࡧࠊග໬Ꮫ཯ᛂ࡜ࡋ࡚㉳ࡇࡿ࡜ᮇᚅࡉࢀࡿ 2+ ⤖ྜࡢゎ㞳࡟ࡘ࠸࡚ࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡢィ⟬࡟ࡼࡿ཯ᛂᶵᵓࡢゎ᫂ࢆ┠ᣦࡍࠋ≉࡟ࠊ෇㗹஺ᕪࢆ௓ࡋࡓ㧗㏿↓㍽ᑕኻάࡢ᭷↓࡟ࡘ࠸᳨࡚ウࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ◊✲┠ⓗ࡛グࡋࡓ㡯┠㸦㸯㸧㸦㸰㸧ࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊୗグࡢィ⟬ࢆᐇ⾜ࡋࡓࠋ㸦㸯㸧࢖ࣥࢹ࢕ࢦ⣔Ⰽ⣲࡟࠾ࡅࡿග␗ᛶ໬
࢖ࣥࢹ࢕ࢦ࠾ࡼࡧࢳ࢜࢖ࣥࢹ࢕ࢦ࡟ࡘ࠸࡚ࠊບ㉳≧ែ࡟࠾ࡅࡿࢺࣛࣥࢫయ࠿ࡽࢩࢫయ࡬ࡢ␗ᛶ໬࡟㛵ࡍࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡢ㔞Ꮚ໬Ꮫィ⟬ࢆᐇ᪋ࡋࡓࠋ୧➃ࡢභဨ⎔ࢆ┬␎ࡋࡓࣔࢹࣝศᏊࢆᐇ㝿ࡢィ⟬ᑐ㇟࡜ࡋࠊʌʌ ࠊQʌ ࠊʌʌ ࡢ୕㏻ࡾࡢບ㉳≧ែ࡟ࡘ࠸࡚ࠊග␗ᛶ໬ࡢ཯ᛂᗙᶆ㸦&& ⤖ྜࡢࡡࡌࢀゅ㸧ࢆᵝࠎ࡞್࡟ᅛᐃࡋࡓᵓ㐀᭱㐺໬ࢆ &$66&) ἲ࡛ᐇ⾜ࡋࡓࠋࡉࡽ࡟ࠊᚓࡽࢀࡓ᭱㐺໬ᵓ㐀ࡢࡑࢀࡒࢀ࡟ᑐࡋࠊ&$637
ἲࢆ⏝࠸࡚ᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែ࢚ࢿࣝࢠ࣮ࡢ෌ィ⟬ࢆ⾜ࡗࡓࠋ&$66&) ࠾ࡼࡧ &$637 ィ⟬ࡢ DFWLYH ✵㛫ࡣࠊʌʌ  ≧ែࡢィ⟬࡛ࡣ  㟁Ꮚࢆ  ಶࡢ ʌ ㌶㐨࡟㓄⨨ࡉࡏࡿ  ࠊQʌ  ≧ែࡢィ⟬࡛ࡣ  㟁Ꮚࢆ ಶࡢ ʌ ㌶㐨࠾ࡼࡧ  ಶࡢ㠀⤖ྜᛶ㌶㐨㸦Q ㌶㐨㸧࡟㓄⨨ࡉࡏࡿ   ࡜ࡋࡓࠋ௨ୖࡢィ⟬࡟ 0ROSUR ࢆ౑⏝ࡋࡓࠋ- 221 -

㸦㸰㸧ࢢࣝࢥ࣮ࢫ࡜ࡑࡢ஧㔞య࡟࠾ࡅࡿ 2+ ⤖ྜࡢගゎ㞳ࡣࡌࡵ࡟ࠊᇶᗏ≧ែࡢᏳᐃᵓ㐀࡟࠾ࡅࡿࢢࣝࢥ࣮ࢫ࠾ࡼࡧࢭࣟࣅ࣮࢜ࢫࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ 7'')7 ἲ࡛ィ⟬ࡋࡓࠋ2+ ⤖ྜࡢගゎ㞳࡛ࡣࠊ✵㛫ⓗ࡟኱ࡁࡃᗈࡀࡗࡓ ı ㌶㐨࡬ࡢບ㉳ࡀᮏ㉁ⓗ࡞ᙺ๭ࢆᯝࡓࡍ࡜ண᝿
ࡉࢀࡿࠋࡑࡢࡓࡵࠊᇶᗏ㛵ᩘ࡟ GLIIXVH 㛵ᩘࢆຍ࠼࡚ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊı ㌶㐨࡬ࡢບ㉳࡛ࡣ㟁Ⲵࡀ኱ࡁࡃ
⛣ືࡍࡿࡓࡵࠊ')7 ࡢ஺᥮┦㛵ỗ㛵ᩘ࡜ࡋ࡚ࠊ㟁Ⲵ⛣ື≧ែࢆ㐺ษ࡟ィ⟬࡛ࡁࡿ㛗㊥㞳⿵ṇࢆ᪋ࡋࡓỗ㛵ᩘ
࡛࠶ࡿ &$0%/<3 ࢆ⏝࠸ࡓࠋḟ࡟ࠊບ㉳࢚ࢿࣝࢠ࣮ࡢィ⟬࡛ᚓࡽࢀࡓ 6 ≧ែ࡟ࡘ࠸࡚ࠊ2+ ⤖ྜ㛗࡟ἢࡗࡓ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࢆ 7'')7 ἲ࡛ィ⟬ࡋࡓࠋࢢࣝࢥ࣮ࢫ࡛ࡣ  ࠿ᡤࠊࢭࣟࣅ࣮࢜ࢫ࡛ࡣ  ࠿ᡤ
࠶ࡿ 2+ ⤖ྜࡢࡑࢀࡒࢀ࡟ᑐࡋࠊ⤖ྜ㛗ࢆᅛᐃࡋࡓᵓ㐀᭱㐺໬ࢆ 6 ≧ែ࡟㛵ࡋ࡚ᐇ⾜ࡋࡓࠋ௨ୖࡢィ⟬࡟
*$0(66 ࢆ౑⏝ࡋࡓࠋ




◊✲ᡂᯝ
࢖ࣥࢹ࢕ࢦ⣔Ⰽ⣲࡟ࡘ࠸࡚㸸ィ⟬ࡋࡓ୕㏻ࡾࡢບ㉳≧ែ㸦ʌʌ ࠊQʌ ࠊʌʌ 㸧ࡢ࠺ࡕࠊʌʌ ≧ែ࡛ࡣ࢖ࣥࢹ

࢕ࢦ࡜ࢳ࢜࢖ࣥࢹ࢕ࢦࡢ୧᪉࡟ࡘ࠸࡚㞀ቨࡢ኱ࡁࡉࡀ  H9 ࢆ㉸࠼ࠊᇶᗏ≧ែ࡜ࡢ෇㗹஺ᕪࡶぢࡽࢀ࡞࠿ࡗ
ࡓࠋࡋࡓࡀࡗ࡚ࠊʌʌ ≧ែ࡟࠾ࡅࡿ␗ᛶ໬ࡣ࠸ࡎࢀࡢศᏊ࡛ࡶ㠀ᖖ࡟㉳ࡇࡾ࡟ࡃ࠸࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊQʌ≧ែ࡜ ʌʌ ≧ែ࡛ࡣ && ⤖ྜࡀ ⛬ᗘࡡࡌࢀࡓᵓ㐀࡛ᇶᗏ≧ែ࡜ࡢ࢚ࢿࣝࢠ࣮ࡀ᥋㏆ࡋࠊ≉࡟ ʌʌ ≧ែ࡛ࡣᇶᗏ≧ែ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࡀ࡯ࡰ  ࡜࡞ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ୕㔜㡯≧ែ࡟࠾ࡅࡿ␗ᛶ໬ࡀ୍㔜㡯≧ែࡼࡾࡶ㉳ࡇࡾࡸࡍ࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡲࡓࠊ࠸ࡎࢀࡢບ㉳≧ែ࡟࠾࠸࡚ࡶࠊ␗ᛶ໬ࡢ཯ᛂ㞀ቨࡣࢳ࢜࢖
ࣥࢹ࢕ࢦࡢ᪉ࡀ࢖ࣥࢹ࢕ࢦ࡟ẚ࡭࡚ᑠࡉ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ
ࢢࣝࢥ࣮ࢫ࠾ࡼࡧࡑࡢ஧㔞య࡟ࡘ࠸࡚㸸ບ㉳࢚ࢿࣝࢠ࣮ィ⟬ࡢ⤖ᯝࠊࢢࣝࢥ࣮ࢫ࡜ࢭࣟࣅ࣮࢜ࢫࡢ୧᪉࡟
࠾࠸࡚⣸እ㡿ᇦࡢග྾཰࡛㑄⛣࡛ࡁࡿ 6 ≧ែࡀᏑᅾࡋࠊ㓟⣲ཎᏊୖࡢ Q ㌶㐨࠿ࡽ 2+ ⤖ྜࡢ ı ㌶㐨࡬ࡢ㑄⛣࡛≉ᚩ࡙ࡅࡽࢀࡿ Qı ≧ែ࡛࠶ࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡲࡓࠊගゎ㞳ࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ィ⟬࡛ࡣࠊ࠿ᡤࡲࡓࡣ  ࠿ᡤ࠶ࡿ 2+ ⤖ྜࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊࡑࡢゎ㞳࡟కࡗ࡚ 6 ≧ែ㸦Qı ≧ែ㸧࡜ 6 ≧ែࡢ࢚ࢿࣝࢠ࣮ࡀ኱ࡁࡃ᥋㏆ࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ⣸እ⥺࡟ࡼࡿගບ㉳ᚋࠊ࡝ࡢ 2+ ⤖ྜ࡟࠾࠸࡚ࡶ⤖ྜゎ㞳࠾ࡼࡧ෇㗹஺ᕪࢆ௓ࡋࡓ↓㍽ᑕኻάࡀ㉳ࡇࡿྍ⬟ᛶࢆ♧၀ࡋ࡚࠸ࡿࠋࡲࡓࢭࣟࣅ࣮࢜ࢫ࡛ࡣࠊ
¶఩ࡢ 2+ ⤖ྜࢆゎ㞳ࡉࡏࡓ࡜ࡁࡢ 6 ≧ែࡢ࢚ࢿࣝࢠ࣮ࡀ௚ࡢ 2+ ⤖ྜࡼࡾࡶపࡃࠊගゎ㞳ࡀࡼࡾ㉳ࡇࡾࡸࡍ࠸ࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋࡇࢀࡣࠊ¶఩ࡢ 2+ ⤖ྜࡢ㏆ࡃ࡟௚ࡢཎᏊࡀᑡ࡞ࡃࠊı ㌶㐨ࡀࡼࡾ✵㛫ⓗ࡟኱ࡁࡃᗈࡀࡗ࡚࠸ࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

࡞ࡋ




ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

࡞ࡋ- 222 -

εήψϩఽୣΝ੏‫ͤޜ‬Ζ‫ڌ‬୉νϱϏέ࣯෵߻ର͹෾ࢢಊྙָεϝϣϪʖεϥϱͶΓΖಊద੏‫ߑؽޜ‬մ໎



0ROHFXODU'\QDPLFVVLPXODWLRQVWXGLHVRQ
WKHG\QDPLFDOORVWHULFVLJQDOUHJXODWLRQPHFKDQLVPRIDKXJHSURWHLQFRPSOH[‫ۑ‬⡿⃝ ᗣ⁠㸦㏆␥኱Ꮫ㸧1◊✲┠ⓗ/LYHU .LQDVH % /.%ɼพ໌ 67.ʥͺ͗Ξཊ੏ҾࢢͲ͍Εಝఈ෨Ғ͹Πϝό࢐รҡ͗൅͗ΞΝ΍ͪΔ

ͤ͞ͳ͗ๅࠄ͠Ηͱ͏Ζɿ/.% ͺιϨϱηϪΨωϱϨϱ࢐Կ߮ોͲɼࡋ๖͹େःʀଁ৫ʀ‫ۅ‬੓Ͷ‫ؖ‬ΚΖ॑གྷ͵੏‫ޜ‬Ҿࢢ͹ҲͯͲ͍Εɼࡋ๖͹Φϋϩάʖਫ਼ࢊ௒੖Ͷ਄͚‫ؖ‬ΚΖ $03DFWLYDWHGSURWHLQNLQDVH $03.
‫׈‬੓Ν੏‫ͤޜ‬Ζɿ /.% ͺ 02Ѝ ͳ 675$'Ѝ ‫ ;ٶ‬/.% ͹  ͯ͹νϱϏέ࣯ҾࢢͲߑ੔͠ΗΖϖτϫ෵߻ର‫ܙ‬੔ͶΓͮͱ‫׈‬੓ԿͤΖ͞ͳ͗ๅࠄ͠Ηͱ͕Εɼ; ત݃ধߑଆմੵ΍੔͠Ηͱ͏Ζ  /.% ߑଆ͹‫׈‬੓Կϩʖϕͺ /.% ͹Ϩϱ࢐Կ‫׈‬੓൅‫ݳ‬Ͷ਄͚‫ؖ‬༫ͤΖɿ͠ΔͶ෵߻ର஦͹ /.% ͳ 675$'Ѝ ‫ ;ٶ‬02ЍؔͶಉ͚ಊద͵ΠϫητϨρέްՎͺ /.% ͹‫׈‬੓੏‫ޜ‬Ͷ॑གྷ͵ༀׄΝՎͪ͢ͱ͏ΖՆ೵੓͗ࣖࠨ͠Ηͱ͏
Ζɿ͖͢͢͞͹෵߻ର‫ܙ‬੔ͶΓͮͱ /.% Ν‫׈‬੓ԿͤΖ෾ࢢ‫ߑؽ‬͹ಊదଈ໚ͺ͞ΗΉͲຈʹ‫͠ڂݜ‬Ηͱ͏͵
͏ɿ/.% ͹‫׈‬੓੏‫ޜ‬Ͷ‫ؖ‬ΚΖΠϫητϨρέ͵ಊదްՎ͹‫ڂݜ‬ͺࡋ๖಼͹෾ࢢ੏‫ߑؽޜ‬͹સ༲ཀྵմͶͳͮͱ॑གྷ͵எ‫͍Ͳݡ‬Ζɿ/.% ͳ 675$'Ѝ ‫ ;ٶ‬02Ѝ ͖Δ੔ΖνϱϏέ࣯෵߻ରߑଆʤ:7.ʥΝਦ  Ͷࣖͤɿ ਦ  /.%675$'Ѝ02Ѝ ෵߻ରߑଆɿबΕͶഓ஖ͪ͢༻ഖਭ෾ࢢΏ΢Ψϱ‫ࢢݬ‬౵ͺ঴ྲྀ͢ͱ͏Ζɿࢷ৯ͺ 02Ѝ Νԭ৯ͺ 675$'Ѝ Νɼ੼৯ͺ /.% ΝͨΗͩΗࣖ͢ͱ͏Ζɿຌ‫ڂݜ‬ͺ෾ࢢಊྙָεϝϣϪʖεϥϱʤ0' εϝϣϪʖεϥϱʥ‫ؽͳࢋܯ‬փָस౵Ν‫ͪ͢༽׈‬υʖν਼ཀྵմੵघ๑Νۨ࢘͢ͱɼ/.% ͹‫׈‬੓Ν੏‫ͤޜ‬Ζ‫ڌ‬୉෵߻ର͹ಊద͵ΠϫητϨρέ෾ࢢ‫ߑؽ‬Νմ໎ͤΖ͞ͳΝ໪దͳ͢ͱ͏Ζɿ- 223 -

2◊✲᪉ἲࠊィ⟬᪉ἲ
3URWHLQ'DWD%DQNʤ3'%ʥͶౌ࿧͠Ηͱ͏Ζ 02Ѝɼ675$'Ѝɼ‫ ;ٶ‬/.% ͹෵߻ରߑଆ৚ๅʤ:7.ʥ

͖ΔεϝϣϪʖεϥϱ͹‫ܧ‬Νߑ஛ͪ͢ɿ0' εϝϣϪʖεϥϱͶͺ *520$&6 ϕϫήϧϞΝ༽͏ͪɿ /.%͹໼ਫ਼‫ܗ‬෵߻ର͹ 0' εϝϣϪʖεϥϱͶՅ͓ͱɼ෵߻ର‫ܙ‬੔͹ްՎΝ‫ͤৄݗ‬ΖҟͶ෵߻ର஦͹  ͯ͹νϱϏέ࣯ΝͨΗͩΗୱྖରͶ෾཯͢ͱพ‫ݺ‬Ͷ 0' εϝϣϪʖεϥϱ‫͢ࢋܯ‬ɼͨΗͩΗմੵͶචགྷ͵φϧζΥέ
φϨʖυʖνΝਫ਼੔ͤΖɿ ͞ΗΉͲͶ෵߻ର͖Δ෾཯ͪ͢ 02Ѝɼ675$'Ѝ ‫ ;ٶ‬/.% ֦ୱྖରνϱϏέ࣯͹ 0' εϝϣϪʖεϥϱ͹φϧζΥέφϨʖυʖνΝफॄͪ͢ɿ‫ࡑݳ‬ͺ෵߻ର͹ 0' εϝϣϪʖεϥϱυʖνΝफॄ஦Ͳ͍Ζɿ


3

◊✲ᡂᯝ
ਦ  Ͷ෵߻ର͖ΔୱྖରͶ෾཯͢ͱ 0' εϝϣϪʖεϥϱΝࣰࢬ͢ͱಚΔΗͪυʖν͹
506'ʤ5RRWPHDQVTXDUHGHYLDWLRQʥմੵ݃Վ
Νࣖͤɿ 02Ѝɼ675$'Ѝɼ/.% ͹ 506'஍ͺ҈ఈ͢ͱ͕Ε֦ʓ͹ 0' εϝϣϪʖεϥϱ͗ Ά · ฑ ߩ য় ସ Ͷ ୣ ͢ ͱ ͏ Ζ ͞ ͳ ͗ ൓ Ζ 
675$'Ѝ ͹ 506' ஍ͶͺҲ෨୉͘͵ߑଆรԿ͗೟ΌΔΗΖ͗ɼ͞ΗͺϓϪΫεϔϩ͵ߑଆ෨
෾༵Δ͙͹ൕӫͲ͍Ζ ਦ  Ͷୱ෾ࢢͶ෾཯͢ͱ 0' εϝϣϪʖεϥϱ Νࣰ ࢬ ͪ͢ ̑ ͯ͹ͪΞͼ͚࣯ɼ02Ѝɼਦ  ৏͖Δɼ02Ѝɼ675$'Ѝɼ/.% ͹ 506'

675$'Ѝɼ/.% ͹ 506)ʤ5RRWPHDQVTXDUH஍͹࣎ؔรԿIOXFWXDWLRQʥ஍Νࣖͤɿ506) մੵ͖ΔͨΗͩΗ͹ͪΞͼ͚࣯෾ࢢ͹ୱ෾ࢢয়ସͶ͕͜Ζक࠱
ߑଆ༵Δ͙͹ܑ޴֮͗೟͠Ηͪɿࠕ‫ޛ‬ͺɼ0' εϝϣϪʖεϥϱυʖνմੵͶɼ‫ؽ‬փָसͲ༽͏ΔΗΖ਼ཀྵմੵघ๑ΏυΡʖϕϧʖωϱήΝ࢘ͮͱɼνϱϏέ಼࣯෨‫;ٶ‬νϱϏέ࣯ؔ͹ಊద‫ܐؖ‬Ν੠ືͶ਼஍ԿͤΖްՎద͵մੵʀ඲ՃΝࣰࢬ͢ɼಊదΠϫητϨρέްՎͶ‫ͤؖ‬Ζ৿‫͖॑ͯو‬གྷ͵எ‫ݡ‬͹பड़Ν໪ࢨͤɿ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ͵͢ฟ∧ᐇ⦼ࡲࡓࡣணᐃਦ  ৏͖Δ 02Ѝɼ675$'Ѝɼ/.% ͹ 506)
஍ɼॐ࣢͹ୱҒͺ QP Ͳԥ࣢ͺΠϝό࢐࢔‫خ‬൬ߺΝ
ࣖͤ

͵͢

- 224 -

㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ࡑࡢ཯ᛂᛶ
Theoretical investigation on structures of metal clusters andtheir reactivity‫ۑ‬ᑠᏳ ႐୍㑻 1,2㸪㧘㔝 ៅ஧㑻 1㸪ቑ⏣ ᫴ஓ 1㸪୰ᮧ ຾அ௓ 1㸪ఀ⸨ 㥴 1㸪Wang Lewei1㸪ᒾᮏ ᑗྐ 1㸪௒ᕝ ᣅග 1㸪⸨ཎ ᭷ᕼ 1㸦1 ᮾ኱㝔⌮㸧1◊✲┠ⓗᩘಶ࠿ࡽᩘⓒಶࡢ㔠ᒓཎᏊࡀ᭷ᶵ㓄఩Ꮚ࡛⿕そࡉࢀࡓ㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡣ㸪ࣂࣝࢡࡢ㔠ᒓࡸࢼࣀ⢏Ꮚ࡟ࡣぢࡽࢀ࡞࠸≉␗ⓗ࡞ᗄఱᵓ㐀ࡸ㞳ᩓⓗ࡞㟁Ꮚᵓ㐀ࢆࡶࡕ㸪ࡑࢀࡽ࡟⏤᮶ࡍࡿࣘࢽ࣮ࢡ࡞≀ᛶࢆⓎ⌧ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡲࡓ㸪㟁Ꮚᵓ㐀ࡣ㔠ᒓࢥ࢔࡟ᙧᡂࡉࢀࡿ㉸ཎᏊ㌶㐨㸦1S㸪1P͐㸧࡟ࡼࡗ࡚グ㏙ࡉࢀ㸪ࡇࢀࡽࡢ㌶㐨ࡢ‽఩ࡸ㓟໬㑏ඖᣲື࡟ࡣ㸪㔠ᒓࢥ࢔ࡢࢧ࢖ࢬ࣭ᙧ≧ࡔࡅ࡛࡞ࡃ㸪㓄఩Ꮚᒙࡢ✀㢮ࡸᴟᛶࡶᙳ㡪ࢆཬࡰࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ㸪ṇ஧༑㠃యᆺࡢ Pt@Au12 ㉸ཎᏊࢆ࢔ࣝ࢝ࣥࢳ࣮࢜ࣛࢺ㓄఩Ꮚ SCnH2n+1㸦SCnn = 4, 8, 12, 16㸧࡟ࡼࡿ 6 ಶࡢ Au2(SCn)3 ࣘࢽࢵࢺࡀಖㆤࡋࡓ㸪[PtAu24(SCn)18]–q ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ ᐃࡋ㸪DFT ィ⟬ࢆ୪⏝ࡋ࡚ㄏ㟁యᒙ࡜ࡋ࡚ࡢ㓄఩Ꮚᒙࡀ㟁Ꮚᵓ㐀࡟ᑐࡋ࡚ཬࡰࡍຠᯝࢆㄪ࡭
ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
DFT ィ⟬ࡣ Gaussian16 ࣃࢵࢣ࣮ࢪ࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚ PBE ࢆ㸪ᇶᗏ㛵ᩘ࡜ࡋ࡚ Au ࡜ Pt ࡟ᑐࡋ࡚ࡣ Lanl2dz ࢆ㸪C, H, S ࡟ᑐࡋ࡚ࡣ 6–31G(d)ࢆ㐺⏝ࡋࡓࠋᑐ㇟ࢡࣛࢫࢱ࣮࡛ࡣ SCn ࢆ࣓ࢳࣝࢳ࣮࢜ࣛࢺ
㸦SCH3㸧࡛⡆␎໬ࡋ㸪[PtAu24(SCH3)18]–q㸦q = 0–2㸧ࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗ࡚᩿⇕㟁Ꮚぶ࿴ຊࡸᆶ┤⬺㞳࢚ࢿࣝࢠ࣮ࢆぢ✚ࡶࡗࡓࠋึᮇᵓ㐀ࡣ᪤ሗࡢࢡࣛࢫࢱ࣮[PtAu24(SCH3)18]0 ࡢ᭱㐺໬ᵓ㐀ࢆཧ↷ࡋ㸪᣺ືᩘィ⟬࠿ࡽ⹫ᩘ᣺ືࡀྵࡲࢀ࡞࠸ᒁᡤᏳᐃᵓ㐀࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ

3◊✲ᡂᯝ
[PtAu24(SCn)18]q㸦q = 1 ࠾ࡼࡧ 2㸧ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ ᐃ࠿ࡽ㸪[PtAu24(SCn)18]q㸦q = 0 ࠾ࡼࡧ 1㸧ࡢ᩿⇕㟁Ꮚぶ࿴ຊ㸦AEA㸧ࡣ 1 ౯ࡢ᪉ࡀ኱ࡁ࠸ࡇ࡜㸪ࡲࡓ AEA ࡣ㙐㛗 n ࡜࡜ࡶ࡟ቑຍࡋ㸪ࡑࡢቑຍᖜࡣ 1 ౯ࡼࡾࡶ2 ౯㈇࢖࢜ࣥࡢ᪉ࡀ኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡑࡇ࡛㸪࣓ࢳࣝࢳ࣮࢜ࣛࢺಖㆤࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚ᵓ㐀᭱㐺໬ࡋ࡚㟁Ꮚぶ࿴ຊࢆぢ✚ࡶࡗࡓ࡜ࡇࢁ㸪୰ᛶࡢ᪉ࡀ 1 ౯㈇࢖࢜ࣥࡼࡾࡶ AEA ࡀᑠࡉࡃ㸪࠸ࡎࢀࡢ౯ᩘࡢ AEA
ࡶ n = 4 ࡼࡾᑠࡉ࠸್࡛࠶ࡾ㸪ᐇ㦂⤖ᯝࡀ෌⌧ࡉࢀࡓࠋࡇࡢ㙐㛗౫Ꮡᛶࡣ㸪n ࡢቑຍ࡟ࡼࡿㄏ㟁⋡ࡢቑຍ࡟㉳
ᅉࡋ࡚㈇㟁ⲴࡀᏳᐃ໬ࡉࢀࡿࡇ࡜࡟㉳ᅉࡍࡿ࡜⪃࠼ࡽ࠼ࡿࠋࡲࡓ㸪ศᏊ㌶㐨ࡢ࢚ࢿࣝࢠ࣮ࢆゎᯒࡋࡓ࡜ࡇࢁ㸪
2 ౯㈇࢖࢜ࣥ㸦8 㟁Ꮚ㛢Ẇ㸧࡛ࡣ㉸ཎᏊ 1P ㌶㐨ࡀ 3 㔜⦰㏥࡛࠶ࡿ୍᪉㸪1 ౯㈇࢖࢜ࣥࡸ୰ᛶ࡛ࡣ⦰㏥ࡀゎࡅ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

4Ⓨ⾲࣭ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬S. Hasegawa, S. Masuda, S. Takano, K. Harano, T. TsukudaࠊACS Catal. 2022, 12, 6550–6558.
[2] ‫ۻ‬T. Shigeta, S. Takano, T. TsukudaࠊAngew. Chem., Int. Ed. 2022, 61, e202113275.
[3] ‫⏣ۻ‬ᆏ ♸㔛Ꮚ㸪ఀ⸨ 㥴㸪㝡ᒣ ࡵࡄࡳ㸪ࠐᑠᏳ ႐୍㑻㸪ఢ㐩ဢ㸪ศᏊ⛉Ꮫウㄽ఍㸪2022 ᖺ 9 ᭶ 19 ᪥㸪៞᠕⩏ሿ኱Ꮫ㸦ᶓ὾㸧㸪ཱྀ㢌Ⓨ⾲

- 225 -

ኳ↛⣸እ⥺㜵ᚚ≀㉁࣐࢖ࢥࢫ࣏ࣜࣥᵝ࢔࣑ࣀ㓟ࡢ㧗㏿⬺ບ㉳ᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDOVWXG\RIWKHIDVWGHH[FLWDWLRQPHFKDQLVPRIQDWXUDO89
VFUHHQLQJFRPSRXQGVP\FRVSRULQHOLNHDPLQRDFLGV
‫␊ۑ‬ᒣ



ඔ㸦ᒣཱྀᮾி⌮⛉኱Ꮫ㸧◊✲┠ⓗ࣐࢖ࢥࢫ࣏ࣜࣥᵝ࢔࣑ࣀ㓟㸦Mycosporine-like Amino AcidsࠊMAAsࠊᅗ 1a㸧ࡣᾏ⸴ࡸᾏὒᛶᚤ⏕≀࡟ࡼࡗ࡚⏕ྜᡂࡉࢀ࡚࠸ࡿ㠀ⰾ㤶᪘ᛶ໬ྜ≀࡛࠶ࡾࠊ⣸እ⥺ࢆ㧗ຠ⋡࠿ࡘᏳᐃ࡟྾཰ࡍࡿኳ↛ࡢ⣸እ⥺㜵ᚚ๣࡜ࡋ࡚
ᾏὒ⏕≀⏺࡛ά⏝ࡉࢀ࡚࠸ࡿࠋࡑࡢ≉ᛶ࠿ࡽ MAAs ࡣᾏὒ⏕≀ࡢ⣸እ⥺㐺ᛂ⬟ࢆ⣣ゎࡃ㘽࡜ࡋ࡚⪃࠼ࡽࢀ࡚࠾ࡾࠊࡲࡓࠊ࠸ࢃࡺࡿ᪥↝ࡅṆࡵࡢ᪂つ⣲ᮦ࡜ࡋ࡚ࣄ࣮࣐ࣗࣥ࣊ࣝࢫࢣ࢔࡬ࡢά⏝ࡶ㏆ᖺὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ
➹⪅ࡣࡇࢀࡲ࡛ࠊMAAs ࡟ࡼࡿ⣸እ⥺㜵ᚚࡢᶵᵓゎ᫂ࢆ┠ⓗ࡜ࡋࡓศᏊ⛉Ꮫ◊✲࡟ྲྀࡾ⤌ࡳࠊࡑࡢග㟁Ꮚບ㉳≧ែࡀᇶᗏ≧ែ࡬࡜࢚ࢿࣝࢠ࣮஺ᕪⅬ㸦෇㗹஺ᕪ㸧ࢆ㏻ࡌ࡚ᐜ᫆࡟↓㍽ᑕ⬺ບ㉳ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ
࡚ࡁࡓ㸦ᅗ 1b㸧ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊMAAs ࡀᐇ㝿࡟↓㍽ᑕ⬺ບ㉳ࡍࡿᵝᏊࡢ᫬⣔ิࢆ㠀᩿⇕ศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾㄪᰝࡋࡓࠋࡲࡓࠊඛ㏙ࡋࡓ࢚ࢿࣝࢠ࣮஺ᕪⅬࡢ⤖ᯝࢆᡂᯝⓎ⾲ࡍࡿ࡟࠶ࡓࡾ㏣ຍィ⟬ࡀ
ู㏵ᚲせ࡟࡞ࡗࡓࡓࡵࠊࡑࡢⅬ࡛ࡶ RCCS ࢆᮏᖺᗘ฼⏝ࡋࡓࠋᅗ 1㸬
㸦a㸧௦⾲ⓗ࡞ 4 ✀ࡢ MAAs ࡢᵓ㐀ᶍᘧᅗࠊ㸦b㸧MAAs ࡢບ㉳๓ᚋࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝᶍᘧᅗ

◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬ࣃࢵࢣ࣮ࢪࡢ OpenMolcas v21.10 ࢆ฼⏝ࡋ࡚ Tully ࡢ᭱ᑠࢫ࢖ࢵࢳ⾲㠃࣍ࢵࣆࣥࢢἲࢆᐇ᪋ࡋ

ࡓࠋࡇࡢᡭἲࡣ␗࡞ࡿ㟁Ꮚ≧ែ㛫ࡢ☜⋡ⓗ㑄⛣ࢆチᐜࡋࡘࡘศᏊ⣔ࡢ᫬㛫Ⓨᒎࢆ㏣㊧ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ
ἲ࡛࠶ࡾࠊMAAs ࡢග㟁Ꮚບ㉳≧ែ࠿ࡽᇶᗏ≧ែ࡬ࡢ↓㍽ᑕ⬺ບ㉳ࢆ㏣㊧ྍ⬟࡟ࡍࡿࠋᮏ◊✲࡛ࡣ㑄⛣☜⋡ࢆ㟁Ꮚ≧ែ㛫ࡢ㔜࡞ࡾ࡟ᇶ࡙࠸࡚ホ౯ࡋ㸦Hammes-Schiffer ࡽ࡟ࡼࡿ㏆ఝἲ㸧ࠊࡲࡓࠊ㟁Ꮚ≧ែ㛫ࡢ⤡ࡳྜ࠸㸦ࢥࣄ࣮ࣞࣥࢫ㸧ࡀ㐣኱ホ౯ࡉࢀࡿၥ㢟࡟ࡘ࠸࡚ Granucci ࡽ࡟ࡼࡿಟṇἲࢆ㐺⏝ࡋ࡚ྲྀࡾ⤌ࢇࡔࠋࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࡢ᫬㛫Ⓨᒎࡣᇶᗏ≧ែ࠿ࡽග㟁Ꮚບ㉳ࡋࡓ┤ᚋࡢ MAAs ࡢᣲືࢆ 0.5fs ้ࡳ࡛㏣㊧ࡋࡓࠋࢩ࣑ࣗࣞ
࣮ࢩࣙࣥึᮇ≧ែ࡛࠶ࡿᇶᗏ≧ែࡣ⇕ᖹ⾮໬ࡉࡏࡓ MAAs ࢆ 200ps ẖ࡟ࢧࣥࣉࣜࣥࢢࡋ࡚‽ഛࡋࡓࠋ- 226 -◊✲ᡂᯝMAAs ࡀ⣸እ⥺྾཰ᚋࡢග㟁Ꮚບ㉳≧ែ㸦S1㸧࠿ࡽᇶᗏ≧ែ㸦S0㸧࡬࡜⬺ບ㉳ࡍࡿᵝᏊࢆ㠀᩿⇕ศᏊືຊᏛ

ࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽ㏣㊧ฟ᮶ࡓ㸦ᅗ 2㸧ࠋᐇ㝿࡟ࡣࠊࡇࢀࡲ࡛࡟ึᮇ≧ែࡢ‽ഛ㸦⇕ᖹ⾮໬㸧ࡀ᏶஢ࡋࡓ 10ᮏࡢࢧࣥࣉࣝ࡟ࡘ࠸࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࡓࡔࡅࡢẁ㝵ࡔࡀࠊ10 ᮏࡢࢧࣥࣉࣝ඲࡚࡟࠾࠸࡚⣸እ⥺྾཰ᚋ
200-500fs ࡛ MAAs ࡢ୺࡞༨᭷⋡ࡀ S1 ࠿ࡽ S0 ࡬⛣ࡾኚࢃࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿ㸦ᅗ 2a㸧
ࠋ200-500fs ࡜࠸࠺⬺ບ㉳ࡲ࡛ࡢ᫬㛫ࡣࠊMAAs ࡢග㟁Ꮚບ㉳≧ែࡢᑑ࿨ࡀ 200-300fs ࡛࠶ࡿ࡜࠸࠺ᐇ㦂◊✲ࡢሗ࿌㸦J. Phys. Chem.
Lett., 2021, 12, 3641-3646㸧࡜ⱝᖸࡢࡎࢀࡀ࠶ࡿࡶࡢࡢࠊᐃᛶⓗ࡟ࡣᴫࡡ୍⮴ࡋ࡚࠸ࡿࠋ⬺ບ㉳๓ᚋࡢศᏊᵓ㐀࡟ὀ┠ࡍࡿ࡜ࠊศᏊෆ⎔ᵓ㐀࡜࢔࣑ࣀ㓟ࡢ㐃⤖㒊ศࡀኚᙧࡋࠊࡼࡾලయⓗ࡟ࡣࠊ㐃⤖ࢆᢸ࠺ CN ⤖ྜࡀ⎔ࡢ㠃࠿ࡽ㉳ࡁୖࡀࡿࡼ࠺࡟ື࠸࡚࠸ࡓࠋࡇ࠺ࡋࡓືࡁࡣ㟼ⓗ࡞㔞Ꮚ໬Ꮫィ⟬࠿ࡽண᝿ࡉࢀ࡚࠸ࡓບ㉳ MAAs ࡢኚᙧ࡜㢮ఝࡋ࡚࠸ࡓࡀ㸦ᅗ 1b㸧ࠊ⣽㒊࡛ࡣண᝿࡜␗࡞ࡿⅬࡶぢࡽࢀࡓࠋලయⓗ࡟ࡣࠊ㠀᩿⇕ࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࡀ♧ࡋࡓᐇ㝿ࡢືࡁࡣࠊศᏊෆ⎔ᵓ㐀࡜࢔࣑ࣀ㓟ࡢ㐃⤖㒊ศࡀᒁᡤⓗ࡟ኚᙧࡋࡘࡘࡶศᏊ඲య࡛ࡣࡑࢀ࡯࡝
┠❧ࡗ࡚ኚᙧࡋ࡞࠸ࡶࡢ࡛࠶ࡾ㸦ᅗ 2b㸧ࠊࡇࢀࡣບ㉳ MAAs ࡣ඲㌟ࡀኚᙧࡍࡿ࡜࠸࠺㔞Ꮚ໬Ꮫィ⟬ࡢண᝿ࡗ࡜ࡣࡸࡸ␗࡞ࡿࡶࡢ࡛࠶ࡗࡓࠋ㠀᩿⇕ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜㟼ⓗ࡞㔞Ꮚ໬Ꮫィ⟬ࡢ㐪࠸ࡀ⏕ࡌࡓ⌮⏤࡟ࡘ࠸࡚ࡣࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢧࣥࣉࣝࢆࡼࡾ⵳✚ࡋ࡚⤫ィⓗ࡞ゎᯒ࠿ࡽ᫂ࡽ࠿࡟ࡋࡓ࠸࡜⪃࠼࡚࠸ࡿࠋ

ᅗ 2㸬
㸦a㸧⣸እ⥺྾཰ᚋࡢ MAAs 㠀᩿⇕≧ែ࡟࠾ࡅࡿྛ㟁Ꮚ≧ែࡢ༨᭷⋡ࡢ᫬㛫ኚ໬㸦ග㟁Ꮚບ㉳≧ែ S1㸦ᐇ⥺㸧࡜ᇶᗏ≧ែ S0㸦Ⅼ⥺㸧ࡢ༨᭷⋡ࡢኚ໬ࢆึᮇ≧ែࢧࣥࣉࣝẖ࡟⥺Ⰽࢆኚ࠼࡚⾲♧ࡋࡓ㸧ࠊ㸦b㸧ࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ୰ࡢศᏊᵓ㐀ࡢ௦⾲౛ࢆ㔜ࡡࡓᶍᘧᅗ㸦୙㏱᫂ࡢᲬ⌫⾲♧㸹⣸እ⥺྾཰┤ᚋࡢᵓ㐀㸹༙㏱᫂ࡢᲬ⌫⾲♧㸹⣸እ⥺྾཰ᚋ 200-500fs ᫬Ⅼ࡛ࡢ⬺ບ㉳୰ࡢᵓ㐀㸧

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫“ ۻ‬ᾏ⸴⏤᮶ࡢ⣸እ⥺㜵ᚚ≀㉁࣐࢖ࢥࢫ࣏ࣜࣥᵝ࢔࣑ࣀ㓟࡟࠾ࡅࡿ⬺ບ㉳㐣⛬ࡢ㠀᩿⇕ศᏊࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ”, ␊ᒣඔ, ➨ 36 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬Makoto Hatakeyama, Shinichiro Nakamura, “Intrinsic Nature of the Ultrafast Deexcitation Pathway of
Mycosporine-like Amino Acid Porporphyra-334”, J. Phys. Chem. A, 2022, 126, 7460-7467.

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Ỉࡣ⁐፹࡜ࡋ࡚ከࡃࡢ໬Ꮫ཯ᛂ࡟࠾࠸࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋỈ୰࡛ࡢග໬Ꮫ཯ᛂ࡞࡝㸪ࡑࡢศᏊㄽⓗ࣓࢝ࢽࢬ࣒ࢆ⌮ゎࡍࡿࡓࡵ࡟ࡣ㸪Ỉࡢ㟼ⓗᵓ㐀ࡢࡳ࡞ࡽࡎບ㉳ࢲ࢖ࢼ࣑ࢡࢫࢆ⌮ゎࡍࡿᚲせࡀ࠶ࡿࠋᮏ
◊✲ࡣ㸪ࡇࢀࡲ࡛ࣂࣝࢡỈ㸪࠶ࡿ࠸ࡣ✵ẼỈ⏺㠃ࡢ2+᣺ືࡢ⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࢆ㸪➨୍ཎ⌮ศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ᣺ືࡢ⮬⏤ᗘࢆ୍㒊ᣊ᮰ࡍࡿࡇ࡜࡛⦆࿴⤒㊰ࢆ㝈ᐃࡍࡿ᪉ἲ࡟ࡼࡾỴᐃࡋᡂᯝࢆ࠶ࡆ
࡚ࡁࡓ>@ࠋ௒ᅇࡣ㸪Ỉࡢኚゅ᣺ື࣮ࣔࢻࢆບ㉳ࡋ㸪ࡑࡢ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࢆ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋỈࡢኚゅ᣺ື⦆࿴ࢆ㆟ㄽࡍࡿᐇ㦂࡜ࡋ࡚㸪ࡇࢀࡲ࡛㉥እSXPSSUREHศගἲ࡞࡝ࡀ⏝࠸ࡽࢀ࡚ࡁࡓࠋࡇࢀࡲ࡛ࡢ◊✲࡛ࡣ㸪ኚゅ᣺ືࡢ⦆࿴⤒㊰࡜ࡋ࡚ࡣ㸪  ศᏊෆࡢᅇ㌿ OLEUDWLRQ 㐠ື࡜ࡢ㠀ㄪ࿴࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾ⦆࿴ࡍࡿࢣ࣮ࢫ㸪  +2+ኚゅ᣺ືࡢಸ㡢࡜2+᣺ືࡀ࢝ࢵࣉࣜࣥࢢࡋ࡚ )HUPLඹ㬆ࡋ࡚ ⦆࿴ࡍࡿࢣ࣮ࢫ㸪  ศᏊ㛫ࡢኚゅ᣺ືࡀ࢝ࢵࣉࣝࡋ࡚⦆࿴ࡍࡿࢣ࣮ࢫ㸪ࡀࡇࢀࡲ࡛୺࡟㆟ㄽࡉࢀ࡚ࡁࡓࠋ&DUSHQWHUࡽ>@ࡣ㸪ୖグࡢ୰࡛ࡶ୺࡟  ࡸ  ࡢຠᯝࡢ㔜せᛶࢆ୺ᙇࡋࡓࡢ࡟
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⤒㊰ࡢ㔜せᛶࡀࡑࢀࡒࢀಶู࡟㆟ㄽࡉࢀ࡚ࡁࡓࡀ㸪ບ㉳ࡉࢀࡓኚゅ᣺ື࢚ࢿࣝࢠ࣮ࡀ࡝ࡢ⛬ᗘࡢ๭ྜ࡛  㹼 ࡢ⤒㊰ࢆ㏻ࡗ࡚⦆࿴ࡋ࡚࠸ࡃࡢ࠿ࡣ㆟ㄽࡉࢀ࡚ࡇ࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣ㸪௨ୗࡢ᪉ἲ࡟ࡼࡾ㸪ࡇࢀࡽ 㹼  ࡢ⦆࿴࢚ࢿࣝࢠ࣮ࡢ๭ྜࢆ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾᐃ㔞ⓗ࡟ホ౯ࡋ㸪ࡑࡢ⦆࿴࣓࢝
ࢽࢬ࣒ࡢゎ᫂ࢆヨࡳࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
ኚゅ᣺ື⦆࿴࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ⾜࠺ୖ࡛㸪௚ࡢ᣺ື࣮ࣔࢻ࡜ࡢ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡿ⦆࿴⤒㊰ࢆࡑࢀࡒࢀ

⊂❧࡟≉ᐃࡍࡿᚲせࡀ࠶ࡿࠋィ⟬᪉ἲ࡜ࡋ࡚ࡣ㸪ບ㉳ࡍࡿኚゅ᣺ື࡟㐠ື࢚ࢿࣝࢠ࣮ࢆ୚࠼㠀ᖹ⾮$,0'ࢩ
࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺஦࡟ࡼࡾ⦆࿴㏿ᗘࡢ᫬ᐃᩘ 7᫬㛫 ࢆ⟬ฟࡋࡓࠋୖグ  㹼  ࡢ⦆࿴⤒㊰ࢆಶู࡟ィ⟬ࡍࡿࡓࡵ࡟㸪ὀ┠ࡍࡿ᣺ື࣮ࣔࢻ௨እࡢ᣺ື㐠ື࡟ᣊ᮰ࢆ࠿ࡅࡿࡇ࡜࡟ࡼࡾ㸪ಶࠎࡢ᣺ື⦆࿴࣮ࣔࢻࡢࡳࢆ
ྍ⬟࡟ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡇࢀࢆ+2࡜+'2LQ'2⣔࡟ᑐࡋ࡚ ᣊ᮰࡞ࡋࡀ✀㢮㸪ᣊ᮰࠶ࡾࡀ
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⛬ᗘࡢ᫬ᐃᩘ࡛⦆࿴ࡍࡿ࠿ࢆィ⟬ࡋࡓ ᅗ ࠋᅗDࡢJUHHQFLUFOHࡣ㸪⣧Ỉ⣔>+2LQ+2 FDVH @࡟࠾ࡅࡿ㐣๫࢚ࢿࣝࢠ࣮ȟ‫ࡣ࠸ࡿ࠶> ܧ‬ᗘᅗ+2LQ+2 FDVH㸪ୖẁ ࡜ +'2LQ'2 FDVH㸪ୗẁ ࡟ᑐࡍࡿ D ບ㉳ኚゅ᣺ື࢚ࢿࣝࢠ࣮⦆࿴ࡢ᫬㛫Ⓨᒎȟ‫ ࡜ܧ‬E ᣺ື≧ែᐦᗘ 9'26 ࠋȟܶ = ܶ(‫ )ݐ‬െ ܶ ௚ , ܶ ௚ = 300 .@ࡢ᫬㛫Ⓨᒎࢆ⾲ࡋ࡚࠸ࡿࠋᐇ⥺ࡣȟ‫ܭ = ܧ‬ଵ exp(െ‫ ݐ‬ോ ܶଵ + ‫ܭ‬଴ )ࡢᘧ࡛ILWWLQJࡋࡓ⤖ᯝࢆ⾲ࡋ࡚࠾ࡾ㸪ܶଵ = 127 IVࡢ⤖ᯝࡀᚓࡽࢀࡓࠋᅗD࡟ࡣ㸪㔜Ỉ⣲⨨᥮ࡉࢀࡓ⣔>+'2LQ'2 FDVH @࡟࠾ࡅࡿ⤖ᯝࢆ♧ࡋ࡚࠾ࡾ㸪ܶଵ = 140 IVࡢ⤖ᯝࡀᚓࡽࢀࡓࠋ௨๓⾜ࡗࡓࣂࣝࢡỈ࡟࠾ࡅࡿບ㉳2+᣺ື⦆࿴ࡢሙ
ྜ࡛ࡣ㸪+2LQ+2࡛ࡣܶଵ = 110 IV㸪+'2LQ'2࡛ࡣܶଵ = 740 IVࡀᚓࡽࢀ࡚࠾ࡾ㸪㔜Ỉ⣲ᕼ㔘ࡢᙳ㡪ࡀ࠿࡞ࡾ኱ࡁ࠿ࡗࡓࡀ㸪௒ᅇࡢኚゅ᣺ື⦆࿴ࡢሙྜ࡟ࡣ࡯࡜ࢇ࡝㔜Ỉ⣲ᕼ㔘ࡢᙳ㡪ࡀぢࡽࢀ࡞࠸ࡇ࡜ࡀศ࠿ࡿࠋ
ࡇࢀࡣ᭱㏆ࡢᐇ㦂⤖ᯝ>@࡜୍⮴ࡋ࡚࠾ࡾ㸪ኚゅ᣺ືࡢሙྜࡣศᏊ㛫ࡢ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡿ࢚ࢿࣝࢠ࣮⦆࿴ࡢ
ᙳ㡪>ୖグ⦆࿴⤒㊰ղճ@ࡀᑠࡉ࠸஦ࢆ♧၀ࡋ࡚࠸ࡿࠋࡇࢀࡲ࡛ࡢᐇ㦂࡛ࡣ㸪SXPSSUREHᐇ㦂࡟ࡼࡾኚゅ᣺ື

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ࡢ⦆࿴᫬㛫ࢫࢣ࣮ࣝ ܶଵ ࡀIV࠿ࡽIVࡢ⠊ᅖ࡛ሗ࿌ࡉࢀ࡚࠾ࡾ㸪௒ᅇࡢィ⟬⤖ᯝ ܶଵ = 127 IV ࡣᐇ㦂࡟ࡼࡿሗ࿌ࡼࡾⱝᖸᑠࡉ࡞್࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ
௒ᅇࡢィ⟬࡛ࡣ㸪ࢩ࣑࣮ࣗࣞࢩࣙࣥࢭࣝ୰ࡢ㸯ศᏊࡢࡳࡢኚゅ᣺ືࢆບ㉳ࡋ /RFDOH[FLWDWLRQ 㸪ࡑࡢ⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࢆ㏣㊧ࡋ࡚࠸ࡿࡀ ᅗୖ 㸪ᐇ㦂࡛ࡣእሙ࡟ࡉࡽࡉࢀࡓ඲࡚ࡢศᏊࡢኚゅ᣺ືࡀ㞟ᅋⓗ࡟ບ㉳ࡉࢀࡿ &ROOHFWLYHH[FLWDWLRQ ࠋࡇࡢ㞟ᅋບ㉳ࡢᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟㸪ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚඲࡚ࡢ
ỈศᏊࡢኚゅ᣺ືࢆບ㉳ࡉࡏࡓ㝿ࡢ⦆࿴᫬㛫ࢆィ⟬ࡋࡓ ᅗୗ ࠋィ⟬⤖ᯝ࡜ࡋ࡚ܶଵ = 174 IVࡀᚓࡽࢀ㸪ᐇ㦂⤖ᯝ࡟㏆࡙ࡃࡇ࡜ࡀศ࠿ࡗࡓࠋ&ROOHFWLYH
H[FLWDWLRQ࡟࠾࠸࡚ܶଵ ࡀቑຍࡍࡿࡢࡣ㸪኱ࡁࡃࡣ࡞࠸ࡀ↓ど࡛ࡁ࡞࠸ศᏊ㛫᣺ື࢝ࢵࣉࣜࣥࢢ࡟ࡼࡿ࢚ࢿ
ࣝࢠ࣮⦆࿴ࡀ&ROOHFWLYHH[FLWDWLRQ࡟ࡼࡾLQDFWLYH࡟࡞ࡾ㸪࢚ࢿࣝࢠ࣮⦆࿴ࡀ㐜ᘏࡍࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽᅗ +2 LQ +2 ࡟࠾ࡅࡿኚゅ᣺ືࡢᒁᡤບ㉳/RFDO H[FLWDWLRQ ࠾ ࡼ ࡧ 㞟 ᅋ ບ ㉳ &ROOHFWLYHࢀࡿࠋᮏ◊✲࡛ࡣ࠸ࡃࡘ࠿ࡢ᣺ືࡢ⮬⏤ᗘ࡟ᣊ᮰᮲௳ࢆ
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H[FLWDWLRQ ࡟ᑐࡍࡿ࢚ࢿ ࣝ ࢠ࣮⦆࿴ ࡢ᫬㛫 Ⓨᒎȟ‫ࠋܧ‬ࢠ࣮㏿ᗘࢆ$,0'ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥぢ✚ࡶࡿࡇ࡜ࢆྍ⬟࡟ࡋࡓࠋ⣬㠃ࡢ㒔ྜୖ㸪ࡇࡢᣊ᮰࡟㛵ࡍࡿ⤖ᯝࡢヲ⣽ࡣ┬␎ࡋ㸪ࡇࡇ࡛ࡣ⤖ᯝࡢᴫせࡢࡳࢆ㆟ㄽࡍࡿࠋᅗ㸰ྑᅗ࡟ᣊ᮰ࢆ࠿ࡅ࡚࠸࡞࠸ሙྜࡢ⣧Ỉ⣔ ୖᅗ ࡜㔜Ỉ⣲ᕼ㔘⣔ ୗᅗ ࡟࠾ࡅࡿ᣺ື≧ែᐦᗘࢆ♧ࡍࠋᅗ㸰ྑୖᅗࡼࡾ㸪⣧Ỉ⣔࡛ࡣኚゅ᣺ືࡀ࿘ᅖศᏊࡢኚゅ᣺ື࡜ศᏊ㛫࢝ࢵࣉࣜࣥࢢ㸪࠾ࡼࡧᅇ㌿᣺ືࡢ㸰ಸ㡢࡜ศᏊෆ࢝ࢵࣉࣝࡍࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ୍
᪉㸪㔜Ỉ⣲ᕼ㔘⣔ࡢᅗ㸰ྑୗᅗࢆࡳࡿ࡜㸪ศᏊ㛫ࡢኚゅ᣺ືࡢ࢝ࢵࣉࣜࣥࢢࡣ࡯࡜ࢇ࡝࡞࠸ࡀ㸪ᅇ㌿᣺ືࡢ㸰ಸ㡢࡜ࡢศᏊෆ࢝ࢵࣉࣜࣥࢢࡣᏑᅾࡍࡿࠋᮏ◊✲࡛ぢ✚ࡶࡽࢀࡓບ㉳ኚゅ᣺ືࡢྛ⤒㊰࡬ࡢ⦆࿴⋡ࢆ⾲㸯࡟♧ࡍࠋ⣧Ỉ⣔࠾ࡼࡧ㔜Ỉ⣲ᕼ㔘⣔࡛ᅇ㌿᣺ືࡢ㸰ಸ㡢࡜ࡢศᏊෆ࢝ࢵࣉࣜࣥࢢࡀ୺࡞⦆࿴⤒㊰࡛࠶ࡿࡇ࡜
ࡀศ࠿ࡾ㸪ࡇࢀࡣܶଵ ࡀྠ఩యຠᯝ࡟㕌ឤ࡛࠶ࡗࡓ⤖ᯝ࡜FRQVLVWHQW࡛࠶ࡿࠋ+2LQ+2ࡢ⣔࡛ࡣ㸪ศᏊ㛫ࡢኚ
ゅ᣺ື࢝ࢵࣉࣜࣥࢢࡀᏑᅾࡍࡿࡓࡵ㸪ࡇࡢ⦆࿴⤒㊰ࡢ᭷↓ࡀ㸪ୖグࡢ/RFDOH[FLWDWLRQ ܶଵ = 127 IV ࡜
&ROOHFWLYHH[FLWDWLRQ ܶଵ = 174 IV ࡢ⤖ᯝࡢ㐪࠸ࢆ⏕ࡴཎᅉ࡟࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋ ⾲$,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿບ㉳ኚゅ࢚ࢿࣝࢠ࣮ࡢ᣺ື⦆࿴⋡
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䖩1<DVRVKLPD7,VKL\DPDDQG10DWXED\DVL㻌 $GVRUSWLRQ(QHUJHWLFVRI$PLQR$FLG$QDORJVRQ3RO\PHU:DWHU,QWHUIDFHV6WXGLHGE\$OO$WRP0ROHFXODU'\QDPLFV6LPXODWLRQDQGD7KHRU\RI6ROXWLRQV䠈-3K\V&KHP%126  䖩<0LXUD<<DPDPRWR6.DUDVKLPD12ULPR$+DUD.)XNXRND7,VKL\DPDDQG76X]XNL㻌 )RUPDWLRQRI/RQJ/LYHG'DUN6WDWHVGXULQJ(OHFWURQLF5HOD[DWLRQRI3\ULPLGLQH1XFOHREDVHV6WXGLHG8VLQJ([WUHPH8OWUDYLROHW
7LPH5HVROYHG3KRWRHOHFWURQ6SHFWURVFRS䠈-$P&KHP6RF145  ୍⯡ㅮ₇㸸ศᏊ⛉Ꮫウㄽ఍  ௳ࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍  ௳ࠊ㧗ศᏊᏛ఍໭㝣ᨭ㒊ㅮ₇఍  ௳㸪᪥ᮏ໬Ꮫ఍໭㝣ᨭ㒊ㅮ₇఍㸱௳㸪ᣍᚅㅮ₇  ௳

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ḟୡ௦෌⏕ྍ⬟࢚ࢿࣝࢠ࣮ࢆ┠ᣦࡋࡓ᪂つࢹࣂ࢖ࢫࡢศᏊㄽⓗゎ᫂
0ROHFXODU7KHRU\RI1RYHO'HYLFHVIRU1H[W*HQHUDWLRQ5HQHZDEOH
(QHUJ\‫ۑ‬ᮧᒸ ᱻࠊ኱᳃ 㕥㡢ࠊᓠୗ ᜨࠊ㤿ሙ ၏ⰼࠊ⸨ཎ ᡂ⨾ࠊ༡ ᰆ㤶㸦᪥ᮏዪ㝔࣭⌮㸧◊✲┠ⓗ1-1 ኴ㝧㟁ụ࡟࠾ࡅࡿ㟁Ⲵ⛣ືᆺ࣓࢝ࢽࢬ࣒ࡢゎ᫂᭷ᶵⷧ⭷ኴ㝧㟁ụࡣࠊ⣲Ꮚ࡟ගࢆ↷ᑕࡍࡿ࡜ࠊࢻࢼ࣮(D)ᒙ࡜࢔ࢡࢭࣉࢱ࣮(A)ᒙࡢ⏺㠃࡛⏕ᡂࡋࡓ࢟ࣕࣜ࢔
㟁Ꮚ࡜ṇᏍࡀࠕ࢚࢟ࢩࢺࣥࠖࢆᙧᡂࡋࠊ㟁Ⲵศ㞳ࡋ࡚㟁ᴟ࡟㟁ὶࢆὶࡍࡇ࡜ࡼࡾࠊຠ⋡ⓗ࡞㟁ὶ⏕ᡂ࡟ࡣࠊ࢚࢟ࢩࢺࣥࡢศゎ࡜⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡀ㔜せ࡛࠶ࡿࠋ㏆ᖺࠊ㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢᐇ⏝໬࡟ྥ
ࡅ࡚ࠊD/A ᭷ᶵᮦᩱ⮬యࡢ㧗ᛶ⬟໬ࡸࠊྜ⌮ⓗ࡞ D/A ⏺㠃ࡢタィἲࡀồࡵࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊ㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ D/A ⏺㠃ࡢタィࡸ࣓࢝ࢽࢬ࣒ࡢゎ᫂࡟ࡴࡅ࡚ࠊ┦⏺㠃࡟࠾ࡅࡿ࢚࢟ࢩࢺࣥ⏕ᡂ࡜ゎ㞳࡜⮬⏤㟁Ꮚࡢ㟁ᴟ࡬ࡢ࢟ࣕࣜ࢔ࢆಁ㐍ࡍࡿ࣓࢝ࢽࢬ࣒࡟ὀ┠ࡋࡓࠋ
1-2 ගゐ፹ኴ㝧㟁ụ࡟࠾ࡅࡿỈ㓟໬㐣⛬ࡢ཯ᛂᶵᵓ
໬▼⇞ᩱࡢ኱㔞౑⏝࡟ࡼࡾ᪂࢚ࢿࣝࢠ࣮ศ㔝ࡢ◊✲ࡀຍ㏿ࡋ࡚࠸ࡿࠋ≉࡟ேᕤගྜᡂࡣගゐ፹࡜㓟⣲Ⓨ⏕཯ᛂࡍࡿࡇ࡜࡛⇞ᩱࢆ⏕ᡂࡍࡿ࣓࢝ࢽࢬ࣒ࢆ᭷ࡍࡿ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋᮏㄢ㢟࡛╔┠ࡍࡿ㓟໬ࢥࣂࣝࢺ
ࡶỈࡢ 4 㟁Ꮚ㓟໬཯ᛂ࡟ࡼࡗ࡚㓟⣲ࢆⓎ⏕ࡍࡿࠋZhang ࡽࡣࠊ᫬㛫ศゎ FTIR ἲ࡟ࡼࡾࠊ2 ࡘ㸦1 ࢧ࢖ࢺ㸧࡞
࠸ࡋࡣ 1 ࡘࡢ OH ᇶ㸦1 ࢧ࢖ࢺ㸧࡛཯ᛂࢆ㐍⾜ࡍࡿࡇ࡜ࠊ㸰ࢧ࢖ࢺ࡛ OO ⤖ྜࡀ⏕ᡂࡉࢀࡿ཯ᛂ㏿ᗘࡀࠊ㸯ࢧ࢖ࢺࡼࡾ 10 ಸ௨ୖ㧗㏿࡛࠶ࡿ࡜⤖ㄽ௜ࡅࡓࠋࡑࡇ࡛ࠊ㓟໬ࢥࣂࣝࢺගゐ፹ࡢ 1 ࢧ࢖ࢺ࡜ 2 ࢧ࢖ࢺࡢ཯ᛂ࡟࠾
ࡅࡿ཯ᛂ⤒㊰ࡸ཯ᛂ㏿ᗘ࡟ࡘ࠸࡚⪃ᐹࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ

2-1 ኴ㝧㟁ụ࡟࠾ࡅࡿ㟁Ⲵ⛣ືᆺ࣓࢝ࢽࢬ࣒ࡢゎ᫂
Gaussian 16 ࢆ⏝࠸ࡓࠋእ㒊㔞Ꮚຠ⋡ࡀ኱ࡁࡃࠊᗈᇦ࡞྾཰≉ᛶࢆᣢࡘ㠀ࣇ࣮ࣛࣞࣥᆺపศᏊ࢔ࢡࢭࣉࢱ࣮ITIC ࡜ࠊ㧗࠸࢟ࣕࣜ࢔⛣ືᗘࢆ♧ࡍ࣏࣐࣮ࣜࢻࢼ࣮PBDBT ࡟ࡼࡿ⤌ࡳྜࢃࡏࡢࠊPBDB-T/ITIC㸦D/A㸧」ྜయࠊࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮ࢆ୍㒊ࣇࢵ⣲⨨᥮ࡋࡓ PBDB-T-SF/ITIC㸦FD/A㸧」ྜయࠊPBDB-T/IT4F㸦D/FA㸧」ྜయ࡟╔┠ࡋࠊᐦᗘỗ㛵ᩘἲࢆ⏝࠸࡚ࠊࣇࢵ⣲⨨᥮ࡀ OSCs ࡬୚࠼ࡿᙳ㡪࡟ࡘ࠸࡚ࠊᇶᗏ≧ែ࡜ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࠊbinding energyࠊ྾཰ࢫ࣌ࢡࢺࣝࡢほⅬࡼࡾࠊ⪃ᐹࡍࡿࠋィ⟬ࣞ࣋ࣝࡣ ωB97XD/6-31G(d)࡛࠶ࡿࠋ
2-2 ගゐ፹ኴ㝧㟁ụ࡟࠾ࡅࡿỈ㓟໬㐣⛬ࡢ཯ᛂᶵᵓ

ᅗ 1. ໬Ꮫᘧ
(a)ITIC (b) PBDB-T

Gaussian16 ࢆ⏝࠸ࡓࠋࠋ㓟໬ࢥࣂࣝࢺࡢ⾲㠃ࢡࣛࢫࢱࣔࢹࣝ࡟ࡘ࠸࡚ࠊᵓ㐀᭱㐺໬࡜᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋࡇࡢᵓ㐀࡟࠾ࡅࡿ཯ᛂࡀ㉳ࡁࡿ OH ᇶࢆほᐹࡍࡿࠋࡑࡢࡓࡵ཯ᛂ࡟ᐤ୚ࡋ࡞࠸࡜⪃࠼ࡽࢀࡿゐ፹ࡢ⾲㠃㒊ศࡣᅛᐃࡋࠊ཯ᛂࡍࡿ OH ᇶࡢ㒊ศࡣ⮬⏤ᗘࢆࡶࡓࡏ࡚ィ⟬ࢆࡋࡓࠋ౑⏝ࡋࡓỗ㛵ᩘࡣ B3LYPࠊᇶᗏ㛵ᩘࡣࠊỈ⣲࡟ࡣ 6-31G(d,p)ࠊ㓟⣲࡟ࡣ 6-31G(d)ࠊCo ࡟ࡣ LanL2DZ ࢆ⏝࠸ࡓࠋ- 232 -◊✲ᡂᯝ

3-1 ኴ㝧㟁ụ࡟࠾ࡅࡿ㟁Ⲵ⛣ືᆺ࣓࢝ࢽࢬ࣒ࡢゎ᫂
ศᏊ㌶㐨ࡼࡾࠊD/A 」ྜయ࡜ D/FA 」ྜయࡣ A ศᏊෆ㑄⛣ࠊFD/A 」ྜయࡣࠊD/A 㟁Ⲵ⛣ືࡀ☜ㄆ࡛ࡁࡓࠋ
ࡇࢀࡣ D ࡢ F ⨨᥮ࡀ D/A 㛫࡛ࡢ㟁Ⲵ⛣ືࢆಁ㐍ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊྛ」ྜయࡢ㟁Ⲵ⛣ື㔞࣭㟁Ⲵ⛣ື㊥㞳ࢆẚ㍑ࡍࡿ࡜ࠊD/A 」ྜయ࡟ẚ࡭࡚ࠊFD/AࠊD/FA 」ྜయ࡟࠾ࡅࡿ㟁Ⲵ⛣ື㔞࡜㟁Ⲵ⛣ື㊥㞳ࡀቑຍࡋࡓࠋ㟁Ⲵ⛣ື㊥㞳ࡣບ㉳Ꮚࡢ኱ࡁࡉࢆᣦࡋ࡚࠸ࡿࠋᚑࡗ࡚ࠊ㟁Ⲵ⛣ື㊥㞳ࡢቑຍࡣࠊ㟁Ꮚ࡜࣮࣍ࣝࢆࡼࡾᘬ
ࡁ㞳ࡋࠊゎ㞳ࡋ࡚࠸ࡿࡇ࡜࡟┦ᙜࡍࡿࠋ௨ୖࡼࡾࠊD ศᏊࡢ୍㒊ࢆ F ⨨᥮ࡍࡿ࡜ࢡ࣮ࣟࣥຊࡀᙅࡵࡽࢀࡿࡇ
࡜࡛㟁Ꮚ࡜࣮࣍ࣝ㛫ࡢ㊥㞳ࡀ㛗ࡃ࡞ࡾບ㉳Ꮚࡢ᮰⦡≧ែࡀゎ࠿ࢀ࡚㟁Ⲵศ㞳ࡋࡸࡍࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
3-2 ගゐ፹ኴ㝧㟁ụ࡟࠾ࡅࡿỈ㓟໬㐣⛬ࡢ཯ᛂᶵᵓ

ࢿࣝࢠ࣮ࡢኚ໬࡛࠶ࡿࠋ࠸ࡎࢀࡢࢧ࢖ࢺ࡟࠾࠸࡚ࡶࠊ4 㟁Ꮚ཯ᛂ࡟ࡼ
ࡾ㓟⣲ࡀ⏕ᡂࡍࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋ2 ࢧ࢖ࢺ࡜ 1 ࢧ࢖ࢺࡢ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ࡢኚ໬ࢆẚ㍑ࡍࡿ࡜ࠊ3rd ࡛ 1 ࢧ࢖ࢺࡢ⮬⏤࢚ࢿࣝࢠ࣮
ࡀ-1.47eV ࡜ⴭࡋࡃపࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ
ࡇࢀࡣ 1 ࢧ࢖ࢺࡢ 3rd ࡛ࠊ⾲㠃࡟ࣉࣟࢺࣥࡀ྾╔ࡍࡿࡓࡵ࡟Ᏻᐃࡋࠊ࢚ࢿࣝࢠ࣮ࡀపࡃ࡞ࡗ࡚
࠸ࡿ࡜ࢃ࠿ࡗࡓࠋࡼࡗ࡚ࠊ1 ࢧ࢖ࢺ࡛ࡣ 3rd ࠿ࡽ 4th ࡢ཯ᛂ࡟㐍ࡴࡓ
ࡵ࡟ࠊ5.67 eV ࡢ኱ࡁ࡞࢚ࢿࣝࢠ࣮㞀ቨࢆ㉸࠼ࡿᚲせࡀ࠶ࡾࠊࡇࡢ㞀

Gibbs Free Energy (eV)

ᅗ 2 ࡣࠊ2 ࢧ࢖ࢺ࡜ 1 ࢧ࢖ࢺࡢྛࢫࢸࢵࣉ࡟࠾ࡅࡿ Gibbs ⮬⏤࢚

1st

12
10
8
6
4
2
0

7th

10.33
5th

7.11 7.33

3rd

12.92

9.81

5.87

4.13

2nd
1st

4.20

1.67

6.35
4.73

6th

4th

-1.47

1 site2 siteᅗ 2 ࢠࣈࢬࡢ⮬⏤࢚ࢿࣝࢠ࣮ࡢኚ໬

ቨࡀ཯ᛂ㏿ᗘࢆ㐜ࡃࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

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&KLFDJR RQOLQH   ★ $ $Q]DL< .XURVDNL0 6DHNL$ 0XUDRND$360DUFK0HHWLQJ &KLFDJR RQOLQH   ★ 6 ,NH\DPD1 2KWD5 7DFKLEDQD. <DPDVKLWD$ 0XUDRND$360DUFK0HHWLQJ&KLFDJR RQOLQH   ★ ᑠᬽ ኱᳃ 㔠Ꮚ ᒣୗ ᮧᒸ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ 㛗㔝 ᖺ  ★ ᒣ⏣Ᏻᩪ 㯮ᓮ బ఑ ᮧᒸ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ 㛗㔝  ᖺ  ★ ྜྷ⏣ ❧ⰼ ᓠୗ ༡ᮧᒸ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ 㛗㔝  ᖺ  ★ 㤿ሙ Ḉ஭ ᮧᒸ ➨  ᅇศᏊ⛉Ꮫウㄽ఍  ᶓ὾  ᖺ  ★ ⸨ཎ ᒣୗ ᮧᒸ ➨  ᅇศᏊ⛉Ꮫウㄽ఍  ᶓ὾   ★ ༡ ụᒣ ᮧᒸ➨  ᅇศᏊ⛉Ꮫウㄽ఍  ᶓ὾  ᖺ  ★ ᓠୗ ᮧᒸ ➨  ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍ ௝ྎ ᖺ  ★ 㤿ሙ Ḉ஭ ᮧᒸ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ᫓Ꮨᖺ఍ ኱ᒸᒣ  ᖺ  ★ ⸨ཎ ᒣୗᮧᒸ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ᫓Ꮨᖺ఍ ኱ᒸᒣ  ᖺ㸦6&&-$QQXDO 0HHWLQJ  6SULQJ 3RVWHU$ZDUG$UWLFOH㸧  ★ $ 0XUDRNDUG&6-$QQXDO0HHWLQJ  ࢔ࢪ࢔ᅜ㝿ࢩ࣏ࣥࢪ࣒࢘ 㔝⏣

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ ۻ‬M. Kaneko, A. Suzaki, A. Muraoka, K. Gotoh, K. Yamashita, J. Mater. Inf., 3, 8 (2023).
Muraoka, J. Comput. Chem. Jpn., 21, 55-47 (2022).
21, 45-47 (2022).

‫ ۻ‬Y. Baba, H. Sakurai, A.

‫ ۻ‬N. Fujiwara, K. Yamashita, A. Muraoka, J. Comput. Chem. Jpn.,‫ ۻ‬S. Jinnai, K. Murayama, K. Nagai, M. Mineshita, K. Kato, A. Muraoka, A. Yamakata, A. Saeki,

Y. Kobori, Y. Ie, J. Mater. Chem. A., 10, 20035-20047 (2022)- 233 -

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Theoretical Studies on Vibronic Couplings
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࠸࡚᪂ࡋ࠸≀㉁࣭ᮦᩱࢆ⌮ㄽⓗ࡟タィࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ2022 ᖺᗘࡣ୺࡟ (1) ⓑ㔠ࢡࣛࢫࢱ࣮ࡢᵓ㐀㛫㑄⛣࡜㏿ᗘㄽ (2) ᅛయ໬Ꮫ཯ᛂࡢศᏊㄽⓗ཯ᛂ㐣⛬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ (3) ศගࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ⏺㠃ỈࡢศᏊ㛫᣺ືࡢゎᯒࢆ⾜ࡗࡓࠋ
1.1 ⓑ㔠ࢡࣛࢫࢱ࣮ࡢᵓ㐀㛫㑄⛣࡜㏿ᗘㄽ㧗άᛶ࡞㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢ㔜せ࡞≉ᚩࡣ≉␗࡞㟁Ꮚ≧ែ࡜ᰂ㌾࡞ᵓ㐀ᦂࡽࡂࢆᣢࡘࡇ࡜࡛࠶ࡿࠋᚑࡗ࡚ࠊゐ፹άᛶࢆᮏ㉁ⓗ࡟⌮ゎࡍࡿ࡟ࡣ㟁Ꮚ≧ែࡢゎ᫂ࡔࡅ࡛࡞ࡃࠊᵓ㐀ᦂࡽࡂ࡟ࡶὀពࢆᡶ࠺ᚲせࡀ࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊゐ፹άᛶ࡟㛵ࡍࡿከࡃࡢඛ⾜◊✲࡛ࡣᏳᐃᵓ㐀ࡢ㟁Ꮚ≧ែゎᯒ࡟␃ࡲࡗ࡚࠾ࡾࠊᇶ㉁྾╔๓ࡢ㔠ᒓࢡࣛࢫࢱ࣮ࡢࡳࡢᵓ㐀ኚ໬࡛ࡉ࠼ࠊࡑࡢ㟁Ꮚ≧ែ࡜ࡢ㛵㐃ࡣ༑ศ࡟⌮ゎࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࢢࣛࣇ࢙ࣥᇶᯈୖࡢⓑ㔠 4 ཎᏊࢡࣛࢫࢱ࣮㸦Pt4㸧ࢆᑐ㇟࡟ࡋ࡚Ᏻᐃᵓ㐀㛫ࡢ㑄⛣ࡢ㏿ᗘㄽ࡜ࡑࢀ࡟క
࠺㟁Ꮚ≧ែኚ໬ࡢゎᯒࢆ⾜ࡗࡓࠋ
1.2 ᅛయ໬Ꮫ཯ᛂࡢศᏊㄽⓗ཯ᛂ㐣⛬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ ᶵ⬟ᛶᮦᩱ࡜ࡋ࡚⏝࠸ࡽࢀࡿ≀㉁ࡣ ࠎ࡟ࡋ࡚ᅛయ࡛࠶ࡾࠊᅛయ⾲㠃࠾ࡼࡧෆ㒊࡛ࡢ໬Ꮫ཯ᛂࡣᬑ㐢ⓗ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡑࡢ」㞧ࡉ࠿ࡽศᏊㄽⓗ࡞⌮ゎࡀ඲ࡃ㐍ࢇ࡛࠸࡞࠸ࠋ≉࡟ࠊᅛయ⾲㠃ࡀỈ⵨Ẽ࡞࡝ࡢእ㒊ศᏊ࡟ࡼࡾ౵㣗ࡉࢀࠊᅛయᵓ㐀⮬యࡀ኱ࡁࡃኚ໬ࡍࡿ཯ᛂ࡛ࡣཎᏊࡢᣑᩓ㐣⛬ࡀ㔜せ࡞཯ᛂᚊ㏿㐣⛬࡜⪃࠼ࡽࢀ࡚࠸ࡿࡀࠊࡑࡢศᏊᶵᵓࡣ୙࡛᫂࠶ࡿࠋᮏ◊✲࡛ࡣࠊ໬Ꮫ⵳⇕ᮦࡢ௦⾲ⓗ཯ᛂ࡛࠶ࡿ㓟໬࣐ࢢࢿࢩ
࣒࢘㸦(MgO) ࡢỈ࿴࡟ࡼࡿỈ㓟໬࣐ࢢࢿࢩ࣒࢘㸦Mg(OH)2㸧ࡢ⏕ᡂࢆᑐ㇟࡟ࡋࠊMgO ⾲㠃࡛ࡢỈศᏊࡢゎ㞳ࠊỈ⣲ཎᏊࡢᅛయෆ㒊࡬ࡢᣑᩓࠊMg(OH)2 ࡢ⤖ᬗ᰾ࡢ⏕ᡂ࡟㛵ࡍࡿᵓ㐀ኚ໬ࢆࢩ࣑࣮ࣗࣞࢺࡋࡓࠋ
1.3 ศගࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ⏺㠃ỈࡢศᏊ㛫᣺ືࡢゎᯒ ⏺㠃ࡣࣂࣝࢡ࡜ࡣ␗࡞ࡿ୙ᆒ୍࡛␗᪉ⓗ࡞⎔ቃ࡛࠶ࡿࠋ≉࡟⏺㠃࡛Ỉ⣲⤖ྜࡀ᩿⤯ࡉࢀࡿỈ࡟࠾࠸࡚ࡣࣂ
ࣝࢡỈ࡜ࡣ␗࡞ࡿศᏊࢲ࢖ࢼ࣑ࢡࢫࢆᣢࡘࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡞≀ᛶࢆㄪ࡭ࡿ࡟ࡣ᣺ືศගἲࡀ᭷
ຠ࡛࠶ࡾࠊᐇ㝿ࠊ㉥እ࣭࣐ࣛࣥศගᐇ㦂࡟ࡼࡗ࡚⣽Ꮝ࡟㛢ࡌ㎸ࡵࡽࢀࡓỈࡣࣂࣝࢡỈ࡟ẚ࡭࡚ศᏊ㛫Ỉ⣲⤖ྜఙ⦰ࡢࣆ࣮ࢡࡀ㧗Ἴᩘഃ࡟ࢩࣇࢺࡍࡿࡇ࡜ࡀほࡉࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣᇶ♏ⓗ࡞▱ぢࢆ⋓ᚓࡍࡿࡓࡵࠊࢢࣛࣇ࢙ࣥᇶᯈୖࡢ㸰ᒙⷧ⭷Ỉࢆᑐ㇟࡜ࡋ࡚࣐ࣛࣥศගィ⟬ࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲࢸ࣮࣐(1)࡛ࡣ VASP ࢆ฼⏝ࡋࡓ PBE ỗ㛵ᩘ࡟ࡼࡿ㑄⛣≧ែᵓ㐀᥈⣴ࢆྵࡴ㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋࢸ࣮࣐

(2)࡛ࡣ LAMMPS ࢆ౑⏝ࡋ࡚཯ᛂᛶຊሙ㸦ReaxFF㸧࡟ᇶ࡙ࡃࣞ࢔࢖࣋ࣥࢺศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢸ࣮࣐(3)࡛ࡣ LAMMPS ࡟ࡼࡾศᏊືຊᏛィ⟬ࢆ⾜࠸ࠊࡑࡢࢺࣛࢪ࢙ࢡࢺࣜ࡟ᇶ࡙࠸࡚ศගィ⟬ࢆ⾜ࡗࡓࠋ- 236 -

◊✲ᡂᯝ

3.1 ⓑ㔠ࢡࣛࢫࢱ࣮ࡢᵓ㐀㛫㑄⛣࡜㏿ᗘㄽ
Pt4 ࡢᏳᐃᵓ㐀ࡣẼ┦୰࡛ࡣ 5 ࡘ࡛࠶ࡗࡓࡢ࡟ᑐࡋࠊࢢࣛࣇ࢙ࣥᇶᯈୖ࡛ࡣ 0.3 eV ௨ෆ࡟ 16 ಶᏑᅾࡋࡓࠋ
16 ಶࡢᏳᐃᵓ㐀㛫ࡢ㑄⛣ࢆㄪ࡭ࡓ࡜ࡇࢁࠊPt4 ࡢᵓ㐀ኚ໬ࡀ࠾ࡼࡑࣆࢥ⛊௨ୖ࡛㉳ࡇࡿ㸦㧗࠸ࣂࣜ࢔ࢆ᭷ࡍ
ࡿ㸧ࡢ࡟ᑐࡋࠊ྾╔ࢧ࢖ࢺࡢ⛣ື㸦Pt4 ࡢ୪㐍㸧࡟ࡼࡿᏳᐃᵓ㐀㛫ࡢ㑄⛣ࡣࣇ࢙࣒ࢺ⛊࠿ࡽࣆࢥ⛊ෆ࡛㉳ࡇࡿ㸦ప࠸ࣂࣜ࢔ࢆ᭷ࡍࡿ㸧ࡇ࡜ࡀࢃ࠿ࡗࡓࠋᇶᯈ࡜ࡢ┦஫స⏝ࡢ㐪࠸࠿ࡽࠊ྾╔ࢧ࢖ࢺࡢ⛣ືࡢࡳ࡛ࡶ d ࣂࣥࢻ୰ᚰࡢኚ໬ࡀ☜ㄆࡉࢀࡓࡇ࡜࠿ࡽࠊPt4 ࡢ㟁Ꮚ≧ែࡣゐ፹཯ᛂࡸᇶ㉁྾╔㏿ᗘ࡟ẚ࡭࡚ᅽಽⓗ࡟㏿ࡃኚ໬ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣ Pt4 ࡢࡼ࠺࡞ᑠࡉ࡞ࢡࣛࢫࢱ࣮ゐ፹࡛ࡣࠊゐ፹཯ᛂ࡜ࢡࣛࢫࢱ࣮ᵓ㐀ࡢኚ໬ࡢືⓗ࡞࢝ࢵࣉࣜࣥࢢࡣᑠࡉ࠸࡜࠸࠺ࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ
3.2 ᅛయ໬Ꮫ཯ᛂࡢศᏊㄽⓗ཯ᛂ㐣⛬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ
࣏ࢸࣥࢩࣕࣝࢫࢣ࣮ࣜࣥࢢ࡟ࡼࡾࣞ࢔࢖࣋ࣥࢺࢆಁ㐍ࡉࡏࡿ᪂つศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥἲ࡟ࡼࡗ࡚ࠊMgOࡢỈ࿴཯ᛂ࠿ࡽ Mg(OH)2 ࡢ᰾⏕ᡂࡀ☜ㄆ࡛ࡁࡓࠋࡑࡢึᮇ㐣⛬ࡣỈศᏊࡢゎ㞳࡛࠶ࡾࠊ⏺㠃ࡢ⣙ 20%ࡀỈ㓟ᇶ㸦Ỉ㓟໬≀࢖࢜ࣥ㸧࡛そࢃࢀ࡚࠸ࡓࠋࡑࡢᚋࠊỈ㓟ᇶ࡟㞄᥋ࡋࡓ Mg ࡀ⏺㠃Ỉෆ࡬࡜⾲㠃ᒙ࠿ࡽ⬺㞳ࡍࡿ㐣⛬ࡀぢࡽࢀࡓࠋࡇࡇ࡛ࠊỈ㓟ᇶࡣ Mg ࡀᢤࡅࡓ✰ࢆỈ⣲࡛㒊ศⓗ࡟ᇙࡵࡿᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋ⬺㞳ࡋࡓMg ࡣ⾲㠃ᒙ㓟⣲ࡢࣈࣜࢵࢪࢧ࢖ࢺ࡟྾╔ࡋࠊ⏺㠃Ỉ୰ࡢỈ㓟໬≀࢖࢜ࣥࢆ㓄఩ࡋ㐃࡞ࡿࡇ࡜࡛ Mg(OH)2 ࡢᒙ࡜࡞ࡗ࡚࠸ࡓࠋ୍᪉ࠊᅛయෆ㒊࡬ࡢỈ⣲ࡢ౵ධ࣭ᣑᩓࡣ☜ㄆ࡛ࡁࡓࡶࡢࡢࠊ⏕ᡂ≀࡬⧅ࡀࡿ኱ࡁ࡞ᵓ㐀ኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࠋࡼࡗ࡚ࠊᅛయෆ㒊ࡢᵓ㐀ࢆቯࡋ⏕ᡂ≀࡬ࡢ኱つᶍኚ໬ࡀ㉳ࡁࡿ࡟ࡣࠊᒁᡤⓗ࡞Ỉ⣲ཎᏊࡢᣑᩓࡔࡅ࡛ࡣ୙༑ศ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
3.3 ศගࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ⏺㠃ỈࡢศᏊ㛫᣺ືࡢゎᯒⷧ⭷ỈࡢศᏊ㛫᣺ື࡟㛵ࡍࡿ࣐ࣛࣥࢫ࣌ࢡࢺࣝࡢᴫᙧࡣࣂࣝࢡỈ࡜ኚࢃࡽࡎࠊ500-900 cmѸ1 ࡟⛗ື㐠ືࠊ
250 cmѸ1 ࡜ 60 cmѸ1 ࡟ࡑࢀࡒࢀỈ⣲⤖ྜࡢఙ⦰ࠊኚゅ᣺ື࡟ᑐᛂࡍࡿࣆ࣮ࢡࡀ☜ㄆࡉࢀࡓࠋࡋ࠿ࡋࠊヲ⣽࡟ࡣⷧ⭷Ỉࡢࢫ࣌ࢡࢺࣝࡣ 900 cmѸ1 ࡢࣆ࣮ࢡࡀᙅࡃࠊ250 cmѸ1 ࡢࣆ࣮ࢡࡀᙉࡃ࡞ࡗ࡚࠸ࡓࠋゎᯒࡢ⤖ᯝࠊࡇࢀࡽ
ࡢࣆ࣮ࢡᙉᗘࡢኚ໬ࡣࠊ⏺㠃࡛Ỉ⣲⤖ྜࡀษࢀ㓄ྥኚ໬ࡢ㐠ືࡀ⦆ࡃ࡞ࡗࡓࡇ࡜ࡀཎᅉࡔ࡜ࢃ࠿ࡗࡓࠋ

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Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ྜྷ ۻ‬ᮧㄔ៞ “ேᕤຊㄏ㉳཯ᛂἲ࡜ࢢࣛࣇ⌮ㄽࢆ⏝࠸ࡓ཯ᛂᶵᵓ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ◊✲” ࢩ࣏ࣥࢪ࣒࢘
ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2022ࠖ, ᶓ὾, 9 ᭶ 18 ᪥ (2022).
‫✄ ۻ‬ᇉὈ୍ “࣏ࢸࣥࢩࣕࣝࢫࢣ࣮ࣜࣥࢢ࣭ࣁ࢖ࣈࣜࢵࢻࣔࣥࢸ࢝ࣝࣟἲࡢ㛤Ⓨ࡜௒ᚋࡢᒎᮃ” ➨ 5 ᅇ࣮࣡ࢡࢩࣙࢵࣉ㸸ࣞ࢔࣭࢖࣋ࣥࢺゎᯒ࡜ࢹ࣮ࢱࢧ࢖࢚ࣥࢫ, Ṋⶶ㔝, 12 ᭶ 4 ᪥ (2022).

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬S. Gocho, H. Nakamura, S. Kanno, Q. Gao, T. Kobayashi, T. Inagaki, and M. Hatanaka “Excited state calculations
using variational quantum eigensolver with spin-restricted ansätze and automatically-adjusted constraints” npj
Comput. Mater. 9, 13 (2023). ‫ ۻ‬7,QDJDNL0+DWDQDNDDQG66DLWR³$QLVRWURSLFDQG)LQLWH(IIHFWVRQ,QWHUPROHFXODU9LEUDWLRQDQG5HOD[DWLRQ'\QDPLFV/RZIUHTXHQF\5DPDQ6SHFWURVFRS\RI:DWHU)LOPDQG'URSOHWRQ*UDSKHQHE\0ROHFXODU'\QDPLFV
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5HODWLRQEHWZHHQFRQWULEXWLRQRIRUGHUUHJXODULW\LQOLTXLGVWUXFWXUHWRWUDQVSRUWSURSHUWLHVRIZDWHUDQGLQWHUDFWLRQSRWHQWLDOV‫ۑ‬኱㫽 ⠊࿴ࠊ ಙኴ ᓧࠊ ぢᕝ ె⃈ࠊ ┦⃝ ᆂభࠊ Ώ㎶ ⿱㸦᪂₲኱Ꮫ⌮Ꮫ㒊  ྠ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉㸧◊✲┠ⓗỈࡣẚ⇕ࢆጞࡵ࡜ࡋ࡚✀ࠎࡢ≉␗ⓗᛶ㉁ࢆ᭷ࡍࡿࡀࠊࡑࡢ㉳※ࡣᾮయᵓ㐀࡟㛵ಀࡍࡿ࡜᥎ ࡉࢀࠊỈ⣲⤖ྜ࡟ࡼࡿ㓟⣲ཎᏊ㛫ࡢᅄ㠃యⓗ㓄ิࡢつ๎ᛶ㸦࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮ q㸧࡜≉␗ⓗᛶ㉁࡜ࡢ┦㛵ࡀ㆟ㄽࡉࢀ࡚ࡁࡓࠋᵓ㐀ⓗつ๎ᛶࡀ㧗࠸࡯࡝ࡼࡾᙉᅛ࡞  ḟඖ⥙┠ᵓ㐀㸦Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡ㸧ࢆᙧᡂࡋࡸࡍ࠸࡜᥎

ࡉࢀࡿࡓࡵࠊ⮬ᕫᣑᩓಀᩘ࡞࡝ࡢ㍺㏦ಀᩘ࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡍ࡜⪃࠼ࡽࢀࡿࠋࡋࡓࡀࡗ࡚ࠊ࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮࡜㍺㏦ಀᩘࡢ㛵ಀࢆゎ᫂ࡍࡿࡇ࡜
ࡣࠊỈࡢ≉␗ⓗᛶ㉁ࢆ⌮ゎࡍࡿୖ࡛㔜せ࡛࠶ࡿࠋỈࢆグ㏙ࡍࡿ┦஫స⏝ࣔࢹࣝ࡜ࡋ࡚ࠊ㠀ศᴟࣔ
ࢹࣝࡢ 7,33ࠊ63&(ࠊ67ࠊP: ࡸࠊศᴟࣔࢹࣝࡢ 'DQ&KDQJ ࡞࡝ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࡀࠊ⮬ᕫᣑᩓಀᩘࡢィ⟬್ࡣࣔࢹࣝ౫Ꮡᛶࡀ኱ࡁ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊ⮬ᕫᣑᩓಀᩘ࡜࣮࢜ࢲ
࣮࣭ࣃ࣓࣮ࣛࢱ࣮ࡢ㛵ಀࡢணഛⓗ࡞ィ⟬࡟ࡼࡿ࡜ࠊ7,33 ࡜ 'DQ&KDQJ ࣔࢹࣝࡢẚ㍑࡛ࡣࠊ
࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮ࡀྠࡌ࡛ࡶࠊ⮬ᕫᣑᩓಀᩘࡀಸ⛬ᗘࡶ␗࡞ࡿሙྜࡀ࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣࠊᵓ㐀つ๎ᛶ௨እࡢᐤ୚ࡀ㍺㏦ಀᩘࢆグ㏙ࡍࡿୖ࡛↓ど࡛ࡁ࡞࠸ࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋᮏ◊✲ࡢ┠ⓗࡣࠊ✀ࠎࡢࣔࢹࣝࢆ⏝࠸࡚ࠊ㐣෭༷≧ែࢆྵࡴᾮయࡢỈࡢᖜᗈ࠸ ᗘ࡜ᐦᗘ㸦య✚㸧㡿ᇦ࡛ࠊ㍺㏦ಀᩘ㸦⮬ᕫᣑᩓಀᩘ㸧࠾ࡼࡧ࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮ࡢ඘ሸ⋡࡜ ᗘࡢ౫Ꮡᛶࢆㄪ࡭࡚ࠊࡇࢀࡽࡢᐃ㔞ⓗ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛࠶ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲỈࡢ୺せ࡞ࣔࢹࣝ࡜ࡋ࡚ࠊ㠀ศᴟࣔࢹࣝࡢ 7,33 ࠾ࡼࡧ 63&( ࣔࢹࣝࠊࡲࡓศᴟࣔࢹࣝࡢ 'DQ&KDQ

ࣔࢹࣝ࡟ࡘ࠸࡚ࠊ. ࠿ࡽ . ࡢ㐣෭༷≧ែ࡟⮳ࡿࡧ࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮ࡢ

ᗘ㡿ᇦ࡟࠾ࡅࡿࠊ㍺㏦ಀᩘ㸦⮬ᕫᣑᩓಀᩘ㸧࠾ࡼᗘ౫Ꮡᛶ࡜඘ሸ⋡౫Ꮡᛶࢆࠊࡑࢀࡒࢀࡢḟᩘ࡜ࡋ࡚ホ౯ࡋẚ㍑ࡋࡓࠋ࡞࠾ࠊ

⮬ᕫᣑᩓಀᩘࡢ඘ሸ⋡౫Ꮡᛶࡣࠊᐦᗘ౫Ꮡᛶ㸦ࡘࡲࡾయ✚౫Ꮡᛶ㸧࠿ࡽ᪤▱㸦⮬᫂㸧࡛࠶ࡿᩘᐦᗘࡢ౫Ꮡᛶ
ࢆ⿵ṇࡍࡿࡇ࡜࡟ࡼࡗ࡚ỴᐃࡋࡓࠋࡲࡓࠊศᏊືຊᏛ㸦0'㸧ィ⟬ࡢࢥ࣮ࢻ࡟ࡣࠊ㠀ศᴟࣔࢹࣝ࡟ࡣ
*URPDFV ࢆࠊศᴟࣔࢹࣝ࡟ࡣ &3. ࢆ⏝࠸ࡓࠋ௨ୖࡢホ౯ࢆ⾜࠺⇕ຊᏛⓗ≧ែࡣࠊᐦᗘࡀ JFP ࡛ࠊᗘࡀ .... ࡢྛ≧ែ࡜ࡋࡓࠋ⣔ࡢ⢏Ꮚᩘࡣࠊ㠀ศᴟࣔࢹ࡛ࣝࡣ  ಶ࡜ࡋࠊศᴟࣔࢹ
࡛ࣝࡣィ⟬ࢥࢫࢺࢆ⪃៖ࡋ࡚  ಶ࡜ࡋࡓࠋ



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ᅗ  ࡟ࠊ7,33 ࣔࢹࣝ࡟ࡼࡿ࣮࢜ࢲ࣮࣭ࣃ࣓࣮ࣛࢱ࣮ࡢ✵㝽⋡㸦Ș㸧౫Ꮡᛶࡢ౫Ꮡᛶࡢḟᩘࡣ

ᗘ࡟౫ࡽࡎ୍ᐃ࡛࠶ࡿࡀࠊ✵㝽⋡౫Ꮡᛶࡢḟᩘࡣᗘࡢపୗ࡜࡜ࡶ࡟ቑ኱ࡋࠊࡇࢀࡽࡢഴ

ྥࡣࣔࢹࣝ࡟౫ࡽࡎඹ㏻ࡋ࡚࠸ࡿࠋᅗ  ࡟ࡣࠊ ✀㢮ࡢࣔࢹࣝ࡟ࡼࡿィ⟬⤖ᯝࢆࠊඹ㏻ࡢ
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ᗘኚ໬ࢆ♧ࡍࠋ ᗘᗘ࡜඘ሸ⋡౫Ꮡᛶ

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5 /9Ý¥¤R¥Pyridine Ring Modification of Indane-1,3-dione Dimers for Control of their Crystal Structure§<DNL\DPD7)XMLQDND01LVKLPXUD56HNL+6DNXUDL   10, 2690–2696.
Þ¥¤R¥"Synthesis of C70 Fragment Buckybowl, Homosumanene and Heterahomosumanenes via Ring-Expansion
Reactions from Sumanenone", M. Nishimoto, Y. Uetake, Y. Yakiyama, F. Ishiwari, A. Saeki, H. Sakurai, J. Org.
Chem. 2022, 87, 2508-2519.
ß¥¤R¥"Dielectric Response of Difluorinated Sumanene Caused by the In-plane Motion", M. Li, J.-Y. Wu, K.
Sambe, Y. Yakiyama, T. Akutagawa, T. Kajitani, T. Fukushima, K. Matsuda, H. Sakurai, Mater. Chem. Front. 2022,
in press (DOI: 10.1039/D2QM00134A).
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1. Rapid access to polycyclic thiopyrylium compounds from unfunctionalized aromatics by thia-APEX reaction.
Kou. P. Kawahara, Hideto Ito,* Kenichiro Itami.* Chem. Commun. 2023, 59, 1157–1160.
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3. One-step synthesis to polycyclic thianthrenes from unfunctionalized aromatics by thia-APEX reaction.
Kou. P. Kawahara, Hideto Ito,* Kenichiro Itami,* Org. Chem. Front. 2023, Advance Article. DOI:
10.1039/D2QO02058K.
4. Expanded [2,1][n]Carbohelicenes with 15- and 17-Benzene Rings. Michihisa Toya, Takuya Omine, Fumitaka
Ishiwari, Akinori Saeki, Hideto Ito,* Kenichiro Itami,* J. Am. Chem. Soc. 2023, 145, ASAP. DOI:
10.1021/jacs.3c00109.
5. Lithium-mediated mechanochemical cyclodehyrogenation. Kanna Fujishiro, Yuta Morinaka, Yohei Ono,
Tsuyoshi Tanaka, Lawrence T. Scott, Hideto Ito,* Kenichiro Itami,* J. Am. Chem. Soc. 2023, 145, 8163–8175.

- 245 -

(OHFWURQLFWUDSSLQJDQGVXUIDFHSURWRQDWLRQLQ7L2QDQRVWUXFWXUHV±
8VDJH5HSRUW○Gergely Juhasz (Tokyo Institute of Technology)

1Introduction
Transition metal oxide surfaces often play important roles in electrochemical and photoelectrochemical applications.

Charge carriers that are responsible for these functions can form polarons in such semiconducting oxides, with various
size and mobility. Understanding the polaronic effects help describe charge carrier dynamics and electrochemical
reactions on the surface more accurately. In spite of their importance, the behavior of polarons are rarely studied in low
dimensional structures like nanoparticles. In this study we focus on polaron formation in anatase-type TiO2 nanoparticles,
where surface absorption of protons, the localized orbital states can play important effect. Previous studies on bulk TiO 2
found that the formation of large polaron can be reasonably well simulate using hybrid-functionals like B3LYP. This
proposal is a continuous effort based on the result of previous year’s proposal.

2

Methods
2.1 Software: The calculations were performed using Density Functional-based Tight Binding (DFTB, software:

DFTB+ ver 19.1) and DFT (software: TURBOMOLE, ver 7.4.1) methods. The DFTB calculations were performed using
the mio+tiorg parameter sets. The DFT calculations were performed using def-SV(P) basis set, pure (PBE) and hybrid(PBE0, B3LYP) functionals. To consider potential dispersion effects, DFT-D3(BJ) dispersion model was applied. No
solvent model was used. We used dense (m4) grid for better SCF convergence; otherwise default convergence criteria
were applied.
2.2 Geometry optimization: The nanoparticle models were manually created and preoptimized using DFTB. Wheneverit was possible, the model with highest possible symmetry were used. The models in closed-shell electronic state were
optimized using pure DFT, which were followed by optimization of models with charge careers and using hybrid
functionals. This was followed by the optimization of nanoparticle models with H+ doped surfaces, then finally added
extra charge. The verification of the geometry stability using frequency calculation were not possible due to the large
computational cost.

3

Results

Using previously optimized models and handmade models, we scheduled the geometry optimizations on several
nanoparticles. The calculations raised several challenges:- Many of the proposed polaronic structure has small bandgap (less than 0.4 eV) causing SCF instability.
- DFT calculations with hybrid functionals (PBE0, B3LYP) require more time and memory, than with the pureone (PBE). These requirements for open shell structures were even more severe, close to and sometimes exceeing
available calculation time and memory size.
- Protons and H-radicals are highly mobile on the nanoparticle surface which made difficult to locate the optimal
geometry in many cases.

- 246 -

Due to these difficulties plus the upgrade of the HPC nodes as well as unrelated scheduling conflicts, we have run outof time. Therefore we focused on the polaron on a single anatase model (Ti98) and different surface modification of it(see figure 1).

Figure 1. Protonation of the 101 surface of anatase (left) and there different positions (a – c) of H on the Ti98
model nanoparticle (position of H indicated by red circle)

Different H positions showed different stability, while all of the showed lattice distortion around the H and a bandgap
between 0.2-0.3 eV. These distortions showed that the absorption of H strongly couples of the polaron formation process
and help the localization of extra electrons. The mechanism of the couple is suspected to be the modification of local
vibration modes, and the extra electron binding capability of the H attached to the surface.
The localization of charge and distortion of the lattice could be observed in calculation using pure and hybrid
functionals as well, showing that at least part of polaron formation and electronic coupling can be estimated even using
pure functionals. Thanks to the significantly more memory and faster CPU in the new RCCES nodes, we continue our
calculations and hope to obtain more calculation point using PBE0 and B3LYP hybrid functionals this year. A detailed
analysis of the lattice distortions and the corresponding energetics is in preparation.

4

Talks and Posters[★] G. Juhasz, “Differences of molecular absorption on titanium-dioxide surface - a computational study”, The 103rd

CSJ Annual Meeting (2023)

5

Publications[‫ۻ‬, in preparation] G. Juhasz, ͆Investigation of polaron formation and charge trapping in anatase-type TiO2

nanoparticles with DFT method using hybrid-functionals͇

- 247 -

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- 248 -

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spin density

HOMO–2.895 eV

Ru : 0.18–2.778 eV

Ru : 0.01–2.732 eV

Ru : 0.01

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Theoretical Studies on Structures and Reactivities ofMetal Complexes with Multifunctional Ligands
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෼͹෾ੵͶ͕͏ͱɼΦϪέφϫηϕϪʖ࣯ྖ෾ੵ͹գఖͶ͕͏ͱ෾մਫ਼੔෼͗ਫ਼ͣΖ͞ͳ΍ๅࠄ͠Ηͱ͕Εɼ‫ޣ‬ಋఈ͹‫ݬ‬Ҿͳ͵ͮͱ͏Ζɽ͞͹ΦϪέφϫηϕϪʖ΢ΨϱԿ࣯ྖ෾ੵ๑Ͳً͞Ζ΢Ψϱ͹෾մͺɼ‫ـ‬૮΢Ψϱ͹Իౕͳ‫ؖ‬࿊͢ͱ͏Ζɽ͞͹‫ـ‬૮΢Ψϱ͹Իౕ͹඲Ճ͹ͪΌͶͺɼ΢Ψϱ͹ԻౕΝන಼ͤ෨Φϋϩάʖͳ෾մଐౕ͹‫ع͗ܐؖ‬எ͹ʰԻౕ‫ܯ‬΢Ψϱʱ͹֋൅͗චགྷͲ͍Ζɽຌ‫Ͳڂݜ‬ͺྖࢢԿָ‫ࢋܯ‬ͶΓͮͱɼ΢Ψϱ͹಼෨Φϋϩάʖͳ෾մଐౕ͹‫ܐؖ‬Ν໎Δ͖Ͷͪ͢৿͢͏Իౕ‫ܯ‬΢Ψϱ͹֋൅Νߨͮͪɽ ‫ࢋܯ‬๏๑ཀྵ࿨‫ࢋܯ‬ͺ *DXVVLDQ ϕϫήϧϞͶΓΖ෾ࢢٌಕ๑ɼືౕ൜‫਼ؖ‬๑ʤ')7ʥͶΓΕߨͮͪɽԻౕ‫ܯ‬΢Ψϱ͹ޫึԿ߻෼Ͷɼ0;'* GS Ν༽͏ͱߑଆ࠹నԿΝߨͮͪɽ࠹నԿ͠ΗͪߑଆͶͯ͏ͱͺ &&6' W FF397= ͲΦϋϩάʖΝ඲Ճͪ͢ɽસͱ͹࠹నԿߑଆͶͯ͏ͱ৾ಊմੵΝߨ͏ɼ҈ఈߑଆ͕Γ;યҢয়ସͲ͍Ζ͞ͳΝ֮೟ͪ͢ɽಚΔΗͪયҢয়ସɼ࢟য়ସɼ͕Γ;शয়ସΓΕɼୱ෾ࢢ͹ൕԢଐౕ͹‫ܯ‬ࢋͶ༽͏ΔΗΖ 55.0 ཀྵ࿨Ν༽͏ͱൕԢଐౕఈ਼Νࢋड़ͪ͢ɽ ‫ڂݜ‬੔ՎΦϪέφϫηϕϪʖ࣯ྖ෾ੵ๑ͶΓΖࣰ‫ݩ‬ͶΓΕɼϗϱζϩΠϱϠωΤϞྪ͗Իౕ৏তͶ൒͑෾մͶΓͮͱϗϱζϩΩοΨϱྪͳΠϱϠωΠ͹ΊΝਫ਼ͣɼԻౕ‫ܯ‬΢Ψϱͳ͢ͱన͢ͱ͏Ζ੓࣯Ν༙ͤΖ͞ͳΝ໎Δ͖
ͳͪ͢ɽ͞͹ϗϱζϩΠϱϠωΤϞྪΝԻౕ‫ܯ‬΢Ψϱͳ͢ͱ࢘༽ͤΖͪΌͶɼྖࢢԿָ‫ࢋܯ‬Ν༽͏ϗϱζϩΠϱϠωΤϞྪ͹෾մͶΓΕਫ਼੔ͤΖϗϱζϩΩοΨϱ͹ਫ਼੔ଐౕͳԻౕ͹‫ܐؖ‬Ν৆ࡋͶ‫ݗ‬౾ͪ͢ɽຌ‫ڂݜ‬Ͳͺɼ झ͹ϗϱζϩΠϱϠωΤϞྪΝ༽͏ͪ͗ɼ͞͞Ͳͺେනద͵  झ͹݃ՎΝਦ  Ͷࣖͤɽ‫خ‬ຌߑଆͲ
͍Ζʤ̐ʥϗϱζϩΠϱϠωΤϞΝ‫خ‬६ͶͤΖͳɼ
ʤ̐ʥϟφΫεϗϱζϩΠϱϠωΤϞͺɼుࢢ‫ڛ‬༫‫͍Ͳخ‬ΖϟφΫε‫ͳخ‬ϟοϩ‫خ‬Ν༙ͤΖͪΌɼʤ̐ʥϗϱζϩΠϱϠωΤϞͶർ΄ͱ෾մً͗͞ΕΏ͚ͤ͵Ζɽ͞ΗͺɼϟφΫε‫خ‬͹ଚࡑͶΓͮͱ෾մਫ਼੔෼Ͳ͍ΖϗϱζϩΩοΨϱ͹ਜ਼ు՛͗ඉ‫ࡑۃ‬Կ͢ɼ҈ఈԿͤΖͪΌͲ͍ΖɿҲ๏ɼʤ̑ʥωφϫϗϱζϩΠϱϠωΤϞͺɼుࢢ‫ٷ‬Ӏ‫͍Ͳخ‬Ζωφϫ‫خ‬Ν༙ͤΖͪΌɼʤ̐ʥϗϱζϩΠϱϠωΤϞͶർ΄ͱ෾մً͗͞ΕͶ͚͏ɽ͞Ηͺɼωφϫ‫خ‬͹ଚࡑͶΓͮͱ෾մਫ਼੔෼Ͳ͍ΖϗϱζϩΩοΨϱ͗෈҈ఈԿͤΖͪΌͲ͍Ζɽ

- 254 -

͞ΗΔ̑झ͹ϗϱζϩΠϱϠωΤϞྪΝΦϪέφϫηϕϪʖ࣯ྖ෾ੵͲ‫ܯ‬଎ͤΖͳਦ̏ͶࣖͤΓ͑Ͷɼ෾մ͠Η͵͏ΉΉ͹ϗϱζϩΠϱϠωΤϞྪͳ෾մਫ਼੔෼Ͳ͍ΖϗϱζϩΩοΨϱ͹΢Ψϱ৶ߺ͗‫ݗ‬ड़͠ΗΖɽ
͞ΗΔ͹΢Ψϱ৶ߺྖ͹ർ͖ΔɼԻౕ‫ܯ‬΢Ψϱ͹ਫ਼ଚིΝ඲Ճͪ͢ɽ࣏ͶಚΔΗͪԻౕ‫ܯ‬΢Ψϱ͹ਫ਼ଚིΝɼྖࢢԿָ‫ٽͲࢋܯ‬ΌͪϗϱζϩΠϱϠωΤϞྪͨΗͩΗ͹෾մΦϋϩάʖͶଲ͢ͱϕϫρφ͢ɼ΢Ψϱ෾մ͹ཀྵ࿨͖Δ༩଎͠ΗΖཀྵ࿨෾մ‫ۄ‬તͲϓΡρτϱήͪ͢ɽ͞͹݃ՎΝਦ̏ࠪ৏Ͷࣖͤɽ੪ɼྚɼ੼͹ϕϫρφͺͨΗͩΗϟφΫεϗϱζϩΠϱϠωΤϞɼϗϱζϩΠϱϠωΤϞɼωφϫϗϱζϩΠϱϠωΤϞͶଲԢ
ͤΖɽϓΡρτϱήͪ͢‫ۄ‬તΝඏ෾ͤΖ͞ͳͲਦ̏ӊԾͶࣖͤ‫ـ‬૮΢Ψϱ͹ԻౕΝන಼ͤ෨Φϋϩάʖ෾ා
͗ಚΔΗͪɽຌ‫֋Ͳڂݜ‬൅ͪ͢ϗϱζϩΠϱϠωΤϞྪΝʰԻౕ‫ܯ‬΢Ψϱʱͳ͢ͱ༽͏Ζ͞ͳͲɼΦϪέφϫηϕϪʖ࣯ྖ෾ੵͲ͹‫ܯ‬଎͹ࡏͶً͞Ζ‫ـ‬૮΢Ψϱ͹Յ೦ͳɼͨΗͶ൒͑΢Ψϱ෾մ͹फི͹඲Ճ͗Ն೵
ͳ͵ΕɼΦϪέφϫηϕϪʖ࣯ྖ෾ੵͲಚΔΗΖ଎ఈ݃Վ͹৶བ੓͹޴৏͗‫غ‬ଶ͠ΗΖɽਦ ʤࠪʥϗϱζϩΠϱϠωΤϞͳϗϱζϩΩοΨϱ͹ߑଆɼϗϱζϩΠϱϠωΤϞྪ͹෾մգఖ͹ໝࣞਦ͕Γ;ϜηηϘέφϩ͹଎ఈྭɽྭͳ͢ͱɼʤ̏ʥϟφΫεϗϱζϩΠϱϠωΤϞɼʤ̐ʥϗϱζϩΠϱϠω
ΤϞɼʤ̑ʥωφϫϗϱζϩΠϱϠωΤϞΝࣖͪ͢ɽʤӊ৏ʥΦϪέφϫηϕϪʖ΢ΨϱԿ࣯ྖ෾ੵ๑ͶΓͮͱਫ਼੔ͪ͢ϗϱζϩΠϱϠωΤϞྪ͹ਫ਼ଚིͳɼྖࢢԿָ‫ٽͲࢋܯ‬Όͪ෾մΦϋϩάʖ͹‫ܐؖ‬͹ϕϫρφɽ੪ɼྚɼ੼͹ϕϫρφͺɼϟφΫεϗϱζϩΠϱϠωΤϞɼϗϱζϩΠϱϠωΤϞɼωφϫϗϱζϩΠϱϠ
ωΤϞͶଲԢͤΖɽഃતͺ΢Ψϱ෾մ͹ཀྵ࿨͖Δ༩଎͠ΗΖཀྵ࿨෾մ‫ۄ‬તͶΓΖϓΡρτϱή݃ՎɽʤӊԾʥϓΡρτϱήͪ͢‫ۄ‬ત͖ΔಚΔΗͪ‫ـ‬૮΢Ψϱ͹ԻౕΝන಼ͤ෨Φϋϩάʖ෾ාɽ

Ⓨ⾲ࠊฟ∧ᐇ⦼‫ ۻ‬1. D. Asakawa, K. Saikusa, J. Am. Soc. Mass Spectrom. 33, 1548-1554 (2022)‫ ۻ‬2. D. Asakawa, K. Todoroki, H. Mizuno, J. Am. Soc. Mass Spectrom. 33, 1716-1722 (2022)‫ ۻ‬3. D. Asakawa, J. Am. Soc. Mass Spectrom. 34, 435-440 (2023)- 255 -

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Interaction analysis of FIV and HIV-1 protease inhibitor
using the FMO methodwÙ Ç, ÑU Öu, W XÚ·wÕO
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+ 2: FIV-ATV ?

HIV-ATV ? *4=1 @7#%6 !.,>'4=

5<. 9);A28./Ý3,('$ ¹Ü Â

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ª¿|0! { SOsaki, T. Matsui, “Interaction analysis of FIV and HIV-1 protease inhibitor using the FMO method”, The 10th

Asian Pacific Association of Theoretical and Computational Chemistry, February 2023, Quy Nhon, Vietnam.
 YKanamaru, T. Matsui, “Machine Learning Assisted DFT Calculation Using Solvation Model”, The 10th Asian
Pacific Association of Theoretical and Computational Chemistry, February 2023, Quy Nhon, Vietnam.

(|0!

{ YKanamaru, T. Matsui, “Factor analysis of error in oxidation potential calculation: A machine learning study”,
Journal of Computational Chemistry 2022, 43, 1504-1512.
 SOnozawa, Y.Nishimura, T.Matsui,“A Theoretical Study on Rate Constants of Excited State Proton Transfer
Reaction in Anthracene-Urea Derivatives”, Bulletin of the Chemical Society of Japan 2023, 96, 215-222.
S Osaki, T. Matsui, “Interaction analysis of FIV and HIV-1 protease inhibitor using the FMO method”, inpreparation.

- 257 -

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[1] Takahiro Ono, Kazuhito V. Tabata, Yuki Goto, Hiroaki Suga, Hiroyuki Noji, Jumpei Morimoto, and Shinsuke Sando
Construction of a lipid bilayer permeability assay for investigation on the structure-permeability relationship ofcyclic peptides, } 59 qB@7:-, 2022 I 10 _ 28 [
[2] y %rze mHEa 1+, SÕ1I<MsB@9:"97«"0, [A- } 143 I-, 2023 I 3 _ 26 [[3] e mH tX 4t

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Lokey ScottEa 1+, 1E:5K½©t¤qB@7:"Ï;E35!&,N¢"0, [A- } 143 I-, 2023 I 3 _ 26 [[4] ~c L.e mHEa 1+, SÕ1I<MsB@9:"E3LNFR",{|"0, [A- } 143 I-, 2023 I 3 _ 28 [
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F, 2022 I 9 _ 10 [
[6] Hanrui Liu, Ryosuke Ueki, Shinsuke Sando, Design of an orthogonal DNA aptamer–receptor pair for the
precise regulation of cell signaling, XXIV International Round Table on Nucleosides, Nucleotides and Nucleic Acids,
2022 I 8 _ 28–31 [[7] Marin Yokomine, Jumpei Morimoto, Yasuhiro Fukuda, Daisuke Kuroda, Takumi Ueda, Koh Takeuchi, Satoru
Nagatoishi, Kouhei Tsumoto, and Shinsuke Sando, “Design of MDM2-binding peptoids and evaluation of the bindingmode”, } 59 qB@7:-, 2022 I 10 _ 26 [[8] Satoshi Uchida, Yuki Hosono, Kayoko Kanamitsu, Mayumi Ishii, Jumpei Morimoto, Scott R. Lokey, Shinsuke
Sando, “Evaluation of the effect of an amide-to-ester substitution on membrane permeability of cyclic hexapeptides
and larger cyclic peptides”, } 59 qB@7:-, 2022 I 10 _ 26 [[9] Moe Shinkai, Yuki Hosono, Takumi Ueda, Koh Takeuchi, Koji Umezawa, Jumpei Morimoto, and Shinsuke Sando“Membrane permeability measurements of a large library of cyclic hexapeptides and conformational analysis ofpermeable cyclic hexapeptides by molecular dynamics simulations”, } 59 qB@7:-, 2022 I 10 _ 26 [
[10] gGvsemH¦txwPt8Ä|4QklHEa1+, “B¿tD"¤ B@
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NK, 2022 I 7 _ 13–14 [- 267 - /C
[1] J. Morimoto, Y. Shiratori, M. Yokomine, T. Ueda, T. Nakamuro, K. Takaba, S. Maki-Yonekura, K. Umezawa, K.
Miyanishi, Y. Fukuda, T. Watanabe, W. Mizukami, K. Takeuchi, K. Yonekura, E. Nakamura, S. Sando, “Bottom-up
design of peptide nanoshapes in water using oligomers of N-methyl-L/D-alanine” ChemRxiv 2023 DOI:
10.26434/chemrxiv-2023-c4mw6. (This content is a preprint and has not been peer-reviewed.)[2] H. Liu, T. Baeumler, K. Nakamura, Y. Okada, S. Cho, A. Eguchi, D. Kuroda, K. Tsumoto, R. Ueki and S. Sando"An Engineered Synthetic Receptor–Aptamer Pair for an Artificial Signal Transduction System", ACS Nano 2023, 17,9039–9048.
[3] Y. Hosono, S. Uchida, M. Shinkai, C. E. Townsend, C. N. Kelly, M. R. Naylor, H.-W. Lee, K. Kanamitsu, M. Ishii,
R. Ueki, T. Ueda, K. Takeuchi, M. Sugita, Y. Akiyama, S. R. Lokey, J. Morimoto and S. Sando, "Amide-to-ester
substitution as a stable alternative to N-methylation for increasing membrane permeability in cyclic peptides", Nat.
Commun. 2023, 14, 1416.
[4] T. Ono, K. V. Tabata, H. Noji, J. Morimoto and S. Sando "Each side chain of cyclosporin A is not essential for highpassive permeability across lipid bilayers", RSC Adv. 2023, 13, 8394–8397.
[5] T. Ono, K. V. Tabata, Y. Goto, Y. Saito, H. Suga, H. Noji, J. Morimoto and S. Sando "Label-free quantification ofpassive membrane permeability of cyclic peptides across lipid bilayers: Penetration speed of cyclosporin A across lipid
bilayers" Chem. Sci. 2023, 14, 345–349.
[6] J. Kim, H. Kobayashi, M. Yokomine, Y. Shiratori, T. Ueda, K. Takeuchi, K. Umezawa, D. Kuroda, K. Tsumoto,J. Morimoto and S. Sando, "Residue-Based Program of a ß-Peptoid Twisted Strand Shape via a Cyclopentane
Constraint" Org. Biomol. Chem. 2022, 20, 6994–7000.

E#0
>@6+RQGD± >@6+RQGD  ±
>@3:LOKHOP   ±
>@6'RELW]  ±
>@-0RULPRWR  ±
>@<)XNXGD ±
>@M. Yokomine      H

- 268 -

')7 ศᏊືຊᏛィ⟬ࢆ⏝࠸ࡓ⁐⼥ሷ୰ࡢᨺᑕᛶᗫᲠ≀ࡢ⁐ゎᗘホ౯(YDOXDWLRQRI6ROXELOLW\RI5DGLRDFWLYH:DVWHLQ0ROWHQ6DOWV8VLQJ')7
0ROHFXODU'\QDPLFV6LPXODWLRQ○᏷ᡞ ༤⣖㸦ᮾ໭኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧



◊✲┠ⓗ
ཎᏊຊⓎ㟁ᡤࡢ㐠㌿࡟కࡗ࡚⏕ࡌࡿ㧗ࣞ࣋ࣝᗫᲠ≀࡟ᑐࡋࠊฎ⌮ฎศ᪉ἲࢆ᪩ᮇ࡟☜❧ࡍࡿࡇ࡜ࡣཎᏊຊ

࢚ࢿࣝࢠ࣮฼⏝࡟࠾ࡅࡿ᭱㔜せㄢ㢟ࡢ୍ࡘ࡛࠶ࡿࠋ㧗ࣞ࣋ࣝᗫᲠ≀࡟ࡣ࣐࢖ࢼ࣮࢔ࢡࢳࣀ࢖ࢻࡸ㛗ᑑ࿨᰾ศ⿣⏕ᡂ≀ࡀྵࡲࢀ࡚࠾ࡾࠊࡇࢀࡽࡣ㉸㛗ᮇࡢ༙ῶᮇ࠿ࡘ㧗࠸ᨺᑕᛶẘᛶࢆ᭷ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ㧗ࣞ࣋ࣝᗫᲠ≀ࢆᆅᒙ୰࡟ฎศࡍࡿ࡟ࡋ࡚ࡶࠊ࠶ࡿ࠸ࡣูࡢฎ⌮᪉ἲࢆ᥇⏝ࡍࡿ࡟ࡋ࡚ࡶࠊ㉸㛗ᮇࡢᏳ඲☜ಖࢆ⪃࠼࡞ࡃ࡚ࡣ࡞ࡽ࡞࠸ࠋࡇࢀ࡟ᑐࡋࠊ㧗ࣞ࣋ࣝᗫᲠ≀᰾✀࡬୰ᛶᏊࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾࠊ▷ᑑ࿨᰾✀ࡲࡓࡣᏳᐃ
᰾✀࡬࡜᰾ኚ᥮ࡍࡿࡇ࡜ࡀᥦ᱌ࡉࢀ࡚࠸ࡿ>@ࠋᚑ᮶ࠊ㧗ࣞ࣋ࣝᗫᲠ≀ࢆྵࡴ୰ᛶᏊ⿕↷ᑕయ㸦ࢱ࣮ࢤࢵࢺ㸧ࡣᖖ࡟ᅛయ࡜᝿ᐃࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࢱ࣮ࢤࢵࢺࢆᾮయ࡜ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤࠊࡑࢀࢆ᰾ኚ᥮ࢩࢫࢸ࣒ࡢ
ෆእ࡟ὶືࡉࡏࡿࡇ࡜࡛ࠊࢱ࣮ࢤࢵࢺࡢᐃᮇⓗ஺᥮ࡀ୙せ࡟࡞ࡿࠊ㐠㌿୰࡟ᡂศࢆㄪᩚࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿ࡞࡝ࠊከࡃࡢᕤᏛⓗ฼Ⅼࡀ⏕ࡌࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡇࡢࡼ࠺࡞᝿ᐃࡢୗࠊ⁐⼥ሷ࡟ࡇࢀࡽ㧗ࣞ࣋ࣝᗫᲠ≀ࢆῧຍࡋࡓ᪂ࡓ࡞᰾ኚ᥮ࢱ࣮ࢤࢵࢺࢆᥦ᱌ࡍࡿࠋཎ
Ꮚຊࢩࢫࢸ࣒࡟࠾ࡅࡿ⁐⼥ሷ࡜ࡋ࡚ࠊLiF ࡜ BeF2 ࡢΰྜ⁐⼥ሷࡀ⏝࠸ࡽࢀ࡚ࡁࡓᐇ⦼ࡀ࠶ࡾࠊ⁐፹࡜ࡋ࡚ࡢ
➨୍ೃ⿵࡜⪃࠼ࡽࢀࡿࠋ୍᪉࡛ࠊ㧗ࣞ࣋ࣝᗫᲠ≀୰ࡢ≉ᐃඖ⣲࡜ࡇࢀࡽ⁐⼥ሷ⁐፹ೃ⿵࡟ࡼࡿΰྜ⣔ࢆᢅࡗࡓ◊✲౛ࡣ࡯࡜ࢇ࡝ሗ࿌ࡉࢀ࡚࠸࡞࠸ࠋᙜヱࢥࣥࢭࣉࢺᡂ❧ᛶࢆ᳨ウࡍࡿࡓࡵ࡟ࠊࡲࡎ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲ࡀ⁐⼥ሷ⁐፹୰࡛Ᏻᐃࡋ࡚Ꮡᅾࡍࡿࡼ࠺࡞໬Ꮫᙧែࢆぢฟࡍᚲせࡀ࠶ࡿࠋ௨ୖࡢ⫼ᬒ࠿ࡽࠊᮏ◊✲࡛ࡣᾮయ᰾ኚ᥮ࢱ࣮ࢤࢵࢺࡢ㛤Ⓨ࡟ྥࡅ࡚ࠊ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲࡜⁐⼥ሷ⁐፹ࡢ㛫࡛Ⓨ⏕ࡍࡿ࡜⪃࠼ࡽࢀࡿ㟁Ꮚ⛣ື཯ᛂࢆศᯒࡋࠊᏳᐃࡋ࡚Ꮡᅾࡍࡿ⁐⼥ሷࢱ࣮ࢤࢵࢺࢆぢฟࡍࡓࡵࡢᩘ್ゎᯒホ౯ࢆᐇ᪋ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ⏦ㄳᙜึࡣ :LGRP ࡢ⢏Ꮚᤄධἲࢆ⏝࠸ࡓ໬Ꮫ࣏ࢸࣥࢩࣕࣝホ౯࡜ࠊࡑࢀ࡟ᇶ࡙࠸ࡓ⁐ゎᗘホ౯ࢆᐇ᪋ࡍࡿ

ணᐃ࡛࠶ࡗࡓࡀࠊవ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢィ⟬ࡀୖᡭࡃ࠸࠿࡞࠸ࡓࡵ࡟᩿ᛕࡋࡓࠋࡑࡇ࡛ᮏ◊✲࡟࠾࠸࡚ࡣࠊ
')70' ィ⟬࡟ࡼࡿ࢚ࢿࣝࢠ࣮ᕪ࠿ࡽ㓟໬㑏ඖ㟁఩ࢆホ౯ࡋࠊ⁐ゎࡢࡋࡸࡍࡉ࡟ࡘ࠸࡚⡆᫆ⓗ࡞ᣦᶆࢆᚓࡿ
ࡇ࡜ࡀྍ⬟࠿ࢆ᳨ウࡍࡿࡇ࡜࡜ࡋࡓࠋ
ᐇ㦂್࡜ࡢẚ㍑ホ౯ࢆ⾜࠺ࡓࡵࠊ⁐፹ /L)±%H) )OLEH  ࡟࠾ࡅࡿ &U ࡢ㓟໬㑏ඖ㟁఩ YV))í  ࢆホ౯ࡍࡿࠋ౛࡜ࡋ࡚ࠊ&U ,,, &U ,, ࡢ㓟໬㑏ඖ཯ᛂࡣḟᘧ࡟࡚⾲ࡉࢀࡿࠋʹ ଷ ሺሻ ൌ ʹ ଶ ሺሻ ൅

ଶ ሺሻ

ሺͳሻ

ୖᘧ࡟ᇶ࡙ࡁࠊ&U ,,, &U ,, ࡢ ))í࡟ᑐࡍࡿ㓟໬㑏ඖ㟁఩ࡣḟᘧࡢ㏻ࡾ⾲ࡉࢀࡿ>@ࠋܸେ୰ሺ୍୍୍ሻȀେ୰ሺ୍୍ሻ ሺ‫ݏݒ‬Ǥ

ଶȀ

ିሻ

ൌെ

ͳ
ሼʹ‫ܧۃ‬ሺ ଶ ൅ ሻ‫ ۄ‬െ ʹ‫ܧۃ‬ሺ ଷ ൅ ሻ‫ ۄ‬൅ ‫ܩ‬ሺ ଶ ሻ ൅ ‫ ܥ‬ௌ ሽ
ʹ݁

ሺʹሻ

ࡇࡇ࡛ࠊH ࡣ㟁Ẽ⣲㔞ࠊ( V\VWHP ࡣ⣔࡟࠾ࡅࡿ඲࢚ࢿࣝࢠ࣮ࠊ* ) ࡣ ) ࢞ࢫࡢ⮬⏤࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋࡉࡽ

- 269 -

࡟ &6 ࡣ࢚ࣥࢺࣟࣆ࣮⿵ṇ㡯࡛࠶ࡾࠊ
‫ܥ‬ௌ ൌ െ࡛⾲ࡉࢀࡿࠋ) ࡣࣇ࢓ࣛࢹ࣮ᐃᩘࠊ7 ࡣͳ൫ܶܵେ୰୊య െ ܶܵେ୰୊మ ൯
‫ܨ‬

ሺ͵ሻ

ᗘࠊ6Į ࡣ⣧≀㉁ Į ࡢ࢚ࣥࢺࣟࣆ࣮࡛࠶ࡿࠋ

ᮏ◊✲࡟࠾ࡅࡿ ')70' ィ⟬࡟ࡣࠊ3$: ᆺᨃ࣏ࢸࣥࢩࣕࣝἲࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘ⌮ㄽィ⟬ࣉࣟࢢ࣒࡛ࣛ࠶
ࡿ 9$63 ࢆ౑⏝ࡋࡓ> @ࠋ')7 ィ⟬࡛ࡣ RSW%YG: ỗ㛵ᩘࢆ⏝࠸ࠊ࢚ࢿࣝࢠ࣮࢝ࢵࢺ࢜ࣇࡣ  H9ࠊN Ⅼ
࣓ࢵࢩࣗࡣ îî ࡜ࡋࡓࠋ0' ィ⟬࡟࠾࠸࡚ࡣࠊ197 ࢔ࣥࢧࣥࣈࣝࠊ᫬㛫ࢫࢸࢵࣉࢆ  IV ࡜ࡋࡓࠋ⁐፹ࡢࢩࢫࢸ࣒ࢧ࢖ࢬࡣ  ಶ࡛࠶ࡾࠊ⁐㉁࡜ࡋ࡚ &Uࠊ&U)ࠊ&U) ࡢ  ⤌ࢆࡑࢀࡒࢀᑟධࡍࡿࡇ࡜࡛ࠊ&Uࠊ&Uࠊ
&Uࡑࢀࡒࢀࡢᣲືࢆホ౯ࡋࡓࠋ



◊✲ᡂᯝ
⾲  ࡟ )OLEH ୰ࡢ . ࡟࠾ࡅࡿ &U ࡢ㓟໬㑏ඖ㟁఩ࢆ♧ࡍࠋ⾲  ୰ࡢᐇ㦂್࡟ࡘ࠸࡚ࡣࠊඛ⾜◊✲>@࡟ࡼࡾሗ࿌ࡉࢀ࡚࠸ࡿ )OLEH ୰ࡢ 1L ,, 1L  㟁ᴟ࠿ࡘ . ࡛ࡢ㓟໬㑏ඖ㟁఩ࢆࠊᮏ◊✲ࡢ᮲௳࡬ኚ᥮ࡋࡓࡶࡢ࡛
࠶ࡿࠋ௒ᅇࡢィ⟬⤖ᯝ࡜ᐇ㦂್࡜ࡢᕪࡣ᭱኱࡛⣙ ࡛࠶ࡗࡓࠋᮏ◊✲࡛ࡣᘧ  ࡟♧ࡍ㏻ࡾࠊ㓟໬㑏ඖ㟁఩ࢆ࢚ࣥࢱࣝࣆ࣮࡛ࡣ࡞ࡃ࢚ࢿࣝࢠ࣮ࡢ್࠿ࡽ⟬ฟࡋ࡚࠸ࡿࠋࡼࡗ࡚ࠊ1S7 ࢔ࣥࢧࣥࣈࣝࢆ⏝࠸ࡓ⁐㉁⣔ࡢᖹ
⾮య✚࡟࠾ࡅࡿ ')70' ィ⟬ࡢᐇ᪋➼࡟ࡼࡾࠊィ⟬⢭ᗘࡣᨵၿࡉࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋ⾲ 1.

/L)±%H) ୰࡟࠾ࡅࡿ㓟໬㑏ඖ㟁఩ . 

5HGR[FRXSOHV

5HGR[SRWHQWLDOV 9YV))í 
3UHVHQWVWXG\([SHULPHQWDOYDOXH>@&U ,,, &U ,, í

í

&U ,, &U  í

í

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋ


ཧ⪃ᩥ⊩
>@06WHLQEHUJ*:RW]DN%0DQRZLW]%1/%URRNKDYHQ1DWLRQDO/DERUDWRU\  >@0$QGHUVRQHWDO'2(1(83  >@9/&KHYULHUHWDO3K\V5HY%  >@*.UDVVHHWDO&RPSXW0DWHU6FL  
>@*.UDVVHHWDO3K\V5HY%  
>@+:-HQNLQVHWDO-(OHFWURFKHP6RF  - 270 -༢ ᒙ &17 ࢝࢖ࣛࣜࢸ࢕ไᚚྜᡂ࡟ྥࡅࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
0ROHFXODU'\QDPLFV6LPXODWLRQIRUWKH&KLUDOLW\&RQWURORI6LQJOH:DOOHG&DUERQ1DQRWXEHV  ‫୸ۑ‬ᒣ ⱱኵ, ᑠᖭ 㑳┿, ᳃ ᅜኸ, ྜྷᕝ ு (ᮾி኱Ꮫ), ஂ㛫 㤾 (ಙᕞ኱Ꮫ)



◊✲┠ⓗ
༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ(SWCNT)ࡣࢢࣛࣇ࢙ࣥࢆ෇⟄≧࡟ᕳ࠸ࡓᵓ㐀ࢆᣢࡘ≀㉁࡛࠶ࡾ, ᕳࡁ᪉(࢝࢖ࣛࣜࢸ࢕)࡟ࡼࡗ࡚㔠ᒓ, ༙ᑟయ୧᪉ࡢᛶ㉁ࢆ♧ࡍ. SWCNT ࡣ࢟ࣕࣜ࢔⛣ືᗘࢆጞࡵ࡜ࡋࡓᕤᏛⓗᛂ⏝࡟㐺ࡋࡓ≀ᛶࢆ᭷ࡍࡿࡀ, ࢝࢖ࣛࣜࢸ࢕ࡢసࡾศࡅࡀᅔ㞴࡛࠶ࡿࡇ࡜ࡀࢹࣂ࢖ࢫᛂ⏝࡟ྥࡅࡓ㞀ᐖ࡜࡞ࡗ࡚࠸ࡿ.
㏆ᖺྜ㔠ࢆゐ፹࡜ࡋ࡚⏝࠸ࡓྜᡂᐇ㦂࡟ࡼࡾ, ࢝࢖ࣛࣜࢸ࢕㑅ᢥᛶࡢྥୖࡀሗ࿌ࡉࢀ࡚࠸ࡿ[1]ࡀ, ࡑࡢ࣓࢝ࢽࢬ࣒ࡣゎ᫂ࡉࢀ࡚࠸࡞࠸. ࡉࡽ࡞ࡿ࢝࢖ࣛࣜࢸ࢕㑅ᢥྜᡂࡢ㧗ᗘ໬࡟ྥࡅ࡚ࡣ, SWCNT ࡢᡂ㛗࣓࢝ࢽࢬ࣒
ࢆゎ᫂ࡋ, ࡑࢀ࡟ᇶ࡙ࡁྜᡂ᮲௳ࡢ᳨ウࢆ⾜࠺ᚲせࡀ࠶ࡿ. ࡑࡇ࡛ᮏ◊✲࡛ࡣ, SWCNT ᡂ㛗ࢆ෌⌧ࡍࡿᶵᲔᏛ⩦࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨ࠾ࡼࡧศᏊືຊᏛἲ࡟ࡼࡿ SWCNT ࡢᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸, SWCNT ᡂ㛗࣓࢝ࢽࢬ࣒ࢆศᯒࡍࡿ.

◊✲᪉ἲࠊィ⟬᪉ἲ᫖ᖺᗘ㛤ⓎࡋࡓᶵᲔᏛ⩦࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚, SWCNT ᡂ㛗㐣⛬ࢆᶍࡋࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ

ᐇ᪋ࡋࡓ. SWCNT ࡣ୍⯡࡟ࡣ 800㹼1200 Υ࡛ 1 nm ⛬ᗘࡢ㔠ᒓᚤ⢏Ꮚ࡟Ⅳ⣲※࢞ࢫࢆ౪⤥ࡍࡿࡇ࡜࡛ྜᡂࡉ
ࢀࡿ. ᮏࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࡇࡢ㐣⛬ࢆᶍࡋ࡚, ࢭࣝෆ࡟ Fe ᚤ⢏Ꮚࢆ㓄⨨ࡋ, Ⅳ⣲ཎᏊࢆ୍ᐃ㛫㝸࡛౪⤥ࡍࡿࡇ࡜࡛ SWCNT ࢆᡂ㛗ࡉࡏࡿ. ࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨ࡟ࡣ DeepMD-kit [3], MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡣ
LAMMPS[4]ࢆ⏝࠸ࡓ.



◊✲ᡂᯝ
SWCNT ᡂ㛗ࡢࡩࡿࡲ࠸ࢆỴᐃࡍࡿ≀ᛶ್࡜ࡋ࡚, ࢢࣛࣇ࢙ࣥࡢḞ㝗⏕ᡂ࢚ࢿࣝࢠ࣮, ࢢࣛࣇ࢙ࣥ➃㠃࢚ࢿࣝࢠ࣮ࡢ࢝࢖ࣛࣜࢸ࢕౫Ꮡᛶ, ゐ፹ᚤ⢏Ꮚࡢ⼥Ⅼ࡞࡝ࡀᣲࡆࡽࢀࡿ. ᮏ◊✲࡛ࡣࡇࢀࡽࡢ≀ᛶ್࡟ᑐࡋ࡚ᶵ
ᲔᏛ⩦࣏ࢸࣥࢩࣕࣝࡢጇᙜᛶࡢ᳨ドࢆ⾜࠸, ➨୍ཎ⌮ィ⟬ࡢ⤖ᯝ࠾ࡼࡧᐇ㦂್࡜ᩚྜࡍࡿ⤖ᯝࡀᚓࡽࢀࡓ.
ࡉࡽ࡟, ᶵᲔᏛ⩦࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚ SWCNT ᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ. Fig.1 ࡟(8,7) SWCNT ᡂ㛗ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ♧ࡍ. ᅗ࡟♧ࡋࡓ SWCNT ࡣ࢟ࣕࢵࣉᵓ㐀࡟ྵࡲࢀࡿ㸴ࡘࡢ஬ဨ⎔ࢆ㝖࠸࡚ࡍ࡭࡚
භဨ⎔ࡢࡳ࡛ᵓᡂࡉࢀ࡚࠸ࡿ↓Ḟ㝗 SWCNT ࡛࠶ࡗࡓ. ࡲࡓ↓Ḟ㝗 SWCNT ࡢᡂ㛗࡟ࡣ, Fig.2 ࡟♧ࡍࡼ࠺࡞,஬ဨ⎔ࡸ୐ဨ⎔࡞࡝ࡢḞ㝗ࡀⅣ⣲㛫⤖ྜࡢ⤌ࡳ᥮࠼࡟ࡼࡗ࡚භဨ⎔࡟ಟ᚟ࡉࢀࡿᶵᵓࡀ኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿ
ࡇ࡜ࡀุ᫂ࡋࡓ.



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
,NXPD.RKDWD5\R<RVKLNDZD.XQLR0RUL.DRUX+LVDPD.HLJR2WVXND6KRKHL&KLDVKL6KLJHR0DUX\DPD ➨ ᅇࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈ࣭ࢢࣛࣇ࢙ࣥ⥲ྜࢩ࣏ࣥࢪ࣒࢘ ྡྂᒇ ᖺ  ᭶
,NXPD.RKDWD5\R<RVKLNDZD.XQLR0RUL.DRUX+LVDPD.HLJR2WVXND6KRKHL&KLDVKL6KLJHR0DUX\DPD17

- 271 -

%RUGHDX[)UDQFH  ᖺ  ᭶ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Ikuma Kohata, Ryo Yoshikawa, Kaoru Hisama, Shigeo Maruyama, “Machine learning molecular dynamics simulationof single-walled carbon nanotube growth”, 2023, arXiv preprint arXiv:2302.09264, submitted.

)LJ  6:&17JURZWKRQ)H DW.7KHUHGFRORUHGSRO\JRQVGHQRWHWKHSHQWDJRQV

Fig.2 Edge healing processes on the developed view of the (8,7) SWCNT. (a) Reformation of a pentagon into a hexagon
on the (8,7) SWCNT. (b) Reformation of a heptagon into a hexagon on the (8,7) SWCNT. The red and blue polygons
denote the pentagon and heptagon, respectively.

ཧ⪃ᩥ⊩ >@<DQJ)HWDO1DWXUH í >@*.UHVVH DQG-+DIQHU3K\V5HY%
  >@ +DQ:DQJ &RPSXWHU3K\VLFV&RPPXQLFDWLRQV   >@ 7KRPSVRQ+HWDO&RPS
3K\V&RPP  

- 272 -

$')

&!(



%!"#

Theoretical Investigation on Selective Separation of Lanthanide/Minor
Actinide Complexes in Solvent ExtractionF#%F " FB(:3F.A F+>F$5?F/.'F"F* DC @-96476E

 4721dt^®Ø Y #"z §&X« "KiÚ"ßCG2:)7ÝLnÞ@)8
I(-3:)7ÝMAÞZ×" Z×¦sY¢¿%#"ßÏ¯Z×Í #"ßZtÇ¯É¥' ¨¡ßÀÙoÈpZU! Ln Ó),G SEIRA (Surface-Enhanced Infrared Absorption) 0?-6DÂ¤_ ß2021 }zMA &­xÛ&xª "³µ°¯ßÑtcuÄ¸!ßLn  MA ÐQtÔ #"Ó),G·RÌ&¹ ß«ÇÈp0?-6D&" #&xÛ #Èp0?-6DÊ " !ßÓ),G·RÌØt¨& w "·RÌHØt¨ßÐQt´

Ln/MA Ï Ô±Õ&  ßLn/MA Ï ZtÇ¯É¥&  " " 47!)F=8!)
[ CONFLEX Ð¹=F.CA&­Zt^m¢!Ó),GÐ¶Ô&¹ ßÁvwÌ&Ln   Eu3+&ßMA   Am3+&Ï ßÐQt  diglycolamide (DGA)&­
2011 }ß # Ò|ßÐQtÔ #"Ó),G SEIRA 0?-6D&"Ð
¹ #vwÌ&[Ì ßÑtcuÄ¸!Øtl~¨Øt`É¨ÌÎcbÃ&¿ÑtcuÄ¸ Gaussian16  ORCA &­ÑtcuÄ¸
! #Èp0?-6D&ßxÛÓ),GÈp0?-6DÊ " !ßÓ),GÌØt¨& w ßÏ ZtÇ¯É¥&  " &° 

 47

&

[ßEu3+/DGA Ó),GcuÑÇÅ ¦£MßEu3+ DGA  1:3 Ó),G&" ² #"ßSEIRA ZU¬nL DGA & S–Au Vºf!ÀÙkw "ßÐQÌ\Ö"Eu3+:DGA = 1:1ß1:2ß1:3 Ó),G«ÇÈp0?-6DxÛ # SEIRA 0?-6D&Ê  $ß1:3 Ó),GJ½¾r   ßSEIRA  Eu3+
 DGA  1:3 Ó),G& " w ßEu3+(DGA)3  Am3+(DGA)3 0?-6DÊ&¿j 1a  Eu3+ Am3+-DGA Ó),G SEIRA 0?-6D&ßj 1b «Ç0?-6D&´ 
SEIRA 0?-6DßEu3+Ó),G 1629cm-1  C=O P»b";G7&´ "y ßAm3+- 273 -

8 cm–1 E47/<6 Q¼;G7&´ "#

E47/<6Tg«Ç0?-6DWª #"ßDGA ±NS­ Eu3+),G! Am3+),GqºÇ

O]¦sY³µ"ß

DGA  Am3+),G! Eu3+&!Üa©Y " ´h#" #   ßDGA ±NS­{ ),GÜa©¦sY #"ßÓ),G±NS­¦sYa©ÔË±Õ"  



0<;
 >G1-C*G+I5D-(GB9*A),GÓRUÆÉeÝK204-4pm-02ß$YÞß'²!ß<>5ß [#tßfDSß$%ß7cuI 103 8,}Ý2022.3.2225,

  &RPSDULVRQ RI FDOFXODWHG ,5
VSHFWUD ZLWK WKH 6(,5$ VSHFWUD IRU(X$P±'*$FRPSOH[HV=«GquUDG0Þ
 Hypervalent Carbon and Iodine Compounds Investigated by Cryogenic Gas-Phase Spectroscopy (K205-4am-02,
Oral),Satoru Muramatsu, Akihito Matsuyama, Daiki Iwanaga, Keijiro Ohshimo, Motoki Kida, Yuan Shi, Rong Shang,
Yohsuke Yamamoto, Fuminori Misaizu, Yoshiya Inokuchiß7cuI 103 8,}Ý2022.3.2225, =«G
quUDG0Þ
MZ6Zt(GB9*A),GÓR "(:cePß$ %ßuN)WX(³µ(A)(06F06I\LRH«Ãlu«WJ"RVÝ2023.3.79, =quTG0Þ Cold Gas-Phase Spectroscopy of Chemical Intermediates Formed in Solution: Development of Electrospray-Based
Isolation Systems for Short-Lived Ions (Selected as Short Talk), Satoru Muramatsu, Yoshiya Inokuchi, Gordon Research
ConferenceGaseous Ions: Structures, Energetics and ReactionsÝ2023.2.1924, ( H>G3CÞ Carbocyanine Dyes Isolated under Cold Gas-Phase Conditions: Electronic Spectra and PhotochemistryÝ1B4bß$
YÞ,9-2ß<>5ß$%ßThe 19th Nano Bio Info Chemistry SymposiumÝ2022.12.1617, 41quÞ
 Development of gas-phase isolation systems for short-lived chemical intermediates in solution and their gas-phase
spectroscopyÝ1A2bß$YÞßÒ@KFßED?ß;Dlß<>5ß$%ßThe 19th Nano Bio Info Chemistry
SymposiumÝ2022.12.1617, 41quÞ
 A Theoretical Study on the Structure of Lanthanide/Minor Actinide Ion Complexes with Organic LigandsÝ1A4bß$YÞßC&Q*ß<>5ß$%ßThe 19th Nano Bio Info Chemistry SymposiumÝ2022.12.1617, 41q
uÞ Combinatorial Synthesis of Diglycolamide Ligands and Infrared Spectroscopy of their Lanthanide ComplexesÝ1C2bß$YÞß+.Aß<>5ß3/0qßBU0:ß$%ßThe 19th Nano Bio Info Chemistry Symposium
Ý2022.12.1617, 41quÞ
KOOp 27 u®À&¿,;
One-Dimensionally Conjugated Carbocyanine Dyes Isolated under Cold Gas-Phase Conditions: Electronic Spectra

and Photochemistry, S. Muramatsu, T. Tokizane, and Y. Inokuchi, J. Phys. Chem. A, 2022, 126, 8127–8135.

- 274 -

࢟ࣀࣜࣥ㦵᱁ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXGLHVRQ7UDQVLWLRQ0HWDO&RPSOH[HV%HDULQJD4XLQROLQH
EDVHG3LQFHU/LJDQG‫⚄ۑ‬㇂ᫀᏹ㸦໭㔛኱Ꮫ

⌮Ꮫ㒊໬Ꮫ⛉㸧◊✲┠ⓗ⏦ㄳ⪅ࡢ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ᭷ᶵ໬ྜ≀ࡢゐ፹ⓗኚ᥮཯ᛂ࡟άᛶࢆ♧ࡍ㑄⛣㔠ᒓ㘒య㸦᭷ᶵྜᡂ⏝ᆒ୍⣔ゐ፹㸧࡟㛵ࡍࡿ◊✲࡟ྲྀࡾ⤌ࢇ࡛ࡁࡓࠋ≉࡟ࠊ2016 ᖺᗘ௨㝆ࠊᮏ᪋タ฼⏝ࢆ㏻ࡌ࡚ᐇ㦂ⓗᡭἲ࡛ࡣྜᡂࠊ༢
㞳ࡢᅔ㞴࡞཯ᛂ୰㛫యࡢ᥎ᐃࡸࠊ᪂つᛶࡢ㧗࠸≉␗࡞㘒యᵓ㐀࡟㛵ࡋ࡚ Gaussian ࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡿゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ2022 ᖺᗘࡣࠊ⏦ㄳ⪅ࡀ⊂⮬࡟㛤Ⓨࡋࡓ࢟ࣀࣜࣥ㦵᱁ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య࡟ࡘ࠸࡚ࠊゐ፹๓㥑య 1 ࡢᵓ㐀ゎᯒ࠾ࡼࡧྠ㘒యࢆ⏝࠸ࡓ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬࡟㛵ࡍࡿ཯ᛂ⤒㊰ࡢ᥈⣴ࢆ⾜ࡗࡓࠋࣄࢻࣟࢩࣜࣝ໬཯ᛂࡣࣃࣛࢪ࣒࢘ࠊⓑ㔠࡞࡝ࡢ 4dࠊ5d 㑄⛣ඖ⣲ࢆ⏝࠸ࡓ཯ᛂ࡟㛵ࡋ࡚᪤࡟ከ
ࡃࡢㄪᰝࡀ⾜ࢃࢀ࡚࠾ࡾࠊChalk-Harrod ᶵᵓ࡞࠸ࡋࡣ Modified Chalk-Harrod ᶵᵓ࡛཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ▱ࡽࢀࡿࠋᮏ⏦ㄳ࡛ࡣࠊୖグࡢ 4d, 5d 㔠ᒓ㘒య࡟㛵ࡍࡿඛ⾜◊✲ࢆཧ⪃࡜ࡋࡘࡘࠊ3d 㑄⛣⣔ิࡢ㑄⛣㔠ᒓゐ፹ࡢ≉᭷ࡢ཯ᛂᶵᵓ࡟ࡘ࠸࡚ゎᯒࢆ㐍ࡵࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᵓ㐀᭱㐺໬࡟ᚲせ࡞ึᮇᵓ㐀࠾ࡼࡧࢫࣆࣥከ㔜ᗘࡣ༢⤖ᬗ X ⥺⤖ᬗᵓ㐀ゎᯒ࡞ࡽࡧ࡟ Evans ἲࢆ⏝࠸ࡓ☢໬⋡ᐃ࡟ࡼࡾᚓࡽࢀࡿᐇ㦂್ࢆࡶ࡜࡟タᐃࡋࡓࠋゐ፹཯ᛂ⤒㊰ࡣࠊMEPࠊTSࠊIRC ィ⟬࡟ࡼࡾ᥈⣴ࡋࠊᚓࡽࢀࡓྛᵓ㐀࡟ᑐࡍࡿ᣺ືィ⟬ࡶྜࢃࡏ࡚⾜ࡗࡓࠋᵓ㐀᭱㐺໬࠾ࡼࡧゐ፹཯ᛂ⤒㊰ࡢጇᙜᛶ࡟ࡘ࠸࡚ࡣィ⟬⤖ᯝ࡜ᐇ㦂⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛ホ౯ࡋࡓࠋィ⟬࡟ࡣ Gaussian 09 ࠾ࡼࡧ 16 ࢆ⏝࠸ࠊᵓ㐀᭱㐺໬࡟ࡣ
B3LYP, B3PW91, M06, M06Lࠊ୍Ⅼィ⟬࡟ࡣ B3LYP, B3PW91, M06, M06L, mPW1PW91, PBE, TPSS, PBE0 ࡢỗ㛵ᩘࢆ⏝࠸ࡓࠋࡲࡓࠊᚲせ࡟ᛂࡌ࡚ศᩓຊ⿵ṇ㸦D3, D3BJ㸧ࢆ㐺⏝ࡋࡓࠋᇶᗏ㛵ᩘ࡟ࡣࠊ㑄⛣㔠ᒓ㸦Fe㸧࡟ᑐࡋ࡚ LanL2DZࠊSDDࠊࡲࡓࡣ def2-SV(P)ࠊࡑࡢ௚ࡢཎᏊ࡟ᑐࡋ࡚ࡣ def2-SV(P), def2-TZVP, 6-311G(d,p) ࢆ⏝࠸࡚ᵓ㐀᭱㐺໬࠾ࡼࡧ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࠋ



◊✲ᡂᯝ
P1

3.1 ࣆࣂࣝ㓟㕲㘒యࡢ⁐ᾮ୰࡟࠾ࡅࡿືⓗᣲື

O4

O3

N2

ᅗ 1 ࡟♧ࡍࣆࣂ࣮ࣞࢺ㘒య 1-3 ࡣ࢔ࣝࢣࣥࡢࣄ

Fe1ࢻࣟࢩࣜࣝ໬࠾ࡼࡧ C-H ࣍࢘⣲໬཯ᛂ࡟άᛶࢆ

N1

O1
O2

N2

O4
O3

Fe1
N1

1a

♧ࡍゐ፹๓㥑య࡛࠶ࡿࠋࡇࢀࡽ㘒యࡢ⤖ᬗᵓ㐀࡟

P1

P1

O4

O2

N2

O3

Fe1

O1

O1

O2
N1

1b

࠾࠸࡚ࠊ஧ࡘࡢ࢝ࣝ࣎࢟ࢩࣛࢺ㓄఩Ꮚࡢ࠺ࡕࠊ୕
ࡘࡢ㓟⣲ཎᏊ࡜㕲ࡣ୍⯡ⓗ࡞ඹ᭷⤖ྜ༙ᚄࡢ࿴
ࡢ⠊ᅖෆ࡛࠶ࡿࡀ㸦2.006–2.347 Å㸧ࠊṧࡾ୍ࡘࡣ㢧ⴭ࡟㛗࠸㸦1a: 2.633(3) Å, 1b: 2.762(3) Å, 2: 2.686(3)Å, 3: 2.965(2) Å㸧ࠋࡇࢀࡽᅄࡘࡢ㓟⣲ཎᏊ࡜㕲࡜ࡢ
ᅗ 1. 㕲㘒యࡢ⤖ᬗᵓ㐀࠾ࡼࡧ᭱㐺໬ᵓ㐀┦஫స⏝࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊ1a ࠾ࡼࡧ- 275 -1c

1b ࢆึᮇᵓ㐀࡜ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ࠸ࡎࢀࡶ㸯ࡘࡢᵓ㐀࡟཰᮰ࡋࡓ㸦1c㸧ࠋᚓࡽࢀࡓ᭱㐺໬ᵓ㐀 1c ୰ࡢ㕲㸫㓟⣲㛫ࡢ㊥㞳ࡣ 1b ࡟㏆ࡃࠊྛඖ⣲㛫࡟ᑐࡍࡿ Wiberg bond index㸦0.11㹼0.31㸧࠾ࡼࡧ Mayer
bond order㸦0.12㹼0.42㸧 ࡣ㕲࡜ᅄࡘࡢ㓟⣲ཎᏊ࡜ࡢ┦஫స⏝ࡢᏑᅾࢆ♧၀ࡋࡓࠋࡇࢀࡽࡢ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊ
⌧ᅾㄽᩥ࡟ᢞ✏ࡋࠊᰝㄞࢆཷࡅ࡚࠸ࡿ㸦5-2㸧ࠋ
3.2 ࢫࣆࣥ⚗ไ㐣⛬ࢆྵࡴ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬཯ᛂ
3.1 ࡢ㕲㘒యࢆ⏝࠸ࡓ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬࡛ࡣࠊᐇ㦂⤖ᯝ࠾ࡼࡧணഛⓗ࡞ィ⟬⤖ᯝ࠿ࡽࠊModified
Chalk-Harrod ᶵᵓ࡟㢮ఝࡋࡓ཯ᛂᶵᵓ࡛཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿ࡜᥎ᐃࡋ࡚࠸ࡿ㸦Organometallics 2020, 39, 3535㸧
ࠋ᥎ᐃᶵᵓ࡟࠾ࡅࡿྛ໬Ꮫ✀ A㸫C ࡟ࡘ࠸࡚ࠊ୍㔜㡯࠾ࡼࡧ୕㔜㡯≧ែ࡟࠾ࡅࡿ཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
ᅗ 2 ࡢ⤖ᯝࡀᚓࡽࢀࡓࠋࢩࣛࣥࡢ㓟໬ⓗ௜ຍ㸦AЍB㸧࠾ࡼࡧࢩࣜࣝᇶࡢ࢔ࣝࢣࣥ࡬ࡢ㌿⛣㸦BЍC㸧ࡢ஧㐣⛬࡟࠾ࡅࡿ஧ࡘࡢࢫࣆࣥ≧ែࡢ஺Ⅼ㸦MECP㸧࡟ࡘ࠸࡚ࡶゎᯒࢆ㐍ࡵ࡚࠾ࡾࠊࡇࢀࡽࡢ⤖ᯝ࡟ࡘ࠸࡚ࡶㄽᩥᢞ✏ࢆணᐃࡋ࡚࠸ࡿࠋ

ᅗ 2. PNN 㕲㘒యࢆ⏝࠸ࡓ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬ࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬4.1 㔠ග࿴ᶞࠊ⚄㇂ᫀᏹࠊᘪ๐⚽㝯ࠊ➨ 26 ᅇࢣ࢖⣲໬Ꮫ༠఍ࢩ࣏ࣥࢪ࣒࢘
‫ۻ‬4.2 ⚄㇂ᫀᏹࠊᘪ๐⚽㝯ࠊ➨ 12 ᅇ AKPS ࢩ࣏ࣥࢪ࣒࢘

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
5-1. Kamitani, M. Earth Abundant 3d Transition Metals (Fe, Co, Ni) for Nondirected C-H Borylation. In Handbook

of CH-Functionalization (Wiley-VCH), Chapter 088, 2022. DOI: 10.1002/9783527834242.chf0088.
‫ۻ‬5-2. Kamitani, M.; Kanemitsu, K.; Yujiri, K.; Yuge, H. Organometallics 2023, submitted for publication.

- 276 -

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿග໬Ꮫ⣔ϩࡢᵓ㐀࣭཯ᛂᶵᵓゎᯒ
4XDQWXPFKHPLFDOFDOFXODWLRQVWXG\RQWKHVWUXFWXUHDQGUHDFWLRQPHFKDQLVPRISKRWRV\VWHP,,‫ۑ‬㔝ཱྀ ᕦࠊຍ⸨ ♸ᶞ㸦ྡྂᒇ኱㝔࣭⌮㸧

1◊✲┠ⓗࠊෆᐜ ග໬Ꮫ⣔ϩ㸦PSII㸧ࡣࠊ᳜≀ࠊ⸴㢮ࠊࢩ࢔ࣀࣂࢡࢸࣜ࢔ࡢࢳࣛࢥ࢖ࢻ⭷࡟Ꮡᅾࡍࡿࢱࣥࣃࢡ㉁」ྜయ࡛࠶
ࡾࠊග࢚ࢿࣝࢠ࣮࡟ࡼࡿỈศゎࢆ⾜࠸ࠊ᭷ᶵ≀ྜᡂࡢࡓࡵࡢ㟁Ꮚࢆ⋓ᚓࡍࡿᙺ๭ࢆᣢࡘࠋ཯ᛂ୰ᚰࢡࣟࣟࣇ
࢕ࣝࡢ୍㔜㡯ບ㉳≧ែ࠿ࡽࡢ㟁Ⲵศ㞳࡟ࡼࡗ࡚㟁Ꮚ⛣ືࡀ㥑ືࡉࢀࠊPSII ࡢ࣮࣓ࣝࣥഃ࡟⤖ྜࡍࡿ Mn4CaO5ࢡࣛࢫࢱ࣮࡟࠾࠸࡚Ỉࡢศゎ࡟ࡼࡿ㓟⣲Ⓨ⏕ࡀ⾜ࢃࢀࡿࠋࡇࡢỈศゎ࣭㓟⣲Ⓨ⏕཯ᛂࡢศᏊᶵᵓࡢヲ⣽ࡣᮍࡔ᫂ࡽ࠿࡜ࡉࢀ࡚࠸࡞࠸ࠋࡲࡓࠊ㟁Ⲵ෌⤖ྜ࡟ࡼࡗ࡚⏕ࡌࡿࢡࣟࣟࣇ࢕ࣝ୕㔜㡯≧ែࡢᾘගᶵᵓࡣࠊPSII ࡢගಖㆤᶵᵓ࡜ࡋ࡚㔜せ࡛࠶ࡿࡀࠊࡑࡢศᏊᶵᵓࡶᮍࡔ୙࡛᫂࠶ࡿࠋᮏ◊✲࡛ࡣࠊ᭱㏆ࠊᡃࠎࡢࢢ࣮ࣝࣉࡀぢฟࡋࡓ Mn4CaO5 ࢡࣛࢫࢱ࣮㓄఩Ꮚࡢ࢔࣑ࣀ㓟ኚ᥮⌧㇟ࡀࠊ⩻ヂᚋ࡟ࢱࣥࣃࢡ㉁࡛ࣞ࣋ࣝ㉳ࡇࡿࡇ࡜ࢆド᫂ࡍࡿࡓࡵࠊD1-D170 㓄఩Ꮚ࡟ 13C ྠ఩యࢆᑟධࡋࡓ㝿ࡢ㉥እࢫ࣌ࢡࢺࣝኚ໬ࢆ quantum mechanics/molecularmechanics㸦QM/MM㸧ィ⟬࡟ࡼࡾ෌⌧ࡋࡓࠋࡲࡓࠊࢡࣟࣟࣇ࢕ࣝ୕㔜㡯࡜ᇶᗏ୍㔜㡯≧ែࡢ㉥እᕪࢫ࣌ࢡࢺ
ࣝࢆゎᯒࡍࡿࡓࡵࠊ཯ᛂ୰ᚰࢡࣟࣟࣇ࢕ࣝࣔࢹࣝ࡟ᑐࡋ࡚ᐦᗘỗ㛵ᩘἲ㸦DFT㸧࡟ࡼࡿᇶ‽᣺ືィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ 36,,ࢱࣥࣃࢡ㉁ࡢ;⥺⤖ᬗᵓ㐀㸦3'%,'8%㸧࠿ࡽࠊ0Q&D2ࢡࣛࢫࢱ࣮ࡢ࿘ᅖc௨ෆࡢ࢔࣑ࣀ㓟ṧᇶ࠾ࡼࡧỈศᏊࢆษࡾྲྀࡾࠊึᮇᵓ㐀࡜ࡋࡓࠋ㓟⣲Ⓨ⏕⣔ࢆᵓᡂࡍࡿ0Q&D2ࢡࣛࢫࢱ࣮࠾ࡼࡧ࢔࣑ࣀ㓟ࠊỈศᏊࢆ40㡿ᇦ࡜ࡋࠊࡑࢀ௨እࢆ00㡿ᇦ࡟ᣦᐃࡋ࡚ࠊ*DXVVLDQୖࡢ21,20ἲ࡟ࡼࡾ4000ィ⟬ࢆ⾜࠸ࠊ40㡿ᇦࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ40ィ⟬࡟ࡣ%/<3㛵ᩘ⣔ࢆ౑⏝ࡋࠊᇶᗏ⣔࡜ࡋ࡚ࠊ&Dཬࡧ0QཎᏊ࡟ࡣ/$1/'=ࢆࠊࡑࡢ௚ࡢཎᏊ࡟ࡣ* G  ࢆ⏝࠸ࡓࠋ''ࡢ≉␗ⓗ&⨨᥮ࡢィ⟬࡛ࡣࠊ'ࡢ㸲ࡘࡢⅣ(S2) D170(S1) C-D170,D61

13

-1000

13

-1500

13

ᇶ‽᣺ືィ⟬ࢆ⾜ࡗࡓࠋ -500(S2) C-D170

ᑐࡋ࡚')7ἲ㸦%/<3* G 㸧࡟ࡼࡿᵓ㐀᭱㐺໬࠾ࡼࡧ0(S2) C-D170,A344

᥮ࡋࠊ㸱ࡘࡢỈศᏊࢆ᪂ࡓ࡟ᤄධࡋࡓࠋࡇࢀࡽࡢࣔࢹࣝ࡟

500(S1) E333,D170

ࡼࡧ'+$ኚ␗యࡢࣔࢹ࡛ࣝࡣࠊ+LV㓄఩Ꮚࢆ$OD࡟⨨1000(S1) D170,E333

ࣔࢹࣝ࡜&KO'࡜3'ࡼࡾ࡞ࡿࣔࢹࣝࢆ⏝ពࡋࠊ'+$࠾

1500

IR Intensity (km/mol)㐀㸦3'%,'$5&㸧ࡢᗙᶆࢆ⏝࠸ࡓࠋ&KO'࡜3'ࡼࡾ࡞ࡿ

13 ཯ᛂ୰ᚰࢡࣟࣟࣇ࢕ࣝࣔࢹࣝࡢึᮇᵓ㐀࡟ࡣ;⥺⤖ᬗᵓ(S1) D61, C-D170⣲ࢆ&࡟⨨᥮ࡋࡓࣔࢹࣝࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ 

3

-2000

◊✲ᡂᯝ

1400

1350

1300
-1

Wavenumber (cm )㸦㸯㸧Mn4CaO5 ࢡࣛࢫࢱ࣮㓄఩Ꮚࡢ࢔࣑ࣀ㓟ኚ᥮
PSII ࡢ Mn4CaO5 ࢡࣛࢫࢱ࣮࠾ࡼࡧ࿘㎶ࢱࣥࣃࢡ㉁ࢆྵࡴ

ᅗ 1㸬13C-D170 ⨨᥮ PSII ࡢ S2/S1 ㉥እᕪࢫ

㓟⣲Ⓨ⏕⣔ࡢࣔࢹࣝ࡟ᑐࡋ࡚ࠊQM/MM ἲࢆ⏝࠸࡚ᵓ㐀᭱࣌ࢡࢺࣝ㸦ᑐ⛠ COOí㡿ᇦ㸧ࡢ QM/MM ࢩ㐺໬࠾ࡼࡧᇶ‽᣺ືゎᯒࢆ⾜࠸ࠊS2 ≧ែ࡜ S1 ≧ែࡢ㉥እ࣑࣮ࣗࣞࢩࣙࣥ

- 277 -

ᕪࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋMn ࡜ Ca ࢆᯫᶫࡍࡿ࢔࣑ࣀ㓟㓄఩Ꮚ࡛࠶ࡿ D1-D170 ࢆ≉␗ⓗ࡟ 13C ⨨᥮ࡋࡓࣔࢹࣝ࡟
ࡘ࠸࡚ࡶྠᵝ࡟ィ⟬ࢆ⾜࠸ࠊ13C ⨨᥮࡟ࡼࡿ COOíఙ⦰᣺ື㡿ᇦࡢ㉥እࢫ࣌ࢡࢺࣝࡢኚ໬ࢆㄪ࡭ࡓ㸦ᅗ㸯㸧ࠋᐇ㦂࡟ࡼࡿࣂࣥࢻࢩࣇࢺࡀ෌⌧ࡉࢀࡓࡇ࡜࠿ࡽࠊ13C-His ࢆᑟධࡋࡓ D1-D170H ኚ␗యࡢ His ࠿ࡽ Asp ࡬ࡢኚ᥮ࡀࠊ⩻ヂᚋ࡟ࢱࣥࣃࢡ㉁࡛ࣞ࣋ࣝ㉳ࡇࡿࡇ࡜ࡀド᫂ࡉࢀࡓ㸦Shimada et al., Nature Commun., 2022㸧
ࠋᅗ 2㸬D2-H197A ኚ␗యࡢ ChlD1-PD2 ࣔࢹࣝࡢ㸦㸰㸧཯ᛂ୰ᚰࢡࣟࣟࣇ࢕ࣝࡢỈ⣲⤖ྜᵓ㐀
PSII ࡢࢡࣟࣟࣇ࢕ࣝ PD2 ࡢࣄࢫࢳࢪࣥ㓄఩Ꮚࢆ࢔ࣛࢽ

DFT ᭱㐺໬ᵓ㐀ࣥ࡟ᨵኚࡋࡓ D2-H197A ኚ␗యࡢ཯ᛂ୰ᚰࢡࣟࣟࣇ࢕ࣝ
ࠊ㔝⏕ᆺࣔࢹࣝࡢ
ࣔࢹࣝ㸦ChlD1-PD2㸧࡟ࡘ࠸࡚ࠊDFT ἲ࡟ࡼࡿᵓ㐀᭱㐺໬࠾ࡼࡧᇶ‽᣺ືゎᯒࢆ⾜࠸㸦ᅗ㸰㸧ィ⟬⤖ᯝ࡜ẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊ୕㔜㡯/୍㔜㡯㉥እᕪࢫ࣌ࢡࢺ࡛ࣝᐇ㦂ⓗ࡟ᚓࡽࢀ࡚࠸ࡓ ChlD1 ࡢࢣࢺ C=O
ఙ⦰᣺ືࡢ㧗Ἴᩘࢩࣇࢺࡀ෌⌧ࡉࢀࠊ㟁Ⲵ෌⤖ྜ࡟ࡼࡾ⏕ࡌࡓບ㉳୕㔜㡯≧ែࡀ୺࡟ ChlD1 ୖ࡟Ꮡᅾࡍࡿࡇ࡜
ࡀ♧ࡉࢀࡓ㸦+D\DVHHWDOJ. Phys. Chem. B㸧ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ★ 㔝ཱྀᕦࠊගྜᡂ㓟⣲Ⓨ⏕ࡢ㉳※࡜㐍໬ࠊ᪥ᮏගྜᡂᏛ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2022 ᖺ 5 ᭶ 20-21 ᪥★ 㔝ཱྀᕦࠊỈศゎ㓝⣲࣭ග໬Ꮫ⣔ϩࡢ㉥እศග◊✲ࠊ⏕యศᏊ⛉Ꮫウㄽ఍ࠊ㫽ྲྀᕷ࡜ࡾࡂࢇᩥ໬఍㤋ᑠ࣍
࣮ࣝࠊ2022 ᖺ 6 ᭶ 30 ᪥㸫7 ᭶ 1 ᪥★Takumi Noguchi, Yuichiro Shimada, Takehiro Suzuki, Takumi Matsubara, Tomomi Kitajima-Ihara, Ryo Nagao, andNaoshi Dohmae, Post-translational amino acid conversion in the oxygen-evolving complex and its implication,
Mechanisms of Water Oxidation, Satellite Meeting to 18th International Congress on Photosynthesis Research,
University of Otago, Dunedin, New Zealand (and online), August 6-7, 20225ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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ᕦࠊග໬Ꮫ⣔ϩ࡟࠾ࡅࡿ⩻ヂᚋ࢔࣑ࣀ㓟ኚ᥮࡜ගྜᡂ㓟⣲Ⓨ⏕ࡢ㉳※ࠊ ග ྜᡂ◊✲ ࠊ   - 278 -

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ࡀ▱ࡽࢀ࡚࠾ࡾࠊࡇࡢ཯ᛂࡣࠕග࢔ࣥࢣ࣮ࢪࣥࢢࠖ࡜ࡋ࡚⏕యෆࡢ⸆≀ศᏊᨺฟ࡟ᛂ⏝ࡉࢀ࡚࠸ࡿࠋ୍⯡࡟ගቑឤ๣࡜ࡋ࡚࣏ࣝࣇ࢕ࣜࣥࢆ⏝࠸ࡿሙྜࠊ཯ᛂࡢㄏ㉳࡟ࡣᇶᗏ୍㔜㡯≧ែ 6  ࠿ࡽບ㉳୍㔜㡯≧ែ 6Q ࡬ࡢ㑄⛣࢚ࢿࣝࢠ࣮࡟ᑐᛂࡍࡿ㟷Ⰽගࡸ⥳Ⰽගࡀᚲせ࡜ࡉࢀࡿࠋ୍᪉ࠊ⏕య࡬ࡢᛂ⏝࡟ᙜࡓࡗ࡚ࡣࠊ⏕య⤌
⧊㏱㐣ᛶࡢ㧗࠸㉥Ⰽගࡢ฼⏝ࡀᮃࡲࢀࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ᭷ᶵ࢖ࣜࢪ࣒࣏࢘ࣝࣇ࢕ࣜࣥ㘒యࡢ 6 ࠿ࡽ᭱పບ㉳୕㔜㡯≧ែ 7  ࡬ࡢ┤᥋㑄⛣ࢆ฼⏝ࡋࡓ㉥Ⰽග࢔ࣥࢣ࣮ࢪࣥࢢἲࡢ㛤Ⓨࢆ┠ᣦࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ᭷ᶵ⁐፹୰࡟࠾ࡅࡿග࢔ࣥࢣ࣮ࢪࣥࢢ⬟ࡢㄪᰝ࡛ࡣࠊ㘒యࡢ㔜࣋ࣥࢮࣥ⁐ᾮ࡟ᑐࡋࠊ㓟⣲㞺ᅖẼୗࡲࡓࡣ✵Ẽୗ࡛㉥Ⰽගࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾᚓࡽࢀࡓ཯ᛂᾮࢆࠊ105 ࢫ࣌ࢡࢺࣝ

ᐃ࡛㏣㊧ࡋࡓࠋࡇࢀࡽ࡜୪⾜ࡋ࡚ࠊ')7  7'')7 ἲ࡟ࡼࡾࠊ㘒యࡢᇶᗏ㸭ບ㉳≧ែ࡟࠾ࡅࡿ㟁Ꮚ≧ែゎᯒࢆࡑࢀࡒࢀᐇ᪋ࡋࡓࠋ⌮ㄽィ⟬࡟ࡼࡿග཯ᛂゎᯒ࡟ࡣࠊ*DXVVLDQ ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࠊ%/<3 ỗ㛵ᩘ࠾ࡼࡧ 'HI7=933 ᇶᗏ㛵ᩘ⣔ࢆ㐺⏝ࡋࡓࠋ⁐፹ຠᯝࡣศᴟ㐃⥆య㸦3&0㸧ࣔࢹࣝ࡟ࡼࡾ⪃៖ࡋࡓࠋ



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⮬ືᵓ⠏ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿ㸬ࡲࡓ㸪࢔ࣝࢦࣜࢬ࣒ࡢ༢⣧ࡉ࠿ࡽ㸪」㞧࡞཯ᛂ࡬ࡢ㐺⏝ᛶࡀ㠀ᖖ࡟㧗ࡃ㸪ࡇࢀࡲ࡛࡟㸪᭷ᶵ཯ᛂ㸪ග཯ᛂ㸪㓝⣲཯ᛂ㸪⾲㠃཯ᛂ㸪⤖ᬗᵓ㐀┦㌿⛣࡞࡝ࡢᗈ⠊࡞໬Ꮫ཯ᛂ࡬࡜ỗ⏝໬ࡀᐇ⌧ࡋ࡚࠸ࡿ㸬ࡉࡽ࡟㸪ᚓࡽࢀࡿ」㞧཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ࡟㐺⏝ࡋᚓࡿ㏿ᗘᐃᩘ⾜ิ⦰⣙ 5&0& ἲࢆ㛤Ⓨ
ࡋ㸪5&0& ἲ࡜ $),5 ἲࢆ⤌ࡳྜࢃࡏࡓ㏿ᗘㄽࢼࣅࢤ࣮ࢩࣙࣥ௜ࡁ཯ᛂ⤒㊰⮬ື᥈⣴ࡶྍ⬟࡛࠶ࡿ㸬⌧ᅾ㸪⏕య⣔࡞࡝࡬ࡢ᭦࡞ࡿỗ⏝໬ࢆ┠ᣦࡋ࡚㛤Ⓨ◊✲ࢆ㐍ࡵ࡚࠸ࡿ㸬ࡲࡓ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡟ࡼࡾ㸪ᡭἲࡢᛂ⏝ࡶ⢭ຊⓗ࡟ᒎ㛤ࡋ࡚࠸ࡿ㸬ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬㈨※ࢆ฼⏝ࡋ࡚㸪᭷ᶵ཯ᛂ㸪ග཯ᛂ㸪㓝⣲཯ᛂ㸪⾲㠃཯ᛂ㸪⤖ᬗᵓ㐀┦㌿⛣࡬ࡢᛂ⏝◊✲ࢆຍ㏿ࡋࡓ࠸࡜⪃࠼࡚࠸ࡿ㸬᭷ᶵ཯ᛂࡸග཯ᛂ࡞࡝㸪ࡍ࡛࡟ᛂ⏝ᐇ⦼ࡢ࠶ࡿ཯ᛂ⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲ࢆ᥎㐍ࡍࡿ࡜࡜ࡶ࡟㸪ᐇ㦂࡟ඛ❧ࡗࡓணࢆᐇ⌧ࡋ࡚࠸ࡃࡇ࡜ࢆ┠ᣦࡍ㸬ࡲࡓ㸪⤖ᬗ┦㌿⛣ࡸ㓝⣲཯ᛂ࡜࠸ࡗࡓ」㞧⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢹ࣮ࢱࡢゎᯒ
ࢆ㏻ࡌ࡚ࡑࡢ㐺⏝ᛶࢆ᳨ドࡍࡿ㸬᫖ᖺᗘࡣ㸪௨ୗࡢ  ࡘࡢㄢ㢟࡟ࡘ࠸࡚୺࡟᳨ウࡋࡓ㸬 㟁Ꮚ⛣ື཯ᛂࡢ⡆᫆ィ⟬ἲࡢ㛤Ⓨ࡜཯ᛂゎᯒ࡬ࡢᛂ⏝㟁Ꮚ⛣ື (7 ཯ᛂࡣ໬Ꮫ཯ᛂࡢ㔜せ࡞ᇶ♏ⓗ㐣⛬࡛࠶ࡿ㸬࣐࣮࢝ࢫ⌮ㄽ࡛ࡣ (7 ๓ᚋ  ≧ែࡢ࣏ࢸࣥࢩࣕ
࢚ࣝࢿࣝࢠ࣮᭤㠃 3(6 ࢆㄪ࿴㏆ఝࡋ㸪(7 ๓ᚋࡢᏳᐃᵓ㐀࠿ࡽ㟁Ꮚ⛣ື㏿ᗘᐃᩘ N(7 ࢆィ⟬࡛ࡁࡿ㸬୍᪉࡛
3(6 ࡢ㠀ㄪ࿴ᛶࡢ⪃៖ࡸศᏊᵓ㐀ኚ໬ࡢヲ⣽࡞ゎᯒ࡛ࡣ 3(6 ஺ᕪ㡿ᇦࡢィ⟬ࡀᚲせ࡜࡞ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪3(6 ஺ᕪ㡿ᇦࢆ $),5 ἲ࡟ࡼࡗ࡚⮬ື᥈⣴ࡍࡿ㝿࡟ࡣ㸪(7 ๓ᚋ  ≧ែࢆዴఱ࡟⮬ື㑅ᢥࡍࡿ࠿ࡀㄢ㢟࡜࡞ࡿ㸬ᮏ◊✲࡛ࡣㄢ㢟ゎỴࡢࡓࡵ㸪21,20 ἲࡢศ๭እᤄィ⟬࡟╔┠ࡋࡓ㸬ศ๭⣔ࡈ࡜࡟㟁Ꮚ≧ែࢆᣦᐃࡋ࡚ィ⟬ࡋࡓ࢚ࢿࣝࢠ࣮ࢆእᤄࡍࡿࡇ࡜࡛ (7 ๓ᚋ  ≧ែࢆ㑅ᢥⓗ࡟ィ⟬ࡍࡿᡭἲࢆ㛤Ⓨࡋ㸪㛤Ⓨᡭἲࢆ⏝࠸ࡓ 3(6 ஺ᕪ㡿ᇦࡢィ⟬࠿ࡽ (7 ࢆヲ⣽࡟ゎᯒࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬 ࢔ࢼࢱ࣮ࢮᆺ 7L2  㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂᶵᵓࡢ⌮ㄽゎᯒ㓟໬≀⾲㠃ࡣ᭱ࡶᗈࡃ฼⏝ࡉࢀ࡚࠸ࡿᕤᴗゐ፹࡛࠶ࡾ㸪㓟໬≀⾲㠃ୖ࡟࠾ࡅࡿ཯ᛂゎᯒᡭἲࡢ☜❧ࡣᏛ⾡ⓗ࡟ࡶ⏘ᴗⓗ࡟ࡶ᭷⏝࡛࠶ࡿ㸬ࡑࡇ࡛㸪$),5 ἲ࡟ࡼࡿ⮬ື᥈⣴ࢆ⏝࠸㸪⇕ຊᏛⓗ࡟Ᏻᐃ࡞࢔ࢼࢱ࣮ࢮᆺ
7L2  㠃ୖ࡟࠾ࡅࡿࢠ㓟ࡢ⇕ศゎ཯ᛂᶵᵓࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬 ⇕ⓗ +XLVJHQ ཯ᛂ⏕ᡂ≀ࡢ఩⨨㑅ᢥᛶไᚚ࡟㛵ࡍࡿ◊✲⇕ⓗ +XLVJHQ ཯ᛂࡣ࢔ࢪࢻ࡜࢔ࣝ࢟ࣥࡀ཯ᛂࡋ࡚ࢺࣜ࢔ࢰ࣮ࣝ⎔ࢆ⏕ᡂࡍࡿ཯ᛂ࡛࠶ࡾ㸪↓ゐ፹᮲௳ୗ࡟
࠾࠸࡚⏕ᡂ≀࡛࠶ࡿ ⨨᥮య࡜ ⨨᥮యࡢ఩⨨㑅ᢥᛶࡀప࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ㸬ᮏ◊✲࡛ࡣ㸪࢔ࢪࢻ࡜- 294 -

࢔ࣝ࢟ࣥࡢ⨨᥮ᇶࡢ⤌ࡳྜࢃࡏࢆ᭱㐺໬ࡋ㸪⨨᥮యࡢ఩⨨㑅ᢥᛶ᭱኱໬ࡍࡿࡇ࡜┠ⓗ࡜ࡋࡓ㸬 ໬Ꮫ཯ᛂࡢỈࢡࣛࢫࢱ࣮ෆ࡟࠾ࡅࡿάᛶ఩⨨࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㏆ᖺ㸪ⷧᒙࡸᚤᑠᾮ⁲࡜࠸ࡗࡓ⣔࡟࠾ࡅࡿ᭷ᶵྜᡂࡀ┒ࢇ࡟⾜ࢃࢀ࡚࠸ࡿ㸬ࡑࡢࡼ࠺࡞⣔࡛ࡣࣂࣝࢡ୰࡜
ẚ㍑ࡋ࡚㸪཯ᛂ㏿ᗘࡢ᱆㐪࠸ࡢୖ᪼ࡸ㸪㏻ᖖ㐍⾜ࡋ࡞࠸཯ᛂࡢ㐍⾜➼ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀ㸪ࡑࡢᚤどⓗ࡞⌮ゎࡣᮍࡔ࡞ࡉࢀ࡚࠸࡞࠸㸬ࡑࡇ࡛㸪ᮏ◊✲࡟࠾࠸࡚ࡣ཯ᛂ⤒㊰ࡢ⣔⤫ⓗ࡞⮬ື᥈⣴࡟ࡼࡗ࡚㸪⁐፹⾲㠃ࡢᏑᅾࡀ᭷ᶵ཯ᛂ࡟୚࠼ࡿᙳ㡪ࢆ⌮ゎࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬 ศᏊᛶ⤖ᬗ⣔࡟࠾ࡅࡿ┦㌿⛣⤒㊰᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝ศᏊᛶ⤖ᬗࡢ⇕ⓗ㸪㟁Ẽⓗ㸪ගᏛⓗ≉ᛶࡣ㸪⤌ᡂࡸ⤖ᬗᵓ㐀࡟኱ࡁࡃ౫Ꮡࡋ࡚࠸ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪㉸పᅽ┦ࡸ㉸㧗ᅽ┦࡟࠾ࡅࡿᏳᐃᵓ㐀ࡸᵝࠎ࡞‽Ᏻᐃ⤖ᬗᵓ㐀ࢆ⌮ㄽⓗ࡟⟬ฟࡍࡿ࡟ࡣ⭾኱࡞ィ⟬㈨※ࢆᚲせ࡜ࡍࡿ㸬ᮏ◊✲࡛ࡣ $),5 ἲࢆศᏊᛶ⤖ᬗ⣔࡟ᣑᙇࡋ㸪ศᏊᛶ⤖ᬗ⣔࡟࠾ࡅࡿ┦㌿⛣⤒㊰ࡢ⡆౽࡞᥈⣴ἲࢆ㛤Ⓨࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ ◊✲᪉ἲ㸪ィ⟬᪉ἲ 㟁Ꮚ⛣ື཯ᛂࡢ⡆᫆ィ⟬ἲࡢ㛤Ⓨ࡜཯ᛂゎᯒ࡬ࡢᛂ⏝㛤Ⓨᡭἲ࡛ࡣ (7 ๓ᚋ  ≧ែࡢ㏱⇕࢚ࢿࣝࢠ࣮ܸଵଵ ࡜ܸଶଶ ࢆ௨ୗࡢᘧ࡛እᤄࡍࡿ㸬‫ࡣܧ‬᩿⇕≧ែࡢ㟁Ꮚ࢚ࢿࣝࢠ࣮࡛࠶ࡾ㸪ῧ࠼Ꮠ &㸪' ࠾ࡼࡧ $ ࡣࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮࠿ࡽ࡞ࡿ㘒య &RPSOH[ 㸪'RQRU ࠾ࡼࡧ $FFHSWRUࢆ⾲ࡍ㸬P ࡜ Q ࡣࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮ࡢ㟁Ꮚᩘࢆ⾲ࡍ㸬3(6 ࡢ໙㓄࡜࣊ࢩ࢔ࣥࡶྠᵝ࡟ィ⟬ࡍࡿ㸬

㛤Ⓨᡭἲࢆ㔠ᒓ㘒య>0 / Q@㛫ࡢ⮬ᕫ㟁Ꮚ஺᥮཯ᛂ࡟㐺⏝ࡋ㸪ᡭἲࡢᛶ⬟ࢆホ౯ࡋࡓ㸬ࡲࡓ㸪㘒య஧㔞య࡟
㛤Ⓨᡭἲࢆ㐺⏝ࡋ࡚ (7 ๓ᚋ  ≧ែࢆィ⟬ࡋ㸪ᡃࠎࡢ *550 ࣉࣟࢢ࣒ࣛ࡟ࡼࡾ 3(6 ஺ᕪ㡿ᇦෆᵓ㐀 6HDP RI
&URVVLQJ 6; ࢆ᭱㐺໬ࡋ㸪࣐࣮࢝ࢫ⌮ㄽࡢ㏿ᗘᘧ࠿ࡽ N(7 ࢆィ⟬ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ *DXVVLDQ ࡢ ')7
ィ⟬ࢆ⏝࠸㸪ỗ㛵ᩘ࡜ᇶᗏ㛵ᩘࡣ 8%/<3'HI69 3 ࠾ࡼࡧ⁐፹ࡢ⪃៖࡟ࡣ &3&0 :DWHU ࢆ⏝࠸ࡓ㸬ࡲࡓ㸪୍Ⅼィ⟬࡟ࡣ 8%/<3'HI7=93 ࢆ⏝࠸ࡓ㸬࠸ࡎࢀࡢィ⟬࡛ࡶ *ULPPH ࡟ࡼࡿศᩓຊ⿵ṇ *' ࢆ⏝࠸࡚࠾ࡾ㸪஧㔞యࡢ⮬⏤࢚ࢿࣝࢠ࣮࡟ࡣ⤒㦂ⓗ࢚ࣥࢺࣟࣆ࣮⿵ṇ íNFDOPRO ࢆຍ࠼࡚࠸ࡿ㸬 ࢔ࢼࢱ࣮ࢮᆺ 7L2  㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂᶵᵓࡢ⌮ㄽゎᯒᮏ◊✲࡛ࡣ 7L2  㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂ࡟╔┠ࡋ㸪$),5 ἲ࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓ㸬㟁Ꮚ≧ែィ⟬ࡣ 6,(67$ ࣉࣟࢢ࣒ࣛࢆ⏝࠸㸪3%(''=3 ࡛ࣞ࣋ࣝ⾜ࡗࡓ㸬᥈⣴࡟⏝࠸ࡓ⾲㠃ᵓ㐀ࡣ îî ᒙࡢࢫࣛࣈࣔࢹࣝ࡜ࡋ㸪c ࡢ┿✵ᒙࢆ☜ಖࡋࡓ㸬⾲㠃ࣔࢹࣝ࡜ࡋ࡚Ύί⾲㠃㸪ࣉࣟࢺࣥ໬⾲㠃㸪㓟⣲Ḟ㝗⾲㠃ࡢ ✀㢮ࡢ⾲㠃ࣔࢹࣝࢆసᡂࡋ࡚཯ᛂ⤒㊰᥈⣴ࢆᐇ᪋ࡋࡓ㸬ྛ᥈⣴࡟ࡼࡾᚓࡽࢀࡓ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ࠿ࡽ
୺せ࡞ᚊ㏿㐣⛬ࢆᢳฟࡋ㸪ࡉࡽ࡞ࡿᵓ㐀᭱㐺໬ࢆ⾜࠺ࡇ࡜࡛ࢠ㓟⇕ศゎ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆᚓ
ࡓ㸬ࡇࢀ࡟ࡼࡾ㏿ᗘㄽⓗ࡟᭱ࡶ᭷฼࡞཯ᛂ⤒㊰ࢆ≉ᐃࡋ㸪཯ᛂᶵᵓࢆỴᐃࡋࡓ㸬 ⇕ⓗ +XLVJHQ ཯ᛂ⏕ᡂ≀ࡢ఩⨨㑅ᢥᛶไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲࢔ࢪࢻ࡜࢔ࣝ࢟ࣥࡢ⨨᥮ᇶࡢೃ⿵ࢆ  ✀㢮ࡎࡘ⏝ពࡋ㸪   ㏻ࡾࡢ୰࠿ࡽ ఩㑅ᢥᛶࢆ᭱኱໬ࡍ
ࡿ⨨᥮ᇶ⤌ࡳྜࢃࡏࢆ᥈⣴ࡋࡓ㸬ᵓ㐀᥈⣴ࡣ $),5 ἲࢆ⏝࠸࡚ %/<3'GHI693%/<3'GHI7=933 ࡛ࣞ࣋ࣝ⾜࠸㸪60' ἲ࡛ '0) ࡢ⁐፹ຠᯝࢆ⪃៖ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓ㸬࢞࢘ࢫ㐣⛬ᅇᖐࡢᐇ⿦࡟ࡣ *3\7RUFK ࢆ⏝࠸㸪≉ᚩ㔞࡟ࡣྛᇶ㉁࠾ࡼࡧࢺࣜ࢔ࢰ࣮ࣝ⎔࠿ࡽᢳฟࡉࢀࡓ㟁Ꮚⓗ࣭❧యⓗᅉᏊࢆ౑⏝ࡋࡓ㸬࣮࢝ࢿࣝ㛵ᩘ࠾ࡼࡧࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱࡣ㸪஺ᕪ᳨ドࡢࢫࢥ࢔ࡀ᭱኱࡜࡞ࡿ⤌ࡳྜࢃࡏࢆࢢࣜࢵࢻࢧ࣮ࢳࡋ࡚Ỵᐃࡋࡓ㸬⋓ᚓ㛵ᩘ࡟ࡣ 8SSHUFRQILGHQWERXQG 㛵ᩘࢆ⏝࠸㸪.ULJLQJEHOLHYHU ࢔- 295 -

ࣝࢦࣜࢬ࣒ࢆ฼⏝ࡋ࡚  ᗘ࡟  ಶ࡙ࡘ⨨᥮ᇶ⤌ࡳྜࢃࡏࢆᥦ᱌ࡋࡓ㸬୪⾜ࡋ࡚㸪ணࡢࣟ࣎ࢵࢺྜᡂ⿦⨨࡟ࡼࡿᐇ㦂ᐇドࡶ㐍ࡵࡓࡀ㸪ࡑࡢヲ⣽ࡣࡇࡇ࡛ࡣ๭ឡࡍࡿ㸬 ໬Ꮫ཯ᛂࡢỈࢡࣛࢫࢱ࣮ෆ࡟࠾ࡅࡿάᛶ఩⨨࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Ỉ  ศᏊ࠿ࡽ࡞ࡿỈࢡࣛࢫࢱ࣮࡟཯ᛂ≀࡛࠶ࡿ࢔ࢭࢺࣥ࠾ࡼࡧ࢔ࣥࣔࢽ࢔ࢆ㓄⨨ࡋࡓ㸬ᵓ㐀ࡢࢧࣥࣉࣜ
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ࡓ㸬ࡲࡓ㸪ィ⟬ࡀ఩⨨㑅ᢥᛶࢆ㐣኱ホ౯ࡍࡿഴྥࡀ☜ㄆࡉࢀࡓ㸬௒ᚋ㸪ࡇࡢィ⟬ㄗᕪࡢせᅉ࡟ࡘ࠸࡚㸪ࡉࡽ- 296 -

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>@;u, W.; Nagata, Y.; Kumagai, N. J. Am. Chem. Soc. 2023, 145, 2609.

>@:atanabe, A. ‡; Hama, K.‡; Watanabe, K.; Fujiwara, Y.;Yokoyama,K.; Murata, S.; Takita, R.
Angew. Chem. Int. Ed. 2022, 61, e202202779. (‡ co-first authors)- 303 -

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᪂ࡋ࠸୙ᩧ᭷ᶵศᏊゐ፹࠾ࡼࡧ㑄⛣㔠ᒓ㘒యゐ፹ࡢ๰〇◊✲ࡣࠊ㏆ᖺࡢ᭷ᶵྜᡂ໬Ꮫ࡟࠾࠸࡚㔜せ࡞◊✲ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ࠊᮏィ⟬ᶵࢆ฼⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊ᪂ࡋ࠸୙ᩧゐ፹ࡢタィࢆ┠ᣦࡍ࡜࡜ࡶ࡟ࠊ᪂
཯ᛂࡢ㛤Ⓨࠊタィࡋࡓゐ፹ᵓ㐀ࡢゎ᫂ࠊ࠾ࡼࡧࡑࡢᶵ⬟ゎ᫂ࢆ┠ᣦࡍࠋࡲࡓࠊᶵᲔᏛ⩦࡟ࡼࡿ᪂ࡓ࡞୙ᩧゐ፹タィ࡟ࡶྲྀࡾ⤌ࡴࡇ࡜࡛ࠊ⤫ィᏛⓗ࡞ゐ፹タィࢆ⾜࠺ࠋ◊✲᪉ἲࠊィ⟬᪉ἲ᪂ࡋࡃタィ࣭ྜᡂࡋࡓ୙ᩧゐ፹࡟㛵ࡋ࡚ᵓ㐀ࡢ᭱㐺໬ࢆ⾜࠸ࠊゐ፹άᛶ࡜ࡢ㛵㐃ᛶࢆㄪᰝࡍࡿ࡜࡜ࡶ࡟ࠊ

ᚓࡽࢀࡓ❧య㑅ᢥᛶࡢⓎ⌧ᶵᵓࡢゎ᫂࡟ᙺ❧࡚ࡓࠋ㔞Ꮚ໬Ꮫィ⟬࡛ࡣࠊGaussian 09 ࠾ࡼࡧ 16 ࣉࣟࢢ࣒ࣛࢆ
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࡞ࡗࡓࠋࡉࡽ࡟ࠊDistortion-Interaction ゎᯒ㸦ୗᅗྑ㸧ࢆ⾜࠺ࡇ࡜࡛ࠊ❧య㑅ᢥᛶ࡟ࡣゐ፹ᵓ㐀ࡢṍࡳࡢຠᯝࡀ኱ࡁ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓࠊNBO ゎᯒࠊNCI ゎᯒࢆ⾜࠺ࡇ࡜࡛ࠊ┦஫స⏝࢚ࢿࣝࢠ≧ែࡢゎᯒࢆ⾜࠸཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

ࡉࡽ࡟ࠊࡇࢀࡲ࡛࡟඲ࡃ୙ᩧྜᡂ཯ᛂࡀ᳨ウࡉࢀ࡚࠸࡞࠸⎔≧ࢣࢳ࣑ࣥ࡬ࡢ࢔ࣞࢽࣝ໬཯ᛂࢆ᳨ウࡋࡓ࡜ࡇࢁࠊࡇࢀࡲ࡛◊✲ᐊ࡛㛤Ⓨࡋ࡚ࡁࡓࣅࢫ࢖࣑ࢲࢰࣜࣥ-ࣃࣛࢪ࣒࢘ࡨࢇࡉ࣮ゐ፹ࢆ⏝࠸ࡿࡇ࡜࡛㧗❧య㑅ᢥ

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࣒࢘✀ࡢ཯ᛂ୰㛫య㛫ࡢᖹ⾮ࡀ㔜せ࡛࠶ࡾࠊ୙Ᏻᐃ࡞୰㛫య㘒య࠿ࡽᏳᐃ࡞㑄⛣≧ែࢆ⤒⏤ࡋ㸦ୗᅗྑ㸧ࠊ㧗❧య㑅ᢥⓗ࡟࢔ࣞࢽࣝ໬⏕ᡂ≀ࢆ୚࠼ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

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ࢫ࣍ࣜࣝ໬཯ᛂࡢ㛤Ⓨ‫ۑ‬ᑠ಴࿴ᶞ࣭஬༑ఫ୍ᶞ࣭୰ᮧಟ୍
‫➨ۻ‬㸲㸶ᅇ཯ᛂ࡜ྜᡂࡢ㐍Ṍࢩ࣏ࣥࢪ࣒࢘ࠊ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻ࡟ࡼࡿ↓ಖㆤࢣࢳ࣑ࣥ࡬ࡢ୙ᩧࣄࢻࣟ࣍ࢫ
࣍ࢽࣝ໬཯ᛂࡢ㛤Ⓨ‫ۑ‬ᑠ಴࿴ᶞ㸪஬༑ఫ୍ᶞ㸪୰ᮧಟ୍௚㸰㸮௳ࡢᏛ఍Ⓨ⾲ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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,PLGD]ROLQH3KRVSKRULF $FLGV .D]XNL 2JXUD ,WVXNL ,VR]XPL 7VXQD\RVKL 7DNHKDUD 7DNH\XNL 6X]XNL 6KXLFKL1DNDPXUD 2UJDQLF/HWWHUV    
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㓟໬≀⤖ᬗ࠾ࡼࡧ⼥య࡟࠾ࡅࡿᵓ㐀⦆࿴ࢆ㥑ືຊ࡜ࡋࡓ୙つ๎㘒యᵓ㐀ࡢ⮬Ⓨⓗᙧᡂ㐣⛬ࡢゎᯒ(YDOXDWLQJIRUPDWLRQPHFKDQLVPRIFRPSOH[LRQLFVWUXFWXUHLQGXFHGE\VWUXFWXUDOUHOD[DWLRQLQR[LGHFU\VWDORUPHOW‫ۑ‬㕥ᮌ ㈼⣖㸦኱㜰኱Ꮫ㸧◊✲┠ⓗࢣ࢖㓟 6L2 ࢆ୺ᡂศ࡜ࡍࡿ㓟໬≀ࡣ㸪㝧࢖࢜ࣥ࡜㓟⣲࢖࢜ࣥࡢ㛫࡟ඹ᭷⤖ྜᛶࡢᙉ࠸⤖ྜࢆᙧᡂࡋ㸪࢖࢜ࣥྠኈࡢ㓄⨨㛵ಀ ࡟኱ࡁ࡞ไ⣙ࢆక࠺㸬⤖ᬗࡸ⁐⼥య࡟࠾࠸࡚ࡣ㏻ᖖ㸪༢఩᱁Ꮚࡸ୰㊥㞳ᵓ㐀ࡢ⠊ᅖෆ࡛⤖ྜࡢᆒ⾮ࡀಖࡓࢀࡿࡀ㸪ᒁᡤⓗ࡞⤖ྜࡢ୙ᆒ⾮ࡀᑟධࡉࢀࡿ࡜௚ࡢ≀㉁⣔ࡼࡾࡶ኱ࡁ࡞㐣๫࢚ࢿࣝࢠ࣮ࡀ
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୙᫂࡞ࡓࡵ⾲㠃ᙇຊࡢணࡣ㠀ᖖ࡟㞴ࡋ࠸㸬⁐⼥㓟໬≀ࡢ⾲㠃ᙇຊࡣ㸪㔠ᒓ〇㘐ࡸ࢞ࣛࢫ〇㐀࡟࠾ࡅࡿ⏺㠃⌧㇟ࢆᨭ㓄ࡍࡿ㔜せ࡞≀ᛶ࡛࠶ࡾ㸪ᗘࡸ⤌ᡂ࡟ᑐࡍࡿ౫Ꮡᛶࢆṇ☜࡟ணࡍࡿయ⣔ࡢ☜❧ࡀồࡵࡽࢀࡿ㸬ⴭ⪅ࡣࡇࢀࡲ࡛㸪኱ᆺᨺᑕග᪋タࢆ⏝࠸ࡓ࢞ࣛࢫヨᩱ࡟ᑐࡍࡿ㌾ ; ⥺྾཰ศගศᯒ࡜⾲㠃ࢆྵࡴ⼥యࣔࢹࣝ࡟ᑐࡍࡿศᏊືຊᏛ㸦0'㸧ィ⟬ࡢ」ྜ◊✲࡟ࡼࡗ࡚㸪⁐⼥㓟໬≀ࡢ⾲㠃⦆࿴ᶵᵓ࠾ࡼࡧ⾲㠃⦆࿴ࡀ⏕ࡌࡓᚋࡢ࢖࢜ࣥ㓄఩ᵓ㐀ࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓ㸬$O2&D2 ⣔⼥య࡟ࡘ࠸࡚⾲㠃ᙇຊࡀ୰㛫ࡢ⤌ᡂ࡛ᴟᑠ್ࢆ♧ࡍഴྥ  ࡟ὀ┠ࡋ㸪$O2 ࡜ &D2 ࡢ⤌ᡂẚࡀ✀ࠎ␗࡞ࡿ⤌ᡂ࡟ࡘ࠸࡚⾲㠃⦆࿴ᚋࡢ࢖࢜ࣥ㓄఩ᙧែࢆゎᯒࡋࡓ⤖ᯝ㸪$O2 ⃰ᗘࡀ 㹼PROࡢ⠊ᅖ࡛ࡣ⾲㠃㡿ᇦ࡛ࡣᯫᶫ㓟⣲㸦$O2$O㸧ࡀ㠀ᯫᶫ㓟⣲㸦$O2&D㸧ࡼࡾࡶᏑᅾ⋡ࡀ┦ᑐⓗ࡟㧗࠸ࡇ࡜ࢆぢฟࡋࡓ㸬ࡍ࡞ࢃࡕ㸪ྠ⼥యࡢ⾲㠃࡛ࡣ $O࢖࢜ࣥࡀ &Dࢆ㟁Ⲵ⿵ൾ࢖࢜ࣥ
࡜ࡋ࡚క࠸ $O2 㓄఩ᵓ㐀ࢆᙧᡂࡋ㸪ࡑࢀࡽࡀ㐃⤖ࡋ࡚ᯫᶫ㓟⣲ࢆᙧᡂࡋ᫆࠸㸬ࡋࡓࡀࡗ࡚㸪⁐⼥㓟໬≀࡟࠾࠸࡚ࡣඹ᭷⤖ྜᛶࡢᙉ࠸⤖ྜࢆకࡗࡓᯫᶫ㓟⣲ࡢඃඛⓗᙧᡂࡀ㸪⾲㠃ᵓ㐀⦆࿴ࡢᨭ㓄ⓗ࡞ᶵᵓ࡜⪃࠼ࡽࢀࡿ㸬ୖグࡢྍ⬟ᛶࢆ᳨ドࡍࡿࡓࡵ࡟㸪ᮏ◊✲࡛ࡣ⾲㠃άᛶᡂศ࡛࠶ࡾ  㸪༢⊂࡛ᯫᶫ㓟⣲ࢆᙧᡂࡍࡿ 6L2 ࡢῧຍࡀ⾲㠃࢖࢜ࣥᵓ㐀࡟୚࠼ࡿᙳ㡪࡟ὀ┠ࡋࡓ㸬$O2&D2 ⤌ᡂẚࢆᅛᐃࡋ࡚ 6L2 ࢆῧຍࡋࡓ⤌ᡂ࡟ࡘ࠸࡚㸪࢖࢜ࣥ㛫ࡢศᴟస⏝ࢆ⪃៖ࡋࡓ 3RODUL]DEOH LRQ PRGHO  ࢆ⏝࠸࡚ 0' ィ⟬࡟ࡼࡗ࡚Ẽᾮ⏺㠃ࢆྵࡴ⼥యࡢᵓ㐀ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋ㸪㌾ ; ⥺ศගศᯒࡢᐇ㦂⤖ᯝ࡜ྜࢃࡏ࡚㸪⾲㠃࢖࢜ࣥ㓄఩ᵓ㐀ࡢゎᯒࢆ⾜ࡗࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ
3RODUL]DEOH LRQ PRGHO㸦3,0㸧ࡣྛ✀࢖࢜ࣥ㛫࡟ാࡃศᴟ࣮࣓ࣔࣥࢺ ȝ ࢆศᴟ⋡ࣃ࣓࣮ࣛࢱ Į ࡜㟁ሙ ( ࡢ✚࡟ࡼࡗ࡚⾲ࡋࡓࡶࡢ࡛࠶ࡿ㸬┦஫స⏝࢚ࢿࣝࢠ࣮ࡣ௨ୗࡢ㛵ᩘࢆ⏝࠸࡚ホ౯ࡋࡓ㸬߶൫‫ݎ‬௜௝ ൯ ൌ

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ࣆ࢏ ή௤ೕ ࢘࢏࢐
య
௥೔ೕ

௜௝

݂ସ ൅

ࣆ࢏ ήࣆ࢐
య௥೔ೕെଷ൫࢘࢏࢐ ήࣆ࢏ ൯ή൫࢘࢏࢐ ήࣆ࢐ ൯ఱ௥೔ೕ൅ ߶ ௗ௜௦௣ ൫‫ݎ‬௜௝ ൯                   

ULM ࡣ⢏Ꮚ LM 㛫ࡢ㊥㞳ࠊTLȝL ࡣ⢏Ꮚ L ࡢ㟁Ⲵ࡜཮ᴟᏊ࣮࣓ࣔࣥࢺࢆ⾲ࡍ㸬➨  㡯࠿ࡽ➨  㡯ࡲ࡛ࡢ┦஫స⏝ࣃ࣓࣮ࣛࢱࡣ➨୍ཎ⌮ 0' ィ⟬࠿ࡽᚓࡽࢀࡿྛ࢖࢜ࣥࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜ຊࢆ෌⌧ࡍࡿࡼ࠺Ỵᐃࡉࢀࡓࡶࡢ
࡛࠶ࡿ㸬ᮏ◊✲࡛ࡣᩥ⊩  ࡟グ㍕ࡢࣃ࣓࣮ࣛࢱࢭࢵࢺࢆ฼⏝ࡋ࡚ィ⟬ࢆ⾜ࡗࡓ㸬- 309 -

ィ⟬ᡭ㡰࡟ࡘ࠸࡚ࡣ㸪ࡲࡎ  ಶ⛬ᗘࡢཎᏊࢆࣛࣥࢲ࣒㓄⨨ࡋࡓ❧᪉యࢭࣝ࡟ࡘ࠸࡚ศᴟࢆ⪃៖ࡋ࡞࠸ຊ
ሙ㸦5LJLG,RQ0RGHO5,0㸧㸪ࡑࡢᚋ 3,0 ࡟ࡼࡿ 0' ィ⟬ࢆᐇ⾜ࡋ㸪୍ᐃᗘ࡛ᖹ⾮໬ࡉࡏࡓ㸬ḟ࡟ࢭࣝࢧ࢖

ࢬࢆ୍㍈᪉ྥ࡟  ಸᣑᙇࡋ࡚ྠᵝࡢᡭ㡰࡛ᖹ⾮໬ࡉࡏࡓᚋ㸪㍈᪉ྥࡢ୧➃࡟┿✵┦ࢆ㓄⨨ࡍࡿࡇ࡜࡟ࡼࡗ࡚
Ẽᾮ⏺㠃ࢆᑟධࡋ㸪෌ᗘᖹ⾮໬ࡉࡏࡓ㸬௨ୖ࡛ࡣ 3,0 㛤Ⓨ⪅࡛࠶ࡿ▼஭ⰋᶞẶ㸦රᗜ┴❧኱Ꮫ㸧ࡀ㛤Ⓨࡋࡓィ⟬ࢥ࣮ࢻࢆ౑⏝ࡋ㸪197 ࢔ࣥࢧࣥࣈࣝ࡟࡚ィ⟬ࢆᐇ⾜ࡋࡓ㸬ࢭࣝෆࡢ඲࢚ࢿࣝࢠ࣮㸦ࣁ࣑ࣝࢺࢽ࢔ࣥ㸧ࡀ࡯ࡰ୍ᐃ್࡟཰᮰ᚋ㸪Ẽᾮ⏺㠃㏆ഐ࠾ࡼࡧෆ㒊࡟࠾ࡅࡿ 2$O2㸪26L2 ࡢ⤖ྜゅศᕸࢆ⤫ィゎᯒࡋ㸪࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ T ࢆ⏝࠸ࡓゎᯒ  ࡟ࡼࡗ࡚ $O2[㸪6L2[㸦[ 㸧㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸࡢホ౯ࢆ⾜ࡗࡓ㸬◊✲ᡂᯝ$O2&D2 ࣔࣝ⤌ᡂẚࢆ  ࡟ᅛᐃࡋࠊ6L2 ࢆ 㹼 PROῧຍࡋࡓ  ඖ⣔⼥య࡟ࡘ࠸࡚㸪⾲㠃ࢆྵࡴᵓ㐀ࣔࢹࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ㸬. ࡛ᖹ⾮໬ࡉࡏࡓᵓ㐀ࣔࢹࣝࡢ୍౛ࢆᅗ  ࡟♧ࡍ㸬ᮏィ⟬᮲௳࡟࠾࠸࡚㸪ୖグࡢ 6L2 ⃰ᗘࡢ⠊ᅖ࡛ࡣ㸪6L ཎᏊࡀ⾲㠃㏆ഐ࡟೫ᯒࡍࡿഴྥࡣ≉ẁぢࡽࢀ࡞࠿ࡗࡓ㸬ࡋ࠿ࡋ㸪6L2[

ᅗ 1. $O2&D26L2 ⣔⼥యࡢ⾲㠃ࢆྵࡴᵓ㐀ࣔࢹࣝ㸦 ཎᏊࠊ㟷ከ㠃య6L2[ ㉥ከ㠃య$O2[㸪ⓑ୸&D ࢆ⾲ࡍ㸧࠾ࡼࡧ $O2[ 㓄఩ᵓ㐀ࡢศᕸ࡟ࡘ࠸࡚ࡣ⾲㠃㏆ഐ࡜ෆ㒊ࡢẚ㍑࡟࠾࠸࡚᫂░࡞㐪࠸ࡀぢࡽࢀࡓ㸬ᅗ  D ࡟♧
ࡍ 6L2[ 㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸ࡟࠾࠸࡚㸪6L2 ⃰ᗘࡀࡢሙྜࡣᵝࠎ࡞㓄఩ᩘࡢ 6L2[ ከ㠃యࡀᏑᅾࡍࡿࡀ㸪⾲㠃㏆ഐ࡛ࡣෆ㒊࡟ẚ࡭࡚ 6L2 ࡢᏑᅾ⋡ࡀഹ࠿࡟㧗࠸㸬୍᪉㸪ᅗ  E ࡟♧ࡍ $O2[ 㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸ࡟ࡘ࠸࡚㸪6L2 ⃰ᗘࡢቑຍ࡟క࠸⾲㠃ࠊෆ㒊࡜ࡶ࡟ $O2࡟ẚ࡭ $O2$O2 ࡢᏑᅾ⋡ࡀቑຍࡍࡿࡀࠊ⾲㠃࡛ࡣෆ㒊࡟ẚ࡭࡚ $O2 ࡢᏑᅾ⋡ࡀ┦ᑐⓗ࡟㧗࠸ഴྥࡀ♧ࡉࢀࡓ㸬ࡉࡽ࡟㸪6L26L$O2$O$O26L ࡢ⤖ྜゅศᕸ

ᅗ 2. (a) 6L2[ 㓄఩ᵓ㐀㸪(b) $O2[ 㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸ㸦㉥⥺㸸⾲㠃 6XUI 㸪㯮⥺㸸ෆ㒊 %XON 㸧ࢆ⤫ィゎᯒࡋࡓ⤖ᯝ㸪࠸ࡎࢀࡶ⾲㠃࡛ࡣෆ㒊࡟ẚ࡭࡚ᅄ㠃యྠኈࡢ㡬Ⅼඹ᭷ࢆ⾲ࡍ ș r௜㏆ࡢ⤖ྜゅࡢᏑᅾ⋡ࡀ㧗࠸ࡇ࡜ࡀ♧ࡉࢀࡓ㸬௨ୖࡢ⤖ᯝ࠿ࡽ㸪$O2&D2 ⣔⼥య࡟ 6L2 ࢆῧຍࡍࡿ࡜⾲㠃࡛ࡣ 6L2 ࡲࡓࡣ$O2 㓄఩ᵓ㐀ࡀඃඛⓗ࡟ᙧᡂࡉࢀ㸪ࡑࢀࡽࡀ஫࠸࡟㐃⤖ࡋ࡚ᯫᶫ㓟⣲ࢆᙧᡂࡍࡿ࡜࠸࠺⾲㠃⦆࿴ᶵᵓࡀ᪂ࡓ࡟ぢฟࡉࢀࡓ㸬௨ୖࡢഴྥࡣ㸪ᨺᑕග᪋タ࡟࠾ࡅࡿ㌾ ; ⥺ศගศᯒ㸦ィ⟬࡛ᢅࡗࡓࡢ࡜ྠࡌ⤌ᡂࡢ⼥యࢆᛴ෭ࡋ㸪⾲㠃⦆࿴ࡢ⇕ฎ⌮ࢆ᪋ࡋࡓ࢞ࣛࢫヨᩱ࡟ᑐࡍࡿ⾲㠃ᵓ㐀ゎᯒ㸧ࡢᐇ㦂⤖ᯝ࡜ࡶᩚྜࡋࡓ㸬

Ⓨ⾲㸪ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@ 㕥ᮌ㈼⣖ࠊᱵဏ๎ṇࠊ▼஭Ⰻᶞ㸸[$O2 [ &D2 [   ⼥యࡢ⾲㠃⦆࿴ᶵᵓ࡟ᑐࡍࡿศᏊືຊ

Ꮫィ⟬ࠊ᪥ᮏ㔠ᒓᏛ఍➨  ᅇ⛅Ꮨㅮ₇኱఍ࠊ⚟ᒸᕤᴗ኱Ꮫࠊ ᖺ  ᭶  ᪥㸬ཧ⪃ᩥ⊩ 9 3(O\XWLQ%60LWLQ<6$QLVLPRY ,]Y9\VVK8FKHEQ=DYHG6HU7VYHWQ0HWDOOXUJ1RS   ྥ஭ᴋᏹ㸪▼ᕝ᭷⨾᪥ᮏ㔠ᒓᏛ఍ㄅ 9RO S   <,VKLL06DODQQH7&KDUSHQWLHU.6KLUDNL..DVDKDUD12KWRUL3K\V&KHP&9ROS   -5(UULQJWRQ3*'HEHQHGHWWL 1DWXUH /RQGRQ  9ROS  - 310 -

ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂(OXFLGDWLRQRIDGKHVLRQPHFKDQLVPRIKLJKO\DGKHVLYHSURWHLQLQZDWHU
E\PROHFXODU G\QDPLFVVLPXODWLRQ
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⣧ࠊᇼ

ඞᩄ㸦ྡྂᒇ኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧◊✲┠ⓗࠊෆᐜ
⣽⳦ $FLQHWREDFWHU6S 7RO ࡣࠊ$WD$ ࡜࿧ࡤࢀࡿ඲㛗⣙ QP ࡢᕧ኱⧄⥔≧ࢱࣥࣃࢡ㉁  ṧᇶࡢ࣏ࣜ࣌ࣉࢳࢻ㙐ࡢ  㔞యࠊศᏊ㔞 N'D ࢆ⣽⬊⾲ᒙ࡟ᣢࡗ࡚࠾ࡾࠊ$WD$ ࢆ௓ࡋ࡚ࣉࣛࢫࢳࢵࢡࠊ㔠ᒓࠊ࢞ࣛࢫ
➼ࡢᵝࠎ࡞≀㉁ࡢ⾲㠃࡟ᙉࡃ᥋╔ࡍࡿࠋ$WD$ ࡢ᥋╔ᛶࡣࠊ୺࡟ࠊࡑࡢඛ➃࡟࠶ࡿ 1KHDG ࡜࿧ࡤࢀࡿࢻ࣓࢖ࣥ ศᏊ㔞 N'D ࡀᢸࡗ࡚࠾ࡾࠊ1KHDG ༢⊂࡛␯Ỉᛶ࠿ࡽぶỈᛶ࡟⮳ࡿᵝࠎ࡞ᮦᩱ㠃࡟ᑐࡋ࡚Ỉ୰࡛ᙉ࠸᥋╔ᛶࢆ♧ࡍ㸦ᅗ㸯㸧ࠋ᥋╔ᶵᵓゎ᫂ࡢࡓࡵ࡟ࠊࡇࢀࡲ࡛࡟⤖ᬗゎᯒ Koiwai K, et al., J Biol
Chem. 291(8), 3705-24(2016). ࠊ ⇕ ኚ ᛶ ᐇ 㦂
Yoshimoto S, et al., Sci Rep. 6:28020 (2016) ࠊ$)0 ࡟ࡼ ࡿ ᥋ ╔ ຊ ࡢ ┤ ᥋ ほ ᐹ Ishii S, et al., J Colloid
Interface Sci. 606, 628-634 (2022) ࠊ4&0' ࡟ࡼࡿ᥋╔᫬ࡢ⭷ཌ௕‫ ڭ‬1KHDG ध‫گ‬णभமାঝ‫ش‬উᐃ ᢞ✏‽ഛ୰ ࢆ⾜ࡗࡓࠋࡲࡓࠊ㈗ࢭࣥࢱ࣮ࡢࢫࣃࢥࣥࢆ౑ࡗࡓศᏊືຊᏛィ⟬㸦MD ィ⟬㸧࡟ࡼࡾࠊ᥋╔࡟㛵୚ࡍࡿ࢔࣑ࣀ㓟ṧᇶࡢྠᐃࠊ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬ࠊ᥋╔࡟ࡼࡾࢱࣥࣃࢡ㉁࡟㉳ࡇࡿࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ࡢゎᯒࢆ⾜ࡗ࡚ࡁࡓࠋ௧࿴ 3 ᖺᗘࡢ᪋タ฼⏝㸦B㸧࡛ࡣࠊ᥋╔㐣⛬ࡢ MD ࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟࠿ࡽࠊNhead ࡣࠊࡑࡢศᏊ⾲㠃࠿ࡽ㣕ࡧฟࡋ࡚࠸ࡿ㸱ࡘࡢ࣮ࣝࣉ L1ࠊL2ࠊL3 ࢆ౑ࡗ࡚ᮦᩱ⾲㠃࡟᥋╔ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࠊ≉࡟ࠊࡇࢀࡽࡢ࣮ࣝࣉ࡟࠶ࡿ 17 ಶࡢ࢔࣑ࣀ㓟ࡀ᥋╔࡟㛵୚ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࡓࡵࠊࡇࢀࡽࡢኚ␗ᐇ㦂ࢆ⾜࠸ࠊኚ␗࡟ࡼࡾ Nead ࡀᮦᩱ࡬ࡢ᥋╔ᛶࢆኻ࠺ࡇ࡜ࢆ☜ㄆࡋࡓࠋࡲࡓࠊࡇࢀࡽ㸱ࡘࡢ࣮ࣝࣉࡣࠊ⇕㐠ືᛶࡀ㧗ࡃࠊᮦᩱ⾲㠃ࡢพฝ࡟ࣇ࢕ࢵࢺࡍࡿᰂ㌾ᛶࢆഛ࠼࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡓࠋ
ࡑࡇ࡛ࠊ௧࿴ 4 ᖺᗘࡣࠊࡇࢀࡽࡢ࣮ࣝࣉ࡟ࣉࣟࣜࣥࡸ S-S ⤖ྜࢆᑟධࡋ࡚ᰂ㌾ᛶࢆపୗࡉࡏࡓ࡜ࡁ࡟᥋╔ᶵ⬟࡟࡝ࡢࡼ࠺࡞ᙳ㡪ࡀཬࡪ࠿ࢆゎᯒࡍࡿ࡜࡜ࡶ࡟ࠊࡇࢀࡽࡢ࣮ࣝࣉࢆ௚ࡢࢱࣥࣃࢡ㉁࡟⛣᳜ࡍࡿࡇ࡜࡟ࡼࡾ
௚ࡢࢱࣥࣃࢡ㉁࡟ࡶ᥋╔ᛶࢆ௜୚࡛ࡁࡿ࠿࡝࠺࠿ࢆ MD ィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Nhead ࡢ㸱ࡘࡢ࣮ࣝࣉࡢᵓ㐀ࢆヲ⣽࡟᳨ウࡋ࡚ࠊࣉࣟࣜࣥ࡬ࡢ⨨᥮ࡸ S-S ⤖ྜࡢᑟධ࡟ࡼࡾᵓ㐀ࢆṍࡲࡏࡿࡇ࡜࡞ࡃ࣮ࣝࣉࡢ㐠ືᛶࢆపୗࡉࡏࡿ࡜⪃࠼ࡽࢀࡿ㒊఩ࢆ」ᩘ㑅ࡧࠊ࣮ࣝࣉ࡟ࡇࢀࡽࡢṧᇶࢆᑟධࡋࡓኚ
␗యࡢᵓ㐀ࣔࢹࣝࢆసᡂࡋࡓࠋࡇࡢኚ␗యࢆࠊ࣏ࣜࢫࢳࣞࣥ㸦PS㸧
ᇶ┙࠿ࡽ 10ύࡢ㊥㞳࡟㓄⨨ࡋࠊ301Kࠊ1atm ࡟࠾࠸࡚ 50ns ࡢ MDィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊኚ␗యࡢᇶ┙࡬ࡢ᥋╔ࢆࢩ࣑࣮ࣗࣞࢺࡋ
ࡓࠋࡲࡓࠊNhead ࡢ᥋╔࡟㛵ࢃࡿ࣮ࣝࣉࢆࢢࣝࢱࢳ࢜ࣥ S-ࢺࣛࣥࢫࣇ࢙࣮ࣛࢮ㸦GST㸧ࠊ࣐ࣝࢺ࣮ࢫ⤖ྜࢱࣥࣃࢡ㉁㸦MBP㸧ࠊ࢘ࢩ௕‫ڮ‬

1KHDG भமା३঑গঞ‫ش‬३ঙথ⾑Ύ࢔ࣝࣈ࣑ࣥ㸦BSA㸧࡟⛣᳜ࡋࠊྠᵝࡢ MD ィ⟬࡟ࡼࡾࠊPS ᇶ┙࡬ࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢱ- 311 -

ࣥࣃࢡ㉁࡜ᇶ┙࡜ Nhead 㛫ࡢᖹᆒຊ㸦PMF㸧ࡢ⟬ฟࡣࠊ୧⪅ࡢ㛫ࡢ㊥㞳ࢆ㸫1 nm ࠿ࡽ 10 nm ࡲ࡛ 0.05 nm 㛫㝸࡛ኚ࠼࡚ࠊࡑࢀࡒࢀࡢ㊥㞳࡟࠾࠸࡚ 10 ns ࡢ NPT ࢔ࣥࢧࣥࣈ࡛ࣝࡢ MD ィ⟬⾜࠸ࠊ2ps ẖ࡟ Nhead ࡟࠿࠿ࡿຊࢆࢧࣥࣉࣜࣥࢢࡋ࡚ࠊࡇࢀࢆᖹᆒࡍࡿࡇ࡜࡟ࡼࡾ⾜ࡗࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬ࡣࠊPMF ࢆ Nhead㸫PSᇶ┙㛫ࡢ㊥㞳࡟ἢࡗ࡚✚ศࡍࡿ࠸ࢃࡺࡿ⇕ຊᏛ✚ศἲ࡟ࡼࡾ⾜ࡗࡓࠋィ⟬ࡣࠊ඲࡚ࣉࣟࢢ࣒ࣛ GROMACS
2021.6 ࢆ⏝࠸࡚༢⢭ᗘ࡛⾜ࡗࡓࠋຊሙ࡟ࡣࠊCHARMM36m ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ㸱ࡘࡢ᥋╔࣮ࣝࣉࡢ㐠ືᛶࢆࠊMD ィ⟬

ࡢ㌶㊧࡟࠾ࡅࡿཎᏊᗙᶆࡢᦂࡽࡂ࡜ࡋ࡚ᐃ
㔞໬ࡋࡓ࡜ࡇࢁࠊ⇕ᦂࡽࡂࡢ኱ࡁࡉࡣࠊ
L1>L3>L2 ࡛࠶ࡗࡓࠋ୍᪉࡛ࠊᮦᩱ⾲㠃࡜ࡢ┦஫స⏝ࡢ㢖ᗘࡣࠊL3㸼L2>L1 ࡛࠶ࡾࠊ࡯
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ඹྠ◊✲⪅ࡢ➲ཎẶࡣࠊ2022 ᖺᗘ࡟༤ኈㄢ⛬ 2 ᖺ࡟࡛࠶ࡾࠊ࢙࢘ࢵࢺࡢᐇ㦂࡜ేࡏ࡚ᮏ◊✲ࡢᡂᯝࢆ 2023ᖺ୰࡟ㄽᩥᢞ✏ࡋࠊ༤ኈㄽᩥ࡟ࡲ࡜ࡵࡿணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 312 -

Computational Investigation of Colossal Dielectric Permittivity Materials
and Chemical Bonding Features of Transition Metal Dioxides (Usage Report)○ Pradeep R. Varadwaj and Ryoji Asahi(Institutes of Innovation for the Future Society, Nagoya University, Aichi 464-8601, Japan)

1

Introduction
Development of high-performance dielectric materials is necessary for device miniaturizationand high-energy density storage applications. The relative dielectric permittivity (Hrel) of dopped
material has shown to increase appreciably (about 2-3 orders of magnitude higher compared to thatof the parent system), especially when rutile TiO2 (R-TiO2) is appropriately co-doped with anappropriate main-group element and/or transition metal (viz. Nb/In). The mechanisms underlying thephenomenological enhancement have not been clarified both for the parent and dopped materials.
There is already a longstanding controversy on the inconsistency between the experimental values of
the ionic dielectric constant of many transition metal dioxides, including TiO2. For example, someearly works reported of the last century claimed colossal dielectric constant for the rutile phase of
TiO2, with Hrel values in the range, 102 – 104. Others have rejected such experimentally observed
claims since their experimental findings (Hrel values between 85 and 211 at different temperaturescales) cannot reproduce such large Hrel values reported in previous studies. Clearly, the research topic
is of significant interest, and the chemical physics and physical chemistry of parent and dopped TiO2
systems, as well as other transition metal dioxide materials with and without co-doping, are yet to be
examined both theoretically and experimentally. Therefore, this study was initiated with the aim toclarify the importance of factors (physical properties) responsible for the enhancement of the parent
TiO2 systems in various phases, as well as to propose dopped transition metal oxide-based materials
that feature large dielectric permittivity.
2

Methods
Density functional theory (DFT) calculations were performed using the Vienna Ab initio Simulation Package(VASP), which was accessible from the user’s account. As planned, several polymorphs of the crystal lattice of TiO2 wasinvestigated using DFT, employing periodic boundary conditions. The DFT functionals included the PBE, PBE+U (U =3.5 eV), PBEsol, PBEsol + U, SCAN and SCAN-rVV10. The results obtained from these calculations were benchmarked
against high-level of theory employed, HSEsol, and HSE06. Since one of the interests was to examine the effect of PAW
potentials and DFT functionals on the physical properties of the parent systems, three different PAW potentials (Ti, Ti_pv,
and Ti_sv) were employed. The polymorphs of TiO2 include rutile, brookite (B), anatase (A), pyrite (P), and fluorite (F)phases, which have been known at different temperature ranges in the crystalline phase.
The physical properties investigated were lattice constants, lattice density, lattice volume, energy stability, band
structure, density of states, charge density features, and mechanical properties. The latter property was evaluated to- 313 -

demonstrate the mechanical stability of the studied materials, including the evaluation of various elastic moduli (viz. Bulk,
Young moduli and Poisson's ratio, etc). The different levels of theory stated above, in conjunction with the three different
PAW potentials (Ti, Ti_pv, and Ti_sv), were utilized. Various k-meshes to sample the Brillouin zone and cut-off energies
for plane-wave and electronic loops for geometry convergence were invoked depending on the system size investigated.
Normal mode vibrations associated with the phonon modes were also calculated at different levels of theory, in
conjunction with the three different PAW potentials (Ti, Ti_pv, and Ti_sv), to demonstrate the dynamical stability of thepolymorphs of TiO2, and several dopped TiO2 materials. Density functional perturbation theory (DFPT) and Frozen
Phonon Finite Difference method (FPFDM) were used. The FPFDM calculates the force constant matrix by displacing
each atom in the crystal lattice and calculating the resulting forces on every other atom. For these calculations, 2u2 and3u3 supercells were used depending on the system size. The phonopy code was used. Gaussian 16 and other codes (ASE)
were used whenever essential and to explore the chemical bonding scenarios at molecular levels.

3

Results
As mentioned above, the polymorphs of TiO2 investigated include the rutile, brookite, anatase, pyrite, andfluorite phases, which are present in different temperature ranges of the crystalline phases. Since the dielectric properties,
especially ionic permittivity, are highly dependent on cutoff energy and k-mesh grid size, we tested the convergence of
cutoff energy and k-mesh. In particular, for each of the cutoff energies of 520, 600, 650, 700, and 750 eV, the k-meshesof 4u4u4 through 5u5u5 to 6u6u6, 7u7u7, 8u8u8, 9u9u9 to 10u10u10 were invoked. Each of these calculations,especially those involved, high k-mesh and cut-off energies were not only computationally expensive but also invoked agreater number of CPU cores. The results of the combined use of the PBEsol functional in conjunction with the standard
PAW potential centered on Ti indicated that the ionic permittivity of TiO2 polymorphs may be comparable to that reported
in inelastic scattering experiments. The use of high-level theory (HSEsol and HSE06) in combination with standard
potentials was very computationally expensive, but the results of dielectric permittivity obtained from this level of theory
were relatively more accurate in reproducing experimental dielectric constants. The density functional perturbation theory,
as well as frozen phonon approximation, was invoked. Table 1 shows, for example, a comparison of ionic (low-frequency)
and electronic (high-frequency) components (Hij(0) and Hij(λ), respectively) of the relative dielectric permittivity tensor Hrof R-, A- and B-TiO2, obtained using three cutoff energies (520, 600 and 750) in combination with the PBEsol and three
PAW potentials Ti_std, Ti_pv and Ti_sv. Both low- and room-temperature experimental values of Hr reported by various
authors are included. Table 2, for example, lists the ionic (low-frequency), electronic (high-frequency) components (Hij(0)and Hij(λ), respectively) of the dielectric permittivity tensor Hr of R-TiO2, obtained using high-level HSEsol and HSE06
calculations in combination with the three PAW potentials Ti_std. A cut-off energy of 700 eV was used.
In order to understand the wide variation of the static dielectric constant, we have attempted to examine thedependance of the charge density profile on the DFT functionals PBE, PBE+U (U = 3.5 eV), PBEsol, PBEsol + U, SCAN,
SCAN-rVV10, HSEsol, and HSE06, all in conjunction with the three PAW potentials Ti_std, Ti_pv and Ti_sv. The results
allowed us to demonstrate the reproducibility of the experimental ionic dielectric constant with the hard PAW potential
centered on Ti, and to clarify the origin of the spurious (soft) nature of the phonon modes predicted by the two soft
potentials Ti_pv and Ti_sv.

- 314 -

Table 1: Comparison of ionic (low-frequency) and electronic (high-

The results obtained for the elastic

frequency) components (Hij(0) and Hij( λ ), respectively) of the relative

properties using various DFT functionals

dielectric permittivity tensor Hr of R-, A- and B-TiO2, obtained using three

noted above, together with the three PAW

cutoff energies in combination with the PBEsol and three PAW potentials

potentials employed, enabled us to

Ti_std, Ti_pv and Ti_sv. Both low- and room-temperature experimental

demonstrate that all the polymorphs

values of Hr reported by various authors are included.

examined were mechanically stable. Table
3, for example, compares the PBEsol(frozen phonon finite difference method)computed elastic properties of brookite
TiO2, obtained using three different PAW
potentials on their corresponding relaxed
lattice geometries. The nature of elastic
anisotropy in the crystal lattice was also
revealed.
In addition, the most crucial
issue was how the subtle change of thecrystal lattice of TiO2 influences andintroduces ferroelectric features. Our
calculations using three different PAW
potentials and computational methods
have enabled us to reveal how strongly
can the induction of the ferroelectricmodes enhances the ionic dielectric
permittivity, especially for the low-lying
IR (and Raman) active vibrational modes.
Calculations of phonon band structuresaReported at the LDA and GGA levels, using Quantum Expresso software.

b

Low-temperature data refer T = 1.6 K.

and density of states allowed us toTable 2: The ionic (low-frequency), electronic (high-frequency) components (Hij(0) and Hij(λ), respectively) of thedielectric permittivity tensor Hr of R-TiO2, obtained using HSEsol and HSE06 in combination with the three PAW
potentials Ti_std. A cut-off energy of 700 eV was used.

- 315 -

Table 3: Comparison of PBEsol (frozen phonon finite difference method) computed elastic properties of B-TiO2,
obtained using three different PAW potentials on their corresponding relaxed lattice geometries.a,ba Properties include the Bulk modulus B, Shear modulus S, Young’s modulus Y, Poison’s ratio V, Pressure-wave modulus P, the Bulk

modulus/Shear modulus ratio B/S, longitudinal velocity vl, transverse velocity vt, average velocity vm, Debye temperature 4D, Zener
anisotropy A, Universal anisotropy index AU and Log-Euclidean anisotropy AL.

understand the dynamical stability ofthe polymorphs of TiO2. Figure 2, forexample, shows the phonon band
structures of the F- and P-phases thatindicatethepossibility

of

any

dynamically unstable lattice, eventhough the R-, A- and B-TiO2 latticewere found to be dynamically stable(not shown), in agreement with

Figure 2: Illustration of phonon dispersion of F- and P-TiO2, respectively,

experiment. The only feature thatobtained using density functional perturbation theory at the [PBEsol/Ti_std]

manifests

combinationlevel. The 4u4u4 (192 atoms) and 2u2u2 (96 atoms) supercells were utilized

between the Hubbard term and DFT isfor the phonon calculations for F- and P-TiO2, respectively. Phonon

the disappearance of all soft (lowfrequencies in the vertical axis are in THz (1 THz = 33.3564 cm-1).

with

the

frequency IR active) phonon modes,
meaning that the combination does not predict the dynamic instability of the R-TiO2 lattice predicted by Ti_pv and Ti_sv
in combination with PBE.
We have examined the isotropic pressure dependence of the geometry, zone-center phonon modes and relative
dielectric constant of R-, A- and B-TiO2. Figure 3, for example, shows such a dependence of the lowest five *-center
phonon modes on the applied pressure of R-TiO2. When the applied pressure increases, it causes the expansion of therutile lattice, as well as the lattices of the other polymorphs. These calculations led us to a rationalization that theferroelectric instability can be induced in the TiO2 lattice by applying negative hydrostatic pressure. At least three lowlying phonon modes (A2u, B1u and Eu) of R-TiO2 are observed to be sensitive not only to the onset of ferroelectric phasetransitions, but also to the hard and soft nature of the three PAW potentials.

- 316 -

The effect of double doping on the rutile latticeof TiO2 was also examined using DFT. The crystal
lattices of various bulk and supercell metal dioxide hostspecies (viz. VO2, MnO2, ZnO2, ReO2, IrO2, MoO2, SiO2,
and SnO2, etc) were geometrically relaxed using very
tight convergence criteria, in conjunction with affordable
high k-mesh grids. Our computational investigation
included the 2×2×3 and 3×3×3 supercell structures ofrutile TiO2 and Nb2O5. We have done so as to examine
the effect of wt% dopants on the physical properties of
the resulting systems discussed already above. Double
dopants (viz. N and In replaces two different Ti sites in
R-TiO2 supercell lattice) were mainly considered. The
dopped systems examined, for example, include VCe,
VEr, VEu, VGd VHo, VLa, VLu, VNd, VPm, VPr, VSc,
Figure 3: (Left) PBEsol level external (hydrostatic)

VSm, VTm, VW, VY, and VYb, as well as NbAs, NbBi,

pressure dependence of the lowest five *-centered phonon

NbN, NbP, NbSb, AsN, HfN, SbN, TaN, ZrN, VAl, VAs,

modes of R-TiO2, obtained with PAW potentials: (a)VB, VBi, VGa, VIn, VN, VP, and VSb, etc. Analysis of

Ti_std; (b) Ti_pv; (c) Ti_sv. (Right) The dependence ofthe computed results of lattice and dielectric properties

dielectric permittivity (ionic) on applied pressure, obtainedof these dropped systems is underway, yet further

PAW potentials: (d) Ti_std; (e) Ti_pv; (f) Ti_sv.

computation of several of these dopped systems isnecessary to arrive at publication quality results sinceconvergence of Born effective charges is identified to be one of the main issues in generating reasonable quality relative
permittivity.

4

Talks and Posters[1]. P.R. Varadwaj, Y. Shimano, R. Asahi, Titanium Dioxide (TiO2) and Its polymorphs: An assessment of the variants ofprojector augmented wave (PAW) potential of Ti on its geometric, electronic, mechanical, dynamical and opticalproperties, The 11th International Conference on Nanostructures, Nanomaterials and Nanoengineering 2022 (ICNNN
2022), November 26-28, 2022, Tokyo, Japan.
[2]. P. R. Varadwaj, R. Asahi, On the polymorphic stability, and bandgap features of Polymorphs of titanium dioxide(TiO2): The nature of dependence of properties on the quality of the density functional and projector augmented wave
(PAW) potential (Ms under preparation).

5

Publications[1] P. R. Varadwaj, Van An Dinh, Yoshitada Morikawa, Asahi, Polymorphsrphs of Titanium Dioxide: An Assessment of
the Variants of Projector Augmented Wave Potential of Titanium on Their Geometric and Dielectric Properties, ACS
Omega 2023, https://doi.org/10.1021/acsomega.3c02038- 317 -

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࡟ Vanitaracin C ࡀⓎぢࡉࢀࠊྛ✀ศගᏛⓗᡭἲ࡜ᐇ㦂໬Ꮫⓗᡭἲ࡟ࡼࡾࠊ┦ᑐ❧య㓄⨨ࡣỴᐃ࡛ࡁࡓࡶࡢࡢࠊ୕⎔ᘧ㦵᱁࡜ഃ㙐ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥ࡟ࡘ࠸
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- 324 -

ࢼࣀ࣮࢝࣎ࣥ࡜᭷ᶵ≀ࢆ⏝࠸ࡓᶵ⬟ᮦᩱࡢィ⟬໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥ
Computational chemistry simulation of functional materials
using nanocarbons and organic materials‫ۑ‬ᡭᓥṇ࿃㸪Ἑᮾ⏣㐨ኵ㸪ᴿ៞୔㸪㟷㔝ಙ἞㸪ᒣ୰⥤㤶㸪ྂ㈡⿱᫂㸪⡿ཎ୔༤ᇛ㔝ுኴ㸪ᒣ⏣㐩▮㸪ᒣ⏣⠜ᚿ㸦㧗ᗘ᝟ሗ⛉Ꮫᢏ⾡◊✲ᶵᵓ㸧1◊✲┠ⓗᙜᶵᵓࡣ JST COI ࣉࣟࢢ࣒ࣛಙᕞ኱Ꮫ࢔ࢡ࢔࣭࢖ࣀ࣮࣋ࢩࣙࣥᣐⅬ࡟ཧ⏬ࡋ㸪ࢼࣀ࣮࢝࣎ࣥᮦᩱᢏ⾡ࢆ㥑౑ࡍࡿࡇ࡜࡛ᆅ⌫ୖࡢከᵝ࡞Ỉ※࠿ࡽᏳ඲࡞Ỉࢆ౪⤥ࡍࡿࢩࢫࢸ࣒ࡢᵓ⠏ࢆ┠ᣦࡋࡓ◊✲ࢆ㐍ࡵ࡚࠸ࡿ㸬ࡑࡇ࡛ࡢ୰ᚰⓗ◊✲ㄢ㢟ࡣ㧗ᶵ⬟࡞Ỉฎ⌮⭷࡟᭷ຠ࡞Ⅳ⣲ᮦᩱࡢ㛤Ⓨ࡛࠶ࡾ㸪ࡇࢀࡲ࡛Ỉฎ⌮⭷ࡢᶵ⬟ゎ᫂ࢆ┠ⓗ࡟୺࡟㏱Ỉ࣭⬺ሷ࣭㜵ởࡢほⅬ࠿ࡽ◊✲ࢆ⾜ࡗ࡚ࡁࡓ㸬ᙜᶵᵓࡀศᢸࡋ࡚࠸ࡿศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟
ࡼࡿ⤖ᯝࡣ┤ࡕ࡟ᐇ㦂◊✲࡬࡜ࣇ࢕࣮ࢻࣂࢵࢡࡋ㸪᪂ࡋࡃィ⏬ࡉࢀࡓᐇ㦂࡛⏕ࡌࡓ⛉Ꮫⓗ␲ၥⅬ࡟෌ࡧศᏊ
ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥྲྀࡾ⤌ࡴ࡜࠸ࡗࡓࢧ࢖ࢡࣝ࡟ࡼࡗ࡚㧗ᛶ⬟࡞⣲ᮦࡢ㛤Ⓨࢆ┠ᣦࡋ࡚࠸ࡿ㸬௒ᖺᗘࡢ◊✲࡛ࡣ㸪㛤Ⓨࡀ㐍ࡵࡽࢀ࡚࠸ࡿ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ(CNT)࡜࡜ࡶ࡟ࢭ࣮ࣝࣟࢫࢼࣀࣇ࢓࢖ࣂ
࣮(CNF)ࢆ」ྜࡋࡓ࣏ࣜ࢔࣑ࢻ(PA)㧗ศᏊࢆ⏝࠸ࡓ㏫ᾐ㏱(RO)Ỉฎ⌮⭷(CNT+CNF/PA)࡟ࡘ࠸࡚㸪᫖ᖺᗘ࡟ᘬ
ࡁ⥆ࡁྛ✀᮲௳ࢆኚ࠼ࡓศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ㏱Ỉᛶ࡜㜵ởᛶࡢᶵ⬟ホ౯ࢆ⾜ࡗࡓ㸬ࡲࡓ㸪C60 ࡞࡝ࡢⅣ⣲ᮦᩱࢆ᭷ᶵ⁐፹࡟ศᩓࡉࡏࡿࡇ࡜ࡣⅣ⣲ᮦᩱࡢᕤᴗ฼⏝࡟࠾࠸࡚ᚲ㡲ࡢ㐣⛬࡛࠶ࡿࡀ㸪୍⯡࡟Ⅳ⣲ᮦᩱࡣ⁐፹࡟ᑐࡋ࡚㞴⁐࡛࠶ࡾࡑࡢ᫆⁐໬ࡀㄢ㢟࡛࠶ࡿ㸬ᡃࠎࡢᐇ㦂ࢢ࣮ࣝࣉ࡛ࡣ࠶ࡿ✀ࡢ᭷ᶵ⁐፹ࡀ C60 ࡟ᑐࡋ࡚≉␗ⓗ࡞⁐፹࿴ᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࢆぢฟࡋ࡚ࡁࡓ㸬ᮏ◊✲࡛ࡣࢺ࢚ࣝࣥࢆጞࡵ࡜
ࡍࡿ᭷ᶵ⁐፹୰ࡢ C60 ࡟ࡘ࠸࡚⁐፹࿴࢚ࢿࣝࢠ࣮ィ⟬࣭C60 ゎ㞳⮬⏤࢚ࢿࣝࢠ࣮ホ౯ࢆ⾜ࡗࡓ㸬2◊✲᪉ἲࠊィ⟬᪉ἲ࠙Ỉฎ⌮⭷ࡢᶵ⬟ホ౯ࠚඹྠ◊✲ඛࡢಙᕞ኱Ꮫࢢ࣮ࣝࣉ࡟ࡼࡗ᳨࡚ウࡉࢀ࡚࠸ࡿ CNT ࡜ CNF ࢆ」ྜࡋࡓỈฎ⌮⭷(CNT+CNF/PA)࡟ࡘ࠸࡚㸪௧࿴ 3 ᖺᗘ࡟⾜ࡗࡓ㏱Ỉᛶ㸪㜵ởᛶホ౯ࡢ⿵ᙉ࡜ࡋ࡚㸪ᐇ㦂ࢢ࣮ࣝࣉ࠿ࡽせᮃࡀ࠶ࡗࡓ㸪␗࡞ࡿ
ᅽຊ࡛ࡢ㏱Ỉᛶ㸪␗࡞ࡿ㏿ᗘࡢỈὶ࡛ࡢ࢘ࢩ⾑Ύ࢔ࣝࣈ࣑ࣥ(Bovine serum albumin; BSA)࡟ᑐࡍࡿ㜵ởᛶ࡟ࡘ࠸࡚඲ཎᏊྂ඾ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒࢆ⾜ࡗࡓ㸬ẚ㍑ࡢࡓࡵᚑ᮶ᆺࡢ PA ࡢࡳࡢ⭷㸪CNT
ࡢࡳࢆ」ྜࡋࡓ CNT/PA 」ྜ⭷㸪CNF ࡢࡳࢆ」ྜࡋࡓ CNF/PA ⭷㸪CNT ࡜ CNF ࢆ࡝ࡕࡽࡶ」ྜࡋࡓ
CNT/CNF/PA 」ྜ⭷ࢆసᡂࡋࡓ㸬ィ⟬ࢯࣇࢺ࢙࢘࢔ࡣ LAMMPS㸪ศᏊຊሙ࡜ࡋ࡚Ỉฎ⌮⭷࡟ࡣ GAFF ࢆ㸪
BSA ࡟ࡣ CHARMM ࢆ㸪ỈศᏊ࡟ࡣ TIP3P ࢆ⏝࠸ࡓ㸬㏱Ỉᛶࡢゎᯒࡢࡓࡵ㸪సᡂࡋࡓ 4 ✀ࡢỈฎ⌮⭷ࢆỈ࡜ࢢࣛࣇ࢙ࣥࡢቨ࡛ᣳࡳ㸪ୖୗࡢࢢࣛࣇ࢙ࣥቨࢆ 1 Ẽᅽ࡛ᢲࡋࡓ≧ែ࡛Ᏻᐃ໬ࡉࡏࡓᚋ㸪ୖ㒊ࡢࢢࣛࣇ࢙ࣥቨ
࡟ᚑ᮶ᆺࡢỈฎ⌮⭷࡛ࡼࡃฎ⌮᫬࡟⏝࠸ࡽࢀࡿ 5 MPa ࡢᅽຊࢆ༳ຍࡋ㏱Ỉࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ㸬㜵ởᛶࡢゎᯒ࡛ࡣ㸪Ỉ࿴ࡉࡏࡓ⭷ୖ࡟ BSA ࢆ㓄⨨ࡋ㸪୍㒊ࡢỈศᏊ࡟⭷⾲㠃࡟ᖹ⾜࡞ຊࢆຍ࠼ࡿࡇ࡜࡛㸪ᐇ㝿ࡢỈฎ⌮᫬࡟⏕ࡌࡿࢡࣟࢫࣇ࣮ࣟࢁ㐣᪉ᘧ࡟ࡼࡿᖹ⾜࡞Ỉὶࢆᶍᨃⓗ࡟ᑟධࡋࡓࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸㸪ᚓࡽࢀࡓࢺࣛࢪ࢙ࢡࢺࣜࡢゎᯒࢆ⾜ࡗࡓ㸬- 325 -

࠙᭷ᶵ⁐፹୰ࡢ C60 ࡢ⁐፹࿴ᵓ㐀ࠚࢺ࢚ࣝࣥ㸪ࢹ࢝ࣥ㸪1-ࣇ࢙ࢽࣝࢼࣇࢱࣞࣥࡢ᭷ᶵ⁐፹࡟ࡘ࠸࡚ C60 ࡢ⁐፹࿴࢚ࢿࣝࢠ࣮ࢆ⇕ຊᏛⓗ✚ศἲ࡟ࡼࡗ࡚ホ౯ࡋࡓ㸬(6 nm)3 ࡢ᱁Ꮚ࡟㸯ศᏊࡢ C60 ࡜ 1000 ศᏊ࠿ࡽ 1500 ศᏊࡢ᭷ᶵ⁐፹ࢆ㐺ᙜ࡞ᐦᗘ࡟࡞ࡿ
ࡼ࠺࡟㓄⨨ࡋࡓ⣔࡟ࡘ࠸࡚ᐇ᪋ࡋࡓ㸬ࡍ࡞ࢃࡕࢺ࢚ࣝࣥ 1500 ศᏊ㸪ࢹ࢝ࣥ 1000 ศᏊ㸪1-ࣇ࢙ࢽࣝࢼࣇࢱࣞ
ࣥ 1000 ศᏊ࡛࠶ࡿ㸬ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ LAMMPS ࢆ⏝࠸㸪ຊሙࡣ OPLS-AA ࢆ⏝࠸ࡓ㸬⇕ຊᏛⓗ✚ศἲ࡛ࡣ୍ࡘࡢ⣔࡟ࡘࡁ 6 Ⅼࡢࣃ࣓ࣛࢱⅬ࡛ࡢィ⟬ࢆࡑࢀࡒࢀ 10 ns ᐇ⾜ࡋ㸪ู࡟ィ⟬ࡋࡓ C60 ࡢ᪼⳹࢚ࢿࣝࢠ࣮
࡜ࡢᕪ࠿ࡽ⁐፹࿴࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓ㸬 ࡲࡓ㸪ࢺ࢚ࣝࣥ⁐፹୰ࡢ C60 ࡢゎ㞳⮬⏤࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚࣓ࢱ
ࢲ࢖ࢼ࣑ࢡࢫἲࢆ⏝࠸࡚ホ౯ࡋࡓ㸬(5 nm)3 ࡢ᱁Ꮚ࡟ 2 ศᏊࡢ C60 ࡜ 650 ศᏊࡢࢺ࢚ࣝࣥࢆ㓄⨨ࡋࡓ⣔࡟ࡘ࠸
࡚ 300 ns㸦100 ns ࡢ࣏ࢸࣥࢩࣕࣝᵓ⠏࡜ 200ns ࡢࣉࣟࢲࢡࢩࣙࣥࣛࣥ㸧ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓ㸬

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◊✲ᡂᯝ

࠙Ỉฎ⌮⭷ࡢᶵ⬟ホ౯ࠚ
㏱Ỉࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࢆᅗ 1 ࡟♧ࡍ㸬ຍ࠼ࡓᅽຊࡀ␗࡞ࡗ࡚ࡶ㸪CNT ㏆ഐ࡛ࡣ㧗㏿࡞㏱Ỉࣃࢫࡀ࡛ࡁ㸪CNF ㏆ഐ࡛ࡣỈࡢศᕸࡀ኱ࡁࡃ࡞ࡿ࡜࠸࠺ഴྥࡣ᫖ᖺᗘ࡜ྠᵝ࡛࠶ࡗࡓ㸬ࡋ࠿ࡋ㸪⭷㡿ᇦࡢỈࡢᣑᩓಀᩘࢆẚ㍑ࡍࡿ࡜㸪㧗ᅽୗ࡛ࡣ CNT/PA 」ྜ⭷㸪PA ࡢࡳࡢ⭷࡛ࡣࢃࡎ࠿࡟ୖ᪼ࡋࡓࡶࡢࡢ㸪CNT/CNF/PA 」ྜ
⭷㸪CNF/PA 」ྜ⭷࡛ࡣᑠࡉࡃ࡞ࡿ࡜࠸࠺⤖ᯝ࡜࡞ࡗࡓ㸬ࡲࡓ㸪ᅗ 1 ୰ࡢ࣮࣐࢝ࣛࢵࣉࡢ⧅ࡀࡾࡀ㸪ᅽຊࡀ㧗࠸ሙྜ࡛ࡣษࢀࡿ㸪ⷧࡃ࡞ࡿ࡜࠸ࡗࡓᵝᏊࡀぢࡽࢀࡓ㸬ᚑ᮶ᆺࡢỈฎ⌮⭷࡛ᚲせ࡞ 5 MPa ࡜࠸࠺㧗ᅽୗ࡛ࡣ㸪⭷ࡀᢲࡋࡘࡪࡉࢀ࡚㏱Ỉࣃࢫࡀᑡ࡞ࡃ࡞ࡿ୍᪉㸪CNT ࡸ CNF ࢆ」ྜࡋࡓ㸪ࡼࡾపᅽ࡛ࡢỈฎ⌮ࡀྍ⬟࡞⭷࡛ࡣ㸪⭷ࡀࡘࡪࢀࡿࡇ࡜࡞ࡃ㧗࠸ᣑᩓಀᩘ࡛㏱Ỉࡍࡿࡇ࡜ࡀண᝿ࡉࢀࡿ㸬ᅗ 1. ㏱Ỉࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡢ⭷㡿ᇦࡢỈࡢᣑᩓಀᩘ㸬Ỉฎ⌮⭷ୖࡢ BSA ࡢࢡࣟࢫࣇ࣮ࣟࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࢆᅗ 2 ࡟♧ࡍ㸬ỈศᏊ࡟༳ຍࡍࡿຊࡢ኱ࡁࡉࢆ
ኚ࠼㸪᫖ᖺᗘࡼࡾࡶ㐜࠸Ỉὶ࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝ㸪ࡸࡣࡾ CNT/CNF/PA 」ྜ⭷ࡣ BSA ࡟ᑐࡍࡿ㧗࠸㜵ởᛶࢆ♧ࡋࡓ㸬ࡑࡢ௚ࡢ⭷࡟㛵ࡋ࡚ࡣ᫖ᖺᗘࡢ㏿࠸Ỉὶ࡛ࡣ BSA ࡀ⭷ୖࢆ㌿ࡀࡿᵝᏊࡀ☜ㄆ࡛ࡁࡓࡢ࡟ᑐ
ࡋ㸪௒ᖺᗘࡢ㐜࠸Ỉὶ࡛ࡣỈ⣲⤖ྜࡀᘬࡁࡣࡀࡉࢀࡿࡇ࡜ࡣᑡ࡞ࡃ㸪BSA ࡣỈὶ࡟ࡼࡗ࡚⭷ୖ࡟ᢲࡋ௜ࡅࡽ
ࢀࡿࡼ࠺࡞ືࡁࢆࡋࡓ㸬୍᪉࡛㸪Ỉὶࡀ㏿࠸᫬࡯࡝⃭ࡋ࠸ືࡁ࡟ࡣ࡞ࡽ࡞࠸ࡓࡵ࠿㸪Ỉ⣲⤖ྜᩘࡣᖹᆒ࡜ࡋ

- 326 -

࡚Ỉὶࡀ㐜࠸᪉ࡀᑡ࡞ࡃ࡞ࡗ࡚࠸ࡿ㸬᫖ᖺᗘྠᵝ㸪CNT/PA 」ྜ⭷㸪CNF/PA 」ྜ⭷࡛ࡣ⾲㠃ࡢฝ㒊࡟ BSA ࡢ୍㒊ࡀ௜╔ࡋ࡚ࡋࡲࡗࡓࡀ㸪CNT/CNF/PA 」ྜ⭷ࡢࡼ࠺࡟༑ศ࡞㜵ởᛶࡀ࠶ࢀࡤ㸪ࢡࣟࢫࣇ࣮ࣟࢁ㐣᪉ᘧ࡛ࡢ⭷࡟ᖹ⾜᪉ྥࡢὶࢀࡀᑡ࡞ࡃ࡜ࡶ BSA ࡢ௜╔ࡀᢚไ࡛ࡁ㸪ࡼࡾ┬࢚ࢿࣝࢠ࣮࡛ࡢືసࡀᮇᚅ࡛ࡁࡿ㸬ᅗ 2. BSA ࣇ࢓࢘ࣜࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝ㸬࠙᭷ᶵ⁐፹୰ࡢ C60 ࡢ⁐፹࿴ᵓ㐀ࠚ⇕ຊᏛⓗ✚ศἲ࡟ࡼࡿ᭷ᶵ⁐፹୰ C60 ࡢ⁐፹࿴࢚ࢿࣝࢠ࣮ࡢ್ࢆ⾲ 1 ࡟♧ࡍ㸬 C60 ࡢ᪼⳹࢚ࢿࣝࢠ࣮ࢆ
C60 “⁐፹”࡬ࡢ C60 “⁐㉁”ࡢ⁐፹࿴࢚ࢿࣝࢠ࣮࡜ᤊ࠼㸪᭷ᶵ⁐፹࡬ࡢ⁐፹࿴࢚ࢿࣝࢠ࣮࡜ྠᵝ࡟ィ⟬ࡋࡓ㸬ࢺ࢚ࣝࣥ㸪ࢹ࢝ࣥ㸪1-ࣇ࢙ࢽࣝࢼࣇࢱࣞࣥࡢ࠸ࡎࢀࡶࡀ C60 ࡢ᪼⳹࢚ࢿࣝࢠ࣮ࢆᇶ‽࡜ࡋ࡚ṇࡢ್࡛࠶ࡾ㸪
C60 ࡢ㞴⁐ᛶࢆ♧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ㸬⾲ 1.

C60 ࡢ⁐፹࿴࢚ࢿࣝࢠ࣮ࡢ್

TI ✚ศ್

⁐፹࿴࢚ࢿࣝࢠ࣮

C60 ᪼⳹ E−40.76 kcal mol−1

(ᇶ‽)

ࢺ࢚ࣝࣥ

−29.58 kcal mol−1

11.19 kcal mol−1ࢹ࢝ࣥ−27.60 kcal mol−113.17 kcal mol−11-ࣇ࢙ࢽࣝࢼࣇࢱࣞࣥ

−36.76 kcal mol−1

4.01 kcal mol−1ᅗ㸱ࡣ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫἲ࡟ࡼࡿࢺ࢚ࣝࣥ⁐፹୰ࡢ C60 ࢲ࢖࣐࣮ࡢゎ㞳⮬⏤࢚ࢿࣝࢠ࣮࡛࠶ࡿ㸬C60 ྠኈࡀ┤᥋᥋ゐࡍࡿ㔜ᚰ㛫㊥㞳ࡀ 1 nm ࡜࡞ࡿ࡜ࡁࡀ᭱Ᏻᐃ࡛㸪ࡑࡇ࠿ࡽゎ㞳ࡍࡿࡢ࡟࠾ࡼࡑ 3 kcal mol−1 ࡶࡢ࢚ࢿࣝࢠ࣮㞀ቨࢆᚲせ࡜ࡋ࡚࠸ࡿࡀ㸪୍᪉࡛㸪ゎ㞳≧ែ࠿ࡽࢲ࢖࣐࣮ࢆᵓᡂࡍࡿ㝿࡟ࡶ 1.5 kcal mol−1 ⛬ᗘࡢ࢚ࢿࣝࢠ࣮㞀ቨࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࡇࡢࡇ࡜ࡣࢺ࢚ࣝࣥ࡟ࡼࡿ C60 ࡢ⁐፹࿴ᵓ㐀ࡀ࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾ㸪ࡇࡢ⁐፹࿴ᵓ㐀ࢆᏳᐃ໬ࡍࡿࡼ࠺࡞ศᏊタィ࡟ࡼࡗ࡚ C60 ࡢ᭷ᶵ⁐፹࡬ࡢ᫆⁐໬࡟ᐤ୚࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿ㸬- 327 -  
ᅗ 3 ࢺ࢚ࣝࣥ୰ࡢ C60 ࢲ࢖࣐࣮ゎ㞳⮬⏤࢚ࢿࣝࢠ࣮࡜ィ⟬࡟⏝࠸ࡓ C60 㔜ᚰ㛫㊥㞳ࡢࢧࣥࣉࣜࣥࢢ㐣⛬ ᅗ㸲ࡣ C60 ࿘ࡾࡢືᚄศᕸ㛵ᩘ࡛࠶ࡿ㸬C60 ⾲㠃࠿ࡽ 0.37 nm ௜㏆࡟࠶ࡿࣆ࣮ࢡ࠿ࡽ㸪C60 ࡟ᑐࡋ࡚ࢺ
࢚ࣝࣥⰾ㤶⎔ࡀྥࡁྜࡗ࡚┦஫స⏝ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ᅗ 4 C60 㔜ᚰ࿘ࡾࡢືᚄศᕸ㛵ᩘ㸦⥳㸸C60 ᵓᡂⅣ⣲㸪⣸㸸ࢺ࢚ࣝࣥDⅣ⣲㸧

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] J.L. Fajardo-Diaz, A. Morelos-Gomez, R. Cruz-Silva, K. Ishii, T. Yasuike, T. Kawakatsu, A. Yamanaka, S. Tejima, K.
Izu, S. Saito, J. Maeda, K. Takeuchi, M. Endo, “Low-pressure reverse osmosis membrane made of cellulose nanofiberand carbon nanotube polyamide nano-nanocomposite for high purity water production” Chemical Engineering Journal,
448, 2022, 137359,- 328 -

ྵ࣊ࢸࣟ㠀ᖹ㠃ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢᵓ㐀࠾ࡼࡧᛶ㉁
6WUXFWXUHVDQG3URSHUWLHVRI1RQSODQDU3RO\F\FOLF$URPDWLF
+\GURFDUERQV&RQWDLQLQJ+HWHURDWRP‫ۑ‬ຍ⸨ ೺ኴࠊṊ⸨ ៞ࠊኴ⏣ ⱥ௓ࠊᫍ ㈗அࠊຍ⸨ ᘯᇶࠊ఍⏣ ࿴ᗈࠊᖹᑿ ࡲࡾ࡞ࠊ℧ᮏ ᫓ᶞࠊ᪥ẚ㔝 ඘㈗㸦᪩✄⏣኱Ꮫ㸧




◊✲┠ⓗ
㠀ᖹ㠃ⰾ㤶᪘໬ྜ≀ࡢྜᡂ⤒㊰᥈⣴ࡸᇶ♏≀ᛶࡢゎ᫂ࢆ┠ᣦࡍࠋከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ 3$+ ࡣࠊࡑࡢȧඹᙺ㦵᱁࡟ᇶ࡙࠸ࡓᚓព࡞㟁ᏊⓗࠊගᏛⓗ࠾ࡼࡧ☢Ẽⓗ≉ᛶࢆࡶࡘࠋࡇࢀࡽࡢ≉ᛶࢆᕦࡳ࡟฼⏝ࡍࡿ᭷ᶵ࢚ࣞࢡ
ࢺࣟࢽࢡࢫࡢ㛤Ⓨࡀ┒ࢇ࡟⾜ࢃࢀ࡚࠸ࡿࠋ3$+ ࡢȧඹᙺ㦵᱁ࡢᨵኚ᪉ἲ࡜ࡋ࡚ࠊ㠀  ဨ⎔ࡢ⤌ࡳ㎸ࡳࡸ࣊ࢸࣟཎ Ꮚ࡜ࡢ⨨᥮ࡀ▱ࡽࢀࡿࠋ㠀  ဨ⎔ࢆ⤌ࡳ㎸ࡴ࡜ 3$+ ࡣ㠀ᖹ㠃ᵓ㐀ࢆ࡜ࡾࠊࡑࡢᵓ㐀࡟㉳ᅉࡋ࡚ᚓព࡞
ືⓗᣲືࡸࣃࢵ࢟ࣥࢢᵓ㐀ࢆ♧ࡍࡼ࠺࡟࡞ࡿࠋࡲࡓࠊᵓᡂⅣ⣲ཎᏊࢆ࣊ࢸࣟཎᏊ࡬࡜⨨᥮ࡍࡿࡇ࡜࡛㟁Ꮚᵓ㐀ࡢ๻ⓗ࡞ᨵኚ࡜ࣝ࢖ࢫ㓟࣭ሷᇶᛶࡢ⋓ᚓࡀྍ⬟࡛࠶ࡿࠋࡇࢀࡽ஧ࡘࡢᨵኚ᪉ἲࢆ⤌ࡳྜࢃࡏࡓ㠀ᖹ㠃࠿ࡘ࣊ࢸࣟཎᏊࢆ᭷ࡍࡿ᪂ወ 3$+ ࡣ࡝ࡢࡼ࠺࡞ᇶ♏≀ᛶࢆ᭷ࡍࡿࡢ࠿࡟⯆࿡ࡀࡶࡓࢀࡿࠋࡋ࠿ࡋࠊ㠀  ဨ⎔ࡢ⤌ࡳ㎸ࡳ࡟ࡣṍࡳ࢚ࢿࣝࢠ࣮ࡢඞ᭹ࡢࡓࡵཝࡋ࠸཯ᛂ᮲௳ࡀᚲせ࡜࡞ࡿ୍᪉࡛࣊ࢸࣟཎᏊࡣࡑࡢཝࡋ࠸᮲௳࡛
ቯࢀ࡚ࡋࡲ࠺ࡇ࡜ࡀண᝿ࡉࢀࡿࠋࡑࡇ࡛ࠊᮏ◊✲ㄢ㢟࡛ࡣࠊ⏕ᡂ≀ࡢ⇕ຊᏛⓗᏳᐃᛶࡸ㑄⛣≧ែࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ぢ✚ࡶࡾࠊጇᙜ࡞ྜᡂ⤒㊰ࢆ⟬ฟࡍࡿࠋࡲࡓࠊྜᡂ࡟ᡂຌࡋࡓศᏊ࡟㛵ࡋ࡚ࡣᵓ㐀᭱㐺໬࡜⥆ࡃᇶ♏≀ᛶ ࡢ⌮ㄽணࢆ⾜࠺ࠋ㠀ᖹ㠃ᵓ㐀ࡢྵ࣊ࢸࣟཎᏊከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢィ⟬࡟࠾࠸࡚ࠊ࠸ࡃࡘ࠿ࡢ

ྜᡂࢱ࣮ ࢤࢵࢺศᏊࡢᵓ㐀Ᏻᐃ໬࡜ᇶ♏≀ᛶࡢணࡀ᏶஢ࡋ࡚࠸ࡿࠋຍ࠼࡚ࠊࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ࢚ࢼࣥ

ࢳ࢜㑅ᢥⓗ⬺ⰾ㤶᪘ⓗᐁ⬟ᇶ໬཯ᛂ࡟࠾ࡅࡿ୙ᩧ㓄఩Ꮚタィ࡟࠾࠸࡚ࡣ୍ᐃࡢᡂᯝࡀᚓࡽࢀࡓࡓࡵࠊ௒ᖺᗘ
୰ࡢㄽᩥ໬ࢆ┠ᣦࡋ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ඾ᆺඖ⣲ࢆྵࡴ㠀ᖹ㠃ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢᵓ㐀࡜≀ᛶ࡟࠾࠸࡚ࡣ୍ᐃࡢᡂᯝࡀᚓࡽࢀ࡚࠸ࡿࠋ௒ᚋࡣࠊ

᪂ࡓ࡞ྜᡂࢱ࣮ࢤࢵࢺࡢᏳᐃᵓ㐀ࡢィ⟬࡜ྠࡌィ⟬࡛ࣞ࣋ࣝࡢᇶ♏≀ᛶࡢணࢆ࠾ࡇ࡞࠺ࠋ
ཎᏊᩘࡀ᭱኱ ಶ࡜࡞ࡿ⣔࡟㛵ࡋ࡚⇕ຊᏛᐃࣃ࣓࣮ࣛࢱ࣮ࡢィ⟬࡟ࡼࡿືⓗᣲືࡢゎ᫂࡜᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ 7'')7 ࢆࡶࡕ࠸ࡓィ⟬࡟ࡼࡾࠊගᏛ≉ᛶࡢゎ᫂ࢆ┠ᣦࡍࠋࢯࣇࢺ࢙࢘࢔ࡣ *DXVVLDQ ࢆ౑⏝ࡍࡿࠋศᏊᵓ㐀ࡢ᭱㐺໬
ࡣ %/<3* G ࠿ࡽ㡰ḟィ⟬ࣞ࣋ࣝࢆୖࡆ࡚⾜࠺ࠋ≉࡟ࣛࢪ࢝ࣝ✀ࡸ࢔ࢽ࢜ࣥ✀ࡢィ⟬࡛ࡣ GLIIXVH 㛵ᩘࢆ⏝࠸ࡿࠋࡲࡓࠊ࣊ࢸࣟཎᏊࢆ௓ࡋࡓ௚ศᏊ࡜ࡢ」ྜయᙧᡂࡀぢ㎸ࡲࢀࡿࡓࡵࠊ」ྜయࡢ⇕ຊᏛⓗࣃ࣓࣮ࣛࢱ
࣮ࡶ⟬ฟࡍࡿணᐃ࡛࠶ࡿࠋࡲࡓࠊ௒ᖺᗘ୰࡟኱ᆺィ⟬ᶵ࡛⾜ࡗ࡚ࡁࡓ◊✲ㄢ㢟ࠊ⬺ⰾ㤶᪘ⓗᐁ⬟ᇶ໬཯ᛂࡢ
࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢⓎ⌧ࢆ┠ᣦࡋࡓ୙ᩧ㓄఩Ꮚタィ࡟㛵ࡋ࡚ࡣࠊ㔜せ୰㛫యᵓ㐀ࡢศᏊሙゎᯒࢆࡶ࡜࡟ࠊᶵ
ᲔᏛ⩦ࢆ⏝࠸࡚᭱㐺㓄఩Ꮚࢆᑟฟࡍࡿࠋ⌧ᅾࠊᮏᡭἲࢆ㑄⛣≧ែࡢศᏊሙゎᯒ࡬ᒎ㛤ࡋࠊ᭱㐺໬ࡢ⢭ᗘࢆ㧗ࡵ࡚࠸ࡿࠋᐇ㦂್࡜ẚ㍑ࡍࡿࡇ࡜࡛᭱㐺࡞㓄఩Ꮚタィࢆࡋࠊ࢚ࢼࣥࢳ࢜㐣๫⋡ࡢྥୖࢆ┠ᣦࡍࠋ



◊✲ᡂᯝ
඾ᆺඖ⣲࡜ࡋ࡚࢝ࣝ࣎࢝ࢳ࢜ࣥ࡜➼㟁Ꮚᵓ㐀࡛࠶ࡿ࣍࢘⣲ࢆࠊ㠀㸴ဨ⎔ᵓ㐀࡜ࡋ࡚ࢧࢻࣝᆺᵓ㐀ࢆㄏ㉳ࡍ

- 329 -

ࡿ㸵ဨ⎔ᵓ㐀ࢆࡑࢀࡒࢀ㑅ᐃࡋࡓࠋ⌮ㄽィ⟬࡟ࡼࡾࠊ┠ⓗ໬ྜ≀ࡢᵓ㐀࠾ࡼࡧග࣭㟁Ꮚ≀ᛶࢆணࡋࡓࠋ⤖ᯝ࡜ࡋ࡚ࠊ┠ⓗ໬ྜ≀ࡀ୕ḟඖⓗ࡟ᗈࡀࡾࠊ࠿ࡘࠊ㟁Ꮚཷᐜࡢ㧗࠸ȧඹᙺ⣔ࢆ᭷ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
ࡇࢀࡲ࡛ࡢ◊✲࡛ࠊ㘽୰㛫య࡛ࡣ┠ⓗ࡜ࡍࡿࠊ࣍࢘⣲ࡀࢻ࣮ࣉࡉࢀࡓ‴᭤ࢼࣀࢢࣛࣇ࢙ࣥࡢྜᡂࡀᅔ㞴࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡑࡢࡓࡵࠊᮏᖺᗘࡣ⦰⎔ᵓ㐀ࢆቑࡸࡋࡓࠊ⦰⎔๓㥑యࢆ⏝࠸ࡿ࣍࢘⣲ࢻ࣮ࣉ‴᭤
ࢼࣀࢢࣛࣇ࢙ࣥࡢྜᡂࢆヨࡳࡓࠋ᪂ࡋ࠸㘽๓㥑యࡢྜᡂࢆ㸱㏻ࡾࡢྜᡂ⤒㊰࡛ヨࡳࡓࡀࠊ࠸ࡎࢀࡶࠊᮃࡳࡢ
ศᏊኚ᥮ࢆ㐍⾜ࡉࡏࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ⌧ᅾࠊࡉࡽ࡟᪂ࡓ࡞㏫ྜᡂゎᯒ࡟ᇶ࡙ࡃྜᡂ⤒㊰࡟࡚ࠊ᪂ࡋ࠸
㘽๓㥑యࡢྜᡂ࡟ྲྀࡾ⤌ࢇ࡛࠸ࡿࠋ᪂ࡓ࡞ྜᡂ⤒㊰ࡣࠊ୙Ᏻᐃ࡞୰㛫యࢆ⤒⏤ࡋ࡞࠸ࡓࡵࠊ┠ⓗ໬ྜ≀ࡢᏳᐃࡋࡓ㔞ⓗ౪⤥ࡀྍ⬟࡟࡞ࡿࡇ࡜ࡀᮇᚅ࡛ࡁࡿࠋ

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㢌Ⓨ⾲࣭࣏ࢫࢱ࣮㸧 ‫℧ۑ‬ᮏ᫓ᶞ࣭఍⏣࿴ᗈ࣭኱໭ಇᑗ࣭⏣୰ၨ௓࣭ኴ⏣ⱥ௓࣭ᒣཱྀ₶୍㑻 ➨  ᅇ᭷ᶵྜ- 330 -

ᡂࢩ࣏ࣥࢪ࣒࢘㸦2㸧ࠊ᪩✄⏣኱Ꮫᅜ㝿఍㆟ሙࠊ ᭶  ᪥ࠕࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿࢪ࢔࣮ࣜࣝࢣࢺࣥࡢ㑏ඖⓗᐁ⬟ᇶ໬཯ᛂࠖ㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬ᓮཎ┒ᩗ࣭㯮⃝⨾ᶞ࣭Ώ㑓⍞Ṍ࣭ᒣཱྀ₶୍㑻 ➨  ᅇࢧࣈ࢙࢘࢖ࢭ࣑ࢼ࣮㸦3㸧ࠊᮾி኱Ꮫ㥖ሙࣜࢧ࣮ࢳ࢟ࣕࣥࣃࢫ ᮾிࠊ ᭶ ᪥ࠕࢽࢵࢣࣝゐ፹࡟ࡼࡿ࢚ࣀ࣮ࣝㄏᑟయ࡜࣋ࣥࢰ࢜࢟ࢧࢰ࣮ࣝ㢮࡜ࡢ࢚ࣀ࣮ࣛࢺࢲࣥࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࠖ
㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬Ᏺᒇ⍛ே࣭Ṋ⸨៞࣭ᒣཱྀ₶୍㑻 ➨  ᅇࢧࣈ࢙࢘࢖ࢭ࣑ࢼ࣮㸦3㸧ࠊᮾி኱Ꮫ㥖ሙࣜࢧ࣮ࢳ࢟ࣕࣥࣃࢫ ᮾிࠊ ᭶  ᪥ࠕከᵝ࡞ศᏊ๰ฟࢆᚿྥࡋࡓࢡ࣓ࣟࣟࢳࣝ࣎ࣜࣝ1ࢺࢩࣝࣄࢻࣛࢰࣥࡢྜᡂ࡜཯ᛂࠖ
㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬ᐑ㷂㱟ஓ࣭Ṋ⸨៞࣭ᒣཱྀ₶୍㑻 ➨  ᅇࢧࣈ࢙࢘࢖ࢭ࣑ࢼ࣮㸦3㸧ࠊᮾி኱Ꮫ㥖ሙࣜࢧ࣮ࢳ࢟ࣕࣥࣃࢫ ᮾிࠊ ᭶  ᪥ࠕගぶ࿴ᛶᶆ㆑ἲࢆ฼⏝ࡋࡓ᳜≀᫬ィࢱࣥࣃࢡ㉁ࡢྠᐃࠖ
㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬ᆏ஭♸⾰ ࣭㰺⸨ᮥᐇ ࣭ኴ⏣ⱥ௓ ࣭୰㐨⠊ே࣭ᒣཱྀ₶୍㑻 ➨  ᅇ &6- ࣇ࢙ࢫࢱ 㸦3 ࠊࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ᮾிࠊ ᭶ ᪥ࠕ⎔≧࢔ࣝࢥ࣮ࣝࡢ⎔㛤⿣ࢆ㘽࡜ࡋࡓࢭࢥࢺࣜࢸࣝ࣌ࣀ࢖ࢻ㢮ࡢྜᡂࠖ㸦࣏ࢫࢱ࣮㸧‫ۑ‬ᙪᆏᣅ࣭ᫍ㈗அ࣭ኴ⏣ⱥ௓࣭ᒣཱྀ₶୍㑻 ➨  ᅇ &6- ࣇ࢙ࢫࢱ 㸦3㸧ࠊࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ᮾிࠊ ᭶  ᪥ࠕከᵝ࡞ศᏊ๰ฟࢆᚿྥࡋࡓࢡ࣓ࣟࣟࢳࣝ࣎ࣜࣝ1ࢺࢩࣝࣄࢻࣛࢰࣥࡢྜᡂ࡜཯ᛂࠖ
㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬ᐑ㷂㱟ஓ࣭Ṋ⸨៞࣭ᒣཱྀ₶୍㑻 ➨  ᅇ &6- ࣇ࢙ࢫࢱ 㸦3㸧ࠊࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ᮾிࠊ ᭶  ᪥ࠕࢪ࢔࣮ࣜࣝࢣࢺࣥࡢゐ፹ⓗ⬺㓟⣲ᆺኚ᥮཯ᛂ࡟ࡼࡿ࣐ࣝࢳ࢔࣮ࣜࣝ࢔ࣝ࢝ࣥࡢྜᡂ ࠖ㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬㯮⃝⨾ᶞ࣭ຍ⸨೺ኴ࣭Ṋ⸨៞࣭ᒣཱྀ₶୍㑻 ➨  ᅇ᭷ᶵྜᡂ໬Ꮫࢭ࣑ࢼ࣮㸦3㸧ࠊ࢔ࢡࢸ࢕ࣈࣜࢰ࣮ࢶ⚟ᒸඵᖭ⚟ᒸࠊ ᭶  ᪥ࠕࢽࢵࢣࣝゐ፹࡟ࡼࡿ࢚ࣀ࣮ࣝㄏᑟయ࡜࣋ࣥࢰ࢜࢟ࢧࢰ࣮ࣝ㢮࡜ࡢ࢚ࣀ࣮ࣛࢺࢲࣥࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࠖ
㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬Ᏺᒇ⍛ே࣭Ṋ⸨៞࣭ᒣཱྀ₶୍㑻 ➨  ᅇ᭷ᶵྜᡂ໬Ꮫࢭ࣑ࢼ࣮㸦3㸧ࠊ࢔ࢡࢸ࢕ࣈࣜࢰ࣮
ࢶ⚟ᒸඵᖭ ⚟ᒸࠊ ᭶  ᪥ࠕྍどගࢆ฼⏝ࡋࡓ⤖ྜ㛤⿣཯ᛂࡢ㛤Ⓨࠖ㸦ᣍᚅㅮ₇㸧 ‫ۑ‬ኴ⏣ⱥ௓ ➨  ᅇ᭷ᶵ໬Ꮫ࣭๰⸆໬Ꮫࢭ࣑ࢼ࣮ࠊ⟃Ἴ኱Ꮫ Ⲉᇛࠊ ᭶  ᪥ࠕࣝ࢖ࢫ㓟ྍどගࣞࢻࢵࢡࢫゐ፹⣔ࢆ฼⏝ࡋࡓ 1࣋ࣥࢰ࢖ࣝࣆࣟࣜࢪࣥࡢ㛤⎔཯ᛂࠖ㸦ཱྀ㢌㸧 ‫ۑ‬ᖹᑿࡲࡾ࡞࣭఍⏣࿴ᗈ࣭ኴ⏣ⱥ௓࣭ᒣཱྀ₶୍㑻 ➨  ᅇ」⣲⎔໬Ꮫウㄽ఍㸦2㸧ࠊ㜰Ꮫࢥࣥ࣋ࣥࢩࣙࣥࢭࣥࢱ࣮ࠊ᭶  ᪥
ࠕࢪࣝࢥࣀࢭࣥྍどගࣞࢻࢵࢡࢫゐ፹ࢆ⏝࠸ࡓȪ⤖ྜ㛤⿣཯ᛂࡢ㛤Ⓨࠖ㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬ኴ⏣ⱥ௓࣭఍⏣࿴ᗈ࣭኱໭ಇᑗ࣭ᖹᑿࡲࡾ࡞࣭⏣୰ၨ௓࣭⯪ᶫ⸛Ꮚ࣭ᒣཱྀ₶୍㑻 ➨  ᅇኳ↛᭷ᶵ໬ྜ≀ウㄽ఍㸦3㸧ࠊ㟼ᒸᕷΎỈᩥ໬఍㤋࣐ࣜࢼ࣮ࢺ 㟼ᒸࠊ ᭶  ᪥ࠕࣆࣛࢰࣟ࢔ࢪࣥ㢮ࡢ㛤⎔ᆺࢪࣇࣝ࢜ࣟ໬཯ᛂࠖ㸦࣏ࢫࢱ࣮㸧 ‫ۑ‬኱ᮌ㢼㇦࣭ᑠᯇ⏣㞞᫭࣭㏆⸨⿱㈗࣭ᒣཱྀ₶୍㑻 ➨  ᅇࣇࢵ⣲໬Ꮫⱝᡭࡢ఍㸦3㸧ࠊ࢜ࣥࣛ࢖ࣥࠊ ᭶  ᪥ࠕࢪࣝࢥࣀࢭࣥ㸫ྍどගࣞࢻࢵࢡࢫ༠ാゐ፹⣔ࢆ฼⏝ࡋࡓ࢔ࣝ࢟ࣝࣇࣝ࢜ࣜࢻࡢ &̽) ⤖ྜ㛤⿣཯ᛂࠖ㸦࣏ࢫࢱ࣮㸧 ‫℧ۑ‬ᮏ᫓ᶞ࣭఍⏣࿴ᗈ࣭ኴ⏣ⱥ௓࣭ᒣཱྀ₶୍㑻 ➨  ᅇࣇࢵ⣲໬Ꮫⱝᡭࡢ఍㸦3㸧ࠊ࢜ࣥࣛ࢖ࣥࠊ ᭶  ᪥ࠕࣝ࢖ࢫ㓟ྍどගࣞࢻࢵࢡࢫゐ፹⣔ࢆ฼⏝ࡋࡓ 1࢔ࢩࣝࣆࣟࣜࢪࣥࡢ㛤⎔཯ᛂࠖ㸦ཱྀ㢌㸧 ‫ۑ‬ᖹᑿࡲࡾ࡞࣭
఍⏣࿴ᗈ࣭ኴ⏣ⱥ௓࣭ᒣཱྀ₶୍㑻 ➨  ᅇ᭷ᶵ཯ᛂⱝᡭࡢ఍㸦2㸧ࠊ࢜ࣥࣛ࢖ࣥࠊ ᭶  ᪥

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ᗘซ㛵ᩘἲ㸦DFT㸧ィ⟬ࡣࠊ」㞧࡞ศᏊᵓ㐀࠿ࡘ㟁Ꮚᵓ㐀ࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒యࡢᛶ㉁ࡢゎ᫂ࡸ཯ᛂᶵᵓゎᯒ࡟࠾࠸࡚ࠊ㢖⧚࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋࡉࡽ࡟ࠊ㏆ᖺ࡛ࡣィ⟬ᶵࡢᛶ⬟ྥୖ࡟ࡼࡾࠊࡑࡢィ⟬⢭ᗘࡣ㠀ᖖ࡟㧗ࡃ࡞ࡾࠊ㑄⛣㔠ᒓゐ፹཯ᛂࢆ⏝࠸ࡓゐ፹཯ᛂ㛤Ⓨ࡟࠾࠸࡚Ḟ࠿ࡍࡇ࡜ࡢ࡛ࡁ࡞࠸ࢶ࣮ࣝ࡜࡞ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊDFT ィ⟬࡟ࡼࡾ཯ᛂ࣓࢝ࢽࢬ࣒ࢆ෌⌧ࡍࡿࡔࡅ࡛ࡣ࡞ࡃࠊ㑄⛣≧ែ࡟࠾ࡅࡿ㟁Ꮚ≧ែࢆヲ⣽࡟ㄪ࡭ࡿࡇ࡜࡛᪂ࡓ࡞཯ᛂ⌮ㄽࡢᥦ᱌ࢆ⾜࠺ࠋᮏ✏࡛ࡣࠊࢺࣜ࢔࣮ࣜࣝ࣍࢘⣲ゐ፹ࢆ⏝࠸ࡓࠊዃ㞧≀ࢆྵ᭷ࡍࡿỈ⣲㸦⢒Ỉ⣲㸧ࡢ᭷ᶵࣁ࢖ࢻࣛ࢖ࢻἲ࡟
ࡼࡿ㈓ⶶ࠾ࡼࡧ⢭〇࡟㛵ࡍࡿ◊✲࡟ࡘ࠸࡚⾜ࡗࡓィ⟬⤖ᯝࢆሗ࿌ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬⏝ࣃࢵࢣ࣮ࢪ࡜ࡋ࡚ Gaussian 16(rev. C.01)ࢆ౑⏝ࡋࠊࢽࢵࢣࣝ(0)㘒యୖ࡟࠾ࡅࡿ୍㓟໬Ⅳ⣲

ࡢ໬Ꮫ྾╔ࠊ⬺╔㐣⛬࡟࠾ࡅࡿศᏊᵓ㐀࡜⮬⏤࢚ࢿࣝࢠ࣮ࢆᐦᗘซ㛵ᩘ⌮ㄽ㸦DFT㸧ィ⟬࡟ࡼࡾồࡵࡓࠋࡲ
ࡓࠊNBO ࢆ⏝࠸࡚㑄⛣≧ែ࡟࠾ࡅࡿ㌶㐨㛫┦஫స⏝ࢆᐃ㔞ࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮࡜㓄఩Ꮚᵓ㐀ࡢ㐪࠸ࡢ㛫࡟₯ࡴヲ⣽ࢆㄪᰝࡋࡓࠋ



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ࢺࣜ࢔࣮ࣜࣝ࣍࢘⣲໬ྜ≀ (B1ࠊB2) ࡜୍㓟໬Ⅳ⣲ (CO) ࡜ࡢ௜ຍయᙧᡂ㐣⛬࡟࠾ࡅࡿ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࠊ࠾ࡼࡧάᛶ໬࢚ࢿࣝࢠ࣮ࢆ DFT ィ⟬࡟ࡼࡗ࡚⟬ฟࡋࡓ (ḟ㡫ᅗ)ࠋ
ᮏ㐣⛬ࡀ྾࢚ࣝࢦࣥⓗ (B1: 'G = +3.2 kcal mol-1ࠊB2: 'G = +8.1 kcal mol-1) ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢ⤖ᯝࡣ B1 ࢆゐ፹࡟⏝࠸ࡓỈ⣲໬཯ᛂ⣔࡟࠾࠸࡚ CO ࡀ཯ᛂࢆ㏿ᗘㄽⓗ࡟㜼ᐖࡍࡿࠊ࡜࠸࠺ᐇ㦂࡟୍⮴ࡍࡿࠋࡲ
ࡓࠊB2 ࢆゐ፹࡟⏝࠸ࡓỈ⣲໬཯ᛂ⣔࡟࠾࠸࡚ CO ࡣ࡯࡜ࢇ࡝㜼ᐖຠᯝࢆ♧ࡉ࡞࠸ࠊ࡜࠸࠺ᐇ㦂஦ᐇ࡟ࡶ▩┪ࡋ࡞࠸ࠋDFT ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ௜ຍయࡢ᭱㐺ᵓ㐀ࡢ⤖ྜゅ࠿ࡽ τ ࢆィ⟬ࡍࡿࡇ࡜࡛ᅄ㠃యᵓ㐀࠿ࡽࡢṍࡳලྜࢆẚ㍑ࡋࡓ࡜ࡇࢁࠊB2 ࡜ CO ࡜ࡢ௜ຍయࡀࡼࡾ⌮᝿ⓗ࡞ᅄ㠃యᵓ㐀࠿ࡽṍࢇࡔᵓ㐀ࢆྲྀࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ⌮᝿ⓗ࡞ᅄ㠃యᵓ㐀࠿ࡽࡢṍࡳࡀ኱ࡁ࠸࡜௜ຍయࡀ୙Ᏻᐃ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡓࡵࠊࡇࢀࡽࡢ⤖ᯝ
ࡶ B2 ࡀ CO ࡟ࡼࡿ㜼ᐖຠᯝࢆཷࡅ࡟ࡃ࠸ࠊ࡜࠸࠺ᐇ㦂஦ᐇ࡜▩┪ࡋ࡞࠸ࠋࡇࢀࡲ࡛ࠊCO ࢆྵࡴ⢒Ỉ⣲᮲௳ୗ࡛ࡢࢺࣜ࢔࣮ࣜࣝ࣍࢘⣲ゐ፹ࢆ⏝࠸ࡓỈ⣲໬཯ᛂࢆᐇ⌧ࡋࠊCO ࡞࡝ࡢዃ㞧≀࡟ࡼࡿ཯ᛂ⣔࡬ࡢᙳ㡪ࢆヲ⣽࡟㆟ㄽࡋࡓ౛ࡣ࡞࠸ࠋᮏ⤖ᯝࡣ⢒Ỉ⣲ࢆ┤᥋฼⏝ࡋࡓ୙㣬࿴໬ྜ≀ࡢỈ⣲໬཯ᛂࢆ㘽࡜ࡍࡿ᪂ࡓ࡞Ỉ⣲⢭〇ࣉࣟࢭࢫࡢᵓ⠏࡬ࡢ㔜せ࡞▱ぢ࡟࡞ࡿ࡜⪃࠼࡚࠸ࡿࠋ

- 335 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
1.

‫ۻ‬Y. Hoshimoto, M. Sakuraba, T. Kinoshita, M. Ohbo, M. Ratanasak, J. Hasegawa, S. Ogoshi Commun. Chem.
2021, 4, 137.

2.

‫ۻ‬Y. Yamauchi, Y. Hoshimoto, T. Kawakita, T. Kinoshita, Y. Uetake, H. Sakurai, S. Ogoshi J. Am. Chem. Soc.
2022, 144, 8818.

3.

‫ۻ‬T. Hashimoto, T. Asada, S. Ogoshi, Y. Hoshimoto Sci. Adv. 2022, 8, eade0189.

4.

‫ۻ‬Y. Hoshimoto, Y. Yamauchi, T. Terada, S. Ogoshi Can. J. Chem. in press.

5.

‫ۻ‬S. Nagai, T. Hinogami, S. Ogoshi, Y. Hoshimoto ChemRxiv preprint (DOI: 10.26434/chemrxiv-2023-qv422v2).

6.

R. Doi, M. Yasuda, N. Kajita, K. Koh, S. Ogoshi J. Am. Chem. Soc. In press.

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ࢺࣟࢫࣉ࣮ࣞ࢖࢜ࣥ໬ἲ࡟ࡼࡾ 90㸫㔠ᒓ㘒యࢆ⏕ᡂࡋࠊᅄ㔜ᴟ㉁㔞ศᯒィ㸦406㸧࡛≉ᐃࡢ࢖࢜ࣥࡢࡳࢆ
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ࡇࡇ࡟Ἴ㛗ྍኚ㉥እ࣮ࣞࢨ࣮ࢆᑟධࡋࠊ㉥እ྾཰࡟ࡼࡾᚓࡽࢀࡓゎ㞳≀ࡢ࢖࢜ࣥ㔞ࢆᚋẁࡢ㉁㔞ศᯒィ࡛ᐃࡍࡿࡇ࡜࡛㉥እ྾཰ࢫ࣌ࢡࢺࣝ࡟┦ᙜࡍࡿ㉥እගゎ㞳㸦,53'㸧ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋỈ࿴ࢡࣛࢫࢱ࣮ࡢྲྀࡾ࠺ࡿᒁᡤᏳᐃᵓ㐀ࢆ ')7 ィ⟬࡟ࡼࡾồࡵࠊ
,53' ࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࠿ࡽศᏊᵓ㐀ࢆᖐᒓࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚%/<3'%-ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ * GS ࢆ⏝࠸ࠊ*DXVVLDQ ࡛ ')7ィ⟬ࢆ⾜ࡗࡓࠋ

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ඃኴࠊὸ㔝

ඞோࠊ῝⃝

ு㍜

㸦ᮾிᕤᴗ኱Ꮫ≀㉁⌮ᕤᏛ㝔㸧1◊✲┠ⓗᮏ◊✲ࡢ┠ⓗࡣࠊ඲ཎᏊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ㓄ྥᶞ⬡ᮦᩱࡢ⇕ఏᑟ≉ᛶࡢ᳨ウ࡛࠶ࡿࠋ㏆ᖺࠊ࢚ࣞࢡࢺࣟࢽࢡࢫࢹࣂ࢖ࢫࡢ㛤Ⓨ࡟࠾࠸࡚ᨺ⇕ᛶࡢྥୖࡀồࡵࡽࢀ࡚࠸࡚ࠊᡂ
ᙧᛶ࡟ඃࢀศᏊタィࡸ」ྜ໬ࡀᐜ᫆࡞㧗ศᏊᮦᩱࡢ㧗⇕ఏᑟ໬ࡢ◊✲࡟ὀ┠ࡀ㞟ࡲࡗ࡚࠸ࡿࠋ
㧗ศᏊᮦᩱࡢ⇕ఏᑟ⋡ࢆྥୖࡉࡏࡿࡓࡵࡢศᏊタィ࡜ࡋ࡚ࠊᾮᬗᙧᡂ⬟ࢆ᭷ࡍࡿᵓ㐀༢఩㸦࣓ࢯࢤࣥ㸧ࢆ㧗ศᏊ㙐ࡢ⧞ࡾ㏉ࡋ༢఩࡟⤌ࡳ㎸ࡴࡇ࡜ࡸࠊ㧗ศᏊ㞟ྜᵓ㐀ࡢ㓄ྥไᚚࢆ฼⏝ࡍࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࣇ࢛
ࣀࣥࡢࣃ࣮ࢥ࣮ࣞࢩࣙࣥࣃࢫࡢᙧᡂࡀ⇕ఏᑟࡢせᅉ࡛࠶ࡿ࡜࠸࠺௬ᐃ࡟ᇶ࡙ࡁࠊ⇕ఏᑟ⋡ྥୖ࡟ࡣ␗᪉ⓗ࡞㓄ྥ㞟ྜᵓ㐀ࡢᙧᡂࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᡃࠎࡣࠊ⮬ᕫ㞟ྜ㓄ྥ≧ែ࡟࠾ࡅࡿ⇕ఏᑟᶵᵓࡢゎ᫂࡜㧗⇕ఏᑟᮦᩱࡢศᏊタィࡢ☜❧ࢆ┠ᣦࡋࠊ㧗ศᏊᾮᬗࡸ㓄ྥࡋࡓᶞ⬡ᮦᩱࡢᵓ㐀࡜ศᏊ㐠ືᛶࡢ⇕ఏᑟ⋡࡟㛵ࢃࡿᐤ୚ࡢ᳨ウࢆ⾜࠺ࠋᡃࠎࡣࠊ୺㙐ᆺ㧗ศᏊᾮᬗࡢ┦㌿⛣ᣲື࡜ࢥ࣓࣮ࣥ࣍ࢩࣙࣥ≉ᛶ࡟ࡘ࠸࡚ࠊ㔜Ỉ⣲ NMR

ᐃ࡜ᅇ㌿␗ᛶ

≧ែ㏆ఝゎᯒࢆ⤌ࡳྜࢃࡏࠊ࢔ࣝ࢟ࣝࢫ࣮࣌ࢧ࣮࡟≉᭷ࡢࢿ࣐ࢳࢵࢡ࣭ࢥ࣓࣮ࣥ࣍ࢩࣙࣥࡢᐃ㔞ⓗゎᯒࢆ⾜࠸ࠊ⇕ຊᏛ㔞ࡢഅወຠᯝࡢཎᅉࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓ[1]ࠋ᫂ࡽ࠿࡟ࡋࡓࢿ࣐ࢳࢵࢡ┦ࡢࢥ࣓࣮ࣥ࣍ࢩࣙࣥࢆ⏝࠸࡚ࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺࠊ☢໬⋡ࡢ␗᪉ᛶࠊගᏛ␗᪉ᛶࡢᐇ㦂್ࢆ᳨ドࡋࡓࠋࡉࡽ࡟ࠊᾮᬗࡢ␗᪉┦㸫➼᪉┦㌿⛣࡟࠾ࡅࡿ≀ᛶኚ໬ࢆศᏊ㓄ྥࡸศᏊࢥ࣓࣮ࣥ࣍ࢩࣙࣥ࡞࡝ࡢศᏊࣞ࣋ࣝࡢ᝟ሗ࡜㛵㐃௜ࡅ࡚ࠊ㓄ྥ␗᪉ᛶሙ࡟࠾ࡅࡿศᏊࡢᯝࡓࡍᙺ๭ࢆᐃ㔞ⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ᐇ㦂ⓗᡭἲ࡟ྜࢃࡏ࡚ศᏊࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢆ⾜࠺ᚲせࡀ࠶ࡿࠋ௦⾲ⓗ࡞ࢧ࣮ࣔࢺࣟࣆࢵࢡ༢㔞యᾮᬗ࡛࠶ࡿ 4-cyano-4’-alkylbiphenyl ࡟ࡘ࠸࡚ࡣࠊ㐺ࡋࡓຊሙಟṇࡀ⾜ࢃࢀ࡚࠸ࡿࠋಟṇ Amber ᆺຊሙࢆ⏝࠸ࡓ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊ➼᪉┦࠿ࡽࢿ࣐ࢳࢵࢡ┦㸦N ┦㸧࡬ࡢ⮬Ⓨⓗ㌿⛣ࢆ෌⌧ࡋࠊᐦᗘࡢ

ᗘ౫Ꮡᛶࡸ┦㌿⛣

ᗘ࡞࡝ࡢᐇ㦂⤖ᯝࢆࡼࡃ෌⌧ࡋࡓࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ

[2,3]ࠋᮏ◊✲࡛ࡣᾮᬗࡢ⌮᝿ⓗ࡞ࣔࢹࣝศᏊ࡛࠶ࡿ༢㔞యᾮᬗࠊ
4-Cyano-4’-pentyloxybiphenyl(5OCB) (Figure 1)࡟ࡘ࠸࡚ࠊMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐺⏝ࡋ࡚ᾮᬗ-➼᪉┦㌿⛣ᣲື࡜⇕ఏᑟᶵᵓࢆ᳨ウࡍࡿࠋࡉࡽ࡟ࠊ࣑ࢡࣟᵓ㐀࡜࣐ࢡࣟ≀ᛶࡢ┦㛵ᛶࡸᖹᆒ஧஌ኚ఩(MSD)࡞࡝
ࡢືⓗ࡞≉ᛶࢆㄪ࡭ࡿࠋ
ࡉࡽ࡟ࠊ㏫㠀ᖹ⾮ศᏊືຊᏛἲ(RNEMD)࡟ࡼࡾ 5OCB ࡢ⇕ఏᑟ⋡ࢆィ⟬ࡋࠊᐇ㦂್࡜ẚ㍑᳨ウࢆ⾜࠸ࠊ⇕ఏᑟ⋡ࡢᡂศศ๭ゎᯒ࡜ࣇ࢛ࣀࣥࡢ≧ែᐦᗘ PDoS ࢆホ౯ࡋ࡚ࠊ⇕ఏᑟᶵᵓ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ- 351 -

2◊✲᪉ἲࠊィ⟬᪉ἲMD ィ⟬ࡣ LAMMPS ࣉࣟࢢ࣒ࣛ 3Mar20 ࣂ࣮ࢪࣙࣥࢆ⏝࠸࡚⾜ࡗࡓࠋࡲࡓࠊ㔞Ꮚ໬Ꮫィ⟬ࡣ Gaussian16ࢆ⏝࠸࡚⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᑐ㇟࡜ࡋࡓศᏊࡣ 5OCB ࡛࠶ࡿࠋ256 ศᏊ࡛⣔ࢆᵓᡂࡋ㸪ቃ⏺᮲௳࡟ࡣ࿘ᮇቃ⏺᮲௳ࢆ⏝࠸ࡓ㸬ຊሙࡣ㧗ᶫࡽ[2]ࡀసᡂࡋࡓࢩ࢔ࣀࣅࣇ࢙ࢽࣝ⏝ಟṇຊሙ࡟ࠊࡉࡽ࡟஧㠃ゅ㡯ࢆ㏣ຍಟṇࡋࡓຊሙࢆ౑⏝ࡋࡓࠋ㟁Ⲵࡣ CHELPG ἲࢆ⏝࠸࡚ MP2/6-31G+(d) ࡛ィ⟬ࡋࡓ㟁Ⲵࢆ⏝࠸ࡓࠋィ⟬ࡢ᫬㛫้ࡳࡣ 1 fs ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᐇ㦂್ࡼࡾపᐦᗘࡢ 0.8 g/cm3 ࡛❧᪉యࢭࣝ࡟ศᏊ㓄⨨ࢆࣛࣥࢲ࣒࡟Ⓨ⏕ࡉࡏࠊ➼᪉┦ࡢᗘ࡛ࠊNPT ᮲௳ୗ࡛⦆࿴ࡉࡏ࡚➼᪉┦ࢆసᡂࡋࡓࠋࡇࢀࢆึᮇᵓ㐀࡜

ࡋ࡚ࠊNPT ࢔ࣥࢧࣥࣈ࡛ࣝࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ㏆ഐࡢ

ᗘᩘⅬ࡛ 5 ns 㛫ࡢィ⟬ࢆ⾜࠸ࠊࡉࡽ࡟ 100 ns

ࡢᖹ⾮໬ࢆ⾜ࡗࡓࠋNPT ィ⟬࡛ࡣࠊNose-Hoover ࢧ࣮ࣔࢫࢱࢵࢺ࡜ Parrinello-Rahman ࣂࣟࢫࢱࢵࢺࢆ⏝࠸ࠊ1bar ࡢᅽຊୗ࡛ᐇ⾜ࡋࡓࠋ⣔ࡢ㓄ྥ࡟ࡘ࠸࡚ࡣࠊ㓄ྥ⛛ᗎᗘ P2 ࢆィ⟬ࡋ࡚ホ౯ࡋࡓࠋ㓄ྥ⛛ᗎᗘ P2 ࡣ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱࢸࣥࢯࣝ Q㸦ᘧ㸯㸧ࡢ᭱኱ᅛ᭷್࡜ࡋ࡚ᚓࡓࠋ

QDE

 N 
¦ PiD PiE  GDE     㸦㸯㸧
N iࡇࡇ࡛ࠊ P iD (D=x, y, z)ࡣศᏊ i ࡢศᏊ㍈࣋ࢡࢺࣝᡂศࠊG DE ࡣࢡࣟࢿࢵ࣮࢝ࡢࢹࣝࢱࠊN ࡣศᏊᩘ࡛࠶ࡿࠋศ
Ꮚ㍈࣋ࢡࢺࣝࡣศᏊࡢ័ᛶࢸࣥࢯࣝࡢ᭱ᑠᅛ᭷್ࢆ୚࠼ࡿᅛ᭷࣋ࢡࢺࣝ࠿ࡽồࡵࡓࠋ㓄ྥࡋࡓ 335 K ࡢࢿ࣐ࢳࢵࢡ㓄ྥ┦ 40 ns ࡢᗙᶆࡢࢺࣛࢪ࢙ࢡࢺࣜ࠿ࡽ MSD ࡜⮬ᕫ┦㛵࡟㛵ࡍࡿ୰㛫ᩓ஘㛵ᩘࢆ⟬ฟࡋࡓࠋ
⇕ఏᑟ⋡ࡣࠊ㏫㠀ᖹ⾮ศᏊືຊᏛἲ[4]࡟ࡼࡾ⟬ฟࡋࡓࠋ㏫㠀ᖹ⾮ศᏊືຊᏛἲ࡛ࡣࠊࢭࣝࢆほ20 ศ๭ࡋ㸪య✚࢚ࢿࣝࢠ୍࣮ᐃ᮲௳ୗ࡛㸪㧗
᮰࡜

ࢫࣛࣈ࡜ప

㍈᪉ྥ࡟

ࢫࣛࣈ࡜ࡢ㛫࡛ 10 ns 㛫㏿ᗘ஺᥮ࢆ⾜࠸ࠊ⇕ὶᗘ໙㓄ࢆⓎ⏕ࡉࡏ Fourier ࡢἲ๎࠿ࡽ⇕ఏᑟ⋡ࢆᚓࡓࠋ⇕ఏᑟ⋡ࡢᡂศศゎゎᯒࡣࠊ඲యࡢ࢚ࢿࣝࢠ࣮

ὶ㏿ࢆᑐὶ㡯ࠊศᏊ㛫ࠊ࠾ࡼࡧศᏊෆࡢ┦஫స⏝࡟ศゎࡋࠊࡑࢀࡒࢀࡢᐤ୚࠿ࡽồࡵࡓࠋ3◊✲ᡂᯝFigure 2 ࡟ྛ

ᗘࡢ MD ィ⟬ࡢ 85㹼90 ns ࡢ 5 ns㛫࡟࠾ࡅࡿᐦᗘࡢᖹᆒ್ࡢ

ᗘ౫Ꮡᛶࢆ♧ࡋࡓࠋMD ィ⟬࠿ࡽᚓࡽࢀࡓ್ࡣᐇ㦂್࡜࡯ࡰྠᵝ࡞ഴྥࡀᚓࡽࢀࡓࠋࡲࡓࠊ343 K ௜㏆࡟࠾࠸࡚ᐦᗘࡢ୙㐃⥆ᛶࡀほࡉࢀ㸪➼᪉┦-ࢿ࣐ࢳࢵࢡ┦ࡢ┦㌿⛣ࡶィ⟬࡛ࡣ෌⌧ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋྛ
ᗘ࡟࠾ࡅࡿ⣔ࡢ㓄ྥ⛛ᗎᗘ P2 ࡢ᫬㛫Ⓨᒎࡢ⤖ᯝ࠿ࡽࠊ335㹼343K ࡟࠾ࡅࡿ P2 ࡀ 0.4~0.6 ࡜࡞ࡾࠊࢿ࣐ࢳࢵࢡ㓄ྥ┦ࡀⓎ⌧ࡋ࡚࠸ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ
Figure 3 ࡟ 335K ࡢࢿ࣐ࢳࢵࢡ┦࡟࠾ࡅࡿ MSD ࡢ᫬㛫Ⓨᒎࢆ♧ࡋࡓࠋࢿ࣐ࢳࢵࢡ┦࡛ࡢ MSD ࡢሙྜࠊศᏊ㓄ྥᖹ⾜᪉ྥ x ㍈ࡢ㛗᫬㛫࡟࠾ࡅࡿኚ఩ࡀࠊ

Figure 2. Temperature dependence of densities
obtained by MD simulations and observed densities.

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ᆶ┤᪉ྥࡢ y ࠾ࡼࡧ z ㍈ࡢ MSD ್ࡼࡾࡶ኱ࡁࡃ࡞ࡗ
࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ▷᫬㛫࡛ࡢኚ఩࡛ࡣࠊࡑࡢ
㏫ࡢഴྥࡢᆶ┤᪉ྥࡀᖹ⾜᪉ྥࡼࡾࡶ኱ࡁ࠸ࡇ࡜ࡀ
ศ࠿ࡗࡓࠋ⮬ᕫ┦㛵࡟㛵ࡍࡿ୰㛫ᩓ஘㛵ᩘࡢ⤖ᯝ࠿ࡽࡣࠊ1 ps ௨ୗࡢ▷᫬㛫㡿ᇦ࡜ 100 ps ௨㝆ࡢ㛗᫬㛫㡿ᇦ࡛≉ᚩⓗ࡞⦆࿴ࡀぢࡽࢀࡓࠋྛཎᏊࡈ࡜࡛ホ౯ࡋࡓ⮬ᕫ┦㛵୰㛫ᩓ஘㛵ᩘ࠿ࡽࠊ2 ࡘࡢ⦆࿴ᣲືࡀ
ほࡉࢀࠊ࢔ࣝ࢟ࣝ㙐ࡢᒁᡤⓗ࡞㐠ື࡜㓄ྥ᪉ྥࡢ⮬ᕫᣑᩓࡀ▷᫬㛫࡜㛗᫬㛫㡿ᇦࡢࡑࢀࡒࢀ࡟ᐤ୚ࡋ
࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

Figure 3. Time evolution of mean squaredisplacements for total molecular motion andthe directions of x, y, and z axes.

ࢿ࣐ࢳࢵࢡ┦ࡢ 335K ࡟࠾ࡅࡿ 5OCB ࡢ⇕ఏᑟ⋡࡜ࡑࡢᡂศศゎࡢ⤖ᯝࢆ Figure 4 ࡟♧ࡋࡓࠋศᏊ㓄ྥ x㍈᪉ྥࡢィ⟬್ 0.20 W m-1 K-1 ࡣࠊᐇ㦂್ 0.22 W m-1
K-1 ࢆⰋዲ࡟෌⌧ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ㓄ྥᖹ⾜᪉ྥ x ㍈ࡢ⇕ఏᑟ⋡ࡀᆶ┤᪉ྥ y ࡜ z ㍈ࡢ⇕ఏᑟ⋡ࡼࡾࡶ኱ࡁࡃࠊ⇕ఏᑟ⋡ࡢ␗᪉ᛶࡶ☜ㄆࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋᡂศศゎࡢ⤖ᯝࠊศᏊ㓄ྥᖹ⾜᪉ྥ࡟࠾ࡅࡿ⇕ఏᑟ⋡.x ࡛ࡣࠊศᏊෆ┦஫స⏝ࡢ㡯㸦⤖ྜఙ⦰ࠊ⤖ྜኚゅࠊ஧㠃ゅࠊ࠾ࡼࡧศᏊෆ㠀⤖ྜ┦஫స⏝㸧࡜ᑐὶ㡯ࡢ๭ྜࡀᆶ┤᪉ྥ࡟ẚ࡭࡚኱ࡁࡃ
࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋศᏊ㐠ືᛶ࡜⇕ఏᑟ⋡ࡢᑐὶ㡯࡜ࡣ┦㛵ᛶࡀ࠶ࡾࠊࢿ࣐ࢳࢵࢡ┦࡛ࡣࠊศᏊ㓄ྥᖹ⾜᪉ྥࡢ㐠ືࡀ⇕ఏᑟ⋡࡟኱ࡁࡃᙳ
㡪ࢆཬࡰࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

)LJXUH  &RQWULEXWLRQV RI FRQYHFWLRQ DQG HDFKW\SH RI LQWHUDFWLRQ WR WKH WKHUPDO FRQGXFWLYLWLHVN[N\ N] LQWKHQHPDWLFSKDVH

5OCB ࡢࢿ࣐ࢳࢵࢡ㓄ྥ┦࡟࠾ࡅࡿ⇕ఏᑟ⋡ࡢ␗᪉ᛶࡢཎᅉࢆゎ᫂ࡍࡿࡓࡵ࡟㸪ࣇ࢛ࣀࣥࡢ≧ែᐦᗘ
PDoS ࢆ xࠊyࠊ࠾ࡼࡧ z ㍈᪉ྥ࡟ศࡅ࡚ホ౯ࡋࡓࠋPDoS ࡣࠊ㏿ᗘࡢ⮬ᕫ┦㛵㛵ᩘࢆࣇ࣮࢚ࣜኚ᥮ࡍࡿࡇ
࡜࡟ࡼࡾ⟬ฟࡋࡓࠋᚓࡽࢀࡓ PDoS ࢆ Figure 5 ࡟♧
ࡋࡓࠋ2100 cm-1 ௜㏆ࡢࣆ࣮ࢡࡣᾮᬗ࣓ࢯࢤࣥࡢࢩ࢔
ࣀᇶࡢఙ⦰᣺ື࡟⏤᮶ࡋࠊศᏊ㓄ྥ x ㍈᪉ྥࡢࣆ࣮
ࢡࡢᙉᗘࡀ y ࡜ z ㍈ࡢࣆ࣮ࢡࡼࡾ኱ࡁ࠸ࠋCN ⤖ྜࡣศᏊ㓄ྥᖹ⾜᪉ྥ࡟୪ࡧࡸࡍࡃࠊ㓄ྥ᪉ྥ࡟ࣇ࢛ࣀࣥ
ࡢ≧ែᐦᗘࡀ኱ࡁ࠸ࡓࡵࠊ⤖ྜ᪉ྥ⏤᮶ࡢ⇕ఏᑟ⋡ࡣ㓄ྥᖹ⾜᪉ྥ࡟㧗ࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ
ࡓࠋ
5OCB ࡢࢿ࣐ࢳࢵࢡ┦࡟࠾ࡅࡿศᏊ㐠ືࡢ␗᪉ᛶ
࡜⇕ఏᑟ⋡ࡢ┦㛵ࡀ᫂ࡽ࠿࡟࡞ࡾࠊ㓄ྥᵓ㐀ࡢ⇕ఏᑟ

Figure 5. Phonon density of states (PDoS) calculated
for each direction [ \ DQG ] D[LV in the nematic
phase

⋡ྥୖࡢศᏊタィ࡟ᐤ୚ࡍࡿᡂᯝࡀᚓࡽࢀࡓࠋ

- 353 -

ࠕཧ⪃ᩥ⊩ࠖ[1] Abe, A., Furuya, H., Zhou, Z., Hiejima, T., and Kobayashi, Y., Adv. Polym. Sci., 181, 121-152 (2005).
[2] Takahashi, Y., Ishikawa, R., and Kawauchi, S., J. Comput. Chem. Jpn., 14, 211-212 (2016).
[3] Sasaki, R., Takahashi, Y., Hayashi, Y., and Kawauchi, S., J. Phys. Chem. B 124, 881̽889 (2020).
[4] Müller-Plathe, F., J. Chem. Phys., 106, 6082–6085(1997).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬1. ὸ㔝 ඞோࠊྂᒇ ⚽ᓠࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᾮᬗࣔࢹࣝศᏊࡢ⇕ఏᑟᶵᵓࡢゎ᫂ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2022 ᖺ᫓Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ‫ۻ‬2. ྂᒇ ⚽ᓠࠊ㉥ሯ ၨ⣖ࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ୺㙐ᆺ㧗ศᏊᾮᬗࣔࢹࣝศᏊࡢ⇕ఏᑟ≉ᛶゎᯒࠊ➨ 71 ᅇ㧗ศᏊᏛ఍㧗ศᏊウㄽ఍㸦2022 ᖺ㸧ࠋ
3. ᑠ㔝⃝ ඃኴࠊᱱ ᬡᩩࠊྂᒇ ⚽ᓠࠊ୰ᔱ ೺ࠊཎᏊ㛫ຊ㢧ᚤ㙾ࢆ⏝࠸ࡓȘ-࣊ࣜࢵࢡࢫࢆᙧᡂࡍࡿ࣏ࣜ࣌
ࣉࢳࢻ୍ᮏ㙐ࡢຊᏛ≀ᛶホ౯ࠊ➨ 71 ᅇ㧗ศᏊᏛ఍㧗ศᏊウㄽ఍㸦2022 ᖺ㸧ࠋ‫ۻ‬4. ὸ㔝 ඞோ, ྂᒇ ⚽ᓠࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᾮᬗࣔࢹࣝศᏊࡢືⓗ≉ᛶཬࡧ⇕ఏᑟᶵᵓࡢゎ᫂ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2022 ᖺ⛅Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ
5. ᕝ℩ 㝧ྖ, ྂᒇ ⚽ᓠ, ஂಖ ᬛᘯ, ▼ẟ ுᖹ, ᩪ⸨ ♩Ꮚࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ᪂つࣂ࢖࣮࢜࣋ࢫ㧗ศᏊᮦᩱࡢ≉ᛶゎᯒࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2022 ᖺ⛅Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ
6. ఀ⸨ 㞙ဢ, ྂᒇ ⚽ᓠࠊ࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺศᏊ࡟࠾ࡅࡿࢥ࣓࣮ࣥ࣍ࢩࣙࣥ≉ᛶࡢศᏊືຊᏛࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2022 ᖺ⛅Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ
7. ගṊ ᣅ㤿, ྂᒇ ⚽ᓠࠊ㧗ศᏊᮦᩱࡢ⇕ఏᑟ⋡࡟࠾ࡅࡿᘏఙಸ⋡౫Ꮡᛶࡢゎ᫂ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ
఍ 2022 ᖺ⛅Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1. Susumu Kawauchi, Akinori Akatsuka, Yoshihiro Hayashi, Hidemine Furuya, Toshikazu Takata, Determining theQ–e values of polymer radicals and monomers separately through the derivation of an intrinsic Q–e scheme for radical
copolymerization, Polymer Chemistry, 13, 1116-1129 (2022): https://doi.org/10.1039/D1PY01190A.
2. Hidemine Furuya, Toshinari Yanagihara, Yuki Orito, Hiroyasu Masunaga, Direct determination of the S-helix
structure and helix transition behavior of poly E-phenethyl L-aspartate) via synchrotron X̺ray diffraction, J. Pept. Sci.,
29, e3459 (2023): https://doi.org/10.1002/psc.3459.

- 354 -

2 

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investigated by simulations of 2 and 3 dimensions( )

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ࢀ࡚࠸ࡿࡀࠊ୍⯡࡟᭷ᶵⰍ⣲ࡢ␗᪉ᛶᅉᏊ (glum) ࡣ 10−3 ⛬ᗘ࡜ᑠࡉ࠸ࡶࡢࡀከࡃࠊࡼࡾ኱ࡁ࡞ glum ࢆ♧ࡍⰍ⣲ࡢ㛤Ⓨࡀᮃࡲࢀ࡚࠸ࡿࠋᡃࠎࡣࢼࣇࢱࣞࣥ⎔ 4 ಶ (ࣅࢼࣇࢳࣝ 2 ಶ) ࡜ࣆࣞࣥࡲࡓࡣ࣌ࣜࣞࣥ 2 ಶࡎࡘ࠿ࡽᡂࡿ⎔≧໬ྜ≀࡟࠾࠸࡚ࠊࣆࣞࣥࡲࡓࡣ࣌ࣜࣞࣥࡀ୍᪉ྥ࡟ࡎࢀ࡚ᅛᐃࡉࢀࡿࡇ࡜࡟ࡼࡾࠊ࢟ࣛࣝ࡞
࢚࢟ࢩ࣐࣮⏤᮶ࡢඃࢀࡓ CPL ࡀⓎ⌧ࡋ࠺ࡿ࡜⪃࠼ࡓࠋᮏ◊✲࡛ࡣࡇࢀࡽࢆྜᡂࡋࠊCPL ࡜ບ㉳≧ែᵓ㐀ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛ࠊ᪂ࡓ࡞ CPL Ⰽ⣲ࡢศᏊタィᣦ㔪ࢆ☜❧ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘἲ (B3LYP/6-31G(d,p) ࡲࡓࡣ CAM-B3LYP/6-31G(d,p)) ࡟ࡼࡾࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢᵓ㐀᭱㐺໬ィ⟬ࠊ᣺ືᩘゎᯒィ⟬ࠊศᏊ㌶㐨ィ⟬ࠊTD ィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࢯࣇࢺࡣ Gaussian16 ࢆ౑⏝ࡋࡓࠋ

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ᅗ 1. ࣅࢼࣇࢳࣝ–ࣆࣞࣥ⎔≧య࡜ࣅࢼࣇࢳࣝ–࣌ࣜࣞࣥ⎔≧య

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ࣥࡢ࢚࢟ࢩ࣐࣮Ⓨගࡢࡳࡀほᐃࡋࡓ࡜ࡇࢁࠊ⺯ගࢫ࣌ࢡࢺ࡛ࣝࡣ (R,R)-1–3 ࡣࣆࣞࣥࡲࡓࡣ࣌ࣜࣞ

ࡉࢀࡓࠋ୍᪉࡛ࠊ(R,R)-4 ࡜ (R,R)-5 ࡣࣆࣞࣥࡢࣔࣀ࣐࣮Ⓨගࡀ୺య࡛࠶ࡗࡓࠋ

ࡇࢀࡣࠊ(R,R)-4 ࡛ࡣ࣓ࢳࣞࣥ㒊఩ࡢ❧య㞀ᐖࠊ(R,R)-5 ࡛ࡣ࢚ࢫࢸࣝ㒊఩ࡢ๛┤ᛶ࡟ࡼࡗ࡚ࠊࣆࣞࣥ⎔ྠኈࡀ㏆௜ࡁ࡟ࡃ࠸ࡓࡵ࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋCPL ࢫ࣌ࢡࢺ࡛ࣝࡣ (R,R)-2 ࡛ࡣṇࠊ(R,R)- ࡜ (R,R)-3–5 ࡛ࡣ㈇ࡢࢩࢢࢼࣝࡀほࡉࢀࠊ|glum| ್ࡣ (R,R)-1 ࡢ 5.3 î 10−2 ࠿ࡽ (R,R)-3 ࡢ 2.2 î 10−3 ࡢ⠊ᅖ࡛࠶ࡗࡓࠋ⺯ගࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࣔࣀ࣐࣮Ⓨගࡀ୺య࡛࠶ࡗࡓ (R,R)-4 ࡜ (R,R)-5 ࡢ |glum| ್ࡀᑠࡉ࠸ࡢࡣࠊCPL ࡣ࢚࢟ࢩ- 360 -

࣐࣮Ⓨගࡢࡳ࡟⏤᮶ࡋ࡚࠸ࡿࡓࡵࡔ࡜⪃࠼࡚࠸ࡿࠋ1–3 ࡢẚ㍑࠿ࡽࠊࡇࡢᡭἲ࡟࠾ࡅࡿ⺯ගᅋ࡜ࡋ࡚ࡣࣆࣞ
ࣥࡢ᪉ࡀ㐺ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡾࠊࣆࣞࣥഃࡢ⤖ྜ఩⨨ࡣ 2,7-఩ࡀ㐺ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
ࡲࡓࠊ1 ࡜ 4 ࡢẚ㍑࠿ࡽ࣮ࣜࣥ࢝ࡣࣅࢼࣇࢳࣝഃ࡟㓟⣲ཎᏊࢆ᭷ࡍࡿ࢚࣮ࢸࣝ⤖ྜࡀ㐺ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂
ࡽ࠿࡟࡞ࡗࡓࠋ᭱ࡶ኱ࡁ࡞ |glum| ್ࢆ♧ࡋࡓ (R,R)-1 ࡢ CPL ࡢ⁐፹౫Ꮡᛶ࡜

ᗘ౫Ꮡᛶࢆㄪᰝࡋࡓ࡜ࡇࢁࠊ౫Ꮡᛶࡣぢࡽࢀ࡞࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ1 ࡣ๛┤࡞࢚࢟ࢩ࣐࣮ࢆᙧᡂࡋ࡚࠾ࡾࠊእ㒊⎔ቃࡢᙳ㡪ࢆ࠶ࡲࡾཷࡅ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋ❧యᵓ㐀࡜ CPL ≉ᛶࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ (TD) DFT ィ⟬ࢆ⾜ࡗࡓࠋ୍౛࡜ࡋ࡚ (R,R)-1 ࡜(R,R)-2 ࡢບ㉳≧ែࡢ᭱Ᏻᐃᵓ㐀ࢆ♧ࡍ (ᅗ 2)ࠋࣆࣞࣥ㒊఩ࡣ (R,R)-1 ࡛ࡣᕥᅇࡾࠊ (R,R)-2 ࡛ࡣྑᅇࡾ࡟ࡡ
ࡌࢀࡓ࢚࢟ࢩ࣐࣮ࢆᙧᡂࡋ࡚࠾ࡾࠊࡇࡢࡇ࡜ࡣ࢚࢟ࢩ࣐࣮࣭࢟ࣛࣜࢸ࢕࣮๎ (J. Am. Chem. Soc. 2020, 142, 1774±
1779.) ࡜▩┪ࡀ࡞࠿ࡗࡓࠋࡲࡓィ⟬࡟ࡼࡗ࡚ồࡵࡓ CPL ➢ྕࡣࠊᐇ࡜୍⮴ࡋࡓࠋ

ᅗ 2. (a) (R,R)-1 ࠾ࡼࡧ (b) (R,R)-2 ࡢບ㉳≧ែᏳᐃᵓ㐀



Ⓨ⾲ᐇ⦼

‫ۻ‬㧗▼࿴ே, ⏤ᾉྐஓ, ᮧୖ ⩧, ๓⏣༓ᑜ, ౫㤿 ṇ, ➨ 32 ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍, ࣆ࢚ࣞࣥ࢟ࢩ࣐࣮ࡢ࢟ࣛ
ࣜࢸ࢕࣮ไᚚ࡜෇೫ගⓎගᛶࡢ⁐፹౫Ꮡⓗ࡞➢ྕ཯㌿, 2022 ᖺ 9 ᭶ 20 ᪥.
‫ۻ‬㧗▼࿴ே, ᐑୗ ⩧, ⸈ୗ ⺯, ๓⏣༓ᑜ, ౫㤿 ṇ, ➨ 15 ᅇ᭷ᶵȧ㟁Ꮚ⣔ࢩ࣏ࣥࢪ࣒࢘, 1,1'-ࣅࢼࣇࢳࣝࡢ
6,6'-㐃⤖⎔≧ከ㔞యࡢྜᡂ࡜⨨᥮ᇶ࡟ࡼࡿ࢟ࣛࣝගᏛ≉ᛶࡢኚ໬, 2022 ᖺ 12 ᭶ 16 ᪥.
‫ۻ‬㧗▼࿴ே, ⏤ᾉྐஓ, ᮧୖ ⩧, ๓⏣༓ᑜ, ౫㤿 ṇ, ➨ 15 ᅇ᭷ᶵȧ㟁Ꮚ⣔ࢩ࣏ࣥࢪ࣒࢘,ࣅࢼࣇࢳࣝᯫᶫࣆ
ࣞࣀࣇ࢓ࣥࡢྜᡂ࡜࢚࢟ࢩ࣐࣮ࡢ❧యไᚚ࡟ࡼࡿ෇೫ගⓎගᛶ, 2022 ᖺ 12 ᭶ 16 ᪥.
‫ۻ‬Kazuto Takaishi, International CPL and CPEL Conference 2023 (ICCC-2023), Circularly polarized luminescenceliquids based on siloxybinaphthyls, 2023 ᖺ 3 ᭶ 7 ᪥.



ฟ∧ᐇ⦼

‫ ۻ‬Kazuto Takaishi, Sho Murakami, Fumiya Yoshinami, Tadashi Ema. Binaphthyl-bridged pyrenophanes: Intense
circularly polarized luminescence based on a D2 symmetry strategy. Angew. Chem. Int. Ed. 2022, 61, e202204609.
‫ۻ‬Kazuto Takaishi, Ritsuki Nishimura, Yuha Toda, Hajime Morishita, Tadashi Ema. One-pot synthesis of dihydropyrans
via CO2 reduction and domino Knoevenagel/oxa-Diels−Alder Reactions. Org. Lett. 2023, 25, 1370–1374.

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- 362 -

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ࡶቯኚຠᯝࡣேయ࡟ධࡗࡓ3Hࡀ⏕య㧗ศᏊෆࡢ 1H࡜⨨᥮ᚋ࡟șቯኚࡋ࡚㉳ࡁࡿຠᯝࡔࡀࠊ௚ 2ࡘࡢᙳ㡪࡜ࡢ༊ูࡀᐇ㦂⣔࡛ࡣᅔ㞴࡞ࡓࡵࠊࡇࡢຠᯝ༢⊂ࡢேయ࡬ࡢᙳ㡪ࡢ◊✲ሗ࿌ࡣṤ࡝࡞࠸ࠋᮏ◊✲࡛ࡣ཯ᛂຊሙࡢReaxFF(C. T. Adri et al., J. Phys. Chem. A (2001) 9396: S. Monti et al., Phys. Chem. Chem. Phys.,2013,15, 15062.)࡟ࡼࡿ MDィ⟬ࢆ⏝࠸࡚ࠊ3Hቯኚຠᯝ࡛ᦆയࡋࡓࣄࢺࢸ࣓ࣟ࢔ DNAࡀDSBsࢆ㉳ࡇࡍᵝᏊࢆ෌⌧ࡋࠊᦆയDNAࡢඹ᭷⤖ྜᙉᗘࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿࠋㄢ㢟 ⏕యศᏊࡢቯኚຠᯝࡢᙳ㡪㸸ᮏ⏦ㄳࡢ୰ᚰ࡛࠶ࡾࠊ2020&2021 ᖺᗘ࠿ࡽྲྀࡾ⤌ࢇ࡛ࡁࡓㄢ㢟࡛࠶ࡿࠋ◊✲⫼ᬒࡣࠊ᰾⼥ྜⓎ㟁࡟࠾࠸࡚ࡶ
⇞ᩱ࡜ࡋ࡚ࢺࣜࢳ࣒࢘ࡢෆ㒊⿕᭚ࡢホ౯ࡢࡓࡵࡢ⏕యศᏊ࡛ࣞ࣋ࣝ෌⌧ᛶࡢ࠶ࡿᐈほⓗ࡞ࢹ࣮ࢱ཰㞟࡛࠶ࡿࠋ⏕యศᏊ࡜ࡋ࡚DNAࢸ࣓ࣟ࢔ᵓ㐀ࢆ᝿ᐃࡋࠊDNAෆࡢ㍍Ỉ⣲࡜⨨᥮ࡋࡓࢺࣜࢳ࣒࢘ࡀ࣒࣊ࣜ࢘3࡬ࡢቯኚ
࡟ࡼࡿDNA ࢸ࣓ࣟ࢔ࡢᵓ㐀ኚ໬ࢆศᏊືຊᏛ(MD)ィ⟬࡛ホ౯ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚ࡁࡓࠋࡇࡢㄢ㢟ࡢ୰㛫ሗ࿌࡜ࡋ࡚ࡣࠊ2020ᖺᗘ࡟ࡣࠊDNAࢸ࣓ࣟ࢔ᵓ㐀ࢆᢅ࠼ࡿ࠶ࡿReaxFF࡜࿧ࡤࢀࡿ࣏ࢸࣥࢩࣕࣝ㸦ຊሙ࡜ゝࢃࢀࡿ㸧ࢆ⏝࠸࡚310K࡛ࡢᏳᐃᵓ㐀ࡢ෌⌧࠿ࡽ㛤ጞࡋࡓࠋ࡜ࡇࢁࡀࠊ᫬㛫ࡀ⤒ࡘ࡟ࡘࢀࢸ࣓ࣟ࢔ᵓ㐀ࡀ⭾ᙇࡍࡿ⤖ᯝ࡟࡞ࡗࡓࠋㄪᰝࡢ⤖ᯝࠊ᥇⏝ࡋࡓReaxFF࡟ཎᅉࡀ࠶ࡿྍ⬟ᛶࡀᾋ࠿ࡧୖࡀࡾࠊูࡢ4✀㢮ࡢReaxFFࢆ౑ࡗ࡚ᵓ㐀ィ⟬ࢆ⾜࠸ࠊ࠶ࡿィ⟬ࢫࢸࢵࣉෆ࡛ࡣᏳᐃ≧ែࢆಖࡘࡇ࡜ࡀ࡛ࡁࡿReaxFF ࢆぢࡘࡅࡿࡇ࡜ࡀ
࡛ࡁࡓ࡜ᛮࡗ࡚࠸ࡓࠋࡋ࠿ࡋࠊ2021ᖺᗘ࡟ࠊᘬࡁ⥆ࡁReaxFFࢆ⏝࠸࡚ࡉࡽ࡟᫬㛫Ⓨᒎࡉࡏࡿ࡜ࠊ୙Ᏻᐃ࡟
࡞ࡗ࡚ࡋࡲࡗࡓࠋࡇࡢၥ㢟ඞ᭹࡟2021ᖺᗘࡣ⭾኱࡞᫬㛫ࢆ㈝ࡸࡋ࡚࠸ࡿࠋ౛࠼ࡤࠊ⁐፹୰ࡢࢼࢺ࣒ࣜ࢘࢖࢜
࣭ࣥሷ⣲࢖࢜ࣥศᕸࡢ㐺ṇ໬ࢆࡋࡓࠋᮏ⣔࡛ࡣࠊึᮇ≧ែ࡜ࡋ࡚⏕య⣽⬊ෆ࡟┦ᙜࡍࡿ⃰ᗘࡢࢼࢺ࣒ࣜ࢘࢖
࣭࢜ࣥሷ⣲࢖࢜ࣥࢆỈࡢ୰࡟ࣛࣥࢲ࣒࡟ศᕸࡍࡿࠋࡇࡢึᮇศᕸࡀࠊ࠶ࡿ᫬㛫ࡀࡓ࡚ࡤࠊDNAࡢ㈇㟁Ⲵࢆ㐽ⶸࡍࡿࡼ࠺࡞Ᏻᐃศᕸ࡟࡞ࡿࠋᙜึࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࡀࡇࡢ⦆࿴᫬㛫ࡼࡾ▷࠿ࡗࡓࡓࡵࠊ᫬㛫ࢆᘏࡤࡍ࡞࡝ࡢᨵⰋࢆ⾜ࡗࡓࠋࡉࡽ࡟ࡣࠊLAMMPS࡜࠸࠺ỗ⏝MDࢥ࣮ࢻࢆ⏝࠸࡚࠸ࡿࡀࠊOpenMP࡛ࡢ୪ิ໬ࣝ
࣮ࢳ࡛ࣥࠊྠࡌィ⟬ࢆࡋ࡚ࡶࠊ㒔ᗘ⤖ᯝࡀኚࢃࡗ࡚ࡋࡲ࠺࡜࠸࠺㒊ศࡶぢࡘࡅࡓࠋ2022ᖺᗘ࡟ࡣࠊၥ㢟ࢆඞ
᭹ࡋDNAࢸ࣓ࣟ࢔ࡢᏳᐃ໬≧ែࡢ⋓ᚓࢆ⾜ࡗࡓࠋࡑࡢᚋࠊDNAࢸ࣓ࣟ࢔ᵓ㐀ࡢ࣮࣋ࢱᔂቯ࡟ࡼࡿയࡢຠᯝ

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ࢆ MD ࡛ㄪ࡭ࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ౑⏝ࡍࡿࢸ࣓ࣟ࢔ᵓ㐀ࡣ, ࣉࣟࢸ࢖ࣥࢹ࣮ࢱࣂࣥࢡ(PDB : Protein Data Bank) ෆࡢ 3sjm.pdb ࡛࠶ࡿ. ࣄࢺࡢࢸ࣓ࣟ࢔ DNA ᵓ㐀ࡢ୰࡛ሷᇶ㓄ิࡀ཯᚟ࡍࡿ㒊ศࢆษࡾྲྀࡾ, ᮎ➃ࢆ OH ᇶ࡛ฎ⌮ࡋࡓࡶࡢ࡟, ࢱࣥࣃࢡ㉁ࡀ௜
ຍࡋࡓ⏕య㧗ศᏊ࡛࠶ࡿ. ᮏ◊✲࡛ࡣ DNA ࡢࡳࢆ⏝࠸ࡿ.
ࡲࡓ,PDB ෆࡢᵓ㐀ࡣ௜ຍࡉࢀ࡚࠸࡞࠸Ỉ⣲ࡀ௜ࡅຍ࠼
ࡽࢀ࡚࠸ࡿ. ࢸ࣓ࣟ࢔ DNA ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆᅗ 1࡟♧ࡍ. ḟ࡟, ࢸ࣓ࣟ࢔ DNA ࡢᶍᘧᅗࢆᅗ 2 ࡟♧ࡍࠋᅗ㸯㸬ࢸ࣓ࣟ࢔ᵓ㐀ࡢሷᇶ㓄ิࡢᶍᘧᅗ ᕥᅗ ࠊ/ࡢ+͛+͇ࢆྲྀࡾ㝖࠸ࡓയࣔࢹࣝ
ࡢᶍᘧȋྑᅗ ࠋ

T,C,A,G ࡛⾲グࡉࢀࡿ㒊ศࡣሷᇶࢆ⾲ࡋ, ࡑࢀࡒࢀࢳ
࣑ࣥ, ࢩࢺࢩࣥ, ࢔ࢹࢽࣥ, ࢢ࢔ࢽࣥ࡜ᑐᛂࡋ࡚࠸ࡿ. ࡲ
ࡓ , ஧ ᮏ ࡢ 㙐 ࢆ ༊ ู ࡍ ࡿ ࡓ ࡵ , ሷ ᇶ 㓄 ิ{TCTAGGGTTAGGGTTAG}

ࡢ

ഃ

ࢆ

L

㙐

,

{AGATCCCAATCCCAATC}ࡢഃࢆ R 㙐࡜⾲グࡍࡿ. ຍ࠼
࡚, ࢜ࣞࣥࢪⰍࡢᅄゅࡣࢾࢡࣞ࢜ࢳࢻ୰ࡢࣜࣥཎᏊࢆ♧ᅗ㸰. ࢾࢡࣞ࢜ࢳࢻࡢᵓ㐀ᘧǤࡋ࡚࠾ࡾ, 㙐 1 ᮏ࡟ࡘࡁ 16 ಶᏑᅾࡍࡿ. ᮏㄽᩥࡢ୰࡛≉ᐃࡢ఩⨨ࡢࣜࣥཎᏊ(࠶ࡿ࠸ࡣࣜࣥཎᏊࢆ୰ᚰ࡜ࡋࡓࢾࢡࣞ࢜ࢳࢻ) ࢆ♧ࡍ㝿ࡣ L8,R12 ࡜࠸ࡗࡓ⾲グࢆ⏝࠸ࡿ.
⏕యෆࡸᐇ㦂⣔࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ࡣ, ከࡃࡢሙྜ┿✵୰࡛ࡣ࡞ࡃỈࡸ᭷ᶵ⁐፹࡜࠸ࡗࡓ⁐፹࡟ᅖࡲࢀࡓ≧ែ࡛Ꮡᅾࡍࡿ. ┿✵୰࡟⨨࠸ࡓࢱࣥࣃࢡ㉁ࢆࡑࡢࡲࡲ MDࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࡼ࠺࡜ࡍࡿ࡜, ᵓ㐀ࡀ୙Ᏻᐃ࡟࡞ࡾ
ᔂቯࡍࡿ࡞࡝ࡢᝏᙳ㡪ࢆཬࡰࡍ. ࡑࡢࡓࡵ, ࿘㎶࡟⁐፹ࡢຠᯝࢆྲྀࡾධࢀࡿᚲせࡀ࠶ࡿ. ⁐፹ຠᯝࡢྲྀࡾධࢀ᪉
࡟ࡣ኱ูࡋ࡚ 2 ✀㢮࠶ࡾ, ௬᝿ࡢ⁐፹ࡢᙳ㡪ࢆㄏ㟁య࡜ᅗ㸱㸬࢖࢜ࣥ࡜DNA

ࡋ࡚ྵࡴ᪉ἲ࡜, ⁐፹ศᏊࢆ࠶ࡽࢃ࡟ຍ࠼ࡿ᪉ἲࡀ࠶ࡿࡀ, ᮏ◊✲࡛ࡣᚋ⪅ࢆ᥇⏝ࡋࡓ. ࢱ࣮ࢤࢵࢺ࡜࡞ࡿࢸ࣓ࣟ࢔DNA ࡣ⏕యෆ࡟࠶ࡿࡓࡵ,Na+, Cl− ࡞࡝ࡢ࢖࢜
ࣥࢆྵࡴỈ࡟ᅖࡲࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ. ⁐፹ศᏊࡢᩜࡁワࡵ᪉࡟ࡣ࠸ࡃࡘ࠿✀㢮ࡀᏑᅾࡍࡿࡀ, ࿘ᮇቃ⏺
᮲௳ࢆ xyz ᪉ྥ࡟᥃ࡅࡿࡇ࡜ࢆ᝿ᐃࡋ, ┤᪉య(❧᪉య) ࡟࡞ࡿࡼ࠺㓄⨨ࡋࡓ.DNA ࢆ୰ᚰ࡜ࡋࡓ 100˚A ❧᪉ࡢ࣎ࢵࢡࢫෆ࡟ィ30, 773 ಶࡢỈศᏊࢆᩜࡁワࡵࡓ.
⁐፹ࡢ࡯࠿࡟,2 ✀㢮ࡢ࢖࢜ࣥࢆຍ࠼ࡿ. ࡇࢀࡣ, ᑐ࢖࢜ࣥ࡟ࡼࡿDNA ࡢ㈇ࡢ㟁Ⲵࡢ୰࿴࡜, ⏕య࡟㏆࠸࢔ࢽ࢜ࣥ, ࢝ࢳ࢜ࣥ⃰ᗘ࡟ࡍࡿࡇ࡜ࡀ┠ⓗ࡛࠶ࡿ. ࡲࡎ, ᑐ࢖࢜ࣥ࡟ࡣNa+ ࢆ㑅ࡧ,DNA ඲యࡢ㈇ࡢ㟁Ⲵ࡜㔮ࡾྜ࠺32 ಶຍ࠼ࡓ. ࢝ࢳ࢜ࣥࡣNa+, ࢔ࢽ࢜ࣥ࡟ࡣCl− ࢆ㑅ᢥࡋ, ࡑࡢ⃰ᗘࡣ0.15mol/L(⏕యෆࡢ⃰ᗘ)
࡜ࡋࡓ. ᅗ3 ࡟࢖࢜ࣥ࡜DNA ࢆ♧ࡍ. ࡓࡔࡋ, ỈศᏊࡣ㠀⾲♧࡛࠶ࡿ. ௒ᅇࡣNa+ ࡀ120 ಶ,Cl− ࡀ88 ಶ↓సⅭ࡟㓄⨨ࡉࢀࡓࠋ⇕ᾎࡢཧ↷ᗘ ࠾ࡼࡧຊሙ࡜᫬้ࡢᑐᛂࡣᅗ ࡢ㏻ࡾ࡛࠶ࡿ ࡑࡢ௚ࡢඹ㏻࡛࡞࠸㒊ศࡣィ⟬ࡢẁ㝵ࡈ

- 370 -

࡜࡟᮲௳ࢆグ㍕ࡍࡿ ࡲࡎ,PDB ࠿ࡽ࡜ࡗ࡚ࡁࡓ DNA ࡟Ỉ࡜࢖࢜ࣥࢆຍ࠼ࡓᵓ㐀࡟ᑐࡋ࢚ࢿࣝࢠ࣮᭱ᑠ໬ࢆ
⾜࠺. ⣔ࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡀࡼࡾప࠸್࡜࡞ࡿࡼ࠺, ᑡࡋࡎࡘཎᏊᗙᶆࢆࡎࡽࡍᕤ⛬࡛࠶ࡿ. ࢚ࢿࣝࢠ࣮᭱ᑠ໬ࢆ⾜ࡗࡓᵓ㐀ࡣึᮇ㏿ᗘࡀࢮࣟࠊࡘࡲࡾ 0K ࡢ≧ែ࡛࠶ࡿ. ࡇࡇ࡛,⣔࡟୚࠼ࡿึᮇ㏿ᗘࢆ࠸ࡁ࡞ࡾ㧗࠸್࡟タᐃࡋ࡚ࡋࡲ࠺࡜, ᫬㛫✚ศࡀⓎᩓࡋࡓࡾ, ᛴ⃭࠿ࡘ୙Ᏻᐃ࡞㐠ື࡟ࡼࡗ࡚㧗ศᏊࡢᵓ㐀ࡀᔂࢀ࡚ࡋࡲ࠺ࡇ࡜ࡀᠱᛕࡉࢀࡿ. ࡑࡇ࡛, ᮏ◊✲࡛ࡣ⇕ᾎࡢཧ↷ᗘࢆᴟప࠿ࡽ᫬㛫ࢆ࠿

ࡅ࡚ୖ᪼ࡉࡏࡿ᪉ἲࢆ࡜ࡿ.36 DNA ࡢᗙᶆ࡜㏿ᗘࢆึᮇ್࡛ᅛᐃࡋ,0.5ns ࠿ࡅ࡚⣔ࡢᗘ

ࢆ 0.1K ࠿ࡽ 310K ࡲ࡛ୖ᪼ࡉࡏࡓ. ィ⟬ࡣNVT ࢔ࣥࢧࣥࣈ࡛ࣝ⾜ࡗࡓ. ⇕ᾎࡢཧ↷ᗘࡣ 310K ࡜ࡋࡓ.
ேయ᮲௳ୗ࡛Ᏻᐃ࡞ DNA ࢆసᡂࡍࡿࡓ
ࡵ,CHARMM ຊሙࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓ. ࡇᅗ㸲㸬⇕ᾎࡢཧ↷ᗘǡ ࠾ࡼࡧຊሙ࡜᫬้࡜ࡢᑐᛂǤࡇ࠿ࡽࡣຊሙࢆ ReaxFF ࡟ษࡾ᭰࠼࡚, Ᏻᐃ࡞ DNA ᵓ㐀ࢆ⥔ᣢࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⾜࠺. ᑐ࢖࢜ࣥ࡟ࡼࡿ㟁Ⲵ㐽ⶸࢆ⾜ࡗࡓᵓ㐀࡟ᑐࡋ, Aniruddh ࡽ࡟ࡼࡗ࡚㛤Ⓨࡉࢀࡓ࣏ࣜ
࣐࣮ࡢᯫᶫ཯ᛂྥࡅࡢ ReaxFF ࣃ࣓࣮ࣛࢱ 39ࢆ⏝࠸࡚ 0.90ns ィ⟬ࢆ⾜ࡗࡓ. ィ⟬ࡣ NPT࢔ࣥࢧࣥࣈ࡛ࣝ⾜ࡗࡓ.⇕ᾎࡢཧ↷ᗘࡣ

310K ࡛, ཧ↷ᅽຊࡣ 1.0bar ࡜ࡋࡓ. ࡉࡽ࡟ࠊDNA ࡢ OH ᮎ➃ 4 ⟠ᡤࢆᅛᐃࡋࡓ. ࡇࢀ
ࡣ,DNA ࡀ࢚ࣅࡒࡾ࡟࡞ࡿࡇ࡜࡟ࡼࡿᮎ➃࠿

ᅗ 5. ᮎ➃ࢆࣆࣥṆࡵࡋࡓሙྜࡢࢫࢼࢵࣉࢩࣙࢵࢺǤࡽࡢᵓ㐀ᔂቯࢆ㜵ࡂ 5HD[)) ࡛ᵓ㐀୙Ᏻᐃ
࡞ '1$ ࢆ㛗᫬㛫⥔ᣢࡉࡏࡿ┠ⓗࡀ࠶ࡿ ᅗ㸳࡟ᅛᐃࡋࡓ⟠ᡤࢆ㉥୸࡛ᙉㄪࡋࡓࢫࢼࢵࣉ
ࢩࣙࢵࢺࢆ♧ࡍࠋ'1$ෆࡢỈ⣲ࡢ࠺ࡕ࡝ࡇࢆྲྀࡾ㝖ࡃ࠿ࡣ'1$ࡢ⁐፹᥋ゐ⾲㠃✚࡟㛵ࡍࡿ◊✲⤖ᯝࢆཧ⪃࡟ࡋࡓࢺࣜࢳ࣒࢘࡜ࢾࢡࣞ࢜ࢳࢻ୰ࡢỈ⣲ࡀ⨨᥮ࡍࡿ㝿࡟ࡣᚲࡎࢺࣜࢳ࣒࢘ࢆྵࡴ
ỈศᏊ࡜ࢾࢡࣞ࢜ࢳࢻࡢỈ⣲ࡀ᥋ゐࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡇࡇ࡛'1$୰ࡢỈ⣲࡜⁐፹

ᅗ6. ࢔ࢹࢽࣥ࡟࠾ࡅࡿ⁐፹᥋ゐ⾲㠃✚ࡢᶍᘧᅗ

ࡢ㛫ࡢ᥋ゐ⾲㠃✚ࡀ㔜せ࡜࡞ࡿ࢔ࢹࢽࣥࡢ⁐፹᥋ゐ⾲㠃✚ࡢᶍᘧᅗࢆᅗ㸴࡟♧ࡍࡇࡢᅗ࡛ࡣཎᏊࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ⾲㠃ࢆ㯮ሬࡢ෇ࣉ࣮ࣟࣈ
⌫ࢆⓑሬࡢ෇ཎᏊࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ⾲㠃࡟ἢࡗ࡚ࣉ࣮ࣟࣈ⌫ࢆ㌿ࡀࡋࡓ࡜ࡁࣉ࣮ࣟࣈ⌫ࡢ୰ᚰࡀࡘࡃࡿ㠃 ᥋ゐ⾲㠃 ࢆⅬ⥺࡛♧ࡍ᥋ゐ⾲㠃ࡢ㠃✚ࡀ⁐፹᥋ゐ⾲㠃✚࡛࠶ࡿࢺࣜࢳ࣒࢘⨨᥮ࡋࡓỈศᏊࡀ
'1$࡟᥋ゐࡍࡿࡇ࡜࡛ࢺࣜࢳ࣒࢘⨨᥮ࡀ⏕ࡌࡿ࡜⪃࠼ࡽࢀࡿࡓࡵỈศᏊࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ༙ᚄ࡛࠶

- 371 -

ࡿࠋǀ$ࢆࣉ࣮ࣟࣈ༙ᚄ࡜ࡋࡓ ᅗ࡟ࢾࢡࣞ࢜ࢳࢻࡢᵓ㐀ᘧࢆ♧ࡍ̓Ⅳ⣲࡜⤖ྜࢆࡶࡘࡘࡢỈ⣲ࢆ㟷࠸୸ᯟ࡛ᙉㄪ
ࡋ࡚࠶ࡿ஬Ⅳ⢾ࡀࡶࡘỈ⣲ࡢ୰࡛⢾ṧᇶࣜࣥ㓟ᇶ㛫ࡢඹ᭷⤖ྜࢆࡶࡘⅣ⣲ ͛ ࡟⤖ྜࡋ࡚࠸ࡿỈ⣲ࡘࡀࡶࡗ࡜ࡶ⁐፹࡜
᥋ゐࡋࡸࡍ࠸ࡘࡲࡾ⨨᥮ࡉࢀࡸࡍ࠸Ỉ⣲࡛࠶ࡿࡇ࡜ࡀ◊✲⤖ᯝࡽ♧ࡉࢀ࡚࠸ࡿ

ᅗ㸵㸬യ࣌࢔ࡢಶᩘࢆኚ᭦ࡋࡓࣔࢹࣝࡢᶍᘧᅗǤᅗ㸦ྑᅗ㸧࡛ࡣࠊ/ࡢࢾࢡࣞ࢜ࢳࢻ୰
ࡢ+͛ࡘࢆྲྀࡾ㝖࠸࡚࠸ࡿࠋࡇࡢࡼ࠺࡞
㝖ཤࢆയ࡜࡞ࡎࡅࡿࠋࡇࡢയࣔࢹࣝࡢసᡂ
ᡭ㡰ࢆḟ࡟♧ࡍ௨㝆ቯኚຠᯝࡢയࢆ⥳ࡢᅄゅ࡛⾲ࡍ࡜ࡍࡿ
യࣔࢹࣝࡢࡶ࡜࡜࡞ࡿ⢏Ꮚᗙᶆ࡜⢏Ꮚ㏿ᗘࡀグ㏙ࡉࢀࡓࣇ࢓࢖ࣝ ௨
ୗGDWDࣇ࢓࢖ࣝ࡜࿧ࡪ ࢆ⏝ពࡍࡿ

GDWDࣇ࢓࢖ࣝ୰ࡢ/࡜/ࡢࢾࢡ

ᅗ㸶. യࡢ㓄⨨ࢆ೫ࡽࡏࡓࣔࢹࣝࡢᶍᘧᅗǤࣞ࢜ࢳࢻࡢ㟁Ⲵࢆ')7ィ⟬ࡢ⤖ᯝ࡟᭩ࡁ᥮࠼ࡿ

GDWDࣇ࢓࢖ࣝ࠿ࡽ/ࡢࢾࢡࣞ࢜ࢳࢻ୰ࡢ&͛࡟⤖ྜࡋ࡚࠸ࡿỈ⣲ +͛+͇ ࡢ᝟ሗࢆ๐㝖ࡍࡿ

GDWDࣇ࢓࢖ࣝ࡟ࡣ⢏Ꮚࡢ⥲ᩘࢆグ㏙ࡋࡓ⾜ࡀ࠶ࡿࡓࡵྲྀࡾ㝖࠸ࡓỈ⣲ࡢᩘࡔࡅ⢏Ꮚࡢ⥲ᩘࢆῶࡽࡍ᭱ᚋ࡟๐㝖ࡋࡓ⢏ᏊࡢᩘࡔࡅᩘᏐࢆࡎࡽࡍࡇ࡜࡛⥲ᩘ࡟⢏Ꮚ␒ྕࢆྜࢃࡏࡿ

ࡇࡢࡼ࠺࡟ࡋ࡚సᡂࡋࡓࣔࢹࣝ࡟㛵ࡋ࡚യࡢಶᩘࡢ౫Ꮡᛶ࣭യࢆධࢀࡿሙᡤࡢ౫Ꮡᛶࢆ☜࠿ࡵࡿ
㸦㸯㸧ಶᩘ౫Ꮡᛶ
ྥ࠿࠸ྜ࠺യࢆ ࣌࢔࡜ࡋ ࣌࢔ࡢಶᩘࢆኚ໬ࡉࡏࡿࡇ࡜࡛ ஧㔜㙐ษ᩿ࡀ࡝ࡢ⛬ᗘࡢയࡢ࣌࢔ᩘ࡛Ⓨ⏕ࡍࡿ࠿ࢆ☜࠿ࡵࡿ'1$ ࡢሷᇶ㓄ิࡢ୰ኸ㒊 /5  ࠿ࡽᮎ➃࡟യࡢᩘࢆቑࡸࡋ࡚࠸ࡁ^`^`^`^`^` ࡢ ࢣ࣮ࢫࢆ⏝ពࡋࡓ യࡢ↓࠸ࣔࢹࣝ^` ࢆྵࡴ ࢣ࣮ࢫࡢᶍᘧᅗࢆ
ᅗ㸶 ࡟♧ࡍ㸦㸧ሙᡤ౫Ꮡᛶ
ಶᩘ౫Ꮡᛶࡢ㡯┠࡛ࡣྥ࠿࠸ྜ࠺࣌࢔࡟ᆒ➼࡟യࢆຍ࠼ࡓࡀሙᡤ౫Ꮡᛶ࡛ࡣ୧⪅ࡢയࡢ㓄ศࢆ೫ࡽࡏࡿ
ᴟ➃࡟೫ࡗࡓ౛࡜ࡋ࡚ ୍᪉ࡢ㙐࡟ ⟠ᡤയࢆࡘࡅ ࡶ࠺୍᪉ࡣ඲ࡃയࢆࡘࡅ࡞࠸ࣔࢹࣝ ^`^`  ࢆ⏝ពࡋࡓ ຍ࠼࡚ ᚋ㏙ࡍࡿ⤖ᯝ࡛ ࣌࢔௨ୖ࡛஧㔜㙐ษ᩿ࡀⓎ⏕ࡍࡿࡓࡵ ୍᪉ࡢ㙐ࡀ ಶࡶ࠺୍᪉ࡢ㙐ࢆ ಶ࡜ࡋ^`^` ࡶ⏝ពࡋࡓ ࢣ࣮ࢫࡢᶍᘧᅗࢆᅗ㸶࡟♧ࡍࠋ◊✲ᡂᯝ㸸 ࢣ࣮ࢫࡢയࣔࢹࣝ࡟ࡘ࠸࡚ィ⟬ࢆ⾜࠸ യࡢಶᩘ౫Ꮡᛶ࠾ࡼࡧሙᡤ౫Ꮡᛶࢆ☜࠿ࡵࡓ 㙐ษ᩿ࡣ୍᫬ⓗ- 372 -

࡟⏕ࡌ࡚ࡶࡍࡄ෌⤖ྜࡍࡿࡇ࡜ࡶ࠶ࡿࡓࡵ 㙐ษ᩿ࡀQV௨ୖᣢ⥆ࡍࡿ⌧㇟ࢆࢠࣕࢵࣉ ∦᪉ࡢ㙐ࡢࡳ࡛ࢠࣕࢵࣉࡀ⏕ࡌࡿࡇ࡜ࢆ66% 6LQJOH6WUDQG%UHDN  ୧ഃࡢ㙐࡛ࢠࣕࢵࣉࡀ⏕ࡌࡿࡇ࡜ࢆ'6%V ࡜ࡼࡤࢀࡿࠋ'1$ ࡢ⥔ᣢ㝈⏺ࡲ࡛࡟ ྜィ ಶ௨ୖࡢയࢆࡘࡅࡓ ࡘࡢࢣ࣮ࢫ ^`^`^`^`࡛ࡣ'6%V ࡀⓎ⏕ࡋ ྜィ ಶ௨ୖ ಶ௨ୗࡢയࢆࡘࡅࡓ ࡘࡢࢣ࣮ࢫ ^`^`^` ࡛ࡣ66%
ࡀⓎ⏕ࡋࡓ^`^` ࡢയࢆࡘࡅࡓ㝿࡟ࡣ⥔ᣢ㝈⏺ࡲ࡛࡟ࢠࣕࢵࣉࡀⓎ⏕ࡋ࡞࠿ࡗࡓ ຍ࠼࡚^`^` ࡛ࡣയࢆࡘࡅࡓഃࡢ㙐ࡢࡳ࡛ࢠࣕࢵࣉࡀⓎ⏕ࡋࡓ௨ୗࠊಶูࡢሙྜ࡟ࡘ࠸࡚ࡲ࡜ࡵࡓࠋ
L^` ࡢW QV ࡟࠾ࡅࡿ'1$ ࡢࢫࢼࢵࣉࢩࣙࢵࢺ ࠾ࡼࡧࢠࣕࢵࣉࡢⓎ⏕⟠ᡤࢆᅗ ࡟^` ࡢW QV ࡟࠾ࡅࡿ'1$ ࡢࢫࢼࢵࣉࢩࣙࢵࢺ ࠾ࡼࡧࢠࣕࢵࣉࡢⓎ⏕⟠ᡤࢆᅗ ࡟♧ࡍ

LL^` ࡢW QV ࡟࠾ࡅࡿ'1$ ࡢࢫࢼࢵࣉࢩࣙࢵࢺ ࠾ࡼࡧࢠࣕࢵࣉࡢⓎ⏕⟠ᡤࢆᅗ࡟
^`ࡢW QV ࡟࠾ࡅࡿ'1$ ࡢࢫࢼࢵࣉࢩࣙࢵࢺ ࠾ࡼࡧࢠࣕࢵࣉࡢⓎ⏕⟠ᡤࢆᅗ࡟♧ࡍ

ᅗ㸷㸬W QV࡟࠾ࡅࡿ

ᅗ㸬W QV࡟࠾ࡅࡿ^`^`ࡢࢫࢼࢵࣉࢩࣙࢵࢺ

ᅗ㸬W QV࡟࠾ࡅࡿ

ࡢࢫࢼࢵࣉࢩࣙࢵࢺ

ᅗ㸬W QV࡟࠾ࡅࡿ^`^`ࡢࢫࢼࢵࣉࢩࣙࢵࢺ

ࡢࢫࢼࢵࣉࢩࣙࢵࢺ

⪃ᐹ㸸ᚓࡽࢀࡓィ⟬⤖ᯝ࠿ࡽ യࡢಶᩘ౫Ꮡᛶ യࡢሙᡤ౫Ꮡᛶ ࠾ࡼࡧࢠࣕࢵࣉࡢⓎ⏕ࡋࡸࡍ࠸⟠ᡤࢆ⪃ᐹࡍࡿྛࣔࢹ࡛ࣝࡢࢠࣕࢵࣉ᭱ึ࡟Ⓨ⏕ࡋࡓ᫬้'6%V ࡀ᭱ึ࡟Ⓨ⏕ࡋࡓ᫬้ ୧㙐ࢆྜࢃࡏࡓࢠࣕࢵࣉࡢ
ᩘࢆࡲ࡜ࡵࡓࡶࡢࡀ⾲ ࡛࠶ࡿ
യࡢಶᩘ౫Ꮡᛶ
യࡢಶᩘࡀ24 ಶ௨ୖࡢィ⟬({16,16}, {12,12}, {16,8},{8,16}) ࡛ࡢࡳ,DSBs ࡢⓎ⏕ࢆほࡍࡿࡇ࡜ࡀ࡛ࡁࡓ.

യࡢಶᩘࡀ16 ಶࡢィ⟬({8,8},{16,0},{0,16}) ࡛ࡣSSB ࡀⓎ⏕ࡋ, ࡑࢀᮍ‶ࡢയ࡛ࡣ⥔ᣢ㝈⏺௨ෆ࡟ࢠࣕࢵࣉ

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ࡣ⏕ࡌ࡞࠸࡜࠸࠺, യࡢಶᩘ࡜ษ᩿ࡋࡸࡍࡉ࡜ࡢ㛫࡟᭷ព࡞┦㛵ࡀࡳࡽࢀࡓ. ࡲࡓ,ࢠࣕࢵࣉࡢಶᩘࡣ{16,16}
ࡀ8ಶ࡟ᑐࡋ,{16,16} ࡀ4 ಶ࡜,{16,16} ࡢ᪉ࡀከࡃ࡞ࡗ࡚࠸ࡿ. ࡉࡽ࡟, {8,8} ࡢSSB ࡣDNA ࡢ⥔ᣢ㝈⏺࡟
ᑐࡋ0.4ns ⛬ᗘ᪩ࡃⓎ⏕ࡍࡿ. ࡇࢀࡣDNA ࡢ⥔ᣢ㝈⏺ࡢ༙ศ௨ୖࡢ᫬㛫࡛࠶ࡾ, DNA ࡀ⬤ࡃ࡞ࡗࡓࡓࡵ࡟ࢠ
ࣕࢵࣉࡀ᪩ࡲࡗࡓ࡜⪃࠼ࡽࢀࡿ. ௨ୖࡢⅬ࠿ࡽ, യࡢಶᩘࢆቑࡸࡍࡇ࡜࡛,DNA ࣂࢵࢡ࣮࣎ࣥࡀ⬤ࡃ࡞ࡗ࡚࠸ࡃ࡜࠸࠼ࡿ. ୍᪉,DSBs ࡀⓎ⏕ࡍࡿࡲ࡛ࡢ᫬้ࡣ{16,16} ࡀ᭱ࡶ㐜ࡃ࡚{8,16} ࡀ᭱ࡶ᪩ࡃ, ࡑࡢᕪࡣ⣙0.2ns࡛࠶ࡿ. ୍ᐃ⟠ᡤᩘ௨ୖ࡛ࡢቯኚຠᯝ࡟ࡼࡿDNA ࡢ⪏ஂᛶࡢపୗࡣぢࡽࢀࡓࡶࡢࡢ, DNA ࡢࢠࣕࢵࣉ
ࡀⓎ⏕ࡍࡿỴᐃᡴࡣ࠶ࡃࡲ࡛⁐፹ࡸ࢖࢜ࣥ࡜࠸ࡗࡓ࿘㎶ࡢຠᯝ࡛࠶ࡾ, Ⓨ⏕ࡲ࡛ࡢ᫬㛫ࡶ࿘㎶ࡢཎᏊศᏊࡀ
ࡶࡓࡽࡍࣛࣥࢲ࣒ᛶࡀᙉ࠸࡜⪃࠼ࡽࢀࡿ.

⾲㸯 ࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝǣࢠࣕࢵࣉࡢⓎ⏕᫬้࡜ᅇᩘ

ሙᡤ౫Ꮡᛶ
{16,0},{0,16} ࡛ࡣയࢆࡘࡅࡓഃࡢ㙐ෆ࡛ࢠࣕࢵࣉࡀⓎ⏕ࡋ, ࡶ࠺୍᪉ࡢ㙐࡟ࡣቯኚࡢᙳ㡪ࡀἼཬࡋ࡞࠿ࡗࡓ.
ຍ࠼࡚, {16,0} ࡢ᭱⤊ⓗ࡞ࢠࣕࢵࣉࡣ9ಶ,{0,16} ࡣ3 ಶ࡜, ྠࡌ୍ᮏ㙐ࡢࡳࡢയ࡛ࡶࢠࣕࢵࣉࡢᩘ(༓ษࢀලྜ) ࡟኱ࡁ࡞ᕪࡀ⏕ࡌ࡚࠸ࡿ. ୍᪉,{16,8} ࣔࢹࣝ࡜{8,16} ࣔࢹ࡛ࣝࡣDSBs ࡀⓎ⏕ࡍࡿࡶࡢࡢ,{16,8} ࣔࢹ࡛ࣝࡣᑡ࡞࠸യࢆࡘࡅࡓ᪉ࡢ㙐ࡢ᪉ࡀࢠࣕࢵࣉࡢᩘࡀከࡃ࡞ࡗ࡚࠸ࡿ. ࡲࡓ, {8,16} ࡛ࡣയࢆࡘࡅ࡚࠸࡞
࠸L15,L16 ࡛ษ᩿ࡀⓎ⏕ࡋ࡚࠾ࡾ, യࡢ఩⨨࡜ษ᩿఩⨨ࡢ㛵㐃ᛶࡣ኱ࡁࡃ࡞࠸࡜⪃࠼ࡽࢀࡿ.

ࡲ࡜ࡵᮏ◊✲࡛ࡣࢺࣜࢳ࣒࢘ࡢቯኚຠᯝ࡛ᦆയࡋࡓࣄࢺࢸ࣓ࣟ࢔DNA ࡀDSBs ࢆ㉳ࡇࡍᵝᏊࢆ෌⌧ࡋ, ᦆയDNA
ࡢඹ᭷⤖ྜᙉᗘࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿࡓࡵ, ቯኚຠᯝ࡟ࡼࡿയࡢಶᩘࡸ㓄⨨ࡢ೫ࡾ᪉ࢆኚ࠼ࡓࣔࢹࣝࢆ⏝ពࡋ,ศᏊືຊᏛἲࢆ⏝࠸ࡓࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ. ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆṇࡋࡃ⾜࠺ࡓࡵ࡟ࡣ, DNA ࢆ⏕య࡜ྠ➼ࡢ⎔ቃୗ࡟⨨ࡁ, യࡢᙳ㡪ࡀࢃ࠿ࡿ⛬ᗘࡢ㛗᫬㛫ࢫࢣ࣮࡛ࣝᵓ㐀ࢆಖࡘᚲせࡀ࠶ࡿ. ຍ࠼࡚, ᮏ◊✲࡟
⏝࠸ࡿReaxFF ຊሙࡣDNA ࡟᭱㐺໬ࡉࢀ࡚࠸࡞࠸ࡓࡵ, CHARMM ࡸAmber ௨ୖ࡟DNA ࡢᏳᐃᛶࢆಖࡘᕤ
ኵࢆồࡵࡽࢀࡿ. ᪂ࡓ࡟DNA ࿘㎶ࡢ࢖࢜ࣥ㞺ᅖẼࢆ⦆࿴ࡋࡓࡾ, DNA ᅄ㝮ࢆᅛᐃࡋ࡚ᮎ➃࠿ࡽࡢᔂቯࢆ㜵࠸ࡔࡾ࡜࠸ࡗࡓᕤኵࢆྲྀࡾධࢀࡿࡇ࡜࡛㐣ཤࡢ◊✲ࡢ୰࡛⪃៖ฟ᮶࡚࠸࡞࠿ࡗࡓ஦㡯ࢆ⿵࠸, DNA ᵓ㐀ࢆ⣙0.7ns ࡢᮇ㛫Ᏻᐃࡋ࡚⥔ᣢ࡛ࡁࡓ. ࡑࡢᏳᐃ᫬㛫࡟࠾ࡅࡿ᭱ึࡢ᫬ⅬࡢDNAᵓ㐀࡟ᑐࡋ, Ỉ⣲ࢆྲྀࡾ㝖࠸࡚㟁Ⲵศᕸࡢኚ໬ࢆྲྀࡾධࢀࡓࠕയࣔࢹࣝࠖࡢࢣ࣮ࢫࢆ10 ࡘసᡂࡋࡓ. ࢣ࣮ࢫࢆ኱ูࡍࡿ࡜DNA ࡢሷᇶ㓄

- 374 -

ิࡢ୰ኸ࠿ࡽയࡢಶᩘࢆᆒ➼࡟ቑࡸࡋ࡚࠸ࡃಶᩘ౫Ꮡᛶ࡜, ྠࡌಶᩘ࡛യࡢ㓄⨨ࢆ೫ࡽࡏ, 㙐ษ᩿ࡢⓎ⏕≧ἣࡢኚ໬ࢆぢࡿሙᡤ౫Ꮡᛶ࡜࡞ࡿ. ⤖ᯝ, ಶᩘ౫Ꮡᛶࢣ࣮ࢫ࡛ࡣ, 16 ሷᇶᑐ(32 ࢾࢡࣞ࢜ࢳࢻ) ࡢDNA ࡟ᑐࡋ࡚, ቯኚຠᯝ࡟ࡼࡿയࢆᣢࡘࢾࢡࣞ࢜ࢳࢻࡀ24 ಶ௨ୖ࡜࡞ࡿᵓ㐀࡛ࡣ஧㔜㙐ษ᩿ࢆほࡍࡿࡇ࡜ࡀ࡛

ࡁࡓ. ࡲࡓ,16 ಶࡢሙྜ࡛ࡣ୍㔜㙐ษ᩿࡟࡜࡝ࡲࡗࡓ. ሙᡤ౫Ꮡᛶࢣ࣮ࢫ࡛ࡣ, ∦᪉ࡢ㙐࡟16 ಶࡢയࡀ㞟୰ࡋࡓሙྜ࡜, ୧᪉ࡢ㙐࡟16:8 ࡢ๭ྜ࡛೫ࡗ࡚യࡀࡘ࠸ࡓሙྜ࡟ࡘ࠸࡚☜࠿ࡵࡓ. ࡑࡢ⤖ᯝ∦᪉ࡢ㙐࡟യࡀ㞟୰ࡋࡓሙྜ യࡢ࠶ࡿ㙐࡛ࡢࡳ㙐ษ᩿ࡀⓎ⏕ࡋ ஧㔜㙐ษ᩿࡟ࡣ⮳ࡽ࡞࠿ࡗࡓ ୍᪉ ࡢ๭ྜ࡛യࢆࡘࡅ
ࡓࡶࡢ࡛ࡣ஧㔜㙐ษ᩿ࡀⓎ⏕ࡋ യࡢᑡ࡞࠸᪉ࡢ㙐࡛ษ᩿ࡀ㢧ⴭ࡛࠶ࡗࡓ ࡇࢀࡽࡢ⤖ᯝࢆ㋃ࡲ࠼ ஧㔜㙐ษ᩿ࡢⓎ⏕ࡢࡓࡵ࡟ࡣ ୧ഃࡢ㙐࡛ቯኚຠᯝࡀⓎ⏕ࡍࡿࡇ࡜ ㏆࠸఩⨨࡛ ಶ௨ୖࡢከᩘࡢയࡀ⏕ࡌࡿࡇ࡜ࡀᚲせ࡜࡞ࡿ࡜⪃࠼ࡽࢀࡿ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
z

K. Ishiguro, Hiroaki Nakamura, Shunsuke Usami, Susumu Fujiwara, Seiki Saito, “Evaluation tolerance of DNA
damaged by tritium beta decay using MD simulation”, The 41th JSST Annual International Conference on
Simulation Technology, Online, 2022.8.31-9.3. (JSST2022 Student Presentation Award ࢆཷ㈹)z

K. Ishiguro, Hiroaki Nakamura, Shunsuke Usami, Susumu Fujiwara, Yuji Hatano, “Evaluation of the effect oftritium decay on the tolerance of DNA structure by MD simulation”, The 31st International Toki Conference on
Plasma and Fusion Research (ITC31) Poster Session 1, Online, 2022.11.8- 375 -

$J ⨨᥮ࢮ࢜ࣛ࢖ࢺ ; ࡟࠾ࡅࡿࣉࣟࣃࣥࣉࣟࣆࣞࣥศ㞳࣓࢝ࢽࢬ࣒ࡢゎ᫂
0HFKDQLVPRISURSDQHSURS\OHQHVHSDUDWLRQLQ
$JH[FKDQJHG;W\SH]HROLWH‫⏣ۑ‬୰ ⚽ᶞ㸪⥴᪉ ᬛᕼ㸦ಙᕞ኱Ꮫඛ㗦ᮦᩱ◊✲ᡤ㸧




◊✲┠ⓗ
⌧ᅾ㸪඲ୡ⏺ࡢ࢚ࢿࣝࢠ࣮ᾘ㈝㔞ࡢ í ࡣ໬Ꮫᕤᴗ࡟࠾࠸࡚⏕⏘ࡉࢀࡿ≀㉁ࡢศ㞳⵨␃࡟ࡼࡗ࡚༨ࡵ

ࡽࢀ࡚࠾ࡾ㸪୰࡛ࡶࢼࣇࢧࡢ⇕ศゎ࡟ࡼࡗ࡚ᚓࡽࢀࡿࣉࣟࣃ࣭ࣥࣉࣟࣆࣞࣥࡢศ㞳⵨␃ሪࡣᩘ  ẁ࡟ࡶ㐩ࡋ㸪ᴟࡵ࡚࢚ࢿࣝࢠ࣮ࢥࢫࢺࡢ኱ࡁ࡞ࣉࣟࢭࢫ࡜࡞ࡗ࡚࠸ࡿࠋࡇࡢࡓࡵ㸪ࡑࡢศ㞳⵨␃ࣉࣟࢭࢫࡢຠ⋡໬ࡸ㸪⵨␃࡟௦ࢃࡿ᪂つศ㞳ᡭἲࡢ㛤Ⓨࡀồࡵࡽࢀ࡚࠸ࡿࡀ㸪᭱㏆࡟࡞ࡗ࡚㸪$J; ࢮ࢜ࣛ࢖ࢺ⭷ ከᏍ㉁࢔࣑ࣝࢼ
⟶ࡢ⾲㠃࡟ࢮ࢜ࣛ࢖ࢺ⤖ᬗࢆᡂ㛗ࡉࡏࡓࡶࡢ ࡀ㧗࠸ࣉࣟࣃ࣭ࣥࣉࣟࣆࣞࣥศ㞳⬟ࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀ㸪⵨␃ሪ࡜ࢮ࢜ࣛ࢖ࢺ⭷ศ㞳࡜ࡢࣁ࢖ࣈࣜࢵࢻ໬࡟ࡼࡿศ㞳ຠ⋡ࡢྥୖࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡇࡢ $J; ࢮ࢜ࣛ࢖ࢺࡣ㸪༢ᡂศࡢࣉࣟࣃࣥ࠾ࡼࡧࣉࣟࣆࣞࣥࢆඹ࡟྾╔ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ࡟ࡶ࠿࠿ࢃࡽࡎ㸪ࣉࣟࣃ࣭ࣥࣉࣟࣆ
ࣞࣥΰྜ࢞ࢫ࡟ᑐࡋ࡚㸪ࣉࣟࣆࣞࣥࡢࡳࢆ㑅ᢥⓗ࡟㏱㐣ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚࠸ࡿࠋࡑࡢศ㞳࣓࢝ࢽࢬ࣒࡜ࡋ࡚ࡣ㸪ࣉࣟࣆࣞࣥࡢS㟁Ꮚ࡜ $J࢝ࢳ࢜ࣥ࡜ࡢ┦஫స⏝࡟ࡼࡿ≉␗྾╔ࡀ⏕ࡌ㸪ࡑࢀ࡟ࡼࡗ࡚⣽Ꮝෆ࡟࠾ࡅࡿࣉࣟࣃࣥࡢᣑᩓࡀ㜼ᐖࡉࢀ࡚࠸ࡿࡇ࡜ࡀྍ⬟ᛶࡢ୍ࡘ࡜ࡋ࡚⪃࠼ࡽࢀ࡚࠸ࡿࡶࡢࡢ㸪ࡑࡢᐇド࡟ࡣ⮳ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛㸪$J; ࢮ࢜ࣛ࢖ࢺ࡟྾╔ࡋࡓࣉࣟࣆࣞࣥ࡟ࡘ࠸࡚ࡢ ab initio 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࡇ࡜࡟ࡼࡾ㸪ࡑࡢ྾╔࣓࢝ࢽࢬ࣒ࢆ⌮ゎࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ$J; ࢮ࢜ࣛ࢖ࢺࡢ SULPLWLYHFHOO ࡟ࣉࣟࣆࣞࣥศᏊࢆᤄධࡋࡓ⣔ࢆᵓ⠏ࡋ㸪197 ࢔ࣥࢧࣥࣈࣝ . ࡟ࡼࡿ ab initio0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ SV ᐇ᪋ࡋࡓᚋ㸪19( ࢔ࣥࢧࣥࣈࣝ࡟ษࡾ᭰࠼㸪ࡉࡽ࡟ SV ௨ୖࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋィ⟬࡟⏝࠸ࡓࣔࢹࣝࡣ ᅗ  㸪ձ ࣉࣟࣆࣞࣥࡢ྾╔ࡋ࡚࠸࡞࠸ $J; ࢮ࢜ࣛ࢖ࢺ㸪ղ $J; ࢮ࢜ࣛ࢖ࢺࡢࢫ࣮ࣃ࣮ࢣ࣮ࢪ୰࡟Ꮡᅾࡍࡿ  ಶࡢ $J࢝ࢳ࢜ࣥࡢෆ㸪 ಶࡢ $J࢝ࢳ࢜ࣥ࡟ࣉ
ࣟࣆࣞࣥศᏊࡀ  ಶࡎࡘ㓄఩ࡋࡓࣔࢹࣝ㸪ճ  ಶࡢ $J࢝ࢳ࢜ࣥ࡟ࣉࣟࣆࣞࣥศᏊࡀ  ಶࡎࡘ㓄఩ࡋࡓࣔࢹ
ࣝ㸪մ ճࡢࣔࢹࣝ࡟  ಶࡢࣉࣟࣆࣞࣥศᏊࢆ㏣ຍࡋࡓࣔࢹ࡛ࣝ࠶ࡿࠋࡇࡇ࡛㸪ࣔࢹࣝմ࡟࠾ࡅࡿࣉࣟࣆࣞࣥ
ࡢ྾╔㔞ࡣ㸪ᐇ㝿ࡢ⭷ศ㞳࡟࠾࠸࡚ᐃᖖ≧ែ࡜࡞ࡗ࡚࠸ࡿ᫬ࡢࣉࣟࣆࣞࣥ྾╔㔞࡟➼ࡋ࠸ࠋab initio0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢヲ⣽ࡣ௨ୗࡢ㏻ࡾࠋࢯࣇࢺ࢙࢘࢔㸸&3.㸪ỗ㛵ᩘ㸸3%(㸪ᇶᗏ㛵ᩘ㸸'=9302/23765*7+㸪
&XWRII㸸5\㸪5HO&XWRII㸸5\㸪᫬㛫ࢫࢸࢵࣉ㸸IV




◊✲ᡂᯝ
Ab initio 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚᫂ࡽ࠿࡜࡞ࡗࡓ $J࢝ࢳ࢜ࣥ࡜྾╔ࣉࣟࣆࣞࣥศᏊࡢࢲ࢖ࢼ࣑ࢡ

ࢫࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋձ VLWH  ࡟Ꮡᅾࡍࡿ $J࢝ࢳ࢜ࣥࡣࢮ࢜ࣛ࢖ࢺࡢ 65 ⎔ࢆฟධࡾࡍࡿ≉␗࡞⛗ື㐠ືࢆ♧ࡍࠋ୍᪉㸪VLWH㹼VLWH ࡢ $J࢝ࢳ࢜ࣥࡣᴟࡵ࡚ᚤᑠ࡞᣺ື㐠ືࢆ♧ࡍ VLWH㸪VLWH㸪VLWH㸪VLWH ࡢ ✀ࡢ VLWH ࡟఩⨨ࡍࡿ $J࢝ࢳ࢜ࣥ࡟ࣉࣟࣆࣞࣥศᏊࡀ㓄఩ࡍࡿ ࠋղ ィ⟬᫬㛫ෆ࡟ࣉࣟࣆࣞࣥศᏊࡢ $J࢝

- 376 -ᅗ  ab initio 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟⏝࠸ࡓᵓ㐀ࣔࢹࣝ㸸ձ ࣉࣟࣆࣞࣥࡢ྾╔ࡋ࡚࠸
࡞࠸ $J; ࢮ࢜ࣛ࢖ࢺ㸪ղ $J; ࢮ࢜ࣛ࢖ࢺࡢࢫ࣮ࣃ࣮ࢣ࣮ࢪ୰࡟Ꮡᅾࡍࡿ  ಶࡢ $J࢝ࢳ࢜ࣥࡢෆ㸪 ಶࡢ $J࢝ࢳ࢜ࣥ࡟ࣉࣟࣆࣞࣥศᏊࡀ  ಶࡎࡘ㓄఩ࡋࡓࣔࢹࣝ㸪ճ 
ಶࡢ $J࢝ࢳ࢜ࣥ࡟ࣉࣟࣆࣞࣥศᏊࡀ  ಶࡎࡘ㓄఩ࡋࡓࣔࢹࣝ㸪մ ճࡢࣔࢹࣝ࡟  ಶࡢࣉࣟࣆࣞࣥศᏊࢆ㏣ຍࡋࡓࣔࢹࣝ
ࢳ࢜ࣥ࠿ࡽࡢ⬺㞳ࡣほࡉࢀ࡞࠸ࠋճ $J࢝ࢳ࢜ࣥ࡟  ಶࡎࡘ㓄఩ࡋࡓࣉࣟࣆࣞࣥศᏊࡀࡑࢀࡒࢀ㏆᥋ࡋ࡚࠸ࡿࡓࡵ࡟㸪ศᏊ㛫ࡢ⾪✺ࡀ⏕ࡌ㸪ࡇࢀ࡟ࡼࡗ࡚ࣉࣟࣆࣞࣥศᏊࡀ⬺㞳ࡍࡿࠋࡲࡓ㸪⬺㞳ࡋࡓࣉࣟࣆࣞࣥศ
Ꮚࡣูࡢ $J࢝ࢳ࢜ࣥ࡟㓄఩ࡋ㸪ࡉࡽ࡟㸪ࡇࡢ  㓄఩ᵓ㐀࠿ࡽ  ಶࡢࣉࣟࣆࣞࣥศᏊࡀ⬺㞳ࡍࡿ⌧㇟ࡀぢࡽࢀࡿࠋࡇࡢ⌧㇟࡟ࡘ࠸࡚ࡣ㸪ࣉࣟࣆࣞࣥศᏊࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆィ⟬ࡋ㸪$J࢝ࢳ࢜ࣥ࡟  ಶ㓄఩ࡋࡓࣉࣟࣆࣞࣥศᏊࡀ⬺㞳ࡍࡿࡓࡵࡢ࢚ࢿࣝࢠ࣮㞀ቨࡣᴟࡵ࡚኱ࡁࡃ㸪⮬㌟ࡢ㐠ື࢚ࢿࣝࢠ࣮ࡢࡳ࡛ࡣ⬺㞳ࡀᅔ㞴࡛࠶ࡿࡇ࡜㸪୍᪉㸪$J࢝ࢳ࢜ࣥ࡟  ಶ㓄఩ࡋࡓࣉࣟࣆࣞࣥศᏊࡢෆ㸪 ಶࡢࣉࣟࣆࣞࣥศᏊࡀ⬺㞳ࡍࡿሙྜࡣ㸪࢚ࢿࣝࢠ࣮㞀ቨࡀศᏊ㐠ື୪ࡳ࡟ᑠࡉࡃ㸪⬺㞳ࡀᐜ࡛᫆࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋմ $J࢝ࢳ࢜ࣥ࡬ࡢ  㓄఩ᵓ㐀࡟ຍ࠼㸪 㓄఩ᵓ㐀ࡶほࡉࢀࡿࠋ௨ୖࡢィ⟬⤖ᯝࡼࡾ⪃࠼ࡽࢀࡿ $J; ࢮ࢜ࣛ࢖ࢺ⭷୰࡛ࡢࣉࣟࣆࣞࣥࡢᣑᩓ࣓࢝ࢽࢬ࣒ࡣ㸪ᐃᖖ≧ែ࡟㐩ࡍࡿ๓ࡢճࡢ≧ែ࡟࠾࠸࡚㸪$J; ࢮ࢜ࣛ࢖ࢺࡢࢫ࣮ࣃ࣮ࢣ࣮ࢪࡀࣉࣟࣆࣞࣥศᏊ࡟ࡼࡗ࡚㛢ሰࡉࢀ㸪ࣉࣟࣃࣥศᏊࡀ྾╔࡛ࡁ࡞ࡃ࡞ࡿࠋࡑࡋ࡚㸪ᐃᖖ≧ែմ࡜࡞ࡿ࡜㸪ࣉࣟࣆࣞࣥศᏊ㛫ࡢ⾪✺࡟ࡼࡗ࡚㸪 㓄఩ᵓ㐀㸪 㓄఩ᵓ㐀ࡢᙧᡂ࣭ᔂቯࡀᐜ᫆࡟⏕ࡌࡼ࠺࡟࡞ࡾ㸪$J࢝ࢳ࢜ࣥ㛫ࢆࣉࣟࣆࣞࣥศᏊࡀάⓎ࡟࣍ࢵࣆࣥࢢࡋ࡚
࠸ࡃࡇ࡜࡟ࡼࡗ࡚㸪㑅ᢥⓗ࡞ࣉࣟࣆࣞࣥศᏊࡢ⭷㏱㐣ࡀ㉳ࡇࡿ࡜࠸࠺ࡶࡢ࡛࠶ࡿࠋࡇࡢࡼ࠺࡟㸪ࣉࣟࣆࣞࣥ
ࡢ≉␗࡞ᣑᩓ࣓࢝ࢽࢬ࣒ࡀ᫂ࡽ࠿࡜࡞ࡾࡘࡘ࠶ࡿࡀ㸪ᮏ◊✲ࢆ᏶⤖ࡉࡏࡿࡓࡵ࡟㸪ࡉࡽ࡟ᚲせ࡜࡞ࡿࡢࡣ㸪ᐃᖖ≧ែմ࡟࠾࠸࡚┿࡟ࣉࣟࣃࣥศᏊࡀ㏱㐣ฟ᮶࡞࠸ࡇ࡜ࢆ♧ࡍࡇ࡜࡛࠶ࡿࠋࡼࡗ࡚㸪 ᖺᗘ࡛ࡣ㸪 ᗘ౫Ꮡᛶ࡟ࡘ࠸࡚ࡢ᳨ウࢆ㐍ࡵࡿ௚㸪࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡗ࡚ࣉࣟࣃࣥࡢ㏱㐣ᣲືࢆィ⟬ࡍࡿ㸪࠶ࡿ࠸ࡣ㸪༢⣧࡞ࣉࣟࣆࣞࣥ㏱㐣⤒㊰࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆィ⟬ࡍࡿࡇ࡜࡛㸪ࣉࣟࣃࣥࡢ㏱㐣ࡀᅔ㞴࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡜ࡍࡿࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫⥴ ۻ‬᪉ ᬛᕼ㸪㓇஭ ồ㸪ᯇ᪉ ṇᙪ㸪ᡭᔱ ຾ᘺ㸪⏣୰ ⚽ᶞ㸪$J ⨨᥮ࢮ࢜ࣛ࢖ࢺ ; ⭷ࡢࣉࣟࣆࣞࣥ྾╔࣓࢝ࢽࢬ࣒ࡢゎ᫂㸪➨  ᅇࢥࣟ࢖ࢻ࠾ࡼࡧ⏺㠃໬Ꮫウㄽ఍㸪࣏ࢫࢱ࣮㸪:HE㸪 ᖺ  ᭶  ᪥‫⥴ ۻ‬᪉ ᬛᕼ㸪㓇஭ ồ㸪ᯇ᪉ ṇᙪ㸪ᡭᔱ ຾ᘺ㸪⏣୰ ⚽ᶞ㸪$J ⨨᥮ࢮ࢜ࣛ࢖ࢺ ; ⭷࡟࠾ࡅࡿࣉࣟࣆࣞࣥ྾
╔࣓࢝ࢽࢬ࣒ࡢィ⟬⛉Ꮫⓗ᳨ウ㸪➨  ᅇ᪥ᮏ྾╔Ꮫ఍◊✲Ⓨ⾲఍㸪࣏ࢫࢱ࣮㸪㛗㔝ᕷ㸪 ᖺ  ᭶  ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ㄽᩥ࡜ࡋ࡚ᢞ✏ࡍࡿࡇ࡜ࢆணᐃࠋ

- 377 -













Design and functional development of molecular hybrids
using metal oxide nanoclusters
'+!&


%+

)

(*


Çn46/:12>UÇn#Çn46ªe'y¼*¤ R¿#°*Ve«qPv Y°'  %¾o¡*Ë"'Çn46/:12>ÇnÅS %
'´[Zµ¬ Tc G$'y#¸dE '  s('|£¦0;>7MeÇnÅS*brÃCeO' ÇnVeÃNÌe
z*PvÈ46/:12>*[{ ' *¶L ! ¾ÇnÅS
'46§Ê*O' ÍL
³Î*'È46/:12> (Ag30,^ 1) *[{Me´[DÑhiy¸dy*@¨' *%£¦ (%´[°#WxyÆeSg¹©jÏ@Î %% ' *¡ $

£¦J¹©* Gaussian 16 7
<0:8*²É CAMB3LYP *apÉ PO  631G*Ag  W  LanL2DZ ECP *





dA1 nm §Ê*'ÇnÅSÈ+-= (ÄÅÈ) *Wx' $&ÇnÅSKÂ
È 16 FÈ+-=*mI S[*d È+-=ÁHQ*Wx' $&È 30 F %'È/:12> (Ag30; ^ 1) *[{Ag30 ÇnÅSÈ/:12>%'Me´[D&¿U®^  Me´[D  ¿Me½À- 378 -

X ¯¿· %iÌez X ¯]Xw­¿ (XAFS)#H¬M %i®ÇnÅSKÂ 30 FÈVebcc `ÃN^$J`/:12> { *% !Ag30 ÁHQ*Wx'^$J`/:12> %ÁH(' *¶L Ag30 Ìez*ÆeSg¹©$&»  (^ 1)Ag30  HOMOHOMOí1HOMOí2 
Ag30 /:12>f_p ½À\l¥y*}Me½À?LUMOLUMO+4  Ag30/:12>f_d ½À\l¥y*}Me½À!HOMO-LUMO ,5;.>.937 3.5 eV Ag30  LUMOLUMO+4

ÇnÅSÐ

Ag30 /:12>f_'Ag30 ÁHQ*Wx' $&Ag30 /:12> %ÁH('jÏ®*~})ÇnÅS Ag /:12> %' Ag30?±  Ag(0)46ªe'ÅSÁHy*} *% Bt£¦uMe´[D¿ÌezWxyÉ'¢¶*¿#Ìez*Pv¸d«kº¹#(*O¸dWxx s(' #"
>@ /" *N FP !+O 0> K( <1 *M G= L R9 3 0' ) ³B@"$

T#SIU

8S

J,?4´ 5:%.

E  6-2  ;AD*.QC  &H 2  7  5
>@.RVXNH6X]XNL³6\QWKHVLVDQGSURSHUWLHVRIDWRPLFDOO\SUHFLVHVLOYHUQDQRFOXVWHUVZLWKSRO\R[RPHWDODWHV´WK$VLDQ&RQIHUHQFHRQ&RRUGLQDWLRQ&KHPLVWU\ $&&& 7DLZDQ7DLSHL 2  7  5"

[1] “6XUIDFHH[SRVHGVLOYHUQDQRFOXVWHUVLQVLGHPROHFXODUPHWDOR[LGHFDYLWLHV”
K. Yonesato, D. Yanai, S. Yamazoe, D. Yokogawa, T. Kikuchi, K. Yamaguchi, K. Suzuki, LQSUHVV '2,VZ [2] “Ligand-Protecting Strategy for Controlled Construction of Multinuclear Copper Cores within Ring-Shaped
Polyoxometalate”
Y. Koizumi, K. Yonesato, K. Yamaguchi, K. Suzuki,
Inorg. Chem. 2022, 61, 9841–9848.
[3] “Supported Anionic Gold Nanoparticle Catalysts Modified Using Highly Negatively Charged Multivacant
Polyoxometalates”
K. Xia, T. Yatabe, K. Yonesato, T. Yabe, S. Kikkawa, S. Yamazoe, A. Nakata, K. Yamaguchi, K. Suzuki,
Angew. Chem. Int. Ed. 2022, 61, e202205873.
[4] “Recent Advances in Hybrid Materials of Metal Nanoparticles and Polyoxometalates”
K. Xia, K. Yamaguchi, K. Suzuki,
Angew. Chem. Int. Ed. 2023, 62, e202214506.
[5] ““Template synthesis” of discrete metal clusters with two- or three-dimensional architectures”
Y. Sunada, K. Yamaguchi, K. Suzuki, Coord. Chem. Rev. 2022, 469, 214673.

- 379 -

SH2 





Binding free energy calculations of a phosphopeptide with SH2 domain
 "+'

*!#,



 !#



:PC5ÀʊED;?¬h!ª¯[86@MTÊ-_+Ï´¨É¤+:PC5ÀÒ¢RX Ôu`Ñ&ÓZ:PC5À  (ED;?Í]-½^¬h+  \qy¶ },+:PC5ÀʊED;?¬h!~ :PC5ÀʊV\q¬h!+-&
V\qL3P? :PC5À[Ìj&,F7<>¬h+ wED;?!:PC5À²Ø¥$¬h+ %¢RXÚk&x)ED;? Ç!V\q"Ö¦Â
*¬hUone+,) Ë(*:PC5ÀʊED;?¬h!:PC5ÀʊV\q¬h"{ (*d¡É¤+®),+; ­¬Ç¶' 105 tÜ(*:PC5ÀʊED;?¬h ³hWÇl ¬hz ¸ª¼"),,)ars ¬ )¡ED;?Í]-½^+S«$ )  
+ >@)\qdarÝ0ROHFXODU'\QDPLFV0'Þ8GJNQ8KP(*:PC5ÀʊED;?
¬h d¡Ç¶&È.+~tÜÇl :PC5ÀʊED;?³hW

0' ·§-±

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!ED;? ÇÂ'\q |Ù f\g*Ã#,:PC5ÀʊED;?¬h À-
¶+!Õ +Ä!Ç ©-bÆ+- 0' ·§(+¶ p#+ >@»Û!tÜ=Q: ¾v),+ 6+Ý6UFKRPRORJ\Þ?I0PLPÎeED;?ÝLPÎ
e;O8PßS<Þ ¬h-w¿c¡Ç ©- 0' ·§(*:PC5ÀED;? d¡¬hI2A9HÅ+

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3URWHLQ'DWD%DQNÝ3'%ÞÐ, * >@¾vÇmlÀ¬h ars(*ED;?Í]w¬hµi'¬hz £),+ ×¡ÇmED;?¹½ S«$-f\º +Y!
G»Û!¬hÇ ++&Ó )¬hµi +Y-g* ED;?¹½
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6@MTÊÉ¤- F+&7/$£),+ars! &'

S<010 Í]¬h7 ª¯-ie+8

S<9.0 Í]¬h+7 ª¯ ie-Y_+&7/$ "L ¬h+-u"{ ¬Ç=

Q:ÝF6+&'3'%,'$8/F6+&7/$3'%,'&,2Ë!), >@»Û!6+ ?I0P &'&7/$ ED;? ¬h-g* [K/PPM-\qdar·§-t_3aÇ!¬ÇÝF6+&'ß3'%,' $8/F6+&7/$ß3'%,' &,2Þ

- 380 -

l XW >@8GJNQ8KP<5!:PC5ÀlÀED;?b\q6 P0 ¢M.&O 0P-<%0W    45q¤IÝ6+ ?I0P5q^ß45q0P\q^ß ¤IÞ ·§8H!%/PNPDLP6-$/·§-±ÝAÞ¬Çl ED;?¬h0> glÝ$UJ$UJ$ODÞ À#PLPÎe;O8

P À#P -7RJd

P? Ý

P? * QVÞ-ED;? }+ JHQHUDOL]HG 5HSOLFD ([FKDQJH ZLWK 6ROXWHÉ¤-¼"fNDL2&]\qdar !Õ),°I jI $-&]+
7HPSHULQJ ÝJ5(67Þ >@ -ÝA Þ·§>-Y),+jI&]+°IÝkÀVROXWHÌ\Þ!6+ ?I0P:PC5À ED;?¬h0> (lÀED;? %Ø1BM4Q¬h¢RX&' 6 &7/$ ³hWwNDL2^! kÀjI!  . 9NDL2*  QVÝh·ȝVÞ ·§-t_0 ·§!\qdar·§>/ *(1(6,6 >@ -±

Umbrella potentials

Half flat-bottom potential

30 Å

Ala48
pTyr

Arg39

Reaction coordinate
COM (R21/R39/A48)…COM(pY)

Arg21

Solute temperingA  /PNPDLP6 J5(67 -¬h·§ QH!#/PNPDLP6-$/·§ ¬:LPÎeED;?

}É¤-¼"+

Ala48

!E

`

A  7RJd ÝED;?¬h0> gl À#PLPÎe;O8P

Arg39

À#P Þ-  c #*Ö @<
D8K<>-ulÀED;? LPÎe;O8P!
,l 6+ ?I0P

$UJ ¨¬h-NW *}~)LPÎl:PC5À L¢RX

Arg21

pTyr

A  /PNPDLP6-·§)}É¤@<D8K<> %:PC5ÀED;?-Zb%
#ÒÇ DM!q>x ( P?

^-B' sT¡:PC5ÀL3P?! ED;? Ý09'ÇÂÞ-®V7RJd sz Q´!8e®+fJ5(67 -·§¬-u !7RJd-sz+ kÀÌ\Ý:P
C5À ¬h0>lÀED;?Þ jI&](*:PC5ÀED;?¢RX-c¡{%- 381 -

ED;? ¬h}-.È+tÖ)S NDL2w:PC5ÀED;? ne-DO<>+¬hnU ):Q>·§ ¬hnU-y2I¬hnUX++

'? ·§! NDL2   NDL2: ¬h}É¤ ),J5(67 ÝA Þ+LPÎeED;? ¬h}É¤ c(( &7/$¬hwJ5(67 ·§  .

© +-u6+  &'C=Q:-NPHDQV 5:Q¶ ¬    ED;? ¬h!LPÎe;O8(*¬hÇ \H-%ÝA ÞP ¬hF7<>b8n F7<> ¬hzË ),O{!¬Ç+     

¬hµi ËÓZ+®),+)¬hÇ!wm¡  ED;?!³^ Í;d¡¬hµi-o+&u=,^±·§ )LPÎeED;? ¬h   

  ?I0P MQDÇ|Ù+&  *d¡¬hnU Ë /OL<5|p&ÓZ+8| u=

,

b)

40

a)

30
10

20

SH2-CD28 binding

Bound

0

Distance (Angstrom)

Unbound

0

1000

2000 3000 4000
Time (x 50 ps)

5000

SH2-CTLA-4 binding

A J5(67 -¬h·§)S NDL2 +:PC5ÀED;?

&'  &7/$neÝDÞ¬hÇÝEÞ
#%»Ûtw!   ?I0P   6  ED;? ¬h  -\qdar8GJNQ8KP-±:PC5ÀED;? d¡¬hI2A9H-cJ5(67 -+/PNPDLP6! LPÎeED;? ¬h}É¤© 8|*    ED;? d¡¬hnUË +-) 'O »Û¬h°1BM4Q-s¡v&*tÜ=Q: c &·§¬ DM--+

(%

YX>FA C-Q. 6+ $;36) 6  <  :W,LX

!$V+ *DNP :=+4)I - 382 -

ZX6X\RQJ5H.HQML0L]XJXFKL%LQGLQJVSHFLILFLW\RISKRVSKRSHSWLGHUHFRJQLWLRQGRPDLQDQDO\]HG
E\J5(67VLPXODWLRQ&%, 4)  62) 6  <  :WK1X
[X>FA6+ $ BS@R7 J/ "% $ $EH) I  0#% 6  <  :W'UX
%



+RVRH<XKL<RKHL0L\DQRLUL6X\RQJ5H6DNL2FKL<X\D$VDKLQD7RUX.DZDNDPL0DVDWDND.XURGD.HQML
0L]XJXFKLDQG0DVD\XNL2GD)(%6-   ( M?T O9 8G&5


&
>@6DQFKHV.HWDO6FL5HS  GRLVZ>@:DQJ-HWDO)URQW0RO%LRVFL  >@0DFKLGD.DQG/LX%$6+'RPDLQV+XPDQD3UHVV>@ 6DWRPL ,QDED 1REXWDND 1XPRWR 6KXKHL 2JDZD +LVD\XNL 0RULL 7HLNLFKL ,NXUD 5\R$EH 1REXWRVKL ,WR DQG0DVD\XNL2GD-%LRO&KHP±  >@0RPRND,L\DPD1REXWDND1XPRWR6KXKHL2JDZD0DVDWDND.XURGD+LVD\XNL0RULL5\R$EH1REXWRVKL,WRDQG
0DVD\XNL2GD0RO,PPXQRO±  >@0RWRVKL.DPL\DDQG<XML6XJLWD-&KHP3K\V  >@-DHZRRQ-XQJ7DNDKDUX0RUL&KLJXVD.RED\DVKL<DVXKLUR0DWVXQDJD7DNDR<RGD0LFKDHO)HLJDQG<XML6XJLWD
:LOH\,QWHUGLVFLSOLQDU\5HYLHZV&RPSXWDWLRQDO0ROHFXODU6FLHQFH±  &KLJXVD.RED\DVKL-DHZRRQ-XQJ<DVXKLUR0DWVXQDJD7DNDKDUX0RUL7DGDVKL$QGR.RLFKL7DPXUD0RWRVKL.DPL\DDQG<XML6XJLWD-&RPSXW&KHP
±  >@ <XKL +RVRH <RKHL 0L\DQRLUL 6X\RQJ 5H 6DNL 2FKL <X\D$VDKLQD 7RUX .DZDNDPL 0DVDWDND .XURGD .HQML
0L]XJXFKLDQG0DVD\XNL2GD)(%6-  






- 383 -

పศᏊࢆㄆ㆑࣭άᛶ໬ࡍࡿ᪂つ㘒య࡟㛵ࡍࡿ◊✲
6WXG\RQPROHFXOHUHFRJQLWLRQDQGDFWLYDWLRQRIQRYHOPHWDOFRPSOH[HV‫ۑ‬ᒣᮏ ဴஓࠊΎỈ ᮍ⣖ࠊᐑᆏ ㄔ㸦ᮾி㟁ᶵ኱Ꮫ㸧

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

◊✲┠ⓗ
⏦ㄳ⪅ࡽࡣࠊ࣍ࢫࣇ࢕ࣥࡸ 1+& ࢆᨭᣢ㓄఩Ꮚ࡜ࡍࡿࢩࢡ࣓ࣟࢱࣝ໬ࣃࣛࢪ࣒࢘㘒యࡣ᭷ᶵ࣍࢘⣲໬ྜ≀ࡢ࢝ࣝ࣎ࢽࣝ໬ྜ≀࡬ࡢ ௜ຍ཯ᛂࡸ ௜ຍ཯ᛂࡢඃࢀࡓゐ፹⬟ࢆ᭷ࡍࡿࡇ࡜ࢆぢฟࡋ࡚࠾ࡾࠊ࣍ࢫࣇ
࢕ࣥࢆᨭᣢ㓄఩Ꮚ࡜ࡍࡿࢩࢡ࣓ࣟࢱࣝ໬ࣃࣛࢪ࣒࢘㘒యࡣ ௜ຍ཯ᛂ࡜ ௜ຍ཯ᛂࡢ࡝ࡕࡽࡢ཯ᛂ࡟ᑐࡋ࡚ࡶゐ፹άᛶࢆ♧ࡍࡢ࡟ᑐࡋࠊ࢖࣑ࢲࢰࣜࣥᆺ 1+& ࢆᨭᣢ㓄఩Ꮚ࡜ࡍࡿࢩࢡ࣓ࣟࢱࣝ໬ࣃࣛࢪ࣒࢘㘒యࡣ ௜ຍ཯ᛂࡢࡳゐ፹ࡍࡿࠋࡇࡢゐ፹άᛶࡢ㐪࠸ࢆ⌮ㄽ໬Ꮫⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬ࡣࡍ࡭࡚ *DXVVLDQ ࢆ⏝࠸࡚⾜ࡗࡓࠋỗ㛵ᩘ࡜ࡋ࡚ %/<3 ࢆ⏝࠸ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ࡣࠊ+ࠊ&ࠊ%ࠊ1ࠊ2ࠊ6ࠊ3 ࡟㛵ࡋ࡚ࡣ * G ࢆࠊ3G ࡟ /DQ/'= ࢆ⏝࠸ࡓࠋ㑄⛣≧ែࡢᵓ㐀ࡣ ,5& ィ⟬࡛☜ㄆࡋࡓࠋ௒ᮇࡣపศᏊࣔࢹࣝࡢィ⟬࡟࡜࡝ࡵࡓࡓࡵィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ࣜࢯ࣮ࢫࢆ౑⏝ࡋ࡞࠿ࡗࡓࠋ



◊✲ᡂᯝ

O
R

࢖࣑ࢲࢰࣜࣥᆺ 1+& ࢆࢺࣜ࢔ࢰ࣮ࣝᆺ 1+& ࡟࠿࠼ࡓࢩࢡ࣓ࣟࢱࣝ໬ࣃࣛࢪ࣒࢘㘒యࡣ࢔࣮ࣜࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢ࢔ࣝࢹࣄࢻ࡬ࡢ ௜ຍ཯ᛂࡔࡅ࡛࡞ࡃࠊ࢚ࣀࣥ

O
Ar B
O

࡬ࡢ ௜ຍ཯ᛂ࡟ᑐࡋ࡚ࡶⰋዲ࡞ゐ፹άᛶࢆ♧ࡍࡇ࡜

N

N

R

ࡀศ࠿ࡗࡓࠋ

Ar

N
Pd
Cl

R

OH

H

EWG

R

EWG
Ar

ᅗ 



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ࠐ0LQRUL 6KLPL]X<XGDL.LWDKDUD 6KRJR 1DPLNL7HWVX\D<DPDPRWRࠊ
͆6\QWKHVLV DQG &DWDO\VLV RI3\ULGLQH
EDVHG&A3W\SH3DOODGDF\FOH&RPSOH[͇ ;;,,,QWHUQDWLRQDO6\PSRVLXPRQ+RPRJHQHRXV&DWDO\VLVࠊ ᖺ ᭶  ᪥ࠊ࣏ࣝࢺ࢞ࣝ
ࠐ1DRNL$UDL<XWR.X]LUDL7HWVX\D<DPDPRWRࠊ͆0,&FRRUGLQDWHGSDOODGLXPFRPSOH[FDWDO\]HGDGGLWLRQRIDU\OERURQDWHVWRDOGHK\GHV͇ 72&$7ࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ㛤ദฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1DRNL $UDL <XJD 6KLEX\D 6KLQLFKL .RJXFKL DQG 7HWVX\D <DPDPRWR ´ +DORJHQ6XEVWLWXWHG 0HVRLRQLF

&DUEHQH3DOODGLXP &RPSOH[HV IRU &DWDO\WLF $U\ODWLRQ RI $OGHK\GHV´  Asian J. Org. Chem. 2023 H
doi.org/10.1002/ajoc.202300076

- 384 -

㧗㟁఩㕲◲㯤ࢱࣥࣃࢡ㉁ࡢάᛶ୰ᚰࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟ࡘ࠸࡚ࡢ⌮ㄽⓗゎᯒ
7KHRUHWLFDODQDO\VLVIRUWKHJHRPHWULFDODQGHOHFWURQLFVWUXFWXUHVRIWKH
DFWLYHFHQWHURIKLJKSRWHQWLDOLURQVXOIXUSURWHLQ‫ۑ‬ᇼ ඃኴࠊబ⸨ ⥤㤶ࠊಥᒇ ኊ኱㑻ࠊΏ㎶ ୐㒔⛥㸦⟃Ἴ኱Ꮫ㸧



◊✲┠ⓗ
㧗㟁఩㕲◲㯤ࢱࣥࣃࢡ㉁㸦HiPIP㸧ࡣࠊගྜᡂ㟁Ꮚఏ㐩⣔࡛ࡣࡓࡽࡃ㟁Ꮚ㐠ᦙࢱࣥࣃࢡ㉁࡛࠶ࡿࠋHiPIP ࡣࠊάᛶ୰ᚰ࡟[4Fe4S]ࡢ࢟ࣗࣂࣥᆺࡢ㕲◲㯤ࢡࣛࢫࢱ࣮ࢆᣢࡘࡀࠊྠᵝࡢ㦵᱁ࢆᣢࡘࣇ࢙ࣞࢻ࢟ࢩࣥ࡟ẚ࡭࡚ᴟࡵ࡚㓟໬㑏ඖ㟁఩ࡀ㧗࠸ࠋࡇࡢཎᅉ࡜ࡋ࡚ࠊ㕲◲㯤ࢡࣛࢫࢱ࣮࿘ࡾࡢᵓ㐀ࡀせᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࠊHiPIP ࡢ㕲◲㯤ࢡࣛࢫࢱ࣮࿘ࡾࡢᵓ㐀⎔ቃ࡟ὀ┠ࡋࠊ࿘㎶ࡢ࢔࣑ࣀ㓟࠿ࡽࡢᙳ㡪ࢆ⪃៖ࡋࡓࢡࣛ
ࢫࢱ࣮ࣔࢹࣝࡢ㟁Ꮚ≧ែࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾィ⟬ࡋࠊᏳᐃᵓ㐀࡜㟁Ꮚ≧ែ࡟ࡘ࠸࡚⪃ᐹࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
HiPIP ࡢ㑏ඖᆺ(2Fe(II)2Fe(II))࡟ࡘ࠸࡚ྲྀࡾୖࡆࡿࠋX ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾᚓࡽࢀࡓ[4Fe4S]ࢡࣛࢫࢱ࣮ࡢ

ᵓ㐀ࢆࡶ࡜࡟ࠊྲྀࡾᚓࡿࢫࣆࣥ㓄⨨࡟ࡘ࠸࡚㟁Ꮚ≧ែゎᯒࢆ⾜ࡗࡓࠋィ⟬࡟ࡣࠊGaussian 16 ࢆ⏝࠸ࡓࠋ



◊✲ᡂᯝ
12 ㏻ࡾࡢึᮇࢫࣆࣥ㓄⨨࡟ᑐࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ4 ㏻ࡾࡢึᮇࢫࣆࣥ㓄⨨࡟ᑐࡋ࡚⾜ࡗࡓィ⟬ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟Ᏻᐃ࡞ᵓ㐀࣭㟁Ꮚ≧ែ࡟཰᮰ࡋࡓࠋᚓࡽࢀࡓᵓ㐀࡟ᑐࡋ࡚ࠊNBO ゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
2 ࡘࡢ Fe 㛫࡛ᙧᡂࡉࢀࡿ㠃ୖ࡛ࢫࣆࣥࡢ㠀ᒁᅾ໬ࡀほࡉࢀࡓࠋࡲࡓࠊ㌶㐨࢚ࢿࣝࢠ࣮ࡢゎᯒ࠿ࡽ HiPIP ࡢ㓟໬㑏ඖ཯ᛂࡣࡑࡢ㠃ୖ࡛㉳ࡇࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ✀ࠎࡢࣔࢹࣝ࡟ᑐࡍࡿィ⟬ࡢ⤖ᯝࠊHiPIP ࡛ࡣࡑࡢ࿘㎶ࡢ࢔࣑ࣀ㓟ࡀ[4Fe-4S]ࢡࣛࢫࢱ࣮ࡢᗄఱᏛⓗ࣭㟁Ꮚⓗᵓ㐀ࢆᏳᐃ໬ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬1. Y. Hori,ࠕComputational Chemical Approaches to the Microscopic Mechanism of Anhydrous Proton Conduction
MaterialsࠖࠊࠗAsia Pacific Conference of Theoretical and Computational Chemistry APATCC-10࠘ࠊQuy Nhon (Vietnam)ࠊ
(February 22, 2023). (Oral) (invited)ࡑࡢ௚ࠊ10 ௳ࡢཱྀ㢌Ⓨ⾲ࠊ10 ௳ࡢ࣏ࢫࢱ࣮Ⓨ⾲ࢆ⾜ࡗࡓࠋฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫( ۻ‬1) Y. Hori, H. Nakamura, T. Sakawa, N. Watanabe, M. Kayanuma, M. Shoji, M. Umemura, Y. Shigeta, Astrobiology,
22(11), 1330–1336 (2022).
‫( ۻ‬2) A. Sato, Y. Hori, Y. Shigeta, Inorg. Chem., 62(5), 2040–2048 (2023).
‫( ۻ‬3) Y. Hori, A. Sato, Y. Shigeta, J. Comp. Chem., Jpn., 21(4) 77–79 (2022).
‫( ۻ‬4) S. Sugiura, T. Kubo, Y. Haketa, Y. Hori, Y. Shigeta, H. Sakai, T. Hasobe, H. Maeda, J. Am. Chem. Soc., in press(2023). DOI: 10.1021/jacs.3c01025
ࡑࡢ௚ࠊ2 ሗࡢㄽᩥࢆฟ∧ࠊ5 ሗࡢㄽᩥࢆᢞ✏୰ࠋ- 385 -

᪂ࡋ࠸἞⒪ἲࡢ☜❧ࢆ┠ᣦࡋࡓ᪂つゐ፹ࡢ㛤Ⓨ
'HYHORSPHQWRI1RYHO&DWDO\VWVIRUWKH(VWDEOLVKPHQWRI1HZ
7KHUDSHXWLF0HWKRGV‫ࢶ୕ۑ‬἟ ἞ಙࠊ㔠஭ ồࠊୖᮧ ♸ఃࠊྂ⏣ ᑗ኱ࠊᒣḟ ೺୕ࠊ㔝ᓮ ከᐇᏊࠊᕴ
ಇᩥࠊᒣ᰿ ୕ዉࠊ⸨ྜྷ ᾈᖹࠊᒣ᲍ ♸᥹ࠊ⏣㎶ 㥴ࠊ㧗ᶫ ࿴ᕼࠊ୰ᑿ ⿱ᗣࠊ㝞⹿Ᏹࠊ∦ᒣ ཭㔛ࠊ⚟⏣ ᬛஅࠊᒾ஭ ⠜ᚿࠊᐑෆ බ኱ࠊᮾᒇ ຬ㒔ࠊᖜᓮ ⨾ᾴࠊධỤ ඃ㸦ᮾ኱㝔⸆㸧



◊✲┠ⓗ
ᮏ◊✲ࡢ┠ⓗࡣࠊ᪂ࡋ࠸἞⒪ἲࡢ㛤Ⓨ࡟ࡘ࡞ࡀࡿ㠉᪂ⓗ࡞ゐ፹ࡢ㛤Ⓨࢆ⾜࠺ࠋᮏ◊✲ࡣ᪂つࢣ࣑࢝ࣝࢫ࣌

࣮ࢫ࡟ྥࡅࡓ」㞧ᵓ㐀ศᏊྜᡂࢆຍ㏿ࡍࡿ㠉᪂ⓗゐ፹๰⏕ࠊ࡜ேᕤゐ፹ࡢ໬Ꮫ௓ධ࡟ࡼࡿゐ፹་⒪ࡢ἞⒪ᛂ
⏝࠿ࡽᡂࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲලయⓗ࡟ࡣձゐ፹ⓗ sp3C-H ⤖ྜάᛶ໬࡟ࡼࡿ sp3 Ⅳ⣲ࣜࢵࢳᵓ㐀ࡢຠ⋡ⓗ࡞㦵᱁ᙧᡂ཯ᛂࡢ㛤Ⓨࠊղࣄࢫࢺࣥࡢ࢔ࢭࢳࣝ໬ゐ፹ࡢ㛤Ⓨ࡟ࡼࡿேᕤ㌿෗ไᚚࠊճ࢔࣑ࣟ࢖ࢻࢱࣥࣃࢡ㉁ࡢ㓟⣲໬ゐ፹ࡢ㛤Ⓨࢆ┠ᣦࡍࠋ࠸ࡎࢀࡢ◊✲࡟࠾࠸࡚ࡶ Gaussian 16, GRRM 14, NBO 6.0 ࡞࡝ྛࢯࣇࢺࣇ࢙࢔ࢆά⏝ࡋࠊᵓ㐀᭱㐺໬ࠊບ㉳≧ែィ⟬࠾ࡼࡧศᏊ㌶㐨ゎᯒ࡟ࡼࡾ⌮ㄽⓗ࡟ศᏊࢆタィࡋࠊᐇ㝿ࡢ཯ᛂ࡟㐺⏝ࡋࠊࡑࡢ⤖ᯝࢆࣇ࢕࣮ࢻࣂࢵࢡ
ࡍࡿࡇ࡜࡛᭦࡞ࡿゐ፹ᵓ㐀ࡢ᭱㐺໬࡟ྲྀࡾ⤌ࡴࠋ



◊✲ᡂᯝ
⣽⬊ෆ࢔ࢩࣝ CoA ࢆάᛶ໬ࡍࡿࣄࢫࢺࣥ࢔ࢩࣝ໬ゐ፹ࡢ㛤Ⓨࣜࢪࣥṧᇶࡢ࢔ࢭࢳࣝ໬࡟௦⾲ࡉࢀࡿࣄࢫࢺࣥࢱࣥࣃࢡ㉁ࡢ⩻ヂᚋಟ㣭ࡣࠊ࢚ࣆࢤࣀ࣒ࢆᵓᡂࡍࡿࡇ࡜࡛

ືⓗ࡞㑇ఏᏊⓎ⌧ࡢไᚚ࡟࠿࠿ࢃࡗ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚ࠊ⣽⬊ෆ࡛ࣄࢫࢺࣥ⩻ヂᚋಟ㣭ࢆ໬Ꮫⓗ࡟ᑟධࡍࡿ
ᡭἲࡢ㛤Ⓨࡣࠊ࢚ࣆࢪ࢙ࢿࢸ࢕ࢵࢡಟ㣭ࡢᶵ⬟ゎ᫂ࡸไᚚ࡟⧅ࡀࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ⏕యෆ࡛ࡣࠊࣄࢫࢺ
ࣥ࢔ࢭࢳࣝ໬㓝⣲ࡀ࢔ࢭࢳࣝ CoA ࢆ၏୍ࡢ࢔ࢭࢳࣝࢻࢼ࣮࡜ࡋ࡚ࣄࢫࢺࣥࡢ࢔ࢭࢳࣝ໬ࢆ⾜ࡗ࡚࠸ࡿࠋࡋ
࠿ࡋࠊࡇࢀࢆᐇ⌧ࡍࡿࡇ࡜ࡢ࡛ࡁࡿ໬Ꮫゐ፹ࡣሗ࿌ࡀ࡞࠿ࡗࡓࠋ᭱㏆ᡃࠎࡣࠊ⣽⬊ෆ࡟ప⃰ᗘ࡛ࡢࡳᏑᅾࡍ
ࡿ࢔ࢭࢳࣝ CoA ࢆάᛶ໬ࡋࠊࣄࢫࢺࣥࣜࢪࣥṧᇶࢆ࢔ࢭࢳࣝ໬࡛ࡁࡿึࡵ࡚ࡢ໬Ꮫゐ፹࡜ࡋ࡚ mBnA ࢆ㛤Ⓨࡋࡓ㸦ୗᅗᕥ㸧ࠋᮏゐ፹ࡣࠊࢳ࢚࢜ࢫࢸࣝᆺࡢ࢔ࢭࢳࣝ CoA ࠿ࡽ࢔ࢭࢳࣝᇶࢆゐ፹ୖ࡬࡜ྲྀࡾ㎸ࡴࡓࡵࡢࢳ࣮࢜ࣝᇶ࡜ࠊ࢔ࢭࢳࣝᇶࢆάᛶ໬ࡍࡿࡓࡵࡢࣄࢻࣟ࢟ࢧ࣒㓟ᆺࡢồ᰾ゐ፹㦵᱁ࢆ᭷ࡍࡿࢹࢨ࢖ࣥ࡜࡞ࡗ࡚
࠸ࡿ(ୗᅗྑ)ࠋᮏ◊✲࡛ࡣࠊmBnA ゐ፹࡟ࡼࡿ࢔ࢭࢳࣝ໬ࡢ࣓࢝ࢽࢬ࣒ゎ᫂࡜ᵓ㐀άᛶ┦㛵࡟㛵ࡍࡿゎᯒࢆࠊ
DFT ィ⟬ࢆ⏝࠸࡚⾜ࡗࡓࠋࡲࡎࠊゐ፹ࡢࢳ࣮࢜ࣝᇶ࡟ྲྀࡾ㎸ࡲࢀࡓ࢔ࢭࢳࣝᇶࡀࣜࢪࣥṧᇶࡢ࢔࣑ࣀᇶ࡬࡜㌿⛣ࡍࡿ཯ᛂ⤒㊰ࡢ᥈⣴ࢆ⾜ࡗࡓ⤖ᯝࠊᙜึࡢ᝿ᐃ཯ᛂᶵᵓࡢ㏻ࡾࠊࣄࢻࣟ࢟ࢧ࣒㓟㒊఩ࡢศᏊෆࢳ࢚࢜ࢫࢸࣝᇶ࡬ࡢồ᰾ᨷᧁ࡟ࡼ
ࡿ࢔ࢭࢳࣝࣄࢻࣟ࢟ࢧ࣓࣮ࢺ✀㸦”OAc” intermediate㸧ࢆ୰㛫య࡜ࡍࡿ⤒㊰ࡀ᭱ࡶᏳᐃ࡞㑄⛣≧ែࢆ୚࠼ࡿ཯
ᛂ⤒㊰࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸦ୗᅗᕥ㸧ࠋࡋ࠿ࡋࠊண᝿࡟཯ࡋ࡚ࠊᚊ㏿ẁ㝵ࡣࣜࢪࣥṧᇶࡀ࢔ࢭࢳࣝࣄ

- 386 -

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┙ᢏ⾡ࢆ๰ฟࡍࡿ㸬㏆ᖺ㸪⤫ィⓗᶵᲔᏛ⩦࡟ᇶ࡙ࡃࢹ࣮ࢱ㥑ືᆺᮦᩱタィࡢᢏ⾡ࡀᮦᩱ◊✲ࡢᵝࠎ࡞ศ㔝࡟
ᛴ㏿࡟ᑟධࡉࢀ࡚࠸ࡿ㸬୍᪉㸪㧗ศᏊᮦᩱศ㔝࡛ࡣ㸪ᐇ㦂࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥඹ࡟ࢹ࣮ࢱ㔞ࡀᅽಽⓗ࡟୙㊊ࡋ࡚࠾ࡾ㸪ࢹ࣮ࢱ㥑ືᆺ࢔ࣉ࣮ࣟࢳࡢ㐍ᒎ࡟኱ᖜ࡞㐜ᘏࡀ⏕ࡌ࡚࠸ࡿ㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ㸪ศᏊືຊᏛ㸦MD㸧ィ⟬ࢆ⏝࠸ࡓ㧗ศᏊ≀ᛶࡢࢹ࣮ࢱ⮬ືィ⟬ࢩࢫࢸ࣒㸪RadonPy ࢆ㛤Ⓨࡍࡿ㸬ᮏࢢ࣮ࣝࣉࡀ㛤Ⓨࡋࡓ RadonPyࢆ⏝࠸࡚㸪ୡ⏺᭱኱⣭ࡢ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࢆᵓ⠏ࡍࡿ㸬◊✲᪉ἲࠊィ⟬᪉ἲᮏ ◊ ✲ ࡛ ࡣ 㸪 ᡃ ࠎ ࡢ ࢢ ࣝ ࣮ ࣉ ࡀ 㛤 Ⓨ ࡋ ࡓ 㧗 ศ Ꮚ ≀ ᛶ ࡢ ⮬ ື ィ ⟬ ࢩ ࢫ ࢸ ࣒ RadonPy㸦https://github.com/RadonPy/RadonPy㸧ࢆ⏝࠸࡚㸪⮬↛⛉Ꮫ◊✲ᶵᵓィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢࢫ࣮ࣃ࣮ࢥࣥࣆ
࣮ࣗࢱ࣮࡛ࡣ୺࡟㔞Ꮚ໬Ꮫィ⟬ࢆᐇ⾜ࡋ㸪ࡑࡢࢹ࣮ࢱࢆ⌮໬Ꮫ◊✲ᡤࡢࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮ࠗᐩᓅ࠘ୖ
࡬ࢥࣆ࣮ࡋ MD ィ⟬ࢆᐇ⾜ࡋࡓ㸬ᮏሗ࿌᭩࡛ࡣ୺࡟㔞Ꮚ໬Ꮫィ⟬ࡢ㒊ศ࡟ࡘ࠸࡚グ㍕ࡍࡿ㸬RadonPy ࡛ࡣ㸪㔞Ꮚ໬Ꮫィ⟬ࡢ࢚ࣥࢪࣥ࡜ࡋ࡚ Psi4㸦https://psicode.org/㸧ࢆ⏝࠸࡚࠸ࡿ㸬MD ィ⟬ࡢᐇ⾜࡟ᚲせ࡞ィ⟬࡜ࡋ࡚㸪ࣔࣀ࣐࣮ࣘࢽࢵࢺࡢ㓄ᗙ᥈⣴㸪ᵓ㐀᭱㐺໬ཬࡧ RESP 㟁Ⲵࡢィ⟬ࢆ⾜ࡗࡓ㸬㓄ᗙ᥈⣴࡛ࡣ㸪ࡲࡎ ETKDG ἲ[2]࡟ࡼࡾ㸪᭱኱ 1000 㓄ᗙࡢ❧యᵓ㐀ࢆ⏕ᡂࡍࡿ㸬ࡑࡢᚋ㸪GAFF2 ຊሙࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸㸪࢚ࢿࣝࢠ࣮ⓗ࡟Ᏻᐃ࡞㓄ᗙࢆ 4 ࡘ㑅ᢥࡍࡿ㸬ࡇࡢ 4 㓄ᗙ࡟ᑐࡋ࡚ࡉࡽ࡟ȰB97M-D3BJ/6-31G(d,p)࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸㸪᭱ࡶᏳᐃ࡞㓄ᗙࢆỴᐃࡋࡓ㸬ࡇࡢ᭱Ᏻᐃᵓ㐀࡟ᑐࡋ࡚㸪GAFF2 ຊሙࢆ౑⏝ࡍࡿ㝿ࡢ RESP 㟁Ⲵィ⟬ἲ࡜ࡋ࡚᥎ዡࡉࢀࡿ HF/6-31G(d)࡟ࡼࡾ RESP 㟁Ⲵィ⟬ࢆ⾜ࡗࡓ㸬ḟ࡟㸪ᒅᢡ⋡ࡢ⟬ฟ࡟ᚲせ࡞ศᴟ⋡ィ⟬ࢆ⾜ࡗࡓ㸬ศᴟ⋡ࡢィ⟬࡟ࡣ᭷㝈㟁ሙࢆ༳ྍࡍࡿ Finite-field㸦FF㸧ἲࢆ⏝࠸ࡓ㸬ศᴟ⋡ィ⟬࡛ࡣ㸪㟁Ꮚศᕸࡢṍࡳࢆグ㏙ࡍࡿࡓࡵࡢ༑ศ࡞ศᴟ㛵ᩘࢆຍ࠼ࡓᇶᗏ㛵ᩘࢆ౑࠺ࡇ
࡜ࡀ㧗࠸ィ⟬⢭ᗘࢆᚓࡿࡓࡵ࡟ᚲ㡲࡛࠶ࡿ[3]ࡓࡵ㸪ᇶᗏ㛵ᩘ࡟ࡣ 6-311+G(2d,p)ࢆ⏝࠸ࡓ㸬᭱⤊ⓗ࡞ᒅᢡ⋡ࡣ㸪
DFT ィ⟬࡛ồࡵࡓศᴟ⋡࡜ MD ィ⟬࡛ồࡵࡓᐦᗘ࠿ࡽ Lorentz̽Lorenz ࡢᘧࢆ⏝࠸࡚⟬ฟࡋࡓ㸬ᒅᢡ⋡ࡢἼ㛗౫Ꮡᛶࡢᣦᶆ࡛࠶ࡿ࢔ࢵ࣋ᩘȤࡣ㸪୍⯡ⓗ࡟ 486 nm㸪589 nm㸪656 nm ࡢἼ㛗࡟࠾ࡅࡿᒅᢡ⋡㸦n486㸪n589㸪n656㸧࠿ࡽ௨ୗࡢᘧ࡛ィ⟬ࡋࡓ㸬

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ߥൌ݊ହ଼ଽ െ ͳ݊ସ଼଺ െ ݊଺ହ଺ࡇࡢἼ㛗౫Ꮡࡢᒅᢡ⋡ࡣ㸪Ἴ㛗౫Ꮡࡢศᴟ⋡࡜ᐦᗘ࠿ࡽ Lorentz̽Lorenz ࡢᘧࢆ⏝࠸࡚⟬ฟࡋࡓ㸬Psi4 ࡛ࡣ
CPHF ἲࢆ⏝࠸ࡓἼ㛗౫Ꮡࡢศᴟ⋡ィ⟬ࡣ DFT ࡟ᑐᛂࡋ࡚࠸࡞࠸ࡓࡵ㸪Time-dependent perturbation theory ࡟ᇶ࡙ࡃ sum-over-states (SOS) approach [4] ࢆ⏝࠸ࡓἼ㛗౫Ꮡศᴟ⋡ࡢィ⟬ࢆ TD-DFT ἲ࡟ࡼࡾ⾜ࡗࡓ㸬ࡇࡢ᪉ἲ࡛ࡣ㸪௨ୗࡢᘧ࡟ࡼࡾ㸪࿘ἼᩘȰ࡟࠾ࡅࡿศᴟ⋡ࢸࣥࢯࣝȘij(Ȱ)ࢆィ⟬ࡍࡿ㸬
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ߤ௜ ߤ௝

԰߱௚௡ െ ሺ԰߱ ଶ ሻȀ߱௚௡ቇࡣᇶᗏ≧ែ࠿ࡽ Q ␒┠ࡢບ㉳≧ែ࡬ࡢ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺ㸦L ㍈㸧࡛㸪԰߱௚௡ ࡣᇶᗏ≧ែ࠿ࡽ Q ␒┠ࡢບ㉳≧ែ࡬ࡢບ㉳࢚ࢿࣝࢠ࣮࡛࠶ࡿ㸬TD-DFT ἲࢆ⏝࠸ࡓἼ㛗౫Ꮡࡢศᴟ⋡ィ⟬࡛ࡣ㸪ගᏛᮦᩱࢆタィࡍࡿୖ࡛ᚲせ࡞྾཰Ἴ㛗ࡢィ⟬್ࡶྠ᫬࡟ᚓࡽࢀࡿ㸬Psi4 ࡛ࡣ TD-DFT ィ⟬ࡀ meta-GGA ࡟ᮍᑐᛂ࡛࠶ࡗࡓࡓ
ࡵ㸪㛗㊥㞳⿵ṇࢆྵࡴ GGA ỗ㛵ᩘ࡛࠶ࡿ CAM-B3LYP ࢆ⏝࠸㸪ᇶᗏ㛵ᩘ࡟ࡣ 6-311+G(2d,p)ࢆ౑⏝ࡋࡓ㸬◊✲ᡂᯝ
3.1 ࠕ㧗ศᏊ≀ᛶ⮬ືィ⟬࢔ࣝࢦࣜࢬ࣒࣭ࢯࣇࢺ࢙࢘࢔ࡢ㛤Ⓨࠖ࢔ࣔࣝࣇ࢓ࢫ࣏࣐࣮ࣜࡢ 17 ≀ᛶࡢ⮬ື ィ ⟬ ࢆ ᐇ ⿦ ࡋ 㸪 ㄽ ᩥ ࡢ බ 㛤 [1] ࡜RadonPy ࡢ ṇ ᘧ ࣜ ࣜ ࣮ ࢫ ࢆ ⾜ ࡗ ࡓ 㸬RadonPy ࡣ 㸪 MD ィ ⟬ ࢯ ࣇ ࢺ ࢘ ࢙ ࢔
LAMMPS ࡟ࡼࡿ㧗ศᏊ≀ᛶィ⟬ࡢ⮬ື໬ࢆᨭ᥼ࡍࡿ Python ࣛ࢖ࣈ࡛ࣛࣜ࠶ࡿ㸬࣏࣐࣮ࣜࡢ⧞ࡾ㏉ࡋ༢఩ࡢ໬Ꮫᵓ㐀ࢆධຊࡋ㸪ຊሙࡢ๭ࡾᙜ࡚㸪ึᮇᵓ㐀ࡢ⏕ᡂ㸪ᖹ⾮࣭㠀ᖹ⾮ MD ィ⟬࡟ࡼࡿ≀ᛶホ౯ࡲ࡛ࡢ඲ᕤ⛬ࢆ᏶඲࡟⮬ື໬ࡍࡿ㸦ᅗ 1㸧㸬࠸ࡃࡘ࠿ࡢ≀ᛶ࡜㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋
ࢫ PoLyInfo ࠿ࡽᢳฟࡋࡓᐇ㦂್࡜ࡢ୍⮴ᅗ 1. RadonPy ࡢ㧗ศᏊ≀ᛶィ⟬ࡢ࣮࣡ࢡࣇ࣮ࣟ

ࢆ⥲ྜⓗ࡟᳨ドࡋࡓ㸬ࡑࡢ⤖ᯝ㸪ᒅᢡ⋡㸪ᐦᗘ㸪⇕ఏᑟ⋡ࡣᐇ㦂್ࢆᐃ㔞ⓗ࡟෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ㸬CP࡟ࡘ࠸࡚ࡶ㸪ྂ඾ⓗ࡞ MD ィ⟬࡛ࡣ㔞Ꮚຠᯝࢆ⾲⌧࡛ࡁ࡞࠸ࡓࡵ࡟⣔⤫ⓗ࡞ࣂ࢖࢔ࢫࡀ࠶ࡿࡶࡢࡢ㸪ィ⟬್ࡣᐇ㦂್࡜㧗࠸┦㛵ࢆ♧ࡋࡓ㸬⥺⭾ᙇಀᩘ࡜య✚⭾ᙇಀᩘ࡟ࡘ࠸࡚ࡣ㸪ィ⟬࡜ᐇ㦂ࡢ୧᪉࡛኱ࡁ࡞ࡤࡽࡘࡁ
࡜୙☜࠿ࡉࡀ࠶ࡿࡓࡵ㸪ィ⟬್࡜ᐇ㦂್ࡢ┦㛵ࡣᙅ࠿ࡗࡓ㸬

3.2 ࠕ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࡢ㛤Ⓨࠖ඲ཎᏊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊ≀ᛶィ⟬ࢆ඲⮬ື໬ࡍࡿ Python ࣛ࢖ࣈࣛࣜ
RadonPy ࢆ⏝࠸࡚㸪ୡ⏺ึ࡜࡞ࡿໟᣓⓗ࡞㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࢆ๰ฟࡍࡿ㸬2022 ᖺ 1 ᭶ࡢᮏ᱁ጞື࠿ࡽ
2023 ᖺ 3 ᭶ࡲ࡛࡟㸪ィ 47,000 ࢔ࣔࣝࣇ࢓ࢫ࣏࣐࣮ࣜࡢィ⟬ࢆᐇ᪋ࡋࡓ㸬ᅗ 4 ࡟♧ࡍࡼ࠺࡟㸪኱㔞ࡢ࣏࣐࣮ࣜ

- 395 -

ࡢ」ᩘ≀ᛶࡢྠ᫬ศᕸࢆほࡍࡿࡇ࡜࡟ᡂຌࡋ

ࡓ㸬ᩘ୓㦵᱁ࡢ࣮࢜ࢲ࣮ࡢ㧗ศᏊ≀ᛶࡢྠ᫬ศᕸࢆほࡋࡓ౛ࡣᡃࠎࡢ▱ࡿ㝈ࡾ᭱ึࡢ౛࡛࠶ࡾ㸪ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮ࡢ⭾኱࡞ィ⟬⬟ຊ࡟ࡼࡾึࡵ࡚ほྍ⬟࡜࡞ࡗࡓ㇟ᚩⓗ࡞ᡂᯝ࡛࠶ࡿ㸬ࡇࢀ࡟ࡼࡾ㸪」ᩘ≀ᛶࡢࣃ࣮ࣞࢺ㠃ࡢ఩⨨ࡀ≉ᐃࡉࢀ࡚㸪ࣃ࣮ࣞࢺ㠃ࢆᵓᡂࡍࡿ࣏࣐࣮ࣜ⩌ࡢᵓ㐀ⓗ≉ᚩ࡟㛵ࡍࡿయ⣔ⓗ࡞▱ぢࢆᚓࡿ࡟⮳ࡗࡓ㸬⇕ఏᑟ⋡ࡢィ⟬࡛ࡣ㸪ࣃ࣮ࣞࢺቃ⏺ࢆ㉸࠼ࡿࡼ࠺࡞≉␗ⓗ࡞ศᏊ㦵᱁ࡀྠᐃࡉࢀࡓ㸬

3.3 ࠕ㌿⛣Ꮫ⩦ࢆ⏝࠸ࡓィ⟬್࡜ᐇ㦂್㛫ࡢ࢟ᅗ  ࣏࣐࣮ࣜ࡟࠾ࡅࡿ」ᩘ≀ᛶࡢྠ᫬ศᕸࡢ

ࣕࣜࣈ࣮ࣞࢩࣙࣥࠖほ ࡜ࣃ࣮ࣞࢺቃ⏺ࡢྠᐃ࠸ࡃࡘ࠿ࡢ≀ᛶࡣ㸪ᐇ㦂್࡜ MD ィ⟬್ࡢ㛫࡟⣔⤫ⓗ࡞ࣂ࢖࢔ࢫࢆྵࡴ୙୍⮴ࡀぢࡽࢀࡓ㸬ຍ࠼࡚㸪MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢึᮇ
ᵓ㐀౫Ꮡᛶ࡟ࡼࡾ㸪ィ⟬ࡉࢀࡓ≀ᛶ್㸪≉࡟⥺⭾ᙇಀᩘ࡜య✚⭾ᙇಀᩘ࡟኱ࡁ࡞ᶆ‽೫ᕪࡀぢࡽࢀࡓ㸬ࡑࡇ࡛ᡃࠎࡣ㸪ᶵᲔᏛ⩦ࢆ㐺⏝ࡍࡿࡇ࡜࡛㸪ࡇࢀࡽࡢࣂ࢖࢔ࢫࡸᶆ‽೫ᕪ
ࡢపῶ࡟㈉⊩࡛ࡁࡿ࡜⪃࠼㸪㌿⛣Ꮫ⩦ࢆ⏝࠸࡚ MD ィ⟬್ࡢ୙୍⮴ࢆ⿵ṇࡋࡓ㸬㌿⛣Ꮫ⩦ࡣ㸪㛵㐃ࡍࡿඖࢻ࣓࢖ࣥࡢᏛ⩦ࣔࢹࣝࡸࢹ࣮ࢱࢆ┠ᶆࢻ࣓࢖ࣥ࡟฼ά⏝ࡍࡿࡓࡵࡢ᪉ἲㄽ࡛࠶ࡿ㸬ࢹ࣮ࢱ㔞ࡢᑡ࡞࠸ᐇ㦂್࡛ࡣᏛ⩦ࡀ㞴ࡋ࠸ሙྜ㸪ࢹ࣮ࢱ㔞ࡢከ࠸ィ⟬್ࡢᏛ⩦ࣔࢹࣝࡸࢹ࣮ࢱࢆ฼⏝ࡍࡿࡇ࡜࡛㸪ࢹ࣮ࢱ㔞ࡢ୙㊊ࢆ⿵࠺ࡇ࡜ࡀ࡛ࡁࡿ㸬௒

ᅗ 3. (a) MD ィ⟬࡜(b) ㌿⛣Ꮫ⩦㸦㟷㸸Ꮫ⩦ࢹ࣮ࢱ㸪㉥㸸ࢸࢫࢺࢹ࣮ࢱ㸧࡟ࡼࡿ≀ᛶ್ࡢ᥎ᐃ⤖ᯝ㸬ᩥ⊩[1]ࡼ
ࡼࡾᘬ⏝ᅇࡢࢣ࣮ࢫ࡛ࡣ㸪ඖࢻ࣓࢖ࣥ࡜ࡋ࡚㸪MD ィ⟬್ࡢࢹ࣮ࢱࢆ⏝࠸࡚Ꮫ⩦ࣔࢹࣝࢆసᡂࡋ㸪ࡇࡢᏛ⩦ࣔࢹࣝࢆ⏝࠸࡚ PoLyInfo ࡢᐇ㦂್ࢆ┠ᶆࢻ࣓࢖ࣥ࡜ࡋ㸪ᶵᲔᏛ⩦ࣔࢹࣝࢆᵓ⠏ࡋࡓ㸬ᅗ 3 ࡟㌿⛣Ꮫ⩦࡟ࡼࡿ≀ᛶ್ࡢ᥎ᐃ⤖ᯝࢆ♧ࡋࡓ㸬MD ィ⟬࡛ࡣ㸪㔞Ꮚຠᯝࡢ᭷↓࡟㉳ᅉࡍࡿ CP ࡢ㐣኱ホ౯ࡀぢࡽࢀࡓࡀ㸪ࡇࡢ⣔⤫ࣂ࢖࢔ࢫࡣ㌿⛣Ꮫ⩦࡟ࡼࡾ⿵ṇࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸬ࡉࡽ࡟㸪MD ィ⟬್࡛ࡣᐇ㦂್࡜ࡢ┦㛵ᛶࡀᙅࡃ㸪ᶆ‽೫ᕪࡶ኱ࡁ࠸⥺⭾ᙇಀᩘ࡜య✚⭾ᙇಀᩘ࡛ࡶ㸪᥎ᐃ⢭ᗘࡢ኱ࡁ࡞ྥୖࡀぢࡽࢀࡓ㸬㧗ศᏊ⣔࡟ᬑ㐢ⓗ࡟㐺⏝࡛ࡁࡿィ⟬᮲௳ࡀᏑᅾࡋ࡞࠸ࡇ࡜ࡸィ⟬㈨※࡟ࡼࡿไ⣙ࡢࡓࡵ㸪඲⮬ື MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽ኱㔞⏕⏘ࡉࢀࡿࢹ࣮ࢱࢭࢵࢺ࡟ࡣ㸪ᵝࠎ࡞✀㢮ࡢ೫ࡾࡸࡤࡽࡘࡁࡀ࠶ࡿࡇ࡜ࡣ㑊ࡅࡽࢀ࡞࠸㸬௒ᅇᚓࡽࢀࡓ⤖ᯝࡣ㸪ᶵᲔᏛ⩦ࡀ㸪⌧ᐇ⣔࡜୙᏶඲࡞ィ⟬ࣔࢹࣝ࡜ࡢ㛫ࡢࢠࣕࢵࣉࢆᇙࡵࡿ኱ࡁ࡞ྍ⬟ᛶࢆᣢࡗ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ㸬

3.4 ࠕRadonPy ࡟ࡼࡿ≀ᛶ⮬ືィ⟬࡜࣋࢖ࢬ᭱㐺໬ࢆ⼥ྜࡋࡓ⮬ືศᏊタィ࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ࡜ᐇドࠖRadonPy ࡟ࡼࡾ๰ฟࡉࢀࡓࢹ࣮ࢱ࣮࣋ࢫࢆึᮇࢹ࣮ࢱ࡜ࡋ࡚⏝࠸㸪ከ┠ⓗ࣋࢖ࢬ᭱㐺໬࡜≀ᛶ⮬ືィ⟬࡟

- 396 -

ࡼࡾ⬟ືⓗ࡟ࢹ࣮ࢱࢆእᤄ㡿ᇦ࡟㏣ຍࡋ࡚࠸ࡃࡇ࡜࡛㸪㠉᪂ⓗ࡞≉ᛶࢆ᭷ࡍࡿ᪂つ㧗ศᏊᮦᩱࡢศᏊタィࢆ⾜࠺㸬࣓࢖ࣥࢱ࣮ࢤࢵࢺ࡜ࡋࡓ≀ᛶ್ࡣ㸪ᒅᢡ⋡࡜ࡑࡢἼ㛗౫Ꮡᛶࡢᣦᶆ࡜࡞ࡿ࢔ࢵ࣋ᩘ㸪ࡉࡽ࡟྾཰Ἴ㛗࡛࠶ࡿ㸬ࡇࡢせồ≉ᛶࡣ㸪ࣞࣥࢬ࡞࡝ࡢගᏛᮦᩱ࡟せồࡉࢀࡿࡶࡢ࡛㸪㧗ᒅᢡ⋡㸪㧗࢔ࢵ࣋ᩘ㸦ᒅᢡ⋡ࡢἼ㛗౫Ꮡᛶࡀప࠸㸧㸪ྍどග㡿ᇦ࡟྾཰ࢆᣢࡓ࡞࠸㸦㏱࡛᫂࠶ࡿ㸧ࡶࡢࡀ⌮᝿࡛࠶ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪᭷ᶵ≀࡛ࡣ↓ᶵ࢞ࣛࢫ࡟༉ᩛࡍࡿ㧗ᒅᢡ⋡࡜㧗࢔ࢵ࣋ᩘࢆ୧❧ࡍࡿᮦᩱࡣࡇࢀࡲ࡛࡟ぢࡘ࠿ࡗ࡚࠸࡞࠸[5]㸬ᮏ◊✲࡛ࡣ㧗ᒅᢡ⋡࡜㧗࢔ࢵ࣋ᩘࢆ୧❧ࡍࡿ㠉᪂ⓗ≉ᛶࢆ᭷ࡍࡿ㧗ศᏊᮦᩱࢆࢹ࣮ࢱ㥑ື࡟ࡼࡾタィࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿ㸬⌧᫬Ⅼ࡛ࡣ㸪ࡲࡔ᥈⣴ࡢ㏵୰࡛࠶ࡿࡀ㸪ᅗ 4 ࡟♧ࡋࡓࡼ࠺࡟ึᮇࢹ࣮ࢱ࡟࠾ࡅࡿᒅᢡ⋡࡜࢔ࢵ࣋ᩘࡢ㝈⏺⥺㸦ࣃ࣮ࣞࢺቃ⏺㸧ࡀ᥈⣴ࢆ㔜ࡡࡿࡈ࡜࡟ᢲࡋୖࡆࡽࢀ࡚࠸ࡃᵝᏊࡀほࡉࢀ࡚࠸ࡿ㸬

ᅗ 4. 㧗ᒅᢡ⋡࣭㧗࢔ࢵ࣋ᩘࢆ୧❧ࡍࡿ㠉᪂ⓗ㧗ศᏊᮦᩱࡢ⮬ື᥈⣴ཧ⪃ᩥ⊩[1] Y. Hayashi, J. Shiomi, J. Morikawa, R. Yoshida, npj Computational Materials, 8, 222 (2022).
[2] S. Riniker, G. A. Landrum, J. Chem. Inf. Model. 55, 2562̽2574 (2015).
[3] S. Ando, Chem. Lett. 47, 1494̽1497 (2018).
[4] J. E. Rice, N. C. J. Handy, Chem. Phys. 94, 4959 (1991).
[5] S. Ando, Kougaku, 44, 298, (2015).

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬ᯘ៞ᾈ㸪➨ 26 ᅇ㧗ศᏊィ⟬ᶵ⛉Ꮫ◊✲఍ㅮᗙ㸦౫㢗ㅮ₇㸧‫ۻ‬ᯘ៞ᾈ㸪࢘ ࢫࢸࣇ࢓ࣥ㸪㔝ཱྀ⍱㸪㧘ᶫឡᏊ㸪ྜྷ⏣ , ➨ 71 ᅇ㧗ศᏊウㄽ఍㸦ཱྀ㢌Ⓨ⾲㸧‫ۻ‬Y. Hayashi, The 23rd Asian Workshop on First-Principles Electronic Structure Calculations㸦౫㢗ㅮ₇㸧
‫ۻ‬Y. Hayashi, Y. Noguchi, A. Takahashi, S. Wu, R. Yoshida, The 17th Pacific Polymer Conference㸦ཱྀ㢌Ⓨ⾲㸧‫ۻ‬ᯘ ៞ᾈ㸪➨㸰ᅇࠕᐩᓅࠖᡂᯝ๰ฟຍ㏿ࣉࣟࢢ࣒ࣛ

◊✲஺ὶ఍㸦࣏ࢫࢱ࣮㸧‫ۻ‬ᯘ ៞ᾈ㸪᪥ᮏ໬Ꮫ఍➨ 103 ᫓Ꮨᖺ఍㸦2023㸧
㸦౫㢗ㅮ₇㸧
‫ۻ‬ᯘ ៞ᾈ㸪࢘ ࢫࢸࣇ࢓ࣥ㸪㔝ཱྀ ⍱㸪㧘ᶫ ឡᏊ㸪ྜྷ⏣ ு㸪➨ 72 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦ཱྀ㢌Ⓨ⾲㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Y. Hayashi, J. Shiomi, J. Morikawa, R. Yoshida, “RadonPy: automated physical property calculation using all-atomclassical molecular dynamics simulations for polymer informatics”, npj Computational Materials, 8, 222 (2022)‫ۻ‬Y. Aoki, S. Wu, T. Tsurimoto, Y. Hayashi, S. Minami, O. Tadamichi, K. Shiratori, R. Yoshida, “Multitask machinelearning to predict polymer-solvent miscibility using Flory-Huggins interaction parameters”, submitted‫ۻ‬M. Kusaba, Y. Hayashi, C. Liu, A. Wakiuchi, R. Yoshida, ”Representation of materials by kernel mean embedding”, inpreparation‫ۻ‬Y. Hayashi, RadonPy version 0.2.7, https://github.com/RadonPy/RadonPy㸦ࢯࣇࢺ࢙࢘࢔බ㛤㸧- 397 -

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ࣛࢪ࢝ࣝゎ㞳ᆺࣇ࢛ࢺࢡ࣑ࣟࢵࢡศᏊࢆ㓄఩Ꮚ࡜ࡋࡓ᪂つࣇ࢛ࢺࢡ࣑ࣟࢵࢡ
㔠ᒓ㘒యࡢ๰〇࡜ගᶵ⬟᥈⣴
'HYHORSPHQWRIQRYHOSKRWRFKURPLFPHWDOFRPSOH[HVZLWKUDGLFDOGLVVRFLDWLRQW\SHSKRWRFKURPLFPROHFXOHVDVOLJDQGVDQGLQYHVWLJDWLRQRIWKHLUSKRWRIXQFWLRQV‫ۑ‬ᑠᯘ ὒ୍ࠊỌ஭ 㑚ᶞࠊᒸᏳ ⚈ᚨࠊྜྷᒸ ኱♸ࠊ℩⌮ ᬛဢࠊ㇏⏣ ᝆᩯ㸦❧࿨㤋኱Ꮫ㸧




◊✲┠ⓗ
ᮏ◊✲࡛ࡣࠊග↷ᑕ࡟ࡼࡗ࡚ศᏊෆ࡟࣊ࢸࣟ

ࣛࢪ࢝ࣝ✀ࢆྍ㏫ⓗ࡟⏕ᡂࡍࡿࣇ࢛ࢺࢡ࣑ࣟࢵ

Scheme 13KRWRFKURPLFUHDFWLRQVFKHPHVRI D PICDQG E 
PICFRRUGLQDWHGLULGLXP ,,, FRPSOH[GHULYDWLYHVࢡศᏊࢆ㓄఩Ꮚ࡜ࡋ࡚⏝࠸ࡓ᪂つࣇ࢛ࢺࢡ࣑ࣟ
ࢵࢡ㔠ᒓ㘒యࢆタィࡋࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾࡑࡢᇶ♏≀ᛶ࠾ࡼࡧ཯ᛂ≉ᛶࢆホ౯ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿ㸦6FKHPH㸧ࠋ ᖺᗘࡣ᪂つࣇ࢛ࢺࢡ࣑ࣟࢵࢡࣛࢪ࢝ࣝ」ྜయ࡜ࡋ࡚࢝ࣝࣂࢰ࣮ࣝࢆ
⤌ࡳ㎸ࢇࡔ᪂つࣇ࢛ࢺࢡ࣑ࣟࢵࢡศᏊࢆ๰ᡂࡋࡓ ࡜ ࡜ ࡶ ࡟ 㸦 &KHP &RPPXQ  
㸧ࠊ࢖ࣜࢪ࣒࢘ࢆ୰ᚰ㔠ᒓ࡜ࡋࡓࣇ࢛ࢺࢡࣟ
࣑ࢵࢡ㔠ᒓ㘒యࡢ㔠ᒓ㘒యࢆ๰ᡂࡋࠊࡑࢀࡽࡢ
㔞Ꮚ⛉Ꮫィ⟬⤖ᯝ࡜᫬㛫ศゎྍどࠊ㉥እศගᐃ⤖ᯝ࡜ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊศᏊ࣭㟁Ꮚ≧ែࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ㄽᩥᢞ✏୰㸧ࠋ◊✲᪉ἲࠊィ⟬᪉ἲ㸯㸧ࣇ࢛ࢺࢡ࣑ࣟࢵࢡ㔠ᒓ㘒యࡢྜᡂࠊ࠾ࡼࡧࣇ࢛ࢺࢡ࣑ࣟࢵࢡ≉ᛶホ౯㸦ࣆࢥ⛊࠿ࡽ࣑ࣜ⛊ࡢᖜᗈ࠸᫬㛫ࢫࢣ࣮ࣝࡢ᫬㛫ศゎศග ᐃ㸧㸰㸧㛢⎔యࠊ୍ࡘࡢࣇ࢛ࢺࢡ࣑ࣟࢵࢡ㒊఩ࡀ཯ᛂࡋࡓ㛤⎔యࡢ᭱Ᏻᐃᵓ㐀ࡢィ⟬㸦*DXVVLDQ 2SW )UHT
8 %/<3*>&+12&O@/$1/'=>,U@㸧㸱㸧㛢⎔యࠊ୍ࡘࡢࣇ࢛ࢺࢡ࣑ࣟࢵࢡ㒊఩ࡀ཯ᛂࡋࡓ㛤⎔యࡢ྾཰ࢫ࣌ࢡࢺࣝࡢィ⟬㸦*DXVVLDQ 7'
8 %/<3*>&+12&O@/$1/'=>,U@ 8 %/<3*>&+12&O@/$1/'=>,U@㸧㸲㸧」ᩘࡢࣇ࢛ࢺࢡ࣑ࣟࢵࢡ㒊఩ࡀ཯ᛂࡋࡓ㛤⎔యࡢ⇕ຊᏛⓗ࡞Ᏻᐃᛶ࡜྾཰ࢫ࣌ࢡࢺࣝࡢィ⟬㸦*DXVVLDQ
7' 8 %/<3*>&+12&O@/$1/'=>,U@ 8 %/<3*>&+12&O@/$1/'=>,U@㸧- 406 -◊✲ᡂᯝ3,& ༢యࡣ  QP ௨ୗ࡟ࡋ࠿྾

཰ࡀ࡞࠸୍᪉ࠊ>,U ȝ&O 3,& @ ࡢ྾཰ࡣ  QP ௨ୖࡲ࡛㛗Ἴ㛗ࢩࣇࢺࡋࡓ㸦)LJ㸧ࠋࡇࡢศᏊࡢ㔞Ꮚ⛉Ꮫィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊྍど㡿ᇦࡢ྾཰ࣂࣥࢻࡣ࢖ࣜࢪ࣒࢘ඖ⣲௜㏆࠿
ࡽ 3,& 㒊఩࡬ࡢ㔠ᒓ㸫㓄఩Ꮚ㟁Ⲵ⛣ື㑄⛣㸦0/&7㸧࡛࠶ࡿࡇ࡜ࡀ᫂
ࡽ࠿࡟࡞ࡗࡓࠋ
⣸እග↷ᑕ࡟ࡼࡗ࡚⏕ᡂࡍࡿ3,& ࡢ㛤⎔యࡣࠊᐊ ࣋ࣥࢮࣥ⁐ᾮ
)LJ OHIW 6WHDG\VWDWHDEVRUSWLRQVSHFWUXPDQG ULJKW PROHFXODURUELWDOVRI[Ir(ȝ-Cl)(PIC)2]2LQ'&0୰࡟࠾࠸࡚༙ῶᮇ  QV ࡛ඖࡢ㛢⎔య࡬࡜ᡠࡿࠋ୍᪉ࠊ>,U ȝ&O 3,& @ ࡣ  QP ࡢບ㉳ග࡟ࡼࡾග⤖ྜゎ㞳཯ᛂࡀ㐍⾜ࡋࠊ㛤⎔య⏤᮶ࡢᡂศࡣ 3,& ༢య࡟ẚ࡭࡚  ಸ௨ୖ࡜࡞ࡿ࣑ࣜ⛊ࢫࢣ୍࣮࡛ࣝḟᣦᩘ㛵ᩘⓗ࡟ࡶ࡜ࡢ≧ែ࡬࡜ᡠࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸦)LJE㸧ࠋࡲࡓࠊ>,U ȝ&O 3,& @ ࡣ  ศᏊ࡟  ࡘࡶࡢ 3,& 㒊఩ࢆ᭷ࡋ࡚
࠸ࡿ࡟ࡶ࠿࠿ࢃࡽࡎࠊບ㉳ගᙉᗘࢆኚ࠼࡚ࡶࢫ࣌ࢡࢺࣝᙧ≧ࡸࢲ࢖ࢼ࣑ࢡࢫ࡟୍ษኚ໬ࡀ࡞࠿ࡗࡓࠋ」ᩘࡢࣇ࢛ࢺࢡ࣑ࣟࢵࢡ
཯ᛂࡀ㐍⾜ࡋࡓศᏊ㸦2)a2)㸧ࡢ᭱㐺໬ᵓ㐀ࡢ⇕ຊᏛⓗᏳᐃᛶ࡜྾཰ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ྾཰ࢫ࣌ࢡࢺࣝࡣ࡝ࢀ
ࡶ㢮ఝࡋࡓࢫ࣌ࢡࢺࣝᙧ≧ࡀணࡉࢀࡿ୍᪉ࠊ⇕ຊᏛⓗ࡞Ᏻᐃᛶ࡟ࡣ᫂☜࡞㐪࠸ࡀ࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡘࡲࡾࠊࡶࡋ
୍ศᏊෆ࡛」ᩘࡢࣇ࢛ࢺࢡ࣑ࣟࢵࢡ཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿࡢ࡛
࠶ࢀࡤࠊບ㉳ගᙉᗘ࡟ࡼࡗ࡚⇕ᡠࡾ཯ᛂ㏿ᗘࡀኚ໬ࡍࡿࡣࡎ࡛
࠶ࡿࠋࡇࢀࡽࡢィ⟬࠿ࡽࠊ>,U ȝ&O 3,& @ ࡣ୍ࡘࡢ 3,& 㒊఩࡛ࡢࡳࣇ࢛ࢺࢡ࣑ࣟࢵࢡ཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

)LJ  D  7UDQVLHQW DEVRUSWLRQ VSHFWUD DQGG\QDPLFVRI[Ir(ȝ-Cl)(PIC)2]2LQ'&0 îí 0  H[FLWHG ZLWK D QP QDQRVHFRQG
ODVHU SXOVH DQG E  VLPXODWHG DEVRUSWLRQVSHFWUDRIWKHULQJRSHQLQJIRUPV ‫ ۻ‬ᐑཎᣅஓࠊᒸᏳ⚈ᚨࠊỌ஭㑚ᶞࠊ㜿㒊஧ᮁࠊᑠᯘὒ୍ࠊ
ࠕࣇ࢙ࣀ࢟ࢩࣝ࢖࣑ࢲࢰࣜࣝࣛࢪ࢝ࣝ」ྜ
యࢆ㓄఩Ꮚ࡜ࡋࡓࣇ࢛ࢺࢡ࣑ࣟࢵࢡ࢖ࣜࢪ࣒࢘㘒యࡢ๰〇ࠖ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍  ࠊ༓ⴥ┴ࠊ ᖺ  ᭶ฟ∧ᐇ⦼ࡲࡓࡣணᐃ ‫<ۻ‬2ND\DVX70L\DKDUD76KLPDGD<1DJDL$6DNDPRWR-$EH<.RED\DVKL͆3KRWRFKURPLFGLQXFOHDULULGLXP ,,,  FRPSOH[HV KDYLQJ SKHQR[\OLPLGD]RO\O UDGLFDO FRPSOH[ GHULYDWLYHV͇ &KHP &RPPXQ Under
revision

- 407 -

㑄⛣㔠ᒓゐ፹࠾ࡼࡧ᭷ᶵゐ፹ࢆ⏝࠸ࡓ୙㣬࿴⤖ྜ࡬ࡢ௜ຍ཯ᛂ࡟࠾ࡅࡿ఩⨨࠾ࡼࡧ❧య㑅ᢥᛶࡢゎ᫂
5HJLR DQG6WHUHRVHOHFWLYLW\LQ2UJDQRFDWDO\WLFDQG7UDQVLWLRQ0HWDO
&DWDO\]HG$GGLWLRQ5HDFWLRQVWR8QVDWXUDWHG%RQGV
‫ۑ‬ඤ⋢


ᣅஓࠊ⸨ᮏ

㞙ᩯࠊ✄ᇉ

ᚭဢ㸦኱㜰኱Ꮫ㸧◊✲┠ⓗࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ࢔ࢩࣝࢩࣛࣥࡢ࢔ࣝࢣࣥ࡬ࡢࢩࢡࣟࣉࣟࣃࣥ໬཯ᛂ1ࡣࠊ&±6L ⤖ྜ࡬ࡢࣃࣛࢪ࣒࢘࡬

ࡢ㓟໬ⓗ௜ຍ࡜ࠊ⥆ࡃࢣ࢖⣲ࡢ㌿఩࡟ࡼࡿ࢝ࣝ࣋ࣥ㘒యࡢ⏕ᡂ࡜࠸࠺཯ᛂᶵᵓୖ᪂ࡋ࠸㐣⛬ࢆ⤒ࡿࠋᮏ㐣⛬ࢆ⪃ᐹࡍࡿࡓࡵ࡟ࠊDFT ィ⟬ࢆ⏝࠸࡚㓄఩Ꮚຠᯝࢆ᳨ウࡋࡓࠋࡲࡓࠊࢃࢀࢃࢀࡀ㏆ᖺሗ࿌ࡋࡓ໬ྜ≀࡟ᑐࡋ࡚Ⅳ⣲ཎᏊࡢࡳࢆᤄධ
ࡍࡿ single-carbon atom doping㸦SCAD㸧཯ᛂ2ࡢ㑄⛣≧ែࢆ᥈⣴࡜཯ᛂ⤒㊰ゎ᫂ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᅗ 1.

ࢩࢡࣟࣉࣟࣃࣥ໬཯ᛂ

ྛ཯ᛂࡢ୰㛫య࠾ࡼࡧ㑄⛣≧ែࢆ Gaussian 09 ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡾホ౯ࡋࡓࠋィ⟬ࡣ ωB97XD/SDD-6311+G(d)//ωB97XD/LANL2DZ-6-31G(d)࠾ࡼࡧ M062X/6-31G(d)࡛ࣞ࣋ࣝᐇ᪋ࡋࡓࠋ◊✲ᡂᯝ
Pd-IPr,ࠊPd-IPr*ࡢ࢝ࣝ࣋ࣥ␗ᛶ໬࡟㛵ࡋ࡚ࠊIPr ࡟ẚ࡭࡚ IPr*ࡢ᪉ࡀ࢔ࢩࣝࢩࣛࣥࡢ &±6L ⤖ྜ࡟ᑐࡍࡿ㓟໬ⓗ௜ຍࡢάᛶ໬࢚ࢿࣝࢠ࣮
ࡀୖ᪼ࡋࡓࡢ࡟ᑐࡋࠊ࢝ࣝ࣋ࣥ㘒య࡬ࡢ␗ᛶ໬࡟㛵ࡋ࡚ࡣῶᑡࡍࡿ
⤖ᯝࡀᚓࡽࢀࡓࠋࡲࡓࠊ࢝ࣝ࣋ࣥ㘒యࡢ⇕ຊᏛⓗ࡞Ᏻᐃᛶ࡟㛵ࡋ࡚
ࡶࠊPd-IPr ࡼࡾࡶ Pd-IPr*ࡢ᪉ࡀ⇕ຊᏛⓗ࡟Ᏻᐃ࡛࠶ࡿ࡜࠸࠺⤖ᯝࡀᚓࡽࢀࡓࠋSCAD ཯ᛂ࡟㛵ࡋ࡚ࡣࠊ」ᩘࡢ㑄⛣≧ែࡢ᥈⣴࡟ᡂຌࡋࠊ
࢔࣑ࣥୖࡢ⬺ࣉࣟࢺࣥ໬࡟ࡼࡗ࡚Ⅳ⣲ཎᏊᤄධࡀ኱ᖜ࡟ಁ㐍ࡉࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
ᅗ 2.
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1.

✄ᇉࠊඤ⋢ࠊ㬇ᕢࠊ᪥ᮏ໬Ꮫ఍➨ 103 ᫓Ꮨᖺ఍ࠊ2023༓ⴥ2.

௰ಖࠊ⸨ᮏࠊ㬇ᕢࠊ᪥ᮏ໬Ꮫ఍➨ 103 ᫓Ꮨᖺ఍ࠊ2023

༓ⴥ࢝ࣝ࣋ࣥ␗ᛶ໬཯ᛂࡢ࢚ࢿ
ࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ᅜ㝿ㄅ࡟ᢞ✏ணᐃ

6DNXUDL6,QDJDNL7.RGDPD7<DPDQDND07RELVX0-$P&KHP6RF .DPLWDQL01DND\DVX%)XMLPRWR+<DVXL..RGDPD77RELVX06FLHQFH

- 408 -

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'HYHORSPHQWRI1HZ5HDJHQWVDQG&LUFXODUO\3RODUL]HG/XPLQHVFHQW0DWHULDOV&RQWDLQLQJ+HWHUR(OHPHQWVE\8VLQJ$UWLILFLDO)RUFH,QGXFHG5HDFWLRQ0HWKRG‫ۑ‬㛗⏣ ⿱ஓࠊ⛅ᒣ ୡ἞ࠊ$PUXWKD$PPDWKQDGX6XGKDNDUࠊ㎷ ಙᘺ㸦໭ᾏ㐨኱Ꮫ ໬Ꮫ཯ᛂ๰ᡂ◊✲ᣐⅬ㸧




◊✲┠ⓗ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ୺࡜ࡋ࡚཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ฼⏝ࡋࠊ᪂཯ᛂࡢ㛤Ⓨཬࡧࡑࡢᶵᵓゎᯒ࡜᪂ᮦᩱࡢ㛤Ⓨ࡟ྥࡅ᳨࡚ウࢆ⾜ࡗࡓࠋ๓⏣ࡽ࡟ࡼࡗ࡚㛤Ⓨࡉࢀࡓ཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ୍ࡘ࡛࠶ࡿேᕤຊㄏ㉳཯ᛂ $),5
ἲࡣࠊ཯ᛂࢧ࢖ࢺྠኈࢆᢲࡋ௜ࡅࡿࠊࡲࡓࡣᘬࡁ㞳ࡍ࡜࠸࠺༢⣧࡞᧯స࡟ࡼࡗ࡚཯ᛂ⤒㊰ࢆồࡵࡿࡇ࡜ࡀ࡛
ࡁࠊẚ㍑ⓗ༢⣧࡞࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸ࡿࡓࡵ࡟」㞧࡞཯ᛂ࡬ࡢ㐺⏝ᛶࡀ㧗ࡃࠊࡇࢀࡲ࡛࡟ᗈ⠊࡞໬Ꮫ཯ᛂ࡟
㐺⏝ࡉࢀ࡚ࡁࡓࠋᮏ◊✲ㄢ㢟࡛ࡣࠊ୺࡟ࢪ࢚ࣥ㢮ࡢ␗ᛶ໬཯ᛂ࡟ $),5 ἲࢆ㐺⏝ࡋࠊ᭷⏝࡞ศᏊኚ᥮ἲ࡜᪂つ໬ྜ≀ࡢ๰ฟࢆ┠ᣦࡋࡓࠋࡉࡽ࡟㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ⥙⨶ⓗ࡞ࢫࢡ࣮ࣜࢽࣥࢢࢆ฼⏝ࡋࡓ࢟ࣛࣝࣅࢼࣇࢳࣝ
ᵓ㐀ࢆᇶᮏ㦵᱁࡜ࡋ࡚⏝࠸ࡓ෇೫ගᮦᩱࡢ㛤Ⓨ࡟ࡘ࠸࡚ࡶ᳨ウࢆ㐍ࡵࠊ㧗࠸㠀ᑐ⛠ᛶᅉᏊࢆ᭷ࡍࡿ᪂ᮦᩱࡢ
๰ฟࢆ┠ᣦࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡢ␗ᛶ໬཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡣ 'LHOV$OGHU ཯ᛂࡢᇶ㉁࡜ࡋ࡚ᗈࡃ฼⏝ࡉࢀ࡚࠾ࡾࠊ」㞧໬ྜ≀ྜᡂࡢฟⓎ≀㉁࡜ࡋ࡚ᴟࡵ࡚᭷⏝࡛࠶ࡿࠋ୍⯡࡟ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡣࠊᑐᛂࡍࡿ࣋ࣥࢮࣥ㢮ࡢ %LUFK 㑏ඖ࡟ࡼࡗ࡚
ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࢆྜᡂࡋࡓࡢࡕࠊ✀ࠎࡢ཯ᛂ๣ࢆ⏝࠸࡚␗ᛶ໬ࢆ⾜࠺ࡇ࡜࡛ྜᡂࡉࢀ࡚ࡁࡓࠋᮏ◊✲ࡢึᮇẁ㝵࡛ࡣ✀ࠎࡢ࣊ࢸࣟඖ⣲ྵ᭷ヨ⸆࡟ࡘ࠸࡚⌮ㄽⓗ᳨ウ㐍ࡵ࡚ࡁࡓࡀࠊᐇ㦂ⓗ᳨ウࡢ⤖ᯝࠊࢩࢡ
ࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡢ⁐ᾮ࡟ゐ፹㔞ࡢᅄ⮯໬Ⅳ⣲ࢆຍ࠼ࡓࡢࡕ▷Ἴ㛗ࡢගࢆ↷ᑕࡍࡿࡇ࡜࡛ຠ⋡ⓗ࡟཯ᛂࡀ㐍ࡴࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋᮏ◊✲࡛ࡣࡑࡢ཯ᛂᶵᵓཬࡧᇶ㉁㑅ᢥᛶ࡟ࡘ࠸࡚ࠊ*550 ࣉࣟࢢ࣒ࣛཬࡧ *DXVVLDQ ࢆ⏝࠸࡚⌮ㄽⓗ᳨ウࢆ⾜ࡗࡓࠋᮏ◊✲ࡣࠊ໭ᾏ㐨኱Ꮫ⥲ྜ໬Ꮫ㝔 ಟኈㄢ⛬Ꮫ⏕ ᓥ⏣ᐇṌ Ặࠊ໭ᾏ㐨኱Ꮫ๓⏣⌮ ᩍᤵ࡜༠ຊࡋ࡚㐙⾜ࡋࡓࠋ ࢟ࣛࣝࣅࢼࣇࢳࣝᵓ㐀ࢆᇶᮏ㦵᱁࡜ࡋ࡚⏝࠸ࡓ෇೫ගᮦᩱࡢ㛤Ⓨ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウ᪂つ෇೫ගⓎගᮦᩱࡢ㛤Ⓨࢆ┠ⓗ࡜ࡋ࡚ẕ㦵᱁࡜ࡋ࡚࢟ࣛࣝࣅࢼࣇࢳࣝᵓ㐀࡟╔┠ࡋࠊ✀ࠎࡢ⨨᥮ᇶࢆᑟධࡋࡓ㢮⦕యࡢ෇೫ගⓎග≉ᛶ࡟ࡘ࠸᳨࡚ウࢆ⾜࡞ࡗࡓࠋࡲࡎィ⟬᪉ἲ࡟ࡘ࠸࡚༑ศ࡟᳨ウࡋࡓࡢࡕࠊ
%,29,$0DWHULDOV6WXGLR9LVXDOL]HU%XLOG$QDORJV7RRO ࢆ⏝࠸࡚࢟ࣛࣝࣅࢼࣇࢳࣝᵓ㐀࡟ᑐࡋ࡚✀ࠎࡢ⨨᥮ᇶࢆᑟධࡋࡓᵓ㐀ࢆ⏕ᡂࡋࠊࡉࡽ࡟ࠊ*DXVVLDQ  Ȧ%;'* G  OHYHO  ࡟࡚ ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ 7LPH
GHSHQGHQW GHQVLW\IXQFWLRQDO WKHRU\7'')7 ἲ  ࢆ⏝࠸࡚ 6 ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ㟁Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜☢Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࢆồࡵࡿࡇ࡜࡛ࠊ෇೫ගⓎග࡟࠾ࡅࡿ㠀ᑐ⛠ᛶᅉᏊ JOXP ࢆ᥎ᐃࡋࡓࠋ

- 409 -

ࡉࡽ࡟ࠊᚓࡽࢀࡓ⤖ᯝࢆ㠀ᑐ⛠ᛶᅉᏊ࡟ᚑࡗ࡚⏕ᡂࡋࡓ࢟ࣛࣝࣅࢼࣇࢳࣝㄏᑟయࢆࢯ࣮ࢺࡍࡿࡇ࡜࡛ࠊྜᡂ
ᐇ㦂࡟ྥࡅࡓඃඛ㡰఩௜ࡅࢆ⾜࡞ࡗࡓࠋᮏ◊✲ࡣࠊ໭ᾏ㐨኱Ꮫ⥲ྜ໬Ꮫ㝔 ಟኈㄢ⛬Ꮫ⏕ Ỉ㔝‶㔛ዉ Ặࠊ໭ᾏ㐨኱Ꮫ ཎῲ♸ ༤ኈࠊ๓⏣⌮ ᩍᤵ࡜༠ຊࡋ࡚㐙⾜ࡋࡓࠋ



◊✲ᡂᯝ



ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡢ␗ᛶ໬཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウᐇ㦂ࡢࡼࡿணഛⓗ᳨ウ࡟࠾࠸࡚ࠊゐ፹㔞ࡢᅄ⮯໬Ⅳ⣲࡜  PRO ࡜ග↷ᑕ࡟ࡼࡗ࡚ ࣓ࢺ࢟ࢩࢩࢡࣟ࣊࢟
ࢧࢪ࢚ࣥ D ࡢ␗ᛶ໬཯ᛂࡀຠ⋡ⓗ࡟㐍ࡴࡇ࡜ࡀ᫂ࡽ
࠿࡟࡞ࡗࡓࡶࡢࡢ㸦ᅗ㸯 ୖᘧ㸧ࠊྠᵝࡢ཯ᛂ᮲௳࡟௜ࡋ
ࡓሙྜ࡛ࡶ ࣓ࢳࣝࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ E ࡣ඲ࡃ཯ᛂࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸦ᅗ  ୗᘧ㸧ࠋࡇࡢᇶ㉁㑅
ᢥᛶ࡟ࡘ࠸࡚ *550 ࣉࣟࢢ࣒ࣛཬࡧ *DXVVLDQ Ȧ%;
''HI6933&0EHQ]HQH ࢆ⏝࠸᳨࡚ウࢆ⾜ࡗࡓ࡜ࡇࢁࠊᅗ  ࡟♧ࡍ࢚ࢿࣝࢠ࣮ࢲ࢖ࣖࢢ࣒ࣛࢆᚓࡓࠋࡍ࡞ࢃࡕ࣓
ࢳࣝ⨨᥮య࡛ࡣࠊ཯ᛂࡢ᭱ึࡢ ௜ຍ཯ᛂ࠾ࡼࡧࠊ(⬺㞳཯ᛂ࡜ࡶ࡟άᛶ໬࢚ࢿࣝࢠ࣮ࡣࡑࢀࡒࢀ 

ᅗ 1. ゐ፹㔞ࡢᅄ⮯໬Ⅳ⣲࡜ග↷ᑕ࡟ࡼࡿ 1-࣓

N-PRO ࡛࠶ࡿࡢ࡟ᑐࡋ࡚ࠊ࣓ࢺ࢟ࢩ⨨᥮య࡛ࡣ 

ࢺ࢟ࢩ-1,3-ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ (1a) ࡢ␗ᛶ໬N-PRO ࡜ࠊN- ⛬ᗘάᛶ໬࢚ࢿࣝࢠ࣮ࡀపୗࡋ࡚࠸ࡿࡇ

཯ᛂ㸦ୖᘧ㸧
ࠋ୍᪉࡛ࠊ1-࣓ࢳࣝ-1,3-ࢩࢡࣟ࣊࢟

࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣࠊ࣓ࢺ࢟ࢩ⨨᥮యࡢ㑄⛣≧ែࡢᵓࢧࢪ࢚ࣥ (1b) ࡣ඲ࡃ཯ᛂࡋ࡞࠸㸦ୗᘧ㸧ࠋ㐀࡟࠾࠸࡚ࠊ㓟⣲Ⅳ⣲㛫ࡢ⤖ྜ㛗ࡀ㏻ᖖࡼࡾࡶ▷ࡃ࡞ࡗ࡚࠸ࡿ࡜࠿ࡽࠊ࣓ࢺ࢟ࢩᇶࡢ㓟⣲ཎᏊࡀ࢝ࣝ࣎࢝ࢳ
࢜ࣥᛶࡢ㑄⛣≧ែࢆᏳᐃ໬ࡋࡓࡓࡵࡔ࡜⪃࠼ࡽࢀࠊᇶ㉁ୖࡢ㓟⣲ཎᏊࡢ᭷↓ࡀ㧗࠸ᇶ㉁㑅ᢥᛶࡢཎᅉ࡜࡞ࡗ
࡚࠸ࡿࡇ࡜ࡀᙉࡃ♧၀ࡉࢀࡓࠋᅗ  ᅄ⮯໬Ⅳ⣲࡬ࡢග↷ᑕ࡟ࡼࡗ࡚⏕ࡌࡓ⮯໬Ỉ⣲ +%U ࢆゐ፹࡜ࡋࡓ ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡢࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮࡬ࡢ␗ᛶ໬཯ᛂ⤒㊰ Ȧ%;''HI6933&0 EHQ]HQH- 410 -

࢟ࣛࣝࣅࢼࣇࢳࣝᵓ㐀ࢆᇶᮏ㦵᱁࡜ࡋ࡚⏝࠸ࡓ෇೫ගᮦᩱࡢ㛤Ⓨ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウ෇೫ගⓎග≉ᛶࡢ≉ᛶ᳨ウ࡟࠾ࡅࡿึᮇ᳨ウ࡜ࡋ࡚ࠊບ㉳≧ែィ⟬࡟࠾ࡅࡿỗ㛵ᩘཬࡧᇶᗏ㛵ᩘ࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋከࡃࡢ໬ྜ≀࡟ࡘ࠸࡚⥙⨶ⓗ࡞ࢫࢡ࣮ࣜࢽࣥࢢࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ⢭ᗘࡢ㧗ࡉ࡜㧗㏿ᛶࡢ୧❧ࢆ┠ᣦࡋ᳨࡚ウࢆ㐍ࡵࡓࠋࡲࡎࠊ᪤࡟ JOXP ್ࡀሗ࿌ࡉࢀ࡚࠸ࡿ㸴✀㢮ࡢ෇೫ගⓎගᮦᩱ㸦ᅗ 㸧࡟ࡘ࠸࡚ࠊ✀ࠎࡢ᮲௳࡛ィ⟬ࢆ㐍ࡵࡓࠋ᳨ウ⤖ᯝࡣᅗ  ࡜ࡋ࡚ࡲ࡜ࡵࡓࠋ

ᅗ 3. ィ⟬᮲௳ࡢ᳨ウࡢࡓࡵ࡟⏝࠸ࡓ᪤▱ࡢ෇೫ගⓎගᮦᩱࡢᵓ㐀㸦3-8㸧ࠋ༢⣧໬ࡢࡓࡵࠊ5 ࡜ 8 ࡢ࢔ࣝ࢟ࣝᇶࡣ࣓ࢳࣝᇶ࡟⨨ࡁ᥮࠼࡚ィ⟬ࡋࡓࠋ(cf. Kubo, H.; Hirose, T.; Nakashima, T.; Kawai, T.; Hasegawa, J.;
Matsuda, K. J. Phys. Chem. Lett. 2021, 12, 686−695. See also the SI.)ᅗ  ✀ࠎࡢィ⟬ᡭἲ࡜ JOXP ್ࡢ┦ᑐㄗᕪࡢᖹᆒ್ཬࡧ┦ᑐィ⟬᫬㛫ࡢᖹᆒ್
JOXP ್ࢆ᥎ᐃࡍࡿ࡟࠶ࡓࡗ࡚ࠊỗ㛵ᩘ࡜ࡋ࡚ %/<3 ࢆ⏝࠸ࡓሙྜࡣㄗᕪࡀ኱ࡁࡃࠊࡉࡽ࡟኱ࡁ࡞ᇶᗏ㛵ᩘࢆ⏝࠸࡚ࡶㄗᕪࡣ⦰ᑠࡋ࡞࠸ࠋࡇࡢഴྥࡣศᩓຊ⿵ṇࢆຍ࠼࡚ࡶᨵၿࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋỗ㛵ᩘ࡜ࡋ࡚&$0%/<3 ࡲࡓࡣ Ȧ%;' ࢆ⏝࠸ࡓሙྜ࡟ㄗᕪࡀᑠࡉࡃࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ୍᪉ࠊࡇࢀࡽࡢሙྜ࡟࠾࠸࡚
ࡶỗ㛵ᩘࢆ኱ࡁࡃࡋ࡚ࡶ⢭ᗘࡣ࠶ࡲࡾᨵၿࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋィ⟬ࢥࢫࢺ࡜ࡢࣂࣛࣥࢫࢆ⪃࠼ࡿ࡜ࠊỗ㛵ᩘ࡜ࡋ࡚ Ȧ%;'ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ * G ࢆ⏝࠸ࡿࡢࡀⰋ࠸࡜⪃࠼ࡽࢀࡿࠋ

- 411 -

⥆࠸࡚ࠊ࣓ࢳࣞࣥᯫᶫ 6 ࣅࢼࣇࢺ࣮ࣝᵓ㐀ࢆᇶᮏ㦵᱁࡜ࡋ࡚ࠊ ✀㢮ࡢ⨨᥮ᇶࢆᑟධࡋࡓᵓ㐀ࢆ %,29,$0DWHULDOV6WXGLR9LVXDOL]HU%XLOG$QDORJV
7RRO ࢆ ⏝ ࠸ ࡚ ⏕ ᡂ ࡋ ࠊ ࡉ ࡽ ࡟ ࠊ *DXVVLDQ 
Ȧ%;'* G  OHYHO  ࡟࡚ ᫬㛫౫Ꮡᐦᗘỗ
7LPHGHSHQGHQW GHQVLW\IXQFWLRQDO WKHRU\ᅗ 5. ࣓ࢳࣞࣥᯫᶫ (S)-ࣅࢼࣇࢺ࣮ࣝᵓ㐀ࢆᇶᮏ㦵᱁7'')7 ἲ  ࢆ⏝࠸࡚ 6 ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࢆ࡜ࡋ࡚ࠊ5 ✀㢮ࡢ⨨᥮ᇶࢆᑟධࡋࡓᵓ㐀ࡢ⏕ᡂ㸦666

⾜࠸ࠊ㟁Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜☢Ẽ㑄⛣཮ᴟ

✀㢮㸧

㛵ᩘἲ

Ꮚ࣮࣓ࣔࣥࢺࢆồࡵࡿࡇ࡜࡛ࠊ෇೫ගⓎග࡟࠾ࡅࡿ 㠀 ᑐ ⛠ ᛶ ᅉ Ꮚ JOXP ࢆ᥎ᐃࡋࡓࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊྠ୍ࡢ࢟ࣛࣝẕ㦵᱁ࢆ⏝࠸࡚࠸ࡿ࡟ࡶ㛵ࢃࡽࡎࠊᑟධࡋࡓ⨨᥮ᇶ࡟ᛂࡌ࡚෇೫ගⓎගࡢ࢟ࣛࣜ
ࢸ࢕ࡣṇ㈇୧᪉ࡢ್ࢆྲྀ
ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠾
ࡾࠊ෇೫ගⓎගᮦᩱ㛤Ⓨ࡟࠾ࡅࡿ᪂ࡓ࡞ᣦ㔪࡜࡞ࡿྍ⬟ᛶࡀ࠶ࡿࠋ



ᅗ 5. TDDFT ィ⟬ (Gaussian 16, ȦB97X-D/6-31G(d) level) ࠿ࡽ᥎ᐃࡋࡓ࣓ࢳࣞ
ࣥᯫᶫ (S)-ࣅࢼࣇࢺ࣮ࣝㄏᑟయ㸦666 ✀㢮㸧ࡢ glum ್ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

★ᅄ⮯໬Ⅳ⣲ࢆගゐ፹࡜ࡋ࡚⏝࠸ࡿ 㸪ࢩࢡࣟ࣊࢟ࢧࢪ࢚ࣥ㢮ࡢ␗ᛶ໬཯ᛂࡢ㛤Ⓨ  ۵ᓥ⏣ᐇṌ㸪 ⛅ᒣୡ἞㸪 ๓⏣⌮㸪 㛗⏣⿱ஓ ➨  ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍3 ி㒔ࣃࣝࢫࣉࣛࢨ

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ᡂศ࡛࠶ࡿࣄࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ(HAp)ࡣᨺᑕ⥺↷ᑕ࡟ࡼࡾⅣ㓟ࣛࢪ࢝ࣝࢆ⏕ᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ
ࡇࡢⅣ㓟ࣛࢪ࢝ࣝࡣṑࡢ୰࡛㛗ᮇ࡟ࢃࡓࡾᏳᐃ࡛࠶ࡿࡇ࡜࠿ࡽ࢚ࢼ࣓ࣝ㉁୰ࡢⅣ㓟ࣛࢪ࢝ࣝᙉᗘࢆ㟁Ꮚࢫࣆࣥඹ㬆(ESR)ἲ࡟ࡼࡾ

ᐃࡍࡿࡇ࡜࡛ṑࡢᡤ᭷⪅ࡢ⣼✚ࡢ⿕ࡤࡃ⥺㔞ࢆ᥎ᐃࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ

୍᪉࡛ࠊHAp ୰ࡢⅣ㓟ࣛࢪ࢝ࣝᙉᗘࡀᴟࡵ࡚ᚤᙅ࡛࠶ࡾࠊ୙⣧≀⏤᮶࡜⪃࠼ࡽࢀࡿࢩࢢࢼࣝࡀࣀ࢖ࢬ࡜ࡋ࡚ほࡉࢀ࡚࠾ࡾࠊࡇࢀࡽࢆ㝖ཤࡍࡿࢧࣥࣉࣝฎ⌮ἲࡢ㛤Ⓨࡸ ESR ࢫ࣌ࢡࢺࣝゎᯒࡢ᭱㐺໬ࡀồࡵࡽࢀࡿࠋ

ᮏ◊✲ࡢ᭱⤊┠ⓗࡣィ⟬࡟ࡼࡾ HAp ୰࡟୙⣧≀ࢆྵࢇࡔ ERS ࢫ࣌ࢡࢺࣝࢆồࡵࠊ୙⣧≀࡟ࡘ࠸࡚ࠕᙜࡓࡾࠖ
ࢆࡘࡅࡿࡇ࡜࡛࠶ࡿࡀࠊࡲࡎィ⟬࡟ࡼࡿ ESR ࢫ࣌ࢡࢺࣝ࡜ᐇ㝿ࡢᐃ⤖ᯝ࡜ẚ㍑ࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
ESR ࢫ࣌ࢡࢺࣝࢆィ⟬࡟ࡼࡾồࡵࡿ᪉ἲ࡜ࡋ࡚ࠊMATLAB ࢆ࣮࣋ࢫ࡟ࡋࡓࠕEasySpinࠖࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋ࡚ồࡵࡿ᪉ἲࡀ࠶ࡿࠋ
ࡇࡢ EasySpin ࡛ࡣ ORCA ࣃࢵࢣ࣮ࢪࢆ౑⏝ࡋࡓィ⟬⤖ᯝࣇ࢓࢖ࣝࢆ౑⏝ࡍࡿࡇ࡜࠿ࡽࠊᮏ◊✲࡛ࡣ Gaussian ࣃࢵࢣ࣮ࢪࢆ⏝࠸࡚ᗄఱᵓ㐀ࢆồࡵࡓᚋ࡟ ORCA ࢆ⏝࠸࡚෌ᗘィ⟬ࢆ⾜࠸ࠊࡑࡢ⤖ᯝ࠿ࡽ EasySpin ࡟ࡼࡾ ESR ࢫ࣌ࢡࢺࣝࢆồࡵࡿࠋ
ESR ࡢᰯṇ⏝ヨᩱ࡜ࡋ࡚⏝࠸ࡽࢀࡿ TEMPONE ศᏊ(C9H16NO2)
ࡢ ESR ࢫ࣌ࢡࢺࣝࢆồࡵࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࢆ⾜࠺ࠋ



◊✲ᡂᯝ
ᅗ 1 ࡟ TEMPOL ศᏊ(C9H16NO2)ࡢᏳᐃᵓ㐀࡜ᐇ㦂࡟࠾ࡅࡿ ESRࢫ࣌ࢡࢺࣝࠊTEMPONE ศᏊࡢィ⟬ࡋࡓ ESR ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ⁐፹ࡢ᭷↓࡞࡝࡟ࡼࡾⱝᖸࡢᕪ␗ࡣぢࡽࢀࡿࡀࠊ୰ኸࡢ g ್ࡣࡼ࠸୍⮴ࢆ♧ࡋ࡚࠾ࡾࠊ௒ᚋ HAp ࡛ࡢィ⟬ࢆᐇ᪋ࡋ࡚࠸ࡃࠋ



ᅗ 1. (a)TEMPOL ศᏊࡢᏳᐃᵓ㐀ࠊ(b)TEMPOL(ᐇ㦂)ࠊTEMPONE(ィ⟬)ࡢ ESR ࢫ࣌ࢡࢺࣝ

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Dynamics Simulations”, The 41st JSST Annual International Conference on Simulation Technology, 2022/9, online
Ayata Ueno, Tomoko Mizuguchi, “Configurational Entropy of a Monatomic Glassy System”, The 41st JSST Annual

International Conference on Simulation Technology, 2022/9, online
Tomoko Mizuguchi, Takashi Odagaki, “Determination of cooperatively rearranging regions in binary glass former”,

The 18th International Conference on Liquid and Amorphous Metals, 2022/9, Hiroshima, Japan
Ayata Ueno, Tomoko Mizuguchi, “Configurational entropy of an isotropic monatomic glass”, The 18th International

Conference on Liquid and Amorphous Metals, 2022/9, Hiroshima, Japan(&x, z% ª\`¥.

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&17 ࡬ ࡢ࢔ࣝ࢝ࣥΰྜ⁐፹࠿ࡽࡢ㛗㙐㑅ᢥⓗ྾ⶶ࡜ࡑࡢ⌮ゎ
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࡟ࡼࡗ࡚ㄪ࡭ࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋලయⓗ࡟ࡣࠊ㛗▷ࡢ࢔ࣝ࢝ࣥΰྜ⁐፹࠿ࡽࡢ࢔ࣝ࢝ࣥࡢ㑅ᢥⓗ྾ⶶࡢ᭷↓ࡸࠊCNT ෆ㒊࡛ࡢ࢔ࣝ࢝ࣥศᏊࡢ㓄⨨࡟ࡘ࠸࡚ゎᯒࡍࡿࠋ࡞࠾ࠊ⌧᫬Ⅼ࡛ࡣࣜࣂ࣮ࢫࣔࣥࢸ࢝ࣝࣟἲ࡟ධ
ຊࡍࡿึᮇ≧ែࢆศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾồࡵࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
GROMACS ࢆ⏝࠸ࠊ᭱ึ࡟ 7 nm x 7 nm x 15 nm ࡢ z ㍈᪉ྥ࡟㛗࠸࣊࢟ࢧࣥ⣧⁐፹ࡢ⣔ࢆసᡂࡋࡓࠋලయⓗ࡟ࡣࠊNVT ࢔ࣥࢧࣥࣈ࡛ࣝ 200ps ⦆࿴ࡉࡏࠊࡑࡢᚋ NPT ࢔ࣥࢧࣥࣈ࡛ࣝ 200ps ࡢィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⣔ෆ
࡟ࠊCNT ࡢ㍈ࡀ z ㍈᪉ྥ࡟ྥࡃࡼ࠺࡟㓄⨨ࡋࠊCNT̿࣊࢟ࢧࣥΰྜ⣔ࢆᵓᡂࡋࡓࠋྠᵝࡢ᪉㔪࡛ CNT̿ࢹ࢝ࣥ⣔ࡸࠊCNT̿࣊࢟ࢧ࣭ࣥࢹ࢝ࣥΰྜ⣔ࢆసᡂࡋࡓࠋᚓࡽࢀࡓᵓ㐀ࢆࣉࣟࢢ࣒ࣛ RMCProfile ࡟ㄞࡳ㎸ࡲࡏᐇ㦂࡛ᚓࡽࢀࡓᵓ㐀ᅉᏊ S(Q)࡟ྜ࠺ࡼ࠺ࣜࣂ࣮ࢫࣔࣥࢸ࢝ࣝࣟ(RMC)࡟ࡼࡿᵓ㐀ࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝྑᅗ(a)࡟ࠊCNT̺ࢹ࢝ࣥΰྜ⣔ࡢᵓ㐀ᅉᏊ F(Q)ࡢணഛⓗ࡞ᐇ㦂ࢹ࣮ࢱ࡜ RMC ࡟ࡼࡗ࡚᭱㐺໬ࡉࢀࡓ F(Q)ࢆ ♧ ࡍ ࠋ (b) ࡟ ࠊ RMC ࡢึ ᮇ㓄⨨࡜ࡋ ࡚⏝࠸ࡓ
GROMACS ࡟ࡼࡾసᡂࡋࡓཎᏊ㓄⨨ࢆ♧ࡍࠋᅗࡣ
CNT ࡢ㍈࡟ᆶ┤࡞᩿㠃ࢆ♧ࡋ࡚࠸ࡿࠋ(a)ࡢᐇ㦂ࢹ࣮ࢱ࡟ࡘ࠸࡚ࡣ

ᐃ᫬㛫ࡢ୙㊊࡟ࡼࡾࣀ࢖ࢬࡀ㢧ⴭ࡛࠶ࡿࡢ࡛ࠊ2023 ᖺ 6 ᭶࡟ SPring-8 ࡢ BL04B2 ࡟࠾ࡅࡿ㛗᫬㛫ᐃࢆணᐃࡋ࡚࠸ࡿࠋࡲࡎࡣࡇࡢࡼ࠺࡟

CNT㸫ࢹ࢝ࣥ⣔ࡢᵓ㐀ࢆㄪ࡭ࠊࡑࡢᚋࡢࢫࢸࢵࣉ࡜
ࡋ࡚ CNT㸫࣊࢟ࢧ࣭ࣥࢹ࢝ࣥΰྜ⣔ࡢᵓ㐀ࢆㄪ࡭ࡿணᐃ࡛࠶ࡿࠋ

ᅗ㸸(a) RMCProfile ࡟ࡼࡾ෌⌧ࡋࡓ CNT̿ࢹ࢝ࣥ⣔ࡢᵓ㐀ᅉᏊ F(Q) ࡜ ᐇ 㦂 ࡛ ᚓ ࡽ ࢀ ࡓ
F(Q)ࠋ(b) GROMACS ࡟ࡼࡾసᡂࡋࡓ RMC ࡢึᮇ㓄⨨ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᚓࡽࢀࡓணഛⓗ࡞⤖ᯝࡣࠊ⛉◊㈝ኚ㠉㡿ᇦ㸦A㸧
ࠕ㉸⛛ᗎᵓ㐀⛉Ꮫࠖᡂᯝሗ࿌఍࡟࡚ 2023 ᖺ 3 ᭶࡟ཱྀ㢌Ⓨ⾲ࡋࡓࠋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
2023 ᖺᗘࡲ࡛࡟ࠊCNT ࡜⣧⁐፹⣔࡟ࡘ࠸࡚ࡢ⤖ᯝࢆㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡍࡿணᐃ࡛࠶ࡿࠋ2024 ᖺᗘ௨㝆࡟ CNT

࡜ΰྜ⁐፹⣔࡟ࡘ࠸࡚⤖ᯝࢆࡲ࡜ࡵࡿணᐃ࡛࠶ࡿࠋ

- 421 -

$QWLERG\$QWLJHQFRPSOH[SUHGLFWLRQRSWLPL]HGE\$OSKD)ROG ,06í& ○Zichang Xu (BIKEN, Osaka University)

1

Introduction
The adaptive immune system's ability to recognize non-self molecules through specific antibody-antigen interactions

has been utilized to create antibodies for uses such as lab tests and targeted protein treatments. However, pinpointing thecomplex structures or interactive residues of these antibody-antigen pairs remains a daunting task. Although numerous
computational methods have been designed for this purpose, integrating them for a strong, cohesive solution remains
difficult. With advancements in protein structural modeling using Deep Learning, we've reassessed this issue tounderstand the effect of modern protein modeling on antibody-antigen binding and docking. AbAdapt merges antibody
and antigen modeling with docking and scoring to identify specific features for epitope prediction. Its accuracy is closely
tied to the quality of input models. It uses Repertoire Builder for antibody modeling by default, but can also accept
structures. We've evaluated the performance of AlphaFold2 antibody models within AbAdapt using extensive benchmarks,
including a cross-validation and a diverse holdout set.

2

Methods

AbAdapt and AbAdapt-AF pipelines: AbAdapt was run using default parameters, as described previously. In brief,
antibodies were modeled using Repertoire Builder16 and antigens were modeled using Spanner. Here, any templates withbound antibodies overlapping with the true epitope were excluded. Two docking engines (Hex and Piper) were used tosample rigid docking degrees of freedom. Machine learning models were used to predict initial epitope and paratopes,
score Hex poses, score Piper poses, score clusters of Hex and Piper poses, and predict antibody-specific epitope residues.
For LOOCV calculations, each time an antibody-antigen pair was used as a query, each ML model was re-trained. For theHoldout datasets, training was performed on the entire LOOCV dataset. For the AbAdapt-AF pipeline, the only procedural
difference was that AlphaFold2 was used for antibody prediction instead of the default Repertoire Builder method.
Naturally, all ML models were re-trained specifically for this use case.

3

Results
We took advantage of AlphaFold2, a state-of-the-art protein modelling tool provided on the RCCS server, integrating

it within the AbAdapt pipeline. The fundamental expectation from this integration was to achieve superior accuracy inmodelling antibodies, subsequently translating to better paratope predictions, docking results, and epitope identification
specific to the antibody. Our hypothesis was validated as we witnessed substantial improvement in multiple areas of ourpipeline. The incorporation of more accurate antibody models derived from AlphaFold2 contributed to our pipeline's
effectiveness. This integration was particularly evident when we applied AbAdapt-AF to an anti-receptor binding domain(RBD) antibody complex benchmark. We observed that AbAdapt-AF exceeded the performance of three alternative
docking methods and displayed superior epitope prediction accuracy compared to other epitope prediction tools tested on
the same benchmark (Fig. 1).

- 422 -

Fig. 1. Docking performance of 25 anti-RBD antibody complexes. (A) The CAPRI quality of the best model from top
1/5/10 ranked models by ZDOCK, top 1/5/10/30/50/100/all ranked models by AbAdapt and AbAdapt-AF, and top
1/5/10/30/50/100 by HawkDock and HDOCK. The color of each cell was their corresponding CAPRI quality showed as
acceptable (grey) and medium (orange). (B) The number of successful queries by ZDOCK, AbAdapt, AbAdapt-AF,
HawkDocK, HDOCK.

Moreover, our study also demonstrated that while the integration of AlphaFold2 with AbAdapt represents a robust andincremental way of improving antibody-specific epitope predictions, there remains considerable scope for enhancement.
False-positive epitope predictions were still prominent, indicating the need for a broader benchmark comprising various
antigens for a fair and systematic performance comparison of AbAdapt-AF and other tools (Fig. 2).

- 423 -

Fig. 2. Epitope prediction of 25 anti-RBD antibody complexes. The comparison of epitope prediction performanceusing probability (A) and a threshold for epitope classification (B). The performance indices are calculated in evaluation
metrics and averaged. Bold character indicated the highest value of each item. (C) Epitope map visualization ofrepresentative queries. The native epitope (column 1) and predicted epitope by EpiPred (column 2), AbAdapt (column 3),
and AbAdapt-AF (column 4) are colored red on the RBD surface. The probability of prediction by AbAdapt and AbAdaptAF are shown in columns 5 and 6. The value below each prediction is indicated as F1 score (left) and ROC AUC (right).

- 424 -

4

Publications
Xu, Z., Davila, A., Wilamowski, J., Teraguchi, S., & Standley, D. M. (2022). Improved Antibody̺̺Specific

Epitope

Prediction

Using

AlphaFold

and

AbAdapt.

ChemBioChem,

23(18),

e202200303.

https://doi.org/10.1002/cbic.202200303
$FNQRZOHGJPHQWWH[W
The computation was performed using Research Center for Computational Science, Okazaki, Japan (Project: 21IMS−C116 and 22-IMS−C136).

- 425 -

ィ⟬໬Ꮫ࡟ࡼࡿ᭷ᶵゐ፹ཬࡧ᭷ᶵ㔠ᒓゐ፹ࢆ⏝࠸ࡓ᪂つ཯ᛂࡢᶵᵓゎ᫂&RPSXWDWLRQDO0HFKDQLVWLF6WXGLHVRI1RYHO2UJDQLFDQG
2UJDQRPHWDOOLF5HDFWLRQV‫ۑ‬ᒣᓮ ㈼㸦ᒸᒣ኱ᏛᏛ⾡◊✲㝔⮬↛⛉Ꮫ◊✲⛉㸧1◊✲┠ⓗ᭷ᶵゐ፹ࡸ᭷ᶵ㔠ᒓゐ፹ࡣᵝࠎ࡞཯ᛂ࡟᭷⏝࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࢳ࣮ࣗࢽࣥࢢᛶࡢ㧗࠸ゐ፹ࡣ≉

ᐃࡢᇶ㉁ࡢࡳࢆ┠ⓗ໬ྜ≀࡟ኚ᥮ࡍࡿྍ⬟ᛶࢆ⛎ࡵ࡚࠸ࡿࡀࠊከ✀ከᵝ࡞཯ᛂᶵᵓ࡛㐍⾜ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡓࡵࠊゐ፹ࢆࢹࢨ࢖ࣥࡍࡿࡓࡵ࡟ࡣ⭾኱࡞᫬㛫࡜ປຊࡀᚲせ࡞ᐇ㦂ⓗ᳨ドࡀᚲ㡲࡛࠶ࡿࠋࡑࡢࡓࡵࠊ
ィ⟬໬ᏛࡢほⅬ࠿ࡽ᪂つゐ፹཯ᛂࡢヲ⣽࡞཯ᛂᶵᵓゎᯒࢆ⾜࠺ࡇ࡜ࡣࠊࡉࡽ࡞ࡿ཯ᛂ㛤Ⓨ࡟⧅ࡀࡿࠋࡑࡇ࡛
ᮏ◊✲࡛ࡣࠊヲ⣽࡞ᶵᵓࡸ㑅ᢥᛶࡀࡼࡃศ࠿ࡗ࡚࠸࡞࠸᪂つ཯ᛂࢆྲྀࡾୖࡆࠊᐇ㦂ⓗ࡟ᥦၐࡉࢀࡓᶵᵓࢆᇶ
࡟ࠊᐦᗘỗ㛵ᩘἲ㸦DFT ἲ㸧ࢆ⏝࠸࡚⥙⨶ⓗ࡟཯ᛂ⤒㊰ࢆㄪ࡭ࠊ㎿㏿࡞཯ᛂ᭱㐺໬ཬࡧࢪ࢔ࢫࢸ࣭࢚ࣞ࢜ࢼ
ࣥࢳ࢜㑅ᢥᛶࡢ㉳※ࢆ᥈⣴ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ඲࡚ࡢィ⟬ࡣ Gaussian 09 㸦G09㸧ࡲࡓࡣ Gaussian 16 㸦G16㸧ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚⾜ࡗࡓࠋᏳᐃ≧ែ࠾ࡼࡧ㑄⛣≧ែࡢᵓ㐀᭱㐺໬ࡣ࣓ࢱΰᡂ GGA ỗ㛵ᩘ㸦M06-2X㸧ࡶࡋࡃࡣΰᡂỗ㛵ᩘ㸦B3LYP㸧ࢆ⏝࠸ࡓࠋB3LYP࡛ࡢィ⟬ࡢሙྜࠊGrimme ࡢ D3 ศᩓຊ⿵ṇࡶࡋࡃࡣ D3BJ ศᩓຊ⿵ṇࢆᑟධࡋࡓࠋᇶᗏ㛵ᩘࡣࠊHࠊCࠊNࠊOࠊPࠊF ཎᏊ࡟ᑐࡋ࡚ࡣ def2SVP ࡶࡋࡃࡣ 6-31G(d)ࢆࠊNi ཎᏊ࡟ᑐࡋ࡚ࡣ Lanl2dz ࢆ⏝࠸ࡓࠋࡇࢀࡽࡢィ⟬࡟࠾࠸࡚ࡣࠊ⁐፹ຠᯝ࡜ࡋ࡚ SMD ⁐፹࿴ࣔࢹࣝࢆ⏝࠸ࡓࠋ඲࡚ࡢᵓ㐀ࡣࠊᵓ㐀᣺ືゎᯒ࡟ࡼࡗ࡚Ᏻᐃ≧ែ㸦⹫
ᩘ᣺ື 0 ಶ㸧ࡶࡋࡃࡣ㑄⛣≧ែ㸦⹫ᩘ᣺ື 1 ಶ㸧࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ඲࡚ࡢᚓࡽࢀࡓᵓ㐀࡟ᑐࡋ࡚ࠊ࣓
ࢱΰᡂ GGA ỗ㛵ᩘ㸦M06-2XࠊM06㸧ࢆ⏝࠸୍࡚Ⅼィ⟬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣࠊHࠊCࠊNࠊOࠊPࠊF ཎᏊ࡟ᑐࡋ࡚ࡣ def2TZVP ࡶࡋࡃࡣ 6-311+G(d,p)ࢆࠊ
Ni ཎᏊ࡟ᑐࡋ࡚ࡣ SDD ࢆ⏝࠸ࡓࠋศᏊࡢྍど໬࡟ࡣ CYLView20
࠾ࡼࡧ PyMOL ࢆࠊ㠀ඹ᭷┦஫స⏝ࡢྍど໬࡟ࡣ NCIPLOT4 ࢆ⏝࠸ࡓࠋ- 426 -

3◊✲ᡂᯝᮏ◊✲࡛ࡣࠊ࢜ࢵࢡࢫࣇ࢛࣮ࢻ኱Ꮫࡢ Dixon ࡽ ࡀ㛤Ⓨࡋࡓ஧ᐁ⬟ᇶᛶ࢖࣑ࣀ࣍ࢫ࣍ࣛࣥ᭷ᶵゐ፹㸦Bifunctional Iminophosphorane, BIMP㸧ࢆ୰ᚰ࡟ࠊᵝࠎ࡞ゐ፹཯ᛂࡢᶵᵓゎ᫂ࢆ⾜ࡗࡓࠋࡲࡎึࡵ࡟ࣜࣥ㓟࢚ࢫࢸࣝࡢ୙ᆒ໬཯ᛂࢆྲྀࡾୖࡆࠊࡑࡢゐ፹ࢧ࢖ࢡࣝࢆィ⟬ࡋࡓࠋᰂ㌾࡞ゐ፹ᵓ㐀࠿ࡽ⏕ࡌࡿ」ᩘࡢ㓄ᗙࡸࠊゐ፹࡜ᇶ㉁࡜ࡢ㛫࡟Ꮡᅾࡍࡿ」ᩘࡢỈ⣲⤖ྜࢆ⪃៖ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ஧ࡘࡢ࢚ࢼࣥࢳ࣐࣮࢜ࡀ⏕ᡂࡍࡿ⤒㊰ࡢ୰࡛᭱ࡶ࢚ࢿࣝࢠ࣮ⓗ࡟᭷฼࡞ࡶࡢࢆྠᐃࡋࡓࠋᚊ㏿ẁ㝵࡛࠶ࡿࣜࣥ୰ᚰ࡛ࡢồ᰾ᨷᧁࡢ㑄⛣≧ែࡢ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿ࡜ࠊ୙ᩧ཰⋡ࡢ⌮ㄽ್ࡀᐇ್࡜㧗࠸⢭ᗘ୍࡛⮴ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡉࡽ࡟ࠊʌʌ ┦஫స⏝࡟ࡼࡗ࡚୙ᩧ཯ᛂࡀຠ⋡ⓗ࡟㐍⾜ࡍࡿࡇ࡜ࢆࠊNCI ࡢྍど໬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡋࡓࠋࡑࡢ௚࡟ࡶࠊĮȕ୙㣬࿴࢚ࢫࢸࣝ࡬ࡢࢽࢺࣟ࢔ࣝ࢝ࣥࡢ୙ᩧ௜ຍ཯ᛂ࡟㛵ࡋ࡚ࡶᶵᵓゎ᫂ࢆ⾜ࡗࡓࠋ㘽࡜࡞ࡿⅣ⣲㸫Ⅳ⣲⤖ྜࡀᙧᡂࡍࡿᚊ㏿ẁ㝵࡟࠾࠸࡚ࠊᇶ㉁࡜୙ᩧゐ፹࡜ࡢ❧య㞀ᐖ࡟㉳ᅉࡍࡿỈ⣲⤖ྜࡢࡡࡌࢀࡀ࢚ࢿࣝࢠ࣮ᕪࢆ
⏕ࡌࡉࡏࠊ㧗࠸୙ᩧ཰⋡ࢆᘬࡁ㉳ࡇࡍࡇ࡜ࡀぢฟࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
“Ligand-Controlled Regiodivergence in Nickel-Catalyzed Vinylcyclopropane Rearrangement”, Irifune, K.; Yamazaki,

K.; Nakamuro, T.; Murakami, M.; Miura, T., 7th UK-Japan Catalysis Meeting, Department of Chemistry, University of
Oxford, 17-18th April 2023. Poster Presentation.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬Formica, M.; Rogova, T.; Shi, H.; Sahara, N.; Ferko, B.; Farley, A. J. M.; Christensen, K. E.; Duarte, F.; Yamazaki,

K.; Dixon, D. J. Catalytic Enantioselective Nucleophilic Desymmetrisation of Phosphonate Esters. Nat. Chem. 2023, 15,714-721.
‫ ۻ‬Rozsar,

D.;

Farley,

A.

J.

M.;

McLauchlan,

I.;

Yamazaki,K.;

Dixon,D.

J.

Bifunctional

Iminophosphorane-Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β-Unsaturated Esters. Angew.
Chem. Int. Ed. 2023, 62, e2023033.
‫ ۻ‬Irifune, K.; Yamazaki, K.; Nakamuro, T.; Murakami, M.; Miura, T. Ligand-Controlled Regiodivergence in
Nickel-Catalyzed Vinylcyclopropane Rearrangement. in preparation.

- 427 -

Ⅳ⣲㸫࣊ࢸࣟཎᏊ⤖ྜࡢษ᩿࠾ࡼࡧᙧᡂࢆక࠺㦵᱁㌿఩཯ᛂࡢ
ィ⟬໬Ꮫ࡟ࡼࡿᶵᵓゎ᫂&RPSXWDWLRQDOVWXG\RIVNHOHWDOUHDUUDQJHPHQWUHDFWLRQVYLDFDUERQ±KHWHURDWRPERQGFOHDYDJHIRUPDWLRQ㮵ཪ ႛᖹ㸦኱㜰኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲⛉㸧1◊✲┠ⓗ᭷ᶵྜᡂ໬Ꮫ࡟࠾࠸࡚ࠊⅣ⣲㸫࣊ࢸࣟཎᏊ㸦N, O, P ࡞࡝㸧⤖ྜࡢ⤖ྜ࡜ษ᩿ࢆక࠺㦵᱁㌿఩཯ᛂࡣࠊ௚ࡢ

ᡭἲ࡛ࡣྜᡂᅔ㞴࡞ศᏊ㦵᱁ࢆຠ⋡ⓗ࡟ᵓ⠏࡛ࡁࡿඃࢀࡓᡭἲ࡛࠶ࡾࠊ✀ࠎࡢゐ፹ⓗ࠾ࡼࡧ㠀ゐ፹ⓗ཯ᛂࡀάⓎ࡟◊✲ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ㌿఩ཎᏊࡢ⤖ྜࡀ࡝ࡢࡼ࠺࡟άᛶ໬ࡉࢀࠊ࡝ࡢࡼ࠺࡞཯ᛂ⤒㊰࡛⏕ᡂ≀࡬࡜⮳ࡿࡢ࠿ࠊྂ඾ⓗ࡞ྜᡂ཯ᛂ࡜␗࡞ࡾᮍゎ᫂࡞㒊ศࡶከ࠸ࠋ
᭱㏆ᡃࠎࡣࠊࢺࣜ࢔࣮ࣜࣝ࣍ࢫࣇ࢕ࣥ 1 ࡜ࣉࣟࣆ࣮࢜ࣝ㓟࢚ࢫࢸࣝ 2 ࡜ࡢ཯ᛂ࡟࠾࠸࡚ࠊ㔞ㄽ㔞ࡢỈࡀᏑᅾࡍࡿ࡜ࠊMichael ௜ຍ࡟⥆࠸࡚ࠊࣜࣥཎᏊୖࡢ࢔࣮ࣜࣝᇶࡀ C–P ⤖ྜࡢษ᩿ࢆకࡗ࡚ 1,2-㌿఩ࡋࠊࠊE-ࢣࢺ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻ 3 ࡀ⏕ᡂࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸦ᅗ㸯㸧ࠋᮏ཯ᛂࡣᇶ㉁୍⯡ᛶࡀᗈࡃࠊE-ࢣࢺ࣍ࢫࣇ࢕ࣥ࢜
࢟ࢩࢻࢆྜᡂࡍࡿඃࢀࡓᡭἲ࡛࠶ࡗࡓࡓࡵࠊࠊ㔞Ꮚ໬Ꮫ㸦DFT㸧ィ⟬࡟ࡼࡾ཯ᛂᶵᵓࡸᚊ㏿ẁ㝵ࢆヲ⣽࡟ゎᯒࡍࡿࡇ࡜࡜ࡋࡓࠋ

ᅗ 1. ࣍ࢫࣇ࢕ࣥ࡜ࣉࣟࣆ࣮࢜ࣝ㓟࢚ࢫࢸࣝ࡜ࡢࢱࣥࢹ࣒ᆺ Michael ௜ຍ㸭࢔࣮ࣜࣝ㌿఩཯ᛂ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian09 ࢆ⏝࠸࡚ᐦᗘỗ㛵ᩘ㸦DFT㸧ἲ࡟ࡼࡾ㑄⛣≧ែࡢᵓ㐀ࢆ᭱㐺໬ࡋࡓࠋỗ㛵ᩘ࡟ࡣ B3LYPࠊᇶᗏ㛵ᩘ࡟ࡣ 6-31G(d)ࢆ⏝࠸ࡓࠋ᣺ືゎᯒ࡟ࡼࡾ㑄⛣≧ែࢆ☜ㄆࡋࠊᚓࡽࢀࡓᵓ㐀࡟ᑐࡋ࡚ᅛ᭷཯ᛂᗙᶆ㸦IRC㸧ィ⟬ࢆᐇ᪋ࡋ࡚཯ᛂ⤒㊰ࢆゎᯒࡋࡓࠋィ⟬ࡣ⮬↛⛉Ꮫ◊✲ᶵᵓ ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࢆ฼⏝ࡋࡓࠋ

3◊✲ᡂᯝࢺࣜࣇ࢙ࢽࣝ࣍ࢫࣇ࢕ࣥ 1 ࡢࣉࣟࣆ࣮࢜ࣝ㓟࢚ࢳࣝ࡬ 2 ࡢ௜ຍ㸭㌿఩ࢆࣔࢹࣝ࡜ࡋ࡚ࠊ཯ᛂࡢྛ㑄⛣≧- 428 -

ែ࡜୰㛫యࢆゎᯒࡋࡓ㸦ᅗ㸰㸧ࠋࢺࣜࣇ࢙ࢽࣝ࣍ࢫࣇ࢕ࣥࡀࣉࣟࣆ࣮࢜ࣝ㓟࢚ࢳࣝ࡟ඹᙺ௜ຍࡋ࡚ IntA ࢆᙧᡂࡋࡓᚋࠊỈศᏊ࡜㘒ᙧᡂࡋ࡚ IntB ࢆᙧᡂࡋࡓࠋࡑࡢᚋࠊTS1 ࢆ௓ࡋ࡚Ș-Ⅳ⣲ࢆࣉࣟࢺࣥ໬ࡋࡓᚋࠊ┤ࡕ࡟࣍ࢫ࣍ࢽ࣒࢘㒊఩࡟ࣄࢻࣟ࢟ࢩᇶࡀ௜ຍࡋ࡚ IntC ࢆᙧᡂࡋࡓࠋ᭱ᚋ࡟ࠊTS2 ࢆ⤒࡚ C–P ⤖ྜࡢษ᩿ࢆక
࠺ࣇ࢙ࢽࣝᇶࡢ 1,2-㌿఩ࡀ㉳ࡇࡾࠊࡑࡢᚋࡢ࣍ࢫ࣍ࣜࣝ㓟⣲࠿ࡽȘ-Ⅳ⣲࡬ࡢศᏊෆࣉࣟࢺࣥ⛣ື࡟ࡼࡾࠊ3ࡀ⏕ᡂࡋࡓࠋ



ᅗ 2. ཯ᛂࡢ࢚ࢿࣝࢠ࣮ᅗ㸦B3LYP/6-31G*㸧

4
1)
2)


Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬N. Dhiman, G.A.I. Moustafa, K. Kasama, K. Kanomata, S. Akai, manuscript in preparation.
‫ ۻ‬T. Z. Aye, M. Kondo, K. Kanomata, H. Sasai, S. Takizawa, manuscript in preparation.
6+RULQR71LVKLR6.DZDQLVKL62NL.1LVKLKDUD7,NDZD..DQRPDWD.:DJQHU+

*U|JHU6$NDLChem. Eur. J.202228H
‫ ۻ‬0 6DNR . .DQRPDWD 0 6 + 6DOHP 7 )XUXNDZD + 6DVDL 67DNL]DZD Org. Chem. Front.
2022±

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 429 -

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- 431 -

Exploiting weak interactions in apolar ices. Phase I. Benchmark
study, H on CO, and CO2User List
1. (◦) Aikawa, Yuri
2. Takayanagi, Toshiyuki
3. Furuya, Kenji
4. Molpeceres, German(The University of Tokyo, Saitama University, National Observatory of Japan, The University of Tokyo)
1

Introduction

Interstellar molecular clouds are regions of space characterized by very low temperatures (10 K) and densityof particles (104 particles cm−3 ). Because of the low temperature conditions, abundant molecules accrete
on top of micrometer sized dust grains, forming interstellar ices. Despite the harsh conditions, these ices
sport a rich chemistry, that are thought to be dominated by hydrogenation reactions by the H atom, owing
to the high mobility and the possibility of said atom to tunnel through potential energy barriers.
Interstellar ices chemical composition is varied and depends on many environmental factors, such as dust
temperature, local particle density or visual extinction. Remarkably, polar ices like H2 O and NH3 dominate
at earlier stages in a molecular cloud, because they are efﬁciently formed from the hydrogenation of atoms
on bare interstellar dust, creating an ice mantle through reactions of the type: O + 2 H −−→ H2 O, or N +3 H −−→ NH3 . At later stages, other molecules are either synthesized on the newly formed ice surface (i.e.
CO2 ) or in the gas-phase (i.e CO, N2 ).
With the formation of apolar molecules like CO, N2 or CO2 , the interstellar ice surface starts to be populatedwith molecules whose intermolecular interactions are radically different than H2 O or NH3 . This means thatthe molecules formed or depleted on ices whose major composition is for example CO, will be less strongly
bound to the surface, enabling diffusive chemistry otherwise inhibited.
In this project spanning two ﬁscal years, we study the differences in the chemistry of polar ices (H2 O) andapolar ones (CO, CO2 ). We mainly focus on three distinct topics:• Gas-phase reactions enriching polar and apolar ices.
• Chemistry on polar and apolar ices.
• Differences in physical processes on polar and apolar ices.
In the ﬁrst part of the project, we have studied the binding properties of a series of adsorbates on CO ice
and compared with the binding on H2 O, complementing our results with astrochemical models. We havealso undertaken the creation of a reactive potential for the dynamical study of the hydrogenation of CO ice.
Additionally we studied the formation mechanism of CO2 ice and how this mechanism changes on H2 O andCO ices. Finally, we have complemented our solid phase studies with auxiliary calculations on gas-phaseprocesses relevant for interstellar chemistry.

2

Methods

Our methodology is eminently computational, with an interplay of electronic structure calculations (density
functional and wave function theory based), molecular dynamics (using neural network interatomic potentials), rate equation theories (transition state theory, RRKM theory, instanton theory) and astrochemical
modelling. In particular, the RCCS resources are mostly allocated for the expensive sampling calculations
using DFT. For this ﬁscal year, most of the calculations involved DFT evaluation of the binding energies ofa series of adsorbates on CO and H2 O clusters.
For FY2023 our methodology also is planned to include automatic reaction discovery searches through the
GRRM code (ADDf and AFIR calculations).

- 432 -

3

Results

We made the most of the computer time that we were granted, even though we could not employ it during
the whole second term of the 2022 ﬁscal year due to RCCS renovations. Thus the results covered here
include the calculations performed between February–April 2023. Speciﬁcally, we carried out calculations
that are currently included in three papers close to submission on in revision, along with an ancillary project
on reaction discovery whose calculations are ﬁnished and for which the manuscript preparation will begin
shortly. The ﬁnished projects are:
1. Floating in Space: How to Treat the Weak Interaction between CO Molecules in Interstellar Ices.
2. Enhanced complex organic molecules formation on CO ice.
3. Cracking the Puzzle of CO2 Formation on Interstellar Ices.
Project (1) is part of a collaboration with Leiden University to characterize the nature of the weak interaction
on CO ice by means of accurate pair potentials ﬁtted to CCSD(T)/AVTZ data, and use the highly accurate
resulting force-ﬁeld to benchmark DFT to accurately and affordably study reactions contemplated in project(2). We found that the ωB97M-V/ma-def2-TZVP method is able to capture the physics of CO ice quantitatively. The publication supporting this results is undergoing peer review. In project (2) we revealed that
CO ice is an excellent promoter of complex chemistry at very low temperatures in comparison with H2 O,
this is mainly due to the weak intermolecular interaction of certain molecules, most notably CH3 , HCO or
H3 CO with CO, that in turn promotes radical-radical reactions on its surface, forming efﬁciently complex(and prebiotic) molecules like CH3 CHO, CH3 OCH3 or NH2 CHO. The publication summarizing these results
is undergoing peer review. Finally, in project (3) we undertook a theoretical effort to characterize the CO +OH −−→ CO2 + H reaction on H2 O and CO ices. We found that the reaction is rather inefﬁcient and does notproceed at low temperatures, stopping at the stable HOCO radical. Moreover, we conﬁrmed that, thanks tothe surface stabilization promoted by the H2 O ice, the formation of HOCO is favoured on these ices, andthat on CO such a reaction requires further energy input from the media. Our results are reconciled withthe literature relying on a second reaction step HOCO + H −−→ CO2 + H2 . The publication supporting thisresults is ﬁnished and will be submitted shortly. The RCCS resources were employed during February andMarch 2023 to carry out expensive calculations for these projects. Some calculations needed to be ﬁnishedwith the FY2023 budget. In addition to the above described calculations, some RCCS resources were also
allocated to study reactivity in the gas and surface phase, utilizing the GRRM code in tandem with electronic structure solvers to deepen in the chemical reactivity of important prebiotic precursors and also to
ﬁnd elusive transition states on CO and H2 O clusters. Finally, we are in the ﬁnal stages of the constructionof a neural-network based reactive potential to study the CO + H −−→ HCO reaction on CO ices.

4

Talks and Posters• Physical Processes on Apolar Ices. Invited talk Next Astrochemistry International Meeting (December2022).
• Reaction dynamics on amorphous solid water surfaces using interatomic machine learned potentials.
Contributed talk. Next Astrochemistry Local Meeting (March 2023).
• Atomistic Insights on the Chemistry of the Interstellar Medium. Invited seminar at the University ofTokyo (April 2023)

5

Publications

The following publications are the ones that employ computational resources from RCCS.
• Ferrari. B., Molpeceres, G., Kästner, J.,Aikawa, Y., van Hemert, M., Meyer, J. and Lamberts, T.
Floating in Space: How to Treat the Weak Interaction between CO Molecules in Interstellar Ices. ACS
Earth Sp. Chemistry, Submitted • Molpeceres, G., Furuya, K. and Aikawa, Y. Enhanced formation of interstellar complex organic moleculeson carbon monoxide ice. Astrophys. J., Submitted. • Molpeceres, G., Enrique-Romero, J. and Aikawa, Y. Cracking the Puzzle of CO2 Formation on Interstellar Ices. In preparation. - 433 -

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 ࢔ࣉࢱ࣐࣮51$ ࡢ❧యᵓ㐀ண 
FebRNA ࡟ࡼࡾ⏕ᡂࡋࡓ RNA ᵓ㐀ࡢ࠺ࡕࠊୖ఩ 100 ᵓ㐀࡟ᑐࡋ࡚ࠊX ⥺⤖ᬗᵓ㐀㸦௨ୗࠊṇゎᵓ㐀㸧࡟ᑐࡍࡿ RMSd ࢆゎᯒࡋࡓࠋṇゎᵓ㐀࡟ᑐࡋ࡚ࠊࡇࢀࡽࡢᵓ㐀ࡣ RMSd ࡛ 6ύ࠿ࡽ 7ύ㞳ࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ
ࡓࠋ100 ᵓ㐀ࡢ࠺ࡕࠊ1 ఩࠿ࡽ 10 ఩㛫㝸࡛ 10 ᵓ㐀ࢆྲྀࡾฟࡋࠊࡑࢀࡒࢀ࡟ᑐࡋ࡚ 100 ࢼࣀ⛊ࡢศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࠊᚓࡽࢀࡓࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆ⏝࠸࡚ RMSd ࡢศᕸࢆィ⟬ࡋࡓࠋRMSd ࡢ᭱ᑠ್ࡀ 4.5
ύ࡜࡞ࡾ⏕ᡂᵓ㐀ࡼࡾࡶṇゎ࡟㏆࡙࠸ࡓ୍᪉ࠊ᭱኱್ࡣ 11.6ύ࡜࡞ࡾࠊṇゎ࠿ࡽ㐲ࡊ࠿ࡿሙྜࡶ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋḟ࡟ୖグࡢ 100 ᵓ㐀ࢆ Molearn ࡢᏛ⩦࡟⏝࠸ࡓࠋ100 ᵓ㐀ࢆ⏝࠸࡚⏕ᡂࡋࡓᵓ㐀࣌࢔ࠊ45 ⤌ࡢ࠺ࡕ RMSd᭱኱ࡢࡶࡢࢆ⏝࠸࡚ࠊᏛ⩦ᶵ࡟ࡼࡿᵓ㐀⏕ᡂࢆ⾜ࡗࡓࠋࡇࢀࡽࡢᵓ㐀࡟ᑐࡍࡿ RMSd ࡢ್ࡣࠊ4.2ύ࠿ࡽ 7.1
ύ࡛࠶ࡗࡓࠋMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᶵᲔᏛ⩦ჾ Molearn ࡢ࠸ࡎࢀ࡛ࡶࠊ⏕ᡂᵓ㐀ࢆṇゎᵓ㐀࡟㏆࡙ࡅࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡓࡔࡋࠊ๓⪅࡛ࡣࠊṇゎ࠿ࡽ㐲ࡊ࠿ࡿᵓ㐀ࡶ⌧ࢀࡿࠋ୍᪉ࠊMolearn ࡛ࡣ RMSd ࡢ᭱኱್ࡣ࡯ࡰ
ኚ໬ࡋ࡞࠸ࠋMolearn ࡛ࡣṇゎ࠿ࡽ㐲ࡊ࠿ࡽ࡞࠸ࡼ࠺࡟ RNA ᵓ㐀ࢆ᥈⣴࡛ࡁࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ
Molearn ࡟ࡘ࠸࡚ࡣࠊࣂࢵࢳࢧ࢖ࢬࡸࣃ࣮࣓ࣛࢱࡢᏛ⩦᮲௳ࢆከᩘ⏝ពࡋࠊᵓ㐀⏕ᡂ࡬ࡢᙳ㡪ࢆ᳨ドࡋࡓࠋ௒ᅇ㓄ศ࠸ࡓࡔ࠸ࡓ฼⏝Ⅼᩘ 180,000 ࡢ኱㒊ศࡣࡇࡢసᴗ࡛ᾘ㈝ࡋࡓࠋ
 ࢫࣉࣛ࢖ࢩࣥࢢᅉᏊࡢ༠ྠⓗᏳᐃ໬ᶵᵓ
௒ᖺᗘࡣ㓄ศࡋ࡚࠸ࡓࡔ࠸ࡓィ⟬᫬㛫ࢆㄢ㢟 2-1 ࡢ㐙⾜࡛౑࠸ษࡗ࡚ࡋࡲࡗࡓࠋࡇࡕࡽࡢㄢ㢟࡟ࡣ╔ᡭࡋ࡞࠿ࡗࡓࡓࡵࠊලయⓗ࡞◊✲ᡂᯝࡣ↓࠸ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋࠕཧ⪃ᩥ⊩ࠖ
[1] Zhou et al., Biophys. J., 121, 3381-3392 (2022). [2]Venkata et al. (2021), Phys. Rev. X 11; 011052.

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จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲
Theoretical studies of relaxations and reaction dynamics
in condensed phase‫ۑ‬ᩧ⸨ ┿ྖࠊ⏥⏣ ಙ୍ࠊ‫ ‮‬அஓࠊ▼⏣ࠊᖸᇛࠊᑠἨ ឡࠊZHU Zhe㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏᖺᗘࡣࠊ1. ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࠊ2. 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)ບ㉳࢚ࢿࣝࢠ࣮⛣ືᶵᵓࠊ3.㐣෭༷ᾮయཬࡧ⏕యศᏊ⣔࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫ࡟⌧ࢀࡿືⓗᦂࡽࡂࠊ࢖࢜ࣥᾮయࡢ◊✲࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ
1.1 KaiC ୖࡢ KaiB-KaiB, KaiB-SasA, SasA-SasA ┦஫స⏝ࡢ኱ࡁࡉࡢぢ✚ࡶࡾࢩࢩ࢔ࣀࣂࢡࢸࣜ࢔ࡢᴫ᪥ࣜࢬ࣒ࡣ 3 ✀ࡢࢱࣥࣃࢡ㉁(KaiA, KaiB, KaiC)ࡢ┦஫స⏝࡟ࡼࡗ࡚⏕ࡌࡿࠋࡇࡢ
ᴫ᪥ࣜࢬ࣒ࡣ KaiC භ㔞యࡢ୰࡛⏕ࡌࡿࣜࣥ㓟໬཯ᛂࡀ KaiA ࠾ࡼࡧ KaiB ࡟ࡼࡗ࡚ಁ㐍ࡸᢚไࡉࢀࡿࡇ࡜࡛
⏕ࡌࡿࠋ㏆ᖺ࡛ࡣ KaiABC ᣺ືᏊࡢฟຊ⣔࡟ࡶ◊✲ᑐ㇟ࡀᣑ኱ࡉࢀࡘࡘ࠶ࡿࠋฟຊ⣔࡜ࡣࠊ᣺ືᏊࡀ⮬ᚊⓗ࡟้ࡴ᫬㛫᝟ሗࢆ⏕య඲య࡟ఏ㐩ࡉࡏࡿ௙⤌ࡳ࡛࠶ࡾࠊ୰ᯡࡢ᣺ືᏊ࡜ྠ➼࡟㔜せ࡞⣔࡛࠶ࡿࠋࢩ࢔ࣀࣂࢡ
ࢸࣜ࢔ࡢฟຊ⣔࡛ࡣ SasA ࡜ KaiC ࡀ⤖ྜࡍࡿࡇ࡜࡛᫬㛫᝟ሗࢆእ㒊࡟ఏ㐩ࡍࡿࠋKaiC-SasA ࡢ⤖ྜࢧ࢖ࢺࡣ
KaiC-KaiB ࡢࡑࢀ࡜ඹ㏻ࡋ࡚࠾ࡾࠊࡇࡢ 2 ✀ࡢ」ྜయᙧᡂࡣ➇ྜࡍࡿࠋࡋ࠿ࡋࠊᐇ㝿ࡣఱࡽ࠿ࡢ࣓࢝ࢽࢬ࣒
࡟ࡼࡾࡇࢀࡽࡣᕦጁ࡟ࢫࢣࢪࣗࣜࣥࢢࡉࢀ࡚࠾ࡾࠊ㡰ᗎࡔࡗ࡚」ྜయࡀᙧᡂࡉࢀࡿࠋᮏ◊✲ࡣࡑࡢ࣓࢝ࢽࢬ
࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋ
KaiC ࡣ⎔≧ࡢභ㔞య࡛࠶ࡾ KaiB ࠾ࡼࡧ SasA ࡶ KaiC ୖ࡟⎔≧࡟⤖ྜࡍࡿࠋࡇࡢ㝿ࠊKaiB 㛫࠾ࡼࡧ SasA 㛫ࡢ┦஫స⏝ࡀఱࡽ࠿ࡢᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡢ࡛ࠊࡇࢀࢆヲࡋࡃㄪ࡭ࡿࠋ
1.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ගྜᡂ⣽⳦ࡸ⥳Ⰽ᳜≀ࡢගྜᡂ࡟࠾ࡅࡿ᭱ึࡢࢫࢸࢵࣉࡣࠊගᤕ㞟࢔ࣥࢸࢼ࡜࿧ࡤࢀࡿࢱࣥࣃࢡ㉁࡟ࡼࡿ
ග࢚ࢿࣝࢠ࣮ࡢ྾཰࠾ࡼࡧ཯ᛂ୰ᚰ࡬ࡢఏ㐩࡛࠶ࡿࠋࡑࡢึᮇ㐣⛬࡛࠶ࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື㸦EET㸧ࡣ㠀ᖖ࡟㧗ຠ⋡࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋEET ࡢ⌮ゎ࡟ࡣࠊගᤕ㞟࢔ࣥࢸࢼࢱࣥࣃࢡ㉁୰ࡢⰍ⣲ࡢບ㉳࢚ࢿࣝࢠ࣮࡜ࡑࡢᦂࡽࡂࡀ୙ྍḞ࡛࠶ࡿࡀࠊᐇ㦂ࡔࡅ࠿ࡽࡇࢀࡽࡢ᝟ሗࢆᢳฟࡍࡿࡇ࡜ࡣ㠀ᖖ࡟ᅔ㞴࡛࠶ࡾࠊ⌮ㄽィ⟬ࡀồࡵࡽࢀࡿࠋࡇࢀࡲ࡛࡟ࠊᡃࠎࡣࠊChl ศᏊࡢ⁐፹ࡸᒁᡤ⎔ቃ࡟ࡼࡿບ㉳࢚ࢿࣝࢠ࣮ࡢኚ໬ࢆ㐺ษ࡟グ㏙ࡍࡿ(TD)DFT ィ⟬࡟⏝࠸ࡿࣃ࣓࣮ࣛࢱࡢỴᐃࢆ⾜ࡗࡓࠋບ㉳࢚ࢿࣝࢠ࣮ᦂࡽࡂࢆ㐺ษ࡟グ㏙ࡍࡿࡓࡵ࡟
ࡣศᏊືຊᏛ㸦MD㸧ィ⟬ࡶᚲせ࡜࡞ࡿࡀࠊMD ィ⟬࡟⏝࠸ࡿຊሙࡣⰍ⣲ศᏊࢆ㐺ษ࡟グ㏙ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞
࠸ࠋࡑࡇ࡛ࠊChl ศᏊࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ㐺ษ࡟グ㏙ࡍࡿࡇ࡜ࡀྍ⬟࡞ MD ィ⟬࡟⏝࠸ࡿࣃ࣓࣮ࣛࢱࡢỴᐃࢆ⾜ࡗࡓࠋ1.3 㐣෭༷ᾮయཬࡧ⏕యศᏊ⣔࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫ࡟⌧ࢀࡿືⓗ஘ࢀ࡟㛵ࡍࡿ◊✲㑄⛣≧ែ⌮ㄽ࡞࡝࡛ࡣࠊ࢚ࢿࣝࢠ࣮㞀ቨࡀ㧗ࡃ཯ᛂࡣ⣔ෆࡢ௚ࡢ㐠ືࡢ᫬㛫ࢫࢣ࣮ࣝ࡟ẚ࡭㠀ᖖ࡟㐜ࡃࠊ཯ᛂ㐣⛬ࡣ࣏࢔ࢯࣥ⤫ィ࡟ᚑ࠺࡜ᬯ㯲࡟௬ᐃࡉࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ཯ᛂ࢖࣋ࣥࢺ㛫㝸ࡢศᕸࡣ཯ᛂ㏿ᗘᐃ࡛୚࠼ࡽࢀࡿᩘᣦᩘ㛵ᩘ࡛⾲ࡉࢀࡿࠋࡋ࠿ࡋࠊᾮయࡸ⏕యศᏊ࡞࡝ࡢ⣔࡛ࡣࠊᖜᗈ࠸᫬✵㛫ࢫࢣ࣮ࣝࡢᵓ㐀ᦂࡽࡂࡸኚ໬ࡀぢࡽࢀࡿࠋ࡜ࡃ࡟ࠊ཯ᛂ࡜ࡑࡢ௚ࡢ㐠ືࡢ᫬㛫ࢫࢣ࣮ࣝࡀ㏆ࡃ࡞ࡿ࡜ࠊ࣏࢔ࢯࣥ⤫ィ࠿ࡽࡎ- 436 -

ࢀࠊ཯ᛂ㏿ᗘࡣ᫬㛫࡜࡜ࡶ࡟ᦂࡽࡂࠊࡇࢀࡣືⓗ஘ࢀ࡜࿧ࡤࢀࡿࠋືⓗ஘ࢀࡢᐇ㦂࣭⌮ㄽ◊✲ࡀ⾜ࢃࢀ  ᖺ௨ୖ⤒ࡗࡓ⌧ᅾ࡛ࡶࠊືⓗ஘ࢀࡀ࡝ࡢࡼ࠺࡞ศᏊࡢ㐠ື࡟ࡼࡾࠊ࡝ࡢࡼ࠺࡟ᘬࡁ㉳ࡇࡉࢀࡿࡢ࠿࡟ࡘ࠸࡚ࡣ
ᮍࡔ࡟᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊỈࡸࣔࢹࣝ㸦.RE$QGHUVHQ㸦.$㸧ࣔࢹࣝࠊ:DKQVWỦP㸦:$+1㸧ࣔࢹࣝ࡜ࢿࢵࢺ࣮࣡ࢡᙧᡂ 17: ࣔࢹࣝ㸧ࡢ㐣෭༷ᾮయ࠿ࡽ⏕యศᏊࡢ⣔ࢆ◊✲ᑐ㇟࡟ࠊ୍㐃ࡢゎᯒᡭἲࢆ☜❧ࡍࡿ࡜࡜ࡶ࡟ࠊศᏊືຊᏛ㸦0'㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚ືⓗ஘ࢀࡢศᏊᶵᵓࡢゎ᫂ࢆ┠ⓗ࡜ࡍࡿࠋ
1.4 ࢖࢜ࣥᾮయ࡟ࡼࡿࣂ࢖࣐࢜ࢫ㈨※ࡢ⁐ゎ࣭ศゎ㐣⛬࡟㛵ࡍࡿ◊✲࢖࢜ࣥᾮయࡣ㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏࢆኚ࠼ࡿࡇ࡜࡛ᛶ㉁ࡀ␗࡞ࡿ✀㢮ࡢ࢖࢜ࣥᾮయࡀྜᡂྍ⬟࡛࠶ࡾࠊࢭ࣮ࣝࣟࢫ㧗ศᏊࡢ⁐ゎᗘࡢྥୖࢆ┠ᣦࡋࡓ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋࡇࡇ࡛ࡣࠊࢭ࣮ࣝࣟࢫࡢ⁐ゎ࣭ศ㞳࡟㐺ࡋࡓ㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
2.1 KaiC ୖࡢ KaiB-KaiB, KaiB-SasA, SasA-SasA ┦஫స⏝ࡢ኱ࡁࡉࡢぢ✚ࡶࡾᮏᖺᗘࡣ KaiC ࡜ KaiB ࡢ」ྜయᙧᡂࢆヲ⣽࡟ㄪ࡭ࡿࡇ࡜࡟ࡋࡓࠋKaiB ࡣ 2 ✀ࡢ␗࡞ࡿᏳᐃࡋࡓᢡࡾࡓࡓࡳ

ᵓ㐀ࢆᣢࡘ≉Ṧ࡞ࢱࣥࣃࢡ㉁࡛࠶ࡾࠊࡇࡢᵓ㐀ኚ໬࡟╔┠ࡋࡓࠋࡇࡢᵓ㐀ኚ໬ࡢ㐣⛬ࢆㄪ࡭ࡿࡓࡵ࡟ࡣࠊࡲ
ࡎᵓ㐀ኚ໬ࡢ⤒㊰ࡢึᮇ᥎ᐃࡀᚲせ࡜࡞ࡿࡀࠊKaiB ࡢࡼ࠺࡞ⴭࡋࡃ␗࡞ࡿ஧ࡘࡢᵓ㐀ࢆࡘ࡞ࡄ⤒㊰ࢆ⏝ពࡍࡿࡇ࡜ࡣᐜ࡛᫆ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣ㑄⛣≧ែ࡜஧ࡘࡢᏳᐃ≧ែࢆࡘ࡞ࡄ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰ࢆồࡵࡿᙉຊ࡞
࢔ࣝࢦࣜࢬ࣒ࢆ㛤Ⓨࡋࡓୖ࡛ࠊ❧య㞀ᐖࢆᕦጁ࡟㑊ࡅࡿࡓࡵࡢ␲ఝⓗ࡞࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࢆ⪃᱌ࡍࡿࡇ࡜ࢆ┠ᣦࡋࠊࡑࡢᐇ⏝໬ࢆ㐍ࡵࡿࠋ
2.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ບ㉳࢚ࢿࣝࢠ࣮⛣ືࡢゎ᫂࡟ࡣࠊྛⰍ⣲ศᏊࡢບ㉳࢚ࢿࣝࢠ࣮ࠊບ㉳≧ែ㛫ࡢ࢝ࢵࣉࣜࣥࢢ࠾ࡼࡧບ㉳࢚ࢿࣝࢠ࣮ࡢᦂࡽࡂ㸦ࢫ࣌ࢡࢺࣝᐦᗘ㸧ࡀᚲせ࡜࡞ࡿࠋLHCII ⣔ࡢ QM/MM-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ Chl a
࠾ࡼࡧ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮࠾ࡼࡧ᫬⣔ิ࡟ἢࡗ࡚ᦂࡽࡂࢆィ⟬ࡍࡿࡇ࡜ࡣ୙ྍ⬟࡛࠶ࡿࠋࡑࡇ࡛ࠊᡃࠎ
ࡢࢢ࣮ࣝࣉ࡛㛤Ⓨࡋࡓຠ⋡࠿ࡘ⢭☜࡞ศᏊຊሙࢩ࢙ࣃ࣮ࢻ⿵㛫⿵ṇ㸦MMSIC㸧ἲ࡟ᇶ࡙ࡁࠊLHCII ࡟࠾ࡅࡿChl a ࠾ࡼࡧ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮࡜ࡑࡢࡺࡽࡂࢆホ౯ࡍࡿࠋLHCII ࣔࣀ࣐࣮୰ࡢ 14 ಶࡢ Chl a ࠾ࡼࡧ Chl b࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮࡜ࡑࡢࡺࡽࡂࡢゎᯒࢆ MMSIC ἲࡢࣃ࣓࣮ࣛࢱࡢ㛤Ⓨࢆ㐍ࡵࡓࠋChl a ࠾ࡼࡧ Chl b ࡟ᑐࡍࡿࢱࣥࣃࢡ⎔ቃ࠿ࡽࡢỈ⣲⤖ྜ⿵ṇ࡜ࣜ࢞ࣥࢻࡢ㓄఩⿵ṇࢆ QM/MM ἲ࡛ồࡵࡿࠋࡲࡓࠊChl ศᏊ㛫ࡢ㟁Ꮚ࢝ࢵࣉࣜࣥࢢ࡟ࡘ࠸࡚ࡣࠊᡃࠎࡢࢢ࣮ࣝࣉ࡟࠾࠸࡚ Charge response kernel㸦CRK㸧ἲࢆᛂ⏝ࡋࠊᦂࡽࡂࢆ㐺ษ࡟グ㏙ྍ⬟࡞ TrCRK ἲࡶ㛤ⓎࡋࡓࠋMMSIC ἲࡢ㟁Ⲵ㛵ࡍࡿࣃ࣓࣮ࣛࢱࡀỴᐃࡋࠊTrCRK ἲ࡟ᇶ࡙ࡃ ChlศᏊ㛫ࡢ㟁Ꮚ࢝ࢵࣉࣜࣥࢢࡢィ⟬࡟ྲྀࡾ⤌ࡴࠋ
2.3 㐣෭༷ᾮయཬࡧ⏕యศᏊ⣔࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫ࡟⌧ࢀࡿືⓗ஘ࢀ࡟㛵ࡍࡿ◊✲ᮏ◊✲ࡣ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚㐣෭༷ᾮయࡸ⏕యศᏊ⣔࡟࠾ࡅࡿ཯ᛂ࡛⌧ࢀࡿືⓗ஘ࢀࡢゎᯒࢆ⾜࠺ࠋ௒ᖺᗘࡣࠊ㐣෭༷ࡸ࢞ࣛࢫࡢ◊✲࡟⏝࠸ࡽࢀࡿ .$ ࣔࢹࣝ࡜࣒࢝ࣜ࢘࢖࢜ࣥࢳࣕࣥࢿࣝ .Y ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ゎᯒࢆᐇ᪋ࡋࡓࠋ.$ ࣔࢹ࡛ࣝࡣࠊ5HGXFHG8QLW ࡛グ㏙ࡍࡿ㧗 ࡢ  ࠿ࡽ㐣෭༷㡿ᇦࡢ ࡲ࡛ࡢ㸵ࡘࡢ

ᗘ࡛᏶඲࡞ᖹ⾮໬࡟㐩ࡋ࡚࠿ࡽࣉࣟࢲࢡࢩࣙࣥࣛࣥࢆ⾜ࡗࡓࠋ୰㛫ᩓ஘㛵ᩘࡢ⮬ᕫ㒊ศࡸᖹᆒ஧஌ኚ఩࡞࡝ࡢゎᯒ࡛ᚑ᮶ࡢ◊✲࡜ྠᵝ࡞ᣲືࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋࠊ⢏Ꮚࡢኚ఩࡟ࡼࡾ཯ᛂᗙᶆࢆᐃ⩏ࡋࠊᵓ㐀ࡢ㐪࠸ࡼࡾ㐣Ώⓗ≧ែ࡜ᇶᗏ≧ែࡢ⢏Ꮚࢆ༊ูࡋࡓࠋࡉࡽ࡟ࠊືⓗ஘ࢀࡢ㉳※࡜ᛮࢃࢀࡿ୍ḟඖ࡟せ⣙- 437 -

࡛ࡁ࡞࠸ከḟඖࡢ࢝ࢵࣉࣜࣥࢢࢆ᥈ࡿࡓࡵ࡟ゎᯒࢆ⾜ࡗࡓࠋࡲࡓࠊ࢖࢜ࣥࢳࣕࣥࢿࣝ .Y ࡛ࡣࠊ㟁Ẽ⏕⌮Ꮫᐇ㦂ࡢ⃰ᗘࡢ PRO/ ࡜ 㹫9 ࡢ㟁఩࡛  ࣐࢖ࢡࣟ⛊⛬ᗘࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ࢖࢜ࣥ㏱㐣࡟㛵ࡍࡿゎᯒࢆ⾜ࡗࡓࠋ
2.4 ࢖࢜ࣥᾮయ࡟ࡼࡿࣂ࢖࣐࢜ࢫ㈨※ࡢ⁐ゎ࣭ศゎ㐣⛬࡟㛵ࡍࡿ◊✲ศᏊືຊᏛ㸦0'㸧ィ⟬࡟ࡼࡾ࢖࢜ࣥᾮయ୰࡟࠾ࡅࡿ㧗ศᏊࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ㐣⛬ࡢゎᯒࢆ⾜ࡗࡓࠋ࢖࢜ࣥᾮయ࡟ࡣ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ㸦>&PLP@>$FHWDWH@㸧࡟ຍ࠼࡚ࠊ㝜࢖࢜ࣥࢆ᭰࠼ࡓ࣓
ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2 + 32@㸧࡜ࠊᐊ ࡛ࡢ⢓ᛶࡀᑠࡉࡃ཯ᛂᛶࡢ㧗࠸ูࡢ࢖࢜ࣥᾮయ㸦>&PLP@>+32@㸧ࡢ㸰✀㢮ࢆ㑅ࢇ࡛㧗ศᏊࢭ࣮ࣝࣟࢫࢆ⁐㉁࡜ࡋ࡚ 0' ィ⟬ࢆ⾜ࡗࡓࠋ㸯㸮ಶࡢࢢࣝࢥ࣮ࢫࢆྵࢇࡔ㧗ศᏊ㙐ࢆከᩘ⏝࠸࡚✚ᒙᵓ㐀࡟ࡋࡓ㧗ศᏊࢭ࣮ࣝࣟࢫ࡟㛵ࡋ࡚ୖグ㸱✀㢮ࡢ࢖࢜ࣥᾮయ୰࡛ࡢ⁐ゎ࣭ศゎ㐣⛬ࡢẚ㍑ࢆ⾜ࡗࡓࠋᗘຠᯝ࡟㛵ࡋ࡚ࡣࠊ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ

࡜࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷࢖࢜ࣥᾮయࡢྛࠎ࡟ࡘ࠸࡚ ࠊࠊΥ࡟ᗘࢆタᐃࡋ࡚ࢩ࣑࣮ࣗࣞࢩࣙ

ࣥࢆᐇ⾜ࡋࡓࠋ≉࡟ࢭ࣮ࣝࣟࢫෆࠊཬࡧࢭ࣮ࣝࣟࢫ㛫Ỉ⣲⤖ྜࡢษ᩿㐣⛬ࡀ㝜࢖࢜ࣥࡢ✀㢮ࢆኚ࠼ࡿ㸦ࡇࡢሙྜࡣ࢖࢜ࣥࡢ኱ࡁࡉ㸧ࡇ࡜࡛࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ࢆㄪ࡭ࡓࠋࡉࡽ࡟ࢭ࣮ࣝࣟࢫศᏊෆ࣭㛫Ỉ⣲⤖ྜࡢษ᩿࡟కࡗ࡚㝧࣭㝜࢖࢜ࣥࡀ㧗ศᏊࣇ࢓࢖ࣂ࣮ෆ࡬࡜౵ධࡋ࡚࠸ࡃ㐣⛬ࡀୖグ㸱ࡘࡢ࢖࢜ࣥᾮయ࡛࡝ࡢࡼ࠺࡟
␗࡞ࡿࡢ࠿ࢆゎᯒࡋࡓࠋࡲࡓࠊࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ࢆྲྀࡾᅖࡴࢭ࣑࣮࣊ࣝࣟࢫࡢ◊✲࡟㝿ࡋ࡚ࡣࢭ࣮ࣝࣟ
ࢫ࡜࣑࣊ࢭ࣮ࣝࣟࢫ࠿ࡽ࡞ࡿࣔࢹࣝࣂ࢖࣐࢜ࢫࢆᵓ⠏ࡋࠊ⁐፹࡟ࡣỈࢆ㑅ࡧࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋ඲࡚ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥィ⟬ࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ *520$&6 ࢆ⏝࠸࡚⾜ࡗࡓࠋ


3

◊✲ᡂᯝ
3.1 KaiC ୖࡢ KaiB-KaiB, KaiB-SasA, SasA-SasA ┦஫స⏝ࡢ኱ࡁࡉࡢぢ✚ࡶࡾࡲࡎࠊ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰ࢆồࡵࡿ࢔ࣝࢦࣜࢬ࣒ࢆ㛤Ⓨࡋࡓࠋࡇࢀࡣࠊ⤒㊰᥈⣴ࢆ࠶ࡿ➼౯࡞᭱ᑠ໬ၥ㢟࡟᭩ࡁ᥮࠼ࠊࡑࢀࢆỗ⏝ࡢ㠀⥺ᙧ᭱ᑠ໬ၥ㢟ࢯࣝࣂ (IPOPT) ࢆ⏝࠸࡚ゎࡃ࢔ࣝࢦࣜࢬ࣒࡜࡞ࡗ࡚࠸ࡿࠋ࡞࠾ࠊ
ࡇࡢ⤒㊰᥈⣴࢔ࣝࢦࣜࢬ࣒ࡣࢱࣥࣃࢡ㉁ᵓ㐀ኚ໬ࡔࡅ࡛࡞ࡃࠊ࠶ࡽࡺࡿ㑄⛣≧ែ᥈⣴࡟⏝࠸ࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ࡑࡇ࡛㔞Ꮚ໬Ꮫィ⟬࡜ࡢే⏝ࢆᛕ㢌࡟⨨ࡁࠊAtomic Simulation Environment (ASE) ࢆ࢖࣏࣮ࣥࢺࡍࡿࡇ࡜࡛ᐜ
᫆࡟㑄⛣≧ែ᥈⣴ࡀ⾜࠼ࡿ࢔ࣉࣜࢣ࣮ࢩࣙࣥ㛤Ⓨࡶ⾜ࡗࡓࠋ୍᪉ࠊ❧య㞀ᐖࢆᕦጁ࡟㑊ࡅࡿ␲ఝⓗ࡞࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡶ⪃᱌ࡋࠊୖグࡢ⤒㊰᥈⣴࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸ࡿࡇ࡜࡛ࠊ㐣ᗘࡢ❧య㞀ᐖࡀ࡞࠸⤒㊰ࢆసࡿࡇ࡜ࡀ࡛ࡁࡿࡼ࠺࡟࡞ࡗࡓࠋ⌧ẁ㝵࡛ࡣᩘ༑ཎᏊ⛬ᗘࡢศᏊࡲ࡛࠺ࡲࡃồࡲࡿࡇ࡜ࡀ☜ㄆ࡛ࡁ࡚࠸ࡿࡢ࡛ࠊ
௒ᚋࢱࣥࣃࢡ㉁࡞࡝ࡢ኱ࡁ࡞ศᏊ࡟ࡶ㐺⏝⠊ᅖࢆᗈࡆ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ
3.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ࡇࡢ᭱㐺໬ࡉࢀࡓࣃ࣓࣮ࣛࢱࢆ⏝࠸࡚ࠊQM/MM ࡢィ⟬࡛ LHCII ࡢ 14 ಶࡢ Chl ࡢᵓ㐀ࢆ᭱㐺໬ࡋࠊࡇࢀࡽ
ࡢⰍ⣲࡟ᑐࡍࡿỈ⣲⤖ྜ⿵ṇ࡜㓄఩⿵ṇࡶ⪃៖ࡋࠊ㐺ษ࡞ TD-DFT ィ⟬࡟ࡼࡿບ㉳࢚ࢿࣝࢠ࣮ࢆ෌⌧ࡍࡿࡇ࡜ࡢ࡛ࡁࡿ MMSIC ࣃ࣓࣮ࣛࢱࢆỴᐃࡋࡓࠋࡑࡢ⤖ᯝࠊࡇࡢࡼ࠺࡟Ỵᐃࡋࡓ MMSIC ࣃ࣓࣮ࣛࢱࢆ⏝࠸ࡓ
MMSIC-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊLHCII ୰ࡢ 14 ಶࡢ Chl ࡢ QM/MM ບ㉳࢚ࢿࣝࢠ࣮ࢆṇ☜࡟෌⌧ࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡗࡓࠋ
3.3 㐣෭༷ᾮయཬࡧ⏕యศᏊ⣔࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫ࡟⌧ࢀࡿືⓗ஘ࢀ࡟㛵ࡍࡿ◊✲.$ ࣔࢹࣝ⣔࡛ࡣࠊᡃࠎࡣ⢏Ꮚࡢኚ఩࡟ὀ┠ࡋ࡚ゎᯒࢆ⾜ࡗࡓࠋ ᗘࡀపୗࡍࡿ࡟ࡘࢀࠊ୰㛫ᩓ஘㛵ᩘࡢࢭ- 438 -

ࣝࣇ㡯ࡀ♧ࡍࢲ࢖ࢼ࣑ࢡࢫࡢ⦆࿴᫬㛫ࡣ㛗ࡃ࡞ࡿ࡜࡜ࡶ࡟ࠊᵓ㐀ኚ໬ࡢ࢖࣋ࣥࢺ㛫ࡢ᫬㛫㛫㝸ࡢศᕸࡀᣦᩘ
㛵ᩘ࠿ࡽࢬࣞࠊ࣏࣡ࢯࣥ⤫ィ࠿ࡽኚ໬ࡋ࡚࠸ࡃᵝᏊࡀぢࡽࢀࡿࠋゎᯒࢆ⾜ࡗ࡚࠸ࡿᗘࡢ୰୍࡛␒ప࠸

ᗘࡢ  ࡟࠾࠸࡚ࡶࠊ$ ⢏Ꮚࡢ☜⋡㐣⛬ࡢ࣏࣡ࢯࣥ㐣⛬࠿ࡽࡢࡎࢀࡣ㠀ᖖ࡟኱ࡁࡃࡣ࡞࠸ࡀࠊ% ⢏Ꮚ࡟㛵ࡋ࡚ࡣ࣏࣡ࢯࣥ⤫ィ࠿ࡽ኱ࡁࡃࢬ࡚ࣞ࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓᡃࠎࡀᐃ⩏ࡋࡓ཯ᛂᗙᶆ࡟ἢࡗ࡚ᵓ㐀ኚ໬ࡢᵝ┦ࢆㄪ࡭ࡿ࡜࡜ࡶ࡟ࠊືⓗ஘ࢀࡀ࡝ࡢࡼ࠺࡟Ⓨ⏕ࡋ࡚࠸ࡿࡢ࠿ࠊࡑࡢศᏊ㉳※ࡢゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋࡲࡓࠊ
࢖࢜ࣥࢳࣕࣥࢿࣝ .Y ࡢゎᯒࢆ㐍ࡵࠊ㟁Ẽ⏕⌮Ꮫᐇ㦂ࡢ⃰ᗘࡢ PRO/ ࡜ P9 ࡢ᮲௳࡛ .Y ࡢ࢖࢜
ࣥ㏱㐣཯ᛂࡣ࣏࢔ࢯࣥ㐣⛬࠿ࡽ኱ࡁࡃࢬ࡚ࣞ࠸࡞࠸ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ௒ᚋࠊࡉࡽ࡟௚ࡢ᮲௳࡛ࡢィ⟬ࢆᐇ᪋ࡋࠊ࢖࢜ࣥࢳࣕࣥࢿࣝࡢ࢖࢜ࣥ㏱㐣཯ᛂࡢࢲ࢖ࢼ࣑ࢡࢫࢆㄪ࡭ࡿணᐃ࡛࠶ࡿࠋ
3.4 ࢖࢜ࣥᾮయ࡟ࡼࡿࣂ࢖࣐࢜ࢫ㈨※ࡢ⁐ゎ࣭ศゎ㐣⛬࡟㛵ࡍࡿ◊✲MD ィ⟬ࡢ⤖ᯝ࠿ࡽࠊࣜࣥ㓟ࢆྵࡴ࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయࡢ᭷⏝ᛶࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥ࡟ẚ࡭࡚ࠊࣜࣥ㓟ࢆྵࡴ࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయࡣ㧗ศᏊࢭ࣮ࣝࣟࢫࢆࡼࡾ▷᫬㛫࡛ຠ⋡ࡼࡃศゎ࣭⁐ゎࢆ㐍ࡵࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥࢆྵࡴ࢖࢜ࣥᾮయࡣ⇕ⓗᏳᐃᛶ࡟ஈࡋࡃࠊ㧗࡛ࡢ౑⏝࡟ࡣၥ㢟ࡀ࠶ࡿࡇ࡜ࡀᐇ㦂◊✲࠿ࡽࡶᣦ᦬ࡉࢀ࡚࠸ࡿࡀࠊィ⟬⤖ᯝ࠿ࡽࡶ⇕ⓗᏳᐃᛶࡢ࠶ࡿࣜࣥ
㓟ྵ᭷࢖࢜ࣥᾮయࡢ᪉ࡀ㧗࡛ࡢࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ࡟ࡣ㐺ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊࢭ

࣮ࣝࣟࢫ࡜࣑࣊ࢭ࣮ࣝࣟࢫ࠿ࡽ࡞ࡿࣔࢹࣝࣂ࢖࣐࢜ࢫࡢᵓ㐀࡟ࡘ࠸࡚ࡣィ⟬࠿ࡽࠊࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ෆ
ࡢỈ⣲⤖ྜ࡬ࡢ⁐፹ࡢ᥋㏆ࢆ㜼ᐖࡍࡿࡼ࠺࡟࣑࣊ࢭ࣮ࣝࣟࢫࡣࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ࢆྲྀࡾᅖࡴࡼ࠺࡟㓄⨨ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣᐇ㦂◊✲ࡢሗ࿌ࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫⏣⏥ ۻ‬ಙ୍㸪ᩧ⸨┿ྖ㸪”㠀⥺ᙧィ⏬ၥ㢟ỗ⏝ࢯࣝࣂࢆ⏝࠸ࡓ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰᥈⣴͇㸪 ➨ 24 ᅇ⌮ㄽ໬Ꮫウㄽ఍, 㔠ἑ, Mar. 18 (2022).
‫⏣⏥ۻ‬ಙ୍㸪ᩧ⸨┿ྖ㸪”ヲ⣽࡞཯ᛂࣔࢹࣜࣥࢢ࡜࣋࢖ࢬ᥎ᐃ࡟ᇶ࡙ࡃ᫬ィࢱࣥࣃࢡ㉁ KaiC ࡢᵓ㐀ᶵ⬟┦㛵ࡢゎ͇᫂, ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍, ᶓ὾, Sept. 20 (2022).
‫⏣⏥ۻ‬ಙ୍㸪ᩧ⸨┿ྖ㸪”Functional roles of the multimeric structure of KaiC revealed by detailed kinetic modelingand Bayesian parameter inference͇, ➨ 60 ᅇ⏕≀≀⌮Ꮫ఍ᖺ఍, ภ㤋, Sept. 28 (2022).
‫ ۻ‬S. Saito, "Conformational Dynamics of Proteins and Liquids", Department Seminar, IIT Kanpur, Kanpur, India,
March 10 (2023).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬T. Mori and S. Saito, “Molecular insights into the intrinsic dynamics and their roles during catalysis in Pin1

peptidyl-prolyl isomerase”, J. Phys. Chem. B 126, 5185-5193 (2022).
‫ ۻ‬T. Inagaki, M. Hatanaka, and S. Saito, “Anisotropic and finite effects on intermolecular vibration and relaxation
dynamics: Low-frequency Raman spectroscopy of water film and droplet on graphene by molecular dynamics
simulations”, J. Phys. Chem. B (in revision).

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㧗⢭ᗘ㟁Ꮚ≧ែ⌮ㄽ࡟ࡼࡿග㟁Ꮚ㐣⛬࡜ゐ፹཯ᛂ࡟㛵ࡍࡿ◊✲
Theoretical studies on the photo-electronic processes and catalytic
reactions using the accurate electronic structure theories‫ۑ‬Ụཎṇ༤ࠊPei Zhaoࠊ✄஭┤ே㸦ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࠊศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ㧗⢭ᗘ㟁Ꮚ≧ែ⌮ㄽࢆᇶ┙࡜ࡋ࡚」㞧࣭」ྜ⣔ࡢ໬Ꮫ஦㇟ࢆ◊✲ࡋࠊ᪂ࡋ࠸໬Ꮫᴫᛕࢆ

ᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ≉࡟ࠊ㧗⢭ᗘ࡞㟁Ꮚ≧ែ⌮ㄽࢆ㛤Ⓨࡋࠊග≀ᛶ⛉Ꮫࡸ୙ᆒ୍
⣔ゐ፹࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋᮏᖺᗘࡣࠊ1) 㔞Ꮚ㏫タィ⌮ㄽ࡟ࡼࡿศᏊ㸫㔠ᒓࢼࣀ⢏Ꮚ⣔ࡢග≀ᛶࡢ᭱㐺໬ࠊ2) ⣽⬊ෆ࡛ࣜࣥගⓎගࡍࡿ CAu6Ag2 ࢡࣛࢫࢱ࣮㸸Ⓨගࡢ࣓࢝ࢽࢬ࣒࡜㔞Ꮚ཰⋡ࡢ⌮ㄽゎᯒࠊ3) จ⦰┦㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢࢤࢫࢺศᏊ࡟ࡼࡿ࢟ࣛࣜࢸ࢕཯㌿ไᚚࡢᶵᵓࠊ4) ಟ㣭༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ⨨᥮ᇶ࡟ࡼࡿⓎගἼ㛗ไᚚࠊ5) ⓑ㔠᪘ᢸᣢᚤ⢏Ꮚゐ፹࡟ࡼࡿ NO άᛶ໬ࡢᢸయຠᯝ࡟㛵ࡍࡿ⣔⤫ⓗ࡞⌮ㄽゎᯒࠊ6) ⷧ⭷ኴ㝧㟁ụࡢ⏺㠃ࡢᏳᐃ໬࡟ࡼࡿග㟁ኚ᥮ຠ⋡ࡢྥୖ࡟㛵ࡍࡿ⌮ㄽゎᯒ࡟ࡘ࠸࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬᪉ἲࡣ Gaussian 09࣭Gaussian16 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ DFT/TD-DFT ἲ࠾ࡼࡧ VASP ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿࢫࣛ

ࣈࣔࢹࣝ DFT ἲࢆ⏝࠸࡚ࠊ⌮ㄽィ⟬ࢆᐇ᪋ࡋࡓࠋ3.1.ࡢ㔞Ꮚ㏫タィ⌮ㄽࡢ◊✲࡛ࡣࠊ⊂⮬࡟㛤Ⓨࡋࡓࣉࣟࢢ
࣒ࣛࢆ⏝࠸ࡓࠋ

3◊✲┠ⓗࠊෆᐜ

3.1. 㔞Ꮚ㏫タィ⌮ㄽ࡟ࡼࡿศᏊ㸫㔠ᒓࢼࣀ⢏Ꮚ⣔ࡢග≀ᛶࡢ᭱㐺໬ศᏊࡢග≀ᛶࡣ㔠ᒓࢼࣀ⢏Ꮚ㏆ഐ࡛኱ࡁࡃቑᖜࡉࢀ㸪ศᏊí㔠ᒓࢼࣀ⢏Ꮚ⣔ࡣከᵝ࡞ගᶵ⬟ࢆࡶࡘࠋศᏊ㔠ᒓࢼࣀ⢏Ꮚ⣔ࡢᶵ⬟ࡢ࣏ࢸࣥࢩࣕࣝࢆᘬࡁฟࡍ࡟ࡣ㸪㐺ษ࡞タィᣦ㔪ࡀᚲせ࡛࠶ࡿࠋᮏ◊✲࡛ࡣ㸪㔞Ꮚ㏫
タィ⌮ㄽ࠾ࡼࡧ㔞Ꮚ᭱㐺ไᚚ⌮ㄽࢆ㛤Ⓨ࣭ᐇ⿦ࡋ㸪ᡤᮃࡢග≀ᛶࢆⓎ⌧ࡍࡿ᭱㐺࡞ศᏊí㔠ᒓࢼࣀ⢏Ꮚ⣔࡜ධᑕ㟁ሙࡢタィࢆ⾜ࡗࡓࠋ㏫タィ⌮ㄽ࡛ࡣ㸪ࠕᶵ⬟✵㛫ࠖࡢ໙㓄࡟ᇶ࡙ࡃ᭱㐺໬࡜᥈⣴ࢆ⾜࠸㸪ࠕ໬Ꮫ✵㛫ࠖࡢタィࢆ⾜࠺ࠋᮏ◊✲࡛ࡣ㸪ศᏊࢆ᫬㛫౫Ꮡ㓄⨨㛫┦஫స⏝ἲ࡛グ㏙ࡋ㸪㔠ᒓࢼࣀ⢏Ꮚࢆㄏ㟁యࣔࢹࣝ࡟ᇶ࡙ࡃቃ⏺せ⣲ἲ࡛グ㏙ࡋ࡚ศᏊí㔠ᒓࢼࣀ⢏Ꮚ⣔ࢆ⾲⌧ࡋ㸪ྛせ⣲ࡢ᭱㐺໬ၥ㢟࡟ᖐ╔ࡋࡓࠋࡲࡓ㸪ධᑕ㟁ሙࡣ㔞Ꮚ᭱㐺ไᚚ⌮ㄽ࡛᭱㐺໬ࡋࡓࠋࡇࢀࡽࡢ⌮ㄽ࡟ࡼࡾ㸪ศᏊ✀࣭✵㛫㓄⨨㸪㔠ᒓࢼࣀ⢏Ꮚࡢ㔠ᒓ✀࣭ᙧ≧㸪ධᑕ㟁ሙࡢ᭱㐺໬࡟ᡂຌࡋࡓࠋᮏᡭἲࡣ㸪ศᏊí㔠ᒓࢼࣀ⢏Ꮚ⣔࡜ධᑕ㟁ሙࡢタィ᪉ἲ࡜ࡋ࡚᭷ᮃ࡛࠶ࡾ㸪ศᏊࣉࣛࢬࣔࢽࢡࢫࢩࢫࢸ࣒࡬ࡢ㐺⏝ࡀᮇᚅࡉࢀࡿࠋ
3.2. ⣽⬊ෆ࡛ࣜࣥගⓎගࡍࡿ CAu6Ag2 ࢡࣛࢫࢱ࣮㸸Ⓨගࡢ࣓࢝ࢽࢬ࣒࡜㔞Ꮚ཰⋡ࡢ⌮ㄽゎᯒⓎගᛶ㔠ᒓࢼࣀࢡࣛࢫࢱ࣮ࡣ㸪㓄఩Ꮚᵓ㐀ࡸ㔠ᒓࡢ✀㢮࣭᰾ᩘࡸ㓄ิ࡟ࡼࡾ㸪ࢡࣛࢫࢱ࣮ᵓ㐀࡟≉␗࡞≀
ᛶࡀⓎ⌧ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋᮏ◊✲࡛ࡣ㸪ྵ❅⣲」⣲⎔≧࢝ࣝ࣋ࣥ㸦NHC㸧㓄఩Ꮚࢆ⏝࠸ࡓⅣ⣲୰ᚰ㔠㖟㸦CAu6Ag2㸧ࢡࣛࢫࢱ࣮ࢆタィ࣭ྜᡂࡋ㸪ࡇࡢࢡࣛࢫࢱ࣮ࡀ⁐ᾮ୰࡛ᙉ࠸ࣜࣥගࢆⓎගࡍࡿࡇ࡜ࢆぢฟࡋ㸪
NHC 㓄఩ᏊࡀࣜࣥගⓎග࡟ᐤ୚ࡍࡿࡇ࡜ࢆ⌮ㄽィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓ㸪ࢫࣆࣥ㌶㐨┦஫స⏝ࢆྵࡴゎᯒ࡟ࡼࡗ࡚Ⓨග㏿ᗘᐃᩘࢆ⟬ฟࡋ㸪᭱ᑠ࢚ࢿࣝࢠ࣮஺ᕪⅬ࡬ࡢ࢚ࢿࣝࢠ࣮㞀ቨ࡛㔞Ꮚ཰⋡ࢆ㆟ㄽࡋࡓࠋࡉ

- 440 -

ࡽ࡟㸪ࡇࡢⓎගᑑ࿨ࡢ㛗࠸ࣜࣥගᛶ㔠㖟ࢡࣛࢫࢱ࣮ࢆ⣽⬊࢖࣓࣮ࢪࣥࢢ࡟⏝࠸ࡓ࡜ࡇࢁ㸪⣽⬊࡬ࡢྲྀ㎸ࡳࡢ⤒㊰ࡸ≉ᐃࡢᑠჾᐁ࡟㑅ᢥⓗ࡟ᒁᅾࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡾ㸪ᚑ᮶ࡢ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚࡢ㠀㑅ᢥⓗ࡞ྲྀ㎸ࡳ࡜ࡣ␗࡞ࡿඃࢀࡓᶵ⬟ࡀ☜ㄆࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽ㸪㧗タィᛶࡢ㓄఩Ꮚ࡜㔠ᒓ࢖࢜ࣥ࠿ࡽᡂࡿከ᰾㔠ᒓ࢖࢜ࣥࢡࣛࢫࢱ࣮ࡀ㸪ᙉࣜࣥගᛶࡢ᪂≀㉁⩌࡜ࡋ࡚㸪ගࣂ࢖࢜ศᯒࡢⓎᒎ࡟㈉⊩ࡋ࠺ࡿࡇ࡜ࢆ♧ࡋࡓࠋ
3.3. จ⦰┦㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢࢤࢫࢺศᏊ࡟ࡼࡿ࢟ࣛࣜࢸ࢕཯㌿ไᚚࡢᶵᵓ
㔠ᒓࢡࣛࢫࢱ࣮ࡣ㸪࢟ࣛࣜࢸ࢕ࢆᑟධࡍࡿࡇ࡜࡛ᶵ⬟ࡸᛂ⟅ᛶࢆ௜୚ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋᮏ◊✲࡛ࡣ㸪ࢤࢫࢺศᏊࡢᑟධ࡟ࡼࡗ࡚㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢ࢟ࣛࣜࢸ࢕ไᚚࢆ⾜ࡗࡓࠋ㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢྜᡂ࡟࢚ࢼࣥࢳ
࣐࣮࢜㓄఩Ꮚ࡛࠶ࡿ Į-ࢪࣄࢻ࣏ࣟࣜ㓟㸦DHLA㸧ࢆ⏝࠸ࡿ࡜㸪㖟-ࢪࢳ࣮࢜ࣞࢺ㦵᱁࠿ࡽ࡞ࡿ∦ᡭ࢟ࣛࣝ࡞
Ag29(DHLA)12 ࢡࣛࢫࢱ࣮ࢆ⏕ᡂࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡉࡽ࡟㸪ࣆࣜࢪࣥ➼ࡢᑠࡉ࡞ࣝ࢖ࢫሷᇶศᏊࢆࢤࢫࢺศ
Ꮚ࡜ࡋ࡚ᑟධࡋ㸪ྑᡭ⣔࡜ᕥᡭ⣔ࡢࢼࣀࢡࣛࢫࢱ࣮ࡢ┦ᑐⓗᏳᐃᛶࢆ㏿ᗘㄽⓗ࡟㏫㌿ࡉࡏ㸪࢟ࣛࣜࢸ࢕ࡀ㏫㌿ࡋࡓࢼࣀࢡࣛࢫࢱ࣮ࢆ⏕ᡂࡍࡿࡇ࡜࡟ᡂຌࡋࡓ[4]ࠋ⌮ㄽィ⟬ࢆ⏝࠸࡚㸪ࢤࢫࢺศᏊ࡟ࡼࡗ࡚࢟ࣛࣜࢸ࢕ࡀ
㏫㌿ࡍࡿ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ࣓࢝ࢽࢬ࣒ࡣ㸪ࢼࣀࢡࣛࢫࢱ࣮㛫ࡢ┦஫స⏝࡟ࡼࡿ࢟ࣛࣜࢸ࢕ࡢ
⮬ᕫไᚚࡸ⮬ᕫ」〇࡬࡜ᣑᙇࡉࢀࡿࠋ㻌
3.4. ಟ㣭༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ⨨᥮ᇶ࡟ࡼࡿⓎගἼ㛗ไᚚ༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ㸦SWNT㸧࡟⨨᥮ᇶࢆᑟධࡍࡿࡇ࡜࡟ࡼࡗ࡚㸪Ⓨගࣆ࣮ࢡࡣ㉥Ⰽࢩࣇࢺࡋ㸪Ⓨගᙉᗘࡀྥୖࡍࡿࠋࡋ࠿ࡋ㸪໬Ꮫಟ㣭࡜ⓎගἼ㛗ࡢ⢭ᐦไᚚࡣ౫↛࡜ࡋ࡚ㄢ㢟࡛࠶ࡿࠋᮏ◊✲࡛ࡣ㸪SWNT ࢆẁ㝵ⓗ࡟໬Ꮫಟ㣭ࡍࡿࡇ࡜࡛㸪㒊఩≉␗ⓗ࡞ᶵ⬟໬ࡀ࡞ࡉࢀ㸪Ⓨගᙉᗘ࣭Ἴ㛗ࢆไᚚ࡛ࡁࡿࡇ࡜ࢆᐇ㦂࠾ࡼࡧ⌮ㄽィ⟬࡟ࡼࡗ࡚♧ࡋࡓࠋᩘ✀㢮ࡢ࢟ࣛࣝゅࢆࡶࡘ SWNT ࡟ࡘ࠸࡚㸪nBu-SWNTs-nBu ࠾ࡼࡧ nBu-SWNTsH ௜ຍయࢆྜᡂࡋ㸪ࡑࢀࡒࢀ E11**Ⓨග࠾ࡼࡧ E11*Ⓨගࡀ୺࡟ᚓࡽࢀࡿࡇ࡜ࢆᐇドࡋࡓ[10]㸬DFT/TD-DFT ἲ࡟ࡼࡾ㸪SWNT ࡢ 1,2-࠾ࡼࡧ 1,4-௜ຍయࡢ⇕ຊᏛⓗᏳᐃᛶ࡜㑄⛣࢚ࢿࣝࢠ࣮࡟ᇶ࡙࠸࡚Ⓨගࢆ⣔⤫ⓗ࡟ᖐᒓࡋࡓࠋࡑࡢ⤖ᯝ㸪௜ຍᇶࡢ❧య㞀ᐖ࡜ R ್((n,m)-ࢼࣀࢳ࣮ࣗࣈࡢ R=mod(n-m,3))ࡀ㸪௜ຍ఩⨨࡜ᒁᡤࣂࣥࢻࢠ
ࣕࢵࣉࡢ኱ࡁࡉࢆไᚚࡍࡿ㔜せ࡞ᅉᏊ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓࠋ㻌
3.5. ⓑ㔠᪘ᢸᣢᚤ⢏Ꮚゐ፹࡟ࡼࡿ NO άᛶ໬ࡢᢸయຠᯝ࡟㛵ࡍࡿ⣔⤫ⓗ࡞⌮ㄽゎᯒⓑ㔠᪘㔠ᒓࡣ㸪⮬ື㌴࠿ࡽ᤼ฟࡉࢀࡿ᭷ᐖ≀㉁ࢆపῶࡍࡿࡓࡵࡢ୕ඖゐ፹࡜ࡋ࡚ᗈࡃ฼⏝ࡉࢀ࡚࠸ࡿࠋᢸ
ᣢᚤ⢏Ꮚゐ፹࡛ࡣ㸪㔠ᒓᚤ⢏Ꮚ࡜㔠ᒓ㓟໬≀ࡢ⏺㠃ࡀ㔜せ࡞ᙺ๭ࢆᣢࡘࠋᮏ◊✲࡛ࡣ㸪NO ⤖ྜάᛶ໬࡟ࡘ࠸
࡚㸪Sr3Ti2O7㸪Sr3Fe2O7㸪CeO2㸪TiO2㸪ZrO2㸪Ȗ-Al2O3 ᢸయ࡜ⓑ㔠᪘㔠ᒓࢡࣛࢫࢱ࣮㸦Pd㸪Pt㸪Rh㸧ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡿ㔠ᒓ㸭㓟໬≀⏺㠃࡟ࡘ࠸࡚ Slab model DFT ィ⟬࡟ࡼࡾ⣔⤫ⓗ࡟◊✲ࡋࡓ[2]ࠋ㔠ᒓࢡࣛࢫࢱ࣮࡟㏆࠸㓟⣲✵Ꮝࢆ୍ࡘᵓ⠏ࡋ㸪Mars van Krevelen ᶵᵓ࡟ࡼࡿ㸪NO ࡢάᛶ໬ࢆホ౯ࡋࡓࠋNO ࡢ O ཎᏊࡣ NO ࡢゎ㞳ᚋ࡟㔠ᒓ㓟໬≀ࡢ㓟⣲Ḟ㝗ࢆᇙࡵ㸪N ཎᏊࡣ㔠ᒓࢡࣛࢫࢱ࣮ୖ࡟ṧࡉࢀࡿࠋ㓟⣲Ḟ㝗ࡀ࠶ࡿሙྜ㸪NO ࡢάᛶ໬࡛ࡣⓎ⇕㐣⛬ࡀ☜ㄆࡉࢀ㸪㔠ᒓࢡࣛࢫࢱ࣮࡜㓟⣲Ḟ㝗ࡢ┦஫స⏝ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ㻌
3.6. ⷧ⭷ኴ㝧㟁ụࡢ⏺㠃ࡢᏳᐃ໬࡟ࡼࡿග㟁ኚ᥮ຠ⋡ࡢྥୖ࡟㛵ࡍࡿ⌮ㄽゎᯒⷧ⭷ኴ㝧㟁ụࡢ⏺㠃ࡣࠊࢹࣂ࢖ࢫࡢຠ⋡࡜⪏ஂᛶࢆỴᐃࡍࡿୖ࡛ᴟࡵ࡚㔜せ࡞ᙺ๭ࢆᢸࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊᐇ㦂ⓗ࡟࣌ࣟࣈࢫ࢝࢖ࢺ⾲㠃ࢆࣆ࣌ࣛࢪࣥ㸦PP㸧࡛ฎ⌮ࡍࡿ࡜㟁Ⲵᢳฟࡀಁ㐍ࡉࢀࠊC60 ࣆࣟࣜࢪࣥ
ࢺࣜࢫ࢔ࢩࢵࢻ㸦CPTA㸧࡛ฎ⌮ࡍࡿ࡜ࣄࢫࢸࣜࢩࢫࡀῶᑡࡋ࡚ࠊග㟁ኚ᥮ຠ⋡ࡀ᭱኱ 22.7㸣࡟ቑᙉࡉࢀࡿࡇ࡜ࢆぢฟࡋࡓࠋࡉࡽ࡟ࠊDFT ィ⟬࡟ࡼࡗ࡚࣌ࣟࣈࢫ࢝࢖ࢺ⾲㠃ࡢ A ࢧ࢖ࢺ✵Ꮝࡣ PP2+࢝ࢳ࢜ࣥ࡟ࡼࡗ࡚Ᏻᐃ໬ࡉࢀࠊCPTA ࡣ⾲㠃ࡢࣚ࢘໬≀✵Ꮝ࡟྾╔ࡍࡿࡇ࡜ࢆ♧ࡋࡓࠋࡲࡓࠊPb2+ࡼࡾࡶ Sn2+ࡢ᪉ࡀḞ㝗ᙧᡂ࢚ࢿࣝ
ࢠ࣮ࡀప࠸ࡓࡵࠊCPTA ࡣ⭷⾲㠃ࡢ Sn2+ࢧ࢖ࢺ࡟ඃඛⓗ࡟⤖ྜࡍࡿࡇ࡜ࡶ♧ࡋࡓ[11]ࠋ㻌- 441 -

4Ⓨ⾲ᐇ⦼1) Theoretical Design of Photofunctional Molecular Aggregates and Molecule-Nanocluster Systems for Optical Properties
with Inverse Design Approach
M. Ehara and T. Shiraogawa
The 10th Asian Pacific Conference of Theoretical & Computational Chemistry (APCTCC), Vietnam, February 19-23,
2023 (Invited Talk).
2)Theoretical Studies of Photofunctional Systems and Heterogeneous Catalysts
M. Ehara
CMDR workshop, On-line (Zoom), September 9, 2022 (Invited Talk).
3)Inverse Design Approach of Photofunctional Molecular Aggregates and Molecule-Nanocluster Systems (English)
Masahiro Ehara
Workshop 2022 on Multiscale Simulation of Complex Reacting Systems (StudyCamp2022), ⁠㈡, 3 ᭶ 6-7 ᪥, 2023.
4)ศᏊ㞟ྜ⣔࡜㔠ᒓࢡࣛࢫࢱ࣮ࡢග≀ᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲Ụཎṇ༤࣮࣡ࢡࢩࣙࢵࣉࠕ࢟ࣛࣝ࡞ග࡜࢟ࣛࣝ࡞≀㉁ࠖ, ኱㜰(ࣁ࢖ࣈࣜࢵࢻ), 3 ᭶ 1 ᪥, 2023.
5)ከᏍᛶศᏊ⤖ᬗ PdII-MMF ࡟ࡼࡿග↷ᑕ࢜ࣞࣇ࢕ࣥ⛣ື཯ᛂࡢ཯ᛂᶵᵓ
Ụཎṇ༤
IQCE 㔞Ꮚ⛉Ꮫ᥈⣴ㅮ₇఍ 2022ࠕ㔞Ꮚ໬Ꮫ࡛᥈ࡿ໬Ꮫࡢ᭱ඛ➃ࠖ㸪࢜ࣥࣛ࢖ࣥ㸪1 ᭶ 21 ᪥, 2023.
6)ບ㉳Ꮚ⤖ྜἲ࡜㔞Ꮚ㏫タィ⌮ㄽࡢග≀ᛶ࡬ࡢᛂ⏝Ụཎṇ༤࢟ࣛࣝග≀㉁⛉Ꮫ➨ 1 ᅇࢺ࣮ࣞࢽࣥࢢᕤᡣ, ࢜ࣥࣛ࢖ࣥ㸪12 ᭶ 21 ᪥, 2022.
7)DFT࣭TDDFT ἲࡢᇶ♏㸸ศᏊ⣔࣭㔠ᒓࢡࣛࢫࢱ࣮⣔ࡢ࢟ࣛࣝග≀ᛶࡢ⌮ㄽィ⟬Ụཎṇ༤࢟ࣛࣝග≀㉁⛉Ꮫ➨ 1 ᅇࢺ࣮ࣞࢽࣥࢢᕤᡣ, ࢜ࣥࣛ࢖ࣥ㸪12 ᭶ 14 ᪥, 20228)୙ᆒ୍⣔ゐ፹࣭ࢡࣛࢫࢱ࣮ゐ፹ࡢ⌮ㄽ࣭ィ⟬⛉ᏛỤཎṇ༤
ゐ፹Ꮫ఍ ⏺㠃ศᏊኚ᥮◊✲఍࣮࣡ࢡࢩࣙࢵࣉࠕᅛయゐ፹ࡢάᛶᵓ㐀ࢆ▱ࡿࠖ, ࢜ࣥࣛ࢖ࣥ, 11 ᭶ 28 ᪥, 2022.
9)ศᏊ㞟ྜయ࣭㔠ᒓࢡࣛࢫࢱ࣮ࡢ࢟ࣛࣝග≀ᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Ụཎṇ༤ィ⟬࢔ࢫࢺࣟࣂ࢖࢜ࣟࢪ࣮2022㸪⟃Ἴ, 11 ᭶ 10-11 ᪥, 2022.
10)Theoretical Studies on Photofunctional Systems and Heterogeneous Catalysts (English)
Masahiro Ehara➨ 41 ᅇ CMD3 ࣮࣡ࢡࢩࣙࢵࣉ㸦ඛ➃஦౛ㅮ⩏㸧኱㜰኱Ꮫ࢚࣐࣮ࢪࣥࢢࢧ࢖࢚ࣥࢫࢹࢨ࢖ࣥ R3 ࢭࣥࢱ࣮, ࢜ࣥࣛ࢖ࣥ, 9 ᭶ 9 ᪥, 2022.

ฟ∧ᐇ⦼1)մY. Konno, R. Morooka, T. Morishita, P. Zhao, N. Miyasaka, K. Ono, A. Noda, D. Uchida, R. Iwasaki, M. Yamada, M.
Ehara, Y. Maeda, ”Photoluminescence Properties of Single-Walled Carbon Nanotubes Influenced by the Tether Length of
Reagents with Two Reactive Sites”, Chem. Eur. J in press (2023).
2)մ P. Zhao, M. Ehara, ”Theoretical Insights into the Support Effect on the NO Activation over Platinum-Group Metal
Catalysts”, J. Chem. Phys. 158, 134701 (2023).
3)մY. Maeda, R. Morooka, P. Zhao, D. Uchida, Y. Konno, M. Yamada, M. Ehara, ”Controlling Near-Infrared
Photoluminescence Properties of Single-Walled Carbon Nanotubes by Substituent Effect in the Stepwise Chemical
Functionalization”, J. Phys. Chem. C. 127, 2360–2370 (2023).
4)մS. Hu, P. Zhao, K. Nakano, R. D. J. Oliver, J. Pascual, J. A. Smith, T. Yamada, M. A. Truong, R. Murdey, N. Shioya,
T. Hasegawa, M. Ehara, M. B. Johnston, K. Tajima, Y. Kanemitsu, H. J. Snaith, A. Wakamiya, ”Synergetic Surface
Modification of Tin-Lead Perovskite Solar Cells”, Advanced Materials, 35, 2208320 (2023).

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5) Y. Shui, G. Pei, P. Zhao, M. Xiong, S. Li, M. Ehara, T. Yang, ”Understanding Electronic Structures, Chemical Bonding,and Fluxional Behavior of Lu2@C2n (2n = 76 - 88) by a Theoretical Study”, J. Chem. Phys. 157, 184306 (2022).
6)մT. Shiraogawa, G. Dall’Osto, R. Cammi, M. Ehara, S. Corni, ”Inverse Design of Molecule-Metal Nanoparticle
Systems Interacting with light for the Desired Photophysical Properties”, Phys. Chem. Chem. Phys. 24, 22768 - 22777(2022).
7) P. Zhao, K. Ueda, R. Sakai, M. Ehara, A. Satsuma, S. Sakaki, ”Surface Modification of MCr2O4 (M = Mg and Zn) by
Cu-Doping: Theoretical Prediction and Experimental Observation of Enhanced Catalysis for CO Oxidation”, Appl. Sur.
Sci. 605, 154681 (2022).
8)մZ. Lei, M. Endo, H. Ube, T. Shiraogawa, P. Zhao, K. Nagata, X.-L. Pei, T. Eguchi, T. Kamachi, M. Ehara, T. Ogawa,M. Shionoya, ”N-Heterocyclic Carbene-based C-centered Au(I)-Ag(I) Clusters with Intense Phosphorescence and theOrganelle-selective Translocation in Cells”, Nature Commun. 13, 4288-1-9 (2022). (Press Release)9) M. Han, S. Tashiro, T. Shiraogawa, M. Ehara, M. Shionoya, ”Substrate-Specific Activation and Long-range Olefin
Migration Catalysis at the Pd Centers in a Porous Metal-Macrocycle Framework”, Bull. Chem. Soc. Jpn. 95, 1303-1307(2022).
10)մS. Hu, P. Zhao, B. Li, P. Yu, L. Yang, M. Ehara, P. Jin, T. Akasaka, X. Lu, ”Cluster-Geometry-Associated MetalMetal Bonding in Trimetallic Carbide Clusterfullerenes”, Inorg. Chem. 61, 11277–11283 (2022).
11)T. Nakashima, R. Tanibe, H. Yoshida, M. Ehara, M. Kuzuhara, T. Kawai, ”Self-regulated Pathway-dependent Chirality
Control of Silver Nanoclusters”, Angew. Chem. Int. Ed. 61, e202208273-1-8 (2022).

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ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿࢱࣥࣃࢡ㉁ࡢจ㞟࡜จ㞟㜼ᐖProtein aggregation and its inhibition observed by molecular dynamics
simulations‫ۑ‬ዟᮧஂኈ㸪ఀ⸨ᬡ㸪㇂ᮏ຾୍㸪⚟ཎ኱㍤㸪኱ከ࿴ඞ⣖㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗ㸪ෆᐜ
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ࢽࣥ㸦SRO\$㸧ࡢจ㞟యࡣ࣏ࣜ࢔ࣛࢽࣥ⑓ࢆᘬࡁ㉳ࡇࡍࠋࢱࣥࣃࢡ㉁ࡸ࣌ࣉࢳࢻࡢจ㞟యࡀࡇࢀࡽࡢ⑌ᝈࢆᘬ
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ࣜ࢝⨨᥮ࢯ࣮ࣜࣗࢺࢸࣥࣃࣜࣥࢢἲࠖࡢ

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ࣜࢦ࣐࣮໬㐣⛬ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿࠋࡋ࠿ࡋࠊ$ȕ ࡢ & ᮎ➃ࡢ  ṧᇶࡀจ㞟࡟࠾࠸࡚࡝ࡢࡼ࠺
࡞ᙺ๭ࢆᯝࡓࡍ࠿ࡣ୙࡛᫂࠶ࡗࡓࠋࡲࡓࠊ$ȕ ࡜ $ȕ ࡢ࢜ࣜࢦ࣐࣮໬㐣⛬ࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣࠊ
࢜ࣜࢦ࣐࣮໬ࡢ࢝ࢠ࡜࡞ࡿ࢔࣑ࣀ㓟ṧᇶࢆ≉ᐃࡍࡿࡓࡵ࡟ࡶ୙ྍḞ࡛࠶ࡿࠋࡑࡇ࡛ࠊ࢜ࣜࢦ࣐࣮໬ࡢึᮇ㐣⛬࡛࠶ࡿ஧㔞య໬㐣⛬ࢆㄪ࡭ࡿࡓࡵࠊ$ȕ ࡜ $ȕ ࡟ࡘ࠸࡚ࣁ࣑ࣝࢺࢽ࢔ࣥࣞࣉࣜ࢝⨨᥮ศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ$ȕ ࡢ & ᮎ➃࡟࠶ࡿ  ࡘࡢṧᇶࡣࠊ& ᮎ➃ࡀ㟼㟁ᘬຊ࡟ࡼࡾ $UJ ࡜ࢥࣥࢱࢡࢺࡋࡸࡍࡃࡋࠊࡇࡢࢥࣥࢱࢡࢺ࡟ࡼࡾ ȕ࣊࢔ࣆࣥࡀᏳᐃ໬ࡍࡿࡇ࡜ࢆⓎぢࡋࡓࠋࡇࡢ ȕ ࣊࢔ࣆࣥࡣศᏊ㛫ࡢ ȕ ࣈࣜࢵࢪࢆᙧᡂࡋ࡚஧㔞యᙧᡂࢆಁ㐍ࡍࡿࡇ࡜ࡶศ࠿ࡗࡓࠋࡇࡢⓎぢ࠿ࡽ $ȕ ࡢ஧㔞య໬ࡢ㘽࡜࡞ࡿṧᇶࡀ  ␒┠ࡢ࢔࣑ࣀ㓟ṧᇶ࡛࠶ࡿ࢔ࣝࢠࢽࣥ $UJ ࡛࠶ࡿࡇ࡜ࢆ⌮ㄽⓗ࡟ணゝࡋࡓࠋࡲࡓࠊ$UJ ࢆ௚ࡢ࢔࣑ࣀ㓟ṧᇶ࡟⨨᥮ࡍࡿ࡜ ȕ ࣊࢔ࣆࣥࡀᙧᡂࡉࢀ࡟ࡃࡃ࡞ࡾจ㞟ࡀᢚไࡉࢀࡿࡢ࡛ࡣ࡞࠸࠿࡜ண᝿ࡋࡓࠋࡇ
ࡢண᝿ࢆ☜࠿ࡵࡿࡓࡵࠊ㔝⏕ᆺࡢ $ȕࠊ$UJ ࢆࢢࣝࢱ࣑ࣥ㓟࡟ኚ␗ࡉࡏࡓ 5(ࠊ$UJ ࢆࢢࣜࢩࣥ࡟ኚ␗ࡉࡏ
ࡓ 5* ࡢ  ✀㢮࡟ࡘ࠸࡚࢝ࣀࢽ࢝ࣝศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ࡜ࡇࢁࠊ㔝⏕ᆺ࡛ࡣ ȕ ࣊࢔ࣆࣥࡀ
ᙧᡂࡉࢀࡸࡍ࠸ࡢ࡟ᑐࡋࠊ5( ࡸ 5* ኚ␗య࡛ࡣ ȕ ࣊࢔ࣆࣥࡀᙧᡂࡉࢀ࡟ࡃ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ࡟ࠊ⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮ࡢຍ⸨᫭୍ᩍᤵࡽ࡟࠾㢪࠸ࡋ࡚㔝⏕ᆺࠊ5(ࠊ5* ࡟ࡘ࠸࡚ࢳ࢜ࣇࣛࣅࣥ 7 ⺯ගᐇ㦂ࢆ

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⾜ࡗ࡚ࡶࡽࡗࡓ࡜ࡇࢁࠊᡃࠎࡢணゝ㏻ࡾ㔝⏕ᆺࡢ $ȕ ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆᙧᡂࡋࡓࡢ࡟ᑐࡋࠊ5( ࠾ࡼࡧ5* ኚ␗య࡛ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ࡣ࡯࡜ࢇ࡝ᙧᡂࡉࢀࡎจ㞟ࡀ㢧ⴭ࡟ᢚไࡉࢀࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࡢࡇ࡜
࠿ࡽᡃࠎࡢ⌮ㄽⓗணゝ㏻ࡾ $UJ ࡀจ㞟ࡢ࢝ࢠ࡜࡞ࡿṧᇶ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸦ᅗ 㸧ࠋࡉࡽ࡟ $UJ ࡢኚ␗ࡣ $ȕ ࡢจ㞟ࡶᢚไࡋࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊ$UJ ࡣ $ȕ ࡀศᏊ㛫᥋ゐࢆᙧᡂࡍࡿࡓࡵ࡟㔜せ࡛࠶ࡿࡇ࡜ࡶศ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊ$UJ ࡢ࢜ࣜࢦ࣐࣮໬㐣⛬࡟࠾ࡅࡿᙺ๭ࡣࠊ& ᮎ➃ࡢ  ࡘࡢṧᇶ࡟ࡼࡗ࡚
␗࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
ᅗ  㸦ୖ㸧$ȕ ࡛ࡣ $UJ ࡀ & ᮎࡢ㏆ࡃ࡟᮶࡚㟼㟁┦஫స⏝࡛ᘬࡁྜ࠺ࡓࡵࠊȕ ࣊࢔ࣆࣥࡀᏳᐃ໬ࡉࢀࡿࠋ
㸦ᕥୗ㸧ศᏊෆ࡛ ȕ ࣊࢔ࣆࣥࢆᙧᡂࡋࡓ⟠ᡤ࡛ศᏊ㛫ࡢ ȕ ࢩ࣮ࢺࡀᙧᡂࡉࢀࡿࠋ㸦ྑୗ㸧㔝⏕ᆺ㸦:7㸧
࡛ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ࡀᙧᡂࡉࢀࡿࡢ࡟ᑐࡋࠊ$UJ ࢆࢢࣜࢩࣥ࡟⨨᥮ࡋࡓኚ␗య㸦5*㸧࠾ࡼࡧࢢࣝࢱ
࣑ࣥ㓟࡟⨨᥮ࡋࡓኚ␗య㸦5(㸧࡛ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ᙧᡂࡀᢚไࡉࢀࡿࠋ
ࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢἲࡢᨵⰋ
⏕యศᏊ࡞࡝」㞧࡞⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆᣢࡘ⣔ࡢᵓ㐀ࢧࣥࣉࣜࣥࢢࢆຠ⋡ⓗ࡟⾜࠺ࡓࡵࠊࣞࣉࣜ࢝஺᥮

ἲ࡞࡝ࡢᣑᙇ࢔ࣥࢧࣥࣈࣝศᏊືຊᏛἲࡀࡼࡃ⏝࠸ࡽࢀ࡚࠸ࡿࠋᡃࠎࡣࣞࣉࣜ࢝஺᥮ἲࡼࡾࡶຠ⋡ࡢⰋ࠸ᡭἲ࡛࠶ࡿࣞࣉࣜ࢝⨨᥮ἲࢆ᭱㏆㛤Ⓨࡋࡓࠋࡇࡢ᪉ἲ࡛ࡣ」ᩘࡢ⣔ࡢࢥࣆ࣮㸦ࣞࣉࣜ࢝㸧ࢆ⏝ពࡋࠊࡑࢀࡒࢀ
ࡢࣞࣉࣜ࢝࡟␗࡞ࡿ

ᗘࢆ๭ࡾᙜ࡚ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ㏵୰࡟  ࡘ௨ୖࡢࣞࣉࣜ࢝ࡢ㛫࡛ࡇ࠺ࡍࡿࡇ࡜࡛ྛࣞࣉࣜ࢝ࡢ ࡘࡢࣞࣉࣜ࢝ࡢ㛫࡛ᗘࠊ⣔඲యࡢ

ᗘࢆୖୗࡉࡏࠊ⮬⏤࢚ࢿࣝࢠ࣮ᴟᑠ≧ែ࠿ࡽྛ⣔ࢆ⬺ฟࡉࡏࡿࠋࡇࡢ᪉ἲࡣ

ᗘࢆ஺᥮ࡍࡿࣞࣉࣜ࢝஺᥮ἲࡼࡾࡶᙉຊ࡞᪉ἲ࡛࠶ࡿࠋࡇࡢᡭἲࢆඖ࡟ᡃࠎࡣ᫖ᖺ

ᗘ࡛ࡣ࡞ࡃ⁐㉁ࡢ

ᗘࡔࡅ࡟ὀ┠ࡋ࡚ࡑࡢᗘࢆ⨨᥮ࡍࡿ᪉ἲࠕࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣜࣗࢺࢸ

ࣥࣃࣜࣥࢢ㸦5367㸧ἲࠖࢆ㛤Ⓨࡋࡓࠋࡇࡢ᪉ἲ࡛ࡣࣞࣉࣜ࢝࡜
ࡵసᡂࡍࡿࠋ௒ᖺᗘࡣࡇࡢࣜࢫࢺࡢసࡾ᪉࡟ࡼࡗ࡚⁐㉁࡜ࡣࣞࣉࣜ࢝࡜

ᗘࢆ⨨᥮ࡍࡿࠋ

ᗘࡢ⤌ྜࡏࢆᑐᛂࡉࡏࡿࣜࢫࢺࢆ࠶ࡽ࠿ࡌ

ᗘࡢ㑄⛣☜⋡ࡀኚ໬ࡍࡿࡇ࡜ࢆሗ࿌ࡋࡓࠋࡶ࡜ࡶ

ᗘࡢ⤌ྜࡏࣜࢫࢺࢆ≧ែࣛ࣋ࣝ࡟㡰␒࡟๭ࡾᙜ࡚࡚࠸ࡓࡀࠊࡑࡢሙྜࠊࣞࣉࣜ࢝␒ྕࡀ኱

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ࡁ࠸ሙྜ࡟㑄⛣☜⋡ࡀపୗࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡋ࠿ࡋࠊ≧ែࣛ࣋ࣝࢆࣛࣥࢲ࣒࡟୪࡭ࡿࡇ࡜࡛ࡇࡢၥ㢟ࢆゎỴ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋලయⓗ࡟ࡣಟṇࡋࡓࣜࢫࢺࢆ⏝࠸ࡓሙྜ࡜ᚑ᮶ࡢࣜࢫࢺࢆ⏝࠸ࡓሙྜࢆẚ㍑ࡍࡿ
ࡓࡵࠊ࢔࣑ࣟ࢖ࢻ ȕ  ࣌ࣉࢳࢻࡢࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣜࣗࢺࢸࣥࣃࣜࣥࢢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࣛࣥࢲ࣒࡟≧ែࢆ୪࡭ࡓሙྜ࡟ࡣ㑄⛣☜⋡ࡢపୗࡀゎᾘࡉࢀࠊࢧࣥࣉࣜࣥࢢຠ⋡ࡀྥୖࡋࡓࡀࠊᚑ᮶ࡢ୪࡭᪉࡛ࡣࢧࣥࣉࣜࣥࢢຠ⋡ࡀྥୖࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ

㉥እ⥺࣮ࣞࢨ↷ᑕ࡟ࡼࡿ࣏ࣜ࢔ࣛࢽࣥจ㞟యࡢ◚ቯࢩ࣑࣮ࣗࣞࢩࣙࣥ
࢔ࣛࢽࣥࡀ㐃⥆ࡋ࡚࠸ࡿ SRO\$ ࢱࣥࣃࢡ㉁ࡣจ㞟ࡋࠊ࣏ࣜ࢔ࣛࢽࣥ⑓ࢆᘬࡁ㉳ࡇࡍࠋSRO\$ ⑓ࡢ἞⒪ἲࡣࡲࡔ☜❧ࡉࢀ࡚࠸࡞࠸ࡀࠊSRO\$ จ㞟యࢆゎ㞳ࡉࡏࡿࡇ࡜࡛ SRO\$ ࡢ⣽⬊ẘᛶࢆపୗ࡛ࡁࡿྍ⬟ᛶࡀ㧗࠸࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ୰㉥እ⥺⮬⏤㟁Ꮚ࣮ࣞࢨࡣࡇࢀࡲ࡛࠸ࡃࡘ࠿ࡢࢱࣥࣃࢡ㉁จ㞟యࡢゎ㞳࡟ᡂຌࡋ࡚࠸ࡿࠋ
ᡃࠎࡣࡇࢀࡲ࡛࡟⮬⏤㟁Ꮚ࣮ࣞࢨࡀ $ȕ ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆ◚ቯࡍࡿ㐣⛬ࢆ᭱㏆᫂ࡽ࠿࡟ࡋࡓࠋ௒ᖺᗘࡣ⮬⏤㟁Ꮚ࣮ࣞࢨࡀ SRO\$ จ㞟యࢆゎ㞳ࡉࡏࡿ㐣⛬ࢆศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥㄪ࡭ࡓࠋࡇࡇ࡛ࡣ  ಶࡢ࢔ࣛࢽࣥṧᇶ࠿ࡽ࡞ࡿ SRO\$ ࣌ࣉࢳࢻจ㞟࡟⮬⏤㟁Ꮚ࣮ࣞࢨࢆ↷ᑕࡋࡓሙྜࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ
⾜ࡋࠊࡑࡢゎ㞳㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 㸧ࠋࡑࡢ⤖ᯝࠊ࣮ࣞࢨ↷ᑕ࡟ࡼࡾࠊSRO\$ จ㞟యࡢศᏊ㛫 ȕ ࢩ࣮ࢺࡀゎ㞳ࡋࠊ࣊ࣜࢵࢡࢫᵓ㐀ࢆᣢࡘࣔࣀ࣐࣮࡟ศ㞳ࡍࡿᵝᏊࢆほᐹࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ$ȕ ࢔࣑ࣟ࢖ࢻ⥺⥔ࡢ᫬࡜ྠࡌࡼ࠺࡟࣮ࣞࢨ↷ᑕ࡟ࡼࡾ SRO\$ ࣌ࣉࢳࢻᴗ✀యࡀ୍ᗘゎ㞳ࡋࡓᚋࠊSRO\$ ࣌ࣉࢳࢻ㛫࡟ỈศᏊࡀධࡾ㎸ࡳࠊSRO\$ ࡀ෌ࡧจ㞟ࡍࡿ㐣⛬ࢆ㜼ᐖࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊ࣏ࣜ࢔ࣛࢽࣥ⑓࡜࢔ࣝࢶࣁ࢖
࣐࣮⑓࡜࠸࠺␗࡞ࡿ⑓Ẽࡢཎᅉ࡜࡞ࡿࢱࣥࣃࢡ㉁จ㞟యࡢゎ㞳࡟ࡣࠊඹ㏻ࡢ࣓࢝ࢽࢬ࣒ࡀᏑᅾࡍࡿࡇ࡜ࡀศ
࠿ࡗࡓࠋࡋ࠿ࡋࠊSRO\$ จ㞟యࡣ $ȕ จ㞟యࡼࡾࡶゎ㞳ࡋ࡟ࡃࡃࠊࡼࡾ㛗࠸᫬㛫࣮ࣞࢨࢆ↷ᑕࡍࡿᚲせࡀ࠶ࡿࡇ࡜ࡶศ࠿ࡗࡓࠋࡇࡢ⌮⏤ࡣ SRO\$ ࡀ␯Ỉᛶ࢔࣑ࣀ㓟ṧᇶࡢࡳ࡛ᵓᡂࡉࢀ࡚࠸ࡿࡓࡵ࡛࠶ࡿ࡜ㄝ࡛᫂ࡁࡓࠋ
ᅗ  ㉥እ⥺࣮ࣞࢨ↷ᑕ࡟ࡼࡿ࣏ࣜ࢔ࣛࢽࣥจ㞟య◚ቯ㐣⛬ࠋ D  ࣮ࣞࢨ↷ᑕ๓ࠋ E  ࣮ࣞࢨࣃࣝࢫ  Ⓨ↷
ᑕᚋࠋ F  Ⓨ↷ᑕᚋࠋ G  Ⓨ↷ᑕᚋࠋ H  Ⓨ↷ᑕᚋࠋ I  Ⓨ↷ᑕᚋࠋ- 446 -

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ศᏊືຊᏛィ⟬࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᾮయࡢศᏊ㛫┦஫స⏝ࡢ◊✲
Molecular interactions in liquid phase studied by molecular dynamics
simulations and quantum chemical calculations
‫ۑ‬㛗ᆏ

1

ᑗᡂ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧◊✲┠ⓗᡃࠎࡣศᏊ◊ UVSOR-III ࡢ㌾ X ⥺ࣅ࣮࣒ࣛ࢖ࣥ BL3U ࡟࠾࠸࡚ࠊᵝࠎ࡞ᾮయヨᩱࡢ㌾ X ⥺྾཰ศග(XAS)ᐃࢆ⾜ࡗ࡚ࡁࡓࠋXAS ࢫ࣌ࢡࢺࣝࡢ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡣࠊࡑࡢศᏊ㛫┦஫స⏝࡟⏤᮶ࡍࡿࠋࡑࡢࡓࡵࠊᾮ

యࡢศᏊືຊᏛ(MD)ィ⟬࡜㔞Ꮚ໬Ꮫ࡟ᇶ࡙ࡃෆẆບ㉳ィ⟬ࢆ⾜࠸ࠊᐇ㦂࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊᾮయࡢᵓ㐀ゎᯒࡀ⾜࠼ࡿࠋᮏᖺᗘࡣࠊᾮయࡢᵓ㐀ࡺࡽࡂࢆ⪃៖ࡋࡓᵓ㐀ゎᯒ᪉ἲࢆ⪃᱌ࡋ࡚ࠊᾮయ࢚ࢱࣀ࣮ࣝ(EtOH)ࡢⅣ⣲
K ྾཰➃ XAS ࢫ࣌ࢡࢺࣝࡢ෌⌧ࢆ┠ᣦࡋࡓ[3]ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
ᾮయ EtOH ࡢ MD ィ⟬࡟ࡣࠊGROMACS ࢆ⏝࠸ࡓࠋィ⟬࡟ࡣ 1000 ಶࡢ EtOH ศᏊࢆ⏝࠸࡚ࠊ25 °C ࡛ 1 atmࡢ᮲௳࡛ᾮయࡢᖹ⾮ᵓ㐀ࢆᚓࡓࠋෆẆບ㉳ィ⟬࡟ࡣᑠᮡಙ༤ᩍᤵࡢ㛤Ⓨࡋࡓ GSCF3 ࢆ⏝࠸ࡓࠋᅗ 1 ࡟♧ࡍࡼ࠺࡟ࠊෆẆບ㉳ࡍࡿ୰ᚰࡢ EtOH ศᏊ࡜ CH2 – CH2 ㊥㞳ࡀ 6 Å ௨ෆࡢ࿘ࡾࡢ EtOH ศᏊࢆྵࡴᑠࡉ࡞ࢡࣛࢫࢱ
࣮ᵓ㐀ࢆ 1000 ಶᢳฟࡋ࡚ࠊࡑࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࡢᖹᆒࢆồࡵࡿࡇ࡜࡛ࠊᵓ㐀ࡺࡽࡂࢆྵࡴᾮయ EtOH ࡢⅣ⣲ K ྾཰➃ࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋ3◊✲ᡂᯝᅗ 1(a)࡜(b)࡟ᐇ㦂࡜ෆẆບ㉳ィ⟬࡛ᚓࡽࢀࡓࠊẼయ࡜ᾮయ≧ែࡢ EtOH ࡢⅣ⣲ K ྾཰➃ XAS ࢫ࣌ࢡࢺࣝ

ࢆࡑࢀࡒࢀ♧ࡍࠋࢫ࣌ࢡࢺࣝ࡟ࡣ 4 ࡘࡢࣆ࣮ࢡࡀ☜ㄆ࡛ࡁ࡚ࠊࡑࢀࡒࢀ CH3 ᇶࡢ C 1s 㟁Ꮚࡀ 3s, 3p ㌶㐨࡟ບ㉳ࡋࡓࡶࡢࡢ࡜(CH3 3s, CH3 3p1, CH3 3p2)ࠊCH2 ᇶࡢ C 1s 㟁Ꮚࡀ 3s ㌶㐨࡟ບ㉳ࡋࡓࡶࡢ(CH2 3s)࡟ᑐᛂࡍࡿࠋ

ᅗ 1. (a) ᐇ㦂࡛ᚓࡽࢀࡓ࢚ࢱࣀ࣮ࣝࡢẼయ࡜ᾮయ≧ែࡢⅣ⣲ K ྾཰➃ XAS ࢫ࣌ࢡࢺࣝࠋ(b) ィ⟬࡛ᚓࡽࢀࡓ࢚ࢱࣀ࣮ࣝࡢẼయ࡜ᾮయ≧ែࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࠋᾮయ≧ែ࡛ࡣ CH2 – CH2 ㊥㞳ࡀ 6 Å ௨ෆࡢ࢚ࢱࣀ࣮
ࣝࡢᑠࡉ࡞ࢡࣛࢫࢱ࣮ᵓ㐀ࡢෆẆບ㉳ィ⟬ࢆከᩘ⾜ࡗࡓࠋ- 448 -

ᅗ 1(a)࡟♧ࡍࡼ࠺࡟ࠊXAS ᐇ㦂࡛ࡣ EtOH ࡀẼయ࠿ࡽᾮయ࡟࡞ࡿ࡜ࠊ᭱ࡶప࢚ࢿࣝࢠ࣮࡟࠶ࡿ CH3 3s ࣆ࣮ࢡࡀ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿࠋࡲࡓࠊẼయ࡛ࡣ CH3 3p1 ࣆ࣮ࢡ࡜ CH3 3p2 ࣆ࣮ࢡࡢ࢚ࢿࣝࢠ࣮఩⨨ࡣ㏆࠸ࡓ
ࡵࠊ1 ࡘࡢࣈ࣮ࣟࢻ࡞ࣆ࣮ࢡ࡟࡞ࡿࡀࠊᾮయ࡟࡞ࡿ࡜ࠊCH3 3p2 ࣆ࣮ࢡࡀ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿࡓࡵࠊ2 ࡘࡢࣆ࣮ࢡ࡟ศ๭ࡉࢀࡿࠋ
ᅗ 1(b)࡟ィ⟬࡛ᚓࡽࢀࡓẼయ࡜ᾮయ≧ែࡢ EtOH ࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᐇ㦂ྠᵝ࡟ 4 ࡘࡢࣆ࣮ࢡ
ࡀᚓࡽࢀࡿ࡜ඹ࡟ࠊẼయ≧ែ࡟࠾࠸࡚ࠊCH3 3p1 ࣆ࣮ࢡ࡜ CH3 3p2 ࣆ࣮ࢡࡢ࢚ࢿࣝࢠ࣮఩⨨ࡀ㏆࠸ࡓࡵࠊ1 ࡘࡢࣈ࣮ࣟࢻ࡞ࣆ࣮ࢡ࡜࡞ࡿࡇ࡜ࡀ෌⌧࡛ࡁࡓࠋࡑࡋ࡚ࠊẼయ࠿ࡽᾮయ≧ែ࡟࡞ࡿ࡜ࠊᐇ㦂⤖ᯝ࡜ྠᵝ࡟ࠊCH3
3s ࣆ࣮ࢡࡣ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿࠋࡲࡓࠊCH3 3p2 ࣆ࣮ࢡࡀࠊCH3 3p1 ࣆ࣮ࢡࡼࡾ኱ࡁ࡞㧗࢚ࢿࣝࢠ࣮ࢩࣇ
ࢺࢆ♧ࡍࡓࡵࠊẼయ࡛ࡣ 1 ࡘࡢࣈ࣮ࣟࢻ࡞ࣆ࣮ࢡ࡛࠶ࡗࡓࡢ࡟ᑐࡋ࡚ࠊᾮయ࡛ࡣ 2 ࡘࡢࣆ࣮ࢡ࡜ࡋ࡚ศ๭ࡉ
ࢀࡿࠋࡇࢀࡣᐇ㦂࡛ᚓࡽࢀࡓẼయ࠿ࡽᾮయ≧ែࡢኚ໬࡟ࡼࡿࠊXAS ࢫ࣌ࢡࢺࣝࡢᙧ≧ኚ໬ࢆⰋࡃ෌⌧ࡍࡿࠋ௨ୖࡢࡼ࠺࡟ࠊࡺࡽࡂࢆ⪃៖ࡋࡓᾮయ EtOH ࡢෆẆບ㉳ィ⟬࡟ࡼࡾࠊᐇ㦂࡛ᚓࡽࢀࡓ EtOH ࡢⅣ⣲ K ྾཰
➃ XAS ࢫ࣌ࢡࢺࣝࡢᙧ≧ኚ໬ࢆⰋࡃ෌⌧࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊ⌧ᅾࡢෆẆບ㉳ィ⟬࡛ࡣࠊẚ㍑ⓗ㛗㊥㞳ຊ࡛࠶ࡿㄏ㉳ศᴟࡢຠᯝࢆ᏶඲࡟ྲྀࡾධࢀ࡚࠸࡞࠸ࡓࡵࠊᾮయࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࡣᐇ㦂ࡼࡾࡶ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡍࡿഴྥ࡟࠶ࡿࠋ㛗㊥㞳ຊࡢෆẆບ㉳ィ⟬࡬ࡢ཯ᫎ࡟ࡘ࠸࡚ࡣࠊ௒ᚋࡢㄢ㢟࡛࠶ࡿ࡜࠸࠼ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫“ ۻ‬Development of Time-Resolved Soft X-ray Absorption Spectroscopy for Observing Photochemical Reaction in
Solution”, M. Nagasaka, Conference on Laser and Synchrotron Radiation Combination Experiment 2022 (LSC 2022),
OPTICS & PHOTONICS International Congress 2022, Yokohama (Japan), 2022/4/21. (ᣍᚅㅮ₇)[2] ‫“ ۻ‬Hydrogen bond network in aqueous dimethyl sulfoxide solutions observed by oxygen K-edge X-ray absorption
spectroscopy”, M. Nagasaka, The 18th International Conference on X-Ray Absorption and Fine Structure (XAFS 2022),
Online Conference, 2022/7/11.
[3] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿࢪ࣓ࢳࣝࢫࣝ࣍࢟ࢩࢻỈ⁐ᾮࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢゎ᫂”, 㛗ᆏᑗᡂ,➨ 25 ᅇ XAFS ウㄽ఍, ࢜ࣥࣛ࢖ࣥㅮ₇఍, 2022/8/3.
[4] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿࢪ࣓ࢳࣝࢫࣝ࣍࢟ࢩࢻỈ⁐ᾮࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢゎ᫂”, 㛗ᆏᑗᡂ,➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍, ៞᠕⩏ሿ኱Ꮫ▮ୖ࢟ࣕࣥࣃࢫ, 2022/9/19.
[5] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿ⁐ᾮࡢ໬Ꮫ⌧㇟ࡢゎ᫂”, 㛗ᆏᑗᡂ, ➨ 130 ᅇゐ፹ウㄽ఍, ᐩᒣ኱Ꮫ஬⚟࢟ࣕࣥࣃࢫ (ᐩᒣ), 2022/9/20. (ᣍᚅㅮ₇)[6] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿ⁐ᾮ཯ᛂࡢ࢜࣌ࣛࣥࢻほ”, 㛗ᆏᑗᡂ, ➨ 12 ᅇᒾ⃝ࢥࣥࣇ࢓ࣞࣥࢫࠕࢧࢫ

ࢸࢼࣈࣝ♫఍ࡢࡓࡵࡢゐ፹໬Ꮫ࣭⾲㠃⛉Ꮫࡢ᭱๓⥺ࠖ, ᕤᏛ㝔኱Ꮫ᪂ᐟ࢟ࣕࣥࣃࢫ (ᮾி), 2023/3/29. (ᣍᚅㅮ₇)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫ ۻ‬M. Nagasaka, M. Bouvier, H. Yuzawa, and N. Kosugi, “Hydrophobic Cluster Formation in Aqueous Ethanol
Solutions Probed by Soft X-ray Absorption Spectroscopy”, J. Phys. Chem. B 126, 4948-4955 (2022).
[2] ‫ ۻ‬M. Nagasaka, “Site selective analysis of water in hydrogen bond network of aqueous dimethyl sulfoxide solutionsby oxygen K-edge X-ray absorption spectroscopy”, J. Mol. Liq. 366, 120310 (7 pages) (2022).
[3] ‫ ۻ‬M. Nagasaka, “Carbon K-edge X-ray absorption spectra of liquid alcohols from quantum chemical calculationsof liquid structures obtained by molecular dynamics simulations”, J. Chem. Phys. 158, 024501 (7 pages) (2023).

- 449 -

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!*o£*T. Kosugi, T. Iida, M. Tanabe, R. Iino, and *N.Koga, De novo design of allosteric control into rotary
motor V1-ATPase by restoring lost function, Nature Chemistry (2023) (accepted).

#S. Minami, #N. Kobayashi, T. Sugiki, T. Nagashima, T. Fujiwara, R. Koga, G. Chikenji, *N. Koga,
Exploration of novel αβ-protein folds through de novo design, Nature Structural & Molecular Biology(2023) (accepted).

- 452 -

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Dive into Data of Life , 2023 ] 2 uNobuyasu Koga “De novo design of protein structures”, iNANO-IMS-ExCELLS Interdisciplinary Nanoscience

Joint Meeting, Japan 2022 ] 12 u
   ¾ªw© Design of Heme-binding proteins using coiled-coil-bridged de novo design structures ,  5 I
ExCELLS ;[P<S, ,ÀX±³¡ª|tj³>[@\[gL>, 2022 ] 12 u 12 q   Yy¹ @[J6ÊÅÄÂ1«ªinwXAd1¨±$9c/ ÜwXAd!PD[;!XtÈ4RB6=Ü+ÃÜ2022 ] 12 u
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Takahiro Kosugi "Allosteric control of rotary molecular motor by redesigning non-catalytic interface", Sendai2022

Workshop, Sendai (Aug. 2022)Ï
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journal clubÜ2022 ] 05 u.
  Nobuyasu Koga "De novo design of novel protein structures", ADVANCES IN PROTEIN FOLDING,EVOLUTION, AND DESIGN 2022, Bayreuth, Germany (Apr. 2022)Ï
- 453 -

ศᏊືຊᏛィ⟬࡟ࡼࡿᢠయࡢศᏊෆࢿࢵࢺ࣮࣡ࢡࡢ᥈ᰝ
Exploration of intramolecular networks of antibodies by molecular
dynamics simulation‫ۑ‬㇂୰ ෪Ꮚ㸦⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮/ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗᢠయࡢᶵ⬟ࡣࠊ⏕యෆ࡟⣽⳦ࡸ࢘࢖ࣝࢫ࡞࡝ࡢ␗≀ࡀ౵ධࡋࡓ㝿࡟ࠊࡑࢀࡽࢆ᤼㝖ࡍࡿࡼ࠺࡟ච␿ࢩࢫࢸ

࣒ࢆάᛶ໬ࡉࡏࡿࡇ࡜࡛࠶ࡿࠋᢠయ࡟ࡼࡿච␿ᶵ⬟ࡀⓎືࡉࢀࡿ㝿࡟ࡣࠊᢠཎ࠾ࡼࡧ࢚ࣇ࢙ࢡࢱ࣮ศᏊ࡜ࡢ
┦஫స⏝ࡀᚲせ୙ྍḞ࡛࠶ࡾࠊᢠཎࢆㄆ㆑ࡋࡓ࡜࠸࠺᝟ሗࡀ࢚ࣇ࢙ࢡࢱ࣮ศᏊ࡜⤖ྜࡍࡿ㡿ᇦࡢ≧ែ࡟཯ᫎࡉࢀ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡑࡢヲ⣽࡞࣓࢝ࢽࢬ࣒ࡣ᫂ࡽ࠿࡜࡞ࡗ࡚࠸࡞࠸ࠋᢠయࡣᢠཎ
ࡸ࢚ࣇ࢙ࢡࢱ࣮ศᏊ࡜ࡢ┦஫స⏝࡟కࡗ࡚ࠊࢻ࣓࢖ࣥࡢ┦ᑐ㓄⨨ࡀኚ໬ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ⤖ᬗᵓ㐀࠿ࡽᚓࡽࢀࡓ᩿∦ⓗ࡞▱ぢ࡟࡜࡝ࡲࡗ࡚࠸ࡿࠋࡑࡢࡓࡵࠊᢠཎ⤖ྜࡀࠊᢠయศᏊࡢᰂᵓ㐀ࡢ୰࡟㞃ࡉࢀࡓศᏊ⤒⤡ࢆ㏻ࡌ࡚ࠊ㐲఩࡟఩⨨ࡍࡿ௚ศᏊ࡜ࡢ┦஫స⏝㒊఩ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥ࡟࢔ࣟࢫࢸࣜࢵࢡ࡟ኚ໬
ࢆࡶࡓࡽࡍຠᯝ࡟ࡘ࠸࡚ࠊయ⣔ⓗ࡟⌮ゎࡉࢀ࡚࠸࡞࠸ࡢࡀ⌧≧࡛࠶ࡿࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊᢠయ඲㛗ࡢືⓗᵓ㐀࢔ࣥࢧࣥࣈࣝࢆᚓ࡚ࠊࡑࡢศᏊෆࢿࢵࢺ࣮࣡ࢡ
ࢆゎㄞࡍࡿࡇ࡜࡛ࠊᢠయࡢศᏊෆࢿࢵࢺ࣮࣡ࢡ࡟╔┠ࡋࡓᨵኚ࡟ࡼࡿ㧗ᶵ⬟ᛶᢠయࡢタィࡀྍ⬟࡜࡞ࢀࡤࠊ
ᢠయᕤᏛࡢྍ⬟ᛶࡣ኱ࡁࡃᗈࡀࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࡇࢀࡲ࡛ᡃࠎࡣච␿⣔࡟࠾࠸࡚୺せ࡞ᙺ๭ࢆᢸ࠸ࠊ⤖ᬗᵓ㐀᝟ሗࡀ㇏ᐩ࡟࠶ࡿᢠయࡢ Fc 㡿ᇦ࡟╔┠ࡋࠊࡑࡢືⓗ࡞❧యᵓ㐀࡟ࡘ࠸࡚ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜᰾☢Ẽඹ㬆㸦NMR㸧ἲ࠾ࡼࡧ X ⥺ᑠゅᩓ஘㸦SAXS㸧ἲࢆ⏝࠸ࡓᵓ㐀ゎᯒᡭἲࢆ☜❧ࡋ࡚ࡁ࡚ࡁࡓࠋࡇࡢᡭἲࢆᵝࠎ࡞⢾㙐ᵓ㐀ࢆᣢࡘᢠయࡢ Fc 㡿ᇦࡸᢠయ඲㛗࡟ᛂ⏝ࡋࠊ⢾ࢱࣥࣃࢡ㉁ࡢືⓗᵓ㐀ኚ໬ࡀᶵ⬟ࡢⓎື࡟⤖ࡧࡘࡃศᏊ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜࡟ྲྀࡾ⤌ࢇࡔࠋᢠయࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡣ AMBER ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࠾ࡼࡧ GLYCAM06 ຊሙࢆ฼⏝ࡋࡓࠋᢠయ
ࡢ Fc 㡿ᇦࢆศᏊ⏕≀Ꮫᡭἲ࡟ࡼࡗ࡚ㄪ〇ࡋࠊศᏊ⛉Ꮫ◊✲ᡤࡢ㧗☢ሙ NMR ⿦⨨ࢆ฼⏝ࡋࡓከḟඖィ࡟ࡼࡗ࡚ࠊࡑࡢ❧యᵓ㐀᝟ሗࡶྲྀᚓࡋࡓࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓᐇ㦂್࡜⌮ㄽ್ࢆẚ㍑ࡋࠊᵓ㐀ࢧࣥࣉࣜࣥࢢ
ࡢ㐺ษࡉࢆホ౯ࡋࠊᢠయࡢ⢾㙐㒊ศ࡜ࢱࣥࣃࢡ㉁㒊ศ཮᪉ࡢ❧యᵓ㐀ࢆ⁐ᾮ୰࡛ࡢࢲ࢖ࢼ࣑ࢡࢫࢆྵࡵ࡚᫂
ࡽ࠿࡟ࡍࡿࡇ࡜ࢆヨࡳࡓࠋࡉࡽ࡟ᢠయࡢศᏊෆ┦஫స⏝ࢿࢵࢺ࣮࣡ࢡࢆゎᯒࡋࠊ࣑ࢡࣟ࡞┦஫స⏝ࢿࢵࢺ࣮࣡ࢡ࡜࣐ࢡࣟ࡞ᅄḟᵓ㐀ኚ໬࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ྲྀࡾ⤌ࢇࡔࠋ

3◊✲ᡂᯝ✀ࠎࡢ␗࡞ࡿࢢࣛ࢖ࢥࣇ࢛࣮࣒ࡢ Fc ࣇࣛࢢ࣓ࣥࢺ࡟ࡘ࠸࡚ྲྀᚓࡋࡓືⓗᵓ㐀࢔ࣥࢧࣥࣈࣝࢆᑐ㇟࡟ศᏊ

ෆ࡟ᙇࡾᕠࡽࡉࢀࡓࢿࢵࢺ࣮࣡ࢡࡢゎᯒࢆᐇ᪋ࡋࡓࠋࡇࡇ࡛⏝࠸ࡓືⓗᵓ㐀࢔ࣥࢧࣥࣈࣝࡣ㔞Ꮚࣅ࣮࣒⁐ᾮᩓ஘ἲ࡞࡝࡟ࡼࡿᐇ㦂ࢹ࣮ࢱ࡟ࡼࡿ᳨ドホ౯࡟ᇶ࡙࠸࡚ࣉࣟࢺࢥࣝࢆ᭱㐺໬ࡋࡓ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡗ࡚ᚓࡽࢀࡓࡶࡢ࡛࠶ࡿࠋศᏊෆࢿࢵࢺ࣮࣡ࢡࢆᢳฟࡍࡿࡓࡵ࡟ࠊືⓗᵓ㐀࢔ࣥࢧࣥࣈࣝ࡟ᑐࡋ࡚᝟ሗ⛉Ꮫⓗ࣭⤫ィᏛⓗゎᯒࢆᛂ⏝ࡋࠊ✀ࠎࡢཎᏊ㛫ࡢ㊥㞳ࡢ᝟ሗࢆ 25,600 ಶࡢ Fc ࡢࢥࣥࣇ࢛࣐࣮㛫࡛ẚ㍑ࡋࠊཎᏊ㛫㊥㞳ࡢ┦㛵㛵ಀࢆ᫂ࡽ࠿࡟ࡋࡓࠋ≉࡟ࠊFc ࢆಟ㣭ࡍࡿ N ᆺ⢾㙐ࡢ⬺࢞ࣛࢡࢺࢩࣝ໬࡟క࠺ศᏊෆࢿࢵࢺ࣡

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࣮ࢡࡢኚ໬࡟╔┠ࡋࡓゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ⢾㙐࡜࣏ࣜ࣌ࣉࢳࢻ㙐ࡢ㛫ࡢ┦஫స⏝ࡀ᩿ࡕษࡽࢀࡿࡇ࡜
࡛ࠊࡑࢀࡀ࢚ࣇ࢙ࢡࢱ࣮ศᏊ࡜ࡢ┦஫స⏝㒊఩ࢆྵࡴศᏊࡢ 4 ḟᵓ㐀ኚ໬࡬࡜ᒎ㛤ࡍࡿ௙⤌ࡳࢆࠊFc ࡟ᙇࡾᕠࡽࡉࢀࡓศᏊࢿࢵࢺ࣮࣡ࢡࡢኚ໬࡜ࡋ࡚ᤊ࠼ࡿࡇ࡜ࡀ࡛ࡁࡓࠋ
ࡇ࠺ࡋࡓᡂᯝࢆ㋃ࡲ࠼࡚ࠊIgG ඲㛗ࡢືⓗᵓ㐀ゎᯒࢆ⾜࠺ᇶ┙ᩚഛ࡟╔ᡭࡋࡓࠋIgG ࡣ Fc ࡢ⣙㸱ಸࡢศᏊ㔞ࢆᣢࡘࡇ࡜࡟㚷ࡳ࡚ࠊࡲࡎࡣ⢒ど໬ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᑟධࡍࡿࡇ࡜࡛ຠ⋡ࡼࡃࢥࣥࣇ࢛࣓࣮ࢩࣙࣥ✵㛫ࢆ᥈ᰝࡍࡿࡇ࡜ࢆ᳨ウࡋࡓࠋࡑࡢ㝿ࠊ⢾㙐ࢆྵࡵࡓ⢒ど໬ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࣉࣟࢺࢥࣝࡢ☜❧ࡀᚲせ୙ྍḞ࡛࠶ࡿࡇ࡜࠿ࡽࠊFc ࢆࣔࢹࣝ⣔࡜ࡋ࡚ࡇࡢၥ㢟࡟ྲྀࡾ⤌ࢇࡔࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

㸦‫ۻ‬㸧S. Yanaka, R. Yogo, H. Yagi, K. Kato, “Multifaceted observation of conformational dynamics and interactions ofantibodies”, ABA-APPA-TBS Joint Congress in Taiwan㸦ᣍᚅㅮ₇㸧㸦‫ۻ‬㸧S. Yanaka, K. Kato, “Integrative approach for the observation of conformational dynamics and interactions ofantibodies”, The 7th International Symposium on Drug Discovery and Design by NMR㸦ᣍᚅㅮ₇㸧㸦‫ۻ‬㸧S. Yanaka, K. Kato, “Investigation of conformational dynamics and interactions of antibodies towards theirfunctional improvement”, ᪥ᮏ⸆Ꮫ఍➨ 143 ᖺ఍ ḟୡ௦⸆Ꮫ࢔ࢪ࢔ࢩ࣏ࣥࢪ࣒࢘ 2㸦ᣍᚅㅮ₇㸧㸦‫ۻ‬㸧S. Yanaka, R. Yogo, H. Yagi, K. Kato, “IExploring the Structural Dynamics and Interactions of Antibodies: A
Multidisciplinary Approach”, Symposium on Frontier Research for Disease-related Proteins 2023 Korea-Japan Joint
Meeting for Molecular Sciences㸦ᣍᚅㅮ₇㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

㸦‫ۻ‬㸧Kato KoichiࠊYagi HirokazuࠊYanaka Saeko, “Four-dimensional Structures and Molecular Designs of Glycans”,
Trends in Glycoscience and Glycotechnology, 34, 2022

- 455 -

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1zE. Minamitani, T. Shiga, M. Kashiwagi, I. Obayashi, “Topological descriptor of thermal conductivity in amorphous
Si ”, The Journal of Chemical Physics, 156, 244502 (2022)
2zHui-Nan Xia, Emi Minamitani, Rok Žitko, Zhen-Yu Liu, Xin Liao, Min Cai, Zi-Heng Ling, Wen-Hao Zhang,
Svetlana Klyatskaya, Mario Ruben, Ying-Shuang Fu, “Spin-orbital Yu-Shiba-Rusinov states in single Kondo molecularmagnet”, Nat. Commun. 13, 6388 (2022)- 462 -

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RN4QXRo#,.(6,6)9XNVEHKRD$$s_/@;T[6]IPJ6FSV-Z-7FSV-1Gp

6$»¿qy2D/ÅÜKRD2

r#d¼DFTÉ¾#,&)7GR:
X$¾j2Æw§!"/JP<VDky2Ð}]MC;'>#,'>N2

¾j!^-L

!#&)7GR:X$?5AbzCPP+9XNVEHKRDÞCNBß!x±"/!1

/#T,–2

/!1#CNB%?5Ax"/&)M8&)7GR:X%n #H
/Y s»¿KRDÞN-beltß%n = 6, 8

T$E7$!2!.7Þn = 4ß*x 1rÞn = 12, 14, 16ß*&)x"/!1®&)$" ¬1r

0%s»¿7.

ÙÚ@0C.Î$@0C.b!KRD$C.bi- 465 -

1r#&)E7#"/

/$, #kydÉ##6f/! &)2Zu/?Q)Ä
¡#[6]N-belt$JTV#HOMOD

4gk§^

@0CÅÜ®2Ï#/!2T

,'k:2DFTÉ¾#,¾j/#T,@4FQVl^LUMOKRDil#90o.mo'>#,P/98VP 9R%D @4FQVl^##z0/!k4²_jO4[(%Z}(1)  N-doped Nonalternant Aromatic Belt via a Six-fold Annulative Double N-Arylation
Hiroki Sato, Rie Suizu, Tomoki Kato, Akiko Yagi, Yasutomo Segawa,* Kunio Awaga, Kenichiro Itami*
Chem. Sci. 2022, 13, 9947-9951. DOI: 10.1039/D2SC02647C(2)  Perfluorocycloparaphenylenes: Fully fluorinated carbon nanorings by Ni-mediated one-pot synthesis
Hiroki Shudo, Motonobu Kuwayama, Masafumi Shimasaki, Taishi Nishihara, Youhei Takeda, Takuya
Kuwabara, Akiko Yagi, Yasutomo Segawa* and Kenichiro Itami*
Nature Commun. 2022, 13: 3713. DOI: 10.1038/s41467-022-31530-x(3)  Synthesis of a Möbius carbon nanobelt
Yasutomo Segawa,* Tsugunori Watanabe, Kotono Yamanoue, Motonobu Kuwayama, Kosuke Watanabe,
Kenichiro Itami*
Nature Synth. 2022, 1, 535–541. DOI: 10.1038/s44160-022-00075-8(4) Half-substituted fluorocycloparaphenylenes with high symmetry: Synthesis, properties and derivatization
to densely substituted carbon nanorings
Hiroki Shudo, Motonobu Kuwayama, Yasutomo Segawa, Akiko Yagi, Kenichiro Itami*
ChemRxiv 2023, DOI: 10.26434/chemrxiv-2023-zsvnt(5) An Electron-Deficient CpE Iridium(III) Catalyst: Synthesis, Characterization, and Application to EtherDirected C–H Amidation
Eiki Tomita, Masahiro Kojima, Yuki Nagashima, Ken Tanaka, Haruki Sugiyama, Yasutomo Segawa,Atsushi Furukawa, Katsumi Maenaka, Satoshi Maeda, Tatsuhiko Yoshino, Shigeki Matsunaga*
Angew. Chem. Int. Ed. 2023, DOI: 10.1002/anie.202301259(6) Polarized Raman spectroscopy on topological semimetal Co3Sn2S2
Kenya Tanaka, Taishi Nishihara, Akira Takakura, Yasutomo Segawa, Kazunari Matsuda, Yuhei
Miyauchi*J. Raman Spectrosc. 2022, 54, 93–100. DOI: 10.1002/jrs.6459- 466 -

㑄⛣㔠ᒓ㘒యゐ፹ࢆ⏝࠸ࡿ᭷ᶵ཯ᛂࡢ཯ᛂᶵᵓ◊✲̿ࣁࣟࢤࣥȪ⤖ྜࢆ฼⏝ࡋࡓศᏊㄆ㆑ᶵᵓࡢゎ᫂㸫Theoretical Study on Transition-Metal-Catalyzed Organic Reactions-Investigation of Halogen V-Bonding Interactions toward Effective Molecular Recognition˕߶୫ ޭʤ෾ࢢՌָ‫ॶڂݜ‬ʀఉ‫ښ‬Ռָ୉ָʥ
ɾ‫ٳ‬ฯ ୕໷ʤ‫౐ښ‬୉ָ୉ָӅ޽ָ‫ڂݜ‬Ռʥɾۜඎ ӵ༐ʤ‫౐ښ‬୉ָ୉ָӅ༂ָ‫ڂݜ‬Ռʥ̏ɿ‫ڂݜ‬໪దύϫΰϱ݃߻ͺඉ৙Ͷࢨ޴੓͹߶͏૮‫͍Ͳ༽ࡠޕ‬Εɼࣙ‫ހ‬ૌ৭ԿͶΓΖ‫ؽ‬೵੓ࡒྋઅ‫ܯ‬͹‫͵ྙک‬ςʖϩͳ͢ͱ‫غ‬ଶ͠Ηͱ͏Ζɽύϫΰϱ݃߻Νཤ༽ͪ͢෾ࢢ೟ࣟ෨ҒΝ࣍ͯ෾ࢢ੓΢ϱϕϨϱφ߶෾ࢢʤMIPʥΝ߻੔ͤΖ৿͢͏કྲྀΝ֋୕ͪ͢ɽMIP ௒੣࣎͹ 2 ͯ͹ҡ͵Ζ௔෾ࢢघ๑ͶΓΕɼύϫΰϱ݃߻Νղ͢ͱ๗ߵଔ‫؂‬৏͹ύϫΰϱ஖‫خ׷‬͹Ғ஖Νમ୔దͶ೟ࣟͤΖ͞ͳ͗Ͳͪ͘ɽ୊Ҳ͹๏๑ͺɼல‫ܗ‬෾ࢢ͹๗ߵଔϓρો஖‫׷‬ͶΓͮͱ ı ϙʖϩ͹γ΢θͳਜ਼͹੫ుϛτϱεϡϩΝ୉͚͘͢ɼ௔෾ࢢ஦͹ύϫΰϱ݃߻Ν‫ک‬ԿͤΖ΍͹Ͳ͍ͮͪɽ୊್͹๏๑ͺɼல‫ܗ‬෾ࢢ͹ਭો‫ࢢݬ‬ΝɼྣંͤΖ 2 ͯ͹๗ߵଔ୺ોͶ݃߻ͪ͢Ϧʖχ஖‫خ׷‬͹ؔͶ‫ڮ‬΋๏๑Ͳ͍ΖɽϦʖχ஖‫خ׷‬ͺɼԚ‫خ‬੓‫ׯ‬೵‫خ‬ϠόϜʖ͹ਭો‫΃ࢢݬ‬͹Πέιη੓Ν୉෱ͶఁԾͦ͠ɼύϫΰϱ݃߻ͳ‫ͤ߻ڟ‬Ζਭો݃߻Νཊ੏ͤΖͳߡ͓ΔΗΖɽ1H/13C NMR ͕Γ; X ત‫ٷ‬फ෾ޭʤXASFʥΝཤ༽͢ͱ‫ؽ‬೵੓ϠόϜʖͳτϱϕϪʖφ͹૮‫༹ࣞ༽ࡠޕ‬͹ಋఈͳఈྖΝߨ͏ɾಚΔΗͪ௔෾ࢢߑଆͳ҈ఈԿΝ߶੠ౕΦϋϩάʖ‫ࢋܯ‬ͶΓͮͱ‫ͪ͢ৄݗ‬ɽ̐ɿ‫ࢋܯ‬๏๑ͳ‫݃ڂݜ‬Վ0,3 Ν‫ ͪ͢ͳࡒخ‬+3/& ΩϧϞΝ༽͏ͱɾ༹ʓ͵ύϫΰϱ஖‫׷‬๗ߵଔʤεέϫϖΫγϱ༻ӹʥ͹ฯ࣍࣎ؔͳ෾཯‫ڏ‬ಊΝ֮೟ͪ͢ͳ͞ΘɾϦΤો஖‫׷‬ϗϱκϱ͕Γ;ϦΤોʗϓρો஖‫׷‬ϗϱκϱ͗࠹΍߶͏೟ࣟ೵Νࣖͪ͢ɽ͞ΗΔ͹஖‫׷‬ϗϱκϱ͹෾ࢢ΢ϱϕϨϱφ೵ͳҒ஖ҡ੓ର೟ࣟ೵Νմ໎ͤΖͪΌɾືౕ൜‫਼ؖ‬ཀྵ࿨ʤ')7ʥ‫ࢋܯ‬ʤ0; ϪϗϩʥΝߨ͏ɾϦΤોϓρો஖‫׷‬τϱϕϪʖφ෾ࢢ͹੫ుಝ੓ɾτϱϕϪʖφ෾ࢢͳ௔෾ࢢߑଆΝ࣍ͯϑωϩ΢ϝξμʖϩʤVIʥ‫ؽ‬೵੓ϠόϜʖؔ͹҈ఈԿΦϋϩάʖʤEbindingʥΝ඲Ճͪ͢ɽ
M06-2x/6-31Gʤd,pʥϪϗϩ͹ືౕ൜‫਼ؖ‬ཀྵ࿨ʤDFTʥ‫͖ࢋܯ‬ΔಚΔΗͪ੫ుϛτϱεϡϩΝ౵ືౕ໚Ͷ৯෾͜͢ͱϜρϒϱήΝߨͮͪʤਦ 1ʥ
ɽDFT ‫ࢋܯ‬Νߨ͑ࡏ͹ճ߻ର͹ॵ‫ߑغ‬ଆͺɾর͘͵Ή͢๑ʤSAʥͶΓͮͱ୵ࡩΝߨ͏ɾ࠹҈ఈΦϋϩάʖΝ༙ͤΖ෾ࢢߑଆͶͯ͏ͱ DFT ‫ࢋܯ‬ʤM06-2x/6-31G(d,p)ʥΓΖߑଆ࠹నԿΝߨͮͪɽ࠹నԿ‫ޛ‬ͶಚΔΗͪճ߻ߑଆͶͯ͏ͱ M06-2x/cc-pVDZʤaug-cc-pVDZ for fluorine, aug-cc-pVDZ-pp for
iodineʥϪϗϩ͹ DFT ‫ࢋܯ‬Νߨ͏ɾ‫خ‬ఊιρφ͹॑͸߻Κͦ‫ࠫޣ‬Νঈ‫ͤڊ‬Ζ͞ͳͶΓͮͱɾ΢ϝξμʖϩ෨Ғʷύϫΰϱ݃߻͹‫ܙ‬੔ͶΓΖ҈ఈԿΦϋϩάʖEbinding Νࢋड़ͪ͢ɽ

̑ɿ‫ڂݜ‬੔Վ৏‫ࢋܯى‬͹݃Վɾm-DIB Ͳͺɼ4-,5-,6 Ғ͹ਭો‫ࢢݬ‬Ͷ୉͘͵ਜ਼ు՛྘Ү͗؏ࡱ͠Ηͪɽ͞͹྘Ү΃͹ుࢢ‫ڛ‬༫ରʤ΢ϝξμʖϩ N ‫ࢢݬ‬ʥͳ͹݃߻Ν؏ࡱͤΖͳɾ2 Ғਭો‫ࢢݬ‬৏͹‫͏ڳ‬ਜ਼ు՛྘Үͳ΢ϝξμʖϩ N‫ͳࢢݬ‬͹݃߻ΓΕ΍݃߻‫͏୻͗཯ړ‬ɽ͠ΔͶ m-DIB ͳ 2 ‫ݺ‬͹΢ϝξμʖϩ‫ͳ؂‬෵߻ର 3 झྪͶͯ͏ͱ Ebinding͹஍Νർֳͪ͢ɽ1 ͯͺϦΤોͳ΍͑ 1 ͯͺ m-DIB ͹ਭો‫ࢢݬ‬͹͏ͥΗ͖ 1 ͯͳ૮‫ͤ༽ࡠޕ‬Ζʤਦ 2ʥɽͨ͹݃Վɼ2 ਭો‫ؖ͗ࢢݬ‬༫ͤΖ෵߻ର 1 ͗࠹΍ఁ͏ Ebinding Νࣖͪ͢ɽ͞ΗΔ͹݃ՎͺɾྣંͤΖ 2 ͯ͹๗ߵଔ୺ોͶ݃߻ͪ͢Ϧʖχ஖‫خ׷‬͹ؔͶ‫ڮ‬ΉΗͪϕϫφϱͶଲͤΖԚ‫خ‬੓‫ؽ‬೵ϠόϜʖ͹Πέιη੓͗ఁ͏͞ͳ

- 467 -

Ν‫͏ͱ࣍͢ࢩ͚ک‬ΖɽΉͪɾસͱ͹ல‫ܗ‬෾ࢢͲਜ਼͹О-hole ͗؏଎͠Ηɼύϫΰϱ݃߻ͶΓΕ҈ఈ͵ࡪରΝߑ
஛ͤΖ͞ͳ͗Ͳͪ͘ɽಝͶ m-TFDIB ͹ ı ϙʖϩͺɼ๗ߵଔϓρો஖‫׷‬ͶΓΕ୉͚͘͵ͮͱ͕Εɾଠ͹τϱϕϪʖφ෾ࢢΓΕ΍ύϫΰϱ݃߻Ͷ༙ཤ͵ߑଆͶ͵ͮͱ͏ͪɽ༻ӹ૮๎ࣻޭ XAS ͶΓΕεέϫϖΫγϱ஦͹ϦΤો‫ࢢݬ‬͹ు՛য়ସΝ඲Ճͪ͢ͳ͞Θɾm-DIB ͕Γ; TIB ஦͹ϦΤો‫ࢢݬ‬͹ XANES ͕Γ; EXAFS ηϘέφϩͺɾ‫݃ࢋܯ‬Վ͖ΔಚΔΗͪుࢢয়ସ/ճ߻ϕϫϓΟ΢ϩͳΓ͚Ҳ஗͢͢ͱ͕ΕɾεέϫϖΫγϱ஦͹ύϫΰϱ݃߻Πέιϕνʖͳ͢ͱಋ༹͹ಉ͘ΝͤΖ͞ͳ֮͗೟͠ΗͪɽҲ๏ɾm-TFDIB ͹ XANES ͹ I-K ୼ͺ mDIB Ώ TIB ͳർ΄ͱఁ͏ΦϋϩάʖͲ؏଎͠Ηɾm-TFDIB ͹ϦΤો‫͗ࢢݬ‬ଠͳർ΄ͱઞࡑదͶుࢢ෈ଏͲ͍
Ζ͞ͳ͗ࢨࣖ͠Ηͪɽࣰࡏɾm-TFDIB ͺύϫΰϱ݃߻ͶΓΕ VI ‫ׯ‬೵੓ϠόϜʖͳ߶҈ఈ͵௔෾ࢢΝߑ஛ͤ
Ζ͞ͳ͗Ն೵Ͳ͍ΕɾDFT ‫݃ࢋܯ‬Վ͖Δ΍࠹΍߶͏ Ebinding Νࣖͤ͞ͳ͗໎Δ͖ͳ͵Εɾ‫݃ࢋܯ‬Վͳ HPLC ࣰ‫ݩ‬ͶΓͮͱࢋड़͠Ηͪճ߻ఈ਼͹୉ঘ‫ܐؖ‬͹߶͏Ҳ஗֮͗೟͠Ηͪɽ

ਦ 1. m-DIB, TIB, m-TFDIB ͹ ESP Ϝρϕਦ 2. m-DIB/TIB/m-TFDIB-MeIM ͹ Ebinding̒ɿ൅නࣰ੹
ໃ̓͢ɿड़൝ࣰ੹Ήͪͺ༩ఈ
Anal. Chem. ࢿͶ‫ࡎܟ‬णཀྵ͠Ηͪ- 468 -

                   !"# $!%   & '    (  &         (  ) &       * !+   ,  &    (- ,/-    0 &   (  0       )  1& & !2&)        ,- &   0  &)
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(  &&   ) !$  ( /   &  & &    0 & 3      )   1&   ) #45/  !# 0(  & &   &    *   &    6/7                     0           (        
&   +778+!$ &  ( )    90:+4;+ :268;!

<$
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     0 * & )   (0 )) 3 , 3 46-!+  0         ) !!# <+4;+)  &  <<C <<<A     !

10 or β8722

5 or α
3
2

12
13

NH

23N
N 21
24
O HN

17

R

20 or δ15 or γO

1819     

 !

  
8     &          &      )     2 !  0  &  !  / ()              0)) E6FG=6  +)/80  !
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3)     I;DJ<<H  ) H )) /$;C5%4H  )CH ))!   KCL <+MN4  <0&       !'  )     &   )  )0   &))   KCOLP <
+MN47 &) <  )   )     )  0    !'
4   0 &   0( 0 &)  KCLC !46  0   0 0 &LQ 7C      0*   )  )        (78+)!  I;DJ5Q 7C  0 &     2Q  &  ) !+  (   &     ( &  CRCR<?=  46    )  & !
7&     /7 & 0 2 $4A!!A2!!36/7 0   &  2A!<!0;<45%4&  !#3)   )     DCH
3) 5%)4&  5%4 <DH3)(     $ 4   &  !+   A<  ) , &   -  3 0 &    / &  3)) ,> /2J-!+&3   0  &  (& &3
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- 469 -

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  &   0  ( )  !<! N$7!!C!

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8)&JJJ  0  &  0   46     0;C5%4KCL0                0         
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      &)46   *   (   S  !  0
(    T <  T!2 7C  46    )
   &                    )   (   (      !
 ) ;C5%4KCL ;C5%4 <+MN4  0 )      07C  0 ) 0    0 &!+  & (  ;C5%4)        )  &    0&    0     4  !/   )  &    /$;C5%4 I;DJ7C0    0 ))      B@U@0 )   (  !UK!C   (!+( )    (         A<!@   A!=U<!   <K!DUD!D     T!8        3         <  0
(   )    AC   T      !  +    &         )  
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&'()#*+' , **, -.'& /*  
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 &       (  3  # <+4;+  &!$  (   &) 0   0       1&    &  )   3   &  & 3   3)0       !

- 470 -

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8  &  6/7  $:+4;+  ) &   0 (  
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;<45%4&       !/ &   &   * 0  3   !>)V&& :+4;+ & &   ;<45%4+778+ &   !L( )    (        )  ! 0   )     6/7(#2$25"$2         AKD &     0 !+)    (    3  !!D@!

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:+4;+ & &   ;<45%4+778+ &   !L( )    (       )  ! 0   )      6/7(#2$25"$2         A<  &     (!+)    (    3  !K!@!

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2 " 3" 

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⍞Ꮨ㸦ಙᕞ኱Ꮫ⥲ྜ⌮ᕤᏛ◊✲⛉㸧◊✲┠ⓗᮏ◊✲ࡣࠊȘࢳ࣮ࣗࣈࣜࣥᮎ➃࡟࠾ࡅࡿ⩻ヂᚋಟ㣭ࡀࡶࡓࡽࡍᵓ㐀ኚ໬ࢆ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ

ࣙࣥ࡟ࡼࡗ࡚ゎ᫂ࡍࡿࡇ࡜࡛࠶ࡿࠋȘࢳ࣮ࣗࣈࣜࣥ࠾ࡼࡧșࢳ࣮ࣗࣈࣜࣥࡣᚤᑠ⟶ࢆᵓᡂࡍࡿࢱࣥࣃࢡ㉁࡛
࠶ࡾࠊ⏕࿨࡟࡜ࡗ࡚ᚲ㡲ࡢ⣽⬊㦵᱁ࢆᙧᡂࡋ࡚࠸ࡿࠋȘࢳ࣮ࣗࣈࣜࣥࡢ C ᮎ➃㸦ȘCTT㸧㡿ᇦࡣ⬺ࢳࣟࢩࣥ໬ࡸ࣏ࣜࢢࣝࢱ࣑ࣥ㓟໬࡞࡝ࡢ⩻ヂᚋಟ㣭ࢆཷࡅࠊᚤᑠ⟶ࡢ⏕⌮άᛶࡢㄪᩚ࡟㛵୚ࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ
ȘCTT 㡿ᇦࡣኳ↛ኚᛶ㡿ᇦ࡛࠶ࡾࠊ❧యᵓ㐀ࡢᦂࡽࡂࡀ኱ࡁࡃࠊᚤᑠ⟶ࡢ⏕⌮άᛶㄪ⠇࡟㛵ࢃࡿ⩻ヂᚋಟ㣭࡟ࡼࡿศᏊᵓ㐀ࡢືⓗ≉ᚩࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊȘCTT ࡢ⬺ࢳࣟࢩࣥ໬/ࢳࣟࢩࣥ໬࡟ࡼࡿ⩻ヂᚋಟ㣭࡟╔┠ࡋࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐺⏝ࡍࡿࡇ࡜࡛ࠊ⬺ࢳࣟࢩࣥ໬/ࢳࣟࢩࣥ໬࡟ࡼࡿศᏊㄆ㆑
ᶵᵓࢆゎᯒࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢯࣇࢺ࢙࢘࢔࡟ࡣࠊAmber20 ࠾ࡼࡧ Amber22 ࢆ⏝࠸ࡓࠋࢱࣥࣃࢡ㉁ࡢຊሙ

࡟ Amber ff14SB ࢆࠊỈศᏊࡢຊሙ࡟ࡣ TIP3P ࢆ⏝࠸ࡓࠋࡲࡓࠊ࢖࢜ࣥ⃰ᗘࡣ KCl 100mM ┦ᙜ࡟࡞ࡿࡼ࠺࡟
K+࠾ࡼࡧ Cl-࢖࢜ࣥࢆຍ࠼ࡓࠋィ⟬⣔ࡈ࡜࡟ࠊ࢚ࢿࣝࢠ࣮ᴟᑠ໬ࡢᚋࠊ᪼

࠾ࡼࡧᖹ⾮໬ࢆ⤒࡚ࠊ310K ࡟࠾

ࡅࡿ 1 ࣐࢖ࢡࣟ⛊ࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ 10 ᮏ⟬ฟࡋࡓࠋ100 ࣆࢥ⛊࠾ࡁ࡟ࢹ࣮ࢱࢆಖᏑࡋࠊゎᯒ࡟⏝࠸ࡓࠋィ⟬⣔ࡣࠊ౑⏝࣓ࣔࣜୖ㝈ࡢไ⣙࠿ࡽࠊȘCTT 㡿ᇦࡢ᩿∦㸦437-451 ࢔࣑ࣀ㓟ṧᇶ㸧ࢆ⏝࠸ࡓࠋȘCTT ࡢ C
ᮎ➃ Y451 ࡣ㓝⣲ VASH-SVBP ࡟ࡼࡗ࡚⬺ࢳࣟࢩࣥ໬ࡉࢀࡿࠋ⬺ࢳࣟࢩࣥ໬ȘCTT ᩿∦㸦ǼY-CTT㸧࠾ࡼࡧࢳࣟࢩࣥ໬ȘCTT ᩿∦㸦Y-CTT㸧࡟ࡘ࠸࡚ࠊࡑࢀࡽࢆศᏊㄆ㆑ࡍࡿࢱࣥࣃࢡ㉁࡜ࡢ┦஫స⏝ࢆィ⟬ᑐ㇟࡜ࡋࡓࠋ
ලయⓗ࡞ィ⟬⣔࡜ࡋ࡚ḟࡢ 5 ࡘ㸦Y-CTTࠊǼY-CTT ࠾ࡼࡧ」ྜయ 3 ࡘ㸧ࢆタᐃࡋࡓ㸦ᅗ 1㸧
ࠋ」ྜయ࡟ࡣࠊ
TTL㸦Tubulin Tyrosine Ligase㸧࡜ǼY-CTTࠊVASH㸦Vasohibin㸧-SVBP㸦Small Vasohibin Binding Protein㸧࡜ YCTTࠊCAP-Gly㸦Cytoskeleton-Associated Protein Glycine rich㸧domain ࡜ Y-CTT ࢆᑐ㇟࡜ࡋࡓࠋࡇࢀࡽࡢ㐟㞳≧ែ࠾ࡼࡧ⤖ྜ≧ែ࡟࠾ࡅࡿ CTT ࡢᵓ㐀㞟ᅋࢆゎᯒࡍࡿࡇ࡜࡛ࠊ⬺ࢳࣟࢩࣥ໬/ࢳࣟࢩࣥ໬ࡢᙳ㡪ࢆゎᯒࡋࡓࠋᅗ 1. ィ⟬ᑐ㇟ࡢ⣔ 5 ࡘ- 473 -

3◊✲ᡂᯝ
5 ࡘࡢィ⟬⣔࡟ࡘ࠸࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࠊ

CTT 㡿ᇦࡢ㐟㞳≧ែ࠾ࡼࡧ⤖ྜ≧ែ࡟࠾ࡅࡿᵓ㐀ࡺࡽࡂࢆゎᯒࡋ

ᅗ 2. Y-CTT ࠾ ࡼ ࡧ Ǽ Y-CTT ࡢ
RMSD ኚ໬

ࡓࠋ㐟㞳≧ែ࡟࠾ࡅࡿᵓ㐀ኚ໬࡜ࡋ࡚ࠊึᮇᵓ㐀࠿ࡽࡢ RMSD
㸦Root-Mean-Square Deviation㸧ࢆồࡵࡓ㸦ᅗ 2㸧ࠋᮏィ⟬ࢹ࣮ࢱ࠿
ࡽ 1 ࣐࢖ࢡࣟ⛊ࡢ᫬㛫ෆ࡛ Y-CTT ࠾ࡼࡧǼY-CTT ࡀ኱ࡁࡃᵓ㐀ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋC ᮎ➃ࢳࣟࢩࣥṧᇶࡢ᭷↓ࡣ㐟㞳≧ែࡢᵓ㐀㞟ᅋ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼࡚࠸࡞࠸࡜⪃࠼ࡽࢀࡿࠋ
⥆࠸࡚ࠊᵓ㐀ࡺࡽࡂ࡜ࡋ࡚ RMSF㸦Root-Mean-Square Fluctuation㸧ࢆ⟬ฟࡋࡓ㸦ᅗ 3㸧ࠋ㐟㞳≧ែࡢ RMSF ್㸦ᅗ 3 ୰ࡢⅬ⥺㸧࡟኱ᕪࡣぢࡽࢀࡎࠊC ᮎ➃ࢳࣟࢩࣥṧᇶࡢ᭷↓ࡣ CTT ᩿∦ࡢᵓ㐀ࡺࡽࡂ࡟ᙳ㡪ࢆ୚࠼࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋ⤖ྜ≧ែ࡟࠾ࡅࡿ CTT ᩿∦ࡢᵓ㐀ࡺࡽࡂࡣࠊTTL ࡜ࡢ」ྜయ࡟
࠾࠸࡚ RMSF ್ࡀపୗࡋ࡚࠸ࡓࠋ≉࡟ࠊǼY-CTT ࡢ C ᮎ➃ഃ࡟࠾࠸࡚㐟㞳≧ែࡼࡾࡶ RMSF ್ࡀపୗࡋ࡚࠸ࡓࠋTTL ࡜ࡢ┦஫స⏝

ᅗ 3. 㐟㞳≧ែ࠾ࡼࡧ⤖ྜ≧ែ࡟࠾ࡅࡿᵓ㐀ࡺࡽࡂ

࡟ࡼࡗ࡚ࠊǼY-CTT ࡢᵓ㐀ࡀᏳᐃ໬ࡉࢀࠊᵓ㐀ࡺࡽࡂࡀᢚ࠼ࡽࢀ
ࡓ࡜⪃࠼ࡽࢀࡿࠋVASH-SVBP ࡜ࡢ⤖ྜ≧ែ࡟࠾࠸࡚ࠊC ᮎ➃ࢳࣟࢩࣥṧᇶ Y451 ࡢࡺࡽࡂࡀᢚ࠼ࡽࢀ࡚࠸ࡓࠋCAP-Gly ࡜ࡢ」ྜయ
࡟࠾࠸࡚ࡣ Y-CTT ࡢᵓ㐀ࡺࡽࡂ࡟኱ࡁ࡞ᕪࡣぢࡽࢀ࡞࠿ࡗࡓࠋ
TTL ࡣ⬺ࢳࣟࢩࣥ໬ CTT ࢆㄆ㆑ࡋ࡚ࠊC ᮎ➃࡟ࢳࣟࢩࣥṧᇶࢆ௜ຍࡍࡿ㓝⣲࡛࠶ࡿࠋTTL ࡜ࡢ⤖ྜ≧ែ࡟࠾࠸࡚ǼY-CTT ࡢᵓ㐀ࡺࡽࡂࡀᢚ࠼ࡽࢀ࠾ࡾࠊ෇⁥࡞㓝⣲཯ᛂࢆ㐍ࡵࡿࡓࡵ࡟ᇶ㉁ࢆᅛ
ᐃࡍࡿຠᯝࡀ♧၀ࡉࢀࡿࠋ୍᪉ࠊVASH-SVBP ࡣࢳࣟࢩࣥ໬ CTTࢆㄆ㆑ࡋ࡚ࠊ⬺ࢳࣟࢩࣥ཯ᛂ࡟ാࡃࠋVASH-SVBP ⤖ྜ≧ែ࡟࠾࠸࡚ Y-CTT ࡢ C ᮎ➃ࢳࣟࢩࣥṧᇶ Y451 ࡢࡺࡽࡂࡀᢚ࠼ࡽࢀ࡚࠾ࡾࠊ࣌ࣉࢳࢻ⤖ྜࡢศゎ࡟ᐤ୚ࡍࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊY451 ࡜E450 ௨እࡢṧᇶ࡛ࡣ VASH-SVBP ࡜ࡢ⤖ྜ≧ែ࡟࠾࠸࡚ᵓ㐀ࡺࡽࡂࡣ㐟㞳≧ែ࡜኱ᕪ࡞࠿ࡗࡓࠋC ᮎ➃ࡢࡳᅛᐃࡍࡿࡇ࡜࡛ࠊ⤖ྜ࡟క࠺㓄ᗙ࢚ࣥࢺࣟࣆ࣮ࡢᦆኻࢆᢚ࠼ࠊ㓝⣲཯ᛂ࡟㛵ࢃࡿ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࢆୗࡆ࡚࠸ࡿࡢ࠿ࡶࡋࢀ࡞࠸ࠋ௒ᚋࡣࠊCTT ᩿∦࡜ࡢ┦஫స⏝࢚ࢿࣝࢠ࣮ࢆṧᇶࡈ࡜࡟ゎᯒࡍࡿࡇ࡜࡛ࠊTTL ࡸ
VASH-SVBP ࡢ┦஫స⏝㒊఩ࡸᇶ㉁ࡢᵓ㐀Ᏻᐃ໬ᶵᵓࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡁࡓ࠸ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ◊✲ᡂᯝࡢ୍㒊ࡣࠊಙᕞ኱Ꮫ㎰Ꮫ㒊㎰Ꮫ⏕࿨⛉Ꮫ⛉ࡢᑓᨷ◊✲ㄽᩥ㸦ㄽᩥ㢟┠㸸ࠕȘࢳ࣮ࣗࣈࣜࣥ C ᮎ➃ࢳࣟࢩࣥṧᇶࡢ⩻ヂᚋಟ㣭࡟㛵ࡍࡿศᏊ㛫┦஫స⏝ࡢゎ᫂ࠖẶྡ㸸๓⏣኱ክ㸧࡜ࡋ࡚ࡲ࡜ࡵࡿࡇ࡜ࡀ࡛ࡁ

ࡓࠋ௒ᚋࠊᮏ◊✲ࢹ࣮ࢱࡢゎᯒࢆ⥅⥆ࡋ࡚ࠊ◊✲ᡂᯝࢆ➨ 61 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍࡟࡚Ⓨ⾲ࡍࡿணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ࡇࢀࡲ࡛ࡢᡂᯝ࡜࡜ࡶ࡟ᑓ㛛ㄅ࡟ᢞ✏ࡍࡿணᐃ࡛࠶ࡿࠋ

- 474 -

࢖࢜ࣥࢳࣕࢿࣝࡢ࢖࢜ࣥ㑅ᢥᛶᶵᵓࡢゎᯒࡢࡓࡵࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ
Molecular dynamic simulation for the ion selectivity analysis of the ionchannelsධỤ ඞ㞞㸦࿴ḷᒣ┴❧་⛉኱Ꮫ⸆Ꮫ㒊㸧1◊✲┠ⓗ㑅ᢥⓗ࡞࢖࢜ࣥ㏱㐣ࡣཎጞ⏕࿨ࡀᡭ࡟ࡋࡓ᰿※ⓗ࡞᝟ሗఏ㐩ࡢᡭẁ࡛࠶ࡿࠋࡇࢀࢆྍ⬟࡟ࡍࡿ⭷㟁఩ឤཷᛶ࢖࢜ࣥࢳࣕࢿࣝࡣᡃࠎࡢ⚄⤒⣽⬊࡟࠾ࡅࡿ᝟ሗఏ㐩࡟ࡶḞ࠿ࡏ࡞࠸ࠋࡇࢀࡽࡢࢳࣕࢿࣝࡢ୺せᶵ⬟ࡣ㑅ᢥⓗ࡞࢖࢜ࣥ㏱㐣࡜⭷㟁఩ࡢឤ▱࡛࠶ࡿࠋࢼࢺ࣒ࣜ࢘࢖࢜ࣥ࡜࣒࢝ࣜ࢘࢖࢜ࣥ࡟ࡼࡿάື㟁఩ࡢⓎ⏕࡜ᾘኻࠊ࢝ࣝࢩ࣒࢘࢖࢜ࣥ࡟ࡼࡿグ᠈ᙧᡂ࡞࡝ࡢ㛗ᮇⓗ࡞ᛂ⟅ࡣࡇࢀࡽࡢ࢖࢜ࣥࢳࣕࢿࣝࡀ⭷㟁఩ࢆឤ▱ࡍࡿࡇ࡜ࡀ
ࡁࡗ࠿ࡅ࡜࡞ࡗ࡚Ⓨฟࡍࡿࠋࡑࡢࡓࡵࠊࡇࢀࡽࡣ㔜せ࡞๰⸆ᶆⓗ࡟ࡶ࡞ࡗ࡚࠸ࡿࠋ࢖࢜ࣥ㑅ᢥᛶࡢศᏊᶵᵓ
ࡢ⌮ゎࡢࡓࡵ࡟ࡣࠊࢳࣕࢿࣝࢆ㏱㐣ࡍࡿ࢖࢜ࣥࡢᣲືࢆヲ⣽࡟ゎᯒࡍࡿᚲせࡀ࠶ࡿࠋ୍ࡘࡢ࢖࢜ࣥࡢࢳࣕࢿ
ࣝ㏱㐣࡟࠿࠿ࡿ᫬㛫ࡣ 1 ࢼࣀ⛊⛬ᗘ࡜㠀ᖖ࡟▷ࡃࠊࡇࡢ㛫࡟࢖࢜ࣥࡣ㏱㐣⤒㊰୰ࡢỈศᏊ࡜」ᩘᅇࡢỈ࿴࡜⬺Ỉ࿴ࢆ⧞ࡾ㏉ࡍࠋࡇࡢࡼ࠺࡞ᚤᑠ᫬㛫࡛᏶஢ࡍࡿ⌧㇟ࢆ┤᥋ほᐹࡍࡿࡇ࡜ࡣᅔ㞴ࡔࡀࠊศᏊືຊᏛィ⟬࡛ࡣࣆࢥ⛊ࢆୖᅇࡿ᫬㛫ศゎ⬟࡛஦㇟ࢆ෌⌧࡛ࡁࡿࠋࡑࡇ࡛ࠊศᏊືຊᏛィ⟬࡟ࡼࡾ࢖࢜ࣥ㏱㐣㐣⛬ࢆゎᯒࡋࡓ࠸ࠋ⏦ㄳ⪅ࡣཎ᰾⏕≀ࡢࢼࢺ࣒ࣜ࢘ࢳࣕࢿࣝ࡟࠾࠸࡚஧౯࢝ࢳ࢜ࣥ࡟ࡼࡿάᛶ㜼ᐖࢆཷࡅࡿኚ␗యࢆ㟁Ẽ⏕⌮ᐇ㦂࠿ࡽྠᐃࡋ࡚࠾ࡾࠊࡇࢀࡽኚ␗యࡢ⤖ᬗᵓ㐀ゎᯒࢆ᏶஢ࡋ࡚࠸ࡿࠋࡑࡇ࡛ࠊࡇࡢ㜼ᐖᶵᵓࡢヲ⣽ࢆ▱ࡿࡓࡵ࡟ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ㑅ᢥᛶࡢኚ໬࡜஧౯࢝ࢳ࢜ࣥ࡟ࡼࡿ㜼ᐖࡀ⏕ࡌࡿᶵᵓࡢゎ᫂ࢆ┠ᣦࡍࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ◊✲ᑐ㇟ࡣࢼࢺ࣒ࣜ࢘ࢳࣕࢿ࡛ࣝ࠶ࡿࠋࡇࡢࢼࢺ࣒ࣜ࢘ࢳࣕࢿࣝࡢ஧౯࢝ࢳ࢜ࣥ࡟ࡼࡿ㜼ᐖࢆཷࡅࡿኚ␗

యࡢ࢖࢜ࣥ㏱㐣ࢆ⾜࠺㡿ᇦ࡛࠶ࡿ࣏࢔ࢻ࣓࢖ࣥࢆษࡾฟࡋࠊࢳࣕࢿࣝศᏊࢆ୍ศᏊྵࡳࠊ⬡㉁ࠊỈࠊ࢖࢜ࣥࢆྵࢇࡔ≧ែ࡛ 55000 ಶࡢศᏊࡀྵࡲࢀ࡚࠸ࡿ⣔࡛ࡢィ⟬ࢆ⾜࠺ࠋ㜼ᐖࢆཷࡅࡿኚ␗యࡣᅄ✀㢮࠶ࡾࡇࢀࡽ
ኚ␗య࡜㔝⏕ᆺ࡛ࡢ࢝ࣝࢩ࣒࢘࢖࢜ࣥᏑᅾୗ࡛ࡢ⭷㟁఩ࢆ-300mV Ⓨ⏕ࡉࡏࡓ≧ែ࡛ࡢ㠀ᖹ⾮≧ែ࡛ࡢ࢖࢜
ࣥࡢ㏱㐣ࢆィ⟬ࡍࡿࠋẚ㍑ࡢࡓࡵ࡟ࠊࢼࢺ࣒ࣜ࢘࢖࢜ࣥࡢࡳࢆྵࡴ᮲௳ࡢィ⟬ࡶ⾜࠺ࠋྛኚ␗యࡣึᮇᗙᶆ
ࢆࡑࢀࡒࢀ㸲ࡘ⏝ពࡋࠊྛᗙᶆ࡟ࡘ࠸࡚⊂❧࡟ 300nsec ௨ୖࡢィ⟬ࢆ⾜࠺ࠋィ⟬࡟ࡣ NAMD2 ࢆ౑⏝ࡋຊሙ࡟ࡣࠊࢱࣥࣃࢡ㉁࡜⬡㉁࡟ࡣ CHARMM36ࠊỈศᏊ࡟ࡣ TIP3P ࢆ౑⏝ࡋࡓ. ࢖࢜ࣥ࡟ࡣ electronic continuum
correction ἲ㸦ECC ἲ㸧ࢆ㐺⏝ࡋࡓࠋ3◊✲ᡂᯝᚑ᮶ࡢィ⟬ἲ࡛ࡣࠊCa2+ࡢࡼ࠺࡞஧౯࢝ࢳ࢜ࣥࡣ㈇㟁Ⲵࢆࡶࡘ㑅ᢥᛶࣇ࢕ࣝࢱ࣮࡟ᙉࡃ⤖ྜࡋࠊᮏ᮶ Ca2+࡟ࡼࡿ㜼ᐖࢆཷࡅ࡞࠸㔝⏕ᆺࡢ NavAb ࡛ࡶ Na+ࡢ㏱㐣ࡀ㜼ᐖࡉࢀ࡚ࡋࡲ࠺ࠋࡇࡢၥ㢟ࡢゎỴࡢࡓࡵ࡟ࠊECC
ἲ(Electronic continuum correction method)㸦Melcr et al. J Phys. Chem. 2018㸧࡜࿧ࡤࢀࡿࠊ⁐ᾮ୰ࡢ࢖࢜ࣥࡢⲴ㟁- 475 -

≧ែࢆṇ☜࡟ぢ✚ࡶࡿᡭἲࡢ㐺⏝ࢆ᳨ウࡋࡓࠋࡇࢀ࡟ࡼࡾ Ca2+Ꮡᅾୗ࡛ࡢ㔝⏕ᆺ࡛ࡢ Na+ࡢ㏱㐣ࢆ෌⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡉࡽ࡟ࠊࡇࡢ᮲௳࡛㜼ᐖࢆཷࡅࡿኚ␗య࡛ࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊCa2+Ꮡᅾୗ࡛ࡢ Na+ࡢ㏱㐣ࡢ㜼ᐖࡀほᐹࡉࢀࡓ(ᅗ 1)ࠋࡲࡓࠊィ⟬⤖ᯝ࠿ࡽ⟬ฟࡋࡓࠊࢳࣕࢿࣝᙜࡓࡾࡢⓎ⏕㟁ὶ್ࡀ㟁Ẽ⏕⌮ᐇ㦂࡛ᚓࡽࢀࡓࢩࣥࢢࣝࢳࣕࢿࣝ㟁ὶ࡜ࡼࡃ୍⮴ࡋ࡚࠾ࡾࠊᐇ㝿ࡢ≧ἣࢆࡼࡃ཯ᫎࡋࡓィ⟬⤖ᯝࡔ࡜ุ᩿ࡋࡓࠋ

ᅗ㸯. ࢝ࣝࢩ࣒࢘࢖࢜ࣥᏑᅾୗ࡟࠾ࡅࡿ Na+㏱㐣ࢆ෌⌧ࡋࡓศᏊືຊᏛィ⟬ࡢ⤖ᯝࠋⓑ⥺ࡣ Na+ࡢ㏱㐣ࡀ⏕ࡌ࡚࠸ࡿ௦⾲ⓗ࡞᫬㛫ᖏࠊ㯮⥺ࡣ࣏࢔㡿ᇦෆ࡟ Ca2+ࡀ⁫␃ࡍࡿ᫬㛫ᖏࢆࡋࡵࡍࠋ㔝⏕ᆺ࡛ࡣ Ca2+ࡢ⁫␃ࡣ୍᫬ⓗࡔࡀࠊCa2+࡟ࡼࡿ㜼ᐖࢆ࠺ࡅࡿ L176Q ኚ␗య࡛ࡣ Ca2+ࡢ⁫␃ࡀ㛗᫬㛫⥅⥆ࡍࡿࠋ ࡇࡢ᮲௳ୗ࡛ࠊ㜼ᐖࢆཷࡅࡿኚ␗య࡟ࡘ࠸࡚ࡶྠᵝ࡟ Na+ࡢࡳࢆྵࡴ᮲௳࡜ࡉࡽ࡟ Ca2+Ꮡᅾୗࢆྵࡴ࡜
࠸࠺஧ࡘࡢ᮲௳࡛ࡢィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊCa2+࡟ࡼࡿ㜼ᐖࢆཷࡅࡿኚ␗య࡛ࡣ࣏࢔ෆ⭍࡟ Ca2+ࡀ㛗᫬㛫⁫␃ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢ⁫␃ࡀ㟁ὶ㜼ᐖࡢཎᅉ࡜࡞ࡿ࡜⪃࠼ࡽࢀࡓࠋ
⌧ᅾࡇࡢ⤖ᯝ࡟ࡘ࠸࡚ࡲ࡜ࡵࡓㄽᩥࢆ Nature Communications ㄅ࡟ᢞ✏ࡋࠊᰝㄞࢆཷࡅࣜࣂ࢖ࢫཎ✏ࢆ㏉㏦ࡋࡓ࡜ࡇࢁ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫⤖ۻ‬ᬗᵓ㐀࡜ศᏊືຊᏛィ⟬࡟ࡼࡿ࢖࢜ࣥࢳࣕࢿࣝ࡟࠾ࡅࡿ ஧౯࢝ࢳ࢜ࣥࡢ㜼ᐖᶵᵓࡢゎᯒධỤඞ㞞᪥ᮏ⸆Ꮫ఍ ➨㸯㸲㸱ᖺ఍ 2023 ᖺ 3 ᭶ 27 ᪥‫ۻ‬ཎ᰾⏕≀⏤᮶ࢼࢺ࣒ࣜ࢘ࢳࣕࢿࣝ࡟๰ฟࡉࢀࡓ஧౯࢝ࢳ࢜ ࣥ࡟ࡼࡿ㟁ὶ㜼ᐖࡢศᏊᶵᵓධỤ ඞ㞞᪥ᮏ⏕⌮Ꮫ఍➨ 100 ᅇグᛕ኱఍ 2023 ᖺ 3 ᭶ 16 ᪥‫ۻ‬ᅄ㔞యᆺ࢖࢜ࣥࢳࣕࢿࣝ࡟࠾ࡅࡿ ஧౯࢝ࢳ࢜ࣥ࡟ࡼࡿ㜼ᐖᶵᵓࡢ ᵓ㐀ᇶ┙ࡢゎᯒධỤ ඞ㞞⏕⌮◊◊✲఍ ”ᵓ㐀᝟ሗᵓ㐀᝟ሗࢆᵓ㐀᝟ሗࢆᇶ┙࡜ࡋࡓᇶ┙࡜ࡋࡓ⭷ᶵ⬟ศᏊ࡜ࡋࡓ⭷ᶵ⬟ศᏊࡢ⭷ᶵ⬟ศᏊࡢ⏕⌮ᶵ⬟⌮ゎ࡟⏕⌮ᶵ⬟⌮ゎ࡟ྥࡅ࡚”ࡅ࡚ 2022 ᖺ 9 ᭶ 6 ᪥

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬The structural basis of the divalent cation blocking on tetrameric cation channel
Katsumasa Irie, Yoshinori Oda, Takashi Sumikama, Atsunori Oshima, Yoshinori Fujiyoshi
Research Square 2023 ᖺ 1 ᭶ 11 ᪥ୖグࣉࣞࣉࣜࣥࢺࢆ Nature Communications ㄅ࡟ࣜࣂ࢖ࢫᢞ✏୰- 476 -

4 ḟඖ MRI ࡟ࡼࡿ⬻ࡢᶵ⬟ཬࡧᵓ㐀ゎᯒFunctional and structural analysis of four dimensional MRI of the brain.
‫⚟ۑ‬Ọ 㞞႐㸦⏕⌮Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ

ᮏㄢ㢟ࡣࠊMRI(☢Ẽඹ㬆⏬ീἲ)ࢆ⏝࠸࡚཰㞟ࡉࢀࡓࠊ4 ḟඖⓗ⬻⏬ീࢹ࣮ࢱࢆ⏝࠸࡚ࠊ⬻⓶㉁ཌࠊ⬻ᅇ༢఩࡛ࡢ⓶㉁࣭ⓑ㉁య✚ࠊ⓶㉁⾲㠃✚➼ࡢᐃ㔞ⓗ࡞ゎ๗Ꮫⓗ⬻ᵓ㐀᝟ሗࡢ⟬ฟ࡜ࠊᏳ㟼᫬ཬࡧྛ✀ㄢ㢟ࠊ㈇Ⲵ
᫬ࡢ⬻άື᝟ሗࡢᢳฟࢆ⾜࠸ࠊࡇࢀࡽࡢ⬻ᵓ㐀࡜⬻ᶵ⬟ࡢ┦஫㐃㛵࡟ࡘ࠸࡚ゎᯒࠊᶵ⬟ⓗ࠾ࡼࡧᵓ㐀ⓗ⤖ྜᛶࣔࢹࣜࣥࢢࡢᐇ᪋ࢆ┠ⓗ࡜ࡍࡿࠋࡇࢀࡲ࡛ࠊ」ᩘࡢ᪋タ࡟࠾࠸࡚೺ᖖ⪅ཬࡧ⢭⚄⚄⤒⑌ᝈᝈ⪅࠿ࡽ཰㞟ࡉࢀࡓ⣙ 6000 ྡࡢ 4 ḟඖⓗ⬻ MRI ⏬ീࢹ࣮ࢱࢆ⏝࠸࡚ࠊ⓶㉁ୗᵓ㐀ࡢᐃ㔞ⓗ⏬ീィࡣࠊୖグࠊᐃ㔞ⓗ⬻ィࢆᐇ᪋ࡋࡓࠋ2022 ᖺᗘ࠾ࡼࡧ⬻ᶵ⬟⏬ീࢆ⏝࠸ࡓάື᳨ฟࢆᐇ᪋ࡋࠊࣔࢹࣝࡢ᭱㐺໬ࢆᐇ᪋ࡍࡿ࡜ඹ࡟ࠊ

᭱᪂ࣂ࣮ࢪࣙࣥࡢᐃ㔞ⓗ⬻ᵓ㐀ィࣉࣟࢢ࣒ࣛࢆᑟධࡋࠊᾏ㤿ளศ⏬ࠊᡥ᱈యள᰾ࠊどᗋள᰾ࠊどᗋୗ㒊ள᰾ࡢྠᐃ࠾ࡼࡧ⓶㉁༊⏬ྠᐃࢆ᭦᪂ࡍࡿ࡜࡜ࡶ࡟ࠊࡇࢀࡽࡢࢹ࣮ࢱࢆඖ࡟⿵ຓデ᩿ἲ࡜ࡋ࡚ᛂ⏝ࢆど㔝࡟᳨ウࢆ㐍ࡵࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㸱ḟඖ MRI ⏬ീ࠿ࡽࠊᇶᗏ᰾࡞࡝⓶㉁ୗᵓ㐀ࡢయ✚ࠊ኱⬻⓶㉁ཌࠊ኱⬻⾲㠃✚ࠊ⬻ᅇ࣭⬻⁁⾲㠃ࡢ᭤⋡࡞࡝ᐃ㔞ⓗ⬻ᵓ㐀᝟ሗࡢᢳฟ࡟ࡣ᭱᪂∧ࡢ FreeSurfer v7.2 (http://surfer.nmr.mgh.harvard.edu/)ࢆࠊ㸲ḟඖᣑᩓᙉㄪ
MRI ⏬ീ࠿ࡽⓑ㉁⥺⥔᮰ࡢᐃ㔞ⓗᣑᩓࣃ࣓࣮ࣛࢱࡢᢳฟ࡟ࡣ FSL v5.0.11 (https://fsl.fmrib.ox.ac.uk /fsl/fslwiki/)ࢆ⏝࠸࡚ᢳฟࡋࠊࢡࣛࢫࢱ࣮ࢩࢫࢸ࣒࡟ࡼࡿ୪ิ໬࡟ࡼࡾຠ⋡໬ࢆᅗࡗࡓࠋࡲࡓࠊᵓ㐀ⓗࢿࢵࢺ࣮࣡ࢡゎᯒࣉࣟࢢ࣒ࣛ TBSS ࠾ࡼࡧ BedpostXࠊ ProbTrackX ࡢࢡࣛࢫࢱࢩࢫࢸ࣒࡬ࡢᐇ⿦ࠊᶵ⬟ⓗࢿࢵࢺ࣮࣡ࢡゎᯒࣉࣟࢢ࣒ࣛ MELODIC/FIX ࠾ࡼࡧ HCPpipeline, fMRIprep, BIDS ࡢᐇ⿦ࢆࡍࡍࡵࡓࠋ3 ḟඖⓗ MRI ᵓ㐀⏬ീゎᯒࡣࠊ኱㜰኱Ꮫ࡯࠿ᅜෆ 13 ᪋タ࡛཰㞟ࡉࢀࡓ 8000 ྡࢆࡇ࠼ࡿ೺ᖖ⪅ࠊ⤫ྜኻㄪ⑕ࠊ཮ᴟᛶ㞀ᐖࠊ⮬㛢⑕ࢫ࣌ࢡࢺ࣒ࣛ㞀ᐖࠊ࠺ࡘ⑓ᛶ㞀ᐖࠊࡑࡢ௚ࡢ⑌ᝈࢆᑐ㇟࡜ࡋࡓࠋᚑ᮶ࡢ⓶㉁ࠊ⓶㉁ୗ⬻㡿ᇦ࡟ຍ࠼ࠊ⬻ᖿࠊᡥ᱈యࠊᾏ㤿ࡢள㡿ᇦ࡟ᑐࡍࡿ㡿ᇦయ✚ࠊ⓶㉁ཌࠊ⓶㉁⾲㠃✚➼ࢆ⟬ฟࡋࡓࠋ࠸ࡎࢀࡢゎᯒࡶࠊᅜ㝿ⓗ⬻⏬
ീ㑇ఏᏛࣉࣟࢪ࢙ࢡࢺ࡛࠶ࡿ ENIGMA㸦Enhancing Neuro Imaging Genetics through Meta-Analysis㸸ୡ⏺࡛ 100ࢆ㉸࠼ࡿࢢ࣮ࣝࣉࡀཧຍࡍࡿࠊ኱つᶍࢹ࣮ࢱ཰㞟ᆺࡢ⬻⏬ീ-㑇ఏᏊ㛵㐃ゎᯒ◊✲ࡢࢥࣥࢯ࣮ࢩ࢔࣒㸸
http://enigma.ini.usc.edu/ongoing/enigma-schizophrenia-working-group/㸧ࡢࣉࣟࢺࢥ࣮ࣝ࡟‽ᣐࡋᐇ᪋ࡋࡓࠋ

3◊✲ᡂᯝᐃ㔞ⓗ⬻⏬ീゎᯒࡣࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡟࠾࠸࡚ᐇ᪋ࡋࠊ඲⿕㦂⪅ࡢᐃ㔞ⓗࢹ࣮ࢱ㸦⓶㉁ୗᇶᗏ᰾࠾

ࡼࡧ⬻ᖿࠊᡥ᱈యࠊᾏ㤿ࡢள㡿ᇦࡢయ✚ࠊ⓶㉁ᵓ㐀ࡢయ✚ࠊ⓶㉁ཌ࠾ࡼࡧᣑᩓࣃ࣓࣮ࣛࢱ࣮㸧ࡢ⟬ฟࢆ⾜࠸ࠊࡇࢀࡽࢆࡶ࡜࡟⢭⚄⑌ᝈ≉␗ⓗࠊ⑌ᝈඹ㏻ࡢ⬻ᵓ㐀ኚ໬ࢆྠᐃࡋࠊㄽᩥࠊᏛ⾡Ꮫ఍࡛ሗ࿌ࡋࡓࠋ

- 477 -

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬ఀ⸨㣁ጲ, ୕ᾆ೺୍㑻, ᐑᒣᮍ᮶஀, ᯇᮏ⣧ᘺ, ⚟Ọ㞞႐, ▼୸ᚄ୍㑻, ⸨ᮏ⨾ᬛᏊ, Ᏻ⏣⏤⳹, Ώ㑓჆அ,ᶫᮏுኴ ⤫ྜኻㄪ⑕࡟࠾ࡅࡿῐ⵬⌫ࡢ⫧኱໬࡜㝧ᛶ⑕≧ࡢ㔜⑕ᗘࡢ㛵㐃㸦2022.11.4-6㸧⏕≀Ꮫⓗ⢭⚄་Ꮫ఍㺂⮫ᗋ⢭⚄⚄⤒⸆⌮Ꮫ఍㺂⚄⤒⢭⚄⸆⌮Ꮫ఍㺂⢭⚄⸆Ꮫ఍ྜྠᖺ఍ (BPCNPNPPP)‫ۻ‬ᐑᒣᮍ᮶஀, ୕ᾆ೺୍㑻, ఀ⸨㣁ጲ, ᯇᮏ⣧ᘺ, ⚟Ọ㞞႐, ▼୸ᚄ୍㑻, ⸨ᮏ⨾ᬛᏊ, Ᏻ⏣⏤⳹,ᒣ᳃ⱥ㛗, Ώ㑓჆அ, ᶫᮏுኴ ⤫ྜኻㄪ⑕࡟࠾ࡅࡿປാ᫬㛫࡜⬻ᵓ㐀ࡢ㛵㐃ཬࡧㄆ▱ᶵ⬟㞀ᐖࡢ፹௓ຠᯝࡢ
᳨ウ㸦2022.11.4-6㸧⏕≀Ꮫⓗ⢭⚄་Ꮫ఍㺂⮫ᗋ⢭⚄⚄⤒⸆⌮Ꮫ఍㺂⚄⤒⢭⚄⸆⌮Ꮫ఍㺂⢭⚄⸆Ꮫ఍ྜྠᖺ఍
(BPCNPNPPP)‫ۻ‬ᯇᮏ⣧ᘺ㺂⚟Ọ㞞႐㺂୕ᾆ೺୍㑻㺂᰿ᮏΎ㈗㺂ᒸ⏣┤኱㺂ᶫᮏ┤ᶞ㺂᳃⏣೺ኴ㑻㺂㉺ᒣኴ㍜㺂኱஭୍㧗㺂㧗ᶫດ㺂⫧⏣㐨ᙪ㺂ᒣ᳃ⱥ㛗㺂⸨ᮏ⨾ᬛᏊ㺂Ᏻ⏣⏤⳹㺂㛗㇂ᕝᑦ⨾㺂ఀ⸨㣁ጲ㺂ᡂ⏣ᑦ㺂ᶓᒣோྐ㺂୕ᔱு㺂ἙᓥᏕᙪ㺂ᑠᯘ♸Ꮚ㺂➲ᯘ኱ᶞ㺂ཎ⏣೺୍㑻㺂ᒣᮏ┿Ụ㔛㺂ᖹ㔝⨺Ⴙ㺂ᯈᶫ㈗ྐ㺂୰℧⌮ோ㺂ᶫᮏ㱟୍㑻㺂ࢱ࢟ࣥ࢟ࣥ㺂ᑠụ㐍௓㺂ᯇཎᩄ㑻㺂ᒸ⏣๛㺂ྜྷᮧ⋹ඣ㺂㜿㒊ಟ㺂㨣ሯಇ᫂㺂Ώ㑔჆அ㺂ᯇᑿᖾ἞㺂ᒣᮎⱥ඾㺂ᒸᮏὈᫀ㺂㕥ᮌ㐨㞝ࠊᑿᓮ⣖ኵ㺂➟஭ΎⓏ㺂ᶫᮏுኴ ⤫ྜኻㄪ⑕࣭཮ᴟᛶ㞀ᐖ࣭࠺ࡘ⑓࣭⮬㛢ࢫ࣌ࢡࢺ࣒ࣛ⑕ࡢከ᪋タ኱つᶍࢹ࣮ࢱ࡟ࡼࡿ⑌ᝈᶓ᩿ⓗ࡞኱⬻⓶㉁ᵓ㐀ࡢ㢮ఝᗘࡢゎᯒ㸦2022.11.4-6㸧⏕≀Ꮫⓗ⢭⚄་Ꮫ఍㺂⮫ᗋ⢭⚄⚄⤒⸆⌮Ꮫ఍㺂⚄⤒⢭⚄⸆⌮Ꮫ఍㺂⢭⚄⸆Ꮫ఍ྜྠᖺ఍ (BPCNPNPPP)‫ۻ‬ᒣ㷂㱟୍ , ᯇᮏ⣧ᘺ, ᰿ᮏΎ㈗, ⚟Ọ㞞႐, ᶫᮏ┤ᶞ, ᑠ㧗ᩥ⫄, 㧘㔝ᬕᡂ, ఀ⸨㣁ጲ, 㛗㇂ᕝᑦ⨾, Ᏻ⏣⏤⳹, ⸨ᮏ⨾ᬛᏊ, ᒣ᳃ⱥ㛗, Ώ㑓჆அ, ୕ᾆ೺୍㑻, ᶫᮏுኴ ⤫ྜኻㄪ⑕࡟≉ᚩⓗ࡞⬻య✚ῶᑡࣃࢱ࣮ࣥࡢ⤒᫬ኚ໬㸦2022.11.4-6㸧⏕≀Ꮫⓗ⢭⚄་Ꮫ఍㺂⮫ᗋ⢭⚄⚄⤒⸆⌮Ꮫ఍㺂⚄⤒⢭⚄⸆⌮Ꮫ఍㺂⢭⚄⸆Ꮫ఍ྜྠᖺ఍ (BPCNPNPPP)

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬

Sønderby IE, van der Meer D, Moreau C, Kaufmann T, Walters GB, Ellegaard M,Abdellaoui A, Ames D, Amunts
K, Andersson M, Armstrong NJ, Bernard M, BlackburnNB, Blangero J, Boomsma DI, Brodaty H, Brouwer RM,
Bülow R, Bøen R, Cahn W,Calhoun VD, Caspers S, Ching CRK, Cichon S, Ciufolini S, Crespo-Facorro B,Curran
JE, Dale AM, Dalvie S, Dazzan P, de Geus EJC, de Zubicaray GI, de ZwarteSMC, Desrivieres S, Doherty JL,
Donohoe G, Draganski B, Ehrlich S, Eising E,Espeseth T, Fejgin K, set al; ENIGMA-CNVworking group. 1q21.1
distal copy number variants are associated with cerebraland cognitive alterations in humans. Transl Psychiatry.
11:182 2021 doi: 10.1038/s41398-021-01213-0.

‫ۻ‬

Schijven D, Postema MC, Fukunaga M, Matsumoto J, Miura K, de Zwarte SMC, van Haren NEM, Cahn W,
Hulshoff Pol HE, Kahn RS, Ayesa-Arriola R, Ortiz-García de la Foz V, Tordesillas-Gutierrez D, Vázquez-Bourgon
J, Crespo-Facorro B, Alnæs D, Dahl A, Westlye LT, Agartz I, Andreassen OA, Jönsson EG, Kochunov P,
Bruggemann JM, Catts SV, Michie PT, Mowry BJ, Quidé Y, Rasser PE, Schall U, Scott RJ, Carr VJ, Green MJ,
Henskens FA, Loughland CM, Pantelis C, Weickert CS, Weickert TW, de Haan L, Brosch K, Pfarr JK, Ringwald.*6WHLQ)-DQVHQ$.LUFKHU77-1HQDGLü,.UlPHU%*UXEHU2 Satterthwaite TD, Bustillo J, Mathalon DH,
Preda A, Calhoun VD, Ford JM, Potkin SG, Chen J, Tan Y, Wang Z, Xiang H, Fan F, Bernardoni F, Ehrlich S , et al.
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Acad Sci U S A. 120:e2213880120. 2023 doi:10.1073/pnas.2213880120.

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ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⬻ᶵ⬟⏬ീゎᯒ
1HXURLPDJLQJGDWDDQDO\VLVZLWKPDFKLQHOHDUQLQJ‫ۑ‬㏆ῧ῟୍ࠊTrung Quang Pham㸦⏕⌮Ꮫ◊✲ᡤ㸧1◊✲┠ⓗィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢᙉຊ࡞ィ⟬㈨※ࢆ฼⏝ࡋ࡚ࠊ⬻ᶵ⬟⏬ീࢹ࣮ࢱ࡟ᑐࡋ࡚ࠊᶵᲔᏛ⩦ⓗゎᯒࢆ㐺⏝ࡍࡿࠋ≉࡟ࠊ῝ᒙᏛ⩦࡟࠾ࡅࡿィ⟬㈨※࡟㛵ࡋ࡚ࠊᙜࢭࣥࢱ࣮ࡣᅽಽⓗ࡛࠶ࡿࡓࡵࠊࡇࢀࢆ฼⏝ࡍࡿࡇ࡜࡟
ࡼࡾࠊ༢୍ࡢ◊✲ᐊ࡛ࣞ࣋ࣝࡣ୙ྍ⬟࡞ࠊ኱つᶍ࡞ィ⟬ࡀྍ⬟࡜࡞ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲゎᯒ࡟࠾࠸࡚ࡣࠊmatlab runtime ࢆ౑⏝ࡋ࡚࠸ࡿࠋMatlab compiler ࢆ⏝࠸࡚ࠊmatlab code ࢆࢥࣥࣃ࢖ࣝࡋࠊ

stand alone ⎔ቃ࡛㸦matlab ࣛ࢖ࢭࣥࢫࢆ౑⏝ࡏࡎ㸧ࠊmatlab code ࢆ㉮ࡽࡏࡽࢀࡿࡼ࠺࡟ࡋࡓࠋࡲࡓࠊ⌧ᅾࠊ඲ࡃ᪂ࡋ࠸ࢥࣥࢭࣉࢺ࡟ᇶ࡙ࡃࠊ⬻ᶵ⬟⏬ീࢹ࣮ࢱゎᯒἲࡢ㛤Ⓨࢆヨࡳ࡚࠸ࡿࠋ㏻ᖖࡢᶵ⬟ⓗ MRI ㄽᩥ࡟࠾࠸
࡚ࡣࠊ᫬㛫㹶✵㛫ࡢ⬻ᶵ⬟⏬ീࢹ࣮ࢱ࡟࠾࠸࡚ࠊ༢୍⏬⣲ࡢ᫬⣔ิࢆ⿕ㄝ᫂ኚᩘࠊ่⃭ᥦ♧ࡢࢱ࢖࣑ࣥࢢ࠶
ࡿ࠸ࡣ⿕㦂⪅ࡢ཯ᛂ᝟ሗࢆㄝ᫂ኚᩘ࡜ࡋࡓᅇᖐศᯒ࡟ࡼࡗ࡚ࠊࡑࡢ⏬⣲࡟࠾ࡅࡿㄆ▱ᶵ⬟ࡢᐤ୚ᗘࢆ᥎ᐃࡍ
ࡿࠋᮏ◊✲࡟࠾࠸࡚ࡣࠊࡇࡢၥ㢟ࢆ㌿⨨ࡋࠊ༢୍᫬Ⅼࡢ⬻άື࣐ࢵࣉࢆࠊㄆ▱ᶵ⬟࣐ࢵࣉ࡟ࡼࡗ࡚ᅇᖐࡍࡿ᪂つゎᯒᡭἲࢆ㛤Ⓨࡋࡓ㸦ᅗ㸯ࠊKoyama et al., ㄽᩥᢞ✏ணᐃ㸧ࠋࡇࡢᡭἲ࡟࠾࠸࡚ࡣࠊ࢜ࣥࣛ࢖ࣥୖ࡛࣓ࢱ
࢔ࢼࣜࢩࢫࢆ⾜࠺ Neurosynth ࢆ฼⏝ࡋ࡚ࠊㄆ▱ᶵ⬟࣐ࢵࣉࢆసᡂࡍࡿࠋ༢୍᫬Ⅼࡢ⬻άື࣐ࢵࣉࢆࡇࢀࡽࡢ
࣐ࢵࣉ࡛ᅇᖐࡍࡿ࡜ࠊㄆ▱ᶵ⬟ࡢάືࣞ࣋ࣝ࡟㛵ࡍࡿ᫬⣔ิ᝟ሗࢆྲྀᚓࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡿࠋࡇࡢ᪉ἲ࡛
ྲྀᚓࡋࡓ᫬⣔ิ᝟ሗࡣࠊ่⃭ᥦ♧ࡢࢱ࢖࣑ࣥࢢࡸ⿕㦂⪅ࡢ཯ᛂ᝟ሗ࡜▩┪࡞࠸ࣃࢱ࣮࡛ࣥ࠶ࡗࡓୖ࡟ࠊಶே
ࡢㄆ▱⬟ຊࢆ཯ᫎࡋࡓࡶࡢ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᅗ㸯㸸ᚑ᮶ἲࡣࠊ༢୍⏬⣲ࡢάືࢆᅇᖐࡋࠊࡇ
ࢀࢆ඲࡚ࡢ⏬⣲࡛⧞ࡾ㏉ࡍࡇ࡜࡟ࡼࡾࠊ⬻ᶵ⬟࣐ࢵࣉࢆᚓࡿࠋ᪂つἲ࡛ࡣࠊ༢୍᫬Ⅼࡢάືࢆᅇᖐࡋࠊࡇࢀࢆ඲࡚ࡢ᫬Ⅼ࡛⧞ࡾ㏉ࡍࡇ࡜࡟ࡼ
ࡾࠊㄆ▱ᶵ⬟ࡢάືࣞ࣋ࣝࡢ᫬⣔ิࢆᚓࡿࡇ࡜
ࡀ࡛ࡁࡿࠋࡉࡽ࡟ࠊࡇࡢᡭἲࢆⓎᒎࡉࡏࠊ⮬ᕫ➢ྕ໬ჾࢆ⏝࠸࡚ࠊㄆ▱ᶵ⬟࣐ࢵࣉࡢಶே᭱㐺໬࡜ࠊ⬻άືࡢ᫬⣔ิ᝟ሗࡢ᥎ᐃࢆྠ᫬࡟⾜࠺ゎᯒἲࡢ㛤Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋ
ࡇࡕࡽࡣࠊࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱࡀ㠀ᖖ࡟ከࡃࠊ࠿ࡘࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ㛫ࡢ┦஫౫Ꮡᛶࡀ㧗࠸ࡓࡵࠊgrid
search ࡞࡝ࡢࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ᥈⣴ἲࡀ౑࠼࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ᥈⣴࡟࣋࢖ࢬ᭱㐺໬ࢆᑟධࡋࡓ࡜ࡇࢁࠊᩘⓒ࢚࣏ࢵࢡ࡛ࠊ⤖ᯝࡢ཰᮰ࡀࡳࡽࢀࠊୖ㏙ࡢᅇᖐࢆ୺య࡟ࡋࡓゎᯒἲࡼࡾࡶ㧗࠸
goodness of fit ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢ⤖ᯝࡶㄽᩥ࡟ࡲ࡜ࡵ࡚Ⓨ⾲ࡍࡿ㸦2023 ᖺ 6 ᭶࡟ࡣ biorxiv ࡟࡚බ㛤㸧ࠋ

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3◊✲ᡂᯝᮏᖺᗘࡣᘬࡁ⥆ࡁࢹ࣮ࢱゎᯒࢆ㐍ࡵࡓࠋ
AMED ࡢࣉࣟࢪ࢙ࢡࢺࡢ୍㒊࡜ࡋ࡚ࠊ⬻㡿ᇦ㛫ࡢᶵ⬟ⓗ⤖ྜᛶࡢホ౯ࢆ⾜࠺᪂つᡭἲࢆ㛤Ⓨࡋࡓࠋᚑ᮶ࡢ

ゎᯒἲ࡛ࡣࠊ⬻㡿ᇦࢆᩘ༑㹼ᩘⓒࡢᑠ㡿ᇦ࡟ศ๭ࡋࠊ⬻㡿ᇦෆࡢ⬻άືࡢᖹᆒࢆィ⟬ࡋࡓᚋࠊࡑࢀࡽࡢ timecourse ࢆసᡂࡋࠊࡇࡢ time course 㛫ࡢ┦㛵ࢆ඲࡚⬻㡿ᇦࡢ⤌ࡳྜࢃࡏ࡛ィ⟬ࡍࡿᡭἲࡀ୍⯡ⓗ࡛࠶ࡗࡓࠋࡋ
࠿ࡋࠊࡇࡢᡭἲ࡛ࡣࠊ⬻㡿ᇦࡢάືࡢᚤ⣽࡞✵㛫ⓗࣃࢱ࣮ࣥࡢ᝟ሗࡀᖹᆒ໬࡟ࡼࡗ࡚ኻࢃࢀࡿࠋᚤ⣽࡞✵㛫ⓗࣃࢱ࣮ࣥࡢ᝟ሗࡣࠊᇶᮏ࿡ぬࡢ㆑ู㸦Chikazoe et al., 2019, Nature Communications㸧ࡸどぬ᝟ሗࡢ㆑ู
㸦Kamitani and Tong, 2005, Nature Neuroscience㸧ࢆྍ⬟࡟ࡍࡿࠊ㠀ᖖ࡟ rich ࡞᝟ሗࢆᣢࡘࡇ࡜ࡀ♧၀ࡉࢀ࡚࠾
ࡾࠊࡇࢀࢆ᭷ຠ࡟ά⏝ࡍࡿゎᯒᡭἲࡢ㛤Ⓨࡀᚅࡓࢀࡿࠋࡑࡇ࡛ࠊᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊ࠶ࡿ⬻㡿ᇦࡢάືࡢ
✵㛫ⓗࣃࢱ࣮ࣥ࠿ࡽࠊูࡢ⬻㡿ᇦࡢάືࡢ✵㛫ⓗࣃࢱ࣮ࣥࢆ᥎ᐃࡍࡿࣔࢹࣝࢆసᡂࡋࠊࡇࡢ᥎ᐃᡂ⦼࡟ᇶ࡙
ࡃᶵ⬟ⓗ⤖ྜࡢホ౯ἲࢆ㛤Ⓨࡋࡓࠋࡇࡢ᝟ሗࢆ⏝࠸ࡿ࡜ࠊᛶูࠊᖺ㱋ࠊ⑌ᝈࡢ᭷↓࡟ຍ࠼࡚ࠊworking memory ㄢ㢟ࡢᡂ⦼࡞࡝ࡢಶே≉ᛶࡢ᥎ᐃࡀ᭷ព࡟ᨵၿࡉࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟࡞ࡗࡓࠋ⌧ᅾࡣࠊࡇࡢ⤖ᯝࢆㄽᩥ࡟ࡲ࡜ࡵ࡚Ⓨ⾲‽ഛ୰࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃⓎ⾲ᐇ⦼‫ۻ‬㏆ῧ῟୍ࠕAutoencoder ࡟ࡼࡿ fMRI ࢹ࣮ࢱ࠿ࡽࡢㄆ▱ᶵ⬟ࡢ᫬⣔ิ᝟ሗࡢゎㄞࠖࠊ⏕⌮◊◊✲఍ࠕ➨ 2 ᅇேᕤ▱⬟ᢏ⾡࡜⛉Ꮫࡢ༠ㄪ࡜ᒎ㛤ࠖᒸᓮࠊ2022 ᖺ 7 ᭶ 14 ᪥ࠊ15 ᪥‫ۻ‬Junichi Chikazoe ࠕಶேࡢႴዲࢆᶍೌࡍࡿᶵᲔࠖࠊNeuro2022ࠊࢩ࣏ࣥࢪ࣒࢘ࠕ᝟ື᝟ሗゎㄞ࡟ࡼࡿேᩥ⣔Ꮫၥࡢ෌ᵓ
⠏ࠖἈ⦖ࠊ2022 ᖺ 6 ᭶ 30 ᪥㹼7 ᭶ 3 ᪥

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ฟ∧ணᐃ˔Yutaro Koyama, Tetsuya Yamamoto, Jun-ichiro Hirayama, Koji Jimura, Norihiro Sadato, and Junichi Chikazoe, Cognitive
Dynamics Estimation: A whole-brain spatial regression paradigm for extracting the temporal dynamics of cognitive
processes- 480 -

㻞㻚䚷㻞㻜㻞㻞ᖺᗘ㻌ィ⟬≀㉁⛉Ꮫ䝇䝟䝁䞁ඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟䛚䜘䜃฼⏝ሗ࿌᭩ᖺᗘࡼࡾࠊᮾ໭኱Ꮫ㔠ᒓᮦᩱ◊✲ᡤࠊᮾி኱Ꮫ≀ᛶ◊✲ᡤࠊ⮬↛⛉Ꮫ◊✲ᶵᵓศᏊ⛉Ꮫ◊✲ᡤ࣭ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ㸱◊✲ᡤ࡛ࡣࠊᮦᩱ⛉Ꮫࠊ≀ᛶ⛉ᏛࠊศᏊ⛉Ꮫࡢྛศ㔝ࢥ࣑ࣗࢽࢸ࢕࡟࠾ࡅࡿ୪ิィ⟬ࡢ㧗ᗘ໬࡬ࡉࡽ࡞ࡿྲྀࡾ⤌ࡳࢆಁࡍࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸱ศ㔝࡟ඹ㏻ᛶࡢ㧗࠸኱つᶍ୪ิィ⟬ࢆᚿྥࡋࡓ኱ᆺࣉࣟࢪ࢙ࢡࢺࢆᨭ᥼ࡋ࡚ࡁࡲࡋࡓࠋࡇࢀࡲ࡛ᨭ᥼ᑐ㇟࡜࡞ࡗࡓࡶࡢ
࡜ࡋ࡚ࠊᩥ⛉┬࣏ࢫࢺࠕிࠖ㔜Ⅼㄢ㢟ࠊྠࡌࡃ࣏ࢫࢺࠕிࠖⴌⱆⓗㄢ㢟ࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕᐩᓅࠖᡂᯝ๰ฟຍ㏿ࣉࣟࢢ࣒ࣛ
ㄢ㢟ࠊ-67⛉Ꮫᢏ⾡ேᮦ⫱ᡂࡢࢥࣥࢯ࣮ࢩ࢔࣒ࡢᵓ⠏஦ᴗࠊඖ⣲ᡓ␎ࣉࣟࢪ࢙ࢡࢺ㸺◊✲ᣐⅬᙧᡂᆺ㸼࡞࡝ࡀ࠶ࡾࡲࡍࠋ
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ࠉᖺᗘࡼࡾ඲&38㈨※ࡢ㸦ᖺᗘࡼࡾ⛬ᗘ㸧ࢆୖ㝈࡜ࡍࡿࠕィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟࠖࢆタ⨨ࡋࡲࡋࡓࠋ௨ୗ࡟ࠊᖺᗘ࡟ィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ◊✲ㄢ㢟࡜ࡋ࡚᥇ᢥࡉࢀࡓ◊✲ㄢ㢟ྡ୍ぴ࡜฼⏝ሗ࿌᭩ࢆᥖ㍕ࡋࡲࡍࠋ◊✲ᢸᙜ⪅ྡ
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ḟୡ௦஧ḟ㟁ụ࣭⇞ᩱ㟁ụ㛤Ⓨ࡟ࡼࡿ(7㠉࿨࡟ྥࡅࡓ
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㤋ᒣెᑦ

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- 481 -

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ィ⟬࣭ࢹ࣮ࢱᮦᩱ⛉Ꮫ◊✲㸦㺀ᐩᓅ㺁㟁ụㄢ㢟㸧&RPSXWDWLRQDODQG'DWD6FLHQFH6WXG\IRU(75HYROXWLRQE\'HYHORSPHQW
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=+28:HQFKRQJࠊ/821+XX'XFࠊ-$1*6HRQJ+RRQ㸦≀ᮦᶵᵓ㸧ࠊᮡ㔝ಟࠊ᫓ᒣ₶ࠊ∦ᒸభኴࠊ$5*8(//(6(OYLV)ODYLDQRࠊ08+$00$'<
6KLEJKDWXOODKࠊ୰す❶ᑛ㸦ᮾ኱≀ᛶ◊㸧ࠊᒸᓮ㐍ࠊᕊ⃝⠊⾜ࠊ㔠Ꮚᩄᏹࠊ୕ᔱ
ᾈ࿴㸦ᮾ኱㝔᪂㡿ᇦ㸧ࠊ㛗ᒸṇ㝯ࠊ⏣୰భ୍㸦ྡྂᒇ኱㝔᝟ሗ㸧ࠊ➉୰つ㞝㸦ᮾ኱㝔ᕤ㸧ࠊ✄ᇉὈ୍㸦៞᠕኱⌮ᕤ㸧ࠊ໭ᮧຬྜྷ㸦㟼ᒸ኱ᕤ㸧ࠊ᳃ᕝⰋᛅࠊ
℈⏣ᗄኴ㑻ࠊ✄ᇉ⪔ྖࠊ℈ᮏ㞝἞ࠊ7KDQK1JRF3+$0ࠊ%HDWUL]$QGUHD&KRL
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◊✲┠ⓗ
㺀ᐩᓅ㺁㟁ụㄢ㢟ࡣࠊ࢔ࣉࣜࢣ࣮ࢩࣙࣥࢆ㺀ᐩᓅ㺁࠾ࡼࡧ +3&, ࡟࠾࠸࡚฼ά⏝ࡍࡿࡇ࡜࡛ࠊ஧ḟ㟁ụ࠾ࡼࡧ⇞ᩱ㟁ụࡢᚤどⓗ཯ᛂᶵᵓࢆ⌮ゎ࣭ゎ᫂ࡋࠊ࠿ࡘḟୡ௦㟁ụ㛤Ⓨ࡟ྥࡅࡓࢩ࣑࣮ࣗࣞࢩ࣭ࣙࣥࢹ࣮ࢱᮦᩱ⛉Ꮫᢏ⾡ࡢ♫఍ᐇ⿦ࢆᙉຊ࡟᥎㐍ࡍࡿࡇ࡜࡟ࡼࡾࠊ⇚Ⅿ࡞ᅜ㝿➇தࡢ୰࡛ࡢᡃࡀᅜࡢ᪂つ㟁ụᮦᩱ㛤Ⓨ࣭ᐇ⏝໬࡟㈉⊩ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ඲ᅛయ㟁ụࡢ᪂つᅛయ㟁ゎ㉁ࡢᮦᩱཬࡧ⏺㠃ᣦ㔪ࡢᥦ᱌࡛ࡣࠊᅛయ⣔࡛࠶ࡿࡇ࡜࡜㑄⛣㔠ᒓࢆྵࡴࡇ࡜࠿

ࡽ୺࡟ 9$63 ࢆ⏝࠸ࡓィ⟬ᐇ⾜ࢆ⾜ࡗࡓࠋ⢏⏺ィ⟬࡟ࡘ࠸࡚ࡣᩘⓒཎᏊࣞ࣋ࣝࡢࢫ࣮ࣃࢭࣝ࡜ከᩘࡢ␗࡞ࡿ
ึᮇᵓ㐀ࢆ⏝࠸ࡓ➨୍ཎ⌮ศᏊືຊᏛ 0' ࢧࣥࣉࣜࣥࢢࡀᚲせ࡞ࡇ࡜࠿ࡽࠊ9$63 ࡢ୪ิィ⟬ຠ⋡໬ࢆ㐍ࡵࡓࠋࡉࡽ࡟➨୍ཎ⌮ 0' ࢧࣥࣉࣜࣥࢢࢆ⏝࠸ࡓ࢖࢜ࣥఏᑟᗘィ⟬ࡢࣁ࢖ࢫ࣮ࣝࣉࢵࢺ໬࡟࠾࠸࡚ࡣྛࢧࣥࣉ
ࣜࣥࢢ࡟࠾ࡅࡿ୪ิ໬࡟ຍ࠼࡚ከᩘࣀ࣮ࢻ≉ᛶࢆ༑ศ⪃៖ࡋࡓ୪ิィ⟬ࢆᐇ⾜ࡋࡓࠋ⇞ᩱ㟁ụⓑ㔠௦᭰㟁ᴟゐ፹ =U2 ࡢ㓟⣲㑏ඖάᛶࡢண

◊✲࡛ࡣࠊḞ㝗ࢆྵࡴ =U2 ࢫࣛࣈ㸦 ཎᏊ㸧ࢆ⏝࠸ࡓ➨୍ཎ⌮ィ⟬⏝ࢭࣝࡢࣔࢹࣝࢆ⏝࠸࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋࡇࡢィ⟬࡛ࡣ DE,&6 ࢆ⏝࠸ࡓ➨୍ཎ⌮ィ⟬ࣔࣥࢸ࢝ࣝࣟィ⟬ࢆ⾜ࡗࡓࠋ⇞ᩱ㟁ụ㟁ゎ㉁⭷ศᏊタィᣦ㔪ࡢᥦ᱌ࡢࡓࡵࠊ㧗ศᏊ㟁ゎ㉁⭷ࣂࣝࢡ୰ࡢỈ⣲ศᏊ࡟ᑐࡋࠊ㟁ゎ㉁⭷ࡢ୙ᆒ୍ᛶࡼࡾࡶ኱ࡁ࡞✵㛫ࢫࢣ࣮࡛ࣝࡢ㛗᫬㛫ࡢືⓗࣔࣥࢸ࢝ࣝࣟィ⟬ࢆᐇ᪋ࡋࠊࡑࡇ࡛ᚓࡽࢀࡓ  ᮏࢆ㉺࠼ࡿ㌶㊧ࢆゎᯒࡍࡿࡇ࡜࡟ࡼࡾ㍺㏦ࢲ࢖ࢼ࣑ࢡࢫࡢ࣑ࢡࣟᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋ㟁ゎᾮ⣔஧ḟ㟁ụࡢᐃ㟁఩ィ⟬࡟ࡼࡿ඘ᨺ㟁᫬ࡢ኱ᇦⓗ⏺㠃ᵓ㐀ࡢゎ᫂ࡢࡓࡵࠊ
⊂⮬㛤Ⓨࡋࡓ /$0036 ࣮࣋ࢫࡢ 5HG0RRQ ࢆ⏝࠸ࡓࠋ5HG0RRQ 50 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ 6,% ࡟࠾ࡅࡿᅛ
య㟁ゎᾮ┦㛫 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢⅣ㓟ࣇ࢚ࣝ࢜ࣟࢳࣞࣥ )(& ῧຍ๣⃰ᗘ౫Ꮡᛶ࡜ࠊࣜࢳ࣒࢘࢖࢜ࣥ㟁ụ/,% ࡟࠾ࡅࡿ 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢ඘㟁㟁఩౫Ꮡᛶ࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋ⇞ᩱ㟁ụ༢ཎᏊゐ፹ࡢ㓟⣲㑏ඖ࣭&2 㓟໬཯ᛂࡢᶵᵓゎ᫂ࡢࡓࡵࠊⅣ⣲ཎᏊࠊ㓟⣲ཎᏊࠊ࠾ࡼࡧࠊỈ⣲ཎᏊ

- 482 -

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Ⓨࡋ࡚࠸ࡿ➨୍ཎ⌮ศᏊືຊᏛἲࣉࣟࢢ࣒ࣛ 6LPXODWLRQ7RROIRU$WRP7(FKQRORJ\ 67$7(  ࢆ౑⏝ࡋࡓࠋ



◊✲ᡂᯝ

3.1

඲ᅛయ㟁ụࡢ᪂つᅛయ㟁ゎ㉁ࡢᮦᩱཬࡧ⏺㠃ᣦ㔪ࡢᥦ᱌ᅛయ㟁ゎ㉁࡟㛵ࡍࡿࡇࢀࡲ࡛࡟ࡣ࡞࠸኱つᶍ࡞➨୍ཎ⌮ 0' ィ⟬ゎᯒࢆᐇ⾜ࡋࡓࠋࡉࡽ࡟ࡑࡢ୰࡛ᾋ࠿ࡧ
ୖࡀࡗ࡚ࡁࡓㄢ㢟ࢆࡶ࡜࡟ࠊ᪂つ࢖࢜ࣥఏᑟᗘィ⟬ᡭἲ㛤Ⓨࢆヨࡳࡓࠋࡲࡎᅛయ㟁ゎ㉁࡟୙ྍ㑊࡜࡞ࡿ⢏⏺࡟࠾ࡅࡿ࢖࢜ࣥఏᑟᶵᵓࡢᏛ⌮ࢆᵓ⠏ࡍࡿࡓࡵ࡟ࠊ᭱᭷ຊ㓟໬≀ᅛయ㟁ゎ㉁࡛࠶ࡿ /L/D=U2 ⣔ࡢ⢏⏺࢖࢜ࣥఏᑟゎᯒ࡜ࡑࡢࢻ࣮ࣆࣥࢢ $O*D1E7D ຠᯝ࡟ࡘ࠸࡚ㄪ࡭ࡓࠋࢻ࣮
ࣃࣥࢺࡢᏳᐃᛶ࠿ࡽᏳᐃ⢏⏺௜㏆࡟೫ᯒࡋ࠺ࡿࡇ࡜ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟♧ࡉࢀࠊࡑࡢᏳᐃ㓄⨨࡟ᑐࡋ࡚➨୍ཎ⌮ 0' ࢆᐇ⾜ࡋᖹᆒ஧஌ኚ఩࠿ࡽᣑᩓಀᩘࢆồࡵࡓࠋࡑࡢ⤖ᯝ 1E7D ⣔࡛ࡣ⢏⏺࢖࢜ࣥఏᑟࢆຍ㏿ࡍࡿຠᯝࢆᣢࡘྍ⬟ᛶࡀ࠶ࡾࠊࡑࢀࡣ /L ࢖࢜ࣥఏᑟ⤒㊰ࡢ㐃⤖ᛶ࡜㛵㐃ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ 㸧ࠋࡲࡓࢹࣥࢻࣛ࢖
ࢺᙧᡂ࡟ࡘ࠸࡚ࡣᢚไຠᯝࡀ࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ>@ࠋᅗ 㸬 D  ᅛయ㟁ゎ㉁ /L/D=U2 ࡢ Ȉ  ⢏⏺௜㏆ࡢࢻ࣮ࣉ࡞ࡋࠊ$O ࢻ࣮ࣉࠊ1E ࢻ࣮ࣉ⣔࡟ᑐࡍࡿ⮬ᕫᣑᩓಀᩘࡢィ⟬್ࠋ1E ࢻ࣮ࣉ࡟ࡼࡾ⮬ᕫᣑᩓಀᩘࡀྥୖࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
EG  ࢻ࣮ࣉ࡞ࡋࠊ$O ࢻ࣮ࣉࠊ1E ࢻ࣮ࣉ⣔ࡢ /L ࢖࢜ࣥศᕸࠋ$O ࢻ࣮ࣉ⣔࡛ࡣ /L ఏᑟࣃࢫࡀษ᩿ࡉࢀ࡚࠸ࡿࠋ
ࡲࡓ㧗࢖࢜ࣥఏᑟᗘᅛయ㟁ゎ㉁ᮦᩱࡑࡢࡶࡢࡢ᥈⣴ࡶ࠸ࡲࡔ࡟㝈ࡽࢀࡓᮦᩱࣃ࣓࣮ࣛࢱ✵㛫࡛⾜ࢃࢀ࡚࠸ࡿㄢ㢟ࡀ࠶ࡗࡓࠋࡇࢀ࡟ᑐࡋ࡚ࠊ␗࡞ࡿ⤖ᬗᵓ㐀㛫ࡢ࢖࢜ࣥఏᑟᗘẚ㍑ࢆྠ୍ᇶ‽࡛⾜࠺ࡇ࡜ࠊ➨୍ཎ⌮ィ⟬࡛ࣞ࣋ࣝぢ✚ࡶࡾࡍࡿࡇ࡜ࢆ┠ᶆ࡜ࡋ࡚ࠊࣁ࢖ࢫ࣮ࣝࣉࢵࢺ➨୍ཎ⌮ 0' ࢧࣥࣉࣜࣥࢢࣇ࣮ࣟࡢᵓ⠏ࢆ⾜࡞ࡗࡓࠋࡇࢀ࡟ࡼࡾᩘ༓୓ࡢཎᏊ㓄⨨ࡢ୰࠿ࡽᩘ༑ࡢ᭷ᮃ࡞㓄⨨ࢆຠ⋡ⓗ࡟ồࡵࡽࢀࡿࡇ࡜ࢆᐇドࡋࡓࠋࡑࡢ⤖ᯝᗄࡘ࠿ࡢ᭷ᮃ࡞ 1D ࢖࢜ࣥ◲໬≀㟁ゎ㉁ࡢᥦ᱌࡟⮳ࡗࡓࠋࡉࡽ࡟ከᩘࡢィ⟬ࢹ࣮ࢱࢆᶵᲔᏛ⩦࡟࠿ࡅࡿࡇ࡜࡟ࡼࡾࠊ㧗࢖࢜ࣥఏᑟᗘࡢࡓࡵ࡟㔜せ࡞グ㏙Ꮚࡢᢳฟࡶ⾜࡞ࡗࡓ㸦ᅗ 㸧ࠋᚓࡽࢀࡓグ㏙Ꮚࡣࠊ㏆ᖺᥦ᱌ࡉࢀ࡚࠸ࡿᵝࠎ࡞ᴫᛕ࡜ࡶᩚྜࡍࡿࡶࡢ࡜࡞ࡗ࡚࠾ࡾࠊ᫬㛫ࡢ࠿࠿ࡿ➨୍ཎ⌮ 0' ࢆ௦࡛᭰ࡁࡿྍ⬟ᛶࢆ⛎ࡵ࡚࠸ࡿ>@ࠋ- 483 -ᅗ 㸬㸦ᕥ㸧㧗࢖࢜ࣥఏᑟᗘᅛయ㟁ゎ㉁᥈⣴ࡢࡓࡵࡢࣁ࢖ࢫ࣮ࣝࣉࢵࢺࢫࢡ࣮ࣜ
ࢽࣥࢢࡢᴫ␎ᅗࠋ
㸦ྑ㸧ィ⟬ࢹ࣮ࢱࢆࡶ࡜࡟ᚓࡽࢀࡓ 1D ࢖࢜ࣥᐊ⮬ᕫᣑᩓಀᩘࡢᅇᖐᘧࠋ㸱ࡘࡢ୺せグ㏙Ꮚࡣ⌧㇟ࢆ࠺ࡲࡃㄝ᫂ࡋ࡚࠸ࡿࠋ

ࡇࡢࡼ࠺࡞ࣁ࢖ࢫ࣮ࣝࣉࢵࢺ࢖࢜ࣥఏᑟᗘィ⟬ࡀ➨୍ཎ⌮ィ⟬࡛ࣞ࣋ࣝྍ⬟࡟࡞ࡗࡓࡀࠊࡉࡽ࡟࢖࢜ࣥఏ
ᑟィ⟬ࡢຠ⋡໬ࢆᅗࡿࡓࡵ࡟ᡃࠎࡣ㠀ᖹ⾮ 0' ἲࡢࣇ࣮࣒࣮ࣞ࣡ࢡࡢᣑᙇࢆヨࡳࡓࠋ㟁Ⲵ࡜ࡋ࡚࢖࢜ࣥࡢᐇ
㟁Ⲵࢆ⪃៖ࡋࡓタᐃࢆ⾜࠺ &KHPLFDO &RORU 'LIIXVLRQ ἲࢆ᪂ࡓ࡟㛤Ⓨࡋࠊ᪤Ꮡࡢ◲໬≀ᅛయ㟁ゎ㉁࡟㐺⏝ࡋ࡚ጇᙜᛶࢆ᳨ドࡋࡓ࡜ࡇࢁࠊ⢭ᗘࢆ࣮࢟ࣉࡋ࡞ࡀࡽ⣙㸯㸮ಸࡢィ⟬㏿ᗘྥୖࡀᅗࡽࢀࡿࡇ࡜ࡀᐇドࡉࢀࡓ㸦ᅗ㸧ࠋᮏᡭἲࡣ࢖࢜ࣥྠኈࡢ┦㛵ࢆࡼࡾ㧗⢭ᗘ࡟ᢅ࠼ࡿࡇ࡜࠿ࡽࠊ᭱ඛ➃࢖࢜ࢽࢡࢫィ⟬ࢆྍ⬟࡟ࡍࡿࡶࡢ࡜
࡞ࡗ࡚࠸ࡿ>@ࠋᅗ 㸬㸦ᕥ㸧/L*H36 ࣔࢹࣝ⣔࡟࠾ࡅࡿ /L ࢖࢜ࣥࠊ࢔ࢽ࢜ࣥࣘࢽࢵࢺࡢ㟁Ⲵ࠾ࡼࡧ࣮࢝ࣛ㟁Ⲵࣇࣛࢵࢡࢫࡢᐃ⩏ࠋ㸦ྑ㸧⮬ᕫ┦㛵࠾ࡼࡧ࢖࣮࢜ࣥ࢖࢜ࣥ┦㛵ࢆ⪃៖ࡋࡓ࢖࢜ࣥఏᑟᗘࡢᐃ⩏ࠋ&&'1(0' ࡟ࡼࡾ࢖࢜ࣥ┦㛵ࢆ⪃៖ࡋࡓ࢖࢜ࣥఏᑟᗘࡢ 0' ィ⟬ࡢ⤫ィ཰᮰ᛶࡀᚑ᮶ࡢ⣙㸯㸮ಸ㏿ࡃ࡞ࡗࡓࠋᮏᡭἲࡣ࢖࢜ࣥఏᑟᗘゎᯒࢆಁ㐍ࡍࡿࡶࡢ࡛࠶ࡿࠋ

3.2 ⇞ᩱ㟁ụⓑ㔠௦᭰㟁ᴟゐ፹ ZrO2 ࡢ㓟⣲㑏ඖάᛶࡢணⓑ㔠௦᭰㟁ᴟゐ፹ =U2 ୖ࡛␗ඖ⣲ࢻ࣮ࣉ࡟ࡼࡿ㓟⣲㑏ඖ཯ᛂࡢάᛶ໬ᶵᵓゎ᫂ࡢࡓࡵ࡟ࠊࢻ࣮ࣃࣥࢺศᕸ
ࡸᢸయࠊỈ⁐ᾮࡢᙳ㡪ࢆ⪃៖ࡋࡓィ⟬㸦ィ⟬ᶵᐇ㦂㸧ࢆ⾜ࡗࡓࠋࢻ࣮ࣃࣥࢺศᕸࢆᚓࡿࡓࡵ࡟➨୍ཎ⌮ィ⟬ࣔࣥࢸ࢝ࣝࣟィ⟬ࢆ⾜ࡗࡓࡀࠊ㏵୰⤒㐣ࢆᶵᲔᏛ⩦ࡋ࡚ຊሙ࣏ࢸࣥࢩࣕࣝࡀᵓ⠏࡛ࡁࡿࡢ࡛ࠊィ⟬᫬㛫ࢆ▷⦰ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋィ⟬⤖ᯝ࡟ᇶ࡙ࡁࠊ㓟⣲✵Ꮝࡣᗈࡃศᕸࡍࡿࡀࠊ❅⣲୙⣧≀ࡣ⏺㠃௜㏆࠿ࡽ㞳ࢀ࡚ศ- 484 -

ᕸࡍࡿࡇ࡜࡞࡝ᵓ㐀࡟㛵ࡍࡿ≉ᚩࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋᚓࡽࢀࡓᵓ㐀ࢆ⏝࠸࡚ࠊ㓟⣲㑏ඖ཯ᛂᶵᵓ
ࡢィ⟬ࠊỈ⁐ᾮ⏺㠃ࡢィ⟬ࢆࡑࢀࡒࢀ⾜ࡗࡓࠋ๓⪅ࡢィ⟬ࡢࡓࡵ࡟ࠊࡲࡎ⾲㠃ᵓ㐀ࡢ୰࠿ࡽ㔜せ࡛࠶ࡿ࡜᝿
ᐃࡉࢀࡿḞ㝗ࡢศᕸࡸ཯ᛂࢧ࢖ࢺࢆ඲࡚⏝࠸ࠊ཯ᛂ⤒㊰ࡢィ⟬ࢆ⾜ࡗࡓ㸦ᅗ 㸧ࠋḞ㝗࠶ࡾࡢᶍᆺ࡜Ḟ㝗࡞ࡋࡢᶍᆺ࡛᭱ࡶάᛶ࡞ࢧ࢖ࢺࢆẚ࡭ࡿ࡜ࠊ࡯࡜ࢇ࡝㐪࠸ࡀ⌧ࢀ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊ㟁ᴟゐ፹ࢆ㟁Ꮚ౪⤥⬟࡜άᛶ⬟࡟ศゎࡋ࡚⪃࠼ࡓ᫬ࠊ๓⪅ࡀ᭱ࡶ㔜せ࡞ᅉᏊ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿࡶࡢ࡛࠶ࡾࠊゐ፹タィ࡟࡜ࡗ࡚㔜せ࡞▱ぢ࡜࡞ࡗࡓ>@ࠋ㼆㼞 㻻ᅗ 㸬W=U2  ୖ࡛ࡢ㓟⣲㑏ඖ཯ᛂ⤒㊰ࠋከᩘࡢ㓟⣲✵Ꮝ࡜❅⣲୙⣧≀ࠊ཯ᛂ୰㛫యࡢ⤌ࡳྜࢃࡏ࠿ࡽ㔜せ࡞ࡶࡢᩘⓒ㏻ࡾࢆ⥙⨶ⓗ࡟⪃៖ࡋ࡚཯ᛂ⤒㊰ࢆồࡵࡓࠋከᵝ࡞⤖ྜᙧែࢆྲྀࡿ஦ࡀάᛶ
໬࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡋ࡚࠸ࡿᵝᏊࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
ᚋ⪅ࡢᅛᾮ⏺㠃ࡢᵓ㐀ࡢィ⟬ࡢࡓࡵ࡟ࡣࠊỈࡢึᮇᵓ㐀ࢆ᝿ᐃࡋ࡚ᇶ࡙ࡁ➨୍ཎ⌮ศᏊືຊᏛィ⟬ࢆࡲࡎ⾜࠸ࠊࡑࡢ⤖ᯝ࡟ᇶ࡙ࡁᶵᲔᏛ⩦ຊሙ࣏ࢸࣥࢩࣕࣝࡢᵓ⠏ࢆ⾜ࡗࡓ>@ࠋࡉࡽ࡟ຊሙࢆ⏝࠸ࡓ  QV つᶍࡢศᏊືຊᏛィ⟬ࢆ  ㏻ࡾ⾜࠸ࠊ⤫ィࢧࣥࣉࣜࣥࢢࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ᝿ᐃࡉࢀࡓᵓ㐀࡜ຊሙィ⟬࠿ࡽᚓࡽࢀ
ࡓᵓ㐀ࡀ୍⮴ࡍࡿࡲ࡛⮬ᕫ↓᧐╔ィ⟬ࢆ⾜ࡗࡓࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓᵓ㐀࠿ࡽࠊỈศᏊࡀ㒊ศⓗ࡟஋㞳྾╔ࡋ࡚㓟⣲㑏ඖ཯ᛂࢆࣈࣟࢵࢡࡍࡿᵝᏊࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦ᅗ 㸧ࠋᅗ 㸬W=U2  ୖ࡛ࡢỈࡢᵓ㐀ࠋᅛయഃࡢḞ㝗ศᕸࢆ࠶ࡽ࠿ࡌࡵ➨୍ཎ⌮ィ⟬ࣔࣥࢸ࢝ࣝࣟィ⟬➼࡛ồࡵࡓୖ࡛⾲㠃ࢆỈศᏊ࡛そ࠸ࠊ➨୍ཎ⌮ศᏊືຊᏛィ⟬ࢆ  ㏻ࡾᐇ᪋ࡋ࡚⏺㠃ᵓ㐀ࢆỴᐃࡋࡓࠋ⏺㠃࡛Ỉࡀ஋㞳྾╔ࡋ࡚㟁Ẽ஧㔜ᒙࢆᙧᡂࡋࠊ㓟⣲㑏ඖ཯ᛂ࡟ᙳ㡪ࢆཬࡰࡍᵝᏊࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
- 485 -

3.3

⇞ᩱ㟁ụ㟁ゎ㉁⭷ศᏊタィᣦ㔪ࡢᥦ᱌⇞ᩱ㟁ụ㟁ᴟ⏺㠃ᵓ㐀ࡢྜ⌮ⓗタィࡢࡓࡵࡢ⏺㠃タィᣦ㔪ࡢ⋓ᚓ࡟ྥࡅ࡚ࠊ௧࿴㸱ᖺᗘࡲ࡛࡟㛤Ⓨࡋࡓ᪂つືⓗࣔࣥࢸ࢝ࣝࣟἲ࡟ᇶ࡙࠸࡚ࠊ㏻ᖖࡢศᏊືຊᏛィ⟬࡛ࡣ୙ྍ⬟࡞ࠊ㧗ศᏊ㟁ゎ㉁⭷୰࡛ࡢỈ⣲ศᏊࡢ㛗᫬㛫࡟ࢃࡓࡿ㌶㊧ࢆ㸯୓ᮏ௨ୖ⏕ᡂࡋࠊᚓࡽࢀࡓỈ⣲ࡢ኱㔞ࡢ㌶㊧࠿ࡽᣑᩓ⤒㊰ࡢ≉ᚩࢆᢳฟࡋࠊ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡸศᏊࡀ㢖⦾࡟㏻ࡿ⤒㊰ୖࡢሙᡤ࡞࡝ࢆゎ᫂ࡋࡓ㸦ᅗ 㸧ࠋࡇࢀࡽࡢゎᯒ࠿ࡽࠊ㟁ゎ㉁⭷࡜⁐፹࡛࠶ࡿỈࡢᒁᡤⓗ࡞ᐦᗘࡀỈ⣲ศᏊࡢ㍺㏦ࢆỴᐃࡍࡿ኱ࡁ࡞ᅉᏊ࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࠊ㟁ゎ㉁⭷タィࡢࡦ࡜ࡘࡢᣦ㔪ࢆᚓࡓ>@ࠋᅗ 㸬᪂つືⓗࣔࣥࢸ࢝ࣝࣟἲ࡟ࡼࡾ⏕ᡂࡋࡓỈ⣲ศᏊࡢ㧗ศᏊ㟁ゎ㉁⭷୰ࡢ኱ᇦⓗ࡞㌶㊧࡜ࠊ㌶㊧࠿ࡽᢳฟࡋࡓᣑᩓ⤒㊰ࡢ≉ᚩࠋࡇࡢᢏ⾡࡟ᑐࡋ࡚ࡣࠊ௻ᴗ࡜ࡢඹྠ◊✲ࡸࠊ࣒࣮ࣥࢩࣙࢵࢺࣉࣟࢪ࢙ࢡࢺ࡞࡝௚ࡢᅜᐙࣉࣟࢪ࢙ࢡࢺ࡬ࡢ
ᒎ㛤➼ࢆ㏻ࡋ࡚♫఍ᐇ⿦ࢆ⾜ࡗࡓࠋ3.4㟁ゎᾮ⣔஧ḟ㟁ụࡢᐃ㟁఩ィ⟬࡟ࡼࡿ඘ᨺ㟁᫬ࡢ኱ᇦⓗ⏺㠃ᵓ㐀ࡢゎ᫂ձࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢ )(& ῧຍ๣⃰ᗘ౫Ꮡᛶ>@6(, ⭷ࡢ඘ᨺ㟁ࢧ࢖ࢡࣝ୰ࡢᏳᐃᛶࡣࠊࡑࡢᚤどⓗᙎᛶ⋡࡜ᐦ᥋࡟㛵ಀࡋ࡚࠸ࡿࠋࡑࡇ࡛ࠊ)(& ࡀῧຍࡉࢀࡓ࣊࢟ࢧࣇࣝ࢜ࣟࣜࣥ㓟ࢼࢺ࣒ࣜ࢘ 1D3) Ⅳ㓟ࣉࣟࣆࣞࣥ 3& ⣔ 6,% ࡟࠾ࡅࡿ 50 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟
ࡼࡗ࡚ᚓࡽࢀࡓ 6(, ⭷࡟ᑐࡋ࡚ຊᏛⓗ≉ᛶィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ)(& ῧຍ๣⃰ᗘࡀ  YROࡢ࡜ࡁ࡟ᙎ
ᛶಀᩘࡢྛᡂศࡀ᭱኱࡜࡞ࡿࡇ࡜ࡀึࡵ࡚⌮ㄽⓗ࡟᫂ࡽ࠿࡜࡞ࡗࡓࠋᙎᛶಀᩘࡢ )(& ῧຍ๣⃰ᗘ౫Ꮡᛶࡢゎᯒ࠿ࡽࠊ)(& ῧຍ๣ప⃰ᗘ࡛ᙧᡂࡉࢀࡓ 6(, ⭷ࡣᘬᙇኚᙧࡸࡏࢇ᩿ኚᙧ࡟ᑐࡋ࡚ࡼࡾ⪏ᛶࡀ࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ᭱㐺࡞◳ᗘࡣ )(& ῧຍ๣⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀ࡚༢ㄪ࡟ῶᑡࡍࡿࡀࠊప࠸ )(& ῧຍ๣⃰ᗘ࡛ࡣᩄឤ࡛
࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸦⾲ 㸧ࠋࡇࢀࡣࠊప⃰ᗘ࡛ࡣᑠࡉ࡞✵Ὕࢆᣢࡘ㧗ᐦᗘ࡞ 6(, ᵓ㐀ࡀᙧᡂࡉࢀࡿࡓࡵ࡛࠶⾲  ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢ )(& ῧຍ๣⃰ᗘ౫Ꮡᛶࠋ

- 486 -

ࡿࠋࡇࡢ⤖ᯝࡣᐇ㦂⤖ᯝ࡜㠀ᖖ࡟ࡼࡃ୍⮴ࡋ࡚࠾ࡾࠊ50 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ㄪ〇ࡉࢀࡓ 6(, ⭷ࡀࠊ⌧ᐇࡢ 6(, ⭷ࡢຊᏛⓗᏳᐃᛶ࡜ࠊࡑࡢ )(& ῧຍຠᯝࢆᚤどⓗ࡟ࡼࡃࣔࢹࣝ໬࡛ࡁ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ
ղࣜࢳ࣒࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢ඘㟁㟁఩౫Ꮡᛶ ձ࡜ྠᵝ࡟ࠊ࣊࢟ࢧࣇࣝ࢜ࣟࣜࣥ㓟ࣜࢳ࣒࢘ /L3) Ⅳ㓟࢚ࢳࣞࣥ (& ⣔ /,% ࡟࠾ࡅࡿᐃ㟁఩ 50 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ᚓࡽࢀࡓ 6(, ⭷࡟ᑐࡋ࡚ຊᏛⓗ≉ᛶィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ& ࢆ㝖ࡃᙎᛶಀᩘࡢྛᡂ
ศࡀࠊ㟁ᴟ㟁఩ࡢቑຍ࡟క࠸ቑຍࡍࡿഴྥࡀ♧ࡉࢀࡓ㸦⾲ 㸧ࠋࡇࢀࡽࡢᙎᛶಀᩘࡢྛᡂศࡢቑຍࡣࠊ㟁ᴟ㟁఩ࡢቑຍ࡟ࡼࡾ◳࠸↓ᶵᡂศ /L&2 ࡀቑຍࡋࡓࡇ࡜ࡀせᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ◳࠸↓ᶵᡂศࡣ㟁ゎᾮࡢ⁐፹ศᏊࡢ  㟁Ꮚ㑏ඖ⏕ᡂ≀࡛࠶ࡿࠋ㟁ᴟ㟁఩ࡢቑຍ࡟ࡼࡾ㈇ᴟࡢ㈇㟁Ⲵࡀቑຍࡋࡓࡇ࡜࡛ࠊ㟁ゎᾮࡢ㑏ඖࡀಁ㐍ࡉࢀࡓࡓࡵ࡟↓ᶵᡂศࡀቑຍࡋࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ≀㉁ࡢᘏᛶࢆ⾲ࡍ 3XJK ẚࡢ್ࡣ㟁ᴟ㟁఩ࡢቑຍ࡟క࠸ቑຍഴྥࢆ♧ࡋࡓࠋࡘࡲࡾࠊ㧗㟁఩࡛ᙧᡂࡉࢀࡓ 6(, ⭷ࡣࡼࡾᘏᛶ࡟ඃࢀࡿ⪏ஂᛶࡢ࠶ࡿ⭷࡛࠶ࡿ࡜ゝ࠼ࡿࠋ⾲  ࣜࢳ࣒࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 6(, ⭷ࡢຊᏛⓗ≉ᛶࡢ඘㟁㟁఩౫Ꮡᛶࠋ

3.5 ⇞ᩱ㟁ụ༢ཎᏊゐ፹ࡢ㓟⣲㑏ඖ࣭CO 㓟໬཯ᛂࡢᶵᵓゎ᫂ᅛయ㧗ศᏊᙧ⇞ᩱ㟁ụ࡛ࡣࠊ3W ࢆ୺࡜ࡍࡿྜ㔠ࡀ㟁ᴟゐ፹࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࢔ࣀ࣮
ࢻᴟ࡛ࡣ &2 ⿕ẘࠊ࢝ࢯ࣮ࢻᴟࡣ㧗࠸㐣㟁ᅽࡢၥ㢟ࡀ࠶ࡿࠋ⇞ᩱ㟁ụࢆᬑཬࡉࡏࡿࡓࡵ࡟ࠊ㧗౯࡞ 3W ࡢ౑⏝㔞ࢆ࡛ࡁࡿ㝈ࡾῶࡽࡋࠊ࠿ࡘࠊ㧗࠸άᛶࢆᣢࡘゐ፹ࡢ㛤Ⓨࡀᮃࡲࢀ࡚࠸ࡿࠋ㏻ᖖࠊ3W ⢏Ꮚࡣ࣮࢝࣎ࣥࣈࣛࢵ
ࢡ࡜࿧ࡤࢀࡿⅣ⣲㟁ᴟ࡟ᢸᣢࡋࡓࡶࡢࡀ⏝࠸ࡽࢀࡿࠋᢸᣢࡍࡿᮦᩱࢆࢢࣛࣇ࢙ࣥ࡟ࡋࡓ࡜ࡇࢁࠊ&2 ⪏ᛶࡀ㧗࠸஦ࡀ♧ࡉࢀࡓࠋࡉࡽ࡟ࠊ༢ཎᏊࡢ 3W ࢆࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡋࡓゐ፹ࡶ &2 ⪏ᛶࡸ㓟⣲㑏ඖ཯ᛂ࡟ᑐࡋ࡚㧗࠸άᛶࢆᣢࡘ஦ࡀ♧ࡉࢀࠊ┬ⓑ㔠࠿ࡘ㧗άᛶ࡞ゐ፹࡟࡞ࡾᚓࡿ࡜ᮇᚅࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡑࡢᚤどⓗ࡞άᛶᶵᵓࡣࠊᢸᣢᵓ㐀ࢆྵࡵ࡚ࡲࡔ୙᫂࡞Ⅼࡀከ࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ➨୍ཎ⌮㟁Ꮚ≧ែィ⟬ᡭἲ࡜ᶵᲔᏛ⩦ἲࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾࠊ3W ࡀࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡉࢀ࡚࠸ࡿᵓ㐀ࢆồࡵࠊࡉࡽ࡟ࡑࡢᵓ㐀࡜཯ᛂᛶࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋᮏ◊✲࡟ࡼࡾࠊ3W ࡀࢢࣛࣇ࢙࢚ࣥࢵࢪ࡟ᢸᣢࡉࢀࡓᵓ㐀ࢆࠊ₶Ᏻᐃ࡞ࡶࡢࡲ࡛ྵࡵ࡚ከᩘồࡵࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡉࡽ࡟ࠊࡑࢀࡽࡢ 3W ୖ࡛ࡢ &2 ⪏ᛶࠊ࠾ࡼࡧࠊ㓟⣲㑏ඖ཯ᛂࡢ཯ᛂᛶ࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 㸧ࠋࡉࡽ࡟ࠊ1 ࢆࢻ࣮ࣉࡋࡓࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡋࡓ 3W ࡢᵓ㐀࡟ࡘ࠸࡚ࡶ᥈⣴ࡋࠊࡑࡢ཯ᛂᛶ࡟ࡘ࠸࡚ࡶㄪ࡭࡚࠸ࡿࠋ
ࡉࡽ࡟ࠊࢢࣛࣇ࢙ࣥ㢮ఝࡢ஧ḟඖ≀㉁ࠊ≉࡟ 1 ࢻ࣮ࣉ *UDSKGL\QH ࡢ㓟⣲㑏ඖ཯ᛂᛶ࡟㛵ࡋ࡚ࡶ◊✲ࢆ㐍ࡵࡓࠋࡇࡢ⣔ࡶࠊ᪂ࡋ࠸Ⅳ⣲ࡢ஧ḟඖᮦᩱ࡛ࠊ㓟⣲㑏ඖ཯ᛂ࡟㛵ࡋ࡚㧗άᛶࢆ♧ࡍ᪂ゐ፹࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ≉࡟ 1 ࢻ࣮ࣉ࡟ࡼࡗ࡚άᛶࡀୖࡀࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ 1 ࡀࢻ࣮ࣉࡉࢀࡿᵓ㐀࡟ࡘ࠸࡚ࠊࡉࡲࡊࡲ࡞ሙྜࢆㄪ࡭ࠊࡑࡢ཯ᛂᛶࢆㄪ࡭ࡓ>@ࠋ᭱㏆ࠊูࡢࢢ࣮ࣝࣉ࡟ࡼࡗ࡚ࠊྠࡌ⣔ࡢ◊✲⤖ᯝࡀⓎ- 487 -

⾲ࡉࢀࡓࡀࠊࡑࡢ⤖ᯝ࡟ࡼࡿ࡜ࠊ㓟⣲྾╔ࢧ࢖ࢺ࡜ࡋ࡚‽Ᏻᐃ࡞ᵓ㐀ࢆ௬ᐃࡋ࡚࠸ࡓࠋࡋ࠿ࡋࠊᮏ᮶ࠊ᭱ࡶ
Ᏻᐃ࡞ᵓ㐀ࢆ࡜ࡿࡣࡎ࡛࠶ࡾࠊࡑࡢ⤖ᯝ࡟ࡣ␲ၥࡀ࠶ࡿࠋࡑࡢࡓࡵࠊࡉࡽ࡟ᗈ⠊࡟཯ᛂᛶࢆㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊ཯ᛂᛶࡀ㧗ࡃ࡞ࡿ᮲௳ࢆ᫂ࡽ࠿࡟ࡍࡿ஦ࡀ࡛ࡁࡓࠋᮏ◊✲ࡢ⤖ᯝࡣ᪂ࡓ࡞ゐ፹ࢆタィࡍࡿୖ࡛㔜せ࡞タィࡢᣦ㔪ࢆ୚࠼ࡿ࡜⪃࠼ࡽࢀࡿࠋᅗ 㸬ࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡉࢀࡓ༢ཎᏊ 3W ࡢࡉࡲࡊࡲ࡞⤖ྜᵓ㐀࡟࠾ࡅࡿ &2 ࡜ 2+ࡢ྾╔࢚ࢿࣝࢠ࣮ࠋ
ᅗࡢᕥୖ࡟⾜ࡃ࡯࡝ &2 ⪏ᛶࡢ㧗࠸ゐ፹࡜࡞ࡿࡇ࡜ࢆண

ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
㏆⸨ᐂᬦࠊᕝ℩ᬛඖࠊ6DNDNL 1LVULQHࠊ⏣୰భ୍ࠊ㛗ᒸṇ㝯ࠊ ➨  ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊ࢜ࣥࣛ࢖ࣥࠊᮾிᕤᴗ኱Ꮫࠊ ᖺ  ᭶㤋ᒣ ెᑦࠕ➨୍ཎ⌮ 0' ࢆ⏝࠸ࡓ⵳㟁ụࡢ࢖࢜ࣥఏᑟィ⟬ᡭἲࡢ㛤Ⓨ࡜ᛂ⏝ࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨ ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 1,06 ୪ᮌ :3,0$1$ ࣮࢜ࢹ࢕ࢺ࣒ࣜ࢘㸩࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶ᮡ㔝 ಟ ࠕ㠀ⓑ㔠㟁ᴟᮦᩱࡢィ⟬ணࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧

1,06 ୪ᮌ :3,0$1$ ࣮࢜ࢹ࢕ࢺ࣒ࣜ࢘㸩࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶ᒸᓮ 㐍 ࠕ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ 02'</$6 ࡢ㛤Ⓨ࡞ࡽࡧ࡟ࡑࢀࢆ⏝࠸ࡓ 0'ィ⟬࡜ືⓗ 0& ィ⟬ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡿ⇞ᩱ㟁ụ㧗ศᏊ㟁ゎ㉁⭷୰ࡢ≀㉁㍺㏦ࡢ◊✲ࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 1,06 ୪ᮌ :3,0$1$ ࣮࢜ࢹ࢕ࢺ࣒ࣜ࢘㸩࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶㛗ᒸ ṇ㝯ࠕ஧ḟ㟁ụ㟁ᴟ⏺㠃ᵓ㐀ࡢ඘㟁㟁఩౫Ꮡᛶ࡜ຊᏛ≉ᛶࡢ◊✲ࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧1,06 ୪ᮌ :3,0$1$ ࣮࢜ࢹ࢕ࢺ࣒ࣜ࢘㸩࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ ᭶᳃ᕝ Ⰻᛅࠕࢻ࣮ࣉࡉࢀࡓⅣ⣲⣔㟁ᴟゐ፹ࡢᵓ㐀࡜⇞ᩱ㟁ụ㟁ᴟ⏺㠃཯ᛂࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧1,06 ୪ᮌ :3,0$1$ ࣮࢜ࢹ࢕ࢺ࣒ࣜ࢘㸩࢜ࣥࣛ࢖ࣥ㛤ദᖺ  ᭶

- 488 -

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భேࠊỈ㔝

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㸦⚄ᡞ኱Ꮫ ⛉Ꮫᢏ⾡࢖ࣀ࣮࣋ࢩࣙࣥ◊✲⛉࣭ࢩࢫࢸ࣒᝟ሗᏛ◊✲⛉㸧
1. ◊✲┠ⓗը͗ࠅͺɼ ೧ΉͲͶ࠸ਫ਼Ն೵ΦϋϩάʖΝ૱൅ు͹कྙͳͤΖͳ͢ͱ͕Εɼ஦Ͳ΍ଢཇޭͲਭΝ҈Ճ͵ਭોͶ௜ંร‫ͤ׷‬Ζਕ޽ޭ߻੔ͺາཔΝ୴͑ໂ͹ٗढ़Ͳ͍Ζɽਭ͹࢐ԿͶΓΕుࢢΝ‫ͤڇڛ‬Ζ࢐ો൅ਫ਼‫ܧ‬ͳɼుࢢΝण͜खΕਭ͹ؒ‫Ͳݫ‬ਭોΝਫ਼੔ͤΖਭો൅ਫ਼‫ܧ‬͹ൔ಍ରͲͺɼ߶ްི͵ྖࢢफིͳՆࢻޭԢ౶Ͷ
ΓΖ߶͏ร‫ི͗ް׷‬གྷ‫͠ٽ‬ΗΖɽൔ಍ରࡒྋࣙରͶͺన઀͵ώϱχάϡρϕʀώϱχ୼Ғ஖ͳ࢐Կؒ‫ݫ‬ుҒ͹ড়͍݇͗Εɼਭ࢐͹࢐ԿͲͺ࢐ોɼգ࢐Կਭો൅ਫ਼ɼ2+ ϧζΩϩ൅ਫ਼͗෵ࡸ͵ηϒϱয়ସΝखΖৰഖʀঁৰഖ৏Ͳ‫߻ڟ‬దͶً͞Εɼͨ͹ཀྵ࿨અ‫ܯ‬ͺָढ़దͶ΍ऀճదͶ΍॑གྷ͵қٝΝ༙ͤΖ՟ୌͲ͍Ζɽຌ‫ڂݜ‬Ͳͺɼ㠉᪂ⓗ࡞Ỉ⣲〇㐀ගゐ፹࡟ࡼࡿ㧗ຠ⋡࡞ྍどගேᕤගྜᡂࡢᐇ
⌧ࢆ┠ᣦࡋ࡚ࠊ༙ᑟయගゐ፹㸦ೃ⿵ᮦᩱ㸸6U7L2$O7D1<7L26 ࡞࡝㸧ࡢ➨୍ཎ⌮ィ⟬ࢆ⾜࠺ࠋೃ⿵ᮦᩱࡢゐ፹ࣉࣟࢭࢫࠊ༶ࡕࠊྍどගᛂ⟅ᛶࡸ཯ᛂᛶ㸦ࣂࣥࢻ࢔ࣛ࢖࣓ࣥ
ࢺ㸧ࠊᛶ⬟ྥୖࡢࡓࡵࡢࢻ࣮ࣃࣥࢺࡸຓゐ፹ࡢຠᯝࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡋࠊྜᡂࣉࣟࢭࢫࡢᥦ᱌ࡸࠊࡼࡾ
㧗ᛶ⬟࡞ගゐ፹ࡢ≀㉁タィࢆ⾜࠺ࠋࡇࢀ࡟ࡼࡾࠊ኱㔞ࡢỈ⣲ࢆᏳ౯࡟〇㐀ࡍࡿගゐ፹ࢆ฼⏝ࡋࡓỈ⣲♫఍ࡢᐇ⌧ࡸࠊᑗ᮶ࡢ࢚ࢿࣝࢠ࣮ၥ㢟࡜ᬮ໬࡞࡝ࡢ⎔ቃၥ㢟ࡢゎỴ࡟ࡶ㈉⊩ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ

ᅗ 1. (ᕥ) Ḟ㝗ᵓ㐀. (ྑୖ) ᑕᙳ≧ែᐦᗘ. (ྑୗ) ᙧᡂ࢚ࢿࣝࢠ࣮.

◊✲᪉ἲࠊィ⟬᪉ἲᮏሗ࿌᭩࡛ࡣࠊᐇ᪋ࡋࡓ◊✲ࡢෆࠊ௨ୗ࡟ࡘ࠸࡚㔜Ⅼⓗ࡟ሗ࿌ࡍࡿࠋօ ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺ༙ᑟయගゐ፹ Y2Ti2O5S2 ࡢ㠃Ḟ㝗ࡢゎᯒֆ ࣂࢼࢪࣥ㓟ࣅࢫ࣐ࢫࡢࡣỈ㓟໬཯ᛂࡢゎᯒ ◊✲ᡂᯝ
(1) ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺ༙ᑟయගゐ፹ Y2Ti2O5S2㸦YTOS㸧࡟⏕ࡌࡿ≉ᚩⓗ࡞㠃Ḟ㝗ࡢᩘ್ゎᯒࢆ⾜࡞ࡗࡓࠋᇽ

- 490 -

ච㸦ᮾ኱㸧
࣭ஂᐩ㸦ಙᕞ኱㸧ࢢ࣮ࣝࣉࡀࣇࣛࢵࢡࢫἲ࡟ࡼࡗ
࡚ྜᡂࡋࡓ YTOS ࡟ࡣ Mg ࡜ S ࠿ࡽᵓᡂࡉࢀࡿ஧ḟඖⓗ࡞Ḟ㝗ࡢᙧᡂࡀ㏱㐣㟁Ꮚ㢧ᚤ㙾࡜ඖ⣲ศᯒ࡟ࡼࡗ࡚☜ㄆࡉࢀ࡚࠾ࡾࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ࡇࡢ㠃Ḟ㝗ᵓ㐀ࡢྠᐃ࡜㟁Ꮚ≀ᛶࡢゎᯒࠊ㠃Ḟ㝗ࡢᙧᡂ࢚ࢿࣝࢠ࣮ࡢホ౯ࢆ⾜࡞ࡗࡓࠋᩘ್ࢩ࣑ ࣗࣞ ࣮ࢩࣙ ࣥ࡟ࡣ The Vienna Ab Initio Simulation
Package (VASP)ࢆ౑⏝ࡋࠊ஺᥮┦㛵ỗ㛵ᩘ࡟ࡣ Perdew-Burke-ᅗ 2. ࣇ࢙࣑ࣝࣞ࣋ࣝ vs ᙧᡂ࢚ࢿࣝࢠ࣮.

Ernzerhof (PBE)+U ࢆ⏝࠸ࡓࠋࡇࡇ࡛ Hubbard U ࡣࣂࣥࢻࢠ
ࣕࢵࣉࡢᐇ㦂್㸦⣙ 1.95 eV㸧ࢆ෌⌧ࡍࡿࡼ࠺࡟ Ti-3d ㌶㐨࡟௜୚ࡋࡓࠋMgS2 㠃Ḟ㝗ࢆྵࡴࢫ࣮ࣃ࣮ࢭࣝᶍᆺࡢᵓ㐀᭱㐺໬ࡢ⤖ᯝࠊ࣑ࢡࣟ࡞㠃Ḟ㝗ᵓ㐀࡜ࡋ࡚ Mg ࡀ ab ṇ᪉᱁Ꮚࡢ୰ᚰ࡟㓄⨨ࡉࢀࡓ Mg ୰ᚰᵓ㐀ࡀᏳᐃ໬ࡉࢀࡿࡇ࡜ࢆ♧ࡋࡓࠋࡇࢀࡣᐇ㦂࡛ᚓࡽࢀࡓ㠃Ḟ㝗ᵓ㐀ࢆࡼࡃ෌⌧ࡍࡿ㸦ᅗ 1 ᕥ㸧ࠋࡲࡓࠊࡇࡢᵓ㐀࡟࠾ࡅࡿ㟁Ꮚ≧ែࢆゎᯒࡋࡓ⤖ᯝࠊࣂࣥࢻࢠࣕࢵࣉࡢ㛫࡟ MgS2 㠃Ḟ㝗⏤᮶ࡢḞ㝗‽఩ࡀᙧᡂࡉࢀࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 1 ྑୖ㸧ࠋࡇࡢࡼ࠺࡞Ḟ㝗‽఩ࡣගບ㉳ࡉࢀࡓ㟁Ꮚ࣭ṇᏍ࢟ࣕࣜ࢔ࡢ෌⤖ྜ୰ᚰ࡜ࡋ࡚స⏝ࡍࡿྍ⬟ᛶࡀ࠶ࡿࡓࡵࠊゐ፹άᛶࢆపୗࡉࡏࡿせᅉ࡜ࡋ࡚ᢚไࡉࢀࡿ࡭ࡁ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ᭦࡟ࠊḞ㝗ࡢᙧᡂ࢚ࢿࣝࢠ࣮ࢆホ౯ࡍࡿࡇ࡜࡟
ࡼࡗ࡚ Mg-poor ࡸ S-poor ࡢ᮲௳ୗ࡛ MgS2 㠃Ḟ㝗ࡀᢚไࡉࢀࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 1 ྑୗ㸧ࠋᮏ◊✲ࡣᇽච㸦ᮾ኱㸧࣭ஂᐩ㸦ಙᕞ኱㸧ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡜ࡋ࡚ 2023 ᖺ 4 ᭶

ᅗ 3. ໬Ꮫ࣏ࢸࣥࢩࣕࣝ┦ᅗࡢ㡿ᇦ vs ᙧᡂ࢚ࢿࣝࢠ࣮.

14 ᪥௜࡛ The Journal of Physical Chemistry C ㄅ࡟ᥖ㍕ࡉࢀࡓࠋ
ḟ࡟ࠊYTOS ࡟⏕ࡌࡿⅬḞ㝗࡜ࡑࡢ㟁Ꮚ≀ᛶ࡬ࡢᙳ㡪ࢆㄪ࡭ࡓࠋ➨୍ཎ⌮ゎᯒ࡛ࡣ VASP ࢆ౑⏝ࡋ஺᥮┦㛵ỗ㛵ᩘ࡟ࡣ PBE+U ࢆ⏝࠸ࡓࠋࡇࡇ࡛ Hubbard U ࡢ್ࡣ⥺ᙧᛂ⟅࡟ࡼࡗ࡚Ỵᐃࡋ Ti-3d ࡜ Y-4d ㌶㐨࡟௜୚ࡋࡓࠋࡲࡓⅬḞ㝗ࢆ⾲⌧ࡍࡿࡓࡵ࡟ࢫ࣮ࣃ࣮ࢭࣝᶍᆺࢆ⏝࠸ࠊ␗࡞ࡿࢧ࢖ࢬࡢࢫ࣮ࣃ࣮ࢭࣝィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡗ࡚᭷㝈ࢧ࢖ࢬຠᯝࡶ⪃៖ࡋࡓࠋ᱁ᏊḞ㝗ࡢᙧᡂ࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓ⤖ᯝࠊ㟁Ⲵ୰ᛶୗ࡟࠾࠸࡚ࡣ࢝
ࢳ࢜ࣥḞ㝗ࡼࡾࡶ࢔ࢽ࢜ࣥḞ㝗ࡀᙧᡂࡉࢀࡸࡍࡃࠊS-rich ࡢ᮲௳ୗ࡛ࡣ࢔ࢽ࢜ࣥḞ㝗ࡀᢚไࡉࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊⲴ㟁≧ែࢆ⪃៖ࡋࡓᩘ್ィ⟬࡟ࡼࡗ࡚ࣇ࢙࣑ࣝࣞ࣋ࣝࡀ౯㟁Ꮚᖏ㸦ఏᑟᖏ㸧ࡢ௜㏆࡟࠶ࡿሙྜ࡟ S㸦O㸧Ḟ㝗ࡀᙧᡂࡉࢀࡸࡍ࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸦ᅗ 2㸧ࠋ᭦࡟ࠊࡇࢀࡽ࢔ࢽ࢜ࣥḞ㝗ࡣࣂࣥࢻࢠࣕࢵࣉࡢ㛫࡟୙⣧≀‽఩ࢆㄏ㉳ࡍࡿࡇ࡜ࡀ♧ࡉࢀࠊ㟁Ꮚ࣭ṇᏍ࢟ࣕࣜ࢔ࡢ෌⤖ྜ୰ᚰ࡜ࡋ࡚స⏝ࡍࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ௨ୖࡢ⤖ᯝࢆ㋃ࡲ࠼࡚ゐ፹ᛶ⬟ྥୖࡢࡓࡵࡢຠᯝⓗ࡞ࢻ࣮ࣃࣥࢺࡢ᥈⣴ࢆᘬࡁ⥆ࡁ㐍ࡵ࡚࠸ࡿࠋ  ᭱ᚋ࡟ࠊ࣌ࣟࣈࢫ࢝࢖ࢺ༙ᑟయගゐ፹ SrTiO3㸦STO㸧ࡢ Al ࢻ࣮ࣆࣥࢢ㸦STO:Al㸧ࡢ㟁Ꮚ≀ᛶࡢᩘ್ゎᯒࢆ⾜࠺࡜࡜ࡶ࡟ࠊSTO ࡟࠾ࡅࡿࡼࡾຠᯝⓗ࡞ࢻ࣮ࣃࣥࢺࡢ᥈⣴ࢆ⾜࡞ࡗࡓࠋゎᯒ࡛ࡣ VASP ࢆ౑⏝ࡋࡓ➨୍ཎ⌮ィ⟬ࢆ⾜࠸ࠊ஺᥮┦㛵ỗ㛵ᩘ࡟ࡣ PBE+U ࢆ⏝࠸ࡓࠋࡲࡓࠊⅬḞ㝗ࡸࢻ࣮ࣆࣥࢢࢆ⾲⌧ࡍࡿࡓࡵ࡟ࢫ࣮ࣃ࣮
ࢭࣝᶍᆺࢆ⏝࠸࡚᭷㝈ࢧ࢖ࢬຠᯝࡶ⪃៖ࡋࡓࠋAl ࢻ࣮ࣆࣥࢢࡣ࢖༙࢜ࣥᚄࡢほⅬ࠿ࡽ Ti ࢧ࢖ࢺࡢ⨨᥮࡜ぢ࡞ࡉࢀࠊSTO ྜᡂ᫬࡟⏕ࡌࡿෆᅾⓗ࡞ O Ḟ㝗⏤᮶ࡢ୙⣧≀‽఩ࢆᡴࡕᾘࡍస⏝ࢆᣢࡘࠋࡇࡢࡇ࡜ࡣ O Ḟ㝗࿘㎶ࡢ 2 ⟠ᡤࡢ Ti ࢆ Al ࡛⨨᥮ࡋࡓࢫ࣮ࣃ࣮ࢭࣝᶍᆺࡢィ⟬࡛ࡶ☜ㄆࡉࢀࡓࠋࡑࡇ࡛ࠊྠᵝࡢຠᯝࡀᮇᚅ࡛ࡁ
ࡿࢻ࣮ࣃࣥࢺ࡜ࡋ࡚ B, Ga, In, Sc, Mg ࢆ⪃࠼ࡓࠋࡇࢀࡽࢻ࣮ࣃࣥࢺࡣࠊᙧᘧ㟁Ⲵࡢ౯ᩘࡀ Ti ࡢࡑࢀࡼࡾᑠࡉ
ࡃ p ᆺࢻ࣮ࣆࣥࢢ࡜ࡋ࡚ാࡃࡇ࡜ࡀᮇᚅࡉࢀࠊ࢖༙࢜ࣥᚄࡀ Ti ࡢࡑࢀ࡜㏆࠸ඖ⣲࡛࠶ࡿࠋ㟁Ꮚ≧ែࡢゎᯒࡢ⤖ᯝࠊࡇࢀࡽࡢࢻ࣮ࣃࣥࢺࡣ඲࡚ Al ࢻ࣮ࣆࣥࢢ࡜ྠᵝ࡟ O Ḟ㝗⏤᮶ࡢ୙⣧≀‽఩ࢆᡴࡕᾘࡍస⏝ࢆᣢࡘࡇ- 491 -

࡜ࢆ♧ࡋࡓࠋ᭦࡟ࠊࢻ࣮ࣃࣥࢺࡢᙧᡂ࢚ࢿࣝࢠ࣮ࡢホ౯࠿ࡽ Ga, Sc, Mg ࡣࢻ࣮ࣆࣥࢢ࡟㛵ࡋ࡚ Al ࡼࡾ᭷฼࡛
࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ 3㸧ࠋ௨ୖࡢ⤖ᯝࢆ㋃ࡲ࠼࡚᭦࡟ຠᯝⓗ࡞ࢻ࣮ࣃࣥࢺࡢ᥈⣴ࢆᘬࡁ⥆ࡁ㐍ࡵ࡚࠸ࡿࠋ
(2) ࣂࢼࢪࣥ㓟ࣅࢫ࣐ࢫ (BiVO4) ࡣྍどගᛂ⟅ᛶࢆᣢࡕࠊ㓟⣲Ⓨ⏕཯ᛂࢆᘬࡁ㉳ࡇࡍගゐ፹࡜ࡋ࡚▱ࡽࢀ࡚ࡁࡓࡀࠊ㏆ᖺ➇ྜࡍࡿ㐣㓟໬Ỉ⣲Ⓨ⏕཯ᛂࡀඃ఩࡟㉳ࡇࡿࡇ࡜ࡀᣦ᦬ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇ࠺ࡋࡓ
㆟ㄽࡣࠊNørskov ࡽ࡟ࡼࡗ࡚ᥦ᱌ࡉࢀࡓ≉ᐃࡢ྾╔≧ែࡢ࢚ࢿࣝࢠ࣮ࡢࡳࢆ⏝࠸ࡓ㠀ᖖ࡟⡆⣲໬ࡉࢀࡓࣔࢹ
࡛ࣝ⾜ࢃࢀ࡚࠸ࡿࡓࡵࠊᮏ᮶」㞧࡞Ỉ㓟໬཯ᛂ࡟⌧ࢀࡿᵝࠎ࡞཯ᛂ㐍⾜⤒㊰ࡢྍ⬟ᛶࢆ᤼㝖ࡋ࡚ࡋࡲࡗ࡚࠾

㸦㓟⣲Ⓨ⏕཯ᛂ㸧‫כ‬൅㸦㐣㓟໬Ỉ⣲Ⓨ⏕཯ଶ  ՜‫ כ‬

ା

൅

൅ ݁ି

(1)

‫ כ‬՜‫כ‬൅ା ൅ ݁ି

(2)

‫כ‬൅



ଶ ՜ ‫כ‬ା ൅ ݁ି

‫  כ‬՜‫  כ‬൅‫  כ‬՜ ‫  כ‬൅

(1’)

ᛂ㸧
ା

(2’)

(3)

൅ ݁ି

(3’)

(4)

ା

‫כ‬൅

ଶ  ՜‫ כ‬‫  כ‬՜ ‫  כ‬൅

(5)ା ൅ ݁ି

(6)‫  כ‬՜ ‫ כ‬൅ଶ൅൅ ݁ି‫  כ‬՜‫ כ‬൅ଶ ଶࡾࠊ␗࡞ࡿ୺⏕ᡂ≀࡟ᑐࡍࡿゐ፹᮲௳ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࡣࡼࡾ㋃ࡳ㎸ࢇࡔ཯ᛂ࣓࢝ࢽࢬ࣒ゎᯒࡀᚲせ࡛࠶ࡗࡓࠋᮏ◊✲࡛ࡣᐇ㝿ࡢ཯ᛂ࣓࢝ࢽࢬ࣒ࢆヲ⣽࡟㏣࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࠊ➨୍ཎ⌮ィ⟬࡟࠾ࡅࡿ᭱Ᏻᐃ⾲㠃ᵓ㐀ࡢỴᐃ࡜ࡑࢀࢆ⏝࠸ࡓỈศゎ཯ᛂࡢ⇕ຊᏛ࡞❧ሙ࠿ࡽ᳨ウࢆ⾜ࡗࡓࠋ22 +H
22+ +H

ϸ* H92 +H+2 +H

2 +H

+22+ +H

2+ DT


2+ +H




5HDFLRQ&RRUGLQDWH

+2ਦ࢐ો൅ਫ਼ൕԢϟΩωθϞ⾲㠃ᵓ㐀ࡢᏳᐃᛶࢆ㆟ㄽࡍࡿࡓࡵ࡟ࠊ(110)᪉ྥ࡟ᵝࠎ࡟ษࡾฟࡋࡓ BiVO4 ⾲㠃ࢆࣔࢹࣝ໬ࡋࡓཌࡉ 15 ࢜ࣥࢢࢫࢺ࣮࣒ࣟ⛬ᗘࠊ2x1 ࢫ࣮ࣃ࣮ࢭࣝࡢࢫࣛࣈࣔࢹࣝࢆసᡂࡋࠊࡇࢀࡽ࡟ࡘ࠸࡚ᐦᗘỗ㛵ᩘ࡟ࡼࡿᵓ㐀᭱㐺໬࠾ࡼࡧ࢚ࢿࣝࢠ࣮ࡢぢ✚ࡶࡾࢆ⾜࠸ࠊ⇕ຊᏛⓗฝໟ࡟ࡼࡿゎᯒࢆ⾜ࡗࡓࠋฝໟࢆసࡿ BiO2ࠊBi4Oࠊ
Bi2O3ࠊV3(Bi3O8)2ࠊV2O5ࠊVO2ࠊV3OࠊV2O3 ࡀᯒฟࡏࡎ BiVO4 ࡀᙧᡂࡉࢀࡿ໬Ꮫ࣏ࢸࣥࢩࣕࣝ㡿ᇦ࡟࠾࠸࡚ࠊO ࡢ໬Ꮫ࣏ࢸࣥࢩࣕࣝࢆኚᩘ࡟ྲྀࡾ⾲㠃࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ໬Ꮫ㔞ㄽẚࢆṇࡋࡃ‶ࡓࡋ VO4 ࡢᵓ㐀ࢆಖࡘࡼ࠺࡞ Bi 㟢ฟᆺᵓ㐀ࡀࠊO ࡢ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ್ (O-rich ࠿ O-poor ࠿) ࡟ࡼࡽࡎ᭱
ࡶᏳᐃ࡛࠶ࡿࡇ࡜ࢆᐃ㔞ⓗ࡟᫂ࡽ࠿࡟ࡋࡓࠋ

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ࡇ࠺ࡋ࡚ᚓࡽࢀࡓᵓ㐀ࢆ⏝࠸࡚ࠊ⾲㠃࡛㉳ࡇࡿ཯ᛂࢆ㏣㊧ࡋࡓࠋලయⓗ࡟ࡣ⾲ࡢࡼ࠺࡞⣲཯ᛂ㐣⛬࡟ࡘ࠸࡚㓟⣲Ⓨ⏕཯ᛂ࡜㐣㓟໬Ỉ⣲Ⓨ⏕཯ᛂࢆ᳨ウࡋࡓࠋࡓࡔࡋ݁ ି ࡢ࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࡢࡣᅔ㞴࡛࠶ࡿࡓࡵࠊࣉࣟࢺࣥ࡜㟁Ꮚࡀྠ᫬࡟㞳⬺ࡍࡿ Proton Coupled
Electron Transfer ࢆ௬ᐃࡋࠊィ⟬ᶆ‽Ỉ⣲㟁ᴟࢆ⏝࠸࡚
ଵ

ࡼࡗ࡚ଶ

ଵ
ଶ

ଶ ֖ ‫ܪ‬ା൅ ݁ ି ࡢ㟁ᴟ㟁఩ࢆࢮࣟ࡜ᐃ⩏ࡍࡿࡇ࡜࡟ଶ ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆ௦᭰ࡋ࡚⏝࠸ࡓࠋ㓟⣲Ⓨ⏕཯ᛂ࡟ࡘ࠸࡚ࡣᅗ

4 ࡟♧ࡍ࡜࠾ࡾࠊ඲యࡢ࣑ࣜࢸ

࢕ࣥࢢࢫࢸࢵࣉࡣ཯ᛂ(2)࡛࠶ࡿࡼ࠺࡟ぢ࠼ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ཯ᛂ(3)࡟࠾࠸࡚ᚓࡽ
ࢀࡿ*  ᵓ㐀ࡣଶ ଶ ࡀ⾲㠃྾╔ࡋ࡚࠸ࡿᵓ㐀࡛࠶ࡾࠊ㧗࢚ࢿࣝࢠ࣮࡞*O ࢆ௓ࡉࡎ࡟㐣㓟໬Ỉ⣲཯ᛂࡢࡼ࠺࡟* ࠿ࡽ┤᥋཯
ᛂ(2’)ࡀ㉳ࡇࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࡇࡢሙ
ྜࠊ㐣㓟໬Ỉ⣲ࡀ⮬↛࡜Ⓨ⏕ࡍࡿࡇ࡜ࡀࢃ
࠿ࡗࡓࠋ୍᪉࡛ࠊ཯ᛂ(4)ཬࡧ(5)ࡀ㉳ࡇࡿࡓࡵ࡟࣮࣍ࣝࡀᣢࡘ࡭ࡁᚲせ࡞⮬⏤࢚ࢿࣝࢠ࣮ࡣࠊ཯ᛂ( 1)ࡢ*OH ⏕ᡂ࢚ࢿࣝࢠ࣮ࡼࡾࡶ
ᑠࡉ࠸ࡓࡵࠊ㓟⣲Ⓨ⏕ࡶྠ᫬࡟㉳ࡇࡿࡇ࡜ࡀ♧၀ࡉࢀࡿ (ᅗ 5)ࠋBiVO4 ࡢ(110)㠃࡟࠾ᅗ 5.Ỉࡢ㓟໬཯ᛂ࣓࢝ࢽࢬ࣒.

࠸࡚ࡣ୧཯ᛂࡀ➇ྜࡋ࡚㉳ࡇࡗ࡚࠸ࡿࡶࡢ
ࡢࠊ඲య࡜ࡋ࡚ࡣ㐣㓟໬Ỉ⣲Ⓨ⏕཯ᛂࡢ᪉ࡀ᭷฼࡛࠶ࡿ஦ࡀ♧ࡉࢀࡓࠋࡇࡢࡼ࠺࡟ࠊ㐣㓟໬Ỉ⣲Ⓨ⏕ࡢࡳࡀ㉳ࡇࡿ࡜ணࡉࢀࡿ Nørskov ࡽࡢࣔࢹࣝࢆ㉸࠼ࡓ⤖ㄽࢆᑟࡁฟࡍࡇ࡜࡟ᡂຌࡋࡓࠋ

Ⓨ⾲ᐇ⦼
x

すཱྀ࿴Ꮥࠊ୰ᯘ㯞⨾Ꮚࠊᱱᕼኊࠊஂᐩ㝯ྐࠊᅵᣢᓫႹࠊᰘ⏣┤ဢࠊᇽච୍ᡂࠊኳ⬟⢭୍㑻ࠊᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺගゐ፹ <7L26 ࡟࠾ࡅࡿ㠃Ḟ㝗ࡢ⌮ㄽⓗ◊✲ࠊศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥x

ᙇ ୺㌷ࠊᅵᣢ ᓫႹࠊఀዉ ⛱ဴࠊ㝰㒊 ెᏕࠊṊ⸨ ಇ௓ࠊᑿཎ ᖾ἞ࠊᒣ⏣ ኱㈗ࠊኳ⬟ ⢭୍㑻ࠊ❧ᕝ㈗ኈࠊ࣐࣊ࢱ࢖ࢺ࣓ࢯ⤖ᬗග㟁ᴟࢆ⏝࠸ࡓ㧗ຠ⋡࣭㧗㑅ᢥⓗ㐣㓟໬Ỉ⣲⏕ᡂࠊ ᖺග໬Ꮫウㄽ఍ࠊᖺ  ᭶  ᪥ฟ∧ᐇ⦼
&KDUDFWHUL]DWLRQ RI SODQDU GHIHFW LQ OD\HUHG SHURYVNLWH SKRWRFDWDO\VW <7L26 E\ HOHFWURQ PLFURVFRS\ DQG ILUVWSULQFLSOHVFDOFXODWLRQV01DNDED\DVKL.1LVKLJXFKL;/LDQJ7+LVDWRPL77DNDWD77VXFKLPRFKL16KLEDWD
.'RPHQDQG6/7HQQR -3K\V&KHP &     - 493 -

┬࢚ࢿࣝࢠ࣮ḟୡ௦༙ᑟయࢹࣂ࢖ࢫ㛤Ⓨࡢࡓࡵࡢ㔞Ꮚㄽ࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥ
Quantum-theory-based multiscale simulation for the development of thenext-generation power devices‫ۑ‬ᢲᒣ῟ 1ࠊࣈ࢖ ࢩ࢚࢟࢘ ࣑ 1ࠊᐮᕝ⩏⿱ 2ࠊⲡሙᙲ 2ࠊไ㔝࠿࠾ࡾ 1ࠊᯇୗ㞝୍㑻 3
1

1

ྡྂᒇ኱Ꮫ ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤࠊ2 ஑ᕞ኱Ꮫᛂ⏝ຊᏛ◊✲ᡤࠊ3 ᮾிᕤᴗ኱Ꮫ≀㉁᝟ሗ༟㉺◊✲㝔◊✲┠ⓗ㔞Ꮚㄽ➨୍ཎ⌮ィ⟬࡟ࡼࡾࠊ༙ᑟయⷧ⭷ᡂ㛗ࡢᚤどⓗᶵᵓࢆ᫂ࡽ࠿࡟ࡋࠊࡲࡓ࢔ࣔࣝࣇ࢓ࢫࢤ࣮ࢺ⤯⦕⭷㸭༙ᑟయ࡟௦⾲ࡉࢀࡿࢹࣂ࢖ࢫ⏺㠃ࡢ≉ᛶࢆゎ᫂ࡋࠊࡉࡽ࡟➨୍ཎ⌮ィ⟬࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜༙ᑟయࢹࣂ࢖
ࢫࢩ࣑࣮ࣗࣞࢱ࠾ࡼࡧ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࣉࣟࢭࢫࢩ࣑࣮ࣗࣞࢱ࡜ࢆ⤫ྜࡋࡓ᪂ࡓ࡞ࢩ࣑࣮ࣗࣞࢩࣙࣥᢏ⾡ࢆ☜❧ࡍࡿࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝ࡜ᐇ㦂⤖ᯝࡢ᳨ド࡟ࡼࡾࠊḟୡ௦┬࢚ࢿࣝࢠ࣮༙ᑟయࢹࣂ࢖ࢫ࡟࠾ࡅࡿ⛉Ꮫ࡜〇㐀ᢏ⾡ࡢⓎᒎ࡟㈨ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚㄽ➨୍ཎ⌮ィ⟬࡟࠾ࡅࡿ୺ࡓࡿᡭἲࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT: Density Functional Theory㸧࡟ᇶ࡙ࡃ Kohn-

Sham ᪉⛬ᘧࢆᐇ✵㛫ࡢ࣓ࢵࢩࣗୖ࡛ゎࡃᐇ✵㛫ᐦᗘỗ㛵ᩘἲ㸦ࢥ࣮ࢻྡ㸻RSDFTࠊReal-Space DensityFunctional Theory㸧࠾ࡼࡧࣛࢢࣛࣥࢪ࢙ᙧᘧࡢ᫬㛫౫Ꮡ᪉⛬ᘧࢆゎࡃᐇ✵㛫 Car-Parrinello ศᏊືຊᏛἲ㸦ࢥ
࣮ࢻྡ㸻RS-CPMDࠊReal-Space Car-Parrinello Molecular Dynamics㸧࡛࠶ࡿࠋࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘ㸦NEGF: Non-Equilibrium Green’s Function㸧ἲ࡟ࡼࡗ࡚ᐇ⾜ࡉࢀࡓࠋNEGF ࢥ࣮ࢻࡣ RSDFTࢥ࣮ࢻ࡜⤫ྜࡉࢀ࡚࠸ࡿࠋ࠸ࡎࢀࡢࢥ࣮ࢻࡶᮏࢢ࣮ࣝࣉ࡟࠾ࡅࡿ⊂⮬㛤Ⓨࡢࡶࡢ࡛࠶ࡿࠋࡲࡓ᫖ᖺᗘ௨㝆ࠊࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࢆά⏝ࡋࡓ࣮࢜ࢲ࣮N࣭orbital-free DFT ࢥ࣮ࢻࡶ㛤Ⓨࡉࢀࡓࠋ3◊✲ᡂᯝᮏᖺᗘࡢᡂᯝ࡜ࡋ࡚ࡣࠊi) SiC ࠾ࡼࡧ GaN ➼ࡢ࣡࢖ࢻࢠࣕࢵࣉ༙ᑟయࠊ࠾ࡼࡧࢢࣛࣇ࢙ࣥࡢ࢚ࣆࢱ࢟ࢩࣕ

ࣝᡂ㛗ᶵᵓ࡜୙⣧≀ΰධࡢᶵᵓゎ᫂[ฟ∧ᐇ⦼ࣜࢫࢺ 1-4,9,10]ࠊ ii) SiC/SiO2ࠊGaN/GeOx/SiO2 ࡛ࡢ࣮࢟ࣕࣜࣖ
ࢺࣛࢵࣉࡢྠᐃ࡜㧗ရ㉁⏺㠃సᡂࡢฎ᪉⟢ࡢᥦ♧[ࣜࢫࢺ 5]ࠊiii) ┬࢚ࢿࣝࢠ࣮୙᥹Ⓨᛶࣇࣛࢵࢩ࣓࣮ࣗࣔࣜ
ࡢ࣓࣮ࣔࣜᶵ⬟ゎ᫂[ࣜࢫࢺ 6,7]ࠊiv)㔞Ꮚࢥࣥࣆ࣮ࣗࢸ࢕ࣥࢢ࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ[ࣜࢫࢺ 8]ࠊ➼ࡢ⤖ᯝࡀᚓࡽࢀ࡚࠸ࡿࠋ௨ୗ࡛ࡣ i)ࠊiii)ࡢᡂᯝࡢ୍㒊ࢆㄝ᫂ࡍࡿࠋ
SiC ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗࡟࠾ࡅࡿ❅⣲ࢻࢼ࣮ࡢྲྀࡾ㎸ࡳᶵᵓゎ᫂
SiC ࡢ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࡣ SiH4ࠊC3H8 ࢆࢯ࣮ࢫ࢞ࢫ࡜ࡋ࡚⏝࠸ࡿ CVD ἲ࡛⾜ࢃࢀࡿࠋࡉࡽ࡟⭷㉁ྥୖ
࡜ᡂ㛗㏿ᗘቑ㐍ࡢࡓࡵ࡟ HCl ࢆຍ࠼ࡓ HCVD ἲࡶࡋࡤࡋࡤ౑ࢃࢀࡿࠋᡂ㛗࡟ࡣᚤഴᩳ㠃ࡀ⏝࠸ࡽࢀࡿࡢ࡛ࠊ
⾲㠃ࡣࢸࣛࢫ࡜ཎᏊࢫࢸࢵࣉ࠿ࡽᵓᡂࡉࢀࠊ཯ᛂᛶࡢ㧗࠸ཎᏊࢫࢸࢵࣉ࠿ࡽࠊẼ┦཯ᛂࡢ⤖ᯝ࠿ࡽ⏕ࡌࡓ
SiCl2 ࡜ C2H2 ࡀྲྀࡾ㎸ࡲࢀࠊࢫࢸࢵࣉࣇ࣮ࣟࡢ࢚ࣆᡂ㛗ࡀ⏕ࡌࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡲࡓࠊࢻࢼ࣮ࠊ࢔ࢡࢭࣉ

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ࢱ࣮ཎᏊࡢὀධࡶࠊከࡃࡢሙྜ࢚ࣆᡂ㛗୰࡟⾜ࢃࢀࠊ࡜ࡃ࡟ࢻࢼ࣮
࡛࠶ࡿ❅⣲ཎᏊࡢὀධࡣ❅⣲ศᏊࡢࢫࢸࢵࣉ➃࡛ࡢ஋㞳ྲྀࡾ㎸ࡳ࡟ࡼࡾ㐩ᡂࡉࢀࡿ࡜ㄆ㆑ࡉࢀ࡚࠸ࡿࡀࠊࡑࡢྲྀࡾ㎸཯ᛂࡢᚤどⓗᶵᵓࡣࢃ࠿ࡗ࡚࠸࡞࠸ࠋSiC(0001)㠃࡟ࡣࠊ5 ✀㢮ࡢࢫࢸࢵࣉ➃ SC, S2, S3,
C1, C2 ࡀᏑᅾࡋᚓࡿࠋ
㸦ࢫࢸࢵࣉ➃࡟ฟ⌧ࡍࡿཎᏊࡀ Si ࡢሙྜࢆ Sࠊ
C ࡢሙྜࢆ Cࠊ࠶ࡽ࡟ᵓ㐀⦆࿴๓ࡢ dangling bond ࡢᩘ࡛ྡ⛠ࢆࣛ࣋ࣝࡋࡓ 㸧ࠋࡑࢀࡒࢀࡢࢫࢸࢵࣉᵓ㐀࡜Ỉ⣲྾╔࢚ࢿࣝࢠ࣮ࢆ⥙⨶ⓗ࡟ィ⟬࡛ㄪ࡭㸦⣙ 30 ㏻ࡾࡢྍ⬟ᛶ㸧ࠊࡑࢀࡒࢀࡢᵓ㐀ࡢỈ⣲⿕そ⋡ࢆồࡵࡓࠋࡑࡢ⤖ᯝࠊCVD ᡂ㛗ᗘ࡛ࡣࠊSi3 ࢫࢸࢵࣉࡢỈ⣲⿕そ⋡ࡀ㢧ⴭ࡟ప࠸ࡇ࡜ࡀุ᫂ࡋࡓࠋࡑࢀ࡟⥆ࡃࡢࡀ SC ࢫࢸࢵࣉࠊSi2
ࢫࢸࢵࣉ࡛࠶ࡿࠋỈ⣲⿕そ⋡ࡀప࠸ሙᡤࡀྲྀࡾ㎸཯ᛂࡢ࣍ࢵࢺࢫ࣏
ࢵࢺ࡟࡞ࡿ࡜⪃࠼ࡽࢀࡿࡢ࡛ࠊ௒ᅇࠊSi3, Si2, SC ࢫࢸࢵࣉ➃࡛ࡢ N2
ࡢ྾╔஋㞳ࢆㄪ࡭ࡓࠋᅗ 1 ࡣᏳᐃ࡞❅⣲ࡢ྾╔ᵓ㐀࡛࠶ࡿࠋ஋㞳྾╔ࡍࡿࡇ࡜ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟ᚓ࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋN2 ศᏊᙜࡓࡾࡢ྾╔࢚ࢿࣝࢠ࣮ࡣࠊSi2 ࢫࢸࢵࣉࡢሙྜࠊ2.51 eV (Si2-A)ࠊ2.68
eV (Si2-B)ࠊSi3 ࢫࢸࢵࣉࡢሙྜࠊ3.46 eV (Si3-A)ࠊ4.16 eV(Si3-B)࡜ィ⟬ࡉࢀࡓࠋࡉࡽ࡟ N2 ศᏊࡀẼ┦࠿ࡽ㣕᮶ࡋ࡚ࠊࡇࡢ஋㞳྾╔ᙧែࢆᅗ 1: N2 ࡢ Si2 ࢫࢸࢵࣉ(a,b)ࠊ࠾
ࡼࡧ Si3 ࢫࢸࢵࣉ(c,d)࡛ࡢ஋㞳྾╔ᵓ㐀ࠋ㟷㸸SiࠊⲔ㸸Cࠊ⥳㸸࢚ࢵ
ࢪࡢ Siࠊ⅊㸸Nࠋ࡜ࡿࡲ࡛ࡢཎᏊ཯ᛂ⤒㊰ࢆ᥈⣴ࡋࡓࠋࡑࡢ⤖ᯝࠊ཯ᛂ࢚ࢿࣝࢠ࣮㞀ቨࡀࠊỈ⣲ࣜࢵࢳ㸭ࣉ࢔࡞⎔ቃ࡟౫Ꮡࡋ࡚ࠊ1.16 eV - 1.40 eV ࡛࠶ࡿ⤒㊰ࡀぢࡘ࠿ࡗࡓࠋ1600Υࡢ CVD ᡂ㛗ᗘ࡛ࡣࠊ༑ศ㢖ᗘࡢ㧗࠸ࣉࣟࢭࢫ࡛࠶ࡿࠋ
ࣇࣛࢵࢩ࣓࣮ࣗࣔࣜグ᠈せ⣲࡛࠶ࡿ SiN ୰ࡢ floating state ࡢⓎぢ࡜ࡑࡢᶵ⬟༙ᑟయ࠶ࡿ࠸ࡣ⤯⦕య୰ࡢⅬḞ㝗ࡣࠊࣈࣟࢵ࣍≧ែ➼ࡢᗈࡀࡗࡓ㟁Ꮚ≧ែ࡜ࡣ␗࡞ࡿᒁᅾ㟁Ꮚ≧ែࢆ⏕ࡳࡔࡋࠊࡑࢀࡽࡢᒁᅾ≧ែࡣࢫ࣌ࢡࢺࣝ࡜ࡋ࡚ࡣࠊ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ୰࡟ࡋࡤࡋࡤ᪂ࡓ࡞‽఩ࢆᘬࡁ㉳ࡇࡍࠋࡑࢀࡽࡣ㟁Ꮚࢹࣂ࢖ࢫ࡟࠾ࡅࡿ࣮࣭࢟ࣕࣜࣖࢺࣛࢵࣉ࡜ࡋ࡚ࠊࡲࡓගᏛ㑄⛣ࡢᤕ⋓୰ᚰ࡜ࡋ࡚ࠊ㟁ᏊⓗගᏛⓗ⌧㇟࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡍࠋࢸࢡࣀࣟࢪ࣮ⓗ࡟ࡣከࡃࡣ㈇ࡢᙳ㡪࡛࠶ࡿ࡜ࡉࢀ࡚࠸ࡿࡀࠊᒁᅾ≧ែ࡟㟁Ⲵࢆᤕ⋓ࡉࡏࡿࠊ࠶ࡿ࠸ࡣࡑࡇ࠿ࡽ㟁Ⲵࢆྲྀࡾฟࡍ࡜࠸࠺ࡇ࡜ࡣࠊ࣓࣮ࣔࣜ࡬ࡢ᝟ሗࡢ᭩ࡁ㎸ࡳ࣭ㄞࡳฟࡋ࡟
௚࡞ࡽ࡞࠸ࠋࡍ࡞ࢃࡕⅬḞ㝗➼࡟ࡼࡿᒁᅾ㟁Ꮚ≧ែࡣ✲ᴟࡢ࣓࣮ࣔࣜࣘࢽࢵࢺ࡟ᡂࡾᚓࡿࠋࡑࡢࡼ࠺࡞౛ࡣࠊ
㐣ཤࡢ࢚ࣞࢡࢺࣟࢽࢡࢫ⏘ᴗ࡛ࡣ⛥࡛࠶ࡗࡓࡀࠊ⌧ᅾࡢࢹ࣮ࢱ♫఍ࢆᨭ࠼࡚࠸ࡿࣇࣛࢵࢩ࣓࣮࡛ࣗࣔࣜࡣࠊ
ࡲࡉ࡟ࡑࡢࡼ࠺࡞ࡇ࡜ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࡀࠊ௒ᖺᗘࡢᡃࠎࡢィ⟬࡛᫂ࡽ࠿࡟࡞ࡗ࡚ࡁࡓࠋ
⌧ᅾࡢ 3D-NAND ࣇࣛࢵࢩ࣓࣮ࣗࣔࣜࡣ Si-MOS ᵓ㐀⏺㠃࡟✚ᒙࡉࡏࡓ࢔ࣔࣝࣇ࢓ࢫ SiN ࢆ࣓࣮ࣔࣜࣘ
ࢽࢵࢺ࡜ࡋ࡚⏝࠸࡚࠸ࡿࡀࠊࡑࡢ࣓࣮ࣔࣜᶵ⬟Ⓨ⌧ࡢ࣑ࢡࣟᶵᵓࡣࢃ࠿ࡗ࡚࠸࡞࠸ࠋᐇ㦂ⓗ࡟ࢃ࠿ࡗ࡚࠸ࡿ
ࡢࡣࠊ࢔ࣔࣝࣇ࢓ࢫ SiN ࡣ Si ࣜࢵࢳ㸦N ࣉ࢔㸧࡛࠶ࡿࡇ࡜ࠊ 1020 cm-3 ಶ௨ୖࡢỈ⣲ཎᏊࡀྵࡲࢀ࡚࠸ࡿ
ࡇ࡜ࠊࡢ 2 Ⅼ࡛࠶ࡿࠋࡑࡇ࡛௒ᖺᗘࡣࠊSiN ࡢ⤖ᬗᆺ
࡛࠶ࡿE-Si3N4 ࢆ౛࡟࡜ࡾࠊࡑࡇ࡛ࡢ❅⣲ཎᏊ✵Ꮝ
㸦VN㸧ᵓ㐀࡜㟁Ꮚ≧ែࢆ DFT ࡢࣁ࢖ࣈࣜࢵࢻ㏆ఝ࡟ࡼࡗ࡚ㄪ࡭ࡓࠋ᭱ึࡢ኱ࡁ࡞Ⓨぢࡣࠊ࣍ࢫࢺࡢ SiN ࡢ- 495 -

ᅗ 2: E-Si3N4 ࡢఏᑟᖏୗ➃ࡢ㟁Ꮚ㌶㐨ࠋ(a) c ㍈᪉ྥ࡜(b)ࡑࢀ࡟ᆶ┤࡞᪉ྥ࠿ࡽࡢ㌶㐨ࡢ➼್㠃㸦㟷+ࠊ㯤̿㸧ࠋ㟷࡜ⓑࡢ⌫ࡣࡑࢀࡒࢀ SiࠊN ཎᏊࠋఏᑟᖏࡢᛶ㉁࡛࠶ࡿࠋᅗ 2 ࡣE-Si3N4 ࡢఏᑟᖏୗ➃ࡢ㟁Ꮚ㌶㐨㸦KS ㌶㐨㸧࡛࠶ࡿࠋ㌶㐨ࡣᵓᡂཎᏊࡢ㌶㐨࠿ࡽᵓᡂࡉࢀ࡚࠸ࡿࢃࡅ࡛ࡣ࡞ࡃࠊ᱁Ꮚ㛫࡟ᗈࡀࡗࡓ floating ≧ែ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣ␯࡞≀㉁⩌ࠊ౛ࢆ࠶ࡆࢀࡤ඾ᆺⓗ༙ᑟయ㸦඘ሸ⋡ 0.34㸧ࠊⅣ⣲ࢼࣀ≀㉁➼࡟⾲ࢀࡿ≧ែ࡛࠶ࡾࠊࣃ࣮༙࣡ᑟయ SiC ࡛ࡣࢹࣂ࢖ࢫ⏺㠃≉ᛶࡢ㘽ࢆᥱࡿ≧ែ࡛࠶ࡗࡓࠋSiN ࡢ඘ሸ⋡ࡣ 0.28 ࡛࠶ࡾࠊfloating ≧ែࡀฟ⌧ࡍࡿࡢࡣᙜ↛࡜ࡶப࠼ࡿࠋ
SiN ୰ N ཎᏊࡣ࿘ᅖࡢ 3 ࡘࡢ Si ཎᏊ࡜࣎ࣥࢻࢆᙧᡂࡋ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚ࠊ
VN ࡀ⏕ࡌࡿ࡜᭱㏆᥋ࡢ 3 ࡘࡢ Si ཎᏊ࠿ࡽࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻ㸦db㸧ࡀฟ⌧ࡋࠊ୰ᛶ≧ែ࡛ࡣࡑࡇ࡟㸱㟁Ꮚࡀᒁᅾࡍࡿࠋ
3 ࡘࡢ db ≧ែࡣࠊཎᏊᵓ㐀ࡢᑐ⛠ᛶ࠿ࡽࠊ඲ᑐ⛠ࡢ≧ែࡦ࡜ࡘ࡜ 3Si ཎᏊ㛫࡟⠇ࢆࡶࡘ 2 ࡘࡢ≧ែ࡟ศ⿣ࡋࠊ๓⪅ࡣ౯㟁Ꮚᖏ୰࡟ࠊࡲࡓᚋ⪅ࡣࢠࣕࢵࣉ୰࡟Ꮡ

ᅗ 3: VN ࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡓࢠࣕࢵࣉ௜㏆ࡢ㟁Ꮚ≧ែࠋVN ࡣ+1
࠿ࡽ-5 ࡲ࡛ࡢⲴ㟁≧ែࢆྲྀࡾᚓࡿࠋ6eV ௨ୗࠊ11 eV ௨ୖࡢ㟷⥺ࡣࠊ౯㟁Ꮚᖏࠊఏᑟᖏ࡟ᑐᛂࠊ௚ࡢ㟷⥺ࡣ db ≧ែࠋ㉥⥺ࡀ᪂ࡓ࡟Ⓨぢࡉࢀࡓᒁᅾ floating ≧ែࠋᅾࡍࡿ㸦ᅗ 3㸧ࠋࡋࡓࡀࡗ࡚୰ᛶ≧ែ࡛ࡢ 3 ಶࡢ㟁Ꮚࡣ඲ᑐ⛠≧ែ࡟ 2 ಶࠊࢠࣕࢵࣉ୰≧ែ࡟ 1 ಶࡢ㟁Ꮚࢆ཰ᐜࡍ
ࡿࠋࢠࣕࢵࣉ୰ࡢࣇ࢙࣑ࣝ‽఩ࡢ఩⨨࡟౫Ꮡࡋ࡚ࠊࡇࢀ
ࡽࡢࢠࣕࢵࣉ୰≧ែࡣ 0 ಶ࠿ࡽ 4 ಶࡲ࡛ࡢ㟁Ꮚࢆ཰ᐜ
ࡋࠊVN ࡣ+1 ࠿ࡽ-3 ࡲ࡛ࡢⲴ㟁≧ែࢆྲྀࡿࠋ
ࡇ࠺ࡋࡓⲴ㟁≧ែ࡜ࡣᮏ㉁ⓗ࡟␗࡞ࡿ≧ែࡀᏑᅾࡍࡿ
ࡇ࡜ࡀィ⟬ุ࡛᫂ࡋࡓࠋࡑࢀࡣᒁᅾ floating ≧ែ࡜࠸࠺࡭ࡁࡶࡢ࡛ࠊᅗ 4 ࡟ࡑࡢ㌶㐨≧ែࢆ♧ࡍࠋVN ᭱㏆᥋ࡢ 3Si

ᅗ 4: ᒁᅾ floating ≧ែࡢ㟁Ꮚ㌶㐨ࠋVN ㏆᥋ࡢ
3Si ཎᏊࡢᡂࡍᖹ㠃࡟ᆶ┤᪉ྥ(a)࠾ࡼࡧᖹ⾜᪉ྥ(b)࠿ࡽࡢ㌶㐨ࡢ➼್㠃㸦㟷+ࠊ㯤̿㸧ࠋ㟷࡜ⓑࡢ⌫ࡣࡑࢀࡒࢀ SiࠊN ཎᏊࠋཎᏊ࿘ᅖࡢ✵㛫࡟ᾋ࠿ࢇ࡛࠸ࡿࡼ࠺࡞≧ែ࡛࠶ࡿࠋdb ㌶
㐨ࡢᡂศࡣࡍ࡛࡟ูࡢࢠࣕࢵࣉ୰ࡢ㟁Ꮚ≧ែ࡜࡞ࡗ࡚࠸ࡿࡢ࡛ࠊࡇࢀࡣ࣍ࢫࢺ୰࡟Ꮡᅾࡋࡓ floating ≧ែ(ᅗ2)ࡢෆࡢࡦ࡜ࡘࡀࠊ❅⣲✵Ꮝ௜㏆ࡢᘬຊ࣏ࢸࣥࢩࣕࣝ㸦SiN ୰ࡢ N ࡣ㈇࡟ᖏ㟁ࡋ࡚࠸ࡿࡢ࡛ࠊࡑࡢḞᦆࡣᘬຊ࣏ࢸࣥࢩࣕࣝࢆ⏕ࡴ㸧ࢆឤࡌ࡚ᒁᅾࡋࡓࡶࡢ࡛࠶ࡿࠋ㟁Ꮚ‽఩ࡢ࢚ࢿࣝࢠ࣮఩⨨࡜ࡋ࡚ࡣࠊᅗ 3 ࡢ㉥⥺࡛♧ࡍࡼ࠺࡟ࠊ㟁Ꮚᤕ⋓࡟ࡼࡾ኱ࡁࡃୗ᪉ࢩࣇࢺࡋࠊࢠࣕࢵࣉ୰࡟ฟ⌧ࡍࡿࠋࡇࢀࡽࡢᒁᅾ floating ≧ែࡣࠊdb≧ែ࡜ࡣ኱ࡁࡃ␗࡞ࡾࠊ㟁Ꮚࡢᤕ⋓࣭ᨺฟ࡟ᑐࡋ࡚ཎᏊᵓ㐀ࠊ࣎ࣥࢻ㓄⨨ࡢ෌ᵓᡂࡀぢࡽࢀ࡞࠸ࠋゝ࠸᥮࠼ࢀࡤࠊᤕ⋓࣭ᨺฟࡀྍ㏫ⓗ࡛࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊ࣓࣮ࣔࣜᶵ⬟ࡢⓎ⌧࡟ࡣ᭷฼࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ
ࡉࡽ࡟ࠊᐇ㝿ࡢࢧࣥࣉࣝ࡟ࡣỈ⣲ཎᏊࡀከ㔞࡟ྵࡲࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊVN ࡜Ỉ⣲ࡢ」ྜయࡢᵓ㐀࡜㟁Ꮚ≧ែࢆ DFT㸫ࣁ࢖ࣈࣜࢵࢻ㏆ఝ࡛ㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊH ཎᏊࡣ VN ࡜」ྜయࢆᙧᡂࡋࠊ᭱Ᏻᐃ࡞」ྜయ࡛ࡣࠊ+2ࠊ୰ᛶࠊ-2 ࡢⲴ㟁≧ែࢆྲྀࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ᣍᚅㅮ₇㸦୍㒊㸧(1) ‫ۻ‬A. Oshiyama, “Clarification of Microscopic Mechanisms of GaN Epitaxial Growth and Interface
Formation by Density-Functional Calculations” The 20th International Conference on Metal-organic
Vapor Phase Epitaxy (ICMOVPE XX) (Fellbach, Germany, July 10-15, 2022)- 496 -

(2) ‫ۻ‬A. Oshiyama, “Computics approach to development of the next-generation semiconductor science”
The 30th Anniversary Symposium of the Center for Computational Sciences at the University ofTsukuba (Tsukuba, Japan, October 13-14, 2022).
(3) ᯇୗ㞝୍㑻ࠊᒾ⏣₶୍ࠊᑠᮡኴ୍ࠊࢺࣛࣥࣂࣇࣥࠊす㇂ౡᑗࠊす⣫ྐ, “ᮦᩱィ⟬㸸ྂ඾ࢥࣥࣆ࣮ࣗࢱ࡛
࡛ࡁࡿࡇ࡜ࠊ㔞Ꮚࢥࣥࣆ࣮ࣗࢱ࡛ࡋ࠿࡛ࡁ࡞࠸ࡇ࡜ࠥᮦᩱィ⟬ࣉࣛࢵࢺࣇ࢛࣮࣒ Quloud-RSDFT ࢆ౛࡟”, ࢩࣜࢥࣥᮦᩱ࣭ࢹࣂ࢖ࢫ◊✲఍㸦SDM㸧, 2022 ᖺ 11 ᭶, ࢜ࣥࣛ࢖ࣥ.
(4) ‫ۻ‬ᐮᕝ⩏⿱, “GaN MOCVD ࡟࠾ࡅࡿࣉࣟࢭࢫ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࡢ㐍ᒎ”, ໬ᏛᕤᏛ఍ CVD ཯ᛂศ⛉఍➨ 37 ᅇࢩ࣏ࣥࢪ࣒࢘ࠕCVD ࡜ⷧ⭷ࡢィ⟬⛉Ꮫࠖ, (ᮾி / Onlineࠊ2023.3.13).
(5) ‫(ۻ‬ᇶㄪㅮ₇) ᐮᕝ⩏⿱, “❅໬≀༙ᑟయࣉࣟࢭࢫ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࡢ㛤ᣅ”, ᪥ᮏᮦᩱᏛ఍ ࢼࣀᮦᩱ㒊㛛ጤဨ఍࣭ ༙ᑟయ࢚ࣞࢡࢺࣟࢽࢡࢫ㒊㛛ጤဨ఍ ྜྠ◊✲఍, (ி㒔኱Ꮫࠊ2022.11.19).
(6) (Tutorial) ᐮᕝ⩏⿱, “༙ᑟయᮦᩱ㛤Ⓨࡢ᪂ᶵ㍈?ࣉࣟࢭࢫ࣭࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ?”, ࣡࢖ࢻࢠࣕࢵࣉ༙ᑟ
యᏛ఍➨ 10 ᅇ◊✲఍㸦ࢳ࣮ࣗࢺࣜ࢔ࣝㅮ₇఍㸧, (࢘࢖ࣥࢡឡ▱ / Onlineࠊ2022.10.06-07).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1)‫ۻ‬M. Boero, K. M. Bui, K. Shiraishi, K. Ishisone, Y. Kangawaa, and A. Oshiyama, “An atomistic insight into
reactions and free-energy profiles of NH3 and Ga on GaN surfaces during the epitaxial growth” Appl. Surf. Sci. 599,
153935 (2022).

(2)‫ۻ‬T. Kimura, K. Chokawa, K. Shiraishi, and A. Oshiyama, “Microscopic identification of stepped SiC (0001) andthe reaction site of hydrogen-rich epitaxial growth” Phys. Rev. B 106, 035309 (2022).

(3)‫ۻ‬M. Boero, F. Imoto and A. Oshiyama, “Atomistic insight into initial stage of graphene formation on SiC (0001)
surfaces” Phys. Rev. Materials 6, 093403 (2022).

(4)‫ۻ‬K. M. Bui, K. Shiraishi and A. Oshiyama, “Insight into the Step Flow Growth of Gallium Nitride based on Density
Functional Theory" Appl. Surf. Sci. 613, 155840 (2023).

(5)‫ۻ‬K. Chokawa, K. Shiraishi and A. Oshiyama, “Atomic and electronic structures of interfaces between amorphous(Al2O3)1-x(SiO2)x and GaN polar surfaces revealed by first-principles simulated annealing technique” J. Appl. Phys
133, 065301 (2023).

(6)‫ۻ‬F. Nanataki, K. Shiraishi, J.-I. Iwata, Y.-i. Matsushita, and A. Oshiyama, “Atomic and electronic structures ofnitrogen vacancies in silicon nitride: Emergence of floating gap states” Phys. Rev. B 106, 155201 (2022).

(7)‫ۻ‬F. Nanataki, J.-i. Iwata, K. Chokawa, M. Araidai, A. Oshiyama and K. Shiraishi, “Microscopic physical origin of
charge traps in 3D NAND flash memories” Jpn. J. Appl. Phys. 62, SC1038 (2023).

(8)

T. Kosugi, Y. Nishiya, H. Nishi and Y.-i. Matsushita, “Imaginary-time evolution using forward and backward realtime evolution with a single ancilla: First-quantized eigensolver algorithm for quantum chemistry” Physical Review
Research 4, 033121/1-13 (2022).

(9)ᢲᒣ῟ࠊⓑ▼㈼஧, “GaN ⷧ⭷ᡂ㛗ᶵᵓゎ᫂࡬ࡢ㔞Ꮚㄽィ⟬⛉Ꮫࡢ࢔ࣉ࣮ࣟࢳ” ᪥ᮏ⤖ᬗᡂ㛗Ꮫ఍ㄅ 50,
50-1-03 (2023).

(10) ⲡሙᙲ, ᐮᕝ⩏⿱, ஂಖᒣဴ஧, ᪂⏣ᕞ࿃, ⓑ▼㈼஧, ᢲᒣ῟, “GaN ᭷ᶵ㔠ᒓẼ┦ᡂ㛗࡟࠾ࡅࡿࢹࢪࢱࣝ
ࢶ࢖ࣥ㛤Ⓨࡢ⌧≧” ᪥ᮏ⤖ᬗᡂ㛗Ꮫ఍ㄅ 50, 50-1-05 (2023).

- 497 -

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2.1 ⰾ㤶᪘ศᏊ࡟࠾ࡅࡿ㹖⥺ㄏ㉳㠀᩿⇕㑄⛣ࡢ᫬ᐃᩘ࡟ᑐࡍࡿศᏊࢧ࢖ࢬ౫Ꮡᛶ
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LLL ౯࢝ࢳ࢜ࣥࡢ㟁Ꮚ≧ែᩘࡀ౯㟁Ꮚᩘ 1 ࡢ  ஌࡟ẚ౛ࡍࡿࡇ࡜ࡢ  ࡘࢆ⏝࠸࡚ Ĳ1$7 ࡜ Nv ࡢ㛵ಀᘧࢆෆ㒊㌿᥮࣭㡯㛫஺ᕪࡢ཮᪉࡟ᑐᛂ࡛ࡁࡿᙧᘧ࡛ᑟฟࡋࡓ㸬ࡑࡢ⤖ᯝ㸪
Ĳ1$7 Nv = ĲOQ Nv14' ࡜࠸࠺ࢫࢣ࣮ࣜࣥࢢ๎ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ>@㸬ࡇࡇ࡛ Ĳ ࡣཧ↷࡜࡞ࡿศᏊࡢ㠀᩿⇕㑄⛣᫬ᐃᩘ㸪14' ࡣཧ↷ศᏊ࡟࠾࠸࡚㸪ᨃ⦰㏥㧗㟁Ꮚບ㉳஧౯࢝ࢳ࢜ࣥ≧ែࢆᙧᡂࡍࡿࡢ࡟ᚲせ࡞౯㟁Ꮚᩘࢆ⾲ࡍ㸬14' ࡜ Ĳ ࢆࢳ࢜ࣇ࢙ࣥศᏊ 1  ࡢᐇ㦂್ Ĳ1$7 Ĳ IV >G@࠿ࡽồࡵ㸪WURSRQH 1Y  XUDFLO 1Y  JXDQLQH
1Y   ࡟㐺⏝ࡋࡓ㸬࡞࠾㸪WURSRQH ࡟ࡘ࠸࡚ࡣ㸪 ✵Ꮝ≧ែࢆࡍ࡭࡚⪃៖ࡋࡓ≧ែᖹᆒ &$66&) ἲ࡛ィ⟬ࡋࡓ OLQHDUYLEURQLFFRXSOLQJ ࣔࢹࣝࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸ࡓ 6XUIDFHKRSSLQJ ᆺ㠀᩿⇕཯ᛂືຊᏛィ⟬>@࠿ࡽ⟬ฟࡋࡓ᫬ᐃᩘ Ĳ0' ࡜ࡶẚ㍑ࡋࡓ㸬- 498 -◊✲ᡂᯝ(1) ᘧࢆ tropone2+ࡢᨃ⦰㏥㧗㟁Ꮚບ㉳஧౯࢝ࢳ࢜ࣥ≧ែ࡟㐺⏝ࡋࡓ⤖ᯝࢆ⾲㸯࡟♧ࡍ>@㸬tropone ࡢȫNAT ࡣ 226 s 18 fs ࡜ィ⟬ࡉࢀ㸪㠀᩿⇕཯ᛂືຊᏛィ⟬࠿ࡽᚓࡽࢀࡓ್ ȫMD 㸻234 s 1 fs ࡜ᐃ㔞ⓗ࡟୍⮴ࡋࡓ㸬ࡇࢀࡣ㸪(1)ᘧࡀᑡ࡞ࡃ࡜ࡶ༙ᐃ㔞ⓗ࡞⢭ᗘࢆᣢࡗ࡚࠸ࡿࡇ࡜ࢆ♧ࡍ㸪ࡲࡓ㸪tropone2㸩ࡢప࢚ࢿࣝࢠ
࣮㟁Ꮚບ㉳≧ែ࡟࠾ࡅࡿ㠀᩿⇕㑄⛣ࡢ᫬ᐃᩘࡣ㠀᩿⇕཯ᛂືຊᏛィ⟬࠿ࡽ㸪   IV ࡜ぢ✚ࡶࡽࢀ࡚࠾ࡾ㸪ȫMD ࡢ⣙ 1/3 ࡛࠶ࡿ㸬௨ୖࡢ⤖ᯝࡣᨃ⦰㏥㧗㟁Ꮚບ㉳஧౯࢝ࢳ࢜ࣥ≧ែ࡟࠾ࡅࡿ㠀᩿⇕㑄⛣㐣⛬࡟࠾࠸࡚ࠕSRSXODWLRQWUDSࠖࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ㸬 ࡉࡽ࡟㸪(1)ᘧࢆ᰾㓟ሷᇶ Uracil ཬࡧ Guanine ࡟ࡶ㐺⏝ࡋࡓ㸬ࡑࡢ⤖ᯝ㸪Tropone ࡜౯㟁Ꮚᩘࡀ࡯ࡰྠࡌ uracil
࡛ࡣ tropone ࡜ྠᵝ࡟ 200fs ⛬ᗘࡢ population trap ࡀ㸪౯㟁Ꮚᩘࡀ tropone ࡼࡾ 16 㟁Ꮚከ࠸ guanine ࡛ࡣ 300 fs⛬ᗘࡢ Population Trap ࡀᨃ⦰㏥ࡋࡓ dication ࡢ㧗㟁Ꮚບ㉳≧ែ࡛㉳ࡁࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ>@㸬௨ୖࡢࡼ࠺࡟㸪(1)ᘧࢆ⏝࠸ࡿࡇ࡜࡛㸪㧗ィ⟬ࢥࢫࢺࡢ㠀᩿⇕཯ᛂືຊᏛィ⟬ࢆ⏝࠸ࡎ࡟㸪X ⥺↷ᑕ࡟ࡼࡗ࡚⏕ࡌࡿⰾ㤶᪘ศᏊࡢᨃ⦰㏥㧗㟁Ꮚບ㉳஧౯࢝ࢳ࢜ࣥ≧ែ࡟࠾ࡅࡿ㠀᩿⇕㑄⛣᫬ᐃᩘ Ĳ1$7 ࢆ༙ᐃ㔞ᐃᮇ࡞⢭ᗘ࡛ぢ✚ࡶࡿࡇ࡜ࡀྍ⬟࡟࡞ࡗࡓ㸬   ᘧࢆ⏝࠸ࡿࡇ࡜࡛㸪 Ⰽࣇ࢙࣒ࢺ⛊ ; ⥺᫬㛫ศゎศගἲ࡟࠾࠸࡚᭱ప㝈ᚲせ࡞᫬㛫ศゎ⬟ࢆ⡆౽࡟ぢ✚ࡶࢀࡿࡓࡵ㸪ᐇ㦂ࡢィ⏬❧᱌ࡸ⤖ᯝ᳨ドࡀࡼࡾᐜ᫆࡟࡞ࡿ࡜ᮇᚅࡉࢀࡿ㸬⾲1

Thiophene, tropone, guanine ࡢศᏊᵓ㐀ᘧ࣭(1)ᘧࢆ⏝࠸࡚ィ⟬ࡉࢀࡓ Ĳ1$7㸬7URSRQH ࡟࠾ࡅࡿ㠀᩿⇕ືຊᏛィ⟬>@࠿ࡽ⟬ฟࡋࡓ᫬ᐃᩘ Ĳ0'

Thiophene[d](Reference)*
Nv

TroponeUracilGuanine

26

40

42

56

τNAT (fs)*

158  12226  18234  18279  18

τMD (fs)---

234  1------

*Thiophene: τ0 = 158  12 fs , NQD =Nv(Ref) / e ٙ 9.57  1.03

ཧ⪃ᩥ⊩[a] C. Liekhus-Schmaltz et al. Nat. Commun. 6, 8199(2015)[b] X. Wang et al., Nat. Photo. 15, 187, (2021)[c] M. Hervé et al., Nat. Phys. 17, 327 (2021)[d] E. Kukk et al., Phys. Rev. Res. 3, 013221 (2021)- 499 -

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Computational Investigations of Exciton Dynamics inOrganic Optoelectronic Materials Based onLarge-Scale Electronic Structure Calculations‫ ⏣⸨ۑ‬㈗ᩄ 㸦㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓ㸧1◊✲┠ⓗInternet-of-Thing ᫬௦ࡢࣇࣞ࢟ࢩࣈࣝࢹࣂ࢖ࢫ࡜ࡋ࡚᭷ᶵ༙ᑟయᮦᩱࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ᭷ᶵ༙ᑟయᮦᩱ

ࡣ஘ࢀࡓศᏊ㞟ྜయ࡛࠶ࡾࠊࡑࡢග㟁Ꮚ≀ᛶࡣ᭷ᶵศᏊࡢᛶ㉁࣭ศᏊ㛫ࡢࣃࢵ࢟ࣥࢢᵓ㐀࣭ᵓ㐀஘ࢀ࡞࡝ࡢ
ᵝࠎ࡞ᅉᏊ࡟౫Ꮡࡍࡿࠋ㟁⏺ຠᯝࢺࣛࣥࢪࢫࢱࡢ㟁Ⲵ㍺㏦ࡸ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ㟁Ⲵศ㞳࡞࡝ࠊࢹࣂ࢖ࢫ≉ᛶࢆỴࡵ࡚࠸ࡿ⣲㐣⛬ࡣ⏺㠃࡛㉳ࡁࡿࠋࡘࡲࡾࠊࢹࣂ࢖ࢫ≉ᛶணࡢࡓࡵ࡟ࡣ⏺㠃㏆ഐ࡛ࡢ㟁Ꮚ≀ᛶࢆゎᯒࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ኱つᶍ㟁Ꮚ≧ែ⌮ㄽࡸ㔞ᏊືຊᏛ⌮ㄽࢆ㥑౑ࡋ࡚ࠊ஘ࢀࡓ᭷ᶵ/᭷ᶵ⏺㠃⣔࡟࠾ࡅࡿ㟁Ꮚ≧ែ࣭ග≀ᛶ࣭㟁Ⲵศ㞳࣭㟁Ⲵ෌⤖ྜࢆゎᯒࡋࠊࢹࣂ࢖ࢫᛶ⬟࡜ࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࠋࡉࡽ࡟ࠊ
ࡇࢀࡲ࡛㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨(FMO)ἲࢆ࣮࣋ࢫ࡜ࡋ࡚ࠊບ㉳Ꮚࡢᐇ᫬㛫ࢲ࢖ࢼ࣑ࢡࢫࡸ
ศගࢩࢢࢼࣝࢆィ⟬ࡍࡿࡓࡵࡢ⌮ㄽ࣭ィ⟬ᇶ┙ࢆ☜❧ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࣉࣟࢢ࣒ࣛࡣ GAUSSIAN, ABINIT-MP, ࡉࡽ࡟⮬సࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࣭ศගࢩࢢࢼࣝィ⟬⏝ࡢࣉࣟࢢ࣒ࣛ

ࢆ⏝࠸ࡓࠋGaussian ࡛ࡣᏙ❧୍ศᏊࡢᵓ㐀᭱㐺໬࣭ບ㉳≧ែィ⟬ࢆ⾜࠺ࠋABINIT-MP ࡣᙜࢢ࣮ࣝࣉ࡛㛤Ⓨࢆ㐍ࡵ࡚࠸ࡿࣉࣟࢢ࣒࡛ࣛ࠶ࡾࠊFMO ἲ࡟ࡼࡿ኱つᶍ㟁Ꮚ≧ែィ⟬ࢆ⾜࠺ࠋ⏺㠃ᵓ㐀సᡂ࡞࡝ࡣ TINKER ࢆ౑ࡗ࡚‽ഛࡍࡿࠋ3◊✲ᡂᯝ
A. P3HT/PCBM ࡢ㟁Ⲵศ㞳ࢲ࢖ࢼ࣑ࢡࢫ࡜㐣Ώ྾཰ࢫ࣌ࢡࢺࣝ
࣏ࣥࣉ-ࣉ࣮ࣟࣈศගἲࡸ 2 ḟඖ㟁Ꮚศගἲ࡞࡝✀ࠎࡢ᫬㛫ศゎศගἲࡣගບ㉳ᚋࡢࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒࡍࡿࡓࡵࡢᐇ㦂ᡭἲ࡛࠶ࡾࠊ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ㟁Ⲵศ㞳ࡢゎᯒ࡟⏝࠸ࡽࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ࣑ࢡࣟ࡞ᵓ㐀ࢆᚓࡿࡢࡀ㞴ࡋࡃࠊࢫ࣌ࢡࢺࣝࡢᖐᒓ࡟ࡘ࠸࡚ࡶ᭕᫕ࡉࡀṧࡿࡓࡵࠊບ㉳Ꮚࡸ࢟ࣕࣜ࢔ࡢ
ࢲ࢖ࢼ࣑ࢡࢫ࡜ศගࢩࢢࢼࣝ࡜ࡢᑐᛂࡣ༑ศ࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿ࡜ࡣゝ࠸㞴࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣ P3HT ࡜ PCBM ࠿ࡽ࡞ࡿ࢔ࣔࣝࣇ࢓ࢫᵓ㐀ࢆ MD ἲ࡛సᡂࡋࡓࠋᚓࡽࢀࡓᵓ㐀࠿ࡽ࠾ࡼࡑ 30 ศᏊࢆษࡾฟࡋࡓᵓ㐀ࢆ P3HT/PCBM ⏺㠃ࡢࣔࢹࣝ࡜ࡋ࡚(ᅗ(a))ࠊ㟁Ꮚ≧ែ࣭ບ㉳Ꮚࢲ࢖ࢼ࣑ࢡࢫ࣭ศ
ගࢩࢢࢼࣝ㸦྾཰ࢫ࣌ࢡࢺࣝ࡜㐣Ώ྾཰ࢫ࣌ࢡࢺࣝ㸧ࢆィ⟬ࡋࡓࠋ㟁Ꮚ≧ែィ⟬ࡼࡾᚓࡽࢀࡓ࢚ࢿࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛ㸦㟁Ꮚ-ṇᏍ㊥㞳 vs ບ㉳࢚ࢿࣝࢠ࣮㸧ࢆᅗ(b)࡟♧ࡍࠋ- 502 -

㉥Ⅼࡀ P3HT ࡢບ㉳Ꮚ≧ែࠊ⥳Ⅼࡀ CT ≧ែࠊ㟷ⅬࡀṇᏍບ㉳ࡋࡓ CT ≧ែ࡛࠶ࡿࠋᅗ(c)ࡀ྾཰ࢫ࣌ࢡࢺ࡛ࣝ
࠶ࡾ P3HT ࡢບ㉳Ꮚ≧ែࡀ୺࡟ᐤ୚ࡍࡿࠋᮏ◊✲ࡢບ㉳≧ែࡢࣔࢹ࡛ࣝࡣࠊ࣏ࣥࣉග࡛ P3HT ࡢ࢚࢟ࢩࢺࣥ
≧ែࡀ⏕ᡂࡉࢀ(ᅗ(b)㸸㉥Ⅼ)ࠊ㟁Ⲵ⛣ື(ᅗ(㉥ⅬЍ⥳Ⅼ)ᚋࡢ CT ≧ែࡀࣉ࣮ࣟࣈගࢆ྾཰ࡋ࡚ṇᏍບ㉳ࡍࡿ
(⥳ⅬЍ㟷Ⅼ)ࠋࡉࡽ࡟ࠊ㟁Ⲵศ㞳ࢲ࢖ࢼ࣑ࢡࢫ࡜㐣Ώ྾཰ศගࢩࢢࢼࣝࢆヲ⣽࡟ẚ㍑ࡋࡓ࡜ࡇࢁࠊ࣏ࣥࣉ-ࣉ࣮ࣟࣈࡢ ESA ࡢ␗᪉ᛶࡢࢲ࢖ࢼ࣑ࢡࢫࡀࠊ㟁Ⲵศ㞳ࡢ᫬ᐃᩘ࡜ࡼࡃ┦㛵ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡋࡓࠋ

ᅗ:(a)P3HT(㉥)/PCBM(㟷)ࡢ࢔ࣔࣝࣇ࢓ࢫᵓ㐀ࠋ(b)㟁Ꮚ-ṇᏍ㊥㞳(ᶓ㍈)-ບ㉳࢚ࢿࣝࢠ࣮(⦪㍈)ࡢ
࢚ࢿࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛࠋ(c)྾཰ࢫ࣌ࢡࢺࣝ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ⏣⸨ۻ‬㈗ᩄ, ͇ ࣇࣛࢢ࣓ࣥࢺศ๭ᆺ GW/BSE ἲࡢ㛤Ⓨ࡜ᛂ⏝͇,ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔

࣒㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍ 2020, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ
2 ᭶ 15 ᪥‫ ⏣⸨ۻ‬㈗ᩄ, “ග㟁ኚ᥮㐣⛬ࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡜᫬㛫ศゎศග”,ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔

࣒㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘ 㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍ 2022

2023 ᖺ 2 ᭶ 13 ᪥‫ ⏣⸨ۻ‬㈗ᩄ, “P3HT/PCBM ࡟࠾ࡅࡿ㟁Ⲵศ㞳ࢲ࢖ࢼ࣑ࢡࢫ࡜ศගࢩࢢࢼࣝࡢ⌮ㄽゎᯒ”, ➨ 70 ᅇᛂ⏝≀⌮Ꮫ఍ ᫓ᏘᏛ⾡ㅮ₇఍

2023 ᖺ 3 ᭶ 16 ᪥

‫ ⏣⸨ۻ‬㈗ᩄ, “኱つᶍ㟁Ꮚ≧ែィ⟬ࢆ⏝࠸ࡓ᭷ᶵ༙ᑟయᮦᩱࡢග㟁Ꮚ≀ᛶ”, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡ
ࢩࣙࢵࣉ 2022ࠕ 」㞧㟁Ꮚ≧ែࡢ⌮ㄽ࣭ィ⟬⛉Ꮫࠖ

2023 ᖺ 1 ᭶ 17 ᪥

‫ ⏣⸨ۻ‬㈗ᩄ, “㟁Ꮚ≧ែィ⟬࡜᫬㛫ศゎศග࡟ࡼࡿ P3HT/PCBM ࡢ㟁Ⲵศ㞳ࡢゎᯒ”, ➨ 83 ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍

52022 ᖺ 9 ᭶ 21 ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Masaaki Tsubouchi, Nobuhisa Ishii, Yuji Kagotani, Rumi Shimizu, Takatoshi Fujita, Motoyasu Adachi, Ryuji Itakura,“Beat-frequency-resolved two-dimensional electronic spectroscopy: disentangling vibrational coherences in artificial
fluorescent proteins with sub-10-fs visible laser pulses”, Optics Express, vol. 31, pp. 6890-6906. (2023).
‫ۻ‬Takatoshi Fujita, Takeo Hoshi, “Ab Initio Study of Charge Separation Dynamics and Pump–Probe Spectroscopy in
the P3HT/PCBM Blend”, submitted, DOI: https://doi.org/10.26434/chemrxiv-2023-773xs.

- 503 -

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䜎䛩䚹ᥖ㍕㡰ᗎ䛿ཎ๎䛸䛧䛶ᙜ䝉䞁䝍䞊䜈ᥦฟ䛥䜜䛯㡰䛻㏻䛧␒ྕ䜢௜䛡䜎䛧䛯䚹ㅰ㎡䛾グ㍕䛜䛺䛔ㄽᩥ䛿ῐⰍ䛷⾲♧䛧䜎䛧䛯䚹㻌

1.

"Key Residue for Aggregation of Amyloid-ȕ3HSWLGHV
Satoru G. Itoh, Maho Yagi-Utsumi, Koichi Kato and Hisashi Okumura
ACS Chem. Neurosci., 13(22), 3139-3151 (2022)

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Journal of Inorganic Biochemistry, 246(), 112292 (2023)

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Kenji Tsukamoto, Koji Takagi, Seihou Jinnai, Yutaka Ie, Mitsuo Hara and Takanori Fukushima
Mol. Syst. Des. Eng., 7(12), 1639-1649 (2022)

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J. Phys. Chem. B, 126(26), 4948-4955 (2022)
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European Journal of Medicinal Chemistry, 252(), 115271 (2023)

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J. Org. Chem., 87(19), 12653-12672 (2022)

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Koichi Nagata, Ayako Hino, Hitoshi Ube, Hiroyasu Sato and Mitsuhiko Shionoya
Dalton Trans., 52(11), 3295-3299 (2023)
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ᶓᒣࠉ኱㍜


FU
Ṋḟࠉᚭஓ


FV
5DHELJHU+DQQHV

FW
ୖ⏣ࠉ୍⩏



- 539 -

ㄽᩥ␒ྕ

















ࢥ࣮ࢻ
FY
FY
FZ
FZ
FZ
F[
F\
F\
F\
F]
GD
GE
GE
GF
GF
GF
GI
GJ
GJ
GK
GK
GL
GM
GM
GN
GT
GV
GX
GX
GZ
G[
HE
HH
HK
HK
HN
HN
HP
HP
HS
HT
HT
HT
HV
HW
HX
HY
HZ

௦⾲⪅ྡ
బ⸨ࠉၨᩥ
㔠㔝ࠉ኱ຓ
㰻⸨ࠉ኱᫂
‫‮‬஭ࠉᩄᩥ
ᒸᓮࠉ㐍
ྜྷ⏣ࠉ೺
ᒾᮏࠉၨ
⛅ὠࠉ㈗ᇛ
ᐑ⏣ࠉ❳ᙪ
ᒣཱྀࠉ඙
㛗㇂ᕝࠉ┿ኈ
ஂ᪂ࠉⲮ୍㑻
ὠ␃ᓮࠉ㝧኱
ᒣ໭ࠉెᏹ
ఀ⸨ࠉ႐ග
ᓲࠉ㝯ᇶ
ᒣᮏ඾ྐ
୕஭ࠉṇ᫂
ᑎ⏣ࠉᬛᶞ
ᯘࠉ㔜ᙪ
ධబࠉṇᖾ
ᯇᮏࠉṇ࿴
୰ᔱࠉ㝯ே
ᰰ἟ࠉឡ
᳃ḟࠉᆂ
ຍ⸨ࠉᫀᏊ
⬟Ⓩࠉ㤶
୰ᮧࠉᰤ୍
㧗ᶫࠉಟ
ᒣୗࠉ᫭୍
኱࿴⏣ࠉᬛᙪ
బࠎᮌࠉᓅᙪೖࠉ๛ஂᕷᶫࠉṇᙪ࿴బ⏣ࠉ⿱᫛
ᅵ⏣ࠉᩔᏊ
ᮏከࠉ୍ᙪ
㫽ᒃࠉ⫕
Ώ㎶ࠉ㇦
୰஭ࠉᾈᕭ
୰㔝ࠉᖾྖ
ᕝཱྀࠉ୍᭸
✄ⴥࠉ▱ኈ
᳃ࠉ⪷἞
ఀ⸨ࠉᙲᾈ
ᑠ㔝ࠉඞᙪ
ᕤ⸨ࠉ⪽
Ἴ⏣ࠉ㞞ᙪ

࣓ࣥࣂ࣮ᩘ

















































- 540 -

ㄽᩥᩘ


ㄽᩥ␒ྕ
















































ࢥ࣮ࢻ
H[
H\
H]
H]
ID
ID
IE
IE
IE
IF
IF
IF
IF
IG
IG
IG
IG
IG
IG
IH
IH
II
IJ
IJ
IJ
IJ
IJ
IK
IK
IK
IK
IK
IK
IL
IL
IL
IM
IM
IN
IN
IO
IO
IO
IP
IP
IP
IP
IQ

௦⾲⪅ྡ
ⓑ▼ࠉ㈼஧
㯮ᓮࠉㆡ
໭ᑿࠉᙲᮁ
⛅ᒣࠉ஽
㧘ᶫࠉ༟ஓ
ᆏ⏣ࠉ೺
ኴ⏣ࠉ㞝኱
㑦ḟࠉᬛ
኱ୗࠉ៞ḟ㑻
ࣜࣥࢺࢗࣝ࢜ࢺࠉṇ⨾
ෆ⏣ࠉᖾ᫂
୰㔝ࠉ⩏᫂
㔠ࠉ㗰
ᒣᓮࠉ⚈ᖹ
⏣୰ࠉு
Ᏹ⏣ᕝࠉኴ㑻
⡿⃝ࠉᗣ⁠ᑠᏳࠉ႐୍㑻
ᙳᓥࠉ༤அ
␊ᒣࠉඔ
⏣୰ࠉ኱㍜
୕⏣ࠉᩥ㞝
▼ᒣࠉ㐩ஓ
ᮧᒸࠉᱻ
బ⸨ࠉᚭ
⏿୰ࠉ⨾✑
኱㫽ࠉ⠊࿴
Ḉ஭ࠉⱥ༤
ఀ⸨ࠉⱥே
*HUJHO\-XKDV]
㛵ࠉಟᖹ
ྜྷ⏣ࠉ⣧
ᰗ⏣ࠉு
⏣୰ࠉ⿱ஓ
ὸᏊࠉኊ⨾
ᖹ㔝ࠉᜏኵ
ὸᕝࠉ኱ᶞ
ᯇ஭ࠉ஽
ྜྷ⏣ࠉ⣖⏕
๓⏣ࠉ኱ග
ᾆࠉᗣஅ
⏣௦ࠉᇶ៞
᪂ᇼࠉె⣖
ᒣୗࠉ೺୍
᳃ᮏࠉ῟ᖹ
᏷ᡞࠉ༤⣖
すෆࠉᬛᙪ
୸ᒣࠉⱱኵ

࣓ࣥࣂ࣮ᩘ
















































- 541 -

ㄽᩥᩘ

ㄽᩥ␒ྕ
































































ࢥ࣮ࢻ
IQ
IQ
IQ
IR
IR
IR
IR
IR
IR
IS
IS
IS
IT
IT
IT
IT
IT
IT
IU
IU
IU
IU
IU
IU
IU
IU
IV
IV
IV
IV
IV
IV
IW
IW
IW
IX
IX
IX
IX
IY
IY
IY
IY
IZ
IZ
IZ
IZ
IZ

௦⾲⪅ྡ
஭ཱྀࠉెဢ
⚄㇂ࠉᫀᏹ
㔝ཱྀࠉᕦ
ᮧ⏣ࠉ្
బ⸨ࠉஂᏊ
ᮾᯘࠉಟᖹ
ⰼᮧࠉோႹ
኱⃝ࠉṇஂ
኱㔝ࠉ┿ஓ
ᒸࠉ┿ᝆᏊ
Ώ㑔ࠉ⥲୍㑻
㣤᳃ࠉಇᩥ
⊁㔝ࠉ┤࿴
஭ᡭࠉᬛோ
ΎỈࠉ❶ᘯ
୕Ꮿࠉு௓
ఀ⸨ࠉ⫕
ᓥ⏣ࠉᩄᏹ
⠛⏣ࠉᜨᏊ
ᆏᮏࠉ㐨᫛
㯮⏣ࠉ኱♸
๓⏣ࠉ⌮
ఀໃᕝࠉ⨾✑
ᐑᓮࠉ⚽ಇ
㓇ᕳࠉ኱㍜
ᯘࠉ⪽Ꮚ
⁪⏣ࠉⰋ
ᒣඖࠉ῟ᖹ
ᙳᒣࠉⳀἋ
ᑠỮࠉె♸
℩㧗ࠉ΅
୰ᮧࠉಟ୍
㕥ᮌࠉ㈼⣖
㕥ᮌࠉ῟ᕧ
3UDGHHS5LVLNULVKQD9DUDGZDM

ᰗ஭ࠉẎ
⛅ᒣࠉⰋ
⏣୰ࠉៅ୍㑻
㛗⏣ࠉᾈ୍
ᩧ⸨ࠉ❳⏨
ᮧ஭ࠉᚁྐ
㯮ᮌࠉᑲ
ṇ஭ࠉᏹ
ᡭᓥࠉṇ࿃
▼ᶫࠉᏕ❶
ᑠᐊࠉ㈗ኈ
᳜⏣ࠉ୍ṇ
す㛗ࠉ஽

࣓ࣥࣂ࣮ᩘ

















































- 542 -

ㄽᩥᩘ


ㄽᩥ␒ྕ
























































ࢥ࣮ࢻ
IZ
IZ
I[
I[
I[
I[
I[
I\
I\
I\
I\
I\
I\
I]
I]
I]
I]
I]
I]
I]
JD
JD
JD
JD
JD
JD
JE
JE
JE
JE
JE
JE
JF
JF
JF
JF
JF
JF
JG
JG
JG
JG
JG
JG
JG
JG
JG
JH

௦⾲⪅ྡ
ᑠᮡࠉ೺ᩯ
ຍ⸨ࠉ೺ኴ
ᯇ⏣ࠉḠஅ
࿃㒓ࠉ཭ᏹ
ᒣᓮࠉ⚈Ꮚ
ᫍᮏࠉ㝧୍
ዟᒣࠉඞᙪ
୰ᒣࠉဴ
⠛⏣ࠉ΅
▼஭ࠉⰋᶞ
ᖹ⏣ࠉᆂ♸
ᒣ㛛ࠉ㝠ᖹ
ྂᒇࠉ⚽ᓠ
ᮎᯇࠉᏳ⏤⨾
Ⅳ❤ࠉாྖ
㧗▼ࠉ࿴ே
⯪᭥ࠉ୍ṇ
)ORULVYDQ(HUGHQ
୰ᮧࠉᾈ❶
⏣୰ࠉ⚽ᶞ
㕥ᮌࠉᗣ௓
ෆᒣࠉὒ௓
ᯇᮏࠉ๛᫛
㧗ᮌࠉᖾ἞
ᮤࠉ⚽ᰤ
ᒣᮏࠉဴஓ
ᜏᕝࠉⱥ௓
ಙ⏣ࠉᑦẎ
᪂ᯘࠉ༟ஓ
἟⏣ࠉ᐀඾
1JX\HQ7KDQK3KXF
すᮏࠉ⬟ᘯ
ᑠᓥṇᐶ
஬༑ᔒࠉ᫂๎
ᇼࠉඃኴ୕ࢶ἟ࠉ἞ಙ
᳃ࠉಇᩥ⏥㈡ࠉ◊୍㑻
ᯘࠉ៞ᾈ
⏣ཱྀࠉ┿ᙪ
᱓ཎࠉ✨
㞵ኪࠉᚭ
⏣௦ࠉ┬ᖹ
ᑎ⏣ࠉ┾ᾈ
᳜ᮧࠉ୍ᗈ
ᮡ⏣ࠉ୍
ྜྷ⏣ࠉᝆ୍㑻
ᖹ஭ࠉ๛

࣓ࣥࣂ࣮ᩘ

















































- 543 -

ㄽᩥᩘ

ㄽᩥ␒ྕ


































































ࢥ࣮ࢻ
JH
JH
JH
JH
JH
JH
JI
JI
JI
JI
JI
JI
JJ
JJ
JJ
JJ
JJ
JJ
JJ
JJ
JJ
JJ
JK
JK
JK
JK
JK
JK
JK
JK
JK
JK
JL
JL
JL
JL
JL
JL
JL
JL
JL
JL
JM
JM
JM
JM
LD
LD

௦⾲⪅ྡ
㏆⸨ࠉ೺
Ύ㔝ࠉ῟ྖ
ྜྷ⏣ࠉᣑே
㧗᳚ࠉ฼ᖾ
ᑠᯘࠉὒ୍
ඤ⋢ࠉᣅஓ
㛗⏣ࠉ⿱ஓ
ග⸨ࠉ⪔୍
ዟὠࠉ㈼୍
Ỉཱྀࠉ᭸Ꮚ
⸨ᮏࠉ࿴ኈ
༓ⴥࠉᩥ㔝
ᚎࠉᏊᬸ
㇂ࠉὒ௓
Ἑ㔝ࠉ⩧ஓ
ඵᮌࠉளᶞᏊ
బஂ㛫ࠉ⯟ஓ
ᐑ㷂ࠉᗣ඾
ᑎᮏࠉ㧗ၨ
ᒣᓮࠉ㈼
㮵ཪࠉႛᖹ
┦⃝ࠉ┤▮
ᑠụࠉ㝯ྖ
▼๭ࠉᩥᓫ
㛗㇂ᕝࠉៅ࿃
኱ஂಖࠉᩗ
ᖹᏊࠉ┤ὒ
ᒣᮏࠉᾈྖ
୰ᮧࠉ㞞᫂
┦㈡ࠉ๎ᏹ
ᒸᮏࠉ୍ኸ
Ṋ⏣ࠉὒᖹ
୰ᮧࠉ㢧ᩯ
⸨ᮏࠉ෸Ꮚ
ྜྷ஭ࠉ✲
బྂࠉ┿
⁪⃝ࠉᚸ
4,$1*ࠉ<8(
಴ᣢࠉᝆ㍜
㛵ᕝࠉ༟ஓ
Ụཱྀࠉ኱ᆅ
┦ᕝࠉ♸⌮
὾⏣ࠉ㐨᫛
ᒣᓮࠉ㞞ே
ᒸᮏࠉ࿴⣫
኱ᶫࠉ࿴ᙪ
⚟Ọࠉ㞞႐
㏆ῧࠉ῟୍

࣓ࣥࣂ࣮ᩘ

















































- 544 -

ㄽᩥᩘ

ㄽᩥ␒ྕ













































ࢥ࣮ࢻ
ND
TF
TF
TF
YD
YE
YF
YF
YF
YF
YH
YH
YH

௦⾲⪅ྡ
ධỤࠉඞ㞞
ᱵ⃝ࠉබ஧
㢠㈡ࠉ㊰჆
ᖭᕝࠉ♸㈨
ᒸᓮࠉ㐍
ᢲᒣࠉ῟
㤋ᒣࠉెᑦ
⸨⏣ࠉ㈗ᩄ
ᒣᓮࠉ㤾
㛗ᒸࠉṇ㝯
ᮡ㔝ࠉಟ
ኳ⬟ࠉ⢭୍㑻
᳃ᕝࠉⰋᛅ

࣓ࣥࣂ࣮ᩘ














- 545 -

ㄽᩥᩘ


ㄽᩥ␒ྕ










ࢭࣥࢱ࣮࣏࣮ࣞࢺ 23
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