II 㒊┠ḟ1 2021 ᖺᗘ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩1.1 2021 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩ᥦฟ≧ἣ(๭ᙜⅬᩘ 30,000 Ⅼ௨ୗ) ··········· 11.2 2021 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩(๭ᙜⅬᩘ 30,000 Ⅼ㉸)·························· 7
2 2021 ᖺᗘィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩ ······· 492
3 ࣮ࣘࢨⓎ⾲ㄽᩥ
3.1 ࣮ࣘࢨㄽᩥ୍ぴ················································································ 514
3.2 ࣉࣟࢪ࢙ࢡࢺูㄽᩥูๅᥦฟ≧ἣ························································ 540

㻝㻚䚷㻞㻜㻞㻝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

㻝㻚㻝㻌㻌㻞㻜㻞㻝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฼⏝ $
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FE

ỈࡢศᏊ㛫ཬࡧศᏊෆ᣺ື࣮ࣔࢻ
࡟ᑐࡍࡿከḟඖ᣺ືศගࡢ㔞Ꮚࢩ࣑࣮ࣗࣞࢩࣙࣥ

ி኱㝔
⌮

㇂ᮧྜྷ㝯


 㸭 

᭷ᶵ໬ྜ≀࡟࠾ࡅࡿ⨨᥮ᇶຠᯝࡢ
ᚤどⓗᶵᵓ

㫽ྲྀ኱
ᕤ

᪩℩ಟ୍


 㸭 

Ỉ⣲⤖ྜᆺᙉㄏ㟁≀㉁ࡢ➨୍ཎ⌮◊✲㧗࢚ࢿࣝࢠ࣮ຍ㏿ჾ
◊✲ᶵᵓ

ᒾ㔝ࠉ⸅


 㸭 

㟼ᒸ⌮ᕤ⛉኱⌮ᕤ㛵ᒣ⚽㞝 㸭 

໭㔛኱
⌮

▼ᕝ᫓ᶞ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᢠ&29,'⸆๣ೃ⿵࡟㛵ࡍࡿ⌮ㄽ◊✲᪥ᮏཎᏊຊ◊✲㛤Ⓨᶵᵓࢩࢫࢸ࣒ィ⟬⛉Ꮫ
ࢭࣥࢱ࣮

ᩘ⣡ᗈဢ


 㸭 

GࡲࡓࡣG㔠ᒓࢆྵࡴከ᰾㔠ᒓ㘒యࡢ㟁Ꮚ≧ែ

ᒱ㜧኱
ᕤ

ᾏ⪁ཎᫀᘯ


 㸭 

ศᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀ไᚚ࡟ࡼࡿ
໬Ꮫ཯ᛂࡢᵓ㐀౫Ꮡᛶࡢ◊✲

໭㔛኱
⌮

Ỉ℩㈼ኴ


 㸭 

⸆≀࡜㣧㣗≀࡟ྵࡲࢀࡿ⏕⌮άᛶ≀㉁࡜ࡢ┦஫స⏝ゎᯒ

⚟ᒸ኱
⸆

ụ⏣ᾈே


 㸭 

పศᏊ㠀ᬗ㉁᭷ᶵ༙ᑟయᮦᩱࡢᅛ
య⭷୰࡟࠾ࡅࡿ㓄ᗙศᕸ࡟㛵ࡍࡿィ⟬ᒣᙧ኱㝔᭷ᶵᮦᩱࢩࢫࢸ࣒

ᶓᒣ኱㍜ 㸭 

ᚤ⣽ᵓ㐀ࢆㄆ㆑ࡍࡿ㉸ศᏊ」ྜ⣔ࡢᵓ⠏࡜ᵓ㐀ゎᯒ

᪂₲኱㝔
⮬↛⛉Ꮫ

ᒾᮏࠉၨ


 㸭 

ࢩࢵࣇሷᇶ㔠ᒓ㘒యࡢ㟁Ꮚᵓ㐀࡜⺮ⓑ㉁࡬ࡢࢻࢵ࢟ࣥࢢ᥈⣴

ᮾி⌮⛉኱
⌮

⛅ὠ㈗ᇛ


 㸭 

FE

FH

FJ

FJ

FL

FO

FP

FR

FS

F\

F\

㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Ỉ⣲⤖ྜࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ㉥እㄏ㉳␗ᛶ໬཯ᛂࡢほ ࡜␗ᛶ໬⤒㊰ࡢ᥈⣴㸦㸰㸧

-1-㸦࣓ࣥࣂ࣮ᩘ㸧

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

◊✲ㄢ㢟ྡ

ᡤᒓ

GD

᪂ࡋ࠸Ⓨගᛶȧඹᙺ⣔໬ྜ≀ࡢྜᡂ◊✲࡜ග≀ᛶ

໭㔛኱
⌮

㛗㇂ᕝ┿ኈ


 㸭 

ࢼࣀ࣮࣭࢝࣎ࣥ࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊
✲

㟁㏻኱㝔
᝟ሗ⌮ᕤ

ᒣ໭ెᏹ


 㸭 

࢟ࣛࣝ㉸ศᏊ㞟ྜయࡢ⌮ㄽⓗ᳨ウ

ᮾ኱㝔
ᕤ

ఀ⸨႐ග


 㸭 

⺮ⓑ㉁࡟ࡼࡿ'1$ຍỈศゎ࡟࠾ࡅࡿ
⁐፹ࡢᙺ๭

஑ᕤ኱㝔
᝟ሗᕤ

ධబṇᖾ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ཯ᛂᶵᵓࡢゎ᫂⏘ᴗᢏ⾡⥲ྜ◊✲ᡤᰰ἟ࠉឡ 㸭 

ᮾ኱㝔
⌮

୰ᮧᰤ୍


 㸭 

ᾮ┦⢾㢮ศᏊࡢᣲື࡜;$6ࢫ࣌ࢡࢺ
ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱㝔᪂㡿ᇦ๰ᡂ⛉Ꮫబࠎᮌᓅᙪ 㸭 

ࢡࣛࢫࢱ࣮」ྜయࡢ཯ᛂゎ᫂࡟ྥ
ࡅ࡚

㇏⏣ᕤᴗ኱
ࢡࣛࢫࢱ࣮◊✲ᐊᕷᶫṇᙪ 㸭 

㑄⛣⣔ิ࢖࢜ࣥࢆྵࡴ໬ྜ≀ࡢ཯ᛂไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᒱ㜧኱
ᆅᇦ⛉Ꮫ

࿴బ⏣⿱᫛


 㸭 

㑄⛣㔠ᒓ໬ྜ≀ࡢᵓ㐀࣭཯ᛂ࣭ศ
Ꮚ㛫┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

࠾Ⲕ኱㝔
⮬↛⛉Ꮫ⣔

㮚㔝ᬒᏊ


 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿศᏊ
㞟ྜయࡢ◊✲

ྡྂᒇᩥ⌮኱ᮏከ୍ᙪ 㸭 

࢔ࣝࣈ࣑ࣥࢆ⏝࠸ࡿගᏛάᛶయࡢ
ྜᡂ

᫂ᫍ኱
⌮ᕤ

ᯇᮏ୍Ⴙ


 㸭 

⢾㙐ࢱࣥࣃࢡ㉁」ྜయ࡟࠾ࡅࡿศ
Ꮚ㛫┦஫స⏝බ┈㈈ᅋἲே
㔝ཱྀ◊✲ᡤ

ᒣ⏣୍స


 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኱
ᕤ

ᑠ㔝ඞᙪ


 㸭 

GF

GF

GK

GM

GX

HE

HK

HK

HN

HN

HT

HT

HT

HT

HX

ศᏊ㌶㐨ἲ࡟ࡼࡿ཯ᛂண
࡜ࡍࡿ᪂᭷ᶵ཯ᛂࡢ㛤Ⓨ

ࢆᇶ┙

-2-

㸦࣓ࣥࣂ࣮ᩘ㸧

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

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ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

H[

ID

IE

IE

IG

IH

IK

IK

IK

IO

IO

IP

IR

IR

IR

IR

◊✲ㄢ㢟ྡ

ᡤᒓ

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧➨୍ཎ⌮ཬࡧྂ඾ศᏊືຊᏛィ⟬࡟ࡼࡿḟඖࢼࣀ≀㉁ࡢᵓ㐀ᙧᡂࣉ ⏘ᴗᢏ⾡⥲ྜ◊✲ᡤࣟࢭࢫ࡜㟁Ꮚ≀ᛶࡢゎ᫂᳃ୗᚭஓ 㸭 

⏕యศᏊ࠾ࡼࡧ⁐፹ࡢᵓ㐀ᶵ⬟┦
㛵ࡢゎ᫂

❧࿨㤋኱
⏕࿨⛉Ꮫ

㧘ᶫ༟ஓ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ࢚ࢿࣝࢠ࣮ኚ᥮ゐ፹ࡢศᏊᶵᵓࡢゎ᫂ᒣཱྀᮾி⌮⛉኱Ꮫᕤኴ⏣㞝኱ 㸭 

⌮ㄽィ⟬࡟ࡼࡿ㓟໬≀ᅛᐃ໬࢟ࣛ
ࣝ7E㘒యࡢ⾲㠃ᵓ㐀ゎ᫂

ྡ኱㝔
⌮

㑦ḟࠉᬛ


 㸭 

㓄఩㔜ྜ࡟࠾ࡅࡿ%URQVWHG㓟ᛶ୰ᛶ࣍࢘⣲໬ྜ≀ࡢຓゐ፹స⏝

ᗈ኱㝔
ඛ㐍⌮ᕤ

⏣୰ࠉு


 㸭 

ࣜࢳ࣒࢘࢖࢜ࣥ㟁ụ࡬ࡢᛂ⏝ࢆᚿྥࡋࡓ⤖ᬗᛶከᏍ㉁࣊࢟ࢧ࢔ࢨࢺ
ࣜࣇ࢙ࢽࣞࣥㄏᑟయ

㛵すᏛ㝔኱
⌮

⏣୰኱㍜


 㸭 

ி኱㝔
ᕤ

㛵ࠉಟᖹ


 㸭 

㓟໬㑏ඖάᛶ࡞ࣝࢸࢽ࣒࢘ࢺ࣏ࣟ
ࣟࣥ㘒యࡢ࢟ࣛࣝගᏛ≉ᛶࡢホ౯

᪥኱
ᩥ⌮

ྜྷ⏣ࠉ⣧


 㸭 

9LEVDQLQ%ࡢR[\&RSH㌿఩ࡢ㑄⛣
≧ែゎᯒ

㤶ᕝ኱
㎰

ᰗ⏣ࠉு


 㸭 

ከᗙ㓄఩Ꮚ࡛ᵓ㐀つไࡉࢀࡓ㑄⛣㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀㸪㟁Ꮚ≧ែ࠾ࡼࡧ཯ᛂᛶ

ዉⰋዪ኱㝔
⮬↛⛉Ꮫ

ᾆࠉᗣஅ


 㸭 

㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡢບ㉳
≧ែࡢゎ᫂

❧ᩍ኱
⌮

᪂ᇼె⣖


 㸭 

㔠ᒓࢼࣀࢡࣛࢫࢱ࣮୰ࡢࣄࢻࣜࢻ
ࡢᣲືࡢゎ᫂

ᗈ኱㝔
ඛ㐍⌮ᕤ

Ỉ⏣ࠉຮ


 㸭 

᣺ື෇஧Ⰽᛶศගἲࡢ㉸ศᏊ࢟ࣛࣜࢸ࢕࡬ࡢᛂ⏝

ឡ፾኱㝔
⌮ᕤ

బ⸨ஂᏊ


 㸭 

㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ᭷ᶵྜᡂ཯
ᛂᶵᵓ࠾ࡼࡧ≀ᛶࡢゎ᫂

៞᠕኱
⸆

ᮾᯘಟᖹ


 㸭 

Ⓨගᛶ㔠ᒓ㘒యࡢບ㉳≧ែࡢ◊✲

᪥ᮏᕤᴗ኱
ᇶᖿᕤ

኱⃝ṇஂ


 㸭 

ᶓ὾ᅜ኱㝔
ᕤ

኱㔝┿ஓ


 㸭 ᪂つȧඹᙺ⣔ࡢ≀ᛶ໬Ꮫ◊✲ࢩࣜࢥࣥᇶᯈୖࡢ᭷ᶵศᏊ྾╔ᵓ㐀࡜㟁Ꮚ≧ែࡢゎᯒ

-3-

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

◊✲ㄢ㢟ྡ

ᡤᒓ

IS

㉁㔞ศᯒ࡟࠾ࡅࡿ᭷ᶵ㐣㓟໬≀ࡢᏳᐃᛶࡢ⪃ᐹ

ᮾ㑥኱
་

ᒸ┿ᝆᏊ


 㸭 

ṍࢇࡔከ⎔ⰾ㤶᪘໬ྜ≀ࡢᵓ㐀࡜
ᛶ㉁

ᮾ㑥኱
⌮

Ώ㑔⥲୍㑻


 㸭 

ගᶵ⬟ᛶศᏊࡢ㟁Ꮚບ㉳≧ែࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧᵓ㐀ࡢ◊✲

ᐊ⹒ᕤᴗ኱
ᕤ

㣤᳃ಇᩥ


 㸭 ᪂つ࡞඾ᆺඖ⣲໬ྜ≀ࡢᵓ㐀࡜཯
ᛂࡢ◊✲

Ꮫ⩦㝔኱
⌮

⊁㔝┤࿴


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࿴ḷᒣ኱
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࢟ࣛࣝศᏊ⤖ᬗࡢᶞ≧ᡂ㛗࡟࠾ࡅࡿศᏊⓗ࣓࢝ࢽࢬ࣒ゎ᫂

⟃Ἴ኱
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 㸭 

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ᮾி㒔❧⏘ᴗᢏ⾡◊✲ࢭࣥࢱ࣮ᑠỮె♸ 㸭 

㧗࿘ᮇ㸯㸲᪘ඖ⣲ࢆྵࡴ໬ྜ≀ࡢᵓ㐀≀ᛶ⌮ㄽィ⟬ᮾி㒔኱㝔㒔ᕷ⎔ቃ⛉Ꮫ℩㧗ࠉ΅ 㸭 

㔞Ꮚ໬Ꮫィ⟬࡜⤫ィຊᏛⓗ࢔ࣉ࣮ࣟࢳࢆ㥑౑ࡋࡓ࣏ࣜ࢜࢟ࢯ࣓ࢱ
࣮ࣞࢺࡢ⌮ㄽⓗ᳨ウ

ᮾ኱㝔
⥲ྜᩥ໬

ᶓᕝ኱㍜
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 㸭 

ᒙ≧໬ྜ≀ࡢ㟁Ꮚ≧ែࡢ➨୍ཎ⌮ィ⟬㜰኱⏘ᴗ⛉Ꮫ◊✲ᡤ⏣୰ៅ୍㑻 㸭 

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓȧඹᙺ
ศᏊࡢ㛤Ⓨ

Ⲉᇛ㧗ᑓ

ỤᕝὈᬸ
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 㸭 

㔠ᒓඖ⣲ࢆྵࡲ࡞࠸ᶵ⬟ᛶ㏆㉥እ
Ⓨග⣲Ꮚࡢ㛤Ⓨ

ྡ኱㝔
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ᮧ஭ᚁྐ
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 㸭 

㑏ඖ཯ᛂࢆ㉳Ⅼ࡜ࡍࡿከ᰾㔠ᒓ㘒య཯ᛂሙࡢᵓ⠏࡜ᶵ⬟

ᒸᒣ኱㝔
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 㸭 

▷ᑑ࿨✀ࡸ⏺㠃໬Ꮫ✀ࡢ᣺ືࢫ࣌
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 㸭 

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ෆໟࣇ࣮ࣛࣞࣥ࠾ࡼࡧࡑࡢㄏᑟయ
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 㸭 

ࢪࢳ࢔ࢩࢡࣟ࣌ࣥࢸࣥ⎔ࢆ⏝࠸ࡓ㏆㉥እග྾཰ᮦᩱࡢタィ࡜ᅛయ୰࡛ࡢ㞄᥋ȧඹᙺ㛫┦஫స⏝ࡢゎ᫂

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᳜⏣୍ṇ
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➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ
ᅛయ㓟໬≀ゐ፹ࡢᶵ⬟ゎ᫂

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୰ᒣࠉဴ
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 㸭 ᪂つ཮ᴟᛶ᭷ᶵ඾ᆺඖ⣲໬ྜ≀ࡢ๰ᡂ࡜32⤖ྜ࡟ᑐࡍࡿඖ⣲ຠᯝ

໭㔛኱
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࠿ࡽ࡞ࡿ࣋ࣝࢺ≧ࣃ࢖ඹᙺศᏊࡢ
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 㸭 

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ࢭࢩࢫ཯ᛂᐇ⌧࡟ྥࡅࡓ᪂つᨭᣢ㓄఩Ꮚࡢタィ

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 㸭 

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

 㸭 

⣽⬊ෆࡢ㉸◲㯤ศᏊࡢ᣺ືゎᯒ

ᮾ໭኱㝔
⸆

ᙳᒣⳀἋ


 㸭 

ศᏊ㔠ᒓ㘒య࠾ࡼࡧከ᰾ࢡࣛࢫ
ࢱ࣮ࡢ⢭ᐦไᚚ࡜ᶵ⬟ࡢゎ᫂

ᮾ໭኱㝔
⌮

㛗⏣ᾈ୍


 㸭 

Ẽ┦ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢ⾪✺㏿ᗘ࡟㛵ࡍࡿศᏊືຊᏛⓗゎᯒ

㔠ἑ኱
⌮ᕤ

⋢⯓▱ஓ


 㸭 

඾ᆺඖ⣲ࢆྵࡴ㠀ᖹ㠃ከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢᵓ㐀࡜≀ᛶ

᪩኱
⌮ᕤ

ຍ⸨೺ኴ


 㸭 

FE

GE

GJ

HH

H\

IJ

IO

IP

IP

IT

IV

IX

IY

IZ

-7-

㸦࣓ࣥࣂ࣮ᩘ㸧































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

◊✲ㄢ㢟ྡ

ᡤᒓ

I[

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓගᶵ⬟ᛶศᏊࡢ㛤Ⓨ

Ⲉᇛ኱
ᕤ

࿃㒓཭ᏹ


 㸭 

')7ィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢゎ᫂࡟ࡼࡿຠ⋡ⓗ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ

ዉⰋᩍ⫱኱
⌮

ᒣᓮ⚈Ꮚ


 㸭 

㟁Ꮚບ㉳࢖ࢯࢩࣥ㓟ࣇ࢙ࢽࣝㄏᑟ
యࡢศᏊᵓ㐀

᪥኱
ᕤ

ዟᒣඞᙪ


 㸭 ᪂つᶵ⬟ᛶ᭷ᶵⰍ⣲ࡢ㛤Ⓨ

ᒱ㜧኱
ᕤ

⯪᭥୍ṇ


 㸭 

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

἟⏣᐀඾ 㸭 

7KHRUHWLFDOVWXGLHVRIOLJKWPDWWHULQWHUDFWLRQVLQ
PROHFXODUV\VWHPVி኱㝔ᕤ

1JX\HQ7KDQK
3KXF㠀⮬᫂࡞ࢫࣆࣥ≧ែࢆ⤒⏤ࡍࡿ㑄⛣㔠ᒓゐ፹཯ᛂࡢィ⟬໬Ꮫⓗᶵᵓ
ゎᯒ

໭኱㝔
⸆

ᑠᓥṇᐶ


 㸭 

ࢢࣝࢱ࣑ࢻ㉸ศᏊࢼࣀᵓ㐀య࡟࠾ࡅࡿᶵ⬟ᛶᐁ⬟ᇶࡢ㓄ྥᵓ㐀ゎᯒ

⇃ᮏ኱㝔
ඛ➃⛉Ꮫ

᱓ཎࠉ✨


 㸭 

ゐ፹ⓗ㦵᱁㌿఩཯ᛂࡢ཯ᛂᶵᵓゎ
ᯒ

ᮾ໭኱㝔
⌮

୰ᮧࠉ㐩


 㸭 

ȧ㟁Ꮚ⣔㓄఩Ꮚࢆ㘽࡜ࡍࡿ㛤Ẇᛶ඾ᆺඖ⣲㘒యࡢ㛤Ⓨ

㜰኱㝔
ᕤ

ඤ⋢ᣅஓ


 㸭 

I[

I[

I]

JE

JE

JF

JG

JG

JH

㸦࣓ࣥࣂ࣮ᩘ㸧










 㸭 










᪋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 

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 

FF

FF

FG

-8-

㸦࣓ࣥࣂ࣮ᩘ㸧









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

◊✲ㄢ㢟ྡ

ᡤᒓ

FG

㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡿືⓗ≀ᛶ㔞ࡢ⌮ㄽⓗ◊✲

㜰኱㝔
ᇶ♏ᕤ

୰㔝㞞⏤


 㸭 

ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃᒁᡤ≀⌮㔞࡟ࡼࡿࢫࣆࣥࢲ࢖ࢼ࣑ࢡࢫゎᯒ

ி኱㝔
ᕤ

℩Ἴ኱ᅵ


 㸭 

㧗཯ᛂᛶࡢࢪ࣎ࣛࣥ  ࣭$O%໬ྜ
≀ࡢᛶ㉁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⨨᥮ᇶຠᯝࡢ⌮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 

Ⰽ⣲ቑឤග㟁ᴟ࣭ගゐ፹➼ࡢィ⟬
໬Ꮫⓗ◊✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ⲡ㛫ࠉோ


 㸭 ⏕యศᏊ」㞧⣔ࡢ඲ཎᏊ࣭⢒ど໬ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲⚄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 

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 ⰾ㤶᪘஧㔞యࢡࣛࢫࢱ࣮ࡢȧ㟁Ꮚඹ㬆≧ែࡢ㉥እศග࡟ࡼࡿᵓ㐀◊
✲

࠾Ⲕ኱
ᇶᖿ◊✲㝔

ᐑᓮ඘ᙪ


 㸭 

FI

FI

FJ

FJ

FK

FL

FN

FN

FO

FP

FP

FQ

FQ

FR

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ
࠿ࡽ㉥እ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝ
ゎᯒ-9-㸦࣓ࣥࣂ࣮ᩘ㸧































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

◊✲ㄢ㢟ྡ

ᡤᒓ

FU

➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫ࡜ඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽࡢከゅⓗᒎ㛤

໭኱㝔
⌮

Ṋḟᚭஓ


 㸭 

➨୍ཎ⌮ィ⟬࡟ࡼࡿࣇ࣮ࣟࣟ࢝࣎
ࣥࣉࣛࢬࢻࣛ࢖࢚ࢵࢳࣥࢢ࡟ࡼࡿ
㓟໬⭷⾲㠃ࡢㄏ㟁ᛶ㉁ࡢゎ᫂

ᶓ὾ᅜ኱㝔
ᕤ

5DHELJHU+DQQHV 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 

⎔໬཯ᛂ࡟ࡼࡿⅣ໬⎔ᘧ࠾ࡼࡧ」⣲⎔ᘧ໬ྜ≀ྜᡂ࡟࠾ࡅࡿ⁐፹ຠᯝ࡜཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽ◊✲㧗▱኱㝔⥲ྜே㛫⮬↛⛉Ꮫ㔠㔝኱ຓ 㸭 

ࣜࣥ⬡㉁ࣇࣜࢵࣉࢆㄏ㉳ࡍࡿ⭷㈏㏻࣌ࣉࢳࢻࡢィ⟬ศᏊタィ

໭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 

ࢼࣀ⊃ᑠ✵㛫࡟࠾ࡅࡿศᏊ࠾ࡼࡧ
࢖࢜ࣥࡢ⁐፹࿴࡜ືែࡢゎᯒᚨᓥ኱㝔♫఍⏘ᴗ⌮ᕤ

ྜྷ⏣ࠉ೺ 㸭 

ࣔࢹࣝ⁐⼥ሷࢆ⁐፹࡜ࡋࡓ࡜ࡁࡢ
஧ཎᏊ⁐㉁ศᏊࡢ⁐፹࿴ࢆグ㏙ࡍ
ࡿ$$2=⌮ㄽࡢ㛤Ⓨ

ឡ፾኱㝔
⌮ᕤ

ᐑ⏣❳ᙪ


 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 

จ㞟ㄏ㉳Ⓨග࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊
✲

༓ⴥ኱
ᕤ

ᒣᮏ඾ྐ


 㸭 

࣓࢝ࣞ࢜ࣥࣔࢹࣝ࡟ࡼࡿࢱࣥࣃࢡ
㉁ᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥ
ࢻࢫࢣ࣮ࣉゎᯒ

ྡ኱㝔
ᕤ

ᑎ⏣ᬛᶞ


 㸭 

⏕యศᏊ࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟
ࡢ⌮ㄽィ⟬

ி኱㝔
⌮

ᯘࠉ㔜ᙪ


 㸭 

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

ᯇᮏṇ࿴


 㸭 

FV

FW

FY

FY

FZ

FZ

FZ

F[

F\

F]

GE

GI

GJ

GK

GL

- 10 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

GM

㔞ᏊศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔
17&KHP࡟ࡼࡿࢼࣀࢧ࢖ࢬศᏊࡢศ
Ꮚᶵ⬟ࡢゎ࣭᫂タィ⌮໬Ꮫ◊✲ᡤ

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫ
ࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ

GN

GT

GV

GX

GZ

G[

HI

HP

HP

HS

HT

HV

HW

HY

HZ

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧୰ᔱ㝯ே 㸭 

ᶓ὾ᕷ኱㝔
⏕࿨་⛉Ꮫ

᳃ḟࠉᆂ


 㸭 

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ
࣮ࣟࢳ

໭኱㝔
⌮

ຍ⸨ᫀᏊ


 㸭 

⢾㙐⤖ྜ࡟ࡼࡿ⏕యศᏊㄆ㆑࡟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 

ᮾ኱㝔
⸆

኱࿴⏣ᬛᙪ


 㸭 

ᮾ኱ඛ➃⛉Ꮫᢏ⾡
ࢭࣥࢱ࣮

ᒣୗ㞝ྐ


 㸭 ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࡢᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭ศᏊ㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝ

㟼ᒸ኱
ᕤ

㫽ᒃࠉ⫕


 㸭 

඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ
࡛ࣥゎ᫂ࡍࡿࢯࣇࢺ࣐ࢸࣜ࢔ࣝࡢ
ᚤどⓗᵓ㐀

໭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ⓗ◊✲

ி኱㝔
ᕤ

ఀ⸨ᙲᾈ


 㸭 

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 

࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉ᏛศᏊ㌶㐨ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂ࠾ࡼ
ࡧ᭷ᶵศᏊᵓ㐀ࡢタィ࡜ゎᯒ㧗⢭ᗘ࡞⢾㙐ຊሙࡢᵓ⠏- 11 -

































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

◊✲ㄢ㢟ྡ

ᡤᒓ

H[

ḟୡ௦,7♫఍ཬࡧḟୡ௦పⅣ⣲♫఍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࡟ࡶ࡜࡙ࡃࢼࣀ
ᵓ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

ࣜࣥ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 

࢞ࣛࢫ⣔࡟࠾ࡅࡿ㐜࠸ࢲ࢖ࢼ࣑ࢡ
ࢫࡢ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲

㜰኱㝔
ᇶ♏ᕤ

㔠ࠉ㗰


 㸭 

᭷ᶵศᏊ࡟࠾ࡅࡿග໬Ꮫ㐣⛬ࡢ⌮
ㄽⓗ◊✲

ᘯ๓኱㝔
⌮ᕤ

ᒣᓮ⚈ᖹ


 㸭 

ཎᏊ᰾ࡢ㔞Ꮚຠᯝࢆ⪃៖ࡋࡓ⌮ㄽィ⟬ᡭἲ࡟ࡼࡿ㔜Ỉ⣲ྠ఩యຠᯝ
ࡢゎᯒ

ᒱ㜧኱
ᕤ

Ᏹ⏣ᕝኴ㑻


 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 

➨୍ཎ⌮ィ⟬ᡭἲ࡟ᇶ࡙ࡃࢼࣀ㟁Ꮚᮦᩱࡢࣉࣟࢭࢫᶵ⬟ไᚚ࡟㛵ࡍ
ࡿ◊✲

ᓥ᰿኱
⥲ྜ⌮ᕤ

ᙳᓥ༤அ


 㸭 

ኳ↛⣸እ⥺㜵ᚚ≀㉁࣐࢖ࢥࢫ࣏ࣜ
ࣥᵝ࢔࣑ࣀ㓟ࡢගບ㉳ࢲ࢖ࢼ࣑ࢡ
ࢫ࡜⁐፹࿴ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ᒣཱྀᮾி⌮⛉኱⸆␊ᒣࠉඔ 㸭 

H]

H]

ID

IE

IF

IF

IF

IF

IG

IG

IG

IG

IG

IH

- 12 -

㸦࣓ࣥࣂ࣮ᩘ㸧










 㸭 




















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

◊✲ㄢ㢟ྡ

ᡤᒓ

IJ

➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟ࡼࡿỈ⾲㠃ࡢ⮬⏤2+㸪Ỉ⣲⤖ྜ2+ࡢ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫ
ࡢ⌮ㄽ◊✲

ᐩᒣ኱
⌮ᕤ

▼ᒣ㐩ஓ


 㸭 

ග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵ⛣ື࣓࢝
ࢽࢬ࣒

᪥ᮏዪᏊ኱
⌮

ᮧᒸࠉᱻ


 㸭 

᭷ᶵศᏊᅛయ୰ࡢ㔠ᒓࢼࣀࢻࢵࢺ
ࡢᖏ㟁Ᏻᐃᛶ㸸➨୍ཎ⌮ィ⟬࡟ࡼ
ࡿ◊✲

༓ⴥ኱㝔
⌮

୰ᒣ㝯ྐ


 㸭 

ゐ፹࠾ࡼࡧᶵ⬟ᛶ≀㉁ࡢᶵᵓゎ᫂࡜ศᏊࢹࢨ࢖ࣥ

៞᠕኱
⌮ᕤ

⏿୰⨾✑


 㸭 

࢖࢜ࣥᛶᾮయ࡟࠾ࡅࡿ࢖࢜ࣥఏᑟ
⋡ࠊෆ㒊⛣ືᗘࠊ࠾ࡼࡧ+DYHQẚࡢໟᣓⓗ◊✲㸰㸸࢖࢜ࣥࢧ࢖ࢬ౫Ꮡ
ᛶ

᪂₲኱
⌮

኱㫽⠊࿴


 㸭 

࣎࢘ࣝᆺඹᙺ໬ྜ≀ࡢ≀ᛶㄪᰝࠊ࠾ࡼࡧ㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢάᛶ
ホ౯◊✲

㜰኱㝔
ᕤ

Ḉ஭ⱥ༤


 㸭 

ࢪ࣮ࣚࢻࣅ࢔࣮ࣜࣝࢆ⏝࠸ࡓ$3(;཯ᛂࡢ཯ᛂᶵᵓゎ᫂࡜ࢼࣀ࣮࢝࣎
ࣥศᏊࡢᵓ㐀≀ᛶゎ᫂◊✲

ྡ኱㝔
⌮

ఀ⸨ⱥே


 㸭 (OHFWURQLFWUDSSLQJVLWHVDQG
SRODURQIRUPDWLRQ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 

㉁㔞ศᯒἲ࡟ࡼࡿ⏕యศᏊࡢẼ┦཯ᛂ㐣⛬࡟㛵ࡍࡿ◊✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ὸᕝ኱ᶞ


 㸭 

㔠ᒓ㘒యࡢ㓟໬㑏ඖ㟁఩࡟㛵ࡍࡿࢹ࣮ࢱ࣮࣋ࢫసᡂ

⟃Ἴ኱㝔
ᩘ⌮≀㉁

ᯇ஭ࠉ஽


 㸭 

ᾮయࡢ⤫ィຊᏛ⌮ㄽ࡟ࡼࡿ⏕యศᏊᶵ⬟ࡢゎᯒ

஑ᕞ኱㝔
⌮

ྜྷ⏣⣖⏕


 㸭 ᪂つȧ㟁Ꮚ⣔࢖࢜ࣥࡢタィ࣭ྜᡂࢆᇶ㍈࡜ࡋࡓ㉸ศᏊ㞟ྜయࡢ๰〇

❧࿨㤋኱
⏕࿨⛉Ꮫ

๓⏣኱ග


 㸭 

ࢱࣥࣃࢡ㉁࡟⤖ྜࡍࡿேᕤ࢜ࣜࢦ
࢔࣑ࢻࡢ࢖ࣥࢩࣜࢥタィ

ᮾ኱㝔
ᕤ

᳃ᮏ῟ᖹ


 㸭 

IJ

IJ

IJ

IJ

IK

IK

IK

IL

IL

IL

IM

IM

IN

IN

IP

- 13 -

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⟬࡟ࡼࡿ᰾ኚ᥮
⁐⼥ሷࢱ࣮ࢤࢵࢺࡢ㟁Ꮚ⛣ື཯ᛂ
ᛶホ౯

ᮾ໭኱㝔
ᕤ

᏷ᡞ༤⣖


 㸭 ྜ㔠ゐ፹࡟ࡼࡿ࣮࢝࣎ࣥࢼࣀ
ࢳ࣮ࣗࣈࡢᡂ㛗࣓࢝ࢽࢬ࣒ゎ᫂࡬ྥࡅࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ

ᮾ኱㝔
ᕤ

୸ᒣⱱኵ


 㸭 㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿࣛࣥࢱࣀ࢖ࢻ
㸭࣐࢖ࢼ࣮࢔ࢡࢳࣀ࢖ࢻ㘒࢖࢜ࣥࡢᵓ㐀᥈⣴࡜㉥እࢫ࣌ࢡࢺࣝィ⟬

ᗈᓥ኱㝔
⌮

஭ཱྀెဢ


 㸭 

ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

໭㔛኱
⌮

⚄㇂ᫀᏹ


 㸭 㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿග໬Ꮫ⣔ϩ࡟࠾ࡅࡿỈศゎ࠾ࡼࡧ࢟ࣀࣥ㑏ඖ཯ᛂࡢศᏊᶵᵓゎᯒ

ྡ኱㝔
⌮

㔝ཱྀࠉᕦ


 㸭 

⸆๣ศᏊᨺฟࢆᚿྥࡋࡓ᭷ᶵ㔠ᒓࣇࢱࣟࢩ࢔ࢽࣥࡢග཯ᛂ㛤Ⓨᮾ኱⏕⏘ᢏ⾡◊✲ᡤᮧ⏣ࠉ្ 㸭 

」㞧࡛ከᵝ࡞ศᏊᵓ㐀࡜㟁Ꮚ≧ែ࠾ࡼࡧ໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲ி኱ゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬ⚟⏣Ⰻ୍ 㸭 

⌮ㄽィ⟬࡞ࡽࡧ࡟ᶵᲔᏛ⩦ࢆ฼⏝ࡋࡓ᪂つᮦᩱ࣭ゐ፹㛤Ⓨ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

ⰼᮧோႹ


 㸭 

᭷ᶵ໬Ꮫ཯ᛂࡢ཯ᛂ࣓࢝ࢽࢬ࣒ゎ᫂ࢆ┠ᣦࡋࡓィ⟬໬Ꮫⓗゎᯒ

எ༲◊✲ᡤ

㯮ෆᐶ᫂


 㸭 

ィ⟬໬Ꮫࢆ⏝࠸ࡓゐ፹ࡢ⌮ㄽタィ࠾ࡼࡧ᭷ᶵⓎගᮦᩱࡢ≀ᛶゎᯒ

໭኱㝔
ᕤ

ఀ⸨ࠉ⫕


 㸭 

Ⅳ⣲࣭㧗ศᏊ」ྜᮦᩱ࡟࠾ࡅࡿప
Ἴᩘ࣐ࣛࣥࢆ୚࠼ࡿศᏊ㛫᣺ື࣮ࣔࢻࡢゎᯒ

໭኱㝔
ᕤ

ᓥ⏣ᩄᏹ


 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ⭷ࢱࣥࣃࢡ㉁̾⭷⣔ࡢ┦஫స⏝ࠊᶵ⬟ࠊࢲ࢖ࢼ࣑ࢡࢫゎᯒᮾ኱⏕≀⏕⏘ᕤᏛ
◊✲ࢭࣥࢱ࣮

⠛⏣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 

஑኱,t&1(5ఀໃᕝ⨾✑ 㸭 

IQ

IQ

IQ

IQ

IR

IR

IR

IS

IT

IT

IU

IU

IU

IU

IU

')7ィ⟬࡟ࡼࡿ࢞ࢫศ㞳⭷ཬࡧ⇞ᩱ㟁ụ࡟ᛂ⏝ࡍࡿゐ፹ࡢタィ- 14 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































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

◊✲ㄢ㢟ྡ

ᡤᒓ

IU

➨୍ཎ⌮ィ⟬ࢆά⏝ࡋࡓᵓ㐀୰ࡢṍࢆ฼⏝ࡋࡓ㧗ᶵ⬟⇕㟁ኚ᥮ᮦᩱ
ࡢ㛤Ⓨ

ྡᕤ኱㝔
ᕤ

ᐑᓮ⚽ಇ


 㸭 

ᐇ㦂࡜ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂᶵᵓゎ
ᯒ

ᮾ኱㝔
⸆

⁪⏣ࠉⰋ


 㸭 

ࣄࢺ࡟࠾࠸࡚㧗ຠ⋡࡞⣸እ⥺ᦆയ
'1$ಟ᚟ࢆྍ⬟࡜ࡍࡿ᪂ࡓ࡞ศᏊ⣔
ࡢ๰ᡂ

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

బ⸨❳㤿


 㸭 

IV

IV

IV

IV

IW

IW

IX

IX

IY

IZ

IZ

I[

I[

I\

I\

㸦࣓ࣥࣂ࣮ᩘ㸧







໭኱
⛉Ꮫ◊✲ᡤ

:0&
6DPHHUD


ྡᕤ኱
ᕤ

୰ᮧಟ୍


 㸭 

ศᴟຠᯝࢆ⪃៖ࡋࡓศᏊືຊᏛィ⟬࡟ࡼࡿ㓟໬≀⼥యࡢ⾲㠃⦆࿴࢖࢜ࣥ㓄఩ᵓ㐀ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ
࠾ࡼࡧᵓ㐀ᙧᡂ࢚ࢿࣝࢠ࣮ࡢホ౯

㜰኱㝔
ᕤ

㕥ᮌ㈼⣖


 㸭 ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂

ྡ኱㝔
ᕤ

㕥ᮌ῟ᕧ


 㸭 

ศᏊືຊᏛἲࢆ⏝࠸ࡓ⏕యᕧ኱ศᏊࡢᣑᩓಀᩘࡢ⇕ຊᏛ≧ែ౫Ꮡᛶ

஑኱㝔
⌮

⛅ᒣࠉⰋ


 㸭 

ᶵᲔᏛ⩦࢔ࣉ࣮ࣟࢳ࡟ࡼࡿ㠀ᑐ⛠ࢥ࣐ศᏊࡢ࣮ࣞࢨ࣮ㄏ㉳㸱ḟඖᩚิࡢไᚚᶵᵓࡢண

ᮾ໭኱㝔
⌮

኱ᵳᖾ⩏


 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 

ຍỈศゎ㓝⣲ࢆ⏝࠸ࡿ㏿ᗘㄽⓗගᏛศ๭ࡢᶵᵓゎ᫂࡜ྜᡂ໬Ꮫⓗᛂ
⏝

㜰኱㝔
⸆

㉥஭࿘ྖ


 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 

⏕య࣭㧗ศᏊ⮬ᕫ㞟ྜ⣔ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᒸᒣ኱␗ศ㔝ᇶ♏⛉Ꮫ
◊✲ᡤ

⠛⏣ࠉ΅


 㸭 

ᶵ⬟ᛶศᏊ㞟ྜయࡢศᏊືຊᏛ◊✲㸸ḟඖࢼࣀࢳࣕࢿࣝࡀࡶࡘỈ
ࡢ㍺㏦ᶵᵓゎᯒරᗜ┴኱㝔ࢩ࣑࣮ࣗࣞࢩࣙࣥ

▼஭Ⰻᶞ 㸭 

0XOWLVFDOHPRGHOLQJRILQWHUVWHOODUUDGLFDOVSHFLHVRQZDWHULFH
᪂つ㧗ᶵ⬟ᛶࡢ୙ᩧゐ፹◊✲ప- 15 -

 㸭 


























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

◊✲ㄢ㢟ྡ

ᡤᒓ

I\

ேᕤගྜᡂࡢࡓࡵࡢ⏺㠃ࡢ◊✲࡜ᙉ┦㛵ࢯࣝࣂ࣮ࡢ᳨ド

⚄ᡞ኱
⛉Ꮫᢏ⾡
࢖ࣀ࣮࣋ࢩࣙࣥኳ⬟⢭୍㑻 㸭 

⏕యศᏊࡢᚤどⓗ࡞Ỉ࿴ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᮾᕤ኱⛉Ꮫᢏ⾡๰ᡂ◊✲㝔ᖹ⏣ᆂ♸ 㸭 

࢖࢜ࣥᛶⰍ⣲ࢆྵࡴ᪂つȧ㟁Ꮚ⣔ࡢྜᡂ࡜㓄ิไᚚ

ᒣᙧ኱᭷ᶵᮦᩱࢩࢫࢸ࣒

ᒣ㛛㝠ᖹ 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ␗᪉ⓗ㞟ྜ㓄ྥᮦᩱࡢ⇕ఏᑟ≉ᛶゎᯒ

ᮾᕤ኱
≀㉁⌮ᕤ

ྂᒇ⚽ᓠ


 㸭 

Ẽᾮ┦ቃ⏺㏆ഐ࡟࠾ࡅࡿ㡢Ἴఏ᧛ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱
≀ᛶ◊✲ᡤ

ὸ㔝ඃኴ


 㸭 

✚ศ᪉⛬ᘧ⌮ㄽ࡟ࡼࡿࢱࣥࣃࢡ㉁ࡢ⁐ゎᗘ㸹࣍ࣇ࣐࢖ࢫࢱ࣮⣔ิࡢ
෌ᵓ⠏

஑⏘኱
⌮ᕤ

ᮎᯇᏳ⏤⨾


 㸭 

✀ࠎࡢศᏊࡢཎᏊ㛫ຊ㢧ᚤ㙾ീࡢ
⌮ㄽィ⟬

㔠ἑ኱
ࢼࣀ⏕࿨⛉Ꮫ

Ⅳ❤ாྖ 㸭 

࢟ࣛࣝ࡞኱⎔≧໬ྜ≀ࡢບ㉳≧ែ
ᵓ㐀ࡢゎ᫂

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

㧗▼࿴ே


 㸭 ,PSRUWDQFHRI7FHOOUHFHSWRU
IOH[LELOLW\RQ7FHOODFWLYDWLRQ㜰኱ච␿Ꮫࣇࣟࣥࢸ࢕࢔
◊✲ࢭࣥࢱ࣮

)ORULV-DQ
YDQ(HUGHQ5HD[))ࢆ⏝࠸ࡓࢺࣜࢳ࣒࣮࢘࣋ࢱ
ᔂቯࡢ'1$ࢸ࣓ࣟ࢔ᵓ㐀࡬ࡢᙳ㡪

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

㔠ᒓ᭷ᶵᵓ㐀య࡟ࡼࡿỈྠ఩యศᏊㄆ㆑ಙᕞ኱ඛ㗦ᮦᩱ◊✲ᡤ⏣୰⚽ᶞ 㸭 

㔠ᒓ㓟໬≀ࢼࣀࢡࣛࢫࢱ࣮ࡢ⢭ᐦタィ࡜ᶵ⬟㛤ᣅ

ᮾ኱㝔
ᕤ

㕥ᮌᗣ௓


 㸭 

ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࢆ⏝࠸ࡓ⢾㙐ࢡࣛࢫࢱࡢᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫゎᯒ་⸆ᇶ┙࣭೺ᗣ࣭
ᰤ㣴◊✲ᡤ

ᮤࠉ⚽ᰤ


 㸭 

᭷ᶵ㔠ᒓゐ፹ࢆ⏝࠸ࡓ཯ᛂᶵᵓ࡟
㛵ࡍࡿ⌮ㄽⓗ◊✲

ᮾி㟁ᶵ኱
ᕤ

ᒣᮏဴஓ


 㸭 

㓟໬ᆺࣄࢻࣟࢤࢼ࣮ࢮάᛶ୰ᚰࡢ
ᒁᡤᵓ㐀࡜㟁Ꮚ≧ែࡢ⌮ㄽⓗỴᐃ⟃Ἴ኱ィ⟬⛉Ꮫ◊✲
ࢭࣥࢱ࣮

ᇼࠉඃኴ


 㸭 

᪂ࡋ࠸἞⒪ἲࡢ☜❧ࢆ┠ᣦࡋࡓ᪂
つゐ፹ࡢ㛤Ⓨ

ᮾ኱㝔
⸆

୕ࢶ἟἞ಙ


 㸭 

I\

I\

I\

I]

I]

I]

I]

I]

I]

I]

JD

JD

JD

JF

JF

- 16 -

㸦࣓ࣥࣂ࣮ᩘ㸧
















 㸭 
















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

◊✲ㄢ㢟ྡ

ᡤᒓ

JF

⏕యศᏊ࡛㉳ࡇࡿ໬Ꮫ཯ᛂ࡜ᶵ⬟┦㛵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⠏⤫ィᩘ⌮◊✲ᡤᯘࠉ៞ᾈ 㸭 

ගάᛶ໬࢔ࢹࢽࣝ㓟ࢩࢡ࣮ࣛࢮࡢ
ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᶵ⬟ゎᯒ㔞Ꮚ⛉Ꮫᢏ⾡◊✲
㛤Ⓨᶵᵓ

⏣ཱྀ┿ᙪ


 㸭 

6+ࢻ࣓࢖ࣥ࡟ᑐࡍࡿ≉␗ⓗ⤖ྜࣜࣥ㓟໬࣌ࣉࢳࢻࡢ㛤Ⓨ་⸆ᇶ┙࣭೺ᗣ࣭
ᰤ㣴◊✲ᡤ

Ἑཎṇᾈ


Ᏻᐃࣛࢪ࢝ࣝࢆⓎ⏕ࡍࡿᖹ⾮⣔࡟
㛵ࡍࡿ◊✲

ᮾᕤ኱
≀㉁⌮ᕤ

㟷ᮌ኱㍜


 㸭 

ศᏊືຊᏛࢆ⏝࠸ࡓேᕤ᰾㓟ࢆྵࡴ᰾㓟࢜ࣜࢦ࣐࣮ࡢᏳᐃᛶ◊✲་⸆ᇶ┙࣭೺ᗣ࣭
ᰤ㣴◊✲ᡤ

㯮⏣ṇᏕ


 㸭 

⁐፹ᴟᛶ࡜ ᗘ࡟ᛂ⟅ࡍࡿࢱࣥࣃ
ࢡ㉁␯Ỉ࣏ࢣࢵࢺࡢືⓗᵓ㐀ኚ໬
ࡢゎ᫂

ᮾி⌮⛉኱
ඛ㐍ᕤ

ᱵ⃝㞞࿴


 㸭 

཯ᛂ⮬ື᥈⣴ἲ࡟ࡼࡿ࣊ࢸࣟඖ⣲ࢆά⏝ࡋࡓ᪂཯ᛂࡢ๰ฟ࡜᪂ᮦᩱ
ࡢ㛤Ⓨ໭኱໬Ꮫ཯ᛂ๰ᡂᣐⅬ㛗⏣⿱ஓ 㸭 

ࣉࣟࢪ࢙ࢡࢺ
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⏝

JF

JG

JG

JG

JG

JH

JI

JI

㸦࣓ࣥࣂ࣮ᩘ㸧








 㸭 










ᡤෆ

DG

DG

DI

DI

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

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮Ụཎṇ༤ 㸭 

ࢱࣥࣃࢡ㉁จ㞟࡜จ㞟㜼ᐖ๣ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

⏕࿨๰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 

- 17 -











ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DI

ᢠయࡢศᏊෆ┦஫స⏝ࢿࢵࢺ࣮࣡
ࢡ࡜ᶵ⬟ࡢ㐃㛵ࡢゎ᫂⏕࿨࣭㘒యศᏊ⛉Ꮫ⏕యศᏊ࣐ࢩࣥ࡟࠾ࡅࡿ࣐ࣝࢳࢫ
ࢣ࣮ࣝ࡞ᶵ⬟Ⓨ⌧ࢲ࢖ࢼ࣑ࢡࢫࡢ
ࢩ࣑࣮ࣗࣞࢩࣙࣥ

DJ

DJ

DJ

DK

DK

DK

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧㇂୰෪Ꮚ 㸭 

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮

ᒸᓮᆂ୍ 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢖࢜
ࣥᾮయࡢ◊✲⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ▼⏣ᖸᇛ 㸭 

ศᏊ⣔࡟࠾ࡅࡿ☢ᛶ࠾ࡼࡧࣇ࢛ࣀ
ࣥ≀ᛶࡢ➨୍ཎ⌮ィ⟬⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ༡㇂ⱥ⨾ 㸭 

ᶵ⬟ᛶ㛤ẆศᏊᮦᩱࡢᵓ㐀≀ᛶ̿⏕࿨࣭㘒యศᏊ⛉Ꮫ㟁Ꮚ≧ែ┦㛵ࡢゎ᫂ⲡᮏဴ㑻 㸭 

ḟඖඹᙺᵓ㐀ࢆࡶࡘศᏊ㞟ྜయࡢ⏕࿨࣭㘒యศᏊ⛉Ꮫ
๰〇

℩ᕝὈ▱


 㸭 

㑄⛣㔠ᒓ㘒యゐ፹ࢆ⏝࠸ࡿ᭷ᶵ཯
ᛂࡢ཯ᛂᶵᵓ◊✲㧗㇂ࠉග 㸭 

ගศᏊ⛉Ꮫ















ࠑᇶ♏⏕≀Ꮫࠒ᪋タ฼⏝ %
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

TF

ࣄࢺᚤᑠ⟶࡜ࢱ࢘ࡢ⤖ྜ≧ែ࡟࠾ࡅࡿᚤᑠ⟶ࡢᵓ㐀Ᏻᐃᛶ࠾ࡼࡧ&ᮎ➃ኳ↛ኚᛶ㡿ᇦࡢศᏊᣲືゎᯒಙᕞ኱㎰௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᱵ⃝බ஧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 
ࠑ⏕⌮Ꮫࠒ
ᡤෆࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

LD

ḟඖ05,࡟ࡼࡿ⬻ࡢᶵ⬟ཬࡧᵓ㐀
ゎᯒ

ᚰ⌮⏕⌮Ꮫ

ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⬻ᶵ⬟⏬ീゎᯒ⏕యᶵ⬟᝟ሗゎᯒᐊ

LD

- 18 -

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



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 Dynamic Structures of Biological Molecules Revealed bySpectroscopy, Quantum Chemical Calculations, and Molecular
Dynamics Simulations
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Unno, M., Kikukawa, T., Fujisawa, T., Hoff, W.D. 11th International Conference on Advanced Vibrational

Spectroscopy

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Okuda, Y., Miyoshi, R., Kamo, T., Fujisawa, T., Nagae, T., Mishima, M., Eki, T., Hirose, Y., Unno, M.

J. Phys. Chem. B 126, 813-821 (2022)
Fujisawa, T., Nishikawa, K., Tamogami, J., Unno, M. J. Phys. Chem. Lett. 12, 9564-9568 (2021)
Unno, M., Hirose, Y., Mishima, M., Kikukawa, T., Fujisaewa, T., Tamogami, J. Biophys. Physicobiol. 18, 127-130(2021)Nagae, T., Unno, M., Koizumi, T., Miyanoiri, Y., Fujisawa, T., Masui, K., Kamo, T., Wada, K., Eki, T., Ito, Y.,
Hirose, Y., Proc. Natl. Acad. Sci. USA 118, e2024583118 (2021)- 19 -

Ў‫܇‬ϋấợỎЎ‫᧓܇‬ᩓ‫܇‬ᆆѣể҄‫ܖ‬Ӓࣖೞನỉᄂᆮᴾᵧᶌᶒᶐᵿᴾ ᴾ ᵿᶌᶂᴾ ᴾ ᵧᶌᶒᶃᶐᵋᵫᶍᶊᶃᶁᶓᶊᵿᶐᴾ ᾒᾷᾰ῁ᾶᾴᴾ ᵲᶐᵿᶌᶑᶄᶃᶐᴾ ᴾ ᵫᶃᶁᶆᵿᶌᶇᶑᶋᴾᶍᶄᴾ
ᵡᶆᶃᶋᶇᶁᵿᶊᴾ ᵰᶃᵿᶁᶒᶇᶍᶌᴾ ᴾ ᴾ     ‫⏣ۑ‬௰஧ᮁ 㸦⚄ዉᕝ኱Ꮫ ⥲ྜ⌮Ꮫ◊✲ᡤ㸧㸯 ◊✲┠ⓗࠊෆᐜ㸯㸬㸯ࢢࣜࢽ࣮ࣖ཯ᛂࡢ࣓࢝ࢽࢬ࣒

ࡇࢀࡲ࡛㛗࠸㛫ࠊࢢࣜࢽ࣮ࣖ཯ᛂࡢ࣓࢝ࢽࢬ࣒ࢆ◊✲ࡋ࡚ࠊࣛࢪ࢝ࣝ཯ᛂ࡟ࡼࡿሙྜ࡜ࠊ
㟁Ꮚᑐ⛣ືࢆ⤒⏤ࡍࡿሙྜࡀ࠶ࡿࡇ࡜ࢆࠊ᫂ࡽ࠿࡟࡛ࡁࡓࠋ࢔ࢭࢺࣥ࡜࣋ࣥࢰࣇ࢙ࣀࣥ࡟ᑐ
ࡋ࡚ࠊ40 ✀㢮ࡢࢢࣜࢽ࣮ࣖ཯ᛂࡢ㏿ᗘᐃᩘ࡜㛵㐃࡙ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ཯ᛂࡢ࣓࢝ࢽࢬ࣒࡜ࡋ࡚ࠊ㞳ࢀࡓ㊥㞳୍࡛㟁Ꮚ⛣ື࡟ࡼࡾࠊ࢔ࢽ࢜ࣥ ࣛࢪ࢝ࣝࡢ⏕ᡂࢆ⤒࡚࠿ࡽࠊḟ➨࡟᥋㏆ࡋ࡚࠿ࡽࠊ⤖ྜࡀ࡛ࡁࡿࡶࡢ࡜ࠊConcerted Mechanism ࡜࠸ࢃࢀࡿࠊ㟁Ꮚᑐࡢ⛣ື࡛࠾ࡇࡿ࣮ࣝࢺ࡜ࡀ࠶ࡿࠋ㛫య࡜ࡋ࡚ࠊ࡝࠺࠸࠺᮲௳࡛ࣛࢪ࢝ࣝ཯ᛂ࡟࡞ࡿࡢ࠿ࠊ
㟁Ꮚᑐ⛣ື࡟࡞ࡿࡢ࠿ࠊࡑࢀࡽࡀ㉳ࡇࡿ᮲௳ࢆࠊ◊✲ࡋࡓࠋ㸯㸬㸰 ࢥࣟࢼ࢘࢖ࣝࢫ࡜ࠊᢠయ࡜ࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࡢぢ✚ࡶࡾ୍᫖ᖺ᮶ࠊࢥࣟࢼ࢘࢖ࣝࢫࡢୡ⏺ⓗ࡞ὶ⾜࡜ឤᰁ࡟࡜ࡶ࡞ࡗ࡚ࠊ࢘࢖ࣝࢫࡢ⤖ྜຊࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀࠊᛴົ࡟࡞ࡗ࡚࠸ࡿࠋX ⥺⤖ᬗᵓ㐀ゎᯒ࡜ࠊࢡࣛ࢖࢜㟁Ꮚ㢧ᚤ㙾ゎᯒ࡟ࡼࡾࠊᵓ㐀ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚ࡁࡓࡢ࡛ࠊỈ⣲⤖ྜ࡟ࡼࡿ࢚ࢿࣝࢠ࣮ࡢィ⟬ࢆ⾜ࡗࡓࠋ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲ ࡍ࡭࡚ࡢィ⟬ࡣࠊG09 ࣉࣟࢢ࣒࡛ࣛ⾜ࡗࡓࠋ㛢Ẇ⣔ࡢィ⟬࡛ࡣࠊ-B3LYP ἲ࡛⾜࠸ࠊ㛤᰾⣔ࡢィ⟬࡛ࡣࠊUB3LYP ἲ࡛⾜ࡗࡓࠋ㑄⛣≧ែࡢᵓ㐀࡜࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚ࠊฟⓎศᏊ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࢆィ⟬ࡋ࡚ࠊࡇࢀࢆ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮࡜ࡳ࡞ࡋ࡚ࠊᐇ㦂⤖ᯝ࡜ẚ
㍑ࡋࡓࠋᇶᗏ㛵ᩘࡣࠊ6-31+g(d,p) ࡜ 6-31g ࡛࠶ࡿࠋ㸱 ◊✲ᡂᯝ
Holm ࡢሗ࿌࡟࠶ࡿࠊ㸰㸮✀㢮ࡢࠊRMgX ࡜ R2Mg ࡜ acetone ࡜ benzophenone ࡜ࡢ཯ᛂ࡟ࡘ࠸࡚ࠊࡍ࡭࡚࡛㸲㸮✀㢮ࡢ཯ᛂࡢ཯ᛂ㏿ᗘࡢᐇ㦂್ࢆࠊሗ࿌ࡋ࡚࠶ࡿࠋィ⟬ࡋࡓάᛶ

- 20 -

໬࢚ࢿࣝࢠ್࣮࡜ᐇ㦂್ࢆẚ㍑ࡋ࡚ࠊacetone ࡜ࠊbenzophenone ࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊᐇ
㦂್࡜ࠊィ⟬್ࡢ㛫࡟ࠊࡼ࠸┦㛵㛵ಀࡀ♧ࡉࢀࡓࠋAcetone ࡢሙྜ࡜ࠊBenzophenone ࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊ཯ᛂ㏿ᗘ࡜ࠊィ⟬ࡋࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡢ㛫࡟ࡣࠊࡼ࠸┤⥺㛵ಀࡀᚓࡽࢀࡓࠋ཯ᛂࡀࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴࡢࡣࠊ benzophenone ࡜ࡢ཯ᛂࡢሙྜࡔࡅ࡛࠶ࡿࡀࠊࡑࢀ࡟
ࡶ᮲௳ࡀ࠶ࡿࡇ࡜ࡀࠊ᫂ࡽ࠿࡟ࡉࢀࡓࠋHolm ࡢㄽᩥ࡟ࡣࠊ୍ࡘࡢࢢࣜࢽ࣮ࣖヨ⸆ RMgX࡟ࡘ࠸࡚ࠊ஧ࡘࡢᩘ್ࡀ࡛࡚࠸ࡿሙྜࡀ࠶ࡿࡀࠊࡇࢀࡣ ࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴሙྜ࡜ࠊ㟁Ꮚᑐ⛣ື࡛࠾ࡇࡿሙྜࡢ୧᪉ࡀ࠶ࡿࡓࡵ࡛࠶ࡿࠋ
ࣛࢪ࢝ࣝ཯ᛂ࡛ࠊ᪂ࡋ࠸⤖ྜࡀ࡛ࡁࡿࡓࡵ࡟ࡣࠊ཯ᛂࡢ㑄⛣≧ែ࡛ࠊ⤖ྜࡢ࡛ࡁࡿ࡜ࡇࢁ
࡛ࠊ୍㔜㡯≧ែ࡟࡞ࡽ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋ᭱ึࡢࣛࢪ࢝ࣝࡣ୕㔜㡯≧ែ࡛࠶ࡿ࠿ࡽࠊ㑄⛣≧ែ࡛⣔㛫஺ᕪࡀ㉳ࡇࡿࡇ࡜࡟࡞ࡿࡀࠊࡇࡢࡓࡵ࡟ࡣ࠶ࡿ᮲௳ࡀᚲせ࡟࡞ࡿࠋGrignard ཯ᛂࡀࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴࡓࡵ࡟ࡣࠊ࠸ࢁ࠸ࢁࡢ᮲௳ࡀᩚࡗ࡚࠸࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࡢ࡛ࠊ௒᪥ࡲ
࡛ࡇࢀࡽࡢⅬࡀࠊ῝ࡃ◊✲ࡉࢀ࡚࠸࡞࠿ࡗࡓࠋ≉࡟ R2Mg ࡜ Benzophenone ࡢ཯ᛂࡣ
ࣛࢪ࢝ࣝ⤒⏤࡛࠾ࡇࡿࡀࠊ୰㛫యࡀ୙Ᏻᐃ࡞ࡓࡵ࡟◊✲࡟᫬㛫ࡀ࠿࠿ࡗ࡚࠸ࡿࠋ

㸰㸬ࢥࣟࢼ࢘࢖ࣝࢫࡢ⤖ྜຊ COVID19 ࡀ୰ᅜ࡛Ⓨ⏕ࡋ࡚࠿ࡽࠊ࢘࢖ࣝࢫ࡜ᢠయ࡜ࡢ⤖ྜࡀ኱ࡁ࡞ၥ㢟࡜࡞ࡾࠊࡲࡓ
࢘࢖ࣝࢫࡀࠊኚ␗ࢆ㔜ࡡࡿ୰࡛ࠊឤᰁຊࡀቑ኱ࡋ࡚ࠊୡ⏺୰࡛኱ࡁ࡞ၥ㢟࡟࡞ࡗ࡚࠸ࡿࠋ
ࡇࡢ⤖ྜࡢ୺࡞ຊࡣࠊ࢘࢖ࣝࢫศᏊ୰ࡢࢳࣟࢩࣥṧᇶ࡞࡝࡜ࠊᢠయ୰ࡢࠊ࢔࣑ࣀ㓟ṧᇶࡢỈ㓟ᇶ࡞࡝࡜ࡢ࢖࢜ࣥ⤖ྜࠊỈ⣲⤖ྜ࡟ࡼࡿࡶࡢ࡛࠶ࡿࠋࡑࡢ⤖ྜຊࡢᐃ㔞ⓗ࡞ぢ✚ࡶࡾࡣࠊឤᰁຊࡢቑ኱ࡢၥ㢟ࠊ࣡ࢡࢳࣥࡸ἞⒪⸆ࡢ㛤Ⓨ࡞࡝࡜㛵ಀࡋ࡚ࠊ኱ࡁ࡞ㄢ㢟࡛࠶ࡿࠋ⌧ᅾࠊᩘ✀㢮ࡢ࢘࢖ࣝࢫ࡟ࡘ࠸࡚ࠊ⤖ᯝࡀᚓࡽࢀࡓࡢ࡛ࠊ᪩ࡃⓎ⾲࡛ࡁࡿࡼ࠺࡟ࠊ‽ഛ୰࡛࠶ࡿࠋⓎ⾲ ฟ∧ணᐃ ⏣௰ࠊ ᯇᮏ  ௒ᖺ୰࡟ㄽᩥᢞ✏ࡢணᐃࠋ- 21 -

᭷ᶵࢣ࢖⣲໬ྜ≀ࡢᵓ㐀࡜ᛶ㉁
6WUXFWXUHVDQG3URSHUWLHVRI2UJDQRVLOLFRQ&RPSRXQGV‫ஂۑ‬᪂ Ⲯ୍㑻ࠊⳢ㔝 ◊୍㑻ࠊᒾ⏣ ࿴ဢࠊᕝ࿴⏣ ඃ㤶㔛ࠊ⏣୰ ᬛ኱ࠊỤᕝ ဏᕼࠊ኱ሯ ┤⣖ࠊ୕⏣ ᰟᩯ㸦⩌㤿኱Ꮫ኱Ꮫ㝔⌮ᕤᏛᗓ㸧 ◊✲┠ⓗ᫖ᖺ࡟ᘬࡁ⥆ࡁࠊ࣓࣌ࣝࢳࣝ࢜ࣜࢦࢩࣛࣥࡀ୧ぶ፹ᛶ≀㉁ࡢᵓ㐀ࢆࡶࡓ࡞࠸࡟ࡶ࠿࠿ࢃࡽࡎࠊ༢ศᏊ⭷ࡸ஧ศᏊ⭷ࢆᙧᡂࡍࡿ⌮⏤࡟ࡘ࠸࡚ࠊศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡢほⅬ࠿ࡽ᳨ウࡋࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲࢣ࢖⣲㦵᱁ࡀ all-anti ᵓ㐀ࡢ࣓࣌ࣝࢳࣝ࢜ࣜࢦࢩࣛࣥࢆ⏝࠸࡚ 2 ศᏊࡢ㓄⨨ࡸ㊥㞳ࢆኚ໬ࡉࡏ࡚ࠊศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ Gaussian ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ ◊✲ᡂᯝ
໬ྜ≀ 1 ࡢ 2 ศᏊࡢ㓄⨨ࡀ A㹼D ࡢሙྜ࡟ࡘ࠸࡚ࠊศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋศᏊ㛫㊥㞳ࡀ
7.0㹼8.3 c ࡢ࡜ࡁ࡟ 㹼NFDOPRO± ࡢ್࡟࡞ࡗࡓ㸦ᅗ 㸧ࠋࡇࢀࡣỈ⣲⤖ྜ࡜ྠ⛬ᗘ࠿ࡑࢀ௨ୖࡢᙉࡉ࡛
࠶ࡿࠋࡲࡓࢣ࢖⣲㙐ࡀ㛗ࡃ࡞ࡿ࡜ࠊศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡀ┤⥺ⓗ࡟ቑຍࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸦ᅗ 㸧ࠋ

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ᅗ 1. 2 ศᏊࡢ 1 ࡢศᏊ㛫┦஫స⏝࢚ࢿࣝ ᅗ 2. 㓄⨨ A ࡢሙྜࡢ 2 ศᏊࡢ 1㹼3 ࡢศᏊ㛫ࢠ࣮ࡢኚ໬㸦MP2/cc-pVDZ ࣞ࣋ࣝ㸧㸬  ┦஫స⏝࢚ࢿࣝࢠ࣮㸦MP2/cc-pVDZ ࣞ࣋ࣝ㸧㸬 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) ஂ᪂Ⲯ୍㑻㸪᭷ᶵࢣ࢖⣲໬ྜ≀ࡢ㉸ศᏊ໬Ꮫ࠾ࡼࡧືⓗᣲື࡟㛵ࡍࡿ᭱㏆ࡢ◊✲, ➨ 55 ᅇ᭷ᶵ཯ᛂⱝᡭ
ࡢ఍, ࢜ࣥࣛ࢖ࣥ㛤ദ㸪2021 ᖺ 8 ᭶ 18 ᪥㹼20 ᪥㸦≉ูㅮ₇㸧㸬 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) A. Tsurusaki, H. Sato, S. Kyushin, Organometallics 2021, 40, 2852 (supplementary cover ࡟᥇ᢥ㸧㸬‫ۻ‬2) S. Kyushin, H. Fujii, K. Negishi, H. Matsumoto, Mendeleev Commun. 2022, 32, 87㸦invited paper㸧㸬‫ۻ‬3) S. Kyushin, Y. Suzuki, Molecules 2022, 27, 2241㸦invited paper㸧㸬- 22 -

ග䜰䝑䝥䝁䞁䝞䞊䝆䝵䞁䛾䛯䜑䛾㓄఩Ꮚಖㆤ㔠ᒓ䜽䝷䝇䝍䞊ቑឤ๣㻌䛻㛵䛩䜛ィ⟬⛉Ꮫⓗ◊✲㻌㻯㼛㼙㼜㼡㼠㼍㼠㼕㼛㼚㼍㼘㻌㼟㼠㼡㼐㼥㻌㼛㼚㻌㼘㼕㼓㼍㼚㼐㻙㼜㼞㼛㼠㼑㼏㼠㼑㼐㻌㼙㼑㼠㼍㼘㻌㼏㼘㼡㼟㼠㼑㼞㻌㼟㼑㼚㼟㼕㼠㼕㼦㼑㼞㼟㻌㼒㼛㼞㻌㼜㼔㼛㼠㼛㼚㻌㼡㼜㼏㼛㼚㼢㼑㼞㼟㼕㼛㼚㻌‫୕ۑ‬஭ṇ᫂㸦❧ᩍ኱Ꮫ⌮Ꮫ㒊㸧1◊✲┠ⓗ୕㔜㡯୕㔜㡯ᾘ⁛࡟ᇶ࡙ࡃග࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ㸦77$8&㸧ࡣࠊኴ㝧ග⛬ᗘࡢᙅ࠸ග࡛ࡶ㧗ຠ⋡࡞࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽ㠉᪂ⓗ࡞࢚ࢿࣝࢠ࣮ኚ᥮ᢏ⾡࡜ࡋ࡚⌧ᅾ኱ࡁ࡞ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࠊ77$8& ࡢ୕㔜㡯ቑឤ๣࡜ࡋ࡚ᶵ⬟ࡍࡿ࠶ࡿ࠸ࡣᶵ⬟ࡍࡿྍ⬟ᛶࡢ࠶ࡿ㓄఩Ꮚಖㆤ㈗㔠ᒓࢡࣛࢫࢱ࣮࡟ᑐࡋ࡚⣔⤫ⓗ࡞⌮ㄽィ⟬ࢆᐇ᪋ࡋࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳୍㔜㡯࣭୕㔜㡯≧ែ࡟࠾ࡅࡿᏳᐃᵓ㐀ࠊᇶᗏ≧ែ࠿ࡽྛບ㉳≧ែ࡬ࡢ㟁Ꮚ㑄⛣ࡢ≉ᛶ㸦㑄⛣࢚ࢿࣝࢠ࣮ࠊ㑄⛣࣮࣓ࣔࣥࢺࠊ᣺ືᏊᙉᗘ࡞࡝㸧ࢆ᫂ࡽ࠿࡟ࡍࡿࠋᐇࢹ࣮ࢱ࡜ࡢᑐᛂ࡟ࡘ࠸࡚ࡶヲ⣽࡟᳨ウࡋࠊ୕㔜㡯ቑឤ๣࡜ࡋ࡚ຠ⋡ࡼࡃᶵ⬟ࡍࡿ㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࣭⤌ᡂࡢ᥈⣴ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ⏦ㄳ⪅ࡽࡀ᪤࡟ 77$8& ࡢቑឤ๣࡜ࡋ࡚ᶵ⬟ࡍࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿ㔠ᒓࢡࣛࢫࢱ࣮㸦$X&Xࠊ

$X&Xࠊ$Jx$Xx x  㸧࡟ᑐࡋ࡚ࠊ*DXVVLDQ ࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘ㸦')7㸧ἲ࠾ࡼࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ㸦7'')7㸧ἲ࡟ࡼࡿ⌮ㄽィ⟬ࢆᐇ᪋ࡋࡓࠋලయⓗ࡟ࡣࠊ  ⁐ ፹ ຠᯝࢆྲྀࡾධࢀࡓᇶᗏ≧ែࡢᏳᐃᵓ㐀ࡢ᥈⣴㸦ᵓ㐀᭱㐺໬࡜ᇶ‽᣺ືゎᯒ㸧ࠊ2) ບ㉳୍㔜㡯࠾ࡼࡧບ㉳୕㔜㡯≧ែ࡬ࡢᆶ┤㑄⛣࢚ࢿࣝࢠ࣮ࠊ㑄⛣࣮࣓ࣔࣥࢺࠊ᣺ືᏊᙉᗘࠊ  ບ㉳୍㔜㡯≧ែࡢᏳᐃᵓ㐀ࡢホ౯ࢆᐇ᪋ࡋࡓࠋ3◊✲ᡂᯝ
$Jx$Xx x   ࡟ᑐࡍࡿ⌮ㄽィ⟬࠿ࡽࠊ㸰ࡘࡢṇ஧༑㠃యᵓ㐀ࣘࢽࢵࢺ࡟ࡼࡗ࡚ඹ᭷ࡉࢀࡓ୰ᚰ

ཎᏊࡀ㔠ཎᏊ࠿ࡽ㖟ཎᏊ࡟⨨ࡁ᥮ࢃࡿ࡜ࠊບ㉳୕㔜㡯㸦7㸧≧ែࡀࣈ࣮ࣝࢩࣇࢺࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࠊx  ࠿ࡽ x ࠊ ࡬࡜⇥ග㔞Ꮚ཰⋡ࡀቑ኱ࡋ࡚࠸ࡃ࡜࠸࠺ᐇ㦂⤖ᯝࢆྜ⌮ⓗ࡟ㄝ᫂ࡉࢀࡓࠋࡲࡓࠊ
࠸ࡎࢀࡢࢡࣛࢫࢱ࣮࡟࠾࠸࡚ࡶ 67 㛫࡛┤᥋ⓗ࡞ࢫࣆࣥ㌶㐨┦஫స⏝ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࠊᐇ࡛࡯ࡰ ࡢ㡯㛫஺ᕪ㸦,6&㸧཰⋡ࡀᚓࡽࢀ࡚࠸ࡿࡇ࡜࡜ࡼ࠸ᑐᛂࡀࡳࡽࢀࡓࠋ$X&X ྜ㔠ࢡࣛࢫࢱ࣮࡟࠾࠸࡚ࡣࠊ$X&X ࠿ࡽ $X&X ࡬࡜ ,6& ཰⋡ࡀ  ಸ⛬ᗘቑ኱ࡍࡿࡢࡣࠊ7 ≧ែࡢࣈ࣮ࣝࢩࣇࢺ࡜ 67࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡢῶᑡ࡟ࡼࡿࡶࡢ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1) ⡿㇂ᶞ࣭ᯇᮌὒ᠇࣭᪂ᇼె⣖࣭୕஭ṇ࣭᫂ⱴཎᰤ୍࣭ᒣᏊⱱ࣭ᑠᯘ೺஧㸪ࣈࢱࢪ࢖୍࡛ࣥ㒊⨨᥮ࡋࡓ⎔≧࣊࢟ࢧ-2,7-࢔ࣥࢺ࢚ࣜࣞࣥࢳࢽࣞࣥㄏᑟయࡢྜᡂ࡜[10]CPP ໟ᥋㸪2021 ᖺ᪥ᮏ໬Ꮫ఍᫓Ꮨᖺ఍  ᪂ᇼె⣖࣭࿴⏣ᝆᖿ࣭୕஭ṇ᫂㸪nࢳ࣮࢜ࣛࢺಖㆤ㖟ࢡࣛࢫࢱ࣮ࢆ୕㔜㡯ቑឤ๣࡟⏝࠸ࡓ㏆㉥እ-㟷Ⰽග࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ”㸪ࢼࣀᏛ఍➨ 19 ᅇ኱఍㸪2021 ᖺ 5 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ3) ᭷㤿኱ᆅ࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪㓄఩Ꮚಖㆤ Au2Cu6 ࢡࣛࢫࢱ࣮࡟࠾ࡅࡿບ㉳୕㔜㡯≧ែ⏕ᡂ࡟㛵ࡍࡿ◊✲㸪ࢼࣀᏛ఍➨ 19 ᅇ኱఍㸪2021 ᖺ 5 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ4) ᭷㤿኱ᆅ࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪ഓҒࢢฯ‫ ޤ‬Au2Cu6 έϧηνʖ͹‫ॄڿ‬༢ً൅ޭ㸪2021 ᖺග໬Ꮫウㄽ఍㸪
2021 ᖺ 9 ᭶ɾΨϱϧ΢ϱ֋࠷ Ⲩᒃ኱࿴࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪ࢳ࣮࢜ࣛࢺಖㆤ Ag25 ࢡࣛࢫࢱ࣮ࡢග࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ≉ᛶ࡟ᑐࡍࡿ␗ཎᏊࢻ࣮ࣆࣥࢢຠᯝ㸪2021 ᖺග໬Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶ɾΨϱϧ΢ϱ֋࠷6) 㧗ᶫ┤ஓ࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪ࢳ࣮࢜ࣛࢺಖㆤ Ag29 ࢡࣛࢫࢱ࣮࡟ࡼࡿ୕㔜㡯ቑឤ࡜ග࢔ࢵࣉࢥࣥࣂ࣮ࢪ

- 23 -

ࣙࣥ㸪2021 ᖺග໬Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶ɾΨϱϧ΢ϱ֋࠷7) ୕஭ṇ࣭᫂ᑠᯘ᭷ᕼ࣭᭷㤿኱ᆅ࣭᪂ᇼె⣖㸪㧗Ⓨගᛶ Ag13Au12 ࢡࣛࢫࢱ࣮ࡢⓎග㐣⛬࡟࠾ࡅࡿ୕㔜㡯ᛶࡢᐤ୚㸪➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍ɾΨϱϧ΢ϱ֋࠷8) ᪂ᇼె⣖࣭ෆ⏣ᝡᮌ࣭୕஭ṇ᫂㸪ⓑ㔠ࢻ࣮ࣉ㖟ࢡࣛࢫࢱ࣮ࡢග࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ≉ᛶ࡟ᑐࡍࡿ㓄఩Ꮚࡢᙳ㡪㸪➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶㸪Ψϱϧ΢ϱ֋࠷9) ࿴⏣ᝆᖿ࣭᪂ᇼె⣖࣭ྜྷἼᣅᕭ࣭ᑠᯘ೺஧࣭୕஭ṇ᫂㸪㓄఩Ꮚಖㆤ㔠ࢡࣛࢫࢱ࣮ࢆ୕㔜㡯ቑឤ๣࡟⏝࠸ࡓග࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ㸪➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶㸪Ψϱϧ΢ϱ֋࠷10) ᭷㤿኱ᆅ࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪Au2Cu6 ࢡࣛࢫࢱ࣮ࡢບ㉳≧ែ⦆࿴㐣⛬࡟ᑐࡍࡿ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚࡢᙳ㡪㸪➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ11) ᑠᯘ೺஧ʀӮౣ߁୉ʀธ୫धʀন໨༺‫ݓ‬ʀՑ߻৶೯ืʀ৿ຉՄ‫ن‬ʀ୕஭ṇ࣭᫂ⱴཎᰤ୍࣭ᒣᏊⱱ㸪⎔≧࣊࢟ࢧ-2,7-(4,5-ࢪ࢔࣮ࣜࣝ)࢔ࣥࢺ࢚ࣜࣞࣥࢳࢽࣞࣥㄏᑟయࡢྜᡂ࡜ᛶ㉁㸪➨ 52 ᅇ ୰㒊໬Ꮫ㛵ಀᏛ༠఍ᨭ㒊㐃ྜ⛅Ꮨ኱఍㸦㟼ᒸ㸧

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³ࢳ࣮࢜ࣛࢺಖㆤ㈗㔠ᒓࢡࣛࢫࢱ࣮ࡢග≀⌮㸸ࡑࡢ⌮ゎࡢ⌧≧࡜ᛂ⏝´ࠊ᪂ᇼె⣖ࠊ୕஭ṇ᫂ࠊග໬Ꮫࠊ
ᕳྕࠊSS

- 24 -

FixL 

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Molecular mechanism of oxygen sensor protein FixL dimer Tingting WANG( *',

-

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 w  Ärwp+J;9XRÄrw # _×c  ÅÄÔÞxeß(hÛ|®Í¿ !(HKnzEPLX:X(¥% GT1PK(²  # M>R  (Ë)V4VFR(°% YÎ)V4VFR^aÌ«#kµ  (Ë #   ?P6,0?QX(%C*=*F3V:0? %¬W-CR/X¨I0?R()JDÖ¡y Á%
&#Í¿ ¯ÈØµ  """!(²%¬W-CR/X¨
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 #$
FixL Q.V@Ärw"ÜÄrw¬W-CR/XÑÓC<?UX0(¢Ð%]Ç X ÅÄÔ´!Ú'#C<?UX0jÆHKÒg#_×c³Ý¦p
_×c³ÝQ.V@Är")JDÖ¡yÙ¶`d² Ê $   51ARbÕÚ\%  ºt&CURP GT1PK(¬¨Í¿:VE0^  ¬¨[JPCB(2022)126, 3029](Øµ)&
(Invited Talk) Takahisa Yamato, “Network model of vibrational energy transfer in proteins”, Telluride Science

Research Center Workshop on Protein Dynamics, (Online), Telluride, CO, USA, Jul. 15, (2021).
(Invited Talk) Takahisa Yamato, “Network model of vibrational energy transfer in proteins”, Pacifichem 2021,
Symposium #200 Biomolecules at interfaces defining the cellular environment: From conformational dynamics toinformatic approaches. (Online) Hololulu, HI, USA. Dec. 16-17, (2021)

&                  #           $  %)'))&()+ *'),"*+! - 25 -

ග໬Ꮫ཯ᛂࡢไᚚ࡜ᛂ⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on the control and application of photochemical reactions۵㯮ᓮ ㆡࠊబ఑ ┒ஂ㸦㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓ㸧◊✲┠ⓗࠊෆᐜᮏ◊✲ࡣḟࡢ஧ࡘࡢࣉࣟࢪ࢙ࢡࢺ࠿ࡽᡂࡿ㸸㸦㸧㉸▷ࣃࣝࢫ࣮ࣞࢨ࣮࡟ࡼࡿ㔞Ꮚไᚚ㸹  㓟ᛶ⁐ᾮ୰࡛ࡢ࢖࢜ࣥ㘒యࡢᵓ㐀◊✲ࠋ㸦㸧࡛ࡣࠊ/L&O ศᏊࡢΰྜ≀ /L&O ࡜ /L&O ࡢྠ఩య㑅ᢥⓗศᏊ㓄ྥࢆᐇ⌧ࡍࡿ᭱㐺ไᚚࣃࣝࢫࡢ⟬ฟࢆ┠ⓗ࡜ࡍࡿࠋ㸦㸧࡛ࡣࠊ  ࣮ࣞࢨ࣮ᚤ⢏Ꮚ໬ἲ࡟ࡼࡿ 3G ⏕ᡂᶵᵓࡢゎ᫂ࠊ ࣏ࣜࣔࣜࣈࢹࣥ㓟ࡢᏳᐃᵓ㐀᥈⣴࠾ࡼࡧศගࢹ࣮ࢱィ⟬ࠊࢆ┠ⓗ࡜ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㸦㸧୍ගᏊ࠾ࡼࡧ஧ගᏊ㐣⛬ࢆ⪃៖ࡋࡓࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ࠊ/L&O ศᏊࡢྠ఩య㑅ᢥⓗ࡞ศᏊ㓄ྥࢆᐇ⌧ࡍࡿ᭱㐺㟁ሙࢆ᭱㐺ไᚚ⌮ㄽ࡟ࡼࡾồࡵࡿࠋἼ᮰ࡢ᫬㛫Ⓨᒎィ⟬ࡣࠊᅇ㌿⮬⏤ᗘࡢࡳࢆ⪃៖ࡋ࡚VSOLWRSHUDWRU ἲ࡟ࡼࡾ⾜࠺ࠋ㸦㸧0ROSUR ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊ3G&OศᏊࡢᵓ㐀࡜㑄⛣࢚ࢿࣝࢠ࣮ࢆ 05&,ἲ࡛ィ⟬ࡍࡿࠋᇶᗏ㛵ᩘࡣ 3G ࡟ DXJFFS97=33ࠊ&O ࡟ DXJFFS97= ࢆ⏝࠸ࡿࠋ  *DXVVLQ ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊ')7 ィ⟬࡟ࡼࡾࢭࢩ࣒࢘࢖࢜ࣥ &V࡟ᑐࡋ࡚㧗࠸྾╔ᛶ⬟ࢆ♧ࡍࣜࣥࣔࣜࣈࢹࣥ㓟 30R2̽ࢆᑐ
㇟࡟ࡋ࡚ࠊࡑࡢ㘒యᵓ㐀ࢆㄪ࡭ࠊ; ⥺྾཰ศගᐇ㦂ࡢ⤖ᯝ࡜ẚ㍑ࡍࡿࠋ◊✲ᡂᯝ 㸦㸧᭱㐺ไᚚィ⟬ࡢ⤖ᯝࠊ2 ࡘࡢྠ఩యศᏊࢆ㧗ຠ⋡࡛㏫ྥࡁ࡟㓄ྥࡉࡏࡿ᭱㐺ࣃࣝࢫࡀᚓࡽࢀࡓࠋࡇࡢ
࡜ࡁᚓࡽࢀࡓࣃࣝࢫࡣࠊ୍ගᏊ࠾ࡼࡧ஧ගᏊ㐣⛬ࡀ┦஌ⓗ࡟స⏝ࡍࡿ⌮᝿ⓗ࡞ࡶࡢ࡛࠶ࡗࡓࠋ(2-1) ࡇࢀࡲ࡛ࡢ◊✲࡟ࡼࡾࠊ᭱ึ࡟⁐ᾮ୰࡟Ꮡᅾࡍࡿ>3G&O@㘒యࡣ 89 ↷ᑕ࡟ࡼࡾ 3G&O&O&Oࡢࡼ࠺࡟ゎ㞳ࡍࡿࡇ࡜ࡀ
♧၀ࡉࢀ࡚࠸ࡿࠋ3G&O ࢔ࢽ࢜ࣥࡢᵓ㐀࡜࢚ࢿࣝࢠ࣮ࢆồࡵࡓ⤖ᯝࠊࡇࡢ࢔ࢽ࢜ࣥࡢ࢚ࢿࣝࢠ࣮ࡣྠࡌ
JHRPHWU\ ࡢ୰ᛶ 3G&O ศᏊࡢࡑࢀࡼࡾࡶపࡃぢ✚ࡶࡽࢀࠊ࢔ࢽ࢜ࣥࡀᏳᐃ࡟Ꮡᅾࡋᚓࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ
Cs+...PMo12O403–㘒యࡢᵓ㐀ࢆࠊ㸲✀㢮ࡢ஺᥮┦㛵ỗ㛵ᩘ㸦M08-HX, B3LYP, M06, M06-L㸧ࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡾㄪ࡭ࡓࠋB3LYP, M06, M06-L ࡛ࡣ࡝ࡢᇶᗏ㛵ᩘ࡜ࡢ⤌ࡳྜࢃࡏ࡛ࡶᵓ㐀᭱㐺໬࡟᫬㛫ࢆせࡋࠊ཰᮰࡟
ࡣ⮳ࡽ࡞࠿ࡗࡓࠋ୍᪉ࠊM08-HX ࢆ౑ࡗࡓሙྜ࡟ࡣࠊᇶᗏ㛵ᩘ࡟౫ࡽࡎẚ㍑ⓗ㏿ࡸ࠿࡟᭱Ᏻᐃᵓ㐀ࡀᚓࡽࢀ
ࡓࠋM08-HX / SDD for Cs&Mo; 6-311G** for P; 6-311G for P ࣞ࣋ࣝࡢィ⟬࡛᭱㐺໬ࡋࡓ Cs+...PMo12O403–㘒యᵓ㐀ࢆᇶ࡟ࠊX ⥺྾཰ศග࡟ࡼࡾᚓࡽࢀࡓᗈᇦ X ⥺྾཰ᚤ⣽ᵓ㐀㸦EXAFS㸧ࢆゎᯒࡋࡓ⤖ᯝࠊCs+ࡣ㸰ಶࡢ
PMo12O403–࡜㘒ᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬㯮ᓮࠊᶓᒣࠊ኱ᵳࠊ͆ྠ఩య㑅ᢥⓗศᏊ㓄ྥࡢ㔞Ꮚไᚚ͇ࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶ࠊᮐᖠ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬㯮ᓮࠊ୰すࠊబ఑ࠊ኱ሙࠊ͆$ELQLWLRVWXG\RISDOODGLXPGLFKORULGH3G&ODQGLWVDQLRQ3G&OѸ͆
&KHP3K\V  ‫ࠊྂ℩ۻ‬బ఑ࡽࠊ;$)6DQDO\VLVRI&VDGVRUEHGDPPRQLXPSKRVSKRPRO\EGDWHW\SHJUDIWHGDGVRUEHQWDQG
YLVXDOL]DWLRQRILWVVHOHFWLYLW\ࠊᢞ✏‽ഛ୰- 26 -



Theoretical Studies on Vibronic Couplings
Uâ ĉSûy~ÏRñHîÍÑ7F9GĊ

1 ÍÑÉÈ[d~iö!nTVØ)wd, Ì*- +nTVb®!mjÁ oJ(fá]| ]ë_^Ä-,nTVb®!]|  ĆsnTVØ/ã W}¿=:B:ôTi!ôT,´Ô ý´Ôd b®È,]|  ĆsnTVØ/ã
-#i Xø_-,gĆsnTVb®/ë£ -"nTVb®/^Äi_ kÚ,Ù *-,nTVb®!N8E¼2;C4G (ZPE) êæ² (DC)Æ¬,
-$x ë­! ZPE ËÉòð-DC !Ù- ©ÍÑ!d~i ZPE  DCL¢/ÙnTVØ`ĆsnTVb®/ÂðÈ£* 2 ÍÑ¢¸íÒ¢¸tÀíÒ!¶ÿ¸(DFT))+ãíÒD>C! B3LYP/6-311G(d,p)DFT íÒ!

Gaussian16 /Ä3 ÍÑ®
l´Ô/ý´ÔdĂÃ,¹dăv,nTVb® ΔEa h|K ΔEa(A)/íÒ Ö®iÊÿK,´Ô ý´Ôd nTVb®y K, ] ĉH±nTVb®Ċ
$iÊÿK´Ô ý´Ôd),nTVb®'ï£,  ĉQ±nTVb®Ċ¹dăv ºK,´Ô %uaK,´Ô %/--Zý´ÔdØ` cë­/é,¬¸)¹dăv wd/µ&.©¸P»-õ+¹dăv!ºua¥'b®Èi/Xø_,Ø<9GF/, 

4 Çä×$!P[1] rþ §, yÅ Ý, ye ÞÃ, Uâ ¦°àÛzāą·ª¡ ITICÜÇÈ Ð Î-),ąß]ĄÀ Ã Sûy~ÏRñHîÍÑ7F9G3FA0F5F?61@ (2022).
[2] yè ćO, yÅ Ý, ĈY Ā, ¤Å Ê³, Õ Iú, « ñzú, ÅM å, Uâ Sr-Ti Óçmüd¾ Pd ì{ óq¨¯÷ NO pË Ćsù Sûy~ÏRñHîÍÑ7F9G3FA0
F5F?61@ (2022).

5 \½×$!P
[1] Masaki Takahashi, Nozomu Ito, Naoki Haruta, Hayato Ninagawa, Kohei Yazaki, Yoshihisa Sei, Tohru Sato, Makoto
Obata, Commun. Chem., 4, 168 (2021).

- 27 -

」㞧࡞ᫍ㛫᭷ᶵศᏊ⏕ᡂ཯ᛂࡢ⌮ㄽⓗ◊✲Theoretical study on formation of interstellar complex organic
molecules‫⏣ۑ‬௦ ᇶ៞ࠊၿ἞ ᰟᖹ㸦ᮾὒ኱Ꮫ㸧1◊✲┠ⓗᫍᙧᡂࡢฟⓎⅬ࡛࠶ࡿศᏊ㞼ෆ࡟࠾࠸࡚,⣲⣔⢏Ꮚ࡟྾╔ࡋᅛ໬ࡍࡿ.
ࡣ H2O ࠿ࡽᡂࡿࡀ,ࡓ,Ẽ┦୰ࡢ H2O, CO, NH3 ࡞࡝ࡢ᥹ⓎᛶศᏊࡣࢣ࢖㓟ሷ⢏ᏊࡸⅣࡇࢀ࡟ࡼࡾ⢏Ꮚࡢ࿘ࡾ࡟ࡣᫍ㛫ị࡜࿧ࡤࢀࡿịࡀᙧᡂࡍࡿ.

ศᏊ㞼ࡀᡂ㛗ࡋẼ┦୰ࡢศᏊࡀቑ࠼ጞࡵࡿ࡜, CO ࡢị⾲㠃࣊ࡢ྾╔ࡀከࡃ࡞ࡿ.

྾╔ࡋࡓ CO ࡀỈ⣲໬ࡍࡿࡇ࡜࡛ H2CO ࡸ CH3OH ࡞࡝ࡢ᭷ᶵศᏊࡀ⏕ᡂࡍࡿࡓࡵ,࠾ࡅࡿ」㞧࡞᭷ᶵศᏊ

ᫍ㛫ịࡢ኱㒊ศࡲᫍ㛫ịࡣᫍ㛫࡟(Interstellar Complex Organic Molecules; iCOMs)ᙧᡂࡢ཯ᛂሙ࡜࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚

࠸ࡿ. ࡋ࠿ࡋ, ศᏊ㞼ෆࡣᴟࡵ࡚ప

࡟࡞ࡿࡓࡵ, iCOMs ᙧᡂࡢ࠸ࡃࡘ࠿ࡣࣛࢪ࢝ࣝ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡿࣂ

ࣜ࢔ࣞࢫ࡞཯ᛂ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡇ࡜ࡀከ࠸. ࡑࡢࡓࡵ㏆ᖺ࡛ࡣ, ࣛࢪ࢝ࣝ཯ᛂ࡟ࡼࡿศᏊᙧᡂࡀάⓎ࡟◊✲ࡉࢀ࡚࠸ࡿ. ≉࡟࣒࣍ࣝ࢔࣑ࢻ(NH2CHO) ࡣ, ᵝࠎ࡞ᫍᙧᡂ㡿ᇦ࡛Ꮡᅾࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡾ, ⏕≀Ꮫⓗ࡟㔜せ࡞ 4 ࡘࡢඖ⣲(H, C, N, O)ࢆྵࡴࡶࡢࡢ୰࡛᭱ࡶ༢⣧࡞ iCOMs ࡛࠶ࡿࡓࡵ㠀ᖖ࡟ὀ┠ࡉࢀ࡚࠸ࡿ.
ᮏ◊✲࡛ࡣ, CO ࡀ㇏ᐩ࡞ị⾲㠃ࢆ᝿ᐃࡋ, ࡑࡢୖ࡛㉳ࡇࡿ HCO + NH2 ཯ᛂࢆ ab initio molecular dynamics(AIMD)࡛ィ⟬ࡋࡓ. ࡲࡓ, ⏕ᡂࡋࡓศᏊࡀ⾲㠃࠿ࡽ⬺㞳ࡍࡿ࠿ྰ࠿ࡣ, Ẽ┦࡟Ꮡᅾࡍࡿከᵝ࡞ศᏊࡢ㉳※ࢆ
ㄝ᫂ࡍࡿୖ࡛㔜せ࡛࠶ࡿࡓࡵ, ⏕ᡂ≀ࡢ⬺㞳☜⋡ࡶồࡵࡓ.

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࡣ Gaussian16 ࢆ⏝࠸࡚⾜ࡗࡓ. 32 ศᏊࡢ CO ࢡࣛࢫࢱ࣮ࢆ

B3LYP/6-31+G(d,p)+D3 ࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬ࡋࡓᚋ, ࢡࣛࢫࢱ࣮ࡢ
࿘ࡾ࡟, ṇ஧༑㠃యࡢ㡬Ⅼࡢ఩⨨࡟࡞ࡿࡼ࠺࡟, HCO, NH2, CH3 ࢆࡑࢀࡒࢀ㓄⨨ࡋࡓ(ᅗ 1.a). ࡑࢀࡒࢀࡢ఩⨨࡛ࡉࡽ࡟ᵓ㐀᭱㐺໬ࡋ࡚CO ࢡࣛࢫࢱ࣮࣊ࡢࣛࢪ࢝ࣝศᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓ. ḟ
࡟ 192 ศᏊࡢ CO ࢡࣛࢫࢱ࣮(ᅗ 1.b)࡟ᑐࡋ࡚ࡶࣛࢪ࢝ࣝศᏊࡢ྾
╔࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓᚋ, 㑄⛣≧ែᵓ㐀(TS)࠿ࡽ AIMD ィ⟬ࢆ㛤ጞࡋࡓ. ࡇࡢィ⟬ࡣ NVE ⣔,ࢫࢸࢵࣉࢧ࢖ࢬ 1.0 fs ࡛⾜ࡗࡓ. ࡲ
ࡓ , ONIOM ἲ ࢆ ⏝ ࠸ ࡚ , ྾ ╔ ศ Ꮚ ࡜ ࡑ ࡢ ㏆ ࡃ ࡢ CO ࡣ
B3LYP/6-31+G(d,p)+D3 ࡛, ࡑࢀ௨እࡢ CO ࡣ B3LYP/STO-3G+D3
࡛⾜ࡗࡓ. ࡲࡓ, ⏕ᡂ≀ࡀị࠿ࡽ⬺㞳ࡋẼ┦୰࡟ᨺฟࡉࢀࡿ☜⋡ࢆ
Rice-Ramsperger-Kessel ⌮ㄽ࡟ᇶ࡙࠸࡚ィ⟬ࡋࡓ.

ᅗ㸯 CO ࢡࣛࢫࢱ࣮

- 28 -

3◊✲ᡂᯝ
⾲ 1 ࡟ CO ࢡࣛࢫࢱ࣮࡟ᑐࡍࡿྛࣛࢪ࢝ࣝศᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࢆỈࢡࣛࢫࢱ࣮࡟ᑐࡍࡿࡶࡢ࡜ẚ㍑ࡋ࡚

♧ࡋࡓ. CO ࡟ᑐࡍࡿࣛࢪ࢝ࣝศᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࡣỈ࡜ẚ࡭ࡿ࡜ప࠸ഴྥ࡟࠶ࡿ. CO ࢡࣛࢫࢱ࣮࡟ᑐࡋ࡚
NH2 ࡀ᭱ࡶᙉࡃ྾╔ࡋ,྾╔࢚ࢿࣝࢠ࣮ࡣᖹᆒ࡛ 0.23 eV ࡛,᭱ࡶᙉࡃ྾╔ࡋࡓሙᡤ࡛ 0.30 eV ࡛࠶ࡗࡓ.

AIMD 㛤ጞ┤ᚋ HCO ࡜ NH2 ࡣ࠾஫࠸࡟⛣ືࡋ, ⣙400 fs ⤒㐣ᚋ 2 ࡘࡢࣛࢪ࢝ࣝࡣ⤖ྜࡋ NH2CHO ࢆᙧᡂࡋࡓ(ᅗ 2). ࡑࡢᚋᅗ 3 ࡟♧ࡍࡼ࠺࡟ NH2CHO ࡢ࢚ࢿࣝࢠ࣮ࡣᚎࠎ࡟ị࡟྾཰ࡉࢀ࡚࠸ࡃࡇ࡜ࡀࢃ࠿ࡿ. ᅗ 4 ࡟ࡣ཯ᛂ≀ࡢ HCO ࡜ NH2 ࡢ㊥㞳࠾ࡼࡧ HCO ࡜⾲㠃࡜E b [eV]

⾲㸯
32CO

32H2O

HCO

0.162

192CO
0.161

NH2

0.233

0.670

0.460

CH3

0.112

0.237

0.170

0.309

ࡢ㊥㞳ࡢኚ໬ࢆ♧ࡋࡓ. ᅗ 4 ࠿ࡽ NH2CHO ࡀ⤖ྜࢆಖࡗࡓࡲࡲ CO ࢡࣛࢫࢱ࣮࠿ࡽᚎࠎ࡟⬺㞳ࡋ࡚࠸ࡃࡇ࡜ࡀࢃ࠿ࡿ. ⾲㠃ศᏊ࡟ࡼࡿ࢚ࢿࣝࢠ࣮ࡢ྾཰ࡀ NH2CHOࢆᏳᐃ໬ࡉࡏ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ. ࡲࡓ RRK ⌮ㄽ࡟ᇶ࡙ࡃᘧ࡛ NH2CHO ࡢ⬺㞳☜⋡ࢆィ⟬ࡍࡿ࡜ 2.4 %࡜
࡞ࡗࡓ. ࡇࢀࡣ Morisset ࡽࡀ࣓ࢱࣀ࣮ࣝ࡞࡝࡛ィ⟬ࡋࡓࡶࡢ࡜ẚ㍑ࡍࡿ࡜኱ࡁ࡞್࡛࠶ࡿ. ࡇࢀࡽࡢ⤖ᯝ࠿ࡽ, CO ࢡࣛࢫࢱ࣮ୖ࡛ HCO ࡜ NH2 ࡣᏳᐃⓗ࡟ NH2CHO ࢆ⏕ᡂࡋ, ⏕ᡂࡋࡓ NH2CHO ࡣ⾲㠃࠿ࡽ⬺㞳ࡍࡿྍ⬟ᛶࡀ㧗࠸࡜⪃࠼ࡽࢀࡿ.
ᅗ 㻞㻌

4ᅗ 㻟㻌㻺㻴㻞㻯㻴㻻㻔ᐇ⥺㻕䛸 㻯㻻 䜽䝷䝇䝍ᅗ 㻠㻌 ཯ᛂ≀ྠኈ㻔ᐇ⥺㻕䛚䜘䜃཯䞊㻔◚⥺㻕䛾㐠ື䜶䝛䝹䜼䞊ᛂ≀䛸⾲㠃䛾㊥㞳䛾ኚ໬㻔◚⥺㻕㻌

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃzᖹ⏣ᑗ኱,⏣௦ᇶ៞,ࠕࣔࣥࢸ࢝ࣝࣟᮌ᥈⣴࡜῝ᒙᏛ⩦ࢆ⏝࠸ࡓගᏛάᛶศᏊࡢ⏕ᡂࠖ,➨ 15 ᅇศᏊ⛉Ꮫ
ウㄽ఍,2021 ᖺ 9 ᭶zၿ἞ᰟᖹ,⏣௦ᇶ៞,ࠕᫍ㛫ị⾲㠃࡛ࡢศᏊᙧᡂࠖ, ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍,2021 ᖺ 9 ᭶z➲ᑿⓏ,⏣௦ᇶ៞,⏣୰ᐇ,ࠕ㌶㐨ゅ㐠ື㔞ࢆࡶࡘ࣐࢞ࣥ⥺ࡢ᪂ࡓ࡞⏕ᡂἲࠖ,᪥ᮏ≀⌮Ꮫ఍➨ 77 ᅇᖺḟ኱఍,2022 ᖺ 3 ᭶zMotomichi Tashiro, Noboru Sasao, Minoru Tanaka, “Generation of Twisted Gamma-Rays via Two-Photon
Transition”, arXiv preprint, https://doi.org/10.48550/arXiv.2203.06988- 29 -

2022 ᖺ 3 ᭶

᪂つࣃ࢖ඹᙺ໬ྜ≀ࡢᵓ㐀㸫≀ᛶ┦㛵ࡢゎ᫂࡟㛵ࡍࡿ⌮ㄽ◊✲
Theoretical study on the elucidation of the structure-property
relationships for the novel S-conjugated compounds‫ۑ‬ᒣୗ೺୍ࠊ㇂ὒ௓ࠊᑠᮧ┿ኸ㸦㜰኱㝔⌮㸧

1◊✲┠ⓗࠊෆᐜ
ᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊ࣏ࣝࣇ࢕ࣜࣥࠊࢳ࢜ࣇ࢙ࣥ࡞࡝ࡢࣃ࢖ඹᙺ໬ྜ≀ࢆ୺㦵᱁࡜ࡍࡿᵝࠎ࡞ᶵ⬟ᛶศᏊࡢྜᡂ࡜ホ౯ࢆ⾜ࡗ࡚࠸ࡿࠋࡇࢀࡽࡢᶵ⬟ᛶศᏊࡢ DFT ィ⟬࠿ࡽᵓ㐀―≀ᛶ┦㛵ࢆ᫂ࡽ࠿࡟ࡋࠊ㧗ᛶ⬟໬ࡢࡓࡵࡢศᏊタィࡢ⣒ཱྀࢆぢࡘࡅࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ2◊✲᪉ἲࠊィ⟬᪉ἲX ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾᚓࡽࢀࡓᵓ㐀ࡲࡓࡣ᥎ᐃᵓ㐀ࢆࡶ࡜࡟ࠊGaussian16 ࢆ⏝࠸ࡓ DFT ィ⟬ࢆ⾜࠸ࠊࡑࡢ᭱Ᏻᐃᵓ㐀ࠊ㟁Ꮚ≧ែࠊ྾཰࣭Ⓨග≉ᛶࠊⰾ㤶᪘ᛶࡢゎ᫂ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝࡇࡇ࡛ࡣࠊ཯ⰾ㤶᪘໬ྜ≀ࡢ⣔⤫ⓗⓎග≉ᛶホ౯࡟㛵ࡍࡿ◊✲࡟ࡘ࠸࡚⤂௓ࡍࡿࠋࡇࢀࡲ࡛࡟ࠊ㸰㸮ȧ཯ⰾ㤶᪘໬ྜ≀࡛࠶ࡿ࢖ࢯࣇࣟࣜࣥࡀࠊከ㔜Ⓨගࠊ࠾ࡼࡧ㏆㉥እⓎගࢆ♧ࡍࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡿࠋ཯ⰾ㤶᪘ᛶ࡜཯࢝ࢩࣕⓎග≉ᛶࡢ┦㛵ࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚ࠊ✀ࠎࡢ࢖ࢯࣇࣟࣜࣥࡢⓎග≉ᛶࢆホ౯ࡋࡓ࡜ࡇࢁࠊ཯
ⰾ㤶᪘ᛶࢆ♧ࡍࡶࡢࡣࡍ࡭࡚཯࢝ࢩࣕⓎග≉ᛶࢆ♧ࡋࡓࡢ࡟ᑐࡋࠊ཯ⰾ㤶᪘ᛶࢆ♧ࡉ࡞࠸ศᏊࡣࠊⓎග≉ᛶࢆ♧ࡉ࡞࠸ࠊࡍ࡞ࢃࡕ཯࢝ࢩࣕⓎග≉ᛶࡀⓎග≉ᛶ࡟㔜せ࡛࠶ࡿࡇ࡜ࡀᐇ㦂ⓗ࡟♧၀ࡉࢀࡓࠋDFT, TDDFTィ⟬࡟ࡼࡾࠊ཯ⰾ㤶᪘ᛶࢆ᭷ࡍࡿ࢖ࢯࣇࣟࣜࣥࡣ཯࢝ࢩࣕⓎග≉ᛶࡢ

LUMO+1

1RQDURPDWLF
űƒŃƈƐƌƖƖƌƒƑ

Energy / eV

$QWLDURPDWLF
ŤƑƗƌŐŮƄƖƋƄŃƇƘƄƏŃƈƐƌƖƖƌƒƑ

-4
-5
-6

LUMO

6



HOMO-162 62
$QWLDURPDWLF

O4Iph

6

1RQDURPDWLF)URQWLHURUELWDORI2

Vis emission

NIR emission
LUMO+1

6



6
6

HOMO

2

ᖖࡢ᭷ᶵศᏊ⛬ᗘࡲ࡛ᑠࡉࡃ

4

6
6

-3

ࢵࣉࡀ 11377cm-1 ࡜኱ࡁࡃࠊ୍

࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

TD-B3LYP/6-311G(d,p)

B3LYP/6-311G(d,p)ᣦᶆ࡜࡞ࡿບ㉳≧ែ㛫ࡢࢠࣕ᪉ࠊ㠀ⰾ㤶᪘࡛ࡣ 4475cm-1 ࡜㏻([FLWDWLRQHQHUJ\)URQWLHURUELWDOHQHUJ\

LUMO

HOMO



6

6

2

6

HOMO-1Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

┬␎

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Room-temperature phosphorescence of a supercooled liquid: kinetic stabilisation by desymmetrisation. Komura, M.;
Tani, Y.; Ogawa, T. Chem. Sci. 2021, 14363–14368.
‫ۻ‬Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange.
Takewaki, Y.; Ogawa, T.; Tani, Y.; Front. Chem. 2022, 9, 812593.
‫ۻ‬20S antiaromatic isophlorins without metallation or core modification. Sugimura, H.; Nakajima, K.; Yamashita, K.;
Ogawa, T. Submitted.

- 30 -

ȧࢡࣛࢫࢱ࣮ศᏊࡢ㟁Ꮚ≀ᛶࡢゎ᫂Investigation of the electronic properties of pi-cluster molecules‫ۑ‬すෆ ᬛᙪࠊஂಖ Ꮥྐ㸦኱㜰኱Ꮫ㸧1◊✲┠ⓗᮏ◊✲࡛ࡣࠊȧ㟁Ꮚࡀ㇏ᐩ࡞ⰾ㤶⎔ࢆศᏊෆ࡟ᐦ࡟㞟✚ࡉࡏࡓ໬ྜ≀ࠕSࢡࣛࢫࢱ࣮ศᏊࠖࡢྜᡂ࡜ࡑࡢ≀ᛶࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋᙜヱᖺᗘ࡟࠾࠸࡚ࡣࠊȧᣑᙇᆺࢳࢳࣂࣅࣥⅣ໬Ỉ⣲ 1 ࡀ♧ࡍ㛢Ẇ Folded ᵓ㐀࡜㛤Ẇ Twisted ᵓ㐀ࡢ␗ᛶ໬ᣲື࡟ࡘ࠸࡚㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࣉࣟࢢ࣒ࣛࡣ Gaussian16 ࢆ౑⏝ࠋᇶᗏ≧ែ࡟࠾ࡅࡿᵓ㐀᭱㐺໬ࡣ(U)ZB97X-D ỗ㛵ᩘࢆ⏝࠸࡚ホ౯ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ 6-31G(d,p)ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝྑ࡟ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ␗ᛶ໬๓ᚋࡢ࢚ࢿࣝࢠ࣮┦㛵ᅗࢆ♧ࡍࠋ1-Twisted ࡣ 1-Folded ࡼࡾࡶ+11 kcal mol-1 ࢚ࢿࣝࢠ࣮ࡀ㧗ࡃࠊ㛤Ẇ୍㔜㡯࡜୕㔜㡯࡛࡯࡜ࢇ࡝ᕪࡀࡳࡽࢀ࡞࠸ࠋ㑄⛣≧ែࡢᵓ㐀ࢆぢ✚ࡶࡿࡇ࡜࡟ࡶᡂຌࡋࠊࡑࡢ᫬ࡢ'G‡ࡣ+20 kcal mol-1 ࡜ぢ✚ࡶࡽࢀࡓࠋࡇࢀࡣᐇ㦂್࡜㠀ᖖ࡟㏆࠸ࡓࡵ㸦+18.5 kcal mol1㸧ࠊ␗ᛶ໬ࡢᵓ㐀ኚ໬ࡢ㐣⛬ࢆィ⟬࡟ࡼࡗ࡚ゎ࡛᫂ࡁࡓ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼‫[ۻ‬1] すෆᬛᙪ࣭஬᭶ዪග࣭⚟ෆ⌮Ἃ࣭㙊⏣㈼ྖ࣭ᐑᆏ༤࣭ஂಖᏕྐ
ࠕ↓⨨᥮ࢺࣜࣇ࢙ࢽ࣓ࣝࢳࣝ࢝ࢳ࢜ࣥࡢ⤖ᬗ≧ែ࡟࠾ࡅࡿ≉␗࡞ගᏛ≀ᛶࠖ㸦ཱྀ㢌Ⓨ⾲, 3C08㸧
➨ 31 ᅇᇶ♏᭷ᶵ໬Ꮫ఍㸦2021 ᖺ㸧ͤྠᏛ఍࡟࡚௚ 2 ௳࣏ࢫࢱ࣮Ⓨ⾲᭷(‫ۻ‬1P016, ‫ۻ‬2P005 )‫[ۻ‬2] ୖ㔝ెᏊ࣭すෆᬛᙪ࣭ஂಖᏕྐ
ࠕ1, 8 ఩࡛㐃⤖ࡋࡓࣇࣝ࢜ࣞࢽࣝ኱⎔≧໬ྜ≀ࡢྜᡂ࡜≀ᛶホ౯ࠖ㸦ཱྀ㢌Ⓨ⾲, K3-1vn-07㸧
᪥ᮏ໬Ꮫ఍ ➨ 101 ᅇ᫓Ꮨᖺ఍㸦2022 ᖺ㸧ͤྠᏛ఍࡟࡚௚ 2 ௳ཱྀ㢌Ⓨ⾲(‫ۻ‬K3-1vn-06, ‫ۻ‬K3-1vn-08 )ࠊ1 ௳࣏ࢫࢱ࣮Ⓨ⾲᭷(‫ۻ‬P1-3vn-24 )5ฟ∧ᐇ⦼‫[ۻ‬1] T. Nishiuchi,* T. Kubo*, et al., J. Am. Chem. Soc., 144, 7479-7488 (2022).
‫[ۻ‬2] T. Nishiuchi,* T. Kubo*, et al., Chem. Eur. J., 28, e202200286 (2022).
‫[ۻ‬3] T. Nishiuchi,* T. Kubo*, et al., Chem. Commun., 58, 3306-3309 (2022).
‫[ۻ‬4] T. Nishiuchi,* T. Kubo*, et al., Chem. Eur. J., 28, e202104245 (2022).
‫[ۻ‬5] T. Nishiuchi,* T. Kubo*, et al., Aggregate, 2, e126 (2021).

- 31 -᪂つᶵ⬟ᛶȧඹᙺศᏊࡢྜᡂ࡜≀ᛶ࡟㛵ࡍࡿ◊✲
6\QWKHVLVDQG3URSHUWLHVRI1RYHO)XQFWLRQDOʌ&RQMXJDWHG0ROHFXOHV‫ۑ‬ΎỈ ❶ᘯࠊụ⏣ ⩧ࠊ᭷ᕝ ᚸࠊᯘ⏣ 㞞❶ࠊⱱᗞ ᘯ࿴ࠊ᳃⭜ ဴஓࠊᶓ⏣ ⾨ࠊᮤ ᮾⅡࠊ㧘ᮌ ᶞࠊእᕝ ⵬㔝ࠊℊ⏣ ᑦஓࠊ⸨⏣ ῟⏕ࠊ᪂㇂ ு㸦኱㜰኱Ꮫ኱Ꮫ㝔ᇶ♏ᕤᏛ◊✲⛉㸧 ◊✲┠ⓗᇶᗏ୕㔜㡯ࡢ㠀ࢣࢡࣞⅣ໬Ỉ⣲࡛࠶ࡿࠊࢺࣜ࢔ࣥࢠࣗࣞࣥㄏᑟయࢆྜᡂ࣭༢㞳ࡋࠊ㟁Ꮚ≧ែࡸ≀ᛶࢆヲ⣽࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡟◊✲ࢆ⾜ࡗࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ ࢆ⏝࠸࡚ࠊᐦᗘỗ㛵ᩘἲ %/<3'* GS  ࡛ィ⟬ࢆ⾜ࡗࡓࠋ㛢Ẇ࡜㛤Ẇࡢ୍㔜㡯࠾ࡼࡧ୕㔜㡯ࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᭱㐺໬ࡋࡓᵓ㐀ࢆ⏝࠸࡚ࠊ໬Ꮫࢩࣇࢺ್ࠊ1,&6 ್ࠊບ㉳࢚ࢿࣝࢠ࣮ࠊศᏊ㌶㐨ࠊࢫࣆࣥᐦᗘࠊ⾲㠃㟁Ⲵࠊ㛤Ẇᛶࡢィ⟬ࢆ⾜ࡗࡓࠋ ◊✲ᡂᯝ
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್ࡣィ⟬್࡜ࡼࡃ୍⮴ࡋ࡚࠾ࡾࠊࡲࡓࠊ⤖ྜḟᩘ࠾ࡼࡧ 1,&6  ]] ್ࠊ$&,' ィ⟬ࡢ⤖ᯝࡼࡾࠊ࠸ࡎࢀࡢ  ဨ⎔ࡶⰾ㤶᪘ᛶࢆ♧ࡍࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

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‫ۻ‬6\QWKHVLVDQG&KDUDFWHUL]DWLRQRI3RO\F\FOLF+\GURFDUERQVZLWKD7ULSOHW*URXQG6WDWH
6KLPL]X$$ULNDZD60RULNRVKL76KLRPL'6DWR.7DNXL76KLQWDQL5
WK,83$&,QWHUQDWLRQDO&RQIHUHQFHRQ3K\VLFDO2UJDQLFFKHPLVWU\ ,&32& +LURVKLPD-XO\ ணᐃ ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬6\QWKHVLVDQG,VRODWLRQRID.LQHWLFDOO\6WDELOL]HG&U\VWDOOLQH7ULDQJXOHQH$ULNDZD66KLPL]X$6KLRPL'
6DWR.6KLQWDQL5J. Am. Chem. Soc. 143±‫ۻ‬$QWKUDFHQH%DVHG =ZLWWHULRQ ZLWK D 6PDOO +202±/802 (QHUJ\ *DS .D\DPD$ 6KLPL]X$ 6KLQWDQL 5
Synthesis 53±

- 32 -

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

ⳀἋࠊ㧗ᶫ

኱ᬛࠊ୰ᯘ Ꮥ࿴㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲⛉㸧◊✲┠ⓗ㉸◲㯤ศᏊ࡜ࡣࠊศᏊෆ࡟㐣๫࡟㐃⤖ࡋࡓ◲㯤ཎᏊࢆࡶࡘ⏕యศᏊ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㉸◲㯤ศᏊࡢᵓ㐀ゎᯒ࠾ࡼࡧ᣺ືゎᯒ࡟ࡘ࠸࡚ *DXVVLDQ ࢆ⏝࠸࡚ィ⟬ࡋࠊ⏕⣽⬊ෆ࡟࠾ࡅࡿ㉸◲㯤ศᏊࡢᵓ㐀ࢆணࡍࡿࡇ࡜ࢆヨࡳࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ
Cysteine persulfide ࠾ࡼࡧ Glutathione persulfide ࡟ࡘ࠸࡚ࠊGaussian 16 ࢆ⏝࠸࡚ᵓ㐀ゎᯒ࡜᣺ືゎᯒࢆ⾜ࡗࡓࠋィ⟬ᡭἲ࡟ࡣࠊB3LYP/6-311+G(2d,p)ࢆ⏝࠸ࡓࠋ⁐፹ຠᯝࢆྲྀࡾධࢀࡓィ⟬࡟ࡣࠊIEFPCM ࢆ⏝࠸ࡓࠋ◊✲ᡂᯝ᫖ᖺᗘ࡟ᘬࡁ⥆ࡁࠊCysteine persulfide ࡢᏳᐃᵓ㐀ࢆᅗ 㸸&\VWLQH ࡜ &\VWHLQHSHUVXOILGH ࡢ᭱Ᏻᐃᵓ㐀ィ⟬ࡋࡓࠋࡇࢀࡲ࡛ࡢィ⟬࡛ࠊ㓑㓟஧㔞య࡛ぢࡽࢀࡿࡼ࠺࡞࢝ࣝ࣎ࢽࣝᇶྠኈࡀศᏊෆỈ⣲⤖ྜࢆᙧᡂࡋࠊ⎔≧ᵓ㐀࡜ࡋ࡚Ᏻᐃ໬ࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿ(ᅗ 1)ࠋ
ᮏᖺᗘࡣࠊS-Sn-S ⤖ྜ௜㏆ࡢ஧㠃ゅࡢᏳᐃᛶ࡜ศᏊෆỈ⣲⤖ྜࡢ✀㢮࡟╔┠ࡋࠊᏳᐃᵓ㐀ࢆ⥙⨶ⓗ࡟ィ⟬ࡋࡓ࡜ࡇࢁࠊୖグࡢࡼ࠺࡞⎔≧ᵓ㐀ࡀ᭱Ᏻᐃᵓ㐀࡛࠶ࡿࡇ࡜࡟▩┪ࡋ࡞࠸⤖ᯝࡀᚓࡽࢀࡓࠋ௨ୖࡢ⤖ᯝ࠿ࡽࠊ
Cysteine persulfide ࡣẼ┦୰࡛㓑㓟஧㔞యᵝࡢศᏊෆỈ⣲⤖ྜࢆᙧᡂࡋࠊ⎔≧ᵓ㐀࡜ࡋ࡚Ꮡᅾࡍࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ⌧ᅾࠊཎⴭㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡍࡿ‽ഛࢆࡋ࡚࠸ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬ᙳᒣⳀἋࠊ୰ᯘᏕ࿴

ᐇ㦂་Ꮫࠊ39ࠊ2103 (2021)‫ۻ‬ᙳᒣⳀἋࠊ୰ᯘᏕ࿴

⏕໬Ꮫࠊ93ࠊ621 (2021)‫ۻ‬ᙳᒣⳀἋࠊ୰ᯘᏕ࿴

➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2021‫ۻ‬㧗ᶫ኱ᬛࠊᲚᮏ┿ྖࠊ୰ᯘᏕ࿴
‫ۻ‬ᙳᒣⳀἋࠊ୰ᯘᏕ࿴

࢜ࣥࣛ࢖ࣥ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2021

᪥ᮏ໬Ꮫ⣔༠఍ᮾ໭ᨭ㒊኱఍ࠊ2021‫ۻ‬㧗ᶫ኱ᬛࠊᲚᮏ┿ྖࠊ୰ᯘᏕ࿴

࢜ࣥࣛ࢖ࣥ➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ2021‫ۻ‬୰ᯘᏕ࿴ࠊᲚᮏ┿ྖࠊ⏣ཎ㐍ஓࠊᙳᒣⳀἋࠊ㧗ᶫ኱ᬛࠊ㰻⸨ᙬኟࡢࢩ࣏ࣥࢪ࣒࢘ࠊ2022



࢜ࣥࣛ࢖ࣥ

࢜ࣥࣛ࢖ࣥ

➨ 2 ᅇࣞࢻࢵࢡࢫ R&D ᡓ␎ጤဨ఍᫓

௝ྎฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Lisa Kageyama, Shinya Tahara, Shinji Kajimoto, Takakazu Nakabayashi, Phys. Chem. Chem. Phys., ᢞ✏‽ഛ୰- 33 -

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Fine Control of Molecular Metal Complexes and Multinuclear Clusters,and Elucidation of their Functions
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diagram showing the frontier Kohn−Sham orbitals and energy values for 1 (left) and 2 (right), calculated at theB3LYP/Def2SVP level of theory (isosurface level: 0.04 e·au–3). 

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$*5 +*'+ L. Zhen, M. Endo, H. Ube, T. Shiraogawa, P. Zhao, K. Nagata, X.-Li Pei, T. Eguchi, T. Kamachi, M. Ehara,
T. Ozawa, M. Shionoya* accepted.

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- 35 -

8DẼ┦ࢼࣀࢡࣛࢫࢱ࣮ࡢ⾪✺㏿ᗘ࡟㛵ࡍࡿศᏊືຊᏛⓗゎᯒ
Molecular dynamics analysis of the nanocluster collision rate in gas‫▱ ⯓⋢ۑ‬ஓ㸦㔠ἑ኱Ꮫ㸧
1◊✲┠ⓗࠊෆᐜ
Ẽ┦୰࡟࠾ࡅࡿᚤ⢏Ꮚࡢᖏ㟁ᩘศᕸィ⟬ࡣ࢚࢔ࣟࢰࣝࣉࣟࢭࢫࡢタィ࡟࠾࠸࡚㔜せ࡞ᙺ๭ࢆࡶࡕࠊ౛࠼

ࡤࠊᚤศᆺ㟼㟁ศ⣭ჾࢆ⏝࠸ࡓ⢏Ꮚᚄศᕸࡢ
ศᕸࡢணᐃࡣᖏ㟁ᩘศᕸࡢ⢭ᗘ࡟ࡼࡗ࡚኱ࡁࡃኚ໬ࡍࡿࠋࡇࡢᖏ㟁ᩘ࡟ࡣ㸦㸯㸧↓ᖏ㟁⢏Ꮚ࡜࢖࢜ࣥ㛫ࡢ⾪✺㏿ᗘᐃᩘ࡟࠾ࡼࡧࠊ
㸦㸰㸧ᖏ㟁⢏Ꮚ࡜࢖࢜ࣥ㛫ࡢ⾪✺㏿ᗘ

ᐃᩘࡀᚲせ࡛࠶ࡾࠊFuchs ࡢ⌮ㄽ㸦Fuchs, J. Aero. Sci., 1963㸧ࡸ Gopalakrishnan ࡽࡢࢢ࣮ࣝࣉࡢᘧ
㸦Li et al., J. Aero.
Sci., 2020㸧࠿ࡽᚓࡽࢀࡿࠋࡋ࠿ࡋࠊ
㸦㸯㸧ࡢ⢏Ꮚ㸫࢖࢜ࣥ㛫࡟ാࡃ࣏ࢸࣥࢩࣕࣝࡀ㏆㊥㞳࠿ࡘᑠࡉ࠸ࢣ࣮ࢫࡸࠊ
㸦㸰㸧ࡢ୰࡛࣏ࢸࣥࢩࣕࣝࡀ᩺ຊ࡜ࡋ࡚ാࡃࢣ࣮ࢫ㸦㏫ᴟᛶࢆࡶࡘ⢏Ꮚ࡜࢖࢜ࣥࡢ⾪✺㸧ࡣ⌮ㄽࠊᐇ㦂࠾ࡼࡧࣔࢹࣜࣥࢢࡀⰋዲ࡟୍⮴ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ㏫ᴟᛶࡢ⾪✺⌮ㄽ࠾ࡼࡧ᥎ᐃᘧࡣᮍࡔ☜❧ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊᘬຊࡀാࡃࢣ࣮ࢫࡢ⢏Ꮚ㸫࢖࢜ࣥ㛫⾪✺ࡢࣔࢹࣜࣥࢢࢆ⾜ࡗ࡚࠸ࡿࠋ➹⪅ࡣ㸰㸮㸰㸮ᖺᗘࡲ࡛ࡢ฼⏝ᮇ㛫࡛㐃⥆య̿ศᏊືຊᏛࣁ࢖ࣈࣜࢵࢺἲࢆ㛤ⓎࡋࠊNO2 㸫 ࡜ NH4+ ࡢ࣒࣊ࣜ࢘୰࡛ࡢ⾪✺
㸦Tamadate et al., JCP, 2020㸧࠾ࡼࡧࠊከ౯࡟ᖏ㟁ࡋࡓ࣏࣐࣮ࣜ㸦࣏࢚ࣜࢳࣞࣥࢢࣜࢥ࣮ࣝࠊPEG㸧࡜ NO2㸫ࡢ❅⣲ศᏊୗ࡟࠾ࡅࡿ⾪✺㐣⛬ࡢィ⟬㸦Tamadate et al., PCCP, 2020㸧ࢆᐇ᪋ࡋࠊᐇ㦂⤖ᯝ࡜ࡢᩚྜᛶࢆ☜ㄆࡋ࡚࠸ࡿࠋᮏᖺᗘࡣࡇࡢᡭἲࡢ㐺⏝⠊ᅖᣑ኱࡟ྥࡅ࡚ࠊࣉࣛࢬ࣐୰࡟࠾ࡅࡿࢩࣜࢥࣥࢡࣛࢫࢱ࣮㸦ᗓ࡟ᖏ㟁㸧࡜࢔ࣝࢦࣥ࢖࢜ࣥ㸦ṇ࡟ᖏ㟁㸧ࡢ⾪✺㐣⛬ࢆ෌⌧ࡋࠊSi ࢡࣛࢫࢱ࣮ࡢᖏ㟁ᩘศᕸࡢண

2ࢆᐇ᪋ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛⏝࠸ࡓ㐃⥆య̿ศᏊືຊᏛࣁ࢖ࣈࣜࢵࢺἲࡣࠊ⢏Ꮚࡢ࿘ࡾ࡟༙ᚄțࡢ௬᝿⌫Ẇࢆ⪃࠼ࠊᣑᩓ᪉

⛬ᘧࢆ⏝࠸࡚࢖࢜ࣥࡢ௬᝿⌫Ẇ࡬ࡢὶධࣇࣛࢵࢡࢫࢆィ⟬ࡍࡿ㸦㐃⥆య㏆ఝ㸧ࠋ୍᪉࡛ࠊ௬᝿⌫Ẇෆ࡟࠾ࡅࡿ
࢖࢜ࣥࡢ㌶㊧ࢆ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎࡁࠊ⢏Ꮚ࡜ࡢ⾪✺ᩘ࡜ὶධᩘࡢẚ࠿ࡽ⾪✺☜⋡ࢆィ⟬ࡋࠊὶධࣇࣛࢵࢡࢫ࡜ࡢࣂࣛࣥࢫ࠿ࡽ⾪✺㏿ᗘᐃᩘࢆᚓࡿࠋᮏ◊✲࡛ࡣࠊ࠾ࡼࡑ n = 50~500 ࡢ㈇ࡢ㸯౯࠾ࡼࡧ㸰౯࡟ᖏ㟁ࡋࡓࢩࣜࢥࣥࢡࣛࢫࢱ࣮࡜࢔ࣝࢦࣥ࢖࢜ࣥࡢ⾪✺ࢆィ⟬ࡋࡓࠋࡲࡓࠊ⾪✺࡟ࡼࡿ࢚ࢿࣝࢠ࣮஺᥮ࡢண
ࢆ⾜࠸ࠊ࢔ࣝࢦࣥ࢖࢜ࣥ࡜ࡢ⾪✺࡟ࡼࡿ⢏Ꮚࡢຍ⇕࠾ࡼࡧࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࡢྍ⬟ᛶ࡟ࡘ࠸࡚ࡶ᳨ウࡋࡓࠋࡲࡓࠊMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ࠊࢩࣜࢥࣥࡢ࣏ࢸࣥࢩࣕࣝ࡜ࡋ࡚ Stillinger-Weber ࣏ࢸࣥࢩࣕࣝ
ࢆ⏝࠸࡚࠸ࡿࡀࠊィ⟬ࢆ㧗㏿໬ࡍࡿࡓࡵ㛗㊥㞳࡟࠾࠸࡚ࡣ⢏Ꮚ࡜࢖࢜ࣥ㛫࡟ാࡃ࣏ࢸࣥࢩࣕࣝࢆ⢒ど໬ࡋ࡚ィ⟬ࢆᐇ᪋ࡋࡓࠋ

3◊✲ᡂᯝ⾪✺㏿ᗘᐃᩘࡣ PEG ࡟࠾ࡅࡿィ⟬⤖ᯝ࡜ྠᵝ࡟ࠊFuchs ࡢ⌮ㄽ࡜ Gopalakrishnan ࡽࡢᘧࡢ㛫ࡢ㏿ᗘᐃᩘࢆணࡋࡓࠋࡲࡓࠊ⢏Ꮚ㸫࢖࢜ࣥ㛫࡟ാࡃᘬຊࡢࡓࡵࠊ⾪✺㏿ᗘࡣ኱ࡁ࡞್ࢆ♧ࡋࠊ㐃⥆ⓗ࡞⾪✺࡟ࡼࡾ⢏Ꮚࡀຍ⇕ࡉࢀࡿྍ⬟ᛶࢆ♧၀ࡋࡓࡀࠊࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥࢆᘬࡁ㉳ࡇࡍ࡯࡝ࡢ⾪✺ࡣほ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 36 -

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Kei Muto, Hiroki Kato, Aika Yanagimoto, Yota Uwabe, Qikun Wu, Itsuki Musha, Masaaki Komatsuda,
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Zs G h 48 44L J=?8Q2021 R""Deoxygenative Reaction for Tetraarylethanes, Tryarylmethanes, Diarylmethanes" Miki B. Kurosawa, Mizuho
Watanabe, Kei Muto, Kenta Kato, Junichiro Yamaguchi, 13th AFMC International Medicinal Chemistry
Symposium (AIMECS2021)PO-106
Online11 N 29 K12 N 2 K"Synthesis of a Novel Triazolopyridinylidene Ligand toward Inert Bond Activation" Keiichiro Iizumi, Kenta Kato,Kei Muto, Junichiro Yamaguchi, 13th AFMC International Medicinal Chemistry Symposium (AIMECS2021)PO100) Online11 N 29 K12 N 2 K
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AFMC International Medicinal Chemistry Symposium (AIMECS2021)PO-127
Online11 N 29 K12 N 2
K
"Pd-Catalyzed Tandem Ester Dance/ Decarbonylative Coupling Reactions" Masayuki Kubo, Naomi Inayama,
Eisuke Ota, Junichiro Yamaguchi, 13th AFMC International Medicinal Chemistry Symposium (AIMECS2021)PO109
Online11 N 29 K12 N 2 K
"Dechlorinative Functionalization of Alkyl Chlorides using Zirconocene and Photoredox Catalysis" Toshimasa
Okita, Keisuke Tanaka, Eisuke Ota, Junichiro Yamaguchi, 13th AFMC International Medicinal Chemistry- 38 -

Symposium (AIMECS2021)PO-105Online11 N 29 K12 N 2 K
"Development of an Asymmetric Intramolecular Buchner Reaction of alpha-Diazoesters and Synthetic Study
toward Pseudolaric Acid B" Takayuki Hoshi, Eisuke Ota, Junichiro Yamaguchi, 13th AFMC International Medicinal
Chemistry Symposium (AIMECS2021)PO-103Online11 N 29 K12 N 2 K
"Regioselective CO Bond Homolysis of Epoxides with Zirconocene-Photoredox Catalysis" Kazuhiro Aida,
Marina Hirao, Aiko Funabashi, Natsuhiko Sugimura, Eisuke Ota, Junichiro Yamaguchi, 13th AFMC International
Medicinal Chemistry Symposium (AIMECS2021)PO-98
Online11 N 29 K12 N 2 K
Chrono Chemical Biology of PHA and BML” Ami N. Saito, Tomoaki T. Takahara, Eisuke Ota, Norihito
Nakamichi, Junichiro Yamaguchi, 13th AFMC International Medicinal Chemistry Symposium (AIMECS2021)
PO-62Online11 N 29 K12 N 2 K
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Ring-Opening Fluorination of Bicyclic Azaarenes. Komatsuda Masaaki, Suto Ayane, Kondo Hiroki Jr. Takada
Hiroyuki, Kato Kenta, Saito Bunnai, Yamaguchi Junichiro* Chem. Sci. 2022, 13, 665–670.
Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis. Aida Kazuhiro,
Hirao Marina, Funabashi Aiko, Sugimura Natsuhiko, Ota Eisuke, Yamaguchi Junichiro Chem 2022, in press.
 Palladium-Catalyzed Tandem Ester Dance/Decarbonylative Coupling Reactions, Masayuki Kubo, Naomi
Inayama, Eisuke Ota, Junichiro Yamaguchi Org. Lett. 2022, accepted.

- 39 -

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓගᶵ⬟ᛶศᏊࡢ㛤Ⓨ
'HYHORSPHQWRI2SWRIXQFWLRQDO0ROHFXOHVE\7DNLQJ$GYDQWDJHRI0DLQ*URXS(OHPHQWV‫ۑ‬࿃㒓 ཭ᏹ㸦Ⲉᇛ኱Ꮫ㸧1◊✲┠ⓗᮏ◊✲࡛ࡣࠊ⌮ㄽ໬Ꮫィ⟬࡟ࡼࡗ࡚㧗ຠ⋡Ⓨග≉ᛶࡸ෇஧Ⰽᛶ࡞࡝ࡢගᶵ⬟ᛶᛶࢆᣢࡘศᏊᮦᩱ࠾ࡼࡧ᭷

ᶵࣇࢵ⣲ᶵ⬟ᛶᮦᩱࡢタィ࡜ホ౯ࢆᐇ᪋ࡍࡿࠋᮏᖺᗘࡣ᧕Ỉ࣭᧕Ἔᛶࡢ᭷ᶵࣇࢵ⣲ᮦᩱࡢタィࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ᐇ᪋ࡋࡓࠋࡲࡓࠊ᭷ᶵ࣍࢘⣲ⓎගศᏊࡢ⣔࡟ࡘ࠸࡚ࡣࠊ᭷ᶵ EL ⏝Ⓨගయࡢタィ࡜ホ౯ࠊ࠾ࡼࡧග
ゐ፹࡬ࡢᛂ⏝࡟ࡘ࠸࡚ࡢศᏊタィ࡜ホ౯ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚㐍ࡵࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
DFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬࡜ TD-DFT ィ⟬㸦࡟ࡼࡿບ㉳≧ែィ⟬ࢆ⾜ࡗࡓࠋィ⟬࡟ࡣ Gaussian 16 (Rev. C.01)

ࢆ⏝࠸ࡓࠋࡲࡓ⇕άᛶ໬㐜ᘏ⺯ග㸦TADF㸧≉ᛶࡢホ౯ࡢࡓࡵ࡟ ORCA (4.2.1)ࢆ⏝࠸ࡓ spin-orbit coupling ィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࣔࢹࣝࡢసᡂཬࡧ⤖ᯝࡢྍど໬࡟ࡣ GaussView (ver. 6.1.1)ࢆ฼⏝ࡋࡓࠋ3◊✲ᡂᯝྵ࣍࢘⣲⦰⎔ᵓ㐀ࡢࢫ࢝࢖ࣈ࣮ࣝTADF Ⓨගయࡀ᭷ᶵ EL ࡢ࣮ࣟࣝ࢜ࣇ⌧㇟ࡢᨵၿ࡟᭷ຠ࡛࠶ࡿࡇ࡜ࢆぢฟࡋࠊTD-DFT ィ⟬࡜ spin-orbit coupling ィ⟬࠿ࡽ୕㔜㡯㸫୍㔜㡯㡯㛫஺ᕪࡢຍ㏿ࡀᛶ⬟ྥୖࡢ㉳※࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓྵ࣍࢘⣲⺯ගศᏊࢆ㓟⣲㓟໬཯ᛂࡢගゐ፹࡟㐺⏝ࡋࠊࡑࡢᶵᵓࢆ㔞Ꮚ໬Ꮫィ⟬࡛᫂ࡽ࠿࡟ࡋࡓࠋࡑࡢ௚ࠊྵࣇࢵ⣲⾲㠃ฎ⌮๣ࡢタィ࡜ホ౯ࡶ⾜࠸ࠊ௨ୖࡢᡂᯝࡣ௨ୗࡢᏛ⾡ㄽᩥ➼࡛ሗ࿌ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼‫ⴥۻ‬ᒣ ⩧ኴ࣭࿃㒓 ཭ᏹ࣭⚟ඖ ༤ᇶࠊࢻࢼ࣮࣭࢔ࢡࢭࣉࢱ࣮࣭ࢻࢼ࣮ᆺࢪࢳ࢚ࣀࢳ࢔࣎ࣜࣥࡢྜᡂ࡜

ᛶ㉁ࠊ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍ࠊ2022 ᖺ 3 ᭶ 23㹼26 ᪥ࠊ࢜ࣥࣛ࢖ࣥ㛤ദ5ฟ∧ᐇ⦼‫ۻ‬T. Agou et al., Catalytic aerobic photooxidation of triarylphosphines using dibenzo-fused 1,4-azaborines, Chemical

Communications 2022, 58, 5001-5004. DOI: 10.1039/D2CC00782G.
T. Agou et al., Synthesis, Characterization, and Formation of Self-Assembled Monolayers of a Phosphonic Acid
BearingaVinylene-Bridged

Fluoroalkyl

Chain,

AppliedSurface

Science

2022,

577,

151959.

DOI:

10.1016/j.apsusc.2021.151959.
‫ۻ‬T. Agou et al., Fused-Nonacyclic Multi-Resonance Delayed Fluorescence Emitter Based on Ladder-Thiaborin
Exhibiting Narrowband Sky-Blue Emission with Accelerated Reverse Intersystem Crossing Angewandte ChemieInternational Edition 2021, 60, 20280-20285. DOI: 10.1002/anie.202108283.

- 40 -

㹂㹄㹒ィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢゎ᫂࡟ࡼࡿ㑅ᢥⓗ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ
Development of selective synthetic reactions by elucidation of reaction
mechanisms using DFT calculations‫ۑ‬ᒣᓮ ⚈Ꮚ㸦ዉⰋᩍ⫱኱Ꮫ㸧1◊✲┠ⓗ1.1 Ș-ࣈࣟࣔࢫࢳࣞࣥಟ㣭ࣇ࣐ࣝ㓟࢔࣑ࢻࡢศᏊෆ Diels-Alder ཯ᛂࢆ฼⏝ࡋࡓࢼࣇࢱࣞࣥㄏ

ᑟయࡢྜᡂࢼࣇࢱࣞࣥࡣ⏕⌮άᛶ≀㉁ࡸᶵ⬟ᛶ≀㉁࡟ከࡃぢࡽࢀࡿ᭷⏝࡞㦵᱁࡛࠶ࡿࠋα-ࣈࣟࣔࢫࢳࣞࣥ㒊ศࢆࢪ࢚ࣥᡂศ࡜ࡋ࡚฼⏝ࡋࡓศᏊෆ Diels-Alder ཯ᛂ࡛ࡢࢼࣇࢱࣞࣥㄏᑟయྜᡂࢆ᳨ウࡋࡓ (ᅗ 1)ࠋ✀ࠎࡢ⨨᥮ᇶㄏᑟయ࡟ࡘ࠸࡚ሷᇶ࡞࡝ࡢ཯ᛂ᮲௳ࢆ᳨ウࡋỗ⏝ᛶࢆㄪ࡭ࠊ཯ᛂᶵᵓࢆィ⟬⛉Ꮫࢆ⏝࠸࡚ㄝ᫂ࡋࡓࠋ
CO2Me
O
Ph

N
Br
1: Y = H, Me,OMe,
Cl, Br,I

Y Et3N(1-4
equiv) Ph
toluene110 °C

O

CO2Me

N
2
Y = H, Me,OMe,
Cl, Br (50-64%)

Cs 2CO3(Rb2CO3)
Y (1.4Ph
equiv)
toluene110 °C(55-81%)

O

CO2Me
Y

N
3

M2CO3, M = Cs, Rb, K, Y = Cl, Br, I
toluene, 110 °C (55-67%)

1.228 ÅTS7a
(M=K,Y=H)

1.389 Åᅗ 1. ศᏊෆ Diels-Alder/⬺ HBr/ࣉࣟࢺࣥ⛣ື㸫⬺Ỉ⣲1.2 ᭷ᶵⓎගᛶ≀㉁ྜᡂ◊✲࢔ࣥࢺࣛࢭࣥㄏᑟయⓎගᛶ≀㉁࡟ࡘ࠸࡚ࠊ஧㔞యࣔࢹࣝࡢບ㉳≧ែࡢࣔࢹࣝィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
GAUSSIAN 09, 16 ࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜ࡗࡓࠋ཯ᛂᶵᵓࢆ ωB97X-D/6-31G*࠾ࡼࡧ PCM ⁐፹ຠᯝࡢィ⟬࡛ㄪ࡭ࡓࠋωB97X-D /6-311+G(d,p) , SCRF = (PCM, solvent) ࡛࢚ࢿࣝࢠ࣮ΔG ࡢ㸯Ⅼィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝα-ࣈࣟࣔࢫࢳࣞࣥಟ㣭ࣇ࣐ࣝ㓟࢔࣑ࢻࢆࢺ࢚ࣝࣥ୰ 110 °C ࡛ຍ⇕ࡋࡓ࡜ࡇࢁࠊEt3N Ꮡᅾୗ࡛ 1,4-ࢪࣄࢻࣟࢼࣇࢱࣞࣥࡀᚓࡽࢀࡿࡀࠊK,Rb,Cs Ⅳ㓟ሷᏑᅾୗ࡛ࡣࠊⰾ㤶⎔ୖࡢ⨨᥮ᇶࡀࣁࣟࢤࣥࡢ࡜ࡁࠊࡉࡽ࡟⬺Ỉ⣲ࢆక࠸ࢼࣇࢱࣞࣥㄏᑟయࡀᚓࡽࢀࡓࠋ1,4-ࢪࣄࢻࣟࢼࣇࢱࣞࣥࡢ Cs2CO3(ཪࡣ Rb2CO3)࡜ࡢ 110 °C ࡛ࡢຍ⇕࡛ࡶࢼࣇࢱࣞࣥㄏᑟయࡀᚓࡽࢀࡓࠋ⬺Ỉ⣲ࡢ཯ᛂᶵᵓ࡟ࡘ࠸࡚ࠊDFT ィ⟬࡟ࡼࡾࠊ⏕ᡂࡍࡿ࢚ࣀ࣮ࣛࢺ࡜㓟⣲࡟ࡼࡿࣛࢪ࢝ࣝ཯ᛂ࡜⪃ᐹࡋࡓࠋࡑࡢ௚ࡢ཯ᛂཬࡧ᭷ᶵⓎගᛶ≀㉁ࡢⓎග࡟ࡘ࠸࡚ࡶ DFT ィ⟬࡟ࡼࡾᐇ㦂⤖ᯝࢆㄝ᫂ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼‫ ۻ‬Yamazaki, S.; Katayama, K.; Wang, Z.; Mikata, Y.; Morimoto, T.; Ogawa, A. ACS Omega 2021, 6, 28441-28454.

- 41 -

㟁Ꮚບ㉳࢖ࢯࢩ࢔ࣥ㓟ࣇ࢙ࢽࣝㄏᑟయࡢศᏊᵓ㐀
0ROHFXODU6WUXFWXUHVRI3KHQ\O,VRF\DQDWH'HULYDWLYHVዟᒣඞᙪ㸦᪥ᮏ኱ᏛᕤᏛ㒊㸧㸯 ◊✲┠ⓗ ⤖ྜ㍈࡟ᑐࡋᕥྑ㠀ᑐ⛠࡞⨨᥮ᇶࡀ࣓ࢱ఩࡟㸯ࡘࠊࡲࡓࡣࣃࣛ఩࡟㸰ࡘ࠶ࡿ࣋ࣥࢮࣥㄏ
ᑟయ࡟ࡣ cis ࡜ trans ࡢᅇ㌿␗ᛶయࡀⓎ⏕ࡍࡿࠋ࢖ࢯࢩ࢔ࣥ㓟ᇶࡶ㠀ᑐ⛠࡞⨨᥮ᇶ࡛࠶ࡿࠋࡇࡢࡼ࠺࡞ᅇ㌿␗ᛶయࡣࠊ⏕ᡂ࢚ࢿࣝࢠ࣮ࡢᕪࡀᑠࡉ࠸ࡇ࡜࠿ࡽ༢㞳ࡣ㞴ࡋࡃࠊࡲࡓࠊศᏊෆຊሙࡶᴟࡵ࡚ఝ࡚࠸ࡿࡇ࡜࠿ࡽ
ᇶᗏ≧ែ࡟࠾ࡅࡿᇶ‽᣺ືࡢ᣺ືᩘࡶ㓞ఝࡋ࡚࠸ࡿࠋᚑࡗ࡚ࠊ㏻ᖖࡢ㉥እ࣭࣐ࣛࣥศග࡛ࡣΰྜయ࡛ࡋ࠿ほࡉࢀࡎࠊศᏊศගᏛࡢ㞴㢟ࡢࡦ࡜ࡘ࡛࠶ࡗ

Table 1 Comparison of averaged deviation a)
Basis Setࡓࠋࡇࢀ࡟ග᫂ࢆྥࡅࡓࡢࡣࠊ㉸㡢㏿ศᏊὶࣞType࣮ࢨ࣮ศගἲ࡟ࡼࡿ㟁Ꮚࢫ࣌ࢡࢺࣝࡢ

Split Valenceࡿࠋᇶᗏ≧ែෆࡢ㑄⛣࡛ࡣᩘ cm-1 ࡢᕪࡋ࠿࡞࠸

ࡀྍ⬟࡟࡞ࡗࡓࠋᑐ㇟ศᏊࡀ⺯ගᛶ࡞ࡽ࢖ࢯࢩ࢔ࣥ㓟ࡸ p-ࢪ࢖ࢯࢩ࢔ࣥ㓟ࣇ࢙ࢽࣝࡣᅇ

0:08:070.299

305.890:06:21

1.247

68.12

1:10:59

0:11:100.271

288.78

0:09:26

1.255

60.75

2:04:220.279

241.23

0:03:210.270

286.690:10:24

1.255

60.91

2:11:256-311G(d)

0.133

69.90

0:09:41

0.196

93.63

0:12:43

1.450

8.37

2:09:366-311G(2d)

0.139

67.21

0:14:09

0.199

85.19

0:21:51

1.450

18.44

4:39:106-311G(d,p)

0.154

69.26

0:10:24

0.185

93.01

0:12:41

1.440

8.37

2:53:57

cc-pVDZ

0.185

93.01

0:12:41

0.189

36.29

0:11:18

1.436

51.99

1:28:45cc-pVTZ

0.152

23.31

0:07:530.179

104.24

1:25:54

1.424

28.93

21:40:18

Split Vlance+
DiffuseSplit Vlance+
Diffuse+Polarizea)ࡋࠊᅇ㌿␗ᛶయࡢ

Ꮡᅾࢆ☜ㄆࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊᑐ㇟ศᏊࡣ㠀⺯ගᛶ࡛࠶ࡾࠊࡉࡽ࡟ほConstantb) CPU time(MHz)

259.23㌿␗ᛶయࢆࡶࡘࠋᡃࠎࡣࡇࢀࡽࡢ㟁Ꮚࢫ࣌ࢡࢺ
ࣝࢆ㉸㡢㏿ศᏊὶ࡟ࡼࡾほConstantb) CPU time(MHz)

Rotational

242.61࡛ࡁࡿࠋ ࢖ࢯࢩ࢔ࣥ㓟ࣇ࢙ࢽࣝㄏᑟయ࡛࠶ࡿ m-ࢺࣜࣝ

CPU time

MP2
Relative
MO
Energy(eV)Rotational

0.500ࡤࠊ༢୍᣺㟁‽఩⺯ගศගἲࢆ㐺ᛂྍ⬟࡛ࠊᇶᗏ≧ែࡢ᣺ືᩘࡣูࠎ࡟ほb)Constant(MHz)

Relative
MO
Energy(eV)

0.294᣺ືᩘࡀࠊ㟁Ꮚ㑄⛣࡛ࡣⓒᩘ༑ cm ࡟࡞ࡾࠊᓧ

6-311G

CAM-B3LYP

Rotational

Split Valence 6-311+G
Polarize
6-311++G-1

ูほFunction

ᐃ࡛࠶

B3LYP
Relative
MO
Energy(eV)

cc-pVQZ

0.173

84.06

0:53:200.177

105.10

17:13:34

1.420

37.46 15:21:47:34

6-311+G(d)

0.142

68.17

0:13:33

0.184

93.26

0:19:06

1.455

16.12

6-311+G(2d)

0.142

68.26

0:22:21

0.187

87.71

0:31:50

1.448

20.08

4:58:01

6-311+G(d,p)

0.161

67.35

0:17:43

0.174

92.50

0:23:56

1.444

17.89

4:58:01

6-311++G(d)

0.145

68.17

0:13:33

0.184

93.35

0:19:03

1.455

16.23

4:23:156-311++G(2d)

0.142

68.41

0:23:50

0.187

87.86

0:33:57

1.440

57.24

6:32:16

6-311++G(d,p)

0.161

67.45

0:19:28

0.174

92.66

0:21:19

1.448

20.66

8:40:53

aug-cc-pVDZ

0.170

26.39

0:26:33

0.172

42.58

0:36:04

1.440

57.24

6:32:16

aug-cc-pVTZ

0.180

85.38

5:32:020.174

106.58

9:49:30

1.418

26.65

7:15:20

aug-cc-pVQZ

0.178

84.36

3:21:31:00

0.175

105.15

5:05:39:06

4:06:10

Average of deviation was calculated the follow equation.
൫௖௔௟௖Ǥሺ௜ሻି௢௕௦Ǥሺ௜ሻ൯           ൌ ටσ௡௜ୀଵb)
Rotational constant consists of A, B, and C.

௡

మ



ࡉࢀࡓ᣺㟁‽఩ࡣᖜᗈ࡛࣮ࣞࢨ࣮ศᏊศගἲࡔࡅ࡛ࡣࠊ㟁Ꮚ≧ែࡢᖐᒓࡍࡽᐜ࡛᫆࡞࠸ࠋࡑࡇ࡛ࠊᙜࢭࣥࢱ࣮ࡢ኱ᆺィ⟬ᶵ࡟ࡼࡿ኱ᐜ㔞ࡢ㔞Ꮚ໬Ꮫィ⟬ࢆ⾜࠸ࠊ᭱⤊ⓗ࡟ࡣᅇ㌿␗ᛶయࡢศගᏛⓗᖐᒓࢆ᏶⤖ࡉࡏࡓ࠸࡜⪃࠼࡚࠸ࡿࠋ◊✲ࢆ㐍ࡵࡿ࡟ᙜࡓࡾࠊ㛗ᔱ㞼රẶࡼࡾࠊࠕࡲࡎࡣぶศᏊ࢖ࢯࢩ࢔ࣥ㓟ࣇ࢙ࢽࣝࡢᇶᗏ≧ែࢆ☜ᐃࡉࡏࢁࠖ࡜ࡢຓ
ゝࢆ㡬࠸ࡓࠋ㟁Ꮚ㑄⛣࡟࠾ࡅࡿᅇ㌿␗ᛶయࢆᖐᒓࡍࡿࡓࡵ࡟ࡣࠊศᏊᵓ㐀ࡢࡳ࡞ࡽࡎศᏊ㌶㐨ࢆⓗ☜࡟⾲⌧࡛ࡁࡿィ⟬᪉ἲ࡜ᇶᗏ㛵ᩘࢆ≉ᐃࡏࡡࡤ࡞ࡽ࡞࠸ࠋᮏᖺᗘࡣࡇࢀࢆ◊✲┠ⓗ࡜ࡋࡓࠋ㸰 ィ⟬᪉ἲ  ィ⟬᪉ἲࡣ Gaussian09 ࣃࢣ࣮ࢪࡢ B3LYPࠊCAM-B3LYPࠊMP2ࠊᇶᗏ㛵ᩘࡣ Split
valence ࠿ࡽ Diffuse 㛵ᩘ࠾ࡼࡧ Polarize 㛵ᩘࢆຍ࠼ࡓ 18 ✀㢮࡛࠶ࡿࠋ⤌ࡳྜࢃࡏࡣ 53 ㏻ࡾ࡟࡞ࡿࠋ㸱 ◊✲ᡂᯝ ග㟁Ꮚศගἲ [1] ほ ࡉࢀࡓ㸴ࡘࡢ⿕༨᭷㌶㐨࢚ࢿࣝࢠ್࣮࡜࣐࢖ࢡࣟἼศගἲ [2] ࡛ᚓࡽࢀࡓ㸱ࡘࡢᅇ㌿ᐃᩘࢆཧ↷ᐇ㦂್࡜ࡋࠊᕪࡢ⮬஌࿴ࢆᩘ್ᩘ࡛๭ࡾᖹ᪉᰿ࢆホ౯್࡜ࡋࡓࠋࡍ࡞ࢃࡕࠊ
ࡇࢀࡣᖹᆒ໬ࡉࢀࡓࡎࢀ್㸦averaged deviation㸧࡛࠶ࡾࠊ༢఩ࢆࡶࡘࠋࡑࡢ⤖ᯝࠊ⾲ࡢ୰࡟ኴᏐ࡛⾲ࡋࡓࠊ
B3LYP ἲࢆ⏝࠸࡚ࠊᇶᗏ㛵ᩘࡣ cc-pvTZ ࡜ aug-cc-pVDZ ࡀ᭱ࡶⰋ࠸⤖ᯝࢆ୚࠼ࡓࠋ

㸲 Ⓨ⾲ᐇ⦼ ‫  ۻ‬㛗἟ࠊ▼ᶫࠊዟᒣࠊศᏊ⛉Ꮫウㄽ఍ 2021㸦ᮐᖠ㸧2A012 ୍⯡ཱྀ₇ࠋ‫  ۻ‬ዟᒣࠊ௧࿴㸱ᖺᗘ໬Ꮫ⣔ᮾ໭኱఍㸦᪥ᮏ໬Ꮫ఍୺ദ㸧㸦㒆ᒣ㸧౫㢗බ₇ 3A3ࠋ‫   ۻ‬㛗἟ࠊ▼ᶫࠊዟᒣࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ⛅Ꮨᖺ఍ࠊ୍⯡ཱྀ₇ 2O02ࠋ㸳 ฟ∧ᐇ⦼ ‫ۻ‬Y. Naganuma, D. Ishibashi, K. Okuyama, J. Comput. Chem. Jpn. , 20(4), 129-131 (2021).
ཧ⪃ᩥ⊩[1] T. Kobayashi, S. Nagakura, J. Electron Spectrosc., 7 (1975) 488-491.
[2] S. Wenhao, et al., J.Phys. Chem. A, 123, (2019) 2351-2360.

- 42 -᪂ つᶵ⬟ᛶ᭷ᶵⰍ⣲ࡢ㛤Ⓨ
Development of new functional organic dyesż⯪᭥ ୍ṇ㸦ᒱ㜧኱ᏛᕤᏛ㒊㸧1◊✲┠ⓗࠊෆᐜ
ᡃࠎࡢ◊✲ᐊ࡛ࡣࠊᵝࠎ࡞᪂つᶵ⬟ᛶ᭷ᶵⰍ⣲ࡢྜᡂࢆ⾜࠸ࠊྛ✀≀ᛶࢆホ౯ࡋ࡚࠸ࡿࠋࡑࡢⰍ⣲ࡣࠊගᏛࣇ࢕ࣝࢱ࣮ࠊኴ㝧㟁ụࠊ᭷ᶵ ELࠊ໬Ꮫࣉ࣮ࣟࣈ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࡿࡶࡢ࡞࡝ከᒱ࡟ࢃࡓࡿࠋᮏ◊✲ࡢ┠ⓗࡣࠊࡑࡢⰍ⣲ศᏊࡢ⏝㏵࡟ྜࢃࡏࠊタィẁ㝵࡛ࡢ≀ᛶࡢணࠊ࠶ࡿ࠸ࡣྜᡂࡋࡓⰍ⣲ࡀ♧ࡋࡓ≀ᛶ࡟ᑐࡋ࡚⪃ᐹࢆ⾜࠺ࡓࡵ࡟ࠊศᏊ㌶㐨ィ⟬࡟ࡼࡾ⟬ฟࡋࡓ㌶㐨ࡢ࢚ࢿࣝࢠ࣮‽఩ࡸ㟁Ꮚศᕸ➼ࢆά⏝ࡋࠊࡇࢀࡲ࡛
ࡢ≉ᛶࢆ㠉᪂ࡉࡏࡿ᭷ᶵⰍ⣲ࢆ㛤Ⓨࡍࡿࡇ࡜࡛࠶ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࡣࡍ࡭࡚ Gaussian 16 ࢆ౑⏝ࡋ࡚⾜ࡗࡓࠋB3LYP/6-31G(d,p)ࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜࠸ࠊࣇࣟࣥࢸ࢕࢔㌶

㐨ࡢ࢚ࢿࣝࢠ࣮‽఩ࠊ㟁Ꮚศᕸࢆ⟬ฟࡋࠊⰍ⣲ศᏊࡀ♧ࡍගᏛ≉ᛶࡢணࠊᚓࡽࢀࡓ⤖ᯝ࡟ᑐࡍࡿ⪃ᐹࢆ⾜

ࡗࡓࠋ

3

◊✲ᡂᯝ
ᶵ⬟ᛶⰍ⣲ࡢ୍✀࡛࠶ࡿ࢔ࢽ࢜ࣥᛶ࣊ࣉࢱ࣓ࢳࣥࢩ࢔ࢽࣥⰍ⣲ࡢศᏊ㦵᱁୰࡟ࣇࢵ⣲⨨᥮ᇶࢆᑟධࡍࡿࡇ

࡜࡟ࡼࡗ࡚ගᏳᐃᛶࢆ኱ࡁࡃྥୖࡉࡏࡓࠋࢩ࢔ࢽࣥⰍ⣲ࡢගศゎᶵᵓࡣࠊ୍⯡ⓗ࡟ගບ㉳ࡋࡓⰍ⣲ศᏊ࡜ࡢ࢚ࢿࣝࢠ࣮஺᥮࡟ࡼࡗ࡚⏕ᡂࡍࡿ୍㔜㡯㓟⣲ࡢồ㟁Ꮚ௜ຍ࡟ࡼࡗ࡚ศゎࡍࡿ࡜ሗ࿌ࡉࢀ࡚࠸ࡿࠋᡃࠎࡣࠊⰍ
⣲ࡢගศゎ≀ࢆ㧗ศゎ⬟࣐ࢫࢫ࣌ࢡࢺ࡛ࣝ

ᐃࡍࡿࡇ࡜࡟ࡼࡾࠊ㛤Ⓨࡋࡓ࢔ࢽ࢜ࣥᛶ࣊ࣉࢱ࣓ࢳࣥࢩ࢔ࢽࣥ

Ⰽ⣲ࡶྠᵝࡢᶵᵓ࡛ศゎࡍࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋࡓࠋ')7 ィ⟬ࡢ⤖ᯝࡣࠊィ⏬ࠊᐇ᪋ࡋࡓࢩ࢔ࢽࣥⰍ⣲࡬ࡢࣇࢵ⣲⨨᥮ᇶࡢᑟධࡀࠊⰍ⣲ࡢ㌶㐨ࡢ࢚ࢿࣝࢠ࣮‽఩ࢆᏳᐃ໬ࡋࠊ୍㔜㡯㓟⣲ࡢ⏕ᡂ࠾ࡼࡧ௜ຍࢆ኱ࡁࡃᢚไࡍ
ࡿࡇ࡜࡟ࡼࡾࠊ࢝ࢳ࢜ࣥᛶ࣊ࣉࢱ࣓ࢳࣥࢩ࢔ࢽࣥⰍ⣲࡜ྠᵝ࡟࢔ࢽ࢜ࣥᛶ࣊ࣉࢱ࣓ࢳࣥࢩ࢔ࢽࣥⰍ⣲ࡢ⪏ගᛶࢆ኱ࡁࡃྥୖࡉࡏࡓࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃմ ᒣᮏ, ❑⏣, ≟ሯ, ⯪᭥, ࠕ㏆㉥እ㡿ᇦ࡟྾཰ࢆᣢࡘࣉࢵࢩࣗ-ࣉࣝᆺⰍ⣲ࡢ㛤Ⓨࠖ 2021 ᖺᗘⰍᮦ◊✲Ⓨ⾲఍ (࢜ࣥࣛ࢖ࣥ㛤ദ), 㸦P12㸧,㸦2021, 9/17)㸦࣏ࢫࢱ࣮Ⓨ⾲㸧

5. ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

մ ࠕ Synthesis of

1-Trifluoromethylated

Propargyl Alcohols by Two

Successive

Reactions of

Cyclopentylmagnesium Bromide in a One-Pot MannerࠖR. Kani, T. Inuzuka, Y. Kubota, K. Funabiki*, Asian J.
Org. Chem. No. 2, e202100700 (2022)2.

ࠕPhotostability and Halochromic Properties of Near-Infrared Absorbing Anionic Heptamethine Cyanine Dyes ࠖ
Y. Arisawa, Y. Kubota, T. Inuzuka, K. Funabiki*, ChemistrySelect, No. 5, e20210421 (2022)- 43 -

࣐࢖ࢡࣟࣇ࣮ࣟ཯ᛂሙࢆ⏝࠸࡚๰〇ࡉࢀࡿ‽Ᏻᐃ㉸ศᏊᵓ㐀ࡢゎᯒCalculation of metastable supramolecular structures createdin a microflow field‫ۑ‬἟⏣ ᐀඾㸦ி㒔ᗓ❧኱Ꮫ㸧

1

◊✲┠ⓗ㸸
ᙜ◊✲ᐊ࡛ࡣ࣐࢖ࢡࣟࣇ࣮ࣟ✵㛫ෆࡢືⓗ࡞⁐ᾮࢆ཯ᛂሙ࡜ࡋࡓ⊂⮬ࡢศᏊ㞟✚ࢩࢫࢸ࣒ࡢ㛤Ⓨࢆ⾜࡞ࡗ࡚࠸ࡿࠋᮏ⏦ㄳ࡛ࡣࠊ*DXVVLDQ ࡟ࡼࡿ ')7 ィ⟬ࢆᐇ᪋ࡋࠊ๰〇ࡋࡓ㉸ศᏊᵓ㐀ࡢᏳᐃ໬࢚ࢿࣝࢠ࣮ࡸࢫ࣌ࢡࢺࣝࡢ᥎ᐃࠊศᏊ఍ྜࡢ㝿ࡢ㑄⛣≧ែࡢண ࡞࡝ࢆᐇ᪋ࡋࡓ࠸ࠋ࣐࢖ࢡࣟ✵㛫ෆ࡛๰〇ࡍࡿ㉸ศᏊᵓ㐀ࡣࠊ୍᫬ⓗ㸦‽Ᏻᐃ㸧࡞ᵓ㐀ࡀከࡃྵࡲࢀࡿࠋᐇ㦂ⓗ࡞ᵓ㐀ỴᐃࡸศගᏛⓗ࡞ ᐃࡀᅔ㞴࡜࡞ࡿሙྜࡀከ࠸ࠋィ⟬࡟ࡼࡾồࡵࡽࢀࡓ㉸ศᏊᵓ㐀ࡢ࢚ࢿࣝࢠ್࣮ࡸࢫ࣌ࢡࢺࣝ࡜ࡇࢀࡲ࡛⵳✚ࡉࢀࡓᐇ㦂ࢹ࣮ࢱ࡜ࡢ┦㛵㛵ಀࢆ᫂ࡽ࠿࡜ࡋࡓ࠸ࠋ㠀ᖹ⾮⣔࡟࠾࠸࡚ศᏊ㛫ຊࡀ࡝ࡢࡼ࠺࡟ㄏ
Ⓨࡉࢀ≉Ṧ࡞㞟✚ᵓ㐀࡟⤖ࡧࡘࡃࡢ࠿ࢆゎ᫂ࡍࡿࡇ࡜ࡀ᭱⤊┠ᶆ࡛࠶ࡿࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ㸸ᮏㄢ㢟࡟࠾࠸࡚ࡣࠊ*DXVVLDQ ࢆ⏝࠸࡚ᵝࠎ࡞ศᏊ㞟✚ᵓ㐀ࢆࢱ࣮ࢤࢵࢺ࡜ࡋ࡚ %/<3* ࣞ
࣋ࣝࡢ ')7 ィ⟬ࢆᐇ᪋ࡋࡓࠋ ᖺᗘࡣ✀ࠎࡢȧඹᙺ⣔ศᏊࡢ୰࡛ࡶ≉࡟ࠊ ḟඖ㞟✚ᵓ㐀㸦㉸ศᏊ࣏࣐࣮ࣜ㸧ࢆసࡾฟࡍ࣌ࣜࣞࣥࣅࢫ࢖࣑ࢻㄏᑟయ࡟
ࡘ࠸࡚ࠊ㸰㔞యᵓ㐀ࡢᏳᐃ໬࢚ࢿࣝࢠ࣮ࢆศᩓຊ⿵
ṇ࡜ %66( ࢆ⪃៖ࡋ࡚ホ౯ࡋࡓ㸦ᅗ㸯㸧ࠋࡇࢀࡽࡢ㸰
㔞యᵓ㐀ࡣ㉸ศᏊ࣏࣐࣮ࣜᵓ㐀ࡢᇶᮏⓗ࡞⧞ࡾ㏉ᅗ㸯㸸')7 ィ⟬࡟ࡼࡗ࡚ồࡵࡓ࣌ࣜࣞ
ࣥࣅࢫ࢖࣑ࢻㄏᑟయࡢ㸰㔞యࡢᵓ㐀ࡋ༢఩࡛࠶ࡾࠊࡇࡢ࢚ࢿࣝࢠ࣮ࡀศᏊ㞟ྜయ඲యࡢ 㸦%/<3* 㸧࢚ࢿࣝࢠ࣮࡜┦㛵ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋᐇ㝿࡟ࠊ࠸ࡃࡘ࠿ࡢศᏊ࡟ࡘ࠸࡚ࠊィ⟬࡟ࡼࡾồࡵࡓᏳᐃ໬࢚ࢿࣝࢠ࣮ࡣࠊࡇࢀࡲ࡛ᐇ㦂ⓗ࡟ホ౯ࡋ࡚ࡁࡓ㉸ศᏊᵓ㐀ࡢᏳᐃᛶࡢᗎิ࡜ࡼࡃ┦㛵ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᮏᡂᯝࡣࠊ࣐
࢖ࢡࣟࣇ࣮ࣟ✵㛫࡟࠾ࡅࡿศᏊࡢ᣺ࡿ⯙࠸ࢆ⌮ゎࡍࡿୖ࡛㔜せ࡞▱ぢ࡜࡞ࡗࡓࠋ ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Matoba, S.; Kanzaki, C.; Yamashita, K.; Kusukawa, T.; Fukuhara, G.; Okada, T.; Narushima, T.;Okamoto, H.; Numata, M. Directional Supramolecular Polymerization in a Dynamic Microsolution:
A Linearly Moving Polymer’s End Striking Monomers, J. Am. Chem. Soc., 2021, 143, 8731-8746.

- 44 -

ศᏊ⣔࡟࠾ࡅࡿග࣭≀㉁┦஫స⏝ࡢ⌮ㄽ◊✲
Theoretical Studies of Light-Matter Interactions in Molecular Systems‫ۑ‬Nguyen Thanh Phuc㸦ி㒔኱Ꮫ㸧1◊✲┠ⓗThis research project aims to study the physical and chemical properties of molecular systems in the presence ofstrong/ultrastrong coupling between molecules and light.

2◊✲᪉ἲࠊィ⟬᪉ἲThe quantum dynamics and two-dimensional spectroscopy were calculated based on the model Hamiltonian.

3◊✲ᡂᯝI have shown that a superreaction with the collective enhancement of the reaction rate can be realized in molecularpolaritonic systems, and that quantum many-body interactions can be directly probed by the coherent 2D spectroscopy.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬N. T. Phuc, Molecular polariton: from chemical reactivity control to superreactionࠊ➨ 23 ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠋ‫ۻ‬N. T. Phuc, ศᏊ࣏ࣛࣜࢺࣥ㸸໬Ꮫ཯ᛂࡢไᚚ࠿ࡽࢫ࣮ࣃ࣮཯ᛂࡲ࡛, ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2021 ᖺ.
‫ۻ‬N. T. Phuc, Superreaction: the collective enhancement of a reaction rate by molecular polaritons in the presence ofenergy fluctuations, ᪥ᮏ≀⌮Ꮫ఍ 2021 ᖺ⛅Ꮨ኱఍.
‫ۻ‬N. T. Phuc, Controlling exciton and charge quantum dynamics in condensed-phase molecular systems: from
Floquet engineering to molecular polariton, Pacifichem 2021㸦ᣍᚅㅮ₇㸧.
‫ۻ‬N. T. PhucࠊศᏊ࣏ࣛࣜࢺࣥ㸸໬Ꮫ཯ᛂࡢไᚚ࠿ࡽࢫ࣮ࣃ࣮཯ᛂࡲ࡛ࠊ⌮ㄽ໬Ꮫ఍ㄅࣇࣟࣥࢸ࢕࢔࡟㛵㐃ࡋࡓࢩ࣏ࣥࢪ࣒࢘㸦ᣍᚅㅮ₇㸧ࠊ2021 ᖺ.
‫ۻ‬N. T. Phuc, Bose enhancement of excitation energy transfer with molecular-exciton polariton condensates, ᪥ᮏ≀⌮Ꮫ఍➨ 77 ᅇᖺḟ኱఍ࠊ2022 ᖺ.
‫ۻ‬N. T. Phuc, Superreaction: the collective enhancement of a reaction rate by molecular polaritons in the presence ofenergy fluctuationsࠊ᪥ᮏ໬Ꮫ఍➨ 102 ᫓Ꮨᖺ఍ࠊ2022 ᖺࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬N. T. Phuc and P. Q. Trung, Direct and ultrafast probing of quantum many-body interaction through coherent

two-dimensional spectroscopy: From weak- to strong-interaction regimes, Phys. Rev. B 104, 115105 (2021).
‫ۻ‬N. T. Phuc, Super-reaction: The collective enhancement of a reaction rate by molecular polaritons in the presenceof energy fluctuations, J. Chem. Phys. 155 014308 (2021).
(selected for JCP 2021 JCP Emerging Investigators Special Collection)- 45 -

㠀⮬᫂࡞ࢫࣆࣥ≧ែࢆ⤒⏤ࡍࡿ㑄⛣㔠ᒓゐ፹཯ᛂࡢィ⟬໬Ꮫⓗᶵᵓゎᯒ
7KHRUHWLFDOLQYHVWLJDWLRQRIRUJDQRPHWDOOLFUHDFWLRQVLQYROYLQJQRQREYLRXVVSLQVWDWHV‫ۑ‬ᑠᓥ ṇᐶࠊྜྷ㔝 㐩ᙪࠊ෠⏣ Ọᕼࠊ⚄ᒣ 㣁リࠊຍ⸨ ె⨾㸦໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⸆
Ꮫ◊✲㝔㸧
1

◊✲┠ⓗ
➨୍ิ㑄⛣㔠ᒓࡣᣢ⥆ྍ⬟࡞㈨※࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ୍᪉ࠊࡇࢀࡽࡢ㔠ᒓࢆゐ፹࡜ࡍࡿኚ᥮ࡣ୰㛫యࡢ୙Ᏻᐃᛶࠊ࠾ࡼࡧࢫࣆࣥ≧ែࡢ୙☜ᐃᛶࡺ࠼࡟཯ᛂᶵᵓ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡇ࡜ࡀ㞴ࡋ࠸ࠋᡃࠎࡣᐇ㦂໬Ꮫ࡜⌮ㄽ໬Ꮫࡢ୧㠃࠿ࡽࠊ➨୍ิ㑄⛣㔠ᒓࢆ⏝࠸ࡓ᪂つ཯ᛂࡢ㛤Ⓨ࡜཯ᛂᶵᵓゎ᫂࡟ྲྀࡾ⤌ࢇࡔࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᡃࠎࡢࢢ࣮ࣝࣉ࡛Ⓨぢࡋࡓࢥࣂࣝࢺࢆゐ፹࡜ࡍࡿኚ᥮࡟ࡘ࠸࡚ࠊ᝿ᐃ཯ᛂᶵᵓࡢጇᙜᛶࢆ㔞Ꮚ໬Ꮫィ⟬࡟᳨࡚ドࡋࡓࠋGRRM17 ࡢ stable=opt ࢜ࣉࢩࣙࣥࢆά⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊἼື㛵ᩘࡢᏳᐃᛶࢆᢸಖࡋࡓ≧ែ࡟࡚ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊ໬Ꮫ✀ࡢࢫࣆࣥ≧ែࡢ⢭☜࡞ぢ✚ࡶࡾࢆヨࡳࡓࠋ3◊✲ᡂᯝࢥࣂࣝࢺゐ፹ࢆ⏝࠸ࡓỈ⣲ཎᏊ⛣ືᆺ཯ᛂ࡟ࡘ࠸࡚ࠊ཯ᛂᶵᵓࡢ඲ᐜࢆ DFT ࡛ゎ᫂ࡍࡿࡇ࡜࡟ᡂຌࡋࠊࣛ

ࢪ࢝ࣝⓗ࡟㐍⾜ࡍࡿ཯ᛂࢹࢨ࢖ࣥࡢጇᙜᛶࢆᨭᣢࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋࡇࡢᡂᯝ࡟ࡘ࠸࡚ࡣ㸰௳ࡢᏛ఍Ⓨ⾲࡜㸯௳ࡢㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋࡲࡓࢥࣂࣝࢺゐ፹࡜Ⅳ⣲ࣛࢪ࢝ࣝࢆ⏝࠸ࡓ࢔ࣜࣝ఩⨨᥮཯ᛂ࡟ࡘ࠸࡚ࡶ DFT ࡟ࡼࡿ཯ᛂᶵᵓゎᯒࢆ⾜࠸ࠊ཯ᛂ㐍⾜᫬ࡢࢥࣂࣝࢺࡢࢫࣆࣥ≧ែࡀ triplet ࡛࠶ࡿ࡜ࡢ⯆࿡῝࠸▱ぢࡀᚓࡽࢀࡓࠋ
ࡇࡢᡂᯝ࡟ࡘ࠸࡚ࡣ㸯௳ࡢㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ࠕۻ‬ග㓟໬㑏ඖゐ፹/ࢥࣂࣝࢺゐ፹ࡢ༠ാ࡟ࡼࡿ⎔ቃㄪ࿴ᆺศᏊෆ HAT ࣄࢻࣟ࢔࣮ࣜࣝ໬཯ᛂ(1P-40)ࠖ
ࠐᒣཱྀඃ෤ 1ࠊட஭ᐋ἞ 1ࠊΎ㔝భ௓ 2ࠊ㕥ᮌᬗᙪ 2ࠊྜྷ㔝㐩ᙪ 1ࠊᑠᓥṇᐶ 1ࠊᯇỌⱱᶞ 1,3 㸦1 ໭኱㝔⸆ࠊ

2 ໭኱⸆ࠊ3GI-CoRE㸧➨ 47 ᅇ཯ᛂ࡜ྜᡂࡢ㐍Ṍࢩ࣏ࣥࢪ࣒࢘ 2021 ᖺ 10 ᭶ ࢜ࣥࣛ࢖ࣥ㛤ദ ࣏ࢫࢱ࣮Ⓨ⾲‫“ۻ‬Hydrogen atom transfer hydrofunctionalization of alkenes using ascorbic acid and cobalt-photoredox dual catalysis”
ࠐMasahiro Kojima1 (1Hokkaido University, Faculty of Pharmaceutical Sciences)
2nd GSD/GI-CoRE international symposium 27th Pharmascience Forum 2022 ᖺ 3 ᭶ ࢜ࣥࣛ࢖ࣥ㛤ദ ཱྀ㢌Ⓨ⾲5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫“ۻ‬Regioselective Deaminative Allylation of Aliphatic Amines via Dual Cobalt and Organophotoredox Catalysis”
T. Sekino, S. Sato, T. Yoshino, M. Kojima, S. Matsunaga Org. Lett. 2022, 24, 2120-2124.
‫“ۻ‬Intramolecular Hydrogen Atom Transfer Hydroarylation of Alkenes toward δ-Lactams Using Cobalt-Photoredox

Dual Catalysis”
Y. Yamaguchi, Y. Seino, A. Suzuki, Y. Kamei, T. Yoshino, M. Kojima, S. Matsunaga Org. Lett. 2022, 24, 2441-2445.

- 46 -

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Study for molecular orientation of functional groups in supramolecular
nano-structures of glutamide derivatives
+ 7?/)@ 5843
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1. M. Ito, Y. Kuwahara, N. Ryu, T. Mani, H. Ihara, M. Takafuji, Chiroptical properties and their stability forsupramolecular assemblies of viologen-modified glutamide derivatives and their reduced derivatives, The 2020
International Chemical Congress of Pacific Basin Societies (Pacifichem 2020), Online, Dec. 2021.
2. U´Ø, f¨, UfeÕ, Þ¼Ä, ß£o, ©*c, ;ILJÃ{WÉ_s®²c%(]Z\·¡ÒcÅ[,  59 OctÔÃuÐjK(aT., `, 2022 b 7 |Ñ)wÒ

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Y. Kuwahara, M. Ito, T. Iwamoto, M. Takafuji, H. Ihara, N. Ryu, T. Mani, RSC Advances, 12, 4, 2019-2025, 2022.
Sn)w 1 -- 47 -

ゐ፹ⓗ㦵᱁㌿఩཯ᛂࡢ཯ᛂᶵᵓゎᯒMechanistic studies on catalytic rearrangement reactions‫ۑ‬୰ᮧ 㐩㸦ᮾ໭኱㝔⌮㸧1◊✲┠ⓗᡃࠎࡣ࢜ࣝࢺ఩࡟㟁Ꮚ౪୚ᛶ⨨᥮ᇶࢆ᭷ࡍࡿ N-࢔ࣝࢥ࢟ࢩ࢔ࢽࣜࣥ࡟ᑐࡍࡿ㖡ゐ፹ࢆస⏝ࡉࡏࡿࡇ࡜࡟ࡼ

ࡾ[1,3]-࢔ࣝࢥ࢟ࢩ㌿఩ࢆ⤒࡚࢜ࣝࢺ-࢟ࣀ࣮ࣝ࢖࣑ࣥ୰㛫య 1 ࡀຠ⋡ⓗ࡟Ⓨ⏕ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡉࡽ࡟ࠊ
ࢫࢳࣞࣥ࡜ࡢ࢝ࢫࢣ࣮ࢻᆺゐ፹ⓗ[1,3]-㌿఩̿Diels-Alder ཯ᛂࡀ఩⨨㑅ᢥⓗ࠿ࡘ❧య㑅ᢥⓗ࡟㐍⾜ࡍࡿࡇ࡜ࢆᐇ㦂ⓗ࡟᫂ࡽ࠿࡟ࡋࡓࠋࡑࡇ࡛ᮏ◊✲࡟࠾࠸࡚ࠊࡇࡢ㘽୰㛫య࡟࠾ࡅࡿ㑅ᢥᛶࡢⓎ⌧ᶵᵓࢆィ⟬⛉Ꮫⓗᡭἲ࡟ࡼࡾゎᯒࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 ࢆ౑⏝ࡋࠊB3LYP/6-31G+(d,p)࡛ࡢ DFT ィ⟬࡟ࡼࡾᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝortho-Quinol imine 1 ࡬ࡢ௜ຍ⏕ᡂ≀ࢆ୚࠼ࡿ㑄⛣≧ែ TSA ࡀࡑࡢ఩⨨␗ᛶయࢆ୚࠼ࡿ㑄⛣≧ែ TSB ࡼࡾ

5.1 kcal/mol Ᏻᐃ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢ㑄⛣≧ែ TSA ࡣ㠀ྠᮇⓗ࡛࠶ࡾࠊ㖡ゐ፹࡟ࡼࡾຍ㏿ࡉࢀࡿᐇ㦂⤖ᯝ࡜୍⮴ࡍࡿࠋ௚᪉ࠊ㑄⛣≧ែ TSB ࡛ࡣࢫࢳࣞࣥࡢࣇ࢙ࢽࣝᇶ࡜࢔ࣝࢣࣥ㒊఩࡜ࡢඹᖹ㠃ᛶࡀࠊ཯ᛂᗑ
ࡢ㏆᥋࡟ࡼࡿ❧యⓗᙳ㡪ࡢࡓࡵపୗࡍࡿࠋ௒ᚋ[1,3]-࢔ࣝࢥ࢟ࢩ㌿఩㐣⛬ࡢヲ⣽࡞᳨ウࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ
O
N

O
Ph

Me

from MeO side
endo
N

OMe
Me

+

OMe
2.89 Å

1.97 Å Ph
TS1(''G = 0.0 kcal/mol)

Ph

O
N

Ph
Me

Ph
single regioisomerOortho-quinol imine 1

O

N

Me
B3LYP/6-31G+(d,p)

Ar
OMe
2.24 Å

N
Me

2.24 Å

Ph
TS2(''G = 5.1 kcal/mol)

4

Ph

OMe

Ph

OMe
Ph
not obtainedⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ୰ᮧ 㐩ࠊRecent Progress on Catalytic Skeletal Rearrangement Reactions for Heterocyclic Synthesisࠊ௧࿴ 3 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍᭷ᶵ໬Ꮫࢥ࣒ࣟ࢟࢘ࠊ2021 ᖺ 10 ᭶ 2~3 ᪥࢜ࣥࣛ࢖ࣥ㛤ദ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
I. Nakamura, K. Masukawa, Y. Ishida, M. Terada, Org. Lett. 2021, 23, 4127

- 48 -

ȧ㟁Ꮚ⣔㓄఩Ꮚࢆ㘽࡜ࡍࡿ㛤Ẇᛶ඾ᆺඖ⣲㘒యࡢ㛤Ⓨ'HYHORSPHQWRI1RYHO2SHQ6KHOO0DLQ*URXS&RPSOH[HV%DVHGRQS(OHFWURQLF/LJDQGV‫ۑ‬ඤ⋢ᣅஓ㸦኱㜰኱Ꮫ㸧◊✲┠ⓗᡃࠎࡣࠊ⇕ຊᏛⓗ࡟Ᏻᐃ࡞㛤Ẇ S 㟁Ꮚ⣔㓄఩Ꮚ࡛࠶ࡿࣇ࢙ࢼࣞࢽࣝ(PLY)ᆺ

㓄఩Ꮚ࡟╔┠ࡋࡓ㛤Ẇ඾ᆺඖ⣲㘒య[Ar(N,N)-PLY]E:ࡢ㛤Ⓨ࡟ྲྀࡾ⤌ࢇ࡛࠸ࡿࠋ
ᮏ◊✲࡛ࡣ᭱㏆ྜᡂࢆ㐩ᡂࡋࡓ㛤Ẇ 2 ౯ࢤ࣐ࣝࢽ࣒࢘✀[Dipp(N,N)-PLY]Ge:࡟㛵ࡋ࡚ィ⟬⛉Ꮫᡭἲࢆ⏝࠸࡚ࡢ㟁Ꮚᵓ㐀ࢆゎ᫂ࡋࠊᐇ㦂⤖ᯝ࡜ేࡏ࡚ࡑࡢᥥീࢆ
᫂ࡽ࠿࡟ࡍࡿࠋ

ᅗ >'LSS 11 3/<@*H:◊✲᪉ἲࠊィ⟬᪉ἲ

[Dipp(N,N)-PLY]Ge:ࡢᇶᗏ≧ែࡢศᏊᵓ㐀࡜㟁Ꮚ≧ែ࡟㛵ࡋ࡚ࠊGaussian 09 ࢆ౑⏝ࡋ DFT ィ⟬࡟ࡼࡿホ౯ࢆ⾜ࡗࡓࠋィ⟬ࡣ UM06-2X/6-31G(d,p)࡛ࣞ࣋ࣝᐇ᪋ࡋࡓࠋ

◊✲ᡂᯝ[Dipp(N,N)-PLY]Ge:࡟㛵ࡋ࡚ Gaussian 09 ࢆ⏝࠸࡚ᇶᗏ≧ែࡢ DFT ィ⟬ࢆᐇ᪋ࡋࡓ࡜ࡇࢁࠊD-SOMO ࡣࣇ࢙ࢼࣞࢽࣝࡢ NBMO ㌶㐨ࠊD-LUMO ࡣࢤ࣐ࣝࢽ࣒࢘ࡢ✵ࡢ S ㌶㐨࡟⏤᮶ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࢫࣆࣥᐦ
ᗘゎᯒ࡟ࡼࡾࠊࢫࣆࣥࡣ㓄఩Ꮚୖ࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀぢ✚ࡶࡽࢀࡓࠋᐇ㝿࡟ࠊESR ࢫ࣌ࢡࢺࣝࡢ㉸ᚤ⣽⤖ྜᐃᩘࡣࠊィ⟬࡟ࡼࡾணࡉࢀࡓ್࡜ࡼ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࠋࡲࡓ[Dipp(N,N)-PLY]Ge:ࡣࢫࣆࣥᐦᗘࡢ኱ࡁ࠸Ⅳ⣲㛫࡛஧㔞໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡶ᫂ࡽ࠿࡜࡞ࡗࡓࠋᅗ >'LSS 11 3/<@*H:ࡢ(a) D-SOMO, (b)D-LUMO ࠾ࡼࡧ(c)ࢫࣆࣥᐦᗘ࣐ࢵࣉ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬1. ෆ⏣ࠊඤ⋢ࠊ୰➽ࠊᓊࠊ໭Ἑࠊ୰㔝ࠊ㬇ᕢࠊ᪥ᮏ໬Ꮫ఍➨ 102 ᫓Ꮨᖺ఍ࠊ2022
2. ୰➽ࠊᓊࠊ໭Ἑࠊඤ⋢ࠊࠊ୰㔝ࠊ㬇ᕢࠊ᪥ᮏ໬Ꮫ఍➨ 102 ᫓Ꮨᖺ఍ࠊ2022ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ᅜ㝿ㄅ࡟ᢞ✏ணᐃ- 49 -

࢜ࣥࣛ࢖ࣥ

࢜ࣥࣛ࢖ࣥ

⏕యศᏊࡢᶵ⬟Ⓨ⌧཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical research on reaction mechanisms in biomolecules‫ۑ‬ᫍ㔝 ᛅḟࠊຍⱱ ኱ᆅࠊ㒌 Ⰿࠊᓥ⏣ ୍⚽ࠊΏ㑓 ୍ᶞࠊႛ Ḡᝋࠊ㝣 ្⇩㸦༓ⴥ኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧



◊✲┠ⓗ
+,9 ㏫㌿෗㓝⣲࡟ෆໟࡉࢀࡿ 51$ ศゎ㓝⣲άᛶ㸦51DVH +㸧ࢆᶆⓗ࡜ࡍࡿ⸆≀ࡣࠊ⌧ᅾ౑⏝ࡉࢀ࡚࠸ࡿ

ᢠ +,9 ⸆࡜」ྜᢞ୚࡛ࡁࡿ࡜ᮇᚅࡉࢀࡿࠋᚑࡗ࡚ࠊ51DVH + άᛶࡣ᪂つࢡࣛࢫࡢᢠ࢘࢖ࣝࢫ⸆࡜ࡋ࡚㨩ຊⓗ࡞ᶆⓗࡢ  ࡘ࡛࠶ࡿࠋ+,9 ㏫㌿෗㓝⣲ࡢ 51DVH+ άᛶ㒊఩࡟ࡣࠊ ࡘࡢ஧౯㔠ᒓࡀᏑᅾࡋࠊゐ፹࡜ࡋ࡚ᶵ
⬟ࡍࡿࠋάᛶ㒊఩ࡢ  ಶࡢ࢝ࣝ࣎࢟ࢩࣝᇶࡀ  ಶࡢ㔠ᒓ࢖࢜ࣥࢆಖᣢࡋ࡚࠸ࡿࠋࡇࡢࡓࡵከࡃࡢ 51DVH+ 㜼ᐖ๣ࡣゐ፹୰ᚰ࡟⤖ྜࡋ࡚ࠊ஧౯㔠ᒓ࢖࢜ࣥ࡜┦஫స⏝ࡍࡿࠋᡃࠎࡣࠊࡇࢀࡲ࡛࡟ 51DVH+ άᛶࢆ㜼ᐖࡍࡿ໬ྜ≀ࢆࠊLQYLWUR ࢫࢡ࣮ࣜࢽࣥࢢ࡟ࡼࡗ࡚ྠᐃࡋࡓࠋࢽࢺࣟࣇࣛࣥ࢝ࣝ࣎ࣥ㓟࢚ࢫࢸࣝ㒊఩ࢆ᭷ࡍࡿ໬
ྜ≀ࡣ +,9 ࡢ」〇ࢆᢚไࡍࡿࠋࢽࢺࣟࣇࣛࣥ࢝ࣝ࣎ࣥ㓟࢚ࢫࢸࣝࡢᵓ㐀ⓗ≉ᚩࡣࠊࢽࢺࣟᇶࡢ㓟⣲ཎᏊࠊࣇࣛࣥᇶࡢ㓟⣲ཎᏊࠊ࢝ࣝ࣎ࢽࣝᇶࡢ㓟⣲ཎᏊࡀࠊ୪ࢇ࡛఩⨨ࡍࡿࡇ࡜࡛࠶ࡿࠋࣄࢵࢺ໬ྜ≀ࡢࢽࢺࣟ
ࣇࣛࣥ࢝ࣝ࣎࢟ࢩࣝᇶࡣ࢚ࢫࢸࣝ⤖ྜࢆ௓ࡋ࡚࣓ࢳࣞࣥᇶ࡟⤖ྜࡋ࡚࠸ࡿࠋ࣓ࢳࣞࣥࡣࡉࡽ࡟࢔࣑ࢻ⤖ྜᙧᡂ࡟ࡼࡾ␯Ỉᛶᇶ࡟⤖ྜࡋ࡚࠸ࡿࠋࣇࣛࣥᇶࡢ㓟⣲ཎᏊࡀ◲㯤ཎᏊ࡟⨨ࡁ᥮࠼ࡽࢀࡓ ࢽࢺࣟࢳ࢜ࣇ࢙ࣥ
࢝ࣝ࣎ࣥ㓟࢚ࢫࢸࣝࡶࠊ51DVH+ άᛶࢆ㜼ᐖࡍࡿࠋ
ᵓ㐀᝟ሗࡣࠊ⸆≀㛤Ⓨࢆຠ⋡ࡼࡃᐇ᪋ࡍࡿࡓࡵ࡟ᚲせ࡛࠶ࡿࠋྜᡂ໬ྜ≀ࡢάᛶ㒊఩࡬ࡢ⤖ྜᵝᘧ࡟㛵ࡍࡿ▱ぢࡣࠊ⸆≀ࡢ᭱㐺໬ࢆㄽ⌮ⓗ࡟⾜࠺㔜せ࡞▱ぢ࡜࡞ࡿࠋ㜼ᐖάᛶࢆ᭷ࡍࡿ໬ྜ≀ࡢྜ⌮ⓗタィ࡟ࡣィ⟬ᶵゎᯒࡶ୙ྍḞ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ ࡘࡢྜᡂ໬ྜ≀࡜ 51DVH+ άᛶ㒊఩ࡢ」ྜయ࡟ࡘ࠸࡚ ; ⥺⤖ᬗゎᯒࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ⤖ᬗᵓ㐀࡟ᇶ࡙ࡁࠊศᏊືຊᏛ 0'  ἲ࡟ࡼࡿィ⟬ᶵࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ㜼ᐖ໬ྜ≀ࡢ⤖ྜᵓ㐀ࡢᏳᐃᛶࢆゎᯒࡋࡓࠋྛ໬ྜ≀࡟ࡘ࠸࡚ࠊ51DVH + ⤌᥮࠼ࢱࣥࣃࢡ㉁ࢆ⏝࠸ࡓ」ྜࣔࢹ࡛ࣝ
QV0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ51DVH+ άᛶ㒊఩࡟⤖ྜࡋࡓ໬ྜ≀ࡢᏳᐃᛶࢆㄪ࡭ࡿࡓࡵ࡟ࠊࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ୰ࡢ⸆≀⤖ྜ㒊఩ࡢኚືࢆほࡋࡓࠋィ⟬ᶵゎᯒ࠿ࡽࡢ▱ぢ࡟ᇶ࡙ࡁࠊࢽࢺࣟࣇࣛࣥ࢝ࣝ࣎࢟ࢩ

ࣝᇶ࡜ࢽࢺࣟࢳ࢜ࣇ࢙ࣥ࢝ࣝ࣎࢟ࢩࣝᇶࡢ໬Ꮫᵓ㐀࡟㉳ᅉࡍࡿ┦஫స⏝ࡢ㐪࠸࡟ࡘ࠸࡚ࠊヲ⣽࡟ゎᯒࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
51DVH+ άᛶ㒊఩࡟኱⭠⳦ࡢ 51DVH+ 㓝⣲ࢆ⤖ྜࡉࡏ࡚⤌᥮࠼㒊ศࢱࣥࣃࢡ㉁ࢆᵓᡂࡋࡓࠋ+,9 ࡢ 51DVH+ άᛶ㒊఩ࡣࠊࡑࡢศᏊ㔞࠿ࡽ S ࡜࿨ྡࡉࢀࡿࠋ⤌᥮࠼ S ࡣ༢⊂࡛ࡣ㓝⣲άᛶࢆ♧ࡉ࡞࠸ࠋ኱⭠⳦ 51DVH+ ࡢ୍ࡘࡢ࣊ࣜࢵࢡࢫࢆ⤌ࡳ㎸ࡴ࡜ࢾࢡࣞ࢔࣮ࢮάᛶࢆⓎ᥹ࡍࡿࠋࡇࡢ⤌᥮࠼ࢱࣥࣃࢡ㉁ S(F ࢆ⏝࠸ࡓࠋ⤌᥮࠼ S(F ࢆࠊ⼥ྜࢱࣥࣃࢡ㉁ 1XVWDJ ࢆࢥ࣮ࢻࡍࡿ࣋ࢡࢱ࣮࡛ᙧ㉁㌿᥮ࡋࡓ኱⭠⳦ 5RVHWWD ᰴ࡛Ⓨ⌧ࡉࡏࡓࠋ⼥ྜࢱࣥࣃࢡ㉁ࢆࠊึࡵ࡟ &R ࢔ࣇ࢕ࢽࢸ࢕࣮࣒࡛࢝ࣛ⢭〇ࡋࡓࠋ1 ᮎ➃ഃࡢ 1XVWDJ ࢆ +59& ࣉࣟࢸ࢔࣮ࢮ࡛ษ᩿ࡋࠊ⥆࠸࡚ 1XVWDJࠊ+59&ࠊษ᩿ࡉࢀ࡚࠸࡞࠸⼥ྜࢱࣥࣃࢡ㉁ࢆ 1L ࣒࡛࢝ࣛ㝖ཤࡋࡓࠋࡉ
ࡽ࡟ᶆⓗࢱࣥࣃࢡ㉁ࢆ࢖࢜ࣥ஺᥮ࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡜ࢤࣝࢁ㐣࡟ࡼࡾ⢭〇ࡋࡓࠋP0 ࡢ 0(6P0 ࡢ=Q62P0 ࡢ 0Q&O ཬࡧ  YY  ࡢ 3(* ࢆྵࡴỈ⁐ᾮ S+ ࢆ⏝࠸ࠊ⵨Ẽᣑᩓἲ࡟ࡼࡗ࡚ S(F ࡢ༢⤖ᬗࢆᡂ㛗ࡉࡏࡓࠋ㜼ᐖ໬ྜ≀ࢆࢯ࣮࢟ࣥࢢἲ࡟ࡼࡾࢱࣥࣃࢡ㉁⤖ᬗ࡟ᑟධࡋࡓࠋ

- 50 -

ศᏊືຊᏛ 0'  ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊྛ㜼ᐖ໬ྜ≀ࡢ⤖ྜᏳᐃᛶࢆㄪ࡭ࡓࠋ0' ィ⟬ࡣࠊ㸴ࡘࡢࣔࢹࣝ࡟ࡘ࠸࡚ QV ᐇ᪋ࡉࡋࡓࠋࡍ࡭࡚ࡢึᮇࣔࢹࣝࡣࡑࢀࡒࢀࡢ⤖ᬗᵓ㐀࠿ࡽᵓ⠏ࡋࡓࠋS(F ࡜  ࡘࡢ㜼ᐖ໬ྜ≀ࡢ」ྜయࢆ 7,33 Ỉ࡛‶ࡓࡉࢀࡓ㛗᪉ᙧࡢ࿘ᮇⓗቃ⏺࣎ࢵࢡࢫ࡟⨨ࡁࠊ࢖࢜ࣥࢆຍ࠼࡚ࣔࢹࣝ⣔ࢆ୰ᛶ࡟ࡋࡓࠋຊሙࣃ࣓࣮ࣛࢱࡣࠊࢱࣥࣃࢡ㉁࡟ࡘ࠸࡚ II6% ࢆࠊ໬ྜ≀࡟ࡘ࠸࡚ JDII ࢆ⏝࠸ࡓࠋィ⟬ࡣࠊ
$0%(5 ࢆ⏝࠸࡚ࠊ*38 ࡛ࡢᐇ⾜ྍ⬟࡞ SPHPG ࣔࢪ࣮ࣗࣝࢆ౑⏝ࡋࡓࠋ◊✲ᡂᯝ᭷ᶵྜᡂࡋࡓ໬ྜ≀  ✀㢮࡟ࡘ࠸࡚ࠊS(F ࡢ༢⤖ᬗࢆᚓ࡚ࠊ; ⥺ᵓ㐀ゎᯒࢆ⾜࠸ࠊ⤖ྜᵓ㐀ࢆ  ࡢศゎ⬟࡛ᚓࡓࠋ3'% Ⓩ㘓␒ྕࡣࠊ;,6;-;,7;,9;-;-ᅗ㸯㸸ࢽࢺࣟࣇࣛࣥ㦵᱁ࢆࡶࡘ㜼ᐖ๣ L  ࡜ࢽࢺࣟࢳ࢜ࣇ࢙ࣥ㦵᱁ࢆࡶࡘ㜼ᐖ๣ LL ࡢẚ㍑ࠋ L ࡢ໬ྜ≀ࡣࢽࢺࣟࣇࣛࣥㄏᑟయࡢ
༢⣧࡞໬Ꮫᵓ㐀࡛࠶ࡾࠊ
LL ࡢ໬ྜ≀ࡣࢽࢺࣟࢳ࢜
ࣇ࢙ࣥㄏᑟయࡢ༢⣧࡞ᵓ㐀࡛࠶ࡿࠋ D ⤖ᬗᵓ㐀ࠋ E 
0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡗ࡚ᚓࡽࢀࡿ௦⾲ⓗ࡞ᵓ㐀ࠋ F 㜼ᐖ໬ྜ≀࠿ࡽྛ
0Q ࢖ ࢜ ࣥ ࡲ ࡛ ࡢ ᭱ ▷ ㊥㞳ࡢ᫬㛫⤒㐣ࣉࣟࢵࢺࠋ
0Q ࡜ࡢ㊥㞳ࡣ㟷Ⰽ࡛࠶
ࡾࠊ0Q ࡜ࡢ㊥㞳ࡣ㉥Ⰽ࡛
࠶ࡿࠋ G  ಶࠎࡢṧᇶࡢ %ᅉᏊࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜
⤖ᬗᵓ㐀ࡢ % ᅉᏊࢆࡑࢀࡒ
ࢀ㟷࡜㉥ࡢ⥺࡛⾲ࡋࡓࠋ࣮ࣝࣉ㡿ᇦࡢṧᇶࢆࢩ࢔ࣥࡢ
ᩥᏐ࡛♧ࡍࠋ

- 51 -

⤖ᬗᵓ㐀ࡢᚓࡽࢀࡓ໬ྜ≀ࡢ࠺ࡕࠊ໬ྜ≀ L ࡣࢽࢺࣟࣇࣛࣥ࢝ࣝ࣎࢟ࢩࣝᇶࢆ㦵᱁ᵓ㐀࡟ᣢࡘࠋ໬ྜ≀ LLࡣࢽࢺࣟࢳ࢜ࣇ࢙ࣥ࢝ࣝ࣎࢟ࢩࣝᇶࢆ㦵᱁ᵓ㐀࡟ᣢࡘࠋ໬ྜ≀ L ࡣࠊࣇࣛࣥ 2 ཎᏊࡀ୍ࡘࡢ㔠ᒓ࢖࢜ࣥࡢ
㏆ഐ࡟఩⨨ࡋ࡚࠸ࡓࠋ%U ཎᏊࡣ⁐፹୰࡟఩⨨ࡋࠊᶆⓗ࡬ࡢ⤖ྜ࡬ࡢᐤ୚ࡣᑠࡉ࠸ࠋ໬ྜ≀ LL ࡛ࡣࠊ஧ࡘࡢ㔠ᒓ࢖࢜ࣥࡣࢳ࢜ࣇ࢙ࣥ⎔ࡢ㠃እ࡟࠶ࡾࠊࢽࢺࣟ࠾ࡼࡧ࢝ࣝ࣎ࢽࣝ 2 ཎᏊࡣ㔠ᒓ࢖࢜ࣥ࠿ࡽ㞳ࢀ࡚࠸ࡓࠋ
໬ྜ≀ L ࡜ LL ࡢ⤖ᬗᏛⓗゎᯒ࡜ィ⟬ゎᯒࢆᑐẚࡋ࡚ࠊࣇࣛࣥ⣔࡜ࢳ࢜ࣇ࢙ࣥ⣔㊊ሙࡢ⤖ྜ఩⨨ࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡋࡓ>ᅗ @ࠋ⤖ᬗᵓ㐀࡟࠾࠸࡚ࠊ ࡘࡢ㔠ᒓ࢖࢜ࣥࢆ⤖ࡪ⥺ࡣࠊࣇࣛࣥ㦵᱁ࡢࣇࣛࣥ⎔ࡢᖹ㠃࡟ᖹ⾜࡛࠶ࡿྍ⬟ᛶࡀ㧗࠸>ᅗ  DL @ࠋᑐ↷ⓗ࡟ࠊࢳ࢜ࣇ࢙ࣥ 6 ཎᏊࡣ  ࡘࡢ㔠ᒓࡢ㛫࡟௓ᅾࡋ࡚࠸ࡿྍ⬟ᛶࡀ㧗ࡃࠊ᥋⥆⥺ࡣࢳ࢜ࣇ࢙ࣥ⎔࡟ᆶ┤࡟㏆࠸>ᅗ  DLL @ࠋࢩ࣑࣮ࣗࣞࢩࣙࣥᵓ㐀࡛ࡣ  ࡘࡢ㔠ᒓ࢖࢜ࣥ࡜ࣇࣛࣥ⎔ࡀࡼࡃᩚิࡋ࡚࠸ࡿࠋ୍᪉ࡢࢽࢺࣟ 2 ཎᏊࡣ୍᪉ࡢ㔠ᒓ࢖࢜ࣥ࡟ᙉࡃ㓄఩ࡋ࡚࠾ࡾࠊ࢝ࣝ࣎ࢽࣝ 2 ཎᏊࡣ௚᪉
ࡢ㔠ᒓ࢖࢜ࣥ࡟Ᏻᐃ࡟㓄఩ࡋ࡚࠸ࡿ>ᅗ  EL @ࠋᑐ↷ⓗ࡟ࠊࢳ࢜ࣇ࢙ࣥ 6 ཎᏊࡣ㔠ᒓ࠿ࡽ㞳ࢀ࡚࠾ࡾࠊ࢝ࣝ࣎
ࢽࣝ 2 ཎᏊࡣάᛶ㒊఩࡛ࢳ࢜ࣇ࢙ࣥ㒊ศࢆᙉࡃ⤖ྜࡋ࡚࠸ࡿ>ᅗ  ELL @ࠋ໬ྜ≀࠿ࡽྛ㔠ᒓ࢖࢜ࣥࡲ࡛ࡢ᭱
㏆᥋㊥㞳ࡣ㓄఩ࡢ㐪࠸ࢆ♧ࡋࡓࠋࣇࣛࣥ㦵᱁ࢆࡶࡘ㜼ᐖ๣࡛ࡣࠊ୧᪉ࡢ㔠ᒓ࢖࢜ࣥ࡬ࡢ㊥㞳ࡣᖖ࡟ᑠࡉ࠸>ᅗ
 FL @ࠋᑐ↷ⓗ࡟ࠊࢳ࢜ࣇ࢙ࣥ㦵᱁ࡢ  ࡘࡢ㔠ᒓ࢖࡛࢜ࣥࡣ㓄఩ࡣほᐹࡉࢀ࡞࠸>ᅗ  FLL @ࠋ௚᪉ࡢ㔠ᒓ࡜ࡢ᭱ࡶ㏆࠸㊥㞳ࡣ୍ᐃ࡟ಖࡓࢀࡿࠋࢳ࢜ࣇ࢙ࣥ㊊ሙࢆ᭷ࡍࡿ㜼ᐖ๣ࡣ⤖ᬗᵓ㐀࠿ࡽ᭷ព࡟㐓⬺ࡋࡓࡀ% ᅉᏊศᯒࡣࣇࣛࣥ㊊ሙ࡜ẚ㍑ࡋ࡚ప࠸ᰂ㌾ᛶࢆ♧ࡍ>ᅗ  GL ࠾ࡼࡧ  GLL @ࠋࡋࡓࡀࡗ࡚ࠊ6 ࢆ 2 ࡛⨨᥮ࡍࡿ࡜ࠊ㜼ᐖᛶㄏᑟయ໬ྜ≀ࡢ⤖ྜᵓ㐀࡟ⴭࡋ࠸ᕪࡀ⏕ࡌࡿࠋ ✀㢮ࡢ໬ྜ≀࡟ࡘ࠸࡚ࠊ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ⤖ᯝ࡛ࡣࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ୰ࠊ඲࡚ࡢ໬ྜ≀ࡣ㓝⣲άᛶ㒊఩࡟␃ࡲࡗ࡚࠸ࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⤖ྜᏳᐃᛶࡣࠊࢽࢺࣟࣇࣛࣥࢆ㦵᱁ᵓ㐀࡟᭷ࡍࡿ㜼ᐖ๣࡜ࢽࢺࣟࢳ࢜ࣇ࢙ࣥࢆ㦵᱁ᵓ㐀࡟᭷ࡍࡿ㜼ᐖ๣ࡢ㛫࡛␗࡞ࡿࠋࢽࢺࣟࣇࣛࣥ࢝ࣝ࣎ࢽࣝ㒊఩ࡣ  ࡘࡢ㔠ᒓ࢖࢜ࣥ࡜ᙉᅛ࡟⤖ྜࡋ࡚࠾ࡾࠊᏳᐃ࡞」ྜయࢆᙧᡂࡋ࡚࠸ࡿࠋࢽࢺࣟࣇࣛࣥ㒊ศࡢィ⟬ᚋࡢ⤖ྜ఩⨨ࡣ  ✀ࡢ໬ྜ≀㛫࡛࡯࡜ࢇ࡝ྠ୍࡛࠶ࡗࡓࠋࢽࢺࣟࣇࣛࣥ㒊ศࡢࡍ࡭࡚ࡢཎᏊ࡜  ࡘࡢ㔠ᒓࡣࣇࣛࣥ⎔ࡢᖹ㠃ୖ࡟ᩚิࡋ࡚࠸ࡿࠋ஧౯㔠ᒓ࢖࢜ࣥࡣࣇࣛࣥ⎔ࡢྠ୍ᖹ㠃ୖ࡟఩⨨ࡍࡿࠋᑐ↷ⓗ࡟ࠊࢽࢺࣟࢳ࢜ࣇ࢙ࣥ࢝ࣝ࣎ࢽࣝ㒊఩ࡣ㓝⣲ࡢ  ࡘࡢ㓟ᛶṧᇶ࡟ࡼࡿ㔠ᒓ࢖࢜ࣥࡢ࣮࢟ࣞࢺࢆᨩ஘ࡍࡿࠋ⤖ᬗᵓ㐀࡟࠾࠸࡚ࠊࢳ࢜ࣇ࢙ࣥ 6 ཎᏊࡣ஧ࡘࡢ㔠ᒓ࢖࢜ࣥࡢ୰㛫఩⨨࡟఩⨨ࡋ࡚࠸ࡓࠋ஧ࡘࡢ㔠ᒓ࢖࢜ࣥࡢ఩⨨ࡣࢳ࢜ࣇ࢙ࣥ⎔ࡢ㠃እ࡟࠶ࡿࠋィ⟬ᚋࡢ⤖ྜ࣏࣮ࢬ࡛ࡣࠊࢳ࢜ࣇ࢙ࣥ 6 ཎᏊࡣ㔠ᒓ࢖࢜ࣥ࠿ࡽ㞳ࢀ࡚࠸ࡓࠋࡋ࠿ࡋࠊ ✀ࡢ໬ྜ≀ࡣࡍ࡭࡚ά
ᛶ㒊఩ࡢ࿘ᅖ࡟Ᏻᐃ࡟Ꮡᅾࡋࡓࠋ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊࣇࣛࣥ࡜ࢳ࢜ࣇ࢙ࣥ໬Ꮫ㦵᱁ࡢ㛫ࡢ⤖ྜ࣏࣮ࢬࡢ㐪࠸ࢆ♧ࡋࡓࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫@>ۻ‬.DPR72ED\DVKL+*XR<<DPDPRWR11LVKLGD1+RVKLQR7࢖ࣥࣇ࢚ࣝࣥࢨ࢘࢖
ࣝࢫࡢ 51$ ࣏࣓࣮ࣜࣛࢮ㜼ᐖάᛶࢆ᭷ࡍࡿ໬ྜ≀ࡢ᥈⣴◊✲㺂᪥ᮏ⸆Ꮫ఍➨  ᖺ఍ྡྂᒇ࣏ࢫࢱ࣮
Ⓨ⾲㸦㸧‫ @>ۻ‬㒌Ⰿ㸪▞Ⰻ㸪す⏣⣖㈗㸪ᫍ㔝ᛅḟ,QIOXHQFH RI (OHFWURVWDWLF 3RWHQWLDOV RQ WKH 3URWHLQV&U\VWDOOL]DWLRQE\$PPRQLXP6XOIDWHࠊ᪥ᮏ⸆Ꮫ఍➨  ᖺ఍ྡྂᒇ࣏ࢫࢱ࣮Ⓨ⾲㸦㸧‫@>ۻ‬.DPR7*XR<<RQHGD71XNDJD01LVKLGD1+RVKLQR7ᢠ⏕≀㉁ే⏝๣࡜ࡋ࡚ࡢ࣓ࢱࣟșࣛࢡࢱ࣐࣮ࢮ㜼ᐖ๣ࡢ᥈⣴◊✲㺂 ᖺᗘ㔞Ꮚࣅ࣮࣒ࢧ࢖࢚ࣥࢫࣇ࢙ࢫࢱ࢜ࣥࣛ࢖ࣥ࣏
ࢫࢱ࣮Ⓨ⾲‫ @>ۻ‬㒌Ⰿ㸪ᫍ㔝ᛅḟ ,QIOXHQFH RI (OHFWURVWDWLF 3RWHQWLDOV RQ WKH 3URWHLQV &U\VWDOOL]DWLRQ E\$PPRQLXP6XOIDWH㺂 ᖺᗘ㔞Ꮚࣅ࣮࣒ࢧ࢖࢚ࣥࢫࣇ࢙ࢫࢱ࢜ࣥࣛ࢖ࣥ࣏ࢫࢱ࣮Ⓨ⾲- 52 -

‫@>ۻ‬2ED\DVKL+*XR<.DPR71XNDJD0<DPDPRWR11LVKLGD1+RVKLQR7࢖ࣥࣇ࢚ࣝࣥࢨ࢘࢖ࣝࢫ 51$ ࣏࣓࣮ࣜࣛࢮ㜼ᐖ๣ࡢ᥈⣴࡜ ; ⥺⤖ᬗᵓ㐀ゎᯒ㺂 ᖺᗘ㔞Ꮚࣅ࣮࣒ࢧ࢖࢚ࣥࢫ
ࣇ࢙ࢫࢱ࢜ࣥࣛ࢖ࣥ࣏ࢫࢱ࣮Ⓨ⾲‫@>ۻ‬ຍⱱ኱▱⡿⏣཭㈗㢠㈡㊰჆す⏣⣖㈗ᫍ㔝ᛅḟ࣓ࢱࣟșࣛࢡࢱ࣐࣮ࢮ㜼ᐖάᛶࢆ᭷ࡍࡿ໬
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Molecular simulations by generalized-ensemble algorithms
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ࡾ࡛࡞ࡃࠊࢱࣥࣃࢡ㉁ࡢᢡࡾ␚ࡳ࡟㛵ࡍࡿ⇕ຊᏛⓗ⪃ᐹࢆ⾜࠺ࡇ࡜ࡶ┠ⓗ࡜ࡋ࡚࠸ࡿࠋศᏊ࠾ࡼࡧศᏊ㞟ᅋࢆᢅ࠺ศᏊ⛉Ꮫࡢ◊✲࡟ࡣࠊ኱ࡁ࡞ᅔ㞴ࡀᏑᅾࡍࡿࠋࡑࢀࡣࠊࡇࡢࡼ࠺࡞ከ⮬⏤ᗘ」㞧⣔࡟ࡣࠊ࢚ࢿࣝࢠ࣮
ᴟᑠ≧ែࡀ↓ᩘ࡟Ꮡᅾࡍࡿࡓࡵ࡟ࠊᚑ᮶ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࢆ⏝࠸࡚࠸࡚ࡣࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࡀࡑࢀ
ࡽࡢ࢚ࢿࣝࢠ࣮ᴟᑠ≧ែ࡟␃ࡲࡗ࡚ࡋࡲ࠸ࠊㄗࡗࡓ⤖ᯝࢆᑟ࠸࡚ࡋࡲ࠺ࡇ࡜࡟㉳ᅉࡍࡿࠋᡃࠎࡣࢩ࣑࣮ࣗࣞ
ࢩࣙࣥࡀ࢚ࢿࣝࢠ࣮ᴟᑠ≧ែ࡟␃ࡲࡿࡢࢆຠ⋡Ⰻࡃ㑊ࡅࡿࡇ࡜ࡀ࡛ࡁࡿࠊᣑᙇ࢔ࣥࢧࣥࣈࣝἲ JHQHUDOL]HGHQVHPEOHDOJRULWKP ࡜⥲⛠ࡉࢀࡿᡭἲࢆࡇࡢၥ㢟࡟㐺⏝ࡍࡿࡇ࡜ࢆᥦၐࡋࠊᵝࠎ࡞ศᏊ⛉Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡟㐺⏝ࡋ࡚ࡁࡓ㸦᭱㏆ࡢゎㄝ࡜ࡋ࡚ࡣࠊ౛࠼ࡤࠊ௨ୗࢆཧ↷ࡉࢀࡓ࠸ࠋᒸᮏࠊBiophysics and Physicobiology
  㸧ࠋᮏ◊✲ࡢ┠ⓗࡣࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ᭷ຠ࡞ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࢆ᭦࡟㛤Ⓨࡋ࡚࠸ࡃࡇ࡜࡛࠶ࡿࠋ

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࠸ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࢆ㛤Ⓨࡋࡓࡾࡋ࡚ࡁࡓࠋ≉࡟ࠊ ᖺ࡟㛤Ⓨࡋࡓࣞࣉࣜ࢝஺᥮ศᏊືຊᏛἲ ᮡ⏣ࠊᒸ
ᮏࠊChem. Phys. Lett.  ࡣࠊࡑࡢ㐺⏝ࡢᐜ᫆ࡉࡢࡓࡵ࡟ࠊᅜ㝿ⓗ࡟ᗈࡃཷࡅධࢀࡽࢀࠊ⇿Ⓨⓗ࡞◊✲άືࢆㄏ㉳ࡋ࡚ࡁࡓࠋᡃࠎࡣ  ᖺ࡟㛤Ⓨࡋࡓᣑᙇ࢔ࣥࢧࣥࣈࣝἲ ከḟඖࣞࣉࣜ࢝஺᥮ἲࠊࣞࣉࣜ࢝
஺᥮࣐ࣝࢳ࢝ࣀࢽ࢝ࣝἲࠊ࣐ࣝࢳ࢝ࣀࢽ࢝ࣝࣞࣉࣜ࢝஺᥮ἲࠊࣞࣉࣜ࢝஺᥮↝ࡁᡠࡋἲ࡞࡝ ࢆ㥑౑ࡍࡿ࡜࡜
ࡶ࡟ࠊ᪂ࡋࡃᙉຊ࡞ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࢆ㛤Ⓨࡋ࡚ࡁࡓࠋ≉࡟ࠊඛᖺࠊከḟඖࣞࣉࣜ࢝஺᥮ἲࠊከḟඖ࣐ࣝࢳ࢝ࣀࢽ࢝ࣝἲࠊከḟඖ↝ࡁᡠࡋἲࡢ୍⯡ㄽࡢᐃᘧ໬࡟ᡂຌࡋࠊࡇࢀࡽࡢ୍㐃ࡢᡭἲ㛤Ⓨ࡟୍ࡘࡢ༊ษࡾࢆࡘࡅࡓ ගṊࠊᒸᮏࠊJ. Chem. Phys.  ࠋᮏ⏦ㄳࡣ⺮ⓑ㉁ࡢᢡࡾ␚ࡳࢆ୺ၥ㢟࡜ࡋ࡚ࠊ㛗࠸㛫⥅⥆⏦ㄳࢆ⧞ࡾ㏉ࡋ࡚ࡁࡓࡀࠊ᭱㏆࡛ࡣࠊࡼࡾᖜᗈ࠸ศᏊ⛉Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥࡢၥ㢟࡟ࢸ࣮࣐ࢆᣑ኱ࡋ࡚ࡁ
ࡓࠋ౛࠼ࡤࠊ⺮ⓑ㉁࡬ࡢ⸆๣ೃ⿵ศᏊࡢࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᡃࠎࡀ㛤Ⓨࡋࡓࣞࣉࣜ࢝஺᥮ചࢧࣥ
ࣉࣝἲࢆ㐺⏝ࡋࠊᑠศᏊࡢ⤖ྜᵓ㐀ࡢண࡟ᡂຌࡋࡓࡀࠊ ḟඖࣞࣉࣜ࢝஺᥮ἲ࡟ࡼࡿࢻࢵ࢟ࣥࢢࢩ࣑ࣗࣞ

࣮ࢩࣙࣥࡼࡾࠊᑠศᏊࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬ἲࡶᥦ᱌ࡋࡓࠋ᭦࡟ࠊࡇࢀࡲ࡛ࡣ୺࡟ྂ඾ຊᏛ࡟ᇶ࡙ࡃ
ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࡀࠊඛᖺࠊᐦᗘỗ㛵ᩘἲ ')7 ࡸᙉ⤖ྜ㏆ఝᐦᗘỗ㛵ᩘἲ ')7% ࡛㔞Ꮚຠᯝࢆྲྀࡾධࢀࡓᣑᙇ࢔ࣥࢧࣥࣈࣝἲࡢ㛤Ⓨ࡟ࡶᡂຌࡋࡓࠋ ᡃࠎࡢ᪉ἲࡢ≉ᚩࡣࠊึᮇᵓ㐀࡜ࡋ࡚≉ᐃࡢࡶࡢࢆ⏝࠸ࡓࡾࠊ᪤▱ࡢᐇ㦂⤖ᯝ࡟ྥ࠿࠺ࡼ࠺࡞㔜ࡳࡣ୍ษ௜ࡅࡎࠊࣛࣥࢲ࣒࡞ึᮇᵓ㐀࠿ࡽࢩ࣑࣮ࣗࣞࢩࣙࣥࢆጞࡵࡿࡇ࡜࡟࠶ࡿࠋ

- 58 -

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ࡋ࡚ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ♧ࡍࠋᮎ➃ࡢ࢔࣑ࣀ㓟ṧᇶ /\V ࡜ *OX ࡢഃ㙐ࡢ㟼㟁┦஫స⏝ࡢࡓࡵ࡟ࠊ཯ᖹ⾜șࢩ࣮ࢺᵓ㐀ࡀከࡃぢࡽࢀࡿࡀࠊᩘᐦᗘࡀ㧗࠸⣔࡟࠾࠸࡚ࡣࠊᖹ⾜șࢩ࣮ࢺࡢᙧᡂࡶᑡࡋ
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ㄽᩥ  ᴿࠊᕝ㷂ࠊᒸᮏ                     ACS Omega  - 61 -

㹢㟁Ꮚ」ྜ⣔ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊ཯ᛂ㐣⛬࡟㛵ࡍࡿ⌮ㄽⓗ◊✲$7KHRUHWLFDO6WXG\RI*HRPHWULHV(OHFWURQLF6WUXFWXUHVDQG5HDFWLRQ
3URFHVVHVRIG(OHFWURQ&RPSOH[&KHPLFDO6\VWHP ‫ۑ‬ᴬ ⱱዲࠊடᑿ ⫕ࠊBo Zhu, Zhao Peng, JunQing Yin㸦ி㒔኱Ꮫ ゐ፹࣭㟁ụඖ⣲ᡓ␎◊✲ࣘࢽࢵࢺ㸧1◊✲┠ⓗࠊෆᐜ
㑄⛣㔠ᒓඖ⣲ࡣVS㌶㐨࡟ຍ࠼ࠊG㌶㐨ࡀཎᏊ౯㌶㐨࡜࡞ࡿࠋGẆࡣᡂศࢆᣢࡕࠊࡑࡢ⤖ᯝࠊ⤖ྜᛶࠊ཯⤖ྜᛶ㌶㐨࡜࡜ࡶ࡟ࠊ⤖ྜ࡟㛵୚ࡋ࡞࠸㠀⤖ྜᛶG ㌶㐨ࡀᏑᅾࡍࡿࡓࡵࠊGG ㌶㐨࢚ࢿࣝࢠ࣮ᕪࡀᑠࡉ࠸࡜ゝ࠺≉ᚩࡀ࠶ࡾࠊከᵝ࡞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」ྜ⣔ࡣࠊ㟁Ꮚ≧ែࡢከᵝᛶࡀ୍ᒙ㇏࠿࡟࡞ࡾࠊᰂ㌾࡞㟁Ꮚ≧ែࢆྲྀࡾ࠼ࡿࡼ࠺࡟࡞ࡿࠋG࡞ᵓ㐀ࠊ⤖ྜࠊศᏊ≀ᛶࠊ཯ᛂᛶࢆ♧ࡍࡢࡣࡑࡢ⤖ᯝ࡛࠶ࡿࠋᚑࡗ࡚ࠊG㟁Ꮚ」ྜ⣔ࡀከᵝ

㟁Ꮚ」ྜ⣔ࡣศᏊᛶゐ፹ࠊᅛయゐ፹ࠊ㔠ᒓ㓝⣲ࠊኴ㝧㟁ụࡢቑឤ๣ࠊ᭷ᶵ (/ ࡢⓎග⣲ᏊࠊศᏊ☢▼࡞࡝࡜ࡋ࡚ࠊ⌧௦ࡢ໬Ꮫࡢ୰ᚰⓗ࡞◊✲ᑐ㇟࡜࡞ࡗ࡚࠸ࡿࠋࡑࢀࡽࡢᵓ㐀ࠊศᏊ≀ᛶࠊᶵ⬟ࠊ཯ᛂᛶࡣᇶ♏໬Ꮫࠊᛂ⏝໬Ꮫ࠸ࡎࢀ࡟࠾࠸࡚ࡶ㔜せ࡛࠶ࡿࠋࡑࢀࡽࡢᶵ⬟࡜ G 㟁Ꮚ」ྜ⣔ࡢ㟁Ꮚ≧ែ࡜ࡣᐦ᥋࡟┦㛵ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊG 㟁Ꮚ」ྜ⣔ࡢ໬Ꮫࢆ㟁Ꮚㄽ࡟ᇶ࡙࠸࡚ゎ᫂ࡋࠊணG

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࡞ࢱ࣮ࢤࢵࢺ࡛࠶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ಀ࡛ࡣࢽࢵࢣࣝ ,, ࣄࢻࣜࢻ㘒య࡟ࡼࡿ &) ࢢ࣮ࣝࣉࡢ⬺ࣇࢵ⣲Ỉ⣲໬཯ᛂࡢ཯ᛂᶵᵓ࡜ゐ፹άᛶࢆᨭ
㓄ࡍࡿᅉᏊࡢゎ᫂ࠊ LL  㔠ᒓ㘒యࡢᵓ㐀࡜⤖ྜ࡟㛵ࡍࡿ◊✲࡛ࡣࠊG 㟁Ꮚ㓄⨨ࡢ5K࡜G 㟁Ꮚ㓄⨨ࡢ3Gࡢ㛫ࡢ┤᥋⤖ྜࢆࡶࡘ㸰᰾㘒యࡢ㔠ᒓ㛫⤖ྜࡢ⌮ㄽゎᯒࠊ LLL  㔠ᒓᚤ⢏Ꮚ㛵ಀ࡛ࡣࠊ➨㸶᪘࠿ࡽ➨㸯㸯᪘ࡢ➨୍㑄⛣࿘ᮇ㔠ᒓᚤ⢏Ꮚࠊ)H&R1L&X ࡟ࡼࡿ12ࡢゎ㞳྾╔཯ᛂᛶࡢẚ㍑ࠊ&R#3W ࠾ࡼࡧ1L#3W ࢥ࢔ࢩ࢙ࣝᚤ⢏Ꮚ࡟ࡼࡿ㓟⣲ศᏊ㑏ඖ཯ᛂࡢ཯ᛂᶵᵓ࡜཯ᛂάᛶࡢ⌮ㄽⓗゎ᫂ࠊ LY  ᅛయゐ፹཯ᛂ㛵ಀ࡛ࡣࠊࢡ࣒ࣟࢆ୺ᡂศ࡜ࡍࡿࢫࣆࢿࣝᆺ㓟໬≀ 0&U2 ࡟ࡼࡿ &2 㓟໬཯ᛂࡢ཯ᛂᶵᵓ࡜ゐ፹άᛶࢆᨭ㓄ࡍࡿ㔜せ࡞ᅉᏊࡢゎ᫂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,
MP2 to MP4(SDQ), CCSD(T)ἲ᳨࡛ウࡋࡓࠋDFTィ⟬࡟ࡣB3PW91-D3࠶ࡿ࠸ࡣZB97XD஺᥮┦㛵ỗ㛵ᩘࢆ⏝- 62 -

࠸ࡓࠋ㑄⛣㔠ᒓඖ⣲ࡢෆẆ㟁Ꮚࡣ Hay-Wadt ࡶࡋࡃࡣ Stuttgart-Dresden-Bonn ࡢ᭷ຠෆẆ࣏ࢸࣥࢩࣕࣝ(ECP)࡛
⨨ࡁ᥮࠼ࠊཎᏊ౯㟁Ꮚࡣ split-valence ᆺࡶࡋࡃࡣ triple-zeta ᆺᇶᗏ㛵ᩘ࡛⾲ࡋࡓࠋࡲࡓࠊ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౑⏝ࡋࡓࠋ཯ᛂ࡟┤᥋㛵ಀࡍࡿཎᏊ࡟ࡣ d ศᴟ㛵ᩘࢆຍ࠼ࡓࠋᵓ㐀᭱㐺໬࡜ DFT ィ⟬࡟ࡣࠊ୺࡟ࠊGaussian09 ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋ㔠ᒓࢡࣛࢫࢱ࣮/ᚤ⢏Ꮚ࠾ࡼࡧᅛయゐ፹ࡢ⌮ㄽ◊✲࡛ࡣ࿘ᮇቃ⏺᮲௳ DFT ἲ࡜ᖹ㠃Ἴᇶᗏࢆ⏝࠸ࠊVASP ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 ࢽࢵࢣࣝ(II)ࣄࢻࣜࢻ㘒య࡟ࡼࡿ CF3 ᇶࡢ⬺ࣇࣝ࢜ࣟỈ⣲໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸ࣇࢵ⣲໬ྜ≀ࡣ་⸆ရ࡞࡝࡛㔜せ࡞໬ྜ≀࡛࠶ࡿࠋ໬ྜ≀ࡢ୰ࡢ F ࡢᩘࢆไᚚࡍࡿᚲせࡀ࠶ࡿࡀࠊࡑࡢ㔜せ࡞཯ᛂ࡜ࡋ࡚ CF3 ᇶࡢ F
ࢆ H ࡟⨨᥮ࡍࡿ defluorohydrogenation ࡀ࠶ࡿࠋࡋ࠿ࡋࠊC(sp3)-F⤖ྜࡣᴟࡵ࡚ᙉᅛ࡛࠶ࡾࠊࡑࡢษ᩿ࠊάᛶ໬ࡣᐜ࡛᫆࡞࠸ࠋ
᭱㏆ࠊࢽࢵࢣࣝ(II)ࣄࢻࣜࢻ㘒యࢆ⏝࠸࡚ CF3 ᇶࢆኚ᥮ࡍࡿ཯
ᛂ(Scheme 1)ࡀሗ࿌ࡉࢀࡓࡀࠊ཯ᛂᶵᵓࡣ㺂ࢫࢳࣞࣥㄏᑟయࢆ
ᇶ㉁࡜ࡋ࡚࠸ࡿ࡟ࡶ㛵ࢃࡽࡎࠊᐇ㦂ⓗ࡟ࡣ Ni-H ࡬ࡢ C=C ஧㔜⤖ྜࡢᤄධ཯ᛂ࡛࡞ࡃࠊ㏻ᖖࡣ⪃࠼ࡽࢀ࡞࠸ H ⛣ື཯ᛂࡀᥦ
᱌ࡉࢀ࡚࠸ࡿࠋᙉᅛ࡞ C-F ⤖ྜࡢάᛶ໬㐣⛬࡜ࢫࢳࣞࣥᤄධ
཯ᛂ࡛࡞ࡃỈ⣲⛣ືࡀᥦ᱌ࡉࢀࡓ⌮⏤࡟⯆࿡ࢆᣢࡕࠊࡇࡢ཯
ᛂࡢ⌮ㄽⓗ◊✲ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ཯ᛂࡣ Scheme 2 ࡟♧ࡍࡼ࠺࡟ࠊH ⛣ື࡛࡞ࡃࠊࣄࢻࣜࢻ⛣ືࡀ㉳ࡇࡾࠊ࢖࢜ࣥᑐ୰

Scheme 1. Ni(II)-H 㘒య࡟ࡼࡿ CF3 ᇶࡢኚ㛫యࢆ⏕ᡂࡋࠊࡘࡂ࡟Ⅳ⣲࢔ࢽ࢜ࣥ࠿ࡽ Ni(II)࡬ࡢ㟁Ꮚ⛣ືࠊ᥮཯ᛂ

Ni-C ⤖ྜᙧᡂࠊC-F ⤖ྜࡢษ᩿࡟ࡼࡿ⏕ᡂ≀࡜
Ni(II)-F 㘒యࡢ⏕ᡂࠊPhSiH3 ࡜ࡢ཯ᛂ࡟ࡼࡿ㉸ཎ
Ꮚ౯ Si ࢔ࢽ࢜ࣥ࡜ࡢ࢖࢜ࣥᑐᙧᡂࢆ⤒࡚ฟⓎࡢ
Ni(II)-H 㘒యࡀ෌⏕ࡉࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ㏵୰ࠊ
Ni 㘒యࡣ closed-shell singlet ࠿ࡽ triplet ࡟ኚ໬ࡋࠊ
ࡑࡢᚋࠊNi-F ⤖ྜࡀษ᩿ࡉࢀ Ni-H ⤖ྜࡀ⏕ᡂࡍࡿ㝿࡟ࠊclosed-shell singlet ࡟ᡠࡿࠋࡇࡢ C-F ⤖ྜኚ᥮཯ᛂࡀᡂຌࡍࡿࡢࡣࠊNi ࡀ࢖࢜ࣥᑐࢆᙧᡂࡍࡿࡇ࡜ࠊsinglet ࠿ࡽ triplet ࡟ࢫࣆ

Scheme 2.ࣥ≧ែࡀᐜ᫆࡟ኚ໬ࡍࡿࡇ࡜ࡀ㘽࡛࠶ࡿࡇ࡜ࡀ཯ᛂᶵᵓ

Ni(II)-H 㘒య࡟ࡼࡿ CF3 ᇶࡢኚ᥮཯ᛂࡢ

♧ࡉࢀࡓࠋᐇ㝿ࠊ㢮ఝࡢ཯ᛂࢆ Pd(II)-H 㘒య᳨࡛ウࡋࡓ࡜ࡇࢁࠊPd ࡛ࡣᖖ࡟ closed-shell singlet ࡀᏳᐃ࡞ࡓࡵࠊ୰㛫యࡀᴟࡵ࡚୙Ᏻᐃ࡟࡞ࡾࠊࡇࡢゐ፹཯ᛂࡀ㐍⾜ࡋ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊࢫࢳࣞࣥᤄධ཯ᛂࡀ㉳ࡇࡽ࡞࠸ࡢࡣࠊ㓄఩Ꮚࡢᖹ㠃ᛶࡀᙉ࠸ࡓࡵ࡛࠶ࡿࡇ࡜ࡀࠊScheme 1(b)࡟♧ࡍࣔࢹࣝ㓄఩Ꮚࢆ᥇⏝ࡋࡓィ⟬⤖ᯝ࠿ࡽ♧ࡉࢀࡓࠋ௨ୖ࠿ࡽࠊC-F ⤖ྜ࡜ゝ࠺ᅔ㞴࡞㐣⛬ࢆྵࡴゐ፹཯ᛂࢆᡂ
ຌࡉࡏࡿ࡟ࡣ spin ≧ែࡀࣇࣞ࢟ࢩࣈࣝ࡞ Ni ࡜ᖹ㠃ᛶࡢᙉ࠸㓄఩Ꮚࡢ౑⏝ࡀ㘽࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ㸦B. Zhu,
S.Sakaki, ACS. Cat. 2021, 11, 10681−10693㸧

- 63 -

3.2 Fe55, Co55, Ni55, ཬࡧ Cu55 ᚤ⢏Ꮚୖ࡛ࡢ NO ࡢゎ㞳྾╔཯ᛂᛶࡢ⌮ㄽⓗ◊✲㸸NO ࡢゎ㞳྾╔ࡣ NOx 㑏ඖ཯ᛂࡢ㔜せ࡞⣲཯ᛂ㐣⛬࡛࠶ࡿࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊNOࡢゎ㞳྾╔཯ᛂᛶࡣ㔠ᒓඖ⣲ࡢ࿘ᮇ⾲ୖ࡛ࡢ఩⨨࡟౫Ꮡࡋ࡚࠸ࡿࠋ3d 㔠ᒓ࡛ࡣ Fe, Co, Ni ࡣゎ㞳྾╔ࢆࠊCu࡛ࡣ஧㔞໬ࢆ㐍⾜ࡉࡏࡿࠋ4d 㔠ᒓ࡛ࡣ Ru, Rh ࡛ࡣゎ㞳྾╔ࢆࠊPd ࡛ࡣศᏊ≧྾╔ࢆࠊAg ࡛ࡣ஧㔞໬ࢆ㐍⾜ࡉࡏࡿࠋᐇ㝿࡟ M55 ࢆࣔࢹࣝ࡜ࡋ࡚ NO ࡢ཯ᛂᛶࢆ᳨ウࡋࡓ࡜ࡇࢁࠊFig. 1 ࡟♧ࡋ࡚࠸ࡿࡼ࠺࡟ࠊCu ࡛ࡢゎ㞳྾╔ࡣᅔ㞴࡛࠶ࡿࡀࠊࡑࢀ௨እࡢ㔠ᒓ࡛ࡣᐜ᫆࡟
㐍⾜ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ4d 㔠ᒓ࡟ࡘ࠸࡚ࡣ᫖ᖺᗘ᳨ウࢆ῭ࡲࡏ࡚࠸ࡿࠋCu ୖ࡛ࡢ NO ஧㔞໬ࡣࡍ࡛࡟᳨ウ

Fig. 1. Energy change in NO dissociative adsorptionࡋ࡚ሗ࿌῭ࡳ࡛࠶ࡿࠋNO ゎ㞳྾╔ࡢ㑄⛣≧ែࡢ࢚ࢿon Fe55, Co55, Ni55, and Cu55particlesࣝࢠ࣮࠿ࡽ཯ᛂᛶࡣ Fe < Co < Ni <<Cu ࡢ㡰࡟኱ࡁࡃ࡞ࡗ࡚࠸ࡿ(Table 1)ࠋd-valence band top ࡢ࢚ࢿࣝࢠ࣮, d-valenceband center ࡢ࢚ࢿࣝࢠ࣮ࡀపࡃ࡞ࡿ࡟ᚑ࠸ࠊM-N ࠾ࡼࡧ M-O⤖ྜࡣᙅࡃ࡞ࡾࠊTS ࡣ࢚ࢿࣝࢠ࣮ⓗ࡟పࡃࠊM-N, M-O ⤖ྜࡣᙉࡃ࡞ࡿࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ㹢㌶㐨ࡀ NO ࡢ⤖ྜษ᩿࡜
M-N, M-O ⤖ྜᙧᡂ࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠾ࡾࠊࡑࡢ㌶㐨
࢚ࢿࣝࢠ࣮ࡀ㧗࠸࡯࡝ࠊNO ࡬ࡢ㟁Ⲵ⛣ືࡀᙉࡃࠊࡲࡓࠊཎ
Ꮚ౯㌶㐨ࡢ࢚ࢿࣝࢠ࣮ࡢప࠸ N ࠾ࡼࡧ O ཎᏊ࡜㔠ᒓᚤ⢏Ꮚ࡜ࡢ⤖ྜࡀᙉࡃ࡞ࡿࡓࡵ࡛࠶ࡿࠋ (N. Takaki, M. Ehara, S.

Table 1. Activation bariier (Ea), d-valence band
top H(d-top), d-valence band center, and M-N,
M-O bond energies.
E(TS)
(Ea)

Fe55
-49.6
(14.0)

Co55-40.2(25.2)

Ni55-37.3(18.2)

Cu55
65.8(90.4)'E
H(d-top)H(d-c)
BE(M-N)
BE(M-O)-126.6
-3.30
-5.00
143
150

-107.5
-3.20
-5.67
129
138

-98.8
^3.60
^6.27
130
134

-51.9
-5.40
-7.21
101
117

Sakaki, ACS Omega., 6, 4888-4898 (2021)).
3.3 Co13@Pt42 ࠾ࡼࡧ Ni13@Pt42 ୖ࡛ࡢ㓟⣲㑏ඖ཯ᛂࡢ⌮ㄽⓗ◊✲㸸⇞ᩱ㟁ụ㟁ᴟ࡟ࡣⓑ㔠ࡀ౑⏝ࡉࢀ࡚࠸ࡿࡀࠊ
࿘▱ࡢࡼ࠺࡟ⓑ㔠ࡣ㧗౯࣭ᕼᑡ࡛࠶ࡿࠋⓑ㔠ࢆࢩ࢙ࣝ࡜ࡋࠊࢥ࢔࡟Ᏻ౯࡞ 3d 㔠ᒓࢆ౑⏝ࡋࡓࢥ࢔ࢩ࢙ࣝ㔠ᒓᚤ⢏Ꮚࡣࠊⓑ㔠࡜ྠᵝࡢάᛶࢆᣢࡕࠊⓑ㔠౑⏝㔞ࡣῶᑡࡉࡏࡿࡇ࡜ࡀฟ᮶ࡿࠋࡑࡇ࡛ࠊCo ࠾ࡼࡧ Ni ࢆࢥ࢔࡜ࡍࡿࢥ࢔ࢩ࢙ࣝᚤ⢏ᏊࠊCo13@Pt42 ࠾ࡼࡧ

Scheme 3. All possible elementary steps in
Fig. 2 Energy changes in O2 reduction on Co13@Pt42 core-shell particle
Pt-catalyzed O2 reduction reaction- 64 -

Ni13@Pt42 ୖ࡛ࡢ㓟⣲㑏ඖ཯ᛂࡢ⌮ㄽⓗ◊✲ࢆ DFT ィ⟬ࢆ⏝࠸࡚⾜࠸ࠊPt55 ୖ࡛ࡢࡑࢀ࡜ẚ㍑ࡋࡓࠋScheme 3࡟♧ࡍࡼ࠺࡞඲࡚ࡢ⣲཯ᛂ㐣⛬ࢆ᳨ウࡋࠊ཯ᛂࡣ O2 ྾╔ÆH+, e௜ຍÆOO ⤖ྜ㛤⿣ÆOH ⏕ᡂÆ H+, e௜ຍÆH2O ⏕ᡂÆ H+, e௜ຍÆOH ⏕ᡂÆ H+, e௜ຍÆH2O ⏕ᡂ࡛㐍⾜ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋCo13Pt42 ࡢሙྜࡢ࢚ࢿࣝࢠ࣮ኚ໬ࢆ Fig. 2 ࡟♧ࡋࡓࡀࠊᚊ㏿ࡣ 2 ࡘࡵࡢ OH ⏕ᡂ࡛࠶ࡿࠋNi13Pt42 ࡟ሙྜࡶྠᵝ࡛࠶ࡗࡓࠋࡋ࠿
ࡋࠊPt55 ࡛ࡣ 2 ศᏊ┠ࡢ H2O ⏕ᡂࡀᚊ㏿࡛࠶ࡾࠊࡇࢀࡽࡢάᛶ㞀ቨࡣ Ni (0.66 eV) < Co (0.80 eV) < Pt (1.10 eV)ࡢ㡰࡟኱ࡁࡃ࡞ࡿࠋ⇞ᩱ㟁ụ㟁ᴟゐ፹ࡣࠊάᛶ㞀ቨࡔࡅ࡛࡞ࡃࠊonset potential ࡟ࡶ౫ᏑࡍࡿࠋOnset potential
ࡣ Co (0.69 eV) > Ni (0.59 eV) > Pt (0.54 eV)࡜࡞ࡾࠊNi13@Pt42 ࠾ࡼࡧ Co13@Pt42 ࢥ࢔ࢩ࢙ࣝᚤ⢏Ꮚࡣ࠸ࡎࢀࡶ
Pt55 ࡼࡾࡶ㧗άᛶ࡛࠶ࡾࠊ㟁఩ࡶ኱ࡁࡃ࡞ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊࢥ࢔ࢩ࢙ࣝᚤ⢏Ꮚࡢ㹢ཎᏊ౯‽఩ࡢ࢚ࢿࣝࢠ࣮ࡀప࠸ࡇ࡜࠿ࡽㄝ᫂ฟ᮶ࡓࠋᚑࡗ࡚ࠊࢥ࢔ࢩ࢙ࣝᚤ⢏ᏊࡣᏳ౯࡟࡞ࡿ࡜ඹ࡟ࠊ㟁ᴟゐ፹ࡢᛶ⬟ࡶྥୖࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ(B. Zhu, S. Sakaki, J. Cat., 397, 13-26 (2021)).
3.4 Chromate spinel MCr2O4 (M = Mg, Co, Cu, and Zn)ୖ࡛ࡢ CO 㓟໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸⮬ື㌴᤼Ẽ࢞ࢫί໬ゐ፹࡛ࡣ࢞ࢯࣜࣥṧᕪࡸ CO ࢆ᏶඲࡟⇞↝ࡉࡏࡿࡓࡵ Pd, Pt ᚤ⢏Ꮚࡀ౑⏝ࡉࢀ࡚᮶ࡓࠋ᭱㏆ࠊPd, Pt ᚤ⢏Ꮚ࡟௦ࢃࡾ Cr ࡢࢫࣆࢿࣝᆺ㓟໬≀ࡀ౑⏝ྍ⬟࡞ࡇ࡜ࡀ⸃ᦶࡽ࡟ࡼࡾሗ࿌
ࡉࢀࡓࡀࠊCr ࡢࢫࣆࢿࣝᆺ㓟໬≀ࡢゐ፹స⏝ࡸ཯ᛂᶵᵓࡣ୙࡛᫂࠶ࡿࠋ
ࡑࡇ࡛ࠊMCr2O4 (M = Mg, Co, Cu, and Zn)ୖ࡛ࡢ CO 㓟໬཯ᛂࡢ⌮ㄽ◊✲ࢆ periodic-DFT ィ⟬࡟ࡼࡾ⾜ࡗࡓࠋCO ࡣ⾲㠃ࡢ㔠ᒓ࡛࡞ࡃ⾲㠃㓟⣲࡟྾╔ࡋࠊCO2 ࡟ኚ᥮ࡉࢀࠊ⏕ᡂࡋࡓ㓟⣲Ḟ㝗(Ov-site)࡟Ẽ┦୰࠿ࡽศᏊ≧㓟⣲ࡀ྾╔ࡋࠊᮎ➃ࡢάᛶ㓟⣲ཎᏊࡀḟ࡟྾╔ࡋࡓ CO ࡜཯ᛂࡋ࡚㐍⾜ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋάᛶࡣ CuCr2O4(111) < cubic MgCr2O4(111) < cubic
CoCr2O4(111)-A < cubic ZnCr2O4(111) < cubic-CoCr2O4(111)-B < tetragonal
CuCr2O4(100) ࡢ 㡰 ࡟ ኱ ࡁ ࡃ ࡞ ࡿ ࠋ tetragonal CuCr2O4(100) ࠊ cubic
CoCr2O4(111)-Aࠊ
tetragonal CuCr2O4(100)ࡣ 2 ࡘࡵࡢ CO2 ⏕ᡂ㺂ࡑࢀ௨እࡣࠊ
1 ࡘࡵࡢ CO2 ⏕ᡂ࡛࠶ࡿࠋάᛶ࡜ Ov ⏕ᡂ࢚ࢿࣝࢠ࣮㛫࡟ⅆᒣᆺ┦㛵ࡀ࠶ࡿࡇ࡜ࡀぢ࠸ࡔࡉࢀࡓ㸦Fig. 3㸧
ࠋ㔠ᒓ M ཎᏊࡢຠᯝࡣ M ࡀ࡝ࡢࡼ࠺
࡞㓟໬ᩘࢆྲྀࡿ࠿ࠊ㟁Ẽ㝜ᛶᗘࡢ኱ᑠ࡛⌮ゎฟ᮶ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋ
(P. Zhao, M. Ehara, A. Satsuma, S. Sakaki, J. Cat., 393, 30–41 (2021)).

4

Fig. 3 CO adsorption energy andactivation barrier vs. Ov formationenergyⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

ཎⴭㄽᩥ‫ۻ‬P. Zhao, M. Ehara, A. Satsuma, S. Sakaki, J. Cat., 393, 30–41 (2021). ‫ۻ‬N. Takagi, M. Ehara, S. Sakaki,
ACS Omega, 2021, 6, 7, 4888–4898. N. Hara, K. Yamamoto, Y. Tanaka, T. Saito, S. Sakaki,* Y. Nakao, Bull. Chem.
Soc. Jpn. 94, 1859-1868 (2021). ‫ۻ‬B. Zhu, J. Lu, S. Sakaki, J. Cat., 397, 13-26 (2021). Y. Gu, J.-J. Zheng, K. Otake, M.
Shivanna, S. Sakaki, H. Yoshino, M. Ohba, S. Kawaguchi, Y. Wang, F. Li, S. Kitagawa, Angew. Chem. Int. Ed. 60,
11688–11694 (2021). I. Inoue, K. Yamamoto, S. Sakaki, T. Murahashi, Chem. Eur. J. 27, 10558 –10562 (2021). ‫ۻ‬B.
Zhu, S. Sakaki, ACS Catal., 11, 10681–10693 (2021), N. Hara, K. Aso, Q.-Z. Li, S. Sakaki, Y. Nakao, Tetrahedron, 95,
132339 (2021), D. Yang, P. Bao, Z. Yang, Z. Chen, S. Sakaki, S. Maeda, G. Zeng, ChemCatChem, 13, 1–6 (2021), ‫ۻ‬P.
Zhao, M. Ehara, A. Satsuma, S. Sakaki, J. Phys. Chem. C., 125, 25983-26002 (2021). J.-J. Zheng and S. Sakaki, J.
Photochem. Photobio. C, 51, 100482 (2022). ‫ۻ‬J. Yin, M. Ehara, S. Sakaki, Phys. Chem. Chem. Phys. 2022, 24,10420-10438. Q. Z. Li, N. Hara, K. Semba, Y. Nakao, S. Sakaki, Topics in Cat., 65, 392–417 (2022). ‫ۻ‬R.-L. Zhong, K.
Suzuki, M. Yamashita, S. Sakaki, ACS Catal., 12, 4880–4897 (2022).
Ꮫ఍Ⓨ⾲㸸ゐ፹ウㄽ఍㸹ཱྀ㢌Ⓨ⾲  ௳ࠊ㘒య໬Ꮫウㄽ఍㸹ཱྀ㢌Ⓨ⾲  ௳ࠊ3DFLILFKHP ᣍᚅㅮ₇  ௳- 65 -

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ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃᒁᡤ≀⌮㔞࡟ࡼࡿࢫࣆࣥࢲ࢖ࢼ࣑ࢡࢫゎᯒ
6SLQG\QDPLFVDQDO\VLV 
E\ORFDOTXDQWLWLHVEDVHGRQTXDQWXPILHOGWKHRU\‫℩ۑ‬Ἴ ኱ᅵ, 㯮⏣ ┤ஓ, ᓥ⏣ 㝯ྐ, ྜྷ⏣ ዴᐶ, 㯮⏣ ᣅᮭ, ⏣୰ ᾏᩯ㸦ி㒔኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧◊✲┠ⓗࡽࡏࢇᙧ≧ࢆࡶࡘ᭷ᶵศᏊ୰ࢆ㟁Ꮚࡀ㏻㐣ࡍࡿ㝿࡟ࢫࣆࣥࡀศᴟࡍࡿ⌧㇟࡜ࡋ࡚ࠊ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡀ᭱㏆Ⓨぢࡉࢀࡓࠋࢫࣆࣥศᴟࡣࢫࣆࣥ㌶㐨┦஫స⏝࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࡀࠊࡇࡢࡼ࠺࡞኱ࡁ࡞ࢫࣆࣥ
㌶㐨┦஫స⏝ࡀ࡝ࡇ࠿ࡽ⏕ࡌ࡚࠸ࡿࡢ࠿ࢃ࠿ࡽࡎࠊ࡝ࡢࡼ࠺࡞࣓࢝ࢽࢬ࣒࡛࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡢࢫࣆࣥศᴟࡀ㉳ࡇࡿ࠿ࡣ୙࡛᫂࠶ࡿࠋሙࡢ㔞Ꮚㄽ࡟࠾ࡅࡿࢫࣆࣥࢲ࢖ࢼ࣑ࢡࢫࡢグ㏙࡟ࡣࠊ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕
ㄏ㉳ࢫࣆࣥࢺࣝࢡ࡛࠶ࡿࢶ࢙࣮ࢱຊࡀᏑᅾࡍࡿࡇ࡜ࡀ㏆ᖺ㆟ㄽࡉࢀ࡚࠸ࡿࠋ࢚ࢿࣝࢠ࣮ࡢどⅬ࡛࠶ࡿࢫࣆࣥ
㌶㐨┦஫స⏝࠿ࡽ㞳ࢀ࡚ࢫࣆࣥࢺࣝࢡࡢどⅬ࠿ࡽ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶ࡜ࢶ࢙࣮ࢱຊࡢ┦㛵ᛶࢆ᫂ࡽ࠿
࡟ࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡣ㟁Ꮚࡢὶࢀࢆక࠺⌧㇟࡛࠶ࡿࡢ࡛ࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲࢆ⏝࠸࡚㟁Ẽఏᑟ㔞Ꮚ≧ែィ⟬ࢆ⾜࠺ࠋࡇࡢィ⟬ࡣࠊࢫࣆࣥ㌶㐨┦஫స⏝ࢆྲྀࡾධࢀࡓィ⟬ࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽ OpenMX ࢆ⏝࠸࡚ᐦᗘỗ㛵ᩘἲ࡟ࡼࡾἼື㛵ᩘࡢィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࡋ࡚ᚓࡓἼື㛵ᩘ࡟ᑐࡋ࡚ࠊࢶ࢙࣮ࢱຊࡸࢫࣆࣥ
ศᴟ࡞࡝ࡢ≀⌮㔞ࡣ QEDynamics ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ



◊✲ᡂᯝ
ࡽࡏࢇᵓ㐀ࡢ᭷ᶵศᏊෆࢆ㟁Ꮚࡀ㏻㐣ࡍࡿ㝿࡟ࢫࣆࣥࡀศᴟࡍࡿ࡜࠸࠺࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡢ࣓࢝

ࢽࢬ࣒ゎ᫂࡟ྥࡅ࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㏻ࡌࡓ⌮ㄽ◊✲ࢆ⾜ࡗࡓࠋ≉࡟ࢫࣆࣥࡢྥࡁࢆኚ࠼ࡿࢺࣝࢡ࡟ὀ┠ࡋ࡚◊✲ࢆ⾜ࡗࡓࠋᡃࠎࡣ࢝࢖ࣛࣝ࡞ᵓ㐀ࢆᣢࡘศᏊ࡜ࡋ࡚ࠊࡽࡏࢇᵓ㐀ࢆᣢࡘ࣊ࣜࢭࣥ࡜ࡽࡏࢇᵓ㐀࡛ࡣ࡞࠸࢔ࣛࢽࣥࢆᑐ㇟࡜ࡋࡓࠋศᏊࢆ㏻㐣ࡍࡿ㟁Ꮚࡣࢫࣆࣥࢺࣟࢽࢡࢫ࡬ࡢᛂ⏝ࡶ⪃࠼㟁Ẽఏᑟ≧ែࢆ᝿ᐃࡋࠊ
㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲࢆ⏝࠸࡚㔞Ꮚ≧ែࢆィ⟬ࡋࡓࠋ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡀ⏕ࡳฟࡍࢫࣆࣥศᴟࡢ㔞࡜ఏᑟ㟁Ꮚࡀཷࡅࡿࢶ࢙࣮ࢱຊࡢ㛫┦㛵ࡀ࠶ࡿࡇ࡜ࢆ♧ࡋࡓࠋࡇࡢ┦㛵ࡣ࣊ࣜࢭࣥ࡜࢔ࣛࢽࣥࡢ㛫࡛኱ࡁ࡞ᕪࡣ࡞ࡃࠊඛ⾜◊✲࡛ᣦ᦬ࡉࢀ࡚࠸ࡓࡽࡏࢇᵓ㐀࡛ࡣ࡞ࡃ࡚ࡶ࢝࢖࡛ࣛࣝ࠶ࢀࡤ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࢆ♧ࡍࡇ࡜ࢆ෌⌧ࡋࡓࠋ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲ࡟ࡼࡿࢫࣆࣥศᴟ㔞ࡣඛ⾜◊✲ྠᵝ࡟ᐇ㦂࡛ほࡉࢀࡿࢫࣆࣥศᴟ㔞࡯࡝ࡢ኱ࡁࡉ࡜ࡣ࡞ࡽ࡞࠿ࡗࡓࡀࠊ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡢ◊✲ࢆ⾜࠺࡟༑ศ࡞㔞ࡢศᒁࡀᚓ
ࡽࢀࡓࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] Masato Senami, (Plenary), “Electron chirality in chiral molecules and chirality induced spin selectivity”, The 7th
Quantum Science (QS) symposium -The Main Symposium of International Conference of Computational Methods inSciences and Engineering (ICCMSE) 2021, 2021/9/4-7, Galaxy Hotel, Crete, Greece and online.

- 68 -

[2] Naoya Kuroda, Ayaki Sunaga, and Masato Senami, (Oral), “Understanding of T, P violating interaction parameters inpolyatomic polar molecules”, The 7th Quantum Science (QS) symposium -The Main Symposium of International
Conference of Computational Methods in Sciences and Engineering (ICCMSE) 2021, 2021/9/4-7, Galaxy Hotel, Crete,
Greece and online.
[3] Ayaki Sunaga, Naoya Kuroda, Takumi Oho, and Masato Senami, ͆Parity-violating energy difference in chiralmolecules enhanced by electronic excitation”, (Oral, Invited), The 7th Quantum Science (QS) symposium -The Main
Symposium of International Conference of Computational Methods in Sciences and Engineering (ICCMSE) 2021,
2021/9/4-7, Galaxy Hotel, Crete, Greece and online.
[4] Naoya Kuroda, Takumi Oho, Ayaki Sunaga, and Masato Senami, ͆Enhancement of Parity-Violating energy differenceof H2X2 molecules by electronic excitation”, The 2021 International Chemical Congress of Pacific Basin Societies(Pacifichem 2021), Honolulu, December, 2021.
[5] Yukihiro Yoshida, and Masato Senami, ͆Theoretical study on the spin-dependent component of the electron tension
density in electrical conduction phenomena”, The 2021 International Chemical Congress of Pacific Basin Societies(Pacifichem 2021), Honolulu, December, 2021.
[6] 㯮⏣ ┤ஓ㸪℩Ἴ ኱ᅵ, ͆ᴟᛶከཎᏊศᏊ࡟࠾ࡅࡿ᫬㛫࣭✵㛫཯㌿ᑐ⛠ᛶ◚ࢀࡢ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡢゎᯒ͇(ཱྀ㢌), ➨ 23 ᅇ ⌮ㄽ໬Ꮫウㄽ఍, ࢜ࣥࣛ࢖ࣥ㛤ദ.
[7] ྜྷ⏣ ዴᐶ, ℩Ἴ ኱ᅵ͆㟁Ẽఏᑟ⌧㇟࡟࠾ࡅࡿ㟁Ꮚࢸࣥࢩࣙࣥᐦᗘࡢࢫࣆࣥ౫Ꮡᡂศ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲͇(࣏ࢫࢱ࣮) , ➨ 23 ᅇ ⌮ㄽ໬Ꮫウㄽ఍, ࢜ࣥࣛ࢖ࣥ㛤ദ.
[8] 㯮⏣ ┤ஓ㸪᪊ಖ໶㸪◁㈡ᙬග㸪℩Ἴ኱ᅵ, ͆ࣃࣜࢸ࢕ࡢ◚ࢀ࡟㉳ᅉࡍࡿ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪࡢ㟁Ꮚບ㉳࡟ࡼࡿቑ኱͇ (ཱྀ㢌), ᪥ᮏ≀⌮Ꮫ఍ 2021 ᖺ⛅Ꮨ኱఍, 21aA1-8, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2021 ᖺ 9 ᭶ 21 ᪥.
[9] 㯮⏣ ┤ஓ㸪᪊ಖ໶㸪◁㈡ᙬග㸪℩Ἴ኱ᅵ, ͆┦ᑐㄽⓗ EOM-CC ἲࢆ⏝࠸ࡓ㙾ീ␗ᛶయ㛫ࡢ࢚ࢿࣝࢠ࣮ᕪ
ࡢィ⟬: 㟁Ꮚບ㉳࡟ࡼࡿ≉␗ⓗቑ኱͇ (ཱྀ㢌), ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍,4E03, ໭ᾏ㐨኱Ꮫ(࢜ࣥࣛ࢖ࣥ), 2021
ᖺ 9 ᭶ 18-21 ᪥[10] ྜྷ⏣ ዴᐶ㸪℩Ἴ ኱ᅵ, ͆㟁Ẽఏᑟ⌧㇟࡟࠾ࡅࡿࢫࣆࣥศᴟ࡜㟁Ꮚࢸࣥࢩࣙࣥᐦᗘࡢ㛵ಀ͇(࣏ࢫࢱ࣮),➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍, 4P088, ໭ᾏ㐨኱Ꮫ(࢜ࣥࣛ࢖ࣥ), 2021 ᖺ 9 ᭶ 18-21 ᪥[11] ᓥ⏣ 㝯ྐ㸪℩Ἴ ኱ᅵ, ͆㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲࢆ⏝࠸ࡓ㟁Ẽఏᑟィ⟬࡟࠾ࡅࡿ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶ࡜ࢶ࢙࣮ࢱຊࡢ㛵ಀ͇ (ཱྀ㢌), ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍, 2E12, ໭ᾏ㐨኱Ꮫ(࢜ࣥࣛ࢖ࣥ), 2021 ᖺ 9 ᭶ 1821 ᪥
[12] 㯮⏣ ┤ஓ㸪᪊ಖ໶㸪◁㈡ᙬග㸪℩Ἴ኱ᅵ, ͆㟁Ꮚບ㉳࡟ࡼࡿ㙾ീ␗ᛶయ㛫࢚ࢿࣝࢠ࣮ᕪࡢቑ኱-┦ᑐㄽⓗ
EOM-CC ἲ࡟ࡼࡿホ౯͇ (ཱྀ㢌), ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨᖺ఍, 1O15,⟃Ἴ኱Ꮫィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮(࢜ࣥࣛ࢖ࣥ), 2021 ᖺ 11 ᭶.
[13] 㯮⏣ ┤ஓ㸪◁㈡ᙬග㸪℩Ἴ኱ᅵ, ͆㟁Ꮚ EDM ࡢ᥈⣴ࢆ┠ᣦࡋࡓከཎᏊᴟᛶศᏊ࡟࠾ࡅࡿ᫬㛫࣭✵㛫཯㌿ᑐ⛠ᛶ◚ࢀࡢゎᯒ͇ (ཱྀ㢌), ᪥ᮏ≀⌮Ꮫ఍ 2022 ᖺ ᖺḟ኱఍, 17pE26-3, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2022 ᖺ 3 ᭶.

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@ 1DR\D .XURGD 7DNXPL 2KR $\DNL 6XQDJD DQG 0DVDWR 6HQDPL ³(QKDQFHPHQW RI WKH SDULW\YLRODWLQJ HQHUJ\
GLIIHUHQFHRI+;PROHFXOHVE\HOHFWURQLFH[FLWDWLRQ´3K\V5HY$ - 69 -

"(4)Al-B !

 C-H 

Elucidating properties of reactive diborane(4)s and Al-B bonded
compounds, and design of homogeneous catalyst toward C-H activationof methane #%

$&

 ¡Ã´*"¾Öu% a[!_Ü/º 
VACPCQR<LPU0R96;DÔÕd!n )+<0QWRLQRÔÕd p ,
V<0R6R²  0E4U 8TTLPUn  l°p/,kx©/\,V  HU:W Õd/¼v ,O>U3?SU nsn Ë·,
VGDT6;2NDÀ~d/~g  /¿½Vp-/Òkjn,Òk46;RP<5R ¢,¡Ã"a[! 5 ÂÝ/¦«¤£ª"=KW=!ÐpZ(2)!&§ <0QWRLQRÔÕd!0R6UÞ!n¢¸Ä   l°pkx©!Ûw£Æ¢¸Ä   HU:W Õd ¼v,O>U3?SU!n¢¸  HU:W Õd!Ñbw¿½$q®n»¢¸  46;RP<5R!=HU}h»¢¸ "°ÊBW>/f Gaussian 16)#Î¨

)+ 3-5 !ÊÍk/·p.-*/ ]×d!ÊÍk/·--!n¯Ç!3FR7W/'(M06-2X/6-31+G(d)S

JR, PCM(SMD, benzene), DFT-D3BJ ¹) 
É" Al 0E4U 1 / Mes2BF n,2

Scheme 1.
Si Si

* I@k24U/¶Ú0R

MLPU 3,! 3

DMSO /n, Al  B !× Ò®mw g- 4/n,YÓ°p i- 5
/{ß£

CO

,

º(Scheme 1)¦«"!

n/»,'DFT ½­/·

AlK

Mes2BF(1 eq.)
toluene
r.t.
84%

Si Si
Al

B

Mes

F
Si Si
Si Si
(Et2O)2K
1
Si = SiMe3, Mes = 2,4,6-(Me)3C6H2

2

O
S

Et2O
r.t.
51%

Si Si
Al B

Mes
Mes

Si Si
3
Si Si

Mes
CO
C
3
Al O Bbenzenebenzene Al O B H
Mes
r.t.
r.t.
4
5 Mes
85%
39%

% DFT ½­ )+ 3 !ITUA10ÈÌ/»[Scheme 2(a)]HOMO "^- 70 -

SiOTf(1 eq.)

Al =

Al

Si Si
Si = SiMe3

Al–B l°p)#Mes r!ÈÌ!|\ t

LUMO "^

B mwZ!¬! 2p ÈÌ)# Mes r!*ÈÌ!|\ t 3  DMSO !n[Scheme 2(b)(c)]"DMSO !Ò®mw
n Öu,³*-, OzÑb ±Ñb]×d Int_6 !

Al

3 ! Al %" B mw ÑbÑb]×d Int_7 )+yB

BMes2 Ïb%" Al Ïb! 1,2-shift !k3FR7W"-(]×d!yz

/n TS6-4 ! c -".DMSO !Å  ÛÒ®mw )+Û£ Ø Al mw$ÑbÁ oµ,X3  CO !n"CO !®mw
]×d Int_8 !

ÑbBÑb]×d Int_11 )+yz[Scheme 2(d)(e)]-"] É

Al

CO !®mw Ñb,Ù"ÈÌ¥`e /',' )+3FR7W£ c 2p ÈÌ[Scheme 2(a)]/  B mw$Ñb, Ó+h(tInt_8 !  " Al Ïb! 1,2-shift

3FR7W£)+ Al $ÑbLP>AU Int_10 ! Mes r! 1,2-shift,LP0RU Int_13 ! AlO Ïb! 1,2-shift ±
Int_15 ! hw k )+ 5

Si Si

CO
Al

B

Al

B

Mes

3

3

HOMO
(b)
Me2S O

Me
S Me
O
Mes
Al B
Mes
Int_6

3
Me2S OMeMe SOAl B Mes
Mes
Int_7

(c)

CO

LUMO
Me
Me
S
O
Mes
Al B
Mes
TS6-4
Me
Me
S
O
Al

B

4

Al =

Al

B
Mes
TS10-13

B
Mes
Mes
Int_10

Mes

Mes
C
B
Mes

C

O

B Mes
Mes
Int_12

Al O

Int_13

O
C

Mes
C
C

B
Mes

AlO B

Mes
Int_14TS13-14

Mes
Mes

Int_14
TS6-4
18.1

H

5
C

C

AlO B
Mes
TS14-15

10.7
Int_7

B-coordination
pathway

B Mes

Int_9

Al

Al O

Al
C

Al

B Mes
Mes
TS8-9

C Mes

Int_10

Si Si
Si = SiMe3

TS7-4

SMe2
0.0
3

O

C

O
C

Me2SO

–119.5
4

Al

Al O

Si Si

TS7-4
19.9

SMe2

O

Mes
Al B
Mes
Int_11(+19.1 vs. Int_8)

–SMe2

–SMe2

O
C
Al B Mes
Mes
Int_8

2.7
Int_6

–119.5
4
Al-coordination

pathway(e)Int_11
18.2

Energy (kcal/mol)

Energy (kcal/mol)

C-H °pi ),4RC6<O>U]×d

(d)

Si Si
Mes

CO
0.0
3

AlO B

C

H

AlO B

Mes
Int_15

Int_12
1.7

3.4
–0.9
Int_8 TS8-9 –11.7 –5.1
Int_10
Int_9

TS3
–1.8

H

Mes
TS15-5

TS4
–4.9

TS5
–10.3

–13.7
Int_13

TS6
–38.9

–31.4
Int_14–53.4
Int_15



!



)

,/* Scheme 2.
(a)

Al B

 'Á-,x¢¸"
1.

Suzuki, A.; Wu, L.; Lin, Z.; Yamashita, M., Angew. Chem. Int. Ed. 2021, 60, 21007-21013.

2.

Wu, L.; Kojima, C.; Lee, K.-H.; Morisako, S.; Lin, Z.; Yamashita, M., Chem. Sci. 2021, 12, 9806-9815.

3.

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

4.

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

- 71 -–68.95

㔠ᒓ⺮ⓑ㉁ࡢ㟁Ꮚᵓ㐀ไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study of the electronic structures of metalloprotein‫ۑ‬㮚㔝ඃ㸪㰻⸨ᚭ㸪㏆⸨ᐶᏊ㸪වᯇభ඾
㸦ᗈᓥᕷ❧኱Ꮫ࣭໭ぢᕤᴗ኱Ꮫ࣭ᗈᓥ኱Ꮫ㸧◊✲┠ⓗࠊෆᐜ
㔠ᒓ⏕యศᏊ┦஫స⏝ࡢゎ᫂ࡣ⏕࿨⌧㇟ࡢ⌮ゎࢆ῝ࡵࡿࡔࡅ࡛࡞ࡃࠊ᪂ࡋ࠸ࣉ࣮ࣟࣈࡸ⸆๣ࡢྍ⬟ᛶࢆ୚࠼ࡿࠋࡑࡢゎ᫂࡟ࡣάᛶ୰ᚰࡢ」㞧࡞㟁Ꮚ≧ែ࡜ࡑࡢࡲࢃࡾ࡟㓄఩ࡋ࡚࠸ࡿ⺮ⓑ㉁ࢆྵࢇࡔᕧ኱࡞⣔ࢆྠ᫬࡟ྲྀࡾᢅࢃ࡞ࡅࢀࡤ࡞ࡽࡎ㧗ᛶ⬟࡞ࢥࣥࣆ࣮ࣗࢱࢆᚲせ࡜ࡍࡿࠋࡑࡇ࡛ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬㈨※ࢆ฼⏝ࡋ࡚ࠊ࿘ࡾࡢ⺮ⓑ㉁ࡢຠᯝࢆྲྀࡾ㎸ࢇࡔ㔠ᒓ⺮ⓑ㉁ࡢ㟁Ꮚ≧ែィ⟬ィ⟬࡟ࡼࡾ㔠ᒓ࡜⏕యศᏊࡢ┦஫స⏝ࡢศᏊ࡛ࣞ࣋ࣝࡢゎ᫂ࢆ┠ᣦࡋࡓࠋලయⓗ࡟ࡣ௨ୗࡢࡇ࡜ࢆ⾜ࡗࡓࠋ࣒࣊⺮ⓑ㉁࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎᯒ࣒࣊⺮ⓑ㉁ࡣ࣒࣊ࢆ⿵ᅉᏊ࡟ࡶࡘ⺮ⓑ㉁ࡢ⥲⛠࡛࠶ࡾࠊྠ୍ࡢᇶᮏ㦵᱁ࢆᣢࡘ࡟ࡶ࠿࠿ࢃࡽࡎ㸪」ྜయࢆ
ᙧᡂࡍࡿ⺮ⓑ㉁࡟ࡼࡾ␗࡞ࡿᶵ⬟ࢆⓎ⌧ࡍࡿࠋ࣒࣊ࡢᶵ⬟ไᚚ࣓࢝ࢽࢬ࣒ࡣᮍࡔ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡽࡎ㔜せ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋඛ⾜◊✲࡛ࡣࠊ࣒࣊ࡢṍࡳ࡟ࡼࡿ࣒࣊ࡢ≀ᛶࡸ⺮ⓑ㉁ᶵ⬟࡬ࡢ㛵୚ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋ
ࡑࡇ࡛ࠊ࣒࣊ࡢṍࡳ㸦ศᏊᵓ㐀㸧࡜⺮ⓑ㉁࣏ࢣࢵࢺࡢᵓ㐀ࡢ┦㛵ࡢ᭷↓ࢆㄪ࡭ࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ῝ᒙᏛ⩦ࢆ⏝࠸࡚࣒࣊ࡀ⤖ྜࡋ࡚࠸ࡿ⺮ⓑ㉁࣏ࢣࢵࢺࡢ❧యᵓ㐀࠿ࡽ࣒࣊ࡢṍࡳࢆண࡛ࡁࡿ࠿࡝࠺࠿ࢆ᳨ウࡋࡓࠋ3QRU ࡢ 12 ⏕ᡂ཯ᛂ㐣⛬ࡢゎᯒ

3QRU 䛿୍㓟໬❅⣲ 12 䜢 12 䛻㑏ඖ䛩䜛䝦䝮䝍䞁䝟䜽㉁䛷䛒䜛䚹䛭䛾཯ᛂ䝃䜲䜽䝹㐣⛬䛿䚸䝦䝮ୖ䛻Ỉ䜢㓄఩䛧䛯ఇṆᆺ䚸ᇶ㉁䛾୍㓟໬❅⣲䜢⤖ྜ䛧䛯 12 ᆺ䚸 1$'+ 䛻䜘䛳䛶 12 䜢㑏ඖ䛧䛯୰㛫య䛻኱ู䛥䜜䜛䚹㏆ᖺᡃ䚻䛿୰㛫య䛾ᵓ㐀䛜䝠䝗䝸䝗 㑏ඖ䛥䜜䛯┤ᚋ䛾 +12±䛾≧ែ䛷Ꮡᅾ䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹䜎䛯䚸᫬㛫ศゎ䝅䝸䜰䝹䝣䜵䝮䝖⛊⤖ᬗᏛ 756); 䛻䜘䜛 3QRU 䛾୰㛫య䛾⤖ᬗᵓ㐀䜒ゎ䛛䜜䛶䛚䜚䚸䛣䜜䜢䜒䛸䛻䛧䛯⌮ㄽゎᯒ䛻䜘䜚 3QRU 䛾୰㛫యᚋ䛾཯ᛂ㐣⛬䛾ヲ⣽䛺ᶵᵓ䛾ゎ᫂䛻䛴䛺䛜䜛䛸ᮇᚅ䛥䜜䛶䛔䜛䚹䛭䛣䛷ᡃ䚻䛿㔞Ꮚ໬Ꮫィ⟬䜢⏝䛔䛶 3QRU ཯ᛂ୰㛫య䛾άᛶ䜢⌮ㄽⓗ䛻ホ౯䛩䜛䛣䛸䛷䚸୰㛫య䛛䜙 12 ⏕ᡂ䛻䛔䛯䜛䜎䛷䛾཯ᛂ㐣⛬䛾ศᏊᶵᗎ䜢ゎᯒ䛧䛯䚹◊✲᪉ἲࠊィ⟬᪉ἲ࣒࣊⺮ⓑ㉁࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎᯒ

3URWHLQ'DWD%DQN 㸦3'%㸧࠿ࡽ࣒࣊ DEFR ࡢ࠸ࡎࢀ࠿ࢆྵࡳࠊศゎ⬟ࡀ c ௨ୗࡢ࢚ࣥࢺ࣮ࣜࢆᢤࡁฟ
ࡋࡓࠋࡇࢀࡽࡢ࢚ࣥࢺ࣮ࣜ࠿ࡽࠊ㍈㓄఩Ꮚࡀ࢔࣑ࣀ㓟ṧᇶࡢࡳ࡛࠶ࡾࠊ࠿ࡘ⺮ⓑ㉁࣏ࢣࢵࢺࡀᶆ‽࢔࣑ࣀ㓟ࡢࡳ࠿ࡽ࡞ࡿ㙐ࢆᢤࡁฟࡋࠊ3,6&(6 ࢧ࣮ࣂࢆ⏝࠸࡚㓄ิ㢮ఝᛶࡀ  ௨ୗ࡜࡞ࡿ㙐ࡢࢭࢵࢺࢆసᡂࡋࡓ
㸦㠀෕㛗ࢹ࣮ࢱࢭࢵࢺ㸧ࠋ⺮ⓑ㉁࣏ࢣࢵࢺࡣࠊ࣒࣊ࡢ࣏ࣝࣇ࢕ࣜࣥࢆᵓᡂࡍࡿ  ಶࡢ㔜ཎᏊࡢྛཎᏊ࠿ࡽ c ௨ෆ࡟  ࡘ௨ୖࡢཎᏊࡀධࡗ࡚࠸ࡿ࢔࣑ࣀ㓟ṧᇶࡢࢭࢵࢺ࡜ࡋࡓࠋ࣒࣊ࡢᗙᶆࢆࡶ࡜࡟⺮ⓑ㉁࣏ࢣࢵࢺࡢ
㡿ᇦࢆỴᐃࡋࠊࡑࢀࢆྛ㎶ࡢ㛗ࡉࡀ  c ࡢ❧᪉య㸦࣎ࢡࢭࣝ㸧࡟ศ๭ࡋ࡚࣏ࢣࢵࢺᵓ㐀ࢆ⾲⌧ࡋࡓࠋྛ࣎ࢡ
ࢭࣝ࡟ࡣཎᏊࡢ᭷↓࡟ࡼࡾ  ࡲࡓࡣ  ࡢᩘ್ࢆ๭ࡾᙜ࡚ࡓࠋ῝ᒙᏛ⩦ᡭἲࡢ &RQYROXWLRQDO 1HXUDO 1HWZRUN
&11  ࢆ⏝࠸࡚ࠊ⺮ⓑ㉁࣏ࢣࢵࢺࡢ❧యᵓ㐀࠿ࡽ࣒࣊ࡢṍࡳࡢண- 72 -

ࢆ⾜࠸ࠊ⺮ⓑ㉁⎔ቃ࡜࣒࣊ࡢṍࡳࡢ┦㛵ࢆゎᯒࡋࡓࠋ࣒࣊ࡢṍࡳࡢホ౯࡟ࡣ QRUPDOFRRUGLQDWHVWUXFWXUDOGHFRPSRVLWLRQ㸦16'㸧ࢆ⏝࠸ࠊ௦⾲ⓗ࡞  ಶࡢ ࣔ ࣮ ࢻ 㸦 VDGGOLQJ UXIIOLQJ GRPLQJ ZDYLQJ [  ZDYLQJ \  SURSHOOHULQJ PHVRVWUHWFKLQJ 1S\UUROH VWUHWFKLQJWUDQVODWLRQ [ WUDQVODWLRQ \ EUHDWKLQJURWDWLRQ㸧ࢆゎᯒᑐ㇟࡜ࡋࡓࠋ
࣒࣊⺮ⓑ㉁࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎᯒඹྠ◊✲⪅ࡼࡾᥦ౪ࡉࢀࡓ 3QRU ୰㛫యࡢ⤖ᬗᵓ㐀ࢆࡶ࡜࡟ࠊ40 㡿ᇦ࡜ࡋ࡚ࢱࣥࣃࢡ㉁ࡢ᭱ᑠ㝈ࡢάᛶ㒊఩㸦ᅗ 㸧ࢆษࡾฟࡋࡓࣔࢹࣝࢆᵓ⠏ࡋࡓࠋ40 㡿ᇦࡣ %/<3 ỗ㛵ᩘ࡛ྲྀࡾᢅࡗࡓࠋᇶᗏ㛵ᩘ⣔ࡣ )H1
2 6 ཬࡧᇶ㉁ୖࡢỈ⣲ཎᏊ࡟ࡣ * GS ࠊࡑࢀ௨እࡢཎᏊ࡟ࡣ GHIVYS ࢆ⏝࠸ࡓࠋ୰㛫య࡟ᑐࡋ࡚㸰ࡘ┠ࡢ 12 ศᏊࡀ཯ᛂࡋ 12 ࢆ⏕ᡂࡍࡿ཯ᛂࡢ⤒㊰᥈⣴ࢆ⾜࡞ࡗࡓࠋ



◊✲ᡂᯝ


࣒࣊⺮ⓑ㉁࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎᯒ

&11 䛻䜘䜛┦㛵ゎᯒ䛷䛿䚸䜎䛪䠈16' 䛷ᚓ䜙䜜䛯  ಶ䛾᣺ື䝰䞊䝗䜢⧳䜑䛶ண䛧䛯䚹ྛ᣺ື䝰䞊䝗䛻䛴䛔䛶ண್䛸ほ ್䛾┦㛵ಀᩘ䜢ゎᯒ䛧䛯䛸䛣䜝䚸ୖ఩  䛴䛾᣺ື䝰䞊䝗䠄VDGGOLQJ UXIIOLQJ GRPLQJ DQG ZDYLQJ [ 䠅䛻䛴䛔䛶ẚ㍑ⓗ㧗䛔┦㛵䛜ぢ䜙䜜䛯䚹䛣䜜䜙  䛴䛾᣺ື䝰䞊䝗䛾䛖䛱䚸䝦䝮䛾㓟໬㑏ඖ㟁఩䜔㓟⣲ぶ࿴ᛶ䛸䛾┦㛵䛜▱䜙䜜䜛 VDGGOLQJ UXIIOLQJ GRPLQJ 䛻䛴䛔䛶䚸䛭䜜䛮䜜䛻≉໬䛧䛯 &11 䝰䝕䝹䜢సᡂ䛧䛯䚹 ᅇ஺ᕪ᳨ド䜢⾜䛳䛯⤖ᯝ䚸䛣䜜䜙䛾  䛴䛾ṍ䜏䛻䛴䛔䛶䝫䜿䝑䝖ᵓ㐀䛸䝦䝮䛾ṍ䜏䛾┦㛵䛜♧၀䛥䜜䛯䚹ධຊ䝕䞊䝍䛾᝟ሗ䜢㒊ศⓗ䛻๐䛳䛯ゎᯒ䜘䜚䝦䝮䛾ṍ䜏䛾ண䛻䛿䝫䜿䝑䝖⾲㠃௜㏆䛾᝟ሗ䛜㔜せ䛷䛒䜛䛣䛸䛜♧၀䛥䜜䛯䛣䛸䛛䜙䚸⺮ⓑ㉁䝫䜿䝑䝖䛾❧య㞀ᐖ䛜䝦䝮䛾ศᏊᵓ㐀䛻኱䛝䛟ᙳ㡪䛧䛶䛔䜛ྍ⬟ᛶ䛜䛒䜛䚹䜎䛯䚸㠀෕㛗䝕䞊䝍䝉䝑䝖䛻ᑐ䛩䜛⺮ⓑ㉁䛾䝫䜿䝑䝖ᵓ㐀䠄✵Ὕ㒊ศ䛾ᵓ㐀䠅䛾ẚ㍑䛛䜙䚸䝫䜿䝑䝖ᵓ㐀䛜ఝ䛶䛔䜜䜀䝦䝮䛾ศᏊᵓ㐀䜒ఝ䛶䛔䜛䛣䛸䛜♧䛥䜜䛯䚹

3QRU ࡢ཯ᛂάᛶࡢゎᯒ᫖ᖺࡢ᳨ウ࡛ᅗ  ࡢ㟷⥺࠾ࡼࡧ◚⥺࡛♧ࡋࡓ཯ᛂ࢚ࢿࣝࢠ࣮
ࣉࣟࣇ࢓࢖ࣝࢆᚓ࡚࠸ࡓࡀࠊ௒ᖺᗘࡢ㏣ຍࡢ᳨ウ࡟ࡼࡗ࡚᭱ึ
ࡢ 11 ⤖ྜ⏕ᡂ㐣⛬࡟ࡘ࠸࡚࢚ࢿࣝࢠ࣮㞀ቨࡢప࠸⧄⥔≧ែࢆぢฟࡋࡓࠋࡇࡇ࡛ᐇ⾜ࡋࡓࡢࡣάᛶ㒊఩ࢆษࡾฟࡋࡓࣔࢹ࡛ࣝ
࠶ࡿࡀࠊ21,20 ἲ࡛ࢱࣥࣃࢡ㉁ࡶྲྀࡾධࢀࡓࣔࢹࣝࡢᵓ⠏ࡶヨࡳࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊάᛶ㒊఩࡟  ࡘ┠ࡢ 12 ศᏊࡀᏳᐃ࡟
ᅗ 1+2±୰㛫య12㸦5㸧࠿ࡽ᭱⤊⏕ᡂ≀Ꮡᅾࡍࡿᵓ㐀ࢆぢฟࡍࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ

122+±㸦3㸧࡟⮳ࡿࡲ࡛ࡢ࢚ࢿࣝࢠ࣮ࣉࣟ



Ⓨ⾲ᐇ⦼

࢖



ཱྀ㢌Ⓨ⾲㸦ࢭࣥࢱ࣮฼⏝࡟ࡼࡿࡶࡢ඲  ௳࠺ࡕᣍᚅㅮ₇  ௳㸧‫ۻ‬㏆⸨➨  ᅇ᪥ᮏ⺮ⓑ㉁⛉Ꮫ఍ࢩ࣏ࣥࢪ࣒࢘ࠊᣍᚅㅮ₇࡞࡝

࣏ࢫࢱ࣮Ⓨ⾲㸦ࢭࣥࢱ࣮฼⏝࡟ࡼࡿࡶࡢ඲㸱௳㸧‫ۻ‬௰ྜྷࠊ㮚㔝ࡽ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ࠊ࣏ࢫࢱ࣮Ⓨ⾲࡞࡝ฟ∧ᐇ⦼㸦ㄽᩥ඲  ௳㸧‫ۻ‬㏆⸨ࡽ *OREDODQDO\VLVRIKHPHSURWHLQVHOXFLGDWHVWKHFRUUHODWLRQEHWZHHQKHPHGLVWRUWLRQDQGWKHKHPHELQGLQJSRFNHWJ. Chem. Info. Model. 62

- 73 -

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



◊✲┠ⓗ
⏕⌮άᛶศᏊࡸ⏕యศᏊࡢᵓ㐀ࡢ≉ᚩࡸᶵ⬟Ⓨ⌧㸪཯ᛂࡢ࣓࢝ࢽࢬ࣒㸪ࡲࡓ㸪ࡑࢀࡽ࡬ࡢ⁐፹ࡸ࿘ࡾࡢศ

Ꮚ࠿ࡽࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸪୺࡟㠀⤒㦂ⓗศᏊ㌶㐨ἲ㸪ᐦᗘỗ㛵ᩘ⌮ㄽ㸪ศᏊືຊᏛἲ㸪ࣔࣥࢸ࢝ࣝࣟἲࢆ⏝࠸ࡓ◊✲ࢆ㐍ࡵࡓ㸬ᮏᖺᗘࡢ୺࡞◊✲ෆᐜࡣḟࡢ஧ࡘ࡛࠶ࡿ㸬
1.1 ⁐፹ศᏊࡢᙳ㡪ࢆゎᯒྍ⬟࡞⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤Ⓨ

NMR 㐽ⶸᐃᩘࡣཎᏊ᰾ࡢ⎔ቃ࡟㗦ᩄ࡛࠶ࡿࡓࡵ㸪⁐ᾮ୰ࡢ NMR ໬Ꮫࢩࣇࢺࡣ⁐፹࡟౫Ꮡࡋ㸪≉࡟⁐㉁̽
⁐፹㛫ࡢỈ⣲⤖ྜࡀᏑᅾࡍࡿ⣔࡛ࡣẼ┦࠿ࡽࡢᕪ␗ࡀ኱ࡁ࠸㸬㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚⁐㉁ศᏊࡢ㐽ⶸᐃᩘࢆᐃ㔞ⓗ࡟ィ⟬ࡍࡿࡓࡵ࡟ࡣ㸪⁐㉁࿘ࡾࡢ⁐፹ศᏊࢆ࠶ࡽࢃ࡟ྲྀࡾධࢀ㸪ከࡃࡢ⁐፹࿴ᵓ㐀ࡢ࢔ࣥࢧࣥࣈࣝᖹ
ᆒࢆ࡜ࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿ㸬ࡋ࠿ࡋ㸪ࡇࡢࡼ࠺࡞᪉ἲࡣィ⟬ࢥࢫࢺࡀẚ㍑ⓗ኱ࡁ࠸㸬ࡲࡓ㸪ࡑࢀࡒࢀࡢᵓ㐀࡛ィ⟬ࡉࢀࡿ㐽ⶸᐃᩘࡣ㸪⁐፹ศᏊࡢ㓄⨨࡟౫Ꮡࡋ࡚ࡤࡽࡘࡁ㸪⁐፹ຠᯝࢆ཯ᫎࡋ࡚࠸ࡿ㸬ࡑࡇ࡛㸪⁐ᾮ୰ࡢ NMR 㐽ⶸᐃᩘࢆண

ࡋ㸪㐽ⶸᐃᩘ࡬ࡢ⁐፹ຠᯝࢆゎᯒࡍࡿᡭἲࢆ㛤Ⓨࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬

1.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂RNA interference (RNAi)ࡣ㸪siRNA ࡜࿧ࡤࢀࡿ▷࠸஧ᮏ㙐 RNA ࡀ㑇ఏᏊⓎ⌧ᢚไຠᯝࢆ♧ࡍ⌧㇟࡛࠶ࡿ㸬siRNA ࡣ Argnaute (AGO)࡜࠸࠺ࢱࣥࣃࢡ㉁ୖ࡛஧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ࡲࡓ㸪RNAi ࡛ࡣ㸪࢞࢖ࢻ㙐࡜㒊ศⓗ࡟┦⿵ⓗ࡞㓄ิࢆࡶࡘᮏ᮶ᶆⓗ࡛ࡣ࡞࠸ mRNA ࡢⓎ⌧ࢆᢚไࡍࡿ࢜ࣇࢱ࣮ࢤ
ࢵࢺຠᯝࡀၥ㢟࡜࡞ࡗ࡚࠸ࡿ㸬࢞࢖ࢻ㙐ࡢ≉ᐃࡢ఩⨨ࡢࢾࢡࣞ࢜ࢳࢻࡢ࣮ࣜ࣎ࢫࢆ໬Ꮫಟ㣭ࡍࡿࡇ࡜࡛㸪άᛶ࡟ᙳ㡪ࡀ࠶ࡿࡇ࡜ࡀᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡾ㸪RNAi άᛶࢆಖࡗࡓࡲࡲ࢜ࣇࢱ࣮ࢤࢵࢺຠᯝࢆῶᙅࡉ
ࡏࡿྍ⬟ᛶࡀ♧၀ࡉࢀ࡚࠸ࡿ㸬ࡑࡇ࡛㸪ࡇࡢ໬Ꮫಟ㣭ࡢຠᯝࡢ࣓࢝ࢽࢬ࣒ࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸪⌮ㄽ໬Ꮫⓗ࡞◊✲ࢆ㐍ࡵ࡚࠸ࡿ㸬ᮏᖺᗘࡣ±NHCHO ࢆᑟධࡋࡓィ⟬ࢆ⾜࡞ࡗࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 ⁐፹ศᏊࡢᙳ㡪ࢆゎᯒྍ⬟࡞⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤Ⓨ࣓ࢱࣀ࣮ࣝỈ⁐ᾮ࡟࠾ࡅࡿ࣓ࢱࣀ࣮ࣝࡢࣄࢻࣟ࢟ࢩᇶࡢ 1H NMR 㐽ⶸᐃᩘࢆண

ࡍࡿࣔࢹࣝࢆసᡂࡋࡓ㸬ࡲࡎ㸪 NAMD ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋ࡚㸪࣓ࢱࣀ࣮ࣝỈ⁐ᾮࡢ MD ࢆ⾜࡞ࡗࡓ㸬MD ࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽ
࣓ࢱࣀ࣮ࣝศᏊ࡜ࡑࡢ㏆ഐࡢỈศᏊࢆᢤࡁฟࡋࡓ㸬ᚓࡽࢀࡓࢡࣛࢫࢱ࣮ᵓ㐀࡟ࡘ࠸࡚㸪 GIAO ἲࢆ⏝࠸
B3LYP/aug-cc-pVDZ ࡛ࣞ࣋ࣝ NMR 㐽ⶸᐃᩘࢆィ⟬ࡋࡓ㸬⁐፹ỈศᏊࡀ࡞࠸ሙྜࡢ㐽ⶸᐃᩘࡶィ⟬ࡋ࡚㸪ᕪࢆ࡜ࡿࡇ࡜࡟ࡼࡾ NMR 㐽ⶸᐃᩘࡢ⁐፹ࢩࣇࢺ㔞ǼQM ࢆồࡵࡓ㸬ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ Gaussian 16 ࢆ⏝࠸ࡓ㸬ணࣔࢹࣝࡣ㸪⁐፹ࢩࣇࢺ㔞Ǽmodel ࢆ⁐㉁ศᏊ࡜⁐፹ 1 ศᏊࡢᗙᶆࡀධຊ࡜࡞ࡿ 2 యࡢ㛵ᩘࡢ࿴࡜⁐㉁ศ

Ꮚ࡜⁐፹ 2 ศᏊࡢᗙᶆࡀධຊ࡜࡞ࡿ 3 యࡢ㛵ᩘࡢ࿴࡛⾲ࡋ㸪2 యࡢ㛵ᩘ࡜ 3 యࡢ㛵ᩘࢆࡑࢀࡒࢀࢽ࣮ࣗࣛࣝ
ࢿࢵࢺ࣮࣡ࢡ㸦NN㸧࡛⾲⌧ࡋࡓ㸬ྛ㡯ࡢ⥲࿴࡛࠶ࡿࣔࢹࣝࡢ⁐፹ࢩࣇࢺ㔞Ǽmodel ࡀ㔞Ꮚ໬Ꮫィ⟬࡛ồࡵࡓ⁐- 74 -

፹ࢩࣇࢺ㔞ǼQM ࢆ෌⌧ࡍࡿࡼ࠺࡟Ꮫ⩦ࡉࡏࡓ㸬NN ࡣ PyTorch ࢆ฼⏝ࡋ࡚ᐇ⿦ࡋࡓ㸬
2.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂
AGO ࢱࣥࣃࢡ㉁࡜ siRNA ࡢ୍ᮏ㙐࡛࠶ࡿ࢞࢖ࢻ㙐࡜ࡢ」ྜయ࡟ᑐࡍࡿ⨨᥮ᇶࡢᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟㸪ࢱ
ࣥࣃࢡ㉁ഃ㙐࡜࢜ࣜࢦࢾࢡࣞ࢜ࢳࢻࢆᢤࡁฟࡋࡓࣔࢹࣝ⣔ࢆᵓ⠏ࡋࡓ㸬ࡑࡢࣔࢹࣝ⣔ࢆ ȦB97X-D/6-31G(d)ࣞ
࡛࣋ࣝᵓ㐀᭱㐺໬ࢆ⾜࡞ࡗࡓ㸪ࡲࡓ㸪ᐇ㦂ࡀ⾜ࢃࢀ࡚࠸ࡿࡼ࠺࡟࠸ࡎࢀ࠿ࡢࢾࢡࣞ࢜ࢳࢻࡢ 2¶఩ࡢ±OH ࢆ±NHCHO ࡟⨨᥮ࡋ࡚ྠᵝ࡟ᵓ㐀᭱㐺໬ࢆ⾜࡞ࡗࡓ㸬ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ Gaussian 16 ࢆ⏝࠸ࡓ㸬



◊✲ᡂᯝ

3.1 ⁐፹ศᏊࡢᙳ㡪ࢆゎᯒྍ⬟࡞⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘணࣔࢹࣝࡢ㛤Ⓨ

NMR 㐽ⶸᐃᩘࡢ⁐፹ࢩࣇࢺ㔞࡜ࢡࣛࢫࢱ࣮ᵓ㐀ࡢ⤌ࡢࢹ࣮ࢱ 19774 ⤌ࢆᏛ⩦ࢹ࣮ࢱ࡜ホ౯ࢹ࣮ࢱ࡟ศࡅ㸪ணࣔࢹࣝࢆᏛ⩦ࡉࡏࡓ㸬ᚓࡽࢀࡓࣔࢹࣝࡢホ౯ࢹ࣮ࢱ࡟ᑐࡍࡿண

0.43 ppm ࡛࠶ࡗࡓ㸬ண⢭ᗘࡣ㸪RMSE ࡀ 0.55 ppm㸪MAE ࡀࣔࢹࣝ࡟ᇶ࡙࠸࡚㸪㐽ⶸᐃᩘࡢ⁐፹ࢩࣇࢺࢆྛ㡯࡟ศ๭ࡋ࡚ゎᯒࡍࡿ࡜㸪౑⏝ࡋࡓࡍ࡭࡚ࡢࢡࣛࢫࢱ࣮ᵓ㐀࡟ࡘ࠸࡚ 2 యࡢ㡯ࡢ࿴ࡣ 3 యࡢ㡯ࡢ࿴ࡼࡾ኱ࡁࡃ㸪2 యࡢ㡯ࡀᨭ㓄ⓗ࡛࠶ࡗࡓ㸬ࡲࡓ㸪2 యࡢ㡯ࡢ୍ࡘࡔࡅࡀ௚ࡢ㡯࡟ẚ࡭࡚኱ࡁ࡞್ࢆ♧ࡍᵓ㐀ࡀከࡃ࠶ࡾ㸪ࡑࡢሙྜ㸪ࡑࡢ㡯ࡣ࢚ࢱࣀ࣮ࣝࡢ
OH ࡜Ỉ⣲⤖ྜࡋࡓỈศᏊ࡜ࡢࡶࡢ࡛࠶ࡗࡓ㸬Ꮫ⩦ࡋࡓ 2 యࡢ NN ࡢ㛵ᩘࢆ⏝࠸࡚㸪⁐፹ࢩࣇࢺ㔞ࢆỈศᏊࡢ㓄⨨ࡢ㛵ᩘ࡜ࡋ࡚࣐ࢵࣉࢆసᡂࡋࡓ㸬ᙉ࠸Ỉ⣲⤖ྜࡀᙧᡂ࡛ࡁࡿ㓄⨨࡛㸪኱ࡁ࡞⁐፹ࢩࣇࢺ♧ࡋ㸪Ꮫ⩦ࡋࡓ
2 యࡢ NN ࡢ㛵ᩘࡢጇᙜᛶࢆᨭᣢࡍࡿ⤖ᯝ࡜࡞ࡗࡓ㸬
3.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂siRNA ࡢ࢞࢖ࢻ㙐ࡢ 2 ␒┠࠿ࡽ 8 ␒┠ࡲ࡛ࡢ࠸ࡎࢀ࠿ࡢࢾࢡࣞ࢜ࢳࢻࡢ 2̓఩ࡢ±OH ࢆ±1+&+2 ࡟⨨᥮ࡋࡓᐇ㦂࡛㸪2㸪5㸪8 ␒┠࡟±1+&+2 ࢆᑟධࡋࡓሙྜ࡟࢜ࣇࢱ࣮ࢤࢵࢺຠᯝࡀ᭷ព࡟ῶᙅࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬
2 ␒┠ࡢࢾࢡࣞ࢜ࢳࢻ࡟±1+&+2 ࢆᑟධࡋࡓࣔࢹࣝィ⟬ࡢ⤖ᯝ㸪±2+ య࡟ẚ࡭࡚ 2 ␒┠㸪3 ␒┠ࡢሷᇶࡢྥ
ࡁࡀኚ໬ࡋ㸪ሷᇶᑐྜࡢ㜼ᐖࡀ♧၀ࡉࢀࡓ㸬ࣔࢹࣝィ⟬ࡢጇᙜᛶࢆ᳨ウࡍࡿ࡜࡜ࡶ࡟㸪௚ࡢࢾࢡࣞ࢜ࢳࢻ࡬
ࡢ⨨᥮ᇶࡢᑟධࡋࡓࣔࢹࣝ⣔ࢆィ⟬୰࡛࠶ࡿ㸬

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫(ۻ‬1) Ᏻᡂ㙠㸪ᑠᯘⰾ᫂㸪㔝ᮧᾈᖹ㸪㉥℩኱㸪ᮌᮧᗣ᫂㸪㜿㒊ὒ㸪┦⏣⨾◁Ꮚ㸪⛬ஂ⨾Ꮚ㸪᪥ᮏ᰾㓟་⸆Ꮫ఍➨ 6 ᅇᖺ఍㸦2021 ᖺ 6 ᭶ 27 ᪥㸪࢜ࣥࣛ࢖ࣥ㸧‫(ۻ‬2) Yoshiaki Kobayashi, Shen Tian, Daiki Fukuhara, Dai Akase, Misako Aida, Kumiko Ui-Tei㸪➨ 22 ᅇ᪥ᮏ RNAᏛ఍ᖺ఍㸦2021 ᖺ 7 ᭶ 7 ᪥㸪࢜ࣥࣛ࢖ࣥ㸧‫(ۻ‬3) ᑠᯘⰾ᫂㸪⏣⏦㸪⚟ཎ኱㍤㸪㉥℩኱㸪┦⏣⨾◁Ꮚ㸪⛬ஂ⨾Ꮚ㸪➨ 44 ᅇ᪥ᮏศᏊ⏕≀Ꮫ఍ᖺ఍㸦2021
ᖺ 12 ᭶ 1 ᪥㸪⚄ዉᕝ┴ᶓ὾ᕷ㸧‫(ۻ‬4) Seongjin An, Yoshiaki Kobayashi, Nomura Kohei, Dai Akase, Yasuaki Kimura, Hiroshi Abe, Misako Aida,
Kumiko Ui-Tei㸪➨ 44 ᅇ᪥ᮏศᏊ⏕≀Ꮫ఍ᖺ఍㸦2021 ᖺ 12 ᭶ 2 ᪥㸪⚄ዉᕝ┴ᶓ὾ᕷ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Yoshiaki Kobayashi, Daiki Fukuhara, Dai Akase, Misako Aida, Kumiko Ui-Tei, ACS Omega 7, 2398–2410(2022). DOI: 10.1021/acsomega.1c06455‫[ۻ‬2] Wataru Miyanishi, Makoto Ojika, Dai Akase, Misako Aida, Yasuhiro Igarashi, Yukishige Ito, Yu Nakagawa,Bioorgan. Med. Chem. 55, 116590 (2022). DOI: 10.1016/j.bmc.2021.116590- 75 -

ṑ㌴≧୧ぶ፹ᛶศᏊ (GSA)ࡢ⇕ຊᏛⓗᏳᐃᛶཬࡧⓎගࢫ࣌ࢡࢺࣝ࡟ᑐࡍࡿ⨨᥮ᇶຠᯝࡢ⌮ㄽⓗ◊✲Theoretical and computational study on substitution effect for thermal
stability and emission spectra of GSA‫❧ۑ‬ᕝ ோ඾ࠊ໭ ᖾᾏࠊᓥᓮ ᬛᐇࠊᑠᯘ ⌮ࠊྂᓥ ᘺ᮶ࠊྜྷ⏣ ኱㍜ࠊᆏୖ ᘯ㍤ࠊᮧ⏣ ⴌ㸦ᶓ὾ᕷ❧኱Ꮫ㸧1◊✲┠ⓗᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣᮾி኱Ꮫࡢᖹᒸᩍᤵ࡜ඹྠ࡛ࠊṑ㌴≧୧ぶ፹ᛶศᏊ(GSA)ࡀỈ୰࡛ᙧᡂࡍࡿ⟽ᆺ 6 㔞య࡛࠶ࡿࢼࣀ࣮࢟ࣗࣈࡢ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡣ S6 ⩌࡟ᖐᒓࡉࢀࠊศᏊ࡟ྵࡲࢀࡿ 3ࡘࡢ࣓ࢳࣝᇶࡀჶࡳྜࡗࡓࠕ໭ᴟࠖཬࡧࠕ༡ᴟࠖ࡜ࠊࣆࣜࢪࢽ࣒࢘࢝ࢳ࢜ࣥཬࡧࣇ࢙ࢽࣝᇶ࠶ࡿ࠸ࡣࣆࣜࢪ
ࣝᇶࡀᙧᡂࡍࡿࠕtriple π-stackingࠖࡀ୪ࡪࠕ㉥㐨ࠖ࡜࠸࠺ࠊ≉ᚩⓗ࡞ᵓ㐀ࢆ᭷ࡍࠋGSA ࡟ࡼࡾᙧᡂࡉࢀࡓࢼࣀ
࣮࢟ࣗࣈࡣࡑࡢෆ㒊ࡢ✵㛫࡟ࠕࢤࢫࢺศᏊࠖ࡜࿧ࡤࢀࡿ GSA ࡸ⁐፹࡜ࡣ↓㛵ಀ࡞➨ 3 ࡢศᏊࢆໟ᥋ࡍࡿࡇ࡜
ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀᐇ㦂࠿ࡽ☜ㄆࡉࢀ࡚࠾ࡾ[1]ࠊGSA ࡀᙧᡂࡍࡿࢼࣀ࣮࢟ࣗࣈࡣ GSA ࡢᵓ㐀ࢆ໬Ꮫⓗ࡟ಟ㣭ࡍࡿࡇ࡜࡟ࡼࡾࠊ⇕ⓗᏳᐃᛶࡸࢤࢫࢺศᏊࡢໟ᥋㏿ᗘࢆไᚚࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀᐇ㦂ⓗ࡟ࢃ࠿ࡗ࡚࠸ࡿ[1,2]ࠋ୍᪉ࠊᙜࢢ࣮ࣝࣉ࡛ࡣศᏊືຊᏛࡢᡭἲࢆ⏝࠸ࠊࡇࢀࡲ࡛࡟ GSA ࡀࢡ࣒ࣟࣟ࣍ࣝ୰࡛ࡣ 4 㔞యࢆᙧᡂࡍࡿࡇ࡜ࡸࠊࢼࣀ࣮࢟ࣗࣈࡀࢤࢫࢺศᏊࢆྲྀࡾ㎸ࡴࡇ࡜ࡢ෌⌧࡟ᡂຌࡋࡓࠋ
ࢼࣀ࣮࢟ࣗࣈࡢᏳᐃᛶࡣ㉥㐨ୖࡢ triple π-stacking ࡟ࠊᙜ◊✲ᐊ࡛ࡢ㐣ཤࡢ◊✲࠿ࡽࢤࢫࢺศᏊࡢෆໟ㏿ᗘࡣᴟࡢ❧యⓗ࡞࠿ࡉ㧗ࡉ࡟ࡼࡾไᚚ࡛ࡁࡿ࡜ண᝿ࡉࢀࠊᐇ㦂ⓗ࡟ࡶ࣓ࢳࣝᇶࡀᏑᅾࡋ࡞࠸࡯࠺ࡀෆໟ㏿ᗘࡀ
㏿ࡃ࡞ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋࡑࡇ࡛ᮏᖺᗘࡣࠊ໭ᴟཬࡧ༡ᴟࡢ࣓ࢳࣝᇶࢆỈ⣲࡛⨨᥮ࡋࡓࢼࣀ࣮࢟ࣗࣈ࡟
ࡘ࠸࡚ศᏊືຊᏛ(MD)ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ⌮ㄽィ⟬ࡢほⅬ࠿ࡽ⨨᥮ᇶࡢࢼࣀ࣮࢟ࣗࣈࡢ⇕Ᏻᐃᛶ࡜ෆ
ໟ㏿ᗘ࡟ᑐࡍࡿᙳ㡪ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋᮏᖺᗘࡣ≉࡟࡝ࡇࡢ࣓ࢳࣝᇶࡀ⇕ຊᏛⓗᏳᐃᛶ࡜ෆໟ㏿ᗘ࡟ᑐࡋ࡚ᙳ㡪ࢆ୚࠼ࡿࡢ࠿ࢆࡶㄪ࡭ࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊᚋ㏙ࡢࡼ࠺࡟ GSA ෆࡢ࣋ࣥࢮࣥ⎔࡟⤖ྜࡍࡿ(a)ࡍ࡭࡚ࡢ࣓ࢳࣝᇶࢆṧࡋࡓࡶࡢࠊ(b)ࡍ࡭࡚ࡢ࣓ࢳࣝᇶࢆỈ⣲ཎᏊ࡟⨨᥮ࡋࡓࡶࡢࠊ(c)ࢼࣀ࣮࢟ࣗࣈ࡟ࡋࡓ࡜
ࡁᴟ࡟఩⨨ࡍࡿ࣓ࢳࣝᇶࡢࡳࢆỈ⣲ཎᏊ࡟⨨᥮ࡋࡓࡶࡢࠊ
ࡢ 3 ✀㢮࡟ࡘ࠸࡚ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡲࡓ GSAࠊࢼࣀ࣮࢟ࣗࣈࡣ⺯ගࢫ࣌ࢡࢺࣝࡢ

ᐃࡶ⾜ࢃࢀ࡚࠾ࡾࠊ኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࡶ☜ㄆࡉࢀ࡚࠸ࡿࠋศᏊෆ࡛ࡢ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ(TDDFT)ἲࢆ⏝࠸ࡓィ⟬࡛ࡣ኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࢆ☜ㄆ࡛ࡁ࡞࠿
ࡓࡇ࡜࠿ࡽࠊศᏊ㛫㟁Ⲵ⛣ືࡢほⅬ࠿ࡽࢆࡶィ⟬ࢆ⾜ࡗࡓࠋࡓࡔࡋࠊ⣬㠃ࡢ㒔ྜ࠿ࡽᮏሗ࿌࡛ࡣ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟㆟ㄽࢆ⤠ࡾグ㏙ࡍࡿࠋ࠙ཧ⪃ᩥ⊩ࠚ
[1] Hiraoka, S. et al., J. Am. Chem. Soc., 132, 13223–13225 (2010). [2] Zhan, Y. Y. et al., Commun. Chem. 1, 14 (2018).

2◊✲᪉ἲࠊィ⟬᪉ἲ
Fig. 1 ࡢ㟷Ⰽ࡛♧ࡋࡓ㒊ศࡀࣆࣜࢪ࡛ࣥ࠶ࡿศᏊ࡛ᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡢ X ⥺ᅇᢡ࡟ࡼࡾᚓࡽࢀࡓᵓ

㐀ࢆࡶ࡜࡟ࠊFig. 1 ࡢ 1612+,2612+, 3612+ࡢศᏊືຊᏛ࡟㐺⏝ࡍࡿᗙᶆࡢࢹ࣮ࢱࢆసᡂࡋࡓࠋࡓࡔࡋࠊ2612+ࡢ㔜Ỉ⣲ࡣ㍍Ỉ⣲ཎᏊ࡜ࡋ࡚ᢅࡗࡓࠋࢼࣀ࣮࢟ࣗࣈࡣ+12 ࡢṇ㟁Ⲵࢆᣢࡘࡓࡵ 12 ཎᏊࡢࣚ࢘໬≀࢖࢜ࣥ࡟ࡼࡾ⣔ࢆ

- 76 -

㟁Ẽⓗ࡟୰ᛶ࡟ࡋࠊࡉࡽ࡟ෆໟࢆ㉳ࡇࡾࡸࡍࡃࡍࡿࡓࡵ࡟ 12 ಶࡢࣚ࢘໬
ࢼࢺ࣒ࣜ࢘ࢆ⣔࡟ຍ࠼ࡓ(ࡍ࡞ࢃࡕࣚ࢘໬≀࢖࢜ࣥࡣ⣔࡟ 24 ཎᏊྵࡲࢀࡿ) ࠋࡲࡓࢼࣀ࣮࢟ࣗࣈࡣỈ୰࡛ᙧᡂࡉࢀࡿࡓࡵ⁐፹ศᏊ࡜ࡋ࡚ỈศᏊࢆຍ࠼ࡓࠋຍ࠼ࡽࢀࡓỈศᏊࡣ(a)1612+, (b)2612+, (c)3612+ ࡟ࡘ࠸࡚ࡑࢀࡒࢀ
15550, 15461, 14592 ศᏊ࡛࠶ࡗࡓࠋࡇࡇ࡛ࠊࢼࣀ࣮࢟ࣗࣈෆእࡢࠕỈᅽࠖࡢᕪ࡛ࢼࣀ࣮࢟ࣗࣈࡀኚᙧࡋ࡞࠸ࡼ࠺ࠊࢼࣀ࣮࢟ࣗࣈෆ㒊࡟ࡣ 17 ศᏊࡢỈศᏊࡀྵࡲࢀࡿࡼ࠺࡟⣔ࡢึᮇᵓ㐀ࢆὀព῝ࡃసᡂࡋࡓࠋసᡂࡋࡓ⣔࡟ᑐࡍࡿศᏊຊሙࡣ AmberTools20 ࡼࡾ౑⏝࡛ࡁࡿ Antechamber ཬࡧ xLEaPࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚సᡂࡋࡓࠋࢼࣀ࣮࢟ࣗࣈࡢศᏊຊሙࡢసᡂ࡟࠾࠸࡚ࡣ
General Amber force field (GAFF) ࡢ ࣃ ࣛ ࣓ ࣮ ࢱ ࢭ ࢵ ࢺ ࢆ ⏝ ࠸ ࠊ 㟁 Ⲵ ࡣGaussian 16 (Rev. A.03)࡟ࡼࡾ Hartree-Fock/6-31G(d)ἲࢆ⏝࠸࡚⾜ࡗࡓ㔞ᏊFig. 1. The structure of the target໬ Ꮫ ィ ⟬ ࡟ ࡼ ࡾ Ỵ ᐃ ࡉ ࢀ ࡓ 㟼 㟁 ࣏ ࢸ ࣥ ࢩ ࣕ ࣝ ࡟ ᇶ ࡙ ࡃ Restrained

system.

electrostatic potential (RESP) 㟁Ⲵࢆ⏝࠸ࡓࠋỈศᏊࡢศᏊຊሙࡣ TIP4P ࣔࢹࣝࢆ⏝࠸ࠊࣚ࢘໬≀࢖࢜ࣥ࠾ࡼࡧ
ࢼࢺ࣒ࣜ࢘࢖࢜ࣥࡢศᏊຊሙࡣ ff14SB ศᏊຊሙࡢࣃ࣓࣮ࣛࢱࢆ⏝࠸ࡓࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᐇ᪋
࡟࠾࠸࡚ࡣィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ⏝࠸ࠊAMBER20 ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࡼࡾ౑⏝࡛ࡁࡿ pmemd
ࣔࢪ࣮ࣗࣝࢆ⏝࠸ࡓࠋィ⟬ࡣึᮇᵓ㐀ࢆసᡂࡍࡿࡓࡵࡢணഛィ⟬࡜ࡋ࡚ 300 K, 1 atm ࡛ࡢ NPT ᮲௳࡟࠾ࡅࡿ
MD ࢆ⾜ࡗࡓᚋࠊLangevin ⇕ᾎࢆ⏝࠸ 300 K ࡛ࡢ NVT ᮲௳࡛⾜ࡗࡓࠋ(a)1612+, (b)2612+, (c)3612+࡟ࡘ࠸࡚ࠊᚓࡽ
ࢀࡓ⣔ࡢᐦᗘࡣࡑࢀࡒࢀ 1.00, 1.00, 1.00 g cm-3 ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋᮏィ⟬࡟࠾࠸࡚ࡣỈ⣲ࢆྵࡴ໬Ꮫ⤖ྜ࡟ࡘ࠸࡚ࡣ SHAKE ࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸⤖ྜ㛗ࢆᅛᐃࡋࡓࠋ1612+, 2612+, 3612+࡟ࡘ࠸࡚ࡑࢀࡒࢀ 34, 33, 34 ࡢึᮇ㐠ື㔞࠿ࡽࠊࡑࢀࡒࢀ 2.0 fs ࡢ᫬㛫้ࡳ࡛ 5 ns (2,500,000 step)᫬㛫Ⓨᒎࢆ⾜ࡗࡓࠋᚓࡽࢀࡓྂ඾㌶㐨ࡢ࠺ࡕࣚ࢘໬≀࢖࢜ࣥࡀෆໟࡉࢀࡓࡶࡢ࡟ࡘ࠸࡚ヲ⣽࡞ゎᯒࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
1612+, 2612+, 3612+࡟ࡘ࠸࡚ࠊ5 ns ௨ෆ࡟ࣚ࢘໬≀࢖࢜ࣥࡢෆໟࡀ☜ㄆ࡛ࡁࡓྂ඾㌶㐨ࡢᩘࡣࡑࢀࡒࢀ 4, 26, 10ᮏ࡛࠶ࡗࡓࠋෆໟࡀ㉳ࡇࡗࡓࡍ࡭࡚ࡢྂ඾㌶㐨࡟࠾࠸࡚ࣚ࢘໬≀࢖࢜ࣥࡣᴟ㒊ศ࠿ࡽෆໟࡉࢀࡓࠋ1612+, 3612+
ࡣࠕ༡ᴟࠖ࡜ࠕ໭ᴟࠖࡢ㒊ศ(3 ࡘࡢ 12+, 22+, 32+ࡀ㞟ࡲࡿ S6 ㍈ୖࡢ఩⨨)࡟࠾࠸࡚࣓ࢳࣝᇶࡢ᭷↓ࡀ␗࡞ࡿ୍᪉ࠊ
㉥㐨㒊ศ(༡ᴟ࡜໭ᴟࡢ୰Ⅼࢆ㏻ࡾ S6 ㍈࡟┤஺ࡍࡿᖹ㠃ୖࡢ఩⨨)࡟࠾࠸࡚ศᏊࡢᵓ㐀ୖࡢᕪ␗ࡣ࡞࠸ࠋࡋࡓ
ࡀࡗ࡚ࠊᴟ㒊ศࡢᵓ㐀ࡣෆໟࡢ㉳ࡇࡾࡸࡍࡉ࡟ᙳ㡪ࢆ୚࠼ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ᚓࡽࢀࡓྂ඾㌶㐨࡟࠾ࡅࡿࠊ᫬㛫࡟ᑐࡍࡿᵓ㐀ኚ໬ࢆゎᯒࡍࡿࡓࡵ
ଵଶܴ‫ܦܵܯ‬ሺ‫ݐ‬ሻ ൌ  ටெ  σே௜ୀଵሾ݉௜  ሼܺ௜ ሺ‫ݐ‬ሻ െ ܺ௜ ሺͲሻሽሿ

(1)࡛ᐃ⩏ࡉࢀࡿᖹᆒ஧஌೫ᕪ(RMSD)ࢆィ⟬ࡋࡓ(Fig.2)ࠋࡇࡇ࡛ࠊ‫ܯ‬,݉௜ ,ܺ௜ ሺ‫ݐ‬ሻࡣࠊࡑࢀࡒࢀᑐ㇟࡜ࡍࡿཎᏊࡢ㉁㔞ࡢ⥲࿴ࠊ݅␒┠ࡢཎᏊࡢ㉁㔞ࠊ᫬㛫‫ࡿࡅ࠾࡟ݐ‬୪㐍࣭ᅇ㌿ࢆ㝖࠸ࡓ݅␒┠ࡢཎᏊࡢᗙᶆࢆ♧ࡍࠋࡲࡓ Fig. 2 ࡣ⣔඲యࢆ⪃៖ࡋࡓ RMSD ࡛࠶ࡾࠊܰࡣ⣔඲య࡟ྵࡲࢀࡿཎᏊᩘࢆ⾲ࡍࠋ ෆໟࡢ㉳ࡇࡗࡓྂ඾㌶㐨࡟ࡘ࠸࡚ RMSD ࡢࣄࢫࢺࢢ࣒ࣛࢆసᡂࡋࡓࠋFig. 3(a), (c)࡟♧ࡍ 1612+, 3612+࡟ࡘ࠸࡚ࡣෆໟࡢ㉳ࡇࡗࡓࡍ࡭࡚ࡢྂ඾㌶㐨ࢆࠊFig. 3(b)࡟♧ࡍ 2612+࡟ࡘ࠸࡚ࡣෆໟࡢ㉳ࡇࡗࡓ 26 ᮏࡢྂ඾㌶㐨࠿ࡽ↓సⅭ࡟ 10 ᮏࢆ㑅ᢥࡋゎᯒ࡟౑⏝ࡋࡓࠋ- 77 -

(a)

(b)

(c)

0.7

0.7

1.0
1.6

2.6

1.8

2.5

1.5

Fig. 2. RMSD ࡢ㢖ᗘศᕸࠋ(a)4 ᮏࡢ 1612+, (b)10 ᮏࡢ 2612+, (c)10 ᮏࡢ 3612+ࡢࣚ࢘໬≀࢖࢜ࣥࡀෆໟࡉࢀࡓ
ྂ඾㌶㐨ࢆ౑⏝ࡋࡓࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊRMSD ࡣ࠸ࡃࡘ࠿ࡢ㞳ᩓⓗ࡞್ࡢ࿘ࡾ࡟㞟୰ࡍࡿࡇ࡜ࡀ Fig. 2 ࠿ࡽ᫂ࡽ࠿࡟࡞ࡗࡓࠋ1612+
࡟ࡘ࠸࡚ࡣ 3 ࡘࡢ᫂☜࡞ࣆ࣮ࢡࡀ☜ㄆࡉࢀࠊᑡ࡞ࡃ࡜ࡶ 3 ࡘࡢᏳᐃᵓ㐀ࡀᏑᅾࡍࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡇ
ࡇ࡛ࠕᑡ࡞ࡃ࡜ࡶࠖ࡜࠸࠺ࡢࡣᵓ㐀ࡀ␗࡞ࡾ RMSD ࡀྠࡌ࡜࡞ࡿሙྜࢆྰᐃ࡛ࡁ࡞࠸ࡓࡵ࡛࠶ࡿࠋ
2612+ࡣ 1612+࡟ẚ࡭ᵓ㐀ࡢศ㞳ࡀ୙᫂░࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣ 2612+࡟࠾ࡅࡿᵓ㐀ࡀኚᙧࡋࡸࡍ࠸ࡇ
࡜ࢆ཯ᫎࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ᭱ࡶᕥࡢࣆ࣮ࢡࡣ᭱ࡶᏳᐃ࡞ᵓ㐀࡟ᑐᛂࡍࡿ࡜⪃࠼ࡽࢀࡿࡀ 1612+࡟ẚ࡭
2612+࡛ࡣࡑࡢࣆ࣮ࢡࡢ㧗ࡉࡀ㢧ⴭ࡟పࡃ࡞ࡗ࡚࠾ࡾ᭱Ᏻᐃᵓ㐀ࡢ⇕ຊᏛⓗᏳᐃᛶࡀ 1612+࡟ẚ࡭┦ᑐⓗ࡟୙Ᏻᐃ࡟࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࠊࡲࡓࠊ1.8 Å ࡜ 2.5 Å ࡢ㛫ࡢ㇂ࡀᑠࡉࡃ㸦್࡜ࡋ࡚ࡣ኱ࡁࡃ㸧࡞ࡗ࡚࠸ࡿࡇ࡜࠿
ࡽ 2 ࡘࡢ‽Ᏻᐃᵓ㐀ࡢ┦஫ኚ᥮ࡀ㉳ࡇࡾࡸࡍࡃ࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ3612+࡟ࡘ࠸࡚ࡣ᭱ࡶྑഃࡢࣆ࣮ࢡ
ࡀ࡯࡜ࢇ࡝ᾘኻࡋࡓࠋᙜ◊✲ᐊ࡛ࡣヲ⣽࡞ゎᯒ࠿ࡽࢼࣀ࣮࢟ࣗࣈࡣࣚ࢘໬≀࢖࢜ࣥࢆෆໟࡍࡿ࡜ᵓ㐀ࡀኚᙧࡋ࡟ࡃࡃ࡞ࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠾ࡾࠊ3612+࡟࠾࠸࡚ࡣࣚ࢘໬≀࢖࢜ࣥࡢෆໟࡀ᪩࠸ࡓࡵ࡟኱ࡁࡃኚᙧࡋࡓᵓ㐀࡟ᑐᛂࡍࡿ᭱ࡶྑഃࡢࣆ࣮ࢡࡀᾘኻࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
1.

‫ۻ‬ᮧ⏣ⴌ, 㝞ᘯ⇝, ᑠᯘ⌮, ᓥᓮᬛᐇ, ᖹᒸ⚽୍, ❧ᕝோ඾, “⮬ᕫ㞟ྜᛶࢼࣀ࣮࢟ࣗࣈࡢᏳᐃ໬࡜ศᏊ
ෆໟ࣓࢝ࢽࢬ࣒ࡢ⌮ㄽⓗ◊✲”, ᪥ᮏ໬Ꮫ఍➨ 102 ᫓Ꮨᖺ఍(2022), H201-2pm-12, ࢜ࣥࣛ࢖ࣥ㛤ദ,2022 ᖺ 3 ᭶2.

‫ۻ‬ᮧ⏣ⴌ, 㝞ᘯ⇝, ᑠᯘ⌮, ᓥᓮᬛᐇ, ᖹᒸ⚽୍, ❧ᕝோ඾, “⮬ᕫ㞟ྜᛶࢼࣀ࣮࢟ࣗࣈࡢᏳᐃ໬࡜ศᏊ
ෆໟ࣓࢝ࢽࢬ࣒ࡢ⌮ㄽⓗ◊✲”, ➨ 24 ᅇ⌮ㄽ໬Ꮫウㄽ఍, 2P06, ࢜ࣥࣛ࢖ࣥ, 2022 ᖺ 5 ᭶3.

ྜྷ⏣኱㍜,໭ᖾᾏ, ᓥᓮᬛᐇ, ❧ᕝோ඾, ͆Ẽ┦ 2 ᡂศỈ⣲⤖ྜࢡࣛࢫࢱ࣮ࡢ㝧㟁Ꮚぶ࿴ᛶࡢ⌮ㄽணぢ͇,᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨ኱఍, 2O09, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ 11 ᭶

4.

ྂᓥᘺ᮶,ྜྷ⏣኱㍜,໭ᖾᾏ,ᓥᓮᬛᐇ,❧ᕝோ඾, "van der Waals ࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ㝧㟁Ꮚ᮰⦡ࡢ⌮ㄽⓗ◊✲" ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨᖺ఍, 2O08, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ 11 ᭶

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

‫ۻ‬Taro Udagawa, Kazuaki Kuwahata, and Masanori Tachikawa, "Competitive nuclear quantum effect and H/Disotope effect on torsional motion of H2O2: An ab initio path integral molecular dynamics study", Comp. Theor.
Chem, 1208, 113542 (2022). DOI: 10.1016/j.comptc.2021.113542

2.

Takuma Yamashita, Emiko Hiyama, Daisuke Yoshida, and Masanori Tachikawa, "Spontaneous radiative- 78 -

dissociation of the second bound state of positronium hydride", Phys. Rev. A, 105, 012814 (2022). DOI:
10.1103/PhysRevA.105.012814
3.

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

4.

‫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

5.

‫ 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

6.

Ryusei Iida, Haruya Suzuki, Toshiyuki Takayanagi, and Masanori Tachikawa, "Contribution of vibrational
overtone excitations to positron annihilation rates for benzene and naphthalene", Phys. Rev. A, 104, 062807 (9pages) (2021). DOI: 10.1103/PhysRevA.104.062807

7.

Kazuaki Kuwahata and Masanori Tachikawa, "Path Integral Molecular Dynamics Study on NH4+(H2O)", FewBody Systems, 62, 96 (2021). DOI: 10.1007/s00601-021-01689-y8.

‫ۻ‬Maya Ozaki, Daisuke Yoshida, Yukiumi Kita, Tomomi Shimazaki, and Masanori Tachikawa, "Positron Binding
and Annihilation Properties of Amino Acid Systems", ACS Omega, 6, 29449-29458 (2021). DOI:
10.1021/acsomega.1c03409

9.

Masanori Tachikawa and Daisuke Yoshida, "Theoretical Study For Positron Binding and Annihilation of Alcohol
Clusters", Few-Body Systems, 62, 48 (2021). DOI: 10.1007/s00601-021-01636-x

10. ‫ ۻ‬Takayoshi Ishimoto, Hiroki Sakagami, Yusuke Kanematsu, and Masanori Tachikawa, H/D isotope effectbetween adsorbed water (H2O, D2O, and HDO) and H2O- and D2O-ice Ih(0001) basal surfaces based on the
combined plane wave and localized basis set method", Applied Surface Science, 561, 150100 (2021). DOI:
10.1016/j.apsusc.2021.150100.
11. Tomomi Shimazaki, Masanori Tachikawa, A theoretical study on solvatofluorochromic asymmetricthiazolothiazole (TTz) dyes using dielectric-dependent density functional theory", Phys. Chem. Chem. Phys., 23,21078-21086 (2021). DOI: 10.1039/D1CP02047A.
12. ‫ۻ‬Miku Furushima, Daisuke Yoshida, Yukiumi Kita, Tomomi Shimazaki, and Masanori Tachikawa, Theoreticalinvestigation of the enhancement of positron affinity by the vibration and dimerization of non-polar carbon
disulfide", Phys. Chem. Chem. Phys., 23, 21512-21520 (2021). (Cover Image and selected as "2021 PCCP HOT
Articles") DOI: 10.1039/D1CP02808A.
13. ‫ۻ‬Taro Udagawa, Rhys B. Murphy, Tamim A. Darwish, Masanori Tachikawa, and Seiji Mori, "H/D isotope effects
in keto-enol tautomerism of β-dicarbonyl compounds importance of nuclear quantum effects of hydrogen nuclei",
Bull. Chem. Soc. Jpn., 94, 1954-1962 (2021). DOI: 10.1246/bcsj.20210083
14. Nuttapon Yodsin, Hiroki Sakagami, Taro Udagawa, Takayoshi Ishimoto, Siriporn Jungsuttiwong, and Masanori
Tachikawa, "Metal-doped carbon nanocones as highly efficient catalysts for hydrogen storage: Nuclear quantum
effectonhydrogenspillovermechanism",

Molecular

10.1016/j.mcat.2021.111486- 79 -

Catalysis,504,

111486(2021).

DOI:

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ࠿ࡽ㉥እ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝゎᯒ
6SHFWUDO$QDO\VLVIURP7HUDKHUW]WR0LG,QIUDUHG5HJLRQRQ&RPSOH[6\VWHPVᐩỌ ᆂ௓㸦⚄ᡞ኱ᏛศᏊࣇ࢛ࢺࢧ࢖࢚ࣥࢫ◊✲ࢭࣥࢱ࣮㸧 ◊✲┠ⓗࢸࣛ࣊ࣝࢶᖏ㸦7+] FP㸧࠿ࡽ㉥እ㡿ᇦ㸦FPaFP㸧࡟࠾ࡅࡿ࿘ἼᩘᖏࡣࠊศᏊ⣔ࡢศᏊෆ࠾ࡼࡧศᏊ㛫᣺ື࣮ࣔࢻ࡟┦ᙜࡋࠊỈ⣲⤖ྜᛶᾮయࡸ⁐ᾮࠊࡲࡓࢱࣥࣃࢡ㉁ࠊᑟ㟁ᛶ㧗ศᏊ➼ࡢ」㞧ศᏊ⣔࡟࠾ࡅࡿືⓗᣲືࡸᒁᡤᵓ㐀ࠊศᏊ㛫ࡢ┦஫స⏝➼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ศග➼ࢆ⏝࠸࡚ࠊࡇࢀࡽࡢ」㞧ศᏊ⣔࡟㛵ࡍࡿศගᏛⓗ࡞◊✲ࢆ᥎㐍ࡋ࡚࠸ࡿࠋ
ᮏ◊✲ㄢ㢟࡛ࡣࠊࡇࢀࡽࡢᐇ㦂⤖ᯝ࠿ࡽᐃ㔞ⓗ࡞᝟ሗࢆᚓࡿࡓࡵ࡟ࠊ኱ᆺィ⟬ᶵࢆ⏝࠸ࡓ⢭ᐦィ⟬ࢆ⾜࠺ࠋලయⓗ࡟ࡣࠊỈ⁐ᾮ୰࡟࠾ࡅࡿ࢝ࣝ࣎ࢽࣝ໬ྜ≀ࡢ᣺ືᩘᦂࡽࡂࠊỈ⁐ᾮ୰࡟࠾ࡅࡿ

ᗘᛂ⟅ᛶ㧗ศᏊࡢࢲ

࢖ࢼ࣑ࢡࢫࠊ」㞧⣔ࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢゎ㔘࡛࠶ࡿࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ ḟඖ᣺ືศග㸸ᅗ  ࡟♧ࡍⅣ໬Ỉ⣲ᇶࢆ᭷ࡍࡿศᏊࡢỈ୰࡟

࠾ࡅࡿ &2 ఙ⦰᣺ືࡢ㑄⛣᣺ືᩘࡢᦂࡽࡂࢆホ౯ࡋࡓࠋ஧ḟඖ㉥እศග ᐃ࡟ࡼࡿ⤖ᯝ࡜ẚ㍑ࡍࡿࡓࡵࠊᅗ D ࠾ࡼࡧᅗ F ࡢศᏊࡢ࢝ࣝ࣎࢟ࢩࣝᇶࡣ࢖࢜ࣥ໬ࡉࡏࠊ࢔ࣝࢹࣄࢻᇶࡲࡓࡣ࢝
ࣝ࣎ࢽࣝᇶࡢ &2 ఙ⦰᣺ືࡢ㑄⛣᣺ືᩘࢆ⪃࠼ࡿࠋᅗ  ࡟♧ࡋࡓ ⁐ ㉁ ศ Ꮚ ࡟ ࡘ ࠸ ࡚ ࠊ %/<3* GISG ࣞ ࣋ ࣝ ࡛ᅗ 㸬࢝ࣝ࣎ࢽࣝ໬ྜ≀ࡢศᏊᵓ㐀ࠋ*DXVVLDQ  ࣉࣟࢢ࣒ࣛ࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ⣙  ಶࡢ
7,33 ỈศᏊ࡛Ỉ࿴ࡋࡓ⣔ࢆసᡂࡍࡿࡇ࡜࡛ $0%(5 ࡟ࡼࡿศᏊືຊᏛィ⟬ࢆ⾜ࡗࡓࠋ ࠶ࡿ᫬้࡟࠾ࡅࡿ㑄⛣᣺ືᩘࢆホ౯ࡍࡿࡓࡵࠊ཮ᴟᏊ┦஫స⏝㏆ఝ࡟ᇶ࡙ࡃࣔࢹࣝࢆ౑⏝ࡋࡓ>@ࠋ┦஫స⏝ࢸࣥࢯࣝࢆ Tijࠊ⁐፹ࡢ཮ᴟᏊࢆPj ࡜ࡍࡿ࡜ࡁࠊ᣺ືᩘᦂࡽࡂ'Z t ࡢ᫬㛫┦㛵㛵ᩘࡣࠊ

'Z t 'Z  v¦T t P t ¦T  P 
ij

j

j

ij

j





j

࡜ࡋ࡚⾲ࡉࢀࡿࠋࡇࢀࢆ᣺ືᩘ᣺ືᩘ᫬㛫┦㛵㛵ᩘ ))7&) ࡜ᐃ⩏ࡍࡿࠋ⁐㉁࡟࠾ࡅࡿ┦஫స⏝Ⅼࢆ &2 ᇶࡢ୰Ⅼ࡜ࡋࠊᅗ  ࡟♧ࡍศᏊࡢ ))7&) ࡢῶ⾶ࡢ᫬ᐃᩘࢆᚓࡓࠋ
ᗘᛂ⟅ᛶ㧗ศᏊࡢࢲ࢖ࢼ࣑ࢡࢫ㸸 ᗘᛂ⟅ᛶ㧗ศᏊ࡛࠶ࡿ࣏
ࣜ 1࢖ࢯࣉࣟࣆࣝ࢔ࢡࣜࣝ࢔࣑ࢻ
㸦31L3$ࠊᅗ 㸧ཬࡧ࣏ࣜ 11ࢪ࢚ࢳࣝ࢔ࢡࣜࣝ࢔࣑ࢻ㸦3G($ࠊᅗ 㸧ࡢ┦㌿⛣⌧㇟ࢆ᳨ウࡋࡓࠋప ࡛ࡣศᏊ㙐ࡀఙࡧࡓࢥ࢖ࣝ≧ែ࡟࡞ࡾࠊ㧗 ࡛ࡣศᏊ㙐ࡀจ⦰ࡋࡓࢢࣟࣅ࣮ࣗࣝ≧ែ࡟࡞ࡿࠋࡇࡢ┦㌿⛣ࡢ࣓࢝ࢽࢡ

ࢫࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡓࡵࠊ*URPDFV ࢆ⏝࠸࡚ศᏊື
ຊᏛィ⟬ࢆ⾜ࡗࡓࠋຊሙ࡜ࡋ࡚ 23/6$$ ࢆ㐺⏝ࡋࠊỈ⁐ᾮࡢ

- 80 -ᅗ 㸬ᗘᛂ⟅ᛶ㧗ศᏊࡢศᏊᵓ㐀ࠋ

⼥Ⅼࢆṇ☜࡟⾲⌧ࡍࡿࡓࡵ࡟ 7,33,FH ࢆ⏝࠸ࡓࠋ༢㔞యࡀ  ಶ㐃⤖ࡋࡓࡶࡢࢆ⏝ពࡋࠊศᏊࡢ❧యつ๎ᛶࢆᐇ㦂ⓗ࡟ᚓࡽࢀࡿࡶࡢ࡟㏆࡙ࡅࡓࡶࡢࢆ⏝࠸ࡓ㸦PHVRG\DGa㸧ࠋNPT ᮲௳ୗ࡛ QV ࡢᵓ㐀ᖹ⾮໬ࢆ⾜࠸ࠊࡑࡢᚋ QV ࡢࢹ࣮ࢱࢆ IV 㛫㝸࡛グ㘓ࡋࡓࠋ ᗘࡣ . ࠿ࡽ . ࡲ࡛ . ࡎࡘኚ໬ࡉࡏࡓࠋ
ࢸࣛ࣊ࣝࢶศග㸸ࢸࣛ࣊ࣝࢶᖏࡢ᣺ືࢫ࣌ࢡࢺࣝࡢィ⟬࡛ࡣࠊᅛయᐦᗘỗ㛵ᩘἲࢆ⏝࠸ࡓࡀࠊ&5<67$/ࢆ౑⏝ࡋࡓࠋ⤖ᬗࡢ୪㐍ᑐ⛠ᛶࢆ⪃៖ࡍࡿࡓࡵ࡟࿘ᮇቃ⏺᮲௳ࢆ᥇⏝ࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚ࠊ*ULPPH ࡢศᩓຊࢆ⪃៖ࡋࠊ%/<3' ࢆ⏝࠸ࡓࠋᇶᗏ㛵ᩘ࡜ࡋ࡚ * GS  ࢆ⏝࠸ࡓࠋᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋ ◊✲ᡂᯝ ḟඖ᣺ືศග㸸ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓྛ⁐㉁㸦ᅗ 㸧ࡢつ᱁໬ࡉࢀࡓ ))7&) ࢆᅗ  ࡟♧ࡍࠋࡇࡢῶ⾶㐣⛬ࢆᐃᩘ㡯࡜஧ࡘࡢᣦᩘ
㛵ᩘࡢ࿴࡛ࣇ࢕ࢵࢸ࢕ࣥࢢࡋࠊᚓࡽࢀࡓῶ⾶ࡢ᫬ᐃᩘࢆᅗ୰࡟♧ࡋ࡚࠸ࡿࠋྛ⁐㉁࡟ඹ㏻ࡍࡿ᫬ᐃᩘ࡜ࡋ࡚⣙  SV ࡢࡶࡢࡀᚓ

ࡽࢀࠊࡇࢀࡣỈศᏊࡢ㠀ᖖ࡟᪩࠸୪㐍㐠ືࢆ཯ᫎࡋࡓࡶࡢ࡛࠶ࡿ

࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊῶ⾶඲యࢆ≉ᚩ௜ࡅࡿ᫬ᐃᩘࡣࠊᅗ D ࡜ᅗE ࡢศᏊ࡛ࡣ⣙  SVࠊᅗ F ࡢศᏊ࡛ࡣࡼࡾ㐜࠸  SV ࡢ᫬ᐃᩘࡀᚓࡽࢀࡓࠋࡇࢀࡣỈ⣲⤖ྜࡢ⤌ࡳ࠿࠼㐣⛬ࢆ཯ᫎࡋࠊ஧ḟඖ㉥እศග ᐃ࠿ࡽᚓࡽࢀࡓ್ࡣࡑࢀࡒࢀ ࠊࠊSV ࡢࡓࡵࠊᦤືㄽ࡟ᇶ࡙ࡃᘧ  ࡢࣔࢹࣝࡀⰋ࠸㏆ఝ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿࠋࡲࡓࠊᅗ E ࡜ᅗ F ࡢศᏊᵓ㐀ࡣ࡯࡜ࢇ࡝ྠࡌ࡛࠶ࡿ࡟ࡶ㛵ࢃࡽࡎࠊࡑࡢῶ⾶ࡢ᫬ᐃᩘࡣᐇ㦂࠾ࡼࡧィ⟬⤖ᯝඹ࡟⣙  ಸ␗࡞ࡿࠋᅗ 㸬ྛ⁐㉁ࡢ ))7&) ࡢィ⟬⤖ᯝࠋࡇࡢ᫬ᐃᩘࡢᕪࡣࠊ᣺ືࣉ࣮ࣟࣈ࡛࠶ࡿ &2 ᇶ࡜࿘ᅖࡢⅣ໬Ỉ⣲⎔࡜ࡢ┦ᑐ఩⨨࡟㉳ᅉࡍࡿࠋ᣺ື≧ែࡣࠊࡑࡢ᣺ື㍈᪉ྥ࡟ᑐࡍࡿ࿘ᅖࡢ⁐፹ࡢᦂࡽࡂ࡟ᛂࡌ࡚᭱ࡶ㢧ⴭ࡟ኚ໬ࡍࡿࠋࡋࡓࡀࡗ࡚ࠊᅗ F ࡢศᏊ࡛ࡣⅣ໬Ỉ⣲⎔࠾ࡼࡧ࢖࢜ࣥ㒊ศࡢᏑᅾ࡟ࡼࡾࠊືࡁࡀᢚไࡉࢀࡓỈศ
Ꮚࡀ &2 ᇶ㏆ഐ࡟Ꮡᅾࡋࠊᒁᡤⓗ࡞ㄏ㟁⎔ቃࡀ௚ࡢࡶࡢ࡜ࡣ␗࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊᅗ D ࡸᅗ E ࡢศ
Ꮚ࡛ࡣࠊ&2 ㍈᪉ྥ࡟ẚ㍑ⓗ⮬⏤࡞ỈศᏊࡀ᥋㏆ࡋࡸࡍ࠸ࡓࡵࠊࡑࡢ᪩࠸㐠ືࢆ཯ᫎࡋ࡚᫬ᐃᩘࡀ▷ࡃ࡞ࡗࡓ࡜⪃࠼ࡽࢀࡿࠋ௨ୖࡼࡾࠊᚤどⓗ࡞ศᏊᵓ㐀࡟ࡼࡾࠊศᏊࡀཷࡅࡿ࿘ᅖ࡜ࡢ┦஫స⏝ࡀ኱ࡁࡃኚ໬ࡍࡿࡇ࡜
ࡀ♧ࡉࢀࡓࠋ
ᗘᛂ⟅ᛶ㧗ศᏊࡢࢲ࢖ࢼ࣑ࢡࢫ㸸ᗘᛂ⟅ᛶ㧗ศᏊࡢ┦㌿⛣࡟ࡘ࠸࡚㆟ㄽࡍࡿࠋ┦㌿⛣ࡢ㐍⾜ࡣᅇ㌿༙ᚄࡢ᫬㛫ኚ໬࡜㛵㐃௜ࡅࡽࢀࠊᅗ DࠊG ࡟ྛᗘࡢᖹᆒ್ࢆ♧ࡍࠋ┦㌿⛣ࡣ⣙ Υ࡛㉳ࡇࡿࡇ࡜ࡀ▱ࡽࢀࠊᅗ

DࠊG ୰ࡢ . ௜㏆ࡢᛴ⃭࡞ RJ ࡢῶᑡࡣࠊศᏊࡀࢢࣟࣅ࣮ࣗࣝ≧ែ࡟ኚ໬ࡋࡓࡇ࡜࡟ᑐᛂࡍࡿࠋࡇࡢ┦㌿⛣࡛ࡣࠊศᏊෆỈ⣲⤖ྜࡢᙧᡂࡸᵓ㐀ኚ໬࡟క࠺Ⅳ໬Ỉ⣲ᇶ㸦ഃ㙐ࡢ࣓ࢳࣝᇶࡢⅣ⣲ཎᏊ㸧ྠኈࡢ᥋ゐࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡇ࡛ࡣࠊ஧ࡘࡢ༢㔞య༢఩㛫ࡢⅣ໬Ỉ⣲ᇶྠኈࡢ᥋ゐᩘࡢᙧᡂ఩⨨࡟ࡘ࠸࡚ศ㢮ࡋࠊᵓ㐀ኚ໬ࢆࡶࡓࡽࡍࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸᳨࡚ウࡋࡓࠋn㸦n «㸧␒┠ࡢ༢㔞య఩⨨࡜ nk ␒┠ࡢ఩⨨ࡢࡶࡢࡀ᥋ゐࡍࡿ࡜ࡁࠊk ࡀ  ௨ୗࡢ᫬࡜  ௨ୖࡢ᫬࡛ሙྜศࡅࢆ⾜ࡗࡓࠋ࡞࠾ࠊணࡵィ⟬ࡋࡓศᏊෆືᚄ
ศᕸ㛵ᩘ࠿ࡽࠊ31L3$ ࡛ࡣ && ㊥㞳ࡀ Ⴒ ௨ୗࡢ࡜ࡁࠊ3G($ ࡛ࡣ Ⴒ ௨ୗࡢ᫬࡟᥋ゐࡋ࡚࠸ࡿ࡜ࡳ࡞ࡋࡓࠋᅗ EࠊFࠊHࠊI ࡟Ⅳ໬Ỉ⣲ᇶࡢᖹᆒ᥋ゐᩘࡢ ᗘኚ໬ࢆ♧ࡍࠋࡑࡢ⤖ᯝࠊk ࡢ್࡟ᛂࡌ࡚ ᗘ౫Ꮡᛶࡀ␗
࡞ࡿࡇ࡜ࡀ♧၀ࡉࢀࠊk ࡀ  ௨ୗࡢሙྜࡣ ᗘ࡟࡯࡜ࢇ࡝౫Ꮡࡏࡎࠊ㏫࡟  ௨ୖࡢሙྜࡣࢩࢢࣔ࢖ࢻᆺࡢࡼ
࠺࡞ኚ໬ࢆ♧ࡋࡓࠋࡇࡢᕪࡢཎᅉ࡜ࡋ࡚ࠊ㞳ࢀࡓ఩⨨ྠኈ࡛ᙧᡂࡉࢀࡿࡇ࡜࡟ࡼࡗ࡚ึࡵ࡚㦵᱁ࡢࡡࡌࢀࡀ

- 81 -

ㄏⓎࡉࢀࡿࡀࠊ㏆᥋ࡍࡿࡶࡢࡣ

ᗘ࡟ࡼࡽࡎ࡯ࡰ୍ᐃࡢ๭ྜ࡛Ꮡᅾࡋࠊࢢࣟࣅ࣮ࣗࣝ≧ែ࡬ࡢ㑄⛣࡟ࡣᙳ㡪ࡋ࡞࠸ࡓࡵ࡛࠶ࡿࠋ31L3$ ࡜ 3G($ ࡢ⤖ᯝࢆẚ㍑ࡍࡿ࡜ࠊ3G($ ࡢ᪉ࡀᖹᆒ᥋ゐᩘࡀᑡ࡞ࡃࠊࡲࡓ

ᗘ࡟ᑐࡍࡿ౫Ꮡᛶࡀ 31L3$ ࡟ẚ࡭ࡿ࡜࡞ࡔࡽ࠿࡛࠶ࡿࠋศᏊෆỈ⣲⤖ྜ࡟ࡼࡿᵓ㐀ࡢᏳᐃ໬ࡢᕪ࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࡿࡀࠊヲ⣽ࡣ௒ᚋࡢㄢ㢟࡛࠶ࡿࠋࡲ࡜ࡵ࡜ࡋ࡚ࠊᵓ㐀ࡢ┦㌿⛣ࢆ≉ᚩ௜ࡅࡿୖ࡛ศᏊෆỈ⣲⤖ྜࡸⅣ໬Ỉ⣲ᇶࡢ᥋ゐ఩⨨ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
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ᅗ 㸬 D 31L3$ ࠾ࡼࡧ G 3G($ ࡢᅇ㌿༙ᚄ㸦RJ㸧ࡢᖹᆒ್ࡢ ᗘኚ໬ࠋ E 31L3$ ࠾ࡼࡧ H 3G($ ࡢ k ࡀ ௨ୗࡢ᫬ࡢⅣ໬Ỉ⣲ᇶࡢ᥋ゐᩘࠋ F 31L3$ ࠾ࡼࡧ I 3G($ ࡢ k ࡀ  ௨ୖࡢ᫬ࡢⅣ໬Ỉ⣲ᇶࡢ᥋ゐᩘࠋࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢゎ㔘㸸ࣔࣥࣔࣜࣟࢼ࢖ࢺ㸦㹋0W㸧ࡣࠊᒙ≧ࢣ࢖㓟ሷ㖔≀ࡢ୍✀࡛࠶ࡾࠊࢣ࢖㓟࠿ࡽ࡞ࡿࢩ࣮ࢺࡀᒙ≧࡟ᙧᡂࡉࢀࡿࠋࡇࡢᒙࡢ㛫࡟Ỉࡸ㔠ᒓ࢖࢜ࣥࢆᐜ᫆࡟ྲྀࡾ㎸ࡳࡲࡓᨺฟࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ᡃࠎࡣࡇࡢ 00W ࡢ஝⇱≧ែࠊ࠾ࡼࡧỈ࿴≧ែࡢࢸࣛ࣊ࣝࢶศගࡢほࢆጞࡵ࡚࠸ࡿࠋᮏィ⟬࡛ࡣࠊ஝⇱≧ែ࡜Ỉ࿴≧ែࢆ෌⌧ࡍࡿࣔࢹࣝ⣔ࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ1D ࢖࢜ࣥࢆྵࡴ 00W ࢆᑐ㇟࡜ࡋࡓࡀࠊ஝⇱≧ែ࡛ 1D ࢖࢜ࣥࡢ఩⨨㸦ᒙ㛫࠿ࠊᒙࡢ୰࠿㸧ࢆ୍ࡘࡢதⅬ࡜ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋᅗ  ࡟ࡣ 1D ࢖࢜ࣥࡀᒙࡢ
୰࡟Ꮡᅾࡍࡿ࡜ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋᅗ  E ࡟ᐇ ࡜ィ⟬ࡢ ;5' ࡢ⤖ᯝࢆ♧ࡍࡀࠊࡼ࠸୍⮴ࡀ࠼ࡽࢀ࡚࠸ࡿࠋᅗ  ࡟Ỉ࿴ࡋࡓ 00W ࡢᵓ㐀᭱㐺໬ࡢ⤖ᯝ࡜ᐇ ཬࡧィ⟬ࡢ ;5' ࡢ⤖ᯝࢆ♧ࡍࠋỈࡢྵ㔞ࡣ㔜㔞㸣࡛ 㸣࡛
࠶ࡿࠋ1D ࢖࢜ࣥࡣỈࡀᏑᅾࡍࡿࡓࡵࠊᒙ㛫࡟㓄⨨ࡋࡓࠋࡑࢀ࡟ࡼࡾ࢖࢜ࣥࡢỈ࿴ࡀ㉳ࡇࡗ࡚࠸ࡿࠋ;5' ࡟ࡘ࠸࡚ᐇ㦂࡜ィ⟬ࡣࡼ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࠋD

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ᅗ 㸬஝⇱≧ែࡢ 00W ࡟ᑐࡍࡿ᭱㐺໬ࡋࡓᵓ㐀㸦D㸧࡜⢊ᮎ ; ⥺ᅇᢡࣃࢱ࣮ࣥࡢᐇ㦂್࡜ィ⟬್㸦E㸧ࠋ

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ਦ ɿỈ࿴≧ែࡢ 00W ࡟ᑐࡍࡿ᭱㐺໬ࡋࡓᵓ㐀㸦D㸧࡜⢊ᮎ ; ⥺ᅇᢡࣃࢱ࣮ࣥࡢᐇ㦂್࡜ィ⟬್㸦E㸧ࠋỈศ㔞ࡣ㔜㔞㸣࡛ ࡜ࡋ࡚࠸ࡿࠋ

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- 83 -

㔞ᏊຊᏛ㸦40㸧ศᏊຊᏛ㸦00㸧ἲ࡜ศᏊືຊᏛィ⟬࡟ࡼࡿࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲ࡢ཯ᛂᶵᵓゎᯒ
$QDO\VLVRIUHDFWLRQPHFKDQLVPRIKDORDFLGGHKDORJHQDVH 
E\4XDQWXPPHFKDQLFV 40 0ROHFXODUPHFKDQLFV 00   DQGPROHFXODUG\QDPLFVPHWKRG‫ ۑ‬୰ᮧ ༟㸦㛗὾ࣂ࢖࢜኱Ꮫ㸧㸯 ◊✲┠ⓗࠊෆᐜᡃࠎࡢ◊✲ᐊ࡛ࡣ⌧ᅾࠊ᭷ᶵࣁࣟࢤࣥ໬ྜ≀ࡢศゎ㓝⣲࡜ࡋ࡚᭷ᐖ≀㉁ศゎ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࡿ L-2-ࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲㸦L-DEX㸧ࢆࢱ࣮ࢤࢵࢺ㓝⣲࡜ࡋ࡚ࠊᐇ㦂࡜ィ⟬࡟ࡼࡾ㓝⣲཯ᛂᶵᵓࢆศᏊ࡛ࣞ࣋ࣝ
ゎ᫂ࡋࠊࡑࡢ▱ぢࢆ⏝࠸࡚㔝⏕ᆺࡢ㓝⣲ࡼࡾࡶ㧗ᶵ⬟࡞ᨵኚ㓝⣲ࢆࢹࢨ࢖ࣥࡋ࡚ᐇ㝿࡟๰ࡾฟࡍࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋࡑࡢࡓࡵ࡟ࠊL-DEX ᮏ᮶ࡢᇶ㉁࡛࠶ࡿ L-2-ࢡࣟࣟࣉࣟࣆ࢜ࣥ㓟㸦L-2-CPA㸧ࢆ⏝࠸࡚ࠊL-DEX ࡢ㓝⣲཯ᛂ⤒㊰ࢆᐦᗘ༙㛵ᩘἲ㸦DFT㸧࡟ࡼࡾィ⟬ࡋࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡍࡿ཯ᛂ⤒㊰ࢆ᥎ᐃࡍࡿࡇ࡜ࢆ⪃࠼ࡓࠋ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲ
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 16 ࢔࣑ࣀ㓟㸦Asp10ࠊArg41ࠊLys151ࠊAsp180 ࡞࡝㸧ࡢഃ㙐㒊ศ࡜ྜィ 185 ཎᏊࡢ⣔ࢆ QM 㡿ᇦ࡟ᣦᐃࡋࠊࡑࢀ௨እࢆ 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⟬⤖ᯝ࡛ࡣࠊ཯ᛂࡢᚊ㏿ẁ㝵࡜࡞ࡿ 2 ẁ㝵┠ࡢຍỈศゎ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ 30 ࠿ࡽ
40 kcal/mol ࡛ᐇ㦂⤖ᯝ࡜ᑐᛂࡋ࡞࠿ࡗࡓࠋ2020 ᖺᗘࡣ QM 㡿ᇦࢆ 118 ཎᏊ࠿ࡽ 185 ཎᏊ࡟ᣑᙇࡋࠊQM ィ⟬ࡶ B3LYP/6-31G(d)࠿ࡽZB97X-D/6-31G (d)ࣞ࣋ࣝ࡟ࡋ࡚ィ⟬ࡋࡓ࡜ࡇࢁࠊάᛶ໬࢚ࢿࣝࢠ࣮ࡀ 29.43
kcal/mol ࡜࡞ࡾࠊࡇࢀࡲ࡛࡛᭱ࡶᑠࡉ࠸್࡜࡞ࡗࡓࠋࡉࡽ࡟ࠊຍỈศゎ཯ᛂࡢ TS ᵓ㐀࠿ࡽ IRC ィ⟬࡛ᚓࡽࢀࡓ཯ᛂ๓ᵓ㐀ࡀࠊ㸯ẁ㝵┠ࡢ⬺ࣁࣟࢤࣥ໬཯ᛂࡢ཯ᛂ⏕ᡂ≀ᵓ㐀࡜࡯ࡰ୍⮴ࡋࠊ୍㐃ࡢ཯ᛂࡀ㐃⥆ⓗ࡟ゎᯒ࡛ࡁࡿࡼ࠺࡟ᛮࢃࢀࡓࠋ

㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ㸳 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Liu, Y., Li, Y., Chen, G., Wang, X.F., Fujii, R., Yamano, Y., Kitao, O., Nakamura, T., and Sasaki, S.
Adv. Mater. Interfaces , 2101303.

- 84 -

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

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ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡣࠊ໬Ꮫ࣭⏕≀Ꮫ࣭≀㉁≀⌮Ꮫࢆᨭ㓄ࡍࡿ᪉⛬ᘧ࡛࠶ࡾࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞

᪉⛬ᘧࢆṇ☜࠿ࡘᐜ᫆࡟ゎࡃ⌮ㄽࡀᏑᅾࡋࠊࡑࢀࢆㄡࡶࡀ౑࠼ࡿィ⟬ࣉࣟࢢ࣒ࣛࡀ᏶ᡂࡍࢀࡤࠊ໬Ꮫ⌧㇟ࢆᐇ㦂ࡢࡳ࡛࡞ࡃ⌮ㄽ࡜ィ⟬࡟ࡼࡗ࡚ࡶṇ☜࡟ணゝࡍࡿ㐨ࡀ㛤ࡅࡿࠋᮏ◊✲ㄢ㢟௦⾲⪅ࡣࡇࡢ᪉⛬ᘧࡢ୍⯡ゎἲࢆୡ⏺࡛ึࡵ࡚Ⓨぢࡋ 3K\V5HY/HWW   ࠊࡑࡢゎἲࢆ⮬⏤᏶ဨ㛵ᩘ⌮ㄽ )UHH &RPSOHPHQW)&  WKHRU\ ࡜ࡋ࡚⌮ㄽయ⣔ࢆᵓ⠏ࡋࡓࠋᮏㄢ㢟ࡢ┠ⓗࡣࠊࡇࡢ⌮ㄽࢆࡉࡽ࡟㐍໬ࡉࡏࠊㄡࡶࡀࠕᐜ᫆ࠖ࠿ࡘ
ࠕᏳᐃࠖ࡟ࠕṇ☜ࠖ࡞ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࢆࠕ㧗㏿ࠖ࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ⌮ㄽ࡜᪉ἲࢆ㛤Ⓨࡍࡿࡇ࡜࡛࠶ࡿࠋࡑࢀࡀ☜❧ࡉࢀࢀࡤࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ࣞ࣋ࣝࡢணゝⓗ㔞Ꮚ໬Ꮫࡀࠊ┿࡟໬Ꮫࡢணゝⓗࢶ࣮ࣝ࡜ࡋ࡚ᗈࡃ฼⏝ࡉࢀࡿࡼ࠺࡟࡞ࡾࠊ㔞Ꮚ໬Ꮫࡢணゝ⬟ࡣ᱁ẁ࡜ྥୖࡋࠊ໬Ꮫ඲యࡀ⤒㦂ⓗ≀㉁Ꮫ࠿ࡽࡼࡾ⌮ㄽⓗ࡞≀㉁Ꮫ࡟⛣⾜ࡋࠊ኱ࡁࡃ㐍Ṍࢆ㐙ࡆࡿ࡛࠶ࢁ࠺ࡇ࡜ࡀண

ࡉࢀࡿࠋࡇࡢ┠ⓗ㐩ᡂ࡟ྥࡅࠊᮏィ⟬ᶵ฼⏝ཬࡧィ⟬ࢭࣥࢱ࣮ࡢከ኱࡞ࢧ࣏࣮ࢺ࡜ඹ࡟ࠊ⥅⥆ⓗ࣭㠉᪂ⓗ࡞◊✲ࢆᒎ㛤ࡋࠊࡑࡢᇶ♏ⓗ࡞⌮ㄽయ⣔ࡣ࡯ࡰ☜❧ࡉࢀࠊ╔ᐇ࡟㐩ᡂ࡬࡜㐍ࢇ࡛࠸ࡿࠋ ᖺᗘࡣࠊࡇࢀࢆᐇ⏝໬ࣇ࢙࣮ࢬ࡟⛣⾜ࡍࡿࡓࡵᗄࡘ࠿ࡢ㔜せ࡞᪉ἲࢆᥦ᱌ࡋⓎᒎࡉࡏࡓࠋࡇࡢヲ⣽ࢆ  ❶௨㝆࡟㏙࡭ࡿࠋࡲࡓࠊࡶ࠺୍᪉ࡢࢸ࣮࣐࡛࠶ࡿ SAC-CI ἲࡢ⌮ㄽⓗᒎ㛤࡜ᛂ⏝࡟࠾࠸࡚ࡣࠊෆẆ࢖࢜ࣥ໬࠾ࡼࡧෆẆບ㉳ࡢ⌧㇟࡟ᛂ⏝ࡋࠊᐇ㦂ᐙ࡜ࡢඹྠ◊✲ࡶ㐍ࡵࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ

2.1. Ἴື㛵ᩘࡢ㧗⢭ᗘ໬FC ⌮ㄽ࡟ࡼࡗ࡚ࠊィ⟬㈨※ෆ࡛ᐇ⏝ⓗ࡟ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࡟ゎࡃࡓࡵ࡟ࡣࠊἼື㛵ᩘࢆ࡛ࡁࡿࡔࡅຠ⋡ⓗ࡟ potentially exact ࡞ᙧ࡛ᵓᡂࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋࡑࡢࡓࡵ࡟ࠊ⣔࡟㐺ࡋࡓึᮇ㛵ᩘ࡜ࢫࢣ࣮ࣜࣥࢢ㛵ᩘ(g 㛵ᩘ)ࡢ㑅ᢥࡀ≉࡟㔜せ࡛࠶ࡿࠋ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ: ึᮇ㛵ᩘᵓ⠏࡟ࡘ࠸࡚ࡣࠊ໬Ꮫ⪅ࡢ໬Ꮫᴫᛕ(ศᏊᵓ㐀ᘧࡸ໬Ꮫ཯ᛂᘧ)࡜ᑐᛂࡍࡿ
Ἴື㛵ᩘࢆᵓ⠏ࡍࡿ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽࢆᥦ᱌ࡋࡓ(J. Chem. Phys. 149, 114105 (2018).)ࠋࡇࡢ᪉ἲࡣࠊ໬Ꮫ
ⓗ࡞ᮏ㉁ࢆἼື㛵ᩘ࡟཯ᫎࡍࡿࡓࡵࠊṇ☜ࡉ࡜ྠ᫬࡟໬Ꮫⓗ⌮ゎ࡟ࡶ⧅ࡀࡿࠋࡲࡓࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ࡟ἢ
ࡗࡓᒁᡤⓗ࡞Ἴື㛵ᩘ࡜ࡋ࡚グ㏙ࡉࢀࡿࡓࡵࠊiExg ⌮ㄽ(J. Chem. Phys. 142, 194101 (2015).)࡜㐃ᦠࡋ኱ࡁ࡞⣔࡬ࡢᣑᙇ࡟ࡶ⧅ࡀࡿࠋ
ṇࡋ࠸ࢫࢣ࣮ࣜࣥࢢ㛵ᩘ: ୍᪉ࠊ2004 ᖺࡢㄽᩥࡢ᰿ᖿࡣࠊscaled Schrödinger equation: J +  ( \ ࡢᑟධ࡟ࡼࡗ࡚ࠊᚑ᮶ࡣゎࡅ࡞࠿ࡗࡓࢡ࣮ࣟࣥⓎᩓၥ㢟ࢆゎỴࡋࡓࡇ࡜࡟࠶ࡿࠋࡇࡇ࡛ᑟධࡉࢀࡓ g 㛵ᩘ࡟࠾࠸࡚ࠊ≉࡟ 2 㟁Ꮚ㡯: gij ࡟ࡘ࠸࡚ࠊձ⾪✺఩⨨࡛ࡢⓎᩓࢆ㜵ࡄ࡜ྠ᫬࡟⾪✺఩⨨࡛ࡢ᝟ሗࢆᾘࡉ࡞࠸(࢝ࢫࣉ᮲௳ࢆ‶ࡓࡍ)ࡇ࡜ࠊղ⾪✺ࡢ࡞࠸㡿ᇦ࡛ࡣ scaled ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡀඖࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟₞㏆ࡍࡿࡇ࡜ࠊ࡜࠸࠺ 2 ᮲௳ࢆ‶ࡓࡍ㛵ᩘ(correct 㛵ᩘ࡜࿧ࡪ)ࢆᑟධࡋࡓࠋձ, ղࡢ୧⪅ࢆ‶ࡓࡍ㛵ᩘࢆ”correct”, ձࡢࡳ‶ࡓࡍ㛵ᩘࢆ”reasonable”, ձࢆ‶ࡓࡉ࡞࠸㛵ᩘࢆ”approximate”࡜ࡋࡓࠋㄽᩥ(J. Chem. Phys.

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156, 014113 (2022).)ࡸ๓ᖺᗘሗ࿌᭩࡛㏙࡭࡚࠸ࡿࡼ࠺࡟ࠊ”correct”㛵ᩘࢆ⏝࠸ࡿ࡜”reasonable”ࡸ”approximate”
㛵ᩘࡼࡾࡶ᫂ࡽ࠿࡟཰᮰ࡀ㏿࠿ࡗࡓࠋᣦᩘ✚ศ㛵ᩘ(exponential integral (Ei))㛵ᩘࡣࠊ࠿ࡘ࡚ He ཎᏊࡢ 43 ᱆ࡢ࢚ࢿࣝࢠ࣮ࡢィ⟬࡛ࡶ᭷⏝࡛࠶ࡾ(Phys. Chem. Chem. Phys. 10, 4486 (2008).)ࠊ”correct”㛵ᩘࡢ୰࡛᭱ࡶ
performance ࡀⰋ࠿ࡗࡓࠋ୍⯡ⓗ࡞ཎᏊ࣭ศᏊ࡬ࡢᛂ⏝࡟࠾࠸࡚ࡶࠊࡇࡢࡼ࠺࡞”correct”ࡢ gij 㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡛ࠊἼື㛵ᩘࡢᛶ㉁ࢆ㧗ࡵࡿࡇ࡜ࡀ࡛ࡁࠊᚑ᮶ࡢ rij 㡯ࡼࡾࡶ exact ゎ࡬ࡢ཰᮰ࢆ㏿ࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡲ
ࡓࠊᛶ㉁ࡢ␗࡞ࡿ gij 㛵ᩘࢆ」ᩘ⏝࠸ࡿ᪉ἲ࡞࡝ࠊᐇ⏝ᛶ࣭ỗ⏝ᛶࢆᣑࡆࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

2.2. ┤᥋ἲ(Direct Local Sampling ἲ)࡟ࡼࡿࢧࣥࣉࣜࣥࢢ⏕ᡂ᏶ဨ㛵ᩘࡢ✚ศࡀྍ⬟࡛࠶ࡿሙྜࡣኚศἲࢆ⏝࠸ࡿࡇ࡜ࡀ࡛ࡁࡿࡀࠊࡑ࠺࡛࡞࠸ሙྜࡣࢧࣥࣉࣜࣥࢢᡭἲ
࡛࠶ࡿ Local Schrödinger Equation (LSE) ἲ(Phys. Rev. Lett. 99, 240402 (2007).)ࢆ⏝࠸ࡿࡇ࡜࡛ࠊFC ⌮ㄽࡢἼື㛵ᩘࢆ✚ศࡢไ⣙࡞ࡃ㛵ᩘᮏ᮶ࡢṇ☜ࡉ࡛グ㏙ࡋࠊexact ゎࢆ㏣ồࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ୍᪉ࠊ㔞Ꮚࣔࣥࢸ࢝ࣝ
ࣟἲ࡞࡝ࡢࢧࣥࣉࣜࣥࢢ࡟ᇶ࡙ࡃ㔞Ꮚ໬Ꮫ⌮ㄽࡢ࡯࡜ࢇ࡝(࡯ࡰ඲࡚)ࡀࠊ࠸ࢃࡺࡿ࣓ࢺ࣏ࣟࣜࢫἲࢆ⏝࠸࡚࠸ࡿࠋࡇࡢ᪉ἲࡣࠊྂ඾⤫ィᏛ࡟ᇶ࡙ࡁྂ඾ⓗ࢛࣮࣮࢘࢝ࢆࢩ࣑࣮ࣗࣞࢺࡍࡿࡶࡢ࡛࠶ࡾࠊࣛࣥࢲ࣒ᛶࡸࢩ࣑
࣮ࣗࣞࢩࣙࣥࡢ᪉ἲࡢ౫Ꮡᛶ࡞࡝ࡢ᪂ࡓ࡞᭕᫕ᛶࢆྲྀࡾ㎸ࢇ࡛ࡋࡲ࠺ࠋ
ᡃࠎࡣࠊexact ࣞ࣋ࣝࡢィ⟬࡟㐺ࡋࡓ࡛ࡁࡿࡔࡅ㔞ᏊຊᏛⓗ࡞Ỵᐃㄽⓗ࡞ࢧࣥࣉࣜࣥࢢࢆసࡿࡇ࡜ࢆ┠ᣦࡋࠊ௨๓࡟ᥦ᱌ࡋ࡚࠸ࡓ Local Sampling ἲ(J. Chem. Phys. 149, 114106 (2018).)ࢆⓎᒎࡉࡏࠊከḟඖࡢ”㏫ኚ᥮ἲ”࠶ࡿ࠸ࡣ”┤᥋ἲ”(ὠ⏣ Ꮥኵ, ͆ࣔࣥࢸ࢝ࣝࣟἲ࡜ࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ, ᇵ㢼㤋. L. Devroye, “Non-Uniform
Random Variate Generation”, New York, Springer-Verlag (1986).)ࢆࢧࣥࣉࣜࣥࢢⅬ⏕ᡂ࡟ᛂ⏝ࡍࡿ᪉ἲࢆᑟධࡋ
ࡓࠋࡲࡎࠊࡑࡢᇶ♏࡛࠶ࡿ 1 ḟඖ㏫ኚ᥮ἲ࡟ࡘ࠸࡚ᴫᛕࢆㄝ᫂ࡍࡿࠋ࠶ࡿ 1 ḟඖࡢᐦᗘ㛵ᩘ(ศᕸ㛵ᩘ):I [[ >D E@ ࡟ἢ࠺ࢧࣥࣉࣜࣥࢢⅬࢆ⏕ᡂࡍࡿሙྜࠊ[0,1]ࡢ୍ᵝศᕸࢆ I [ ࡢศᕸ࡟࣐ࢵࣆࣥࢢࡍࡿࠋ

ࡍ࡞ࢃࡕࠊ
[

³ G[

[



K

/ ³ G[ I [Dࡀᡂࡾ❧ࡘࡼ࠺࡟ K ࢆỴࡵࡿࠋࡇࡇ࡛ࠊ [ ࡣ[0,1]ࡢ୍ᵝศ

f 䛾ศᕸ

[0,1]䛾୍ᵝศᕸ

ᕸࡢ୍Ⅼࠊ/ ࡣ I [ ࡢつ᱁໬ᐃᩘ࡛࠶ࡿࠋᅗ 1 ࡟♧ࡍࡼ࠺
࡟ࠊ(1)ᘧࡢᕥ㎶ࡣ[0, [ ]ࡢ㧗ࡉ 1 ࡢ㛗᪉ᙧࡢ㠃✚ࠊྑ㎶ࡣ[a,K ]ࡢ I [ ࡀᡂࡍ㠃✚࡛࠶ࡾࠊ୧⪅ࡀ୍⮴ࡍࡿ᮲௳࡛ K ࡀỴࡵࡽࢀࠊࡇࡢ K ࡢศᕸࡇࡑࡀ I [ ࡢศᕸ࡟ᑐᛂࡋ࡚࠸ࡿࠋ 0[ࡇࡢ࣐ࢵࣆࣥࢢ࡟࠾࠸࡚ࠊ஘ᩘ(ࢧ࢖ࢥࣟ)ࡣ౑ࢃࢀ࡞࠸ࠋᅗ  ㏫ኚ᥮ἲࡢᴫᛕ

1

a

K

b

ḟ࡟ࠊ୍⯡࡟ p 㟁Ꮚࡢᐦᗘ㛵ᩘ I S [  [   [ S ࡟ᑐࡍࡿࢧࣥࣉࣜࣥࢢศᕸࡢ⏕ᡂࢆ⪃࠼ࡿࠋࡇࡢከ㟁Ꮚ ከḟඖ ࡢ㏫ኚ᥮ἲࡢࢫࢸࢵࣉࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋL  [  [  [LL ࡣ᪤࡟ỴࡲࡗࡓᗙᶆⅬ [P  [P  [L P ࡀ୚࠼ࡽࢀ࡚࠸ࡿ࡜ࡍࡿࠋLL  ࡇࡢ᮲௳ୗ࡛㟁Ꮚ L ࠿ࡽ S ࡲ࡛✚ศࡋࡓ L ḟࡢ⦰⣙ᐦᗘ㛵ᩘ I L [P  [P  [L P  [Lࢆィ⟬ࡍࡿࠋ LLL  ࡣ㟁Ꮚ L ࡔࡅࡢ㛵ᩘ࡛࠶ࡾ  㟁Ꮚࡢ㏫ኚ᥮ἲࢆ㐺⏝ࡍࡿࠋࡍ࡞ࢃࡕࠊ

ȟLȘL

/L ³ G[L I L [P  [P  [L P  [Lࢆ‶ࡓࡍ ȘL ࢆồࡵࡿࠋࡇࡇ࡛ࠊ ȟ L ࡣ୍ᵝศᕸࡢ  ࡘࡢⅬ࡛࠶ࡿࠋ / L ࡣ I L [P  [P  [L P  [L ࡢつ᱁໬ᐃᩘ࡛࠶ࡿࠋ[L ࡣ  ḟඖ࡛࠶ࡾᐇ㝿ࡣࡇࢀࢆࡉࡽ࡟⦰⣙ࡋ࡚  ḟඖࡢ㏫ኚ᥮ἲ  ᘧ ࢆ  ᅇ⾜࠺ࠋȘL ࡣ㟁Ꮚ L ࡢⅬ

[L PȘL ࡜࡞ࡿࠋ LY  L 㹼 LLL ࢆ㟁Ꮚ  ࠿ࡽ S ࡲ࡛⧞ࡾ㏉ࡍࡇ࡜࡛ࠊ I S ࡢศᕸ࡟ᚑ࠺ S 㟁Ꮚᗙᶆࡢ  ࡘࡢࢧ- 86 -

ࣥࣉࣜࣥࢢⅬ UP S[P  [P  [ SP ࢆᚓࡿࠋS  ࡢሙྜࠊྛ㟁ᏊࡢࢧࣥࣉࣜࣥࢢⅬࢆ I  [*  [ _ [  㟁Ꮚᐦᗘ ࡟ᑐࡋ࡚⏕ᡂࡍࡿ᪉ἲࢆ *  ࢧࣥࣉࣜࣥࢢἲ࡜࿧ࡪࠋS  ࡢሙྜࠊ㟁Ꮚࡢࣁ࣑ࣝࢺࢽ࢔ࣥࡣ  㟁Ꮚ₇⟬Ꮚࡲ࡛ࡋ࠿ྵࡲ࡞࠸ࡓࡵࠊṇ☜࡞
1UHSUHVHQWDELOLW\ ࢆ‶ࡓࡍ *  ࡟ᇶ࡙ࡃࢧࣥࣉࣜࣥࢢ⏕ᡂࡣ㔜せࡔࡀࠊ≉࡟㟢ࢃ࡞㟁Ꮚ┦㛵㡯ࢆᢅ࠺ሙྜࡣ✚ศᅔ㞴࡞ၥ㢟ࡀ࠶ࡿࠋS 1 ࡢሙྜࠊ1 㟁ᏊἼື㛵ᩘ < ࡟ᑐࡍࡿ඲㟁Ꮚᐦᗘ I 1*1<  ࡟ἢ࠺ࢧࣥࣉࣜࣥ

ࢢ⏕ᡂࢆ * 1 ࢧࣥࣉࣜࣥࢢἲ࡜࿧ࡪࠋࡇࢀࡽࡢ᪉ἲࢆ⏝࠸ࡿࡓࡵ࡟ࡣࠊ(1), (2)ᘧࡢᐦᗘ㛵ᩘࡢ✚ศࡀᚲせ࡛࠶ࡾࠊࡇࢀࡀᐜ᫆࡟ᐇ⾜ྍ⬟࡛࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋࡑࡢࡓࡵࠊᐦᗘ I<  ࢆᵓᡂࡍࡿἼື㛵ᩘ࡜ࡋ࡚ࡣࠊrij㡯ࢆ㟢ࢃ࡟ྵࡲ࡞࠸Ἴື㛵ᩘ < ࢆ⏝࠸ࡿࡇ࡜ࡀ⌧ᐇⓗ࡛࠶ࡿࠋࡋ࠿ࡋࠊ┠ⓗࡣᡤヮࢧࣥࣉࣜࣥࢢⅬ⏕ᡂ࡛࠶ࡾࠊࡇࡢ < ࡀ⣔ࡢᛶ㉁ࢆ཯ᫎࡋ࡚࠸ࡿࡶࡢ࡛࠶ࢀࡤ᭷⏝࡛࠶ࡿࠋ < ࡜ࡋ࡚ࠊHartree-Fock (HF)ࡸ post-HF Ἴື㛵ᩘ, ཎᏊ౯⤖ྜ(VB)Ἴື㛵ᩘ࡞࡝ᚑ᮶ࡢ㔞Ꮚ໬ᏛࡢἼື㛵ᩘࢆ౑࠺ࡇ࡜ࡶ࡛ࡁࠊFC ἲ࡟࠾ࡅࡿึᮇ㛵ᩘ,sij Ἴື㛵ᩘ(Phys. Rev. A 101, 062508 (2020).)࡞࡝ࢆ⏝࠸ࡿࡇ࡜ࡶ࡛ࡁࡿࠋ

2.3. ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࡢࢥࣥࣃࢡࢺ࡞グ㏙: ᏶ဨ㛵ᩘ㑅ᢥἲFC ⌮ㄽࡣࠊ㟁Ꮚ⣔ࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟㝈ࡽࡎ࠶ࡽࡺࡿࣁ

10.0࣑ࣝࢺࢽ࢔࡛ࣥᡂࡾ❧ࡘ⌮ㄽ࡛࠶ࡾࠊྠᙧࡢࣁ࣑ࣝࢺࢽ࢔ࣥࡀ࢝ࣂ࣮ࡍ

8.0

ࡲୖࡆࡿ࡜⮬⏤ᗘ: M(᏶ဨ㛵ᩘࡢḟඖ)ࡀ኱ࡁࡃ࡞ࡗ࡚ࡋࡲ࠺ࠋࡋ࠿ࡋࠊ
ཎᏊ࣭ศᏊࡢ≉ᐃࡢ㟁Ꮚ≧ែࢆᑐ㇟࡜ࡋࠊ≉࡟໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ΔE (kcal/mol)ࡿ⣔ࢆṇ☜࡟グ㏙ࡍࡿ᏶ဨ㛵ᩘࢆ⏕ᡂࡍࡿࠋࡑࡢࡓࡵࠊorder ࢆࡑࡢࡲ

9.0
7.0
6.0
5.0

M=129 (ΔE < 1 kcal/mol)

4.0
3.0

M=285 (ΔE < 0.5 kcal/mol)

2.0ᇶ࡙ࡃᒁᡤⓗ࡞グ㏙࡛ࡣࠊ⤖ᯝ࡟࡯࡜ࢇ࡝ᙳ㡪ࢆ୚࠼࡞࠸୙せ࡞᏶ဨ㛵ᩘࡀከࡃᏑᅾࡍࡿࠋᡃࠎࡣࠊಀᩘࡢᑠࡉ࠸ࡶࡢࢆ᤼㝖ࡍࡿ᪉ἲࡸྛ᏶ဨ
㛵ᩘࡢ࢚ࢿࣝࢠ࣮ᐤ୚ࢆุ᩿ࡍࡿ᪉ἲ➼࡟ࡼࡾࠊ᏶ဨ㛵ᩘࢆຠ⋡ⓗ࡟
5 o3㑅ᢥࡍࡿ᪉ἲࢆ㛤Ⓨࡋࡓࠋ౛࠼ࡤࠊC( S ,sp )ཎᏊࡢኚศἲࡢィ⟬࡛ࡣ

1.0
0.0
0

500

1000
1500
M (Dimension)2000

ᅗ  & 6RVS ཎᏊࡢ )&ኚศἲࡢィ⟬᏶ဨ㛵ᩘ㑅ᢥἲࡢ㐺⏝(Phys. Rev. A 102, 052835 (2020).)ࠊorder(n)=3 ࠿ࡽ᏶ဨ㛵ᩘࢆ㑅ᢥࡍࡿ࡜ࠊഹ࠿ 129 ಶࡢ᏶ဨ㛵ᩘ࡛⤯ᑐゎ࡜ࡋ
࡚ 1 kcal/mol ௨ୗࡢ໬Ꮫ⢭ᗘࢆ‶ࡓࡋࠊ285 ಶࡢ᏶ဨ㛵ᩘ࡛ 0.5 kcal/mol ௨ୗࡢ⤖ᯝࡀᚓࡽࢀࡓ(ᅗ 2)ࠋࡑࢀ௨
ୖࡢ n=3 ࡢ᏶ဨ㛵ᩘࢆᑟධࡋ࡚ࡶࠊᑡ࡞ࡃ࡜ࡶ࢚ࢿࣝࢠ࣮ࡢᨵၿ࡟ࡣ⧅ࡀࡽࡎࠊࡑࢀࡼࡾࡶࡼࡾ㧗ḟࡢ㛵ᩘࢆᑟධࡍࡿ᪉ࡀ᭷⏝࡛࠶ࡿࠋḟ order ࡢ㛵ᩘ⏕ᡂ࡛ࡣࠊ㑅ᢥࡉࢀࡓ᏶ဨ㛵ᩘࡢࡳ࡟ FC ἲࢆ apply ࡍࡿࡇ࡜࡟
ࡼࡗ࡚ࠊexact ࡟㏆࡙ࡅࡿ㧗ḟ㛵ᩘࢆຠ⋡ⓗ࡟⏕ᡂࡍࡿࡇ࡜ࡀ࡛ࡁࠊィ⟬㈨※ࡢ⠊ᅖෆ࡛ࡶṇ☜࡞ゎ࡬ࡢ཰᮰ࢆຠ⋡ⓗ࡟㏿ࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ



◊✲ᡂᯝ

3.1. FC-LSE ἲ: ➨஧࿘ᮇཎᏊࡢィ⟬
ࡲࡎࠊFC-LSE ἲࢆୖ㏙ࡢ⌮ㄽ࣭ィ⟬ἲࢆ⏝࠸࡚➨஧࿘ᮇཎᏊ(Li㹼Ne ཎᏊ)࡟ᛂ⏝ࡋࡓࠋึᮇ㛵ᩘࡣࠊAufbau
principle ࡟ἢ࠺㓄⨨࡛ᵓᡂࡋࠊ
2s, 2p 㟁Ꮚ࡟࠾࠸࡚ࡣ double-zeta, 㛢Ẇࢩ࢙ࣝ࡟ࡣ in-out correlation ࢆᑟධࡋࡓࠋ
ࡲࡓࠊ2s, 2p ࡀᨃ⦰㏥࡟㏆࠸ B, C ཎᏊ࡛ࡣࠊูࢫࣆࣥ㛵ᩘཬࡧ 2 㟁Ꮚບ㉳㓄⨨ࢆᑟධࡋࡓࠋ
⾲ 1 ࡟ࠊ
B(2P)ཎᏊ࡛ FC-LSE ἲࡢ཰᮰࡜ gij 㛵ᩘ: ձ (L J LM ULM  J LM  (L J LM  ղ   H[S J LM ULM  ճ ULM  ULM  DLM  մ
DUFWDQ J LM ULM ࢆ᳨ドࡋࡓ⤖ᯝࢆ♧ࡋࡓࠋorder(n)ࢆ㐍ࡵࡿࡇ࡜࡛ࠊExact ࡢぢ✚ࡶࡾ࡜ࡢᕪ࡛࠶ࡿ ǻ( ࡣ 0 ࡟㏆࡙ࡁࠊn=2 ࡛ࡣ 1 kcal/mol ௨ୗࡢ໬Ꮫ⢭ᗘࢆ㐩ᡂࡋ࡚࠸ࡿࠋn=2 ࡟࠾࠸࡚ࠊgij ࢆ 1 㡯⏝࠸ࡓ࡜ࡁ(ձࡢሙྜ)ࡣ
ǻ(=0.493 kcal/mol ࡔࡗࡓࡀࠊgij ࢆ 3 㡯, 4 㡯⏝࠸ࡓ࡜ࡁࡣ 0.1 kcal/mol ௨ୗࡢ⤖ᯝࡀᚓࡽࢀ࡚࠸ࡿࠋࡇࡢࡼ࠺
࡟ࠊ」ᩘࡢᛶ㉁ࡢ␗࡞ࡿ gij 㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡛ࠊ஫࠸ࢆ⿵᏶ࡋ⤖ᯝࢆᨵၿࡍࡿࡇ࡜ࡀ࡛ࡁ࡚࠸ࡿࠋ✚ศἲ࡛- 87 -

ࡣࠊ≉࡟」ᩘࡢ gij 㛵ᩘࢆ⏝࠸ࡿ࡜✚ศィ ⾲  % 3 ཎᏊ)&/6( ἲࡢ཰᮰࡜ JLM 㛵ᩘࡢ᳨ド
JLMD⟬ࡀᅔ㞴ࡔࡀࠊࢧࣥࣉࣜࣥࢢἲ࡛ࡣᐜ᫆

0+VTXDUHHUURU (QHUJ\ DX ǻ( NFDOPROQ  9DULDWLRQDO࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ



⾲ 2 ࡣࠊN(4S)ཎᏊ࡟ᛂ⏝ࡋࡓ⤖ᯝࢆ♧
ࡋࡓࠋgij 㛵ᩘࡣ Ei ᆺࢆ⏝࠸ࡓࠋn=1 ࡲ࡛  㡯 ձ 㡯 ղࡣᚑ᮶㏻ࡾ᏶ဨ㛵ᩘࢆ⏕ᡂࡋࠊࡑࡇ࡛᏶  㡯 ձղဨ㛵ᩘ㑅ᢥࢆ⾜ࡗࡓ m0=63 ಶࢆ᪂ࡓ࡞ \   㡯 ձղճ 㡯 ձղճմ

࡜ࡋ࡚᪂ࡋ࠸ n=1 ࡢ cf ࢆ⏕ᡂࡋࡓࠋࡇࡢ

ᡭ㡰ࢆ⧞ࡾ㏉ࡋࠊorder ࢆ㐍ࡵࡿ࡜ H[DFW  㡯 ձ
࡬㏆࡙ࡁࠊnew n=3 ࡛ࡣḟඖ(M)ࡢቑຍࡣ  㡯 ղ 㡯 ձղᑠ ࡉ ࡃ ᢚ ࠼ ࡽ ࢀ ࡚ ࠸ ࡿ ࡟ ࡶ 㛵 ࢃ ࡽ ࡎ  㡯 ձղճ
ǻ(=0.0840 kcal/mol ࡢ㧗⢭ᗘ࡞⤖ᯝࡀᚓ  㡯 ձղճմ
(VWH[DFWࡽࢀࡓࠋD⾲ 3 ࡟ࡣࠊLi㹼Ne ཎᏊࡢ⤖ᯝࢆࡲ࡜ࡵ












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
















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





ձ (L J LM ULM  J LM  (L J LM  ղ   H[S J LM ULM  ճ ULM  ULM  DLM  մ DUFWDQ J LM ULMࡓࠋ඲࡚ࡢཎᏊ࡛ 1 kcal/mol ௨ୗ ⾲  1 6 ཎᏊ ᏶ဨ㛵ᩘ㑅ᢥἲࢆ⏝࠸ࡓ )&/6( ἲࡢ཰᮰ࡢ໬Ꮫ⢭ᗘࡢゎࡀᚓࡽࢀ࡚࠸ࡿࠋ

Q


QHZ
QHZ
QHZ

Li㹼F ཎᏊࡢィ⟬ࡣ 2018 ᖺࡢㄽᩥ (J. Chem. Phys. 149, 114106(2018).)࡛ࡶ⾜ࡗࡓࡀࠊᙜ᫬ࡣ࣓
ࢺ࣏ࣟࣜࢫἲࢆᨵⰋࡋࡓ LMn ࢧ0P  э FIJHQ P  э FIJHQ P  э FIJHQ 

+VTXDUHHUURU (QHUJ\ DX ǻ( NFDOPRO

YDULDWLRQDO




(VWH[DFW








ࣥࣉࣜࣥࢢἲࢆ⏝࠸࡚࠾ࡾࠊࢩ࣑
࣮ࣗࣞࢩࣙࣥཬࡧ⧞ࡾ㏉ࡋ࡛ከࡃࡢィ⟬᫬㛫ࡀ࠿࠿ࡾࠊ཰᮰ࡢุᐃࡶᅔ㞴࡛࠶ࡗࡓࠋࡑࢀ࡟ᑐࡋࠊ௒ᅇࡣ 1ᗘࡢࢧࣥࣉࣜࣥࢢⅬ⏕ᡂ࡛ゎࢆィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࠊィ⟬᫬㛫ࡶᑡ࡞ࡃ῭ࢇ࡛࠸ࡿࠋ⾲  ➨஧࿘ᮇཎᏊࡢィ⟬ ࡲ࡜ࡵ)&/6(WKHRU\$WRPD/L 6%H 6% 3& 3VS& 6RVS
1 6
2 3
) 3
1H 60+VTXDUH
HUURU



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
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


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


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
(QHUJ\DX

ǻ( RIUHIHUHQFHV NFDOPROǻ(NFDOPRO

7LPLQJD

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

PLQ
PLQ
PLQPLQ
PLQPLQ
KRXU
KRXU
KRXU(VW H[DFW'LIIXVLRQ
'0&0'5RU
0RQWH&DUOR
F)&&6'
%)
7G
'0& E



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
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



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



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

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

D

 VDPSOLQJDW,06 FRUHV E(%XHQGLD)-*DOYH]30DOGRQDGRDQG$6DUVD-&KHP3K\V   F0'%URZQ-57UDLO3/RSH]5LRVDQG5-1HHGV -&KHP3K\V    G-1RJD6 .HG]XFK-6LPXQHNDQG6
7HQQR-&KHP3K\V  

3.2. FC-LSE ἲ: ศᏊࡢᇶᗏ࣭ບ㉳≧ែ࡜࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ
ศᏊࡢィ⟬࡛ࡣࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᇶ࡙ࡁࠊཎᏊࡢ㔞Ꮚ≧ែࢆඖ࡟ྛ㟁Ꮚ≧ែ(ᇶᗏ࣭ບ㉳≧ែ)࡟ᑐ

- 88 -

ᛂࡍࡿᒁᡤᵓ㐀ࡢ㓄⨨ࢆᵓᡂࡋࠊࡇࢀࢆึᮇ㛵ᩘ࡜ࡋ FC ⌮ㄽࢆ㐺⏝ࡍࡿࠋ
Li2 ศᏊ: Li2 ศᏊࡢィ⟬࡛ࡣࠊLi ཎᏊࡢ 2s ㌶㐨ྠኈࡢ⤖ྜ㓄⨨࡜ 2s ㌶㐨࡟㏆᥋ࡍࡿ 2p ㌶㐨ࡢ⤡ࡴ⤖ྜ㓄⨨࠾ࡼࡧࡑࢀࡽࡢ࢖࢜ࣥ㓄⨨ࢆᑟධࡋࡓࠋ౛࠼ࡤࠊȈJ≧ែࡢึᮇ㛵ᩘࡣࠊ&RYDOHQW㡯 /L V /L V  \ /L V /L S [  \ 

VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED  V $ V% DE  ED
VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED  V $  S[  % DE  ED  $ l %/L S [ /L S [  \ 

VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED   S[  $  S[  % DE  ED

,RQLF㡯 /L V $   \ 

VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED  V $  DE  $ l %/L V $ S [$  \ 
/L S [$   \ 

VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED  V $  S[ $ DE  ED  $ l %VLQ $VRXW  $ DE  ED  VLQ % VRXW  % DE  ED   S[  $  DE  $ l %ࢆ⏝࠸ࡓࠋgij 㛵ᩘࡣ Ei
ᆺࢆ⏝࠸ࠊ2s, 2p 㟁Ꮚࡢ㛵 㐃 ࡍ ࡿ ࡍ ࡭ ࡚ ࡢvalence ᇶᗏ࣭ບ㉳≧ែ;ȈJ $ȈXȈJ%ȆXȆJ DȈX ȆX EȈJȆJ ࡢ࣏ࢸࣥࢩࣕࣝ࢝
࣮ࣈࡢィ⟬ࢆ⾜ࡗࡓࠋXȈJ ≧ ែ( ᇶᗏ≧ែ) ࡢᖹ⾮఩⨨(Req=5.051 a.u.)࡛ࡣࠊṇ☜࡞࢚ࢿࣝࢠ࣮ࡢぢ✚ࡶࡾ್࡜ࡢᕪ:ᅗ  Li2 ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ: (a) ᐇ㦂 RKR, (b) FC ⌮ㄽǻ(  NFDOPRO ࡛࠶ࡾࠊ⤯ᑐゎ࡜ࡋ࡚໬Ꮫ⢭ᗘࢆ༑ศ࡟‶㊊ࡍ
ࡿ⤖ᯝࡀᚓࡽࢀࡓࠋᅗ 3(a)࡟ࠊᐇ㦂࠿ࡽồࡵࡽࢀࡓ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ(RKR ࣏ࢸࣥࢩࣕࣝ)ࠊᅗ 3(b)࡟ FC-LSE ἲࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝
ࣈ(n=3)ࢆ♧ࡋࡓࠋᐇ㦂 RKR ࣏ࢸࣥࢩࣕࣝࡣࠊᐇ㦂࡛ほྍ⬟࡞᣺ື࣭ᅇ㌿‽఩࠿ࡽ⟬ฟࡍࡿࡓࡵࠊ᳨ฟྍ⬟࡞㟁Ꮚ≧ែࡸ᰾㛫㊥㞳 Rࡀ㝈ࡽࢀ࡚࠸ࡿࠋ౛࠼ࡤࠊ୕㔜㡯≧ែࡢ ȆXȆJ ࡢࢹ࣮ࢱࡣ࡞ࡃࠊ
ȈXEȈJȈJ➼࡛ࡣࠊ5 ࡢ⠊ᅖࡀ࠿࡞ࡾ㝈ࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊ)&⌮ㄽ࡟ࡼࡿ⌮ㄽィ⟬࡛ࡣ࠶ࡽࡺࡿ㟁Ꮚ≧ែ 5 ࡢ⤖ᯝࡀ⢭ᐦ࡟ᚓࡽࢀ࡚࠸ࡿࠋᅗ  ࡣࠊᐇ㦂 5.5 ࣏ࢸࣥࢩࣕࣝ࡜ FC ⌮ㄽࡢ࣏ࢸࣥࢩࣕ
࣮ࣝ࢝ࣈࢆ㔜ࡡྜࢃࡏࡓᅗࢆ♧ࡋࡓࠋࡇࡇ࡛ࠊ࢚ࢿࣝࢠ࣮ࡣ୍ษࢩ
ࣇࢺࡋ࡚࠸࡞࠸ࠋ࠶ࡽࡺࡿ㟁Ꮚ≧ែ࡟࠾࠸࡚ࠊࡲࡓ࠶ࡽࡺࡿ᰾㛫㊥㞳 R ࡟࠾࠸࡚ࠊࡇࢀࡽࡣ᏶඲࡟୍⮴ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋRKRᅗ  Li2 ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ
ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ:ࣈᐇ㦂 RKR ࡜ FC ⌮ㄽࡢᅗࢆ㔜ࡡྜࢃࡏ࣏ࢸࣥࢩࣕࣝ, FC ⌮ㄽ࡜࠸࠺඲ࡃ␗࡞ࡿ⌮ㄽ, ᡭἲ࡛ࡶࡇࡇࡲ୍࡛⮴ࡍࡿࡇ࡜ࡣ㦫ࡁ࡛࠶ࡿࠋ
1985 ᖺ࡟ᡃࠎࡣ SAC-CI ἲ࡛ Li2 ศᏊࡢࡇࢀࡽࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆඛ㥑ࡅ࡚ィ⟬ࡋࡓ
(Can. J. Chem. 63, 1857 (1985).)ࠋࡇࡢ⤖ᯝࢆ SAC-CI(1985)࡜࿧ࡪࡇ࡜࡟ࡍࡿࠋከࡃࡢ≧ែࡢᐇ㦂ࡢ RKR ࣏ࢸ- 89 -

ࣥࢩࣕࣝࡀሗ࿌ࡉࢀࡿࡼ࠺࡟࡞ࡗࡓࡢࡣࠊࡑࡢ ⾲ /L ศᏊ ᖹ⾮఩⨨ ᩿⇕ບ㉳࢚ࢿࣝࢠ࣮ ゎ㞳࢚ࢿࣝࢠ࣮
⩣ᖺ௨㝆࡛࠶ࡿࠋᙜ᫬ࡣィ⟬ᶵࡢไ⣙࠿ࡽᇶᗏ≧ែᖹ⾮఩⨨ ບ㉳࢚ࢿࣝࢠ࣮ゎ㞳࢚ࢿࣝࢠ࣮
5HT Ⴒ 
7H H9 'H NFDOPRO  ᪉ἲ㛵ᩘ, ィ⟬ἲ➼࡟኱ࡁ࡞ไ⣙ࡀ࠶ࡗࡓࡓࡵࠊ኱

;J
)&
ࡁ࡞ᇶᗏ㛵ᩘ: jorge-6ZP (uncontracted)࡜ᦤື㑅
([SWO


6$&&,  
ᢥ࡞ࡋࡢ᪉ἲ࡟ࡼࡗ࡚ࠊSAC-CI ィ⟬ࢆࡸࡾ┤ࡋ$ X 
)&
ࡓ(SAC-CI(2022)࡜࿧ࡪࡇ࡜࡟ࡍࡿ)ࠋࡲࡓࠊ㏆
([SWO


6$&&,  
ᖺࠊศᏊ㌶㐨ἲ࣮࣋ࢫࡢ )6&&6'  ἲ ᇶᗏ
J
)&
㛵ᩘ$125&&(uncontracted) ࡛ࡢሗ࿌ࡶ࠶ࡿ

([SWO

0 0XVLDá DQG 6 $ .XFKDUVNL - &KHP 7KHRU\
6$&&,  Ȇ %)&X &RPSXW   ࠋX ȈJ ≧ែࡢᖹ⾮఩⨨([SWO

࡛⤯ᑐ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿ࡜ࠊSAC-CI(1985),

6$&&,  
)&
FS-CCSD(2,0), SAC-CI(2022), FC ⌮ㄽ࡛ࡑࢀࡒ  ȆJ([SWO

ࢀࠊǻ( NFDOPRO ࡛࠶
6$&&,  
ࡗࡓࠋ6$&&,  ࡢ್ࡣ )6&&6'  ࡢ್ࡼ DX)&

([SWO

ࡾഹ࠿࡟ప࠿ࡗࡓࠋ)& ⌮ㄽࡢ⤖ᯝࡣᅽಽⓗ࡟⢭
6$&&,  
ᐦ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ5.5 ࣏ࢸࣥࢩࣕࣝ࡜ẚ ȆX)&

([SWO

㍑ྍ⬟࡞ᇶᗏ࣭ບ㉳≧ែࡢᵝࠎ࡞ 5 ࡛ࡢᖹᆒࡣࠊ

6$&&,  
SAC-CI(1985), SAC-CI(2022), FC ⌮ㄽ࡛ࡑࢀࡒE J 
)&
ࢀࠊǻ(DYH     NFDOPRO([SWO


6$&&,

࡛࠶ࡗࡓࠋࡑࡢࡓࡵࠊ)& ⌮ㄽ௨እ࡛ࡣࠊ࣏ࢸࣥ
ȆJ
5HSXOVLYH



















  
  
  

 



  
  
  
ࢩ࣮ࣕࣝ࢝ࣈࢆ ǻ(DYH ࡔࡅ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡋ

࡞࠸࡜ᐇ㦂 5.5 ࣏ࢸࣥࢩࣕࣝ࡜┤᥋ẚ㍑࡛ࡁ࡞࠸ࠋ
⾲㸲࡟ࠊྛ㟁Ꮚ≧ែࡢᖹ ⾮఩⨨ 5HT  ᩿⇕ບ㉳࢚ࢿࣝࢠ࣮ 7H  ゎ㞳࢚ࢿࣝࢠ࣮ 'H ࡢ್ࢆ♧ࡋࡓࠋ
6$&&,  ࡢ⤖ᯝࡶᐇ㦂್࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࡀࠊ)& ⌮ㄽࡢ⤖ᯝࡣࡑࢀ௨ୖ࡟Ⰻ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࠋ≉࡟ 7H ࡣࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ5HT ࡸ 'H ࡣ᪂ࡋ࠸ᐇ㦂࡟ࡼࡗ್࡚ࡀ᭦᪂ࡉࢀࡿࡇ࡜ࡶከࡃࠊᐇ㦂࡟࠾ࡅࡿㄗᕪࡶ
࠶ࡾᚓࡿࠋྛ᰾㛫㊥㞳 R ࡟࠾ࡅࡿᆶ┤ບ㉳࢚ࢿࣝࢠ࣮ࡢ RKR ࣏ࢸࣥࢩࣕࣝ࡜ࡢᕪ ǻ(; ࡢᖹᆒࡣࠊ
SAC-CI(1985), SAC-CI(2022), FC ⌮ㄽ࡛ࡑࢀࡒࢀ 0.03353, 0.02862, 0.00215 eV ࡛࠶ࡗࡓࠋSAC-CI ἲࡢ⤖ᯝࡶ༑ศ࡟㧗⢭ᗘ࡛࠶ࡿࡀࠊFC ἲࡢ⤖ᯝࡣࡉࡽ࡟ 10 ಸ௨ୖࡢ⢭ᗘ࡛ᐇ㦂࡜୍⮴ࡋ࡚࠸ࡓࠋ
H4 ศᏊ: H4 ศᏊࡣ⡆༢࡞ 4 㟁Ꮚ⣔ࡢศᏊࡔࡀࠊከ㓄⨨ᛶࡀᙉ

H࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ㔞Ꮚ໬Ꮫィ⟬ࡢ࣋ࣥࢳ࣐࣮ࢡ࡜ࡋ࡚ࡼ

R

ࡃ౑ࢃࢀ࡚࠸ࡿ(T. V. Voorhis and M. Head-Gordon, J. Chem. Phys.
113, 8873 (2000). H. G. A. Burton and A. J. W. Thom, J. Chem.
Theory Comput. 12, 167 (2016). D. Pfau, J. S. Spencer, and A. G. D.

H

H

ș

R=3.2843 a.u. (=1.70 Ⴒ) ᅛᐃș䜢ኚ໬(ș=90ᗘ: ṇ᪉ᙧ)H
ᅗ + ศᏊࡢᵓ㐀

G. Matthews, Phys. Rev. Research 2, 033429 (2020).)ࠋᡃࠎࡣࠊVB ᆺࡢグ㏙࡛ᒁᡤⓗ࡞ඹ᭷⤖ྜ㡯࡜࢖࢜ࣥ㡯ࢆᑟධࡋࡓึᮇ㛵ᩘࢆ⏝࠸ࠊFC-LSE ἲࡢィ⟬ࢆ⾜ࡗࡓࠋࡇࡇ࡛ࠊgij 㛵ᩘࡣ Ei ᆺࢆ⏝࠸ࡓࠋィ⟬ࡣࠊ࣋ࣥࢳ࣐࣮ࢡ࡛౑ࢃࢀ࡚࠸ࡿᵓ㐀(ᅗ 5)࡛ ș ࡢኚ໬࡟ᑐࡍࡿ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆィ⟬ࡋࡓࠋgij㛵ᩘࡣ Ei ᆺࢆ⏝࠸ࡓࠋࡲࡎࠊ I\   ࡢᐦᗘศᕸ࡟ᑐࡋ࡚┤᥋ἲ( * 1 ࢧࣥࣉࣜࣥࢢ)࡟ࡼࡗ࡚⏕ᡂࡉࢀࡓࢧࣥ

ࣉࣜࣥࢢⅬࡢศᕸࢆ᳨ドࡋࡓࠋᅗ 6 ࡟♧ࡍࡼ࠺࡟ࠊ㟁Ꮚ 1 ࡢᗙᶆⅬࢆࣉࣟࢵࢺࡍࡿ࡜ࠊ4 ࡘࡢ H ཎᏊ࡟➼౯- 90 -

࡟ศᕸࡋ࡚࠾ࡾࠊࡇࢀࡣ㟁Ꮚᐦᗘࡢศᕸ࡟ᑐᛂࡍࡿࠋḟ࡟ࠊ㟁Ꮚ 1
ࡀ᰾ A ㏆ഐ࡟Ꮡᅾࡍࡿ᮲௳ୗ࡛㟁Ꮚ 2 ࡢᗙᶆⅬࢆࣉࣟࢵࢺࡍࡿ࡜ࠊ
㟁Ꮚ 2 ࡣ᰾ A ㏆ഐ࡟Ꮡᅾࡍࡿ amplitude ࡣ࡯ࡰࢮ࡛ࣟࠊ᰾ B,C,D ㏆

C

D

C

D

A

B

㟁Ꮚ1
A

B

ഐ࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡉࡽ࡟᰾ B,C ࡼࡾࡶࠊ᰾ A ࠿ࡽ㐲㟁Ꮚ1䛾ศᕸ(㟁Ꮚᐦᗘศᕸ)࠸᰾ D ㏆ഐࡢ amplitude ࡀ᭱ࡶ኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡿࠋྠᵝ࡟ࠊ㟁Ꮚ 1
ࡀ᰾ A, 㟁Ꮚ 2 ࡀ᰾ D ㏆ഐ࡟Ꮡᅾࡍࡿ᮲௳ୗ࡛ࡣ㟁Ꮚ 3 ࡣ᰾ B,C ㏆

㟁Ꮚ2䛾ศᕸ
(㟁Ꮚ1䛜᰾A㏆ഐ(< 3.0 a.u.))

㟁Ꮚ2

㟁Ꮚ2

ഐ࡟Ꮡᅾࡋࠊ㟁Ꮚ 1,2,3 ࡀࡑࢀࡒࢀ᰾ A,D,B ㏆ഐ࡟Ꮡᅾࡍࡿ᮲௳ୗ

CD

࡛ࡣ㟁Ꮚ 4 ࡣṧࡾࡢ᰾ C ㏆ഐ࡟Ꮡᅾࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊ┤᥋ἲ

㟁Ꮚ1
A

B

C

D

㟁Ꮚ1

㟁Ꮚ3

A

B

࡟ࡼࡗ࡚ࠊᒁᡤᛶ࣭཯ᑐ⛠ᛶࢆ཯ᫎࡍࡿࢧࣥࣉࣜࣥࢢⅬࡀṇࡋࡃ⏕ᡂࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ⤖ᯝⓗ࡟ࠊ1 ࡘࡢࢧࣥࣉࣜࣥࢢ(4 㟁Ꮚ㟁Ꮚ3䛾ศᕸ
㟁Ꮚ4䛾ศᕸ
(㟁Ꮚ1,2䛜䛭䜜䛮䜜᰾A,D㏆ഐ) (㟁Ꮚ1,2,3䛜䛭䜜䛮䜜᰾A,D,B㏆ഐ)ࡢᗙᶆ)୰ࡢ 4 ࡘࡢ㟁Ꮚࡣࠊ᰾ A, B, C, D ࡟ 1 ࡘࡎࡘศᕸࡍࡿᅗ + ศᏊࡢࢧࣥࣉࣜࣥࢢⅬࡢゎᯒamplitude ࡀ᭱ࡶ኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡿࠋᅗ 7 ࡟ࠊࡇࡢࢧࣥࣉ
ࣜࣥࢢⅬࢆ⏝࠸࡚ィ⟬ࡋࡓ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ(ș ࢆኚ໬)ᇶᗏ㛵ᩘ(DZP))( T. V. Voorhis and M. Head-Gordon, J. Chem.
Phys. 113, 8873 (2000).)ࠊ
Full-CI ἲ(Slater ᆺ CVB2 ᇶᗏ㛵ᩘ)ࠊ
CCSD(CVB2 ᇶᗏ㛵ᩘ) ࡛ࡢ⤖ᯝࡶ♧ࡋ࡚࠸ࡿࠋ ࡲࡎࠊ

Energy (a.u.)ࢆ♧ࡍࠋẚ㍑ࡢࡓࡵࠊFull-CI ἲ(double-zeta+ศᴟࡢ Gauss

CCSD(CVB2)ࡢ⤖ᯝࡣࠊș=90r࡛࢚ࢿࣝࢠ࣮ࡀ኱ࡁࡃୗࡀ
ࡾࠊ࣏ࢸࣥࢩࣕࣝᙧ≧ࡶṇࡋࡃ࡞࠸ࠋࡇࡢࡼ࠺࡟ࠊࡇࡢ⣔ࡣከཧ↷ᛶࡀᙉࡃ༢ཧ↷ࡢ㠀ኚศⓗ post-HF ⌮ㄽࡣୖᡭࡃ

-1.995-2.000-2.005-2.010-2.015-2.020-2.025-2.030-2.035-2.040-2.045-2.050

Full CI (DZP)
Full CI (CVB2)

CCSD (CVB2)
FC-LSE
60.0 70.0 80.0 90.0 100.0 110.0 120.0
ș (degree)ᅗ + ศᏊࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ

࠸࠿࡞࠸ࠋ୍᪉ࠊFull CI (DZP)ࡢ⤖ᯝࡣࠊș ࡀ኱ࡁ࠸࡜ࡁᙧ
≧ࡀὸ࠸࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ࡟࡞ࡗ࡚࠸ࡿࠋFull CI ἲ࡛ࡶᇶᗏ㛵ᩘࡀ୙㊊ࡍࡿ࡜┦ᑐⓗ࡟ࡶṇࡋࡃ࡞࠸ሙྜࡀ࠶ࡾᚓࡿࠋFull CI (CVB2)ࡢ⤖ᯝࡣࠊFC-LSE ἲࡢ⤖ᯝ࡟࠿࡞ࡾ㏆࠸ࡀࠊ⤯ᑐ࢚ࢿࣝࢠ࣮ࡀഹ࠿࡟㧗࠸ࠋș ࡟࠾࠸࡚ࠊFC-LSE ἲࡢ࢚ࢿࣝࢠ࣮ࡼࡾࠊFull CI (DZP)
ࡣ 8.2 kcal/mol, Full CI (CVB2)ࡣ 0.58 kcal/mol 㧗ࡃࠊCCSD(CVB2)ࡣ 4.4 kcal/mol ప࠿ࡗࡓ(ኚศⓗ࡟ṇࡋࡃ࡞࠸)ࠋFC-LSE ἲ࡛ࡣࠊ඲㡿ᇦ࡛⤯ᑐゎ࡜ࡋ࡚ṇ☜࡛⁥ࡽ࠿࡞࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡀᚓࡽࢀ࡚࠸ࡿࠋ
CH+ศᏊ: CH+ศᏊࡢᇶᗏ≧ែ(XȈ)ࡣ C+ཎᏊ, H ཎᏊ࡟-37.0ඹ᭷⤖ྜゎ㞳ࡍࡿࡀࠊ Ȉ ࡢບ㉳≧ែ(Ȉ Ȉ)ࡣ C(1D),-37.2

C(1S)ཎᏊ࡜ H+ཎᏊ࡟࢖࢜ࣥゎ㞳ࡍࡿࠋࡑࡢࡓࡵࠊ໬Ꮫࣇ

-37.4

࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᇶ࡙ࡁࠊC ࡢ 2px ࡜ H ࡢ 1s ࡀ⤖ྜࡍࡿඹ᭷⤖ྜᆺ㓄⨨, C+ࡢ 2s ࡜ H ࡢ 1s ࡀ⤖ྜࡍࡿඹ᭷⤖ྜᆺ㓄⨨ࠊC(1D)H+, C(1S)H+ࡢ࢖࢜ࣥᆺ㓄⨨ࢆึᮇ㛵ᩘ࡜ࡋ࡚⏝࠸

Energy (a.u.)+

㽢: FC-LSE

-37.6
-37.8

⾲ 5 ࡟ࠊ
ࡓ(ศᏊ㍈ࡣ x ㍈࡜ࡍࡿ)ࠋ
gij 㛵ᩘࡣ Ei ᆺࢆ⏝࠸ࡓࠋ-38.0

ᖹ⾮఩⨨(Req=2.137 a.u.)࡟࠾ࡅࡿᇶᗏ(XȈ , ບ㉳≧ែ(2Ȉ,-38.2

3Ȉ)ࡢィ⟬⤖ᯝࢆ♧ࡋࡓࠋorder ࢆୖࡆࡿ࡜ṇ☜࡞࢚ࢿࣝࢠ
࣮࡟㏆࡙ࡁࠊᇶᗏ≧ែࡣ niA=3, nij=2 (niA, nij ࡣࡑࢀࡒࢀ riA

31Σ+C(1S) + H+
C(1D) + H+

21Σ+

C+ + HX1Σ+1Σ+

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
R (a.u.)ᅗ &+ศᏊࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ

㒊఩, gij 㒊఩ࡢ order)࡛ࠊǻ(=0.427 kcal/mol ࡜࡞ࡾ໬Ꮫ⢭ᗘ(< 1 kcal/mol)ࢆ㐩ᡂࡋࡓࠋཧ↷࡜࡞ࡿィ⟬࡜ࡋ࡚ࠊ
Full CI ἲ(J. Olsen, A. M. Sanchez de Meras, H. J. Aa. Jensen, and P. Jørgensen, Chem. Phys. Lett. 154, 380 (1989).)ࡸ

- 91 -MRCI ἲ(Z. Biglari, A. Shayesteh, and A. Maghari, Comput. Theor. Chem. 1047, 22 (2014).)ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊࡑࢀࡒࢀ ǻ(=42.646, 34.685 kcal/mol ࡛࠶ࡾࠊᡃࠎࡢ order 1 ࡢ⤖ᯝࡼࡾࡶ㧗࠸್ࡔࡗࡓࠋ2Ȉ, 3Ȉ≧ែ࡬ࡢᖹ⾮఩⨨࡟࠾ࡅࡿᆶ┤ບ㉳࢚ࢿࣝࢠ࣮ࡣࠊࡑࢀࡒࢀ 8.218, 13.382 kcal/mol (niA=3, nij=2)࡛࠶ࡗࡓࠋFull CI (1989)ࡢ
⤖ᯝࡣⱝᖸ㧗ࡃࠊMRCI (2014)ࡢ್࡟㏆࠿ࡗࡓࠋᅗ 8 ࡟ᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆ♧ࡋࡓࠋFC⌮ㄽࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡣࠊᵝࠎ࡞ R ࡟࠾࠸࡚ XȈ, 2Ȉ Ȉ≧ែඹ࡟⤯ᑐゎ࡜ࡋ࡚໬Ꮫ⢭ᗘෆ࡛⢭ᐦ࡟ồࡲࡗ࡚࠸ࡿࠋ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࡢ┦ᑐⓗ࡞ᙧ≧ࡣ MRCI ἲ࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࡀࠊMRCI ἲࡣṇ☜࡞࢚ࢿࣝࢠ࣮ࡼࡾ⣙ 35 kcal/mol 㧗ࡃ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡀᚲせ࡛࠶ࡿࠋ⌧≧ࠊᅗ 8 ࡟༉ᩛࡍࡿ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ
ࡣࠊ⌮ㄽ, ᐇ㦂ඹ࡟࡞ࡃࠊ≉࡟ᐇ㦂࡛ࡢ RKR ࣏ࢸࣥࢩࣕࣝ➼ࡢ⢭ᐦゎࢆᚅࡕᮃࢇ࡚࠸ࡿࠋ⾲ &+ศᏊࡢ Ȉᑐ⛠ᛶࡢᇶᗏ࣭ບ㉳≧ែࡢ )&/6( ἲࡢ⤖ᯝ ᖹ⾮఩⨨5HT DX ;ȈVWDWHȈVWDWH
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C2 ศᏊ: C2 ศᏊࡢᇶᗏ≧ែࡣࠊC(3P, s2p2)ཎᏊ࡟ゎ㞳ࡍࡿࡀࠊᖹ⾮఩⨨࡛ࡣ C(5So,sp3)ཎᏊࡢ≉ᚩࡀᙉ࠸ࡇ࡜
ࡀ▱ࡽࢀ࡚࠸ࡿ(S. Shaik, D. Danovich, W. Wu, P. Su, H. S. Rzepa, P. C. Hiberty, Nature Chem. 4, 195 (2012).)ࠋࡑࡢ
ࡓࡵࠊᖹ⾮఩⨨࡛ࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࡢィ⟬࡟࠾࠸࡚ࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᚑ࠸ C(5So,sp3)ཎᏊࡢ㓄⨨࡛ᵓᡂࡍࡿ௨ୗࡢึᮇ㛵ᩘࢆ⏝࠸ࡓࠋ&RYDOHQW㡯 \ 

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(2s-2px)(2px-2s)࡜࡞ࡗ࡚࠸ࡿ㓄⨨࡛࠶ࡿ(ศᏊ㍈ࡣ x ㍈)ࠋgij 㛵ᩘࡣ Ei ᆺࢆ⏝࠸ࡓࠋ\  㹼\  ࡣࠊࡇࢀࡽ࡟ᑐ
ᛂࡍࡿ࢖࢜ࣥ㡯࡛࠶ࡿࠋ᏶ဨ㛵ᩘ⏕ᡂ᫬ࠊFC ⌮ㄽࡢ⌮ㄽ㏻ࡾ࡟ࠊཎᏊ㛫ࡢ Inter- UL % 㡯, Inter-gij 㡯ࡶྵࡵ࡚⏕$ᡂࡋ࡚࠸ࡿࠋࡇࡇ࡛ࠊInter- UL % 㡯ࡣࠊཎᏊ A ࡟ᒓࡍࡿ㟁Ꮚ i ࡜ཎᏊ B 㛫ࡢ㊥㞳ࢆ⾲ࡋ࡚࠾ࡾࠊ㟁Ꮚ i ࡢཎᏊ᰾$B ୖࡢ࢝ࢫࣉ᮲௳ࡢᨵⰋ࡜㟁Ꮚ i ࢆศᴟࡉࡏࡿᙺ๭ࡀ࠶ࡿࠋ୍⯡࡟✚ศࡀᐜ࡛᫆࡞࠸ࡓࡵࠊᚑ᮶ࡢ㔞Ꮚ໬Ꮫ- 92 -

ィ⟬࡟ࡣ㏻ᖖ౑ࢃࢀ࡞࠸ࡀࠊFC ⌮ㄽࡀ⏕ᡂࡍ ⾲  & ศᏊ ᇶᗏ≧ែ 5HT DX ࡛ࡢ )&/6( ἲࡢ⤖ᯝ
QL$D

QLMD

ࡀ࡛ࡁࡿࠋ⾲ 6 ࡟ࠊᇶᗏ≧ែ(ᖹ⾮఩⨨:

Req=2.348 a.u.)࡟࠾ࡅࡿ FC-LSE ἲࡢ཰᮰㐣⛬(VWH[DFWࡿ㡯࡜ࡋ࡚㔜せ࡛࠶ࡿࠋࡇࢀࡽࡣࠊࢧࣥࣉࣜ
ࣥࢢἲ࡛࠶ࡿ LSE ἲ࡛ࡣᐜ᫆࡟ྲྀࡾᢅ࠺ࡇ࡜

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ࢆ♧ࡍࠋorder(n)ࢆୖࡆࡿ࡜ᛴ㏿࡟ゎࡣᨵၿࡋࠊniA=2, nij=1 ࡛ࡶ⤯ᑐゎ࡛໬Ꮫ⢭ᗘࢆ‶ࡓࡍゎࡀᚓࡽࢀࡓࠋࡓ
ࡔࡋࠊḟඖࡣẚ㍑ⓗ኱ࡁࡃࠊศᏊࡢィ⟬࡛ࡣཎᏊ࡛ࡣ⏕ᡂࡉࢀ࡞࠸ᑐ⛠ᛶࢆᔂࡍ㛵ᩘࡀ஫࠸࡟⿵᏶ࡋࠊ཰᮰
ࢆ㏿ࡵ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋࡘࡲࡾࠊศᏊࡢグ㏙ࡣࠊᑐ⛠ᛶࡢ㧗࠸ཎᏊࡼࡾࡶ࠿࠼ࡗ࡚ᐜ࡛᫆࠶ࡿሙྜࡶ࠶
ࡾᚓࡿࠋࡋ࠿ࡋࠊ⌧≧ࡢ⤖ᯝࡣࠊࢧࣥࣉࣜࣥࢢ౫Ꮡᛶࡀྰࡵ࡞࠸ࡓࡵࠊࢧࣥࣉࣜࣥࢢ⏕ᡂ⌮ㄽࡢᨵⰋ, ࢧࣥࣉࣜࣥࢢ⏕ᡂ࡟⏝࠸ࡿᐦᗘ㛵ᩘࡢᨵⰋࡸࢧࣥࣉࣜࣥࢢⅬࢆቑࡸࡍࡇ࡜➼࡟ࡼࡗ࡚ࠊࡼࡾ☜ᐇ࡛Ᏻᐃ࡞ィ⟬ࢆ⾜࠺ࡼ࠺࡟ࡍࡿࠋࡲࡓࠊ⤯ᑐゎ࡜ࡋ࡚໬Ꮫ⢭ᗘࢆ‶㊊ࡍࡿ⢭ᗘ࡛ࡢᇶᗏ࣭ບ㉳≧ែࡢ⤖ྜゎ㞳࣏ࢸࣥࢩࣕࣝ
࣮࢝ࣈࡢィ⟬ࡶ㐍ࡵ࡚࠸ࡿࠋ

3.3. SAC-CI ἲ: ෆẆ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝ
ᮏ 6$&&, ἲ࡟ࡼࡿ◊✲ࡣࠊ㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓࡢᶓ㇂᫂ᚨඛ⏕ࡢᐇ㦂࡟ᇶ࡙ࡃඹྠ◊✲࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㏆ᖺᶓ㇂ࡽ࡟ࡼࡗ࡚

ᐃࡉࢀࡓ 7K\PLQH 7 ཬࡧ

%URPRXUDFLO %U8  ࡢෆẆ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝࢆ 6$&&, ἲ࡟ࡼࡗ࡚ゎᯒࡋࠊࣆ࣮ࢡࡢྠᐃࢆ⾜ࡗࡓࠋィ⟬࡟⏝࠸ࡓ 7 ཬࡧ %U8 ࡢᵓ㐀ࢆᅗ㸷࡟♧ࡍࠋ6$&&, ἲ࡟ࡼࡾィ⟬ࡉࢀࡓ 7 ࡢ 2 V 1V &V ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝࡣᐇ㦂ࢫ࣌ࢡࢺࣝ࡜ᖹᆒ H9 ௨ෆࡢㄗᕪ࡛ồࡲࡗࡓࠋḟ࡟ࠊ %U8 ࡢ ;36 ࢫ࣌ࢡࢺࣝཬࡧ 6$&&, ἲ࡟ࡼࡾ DVVLJQ ࡉࢀࡓ %UV%US2V1V&V%Uᅗ 9. 5-Bromouracil㸦BrU㸧࡜ Thymine(T)ࡢ᭱㐺໬ᵓ㐀࡜ཎᏊࣛ࣋ࣝ

V%US%UV%US ࡢ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝࢆᅗ  ࡟♧ࡍࠋࡇࡢᐇ㦂ࢫ࣌ࢡࢺࣝࡣ ILOP ≧ࢧࣥࣉ࡛ࣝ

ᐃࡉࢀࡓࡶࡢ࡛࠶ࡾࠊ6$&&, ࢫ࣌ࢡࢺࣝࡣࡇࡢᐇ㦂࡜ẚ࡭ࠊᖹᆒ H9 ࡢㄗᕪࡀ࠶ࡗࡓࠋ┿✵୰࡛ᐃࡉࢀࡓ

%U8 ࡢࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿ࡜ 6$&&, ࢫ࣌ࢡࢺࣝࡣ
ᖹᆒㄗᕪ H9 ௨ୗ࡛ồࡲࡗࡓࠋᚓࡽࢀࡓ 7 ࡢ &V
ཬࡧ &V ࢖࢜ࣥ໬≧ែࡣࠊV ㌶㐨࠿ࡽࡢ࢖࢜ࣥ໬㓄⨨ཬࡧ +202 ࠿ࡽ 5\GEHUJ ㌶㐨࡬ࡢ  㟁Ꮚບ㉳㓄⨨ࡀ୺㓄⨨࡜࡞ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊෆẆ࢖࢜ࣥ໬≧ែࡢィ⟬࡟࠾࠸࡚ࠊከ㟁Ꮚບ㉳ࠊ㌶㐨⦆࿴ࠊ㟁Ꮚ┦㛵࡞࡝ᅗ  %URPRXUDFLO ࡢ ;36 ࢫ࣌ࢡࢺࣝ 㯮 ཬࡧ
6$&&, ἲ࡛ィ⟬ࡉࢀࡓࢫ࣌ࢡࢺࣝ 㟷 ࡢከ㟁Ꮚ㐣⛬ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

ㅰ㎡ศᏊ◊ィ⟬ᶵࢭࣥࢱ࣮࡟ࡣࠊ ᖺᗘࡶᑓ᭷ࢡࣛࢫࢱ࣮ࡢ฼⏝ࢆㄆࡵ࡚㡬ࡁࠊࡑࡢィ⟬ᶵࣃ࣮࣡࡟ࡼࡗ࡚
◊✲ࡀ኱ࡁࡃ㐍ᒎࡋࡓࡇ࡜ࢆ῝ࡃឤㅰ⏦ࡋୖࡆࡿࠋ௒ᚋࡶࠊ㈗ࢭࣥࢱ࣮ࡢィ⟬ᶵ㈨※ࡢࡼࡾຠ⋡ⓗ࡞฼⏝࡟ࡼࡗ࡚ࠊᘬࡁ⥆ࡁ᪉ἲㄽ࡜ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ࣭ᨵⰋࢆ㐍ࡵࠊ㔞Ꮚ໬Ꮫࡢ◊✲ศ㔝ࢆඛᑟࡋ⥆ࡅࡽࢀࡿࡼ࠺࡞ࠊ

- 93 -

໬Ꮫⓗ౯್ࡢ㧗࠸ィ⟬ࢆᐇ⾜ࡋ࡚࠸ࡁࡓ࠸ࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) ୰㎷ ༤  $&6 PHHWLQJ 3URPLQHQW ,GHDV LQ 4XDQWXP &KHPLVWU\  ࢜ࣥࣛ࢖ࣥ ࢔࣓ࣜ࢝໬Ꮫ఍,QYLWHG ‫ۻ‬2) ୰㎷ ༤  7KHRU\ DQG &RPSXWDWLRQ IRU &RPSOH[ 0ROHFXODU 6\VWHPV ,Q 0HPRU\ RI ODWH 3URI .HLML
0RURNXPD 3DFLILFKHP ࢜ࣥࣛ࢖ࣥ ,QYLWHG ‫ۻ‬3) ୰㎷ ༤  &KHPLFDO&RQFHSWVIURP7KHRU\DQG&RPSXWDWLRQ3DFLILFKHP ࢜ࣥࣛ࢖ࣥ ,QYLWHG ‫ۻ‬4) ୰ᔱ ᾈஅ ୰㎷ ༤  ⌮ㄽ໬Ꮫウㄽ఍ ࢜ࣥࣛ࢖ࣥ‫ۻ‬5) 㯮ᕝ ᝆ⣴ ୰㎷ ༤  ⌮ㄽ໬Ꮫウㄽ఍ ࢜ࣥࣛ࢖ࣥ‫ۻ‬6) ୰㎷ ༤ ୰ᔱ ᾈஅ 㯮ᕝ ᝆ⣴  ศᏊ⛉Ꮫウㄽ఍ ࢜ࣥࣛ࢖ࣥ‫ۻ‬7) ୰ᔱ ᾈஅ ୰㎷ ༤  ศᏊ⛉Ꮫウㄽ఍ ࢜ࣥࣛ࢖ࣥ‫ۻ‬8) 㯮ᕝ ᝆ⣴ ୰㎷ ༤  ศᏊ⛉Ꮫウㄽ఍ ࢜ࣥࣛ࢖ࣥ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) +1DNDWVXML+1DNDVKLPD<,.XURNDZD  ³$FFXUDWHVFDOLQJIXQFWLRQVRIWKHVFDOHG6FKU|GLQJHUHTXDWLRQ´-&KHP3K\V  ‫ۻ‬2) H. Nakatsuji and H. Nakashima, “Potential curves of the lower nine states of Li2 molecule: Accurate
calculations with the free complement theory and the comparisons with the SAC/SAC-CI results”, J. Chem. Phys.,submitted.
‫ۻ‬3) H. Nakatsuji and H. Nakashima, “Direct local sampling method for solving the Schrödinger equations by thefree complement - local Schrödinger equation theory”, Chem. Phys. Lett., submitted.
‫ۻ‬4) H. Nakashima and H. Nakatsuji, “Potential energy curves of ground and low-lying excited states of CH+
molecule by the free complement - local Schrodinger equation method”, in preparation.
‫ۻ‬5) H. Nakashima and H. Nakatsuji, “Benchmark calculations of H4 molecule by the free complement - local
Schrodinger equation method with the direct local sampling method”, in preparation.
‫ۻ‬6) H. Nakashima and H. Nakatsuji, “Variational calculation of the ground state of a boron atom by the freecomplement sij-assisted rij theory”, in preparation.
‫ۻ‬7) Y. I. Kurokawa, H. Nakatsuji, M. Hirato, and A. Yokoya, “X-ray Photoelectron Spectroscopy of Thymine and5-Bromouracil Studied by the Symmetry-Adapted-Cluster Configuration-Interaction (SAC-CI) Theory”, Chem.
Phys. Lett., submitted.

- 94 -

Ⰽ⣲ቑឤග㟁ᴟ࣭ගゐ፹➼ࡢィ⟬໬Ꮫⓗ◊✲Computational study on dye-sensitized photoelectrolysis andphotocatalysis‫ⲡۑ‬㛫 ோ㸦ᅜ❧◊✲㛤Ⓨἲே⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ㸧




◊✲┠ⓗ
S ᆺⰍ⣲ቑឤග㟁ᴟ㸦㝜ᴟ㸧ࡣࠊኴ㝧ග୰ࡢ▷Ἴ㛗ගࡋ࠿྾཰࡛ࡁ࡞࠸ 1L2 ➼ࡢ S ᆺ༙ᑟయ⾲㠃࡟ቑឤⰍ⣲ࢆ⤖ྜࡋࠊගࡢ྾཰ࢆྍど㉥እ㡿ᇦ࡬࡜኱ࡁࡃᗈࡆࡿࡇ࡜࡟ࡼࡾኴ㝧ග࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ㧗ࡵࡿࠋග྾཰࡟ࡼࡗ࡚ +202 ࠿ࡽ /802 ࡬Ⰽ⣲ࡀບ㉳ࡉࢀࠊS ᆺ༙ᑟయࡢ౯㟁Ꮚᖏ࡬ṇᏍࡀὀධࡉࢀࡿࠋ㑏ඖ≧ែ࡜࡞ࡗࡓⰍ⣲ࡣᇶ㉁࡟㟁Ꮚ౪୚ࡋඖࡢᇶᗏ≧ែ࡟ᡠࡾࠊᇶ㉁ࡢ㑏ඖ཯ᛂ࡟ࡼࡗ࡚┠ⓗ⏕ᡂ≀ࡀᚓࡽࢀࡿࠋᮏ
◊✲ㄢ㢟ࡢ┠ⓗࡣࠊࡇࢀࡽࡢ཯ᛂ୰㛫యᵓ㐀ࡸ཯ᛂᶵᵓࠊ཯ᛂάᛶཬࡧ⏕ᡂ≀㑅ᢥᛶ࡟ᑐࡍࡿᨭ㓄ᅉᏊࢆィ⟬໬Ꮫⓗ࡟ゎ᫂ࡋࠊ༙ᑟయཬࡧⰍ⣲タィ➼ᐇ㦂࡟ࣇ࢕࣮ࢻࣂࢵࢡࡍࡿࡇ࡜࡛࠶ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ  ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊỈ୰ 3&0 ࡢⰍ⣲ศᏊཬࡧࡑࡢ㑏ඖయࠊᇶ㉁ࡢ㓟⣲ศᏊࠊཬࡧࡇࢀࡽࡢ

」ྜయ➼ࢆ ')7 ἲ %/<3* GS ࡟࡚ᵓ㐀᭱㐺໬ࡋࡓࠋ⥆࠸࡚᣺ືᩘ࣭⇕ຊᏛ㔞ィ⟬࡜㟁Ꮚᐦᗘゎᯒ
0XOOLNHQ13$ ➼ࢆ⾜ࡗࡓࠋ



◊✲ᡂᯝ
COOH

Ⰽ⣲ቑឤග㝜ᴟࢆ⏝࠸ࡓỈ࡜㓟⣲࠿ࡽࡢ㑏ඖⓗ㐣㓟໬Ỉ⣲⏕ᡂ཯ᛂࢆ᳨ウࡋࡓࠋᅗ  ࡢࢡ࣐ࣜࣥ  ཬࡧ࣌ࣜࣞࣥࣔࣀ࢖࣑ࢻ
㸦30,㸧

N

O

O

coumarin 343

Ⰽ⣲㑏ඖయࡢ &+ ᇶࡣ 2 ศᏊ࡜ +㺃㺃㺃2 ศᏊ㛫Ỉ⣲⤖ྜࢆᙧᡂࡋ཯
ᛂ୰㛫యࢆ୚࠼ࡓࠋ㟁Ꮚᐦᗘゎᯒࡢ⤖ᯝࠊ2 ࡣ᏶඲࡟㑏ඖࡉࢀ 2íƔOS࡟ኚ໬ࡋࡓࠋ⇕ຊᏛ㔞ィ⟬࡟ࡼࡿ཯ᛂ๓ࠊ཯ᛂ୰㛫యࠊཬࡧ཯ᛂᚋ

N

PMI

ࡢࢠࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬࠿ࡽࠊⰍ⣲㑏ඖయ࡟ࡼࡿ 2 㑏ඖ཯ᛂOࡣ⮬Ⓨⓗ࡟㐍⾜ࡋࠊ࠿ࡘ 2íƔࡣ㏿ࡸ࠿࡟Ⰽ⣲࠿ࡽゎ㞳ࡍࡿࡇ࡜ࢆ᫂

ᅗ Ⰽ⣲ࡢᵓ㐀ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊ཯ᛂ୰㛫యࡣ +ࡸ +2Ɣ࡜ࡣ཯ᛂࡏࡎ㟁Ꮚ⛣ືࡶ㉳ࡇࡽ࡞࠿ࡗࡓࠋ௨ୖࡢ⤖ᯝࡣࠊ2 㑏ඖᚋ࡟Ⰽ⣲ࡀ 2íƔ࡜ +ࡸ +2Ɣ࡜ࡢ୙ᆒ໬཯ᛂ࡟㛵୚ࡏࡎࠊ+2Ɣཬࡧ +2íࢆ⤒⏤ࡍࡿ +2 ⏕ᡂ཯ᛂࡀຠ⋡ⓗ࡟㉳ࡇࡿࡇ࡜ࢆ♧၀ࡋࠊࡇࢀࡽⰍ⣲ᵓ㐀ࡢ᭷ຠᛶࢆ⿬௜ࡅࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬+LUR\XNL 7DWHQR<XJR0LVHNL+LWRVKL.XVDPD 6KLK<XDQ &KHQ 7DNHKLVD 0RFKL]XNL .D]XKLUR6D\DPD$&6

6XVWDLQDEOH&KHPLVWU\ (QJLQHHULQJ  ‫ۻ‬+LWRVKL.XVDPD-RXUQDORI3KRWRFKHPLVWU\ 3KRWRELRORJ\$&KHPLVWU\  - 95 -

⏕యศᏊ」㞧⣔ࡢ඲ཎᏊ࣭⢒ど໬ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲All-atom/coarse-grained molecular simulation studies of complex
biomolecular systems‫⏣ۑ‬୰ ᡂ඾㸪᳃ ⩏἞㸪ᰩᓮ ௨ஂ⏨㸪ᒾᇛ 㞝┿㸪ලᚿሀ ᨻᩥ㸪⏣୰ ኱㞞㸪୰⏣ ᯻ஓ㸦⚄ᡞ኱Ꮫ኱Ꮫ㝔ࢩࢫࢸ࣒᝟ሗᏛ◊✲⛉㸧




◊✲┠ⓗ

 ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ *$%$$ ཷᐜయࡢసືᶵᵓࡢゎ᫂*$%$$ ཷᐜయࡣ୰ᯡ⚄⤒⣔࡟࠾࠸࡚ᢚไᛶࡢാࡁࢆࡍࡿ &O࢖࢜ࣥࢳࣕࢿ࡛ࣝ࠶ࡾ㸪⚄⤒ఏ㐩≀㉁࡛࠶ࡿ
*$%$ ࡀ⤖ྜࡍࡿࡇ࡜࡟ࡼࡾ࢖࢜ࣥࢳࣕࢿࣝࡀ㛤ཱྀࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ*$%$$ ཷᐜయࡣ඲㌟㯞㓉࡟㛵ࢃࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࡀ㸪඲㌟㯞㓉⸆స⏝ࡢศᏊᶵᵓࡣ୙᫂࡞Ⅼࡀከ࠸ࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪඲㌟㯞㓉⸆ࡢస⏝ࡸࡑࢀ࡟క࠺ཷᐜయࡢᵓ㐀ኚ໬࡟㛵ࡍࡿศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ
 ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ࣜ࣎ࢯ࣮࣒ࡣ⣽⬊࡟࠾࠸࡚ࢱࣥࣃࢡ㉁ྜᡂࢆࡘ࠿ࡉ࡝ࡿᕧ኱࡞ࢱࣥࣃࢡ㉁࣭51$ 」ྜయ࡛࠶ࡿࠋࣜ࣎ࢯ࣮
࣒࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ྜᡂࡢ㛤ጞ㐣⛬࡛ࡣ㸪ࣜ࣎ࢯ࣮࣒࡜㛤ጞẁ㝵≉᭷ࡢࢱࣥࣃࢡ㉁࠿ࡽᵓᡂࡉࢀࡿ⩻ヂ㛤ጞ」ྜయࡀᙧᡂࡉࢀࡿࠋࡇࡢ࡜ࡁṇ☜࡞ W51$ ࡢ⤖ྜࡢࡓࡵ࡟ࡣࣜ࣎ࢯ࣮࣒ࢆᵓᡂࡍࡿࣜ࣎ࢯ࣮࣒ࢱࣥࣃࢡ㉁ࡢ࠸ࡃࡘ࠿ࡀ✚ᴟⓗ࡟㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪ࡇࢀࡽࡢࣜ࣎ࢯ࣮࣒
ࢱࣥࣃࢡ㉁ࡢᙺ๭ࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ *$%$$ ཷᐜయࡢసືᶵᵓࡢゎ᫂*$%$$ ཷᐜయ࡜ࣜ࢞ࣥࢻ」ྜయᵓ㐀࡟ࡘ࠸࡚⬡㉁஧㔜⭷࡜Ỉ⁐፹࡜࡟ᇙࡵ㎸ࢇࡔ⣔ࢆ⏝ពࡋࡓࠋ*$%$$
ཷᐜయࡢཎᏊᩘࡣ⣙  ࡜࡞ࡾ㸪⁐፹࡞࡝ࢆྵࡵࡓ඲ཎᏊᩘࡣ⣙  ࡛࠶ࡿࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀ
ࡓ⣔࡟ᑐࡋ࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ *520$&6 ࡟ࡼࡾᐇ⾜ࡋࡓࠋࢱࣥࣃࢡ㉁࡞࡝ࡢຊሙ࡜ࡋ࡚ࡣ
&+$500P ࢆ౑⏝ࡋࡓࠋࣜ࢞ࣥࢻ⤖ྜ≧ែࡢཷᐜయ࡟ᑐࡋ࡚  QV ࡢィ⟬ࢆ  ᅇᐇ⾜ࡋ㸪ྵࡲࢀࡿࣜ࢞
ࣥࢻ࡟౫Ꮡࡋࡓࢱࣥࣃࢡ㉁」ྜయࡢᏳᐃᛶࡸᵓ㐀ኚ໬ࢆゎᯒࡋࡓࠋࡉࡽ࡟㸪ࣜ࢞ࣥࢻࢆึᮇᵓ㐀࠿ࡽ㝖࠸ࡓ⣔࡛ࡶ QV ࡢィ⟬ࢆ  ᅇᐇ⾜ࡍࡿࡇ࡜࡟ࡼࡾ㸪ࣜ࢞ࣥࢻࡢ᭷↓࡟ࡼࡿᵓ㐀ࡢẚ㍑ࢆ⾜ࡗࡓࠋ ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ィ⟬ᑐ㇟ࡢ」ྜయ࡜ࡋ࡚ࣜ࣎ࢯ࣮࣒ᑠࢧࣈࣘࢽࢵࢺ㸪P51$ ศᏊ㸪㛤ጞ W51$ ศᏊ㸪㛤ጞᅉᏊ ,)࣭,)࣭
,) ࠿ࡽᵓᡂࡉࢀࡿࡶࡢࢆ౑⏝ࡋࡓࠋࡇࢀࡽࡢᵓ㐀ࢆ⢒ど໬ࣔࢹࣝ 0$57,1, ࡛ᢅࡗࡓࠋ⢒ど໬ࡉࢀࡓ⩻ヂ㛤ጞ」ྜయࡣ⣙  ⢏Ꮚ࡛࠶ࡿࠋࡲࡓ⁐፹࡞࡝ࢆྵࡵࡓ඲⢏Ꮚᩘࡣ⣙  ࡜࡞ࡗࡓࠋศᏊືຊᏛィ⟬ࡣ
*520$&6 ࡟ࡼࡾᐇ⾜ࡋࡓࠋࣜ࣎ࢯ࣮࣒ࢱࣥࣃࢡ㉁ࡢᏑᅾࡀ㛤ጞ W51$ ࡟㛵ࡍࡿᏳᐃᛶ࡟ᑐࡋ࡚࡝ࡢࡼ࠺࡟
ᐤ୚ࡋ࡚࠸ࡿ࠿ࢆ⌮ゎࡍࡿࡓࡵ࡟㸪㛤ጞ๓」ྜయࡢᵝࠎ࡞≧ែ࡟ᑐࡋ࡚  ȣV ࡢ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢࢩ
࣑࣮ࣗࣞࢩࣙࣥࢆ  ᅇࡎࡘᐇ⾜ࡋ㸪W51$ ࡢゎ㞳⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ- 96 -

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ࡾ㸪᭱⤊ⓗ࡟࢖࢜ࣥࡢ㏱㐣ᛶࢆไᚚࡋ࡚࠸ࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋᅗ  ࢳࣕࢿࣝ 3RUH ༙ᚄ ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ࣜ࣎ࢯ࣮࣒⣔࡟࠾࠸࡚ W51$ ࡢ⤖ྜࡀ࡯ࡰ᏶⤖ࡋࡓ≧ែ࡛ࡣ W51$
⤖ྜ≧ែࡀᏳᐃ࡛࠶ࡾ㸦ᅗ  㟷㸧㸪ゎ㞳ࡍࡿࡓࡵࡢάᛶ໬㞀ቨࡣ㧗ࡃ࡞ࡗ࡚࠸ࡓࠋ୍᪉࡛ W51$ ⤖ྜ᏶⤖㏵୰ࡢ≧ែ࡛ࡣ W51$ ⤖ྜ≧ែ࡜ゎ㞳≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᕪࡀᑠࡉࡃ㸪ゎ㞳ࡋࡸࡍ࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸦ᅗ  ㉥㸧ࠋࣜ࣎ࢯ࣮࣒࣭51$ 」ྜయࡢᵓ㐀ࢆゎᯒࡍࡿࡇ࡜࡟ࡼࡾ㸪ࡇࡇࡢࡼ࠺࡞⮬⏤࢚ࢿࣝࢠ࣮ࡢᕪ␗ࡣ≉ᐃࡢࣜ࣎ࢯ࣮࣒ࢱࣥࣃࢡ㉁࡜
࡜ᅗ  W51$ ゎ㞳⮬⏤࢚ࢿࣝࢠ࣮

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ÛÜ Mori H., invited, Materials informatics for designing functional liquid materials: Perspective from fragmentbased molecular theory, PACIFICHEM 2020, PHYS, (Innovative Computational Chemistry Powered by Big
Data and Machine Learning (#49)), Online (Honolulu, USA) (Dec. 2021).
ÛÜ Nahoko Kuroki, Mori H., invited, Materials informatics for designing CO2 capturing liquids with selectivity,
The 1st Symposium on Carbon Ultimate Utilization Technologies for the Global Environment (CUUTE-1), B45, Online (Nara, Japan) (Dec. 2021).
ÛÜ Suzuki R., Kuroki N., Mori H.), Designing ionic liquids for efficient CO2 capture: A materials informatics
study, Anionic state play more important role: electronic structure informatics of gas-phase acidity toward fastand precies acids design for engineering, 9th International Symposium on Molecular Thermodynamics andMolecular Simulation (MTMS 2021), PA12, Online (Sep. 2021).
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ÛÜ Goto D., Takashima K., Kanebako Y., Kuroki N., Mori H.*, Submitted, (2022).
ÛÜ Suzuki R., Kuroki N., Mori H.*, Submitted, (2022).
ÛÜ Kuroki N., Uchino Y., Funakura T., Mori H.*, Electronic fluctuation in physiological solutions: Trimethylamine
N-oxide and tert-butyl alcohol https://doi.org/10.26434/chemrxiv-2022-hj9l4 (2022).
ÛÜ Kuroki N., Mori H.*, selected as Inside Cover, Comprehensive Physical Chemistry Learning Based on
Blended Learning: A New Laboratory Course, J. Chem. Edu. 12, 3864-3870 (2021).,ÛOpen AccessÜ
ÛÜ Ono T., Kimura K. , Ihara M., Yamanaka Y., Sasaki M., Mori H., Hisaeda Y., selected as Front Cover, Roomtemperature Phosphorescence Emitters Exhibiting Red to Near-infrared Emission Derived from Intermolecular
Charge-transfer Triplet States of Naphthalenediimide-Halobenzoate Triad Molecules, Chem. Eur. J , 27, 93359541 (2021).

- 101 -

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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
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᫬ࠎ้ࠎ࡛ࡢ⏺㠃⣔ࡢศᴟࢆィ⟬ࡍࡿ 0' ࣉࣟࢢ࣒ࣛ &DOQRV ࡢ㛤Ⓨࢆᮏࢢ࣮ࣝࣉ࡛㐍ࡵࡘࡘࠊࡑࢀࢆ⏝࠸ࡓ◊✲ࢆ㐙⾜ࡋ࡚ࡁࡓࠋỈ⾲㠃࡛ࡢග໬Ꮫ཯ᛂᶵᵓࡢゎᯒ࡟࠾࠸࡚ࡣࠊ㟁Ꮚບ㉳≧ែࡢィ⟬࡜ࡑࡢ⁐፹ຠᯝࡢぢ✚ࡶࡾࡀᚲせ࡛ࠊࡑࡢࡓࡵ࡟ࡣ୺࡜ࡋ࡚ᮏࢭࣥࢱ࣮ࡢ 0ROSUR ࢆ౑⏝ࡋࡓࠋ
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 ⏺㠃࿴࿘Ἴศග࡟࠾ࡅࡿ )UHVQHO ಀᩘศᩓࡢ㔜せᛶ >@ ⏺㠃ࢆ㑅ᢥⓗ࡟ᤊ࠼ࡿ᭷ຊ࡞ᡭἲ࡜ࡋ࡚ࠊ࿴࿘ἼⓎ⏕ࢫ࣌ࢡࢺࣝࡀ࠶ࡾࠊᗈࡃᐇ⏝ⓗ࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋ
ࡑࡢゎᯒ࡟࠾࠸࡚㉥እ᣺ືᩘ㡿ᇦࡢࢫ࣌ࢡࢺࣝࡣࠊ㠀⥺ᙧឤཷ⋡ F   ࡢ᣺ືᩘ౫Ꮡᛶࢆ⾲ࡍ࡜⪃࠼ࡽࢀ࡚ࡁ
ࡓࠋࡋ࠿ࡋࠊ⏺㠃ศගࡢᙉᗘࡣࠊF   ࡟ຍ࠼࡚ࠊ⏺㠃࡟࠾ࡅࡿ㟁ሙࡢᙉࡉࢆ୚࠼ࡿ )UHVQHO ಀᩘ࡟ࡶ౫Ꮡࡋࠊ
ࡑࢀࡀ᣺ືᩘ౫Ꮡᛶࢆᣢࡘሙྜ࡟ࡣ࿴࿘Ἴࢫ࣌ࢡࢺࣝᙧ≧࡟ᨭ㓄ⓗ࡞ᙳ㡪ࡀ࠶ࡾ࠺ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
ࡑࡢࡼ࠺࡞ሙྜࡣࠊ⏺㠃ࡢ」⣲ᒅᢡ⋡࡟㢧ⴭ࡞ศᩓࢆࡶࡘ࡜ࡁ࡟⪃࠼ࡽࢀࠊࡑࢀࡣᙉࡃ࡚⊃࠸྾཰ࢆࡶࡘ᣺
ືࣂࣥࢻࡢ୰ࡢ㡿ᇦ࡛⌧ࢀࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ᮾ໭኱ྔࢢ࣮ࣝࣉࡢᐇ㦂࡜ඹྠࡋ࡚ࠊࡲࡎ୺࡞᣺ືࣂࣥ
ࢻࡢ୰࡛ࡢ」⣲ᒅᢡ⋡ࡢศᩓࢆᐃ㔞ⓗ࡟ ᐃࡋࡓࠋࡑࡋ࡚ࠊࡑࡢࢹ࣮ࢱࢆࡶ࡜࡟ )UHVQHO ಀᩘࡢศᩓࡢ኱ࡁࡉ
࡜ࡑࡢࢫ࣌ࢡࢺࣝゎᯒ࡬ࡢᙳ㡪ࡢ඲యࢆ᫂ࡽ࠿࡜ࡋࠊᐇ㦂ࢆゎᯒࡍࡿ㝿ࡢᣦ㔪ࢆᥦ♧ࡋࡓࠋ࡜ࡃ࡟ᙉࡃ࡛⊃࠸྾཰ࢆࡶࡘ᣺ືࣂࣥࢻ࡛ࠊF   ࡢ᣺ື㠀ඹ㬆ࡢࣂࢵࢡࢢࣛ࢘ࣥࢻࢩࢢࢼࣝࡀ኱ࡁ࠸ሙྜࠊ)UHVQHO ಀᩘศᩓࡀᨭ㓄ⓗ࡜࡞ࡿࠋࡇࢀࡣᅛᾮ⏺㠃ࡢ 6)* ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࡳࡽࢀ࡚࠸ࡓࡇ࡜ࡶ᫂ࡽ࠿࡜࡞ࡗࡓࠋ ᮏ◊✲࡛ࡣࠊ」⣲ᒅᢡ⋡ࡢศᩓࢆᐃ㔞ⓗ࡟ᐃࡍࡿᐇ㦂ࡢゎᯒ⏝ࣉࣟࢢ࣒ࣛࡶ㛤Ⓨࡋࠊࡑࢀࡶ :HE ୖ࡛- 102 -

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ʤ +4 ʥΝ̐ʁ̏͹౲ྖർͲࠠ߻ͤΖ͞ͳͲɼφϨϕοιϱࠐ֪Ͷ̐ͯ͹ %4 ෨Ғͳ̏ͯ͹ +4 ෨ҒΝ‫ڠ‬ଚͦͪ͠φϨϕοιϱϠόϐχϫΫόϱζϗϱμΫόϱʤ +4  %4  ʥ͹߻੔Νߨ͏Ήͪ͢ɽಚΔΗͪ
+4  %4  ͹Կָద੓࣯Ν໎Δ͖ͶͤΖͪΌɼ‫ݽ‬ରɼ༻ӹྈয়ସͶ͕͏ͱ 899LV ଎ఈΝߨ͏ɼͨ͹ηϘέφϩͳ 7'')7 ͶΓΖηϘέφϩ༩૟ͳ͹ർֳΝߨ͏Ήͪ͢ )LJXUH-2UJ&KHP t ɽ- 108 -)LJXUH ༻ӹ D ͳ‫ݽ‬ର E Ͳ͹ 899LV ηϘέφϩͳηϘέφϩ༩૟͹ർֳʤࠉતʥ
͞͹ർֳͶΓΕɼ෾ࢢٌಕ͖Δ༩૟͠ΗΖ 899LV ηϘέφϩ͹‫ٷ‬फΓΕௗഀௗ྘ҮͶϔϫʖχ͵ϒʖέ͗‫ݡ‬ΔΗɼ༻ӹ஦‫ݽ‬ର஦૔๏Ͷ͕͏ͱ෾ࢢؔͲ͹ు՛Ңಊ૮‫༽ࡠޕ‬͹ଚࡑ͗ࣖࠨ͠ΗΉͪ͢ɽ͞͹எ‫ݡ‬Ν‫͖׈‬͢ɼ͞͹෾ࢢ͹࢐Կؒ‫ݫ‬ಝ੓Ώɼҡ๏੓Νਫ਼͖ͪ͢υώ΢ηԢ༽΃޴͜ͱ͠Δ͵Ζ‫ڂݜ‬Νߨ͑༩ఈͲͤɽ̒ ൅නࣰ੹Ήͪͺ༩ఈʀϟνϨϱ࢐ΠϩϝωΤϞ୴࣍പۜৰഖͶΓΖ &t2 ݃߻͹મ୔దՅਭો෾մൕԢ ۜ ༦ܾʀ݆ଞ ཨॻʀᦶ
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յ &6- ԿָϓΥην  Ψϱϧ΢ϱ  ೧  ݆ t ೖ 3 ϛηνʖ 
ʀ3W$O 32  ৰഖͶΓΖΠϩαʖϩ‫;ٶ‬ΩϩϚωϩԿ߻෼͹ΠϩΩϱ΃͹Յਭો෾մൕԢ ԣీ ‫ݓ‬ਕʀۜ༦ܾʀ໼࡜ ‫ ࢢښ‬୊  յ &6- ԿָϓΥην  Ψϱϧ΢ϱ  ೧  ݆ t ೖ 3 ϛηνʖ ˔ζϚϨϩΩϩϗό΢χ͹߻੔ͳϩ΢η࢐੓Ωϩϗϱ౵Ճରͳ͢ͱ͹੓࣯ ᖄ୫ ༒‫س‬ʀ೉ຌ बฑʀ໼࡜ ‫ښ‬ࢢ ୊  յ &6- ԿָϓΥην  Ψϱϧ΢ϱ  ೧  ݆ t ೖ 3 ϛηνʖ 
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बฑʀ໼࡜ ‫ࡪ ࢢښ‬ରԿָճ୊  յ౾࿨ճ Ψϱϧ΢ϱ  ೧  ݆  ೖ ' ޳ಆ 
˔1R[\O ϧζΩϩͳ୴࣍ಖৰഖΝ༽͏ͪ‫࢐ـۯ‬ԿͶΓΖΠϩΩϱ͹୦ਭોൕԢ ґ౽ ༐ʀۜ ༦ܾʀ໼࡜ ‫ښ‬ࢢ ୊  յৰഖ౾࿨ճ Ψϱϧ΢ϱ  ೧  ݆  ೖ ' ޳ಆ ʀϟνϨϱ࢐ΠϩϝωΤϞ୴࣍ 3W ψόཽࢢৰഖͶΓΖΠϩαʖϩ‫;ٶ‬ΩϩϚωϩԿ߻෼͹ΠϩΩϱ΃͹Յਭો෾մൕԢ ԣీ ‫ݓ‬ਕʀۜ ༦ܾʀ໼࡜ ‫ ࢢښ‬୊  յৰഖ౾࿨ճ Ψϱϧ΢ϱ  ೧  ݆ t ೖ '޳ಆ ˔ϖΫγΠϨʖϩϫε㿈ΤϞ࢐ ,,, ͕Γͽ㿈΢Ϩε㿈ΤϞ࢐ ,,, ϨοΤϞt‫ݽ‬ର஦͕Γͽ㿈༻ӹ஦͹ߑଆ ‫آ‬㟔 ޻‫ن‬ʀ኏Ԯ ༠ࢢʀ‫ ݬ‬ਜ਼ٕʀ࣋ీ ๮ʀ߶୫ ޭʀຌؔ బਫ਼ʀ໼࡜ ‫ ࢢښ‬୊  յ༙‫ۜؽ‬଒Կָ౾࿨ճ Ψϱϧ΢ϱ  ೧  ݆ t ೖ 2 ޳ಆ 

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‫ ࢢښ‬୊  յ༙‫ۜؽ‬଒Կָ౾࿨ճ Ψϱϧ΢ϱ  ೧  ݆ t ೖ 3& ϛηνʖ ˔ుࢢ෈ଏεέϫϘϱνζΦόϱۜ଒ࡪରͶΓΖۜ଒tഓҒࢢ‫ڢ‬ಉద݃߻઀இൕԢ ౨ ୕໷ ୊  յ༙‫ۜؽ‬଒ऑघ͹ճՈ͹ָߏ ౨‫ښ‬୉ָછ໼ΫϡϱϏη ౨‫  ښ‬೧  ݆ t ೖ </ ऑघߪԍ ˔યҢۜ଒ΠωΨϱझ͹ৰഖ‫ؽ‬೵ ‫آ‬㟔 ޻‫ ن‬୊  յ‫ܜ‬ጱ༙‫ؽ‬ԿָऑघεϱϛζΤϞ Ψϱϧ΢ϱ  ೧ ݆  ೖ ডଶߪԍ ̓ ड़൝ࣰ੹Ήͪͺ༩ఈ
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WKHDQWKUDFHQH +2  FOXVWHUฟ∧ᐇ⦼‫ۻ‬M. Miyazaki, T. Kamiya, M. Wohlgemuth, K. Chatterjee, R. Mitrić, O. Dopfer, M. Fujii, “Real-time observation ofphotoionization-induced water migration dynamics in 4-methylformanilide±water by picosecond time-resolved infrared
spectroscopy and ab initio molecular dynamics simulations”, Phys. Chem. Chem. Phys. 24(1), 73±85 (2022).

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ࡍࡿ┤ほⓗᥥീࡀᚓࡽࢀࡿࠋ,5& ࢆᵓᡂࡍࡿศᏊᵓ㐀⩌ࡣ N ±  ḟඖࡢከḟඖࢹ࣮ࢱ࡛࠶ࡿࡓࡵࠊ㐺ษ࡞పḟඖ✵㛫࡬ࡢྍど໬ࡣᅔ㞴࡛࠶ࡗࡓࠋᡃࠎࡣࡇࢀࡲ࡛࡟ࠊከḟඖࢹ࣮ࢱ㛫ࡢ㊥㞳㛵ಀࢆ࡛ࡁࡿࡔࡅಖࡘࡼ
࠺࡞ḟඖ⦰⣙ἲ࡛࠶ࡿྂ඾ⓗከḟඖᑻᗘᵓᡂ㸦&0'6㸧ἲࢆ ,5& ࡟ἢࡗࡓศᏊᵓ㐀⩌࡟㐺⏝ࡍࡿࡇ࡜࡛ࠊ཯ᛂᶵᵓ࡟㛵ࡍࡿ஦๓▱㆑࡞ࡋ࡟཯ᛂࢆグ㏙ࡍࡿ୺ᗙᶆࢆᚓࡿࡇ
࡜ࠊཬࡧ RXWRIVDPSOH ࡟ᣑᙇࡉࢀࡓ &0'6
ἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊ,5& ࢿࢵࢺ࣮࣡ࢡ
࡟ࡼࡗ࡚ᐃ⩏ࡉࢀࡓ୺ᗙᶆ✵㛫ୖ࡟
RQWKHIO\ 0' ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡿࢺࣛࢪ
࢙ࢡࢺࣜࢆᑕᙳࡍࡿ᪉ἲࢆ UHDFWLRQ VSDFH
SURMHFWRU 5H63HU ࡜ࡋ࡚ᥦ᱌ࡋ࡚ࡁࡓࠋᮏ◊✲࡛ࡣࠊ㔠ࢡࣛࢫࢱ࣮$X ࡢྠ✀᰾⨨᥮཯㌿␗ᛶ໬཯ᛂࡢ཯ᛂ⤒㊰ᆅᅗ࡜ࡑࡢ 0' ࢺࣛࢪ࢙ࢡࢺࣜ࡟ᑐࡋ࡚ 5H63HU ࢆ㐺⏝ࡋࠊศᒱᅗ  ࡘࡢ ,5& ࢆཧ↷ᵓ㐀࡜ࡋ࡚ᵓ⠏ࡉࢀࡓ  ḟඖࡢ཯ᛂ✵㛫ୖ࡟ᑕᙳࡉࢀࡓࢺࣛࢪ࢙ࢡࢺࣜࠋጞⅬࡣ $X ࡢ 76G
Cs ㏆ഐ࡜ࡋࡓࠋࢺࣛࢪ࢙ࢡࢺࣜࡣ D  ,5& ࡟ἢࡗ࡚ 0,1
C2v ࡟⮳ࡿࡶࡢࠊ E  76E C2v ࢆ㏻ࡗ࡚ 0,1 ࡟⮳ࡿࡶࡢࠊ F  ືⓗศᒱ࡟ࡼࡾ 0,1¶¶࡟⮳ࡿࡶࡢࠊ G 76E ࢆ㏻
ࡗ࡚ 0,1¶¶࡟⮳ࡿࡶࡢࠊࡢ  ✀㢮࡟ศ㢮࡛ࡁࡿࠋ

཯ᛂ࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫࡢຠᯝࢆヲ⣽࡟ㄪᰝࡋࡓࠋࡲࡎࠊ᭱Ᏻᐃᵓ㐀 0,1 C2v ࡜ࡑࡢྠ✀᰾⨨᥮␗ᛶయ 0,1¶¶ࢆ 76E C2v ࡛ࡘ࡞ࡄ ,5& ࡜ 76G
Cs ࡜ 0,1 ཬࡧ 0,1¶¶ࢆࡘ࡞ࡄ ,5& ࢆཧ↷ᵓ㐀࡜ࡋ࡚ࠊ ḟඖࡢ཯ᛂ✵㛫ࢆỴᐃࡋࡓࠋࡇࡢ཯ᛂ✵㛫ୖ࡟ࠊ
76G ࠿ࡽࡢ  ᮏࡢࢺࣛࢪ࢙ࢡࢺࣜࢆᑕᙳࡋࡓ⤖ᯝࢆᅗ  ࡟♧ࡍࠋ,5& ࠿ࡽ㐓ࢀࡓ 0,1¶¶࡟⮳ࡿࢺࣛࢪ࢙
ࢡࢺࣜࡀከᩘᚓࡽࢀࡿࡀࠊࡇࢀ࡟ࡣ኱ࡁࡃศࡅ࡚ࠊືⓗ࡞ศᒱ࡟ࡼࡾ ,5& ࢆ㣕ࡧ⛣ࡿ࣓࢝ࢽࢬ࣒ F ࡜ࠊືຊᏛຠᯝ࡟ࡼࡾ ,5& ࢆእࢀ࡚ 76E ௜㏆ࡲ࡛฿㐩ࡋ࡚࠿ࡽ 0,1¶¶࡟⮳ࡿ࣓࢝ࢽࢬ࣒ G ࡢ஧✀㢮ࡀ࠶ࡿࡇ࡜ࡀ
᫂ࡽ࠿࡜࡞ࡗࡓࠋ
 ཯ᛂ࡟㛵୚ࡋ࡚࠸ࡿ㌶㐨ࢆ≉ᐃࡍࡿ QDWXUDOUHDFWLRQRUELWDO ἲࡢ㛤Ⓨ ㏆ᖺࠊᐇ㦂ࡸゎᯒࡢ⮬ື໬ࡀὀ┠ࡉࢀ࡚࠸ࡿࡀࠊィ⟬໬Ꮫ࡟࠾࠸࡚ࡶ⮬ື໬ࡢὶࢀࡀࢺࣞࣥࢻ࡜࡞ࡗ࡚࠸
ࡿࠋᅛ᭷཯ᛂᗙᶆ㸦,5&㸧࡟ἢࡗࡓ໬Ꮫ཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᶆ‽ⓗ࡞ゎᯒࡣࠊ  㑄⛣≧ែᵓ㐀ࡢィ⟬ࠊ άᛶ໬㞀ቨࡢィ⟬ࠊ  ㏿ᗘㄽゎᯒࡢࡼ࠺࡞ᡭ㡰࡛⾜ࢃࢀࡿࡀࠊࡇࢀࡽࡣᴫࡡ⮬ື໬ࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊ཯ᛂ
ᶵᵓࢆ⌮ゎࡍࡿୖ࡛ࡣࠊࡇ࠺ࡋࡓ཯ᛂ⤒㊰ゎᯒ࡟ຍ࠼࡚ศᏊ㌶㐨࡟ᇶ࡙ࡃゎᯒࡀᚲせ࡜࡞ࡿࠋศᏊ㌶㐨࡟ᇶ࡙ࡃ཯ᛂ⌮ㄽ࡟ࡘ࠸࡚ࡣᐃᘧ໬ࡉࢀࡓࡶࡢࡀ࠶ࡿࡀࠊᐇ㝿࡟㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚୚࠼ࡽࢀࡓศᏊ㌶㐨࡟ᇶ࡙ࡁࣇࣟࣥࢸ࢕࢔㌶㐨⌮ㄽࢆ㐺⏝ࡍࡿ࡜㛫㐪ࡗࡓ⤖ㄽ࡟⮳ࡿሙྜࡶぢࡽࢀࡿࠋṇ☜࠿ࡘ㎿㏿࡞⮬ື㌶㐨ゎᯒ- 115 -

ࢆᐇ⌧ࡍࡿࡇ࡜ࡣࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃ୖࡢ཯ᛂ⤒㊰ࡢゎᯒ࡟ຍ࠼ࠊᵓ㐀ኚ໬࡟క࠺㟁Ꮚ⛣ື࡟ᇶ࡙ࡁ཯ᛂᶵᵓࡢ໬Ꮫⓗ⌮ゎࢆ୚࠼ࡿ࡜࠸࠺ほⅬ࠿ࡽࡶࡁࢃࡵ࡚㔜せ࡜⪃࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚୚࠼ࡽࢀࡿศᏊ㌶㐨ࢆゎᯒࡍࡿ࠺࠼࡛ၥ㢟࡜࡞ࡿ  㠀༨᭷㌶㐨ࡢ㠀ᒁᅾᛶࠊ  㠀༨᭷㌶㐨ࡢᇶᗏ㛵ᩘ౫Ꮡᛶࢆゎᾘࡋࠊ཯ᛂάᛶ࡞ศᏊ㌶㐨ࢆ⣔⤫ⓗ࡟⮬ືᢳฟࡍࡿ QDWXUDOUHDFWLRQRUELWDO 152 ἲࢆ㛤Ⓨࡋࡓࠋᅗ  ࡣ࢚ࢳࣞࣥ࡜ ࣈࢱࢪ࢚ࣥࡢ 'LHOV$OGHU ཯ᛂࡢ㑄⛣≧ែ㸦76㸧ᵓ㐀࡟࠾࠸࡚⮬ືᢳฟࡋࡓ 152 ᑐࡢ࠺ࡕࠊ㟁Ꮚ⛣ືࡢᐤ୚ࡀ᭱ࡶ኱ࡁ࠸  ⤌࡜ࠊࡑࢀࡽࡢΰྜ࡟ࡼࡿ㟁Ꮚᐦᗘࡢኚ
໬ࢆ♧ࡋࡓࡶࡢ࡛࠶ࡿࠋࡇࡢ 76 ࡣ Cs ᑐ⛠ᛶࢆ᭷ࡋࠊ཯ᛂᗙᶆ
ࡣ Cs ᑐ⛠ᛶࢆಖᣢࡍࡿ᪉ྥࢆྥ࠸࡚࠸ࡿࠋࡋࡓࡀࡗ࡚ࠊΰྜࡀ
チࡉࢀࡿ㌶㐨ࡢᑐ⛠ᛶࡢ⤌ࡣྠࡌ᪤⣙⾲⌧ྠኈࡢࡶࡢ࡟㝈ࡽࢀࠊᅗ  ࡛ࡣ $ ྠኈࠊ$ ྠኈࡀ཯ᛂάᛶ࡞ศᏊ㌶㐨࣌࢔࡜ࡋ࡚ᢳฟ
ࡉࢀ࡚࠸ࡿࠋᮏᡭἲ࡛ࡣࡇࡢࡼ࠺࡟㌶㐨ࡢᑐ⛠ᛶࡀ㐺ษ࡟⪃៖ࡉࢀࠊ:RRGZDUG+RIIPDQQ ࡢ㌶㐨ᑐ⛠ᛶࡢಖᏑࡢ⌮ㄽ࡜ᩚྜⓗ࡛࠶ࡿࠋࡲࡓࠊࡇࢀࡽ  ࡘࡢ 152 ᑐࡣࠊ76 ࡟࠾ࡅࡿ㌶㐨ࡢΰྜ඲యࡢ ࢆ⾲⌧ࡋ࡚࠾ࡾࠊ'LHOV$OGHU ཯ᛂࡀࡇࢀࡽ  ⤌ࡢ㌶㐨ࡢࡳ࡛࠾࠾ࡼࡑ⌮ゎ࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡿࠋᮏᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡇࡢࡼ࠺࡟⭾኱࡞ᩘࡢ㌶㐨࠿ࡽ཯ᛂ࡟㛵ࡋᮏ㉁ᅗ  ࢚ࢳࣞࣥ࡜ ࣈࢱࢪ࢚ࣥࡢ
'LHOV$OGHU ཯ᛂࡢ 76 ࡟࠾ࡅࡿ᭱ࡶ
㟁Ꮚ⛣ືࡢᐤ୚ࡀ኱ࡁ࠸ 152 ᑐⓗព࿡ࢆᣢࡘᑡᩘࡢ㌶㐨ࢆᢳฟࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡗࡓࠋࡇࢀࡣྠ᫬࡟ࠊ᝟ሗ㔞ࡢᅽ⦰ࡶᐇ⌧࡛ࡁࡓࡇ࡜ࢆ
ព࿡ࡋ࡚࠸ࡿࠋ

)UR]HQFRUHSRWHQWLDO ㏆ఝࢆ⏝࠸ࡓᕼᅵ㢮㘒యࡢᇶᗏ࣭ບ㉳≧ែࡢ⡆౽࡞ィ⟬ἲࡢ㛤Ⓨᕼᅵ㢮㘒యࡣࠊ
II 㑄⛣࡟⏤᮶ࡋࡓⰍ⣧ᗘࡢ㧗࠸Ⓨගࢆ♧ࡍⓎගᮦᩱ࡜ࡋ࡚ᵝࠎ࡞ࡶࡢ࡟ᐇ⏝໬ࡉࢀ࡚࠸ࡿࠋ
ෆẆࡢ I 㟁Ꮚࡣ⤖ྜࡢᙳ㡪ࢆཷࡅ࡟ࡃ࠸ࡓࡵࠊII 㑄⛣ࡢⓎගἼ㛗ࡣ㓄఩Ꮚ࡟࡯࡜ࢇ࡝౫Ꮡࡋ࡞࠸ࠋ୍᪉ࠊⓎ
ගࡢ㍤ᗘࡸ㔞Ꮚ཰⋡ࡣ௚ࡢ㟁Ꮚບ㉳≧ែ࡟ᙳ㡪ࡉࢀኚ໬ࡍࡿࡓࡵࠊᕼᅵ㢮㘒యࡢⓎග≉ᛶࢆ㆟ㄽࡍࡿ࡟ࡣᵓ
㐀࡜࢚ࢿࣝࢠ࣮‽఩ࡢ㛵ಀᛶࢆỴᐃࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋᕼᅵ㢮㘒యࡢ㟁Ꮚ≧ែࡣ㛤Ẇᛶ I 㟁ᏊࡢᏑᅾ࡟
ࡼࡾᨃ⦰㏥⣔ࢆᙧᡂࡍࡿࡓࡵࠊ࣏ࢸࣥࢩࣕࣝ᭤㠃ࢆ⢭ᗘⰋࡃグ㏙ࡍࡿ࡟ࡣ⢭⦓࡞㟁Ꮚ≧ែィ⟬ࡀᚲせ࡜࡞ࡿࡀࠊࡇࢀࢆᕼᅵ㢮㘒య࡟㐺⏝ࡍࡿࡇ࡜ࡣࢥࢫࢺⓗ࡟ᅔ㞴࡛࠶ࡿࠋࡲࡓࠊ')7 ィ⟬ࢆ⏝࠸ࡿ࡜ࡋ࡚ࡶ㧗ࢫࣆࣥࡢບ㉳≧ែィ⟬ࡣᐜ࡛᫆ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊ෾⤖ෆẆ࣏ࢸࣥࢩࣕࣝ㸦)&3㸧ἲࢆ⏝࠸࡚ᕼᅵ㢮ࡢ I 㟁Ꮚࢆᡤᮃࡢ㟁Ꮚ≧ែ࡛෾⤖ࡍࡿࡇ࡜࡟ࡼࡾࠊᕼᅵ㢮㘒యࡢᇶᗏ࣭ບ㉳≧ែࢆ⡆౽࡟ィ⟬ࡍࡿ᪉ἲࢆ᪂ࡓ࡟ᥦ᱌ࡋ
ࡓࠋ)&3 ἲࡣᙧᘧⓗ࡟ࡣ HORQJDWLRQ ἲ࡜➼౯࡛࠶ࡿࡇ࡜ࢆ฼⏝ࡋࠊࡇࢀࢆ *$0(66 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ HORQJDWLRQἲࡢ࣮ࣝࢳ࡛ࣥᐇ⾜ࡋࡓࠋࡉࡽ࡟෾⤖ࡋࡓ I ㌶㐨ࡢᅇ㌿⮬⏤ᗘࡢ⦆࿴ࢆ⪃៖ࡍࡿ᪉ἲࡶ㛤Ⓨࡋࡓࠋ
(X WPK  WSSR 㘒యࡢᇶᗏ㸦6)㸧≧ែࠊII ບ㉳㸦6'㸧≧ែࠊ㓄఩Ꮚ 7 ບ㉳㸦7)㸧≧ែࡢ +) ィ⟬ࢆ )&3 ἲ࡜㏻ᖖἲ࡛⾜࠸ࠊ඲࢚ࢿࣝࢠ࣮࡜ບ㉳࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡋࡓ㸦⾲ 㸧ࠋ඲࢚ࢿࣝࢠ࣮࡛ẚ㍑ࡍࡿ࡜ࠊ)&3 ἲ࡜㏻ᖖἲࡢ࢚ࢿࣝࢠ࣮ᕪࡣ H9 ௨ୖ࡜኱ࡁ࠸ࡀࠊບ㉳࢚ࢿࣝࢠ࣮࡛ࡣ H9 ௨ෆࡢᕪ࡜࡞ࡾࠊ㧗࠸⢭ᗘ࡛෌⌧࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᅇ㌿⮬⏤ᗘࢆ⦆࿴ࡋࡓሙྜ㸦)&3URW㸧ࠊ࢚ࢿࣝࢠ࣮ࡣపࡃ࡞ࡗࡓࡀࡑࡢຠ
ᯝࡣ㝈ᐃⓗ࡛࠶ࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ࡞࠾ࠊ㏻ᖖἲ࡛ࡣ 6&) ࡢ཰᮰ᛶࡀᝏ࠸ሙྜ࡛࠶ࡗ࡚ࡶࠊ)&3 ἲࢆ⏝࠸ࡓィ⟬ࡣ཰᮰ࡋ࡚࠾ࡾࠊ㏻ᖖィ⟬ࡢ LQLWLDOJXHVV ࡜ࡋ࡚ࡶ౑⏝࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

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ࠖCSJ ໬Ꮫࣇ࢙ࢫࢱ

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Study of the structure and functions of biomacromolecules and functional materials using molecular
dynamics and quantum chemical calculations - Photochemical reaction of ketoprofen with amidacid residues.
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࣮ࣞࢩࣙࣥ࠾ࡼࡧศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ᳨ウࡋᐇ㦂⤖ᯝ࡜⥲ྜࡋ࡚ +6$ ୰ࡢ .3 ࡜࢔࣑ࣀ㓟ഃ㙐ࡢග໬Ꮫ཯ᛂ࡟ࡘ࠸࡚㆟ㄽࡋࡓࠋ

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࢟ࢩ࣮ࣛࢺ࢔ࢽ࢜ࣥ .3 㸫 ࡜ࡋ࡚Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࢆ⪃៖ࡋ࡚ࡑࢀࡒࢀࡢ࢔ࢽ࢜ࣥ 5 .3㸫ࠊ 6 .3㸫ࢆసᡂࡋࠊ
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Fig. 1 Structure of ketoprofen࡜࡟⛣ືࠊࡲࡓྛ఩⨨࡛ r㛫㝸࡛ᅇ㌿ࡉࡏࡑࢀࡒࢀࡢ㓄⨨࡛ .3 ࡟ᑐࡋ࡚࢚ࢿࣝࢠ࣮ᴟᑠ໬ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢᚋࠊ+6$ࢆྵࡵࡓ」ྜయ඲య࡟࢚ࢿࣝࢠ࣮ᴟᑠ໬ィ⟬ࢆ⾜࠸ࠊ+6$࡜ .3 ࡢ⤖ྜࡢᏳᐃᵓ㐀ࢆồࡵࡓࠋࡲࡓࠊồࡵࡓᏳᐃᵓ㐀࡟ࡘ࠸࡚ࡣࡑࡢ⤖ྜࡢᏳᐃᛶࢆ᳨ウࡍࡿࡓࡵศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ
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$UJ ࡢഃ㙐❅⣲ཎᏊ㛫ࡢ㊥㞳ࡢ᫬㛫ኚ໬ࢆㄪ࡭ࡓ࡜ࡇࢁࠊほࡢ඲᫬㛫⠊ᅖ࡟࠾࠸࡚ 5 .3㸫ࠊ 6 .3㸫ࡣ࡝ࡕࡽࡢሙྜࡶ +6$ ୰ࡢ 7\U ࡜ $UJ ࡢ㏆ഐ࠿ࡽ㞳ࢀࡿࡇ࡜࡞ࡃᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
ࡇࢀࡽࡢࢻࢵ࢟ࣥࢢ࡜ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࡢ⤖ᯝࢆ㐣Ώ྾཰ศගἲ࡟ࡼࡾᚓࡽࢀࡿ KP㸫࡜ HSA
ࢆᵓᡂࡍࡿ࢔࣑ࣀ㓟࡜ࡢ཯ᛂᛶࡢ⤖ᯝ࡜⥲ྜࡋ࡚ࠊ.3

Fig. 2. Snapshot of the stable structures for thecomplex R-(-)-KP-.(Ref. 1)

㸫ࡀ +6$ ୰࡛ 7\U ࡸ $UJ ࡞࡝ࡢ࢔࣑ࣀ㓟ṧᇶ࡜ග໬Ꮫ

཯ᛂࢆ㉳ࡇࡋ࡚࠸ࡿྍ⬟ᛶࢆ♧ࡍࡇ࡜ࡀฟ᮶ࡓࠋࡇࢀࡽࡢ▱ぢࡣ⸆๣ᛶග⥺㐣ᩄ⑕ࡢ཯ᛂึᮇ㐣⛬ࡢゎ᫂ࡢࡓࡵ࡟᭷⏝࡛࠶ࡿࠋၟ⏝࡛౑⏝ྍ⬟࡞ .3 ࡣࣛࢭ࣑య࡛࠶ࡾࠊࡇࡢ⤖ᯝ࠿ࡽࡣ 5 ࡜ 6 ࡢ୧ࣛࢭ࣑యࡀ
⸆๣ᛶග⥺㐣ᩄ⑕ࢆᘬࡁ㉳ࡇࡍྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ

ཧ⪃ᩥ⊩
[1]

Wataru Kashihara, et. al., J. Phys. Chem. B, 126,

2098-2107 (2022).

Fig. 3. Snapshot of the stable structures for thecomplex S-(+)-KP-. (Ref. 1)

Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ "ۻ‬Photochemical Reaction of Ketoprofen with Proteinogenic Amino AcidsPhotochemical

Reaction of Ketoprofen with Proteinogenic Amino Acids”Wataru Kashihara, Mio Shinoda, Kiyoka
Tsuchiya, Tasuku Isozaki, Batsaikhan Mijiddorj, Kazuyoshi Ueda, and Tadashi Suzuki, J. Phys. Chem. B,
126, 2098-2107 (2022). https://doi.org/10.1021/acs.jpcb.1c10108- 121 -

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@hMasahiro Higashi, “Toward a molecular understanding of photosynthetic proteins,” Pacifichem, Online, December
2021.

- 124 -

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Hirofumi Sato, “Multi-scale couplings for chemical processes at molecular level: quantum chemistry and statisticalmechanics,” Pacifichem, Online, December 2021.
Masahiro Higashi, “Theoretical study on donor-acceptor-linked molecules,” The 11th International Conference on
Flexible and Printed Electronics, Online, September-October 2021.
Ò_?
#$=4/-=È§K`À¼?2021 iJPa½À ?<70<?2021 i 9 '.
Masahiro Higashi, “Toward a molecular understanding of photoinduced charge separation process in organic solar
cells with computational approaches,” 239th ECS Meeting, Online, May-June 2021.

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Xue Peng, Yuki Hirao, Shunsuke Yabu, Hirofumi Sato, Masahiro Higashi, Takuya Akai, Shigeyuki Masaoka,
Harunobu Mitsunuma, and Motomu Kanai, “A catalytic alkylation of ketones via sp C-H bond activation,” J. Org.
3

Chem. in press.
Akihiko Takamatsu, Masahiro Higashi, and Hirofumi Sato, “Free energy and solvation structure analysis foradsorption of aromatic molecules at Pt(111)/water interface by 3D-RISM theory,” Chem. Lett. in press.
 Kaho Nakatani, Sho Teshigawara, Yuta Tanahashi, Kento Kasahara, Masahiro Higashi, and Hirofumi Sato,“Solvation in nitration of benzene and the valence electronic structure of Wheland intermediate,” Phys. Chem. Chem.
Phys. in press.
Kosuke Imamura, Masahiro Higashi, Yoji Kobayashi, Hiroshi Kageyama, and Hirofumi Sato, “Chemical shift ofsolvated hydride ion: Comparative study with solvated fluoride ion,” J. Phys. Chem. B 2022, 24, 1712-1721.
Tomoaki Yagi and Hirofumi Sato, “Self-consistent construction of grand potential functional with hierarchicalintegral equations and its application to solvation thermodynamics,” J. Chem. Phys. 2022, 156, 054116 (X pages).
Hiromu Fuse, Yu Irie, Masaaki Fuki, Yasuhiro Kobori, Kosaku Kato, Akira Yamakata, Masahiro Higashi, Harunobu
Mitsunuma, and Motomu Kanai, “Identification of a self-photosensitizing hydrogen atom transfer organocatalyst
system,” J. Am. Chem. Soc. 2022, 144, 6566-6574.
Kaho Nakatani, Hirofumi Sato, and Ryoichi Fukuda, “Catalyzed E/Z isomerization mechanism of stilbene usingpara-benzoquinone as a triplet sensitizer,” Phys. Chem. Chem. Phys. 2022, 24, 1712-1721.
Minami Kimura, Tadashi Ito, Hirofumi Sato, and Masahiro Higashi, “Theoretical study on isomerization of Į-acids:
A DFT calculation,” Food Chem. 2021, 364, 130418 (6 pages).
Yuichiro Yoshida, Satoru Iuchi, and Hirofumi Sato, “A quantum chemical model for a series of self-assembled
nanocages: the origin of stability behind the coordination-driven formation of transition metal complexes up to[M L ] ,” Phys. Chem. Chem. Phys. 2021, 23, 866-877.
12

24

24+

Keiji Naka, Hirofumi Sato, and Masahiro Higashi, “Theoretical study of the mechanism of the solvent dependencyof ESIPT in HBT,” Phys. Chem. Chem. Phys. 2021, 23, 20080-20085.

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6FKHPH&\FOL]DWLRQUHDFWLRQRIEURPREXWHQRQHZLWKWKLRXUHDD◊✲᪉ἲࠊィ⟬᪉ἲ᭱ࡶ༢⣧࡞ᇶ㉁࡜ࡋ࡚ 1-ࣈࣟࣔࣈࢸࣀࣥ 1 ࢆྜᡂࡋ㸪ࢳ࢜ᒀ⣲ 2a ࡜ࡢ཯ᛂ࡟ࡼࡿ⎔໬཯ᛂࢆ⾜ࡗࡓࠋ཯ᛂ

ࡢ㝿࡟ࡣ㔠ᒓゐ፹ࡣ⏝࠸ࡎ㸪⁐፹࡟ PEG200 ࢆ⏝࠸ࡿࡇ࡜࡛⎔ቃㄪ࿴ᆺࡢ཯ᛂ᮲௳࡜ࡋࡓࠋࡲࡓ཯ᛂ᮲௳᳨ウࢆ⾜࠺㝿࡟ࡣ㸪⎔໬཯ᛂࡢࣔࢹࣝ໬ྜ≀࡜ࡋ࡚ࣁࣟࢤࣥ໬࢔ࣝ࢟ࣝ࡟⮯໬࣋ࣥࢪࣝ 5㸪ᮎ➃࢚ࣀࣥ࡟࣓ࢳ
ࣝࣅࢽࣝࢣࢺࣥ 6 ࢆྲྀࡾୖࡆ㸪ᐇ㦂࡟ࡼࡗ࡚ࢳ࢜ᒀ⣲࠾ࡼࡧࢳ࢜ᒀ⣲ㄏᑟయࢆ⏝࠸ࡓࢫࣝࣇ࢕ࢻྜᡂ཯ᛂࡢ᮲௳᳨ウࢆ⾜ࡗࡓࠋࡲࡓ㸪ྠᵝࡢ཯ᛂࢆᵝࠎ࡞⁐፹୰࡛⾜࠺ࡇ࡜࡛㸪⁐፹ࡢᴟᛶ࡟ࡼࡿ཯ᛂ㏿ᗘࡢ㐪࠸ࡶ᳨ウࡋࡓࠋࠋ୍᪉࡛㸪ศᏊ㌶㐨ィ⟬㸦Gaussian16 ࣉࣟࢢ࣒ࣛ㸧ࢆ⏝࠸࡚㸪ᮏ཯ᛂ࡟࠾ࡅࡿᇶᗏ≧ែࡸ㑄⛣≧ែࡢᵓ㐀᭱㐺໬࠾ࡼࡧ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࠋ࠸ࡎࢀࡢᑐ㇟໬ྜ≀࡟࠾࠸࡚ࡶ」ᩘࡢ㓄ᗙ␗ᛶయࡀᏑᅾࡍࡿࡓ
ࡵ㸪cam-B3LYP/6-31+G(d,p)ࣞ࣋ࣝࡢィ⟬࡟࠾࠸࡚ࡍ࡭࡚ࡢ㓄ᗙ␗ᛶయ࡟ࡘ࠸࡚ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚㸪CPCM ἲ࡟ࡼࡿ⁐፹ຠᯝィ⟬ࢆ⾜࠺ࡇ࡜࡛᭱ࡶඃໃ࡜⪃࠼ࡽࢀࡿ཯ᛂᶵᵓࡢ᳨ウࢆ⾜ࡗࡓࠋ- 126 -

◊✲ᡂᯝPEG-Ỉΰྜ⁐፹୰࡛Ⅳ㓟ࢼࢺ࣒ࣜ࢘ࢆゐ፹࡟⏝࠸࡚ 1-ࣈࣟࣔࣈࢸࣀࣥ 1 ࡜ࢳ࢜ᒀ⣲ࢆ཯ᛂࡉࡏࡓ࡜ࡇࢁ

(Scheme 1)㸪࢔࣑ࣀࢳ࢔ࢰ࣮ࣝ 3a ࡢࡳࡀᐃ㔞ⓗ࡟ᚓࡽࢀ㸪thia-Michael ཯ᛂ࡟ࡼࡿࢳ࢜ࣛࣀࣥ 4 ࡣᚓࡽࢀ࡞࠿
ࡗࡓࠋࡑࡇ࡛ࣁࣟࢤࣥ໬࢔ࣝ࢟ࣝ࡟⮯໬࣋ࣥࢪࣝ㸪ᮎ➃࢚ࣀࣥ࡟࣓ࢳࣝࣅࢽࣝࢣࢺࣥ㸪◲㯤※࡟ࢳ࢜ᒀ⣲ࢆ⏝࠸࡚㸪thia-Michael ཯ᛂࡢ཯ᛂ᮲௳᳨ウࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝ㸪཯ᛂ㏿ᗘࡣᴟᛶ⁐፹ࡢ᪉ࡀ㧗ࡃ㸪ࢳ࢜ᒀ⣲ࢆ⏝࠸࡚ THF ୰࡛཯ᛂࡉࡏࡿ࡜㸪ᐊ࡛ࡶ༑ศ࡟ thia-Michael ཯ᛂࡀ㐍⾜ࡋ࡚ࢫࣝࣇ࢕ࢻࡀ⏕ᡂࡍࡿࡇ࡜ࡀ᫂

ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓ㸪ࢳ࢜ᒀ⣲ࡢ❅⣲ୖ࡟ᵝࠎ࡞࢔ࣝ࢟ࣝ⨨᥮ᇶࢆᑟධࡋࡓሙྜ㸪1,3-ࢪ࣓ࢳࣝయࢆ⏝࠸ࡓሙྜ࡟᭱ࡶ཯ᛂࡀάᛶ໬ࡍࡿ࡜࠸࠺⤖ᯝ࡟࡞ࡗࡓࠋḟ࡟ศᏊ㌶㐨ィ⟬࡟ࡼࡗ࡚㸪⮯໬࣋ࣥࢪࣝ 5 ࡜཯ᛂ࡟⏝࠸ࡓྛ✀ࢳ࢜ᒀ⣲ㄏᑟయ࡟ࡘ࠸࡚㸪ᚊ㏿ẁ㝵࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁ㸪⏕ᡂࡍࡿ୰㛫య࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࡣ㸪1,3-ࢪ࣓ࢳࣝࢳ࢜ᒀ⣲ࢆ⏝࠸ࡓሙྜࡀ᭱ࡶపࡃ㸪ᐇ㦂⤖ᯝࢆ⿬௜ࡅࡿ⤖ᯝ࡜࡞ࡗࡓࠋ

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[1] ‫ۻ‬M. Ishitate, H. Saigo, M. Tabei, M. Shigehara, C. Yamasaki, K. Maeda, D. Kaneno, The 2021 International

Chemical Congress of Pacific Basin Societies, 18th December 2021, Online, [2] ‫ۻ‬ᫀᮏ㸪ྜྷỌ㸪㔠㔝㸪᪥ᮏ໬Ꮫ఍➨102 ᅇ᫓Ꮨᖺ఍㸪2022 ᖺ 3 ᭶ 24 ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[3] ‫▼ۻ‬ᘓ㸪す㒓㸪⏣㒊஭㸪๓⏣㸪⦾ཎ㸪㔠㔝㸪᪥ᮏ໬Ꮫ఍➨ 102 ᅇ᫓Ꮨᖺ఍㸪2022 ᖺ 3 ᭶ 26 ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[4] ‫▼ۻ‬ᘓ㸪す㒓㸪⏣㒊஭㸪๓⏣㸪⦾ཎ㸪ᒣ㷂㸪㔠㔝㸪➨ 31 ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸪2021 ᖺ 9 ᭶ 22 ᪥㸪࢜ࣥࣛ࢖ࣥ

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, [2] ‫ۻ‬Ichikawa, Y.;
Kaneno, D.; Saeki, N.; Minami, T.; Matsuda, T.; Yoshida, K.; Kondo, T.; Ochi, R., Carbohydr. Res., 2021, 505, 108280.

- 127 -

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Sampling Ü ¿ %Ý½£¤|O5MPE:<)}¹'Þ
O³ÆDL:E)]Í' TM GE9=ÛUÓ©rÚ$£º("Ü)HPOPC ´®-@M0P½£)³ÞrÚ ¿}¹"³ÝTM GE9=v_$'³ÆDL:E²me)7Z% 'Þ W! POPC ) 128 1Ýbo) 8192 1 POPC ³ÆWÒy´)[Ý()?«h³Æ´ POPC bo( &5 PM(CHOL)ÝKH=(CER)Ý*M2L PM(DAG)Ý5
D+NH-LN(PSM));[bo|5 20 mol%MD 4HP4N5qOqNw)S(T=303K, P=1atm)r³³Æ:R CHARm36 )[2]Ý;M TIP3 )PMF ½£*N3NELN2ÛUSÜ[3] LogMFD[4]Ý¦×r)¿\@ia z ¾Û´=rGÜÝPOPC ³Æ P >o)´aUhrG¥dRh PMF )´ÄÇ
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8Ö<z PSM < DAG < CER < CHOL ' ¤((%8Ö<zÈ;boÌ#¡X[ÈÛbo9Ý~lnwÝ¬¥hoÈÜ$'«%('
M 1  PMF ½£$&f%(E« ' POPC ´=rGY'®-@M0P¨¥z)¤®-@M0P¨~w POPC  P >o´a '^´-©Û $ z = 20'ÂÜYi'z = 0 ´aUh-©Yi' PMF 3ÛFlip-flop ®-@M0PÑTÜ&Ýz = 40YÐBM1ÖQ&ÝPMF 3 POPC ´« %­Ò (desorption)-@M0P3Yi'M¤$*NK3NELN2ÛUSÜ¿\ PMFÛÓ¨Ü LogMFD ¿\ PMFÛ½O§¨Ü
Ø{° Q¯'¥z ¤(LogMFD "¤|° ³Æ´ÄÇ®-@M0P¨ ¿\(' ¤(  PMF ¨ f%(' ¦½£5:Eo) US  LogMFD  ¿
LogMFD r$ 1.8 2 |½£< ° ¤(&d5 PMÝKH=Ý*M2L PMÝ5D+NH-LN)H « PMF ¥z"rs'

Table1. Membrane structural parameters for mixed
POPC bilayers

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1. Kazutomo Kawaguchi, Seiichiro Ito, Hiroaki Saito, Hidemi Nagao, “Molecular dynamics study of lipid bilayer
asymmetry induced by ion concentration gradient and electronic polarizability”, Molecular Simulation (2022) 48:6, 477483.
2Naoki Kanoh, Ryusei Terashima, Hiromichi Nishiyama, Yuta Terajima, Shota Nagasawa, Yusuke Sasano,
Yoshiharu
Iwabuchi, Hiroaki Saito, Syusuke Egoshi, Kosuke Dodo, Mikiko Sodeoka, Chengqian Pan, Yoshinobu Ikeuchi, Shinichi
Nishimura, and Hideaki Kakeya, “Design, Synthesis, and Antifungal Activity of 16,17- Dihydroheronamide C and entHeronamide C”, The Journal of Organic Chemistry (2021) 86 (23), 16249-16258.
3. Û²nÝD,bod:p4HP4N) >H=×´aÌ8Ö(epH?P4ND N+*¢ 8L6Î4NIÛ.NK,NÜ7u, 2021.)- 130 -

4. Uzª, Ú²Ê±, y¼I, Óvt±, Ù\À, Û²n, zU^, ²/K, Rr, |M
N-BXZ¡X[sT'lc;2 NÐcFq(¢ 15 LB,.ÏÆep4NIÛ.NK,NÜ,9 u, 2021)
5. Û²nÝD,bod:p4HP4N) >H=×´aÌ¥h (¢ 35 L
bo4HP4N·Ä*Û.NK,NÜ12 u, 2021.)
6. y ¼I, ;²0, Óvt±, Uzª, Khurram Bashir, Andrea Chini, Ù¬C, Û²n, É, Ù\À, U], Ój, Ï>, Roberto Solano, Rr, >9N¨ZZDP/5=K,KLP)5NÑBXZ37,ELN=Î(vp* 2022,  , 3 u, 2022)
+LURDNL6DLWR1DRNL.DQRK³'\QDPLFDOVWUXFWXUHDQGWKHUPDOVWDELOLW\RISRO\HQHPDFURODFWDPKHURQDPLGHVLQOLSLGELOD\HU $ PROHFXODU G\QDPLFV VWXG\´ 7KH ,QWHUQDWLRQDO &KHPLFDO &RQJUHVV RI 3DFLILF %DVLQ 6RFLHWLHV 
 3$&,),&+(0   &KHPLFDO &RPPXQLFDWLRQV WKURXJK 1DWXUDO DQG 6\QWKHWLF %LRDFWLYH &RPSRXQGV  'HFHPEHU_9LUWXDO - 131 -

ᵓ㐀ከ⢾ᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲Molecular dynamics study of structural polysaccharides
and carbohydrate-related proteinsࠐ‫‮‬஭ ᩄᩥࠊᏱ㒔 ༟ஓ㸦ᐑᓮ኱ᏛᕤᏛ㒊㸧㸯㸬◊✲┠ⓗࠊෆᐜᵓ㐀ከ⢾㢮࡛࠶ࡿࢭ࣮ࣝࣟࢫ࡜࢟ࢳࣥࡣᮌ㉁⣽⬊ቨࡸ⏥Ẇ㢮እ㦵᱁࡞࡝ࡢ୺ᡂศ࡛ࠊఱᮏࡶࡢศᏊ㙐ࡀ㞟ྜࡋࡓ㧗⤖ᬗᛶ⧄⥔࡜ࡋ࡚⏕⏘ࡉࢀࡿࠋࢭ࣮ࣝࣟࢫࡣゎ⧄ࠊ⁐ゎ࣭෌⏕ฎ⌮ࠊㄏᑟయ໬ࠊຍỈศゎ࡞࡝ࢆ⤒࡚ࠊ⧄⥔࣭ࣂ࢖࢜ࢣ࣑࢝ࣝ⣲ᮦࡸࣂ࢖࢜⇞ᩱ࡜࠸ࡗࡓ⏘ᴗ฼⏝ࡀ᥎㐍ࡉࢀ࡚࠸ࡿࠋ㏆ᖺࠊኳ↛ࢭ࣮ࣝࣟࢫ⧄⥔ࢆゎ⧄ࡋ࡚ࢼࣀࣇ࢓࢖ࣂ࣮໬ࡋࡓࢭ࣮ࣝࣟࢫࢼࣀࣇ࢓࢖ࣂ࣮㸦&1)㸧ࡀ⎔ቃㄪ࿴ᆺࡢࢼࣀ⣲ᮦ࡜ࡋ࡚ὀ┠ࡉࢀࠊ⏘Ꮫᐁ࡟ࡼࡿ◊✲㛤Ⓨࡀ⾜ࢃࢀ࡚࠸ࡿࠋ୍᪉ࠊ࢟ࢳࣥ࠾ࡼࡧࡣ࢟ࢳࣥࡢ⬺࢔ࢭࢳࣝ໬࡟ࡼ
ࡗ࡚ᚓࡽࢀࡿ࢟ࢺࢧࣥࡣ⎔ቃί໬ᮦᩱࡸ་⒪ᮦᩱ࡞࡝ࡢ⏝㏵ࡀᮇᚅࡉࢀ࡚࠸ࡿࡀࠊ࢟ࢳࣥࡀࢭ࣮ࣝࣟࢫࡼ
ࡾࡶࡉࡽ࡟ྲྀᢅ࠸ࡀ㞴ࡋ࠸ࡓࡵࠊࡑࡢ࡯࡜ࢇ࡝ࡀᮍ฼⏝ࡢࡲࡲ࡛ᗫᲠࡉࢀ࡚࠸ࡿࡢࡀ⌧≧࡛࠶ࡿࠋୡ⣖ᮎ࡟ኳ↛ࢭ࣮ࣝࣟࢫ⧄⥔ࢆ⁐፹࡛⁐࠿ࡋࠊ㐃⥆ⓗ࡞⧄⥔࡟ྜᡂࡋࡓ෌⏕ࢭ࣮ࣝࣟࢫ⧄⥔ࡀ㛤Ⓨࡉࢀࠊ㏆ᖺࠊ࢖࢜ࣥᾮయࢆྵࡵࡓ⎔ቃ࡬ࡢ㈇ᢸࡢᑡ࡞࠸⁐፹㛤Ⓨࡀヨࡳࡽࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࢭ࣮ࣝࣟࢫ࡟௦⾲ࡉࢀࡿᵓ㐀ከ⢾ᮦᩱ࡟ࡣ㧗⤖ᬗᛶ⧄⥔ࡢࡵ࡟Ỉࡸ୍⯡ⓗ࡞᭷ᶵ⁐፹࡟㞴⁐࡛ຍᕤᛶ࡟ஈࡋ࠸ࠋᵓ㐀ከ⢾㢮ᮦᩱࡢ㧗ᶵ⬟໬࡟㛵ࢃࡿゎ⧄ࠊྍ⁐໬ࠊ┦㌿⛣ࠊ࢟ࣛࣝㄆ㆑ࠊ㓝⣲ศゎ࡞࡝ࡢ⌧㇟ࡣࠊ㧗ḟᵓ㐀ᙧᡂࡸከ⢾⤖ᬗ⏺㠃≉ᛶࡀ㛵୚ࡋࠊࡑࢀࡽࡢ࣓࢝ࢽࢬ࣒࡟㛵ࡍࡿศᏊㄽⓗ⌮ゎࡣ୙᫂࡞ࡲࡲ࡛࠶ࡿࠋࡑࡢࡓࡵࠊ㧗ᶵ⬟ᛶᵓ㐀ከ⢾ᮦᩱࡢ◊✲࣭㛤Ⓨࡢࣈ࣮ࣞࢡࢫ࣮ࣝࡢࡁࡗ࠿ࡅ࡟࡞ࡾ࠺ࡿࡶࡢ࡜ࡋ࡚ࠊࡇࢀࡽࡢศᏊㄽⓗ⌮ゎ࡟ᑐࡍࡿせồࡀ㧗ࡲࡾࡘࡘ࠶ࡿࠋ
ᮏ◊✲ࢢ࣮ࣝࣉࡣࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᡭẁ࡜ࡋ࡚ࠊᵓ㐀ከ⢾㢮ࡀ㛵୚ࡍࡿୖグࡢศᏊㄽⓗ⌮ゎࢆ┠ⓗ࡜ࡋࠊࡉࡽ࡟ᐇ㦂◊✲⪅࡜ࡢඹྠ࡛ᵓ㐀ከ⢾㢮ᮦᩱࡢฎ⌮ࣉࣟࢭࢫࡢᨵⰋࡸ㧗ᶵ⬟ᛶᮦᩱタィࢆ┠ᣦࡋ࡚࠸ࡿࠋࡑࡢ㝿ࠊ✀ࠎࡢᣑᙇ࢔ࣥࢧࣥࣈࣝἲࡸ4000ἲࢆຠᯝⓗ࡟⤌ࡳྜࢃࡏ࡚ࠊᑐ㇟࡜ࡍࡿ⌧㇟࡟㛵ࢃࡿ❧య㓄⨨ࣔࢹࣝ⩌ࢆຠ⋡ⓗ࡟ࢧࣥࣉࣜࣥࢢࡋࠊ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬㔞ࡸ཯ᛂゎᯒࢆྵࡵࡓ㟁Ꮚᵓ㐀≉ᛶࢆ㧗⢭ᗘ࡟ホ౯ࡍࡿࡇ࡜࡛ࠊୖグ┠ⓗࡢ㐩ᡂࢆ┠ᣦࡋࡓࠋ

㸰㸬◊✲ᡭẁ $PEHU ࢆ⏝࠸ࡓศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ୺ࡓࡿᡭẁ࡜ࡍࡿࠋ㏻ᖖࡢศᏊືຊᏛィ⟬㸦0'㸧࡟ຍ࠼ࠊ◊✲┠ⓗ࡟ᛂࡌ࡚ᣑᙇ࢔ࣥࢧࣥࣈࣝἲ࡛࠶ࡿ᧯⯦ศᏊືຊᏛ㸦60'㸧ἲࠊ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢ㸦86㸧ἲࠊ࠾ࡼࡧࣞࣉࣜ࢝஺᥮㸦5(0'㸧ἲࢆ㐺⏝ࡋࡓࠋ㓝⣲཯ᛂࡸศᏊຊᏛἲࡢ㐺⏝⠊ᅖࢆ㉸࠼ࡓィ⟬ᑐ㇟࡟
ᑐࡋ࡚ࠊ4000 ἲࢆ᥇⏝ࡋࠊ㧗⢭ᗘࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࢆᚓࡓࠋ$PEHU ࣛ࢖ࣈ࣮ࣛࣜ࡟ᐇ⿦ࡉࢀ࡞
࠸ຊሙࣃ࣓࣮ࣛࢱ࡟ࡘ࠸࡚ࡣ⊂⮬࡟㛤Ⓨࡋࡓࠋࣃ࣓࣮ࣛࢱ㛤Ⓨࡸ 0' ィ⟬࡛ᚓࡽࢀࡓᵓ㐀࡟ᑐࡍࡿ㟁Ꮚ≀ᛶࡢゎᯒ࡟ࡣࠊ*DXVVLDQ ࢆ฼⏝ࡋࡓࠋ㸬◊✲ᡂᯝ
㸱㸫㸯㸬ᵓ㐀ከ⢾㢮⤖ᬗᮦᩱࡢᣑᙇ࢔ࣥࢧࣥࣈࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ኳ↛ , ᆺࢭ࣮ࣝࣟࢫ⤖ᬗࢆ✀ࠎࡢ࢔࣑ࣥ㢮࡛ฎ⌮ࡍࡿࡇ࡜࡟ࡼࡾࠊࢭ࣮ࣝࣟࢫ࢔࣑ࣥ」ྜయࢆ⤒࡚ࠊრ, ᆺ⤖ᬗ࡬࡜㌿⛣ࡍࡿ⌧㇟ࡣࠊ໬Ꮫⓗ࣭⏕໬Ꮫⓗ࡟άᛶ࡞რ, ᆺࢭ࣮ࣝࣟࢫᮦᩱࢆྜᡂࡍࡿ⏘ᴗⓗ࡟ࡶ㔜せ࡞㐣⛬࡛࠶ࡿࠋᮏ◊✲ࢢ࣮ࣝࣉࡣࠊ㏻ᖖࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥᡭẁ࡟ࡼࡿࢭ࣮ࣝࣟࢫ , ᆺ㸫࢚ࢳ- 132 -

ࣞࣥࢪ࢔࣑ࣥ㸦('$㸧」ྜయ⤖ᬗࣔࢹࣝ࠿ࡽࡢ
('$ ศᏊ⬺㞳ᣲືࡢゎᯒࢆヨࡳࡓ㸦78WRet al.
J, Phys. Chem. B 㸧ࠋࡋ࠿ࡋࠊࢼࣀ⛊࣮࢜ࢲ࣮ࡢࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣ⤖ᬗ⾲㠃࠿ࡽ ('$ศᏊࡢ⬺㞳ࡀほᐹࡉࢀࡿࡢࡳ࡛࠶ࡗࡓࠋࡑࡇ࡛ࠊ
6WHHUHG0ROHFXODU'\QDPLFV㸦60'㸧ἲࢆ㐺⏝ࡋࠊ⤖ᬗෆ㒊ࡢᶆⓗ ('$ ศᏊࢆእຊ࡟ࡼࡗ࡚⤖ᬗ⾲㠃ࡲ࡛⛣ືࡉࡏࠊࡑࡢᣑᩓ࡟࡜ࡶ࡞࠺⮬⏤࢚ࢿࣝࢠ࣮㸦3RWHQWLDORI0HDQ)RUFH30)㸧ኚ໬㔞࡜⬺㞳ᣲື࡟ࡘ࠸࡚ゎᯒࡋࡓ㸦ㄽᩥ߇ 7 <XLDQGᅗ 㻝㻚㻌 䝉䝹䝻䞊䝇䊠ᆺ㻙EDA 」ྜయ⤖ᬗ䝰䝕䝹䛻䛚䛡䜛ᕥ䠅Accelerated MD ἲ䛻䜘䜛 EDA ศᏊ⬺㞳ᣲື䚸ྑ䠅Steered MD 䛸 Umbrella Sampling ἲ䛾⤌ྜ䛫䛻
䜘䜛 EDA ᣑᩓ䛻䛸䜒䛺䛖⮬⏤䜶䝛䝹䜼䞊ኚ໬᭤⥺7 8WR Cellulose 㸧
ࠋ60' ἲ࡛ᚓࡽࢀࡓ ('$ ศᏊ⛣ື㌶㊧ࢆࡶ࡜࡟ 8PEUHOOD6DPSOLQJ㸦86㸧ἲࢆ㐺⏝ࡋࠊ⮬⏤࢚ࢿࣝࢠ࣮㔞ࡢ෌ホ౯ࢆ⾜ࡗࡓ㸦ᅗ  ྑ㸧ࠋࡉࡽ࡟ࠊ」ྜయ⤖ᬗࣔࢹࣝ࡟ᑐࡋ࡚ࠊ࣏ࢸࣥࢩࣕࣝ
᭤㠃ࢆᖹ⁥໬ࡉࡏࢧࣥࣉࣜࣥࢢຠ⋡ࢆ㧗ࡵࡿ $FFHOHUDWHG0ROHFXODU'\QDPLFV㸦$0'㸧ἲࢆ㐺⏝ࡋࠊ௨ୖࡢ ('$ ศᏊ⬺㞳ࢆほᐹࡋࠊࢭ࣮ࣝࣟࢫศᏊ㙐㛫ࡢࢳࣕࢿࣝࢆ」ᩘࡢ ('$ ศᏊࡀྠ᫬࡟ᣑᩓࡍࡿࡢ࡛ࡣ
࡞ࡃࠊ⁐፹ỈศᏊ࡟ࡼࡿỈ࿴ࢆక࠸ࡘࡘ ('$ ࡀ୍ศᏊࡈ࡜࡛⬺㞳ࡍࡿᣲືࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ  ᕥ㸧ࠋྠᵝ࡞ 60' ィ⟬ᡭẁࢆࢭ࣮ࣝࣟࢫ , ᆺ㸫1+ 」ྜయ⤖ᬗࣔࢹࣝ࡟㐺⏝ࡋࡓ࡜ࡇࢁࠊ1+ ศᏊࡀࢭࣝ
࣮ࣟࢫศᏊ㙐ᒙࢆ㏻㐣ࡍࡿᗘ࡟⣙ NFDOPRO ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀⓎ⏕ࡋࠊ1+ ศᏊ⬺㞳࡟せࡍࡿ࢚ࢿࣝࢠ࣮㔞ࢆ㐣๫࡟ぢ✚ࡶࡗࡓࡇ࡜ࡀ᥎ᐃࡉࢀࡓ 7<XLet al. ᢞ✏‽ഛ୰ ࠋࡑࡢࡓࡵࠊᶆⓗ࢔ࣥࣔࢽ࢔
ศᏊ࠾ࡼࡧྠศᏊࡢ⛣ື⤒㊰ࢆᵓᡂࡍࡿࢭ࣮ࣝࣟࢫศᏊ㙐㒊ศᵓ㐀ࢆ 40 㡿ᇦ࡜ࡍࡿ 400060' ࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐺⏝ࡋࡓ⤖ᯝࠊ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ⣙ 㸫 NFDOPRO ࡲ࡛ῶᑡࡋࡓࠋ
࢟ࢺࢧࣥࡣ✀ࠎࡢ㔠ᒓሷ࡜࢟ࢺࢧࣥ㔠ᒓ㘒య⤖ᬗࢆᙧᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋඛᖺࠊᡃࠎࡣ࢟ࢺ
ࢧࣥ㸫ሷ໬ள㖄」ྜయࡢ ; ⥺⤖ᬗᵓ㐀ゎᯒ࡟ᡂຌࡋࡓ㸦7 <XLet al.Nanomaterials 㸧ࠋ⥆ࡅ࡚ࠊࢩ࣑
࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚⤖ᬗᵓ㐀ࢆ⢭ᐦ໬ࡉࡏࠊ࢟ࢺࢧࣥ࡜ሷ໬ள㖄ࡢ」ྜయᙧᡂ࡟ࡘ࠸࡚ࡢヲ⣽ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦7 <XLet al.Nanomaterials 㸧ࠋ௒ᅇࠊࢭ࣮ࣝࣟࢫ㸫࢔࣑ࣥ」ྜయ⤖ᬗᵓ㐀࡟㐺⏝ࡋࡓ 60'ィ⟬ࢆ࢟ࢺࢧࣥʊሷ໬ள㖄」ྜయ⤖ᬗᵓ㐀࡟ᑐࡋ࡚ᐇ᪋ࡋࠊ⤖ᬗᵓ㐀ෆ࡛ࡢሷ໬ள㖄ศᏊࡢ⛣ື࡟క࠺⮬⏤࢚ࢿࣝࢠ࣮ኚ໬࡜࿘ᅖࡢᵓ㐀ኚ໬ࢆほᐹࡋࡓࠋࡑࡢ⤖ᯝࠊ⤖ᬗᵓ㐀୰࡛࢟ࢺࢧࣥ  ఩Ỉ㓟ᇶ࡜㘒యࢆᙧᡂࡍࡿሷ໬ள㖄ศᏊࡣࠊ ఩࢔࣑ࣀᇶ㏆ഐ࡟࠾࠸࡚ࡶ┦஫స⏝ࡀ⏕ࡌࡓࠋࡲࡓࠊ࢟ࢺࢧࣥሷ໬ள㖄」ྜయ⤖ᬗヨᩱ࡛ồࡵࡓ⤖ᬗᐦᗘ࡜୍⮴ࡍࡿỈ࿴ᵓ㐀ࡢᙧᡂࢆ☜ㄆࡋࡓࠋᏛእࢢ࣮ࣝࣉࡀᐇ㦂ࢆᢸᙜࡋࠊᡃࠎࡀࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᢸᙜࡍࡿࢭ࣮ࣝࣟࢫ⤖ᬗࢆᑐ㇟࡜ࡋࡓඹྠ
◊✲ࢆᐇ᪋ࡋࡓࠋ㔠ἑ኱ࢢ࣮ࣝࣉࡀᥦ᱌ࡋࡓࢭ࣮ࣝࣟࢫ⁐ゎᛶ࡛పẘᛶࡢ࢝ࣝ࣎ࣥ㓟⣔୧ᛶ࢖࢜ࣥᾮయ㸦2(LP&&㸧࡟ࡘ࠸࡚ࠊ࢖࢜ࣥᾮయࡢഃ㙐ᵓ㐀ࢆኚ໬࡟ࡼࡿ⣽⬊ẘᛶ࡟ᑐࡍࡿᙳ㡪࡟ࡘ࠸࡚య⣔ⓗホ౯ࢆ⾜ࡗࡓ㸦ㄽᩥߊ 7 .RPRULet al. ACS Sustainable Chem. Eng. 㸧ࠋࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥண

ࡋࡓᵝࠎ࡞࢖࢜ࣥᾮయ୰࡟࠾ࡅࡿ⬡㉁஧㔜⭷ࡢ❧యᵓ㐀Ᏻᐃᛶࡣࠊᐇ㦂⤖ᯝࡢഴྥࢆᐃᛶⓗ࡟෌⌧ࡋࡓࠋࡑࡢ⤖ᯝࠊ࢔ࢽ࢜ࣥഃ㙐ࢫ࣮࣌ࢧ࣮ࡢ㐪࠸ࡶẘᛶ࡟ᙳ㡪ࡋࠊపẘᛶࢭ࣮ࣝࣟࢫ⁐፹࡜࡞ࡾᚓࡿ୧ᛶ࢖࢜ࣥᾮయ
ࡢタィᣦ㔪࡜ࡋ࡚ࠊ࢜ࣜࢦ࢚࣮ࢸࣝࡸ▷࠸࢔ࢽ࢜ࣥഃ㙐ࡢᑟධࡀᮃࡲࡋ࠸ࡇ࡜ࢆᥦ᱌ࡋࡓࠋ኱㜰኱Ꮫ⏘ᴗ⛉Ꮫ◊✲ᡤࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡜ࡋ࡚ࠊࢭ࣮ࣝࣟࢫࢼࣀࣇ࢓࢖ࣂ࣮㸦&1)㸧ࡢ㧗ᗘ฼⏝ࢆᛕ㢌࡟ࠊࣇ࢓࢖ࣂ࣮ᙧែࡸศᏊ㙐ࡢ❧యᵓ㐀ࡀᙳ㡪ࡍࡿගᙎᛶᣲືࢆ᳨ウࡋࡓ㸦ㄽᩥ䐤 . 8HWDQLet al.Carbohydr.
Polym. Technol. Appl. 㸧ࠋ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ࠊ⧞㏉ࡋ༢఩࡛࠶ࡿࢭࣟࣅ࣮࢜ࢫࡢᵓ㐀ኚᙧ࡟క࠺
」ᒅᢡ⋡ኚ໬ࢆศᴟ⋡࡟ࡼࡗ࡚ࠊࢭ࣮ࣝࣟࢫศᏊ㙐࡟࠾ࡅࡿගᙎᛶ≉ᛶࢆホ౯ࡋࡓࠋࣂࢡࢸࣜ࢔ࢭࣝࣟ
࣮ࢫࡢ㓄ྥᛶヨᩱ࡞࡝ࢆᑐ㇟࡜ࡋࡓᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࠊ⤖ᬗᵓ㐀࡟㉳ᅉࡍࡿගᙎᛶ≉ᛶࢆ≉ᚩ࡙ࡅࡓࠋ

- 133 -

㸱㸫㸰㸬ከ⢾ㄏᑟయࡀ♧ࡍ࢟ࣛࣝㄆ㆑⌧㇟௒᪥ࠊ་⸆ရ࡟௦⾲ࡉࢀࡿ࢟ࣛࣝ໬ᡂရࡢ⣙ ࡣከ⢾ㄏᑟయࢆ࢟ࣛࣝࢭ
ࣞࢡࢱ࣮࡜ࡍࡿࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ἲ࡟ࡼࡗ࡚ගᏛศ๭ࡉࢀࡿࠋከ⢾ㄏᑟయ࡟ࡼࡿ࢟ࣛࣝㄆ㆑ࡣࠊᛂ⏝㠃ࡢ㔜せᛶ࡟࡜࡝ࡲࡽࡎᏛ⾡ⓗ࡟ࡶ⯆࿡῝࠸⌧㇟࡛࠶ࡿࡀࠊࡑࡢᶵᵓ࡟ࡘ࠸࡚ࡣ඲ࡃ୙࡛᫂࠶ࡿࠋ᫖ᖺࡼࡾࠊᡃࠎࡣከ⢾ㄏᑟయ࡟ࡼࡿ࢟ࣛࣝㄆ㆑࣭࢟ࣛࣝศ㞳⌧㇟ࢆᑐ㇟࡜ࡋࡓศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࢆ㛤ጞࡋࡓࠋ࢟ࣛࣝศ㞳⌧㇟ࡢศᏊㄽⓗゎ᫂ࢆ┠ᣦࡍ࡜࡜ࡶ࡟ࠊ᪤Ꮡከ⢾ㄏᑟయ࢟ࣛࣝࢭࣞࢡࢱ࣮ࡀ♧ࡍ࢟ࣛࣝศ㞳ᵝᘧࡢணᡭẁࠊ࠾ࡼࡧ᪂つከ⢾ㄏᑟయ࢟ࣛࣝࢭࣞࢡࢱ࣮タィᡭẁ࡬ࡢᒎ㛤ࢆ┠ᶆ࡜ࡋࡓࠋ
㸦ᰴ㸧ࢲ࢖ࢭࣝࡼࡾ࢟
ࣛࣝࢭࣞࢡࢱ࣮࡜ࡋ࡚ᕷ㈍ࡉࢀ࡚࠸ࡿ  ✀ࡢከ⢾ㄏᑟయࠊFHOOXORVH WULV GLPHWK\OSKHQ\O FDUEDPDWH 㸦&7'3&㸧ࠊFHOOXORVH WULV PHWK\OEHQ]RDWHᅗ䠎㻚 䜻䝷䝹䝉䝺䜽䝍䞊ศᏊ㙐䠄㻯㼀㻰㻼㻯䠅&70%㸧ࠊ࠾ࡼࡧ DP\ORVH WUL GLPHWK\OSKHQ\OFDUEDPDWH 㸦$'03&㸧ࢆᑐ㇟࡜ࡋࡓ࢟ࣛࣝศ㞳⌧㇟ࡢ෌⌧࡜ㄆ㆑ᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋࢺ࣮࣮ࣞ࢞ሷᇶ➼ࡢࣔࢹࣝ࢟ࣛࣝศᏊࢆタᐃࡋࠊ60' ィ⟬࡟ࡼࡗ࡚࢟ࣛࣝࢭࣞࢡࢱ࣮ศᏊ㙐⾲㠃࡛࢟ࣛࣝศᏊࢆ㉮ᰝࡋࠊ࢟ࣛࣝศᏊࡢ⛣ື࡟せࡍࡿ࢚ࢿࣝࢠ࣮㔞ࢆẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊྠᡭẁ࡟ࡼࡿࢩ࣑ࣗ
࣮ࣞࢩࣙࣥィ⟬ࡣ᭷ព࡞ᕪ࡛࢟ࣛࣝศᏊࡢ࢟ࣛࣜࢸ࢕ࡢ㐪࠸ࢆ᳨ฟࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡓࡔࡋࠊ࢟ࣛ
ࣝศᏊ࡟ࡼࡗ࡚ࡣ࢟ࣛࣝศ㞳⤖ᯝࡀᚓࡽࢀࡎࠊࡲࡓࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟せࡍࡿィ⟬㈇Ⲵࡀᴟࡵ࡚኱ࡁ࠸
ࡇ࡜࠿ࡽࠊỗ⏝࢟ࣛࣝศ㞳ணᡭẁ࡜ࡋ࡚ᒎ㛤ࡍࡿࡓࡵ࡟ࠊከࡃࡢㄢ㢟ࡀṧࡉࢀ࡚࠸ࡿࠋ

㸱㸫㸱㸬⢾㉁㛵㐃ࢱࣥࣃࢡ㉁࡟ࡼࡿ⢾㙐ᇶ㉁ㄆ㆑
࢚ࢡࢫࣃࣥࢩࣥࡣ⣽⬊ᡂ㛗ࡸⰼ⢊⟶ఙ㛗ࡢ㝿࡟Ⓨ⌧ࡋࠊᡂ㛗࡟కࡗ࡚⏕ࡌࡿ⣽⬊ቨࡢᛂຊ⦆࿴ࡸࢡࣜ
࣮ࣉ࡟㛵୚ࡍࡿࠋᮏ◊✲࡛ࡣࠊ❧యᵓ㐀ⓗ࣭⏕⌮ᶵ⬟ⓗ࡟᳜≀⏤᮶࢚ࢡࢫࣃࣥࢩࣥ࡜㢮ఝࡍࡿᚤ⏕≀㸦Bacillus subtilis㸧⏤᮶࢚ࢡࢫࣃࣥࢩࣥ㸦(;/;㸧ࡢࢭ࣮ࣝࣟࢫᇶ㉁ㄆ㆑࡟㛵ࡍࡿศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ
◊✲ࢆ⾜࠸ࠊ(;/; ࡜ᇶ㉁ࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ」ྜయࣔࢹࣝࢆᥦ᱌ࡋࡓࠋ᭱Ᏻᐃࣔࢹࣝ࡟࠾࠸࡚ࠊ$VS
࡜ $VS ࡀࢭ࣮ࣝࣟࢫࢢࣜࢥࢩࢻ⤖ྜ㒊఩࡟㏆᥋ࡋࡓࡇ࡜࠿ࡽࠊ$VS ࢆࣉࣟࢺࣥ౪୚య࡟タᐃࡋࡓ
4000 ィ⟬ࢆᐇ⾜ࡋࠊ(;/; ࡢຍỈศゎゐ፹άᛶ⬟ࡢྍ⬟ᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ㸲㸬Ⓨ⾲ᐇ⦼㸦Ꮫ఍Ⓨ⾲࣭ㅮ₇㸧
 մᏱ㒔༟ஓࠕ࢟ࢳࣥ⤖ᬗ⧄⥔ࡢ⭾₶࣭⁐ゎᶵᵓ࡟㛵ࡍࡿ ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࠖ ➨  ᅇ᪥ᮏ࢟ࢳ࣭ࣥ࢟ࢺࢧࣥᏛ఍኱఍㸪࢜ࣥࣛ࢖ࣥ㸦ᣍᚅㅮ₇㸪 ᖺ  ᭶㸧 մᏱ㒔༟ஓࠕᵓ㐀ከ⢾ᮦᩱ࡜⢾㉁㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࠖ  ᖺᗘᛂ⏝⢾㉁⛉Ꮫ఍஑ᕞᨭ㒊ㅮ₇఍㸪࢜ࣥࣛ࢖ࣥ㸦ᣍᚅㅮ₇㸪 ᖺ  ᭶㸧 մᏱ㒔༟ஓࠕከ⢾࢖࢜ࣥᾮయࡢィ⟬໬Ꮫ◊✲࡟࠾ࡅࡿࢹ࣮ࢱ㥑ືᆺゎᯒࡢྍ⬟ᛶࠖ ⏘⥲◊᥋╔࣭᥋ྜᢏ⾡ࢥࣥࢯ࣮ࢩ࢔࣒ ➨  ᅇࢹ࣮ࢱ㥑ື :*㸪࢜ࣥࣛ࢖ࣥ㸦ᣍᚅㅮ₇㸪 ᖺ  ᭶㸧 մᏱ㒔༟ஓࠕ⢾㙐㧗ศᏊࡸ࢖࢜ࣥᾮయ࡟࠾ࡅࡿᵓ㐀ᶵ⬟┦㛵ࡢゎ᫂ࢆ┠ᣦࡋࡓศᏊࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ◊✲ࠖඛ㥑ⓗ⛉Ꮫィ⟬࡟㛵ࡍࡿࣇ࢛࣮࣒ࣛ 㸪࢜ࣥࣛ࢖ࣥ㸦ᣍᚅㅮ₇㸪 ᖺ  ᭶㸧 մṊඖభᶞ㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕከ⢾ㄏᑟయ࡟ࡼࡿ࢟ࣛࣝศ㞳ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࠖ  ᖺ⧄⥔Ꮫ఍ᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մ㔝⏣⹡኱㑻㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕࢭ࣮ࣝࣟࢫ , ᆺ㸫࢔ࣥࣔࢽ࢔」ྜయ⤖ᬗ࡟࠾ࡅࡿ࢔ࣥࣔࢽ࢔ศᏊ
ࡢᣑᩓᣲື࡟㛵ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࠖ ᖺ⧄⥔Ꮫ఍ᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մ㔝⏣⹡኱㑻㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕኳ↛ࢭ࣮ࣝࣟࢫ , ᆺ㸫࢔ࣥࣔࢽ࢔」ྜయ⤖ᬗࡢィ⟬໬Ꮫ◊✲ࠖ➨  ᅇ໬Ꮫ㛵㐃ᨭ㒊ྜྠ஑ᕞ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մᑎ⏣ᩗᩯ㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕ࣮࢝ࢻࣛࣥ୕㔜ࡽࡏࢇᵓ㐀ᙧᡂ࡜ᙧែ࡟㛵ࡍࡿ◊✲ࠖ➨  ᅇ໬Ꮫ㛵㐃ᨭ㒊ྜྠ஑ᕞ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧

- 134 - մṊඖభᶞ㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕከ⢾ㄏᑟయ࢟ࣛࣝࢭࣞࢡࢱ࣮࡟࠾ࡅࡿ࢟ࣛࣝㄆ㆑࡟㛵ࡍࡿ◊✲ࠖ➨  ᅇ໬Ꮫ㛵㐃ᨭ㒊ྜྠ஑ᕞ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մᯇཎ⪽㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕࣜࢰࢳ࣮࣒࡟ࡼࡿ࢟ࢳࣥࡢຍỈศゎ཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ➨ ᅇ᪥ᮏ࢟ࢳ࣭ࣥ࢟ࢺࢧࣥᏛ఍኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մ㔝⏣⹡኱㑻㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕ࢟ࢺࢧࣥሷ໬ள㖄ࡢ⤖ᬗᵓ㐀ゎᯒࠖ➨  ᅇ᪥ᮏ࢟ࢳ࣭ࣥ࢟
ࢺࢧࣥᏛ఍኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մṊඖభᶞ㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕከ⢾ㄏᑟయ࡟ࡼࡿ࢟ࣛࣝศ㞳ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ࠖࢭ࣮ࣝࣟࢫᏛ఍➨  ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մᒾᮏᡂ⍠㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕࣇ࢙ࢽࣝ࢝ࣝࣂ࣓࣮ࢺከ⢾ㄏᑟయ࡟࠾ࡅࡿ ࢟ࣛࣝㄆ㆑ࠖࢭࣝࣟ
࣮ࢫᏛ఍➨  ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մ⏣ᔱ⯟㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕ&HO$ ⢾⤖ྜᛶࣔࢪ࣮ࣗࣝ࡟ࡼࡿࢭ࣮ࣝࣟࢫ⤖ᬗ㠃ㄆ㆑ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࠖࢭ࣮ࣝࣟࢫᏛ఍➨  ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մᑎ⏣ᩗᩯ㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕ࣮࢝ࢻࣛࣥ୕㔜ࡽࡏࢇᵓ㐀ᙧᡂ࡜ᙧែ࡟㛵ࡍࡿ◊✲ࠖࢭ࣮ࣝࣟ
ࢫᏛ఍➨  ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մᮏ⏣ㄹኴ㑻㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕᚤ⏕≀⏤᮶࢚ࢡࢫࣃࣥࢩࣥ࡟ࡼࡿᇶ㉁ㄆ㆑ࠖࢭ࣮ࣝࣟࢫᏛ఍
➨  ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧 մ㔝⏣⹡኱㑻㸪Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥࠕ࢟ࢺࢧࣥሷ໬ள㖄ࡢ⤖ᬗࣔࢹࣜࣥࢢ◊✲ࠖࢭ࣮ࣝࣟࢫᏛ఍➨ ᅇᖺḟ኱఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸪 ᖺ  ᭶㸧㸳㸬ฟ∧ᐇ⦼ ᰝㄞ௜ࠊཎⴭㄽᩥ࣭⥲ㄝ մ7<XL78WR([WHQGHGHQVHPEOHPROHFXODUG\QDPLFVVWXG\RIFHOOXORVH,±HWK\OHQHGLDPLQHFRPSOH[FU\VWDOPRGHOVDWRPLVWLFSLFWXUHRIGHVRUSWLRQEHKDYLRUVRIHWK\OHQHGLDPLQHCellulose ±
 >,)@ .7DMLPD7,PDL7<XL0<DR,6D[HQD&HOOXORVHV\QWKHVL]LQJPDFKLQHU\LQEDFWHULDCellulose 
±  >,)@ . <RVKLL 7 8WR 7 2QLVKL ' .RVXJD 1 7DFKLNDZD <.DWD\DPD (WKHUIXQFWLRQDOL]HG S\UUROLGLQLXPEDVHG URRP
WHPSHUDWXUHLRQLFOLTXLGV3K\VLFRFKHPLFDOSURSHUWLHVPROHFXODUG\QDPLFV DQG WKH OLWKLXP LRQ FRRUGLQDWLRQ HQYLURQPHQWChemPhysChem  ±   >,) @ &RYHU)HDWXUH 䠄ᅗ 㸧 7 .RPRUL + 6DWULD . 0L\DPXUD $ ,WR 0 .DPL\D $
6XPLQR 7 2QLVKL . 1LQRPL\D .7DNDKDVKL -/$QGHUVRQ
7 8WR . .XURGD (VVHQWLDO UHTXLUHPHQWV RI ELRFRPSDWLEOHFHOOXORVHVROYHQWVACS Sustainable Chemistry & Engineering ±  >,)@ < .DWR 7 8WR ' 7DQDND . ,VKLEDVKL $ .RED\DVKL 0
+D]DZD 5 : :RQJ . 1LQRPL\D . 7DNDKDVKL ( +LUDWD  . .XURGD 6\QWKHWLF ]ZLWWHULRQV DV HIILFLHQW QRQSHUPHDEOHFU\RSURWHFWDQWV Communications Chemistry $UWLFOHQXPEHU  >,)@ . 8HWDQL 7 8WR 2IID[LV SKRWRHODVWLFLW\ E\ DQLVRWURSLF
PROHFXODUGHIRUPDWLRQRIXQLD[LDOO\DOLJQHGFHOOXORVHQDQRILEHU ᅗ䠏䠊Cover Feature, K. Yoshii,
ILOPV Carbohydrate Polymer Technologies and Applications  T. Uto, et al., ChemPhysChem
22 (2021)$UWLFOHQXPEHU 㸴㸬ฟ∧ᐇ⦼ ᰝㄞ↓ࠊⴭ᭩࣭⥲ㄝ  մᏱ㒔༟ஓࠕศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㞴⁐ᛶࣂ࢖࣐࢜ࢫࡢ⁐፹᥈⣴ࠖBioscience & Industry 
±  մୖ㇂ᖾ἞㑻 Ᏹ㒔༟ஓࠕࢼࣀࢭ࣮ࣝࣟࢫࡢ㓄ྥไᚚࡀᣅࡃఏ⇕࣭ගᏛ≀ᛶ࡜ᛂ⏝ࠖࢩ࣮࢚࣒ࢩ࣮
ฟ∧ࠗࢼࣀ࣮࣭࢝࣎ࣥࢼࣀࢭ࣮ࣝࣟࢫࡢศᩓ࣭㓄ྥไᚚᢏ⾡࠘➨  ❶ - 135 -

඲ཎᏊศᏊືຊᏛィ⟬ࡢ㧗ศᏊ◊✲࡬ࡢᒎ㛤
$SSOLFDWLRQRI$OO$WRP0ROHFXODU'\QDPLF6LPXODWLRQWR3RO\PHU
&KHPLVWU\‫ۑ‬ᒸᓮ 㐍ࠊỌ஭ ဴ㑻ࠊ‫ ‮‬அஓࠊ㔠Ꮚ ᩄᏹࠊᕊ⃝ ⠊⾜ࠊ୕ᔱ ᾈ࿴ࠊᙇ ⮳Ᏹ㸦ᮾி኱Ꮫ኱Ꮫ㝔᪂㡿ᇦ๰ᡂ⛉Ꮫ◊✲⛉㸧



◊✲┠ⓗ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚⇞ᩱ㟁ụ࡟࠾ࡅࡿ≀㉁㍺㏦ࡸ㧗⪏⇕ࢆᣢࡘ㧗ศᏊᮦᩱࡢศᏊᶵᵓゎ᫂➼ࢆ┠ᣦࡋ࡚◊✲ࢆᒎ㛤ࡍࡿࠋࡇࡢ┠ⓗࡢࡓࡵ࡟ࠊศᏊືຊᏛἲࡢᡭἲ㛤Ⓨࢆ⾜࠸ࠊ㧗ศᏊࡢㅖ⌧㇟࡟ᛂ⏝ࡍࡿࠋ≉࡟ࠊ㧗ศᏊෆ㒊࡛ࡢ≀㉁㍺㏦࡜㠀ᬗᶞ⬡ࡢຊᏛ≉ᛶ࡞࡝ࢆศᏊࣞ࣋ࣝ࠿
ࡽ᫂ࡽ࠿࡟ࡍࡿࠋ
1.1 㧗ศᏊෆ㒊࡛ࡢ≀㉁㍺㏦ࡢゎ᫂㧗ศᏊෆ㒊࡞࡝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㒊࡛ࡢᑠศᏊ
ࡢ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࠿࡟ࡍࡿࠋຍ࠼࡚ࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆ Smoluchowski ᪉⛬ᘧࡸ㐣ῶ⾶ࡢ Langevin ᪉⛬ᘧ࡟฼⏝ࡍࡿࡇ࡜࡛ࠊᑠศᏊ࡟ᑐࡍࡿ⢒ど໬ࢲ࢖ࢼ࣑ࢡࢫࢆసᡂࡍࡿࡇ࡜ࡶ࡛ࡁࡿࠋ
ࡉࡽ࡟ࠊ⢒ど໬ࢲ࢖ࢼ࣑ࢡࢫࢆࣔࣥࢸ࢝ࣝࣟἲ࡞࡝࡟ࡼࡾゎࡃࡇ࡜࡛ࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࡢ᫬㛫ࢆ㉸࠼ࡓ㛗᫬㛫ࡢࢲ࢖ࢼ࣑ࢡࢫࢆண

࡛ࡁࡿࠋᡃࠎࡣ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢホ౯᪉ἲࢆ᪂ࡓ࡟ᥦ

᱌ࡋࠊ⇞ᩱ㟁ụ࡟฼⏝ࡉࢀࡿ Nafion™ ⭷ࡸ⏕య⭷ࡢ≀㉁㏱㐣࡟࠾࠸࡚◊✲ࢆ⾜࠺ࠋ㧗ศᏊ㟁ゎ㉁⭷࡜ྜࢃࡏ࡚ࠊẼయศ㞳ࢆ┠ⓗ࡜ࡍࡿ↓ᶵ⣔Ⅳ⣲⭷ࡢ◊✲ࡶ⾜࠺ࠋ≉࡟ࠊ஧㓟໬Ⅳ⣲ࡢศ㞳ࢆ┠ⓗ࡜ࡋࠊⅣ⣲⭷ࡢᵓ㐀࡜Ẽయᣑᩓࡢ㛵ಀ࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡍࡿࠋ

1.2 㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶ㧗⪏⇕ᛶཬࡧ㧗ᙎᛶ⋡ࢆᣢࡘᙉ㠌࡞ࣂ࢖࣏࣐࣮࢜ࣜ࡟࠾ࡅࡿ◊✲ࡢ୍⎔࡜ࡋ࡚ࠊ⏕ྜᡂ⏤᮶ࡢࣔࣀ࣐࣮ࢆ
⏝࠸࡚ྜᡂࡉࢀࡓࣂ࢖࣏࣐࣮࢜ࣜ࡟ᑐࡋ࡚኱つᶍ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᘬᙇᙎᛶ⋡ࠊ㝆అᛂຊࠊ࢞ࣛࢫ㌿⛣ᗘ࡞࡝ࡢຊᏛ≉ᛶࡸ⇕ⓗ≉ᛶࢆᨭ㓄ࡍࡿศᏊᶵᵓࢆゎ᫂ࡍࡿࠋᚑ᮶ࡢ⢒ど໬ࣔࢹࣝ࡟ᇶ࡙࠸ࡓ◊✲࡟ᑐࡋ࡚ࠊᮏ◊✲ࡣᐇ㦂࡛ᚓࡿࡇ࡜ࡢ㞴ࡋ࠸ศᏊᵓ㐀࡜ㅖ≀ᛶ࡜ࡢ㛵ಀ࡟ᑐࡍࡿ⌮ゎࢆ῝ࡵࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ
ࡇࢀࡲ࡛᪤࡟ PMMA ࡸ PC ࡞࡝ࡢ௦⾲ⓗ࡞㠀⤖ᬗᛶ㧗ศᏊᶞ⬡࡟ᑐࡋࠊ࢞ࣛࢫ㌿⛣ࠊ
ᙎᛶኚᙧࠊ㝆అࠊṍࡳ㌾໬ཬࡧṍࡳ◳໬࡞࡝ࡢ⌧㇟ࢆ෌⌧ࡍࡿࡇ࡜ࢆ࡞ࡾ㐙ࡆࡓࠋࡑࡋ࡚ࠊᘏᛶ◚ቯ࡜⬤ᛶ◚ቯࡢྠ␗ཬࡧ㝆అ⌧㇟ࡢ㉳※࡞࡝ࡢศᏊㄽࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓࠋᮏ◊✲࡛ࡣ㧗⪏⇕ᛶࢆ㄂ࡿ࣏ࣜ࣋ࣥࢰ࢖
࣑ࢲࢰ࣮ࣝ㸦PBI㸧㢮㧗ศᏊࢆ◊✲ᑐ㇟࡜ࡋࠊ㧗ศᏊࡢຊᏛ≉ᛶ࡜⇕ⓗ≉ᛶࢆ໬Ꮫᵓ㐀ࡸศᏊᶵᵓ࡜㛵㐃ࡘࡅ࡚ࠊゎ᫂ࡍࡿࠋ

- 136 -

◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 㧗ศᏊෆ㒊࡛ࡢ≀㉁㍺㏦ࡢゎ᫂ྵỈ⋡ࢆኚ࠼ࡓ 4 ✀㢮ࡢ Nafion™ ⭷ࢆ⏝ពࡋࡓ㸦65, 81, 88, and 95 %㸧ࠋ఩⨨࡟౫Ꮡࡋࡓ⮬⏤࢚ࢿࣝࢠ࣮ࢆ
ᚓࡿࡓࡵ࡟ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࢭࣝࢆ 0.4 nm ⛬ᗘࡢ࣓ࢵࢩࣗ (voxel) ࡟ศゎࡋࠊ⢏Ꮚᤄධἲ࡟ࡼࡿィ⟬ࢆ⾜ࡗࡓࠋNVT ࢔ࣥࢧࣥࣈ࡛ࣝྂ඾ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ5 ns ࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽ 5,000 ಶࡢᵓ㐀ࢆᚓࡓࠋྛᵓ㐀ࡢ voxel ୍ࡘ୍ࡘ࡟ࠊỈ⣲㸦㓟⣲㸧ศᏊࡢᤄධࢆ 320 (400) ᅇヨ⾜ࡋࡓࠋࡍ࡞ࢃࡕࠊvoxel
ࡈ࡜࡟ 1,600,0000 (2,000,000) ᅇ࡛࠶ࡿࠋ⢏Ꮚᤄධἲࡢ⢭ᗘࢆ☜ㄆࡍࡿࡓࡵ࡟ࠊ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬࡟ overlapping distribution ἲࢆ㐺⏝ࡋࡓࠋᤄධࡋࡓẼయศᏊࢆ flat-bottom ࣏ࢸࣥࢩ࡛ࣕࣝᣊ᮰ࡋࡓࠋNVT ࢔ࣥࢧࣥࣈ࡛ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ⁐㉁̽⁐፹㛫ࡢ┦஫స⏝ࢆィ⟬ࡋࡓࠋࣃ࣮ࢥ࣮ࣞࢩࣙࣥ̽ࢡࣛࢫࢱゎᯒࢆ⾜࠸ࠊẼయศᏊࡢᣑᩓ⤒㊰ࢆྠᐃࡋࡓࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊGROMACS ࠾ࡼࡧ MODYLAS ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ฼⏝ࡋࡓࠋ↓ᶵ⣔Ⅳ⣲⭷ࡢィ⟬࡛ࡣࠊ࣏ࣜ࢖࣑ࢻ⏤᮶ࡢ࣏࣐࣮࡛ࣜ࠶ࡿ࣐ࢺ࣑ࣜࢻ®ࡢ⇕ศゎ㐣⛬ࢆ LAMMPS ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ཯ᛂຊሙࢆ᥇⏝ࡋࡓࠋ஧㓟໬Ⅳ⣲࡜⏕ᡂࡋࡓⅣ⣲⭷ࡢ」ྜ⣔࡟ࡘ࠸࡚ࠊGROMACS ࡛ྂ඾ศᏊື
ຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᖹᆒ஧஌ኚ఩࠿ࡽᣑᩓಀᩘࢆồࡵࡓࠋ

2.2 㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶࡇࢀࡲ࡛సᡂࡋࡓ PMMAࠊPC ཬࡧ PS ࡢ⣔࡛ࠊศᏊ㔞ศᕸࠊ࠿ࡽࡳ࠶࠸ᐦᗘ࡜័ᛶ༙ᚄࡢㄪᩚࡢ᭷↓ཬࡧࡑࢀࡒࢀࡢ෭༷㏿ᗘࡣ࢞ࣛࢫ㌿⛣సᡂࡋࠊ࢞ࣛࢫ㌿⛣ᗘ࡜ᘬᙇᙎᛶ⋡࡟ᙳ㡪ࢆ᳨ウࡋ࡞ࡀࡽ㐺ษ࡞ࣂ࢖࢜㧗ศᏊࡢࣔࢹࣝ⣔ࢆᗘཬࡧᘬᙇᙎᛶ⋡ࢆィ⟬ࡋࡓࠋᮏ◊✲࡛ࡣ࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢ PBIࠊPBI̽pPAࠊ

PBI̽PBO̽mPA ࡜ PBI̽PBO̽pPA ࡢ 4 ✀㢮ࡢ㧗ศᏊ࡟࠾࠸࡚ศᏊ㔞ศᕸཬࡧ័ᛶ༙ᚄࢆᐇ㦂ࢹ࣮ࢱ࡟ྜࢃࡏ࡚
ࡑࢀࡒࢀࡢ㧗ศᏊࡢⓒ୓ཎᏊࢆᣢࡘ඲ཎᏊࣔࢹࣝ⣔ࢆసᡂࡋࠊ㧗ࡢ 1,200 K ࠿ࡽᐊࡢ 300 K ࡲ࡛ 20 ࢼࣀ⛊ẖ࡟ 20 K ࢆୗࡆ࡞ࡀࡽᖹ⾮໬ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ෭༷ィ⟬ࡢ⤖ᯝࢆ⏝࠸࡚ࡑࢀࡒࢀࡢ㧗ศᏊࡢ࢞ࣛࢫ㌿⛣ᗘࢆ⥺ࢆࡗࡓࠋࡑࡢᚋࠊࡑࢀࡒࢀ࡟ࣔࢹࣝ࡟ᑐࡋ࡚ࠊ୍㍈ᘏఙࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࠊᛂຊࡦࡎࡳ᭤

ࡗࡓࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣ MODYLAS ࡜ GROMACS ࡜࠸࠺ࢯࣇࢺ࢙࢘࢔ࢆ฼⏝ࡋ࡚⾜ࡗ

ࡓࠋ



◊✲ᡂᯝ

3.1 㧗ศᏊෆ㒊࡛ࡢ≀㉁㍺㏦ࡢゎ᫂⇞ᩱ㟁ụࡢຠ⋡ࢆྥୖࡉࡏࡿࡓࡵ࡟ࡣࠊ㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ㓟⣲ࡸỈ⣲࡜࠸ࡗࡓᑠศᏊẼయࡢᾐ㏱ᶵᵓࡢ⌮ゎࡀ㘽࡜࡞ࡿࠋ≉࡟ࠊ࣏࣐࣮࣭ࣜỈ࣭ቃ⏺ࡢ 3 ࡘࡢ㡿ᇦࡢ࠺ࡕࠊ࡝ࡢ┦ࡀᣑᩓ࡛㔜せ࡞ᙺ๭ࢆᢸࡗ࡚
࠸ࡿ࠿᫂ࡽ࠿࡟ࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ࠊNafion™ ⭷࡟࠾ࡅࡿ㓟⣲ศᏊཬࡧỈ⣲ศᏊࡢ 3 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆసᡂࡋࠊࡇࢀࡽẼయࡢᣑᩓ⤒㊰ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡎࠊ
⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ࡜ศᏊࡢᵓ㐀ࢆ㔜ࡡྜࢃࡏࡿ࡜୧⪅࡟ࡣ┦㛵ࡀぢࡽࢀࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟㧗࠸ࡢࡣࠊ࣏࣐࣮ࣜ┦࡛ࣄࢻࣟࢽ࣒࢘࢖࢜ࣥ࡟ᅖࡲࢀࡓࢫࣝ࣍ࣥ㓟ᇶࡢ㡿ᇦ࡛࠶ࡗࡓࠋ୍᪉ࠊ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟ప࠿ࡗࡓࡢࡣࠊ࣏࣐࣮ࣜ┦ࡢ㡿ᇦ࠶ࡿ࠸ࡣ࣏࣐࣮࣭ࣜỈࡢቃ⏺㡿ᇦ࡛࠶ࡗࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ࡣ࣏࣐࣮ࣜ┦࡛ࡣ
ୖ㏙ࡢ㏻ࡾ㧗పࡀぢࡽࢀࡓࡀࠊỈ┦࡛ࡣẚ㍑ⓗᖹᆠ࡛࠶ࡗࡓࠋࣃ࣮ࢥ࣮ࣞࢩࣙࣥ̽ࢡࣛࢫࢱゎᯒ࡟ࡼࡿ࡜ࠊ࣏
࣐࣮ࣜ┦ࡢ㡿ᇦ࠶ࡿ࠸ࡣ࣏࣐࣮࣭ࣜỈࡢቃ⏺㡿ᇦ࡛⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟పࡃࠊࡘ࡞ࡀࡗࡓ⤒㊰ࡀⓎぢࡉࢀࡓࠋ- 137 -

ࡋࡓࡀࡗ࡚ࠊᣑᩓࡣ୺࡟ࡇࡢ㡿ᇦ࡛㉳ࡇࡿ࡜ண᝿ࡉࢀࡿࠋࡲࡓࠊ⤒㊰ࡢ࠺ࡕࠊ⣙ 70 (30) %ࡀ࣏࣐࣮ࣜ㸦ቃ⏺㸧┦࡟ᑐᛂࡋ࡚࠾ࡾࠊỈ┦࠿ࡽࡢᐤ୚ࡣṤ࡝࡞࠿ࡗࡓࠋࡓࡔࡋࠊỈ┦ࡣ ~1–2 kBT ⛬ᗘ࢚ࢿࣝࢠ࣮ⓗ࡟㧗࠸ࡔࡅ࡛࠶ࡾࠊᣑᩓ࡟࠾ࡅࡿ๪ḟⓗ࡞ᐤ୚ࡀ⪃࠼ࡽࢀࡿࠋࡇࢀ
ࡣ௒ᚋࡢ᳨ウㄢ㢟࡛࠶ࡿࠋྵỈ⋡ࢆቑຍࡉࡏ࡚ィ⟬ࡋࡓ࡜ࡇࢁࠊ࣏࣐࣮ࣜ┦ࡢ㡿ᇦ࠶ࡿ࠸ࡣ࣏࣐࣮ࣜ㸫Ỉࡢቃ⏺㡿ᇦ࡛⮬⏤࢚ࢿࣝࢠ࣮ࡀ⁥ࡽ࠿࡜࡞ࡾࠊᣑᩓࡀ㐍⾜ࡋࡸࡍࡃ࡞ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
௒ᚋࡢணᐃ࡜ࡋ࡚ࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢィ⟬࡜ 3 ḟඖᣑᩓಀᩘ࣐ࢵࣉࡢసᡂࡀ࠶ࡆࡽࢀࡿࠋࡑࡢ➨୍Ṍ࡜ࡋ࡚ࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࢆక࠺ᣑᩓ᪉⛬ᘧࢆ‶㊊ࡍࡿࡼ࠺࡞ືⓗࣔࣥࢸ࢝ࣝࣟἲࢆᑟฟࡋࡓࠋ
⢒ど໬࡜఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡟ࡼࡾࠊ㛗㊥㞳࣭㛗᫬㛫ࢫࢣ࣮ࣝ࡟࠾ࡅࡿ≀㉁㍺㏦ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡬ࡢ
ᛂ⏝ࡀぢ㎸ࡲࢀࡿࠋᮏ◊✲ࡢ㧗ศᏊ㟁ゎ㉁⭷ࡢࡼ࠺࡞୙ᆒ୍⣔࡟࠾ࡅࡿヲ⣽࡞ᣑᩓ⤒㊰ࡢ᥈⣴࡜ᣑᩓ㏿ᗘࡢᅗ 1. ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ⟬ฟࡋࡓィ⟬࡬ࡢ㐺⏝ࢆ᳨ウࡋ࡚࠸ࡿࠋ
↓ᶵ⣔Ⅳ⣲⭷୰࡟࠾ࡅࡿ஧㓟໬Ⅳ⣲ࡢᣑᩓࢩ࣑ࣗࣞ

࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢ࢞ࣛࢫ㌿⛣ᗘ࣮ࢩࣙࣥࢆ⾜ࡗࡓࠋ཯ᛂຊሙࡢศᏊືຊᏛィ⟬࡟ࡼࡾࠊ↝ᡂᗘࡀ㧗࠸࡯࡝Ⅳ໬⋡ࡶୖ᪼ࡋࠊⅣ⣲㠃ࡀⓎ㐩ࡍࡿࡢࡀ☜ㄆࡉࢀࡓࠋᐇ㦂࡛ᐃࡉࢀࡓඖ⣲ศᯒࡸᩓ஘

ᵓ㐀ᅉᏊ࣭ືᚄศᕸ㛵ᩘࢆᐃᛶⓗ࡟෌⌧࡛ࡁ࡚࠾ࡾࠊཎ
Ꮚ㛫㊥㞳⛬ᗘࡢᚤどⓗ࡞ࣞ࣋ࣝࡢᵓ㐀ࡢಙ㢗ᛶࡀ☜ㄆࡉࢀࡓࠋ୍᪉㸪ࢼࣀ࣓࣮ࢺࣝ⛬ᗘࡢᵓ㐀⛛ᗎ㸦ᐦᗘࡸ✵Ꮝࢧ࢖ࢬศᕸ㸧ࡸᣑᩓಀᩘࡢ
࠿ࡗࡓࠋ≉࡟㧗ᗘ౫Ꮡᛶࡣㄝ࡛᫂ࡁ࡞

㡿ᇦ࡛ࡢᣑᩓಀᩘࡢ㐣኱ホ౯ࡣ㸪࣐࢖ࢡࣟᏍࡀ⣔࡟ᗈࡃᏑᅾࡋ࡚࠸ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ

3.2

ᅗ 2. ᛂຊࡦࡎࡳ᭤⥺㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶ࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢᶵᲔⓗ≉ᛶཬࡧ⇕ຊᏛ≉ᛶࢆ◊✲ࡍࡿࡓࡵ࡟ࠊ኱つᶍศᏊືຊᏛࢩ࣑࣮ࣗࣞ
ࢩࣙࣥࢆ⾜ࡗࡓࠋศᏊ㔞ศᕸࡸ័ᛶ༙ᚄࢆᐇ㦂ࢹ࣮ࢱ࡟ྜࢃࡏ࡚ᅄ✀㢮ࡢ PBI 㢮㧗ศᏊࡢⓒ୓ཎᏊ⣔ࢆసᡂࡋࡓࠋ⥆࠸࡚ࠊ1,200 K ࡢ㧗࠿ࡽ 20 ࢼࣀ⛊ẖ࡟ 20 K ࡢ㏿ᗘ࡛ࡑࢀࡒࢀࡢࣔࢹࣝࢆ࢔ࢽ࣮ࣜࣥࢢࡋࡓࠋ300

K ࡲ࡛෭༷ࡋࡓᚋ୍࡛㍈ᘏఙࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᛂຊࡦࡎࡳ᭤⥺ࢆࡢ㧗ศᏊࡢ࢞ࣛࢫ㌿⛣ᗘࢆࡗࡓࠋ෭༷㐣⛬࠿ࡽࡑࢀࡒࢀ

ࡗࡓ㸦ᅗ 1㸧ࠋᅗ 2 ࡟♧ࡋࡓ㏻ࡾ࡟ࠊࡍ࡭࡚ࡢᛂຊࡦࡎࡳ᭤⥺ࡣᘏᛶࡢࡼ࠺࡟

࡞ࡿࠋᮏ◊✲࡛ࡣࠊࡑࢀࡒࢀࡢ㧗ศᏊࡢᘬᙇᙎᛶ⋡ࠊ㝆అᛂຊࠊ࣏࢔ࢯࣥẚ࡞࡝ࡢᶵᲔⓗᛶ㉁ࡣᐊ
Ỉ⣲⤖ྜࡢᩘ࡟ࡼࡿỴࡲࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊ࢞ࣛࢫ㌿⛣

ᗘࡣ㧗

ᐦᗘ࡜

࡛⌧ࢀࡿࡢ࡛ࠊỈ⣲⤖ྜ࡜ࡢ┦㛵ࡣᙅ࠸࡜⪃࠼ࡽࢀࡿࠋࡇࢀ࠿ࡽࠊࡑࢀࡽࡢ㧗ศᏊࡢ⇕ⓗ≉ᛶ࡜ຊᏛ≉ᛶ࡟ࡘ࠸࡚᭦࡟ゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

- 138 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
x‫ۻ‬Ọ஭ ဴ㑻ࠊ⸨ᮏ ࿴ኈࠊᒸᓮ 㐍ࠕ㧗ศᏊ㟁ゎ㉁⭷࡟࠾ࡅࡿ࢞ࢫศᏊ㍺㏦ࡢ඲ཎᏊศᏊࢩ࣑ࣗࣞ
࣮ࢩࣙࣥ◊✲ࠖ➨ 70 ᅇ㧗ศᏊウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧࣏ࢫࢱ࣮Ⓨ⾲xỌ஭ ဴ㑻ࠊᒸᓮ 㐍ࠕ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࡢศᏊᶵᵓゎ᫂࡟ྥࡅࡓ୍᪉ἲㄽ ̿ືⓗࣔࣥࢸ࢝ࣝࣟἲࡢ㐺⏝̿ࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ཱྀ㢌Ⓨ⾲x‫ۻ‬Ọ஭ ဴ㑻ࠊ⸨ᮏ ࿴ኈࠊᒸᓮ 㐍ࠕ⮬⏤࢚ࢿࣝࢠ࣮࡜఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡟ࡼࡿ㧗ศᏊ㟁ゎ
㉁⭷࡟࠾ࡅࡿ࢞ࢫศᏊࡢ≀㉁㍺㏦ࡢゎ᫂ࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ཱྀ㢌Ⓨ⾲xỌ஭ ဴ㑻ࠊᒸᓮ 㐍ࠕ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦࡬ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽࡢ࢔ࣉ࣮ࣟࢳ㸸ィ⟬ᡭἲࡢ᳨ウࠖ➨ 35 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᒸᒣ㸧ཱྀ㢌Ⓨ⾲x‫ۻ‬Ọ஭ ဴ㑻ࠊ⸨ᮏ ࿴ኈࠊᒸᓮ 㐍ࠕ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦࡬ࡢศᏊࢩ࣑ࣗ ࣮ࣞࢩࣙࣥ࠿ࡽ
ࡢ࢔ࣉ࣮ࣟࢳ㸸㧗ศᏊ㟁ゎ ㉁⭷࡬ࡢᛂ⏝ࠖ➨ 35 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᒸᒣ㸧ཱྀ㢌Ⓨ⾲x‫ ‮ۻ‬அஓࠊᒸᓮ 㐍 "All-atomistic molecular dynamics study of the glass transition phenomenon of
amorphous polymers" ➨ 70 ᅇ㧗ศᏊウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ཱྀ㢌Ⓨ⾲x‫ ‮ۻ‬அஓࠊᒸᓮ 㐍ࠕ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㠀ᬗᛶ㧗ศᏊࡢ࢞ࣛࢫ㌿⛣ࡢศᏊㄽࠖ➨ 35 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᒸᒣ㸧ཱྀ㢌Ⓨ⾲x‫ۻ‬㔠Ꮚ ᩄᏹࠊ⸨ᮏ ࿴ኈࠊ▼ᕝ ༤❶ࠊୗᒸ ⛱ࠊᒸᓮ 㐍 "All-atom molecular dynamics simulation
study on dielectric properties of p-hydroxybenzoic acid polymer crystal" ➨ 70 ᅇ㧗ศᏊウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ཱྀ㢌Ⓨ⾲x‫ۻ‬㔠Ꮚ ᩄᏹࠊ⸨ᮏ ࿴ኈࠊ▼ᕝ ༤❶ࠊୗᒸ ⛱ࠊᒸᓮ 㐍ࠕ඲ཎᏊศᏊືຊᏛィ⟬࡟ࡼࡿ p-ࣄࢻࣟ࢟ࢩᏳᜥ㤶㓟㔜ྜయ⤖ᬗࡢㄏ㟁ศᩓ࡜ࡑࡢศᏊㄽⓗ㉳※ࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ཱྀ㢌Ⓨ⾲x‫ۻ‬㔠Ꮚ ᩄᏹࠊ໭⏿ 㞞ᘯࠊᒸᓮ 㐍ࠕ⁐፹㸫⁐㉁ࡢ኱㔞ྠ᫬ኚ᥮ࢆྍ⬟࡜ࡍࡿ⇕ຊᏛⓗ✚ศἲ࡟ᇶ࡙ࡃΰྜ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡢᥦ᱌ࠖ➨ 35 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᒸᒣ㸧࣏ࢫࢱ࣮Ⓨ⾲x‫ۻ‬ᕊ⃝ ⠊⾜ࠊ໭⏿ 㞞ᘯࠊᒸᓮ㐍ࠕ཯ᛂຊሙศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿⅣ⣲⭷ࡢᵓ㐀⏕ᡂ࡜Ẽయᣑᩓࠖ➨ 35 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦ᒸᒣ㸧࣏ࢫࢱ࣮Ⓨ⾲ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
x‫ۻ‬Nagai, T.; Fujimoto, K.; Okazaki, S. Three-dimensional free-energy landscape of hydrogen and oxygen
molecules in polymer electrolyte membranes: Insight into diffusion paths. J. Chem. Phys. 2022, 156, 044507.

x‫ۻ‬Nagai, T.; Yoshimori, A.; Okazaki, S. Dynamic Monte Carlo calculation generating particle trajectories
that satisfy the diffusion equation for heterogeneous systems with a position-dependent diffusion coefficientand free energy. J. Chem. Phys. 2022, 156, 154506.

x‫ۻ‬Tang, Z.; Fujimoto, K.; Okazaki, S. A comparison of the brittle PMMA with the ductile PC on the elasticity
and yielding from a molecular dynamics perspective. Polymer 2021, 226, 123809.

- 139 -

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Analysis of Solvation and Dynamics of Molecules and Ionsin Nanoscale Space


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[2] T. Horikawa, N. Sakao, D.D. Do, Carbon, 56, 183 (2013).
[3] T. Horikawa, S. Tan, D.D. Do, K.-I. Sotowa, J.R. Alcántara-Avila, D. Nicholson, Carbon, 124, 271 (2017).
[4] K. Yoshida and M. Nakahara, J. Chem. Phys. 150, 174505 (2019).

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ØÚÙKen Yoshida : Stability and reactivity of film-forming amines in supercritical water: 14N NMR study on model
alkylamines, 2021 IAPWS PCAS Symposium, Online, Aug. 2021.
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ØÙNaoki Noguchi, Takuya Yonezawa, Yu Yokoi, Tomoki Tokunaga, Taro Moriwaki, Yuka Ikemoto and Hidekazu
Okamura : Dynamics and cage occupancies of methane hydrates at low temperatures and high pressures: An infrared andRaman spectroscopic study, 10th Asian Conference on High Pressure Research, Nov. 2021.
ØÙKen 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.

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ࢀࡓࠋLJ ࣏ࢸࣥࢩࣕࣝࡔࡅࡢ࡜ࡁ࡟ࡣᖖ࡟㐣኱ホ౯࡛࠶ࡗࡓࡀࠊࡑࢀ࡜ࡣᑐ↷ⓗ࡛࠶ࡿࠋ୍᪉ࠊAAOZ ⌮ㄽࢆ౑࠼ࡤᇙࡶࢀࡓཎᏊ࡟ᑐࡍࡿグ㏙ࡣ㢧ⴭ࡟ᨵၿࡋࡓࠋࡋ࠿ࡋࠊᇙࡶࢀ࡚࠸࡞࠸ཎᏊ࡟ࡘ࠸࡚ࡣ AAOZ ⌮ㄽ࡛ࡣグ㏙ࡀࡼࡃ࡞࠸ࡇ࡜ࡀุ᫂ࡋࡓࠋࡴࡋࢁࠊᇙࡶࢀ࡚࡞࠸ཎᏊ࡟ࡘ࠸࡚ࡣ RISM ⌮ㄽ࡛ࡶ࠿࡞ࡾࡼࡃグ㏙࡛ࡁࡿࠋᮏ◊✲ᡂᯝ࡜ࡋ࡚ࠊᇙࡶࢀࡓཎᏊ࡟ࡘ࠸࡚ࡣ AAOZ ⌮ㄽࢆ౑࠸ࠊᇙࡶࢀ࡚࡞࠸ཎᏊࡣ RISM ⌮ㄽࢆ౑࠺ࠊ࡜࠸࠺౑࠸ศࡅࡀ᭷ຠ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡉࡽ࡟ヲࡋ࠸ゎᯒࡢ⤖ᯝࠊᇙࡶࢀࡓཎᏊ࡟ᑐࡋ࡚
AAOZ ⌮ㄽࡣ⥲ࡌ࡚ࡼ࠸㏆ఝࢆ୚࠼ࡿࡀࠊAAOZ ⌮ㄽࡢゅᗘ౫Ꮡ 1 ḟඖศᕸ㛵ᩘࡣゅᗘ࡟ࡼࡗ࡚ㄗᕪࡀ↓ど࡛ࡁ࡞࠸ሙྜࡀ࠶ࡿࡇ࡜ࡶศ࠿ࡗࡓ㸦ゅᗘᖹᆒ࡛ぢࢀࡤ࠶ࡲࡾㄗᕪࡢᙳ㡪ࡣฟ࡞࠸ࡼ࠺࡛࠶ࡿ㸧ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ‫[ ۻ‬1] Tatsuhiko Miyata, “Development of concepts and bridge functions to improve the accuracy of solvation freeenergy for molecular liquids”, December 16-21, 2021, Pacifichem 2021, Virtualฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫[ ۻ‬1] T. Miyata, S. Murata, M. Sakamoto, and Y. Sasaki, AIP adv., 12 (2022) 035248.

- 144 -

ගྜᡂ㓟⣲Ⓨ⏕୰ᚰ &D0Q2 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែ࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDOVWXGLHVRIHOHFWURQLFDQGVSLQVWDWHVDQGUHDFWLYLW\RIWKH
&D0Q2FOXVWHULQWKHR[\JHQHYROYLQJFRPSOH[RISKRWRV\VWHP,,‫ۑ‬ᒣཱྀ ඙㸦኱㜰኱Ꮫࢼࣀࢧ࢖࢚ࣥࢫᩍ⫱◊✲ࢭࣥࢱ࣮㸧ࠊỿ ೺ோࠊ☾㒊 ᐶ㸦ᒸᒣ኱Ꮫ␗ศ㔝ᇶ♏◊✲ᡤ㸧ࠊ୰㇂࿴ᙪ㸦኱㜰኱Ꮫ⏘ᴗ⛉Ꮫ◊✲ᡤ㸧ࠊ⚄㇂ಙኵ㸦኱㜰ᕷ❧኱Ꮫ」ྜඛ➃◊✲ᶵᵓ㸧ࠊᗉྖග⏨ࠊᐑᕝ᫭୍㸦⟃Ἴ኱Ꮫィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㸧
ࠊᕝୖ㈗㈨㸦኱㜰኱Ꮫ⌮Ꮫ◊✲⛉㸧◊✲┠ⓗᮏ◊✲ࡣኳ↛ගྜᡂ⣔ (PSII) ࡢ㓟⣲Ⓨ⏕ࢧ࢖ࢺ (OEC)࡟࠾ࡅࡿኴ㝧ගࢆ฼⏝ࡋࡓỈศゎ཯ᛂᶵᵓࢆᙜヱศ㔝ࡢඛᑟ㒊㝲࡛࠶ࡿᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡟ࡼࡾゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋኳ↛⣔ (PSII) ࡟࠾ࡅࡿỈศゎ཯ᛂࡣኴ㝧ග࢚ࢿࣝࢠ࣮ (4hv) ࢆ㥑ືຊ࡜ࡋࠊCaMn4O5 ࢡࣛࢫࢱ࣮ࢆゐ፹࡜ࡋ࡚ 5 ẁ㝵 (S0 ~ S4) ࡢࢫࢸࢵࣉࢆ⤒࡚㐍⾜ࡍࡿ
(Kok ࢧ࢖ࢡࣝ࡜⛠ࡉࢀࡿ) (ᅗ 1)ࠋ:
2H2O + 4hν → O2 + 4H+ + 4e–(1)

᭱㏆࡛ࡣ PSII ࡟㛵ࡍࡿ⮬⏤㟁Ꮚ࣮ࣞࢨ࣮(XFEL)ᐇ㦂ࡀ㐍ᒎࡋࠊ౛࠼ࡤศᢸ⪅ỿࡽ (Suga et al., Nature, 543, 131 (2017))

ᅗ1

Kok ࢧ࢖ࢡࣝ

࡜ࡈࡃ᭱㏆ࡢ Berkeley(LBL)ࡢ Kern, Yano, Yachandra ࡽ࡟ࡼࡿ㧗ศゎ⬟ XFEL ࡟ࡼࡿ S3 ᵓ㐀 (Kern et al., Nature, 563, 421 (2018))ࠊ཯ᛂᶵᵓࡢゎ᫂ࡢࡓࡵࡢᵓ㐀ⓗᇶ┙ࡀゎ᫂ࡉࢀࡘࡘ࠶ࡿࠋ୍᪉ࠊCaMn4O5 ࢡࣛࢫࢱ࣮ࡣ⌮ㄽⓗ࡟ࡣ㟁Ꮚ┦㛵ຠᯝࡀ㔜せ࡛࠶ࡿࡇ࡜ࡼࡾࠊゐ፹ᶵ⬟ࡢゎ᫂࡟ࡣࡑࡢ㟁Ꮚ࣭ࢫࣆࣥ≧ែࡢゎ᫂ࡀ୙ྍḞ࡛࠶ࡿࠋࡇࢀࡽࡢᐇ㦂⤖ᯝࢆゎᯒࡍࡿࡓࡵ࡟ᚑ᮶࠿ࡽࠊ
Broken Symmetry (BS)-ᐦᗘỗ㛵ᩘ⌮ㄽ (DFT) ࡢᡭἲࢆ⏝࠸ࡓ QM ࡸ QM/MM ィ⟬࡟ࡼࡾ OEC ࡢ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែࠊ཯ᛂ㐣⛬ࡢゎᯒ࡟࠾࠸࡚ BS-DFT ࡢᡭἲࡢ᭷⏝ᛶࢆ♧ࡋ࡚ࡁࡓ(Kanda
et al., Polyhedron, 30, 3256 (2011); Isobe et al., Dalton Trans., 41, 13727 (2012); Shoji et al., Faraday Discuss., 198, 83(2017) ➼)ࠋᚑࡗ࡚ࠊPSII ࡢ㓟⣲Ⓨ⏕ゐ፹ࢧ࢖ࢺ (OEC) ࡣᙉ┦㛵㟁Ꮚ⣔ (SCES) CaMn4O5 ࢡࣛࢫࢱ࣮ࡀ PSIIࡢ⺮ⓑሙ࡟㛢ࡌ㎸ࡵࡽࢀࡓศᏊࢩࢫࢸ࣒࡛࠶ࡿ࡜⪃࠼ࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋ⏦ㄳ⪅ࡽࡣࡇࡢࡼ࠺࡞どⅬ࡛
OEC ࡟࠾ࡅࡿỈศゎ཯ᛂᶵᵓࡢ㟁ᏊࠊཎᏊࠊศᏊ࡛ࣞ࣋ࣝࡢゎ᫂ࢆ┠ᣦࡋ⣔⤫ⓗ࡟ィ⟬ᶵᐇ㦂ࢆᐇ⾜ࡋ࡚ࡁࡓࠋ⌧ᅾࡲ࡛ࡢ◊✲⤖ᯝࢆ XFEL ᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿ࡜ࠊᑐ⛠ᛶࡢ◚ࢀࡓ (Broken Symmetry, BS) ᐦᗘỗ㛵ᩘ(HDFT) ࢆ⏝࠸ࡓ QM (᭱኱ 380 ཎᏊ) / MM ィ⟬ࡣᵓ㐀᭱㐺໬࡟㛵ࡋ࡚ࡣ༑ศಙ㢗࡛ࡁࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸
ࡿࠋ୍᪉ࠊKok ࢧ࢖ࢡࣝࡢྛ≧ែ࡛⏕ᡂྍ⬟࡛࠶ࡿ୰㛫యࡢ┦ᑐ࢚ࢿࣝࢠ࣮ࡢゎ᫂࡟㛵ࡋ࡚ࡣ BS (HDFT) ἲ࡟ྵࡲࢀࡿ HF ᡂศࡢ๭ྜ࡟ᩄឤ࡞ሙྜࡀ࠶ࡾ(Isobe et al., Inorg. Chem., 55, 502 (2016))ࠊcoupled cluster (CC)ἲ࡞࡝ࡢ㧗⢭ᗘィ⟬⤖ᯝ࡜ࡢẚ㍑᳨ウࡀᚲせ୙ྍḞ࡛࠶ࡗࡓࠋࡑࡇ࡛ࠊ⏦ㄳ⪅ࡽࡣ DLPNO-CC ἲ(Saitow et- 145 -

al., J. Chem. Phys., 146, 164105 (2017))ࢆィ⟬ྍ⬟࡞ẚ㍑ⓗᑠࡉ࠸ CaMn4O5 㘒య࡟㐺⏝ࡋࠊBS DFT ィ⟬⤖ᯝ࡜ẚ㍑᳨ウࡋࠊ㟁Ꮚ┦㛵ຠᯝࡢ㔜せᛶࢆᐇドࡋ࡚ࡁࡓ(Miyagawa et al., Chem. Phys Lett., 732, 13660 (2019); Phys.
Chem. Chem. Phys., 22, 27191 (2020) ➼)ࠋࡋ࠿ࡋࠊPSII ࡢᶵ⬟Ⓨ⌧ࡢゎ᫂࡟ࡣ⺮ⓑሙࡢຠᯝࢆ⪃៖ࡍࡿࡇ࡜ࡀ
ᚲ㡲࡛࠶ࡿࠋࡇࡢࡼ࠺࡞どⅬ࠿ࡽࠊ๓ᖺᗘࡢᚋ༙࠿ࡽከ㝵ᒙ㐃⤖ィ⟬ࠊQM1 (DLPNO-CC) / QM2 (BS DFT) /MM ࡞࡝ࡢ᭷ຠᛶࡢ᳨ウࢆጞࡵ࡚ࡁࡓࡀࠊ௒ᖺᗘ࠿ࡽࡣ CaMn4O5 㘒యࢥ࢔ࡢ࿘ࡾࡢ⺮ⓑሙࢆ⪃៖ࡋࡓ 300 ཎᏊ⣔ࡢከ㝵ᒙ㐃⤖ィ⟬ࢆᮏ᱁ⓗ࡟ᐇ⾜ࡋࠊ⺮ⓑሙ࡜ᙉࡃ㐃⤖ࡋࡓ SCES (CaMn4O5) ࢩࢫࢸ࣒ࡢゐ፹ᶵ⬟ࡢᮏ㉁ࡢゎ᫂ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
2019 ᖺ࡟ሗ࿌ࡉࢀࡓⳢࡽࡢ S3 ≧ែࡢ SFX XFEL ᵓ㐀(PDB ID 6JLL)ࢆ⏝࠸ᅗ 2 ࡟♧ࡋࡓࡼ࠺࡟ࠊO(5)ࠊO(6)ཎᏊཬࡧ Mn4 ཎᏊ࡟㓄఩ࡋ࡚࠸ࡿ W2ࠊW1 ศᏊࡢࣉࣟࢺࣥ໬≧ែࢆኚ໬ࡉࡏࡓᵓ㐀ࢆసᡂࡋࡓࠋྛᵓ㐀࡟ᑐࡋ࡚ࡢᵓ㐀᭱㐺໬ࡣ NWChem ࢆ⏝࠸ࠊQM ィ⟬ࢆᐇ⾜ࡋࡓࠋᵓ㐀᭱㐺໬ࡢᡭἲ࡟ࡣ UB3LYP ࡟ Grimme ࡢ
D3 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-largeࣔࢹࣝࢆసᡂࡋ UB3LYP-D3 ࡢᡭἲ࡛᭱㐺໬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘ࡟ࡣࢥ࢔ࡢᵓ㐀࡟ࡣ Def2-TZVP ࡢᇶᗏࢆࠊ
semi-large ࣔࢹ࡛ࣝ᪂ࡓ࡟ຍ࠼ࡓ㓄఩Ꮚ࡟ࡣ Def2-SVP ᇶᗏࡢ 2 ᒙࡢᇶᗏ㛵ᩘࢆ⏝࠸(⣙ 4000 ᇶᗏ)ࠊ⎔ቃຠᯝࢆ COSMO ࡟ࡼࡾྲྀࡾධࢀࡓࠋ᭱㐺໬࡟ࡣྛᵓ㐀࡟ࡘ࠸࡚ࠊ⣙ 100 ࢧ࢖ࢡࣝ⛬ᗘࡢ཯᚟ࡀᚲせ࡜࡞ࡾࠊ406Rh2 ࢆ୪ิ౑⏝ࡍࡿࡇ࡜࡟ࡼࡾ㧗㏿࡞ィ⟬ࡀྍ⬟࡜࡞ࡗࡓࠋ
┦ᑐ࢚ࢿࣝࢠ࣮ࡢẚ㍑ࡢࡓࡵ HDFT ࡜ DLPNO-CC ࡢᡭἲࢆ⏝࠸ࠊ᭱㧗ࢫࣆࣥ≧ែ (S = 13/2ࠊPeroxo ࣔࢹ
ࣝࡢࡳ S = 15/2) ࡟ᑐࡋ࡚ᇶᗏ㛵ᩘ࡟ࡣ Def2-TZVPP ࢆ⏝࠸࡚ィ⟬ࢆ⾜࠸ (⣙ 2500 ᇶᗏ)ࠊ⎔ቃຠᯝ࡟ࡣCOSMO ࡲࡓࡣ CPCM ࢆ⏝࠸ࡓࠋHDFT ࡟ࡣ B3LYP ࡜ࡑࡢࡢ 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)ἲࢆࡑࢀࡒࢀ 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 ࡢࣉࣟࢢ࣒ࣛ
ࢆ OpenMPI3 ࡛୪ิฎ⌮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 ࡢ౑⏝࡟ࡼࡾຠ⋡ࡢⰋ࠸ィ⟬ࡀྍ⬟࡛࠶ࡗࡓࠋ
ᅗ2

S3 ≧ែࡢィ⟬ࣔࢹࣝ࡜ィ⟬ࡢᴫせ◊✲ᡂᯝᮏᖺᗘࡢሗ࿌᭩࡛ࡣࠊKok ࢧ࢖ࢡࣝࡢ S3 ≧ែࡢ CaMn4O6 ࢡࣛࢫࢱ࣮ࡢࢥ࢔ᵓ㐀࡟╔┠ࡋࡓࣔࢹࣝ࡟ࡘ࠸

࡚ࠊ⌮ㄽⓗ࡟ྍ⬟࡞୰㛫య㛫ࡢ┦ᑐ࢚ࢿࣝࢠ࣮࡜ࡑࢀࡒࢀࡢࢫࣆࣥ≧ែࢆྫྷ࿡ࡋࡓ⤖ᯝ[2]࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
OEC ࡢ࣐ࣥ࢞ࣥࡢ㓟໬≧ែࡣ High-valent ࡞㓟໬≧ែࢆ௬ᐃࡋࠊ࣐ࣥ࢞ࣥࡢ≧ែࢆ (Mn1, Mn2, Mn3, Mn4) = (IV,- 146 -

IV, IV, IV)࡜௬ᐃࡋ(Peroxo ≧ែࡢࡳ(III, IV, IV, III)ࡢࣂࣞࣥࢫ≧ែ)ࠊࡑࢀࡒࢀ୰㛫యࡢ࢚ࢿࣝࢠ࣮ẚ㍑ࢆ⾜ࡗࡓࠋ୰㛫యᵓ㐀ࡣ࢟ࣗࣂࣥᵓ㐀ࡀ㛤࠸ࡓ(R)ᵓ㐀࡜㛢ࡌࡓ(L)ᵓ㐀ࢆ௬ᐃࡋࠊᤄධࡉࢀࡓỈ(O(6)ཎᏊ)ࡢ㓟໬≧ែ࡟ᛂࡌ࡚ࡑࢀࡒࢀ Oxo ≧ែ(O2-)ࠊOH ≧ែ(OH-)ࠊH2O ≧ែ࡜࿨ྡࡋࡓࠋᵓ㐀᭱㐺໬ࡢ⤖ᯝࠊ(R)ᵓ㐀࡛ࡣࠊOH≧ែ࡟࠾࠸࡚ O(6)H ࡢỈ⣲⤖ྜࡢ᪉ྥࡀࠊO(5)ཎᏊ࡜Ỉ⣲⤖ྜࢆ࡜ࡿࡶࡢ(OH)࡜ Ca ࡜ Mn1 ࡟㓄఩ࡍࡿ Glu189
ࡢ࢝ࣝ࣎ࢽࣝ㓟⣲࡟㓄఩ࡍࡿ≧ែ(OHglu)࡜ࡀ࡛ࡁࠊH2O ࡢᵓ㐀ࡣᤄධࡉࢀࡓỈศᏊࡢỈ⣲ཎᏊࡢ⛣ື࡟ࡼࡾO(5)H ࡜ O(6)H ࡜࡟ศ࠿ࢀࡓࡓࡵࠊOHw ࡜࿨ྡࡋ࡚࠸ࡿࠋ(L)ᵓ㐀࡛ࡣ oxo ≧ែ࡟࠾࠸࡚Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡ
ࡢ␗࡞ࡿ≧ែࡀ⌧ࢀࠊࡑࢀࡒࢀ L1 ࡜ L2 ࡜࿨ྡࡋࡓࠋ
ࡑࢀࡒࢀࡢ࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚ࡳࡿ࡜ᅗ 3 ࡟ࡲ࡜ࡵࡓࡼ࠺࡟ࠊS3abca(R)-OHglu ᵓ㐀ࡣࠊHF 㡯ࡢ㔜㔞 (w) ࢆኚ࠼ࡓ HDFT ࡢ⤖ᯝ࡜ DLPNO-CCSD(T0)ࡢ⤖ᯝ࡛ S3 ୰㛫యࡢ୰࡛᭱ࡶᏳᐃ࡛࠶ࡗࡓࠋ୍᪉ࠊS3abca(L)-OH ᵓ㐀ࡣࠊHDFT(B3LYP)ࡢࣞ࣋ࣝ(w = 10ࠥ20%)࡛ S3abca(R)-OH ࡜ẚ㍑ࡋ࡚⣙ 6ࠥ7 kcal/mol ୙Ᏻᐃ࡛࠶ࡗࡓࠋࡋ࠿
ࡋࠊࢲࣈࣝ HDFT (UB2PLYP)࡛ࡣ L-OH ࡜ R-OH ࡢ㛫ࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣ࡯ࡰࢮࣟ࡟࡞ࡾࠊDLPNOCCSD(T0)࡛ࡣ L-OH ࡣ R-OH ࡼࡾࡶ 2ࠥ3kcal/mol ⛬ᗘᏳᐃ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋS3acca(R)-Oxo ᵓ㐀ࡣࠊࣁ࢖ࣈࣜࢵࢻ DFT (UB3LYP) (w = 10 ~ 20%) ࠾ࡼࡧ UB2PLYP ࡛ࣞ࣋ࣝࡣ S3abca(R)-OH ࡜ẚ㍑ࡋ࡚⣙ 15 ~ 16kcal/mol ୙Ᏻᐃ࡛࠶ࡾࠊࡇࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣ DLPNO-CCSD(T0)ἲ࡛ࡶኚ໬ࡋ࡞࠿ࡗࡓࠋS3acca(L1)-Oxo࡜ S3acca(L2)-Oxo ᵓ㐀ࡣ HDFT ࡛ࣞ࣋ࣝࡣ S3abca(R)-OH ࡜ẚ㍑ࡋ࡚⣙ 7 ~ 9 kcal/mol ୙Ᏻᐃ࡛࠶ࡗࡓࠋUB2PLYP࡜ DLPNO-CCSD ࡛ࡣࡑࢀࡒࢀ⣙ 2 kcal/mol ࡜ 4 kcal/mol ࡲ࡛ῶᑡࡋࠊDLPNO-CCSD(T0) ࡛ࡣ S3abca(R)-OH
ࡼࡾࡶ⣙ 1 kcal/mol Ᏻᐃ࡛࠶ࡗࡓࠋS3bbba(R)-OHw ࡣ S3abca(R)-OH ࡜ẚ㍑ࡋ࡚ HDFT ࠾ࡼࡧ DHDFT ࡛ࡣࠊ1 ~2kcal/mol ⛬ᗘᏳᐃ࡛࠶ࡗࡓ୍᪉ࠊDLPNO-CCSD(T0)࡛ࡣ┦ᑐᏳᐃᛶࡀ㏫㌿ࡋࡓࠋS3acca(L)-H2O ᵓ㐀ࡣࠊHDFT
࡛ࣞ࣋ࣝࡣ S3abca(R)-OH ࡜ẚ㍑ࡋ࡚⣙ 6 ~ 7 kcal/mol ୙Ᏻᐃ࡛࠶ࡗࡓࡀࠊDLPNO-CCSD(T0)࡛ࡣ 1ࠥ
2kcal/mol ࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ࡜࡞ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋྛ୰㛫యᵓ㐀࡟ࡘ࠸࡚ࢫࣆࣥ≧ែࡢホ౯ࢆ⾜࠺ࡓࡵ࡟ BS-DFT ࡟ࡼࡾྛᵓ㐀࡟ࡘ࠸࡚୰㛫ࢫࣆࣥ≧ែࢆồࡵ᭷ຠ஺᥮✚ศࢆ (J ್) ィ⟬ࡋࡓࡢࡕࠊࢫࣆࣥࣁ࣑ࣝࢺࢽ࢔ࣥ⾜ิࡢཝᐦᑐゅ໬࡟ࡼࡾࢫࣆࣥ≧ែ㛫ࡢࢠࣕࢵࣉ࡜ྛ࣐ࣥ࢞ࣥࢧ࢖ࢺ࡟ࡘ࠸࡚ࡢࣉࣟࢪ࢙ࢡࢩࣙࣥࣇ࢓ࢡࢱ࣮ (ȡ  ࢆồࡵࡓࠋྛᵓ㐀ࡢࣉࣟࢪ࢙ࢡࢩࣙࣥ
ࣇ࢓ࢡࢱ࣮ࡣ⾲ 1 ࡟ࡲ࡜ࡵࡓࠋS3abca(R)-OHࠊS3abca(R)-OHgluࠊS3bbba(R)-OHw ࡢᇶᗏࢫࣆࣥ≧ែࡣࠊCox ࡸ Boussac
ࡽࡢ EPR ࡢᐇ㦂᳨࡛ฟࡉࢀࡓ୰㛫ࢫࣆࣥ≧ែ(IS) (S = 3) ≧ែ࡜୍⮴ࡋ࡚ࠊSeptet (S = 3) ≧ែ࡛࠶ࡗࡓࠋSeptetᅗ3S3 ≧ែࡢ┦ᑐ࢚ࢿࣝࢠ࣮

- 147 -

⾲ 1.

S3 ≧ែࡢࢫࣆࣥ≧ែࠊບ㉳≧ែ࡜ࣉࣟࢪ࢙ࢡࢩࣙࣥࣇ࢓ࢡࢱ࣮(ȡStructures

S

E [cm–1]

ρ (Mn1)

ρ (Mn2)

ρ (Mn3)

ρ (Mn4)

S3abca(R)-OH

3

0.0

0.477

0.471

0.053

-0.001

4

3.94

0.368

0.367

0.139

0.126

3

0.0

0.500

0.478

0.247

-0.225

4

4.31

0.375

0.369

0.184

0.072

3

0.0

0.488

0.464

0.394

-0.346

4

15.7

0.370

0.351

0.275

0.004

4

0.0

0.343

0.374

0.014

0.269

3

1.87

0.452

0.496

–0.329

0.381

6

0.0

0.250

0.250

0.250

0.250

5

31.2

0.205

0.294

0.292

0.209

6

0.0

0.250

0.250

0.250

0.250

5

43.5

0.218

0.291

0.297

0.194

3

0.0

0.497

0.492

0.223

–0.211

4

15.3

0.375

0.373

0.173

0.080

3

0.0

0.496

0.470

0.340

–0.306

4

62.5

0.372

0.360

0.230

0.036

S3abca(R)-OHglu
S3acba(L)-OH
S3acca(R)-Oxo
S3acca(L1)-Oxo
S3acca(L2)-Oxo
S3bbba(R)-OHw
S3abba(L)-H2O(S = 3) ≧ែ࡜ Nonet (S = 4) ≧ែࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣࡑࢀࡒࢀ 3.94ࠊ4.31ࠊ15.3 cm-1 ࡛࠶ࡗࡓࠋࡋࡓࡀࡗ
࡚ࠊ⾲ 1 ࡟࠶ࡿࡼ࠺࡟ࣉࣟࢪ࢙ࢡࢩࣙࣥࣇ࢓ࢡࢱ࣮࠿ࡽุ᩿ࡍࡿ࡜ࠊIS (S = 3) ࡢ EPR ࢩࢢࢼࣝࢆᣢࡘ S3EPR(R)(Cox et al., Science, 345, 804 (2014)) ࡢೃ⿵࡜ࡋ࡚ࡣࠊS3abca(R)-OHࠊS3abca(R)-OHgluࠊS3bbba(R)-OHw ࡀ⪃࠼ࡽࢀࠊᅗ 3 ࡢ┦ᑐ࢚ࢿࣝࢠ࣮࡜࠿ࡽ S3abca(R)-OHglu ࡀ᭱ࡶ☜࠿ࡽࡋ࠸࡜ゝ࠼ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋS3abca(L)-OH ࡜
S3abba(L)-H2O ࡢᇶᗏࢫࣆࣥ≧ែࡶ Septet ࡛࠶ࡾࠊNonet ≧ែ࡜ࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣࡑࢀࡒࢀ 15.7ࠊ62.5 cm1࡛࠶ࡗࡓࠋࡋࡓࡀࡗ࡚⾲ 1 ࡢࣉࣟࢪ࢙ࢡࢩࣙࣥࣇ࢓ࢡࢱ࣮࡜࠿ࡽࠊS3abca(L)-OH ࡜ S3abba(L)-H2O ࡣ IS (S = 3)

ࡢ EPR ಙྕࢆᣢࡘ S3EPR(L) (Chrysina et al., PNAS, 116, 16841 (2019)) ࡢೃ⿵࡛࠶ࡿྍ⬟ᛶࡀ࠶ࡿࠋࡋ࠿ࡋࠊ
S3abca(L)-OH ࡣ S3abba(L)-H2O ࡼࡾ࢚ࢿࣝࢠ࣮ⓗ࡟᭷฼࡛࠶ࡿ୍᪉ࠊS3abba(L)-H2O ࡣࠊᴟప࡛ࡢ㏆㉥እ⥺࡟ࡼࡿ㟁Ꮚ⛣ື࡛ IS (S = 5/2) + Tyr-O ࣛࢪ࢝ࣝࢆᣢࡘ S2abba(L)-H2O ࡟ᡠࡿࡇ࡜ࡢ࡛ࡁࡿ S3 ୰㛫యࡢ㔜せ࡞ᵓ㐀࡜⪃࠼ࡽࢀࡿࠋS3acca(L1)-Oxo ࡜ S3acca(L2)-Oxo ࡢᇶᗏ≧ែࡣ㧗ࢫࣆࣥ(S = 6)࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋບ㉳≧ែ(S= 5)࡜ࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣࠊࡑࢀࡒࢀ 32.2cm-1 ࡜ 43.5 cm-1 ࡛࠶ࡗࡓࠋS3acca(L1)-Oxo ࡜ S3acca(L2)-Oxoࡣ EPR ࠿ࡽᥦ᱌ࡉࢀࡓ EPR silent ࡞ᵓ㐀(Boussac et al., BBA, 1859, 342 (2018))ࡢೃ⿵࡛࠶ࡿࠋࡇࢀࡽ࠿ࡽࠊPSII
ࡢ OEC ࡢ S3 ≧ែ࡟ࡣ」ᩘࡢ୰㛫యࡀᏑᅾࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
ࡲࡓỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࠊ࡜ࡃ࡟ Glu189 ࿘ࡾࡢ⎔ቃࡢ㔜せᛶ࠿ࡽ CaMn4O6 ࢡࣛࢫࢱ࣮ࡢ➨஧㓄఩Ꮚ࡟ࡶ╔┠ࡋࡓ semi-large QM ࣔࢹࣝ (227 ཎᏊ⣔) ࡟ࡼࡿ᭱㐺໬ᵓ㐀ࢆ⾜ࡗࡓ࡜ࡇࢁࠊOHglu ᵓ㐀࡛ࡣỈศᏊ W7
࡜ O(6)H-࡜ࡀ Glu189 ࡟Ỉ⣲⤖ྜࡋࠊࡲࡓ W7 ࡜ W5 ࡀỈ⣲⤖ྜࡋ࡚࠸ࡿᵝᏊࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢࡇ࡜࠿
ࡽࠊS3abca(R)-OHgluЍW7ЍW5ЍS3acca(R)-Oxo ࡲࡓࡣ S3acca(R)-Oxyl ࡜࠸࠺ࣉࣟࢺࣥ⛣ື⤒㊰ࡀ♧၀ࡉࢀࠊGlu189
ࡀ Oxo(R)ᵓ㐀ࡸ Oxyl ᵓ㐀ࡢᙧᡂ࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊPSII ࡢࢱࣥࣃ- 148 -

ࢡ㉁ሙ࡜ᙉࡃ⤖ྜࡋࡓ Mn-oxyl ୰㛫యࡢ S3 ≧ែ࡛ࡢᏳᐃ໬ᶵᵓࢆゎ᫂ࡍࡿࡓࡵ࡟ࡣࠊỈࡢศゎ཯ᛂ࡟࠾ࡅࡿ
O-O ⤖ྜᙧᡂ࡟ Ca ࢖࢜ࣥ(ࣝ࢖ࢫ㓟)ࡢᙺ๭ࢆᢸࡗ࡚࠸ࡿࡇ࡜࡞࡝࡜ࡶ㛵㐃ࡋࡓ㆟ㄽࡀᚲせ࡜࡞ࡾࠊᣑᙇࢡࣛ
ࢫࢱ࣮ࣔࢹࣝࢆ⏝࠸ࡓ᫬㛫ࡢ࠿࠿ࡿ DLPNO-CCSD(T)ィ⟬ࡀᚲせ࡛࠶ࡿࡓࡵ⌧ᅾゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ගᏛ⣔ II ࡟࠾ࡅࡿ㓟⣲Ⓨ⏕୰ᚰࡢ S3 ≧ែ࡛ࡢ୰㛫యᵓ㐀ࡢ㟁Ꮚ≧ែࡢ DFT ࡜ CC ἲ࡟ࡼࡿゎᯒ, ᐑᕝ᫭୍, ᕝୖ㈗㈨, ᗉྖග⏨, ☾㒊 ᐶ, ᒣཱྀ඙, ➨ 47 ᅇ⏕యศᏊ⛉Ꮫウㄽ఍ 2021 ᖺ 6 ᭶ 4 ᪥(㔠)㹼5 ᪥(ᅵ), ࢜ࣥࣛ࢖ࣥ㛤ദ, (࣏ࢫࢱ࣮Ⓨ⾲)ගᏛ⣔ II ࡟࠾ࡅࡿ㓟⣲Ⓨ⏕୰ᚰࡢ S1 ≧ែ࡛ࡢ୰㛫యᵓ㐀ࡢ㟁Ꮚ≧ែࡢ DFT ࡜ CC ἲ࡟ࡼࡿゎᯒ, ᐑᕝ᫭୍, ᕝୖ㈗㈨, ᗉྖග⏨, ☾㒊 ᐶ, ᒣཱྀ ඙, 㔜⏣⫱↷, 㘒య໬Ꮫ఍ ➨ 71 ᅇウㄽ఍, 2021 ᖺ 9 ᭶ 16 ᪥(ᮌ)ࠥ19
᪥(᪥), ࢜ࣥࣛ࢖ࣥ㛤ദ (࣏ࢫࢱ࣮Ⓨ⾲)
Mn ୕᰾㘒య(YMn3O4)࡛ࡢ㟁Ꮚ≧ែ࡜☢Ẽⓗ┦஫స⏝࡟㛵ࡍࡿ CASCI-DMRG,-QMC ἲ࡟ࡼࡿゎᯒ, ᕝୖ㈗㈨, ᅵᕝ┿⌮ᜨ, 㕥ᮌ㞝ኴ, ᐑᕝ᫭୍, ᒣ୰⚽௓, ዟᮧග㝯, ୰ᔱ㝯ே, ᒣཱྀ ඙, ศᏊ⛉Ꮫウㄽ఍, 2021 ᖺ 9
᭶ 18 ᪥(ᅵ)ࠥ21 ᪥(ⅆ), ࢜ࣥࣛ࢖ࣥ㛤ദ (࣏ࢫࢱ࣮Ⓨ⾲)㕲࣏ࣝࣇ࢕ࣜࣥ-㓟⣲ࣔࢹࣝ㘒యࡢ඲࡚ࡢ㟁Ꮚ≧ែࡢ hybrid-DFT ࠾ࡼࡧ CAS ἲ࡛ࡢゎᯒ, ᅵᕝ┿⌮ᜨ, ᕝ
ୖ㈗㈨, ᐑᕝ᫭୍, ᒣ୰⚽௓, ዟᮧග㝯, ୰ᔱ㝯ே, ᒣཱྀ ඙, ศᏊ⛉Ꮫウㄽ఍, 2021 ᖺ 9 ᭶ 18 ᪥(ᅵ)ࠥ21 ᪥(ⅆ), ࢜ࣥࣛ࢖ࣥ㛤ദ (࣏ࢫࢱ࣮Ⓨ⾲)
Mn ୕᰾㘒య(YMn3O4)ࡢ➇ྜࡍࡿ☢Ẽⓗ┦஫స⏝⤒㊰࡟㛵ࡍࡿ hybrid DFT ἲ࠾ࡼࡧ CASCI-DMRG ἲ࡟ࡼࡿゎᯒ, ᕝୖ㈗㈨, ᅵᕝ┿⌮ᜨ, 㕥ᮌ㞝ኴ, ᐑᕝ᫭୍, ᒣ୰⚽௓, ዟᮧග㝯, ୰ᔱ㝯ே. ᒣཱྀ ඙, ࢥࣥࣆ࣮ࣗ
ࢱ໬Ꮫ఍ 21 ᖺ 11 ᭶ 2 ᪥-3 ᪥, ⟃Ἴ኱Ꮫ (࢜ࣥࣛ࢖ࣥ㛤ദ), (࣏ࢫࢱ࣮Ⓨ⾲)ගᏛ⣔ II ࡟࠾ࡅࡿ㓟⣲Ⓨ⏕୰ᚰࡢ S1 ≧ែ࡛ࡢ୰㛫యᵓ㐀ࡢ㟁Ꮚ≧ែࡢ DFT ࡜ CC ἲ࡟ࡼࡿゎᯒ, ᐑᕝ᫭୍, ᕝୖ㈗㈨, ᗉྖග⏨, ☾㒊 ᐶ, ᒣཱྀ ඙, 㔜⏣⫱↷, ࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 21 ᖺ 11 ᭶ 2 ᪥-3 ᪥, ⟃Ἴ኱Ꮫ(࢜ࣥࣛ࢖ࣥ㛤ദ), (࣏ࢫࢱ࣮Ⓨ⾲)ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࣊ࣜ࢜ࣟࢻࣉࢩࣥࡢள㖄⤖ྜ࡟㛵ࡍࡿ◊✲, ᐑᕝ᫭୍, ᗉྖග⏨, 㔜⏣⫱↷,ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ 2021, 2022 ᖺ 1 ᭶ 11 ᪥(ⅆ)㹼12 ᪥(Ỉ), Zoom ࡟ࡼࡿ࢜ࣥࣛ࢖ࣥ㛤ദ,(࣏ࢫࢱ࣮Ⓨ⾲)㧗ཎᏊ౯ Mn ୕᰾㘒య([Mn3(IV)O4]4+)ࡢ㟁Ꮚ≧ែ࡜☢Ẽⓗ┦஫స⏝࡟㛵ࡍࡿ CASCI-DMRG ἲ࡟ࡼࡿゎᯒ,
ᕝୖ㈗㈨࣭ᅵᕝ┿⌮ᜨ࣭㫽ᒃ┿ே࣭ᐑᕝ᫭୍࣭ᒣ୰⚽௓࣭ዟᮧග㝯࣭୰ᔱ㝯ே࣭ᒣཱྀ඙, ➨ 102 ᫓Ꮨᖺ఍ 2022
ᖺ 3 ᭶ 23 ᪥(Ỉ)㹼26 ᪥(ᅵ), ࢜ࣥࣛ࢖ࣥ㛤ദ (ཱྀ㢌Ⓨ⾲)ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫[ۻ‬1] Relative energies among proton-shifted S2 isomers in the photosystem II revealed by DLPNO coupled cluster

and hybrid DFT calculations. Proton transfer coupled spin transitions of the CaMn4Ox cluster in OEC of PSII, K.
Miyagawa, M. Shoji, H. Isobe, T. Kawakami, T. Nakajima, and K. Yamaguchi, Chem. Phys. Lett. 790, 139357 (11 pages)(2022). DOI: 10.1016/j.cplett.2022.139357.
‫[ۻ‬2] Relative energies among S3 intermediates in the photosystem II revealed by DLPNO coupled cluster and hybrid
DFT calculations. Possible pathways of water insertion in the S2 to S3 transition, K. Miyagawa, M. Shoji, H. Isobe, T.
Kawakami, T. Nakajima, and K. Yamaguchi, Chem. Phys. Lett. 793, 139439 (12 pages) (2022). DOI:
10.1016/j.cplett.2022.139439.

- 149 -

‫[ۻ‬3] Isolobal and isospin analogy between organic and inorganic open-shell molecules̾Application to oxygenation
reactions by active oxygen and oxy-radicals and water oxidation in the native and artificial photosynthesis, Kizashi
Yamaguchi, Koichi Miyagawa, Hiroshi Isobe, Mitsuo Shoji, Takashi Kawakami, and Shusuke Yamanaka, in E.J. Brändas
eds., Advances in Quantum Chemistry Volume 84, Elsevier, 2021, pp.425-564. DOI: 10.1016/bs.aiq.2021.10.001.
[4] Mechanism of Water Oxidation in Photosynthesis Elucidated by Interplay Between Experiment and Theory, Kizashi
Yamaguchi, Shusuke Yamanaka, Hiroshi Isobe, Mitsuo Shoji, Takashi Kawakami, and Koichi Miyagawa, in J.-R. Shen,
K. Satoh, and S.I. Allakhverdiev eds. Photosynthesis: Molecular Approaches to Solar Energy Conversion, vol 47, Springer,
Cham., 2021, pp. 39-80. DOI: 10.1007/978-3-030-67407-6_2.
[5] ศᏊືຊᏛィ⟬࡟ࡼࡿࢢ࢔ࢽࣥࣂࣝࢪ DNA ࡟⤖ྜࡍࡿᑠศᏊ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲, ᐑᕝ᫭୍, ࢔ࣥࢧࣥࣈࣝ, 23, 143-147 (2021). DOI: 10.11436/mssj.23.143.

- 150 -

୕ḟඖࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀ᛶ
6WUXFWXUHDQG3URSHUWLHVRI7KUHHGLPHQVLRQDOS&RQMXJDWHG0ROHFXOHV‫ۑ‬ὠ␃㷂 㝧኱㸦኱㜰ᗓ❧኱Ꮫ኱Ꮫ㝔⌮Ꮫ⣔◊✲⛉㸧1◊✲┠ⓗ2021 ᖺᗘ࡛ࡣᮏ⏦ㄳㄢ㢟࡜୪⾜ࡋ࡚ᐇ᪋ࡋ࡚࠸ࡿࠕࢪ࣍ࢫࣇ࢙ࣥ㓄఩Ꮚࢆ⏝࠸ࡓ㑄⛣㔠ᒓゐ፹཯ᛂࡢ㛤Ⓨࠖ࡟㛵ࡍࡿ◊✲࡟ᑐࡋ࡚ࠊィ⟬ࢆ㔜Ⅼⓗ࡟⾜ࡗࡓࡓࡵࡑࡢ◊✲ᡂᯝࢆ௨ୗ࡟♧ࡍࠋ㧗άᛶ࠿ࡘ㧗㑅ᢥⓗ࡞㑄⛣㔠ᒓゐ፹཯ᛂࢆᐇ⌧ࡍࡿ㓄఩Ꮚࡢ㛤Ⓨࡣࠊຠ⋡ⓗ࡞໬ྜ≀ࡢኚ᥮ࡀྍ⬟࡜࡞ࡿࡓࡵ㔜せ࡞◊✲ㄢ㢟ࡢ୍ࡘ࡛࠶ࡿࠋᡃࠎࡣࠊࣜࣥ㸫ࣜࣥ஧㔜⤖ྜࢆ᭷ࡍࡿࢪ࣍ࢫࣇ࢙ࣥ࡟╔┠ࡋ࡚࠾ࡾࠊ᭱
㏆࢚ࢳࣞࣥᯫᶫࣅࢫ(ࣅࢼࣇࢳࣝࢪ࣍ࢫࣇ࢙ࣥ) (S,S)-1 ࢆ㛤Ⓨࡋࡓࠋᚓࡽࢀࡓࣅࢫ(ࢪ࣍ࢫࣇ࢙ࣥ) (S,S)-1 ࡜
PdCl2(cod) ࡜ࡢ㘒ᙧᡂ཯ᛂࢆ᳨ウࡋࡓ࡜ࡇࢁࠊ᪂ࡓ࡞㘒య 2 ࡀᚓࡽࢀࡓ(Scheme 1)ࠋ31P NMR ࠾ࡼࡧ MS ࢫ࣌ࢡࢺࣝᐃ࠿ࡽK1, K2 㓄఩ࡋࡓ༢᰾㘒య࡛࠶ࡿࡇ࡜ࡣ♧၀ࡉࢀࡓࡶࡢࡢࠊX ⥺⤖ᬗᵓ㐀ゎᯒ࡟㐺ࡋࡓ༢⤖ᬗࡀᚓࡽࢀ࡞࠿ࡗࡓࡓࡵࠊ༑ศ࡞ᵓ㐀Ỵᐃ࡟ࡣ⮳ࡽ࡞࠿ࡗࡓࠋ31P NMR ࡢ໬Ꮫࢩࣇࢺ್࠾ࡼࡧ࢝ࢵࣉࣜࣥࢢᐃᩘ
࡟ࡼࡾࠊࣃࣛࢪ࣒࢘ୖࡢሷ⣲ཎᏊࡀࣜࣥཎᏊ࡬࡜㌿఩ࡋࡓ㘒య 2 (Scheme 1)࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋࡑࡇ࡛ࠊィ⟬໬Ꮫࡢᡭἲࢆ⏝࠸࡚ࠊ␗ᛶయ㛫ࡢᏳᐃᛶ࡜ 31P NMRࡢ໬Ꮫࢩࣇࢺ್ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊணᵓ㐀ࡢጇᙜᛶࢆホ౯ࡍࡿࡇ࡜࡜ࡋࡓࠋࡲࡓࠊሷ⣲ࡢ㌿఩࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡶ┠ᣦࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ

Scheme 1.

*DXVVLDQ ࠾ࡼࡧ *550 ࢆ฼⏝ࡋࡓࠋ06'' 3G * G  3&O&+  ࣞ࣋ࣝࢆᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊ
Ᏻᐃᵓ㐀࠾ࡼࡧ㑄⛣≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ 3&0 &+&O ࠋᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ࡣࠊྠࣞ࣋ࣝ࡟࡚᣺
ືᩘィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾᏳᐃᵓ㐀ࡶࡋࡃࡣ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡲࡓࠊ㑄⛣≧ែ࡟ࡘ࠸࡚ࡣ ,5&ィ⟬ࢆᐇ᪋ࡋࠊ஧ࡘࡢᏳᐃᵓ㐀ࢆࡘ࡞ࡄ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࡶ࠶ࢃࡏ࡚☜ㄆࡋࡓࠋ105 ィ⟬࡟ࡣࠊ2/<36''
3G * GS  3&O&+  ࣞ࣋ࣝࢆ⏝࠸ࡓ 3&0 &+&O ࠋ3◊✲ᡂᯝሷ⣲ࡢ㌿఩఩⨨ 33 ࠊ3 ࡜ 3 ୖࡢⅣ⣲

⨨᥮ᇶࡢ఩⨨㛵ಀ WUDQV FLV ࡟ࡼࡾࠊ ✀㢮ࡢ␗ᛶయ $' ࡀ⪃࠼ࡽࢀࡿࡀࠊሷ⣲ࡀእഃ
ࡢ 3 ࡟㌿఩ࡋࠊ0HV ᇶ࡜ࣅࢼࣇࢳࣝᇶࡀ
WUDQV 㓄⨨࡜࡞ࡗࡓ $ ࡀ᭱Ᏻᐃ࡛࠶ࡿࡇ࡜
ࡀศ࠿ࡗࡓࠋࡲࡓࠊ$ ࡣ 3G&O ࡟ᑐࡋ࡚஧
ࡘࡢࢪ࣍ࢫࣇ࢙ࣥ㒊఩ࡀ Ș 㓄఩ࡋࡓ㘒య (
࡜ẚ㍑ࡋ࡚  NFDOPROí Ᏻᐃ࡛࠶ࡾࠊ㌿఩ࡀ㐍⾜ࡋ࠺ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
Figure 1.

ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ  ✀㢮ࡢ㘒య࡟ᑐࡋ

- 151 -

࡚ࠊ*,$2 ィ⟬࡟ࡼࡾ 3 ࡢ໬Ꮫࢩࣇࢺ್ࢆ⟬ฟࡋࡓ࡜ࡇࢁ 7DEOH ࠊȘ 㓄఩ࡋࡓ 3 ࡜ 3 ࡢ್ࡣ࠸ࡎࢀࡶ㧗☢ሙ㡿ᇦ࡟୚࠼ࡓࠋ㘒య $ ࡢィ⟬್ࡀᐇ್࡜ẚ㍑ⓗ㏆࠸್ࢆ♧ࡋࡓࠋḟ࡟ࠊሷ⣲ࡀ㌿఩ࡍࡿ⤒㊰࡟ࡘ࠸᳨࡚ウࡋࡓࠋࢪ࣍ࢫࣇ࢙ࣥ(S,S)-1 ࡜> SDOO\O FRG 3G@ 6E) ࡜ࡢ཯ᛂ࡛ࡣࠊȘȘࢪ࣍ࢫࣇ࢙ࣥ㘒యࡀᚓࡽࢀࡿ


3
3
3
3

-33

33
-33



í
+]
+]+]

$
%
&
'
















í+] í+] í+] í+]
+] +] +]
+]
í+] í+] í+] í+]
್ ࠾ࡼࡧ $' ィ⟬್ ࡢ 3105 ໬Ꮫࢩࣇ

Table 1. 㘒య  ᐇࢺ್࠾ࡼࡧ -33 ࢝ࢵࣉࣜࣥࢢࢥࣥࢫࢱࣥࢺ

ࡇ࡜࠿ࡽࠊ(S,S)-1 ࡜ 3G&O FRG ࡜ࡢ཯ᛂ࡛ࡶࠊFRG࡜ࡢ㓄఩Ꮚ஺᥮࡟ࡼࡾ ȘȘࢪ࣍ࢫࣇ࢙ࣥ㘒య ( ࡀ⏕ᡂࡍࡿ࡜᥎

ࡉࢀࡿࠋࡑࡇ࡛ࠊ( ࠿ࡽ $ ࡶࡋࡃࡣ %࡬ࡢᵓ㐀ኚ໬ࢆ᳨ウࡋࡓࠋᚓࡽࢀࡓ⤖ᯝࢆ )LJXUH ࡟♧ࡍࠋࡲࡎࠊ㘒య ( ࡢ୍᪉ࡢࢪ࣍ࢫࣇ࢙ࣥ㒊఩ 3í3
ࡀ᥋㏆ࡋ࡚ᅄဨ⎔ᵓ㐀 3G33&O ࢆᣢࡘ୰㛫య ,QW ࢆ⏕ࡌࡓࡢࡕࠊ3Gí&O ⤖ྜ㛤⿣࡜ 3í&O ⤖ྜᙧᡂࡀ⏕ࡌ࡚୰㛫య ,QW ࢆ୚࠼ࡿࠋࡑࡢᚋࠊ3 ࡢ❧య཯㌿ࡀ㐍⾜ࡋ࡚ࠊࡼࡾᏳᐃ࡞୰㛫య ,QW$ ࡟⮳ࡿࠋ⏕ࡌࡓ୰㛫య ,QW$ ࠿ࡽ┤᥋ 3í3G 㓄఩⤖ྜࡀᙧᡂࡋࡓሙྜ࡟ࡣࠊ㘒య $ ࡀᚓࡽࢀࡿࡢ࡟ᑐࡋࠊ3 ࡢ❧య཯㌿ࢆకࡗࡓሙྜ࡟ࡣ ,QW%ĺ,QW%ĺ% 㘒య % ࡀᚓࡽࢀࡓࠋ76% ࡢάᛶ໬㞀ቨࡀ᭱ࡶ㧗࠸ࡇ࡜࠿ࡽࠊ㘒య % ࡼࡾࡶ㘒య $ ࡢ⏕ᡂࡀ᭷฼࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊࡑࡢ್ࡣᐊ

୰࡛ࡶ༑ศ࡟㐍⾜ࡋ࠺ࡿ࡯࡝ప࠸ࡇ࡜

ࡀศ࠿ࡗࡓࠋ㘒య  ࡢᏳᐃᛶࡢẚ㍑ࠊ3 ࡢ໬Ꮫࢩࣇࢺ್ࡢẚ㍑ࠊሷ⣲ࡢ㌿఩ࡢᶵᵓゎ᫂ࡢ⤖ᯝ࠿ࡽࠊ㘒య
$ ࡀᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀጇᙜ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

)LJXUH ࣃࣛࢪ࣒࢘㘒య ( ࠿ࡽ $ ࡶࡋࡃࡣ % ࡬ࡢኚ᥮࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮ᅗ'* ್ NFDOPROí ࢆグ㍕ 

4

ฟ∧ᐇ⦼

‫ ۻ‬R. Ura, $ 7VXUXVDNL . .DPLNDZD ³3DOODGLXP ,,  &RPSOH[HV RI %LV GLSKRVSKHQH  ZLWK 'LIIHUHQW &RRUGLQDWLRQ%HKDYLRUV´'DOWRQ7UDQV‫ ۻ‬$ <XEXWD $ 7VXUXVDNL . .DPLNDZD ³7UDQVIRUPDWLRQ IURP WULSOH KHOLFHQH WR GRXEOH KHOLFHQH HPEHGGLQJDGMDFHQWVWHUHRJHQLFFDUERQDWRPVDQGD[LDOVWHUHRJHQLFLW\´&KHP&RPPXQ - 152 -



Theoretical Study on the Aggregation-Induced Emission
 

&

#

'

1 ÇuÜYJ¡OÜSgeRÓ&¡O&z(»O¸­£'& ÁRÓ¿Â¡OÚAggregation-Induced Emission ; AIEÛ_'&+5<?(Bµq²^X^ÚBµqSg; ` 1ÛÜSgP«J[¡!È("Ü± ÈE]r or F©Ø zJFÏJ(y}&Þ1ß SgÜsºS{ )»O(¡ÜRÓ&¡Oxw 100 N¨wcV&BµqSg # AIE z(¡&
8*1/7ÜRÓHÈ[ÅÉW~T'&!'&Þ1ßÜ¾®D
&¤ªÜBµqSg¥ AIE Sg, Sg-69=A-:?ÚÔg{½¬@SgWUi½¬Ûb À¢¼\%¯)
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       `  $ &KHPLFDOVWUXFWXUHRIWULVNHOLRQVKDSHGPROHFXOH % ORFDOPLQLPXPVWUXFWXUHRSWLPL]HGDWWKHHOHFWURQLF

JURXQG 6 VWDWH 60,1 DQG & VWUXFWXUHDWWKHPLQLPXPHQHUJ\FRQLFDOLQWHUVHFWLRQEHWZHHQWKH6DQGILUVW
H[FLWHG 6 VWDWHV 660(&,  %BµqSgÔg{Ü.2?m¦z(´|.2?[ÅÑLhlwÒÚSA-SF-TD-DFTÛ(¼DFT Ò BHHLYPÜbvÒ 6-31G(d) (3>,;7 GAMESS(K

 
` 1 ¥#ÜBµqSg+5<?ÍI(³ Ef4?0?ÙÜbv{ËXÈÚS0MIN; ` 1BÛtÖ&ÜS1/S0 QÐGpÚS1/S0-MECI; ` 1CÛ·&4?0?ÙPÝM­ZgC $'&#dyÕtÖ envelope a& $- 153 -

` 2 ¥#Ü¶Ì§ÄÊÚNTOÛ¼$ÜS0S1 Ì§HSgEf4?0?Ù­-­ÑFÎ±^z×¹n& S&Ü ÍIÕtÖa& S1/S0-MECI
ÜS0 {¹ Djk&ÜS1 {Æ¢jk&!ÜS1/S0 ÖGp&´
$'&





` 2. Natural transition orbitals (NTOs) for the S0S1 transition.

` 3A ¥#ÜS0-MIN  S1/S0-MECI (³°Ã" ?- AdX(¼±ÜBµqSgÜOÂ#% S0S3 Ì§^ÜPÍÅÚS3S1Û(°ÜEf4?0?ÙdyÚ` 1C & 3BÛ(H S1/S0 QÐGp·& Ü$*#& $ ÜRÓ{Ü #ÈdX~T'& ÜAIE (¡&´$'&      

` 3. (A) Potential energy profiles and (B) changes in twist angles (defined in Fig. 1A) of the triskelion-shaped

molecule along the path connecting between S0-MIN and S1/S0-MECI.

$!

 ! ,  , +5<?(&BµqSgRÓ¿Â¡OÀ¢¤ª, ' 15  Sg&i)À , ?;?,.A¡(, 2P086, 2021 u 9  19 

 Norifumi Yamamoto, Theoretical insights into the mechanisms of aggregation-induced emission of a cyanostilbene
derivative, Pacifichem 2021, ?;?,.A¡(, 2021 u 12  19 

 ! , C% ,  , BµqSgRÓ¿Â¡O8*1/7À¢¤ª, Xi' 103 u ,.A¡(, P1-3pm-24, 2022 u 3  23 

!
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[1] Ueda, M., Kokubun, M., Mazaki, Y., ChemPhotoChem, Vol. 4, pp. 5159-5167 (2020)- 154 -

࣓࢝ࣞ࢜ࣥࣔࢹࣝ࡟ࡼࡿࢱࣥࣃࢡ㉁ᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉゎᯒ
)UHHHQHUJ\ODQGVFDSHDQDO\VLVRIWKHFRQIRUPDWLRQDOWUDQVLWLRQRISURWHLQVE\WKHFKDPHOHRQPRGHO‫ۑ‬ᑎ⏣ ᬛᶞࠊ➲஭ ⌮⏕㸦ྡྂᒇ኱Ꮫ㸧



◊✲┠ⓗ
㓝⣲཯ᛂࡸศᏊ࣮ࣔࢱ࣮࡞࡝ࠊࢱࣥࣃࢡ㉁ࡢᶵ⬟Ⓨ⌧࣓࢝ࢽࢬ࣒ࢆ⌮ゎࡋไᚚࡍࡿࡓࡵ࡟ࡣࠊࡑࡢ㏵୰࡛㉳ࡇࡿ⌧㇟ࢆ❧యᵓ㐀࡟ࡶ࡜࡙࠸࡚≉ᚩ࡙ࡅࡿᚲせࡀ࠶ࡿࠋࡑࡋ࡚ࡑࡢ᪉ἲ࡜ࡋ࡚᭱㏆ࠊᐇ㦂ⓗ࡟᪤▱ࡢᵓ㐀㌿⛣๓ᚋࡢ❧యᵓ㐀ࢆ⤖ࡪ⤒㊰ࢆࠊ඲ཎᏊศᏊືຊᏛィ⟬࡟ࡼࡗ࡚ᚓࡿ࡜࠸࠺᪉㔪ࡀ࡜ࡽࢀࡿࡼ࠺࡟࡞ࡗ
࡚ࡁࡓࠋࡋ࠿ࡋࠊィ⟬㔞ࡢไ⣙࠿ࡽࠊࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡿᵓ㐀ࡣࠊ᪤▱ࡢᵓ㐀࡝࠺ࡋࢆ┤⥺ⓗ࡟⤖ࡪ⤒㊰ࡢ㏆ഐ࡟㝈ᐃࡉࢀ࡚࠸ࡿࠋ
ᮏ◊✲ࡣࠊᵓ㐀㌿⛣ࡢ኱ᇦⓗ࡞ࣛࣥࢻࢫࢣ࣮ࣉࡢィ⟬ࢆྍ⬟࡟ࡍࡿࡶ࠺୍ࡘࡢ࢔ࣉ࣮ࣟࢳ࡜ࡋ࡚ࠊᒁᡤᵓ
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☜❧ࡍࡿࠋ⏦ㄳ⪅ࡣ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஧ࡘࡢ❧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࡞ࢃࢀ࡚࠸
࡞࠸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

- 155 -

ࢱࢡࢺ࣏ࢸࣥࢩࣕࣝࡢ 3 ✀㢮ࡢ࣏ࢸࣥࢩࣕࣝࡢྜィ࡛⾲ࡉࢀࡿࡀࠊࡑࡢࡑࢀࡒࢀࡀࠊࡑࡢ┦஫స⏝ࡢ࿘ᅖࡢ⎔ቃࡀ 2 ࡘࡢ⎔ቃࡢ࡝ࡕࡽ࡟ࡼࡾ㏆࠸࠿ࢆ⾲ࡍ⎔ቃኚᩘ࡟ኚ໬࡟ᛂࡌ࡚ࠊ2 ࡘࡢ❧యᵓ㐀ࡢ࠺ࡕࡢ࠸ࡎࢀ࠿୍᪉ࡢ୰࡛ࡢ್࡛᭱Ᏻᐃ࡜࡞ࡿࡼ࠺࡞ 2 ✀㢮ࡢ㛵ᩘᙧࡢ࠶࠸ࡔ࡛ࠊ㐃⥆ⓗ࡟ኚ໬ࡍࡿࡼ࠺࡟ᐃ⩏ࡉࢀ࡚࠸ࡿࠋ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡢ᭱ึࡢㄽᩥ (Terada et al., J. Phys. Chem. B
117, 12864-12877 (2013)) ࡢ࠶࡜ࠊࡇࡢࣔࢹࣝࡢᵝࠎ࡞㒊ศ࡟ᑐࡋ࡚ᨵⰋࢆ⾜ࡗ࡚ࡁ࡚࠸ࡿࡀࠊࡲࡔ᳨ウࡢవᆅࡀከࡃṧࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛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⟬࡛ࡣࠊ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡀࣜ࢞ࣥࢻ࡞ࡋ࡛ LID ࢻ࣓࢖ࣥ࡜ CORE ࢻ࣓࢖ࣥࡢ 2ࡘࡀྠ᫬࡟㛤࠸ࡓ≧ែ࡜ྠ᫬࡟㛢ࡌࡓ≧ែࡢ 2 ≧ែࡢ࠶࠸ࡔ࡛ࡢᵓ㐀㌿⛣ࢆ㉳ࡇࡍࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡇࡢ
࡜ࡁࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆ࢚ࢿࣝࢠ࣮ࡢᐤ୚࡜࢚ࣥࢺࣟࣆ࣮ࡢᐤ୚࡟ศゎࡍࡿ࡜ࠊ㛤࠸ࡓ≧ែ࠿ࡽ㛢ࡌࡓ≧ែ࡟ྥ࠿ࡗ࡚࢚ࢿࣝࢠ࣮ࡀ༢ㄪ࡟పୗࡍࡿ࡜࡜ࡶ࡟࢚ࣥࢺࣟࣆ࣮ࡀῶᑡࡍࡿᵝᏊࡀほᐹࡉࢀࠊࡇࢀࡽ஧ࡘ
ࡢ㔞ࡢᚤጁ࡞ࣂࣛࣥࢫ࠿ࡽ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ⏕ࡌ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࢀࡣࢱࣥࣃࢡ㉁ࣇ࢛࣮ࣝ
ࢹ࢕ࣥࢢ࡜ྠᵝࡢ㛵ಀ࡛࠶ࡾࠊ⯆࿡῝࠸⤖ᯝ࡛࠶ࡿࠋ

ᅗ 2㸸࢔ࢹࢽࣝ㓟࢟ࢼ࣮ࢮࡢ 1 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉ
࡜ࠊࡑࢀ࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮࡜࢚ࣥࢺࣟࣆ࣮ࡢᐤ୚ࠋᶓ㍈ࡣ 2 ࡘࡢᵓ㐀࡬ࡢ㢮ఝᗘࡢᕪ࡛࠶ࡾࠊᕥഃࡢᴟᑠࡀ㛤࠸ࡓ≧ែࠊྑഃࡢᴟᑠ
ࡀ㛢ࡌࡓ≧ែ࡟ᑐᛂࡋ࡚࠸ࡿࠋ

- 156 - ࡉࡽ࡟ࠊࣜ࢞ࣥࢻ࠶ࡾࡢ᮲௳࡛ィ⟬ࡉࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉ࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡢ㧗ࡉࡢᗘኚ໬࠿ࡽࠊ㛢ࡌࡓ≧ែ࠿ࡽ㛤࠸ࡓ≧ែ࡬ྥ࠿࠺ᵓ㐀㌿⛣ࡢ㏿ᗘࡢᗘኚ໬ࢆィ⟬ࡋࠊࡑࢀࡀᐇ㦂ⓗ࡟ほ࠸ࡿ཯ᛂ㏿ᗘࡢ

ࡉࢀ࡚

ᗘኚ໬(Wolf-Watz et al., Nature Structural

and Molecular Biology, 11, 945-949 (2004))࡜ࡼࡃ┦㛵ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡇࡢ⤖ᯝࡣ࣓࢝ࣞ࢜ࣥࣔࢹࣝࡀᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉ࡜ࡑࡢ

ᗘኚ໬ࢆࡼࡃグ㏙࡛ࡁ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ
ᅗ 3㸸࣓࢝ࣞ࢜ࣥࣔࢹࣝ࠿ࡽண᝿ࡉࢀࡿᵓ㐀㌿
⛣㏿ᗘࡢ
㏿ᗘࡢ

ᗘኚ໬࡜ᐇ㦂ⓗ࡟ほࡉࢀࡓ཯ᛂᗘኚ໬ࡢẚ㍑ࠋ㸰㸬஧ḟᵓ㐀ࡢ⛣ືࢆ࡜ࡶ࡞࠺࢔ࣟࢫࢸࣜࢵࢡ㌿⛣ࢆ㉳ࡇࡍࢩࣥࢢࣝࢻ࣓࢖ࣥࢱࣥࣃࢡ㉁࡛࠶ࡿ NtrC ࢆᑐ㇟࡟ࡋ
ࡓィ⟬࡛ࡣࠊ஧ḟᵓ㐀ࡢኚ໬࡟࡜ࡶ࡞ࡗ࡚஧㠃ゅࡀ኱ࡁࡃኚࢃࡿࡇ࡜ࡀண᝿ࡉࢀࡿࡓࡵࠊ஧㠃ゅ࣏ࢸࣥࢩࣕࣝࡢ㛵ᩘᙧࡀ┦஫స⏝㒊఩࿘㎶ࡢ⎔ቃኚ໬࡟ᛂࡌ࡚࡝ࡢࡼ࠺࡟ኚ
໬ࡍࡿ࠿࡟ࡘ࠸࡚ࠊ」ᩘࡢྍ⬟ᛶࢆ⪃࠼࡚ẚ㍑᳨ウࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ࿘ᅖ⎔ቃࡢᐃ⩏ࡢࡋ࠿ࡓࡸ࣏ࢸࣥࢩࣕࣝࡢ
㛵ᩘᙧ࡟ࡼࡽࡎ࡟ࠊᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ㧗ࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࡓࡵࠊ࣐ࣝࢳ࢝ࣀࢽ࢝ࣝࢧࣥࣉࣜࣥ
ࢢᡭἲࢆᐇ⿦ࡍࡿࡇ࡜࡟ࡋࡓࠋᙜึࡣࣛࣥࢪࣗࣂࣥศᏊ

ᅗ 4㸸ࣁ࢖ࣈࣜࢵࢻࣔࣥࢸ࢝ࣝࣟἲ࡟ࡼࡗ࡚ィືຊᏛἲ࡜࣐ࣝࢳ࢝ࣀࢽ࢝ࣝἲࢆ⤌ࡳྜࢃࡏࡓ᪉ἲࡢ

⟬ࡉࢀࡓ NtrC ࡢᵓ㐀㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛ

ᐇ⿦ࢆヨࡳࡓࡀࠊ࠺ࡲࡃᏳᐃ࡟ື࠿ࡍࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗ

ࣥࢻࢫࢣ࣮ࣉࠋ㯮࠸ᅄゅ࡛ᅖࡲࢀ࡚࠸ࡿࡢࡀ୙

ࡓࡓࡵࠊ௦ࢃࡾ࡟ࣔࣥࢸ࢝ࣝࣟἲ࡟ࡼࡿᵓ㐀ࢧࣥࣉࣜࣥ

άᛶᵓ㐀௜㏆࡟᪂ࡓ࡟ぢฟࡉࢀࡓ≧ែࠋࢢࢆ⾜࠺ࡇ࡜࡜ࡋࠊ1 ࢫࢸࢵࣉࡈ࡜࡟ࡈࡃ▷࠸ศᏊືຊ
Ꮫἲࢆ⾜ࡗ࡚ᵓ㐀ೃ⿵ࢆ⏕ᡂࡍࡿࣁ࢖ࣈࣜࢵࢻࣔࣥࢸ࢝ࣝࣟ
ἲ(Mukuta and Miura, Biophys. Physicobiol. 17, 14-24 (2020))ࢆᐇ
⿦ࡋࡓࠋࡑࡢ⤖ᯝࠊ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡢ㧗ࡉࡀ࠾ࡼࡑ 10kT࡟࡞ࡾࠊ୍ᐃ

ᗘࡢࣛࣥࢪࣗࣂࣥືຊᏛἲࡢ⤖ᯝ࡜ẚ㍑ࡋ࡚㧗ࡃ࡞ࡿ࡜࡜ࡶ࡟ࠊ୙άᛶᵓ㐀௜㏆ࡢ≧ែࡀ 2 ࡘ࡟ศ࠿ࢀ࡚࠸ࡿ
ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
ࡉࡽ࡟ࠊࡇࡢ஧ࡘࡢ≧ែࡢ㐪࠸ࢆẚ㍑ࡍࡿࡓࡵ࡟ࠊࡇࢀࡽࡢ
≧ែ࡟࠾ࡅࡿྛṧᇶࡢ࿘ᅖ⎔ቃࡢ୙άᛶᵓ㐀࡬ࡢ㏆ࡉࢆィ⟬ࡋᅗ 5㸸ྛṧᇶࡢ࿘ᅖ⎔ቃࡢ୙άᛶᵓ㐀ࡓ࡜ࡇࢁࠊ஧ࡘࡢ≧ែ࡛㐪࠸ࡢ኱ࡁ࠸㡿ᇦࡣࣜࣥ㓟໬ࡍࡿṧᇶ࡛࡬ࡢ㏆ࡉࠋ࢜ࣞࣥࢪࡣᅗ 4 ࡛ྑഃࠊ࠶ࡿ 54 ␒ࡢṧᇶ࡟✵㛫ⓗ࡟᥋ࡋ࡚࠸ࡿ㡿ᇦ࡟㞟୰ࡋ࡚࠸ࡿࡇ࡜

ỈⰍࡣᅗ 4 ࡛ᕥഃࡢ୙άᛶ≧ែ࡟࠾ࡀࢃ࠿ࡗࡓࠋ

ࡅࡿ್ࠋ- 157 -

㸱㸬ᅄḟᵓ㐀ኚ໬ࢆ࡜ࡶ࡞࠺࢔ࣟࢫࢸࣜࢵࢡ㌿⛣ࢆ㉳ࡇࡍ࣐ࣝࢳࢧࣈࣘࢽࢵࢺࢱࣥࣃࢡ㉁࡛࠶ࡿ࣊ࣔࢢࣟࣅࣥࢆᑐ㇟࡟ࡋࡓィ⟬࡛ࡣࠊ࣊ࣔࢢࣟࣅࣥࡀ㓟⣲⃰ᗘࡢୖ᪼࡟కࡗ࡚ᅄḟᵓ㐀㌿⛣ࢆ㉳ࡇࡍᵝᏊࢆ࣓࢝ࣞ࢜ࣥࣔࢹ࡛ࣝ෌⌧࡛ࡁࡿ࠿࡝࠺࠿ࢆ᳨ウࡋࡓࠋࡇࡢࡓࡵࡢᚲせ᮲௳࡜ࡋ࡚ࠊ㓟⣲⤖ྜ㒊఩ࡢ㕲ཎᏊ࿘㎶ࡢᒁᡤⓗ࡞⎔ቃࡢኚ໬࡜ᅄ㔞య඲యࡢᅄḟᵓ㐀ࡢኚ໬ࡢ࠶࠸ࡔ࡟┦㛵ࡀ࠶ࡿ࠿࡝࠺࠿ࢆ᳨ドࡋࠊࣔࢹࣝࡢᨵⰋࡢ⤖ᯝࠊࡇࢀࡽࡀ┦㛵ࢆᙉࡃ࡞ࡿࡼ࠺࡞᮲௳ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢ⤖ᯝࢆ㋃ࡲ࠼
࡚ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᗘࠊ㓟⣲ࡢ⤖ྜ࣭ゎ㞳࡟㛵㐃ࡋࡓࣃ࣓ࣛ

࣮ࢱࡢ᳨ウࢆ⾜ࡗ࡚࠸ࡿࠋ

ᅗ 5㸸࣊ࣔࢢࣟࣅࣥࡢᵓ㐀㌿⛣ࡢ 2 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࠋᕥୖࡢ
ᴟᑠࡀ T ≧ែࠊྑୗࡢᴟᑠࡀ R ≧ែ࡟ᑐᛂࡍࡿࠋ㸲㸬ࢺ࣏ࣟࢪ࣮ࡢ኱ࡁ࡞ኚ໬ࢆ࡜ࡶ࡞࠺࢔ࣟࢫࢸࣜࢵࢡ㌿⛣ࢆ㉳ࡇࡍ࣓ࢱࣔࣝࣇ࢕ࢵࢡࢱࣥࣃࢡ㉁࡛࠶ࡿ
XCL1 ࡟ࡘ࠸࡚ࡶィ⟬ࢆ㛤ጞࡋࡓࡀࠊ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀ㠀ᖖ࡟㧗ࡃࠊ୍ᐃᗘࡢࣛࣥࢪࣗࣂࣥືຊᏛἲ

࡛ࡣᵓ㐀㌿⛣ࡀ඲ࡃぢࡽࢀ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊNtrC ࡟ᑐࡋ࡚౑⏝ࡋࡓࣁ࢖ࣈࣜࢵࢻࣔࣥࢸ࢝ࣝࣟἲࢆ XCL1
࡟ᑐࡋ࡚ࡶ㐺⏝ࡋࡓࡶࡢࡢࠊᏳᐃ࡞ィ⟬ࢆᐇ⌧ࡍࡿ࡜ࡇࢁࡲ࡛ࡣ฿㐩࡛ࡁ࡞࠿ࡗࡓࠋࡇࡢཎᅉࡣ⌧ᅾㄪᰝ୰࡛࠶ࡿࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫ ⏣ྜྷۻ‬ᶞ⏕, ➲஭ ⌮⏕, ᑎ⏣ ᬛᶞ, "࣓࢝ࣞ࢜ࣥࣔࢹࣝ࡟ࡼࡿ࢔ࢹࢽࣝ㓟࢟ࢼ࣮ࢮࡢᵓ㐀㌿⛣ࡢ◊✲",➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ࢜ࣥࣛ࢖ࣥ㛤ദ (2021 ᖺ 11 ᭶)(2) ‫ۻ‬Ọ⏣ ኱ᬕ, ➲஭ ⌮⏕, ᑎ⏣ ᬛᶞ, "Free energy landscape analysis of conformational transition of NtrC by
chameleon model", ➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ࢜ࣥࣛ࢖ࣥ㛤ദ (2021 ᖺ 11 ᭶)ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫ۻ‬Tomoki P. Terada, Qing-Miao Nie, Masaki Sasai, "A landscape-based view on the stepping movement of myosin

VI", ᢞ✏୰㸦2022 ᖺ 5 ᭶ᢞ✏㸧

- 158 -

⏕యศᏊ࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟ࡢ⌮ㄽィ⟬
Theoretical calculations of molecular functions of biomolecules andmolecular assemblies‫ۑ‬ᯘ 㔜ᙪࠊ಴㔜 భ㍤ࠊᡂ ࢭ࢖ࠊ኱ሙ ඃ⏕ࠊᒣᮏ ⿱⏕ࠊᑠᒣ ⣊ࠊ໭ᮧ ┤኱ࠊᯇᒣ ⥤ኟࠊすᑿ ᐀୍㑻ࠊ㮵಴ ၨྐࠊ➉ෆ ⨾ᶞࠊୖ⏣ ዲᶵࠊ᱓⏣ ⚈ᕼࠊᚋ⸨ ᓅࠊୖ⏣ ዲᶵࠊᵽ㔝 ೺ኴ㑻㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧◊✲┠ⓗ㢧ⴭ࡞ศᏊᶵ⬟ࢆ᭷ࡍࡿࢱࣥࣃࢡ㉁ཬࡧศᏊ㞟ྜ⣔࡟㛵ࡋ࡚௨ୗࡢ⌮ㄽィ⟬ࢆ⾜࠺ࠋ1.1ኳ↛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 ≧ែࢆゎᯒࡋࡓࠋࡇࡢ≧ែࡢ㓟໬≧ែ࡟㛵ࡋ࡚ࡣࠊ(65 ᐇ㦂࡜ ; ⥺⤖ᬗᵓ㐀ゎᯒᐇ㦂ࡢ⤖ᯝ࡟㱈㱒ࡀぢࡽࢀࡿࠋ
1.2

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ࢔ࢽ࢜ࣥࢳࣕࢿࣝ *W$5& ࡢගάᛶ໬࡟ࡼࡿ࢖࢜ࣥࢳࣕࢿࣝᙧᡂࡸ࢖࢜ࣥ㑅ᢥᛶ࡞࡝ࡢ࢖࢜ࣥ㍺㏦ࡢศᏊ
ᶵᵓࢆ 0' ཬࡧ 40005:)(6&) ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡋࠊࡼࡾ
ᐇ⏝ⓗ࡞ග㑇ఏᏛࢶ࣮ࣝࡢタィࢆ┠ᣦࡍࠋࡲࡓග㥑ື &O ࣏ࣥࣉ࡛࠶ࡿ K5 ࢱࣥࣃࢡ㉁ࡢගάᛶ໬୰㛫≧ែ࡟㛵ࡋ࡚ࡶ◊✲ࢆ⾜࠸ࠊࢳࣕࢿࣝ㸦ཷື㍺㏦㸧࡜࣏ࣥࣉ㸦⬟ື㍺㏦㸧ࡢ㟼㟁⎔ቃࡸ࢚ࢼࢪ࢙ࢸ࢕ࢡࢫࡢᕪࢆ
᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ࡼࡾࠊ࢖࢜ࣥ㍺㏦ࡢศᏊᶵᵓ࡟㛵ࡍࡿࡼࡾ῝࠸⌮ゎࢆᚓࡿࠋ
1.3

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒ

4000 5:)(6&) ἲࢆ⏝࠸࡚ +,9 ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡋࠊ⸆๣⪏ᛶࡢศᏊᶵᵓ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࠋᮏ◊✲࡛ࡣࠊࡇࢀࡲ࡛ࡢィ⟬࡛ゎᯒࡋࡓỈศᏊ௜ຍ཯ᛂ࡟⥆ࡃࣉࣟࢺࣥ⛣ື࠾ࡼࡧ࢔࣑ࢻ
⤖ྜゎ㞳཯ᛂࡢゎᯒࢆ⾜࠺ࠋ
1.4ࣁ࣐࣮ࣥ࣊ࢵࢻᆺࣜ࣎ࢨ࢖࣒ࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒ

4000 5:)(6&) ἲࠊཬࡧ 0' ἲࢆ⏝࠸࡚ࠊࣁ࣐࣮ࣥ࣊ࢵࢻࣜ࣎ࢨ࢖࣒ࡢ⮬ᕫษ᩿ゐ፹཯ᛂࡢศᏊᶵᵓ
ࢆゎ᫂ࡍࡿࠋᮏ◊✲࡛ࡣࠊࡲࡎࠊ51$ ⣔ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᚲせ࡜࡞ࡿ⣔୰ࡢ 0J ࢖࢜ࣥࡢ㐺ษ࡞ಶᩘࢆỴᐃࡋࠊ40005:)(6&) ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠺ࠋ
1.5㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒ7077) $V) ࡞࡝࡟௦⾲ࡉࢀࡿ 7077) ⣔ࡣᖖ࡛ఏᑟయࠊᴟప

࡛ࡣ⤯⦕໬ࡍࡿࠊ୍ḟඖ᪉ྥ࡟ࡢࡳ┦㛵ࢆᣢࡘᨃ୍ḟඖ᭷ᶵᑟయ࡛࠶ࡿࠋࡇࡢ⣔ࡣ TXDUWHUILOOHG +XEEDUG ࣔࢹ࡛ࣝグ㏙ࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ
≀ᛶࡸ㔞Ꮚ┦ࡣ㠀ᖖ࡟」㞧࡛࠶ࡾࠊᚤᑠ࡞ᵓ㐀ኚ໬࡛኱ࡁ࡞≀ᛶኚ໬ࡀ㉳ࡇࡿᶵᵓࢆ୰ᚰ࡜ࡋ࡚ࡑࡢ඲ᐜࡣ
ᮍࡔࢃ࠿ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊ㏆ᖺᥦၐࡉࢀࡓ㟁Ⲵ⛛ᗎ┦࡟࠾ࡅࡿศᏊෆᵓ㐀ኚ໬࡜ᡃࠎࡀ࿘ᮇቃ⏺᮲௳ࢆຍ࿡ࡋࡓ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚Ỵᐃࡋࡓࣃ࣓࣮ࣛࢱࢆ⏝࠸࡚᱁Ꮚᶍᆺࢆᵓ⠏ࡋ࡚ཝᐦᑐゅ໬ἲ࡛ゎࡃࡇ࡜࡟ࡼࡾࠊ㟁Ⲵ⛛ᗎ┦࡜㉸ఏᑟ┦ࡢ㛵ಀࢆㄪ࡭ࠊ␗ᖖ㉸ఏᑟ࡟ᑐࡍࡿ୍ࡘࡢᶵᵓࢆᥦ᱌ࡍࡿࡇ࡜ࢆ┠ᶆ࡜ࡍࡿࠋ
1.6

㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃపศᏊ㟁Ꮚᮦᩱࡢ㡯㛫஺ᕪ㐣⛬ࡢ⌮ㄽⓗゎᯒ㏆ᖺࠊከ㔜ບ㉳Ꮚศ⿣ࡸࣇ࢛ࢺࣥ࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥࠊ⇕άᛶ໬㐜ᘏ⺯ගࠊືⓗ᰾ࢫࣆࣥ೫ᴟ࡞࡝ࠊ⢭⦓࡞࢚ࢿࣝࢠ࣮‽఩ไᚚ࡟ࡼࡾ 7 ≧ែࢆ✚ᴟⓗ࡟ά⏝ࡍࡿ࡜࠸࠺◊✲ࡀᛴ㏿࡞㐍ᒎࢆぢࡏ࡚࠸ࡿࠋࡋ࠿ࡋࠊጞ
≧ែ࡜⤊≧ែࡢ㛫ࡢࢫࣆࣥ㌶㐨┦஫స⏝ࢆ㏻ࡋࡓ≧ែ㛫࢝ࢵࣉࣜࣥࢢࡸࢲࢩࣥࢫ࣮࢟ᅇ㌿࡞࡝ࡢ≧ែ㛫ࡢ

- 159 -

ᇶ‽᣺ືࡢኚ໬ࡣࠊᐇ㦂ⓗ࡟ࡣ┤᥋Ỵᐃࡍࡿࡇ࡜ࡀᅔ㞴࡛࠶ࡿࡓࡵศᏊタィ࡟Ⓨᒎࡉࡏࡿࡲ࡛࡟ࡣ⌮ゎࡀ㐍ࢇ࡛࠸࡞࠸ࡀࠊ㔜せ࡞ᅉᏊ࡛࠶ࡿࡇ࡜ࡣ⌮ㄽⓗ࡟᫂ࡽ࠿࡛࠶ࡿࠋࡲࡓᇶᗏ≧ែ࡟ẚ࡭࡚ࡣࡿ࠿࡟」㞧࡞ບ㉳≧ែࡢ⌮ㄽⓗゎᯒࡣᐜ࡛᫆ࡣ࡞ࡃࠊ㔞Ꮚ໬Ꮫィ⟬ࡢಙ㢗ᛶࡣ㝈ࡽࢀ࡚࠸ࡓࡀࠊ㏆ᖺࡢィ⟬ᡭἲࡢⓎᒎ࡟ࡼࡾᑡࡋࡎࡘಙ㢗ᛶࡢ㧗࠸ィ⟬ࡀྍ⬟࡟࡞ࡾࡘࡘ࠶ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣඛ➃ⓗ࡞ບ㉳≧ែ⌮ㄽࢆ⏝࠸࡚ࠊࡑࢀ
⮬యࡢಙ㢗ᛶࢆ☜❧ࡍࡿ࡜ඹ࡟ࠊ≧ែ㛫࢝ࢵࣉࣜࣥࢢࡸ࣏ࢸࣥࢩࣕࣝᙧ≧ࡢኚ໬ࡀ࡝ࡢࡼ࠺࡟㡯㛫஺ᕪ㐣⛬ࡢຠ⋡ࢆỴᐃࡋ࡚࠸ࡿࡢ࠿ࢆ⌮ゎࡍࡿࡓࡵୖグࡢ '13 ࢆ౛࡜ࡋ࡚⌮ㄽⓗ◊✲ࢆᐇ᪋ࡍࡿࠋ


2.1◊✲᪉ἲࠊィ⟬᪉ἲ
PSII ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

6 ≧ែࡢ␗࡞ࡿࣉࣟࢺࣥ໬≧ែࡸ㓟໬≧ែ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(66ࠊཬࡧ $PEHU ࢆ⏝࠸࡚⾜ࡗࡓࠋ2.2ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ

*W$&5 ࡟㛵ࡋ࡚ࡣࠊࣉࣟࢺࣥ໬≧ែࢆኚ໬ࡋࡓ୰㛫≧ែࡢࣔࢹࣝࢆᵓ⠏ࡋࠊ4000 5:)(6&) ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬࡟ࡼࡾᵓ㐀ࡢ⢭ᐦ໬ࢆ⾜ࡗࡓࠋࡲࡓࠊ0' ἲࢆ⏝࠸ࡓ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊሷ⣲࢖࢜ࣥ⛣ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆィ⟬ࡋࡓࠋග㥑ື &O ࢖࣏࢜ࣥࣥࣉ࡛࠶ࡿ K5 ࡟㛵ࡋ࡚ࡶࠊࣉࣟࢺࣥ໬≧ែࢆኚ໬ࡋࡓ୰㛫≧ែࣔࢹࣝࡢᵓ㐀⢭ᐦ໬ࢆ⾜ࡗࡓࠋ*W$&5 ཬࡧ K5 ࡢ 0' ⣔ࡣྛࠎ a ཎᏊ⣔࡛࠶ࡾࠊィ⟬ࡣࡑࢀࡒࢀ $PEHU ཬࡧ 1$0' ࢆ⏝࠸ࡓࠋ
2.3

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒࣉࣟࢺࣥ⛣ື࠾ࡼࡧ࢔࣑ࢻ⤖ྜゎ㞳཯ᛂࡢጞ࣭⤊≧ែ࡟ᑐࡋ࡚ 4000 5:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ0' ⣔ࡣ a ཎᏊ⣔࡛ࠊ$PEHU ࢆ⏝࠸ࡓࠋ
2.4ࣁ࣐࣮ࣥ࣊ࢵࢻᆺࣜ࣎ࢨ࢖࣒ࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒ㟁Ⲵࡀ㈇࡟ᖏ㟁ࡋỈ୰࡟࠾࠸࡚ࡶ 0J ࡀከࡃ㓄఩ࡍࡿࣜ࣎ࢨ࢖࣒࡟ᑐࡋࠊ㐺ษ࡞ࣂࣝࢡỈ୰ 0J ⃰ᗘࢆ୚࠼ࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ⣔ࡢ 0J ࡢಶᩘࢆỴᐃࡍࡿࡓࡵࠊ0' ィ⟬୰ࡢ 0J ࡢಶᩘࢆᚎࠎ࡟ቑࡸࡋࡓ
0' ィ⟬ࢆ⾜࠺ࠋᚓࡽࢀࡓ⣔ࢆ⏝࠸࡚ࠊጞ࠾ࡼࡧ୰㛫≧ែ࡟ᑐࡋ࡚ 4000 5:)(6&) ⮬⏤࢚ࢿࣝࢠ࣮ᵓ
㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ0' ⣔ࡣ  ཎᏊ⣔࡛ࠊ$PEHU ࢆ⏝࠸ࡓࠋ
2.5㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒ7077) ⣔ࡢ໬Ꮫⓗᅽຊࡢຠᯝࢆࠊ㔞Ꮚ໬Ꮫⓗᡭἲࢆ⏝࠸࡚᫂ࡽ࠿࡟ࡍࡿࠋ7077) ⣔ࡣᑐ࢔ࢽ࢜ࣥ࡟ࡼࡾ໬
Ꮫⓗᅽຊࢆㄪ⠇࡛ࡁࡿ⣔࡛࠶ࡾࠊᐇ㦂ⓗ࡟ࡣᑐ࢔ࢽ࢜ࣥࡀ኱ࡁ࠸࡯࡝㟁Ⲵ⛛ᗎ㌿⛣ᗘࡀ㧗໬ࡋࠊᙉ࠸㟁

Ⲵ⛛ᗎࡀ⌧ࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊ㌶㐨࢚ࢿࣝࢠ࣮ࡢኚ໬࡛ศᏊෆᵓ㐀ኚ໬ࢆ⾲ࡋࠊ⛣ື✚ศࢆኚ࠼ࡿࡇ࡜࡟ࡼࡾศᏊෆᵓ㐀ኚ໬࡜⛣ື✚ศ࡟ࡼࡿ┦ᅗࢆᥥࡁࠊ㟁Ⲵ⛛ᗎ࡟ࡼࡾ㉸ఏᑟ┦ࡢ㡿ᇦࡀ࡝࠺ኚ໬
ࡍࡿ࠿ㄪ࡭ࡿࠋࡲࡓ໬Ꮫⓗᅽຊ࡜࢔ࢽ࢜ࣥࡢ㛵ಀࢆㄪ࡭ࡿࡓࡵࠊᵝࠎ࡞᱁Ꮚᐃᩘ࡛࢔ࢽ࢜ࣥࡢ㉁㔞ࢆኚ࠼ࠊ࢔ࢽ࢜ࣥࡀ 7077) ศᏊࡢ᪉ྥ࡟ືࡃ࣮ࣔࢻࡢ᣺ືᩘ࡞࡝ࢆゎᯒࡋ 7077) ⣔ࡢ┦ᅗࡢໟᣓⓗ࡞⌮ゎࢆᚓࡿࠋ
2.6

㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃపศᏊ㟁Ꮚᮦᩱࡢ㡯㛫஺ᕪ㐣⛬ࡢ⌮ㄽⓗゎᯒືⓗ᰾ࢫࣆࣥ೫ᴟࡢศᏊᮦᩱ࡟ࡘ࠸࡚୕㔜㡯ࢆ฼⏝ࡋࡓ㟁Ꮚࢫࣆࣥ೫ᴟࡢ೫ᴟ⋡࡜ኚ᥮ຠ⋡ࡢ⌮ㄽゎᯒࢆ⾜࠺ࠋ୕㔜㡯ࢆ฼⏝ࡋࡓ㟁Ꮚࢫࣆࣥ೫ᴟࡢ⏕ᡂࡀᐇ⌧ࡉࢀ࡚࠸ࡿศᏊࡣࠊ࢜ࣜࢦ࢔ࢭࣥ࡜࣏ࣝࣇ࢕ࣜࣥ⣔ࡢ஧ࡘ࡟࡯ࡰ㝈ࡽࢀ࡚࠾ࡾࠊඹ࡟ග↷ᑕ࡟ࡼࡾ⏕ᡂࡋࡓ 6 ≧ែ࠿ࡽ 7n ≧ែ࡬ࡢ㡯㛫஺ᕪࡢࢫࢸࢵࣉ࡟࡚⦰㏥ࡍࡿ୕㔜㡯ࡢ୍ࡘࡢࢫࣆࣥ≧ែ࡬ࡢ㑅ᢥⓗ࡞㑄⛣ࡀ㉳ࡇࡿ࡜⪃࠼ࡿࡢࡀ⌧᫬Ⅼ࡛᭱ࡶྜ⌮ⓗ࡛࠶ࡾࠊ᫖ᖺᗘࡲ
࡛ࡢ◊✲࡛࣌ࣥࢱࢭࣥࢆጞࡵ࡜ࡍࡿ࢜ࣜࢦ࢔ࢭࣥ⣔࡟ࡘ࠸࡚⌮ㄽⓗ࡞ㄝ᫂ࢆ୚࠼ࡓࠋ௒ᖺᗘࡣࠊᚋ⪅ࡢ࣏ࣝࣇ࢕ࣜࣥ⣔㸦㔠ᒓ࣏ࣝࣇ࢕ࣜࣥࢆྵࡴ㸧࡟ࡘ࠸࡚⌮ㄽⓗゎᯒࢆ⾜࠺ࠋ࣏ࣝࣇ࢕ࣜࣥ⣔ࡢ㟁Ꮚࢫࣆࣥ೫ᴟ࡟㛵- 160 -

୚ࡍࡿࡢࡣ㸲ࡘࡢࣇࣟࣥࢸ࢕࢔㌶㐨㛫ࡢ㑄⛣࡛グ㏙ࡉࢀࡿ࠸ࢃࡺࡿ 4[4\ ບ㉳≧ែ࡛࠶ࡾࠊࡇࢀࡽࡢບ㉳≧ែ㛫ࡢࢫࣆࣥ㌶㐨┦஫స⏝ࡢࢫࣆࣥᑕᙳᡂศࡈ࡜ࡢ኱ࡁࡉࡢ㐪࠸࡟ࡼࡾศᒱẚࡢ㐪࠸ࠊࡍ࡞ࢃࡕ㑅ᢥ๎ࡀ⏕ࡌࡿ࡜ண᝿ࡋࠊࡲࡎࡣྛບ㉳≧ែࡢ᭱ᑠⅬ࡛ࡢ࣊ࢵࢩ࢔ࣥィ⟬ࢆ⾜࠺ࠋ


3.1

◊✲ᡂᯝ
PSII ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

6 ≧ែ࡟ᑐࡋ࡚ࠊ ಶࡢྍ⬟࡞ࣉࣟࢺࣥ໬࣭㓟໬≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆᚓࡓࠋ▷᫬㛫ࡢࢺࣛࢪ࢙ࢡࢺࣜ࡟ࡼࡿ⥺ᙧᛂ⟅⮬⏤࢚ࢿࣝࢠ࣮ࡢᴫ⟬࡛ࡣࠊ(65 ᐇ㦂࡛♧၀ࡉࢀ࡚࠸ࡿ K\GUR[RR[R ≧ែࡀࠊ; ⥺⤖ᬗᵓ㐀ゎᯒ࡛ᥦ᱌ࡉࢀ࡚࠸ࡿ R[\OR[R ᵓ㐀ࡼࡾ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟Ᏻᐃ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
3.2

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ

*W$&5 ࡢගάᛶ໬ᚋࡢࣉࣟࢺࣥ໬≧ែࢆኚ໬ࡋࡓ୰㛫≧ែ࡟ᑐࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆᚓࡓࠋࡲࡓࠊ࢖࢜ࣥࢳࣕࢿࣝෆࡢ &O ࢖࢜ࣥࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡢィ⟬ࢆ⾜࠸ࠊᑐ࢖࢜ࣥࡢ࢝ࣝ࣎ࣥ㓟ഃ㙐ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿሙྜ࡟ࡣࠊࢳࣕࢿࣝෆ࡟ &O ࢖࢜ࣥࢆᙉࡃ⤖ྜࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊ
+5 ࡢึᮇ୰㛫≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸ࠊ୰㛫≧ែ⏕ᡂ࡟ࡼࡾ &O ࢖࢜ࣥࡢ⤖ྜ఩⨨ࡀ኱ࡁࡃ⛣ືࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
3.3

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒࣉࣟࢺࣥ⛣ື࠾ࡼࡧ࢔࣑ࢻ⤖ྜゎ㞳཯ᛂࡢጞ≧ែ࡜⤊≧ែ࡟ᑐࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆᚓࡓࠋࡲ
ࡓࠊࡑࢀࡽࡢ㛫ࢆࡘ࡞ࡄ཯ᛂ⤒㊰࡟ᑐࡋ࡚࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸㑄⛣≧ែࡢ㏆ఝⓗᵓ㐀ࢆᚓࡓࡢࡕࠊ㑄⛣≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ࢆ㛤ጞࡋࡓࠋ
3.4

ࣁ࣐࣮ࣥ࣊ࢵࢻᆺࣜ࣎ࢨ࢖࣒ࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒ

0' ィ⟬࡟ࡼࡾࠊ⣔ࡢࣂࣝࢡỈࡢ㒊ศࡢ 0J ⃰ᗘࡀ࠾ࡼࡑᐇ㦂⃰ᗘ࡜࡞ࡿ 0J ࡢಶᩘࢆỴᐃࡋࡓࠋከࡃ
ࡢ 0J ࡀࣜ࣎ࢨ࢖࣒࡟㓄఩ࡋࠊࣂࣝࢡỈࡢ 0J ⃰ᗘࢆ୚࠼ࡿಶᩘࡢ࠾ࡼࡑಸ࡜࡞ࡿಶᩘ࡜࡞ࡗࡓࠋࡑࡢ
⣔ࢆ⏝࠸࡚ࠊ཯ᛂጞ≧ែ࠾ࡼࡧ୰㛫≧ែ࡟ᑐࡋ࡚ 4000 ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ3.5㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒศᏊᛶ⤖ᬗࡢ 7077) ⣔࡟࠾ࡅࡿ໬Ꮫⓗᅽຊࡢຠᯝࢆࠊ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚ᚓࡽࢀࡿ┦஫స⏝ࣃ࣓࣮ࣛࢱ
࠿ࡽᵓ⠏ࡋࡓࣔࢹࣝࣁ࣑ࣝࢺࢽ࢔ࣥࡢ┤᥋ᑐゅ໬ᡭἲ࡟ࡼࡾ᫂ࡽ࠿࡟ࡋࡓࠋ7077) ⣔ࡣᑐ࢔ࢽ࢜ࣥࡀ㔜࠸࡯࡝㟁Ⲵ⛛ᗎ㌿⛣ᗘࡀ㧗໬ࡋࠊᙉ࠸㟁Ⲵ⛛ᗎࡀ⌧ࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ⌧㇟ࡢ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ

࠿࡟ࡍࡿࡓࡵ࡟ࠊඛ⾜◊✲࡟ࡼࡾ♧၀ࡉࢀࡿ஧㔞య໬ࡢゎᯒࢆ⾜࡞ࡗࡓࠋ⤖ᬗ᱁Ꮚࢧ࢖ࢬ࡜ᑐ⛠ᛶࢆಖࡕ࡞
ࡀࡽ㸰ศᏊ㸯⤌࡜ࡋ࡚ศᏊ㛫㊥㞳ࢆኚ໬ࡉࡏ࡞ࡀࡽ」⣲ศᴟ⋡ࡸ 'UXGH 㔜ࡳ࡞࡝ࠊ㔠ᒓ┦࣭⤯⦕┦࣭㉸ఏᑟ┦ࢆศ㢮ࡍࡿ㝿࡟౑⏝ࡉࢀࡿ≀⌮ⓗ࡞ᣦᶆ࡟ࡘ࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ஧㔞య໬࡟క࠺ᵓ㐀ኚ໬࡟ᑐࡋ࡚ࠊ㔞Ꮚ໬Ꮫィ⟬࠿ࡽணࡉࢀࡿ⌧ᐇⓗ࡟ྍ⬟࡞ᵓ㐀ኚ໬ࡢ⠊ᅖ࡟࠾࠸࡚ࡣࠊᑡ࡞ࡃ࡜ࡶᑠࡉ࡞༢఩᱁Ꮚ

ࡢィ⟬࡟࠾࠸࡚ࡣࠊຠᯝࡣప࠸࡜ࡢ⤖ᯝࢆᚓࡓࠋḟ࡟ࠊศᏊᑐࡢᑐ⛠ᛶࢆᔂࡍࡼ࠺࡞ᵓ㐀ኚ໬࡟ἢࡗ࡚ྠᵝࡢᣦᶆࡢィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊᑐ⛠ᛶࡢᔂࢀࡣ TMTTF ⣔ࡢ㔞Ꮚ┦࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
≉࡟ᑐ⛠ᛶࡀᔂࢀࡿࡇ࡜࡟ࡼࡾ௚ࡢᵓ㐀ኚ໬࡟ᑐࡋ࡚㉸ఏᑟ㌿⛣ࡀᢚไࡉࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
3.6

㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃపศᏊ㟁Ꮚᮦᩱࡢ㡯㛫஺ᕪ㐣⛬ࡢ⌮ㄽⓗゎᯒ࢜ࣜࢦ࢔ࢭࣥ⣔࡜࣏ࣝࣇ࢕ࣜࣥ⣔࡟ࡘ࠸࡚ࠊග↷ᑕ࡟ࡼࡾ⏕ᡂࡋࡓ 6 ≧ែ࠿ࡽ 7n ≧ែ࡬ࡢ㡯㛫஺ᕪࡢࢫࢸ
ࢵࣉ࡟࡚⦰㏥ࡍࡿ୕㔜㡯ࡢ୍ࡘࡢࢫࣆࣥ≧ែ࡬ࡢ㑅ᢥⓗ࡞㑄⛣ࡀ㉳ࡇࡿ࡜⪃࠼ࠊ67 㡯㛫஺ᕪ࡟࠾ࡅࡿྛࢫ
ࣆࣥࢧࣈࣞ࣋ࣝࡢ㑄⛣㏿ᗘẚࢆ⟬ฟࡍࡿࡓࡵ࡟≧ែ㛫ࡢࢫࣆࣥ㌶㐨┦஫స⏝ࡢ x, y, z ᡂศࡑࢀࡒࢀ࡟ศࡅࡓ
ẚ㍑ࢆ⾜ࡗࡓࠋ࢜ࣜࢦ࢔ࢭࣥ⣔࡟ࡘ࠸࡚ࠊ㧗⢭ᗘከཧ↷㟁Ꮚ┦㛵⌮ㄽࢆ⏝࠸ࡓບ㉳࢚ࢿࣝࢠ࣮ィ⟬࠿ࡽࠊග- 161 -

チᐜ≧ែ࡛࠶ࡿ S1 ࠿ࡽ㡯㛫஺ᕪ࡟ࡼࡾ୺࡟㑄⛣ࡍࡿࡢࡣ T2 ≧ែ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋS1-T2 㡯㛫஺ᕪࡢ㑄⛣㏿ᗘࢆィ⟬ࡋࡓ࡜ࡇࢁࢫࣆࣥ㌶㐨┦஫స⏝ࡣศᏊࡢᑐ⛠ᛶ࠿ࡽ⚗ไ࡛࠶ࡿࡇ࡜࠿ࡽ࡯ࡰࢮࣟ࡟࡞ࡗࡓࡓ
ࡵࠊศᏊ᣺ື࡟ࡼࡿᑐ⛠ᛶࡢ◚ࢀࡢຠᯝࢆ⪃៖ࡋࡓィ⟬ࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊᇶ‽᣺ືゎᯒ࠿ࡽᚓࡽࢀࡓ
ྛ࣮ࣔࢻ࡟ἢࡗ࡚ᵓ㐀ࢆኚ఩ࡉࡏࡘࡘࠊࢫࣆࣥ㌶㐨┦஫స⏝ࡢኚ໬ࢆ୍ḟࡢ㡯ࡲ࡛⪃៖ࡋ࡚ displacedharmonic oscillator ㏆ఝࡢࡶ࡜ࣇ࢙࣑ࣝ㯤㔠ഃ࡟ᇶ࡙࠸࡚㑄⛣㏿ᗘࢆィ⟬ࡋࡓࠋࡑࡢ⤖ᯝࠊ࢜ࣜࢦ࢔ࢭࣥࡢ
㛗㍈ࢆ xࠊ▷㍈ࢆ yࠊ㠃እ㍈ࢆ z ࡜ᐃ⩏ࡋࡓሙྜ࡟ࠊTx, Ty ࢫࣆࣥࢧࣈࣞ࣋ࣝ࡬ࡢ㑄⛣ࡀ㢧ⴭ࡟ቑᙉࡉࢀࡿࡇ
࡜ࢆ☜ㄆࡋࡓࠋࡇࢀ࠿ࡽ࢜ࣜࢦ࢔ࢭࣥศᏊࡢ୕㔜㡯㟁Ꮚࢫࣆࣥ೫ᴟ࡟࠾࠸࡚ࡣศᏊࡢ㠃እ᣺ື࡟ࡼࡾ೫ᴟࡀ
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Online (ZYux), (GÏEÄ), 2021 _ 11 z 25 s2021 _ 12 z 2 sx

Masakazu Matsumoto, “The polymorphism of ice”, International Conference on Discrete GeometricAnalysis for Materials Design, Online (Nagoya University), September 27, 2021x| l, “%&j²”,ZYux9Æ±c, KG.K (ZYux), 2021 _ 9 z 4 sx

| l, “7?K-.7·pÓ”, qx¨ÎQ>.L"-H  6 MÎQ.²,
KG.K, 2021 _ 7 z 15s'
x

0DVDND]X 0DWVXPRWR 7DNXPD <DJDVDNL DQG +LGHNL 7DQDND ³2Q WKH DQRPDORXV KRPRJHQHLW\ RI
K\GURJHQGLVRUGHUHGLFHDQGLWVRULJLQ´          x

+LGHNL7DQDND7DNXPD<DJDVDNLDQG0DVDND]X0DWVXPRWR2QWKHUROHRILQWHUPROHFXODUYLEUDWLRQDOPRWLRQV IRU LFH SRO\PRUSKV ,,, 0RGH FKDUDFWHULVWLFV DVVRFLDWHG ZLWK QHJDWLYH WKHUPDO H[SDQVLRQ          x0DVDND]X0DWVXPRWR7DNXPD<DJDVDNLDQG+LGHNL7DQDND³1RYHO$OJRULWKPWR*HQHUDWH+\GURJHQ'LVRUGHUHG,FH6WUXFWXUHV´             x|l, “% 7?K-.7pÓ Pauling /K:J?L”, mX§ª 56 (11), 691-699(2021).

- 166 -

㔞ᏊศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ NTChem ࡟ࡼࡿࢼࣀࢧ࢖ࢬศᏊࡢศᏊᶵ⬟ࡢゎ࣭᫂タィ
Applications of quantum molecular science simulation software
NTChem for elucidation and design of molecular functionality ofnanomolecules‫ۑ‬୰ᔱ 㝯ே㸪:LOOLDP'DZVRQ ᯇᒸ ㈗ⱥ㸪ᕝᔱ ⱥభ ⌮໬Ꮫ◊✲ᡤ  㸪㜿ஂ᰿ ᫀᙪ ⚄ᡞ኱Ꮫ 


◊✲┠ⓗ

 ⏕ศゎᛶ࣭ᾏὒศゎᛶ࣏࣐࣮ࣜࡢศゎᛶணᢏ⾡⏕ศゎᛶ࣏࣐࣮ࣜࡢศゎᗘࡣ࣏࣐࣮ࣜ✀ࡔࡅ࡛࡞ࡃ㸪 ᗘ㸪‵ᗘ㸪S+㸪ᚤ⏕≀✀࡞࡝ࡢ⎔ቃせᅉ࡟౫Ꮡࡍࡿ㸬᪤▱࣭ᮍ▱ࡢ࣏࣐࣮ࣜ࡟ࡘ࠸࡚㸪ᐇ㦂࡛ࡇࢀࡽࡢせᅉࢆ⣔⤫ⓗ࡟᳨ドࡍࡿࡇ࡜ࡣ㸪᪥ᩘࡀ࠿࠿ࡿࡇ࡜ࡶ࠶ࡗ
࡚ᅔ㞴࡛࠶ࡿ㸬ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣ⏕ศゎᛶணࢩ࣑࣮ࣗࣞࢱ࡜ศゎ཯ᛂࢩ࣑࣮ࣗࣞࢱࢆ⤌ࡳྜࢃࡏࡿࡇ࡜

࡟ࡼࡗ࡚㸪࣏࣐࣮ࣜࡢศゎᗘ࡜ࡑࢀ࡟࠿࠿ࡿ᫬㛫ࢆ⌮ㄽⓗ࡟ணࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿ㸬

.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢྜᡂ཯ᛂ⤒㊰ゎᯒᣢ⥆ྍ⬟࡞࢚ࢿࣝࢠ࣮♫఍ࡢᐇ⌧࡟㈨ࡍࡿᢏ⾡ࡢ㛤Ⓨࢆ┠ᣦࡋ㸪ᡃࠎࡀ᭱㏆ .HJJLQ ᆺ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ࡛ぢฟࡋࡓከ㟁Ꮚ⛣ືࡢⓎ⌧࣓࢝ࢽࢬ࣒࡟ᇶ࡙࠸࡚ከ㟁Ꮚ⛣ື཯ᛂࢆ௰௓࣭ಁ㐍ࡍࡿྍ⬟ᛶࢆࡶࡘ࢖࢜
༙ࣥᚄࡀ኱ࡁࡃ㟁Ⲵࡢᑠࡉ࡞࣊ࢸࣟ࢝ࢳ࢜ࣥࢆ㦵᱁࡟㛢ࡌ㎸ࡵࡓ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡸ≉␗࡞᣺ࡿ⯙࠸࡛㧗ᶵ⬟ゐ፹࡜࡞ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡿࣉࣟࢺࣥࢆ㦵᱁࡟㛢ࡌ㎸ࡵࡓ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺ㸪࠾ࡼࡧࡑࢀࡽࡢ
ᣑᙇᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࢆ㛤Ⓨࡍࡿ⌮ㄽⓗ࡞タィᣦ㔪ࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿ㸬◊✲᪉ἲࠊィ⟬᪉ἲ ⏕ศゎᛶ࣭ᾏὒศゎᛶ࣏࣐࣮ࣜࡢศゎᛶணᢏ⾡ᮏ◊✲࡛ࡣᾏὒ࡟࠾ࡅࡿ࣏࢚ࣜࢫࢸࣝ࠾ࡼࡧ࣏ࣜ࢔࣑ࢻࡢຍỈศゎࢆᑐ㇟࡜ࡍࡿ㸬࣏࣐࣮ࣜሢࡢᔂቯ࡟࠾ࡅࡿ࣏࣐࣮ࣜ㙐ࡢษ᩿࡜࢜ࣜࢦ࣐࣮ࡢ⁐ฟࢆ☜⋡ࣔࢹࣝ໬ࡍࡿࡇ࡜࡛㸪ศゎᗘ࡜ᑐᛂࡍࡿ᫬㛫ࢆồࡵࡿ .LQHWLF 0RQWH &DUOR ࢩ࣑࣮ࣗࣞࢱࢆ㛤Ⓨࡋࡓ㸬⣔ࡣ❧᪉᱁Ꮚ࡛㸪ྛࢭࣝࢆ࣏࣐࣮ࣜࢭࢢ࣓
ࣥࢺࡲࡓࡣỈࡀ༨᭷ྍ⬟࡛࠶ࡾ㸪࣏࣐࣮ࣜ㙐ࢆ VHOIDYRLGLQJ ࡞ࢭࢢ࣓ࣥࢺࡢ㞟ྜ࡜ࡋ࡚⾲⌧ࡋࡓ㸬ྛ 0RQWH
&DUOR ࢫࢸࢵࣉ࡛Ỉ࡟᥋ゐࡋ࡚࠸ࡿ࣏࣐࣮ࣜࡢษ᩿࡜⁐ฟࡢ㏿ᗘࢆホ౯ࡋ㸪ࡑࢀࢆ㔜ࡳ࡜ࡋ࡚ᐇ⾜ࡍࡿ㐣⛬ࢆ☜⋡ⓗ࡟㑅ᢥࡍࡿ㸬ษ᩿࡜⁐ฟࡢ㏿ᗘ r ࡣ㸪࣏࣐࣮ࣜࢭࢢ࣓ࣥࢺ࡟㓄఩ࡍࡿỈࡢᩘ w ࡞ࡽࡧ࡟࣏࣐࣮ࣜ㙐ࡢ㛗ࡉ L ࢆᘬᩘ࡜ࡍࡿ㸪ࣛࣥࣉࡸࢫࢸࢵࣉ࡞࡝ࡢ㛵ᩘ࡜ࡋ࡚ࣔࢹࣝ໬ࡋࡓ㸬ษ᩿࡜⁐ฟࡢ㏿ᗘࡢ⤯ᑐ್࡛᫬㛫ࢫࢣ࣮ࣝࡀ㸪┦ᑐ್࡛཯ᛂᣑᩓᚊ㏿ࡀỴᐃࡉࢀࡿ㸬⤖ᬗࢆᶍࡋ࡚࣏࣐࣮ࣜ㙐ࢆつ๎ⓗ࡟୪࡭ࡓᵓ㐀࡜㸪࢔ࣔࣝࣇ࢓ࢫࢆᶍࡋ࡚࣏࣐࣮ࣜ㙐ࢆࣛࣥࢲ࣒࡟㓄⨨ࡋࡓᵓ㐀ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ㸬ࡲࡓ㸪㔞Ꮚ໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥᢏ⾡࡜ᶵᲔᏛ⩦࡟ࡼࡿ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫᢏ⾡ࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛㸪㧗㏿࡟ᾏὒศゎࡢศゎᛶ࡜ศゎ᫬㛫ࡢணࢆ⾜࠺ᢏ⾡ࢆ㛤Ⓨࡋࡓ㸬ࡇࡢ㝿࡟㸪㔞Ꮚ໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ

- 167 -

࡙࠸ࡓຍỈศゎ཯ᛂࢩ࣑࣮ࣗࣞࢱ࡟ࡼࡗ࡚⣔⤫ⓗ࡟ษ᩿㏿ᗘࢆィ⟬ࡋ㸪⏕ศゎᛶணࢩ࣑࣮ࣗࣞࢱࡢࣃ࣓ࣛ

࣮ࢱ࡜ࡋ࡚ᑟධࡍࡿ㸬ຍỈศゎ཯ᛂࢩ࣑࣮ࣗࣞࢱ࡛ࡣ㸪࢜ࣜࢦ࣐࣮ࡢຍỈศゎ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⣔⤫ⓗ࡟ィ⟬ࡍࡿᚲせࡀ࠶ࡿࡓࡵ㸪Q\ORQ ࢲ࢖࣐࣮ࡢ㓟ᛶ㸪࢔ࣝ࢝ࣜᛶ㸪࠾ࡼࡧࣛࢪ࢝ࣝࡢຍỈศゎ཯ᛂࢆࡦ࡞ᙧ࡜ࡋࡓ㸬㔞Ꮚ໬Ꮫィ⟬࡟ࡣ 17&KHP ࢆ⏝࠸㸪Ȧ%;'GHI693 ࡛ࣞ࣋ࣝゎᯒࡋࡓ㸬1XGJHG(ODVWLF%DQG
1(%  ἲ࡟ࡼࡾ㸪࢖࣓࣮ࢪᩘ  ࡛཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓ㸬཯ᛂ⣔࡜⏕ᡂ⣔ࡢึᮇᵓ㐀ࡣ 5'.LW ࢆ⏝࠸࡚ 8))࡛᭱㐺໬ࡉࢀࡓᵓ㐀ࢆࡑࢀࡒࢀ  ㏻ࡾ⏝ពࡋࡓ㸬ࡲࡓ㸪⏕ศゎᛶண
0RQWH &DUOR ἲ࡛⏝࠸ࡿษ᩿㏿ᗘ࡟ᑐࡋ࡚㸪ᗘ࡟ᅉᏊ࡜ࡋ࡚࠿࠿ࡿ⎔ቃಀᩘࢆண

ࢩ࣑࣮ࣗࣞࢱ࡛᥇⏝ࡋ࡚࠸ࡿ .LQHWLF

ᗘࡸ S+ ࡞࡝ࡢᐇ㦂᮲௳࡟ࡼࡿᙳ㡪ࢆ⪃៖ࡍࡿࡓࡵ࡟㸪ษ᩿㏿ࡍࡿ῝ᒙᏛ⩦ࣔࢹࣝࢆ 3\7RUFK ࡛ᵓ⠏ࡋࡓ㸬.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢྜᡂ཯ᛂ⤒㊰ゎᯒᵓ㐀᭱㐺໬ィ⟬㸪➨୍ཎ⌮㟁Ꮚ≧ែィ⟬㸪᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰㸦PLQLPXP HQHUJ\ SDWK 0(3㸧᥈⣴ィ⟬ࢆ㸪
17&KHP ࢆ⏝࠸࡚ィ⟬ࣞ࣋ࣝ Ȧ%;'GHI693 ࡛⾜ࡗࡓ㸬: ࠾ࡼࡧ &G ཎᏊ࡟ࡘ࠸࡚ࡣ᭷ຠෆ᰾࣏ࢸࣥࢩ
ࣕࣝࢆ౑⏝ࡋࡓ㸬0(3 ᥈⣴ࡢࡓࡵࡢ 1XGJHG(ODVWLF%DQG 1(%  ἲ࡟ࡼࡿィ⟬࡛ࡣ࢖࣓࣮ࢪᩘࢆ  ࡜ࡋ㸪཰᮰᮲௳࡜ࡋ࡚ຊࡢ㜈್ࢆ KDUWUHHERKU ࡟タᐃࡋࡓ㸬⁐፹㸦ㄏ㟁⋡㸧ࡢຠᯝࢆ⧊ࡾ㎸ࢇࡔィ⟬࡟ࡣ &2602
56 ࢆ⏝࠸ࡓ㸬




◊✲ᡂᯝ

 ⏕ศゎᛶ࣭ᾏὒศゎᛶ࣏࣐࣮ࣜࡢศゎᛶணᢏ⾡

.LQHWLF0RQWH&DUOR ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ⏝࠸ࡓ࣏࣐࣮ࣜ㓄⨨ࡢᶍᘧᅗ࡜࣏࣐࣮ࣜሢࡢᔂቯᗘࡢ᫬㛫ኚ໬ࢆᅗ ࡟♧ࡍ㸬⣔ࡢ኱ࡁࡉࡣ  ࡛㸪࣏࣐࣮ࣜࡢࢭࢢ࣓ࣥࢺᩘࡣ  ࡛࠶ࡿ㸬࠸ࡎࢀࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡟࠾࠸࡚ࡶ㸪⁐ฟ㏿ᗘ࡜ࡋ࡚ rVRO Ĭ íL Ĭ wí 㸦ࡍ࡞ࢃࡕ L ࠿ࡘ w ࡛࠶ࢀࡤ 㸪ࡑ࠺࡛࡞ࡅࢀࡤ 㸧ࢆ㑅ࢇࡔ㸬ࡇࡢࡼ࠺࡟㸪⤖ᬗෆ࡟࠾ࡅࡿ࣏࣐࣮ࣜࡢ㓄ྥ࡞ࡽࡧ࡟㏿ᗘࡢ㠀⥺ᙧᛶ࡟ࡼࡗ࡚ᔂቯ㐣⛬ࡀ␗࡞ࡿࡇ
࡜ࡀ♧ࡉࢀࡓ㸬

- 168 -ᅗ  㸦ୖẁ㸧࣏࣐࣮ࣜ㓄⨨ࡢᶍᘧᅗ㸬ୖ㠃 z  ࡟Ỉ㸬㸦ୗẁ㸧࣏࣐࣮ࣜሢࡢᔂቯᗘࡢ᫬㛫ኚ໬㸬ษ᩿㏿ᗘ
rVFL ࡣỈࡢ㓄఩ᩘ w ࡢ㛵ᩘ࡛㸪ᕥ࠿ࡽ⥺ᙧ㛵ᩘ㸪ࢫࢸࢵࣉ㛵ᩘ㸪ࣛࣥࣉ㛵ᩘ㸦ಀᩘࢆኚ໬ࡉࡏ࡚࠸ࡿ㸧㸬ᅗ 1\ORQ ࢲ࢖࣐࣮ࡢຍỈศゎࡢ཯ᛂ⤒㊰㸬ḟ࡟㸪㔞Ꮚ໬Ꮫィ⟬࡛ᚓࡓ 1\ORQ ࡢຍỈศゎࡢ཯ᛂࢆᅗ  ࡟♧ࡍ㸬࢔࣑ࢻࡢ㓟ᛶ᮲௳࡟࠾ࡅࡿຍỈศゎࡣ㸪」ᩘࡢỈศᏊ࡜཯ᛂࡋ࡚ᅄ㠃యᆺ୰㛫యࢆ⤒⏤ࡋࡓ  ẁ㝵ࡢ཯ᛂ࡛࠶ࡿࡇ࡜ࡀィ⟬࡟ࡼࡾ☜ㄆࡉࢀ࡚࠸ࡿࡀ㸪ᮏィ⟬ࡢ 1\ORQ  ࡛ࡶ෌⌧ࡉࢀࡓ㸬ྠᵝࡢ࢔࣑ࢻ࡟ᑐࡋ࡚ࡶ⣔⤫ⓗ࡟ィ⟬࡛ࡁࡿࡼ࠺࡟㸪ᮏィ⟬⤖ᯝࢆࡦ࡞ᙧ࡜ࡋ࡚ึᮇᵓ㐀ࢆ୚࠼ࡿ᪉ἲࢆᐇ⿦ࡋࡓ㸬- 169 -

⏕ศゎᛶண

ࢩ࣑࣮ࣗࣞࢱ࡟ࡘ࠸࡚ࡣ㸪⎔ቃಀᩘࢆண

ࡍࡿᏛ⩦ࣔࢹࣝࡢㄝ᫂ኚᩘ࡜ࡋ࡚㸪࣏࣐࣮ࣜࡢ⧞ࡾ

㏉ࡋ༢఩ࡢศᏊグ㏙Ꮚ࡜ࢧࣥࣉࣝࡢ⢏ᚄ࡜ᐇ㦂᮲௳㸦ᗘ㸪Ỉศ㔞㸪S+㸪᳜✀※㸧ࢆ᥇⏝ࡋ㸪௵ពࡢ࣏࣐ࣜ

࣮࡟ᑐࡋ࡚⎔ቃಀᩘࢆண

࡛ࡁࡿࡼ࠺࡟ᐇ⿦ࢆ⾜ࡗࡓ㸬ࡲࡓ  Ⅼࡢᩥ⊩ࢹ࣮ࢱࢆྵࡴࢹ࣮ࢱ࣮࣋ࢫ࡟㸪⏕ศゎᛶࡀ☜ㄆࡉࢀ࡚࠸࡞࠸࣏࣐࣮ࣜࡢ᝟ሗࢆ㏣ຍࡍࡿࡇ࡜࡛ᣑᙇࢆ⾜ࡗࡓ㸬ࡇࢀࡽࡢᨵⰋ࡟ࡼࡗ࡚ண

⢭ᗘ R 㸦ࢹ࣮ࢱ࣮࣋ࢫࡢ ࡛Ꮫ⩦ࡋ㸪ṧࡾ ࡟ᑐࡋ࡚ホ౯㸧ࡢᏛ⩦ࣔࢹࣝࡢᵓ⠏࡟ᡂຌࡋࡓ㸬.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢྜᡂ཯ᛂ⤒㊰ゎᯒ.HJJLQ ᆺ㦵᱁ࡢᙧᡂ཯ᛂࡢ୺せ࡞せ⣲཯ᛂࡢ࠺ࡕ㸪භဨ⎔ᵓ㐀࠿ࡽ඲㦵᱁ࡢᙧᡂ࡟㛵ࢃࡿ࢟ࣕࢵࣉᵓ㐀ᙧᡂ཯ᛂࢆヲ⣽࡟ㄪ࡭㸪 ẁ࡛㐍ࡴ཯ᛂ࡜㏲ḟ  ẁ࡛㐍ࡴ཯ᛂࡢ᭱ᑠ࢚ࢿ
ࣝࢠ࣮⤒㊰㸦0(3㸧ࢆ᫂ࡽ࠿࡟ࡋ㸪๓⪅཯ᛂࡀࡼࡾప࠸཯ᛂ
㞀ቨࢆᣢࡘࡇ࡜ࡸ㸪ࡑࡢ཯ᛂࡀࡼࡾ኱ࡁ࡞ㄏ㟁⋡  ࡛᭷฼࡟㐍ࡴྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 㸧㸬ࡲࡓ㸪᪂つࡢ㦵᱁ᣑᙇᆺ㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ : ࡢᙧᡂࡢࡓ
ࡵࡢẕᵓ㐀ೃ⿵࡛࠶ࡿ .HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸ࣮ࢺ: ࡢ✀ศ໬ࢆヲ⣽࡟ㄪ࡭㸪ࡇࢀࡲ࡛ࡑࡢᏑᅾࡀ␲ၥどࡉᅗ  ㏲ḟ㸱ẁ࡛㐍ࡴ࢟ࣕࢵࣉᵓ㐀ᙧᡂ཯ᛂࡢ 0(3㸦ㄏ㟁⋡ 㸧㸬ࢀ࡚࠸ࡓ㸪᪂ࡓ࡞㦵᱁ᣑᙇᆺ㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮
ࢺࡢࣅࣝࢹ࢕ࣥࢢ࣭ࣈࣟࢵࢡ࡜ࡋ࡚฼⏝࡛ࡁࡿ>+:2@íࡢྜᡂࡀ⇕ຊᏛⓗ࠿ࡘ㏿ᗘㄽⓗ࡟ྍ⬟࡛ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 㸧㸬ࡑࡋ࡚㦵᱁࡟ࣉࣟࢺࣥࢆ㛢ࡌ㎸ࡵࡓ᪂つࡢ㦵᱁ᣑᙇᆺ㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ : ࡢ㛤Ⓨἲ☜❧ࢆ┠ᣦࡋࡓ◊✲ࡢඛ⾜ㄪᰝ࡜ࡋ࡚㸪ᵝࠎ࡞ᵓ㐀࣭⤌ᡂࢆࡶࡘᣑᙇᆺ
㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ : ࡸḞᦆᆺ࣏ࣜ࢜࢟ࢯࢱ
ࣥࢢࢫࢸ࣮ࢺ : ࢆㄪ࡭㸪࡝ࡢࡼ࠺࡞࢟ࣕࢵࣉᵓ㐀ࢆᣢࡕ㸪ఱಶࡢࣉࣟࢺࣥࢆ࡝ࡢࡼ࠺࡞㓄⨨࡛㦵᱁࡟㛢ࡌ㎸ࡵࡓᣑᙇᆺ
㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺࡀᏳᐃ࡟Ꮡᅾ࡛ࡁ㸪ࡑࡋ࡚ࡑࡢᣑᙇᆺ㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺࢆᵓ⠏ࡍࡿࡓࡵࡢࣅ
ࣝࢹ࢕ࣥࢢ࣭ࣈࣟࢵࢡ࡜ࡋ࡚࡝ࡢࡼ࠺࡞Ḟᦆᆺ࣏ࣜ࢜࢟ࢯࢱ
ࣥࢢࢫࢸ࣮ࢺࡀ฼⏝ྍ⬟࡞ࡢ࠿➼࡟ࡘ࠸࡚ࡢ᝟ሗࢆከᩘ㞟ࡵࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ 㸧㸬- 170 -

ᅗ  +>+:2@࠿ࡽ>+:2@࡬ࡢࣉ
ࣟࢺࣥ⛣ື཯ᛂࡢ ,5&ᅗ  ᣑᙇᆺ㛢Ẇ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ : ࡢ⤌ᡂ࣭ᵓ㐀࡜Ᏻᐃᛶ㸬㉥ᯟ㸸ᵓ㐀ಖᣢ㸪⥳ᯟ㸸୍㒊ᔂቯ㸪㟷ᯟ㸸ᔂቯࡍࡿ : ࡢ౛㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ࣥࢠࢣࠕۻ‬ᆺ࣏ࣜ࢜࢟ࢯࢱࣥࢢࢫࢸ࣮ࢺ >;:2@ní ࡢᙧᡂ཯ᛂࡢ◊✲ࠖ㜿ஂ᰿ᫀᙪ㸪ᯞ࿴⏨㸪኱ሜ฼⾜㸪୰ᔱ㝯ே ᪥ᮏࢥࣥࣆ࣮ࣗࢱ࣮໬Ꮫ఍⛅Ꮨᖺ఍㸪࢜ࣥࣛ࢖ࣥ㸪
‫ࠕۻ‬.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢྜᡂ⤒㊰࡟㛵ࡍࡿ◊✲ࠖ ▼ୖᛌ㸪኱ሜ฼⾜㸪୰ᔱ㝯ே㸪ᯞ࿴⏨➨  ᅇ࣏࣮ࣛࣟࢢࣛࣇ࢕࣮࠾ࡼࡧ㟁Ẽศᯒ໬Ꮫウㄽ఍㸪࢜ࣥࣛ࢖ࣥ㸪



³0XOWLVFDOHVLPXODWLRQWRSUHGLFWELRGHJUDGDELOLW\RISODVWLFV´(.DZDVKLPD71DNDMLPD PACIFICHEM 2021
RQOLQH

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬71DNDMLPD.+LUDR%&KDQ-&KHP3K\V  



6 7ULEHGL . .LWDXUD 7 1DNDMLPD 5 % 6XQRM Phys. Chem. Chem. Phys.  ±  '&3-.+LUDR71DNDMLPD%XQ&KDQJ. Chem. Phys.  

à %RGD 0 %RF]DU 0 - :yMFLN 7 1DNDMLPD J. Phys. Chem. A  ±  DFVMSFDF

‫ۻ‬$ 0L\DZDNL . (GD 7 0RFKLGD 7 6DNXUDL + 2KWD 7 1DNDMLPD . 7DNDKDVKL Inorg. Chem. í   DFVLQRUJFKHPF

‫ۻ‬.(GD0$NXQH&<DVXPD++RWWD72VDNDL71DNDMLPDInorg. Chem.í  DFVLQRUJFKHPF



67RPLQDND,.DULPDWD70DWVXRND06DNDPRWR71DNDMLPD.2KDUD77DFKLNDZDACS Energy Lett.
±  DFVHQHUJ\OHWWF

+7+HQU\&KDQet al.Chem. Sci.±  '6&$:'DZVRQ$'HJRPPH06WHOOD71DNDMLPD/(5DWFOLII/*HQRYHVHWIREs Comput Mol Sci.H
  ZFPV

 7=KDQJ71DNDMLPD+&DR46XQ+%DQ+3DQ+<X==KDQJ;=KDQJ<6KHQ0:DQJACS
Appl. Mater. Interfaces±  DFVDPLF

- 171 -

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ
0XOWLFRS\DQGPXOWLVFDOHVLPXODWLRQRIELRPROHFXOHV‫ۑ‬᳃ḟ ᆂ㸦ᶓ὾ᕷ኱㝔㸧



◊✲┠ⓗ
◊✲௦⾲⪅ࡣࡇࢀࡲ࡛࡟ࠊḟୡ௦ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࡢ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࡜࡞ࡿ࣐ࣝࢳࢥࣆ࣮࣭࣐ࣝࢳࢫࢣ࣮ࣝศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢘
࢙࢔ࠕP2libࠖࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓ(http://www.csrp.riken.jp/application_j.html)ࠋࡲࡓࠊࡑࡢ࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜ࡋ
࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠ⤒㊰᥈⣴ἲ㸦ࢫࢺࣜࣥࢢἲ㸧࡜ᵓ㐀᥈⣴ἲ㸦MSES ἲ㸧ࡢ◊✲㛤Ⓨࢆ⾜ࡗࡓࠋ௒ᖺᗘ
ࡢ◊✲࡛ࡣࠊࢱࣥࣃࢡ㉁࢟ࢿࢸ࢕ࢵࢡࢫࡢ᝟ሗࢆྲྀࡾධࢀࡓゎᯒἲࡢ☜❧ࢆ┠ᣦࡋࠊ࣐ࣝࢥࣇ≧ែࣔࢹࣝ(Markov State Model: MSM)ࢆྲྀࡾධࢀࡓศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢゎᯒࢆ⾜ࡗࡓࠋMSM ࡢᵓ⠏࡟ࡣࠊ≧ែ㛫㑄⛣ࡢ࣐ࣝࢥࣇᛶࢆ௬ᐃࡋࠊከᩘࡢ▷᫬㛫 MD ࠿ࡽ≧ែ㛫㑄⛣⾜ิࢆィ⟬ࡍࡿࠋࡑࡢᅛ᭷್ၥ
㢟ࢆゎࡃࡇ࡜࡟ࡼࡾࠊ࢟ࢿࢸ࢕ࢵࢡ࡞࣐ࢡࣟ≧ែ࡜≧ែ㛫ࡢ㑄⛣☜⋡ࡀィ⟬࡛ࡁࠊ㉳ࡇࡾ࠺ࡿᵓ㐀ኚ໬ࣃࢫ࢙࢘࢖࡜ࡑࡢ᫬ᐃᩘࢆ⥙⨶ⓗ࡟ᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋᮏ⏦ㄳ࡛ࡣࠊࣇ࢕࣓ࣛࣥࢺᆺ࢔ࢡࢳࣥ࠿ࡽࡢࣜࣥ㓟ሷ(phosphate: Pi)ゎ㞳㐣⛬࡟㐺⏝ࢆヨࡳࠊࣃ࣓ࣛࢱ౫Ꮡᛶࢆྵࡵࡓヲ⣽࡞ゎᯒࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲࢩ࣑࣮ࣗࣞࢩࣙࣥࡢึᮇࣔࢹࣝ࡜ࡋ࡚ࡣࠊྡྂᒇ኱Ꮫ๓⏣ᩍᤵࡽ࡟ࡼࡾゎ࠿ࢀࡓࣇࣛࢢ࣑ࣥ⤖ྜࣇ࢕࣓ࣛ

ࣥࢺᆺ㸦F ᆺ㸧࢔ࢡࢳࣥࢆ⏝࠸ࡓࠋF ᆺᵓ㐀ࢆ⥔ᣢࡍࡿࡓࡵࠊࣇࣛࢢ࣑ࣥ⤖ྜࡢࡲࡲ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ
⾜ࡋࡓࠋࣜࣥ㓟ሷ(phosphate: Pi)࡜ࡋ࡚ࡣࠊATP ࠿ࡽ Pi ࡀゎ㞳ࡍࡿ཯ᛂ࡟㛵ࡍࡿ QM/MM ィ⟬ࡢඛ⾜◊✲࡛ᥦ᱌ࡉࢀࡓ H2PO4-ࡢ protonatino ࢆ㐺⏝ࡋࡓࠋMSES ἲࢆ⏝࠸ࡓඛ⾜◊✲࡛ᚓࡽࢀࡓᵓ㐀࢔ࣥࢧࣥࣈࣝ࠿ࡽࠊ
ᮏ◊✲࡛⏝࠸ࡿ MD ィ⟬ࡢึᮇᵓ㐀ࢆ㸦ᵓ㐀ࢡࣛࢫࢱࣜࣥࢢ࡞࡝࡟ࡼࡾ Pi ࡀ࡛ࡁࡿ㝈ࡾࡤࡽࡅࡓศᕸ࡟࡞ࡿ
ࡼ࠺࡟㸧㑅ᢥࡋࡓࠋィ⟬ࡣࠊࢩࢫࢸ࣒࡟࢖ࣥࢫࢺ࣮ࣝࡉࢀ࡚࠸ࡿศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢙࢘࢔ AMBER
࡟ࡼࡾᐇ⾜ࡋࡓࠋᚋ㏙ࡢ࣐ࣝࢥࣇ≧ែࣔࢹࣝࡢጇᙜᛶ࡟ࡘ࠸࡚⢭ᰝࡋࡘࡘ MD ィ⟬ࡢᮏᩘࢆቑࡸࡋ࡚࠸ࡁࠊ
᭱⤊ⓗ࡟ࡣ 50 ns ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆィ 600 ᮏᐇ⾜ࡋࡓ㸦ᮏࢩࢫࢸ࣒࡛ࡣࠊࡑࡢィ⟬ࡢ୍㒊ࢆᐇ᪋ࡋࡓ㸧ࠋ࣐ࣝࢥࣇ≧ែࣔࢹࣝᵓ⠏࡟ࡘ࠸࡚ࡣࠊ௨ୗࡢࡼ࠺࡟ᚲせ࡞ࣃ࣓ࣛࢱࡢ⢭ᰝࢆࡋࡘࡘタᐃࢆ⾜ࡗࡓࠋ࣭཯ᛂᗙᶆ࡛࠶ࡿ feature ࡜ࡋ࡚ࡣࠊ࢔ࢡࢳࣥࡢࢧࣈࢻ࣓࢖ࣥ 1 ࡜ 2 ࢆཧ↷ᵓ㐀࡟ࣇ࢕ࢵࢺࡋࡓࡢࡕࠊPi ࡢ PཎᏊ Cartesian ᗙᶆࢆ㑅ᢥࡋࡓࠋࡘࡲࡾࠊ◊✲ࡢ➨୍ẁ㝵࡜ࡋ࡚ Pi ࡢ୪㐍ᣑᩓࡘ࠸࡚ࡢࡳ⪃៖ࡋࡓࡀࠊ௒ᚋࡢ
ゎᯒ࡛ࡣ௚ࡢྍ⬟ᛶ࡟ࡘ࠸࡚ࡶ᥈ࡿணᐃ࡛࠶ࡿࠋ
࣭ࡇࡢ feature ࡟ࡘ࠸࡚ࠊk-means ࢡࣛࢫࢱࣜࣥࢢࢆィ⟬ࡍࡿࡇ࡜࡟ࡼࡾ state ࢆᐃ⩏ࡋࡓࠋࢡࣛࢫࢱᩘ࡜࠸࠺
ࣁ࢖ࣃ࣮ࣃ࣓ࣛࢱ࡟ࡘ࠸࡚ࡶ௒ᚋࡢ༑ศ࡞᳨ウࡀᚲ㡲࡛࠶ࡿࡀࠊ30 ಶࡢ state ࡛ᐃ⩏ࡍࡿ࡜ state 㛫ࡢ㊥㞳ࡀc ⛬ᗘ࡟࡞ࡾ㑄⛣ࢿࢵࢺ࣮࣡ࢡࡀ࠺ࡲࡃᵓ⠏ࡉࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ 1 ཧ↷㸧ࠋ࣭Pi ࡀ࢔ࢡࢳࣥ࠿ࡽ᏶඲࡟ゎ㞳ࡋࡓ≧ែࡣ඲᪉ྥⓗ࡟ศᕸࡋ࡚࠾ࡾ⪃៖ࡍࡿࡢࡀ㞴ࡋ࠸ࠋࡑࡢࡓࡵࠊPi ࡀ࢔ࢡࢳࣥ࡜ཎᏊࢥࣥࢱࢡࢺࡋ࡚࠸࡞࠸ᵓ㐀࡟ࡘ࠸࡚ࡣゎᯒ࠿ࡽ㝖እࡋࡓࠋPi ࡢ఩⨨ࡔࡅ࡛࡞ࡃ ADP ࡜ཎᏊࢥࣥࢱࢡࢺࡀ⥔ᣢࡉࢀ࡚࠸ࡿ࠿ࡶ≧ែࡢᐃ⩏࡜ࡋ࡚㔜せ࡟࡞ࡿࡓࡵࠊPi ࡜ ADP ࡀࢥࣥࢱࢡࢺࡋࡓᵓ㐀ࡣูࡢ- 172 -

state ࡜ࡋ࡚ᐃ⩏ࡋࡓࠋ࣭࣐ࣝࢥࣇ≧ែࣔࢹࣝࡢ lag time ࡟ࡘ࠸࡚ࡶࣃ࣓ࣛࢱࢆኚ࠼࡞ࡀࡽᅛ᭷್ࡢ᫬ᐃᩘィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾ⢭ᰝࡋࠊ5 ns ࡛➨୍ᅛ᭷್ࡀ཰᮰ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡇࢀࡽࡢࣃ࣓ࣛࢱタᐃࢆ⏝࠸࡚࣐ࣝࢥࣇ≧ែࣔࢹࣝࢆᵓ⠏ࡋࡓࠋィ⟬࡟ࡣࠊpyEMMA ࡢࢯࣇࢺ࢙࢘࢔ࢆ⏝
࠸ࡓࠋ



◊✲ᡂᯝ
࢔ࢡࢳࣥࡣ 4 ࡘࡢࢧࣈࢻ࣓࢖ࣥ࠿ࡽ࡞ࡿᵓ㐀ࢆྲྀࡗ࡚࠾ࡾࠊF ᆺ࡜ G ᆺ࢔ࢡࢳ࡛ࣥࡣࢧࣈࢻ࣓࢖ࣥ 1-2 ࡜

3-4 ࡢ㛫࡟࠶ࡿࢾࢡࣞ࢜ࢳࢻ⤖ྜ cleft ࡀ㛤㛢ࡍࡿ㐠ືࡀ㉳ࡁ࡚࠸ࡿࠋ
⥙⨶ⓗ࡞ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊ
Pi ࡀゎ㞳ࡍࡿࣃࢫ࡜ࡋ࡚ࠊࢾࢡࣞ࢜ࢳࢻ⤖ྜ cleft ࢆ㏻ࡿࣃࢫ࡜࡜ࡶ࡟ࠊࢧࣈࢻ࣓࢖ࣥࡢ㛫ࢆ㈏㏻ࡍࡿࡼ࠺࡞ࣃࢫࡶぢฟࡉࢀࡓ㸦ᅗ 1㸧ࠋඛ⾜◊✲࡛ࡣ Hic75 ࠾ࡼࡧ Arg179 ࡢ㔜せᛶࡀ♧၀ࡉࢀࡓࡀࠊPDB: 5OOE ࡢ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺᵓ㐀ࢆཧ↷ࡍࡿ࡜ࠊࡑࡢ᪉ྥ࡟ࡣࣇ࢕࣓ࣛࣥࢺࡢูࡢ࢔ࢡࢳࣥศᏊࡀᏑᅾࡋ࡚࠾ࡾ Pi ࡀゎ㞳࡛ࡁ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋ
3 ㏻ࡾࡢࣃࢫ࡟ࡘ࠸࡚ mean first passage time ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊPi ゎ㞳ࡢ᫬ᐃᩘ࡜ࡋ࡚ 10 ࣐࢖ࢡࣟ⛊࣮࢜ࢲ࣮(Path1/2)࡜࣑ࣜ⛊࣮࢜ࢲ࣮(Path3)ࡢ 2 ㏻ࡾ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊࢧࣈࢻ࣓࢖ࣥ㛫ࠊ≉࡟ࢧࣈࢻ࣓࢖ࣥ 3-4 㛫ࡢ㐠ືࡀࢾࢡࣞ࢜ࢳࢻ⤖ྜ cleft 㛤㛢㐠ືࡼࡾࡶ࠿࡞ࡾᑠࡉ࠸ࡇ࡜࠿ࡽྜ⌮ⓗ࡛࠶ࡿ࡜ゝ࠼ࡿࠋࣇ࢕࣓ࣛࣥࢺୖ࡛ࡢ࢔ࢡࢳࣥ ATP ᆺ࠿ࡽ ADP ᆺࡢ㑄⛣ࢆㄪ࡭ࡓ᭱㏆ࡢᐇ㦂࡟࠾࠸࡚ࠊ2 ࡘࡢ᫬㛫࣮࢜ࢲ࣮
㸦㹼10 ࣑ࣜ⛊ࡢ㏿࠸㑄⛣࡜㹼⛊ࡢ㐜࠸㑄⛣㸧ࡢᵓ㐀ኚ໬ࡀぢฟࡉࢀ࡚࠾ࡾࠊࡑࡢᑐᛂ㛵ಀ࡟ࡘ࠸࡚࢔ࢡࢳࣥ
ࡢᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫ࡜࡜ࡶ࡟௒ᚋࡢゎᯒ᳨࡛ウࡍࡿணᐃ࡛࠶ࡿࠋᅗ  ࣐ࣝࢥࣇ≧ែࣔࢹࣝ࡟ࡼࡾᚓࡽࢀࡓ࢔ࢡࢳࣥࣜࣥ㓟ሷゎ㞳ࡢࣃࢫ࢙࢘࢖࡜᫬ᐃᩘࠋ ಶࡢ VWDWH ࢆ VSKHUH ⾲♧ࡋࠊ㑄⛣☜⋡ࡀ኱ࡁ࡞ VWDWH 㛫ࢆ⥺࡛⤖ࢇࡔࠋ⫙Ⰽࡣ 3'%22( ࡢ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺᵓ㐀ࢆ♧ࡍࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
1. Enhanced sampling methods targeting at large proteins, Kei Moritsugu, ᪥ᮏ⏕≀≀⌮Ꮫ఍➨ 59 ᅇᖺ
఍ࠊ2021/11/26, ᅜෆ㸪ཱྀ㢌  9$(GULYHQ PXOWLVFDOH HQKDQFHG VDPSOLQJ Kei Moritsugu, ᪥ᮏ⏕≀≀⌮Ꮫ఍➨ 59 ᅇᖺ఍ࠊ2021/11/26, ᅜෆ㸪ཱྀ㢌ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

Moritsugu K.

Multiscale enhanced sampling using machine learning. Life 2021, 11, 1076.

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Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ࣮ࣟࢳ
Theoretical approach on electronic states of luminescent metal
complexes and their assembled systems‫ۑ‬ຍ⸨ ᫀᏊ㸪㰻⸨ ኱ᑗ㸪▮㔝 ுኴ㸪㰻⸨ ᭸ஓ㸪9HUQHU6llVN㸪ྜྷ⏣ ᑗᕫ㸪ᑠᯘ ཌᚿ㸦㛵すᏛ㝔኱Ꮫ⏕࿨⎔ቃᏛ㒊࣭໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲㝔໬Ꮫ㒊㛛㸧◊✲┠ⓗ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࠸ࠊᵓ㐀᭱㐺໬ࡋࡓࠋᐦᗘỗ㛵ᩘἲ ')7 ࢆ⏝࠸࡚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Ⓨගࡸ࣮࢝ࣛࢳ࣮ࣗࢽࣥࢢࢆᐇ⌧ࡍࡿࡓࡵࡢศᏊᵓ㐀ணࢆ⾜࠸ࠊᐇ㦂໬Ꮫࡢࣇ࢕࣮ࢻࣂࢵࢡ࡟฼⏝ࡋࡓࠋ')7 ࠾ࡼࡧ 7'')7 ィ⟬࡟ࡣ *DXVVLDQࡲࡓࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ



◊✲ᡂᯝ

 㐣෭༷ᾮయ㸭⤖ᬗ┦㌿⛣࡟ࡼࡾⓎගࢆ 212)) ࡍࡿⓑ㔠 ,, 㘒యᙜ◊✲ᐊ࡛㛤ⓎࡋࡓຊᏛ่⃭࡟ࡼࡿ㐣෭༷ᾮయ㸭⤖ᬗ┦㌿⛣࡟క࠸Ⓨගࢆ 212)) ࡍࡿⓑ㔠 ,, 㘒య㸦ྑᅗ㸧࡟ࡘ࠸࡚ࠊࡑࡢⓎග≉ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ≉࡟ࠊศග໬Ꮫ ᐃ࡟ࡼࡾࠊࡇࡢⓑ㔠 ,, 㘒య࢔ࢽ࢜ࣥࡢ
Ⓨග⏤᮶ࡣ㓄఩Ꮚ୰ᚰࡢ ʌʌ ບ㉳≧ែ࡟  0; /&7 㑄⛣ࡀΰྜࡋࡓᛶ㉁ࢆ
ᣢࡘࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡓࡓࡵࠊࡑࡢヲ⣽࡟ࡘ࠸࡚⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ
⤖ᯝࠊࡇࡢ㘒యࡣ୕㔜㡯ບ㉳≧ែ࡟࠾࠸࡚ࢫࣆࣥᐦᗘࡀⓑ㔠ཎᏊ࠾ࡼࡧ㓄఩ࡋ࡚࠸ࡿሷ໬≀࢖࢜ࣥ࡟኱ࡁࡃᒁᅾ໬ࡋ࡚࠸ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋࡇࢀ࡟
ࡼࡾࠊ୕㔜㡯ບ㉳≧ែ࡟ⓑ㔠ཎᏊࡀ኱ࡁ࡞ᐤ୚ࢆࡋ࡚࠸ࡿ࡜࠸࠺ศග໬Ꮫ
ᐃࡢ⤖ᯝࡢጇᙜᛶࡀ᳨ドࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ㧗ຠ⋡᭷ᶵ (/ ⣲ᏊࡸຊᏛ่⃭ࢆ᳨ฟࡍࡿࢭࣥࢧ࣮ࢆ㛤Ⓨࡍࡿࡓࡵࡢ㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ
 ᙉⓎගᛶ 1࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠 ,, 㘒యࡢ⵨Ẽㄏ㉳༢⤖ᬗ㸫༢⤖ᬗ┦㌿⛣ᙜ◊✲ᐊ࡛㛤ⓎࡋࡓᙉⓎගᛶࡢ 1࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠 ,, 㘒య㸦ḟ㡫ᅗࠊ㸧࡟ࡘ࠸࡚ࠊࡑࡢ༢⤖ᬗ㸫༢⤖ᬗ┦㌿⛣ᣲື࡜࣋࢖࣏ࢡ࣑ࣟࢬ࣒࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊࡇࡢ㘒యࡣ⤖ᬗ໬┤ᚋࡢ㸱Ỉ࿴

- 174 -

≀ࡢ≧ែ࡛ࡣ㟷ⰍⓎගࢆ♧ࡍ୍᪉ࠊ஝⇱࡟ࡼࡗ࡚༢⤖ᬗᛶࢆ⥔ᣢࡋࡓࡲࡲ⥳ⰍⓎගᛶࡢ↓Ỉ≀࡜࡞ࡾࠊࡇࢀ࡟Ỉ⵨Ẽࢆ᭚㟢ࡍࡿࡇ࡜࡛
ẁ㝵ⓗ࡟ඖࡢ㸱Ỉ࿴≀ࡀ෌⏕ࡍࡿࠋࡑࡇ࡛ࠊࡇࡢⓎගⰍࡢኚ໬࡟ࡘ
࠸࡚⪃ᐹࢆ⾜࠺ࡓࡵ࡟⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊィ⟬࡟ࡼࡾồࡵࡽࢀࡓ↓Ỉ≀ࡢ +202/802 ࢠࣕࢵࣉࡣ㸱Ỉ࿴≀ࡢࡶࡢ࡜ẚ࡭࡚᭷ព࡟ᑠࡉࡃࠊࡇࡢ↓Ỉ≀࡟࠾ࡅࡿⓎගⰍࡢ㛗Ἴ㛗ࢩࣇࢺࡀ⬺Ỉ࡟ࡼࡿ㔠ᒓ㛫┦஫స⏝ࡢᙉ໬࡟ࡼࡿࡶࡢ࡛࠶ࡿࡇ࡜ࡀ᳨ドࡉࢀࡓࠋᮏᡂᯝࡣእ㒊่⃭࡛ᰂ㌾࡟ᵓ㐀࠾ࡼࡧᶵ⬟ࢆไᚚྍ⬟࡞⤖ᬗᮦᩱࢆタィࡍࡿ࠺࠼࡛㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ

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㌾ ; ⥺ග໬Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXGLHVRQVRIW;UD\3KRWRFKHPLFDO3KHQRPHQD‫ۑ‬㧗ᶫಟ㸪ᒣᮧᾴ௓㸦ᗈᓥ኱㝔⌮㸧㸯㸬◊✲┠ⓗ㸪ෆᐜᮏㄢ㢟࡛⾜ࡗࡓ◊✲ࡢ୰࠿ࡽ௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡑࡢ⤖ᯝࢆ⡆༢࡟㏙࡭ࡿࠋ  ᾮయ䜶䝍䝜䞊䝹䛾Ỉ⣲⤖ྜᵓ㐀䛾ᗘ౫Ꮡᛶ  㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒࡟ࡼࡿ᪂つ ;(6 ィ⟬ᡭἲࡢ㛤Ⓨ㸰㸬◊✲᪉ἲ㸪ィ⟬᪉ἲ㸪◊✲ᡂᯝ  ᾮయ䜶䝍䝜䞊䝹䛾Ỉ⣲⤖ྜᵓ㐀䛾ᗘ౫Ꮡᛶᮏ◊✲࡛ࡣ㌾ ; ⥺Ⓨගศග ;(6 ࢆ⏝࠸ࠊᾮయ࢚ࢱࣀ࣮ࣝࡢỈ⣲⤖ྜ࡟ࡼࡿᵓ㐀ࡢ 㹼. ࡢ㛫ࡢᗘ౫Ꮡ࡟ࡘ࠸࡚⌮ㄽⓗᐇ㦂ⓗゎᯒࢆ⾜ࡗࡓࠋྂ඾ⓗศᏊືຊᏛ 0' ィ⟬࡛  ศᏊ༢఩ࡢ࢚ࢱࣀ࣮ࣝࢆࢩ࣑࣮ࣗࣞࢩࣙࣥࡋ㹼. ࡢᵓ㐀ࢆసᡂࡋࡓࠋࡑࡢᚋྂ඾ⓗ 0' ࡢᵓ㐀࠿ࡽ  ಶࡢ㸯㸵ศᏊ࢚ࢱࣀ࣮ࣝࢡࣛࢫࢱࢆࣆࢵࢡ࢔ࢵࣉࡋ ࡑࡢᵓ㐀࡟ᑐࡋ࡚ࢥ࢔࣮࣍ࣝ≧ែࡢࢲ࢖ࢼ࣑ࢡࢫࡶຍ࿡ࡋ࡚ ;(6 ࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓࠋᐇ㦂࡜ィ⟬ࡢ ;(6 ࢫ࣌ࢡࢺࣝࢆᅗ㸯࡟♧ࡍࠋᐇ㦂࣭ィ⟬ඹ࡟ ᗘࡢୖ᪼࡟క࠸ప࢚ࢿࣝࢠ࣮ഃࡢࣆ࣮
ࢡࡀῶᑡࡋ 㧗࢚ࢿࣝࢠ࣮ഃࡢࣆ࣮ࢡࡀቑຍࡋ࡚࠸ࡿᵝᏊࡀぢࡽࢀࡿࠋࡇࡢࡇ࡜ࡼࡾィ⟬ࡢᵓ㐀ࡣᐇ㦂ࡢᵓ㐀ࢆ࠺ࡲࡃ෌⌧࡛ࡁ࡚࠸ࡿ࡜௬ᐃࡋࠊ0' ࡢᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋບ㉳ศᏊ࿘㎶ࡢỈ⣲⤖ྜᵝᘧࢆᅗ㸰࡟♧ࡍࠋࡇࡇ࡛ 'P$Q ࡢ P ࡜ Q ࡣࡑࢀࡒࢀỈ⣲౪୚యࠊཷᐜయࡢᩘࢆ⾲ࡍࠋࡲࡓỈ⣲⤖ྜࡢ᭷↓࡟ᑐࡍࡿ㜈್ࡣ :HUQHW ࡢᐃ⩏ࢆ㐺⏝ࡋࡓࠋ'$ ࡀᨭ㓄ⓗ࡛࠶ࡾࠊ࢚ࢱࣀ࣮ࣝࡣ୺࡟Ỉ⣲౪୚యỈ⣲ཷᐜయࡀ┤㙐≧࡟ࡘ࡞ࡀࡿࡇ࡜ࢆ♧၀ࡍࡿࠋࡉࡽ࡟ࠊ ᗘࡢୖ᪼࡟క࠸ '$ ࡢᵓ㐀ࡢ๭ྜࡀ኱ࡁࡃῶᑡࡋ࡚
࠸ࡿࠋࡲࡓࡇࡇ࡟ࡣ♧ࡉ࡞࠸ࡀࠊ

ᗘୖ᪼࡟క࠸ࢡࣛࢫࢱࡢࢧ࢖ࢬࡀᑠࡉࡃ࡞ࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ

ࡉࡽ࡟ࡑࢀࡒࢀࡢỈ⣲⤖ྜᒁᡤᵓ㐀࠿ࡽࡢ ;(6 ࢫ࣌ࢡࢺࣝ࡟ࡼࡾࠊ'$ ࡢ ;(6 ࢫ࣌ࢡࢺࣝࡣ . ྛ ᗘ࡟࠾࠸࡚ప࢚ࢿࣝࢠ࣮ഃ࡟኱ࡁ࡞ࣆ࣮ࢡࢆᣢࡘࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡼࡗ࡚࢚ࢱࣀ࣮ࣝࡣᾮయ≧ែ࡟࠾࠸࡚ '$ ࡢ≧ែࢆᇶᮏᵓ㐀࡜ࡋ࡚ᣢࡕࠊ ᗘࡢୖ᪼࡟క࠸ࡑࢀࡀቯࢀ࡚࠸ࡃ࡜⪃࠼ࡽࢀࡿࠋ




100



80

Ratio (%)

Intensity (arb. units)

241K
313K


240 K
340 K



526

Emission energy (eV)

528



60
40
20



0


524

㻌㻞㻠㻜㻌㻷
㻌㻟㻠㻜㻌㻷

D0A0

D0A1

D0A2

D1A0

D1A1

D1A2

Type of H-bonds



Sum





ᅗ  Ỉ⣲ᵓ㐀ᒁᡤゎᯒࠋ'P$Q ࡢ P ࡜ Q ࡣᅗ 㸸ᐇ㦂㸦ୖ㸧࡜ィ⟬㸦ୗ㸧ࡢ ;(6 ࢫ࣌ࡑࢀࡒࢀỈ⣲౪୚య࡜ཷᐜయࡢᩘࠋ

ࢡࢺࣝ



- 177 -  㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒࡟ࡼࡿ᪂つ ;(6 ィ⟬ᡭἲࡢ㛤Ⓨ㌾ ; ⥺ศගἲࡣບ㉳ศᏊ࿘㎶ࡢ໬Ꮫⓗ⎔ቃ࡟ᩄឤ࡛࠶ࡾࠊ㏆ᖺᾮ┦࡟࠾ࡅࡿศᏊࣞ࣋ࣝࡢᵓ㐀ゎᯒ࡟ᑐࡋ࡚ᙉຊ࡞ࢶ࣮ࣝ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ≉࡟㌾ ; ⥺㡿ᇦࡢ ;(6 ἲࡣᇶᗏ≧ែࡢ㓄⨨ࡢࡳ࡞ࡽࡎࠊ
ෆẆṇᏍ≧ែࡢࢲ࢖ࢼ࣑ࢡࢫࡶࢫ࣌ࢡࢺࣝ࡟཯ᫎࡉࢀࠊᚓࡽࢀࡿࢫ࣌ࢡࢺࣝࡢゎ㔘ࢆṇࡋࡃ⾜࠺ࡓࡵ࡟ࡣ㟁Ꮚ≧ែィ⟬࡟ຍ࠼ࢫ࣌ࢡࢺࣝィ⟬ᢏἲࡶ⢭㘐ࡋ࡚࠸ࡃᚲせࡀ࠶ࡿࠋᡃࠎࡀ⏝࠸࡚࠸ࡿ༙ྂ඾ㄽ㏆ఝ
࡟ࡼࡿ .UDPHUV+HLVHQEHUJ 6&.+ ࡢศᩓᘧ࡟ࡼࡿ ;(6 ࢫ࣌ࢡࢺࣝィ⟬ᡭἲࡣ㑄⛣ᙉᗘࡀ᫬㛫ࡢ㛵ᩘ࡜ࡋ࡚ᚓࡽࢀࠊࡑࢀࢆ )RXULHU ኚ᥮࡟ࡼࡾ࢚ࢿࣝࢠ࣮ࡢ㛵ᩘ࡟ኚ᥮ࡍࡿࡇ࡜࡟ࡼࡾࢫ࣌ࢡࢺࣝࢆᚓࡿࠋࡇ
ࡇ࡛ၥ㢟࡜࡞ࡿࡢࡣࠊ㟁Ꮚ≧ែ࡟ࡼࡗ࡚ᚓࡽࢀࡿฟຊࡣ㏻ᖖ࢚ࢿࣝࢠ࣮ࡢప࠸㡰࡟୪࡭ࡽࢀ࡚࠾ࡾࠊ᫬
㛫࡟ᑐࡍࡿ࣏ࢸࣥࢩࣕࣝ᭤⥺ࡣ」㞧࡟஺ᕪ㠀஺ᕪࡀ⏕ࡌࠊᑐᛂࡍࡿ㟁Ꮚ≧ែࡢ㑄⛣ᙉᗘࡣ࡞ࡵࡽ࠿࡟᥋
⥆ࡉࢀ࡞࠸ࠋ6&.+ ᘧࡣࡑࢀࡒࢀࡢ㟁Ꮚ≧ែ࡟ᑐࡋ࡚㐺⏝ࡋ࡞ࡅࢀࡤ࡞ࡽࡎࠊࡑࡢࡓࡵࡑࡢࡲࡲ )RXULHUኚ᥮ࢆ࠿ࡅࡿࡇ࡜࡟ࡼࡾࢫ࣌ࢡࢺࣝࡢࣈ࣮ࣟࢻࢽࣥࢢࡋ࡚ࡋࡲ࠸ࠊࢫ࣌ࢡࢺࣝ⢭ᗘࡢຎ໬ࡢཎᅉࡢ㸯ࡘ࡜࡞ࡗ࡚࠸ࡓࠋᡃࠎࡣ㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒ *$ ࢆ㐺⏝ࡋࠊࢫ࣒࣮ࢬ࡟࣏ࢸࣥࢩࣕࣝ᭤⥺࡜㑄⛣ᙉᗘࢆ᥋⥆ࡍࡿࢫ࣮࣒࢟ࢆ㛤Ⓨࡋࠊ;(6 ィ⟬ࢫ࣌ࢡࢺࣝࡢ⢭ᗘྥୖࢆ⾜ࡗࡓࠋ඾ᆺⓗ䛺౛䛸䛧䛶䚸Ỉ䠑㔞య䛾 ;(6 䝇䝨䜽䝖䝹䜢ᅗ䠏䛻♧䛩䚹*$ 䜢㐺⏝䛩䜛๓䛷䛿䝫䝔䞁䝅䝱䝹᭤⥺䛜⃭䛧䛟஺ᕪ㠀஺ᕪ䜢䛚䛣䛧䚸㑄⛣ᙉᗘ᭤⥺䛿」㞧䛻ධ䜜᭰䜟䜚䜢䛧䛶䛧䜎䛖䛸䛣䜝䛜⏕䛨䛶䛧䜎䛖䛜䚸᪂つ䛻㛤Ⓨ䛧䛯*$ 䛻䜘䜛ฎ⌮䛻䜘䜚䚸㑄⛣ᙉᗘ᭤⥺䛜䝇䝮䞊䝈䛻䛥䜜ⴭ䛧䛟ᨵၿ䛥䜜䛶䛔䜛䚹䛣䛾ᡭἲ䜢⏝䛔 ;(6 䝇䝨䜽䝖䝹ィ⟬䜢⾜䛳䛯䛸䛣䜝䚸㐺⏝๓䛾䝕䞊䝍䛻䜘䜛䝇䝨䜽䝖䝹䛻ẚ䜉䜘䜚㗦䛔ᵓ㐀䛜ᚓ䜙䜜䚸㟁Ꮚ≧ែኚ໬䛾ヲ⣽䛜㆟ㄽ䛷䛝䜛䜘䛖䛻䛺䛳䛯䚹ᮏᡭἲ䜢௒ᚋ኱䛝䛺䜽䝷䝇䝍⣔䛻㐺⏝䛧䚸ᾮయ䛾 ;(6 䝇䝨䜽䝖䝹ィ⟬䛻ᙺ❧䛶䛶䛔䛟ணᐃ䛷䛒䜛䚹ᅗ㸱Ỉ㸳㔞యࡢ㑄⛣ᙉᗘࠋ㸦ᕥ㸧㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒ฎ⌮๓ࠋ㸦୰㸧㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒ฎ⌮ᚋࠋ㸦ྑ㸧ィ⟬࡟ࡼࡿ ;(6 ࢫ࣌ࢡࢺࣝࠋ㯮㸸ฎ⌮๓ࠋ㉥㸸ฎ⌮ᚋࠋ㸱㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᒣᮧࡽ㸪ᨺᑕග⛉Ꮫྜྠࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪ᮾி㸦࢜ࣥࣛ࢖ࣥ㸧㸲㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1)XWDPDWD HWDO&KHP3K\V/HWW SDJHV   7 *HMR HWDO- 3K\V%    SDJHV   /3HWWHUVVRQDQG27DNDKDVKL7KHR&KHP$FF     SDJHV   +<DPDQHHWDO&RPP0DWHULDO   SDJHV  - 178 -

࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉Ꮫ
Computational Science for Energy Conversion Materials‫ۑ‬ᒣୗ᫭୍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፹ࠊ࢚ࢿࣝࢠ࣮㈓ⶶᢏ⾡࡜ࡋ࡚ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ
㟁ụࢆྲྀࡾୖࡆࠊ
ࠕ࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱࡢィ⟬⛉Ꮫࠖࢆ᥎㐍ࡋࡓࠋ௧࿴  ᖺᗘࡣ㸯㸧༙ᑟయගゐ፹ᮦᩱࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜࣏࣮ࣛࣟࣥᙧᡂࡢ⌮ㄽⓗ◊✲࡜ࠊ㸰㸧ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 1D105 㐽ⶸᐃᩘࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⌮ㄽண࡟ࡘ࠸࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ༙ᑟయගゐ፹ᮦᩱࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜࣏࣮ࣛࣟࣥᙧᡂࡢ⌮ㄽⓗ◊✲࣓ࢳࣝ࢔ࣥࣔࢽ࣒࢘㖄࣌ࣟࣈࢫ࢝࢖ࢺࡀග࢚ࢿࣝࢠ࣮ኚ᥮ᮦᩱ࡜ࡋ࡚㧗ຠ⋡ࢆ᭷ࡍࡿせᅉࡢ୍ࡘ࡜ࡋ࡚ࠊ
ග⏕ᡂ࢟ࣕࣜ࢔ࡀ⦪ᆺගᏛࣇ࢛ࣀࣥ࡜┦஫స⏝ࡋࠊࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥࢆᙧᡂࡋ࡚ᣑᩓࡍࡿࡇ࡜࡟࠶
ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ࢟ࣕࣜ࢔㸫ࣇ࢛ࣀࣥ┦஫స⏝ࡢ➨୍ཎ⌮ィ⟬࡟ᇶ࡙࠸࡚ࠊ༙ᑟయගゐ፹ᮦᩱ࡟࠾ࡅࡿࠊග⏕ᡂ࢟ࣕࣜ࢔࡜⦪ᆺගᏛࣇ࢛ࣀࣥࡢ┦஫స⏝࡟ࡼࡿࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥᙧᡂࡢほⅬ࠿ࡽࠊ㸯㸧㉸㧗㏿᫬㛫ศゎ ; ⥺྾཰ศගἲ࡟ࡼࡿගບ㉳ :2 ࡢᒁᡤᵓ㐀ኚ໬࡜ࠊ㸰㸧Ỉศゎගゐ፹ 6U7L2$Oࡢ࢟ࣕࣜ࢔ᣑᩓ࡟ࡘ࠸࡚㆟ㄽࡋࡓࠋᐦᗘỗ㛵ᩘ⌮ㄽ㸦**$3%(㸧࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬ࡢࡓࡵ࡟ 48$1780
(635(662 ࢆ⏝࠸ࠊ:2ࠊ6U7L2$O ࡢ㟁Ꮚ≧ែィ⟬ࠊࣇ࢛ࣀࣥศᩓࠊ㟁Ꮚࣇ࢛ࣀࣥ⤖ྜࡢィ⟬࡟ࡣ❧᪉ᬗࡢᵓ㐀ࢆ⏝࠸ࡓࠋ㟁Ꮚࣇ࢛ࣀࣥ┦஫స⏝ࢆ➨୍ࣈࣜࣜ࢔ࣥ㡿ᇦ࡛ᖹᆒࡋࡓ㟁Ꮚࣇ࢛ࣀ࣭ࣥࢫ࣌ࢡࢺࣝᐦᗘ㸦ȘA㸧ࡢ⾲ᘧ࡟࠾ࡅࡿࣇ࢙࣑࣭࢚ࣝࢿࣝࢠ࣮ࢆ௵ពࡢ࢚ࢿࣝࢠ࣮ e $ ࡜ࡋࠊ௵ពࡢ࢚ࢿࣝࢠ࣮㡿ᇦ࡬ࡢ㐺⏝ࢆྍ⬟࡟ࡋࡓࠋ  ࡇࡇ࡛ࠊgLMȤ k,q ࡣ㟁Ꮚࣇ࢛ࣀࣥ⤖ྜ⾜ิせ⣲࡛ࠊȤࡣࣇ࢛ࣀࣥࡢࣈࣛࣥࢳ࢖ࣥࢹࢵࢡࢫࠊk ࡣ N Ⅼࠊq ࡣࣇ࢛ࣀࣥࡢἼື࣋ࢡࢺࣝࠊi, j ࡣࣂࣥࢻ࢖ࣥࢹࢵࢡࢫࠊe nk eQkq ࡣࣈࣟࢵ࣍≧ែࡢ࢚ࢿࣝࢠ࣮ࠊȰqȤࡣࣇ࢛ࣀࣥ
ࡢ࿘Ἴᩘ࡛࠶ࡿࠋ

ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 1D105 㐽ⶸᐃᩘࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⌮ㄽண- 179 -

㏆ᖺࠊࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ඘ᨺ㟁㐣⛬࡟ࡘ࠸࡚1Dᅛయ105ࢫ࣌ࢡࢺࣝゎᯒ࡟ࡼࡿ◊✲ࡀ┒ࢇ࡟࠾ࡇ࡞ࢃࢀ࡚࠸ࡿࠋ ࡑࡇ࡛ᐦᗘỗ㛵ᩘἲ ')7  ࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬࡟ࡼࡾ⾜࠸ࢢࣛࣇ࢙ࣥ㈇ᴟ࡛⏕ᡂ
ࡉࢀࡿ1Dࢡࣛࢫࢱ࣮ࡢ105ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆ཰㞟ࡋࠊ.76FKWWࡽ࡟ࡼࡾᥦ᱌ࡉࢀࡓࢢࣛࣇࡢ᥋⥆᝟ሗࢆ౑ࢃࡎཎᏊ㛫ࡢ㊥㞳ࢆ฼⏝ࡍࡿࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ6FK1HWࢆ⏝࠸࡚ࠊࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢᵓ㐀࠿ࡽ

1D105ࡢ㐽ⶸᐃᩘࡢண ࢆ⾜ࡗࡓࠋࢹ࣮ࢱࢭࢵࢺࡢసᡂ࡟ࡘ࠸࡚ࠊ⤖ྜ㛗ศᕸゎᯒ࡟ᇶ࡙ࡃ࢔ࣝࢦࣜࢬ࣒

ࡢ 6HFRQGRUGHU%RQG/HQJWK'LVWULEXWLRQ$OJRULWKP 6%/'$ >@ࢆ⏝࠸࡚ࠊࣛࣥࢲ࣒࡞ 1DQ Q  ࣭࣭࣭
 ࢡࣛࢫࢱ࣮ᵓ㐀ࢆ⏕ᡂࡋࡓࠋ6%/'$ࡢࣃ࣓࣮ࣛࢱࡣȝ cࠊȝ cࠊı ı c࡜ࡋࡓࠋ⏕ᡂࡉࢀࡓᵓ㐀࡟ࡘ࠸࡚ࠊ*DXVVLDQࢆ⏝࠸࡚')7ィ⟬࡟ࡼࡾࢫࣆࣥ₇⟬Ꮚ6ࡢᅛ᭷್࠾ࡼࡧ105ࡢ➼᪉ᛶ㐽ⶸᐃᩘıLVRࢆồࡵࡓࠋỗ㛵ᩘ࠾ࡼࡧᇶᗏ㛵ᩘ࡟ࡣࡑࢀࡒࢀ%/<3࡜* G ࢆ⏝࠸ࡓࠋࡇࡢ࡜ࡁࠊࢫࣆࣥởᰁࢆ㑊ࡅࡿࡓࡵࠊࢫࣆࣥ₇⟬Ꮚ6ࡢᅛ᭷್ࡀ௨ୗࡢᵓ㐀ࡢࡳࢆ฼⏝ࡋࠊྛQ࡟ࡘ࠸࡚ᵓ㐀࡟࡞ࡿࡲ࡛ᵓ㐀ࡢ⏕ᡂࢆ⧞ࡾ㏉ࡋࡓࠋ1DQ Q  ࣭࣭࣭ ࢆࢺ࣮ࣞࢽࣥࢢࢭࢵࢺࠊ1DQ Q  ࢆࣂࣜࢹ࣮ࢩࣙࣥࢭࢵࢺࠊ
1DQ Q  ࢆ ࢸࢫࢺࢭࢵࢺ࡜ࡋ࡚ࠊࣂࣜࢹ࣮ࢩࣙࣥࢭࢵࢺ࡟㛵ࡍࡿࣟࢫ㛵ᩘࢆ᭱ᑠ໬ࡍࡿࡼ࠺࡟ࢽ࣮ࣗࣛࣝ
ࢿࢵࢺ࣮࣡ࢡࢆᏛ⩦ࡉࡏࡓࠋࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࡢᏛ⩦ࡣࠊ6FK1HW3DFN ࢆ⏝࠸࡚⾜ࡗࡓࠋ6FK1HW ࡣ୍⯡࡟ྛཎᏊࡢᐤ୚ࢆ㊊ࡋྜࢃࡏ࡚ศᏊࡢ≀ᛶࢆண ࡍࡿࡀࠊ㊊ࡋྜࢃࡍࡇ࡜ࡣࡏࡎ࡟ྛཎᏊࡢᐤ୚ࡢ್ࢆ
ࡑࡢࡲࡲཎᏊࡢ㐽ⶸᐃᩘࡢ್ࡢண ࡜ࡋ࡚⏝࠸ࡓࠋ㐽ⶸᐃᩘࡣࠊࢡࣛࢫࢱ࣮ࡢཎᏊᩘ࡟ࡼࡽࡎ୍⯡໬ࣟࢪࢫࢸ࢕ࢵࢡศᕸ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢศᕸࡣᕥ࡟ṍࢇ࡛࠸ࡿࡢ࡛ࠊᖹᆒ஧஌ㄗᕪࢆࣟࢫ㛵ᩘ࡜ࡋ࡚ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࢆᏛ⩦ࡉࡏࡿ࡜ࠊᑠࡉ࡞್ࢆ㔜どࡋ᭱㢖್௜㏆ࡢ್ࢆ㍍どࡋ࡚ࡋࡲ࠺࡜᥎ ࡉࢀࡿࠋࡑࡇ࡛ࠊ୍⯡໬ࣟࢪࢫࢸ࢕ࢵࢡศᕸࡀṇつศᕸ࡜࡞ࡿࡼ࠺࡟㐽ⶸᐃᩘࢆኚ᥮ࡋࡓࠋࡉࡽ࡟ࠊࣟࢫ㛵ᩘ࡟ศᕸࢆ෌⌧ࡍࡿ㡯ࢆ㏣ຍࡋࡓࠋ䞉䞉䞉㻌 㻔㻝㻕㻌ࡣ ')7 ࡛ィ⟬ࡉࢀࡓ㐽ⶸᐃᩘࠊ ࡣࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࡛ண ࡉࢀࡓ㐽ⶸᐃᩘ࡛࠶ࡿࠋࡲࡓࠊ
ࡧ࠾ࡼࡣࠊ࣑ࢽࣂࢵࢳෆ࡛㐽ⶸᐃᩘࡢ್ࢆࢯ࣮ࢺࡋࡓࡶࡢ࡛࠶ࡿࠋD  ࢆ⏝࠸ࡓࠋ



◊✲ᡂᯝ



༙ᑟయගゐ፹ᮦᩱࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜࣏࣮ࣛࣟࣥᙧᡂࡢ⌮ㄽⓗ◊✲㸯㸧㉸檿㏿᫬㛫ศゎ ; ⥺྾཰ศගἲ࡟ࡼࡿගບ㉳ :2 ࡢᒁᡤᵓ㐀ኚ໬㸸e $ ࢆ 9%0 ࡲࡓࡣ &%0 ࡜ࡋࠊ9%0&%0 ௜㏆ࡢȘ$ ࢆィ⟬ࡋࡓ⤖ᯝࢆᅗ㸯࡟♧ࡍࠋ࡝ࡕࡽࡶȤ  ࡢ⦪ᆺගᏛ㸦/2㸧ࣇ࢛ࣀࣥࡀ኱ࡁ࡞ࣆ࣮ࢡࢆᣢࡗ࡚࠸ࡿࠋࣇ࣮ࣞࣜࢵࣄ⤖ྜᐃᩘ㸦D)㸧ࡣࠊගᏛㄏ㟁⋡㸦H҄㸧ࠊ㟼Ṇㄏ㟁⋡㸦H㸧ࠊࣂࣥࢻ᭷ຠ㉁㔞
㸦m㸧ࠊ/2 ࣇ࢛ࣀࣥࡢ᣺ືᩘ㸦ƫw㸧ࢆ⏝࠸࡚ḟᘧ࡛୚࠼ࡽࢀࡿࠋ        ᅗ㸯㸯 :2 ࡢ㟁Ꮚࣇ࢛ࣀ࣭ࣥࢫ࣌ࢡ
ࢺࣝᐦᗘ D 9%0 E &%0

9%0ࠊ&%0 ࡛ࡢṇᏍࠊ㟁Ꮚ࡟ࡘ࠸࡚D) ࡣ a ࡜ᚓࡽࢀࠊ㟁- 180 -

Ꮚ࣏࣮ࣛࣟࣥࠊṇᏍ࣏࣮ࣛࣟࣥࢆᙧᡂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ㉸㧗㏿᫬㛫ศゎ ; ⥺྾཰ࢫ࣌ࢡࢺࣝ>@࡛ࡣࠊග↷ᑕ࡟ࡼࡗ࡚ : ࿘ࡾࡢᒁᡤᵓ㐀ኚ໬ࡀ㉳ࡇࡾࠊ SV ࡲ࡛ᒁᡤᵓ㐀ṍࡳࡀ㉳ࡇࡿࢧ࢖ࢺࡢ๭ྜࡀቑ࠼࡚࠸ࡃ
࡜ゎ㔘ࡉࢀ࡚࠸ࡿࡀࠊୖグࡢィ⟬⤖ᯝ࠿ࡽග↷ᑕᚋࡢᒁᡤⓗ࡞ᵓ㐀ኚ໬ࢆࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥ⏕ᡂ࡟ࡼࡿ᱁ᏊࡺࡀࡳࡢほⅬ࠿ࡽ㆟ㄽࡋࡓࠋ㸰㸧Ỉศゎගゐ፹ 6U7L2$O ࡢ࢟ࣕࣜ࢔ᣑᩓ $O ࢆࢻ࣮ࣉࡋࡓ 6U7L2࡟࠾࠸࡚ࠊ࡯ࡰ ࡢෆ㒊ኚ᥮㔞Ꮚ཰⋡ࡀᚓࡽࢀࡿࡇ࡜ࡀሗ࿌ࡉࢀࡓ
>@ࠋ㒊ศ≧ែᐦᗘ 3'26 ゎᯒ࠿ࡽࠊ$O ࢻ࣮ࣉࡣࠊ㓟⣲Ḟ㝗࡟ࡼࡾ⏕ᡂ
ࡍࡿ 7L㸩≧ែ࡟㉳ᅉࡍࡿࢺࣛࢵࣉࢧ࢖ࢺࢆࣃࢵࢩ࣮࣋ࢺࡍࡿࡇ࡜ࡀศ࠿
ࡗࡓࠋe $ ࢆ 9%0 ࡲࡓࡣ &%0 ࡜ࡋࠊ9%0&%0 ௜㏆ࡢȘ$ ࢆィ⟬ࡋࡓ⤖ᯝࢆᅗ㸰࡟♧ࡍࠋ࡝ࡕࡽࡶ⦪ᆺගᏛࠊ/2/2 /2ࠊࣇ࢛ࣀࣥࡀ኱ࡁ
࡞ࣆ࣮ࢡࢆᣢࡗ࡚࠸ࡿࠋḞ㝗ࡢ࡞࠸ 6U7L2 ࡟ࡘ࠸࡚ࡢࣇ࣮ࣞࣜࢵࣄ⤖ྜᐃᩘD) ࡣ 㹼 ࡜ᚓࡽࢀࠊ㟁Ꮚ࣏࣮ࣛࣟࣥࠊṇᏍ࣏࣮ࣛࣟࣥࢆᙧ
ᡂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ㟁Ꮚ࣏࣮ࣛࣟࣥ࡜ṇᏍ࣏࣮ࣛࣟࣥࡢ┦஫స⏝ࡣࠊᅗ 6U7L2 ࡢ㟁Ꮚࣇ࢛ࣀ࣭ࣥࢫ
࣌ࢡࢺࣝᐦᗘ ୖ &% ୗ 9%

㟁Ꮚ࡜ṇᏍࡢࢡ࣮ࣟࣥ┦஫స⏝ࡀ 6U7L2 ࡢ኱ࡁ࡞ㄏ㟁⋡࡟ࡼࡾ㐽ⶸࡉࢀ࡚࠸ࡿࡓࡵࠊ࣏࣮ࣛࣟࣥᙧᡂ࡟࡜ࡶ
࡞࠺᱁Ꮚṍࡳࡀ኱ࡁ࠸ሙྜࠊ཯Ⓨⓗ࡞ࡿ࡜ண᝿ࡉࢀࡿ>@ࠋࡋࡀࡗ࡚㟁Ꮚ࣏࣮ࣛࣟࣥ࡜ṇᏍ࣏࣮ࣛࣟࣥࡢ཯Ⓨⓗ࡞┦஫స⏝ࡀࠊELPROHFXODU ࡞෌⤖ྜࢆᢚไࡋࠊ࢟ࣕࣜ࢔ࡢ㛗㊥㞳ᣑᩓࠊࡍ࡞ࢃࡕࠊ࡯ࡰ ࡢෆ㒊ኚ᥮㔞Ꮚ཰⋡ࢆྍ⬟࡟ࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ

ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿ 1D105 㐽ⶸᐃᩘࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⌮ㄽணࢸࢫࢺࢭࢵࢺ࡛࠶ࡿ 1DQ Q  ࡢࢡࣛࢫࢱ࣮ᵓ㐀࡟ࡘ࠸࡚ࠊ')7 ࡛ᚓࡽࢀࡓ㐽ⶸᐃᩘ࡜ࢽ࣮ࣗࣛࣝࢿࢵࢺ
࣮࣡ࢡ࡟ࡼࡗ࡚ண

ࡉࢀࡓ㐽ⶸᐃᩘࡢศᕸࢆẚ㍑ࡋࡓࠋ')7 ࡛ᚓࡽࢀࡓ㐽ⶸᐃᩘࡢศᕸࡣࠊ SSP ௜㏆ࡢࣆ࣮ࢡࢆࡶࡘ୍⯡໬ࣟࢪࢫࢸ࢕ࢵࢡศᕸ࡛࠶ࡗࡓ ᅗ D ࠋࡋ࠿ࡋࠊᖹᆒ஧஌ㄗᕪࢆࣟࢫ㛵ᩘ࡜ࡋ࡚Ꮫ⩦ࡋࡓࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࡣࠊᖹᆒ್ࡣ෌⌧ࡋࡓࡀࠊࣆ࣮ࢡ఩⨨ࡸ SSP ௨ୗࡢ㐽ⶸᐃᩘࢆ෌⌧࡛ࡁ࡞࠿ࡗࡓ ᅗ E ࠋᑐࡋ࡚ࠊᘧ  ࡢࣟࢫ㛵ᩘࢆᑟධࡋࡉࡽ࡟ṇつศᕸ࡬ኚ᥮ࡋࡓ㐽ⶸᐃᩘࢆ฼⏝ࡋࢽ࣮ࣗࣛࣝࢿࢵࢺ
࣮࣡ࢡࢆᏛ⩦ࡉࡏࡿ࡜ࠊ')7 ࡛ᚓࡽࢀࡓ㐽ⶸᐃᩘࡢศᕸࡢᙧࢆ෌⌧ࡋࠊࣆ࣮ࢡࡢ఩⨨ࡶᨵၿࡋࡓ ᅗ F ࠋࡇࡢ࡜ࡁࠊࣆ࣮ࢡ௜㏆ࡢ್ࢆࡼࡃண ࡛ࡁ࡚ᅗ ')7 ィ⟬࡛ᚓࡽࢀࡓ㐽ⶸᐃᩘ࡜ᅗ 1DQ Q  ࡢ㐽ⶸᐃᩘࡢศᕸ D ')7 ィ⟬ E  ࣟࢫ㛵ᩘࡀᖹᆒ஧஌ㄗṇつศᕸ࡬ኚ᥮ࡋࣟࢫ㛵ᩘࢆᖹᆒ஧

F  㐽ⶸᐃᩘࢆṇつศᕸ࡬ኚ᥮ࡋࣟࢫ

஌ㄗᕪ࡜ᘧ  ࡜ࡋࡓࢽ࣮ࣗࣛࣝࢿࢵ

ᕪࡢࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࡢண

㛵ᩘࢆᖹᆒ஧஌ㄗᕪ࡜ᘧ  ࡜ࡋࡓࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࡢண

- 181 -

ࢺ࣮࣡ࢡࡢண ್ࡢ㛵ಀ࠾ࡾࣆ࣮ࢡ࠿ࡽእࢀࡓ್ࡶࠊㄗᕪࡀ኱ࡁ࠸ࡶࡢࡶ࠶ࡿࡀࠊ೫ࡾ࡞ࡃண

࡛ࡁ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ ᅗ㸲 ࠋࡇࡢࣔࢹࣝࡢண ㄗᕪࢆᝏ໬ࡉࡏ࡚࠸ࡿࡢࡣࠊ SSP ௨ୗࡢᑠࡉ࡞್ࡢ㐽ⶸᐃᩘࢆࡶࡘᵓ㐀࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡞ᑠࡉ࡞㐽ⶸᐃᩘࢆ࡜ࡿࡢࡣࠊ㓄఩ᩘࡀ 㹼 ࡢࡼ࠺࡞୰㛫ⓗ࡞㓄఩ᩘࢆ࡜ࡿཎᏊ࡛࠶ࡿࡇ࡜ࡀࠊ
㐽ⶸᐃᩘ࡜㓄఩ᩘࡢ㛵ಀࡢゎᯒ࠿ࡽࢃ࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ6&&')7% ࡞࡝ࡢ ')7 ࡜ẚ࡭࡚ィ⟬ࢥࢫࢺࡢప࠸ᡭἲࢆ⏝࠸࡚㓄఩ᩘࡢ㧗࠸Ᏻᐃ࡞ᵓ㐀ࢆࢧࣥࣉࣜࣥࢢࡍࡿࡇ࡜࡟ࡼࡾࠊࡉࡽ࡞ࡿண

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Insight from Molecular Dynamics Simulations, 17th International Conference of Computational Methods in Sciences andEngineering (QS symposium of ICCMSE 2021) (2021 µ 9 Ó 17 Ï/Online / Keynote speech)Takefumi Yamashita, Physical Insight into Protein Surface through High Performance Computation: Prof. Fujitani’s
research and idea, Stockholm-Tokyo University Partnership Online Workshop2021: Theme 4.1: Large-scale Computationin Life Science with the Memorial of Prof. Fujitani (2021 µ 9 Ó 27 Ï/Online/Invited lecture)±oĻ,

ċđó?TgAl&¬Ĵøtè#¨Ĝě&1&ÝĭaMlXËĊ CBI ªxă 432 Ģéx ċđó?TgAlěą'ĔýĂÆõ:¢7 (2022 µ 3 Ó 17 Ïk@je>jkÇ¾Ģé) *6

T. Yamashita, T. Mitsui, K. Sasaki, M. Wada, A. Matsuura, and N. Kamiya, Effect of N343 Glycosylation and N501Y
Mutation on the SARS-CoV-2 Spike Protein: Modeling and MD simulations, AIP Conf. Proc. (Accepted)

7"+1) Fujitani, H.; Tanida, Y.; Matsuura, A. Phys. Rev. E 2009, 79, 021914.
2) Fujitani, H.; Matsuura, A.; Sakai, S.; Sato, H.; Tanida, Y. J. Chem. Theory Comput. 2009, 5, 1155.
3) Wang, J.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D. A. J. Comput. Chem. 2004, 25, 1157.
4) Ma, Q.; Werner H.-J. WIREs Computational Molecular Science 2018, 8, e1371.

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ィ⟬ᑐ㇟⣔ࡣ㸪๓◊✲ >@ ࡜ྠࡌࡃỈ  㔞య࡛࠶ࡾ㸪ࡇࢀࡣᾮయỈࡢ 0' ィ⟬ࡢ VQDSVKRWV ࠿ࡽ  㔞యࢆษࡾฟࡋࡓࡶࡢ  ㏻ࡾࢆึᮇ㓄⨨࡜ࡋ࡚ᵓ㐀᭱㐺໬ࡋࡓࡶࡢ࡛࠶ࡿࠋࡇࡇ࠿ࡽỈ⣲⤖ྜࡋࡓỈศᏊ࣌࢔ ಶࢆᢤࡁฟࡋ㸪㐺ษ࡞ᗙᶆኚ᥮ࡢࡢࡕ㸪∦ഃศᏊࡎࡘࢆⅬ㟁Ⲵ㞟ྜ㸦&+HOS* ࡢ  ಸ㸧࡛⨨᥮ࡋ㸪㟁Ꮚᐦᗘኚ໬ࢆィ⟬ࡋࡓ㸦 c 㛫㝸㸧ࠋࡇࡢྛࠎࡣ  0 ḟඖࡢ࣋ࢡࢺ࡛ࣝ࠶ࡾ㸪ࡑࡢ  ಶࡢ㞟ྜ࡟ᑐࡋ࡚㸪69' ゎᯒࢆ⾜ࡗࡓࠋศᏊࡢᑐ⛠ᛶࢆ฼⏝ࡋࡓ㒊ศᑐ⛠໬࡜㸪∦ഃࡢ 2+ ࡟࠶ࡿ⛬ᗘᒁᅾ໬ࡋࡓ㟁Ꮚᐦᗘኚ໬࡟㛵ࡍࡿᑐ⛠᧯స࠾ࡼࡧࡑࢀ࡟⥆ࡃ┤஺໬ࢆ᪋ࡋࡓࡢࡕ࡟ᚓࡽࢀࡓ⤖ᯝࡢ୍㒊ࢆ㸪ᅗ㸯࡟♧ࡍࠋࡇࡢ࠺ࡕ D  ࡣ∦ഃࡢ 2+ ཎᏊ㛫ࡢ㟁Ⲵ⛣ືᡂศ㸦ᡂศ D㸧
㸪 E  ࡣ 2 ཎᏊࡢ +2+ ゅ஧➼ศ⥺᪉ྥࡢศᴟ㸦ᡂศ 㸧㸪 F  ࡣ∦ഃࡢ + ཎᏊࡢ㠃ෆୟࡘ⤖ྜᆶ┤᪉ྥࡢศᴟ㸦ᡂศ D㸧㸪 G  ࡣ㟁Ꮚᐦᗘኚ໬ࡢ㧗ḟᡂศ㸦ᡂศ 㸧࡛࠶ࡿࠋ69' ࡟࠾ࡅࡿᅛ᭷್ࡢศᕸࢆ᳨ウࡋࡓ⤖ᯝ㸪୺せ࡞㟁Ꮚᐦᗘኚ໬ࡣ  ಶ⛬ᗘ࡛࠶ࡾ㸪ࡑࡢ⥺ᙧ⤖ྜ࡟ࡼࡾ㸪㟼㟁ศᴟ࡟క࠺࠾ࡼࡑ඲࡚ࡢ㟁Ꮚᐦᗘኚ໬ࢆ㏆ఝⓗ࡟⾲⌧࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ࡟㸪ㄏ㉳཮ᴟᏊࢆⰋࡃ෌⌧ࡍࡿ┦஫స⏝ࣃ࣓࣮ࣛࢱ࣮ࢆᑟฟࡋࡓࠋ
>@+7RULLDQG58NDZDJ. Phys. Chem. B±  - 191 -

ᅗ㸯㸸Ỉࡢ㟼㟁ศᴟ࡟ࡼࡿ㟁Ꮚᐦᗘኚ໬ࢆ 69' ゎᯒࡋࡓ⤖ᯝᚓࡽࢀࡓ୺せᡂศ㹙 D  ᡂศ D E  ᡂศ  F  ᡂศ D G  ᡂศ 㹛ࡢ㸰ḟඖࣉࣟࢵࢺࠋ

ฟ∧࣭Ⓨ⾲ᐇ⦼㸦௧࿴㸱ᖺᗘ㸧‫ ۻ‬.HQWR6DLWRDQG+DMLPH7RULLJ. Phys. Chem. B ±   ‫ ۻ‬+DMLPH7RULLRSC Adv. ±   ‫ ۻ‬㫽ᒃ㸪㬼ᕝ㸪➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪 ᖺ  ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬‫ ۻ‬+DMLPH 7RULL DQG 5\RWD 8NDZD WK ,QWHUQDWLRQDO &RQIHUHQFH RQ 7LPH 5HVROYHG 9LEUDWLRQDO 6SHFWURVFRS\
7596 -XQH ࢜ࣥࣛ࢖ࣥ㛤ദ㸬‫ ۻ‬+DMLPH7RULL4XDQWXP6FLHQFH6\PSRVLXPLQWKHWK,QWHUQDWLRQDO&RQIHUHQFHRI&RPSXWDWLRQDO0HWKRGVLQ
6FLHQFHVDQG(QJLQHHULQJ ,&&06( 6HSWHPEHU SOHQDU\OHFWXUH  ࢜ࣥࣛ࢖ࣥ㛤ദ ‫ ۻ‬㓇஭㸪㫽ᒃ㸪➨  ᅇศᏊ⛉Ꮫウㄽ఍㸪 ᖺ  ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ ‫୕ ۻ‬Ꮿ㸪㫽ᒃ㸪➨  ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ ໭ᮧ㸪㫽ᒃ㸪➨  ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ

- 192 -

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[S´ § ¥¶<zKE¡ÅE616  §  Z  ]¢ª­ 

[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” (submitted).
[2] S. Kumagai, H. Ishii, G. Watanabe, C. P. Yu, S. Watanabe, J. Takeya, and T. Okamoto, “Nitrogen-Containing
Perylene Diimides: Molecular Design, Robust Aggregated Structures and Advances in n-Type Organic
Semiconductors”, Acc. Chem. Res. 55, 660 (2022).
[3] K. Fukushima*, K. Matsuzaki, M. Oji, Y. Higuchi, G. Watanabe, Y. Suzuki, M. Kikuchi, N. Fujimura, N.
Shimokawa, H. Ito, T. Kato, S. Kawaguchi*, and M. Tanaka*, “Anisotropic, Degradable Polymer Assemblies Driven
by a Rigid Hydrogen-Bonding Motif That Induce Shape-Specific Cell Response”, Macromolecules 55, 15 (2022).
[4] C. Ueda, J. Parka, K. Hirose, S. Konishi, Y. Ikemoto, M. Osaki, H. Yamaguchi, A. Harada*, M. Tanaka*, G.
Watanabe*, and Y. Takashima*, “Behavior of supramolecular cross-links formed by host-guest interactions inhydrogels responding to water contents”, Supramol. Mater. 1, 100001 (2022).
[5] A. Yaguchi, M. Oshikawa, G. Watanabe, H. Hiramatsu, N. Uchida, C. Hara, N. Kaneko, K. Sawamoto, T.
Muraoka*, and I. Ajioka*, “Efficient protein incorporation and release by a jigsaw-shaped self-assembling peptidehydrogel for injured brain regeneration”, Nat. Commun. 12, 6623 (2021).

- 195 -

[6] C. P. Yu, N. Kojima, S. Kumagai, T. Kurosawa, H. Ishii, G. Watanabe, J. Takeya, and Toshihiro Okamoto*,“Approaching isotropic charge transport of n-type organic semiconductors with bulky substituents”, Communs.
Chem. 4, 155 (2021).
[7] Y. Ishii*, N. Matubayasi, G. Watanabe, T. Kato*, and H. Washizu*, “Molecular insights on confined water in the
nanochannels of self-assembled ionic liquid crystal”, Sci. Adv. 7, eabf0669 (2021).
[8] S. Shikita, G. Watanabe, D. Kanouchi, J. Saito, and T. Yasuda*, “Alternating Donor–Acceptor ʌConjugatedMacrocycle Exhibiting Efficient Thermally Activated Delayed Fluorescence and Spontaneous Horizontal Molecular
Orientation”, Adv. Photonics Res. 2, 2100021 (2021).
[9] S. Yoneda*, T. Saito, D. Nakajima, and G. Watanabe, “Potential of Mean Force and Umbrella Sampling Simulation
for the Transport of 5-Oxazolidinone in Heterotetrameric Sarcosine Oxidase”, Proteins 89, 811-818 (2021).
[10] C. Zhang, Y. Guo, D. He, J. Komiya, G. Watanabe, T. Ogaki, C. Wang, A. Nihonyanagi, H. Inuzuka, H. Gong, Y.
Yi*, K. Takimiya, D. Hashizume, and D. Miyajima*, “A Design Principle for Polar Assemblies with C3Sym Bowl
Shaped ʌConjugated Molecules”, Angew. Chem. Int. Ed. 60, 3216-3267 (2021). (Selected as a “Very Important
Paper”)- 196 -

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1 ◊✲┠ⓗຌ‫Ͳڂݜ‬ͺɼψόϜτϨΠϩΏਫ਼ର෾ࢢ͗‫ͤܐؖ‬Ζझʓ͹‫ݳ‬েΝྖࢢԿָ‫ࢋܯ‬ͶΓΕखΕѽ͏ɼͨ͹‫ؽ‬೵ʀ෼੓ʀൕԢ੓͹൅‫ߑؽݳ‬Νཀྵ࿨దͶմ໎ͤΖ͞ͳΝ໪ࢨͪ͢ɽΉͪɼͨ͹ͪΌͶචགྷͳ͵Ζཀྵ࿨͹֋൅͕Γ;ϕϫήϧϞ͹ࣰૹ΍ߨͮͪɽҐԾͶ͞͹໪దͶॊͮͱߨͮͪ‫ڂݜ‬͹͑ͬɼ  ඉ‫ࡑۃ‬Կͪ͢ྯًয়ସͶ͕͜Ζඉஇ೦෾ࢢಊྙָεϝϣϪʖεϥϱघ๑͹֋൅ɼ  ੷෾஍υʖνϗʖηͶ‫͚Ͱخ‬૮ଲ࿨దྖࢢԿָ‫ࢋܯ‬͹߶ଐԿघ๑͹֋൅ɼ  ώέτϨΨϫχϕεϱͶ͕͜ΖϕϫφϱҢಊգఖ͹ྖࢢ෾ࢢಊྙָεϝϣϪʖεϥϱɼ  ‫ؽ‬փָस‫ܗ‬ుࢢ૮‫ؖ‬Ϡυϩ͹న༽྘Ү൓ఈͳ‫ؽ‬೵֨௃ Ͷͯ͏ͱๅࠄͤΖɽ

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3 ◊✲ᡂᯝ
3-1.㠀ᒁᅾ໬ࡋࡓບ㉳≧ែ࡟࠾ࡅࡿ㠀᩿⇕ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࡢ㛤Ⓨൔ಍ରͶ͕͜Ζޭྯًয়ସ͹ξ΢ψϝέηͺɼޭుࢢυώ΢η͹ಊࡠ‫ߑؽ‬͹‫ેخ‬Ν͵ͤ॑གྷ͵ଲেͲ
͍Ζɽൔ಍ରͶ͕͜Ζྯًয়ସͲͺɼྯًͶ൒͑ుࢢয়ସรԿ͗ψόηίʖϩͶඉ‫ࡑۃ‬ԿͤΖͪΌɼॊཔ͹ྯًয়ସξ΢ψϝέηεϝϣϪ
ʖεϥϱघ๑Ͳͺ‫ྖࢋܯ‬దͶखΕѽ͏͗ࠖೋͲ͍ͮͪɽ
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๑Ν΍ͳͶɼψόηίʖϩͶඉ‫ࡑۃ‬Կͪ͢ྯًয়ସͶ͕͜Ζుࢢʀߑଆξ΢ψϝέηΝखΕѽ͓Ζඉஇ೦෾ࢢಊ
ྙָ‫ࢋܯ‬घ๑Ν֋൅ͪ͢ɽుࢢয়ସͶͯ͏ͱͺືౕߨ྽͹ࣰ࣎ؔ൅ఴͶΓΕखΕѽ͏ɼ֫Ͷಉ͚ྙͶͯ͏ͱͺɼฑ‫ۋ‬৖ۛࣇʤ(KUHQIHVW ๑ʥͶ‫ື͘Ͱخ‬ౕߨ྽͖Δ‫ͪ͢ࢋܯ‬ɽືౕߨ྽͹࣎ؔ൅ఴΝනͤӣಊ๏ఖࣞΝմ͚Ͷ͍ͪ

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3-2.✚✚ศ್ࢹ࣮ࢱ࣮࣋ࢫ࡟ᇶ࡙ࡃ┦ᑐㄽⓗ㔞Ꮚ໬Ꮫィ⟬ࡢ㧗㏿໬ᡭἲࡢ㛤ⓎྖࢢԿָ‫ࢋܯ‬Ν༽͏ͱ॑‫ݫ‬ોԿ߻෼͹੓࣯Ν༩଎ͤΖͶͺ૮ଲ࿨ްՎ͹खΕࠒΊ͗෈Նܿͳ͵ΖɽԿָͶචགྷ͵੠ౕͲ૮ଲ࿨ްՎΝ‫ى‬फ़Ͳ͘Ζ  ੔෾๑Ͳͺుࢢʀཇుࢢয়ସΝ͍ΔΚͶखΕѽ͑ͪΌ‫ࢋܯ‬αηφ͗๴୉ͳ͵Ζɽͨ͹ͪΌ  ੔෾๑Ͷ͕͜Ζ 'LUDF ๏ఖࣞΝร‫͢׷‬ɼుࢢয়ସ͹ΊΝखΕѽ͑  ੔෾๑͗൅ఴ͢ͱͪ͘ɽ౲‫Ͳ࣪ڂݜ‬ͺ࠹΍߶੠ౕ͵  ੔෾๑Ͳ͍Ζໃ‫  ࣏ݸ‬੔෾ ,27&  ๑Ͷ‫߶͘Ͱخ‬੠ౕ͖ͯ߶ްི͵૮ଲ࿨‫ࢋܯ‬घ๑Ν֋൅͢ͱͪ͘ɽ‫ॶۃ‬ϤωνϨʖร‫ ׷‬/87  ͺ૮ଲ࿨ްՎ͹‫ॶۃ‬੓Ͷ‫͘Ͱخ‬૮ଲ࿨ްՎ͗‫ݨ‬ஸͳ͵Ζ෨෾‫ܧ‬͹ΊΝ૮ଲ࿨దͶखΕѽ͏ϤωνϨʖร‫׷‬Νࢬͤ͞ͳͲ ,27& ๑͹੠ౕΝң࣍ͪ͢ΉΉ‫ࢋܯ‬αηφ͹ત‫ܗ‬ηίʖϨϱήԿΝୣ੔ͪ͢ɽຌ‫Ͳڂݜ‬ͺɼ ుࢢԍࢋࢢͶଲͤΖ /87,27& ๑Ͷ͕͏ͱ‫ࢢݬ‬஦ৼ  ుࢢ੷෾͹ΊΝ૮ଲ࿨దͶखΕѽ͏ɼଡ஦ৼ  ుࢢ੷෾ͺඉ૮ଲ࿨ͳಋ༹ͳ͵Ζ͞ͳͶ஥໪͢ɼ/87 ͹͠Δ͵Ζ߶ଐԿΝߨͮͪɽ‫ࢢݬ‬஦ৼ  ుࢢ੷෾ͺ‫ݫ‬ો͕Γ;‫خ‬ఊ‫਼͗ؖ‬ಋͣͲ͍Ηͻͨ͹੷෾஍ͺߑଆΏ෾ࢢझͶΓΔͥҲఈͲ͍Ζɽͨ͞Ͳຌ‫Ͳڂݜ‬ͺಋҲ͹‫ݫ‬ોʀ‫خ‬ఊ‫ͳ਼ؖ͟‬Ͷ༩Ό ,27& ๑Ͷ‫ࢢݬ͚Ͱخ‬஦ৼ  ుࢢ੷෾Ν‫ࢋܯ‬͢ɼυʖνϗʖηԿͪ͢ɽͨ͢ͱɼࣰࡏ͹෾ࢢ‫ࢋܯ‬͹ࡏͶͺ੷෾஍͹࿒Κ͵‫ࢋܯ‬ͺߨΚͥͶυʖνϗʖη͖ΔಣΊࠒ΋ΠϩβϨθϞʀϕϫήϧϞΝ֋൅ͪ͢ɽ
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ޭण༲ຜνϱϏέ࣯͹ҲझͲ͍ΖώέτϨΨϫχϕεϱʤ%5ʥͲͺɼ൅৯஄͹ޭҡ੓ԿΝ఼ًͳͪ͢
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᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫឤᰁ㜼ᐖࡢศᏊᶵᵓࡢゎ᫂

Molecular mechanism of inhibition of SARS-CoV-2 infection.
‫ۑ‬ᕝཱྀ

1

୍᭸ࠊ➉⏣

ᑜࠊ㠡ᶫ

ᙬ᪩ࠊᰘ⏣

኱㈗㸦㔠ἑ኱Ꮫ⌮ᕤ◊✲ᇦ㸧◊✲┠ⓗ⌧ᅾࡶὶ⾜ࡀ⥆࠸࡚࠸ࡿ SARS-CoV-2㸦᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫ㸧࡬ࡢᑐ⟇ࡣᚲ㡲࡛࠶ࡿࠋ≉࡟་Ꮫ࣭⸆Ꮫⓗ࡞

ほⅬ࠿ࡽ◊✲ࡀ㐍ࡵࡽࢀࠊ἞⒪⸆ࡸ࣡ࢡࢳࣥࡀ㛤Ⓨࡉࢀࡓࠋࡲࡓࠊ࢘࢖ࣝࢫࡢឤᰁᶵᵓࡸឤᰁ㜼ᐖᶵᵓ࡞࡝
ࡢศᏊ⛉Ꮫⓗ࡞ほⅬ࠿ࡽࡶ◊✲ࡀ㐍ࡵࡽࢀࠊ࢘࢖ࣝࢫࢱࣥࣃࢡ㉁ࡸᢠయࡢศᏊᵓ㐀ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚ࡁࡓࠋ
ᮏ◊✲࡛ࡣࠊSARS-CoV-2 ࡢࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁࡜ᢠయ࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࠊ᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫࡢឤᰁ㜼ᐖࡢศᏊᶵᵓ࡟ࡘ࠸᳨࡚ウࡍࡿࠋ࢘࢖ࣝࢫ⾲㠃࡟㟢ฟࡋ࡚࠸ࡿࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁ࡣࠊ࢘࢖ࣝࢫࡀ⣽⬊࡬౵ධࡍࡿ㝿࡟ࠊ᭱ึ࡟⣽⬊⾲㠃ࡢཷᐜయ࡟⤖ྜࡍࡿ㒊఩࡛࠶ࡿࠋࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁࡟㐺ษ࡞ᢠయࡀ⤖ྜࡍࡿࡇ࡜࡛ࠊཷᐜయ࡜ࡢ⤖ྜࢆ㜼ᐖࡋࠊ࢘࢖ࣝࢫࡀ⣽⬊࡬౵ධࡍࡿࡢࢆ㜵ࡄࡇ࡜ࡀ࡛ࡁࡿࠋࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁࡜⣽⬊ഃཷᐜయࡸᢠయ࡜ࡢ」ྜ
యᵓ㐀ࡣឤᰁ㜼ᐖࡢほⅬ࠿ࡽ㔜せ࡛࠶ࡿࠋࡑࡇ࡛ࠊࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁࡜ᢠయࡢࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢆ⾜࠸ࠊ」ྜయᵓ㐀ࡢೃ⿵ࢆᚓࡓࠋᚓࡽࢀࡓ」ྜయᵓ㐀ࢆ⏝࠸࡚ศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ」ྜయࡢᵓ㐀Ᏻᐃᛶࢆゎᯒࡋࡓࠋࡲࡓࠊኚ␗ᰴ࡟ࡘ࠸࡚ࡶྠᵝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ㔝⏕ᰴ࡜ẚ㍑ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁ࡢ S1 㡿ᇦ࡜᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫឤᰁ⑕࠿ࡽᅇ᚟ࡋࡓᝈ⪅࠿ࡽศ㞳ࡉࢀࡓ SARS-CoV-2

࡟ᑐࡍࡿ୰࿴ᢠయ CR3022 ࡜ࡢ」ྜయᵓ㐀㸦PDB ID: 6YOR㸧ࢆ୍ᗘศ㞳ࡋࠊZDOCK ࢆ⏝࠸ࡓࢻࢵ࢟ࣥࢢࢩ
࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚㔝⏕ᰴ࡟ᑐࡍࡿ」ྜయᵓ㐀ࢆసᡂࡋࡓࠋࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࣛࣥࢡࡀ᭱
ࡶ㧗࠸ࡶࡢࢆ㑅ࢇ࡛ࠊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋኚ␗ᰴ࡜ࡋ࡚ࠊE484K/N501Y㸦ࣈࣛࢪࣝᰴ㸧ࢆ⪃࠼ࡓࠋ㔝⏕ᆺࡢ X ⥺ᵓ㐀ࢆ⏝࠸࡚ࠊࡑࢀࡒࢀࡢ࢔࣑ࣀ㓟ࢆኚ␗ࡉࡏࡓᵓ㐀ࢆసᡂࡋࡓࠋᚓࡽࢀ

ᅗ 1. ᖹ⾮໬ᚋࡢᵓ㐀ࠋ(a)ࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁(ྑഃ)࡜ᢠయ㸦ᕥഃ㸧
ࠋ(b)ࢫࣃ࢖ࢡ
ࢱࣥࣃࢡ㉁ࡢࡳࢆᢤࡁฟࡋࡓࡶࡢࠋࢩ࢔ࣥ㸸㔝⏕ᰴࠊ⥳㸸ኚ␗ᰴ- 202 -

ࡓኚ␗ᰴࡢᵓ㐀࡜୰࿴ᢠయ CR3022 ࡢࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊኚ␗ᰴ࡟ᑐࡍࡿ」ྜయᵓ㐀ࢆసᡂࡋࡓࠋ㔝⏕ᰴࡢሙྜ࡜ྠᵝ࡟ MD ࢆᐇ⾜ࡋࡓࠋࡑࢀࡒࢀࡢ」ྜయᵓ㐀ࡢᏳᐃᛶ࡟ࡘ࠸࡚ࠊ㔝⏕ᰴ࡜ኚ␗ᰴ
ࡢᕪࢆㄪ࡭ࡓࠋMD ࡢᐇ⾜࡟ࡣ AMBER ࢆ⏝࠸ࡓࠋࢱࣥࣃࢡ㉁ࠊỈࡢຊሙ࡟ࡣ amberff96SBࠊTIP3P ࢆ⏝࠸ࡓࠋࡑࢀࡒࢀࡢ
」ྜయࡢ࿘ᅖ࡟ỈศᏊ࠾ࡼࡧ࢖࢜ࣥࢆ㓄⨨ࡋࡓᚋࠊ࢚ࢿࣝࢠ࣮᭱ᑠ໬ࢆ⾜࡞ࡗࡓࠋࡑࡢᚋࠊ᫬㛫้ࡳࢆ 2 fs ࡜ࡋ࡚ࠊ310 Kࠊ1 Ẽᅽࡢ NPT ࢔ࣥࢧࣥࣈ࡛ࣝ MD ࢆᐇ⾜ࡋࡓࠋ3◊✲ᡂᯝࡑࢀࡒࢀࡢ」ྜయᵓ㐀࡟ᑐࡋ࡚ 50 ns ࡢ MD ࢆ⾜࡞ࡗࡓࠋ50 ns ᚋࡢᵓ㐀ࢆᅗ 1 ࡟♧ࡍࠋࡑࢀࡒࢀࡢ」ྜయ

ᵓ㐀࡟ᑐࡋ࡚ࠊᢠయ㸦ᅗ 1a ᕥഃ㸧ࡀ㔜࡞ࡿࡼ࠺࡟ᅗ♧ࡋࡓࠋᢠయ࡟ᑐࡋ࡚ࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁㸦ᅗ 1a ྑഃ㸧ࡢ㓄ྥࡀ␗࡞ࡿ⤖ᯝ࡜࡞ࡗࡓࠋ50 ns 㛫ࡢ Root Mean Square Deviation (RMSD)ࡢ᫬㛫ኚ໬ࢆᅗ 2 ࡟♧ࡍࠋ」ྜ
యᵓ㐀࡟ᑐࡍࡿ RMSD㸦ᅗ 2a㸧ࢆぢࡿ࡜ࠊ㔝⏕ᰴ࡛ࡣᢠయ࡜ࡢ」ྜయᵓ㐀ࡀ 50 ns ࡛Ᏻᐃ࡞⤖ᯝ࡜࡞ࡗࡓࠋ
୍᪉࡛ኚ␗ᰴ࡛ࡣࠊ25 ns ௨㝆 RMSD ࡢኚ໬ࡀ኱ࡁࡃ࡞ࡗ࡚࠾ࡾᏳᐃ࡞ᵓ㐀࡜ࡣ࠸࠼࡞࠸ࠋࢫࣃ࢖ࢡࢱࣥࣃ
ࢡ㉁ࡢࡳࡢ RMSD㸦ᅗ 2b㸧ࡣࠊࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡣ㔝⏕ᰴ࡛ࡶኚ␗ᰴ࡛ࡶᏳᐃࡋࡓ⤖ᯝ࡜࡞ࡗࡓࠋ
ࡇࡇࡲ࡛ࡢ MD ࠿ࡽࠊኚ␗ᰴࡢࢫࣃ࢖ࢡࢱࣥࣃࢡ㉁ࡣ㔝⏕ᰴ࡜ẚ࡭࡚ᢠయ࡜ࡢ」ྜయᙧᡂࡀᏳᐃ࡛ࡣ࡞࠸ࡇ
࡜ࡀ♧၀ࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] K. Kawaguchi, H. Nagao, “Theoretical study of complex formation of Plastocyanin and Cytochrome f” ➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍㸦࢜ࣥࣛ࢖ࣥ㸧2021 ᖺ 11 ᭶ 25ࠥ27 ᪥[2] ‫ۻ‬K. Kawaguchi, R. M. Karim, A. C. Pradana, H. Nagao, “Coarse-grained model for protein-nucleotide interaction”,
XXXII IUPAP Conference on Computational Physics (online) 1-5 August 2021.
[3] ‫ۻ‬K. Kawaguchi, H. Nagao, “Development of Coarse-grained model for protein complex”, IUPAB/SBBf/SBBq
2021 Congress (online) 4-8 October 2021.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫ۻ‬K. Kawaguchi, S. Ito, H. Saito, H. Nagao "Molecular dynamics study of lipid bilayer asymmetry induced by ion
concentration
gradient
andelectronic
polarizability",
Molecular
Simulation
1-7
2022,
10.1080/08927022.2022.2025798[2] D. Fitrasari, M. S. Arwansyah,
K. Kawaguchi, A. Purqon,
Suprijadi,
H.
Nagao,"Theoretical
Studyof
Dissociation
Processof
Plastocyanins by PaCS-MD
Simulation", Journal of Physics:
Conference Series 2207(1)012021-012021
2022,
10.1088/17426596/2207/1/012021[3] H. Jayyinunnisya, L. S. Solihat,
K. Sugimori, K. Kawaguchi, H.
Nagao, “Theoretical Study ofᅗ 2. RMSD ࡢ᫬㛫ኚ໬ࠋ(a)」ྜయᵓ㐀࡟ᑐࡍࡿ RMSDࠋ(b)ࢫࣃ࢖
Complex
Aspirinandࢡࢱࣥࣃࢡ㉁ࡢࡳࡢ RMSDࠋ⥳㸸㔝⏕ᰴࠊ⣸㸸ኚ␗ᰴࠋ
Hydroxypropyl-ȕ- cyclodextrin- 203 -

in Solvent Phase”, Journal of Physics: Conference Series, 2207 (2022) 012022 doi:10.1088/17426596/2207/1/012022.

- 204 -

ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂Theoretical Studies on Mechanisms of Catalytic Reactions‫ۑ‬᳃ ⪷἞ࠊAttila Taborosi, ᓥᓮඃ୍ࠊ㕥ᮌ ᓫࠊᗉᮧᗣேࠊ㓇஭┤ᶞࠊ㕥ᮌ 㥴ࠊᒸᮏඃᝅࠊ⸨஭⛸㤿ࠊᆈ ඃెࠊ኱ሯᝆᩯࠊᒣཱྀᓧⱥࠊⳢ஭☐ᐂࠊ▼ᶫ ᜨࠊ✑✚⋹᪊㸦Ⲉᇛ኱Ꮫ㸧

1◊✲┠ⓗᮏ◊✲࡛ࡣ,(1)⌮ㄽ໬Ꮫࢆᇶ┙࡜ࡋࡓ࡞ࡿ࡭ࡃ↓㥏࡞ヨ⸆ࢆ౑⏝ࡋ࡞࠸,࠿ࡘ↓㥏࡞๪⏕ᡂ≀ࢆฟࡉ࡞࠸(ࡍ࡞ࢃࡕ⎔ቃ࡟ඃࡋ࠸)㧗ຠ⋡ⓗゐ፹཯ᛂࡢ㛤Ⓨ(2)⎔ቃ⛉Ꮫⓗ࠶ࡿ࠸ࡣ⏕໬Ꮫⓗ࡟⯆࿡῝࠸ゐ፹཯ᛂᶵᵓࡢゎ᫂ࢆ⾜ࡗ࡚࠸ࡿࠋ2021 ᖺᗘࡢሗ࿌᭩࡛ࡣ◊✲ᡂᯝࡢ࠺ࡕࠊ௦⾲ⓗ࡞㸱౛ࢆሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬ࡸศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣ Gaussian 16

Rev. B. 01 ࠶ࡿ࠸ࡣ Rev. C 01,

ORCA ࠾ࡼ

ࡧ AMBER 18 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋィ⟬ࡣ୺࡟ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ₇⟬ࢧ࣮ࣂ࣮࠾ࡼࡧᙜ◊✲ᐊࡢࢥࣥࣆ࣮ࣗࢱୖ࡛⾜ࡗࡓࠋࡉࡽ࡟ࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝(NCI)ࡢ⾲♧࡟ࡣࠊVMD ࠾ࡼࡧ Multiwfn 3.8 ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

3.1 ࢟ࣛࣝ࡞ࣂࢼࢪ࣒࢘ゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥࡢ㓟໬ⓗ 1,2-ࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬ࡢ⌮ㄽⓗ◊✲᭷ᶵࣇࢵ⣲໬ྜ≀ࡣࠊᵝࠎ࡞ศ㔝࡛฼⏝ࡉࢀ࡚࠾ࡾࠊ≉࡟ࠊ་⸆ศ㔝࡟࠾࠸࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋCF3 ᇶࢆᑟධࡍࡿ࡜ࠊᙉ࠸㟁Ꮚ྾ᘬᛶࠊ㓟໬ⓗ௦ㅰ࡟ᑐࡍࡿᏳᐃᛶࡢྥୖ(ᙉ࠸ C-F ⤖ྜ)ࠊ⬡⁐ᛶࡢྥୖ࡞࡝
ࡢᶵ⬟ࢆ᭷ᶵ໬ྜ≀࡟୚࠼ࡿࡇ࡜ࡀ࡛ࡁࡿࠋtert-ࣟ࢖ࢩࣥ࠿ࡽㄏᑟࡉࢀࡓ୕ᗙ Schiff ሷᇶ㓄఩Ꮚ㸦N-ࢧࣜࢳࣜࢹࣥᆺ㓄఩Ꮚ㸧ࢆྵࡴ࢜࢟ࢯࣂࢼࢪ࣒࢘ゐ፹࡜ Togni ヨ⸆(ࣚ࢘⣲ࢆྵࡴ)ࡢ⤌ࡳྜࢃࡏࢆ⏝࠸࡚ࠊᖖ࡛࢜ࣞࣇ࢕ࣥࡢࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬ࡢ཯ᛂࢆ㉳ࡇࡍࡇ࡜࡟ᡂຌࡋࡓࠋ㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ

໬཯ᛂ࡟ࡼࡿ୙ᩧⅣ⣲ࡢᵓ⠏ࡣศᏊ㛫཯ᛂ࡜ࡋ࡚ึࡵ࡚ࡢ౛࡛࠶ࡿ㸦ᅗ 1㸧[1]ࠋ

ᅗ㸯. ࢟ࣛࣝ࡞ࣂࢼࢪ࣒࢘࢜࢟ࢯゐ፹ࢆ⏝࠸ࡓ㧗࢚ࢼࣥࢳ࢜㑅ᢥⓗ࡞㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂ

ࢫࢳࣞࣥࠊNHPI(N-ࣄࢻࣟ࢟ࢩࣇࢱࣝ࢖࣑ࢻ)࡜࢜ࣞࣇ࢕ࣥࡢ㸱ᡂศ 1,2-㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬ࡢ

- 205 -

཯ᛂᶵᵓࡀ࠸ࡃࡘ࠿⪃࠼ࡽࢀࡿࠋᅗ 2 ࡟཯ᛂᶵᵓࢆ♧ࡍࠋᅗ㸰. ࢜ࣞࣇ࢕ࣥ࡜ NHPI ࡢ㸱ᡂศ 1,2-㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂᶵᵓ

ࡲࡎࠊ࢔ࣝࢥ࣮ࣝࡀ㓄఩ࡋ࡚࠸ࡿࣂࢼࢪ࣒࢘(V)࢜࢟ࢯ㘒య࡟ NHPI ࡀ⤖ྜࡋ࡚ࠊNHPI ࡀࣂࢼࢪ࣒࢘(V)࢜࢟ࢯ㘒య࡜㘒ᙧᡂࡋࡓ㘒య I ࢆ⏕ࡌࡿࠋTogni ヨ⸆࠿ࡽᨺฟࡉࢀࡓ CF3 ࣛࢪ࢝ࣝࡀ࢜ࣞࣇ࢕ࣥᇶ㉁࡟
௜ຍࡋ࡚⏕ᡂࡋࡓ࣋ࣥࢪࣝࣛࢪ࢝ࣝࡀ࢜࢟ࢯ㓟⣲࡜┦஫స⏝ࡋࠊ࢔ࣝࢥ࢟ࢩࣂࢼࢪ࣒࢘(IV)ᆺࡢ㘒య IV࡟࡞ࡿࠋࡇࡢ཯ᛂᶵᵓࢆ DFT ィ⟬㸦UM06(SMD)/def2-TZVPP/W06//UBP86+D3BJ(SMD)/def2-SVP/W06 ࣞ࣋ࣝ㸸⁐፹࡜ࡋ࡚ࡣ 2-propanol (ε = 19.264)㸧᳨࡛ウࡋࡓࡀࠊ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ㧗࠿ࡗࡓࠋ୍᪉ࠊ๓

㏙ࡢ I ࠿ࡽࠊ⏕ᡂࡋࡓ࣋ࣥࢪࣝࣛࢪ࢝ࣝࡀ NOPI 㓄఩Ꮚࡢ O2 ཎᏊ࡟ᨷᧁࡋ࡚ࣛࢪ࢝ࣝ⨨᥮཯ᛂࡀ㉳ࡁࠊ㘒య II ࡀ⏕ᡂࡋࡓࡢࡕ࡟ゎ㞳ࡍࡿ⤒㊰㸦SH2 ཯ᛂⓗ㸧ࡀࡶࡗ࡜ࡶࡽࡋ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ
ࡉࡽ࡟ࠊ᭱ࡶ࢚ࢿࣝࢠ࣮ࡢప࠸ SH2 ཯ᛂ⤒㊰࡟ᑐࡋ࡚ࠊUM06(SMD)/def2-TZVPP//UM06/def2-SVP ࡛ࣞ࣋ࣝࡢ᳨ウࢆ⾜ࡗࡓࠋゐ፹ 1 ࢆ⏝࠸ࡓሙྜ୺⏕ᡂ≀࢚ࢼࣥࢳ࣐࣮࢜࡟⮳ࡿ(S)-TSIa-II ࡢ᪉ࡀࠊ(R)-యࢆ⏕ᡂࡍࡿ㑄⛣≧ែ(R)-TSIa-II ࡟ẚ࡭࡚  N-PRO ࡶప࠿ࡗࡓࠋࡇࡢࡇ࡜ࡣࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝ 1&, ゎᯒ࠿ࡽࡶ⿬௜ࡅ
ࡽࢀࡿࠋ࣋ࣥࢪࣝࣛࢪ࢝ࣝࡢࣇ࢙ࢽࣝᇶ࡜ 123, ࡢ㛫ࡢ π-π ┦஫స⏝ࡢ኱ࡁࡉ࡟㐪࠸ࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
࡯࠿࡟ࡶࠊ(S)-TSIa-II ࡟࠾࠸࡚ࠊC–F···O1 ࡞࡝ࡢ┦஫స⏝ࡀぢࡽࢀࡓࠋ୍᪉ࠊ㓄఩Ꮚࡢ C3 ఩ࡀ(2,5-dimethyl)phenyl ᇶࡢゐ፹ 1 ࡟ࡘ࠸࡚ࡶࠊ࢝ࢵࣉࣜࣥࢢ཯ᛂࡢ㑄⛣≧ែ࡜ࡑࡢ๓ᚋ
ࡢᏳᐃᵓ㐀ࡢ㐣⛬ࢆ᳨ウࡋࡓࠋࡇࡢሙྜࠊ(R)-TSIa-II ࡢ᪉ࡀࠊ(S)-TSIa-II ࡟ẚ࡭࡚ࠊ2.0 kJ/mol ࢚ࢿࣝࢠ࣮ⓗ࡟ప࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋゐ፹ 2 ࢆ⏝࠸ࡓሙྜ(R)-యࢆ୺࡟⏕ᡂࡍࡿ࡜࠸࠺࢚ࢼࣥࢳ࢜㑅ᢥᛶ㸦ࡑࢀ࡯࡝㧗ࡃࡣ࡞࠸ࡀ㸧࡟㛵ࡍࡿᐇ㦂⤖ᯝࡶ ')7 ィ⟬࡛ㄝ࡛᫂ࡁࡓࠋࡇࡢཎᅉ࡟㛵ࡋ࡚ࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝ 1&, ゎᯒ࠾ࡼࡧศᏊෆཎᏊࡢ㔞Ꮚㄽ 47$,0 ゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊ (2,5-dimethyl)phenyl ⨨᥮ᇶ࡜ 123, ࡢ㛫࡟ᇶ㉁⏤᮶ࡢ࣋ࣥࢪࣝࣛࢪ࢝ࣝࡀᣳࡲࡾS-SS┦஫స⏝䛜㉳䛝䛶䛔䜛䛣䛸䛜ㄝ᫂䛷䛝䜛䚹௨ୖࠊࣂࢼࢪ࣒࢘ゐ፹࢜ࣞࣇ࢕ࣥࡢ 1,2-㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂࡢ㛤Ⓨ࡟࠾࠸࡚ࠊ⌮ㄽⓗ᳨ウࡢ㔜せᛶࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
3.2 ᭷ᶵศᏊゐ፹ࢆ⏝࠸ࡿȘ-࢔࣑ࣀ࣐ࣞ࢖࣑ࢻࡢș-ࢽࢺࣟࢫࢳࣞࣥ࡟ᑐࡍࡿ୙ᩧ࣐࢖ࢣࣝ௜ຍ཯ᛂࡢᐇ㦂ⓗ࣭⌮ㄽⓗ◊✲
࣐ࣞ࢖࣑ࢻ㦵᱁ࡣࠊࡑࡢㄏᑟయࡀඃࢀࡓ≀ᛶ࠾ࡼࡧ⏕≀ⓗ≉ᛶࢆᣢࡘࡇ࡜࠿ࡽࠊ᭷ᶵྜᡂୖ᭷⏝࡞㦵᱁࡛࠶ࡿࠋ࣐ࣞ࢖࣑ࢻࡣඃࢀࡓ࣐࢖ࢣࣝ࢔ࢡࢭࣉࢱ࣮࡜ࡋ࡚▱ࡽࢀ࡚࠾ࡾࠊ࣐ࣞ࢖࣑ࢻ࡟ᑐࡍࡿ✀ࠎࡢồ᰾๣࡟- 206 -

ࡼࡿ࣐࢖ࢣࣝ௜ຍ཯ᛂࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࣐ࣞ࢖࣑ࢻࢆồ㟁Ꮚ๣࡜ࡍࡿ࣐࢖ࢣࣝ௜ຍ཯ᛂ࡛
ᚓࡽࢀࡿ⏕ᡂ≀ࡣࠊࡑࡢ㦵᱁ࡀࢫࢡࢩࣥ࢖࣑ࢻ㦵᱁࡬࡜ኚ᥮ࡉࢀࡿࠋ୍᪉ࠊ࣐ࣞ࢖࣑ࢻࢆồ᰾๣࡜ࡋ࡚⏝࠸ࡿ཯ᛂ࡛ࡣࠊ⏕ᡂ≀࡟࣐ࣞ࢖࣑ࢻ㦵᱁ࢆಖᣢ࡛ࡁࡿࡓࡵࠊࡼࡾຠ⋡ⓗ࡟࣐ࣞ࢖࣑ࢻ㦵᱁ࢆྵࡴ໬ྜ≀ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡋ࠿ࡋࠊ࣐ࣞ࢖࣑ࢻࢆồ᰾๣࡜ࡋ࡚⏝࠸ࡿ཯ᛂࡣᑡ࡞ࡃࠊ࡜ࡃ࡟୙ᩧྜᡂ࡟⏝࠸ࡓ཯ᛂࡢሗ
࿌౛ࡣ࡞࠸ࠋ
ࡇࢀ࡟ᑐࡋ࡚ᡃࠎࡣࠊࢩࣥࢥࢼ࢔ࣝ࢝ࣟ࢖ࢻ࠿ࡽㄏᑟࡉࢀࡿᒀ⣲ᆺࡢ᭷ᶵศᏊゐ፹ࢆࢃࡎ࠿ 1 mol%⏝࠸ࡿࡔࡅ࡛ࠊα-࢔࣑ࣀ࣐ࣞ࢖࣑ࢻࡢ β-ࢽࢺࣟࢫࢳࣞࣥ࡟ᑐࡍࡿ୙ᩧ࣐࢖ࢣࣝ௜ຍ཯ᛂࡀࠊ㧗཰⋡ࠊ㧗࢚ࢼࣥࢳ࢜
㑅 ᢥ ⓗ ( ᭱ 㧗 94% ee) ࡟ 㐍 ⾜ ࡍ ࡿ ࡇ ࡜ ࢆ ᫂ ࡽ ࠿ ࡟ ࡋ ࡓ 㸦 ᅗ 㸱 㸧ࠋ B3LYP+D3BJ(SMD)/6-311++G**//M062X(SMD)/6-31G**ࣞ࣋ࣝ࡟ࡼࡿᐦᗘỗ㛵ᩘἲ㸦DFT㸧ィ⟬࡟ࡼࡾࠊ཯ᛂࡣࠊ࣐ࣞ࢖࣑ࢻ α ఩ࡢ࢔࣑ࣀᇶ࠿ࡽࣉ
ࣟࢺࣥࢆᘬࡁᢤࡁࠊࡑࡢ࠶࡜ẁ㝵ⓗ࡟ࠊα-࢔࣑ࣀ࣐ࣞ࢖࣑ࢻ࡜ β-ࢽࢺࣟࢫࢳࣞࣥࡢ㛫࡛Ⅳ⣲̿Ⅳ⣲⤖ྜ⏕ᡂࡀ㉳ࡁࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡉࡽ࡟ࠊN-࣓ࢳ࣐ࣝࣞ࢖࣑ࢻࢆ⏝࠸ࡓ࡜ࡁࡢ཯ᛂࡢ㑅ᢥᛶࢆ᳨ウࡋ࢚ࢼࣥࢳ
࢜㑅ᢥᛶࡣ 78% ee ࡛࠶ࡿࡇ࡜ࡀᐇ㦂࡛ศ࠿ࡗ࡚࠾ࡾࠊ࣐ࣞ࢖࣑ࢻ N ୖࡢ⨨᥮ᇶࢆࡼࡾ࠿ࡉ㧗࠸⨨᥮ᇶ࡟ኚ᭦ࡍࡿ࡜ࠊ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡣྥୖࡍࡿࡢ࡛ࡣ࡞࠸࠿࡜ண

ࡋࡓࠋN-࢖ࢯࣈࢳ࣐ࣝࣞ࢖࣑ࢻ࡟ࡘ࠸࡚ᐇ㦂᳨࡛ウࡋࡓ࡜ࡇࢁࠊ
ண᝿㏻ࡾ᭱㧗 92 %ee ࡜ྥୖࡋࡓࠋ
N-࢖ࢯࣈࢳ࣐ࣝࣞ࢖࣑ࢻࡢ࣐࢖ࢣࣝ௜ຍయࡢ❧య໬Ꮫࡣࠊ
࢔ࢭࢺࢽࢺࣜࣝ⁐ᾮ୰࡛ᐃࡋࡓ ECD ࢫ࣌ࢡࢺࣝ࡜ࠊTD-B3LYP+D3BJ(SMD)/6-311++G**//B3LYP+D3BJ/6-

31G**ࣞ࣋ࣝ࡟ࡼࡿ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ ECD ࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࡛Ỵᐃࡋࡓࠋᅗ㸱 α-࢔࣑ࣀ࣐ࣞ࢖࣑ࢻࡢ β-ࢽࢺࣟࢫࢳࣞࣥ࡟ᑐࡍࡿ୙ᩧ࣐࢖ࢣࣝ௜ຍ཯ᛂ࡜㑄⛣≧ែ

3.3 ᪂つ࢟ࣛࣝ 1,2-ࢪ࢔࣑ࣥゐ፹ࢆ⏝࠸ࡿș఩࡟ᐁ⬟ᇶࢆ᭷ࡉ࡞࠸➨୍⣭࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭ࡢ
ᐇ㦂ⓗ࣭⌮ㄽⓗ◊✲࢟ࣛࣝ࡞࢔ࣝࢥ࣮ࣝࡣ་⸆ရࡸ㎰⸆ࡢྜᡂ࡟࠾࠸࡚㔜せ࡞ྜᡂ୰㛫య࡛࠶ࡾࠊᩘከࡃࡢྜᡂἲࡀሗ࿌ࡉࢀ
࡚࠸ࡿࠋ≉࡟୙ᩧ࢔ࢩࣝ໬࡟ࡼࡿ㏿ᗘㄽⓗගᏛศ๭ࡣࠊ࢟ࣛࣝ࡞➨஧⣭࢔ࣝࢥ࣮ࣝࢆྜᡂࡍࡿ᭷ຊ࡞ᡭẁ࡜ࡋ࡚☜❧ࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊࣄࢻࣟ࢟ࢩᇶࡢ β ఩࡟ᐁ⬟ᇶࢆ᭷ࡉ࡞࠸➨୍⣭࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭ࡣ㠀ᖖ࡟ᅔ㞴࡛࠶ࡾࠊ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀ࡯࡜ࢇ࡝Ⓨ⌧ࡋ࡞࠿ࡗࡓࠋࡑࡇ࡛ᡃࠎࡣࠊβ ఩࡟ᐁ⬟ᇶࢆ᭷ࡉ࡞࠸
➨୍⣭࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭ࢆ㐩ᡂࡍࡿࡓࡵ࡟ࠊ᪂つゐ፹ࡢタィ࣭㛤Ⓨ࡜㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡿゎᯒࢆ⾜ࡗࡓࠋ2,3-ࢪࣄࢻࣟ-1H-࣋ࣥࢰ[de]࢖ࢯ࢟ࣀࣜࣥ㦵᱁ࢆᣢࡘ 1,2-ࢪ࢔࣑ࣥゐ፹ࢆ⏝࠸ࡓሙྜࠊ᭱㧗 10 ࡢs ್㸦Kagan ࡽ࡟ࡼࡗ࡚ᥦ᱌ࡉࢀࡓࠊ㏿ᗘㄽⓗගᏛศ๭ࡢᣦᶆ㸧࡛ศ๭ࡀ㐍⾜ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ
⤖ᯝࢆࡶ࡜࡟㔞Ꮚ໬Ꮫィ⟬㸦M06-2X/6-311++G**//M06-2X/6-31+G**㸧ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ࢔ࣝࢥ࣮ࣝࡢ࣋ࣥࢰ
࢖ࣝ໬ࡢ㑄⛣≧ែ࡟࠾ࡅࡿ 1,2-ࢪ࢔࣑ࣥゐ፹࡟࠾ࡅࡿ࣋ࣥࢰ[de]࢖ࢯ࢟ࣀࣜࣥࡢ࣓ࢳࣞࣥᇶ࡜࢔ࣝࢥ࣮ࣝᇶ㉁ࡢⰾ㤶᪘⨨᥮ᇶ㛫ࡢ CH-π ┦஫స⏝ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝(NCI)ゎᯒ࡛ࢃ࠿ࡗࡓ㸦ᅗ㸲㸧ࠋ- 207 -

ᅗ㸲 ࢟ࣛࣝ࡞ 1,2-ࢪ࢔࣑ࣥゐ፹ࢆ⏝࠸ࡓ β ఩࡟ᐁ⬟ᇶࢆ᭷ࡉ࡞࠸➨୍⣭࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫⸨ۻ‬஭ ⛸㤿, Bang-You Tsai, Tsung-Cheng Chen, Chien-I Lein, Yu-Chang Chang, Pin-Xuan Tseng, Chin-Wei Chuang,

Rachit Agarwal, Chan-Wei Hsu, Chien-Tien Chen, ᳃ ⪷἞, ࢟ࣛࣝ࡞ࣂࢼࢪ࣒࢘ゐ፹ࢆ⏝࠸ࡓ㓟໬ⓗ 1,2-ࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂࡢ⌮ㄽⓗ◊✲, ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍ (2022), 2022 ᖺ㸱᭶㸰㸱㸫㸰㸴᪥ࠊすᐑ‫ۻ‬㓇஭┤ᶞࠊᑠᓥᔞᖹࠊ᳃ ⪷἞ࠊᢡᒣ ๛ࠊ࢟ࣛࣝ ࢪ࢔࣑ࣥゐ፹ࢆ⏝࠸ࡿș఩࡟ᐁ⬟ᇶࢆ᭷ࡉ࡞
࠸➨୍⣭࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭ࠊ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍   ᖺ㸱᭶㸰㸱㸫㸰㸴᪥‫ۻ‬ᒸᮏ ඃᝅࠊ᳃ ⪷἞ࠊࣃࣛࢪ࣒࢘ゐ፹࡟ࡼࡿ Alkenyl Carboxylates ࡢࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࡢ⌮ㄽⓗ◊✲ࠊ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍ (2022), 2022 ᖺ㸱᭶㸰㸱㸫㸰㸴᪥ࠊすᐑ‫ۻ‬᳃ ⪷἞ࠊComputational Perspectives of Non-covalent Interactions in Transition

Metal- and Enzyme-catalyzed

Reactions 㘒య໬Ꮫ఍➨㸵1 ᅇウㄽ఍ࠊ2021 ᖺ 9 ᭶ 16 ᪥,࢜ࣥࣛ࢖ࣥ㸦౫㢗ㅮ₇ࠊS4-05㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1]‫ۻ‬C.-T. Chen, Y.-C. Su, C.-H. Lu, C.-I. Lien, S.-F. Hung, C.-W. Hsu, R. Agarwal, R. Modala, H.-M. Tseng, P.-X. Tseng,
R. Fujii, K. Kawashima, S. Mori, Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by
Chiral Vanadyl Complexes: Importance of Noncovalent Interactions. ACS Catal. 2021, 11, 7160–7175.
[2]‫ۻ‬N. Sakai, K. Kawashima, M. Kajitani, S. Mori, and T. Oriyama, Combined Computational and Experimental Studies
on the Asymmetric Michael Addition of α-Aminomaleimides to β-Nitrostyrenes Using an Organocatalyst Derived from
Cinchona Alkaloid, Org. Lett. 2021, 23, 5714-5718.
[3]‫ۻ‬N. Sakai, K. Ojima, S. Mori, T. Oriyama, Integrated Experimental and Computational Studies on the Organocatalytic Kinetic Resolution of β-Unfunctionalized Primary Alcohols Using a Novel Chiral 1,2-Diamine: The Importanceof Noncovalent Interactions, J. Org. Chem. 2022, 87, 4468–4475[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.

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- 209 -

ከඖ⣲ࢡࣛࢫࢱ࣮ࡢ㉥እゎ㞳ศගࡢࡓࡵࡢ㉥እࢫ࣌ࢡࢺࣝࡢண
3UHGLFWLRQRILQIUDUHGVSHFWUDRIPXOWLHOHPHQWFOXVWHUVIRULQIUDUHGSKRWRGLVVRFLDWLRQVSHFWURVFRS\‫ۑ‬ᕤ⸨ ⪽㸪Ọ⏣



฼᫂㸪ᒣཱྀ

㞞ே㸦ᮾி኱Ꮫ㝔⥲ྜᩥ໬㸧◊✲┠ⓗ㔠ᒓࢡࣛࢫࢱ࣮ୖ࡛ࡢゐ፹཯ᛂࡢ཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ᪼

ගᐇ㦂࡞࡝ࡢᐇ㦂࡜㔞Ꮚ໬Ꮫィ⟬ࢆే⏝ࡋ࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ௒ᮇࡣ

⬺㞳ᐇ㦂ࠊ㉥እゎ㞳ศ

CaMn4O5+ࢡࣛࢫࢱ࣮ࠊRhnNO+ࢡࣛࢫࢱ࣮ࠊRhnIrNO+ࢡࣛࢫࢱ࣮ࠊAu4NO-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

ᐃࡋࠊGaussian09 ࡟ࡼࡿ㔞Ꮚ໬Ꮫィ⟬㸦୺࡟ DFT ィ⟬㸧࡟ࡼࡗ࡚ண
ࡇ࡜࡛ᵓ㐀ࡢỴᐃࢆ࠾ࡇ࡞ࡗࡓࠋࡑࡢ࡯࠿࡟ࠊẼ┦᪼」ྜయ࠿ࡽࡢศᏊ⬺㞳ࡢࡉࢀࡓࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥ࡜ẚ㍑ࡍࡿ

⬺㞳ᐇ㦂࡛ᚓࡽࢀࡓ㔠ᒓࢡࣛࢫࢱ࣮࡜⿕ゐ፹ศᏊࡢᗘ౫Ꮡᛶࢆㄝ᫂ࡍࡿࡓࡵ࡟ࠊ཯ᛂ࡟㛵ࢃࡿ୰㛫యࡸ㑄⛣≧ែࡢᵓ㐀᭱㐺໬ࢆ࠾ࡇ

࡞ࡗࡓࠋ



◊✲ᡂᯝ
CaMn4O5+ࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚ࡣࠊ᫖

ᖺᗘ࡟ᘬࡁ⥆ࡁ CaMn4O5+ࢡࣛࢫࢱ࣮࡟
ỈศᏊࡀ྾╔ࡋࡓ CaMn4O5H2O+ࡢᵓ㐀᥈⣴ࢆ࠾ࡇ࡞ࡗ࡚ࠊᚓࡽࢀࡓᏳᐃᵓ㐀࡟ࡘ࠸࡚᣺ືᩘィ⟬ࡋࠊ㉥እࢫ࣌ࢡࢺࣝࣃ
ࢱ࣮ࣥࢆసᡂࡋ࡚ᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࠋ
ࡲࡓࠊCaMn4O5+ୖ࡛ࡢỈศᏊࡢ⛣ື࡟ࡘ࠸࡚ㄪ࡭ࡿࡓࡵ࡟ࠊỈศᏊ⛣ືࡢ୰㛫యࡸ㑄⛣≧ែࢆィ⟬ࡋࡓࠋᅗ㸯࡟♧ࡋࡓIsomer 1 ࠿ࡽ Isomer 2 ࡬ࡢ␗ᛶ໬࡟࡜ࡶ
࡞࠺ỈศᏊࡢ⛣ືࡢ㞀ቨࡣ+25 kJ mol‫ە‬: Ca, ‫ە‬: Mn, ‫ە‬: O, ࠐ: H

Ѹ1⛬ᗘ࡛࠶ࡾࠊỈศᏊࡣᐜ᫆࡟ືࡁᅇࢀࡿ

ᅗ 1. CaMn4O5+ୖ࡛ࡢỈศᏊ⛣ືࡢ࢚ࢿࣝࢠ࣮ᅗࡢ୍౛

ࡇ࡜ࡀࢃ࠿ࡗࡓࠋCaMn4O5H2O+ ࡢ㉥እゎ㞳ศගࡢ⤖ᯝ࡛ࡣゎ㞳྾╔␗ᛶయࡢࡳࡀほࡉࢀ࡚࠸ࡿࠋᅗ୰ࡢ Isomer 2 ࡢᵓ㐀࠿ࡽ㞀ቨ㸦+19.3 kJ mol-1㸧ࢆ஌ࡾ㉺࠼࡚ỈศᏊࡢゎ㞳ࢆᘬࡁ㉳ࡇࡍ␗ᛶయ࡟⮳ࡿ⤒㊰ࡀࡇࢀࡲ࡛࡟ぢࡘ࠿ࡗ࡚࠸ࡿ㸦2020 ᖺᗘሗ࿌᭩ཧ
↷㸧ࠋ௒ᅇࡢィ⟬⤖ᯝࢆ㋃ࡲ࠼ࡿ࡜ CaMn4O5H2O+୰ࡢỈศᏊࡣྛ྾╔ࢧ࢖ࢺ㛫ࢆ⛣ືࡋゎ㞳཯ᛂࡢධࡾཱྀࡢ
྾╔ࢧ࢖ࢺ࡟฿㐩ࡋࠊࡑࡢᚋࠊゎ㞳ࡢ⤒㊰࡟஌ࡗ࡚ゎ㞳ࡍࡿ࡜⪃࠼ࡿ࡜ࠊศᏊ྾╔␗ᛶయࡀほ࠸࠺⤖ᯝࢆㄝ࡛᫂ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

- 210 -

ࡉࢀ࡞࠸࡜

RhnNO+ ࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚ࡣࠊRh6NO+ ࢡࣛࢫࢱ࣮ࠊRh12+
ࢡࣛࢫࢱ࣮ࠊRh13NO+ࢡࣛࢫࢱ࣮࡞࡝ࢆィ⟬ࡋࡓࠋ୍౛࡜ࡋ࡚ࠊ
Rh12+ࢡࣛࢫࢱ࣮ࡢ㉥እࣃࢱ࣮ࣥࢆ♧ࡍࠋHarding ࡽ࡟ࡼࡾ㉥እゎ㞳ࢫ࣌ࢡࢺࣝࡀሗ࿌ࡉࢀ࡚࠾ࡾ[1]ࠊ࠸ࡎࢀࡢ DFT ࠾ࡼࡧᵓ㐀ࡀࡑࡢࢫ࣌ࢡࢺࣝ࡜୍⮴ࡍࡿࡢ࠿ࢆㄪ࡭ࡓࠋPBE1PBE/SDD࡛ࣞ࣋ࣝィ⟬ࡋࡓࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥࡢ୍㒊ࢆᅗ㸱࡟♧ࡋࡓࠋᅗ୰ࡢ DSC ࡣ double simple cubic ࢆ♧ࡋࠊOHC ࠾ࡼࡧ layer
ࡣ Harding ࡽࡢㄽᩥࡢ⾲グ࡟ᚑࡗ࡚࠸ࡿࠋࡲࡓࠊss ࡢᚋࡢᩘᏐ
ࡣࢫࣆࣥከ㔜ᗘࢆ♧ࡍࠋᅗ୰࡟ࡣ♧ࡋ࡚࠸࡞࠸ࡀ Harding ࡽࡢ㉥እࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿ࡜ࠊlayer ᵓ㐀ࡢࢫࣆࣥከ㔜ᗘࡀ 18ࡢࡶࡢࡀ᭱ࡶࡼࡃ୍⮴ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇ
ࡢᵓ㐀ࡣ᭱ప࢚ࢿࣝࢠ࣮࡛ࡣ࡞ࡃࠊࣆ࣮ࢡࡢᙉᗘẚ࡞࡝ࡶྵࡵ
ࡿ࡜᏶඲࡟୍⮴ࡋ࡚࠸ࡿ࡜ࡣゝ࠼࡞࠸ࡓࡵࠊ௚࡟ࡲࡔ⪃៖ࡋ࡚࠸࡞࠸ᵓ㐀ࡀ࡞࠸࠿࡞࡝࡟ࡘ࠸᳨࡚ウࢆ㐍ࡵ࡚࠸ࡿࠋ
ᅗ㸰Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
x

Rh12+ࡢ㉥እࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥ

‫ۻ‬ᒣཱྀ 㞞ே㸪ᙇ Ᏹ㣕㸪Lushchikova Olga㸪Bakker Joost㸪┿⯪ ᩥ㝯㸪Irn+ࢡࣛࢫࢱ࣮࡟ᑐࡍࡿ NOࡢ྾╔ᵓ㐀࡜ࡑࡢࢧ࢖ࢬ౫Ꮡᛶ㸪➨㸯㸳ᅇศᏊ⛉Ꮫウㄽ఍㸦2021㸧.

x‫ۻ‬Ọ⏣ ฼᫂㸪㝞 㞷ᱵ㸪ᒣཱྀ 㞞ே㸪ᐑᓥ ㅬ㸪┿⯪ ᩥ㝯㸪Ẽ┦᪼⬺㞳ἲ࡟ࡼࡿࣟࢪ࣒࢘ࢡࣛࢫ

ࢱ࣮ୖ࡛ࡢ୍㓟໬❅⣲ศゎ཯ᛂ㐣⛬ࡢ᳨ウ㸪➨㸯㸳ᅇศᏊ⛉Ꮫウㄽ఍㸦2021㸧.

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
x‫ۻ‬Fumitaka Mafuné, Joost M. Bakker, Satoshi Kudoh, Dissociative adsorption of NO introduces flexibility
in gas phase Rh6+ clusters leading to a rich isomeric distribution, Chemical Physics Letters, 780, 138937,
2021.

x

‫ۻ‬Masato Yamaguchi, Yufei Zhang, Olga V. Lushchikova, Joost M. Bakker, Fumitaka Mafuné, Structuresof Nitrogen Oxides Attached to Anionic Gold Clusters Au4− Revealed by Infrared Multiple Photon
Dissociation Spectroscopy, J. Phys. Chem. A, 125, 9040−9047, 2021.

x‫ۻ‬Toshiaki Nagata, Kimihiro Kawada, Xuemei Chen, Masato Yamaguchi, Ken Miyajima and Fumitaka
Mafuné, Decomposition of nitric oxide by rhodium cluster cations at high temperatures, Phys. Chem.
Chem. Phys., 23, 26721, 2021.

x‫ۻ‬Yufei Zhang, Masato Yamaguchi, Kimihiro Kawada, Satoshi Kudoh, Olga V. Lushchikova, Joost M.
Bakker, and Fumitaka Mafuné, Adsorption Forms of NO on Iridium-Doped Rhodium Clusters in the Gas
Phase Revealed by Infrared Multiple Photon Dissociation Spectroscopy, J. Phys. Chem. A, 126, 36−43,
2022.

x

‫ۻ‬Joost M. Bakker, Fumitaka Mafune, Zooming in on the initial steps of catalytic NO reduction using
metal clusters, Phys. Chem. Chem. Phys., 24, 7595, 2022.

ཧ⪃ᩥ⊩[1] D. J. Harding et al., J. Chem. Phys., 133, 214304, 2010.

- 211 -

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫィ⟬
4XDQWXP&KHPLFDO&DOFXODWLRQIRU*URXQGDQG([FLWHG(OHFWURQLF
6WDWHVDQG0ROHFXODU3URSHUWLHVRI0ROHFXOHV&RQWDLQLQJ+HDY\(OHPHQWVżἼ⏣ 㞞ᙪࠊ୰㇂ ┤㍤ࠊ㜿㒊✨㔛ࠊከ⏣ ᐓࠊ∵ᑿ ஧㑻ࠊబ⸨ ᭷ử␃ࠊྜྷ⏣ ⋹ࠊ஭ୖ ᝆ㈗ࠊᮌୗ ⓡྐࠊᐩ⏣ ኱ᶞࠊ+H1DQࠊ㔝ᐑ ᾏ㡢ࠊᒾᐊ ᑑ⨾ᯝࠊᮌᮧ ⿱ኴࠊ኱㇂ ⿱ኴ㑻㸦ᮾி㒔❧኱Ꮫࠊᗈᓥ኱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 ᡂศ┦ᑐㄽἲࢆ⏝࠸ࡓ࢘ࣛࣥ㘒యࡢྠ఩యศูィ⟬࢔ࢡࢳࣀ࢖ࢻ໬ྜ≀࡟ᑐࡍࡿ  ᡂศ┦ᑐㄽἲ࡟ᇶ࡙ࡃᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࡢࣉࣟࢢ࣒ࣛ㛤Ⓨ
5X Ⰽ⣲ࡢỈศゎගゐ፹཯ᛂ࡟࠾ࡅࡿ␯Ỉᇶ࡜⁐፹࿴ຠᯝࡢ᳨ウ㸬ࢳࢱࣥ㘒యࠊࣂࢼࢪ࣒࢘㘒యࠊ࠾ࡼࡧࢽ࢜ࣈ㘒య࡟ࡼࡿ㔜ྜ཯ᛂࡢゎᯒ㸬㑄⛣㔠ᒓࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀᭱㐺໬ࠊ㧗⢭ᗘィ⟬ࠊࣂࣥࢻィ⟬࡜ࡢẚ㍑ࠊ࠾ࡼࡧࢫ࣌ࢡࢺࣝゎᯒ㸬ᫍ㛫ị⾲㠃࡟࠾ࡅࡿ໬Ꮫ㐍໬࡟㛵ࡍࡿ➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲࢸ࣮࣐㸯㹼㸱࡟ࡘ࠸࡚ࡣ +21'2ࠊ*$0(66ࠊ1:&KHP ࢆ࣮࣋ࢫ࡟ᨵⰋࡋࡓᮏ◊✲ᐊࡢࣉࣟࢢ࣒ࣛࠊࢸ࣮
࣐㸲ࠊ 㸳࡟ࡘ࠸࡚ࡣ ',5$&ࠊ *DXVVLDQࠊཬࡧࠊ⮬సࡢࣉࣟࢢ࣒ࣛࠊࡑࡢ௚ࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡣ *DXVVLDQࠊ*DXVVLDQࠊ$')ࠊ02/&$6 ࢆ㐺ᐅ࡟฼⏝ࡋ࡚◊✲ࢆ⾜ࡗࡓࠋ㸱 ◊✲ᡂᯝ

ୖグ◊✲࡟ᑐࡋࠊ୺࡟  ᖺᗘ࡟◊✲㐍ᤖࡀ࠶ࡗࡓࢸ࣮࣐ ࠊࠊࠊ ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋࢸ࣮࣐  ࡛ࡣࠊ✀ࠎࡢ㔜㔠ᒓ㘒యࡢ㔠ᒓ᰾ 105 ໬Ꮫࢩࣇࢺࡢゎᯒࢆᐇ᪋ࡋࡓࠋィ⟬᪉ἲࡣ 5(&3 ἲ ‫ࠊ ڸ‬඲㟁Ꮚ㠀┦ᑐㄽἲ ‫ࠊ ڦ‬6=25$ ἲ ‫ࠊ ە‬㸲ᡂ
ศ 'LUDF ἲ ‫ࠊ࠸౑ࢆ ی‬඲࡚࡟ %/<3࡟ࡼࡿ ')7 ἲࢆ㐺⏝ࡋࡓࠋᅗ㸯࡟ࡣ 3W
㘒య࡜ +J ໬ྜ≀ࡢ 3Wཬࡧ +J105 ໬Ꮫࢩࣇࢺࡢィ⟬್࡜ᐇ㦂್ࡢẚ㍑ࢆ♧ࡋ࡚࠸ࡿࠋ5(&3 ἲཬࡧ㠀┦ᑐㄽἲࡢ

ᅗ㸯㸬3Wཬࡧ +J105 ໬Ꮫࢩࣇࢺࡢィ⟬್࡜ᐇ㦂್ࡢẚ㍑

- 212 -

ィ⟬⤖ᯝࡣ◚⥢ࡋ࡚࠸ࡿࠋ6=25$ ࡜  ᡂศ┦ᑐㄽἲࡢ⤖ᯝࡣᴫࡡⰋዲ࡛࠶ࡿࠋ6=25$ ࡢ⤖ᯝࢆ౑ࡗ࡚ :3W+J ࡢ໬Ꮫࢩࣇࢺ࡜㟁Ꮚ࣏ࣆ࣮ࣗࣞࢩࣙࣥࡸບ㉳࢚ࢿࣝࢠ࣮࡜ࡢ┦㛵࡟ࡘ࠸࡚ゎᯒࢆᐇ᪋ࡋࡓࠋ
ᅗ㸰ࡣ :105 ໬Ꮫࢩࣇࢺ࡜ບ㉳࢚ࢿࣝࢠ࣮ࡢ㏫ᩘࠊཬࡧ㸳㹢㟁Ꮚ࣏ࣆ࣮ࣗࣞࢩࣙࣥ࡜ࡢ㐼㞴࡛࠶ࡿࠋ: ཎᏊࡢ㟁Ꮚ㓄⨨ࡣ G  V  ࡛࠶ࡾࠊ☢Ẽⓗチᐜ࡞ GG㑄⛣ࡀప࢚ࢿࣝࢠ࣮㡿ᇦ࡟Ꮡᅾࡍࡿࡓࡵࠊບ㉳࢚ࢿࣝࢠ࣮ࡢ㏫ᩘ࡜ࡢ
┦㛵ࡀⰋ࠸ࠋ୍᪉࡛㸳㹢㟁Ꮚ࣏ࣆ࣮ࣗࣞ
ࢩࣙࣥ࡜ࡢ┦㛵ࡣᑠࡉ࠸ࠋ132 ゎᯒࡶᐇ᪋ࡍࡿணᐃ࡛࠶ࡿࠋ
ᅗ㸰㸬:105 ໬Ꮫࢩࣇࢺ࡜ບ㉳࢚ࢿࣝࢠཬࡧ㟁Ꮚ࣏ࣆ࣮ࣗࣞࢩࣙࣥ࡜ࡢ┦㛵ࢸ࣮࣐  ࡛ࡣࠊ࢘ࣛࣥྠ఩యศูࡢ໬Ꮫ✀౫Ꮡᛶࢆࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸᳨࡚ドࡋࡓࠋ࢘ࣛࣥࡢ୺せ࡞ྠ఩యࡣ 8 ࡜ 8 ࡛࠶ࡾࠊࡑࡢྠ఩యẚࡢኚືࡣᖺ௦

ᐃࡸྂẼೃࡢゎ᫂࡞࡝࡛ᖜᗈࡃ⏝࠸ࡽࢀࡿࠋࡲࡓࠊ࢘ࣛࣥࡣ &2&+&22&O➼ࡢᵝࠎ࡞࢖࢜ࣥ࡜㘒యࢆᙧᡂࡍࡿࠋࡋ࠿ࡋࠊ࢘ࣛࣥࡢ㓄఩⎔ቃࢆ⪃៖ࡏࡎ࡟Ỵᐃࡉࢀࡓ Å⛬ᗘࡢ್ࡀࠊ ౯ ౯࢘ࣛࣥ㛫ࡢྠ఩యศูಀᩘH ŁG8 ౯ ±G8 ౯
G8Ł 88 VDPSOH 88 VWDQGDUG± ࡢ⌮᝿್࡜ࡋ࡚㆟ㄽ࡟⏝࠸ࡽࢀࡿࡇ࡜ࡀ࠶ࡿࠋ
ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ ✀㢮ࡢ  ౯࢘ࣛࣥ㘒య࡟ᑐࡋ࡚H ࢆ㔞Ꮚ໬Ꮫィ⟬࡛ồࡵࠊH ࡢ໬Ꮫ✀౫Ꮡᛶࢆ᳨ドࡋࡓࠋH ࡣྠ఩య㛫ࡢ᰾య✚ᕪ࡟㉳ᅉࡍࡿ㟁Ꮚ≧ែ㡯 ᰾య✚㡯OQKQY ࡜᰾㉁㔞ᕪ࡟㉳ᅉࡍࡿ᣺ື㡯 ᰾㉁㔞㡯 OQKQP ࡢ࿴࡜ࡋ࡚ィ⟬ࡋࡓࠋOQKQP ࡣ *DXVVLDQ ࡟ࡼࡿ᣺ືゎᯒ࠿ࡽ⟬ฟ࡛ࡁࡿࡀࠊ࢘
ࣛࣥྠ఩యศู࡛ᨭ㓄ⓗ࡞ OQKQY ࡣ┦ᑐㄽຠᯝࡢᙳ㡪ࢆ㢧ⴭ࡟ཷࡅࡿࡓࡵࠊ',5$& ࡟ᐇ⿦ࡉࢀࡓ㧗⢭ᗘ┦ᑐㄽἲ࡛࠶ࡿ ;& ἲࢆ⏝࠸ࠊ+DUWUHH)RFN +) ἲ࠾ࡼࡧᐦᗘỗ㛵ᩘ⌮ㄽ ỗ㛵ᩘ%/<3 ࡟ᇶ࡙ࡃ  ✀㢮ࡢ᪉ἲ࡛ィ⟬ࡋࡓ ௨㝆ࡣࡑࢀࡒࢀ ;&+) ἲ࠾ࡼࡧ ;&%/<3 ἲ࡜⾲グ ࠋ
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     ᅗ㸱 ✀㢮ࡢ࢘ࣛࣥ㘒యࡢH Å ࠾ࡼࡧ᳨ウࡋࡓ㓄఩Ꮚ࠸ࡎࢀࡢᡭἲࢆ⏝࠸ࡓሙྜ࡛ࡶࠊH ࡢ኱ࡁࡉࡣᴫࡡ  ౯ ! ౯ ! ౯࡜࡞ࡾࠊࡲࡓ OQKQY ࡀ OQKQP ࡟ẚ࡭࡚኱ࡁࡃ OQKQY ࡀᨭ㓄ⓗ࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ ᅗ㸱 ࠋH ࡢ㓟໬ᩘ౫Ꮡᛶࡣ    ౯ࡢ㡰࡟ቑຍࡍࡿ f ㌶㐨ෆ㟁Ꮚ࡟ࡼࡿ౯㟁Ꮚ s ss ㌶㐨࡟ᑐࡍࡿ㐽ⶸຠᯝࡢቑ኱ࡀཎᅉ࡛㉳ࡇࡿ 8 ཎᏊ᰾ୖࡢ㟁Ꮚᐦᗘࡢῶᑡ࡟ࡼࡾㄝ࡛᫂ࡁࡿࠋࡲࡓࠊ;&+) ἲ࠾ࡼࡧ ;&%/<3 ἲ࡛ OQKQY ࢆồࡵࡓሙྜ࡛ࠊ ౯ ౯- 213 -

࢘ࣛࣥ㛫ࡢH ࡢ್ᇦࡀࡑࢀࡒࢀ  a Å࠾ࡼࡧ  a Å࡛࠶ࡗࡓࠋࡇࡢࡼ࠺࡟H ࡣᖜᗈ࠸್ࢆ
ྲྀࡿࡓࡵࠊH ࡢ໬Ꮫ✀౫Ꮡᛶࡀᙉ࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࢸ࣮࣐  ࡛ࡣࠊඹྠ◊✲⪅ࡢ㒔❧኱࣭㔝ᮧࢢ࣮ࣝࣉ࡛ྜᡂࡉࢀࡓࢳࢱࣥࠊࣂࢼࢪ࣒࢘ࠊࢽ࢜ࣈ㘒య࡟
ࡼࡗ࡚ゐ፹ࡉࢀࡿ㔜ྜ཯ᛂ࡟ࡘ࠸࡚ࠊ⁐ᾮ୰άᛶ✀ࡢ ;$1(6 ࢫ࣌ࢡࢺࣝ࡜཯ᛂᶵᵓࡢィ⟬ゎᯒࢆ⾜ࡗࡓࠋᮏᖺᗘࡣ୺࡟ࠊࢳࢱࣥゐ፹࡟ࡼࡿࢫࢳࣞࣥ㔜ྜࡢάᛶ✀ྠᐃ࡜❧య㑅ᢥᛶࡢᶵᵓゎ᫂ࠊ࠾ࡼࡧࢽ࢜
ࣈ㘒యࡢ⁐ᾮ୰ ;$1(6 ࢫ࣌ࢡࢺࣝࡢィ⟬ゎᯒࢆ⾜ࡗࡓࠋࢳࢱࣥゐ፹࡟ࡼࡿࢫࢳࣞࣥ㔜ྜ཯ᛂ࡛ࡣࠊゐ፹࡛࠶ࡿ 7L ,9 ࢝ࢳ࢜ࣥ㘒యࡀ⁐ᾮ୰࡛ࢫࢳࣞࣥศᏊ࡟
ࡼࡗ࡚㑏ඖࡉࢀࠊ୰ᛶࡢ 7L ,,, 㘒యࡀ⏕ᡂࡋ࡚࠸ࡿྍ⬟ᛶࡀᐇ㦂ⓗ࡟♧၀ࡉࢀ࡚࠸ࡓࠋࡑࡇ࡛ࠊ7L ,,,㘒య࠾ࡼࡧ 7L ,9 㘒య࡟ࡘ࠸࡚ࠊࢫࢳࣞࣥศᏊࡢᤄධࠊ࠾ࡼࡧఙ㛗཯ᛂࡢィ⟬ゎᯒࢆ⾜ࡗࡓࠋᅗ㸲 ࢳࢱࣥゐ፹࡟ࡼࡿࢫࢳࣞࣥ㔜ྜ཯ᛂࡢ཯ᛂゎᯒ㸸㸦ᕥ㸧QHXWUDO7L ,,, ࠊ㸦ྑ㸧FDWLRQLF7 ,9ᅗ㸲࠿ࡽࠊ୰ᛶࡢ 7L ,,, 㘒య࡛ࡣࠊsi 㠃࡬ࡢࢫࢳࣞࣥᤄධࡢάᛶ㞀ቨࡀ re 㠃࡬ࡢᤄධ࡟ẚ࡭࡚పࡃࠊ❧య㑅ᢥⓗ࡞ࢫࢳࣞࣥᤄධࡀ㉳ࡇࡿࠋ୍᪉࡛ࠊ࢝ࢳ࢜ࣥᛶࡢ 7L ,9 㘒య࡛ࡣࠊsi 㠃ࠊre 㠃࡬ࡢᤄධࡢάᛶ
㞀ቨࡣྠ⛬ᗘ࡛࠶ࡾࠊ㑅ᢥᛶࡣ⌧ࢀ࡞࠸ࠋ௨ୖࡼࡾࠊ⁐ᾮ୰࡛⏕ᡂࡋࡓ୰ᛶࡢ 7L ,,, 㘒యࡀゐ፹ࡢάᛶ✀࡛࠶ࡿ࡜⤖ㄽ௜ࡅࡓࠋ ࡲࡓࠊ1E 9 㘒యࡢ . ➃ ;$1(6 ࢫ࣌ࢡࢺࣝࡢ
ィ⟬ゎᯒ࡛ࡣࠊ᫖ᖺᗘࡲ࡛࡟⾜ࡗ࡚࠸ࡓ 9 9 㘒యࡢィ⟬⤖ᯝ࡜ẚ࡭࡚ᐇ㦂ࢫ࣌ࢡࢺࣝ࡜ࡢ┦㛵ࡀపୗࡍࡿ⤖ᯝ࡜࡞ࡗࡓ㸦ᅗ㸳㸧ࠋ≉࡟ࠊᐇ㦂࡛ࡣ࢔࣮ࣜࣝ࢖࣑ࢻ㓄఩Ꮚࡢ o఩ࡢ⨨᥮ᇶࡢ❧యⓗ࡞࠿ࡉ㧗ࡉ࡟ࡼࡗ࡚ SUHHGJH ࣆ࣮ࢡࡢ఩⨨ࡀᩘ H9 ࢩࣇࢺࡍࡿ࡜࠸࠺⌧㇟ࡀ☜ㄆࡉࢀ࡚࠸ࡿ
ࡀࠊࡇࡢࣆ࣮ࢡࢩࣇࢺࢆィ⟬࡛෌⌧࡛ࡁ࡚࠸࡞
࠸ࡇ࡜ࡀཎᅉࡢ  ࡘ࡛࠶ࡿ࡜⤖ㄽ௜ࡅࡓࠋࡑࡇ
࡛ࠊ࢔࣮ࣜࣝ࢖࣑ࢻ㓄఩Ꮚࡢ o఩ࡢ⨨᥮ᇶ࡜ࡇࢀࡽ࡜┦஫స⏝ࡍࡿࣇ࢙ࣀ࢟ࢩᇶࡢ㓄ྥᛶࢆኚᅗ 㸳  1E 9 㘒 య ࡢ . ➃ ;$1(6 ࢫ ࣌ ࢡ ࢺ ࣝ໬ࡉࡏࡓศᏊࣔࢹࣝࢆసᡂࡋࠊࡑࢀࡒࢀ . ➃㸦SUHHGJH ࣆ࣮ࢡẚ㍑㸧;$1(6 ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࠊẚ㍑ࢆ⾜ࡗࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࠸ࡎࢀࡶᐇ㦂࡛ほࡉࢀࡓࣆ࣮ࢡࢩࣇࢺࢆ෌⌧ࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ3UHHGJH ࣆ࣮ࢡ- 214 -

ࡢࢩࣇࢺࡣ୰ᚰ㔠ᒓࡢ㟁Ꮚ≧ែኚ໬ࢆ཯ᫎࡍࡿࡶࡢ࡛࠶ࡿࡓࡵࠊ௒ᚋࡣ஧㔞໬ࡸ㓟໬≧ែࡢࢫ࣌ࢡࢺࣝ
࡬ࡢᙳ㡪࡟ࡘ࠸࡚ㄪᰝࢆ⥅⥆ࡍࡿணᐃ࡛࠶ࡿࠋ
ࢸ࣮࣐  ࡛ࡣࠊᫍ㛫✵㛫࡟࠾ࡅࡿ໬Ꮫ㐍໬࡟ࡘ࠸࡚ࠊ໭኱࣭㤶ෆࢢ࣮ࣝࣉ࡜ඹྠࡋ࡚࢟ࣛࣝ &2 ⤖ᬗ࡬ࡢ⾲㠃྾╔࡟ࡘ࠸࡚ィ⟬໬Ꮫ࡟ࡼࡿゎᯒࢆ⾜ࡗࡓࠋ࢟ࣛࣝ࡞⤖ᬗ⾲㠃ࡣࠊ࢔࣑ࣀ㓟ࡢ ' య/ యࡢ㉳※ࢆ᥈ࡿ  ࡘࡢᡭࡀ࠿ࡾ࡟࡞ࡿ࡜⪃࠼ࡽࢀࠊᫍ㛫໬Ꮫ࡟࠾ࡅࡿ㔜せ࡞ࢺࣆࢵࢡࢫ࡜࡞ࡗ࡚࠸ࡿࠋ
ᮏᖺᗘࡣࠊᴟపୗ࡛Ⓨぢࡉࢀࡓ &2 ࡢ࢟ࣛࣝศᏊ⤖ᬗ࡟ࡘ࠸࡚ࠊ1 ࡢ࢟ࣛࣝศᏊ⤖ᬗࡢᵓ㐀࡟ᇶ࡙࠸࡚ᅗ㸴࡟♧ࡍᵓ㐀ࣔࢹࣝࢆసᡂࡋࠊྛ྾╔ࢧ࢖ࢺ࡬ࡢཎᏊ྾╔࢚ࢿࣝࢠ࣮ࢆ
&&6' 7 ἲ࡟ࡼࡾồࡵࡓࠋࡑࡢ⤖ᯝࠊ≀⌮྾╔ࡢ྾╔࢚ࢿࣝࢠ࣮ࡀ 1 ཎᏊ㸦6㸧࡛ࡣ⣙ .ࠊ2 ཎᏊ㸦3㸧࡛ࡣ . ࡜ィ⟬ࡉࢀࠊపୗ࡛྾╔ࡀ㉳ࡇࡿ࡜࡜ࡶ࡟ࠊị⾲㠃࡬ࡢ྾╔࢚ࢿࣝࢠ࣮ࡼࡾࡶ ಸ௨ୖᑠࡉ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣࠊ࢟ࣛࣝ࡞ &2 ⤖ᬗ⾲ᅗ㸴 ࢟ࣛࣝ &2 ⤖ᬗ  㠃ࡢィ⟬ࣔࢹࣝ࡜ࠊ❅⣲ཎᏊࡢ≀⌮྾╔ᵝᘧ㠃ୖ࡛ࡣࠊᴟప

ୗ࡟࠾࠸࡚ࡶཎᏊࡢ⾲㠃ᣑᩓࡀ㉳ࡇࡿࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊᫍ㛫✵㛫࡟࠾ࡅࡿ᭷ᶵ໬ྜ≀⏕ᡂࡢ᪂ࡋ࠸
ྍ⬟ᛶ࡜ࡋ࡚⯆࿡῝࠸⤖ᯝ࡜ゝ࠼ࡿࠋ㸲 Ⓨ⾲ᐇ⦼
኱㇂ඃኴ㑻 HWDOࠊ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭኱㇂ඃኴ㑻 HW
DOࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭㔝ᐑᾏ㡢 HWDOࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭஭ୖᝆ㈗ HWDOࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊᖺ  ᭶  ᪥ ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭㔝ᐑᾏ㡢 HWDOࠊࢯࣇࢺࢡࣜࢫࢱࣝඹྠ◊✲᥎㐍఍㆟ࠊ ᖺ ᭶  ᪥ ᪥㸭୰㇂┤㍤ࠊ➨  ᅇ▼Ἔ࣭▼Ἔ໬Ꮫウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥㸭୰㇂┤㍤ࠊ➨  ᅇ㔞Ꮚ໬Ꮫࢫࢡ࣮ࣝ ศᏊ⛉Ꮫ◊✲ᡤ ࠊ ᭶  ᪥ ᭶  ᪥㸭బ⸨᭷ử␃ HWDOࠊ➨  ᅇྠ఩య⛉Ꮫ◊✲఍ࠊ ᖺ  ᭶  ᪥㸦࢜ࣥࣛ࢖ࣥ㸧㸭$6DWRHWDO3DFLILFKHP'HF2QOLQH㸭0$EH
HW DO 3DFLILFKHP  'HF  2QOLQH㸭0 $EH HW DO $&6 )DOO PHHWLQJ  $XJ  
2QOLQH 㸭0$EHHWDO1RUZD\-DSDQV\PSRVLXPRQWKHRUHWLFDODQGH[SHULPHQWDOFKHPLVWU\RIFRPSOH[V\VWHPV
0DU  DQG   2QOLQH㸭0 $EH HW DO +LURVKLPD 8QLYHUVLW\ 1DWLRQDO 7DLZDQ 8QLYHUVLW\ -RLQW

6\PSRVLXPRQ&KHPLVWU\0DU2QOLQH   ฟ∧ᐇ⦼‫ۻ‬6DOPDKDPLQDWLHWDO$&62PHJD  ±    GRLRUJDFVRPHJDF
‫ۻ‬00L\DPRWRHWDOBull. Chem. Soc. Japan      GRLEFVM
‫ۻ‬$<RVKLGDHWDOJ. Chem. Phys$     GRLRUJDFVMSFDF
<6X]XNLHWDOJ. Inorg. Biochem.    GRLRUJMMLQRUJELR  
‫=ۻ‬0DHWDOJ. Comp. Chem     GRLRUJMFF
‫<ۻ‬,VKLPL]XHWDOInorg. Chem.  GRLRUJDFVLQRUJFKHPF
‫ۻ‬$6DWRHWDOGeochim. Cosmochim. Acta  GRLRUJMJFD
- 215 -

ḟୡ௦ IT ♫఍ཬࡧḟୡ௦పⅣ⣲♫఍ࡢᇶ♏࡜࡞ࡿ༙ᑟయ/⤯⦕య⏺㠃ࡢ➨୍ཎ⌮ィ⟬࡟ࡼࡿ◊✲First Principles Studies on Semiconductor/Insulator Interfaces for Next
Generation IT Society and Low-Carbon Society‫ۑ‬ⓑ▼ ㈼஧ࠊ㛗ᕝ ೺ኴ㸦ྡྂᒇ኱Ꮫᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤ㸧ࠊ୐℧ 㢼஬ࠊḈ஭ு௓ࠊ஭ୖ ᑦ㍤ࠊᮌᮧ ཭ဢࠊ㉥▼ ኱ᆅ㸦ྡྂᒇ኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧




◊✲┠ⓗ
㏆ᮍ᮶࡟ᚲせ࡜࡞ࡿ༙ᑟయ㟁⏺ຠᯝᆺࢺࣛࣥࢪࢫࢱ㸦026)(7㸧࡟ᑐࡍࡿタィᣦ㔪ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ㏻ࡋ࡚ࠊḟୡ௦ ,7 ♫఍ࡸḟୡ௦పⅣ⣲♫఍ᐇ⌧ࡢࡓࡵࡢᇶ♏࡜࡞ࡿ༙ᑟయ⤯⦕య⏺
㠃࡟ᑐࡍࡿཎᏊ࣭ࣞ࣋ࣝ㟁Ꮚࣞ࣋ࣝࡢ▱ぢࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚⋓ᚓࡍࡿࡇ࡜ࡀᮏ◊✲ㄢ㢟ࡢ┠ⓗ࡛࠶ࡿࠋ
⌧ᅾࡢ௦⾲ⓗ࡞༙ᑟయࢹࣂ࢖ࢫࡣ 026)(7 ࡛࠶ࡿࠋ026)(7 ࡣ༙ᑟయ⤯⦕యࡢ⏺㠃ࡀ㔜せ࡞ᵓᡂせ⣲࡛ࠊ⤯⦕య┤ୗࡢ༙ᑟయ୰࡟཯㌿ᒙࢆసࡿࡇ࡜࡛ࢺࣛࣥࢪࢫࢱືసࢆࡍࡿࠋࡑࡢࡓࡵ༙ᑟయ㸭⤯⦕య⏺㠃ࡢရ㉁ࡀ 026)(7 ࡢᛶ⬟ࢆᕥྑࡍࡿࠋ
026)(7 ࡢጞࡲࡾࡣࠊ6L  6L2 ⏺㠃ࢆ⏝࠸ࡓ 026)(7 ࡀ  ᖺ࡟࣋ࣝ◊࡛Ⓨ᫂ࡉࢀࡇ࡜ࡀ➃⥴࡛࠶ࡿࡀࠊ᭱㏆ࡢ 6L ⣔ࡢ 026)(7 ࡛ࡣࠊ௚ࡢ㠃᪉఩ࡢ⏺㠃ࡶ⏝࠸ࡿࢼࣀ࣡࢖ࣖᆺࡢ 026)(7 ࢆస〇ࡍࡿᚲせࡀฟ࡚ࡁࡓࠋࡇࡢࡓࡵࠊᚑ᮶ࡢ 6L  6L2 ⏺㠃ࡔ࡛ࡣ࡞ࡃ௚ࡢ㠃᪉఩ࡢ 6L6L2 ⏺㠃࡟ࡘ࠸࡚ࡶ⥥ᐦ࡟ホ౯ࡍࡿᚲせࡀ࡛࡚ࡁࡓࠋᮏ◊✲࡛ࡣ 6L  6L2 ⏺㠃ࡸ 6L  6L2 ⏺㠃➼ 6L  ௨እࡢ㠃᪉఩ࡢ 6L6L2 ⏺㠃࡟ᑐࡋ࡚ཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆ➨୍ཎ⌮ィ⟬࡛᫂ࡽ࠿࡟ࡋࠊ㧗ရ㉁ࡢࢼࣀ࣡࢖ࣖᆺࡢ 6L026)(7 ࡢస〇ࡍࡿࡓࡵࡢᣦ㔪ࢆ᫂ࡽ࠿࡟ࡋࠊḟୡ௦ ,7 ♫఍ࡢ♏ࢆᙧᡂࡍࡿࠋ
ࡲࡓ᭱㏆࡛ࡣࠊ6L/6, ⏝ࡔࡅ࡛ࡣ࡞ࡃࣃ࣮࣡ࢹࣂ࢖ࢫ⏝ࡢ *D1㓟໬≀⏺㠃ࢆ⏝࠸ࡓ 026)(7 ࡀపⅣ⣲♫఍ࡢᐇ⌧ࡢࡓࡵ࡟኱ࡁ࡞ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ*D1026)(7 ⏝ࡢࢤ࣮ࢺ⤯⦕⭷࡜ࡋ࡚ೃ⿵࡟ᣲࡀࡗ࡚࠸ࡿࡢࡀ
6L2 ࡜ $O2 ࡛࠶ࡿࠋᮏ◊✲࡛ࡣ *D16L2 ࡜ *D1$O2 ⏺㠃ࡢཎᏊᵓ㐀࡜㟁Ꮚᵓ㐀ࢆ➨୍ཎ⌮ィ⟬࡛᫂ࡽ࠿࡟ࡍࡿࠋ≉࡟᭱㏆ *D1026)(7 ࡢᐇ⏝໬ࡢ㝿࡟ၥ㢟࡜࡞ࡿ౯㟁Ꮚᖏ௜㏆ࡢ⏺㠃Ḟ㝗࡟ࡘ࠸࡚ࡑࡢ⏺㠃‽఩ࡢཎᏊࣞ࣋ࣝࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡋࠊࡇࡢ౯㟁Ꮚᖏ௜㏆ࡢ⏺㠃‽఩ࢆ㝖ཤࡍࡿࡓࡵࡢฎ᪉⟢ࢆᥦ᱌ࡋࠊḟୡ௦
పⅣ⣲♫఍ࡢᇶ♏ࢆᙧసࡿࠋ
௨ୖࡢࡼ࠺࡞◊✲ࢆ㏻ࡋ࡚ࠊ㏆ᮍ᮶࡟ᚲせ࡜࡞ࡿ༙ᑟయ 026)(7 ࡟ᑐࡍࡿタィᣦ㔪ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ㏻ࡋ࡚ࠊḟୡ௦ ,7 ♫఍ࡸḟୡ௦పⅣ⣲♫఍ᐇ⌧ࡢࡓࡵࡢᇶ♏࡜࡞ࡿ▱ぢࢆィ⟬⛉Ꮫ࡟ࡼࡗ࡚⋓ᚓࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ  *D1D6L2 ⏺㠃*D1D6L2 ⏺㠃ࣔࢹࣝࢆసᡂࡍࡿ‽ഛ࡜ࡋ࡚ࠊࡲࡎᅗ  ࡟♧ࡍึᮇࣔࢹࣝࢆ⏝ពࡋࡓࠋࡇࡢึᮇࣔࢹࣝࡣ
*D1 ⤖ᬗࡢ  ⾲㠃ୖ࡟ࠊȘ6L2 ⤖ᬗࢆ㔜ࡡࡿࡇ࡜࡛సᡂࡋࡓࠋึᮇࣔࢹࣝࡢヲ⣽ࢆ㏙࡭ࡿࠋ*D1 ᒙࡣࠊ- 216 -⾲㠃  ཎᏊࡢ  ᒙ ཌࡉ ύࡢ࢘ࣝࢶ㖔ᆺ *D1 ࣂࣝࢡ *D 1 ࡛࠶ࡾࠊ6L2 ᒙࡣཌࡉ ύ 6L2  ࡢȘ6L2 ⤖ᬗ࡛࠶ࡿࠋࡲࡓࠊ*D1 ࡢ ࡄ
㠃ࢆ௬᝿Ỉ⣲ ౯㟁Ꮚᩘ ࡛ࠊ6L2 ࡢྑ➃ࢆ㏻ᖖࡢỈ⣲ ౯㟁Ꮚᩘ  ࡛ࡑࢀࡒࢀ⤊➃ࡋ࡚࠸ࡿࠋࡇࡢ
⤊➃Ỉ⣲ࡢ఩⨨ࡣᵓ㐀᭱㐺໬࡟ࡼࡾỴᐃࡋࡓࠋࡲ
ࡓࠊ6L2 ࡢྑ➃࡟ࡣ࿘ᮇ᮲௳࡟ࡼࡿᕥྑࡢࢭࣝ࠿ࡽ
ࡢᙳ㡪ࢆ᤼㝖ࡍࡿࡓࡵࡢ┿✵ᒙ ύ ࢆྲྀࡾ௜ࡅ࡚
࠸ࡿࠋ࡞࠾ィ⟬ࡣ 9$63 ࢯࣇࢺ࢙࢘࢔ࢆ⏝࠸࡚⾜ࡗᅗ㸯㸸*D16L2⏺㠃ィ⟬ࣔࢹࣝ ึᮇᵓ㐀ࡓࠋ
GaN⾲㠃ୖ࡛a-SiO2ࢆᙧᡂࡉࡏࡿࡓࡵ࡟ࠊ๓⠇ࡢึᮇࣔࢹࣝ(ᅗc-1.1) ࡟ᑐࡋ࡚➨୍ཎ⌮MDィ⟬ࢆ⾜࠸ࠊ
Melt-Quenchἲ࡛SiO2ᒙࢆ⼥ゎ࣭෭༷ࡍࡿ㐣⛬ࢆ෌⌧ࡋࡓࠋ⼥ゎ㐣⛬࡜ࡋ࡚ࠊ5000K୍ᐃ࡛5psࡢຍ⇕ࢆ⾜࠸ࠊࡑࡢᚋ࡟෭༷㐣⛬࡜ࡋ࡚200K/psࡢ㏿ᗘ࡛0Kࡲ࡛෭༷ࡍࡿィ⟬ࢆ⾜ࡗࡓࠋ࡞࠾ࠊMD ィ⟬ࡢ඲࡚ࡢ㐣⛬࡟࠾࠸࡚GaN ᒙ࡜SiO2ᒙୖ➃㸦⤊➃Ỉ⣲࠿ࡽ➨2㏆᥋ཎᏊࡲ࡛㸧ࡣᅛᐃࡋࠊSiO2ᒙࡢ୰ኸ㒊ศ(ཌࡉ20ύ)ࡢࡳࡀືࡃࡼ࠺࡟タᐃࡋࡓࠋࡲࡓࠊMD ィ⟬⤊஢ᚋ࡟ࡣMD ィ⟬࡛ື࠿ࡋࡓSiO2ᒙ࡟ຍ࠼࡚ࠊ⏺㠃ࡢGaN
ᒙࢆྵࡵ࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ  6L6L2 ⏺㠃Si/SiO2 ⏺㠃ࡢ⇕㓟໬㐣⛬ࢆ⪃࠼ࡿ࡟ᙜࡓࡾSi(100)/SiO2ࠊSi(310)/SiO2 ⏺㠃ࡢslab model ࢆ⏝࠸ࡓࠋ
Si(100)/SiO2ࠊSi(310)/SiO2 ⏺㠃ࡢึᮇࣔࢹࣝࢆࡑࢀࡒࢀᅗ3(a)ࠊᅗ3(b) ࡟♧ࡍࠋSiO2 ࡟ࡣș-quartz ࢆ᥇⏝ࡋ࡚࠸ࡿࠋ┿✵ᒙࡣSi(100)/SiO2 ࣔࢹࣝࡣ20ύࠊSi(310)/SiO2 ࣔࢹࣝࡣ17ύ࡜ࡋࠊSi ഃࡢ⾲㠃࡜SiO2
ഃࡢ⾲㠃ࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡣHཎᏊ࡛⤊➃ࡋࡓࠋࡲࡓSi ⾲㠃ഃࡢH ཎᏊࡢࡳᅛᐃࡋ࡚࠸ࡿࠋࣘࢽࢵࢺ
ࢭࣝࡢཎᏊᩘࡣSi(100)/SiO2 ⏺㠃ࡢึᮇࣔࢹ࡛ࣝࡣSiཎᏊࡀ48ಶࠊOཎᏊࡀ24ಶࠊHཎᏊࡀ16ಶ࡜࡞ࡗ࡚࠾
ࡾࠊSi(310)/SiO2 ⏺㠃ࡢึᮇࣔࢹ࡛ࣝࡣSi ཎᏊࡀ38 ಶࠊOཎᏊࡀ33ಶࠊHཎᏊࡀ10ಶ࡜࡞ࡗ࡚࠸ࡿࠋࡲࡓ
⏺㠃ࣔࢹࣝࡢ௚ࠊSi ᇶᯈ୰ࡢ㓟⣲ཎᏊࡢᣑᩓࢆㄪ࡭ࡿࡓࡵ࡟Si ࣂࣝࢡࣔࢹࣝࢆ⏝࠸ࡓࠋSiࣂࣝࢡࣔࢹࣝࢆ
ᅗ3(c) ࡟♧ࡍࠋࣘࢽࢵࢺࢭࣝࡢཎᏊᩘࡣSiࣂࣝࢡࣔࢹ࡛ࣝࡣSiཎᏊ128ಶࠊOཎᏊ1ಶ࡜࡞ࡗ࡚࠸ࡿࠋᮏィ⟬ࡶVASPࢆ⏝࠸࡚⾜ࡗࡓࠋD E  Fᅗ 㸸 D Si(100)/SiO2 ⏺㠃ࡢึᮇࣔࢹࣝࠋ(b) Si(100)/SiO2 ⏺㠃ࡢึᮇࣔࢹࣝࠋ(c) Si ࣂࣝࢡࣔࢹࣝࠋ

- 217 -

◊✲ᡂᯝ

3.1 GaN/a-SiO2 ⏺㠃ィ⟬ࡢ⤖ᯝᚓࡽࢀࡓ GaN/a-SiO2 ࡢ⏺㠃ᵓ㐀ࢆᅗ 4 ࡟♧ࡍࠋ⏺㠃ࡣࠊGaN ⾲㠃ࡢ Ga ཎᏊࡀ඲࡚ O ཎᏊ࡜⤖ྜࡋࡓᵓ㐀ࢆᙧᡂࡋ࡚࠾ࡾࠊࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡣⓎ⏕ࡋ࡞࠿ࡗࡓࠋ⏺㠃ࡢ Ga-O ⤖ྜ࡟ࡣ 3 ࡘࡢࢱ࢖ࣉࡀ࠶ࡾࠊࡑࢀࡒࢀ
⤖ྜཎᏊࡢᩘ࡜✀㢮࡟㐪࠸ࡀ࠶ࡿࠋ㸯ࡘ┠ࡣࠊO ཎᏊࡀ Siࠊ
Ga ࡜⤖ྜࡋࡓ 2 㓄఩ᵓ㐀(ᅗ 4(a))ࠋ2 ࡘ┠ࡣࠊO ཎᏊࡀ Siࠊ
SiࠊGa ࡜⤖ྜࡋࡓ 3 㓄఩ᵓ㐀(ᅗ 4(b))ࠋ3 ࡘ┠ࡣࠊO ཎᏊᅗ  MD ィ⟬࡛ᙧᡂࡉࢀࡓ GaN/a-SiO2 ࡢ⏺㠃ᵓ㐀ࡀ SiࠊGaࠊGa ࡜⤖ྜࡋࡓ 3 㓄఩ᵓ㐀(ᅗ 4(c))࡛࠶ࡿࠋ
GaN/a-SiO2 ⏺㠃ࣔࢹࣝࡢ㟁Ꮚ≧ែࢆࣂࣥࢻࢠࣕࢵࣉࡀ
෌⌧ࡉࢀࡿࡇ࡜࡛▱ࡽࢀ࡚࠸ࡿHSEἲ࡛ゎᯒࡋࡓࠋᅗ5
SiO2

࡟GaN࡜SiO2࡟ศゎࡋࡓ≧ែᐦᗘᅗࢆ♧ࡍࠋࡇࡢᅗ࠿
ࡽࠊGaN ࡢࣂࣥࢻࢠࣕࢵࣉෆ࡟ࡣḞ㝗‽఩ࡣᏑᅾࡋ࡞
࠸ࠋࡇࡢࡇ࡜ࡣᛴᓧ࡞GaN/a-SiO2⏺㠃ࢆᙧᡂ࡛ࡁࢀࡤࠊ
࣮࣍ࣝࢺࣛࢵࣉࡢ࡞࠸⌮᝿ⓗ࡞⏺㠃ࡀᚓࡽࢀࡿࡇ࡜ࢆ♧ࡋ

VBM

GaN

࡚࠸ࡿࠋ
ᅗ  ᛴᓧ࡞ GaN/a-SiO2 ⏺㠃ࡢ≧ែᐦᗘࠋ
6L6L2 ⏺㠃
6L  6L2ࠊ6L  6L2 ⏺㠃ࡑࢀࡒࢀ࡟ࡘ࠸࡚⏺㠃௜㏆ࡢ 6L6L ⤖ྜ㛫ࡢ᭱ࡶ࢚ࢿࣝࢠ࣮ⓗ࡟ᚓࢆࡍࡿ
఩⨨࡟ 2 ཎᏊࢆᑟධࡋ࡚࠸ࡃࡇ࡜࡛ࠊ⏺㠃࡛ࡢ㓟໬ࢆ෌⌧ࡋࡓࠋ⏺㠃௜㏆ࡢ 6L ཎᏊࡢ⮬Ⓨⓗ࡞ᨺฟࡀ㉳ࡇࡿࡼ࠺࡟࡞ࡿࡲ࡛ 2 ཎᏊࡢᑟධࢆ⾜࠸ࠊḟ࡟ 6L  6L2 ⏺㠃 6L  6L2 ⏺㠃ࡑࢀࡒࢀ࡟ࡘ࠸࡚ 6L ཎᏊᨺฟ๓ࡢ⣔࠿ࡽ⏺㠃௜㏆ࡢ 6L ཎᏊࢆ  ࡘྲྀࡾ㝖ࡁࠊ6L ཎᏊᨺฟᚋࡢ⣔ࢆ⏝ពࡋࡓࠋ࡝ࡕࡽࡢ⏺㠃࡟࠾࠸࡚ࡶ
6L ཎᏊᨺฟᚋࡢ⣔࡛ࡣඛ⾜◊✲࡟࠶ࡿ㏻ࡾࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡀᙧᡂࡉࢀࡓࠋࡇࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࢆ㓟⣲ཎᏊ࡟ࡼࡾ⤊➃ࡋࡓࠋࡑࢀࡒࢀࡢ⏺㠃࡟ࡘ࠸࡚ 6L ཎᏊᨺฟ๓ࡢ⣔࠿ࡽࢲࣥࢢࣜࣥࢢ࣎ࣥࢻ⤊➃ᚋࡢ⣔࡬⛣ࡗࡓ㝿ࡢ࢚ࢿࣝࢠ࣮ኚ໬ࢆィ⟬ࡋࡓࠋࡇࡢ࢚ࢿࣝࢠ࣮ኚ໬ࡣ 6L  6L2 ⏺㠃࡛ࡣH9ࠊ6L  6L2 ⏺
㠃࡛ࡣH9 ࡜࠸࠺㠀ᖖ࡟኱ࡁ࡞࢚ࢿࣝࢠ࣮ኚ໬ࡢ್ࡀᚓࡽࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ6L ཎᏊᨺฟᚋࡢ⣔࡛ࡣ⏺㠃࡟ࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡀᙧᡂࡉࢀ୙Ᏻᐃ࡞ᵓ㐀࡜࡞ࡿࡓࡵ 6L ཎᏊࡢᨺฟࡣ㉳ࡇࡾ࡟ࡃ࠸ࡀࠊ6L ཎᏊᨺฟᚋࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡀ㓟⣲ཎᏊ࡟⤊➃ࡉࢀࡿሙྜ࡟ࡣ 6L ᨺฟᚋࡢᵓ㐀ࡣࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡣ࡞
ࡃ࡞ࡾᏳᐃ࡞ᵓ㐀࡜࡞ࡿࡓࡵ 6L ཎᏊࡢᨺฟࡣ㉳ࡇࡾࡸࡍࡃ࡞ࡾ฼ᚓࡀ኱ࡁࡃ࡞ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

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⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟Conformational change of biological supramolecules andits relation to functions‫ۑ‬໭ᑿ ᙲᮁࠊ➉ᮧ ࿴ᾈࠊTRAN Phuoc DuyࠊSOBEH Mohamed Marzoukࠊᐑ⃝ ెᕼࠊᮌෆ 㱟அ௓ࠊTegar Nurwahyu Wijayaࠊᑿᕝ ᣅᕭࠊᖹ ᝆኴࠊ୕ᰨ ᾴ㞞ࠊ
Flamandita Darinࠊྜྷᒸ ⨾᭶ࠊ୰▮ ගࠊ኱ἑ 㝣㍤㸦ᮾᕤ኱⏕࿨⌮ᕤ㸧

1◊✲┠ⓗࠊෆᐜ
ࢼࣀ࣓࣮ࢺࣝࢧ࢖ࢬࡢศᏊᶵᲔ࡛࠶ࡿ⺮ⓑ㉁ࡸࡑࢀࡽࡢ㞟ྜయ࡛࠶ࡿ⏕య㉸ศᏊࡣࠊ⏕యෆ࡛❧యᵓ㐀ኚ໬ࢆᕦࡳ࡟฼⏝ࡋ࡚ᶵ⬟ࡍࡿࠋᮏ⏦ㄳㄢ㢟࡛ࡣࠊ⺮ⓑ㉁ࡸ⺮ⓑ㉁」ྜయ⣔ࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟࡜ࡢ㛵ಀࢆศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎᯒࡋࠊ⏕࿨⌧㇟ࡢ⣲㐣⛬ࢆྖࡿ⏕య㉸ศᏊࡢศᏊ⛉Ꮫⓗ࡞ືసཎ⌮ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ2021 ᖺᗘࡣୗグࡢ 3 ࡘࡢࢸ࣮࣐ࢆ୰ᚰ࡟ィ⟬ࢆ⾜ࡗࡓࠋࠕ࢔ࢡࢺ࣑࢜ࢩࣥࡢ⤖ྜゎ㞳㐣⛬࡛ࠖᑐ㇟࡜ࡍࡿ࢔ࢡࢺ࣑࢜ࢩࣥࡣࠊ㦵᱁➽ࡢ཰⦰ࢆᢸ࠺⺮ⓑ㉁̿⺮ⓑ㉁」ྜయ࡛࠶ࡿࠋ㦵᱁➽ࡢ཰⦰ࡣࠊ࣑࢜ࢩࣥ㢌㒊࡜࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢ⤖ྜ࣭ゎ㞳ࡢ⧞ࡾ㏉ࡋ࡟ࡼࡗ࡚㉳ࡇࡗ࡚࠸ࡿࠋ࣑࢜ࢩࣥ ATP ࢧ࢖ࢡࣝ࡜࿧ࡤࢀࡿࡇࡢ⌧㇟࡟ᑐࡍࡿ⌮ゎࡣࠊ࢔ࢡࢺ࣑࢜ࢩࣥࡢ㛵ࢃࡿ⏕࿨⌧㇟ࡢゎ᫂ࡸࠊ⣽⬊㐠ືࡸ⣽⬊ෆ㍺㏦ࢆᢸ࠺࣑࢜ࢩ࣭ࣥࣇ࢓࣑࣮ࣜ࡟ᒓࡍࡿ⺮ⓑ㉁ࡢ✺↛ኚ␗࡛㉳ࡇࡿ㑇ఏᛶ⑌ᝈࡢ⑓ᅉ✲᫂࡟࠾࠸࡚㔜せ࡛࠶ࡿࠋ࢔ࢡࢳࣥ 2 ศᏊ࡜ᙅ⤖ྜ≧ែࡢ࣑࢜ࢩࣥ㢌㒊ࢆᑐ㇟࡜ࡋࡓࠊPaCS-MD ἲ࡟ࡼࡿゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࠊ࢔ࢡࢺ࣑࢜ࢩࣥ࡟࠾ࡅࡿཎᏊࣞ࣋ࣝࡢゎ㞳࣓࢝ࢽࢬ࣒ࢆ᳨ウࡋࡓࠋࠕࣄࢫࢺࣥ-DNA ࡢ⤖ྜゎ㞳㐣⛬࡛ࠖࡣࠊ┿᰾⏕≀ࡢࢤࣀ࣒ DNA ࡢᵓ㐀ࡢᇶᮏ༢఩࡛࠶ࡿࢾࢡࣞ࢜ࢯ࣮࣒
ࢆᑐ㇟࡜ࡋࡓィ⟬ࢆ⾜࠺ࠋࢾࢡࣞ࢜ࢯ࣮࣒ࡣࠊ⣙ 147 ሷᇶᑐࡢ DNA ࡜ࢥ࢔ࣄࢫࢺࣥ࡜࿧ࡤࢀࡿ H2A, H2B,
H3, H4 ࡀ 2 ࡘࡎࡘィ 8 ࡘࡢࣄࢫࢺࣥࢱࣥࣃࢡ㉁࡟ࡼࡗ࡚ᵓᡂࡉࢀ࡚࠸ࡿࠋࢾࢡࣞ࢜ࢯ࣮࣒୰ࡢࣄࢫࢺࣥ⩻ヂᚋಟ㣭ࡸࠊ୺せᆺࣄࢫࢺࣥࡀࣄࢫࢺࣥࣂࣜ࢔ࣥࢺ࡟⨨ࡁ᥮ࢃࡿࡇ࡜࡟ࡼࡾࠊࢤࣀ࣒ DNA ࡢ㧗ḟᵓ㐀࡛࠶ࡿࢡ࣐ࣟࢳࣥ୰࡛ࡣከᵝ࡞ࢾࢡࣞ࢜ࢯ࣮࣒ࡀᙧᡂࡉࢀ࡚࠸ࡿࠋPaCS-MD/MSM ἲࢆࢾࢡࣞ࢜ࢯ࣮࣒࡟㐺⏝ࡋࠊ
H2A/H2B ஧㔞యࡀḞࡅࡓᵓ㐀࡛࠶ࡿ࣊࢟ࢧࢯ࣮࣒࡜ H2A/H2B ஧㔞య㛫ࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮࠾ࡼࡧ㏿ᗘᐃᩘホ౯ࢆヨࡳࡓࠋ
ࠕp53-C ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ⤖ྜ㐣⛬࡛ࠖᑐ㇟࡜ࡍࡿࢱࣥࣃࢡ㉁ p53 ࡣࠊ࢞ࣥᢚไࠊ௦ㅰࠊ࢔࣏ࢺ࣮ࢩࢫ
࡞࡝ࡢከࡃࡢ⏕యᶵ⬟࡟࠾࠸࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋp53 ࡣࠊ4 ࡘࡢࢻ࣓࢖ࣥᵓ㐀ࢆᣢࡕࠊࡑࢀࡒࢀ␗
࡞ࡿᙺ๭ࡀ࠶ࡿࠋDNA ⤖ྜࢻ࣓࢖ࣥ࡜ࡋ࡚ࡣࠊࢥ࢔ࢻ࣓࢖ࣥ࡜ C ᮎ➃ࢻ࣓࢖ࣥࡀ࠶ࡿࠋࢥ࢔ࢻ࣓࢖ࣥࡣ≉␗ⓗ࡞ሷᇶ㓄ิ࡟⤖ྜࡍࡿࡢ࡟ᑐࡋࠊC ᮎ➃ࢻ࣓࢖ࣥࡣ㓄ิ࡟ᑐࡋࠊ㠀≉␗ⓗ࡟⤖ྜࡍࡿࠋp53 ࡢ C ᮎ➃ࢻ࣓࢖ࣥࡣኳ↛ኚᛶ㡿ᇦ࡛࠶ࡿࡓࡵࠊཎᏊ࡛ࣞ࣋ࣝࡢ DNA ࡬ࡢ⤖ྜᶵᵓࢆᵓ㐀⏕≀Ꮫⓗ࡟♧ࡍࡇ࡜ࡣᅔ㞴࡛࠶ࡿࠋࡇࡢᵓ㐀ⓗᰂ㌾ᛶࡀࠊp53 ࡢከᵝ࡞ᶵ⬟࡜㛵ࢃࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࠊC ᮎ➃ ࢻ࣓࢖ࣥࡢ DNA ࡬ࡢ⤖ྜᶵᵓࡢゎ᫂ࡣ㔜せ࡛࠶ࡿࠋኳ↛ኚᛶ㡿ᇦ࡛࠶ࡿ C ᮎ➃ ࢻ࣓࢖ࣥࡢከᵝ࡞ᵓ㐀ᚓࡿࡓࡵ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ
࡟ࡼࡾከᵝ࡞ᵓ㐀ࡢࢧࣥࣉࣜࣥࢢ࡟⾜࠸ࠊࢧࣥࣉࣜࣥࢢࡼࡾᚓࡽࢀࡓከᵝ࡞ᵓ㐀ࢆ DNA ࿘㎶࡟㓄ࡋࡓ MDࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡍࡿࡇ࡜࡟ࡼࡾࠊC ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ⤖ྜ࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡸ DNA
ୖ࡛ࡢືࡁࡢ᥎ᐃࢆ⾜ࡗࡓࠋᮏᖺᗘࡣࠊ኱ࡁ࡞ᡂᯝࡀᚓࡽࢀࡓࠕp53-C ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ⤖ྜ㐣⛬ࠖ࡟㛵ࡍࡿ⤖ᯝࢆ୰ᚰ࡟ሗ࿌ࡍࡿࠋ

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2◊✲᪉ἲࠊィ⟬᪉ἲC ᮎ➃ࢻ࣓࢖ࣥࡢᵓ㐀ࢧࣥࣉࣜࣥࢢ࡟⏝࠸ࡓ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫࡣࠊ᪤࡟ࢧࣥࣉࣝࡋࡓᵓ㐀࡟ᑐࡋࣂ࢖࢔ࢫ

࣏ࢸࣥࢩࣕࣝࢆຍ࠼ࡿࡇ࡜࡛ࠊຠ⋡ⓗ࡟ࢧࣥࣉࣜࣥࢢࢆ⾜࠺ᡭἲ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㞟ᅋኚᩘ࡟័ᛶ༙ᚄࠊ
ᮎ➃㛫㊥㞳ࠊRMSD ࢆ⏝࠸ࡓࠋࣂ࢖࢔ࢫ࣏ࢸࣥࢩࣕࣝࡢ኱ࡁࡉࡣࠊ3 kJ/mol ࡜ࡋࠊᖜࡣ 0.04 nm ࡜ࡋࠊ500 stepࡈ࡜࡟ࣂ࢖࢔ࢫ࣏ࢸࣥࢩࣕࣝࢆຍ࠼ࡓࠋᚓࡽࢀࡓ C ᮎ➃ࢻ࣓࢖ࣥࡢከᵝ࡞ᵓ㐀࠿ࡽ 100 ಶࡢ௦⾲ᵓ㐀ࢆ㑅ࡧࠊ
DNA ࿘㎶࡟ࣛࣥࢲ࣒࡟㓄⨨ࠊ୪ิࡋ࡚ 100 ಶࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ 1 ȝs ࡎࡘᐇ⾜ࡋࡓࠋẚ㍑ࡢࡓࡵ࡟ࠊ
C ᮎ➃ࢻ࣓࢖ࣥ༢⊂ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡶᐇ⾜ࡋࡓࠋ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ࡣ PLUMED ࡜࠸࠺ࣛ࢖ࣈࣛࣜࢆ⏝࠸ࡓࠋMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡣࠊGROMACS5.1.4 ࢆ⏝࠸ࠊຊሙࡣ AMBER14SBࠊỈࣔࢹࣝࡣ OPC ࣔࢹࣝࢆ⏝࠸ࡓࠋᚓࡽࢀࡓ 100 ಶࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ࣐ࣝࢥࣇ≧ែࣔࢹࣝ㸦MSM㸧࡟ࡼࡾゎᯒࡋࠊࡼࡾ㛗࠸᫬㛫ࢫࢣ࣮࡛ࣝ
ࡢ C ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ୖ࡛ࡢືࡁࡢ᥎ᐃ࡞࡝ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝࡣࡌࡵ࡟ࠊ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡾ C ᮎ➃ࢻ࣓࢖ࣥࡢᵓ㐀ࢧࣥࣉࣜࣥࢢࢆ⾜ࡗࡓࠋ័ᛶ༙ᚄࠊᮎ➃㛫㊥㞳ࠊึᮇᵓ㐀ࢆཧ↷ᵓ㐀࡜ࡋࡓ RMSD ࢆ㞟ᅋᗙᶆ࡜ࡋࡓࠋ
࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࠿ࡽ᥎ᐃࡉࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࠊ
᭱Ᏻᐃᵓ㐀ࠊᴟᑠᏳᐃᵓ㐀ࢆᅗ㸯࡟♧ࡍࠋ᭱Ᏻᐃᵓ㐀࡛࠶ࡗ࡚ࡶࠊ஧ḟᵓ㐀ࢆᙧᡂࡏࡎࠊᰂ㌾࡞ᵓ㐀࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ୍᪉ࠊᴟᑠᏳᐃᵓ㐀࡛ࡣ஧ḟᵓ㐀ࡢᙧᡂࡀ☜ㄆࡉࢀࡓࠋࡇࡢࡼ࠺࡟ࠊC ᮎ➃ࢻ࣓࢖ࣥࡢከᵝ࡞ᵓ㐀ࡢࢧࣥࣉࣜࣥࢢ࡟ᡂຌࡋࡓࠋ

ᅗ 1 ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡾࢧࣥࣉࣜࣥࢢࡉࢀࡓᵓ㐀ࠊ᥎ᐃࡉࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ

ḟ࡟ࠊC ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ⤖ྜ࣓࢝ࢽࢬ࣒ࢆㄪ࡭ࡓࠋྛ࢔࣑ࣀ㓟ṧᇶࡢ⤖ྜ☜⋡ࢆẚ㍑ࡍࡿ࡜ࠊሷᇶᛶ
࢔࣑ࣀ㓟ࡢ⤖ྜ☜⋡ࡀ㧗࠸㸦ᅗ 2㸧ࠋࡇࡢࡇ࡜࠿ࡽࠊC ᮎ➃ࢻ࣓࢖ࣥࡣ㈇࡟ᖏ㟁ࡋ࡚࠸ࡿ DNA ࡢࣜࣥ㓟㒊ศ࡟㟁Ẽⓗ࡞┦஫స⏝ࢆ㏻ࡋ࡚ࠊ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

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ᅗ 2 ࢔࣑ࣀ㓟ṧᇶࡢ DNA ⤖ྜ☜⋡㸦ᕥ㸧࡜⤖ྜᵓ㐀ࡢ౛㸦ྑ㸧C ᮎ➃ࢻ࣓࢖ࣥࡢ DNA ⤖ྜ࡟క࠺ᵓ㐀ኚ໬࡟ࡘ࠸࡚ㄪ࡭ࠊ័ᛶ༙ᚄࠊRadius ratio ࢆࡶ࡜࡟⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆィ⟬ࡋࡓ㸦ᅗ 3㸧
ࠋRadius ratio ࡜ࡣࠊ㛗ᚄ࡜▷ᚄࡢẚ࡛࠶ࡾࠊ1 ࡟㏆࡙ࡃ࡜⌫ᙧࠊ್ࡀ኱ࡁࡃ࡞ࡿ࡜ࠊ
┤⥺ⓗ࡞ᵓ㐀࡟࡞ࡿࠋ⤖ྜ᫬࡜㠀⤖ྜ᫬࡛኱ࡁࡃ 2 ࡘࡢ┦㐪ࢆほࡋࡓࠋ1 ࡘࡣ DNA ⤖ྜ᫬࡟࡯࡝ࡅࡓᵓ㐀ࡀẚ㍑ⓗ࡟Ᏻᐃࡋ࡚࠸ࡿኚ໬࡛࠶ࡿ㸦ᅗ 3 㟷࠸ᅄゅෆࡢ㡿ᇦ㸧ࠋࡇࢀࡣ C ᮎ➃ࢻ࣓࢖ࣥࡀ DNA ࡢᗈ࠸⠊ᅖ࡟⤖ྜࡍࡿࡇ࡜࡛ࠊ࡯࡝ࡅࡓᵓ㐀ࡀẚ㍑ⓗ࡟Ᏻᐃ໬ࡋ࡚࠸ࡿࡓࡵࡔ࡜⪃࠼ࡽࢀࡿࠋ2 ࡘ┠ࡣ័ᛶ༙ᚄࡀ 1.25~1.5
nm ࡢᵓ㐀ࡀ DNA ⤖ྜ࡟క࠸୙Ᏻᐃ࡟࡞ࡗ࡚࠸ࡿኚ໬࡛࠶ࡿ㸦ᅗ 3 ㉥࠸ᅄゅෆࡢ㡿ᇦ㸧ࠋࡇࢀࡣࠊDNA ࡢ๪⁁࠿ࡽࡣࡳฟࡿࡼ࠺࡞ᵓ㐀ࡀࠊ⁁࡟ἢ࠺ࡼ࠺࡟ᵓ㐀ኚ໬ࡍࡿࡓࡵࡔ࡜⪃࠼ࡽࢀࡿࠋࡘࡲࡾࠊ୰㏵༙➃࡟኱ࡁࡃ⁁࠿ࡽࡣࡳฟࡿࡼ࠺࡞ᵓ㐀ࡀ୙Ᏻᐃ࡟࡞ࡗ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ C ᮎ➃ࢻ࣓࢖ࣥࡣᰂ㌾࡟ᵓ㐀ࢆኚ໬ࡉࡏࠊ
DNA ࡟Ᏻᐃ࡟⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

ᅗ 3 DNA 㠀⤖ྜ᫬㸦ᕥ㸧࡜⤖ྜ᫬㸦ྑ㸧ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ

C ᮎ➃ࢻ࣓࢖ࣥࡀࠊ࡝ࡢࡼ࠺࡟ DNA ୖࢆ⛣ືࡋ࡚࠸ࡿࡢ࠿ㄪ࡭ࡿࡓࡵࠊィ 100 ȝs ࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ⤫ྜࡋࠊMSM ࢆ⏝࠸࡚ゎᯒࡋࡓࠋᅗ 4 ࡟♧ࡋࡓࡼ࠺࡟኱ࡁࡃศࡅ࡚ 2 ✀㢮ࡢ⤒㊰ࡀ᥎ᐃࡉࢀࡓࠋ1 ࡘࡣ DNA
ࡢ⁁ࢆᶓ᩿ࡋ⛣ືࡍࡿ⤒㊰࡛࠶ࡾࠊ2 ࡘ┠ࡣ⁁ࢆᶓ᩿ࡍࡿືࡁ࡜ࠊ๪⁁࡟ἢࡗ࡚ᅇ㌿ࡍࡿືࡁࢆ⤌ࡳྜࢃࡏ࡚⛣ືࡍࡿ⤒㊰࡛࠶ࡿࠋ2 ✀㢮ࡢືࡁࢆ⤌ࡳྜࢃࡏࠊᰂ㌾࡟ DNA ୖࢆ⛣ືࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

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ᅗ 4㸸MSM ࠿ࡽ᥎ᐃࡉࢀࡓ 2 ✀㢮ࡢ⤒㊰

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃx‫ ۻ‬M.M. Sobeh and A. Kitao. Dissociation Pathways of the p53 DNA Binding Domain from DNA and CriticalRoles of Key Residues Elucidated by dPaCS-MD/MSM. J. Chem. Inf. Model 62, 1294 (2022).

x‫ ۻ‬H. Hata, D. Phuoc Tran, M. Marzouk Sobeh and A. Kitao. Binding free energy of protein/ligand complexes
calculated using dissociation Parallel Cascade Selection Molecular Dynamics and Markov state model. Biophysics
and Physicobiology 18, 305-316 (2021).

x‫ ۻ‬S. Hayward and A. Kitao. The role of the half-turn in determining structures of Alzheimer's Abeta wild-type andmutants. J Struct Biol 213, 107792 (2021).

x‫ ۻ‬T. Yamawaki, M. Mizuno, H. Ishikawa, K. Takemura, A. Kitao, Y. Shiro and Y. Mizutani. Regulatory Switchingby Concerted Motions on the Microsecond Time Scale of the Oxygen Sensor Protein FixL. J Phys Chem B 125,6847-6856 (2021).

x‫ ۻ‬J. Chan, K. Takemura, H.R. Lin, K.C. Chang, Y.Y. Chang, Y. Joti, A. Kitao and L.W. Yang. An Efficient Timerand Sizer of Biomacromolecular Motions. Structure 28, 259-269 e258 (2020).

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- 223 -

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ᗘྍኚప࢖࢜ࣥࣔࣅࣜࢸ࢕㉁㔞ศᯒ㸦VT-Cryo-IM-MS㸧ࡢ⮬స⿦⨨ࢆ⏝࠸࡚ࠊ㔠ᒓ㓟໬≀ࢡࣛࢫࢱ࣮ࡸࠊ࣍ࢫࢺ㸫ࢤࢫࢺ໬ྜ≀࡞࡝ࡢ࢖࢜
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㸦Ag+, Na+, K+, NH4+㸧ࡢ㘒య࡟ࡘ࠸࡚ࠊVT-Cryo-IM-MS ࡛ほࡉࢀࡓ฿㐩᫬㛫ศᕸ㸦ATD㸧ࢆゎᯒࡋࠊ␗ᛶ

໬ࡢ㏿ᗘᐃᩘ࡜άᛶ໬࢚ࢿࣝࢠ࣮ࢆỴᐃࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
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ࢺࣜἲࠊ␗ᛶ໬཯ᛂ⤒㊰᥈⣴ィ⟬࡟ࡣ GRRM14 ࢆ⏝࠸ࡓࠋ

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4 ✀㢮ࡢ㘒య࢖࢜ࣥ඲࡚࡟࠾࠸࡚ࠊ101 K ࡛ࡣ 2 ࡘࡢࣆ࣮ࢡ

ࢆᣢࡘ ATD ࡀほ࡟ᖐᒓࡋࡓࠋ

ࡉࢀࠊࡑࢀࡒࢀࢆ closed, open ᵓ㐀㸦ᅗ 1㸧ᗘࡀୖ᪼ࡍࡿ࡜ closed ࡜ open ࡢ㛫ࡢ฿㐩᫬㛫࡛࢖࢜ࣥᙉᗘࡀቑຍࡋࠊ205 K ࡛ࡣ༢୍ࡢࣆ࣮ࢡࢆᣢࡘ ATD ࡀ
ほࡉࢀࡓࠋࡇࢀࡣࠊ

ᗘୖ᪼࡜࡜ࡶ࡟␗ᛶ໬ࡢ㏿ᗘᐃᩘࡀ኱

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ࡢ

ATD ࢆ෌⌧ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ ATD ࢆసᡂࡋ㸦Fig.2㸧ࠊ㏿ᗘᐃᩘࢆỴᐃࡋࡓࠋ࢔ࣞࢽ࢘ࢫࣉࣟࢵࢺ࠿ࡽࠊ␗ᛶ໬ࡢάᛶ໬࢚
ࢿࣝࢠ࣮ࢆ 4.3–8.8 kJ mol−1 ࡜Ỵᐃࡋࡓࠋࡑࡢ⤖ᯝࠊ㘒ᙧᡂ࢚ࢿ
ࣝࢠ࣮Ec = (Ehost + Eguest) − Ecomplex ࡀ኱ࡁ࠸㘒య࡯࡝ࠊάᛶ໬࢚
ࢿࣝࢠ࣮ࡀ኱ࡁ࠸ഴྥࢆぢฟࡋࡓࠋ཯ᛂ⤒㊰᥈⣴ィ⟬࡟ࡼࡾࠊ␗ᛶ໬࡟࠾ࡅࡿ࣋ࣥࢮࣥ⎔㛫ࡢ㊥㞳ࡢ኱ࡁ࡞ኚ໬ࡀࠊC-C ༢⤖ྜࡢᅇ㌿࡟ࡼࡾ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

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‫ࠐۻ‬ゅ⏣ ೺࿃ࠊHe Xiࠊ⨾㰺ὠ ᩥ඾ࠊ኱ୗ ៞ḟ㑻ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿࢡࣜࣉࢱࣥࢻ[2.2.2]㘒యࡢ␗ᛶయศ㞳ࠖࠊ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍‫ࠐۻ‬୰ᓥ ඃᩯࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸ࡓⓑ㔠㓟໬≀ࢡࣛࢫࢱ࣮࢔ࢽ࢜ࣥ
ࡢᵓ㐀ࡢࢧ࢖ࢬ౫Ꮡᛶࠖ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍‫ࠐۻ‬Fangwen Dai, Yuto Nakajima, Keijiro Ohshimo, Fuminori Misaizu ”Structures of scandium oxide cluster cations
studied by ion mobility-mass spectrometry”, ᪥ᮏ໬Ꮫ఍ ➨ 102 ᫓Ꮨᖺ఍‫ࠐۻ‬኱ୗ ៞ḟ㑻ࠕࣉࣟࢺࣥ௜ຍศᏊࡢ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ㸫࢖࢜ࣥศᏊ཯ᛂ࡟ࡼࡿศᏊෆࣉࣟࢺࣥ⛣ື㸫ࠖ᪥ᮏ㉁㔞ศᯒᏛ఍➨ 77 ᅇ࢖࢜ࣥ཯ᛂ◊✲఍ࠊᣍᚅㅮ₇‫ࠐۻ‬బ⸨ Ⰻுࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸ࡓ࢔࣑ࣀᏳᜥ㤶㓟࡟࠾ࡅࡿࣉࣟࢺ
ࣥ⛣ື཯ᛂࡢ◊✲ࠖཎᏊ⾪✺Ꮫ఍➨ 46 ᅇᖺ఍‫ ➎୕ࠐۻ‬ὒኴᮁࠊỌ⏣ ฼᫂ࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸ࡓ㓟໬࢖ࢵࢺࣜ࢘
࣒ࢡࣛࢫࢱ࣮ṇ࢖࢜ࣥࡢᗄఱᵓ㐀࠾ࡼࡧ NO ศᏊ࡜ࡢ໬Ꮫ཯ᛂࡢ◊✲ࠖཎᏊ⾪✺Ꮫ఍➨ 46 ᅇᖺ఍‫ࠐۻ‬኱ୗ ៞ḟ㑻ࠊఀ⸨ ுభࠊHe Xiࠊ⨾㰺ὠ ᩥ඾ࠕᗘྍኚప࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿ࣍ࢫࢺ-ࢤࢫࢺ㘒యࡢ␗ᛶ໬཯ᛂࡢ◊✲ࠖཎᏊ⾪✺Ꮫ఍➨ 46 ᅇᖺ఍ࠊ࣍ࢵࢺࢺࣆࢵࢡㅮ₇‫ࠐۻ‬୰ᓥ ඃᩯࠊỌ⏣ ฼᫂ࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿⓑ㔠㓟໬≀ࢡࣛࢫࢱ࣮ṇ࢖࢜ࣥࡢ୍㓟໬Ⅳ⣲࡜ࡢ཯ᛂࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍‫ࠐۻ‬ఀ⸨ ுభࠊHe Xiࠊ⨾㰺ὠ ᩥ඾ࠊ኱ୗ ៞ḟ㑻ࠕᗘྍኚప࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿࢡ࢚ࣛ࢘ࣥ

࣮ࢸࣝ㘒యࡢ␗ᛶ໬཯ᛂࡢ◊✲ࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍‫ࠐۻ‬He Xiࠊ⨾㰺ὠ ᩥ඾ࠊ኱ୗ ៞ḟ㑻ࠕConformations of transition metal ion-crown ether complexes studied bycryogenic ion mobility-mass spectrometryࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍‫ࠐۻ‬ఀ⸨ ுభࠊHe Xiࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿࢪ࣋ࣥࢰࢡ࢚࣮ࣛ࢘ࣥࢸ
ࣝ-NH4+㘒యࡢ␗ᛶ໬཯ᛂࡢ◊✲ࠖ➨ 69 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍‫ ➎୕ۻ‬ὒኴᮁࠊỌ⏣ ฼᫂ࠊ኱ୗ ៞ḟ㑻ࠊࠐ⨾㰺ὠ ᩥ඾ࠕࢻࣜࣇࢺࢳ࣮ࣗࣈ࡜㣕⾜᫬㛫㉁㔞ศᯒィࢆ⏝࠸ࡓ࢖࢜ࣥࡢᵓ㐀࠾ࡼࡧ཯ᛂ◊✲ࠖ➨ 69 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍‫ࠐۻ‬኱ୗ ៞ḟ㑻ࠕ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸ࡓ࣍ࢫࢺ-ࢤࢫࢺ໬ྜ≀ࡢᵓ㐀࡜␗ᛶ໬཯ᛂࡢ◊✲ࠖ➨ 9 ᅇ࢖࢜ࣥ⛣ືᗘ◊✲఍ࠊᣍᚅㅮ₇‫ࠐۻ‬ఀ⸨ ுభࠊHe Xiࠊ኱ୗ ៞ḟ㑻ࠊ⨾㰺ὠ ᩥ඾ࠕᗘྍኚప࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ࡟ࡼࡿࢡ࢚ࣛ࢘ࣥ

࣮ࢸࣝ㘒యࡢ␗ᛶ໬཯ᛂࡢ◊✲ࠖ➨ 9 ᅇ࢖࢜ࣥ⛣ືᗘ◊✲఍



ฟ∧ᐇ⦼

‫ۻ‬኱ୗ ៞ḟ㑻ࠊᐑ㷂 ⯗ࠊబ⸨ Ⰻுࠊ᭹㒊 ᆂ࿃ࠊ⨾㰺ὠ ᩥ඾ࠕࣉࣟࢺࣥ௜ຍศᏊࡢ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒ㸫࢖࢜ࣥศᏊ཯ᛂ࡟ࡼࡿศᏊෆࣉࣟࢺࣥ⛣ື㸫ࠖJ. Mass Spectrom. Soc. Jpn., 70(1), 36-42 (2022).
‫ۻ‬Ryosuke Ito, Keijiro Ohshimo, and Fuminori Misaizu ”Structures of dibenzo-24-crown-8 complex with an NH4+ ion
studied by cryogenic ion mobility-mass spectrometry" Chem. Phys. Lett., 794, 139510 (2022). (5 pages)‫ۻ‬Toshiaki Nagata, Jenna W. J. Wu, Motoyoshi Nakano, Keijiro Ohshimo, and Fuminori Misaizu "Geometrical Structuresof Gas Phase Cerium Oxide Cluster Cations after Reaction with Nitric Oxide Studied by Ion Mobility Mass Spectrometry",
J. Phys. Chem. A, 126(7), 1204-1210 (2022).

- 228 -

ࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟Ⓨ⌧ࡢ㛵㐃ᛶ
Relation between functional expression and structure in protein‫ࢺ࢜ࣝࢗࢺࣥࣜۑ‬ṇ⨾ (ி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

&X=Q ࢆྵ᭷ࡍࡿ 62' ࡟࠾ࡅࡿᵓ㐀࡜ᶵ⬟ࡢ㛵㐃ᛶ㸱✀Ꮡᅾࡍࡿࣄࢺࡢ 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㉁࡛࠶ࡿࢫ࣮ࣃ࣮࢜࢟ࢧ࢖ࢻ࢔ࢽ࢜ࣥࣛࢪ࢝ࣝ㹍2-ࡢάᛶ㒊఩࡬ࡢ᥋㏆࡟ᑐࡍࡿⅬኚ␗ࡸ༢㔞య໬ࡢᙳ㡪࡟ࡘ࠸࡚㹋㹂ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ୰ᚰ࡟◊✲ࢆ⾜ࡗࡓࠋ&$3 ࡬ࡢ F$03 ⤖ྜࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧ࢔ࣟࢫࢸࣜࢵࢡᵓ㐀ኚ໬኱⭠⳦ࡸࡑࡢ㏆⦕ࡢ⣽⳦࡟Ꮡᅾࡍࡿ &$3 &DWDEROLWH$FWLYDWRU3URWHLQ ࡣ㑇ఏᏊ㌿෗ㄪ⠇ᅉᏊ࡜ࡋ࡚ാ࠸࡚
࠸ࡿࠋ&$3 ࡣ࣍ࣔ஧㔞య࡛ࠊྛࢧࣈࣘࢽࢵࢺࡣ F$03 ⤖ྜࢧ࢖ࢺ࡛࠶ࡿ &%' F$03%LQGLQJ'RPDLQ ࡜ '1$⤖ྜࢧ࢖ࢺ࡛࠶ࡿ '%' '1$ %LQGLQJ 'RPDLQ ࠿ࡽᵓᡂࡉࢀࡿࠋ ศᏊࡢ F$03 ࡀ &$3 ࡟⤖ྜࡍࡿ࡜ࠊ&%'࡜ࡣ㞳ࢀࡓ㡿ᇦ࡛࠶ࡿ '%' ࡢᵓ㐀ࡀ࢔ࣟࢫࢸࣜࢵࢡ࡟኱ࡁࡃኚ໬ࡍࡿࠋࡇࢀ࡟ࡼࡾࠊ&$3 ࡜≉␗ⓗ࡞ '1$㓄ิ࡜ࡢ⤖ྜࡀㄏᑟࡉࢀࡿࠋ௒ᅇࡣ⢒ど໬ࣔࢹࣝࢆ⏝࠸࡚㛗ᮇ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ &$3 ࡀᏑᅾࡋ࡞
࠸᮲௳ୗ࡛ࡢ⤖ྜάᛶ≧ែ࡬ࡢ㑄⛣ࡢྍ⬟ᛶ࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ

 ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ NDOOLNUHLQ ࣇ࢓࣑࣮ࣜࡢゐ፹άᛶ࠾ࡼࡧᇶ㉁≉␗ᛶࢱࣥࣃࢡ㉁ศゎ㓝⣲ ./. ࣇ࢓࣑࣮ࣜ࡟ᒓࡋ࡚࠸ࡿࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛࠶ࡿࢽ࣮ࣗࣟࣉࢩࣥࡣࠊ኱⬻㎶⦕⣔࡛Ⓨ⌧ࡉࢀࠊࡇࡢࢱࣥࣃࢡ㉁ࡢᶵ⬟㞀ᐖࡣ⢭⚄⑌ᝈࡢཎᅉ࡜࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࢽ
࣮ࣗࣟࣉࢩࣥࡢศᏊㄆ㆑ᶵᵓࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᩘ✀ࡢᑠࡉ࡞࣌ࣉࢳࢻࣔࢹࣝࢆᇶ㉁ࡍࡿ㹉㹊㹉㸶㸫࣌ࣉࢳࢻ」ྜయࣔࢹࣝࢆ⏝࠸࡚ࠊᇶ㉁≉␗ᛶࡢỴᐃᅉᏊࡢ᥈⣴ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
SOD㸯࡜ CAP ࡢ MD ィ⟬࡟ࡣ Gromacs2019 ࢆ⏝࠸ࡓࠋึᮇᵓ㐀࡟ࡣ㹖⥺⤖ᬗᵓ㐀ࡸ NMR ᵓ㐀ࢆ⏝࠸ࡓࠋ

୍᪉ࠊKLK8 ࡢ MD ィ⟬࡟ࡣ myPresto ࢆ⏝࠸ࡓࠋ」ྜయࣔࢹࣝࡢึᮇᵓ㐀ࡣ sievgene ࢆ⏝࠸ࢻࢵ࢟ࣥࢢࢆ⾜ࡗ࡚ࣔࢹࣝ໬ࢆ⾜࠸ MD ィ⟬࡟ࡣ cosgene ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

Cu,Zn ࢆྵ᭷ࡍࡿ SOD1 ࡟࠾ࡅࡿᵓ㐀࡜ᶵ⬟ࡢ㛵㐃ᛶ
SOD1 ࡣ Cu ࡜ Zn ཎᏊࡀ཯ᛂάᛶࢧ࢖ࢺࡢᗏ࡟Ꮡᅾࡋ࡚࠾ࡾࠊࡑࡢୖ㒊࡟ࡣ▷࠸Ș࣊ࣜࢵࢡࢫࢆྵࡴ㟼㟁࣮ࣝࣉ࡜࿧ࡤࢀࡿ㒊఩ࡀᏑᅾࡋࠊArg143 ࡀ཯ᛂࢧ࢖ࢺ࣏ࢣࢵࢺධࡾཱྀ௜㏆࡟Ꮡᅾࡍࡿࡇ࡜࡛㈇㟁Ⲵࢆ᭷ࡍ- 229 -

ࡿᇶ㉁ࢆ࣏ࢣࢵࢺࡢᗏ࡟࠶ࡿ Cu ࡬࡜ㄏᑟࡍࡿࠋᡃࠎࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊ㟼㟁࣮ࣝࣉࡣ Cu ࡢ⁐፹࿴⎔ቃࢆಖࡘࡇ࡜࡟㔜せ࡛࠶ࡾࠊ㔝⏕ᆺ࡛ࡣᇶ㉁࡛࠶ࡿ㹍2-ࡣ Arg143 ࡟ᤕᤊࡉࢀ᩿⥆ⓗ࡟ Cu ୖ㒊࡟Ꮡᅾࡋ࡚࠸ࡿྍ⬟ᛶࢆ♧ࡋࡓࠋ௒ᅇࡣ≉࡟㔝⏕ᆺ 2 㔞య࡜༢㔞య࡟ᑐࡋ࡚ co-solvent MD ィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊ㟼㟁࣮ࣝࣉࡢ unfolding ࢆྵࡴᇶ㉁⤖ྜ㒊఩࿘㎶ࡢᵓ㐀ኚ໬ࡣ Cu ࡬ࡢ㹍2-ࡢ᥋㏆ࢆⴭࡋࡃ㐜ࡽࡏࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
ࡲࡓࠊ⤖ྜ㒊఩࿘㎶ࡢᵓ㐀ኚ໬ࡣ Arg143 ࡢᇶ㉁⤖ྜ㒊఩࡟࠾ࡅࡿ఩⨨ࡸᦂࡽࡂ࡟ᙳ㡪ࢆ୚࠼ Cu ࡬ࡢ㹍2-ࡢ
᥋㏆ࢆไᚚࡋ࡚࠸ࡿྍ⬟ᛶࢆぢฟࡋࡓࠋ&$3 ࡬ࡢ F$03 ⤖ྜࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧ࢔ࣟࢫࢸࣜࢵࢡᵓ㐀ኚ໬ࡇࢀࡲ࡛ࡢ඲ཎᏊ MD ィ⟬࡟࠾࠸࡚ cAMP ⤖ྜ࡞ࡋ࡛ CAP ࡣ 2 㔞య໬࡟ࡼࡗ࡚ 2 㔞య᥋ྜ㒊఩࡟࠶ࡿc-helix ࡀఙ⦰ࢆ⧞ࡾ㏉ࡋࠊ㐲㝸࡟࠶ࡿ DBD 㡿ᇦࡢᵓ㐀ኚ໬ࢆࡶࡓࡽࡍ඙ೃࡀぢࡽࢀࡓࠋ௒ᅇࡣ⢒ど໬ࣔࢹࣝࢆ⏝࠸࡚ 1 ȣs ࡢィ⟬ࢆ⾜࠸ࠊcAMP ⤖ྜࡋ࡚࠸࡞࠸≧ែ࡛ DBD 㡿ᇦࡣ୙άᛶ≧ែ࠿ࡽάᛶ≧ែ࡬࡜㑄⛣ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊDBD 㡿ᇦࡢࡳ࡞ࡽࡎ CBD 㡿ᇦࡢ୍㒊 unfolding ࡶぢࡽࢀࡓࡇ࡜࠿ࡽヲ⣽࠿ࡘᩘ✀ࡢฟⓎ≧ែࡢ௬ᐃࢆ⾜࠺࡞࡝ࡢࡉࡽ࡞ࡿ᳨ドࢆ⌧ᅾ⥅⥆୰࡛࠶ࡿࠋ

 ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ NDOOLNUHLQ ࣇ࢓࣑࣮ࣜࡢゐ፹άᛶ࠾ࡼࡧᇶ㉁≉␗ᛶࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛ࡣᇶ㉁ࡢษ᩿㒊఩ࡢ๓᪉࡟࠶ࡿ࢔࣑ࣀ㓟ṧᇶࡢ㔜せᛶ࡟ࡘ࠸࡚㆟ㄽࡉࢀࡿࡇ࡜ࡀ
ከ࠸ࠋ㸱ࡘࡢ࢔࣑ࣀ㓟ṧᇶ࠿ࡽ࡞ࡿᑠࡉ࡞࣌ࣉࢳࢻࣔࢹࣝࢆ⏝࠸࡚ࠊKLK8-࣌ࣉࢳࢻ」ྜయࣔࢹࣝ㸳✀࡟ࡘ࠸࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸㏿ᗘㄽⓗᐇ㦂⤖ᯝ࡜ࡢẚ㍑ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ༑ศ࡞ᇶ㉁⤖ྜ࢚ࢿࣝࢠ࣮ࡣ
」ྜయࡢ⤖ྜᏳᐃ໬ࢆࡶࡓࡽࡋゐ፹ 3 ṧᇶࡢ㐺ṇ࡞Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡᙧᡂࢆಁࡍࡓࡵ࡟ᚲせ࡛࠶ࡿࡀࠊ
ࡑࢀ௨እ࡟ࡶᇶ㉁ษ᩿㒊఩ࡢ㐺ṇ࡞㓄ྥᛶࡸ࢜࢟ࢩ࢔ࢽ࣮࢜ࣥ࣍ࣝࡢᙧᡂ࡞࡝ࡢᅉᏊࡀᩚࡗ࡚ึࡵ࡚཯ᛂࡣ
㐍⾜ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ⤖ྜぶ࿴ᛶࠊゐ፹ 3 ṧᇶࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࠊ࢜࢟ࢩ࢔ࢽ࣮࢜ࣥ࣍ࣝࡢ
ᙧᡂࠊᇶ㉁ࡢ㓄ྥᛶࡀᇶ㉁≉␗ᛶࡢỴᐃᅉᏊ࡛࠶ࡿ࡜⤖ㄽ࡙ࡅࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬SOD1 ࡟࠾ࡅࡿⅬኚ␗ᑟධࡼࡿ㓝⣲άᛶኚ໬ண

ࠊࣜࣥࢺࢗࣝ࢜ࢺṇ⨾ࠊࣜࣥࢺࢗࣝ࢜ࢺࣘࣁࠊ⚟すᛌᩥ(2021: ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᫓Ꮨᖺ఍)‫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 ۻ‬,QYHVWLJDWLRQRQVXEVWUDWHVSHFLILFLW\DQGFDWDO\WLFDFWLYLW\RIVHULQHSURWHDVHQHXURSVLQ0/LQWXOXRWR0$EH
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Fig. 1 0ROHFXODU VWUXFWXUH RI
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6Q,, 3Fí 䛸ྠ䛨䛟䚸㘒య  䛾䝣䝍䝻䝅䜰䝙䞁㒊఩䛿䚸3Fí䛸䛺䛳䛶䛔䜛䛸⪃䛘䜙䜜䜛䚹䜎䛯䚸㉥እ䝇䝨䜽䝖䝹䛻䛚䛔䛶䚸䝣䝍䝻䝅䜰䝙䞁㒊఩䛾౯ᩘ䛻ᩄឤ䛺᣺ື䝰䞊䝗䛜䚸6Q,, 3Fí 䛷䛿 䚸FPí 䛻ほíFP 䛻ほ䛥䜜䛯䛾䛻ᑐ䛧䚸㘒య  䛷䛿䚸䚸䛥䜜䛯䛣䛸䜒䚸㘒య  䛷䛿䝣䝍䝻䝅䜰䝙䞁㒊఩䛜 3Fí䛸䛺䛳䛶䛔䜛䛣䛸䜢ᨭᣢ䛧䛶䛔䜛䚹㘒య  䛾㟁Ꮚ≧ែ䜢᫂䜙䛛䛻䛩䜛䛯䜑䚸')7 ἲ䠄01/䚸016;䚸&$0

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᭷ᶵศᏊ࡟࠾ࡅࡿග໬Ꮫ㐣⛬ࡢ⌮ㄽⓗ◊✲Theoretical studies on photochemical processes in organic molecules‫ۑ‬ᒣᓮ ⚈ᖹ㸪㰻⸨ ႐㸪໭ᕝ 㞞἞㸦ᘯ๓኱㝔⌮ᕤ㸧
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᭷ᶵ໬ྜ≀ࢆගບ㉳ࡋࡓ࡜ࡁ࡟㉳ࡇࡿ⊂⮬ࡢග໬Ꮫ㐣⛬ࡢᶵᵓ࡟ࡘ࠸࡚ࠊ཯ᛂ⤒㊰ࡢ㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙࠸࡚ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ◊✲ࢆ㐙⾜ࡋ࡚࠸ࡿࠋ ᖺᗘࡣࠊ୺࡟ḟࡢ㸦㸯㸧㸦㸰㸧ࡢග໬Ꮫ㐣⛬ࢆᑐ㇟࡜ࡋࡓ◊✲ࢆᐇ᪋ࡋࡓࠋ
㸦㸯㸧࢖ࣥࢹ࢕ࢦ⣔Ⰽ⣲࡟࠾ࡅࡿග␗ᛶ໬
࢖ࣥࢹ࢕ࢦࡣࠊศᏊࡢ୰ኸ࡟Ⅳ⣲̺Ⅳ⣲஧㔜⤖ྜࢆᣢࡘ࡟ࡶ࠿࠿ࢃࡽࡎࠊࡇࡢ⤖ྜࡢࡡࡌࢀ࡟ࡼࡿࢩࢫ̺
ࢺࣛࣥࢫග␗ᛶ໬ࢆ㉳ࡇࡉ࡞࠸ࠋ୍᪉ࠊ࢖ࣥࢹ࢕ࢦࡣ 1+ ᇶ࡜ &2 ᇶࡢ㛫࡛ศᏊෆỈ⣲⤖ྜࢆᙧᡂࡋ࡚࠸ࡿ
ࡀࠊࡇࡢ 1+ ᇶࢆ௚ࡢཎᏊࡲࡓࡣཎᏊᅋ࡛⨨ࡁ᥮࠼ࡓศᏊ࡛ࡣග␗ᛶ໬ࡀ㉳ࡇࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡇࡢ
཯ᛂᛶࡢ㐪࠸࡟ࡣศᏊෆỈ⣲⤖ྜࡢ᭷↓ࡀᙳ㡪ࡍࡿ࡜⪃࠼ࡽࢀࡿࡶࡢࡢࠊ㐪࠸ࢆ⏕ࡌࡉࡏࡿලయⓗ࡞ᶵᵓࡣศ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ࢖ࣥࢹ࢕ࢦ࡜ࡑࡢ⨨᥮యࡢࢩࢫ̺ࢺࣛࣥࢫග␗ᛶ໬࡟ࡘ࠸࡚࣏ࢸࣥࢩ࢚ࣕࣝ
ࢿࣝࢠ࣮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Ⅼࡢゎ᫂ࢆ┠ᣦࡍࠋ㸦㸰㸧ࢢࣝࢥ࣮ࢫ࡟࠾ࡅࡿ 2+ ⤖ྜࡢගゎ㞳⢾㢮ࡣⓎⰍᅋࢆᣢࡓ࡞࠸ࡓࡵ࡟྾཰࣭Ⓨගࢫ࣌ࢡࢺࣝࡢほࡀᅔ㞴࡛࠶ࡾࠊࡑࡢග໬Ꮫⓗᣲື࡟ࡘ࠸࡚ࡣ

Ṥ࡝ศ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊࢢࣝࢥ࣮ࢫศᏊࢆィ⟬ᑐ㇟࡟㑅ࡧࠊග໬Ꮫ཯ᛂ࡜ࡋ࡚㉳ࡇࡿ࡜ᮇᚅࡉࢀ
ࡿ 2+ ⤖ྜࡢゎ㞳࡟ࡘ࠸࡚ࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡢィ⟬࡟ࡼࡗ࡚཯ᛂᶵᵓࢆゎ᫂ࡍࡿࠋ≉࡟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࠸࡚ࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែ࡟࠾ࡅࡿᏳᐃᵓ㐀ࠊ୪ࡧ࡟ග␗ᛶ໬

࡟㛵ࡍࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡢ㔞Ꮚ໬Ꮫィ⟬ࢆᐇ⾜ࡋࡓࠋ୧⪅ࡢศᏊ࡟ࡘ࠸࡚ࠊࡲࡎ୕㔜㡯ບ㉳≧ែ㸦7≧ែ㸧ࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃ࢆィ⟬ࡋࠊࡇࡢ≧ែ࡟࠾ࡅࡿ␗ᛶ໬ࡢྍ⬟ᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡇࡢ
ィ⟬ࡣ ')7 ἲ㸦&$0%/<3 ỗ㛵ᩘ㸧ࢆ⏝࠸࡚ᐇ᪋ࡋࡓࠋࡉࡽ࡟ࠊ୍㔜㡯ບ㉳≧ែ㸦6 ≧ែ㸧࡟࠾ࡅࡿ␗ᛶ
໬ࡢ཯ᛂᛶࢆㄪ࡭ࡿࡓࡵࠊศᏊࡢ୧➃࡟࠶ࡿභဨ⎔ࢆ┬␎ࡋࡓࣔࢹࣝศᏊࡢග␗ᛶ໬࡟ࡘ࠸࡚࣏ࢸࣥࢩࣕࣝ
࢚ࢿࣝࢠ࣮᭤㠃ࢆィ⟬ࡋࡓࠋ෇㗹஺ᕪ࡜ࡑࡢ௜㏆࡟࠾ࡅࡿ㟁Ꮚ≧ែࢆṇࡋࡃᢅ࠺ࡓࡵࠊࡇࡢィ⟬࡟ࡣ &$66&)
ἲࢆ⏝࠸ࡓࠋ&$66&) ィ⟬ࡢ DFWLYH ✵㛫ࡣ  ࡜ࡋࡓࠋ')7 ィ⟬ࡣ *$0(66ࠊ&$66&) ィ⟬ࡣ 0ROSUR ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋ
㸦㸰㸧ࢢࣝࢥ࣮ࢫ࡟࠾ࡅࡿ 2+ ⤖ྜࡢගゎ㞳

- 239 -

ࡣࡌࡵ࡟ࠊᇶᗏ≧ែࡢᏳᐃᵓ㐀࡟࠾ࡅࡿࢢࣝࢥ࣮ࢫࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ 7'')7 ἲ࡛ィ⟬ࡋࡓࠋ2+ ⤖ྜࡢගゎ㞳࡛ࡣࠊ✵㛫ⓗ࡟኱ࡁࡃᗈࡀࡗࡓ ı ㌶㐨࡬ࡢບ㉳ࡀᮏ㉁ⓗ࡞ᙺ๭ࢆᯝࡓࡍ࡜ண᝿ࡉࢀࡿࠋࡑࡢࡓࡵࠊᇶ
ᗏ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࡟ἢࡗࡓ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝ
ࢠ࣮᭤⥺ࢆ 7'')7 ἲ࡛ィ⟬ࡋࡓࠋ ࠿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࢖ࣥࢹ࢕ࢦ࡜ࢳ࢜࢖ࣥࢹ࢕ࢦࡢ୧᪉࡟ࡘ࠸࡚ࠊ7'')7 ィ⟬࡛ࡣࠊ7 ≧ែ࡜ᇶᗏ≧ែ㸦6 ≧ែ㸧ࡢ㛫࡛࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࡀ஺ᕪࡋࠊ& & ⤖ྜࡢࡡࡌࢀࡓᵓ㐀࡛ 7 ≧ែࡢ࢚ࢿࣝ
ࢠ࣮ࡀ 6 ≧ែࢆୗᅇࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ&$66&) ィ⟬࡛ࡶࠊ6 ≧ែ࡜ 6 ≧ែࡢ෇㗹஺ᕪ࡟฿㐩ࡍࡿ࣏ࢸࣥࢩ
ࣕࣝ᭤⥺ࡀᚓࡽࢀࡓࠋ࠸ࡎࢀࡢィ⟬࡛ࡶࠊ཯ᛂ㞀ቨࡣࢳ࢜࢖ࣥࢹ࢕ࢦࡢ᪉ࡀ࢖ࣥࢹ࢕ࢦ࡟ẚ࡭࡚ᑠࡉࡃ࡞ࡾࠊ
ࡇࢀࡣ๓⪅ࡢศᏊ࡛␗ᛶ໬ࡀࡼࡾ㉳ࡇࡾࡸࡍ࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡓࡔࡋࠊ࢖ࣥࢹ࢕ࢦ࡛ࡶග␗ᛶ໬ࡀ㉳ࡇࡿྍ⬟ᛶࡀ࠶ࡿ࡜࠸࠺⤖ᯝࡣほ⤖ᯝ࡜཯ࡋ࡚࠸ࡿࡓࡵࠊ୕㔜㡯≧ែ࡛ࡶ &$66&) ࢆ⏝࠸ࡿࠊ&$66&) ࡢ

DFWLYH ✵㛫ࢆ኱ࡁࡃࡍࡿࠊ&$637 ἲ࡛㟁Ꮚ┦㛵ࡢィ⟬ࢆ⾜࠺➼ࡢ㏣ຍィ⟬࡟ࡼࡿ᳨ウࡀᚲせ࡛࠶ࡿࠋ
ࢢࣝࢥ࣮ࢫ࡟ࡘ࠸࡚㸸ບ㉳࢚ࢿࣝࢠ࣮ィ⟬ࡢ⤖ᯝࠊ⣸እ㡿ᇦࡢග྾཰࡛㑄⛣࡛ࡁࡿ 6 ≧ែࡀᏑᅾࡋࠊ㓟⣲ཎᏊୖࡢ Q ㌶㐨࠿ࡽ 2+ ⤖ྜࡢ ı ㌶㐨࡬ࡢ㑄⛣࡛≉ᚩ࡙ࡅࡽࢀࡿ Qı ≧ែ࡛࠶ࡿ࡜ศ࠿ࡗࡓࠋࡲࡓࠊගゎ㞳ࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ィ⟬࡛ࡣࠊ ࠿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࠸ࡿࠋ
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㛵ࡍࡿ◊✲ࢆᐇ᪋ࡋࡓࠋ
ᙜࢢ࣮ࣝࣉ࡛ࡣࠊ
ྜᡂࡉࢀࡓ᪂つ᭷ᶵศᏊ࡟ࡘ࠸࡚ ')7 ἲ㸦Ȧ%;' ỗ㛵ᩘࠊ*DXVVLDQ ౑⏝㸧࡟ࡼࡿᵓ㐀᭱㐺໬࠾ࡼࡧ +202࣭/802 ࡢ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠸ࠊศᏊࡢ≀ᛶ࡜ࡢ㛵ಀࢆ᳨ウࡋࡓࠋ⌧ᅾࠊࡇࡢ◊✲࡟㛵ࡍࡿㄽᩥࢆᢞ✏୰࡛࠶ࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫   ۻ‬ᒣᓮ⚈ᖹ ³&RPSXWDWLRQDOVWXG\RQWKHSKRWRUHDFWLRQVRILQGLJRDQGLWVGHULYDWLYHV´ ௧࿴  ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍ࠊ㒆ᒣ㸦࢜ࣥࣛ࢖ࣥ㛤ദ㸧ࠊ ᖺ  ᭶  ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫   ۻ‬1)/6DOZDGL*<<HDS6<DPD]DNL1.LPXUDDQG'7DNHXFKLVXEPLWWHG- 240 -

ཎᏊ᰾ࡢ㔞Ꮚຠᯝࢆ⪃៖ࡋࡓ⌮ㄽィ⟬ᡭἲ࡟ࡼࡿ㔜Ỉ⣲ྠ఩యຠᯝࡢゎᯒ
Multicomponent quantum mechanics method to analyze H/D isotope
effect including nuclear quantum effects‫ۑ‬Ᏹ⏣ᕝ
ኴ㑻㸦ᒱ㜧኱ᏛᕤᏛ㒊㸧◊✲┠ⓗỈ⣲ཎᏊࡣᵝࠎ࡞ศᏊ୰࡟ᏑᅾࡋࠊศᏊᵓ㐀ࡸ≀ᛶࡢỴᐃ࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋࡲࡓࠊỈ⣲ཎᏊ᰾ࡣ᭱ࡶ㉁㔞ࡢ㍍࠸ཎᏊ᰾࡛࠶ࡿࡓࡵࠊ㢧ⴭ࡞㔞Ꮚຠᯝ࠾ࡼࡧྠ఩యຠᯝࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿
ࡋ࡞ࡀࡽࠊ୍⯡ⓗ࡞⌮ㄽィ⟬࡛ࡣ %RUQ2SSHQKHLPHU ㏆ఝ࡟ᇶ࡙ࡁࠊཎᏊ᰾ࡢ㔞Ꮚຠᯝࡣ↓どࡉࢀࡿࠋᮏ◊✲࡛ࡣࠊ⏦ㄳ⪅ࡀ㛤Ⓨࡋ࡚ࡁࡓ㔞Ꮚከᡂศ⣔⌮ㄽ࠾ࡼࡧ⤒㊰✚ศศᏊືຊᏛ㸦3,0'㸧ἲࢆ⏝࠸࡚ࠊ✀ࠎࡢ⣔࡟࠾ࡅࡿཎᏊ᰾ࡢ㔞Ꮚຠᯝࡸ㔜Ỉ⣲ྠ఩యຠᯝ࡟ࡘ࠸࡚ゎᯒࡍࡿࠋࡲࡓࠊᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲ㄢ㢟࡟ࡘ࠸࡚ࡶ࠸ࡃࡘ࠿ྲྀࡾ⤌ࢇࡔࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
0&B40 ィ⟬࡟ࡣࠊ⊂⮬࡟ᣑᙇࡋࡓ *$866,$1 *$866,$1 ࢆ⏝࠸ࡓࠋࡲࡓࠊ3,0' ࢩ࣑࣮ࣗࣞࢩࣙ

ࣥࡣ⮬సࡢࢥ࣮ࢻࢆ⏝࠸࡚⾜ࡗࡓࠋᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲ㄢ㢟࡟ࡣࠊ*550 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ◊✲ᡂᯝࡇࡇ࡛ࡣࠊ+2 ࡢෆ㒊ᅇ㌿࡟ᑐࡍࡿ㔞Ꮚຠᯝ࡟ࡘ࠸࡚ 3,0' ἲࢆ⏝࠸࡚ゎᯒࡋࡓ⤖ᯝ࡟ࡘ࠸࡚♧ࡍࠋ+2

୰ࡢ +22+ ᅇ㌿࡟ᑐࡍࡿάᛶ໬࢚ࢿࣝࢠ࣮ࡣ &&6' 7 DXJFFS94= ࡛ࣞ࣋ࣝഹ࠿ NFDOPRO ࡛࠶ࡾࠊᐜ᫆࡟ᅇ㌿ࡀ㉳ࡁ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊ+2 ࡢ +22+ ᅇ㌿࡟ᑐࡍࡿ㔞Ꮚຠᯝ࠾ࡼࡧ ᗘຠᯝࢆヲ⣽࡟᳨ウࡍࡿࡓࡵࠊ7 ....... ࡢྛ ᗘ࡟࠾࠸࡚ 3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
ᐇ᪋ࡋࡓࠋ3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ㟁Ꮚ≧ែࡣࠊ03DXJFFS9'= ࡛ࣞ࣋ࣝィ⟬ࡋࡓࠋ3,0' ࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟࠾࠸࡚ࡣࠊࡑࢀࡒࢀࡢཎᏊ᰾ࡣ  ಶࡢࣅ࣮ࢬ࡛ᒎ㛤ࡋࠊ+2 40 + ࡜ '2 40 ' ࡟ࡘ࠸࡚ࢩ࣑
࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡲࡓࠊẚ㍑ࡢࡓࡵࣅ࣮ࢬᩘࢆ  ࡜ࡋࡓྂ඾ࢩ࣑࣮ࣗࣞࢩࣙࣥ &/ ࡶ⾜ࡗࡓࠋᅗ  ࡟ࡣ D . E . F . ࡢྛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾᚓࡽࢀࡓ 2+ ⤖ྜ㛗ࡢ୍ḟඖศᕸࢆ♧ࡋࡓࠋ࡝ࡢ ᗘ࡟࠾࠸࡚ࡶ &/ ࡟ẚ࡭࡚ 40 ࡢศᕸࡣࣈ࣮ࣟࢻ໬ࡋ࡚࠾ࡾࠊཎᏊ᰾ࡢ㔞Ꮚຠᯝ࡟ࡼࡗ࡚ 2+ ⤖ྜ㛗ࡀᗈ࠸⠊ᅖ࡟ศᕸࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋᅗ  D . E . F . ࡢࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥᚓࡽࢀࡓ 2+ ⤖ྜ㛗  ḟඖศᕸ

- 241 -

ḟ࡟ࠊ2+ ⤖ྜ㛗࡜ +22+ ஧㠃ゅࡢ஧ḟඖศᕸࢆᅗ  ࡟♧ࡋࡓࠋࡇࡇ࡛ࡣࢫ࣮࣌ࢫࡢ㒔ྜୖࠊ୍㒊ࡢ⤖ᯝࡢࡳࢆ♧ࡋࡓࠋ. ࡢ &/ ࡢ⤖ᯝ࡛ࡣ +22+ r௜㏆࡟ࡣṤ࡝ศᕸࡀぢࡽࢀ࡞࠸ࠊࡘࡲࡾ +22+ ࡢᅇ㌿ࡀ㉳ࡁ࡚࠸࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ୍᪉࡛㧗

. ࡢࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࡴࡋࢁ &/ ࡟࠾࠸࡚ +22+ r

௜㏆ࡢศᕸࡀ㢧ⴭ࡟ቑຍࡋࡓࠋࡇࢀࡣࠊཎᏊ᰾ࡢ㔞Ꮚຠᯝ࡟ࡼࡾ 2+ ⤖ྜ㛗ࡀᗈ࠸⠊ᅖ࡟ศᕸࡋࡓࡇ࡜࡛ࠊ
㏫࡟ᅇ㌿ࡢࡓࡵࡢ㞀ቨࡀ㧗ࡃ࡞ࡗ࡚ࡋࡲ࠸ࠊຠ⋡ⓗ࡟ᅇ㌿ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞ࡃ࡞ࡗࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡘࡲࡾࠊ+2 ୰ࡢ +22+ ෆ㒊ᅇ㌿࡟ᑐࡋ࡚ࡣ➇ྜࡍࡿ」ᩘࡢ㔞Ꮚຠᯝࡀぢࡽࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋᅗ  D . F . ࡢࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥᚓࡽࢀࡓ 2+ ⤖ྜ㛗࡜ +22+ ஧㠃ゅࡢ஧ḟඖศᕸ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ᳃⪷἞㸪Ᏹ⏣ᕝኴ㑻㸪❧ᕝோ඾㸪ࢺࣜࢳ࣒࢘◊✲఍ 㸪 ᖺ  ᭶   ⏣୰㍤㸪᱓⏿࿴᫂㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪➨  ᅇⱝᡭ㔜Ỉ⣲◊✲఍㸪 ᖺ  ᭶   ᭹㒊㑳⨾㸪වᯇభ඾㸪▼ඖᏕె㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪➨  ᅇⱝᡭ㔜Ỉ⣲◊✲఍㸪 ᖺ  ᭶   ἅỈ⚈୍㸪ᕝῡⲁ㸪ᒣᮧὈஂ㸪Ᏹ⏣ᕝኴ㑻㸪኱⁪㝯ྐ㸪┈⏣ᫀᶞ㸪୕㍯ὒᖹ㸪㰻⸨୍ᘺ㸪 ᖺ᪥ᮏᾮᬗᏛ఍ウㄽ఍㸪 ᖺ  ᭶   ᭹㒊㑳⨾㸪වᯇభ඾㸪▼ඖᏕె㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ 㸪 ᖺ  ᭶   ᰘ⏣ᬕ▮㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ 㸪 ᖺ  ᭶   ⏣୰㍤㸪᱓⏿࿴᫂㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪➨ ᅇ୰㒊໬Ꮫ㛵ಀᏛ༠఍ᨭ㒊㐃ྜ⛅Ꮨ኱఍㸪 ᖺ  ᭶   ⏣୰㍤㸪᱓⏿࿴᫂㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ LQ ࡘࡃࡤ㸪 ᖺ  ᭶   1XWWDSRQ<RGVLQ +LURNL 6DNDJDPL7DUR
8GDJDZD 7DND\RVKL ,VKLPRWR 6LULSRUQ -XQJVXWLZRQJ 0DVDQRUL 7DFKLNDZD WK -DSDQ7KDL 2QOLQH:RUNVKRS RQ
7KHRUHWLFDODQG&RPSXWDWLRQDO&KHPLVWU\'HFHPEHU   Ᏹ⏣ᕝኴ㑻㸪⏣୰㍤㸪ᖹ㔝ᜏኵ㸪᱓⏿࿴᫂㸪❧ᕝோ඾㸪㤿ሙṇ᫛㸪㛗ᔱ㞼ර㸪➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪 ᖺ  ᭶   ⏣୰㍤㸪᱓⏿࿴᫂㸪❧ᕝோ඾㸪Ᏹ⏣ᕝኴ㑻㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ᫓Ꮨᖺ఍㸪 ᖺ  ᭶  7DUR 8GDJDZD +LNDUX7DQDND .D]XDNL.XZDKDWD0DVDDNL%DED7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDQRUL7DFKLNDZDWK ,QWHUQDWLRQDO6\PSRVLXPRQ
0ROHFXODU6SHFWURVFRS\-XQH  7DUR8GDJDZD5K\V%0XUSK\7DPLP$'DUZLVK0DVDQRUL7DFKLNDZD
6HLML0RULWK ,83$&,QWHUQDWLRQDO&RQIHUHQFHRQ3K\VLFDO2UJDQLF&KHPLVWU\-XO\

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫  ۻ‬7DUR8GDJDZD5K\V%0XUSK\7DPLP$'DUZLVK0DVDQRUL7DFKLNDZD6HLML0RULBull. Chem. Soc. Jpn.
     6KRLFKL .XWVXPL]X$NDQH .DZDIXFKL<DVXKLVD<DPDPXUD 7DUR 8GDJDZD 7DNDVKL 2WDNL 0DVDNL
0DVXGD <RKHL 0LZD .D]X\D 6DLWR Chem. Eur. J.     ‫   ۻ‬7DUR 8GDJDZD .D]XDNL .XZDKDWD
0DVDQRUL7DFKLNDZDComp. Theor. Chem.   ‫  ۻ‬$NDUL.DZDMLUL7DUR8GDJDZD0DR0LQRXUD7RVKLDNL0XUDLChemistryOpen'2,RSHQ ‫  ۻ‬+LNDUX7DQDND.D]XDNL.XZDKDWD0DVDQRUL7DFKLNDZD7DUR8GDJDZDACS Omega  - 242 -

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Ζࣆ͗ࢨఢ͠Ηͱ͏ΖɿҲ๏ɼ/.% ࣙରͺ /.% ͳ 675$'Į ‫ ;ٶ‬02Į ͹  ͯ͹νϱϏέ࣯ҾࢢͲߑ੔͠ΗΖ  ྖର‫ܗ‬͹෵߻ର‫ܙ‬੔ͶΓͮͱ‫׈‬੓ԿͤΖ͞ͳ͗ๅࠄ͠Ηͱ͏Ζ ෵߻ର஦͹ /.% ͳ 675$'Į ‫;ٶ‬02Į ؔͶಉ͚ಊద͵ΠϫητϨρέްՎͺ /.% ͹‫׈‬੓੏‫ޜ‬Ͷ॑གྷ͵ༀׄΝՎͪ͢ͱ͏ΖՆ೵੓͍͗Ζɿ͖͢͢͞͹෵߻ର‫ܙ‬੔ͶΓͮͱ /.% Ν‫׈‬੓ԿͤΖ෾ࢢ‫ߑؽ‬͹ಊదଈ໚ͺ͞ΗΉͲຈʹ‫͠ڂݜ‬Ηͱ͏͵͏ɿ/.% ͹‫׈‬੓੏‫ޜ‬Ͷ‫ؖ‬ΚΖΠϫητϨρέ͵ಊదްՎ͹‫ڂݜ‬ͺࡋ๖಼෾ࢢ੏‫ߑؽޜ‬͹સ༲ཀྵմͶͳͮͱ॑གྷ
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3URWHLQ 'DWD %DQN ʤ3'%ʥͶౌ࿧͠Ηͱ͏Ζ /.%ɼ675$'Įɼ‫ ;ٶ‬02Į ͹෵߻ରߑଆ৚ๅʤ:7.ʥ
Ν༽͏ɼ෾ࢢಊྙָεϝϣϪʖεϥϱͶͺ *520$&6 ϕϫήϧϞΝ༽͏ͪɿ ໼ਫ਼‫ܗ‬෵߻ରͶՅ͓ͱɼ/.% ‫׈‬੓Ͷ॑གྷͲͨ͹รҡ͗‫ؽ‬೵Ν୉͚͘րรͤΖͳๅࠄ͠Ηͱ͏ΖΠϝό࢐รҡର͹਼झྪ΍‫ͤࢋܯ‬Ζ༩ఈͲ͍Ζɿ͞ΗͶՅ͓ͱ෵߻ରΝߑ੔ͤΖ  ͯ͹νϱϏέ࣯΍ͨΗͩΗୱྖରͶ෾཯͢ͱพ‫ݺ‬Ͷ෾ࢢಊྙָεϝϣϪʖεϥϱͲ‫ͤࢋܯ‬Ζɿ͞ΗΔ͹‫ܧ‬Νௗ࣎ؔ෾ࢢಊྙָεϝϣϪʖεϥϱ‫ͱ͢ࢋܯ‬մੵͶචགྷ͵υʖνΝਫ਼੔ͤΖɿ࣏Ͷ‫Ͳࢋܯ‬ಚΔΗͪεϝϣϪʖεϥϱυʖνΝմੵͤΖɿ෾ࢢಊྙָεϝϣϪʖεϥϱ‫ࢋܯ‬஦ͶνϱϏέ࣯෾ࢢͺࣙ༟Ͷด਒ʀյ఺ҢಊͤΖ͗͞͹ްՎΝखΕঈ͚ॊཔ͹ඬ६దघ๑ͺ୉͘͵‫ࠫޣ‬͹‫ݬ‬ҾͲ͍ͮͪɿ
͞͹‫ࠫޣ‬͹Ӫ‫ڻ‬Νఁ‫ͤݰ‬ΖҟͶɼ॑͸߻Κͦ‫ࠫޣ‬Ν࠹ঘԿͤΖϗ΢θਬఈΝ‫ͤ༽׈‬Ζմੵघ๑ʤ0L\DVKLWD
<RQH]DZD-&3ʥΝ༽͏ͱ෵߻ର‫ܙ‬੔࣎ͳୱྖର࣎͹νϱϏέ࣯͹ಊదΑΔ͙Νմੵ͢ͱർֳ͢ɼ෵߻ର
‫ܙ‬੔ͶΓΖಊదรԿΝΓΕਜ਼֮Ͷ඲ՃͤΖɿ͠ΔͶɼ෾ࢢಊྙָεϝϣϪʖεϥϱυʖνմੵͶɼҐԾ͹ D ͳ̳ͶࣖͤΓ͑͵ɼ‫ؽ‬փָसΏ $, Ͳ༽͏ΔΗΖ਼ཀྵմੵघ๑ΏυΡʖϕϧʖωϱήదघ๑Ν࢘ͮͱɼνϱϏέ಼࣯෨‫;ٶ‬νϱϏέ࣯ؔ͹ಊద‫ܐؖ‬Ν੠ືͶ਼஍ԿͤΖ౵͹ްՎద͵մੵʀ඲ՃΝࣰࢬ͢ͱɼಊదΠϫητϨρέްՎͶ‫ͤؖ‬Ζ৿‫͖॑ͯو‬གྷ͵எ‫ݡ‬͹பड़Νୣ੔ͤΖɿ- 243 -

֦νϱϏέ࣯͗෵߻ର‫ܙ‬੔ͤΖ࣎ͳୱྖରͲଚࡑͤΖ࣎͹ͨΗͩΗ͹εϝϣϪʖεϥϱυʖνͶଲ͢ͱɼ
D

क੔෾෾ੵ๑౵Ν༽͏ͱ‫ڢ‬ಉదΑΔ͙ΏߑଆรԿ͹ಝ௅Νபड़ͤΖɿ͞ΗΔΝർֳ͢ͱ෵߻ର‫ܙ‬੔͹ްՎΝ‫ͤৄݗ‬Ζɿ

Eଡ૜ΨʖφΦϱαʖξʖΝ࢘ͮͪಊదಝ௅Νபड़ͤΖυΡʖϕϧʖωϱήմੵ౵Ν༽͏ͱΠϝό࢐࢔‫خ‬ؔ‫཯ړ‬͹࣎ؔรಊ͹ಝ௅Ͷ‫ͱ͏Ͱخ‬νϱϏέ࣯͹ߑଆ྘ҮΝ෾ྪͤΖɿ͠ΔͶ෾ྪ͠Ηͪߑଆ྘Үؔ͹૮‫ޕ‬৚ๅྖ౵΍‫ٽ‬Όͱ෵߻ର‫ܙ‬੔͹ްՎΝ඲ՃͤΖɿ ◊✲ᡂᯝ
/.% ͳ 675$'Į ‫ ;ٶ‬02Į ͖Δ੔ΖνϱϏέ࣯෵߻ରߑଆʤ:7.ʥΝਦ  ͶࣖͤɿνϱϏέ࣯෵߻ର͹ӣಊ੓ͳ෵߻ରΝ‫ܙ‬੔͢͵͏࣎͹‫ݺ‬ʓ͹ୱྖରνϱϏέ࣯͹ӣಊ੓ΝർֳͤΖҟͶɼ෵߻ରߑଆ͖Δ  ͯ͹νϱϏέ࣯Νୱྖରͳ͢ͱ෾཯ͪ͢ɿ͠ΔͶ͞͹෾཯ͪ͢ୱྖରνϱϏέ࣯ߑଆຘͶસ‫ࢢݬ‬ϠυϩΝన઀Ͷߑ஛͢༻ഖ෾ࢢ౵ΝՅ͓  झྪ͹ୱྖରνϱϏέ࣯͹෾ࢢಊྙָεϝϣϪʖεϥϱ༽Ϡυϩ‫ܧ‬Νࡠ੔ͪ͢ɿ
෵߻ର͹સ‫ࢢݬ‬εϝϣϪʖεϥϱ༽Ϡυϩ‫ܧ‬΍ಋ༹Ͷࡠ੔ͪ͢ɿ
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ᅗ  /.%675$'Į02Į 」ྜయᵓ㐀㸬࿘ࡾ࡟㓄⨨ࡋࡓ⁐፹ỈศᏊࡸ࢖࢜ࣥཎᏊ➼ࡣ┬␎ࡋ࡚࠸ࡿ㸬㯤ⰍศᏊࡣ 675$'Į ࢆ♧ࡋࠊ㉥ⰍศᏊࡣ /.% ࢆ♧ࡋࠊ⣸ⰍศᏊࡣ 02Į ࢆ♧ࡋ࡚࠸ࡿ㸬͞ΗΉͲͶɼ෵߻ର͖Δ෾཯ͪ͢ /.%ɼ675$'Į ‫ ;ٶ‬02Į ֦ୱྖରνϱϏέ࣯͹෾ࢢಊྙָεϝϣϪʖεϥϱ‫ࢋܯ‬Νࣰࢬ͢ͱφϧζΥέφϨʖυʖνΝफॄͪ͢ɿ͞ΗͶՅ͓ͱ෵߻ର͹෾ࢢಊྙָεϝϣϪʖεϥϱ‫ࢋܯ‬Ν਒Όͱ͏Ζɿ༩ඍదմੵͺ֦ୱྖରνϱϏέ࣯͹෾ࢢಊྙָεϝϣϪʖεϥϱ‫ࢋܯ‬ͺ҈ఈͶࣰߨ͠Ηͱ͕ΕεϝϣϪʖεϥϱॵ‫غ‬Ͷຈʹฑߩয়ସͶୣ͢ͱ͏ΖࣆΝࣖ͢ͱ͏Ζɿ Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ࡞ࡋ ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

- 244 -

㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ࡑࡢ཯ᛂᛶ
7KHRUHWLFDOLQYHVWLJDWLRQRQVWUXFWXUHVRIPHWDOFOXVWHUVDQG
WKHLUUHDFWLYLW\‫ۑ‬ᑠᏳ ႐୍㑻 㸪㧘㔝 ៅ஧㑻 㸪ቑ⏣ ᫴ஓ 㸪ỤᏲ ᐀ḟ㑻 㸪㛗㇂ᕝ ៅ࿃ 㸪୰ᮧ ຾அ௓ 㸪ఀ⸨ 㥴 㸪᝴㇂ ᘓ௓ 㸪⏣ᆏ ♸㔛Ꮚ 㸪⚟⏣ ᾈ⏕ 㸪ᒾᮏ ᑗྐ 㸦 ᮾ኱㝔⌮㸪 ி኱ (6,&%㸧
1◊✲┠ⓗᩘಶ࠿ࡽᩘⓒಶࡢ㔠ᒓཎᏊࡀ᭷ᶵ㓄఩Ꮚ࡛⿕そࡉࢀࡓ㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡣࠊࣂࣝࢡࡢ㔠ᒓࡸࢼࣀ⢏Ꮚ࡟ࡣぢࡽࢀ࡞࠸ࠊ≉␗ⓗ࡞ᗄఱᵓ㐀ࡸ㞳ᩓⓗ࡞㟁Ꮚᵓ㐀ࢆᣢࡕࠊࡑࢀࡽ࡟⏤᮶ࡍࡿࣘࢽ࣮ࢡ࡞≀ᛶࢆⓎ⌧ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ୰࡛ࡶࠊ࢔ࣝ࢟ࢽࣝ㓄఩Ꮚ㸦&Ł&5㸧ࡣ㔠ࢥ࢔࡜㓄఩Ꮚ࡜ࡢ ʌ ඹᙺࡸ ı ⤖ྜ࡜ ʌ⤖ྜࢆ⤌ࡳྜࢃࡏࡓከᙬ࡞⏺㠃ᵓ㐀ࢆᙧᡂࡍࡿⅬ࡛ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ᭱㏆ࡢ◊✲࡟࠾࠸࡚ᡃࠎࡣࠊ㟁Ꮚồᘬᛶࡢ &) &+&Ł&㸦$U)&Ł&㸧ࢆ⏝࠸ࡿࡇ࡜࡛ࠊ3G$X ࢥ࢔ࡀ  ಶࡢ $X &Ł&$U)  ࢜ࣜࢦ࣐࣮࡛ಖㆤࡉࢀ
ࡓ>3G$X &Ł&$U) @±ࡢ⢭ᐦྜᡂࢆ㐩ᡂࡋࡓࠋࡇࡢࢡࣛࢫࢱ࣮ࡢ㓄఩Ꮚࢆ㟁Ꮚồᘬᛶࡢ &Ł&$U) ࠿ࡽ୍⯡ⓗ࡞&Ł&3K ࡬࡜  ࡘࡎࡘ⨨᥮ࡋ࡚࠸ࡃ࡜ࠊࢫ࣌ࢡࢺࣝࡢ❧ࡕୖࡀࡾ࠿
ࡽồࡵࡓࢡࣛࢫࢱ࣮ࡢ᩿⇕㟁Ꮚぶ࿴ຊ㸦$($㸧ࡀ㓄఩Ꮚࡢ⨨᥮ᩘ࡟ẚ౛ࡋ࡚  PH9 ࡎࡘῶᑡࡍࡿࡇ࡜ࢆ㉁㔞㑅ูẼ┦ග㟁Ꮚศගἲ࡟ࡼࡾぢฟࡋࡓ㸦ᅗ 㸧ࠋᾮ┦࡟࠾ࡅࡿ㓄఩Ꮚࡢ⨨᥮ᩘࡢไᚚࡸ⢭ᐦศ㞳ࡣከ኱࡞ປຊࢆせࡍࡿࡀࠊ㉁㔞㑅ู࡜Ẽ┦ග㟁Ꮚศගࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛≉ู࡞๓ฎ⌮ࢆࡍࡿࡇ࡜࡞ࡃ⨨᥮ᩘ࡟ᛂࡌࡓ㟁Ꮚᵓ㐀ࡢኚ໬ࡢ㏣㊧ࢆ㐩ᡂࡋࡓࠋᮏ◊✲࡛ࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ㸦')7㸧ィ⟬࡟ࡼࡗ࡚>3G$X &Ł&$U) ±[ &Ł&3K [@±㸦[ ᅗ >3G$X &Ł&$U) ±[ &Ł&3K [@±㸦[㸧ࡢᵓ㐀␗ᛶయࢆィ⟬ࡋࠊ⌮ㄽⓗ࡞ᆶ┤㟁Ꮚ⬺㞳࢚ࢿࣝࢠ࣮

±㸧ࡢග㟁Ꮚࢫ࣌ࢡࢺࣝࠋ ࡣ  ග

㸦9'(㸧ࢆ⟬ฟࡋࡓࠋࡲࡓࠊ㟁Ⲵᐦᗘศᕸࡢゎᯒ࠿ࡽ ʌ ඹᙺࡀ㟁Ꮚ㐣⛬࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠋᏊぶ࿴ຊࡢኚ໬࡟୚࠼ࡿຠᯝ࡟ࡘ࠸࡚⪃ᐹࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ')7 ィ⟬ࡣ 7XUERPROH ࣃࢵࢣ࣮ࢪ࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚ 3%( ࢆࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ GHI69 3 ࢆ⏝࠸ࡓࠋࡲࡎࠊሗ࿌ࡉࢀ࡚࠸ࡿ
⤖ᬗᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ࡚ 
౯㈇࢖࢜ࣥࢡࣛࢫࢱ࣮
>3G$X &Ł&$U) @± ࡢ ᵓ 㐀᭱㐺໬ࢆ⾜࠸ࠊD ࢆᚓࡓࠋḟ
࡟ࠊD ࡢ &Ł&$U) 㓄఩Ꮚࡢ ᅗ >3G$X &Ł&$U) ±[ &Ł&3K [@± [   ࡢ᭱㐺໬ᵓ㐀ࠋ㉥Ⰽࡣ⨨᥮ࡋࡓ &Ł&3K ࢆ⾲ࡍࠋ

- 245 -

ಶࢆ &Ł&3K ࡟⨨᥮ࡍࡿࡇ࡜࡛  ⨨᥮యࢆᵓ⠏ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ ✀㢮ࡢ␗ᛶయ DࠊE ࢆᚓࡓࠋE ࡼࡾࡶ H9 Ᏻᐃ࡞ D ࡢᵓ㐀࠿ࡽࡉࡽ࡟  ࡘࡢ㓄఩Ꮚࢆ⨨᥮ࡍࡿࡇ࡜࡛  ⨨᥮యࢆᵓ⠏ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ ✀㢮ࡢ␗ᛶయ DࠊE ࢆᚓࡓࠋD ࡣ E ࡼࡾࡶ  H9 ᏳᐃࡔࡗࡓࠋࡲࡓࠊD ࡜ྠࡌᑐ⛠ᛶ࡟࠶ࡿ  ಶࡢ㓄఩Ꮚࢆ &Ł&3K ࡟⨨᥮ࡍࡿࡇ࡜࡛  ⨨᥮యࢆᵓ⠏ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊD ࢆᚓࡓࠋ᭱ᚋ࡟ࠊࡍ࡭࡚ࡢ㓄఩Ꮚࢆ⨨᥮ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊD ࢆᚓࡓࠋᚓࡽࢀࡓ  ಶࡢ᭱㐺໬ᵓ㐀ࡀᒁᡤᏳᐃᵓ㐀࠿☜ㄆࡍࡿࡓࡵ᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋE ࡜ D ࡟ࡘ࠸࡚ࡣ㈇ࡢ
᣺ືᩘࡀほ ࡉࢀࡓࡀࠊ㓄఩Ꮚࡢᅇ㌿࡜ኚゅ㐠ື࡟క࠺ࡶࡢ࡛⤯ᑐ್ࡀ  FP± ௨ୗ࡜ᑠࡉ࠸ࡶࡢࡔࡗࡓࡓࡵ
᭦࡞ࡿᵓ㐀᭱㐺໬ࡣ⾜ࢃ࡞࠿ࡗࡓࠋẼ┦ග㟁Ꮚศග࡛᫂ࡽ࠿࡟ࡋࡓ $($ ࡟ᑐࡍࡿ㓄఩Ꮚຠᯝࡢ㉳※࡟ࡘ࠸࡚⪃ᐹࡍࡿࡓࡵࠊ ಶࡢᵓ㐀࡟ࡘ࠸࡚  ౯ࡢ㈇࢖࢜ࣥ࡟ࡋࡓ࡜ࡁࡢ࢚ࢿࣝࢠ࣮ࢆ୍Ⅼィ⟬࡛ồࡵࠊ ౯㈇࢖࢜ࣥ
࡜ࡢ࢚ࢿࣝࢠ࣮ᕪ࠿ࡽ 9'( ࢆ⟬ฟࡋࡓࠋࡲࡓࠊ⮬↛⤖ྜ㌶㐨㸦1%2㸧࡟ࡼࡿ㟁Ⲵᐦᗘゎᯒࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ⨨᥮ᩘࡀ  ࡜  ࡢ⤌ᡂ࡟ࡘ࠸࡚㸪ィ⟬ࡋࡓᵓ㐀␗ᛶయ㸦D ࡜ EࠊD ࡜ E㸧ࡢ㛫ࡢ࢚ࢿࣝࢠ࣮ᕪࡣࡑࢀࡒࢀ H9ࠊH9 ࡛࠶ࡿࡢ࡟ᑐࡋࠊ9'( ࡢᕪࡣ࠸ࡎࢀࡶ H9 ࡔࡗࡓࠋࡇࡢ⤖ᯝࡣࠊ㓄఩Ꮚࡢ⨨᥮఩⨨࡟ࡼࡽࡎ␗ᛶయࡢ 9'( ࡣ࡯ࡰྠࡌ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊ⁐ᾮࡢ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࡀ⨨᥮ᩘࡢቑຍ࡟ᑐࡋ࡚୙ኚࡔ
ࡗࡓࡇ࡜࡜୍⮴ࡋ࡚࠸ࡿࠋィ⟬࡛ồࡵࡓ 9'( ࡣ㓄఩Ꮚ⨨᥮ᩘ࡟ẚ౛ࡋ࡚ῶᑡࡋ࡚࠾ࡾࠊᐇ㦂ࡢ $($ ࡢῶᑡࢆ෌⌧ࡋ࡚࠸ࡓ㸦ᅗ 㸧ࠋ+202ࡢ࢚ࢿࣝࢠ࣮ኚ໬ࡀ 9'( ࡢኚ໬࡟㏆࠸್࡛࠶ࡗࡓࡇ࡜࠿ࡽࠊ௒ᅇほࡉࢀࡓ 9'( ࡢῶᑡࡢ┤᥋ⓗ࡞せᅉࡣ㓄఩Ꮚ஺᥮࡟ࡼࡿ +202 ࡢᅗ ')7ィ ⟬ ࡛ ồ ࡵ ࡓ୙Ᏻᐃ໬࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࠋࢡࣛࢫࢱ࣮ࡢ㟁Ⲵᐦᗘศᕸゎᯒࢆ⾜>3G$X &Ł&$U) ±[ &Ł&3K [@± [ ࡗࡓ࡜ࡇࢁࠊ㓄఩Ꮚ⨨᥮࡟ࡼࡿ㟁Ⲵᐦᗘࡢኚ໬ࡣࣇ࢙ࢽࣝ⎔ࡢⅣ⣲  ࡢ 9'( ࡢࣉࣟࢵࢺࠋ

࡜Ỉ⣲࠾ࡼࡧ &) ᇶ࡟ᒁᅾࡋ࡚࠾ࡾࠊ3G$X ࢥ࢔ࡢ㟁Ⲵኚ໬ࡣ㓄఩Ꮚࢆࡍ࡭࡚⨨᥮ࡋࡓሙྜ࡛ࡶ H ࡜ࡈࡃࢃࡎ࠿ࡔࡗࡓࠋࡇࡢ⤖ᯝࡣ㠀ඹᙺᛶࡢࢳ࣮࢜ࣛࢺ㓄఩Ꮚ㸦65㸧࡛ಖㆤࡉࢀࡓ $X 65  ࢡࣛࢫࢱ࣮࡟࠾ࡅ
ࡿඛ⾜◊✲ࡢ⤖ᯝ࡜ྠᵝ࡛࠶ࡾࠊ௒ᅇほ ࡋࡓ㓄఩Ꮚຠᯝࡣ ʌ ඹᙺ࡟ࡼࡿඹ㬆ຠᯝࡼࡾࡶ✵㛫ࡲࡓࡣ⤖ྜࢆ௓ࡋࡓㄏ㉳ຠᯝ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ

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࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋMAAs ࡢ⣸እ⥺㜵ᚚ⬟ࢆࣄ࣮࣐ࣗࣥ࣊ࣝࢫࢣ࢔࡟ᛂ⏝ࡍࡿᒎ㛤ࡶ㏆ᖺὀ┠ࡉࢀ࡚࠾ࡾࠊ
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࢜ࣥ໬ࡀ㏣㊧ྍ⬟࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࠊࡲࡓࠊ࢖࢜ࣥ໬๓ᚋࡢ≧ែࡀ⮬⏤࢚ࢿࣝࢠ࣮᭤㠃ୖࡢ㇂࡜࡞ࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡿ㸦ᅗ1㸧ࠋࣉࣟࢺࣥ⬺╔㒊఩ࢆኚ࠼ࡓࣂ࢚࣮ࣜࢩࣙࣥẖࡢ⮬⏤࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚⌧ᅾゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ

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Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ◊✲⤖ᯝࡢᡂᯝⓎ⾲ࢆ 2022 ᖺᗘෆ࡟ணᐃࡋ࡚࠸ࡿࠋ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ᅗ㸯㸬(a) MAAs ᶍᘧᅗࠊ(b) ࣉࣟࢺࣥ㓄࡞ࡋ఩ᩘኚ໬࡟ἢࡗࡓ⮬⏤࢚ࢿࣝࢠ࣮➼㧗⥺- 249 -

➨୍ཎ⌮ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁䛻䜘䜛㻌Ỉ⾲㠃䛾⮬⏤㻌㻻㻴䠈Ỉ⣲⤖ྜ㻌㻻㻴㻌䛾᣺ື⦆࿴䝎䜲䝘䝭䜽䝇䛾⌮ㄽ◊✲㻌
Theoretical Study of Vibrational Relaxation Dynamics of Free OH andHydrogen-Bonded OH at Air/Water Interface Via Ab initio Molecular
Dynamics Simulation‫▼ۑ‬ᒣ 㐩ஓ  ி⏣ ዉὠᐇ㸦ᐩᒣ኱ᏛᏛ⾡◊✲㒊ᕤᏛ⣔㸧◊✲┠ⓗࠊෆᐜ
Ỉ⾲㠃࡛Ỉ⣲⤖ྜࡋ࡚࠸࡞࠸⮬⏤ )UHH 2+㸪࠶ࡿ࠸ࡣỈ⣲⤖ྜࡋ࡚࠸ࡿ+\GURJHQERQGHG +ERQGHG 2+ࡢ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࡢゎ᫂ࡣ㸪኱Ẽ໬Ꮫ཯ᛂ㸪⏕య཯ᛂ࡞࡝ከࡃࡢ໬Ꮫ཯ᛂ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿୖ࡛㔜せ࡞▱ぢࢆ୚࠼ࡿࠋ㏆ᖺ㸪⌮໬Ꮫ◊✲ᡤࡢࢢ࣮ࣝࣉ࡟ࡼࡿ㉸㧗㏿᫬㛫ศゎ࣊ࢸࣟࢲ࢖᳨ࣥฟ᣺ື࿴࿘Ἴศග
ᐇ㦂࡟ࡼࡾ㸪Ỉ⾲㠃࡛ࡢ⮬⏤2+࡟ᑐࡍࡿ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࡢヲ⣽ࡀሗ࿌ࡉࢀࡓ>@ࠋᐇ㦂࡛ࡣ㸪⣧Ỉ࠾ࡼࡧ㔜Ỉ⣲⨨᥮ࡉࢀࡓỈࡀ⏝࠸ࡽࢀ㸪SXPSSUREHᐇ㦂࡟ࡼࡾ⮬⏤2+᣺ືࡢSRSXODWLRQ⦆࿴᫬㛫 7᫬㛫 ࡀࡑࢀࡒࢀࡢỈ࡛

ᐃࡉࢀࡓࠋ㦫ࡃ࡭ࡁࡇ࡜࡟㸪⣧Ỉ⾲㠃࡜㔜Ỉ⣲ᕼ㔘ࡉࢀࡓỈ⾲㠃࡛ࡢ7᫬㛫ࡣ㸪࡯ࡰྠࡌ್

ࢆ♧ࡍࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࣂࣝࢡࡢỈ⣲⤖ྜ2+᣺ື࡟ᑐࡋ࡚ࡣ㸪⣧Ỉ࡜㔜Ỉ⣲ᕼ㔘ࡉࢀࡓỈ࡛ࡣ㸪⦆࿴᫬ᐃᩘࡀᩘಸ␗࡞ࡿࡇ࡜ࡀ᪤࡟ሗ࿌ࡉࢀ࡚࠾ࡾ㸪ࡑࢀࡀศᏊ㛫࢝ࢵࣉࣜࣥࢢࡢ᭷↓࡟㉳ᅉࡍࡿࡇ࡜ࡶ㆟ㄽࡉࢀ࡚࠸ࡿࡀ㸪⮬⏤2+࡛ࡣ࡞ࡐࡑࡢ㐪࠸ࡀほࡉࢀ࡞࠸ࡢ࠿ศ࠿ࡗ࡚࠸࡞࠿ࡗࡓࠋࡉࡽ࡟⏺㠃࡛⮬⏤2+ࢆࡶࡗ࡚࠸ࡿỈࡢඹᙺ࡞2+ࡣ࡯࡜ࢇ࡝ࡢሙྜỈ⣲⤖ྜࡋ࡚࠸ࡿࡀ㸪ࡑࡢ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࡣࣂࣝࢡ2+ࡢ⦆࿴ࢲ࢖ࢼ࣑ࢡࢫ࡜ྠࡌ࡜⪃࠼࡚Ⰻ࠸ࡢ࠿᫂ࡽ࠿࡛ࡣ࡞࠿ࡗࡓࠋᮏ◊✲ࡣ㸪ศᏊ㛫࣏ࢸࣥࢩࣕࣝࡸศᏊෆ࣏
ࢸࣥࢩࣕࣝࡢࣔࢹࣝࣥࢢࢆᚲせ࡜ࡋ࡞࠸➨୍ཎ⌮ศᏊືຊᏛ DELQLWLRPROHFXODUG\QDPLFV$,0' ࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟ᇶ࡙ࡁ㸪⮬⏤2+࠾ࡼࡧỈ⣲⤖ྜ2+ࡢ᣺ື⦆࿴࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆヨࡳࡓࠋ᣺ື⦆࿴࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ⾜࠺ୖ࡛㸪ᵝࠎ࡞᣺ື࣮ࣔࢻ࡜ࡢ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡿ⦆࿴⤒㊰ࢆ≉ᐃࡍࡿᚲせࡀ࠶ࡿࠋ౛࠼ࡤ㸪୍ࡘࡢ+2ࡢ2+᣺ືࢆບ㉳ࡉࡏࡓሙྜ㸪ࡑࢀࡀ㸪ศᏊෆࡢ2+᣺ື࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾ
⦆࿴ࡍࡿࢣ࣮ࢫ㸪ศᏊෆࡢ+2+ኚゅ᣺ືࡢಸ㡢࡜ࡢ㠀ㄪ࿴࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾ⦆࿴ࡍࡿࢣ࣮ࢫ㸪ศᏊ㛫ࡢ
2+᣺ື࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾ⦆࿴ࡍࡿࢣ࣮ࢫ㸪࠶ࡿ࠸ࡣࡉࡽ࡟2+⤖ྜࡢ෌㓄ྥຠᯝ࡟ࡼࡿ⦆࿴࡞࡝㸪」ᩘࡢ
⦆࿴⤒㊰ࡀ⪃࠼ࡽࢀࡿࠋࡇࢀࢆ⣧Ỉ⣔ +2 ࡜㔜Ỉ⣲ᕼ㔘Ỉ⣔ +'2LQ'2 ࡟ᑐࡋ࡚᣺ື⤒㊰ࡢ⦆࿴㏿ᗘࢆィ⟬ࡍࡿࠋ᪉ἲ࡜ࡋ࡚ࡣ㸪ບ㉳ࡍࡿ2+᣺ື࡟㐠ື࢚ࢿࣝࢠ࣮ࢆ୚࠼㠀ᖹ⾮$,0'ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺஦࡟ࡼࡾ⦆࿴㏿ᗘࡢ᫬ᐃᩘ 7᫬㛫 ࢆ⟬ฟࡍࡿࠋୖグࡢ⦆࿴⤒㊰ࢆಶู࡟ィ⟬ࡍࡿࡓࡵ࡟㸪ὀ┠ࡍࡿ᣺ື࣮ࣔ
ࢻ௨እࡢ᣺ື㐠ື࡟ᣊ᮰ࢆ࠿ࡅࡿࡇ࡜࡟ࡼࡾ㸪ಶࠎࡢ᣺ື⦆࿴࣮ࣔࢻࡢࡳࢆྍ⬟࡟ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⾜࠺ࠋ௒ᅇࡢሗ࿌࡛ࡣ㸪⣬㠃ࡢ㒔ྜୖ㸪⏺㠃࡟࠾ࡅࡿ⮬⏤2+ࡢ⤖ᯝ>@ࡢࡳ↔Ⅼࢆ࠶࡚ࡿࠋࣂࣝࢡ࡛ࡢỈ⣲⤖ྜ2+ࡢ⤖ᯝ࡟㛵ࡋ࡚ࡣ㸪ㄽᩥ>@ࢆཧ↷ࡉࢀࡓ࠸ࠋ  ◊✲᪉ἲࠊィ⟬᪉ἲ$,0'ィ⟬࡟ࡣ&3.ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓࠋ')7ィ⟬࡟ࡣ*ULPPH'⿵ṇࢆ⏝࠸ࡓ%/<3ỗ㛵ᩘࢆ⏝࠸ࡓࠋ*7+ᨃ࣏ࢸࣥࢩࣕࣝࠊ7=93ᇶᗏ㛵ᩘࢆ⏝࠸ࠊᖹ㠃Ἴ࢝ࢵࢺ࢜ࣇ㊥㞳ࢆ5\࡜ࡋࡓࠋಶࡢỈศ- 250 -

Ꮚࢆ⏝࠸࡚ࢫࣛࣈ≧ࡢᾮ⭷ࢆసᡂࡋࡓࠋึᮇᵓ㐀ࡣ3DFNPROࣃࢵࢣ࣮ࢪ࡟ࡼࡾྂ඾ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝ࡗ
࡚ᖹ⾮໬ࡉࡿࡇ࡜࡟ࡼࡾసᡂࡋࡓࠋࡑࢀࢆࡉࡽ࡟$,0'ィ⟬࡛SV⛬ᗘᖹ⾮໬ࡉࡏࠊࡑࡢᚋ௵ពࡢ⮬⏤2+᣺ືࢆບ㉳ࡉࡏ㠀ᖹ⾮0'ィ⟬ࢆ⾜࠺஦࡟ࡼࡾ᣺ື⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒࡋࡓࠋ



◊✲ᡂᯝ

ᅗ㸯࡟㸪Ỉ⾲㠃࡟࠾ࡅࡿບ㉳⮬⏤2+ࡢ᣺ື࢚ࢿࣝࢠ࣮⦆࿴⤒㊰ࡢᶍᘧᅗࢆ♧ࡍࠋࡇࡇ࡛㸪ࡇࢀࡲ࡛ࡢ◊✲࡛୺࡟⪃࠼ࡽࢀ࡚ࡁࡓ⮬⏤2+᣺ືࡢ⦆࿴⤒㊰ࡣ㸱ࡘᏑᅾࡍࡿࠋ➨୍࡟ບ㉳⮬⏤2+᣺ື࡜ࡑࡢ∦ഃࡢ2+ ඹ
ᙺ2+ ࡜ࡢศᏊෆ᣺ື࢝ࢵࣉࣜࣥࢢ 6WUHWFKFRXSOLQJ ࡢ⤒㊰ࡀ⪃࠼ࡽࢀࡿࠋ➨஧࡟ບ㉳⮬⏤2+᣺ື࡜ኚゅ᣺ືࡢ㸰ಸ㡢࡜ࡢศᏊෆ࢝ࢵࣉࣜࣥࢢ EHQGFRXSOLQJ ࡢ⤒㊰ࡀ⪃࠼ࡽࢀࡿࠋ➨୕࡟⮬⏤2+ࡢ෌㓄ྥ
UHRULHQWDWLRQ ࡟ࡼࡿ࢚ࢿࣝࢠ࣮⦆࿴
⤒㊰ࡀ⪃࠼ࡽࢀ
ࡿࠋࡇࢀࡽ㸱ࡘࡢ⦆࿴⤒㊰ࡀ࡝ࢀࡃ
ࡽ࠸ࡢ๭ྜ࡛⮬⏤2+࢚ࢿࣝࢠ࣮⦆࿴
࡟ຠࡃࡢ࠿ࢆ᫂ࡽ
࠿࡟ࡍࡿࡢࡀࡇࡇ
࡛ࡢ┠ⓗ࡛࠶ࡿࠋ
ࡣࡌࡵ࡟㸪ศᏊ

ᅗບ㉳⮬⏤ 2+ ࡢ᣺ື࢚ࢿࣝࢠ࣮⦆࿴⤒㊰ࡢᶍᘧᅗࠋ

࡟඲ࡃᣊ᮰ࢆ࠿ࡅ
ࡿࡇ࡜࡞ࡃບ㉳2+᣺ືࡀ࡝ࡢ⛬ᗘࡢ᫬ᐃᩘ࡛⦆࿴ࡍࡿ࠿ࢆィ⟬ࡋ㸪ᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓ ᅗ ࠋᐇ㦂࡛ࡣ㸪⣧Ỉ⣔࡜㔜Ỉ⣲ᕼ㔘⣔࡛࡯࡜ࢇ࡝⦆࿴㏿ᗘࡀኚ໬ࡋ
࡞࠿ࡗࡓࡀ㸪ࡑࡢഴྥࡀ$,0'ィ
⟬⤖ᯝ࡟࠾࠸࡚ࡶ෌⌧ࡉࢀࡓࠋࡇࡢ⤖ᯝࡣ㸪⮬⏤2+ࡢ᣺ື࢚ࢿ
ࣝࢠ࣮⦆࿴࡟ࡣྠ఩యຠᯝࡀぢ࠿ࡅୖ࡯࡜ࢇ࡝Ꮡᅾࡋ࡞࠸஦ࢆ
ព࿡ࡋ࡚࠸ࡿࠋᅗ㸯ࡢ⦆࿴⤒㊰
ࡢ୰࡛㸪VWUHWFKFRXSOLQJ࡜EHQGᅗᐇ㦂࡜ $,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾ࡅࡿບ㉳⮬⏤2+ ࢚ࢿࣝࢠ࣮ࡢ᫬㛫Ⓨᒎ

- 251 -FRXSOLQJࡣྠ఩యຠᯝࡢᙳ㡪ࢆཷࡅࡿࡣࡎ
࡛࠶ࡿࡀ㸪୍᪉࡛UHRULHQWDWLRQࡣྠ఩యຠ
ᯝࡢᙳ㡪ࢆཷࡅ࡞࠸ࠋࡑࡢࡓࡵ㸪㐣ཤࡢ◊✲࡛ࡣ㸪⮬⏤2+ࡢ᣺ື࢚ࢿࣝࢠ࣮⦆࿴
ࡣ୺࡟UHRULHQWDWLRQ࡟㉳ᅉࡍࡿࡶࡢ࡜⪃࠼ࡽࢀ࡚ࡁࡓ>@ࠋࡋ࠿ࡋ㸪௨ୗ࡛ㄝ᫂ࡍࡿ
ࡼ࠺࡟㸪௒ᅇࡢ$,0'ィ⟬࡛ࡣ㸪⣧Ỉ⣔࡛
ࡣ L VWUHWFKFRXSOLQJ࡜EHQGFRXSOLQJࡢ⦆࿴ࡀ↓ど࡛ࡁ࡞࠸ࡇ࡜㸪ࡉࡽ࡟㔜Ỉ⣲ᕼ㔘⣔࡛ࡣࡑࢀ࡜ྠ➼ࡢ᪂ࡓ࡞ LL ศᏊෆ᣺ື
࢝ࢵࣉࣜࣥࢢ EHQGVWUHWFKFRPELQDWLRQFRXSOLQJ ࡟ࡼࡿ⦆࿴⤒㊰ࡀᏑᅾࡍࡿࡇ࡜ࡀ
᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡽ L ࡜ LL ࡀ࡯ࡰྠࡌ⦆࿴㏿ᗘࢆ୚࠼ࡿࡓࡵ㸪ྠ఩యຠᯝࡀ
࡞࠸ࡼ࠺࡟ぢ࠼ࡿࡇ࡜ࡀᮏ◊✲࡛᫂ࡽ࠿࡟࡞ࡗࡓࠋᮏ◊✲࡛ࡣ࠸ࡃࡘ࠿ࡢ᣺ືࡢ⮬⏤ᗘ࡟ᣊ᮰᮲௳ࢆㄢࡍࡇ࡜࡟ࡼࡾ㸪⪃࠼ࡽࢀࡿ᣺ື⦆࿴⤒㊰ࡢ࢚ࢿࣝࢠ࣮㏿ᗘࢆ$,0'ࢩ
࣑࣮ࣗࣞࢩ࡛ࣙࣥぢ✚ࡶࡿࡇ࡜ࢆྍ⬟࡟ࡋࡓࠋ⣬㠃ࡢ㒔ྜୖ㸪ࡇࡢᣊ᮰࡟㛵ࡍࡿᅗ ⤖ᯝࡢヲ⣽ࡣㄽᩥ>@ࢆཧ↷ࡉࢀࡓ࠸ࠋࡇ

≧ែᐦᗘࠋࡇࡇ࡛㉥⥺ࡣບ㉳⮬⏤ 2+㟷⥺ࡣࡑࢀ࡜ඹᙺ

ࡇ࡛ࡣ⤖ᯝࡢᴫせࡢࡳࢆ㆟ㄽࡍࡿࠋᅗ࡟

࡞ 2+㸪⥳⥺ࡣ㸪ࡑࢀࡽ௨እࡢࡍ࡭࡚ࡢỈศᏊࡢ᣺ື≧ᣊ᮰ࢆ࠿ࡅ࡚࠸࡞࠸ሙྜࡢ⣧Ỉ⣔ ୖᅗ ࡜ែᐦᗘࢆ⾲ࡋ࡚࠸ࡿࠋ⣧Ỉ⣔ ୖᅗ ࡜㔜Ỉ⣲ᕼ㔘⣔ ୗᅗ ࡟࠾ࡅࡿ᣺ື

㔜Ỉ⣲ᕼ㔘⣔ ୗᅗ ࡟࠾ࡅࡿ᣺ື≧ែᐦᗘࢆ♧ࡍࠋᅗୖᅗࡼࡾ㸪⣧Ỉ⣔࡛ࡣ⮬⏤2+᣺ື⾲

$,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿບ㉳⮬⏤ 2+ ࡢ᣺ື⦆࿴⋡)UHH2+ ㉥⥺ ࡀ࠶ࡿ⛬ᗘඹᙺ2+ &RQM2+㟷⥺ ࡜࢝ࢵࣉࣝࡋ࡚࠸
ࡿࡇ࡜ࡀࢃ࠿ࡾ㸪ࡉࡽ࡟ FP࠶ࡓࡾࡢኚ
ゅ᣺ືࡢ㸰ಸ㡢࡜ࡢ࢝ࢵࣉࣜࣥࢢࡀ↓ど࡛ࡁ࡞࠸ࡇ࡜ࡶࢃ࠿ࡗࡓࠋ୍᪉࡛㸪㔜Ỉ⣲ᕼ㔘⣔ࡢᅗୗᅗࢆࡳࡿ࡜㸪⮬⏤2+᣺ື )UHH
2+ ㉥⥺ ࡣ௚ࡢ᣺ື⮬⏤ᗘ࡜࢝ࢵࣉࣝࡋ࡚࠸࡞࠸ࡼ࠺࡟ぢ࠼ࡿࡀ㸪⮬⏤2+ࡢඹᙺ2'᣺ືࡀFP࡟㸪+2'ኚゅ᣺ືࡀFP࡟᣺ືࣂࣥࢻࢆࡶࡘࡓࡵ㸪ࡑࢀࡽࡢ⤖ྜ㡢ࡀ⮬⏤2+᣺ືFP࡜ࡕࡻ࠺࡝࢝ࢵࣉ
ࣝࡍࡿ㛵ಀ࡟࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋᮏ◊✲࡛ぢ✚ࡶࡽࢀࡓບ㉳⮬⏤2+᣺ືࡢྛ⤒㊰࡬ࡢ⦆࿴⋡ࢆ⾲㸯࡟♧ࡍࠋ⣧Ỉ⣔ࡢVWUHWFKFRXSOLQJ࡜EHQGFRXSOLQJࡢྜィࡀ㸪ࡕࡻ࠺࡝㔜Ỉ⣲ᕼ㔘⣔ࡢVWUHWFKEHQGFRPELQDWLRQFRXSOLQJ࡜ྠ⛬ᗘࡢ⦆࿴⋡࡟࡞ࡿࡓࡵ㸪඲య࡜ࡋ࡚ྠ఩యຠᯝࡀ࡯࡜ࢇ࡝ぢ࠼࡞ࡃ࡞ࡿ஦ࡀᮏ◊✲ࡼࡾ᫂ࡽ- 252 -

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ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥᏛ఍࢔ࣥࢧࣥࣈࣝ1R  ୍⯡ㅮ₇㸸㧗ศᏊᏛ఍  ௳ࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍  ௳ࠊᣍᚅㅮ₇  ௳

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

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1-1 ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾ࡅࡿࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮⏺㠃ࡢ㟁Ⲵ⛣ື᭷ᶵⷧ⭷ኴ㝧㟁ụࡢගኚ᥮ຠ⋡ࡣࢩࣜࢥࣥ⣔↓ᶵኴ㝧㟁ụ࡟ẚ࡭࡚ගኚ᥮ຠ⋡ࡣప࠸ࡀࠊ㍍㔞࠿ࡘᰂ㌾ᛶࠊᏳ౯࡛࠶ࡿ฼Ⅼ࡟ࡼࡾࡑࡢỗ⏝ᛶࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾࠸࡚ࠊࢻࢼ࣮(D)ᒙ࡜
࢔ࢡࢭࣉࢱ࣮(A)ᒙࡢ⏺㠃࡛⏕ᡂࡍࡿ࢟ࣕࣜ࢔㟁Ꮚ࡜࣮࣍ࣝࡣບ㉳Ꮚࢆᙧᡂࡍࡿࠋ᭷ᶵⷧ⭷ኴ㝧㟁ụࡀຠ⋡ⓗ࡟㟁ὶ⏕ᡂࡍࡿࡓࡵ࡟ࡣࠊບ㉳Ꮚࡢศゎ࡜⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡢ㟁ᴟ࡬ࡢ⛣ືࢆಁ㐍ࡍࡿ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡀㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋᡃࠎࡣࠊࣂࣝࢡ࡬ࢸࣟ᥋ྜᆺࡢ᭷ᶵ⣔ኴ㝧㟁ụࡢኚ᥮ຠ⋡ྥୖࡢࡓࡵࠊD/A ⏺㠃࡟࠾࠸࡚ࠊ⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࠊࡑࡋ࡚ග࢚ࢿࣝࢠ࣮ኚ᥮࡟᭷ຠ࡟ാࡃ㉳ᅉᏊࡢゎ᫂ࢆ┠ᣦࡋ࡚ࡁࡓࠋ࢔ࢡࢭࣉࢱ࣮ศᏊ࡟ࣇ࣮ࣛࣞࣥᆺࢆ⏝࠸ࡓ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟ຍ࠼ࠊᑠศᏊࡸ࣏࣐࣮ࣜࢆ࢔ࢡࢭࣉ
ࢱ࣮࡜ࡋࡓࣀࣥࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟㛵ࡍࡿ◊✲ࡢ㐍Ṍࡀ┠ぬࡲࡋ࠸ࠋ୰࡛ࡶ࢔ࢡࢭࣉࢱ࣮ศᏊ
ࡢ୍㒊ࢆࣇࢵ⣲໬ྜ≀࡟⨨᥮ࡍࡿࡇ࡜࡟ࡼࡾࠊࣇࢵ⣲ᇶࡀ㟁Ꮚࢆᙉࡃᘬࡁฟࡋࢻࢼ࣮࠿ࡽ㞳ࢀ࡚㟁ὶࢆቑຍࡉࡏࡿ࡜࠸࠺ሗ࿌ࡀ࠶ࡿࠋࡇࡢࡼ࠺࡞ࣇࢵ⣲⨨᥮ࡣ࢔ࢡࢭࣉࢱ࣮ศᏊࡢࡳ࡞ࡽࡎࠊࢻࢼ࣮ศᏊ࡟ࡶ㐺⏝ࡉࢀ࡚࠾ࡾࠊኚ᥮ຠ⋡ࡢྥୖ࡟㔜せ࡞ᙺ๭ࢆ♧ࡋ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲ࡣࠊࣂࣝࢡ࣊ࢸࣟ᥋ྜᆺࡢ᭷ᶵ⣔ኴ㝧㟁ụࡢኚ᥮ຠ⋡ྥୖࢆ┠ⓗ࡜ࡋ࡚ࠊࢻࢼ࣮㸭࢔ࢡࢭࣉࢱ࣮⏺㠃࡟࠾ࡅࡿ྾཰ࢫ࣌ࢡࢺࣝࠊHOMO-LUMO ࣂࣥࢻࢠࣕࢵࣉࠊ㟁Ⲵ⛣ື࠿ࡽ㟁Ⲵゎ㞳࡬ࡢ࢚ࢿࣝࢠ࣮ࣂࣜ࢔ࡢほⅬ࠿ࡽࣇࢵ⣲⨨᥮࡟࠾ࡅࡿ⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡢ
࣓࢝ࢽࢬ࣒ࢆ⪃ᐹࡍࡿࠋ
1-2 Na ࢖࢜ࣥ㟁ụ㈇ᴟᮦᩱ Sn ࡟࠾ࡅࡿ඘ᨺ㟁㐣⛬࡜ NMR ࡢ⌮ㄽⓗ◊✲Li ࢖࢜ࣥ㟁ụࡣࠊ඘㟁ࡢ㏿ࡉࡸ⪏⏝ᖺᩘ࡟ඃࢀ᭷ຠ࡟ά⏝ࡉࢀ࡚࠸ࡿࡀࠊLi ࡀ᭷㝈㈨※࡛࠶ࡿࡇ࡜࠿ࡽ஧
ḟ㟁ụࡢ㟂せ࡬ࡢᏳᐃࡋࡓ౪⤥࡟ㄢ㢟ࢆᣢࡗ࡚࠸ࡿࠋࡑࡇ࡛ Na ࢖࢜ࣥ㟁ụࡀὀ┠ࡉࢀ࡚࠸ࡿࠋNa ࡣ㈨※㔞ࡶ㇏ᐩ࡛࠶ࡿࡓࡵࠊᏳᐃࡋࡓ౪⤥ࠊపࢥࢫࢺࡀᮃࡲࢀࡿࠋࡇࢀࡲ࡛ Na ࢖࢜ࣥ㟁ụࡢᵓᡂせ⣲ࡢ࠺ࡕṇᴟᮦᩱ࡟ࡘ࠸࡚ᗈࡃ◊✲ࡉࢀ࡚࠸ࡿࡀࠊ㈇ᴟᮦᩱ࡟ࡘ࠸࡚ࡢ◊✲౛ࡣᑡ࡞࠸ࠋ㏆ᖺࠊSn ࡣ Na ࡜ྜ㔠໬ࡍࡿࡇ࡜࡛᭱኱ Na15Sn4 ࡲ࡛ࡢ⤌ᡂẚࡢ Na ࢆྲྀࡾ⤌ࡴࡇ࡜ࡀ࡛ࡁࡿࡓࡵࠊNa ࢖࢜ࣥ㟁ụ㈇ᴟᮦᩱ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸
ࡿࠋ⌧ᅾࡲ࡛ࠊᐇ⏝໬࡟ࡴࡅ࡚ Na-Sn ⣔ࡢ sodiation/desodiation 㐣⛬࡟࠾ࡅࡿᵓ㐀ኚ໬ࡢᵝᏊࡀᐇ㦂࣭ィ⟬ࡢ୧᪉㠃࠿ࡽᵝࠎ࡞◊✲ࡀ࡞ࡉࢀ࡚࠾ࡾࠊ≉࡟ Na-Sn ⣔ࡢ඘㟁᭤⥺࡟࠾࠸࡚」ᩘࡢࣉࣛࢺ࣮ࡀᏑᅾࡋ࡚࠸ࡿࡇ
࡜ࡀሗ࿌ࡉࢀࡓࠋᮏ◊✲࡛ࡣࠊNa ࢖࢜ࣥ㟁ụࡢ㈇ᴟᮦᩱ Sn ࡟ࡘ࠸࡚ࠊ඘ᨺ㟁㐣⛬࡟࠾ࡅࡿᵓ㐀ኚ໬ࡸ඘ᨺ
㟁᭤⥺ࠊࡲࡓ 23Na NMR ໬Ꮫࢩࣇࢺ≀ᛶࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ࡼࡾࠊSn ㈇ᴟ࡟࠾ࡅࡿ඘ᨺ㟁㐣⛬ࡢᚤ⣽࡞࣓࢝ࢽࢬ࣒ゎ᫂ࢆ┠ⓗ࡜ࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ

2-1 ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾ࡅࡿࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮⏺㠃ࡢ㟁Ⲵ⛣ືᑐ㇟≀㉁࡟ࡣࠊITIC ࡢࡼ࠺࡞ࣀࣥࣇ࣮ࣛࣞࣥᆺࡢ p ᆺ᭷ᶵ㧗ศᏊ༙ᑟయ࡜ࡋ࡚ࢻࢼ࣮ᮦᩱ࡛࠶ࡿࠋィ⟬ᡭ
ἲ࡟ࡣࠊGaussian 16 ࢆ⏝࠸࡚ບ㉳≧ែィ⟬ࢆ⾜ࡗࡓࠋGaussian 16 ࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜ࡗࡓࠋNTz-Teh-FA
࡜ FNTz-Teh-FA ࡟ࡘ࠸࡚ࠊึᮇᵓ㐀ࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲࢆ⏝࠸࡚ࠊࡇࢀࡽࡢᵓ㐀ࡢບ㉳≧ែィ⟬ࢆ⾜ࡗࡓࠋḟ࡟ࠊNTz-Teh-FA / PCPD-TBT ࡢ㠀ࣇ࣮ࣛࣞࣥᆺ」ྜయ࡜ FNTz-Teh-FA / PCPD-TBTࡢࣇࢵ⣲໬㠀ࣇ࣮ࣛࣞࣥᆺ」ྜయ࡟ࡘ࠸࡚ᇶᗏ≧ែࡢ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮᭱Ᏻᐃᵓ㐀ࢆ᥈⣴ࡋࡓࠋࡑࡋ࡚ࠊ㠀ࣇ࣮ࣛࣞࣥᆺ」ྜయ࡜ࣇࢵ⣲໬㠀ࣇ࣮ࣛࣞࣥᆺ」ྜయ࡟ᑐࡋ࡚㟁Ꮚ⛣ື/ບ㉳࢚ࢿࣝࢠ࣮⛣ື(EET)ィ⟬ࠊ㟁Ⲵ⛣ື㔞࣭㟁Ⲵ⛣ື㊥㞳ࡢィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࣞ࣋ࣝࡣ ωB97XD/6-31G(d)࡛࠶ࡿࠋ
2-2 Na ࢖࢜ࣥ㟁ụ㈇ᴟᮦᩱ Sn ࡟࠾ࡅࡿ඘ᨺ㟁㐣⛬࡜ NMR ࡢ⌮ㄽⓗ◊✲඘ᨺ㟁㐣⛬࡟࠾࠸࡚ࡑࡢᵓ㐀ࡢᏑᅾࡀᐇ㦂ⓗ࡟ண ࡉࢀ࡚࠸ࡿ⤌ᡂࡸࠊ┦ᅗ࡟࠾࠸࡚Ᏻᐃ┦࡜ࡉࢀ࡚࠸ࡿ
ᵓ㐀௨እࡢ⤌ᡂ࡟ࡘ࠸࡚ࠊ⤌ᡂẚࡢ␗࡞ࡿᵝࠎ࡞ Na-Sn ⣔࡟ࡘ࠸࡚ࠊࡑࡢᵓ㐀ࢆ DFT ィ⟬࡟ࡼࡗ࡚ồࡵࡿணᐃ࡛࠶ࡿࠋᵓ㐀ࡢ Na-Sn ⣔ࡢྛᵓ㐀ࡢ formation energy ࢆ⟬ฟࠊNa-Sn ⣔ࡢᵓ㐀ኚ໬࡟࠾ࡅࡿ Na/Sn ⤌ᡂẚ࡟

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ᑐࡍࡿ㟁఩ࡢኚ໬ࢆ᥎⟬ࡍࡿࠋຍ࠼࡚岝Na-Sn ⣔岝Na ༢యࠊNaCl ࡟ࡘ࠸࡚ࠊ໬Ꮫࢩࣇࢺࢸࣥࢯࣝࡢィ⟬ࢆ⾜࠺ࠋNa-Sn ⣔ࡢྛ⤌ᡂ࡟࠾ࡅࡿࠊ⊂❧࡞ Na ࢧ࢖ࢺᩘ࡟ᑐᛂࡍࡿᩘࡢ㐽ⶸຠᯝ್ࠊNaCl ⤖ᬗࢆࣞࣇ࢓ࣞࣥࢫ
࡜ࡋ࡚岝23Na Chemical Shift ࢆ⌮ㄽⓗ࡟⟬ฟࡍࡿࠋィ⟬ᡭἲ࡟ࡣࠊGaussian 16 ࢆ⏝࠸ࡿࠋ



◊✲ᡂᯝ

3-1 ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾ࡅࡿࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮⏺㠃ࡢ㟁Ⲵ⛣ື
Face-on ᵓ㐀ࢆ᭷ࡍࡿࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮」ྜయࡢᵓ㐀ࡢ྾཰ࢫ࣌ࢡࢺࣝࡢ㛗Ἴ㛗ഃࡢᙉ࠸᣺ືᏊᙉᗘ࡟
ࡘ࠸࡚ AƂA 㑄⛣ࡀከࡃ࢔ࢡࢭࣉࢱ࣮⏤᮶࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ㟁Ⲵ⛣ື㔞࣭㟁Ⲵ⛣ື㊥㞳ィ⟬࡟ࡼࡾࠊບ
㉳Ꮚ≧ែ࠿ࡽ㟁Ⲵศ㞳≧ែ฿㐩ࡢ⤒㊰࡟ࡘ࠸࡚⪃ᐹࢆ⾜ࡗࡓࠋ㠀ࣇࢵ⣲໬」ྜయ࡜ࣇࢵ⣲໬」ྜయࢆẚ㍑ࡋ
ࡓ࡜ࡇࢁࠊ㛗Ἴ㛗ഃࡢ㟁Ⲵ⛣ື㔞(‫ ݍ‬஼் )࣭㟁Ⲵ⛣ື㊥㞳(݀ ஼் )࡛ࠊ643nm ࡛ࡣ‫ ݍ‬஼் ࡀ 0.449ࠊ݀ ஼் ࡀ 0.215 ቑຍࡋࠊൎ ͹ͷͲ࡛ࡣࠊ‫ ݍ‬஼் ࡀ 0.101ࠊ݀ ஼் ࡀ 0.093 ቑຍࡋࡓࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡋࡓࡀࡗ࡚ࠊ࢔ࢡࢭࣉࢱ࣮ࡢᙳ㡪ࡀᙉ࠸㛗Ἴ㛗ഃ࡛ບ㉳Ꮚゎ㞳ࡢ㊥㞳ࡀ㛗ࡃ࡞ࡾࠊ㟁Ⲵศ㞳ࡋࡸࡍ࠸࣍ࢵࢺࣉࣟࢭࢫࡢഴྥࡀᙉ࠸ග྾཰ࡀ⪃࠼ࡽࢀࡿࠋḟ࡟ EET ࢝ࢵࣉࣜࣥࢢܸ ୉୉୘ ൌ ܸ ୡ୭୳୪ ൅ ܸ ୣ୶ୡ୦ ൅ ܸ ୭୴୪୮ ࡼࡾࠊࡇࡢ⣔࡛ࡣ Förster ᶵᵓ࡟ࡼࡾࢡ࣮ࣟࣥ┦஫స⏝ࡀ EET ࢝ࢵࣉࣜࣥࢢࢆỴᐃࡋࡓࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௨ୖࡢࡇ࡜ࡼࡾࠊບ㉳Ꮚࡢࢡ࣮ࣟࣥຊࡀᙅࡵࡽࢀࠊ
㟁Ꮚ㸫ṇᏍࡢ㊥㞳ࡀ㛗ࡃ࡞ࡾ㟁Ⲵศ㞳ࡋࡸࡍ࠸ບ㉳Ꮚࡀ⏕ᡂࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊEET ࡀྥୖࡋࡓ
ࡇ࡜࠿ࡽࠊ㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢග㟁ኚ᥮ຠ⋡ྥୖࡢ㉳ᅉᏊ࡛࠶ࡿ ୗେ ࡀྥୖࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ
3-2 Na ࢖࢜ࣥ㟁ụ㈇ᴟᮦᩱ Sn ࡟࠾ࡅࡿ඘ᨺ㟁㐣⛬࡜ NMR ࡢ⌮ㄽⓗ◊✲(Na)n (n = 20, 40)ࡢᏳᐃᵓ㐀࡜ NMR ゎᯒࢆ⾜ࡗࡓࠋn = 20, 40 ࡢᏳᐃᵓ㐀ࡣ࡜ࡶ࡟୕ゅ㠃࠿ࡽᵓᡂࡉࢀࡿᑐ
⛠ᛶࡢ㧗࠸❧యᵓ㐀࡜࡞ࡗࡓࠋNMR ໬Ꮫࢩࣇࢺ್ࡣࠊ࡜ࡶ࡟ 600 ppm ㏆ഐ࡟ࣆ࣮ࢡࢆᣢࡕࠊ600 – 700 ppm
࡟࠿ࡅ࡚ࠊ」ᩘࡢࢫ࣌ࢡࢺࣝࡀぢࡽࢀࡓࠋ600 ppm ㏆ഐࡢࣆ࣮ࢡࡣ Na ࢡࣛࢫࢱ࣮ࡢ⾲㠃ࢆᵓᡂࡍࡿ Na ཎᏊ࠿ࡽࡢᐤ୚࡛࠶ࡾࠊ㧗 ppm ഃࡢࢫ࣌ࢡࢺࣝࡣࢡࣛࢫࢱ࣮ෆẆࡢ Na ཎᏊ࠿ࡽࡢᐤ୚࡟ࡼࡿࡶࡢ࡛࠶ࡗࡓࠋࡲ
ࡓࠊ᭱እẆ 3s ㌶㐨ࡢ㟁Ꮚᐦᗘ࡜໬Ꮫࢩࣇࢺ್࡜ࡢ┦㛵ࡣᚓࡽࢀ࡞࠿ࡗࡓࡀࠊࢡࣛࢫࢱ࣮ෆẆࡢ Na ཎᏊ࡟࠾ࡅࡿ 3p ㌶㐨ࡢ㟁Ꮚᐦᗘࡀቑຍࡍࡿ࡜࠸࠺ഴྥࡀぢࡽࢀࡓࠋࡇࡢ࡜ࡁࠊHOMO ࡣࢡࣛࢫࢱ࣮ෆ㒊࡟㟁Ꮚࡀᒁᅾࡋࠊࢡࣛࢫࢱ࣮⾲㠃࡟⠇ࢆᣢࡘ sp ΰᡂ㌶㐨ศᕸࢆ♧ࡋࡓࡇ࡜࠿ࡽࠊࢡࣛࢫࢱ࣮ෆẆࢆᵓᡂࡍࡿ Na ཎᏊࡢ
NMR ໬Ꮫࢩࣇࢺ್ࡀ㧗 ppm ࡬ࢩࣇࢺࡋࡓ࡜⪃࠼ࡽࢀࡿࠋḟ࡟ࠊ┦ᑐㄽຠᯝࢆྵࡴ NMR ゎᯒࢆ⾜ࡗࡓࠋࡑࡢ
⤖ᯝࠊn = 20 ࡟࠾࠸࡚ࠊࢫࣆࣥ㌶㐨┦ᑐㄽࢆྵࡴሙྜࠊ600 ppm ㏆ഐࡢࢩࣇࢺ್ࡀ඲యⓗ࡟㧗 ppm ࡬ࢩࣇࢺࡋࠊࡑࡢ໬Ꮫࢩࣇࢺ್ࡣࢡࣛࢫࢱ࣮⾲㠃࡟఩⨨ࡍࡿ Na ཎᏊ࡟ࡼࡿᐤ୚࡛࠶ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊࢡࣛࢫࢱ࣮
ࢧ࢖ࢬቑ኱࡟క࠸ࠊࢫࣆࣥ㌶㐨┦ᑐㄽ࡟ࡼࡿᙳ㡪ࡢ⪃៖ࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

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‫ ۻ‬S. Ikeyama, N. Ohta, K. Yamashita, A. Muraoka, Pacifichem2021: 2021. ‫ ۻ‬A. Suzaki, A. Muraoka, K. Yamashita,
Pacifichem2021: 2021. ‫ ۻ‬A. Anzai, Y. Kurosaki, R. Nakanishi, M. Saeki, H. Ohba, A. Muraoka, Pacifichem2021: 2021.
‫ ۻ‬S. Ikeyama, N. Ohta, K. Yamashita, A. Muraoka, APS Marchmeeting 2021, Bull. Am. Phys. Soc: 2021. ‫ ۻ‬A.
Suzaki, A. Muraoka, K. Yamashita, APS Marchmeeting 2021, Bull. Am. Phys. Soc: 2021. ‫ ۻ‬A. Anzai, Y. Kurosaki, R.
Nakanishi, M. Saeki, H. Ohba, A. Muraoka, APS Marchmeeting 2021. ‫ ۻ‬A. Muraoka, EU-Japan workshop on HPCbased material sciences: 1-2. 2021. ‫ ۻ‬ᮧᒸᱻ, ➨ 21 ᅇ኱ࡘࡃࡤ≀⌮໬Ꮫࢭ࣑ࢼ࣮: 2021. ‫ ۻ‬ụᒣ, ኴ⏣, ❧ⰼ, ᒣୗ, ᮧᒸ, ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨᖺ఍: 2021. ‫ ۻ‬Ᏻ㰻, 㯮ᓮ, ୰す, బ఑, ኱ሙ, ᮧᒸ,᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨᖺ఍: 2021. ‫ ۻ‬ᑑᓮ, ᮧᒸ, ᒣୗ, ➨ 11 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2021: 2021
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Muraoka, K. Gotoh, K. Yamashita, Neural Network to Predict 23Na NMR Spectra of NanClusters,2022 (Submitted).

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ᩘ 8 ࡢேᕤ⢾࢔ࣝࢥ࣮ࣝ㸦C8gal㸧ࢆィ⟬⛉Ꮫⓗ࡟ᵓ⠏ࡋ⵳⇕ᐦᗘࢆィ⟬ࡋࡓࠋ
1.3 ࣍࢘⣲ࢻ࣮ࣉࢲ࢖ࣖࣔࣥࢻ㟁ᴟ࡟ࡼࡿ஧㓟໬Ⅳ⣲㑏ඖ཯ᛂࡢ୰㛫≧ែࡢゎᯒ஧㓟໬Ⅳ⣲㸦CO2㸧ࢆࢠ㓟࡞࡝ࡢ⇞ᩱศᏊ࡬࡜ኚ᥮ࡍࡿᢏ⾡ࡢᵓ⠏ࡣ࣮࢝࣎ࣥࢽ࣮ࣗࢺࣛࣝࡢᐇ⌧࡟ྥࡅࡓ㔜せ࡞㐣⛬࡛࠶ࡿࠋຠ⋡ⓗ࡞ CO2 㑏ඖ཯ᛂ㸦CO2RR㸧ࡢ㐩ᡂ࡟ྥࡅ࡚ᵝࠎ࡞᪉ἲࡀ◊✲ࡉࢀ࡚࠸ࡿ୰࡛ࠊ㟁Ẽ໬Ꮫⓗ࡞ CO2RR ࡣ᭷ຠ࡞࢔ࣉ࣮ࣟࢳ࡛࠶ࡿࠋ≉࡟ࠊ࣍࢘⣲ࢻ࣮ࣉࢲ࢖ࣖࣔࣥࢻ㸦BDD㸧㟁ᴟ࡟ࡼࡿ CO2RR
ࡣࠊ㧗࠸⏕ᡂ≀㑅ᢥᛶ࡜㟁ᴟᏳᐃᛶࢆ᭷ࡍࡿࡇ࡜࡛ὀ┠ࡉࢀ࡚࠸ࡿࠋ᭱㏆ࠊᮭࡽࡣ BDD 㟁ᴟ⾲㠃࡛㉳ࡇࡿ
CO2RR ࡢึᮇ㐣⛬࡟⌧ࢀࡿ୰㛫≧ែ࡜ࡋ࡚༢ᗙⅣ㓟ሷ࡜࢝ࣝ࣎࢟ࢩࣝᇶࡢᏑᅾࢆᐇ㦂ⓗ࡟♧ࡋࡓࠋᮏ◊✲࡛ࡣࠊࡑࡢ⌮ㄽⓗᨭᣢࢆᚓࡿࡓࡵ࡟ࠊBDD 㟁ᴟ⾲㠃ୖࡢࡑࢀࡽ୰㛫≧ែࡢᏳᐃᛶࢆホ౯ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲࢸ࣮࣐(1)࡛ࡣ VASP ࢆ฼⏝ࡋࡓ PBE ỗ㛵ᩘ࡟ࡼࡿ㟁Ꮚ≧ែィ⟬ࢆ⾜࠸ࠊGRRM ࣉࣟࢢ࣒ࣛ࡟ࡼࡗ࡚Ᏻᐃ

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ᵓ㐀ࡸ㑄⛣≧ែࡢ᥈⣴ࢆ⾜ࡗࡓࠋࢸ࣮࣐(2)࡜(3)࡛ࡣ Quantum Espresso ࢆ౑⏝ࡋࡓ BLYP ỗ㛵ᩘ࡟ࡼࡿ㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋ≉࡟ࠊࢸ࣮࣐(2)ࡢ⤖ᬗᵓ㐀ண ࡣ⊂⮬࡟ಟṇࡋࡓ UPACK ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊMD ィ⟬ࡣ Gromacs ࢆ౑⏝ࡋ࡚ᐇ᪋ࡋࡓࠋࢸ࣮࣐(3)ࡢ BDD 㟁ᴟ⾲㠃ࡢࣔࢹࣝ໬ࡣ㟁ᴟ㟁఩࡜⁐፹ຠᯝࢆ⪃៖ࡍࡿࡓࡵ ESM-RISM ἲࢆ౑⏝ࡋࡓࠋ



◊✲ᡂᯝ
3.1 ⓑ㔠ࢡࣛࢫࢱ࣮ゐ፹ࡢ⥙⨶ⓗᵓ㐀᥈⣴Ẽ┦୰ࡢ Pt4 ࡢᵓ㐀᥈⣴ࢆ⾜ࡗࡓ⤖ᯝࠊ6 ࡘࡢᒁᡤᏳᐃᵓ㐀࡜ࡑࢀࡽࢆࡘ࡞ࡄ 6 ࡘࡢ㑄⛣≧ែࡀᚓࡽࢀࡓࠋ

Ᏻᐃᵓ㐀ࡣ⣙ 0.8 eV ࡢ⠊ᅖ࡟Ꮡᅾࡋࠊᵓ㐀㛫㑄⛣ࡢࣂࣜ࢔ࡢ㧗ࡉࡣ⣙ 0.2 - 0.7 eV ࡢ⠊ᅖ࡛࠶ࡗࡓࠋࡇࡢ⤖ᯝ࠿ࡽࠊ1 ᅇࡢᵓ㐀㑄⛣ࡢ᫬㛫ࢫࢣ࣮ࣝࡣ㑄⛣≧ែ⌮ㄽ࡟ᇶ࡙ࡃ࡜ࢼࣀ⛊࠿ࡽ࣐࢖ࢡࣟ⛊࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗ
ࡓࠋSTEM ᐇ㦂࡛ࡣ⛊ࢫࢣ࣮࡛ࣝࡢᵓ㐀᫬⣔ิኚ໬ࢆ♧ࡋ࡚࠸ࡿࡓࡵࠊࡑࢀࡽࡢᵓ㐀ࢧࣥࣉࣝิࡣ᭷ព࡞᫬
㛫᝟ሗࢆᣢࡓ࡞࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊᏳᐃᵓ㐀ࡢ㛫࡛ d ㌶㐨୰ᚰࡀ 0.7 eV ࡶᕪࡀฟࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣゐ፹άᛶࡢᵓ㐀౫Ꮡᛶ࡟㛵㐃ࡋ࡚ࡃࡿ࡜⪃࠼࡚࠸ࡿࠋ⌧ᅾࠊࢢࣛࣇ࢙ࣥᇶ┙ୖ࡛ࡢ⥙⨶ⓗᵓ㐀᥈⣴ࢆ⾜࠸ࠊࡼࡾᐇ㦂࡟㏆࠸᮲௳࡛ࡢẚ㍑࠾ࡼࡧᇶᯈࡢᙳ㡪ࡢゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ
3.2 ᭷ᶵ₯⇕⵳⇕ᮦᩱࡢศᏊࢹࢨ࢖ࣥ
ࡲࡎࠊ࢞ࣛࢡࢳࢺ࣮ࣝ⣔Ⅳ⣲ᩘ 8 ࡢேᕤ⢾࢔ࣝࢥ࣮ࣝ㸦C8gal㸧ࡢ⤖ᬗᵓ㐀ࢆணࡋࡓࠋ✵㛫⩌ Pbca ࡢ⤖ᬗ㸦C8gal_Pbca㸧ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟᭱ࡶᏳᐃ࡛࠶ࡗࡓࠋࡓࡔࠊP21/c ✵㛫⩌ࡢᵓ㐀㸦C8gal_P21/c㸧ࡶ࡯ࡰྠᵝ࡞Ᏻᐃᛶ㸦࢚ࢿࣝࢠ࣮ᕪࡣ 0.04 kcal/mol㸧࡛࠶ࡗࡓࡢ࡛ࠊࡑࡢ 2 ࡘࡢᵓ㐀࡛⵳⇕ᐦᗘࢆィ⟬ࡋࡓࠋࡑࡢ⤖ᯝ
ࡣࠊC8gal_Pbca ࡣ 276 kJ/kgࠊC8gal_P21/c ࡣ 269 kJ/kg ࡛࠶ࡾࠊ࢞ࣛࢡࢳࢺ࣮ࣝࢆ㗪ᆺ࡜ࡍࡿேᕤ⢾࢔ࣝࢥ࣮ࣝࡣ₯⇕ⓗ࡟⵳⇕ᮦ࡜ࡋ࡚᭷⏝࡛࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࡢ⌮⏤࡟ࡘ࠸࡚ࡣ⌧ᅾゎᯒ୰࡛࠶ࡿࠋ
3.3 ࣍࢘⣲ࢻ࣮ࣉࢲ࢖ࣖࣔࣥࢻ㟁ᴟ࡟ࡼࡿ஧㓟໬Ⅳ⣲㑏ඖ཯ᛂࡢ୰㛫≧ែࡢゎᯒ
BDD 㟁ᴟ⾲㠃࡟࠶ࡿ༢ᗙⅣ㓟ሷ࡜࢝ࣝ࣎࢟ࢩࣝᇶࡢᏳᐃᛶࢆホ౯ࡋࡓ⤖ᯝࠊ࢝ࣝ࣎࢟ࢩࣝᇶࢆ᭷ࡍࡿ୰㛫≧ែࡀ༢ᗙⅣ㓟ሷࡼࡾ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟ 31 kcal/mol ࡶᏳᐃ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ⏕ᡂ≀࡜ࡋ࡚ࡢࢠ㓟࡜ BDD 㟁ᴟ⾲㠃࡟ࣄࢻࣟ࢟ࢩࣝᇶࡀṧࡗࡓ⤊≧ែ࡛ࡣ࢝ࣝ࣎࢟ࢩࣝᇶࡀᏑᅾࡍࡿ≧ែࡼࡾࡉࡽ࡟ 85
kcal/mol ࡶᏳᐃ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᚑࡗ࡚ࠊ༢ᗙⅣ㓟ሷ࡜࢝ࣝ࣎࢟ࢩࣝᇶࡀ୰㛫≧ែ࡜ࡋ࡚㡰࡟ฟ⌧ࡋࠊ᭱⤊ⓗ࡟ࢠ㓟ࢆ⏕ᡂࡍࡿ࡜࠸࠺㐣⛬ࡣⓎ⇕㐣⛬࡜࡞ࡾࠊᐇ㦂࡛♧၀ࡉࢀࡓ CO2RR ࡢึᮇ㐣⛬ࡢᶵᵓࡀ⌮ㄽⓗ࡟ᨭᣢࡉࢀࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬T. Inagaki and S. Saito ͆Hamiltonian Monte Carlo Method with Potential Scaling for Canonical Multimodal
Distributions and Relaxation Processes͇5th CJK Workshop on Theoretical and Computational Chemistry.

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬

T. Inagaki and S. Saito “Hybrid Monte Carlo method with potential scaling for sampling from the canonicalmultimodal distribution and imitating the relaxation process” J. Chem. Phys. 156, 104111 (2022).

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࢖࢜ࣥᛶᾮయ࡟࠾ࡅࡿ࢖࢜ࣥఏᑟ⋡ࠊෆ㒊⛣ືᗘࠊ࠾ࡼࡧ Haven ẚࡢໟᣓⓗ◊✲㸰㸸࢖࢜ࣥࢧ࢖ࢬ౫Ꮡᛶ
Comprehensive study on the ionic conductivity, internal mobility, andthe Haven ratio in ionic liquids: ionic size dependence‫ۑ‬኱㫽 ⠊࿴ ᕝ➃ ᾏ㒔 㜿㒊 ಇኴ  ಙኴ ᓧ ぢᕝ ె⃈㸦᪂₲኱Ꮫ⌮Ꮫ㒊  ྠ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉㸧
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ࡢ኱ࡁࡉࢆẚ㍑ࡍࡿᑻᗘ࡜ࡋ࡚ࡋࡤࡋࡤ㆟ㄽࡉࢀࡿࠋ+DYHQ ẚࡢ㉳※࠾ࡼࡧᣲືࡢ⌮ゎࡣ࢖࢜ࣥᛶᾮయࡢఏ
ᑟ⋡ࡢᮏ㉁࡟㛵ࢃࡿᇶ♏ⓗၥ㢟࡛࠶ࡿࡀࠊࡑࡢ⌮ゎࡣ࠸ࡲࡔᐃᛶⓗ⠊␪࡟␃ࡲࡗ࡚࠸ࡿ>@ࠋࡍ࡞ࢃࡕࠊ࢖࢜
ࣥఏᑟ⋡ࡸ +DYHQ ẚࢆṇ☜࡟ホ౯ࡋࠊࡑࢀࡽࢆᵓᡂࡍࡿྛ࢖࢜ࣥࡢኚ఩ࡢ┦㛵㡯ࡢᣲືࢆᐃ㔞ⓗ࡟ㄝ᫂ࡍࡿ
ࡇ࡜ࡀࡇࡢၥ㢟ࡢゎỴ࡟ࡘ࡞ࡀࡿࠋ
ᡃࠎࡣࡇࢀࡲ࡛ࠊ/HQQDUG-RQHV /- ⣔࡞࡝ࡢ༢⣧ᾮయࡢ㍺㏦ಀᩘ࡟ࡘ࠸࡚ࠊศᏊືຊᏛ 0' ἲ࡟ᇶ࡙ࡃィ⟬ᶵᐇ㦂࡟ࡼࡗ࡚≉ᐃࡢኚᩘࡢࡳࡢ౫Ꮡᛶࢆㄪ࡭ࡿࡇ࡜࡟ࡼࡗ࡚ࠊᅉᯝ㛵ಀ࡟ᇶ࡙ࡃྛ㍺㏦ಀᩘࡢᐃᘧ໬ࢆ
ヨࡳࠊ⼥Ⅼ࠿ࡽἛⅬ௜㏆ࡲ࡛ࡢᗘ㡿ᇦ࡟ᑐࡋ࡚⾲⌧ྍ⬟࡞ᘧࢆᚓ࡚ࡁࡓ>@ࠋ୍᪉ࠊ༢⣧࡞⁐⼥ሷࡢ௦⾲࡛࠶ࡿ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢᵓ㐀ࡸᛶ㉁ࡣࠊ⤒㦂ⓗ࡞ )XPL7RVL ࡢⅬ㟁Ⲵࣔࢹࣝ )70 ࡟ࡼࡗ࡚ẚ㍑ⓗⰋࡃグ㏙࡛ࡁࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ/- ⣔࡛ࡣཎᏊࢧ࢖ࢬࢆ୍⩏ⓗ࡟ᐃ⩏࡛ࡁࠊࡲࡓཎᏊࢧ࢖ࢬ࡜┦஫స⏝࢚ࢿࣝࢠ࣮ࡢ኱ࡁࡉࢆ⊂❧࡟ไᚚ࡛ࡁࡿࡢ࡟ᑐࡋ࡚ࠊ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀⣔࡛ࡣ࢖࢜ࣥࢧ࢖ࢬ
ࡢᐃ⩏࡟㆟ㄽࡢవᆅࡀ࠶ࡾࠊࡲࡓ࢖࢜ࣥࢧ࢖ࢬ࡜┦஫స⏝࢚ࢿࣝࢠ࣮ࡢ኱ࡁࡉࢆ /- ⣔ࡢࡼ࠺࡟⊂❧࡟ᢅ࠺ࡇ࡜ࡀ࡛ࡁ࡞࠸ࡓࡵࠊ/- ⣔࡛ࡢᡭἲࢆࡑࡢࡲࡲ㐺⏝ࡍࡿࡇ࡜ࡣᅔ㞴࡛࠶ࡿࠋ
᫖ᖺᗘࡣࠊࡲࡎ࢖࢜ࣥ㉁㔞࡜࢖࢜ࣥࢧ࢖ࢬࡀࠊ㝧࢖࢜ࣥ࡜㝜࢖࡛࢜ࣥ➼ࡋ࠸ࠊࡘࡲࡾ඲⢏Ꮚ࡛ඹ㏻࡜ࡋࡓࠕᑐ⛠⣔ࠖࢆᵓ⠏ࡋࠊࡇࢀࢆᇶ‽⣔࡜ࡋ࡚ࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ㛫࡛㉁㔞ࡢᕪ␗ࢆᑟධࡋࡓሙྜ࡟㍺㏦ಀ
ᩘ࡟ཬࡰࡍᙳ㡪࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓࠋ௒ᖺᗘࡣࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ㛫࡛ࢧ࢖ࢬࡢᕪ␗ࢆᑟධࡋࡓሙྜ
࡟㍺㏦ಀᩘ㸦⮬ᕫᣑᩓಀᩘ࡜㟁Ẽఏᑟ⋡㸧࡜ +DYHQ ẚ࡟ཬࡰࡍᙳ㡪࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓࠋ- 259 -

◊✲᪉ἲࠊィ⟬᪉ἲ᫖ᖺᗘࡢᮏ◊✲ㄢ㢟࡛ᵓ⠏ࡋࡓࣔࢹࣝᑐ⛠⣔ࡣࠊ➼ࣔࣝ⤌ᡂࡢ⁐⼥ /L,., ⣔ࡢ㉁㔞࡜࢖࢜ࣥࢧ࢖ࢬࢆᖹᆒ

໬ࡋ࡚ᚓࡽࢀࡓࠋࡍ࡞ࢃࡕࠊ⣔ࢆᵓᡂࡍࡿ  ✀㢮ࡢ㝧࢖࢜ࣥ࡜ඹ㏻ࡢ㝜࢖࡛࢜ࣥ␗࡞ࡿࡢࡣ࢖࢜ࣥ㉁㔞࡜㟁Ⲵࡢࡳ࡛࠶ࡿࡀࠊ㟁Ⲵࡣ  ౯࡛ᖖ࡟୍ᐃ࡛ࠊ࡞࠾࠿ࡘ  ✀㢮ࡢ㝧࢖࢜ࣥࡢ༊ูࡣ࡞࠸ࡶࡢ࡜ࡋࠊᮏ◊✲࡛ࡣ࢖࢜ࣥࢧ࢖ࢬࡢࡳࢆᚋ㏙ࡢࡼ࠺࡟ኚ໬ࡉࡏࡓࠋࣔࢹࣝᑐ⛠⣔ࡢ࢖༙࢜ࣥᚄࡣ SPࠊ㉁㔞ࡣ JPRO ࡛࠶ࡿࠋ⏝࠸ࡓ࣏ࢸࣥࢩࣕࣝ㛵ᩘࡣ )70 ࠿ࡽศᩓຊࢆ㝖࠸ࡓ  ᘧ࡛⾲ࡉࢀࡿࠋ߶௜௝ ൫‫ݎ‬௜௝ ൯ ൌ‫ݖ‬௜ ‫ݖ‬௝ ݁ ଶߪ௜ ൅ ߪ௝ െ ‫ݎ‬௜௝൅ ‫ܣ‬௜௝ ܾ݁‫ ݌ݔ‬൬
൰
‫ݎ‬௜௝
ߩ

ሺ2ሻ 

ࣔࢹࣝᑐ⛠⣔࡟࠾࠸࡚  ᘧࡢ࢖࢜ࣥࢧ࢖ࢬࣃ࣓࣮ࣛࢱߪ௜ ࡜ߪ௝ ࡢ್ࡣ➼౯࡛࠶ࡿࠋߪ௜ ൅ ߪ௝ ࡢ್ࡀࣔࢹࣝᑐ⛠⣔࡛ࡢ್࡜࡞ࡿࡼ࠺୍ᐃ࡟ಖᣢࡋࡘࡘࠊߪ௜ ࡜ߪ௝ ࡢ್࡟ᚎࠎ࡟ᕪࢆࡘࡅࡿࡇ࡜࡛ࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢࢧ࢖ࢬ
࡟㠀ᑐ⛠ᛶࢆᑟධࡋࡓࠋࡇࢀ࡟ࡼࡗ࡚ࠊᅗ  D ࡟♧ࡉࢀࡿࡼ࠺࡟␗✀࢖࢜ࣥ㛫ࡢ࣏ࢸࣥࢩࣕࣝ㛵ᩘࡣ୍ᐃ࡟
ಖࡓࢀࡿࡀࠊྠ✀࢖࢜ࣥ㛫ࡢ࣏ࢸࣥࢩࣕࣝ㛵ᩘࡣࠊᅗ  E ࡜ᅗ  F ࡢࡼ࠺࡟ኚ໬ࡍࡿࠋᅗ୰ࡢᩘ್ࡣ㝜࢖࢜ࣥࡢࢧ࢖ࢬࣃ࣓࣮ࣛࢱ࡟᥃࠿ࡿಸ⋡ࢆ⾲ࡍࠋ


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D 㝧䜲䜸䞁㻙㝜䜲䜸䞁

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F 㝜䜲䜸䞁㻙㝜䜲䜸䞁

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E 㝧䜲䜸䞁㻙㝧䜲䜸䞁

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rLM>Ⴒ@㻢㻤ᅗ ྛ࢖࢜ࣥ✀㛫ࡢ )70 ࡢ࣏ࢸࣥࢩࣕࣝ᭤⥺⣔ࡢ඲⢏Ꮚᩘࡣࠊ ಶ 㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࢆࡑࢀࡒࢀ  ಶࡎࡘ㓄⨨ ࠊᗘࡣ  . ࡜ࡋࠊNVT ࢔ࣥࢧࣥࣈࣝ᮲௳ୗ࡛ 0' ィ⟬ࢆ⾜࠸ࠊ QV ࡟ཬࡪ⣔ࡢ᫬㛫Ⓨᒎࢆồࡵࡓࠋ⮬ᕫᣑᩓಀᩘ D ࡣࠊ⢏Ꮚ i ࡢ᫬้ t࡟࠾ࡅࡿኚ఩‫ݎ‬௜ ሺ‫ݐ‬ሻ െ ‫ݎ‬௜ ሺ0ሻࢆ⏝࠸࡚ࠊ  ᘧ࡟♧ࡍ (LQVWHLQ ࡢᘧ࡟ࡼࡗ࡚ホ౯ࡋࡓࠋ‫ ܦ‬ൌ limଵ௧՜ஶ ଺௧

‫ݎ|ۃ‬௜ ሺ‫ݐ‬ሻ െ ‫ݎ‬௜ ሺ0ሻ|ଶ ‫             ۄ‬㟁Ẽఏᑟ⋡ߪ ୉େ ࡣ  ᘧ࡛⾲ࡉࢀࡿ㟁Ⲵᐦᗘࡢᖹᆒ஧஌ኚ఩࠿ࡽィ⟬ࡋࡓࠋߪ ୉େ ൌߚ݁ ଶlim ሺ6‫ݐ‬ሻିଵ ‫ܳ|ۃ‬ା οା ሺ‫ݐ‬ሻ ൅ ܳି οି ሺ‫ݐ‬ሻ|ଶ ‫  ۄ‬
ܸ ௧՜ஶ

ሺ4ሻ

◊✲ᡂᯝ
ߪ௜ ߪ௝ ࡢ್ࡀࣔࢹࣝᑐ⛠⣔ࡢ್࡜➼ࡋࡃ࡞ࡿࡼ࠺୍ᐃ࡟ಖᣢࡋࡘࡘࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢࢧ࢖ࢬ࡟㠀ᑐ⛠ᛶࢆᑟධࡍ࡭ࡃࠊߪ௜ ࡜ߪ௝ ࡢ್ࢆࡑࢀࡒࢀಸ࠿ࡽಸࡲ࡛ኚ໬ࡉࡏࡓ⣔ࡢྛ࢖࢜ࣥ✀㛫ࡢ஧యศᕸ㛵ᩘࢆᅗ  ࡟♧ࡍࠋᅗ୰ࡢᩘ್ࡣ㝜࢖࢜ࣥࡢࢧ࢖ࢬࣃ࣓࣮ࣛࢱ࡟᥃࠿ࡿಸ⋡ࢆ⾲ࡍࠋྠ✀࢖࢜ࣥ㛫ࡢ➨୍ࣆ࣮ࢡࡢ
㧗ࡉࢆ㝖࠸࡚ࠊ஧యศᕸ㛵ᩘ࡟኱ࡁ࡞ኚ໬ࡣㄆࡵࡽࢀ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋࡇࡢࡇ࡜ࡣࠊᾮయᵓ㐀ࡀᮏ㉁ⓗ࡟ኚ໬ࡋ࡞࠸ࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋࡇࢀࡣࠊᒾሷᆺࡢ⤖ᬗᵓ㐀࡟࠾࠸࡚㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ࢖࢜ࣥࢧ࢖ࢬࡢ
࿴ࡀ୍ᐃ࡟ಖᣢࡉࢀࡓሙྜࠊ⤖ᬗᵓ㐀ࡀ᏶඲࡟ಖᣢࡉࢀࡿࡓࡵࠊண᝿ࡉࢀࡓ⤖ᯝ࡜ゝ࠼ࡿࠋ୍᪉ࠊ஧యศᕸ

- 260 -

㛵ᩘࡢ➨୍ࣆ࣮ࢡࡢ㧗ࡉ࡟╔┠ࡍࡿ࡜ࠊ␗✀࢖࢜ࣥ㛫࡛ࡣኚ໬ࡀ࡞࠸ࡀࠊྠ✀࢖࢜ࣥ㛫ࡣࠊ࢖࢜ࣥࢧ࢖ࢬࡀ
኱ࡁࡃ࡞ࡿ࡟ࡘࢀ࡚㧗ࡃ࡞ࡿഴྥࡀㄆࡵࡽࢀࡿࠋࡍ࡞ࢃࡕࠊᅗ࡟♧ࡋࡓ┦஫స⏝࣏ࢸࣥࢩࣕࣝࡢ᣺ࡿ⯙࠸࠿ࡽࠊ஫࠸࡟᥋㏆ࡍࡿࡇ࡜ࡣ࢚ࢿࣝࢠ࣮ⓗ࡟୙฼࡟࡞ࡾࠊࡑࡢ⤖ᯝࠊᅗ࡛ࡣ➨୍ࣆ࣮ࢡࡢ❧ࡕୖࡀࡾࡢ㒊ศ㸦ᕥ〈㸧ࡀ㐲㊥㞳ഃ࡟ࢩࣇࢺࡍࡿࠋ࡜ࡇࢁࡀࠊ␗✀࢖࢜ࣥ㛫ࡢᙉ࠸┦஫స⏝࡟ࡼࡾࠊྠ✀࢖࢜ࣥ㛫ࡢࣆ࣮ࢡ఩⨨ࡣಖᣢࡉࢀࠊ⤖ᯝ࡜ࡋ࡚➨୍ࣆ࣮ࢡࡢ㧗ࡉࡀቑ኱ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋᅗ  ࡟♧ࡍࡼ࠺࡟ࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢྛ⮬ᕫᣑᩓಀᩘࡣ᭷ព࡟ኚ໬ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡣ⣧⢋࡟࢖࢜ࣥࢧ࢖ࢬẚࡀ⮬ᕫᣑᩓಀᩘ࡟ཬࡰࡍຠᯝ࡜ゝ࠼ࡿࠋண᝿ࡉࢀࡿࡼ࠺࡟ࠊࢧ࢖ࢬࡀᑠࡉ࠸࢖࢜ࣥࡢ⮬ᕫᣑᩓಀᩘࡀ኱ࡁ࡞࢖࢜ࣥࡢ⮬ᕫᣑᩓಀᩘࡼࡾ኱ࡁ࠸ࡇ࡜ࡶ☜ㄆ࡛ࡁࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊᅗ࡟♧ࡋࡓ␗✀࢖࢜ࣥ㛫ࡢ஧యศᕸ㛵ᩘࡀࠊ࢖࢜ࣥࡢࢧ࢖ࢬẚࡀኚ໬ࡋ࡚ࡶ୙ኚ࡛࠶ࡗࡓࡇ࡜ࢆ⪃៖ࡍࡿ࡜ࠊពእᛶࡀ࠶ࡿ࡜ゝ࠼ࡿࠋ୍᪉࡛ࠊᅗ࡛ྠ✀࢖࢜ࣥ㛫ࡢ஧యศᕸ㛵ᩘ࡟࠾ࡅࡿ➨୍ࣆ࣮ࢡࡢ㧗ࡉࡀࠊ࢖࢜ࣥࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡿ
࡟ࡘࢀ࡚㧗ࡃ࡞ࡿ஦ᐇࡀ᫂ࡽ࠿࡟࡞ࡾࠊࡑࡢ⌮⏤ࡣୖ㏙ࡢ࡜࠾ࡾ࡛࠶ࡿࠋࡲ࡜ࡵࡿ࡜ࠊ࢖࢜ࣥࢧ࢖ࢬࡀ኱ࡁ
ࡃ࡞ࡿ࡟ࡘࢀ࡚ὶືᛶࡀୗࡀࡿࡢࡣࠊ➨୍㏆᥋ࡢ␗✀࢖࢜ࣥ㛫ࡢᙳ㡪࡛ࡣ࡞ࡃࠊ➨஧㏆᥋࡟࠶ࡿྠ✀࢖࢜ࣥ㛫ࡢᵓ㐀┦㛵ࡢቑ኱࡟ࡼࡿ⤖ᯝ࡛࠶ࡾࠊࡑࡢ⌮⏤ࡣ┤᥋ⓗ࡟ࡣྠ✀࢖࢜ࣥ㛫ࡢ᩺ຊ┦஫స⏝࡜ࠊ㛫᥋ⓗ࡟ࡣ␗✀࢖࢜ࣥ㛫ࡢᙉຊ࡞ᘬຊ┦஫స⏝࡟ࡼࡿࡶࡢ࡜⤖ㄽࡉࢀࡿࠋ
㝧࢖࢜ࣥ࡟ᑐࡍࡿ㝜࢖࢜ࣥࡢ⮬ᕫᣑᩓಀᩘࡢẚࡢ㝧࢖࢜ࣥ࡟ᑐࡍࡿ㝜࢖࢜ࣥࡢࢧ࢖ࢬẚࡢኚ໬࡟ࡘ࠸࡚ㄪ
࡭ࡓ࡜ࡇࢁ ஌࡟ẚ౛ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢ≀㉁ᅛ᭷ࡢࣃ࣓࣮ࣛࢱ࡛࠶ࡿ )70 ࡢࢯࣇࢺࢿࢫࣃ࣓࣮ࣛࢱߩࡀ⮬ᕫᣑᩓಀᩘ࡟ཬࡰࡍຠᯝࢆ㏣ຍࡍࡿࡇ࡜࡛⾲ᘧ  ࢆᚓࡓࠋ‫ܦ‬௔ߪ௔ ି଴.ହ 1 ଴.ଵହ‫ ן‬൬ ൰
൬ ൰
‫ܦ‬௖
ߪ௖
ߩ

ሺ5ሻ

ᐇᅾ⣔ࡢ⮬ᕫᣑᩓಀᩘẚࡢィ⟬್ࢆ⾲ᘧ  ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓ⤖ᯝࡣࠊᴫࡡཎⅬࢆ㏻ࡿ┤⥺࡟஌ࡗ࡚࠸
ࡿࡀࠊ┤⥺࠿ࡽእࢀ࡚࠸ࡿ⣔ࡶ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ≉࡟ࠊࣔࢹࣝᑐ⛠⣔ࡢᵓ⠏ࡢ㝿࡟ཧ↷ࡋࡓ≀㉁࡛࠶ࡿ
/L, ࡢࣉࣟࢵࢺࡀ┤⥺࠿ࡽእࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊ⾲ᘧ  ࡢໟᣓᛶࡢྥୖ࡟ࡣࠊߪ࠾ࡼࡧߩ౫Ꮡᛶ࡟ࡘ࠸࡚ࠊࡼ
ࡾᗈ⠊࡞㡿ᇦ࡛ࡢㄪᰝࡀᚲせ࡛࠶ࡿࠋᅗ  ࡟♧ࡍࡼ࠺࡟ࠊ㟁Ẽఏᑟ⋡ࡣ⮬ᕫᣑᩓಀᩘ࡜ࡣ␗࡞ࡾࠊ࢖࢜ࣥࢧ࢖ࢬẚ࡟౫Ꮡࡋ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊ࢖࢜ࣥࢧ࢖ࢬẚ࡟ᑐࡍࡿ +DYHQ ẚࡢኚ໬࡜ࠊ࢖࢜ࣥࢧ࢖ࢬẚ࡟ᑐࡍࡿ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ⮬ᕫᣑᩓಀᩘࡢ࿴ࡢኚ໬ࢆㄪ࡭ࡓ⤖ᯝࢆ  ᘧ࡟↷ࡽࡋ࡚⪃࠼ࡿ࡜ࠊ࢖࢜ࣥࡢᗙᶆࡢኚ఩ࡢ⮬ᕫ┦㛵㡯࡜┦஫┦㛵㡯ࡢኚ໬ࡀ஫࠸࡟┦ẅࡋࡓ⤖ᯝࠊᅗࡢࡼ࠺࡟㟁Ẽఏᑟ⋡ࡀ୍ᐃ࡟ಖᣢࡉࢀࡿ࡜⤖ㄽࡉࢀࡓࠋ


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

E 㻌㝧䜲䜸䞁㻙㝧䜲䜸䞁㻡㻚㻜D 㻌㝧䜲䜸䞁㻙㝜䜲䜸䞁
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r>Ⴒ@

ᅗ ࢖࢜ࣥࢧ࢖ࢬࡀ㠀ᑐ⛠໬ࡋࡓ㝿ࡢྛ࢖࢜ࣥ✀㛫ࡢ஧యศᕸ㛵ᩘ

- 261 -

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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.
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Reactions from Sumanenone", M. Nishimoto, Y. Uetake, Y. Yakiyama, F. Ishiwari, A. Saeki, H. Sakurai, J. Org.
Chem. 2022, 87, 2508-2519.
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1Introduction
Titanium-dioxide is a common component of electrode surfaces and photocatalytic systems. Depending on the

preparation, the oxide can be formed in different phases, shapes and morphology which can affect the selectivity andefficiency of the catalytic and photocatalytic reactions. Since the morphology and shape of the nanoparticles can beeasily tuned with experimental conditions, this may offer a new, unexplored strategy to improve electrode properties.
The goal of our computational studies is to understand better how charge carriers behave in these oxide nanoparticles.
Charge carriers (both holes and electrons) tend to form polarons in oxide materials, which poses challenges for
accurate simulations. We have performed the calculations with DFT using pure and hybrid functionals, which offer arelatively cheap simulation in non-periodic systems like our nanoparticle models.

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) andhybrid (PBE0, B3LYP) functionals. When it was relevant, DFT-D3(BJ) dispersion model was applied. 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.

Whenever it 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 O vacancy and H- doped
surfaces. The verification of the geometry stability using frequency calculation were not possible due to the large
computational cost of the task and limited computational time.

3

Results

Following out original plans, we have optimized 4 nanoparticle models (NPs) as described in the methods. When we
attempted the optimization of NPs with extra charge carriers, the convergence of the wavefunction and the optimizationof the structure required longer calculational time than we it was originally planed. In this report I focus on the results
on a small model, NP1 (Ti98O198H4, symmetry: C2h).
When an extra negative (electron) or positive (hole) charge carrier is placed on NP1, this extra charge is unevenly
distributed on the Ti and O atoms (Fig.1. left: the electron density difference due to an extra negative charge). This ispartly due to the Coulomb repulsion of the extra charge on different atoms, and the possible localization of HOMO andLUMO orbitals. For an easy comparison, we relied on the Mulliken-charge difference between the charged and neutral
states and have defined two variables, Δ+ and Δ-:- 269 -''M  M  M   M 

Where M(0) represent the Mulliken charge of the neutral nanoparticle, and M(+)/M(-) are that of the positive (+1) andnegative(-1) charged, respectively. The sign is defined that both an extra electron or a hole

Figure 1. The geometry of NP1 with the electron density difference between negatively charged and neutral
nanoparticle (left), and the extra charge density calculated using different functionals (right, see explanation in

In Fig.1 (right) the Δ+ vs Δ- for NP1 is shown when calculated with pure and hybrid (PBE0 and B3LYP) functionals.
The deviation from the diagonal (Δ+ = Δ-) clearly is due to the difference between HOMO and LUMO orbital
localizations, which is more pronounced when hybrid functionals used. On atoms where LUMO largely localized,
electron trapping can be observed (Δ+ < Δ-), for atoms with HOMO localization, hole trapping can be observed (Δ+ > Δ-).
In spite of the limitations of Mulliken charge, the excess charge (Δ+, Δ-) is a useful metric that we have also used tomonitor the charge trapping sites due to protonation and oxygen vacancy in the anatase lattice.

4

Talks and Posters[★] G. Juhasz, “Charge trapping in TiO2 nanoparticles” (oral, international), ECS, Atlanta, 2022.
[★] G. Juhasz, “Charge trapping and bandgap of TiO2 nanoparticles with different shapes“ (oral, international)

MSE Congress, Darmstadt, 2022.

5

Publications[★] H Eguchi, K Kato, G Juhasz, M Yamauchi, “Selectivity enhancement in the electrochemical reduction ofoxalic acid over titanium dioxide nanoparticles achieved by shape and energy-state control” Catalysis Science &Technology 11 (23), 7592-7597.
[★, in preparation] G. Juhasz, “Investigation of polaron formation and charge trapping in anatase-type TiO2
nanoparticles with DFT method using hybrid-functionals”- 270 -

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>@ <-LQ%5DPDGRVV6$VDNR/,OLHV, iu³   }, 2022 } 3 >@ <0XWRK6$VDNR/,OLHV, ³ Ñ{iuÅ, 2021 } 9 

>@6$VDNR GU<iu  43V=W:VK;4M,  }  >@6$VDNR.7DNDL, 3$&,),&+(0,  }  - 274 -

ィ⟬ศᏊศගᏛ䠖 ศᏊ䛾ᵓ㐀䛚䜘䜃཯ᛂ䛻㛵䛩䜛ィ⟬໬Ꮫ&RPSXWDWLRQDO0ROHFXODU6SHFWURVFRS\&RPSXWDWLRQDO&KHPLVWU\
RQWKH6WUXFWXUHDQG5HDFWLRQRI0ROHFXOHV‫ۑ‬ᖹ㔝 ᜏኵ㸦࠾Ⲕ኱⌮㸧ࠊ㛗ᔱ 㞼ර㸦ᶓᕷ኱㸧ࠊ  ௒ᇛ ᑦᚿ㸦᪥ᮏዪᏊ኱⌮㸧ࠊᕝཱྀ ᘓኴ㑻㸦ᒸᒣ኱㝔㸧 ◊✲┠ⓗࠊෆᐜ๓ᖺᗘ䛾ㄢ㢟䛻ᘬ䛝⥆䛝䚸䛂ィ⟬ศᏊศගᏛ䛃䛾どⅬ䛻❧䛳䛶䚸ḟ䛾  Ⅼ䛻㛵䛩䜛◊✲䜢⾜䛳䛯䚹 ┤⥺  ཎᏊศᏊ䠄䝫䝔䞁䝅䝱䝹䜶䝛䝹䜼䞊᭤㠃䛜┤⥺ᵓ㐀䛷ᴟᑠ䛻䛺䛳䛶䛔䜛  ཎᏊศᏊ䠅䛾᣺ື࣭ᅇ㌿ᖹᆒᵓ㐀࡛࠶ࡿࡀࠊ
┤⥺ᙧ࡛࠶ࡿ࡜ࡍࡿศගᏛࡢᚑ᮶ࡢࣃࣛࢲ࢖࣒࡟ᢠࡋ࡚ࠊほࡍࢀࡤࠕ᭤ࡀࡗ࡚ぢ࠼ࡿࠖ࡜࠸࠺ᡃࠎࡢ୺ᙇ

ࢆ☜❧䛩䜛䛯䜑䛾ドᣐᅛ䜑䛾ィ⟬䜢⾜䛖䚹㻞㻕 䛭䛾ᛂ⏝䛸䛧䛶䚸䝧䞁䝊䞁䛺䛹䛾ⰾ㤶᪘Ⅳ໬Ỉ⣲䛻ぢ䛔䛰䛥䜜䛯୍ぢ␗ᖖ䛺㛵ಀ䚸༶䛱 &௅+ ⤖ྜ㛗䛸 &௅' ⤖ྜ㛗䛜䜋䜌➼䛧䛟䛺䜛஦ᐇ䜢ゎ᫂䛩䜛䛸䛸䜒䛻䚸ᖹ㠃ศᏊ䛾඾ᆺ䛸䛥䜜䛶䛝䛯䝧䞁䝊䞁䛾᣺ືᖹᆒᵓ㐀䜢᳨ウ䛩䜛䚹  ୍⯡䛻 2 䛻䜘䜛㓟໬཯ᛂ䛷䚸ᇶ㉁䛛䜙䛾  㟁Ꮚ⛣⾜䛜㉳䛣䜛䛸  㔜㡯㓟⣲䛸䛾཯ᛂ䛷䜒䚸 㔜㡯㓟⣲䛸䛾཯ᛂ䛷䜒ྠ䛨⏕ᡂ≀䛜ᚓ䜙䜜䜛⌮⏤䜢᫂䜙䛛䛻䛩䜛䚹  f 㟁Ꮚࢆྵࡴࣛࣥࢱࢽࢻ

⣔ࡢศᏊࡢ㧗⢭ᗘ࡞ศᏊ㌶㐨ἲィ⟬ࡣᮍ㛤ᣅ࡞ศ㔝࡞ࡢ࡛ࠊ<E ศᏊࡢศගᐇ㦂ࢆࡸࡗ࡚࠸ࡿᐇ㦂ࡢࢢ࣮ࣝࣉ࡜࡜ࡶ࡟ࠊ◊✲ࢆ㐍ࡵࡿࠋ ◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ศᏊศගᏛ䛷䛿䚸䠄ᐇ㦂䠅ศᏊศගᏛ䛸㐪䛳䛶䚸᭱ึ䛻 ab initio ศᏊ㌶㐨ἲィ⟬䛻䜘䛳䛶 3RWHQWLDO (QHUJ\
6XUIDFH3(6 䜢Ỵ䜑䜛䚹䛭䛧䛶䚸䛭䛾 3(6䜢⏝䛔䛶䚸᣺ື䞉ᅇ㌿䛾 6FKU|GLQJHU᪉⛬ᘧ䜢ゎ䛝䚸ồ䜑䛯Ἴື㛵ᩘ䛾ᮇᚅ್䛸䛧䛶䇾᣺ື䞉ᅇ㌿䜢⪃៖䛧䛯䇿ᖹᆒᵓ㐀 ⤖ྜ㛗䚸⤖ྜゅ 䛾⟬ฟ䜢⾜䛖䚹3(6 䛾ィ⟬䛻䛿 02/352 䜢౑䛔䚸᣺ື䞉ᅇ㌿䛾 6FKU|GLQJHU᪉⛬ᘧ䛿 ḟ䛾ᦤືㄽ䚸䜎䛯䛿 'LVFUHHW 9DULDEOH5HSUHVHQWDWLRQἲ䠄'95䠅䛷ゎ䛔䛯䚹ึ䜑䛛䜙 3(6 䛜ศ䛛䛳䛶䛔䜛䛸䛔䛖䛣䛸䛿䚸ィ⟬ศᏊศගᏛ䛾᭱኱䛾ᙉ䜏䛷䛒䜚䚸௨ୗ䛻㏙䜉䜛ศᏊศගᏛ䛾ᙅⅬ䚸ḞⅬ䜢᫝ṇ䛩䜛䛣䛸䛜ฟ᮶䜛䚹ศᏊศගᏛ䛾෌ᵓ⠏䛷䛒䜛䚹ᖹ㔝䚸㛗ᔱ䚸㤿ሙ䜾䝹䞊䝥䛾ᡭ䛻వ䜛ၥ㢟䛷䛿䛒䜛䛜䚸䝏䝱䝺䞁䝆䛻್䛩䜛㔜せㄢ㢟䛷䛒䜛䛸ᛮ䛳䛶䜔䛳䛶䛔䜛䚹ᡃࠎࡣࠊᖺ࡟┤⥺ศᏊ 1L&1ࡢ᣺ືᅇ㌿ᖹᆒࡢ⤖ྜゅࡢᮇᚅ್ࡀ ࡛࠶ࡿࡇ࡜ࢆぢ࠸ࡔࡋ࡚௨᮶ࠊ┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ࡜୺ᙇࡋ࡚ࡁࡓࠋ ࡈࡃ᭱㏆࡟⮳ࡿࡲ࡛ࠊᅄ㠃ᴆḷ࡛࠶ࡗࡓࡀࠊศᏊ◊ࡢィ⟬⛉Ꮫࢭࣥࢱ࣮࡛ィ⟬ࡋࡓ㉸㧗⢭ᗘ࡞ 3(6࡟ᇶ࡙ࡃ㆟ㄽࢆᒎ㛤ࡋ࡚࠸ࡿ࠺ࡕ࡟ࠊᡃࠎࡢ୺ᙇ࡟㈶ྠ
ࡍࡿศගᏛ⪅ࡀ⌧ࢀ࡚ࡁࡓࠋࡲࡉ࡟ E pur si muove ࡛࠶ࡿࠋ⾲   ┤⥺  ཎᏊศᏊ䛾 ‫ߩۃ‬ҧ ‫ۄ‬0‫ߩۃ‬ҧ ‫ۄ‬0 ศᏊ  ᮇ ᚅ ್ B 䛾 ෌ ゎ 㔘6&2
  
6 )H&2     

3 1&6      

3 %U&1    ) &R&1      
6 0J1&  ' 1L&1     ' )H&1     
6 +&2
    
 

6 '&2     

 
6 +&1       
 
6 '&1       
'  )H1&    6  &V2+     
6 &   ◊✲ᡂᯝ ᪂ࣃࣛࢲ࢖࣒㸸┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ
㔞ᏊຊᏛ䛷䛿䚸䛂⮬↛⏺䠄䝅䝳䝺䞊䝕䜱䞁䜺䞊᪉⛬ᘧ䛾ୡ⏺䠅䛃䛸䛂ᡃ䚻䛃䛿䚸⊂❧䛺஧䛴䛾ୡ⏺䛸⪃䛘䛶䛔䜛䛾䛷䚸⮬↛⏺䛷㉳䛣䛳䛶䛔䜛䛣䛸䜢▱䜚䛯䛡䜜䜀ほ䛧䛺䛡䜜䜀䛺䜙䛪䚸ほ䛧䛶ᚓ䜙䜜䜛䜒䛾䛸⮬↛⏺䛷㉳䛣

- 275 -

䛳䛶䛔䜛䛣䛸䛸䛿ᚲ䛪䛧䜒୍⮴䛧䛺䛔䚹㔞Ꮚ⛉Ꮫ⪅䛾ᖖ㆑䛷䛒䜛䛜䚸ᚑ᮶䛾ศගᏛ䛷䛿䛣䛖䛧䛯どⅬ䛜Ḟ䛡䛶䛔䛯䚹⾲  䛻௒ᖺᗘᮎ䜎䛷䛾◊✲⤖ᯝ䜢⧳䜑䛶♧䛧䛯䚹‫ߩۃ‬ҧ ‫ۄ‬0 ࡣ┤⥺ᵓ㐀࠿ࡽࡢࢬࣞࡢゅᗘ㸦  ⤖ྜゅࡢ⿵ゅ㸧ࠊB ࡣᐇ㦂࡛ồࡵࡽࢀࡓᅇ㌿ᐃᩘࠊῧ࠼Ꮠࡢ³´䛿䚸䝊䝻Ⅼ᣺ື≧ែ䜢⾲䛩䚹䛣䜜䛷䚸ᐇ㦂ⓗ࡟ࡶࠊ⌮ㄽⓗ࡟ࡶ┤⥺  ཎᏊศᏊࡣࠕࡲࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖࡇ࡜ࡀศ࠿ࡗࡓࡇ࡜࡟࡞ࡿࠋ⌮ㄽࡢヲ⣽ࡣࠊᩥ⊩  ࢆࡈぴ㡬ࡁࡓ࠸ࠋ ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡟࠾ࡅࡿ␗ᖖ㸽࡞㛵ಀ㸸 r rH୍⯡࡟ࠊ&௅+ ࡸ 2௅+ ⤖ྜࡢ᣺ືᖹᆒ⤖ྜ㊥㞳 r ࡣࠊ᣺ື࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ᖹ⾮⤖ྜ㊥㞳 rHࡼࡾ㛗ࡃ࡞ࡿ㸦r !rH㸧ࠋࡇࡢᖖ㆑࡟཯ࡋ࡚ࠊ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡛ࡣࠊᐇ㦂࡛ᚓࡽࢀࡿ

⾲኱᣺ᖜኚゅ᣺ື䛩䜛 $௅%௅& ཬ䜃 $௅$௅$ ᆺ┤⥺ศᏊ䛾᣺ືᖹᆒᵓ㐀 +&1    '&1    +2&V   &᣺ືᅇ㌿䛾Ἴື㛵ᩘ䛛䜙䛾ᮇᚅ್rH $௅% RU rH $௅$ c             
   
r $௅% RU r $௅$ c
ኚ఩ゅ䛾ᮇᚅ್ ¢ߩҧ ² GHJUHHV                    
rSURM $௅% RU rSURM $௅$ cᅇ㌿ᐃᩘ䛾ᐇ㦂್ BHII 䛛䜙䛾್           rHII $௅% RU rHII $௅$ c

HIIHFWLYH ࡞ᅇ㌿ᐃᩘ࠿ࡽᑟ
࠿ࢀࡿࢮࣟⅬ᣺ື≧ែ࡛ࡢ᣺ືᖹᆒ⤖ྜ㛗 rHII ࡣࠊࡑࢀࡒࢀࡢᖹ⾮⤖ྜ㛗 rH ࡼࡾ▷ࡃ࡞ࡿࡇ࡜ࡀ࠶ࡿࠋࡇࡢ୍ぢወጁ࡞ࠊᖖ㆑࡟཯ࡍࡿ⌧㇟ࡣࠊᐇࡣࠊᅇ㌿ᐃᩘࡢᐇ㦂್࠿ࡽᚓࡽࢀࡿ⤖ྜ㛗ࡣࠊa ୺㍈࡬ࡢᢞᙳ㛗 rSURM
࡞ࡢ࡛ࠊᢞᙳゅࡀ኱ࡁࡃ࡞ࡿ࡜ࡑࡢᢞᙳ㛗ࡣ▷ࡃ࡞ࡗ࡚ rSURM rH ࡜࡞ࡿࡇ࡜ࡀ࠶ࡿᚓࡿࡇ࡜ࠊ࠾ࡼࡧࠊࡑࡢ
ሙྜ࡛ࡶࠊᩥᏐ㏻ࡾࡢࢮࣟⅬ᣺ື⤖ྜ㛗 r ࡟㛵ࡋ࡚ࡣࠊᚑ᮶ࡢᖖ㆑㏻ࡾ r ! rH ࡀᡂࡾ❧ࡘࡇ࡜ࢆ♧ࡍࡇ࡜ࡀฟ᮶ࡓ 㸧㸦⾲ 㸧ࠋ ᐇ㦂࡛ⰾ㤶⎔࡟ࡘ࠸ࡓ &+ ⤖ྜ㛗࡜ &' ⤖ྜ㛗ࡀྠࡌ㛗ࡉ࡟࡞ࡿ⌮⏤
㏻ᖖࠊఙ⦰᣺ື࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊ&௅+ ࡢ⤖ྜ㛗 r &௅+ ࡣࠊ&௅' ࡢ⤖ྜ㛗 r &௅' ࡼࡾ㛗ࡃ࡞ࡿࠋࡇࢀ࡟཯
ࡋ࡚ࠊ࣋ࣥࢮࣥࡢᅇ㌿ᐃᩘ࠿ࡽồࡵࡓᐇ㦂್   ࡛ࡣ rHII &௅+ # rHII &௅' ࡛࠶ࡗࡓࠋ࣋ࣥࢮࣥࡢ  ḟඖࡢ 3(6 ࢆ ab initio ศᏊ㌶㐨ἲ࡛ồࡵࡿࡇ࡜ࡣ୙ྍ⬟࡞ࡢ࡛ࠊ࣋ࣥࢮࣥࢆ௬᝿ⓗ࡞┤⥺  ཎᏊศᏊ>&+@௅>&@௅>+@ 䛸ぢ❧࡚࡚ࠊ&௅+ ⤖ྜ࡟㛵ࡍࡿࠊఙ⦰᣺ື䠄/VWU䠅ࠊ㠃እኚゅ᣺ື䠄/A䠅࠾ࡼࡧ㠃ෆኚゅ᣺ື䠄/‫ۅ‬䠅ࢆ⪃࠼ࡿࡇ࡜࡟ࡋࡓ㸦ᅗ 㸧ࠋ/VWU ࡛ࡣఙ⦰᣺ືࡢ࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊᖖ㆑
㏻ࡾ &௅+ ⤖ྜࡢ᪉ࡀ &௅' ⤖ྜࡼࡾ㛗ࡃ࡞ࡿࡀࠊ/A࡜ /‫ࡣ࡛ۅ‬䚸&௅+ ⤖ྜࡢᖹᆒኚ఩ゅᗘࡢ᪉ࡀ &௅' ⤖ྜࡢࡑࢀࡼࡾ኱ࡁ࠸ࡢ
࡛ࠊa ㍈࡬ࡢᢞᙳ㛗ࡣ㏫࡟▷ࡃ࡞ࡿࠋࡑࡢ⤖ᯝࠊ୧⪅ࡀ࡯ࡰ࢟ࣕࣥࢭࣝࡋ࡚ࠊ&௅+ ⤖ྜ࡜ &௅' ⤖ྜࡢᕪࡣc ࡜࡞ࡾࠊrHII &௅+  # rHII &௅'  ࡜࡞ࡿ⌮⏤ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀฟ᮶ࡓࠋᅗ௬᝿  ཎᏊศᏊ >&+@௅>&Į@௅>+Į@䛸ぢ❧䛶䛯䝧䞁䝊䞁䛾 &Į௅+Į ⤖ྜ䛾ఙ⦰
/VWU  㠃እኚゅ /A  㠃ෆኚゅ / ̀  ᒁᅾ᣺ື䝰䞊䝗

࣋ࣥࢮࣥࡣࠊ㦵᱁Ⅳ⣲ࡢ sp ΰᡂࡢࡓࡵᖹ㠃ศᏊࡢ඾ᆺ࡜ࡉ
ࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࡢィ⟬࡟ࡼࡿ࡜ &௅+ ⤖ྜࡢ & ⎔㠃࡬ࡢᖹᆒᢞᙳゅࡀ⣙  ᗘ࡞ࡢ࡛ࠊ࣋ࣥࢮࣥࡢ᣺ື
ᖹᆒᵓ㐀࡜ࡋ࡚ࡣࠊ⤫ィⓗ࡟࡛ࡣ࠶ࡿࡀࠊ+ ࡀ & ⎔㠃ࡢୖࠊࡲࡓࡣୗ࡟఩⨨ࡍࡿ SODQDU EXW QRQIODW ࡞ᵓ㐀㸦BJ ᵓ㐀㸧࡟࡞ࡗ࡚࠸ࡿࡇ࡜࡟࡞ࡿࠋࡇࢀࡣࠊᐃㄝ࡟཯ࡍࡿ⤖ㄽ࡛ࡣ࠶ࡿࡀࠊ័ᛶ⬟⋡Ḟᦆࡢ್࡜㟁Ꮚ⥺ᅇᢡࡢࢹ࣮ࢱ࠿ࡽࠊࡇࡢ SODQDUEXWQRQIODW ࡞ᵓ㐀ࡢṇࡋࡉࢆド᫂ࡍࡿࡇ࡜ࡀฟ᮶ࡓ  ࠋ- 276 -

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ゅ㸦ᅗࡢߩҧ 㸧ࡢᮇᚅ್ ¢ߩҧ ²ࡣ࡛ࠊண᝿㏻ࡾࠕ᭤ࡀࡗ࡚ぢ࠼ᅗ  ;H+;H 䛾ᵓ㐀࡚࠸ࡿࠖࡇ࡜ࡀศ࠿ࡗࡓࠋ
 ཯ᛂ࡟࠾ࡅࡿືⓗ㐣⛬ࡢゎᯒ 㔜㡯㓟⣲࡟ࡼࡿ㓟໬཯ᛂ2 ࡟ࡼࡿ㓟໬཯ᛂࡣࠊᇶᮏ୰ࡢᇶᮏࡢ཯ᛂ࡛࠶ࡿࠋ✵Ẽ୰ࡢ㓟⣲ศᏊࡣࠊ 㔜㡯 2 ࡛࠶ࡿࡀࠊ࢔ࢫࢥࣝࣅ
ࣥ㓟࢔ࢽ࢜ࣥ ࣅࢱ࣑ࣥ & ࡢ࢔ࢽ࢜ࣥ ࡜ࡢ཯ᛂ࡛ࡣࠊ 㔜㡯 2 ࡛ࡶࠊ 㔜㡯 2 ࡛ࡶྠࡌ⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ
࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡲࡓࠊ6F 2 ࡢ཯ᛂࡢゎᯒ࠿ࡽࠊ 㔜㡯 2 ࡜ࡢ཯ᛂ࡛ࡶࠊ཯ᛂࡢ㏵୰࡛ 6F ࠿ࡽ 2 ࡬ࡢ 㟁Ꮚ⛣⾜ࡀ㉳ࡁࡿࡓࡵࠊ⤖ᯝ࡜ࡋ࡚ࠊ 㔜㡯 2 ࡜ࡢ཯ᛂ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋ
୍⯡໬ࡍࢀࡤࠊ㟁Ꮚ౪୚ᛶࡢ㧗࠸ศᏊ࡜ 2 ࡜ࡢ཯ᛂ࡛ࡣࠊ཯ᛂࡢ㏵୰࡛㟁Ⲵ⛣ືࡀ㉳ࡇࡿࡓࡵ࡟ࠊ 㔜㡯
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࠸ࡃࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋከ㓄⨨ࡢ 0&6&) ィ⟬࡞ࡢ࡛཰᮰ࡋ࡟ࡃ࠸ࡀࠊ࡯ࡰ ࡢィ⟬ࢆ⤊࠼ࡿࡇ࡜ࡀ࡛
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⏕యศᏊࡢẼ┦࢖࢜ࣥࡢ⏕ᡂ࡜࠸࠺ࣈ࣮ࣞࢡࢫ࣮ࣝࢆ㐩ᡂࡋࡓ㉁㔞ศᯒἲࡣࠊ⏕యศᏊࡢィ࡟Ḟ࠿ࡏ࡞࠸ᢏ⾡࡜࡞ࡗ࡚࠾ࡾࠊ⌧௦ࡢ⏕࿨⛉Ꮫ◊✲ࢆᨭ࠼࡚࠸ࡿࠋࡑࡢ୍᪉࡛ࠊ≉࡟௦ㅰ≀࡞࡝⏕యෆࡢపศᏊ໬ྜ
≀ࡢศᯒ࡟࠾࠸࡚ࠊศゎ⏕ᡂ≀ࡀ⏕ࡌࡿࡇ࡜ࡶሗ࿌ࡉࢀ࡚࠾ࡾࠊㄗྠᐃࡢཎᅉ࡜࡞ࡿࡓࡵࠊゎ㞳ຠ⋡ࢆணࡍࡿᡭἲࡢ㛤Ⓨࡀᚲせ࡜ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ࢚ࣞࢡࢺࣟࢫࣉ࣮ࣞ࢖࢜ࣥ໬㉁㔞ศᯒἲ㸦ESI-MS㸧࡟࠾ࡅࡿ⏕యศᏊࡢศᯒࡢ㝿࡟㉳ࡇࡿ௦ㅰ≀ࡢゎ㞳ࡢຠ⋡ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ண

ࡋࠊࡼࡾຠ⋡ⓗ࡟㉁㔞ศᯒἲࢆ⏝࠸ࡿࡓࡵࡢᇶ┙ᢏ⾡ࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2ィ⟬᪉ἲ⌮ㄽィ⟬ࡣ*DXVVLDQࣉࣟࢢ࣒ࣛ࡟ࡼࡿศᏊ㌶㐨ἲࠊᐦᗘỗ㛵ᩘἲ㸦DFT㸧࡟ࡼࡾ⾜ࡗࡓࠋࡑࢀࡒࢀࡢ⏕యศᏊ࡟ࡘ࠸࡚ࠊMP2(full), B3LYP, ȦB97XD, M06-2X-D3, DSD-PBEP86-D3, PBE0-DHࢆỗ㛵ᩘ࡜ࡋ࡚⏝࠸ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ/6-311++G(d,p)ࢆ⏝࠸ࡓࠋMP2(full)/6-311++G(d,p)࡛᭱㐺໬ࡉࢀࡓᵓ㐀࡟ࡘ࠸࡚ࡣCCSD(t)/cc-PVTZ࡛࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓࠋ඲࡚ࡢ᭱㐺໬ᵓ㐀࡟ࡘ࠸࡚᣺ືゎᯒࢆ⾜࠸ࠊᏳᐃᵓ㐀࠾ࡼࡧ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡉࡽ࡟㑄⛣≧ែࢆጞⅬ࡜ࡍࡿ,5&ࢆ⏝࠸཯ᛂゎᯒࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ㑄⛣≧ែࠊጞ≧ែࠊ࠾ࡼࡧ⤊≧ែࡼࡾࠊRRKM⌮ㄽࢆ⏝࠸࡚཯ᛂ㏿ᗘᐃᩘࢆ⟬ฟࡋࡓࠋ

3

◊✲ᡂᯝ
㉁㔞ศᯒ

ᐃࡢ㝿࡟ศゎࢆཷࡅࡎ࡟᳨ฟࡉࢀࡿ⏕యศᏊࡢ๭ྜࢆSurvival Yield㸦SY㸧࡜ࡋ࡚ᐃ⩏ࡍࡿࠋࡇ

ࡇ࡛ࠊSYࡢィ⟬್㸦SYcalc㸧ࡣࠊ⏕యศᏊࡢෆ㒊࢚ࢿࣝࢠ࣮P(E), ศゎ㏿ᗘᐃᩘk(E)ࠊ᫬ᐃᩘȫ࡟ࡼࡗ࡚ࠊᘧ㸦㸯㸧࡟ࡼࡾᘧ㸦1㸧࡟ࡼࡾồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ஶࡿࢅࢉࢇ࢒ࢉ ൌ ‫׬‬૙ ࡼሺࡱሻ ࢋି࢑ሺࡱሻ࣎ ࢊࡱ ࡇࡇ࡛ࠊ⏕యศᏊࡢෆ㒊࢚ࢿࣝࢠ࣮P(E)ࡣࠊEdwin De Pauw ࡽࡀᥦ᱌ࡋࡓ

ᗘィ࢖࢜ࣥࠕ࣋ࣥࢪࣝࣆࣜࢪࢽ

࣒࢘ࠖࢆ⏝࠸ࡓ࢖࢜ࣥࡢෆ㒊࢚ࢿࣝࢠ࣮ホ౯ἲ࡟ࡼࡗ࡚ࠊ୰ኸ್  kJ mol–1ࠊ್༙ᖜ 110 kJ mol–1 ࡛࠶ࡿࡇ࡜ࢆሗ࿌ࡋ࡚࠸ࡿࠋࡲࡓࠊ᫬ᐃᩘȫࡣ᪤ሗ࡟ᇶ࡙ࡁ 10–4 s ࡜௬ᐃࡋࡓࠋ ཯ᛂ㏿ᗘᐃᩘ k(E)ࡣࠊศᏊ㌶㐨ἲࡲࡓࡣ DFT ࡜ RRKM ⌮ㄽࢆ⏝࠸࡚ồࡵࡓࠋᚓࡽࢀࡓ SYcacl ࢆࠊᘧ㸦2㸧࡛ồࡵࡓ SY ࡢᐇ㦂್㸦SYexp㸧࡜ẚ㍑ࡋ
ࡓࠋࡇࡇ࡛ࠊ⏕యศᏊࢆศᯒࡋࡓ㝿࡟ᚓࡽࢀࡓ࣐ࢫࢫ࣌ࢡࢺࣝ࡟⌧ࢀࡓศゎࢆཷࡅ࡞࠿ࡗࡓ⏕యศᏊࡢࢩࢢ
ࢼࣝࢆࡵࡹశ ࠊศゎࢆཷࡅ࡚ࣇࣛࢢ࣓ࣥࢺ࢖࢜ࣥ࡜ࡋ᳨࡚ฟࡉࢀࡓࢩࢢࢼࣝࢆ࡛ࡵࡲశ ࡜ࡋࡓࠋࡿࢅࢋ࢞࢖ ൌ ࡵࡵࡹశࡹశ ାࡵࡲశ

ᘧ㸦1㸧࡛ᚓࡽࢀࡓ SYcalc ࢆᶓ㍈࡟ࠊᘧ㸦2㸧࡛ᚓࡽࢀࡓ SYexp ࢆ⦪㍈࡟ࣉࣟࢵࢺࡋࡓᅗࢆ Figure 1 ࡟♧ࡍࠋ
Figure 1a-d ࡣ ࡑ ࢀ ࡒ ࢀ ࠊ CCSD(t)/cc-PVTZ//MP2(full)/6-311++G(d,p), B3LYP/6-311++G(d,p), ȦB97XD/6-- 279 -

311++G(d,p), M06-2X-D3/6-311++G(d,p), DSD-PBEP86-D3/6-311++G(d,p), PBE0-DH/6-311++G(d,p)࡟ࡼࡗ࡚ồࡵ
ࡓ཯ᛂ㏿ᗘᐃᩘ k(E)ࢆ⏝࠸࡚ SYcalc ࢆ⟬ฟࡋࡓ⤖ᯝ࡛࠶ࡿࠋCCSD(t)/cc-PVTZ//MP2(full)/6-311++G(d,p)࡛ᚓࡽ
ࢀࡓ SYcalc ࡜ SYexp ࡢ㛵ಀࢆ Figure 1a ࡟ࣉࣟࢵࢺࡋࡓࠋSYcalc ࡜ SYexp ࡣᴫࡡ୍⮴ࡍࡿഴྥ࡛࠶ࡾࠊᮏ◊✲࡛⏝࠸࡚࠸ࡿ༢ศᏊศゎ㐣⛬ࡢࣔࢹࣝ࡟ࡼࡗ࡚ࠊ㉁㔞ศᯒ⿦⨨ෆ࡟࠾ࡅࡿ⏕యศᏊ⏤᮶ࡢ࢖࢜ࣥࡢẼ┦ศゎ཯ᛂࡢホ౯ࡀ⾜࠼ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ୍᪉ࠊB3LYP/6-311++G(d,p)ࢆ౑⏝ࡋࡓሙྜࠊSYcalc ࡜ SYexp ࡜ࡢ୍⮴ᗘࡣపࡃࠊศゎ཯ᛂࢆṇ☜࡟ホ౯࡛ࡁ࡚࠸࡞࠸㸦Figure 1b㸧ࠋࡇࢀࡣ B3LYP/6-311++G(d,p)ࡀศゎ཯ᛂࡢάᛶ໬
࢚ࢿࣝࢠ࣮ࢆ㐣ᑠホ౯ࡍࡿഴྥ࡟࠶ࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋFigure 1c, 1d ࡟♧ࡋࡓࡼ࠺࡟ ȦB97XDࠊM062X-D3 ࡢ౑⏝࡟ࡼࡗ࡚⟬ฟࡉࢀࡿ SYcalc ࡣࠊSYexp ࡜ࡼࡃ୍⮴ࡋࡓࠋࡇࢀࡽࡢỗ㛵ᩘࡣ࢖࢜ࣥࡢゎ㞳࡟ࡘ࠸࡚ࠊ
B3LYP ࡼࡾࡶṇ☜࡞᝟ሗࢆ୚࠼ࡿ࡜⪃࠼ࡽࢀࡿࠋࡼࡾ㧗⢭ᗘ࡞ࢲࣈࣝࣁ࢖ࣈࣜࢵࢻ DFT ἲ࡛࠶ࡿ DSDPBEP86-D3(BJ)ࠊPBE0-DH ࡶ ȦB97XDࠊM06-2X-D3 ࡜ྠᵝ࡟ࠊSYexp ࡜ࡼࡃ୍⮴ࡍࡿ SYcalc ࢆ୚࠼ࡿࡇ࡜ࡀࢃ
࠿ࡿ㸦Figure 1e, 1f㸧
ࠋPost-HF ἲࡸ㐺ษ࡞ࣁ࢖ࣈࣜࢵࢻ DFTࠊࢲࣈࣝࣁ࢖ࣈࣜࢵࢻ DFT ἲࡢ౑⏝࡟ࡼࡗ࡚㉁㔞ศᯒ⿦⨨ෆ࡟࠾ࡅࡿ⏕యศᏊ⏤᮶ࡢ࢖࢜ࣥࡢẼ┦ศゎ཯ᛂ࡟ࡘ࠸࡚ṇ☜࡞᝟ሗࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࡇ࡜ࡀ
᫂ࡽ࠿࡜࡞ࡗࡓࠋ

Figure 1. SYcalc ࡜ SYexp ࡢ㛵ಀࠋSYcalc ࡜ SYexp ࡣࡑࢀࡒࢀᘧ㸦㸯㸧ࠊᘧ㸦㸰㸧࡟ࡼࡾồࡵࡓࠋ◚⥺ࡣ 67㸣ㄗᕪ⠊ᅖࢆ♧ࡍࠋ

4Ⓨ⾲ࠊฟ∧ᐇ⦼‫ ۻ‬1. D. Asakawa, E. Sugiyama, H. Mizuno, K. Todoroki, J. Am. Soc. Mass Spectrom. 32, 2144-2152 (2021)‫ ۻ‬2. D. Asakawa, K. Saikusa, J. Mass Spectrom. 57, e4530 (2022)‫ ۻ‬3. D. Asakawa, H. Takahashi, S. Iwamoto, K. Tanaka, J. Am.Chem. Soc. 144, 3020-3028 (2022)- 280 -

㔠ᒓ㘒యࡢ㓟໬㑏ඖ㟁఩࡟㛵ࡍࡿࢹ࣮ࢱ࣮࣋ࢫసᡂCreation of database on redox potential of metal complexes㔠୸ 㞝ᇶ ෠ኈཎ ₶ ‫ۑ‬ᯇ஭ ஽㸦⟃Ἴ኱㝔ᩘ≀㸧◊✲┠ⓗࠊෆᐜ

㔠ᒓ㘒యࡢ㓟໬㑏ඖ㟁఩ࡣ㟁Ꮚᤵཷࡢࣉࣟࢭࢫࢆ▱ࡿୖ࡛኱஦࡞≀ᛶࡢ୍ࡘ࡛࠶ࡿࡀ ࡇࢀࡽࡢ್ࢆ༶ᗙ
࡟▱ࡿ᪉ἲࡣ⌧ᅾࡢ࡜ࡇࢁ㝈ࡽࢀ࡚࠸ࡿ ࡑࡇ࡛ ィ⟬ ⡆༢ࡢࡓࡵㄏ㟁యࣔࢹࣝ ලయⓗ࡟ࡣ 3&0 ࢆ฼⏝࡟ࡼࡗ࡚ࡑࢀࡽࢆண

ࡋ࡚㓟໬㑏ඖ㟁఩ࡢࢹ࣮ࢱ࣮࣋ࢫࢆసࡿࡇ࡜ࡀᮏ◊✲ࡢ᭱⤊┠ᶆ࡛࠶ࡿࡀ ࡇࢀࢆᐇ⾜ࡍࡿ࡟ࡣ  ࡘࡢ㞀ቨ   ィ⟬ࡢ⢭ᗘࡢ᳨ド   ཧ↷࡜ࡍࡿ㟁ᴟ㟁఩ࡀィ⟬ෆᐜ࡟ࡼࡗ࡚␗࡞ࡿ  㟁Ⲵࢆᣢࡘ㘒యࡢ⁐፹࿴࢚ࢿࣝࢠ࣮࡟⿵ṇࡀᚲせ ࡀ࠶ࡿ ௒ᖺᗘࡢ◊✲࡛ࡣ ≉࡟  ࡟㛵㐃ࡋ࡚ ࡇࢀࡽࡢ㘒య࡟࠾࠸࡚ᐦᗘỗ㛵ᩘ⌮ㄽ ')7 ࡢ⿵ṇ࡟ࡼࡾ㓟໬㑏ඖ㟁఩ࡢ⟬ฟࡀྍ⬟࠿ࢆ᳨ウࡋ࡚ࠕ㔠ᒓ㘒యࡢ㓟໬㑏ඖ㟁఩ࢆ㧗࠸⢭ᗘ࡛ồࡵ ࢹ࣮ࢱ࣮࣋ࢫࢆసᡂࡍࡿࡓࡵࡢᅵྎࢆసࡿࡇ࡜ࠖࢆ┠ⓗ࡜ࡍࡿ

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R   [q-FJ:FJ:ºd 6J>2ÍÃdT~ %!*s*¨ # s1. “Density functional theory of molecular liquids for biophysics and chemical physics,” 3rd International
Conference on Materials Research and Innovation(ICMARI), 2021

12  15, Bangkok, Thailand,

Norio Yoshida, 2. “Development of a hybrid method of three-dimensional reference interaction-site model theory andquantum chemical electronic structure theory for biomolecules,” Pacifichem 2021, Scheduled, Honolulu,
Hawaii, USA, Norio Yoshida, 4 !
1. "Implementation of solvent polarization in three-dimensional reference interaction-site model selfconsistent field theory", Chem. Phys. Lett., (2022) 797, 139579, Norio Yoshida*, Tsuyoshi Yamaguchi,
Haruyuki Nakano
2. “Modeling the interaction of SARS-CoV-2 binding to the ACE2 receptor via molecular theory of solvation,”
New Journal of Chemistry, In press (2021) Alexander E. Kobryn*, Yutaka Maruyama, Carlos A.
Velazquez-Martinez, Norio Yoshida, Sergey Gusarov*
3.

“Temperature-Responsive Morphology Formation of PS-b-PI copolymer: A Dissipative Particle
Dynamics Simulation Study”, Natthiti Chiangraeng, Ukrit Keyen, Norio Yoshida and Piyarat
Nimmanpipug*, Soft Matter, Vol. 17, 6248-6258 (2021)- 284 - π 

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6L<#ÆÅ¡#"i.¼3]V³"$4E>Ñ2RÔ"* N ¾BA;<#ß[Îµ¶ ,&T5I8 N G;J4H=L#¦»O"uÀm2y\×#RÔß[Î"P /Ù#ÈX#Þ2w

 8<

)J=

)

2.1. β 4E>Ñ2RÔ"* N ¾BA;<#ß[Îµ¶97KBL:L2RÔÛ"*4E>Ñ-0/ N ¾BA;<" 0'"#ÓshtÅ¹",-0´Ã2*"¥¢Q#Î2wÚ³"Ç/]V³"$Ud"i½Î2*"ÞÓV#aÎ2¤Z02 gaussian 16 2® B3LYP/631G*2Ö/m|Ö DFT Å¹",ÎÏh#×wÚ³"Î v2Â ×"¥rW®/7KKCJF2 implicit !~¥r Å¹2ÂNwÚ³!Îv$Ò7KKCJF2¥r NMR Å£",.Â
2.2. 5I8 N G;J4H=L#¦»O"uÀm2y\×#RÔß[Î"P /Ù#ÈX $0'5I8 N G;J4H=L#4E<·»O"p!uÀm2y\*RÔ#¸VÐ}
pnh! 2Ã^02b®:L?7ËI6L<#ÆÅ2Â[1]µ¶$
¦»O"¾m2y\*RÔ#ÎY0/2Gaussian 16 2®  DFT Å¹ Gromacs 2® _sgftÜMDÝÅ¹",É

 8<%3.1. β 4E>Ñ2RÔ"* N ¾BA;<#ß[Îµ¶- 287 -

½Î¯#¸VÐ}2 DFT Å¹",.ÎÏh#Î NMR ",i0AK L
E#<E³!D$"20-k186#! 9@0# N ¾BA;<¥¢Q*½Q(-0vÐ}2Y# /9@0
2.2. 5I8 N G;J4H=L#¦»O"uÀm2y\×#RÔß[Î"P /Ù#ÈX
DFT Å¹#½)N G;J4H=LBL: M#Î 1, 3, 5 ,m4"uÀm2y\k#RÔ#Î$pn1-! 9@0'MD Å¹#½)-uÀm#y\$ N ¾BA;<#R
ÔÎ#5"Ù2P ! *9@0-"#½)"m5I8 N G;J4H=L
2C,.o!:L?7ËI6L<2ÆÅ/2:"[2]

 2HA[1] * /, BA <#¸VÐ}ceÁ#zÕ, LiHub >IeÁ, 2021

7'2%

[2] * /, T{Q_sBA <#¸VÐ}c:L?7ËI6L<ÆÅ#zÕ, k
htt­9LD F, 2021

10 ' 16 %[3] +71H2p;O2Ã=!-.*/(, Oligo(N-methylalanine)
as a molecular scaffold for designing protein ligands, > 58  BA;<?A, 2021

10 ' 20 %[4] */, BA <#¸VÐ}µ¶­V_s@B#zÕ, > 58  BA;<?A, 2021
10 ' 22 %[5] Jumpei Morimoto, Marin Yokomine, Yasuhiro Fukuda, Takumu Watanabe, Daisuke Kuroda, Kouhei Tsumoto,Shinsuke Sando, Conformational studies of peptoids with substituents on backbone carbons and application of the
peptoids for rational design of protein ligands, Pacifichem 2021, 2021

12 ' 21 %[6] 3G FO2 Ã= !* /( , N G;JBA;<"Ï®jÀ!
MAH ~#y^, %ht> 103 & , 2022

-A

3 ' 26 %[1] Y. Fukuda, M. Yokomine, D. Kuroda, K. Tsumoto, J. Morimoto, S. Sando, “Peptoid-Based Reprogrammable
Template for Cell-Permeable Inhibitors of Protein–Protein Interactions”, Chem. Sci., 2021, 12, 13292-13300.
[2] T. Ono, K. Aikawa, T. Okazoe, J. Morimoto, S. Sando, “Methyl to trifluoromethyl substitution as a strategy toincrease the membrane permeability of short peptides”, Chem. Sci., 2021, 19, 9386-9389.
[3] Y. Hosono, J. Morimoto, S. Sando, “A comprehensive study on the effect of backbone stereochemistry of a cyclic
hexapeptide on membrane permeability and microsomal stability”, Org. Biomol. Chem., 2021, 19, 10326-10331.
[4] M. Yokomine, J. Morimoto, Y. Fukuda, Y. Shiratori, D. Kuroda, T. Ueda, K. Takeuchi, K. Tsumoto, S. Sando.,“A comprehensive study on the effect of backbone stereochemistry of a cyclic hexapeptide on membrane permeability
and microsomal stability”, Angew. Chem. Int. Ed., 2022, 61, e202200119.

C.
>@-0RULPRWR    ±
>@M. Yokomine  H

- 288 -

CDFT ศᏊືຊᏛィ⟬࡟ࡼࡿ᰾ኚ᥮⁐⼥ሷࢱ࣮ࢤࢵࢺࡢ㟁Ꮚ⛣ື཯ᛂᛶホ౯
Evaluation of Electron Transfer Reactivity of Molten Salt Using
Constrained Density Functional Molecular Dynamics Simulation for
Nuclear Transmutation Targets‫ۑ‬᏷ᡞ ༤⣖㸦ᮾ໭኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧




◊✲┠ⓗ
ཎᏊຊⓎ㟁ᡤࡼࡾ⏕ࡌࡿ㧗ࣞ࣋ࣝᗫᲠ≀ࡢฎ⌮ฎศ᪉ἲࢆ᪩ᮇ࡟☜❧ࡍࡿࡇ࡜ࡣཎᏊຊ࢚ࢿࣝࢠ࣮฼⏝࡟࠾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୰࡟ฎ
ศࡍࡿ࡟ࡋ࡚ࡶࠊ࠶ࡿ࠸ࡣูࡢฎ⌮᪉ἲࢆ᥇⏝ࡍࡿ࡟ࡋ࡚ࡶࠊ㉸㛗ᮇࡢᏳ඲☜ಖࢆ⪃࠼࡞ࡃ࡚ࡣ࡞ࡽ࡞࠸ࠋ
ࡇࢀࢆཷࡅ࡚ࠊ㧗ࣞ࣋ࣝᗫᲠ≀᰾✀࡟ᑐࡋ୰ᛶᏊࢆ↷ᑕࡍࡿࡇ࡜࡛ࠊ▷༙ῶᮇࡲࡓࡣᏳᐃ᰾✀࡬᰾ኚ᥮ࡍࡿ
ࡇ࡜ࡀᥦ᱌ࡉࢀ࡚࠸ࡿ>@ࠋࡇࢀࡲ࡛ࡢ◊✲࡛ࡣ㧗ࣞ࣋ࣝᗫᲠ≀ࢆྵࡴ୰ᛶᏊ⿕↷ᑕయ㸦ࢱ࣮ࢤࢵࢺ㸧ࡣᖖ࡟ᅛయ࡜᝿ᐃࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࢱ࣮ࢤࢵࢺࢆᾮయ࡜ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤࠊࡑࢀࢆ᰾ኚ᥮ࢩࢫࢸ࣒ࡢෆእ࡟
ὶືࡉࡏࡿࡇ࡜࡛ࠊࢱ࣮ࢤࢵࢺࡢᐃᮇⓗ஺᥮ࡀ୙せ࡟࡞ࡿࠊ㐠㌿୰࡟ᡂศࢆㄪᩚࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿ࡞࡝ࠊ
ከࡃࡢᕤᏛⓗ฼Ⅼࡀ⏕ࡌࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡇࡢࡼ࠺࡞᝿ᐃࡢୗࠊ⁐⼥ሷ࡟ࡇࢀࡽ㧗ࣞ࣋ࣝᗫᲠ≀ࢆῧຍࡋࡓ᪂ࡓ࡞᰾ኚ᥮ࢱ࣮ࢤࢵࢺࢆᥦ᱌ࡍࡿࠋཎ
Ꮚຊࢩࢫࢸ࣒࡟࠾ࡅࡿ⁐⼥ሷ࡜ࡋ࡚ࠊࣇࢵ໬ࣜࢳ࣒࢘ /L)  ࡜ࣇࢵ໬࣒࣋ࣜࣜ࢘ %H)  ࡢΰྜ⁐⼥ሷࡀ⏝࠸ࡽࢀ࡚ࡁࡓᐇ⦼ࡀ࠶ࡾࠊ⁐፹࡜ࡋ࡚ࡢ➨୍ೃ⿵࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊỈ㓟໬≀ሷࡶྠᵝ࡟ೃ⿵࡜⪃࠼࡚࠸ࡿࠋỈ㓟໬≀࢖࢜ࣥࡣࣇࢵ໬≀࢖࢜ࣥ࡜ྠᵝ࡟୰ᛶᏊ྾཰᩿㠃✚ࡀᑠࡉࡃࠊ࠿ࡘ୰ᛶᏊࢆῶ㏿ࡉࡏࡿࡇ࡜࠿
ࡽࠊᗫᲠ≀᰾✀ࡢ୰ᛶᏊ྾཰཯ᛂࢆಁ㐍࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࣇࢵ໬≀ሷ࡟ẚࡋ࡚Ỉ㓟໬≀ሷࡢ⼥Ⅼ
ࡣẚ㍑ⓗప࠸ࡇ࡜࠿ࡽࠊప

࡛ὶື࡛ࡁࡿ࡞࡝ࡢ฼Ⅼࡀ⪃࠼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࠶ࡿࠋ
௨ୖࡢ⫼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⏦ㄳᙜึࡣࠊ㟁Ⲵࢆᣊ᮰ࡋࡓᐦᗘỗ㛵ᩘ⌮ㄽィ⟬ &RQVWUDLQHGGHQVLW\IXQFWLRQDOWKHRU\&')7  ࢆᐇ᪋ࡋࠊ

0DUFXV ⌮ㄽ࡟ᇶ࡙࠸ࡓ㟁Ꮚ⛣ື࡟క࠺⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆホ౯ࡍࡿணᐃ࡛࠶ࡗࡓࠋࡇࢀ࡟ࡼࡾࠊ⁐፹ሷࡢྛ࢖࢜ࣥ࡜ῧຍࡋࡓ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲࡟ࡘ࠸࡚ࠊ཯ᛂ๓ࢆጞ≧ែࠊ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲࠿ࡽ⁐፹࢖࢜ࣥ࡬
㟁Ꮚࡀᤵཷࡉࢀࡓ⣔ࢆ⤊≧ែ࡜ࡋࠊ ࡘࡢ≧ែ࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆホ౯ࡍࡿࡇ࡜࡛ࠊᙜヱ཯ᛂࡢ㉳ࡇࡾࡸࡍࡉࢆ᥎

࡛ࡁࡿ࡜⪃࠼ࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊᙜヱᡭἲࢆ⏝࠸ࡓホ౯ࢆ୰Ṇࡋࡓࠋࡑࡇ࡛ᮏ◊✲࡟࠾࠸࡚ࡣࠊ:LGRP ࡢ⢏Ꮚᤄධἲࢆ⏝࠸ࡓ໬Ꮫ࣏ࢸࣥࢩࣕࣝホ౯࡜ࠊࡑࢀ࡟ᇶ࡙࠸ࡓ⁐ゎᗘ

- 289 -

ண

ࢆヨࡳࡓ>@ࠋ࠶ࡿ⁐㉁ࡢ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡣḟࡢࡼ࠺࡟ࠊ⌮᝿Ẽయ࡟ࡼࡿᐤ୚ศ࡜వ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ࿴࡜ࡋ࡚⾲ࡉࢀࡿࠋߤ௚ (ܰ; ܰ + 1) = ߤ௚௜ௗ + ߤ௚௘௫                                      ࡇࡇ࡛ࠊȝg 11 ࡣ⢏Ꮚ 1 ಶ࠿ࡽᡂࡿ⁐፹࡟ᑐࡋࢸࢫࢺ⢏Ꮚࢆᤄධࡋࡓ⣔࡛ࡢ໬Ꮫ࣏ࢸࣥࢩ࡛ࣕࣝ࠶ࡿࠋవ
๫໬Ꮫ࣏ࢸࣥࢩࣕࣝࡣḟᘧࡢ㏻ࡾ⾲ࡉࢀࡿࠋ
ߤ௚௘௫ = െߚଵ lnࡇࡇ࡛ࠊȕ ࡣ㏫

‫࢙݀ ׬ ܸۃ‬ேାଵ exp(െߚȟܷ)‫ۄ‬
‫ۄܸۃ‬

(2)

ᗘࠊV ࡣィ⟬ࢭࣝࡢయ✚ࠊV ࡣィ⟬ࢭ࡛ࣝつ᱁໬ࡉࢀࡓᗙᶆ⣔ࠊ࢔ࣥࢢࣝࣈࣛࢣࢵࢺࡣ 1S7࢔ࣥࢧࣥࣈࣝ࡟࠾ࡅࡿᖹᆒࢆ⾲ࡍࠋࡉࡽ࡟ࠊ
ȟܷ = ܷ(‫ܠ‬ଵ..ே ; ‫ ܠ‬ேାଵ ) െ ܷ(‫ܠ‬ଵ..ே ) െ ܷ଴,௚                                ࡛࠶ࡿࠋU [1 ࡣ⁐፹ࡢ ')7 ィ⟬࡟ࡼࡿ඲࢚ࢿࣝࢠ࣮࡛࠶ࡾࠊU [1[1 ࡣࡇࡢ⁐፹࡟ᑐࡋ࡚ࢸࢫࢺ⢏Ꮚࢆ[1 ࡟ᤄධࡋࡓ㝿ࡢ඲࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋࡲࡓࠊUJ ࡣẼయ≧ែ࡟࠾ࡅࡿࢸࢫࢺ⢏Ꮚࡢཧ↷࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋ
వ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࡣ :LGRP ࡢ⢏Ꮚᤄධἲ࡟ࡼࡾホ౯ࡍࡿ>@ࠋࡲࡎࠊ⁐፹⣔࡟ᑐࡋ࡚ ')7 ィ⟬࡟ᇶ࡙
࠸ࡓ 0' ィ⟬ࢆᐇ᪋ࡋࠊ⢏Ꮚ㓄⨨ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆᩘⓒಶ࡯࡝⏝ពࡍࡿࠋ⥆࠸࡚ࠊ⁐፹⣔ࡢィ⟬ࢭࣝࢆ➼㛫㝸ࡢࢢࣜࢵࢻ࡬ศ๭ࡋࠊࡍ࡭࡚ࡢ᱁ᏊⅬ࡟ࢸࢫࢺ⢏Ꮚࢆᤄධࡋࡓ㝿ࡢ඲࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࠋࡇࢀࢆ
ࡍ࡭࡚ࡢࢫࢼࢵࣉࢩࣙࢵࢺࠊ࠾ࡼࡧࡍ࡭࡚ࡢ᱁ᏊⅬ࡟ᑐࡋ࡚ᐇ⾜ࡋࠊᘧ  ࡼࡾ ȝH[ ࢆホ౯ࡍࡿࠋ࡞࠾ࠊ⢏Ꮚࡢᤄධ఩⨨࡟ࡼࡗ࡚ࡣ⁐፹ཎᏊ࡜㏆ࡍࡂࡿࡓࡵ࡟ 6&) ィ⟬ࡀᐇ᪋࡛ࡁ࡞࠸ࢣ࣮ࢫࡀ࠶ࡾࠊࡑࡢሙྜࡢ᱁ᏊⅬࡣᖹᆒ࠿ࡽ㝖እࡋ࡚࠸ࡿࠋ
ᮏ◊✲࡟࠾࠸࡚ࡣࠊ⁐፹ /L) ࡟ᑐࡍࡿ =U ࡢ⁐ゎᗘࢆホ౯ࡍࡿࠋᙜヱ⣔࡟࠾ࡅࡿ =U ࡢ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ
ኚ໬ࡣḟᘧ࡛⾲ࡉࢀࡿࠋȟߤ௟ ൫Zr௫ (LiF)௬ ; Zr൯ = ߤ௚௘௫ ൫Zr௫ (LiF)௬ ; Zr൯ െ ߤ௚௘௫ (Zr(݈); Zr)                      ῧຍࡍࡿ =U ࢆቑࡸࡋ࡚࠸ࡁࠊǻȝl ࡀṇࡢ್࡟ኚࢃࡿῧຍ㔞ࢆ⁐ゎᗘ࡜᥎ᐃࡍࡿࠋ
ᮏ◊✲࡟࠾ࡅࡿ ')70' ィ⟬࡟ࡣࠊᨃ࣏ࢸࣥࢩࣕࣝἲ࡜ᖹ㠃Ἴᇶᗏ࡟ࡼࡿᐦᗘỗ㛵ᩘ⌮ㄽィ⟬ࣉࣟࢢ࣒ࣛ
࡛࠶ࡿ 4XDQWXP (635(662 ࢆ౑⏝ࡋࡓ>@ࠋ')7 ィ⟬࡟࠾ࡅࡿㅖ᮲௳࡜ࡋ࡚ࡣࠊ3$: ᆺᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࠊᖹ㠃Ἴ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࢆ 5\ࠊ㟁Ⲵ࢝ࢵࢺ࢜ࣇࢆ 5\ࠊN Ⅼ࣓ࢵࢩࣗࡣ îîࠊ6&) ィ⟬཰᮰᮲௳ࡣ í 5\ ࡜ࡋࡓࠋࡲࡓࠊࢫ࣓࢔ࣜࣥࢢ࡜ࡋ࡚ 0DU]DUL±9DQGHUELOW ࡟ࡼࡿ᪉ἲࢆ㐺⏝ࡋࡓࠋ0' ィ⟬࡟࠾ࡅࡿㅖ᮲௳࡜ࡋ࡚ࡣࠊ1S7 ࢔ࣥࢧࣥࣈࣝࠊ᫬㛫ࢫࢸࢵࣉࡣ  DXࠊ

ᗘไᚚࡣ㏿ᗘࢫࢣ࣮ࣜࣥࢢἲࠊᅽຊไ

ᚚࡣ :HQW]FRYLWFK ࡢ᪉ἲ࡜ࡋࡓࠋ⁐፹ࡢࢩࢫࢸ࣒ࢧ࢖ࢬࡣ  ಶ࡛࠶ࡾࠊ/L) ࢖࢜ࣥ࣌࢔ࡀ  ಶ࡛࠶ࡿࠋ



◊✲ᡂᯝ

 ᐦᗘホ౯ࡣࡌࡵ࡟ ')70' ィ⟬࡟ࡼࡿ⁐፹ /L)  ࡢᐦᗘホ౯ࢆᐇ᪋ࡋࡓࠋᮏホ౯࡛ࡣ 1S7 ࢔ࣥࢧࣥࣈ࡛ࣝィ⟬ࡋ࡚࠸ࡿࡓࡵࠊ஺᥮┦㛵ỗ㛵ᩘ࡜ࡋ୍࡚⯡ⓗ࡞ 3%( ࡟ຍ࠼࡚ࠊศᩓຊࢆ⪃៖ࡍࡿࡓࡵ࡟ࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫᐦ
ᗘỗ㛵ᩘ YG:')>@ࢆࡑࢀࡒࢀ⏝࠸࡚ࠊᐦᗘ್࡟ཬࡰࡍᙳ㡪ࢆホ౯ࡋࡓࠋᅗ  ࡟ྛỗ㛵ᩘ࡟࠾ࡅࡿࠊ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫࡟ᑐࡍࡿ /L) ࡢᐦᗘࢆ♧ࡍࠋ⣔ࡢᗘࡣ  . ࡛࠶ࡿࠋᅗ  ࡼࡾࠊ஺᥮┦㛵ỗ㛵ᩘ࡟

3%( ࢆ⏝࠸ࡓሙྜࡣࠊᐇ㦂್࡟ẚࡋ࡚ᐦᗘࢆ㐣኱ホ౯ࡋ࡚࠾ࡾࠊࡑࡢᕪࡣ࠾ࡼࡑ ࡛࠶ࡗࡓࠋ୍᪉࡛ࠊYG:') ࢆ⏝࠸ࡓሙྜࡣẚ㍑ⓗࡼࡃᐇ㦂್ࢆ෌⌧ࡋ࡚࠾ࡾࠊࡑࡢᕪࡣ⣙ ࡛࠶ࡗࡓࠋࡼࡗ࡚ࠊࣇ࢓ࣥࢹ࣮ࣝ࣡

- 290 -

2.3
2.2

-

3)

2.1

Density (gcm

2.0
vdW-DF
PBE

1.9

Experiment

1.8
1.7
1.6
0

2

4

6

8

10

Simulation time (ps)ᅗ ྛỗ㛵ᩘ࡟ࡼࡿ 0' ィ⟬ࢫࢸࢵࣉࡈ࡜ࡢ /L) ᐦᗘ࠾ࡼࡧᐇ㦂್>@㸦ᗘ .㸧

1.80
This study

1.78

This study (regression)Experiment

1.74

-3

)

1.76

Density (gcm

1.72
1.70
1.68
1.66
1.64
1.62
1.60
1200

1250

1300

1350

1400

Temperature (K)ᅗ 

YG:') ỗ㛵ᩘ౑⏝᫬ࡢ /L) ᐦᗘࡢᗘ౫Ꮡᛶ ᐇ㦂್>@ࣝࢫᐦᗘỗ㛵ᩘ YG:') ࢆ౑⏝ࡍࡿࡇ࡜࡛ศᩓຊࡀ㐺ษ࡟⪃៖ࡉࢀࠊ⁐⼥ሷࡢᐦᗘࢆ⢭ᗘࡼࡃホ౯࡛ࡁࡿࡇ
࡜ࡀ☜ㄆࡉࢀࡓࠋ
ᙜヱỗ㛵ᩘࢆ⏝࠸࡚ホ౯ࡋࡓᐦᗘࡢ

ᗘ౫Ꮡᛶࢆᅗ  ࡟♧ࡍࠋྛᗘ࡟࠾ࡅࡿᐦᗘィ⟬⤖ᯝࡣᐇ㦂್࡜ᴫࡡ୍⮴ࡋ࡚࠾ࡾࠊࡑࡢᕪࡣ᭱኱࡛ ࡛࠶ࡗࡓࠋࡋ࠿ࡋࠊ ᗘ࡟ᑐࡍࡿᐦᗘࡢഴࡁࠊࡍ࡞ࢃࡕ⭾ᙇ⋡ࡣᐇ㦂್ࡼࡾࡶ㐣ᑠホ౯ࡋ࡚࠸ࡿᵝᏊࡀぢࡽࢀࡿࠋࡇࢀ࡟ࡘ࠸࡚ࡣࠊ௒ᅇ⏝࠸ࡓࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫᐦᗘỗ㛵ᩘYG:') ࡟ࡣᵝࠎ࡞ᨵⰋ∧ࡀ㛤Ⓨࡉࢀ࡚࠾ࡾࠊࡇࢀࡽࢆ㐺⏝ࡍࡿࡇ࡜࡛ࡼࡾ⢭ᗘࡼࡃᐦᗘࢆண

࡛ࡁࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ
 ໬Ꮫ࣏ࢸࣥࢩࣕࣝ࠾ࡼࡧ⁐ゎᗘホ౯/L) ࢆ⁐፹࡜ࡋࡓ࡜ࡁࡢ =U ࡢ⁐ゎᗘணࢆ⾜࠺ࠋ⁐፹ /L)㸦࢖࢜ࣥ࣌࢔ᩘ  ಶ㸧࡟ᑐࡋࠊࢸࢫࢺ⢏Ꮚ࡜ࡋ࡚  ಶࡢ =U ࢆ⣔࡟ᤄධࡋࡓ᫬ࡢ໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࢆࠊ:LGRP ࡢ⢏Ꮚᤄධἲ࡟ᇶ࡙࠸࡚ᘧ  ࡼࡾホ౯ࡍ- 291 -

⾲ྛ⣔࡟࠾ࡅࡿవ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࡜⢏Ꮚᤄධ࡟ࡼࡿ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢᕪ ǻȝl⁐፹ࢸࢫࢺ⢏Ꮚ

ȝH[k%Tǻȝlk%T/L) 

=Uí  í/L) =U=Uí  í/L) =U=Uí  í

=U 

=U

ࡿࠋィ⟬ࢭࣝࢆ îî ࡟ศ๭ࡋࡓࢢࣜࢵࢻ࡟ࡑࢀࡒࢀࢸࢫࢺ⢏Ꮚࢆᤄධࡋࡓࠋࡇࡢ࡜ࡁࡢࢢࣜࢵࢻ㛫ࡢ㛗ࡉࡣ࠾࠾ࡼࡑ c ࡛࠶ࡿࠋྠᵝ࡟ࡋ࡚ࠊ /L) =Uࠊ /L) =Uࠊ =U  ࢆ⁐፹࡜ࡋ࡚ࢸࢫࢺ⢏Ꮚ =U ࢆ  ࡘᤄධࡋࡓ᫬ࡢవ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࢆホ౯ࡍࡿࠋࡑࡋ࡚ᘧ  ࡼࡾࠊྛ⣔࡛ࡢవ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ࡜ =U ࢆ⁐፹࡜ࡍࡿ⣔ࡢవ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ࡜ࡢᕪࢆྲྀࡿࡇ࡜࡛ࠊǻȝl ࢆホ౯ࡍࡿࠋ⾲  ࡟ᚓࡽࢀࡓవ๫໬Ꮫ࣏ࢸ
ࣥࢩࣕࣝ࡜໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢᕪࢆࡲ࡜ࡵࡿࠋ⾲  ࡼࡾࠊ/L) ࡟ =U ࢆῧຍࡍࡿ⣔࡟࠾࠸࡚ࡣࠊ=U ῧຍ㔞ࡢቑຍ࡟క࠸వ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࡢୖ᪼ࡀ☜ㄆࡉࢀࡓࠋ=U㸦ཎᏊᩘ  ಶ㸧࡟ࢸࢫࢺ⢏Ꮚ =U ࢆᤄධࡋࡓ᫬ࡢ
వ๫໬Ꮫ࣏ࢸࣥࢩࣕࣝ ȝH[ ࡣ㠀ᖖ࡟㧗࠸್ࢆ♧ࡋࡓࠋ⁐ゎᗘண࡟࠾࠸࡚ࡣࠊ⁐㉁ࢆቑࡸࡋ࡚࠸ࡁ ǻȝl ࡀṇࡢ್࡟࡞ࡿ⤌ᡂࢆ௨࡚⁐ゎᗘ࡜ࡍࡿࡀࠊᮏ◊✲࡟࠾࠸࡚ࡣ᫂☜࡞್ࢆᚓࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
x᏷ᡞ༤⣖㸪ᶫ∎⚽฼㸪')7 ศᏊືຊᏛィ⟬࡟ࡼࡿ⁐⼥ሷ୰ࡢᨺᑕᛶᗫᲠ≀ඖ⣲ࡢ⁐ゎᗘホ౯㸪➨ ᅇ⁐⼥ሷ໬Ꮫウㄽ఍㸪ᮾி኱Ꮫ⏕⏘ᢏ⾡◊✲ᡤ㸪 ᖺ  ᭶  ᪥̿ ᪥㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋ


ཧ⪃ᩥ⊩
>@06WHLQEHUJ*:RW]DN%0DQRZLW]%1/%URRNKDYHQ1DWLRQDO/DERUDWRU\  >@0/LXHWDO-(OHFWURFKHP6RF(  >@%:LGRP-&KHP3K\V  >@3*LDQQR]]LHWDO-3K\V&RQGHQV0DWWHU  >@0'LRQHWDO3K\V5HY/HWW  >@*--DQ]HWDO165'61%6  - 292 -

༢ᒙ &17 ࢝࢖ࣛࣜࢸ࢕ไᚚྜᡂ࡟ྥࡅࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ 
0ROHFXODU'\QDPLFV6LPXODWLRQIRUWKH&KLUDOLW\&RQWURORI6LQJOH
:DOOHG&DUERQ1DQRWXEHV  ‫୸ۑ‬ᒣ ⱱኵ, ᑠᖭ 㑳┿, ྜྷᕝ ு (ᮾி኱Ꮫ), ஂ㛫 㤾 (ಙᕞ኱Ꮫ)



◊✲┠ⓗ
༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ(༢ᒙ CNT)ࡣࢢࣛࣇ࢙ࣥࢆ෇⟄≧࡟ᕳ࠸ࡓᵓ㐀ࢆᣢࡘ≀㉁࡛࠶ࡾ, ᕳࡁ᪉(࢝࢖ࣛࣜࢸ࢕)࡟ࡼࡗ࡚㔠ᒓ, ༙ᑟయ୧᪉ࡢᛶ㉁ࢆ♧ࡍ. ༢ᒙ CNT 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, ༢ᒙ CNT ࡢᡂ㛗࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡋ, ࡑࢀ࡟ᇶ࡙ࡁྜᡂ᮲௳ࡢ᳨ウࢆ⾜࠺ᚲせࡀ࠶ࡿ. ࡑࡇ࡛ᮏ◊✲࡛ࡣ, Ⅳ⣲-ྜ㔠୕ඖ⣲⣔࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨ࠾ࡼࡧศᏊືຊᏛἲ࡟ࡼࡿ༢ᒙ CNT ࡢᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸, ྜ㔠ゐ፹࠿ࡽࡢ༢ᒙ
CNT ᡂ㛗࣓࢝ࢽࢬ࣒ࢆศᯒࡍࡿ.

◊✲᪉ἲࠊィ⟬᪉ἲከඖ⣲⣔ᚤ⢏Ꮚࡢ」㞧࡞࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃ࢆ⢭ᗘࡼࡃ㏆ఝࡍࡿࡢࡣ㠀ᖖ࡟ᅔ㞴࡛࠶ࡿ. ࡑࡇ࡛ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࣏ࢸࣥࢩࣕࣝࢆᑟධࡍࡿࡇ࡜࡛, 㧗⢭ᗘ࡞ཎᏊ㛫࣏ࢸࣥࢩࣕࣝࡢᵓ⠏ࢆ⾜࠺. ᮏᖺ
ᗘࡣ, C-Fe ஧ඖ⣲⣔࡟ᑐࡋ࡚ཎᏊ㛫࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨࢆ⾜ࡗࡓ. ᩍᖌࢹ࣮ࢱ࡟ࡣ, Ḟ㝗ࢢࣛࣇ࢙ࣥᵓ㐀, ༢ᒙ CNT ᡂ㛗㐣⛬ࡢཎᏊᵓ㐀, ୙つ๎ᵓ㐀ࡢ୕✀㢮ࡢ୕✀㢮ࡢᵓ㐀ࢹ࣮ࢱ࡟ᑐࡋ࡚ᐦᗘỗ㛵ᩘィ⟬ࢆ⾜ࡗ࡚ᚓࡓ࢚ࢿࣝࢠ࣮ࢆ⏝࠸ࡓ. ᐦᗘỗ㛵ᩘィ⟬࡟ࡣ VASP[2]ࢆ⏝࠸ࡓ. ௒ᅇᩍᖌࢹ࣮ࢱ࡜ࡋ࡚⏝࠸ࡓᵓ㐀ࡣ⣙ 42000
Ⅼ࡛࠶ࡗࡓ. ࡲࡓ, 㛤Ⓨࡋࡓ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚, ༢ᒙ CNT ᡂ㛗㐣⛬ࢆᶍࡋࡓศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢆᐇ᪋ࡋࡓ. ༢ᒙ CNT ࡣ୍⯡࡟ࡣ 800㹼1200 Υ࡛ 1 nm ⛬ᗘࡢ㔠ᒓᚤ⢏Ꮚ࡟Ⅳ⣲※࢞ࢫࢆ౪⤥ࡍࡿࡇ࡜࡛
ྜᡂࡉࢀࡿ. ᮏࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࡇࡢ㐣⛬ࢆᶍࡋ࡚, ࢭࣝෆ࡟㔠ᒓᚤ⢏Ꮚࢆ㓄⨨ࡋ, Ⅳ⣲ཎᏊࢆ୍ᐃ㛫㝸࡛౪⤥ࡍࡿࡇ࡜࡛༢ᒙ CNT ࢆᡂ㛗ࡉࡏࡿ. ࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨ࡟ࡣ DeepMD-kit[3], MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡟ࡣ LAMMPS[4]ࢆ⏝࠸ࡓ.



◊✲ᡂᯝ
カ⦎ࢹ࣮ࢱ࡟ᑐࡍࡿᏛ⩦⤖ᯝࢆ Fig.1 ࡟♧ࡍ. カ⦎ࢹ࣮ࢱ࡟ᑐࡍࡿᏛ⩦⢭ᗘࡣ MAE 0.021eV/atom ࡛࠶ࡗࡓ.

ᩍᖌࢹ࣮ࢱ࡜ࡋ࡚⏝࠸ࡓᵝࠎ࡞ᵓ㐀࡟ᑐࡋ࡚⢭ᗘࡼࡃᏛ⩦ࡀ⾜ࢃࢀ࡚࠾ࡾ, ᖜᗈ࠸఩┦✵㛫ࡢ࢚ࢿࣝࢠ࣮࡟
ᑐࡋ࡚ࣃ࣓࣮ࣛࢱࣇ࢕ࢵࢸ࢕ࣥࢢࡀ⾜ࢃࢀ࡚࠸ࡿࡇ࡜ࡀぢ࡚ྲྀࢀࡿ. ࡲࡓ, Fe60~120 㔞యࢡࣛࢫࢱ࣮࡟Ⅳ⣲ཎᏊࢆ 1100~1500K ࡛౪⤥ࡍࡿศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸, 㸵ဨ⎔࡞࡝ࡢḞ㝗ࢆᣢࡓࡎ, ࢝࢖ࣛࣜࢸ
࢕ࡀ᏶඲࡟≉ᐃ࡛ࡁࡿ༢ᒙ CNT ࢆ෌⌧ࡋࡓ. ≉࡟ armchair ➃ࡀᡂ㛗➃࡜࡞ࡗ࡚༢ᒙ CNT ࡀᡂ㛗ࡋ࡚ࡺࡃᵝᏊࡀほᐹࡉࢀࡓ. ᐇ㦂ⓗ࡟ྜᡂࡉࢀࡿ༢ᒙ CNT ࡣ armchair ᐤࡾࡢ࢝࢖ࣛࣜࢸ࢕ࢆᣢࡘࡶࡢࡀከ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ, armchair ➃ࡢ࢚ࢿࣝࢠ࣮ⓗ࡞Ᏻᐃᛶࡀ armchair ᐤࡾࡢ࢝࢖ࣛࣜࢸ࢕ศᕸࡢ㉳ᅉ࡜࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ.

- 293 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
,NXPD.RKDWD5\R<RVKLNDZD.XQLR0RUL.DRUX+LVDPD.HLJR2WVXND6KRKHL&KLDVKL6KLJHR0DUX\DPD ➨ ᅇࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈ࣭ࢢࣛࣇ࢙ࣥ⥲ྜࢩ࣏ࣥࢪ࣒࢘ ኱㜰 ᖺ  ᭶,NXPD.RKDWD5\R<RVKLNDZD.XQLR0RUL.DRUX+LVDPD.HLJR2WVXND6KRKHL&KLDVKL6KLJHR0DUX\DPD ఏ⇕ࢩ࣏ࣥࢪ࣒࢘ బ㈡ ᖺ  ᭶ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

Fig.2 (9,8) ༢ᒙ CNT ᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥ

Fig.1 カ⦎ࢹ࣮ࢱ࡟ᑐࡍࡿᏛ⩦⤖ᯝཧ⪃ᩥ⊩㻦 [1] Yang, F. et. al., Nature. 2014, 510, 522−524. >@*.UHVVHDQG-+DIQHU3K\V5HY%   >@+DQ:DQJ&RPSXWHU3K\VLFV&RPPXQLFDWLRQV  
[4] Thompson, H. et. al., Comp Phys Comm, 271 (2022) 10817.

- 294 -

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VS%' Ln Ð./EÅi3?08C¾Y ß2021 xs MA +¦pÛ+p¤ ¬®ª©ßÏl]mÀ±%'ß Ln % MA ÍMlÒ~ )(Ð./E°OÊ+³ ß¥ÂÅi3?08C+( )+pÛ&)Åi3?08CÇ( %'ßÐ./E°OÊ×l£+o(°OÊF×l£ßÍMl ­ Ln/MA Ì Ò«Ó+& ßLn/MA Ì VlÂ©Æ+&( (

8;#-A<#W CONFLEX Íz³>D1BA+¦VlXg%'Ð./EÍz¯Ò+³ ß»noÊ+( noÊ+WÊ ßÏl]mÀ±%'×lfy£%×l[Æ£ÊË]\¿+¹Ïl]mÀ± Gaussian16 % ORCA +¦Ïl]mÀ±%'&)Åi3?08C+ßpÛÐ./EÅi3?08CÇ( %'ßÐ./EÊ×l£+oßÌVlÂ©Æ+&( +ª 8;"*c 1  Eu3+ßGd3+ßTb3+./E DGA (diglycolamide) ÁtOÍMl%'~ )(Ð./EÝM3+(DGA)3ÞÀ±Åi3?08C+­ 7G5ßÐ./EÅi3?08C&ÍMl"Åi3?08C+|v3?08C(Eu3+ß
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3 Ð./EI$$N2=8 (Ý1622 cm–1Þ  *'ß Ra$p3?08CH¸( )ßDGA $}Ð./E+~( Gd3+./E( +­b (HßDGA +¦ kUpÛß3 ./E Gd3+r(U· $N
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(2021.9.18-21, /EB.E)
 Structural characterization of hypervalent carbon compounds in the gas phase: penta-versus tetra-coordinatedisomersÝ35GÞßSatoru Muramatsu, Keijiro Ohshimo, Motoki Kida, Yuan Shi, Fuminori Misaizu, Yohsuke
Yamamoto, Yoshiya InokuchißPacifichem 2021 (2021.12.16-21, /EB.E)
 Cold gas-phase spectroscopy: a case study of hypervalent carbon compoundsÝÃ¡ÞßSatoru Muramatsuß
The 18th Nano Bio Info Chemistry Symposium (2021.12.14-15, /EB.E)
 Gas-phase Spectroscopy of Chemical Intermediates Produced in SolutionÝÃ¡ÞßYoshiya Inokuchiß11th
Asian Photochemistry Conference (APC2021) (2021.11.1–4, /EB.E)!6 i 8m ¨º+¹ /?
New Aspect of Photophysics of 7,7,8,8-Tetracyanoquinodimethane and Its Solvated Complexes: Intra- vs. InterMolecular Charge Transfer, S. Muramatsu, N. Chaki, S.-n. Kinoshita, Y. Inokuchi, M. Abe, T. Iimori, and T. Ebata,
RSC Adv., 2021, 11, 22381–22389.
Structural Investigation of Photochemical Intermediates in Solution by Cold UV Spectroscopy in the Gas Phase:
Photosubstitution of Dicyanobenzenes by Allylsilanes, Y. Kitamura, S. Muramatsu, M. Abe, and Y. Inokuchi, J. Phys.
Chem. A, 2021, 125, 6238–6245.
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Phenylhydrazines by DDQ”, S. Machida, M. Kida, S. Muramatsu, T. Hirao, T. Haino, and Y. Inokuchi*, J. Phys. Chem.
A, 2021, 125, 6697–6702.
 ”Spherand Complexes with Li+ and Na+ Ions in the Gas Phase: Encapsulation Structure and Characteristic
Unimolecular Dissociation”, M. Kida, K. Wada, S. Muramatsu, R. Shang, Y. Yamamoto, and Y. Inokuchi, Phys. Chem.
Chem. Phys., 2021, 23, 25029–25037.
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Spectroscopy”, R. Goda, S. Kanazawa, S. Machida, S. Muramatsu, and Y. Inokuchi*, J. Phys. Chem. A., 2021, 125,
10410–10418.

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⌮Ꮫ㒊໬Ꮫ⛉㸧◊✲┠ⓗ㐣ᖺᗘࡢ᪋タ฼⏝ࢆ㏻ࡌ࡚ࠊ࢟ࣀࣜࣥ㦵᱁ࡤ೧ౕΉͲ͹‫ڂݜ‬ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య㸦Fe,
Ni㸧࡟㛵ࡋ࡚ DFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬࠾ࡼࡧࡇࢀࡽ㘒యࢆ⏝࠸ࡓゐ፹཯ᛂࡢ཯ᛂ⤒㊰᥈⣴ࢆ㐍ࡵ࡚ࡁࡓࠋ≉࡟ࠊ᫖ᖺᗘࡣ 6 ✀ࡢ

1a

1b

1c

1d

1e

1f

Πϩίϱ͹ϐχϫεϨϩԿ༽రࡪର

࢟ࣀࣜࣥ㦵᱁ PNN ᆺࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍ
ࡿྛ㕲㘒య 1a㹼1f ࢆྜᡂࡋࠊ࢔ࣝࢣࣥࡢࣄ
ࢻࣟࢩࣜࣝ໬཯ᛂ࡟࠾ࡅࡿゐ፹ᛶ⬟࡜ࡢ┦㛵㛵ಀㄪᰝࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊSambVca 2.1
ࢆ฼⏝ࡋࡓ༙⌫ゎᯒἲ࡟ࡼࡾ⟬ฟࡉࢀࡿ❧య್㸦%VBur, hemiRS㸧ࡀ⏕ᡂ≀㑅ᢥᛶ࠾ࡼࡧ཯
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ຌ೧ౕ࡟ࡘ࠸࡚ᐇ㦂࣭ィ⟬ࡢ୧㠃࠿ࡽᨵࡵ࡚ホ౯ࢆ')7
6DPE9FD ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊୖグࡢ◊✲࠿ࡽᵓ⠏ࡋࡓゐ፹ᛶ⬟ண

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ࡣィ⟬⤖ᯝ࡜ᐇ㦂⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛ホ౯ࡋࡓࠋィ⟬࡟ࡣ Gaussian 09 ࢆ⏝࠸ࠊᵓ㐀᭱㐺໬࡟ࡣ B3LYP,
B3PW91, M06, M06Lࠊ୍Ⅼィ⟬࡟ࡣ B3LYP, B3PW91, M06, M06L, mPW1PW91, PBE, TPSS, PBE0 ࢆ⏝࠸ࠊ୍㒊࡟ࡣศᩓຊ⿵ṇ㸦D3, D3BJ㸧ࢆ㐺⏝ࡋࡓࠋᇶᗏ㛵ᩘ࡟ࡣ㑄⛣㔠ᒓ㸦Fe, Co㸧࡟ LanL2DZ ࡶࡋࡃࡣ SDDࠊࡑࡢ௚ࡢཎᏊ࡟ࡣ def2-SV(P), def2-TZVP, 6-311G(d,p) ࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ- 297 -

◊✲ᡂᯝ3.1 PNN 㕲㘒యࢆ⏝࠸ࡓࣄࢻࣟࢩࣜࣝ໬࡟࠾ࡅࡿண

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1i ࡟ࡘ࠸࡚ UM06/def2-tzvp ࣞ࣋ࣝ㸦S =2㸧࡛ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊSambVca 2.1 ࡟ࡼࡾ❧య್㸦%VBur㸧ࢆ⟬ฟࡋࡓ㸦ᅗ 2㸧ࠋୖグࡢ㐣⛬࡟ࡼࡾᚓࡽࢀࡓ್࠿ࡽࠊ᭱ࡶ
ゐ፹ᛶ⬟ࡀ㧗࠸࡜ண᝿ࡉࢀࡿ㘒య 1hࢆᐇ㝿࡟ྜᡂࡋࠊ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜJ
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9%XUL
9%XUᅗ 2㸬㕲㘒య 1g㹼1i ࡢ᭱㐺໬ᵓ㐀࠾ࡼࡧ❧య್ࢁࠊᮇᚅࡋࡓ࡜࠾ࡾ㧗ኚ᥮⋡㸦98%㸧࠾ࡼࡧ㧗⏕ᡂ≀㑅ᢥᛶ㸦99%௨ୖ㸧ࢆ♧ࡋࡓࠋࡲࡓࠊ㘒య 1h ࡢ⤖ᬗᵓ㐀࠾ࡼࡧ Evans ἲ࡟ࡼࡿ☢໬⋡ᐃࡢ⤖ᯝࡣィ⟬࡟ࡼࡾண᝿ࡋࡓ᭱㐺໬ᵓ㐀ࠊ㟁Ꮚ≧ែ㸦S = 2㸧࡜ࡼ࠸୍⮴ࢆ♧ࡋࡓࠋ௨ୖࡢ⤖ᯝ࠿ࡽࠊ᫖ᖺᗘ㛤Ⓨࡋࡓ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬⏝㕲ゐ፹࡟ᑐࡍࡿண

ࣔࢹࣝࡢጇᙜᛶࡀᐇ㦂ࠊィ⟬ࡢ୧㠃࠿ࡽ⿬௜ࡅࡽࢀࡓࠋ

ࡇࢀࡽࡢᡂᯝ࡟ࡘ࠸࡚ࡣᅜෆࢩ࣏ࣥࢪ࣒࢘࠾ࡼࡧᏛ⾡ㄽᩥࢆ㏻ࡌ࡚Ⓨ⾲ࢆ⾜ࡗࡓࠋ
3.2 PNN ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿࢥࣂࣝࢺ㘒యࡢ㕲㘒య 1b ࡜ྠ୍ࡢ PNN 㓄఩Ꮚࢆ᭷ࡍࡿࢥࣂࣝࢺ㘒య 2b ࡟ࡘ࠸࡚ DFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋࡲࡓࠊEvans ἲ࡟ࡼࡾ⟬ฟࡋࡓ☢໬⋡㸦ᐇ㦂್㸧ࢆࡶ࡜࡟ࠊS = 3/2 ࡢ㧗ࢫࣆࣥ㘒య࡜ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋྛ✀ỗ㛵ᩘ࠾ࡼࡧᇶᗏ㛵ᩘ࡟ࡼࡾᚓࡽࢀࡓᵓ㐀࡜༢⤖ᬗ X ⥺ᵓ㐀ゎᯒ࡟ࡼࡾᚓࡽࢀࡓ⤖ᯝࢆẚ㍑ࡋࡓ࡜ࡇࢁࠊ㕲㘒య࡜ྠᵝ࡟ UM06/def2-tzvp ࡛ࣞ࣋ࣝ⤖ᬗᵓ㐀࡜ࡼ࠸୍⮴ࢆ♧ࡋࡓ㸦ᅗ 3㸧ࠋ㧗ࢫࣆࣥ㘒య࡟࠾ࡅࡿ

ᅗ 4㸬PNN ࢥࣂࣝࢺ㘒య 2b ࡢ᭱㐺໬ᵓ㐀㸦ᕥ㸧ࢥࣂࣝࢺࡢඹ᭷⤖ྜ༙ᚄ㸦⣙ 1.50ύࠊCCDC ࡢ⤫ィ್࠾ࡼࡧ⤖ᬗᵓ㐀㸦ྑ㸧ࡼࡾ㸧ࡣ㧗ࢫࣆࣥ㕲㘒య㸦⣙ 1.52ύࠊྠ⤫ィ್ࡼࡾ㸧ࡢࡶࡢࡼࡾࡶࢃࡎ࠿࡟ᑠࡉࡃࠊ㓄఩Ꮚ඲యࡀࡼࡾ㔠ᒓ࡟᥋㏆ࡋࡓᵓ㐀ࢆ࡜ࡿࠋ⤖ᯝ࡜ࡋ࡚ࠊྠ୍ࡢ㓄఩Ꮚࢆᣢࡘ㕲㘒య 1b ࡼࡾࡶ㓄఩Ꮚࡀ୚࠼ࡿ❧యᙳ㡪ࡀࡼࡾ኱ࡁࡃ࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡇ࡜ࡣ SambVca 2.1 ゎᯒ࡟ࡼࡾ⟬ฟࡋࡓࢥࣂࣝࢺ㘒య 2b ࡢ❧య್ࡀ㕲㘒య1b ࡼࡾࡶቑຍࡋࡓࡇ࡜࠿ࡽࡶ⿬௜ࡅࡽࢀࡿࠋࡲࡓࠊ2b ࢆ⏝࠸ࡓ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬࡟࠾ࡅࡿゐ፹཯
ᛂ࡛ࡣࠊண



ࣔࢹࣝ࡜▩┪ࡋ࡞࠸⤖ᯝࡀᚓࡽࢀࡓࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬4.1 ⚄㇂ᫀᏹࠊ‫‮‬ᑼᾈኴࠊ᪥ୗ᫓ᶞࠊᘪ๐⚽㝯ࠊ➨ 10 ᅇ JACI/GSC ࢩ࣏ࣥࢪ࣒࢘
‫ۻ‬4.2 ⚄㇂ᫀᏹࠊ‫‮‬ᑼᾈኴࠊᘪ๐⚽㝯ࠊ➨ 25 ᅇࢣ࢖⣲໬Ꮫ༠఍ࢩ࣏ࣥࢪ࣒࢘

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
★5-1. Kamitani, M. Chem Commun. 2021, 39, 3535-3539.

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㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿග໬Ꮫ⣔ϩ࡟࠾ࡅࡿỈศゎ࠾ࡼࡧ࢟ࣀࣥ㑏ඖ཯ᛂࡢศᏊ
ᶵᵓゎᯒ
Quantum chemical calculation study on the molecular mechanisms ofwater oxidation and quinone reduction in photosystem II‫ۑ‬㔝ཱྀ ᕦࠊຍ⸨ ♸ᶞࠊᑠᯘ ᬛᖾ㸦ྡྂᒇ኱㝔࣭⌮㸧

1◊✲┠ⓗࠊෆᐜ ග໬Ꮫ⣔ϩ㸦PSII㸧ࡣ 20 ௨ୖࡢࢧࣈࣘࢽࢵࢺࡼࡾ࡞ࡿࢱࣥࣃࢡ㉁」ྜయ࡛࠶ࡾࠊග࢚ࢿࣝࢠ࣮࡟ࡼࡿỈศゎ࠾ࡼࡧࣉࣛࢫࢺ࢟ࣀࣥࡢ㑏ඖࢆ⾜ࡗ࡚࠸ࡿࠋỈศゎ཯ᛂࡣࠊPSII ࡢ࣮࣓ࣝࣥഃ࡟⤖ྜࡍࡿ Mn4CaO5 ࢡࣛࢫࢱ࣮࡟࠾࠸࡚⾜ࢃࢀࡿࠋࡇࡢ Mn4CaO5 ࢡࣛࢫࢱ࣮ࡣ࢔࣏ PSII ࢱࣥࣃࢡ㉁࡬ࡢග↷ᑕ࡟ࡼࡾ Mn2+ࡼࡾ㡰ḟᵓ⠏ࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊࡑࡢᶵᵓࡣ࡯࡜ࢇ࡝୙࡛᫂࠶ࡿࠋ୍᪉ࠊࢫࢺ࣐ࣟഃ࡟⤖ྜࡍࡿࣉࣛࢫࢺ࢟
ࣀࣥ㟁Ꮚཷᐜయ QB ࡢ㓟໬㑏ඖ㟁఩ࡣ pH ࡟ࡼࡗ࡚ኚ໬ࡋࠊࢫࢺ࣐ࣟࡢ pH ኚ໬࡟ᛂࡌ࡚ PSII ෆࡢ㟁Ꮚࣇ࣮ࣟࡀไᚚࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊࡑࡢᶵᵓࡣ᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊࡲࡎࠊMn4CaO5
ࢡ ࣛ ࢫ ࢱ ࣮ ᵓ ⠏ ࡢ ᭱ ึ ࡢ Mn2+ ⤖ ྜ ࡜ ࡑ ࡢ 㓟 ໬ 㐣 ⛬ ࢆ ࠊ ᐦ ᗘ ỗ 㛵 ᩘ ἲ 㸦 DFT 㸧 ィ ⟬ ࠾ ࡼ ࡧ quantum
mechanics/molecular mechanics㸦QM/MM㸧ィ⟬ࢆ⏝࠸࡚ㄪ࡭ࡓࠋࡲࡓࠊࣉࣛࢫࢺ࢟ࣀࣥ QB ࡢ㏆ഐ࡟Ꮡᅾࡍࡿ
ࣄࢫࢳࢪࣥṧᇶ㸦D1-H252㸧ࡢࣉࣟࢺࣥ໬ᵓ㐀ࢆኚ໬ࡉࡏࡓ㝿ࡢ QB ࡢ㓟໬㑏ඖ㟁఩ኚ໬ࠊ࠾ࡼࡧࠊࡇࡢࣄࢫ
ࢳࢪࣥࢆ࢔ࣛࢽࣥ࡟⨨᥮ࡋࡓሙྜࡢ㓟໬㑏ඖ㟁఩ኚ໬ࢆィ⟬ࡋࠊᙜ◊✲ᐊ࡛ᚓࡽࢀࡓᐇ㦂ࢹ࣮ࢱ࡜ẚ㍑ࡍࡿ
ࡇ࡜࡟ࡼࡾࠊQB ࡢ㟁Ꮚ⛣ືไᚚࡢศᏊᶵᵓࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ Mn4CaO5 ࢡࣛࢫࢱ࣮ࡢᵓ⠏ᶵᵓ࡟࠾ࡅࡿ᭱ึࡢ Mn2+⤖ྜ఩⨨࠾ࡼࡧࡑࡢ㓄఩ᵓ㐀࡟ࡘ࠸࡚ࡣࠊMn4CaO5 ࢡࣛࢫࢱ࣮ࢆḞᦆࡋࡓ࢔࣏ PSII ࢱࣥࣃࢡ㉁ࡢࢡࣛ࢖࢜㟁Ꮚ㢧ᚤ㙾ᵓ㐀࠿ࡽ Mn2+⤖ྜ㒊఩࿘㎶ࡢึᮇᵓ㐀ࣔࢹࣝࢆᵓ⠏ࡋࠊGaussian09 ࢆ⏝࠸ࡓ DFT ィ⟬ࢆ⾜ࡗࡓࠋMn2+࠾ࡼࡧ Mn3㸩ࡀ⤖ྜࡋࡓࣔࢹࣝ࡟ࡘ࠸࡚ࠊᵓ㐀᭱㐺໬࠾ࡼࡧᇶ‽᣺ືィ⟬ࢆ⾜࠸ࠊMn3+/Mn2+㉥እᕪࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋࡲࡓࠊࢱࣥࣃࢡ㉁ࢥࣥࣇ࢛࣓࣮ࢩ
ࣙࣥኚ໬ᚋࡢග㓟໬ࡉࢀࡓ Mn3+ࡢ⤖ྜ㒊఩࡟ࡘ࠸࡚ࡣࠊ᏶ᡂᆺ PSII ࡢ X ⥺⤖ᬗᵓ㐀࠿ࡽ Mn4CaO5 ࢡࣛࢫࢱ࣮ࢆ㝖ཤࡋࡓ࢔࣏ PSII ࢱࣥࣃࢡ㉁࡟ Mn3+ࢆ⤖ྜࡉࡏࡓࣔࢹࣝ࡟ࡘ࠸࡚ࠊQM/MM ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ ࣉࣛࢫࢺ࢟ࣀࣥ㟁Ꮚཷᐜయ QB ࡢ㓟໬㑏ඖ㟁఩࡟ࡘ࠸࡚ࡣࠊPSII ࡟⤖ྜࡍࡿ QB ࡜ࡑࡢ࿘㎶ࡢ࢔࣑ࣀ㓟ࠊ㠀࣒࣊㕲࢖࢜ࣥࠊⅣ㓟Ỉ⣲࢖࢜ࣥࠊỈศᏊࡼࡾ࡞ࡿึᮇᵓ㐀ࢆసᡂࡋ㸦ᅗ 1a㸧ࠊ㐃⥆ㄏ㟁యࣔࢹࣝ(PCM)ࢆ⏝࠸
ࡓ DFT ィ⟬ࢆ⾜ࡗࡓࠋ⁐፹࡜ࡋ࡚Ỉ࠾ࡼࡧ DMF ࢆ᥇⏝ࡋࡓࠋ㏆ഐ࡟Ꮡᅾࡍࡿࣄࢫࢳࢪࣥഃ㙐㸦D1-H252㸧
ࢆࣉࣟࢺࣥ໬ࡋࡓప pH ࣔࢹࣝ࡜⬺ࣉࣟࢺࣥ໬ࡋࡓ㧗 pH ࣔࢹࣝ࡟ࡘ࠸࡚ィ⟬ࡋࠊࡉࡽ࡟ࠊࡇࡢ His ṧᇶࢆ
Ala ࡟⨨᥮ࡋࡓ D1-H252A ኚ␗యࡢࣔࢹࣝ࡟ࡘ࠸࡚ࡶィ⟬ࢆ⾜ࡗࡓࠋ

3

◊✲ᡂᯝ

㸦㸯㸧Mn4CaO5 ࢡࣛࢫࢱ࣮ࡢᙧᡂᶵᵓ㸸Mn ⤖ྜ㒊఩࡟Ꮡᅾࡍࡿ࢝ࣝ࣎࢟ࢩࣝᇶ࠾ࡼࡧࣄࢫࢳࢪࣥഃ㙐ࡢ␗࡞ࡿࣉࣟࢺࣥ໬ᵓ㐀࡟ࡘ࠸࡚ DFT ἲ࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮ࡢẚ㍑࠿ࡽ Mn4CaO5 ࢡࣛࢫࢱ࣮ᙧᡂ
࡟࠾࠸࡚᭱ึ࡟ Mn2+ࡀ⤖ྜࡍࡿ࢔࣑ࣀ㓟࠾ࡼࡧ㓄఩ᵓ㐀ࢆ᥎ᐃࡋࡓࠋࡑࡢ᭱㐺໬ᵓ㐀࡟࠾࠸࡚ࠊᇶ‽᣺ືゎᯒࢆ⾜࠸ࠊMn3+࡜ Mn2+ࡢ㉥እᕪࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓ⤖ᯝࠊᙜ◊✲ᐊ࡛ᚓࡽࢀࡓᐇ

- 299 -

ࢫ࣌ࢡࢺࣝࢆ࡯ࡰ෌⌧ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡉࡽ࡟ࠊ࿘㎶ࢱࣥࣃࢡ㉁ࢆྵࢇࡔ QM/MM ἲ࡟ࡼࡾࠊࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ᚋ
ࡢ Mn3+ࡢ⤖ྜ఩⨨ࢆ᥎ᐃࡋࠊ᭱ึࡢ⤖ྜ఩⨨㸦Mn1 ࢧ࢖ࢺ㸧࡜ࡣ␗࡞ࡿ఩⨨࡟⛣ືࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ㸦㸰㸧ࣉࣛࢫࢺ࢟ࣀࣥ㟁Ꮚཷᐜయ QB ࡢ㓟໬㑏ඖ㟁఩ไᚚᶵᵓ㸸 QB ࡢ㏆ഐ࡟Ꮡᅾࡍࡿ D1-H252 ࡀࣉࣟࢺࣥ໬ࡋࡓ࢝
ࢳ࢜ࣥᵓ㐀㸦ప pH ࣔࢹࣝ㸧࠾ࡼࡧ NπH ᆺࡢ୰ᛶᵓ㐀㸦㧗pH ࣔࢹࣝ㸧࡟ࡘ࠸࡚ࠊQB ࠾ࡼࡧ QB−≧ែࡢ࢚ࢿࣝࢠ࣮࠿
ࡽ QB−/QB ᑐࡢ㓟໬㑏ඖ㟁఩ࢆồࡵࡓ㸦ᅗ㸯㸧ࠋࡑࡢ⤖ᯝࠊpH ࡢୖ᪼࡟ࡼࡗ࡚ QB ࡢ㓟໬㑏ඖ㟁఩ࡀపୗࡍࡿࡇ࡜ࡀ♧ࡉࢀࠊᐇࡢ㟁఩ኚ໬ࡀ࡯ࡰ෌⌧ࡉࢀࡓࠋࡲࡓࠊࡇࡢ His

ࢆ Ala ࡟⨨᥮ࡋࡓ㝿ࡢ㟁఩పୗ࡟ࡘ࠸࡚ࡶᐇ㦂್ࢆ࡯ࡰ෌
⌧ࡋࡓࠋࡇࢀࡽࡢィ⟬࠿ࡽࠊࢫࢺ࣐ࣟ⾲㠃࡟Ꮡᅾࡍࡿ
D1-H252 ࡀ pH ࢭࣥࢧ࣮࡜ࡋ࡚ാࡁࠊPSII ࡟࠾ࡅࡿ㟁Ꮚࣇ࣮ࣟࢆไᚚࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᅗ 1㸬(a) ࣉࣛࢫࢺ࢟ࣀࣥ㟁Ꮚཷᐜయ QB ࡢィ⟬ࣔࢹࣝࠋ(b-d) ᭱㐺໬ᵓ㐀ࡢ QB-H(A)252 ࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡
ࢡࠋb: ࢝ࢳ࢜ࣥᆺ, c: ୰ᛶ NπH ᆺ, d: H252A ኚ␗యࠋཎᏊⰍ㸸QB ≧ែࠊ⥳Ⰽ㸸QB−≧ែࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

★1. ᔱ⏣཭୍㑻ࠊ㕥ᮌ೺⿱ࠊ໭ᓥ(஭ཎ)ᬛ⨾ࠊᯇཎᕦࠊ㛗ᑿ㑈ࠊᇽ๓┤ࠊ㔝ཱྀᕦࠊග໬Ꮫ⣔ II ࡢ Mn ࢡࣛࢫࢱ࣮㓄఩Ꮚ࡟≉␗ⓗ࡞࢔࣑ࣀ㓟ኚ᥮ࠊ᪥ᮏගྜᡂᏛ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2021 ᖺ 5 ᭶ 28-29 ᪥★2. ᯇཎᕦࠊ㕥ᮌ೺⿱ࠊᔱ⏣཭୍㑻ࠊ໭ᓥ(஭ཎ)ᬛ⨾ࠊ㛗ᑿ㑈ࠊᇽ๓┤ࠊ㔝ཱྀᕦࠊගྜᡂỈศゎ⣔࡟࠾ࡅࡿ᪂ወ࡞࢔࣑ࣀ㓟ኚ᥮ᶵᵓࠊ➨ 47 ᅇ⏕యศᏊ⛉Ꮫウㄽ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2021 ᖺ 6 ᭶ 4-5 ᪥★3. Takumi Noguchi, Infrared study on the mechanisms of water oxidation at the Mn cluster and its photoassembly inphotosystem II, The 19th Congress of the European Society for Photobiology, On line, Aug 30 - Sep 3, 2021
★4. ᯇཎᕦ, 㕥ᮌ೺⿱, ᔱ⏣཭୍㑻, ໭ᓥ(஭ཎ)ᬛ⨾, 㛗ᑿ㑈, ᇽ๓┤, 㔝ཱྀᕦࠊගྜᡂỈศゎ⣔࡟࠾ࡅࡿ⩻ヂᚋ࢔࣑ࣀ㓟ኚ᥮ࡢ࣓࢝ࢽࢬ࣒ࠊ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2021 ᖺ 11 ᭶ 25-27 ᪥

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

★1. A. Sato, Y. Nakano, S. Nakamura, and T. Noguchi, Rapid-scan time-resolved ATR-FTIR study on thephotoassembly of the water-oxidizing Mn4CaO5 cluster in photosystem II, J. Phys. Chem. B, 125, 4031–4045(2021).
★2. Yuichiro Shimada, Takehiro Suzuki, Takumi Matsubara, Tomomi Kitajima-Ihara, Ryo Nagao, Naoshi Dohmae, andTakumi Noguchi, Origin of photosynthetic oxygen evolution beyond the central dogma, submitted.
★3. Tomoyuki Kobayashi, Yuichiro Shimada, Ryo Nagao, and Takumi Noguchi, pH-dependent regulation of electron
flow in photosystem II by a histidine residue at the stromal surface, submitted.

- 300 -⸆ ๣ศᏊᨺฟࢆᚿྥࡋࡓ᭷ᶵ㔠ᒓࣇࢱࣟࢩ࢔ࢽࣥࡢග཯ᛂ㛤Ⓨ'HYHORSPHQWRISKRWRFKHPLFDOUHDFWLRQVRIRUJDQRPHWDOOLFSKWKDORF\DQLQHVIRUGUXJXQFDJLQJࠐᮧ⏣ ្ࠊ▼஭ ࿴அ㸦ᮾி኱Ꮫ⏕⏘ᢏ⾡◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
㏆ᖺࠊග⥺ຊᏛⓗ⒪ἲ 3KRWRG\QDPLFWKHUDS\3'7  ࡀࠊప๪స⏝ᆺࡢගࡀࢇ἞⒪ἲ࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸

ࡿࠋྠ⒪ἲ࡛ࡣࠊࡀࢇ⣽⬊࡟㞟✚ࡉࡏࡓගቑឤ๣࡟ᑐࡋࠊ࣮ࣞࢨ࣮ගࢆ↷ᑕࡍࡿࡇ࡜࡛ࠊ⭘⒆㑅ᢥⓗ࡟⏕ᡂࡋࡓάᛶ✀࡟ࡼࡿ⣽⬊ᨷᧁࡀᐇ⌧ࡉࢀ࡚࠸ࡿ>@ࠋࡋ࠿ࡋࠊ୍⯡࡟⣔୰㓟⣲࠿ࡽⓎ⏕ࡍࡿάᛶ㓟⣲✀ࡀ⣽⬊ᨷᧁ࡟⏝࠸ࡽࢀࡿࡓࡵࠊάᛶ✀ࡢ㑅ᢥ⫥ࡀ⊃࠸Ⅼࠊ࠾ࡼࡧప㓟⣲⎔ቃୗ࡟࠾ࡅࡿ⣽⬊ᨷᧁࡀᅔ㞴࡞Ⅼ࡟ㄢ㢟ࡀ࠶ࡗࡓࠋ୍᪉ࠊගບ㉳ࢆࢺ࣮ࣜ࢞࡜ࡋ࡚⸆≀ศᏊࢆ⭘⒆㑅ᢥⓗ࡟ᨺฟࡍࡿࢩࢫࢸ࣒ࡣࠕග࢔ࣥࢣ࣮ࢪࣥࢢࠖ
࡜࿧ࡤࢀࡿ>@ࠋᙜ◊✲ᐊ࡛ࡣ௨๓ࠊ㍈఩࡟࢔ࣝ࢟ࣝ㓄఩Ꮚࢆ᭷ࡍࡿࣟࢪ࣒࢘ ,,,  ࣇࢱࣟࢩ࢔ࢽࣥ㘒యࡀࠊ㉥Ⰽࢼࣀ⛊ࣃࣝࢫ࣮ࣞࢨ࣮ගࡢ↷ᑕ࡟ࡼࡾࠊ࢔ࣝ࢟ࣝࣛࢪ࢝ࣝࢆ࢔ࣥࢣ࣮ࢪࣥࢢࡋࠊ㓟⣲ඹᏑୗ࡛ᑐᛂࡍࡿ࢔
ࣝࢹࣄࢻࢆ୚࠼ࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡿ>@ࠋᮏࢩࢫࢸ࣒ࡣࠊ⏕య㏱㐣ᛶࡢ㧗࠸㉥Ⰽග࡟ࡼࡾάᛶⅣ⣲✀ࢆᨺฟࡍࡿࡇ࡜࠿ࡽ⯆࿡῝࠸ࠋࡇࢀࡽࡢ⫼ᬒ࡟ᇶ࡙ࡁᮏ◊✲࡛ࡣࠊ㉥Ⰽග࡟ࡼࡾከᵝ࡞⸆≀ศᏊࢆᨺฟࡍࡿග࢔ࣥ
ࢣ࣮ࢪࣥࢢࢩࢫࢸ࣒ࡢ㛤Ⓨࢆ┠ᣦࡋࡓࠋලయⓗ࡟ࡣࠊࣟࢪ࣒࢘ ,,,  ࣇࢱࣟࢩ࢔ࢽࣥࡢ㍈఩࡟ࠊ࣋ࣥࢪࣝ㓄఩Ꮚ࠶ࡿ࠸ࡣ࣋ࣥࢪࣝ㦵᱁ࢆ᭷ࡍࡿ⸆≀ศᏊ๓㥑ࣘࢽࢵࢺࢆᑟධࡋࡓ㘒య⩌ࢆྜᡂࡋࠊࡑࡢග≀ᛶ࠾ࡼࡧ㉥Ⰽග↷ᑕୗ࡟࠾ࡅࡿ཯ᛂᛶࢆㄪ࡭ࡓࠋ
◊✲᪉ἲࠊィ⟬᪉ἲྜᡂࡋࡓ㘒యࡣࠊ᰾☢Ẽඹ㬆㸦NMR㸧ࢫ࣌ࢡࢺࣝ ᐃࠊ㉁㔞ศᯒࠊ㟁Ꮚ྾཰ࢫ࣌ࢡࢺࣝ ᐃࠊ☢Ẽ෇೫ග

஧Ⰽᛶ㸦MCD㸧ࢫ࣌ࢡࢺࣝ ᐃࠊඖ⣲ศᯒ࡞࡝࡟ࡼࡾྠᐃࡋࡓࠋ᭷ᶵ⁐፹୰࡟࠾ࡅࡿග཯ᛂᛶㄪᰝ࡛ࡣࠊྛ
㘒యࡢ㔜࣋ࣥࢮࣥ⁐ᾮ࡟ᑐࡋࠊ㓟⣲ඹᏑୗ࡛㉥Ⰽගࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾᚓࡽࢀࡓ཯ᛂᾮࢆࠊNMR ࢫ࣌ࢡࢺᐃ࡛㏣㊧ࡋࡓࠋࡇࡢ㝿ࠊບ㉳ග※࡟ࡣࠊ㉥Ⰽ LED㸦660 nm㸧ࢆ⏝࠸ࡓࠋỈ୰࡟࠾ࡅࡿ཯ᛂᛶㄪᰝ࡛ࡣࠊ

ࣝྛ㘒యࢆ 1,2-dipalmitoyl-sn-glycero-3-phosphocholine㸦DPPC㸧࠿ࡽᡂࡿ࣏ࣜࢯ࣮࣒࡟ྲྀࡾ㎸ࡲࡏࡿࡇ࡜࡟ࡼࡾ
Ỉ⁐໬ࡋࡓࠋࡑࡢග཯ᛂᛶㄪᰝ࡛ࡣࠊྛ࣏ࣜࢯ࣮࣐ࣝ㘒యࡢỈ⁐ᾮ࡟ᑐࡋࠊ✵Ẽୗ࡛㉥Ⰽගࢆ↷ᑕࡍࡿࡇ࡜
࡟ࡼࡾᚓࡽࢀࡓ཯ᛂᾮࢆࠊ࢞ࢫࢡ࣐ࣟࢺࢢࣛࣇ㸦GC㸧 ᐃ࡟ࡼࡾศᯒࡋࡓࠋࡲࡓࠊࡇࢀࡽ࡜୪⾜ࡋ࡚ࠊᐦᗘ
ỗ㛵ᩘἲ㸦DFT㸧࠾ࡼࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ㸦TD-DFT㸧࡟ࡼࡾࠊ㘒యࡢᇶᗏ≧ែ࣭ບ㉳≧ែ࡟࠾ࡅࡿ㟁Ꮚ≧ែゎᯒࢆࡑࢀࡒࢀᐇ᪋ࡋࡓࠋ⌮ㄽィ⟬࡟ࡼࡿග཯ᛂゎᯒ࡟ࡣࠊ*DXVVLDQ ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࠊB3LYP ỗ㛵ᩘ࠾ࡼࡧ Def2TZVPP ᇶᗏ㛵ᩘ⣔ࢆ㐺⏝ࡋࡓࠋ⁐፹ຠᯝࡣศᴟ㐃⥆య㸦PCM㸧ࣔࢹࣝ࡟ࡼࡾ⪃៖ࡋࡓࠋ




◊✲ᡂᯝ
㍈఩䛻䝧䞁䝆䝹㓄఩Ꮚ䜢᭷䛩䜛䝻䝆䜴䝮㻌 (III)㻌 䝣䝍䝻䝅䜰䝙䞁㘒య䠄1䠅䜢᪂つྜᡂ䛧䚸༢㞳䜢⾜䛳䛯䚹ࢺ࢚ࣝࣥ୰

࡟࠾ࡅࡿ⣸እྍど྾཰ࢫ࣌ࢡࢺ࡛ࣝࡣࠊ
ࣇࢱࣟࢩ࢔ࢽࣥ⎔ࡢ S-S* 㑄⛣࡟ᇶ࡙ࡃᙉࡃ㗦࠸ Q ᖏࡀ 656 nm ࡟

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ほࡉࢀࡓࠋࡇࢀࡼࡾ㘒య 1 ࡣࠊ⏕య㏱㐣ᛶࡢ㧗࠸㉥Ⰽගࢆຠ⋡ࡼࡃ྾཰ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡲࡓࠊ

ྠ㘒యࡢ MCD ࢫ࣌ࢡࢺ࡛ࣝࡣࠊQ ᖏ࡟ᑐᛂࡍࡿ㡿ᇦ࡟ศᩓᆺࡢ Faraday A 㡯ࡀほ ࡉࢀࠊD4h ᑐ⛠࡞ࣇࢱࣟࢩ࢔ࢽࣥ⎔㦵᱁࡟⏤᮶ࡍࡿ᭱పບ㉳୍㔜㡯≧ែࡢ⦰㏥ࡀ♧၀ࡉࢀࡓࠋ⥆࠸࡚ࠊ㘒య 1 ࡢ㔜࣋ࣥࢮࣥ⁐ᾮ࡟ᑐࡋࠊ㓟⣲ඹᏑୗ࡛㉥Ⰽᐃᖖගࢆ 1 ᫬㛫↷ᑕࡋࡓ࡜ࡇࢁࠊ࣋ࣥࢬ࢔ࣝࢹࣄࢻࡀⰋዲ࡞཰⋡࡛⏕ᡂࡍࡿࡇ࡜ࡀࢃ
࠿ࡗࡓࠋࡇࡢ⤖ᯝࡼࡾࠊගບ㉳ࡉࢀࡓ㘒య 1 ࡣࠊ㍈఩ࡢ㔠ᒓ㸫Ⅳ⣲⤖ྜࡢᆒ➼㛤⿣࡟ࡼࡾࠊ࣋ࣥࢪࣝࣛࢪ࢝
ࣝࢆ࢔ࣥࢣ࣮ࢪࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡑࡇ࡛ࠊᮏ཯ᛂࢆ⏕యᶍೌ⎔ቃୗ࡛ᐇ᪋ࡍࡿࡓࡵ࡟ࠊ㘒య 1 ࢆ DPPCࡢ࣏ࣜࢯ࣮࣒࡟ෆໟࡋࡓ」ྜయࢆྜᡂࡋࡓࠋࡇࡢ」ྜయỈ⁐ᾮࡢᣑᩓ㏱㐣ࢫ࣌ࢡࢺ࡛ࣝࡣࠊ⁐ᾮ୰ࡼࡾࡶࡸ
ࡸᖜᗈ໬ࡋࡓ Q ᖏࡀ 656 nm ࡟ほ ࡉࢀࡓࠋࡑࡇ࡛ࠊྠỈ⁐ᾮ࡟ᑐࡋ࡚ࠊ✵Ẽୗ࡛㉥Ⰽᐃᖖගࢆ 30 ศ㛫↷ᑕࡋࡓ࡜ࡇࢁࠊ࣋ࣥࢬ࢔ࣝࢹࣄࢻ⏕ᡂࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ
㘒య 1 ࡢ᳨ウ⤖ᯝࢆ㋃ࡲ࠼ࠊ࣋ࣥࢪࣝ㦵᱁ࢆྵࡴ⸆≀ศᏊ๓㥑ࣘࢽࢵࢺࢆ᭷ࡍࡿ䝻䝆䜴䝮㻌 (III)㻌 䝣䝍䝻䝅䜰䝙䞁㘒య䠄2䠅䛾ྜᡂ䛚䜘䜃༢㞳䜢⾜䛳䛯䚹㘒య 2 ࡢ㔜࣋ࣥࢮࣥ⁐ᾮ࡟ᑐࡋࠊ㓟⣲ඹᏑୗ࡛㉥Ⰽᐃᖖගࢆ 1 ᫬㛫↷ᑕࡋࡓ࡜ࡇࢁࠊᮇᚅ㏻ࡾࠊᶆⓗ࡜ࡍࡿ⸆≀ศᏊࡀᨺฟࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ㘒య 2 ࢆ DPPC ࡢ࣏ࣜࢯ࣮࣒࡟ෆໟࡋࡓ」ྜయࢆ⏝࠸ࡿ࡜ࠊỈ୰࡟࠾࠸࡚ࡶྠᵝࡢ཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ௒ᚋࠊ㘒య
2 ࡢග⥺ຊᏛⓗຠᯝࢆ⣽⬊ᐇ㦂࡟ࡼࡾホ౯ࡍࡿணᐃ࡛࠶ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Kei Murata, Yuki Saibe, Ryuji Misawa, Yoshiho Ikeuchi, Kazuyuki Ishii, WK(&60HHWLQJ RQOLQH 
‫ۻ‬Mengfei Wang, Yusuke Koike, Daisuke Saito, Masako Kato, Kazuyuki Ishii, WK(&60HHWLQJ RQOLQH 
‫ۻ‬ᮧ⏣្ෆ⏣୓⤖▼஭࿴அ➨  ᅇ㓄఩໬ྜ≀ࡢග໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧‫ۻ‬኱す⯟ᖹᮧ⏣្▼஭࿴அ➨  ᅇ㓄఩໬ྜ≀ࡢග໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧
‫ۻ‬๽⤂ீὠ➃ᓫඖᮧ⏣្▼஭࿴அ➨  ᅇ㓄఩໬ྜ≀ࡢග໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧
‫ۻ‬.RKHL2QLVKL.HL0XUDWD.D]X\XNL,VKLL 㘒య໬Ꮫ఍➨  ᅇウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧
‫ۻ‬6KDRWLQJ/LX7DND\XNL7VXEDWD.HL0XUDWD.D]X\XNL,VKLL㘒య໬Ꮫ఍➨  ᅇウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧
‫ۻ‬.HL0XUDWD7DND\XNL7VXEDWD.D]X\XNL,VKL➨ ᅇ ᭷ᶵ㔠ᒓ໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧
‫ۻ‬㟷㔝⍞⏕ᮧ⏣្▼஭࿴அ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍㸦࢜ࣥࣛ࢖ࣥ㸧       ௚  ௳ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬7DNDQRUL<RNRL.HL0XUDWD.D]X\XNL,VKLLPure Appl. Chem.93
‫ۻ‬6KDR:HL/R7DNDVKL.LWDR<XVXNH1DGD.HL0XUDWD .D]X\XNL,VKLL7DNDVKL8HPXUDAngew. Chem. Int. Ed.
60ཧ⪃ᩥ⊩[1] T. Patrice, Photodynamic Therapy, The Royal Society of Chemistry, London, 2004.
[2] T. A. Shell, D. S. Lawrence, Acc. Chem. Res. 2015, 48, 2866.
[3] K. Murata, Y. Saibe, M. Uchida, M. Aono, R. Misawa, Y. Ikeuchi, K. Ishii, submitted.

- 302 -

」㞧࡛ከᵝ࡞ศᏊᵓ㐀࡜㟁Ꮚ≧ែ࠾ࡼࡧ໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲
7KHRUHWLFDOVWXG\IRUFRPSOH[DQGKHWHURJHQHRXVPROHFXODUDQG
HOHFWURQLFVWUXFWXUHVDQGWKHLUFKHPLFDOUHDFWLRQV‫ࠊ୍Ⰻ ⏣⚟ۑ‬㧗ᯇ ᫭ᙪ㸦ி㒔኱Ꮫ ᐇ㦂࡜⌮ㄽィ⟬⛉Ꮫࡢ࢖ࣥࢱ࣮ࣉࣞ࢖࡟ࡼࡿゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬ㸧
1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣ㸪㔞Ꮚ໬Ꮫィ⟬ࢆᇶ┙ᡭἲ࡜ࡋ㸪ከᡂศ࠿ࡽᵓᡂࡉࢀࡿศᏊ⣔ࡢᵓ㐀㸪㟁Ꮚ≧ែ㸪໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲ཬࡧ㟁Ꮚບ㉳≧ែ࡜࢖࢜ࣥ໬ࡸ㟁Ꮚ௜ຍ≧ែࡢࡼ࠺࡞ከᵝ࡞㟁Ꮚ≧ែࡀ㛵୚ࡍࡿ㸪ศᏊ⣔ࡢග≀ᛶࡸග໬Ꮫ཯ᛂࡢ◊✲ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋᮏᖺࡣ㸪㸯) 」ྜ㔠ᒓ㓟໬≀⾲㠃ཬࡧ㔠ᒓ㓟໬≀㸭㈗㔠ᒓࢡࣛࢫࢱ࣮⏺㠃࡟࠾ࡅࡿゐ፹཯ᛂᶵᵓࡢゎ᫂㸪㸰㸧࣋ࣥࢰ࢟ࣀࣥቑឤ๣ࢆ⏝࠸ࡓࢫࢳࣝ࣋ࣥࡢගゐ፹ⓗ␗ᛶ໬࡟࠾ࡅࡿ཯ᛂᶵᵓࡢゎ᫂㸪㸱㸧ᑐ㏆ఝࢡࣛࢫࢱ࣮ᒎ㛤ἲࡢ㛤Ⓨࢆ⾜ࡗࡓࠋࡇࡇ࡛ࡣ㸰) ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬࡟ࡣ Gaussian 09/16 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ DFT/TDDFT ࢆ⏝࠸ࡓࠋ⁐፹ຠᯝࢆ PCM ࡟ࡼࡾ⪃៖ࡋࡓࠋ3◊✲ᡂᯝ
3.1. ࣋ࣥࢰ࢟ࣀࣥቑឤ๣ࢆ⏝࠸ࡓࢫࢳࣝ࣋ࣥࡢගゐ፹ⓗ␗ᛶ໬࡟࠾ࡅࡿ཯ᛂᶵᵓࡢゎ᫂୕㔜㡯ቑឤⰍ⣲ࢆ⏝࠸ࡓࢫࢳࣝ࣋ࣥ㸦ࢪࣇ࢙ࢽ࢚ࣝࢸࣥ㸧ศᏊࡢ EZ ␗ᛶ໬཯ᛂࡣ㸪ග␗ᛶ໬཯ᛂࡢࣔ

ࢹࣝ࡜ࡋ࡚ࡼࡃ◊✲ࡉࢀ࡚࠾ࡾ㸪཯ᛂࡀᐃᖖ≧ែ࡟㐩ࡋࡓ㝿ࡢ EZ 㑅ᢥẚ࡜ቑឤⰍ⣲࡜ࡢ㛵ಀࡀㄪ࡭ࡽࢀ࡚
࠸ࡿࠋ୍⯡࡟㸪EZ 㑅ᢥẚࡣቑឤⰍ⣲ࡢ୕㔜㡯ບ㉳࢚ࢿࣝࢠ࣮࡜㛵㐃࡙ࡅࡓ㆟ㄽࡀྍ⬟࡛࠶ࡿࠋ'H[WHU ᆺࡢ࢚ࢿࣝࢠ࣮⛣ື཯ᛂࡢ㏿ᗘ࡟⡆౽࡞  ≧ែࣔࢹࣝࢆᑟධࡍࡿ஦࡛㸪ほࡉࢀࡿ EZ 㑅ᢥẚࢆቑឤⰍ⣲ࡢ୕㔜㡯࢚ࢿࣝࢠ࣮࡟ࡼࡾㄝ᫂ࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡿࠋࡋ࠿ࡋ࡞ࡀࡽ㸪୍㒊ࡢⰍ⣲࡛ほࡉࢀࡿ EZ 㑅ᢥẚࡣ㸪ࡇࡢࣔࢹ࡛ࣝண᝿ࡉࢀࡿᩘ್࠿ࡽ኱ࡁࡃእࢀ㸪ูࡢࣔࢹࣝࢆ⪃࠼ࡿᚲせࡀ࠶ࡿࠋࡑࡢ౛ࡀ paraEHQ]RTXLQRQH 3%4
ࢆቑឤⰍ⣲࡜ࡋ࡚⏝࠸ࡓ཯ᛂ࡛࠶ࡿࠋࡇࡢሙྜ㸪'H[WHU ࢚ࢿࣝࢠ࣮⛣ືࣔࢹ࡛ࣝண

ࡉࢀࡿ EZ 㑅ᢥẚ࠿ࡽ኱ࡁࡃእࢀࡓ㸪E 㐣๫࡛࠶ࡿᐇ㦂⤖ᯝࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡑࡢせᅉࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟㔞Ꮚ໬Ꮫィ⟬ࢆ⾜࠸㸪ࢫࢳࣝ࣋ࣥ࡜ 3%4 ࡀບ㉳≧ែ」ྜయࢆ⏕ᡂࡋ࡚⤖ྜᅇ㌿ࡢ᪉ྥࢆไᚚࡍࡿ࣓࢝ࢽࢬ࣒ࢆぢฟࡋࡓࠋ
ィ⟬ࡉࢀࡓ EZ ␗ᛶ໬཯ᛂࡢ࢚ࢿࣝࢠ࣮ᅗࢆ♧ࡍ㸦ᅗ㸯ୖ㸧ࠋᇶᗏ≧ែ 6 ࡛ࡣ␗ᛶ໬ࡢ཯ᛂ㞀ቨࡣ NFDO
PRO ࡜ぢ✚ࡶࡽࢀࡓࠋ୕㔜㡯≧ែ 7 ࡛ࡣ㸪ࡡࡌࢀࡓ≧ែ㸦Tw㸧ࡀ᭱ࡶᏳᐃ࡛࠶ࡿࠋࡇࢀࡣ㸪୕㔜㡯 ʌʌ ບ㉳࡟ࡼࡾ⏕ࡌࡿ㸰ࡘࡢᖹ⾜ࢫࣆࣥ㟁Ꮚ㛫࡟ാࡃ 3DXOL ཯Ⓨࢆᢚ࠼ࡿࡓࡵ㸪ʌ ㌶㐨࡜ ʌ ㌶㐨ࡢ㔜࡞ࡾ✚ศࢆ᭱ᑠ໬ࡍࡿࡓࡵ࡛࠶ࡿࠋ୍᪉࡛࢖࢜ࣥ໬ࡋࡓࢫࢳࣝ࣋ࣥࡣ ʌ ⤖ྜᛶࡀᙅࡲࡿⅭ࡟ 6 ≧ែࡼࡾࡶప࠸࢚ࢿࣝࢠ࣮࡛
␗ᛶ໬཯ᛂࡀ㐍⾜ࡍࡿࠋ3%4 ࡣග㓟໬๣࡜ࡋ࡚ᶵ⬟ࡍࡿྍ⬟ᛶࡶ࠶ࡿࡀ㸪୕㔜㡯ບ㉳≧ែࡢ᪉ࡀ㟁Ⲵ⛣ື≧ែࡼࡾࡶᏳᐃ࡛࠶ࡿࡓࡵ㸪ࢫࢳࣝ࣋ࣥ࢝ࢳ࢜ࣥ⤒⏤ࡢ཯ᛂࡣ୺せ࡞⤒㊰࡛ࡣ࡞࠸࡜⪃࠼ࡽࢀࡿࠋ
3%4 ࡜ࢫࢳࣝ࣋ࣥࡣ㸪୕㔜㡯≧ែ࡛Ᏻᐃ࡞ບ㉳≧ែ」ྜయࢆᙧᡂࡍࡿ஦ࡀศ࠿ࡗࡓ㸦ᅗ㸯ୗ㸧
ࠋ2& & ⤖ྜ⏕ᡂ࡟ࡼࡾ㸪ࢫࢳࣝ࣋ࣥࡢ୰ኸ㒊ࡀ sp Ⅳ⣲࡜࡞ࡾ㸪ᅇ㌿㞀ቨࡣᑠࡉࡃ࡞ࡿࠋྍ⬟࡞ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡢ
࠺ࡕ E య࡬࡜ࡘ࡞ࡀࡿ㓄ᗙࡀ᭱Ᏻᐃ࡛࠶ࡗࡓࠋࡇࡢᏳᐃ㓄ᗙ࠿ࡽ㸪୍㔜㡯ᇶᗏ≧ែ࡟ኻάࡍࡿ࡜㸪3%4 ࡜ࢫࢳࣝ࣋ࣥࡣゎ㞳ࡋ㸪Eࢫࢳࣝ࣋ࣥࢆ⏕ࡎࡿࠋࡇࢀࡀ㸪3%4 ቑឤ๣ࡀ♧ࡍ E 㐣๫཯ᛂࡢ㉳※࡛࠶ࡿࠋ

- 303 -

3%4 ࡜ࢫࢳࣝ࣋ࣥࡀᏳᐃ࡞ບ㉳≧ែ」ྜయ㸦;3㸧ࢆᙧᡂ࡛ࡁࡿࡢࡣ㸪34% ࡢ㟁Ꮚ≧ែ࡟㉳ᅉࡍࡿࠋ3%4
ࡣⰋዲ࡞㟁Ꮚཷᐜయ࡛㸪ࢫࢳࣝ࣋ࣥ࠿ࡽ H ཷࡅྲྀࡾ⤖ྜࢆ⏕ᡂࡍࡿࠋ3%4 ࡜ྠᵝ࡟㸰ࡘࡢ࢝ࣝ࣎ࢽࣝᇶ
ࢆᣢࡘࢪ࢔ࢭࢳࣝ㸦ࣈࢱࣥࢪ࢜ࣥ㸧ࡣ㟁Ꮚཷᐜᛶ⬟ࡀຎࡿࡓࡵ㸪ࡑࡢບ㉳≧ែ」ྜయࡣ୙Ᏻᐃ࡛࠶ࡗࡓࠋ
ᮏ◊✲࡛㸪3%4 ࡀቑឤⰍ⣲ࡔࡅ࡛ࡣ࡞ࡃගゐ፹ⓗ࡟ാࡃ࣓࢝ࢽࢬ࣒ࢆᥦ᱌ࡋࡓࠋࡇࡢ࣓࢝ࢽࢬ࣒࡞ࡽ㸪ほࡉࢀࡓ EZ 㑅ᢥẚࡢ 3%4 ⃰ᗘ౫Ꮡᛶࡶㄝ࡛᫂ࡁࡿࠋண

ࡉࢀࡿ୰㛫యࢆศග

ᐃ➼᳨࡛ฟ࡛ࡁࢀࡤ㸪ࡇࡢᶵᵓࡀ⿬௜ࡅࡽࢀࡿࠋ㏆ᖺ㸪᭷ᶵศᏊゐ፹ࡀὀ┠ࡉࢀ࡚࠸ࡿࡀ㸪᭷ᶵศᏊගゐ፹ࡢྍ⬟ᛶࢆ♧ࡍᡂᯝ࡛࠶ࡿࠋ

ᅗ 1㸬ࢫࢳࣝ࣋ࣥศᏊࡢ E-Z ␗ᛶ໬཯ᛂࡢ࢚ࢿࣝࢠ࣮ᅗ (ୖ) S0, T1, ࢝ࢳ࢜ࣥ≧ែࡢࢫࢳࣝ࣋ࣥ࡜ PBQ ቑឤ๣(ୗ) ບ㉳≧ែ」ྜయࢆ⤒⏤ࡍࡿ཯ᛂ⤒㊰

4

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2020 ᖺ 5 ᭶㸪࢜ࣥࣛ࢖ࣥ
‫ۻ‬㧗ᯇ᫭ᙪ㸪⚟⏣Ⰻ୍㸪ᮾ㞞኱㸪బ⸨ၨᩥࠕ3D-RISM ⌮ㄽ࡟ࡼࡿ Pt㸦111㸧㠃࡟྾╔ࡋࡓⰾ㤶᪘໬ྜ≀ࡢ⁐፹࿴ᵓ㐀ゎᯒࠖ➨ 23 ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪2020 ᖺ 5 ᭶㸪࢜ࣥࣛ࢖ࣥ

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(E61Fmn\/;FFigure 2 ¸e-g SOMO Q RSE ×T[1] K. Mikami, Polymer 2020, 203, 122738.
[2] K. Yanada, S. Kato, D. Aoki, K. Mikami, H. Sugita and H. Otsuka, Chem Commun 2021, 57, 2899.

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1. Mechanochemistry of Bis(9-aryl-9-fluorenyl) Peroxide Derivatives in Cross-Linked Polymers
Yi LU, Hajime SUGITA, Koichiro MIKAMI, Daisuke AOKI, Hideyuki OTSUKA° 70 cÝXjÆÊO
2021 s 9  6

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Yi LU, Hajime SUGITA, Koichiro MIKAMI, Daisuke AOKI, Hideyuki OTSUKA° 70 cÝXjÆÊO
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3. Mechanochemical reactions of Bis(9-aryl-9-fluorenyl) Peroxide Derivatives in Polymer Networks
Yi LU, Hajime SUGITA, Koichiro MIKAMI, Daisuke AOKI, Hideyuki OTSUKA
Materials research meeting 2021
2021 s 12  13()17(Õ)

4. Controlling the thermal-/mechano-responsiveness of mechano-materials through rational design of radical
machanophores using theoretical prediction
Yi LU, Hajime SUGITA, Koichiro MIKAMI, Daisuke AOKI, Hideyuki OTSUKA
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 4.=^_?]Ld_-ÄĸĆ(-ú· ÛÚD]>JbĲuµ<÷#­ŋÚĵ6fÜyÚĵ0-ÈĥÄ¾ä-łûjÒ xr ËÑtċ  Í®t}î£ė2#.m¢¿č 1) Potassium Base-Catalyzed Michael Additions of Allylic Alcohols to α,β-Unsaturated Amides: Scope andMechanistic Insights.
M. Sai and H. Kurouchi, Adv. Synth. Catal. 2021, 363, 3585-3591.
 2) Highly Stereoselective Formation of a Spiro Center by a 1,4-Addition/Elimination Reaction of 3,5Difluorocyclohexa-2,5-dienones.
M. Morita, H. Kurouchi, and N. Nemoto, Synlett, 2022, 33, 589-593.
3) Remarkable Solvent Effect of Fluorinated Alcohols on Azo-Ene Reactions.
Y. Kuroda, Chem. Pharm. Bull. 2020, 70, 359-361.
4) Total Syntheses of Spirooliganones A and B.
M. Morita, N. Nemoto, and K. Ohmori, Synlett, 2022, 33, 581-584.
5) Palladium-Catalyzed [1,3]-O-to-N Rearrangement of Allylic Imidates.
Y. Kuroda, Synlett, 2022, 33, 98-102.

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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࡟᭷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࡜ $),5 ἲࢆ⤌ࡳྜࢃࡏࡓ㏿ᗘㄽࢼࣅࢤ࣮ࢩࣙࣥ௜ࡁ཯ᛂ⤒㊰⮬ື᥈⣴ࡶྍ⬟࡛࠶ࡿ㸬⌧ᅾ㸪⏕య⣔࡞࡝࡬ࡢ᭦࡞ࡿỗ⏝໬ࢆ┠ᣦࡋ࡚㛤Ⓨ◊✲ࢆ㐍ࡵ࡚࠸ࡿ㸬ࡲࡓ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡟ࡼࡾ㸪ᡭἲࡢᛂ⏝ࡶ⢭ຊⓗ࡟ᒎ㛤ࡋ࡚࠸ࡿ㸬ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬㈨※ࢆ฼⏝ࡋ࡚㸪᭷ᶵ཯ᛂ㸪ග཯ᛂ㸪㓝⣲཯ᛂ㸪⾲㠃཯ᛂ㸪⤖ᬗᵓ㐀┦㌿⛣࡬ࡢᛂ⏝◊✲ࢆຍ㏿ࡋࡓ࠸࡜⪃࠼࡚࠸ࡿ㸬᭷ᶵ཯ᛂࡸග཯ᛂ࡞࡝㸪ࡍ࡛࡟ᛂ⏝ᐇ⦼ࡢ࠶ࡿ཯ᛂ⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲ࢆ᥎㐍ࡍࡿ࡜࡜ࡶ࡟㸪ᐇ㦂࡟ඛ❧ࡗࡓணࢆᐇ⌧ࡋ࡚࠸ࡃࡇ࡜ࢆ┠ᣦࡍ㸬ࡲࡓ㸪⤖ᬗ┦㌿⛣ࡸ㓝⣲཯ᛂ࡜࠸ࡗࡓ」㞧⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢹ࣮ࢱࡢゎᯒࢆ㏻ࡌ࡚ࡑࡢ㐺⏝ᛶࢆ᳨ドࡍࡿ㸬᫖ᖺᗘࡣ㸪௨ୗࡢ  ࡘࡢㄢ㢟࡟ࡘ࠸࡚୺࡟᳨ウࡋࡓ㸬㸯㸫㸯㸬࢚ࢿࣝࢠ࣮ศ๭እᤄ࡟ࡼࡿ㏱⇕໬ᡭἲࡢ㛤Ⓨ࡜㟁Ꮚ⛣ື཯ᛂゎᯒ㟁Ꮚ⛣ື (7 ཯ᛂࡣ໬Ꮫ཯ᛂࡢ㔜せ࡞ᇶ♏㐣⛬࡛࠶ࡿ㸬࣐࣮࢝ࢫ⌮ㄽࡣ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃 3(6ࢆㄪ࿴㏆ఝࡍࡿࡇ࡜࡛㸪(7 ๓ᚋ  ≧ែࡢᏳᐃᵓ㐀ࡢࡳ࠿ࡽ㟁Ꮚ⛣ື㏿ᗘᐃᩘ k(7 ࢆィ⟬࡛ࡁࡿ㸬୍᪉࡛ᐇ㝿ࡢ 3(6 ࡢ㠀ㄪ࿴ᛶࡢ⪃៖࡟ࡣ 3(6 ஺ᕪ㡿ᇦࡢィ⟬ࡀᚲせ࡛࠶ࡿ㸬(7 ࡟㛵ࢃࡿ 3(6 ஺ᕪ㡿ᇦࡢィ⟬࡛ࡣ㸪(7๓ᚋ  ≧ែࡢ㑅ᢥⓗィ⟬ࡀㄢ㢟࡜࡞ࡿ㸬ᮏ◊✲࡛ࡣ 21,20 ἲࡢศ๭እᤄィ⟬࡟╔┠ࡋࡓ㸬㟁Ꮚ≧ែࢆኚ࠼࡚ศ๭ィ⟬ࡋࡓ࢚ࢿࣝࢠ࣮ࡢእᤄ࡟ࡼࡾ (7 ๓ᚋ  ≧ែࢆ㏱⇕໬ࡍࡿᡭἲࢆ㛤Ⓨࡍࡿࡇ࡜㸪࠾ࡼࡧ㸪㛤Ⓨᡭἲࢆ⏝࠸ࡓ 3(6 ஺ᕪ㡿ᇦィ⟬࠿ࡽ (7 ࢆゎᯒࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬㸯㸫㸰㸬7L2 ⾲㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂ⤒㊰ࡢ᥈⣴཯ᛂ⤒㊰⮬ື᥈⣴ἲ࡛࠶ࡿேᕤຊㄏ㉳཯ᛂ㸦$),5㸧ἲࡢᶵ⬟ࡀᣑᙇࡉࢀ㸪࿘ᮇቃ⏺⣔࡟ᑐᛂࡋࡓ㸬ࡇࢀ࡟ࡼࡾ⾲㠃཯ᛂࡢ⥙⨶ⓗ࡞཯ᛂ⤒㊰᥈⣴ࡀྍ⬟࡜࡞ࡗࡓ㸬ᮏ◊✲࡛ࡣࡑࡢᛂ⏝࡜ࡋ࡚㸪࢔ࢼࢱ࣮ࢮᆺ 7L2 ࡢ 㠃ୖ࡟࠾ࡅࡿ⇕ⓗ࡞ࢠ㓟ศゎ཯ᛂ࡟ὀ┠ࡋ㸪ࡇࡢ཯ᛂᶵᵓࢆ⣔⤫ⓗ࡟ゎᯒࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬㸯㸫㸱㸬ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ド཯ᛂ㛤Ⓨ࡛ࡣ㸪ᵝࠎ࡞཯ᛂ≀㉁ࡸ཯ᛂ᮲௳ࡢ⤌ࡳྜࢃࡏࢆࢫࢡ࣮ࣜࢽࣥࢢࡍࡿᚲせࡀ࠶ࡿ㸬ࡇࡇ࡛㸪')7ィ⟬࡞࡝࡛ᚓࡽࢀࡓ཯ᛂ㞀ቨࡸ཯ᛂ࢚ࢿࣝࢠ࣮࡞࡝ࡢ᝟ሗ࡟ᇶ࡙࠸ࡓ཯ᛂࢫࢡ࣮ࣜࢽࣥࢢࡣ㸪ᐇ㦂ࢥࢫࢺࡢ๐ῶ࡟᭷ຠ࡛࠶ࡿ㸬ࡋ࠿ࡋ㸪௦ࢃࡾ࡟ィ⟬ࢥࢫࢺࢆせࡍࡿࡓࡵ㸪ᑡ࡞࠸ヨ⾜ᅇᩘ࡛ࢫࢡ࣮ࣜࢽࣥࢢ࡛ࡁࡿᡭ

- 320 -

ἲࡢ㛤Ⓨࡀᚲせ࡛࠶ࡿ㸬ࡇࡢ࡜ࡁ㸪ྛᡭἲࡢᛶ⬟ࢆ༶ᗙ࡟ホ౯࡛ࡁࡿࢹ࣮ࢱࢭࢵࢺࡀ࠶ࡿ࡜㠀ᖖ࡟౽฼࡛࠶
ࡿ㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ㸪ࢡࣛ࢖ࢮࣥ㌿఩཯ᛂ࡟╔┠ࡋ㸪཯ᛂ㞀ቨࡢࢹ࣮ࢱࢭࢵࢺࢆィ⟬࡛సᡂࡋࡓ㸬ࡲࡓ㸪㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒ *$ ࢆ⏝࠸ࡓࢫࢡ࣮ࣜࢽࣥࢢᡭἲࢆᐇ⿦ࡋ㸪ᚓࡽࢀࡓࢹ࣮ࢱࢭࢵࢺࢆ⏝࠸࡚ࡑࡢᛶ⬟ࢆホ౯࡛ࡁࡿ࠿᳨ドࡋࡓ㸬㸯㸫㸲㸬཯ᛂᛶࡢỈࢡࣛࢫࢱ࣮ෆ఩⨨౫Ꮡᛶ࡟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ィ⟬໬Ꮫⓗᡭἲࢆ⏝࠸࡚㸪⁐፹⾲㠃ࡢᏑᅾࡀ᭷ᶵ཯ᛂ
࡟୚࠼ࡿᙳ㡪ࢆ⌮ゎࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓ㸬㸰㸬◊✲᪉ἲ㸪ィ⟬᪉ἲ㸰㸫㸯㸬࢚ࢿࣝࢠ࣮ศ๭እᤄ࡟ࡼࡿ㏱⇕໬ᡭἲࡢ㛤Ⓨ࡜㟁Ꮚ⛣ື཯ᛂゎᯒ
㛤Ⓨᡭἲ࡟ࡼࡿ (7 ๓ᚋ  ≧ែࡢ㏱⇕≧ែ࢚ࢿࣝࢠ࣮V ࡜ V ࡣ௨ୗࡢᘧ࡛ィ⟬ࡉࢀࡿ㸬ྛ E ࡣ㟁Ꮚ࢚ࢿࣝࢠ࣮࡛࠶ࡾ㸪ῧ࠼Ꮠ &㸪' ࠾ࡼࡧ $ ࡣࡑࢀࡒࢀࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮࠿ࡽ࡞ࡿ㘒య &RPSOH[ 㸪'RQRU ࠾ࡼࡧ $FFHSWRU ࢆ⾲ࡍ㸬ࡲࡓ㸪m ࠾ࡼࡧ n ࡣࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮ࡢ㟁Ꮚᩘࢆ⾲ࡍ㸬3(6 ࡢ໙㓄࡜࣊ࢩ࢔ࣥࡶྠ
ᵝ࡟ィ⟬ࡍࡿ㸬

㛤Ⓨᡭἲࢆ㔠ᒓ㘒య>0 / n@㛫ࡢ⮬ᕫ㟁Ꮚ஺᥮཯ᛂ࡬㐺⏝ࡋࡓ㸬ࡲࡎ  ౯࡜  ౯ࡢ࢝ࢳ࢜ࣥ༢㔞య࡟ࡘ࠸࡚ *550 ࣉࣟࢢ࣒ࣛ࡟ࡼࡾᵓ㐀᥈⣴ࡋ㸪᭱Ᏻᐃ࡞  ౯࡜  ౯ࡢ༢㔞యࡢ⮬⏤࢚ࢿࣝࢠ࣮ࡢ࿴ࢆάᛶ໬࢚ࢿࣝ
ࢠ࣮ࡢᇶ‽࡜ࡋࡓ㸬ࡲࡓ㸪஧㔞య࡟㛤Ⓨᡭἲࢆ⏝࠸࡚ (7 ๓ᚋ  ≧ែࢆィ⟬ࡋ㸪*550 ࡟ࡼࡾ஺ᕪ㡿ᇦෆᴟᑠᵓ㐀ࢆ᭱㐺໬ࡋࡓ㸬ࡇࡢᵓ㐀ࢆ㑄⛣≧ែ࡜ࡳ࡞ࡋ㸪άᛶ໬࢚ࢿࣝࢠ࣮ࡸ㟁Ꮚ࢝ࢵࣉࣜࣥࢢ࢚ࢿࣝࢠ࣮ࢆ࣐
࣮࢝ࢫ⌮ㄽࡢ㏿ᗘᘧ࡟௦ධࡋ࡚ k(7 ࢆィ⟬ࡋࡓ㸬ࡑࡢᚋ㸪k(7 ࢆ  ࡘࡢ㔠ᒓ㘒యࡢ୰ᚰ㔠ᒓ㛫㊥㞳࡟ᑐࡋ࡚ᴟ
኱໬ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ *DXVVLDQ ࡢ ')7 ィ⟬ࢆ⏝࠸ࡓ㸬ỗ㛵ᩘ࡜ᇶᗏ㛵ᩘࡣ 8Ȧ%;''HI69 3 ࢆ⏝࠸ࡓ㸬⁐፹ࡢ⪃៖ࡣ &3&0 :DWHU ࢆ⏝࠸ࡓ㸬ࡲࡓ㸪ồࡵࡓ஺ᕪ㡿ᇦࡢ㘒య஧㔞య࡟ $FWLYDWLRQ6WUDLQ0RGHOࢆ㐺⏝ࡋ㸪(7 ࡢάᛶ໬࢚ࢿࣝࢠ࣮㸦஺ᕪ㡿ᇦ࡟฿㐩ࡍࡿࡓࡵ࡟ᚲせ࡞࢚ࢿࣝࢠ࣮㸧ࢆ㘒య㛫┦஫స⏝࡜㘒యෆ㒊ࡢᵓ㐀ኚ໬࡟ࡼࡿ࢚ࢿࣝࢠ࣮ኚ໬࡟ศ๭ࡋ࡚ㄪ࡭ࡓ㸬㸰㸫㸰㸬7L2 ⾲㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂ⤒㊰ࡢ᥈⣴㟁Ꮚ≧ែィ⟬࡟ࡣ 6,(67$ ࣉࣟࢢ࣒ࣛ㸦YHUVLRQ㸧ࢆ౑⏝ࡋ㸪**$3%( ỗ㛵ᩘ࠾ࡼࡧ '=3 ᇶᗏࢆ⏝࠸㸪ศᩓຊࡣ *ULPPH ࡢ ' ศᩓ⿵ṇ࡛⪃៖ࡋࡓ㸬཯ᛂ⤒㊰᥈⣴࡟ࡣ *550 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓ $),5 ἲࢆ⏝࠸ࡓ㸬࢔ࢼࢱ࣮ࢮᆺ 7L2 ࡢᵓ㐀ࡣ 0DWHULDOV3URMHFW ࡀබ㛤ࡋ࡚࠸ࡿ⤖ᬗᵓ㐀ࢹ࣮ࢱ࣮࣋ࢫ࠿ࡽྲྀᚓࡋࡓ㸬9(67$ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚⤖ᬗᵓ㐀ࢆ㐺ษ࡟ᗙᶆኚ᥮ࡋ㸪  㠃ࢆษࡾฟࡋ࡚   ⛬ᗘࡢ┿✵ᒙࢆ☜ಖࡋࢫࣛࣈ
ࣔࢹࣝ࡜ࡋࡓ㸬ィ⟬ᑐ㇟ࡣΎί⾲㠃㸪㓟⣲Ḟ㝗⾲㠃㸪Ỉ⣲྾╔⾲㠃ࡢ  ✀㢮ࡢ⾲㠃࡟ࢠ㓟ࢆຍ࠼ࡓ⤌ᡂࢆ⏝࠸࡚⾲㠃ᵓ㐀ࡢᑐ⛠ᛶࢆಖᣢࡋ࡚ᢅࡗࡓ㸬- 321 -

㸰㸫㸱㸬ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ド↓⨨᥮࢔ࣜࣝࣅࢽ࢚࣮ࣝࢸࣝࡢ  ⟠ᡤࡢỈ⣲ࢆ  ✀㢮ࡢ⨨᥮ᇶ࡛⨨᥮ࡋ㸪 ୓㏻ࡾࡢศᏊࢆ⏕ᡂࡋࡓ ᅗ  㸬ྛศᏊࡢࢡࣛ࢖ࢮࣥ㌿఩࡟࠾ࡅࡿ཯ᛂ㞀ቨࢆ㛤Ⓨ⪅∧ *550 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓேᕤຊㄏ㉳཯ᛂἲࢆ⏝࠸࡚ㄪ࡭㸪཯ᛂ㞀ቨࡢࢹ࣮ࢱࢭࢵࢺࢆసᡂࡋࡓ㸬࡞࠾㸪ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ *DXVVLDQ㸪ィ⟬ᡭἲ࡟ࡣ 30 ࢆ⏝࠸ࡓ㸬ࡲࡓ㸪ྛศᏊࡢ཯ᛂฟ
Ⓨ≀࣭㑄⛣≧ែ㛫ࡢ┦ᑐⓗ࡞Ᏻᐃᛶࢆ⪃៖ࡋ㸪㞀ቨࢆ෌ィ⟬ ᶆ‽໬ ࡋࡓࢹ࣮ࢱࢭࢵࢺࡶసᡂࡋࡓ㸬ᅗ  ࢔ࣜࣝࣅࢽ࢚࣮ࣝࢸࣝࡢ  ࠿ᡤࡢ⨨᥮఩⨨࡜  ✀㢮ࡢ⨨᥮ᇶ㸰㸫㸲㸬཯ᛂᛶࡢỈࢡࣛࢫࢱ࣮ෆ఩⨨౫Ꮡᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲⁐፹ศᏊࡀẼ┦࡜᥋ࡋ࡚࠸ࡿ㡿ᇦ࡜⁐፹ศᏊ࡟ᅖࡲࢀࡓ㡿ᇦࡢ㏆᥋ࡋࡓ⣔࡜ࡋ࡚㸪Ỉ  ศᏊ࠿ࡽ࡞ࡿỈࢡࣛࢫࢱ࣮ࢆᵓ⠏ࡋࡓᅗ  㸬ᢅ࠺཯ᛂࡣࢫࢺࣞࢵ࣮࢝཯ᛂࢆタᐃࡋ㸪཯ᛂ≀࡜⏕ᡂ≀ࡢᵓ㐀ࢆ⧅ࡄ཯ᛂ⤒㊰ࢆ㛤Ⓨ⪅∧ *550 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓ
ேᕤຊㄏ㉳཯ᛂἲࢆ⏝࠸࡚ᚓࡓ㸬㟁Ꮚ≧ែィ⟬ࡣ㸪25&$  ࠾ࡼࡧ ;7% ࢆ⏝࠸ࡓ㸬㸱㸬◊✲ᡂᯝᅗ  Ỉࢼࣀࢡࣛࢫࢱ࣮࡜཯ᛂ≀ศᏊ㸱㸫㸯㸬࢚ࢿࣝࢠ࣮ศ๭እᤄ࡟ࡼࡿ㏱⇕໬ᡭἲࡢ㛤Ⓨ࡜㟁Ꮚ⛣ື཯ᛂゎᯒᅗ  ࡟㟁Ꮚ⛣ື㏿ᗘᐃᩘࡢᑐᩘࣉࣟࢵࢺࢆ♧ࡍ㸬୰ᚰ㔠ᒓ㛫㊥㞳࡟ᑐࡋ࡚ᴟ኱໬ࡉࢀࡓ k(7 kFDOF ࡣᐇ㦂 kH[SW ࡢഴྥࢆᐃᛶⓗ࡟♧ࡋ࡚࠾ࡾ㸪
㛤Ⓨࡋࡓᡭἲࡢ᭷ຠᛶࡀ♧ࡉࢀ࡚࠸ࡿ㸬ࡲࡓ㸪㘒య㛫㠀⤖ྜᛶ┦஫స⏝ࢆゎᯒࡋࡓ࡜ࡇࢁ㸪>&R 1+ @ ࡸ>5X 1+ @࡞࡝ࡣ┦஫స⏝࢚ࢿࣝࢠ࣮ࡀṇ್ࢆ♧ࡋࡓ㸬୍᪉㸪ከࡃࡢ㘒య࡛㈇್ࢆ♧ࡋ㘒యᙧᡂ࡟ࡼࡿ
Ᏻᐃ໬ࡍࡿഴྥࡀぢࡽࢀࡓ㸬ࡉࡽ࡟㸪㟁Ꮚ⛣ື㏿ᗘࢆỴᐃࡍࡿせᅉࡢ୍ࡘ࡛࠶ࡿ㘒యෆ㒊࢚ࢿࣝࢠ࣮ኚ໬ࢆ཯ᛂ⤒㊰࡟ἢࡗ࡚ゎᯒࡋࡓ࡜ࡇࢁ㸪㓄఩⤖ྜ㛗࡜ෆ㒊࢚ࢿࣝࢠ࣮ࡢ୙Ᏻᐃ໬࡟┦㛵ࡀぢࡽࢀࡿࡇ࡜
ࡀࢃ࠿ࡗࡓ㸬௒ᚋࡣ㟁Ꮚ⛣ືࡢヲ⣽࡞ゎᯒࢆ࠾ࡼࡧᛂ⏝ࢆ㐍ࡵࡿ㸬ᅗ  㟁Ꮚ⛣ື㏿ᗘᐃᩘࡢᑐᩘࣉࣟࢵࢺ

㸱㸫㸰㸬7L2 ⾲㠃ୖ࡟࠾ࡅࡿࢠ㓟ศゎ཯ᛂ⤒㊰ࡢ᥈⣴ᅗ  ࡟ᚓࡽࢀࡓ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡࢆ♧ࡍ㸬ᐇ㦂࡛ࡣ㸪㧗᮲௳࡛ +2㸪&2 ࠾ࡼࡧ࣒࣍ࣝ࢔ࣝࢹࣄࢻࡀ୺࡞⬺㞳⏕ᡂ≀࡜ࡋ࡚ࡑࢀࡒࢀ
ほࡉࢀ࡚࠸ࡿ㸬ィ⟬࡛ᚓࡽࢀࡓ཯ᛂࣉࣟࣇ࢓࢖ࣝ࠿ࡽ㸪. ⛬ᗘࡢẚ㍑ⓗప࡛ࡶ㏿ᗘㄽⓗ࡟฿㐩ྍ⬟࡞άᛶ໬㞀ቨ࡛ +2 ࡀ⏕ࡌࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ㸬ࡲࡓ㸪&2 ࠾ࡼࡧ࣒࣍ࣝ࢔ࣝࢹࣄࢻࡀ⏕ᡂࡍࡿάᛶ໬㞀ቨࡣẚ㍑ⓗ㧗ࡃ㸪 . ⛬ᗘࡢ㧗᮲௳ࡀᚲせ࡟࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪ᐇ㦂⤖ᯝ࡜୍⮴ࡍࡿ㸬㓟⣲ྠ఩య 2 ࡢ㇏ᐩ࡞ࣝࢳࣝ
ᆺ 7L2  㠃ࢆ⏝࠸ࡓྠᵝࡢࢠ㓟ศゎ཯ᛂࡣ㸪⬺㞳ࡋࡓ +2 ࡢ㓟⣲ཎᏊࡣࢠ㓟࠾ࡼࡧ 7L2 ⾲㠃ࡢ୧᪉࠿ࡽ౪⤥ࡉࢀ࡚࠸ࡿࡇ࡜ࡀᐇ㦂࡛♧ࡉࢀ࡚࠸ࡿ㸬୍᪉㸪᥈⣴࡛ᚓࡽࢀࡓỈ⣲྾╔⾲㠃ࡢ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡
ࢡ࡟ࡣ㸪ࢠ㓟࠿ࡽ +2 ࡀⓎ⏕ࡍࡿ⤒㊰࡜㸪7L2 ⾲㠃ࡢ㓟⣲ࡀ +2 ࡜ࡋ࡚ᢤࡅࡿ⤒㊰ࡢ୧᪉ࡀᏑᅾࡍࡿ㸬௨ୖࡼࡾ㸪ࢠ㓟ࡢ㑏ඖⓗศゎࣉࣟࢭᅗ  ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ㸬ࢫ࡟࠾࠸࡚ࡣᚲࡎࡋࡶ㓟⣲Ḟ㝗ࡀᚲせ࡛ࡣ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸬D  Ύί⾲㠃㸪E 㓟⣲Ḟ㝗⾲㠃- 322 -

㸱㸫㸱㸬ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ドィ⟬࡟ࡼࡾ  ศᏊ࡛ࢡࣛ࢖ࢮࣥ㌿఩ࡢ㑄⛣≧ែࢆᚓࡓ㸬ྛศᏊ࡟࠾ࡅࡿ཯ᛂ㞀ቨࢆィ⟬࣭ᶆ‽໬࡟ࡼࡾ㸪ᮃࡲࡋ࠸⨨᥮ᇶࡢලయⓗ࡞✀㢮ࡀኚ໬ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬᳨ウࡢ⤖ᯝ㸪࠸ࡎࢀࡢࢹ࣮ࢱࢭࢵࢺ࡟ᑐࡋ
࡚ࡶ㸪 ᅇࡢヨ⾜࡛ ๓ᚋࡢ☜⋡㸪 ᅇࡢヨ⾜࡟࠾࠸࡚ࡣ ࢆ㉺࠼ࡿ☜⋡࡛㸪*$ ࡣᑐ㇟ࡢศᏊࢆⓎぢ࡛ࡁࡓ㸬ୖグࡢ⤖ᯝ࣭ゎᯒ࡟ࡼࡾ㸪ᚓࡽࢀࡓࢹ࣮ࢱࢭࢵࢺࡀ໬Ꮫⓗ࣭ᩘ್ⓗ࡞ほⅬ࠿ࡽ᭷⏝࡞ࢹ࣮ࢱࢭࢵ
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࢚࣏࢟ࢩ໬཯ᛂ࡬ࡢ㐺⏝ࠖ( ➨  ᅇศᏊ⛉Ꮫウㄽ఍໭ᾏ㐨኱Ꮫᮐᖠ㸪ཱྀ㢌Ⓨ⾲>@ࠐఀ⸨⌶☻ཎῲ♸๓⏣⌮ࠕ཯ᛂ⤒㊰⥙࡜➨୍ཎ⌮ศᏊືຊᏛィ⟬࡟ᇶ࡙ࡃศᏊෆ 'LHOV$OGHU ཯ᛂࡢ㏿ᗘㄽゎᯒࠖࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ࢜ࣥࣛ࢖ࣥᮐᖠ㸪࣏ࢫࢱ࣮Ⓨ⾲㸪>@ࠐᮡᒣెዉ⨾๓⏣⌮ࠕࢳࢱࣀࢩࣜࢣ࣮ࢺ࡜㐣㓟໬Ỉ⣲࡟ࡼࡿࣉࣟࣆࣞࣥࡢ࢚࣏࢟ࢩ໬཯ᛂ࡟ᑐࡍࡿ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡࡢᵓ⠏࡜㏿ᗘㄽⓗゎᯒࠖ3 ࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ࢜ࣥࣛ࢖ࣥᮐᖠ㸪࣏ࢫࢱ࣮Ⓨ⾲>@‫ࠐۻ‬භ㎷ᬗ኱ᩧ⏣ㅬ୍㑻๓⏣⌮ࠕศ๭እᤄἲ࡜஺ᕪ᥈⣴࡟ࡼࡿ㔠ᒓ㘒య㛫⮬ᕫ㟁Ꮚ஺᥮཯ᛂࡢ㏿ᗘィ⟬ࠖ3 ࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ
⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ࢜ࣥࣛ࢖ࣥᮐᖠ㸪࣏ࢫࢱ࣮Ⓨ⾲㸪>@‫ࠐۻ‬ᒸ⏣ᣅ᫂๓⏣⌮ࠕ㞀ቨ࡟ᇶ࡙ࡃ཯ᛂࢫࢡ࣮ࣜࢽࣥࢢ࡟ྥࡅ࡚㸸ࢡࣛ࢖ࢮࣥ㌿఩ࡢ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜᳨ドࠖ3 ࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ࢜ࣥࣛ࢖ࣥᮐᖠ㸪࣏ࢫࢱ࣮Ⓨ⾲㸪>@‫⏿ྡࠐۻ‬ኍᚿ๓⏣⌮ࠕ7L2
⾲㠃ୖ࡟࠾ࡅࡿỈᛶ࢞ࢫࢩࣇࢺ཯ᛂ⤒㊰ࡢ⣔⤫ⓗ᥈⣴ࠖ3 ࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ࢜ࣥࣛ࢖
ࣥᮐᖠ㸪࣏ࢫࢱ࣮Ⓨ⾲㻌㸳㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬$0XWVXMLK. Saita, S. Maeda, (about the first topic, in preparation). [2] ‫ۻ‬+1DEDWDS. Maeda, (about the second topic, in preparation). [3]‫ۻ‬H. Okada, S. Maeda, Mol. Inform., 2022, 41, 2100216 (about the third topic). [4] S. Maeda, Y. Harabuchi, T. Hasegawa, K. Suzuki, T. Mita
AsiaChem, 2021, 2, 56. [5] R. Takahashi, A. Hu, P. Gao, Y. Gao, Y. Pang, T. Seo, J. Jiang, S. Maeda, H. Takaya, K. Kubota, H. Ito, Nat. Commun.,
2021, 12, 6691. [6] T. Shibata, T. Shibata, S. Nishibe, H.Takano, S. Maeda, Org. Chem. Front., 2021, 8, 6985. [7] H. Takano, Y. You, H. Hayashi, Y.
Harabuchi, S. Maeda, T. Mita, ACS Omega, 2021, 6, 33846. [8] W. Kanna, Y. Harabuchi, H. Takano, H. Hayashi, S. Maeda, T. Mita, Chem. Asian J.,
2021, 16, 4072. [9] K. Sugiyama, K. Saita, S. Maeda, J. Comput. Chem., 2021, 42, 2163. [10] D. Yang, P. Bao, Z. Yang, Z. Chen, S. Sakaki, S. Maeda,
G. X. Zeng, ChemCatChem, 2021, 13, 3925. [11] K. Takahashi, S. Maeda, RSC Adv., 2021, 11, 23235. [12] T. Ohmura, Y. Morimasa, T. Ichino, Y.
Miyake, Y. Murata, M. Suginome, K. Tajima, T. Taketsugu, S. Maeda, Bull. Chem. Soc. Jpn., 2021, 94, 1894. [13] S. Maeda, Y. Harabuchi, WIREs
Comput. Mol. Sci., 2021, 11, e1538. [14] H. Hayashi, H. Takano, H. Katsuyama, Y. Harabuchi, S. Maeda, T. Mita, Chem. Eur. J., 2021, 27, 10040.
[15] Y. Murata, K. Matsunagi, J. Kashida, Y. Shoji, C. Ozen, S. Maeda, T. Fukushima, Angew. Chem. Int. Ed., 2021, 60, 14630. [16] P. J. Castro, S.
Maeda, K. Morokuma, Int. J. Quantum Chem., 2021, 121, e26663. [17] A. R. Pradipta, P. Ahmadi, K. Terashima, K. Muguruma, M. Fujii, T. Ichino, S.
Maeda, K. Tanaka, Chem. Sci., 2021, 12, 5438. [18] Y. Kamei, Y. Seino, Y. Yamaguchi, T. Yoshino, S. Maeda, M. Kojima, S. Matsunaga, Nat.
Commun., 2021, 12, 966. [19] T. Gimadiev, R. Nugmanov, D. Batyrshin, T. Madzhidov, S. Maeda, P. Sidorov, A. Varnek, J. Chem. Inf. Model., 2021,
61, 554. [20] K. Matsuoka, N. Konami, M. Kojima, T. Mita, K. Suzuki, S. Maeda, T. Yoshino, S. Matsunaga, J. Am. Chem. Soc., 2021, 143, 103. [21]S. Kinoshita, Y. Harabuchi, Y. Inokuchi, S. Maeda, M. Ehara, K. Yamazaki, T. Ebata, Phys. Chem. Chem. Phys., 2021, 23, 834.

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19.6
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O

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H
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N
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ΔG (kcal/mol)

ΔG (kcal/mol)

23.3(22.4)

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0
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C
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O

O
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N
N

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115b0

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CO
CO

CO

CO

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N
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5.8
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115a0

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–1.6
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O
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HC
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N
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TS-2a2c

S
S

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31.6
26.4

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25.9

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7.7
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5.3

3.6

N
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H
NiII

S
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2b’

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2c

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ࣙࣥࠊ᱁ᏊືຊᏛ㸦LD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘ㸦NEGF㸧⌮ㄽ࡞࡝ࡢ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢶ࣮ࣝࡣࠊಙ㢗ᛶࡢ㧗࠸⇕ఏᑟ⋡ࡢணࢆྍ⬟࡟ࡍࡿࡀࠊィ⟬ࢥࢫࢺࡀ㧗࠸ࡇ࡜ࡀㄢ㢟࡜ࡋ࡚ṧࡗ࡚࠸ࡿࠋ

᪂ࡋ࠸ᮦᩱྜᡂᢏ⾡ࡢ㛤Ⓨࡸࠊ≀ᛶࡢ㎿㏿࠿ࡘṇ☜࡞ண࡟ᑐࡍࡿ㟂せࡀᛴ㏿࡟㧗ࡲࡗ࡚࠸ࡿࡇ࡜࠿ࡽࠊ᪂

ࡓ࡞ィ⟬ᡭἲࡀồࡵࡽࢀ࡚࠸ࡿࠋࡑࢇ࡞୰ࠊᶵᲔᏛ⩦㸦ML㸧ἲ࡟ࡼࡿ᭷ᮃ࡞ゎỴ౛ࡀ࠶ࡿࠋ౛࠼ࡤ㸪Liu ࡽ[6]ࡣ㸪ࢧ࣏࣮ࢺ࣋ࢡࢱ࣮ᅇᖐ㸦SVR㸧࡟ᇶ࡙ࡃ ML ࣔࢹࣝࢆ⏝࠸࡚㸪⣧⢋࡞ὶయ࡜ࡑࡢΰྜ≀ࡢ⇕ຊᏛⓗ≉ᛶࢆ◊✲ࡋ㸪ᇶ♏࡜࡞ࡿ≀⌮ⓗ࣓࢝ࢽࢬ࣒ࢆ஦๓࡟▱ࡽ࡞ࡃ࡚ࡶ㸪ὶయࡢ⇕ຊᏛⓗ≉ᛶࢆṇ☜࡟ணࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋWu ࡽ[1]ࡣ㸪␗࡞ࡿ ML ࣔࢹࣝࢆ⏝࠸࡚⏺㠃⇕᢬ᢠࢆணᢠࡀ 51.8s4.510-9 m2/KW ࡜㧗࠸ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ㸪ࡇࢀࡣᐇ㦂ⓗ࡞࡛ࡁࡿࡋ㸪Bi/Si ᮦᩱ⣔ࡢ⏺㠃⇕᢬ᐃ⤖ᯝ࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ୍⯡ⓗ࡟ࠊୖ㏙ࡢ ML ἲࡣࠊᇶ♏ⓗ࡞⇕㍺㏦࣓࢝ࢽࢬ࣒ࢆ▱ࡽ࡞ࡃ࡚ࡶࠊࢹ࣮ࢱゎᯒ࡟ᇶ࡙࠸࡚≀㉁ࡢᕧどⓗ࡞⇕≉ᛶࢆணࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡉࡽ࡟ࠊࡇࢀࡲ࡛ࡢ◊✲࡛ࡣࠊML ࣏ࢸࣥࢩࣕࣝ࡜ᚑ᮶ࡢ㍺㏦ィ⟬ἲࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛ࠊᮦᩱࡢ⇕ఏᑟ⋡ࢆணࡋࠊࡉࡽ࡟ࡣ᰿ᮏⓗ࡞⇕㍺㏦࣓࢝ࢽࢬ࣒ࢆ᥈ࡿࡓࡵࡢ᪂ࡓ࡞ᡭẁ࡜࡞ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋ౛࠼ࡤ㸪Gu ࡽ[2]ࡣ㸪ࢫ࣌ࢡࢺࣝ㏆ഐゎᯒ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚㸪༢ᒙ MoS2(1x)Se2x ྜ㔠ࡢ⇕㍺㏦ࢆ◊✲ࡋ㸪ࡉࡽ࡟㸪㉁㔞ࡢ஘ࢀ࡜ຊሙࡢ஘ࢀࡀ⇕ఏᑟ⋡࡟ཬࡰࡍᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
᭱㏆ࠊ≀㉁ࡢ⇕ⓗ≉ᛶࡢ◊✲࡟ ML ἲࢆ㐺⏝ࡋࡓㄽᩥࡀ┦ḟ࠸࡛Ⓨ⾲ࡉࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊ㛵㐃ࡍࡿᢏ⾡ࡀᵝࠎ࡞≀⌮ⓗ≉ᛶࢆணணࡍࡿࡓࡵࡢᙉຊ࡞ࢶ࣮ࣝ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋᐇ㝿㸪ML ἲࡣ㸪ᵓ㐀㸪ᮦᩱタィ㸪༙ᑟయ〇㐀㸪་⸆ရ㛤Ⓨ࡞࡝㸪ከࡃࡢศ㔝࡛ᗈࡃᛂ⏝ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࢀࡽࡢከࡃ

ࡀ」㞧࡞≉ᚩ㔞ࢆᏛ⩦ࢹ࣮ࢱ࡟౑⏝ࡋ࡚࠸ࡿࡓࡵࠊᮦᩱタィࡢึᮇẁ㝵࡛ࡣά⏝ࡍࡿࡇ࡜ࡀ㞴ࡋ࠸࡜࠸࠺ၥ
㢟Ⅼࡀ࠶ࡿࠋࡑࡇ࡛ࠊᮏㄽᩥ࡛ࡣከᩘࡢ᭷ᮃ࡞≉ᛶࢆ᭷ࡍࡿᮦᩱࢆྵࡴࣇࣝ࣍࢖ࢫ࣮ࣛᵓ㐀࡟╔┠ࡋࠊࡑࢀࡽࡢ⇕ఏᑟ⋡ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚⟬ฟࡍࡿ࡜࡜ࡶ࡟ࠊᇶᮏⓗ࡞≀⌮㔞ࡢࡳࢆ≉ᚩ㔞࡜ࡋ࡚⏝࠸ࡿࡇ࡜࡛
ML ࡟ࡼࡿண

ࡀྍ⬟࠿࡝࠺࠿ࡢ᳨ドࢆ⾜ࡗࡓࠋᮏㄽᩥ࡛ࡣከᩘࡢ᭷ᮃ࡞≉ᛶࢆ᭷ࡍࡿᮦᩱࢆྵࡴࣇࣝ࣍࢖ࢫ࣮ࣛᵓ㐀࡟╔┠ࡋࠊࡑࢀࡽࡢ⇕ఏᑟ⋡ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚⟬ฟࡍࡿ࡜࡜ࡶ࡟ࠊᇶᮏⓗ࡞≀⌮㔞ࡢࡳࢆ≉ᚩ㔞࡜ࡋ࡚⏝࠸ࡿࡇ࡜࡛ ML ࡟ࡼࡿண⬟࠿࡝࠺࠿ࡢ᳨ドࢆ⾜ࡗࡓࠋ- 328 -

ࡀྍ◊✲᪉ἲࠊィ⟬᪉ἲMaterials Project ࢹ࣮ࢱ࣮࣋ࢫ୰ࡢࣇࣝ࣍࢖ࢫ࣮ࣛᵓ㐀ࢆ᭷ࡍࡿ≀㉁ࡢ୰࠿ࡽ⇕ຊᏛⓗ࡟Ᏻᐃ࡞㔠ᒓ㛫໬ྜ≀࡛࠶ࡿ≀㉁ࢆࢫࢡ࣮ࣜࢽࣥࢢࡋࡓ⤖ᯝᚓࡽࢀࡓ 957 ✀㢮ࡢ໬ྜ≀ࡢ cif ࣇ࢓࢖ࣝࢆྲྀᚓࡋࡓࠋࢥ࣮ࢻࡣ
python ࢆ⏝࠸࡚グ㏙ࡋࠊpymatgen ࣛ࢖ࣈࣛࣜࢆ฼⏝ࡍࡿࡇ࡜࡛ࢹ࣮ࢱࡢ཰㞟ࢆ⾜ࡗࡓࠋᅗ 1 ࡟౑⏝ࡋࡓඖ⣲ࢆ㉥ᯟ࡛♧ࡍࠋᅗ 2 ࡟ࢫࢡ࣮ࣜࢽࣥࢢࡢᴫせࢆ♧ࡍࠋᵓ㐀᭱㐺໬࡜ࡣࠊ࢚ࢿࣝࢠ࣮ࢆኚ࠼࡚⧞ࡾ㏉ࡋィ⟬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮ࡢ౫Ꮡᛶࢆぢࡿࡇ࡜࡛ࠊ᭱ࡶ࢚ࢿࣝࢠ࣮ࡢప࠸᱁Ꮚᐃᩘࢆぢࡘࡅࡿࡇ࡜࡛࠶ࡿࠋᚓࡽࢀࡓ
957 ✀㢮ࡢ≀㉁࡟ᑐࡋ࡚ VASP ࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᱁Ꮚᐃᩘࢆ⟬ฟࡋࡓࠋ࣏ࢸࣥࢩࣕࣝࡣ GGA ࢆ᥇⏝ࡋࡓࠋᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓ᱁Ꮚᐃᩘࢆᩍᖌࢹ࣮ࢱ࡜ࡋ࡚ࠊᅇᖐ࡟ࡼࡿண

ࢆ⾜ࡗࡓࠋ≉ᚩ㔞࡜ࡋ࡚ཎᏊ

༙ᚄ࠾ࡼࡧཎᏊ㉁㔞ࢆ⏝࠸ࠊձ⥺ᙧᅇᖐղࣛࣥࢲ࣒ࣇ࢛ࣞࢫࢺճXGBoost ࡢ 3 ✀㢮ࡢᅇᖐ࡟ࡼࡾணࣔࢹࣝࡢᵓ⠏ࢆ⾜ࡗࡓࠋࡑࢀࡒࢀࡢᅇᖐ࡟࠾࠸࡚≉ᚩ㔞ࡣ 4 ࢧ࢖ࢺࡢཎᏊ༙ᚄ(r1㹼r4)ࡢࡳࡢሙྜ࡜ཎᏊ༙ᚄ࡟ຍ࠼
ཎᏊ㉁㔞(m1㹼m4)ࢆຍ࠼ࡓሙྜࡢ 2 ࣃࢱ࣮ࣥࢆ᥇⏝ࡋࡓࠋࡲࡓࠊࡍ࡭࡚ࡢᏛ⩦㐣⛬࡟࠾࠸࡚ࢸࢫࢺࢹ࣮ࢱࢆ
20%࡜ࡋࡓ 5-fold Cross Validation ࢆ⾜࠸ࠊࡉࡽ࡟ 10 ᅇࡢ⧞ࡾ㏉ࡋィ⟬ࢆ⾜࠺ࡇ࡜࡛⤖ᯝࡢ᳨ドࢆ⾜ࡗࡓࠋࡲࡓࠊRF ཬࡧ XGBoost ࡛ࡣࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱࡢㄪᩚࢆ 100 ᅇ⾜࠸ࠊࣔࢹࣝࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓ᱁Ꮚᐃᩘࢆ⏝࠸࡚ࠊphonopy ཬࡧ phono3py ࡟ࡼࡗ࡚ 0K ࠿ࡽ 1000K ࡲ࡛ࡢ᱁Ꮚ⇕ఏᑟ⋡ࡢ

ᗘ౫Ꮡᛶࢆ⟬ฟࡋࡓࠋィ⟬ᑐ㇟ࡣ cif ࢆྲྀᚓࡋࡓ࣍࢖ࢫ࣮ࣛྜ㔠 957 ✀㢮ࡢ୰࠿ࡽࣛࣥࢲ࣒࡟

ᢳฟࡋࡓ 274 ✀㢮࡜ࡋࡓࠋ⟬ฟࡋࡓ᱁Ꮚ⇕ఏᑟ⋡ࢆ┠ⓗኚᩘ࡜ࡋ࡚ࠊXGBoost ࡟ࡼࡿᅇᖐࢆ⾜࠸ࠊ᱁Ꮚ⇕ఏᑟ⋡ࡢணࢆ⾜ࡗࡓࠋᵝࠎ࡞≉ᚩ㔞ࢆึᮇࣃ࣓࣮ࣛࢱ࡜ࡋࠊ≉ᚩ㔞㔜せᗘ࡟ᛂࡌ࡚ḟඖ๐ῶࢆ⾜࠺ࡇ࡜࡛ண

⢭ᗘࡢྥୖࢆヨࡳࡓࠋࡲࡓࠊᏛ⩦㐣⛬࡟࠾࠸࡚ࢸࢫࢺࢹ࣮ࢱࢆ 20%࡜ࡋࡓ 5-fold Cross Validation ࢆ⾜࠸ࠊࡉࡽ࡟ 10 ᅇࡢ⧞ࡾ㏉ࡋィ⟬ࢆ⾜࠺ࡇ࡜࡛⤖ᯝࡢ᳨ドࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱࡢㄪᩚࢆ 100 ᅇ⾜࠸ࠊࣔࢹࣝࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋᅗ1ᶵᲔᏛ⩦࡟⏝࠸ࡓඖ⣲ࡢ୍ぴࠋ㉥࡛ᅖࢇࡔඖ⣲ࢆᮏ◊✲࡟⏝࠸ࡓࠋ- 329 -

ᅗ2

Materials Project ࡟Ⓩ㘓ࡉࢀ࡚࠸ࡿ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡢࢫࢡ࣮ࣜࢽࣥࢢ᪉ἲࠋ

◊✲ᡂᯝ

3.1 䝩䜲䝇䝷䞊໬ྜ≀䛻䛚䛡䜛᱁Ꮚᐃᩘ䛾ᶵᲔᏛ⩦⤖ᯝ
ᅗ 4.1 ࡟ᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓ᱁Ꮚᐃᩘ(DFT LatticeParameter)࡜ cif ࡢ᱁Ꮚᐃᩘ࡜ࡢẚ㍑ࢆ♧ࡍࠋMaterials Project ࡟Ⓩ㘓ࡉࢀࡓ cif ࣇ࢓࢖ࣝ࡟グ㍕ࡉࢀࡓ᱁Ꮚᐃᩘࡢ್ࡣ DFT ィ⟬࡜ࡋ
࡚ VASP-code ࢆ⏝࠸࡚ DFT ィ⟬ࡉࢀࡓ್࡜࡯ࡰ୍⮴ࡋ࡚࠾ࡾࠊ኱つᶍィ⟬࡟ࡼࡾồࡵࡽࢀࡓᮏィ⟬ࡢጇᙜᛶࢆ♧ࡍ⤖ᯝ࡜࡞ࡗࡓࠋᅗ 4 ࡟ྛᅇᖐ࡟ࡼࡿண

್࡜ᵓ㐀᭱㐺໬ࡢ್࡜ࡢ┦㛵ࢆ♧ࡍࠋ༢⣧࡞⥺ᙧᅇᖐ࡟࠾࠸࡚ࡶỴᐃಀᩘࡀ 0.888 ཬࡧ 0.923 ࡜㧗ࡃࠊ᱁Ꮚᐃᩘࢆࡼࡃㄝ࡛᫂ࡁࡿࣔࢹࣝ࡜࡞ࡗ࡚࠸ࡿࠋࡉࡽ࡟ࠊࡼ
ࡾ」㞧࡞ࣔࢹࣝࡢᵓ⠏ࡀྍ⬟࡞ xgboost ࡛ࡣỴᐃಀᩘࡀ 0.904 ཬ
ࡧ 0.984 ࡜㠀ᖖ࡟㧗ࡃࠊ࠾࠾ࡴࡡ᏶⎍࡞ࣔࢹࣝࡢᵓ⠏ࡀ࡛ࡁ࡚࠸ᅗ 
 0DWHULDOVV SURMHFW ࡟Ⓩ㘓ࡉࢀࡿࠋࡲࡓࠊ≉ᚩ㔞ᩘ࡛ぢࡓሙྜࠊ࠸ࡎࢀࡢᅇᖐ࡟࠾࠸࡚ࡶཎᏊ༙

࡚࠸ࡿྛ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡢ᱁

ᚄ 4 ࡘ࡟ຍ࠼ཎᏊ㉁㔞 4 ࡘࡶ≉ᚩ㔞࡟ຍ࠼ࡓ 8 ಶࡢࣃ࣓࣮ࣛࢱࡢ

Ꮚᐃᩘ࡜ ')7 ィ⟬࡟ࡼࡾồࡵࡽ

᪉ࡀ 4 ಶࡢࣃ࣓࣮ࣛࢱ࡟ẚ࡭㧗࠸Ỵᐃಀᩘࢆ♧ࡋ࡚࠾ࡾࠊ᱁Ꮚ

ࢀࡓ᱁Ꮚᐃᩘࡢẚ㍑ࠋ
ࢀࡓ᱁Ꮚᐃᩘ
ẚ㍑ࠋ

ᐃᩘࡣཎᏊ༙ᚄࡔࡅ࡛࡞ࡃཎᏊ㉁㔞ࡶ㛵ಀࡍࡿ࡜࠸࠺」㞧࡞㛵ಀ࠿ࡽᡂࡾ❧ࡗ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋᅗ 4.9
࠿ࡽᅗ 4.11 ࡼࡾࠊㄗᕪࡢ್ࢆぢ࡚ࡶ xgboost_8para ࡟࠾ࡅࡿㄗ
ᕪࡀ᭱ࡶᑠࡉࡃࠊ᭱㐺࡞ࣔࢹ࡛ࣝ࠶ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ୍⯡ⓗ࡟᱁ᏊᐃᩘࡣཎᏊ༙ᚄ࡟ᇶ࡙࠸࡚㆟ㄽࡉࢀࡿࡀࠊᮏ◊✲࡛ࡣཎᏊ༙ᚄࡼࡾࡶཎᏊ㉁㔞ࡢ࡯࠺ࡀ᱁Ꮚᐃᩘࡢ್࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡋ࡚࠸ࡿ࡜࠸࠺⤖ᯝ࡜࡞ࡗࡓࠋཎᅉࡣ⌧ᅾᐃ࠿࡛ࡣ࡞࠸ࡀࠊ
᱁ᏊᐃᩘࡣཎᏊ㉁㔞ࡢほⅬ࠿ࡽࡶ㆟ㄽࡉࢀࡿ࡭ࡁ࡛࠶ࡿࡇ࡜
ࢆ♧၀ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋ
3.2 䝩䜲䝇䝷䞊໬ྜ≀䛻䛚䛡䜛᱁Ꮚ⇕ఏᑟ⋡䛾ᶵᲔᏛ⩦⤖ᯝᅗ  ྛ✀ᅇᖐᡭἲ࠾ࡼࡧྛ✀ࣃ࣓ࣛࢱ࣮ᩘࢆ⏝࠸࡚ᶵᲔᏛ⩦ࡋࡓ᱁ᏊᐃᩘࡢỴᐃ᪉ἲࡢẚ㍑ࠋ

- 330 -

ᅗ 5 ࡟≉ᚩ㔞ࢆ 15 ಶ౑⏝ࡋ࡚ᵓ⠏ࡋࡓࣔࢹࣝ(15para)࡟࠾ࡅࡿ᱁
Ꮚ⇕ఏᑟ⋡ࡢண

್࡜ DFT ィ⟬ࡢ⤖ᯝࡢᩓᕸᅗࢆ♧ࡍࠋࡇࡢࣔࢹ

ࣝ࡟࠾ࡅࡿỴᐃಀᩘࡣ 0.66 ࡛࠶ࡗࡓࠋ≉ᚩ㔞㔜せᗘࡢᐤ୚ࢆㄪᰝ
ࡋࡓ⤖ᯝࠊཎᏊ༙ᚄ࡟㛵ࡍࡿ≉ᚩ㔞ࡣཎᏊ㉁㔞࡟㛵ࡍࡿ≉ᚩ㔞࡜ẚ㍑ࡋ࡚᱁Ꮚ⇕ఏᑟ⋡࡟୚࠼ࡿᙳ㡪ࡀᑠࡉ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇ
ࡢ㡰఩࡟ᛂࡌ࡚≉ᚩ㔞ࢆ๐ῶࡋࡓࣔࢹࣝ࡟࠾ࡅࡿỴᐃಀᩘࢆᅗ 6
࡟♧ࡍࠋ8 ಶࡢࣃ࣓࣮ࣛࢱࠊ5 ಶࡢࣃ࣓࣮ࣛࢱࡲ࡛ࡣྥୖࡋࠊ2 ಶࡢࣃ࣓࣮ࣛࢱ࡛ࡣῶᑡࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋ≉ᚩ㔞ࡢᩘࡀῶᑡࡍࡿ
࡟ࡘࢀ࡚㐣Ꮫ⩦ࡢ㜵Ṇ࡟ࡘ࡞ࡀࡾࠊỴᐃಀᩘࡀྥୖࡋࡓ࡜⪃࠼ࡽࢀࡿࠋㄗᕪࡢほⅬ࠿ࡽࡶ 5 ಶࡢࣃ࣓࣮ࣛࢱࡀ᭱ࡶᑠࡉࡃࠊඃࢀࡓ
ࣔࢹ࡛ࣝ࠶ࡿ࡜ゝ࠼ࡿࠋ5 ಶࡢࣃ࣓࣮ࣛࢱ࡟࠾ࡅࡿண

್࡜ィ⟬್ࡢᩓᕸᅗࢆᅗ 4.16 ࡟♧ࡍࠋࡇࡢࣔࢹࣝ࡟࠾ࡅࡿࡣ 0.78 ࡜㧗ᅗ  ࣍࢖ࢫ࣮ࣛ໬ྜ≀࡟࠾ࡅࡿ⇕ఏᑟ⋡ࡢᶵᲔᏛ⩦࡟ࡼࡾồࡵࡽࢀࡓண್࡜ࡢẚ㍑ࠋ

ࡃࠊ㧗⢭ᗘ࡞ࣔࢹࣝᵓ⠏࡟ᡂຌࡋࡓࠋ᭱ᚋ࡟ 5 ಶࡢࣃ࣓࣮ࣛ
ࢱ࡟࠾ࡅࡿ᱁Ꮚ⇕ఏᑟ⋡ࡢண್࡜ᐇ㦂ⓗ࡟

ᐃࡉࢀࡓ⇕ఏ

ᑟ⋡࡜ࡢ㛵ಀᛶࢆ♧ࡍࠋᐇ㦂್ࡣ⤖ᬗᛶࠊᐦᗘࠊ⤌ᡂẚࠊ⤖ᬗᏊࢧ࢖ࢬࠊ⢏⏺࡞࡝ࡢᙳ㡪ࡀᏑᅾࡍࡿࡓࡵࡎࢀࡀ⏕ࡌ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋᮏ◊✲ࡢᏛ⩦ࣔࢹࣝࡣᐇ㦂್࡟࠾ࡅࡿ⣔⤫ᛶࡶ࡜ࡽ࠼࡚࠾ࡾࠊ⢭ᗘࡢ㧗࠸ࣔࢹ࡛ࣝ࠶ࡿ࡜࠸࠼ࡿࠋ᱁Ꮚ㕲ఏᑟ⋡ࡢ≉ᚩ㔞㔜せᗘࢆゎᯒࡋࡓ⤖ᯝࠊ᱁Ꮚ⇕ఏᑟ⋡ࡢᶵᲔᏛ⩦࡟ࡣࠊ᱁Ꮚᐃᩘࠊ㉁㔞ࡢ࿴ࠊ᭱㏆᥋ཎᏊ㛫ࡢ㉁㔞ᕪࡀୖ఩࡟఩⨨ࡋࡓࠋࡇࡢ⌮⏤࡟ࡘ࠸࡚⪃ᐹࢆ⾜࠺ࠋ᱁Ꮚ⇕ఏᑟ⋡ࡣ callaway ⌮ㄽࡼࡾࠊẚ⇕ࠊ㡢㏿ࠊᖹᆒ⮬⏤⾜⛬ࡢ✚࡟ẚ౛ᅗ  ࣍࢖ࢫ࣮ࣛ໬ྜ≀࡟࠾ࡅࡿ⇕ఏᑟࡍࡿࠋࡉࡽ࡟ࠊ㡢㏿ࡣᐦᗘࡢ㏫ᩘ࡟ẚ౛ࡍࡿ࡜ࡉࢀ࡚࠸ࡿࠋࡘ

⋡ࡢᶵᲔᏛ⩦࡟⏝࠸ࡓࣃ࣓࣮ࣛࢱᩘ

ࡲࡾࠊ᱁Ꮚᐃᩘཬࡧ㉁㔞ࡢ࿴ࡣ㡢㏿ࢆ௓ࡋ࡚᱁Ꮚ⇕ఏᑟ⋡࡜

ࡢẚ㍑ࠋ
ࠋ

┤᥋┦㛵ࡢ࠶ࡿ≀⌮㔞࡛࠶ࡿࡓࡵୖ఩࡟఩⨨ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ᭱㏆᥋ཎᏊ㛫ࡢ㉁㔞ᕪ࡟࠾࠸࡚ࡣࠊ㉁㔞ᕪ࡟ࡼࡿࣇ࢛ࣀࣥᩓ஘ࡢຠᯝࢆ཯ᫎࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࣇ࢛ࣀࣥࢆࡤࡡࣔࢹ࡛ࣝ⪃࠼ࡓሙྜࠊ㏆᥋ཎᏊ㛫ࡢ㉁㔞ᕪࡣ᣺ື࡟㠀ㄪ࿴ᛶࢆࡶࡓࡽࡋࠊ࢚ࢿࣝࢠ࣮ࢆኻ࠺
ࡓࡵࠊ᱁Ꮚ⇕ఏᑟ⋡ࡢῶᑡ࡟ࡘ࡞ࡀࡿࠋࡇࢀࡣ Klemens ࡢ⌮ㄽ[3]࡜୍⮴ࡋ࡚࠾ࡾࠊ࣮ࣜࢬࢼࣈࣝ࡞⤖ᯝ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊ|m1-m2|ཬࡧ|m1-m3|ࡣ࣍࢖ࢫ࣮ࣛᵓ㐀࡟࠾࠸࡚᭱ࡶᩘࡢከ࠸㏆᥋ཎᏊ㛫ࡢ㉁㔞ᕪ࡛࠶ࡿࡓࡵࠊ᱁Ꮚ⇕ఏᑟ⋡࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ
>@ <-:X/)DQJDQG<;X3UHGLFWLQJLQWHUIDFLDOWKHUPDOUHVLVWDQFHE\PDFKLQHOHDUQLQJQSM&RPSXW0DWHU
 
>@ ;*XDQG&<=KDR7KHUPDOFRQGXFWLYLW\RIVLQJOHOD\HU0R6 í[ 6H[DOOR\VIURPPROHFXODUG\QDPLFVVLPXODWLRQVZLWKDPDFKLQHOHDUQLQJEDVHGLQWHUDWRPLFSRWHQWLDO&RPSXW0DWHU6FL  [3] P. G. Klemens : Proc. Phys. Soc., London, Sect. A 68, 1113 (1955).



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>@  Pang, J. H.; Wang, B.; Watanabe, K.; Takita, R.; Chiba, S. Helv. Chim. Acta 2021, 104, e2100120.
>@  Fujiyama, K.; Kato, N.; Re, S.; Kinugasa, K.; Watanabe,K.; Takita, R.; Nogawa, T.;Hino, T.;Osada, H.;
Sugita, Y.;Takahashi, S.; Nagano, S. Angew. Chem. Int. Ed. 2021, 60, 22401-22410.
>@  Yamashita,K.; Hirokawa, R.; Ichikawa, M.; Hisanaga, T.;Nagao, Y.;Takita, R.; Watanabe, K.; Kawato, Y.;
Hamashima, Y. J. Am. Chem. Soc. 2022, 144, 3913-3924.
>@  Mino, T.; Yamaoka, T.; Watanabe, K.; Masuda, C.; Kasano, S.; Yoshida, Y.; Takita, R.; Kasashima, Y.;
Sakamoto, M. J. Org. Chem. 2022, 87, in press. (DOI: 10.1021/acs.joc.2c00588)- 334 -

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 500 ns  MD Äµ)! 5 kx
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(Þ32 5 k 3 k base flipping3  %12'(;8/7<&*.+$I 500 ns aT6 (Þ 35

 5 kI." base flipping Iß  % MetaD %E ($Þ35 baseflipping I MÆ Þ32N.Ë  base flipping IG4T6 ('"MÆ ßÞPLs ¸qºV base flipping )ÇÊ'¼)&Þbase flippingVÎR PLs \eË (ÎRÇ) ( <R©ÎR¹d'ÆÈG¹d^N)]! ¯# ß

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ࡓሙྜࡢẼᾮ⏺㠃㏆ഐ࡟࠾ࡅࡿ $O2[ 㓄఩ᵓ㐀ศᕸࡢኚ໬ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

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3RODUL]DEOH LRQ PRGHO㸦3,0㸧ࡣྛ✀࢖࢜ࣥ㛫࡟ാࡃศᴟ࣮࣓ࣔࣥࢺ ȝ ࢆศᴟ⋡ࣃ࣓࣮ࣛࢱ Į ࡜㟁ሙ ( ࡢ✚࡟ࡼࡗ࡚⾲ࡋࡓࡶࡢ࡛࠶ࡿࠋ┦஫స⏝࢚ࢿࣝࢠ࣮ࡣ௨ୗࡢ㛵ᩘࢆ⏝࠸࡚ホ౯ࡋࡓࠋ
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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ࡍࠋ➨  㡯࠿ࡽ➨  㡯ࡲ࡛ࡢ┦஫స⏝ࣃ࣓࣮ࣛࢱࡣ㸪➨୍ཎ⌮ 0' ィ⟬࠿ࡽᚓࡽࢀࡿྛ࢖࢜ࣥࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜ຊࢆ෌⌧ࡍࡿࡼ࠺࡟Ỵᐃࡉࢀࡓࡶࡢ࡛࠶ࡿࠋᮏ◊✲࡛ࡣᩥ⊩  ࡟グ㍕ࡢࣃ࣓࣮ࣛࢱࢭࢵࢺࢆ฼⏝ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋィ⟬ᡭ㡰࡟ࡘ࠸࡚ࡣ㸪ࡲࡎ  ୓ಶ⛬ᗘࡢཎᏊࢆࣛࣥࢲ࣒㓄⨨ࡋࡓ❧᪉యࢭࣝࡢ୍㍈ୖୗ࡟┿✵┦ࢆ㓄⨨ࡋࡓึᮇᵓ㐀ࢆసࡾ㸪ศᴟ

- 342 -

ຠᯝࢆྵࡲ࡞࠸ຊሙ㸦5LJLG,RQ0RGHO5,0㸧㸪ࡑࡢᚋ 3,0 ࡟ࡼࡿ 0' ィ⟬ࢆᐇ⾜ࡋࡓࠋࡇࢀࢆ⾲㠃ᵓ㐀ࣔࢹࣝ࡜࿧⛠ࡍࡿࠋ୍᪉ࠊ┿✵┦ࢆᣢࡓ࡞࠸❧᪉యࢭࣝ࡟ྠᩘࡢཎᏊࢆࣛࣥࢲ࣒㓄⨨ࡋࡓሙྜ࡟ࡘ࠸࡚ࡶ㸪ྠᵝࡢᡭ㡰࡛ 0' ィ⟬ࢆᐇ⾜ࡋࡓࠋࡇࢀࢆࣂࣝࢡᵓ㐀ࣔࢹࣝ࡜࿧⛠ࡍࡿࠋ௨ୖ࡛ࡣ 3,0 㛤Ⓨ⪅࡛࠶ࡿ▼஭ⰋᶞẶ㸦රᗜ┴❧኱Ꮫ㸧ࡀ㛤Ⓨࡋࡓィ⟬ࢥ࣮ࢻࢆ౑⏝ࡋ㸪࡝ࡕࡽࡶ 197 ࢔ࣥࢧࣥࣈࣝ࡟࡚ィ⟬ࢆᐇ⾜ࡋࡓࠋࢭࣝෆ
ࡢ඲࢚ࢿࣝࢠ࣮㸦ࣁ࣑ࣝࢺࢽ࢔ࣥ㸧ࡀ࡯ࡰ୍ᐃ್࡟཰᮰ࡋࡓᚋ㸪ྛᵓ㐀ࣔࢹࣝࡢ඲య࡟࠾ࡅࡿ 2$O2 ࡢ⤖ྜゅศᕸࢆゎᯒࡋ㸪࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ T ࢆ⏝࠸ࡓゎᯒ  ࡟ࡼࡗ࡚ $O2[㸦[㸧㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸࡢホ౯ࢆ⾜࠺࡜࡜ࡶ࡟㸪$O2&D2 ⤌ᡂẚ࡟ࡼࡿ㐪࠸ࢆ⣔⤫ⓗ࡟ㄪᰝࡋࡓࠋ

◊✲ᡂᯝࡲࡎ㸪$O2&D2 ࣔࣝ⤌ᡂẚࡀ✀ࠎ␗࡞ࡿ $O2&D2 ⣔⼥య࡟ࡘ࠸࡚㸪. ࡟࡚ᖹ⾮໬ࡉࡏࡓࣂࣝࢡ࠾ࡼࡧ⾲㠃ᵓ㐀ࣔࢹࣝ࡟࠾ࡅࡿ
$O2[ 㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸࢆᅗ  ࡟♧ࡍ㸦ࣂࣝࢡ㸸◚⥺ࠊ⾲㠃㸸ᐇ⥺㸧ࠋࣂࣝࢡᵓ㐀࡟ࡘ࠸࡚ࡣ $O2 ⃰ᗘࡢቑຍ࡜࡜ࡶ࡟ $O2 ࡢᏑᅾ⋡ࡀῶᑡࡋ $O2$O2 ࡢᏑᅾ⋡ࡀቑຍࡍࡿഴྥࡀㄆࡵࡽࢀࡓࠋ୍᪉㸪࠸ࡎࢀࡢ⤌ᡂ࡛ࡶ⾲㠃ࢆᣢࡘ⣔࡛ࡣࣂࣝࢡ⣔ࡼࡾࡶ $O2 ࡢᏑᅾ⋡ࡀ኱ࡁࡃ㸪$O2$O2 ࡢᏑᅾ⋡ࡣᑠࡉ࠸ഴྥࡀ♧၀ࡉࢀࡓࠋࡓࡔࡋ㸪$O2⃰ᗘࡀప࠸⤌ᡂ࡛ࡣୖグࡢഴྥࡣ㢧ⴭࡔࡀ㸪$O2 ⃰ᗘࡢቑຍ࡜࡜ࡶ
࡟⾲㠃࡜ࣂࣝࢡ࡛ࡢ $O2[ 㓄఩ᵓ㐀ศᕸࡢ㐪࠸ࡣᑠࡉࡃ࡞ࡗࡓࠋ

ᅗ 1. $O2&D2 ⣔⼥యࡢ⾲㠃࠾ࡼࡧࣂࣝࢡᵓ㐀ࣔࢹࣝ࡟࠾ࡅࡿ $O2[㓄఩ᵓ㐀ࡢᏑᅾ⋡ศᕸࠋࡲࡓ㸪$O2&D2  ࡢ⤌ᡂ࡟ࡘ࠸࡚⾲㠃࠾ࡼࡧࣂࣝࢡᵓ㐀ࣔࢹࣝ࡟ྵࡲࢀࡿ $O2$O ⤖ྜゅศᕸࢆᅗ  ࡟♧ࡍࠋ⾲㠃ࢆྵࡴ⣔ࡢ᪉ࡀࣂࣝࢡ⣔ࡼࡾࡶ ș rࡢᏑᅾ⋡ࡣᑡ࡞ࡃ ș rࡢᏑᅾ⋡ࡀ㧗࠸ࠋࡇࢀࡣ㸪⾲㠃ࢆྵࡴ⣔࡛ࡣ $O2 ṇᅄ㠃యࡀ㡬Ⅼ࡛㓟⣲࢖࢜ࣥࢆඹ᭷
ࡋ࡚㐃⤖ࡋྜ࠺ᵓ㐀ࡀඃඛⓗ࡟ᙧᡂࡉࢀࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ
௨ୖࡢ⤖ᯝ࠿ࡽ㸪$O2&D2 ⣔⼥య࡟࠾࠸࡚ࡣ⾲㠃㸦Ẽᾮ⏺㠃㸧ࢆᑟධࡍࡿ࡜㸪⾲㠃㏆ഐ࡛ࡣ $O2 㓄఩ᵓ㐀ࢆඃඛⓗ࡟ᙧᡂࡍࡿᶵᵓ࡟
ࡼࡿ⾲㠃⦆࿴ࡀ㸪$O2 ⃰ᗘࡀప࠸⤌ᡂ࡯࡝㢧ⴭ࡟⏕ࡌࡿ࡜᥎ᐹࡉࢀ
ࡿࠋ≉࡟ $O2 ⃰ᗘࡀప࠸⤌ᡂ࡛ࡣ $O2 ྠኈࡀ㓟⣲࢖࢜ࣥࢆඹ᭷ࡋ

ᅗ 2. $O2&D2 ⣔⼥యࡢ⾲㠃࠾ࡼࡧࣂࣝࢡᵓ㐀ࣔࢹࣝ࡟࠾ࡅࡿ $O2$O ⤖ྜゅศᕸࠋ $O2&D2 

࡚஫࠸࡟㐃⤖ࡍࡿࡇ࡜࡟ࡼࡗ࡚ᯫᶫ㓟⣲࢖࢜ࣥࡀඃඛⓗ࡟ᙧᡂࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ
௒ᚋࡣ㸪ୖグ࡛ぢฟࡋࡓ⾲㠃⦆࿴࡟క࠺≉␗࡞࢖࢜ࣥ㓄఩ᵓ㐀ࡢᙧᡂࡀ⾲㠃ᙇຊ࡟ཬࡰࡍᙳ㡪ࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿࡓࡵ࡟ᵓ㐀ᙧᡂ࢚ࢿࣝࢠ࣮ࡢホ౯ࢆ㐍ࡵࡿணᐃ࡛࠶ࡿࠋࡉࡽ࡟㸪➨  ᡂศ࡜ࡋ࡚༢⊂࡛ᯫᶫ㓟⣲࢖࢜ࣥࢆᙧᡂࡍࡿ 6L2 ࢆῧຍࡋࡓሙྜࡢ⾲㠃⦆࿴࡟ཬࡰࡍᙳ㡪ࢆㄪᰝࡍࡿணᐃ࡛࠶ࡿࠋ

Ⓨ⾲㸪ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ㸦ࡓࡔࡋ㸪ᖺᗘෆ࡟ㄽᩥᢞ✏ࢆィ⏬㸧ཧ⪃ᩥ⊩ 9 3(O\XWLQ%60LWLQ<6$QLVLPRY ,]Y 9\VVK8FKHEQ=DYHG6HU7VYHWQ0HWDOOXUJ1R S   㕥ᮌ㈼⣖㸪⡿㇂ᐋဢ㸪ᱵဏ๎ṇᮦᩱ࡜ࣉࣟࢭࢫ㸪9RO S   < ,VKLL06DODQQH7&KDUSHQWLHU.6KLUDNL..DVDKDUD12KWRUL3K\V&KHP&9ROS   -5(UULQJWRQ3*'HEHQHGHWWL 1DWXUH /RQGRQ  9ROS  - 343 -

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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1

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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♧ࡍࠋ㸦ᅗ㸯㸧᥋╔ᶵᵓゎ᫂ࡢࡓࡵ࡟ࠊ
ࡇࢀࡲ࡛࡟⤖ᬗゎᯒ ᩥ⊩  ࠊ⇕ኚᛶᐇ㦂 ᩥ⊩  ࠊ$)0 ࡟ࡼࡿ᥋╔ຊࡢ┤᥋ほᐹ ᩥ⊩  ࠊ4&0' ࡟ࡼࡿ᥋╔᫬ࡢ⭷ཌᐃ ᢞ✏‽ഛ୰ ࢆ⾜ࡗࡓࠋࡇࢀࡽࡢᐇ
㦂ࡣࠊ$WD$ ࡢ᥋╔࡟㛵ࡍࡿ⌮ゎࢆ῝ࡵࡓࡀࠊศᏊ࡛ࣞ࣋ࣝ㉳ࡇࡿ┦஫స⏝ࡢヲ⣽ࠊ౛࠼ࡤࠊᮦᩱ⾲㠃࡟᥋╔ࡍࡿ㝿ࡢࢱ
ࣥࣃࢡ㉁ศᏊࡢ㓄ྥࡸ᥋╔࡟㛵୚ࡍࡿ࢔࣑ࣀ㓟➼ࡢ᝟ሗࢆᥦ౪ࡍࡿ࡟⮳ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲ࡣࠊ᥋╔ࡢཎᏊ௕‫ڭ‬

1KHDG म஘‫ر‬ऩ౫મ਀એपமାਙ॑ંघ

ⓗᥥ⏬ࢆ┠ⓗ࡜ࡋ࡚ࠊ1KHDG ࢻ࣓࢖ࣥࠊᮦᩱ⾲㠃ࠊỈࢆྵࡴ⣔ࡢ඲ཎᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࠋ
୍᫖ᖺ㸦௧࿴㸰ᖺᗘ㸧ࡢ᪋タ฼⏝(B)࡛ࡣࠊNhead ࡀ␯Ỉᛶࡢ࣏ࣜࢫࢳࣞࣥ㸦PS㸧⾲㠃࡜ぶỈᛶࡢ SiO2 ⾲㠃㸦ࢩࣜ࢝⾲㠃㸧࡟᥋╔ࡍࡿ㝿ࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆ⇕ຊᏛ✚ศἲ࡟ࡼࡾ⟬ฟࡋࠊ᥋╔᫬ࡢ Nhead ࡢ㓄ྥࡀ⦪㸦Nhead ࡢ⧄⥔㍈ࡀᮦᩱ⾲㠃࡟ᆶ┤㸧࡛ࡶᶓ㸦⧄⥔㍈ࡀᮦᩱ⾲㠃࡟ᖹ⾜㸧࡛ࡶ᥋╔࢚ࢿࣝࢠ࣮࡟࠶ࡲࡾᕪ
ࡀ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࠊNhead ࡣࠊᮦᩱ⾲㠃࡟ᑐࡋ࡚Ỵࡲࡗࡓ㓄ྥ࡛᥋╔ࡋ࡞࠸ྍ⬟ᛶࡀᥦ㉳ࡉࢀࡓࠋࡑࡇ࡛ࠊ௧࿴ 3 ᖺᗘ࡛ࡣࠊᮦᩱ⾲㠃࡟ᑐࡍࡿ Nhead ࡢึᮇ㓄ྥࢆ⦪࣭ᶓ௨እࡢᵝࠎ࡞㓄ྥ࡟ኚ࠼࡚ࠊNheadࡢᇶ┙࡬ࡢ᥋╔ࢆࢩ࣑࣮ࣗࣞࢺࡋࠊ᥋╔࡟㝿ࡋ࡚ 1KHDG ࡀዲࡴ㓄ྥࡀ࠶ࡿ࠿࡝࠺࠿ࢆㄪ࡭ࡓࠋ
ࡲࡓࠊࡇࢀࡲ࡛ࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊ
1KHDG ࡢ  ศᏊࢆ౑ࡗ࡚ࡁࡓࡀࠊLQYLYR ࡛ 1KHDG
ࡣࣂࢡࢸࣜ࢔ࡢ⣽⬊⾲ᒙ࡟ᐦ࡟⏕࠼࡚࠸ࡿ$WD$ ࣇ࢓࢖ࣂ࣮ࡢඛ➃࡟఩⨨ࡍࡿࡓࡵࠊศᏊ㞟ᅋ࡜࡞ࡗࡓ࡜ࡁ࡟ 1KHDG ᮏ᮶ࡢ᥋╔ຊࢆⓎ᥹ࡉࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋ㸦ᅗ㸰ཧ↷㸧ࡑࡇ࡛ࠊศᏊ
㞟ᅋ࡜ࡋ࡚ࡢ 1KHDG ࡢ᥋╔ᣲື࡟ࡘ࠸࡚ࡶ 0'ィ⟬ࢆ౑࠸ㄪ࡭ࡓࠋ

௕‫ڮ‬ƌƑŃƙƌƙƒ द 1KHDG मী৕ૐ੮धखथமାपঢ়ॎॊ

㸺ཧ⪃ᩥ⊩㸼
㸯㸬Koiwai K, Hartmann MD, Linke D, Lupas AN, Hori K, J Biol Chem. 291(8), 3705-24(2016).

- 344 -

㸰㸬Yoshimoto S, Nakatani H, Iwasaki K, Hori K, Sci Rep. 6:28020 (2016).
㸱㸬Ishii S, Yoshimoto S, Hori K, J Colloid Interface Sci. 606, 628-634 (2022)

2◊✲᪉ἲࠊィ⟬᪉ἲ
Nhead ࡢᮦᩱ⾲㠃࡬ࡢ᥋╔㓄ྥࡢ᥈⣴࡛ࡣࠊ࣏ࣜࢫࢳࣞࣥ㸦PS㸧ᇶ┙࠿ࡽ 10ύࡢ㊥㞳࡟ᵝࠎ࡞㓄ྥ࡜ࡋࡓ

Nhead ࢆ㓄⨨ࡋࠊ301Kࠊ1atm ࡟࠾࠸࡚ 50ns ࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊNhead ࡀ࡝ࡢࡼ࠺࡞㓄ྥ࡛ PSᇶ┙࡟᥋╔ࡍࡿ࠿ࢆㄪ࡭ࡿ࡜࡜ࡶ࡟ࠊᇶ┙࡜ࡢ᥋╔࡟㛵ࢃࡿ࢔࣑ࣀ㓟ࡢྠᐃࢆヨࡳࡓࠋNhead ࡢ㓄ྥࡣࠊᇶ┙࡟ᑐࡍࡿ⧄⥔㍈ࡢഴࡁ㸦R2㸧࡜⧄⥔㍈ࡲࢃࡾࡢᅇ㌿㸦R1ࠊR1㸻0r࡛ࡣ࢚࢘ࢵࢺᐇ㦂࡛᥋╔࡟㛵ࢃࡿࡇ࡜࡜♧၀ࡉࢀࡓ Nhead ࡢ࣮ࣝࣉᵓ㐀ࡀᇶ┙࡟᭱ࡶ㏆ࡃ࡞ࡿ㸧ࡢ㸰ࡘࡢゅᗘࣃ࣓࣮ࣛࢱ
࣮ࢆࡑࢀࡒࢀ 30rࡎࡘኚ࠼࡞ࡀࡽ⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾィ 17 ಶࡢ㓄ྥ࡜ࡋࡓࠋ
㸦ᅗ㸱ཧ↷㸧
⏝࠸ࡿ PS ᇶ┙ࡣࠊᇶ┙ࡢཌࡉࢆ 30ύ࡜ࡍࡿࡢ࡟ᚲせ࡞ᮏᩘࡢ㔜ྜᗘ 100 ࡢ࢔ࢱࢡࢳࢵࢡ PS 㙐㸦ศᏊ㔞 5104㸧ࢆ 600K ࡢ┿✵୰࡛⁐ゎࡉࡏ࡚㸯ࡘࡢᾮ⁲࡜ࡋࡓᚋࠊ
z ㍈᪉ྥࡢୖୗ࠿ࡽⅣ⣲ཎᏊ࠿ࡽᡂࡿ௬᝿
ᖹ㠃ࢆᢲࡋᙜ࡚࡚ 1500atm ࡛ᅽᘏࡋࠊࡑࡢᚋࠊ ᗘࢆࡺࡗࡃࡾ࡜ 301K ࡲ࡛ୗࡆࡿࡇ
௕‫گ‬࡜࡟ࡼࡾసᡂࡋࡓࠋ

1KHDG भ 36 ੦ೕपৌघॊੂ਋ଦ਱

ศᏊ㞟ᅋ࡜ࡋ࡚ࡢ Nhead ࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊPS ᇶ┙࠿ࡽ 10ύࡢ㊥㞳࡟ࠊ9 ಶࡢ Nhead ศᏊࢆ⦪㸦⧄⥔㍈ࡀᮦᩱ⾲㠃࡟ᆶ┤㸧ࡲࡓࡣᶓ㸦⧄⥔㍈ࡀᮦᩱ⾲㠃࡟ᖹ⾜㸧ࡢ㓄ྥ࡛භ᪉᱁Ꮚ≧࡟➼㛫㝸࡛㓄⨨ࡋࠊ⧄⥔㍈ࡲࢃࡾࡢᅇ㌿ゅ㸦㸮rࠊ㸱㸮rࠊ㸴㸮rࠊ㸷㸮㸧࡜㞄ࡢศᏊ࡜ࡢ㛫ࡢ㊥㞳㸦㸱ύࠊ㸳ύࠊ㸯㸮ύ㸧ࢆኚ࠼࡞ࡀࡽ 10ns ࡢ MD ィ⟬ࢆ⾜ࡗࡓࠋ㸦ึᮇࣔࢹࣝࡣᅗ㸳ࢆཧ↷㸧MD ィ⟬ࡣࠊ඲࡚ࣉࣟࢢ࣒ࣛ GROMACS 2020.6 ࢆ⏝࠸࡚༢⢭ᗘ࡛⾜ࡗࡓࠋຊሙ࡟ࡣࠊCHARMM36m ࢆ⏝࠸ࡓࠋᇶ┙࡜ Nhead 㛫ࡢᖹᆒຊ㸦PMF㸧ࡢ⟬ฟࡣࠊ୧⪅ࡢ㛫ࡢ㊥㞳㸦㊥㞳 0 ࢆ୧⪅ࡢ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࡀ᭱ప࡜࡞ࡿⅬ࡜ᐃ⩏㸧ࢆ㸫1 nm ࠿ࡽ 10 nm
ࡲ࡛ 0.05 nm 㛫㝸࡛ኚ࠼࡚ࠊࡑࢀࡒࢀࡢ㊥㞳࡟࠾࠸࡚ 10 ns ࡢ NPT ࢔ࣥࢧࣥࣈ࡛ࣝࡢ MD ィ⟬⾜࠸ࠊ
2ps ẖ࡟ Nhead ࡟࠿࠿ࡿຊࢆࢧࣥࣉࣜࣥࢢࡋ࡚ࠊ
ࡇࢀࢆᖹᆒࡍࡿࡇ࡜࡟ࡼࡾ⾜ࡗࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬ࡣࠊࡇ࠺ࡋ࡚ᚓࡽࢀࡓ PMF ࢆ Nhead㸫PS ᇶ┙㛫ࡢ㊥㞳࡟ἢࡗ࡚✚ศࡍࡿ࠸ࢃࡺࡿ⇕ຊᏛ✚ศἲ࡟ࡼࡾ⾜ࡗࡓࠋ3◊✲ᡂᯝ㸦㸯㸧ᮦᩱ⾲㠃࡬ࡢ᥋╔㓄ྥࡢ᥈⣴௕‫ڰ‬- 345 -

1KHDG भமାଦ਱

ᅗ㸲࡟ Nhead ࡢึᮇ㓄ྥࢆኚ࠼࡚࠾ࡇ࡞ࡗࡓ

਀‫ڭ‬᥋╔ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࡢ୍㒊ࢆ♧ࡍࠋࡇமାपঢ়ॎॊ॔঑ঀ෷    ౦હऌभ॔঑ঀ෷म 1KHDG भ਀એঝ‫ش‬উपँॊ    ࡢᅗ࠿ࡽࡶࢃ࠿ࡿࡀࠊNhead ࡢ᥋╔๓ࡢ㓄ྥ࡜᥋╔ᚋࡢ㓄ྥࡣࠊ୍⮴ࡍࡿሙྜࡶ࠶ࢀࡤ␗
࡞ࡿሙྜࡶ࠶ࡿࠋ᥋╔ᚋࡢ㓄ྥ࡜ࡋ࡚ࡣࠊ⧄
⥔㍈ࡀᮦᩱ⾲㠃࡟ᑐࡋ࡚ᩳࡵ࡜࡞ࡗ࡚࠸ࡿࡶ
ࡢࡀከ࠸ࡀࠊ⧄⥔㍈ࡢഴࡁࡸ⧄⥔㍈ࡲࢃࡾࡢᅇ㌿ࡢゅᗘࡣᵝࠎ࡛࠶ࡾࠊ᥋╔ᚋࡢ㓄ྥ࡜ࡋ࡚≉࡟ዲࡲࢀࡿ㓄ྥࡀ࠶ࡿ࡜ࡲ࡛ࡣゝ࠼࡞࠸⤖ᯝ࡛࠶ࡗࡓࠋࡲࡓࠊ⾲㸯࡟ࠊ᥋╔ᚋ࡟ PSᇶ┙࡜┦஫స⏝ࡍࡿ࢔࣑ࣀ㓟ࢆ♧ࡍࠋⰍࡢࡘ
࠸࡚࠸ࡿ࢔࣑ࣀ㓟ࡣࠊNhead ⾲㠃ࡢ࣮ࣝࣉᵓ
㐀࡟ྵࡲࢀࡿ࢔࣑ࣀ㓟࡛࠶ࡿࠋ࢚࢘ࢵࢺࡢᐇ㦂࡛ࡣࠊࡇࢀࡽࡢ⾲㠃ࡢ࣮ࣝࣉࢆḞኻࡉࡏࡿ࡜ Nhead ࡢ᥋╔ຊࡀపୗࡍࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠾ࡾࠊ௒ᅇࡢィ⟬⤖ᯝࢆᨭᣢࡍࡿᐇ㦂⤖ᯝ࡜ゝ࠼ࡿࠋ㸦㸰㸧ศᏊ㞟ᅋ࡜ࡋ࡚ࡢ Nhead ࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩࣙࣥ
ᅗ㸳࡟ PS ᇶ┙࠿ࡽ 10ύ㞳ࡋࠊࡲࡓ㞄᥋ࡍࡿ Nhead ศᏊ㛫ࡢ㊥㞳ࢆ 10ύ࡜ࡋࡓࠕ⦪ࠖ㓄ྥࡢ Nhead ศᏊ㞟ᅋࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࢆ♧ࡍࠋ10ns ࡢ MD ᚋ࡟ PS ᇶ┙࡟᥋╔ࡋࡓࡢࡣࠊ⊂❧࡞ 9 ศᏊࡢ࠺ࡕ 3ศᏊ࡛࠶ࡗࡓࠋྠࡌ⦪㓄ྥࡢ Nhead 1 ศᏊࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊ10ns ௨ෆ࡟࡯ࡰ☜ᐇ࡟ PS ᇶ┙࡟᥋╔ࡍࡿࡢ࡛ࠊศᏊࡢ㞟ᅋ໬࡟ࡼࡿ Nhead ࡢ᥋╔ຊࡢపୗࡀ♧၀ࡉࢀࡓࠋࡇࡢࡇ࡜ࢆ☜ㄆࡍࡿࡓࡵ࡟ศᏊ㞟ᅋࢆᵓᡂࡍࡿ㸯ࡘ㸯ࡘࡢศᏊࡢ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡼ࠺࡜ࡋࡓࡀࠊ⊂❧࡞ 9 ศᏊࡢ࠺ࡕ 1 ศᏊࢆᖹᆒ
ຊࡢᐃࡢࡓࡵ࡟ᅛᐃࡋࠊṧࡾ 8 ศᏊࡣ⮬⏤࡟ࡋ࡚ࠊᅛᐃࡋࡓศᏊ࡟ാࡃຊࢆࢧࣥࣉࣜࣥࢢࡋࡓ࡜ࡇࢁࠊࡲ

ࢃࡾࡢศᏊࡢᙳ㡪࡛ຊࡀᏳᐃࡏ
ࡎࠊ⇕ຊᏛ✚ศἲ࡟౑࠼࡯࡝ࡢ
⢭ᗘ࡛ᖹᆒຊࢆồࡵࡿࡇ࡜ࡣ࡛
ࡁ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊ௚ࡢศᏊ
ࢆึᮇᵓ㐀࡟ᅛᐃࡋ࡚ࠊὀ┠ࡍࡿศᏊࡢࡳ PS ᇶ┙࡜ࡢ㊥㞳ࢆኚ࠼࡞ࡀࡽᖹᆒຊࢆィ⟬ࡋࠊ⇕ຊᏛ✚ศἲ࡛᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚ࡳࡓࠋ
㸦ᅗ㸴㸧ᚓࡽ
ࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ࡣ 32 ࠿ࡽ
99 㹩J/mol ࡲ࡛኱ࡁࡃࡤࡽࡘ࠸
࡚࠾ࡾࠊᖹᆒ 64 kJ/molࠊᶆ‽೫ᕪ 25 kJ/mol ࡛࠶ࡗࡓࠋࡋ࠿ࡋ࡞
ࡀࡽࠊࡇࡢࡼ࠺࡟ࡋ࡚᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓ࡝ࡢศᏊ
ࡶࠊࡲࢃࡾࡢศᏊࡣ඲ࡃྠࡌ

௕‫ڱ‬

1KHDG ী৕ૐ੮पेॊமା३঑গঞ‫ش‬३ঙথ- 346 -

ึᮇᵓ㐀࡟ᅛᐃࡉࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊࡇࡢࡤ
ࡽࡘࡁࡣࠊNhead 㛫ࡢ┦஫స⏝࡟ࡼࡿࡶࡢ࡛
ࡣ࡞ࡃࠊศᏊࡢ఩⨨ࡢ㐪࠸࡟⏤᮶ࡍࡿࡶࡢࠊ
ࡍ࡞ࢃࡕࠊศᏊࡢ⨨࠿ࢀࡓ఩⨨࡟࠾ࡅࡿ PS ᇶ┙ࡢᵓ㐀ࡢ㐪࠸࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡍ
࡞ࢃࡕࠊPS ᇶ┙ࡢ⾲㠃࡟ࡣ Nhead ࡀᙉࡃ᥋╔ࡍࡿሙᡤ࡜ᙅࡃ᥋╔ࡍࡿሙᡤࡀ࠶ࡾࠊ1 ศᏊ࡛ࡢ᥋╔ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊศᏊࡣᙉࡃ᥋
╔ࡍࡿሙᡤ࡟⛣ື࡛ࡁࡿࡓࡵᙉࡃ᥋╔ࡍࡿࡀࠊศᏊ㞟ᅋ࡟࡞ࡿ࡜㞄᥋ࡍࡿศᏊࡀ㑧㨱࡛ᙉࡃ᥋╔࡛ࡁࡿሙᡤ࡟⛣ື࡛ࡁࡎࠊ᥋╔ຊࡢపୗࡀ㉳ࡇࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡇ࡜࠿ࡽࠊ
ࣂࢡࢸࣜ࢔ࡢ⣽⬊⾲ᒙ࡛᥋╔ࢱࣥࣃࢡ㉁ࡀⓎ௕‫ڲ‬⌧ࡍࡿሙྜࠊศᏊᩘࡀቑ࠼࡚㠃ᐦᗘࡀୖࡀࡿ
࡜ࠊศᏊ㸯ࡘ࠶ࡓࡾࡢᖹᆒ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ ଻भী৕ૐ੮রद  ଻॑ੂ਋ଡୗपಕ৒
खञधऌभ‫ڭ‬ী৕भமାঽ૓ग़ॿঝॠ‫ش‬ࡀపୗࡍࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡿࠋࡑࡇ࡛ࠊࡇࡢ⌧㇟ࡢ᳨ドࡢࡓࡵ࡟ࠊ⣽⬊⾲ᒙ࡛ࡢ᥋╔ࢱࣥࣃࢡ㉁ࡢⓎ⌧㔞ࢆᐇ㦂ⓗ࡟ኚ࠼࡚ࠊศᏊᙜࡓࡾࡢ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࡀ࡝࠺ኚࢃࡿ࠿ࢆᐇ㦂ⓗ࡟ࡋࡽ࡭ࡿணᐃ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬1. J. Sasahara, A. Suzuki, K. Fujimoto, S. Okazaki,K. Hori,ࠕMolecular dynamics simulation of adhesion
process of a highly adhesive protein AtaA̓s N-terminal domain in waterࠖPacifichem 2021 (2021.12.19)‫ۻ‬2. ➲ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᇼ ඞᩄࠕศᏊືຊᏛⓗゎᯒ࡟ࡼࡿ㧗᥋╔ࢱࣥࣃࢡ㉁ࡢỈ୰᥋╔㓄ྥ᥎ᐃࠖ➨ 73 ᅇ ᪥ᮏ⏕≀ᕤᏛ఍኱఍ (2021.10.29)‫ۻ‬3. ➲ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᇼ ඞᩄࠕᮦᩱ⾲㠃ࡢ㐪࠸࡟ᛂࡌࡓ㧗᥋╔ࢱࣥࣃࢡ㉁ࡢ᥋╔ᣲືኚ໬ࡢ MD ィ⟬࡟ࡼࡿゎᯒࠖ᪥ᮏ໬Ꮫ఍⛅Ꮨ஦ᴗ ➨ 11 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ (2021.10.19)‫ۻ‬4. J. Sasahara, A. Suzuki, K. Fujimoto, K. Hori,ࠕAnalysis of Interaction of a Highly Adhesive Protein toMaterial Surfaces by Molecular Dynamics Calculationࠖ➨ 15 ᅇࣂ࢖࢜㛵㐃໬Ꮫࢩ࣏ࣥࢪ࣒࢘ (2021.9.8)‫ۻ‬5. ➲ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᇼ ඞᩄࠕMD ィ⟬࡟ࡼࡿ㧗᥋╔ࢱࣥࣃࢡ㉁ࡢᮦᩱ⾲㠃࡜ࡢ┦஫స⏝ゎᯒࠖ➨ 8 ᅇࣂ࢖࢜㛵㐃ࢩ࣏ࣥࢪ࣒࢘ⱝᡭࣇ࢛࣮࣒ࣛ (2021.9.3)‫ۻ‬6. ➲ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᇼ ඞᩄࠕMD ィ⟬ࢆ⏝࠸ࡓ␯Ỉ࣭ぶỈᛶ⾲㠃࡟ᑐࡍࡿ㧗᥋╔ࢱࣥࣃ
ࢡ㉁ࡢ᥋╔ᣲືኚ໬ゎᯒࠖ᪥ᮏ⏕≀ᕤᏛ఍ 2021 ᖺᗘ୰㒊ᨭ㒊౛఍ (2021.8.6)‫ۻ‬7. ➲ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᇼ ඞᩄࠕศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔ࢱࣥࣃࢡ㉁ࡢᮦᩱ⾲㠃࡬ࡢ᥋╔㐣⛬ゎᯒࠖ⏕≀ᕤᏛⱝᡭ◊✲⪅ࡢ㞟࠸ (ⱝᡭ఍)

5ኟࡢ࢜ࣥࣛ࢖ࣥࢭ࣑ࢼ࣮2021 (2021.7.17)

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ඹྠ◊✲⪅ࡢ➲ཎẶࡣࠊ2021 ᖺᗘ࡟༤ኈㄢ⛬࡟㐍Ꮫࡋ࡚࠾ࡾࠊ࢙࢘ࢵࢺࡢᐇ㦂࡜ేࡏ࡚ᮏ◊✲ࡢᡂᯝࢆ
2022 ᖺ୰ࡢᢞ✏ࡍࡿணᐃ࡛࠶ࡿࠋ

- 347 -

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Simulation study of diffusion coefficient of bio-macromolecule undervarious thermodynamic state %

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- 349 -

ᶵᲔᏛ⩦࢔ࣉ࣮ࣟࢳ࡟ࡼࡿ㠀ᑐ⛠ࢥ࣐ศᏊࡢ
࣮ࣞࢨ࣮ㄏ㉳㸱ḟඖᩚิࡢไᚚᶵᵓࡢண
Machine-learning approach for predicting control mechanisms of laserinduced three-dimensional alignment of asymmetric-top molecules‫ۑ‬኱ᵳ ᖾ⩏ࠊ㞴Ἴ ▱ኴ㑻ࠊ▼஭ ⋹㡢㸦ᮾ໭኱㝔⌮㸧1◊✲┠ⓗ࣮ࣞࢨ࣮ㄏ㉳ࡢศᏊ㸱ḟඖᩚิไᚚࡣ㸪ศᏊᅛᐃ⣔࡛ࡢᐃ࣭㔞Ꮚ᧯సࡢࡓࡵࡢᇶ┙ᢏ⾡࡛࠶ࡿࠋᡃࠎࡣ

㠀⥺ᙧ㸦ศᴟ㸧┦஫స⏝࡟ᑐࡍࡿ㔞Ꮚ᭱㐺ไᚚἲࢆ⏝࠸࡚㸪SO2 ศᏊ㸦ไᚚ㐩ᡂᗘࢆẚ㍑ࡍࡿࡓࡵ࡟ࡋࡤࡋࡤ
⏝࠸ࡽࢀࡿࠕᶆ‽ࠖศᏊ㸧ࡢ㸱ḟඖᩚิไᚚ࡟ᑐࡍࡿไᚚ࣮ࣞࢨ࣮ࣃࣝࢫࡢ᭱㐺ゎࢆồࡵࡓࠋࡑࡢ⤖ᯝ㸪(i)஫
࠸࡟┤஺ࡍࡿ┤⥺࣮ࣞࢨ࣮ࣃࣝࢫࡢ⤌ࡀ᭱㐺ゎ࡛࠶ࡾ㸪᭱ᑠࣃࣝࢫ࣌࢔࡛࠶ࡗ࡚ࡶ㸪(ii)஫࠸ࡢᙉᗘࢆㄪᩚࡍ
ࡿࡇ࡜࡛㸪ᛂ⏝࡟༑ศ࡞ᩚิᗘྜ࠸ࡀ㐩ᡂ࡛ࡁࡿࡇ࡜ࢆぢฟࡋࡓࠋ୍⯡ࡢ㠀ᑐ⛠ࢥ࣐ศᏊ࡟ᑐࡋ࡚ࡶ㸪ศᏊࡈ࡜࡟㐺ᙜ࡞㐜ᘏ᫬㛫࡜ᙉᗘẚࢆỴࡵࢀࡤࡼ࠸࡜ᮇᚅ࡛ࡁࡿࠋ᭱ࡶ༢⣧࠿ࡘຠᯝⓗ࡞࢔ࣉ࣮ࣟࢳࡣ㸪ࡇࡢ㸰ࡘࡢไᚚࣃ࣓࣮ࣛࢱ࡟ᑐࡋ࡚ᩚิไᚚࡢ㐩ᡂᗘࢆ⾲♧ࡍࢀࡤࡼ࠸ࠋᮏ◊✲࡛ࡣࡇࡢ㐩ᡂᗘࡢᅗࢆࠕไᚚࣛࣥ
ࢻࢫࢣ࣮ࣉᅗࠖ࡜ࡼࡪࡇ࡜࡟ࡍࡿࠋࡓࡔࡋ 12050㸻6000 Ⅼࢆ᝿ᐃࡋ࡚ࡶ㸪సᅗ࡟ࡣ⭾኱࡞ィ⟬ࡀᚲせ࡛࠶ࡾ㸪ᡃࠎࡣࡑࡢㄢ㢟ゎỴ࡟ᶵᲔᏛ⩦ࡢᛂ⏝ࢆ╔᝿ࡋࡓࠋᐇ㝿㸪2019 ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢᨭ᥼࡟ࡼ
ࡾ㸪SO2 ศᏊࢆ౑ࡗࡓᐇドィ⟬࡛᭷ຠᛶࢆ♧ࡍࡇ࡜ࡀ࡛ࡁᡂᯝࢆᏛ⾡ㄅ࡟ሗ࿌ࡋࡓ[‫ ۻ‬T. Namba, M. Yoshida,
Y. Ohtsuki, J. Chem. Phys. 153, 024120 (2020).]ࠋ2021 ᖺᗘࡣ୍⯡ࡢ㠀ᑐ⛠ࢥ࣐ศᏊ࡬ࡢᣑᙇࢆ┠ᣦࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᅇ㌿࡜ศᴟ⋡ࡢ୺㍈ࡀ୍⮴ࡍࡿ࡜௬ᐃࡍࡿ㸦ከࡃࡢศᏊ࡛ጇᙜᛶࢆ☜ㄆ῭ࡳ㸧࡜㸪㠀ᑐ⛠ࢥ࣐ศᏊࡣ㸱ࡘࡢᅇ㌿ᐃᩘ࡜㸱ࡘࡢศᴟ⋡ᡂศ࡛≉ᚩ࡙ࡅࡽࢀࡿࠋࢧ࢖ࢬࡀ኱ࡁࡃ␗࡞ࡿศᏊࢆᢅ࠺ᚲせࡀ࠶ࡿࡇ࡜࠿ࡽ㸪ࡲࡎ㸪ศᏊࣃ࣓࣮ࣛࢱࢆ↓ḟඖ໬ࡍࡿࠋᅇ㌿ᐃᩘ A ࢆ༢఩࡟࢚ࢿࣝࢠ࣮ࢆ⾲ࡍ࡜࡜ࡶ࡟᫬㛫ࢆ↓ḟඖ໬ࡍࡿࠋ
ศᴟ⋡┦஫స⏝ࡣศᏊࡢᙧ౫Ꮡᛶࡀ኱ࡁ࠸ࡓࡵ㸪‽ഛホ౯࡟ࡼࡾぢฟࡋࡓ⤒㦂ᘧ࡟ᙜ࡚ࡣࡵ࡚┦஫స⏝ࡢ኱ࡁࡉࡢᶆ‽໬ࢆ⾜ࡗࡓࠋ௨ୖࡢ↓ḟඖࣃ࣓࣮ࣛࢱ࡛⾲ࡉࢀࡓᅇ㌿Ἴ᮰ࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆ㸪ᑐ⛠ࢥ࣐ศᏊᇶᗏ㸦࢘࢕ࢢࢼ࣮ࡢᅇ㌿⾜ิ㸧࡛ᒎ㛤ࡋ᫬㛫Ⓨᒎࢆィ⟬ࡍࡿࠋไᚚ࣮ࣞࢨ࣮ࣃࣝࢫࡣ㸪஫࠸࡟┤஺ࡍࡿ㉸▷ࡢ┤⥺೫ග࣮ࣞࢨ࣮ࣃࣝࢫ࣌࢔࡛࠶ࡾ㸪㐜ᘏ᫬㛫࡜ᙉᗘẚࡢ㸰ࡘࡢࣃ࣓࣮ࣛࢱ࡛≉ᚩ࡙ࡅࡽࢀࡿࠋ
ไᚚ࣮ࣞࢨ࣮ࣃࣝࢫࡈ࡜࡟᭱኱ࡢ㸱ḟඖᩚิᗘྜ࠸ࢆ᥈⣴ࡍࡿࡇ࡜࡛㸪ࣛࣥࢻࢫࢣ࣮ࣉᅗࡢ㸯Ⅼࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋᶵᲔᏛ⩦࡟ࡣ keras ࢆ฼⏝ࡋ㸪ไᚚࣃ࣓࣮ࣛࢱ࡜ศᏊࣃ࣓࣮ࣛࢱࢆධຊ࡜ࡋࡓ␚ࡳ㎸ࡳࢽ࣮ࣗࣛ
ࣝࢿࢵࢺ࣮࣡ࢡࣔࢹࣝࢆカ⦎ࡍࡿࠋ3◊✲ᡂᯝไᚚࣛࣥࢻࢫࢣ࣮ࣉᅗࡢᵓ㐀ࡣ㸪ᅇ㌿ࡍࡿࠋࡑࡇ࡛㸪పᗘࡀ༑ศప࠸ሙྜ࡟ศᏊࡸไᚚࣃ࣓࣮ࣛࢱ࡟౫Ꮡࡋ࡚኱ࡁࡃኚ໬

ᴟ㝈ࢆ⪃࠼◊✲᪉ἲ࡟ᚑ࠸ᶵᲔᏛ⩦ࣔࢹࣝࢆカ⦎ࡋࡓࠋᅗ㸯࡟ࡣேᕤศᏊࢆ౑ࡗ࡚ SO2

ࡢไᚚࣛࣥࢻࢫࢣ࣮ࣉᅗࡢண࡟ᑐࡍࡿカ⦎ࡢ཰᮰ࡢᵝᏊࢆ♧ࡍࠋ᳨ドࢹ࣮ࢱ࡟ࡶⰋዲ࡞཰᮰ࡀぢࡽࢀࡿࠋ- 350 -

ᅗ㸯 カ⦎ࡢ཰᮰ࡢᵝᏊᅗ㸰㸦ᕥ㸧ᩘ್ィ⟬⤖ᯝ㸦ྑ㸧ᶵᲔᏛ⩦࡟ࡼࡿணカ⦎ࡉࢀࡓᶵᲔᏛ⩦ࢆ౑ࡗ࡚ᚓࡽࢀࡓ⤖ᯝࢆᅗ㸰࡟♧ࡍࠋண࡜ᐇ㝿ࡢィ⟬ࡣ㠀ᖖ࡟ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ ḟ࡟㸪୍⯡ࡢ㠀ᑐ⛠ࢥ࣐ศᏊ࡟㐺⏝ࡋࡓࠋ㸦೫㛗ࢥ࣐ࡢ㸧22 ಶࡢ㠀ᑐ⛠ࢥ࣐ศᏊ࠿ࡽ kennard-stone ࢔ࣝࢦࣜࢬ࣒࡟ࡼࡾ 11 ศᏊࢆᢳฟࡋ㸪ᐇ㝿࡟ᩚิᗘྜ࠸ࢆィ⟬ࡋࡓࠋḟ࡟㸪ࡇࡢ୰ࡢ 10 ಶࢆ౑࠸ᶵᲔᏛ⩦ࣔࢹࣝࢆカ⦎ࡋ㸪ࡑࢀࢆ౑ࡗ࡚ࣛࣥࢻࢫࢣ࣮ࣉᅗࡢண

ࢆ⾜ࡗࡓࠋࢹ࣮ࢱࡣ♧ࡉ࡞࠸ࡀ㸪カ⦎ࡣ㞴ࡋࡃ㸦ㄗᕪࡣ

SO2 ࡢ‽ഛホ౯࡜ẚ㍑ࡋ࡚ 2 ᱆ᝏ࠸㸧㸪ࢸࢫࢺࢹ࣮ࢱࡢࣛࣥࢻࢫࢣ࣮ࣉᅗࢆ෌⌧ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋࡲ
ࡓ㸪ᶵᲔᏛ⩦ࣔࢹࣝࡢᵓ㐀ࢆኚ࠼࡚ࡶᨵၿ࡛ࡁ࡞࠿ࡗࡓࠋࡑࡇ࡛タᐃࡋࡓၥ㢟ࡀ㞴ࡋࡍࡂࡿࡇ࡜ࡀཎᅉ࡛࠶
ࡿ࡜⪃࠼㸪ࣛࣥࢻࢫࢣ࣮ࣉᅗࢆ㸰್ၥ㢟࡜ࡋ࡚෌⌧ࡍࡿࡇ࡜ࢆヨࡳ࡚࠸ࡿࠋ௨ୗ࡟㸪⤖ᯝࢆࡲ࡜ࡵࡿࠋ

ᅗ㸱 㸰್ၥ㢟࡟ᑐࡍࡿカ⦎ࡢ཰᮰ࡢᵝᏊᅗ㸲㸦ᕥ㸧ᩘ್ィ⟬⤖ᯝ㸦ྑ㸧ᶵᲔᏛ⩦࡟ࡼࡿணᅗ㸱࡟ࡣ㸰್ၥ㢟࡟ᑐࡍࡿカ⦎ࡢᵝᏊࢆ♧ࡍࠋᅗ㸯࡜ࡣ␗࡞ࡾ㸪⦪㍈ࡣṇ☜ࡉࢆ♧ࡋ࡚࠾ࡾ㸪⌮᝿್ࡣ㸯࡛࠶ࡿࠋ୍ぢࡍࡿ࡜㸪カ⦎ࢹ࣮ࢱ࡜᳨ドࢹ࣮ࢱ࠸ࡎࢀࡶⰋዲ࡟཰᮰ࡋ࡚࠸ࡿࡼ࠺࡟ぢ࠼ࡿࠋࡋ࠿ࡋ㸪㸰್ศ㢮ࡢ௙᪉࠿ࡽ㸪ᩚิᗘྜ࠸ࡀ㧗࠸㡿ᇦ㸦್㸯㸧ࡣ඲యࡢ 5㸣ࡋ࠿࡞ࡃ㸪௬࡟ࡍ࡭࡚ࢮࣟ࡜⟅࠼࡚ࡶṇ⟅⋡ࡣ 95㸣
࡛࠶ࡿࠋࡍ࡞ࢃࡕ㸪ᅗ㸱࡟ぢ࠼ࡿ཰᮰್ࡢ㐪࠸ࡣ㸪ࢸࢫࢺࢹ࣮ࢱண

᫬࡟ࡣ኱ࡁ࡞ㄗᕪ࡜ࡋ࡚⾲ࢀ࡚ࡋࡲ࠺ࠋ࡞࠾㸪カ⦎ࢹ࣮ࢱࡢ್ࢆ 1/10 ࡟ࠕ㛫ᘬ࠸࡚ࠖカ⦎ࡋ㸪ṧࡾࡢࢹ࣮ࢱࢆண
ணࡍࡿၥ㢟࡟タᐃࡍࡿ࡜㸪㧗⢭ᗘ࡛ࡀ࡛ࡁࡿ㸦ᅗ㸲㸧ࠋ௨ୖ࠿ࡽ㸪୍⯡ࡢ㠀ᑐ⛠ࢥ࣐ศᏊࡢࣛࣥࢻࢫࢣ࣮ࣉᅗࢆ༑ศ࡟ண

࡛ࡁ࡞࠸ཎᅉࡣ㸪カ⦎ࢹ࣮ࢱ࡟౑ࡗ࡚࠸ࡿศᏊࡢ✀㢮ࡀᑡ࡞ࡍࡂࡿ࠿㸪≉ᚩ࡟೫ࡾࡀ࠶ࡿࡓࡵ࡜⪃࠼ゎỴࢆ┠ᣦࡋ࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬㞴Ἴ▱ኴ㑻㸪ྜྷ⏣ᑗ㝯㸪኱ᵳᖾ⩏㸪ᶵᲔᏛ⩦࡟ࡼࡿ࣮ࣞࢨ࣮ㄏ㉳ࡢศᏊ㸱ḟඖᩚิࡢไᚚࣛࣥࢻࢫࢣ࣮ࣉ
ᅗࡢண㸪➨ 23 ᅇ⌮ㄽ໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧㸪 2021 ᖺ 5 ᭶ 13 ᪥㸫15 ᪥㸦Ⓨ⾲ࡣ 5 ᭶ 13 ᪥㸧ࠋ1L07‫ۻ‬㞴Ἴ▱ኴ㑻㸪኱ᵳᖾ⩏㸪ᶵᲔᏛ⩦࡟ᇶ࡙ࡃไᚚࣛࣥࢻࢫࢣ࣮ࣉᅗࡢண :࣮ࣞࢨ࣮ㄏ㉳ศᏊ 3 ḟඖᩚิࡢᗘ౫Ꮡᛶ㸪➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧 2021 ᖺ 9 ᭶ 18 ᪥㸫21 ᪥㸦Ⓨ⾲ࡣ 9 ᭶ 20 ᪥㸧ࠋ3P003‫ۻ‬㞴Ἴ▱ኴ㑻㸪኱ᵳᖾ⩏㸪ᶵᲔᏛ⩦ࡀணࡍࡿ࣮ࣞࢨ࣮ㄏ㉳ศᏊᩚิࡢไᚚࣛࣥࢻࢫࢣ࣮ࣉᅗ㸪᪥ᮏ໬Ꮫ఍

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2021 ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮฼⏝࡟ࡼࡿᡂᯝࡣ㸪ࡲ࡜ࡲࡾḟ➨Ꮫ⾡ㄅ࡟Ⓨ⾲ணᐃ࡛࠶ࡿࠋ

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e§¾¼È^bs±´`_z|4PUE%Æ)( CNT  CNF +Âr e§¾(CNT+CNF/PA)ÞÐÕ³Þ%:SB3Ë%(C,0OS4Õ³+Ä("Þam{pcg{ki|7JLQU7MS%(Ä+ÀßÍ"w PA  ¾ÞCNT  +Âr  CNT/PA Âr¾ÞCNF  +Âr  CNF/PA ¾ÞCNT  CNF +&#Âr  CNT/CNF/PAÂr¾+[ ßÙØ(±´Þ¾¥Ë FS;IU3Ç©&)(07¿-PDJS(Bovine serum albumin; BSA):SB3Ë+©ßÅC01- LAMMPSÞg{iFe§¾ GAFF +ÞBSA  CHARMM +Þg{ TIP3P +©ßÐÄ"Þ[ 4 e§¾+4NC1SIj ÞVW4NC1SI+ 1 Bf `}Ol
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0.7 MPa Bi+76 Ð7JLQU7MS+Àß[Þ BSA +¬ÈV½¥ t°³ (Ê{ ß[Þ¼g{¾¬ÈWÀi+6( Þ~Ãe§s¨ (3R8CRUÕX%(WÀ+l­S0 7JLQU7MS+ÀÞ\&)N13OÄ+Àße§¾ SARS-CoV-2 t°È^ bs±´`_z|4PUE%Æ)(

SARS-CoV-2 +¤(" GO/MWCNT ?@Ò¾ÞSARS-CoV-2 t°+Ä("a- 353 -

m{pcg{ki|7JLQU7MS+ÀßSARS-CoV-2 a'+o'd7JLQU7MSm{oy ?Å"Þt°4vÕ³¾­(8B/3:SB3Ë>/S+P ©ß8B/3:SB3Ë;·MC( ÁP CHARMM-GUI  COVID-19 Proteins Library À )
( Fully-glycosylated S protein head-only models (residue 1-1146) 6VSB S only P+©ßGO ¬È 2 ~/;vGP Þ4NC1S¬È OH E COOH E+ C:O  5:1 NSK$6 
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MS+¢ GO ¬Èt°³ (Ê{ ß¬Èt°³ ( +±[ÞN13OÄ+Àß &Þ
250ns 7JLQU7MSt[ 10ns N13OR

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      #  ! $%$ $ $')(!
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g{Ý¸k(ÐB8({®&)ßÞCNF/PA Âr¾#ÞCNF Î-¯ CNF YQ &)("gVy (ß)&+&#Âr  CNT/CNF/PA Âr¾Ë+( hº¾2gn)oÝ ¦&)ÞÐ¼Ý !
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CNT/CNF/PA Âr¾W# BSA ¾µÄ+*("Þ9¸#zßCNT/PA
Âr¾ÞCNF/PA Âr¾t°7JLQU7MSs¤ BSA ¾R '¼ $°- 354 -

"Þ CNT/PA Âr¾4v BSA  )({®&)Þ[ BSA ¾V>¶( %'$°ÈHÞPA ¾s BSA ) ºßCNT/PA Âr¾Þ
CNF/PA Âr¾Ù³¢ÈZ>#®&)¬È3¼È©
' FbÞ'e(%  BSA ¼$°  ¦&)(ßA 2. (a) Ð7JLQU7MSXAÞ(b) ¾ÉDgn)oßA 3.

(a) ¾¬È-BSA ¾ ÂµÄÞ(b) BSA 9¸ße§¾ SARS-CoV-2 t°È^8B/3:SB3Ë GO ¬È&Ä)`& 250 ?@7JLQU7MS+~p ºÞ8B/3:SB3Ë8P'ºr>/St4t° Þ~:SB3Ë;@MC( Át° Þ[ÞN w>/S¬Èt°  ÁYQ &)}O
t°( &(A 4(a), (b))ßt°>/SÒ+ÊºÞCH-"[©, -"[©, ¶ºr%'8B/3:SB3Ë N w>/S8P'ºr>/S¬È¯k%Î- Á(A N17, A N74, A N149, A N165, A T343)z} t° ( &(A 4(c), (d))ß
7JLQU7MS\&)N13Ot[ 10 ns(240-250ns)R ÞMM-GBSA §PUÅ+ÀºÞ8B/3:SB3Ët°%'§PU­#}O'Þ~ÜÃ )gÄ¾Ý0/P8t°gÄ¼+mh( ±(A 5)ßt°}OlQ(¥§­"[©
+°¡Ê{  Þ8B/3:SB3ËT Á/GO Â. C,SPUP8iTÇÆ"[©
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A 4. GO e§¾¬È SARS-CoV-2 8B/3:SB3Ët°7JLQU7MSº: (a) 250ns 7JLQU
7MS[t°Ò, (b) GO ¬Èt° m{o, (c) t° ERIUA  N w>/SÒ, (d)t° ERIUA 8P'ºr>/SÒ 

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A 5. ¥§­"[©%gÄ )t°§PUg4 0<:
1. ºª N_, cU :, W. Wongwiriyapan “z}¨ËqHO-J>2UGS?@;LUD(9
PRU8?@C,/AU(G½a l&w´&BÝÐ POU ©?@ÂrÏ¡Ð¾LUP”, COI -3-T/@FU7MS¤  9 >7SH0K, 2022  11 u 30 r, SN/S
2. J. L. Fajardo-Diaz, A. Morelos-Gomez, |x ,, Ìª ¯#, y ¹K, cU ^, ºª N_ “Öl4NC1S-y2UGS?@;LUD?@Ò¾%( SARS-CoV-2 ¤A/8", COI -3-T/@FU
7MS¤  9 >7SH0K, 2022  11 u 30 r, SN/S
3. TX £Ë, cU ^, A. Morelos-Gomez, R. Cruz-Silva, ºª N_ “7JLQU7MS+©?@2UGSÂr¾e§2KÄ", COI -3-T/@FU7MS¤  9 >7SH0K, 2022  11
u 30 r, SN/S

5

-:
1. J. L. Fajardo-Díaz, A. Morelos-Gómez, 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 Nanofiber and Carbon Nanotube Polyamide Nano-Nanocomposite for High Purity Water Production” SSRN:
available at http://dx.doi.org/10.2139/ssrn.4049452.

- 356 -

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Ed. 2006, 45, 2592; Angew. Chem. Int. Ed. 2013, 52, 3654; Green Chem. 2017, 19, 411; Angew. Chem. Int. Ed. 2018,57, 10278 ௚ከᩘ㹛ࠋᮏ DKR ἲࡣධᡭᐜ᫆࡞ࣛࢭ࣑య࢔ࣝࢥ࣮ࣝࢆ࡯ࡰ 100%ࡢ཰⋡࡛ගᏛάᛶయ࡬࡜ኚ᥮࡛
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ࡍᙳ㡪ࡢゎ᫂ࡀ୙ྍḞ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊᙜࢢ࣮ࣝࣉࡀ᭱㏆ሗ࿌ࡋࡓ VMPS ࡜ࣜࣃ࣮ࢮࢆే⏝ࡍࡿࣉࣟࣃ
ࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡢ DKR㹙S. Kawanishi, S. Oki, D. Kundu, S. Akai, Org. Lett., 2019, 21, 2978㹛࡟ࡘ࠸࡚ࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ᪋タࢆ฼⏝ࡋࡓ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾヲ⣽࡞཯ᛂᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋᅗ 1. VMPS ࡢᵓ㐀㸦A㸧࡜ VMPS㸭ࣜࣃ࣮ࢮࡢඹྠゐ፹࡟ࡼࡿືⓗ㏿ᗘㄽⓗගᏛศ๭㸦B㸧

2◊✲᪉ἲࠊィ⟬᪉ἲ
VMPS ࢆ㔞Ꮚ໬Ꮫィ⟬࡛ᢅ࠺ࡓࡵ࡟ࠊάᛶ୰ᚰࡢᵓ㐀ࢆᢳฟࡋ⡆␎໬ࡋࡓࣔࢹࣝ໬ྜ≀A ࢆ⏝࠸࡚཯ᛂᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋࣛࢭ࣑໬㑄⛣≧ែࡢ᥈⣴࡟ࡣ Gaussian ࣉࣟࢢ࣒ࣛ
09 ࠾ࡼࡧ 16 ࡢᐦᗘỗ㛵ᩘ㸦DFT㸧ἲࢆ⏝࠸ࡓࠋỗ㛵ᩘ࡟ࡣ B3LYP-D3ࠊᇶᗏ㛵ᩘ࡟ࡣ
6-31+G(d)ࢆ⏝࠸ࠊSi ࠾ࡼࡧ V ࡟ᑐࡋ࡚ࡣ Lanl2DZ ࢆ౑⏝ࡋࡓࠋᚓࡽࢀࡓ㑄⛣≧ែ࡟ᑐࡋ
GRRM14 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ SADDLE ィ⟬࡜ Intrinsic Reaction Coordination㸦IRC㸧ィ⟬ࢆ⾜࠸ࠊࣛࢭ࣑໬ࡢ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ- 357 -

3◊✲ᡂᯝࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝ   ࡢ '.5 ࡣࠊ9036 ࡜ࡢࣂࢼࢪࣥ㓟࢚ࢫࢸࣝ , ᙧᡂ࡟ࡼࡿࣛࢭ࣑໬࡜ࠊ

ࣜࣃ࣮ࢮ࡟ࡼࡿගᏛศ๭ࢆక࠺࢔ࢩࣝ໬ࡢ㐣⛬࡛ᵓᡂࡉࢀࡿ㸦ᅗ 㸧ࠋࡲࡓࠊ, ࡀࣛࢭ࣑໬ࡍࡿ㝿࡟ >@㌿఩ࢆ⤒࡚୙㣬࿴࢔ࣝࢹࣄࢻ  ࡀ๪⏕ࡍࡿࠋᮏ◊✲࡛ࡣ๪཯ᛂࡢ>@㌿఩ࢆᢚไࡋ࡚⏕ᡂ≀  ࡢ཰⋡ࢆྥୖࡉࡏࡿࡓࡵࡢᣦ㔪ࢆᚓࡿࡓࡵࠊࣛࢭ࣑໬㐣⛬࡜>@㌿఩࡟ࡘ࠸࡚ ')7 ィ⟬࡟ࡼࡾゎᯒࡋࡓࠋ
ᙜึࠊ9036 ゐ፹࡟ࡼࡿ࢔ࣝࢥ࣮ࣝ  ࡢࣛࢭ࣑໬ࡣࣉࣟࣃࣝࢠࣝ࢝ࢳ࢜ࣥ ,,, ࢆ⤒⏤ࡍࡿࡶࡢ࡜᝿ᐃ
ࡋ࡚࠸ࡓࠋࡋ࠿ࡋ ')7 ィ⟬ࡢ⤖ᯝࠊ&±2 ⤖ྜ㛤⿣ࡢ㑄⛣≧ែࡣᚓࡽࢀࡎࠊ⤖ྜࡢ㛤⿣࡜ᙧᡂࡀ༠ዌⓗ࡟㐍⾜ࡍࡿ㑄⛣≧ែ ,9 ࢆ⤒࡚ࣛࢭ࣑໬ࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊ')7 ィ⟬࡟ࡼࡗ࡚⁐፹ຠᯝࡸⰾ㤶⎔ୖࡢ⨨᥮ᇶຠᯝࢆ᳨ウࡋࡓ⤖ᯝࠊ>@㌿఩࡟ᑐࡋ࡚ࣛࢭ࣑໬ࢆඃඛࡉࡏࡿ࡟ࡣ㠀㓄఩ᛶࡢ㧗ᴟᛶ⁐፹ࡀ㐺ࡋ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝࢆᚓࡓࠋ

ᅗ 2. VMPS㸭ࣜࣃ࣮ࢮ࡟ࡼࡿࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡢ DKR

4 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
1) ‫ ۻ‬M. Makino, S. Komagawa, K. Kanomata, T. Ikawa, S. Akai, manuscript in preparation.
2) ‫ ۻ‬M. Sako, K. Kanomata, M. S. H. Salem, T. Furukawa, H. Sasai, S. Takizawa, “Metal-freeC(aryl)–P bond cleavage: experimental and computational studies of the Michael addition/aryl
migration of triarylphosphines to alkynyl esters”, Org. Chem. Front., 2022, 9, 2187–2192.
3) K. Kasama, Y. Hinami, K. Mizuno, S. Horino, T. Nishio, C. Yuki, K. Kanomata, G. A.I.
Moustafa, H. Gröger, S. Akai, “Lipase-catalyzed Kinetic Resolution of C1-Symmetric
Heterocyclic Biaryls”, Chem. Pharm. Bull., 2022, 70, 391–399.
5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 358 -

Ẽ┦ศᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ศᏊ㛫┦஫స⏝ࡢ⌮ㄽⓗゎᯒ࡜࣮ࣞࢨ࣮ศග
◊✲Theoretical and laser spectroscopic investigations of structures andintermolecular interactions of molecular clusters: Structural analysis
and reaction path search calculations of molecular clusters
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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࠺ࠋࡑࡢ୍౛࡜ࡋ࡚ࠊୡ⏺࡛ึࡵ࡚ᐇ⌧ࡉࢀࡓࠊࢮࣟ౯㑄⛣㔠ᒓ㘒యୖ࡟࠾ࡅࡿ୍㓟໬Ⅳ⣲࢞ࢫࡢᐊ2

ྍ㏫໬Ꮫ྾╔㐣⛬ࢆヲ⣽࡟◊✲ࡋࡓࠋ◊✲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⟬࡟ࡼࡾồࡵࡓࠋࡲࡓࠊ
NBO ࢆ⏝࠸࡚㑄⛣≧ែ࡟࠾ࡅࡿ㌶㐨㛫┦஫స⏝ࢆᐃ㔞ࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮࡜㓄఩Ꮚᵓ㐀ࡢ㐪࠸ࡢ㛫࡟₯ࡴヲ⣽ࢆㄪᰝࡋࡓࠋ

3◊✲ᡂᯝ❅⣲ୖ࡟࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻࢆᑟධࡋࡓ N-࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥࢆ᭷ࡍࡿࢽࢵࢣࣝࢺࣜ࢝ࣝ࣎ࢽࣝ㘒య (1)࠿ࡽࡢࢪ࢝ࣝ࣎ࢽࣝ㘒య (2) ⏕ᡂ㐣⛬࡟࠾ࡅࡿ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࠊ࠾ࡼࡧάᛶ໬࢚ࢿࣝࢠ࣮ࢆࠊDFTィ⟬࡟ࡼࡾ⟬ฟࡋࡓ (ḟ㡫ᅗ)ࠋ
ᮏ㐣⛬ࡀ྾࢚ࣝࢦࣥⓗ ('G = +6.1 kcal mol-1)ࠊࡍ࡞ࢃࡕ࢚ࣥࢺࣟࣆ࣮ᨭ㓄࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡣࠊ
ῶᅽ᮲௳ୗ࡟࠾ࡅࡿ 1 ࠿ࡽࡢ CO ⬺╔཯ᛂࠊ࠾ࡼࡧ CO ຍᅽ᮲௳ୗ࡟࠾ࡅࡿ 2 ୖ࡛ࡢ CO ྾╔཯ᛂࡀࠊࡑࢀࡒ
ࢀ㏿ࡸ࠿࡟㐍⾜ࡍࡿࠊ࡜࠸࠺ᐇ㦂஦ᐇ࡜▩┪ࡋ࡞࠸ࠋࡲࡓࠊ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻ࡟ᑐࡋ࡚㐲㝸఩ࡢ CO ࡀゎ㞳ࡍࡿ path A (㉥Ⰽ) ࡟ࡘ࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ㑄⛣≧ែᵓ㐀 (TS-A) ࡢ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ࡣ+13.3 kcal mol-1(vs. 1) ࡛࠶ࡾࠊCO ⬺╔཯ᛂࡀᐊ࡟࠾࠸࡚㏿ࡸ࠿࡟㐍⾜ࡍࡿࡇ࡜࡜୍⮴ࡍࡿ⤖ᯝ࡛࠶ࡗࡓࠋ
㘒య 1 ࠾ࡼࡧ 2ࠊ

TS-A ࡟࠾ࡅࡿྛ⤖ྜ㛗ࡢẚ㍑࠿ࡽࠊCO ⬺╔཯ᛂࡣࠕ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻࡢ Ni ࡬ࡢ㓄఩ࠖ࡜ࠕCO ࡢ Ni ࠿ࡽࡢゎ㞳ࠖࡀྠ᫬࡟㐍⾜ࡍࡿࠕ༠ዌⓗゎ㞳ᶵᵓࠖࢆ⤒ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣࠊ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩ
ࢻࡢ㓄఩ࡀ CO ⬺╔ࢆಁ㐍ࡋ࡚࠸ࡿࡇ࡜ࢆ⿬௜ࡅࡿ⤖ᯝ࡛࠶ࡿࠋࡲࡓࠊTS-A ࢆ⤒ࡓᚋ࡟ 2 ࡜ CO 㛫࡛ van der
Waals 㘒య ÂÂÂ&2 ࢆᙧᡂࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊ㏆᥋఩ࡢ CO ࡀゎ㞳ࡍࡿ path B (㟷Ⰽ) ࡟࠾࠸࡚ TS-B
ࡢ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓ⤖ᯝࠊ+17.0 kcal mol-1 ࡜࡞ࡾࠊTS-A ࡜ࡢ Gibbs ⮬⏤࢚ࢿࣝࢠ࣮ᕪࡣ+3.7 kcal
mol-1 ࡛࠶ࡗࡓࠋࡍ࡞ࢃࡕࠊpath A ࡀᨭ㓄ⓗ࡞཯ᛂ⤒㊰࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
ࡇࢀࡲ࡛ࠊ㓄఩Ꮚ⨨᥮཯ᛂࢆ⤒ࡿ㑄⛣㔠ᒓ࢝ࣝ࣎ࢽࣝ㘒య࠿ࡽࡢྍ㏫ⓗ໬Ꮫ྾╔཯ᛂࢆᐇ⌧ࡋࠊࡑࡢ཯ᛂ

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ᶵᵓ࡟㛵ࡋ࡚ヲ⣽࡟㆟ㄽࡋࡓ౛ࡣ࡞࠸ࠋᮏ⤖ᯝࡣ㧗ຠ⋡࣭㧗㑅ᢥⓗ࡞ CO ࡢྍ㏫໬Ꮫ྾╔⣔ࢆᵓ⠏ࡍࡿ㝿ࡢ㔜せ࡞▱ぢ࡟࡞ࡿ࡜⪃࠼࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
1.
2.
3.
4.
5.
6.

5

Hoshimoto, Y.; Ogoshi, S. Bull. Chem. Soc. Jpn. , 94, 327.
Iwamoto, H.; Tsuruta, T.; Ogoshi, S. ACS Catal. , 11, 6741.
Hoshimoto, Y.; Nagai, S.; Hinogami, T.; Hazra, S.; Ogoshi, S. Asian, J. Org. Chem. , 10, 1085.
Yamauchi, Y.; Nagai, S.; Terada, T.; Hoshimoto, Y.; Ogoshi, S. Chem. Lett. , 50, 1394.
Yamauchi, Y.; Hoshimoto, Y.; Kawakita, T.; Kinoshita, T.; Uetake, Y.; Sakurai, H.; Ogoshi, S. ChemRxiv.
, preprint (10.26434/chemrxiv-2022-nb0fw).
Hashimoto, T.; Asada, T.; Ogoshi, S.; Hoshimoto, Y. ChemRxiv. , preprint(10.26434/chemrxiv-2022-pgbgd).

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[1])-µ, Ü`´, W6, Ý.n, ÜQd¯ &QdÖÙ£,5ÃÇXD4¶jÝLÚÞ, {Ve2ª 102 n2, Ö¹eÔc, 2022 n 3  23-26 {.
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[3]) Yoshiki Ishii, Go Watanabe, Nobuyuki Matubayasi, Takashi Kato, Hitoshi Washizu, “Molecular Insights on Ionic
Nanochannel and the Hydration Properties of Self-Organized Ionic Liquid Crystals (LÚ)”, Pacifichem2021, Honolulu(USA) and Online, 2021/12/16-21.
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[7]) Yoshiki Ishii, Mathieu Salanne, Norikazu Ohtori, Evaluation of Transport Properties of Molten Alkaline-Earth
Halides and Oxyhalides Using Polarizable Ion Model (LÚ, rkÂ), 7th Asian Conference on Molten Salts
Chemistry and Technology, Online, 2021 n 11  20 {.
[8])-µ, ¸r57Qd|t®P 0-D#&Qd;2@D,cÁ MD .9=BF.>D+7¯0ÝLÚßrkÂÞ, zVeq¸uÒE2(JACI) ?©VeE|q¸Í2z­Q¦2 Â
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[18] ) Yoshiki Ishii, Nobuyuki Matubayasi, Hitoshi Washizu, Molecular Modeling of Ionic Liquids and theirAnalogues via Self-Consistent Scheme with MD and DFT Methods ( 0F)”, CCP2021, Online, 2021/8/1-5.
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[24]) Yoshiki Ishii, Nhu Minh Tue Le, Van Sang Le, Hitoshi Washizu, “Structural Properties of Water Molecules aroundthe PEG and alpha-Cyclodextrin onto Gold Surface by MD Simulation ( 0F)”, ª 70 QÜQde2nc2,
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[25])-µ, 3g, Ý.n, 57 |Qd;2@D,_prÃÝLÚÞ, ª 23 QÈVe¼È2, Zoom, 2021 n 5  13-15 {.

5'

[1]) Y. Ishii, N. Matubayasi, G. Watanabe, T. Kato, H. Washizu, “Molecular Insights on Confined Water in the
Nanochannels of Self-Assembled Ionic Liquid Crystal”, Sci. Adv. 7, eabf0669-1/14 (2021). DOI: 10.1126/sciadv.abf0669.
ÖÊB0@@F0 7 I, +F)"F/ .
[2]) Y. Ishii, N. Matubayasi, H. Washizu, submitted (2022).
[3])-µ, r;2@D,']$Qd×Y¯aÕ, Ve¦ª2Ý%Þ, 1, 17-

21 (2022).
[4])-µ, ª 1 ª 5  3)*DKQd;2@D,cÁ.9=BF.>DaÕ, Q

. : c@gß)*DKhaÕP zUP
ß.F:.FP, 2022 n 6 *g.
[5]) Y. Ishii, H. Torii, Y. Ikemoto, Y. Harada, H. Washizu, et al., in preparation (2022).
[6]) K. Shinozaki, Y. Ishii, S. Sukenaga, K. Ohara, “Ultrafast Nanocrystallization of BaF2 in Oxyfluoride Glasses with
Crystal-like Nanostructures: Implications for Upconversion Fiber Devices”, ACS Appl. Nano Mater. 5, 4281-4292 (2022).
DOI: 10.1021/acsanm.2c00205.
[7]) Y. Kawai, J. Park, Y. Ishii, O. Urakawa, S. Murayama, R. Ikura, M. Osaki, Y. Ikemoto, H. Yamaguchi, A. Harada,
T. Inoue, H. Washizu, G. Matsuba, Y. Takashima, “Preparation of Dual Cross-Network Polymers by Knitting Method and
Evaluation of Their Mechanical Properties”, NPG Asia Mater. 14, 32-1/11 (2022). DOI: 10.1038/s41427-021-00348-2.

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ேᕤගྜᡂࡢࡓࡵࡢ⏺㠃ࡢ◊✲࡜ᙉ┦㛵ࢯࣝࣂ࣮ࡢ᳨ド 2
Study of interfaces for artificial photosynthesis and inspection ofsolvers for strong electron correlation2‫ۑ‬ኳ⬟ ⢭୍㑻ࠊᅵᣢ ᓫႹࠊすཱྀ ࿴Ꮥࠊチ ᜠ⳹ࠊᱱ ᭷ᕼࠊ஭㛵 ኱஬ࠊすᕳ኱ᡂࠊ᳃ᝆⓏࠊୗඖຬ┿ࠊᮯᒣ భேࠊὈ஭ 㞞㈗ࠊỈ㔝 Ⰻဢࠊⰾ಴ Ꮥᘯࠊ୰ከ ♸㈗
㸦⚄ᡞ኱Ꮫ ⛉Ꮫᢏ⾡࢖ࣀ࣮࣋ࢩࣙࣥ◊✲⛉࣭ࢩࢫࢸ࣒᝟ሗᏛ◊✲⛉㸧◊✲┠ⓗᡃࡀᅜࡣࠊ ᖺࡲ࡛࡟෌⏕ྍ⬟࢚ࢿࣝࢠ࣮ࢆ⥲Ⓨ㟁ࡢ୺ຊ࡜ࡍࡿ࡜ࡋ࡚࠾ࡾࠊ୰࡛ࡶኴ㝧ග࡛ỈࢆᏳ౯࡞Ỉ⣲࡟┤᥋ኚ᥮ࡍࡿேᕤගྜᡂࡣᮍ᮶ࢆᢸ࠺ክࡢᢏ⾡࡛࠶ࡿࠋ㧗ຠ⋡ேᕤගྜᡂࡢࡓࡵࡢ =ࢫ࣮࣒࢟ᆺග
ゐ፹ࡣࠊỈࡢ㓟໬࡟ࡼࡾ㟁Ꮚ※࡜࡞ࡿ㓟⣲Ⓨ⏕⣔࡜ࠊ㟁ᏊࢆཷࡅྲྀࡾỈ⣲ࢆ⏕ᡂࡍࡿỈ⣲Ⓨ⏕⣔ࡢྍどගᛂ⟅༙ᑟయࠊࡑࢀࡽࢆ⧅ࡄ㔠ᒓࡸ࢖࢜ࣥ࠿ࡽᡂࡿ࣓ࢹ࢕࢚࣮ࢱ࣮ࠊ࢟ࣕࣜ࢔⛣ື࠿ࡽ཯ᛂࢆಁ㐍ࡍࡿຓゐ፹࠿ࡽᵓᡂࡉࢀ࡚࠸ࡿࠋ༙ᑟయᮦᩱ⮬య࡟ࡣ㐺ษ࡞྾ග≉ᛶ࡜㓟໬㑏ඖ㟁఩ࡢᙉ࠸᮲௳ࡀ࠶ࡾࠊ㸲㟁ᏊࡢỈ㓟໬ࢆ⾜࠺㓟⣲Ⓨ⏕ഃࡢຓゐ፹ࡣ」㞧࡞ࢫࣆࣥ≧ែࢆྲྀࡿ㑄⛣㔠ᒓ㓟໬≀ࡸࣜࣥ㓟໬≀ࡀ୺ᮦᩱ࡛࠶ࡿࠋගゐ፹ࡢ⌮ㄽタィࡣᏛ⾡ⓗ࡟ࡶ♫఍ⓗព⩏࠿ࡽࡶ㔜せ࡞◊✲ㄢ㢟࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊගゐ፹ࡢ࢟ࣕࣜ࢔≉ᛶ࡜ゐ፹タィࢆ⏺㠃ࡢほⅬ࠿ࡽ⾜࠺࡜࡜ࡶ࡟ࠊࡇࢀࡲ࡛㛤Ⓨࡋ࡚ࡁࡓ㓟⣲Ⓨ⏕⣔ࡢྲྀࡾᢅ࠸࡟ᚲせ࡞ᙉ┦㛵ࢯࣝࣂ࣮ࡢ᳨ドࢆᩘ್ⓗ࡟⾜࠸ࠊ㧗ຠ⋡ග࢚ࢿࣝࢠ࣮ኚ᥮ࢆᐇ⌧ࡍࡿࡓࡵࡢ⌮ㄽ◊✲ࢆ᥎㐍ࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲᮏሗ࿌᭩࡛ࡣࠊᐇ᪋ࡋࡓ◊✲ࡢෆࠊ௨ୗ࡟ࡘ࠸࡚㔜Ⅼⓗ࡟ሗ࿌ࡍࡿࠋօ ࢜ࢰࣥศᏊࢆ⏝࠸ࡓ㑅ᢥⓗ && ἲ࡜㑅ᢥⓗ &, ἲ࡜ࡢẚ㍑
ֆ 」ྜ㓟໬≀ࢆຓゐ፹࡜ࡋࡓ࣐࣊ࢱ࢖ࢺ࡟࠾ࡅࡿ㐣㓟໬Ỉ⣲Ⓨ⏕ࡢゎᯒև ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺ <7L26 ࡢ㠃Ḟ㝗ࡢ㟁Ꮚ≧ែゎᯒ㡯┠  ࡣ *(//$1 ࢆࠊ㡯┠   ࡟ࡘ࠸࡚ࡣ୺࡟ 9$63 ࢆ⏝࠸ࡓࠋ◊✲᪉ἲ࡟ࡘ࠸࡚ࡣࠊḟ⠇ࡢ◊✲ᡂᯝ࡛ಶู࡟グ㏙ࡍࡿࠋ



◊✲ᡂᯝ

 ࢜ࢰࣥศᏊࢆ⏝࠸ࡓ㑅ᢥⓗ && ἲ࡜㑅ᢥⓗ &, ἲ࡜ࡢẚ㍑
㓟⣲Ⓨ⏕⣔ࡢゐ፹࣭ຓゐ፹ࢆᵓᡂࡍࡿ㑄⛣㔠ᒓ㓟໬≀ࡸ㑄⛣㔠ᒓࣜࣥ㓟໬≀ࡢ࡛ࡣࠊỈࡢ㸲㟁Ꮚ㓟໬࡟㛵ࢃࡿ୰㛫యࡀᙉ࠸㟁Ꮚ┦㛵ࢆ♧ࡋࠊ㏻ᖖࡢ㟁Ꮚ≧ែ⌮ㄽ࡛ࡣṇࡋ࠸ᵓ㐀ࡸࢫࣆࣥࢠࣕࢵࣉࢆᚓࡿࡇ࡜ࡀ㞴ࡋ࠸ࠋࡑࡢࡓࡵࠊᙉ࠸㟁Ꮚ┦㛵ࢆྲྀࡾᢅ࠺ࡓࡵࡢࢯࣝࣂ࣮࡜ࡋ࡚ࠊᑕᙳ₇⟬Ꮚࢆ⏝࠸ࡓ 3URMHFWHG+DUWUHH)RFN 3+)
ἲࡸ SRVW3+) ἲࠊບ㉳≧ែࡢ᏶඲ &, ゎࢆồࡵࡿࡓࡵࡢࣔࢹࣝ✵㛫㔞Ꮚࣔࣥࢸ࢝ࣝࣟ 0640& ἲࠊ᏶඲⤖ྜࢡࣛࢫࢱ࣮࠿ࡽ㑅ᢥⓗ࡟㔞Ꮚ᣺ᖜࢆỴᐃࡍࡿ )&&5 )XOO&RXSOHG&OXVWHU5HGXFWLRQ ἲ >;X8HMLPD7HQQRPhys.
Rev. Lett.  @࡜ࡑࡢᦤື⿵ṇ )&&5  ἲ>;X8HMLPD7HQQRJ. Phys. Chem. Lett.  @ࡢ㛤Ⓨࢆ⾜ࡗ࡚᮶ࡓࠋ≉࡟ࠊ)&&5 ἲࡣࠊ㏆ᖺ┒ࢇ࡟◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿ㑅ᢥ &, ἲࡢࢧ࢖ࢬ▩┪ࡢḞⅬࢆᇙࡵࡿ᭷ຠ࡞ᡭἲ࡛࠶ࡾࠊ㟁Ꮚ≧ែ⌮ㄽࡔࡅ࡛࡞ࡃࠊ㔞Ꮚࢥࣥࣆ࣮ࣗࢸ࢕ࣥࢢศ㔝࡛ࡶ฼⏝ࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ

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᏶඲ &, Ἴື㛵ᩘࡣࠊࡑࢀ࡜➼౯࡞ᣦᩘ㛵ᩘᆺࡢ᏶඲⤖ྜࢡࣛࢫࢱ࣮Ἴື㛵ᩘ࡛⾲⌧ࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋ
Ȳ୊େ୍ = (1 + ‫)ܥ‬Ȱ = exp(T) Ȱᚋ⪅ࡣ 6L]HH[WHQVLYH ࡞⾲⌧࡛࠶ࡾࠊC ࡀ⣔ࡢ኱ࡁࡉ࡟ᑐࡋ࡚ᣦᩘ㛵ᩘⓗ࡟ቑຍࡍࡿࡢ࡟ᑐࡋࠊT ࡣ⥺ᙧ࡟ࡋ࠿ቑຍࡋ࡞࠸࡜࠸࠺࣓ࣜࢵࢺࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊࡇࡢᛶ㉁ࡀ㏻ᖖࡢィ⟬࡛࡝ࡢ⛬ᗘᙳ㡪ࢆ୚࠼ࡿ࠿ࢆㄪ࡭
ࡿ┠ⓗ࡛ࠊᡃࠎࡀ㛤Ⓨࡋࡓ㑅ᢥⓗ && ἲ࡛࠶ࡿ)&&5  ἲ࡜ࠊ8PULJDU ࡽ࡟ࡼࡿ㑅ᢥⓗ &, ἲ࡛࠶ࡿ6+&, ἲࡢẚ㍑ࢆ࢜ࢰࣥศᏊ࡟ᑐࡋ࡚⾜ࡗࡓࠋ⏝࠸ࡓᵓ㐀ࡣ஧ࡘࡢ␗ᛶయ࡛࠶ࡿ࣮࢜ࣉ࣑ࣥࢽ࣐࣒
20 ࠊࣜࣥࢢ࣑ࢽ࣐࣒ 50 ࡜ࠊࡇࢀࡽࡢ㛫ࡢ㑄⛣≧ែ 76 ࡛࠶ࡿࠋᅗ㸯࡟ FFS94= ᇶᗏ㛵ᩘࢆ⏝࠸ࡓ 76 ᵓ㐀࡛ࡢ㑅ᢥⓗ &, ἲ࡜㑅ᢥⓗ && ἲࡢᦤື⿵ṇ๓ࡢ࢚ࢿࣝ
ࢠ࣮࡜ኚศࣃ࣓࣮ࣛࢱࡢᩘࡢ㛵ಀࢆ♧ࡍࠋ㑅ᢥⓗᅗ㸯 76ᵓ㐀࡛ࡢ㑅ᢥⓗ&, ⥳ ࡜㑅ᢥⓗ&& ㉥&, ࡜㑅ᢥⓗ && ࠸ࡎࢀࡢ᪉ἲ࡟࠾࠸࠸࡚ࡶࠊ᭱ࡶ

࡟࠾ࡅࡿኚᩘࡢᩘ࡜࢚ࢿࣝࢠ࣮ࡢẚ㍑

࢚ࢿࣝࢠ࣮ࡢప࠸᭱Ⰻ⤖ᯝࡣࠊ(+ ⛬ᗘ࡛࠶ࡿࡀࠊ㑅ᢥⓗ &, ἲ࡛ࡣ㸯൨ḟඖ௨ୖࡢ &, ᒎ㛤ࡀᚲせ࡛࠶ࡿࡢ࡟ᑐࡋࠊ㑅ᢥⓗ && ἲ࡛ࡣࠊ㸳ⓒ୓ḟඖ⛬ᗘࡢࢡࣛࢫࢱ࣮₇⟬Ꮚ࡛ྠ➼ࡢ⤖ᯝࡀᚓࡽࢀࡿࡇ࡜ࡀศ࠿ࡿࠋḟ࡟ࠊᅗ㸰࡟ 6+&, ἲ࡜ )&&5  ἲࡢ඲࢚ࢿࣝ
ࢠ࣮࡜ᦤື⿵ṇ࡟⥺ᙧ㛵ಀࡀᡂࡾ❧ࡘࡇ࡜ࢆ♧ࡍࠋࡇࡢ⥺ᙧᛶ࠿ࡽᦤື⿵ṇࡀࢮࣟࡢᴟ㝈࡛᏶඲&, ࢚ࢿࣝࢠ࣮ࡢእᤄ್ࢆồࡵࡿࡇ࡜ࡀฟ᮶ࡿࠋࡇ
ࡇ࡛ 6+&, ἲࡣࠊᦤືィ⟬ࢆࣔࣥࢸ࢝ࣝࣟἲ࡟ࡼࡾ㧗㏿࡟᥎ࡋ࡚࠸ࡿࡢ࡛P(+ ⛬ᗘࡢᑠࡉ࡞

እᤄ㊥㞳࡟࡞ࡗ࡚࠸ࡿࠋ᭦࡟㔜せ࡞ࡢࡣࠊ)&&5 ἲࡢഴࡁࡀ 6+&, ἲ࡜ẚ࡭࡚ⴭࡋࡃᑠࡉ࠸ࡇ࡜࡛࠶
ࡿࠋࡇࢀࡣࠊ)&&5 ἲࡢእᤄㄗᕪࡀ 6+&, ἲࡼࡾࡶᑠࡉ࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ௒ᅇࡢࢣ࣮ࢫ࡛
ࡣࠊ࠸ࡎࢀࡢᡭἲࡶ᏶඲ &, ࡢ᥎ᐃ್ࡣ P(+ ௨ෆ࡟཰ࡲࡗ࡚࠸ࡿࡀࠊ㟁Ꮚᩘࡀከ࠸ሙྜࡣࠊ)&&5 ἲᅗ㸰 ඲࢚ࢿࣝࢠ࣮࡜ᦤື⿵ṇࡢ⥺ᙧ㛵ಀ㸸
6+&, ⥳ ࠊ)&&5 03 㯤 ࠊ (1 㟷ࡢඃ఩ᛶࡀࡉࡽ࡟㢧ⴭ࡟࡞ࡿ࡜ண᝿ࡉࢀࡿࠋ
᭱ᚋ࡟ࠊFFS97= ࡜ FFS94= ᇶᗏ㛵ᩘ࠿ࡽእᤄࡋࡓ᏶඲ᇶᗏ㛵ᩘ &%6 ᴟ㝈ࡢ⤖ᯝࢆ⾲㸯࡟♧ࡍࠋ6+&, ࡜ )&&5 ἲࡢ 20 ᵓ㐀ࡢ࢚ࢿࣝࢠ࣮ࡣ P(+ ௨ෆ୍࡛⮴ࡋ࡚࠸ࡿࡀࠊ㓄⨨✵㛫ࣔࣥࢸ࢝ࣝࣟἲ࡛࠶ࡿ $6)&,40& ἲࡢ⤖ᯝࡣࡑࢀࡼࡾࡶ P(+ ௨ୖ㧗࠸ࡇ࡜ࡀศ࠿ࡿࠋࡲ
ࡓࠊ&&6'7 4 ἲࡣ 6+&, ἲࡸ )&&5 ἲࡼࡾࡶⱝᖸప࠸࢚ࢿࣝࢠ࣮ࢆ୚࠼࡚࠸ࡿࠋ␗ᛶయ㛫ࡢ⾲㸯 ␗࡞ࡿᡭἲ࡟ࡼࡿ 20 ᵓ㐀ࡢ &%6 ᴟ㝈࡛ࡢ᏶඲ &, (+ ࡜␗ᛶ໬࢚ࢿࣝࢠ࣮ P(+ ࡢ᥎࢚ࢿࣝࢠ࣮ᕪ࡟ࡘ࠸࡚ࡣ඲࡚ࡢᡭἲ࡛࡯ࡰྠ➼ࡢ⤖ᯝ࡜࡞ࡗ࡚࠸ࡿࠋ

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್ 」ྜ㓟໬≀ࢆຓゐ፹࡜ࡋࡓ࣐࣊ࢱ࢖ࢺ࡟࠾ࡅࡿ㐣㓟໬Ỉ⣲Ⓨ⏕ࡢゎᯒ⚄ᡞ኱Ꮫ❧ᕝࢢ࣮ࣝࣉ࡜㐃ᦠࡋࠊ࣐࣊ࢱ࢖ࢺࢆ࣍ࢫࢺ࡜ࡋ࡚ࢫࢬ࡜ࢳࢱࣥࢆࢻ࣮ࣉࡋࡓ」ྜ㓟໬≀ࡢ㐣㓟໬ Ỉ⣲ Ⓨ⏕ ࡟㛵 ࡍࡿ ➨୍ཎ⌮ゎᯒࢆ⾜࡞ࡗࡓࠋࢫ ࢬ࡜ ࢳࢱ ࣥࢆ ࢻ࣮ ࣉࡋ ࡓ࣊ ࣐ࢱ ࢖ࢺ 」ྜ 㓟໬ ≀㐣 㓟໬ Ỉ⣲ Ⓨ⏕ ࡣ㧗 ࠸㑅 ᢥᛶ ࡛㐣 㓟໬ Ỉ
⣲ Ⓨ⏕ ࢆ⾜ ࠺ࡇ ࡜ࡀ ᐇ㦂ⓗ࡟♧ࡉࢀ࡚࠾ࡾࠊ↝⤖ ࡟ࡼ ࡾ೫ ᯒࡋ ࡓࢫ ࢬࡸ ࢳࢱ ࣥࡢ 㓟໬ ≀ࡀ ຓ
ゐ ፹࡜ ࡋ࡚ ാࡃ ࡶࡢ ࡜ᅗ㸱 㓟໬ࢫࢬࡢ㓟⣲Ḟ㝗ࣔࢹࣝ㸦ᕥ㸧࡜ࠊྛ✀㓟໬≀࡟ᑐࡍࡿ㐣㓟໬Ỉ⣲Ⓨ⏕ࡢ࣎ࣝࢣ࣮ࣀࣉࣟࢵࢺ㸦ྑ㸧⪃ ࠼ࡽ ࢀࡿ ࠋᮏ ◊✲ ࡛ࡣࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ )H27L6Q26Q7L26Q7L26Q2[6Q7L2[ ⾲㠃࡟࠾ࡅࡿ 2+ ࣛࢪ࢝ࣝࡢ྾╔࢚ࢿࣝࢠ࣮࠿ࡽ஧㟁ᏊỈศᏊ㓟໬࡟ࡼࡿ㐣㓟໬Ⓨ⏕ࡢ࣑ࣜࢸ࢕ࣥࢢ࣏ࢸࣥࢩࣕࣝࡢィ⟬ࢆ⾜࡞ࡗࡓࠋᅗ㸱࡟♧ࡍᵝ࡟ࠊ㐣㓟໬Ỉ⣲Ⓨ⏕ࡢ࣑ࣜࢸ࢕ࣥࢢ࣏ࢸࣥࢩࣕࣝࡣࢧࣂࢸ࢕࢚๎࡟ᚑࡗ࡚ࠊ྾╔࢚ࢿࣝࢠ࣮ࡀ
H9 ௜㏆࡛ᴟᑠࢆᣢࡘ࣎ࣝࢣ࣮ࣀᆺࡢ᣺ࡿ⯙࠸ࢆ♧ࡍࠋ࣍ࢫࢺᮦᩱࡢ࣐࣊ࢱ࢖ࢺࡣࡑࡢඛ➃࠿ࡽእࢀࡿ྾
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⏕యศᏊࡢᚤどⓗ࡞Ỉ࿴ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on microscopic hydration structures of biomolecules‫ۑ‬ᖹ⏣ᆂ♸㸦ᮾᕤ኱໬⏕◊㸧◊✲┠ⓗ㏻ᖖ⏕యෆ࡛ศᏊࡣỈ࿴ࡋࡓ≧ែ࡛ᏑᅾࡍࡿࡓࡵࠊศᏊࡢᵓ㐀࡜ᶵ⬟ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿ࠺࠼࡛ศᏊࡢ

Ỉ࿴ᵓ㐀ࢆゎ᫂ࡍࡿࡇ࡜ࡣ㠀ᖖ࡟㔜せ࡛࠶ࡿࠋࡇࡢࡼ࠺࡞どⅬ࡟❧ࡗ࡚ࠊᮏ◊✲࡛ࡣ  .ࢳࣕࢿࣝ㑅ᢥࣇ࢕ࣝࢱ࣮㒊ศ࣌ࣉࢳࢻ㸫㔠ᒓ㘒యࡢỈ࿴ᵓ㐀ࡢゎ᫂ࠊ  ࢽࢥࢳࣥ࠾ࡼࡧ࣋ࣥࢰ࢝࢖ࣥỈ࿴ࢡࣛࢫࢱ࣮ࡢࣉࣟࢺ
ࣥ௜ຍ఩⨨ࡢỴᐃࢆ⾜ࡗࡓࠋࡇࡇ࡛ࡣ⣬㠃ࡢ㒔ྜୖ  ࡟ࡘ࠸࡚㏙࡭ࡿࠋ.ࢳࣕࢿࣝࡣ .ࡢࡳࢆ㏱㐣ࡉࡏࡿ⭷
ࢱࣥࣃࢡ㉁࡛࠶ࡾࠊ1Dࡣࢳࣕࢿࣝ୰ࢆ㏱㐣ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠸ࠋ࡞ࡐ .ࡼࡾ࢖༙࢜ࣥᚄࡀᑠࡉ࠸ 1Dࡣࢳࣕ
ࢿࣝࢆ㏱㐣࡛ࡁ࡞࠸ࡢ࠿ࠊᏍࡢ኱ࡁࡉ࡟ࡼࡽ࡞࠸࢖࢜ࣥ㑅ᢥᛶ࡟⯆࿡ࡀࡶࡓࢀ࡚ࡁࡓࠋ; ⥺⤖ᬗᵓ㐀ゎᯒࡢ⤖ᯝࠊ࢖࢜ࣥ㑅ᢥᛶ࡟ࡣ㑅ᢥࣇ࢕ࣝࢱ࣮࡜࿧ࡤࢀࡿ࣌ࣉࢳࢻ㒊఩ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣ .ࢳࣕࢿࣝ㑅ᢥࣇ࢕ࣝࢱ࣮ࡢ㒊ศ࣌ࣉࢳࢻ㸦ࢢࣜࢩࣥ㸫ࢳࣟࢩࣥ㸫ࢢࣜࢩࣥࠊ௨ୗ *<*㸧࡜㔠ᒓ࢖࢜ࣥࡢ㘒య㸦*<*0㸧ࢆẼ┦୰࡟⏕ᡂࡋࠊࡑࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢศᏊᵓ㐀ࢆゎ᫂ࡍࡿࡇ࡜࡛ࠊ࣑ࢡ
ࣟ࡞Ỉ࿴ຠᯝࡢほⅬ࠿ࡽ࢖࢜ࣥㄆ㆑ᶵᵓࢆ⌮ゎࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ࢚ࣞࢡࢺࣟࢫࣉ࣮ࣞ࢖࢜ࣥ໬ἲ࡟ࡼࡾ┠ⓗࡢ㔠ᒓ㘒యࢆ⏕ᡂࡋࠊᅄ㔜ᴟ㉁㔞ศᯒィ㸦406㸧࡛≉ᐃࡢ࢖࢜ࣥࡢࡳࢆ㑅ูࡋࠊ . ࡲ࡛෭༷ࡋࡓ࢖࢜ࣥࢺࣛࢵࣉ࡟ᑟධࡋࡓࠋࡇࡇ࡟ỈศᏊࢆᑟධࡋࠊỈ࿴ࢡࣛࢫࢱ࣮
ࢆ⏕ᡂࡋࡓࠋ஧ྎ┠ࡢ 406 ࡛┠ⓗࡢỈ࿴ࢡࣛࢫࢱ࣮ࢆ㑅ูࡋࠊ. ࡲ࡛෭༷ࡋࡓ࢖࢜ࣥࢺࣛࢵࣉෆ࡟࢖࢜ࣥ
ࢆᤕᤊࡋࡓࠋࡇࡇ࡟Ἴ㛗ྍኚ㉥እ࣮ࣞࢨ࣮ࢆᑟධࡋࠊ㉥እ྾཰࡟ࡼࡾᚓࡽࢀࡓゎ㞳≀ࡢ࢖࢜ࣥ㔞ࢆᚋẁࡢ㉁㔞ศᯒィ࡛ᐃࡍࡿࡇ࡜࡛㉥እ྾཰ࢫ࣌ࢡࢺࣝ࡟┦ᙜࡍࡿ㉥እගゎ㞳㸦,53'㸧ࢫ࣌ࢡࢺࣝࢆᐃࡋࡓࠋ┠ⓗࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢྲྀࡾ࠺ࡿᒁᡤᏳᐃᵓ㐀ࢆ ')7 ィ⟬࡟ࡼࡾồࡵࠊ,53' ࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࠿ࡽศ
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ࠋ⌮ㄽィ⟬࡜ࡢẚ㍑࠿ࡽࠊ1Dࠊ. 㘒య࡜ࡶ࡟୺せ࡞ࢥࣥࣇ࢛࣐࣮ࡣ஧ᗙ㓄఩ᆺ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡋ࠿ࡋࠊ. 㘒య࡛ࡣỈศᏊ࡟⏤᮶ࡍࡿỈ⣲⤖ྜ 2+ ఙ⦰ࣂࣥࢻࡀほࡉࢀࡓࡀࠊ1D 㘒య࡛ࡣࡑࢀࡀぢࡽࢀ࡞࠿ࡗࡓࠋࡇࢀࡣỈศᏊࡢ㓄⨨ࡀ . 㘒య࡜ 1D 㘒య࡛␗࡞ࡗ࡚࠸ࡿࡇ࡜ࢆព࿡
ࡋ࡚࠾ࡾ㸦ᅗ 㸧
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ᅗ 1. *<*0㘒యࡢ ,53' ࢫ࣌ࢡࢺࣝ㸬࡟఩⨨ࡍࡿࡇ࡜࡛࢖࢜ࣥࡢ㏻ࡾ㐨㸦ࢳࣕࢿࣝࡢᏍ㸧ࢆሰ࠸࡛࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋᐇ㝿ࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣ 1Dࡀࢳࣕࢿࣝࢆ㏻㐣ࡍࡿ࡜ࡁ࡟   Ỉࢆకࡗ࡚㏱㐣ࡋ࡚࠸ࡿࡇ࡜ࠊ  Ỉࡀࢳࣕ

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͆.ၰࢳࣕࢿࣝ㑅ᢥࣇ࢕ࣝࢱ࣮㒊ศ࡮ࣉࢳࢻ࢔ࣝ࢝ࣜ㔠ᒓ࢖࢜ࣥ㘒యỈ࿴ࢡࣛࢫࢱ࣮ࡢ෭༷࢖࢜ࣥࢺࣛࢵࣉศග㸫࢖࢜ࣥ㑅ᢥᛶ࡟ᑐࡍࡿỈ࿴ຠᯝ㸫͇ ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶㸬‫ ۻ‬Ṋ⏣┤ஓࠊᖹ⏣ᆂ♸ࠊ▼ෆಇ୍ࠊ6RWLULV;DQWKHDVࠊ⸨஭ṇ᫂ࠊ͆ࣉࣟࢺࣥ௜ຍࢽࢥࢳࣥỈ࿴ࢡࣛࢫࢱ࣮ࡢ࢚ࣞࢡࢺࣟࢫ
ࣉ࣮࣭ࣞ෭༷࢖࢜ࣥࢺࣛࢵࣉศග㸫ࣉࣟࢺࣥ⛣ື࡜ྠ఩యຠᯝ㸫͇ ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶㸬‫⏣ ۻ‬㑔ᝅࠊᖹ⏣ᆂ♸ࠊ▼ෆಇ୍ࠊ⠏ᒣග୍ࠊ⸨஭ṇ᫂ࠊ͆.ၰࢳࣕࢿࣝ㑅ᢥࣇ࢕ࣝࢱ࣮㒊ศ࣌ࣉࢳࢻ *<* 㔠ᒓ㘒యࡢ෭༷࢖࢜ࣥࢺࣛࢵࣉ㉥እศග㸫$Jၰ㘒యࡢ≉␗ᛶ㸫͇ ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶㸬‫ ۻ‬༓ⴥ኱㞞ࠊゅ⏣⍠㍤ࠊᖹ⏣ᆂ♸ࠊ▼ෆಇ୍ࠊྜྷἑ㐨ேࠊ⠏ᒣග୍ࠊ⸨஭ṇ᫂ࠊ͆ศᏊㄆ㆑ࡍࡿⰾ㤶⎔࢝ࣉࢭࣝࡢ෭༷࢖
࢜ࣥ㉥እศග㸫ᛶ࣍ࣝࣔࣥ㆑ู࣓࢝ࢽࢬ࣒㸫͇ ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶㸬‫ ۻ‬ᖹ⏣ ᆂ♸ࠊ͆෭༷࢖࢜ࣥࢺࣛࢵࣉ㉥እศගἲ࡟ࡼࡿศᏊෆࣉࣟࢺࣥ⛣ື཯ᛂࡢศᏊㄽⓗ⌮ゎ͇➨  ᅇⱝᡭ◊✲⪅࡟ࡼࡿඛ➃ⓗ࣮ࣞࢨ࣮ศගࢩ࣏ࣥࢪ࣒࢘ࠊ ᖺ  ᭶㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫'* ۻ‬6DQWLV17DNHGD.+LUDWD.7VXUXWD6,VKLXFKL66;DQWKHDVDQG0)XMLL submitted.
‫< ۻ‬6X]XNL.+LUDWD-0/LV\6,VKLXFKLDQG0)XMLL submitted.‫ ۻ‬. +LUDWD . .DVDL . <RVKL]DZD * *UpJRLUH 6 ,VKLXFKLDQG0 )XMLL Phys Chem Chem Phys    
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-&3(GLWRU¶V&KRLFH ‫ ۻ‬71HJRUR.+LUDWD-0/LV\6,VKLXFKLDQG0)XMLLPhysChemChemPhys   6HOHFWHGDV%DFN
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- 379 -

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ␗᪉ⓗ㞟ྜ㓄ྥᮦᩱࡢ⇕ఏᑟ≉ᛶゎᯒ$QDO\VLVRIWKHUPDOFRQGXFWLYLW\IRUOLTXLGFU\VWDOSRO\PHUVDQG
DQLVRWURSLFDOO\DVVHPEOHGRULHQWHGPDWHULDOVXVLQJPROHFXODUG\QDPLF
VLPXODWLRQ‫ྂۑ‬ᒇ ⚽ᓠࠊ㉥ሯ ၨ⣖ࠊ㓇஭ 㐩▮ࠊᑠ㔝⃝ ඃኴ㸦ᮾிᕤᴗ኱Ꮫ≀㉁⌮ᕤᏛ㝔㸧1◊✲┠ⓗᮏ◊✲ࡢ┠ⓗࡣࠊ඲ཎᏊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ␗᪉ⓗ㓄ྥᮦᩱࡢ⇕ఏᑟ≉ᛶࡢ᳨ウ࡛࠶ࡿࠋ㏆ᖺࠊ࢚ࣞࢡࢺࣟࢽࢡࢫࢹࣂ࢖ࢫࡢ㛤Ⓨ࡟࠾࠸࡚ᨺ⇕ᛶࡢྥୖࡀồࡵࡽࢀ࡚࠸࡚ࠊ
ᡂᙧᛶ࡟ඃ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஧㔞యᾮᬗࠊ୺㙐ᆺ㧗ศᏊᾮᬗࠊ࠾ࡼࡧࢺࣜࣉࢳࢭࣥㄏᑟయࡢ
஧ḟඖ⮬ᕫ㞟ྜᵓ㐀ࡢ┦㌿⛣ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜⇕ఏᑟ⋡ࡢゎᯒࢆ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࠶ࡿࠋ        )LJXUH0RGHOGLPHUOLTXLGFU\VWDOV௦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]ࠋ

ᮏ◊✲ࡢᑐ㇟࡛࠶ࡿࣔࢹࣝ஧㔞యᾮᬗ㸦ᅗ 1 ཧ↷㸧ࡢ࣓ࢯࢤࣥࡣࠊ4-cyano-4’-alkylbiphenyl ࡜ྠᵝ࡞ᵓ㐀࡞ࡢ࡛ࠊྠࡌಟṇຊሙࢆ⏝࠸࡚ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋᮏ◊✲࡛ࡣࠊ஧㔞యᾮᬗ CB6CB ࡜ CB7CB ࡟- 380 -

ࡘ࠸࡚ࠊ࢔ࣝ࢟ࣝࢫ࣮࣌ࢧ࣮ࡢⅣ⣲ᩘ n ࡟౫Ꮡࡍࡿ┦㌿⛣ᣲືࡢഅወຠᯝ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡲࡓࠊᾮᬗ┦ࡢᵓ㐀࡟ࡘ࠸࡚⣔ࡢ㓄ྥ⛛ᗎᗘࢆồࡵ࡚ࠊ㓄ྥᵓ㐀ࢆㄪ࡭ࡓࠋࡉࡽ࡟ࠊ㏫㠀ᖹ⾮ศᏊືຊᏛἲ(RNEMD)࡟ࡼ
ࡾ஧㔞యᾮᬗࡢ⇕ఏᑟ⋡ࢆィ⟬ࡋࠊᐇ㦂್࡜ẚ㍑᳨ウࢆ⾜࠸ࠊ⇕ఏᑟ⋡ࡢᡂศศ๭ゎᯒ࡟ࡼࡾ⇕ఏᑟᶵᵓ࡟
ࡘ࠸᳨࡚ウࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ MD ィ⟬ࡣ LAMMPS ࣉࣟࢢ࣒ࣛ 3Mar20 ࣂ࣮ࢪࣙࣥࢆ⏝࠸࡚⾜ࡗࡓࠋࡲࡓࠊ㔞Ꮚ໬Ꮫィ⟬ࡣ Gaussian16ࢆ⏝࠸࡚⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᑐ㇟࡜ࡋࡓศᏊࡣ CB6CB ࡜ CB7CB ࡛࠶ࡿࠋࡍ࡭࡚ࡢࢧࣥࣉ࡛ࣝ 100ศᏊ࡛⣔ࢆᵓᡂࡋ㸪ቃ⏺᮲௳࡟ࡣ࿘ᮇቃ⏺᮲௳ࢆ⏝࠸ࡓ㸬ຊሙࡣ㧗ᶫࡽ[2]ࡀసᡂࡋࡓࢩ࢔ࣀࣅࣇ࢙ࢽࣝ⏝ಟṇຊሙࢆ⏝࠸㸪㟁Ⲵࡣ CHELPG ἲࢆ⏝࠸࡚ MP2/6-31G+(d) ࡛ィ⟬ࡋࡓ㟁Ⲵࢆ⏝࠸ࡓ㸬ィ⟬ࡢ᫬㛫้ࡳࡣ 1 fs ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᐇ㦂್ࡼࡾపᐦᗘࡢ 0.8 g/cm3 ࡛❧᪉యࢭࣝ࡟ศᏊ㓄⨨ࢆࣛࣥࢲ࣒࡟Ⓨ⏕ࡉࡏࠊ➼᪉┦ࡢᗘ࡛ࠊNVT ᮲௳ୗ࡛⦆࿴ࡉࡏ࡚➼᪉┦ࢆసᡂࡋࡓࠋࡇࢀࢆึᮇᵓ㐀࡜

ࡋ࡚ࠊNPT ࢔ࣥࢧࣥࣈ࡛ࣝࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ㏆ഐࡢ

ᗘᩘⅬ࡛ 5 ns 㛫ࡢィ⟬ࢆ⾜࠸ࠊࡉࡽ࡟ 30 ns㛫࡛㹶㍈᪉ྥ࡟ࢭࣝࢆ 1.5 ಸ࡟ᘏఙࡋ࡚ศᏊ㓄ྥࢆಁࡋࠊࡑࡢᚋࠊ➼᪉ᅽຊୗ࡛ 10ns ࡢᖹ⾮໬ࢆ⾜ࡗࡓࠋNPTィ⟬࡛ࡣࠊNose-Hoover ࢧ࣮ࣔࢫࢱࢵࢺ࡜ Parrinello-Rahman ࣂࣟࢫࢱࢵࢺࢆ⏝࠸ࠊ1 bar 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⇕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୚࠿ࡽồࡵࡓࠋ

3◊✲ᡂᯝ
CB6CB ࠾ࡼࡧ CB7CB ࡟ࡘ࠸࡚ࠊࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ㏆ഐࡢ

ᗘ࡟࠾ࡅࡿ㓄ྥ⛛ᗎᗘ P2 ࡢ᫬㛫ኚ໬

ࢆ Figure 2 ࡟♧ࡋࡓࠋFigure 2 ୰ࡢ⥳Ⰽ࢚ࣜ࢔ࡢ᫬㛫ᖏࡣࠊࢭࣝࡢᘏఙ㐣⛬ࡢ᫬㛫ᖏ࡛࠶ࡿࠋCB6CB ࡢ 465K
࡛ࡢィ⟬࡛࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱࡀ 0.5 ⛬ᗘ࡜࡞ࡾ㸪ᐇ㦂࡛ᚓࡽࢀࡓ CB6CB ୰ࡢ࢔ࣥࢺࣛࢭࣥࡢ࣮࢜ࢲ࣮ࣃ
࣓࣮ࣛࢱ࡜㏆࠸್࡜࡞ࡗࡓ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪ᘏఙࢆṆࡵࡓ࠶࡜ࡢ᫬้ 35 ns ࠿ࡽ 45 ns ࡟࠾࠸࡚࣮࢜ࢲ࣮ࣃ
࣓࣮ࣛࢱࡢኚືࡀ኱ࡁ࠸ࡇ࡜࠿ࡽ㸪⣔ࡀᑡࡋ୙Ᏻᐃ࡛࠶ࡿࡇ࡜ࡀண᝿ࡉࢀࡿࠋ୍᪉ࠊCB7CB ࡟࠾࠸࡚ࡣࠊ380
K ࡛ᘏఙᚋࡢ 10 ns 㛫࡟࠾࠸࡚࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱࡢኚືࡀẚ㍑ⓗᑠࡉࡃ㸪ᐇ㦂್࡜㏆࠸್࡜࡞ࡗࡓ㸬ࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ⣔ࢆᘏఙࡋࠊ㓄ྥࢆಁࡍࡇ࡜࡟ࡼࡾ CB7CB ࡟ࡘ࠸࡚ࡣᐇ㦂࡛᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࢿ࣐ࢳࢵ
ࢡ┦࡟㏆࠸⛛ᗎᵓ㐀ࢆ෌⌧࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋCB6CB ࡛ࢿ࣐ࢳࢵࢡ┦ࢆ෌⌧࡛ࡁ࡞࠿ࡗࡓࡇ࡜ࡣࠊࢩ࣑
࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ CB6CB ࡢศᏊ㛫࡟ാࡃ┦஫స⏝ࡀᐇ㝿ࡢ⣔ࡼࡾࡶ኱ࡁࡃぢ✚ࡶࡽࢀࡓࡓࡵ࡛࠶ࡿ࡜
⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊࡇࢀࡽࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ୰ࡢࢲ࢖ࣞࢡࢱ࣮ࡢ x ㍈ᡂศࡢ஧஌ࡢ᫬㛫Ⓨᒎࢆホ౯ࡋࡓ- 381 -

⤖ᯝࠊᘏఙࡍࡿ࡟ࡘࢀ࡚㸪ࢲ࢖ࣞࢡࢱ࣮ࡢ x ᡂศࡀ኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ᭱⤊ᵓ㐀(a)࡟࠾࠸࡚ࡣࠊCB6CB ࡜ CB7CB ࡜ࡶ࡟ x ᡂศࡢ஧஌
ࡢ್ࡣ 0.8 ௨ୖ࡜࡞ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ⣔୰ࡢศᏊ㙐ࡣᘏఙࡋࡓ x ᪉ྥ࡟㓄ྥࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ
㏫㠀ᖹ⾮ศᏊືຊᏛἲ࡟ࡼࡾᚓࡽࢀࡓ⇕ఏᑟ⋡ࢆ⾲㸯࡟ࡲ࡜ࡵࡓࠋCB6CB ࡜ CB7CB ࡢ࠸ࡎࢀ࡟࠾࠸
࡚ࡶࠊࢿ࣐ࢳࢵࢡ┦ࡢ⇕ఏᑟ⋡࡛ࡣࠊ㓄ྥᖹ⾜᪉ྥࡢNҋ್ࡀ㓄ྥᆶ┤᪉ྥࡢNԋ ್ࡼࡾࡶ኱ࡁࡃ࡞ࡿ⇕ఏᑟ⋡ࡢ␗᪉ᛶࡀぢࡽࢀࡓࠋࡲࡓࠊࢿ࣐ࢳࢵࢡ┦ࡢ㓄ྥᖹ⾜᪉ྥࡢNҋࡣࠊ➼᪉┦ࡢNiso ࡼࡾࡶ኱ࡁ࠿ࡗࡓࠋ

(b)

CB7CB ࡢሙྜࠊ⇕ఏᑟ⋡࡜ẚ౛ࡍࡿ≀⌮㔞࡛࠶ࡿ⇕ᣑᩓ⋡ࡢᐇ㦂್࡜ẚ㍑ࢆ⾜࠺ࡓࡵ࡟ࠊᚓࡽࢀࡓ
⇕ఏᑟ⋡ࢆࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽồࡵࡓᐦᗘ࡜ẚ⇕ࢆ⏝࠸࡚⇕ᣑᩓ⋡࡟᥮⟬ࡋࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿
ࡽᚓࡽࢀࡓ㓄ྥᖹ⾜᪉ྥ࡜㓄ྥᆶ┤᪉ྥࡢ⇕ᣑᩓ⋡ࡣࠊDҋ= 5.05 × 10−8 m s-2 ࡜Dԋ = 3.85 × 10−8 m s-2 ࡜࡞ࡗࡓࠋᐇ㦂್ࡣ 383K ࡟࠾࠸࡚㸪Dҋ= 1.03 × 10−7 m s-2
࡜Dԋ = 5.90 × 10−8 m s-2 ࡜ሗ࿌ࡉࢀ࡚࠸ࡿࠋィ⟬࡛ᚓࡽࢀࡓ⇕ᣑᩓ⋡ࡢ್ࡣࠊᖹ⾜᪉ྥ࡜ᆶ┤᪉ྥ࡛ࡑࢀࡒࢀᐇ㦂್ࡢ 0.49 ಸ࡜ 0.65 ಸ࡜࡞ࡾࠊᐇ㦂್࡟ẚ࡭ᑠࡉ࠸್࡜࡞ࡗࡓࠋᐇ㦂್࡟࠾ࡅࡿ␗᪉ᛶࡣ⣙1.75 ࡛࠶ࡾࠊᮏ◊✲࡛⟬ฟࡉࢀࡓ␗᪉ᛶࡣ⣙ 1.31 ࡛)LJXUH  7LPH HYROXWLRQ RI RUGHU SDUDPHWHU LQ
VWUHFKLQJ VLPXODWLRQ RI D  &%&% DQG E  &%&%
LQ YDULRXV WHPSDUDWXUHV 7KH JUHHQ DUHD LQGLFDWHVWKHWLPHWKHVWUHWFKLQJLVRSHUDWHG ࠶ࡿࠋᐇ㦂࡟࠾ࡅࡿࢿ࣐ࢳࢵࢡ┦ࡢ⇕ᣑᩓ⋡␗᪉ᛶࡣࠊ⣙ 1.13㹼1.84 ⛬ᗘࡲ࡛ࡢ

Table 1  Thermal conductivities of CB6CB and CB7CBᖜࡀ࠶ࡿࡓࡵࠊᮏ◊✲ࡢィ⟬⤖ᯝࡣᐇ㦂

Nҋ

Nԋ

Niso

ࢆⰋዲ࡟෌⌧ࡋ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ

CB6CB

0.33 (465K)

0.14 (465K)

0.18 (510K)⇕ఏᑟ⋡ࡢᡂศศゎゎᯒࡢ⤖ᯝࢆ

CB7CB

0.22 (380K)

0.17 (380K)

0.21 (400K)

Figure3 ࡟♧ࡋࡓࠋCB6CB ࡜ CB7CB ࡢ୧

Unit: W m-1 K-1᪉࡜ࡶ࡟ࠊ⤖ྜ㡯ࠊゅᗘ㡯ࠊ஧㠃ゅࠊ࠾ࡼࡧศᏊෆ┦஫స⏝ࡢ㡯ࡣࠊ࠸ࡎࢀࡶᖹ⾜᪉ྥࡢ࡯࠺ࡀᆶ┤᪉ྥࡼࡾࡶ኱ࡁ࠿ࡗࡓࠋࡇࢀࡣ༢㔞యࢩ࢔ࣀࣅࣇ࢙ࢽࣝᾮᬗ 7CB ࡟࠾ࡅࡿඛ⾜◊✲࡜ྠࡌ⤖ᯝ࡛࠶ࡗࡓࠋ⣔ࡢ㓄ྥᖹ⾜᪉ྥ࡟⤖ྜࡀ୪ࢇ࡛࠸ࡿࡇ࡜࡟㉳ᅉࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊCB6CB ࡟࠾࠸࡚ࡣࠊᑐὶ㡯ࡶ㓄ྥᖹ⾜᪉ྥࡀᆶ┤᪉ྥࡼࡾ኱ࡁࡃ࡞ࡗࡓࠋࡇࢀࡶ༢㔞యᾮᬗࡢ⤖ᯝ࡜ྠᵝࡢ⤖ᯝ࡛࠶ࡾࠊศᏊࡢ㓄ྥᖹ⾜᪉ྥ࡟ศᏊࡀ㧗࠸㐠ືᛶࢆᣢࡘࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊCB7CB ࡢᑐὶ㡯ࡣ㓄ྥᆶ┤᪉ྥࡢ࡯࠺ࡀᖹ⾜᪉ྥࡼࡾࡶ኱ࡁ࠿ࡗࡓࠋࡇࢀࡣࠊCB7CB ࡣศᏊෆࡢ࣓ࢯࢤࣥᇶྠኈࡀࣁࡢᏐᆺ࡟୪ࢇ࡛࠾ࡾࠊศᏊࡢ㓄ྥᖹ⾜᪉ྥࡢ㐠ືࡀጉࡆࡽࢀ࡚࠸ࡿࡇ࡜࡟㉳ᅉࡍࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓ㸪CB7CB ࡢศᏊ㛫┦஫స⏝ࡢ㡯ࡣࠊ㓄ྥᖹ⾜᪉ྥࡢ᪉ࡀᆶ┤᪉ྥࡼࡾ኱ࡁࡃ࡞ࡗࡓࠋࡇࢀࡣࠊศᏊࡢ㓄ྥᖹ⾜᪉ྥ࡬ࡢ㐠ືࡀጉࡆࡽࢀࡓࡇ࡜࡟ࡼࡾศᏊ
ྠኈࡀ⾪✺ࡋྜ࠸ࠊ⇕ࡀఏࢃࡗࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬ࡇࢀࡽࡢ⤖ᯝ࠿ࡽ㸪࢔ࣝ࢟ࣝᇶഅᩘࡢࢫ࣮࣌ࢧ

- 382 -

࣮ࢆᣢࡘ஧㔞యᾮᬗ࡛ࡣ༢㔞య࡜࡯ࡰྠࡌഴྥࢆ♧ࡍࡀࠊወᩘࡢࢫ࣮࣌ࢧ࣮ࡢ஧㔞యᾮᬗ࡛ࡣ㸪≉␗ⓗ࡞ഴྥࡀ⾲ࢀࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
(b)

(a)

Figure 3. Contributions of convection and various interactions to thermal conductivities of(a) CB6CB and (b) CB7CB.

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).

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3. ᑠ㔝⃝ ඃኴࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊྂᒇ ⚽ᓠࠊཎᏊ㛫ຊ㢧ᚤ㙾ࢆ⏝࠸ࡓ࣏ࣜ㸦Ț-࣋ࣥࢪࣝ L-ࢢࣝࢱ࣓࣮ࢺ㸧ࡢȘ࣊ࣜࢵࢡࢫ୍ᮏ㙐ࡢຊᏛ≀ᛶホ౯ࠊ➨ 70 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2021 ᖺ㸧ࠋ
4. 㓇஭ 㐩▮ࠊἙ⏣ ᝆኴࠊྂᒇ ⚽ᓠࠊᕝෆ 㐍ࠊ㧗⏣ ༑ᚿ࿴ࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡟ࡼࡿ࣐ࢡࣟࢧ࢖ࢡࣝゐ፹ࡢࢩࣕࢺࣜࣥࢢࡢ᳨ウࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᖺ⛅Ꮨᖺ఍㸦2021 ᖺ㸧ࠋ‫ۻ‬5. ὸ㔝 ඞோࠊྂᒇ ⚽ᓠࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᾮᬗࣔࢹࣝศᏊࡢ⇕ఏᑟᶵᵓࡢゎ᫂ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2022 ᖺ᫓Ꮨᖺ఍㸦2022 ᖺ㸧ࠋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1. Yuki Orito, Hiroyasu Masunaga, Hidemine Furuya, Akihiro Abe, Direct determination of helix structures involvedin the screw-sense reversal of poly(β-phenylpropyl l-aspartate) by synchrotron X-ray diffraction, J. Pept. Sci., 27, e3311(2021): https://doi.org/10.1002/psc.3311- 383 -

Ẽᾮ┦ቃ⏺㏆ഐ࡟࠾ࡅࡿ㡢Ἴఏ᧛ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
Molecular Dynamics Simulation of Sound-Wave Propagation near the
Vapor-Liquid Phase Transition
‫ۑ‬ὸ㔝



ඃኴ㸦ᮾ໭኱Ꮫ㔠ᒓᮦᩱ◊✲ᡤ㸧ࠊ㔝ཱྀ༤ྖ㸦ᮾி኱Ꮫ≀ᛶ◊✲ᡤ㸧◊✲┠ⓗ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡣࠊᾮయ୰ࡢᒁᡤⓗ࡞ῶᅽ࡟ࡼࡿẼἻ⏕ᡂࢆక࠺ὶື⌧㇟࡛࠶ࡿࠋ⯪⯧ࡢ᥎㐍ჾࡸࢱ࣮࣎ᶵᲔ࡞࡝ࠊὶయᶵᲔ࡛࢟ࣕࣅࢸ࣮ࢩࣙࣥ⏕ࡌࡿ࡜ࠊᛶ⬟ࡢపୗࠊ㦁㡢ࡸ᣺ືࠊ࢚࣮ࣟࢪࣙࣥ࡞࡝ࢆᘬࡁ㉳ࡇࡍࠋ୍᪉ࠊẼἻࡀᔂቯࡍࡿ㝿࡟Ⓨ⏕ࡍࡿ⾪ᧁἼࡸࠊᒁᡤⓗ࡞㧗㧗ᅽሙࡣࠊὙίࠊ໬Ꮫ཯ᛂࡢಁ㐍ࠊ་⒪࡞࡝ࠊᴟࡵ࡚ᖜᗈ࠸ศ㔝࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚ࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢ࣓࢝ࢽࢬ࣒ࢆ⌮ゎࡍࡿࡇ࡜ࡣࠊ
┬࢚ࢿࡸ⎔ቃᝏ໬㜵Ṇࠊከศ㔝࡬ࡢᛂ⏝ࢆࡍࡿୖ࡛ࠊᴟࡵ࡚㔜せ࡛࠶ࡿࠋࡇࢀࡲ࡛࡟ࠊᐇ㦂ࡸᩘ್ὶయຊᏛ
ィ⟬ࡀ⾜ࢃࢀ࡚ࡁࡓࡀࠊ࣐ࢡࣟ࡞ὶືሙ࡛⏕ࡌࡿ┦㌿⛣ࢲ࢖ࢼ࣑ࢡࢫࢆ㆟ㄽࡍࡿࡇ࡜ࡣᴟࡵ࡚ᅔ㞴࡛࠶ࡾࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢ࣓࢝ࢽࢬ࣒ࡣ༑ศ࡞⌮ゎࡀ࡞ࡉࢀ࡚࠸࡞࠸ࠋ
ᮏ◊✲࡛ࡣࠊศᏊືຊᏛ㸦0'㸧ィ⟬࡟ࡼࡗ࡚㉸㡢Ἴ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢゎᯒࢆ⾜࠸ࠊẼᾮ┦㌿⛣ࡀ㡢Ἴ࡟୚࠼ࡿᙳ㡪ࢆㄪ࡭ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲὶయࡣ༢ཎᏊศᏊ࡛ᵓᡂࡋࠊࡑࡢศᏊ㛫┦஫స⏝ࡣ /HQQDUG-RQHV㸦/-㸧࣏ࢸࣥࢩࣕࣝ㛵ᩘ࡜ࡍࡿࠋ௨ୗࠊ

≀⌮㔞ࡣ඲࡚ /- ⣔࡟≉ᚩⓗ࡞㛗ࡉ࡜࢚ࢿࣝࢠ࣮ࠊཬࡧ /- ⢏Ꮚࡢ㉁㔞࡛↓ḟඖ໬ࡍࡿࠋ⣔ࡣ኱ࡁࡉࡀ
‫ܮ‬௫ × ‫ܮ‬௬ × ‫ܮ‬௭ = 50 000 × 25 × 25ࡢ┤᪉య࡜ࡋࠊ‫ݖ࡜ݕ‬᪉ྥ࡟࿘ᮇቃ⏺᮲௳ࢆㄢࡍࠋ‫ = ݔ‬0, 50 000ࡢ఩⨨࡟ࠊࡑࢀࡒࢀࠊ᣺ືቨ࡜ᅛᐃቨࢆ㓄⨨ࡍࡿࠋቨࡣ /- ⢏Ꮚࢆ‫ݖݕ‬㠃ࡢṇ᪉᱁ᏊⅬ≧࡟㓄⨨ࡍࡿࡇ࡜࡛ࣔࢹࣝ໬ࡍ
ࡿࠋ᣺ືቨࡣṇᘻⓗ࡟᣺ືࡉࡏࠊࡑࡢ᣺ື᣺ᖜ‫࡜ܣ‬࿘ᮇ݂ࡣࠊࡑࢀࡒࢀࠊ‫ = ܣ‬10࡜݂ = 0.001࡜ࡍࡿࠋ࢚ࢿ
ࣝࢠ࣮ᩓ㐓ࡢࡓࡵ࡟⇕ᾎ㡿ᇦ(49 000 ൑ ‫ ݔ‬൑ 50 000)
ࢆタࡅࡿࠋὶయࡢ⇕ຊᏛ≧ែࡣ୍ḟ㌿⛣Ⅼ㏆ഐ࡜⮫⏺Ⅼ㏆ഐ࡜ࡍࡿ㸦ᅗ 㸧ࠋ0' ィ⟬࡟ࡣ /$0036 ࢆ౑⏝ࡋࡓࠋὶయຊᏛィ⟬࡜ࡢẚ㍑ࢆ⾜࠺ࡓࡵ࡟ࠊ%XUJHUV ᪉⛬ᘧࢆ⏝࠸ࡿࠋ㉸⮫⏺㡿ᇦ࡟࠾࠸࡚ࡣࠊ0' ィ⟬ࡢ⤖
ᯝ࡜ %XUJHUV ᪉⛬ᘧࡢ⤖ᯝࡣ㠀ᖖ࡟Ⰻࡃ୍⮴ࡍࡿࠋ◊✲ᡂᯝᅗ  ࡟୍ḟ㌿⛣Ⅼ㏆ഐ㸦㌿⛣

ᗘܶ = 0.85㸧࡛ࡢᅗ  /- ὶయࡢẼᾮ┦ቃ⏺⥺㸦㯮⥺㸧ࠋ㟷▮༳࡜㉥▮༳ࡣࠊࡑࢀࡒࢀࠊ୍ḟ㌿⛣Ⅼ㏆ഐ࡜⮫⏺Ⅼ㏆
ഐࡢ⇕ຊᏛ≧ែࢆ⾲ࡍࠋ㯮୸ࡣ⮫⏺Ⅼࡢ఩⨨࡛࠶ࡿࠋ

- 384 -

Ἴᙧࡢᗘ౫Ꮡᛶࢆ♧ࡍࠋ㌿⛣ᗘ௨ୖ㸦ᅗ 㸦DG㸧㸧

࡛ࡣࠊ0' ィ⟬ࡢ⤖ᯝ࡜ %XUJHUV ᪉⛬ᘧࡢᩘ್ゎࡀ㠀ᖖ࡟Ⰻࡃ୍⮴ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ㌿⛣ᗘ௨ୗࡢ┦ศ㞳㡿ᇦ࡛ࡣࠊ᣺ືቨ㏆ഐ࡟Ẽ┦㡿ᇦࡀⓎ⏕ࡋࠊ㡢Ἴࡢఏᦙࡀⴭࡋࡃ㜼ᐖࡉࢀࡿ㸦ᅗ㸦H㸧㸧ࠋ୍ḟ㌿⛣㡿ᇦ࡛ࡣࠊ┦㌿⛣ࡢᙳ㡪࡟ࡼࡾἼᙧࡀ୙㐃⥆࡟ኚ໬ࡍࡿࠋᅗ  ࡟⮫⏺Ⅼ㏆ഐ㸦ܶ = 0.94㸧࡛ࡢἼᙧࡢ

ᗘ౫Ꮡᛶࢆ♧ࡍࠋ୍ḟ㌿⛣Ⅼࡢሙྜ࡜␗࡞ࡾࠊ┦ቃ⏺ෆ㒊ࡲ࡛Ἴᙧࡀ㐃⥆ⓗ࡟ኚ໬ࡍࡿࠋ0' ィ⟬ࡢ⤖ᯝ࡜%XUJHUV ᪉⛬ᘧࡢᩘ್ゎࡣࠊ୍ḟ㌿⛣Ⅼ㏆ഐࡢሙྜ࡜
ྠᵝ࡟Ⰻࡃ୍⮴ࡍࡿࠋ⮫⏺Ⅼ㏆ഐࡢሙྜࠊ㌿⛣Ⅼ࡟
㏆࡙ࡃ࡟ࡘࢀ࡚⣔ෆࡢᐦᗘᦂࡽࡂࡀቑຍࡍࡿࡀࠊࡑ
ࡢᙳ㡪ࡣ㡢Ἴࡢ྾཰⋡࡜㠀⥺ᙧᛶ࡟⌧ࢀࡿࡇ࡜ࡀ
ࢃ࠿ࡗࡓࠋ㡢㏿࡟ࡣᙳ㡪ࢆཬࡰࡉ࡞࠸ࠋ⣔ ࡢ ࢧ ࢖ ࢬ ࢆ ‫ܮ‬௫ × ‫ܮ‬௬ × ‫ܮ‬௭ = 10 000 × 100 × 100
࡟ࡋ࡚ࠊ୍ḟ㌿⛣Ⅼ㏆ഐ࡛Ἴᙧࡢ᣺ᖜ౫Ꮡᛶࢆㄪ࡭
ࡓࠋ⤖ᯝࢆᅗ  ᕥᅗ࡟♧ࡍࠋᅗ  ࡟ẚ࡭ࡿ࡜ࠊἼᙧ
ࡣ✜ࡸ࠿࡞ኚ໬ࢆ♧ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋᅗ  ྑᅗࡣᐦᗘሙࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ♧ࡍࠋ᣺ᖜ‫ = ܣ‬5࡛ࡣẼἻࡣ⌧ࢀ࡞࠸㸦ᅗ 㸦D㸧㸧ࠋ‫ = ܣ‬10࡛ẼἻࡀⓎ⏕ࡋጞࡵࡿࡀࠊᡂ㛗ࡣࡏࡎ࡟⏕ᡂ࡜ᾘ⁛ࢆ⧞ࡾ㏉ࡍ㸦ᅗ 㸦E㸧㸧ࠋᅗ୰ࡢ㉥Ⰽ㒊ࡣẼ┦㡿ᇦ࡛࠶ࡿࠋ‫= ܣ‬
15࡟࡞ࡿ࡜᣺ືቨ㏆ഐ࡛Ⓨ⏕ࡋࡓከᩘࡢᑠࡉ࡞Ẽᅗ  ୍ḟ㌿⛣Ⅼ㏆ഐ࡟࠾ࡅࡿἼᙧࡢ ᗘ౫Ꮡᛶࠋ㉥⥺Ἳࡀᡂ㛗ࡋࠊ୍ࡘࡢ኱ࡁ࡞ẼἻࢆᙧᡂࡍࡿ㸦ᅗ  ࡣ 0' ィ⟬ࡢ⤖ᯝ࡛࠶ࡾࠊ㯮◚⥺ࡣ %XUJHUV ᪉⛬ᘧࡢ
㸦F㸧㸧ࠋࡇࡢẼἻࡣ㡢Ἴࡢఏᦙ᪉ྥ࡟ࠊ㡢Ἴ࡜ࡢ┦஫ ᩘ್ゎ࡛࠶ࡿࠋస⏝࡟ࡼࡗ࡚⛣ືࡋࠊᾘ⁛ࡍࡿࠋẼἻࡣࠊࡇࡢ⏕ᡂࠊᡂ㛗ࠊ⛣ືࠊᾘ⁛ࡢࢧ࢖ࢡࣝࢆ⧞ࡾ㏉ࡍࠋ᣺ᖜࢆࡉࡽ࡟
኱ࡁࡃࡍࡿ࡜ࠊ࿘ᮇቃ⏺ࡢᙳ㡪ࡀ㢧ⴭ࡟࡞ࡾࠊ᭱⤊ⓗ࡟Ẽ┦㡿ᇦࢆᙧᡂࡍࡿ㸦ᅗ 㸦GH㸧㸧ࠋẼἻᛶᾮయ࡛ࡣࠊ㡢㏿ࡀ๻ⓗ࡟ῶᑡࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟▱ࡽࢀ࡚࠸ࡿࡀࠊᅗ  ࡟♧ࡋࡓ㏻ࡾࠊᮏ◊✲࡛ࡣ
㡢㏿ࡢኚ໬ࡣほࡉࢀ࡞࠿ࡗࡓࠋ㡢㏿ࡢኚ໬࡟ࡣࠊከᩘࡢẼἻ࡟ࡼࡿᙳ㡪ࡀᚲ㡲࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

௒ᚋࡣࠊࡼࡾ኱つᶍ࡞⣔ࡢゎᯒࢆ⾜࠸ࠊẼἻᛶᾮయ࡟࠾ࡅࡿ㡢㏿పୗࡢ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆෇ᰕ࿘ࡾࡢ࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ࡟ᑐࡍࡿ㧗ศᏊῧຍࡢᙳ㡪͇㸪᪥ᮏὶయຊᏛ఍ᖺ఍ 㸪 ᖺ  ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆㉸㡢Ἴ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ
㸪ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ ࠕ⏕యศᏊࡢᵓ㐀࣭ᶵ⬟࣭ࢹࢨ࢖ࣥࡢィ⟬⛉Ꮫࠖ㸪 ᖺ  ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆኱つᶍศᏊືຊᏛィ⟬࡟ࡼࡿ」㞧ὶయ୰ࡢ࣐࢝ࣝࣥ

- 385 -࡜㡢Ἴఏ᧛͇㸪≀ᛶ◊✲ᡤࢫࣃࢥࣥඹྠ฼⏝࣭&&06 ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤ࠖ㸪 ᖺ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪 ஂಖ ⓒྖ ͆኱つᶍศᏊືຊᏛィ⟬࡟ࡼࡿ࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑
࣮ࣗࣞࢩ͇ࣙࣥ㸪➨  ᅇ㔠ᒓᮦᩱ◊✲ᡤㅮ₇఍㸪 ᖺ  ᭶㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫< ۻ‬$VDQR+:DWDQDEHDQG+1RJXFKL³(IIHFWVRISRO\PHUVRQWKHFDYLWDWLQJIORZDURXQGDF\OLQGHU$ODUJH
VFDOHPROHFXODUG\QDPLFVDQDO\VLV´-&KHP3K\V  ‫< ۻ‬$VDQR+:DWDQDEHDQG+1RJXFKL³(IIHFWVRIYDSRUOLTXLGSKDVHWUDQVLWLRQVRQVRXQGZDYHSURSDJDWLRQ$
PROHFXODUG\QDPLFVVWXG\´3K\V5HY)OXLGVLQSUHVVᅗ  ⮫⏺Ⅼ㏆ഐ࡟࠾ࡅࡿἼᙧࡢ
⛬ᘧࡢᩘ್ゎ࡛࠶ࡿࠋᗘ౫Ꮡᛶࠋ㉥⥺ࡣ 0' ィ⟬ࡢ⤖ᯝ࡛࠶ࡾࠊ㯮◚⥺ࡣ %XUJHUV ᪉- 386 -ᅗ  ኱つᶍ⣔࡟࠾ࡅࡿࠊ୍ḟ㌿⛣Ⅼ㏆ഐࡢἼᙧࡢ᣺ᖜ౫Ꮡᛶ㸦ᕥᅗ㸧ࠋ㉥⥺ࡣ 0' ィ⟬ࡢ⤖ᯝ࡛࠶ࡾࠊ㯮◚⥺ࡣ %XUJHUV ᪉⛬ᘧࡢᩘ್ゎ࡛࠶ࡿࠋྑᅗࡣᐦᗘሙࡢࢫࢼࢵࣉࢩࣙࢵࢺ࡛࠶ࡿࠋ㉥Ⰽ㒊ࡀẼἻ࡛࠶ࡿࠋ

- 387 -



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,;?DG,@F v !1. 0F7)§¯Qe! ¢n%'F+%/Qer"v
!2. ¦©0F7)§V­}[| b oZ"|! "v !

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1. “Inverse Schulze-Hardy rule revisited using an integral equation theory” x{gl  w]f,F9-&<('FA%FªS) ^®
2. “Depletion effect arising from lipid molecules on crystallization of bacteriorhodopsins”

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Suematsu and Ryo Akiyama,  w Liquid Matter Conference'FA%FªS 9.0G

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[3] J. Peng et al., Nature  [4] T. Fukuma and R. Garcia, ACS Nano  >@76XPLNDPDHWDOJ. Phys. Chem. Lett. LQSUHVV   >@76XPLNDPD$6)RVWHU7)XNXPDJ. Phys. Chem. C  >@6&UDQIRUGHWDOJ. Mech. Phys. Solids  - 392 -

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෇೫ගⓎගᛶ (CPL; Circularly Polarized Luminescence) ࢆ♧ࡍⰍ⣲ࡣࠊග࢚ࣞࢡࢺࣟࢽࢡࢫศ㔝࡟࠾࠸࡚ḟୡ௦ࡢ⣲ᮦ࡜ࡋ࡚᭷ᮃどࡉࢀ࡚࠾ࡾࠊᅜෆእ࡛㛤Ⓨ◊✲ࡀάⓎ࡛࠶ࡿࠋ୍᪉࡛ 2,2’-ࣅࣆࣜࢪࣝ㢮ࡣᵝࠎ࡞㔠ᒓ࡜㘒యࢆᙧᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡶࡢࡢࠊ㍈ᛶ࢟ࣛࣝ࡞ࣅࣆࣜࢪࣝࢆ᭷ࡍࡿ㔠ᒓ㘒యࡢሗ࿌౛ࡣ࡯࡜
ࢇ࡝࡞࠸ࠋᡃࠎࡣ௨๓࡟ࠊ(S)-ࣅࢼࣇࢳࣝ࡜ࣅࣆࣜࢪࣝ࠿ࡽᡂࡿ࢟ࣛࣝ࡞኱⎔≧໬ྜ≀ (S)-1 ࡟ࡘ࠸࡚ࠊࣅࣆ
ࣜࢪࣝ࡟ S ࡢ㍈ᛶ࢟ࣛࣜࢸ࢕࣮ࢆㄏ㉳࡛ࡁࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊCPL ࢆ♧ࡍ᪂ࡓ࡞㔠ᒓ㘒య CPL Ⰽ⣲㛤Ⓨࢆ┠ᣦࡋࠊ኱⎔≧໬ྜ≀ (S)-1 ࢆ㓄఩Ꮚ࡜ࡍࡿࣝࢸࢽ࣒࢘㘒యࢆྜᡂࡋࠊࡑࡢගᏛ≉ᛶࢆホ౯ࡍࡿ࡜࡜ࡶ࡟❧యᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘἲ (B3LYP) ࡟ࡼࡾࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢᵓ㐀᭱㐺໬ィ⟬ࠊ᣺ືᩘゎᯒィ⟬ࠊTD ィ⟬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ C, H, N, O ཎᏊ࡟ࡣ 6-31+G(d,p) ࡲࡓࡣ 6-31G(d) ࢆࠊRu ཎᏊ࡟ࡣ LanL2DZ ⏝࠸ࡓࠋィ⟬ࢯࣇࢺࡣ Gaussian16 ࢆ౑⏝ࡋࡓࠋ

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(S)-1 ࢆ㓄఩Ꮚ࡜ࡍࡿࣝࢸࢽ࣒࢘㘒యࢆྜᡂࡋࡓ (ᅗ 1)ࠋሷ໬ࣝࢸࢽ࣒࢘Ỉ࿴≀࡜ (S)-1 ࡢΰྜ≀ࢆຍ⇕

ࡋࠊ3 ࡘࡢ (S)-1 ࡜ 1 ࡘࡢࣝࢸࢽ࣒࢘࢖࢜ࣥ࠿ࡽᡂࡿ㘒య '-(S)-2 ࡜ /-(S)-2 ࡀ࠾ࡼࡑ➼㔞ࡎࡘᚓࡽࢀࡓࠋ

ᅗ 1. ࣝࢸࢽ࣒࢘㘒య 2 ࡢྜᡂᚓࡽࢀࡓ㘒యࡢ❧యᵓ㐀ࢆ㔞Ꮚ໬Ꮫィ⟬ࠊX ⥺⤖ᬗᵓ㐀ゎᯒࠊྛ✀ࢫ࣌ࢡࢺࣝ

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⥆࠸࡚㘒య 2 ࡢࢪࢡ࣓ࣟࣟࢱࣥ⁐ᾮࡢⓎග≉ᛶࢆㄪᰝࡋࡓࠋ'-(S)-యࡣ㠀Ⓨගᛶ࡛࠶ࡗࡓࡀࠊ/-(S)-యࡣ㉥
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Ps (20 °C) ࡛࠶ࡾࠊ᪤▱ࡢࢹ࣮ࢱ࡜ࡢẚ㍑࠿ࡽࡇࡢⓎගࡣ⇥ග࡛࠶ࡿ࡜ุ᩿ࡋࡓࠋࡲࡓࠊ/-(S)-యࡣ CPL ࢆ♧ࡋࡓࠋ␗᪉ᛶᅉᏊ glum ࡣ +1.8 u 10–3 ࡛࠶ࡾࠊࣝࢸࢽ࣒࢘㘒య࡜ࡋ࡚ࡣ኱ࡁ࡞್࡛࠶ࡗࡓࠋ'-(S)-2 ࡜ /-(S)-2 ࡢⓎගᛶࡢᕪ␗ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚⪃ᐹࡋࡓࠋⓎග࡟┤᥋㛵ࢃࡿບ㉳୕㔜㡯≧ែࡢᏳᐃᵓ㐀ࢆồࡵࡓ࡜ࡇࢁ (ᅗ 2)ࠊ'-(S)-య࡛ࡣ࣮࣭ࣖࣥࢸ࣮ࣛຠᯝ࡟≉ᚩⓗ࡞ṍࡳࡀ☜ㄆࡉࢀࠊࡇࡢṍࡳࡀ㠀
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9 ᭶ 18 ᪥.

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- 394 -

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żFloris van Eerden, Xu Zichang, Kevin M. Stapleton (Osaka University, Osaka University, Osaka
University) 

  

 

żFloris van Eerden

1 Introduction
T cells are responsible for recognizing foreign antigens, killing infected or cancerous
cells, and maintaining cellular memory of previously encountered antigens. The T cell
receptor (TCR) plays a crucial role in this by binding to the antigens (epitopes) in thecontext of the major histocompatibility complex (MHC). In the first structure of acomplete TCR, the TCR headgroup is tilted with respect to the membrane normal (1),Figure 1. This tilt led us to hypothesize that the TCR headgroup might possess a certain
flexibility. Indeed, we could identify a linker region in the TCRβ subunit, whichcontains two conserved glycine residues, Figure 2. In this project coarse grained (CG)and fine grained (FG) simulations are used to assess the flexibility of the TCR
headgroup, the role of the linker glycines in this flexibility and how TCR headgroupflexibility is important for pMCH binding.

Figure 1: Cryo-EM structure ofa TCR in complex with its CD3
co-receptor. T cell and APC
membranes are indicated by greyboxes.

2 Methods
Our simulations are based on the cryo-EM structures of Dong et al. (PDB ID
6JXR) and Newell et. al (PDB ID 3QIU) (1) (2). Gromacs versions 2019.4,
2020.6 and 2021.1 were used as the molecular dynamics engine (3). Simulations
were performed with the novel Martini 3 forcefield (4) in conjunction with Gōpotentials (5). FG simulations were done in the Charmm36m forcefield (6).
Figure 2: Figure 2: MSA of the

3 Results

putative hinge region. The sequence ofCoarse grained simulations suggests that TCR headgroup flexibility is importantthe putative hinge is well conserved

for TCR-pMHC binding. Simulations were carried out of membrane embedded

among a wide range of organisms, with

TCRs both in free and pMHC condition. When unbound the TCR headgroupthe two glycines (marked in pink) being

adopts a tilted conformations with an headgroup angle ranging from ~80° toperfectly conserved.

~160°, Figure 3A. Interaction with the pMHC however requires a more straightened conformation, with angles ranging
between ~120° and 180°.
To assess whether the two linker glycines are responsible for the headgroup flexibility, a set of more detailed, fine grained(FG) simulations was performed in which the two linker glycines were either mutated to alanines (G240A_G245A) or- 395 -

prolines (G240P_G245P). Preliminary data shows that both mutations result in a less erect TCR, with the angle
distributions of the mutants shifted towards smaller angles, Figure 3B. A shift towards smaller angles could mean that T
cells expressing the mutant TCRs could be more difficult to activate, as pMHC binding requires a more straightened
conformation according to the CG simulations (Figure 3A). Currently in vitro experiments are being performed to test if
this hypothesis holds in the lab.
B

A

Figure 3: Normalized distributions of the angle between the TCR headgroup and the TCR transmembrane
helices. (A) Angle distributions of CG simulations of free TCRs (blue) and pMHC (orange) bound TCRs. At the start ofthe simulations the angle is 142 degrees, as indicated by the green vertical line. (B) Angle distributions of FG
simulations of three different TCR mutants, in which the two linker glycines (Figure 2) have been mutated to alanines(G240A_G245A) or prolines (G240P_G245P), at the start of the simulations the angle is 142 degrees, as indicated by
the green vertical line.

4 Talks and Posters
Talk at the Immunology Frontier Research Center Colloquium, Osaka University (March 2022)

5 Publications
Van Eerden, F.J. et al. In preparation
Shirai et al. [among which Van Eerden, F.J.]. Submitted

References[1]

D. Dong et al., Nature 1 (2019).

[2]

E. W. Newell et al., Journal of immunology (Baltimore, Md.: 1950) 186, 5823 (2011).

[3]

B. Hess, C. Kutzner, D. van der Spoel, E. Lindahl, Journal of Chemical Theory and Computation 4, 435 (2008).

[4]

P. C. T. Souza et al., Nat Methods 1 (2021).

[5]

P. C. T. Souza, S. Thallmair, S. J. Marrink, R. Mera-Adasme, The journal of physical chemistry letters 10, 7740
(2019).

[6]

J. Huang et al., Nature Publishing Group 14, 71 (2016).

- 396 -

 

        
Xu Zichang

1.

Introduction

Antibodies are a highly diverse class of immune receptors whose binding residues (paratopes) are selected to
specifically recognize a given antigen at a given surface patch (epitope). We have developed AbAdapt(https://sysimm.org/abadapt/), an adaptive approach to model antibody-antigen complex structures from sequence.
Recently, AlphaFold2 can predict protein models with accuracies approaching traditional experimentally-determined
structures. Employing the AlphaFold2 may improve the AbAdapt docking performance and hence increase the accuracyof the epitope prediction.

2.

Methods

We adopted a benchmark that consists of a non-redundant 620 antigen-antibody complexes for training and 100 for
holdout testing. AlphaFold2 is the main method for antibody or antigen modeling. The heavy and light chain wereconjugated by 32 G-linker. In this project, we performed the following set of simulations.
1) Systematical analysis 720 antibody queries by AlphaFold2.
2) Systematical analysis 720 antigen queries by AlphaFold2.
After getting the model of antibody, antigen and antibody-antigen complex by AlphaFold, the following assessment will
be conducted.
1) Calculating the epitope/paratope information of antibody/antigen separately.
2) Analysis of the epitope/paratope RMSD and CDR RMSD for antibody.

3.

Results:HJRWWKHIROORZLQJUHVXOWV 7KHDQWLERG\PRGHOLQJDFFXUDF\ZDVKLJKO\LPSURYHGE\WKH$OSKD)ROGZKLFKOHDGLQJWKHVLJQLILFDQWLPSURYHPHQWLQWKHSDUDWRSH506'RIWKHFRUUHVSRQGLQJDQWLERG\  %\ FKHFNLQJ WKH VXFFHVVIXO PRGHO UDQN RI HDFK TXHU\ DQG FRYHUDJH RI VXFFHVVIXO TXHULHV WKHUH ZDV D VLJQLILFDQWLPSURYHPHQWEHWZHHQ$E$GDSWDQG$E$GDSW$)LQERWK/22&9WUDLQLQJDQGKROGRXWWHVWLQJVHWFigure 1: Comparison of the modeling performance between AbAdapt (blue) and AlphaFold2 (green). (A)The paratope RMSD of antibody modelin LOOCV training set and Holdout set by AbAdapt or AlphFold2. (B) The CDR RMSD of antibody model in LOOCV training set.



- 397 -

     Kevin M. Stapleton

1. Introduction
GroEL is a bacterial chaperonin responsible for the assisted folding of nonnative (unfolded) and misfolded polypeptides(substrates) into biologically active proteins. However, the transient nature of a GroEL-substrate complex and the dynamic
nature (flexibility) of unfolded substrates have precluded their precise structural determination by traditional experimental
methods. In addition, a GroEL-substrate binding motif has never been identified, and therefore inducing a GroELsubstrate structure complex for detailed investigation has remained elusive.
In our recent study (manuscript in preparation), we used the experimental method of single-particle cryo-EM to reveal ahigh-resolution landscape of distinct snapshots of an arrested or ‘stalled’ GroEL irreversibly bound to an unfolded
substrate, UGT1A, at 2.7-3.5 Å resolution. From these results, we successfully visualized UGT1A binding density to a
GroEL subunit (Figure 1A); however, we could not assign the atomic coordinates to the UGT1A noncontinuous density
using traditional methods.
This research set the platform to answer a fundamental that until now, could not be experimentally addressed: what is thesequence of residues in UGT1A responsible for the complete arrest of a GroEL-substrate complex? Using a
combinatorial computational approach with Alphafold2 (AF2) Multimer (AF2-m) for protein-complex prediction and ourexperimentally derived cryo-EM structure, we aim to determine the UGT1A binding sequence responsible for substrate
capture and ultimately, arresting the GroEL-UGT1A structure complex.

2. Methods
This research aims to determine the binding sequence of UGT1A to a GroEL subunit using AF2-m.

We truncated theUGT1A sequence (591 residues in length) into short polypeptides containing ten residues (‘10-mer’ polypeptides).
These were then simulated for protein complex formation against 185 residues in the substrate-binding domain from a
GroEL subunit (GroEL*185). We performed simulations with AF2-m to predict the GroEL*185-peptide complex
interactions for 591 10-mer UGT1A peptides.

Leading candidate UGT1A peptides were selected based on calculated

contact residue strength of peptide residues binding to a GroEL*185 subunit and rendered in the 3D visualization program
UCSF Chimera-X to compare the spatial orientation of the 10-mer peptide to experimentally derived position in the
CryoEM data.

3. Results
Our initial benchmarking of AF2 to predict the structure of the truncated GroEL*185 (substrate-binding domain) to thefull-length GroEL subunit, unexpectedly resulted in the accurate prediction of GroEL subunit structure dynamics. These
results contained new confirmations displaying a continuum of flexible motions for a GroEL subunit bound to UGT1A.
Crucially, these subunit conformations were not in the training data of AF2 (Figure 1B). These results suggest that AF2
might have the capacity to predict protein structure dynamics in catalytic systems.

- 398 -

After confirming AF2 correctly predicted the GroEL*185 structure binding domain, our AF2-m simulations resulted in
24 candidate UGT1A 10-mer polypeptides with high contact strengths and binding positions similar to those seen in thecryoEM data (Figure 1C). We observed that our initial predictions of substrate binding length (10-mer) were tooconservative when fitting into the cryoEM density. Therefore, new simulations with extended UGT1A peptide sequences
will be performed, i.e., extending candidate sequences from 10-mer to 15-mer.

Figure 1: Finding the UGT1A Sequence responsible for GroEL arrest by AlphaFold2 Multimer structure complex prediction(A) Experimentally derived CryoEM atomic coordinates (green) and UGT1A binding density (cyan and purple). (B) AF2 predicted
models of GroEL subunit dynamics matching that of experimentally derived dynamics (Elevation in the substrate-binding domains(colored arrow)). (C) Histogram displaying the binding intensity of UGT1A residues interacting with a GroEL*185 from AF2-m
protein-complex predictions. Above the histogram plot are two example output model predictions (atomic coordinates shown ribbon)
from AF2-m candidate high-intensity 10-mer sequences (red ribbon) complexed with a GroEL*185 (green ribbon).

- 399 -

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2 ◊✲᪉ἲࠊィ⟬᪉ἲ࣏࢚ࣜࢳࣞࣥࡢศᏊࣔࢹࣝ࡜ࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋྂ඾ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ 100 K࡟෭༷ࡋ࡚ᚓࡽࢀࡓ୍ᮏࡢ࣏࢚ࣜࢳࣞࣥ㙐 C300H602(඲ཎᏊࣔࢹࣝ)ࡢᢡࡾ␚ࡲࢀࡓ㓄ྥ⛛ᗎᵓ㐀ࢆึᮇ㓄⨨࡜ࡋࡓࠋᦆയࢆ෌⌧ࡍࡿࡓࡵࠊࡇࡢ࣏࢚ࣜࢳࣞࣥࣔࢹࣝ࠿ࡽỈ⣲ࢆࣛࣥࢲ࣒࡟ྲྀࡾ㝖࠸ࡓࠋྲྀࡾ㝖࠿ࢀࡓỈ- 400 -

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0, 0.01, 0.05, 0.1, 0.2 ࡛࠶ࡿࠋྛࣔࢹࣝ࡟ᑐࡋ࡚ࠊྠࡌึᮇ㓄⨨㸦Fig.1(a)㸧࠿ࡽ 100 K ࡟࠾࠸࡚ 1.3 ns (13,000,000ࢱ࢖࣒ࢫࢸࢵࣉࠊ1 ࢱ࢖࣒ࢫࢸࢵࣉࡣ 0.1 fs)ࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ㧗ㄪ࡭ࡿࡓࡵࠊ100 K/ns ࡢ࡛᪼ࡢᵓ㐀ኚ໬ࢆ

㏿ᗘ࡛ 100 K ࠿ࡽ 400 K ࡲ࡛ィ 3 ns (30,000,000 ࢱ࢖࣒ࢫࢸࢵࣉ)ࡢ᪼

ࢩ࣑࣮ࣗࣞࢩࣙࣥࡶ⾜ࡗࡓࠋࡉࡽ࡟ࠊศᏊ㛫ᯫᶫ࡟ὀ┠ࡍࡿࡓࡵࠊୖグ࡜ྠࡌึᮇ㓄⨨ࡢప࡛ࡢ஧ࡘࡢ࣏࢚ࣜࢳࣞࣥࣔࢹࣝ࡟࠾ࡅࡿ

fold 㒊ศࡢࡳ࠿ࡽࠊỈ⣲ࢆྲྀࡾ㝖ࡁࠊᦆയⅣ໬Ỉ⣲ࣔࢹࣝࢆసᡂࡋࡓࠋࡑࡋ࡚ࠊ஧ࡘࡢ࣏࢚ࣜࢳࣞࣥࣔࢹࣝ
࡟࠾ࡅࡿỈ⣲ࢆྲྀࡾ㝖࠿ࢀࡓ㒊఩ࢆ᥋ゐࡉࡏࠊ100 K ࡟࠾࠸࡚ࠊィ 1ns (100,000,000 ࢱ࢖࣒ࢫࢸࢵࣉ)ࡢࢩ࣑ࣗ
࣮ࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ࡞࠾ࠊNVT ࢔ࣥࢧࣥࣈࣝࢆ⏝࠸ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ࣎ࢵࢡࢫࢧ࢖ࢬࢆ 400 Å400 Å
400 Å ࡜ࡋࡓࠋࡲࡓࠊ

ᗘࢆไᚚࡍࡿࡓࡵࠊNosé̽Hoover ἲࢆ⏝࠸ࡓ㸦+ /L 6 )XMLZDUD + 1DNDPXUD 7

0L]XJXFKL $ 1DNDWD 7 0L\D]DNL DQG 6 6DLWR 6WUXFWXUDO &KDQJH RI 'DPDJHG 3RO\HWK\OHQH E\ %HWD'HFD\ RI
6XEVWLWXWHG7ULWLXP8VLQJ5HDFWLYH)RUFH)LHOG-SQ-$SSO3K\V  6$$%ࢆཧ↷㸧ࠋඛ⾜◊✲ࡢຊሙࣃ࣓࣮ࣛࢱࡢẚ㍑࡟ࡼࡾࠊCHO-2006 ࢆ⏝࠸ࡓ㸦K. Chenoweth, A. van Duin, W. A. Goddard: ReaxFF Reactive Force
Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation, J. Phys. Chem. A, 112 (2008), 1040-1153.㸧
ࠋࢯࣇࢺ࢙࢘࢔ࡣ LAMMPS ࢆ⏝࠸ࡓࠋᅗ㸰㸬4 ࡘࡢ཯ᛂ࡟┦ᙜࡍࡿ໬Ꮫᘧࠋ཯ᛂ(a)࡟࠾࠸࡚ࡣࠊ᪂ࡋࡃ࡛ࡁࡿ C㸫C ࣎ࣥࢻࡢᖹᆒ㊥㞳ࡣ 1.51ύࠋ཯ᛂ(b)࡜(c)࡛ࡣࠊ᪂ࡋࡃ࡛ࡁࡿ C㸻C ஧㔜⤖ྜ࣎ࣥࢻࡢᖹᆒ㊥㞳ࡣ 1.35ύࠋ཯ᛂ(d)࡟࠾ࡅࡿඹᙺ⣔࡛ࡢᖹᆒ C㸫C 㛫㊥㞳ࡣࠊ1.40ύ࡟࡞ࡿࠋ㉥࡛᭩࠿ࢀ࡚࠸ࡿ࡜ࡇࢁࡀࠊReaxFF ࡢ MD ࡛᪂ࡓ࡟⤖ྜࡋࡓ㒊ศࠋ㸱 ◊✲ᡂᯝ
ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥᚓࡽࢀࡓࢫࢼࢵࣉࢩࣙࢵࢺ㸦Fig. 1㸧ࡸᖹᆒ஧஌೫ᕪ(RMSD)ࢆゎᯒࡋࡓ⤖ᯝࠊ5%௨ୖ
ࡢỈ⣲ࡀྲྀࡾ㝖࠿ࢀࡓሙྜࠊప

(100 K)࡛ࡶࠊ᫬㛫ࡢ⤒㐣࡜ඹ࡟ࠊ⛛ᗎᵓ㐀ࡢ⛛ᗎᗘࡀᚎࠎ࡟పୗࡍࡿࡇ࡜

ࡀศ࠿ࡗࡓࠋࣛࣥࢲ࣒࡟Ỉ⣲ࢆྲྀࡾ㝖࠸ࡓ⤖ᯝࠊప

(100 K)࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ࠊ Fig. 2 ࡟♧ࡍࡼ࠺࡞໬Ꮫ཯ᛂࡀ≉ᐃᵓ㐀ࡢࢭࢢ࣓ࣥࢺ㒊఩࡛Ⓨ⏕ࡍࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡉࡽ࡟ࠊࡇࢀࡽࡢ≉ᐃࢭࢢ࣓ࣥ
ࢺ㒊఩࡛໬Ꮫ཯ᛂࡢⓎ⏕ࡍࡿ☜⋡ࡀ 100㸣࡛࠶ࡿࡇ࡜ࡶศ࠿ࡗࡓࠋලయⓗ࡟ࡣࠊ஧ࡘࡢ-CH-ࡢ㛫࡟୍ࡘࡢ-CH2-ࡀᏑᅾࡍࡿሙྜ㸦Fig. 2(a)㸧
ࠊ஧ࡘࡢ-CH-ࡢ㛫࡟ࠊ᪂ࡓࡢ C-C ༢⤖ྜࡀ⏕ᡂࡋࠊ୕ဨ⎔ࡢ⎔≧ᵓ㐀࡟࡞ࡿࠋࡲࡓࠊ஧ࡘࡢ-CH-ࡀ㞄᥋ࡍࡿሙྜ㸦Fig. 2(b)-(c)㸧ࠊ᪂ࡓ࡞⤖ྜࡀ⏕ᡂࡋࠊ㞄᥋ࡋࡓ஧ࡘࡢ-CH-㛫ࡢ C-C༢⤖ྜࡀ C=C ஧㔜⤖ྜ࡟࡞ࡿࠋࡉࡽ࡟ࠊ୕ࡘࡢ-CH-ࡀ㞄᥋ࡍࡿሙྜ㸦Fig. 2(d)㸧
ࠊ୕ࡘࡢ-CH-ࡢ㛫ࡢ⤖ྜࡀඹᙺ⤖ྜ࡟࡞ࡾࠊ஧ࡘࡢ⤖ྜゅࡣ⣙ 120˚࡜࡞ࡿࠋ⥆࠸࡚⾜ࡗࡓ㧗࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ࠊ≉ᐃ㒊఩࡛ࡢ㙐ษ᩿ࡀほࡉࢀࡓࠋ㙐ษ᩿ࡢ๓ᚋ࡟࠾

ࡅࡿࠊ≉ᐃࡢࢭࢢ࣓ࣥࢺ㒊఩㸦-CH2-CH-CH2-CH2-CH-CH2-㸧୰ࡢྛ C-C 㛫㊥㞳ࡢᗘኚ໬ࢆ Fig. 3 ࡟♧ࡍࠋ┿ࢇ୰ࡢ-CH2-CH2-࡟࠾ࡅࡿ୙Ᏻᐃ࡞ C-C ⤖ྜ㸦ᅗ୰ࡢ D1ࠊ⤖ྜ㛗⣙ 1.70 Å㸧ࡣࠊ⣙ 348 K ࡛㛤⿣ࡋࠊ㙐ษ- 401 -

᩿ࡀⓎ⏕ࡍࡿࠋࡑࡢᕥࡢ-CH-CH2-࡟࠾ࡅࡿ C-C ⤖ྜ㸦ᅗ୰ࡢ D2ࠊ⤖ྜ㛗ࡣ⣙ 1.46 Å㸧ࡣࠊ⣙ 348 K ࡛Ᏻᐃ࡞ C=C ஧㔜⤖ྜ㸦⤖ྜ㛗⣙ 1.34 Å㸧࡟࡞ࡿࠋ୍␒ᕥࡢ-CH2-CH-࡟࠾ࡅࡿ C-C ⤖ྜ㸦ᅗ୰ࡢ D3㸧ࡣࠊ⤖ྜࡢ⏕ᡂࡸ㛤⿣ࡣ⏕ࡌ࡞࠸ࡀࠊྠࡌ

ᗘ⣙ 348 K ࡟࠾࠸࡚ࠊ୙Ᏻᐃ≧ែ㸦⤖ྜ㛗⣙ 1.48 Å㸧࠿ࡽᏳᐃ≧ែ㸦⤖ྜ㛗⣙ 1.54 Å㸧࡟࡞ࡿࠋ᭱⤊ⓗ࡟ࠊࡇࡢࢭࢢ࣓ࣥࢺࡣࠊ-CH2-CH=CH2 + CH2=CH-CH2-࡟࡞ࡿࠋࡇࡢࡼ࠺࡟ࠊReaxFF ࢆ⏝࠸ࡓ㧗ศᏊࡢ MD ࢆ⾜࠸ࠊඹ᭷⤖ྜࡢ⤌ࡳ᥮࠼࡞࡝ࢆ㐺ษ࡟ィ⟬࡛ࡁࡿࡇ࡜ࢆ☜࠿ࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ௒ᅇ౑ࡗࡓ ReaxFF ࣏ࢸࣥࢩࣕࣝࢆᇶ┙࡜ࡋ࡚㧗ศᏊ⣔࡛ᇵࡗࡓ⤒㦂ࢆࠊࡼࡾ」㞧࡞ᵓ㐀ࢆᣢࡘ DNA ࡢィ⟬ࡢᖹ⾮≧ែ᥈⣴࡟㐍ࡵ࡚࠸ࡁࡓ࠸ࠋ
(c)
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ࠋ⣙ 348K ࡛ࠊ୙Ᏻᐃ࡞㟷Ⰽࡢ⤖ྜࡀษࢀࠊ⣸Ⰽࡢ C-C ༢⤖ྜࡀᏳᐃ࡟࡞ࡾࠊⲔⰍࡢ⤖ྜࡣ୙
Ᏻᐃ࡞ C-C ༢⤖ྜ࠿ࡽᏳᐃ࡞ C=C ஧㔜⤖ྜ࡟ኚ໬ࡍࡿࡇ࡜ࡀࢃ࠿ࡿࠋ

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International Conference on Plasma-Nano Technology & Science (IC-PLANTS2022), Online, March 8, 2022
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Haolun Li, Susumu Fujiwara, Hiroaki Nakamura, Tomoko Mizuguchi, Ayako Nakata, Tsuyoshi Miyazaki, Shinji
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'1$EUHDNV-RXUQDORI$GYDQFHG6LPXODWLRQLQ6FLHQFHDQG(QJLQHHULQJ  ᖺ- 404 -

㔠ᒓ᭷ᶵᵓ㐀య࡟ࡼࡿỈྠ఩యศᏊㄆ㆑
Molecular Recognition of Water Isotopes by MetaíOrganic Frameworks‫⏣ۑ‬୰ ⚽ᶞ㸦ಙᕞ኱Ꮫඛ㗦ᮦᩱ◊✲ᡤ㸧◊✲┠ⓗ㔠ᒓ᭷ᶵᵓ㐀యࡢ୍✀࡛࠶ࡿ &D 㘒య >&D &2 +2@Q >@ࡣ㸪&D ཎᏊ࡟ࢫࢡ࢔ࣜࣥ㓟࢔ࢽ࢜ࣥࡀ㓄఩ࡋ㸪࠿ࡘ㸪ỈศᏊࡀ໬Ꮫⓗ࡟྾╔ F+2 ࡋࡓࣇ࣮࣒࣮ࣞ࣡ࢡᵓ㐀ࢆ᭷ࡋ࡚࠾ࡾ㸪ࡑࡢࣇ࣮࣒࣮ࣞ࣡ࢡ୰ࡢ  ḟඖࢳࣕࣥࢿࣝࡣ㸪ỈศᏊࢆ≀⌮྾╔ S+2㸸᭱኱࡛ &DཎᏊᙜࡓࡾ  ಶ ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ ᅗ  ࠋࡇࡢ≧ែ ࡟ ࠾ ࡅ ࡿ &D 㘒 య S+2F+2 ࡢ D ㍈᪉ྥࡢ᱁Ꮚᐃᩘ . ࢆ㸪LQVLWX;53'ᐃ࡟ࡼࡗ࡚Ỵᐃࡋࡓ࡜ࡇࢁ㸪F+2 ࡢࡳ࠿ࡽ࡞ࡿ &D 㘒యࡼࡾࡶ㸪ࡑࡢᅗ  &D 㘒య>&D &2 +2 ࣭ +2 @Q ࡢᵓ㐀ᵓ㐀ࡀ཰⦰ࡋ࡚࠸ࡿࡇ࡜
ࡀศ࠿ࡗࡓࠋࡑࡇ࡛㸪$,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ DE LQLWLR ศᏊືຊᏛἲ &3. VRIWZDUH>@ ࢆᐇ᪋ࡋࡓ࡜ࡇࢁ㸪S+2 ࡜ F+2 ࡜ࡢ㛫࡟Ỉ⣲⤖ྜࡀᙧᡂࡉࢀ㸪F+2 ࡀ㓄఩ࡍࡿ &D ࢖࢜ࣥ࡟ᑐࡋ࡚㸪 ḟඖࢳࣕࣥࢿࣝࡢ୰
ᚰ㍈࡟ᆶ┤࡞᪉ྥ࡬ࡢᘬຊࢆ⏕ࡌ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡘࡲࡾ㸪&D 㘒యࡣ S+2 ࡜ F+2 㛫ࡢỈ⣲⤖ྜᙧᡂ࡟ࡼࡿᛂ⟅≉ᛶࢆ᭷ࡋ࡚࠸ࡿࡇ࡜࡟࡞ࡿࠋࡉࡽ࡟㸪&D 㘒యࡢ D ㍈᪉ྥࡢ᱁Ꮚᐃᩘࡢ S+2 ྾╔㔞౫Ꮡᛶ . ࢆ LQVLWX;53'ᐃ࡟ࡼࡗ࡚ㄪ࡭ࡓ࡜ࡇࢁ ᅗ  㸪S+2 ྾╔㔞ࡢቑຍ࡟కࡗ࡚㸪᱁Ꮚᐃᩘ D ࡀᑠࡉࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣ㸪S+2 ࡢศᏊᩘࡀከࡃ࡞ࡿ࡟ᚑࡗ࡚㸪S+2 ࡜ F+2 ࡜ࡢ㛫࡟ᙧᡂࡉࢀࡿỈ⣲⤖ྜᩘࡀቑຍࡍࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡑ
ࡇ࡛㸪+2 ࡼࡾࡶᙉ࠸Ỉ⣲⤖ྜࢆᙧᡂࡍࡿ '2 ࢆ&D 㘒య࡟≀⌮྾╔ . ࡉࡏࡓ࡜ࡇࢁ㸪ண᝿࡟཯ࡋ࡚㸪᱁Ꮚᐃᩘ D ࡢ཰⦰ࡣ S+2 ྾╔ࡢሙྜࡼࡾࡶᑠࡉࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡇ࡛㸪ᾮయ≧ែ ࣂࣝࢡ ࡟࠾ࡅࡿ +2 ศᏊ㛫ࡢỈ⣲⤖ྜࡣ'2 ࡢࡑࢀࡼࡾࡶᙅࡃ࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ
ࡀ㸪ࡇࢀࡣ ' ཎᏊࡼࡾࡶ㉁㔞ࡢᑠࡉ࡞ + ཎᏊ࡟࠾ࡅࡿ఩⨨୙☜ᐃᛶࡀ኱ࡁࡃ࡞ࡿࡓࡵ࡟㸪ࣉࣟࢺࣥ࡜㓟⣲ཎᏊ㛫࡟࠾ࡅࡿỈ⣲⤖ྜ࢚ࢿࣝࢠ࣮ࡀ
ᑠࡉࡃ࡞ࡿࡓࡵ࡛࠶ࡿࠋࡍ࡞ࢃࡕ㸪ୖ㏙ࡢ S+2
࡜ S'2 ࡢ྾╔࡟ࡼࡿ &D 㘒యࡢ཰⦰ᣲື࡟࠾ࡅᅗ  ,QVLWX;53' ᐃ࡟ࡼࡿ &D 㘒యࡢ᱁Ꮚᐃᩘ D ࡢ+2 ࠾ࡼࡧ '2 ྾╔㔞౫Ꮡᛶ .

- 405 -

ࡿᕪ␗ࢆィ⟬⛉Ꮫⓗ࡟᳨ウࡍࡿࡓࡵ࡟ࡣ㸪)H\QPDQ ࡢ⤒㊰✚ศἲ࡟ࡼࡗ࡚㸪ࡑࡢ㔞ᏊຊᏛⓗຠᯝࢆ⪃៖ࡍࡿᚲせࡀ࠶ࡿࠋࡑࡇ࡛㸪&3. ࢆእ㒊ࢥ࣮ࢻ࡜ࡍࡿ LSL VRIWZDUH >DELQLWLR ⤒㊰✚ศศᏊືຊᏛ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࡓࡵࡢ 3\WKRQ ࢥ࣮ࢻ>@@ࢆ౑⏝ࡋ ᅗ  㸪S+2 ࡜ S'2 ࡢ྾╔࡟ࡼࡿ &D 㘒యࡢ཰⦰ᣲືࢆ
$,3,0' ࡟ࡼࡗ࡚ヨ㦂ⓗ࡟᳨ウࡋࡓ࡜ࡇࢁ . 㸪ᐇ㦂⤖ᯝ࡟ᐃᛶⓗ࡟୍⮴ࡋ㸪+2 ࡜ '2 ྾╔࡟࠾ࡅࡿ㔞ᏊຊᏛⓗຠᯝࡢᕪ␗ࡀ㸪&D 㘒య࡟Ỉྠ఩యࡢศᏊㄆ㆑⬟ࢆࡶࡓࡽࡋ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ
ࡋ࠿ࡋ㸪ࡇࡢ $,3,0' ࡛ࡣ㸪ཎᏊ᰾ࢆ  ಶࡢㄪ࿴᣺ືᏊࣂࢿ࡛㐃⤖ࡉࢀࡓྂ඾ࣅ࣮ࢬ⩌࡟ࡼࡗ࡚⾲ࡍᚲせࡀ࠶ ࡾ >SDWK LQWHJUDO JHQHUDOL]HG
/DQJHYLQHTXDWLRQWKHUPRVWDW

3,*/(7 ἲࢆ౑⏝@㸪ྛࣅ࣮ࢬ࡟ࡘ࠸࡚ࡢ ')7 ィ⟬ࢆ  ୪ิ࡛ィ⟬ࡍࡿᚲせࡀ࠶ࡿࡓࡵ࡟㸪ᴟࡵ࡚ィ⟬ࢥࢫࢺࡀ㧗࠸ࠋࡇࡢࡓࡵ㸪ࠕ ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝➼ࡢබເࠖ࡟
ᘬࡁ⥆ࡁ㸪ࠕ ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝➼ࡢබເࠖ࡟ᛂເࡋ㸪኱つᶍ࡞ $,3,0'ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡍࡿࡇ
࡜࡛㸪&D 㘒య࡬ࡢỈ྾╔࡟క࠺ᵓ㐀ኚᙧ࡞ࡽࡧ࡟Ỉྠ఩య+2 ࠾ࡼࡧ '2 ࡢศᏊㄆ㆑⬟ᅗ  )H\QPDQ ࡢ⤒㊰✚ศἲ࡟ᇶ࡙ࡃỈศᏊࡢᵓ㐀⾲⌧࡜
LSL&3. ࡟ࡼࡿ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ

ࡢⓎ⌧࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡜ࡍ
ࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲ㸪ィ⟬᪉ἲ&3. ࡟ࡼࡗ࡚㸪>&D &2 F+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S+2@Q ࡢᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓ㸦uuࢭࣝ㸧ࠋᮏィ⟬࡛ࡣ㸪%/<3 ỗ㛵ᩘ㸪'=9302/23765*7+ ᇶᗏ㛵ᩘࢆ⏝࠸㸪&XWRII  5\㸪5HO&XWRII 
 5\ ࠾ࡼࡧ 1*5,'6  ࢆ᥇⏝ࡋࡓࠋࡲࡓ㸪')7' ࡟ࡼࡗ࡚ศᩓຊ⿵ṇࢆ⾜ࡗࡓࠋ ᖺᗘ࡛ࡣ㸪ୖグࡢᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ㸪&3. ࢆእ㒊ࢥ࣮ࢻ࡜ࡍࡿ LSL
VRIWZDUH ࡟ࡼࡗ࡚㸪>&D &2 F+2࣭S+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S'2@Q ࡢ $,3,0' ࢩ࣑࣮ࣗࣞ
ࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ᮲௳ࡣ௨ୗࡢ㏻ࡾ㸸FRQVWDQWVWUHVV 167 HQVHPEOH㸪ᆶ┤ᛂຊ  03D㸪ࡏࢇ᩿ᛂຊࢮࣟ㸪ᗘ .㸪.㸪.㸪.㸪᫬㛫ࢫࢸࢵࣉ IV㸪ࣅ࣮ࢬᩘ  ࡲࡓࡣ 㸪ࣅ࣮ࢬᩘ࠶

ࡓࡾࡢ FRUH ᩘ 㸪%/<3 ỗ㛵ᩘ㸪'=9302/23765*7+ ᇶᗏ㛵ᩘࢆ⏝࠸㸪&XWRII  5\㸪5HO&XWRII 
5\㸪1*5,'6 ࠋࡲࡓ㸪3,*/(7 ࣃ࣓࣮ࣛࢱ࣮ࡣ KWWSFRVPRHSIOJLWKXELRJOHPG ࡟࠾࠸࡚ྲྀᚓࡋࡓࠋ
 ᖺᗘࡣ㸪ୖ㏙ࡢ 167HQVHPEOH ࡛ࡣ↓ࡃ㸪137HQVHPEOH D E J  ࡜ࡋ࡚ィ⟬ࢆᐇ᪋ࡋࡓࠋࡑࡢ
௚ࡢィ⟬᮲௳ࡣ  ᖺᗘ࡟ྠࡌ࡛࠶ࡿࠋ

- 406 -◊✲ᡂᯝᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓ>&D &2 F

+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S+2@Q ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆᅗ  ࡟♧ࡍࠋࡑࢀࡒࢀࡢ
᱁Ꮚᐃᩘࡣ㸪>&D &2 F+2@Q㸸a b c㸪c  c 㸪 >&D &2 F+2 ࣭ S+2@Q㸸a b c㸪c c ࡜࡞ࡾ㸪ᅗ   &3. ࡟ࡼࡿᵓ㐀᭱㐺໬㸸 D >&D &2 F+2@Q
E >&D &2 F+2࣭S+2@Q

S+2 ࡢᏑᅾ࡟ࡼࡗ࡚ᵓ㐀ࡀ཰⦰ࡍࡿࡇ࡜
ࡀศ࠿ࡗࡓࠋィ⟬࡟ࡼࡾᚓࡽࢀࡓ᱁Ꮚᐃᩘ ab ࡢ⤯ᑐ್ࡣᐇ㦂⤖ᯝ ᅗ  ࡼࡾࡶࢃࡎ࠿࡟኱ࡁ࠸ࡀ㸪S+2 ࡢ྾╔࡟క࠺᱁Ꮚᐃᩘࡢኚ໬ࡢ࣮࢜ࢲ࣮ࡣᐇ㦂⤖ᯝ࡟Ⰻࡃ୍⮴ࡋ࡚࠸ࡿࠋ
; ⥺ᅇᢡ

ᐃ ᐊ

࡟ࡼࡾ᫂ࡽ࠿࡜࡞ࡗ࡚࠸ࡿ>&D &2 F+2࣭S+2@Q ࡢᵓ㐀ࡣṇ᪉ᬗ a b cD 

E J  ࡛࠶ࡿࡀ㸪$,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ ࣅ࣮ࢬᩘ 㸸ྂ඾ S+2 ࢆ⾜ࡗࡓ࡜ࡇࢁ㸪 ᗘ . ௨ୗ࡟࠾࠸࡚┦㌿⛣ࡀ⏕ࡌ㸪J  ࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗ
ࡓ>ᗘ . ࠾ࡼࡧ . ࡛ࡣṇ᪉ᬗ@ࠋࡇࢀࡣ㸪&D㘒యࡢኚᙧ࡟ࡼࡗ࡚㸪ࡑࡢࣇ࣮࣒࣮ࣞ࣡ࢡ࡜ S+2 ࡜ࡢ┦஫స⏝ࡀቑᙉࡉࢀࡓࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ୍᪉㸪>&D &2 F+2࣭S+2@Q ࠾ࡼࡧ>&D &2 F+2࣭
S'2@Q ࡟ࡘ࠸࡚ࡢ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ ࣅ࣮ࢬᩘ 㸸㔞Ꮚ S+2 ࠾ࡼࡧ㔞Ꮚ S'2 ࢆᗘ . ࡟࡚⾜ࡗࡓ࡜ࡇࢁ㸪>&D &2 F+2࣭S'2@Q ࡛
ࡣJ 㸪>&D &2 F+2࣭S+2@Q ࡛ࡣJ 
࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢࡇ࡜ࡣ㸪&D 㘒యࡀỈྠ఩యศᏊ࡟࠾ࡅࡿ㔞Ꮚຠᯝࡢᕪ␗ࢆㄆ㆑ࡋ࡚ᵓ㐀㌿⛣ࢆ㉳ࡇࡋ㸪࠿ࡘ㸪ࡑࡢᵓ㐀ࡀ␗࡞ࡿࡶࡢ࡟࡞ࡿࡇ࡜
ࢆ♧၀ࡋ࡚࠸ࡿࠋణࡋ㸪ୖ㏙ࡢࡼ࠺࡟㸪; ⥺ᅇᢡ
ᐊ

࡟ࡼࡗ࡚ほ

ᐃ

ࡉࢀࡓ>&D &2 F+2࣭S+2@Q ࡢᵓ㐀ࡣṇ᪉ᬗ࡛࠶ࡗ࡚㸪༢ᩳᬗ࡛ࡣ↓࠸ࠋࡇࢀࡣ㸪ṇ᪉ᬗ࠿ࡽ༢ᩳᬗ࡬ࡢ┦㌿⛣࡟࠾ࡅࡿ࢚ࢿࣝࢠ
࣮㞀ቨࡀࢩ࣑࣮ࣗࣞࢩࣙࣥࢭࣝᙜࡓࡾ࡛ࡣ༑ศᑠࡉ
࠸ࡢ࡟ᑐࡋ㸪ᩘPP ࣮࢜ࢲ࣮ࡢ༢⤖ᬗ 㔪≧ ࡛ࡣ᭷ព࡟኱ࡁ࡞ࡶࡢ࡜࡞ࡗ࡚࠸ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ
ࡑࡇ࡛㸪 ᖺᗘ࡛ࡣ 137 HQVHPEOH D  E  J  ࢆ⏝࠸㸪. ࡟࠾ࡅࡿ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ ࢆ ⾜ ࡗ ࡓ ࠋ ࡑ ࡢ ⤖ ᯝ 㸪 >&D &2 F+2 ࣭ S+2@Q 㔞Ꮚ +2 ࡢ᱁Ꮚᐃᩘ㸸a c㸪c c㸪>&D &2 F+2࣭S'2@Q 㔞Ꮚ '2ࡢ᱁Ꮚᐃᩘ㸸a c㸪c c ࡜- 407 -

ᅗ   S+2 ࠾ࡼࡧ S'2 ࡢ㒊ศືᚄศᕸ㛵ᩘ
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[1] “Variable control of the electronic states of a silver nanocluster via protonation/deprotonation of polyoxometalate
ligands”
K. Yonesato, S. Yamazoe, S. Kikkawa, D. Yokogawa, K. Yamaguchi, K. Suzuki,   
[2] “A Molecular Hybrid of an Atomically Precise Silver Nanocluster and Polyoxometalates for H2 Cleavage into
Protons and Electrons”
K. Yonesato, S. Yamazoe, D. Yokogawa, K. Yamaguchi, K. Suzuki,
Angew. Chem. Int. Ed. 2021, 60, 16994-16998.
[3] “Nanostructured Manganese Oxides within a Ring-Shaped Polyoxometalate Exhibiting Unusual Oxidation Catalysis”
K. Sato, K. Yonesato, T. Yatabe, K. Yamaguchi, K. Suzuki,
Chem. Eur. J. 2022, 28, e202104051.
[4] “Robotic Stepwise Synthesis of Hetero-Multinuclear Metal Oxo Clusters as Single-Molecule Magnets”
T. Minato, D. Salley, N. Mizuno, K. Yamaguchi, L. Cronin, K. Suzuki,
J. Am. Chem. Soc. 2021, 143, 12809–12816.
[5] “Synthesis of a phosphomolybdate with a tetranuclear vanadium core by installing vanadium atoms in a lacunarytemplate using protecting group strategy”
C. Li, K. Yamaguchi, K. Suzuki,
Chem. Commun. 2021, 57, 6530–6533.

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[1] Casalino, L. et al. ACS Cent. Sci. 2020, 6, 17221734.
[2] Watanabe, Y. et al. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, 73207325.
[3] Re, S.; Mizuguchi, K. J. Phys. Chem. B 2021, 125, 20892097.
[4] Kamiya, M.; Sugita, Y. J. Chem. Phys. 2018, 149:072304.
[5] Jung, J. et al. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2015, 5, 310–323.
[6] Kobayashi, C. et al. J. Comput. Chem. 2017, 38, 2193–2206.
[7] Sugita, Y. et al. Methods in Molecular Biology 2019, 2022, 155–177- 414 -

᭷ᶵ㔠ᒓゐ፹ࢆ⏝࠸ࡓ཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Reaction Mechanisms of Organometallic
Catalysis‫ۑ‬ᒣᮏ ဴஓࠊΎỈ ᮍ⣖ࠊᱵ⏣ ᛭ࠊᐑᆏ ㄔ㸦ᮾி㟁ᶵ኱Ꮫ㸧
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࣓ࢱࣝ໬ࡣ $U ࢆ㑊ࡅࡿ఩⨨࡛㐍⾜ࡋ࡚࠾ࡾࠊ$U ࡢ኱ࡁࡉࡀ཯ᛂ㏿ᗘ࡟኱ࡁࡃᙳ㡪ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

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6\PSRVLXP  ࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ㛤ദ‫ ࠐ ۻ‬,VDPL 1DNDMLPD <XWD 2NXGD 7HWVX\D <DPDPRWR ࠊ͆ &DWDO\VLV RI %XON\ \HW )OH[LEOH 1+& &RRUGLQDWHG
&\FORPHWDODWHG3DOODGLXP+\GUR[LGH&RPSOH[HV͇ VW7HWUDKHGURQ6\PSRVLXP  ࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ㛤ദฟ∧ᐇ⦼ࡲࡓࡣணᐃ
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[NiFe]ࣄࢻࣟࢤࢼ࣮ࢮࡣࠊNi ࡜ Fe ཎᏊࢆྵࡴάᛶ㒊఩࡟࠾࠸࡚ࠊỈ⣲ศᏊࡢศゎ࣭ྜᡂ཯ᛂࢆᖖᖖᅽ࡛ゐ፹ࡍࡿࠋ㓟໬ᆺ[NiFe]ࣄࢻࣟࢤࢼ࣮ࢮ࡟ࡣࠊNi-A ࡜ Ni-B ࡞࡝ࡢάᛶ୰ᚰࡢ≧ែࡀᏑᅾࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸
ࡿࠋࡑࢀࡒࢀ Ni ࡜ Fe ࡢ஧᰾୰ᚰᵓ㐀ࢆᣢࡕࠊ–O ࡶࡋࡃࡣ–OH ࡀ㔠ᒓཎᏊ㛫ࢆᯫᶫࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚
࠸ࡿࠋFe ࡣ 2 ౯≧ែ࡛࠶ࡿ࡜≉ᐃࡉࢀ࡚࠸ࡿࡀࠊNi ཎᏊࡢ㓟໬ᩘࡸࢫࣆࣥ≧ែࡢ≉ᐃ࡟ࡣ⮳ࡗ࡚࠸࡞࠸ࠋࡑ
ࡇ࡛ᮏ◊✲࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾྛ㓟໬≧ែࡢᏳᐃᵓ㐀ࢆ᥈⣴ࡋࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ㓟
໬ᆺ[NiFe]ࣄࢻࣟࢤࢼ࣮ࢮࡢάᛶ୰ᚰࡢᵓ㐀࡜㟁Ꮚ≧ែࢆ≉ᐃࡍࡿࠋ◊✲᪉ἲࠊィ⟬᪉ἲ㓟໬ᆺ[NiFe]ࣄࢻࣟࢤࢼ࣮ࢮࡢྛᯫᶫᵓ㐀࡜ Ni ࡢ㟁Ꮚ≧ែ࡟ᑐࡋ࡚ࠊONIOM ἲ࡟ࡼࡿάᛶ୰ᚰࡢᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋONIOM ἲࡢ High Layer 㡿ᇦࡣࠊBP86 ỗ㛵ᩘࢆ⏝࠸ࡓ DFT ィ⟬ࢆ⾜࠸ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚
6-31G*ࢆ⏝࠸ࡓࠋLow Layer 㡿ᇦࡣࠊAmber ຊሙ࡟ࡼࡿ MM ィ⟬࡟ࡼࡗ࡚⾜ࡗࡓࠋ඲࡚ࡢィ⟬ࡣࠊGaussian 16ࣃࢵࢣ࣮ࢪࢆ⏝࠸࡚⾜ࡗࡓࠋᚓࡽࢀࡓᏳᐃᵓ㐀࡜ X ⥺⤖ᬗᵓ㐀࡜ࡢ RMSD ࢆㄪ࡭ࠊࡶࡗ࡜ࡶᑠࡉ࠸ RMSDࢆᣢࡘࣔࢹࣝࢆㄪ࡭ࡿࡇ࡜࡟ࡼࡾࠊ㓟໬ᆺ[NiFe]ࣄࢻࣟࢤࢼ࣮ࢮࡢྲྀࡾᚓࡿᵓ㐀࡜㟁Ꮚ≧ែࢆỴᐃࡋࡓࠋ

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୍ࡘࡣࠊపࢫࣆࣥ≧ែࡢ Ni3+࡜ OH−ࡢᯫᶫ㓄఩Ꮚࢆᣢࡘ≧ែ࡛ࠊᥦ᱌ࡉࢀ࡚࠸ࡿᵓ㐀࠾ࡼࡧ㟁Ꮚ≧ែ࡜୍⮴ࡋࡓࠋ2 ࡘ┠ࡣࠊపࢫࣆࣥ≧ែࡢ Ni2+࡜ S–O ࡀ Ni ࡜ Fe ࡟ᯫᶫࡋࡓ≧ែ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣࠊࡇ
ࢀࡲ࡛࡟≉ᐃࡉࢀ࡚࡞࠸᪂ࡓ࡞㓟໬≧ែ࡛࠶ࡾࠊ⌮ㄽィ⟬࡟ࡼࡾࠊࡑࡢヲ⣽࡞ᵓ㐀࡜㟁Ꮚ≧ែࡀᚓࡽࢀࡓࠋ

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ࠊ2P02ࠊ࢜ࣥࣛ࢖ࣥࠊ2021 ᖺ 11 ᭶Ώ㎶୐㒔⛥ࠊᗉྖග⏨ࠊᇼඃኴࠊ㔜⏣⫱↷ࠊࠕ㝹▼୰࡛ࡢ࢔࣑ࣀ㓟࢟ࣛࣝቑᖜᶵᵓ࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊✲ࠖࠊࠗ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍࠘
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࣮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
3.1 ࢖࣑ࣀ࢟ࢩࣝࣛࢪ࢝ࣝࢆ฼⏝ࡋࡓࢱࣥࣃࢡ㉁୰ࡢࢳࣟࢩࣥ㑅ᢥⓗಟ㣭ࢱࣥࣃࢡ㉁୰ࡢ≉ᐃࡢṧᇶࢆ໬Ꮫ㑅ᢥⓗ࡟ಟ㣭࡛ࡁࡿᡭἲࡣࢣ࣑࢝ࣝࣂ࢖࢜ࣟࢪ࣮ࢶ࣮ࣝ࡜ࡋ࡚ࡢᛂ⏝ࡸ⩻ヂᚋಟ㣭ࡢ⌮ゎ࡞࡝࡟኱ࡁࡃᙺ❧ࡘࠋ௒ᅇࠊ⏦ㄳ⪅ࡽࡣ࢖࣑ࣀ࢟ࢩࣝࣛࢪ࢝ࣝࡀ໬Ꮫ㑅ᢥⓗ࡟ࢱࣥࣃࢡ㉁୰ࡢࢳࣟࢩࣥ࡟ྵࡲࢀࡿࣇ࢙ࣀ࣮ࣝ㒊఩࡜໬Ꮫ㑅ᢥⓗ࡟཯ᛂࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࡇ࡛࢖࣑ࣀ࢟ࢩࣝࣛࢪ
࢝ࣝࡢ཯ᛂᛶࢆண

ࡍࡿࡓࡵ࡟ࠊᑐᛂࡍࡿࣄࢻࣟ࢟ࢩࣝ࢖࣑ࣥࡢ O-H ⤖ྜࡢ⤖ྜ஋㞳࢚ࢿࣝࢠ࣮㸦BDE㸧ࢆᣦᶆ࡟ࡋ࡚ศᏊタィ࡟⏝࠸ࡿࡇ࡜࡟ࡋࡓࠋ࢖࣑ࣀ࢟ࢩࣝࣛࢪ࢝ࣝ࡜ࢳࣟࢩࣥ࡜ࡢ཯ᛂᛶࡣ⨨᥮ᇶࡢ❧య㞀ᐖ࡟┦㛵ࡋ࡚࠾ࡾࡇࢀࡣ DFT ィ⟬ࡢ⤖ᯝ࡜୍⮴ࡍࡿࡶࡢ࡛࠶ࡗࡓࠋࡇࡢ⤖ᯝࢆ฼⏝ࡋ᭱㐺ࡢศᏊࢆぢฟࡍ࡟⮳ࡗࡓࠋ- 417 -

3.2

࣭࣎ࣟࣥࢩࣜࢥࣥ஧㔜άᛶ໬ᶵᵓ࡟ࡼࡿ࢝ࣝ࣎ࣥ㓟㑅ᢥⓗ࢔ࣝࢻ࣮ࣝ཯ᛂࡢ㛤Ⓨ࢝ࣝ࣎ࣥ㓟ࡣ་⸆ရࡸ⏕≀άᛶศᏊ࡟㢖ฟࡍࡿᐁ⬟ᇶ࡛࠶ࡾࠊࡇࡢᐁ⬟ᇶࡢ໬Ꮫ㑅ᢥⓗ࡞ᐁ⬟ᇶ໬཯ᛂࡣ
་⸆ศᏊྜᡂ࡟኱ࡁࡃᙺ❧ࡘࡇ࡜ࡀண᝿ࡉࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽ࢝ࣝ࣎ࣥ㓟ࡢȘ఩ࣉࣟࢺࣥࡢ pKa ࡣ㠀ᖖ࡟㧗ࡃࠊ໬Ꮫ㑅ᢥⓗ࡟⬺ࣉࣟࢺࣥ໬ࡍࡿࡇ࡜ࡣ㞴ࡋ࠸ࠋ௒ᅇ⏦ㄳ⪅ࡽࡢࢢ࣮ࣝࣉࡣ௨๓࡟ぢฟࡋ࡚࠸ࡓ࣎ࣟࣥゐ፹࡟ຍ࠼ࠊࢩࣜࢥࣥῧຍ๣ࢆῧຍࡍࡿࡇ࡜࡛໬Ꮫ㑅ᢥⓗ࡟࢝ࣝ࣎ࣥ㓟࠿ࡽ࢚ࣀ࣮ࣛࢺࢆᙧᡂ࡛ࡁࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࡢ≉␗࡞ຠᯝࢆゎ᫂ࡍࡿࡓࡵ࡟ࠊ୰㛫య࡜ࡋ࡚᝿ᐃࡉࢀࡿࢩ࢚ࣜࣝࢫࢸࣝࡢ pKa ࢆィ⟬ࡍࡿࡇ࡜࡜ࡋࡓࠋࡑࡢ⤖ᯝࢩ࢚ࣜࣝࢫࢸࣝࡣ௨๓ࡲ࡛࡟⏦ㄳ⪅ࡽࡀぢฟࡋ࡚࠸ࡿ࢚࣎ࣟࣥࢫࢸࣝ࡜ྠ➼ࡢ㓟ᛶᗘࢆᣢࡘࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢάᛶ໬ᶵᵓ࡟ຍ࠼ࠊ࣎ࣟࣥゐ፹ࡢάᛶ໬࡟ࡼࡾࡉࡽ࡟ pKa ࡀୗࡀࡾࠊ໬Ꮫ㑅
ᢥᛶࡢⓎ⌧࡟ࡘ࡞ࡀࡗ࡚࠸ࡿࠋ

3.3

ࢤ࣐ࣝࢽ࣒࢘ゐ፹ࢆ⏝࠸ࡓ⤖ྜᙅ໬ᡓ␎࡟ࡼࡿ୍⣭࢔࣑ࣥȘ఩ C-H ⤖ྜࡢᐁ⬟ᇶ໬཯ᛂࡢ㛤Ⓨ་⸆ရྜᡂ࡟ᙜࡓࡾࠊᏳᐃ࡞᭷ᶵ໬ྜ≀ࡢ C-H ⤖ྜࢆ┤᥋ⓗ࡟ᐁ⬟ᇶ໬ࡍࡿᡭἲࡣᕤ⛬ᩘࡸᗫᲠ≀ࢆ๐ῶ࡛ࡁࡿ᭷⏝࡞ᡭἲ࡛࠶ࡿࠋ୰࡛ࡶ㏆ᖺගゐ፹࣭Ỉ⣲ཎᏊ⛣ື㸦HAT㸧ゐ፹⣔ࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋࡇࡇ࡛ࡣࣛࢪ࢝ࣝゐ፹άᛶ✀ࡀ C-H ᘬᢤࡁࢆ⾜࠺ࡀࠊࡑࡢ఩⨨㑅ᢥᛶࡀၥ㢟࡜࡞ࡗ࡚࠸ࡿࠋ୍᪉࡛≉ᐃࡢᐁ⬟ᇶࡢࡳ㑅ᢥⓗ࡟άᛶ໬ࡋࠊᑐ㇟ࡢ C-H ⤖ྜࢆᙅ໬ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤ໬Ꮫ㑅ᢥⓗ࡟ᐁ⬟ᇶ໬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ୍⣭࢔࣑ࣥࡣ⏕≀άᛶศᏊ࡟ࡼࡃぢࡽࢀࡿ㔜せ࡞ᐁ⬟ᇶ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ୍⣭࢔࣑ࣥȘ఩ C-H 㑅ᢥⓗ࡞άᛶ໬ࡣ௒ࡲ࡛࡟౛ࡀ࡞࠸ࠋࡇࡇ࡛࢔࣑ࣥ࡟㓄఩ࡋ࡚࢔࣑ࣥୖࡢ㟁Ꮚᐦᗘࢆୖࡆࠊ⤖ྜ஋㞳࢚ࢿࣝࢠ࣮ࢆᑠࡉ
ࡃࡍࡿάᛶ໬ゐ፹࡜ࡋ࡚ࢤ࣐ࣝࢽ࣒࢘ゐ፹ࢆ᝿ᐃࡋࡓࠋᐇ㝿࡟ࡇࡢゐ፹࡟ࡼࡾάᛶ໬ࡀ㉳ࡁࡿ࠿ࢆ DFT ィ⟬࡟ࡼࡾ☜࠿ࡵࡿࡇ࡜࡜ࡋࡓࠋィ⟬ࡢ⤖ᯝ࡟ࡼࡿ࡜ᐇ㝿࡟ࢤ࣐ࣝࢽ࣒࢘ࡢ㓄఩࡟ࡼࡾࠊ⤖ྜᙅ໬ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᐇ㝿࡟ࢤ࣐ࣝࢽ࣒࢘ゐ፹ࢆῧຍࡋࡓ࡜ࡇࢁ෇⁥࡟཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟ࡶ☜࠿ࡵࡽࢀࠊィ⟬࡜ࡢᩚྜᛶࡀ☜ㄆࡉࢀࡓࠋ

- 418 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ ➨ ۻ‬47 ᅇ཯ᛂ࡜ྜᡂࡢ㐍Ṍࢩ࣏ࣥࢪ࣒࢘ࠕࢩ࢚ࣜࣝࢫࢸࣝάᛶ໬࡟ࡼࡿ࢝ࣝ࣎ࣥ㓟㑅ᢥⓗゐ፹ⓗ୙ᩧ࢔ࣝࢻ࣮ࣝ཯ᛂࠖ⸨⏣኱ᶞࠊᒣ᰿୕ዉࠊSameera W. M. Cࠊ୕ࢶ἟἞ಙࠊ㔠஭ồ
[2] ‫ ۻ‬᪥ᮏ໬Ꮫ఍➨ 102 ᫓Ꮨᖺ఍ࠕSite-selective α-C(sp3)−H Alkylation of Alcohols and Primary Amines
Promoted by Photoredox, HAT, and Bond-Weakening Hybrid CatalysisࠖKentaro Sakai, Kounosuke Oisaki, Motomu
Kanai[3] ‫ ۻ‬᪥ᮏ⸆Ꮫ఍➨ 142 ᖺ఍ࠕࢤ࣐ࣝࢽ࣒࢘ᆺ᪂つ⤖ྜᙅ໬ゐ፹ࢆ⏝࠸ࡓ 1 ⣭࢔࣑ࣥȘ఩ C(sp3)-H ࢔ࣝ࢟ࣝ໬ࠖᆏ஭೺ኴ㑻ࠊ⏕㛗ᖾஅຓࠊ㔠஭ồฟ∧ᐇ⦼ࡲࡓࡣணᐃ
>@ ‫ ۻ‬0DUX\DPD.,VKL\DPD76HNL<6DNDL.7RJR72LVDNL..DQDL0-$P&KHP6RF


>@ ‫) ۻ‬XMLWD7<DPDQH06DPHHUD:0&0LWVXQXPD+.DQDL0$QJHZ&KHP,QW(G

>@ ‫ ۻ‬6DNDL.2LVDNL..DQDL02UJ/HWW

- 419 -





Theoretical study of chemical reactions andfunctional conformational dynamics of biomolecules *



)

#$+

 #$"!mznw cÉ)¡§^ey  ey½.g*$n #
f¨+*+(n n[ j§^eyUxw¿© ØZ )b¿©Ø*IAT<MQ2EQ6VÝ.Å!* sÛ*$¿©2EQ6VÝ&ÝXÑ±¢Ü¬atnÇÆ wÀ-+ , Ó·n&§^ey½Ø-*mzn eyÌ( &Ð¬¢ ÕÁh.* Ê|ß (( )*$mzn%j+Ø-*>1DK7=¡n[p)Ìum 'É)k£¬n&½«¤ |¤+* .¥Ã* $(+* '§^ey.[ d»¶ *mzn~ÖymzÄ´eyliz<KNRV<OT¥Æmz.¨*nÐ²ey.>1DK7="
( *.­* ¡\YÞ­o)¸/
1.1 Ó· *nØ-*ÎÌumeyÉ¥Æ¬ÃÓ·n +"¹ÌÃj0KFÔuª^.¨nË{ËÆ¬ÃwÀ-+ +~FRET WeyÄ& NMR( `Ó·eynË( &tÈU§ ¾ÚÐ² *Ó·[×¢ Â+Ó·n;17Qb^ *Ó·Ì( &¢Ñ±}ZÕÁ ¯r+*®³ ¿©2EQ6VÝtnËÃjÑ±Ð²>1DK7=|Ùn ÍÀ*Ð²<KNRV<OT.ÀnÐ² Ó·Ìum&Ïl h.¥Ã*.­¡HSPTª
mÓ· Pin1 ._NMR ºqe¯r+*J17S°KP°3V>VÎ>1DK7=
' Pin1 cÉ)"+ ªmn4@HQ* .ey<KNRV<OT.¨
( *.­¬
1.2 <7SB5=CPT.¨*]¼Ò¬ C-H CPGQ3SL?QmnÃ
<7SB5=CPT(  ey8Q9V= (+*¦¢3P:µ)
¦v: ­c: (V7¡o.*+.f¨ Y 4[ey.
Az*  *$ÃIXey³µª u^%¨(+*9Í<7SB5=CPT.¯x¨*_ WK+ * 9Í<7SB5=CPT znØZ*_ aÊ<7SB5=CPT.¨*q0YÒ¬©ÎmH  &+ C
PGQ3SL?Qmn ÍÀ* WK+ Q  CPGQ3SL?Qt &)BªL·ªJ"+*Çf¨^½t*$+"CPGQ3SL?Qt.`=* ~wÂ«+  [%©ÎmH ]¼Ò¬ &+ CPGQ3SL?Qmn
 _ aWK+n_%tÈ¾It.`=*pÁ )o)Ä sÛ- 420 -

MÌ  MÌ%<7SB5=CPT.¨*}N+*<7SB5=CPT.
¨n/DQJORLV ²ªÐ&)621DÑ 7%+3 %X22+ ' )4Q¬CPGQ3SL?Qm ÍÀ*"tÈ.<7SB5=CPTcA *¾It`=]¼Ò I
X* ¬?++ 105 |ß (tÈ <7SB5=CPTcA+*¹ n(+* '<7SB5=CPT 3¨** ®³ ÖymzÄ´eyliz<KNRV<OT.¸#H- *CPGQ3SL?Qmney<7SB5=CPT' n ']¼Ò¬ÍÀ* .( *.­

Q 1. <7SB5=CPT.¨]¼Ò¬ C-H CPGQ3SL?Qmn
1.3 R0 `=+ !PTT¾]y Ir ¯x'*©Î C-H %·mnÃ
%·mHu{n.¥^½tu{ *$ÇfÕÁ[×^*H   ,U ¯x.¨*©ÎmH ]¼Ò¬ &+ %·mn x(+*n ,h¾]y.¨*©ÎST¼{^.¥©

z &+ .%·m *$¨n*(n ©Î¦¼{t ÏijÈ.F¹f¼{n ÛL].Ò¬^½tm *$+"w®³ +   /X ('  51
P'¿^ = !D9)VC &ST %SLQ R0 `=+ !PTT¾]y©Î
0K.¨*q0Yn 6Í+* ¬?+ Q  n 0KÔ·¾]yR0¼e ·¹H.*')6Í+*§(+*"©Î2=
AQXHn 2Y* e* CP (  ®³

 ÖymzÄ´.¨ney.Ã(¾]yº n'jÈ*
.Å!*.­¬

Q 2. R0- !PTT¾]y.¨* Ir ¯x C-H %·mn #$(%
2.1 Ó· *nØ-*ÎÌumeyÉ¥Æ¬Ã
 HSPTªmÓ· Pin1 ÎÌumU¢Ñ±Ð².eyliz<KNRV<OT' Å!
¡tÈ¢

Pin1 >1DK7=jÈ.E .( *$tÈ ¹H apo Tjcis Ttrans TtÈ

Pin1 ¹HXH%°+ +10 J17S

- 421 -

°Á ×eyliz<KNRV<OT. 20 O |À+(C)7CP *T
7ÈÎÏl.( *$+À N-H ¹HØ*®ØØ~.Ä´+(J"+* {~ee.¸)H)=u{' $+(eyliz<KNRV<OT

Amber20 .¨


2.2 <7SB5=CPT.¨*]¼Ò¬ C-H CPGQ3SL?QmnÃ>^¬ &+ CPGQ3SL?QmntÈLC5<$TT.¨tÈ/DQJORLV ²ªÐ&)621DÑ 7%+3 %X22+ .j*'n ÍÀ* .*DXVVLDQ5HY& .¨ÖymzÄ´' Å!(tÈ <7SB5=CPTcA+*Ð² '«H^]{Ì.Å!*$$PEHU .¨ 0' <KNRV<OT.|À
2.3 R0 `=+ !PTT¾]y Ir ¯x'*©Î C-H %·mnÃn

 51P'¿^ ,U/ %SLQ (Z")tÈ &+ Ôm¬/j+%SLQ ¾Ú%SLQ/j»<¬¾Ú'*§ ¾Ú Ð² * Ôm¬/jmÉn ÍÀ*
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2022  3 , GËÐvkÑ
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T. Kikutsuji, Y. Mori, K. Okazaki, T. Mori, K. Kim, N. Matubayasi, “Explaining reaction coordinates of alanine

dipeptide isomerization obtained from deep neural networks using Explainable Artificial Intelligence (XAI)”, J. Chem.
Phys. 156, 154108 (2022)
 T. Mori, S. Saito, “Molecular Insights into the Intrinsic Dynamics and their Roles During Catalysis in Pin1 Peptidylprolyl Isomerase”, (submitted)
 A. Shiozuka, K. Sekine, T. Toki, K. Kawashima, T. Mori, Y. Kuninobu, “Photoinduced Divergent Deaminative
Borylation and Hydrodeamination of Primary Aromatic Amines”, (submitted)
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ሙ ✭ 1 ࠊ༡ ಇ໶ 1 ࠊᒾᒣ ࡵࡄࡳ 1
1. ⤫ィᩘ⌮◊✲ᡤ ࡶࡢ࡙ࡃࡾࢹ࣮ࢱ⛉Ꮫ◊✲ࢭࣥࢱ࣮
2. ᮾிᕤᴗ኱Ꮫ

≀㉁࣭᝟ሗ༟㉺ᩍ⫱㝔◊✲┠ⓗᮏ◊✲࡛ࡣࠊ㧗ศᏊᮦᩱࡢ࣐͆ࢸࣜ࢔ࣝࢬ࢖ࣥࣇ࢛

࣐ࢸ࢕ࢡࢫ㸦MI㸧͇ࢆᑐ㇟࡜ࡋࡓ⤫ィⓗᶵᲔᏛ⩦ࡢᇶ┙ᢏ⾡ࢆᵓ⠏ࡍࡿࠋ୍⯡࡟ᮦᩱ◊✲ࡢタィኚᩘࡢ✵㛫ࡣᴟࡵ࡚ᗈ኱࡛࠶ࡿࠋ౛࠼ࡤ᭷ᶵᮦᩱࡢ᭱ࡶᇶᮏⓗ࡞ᵓᡂせ⣲࡛࠶ࡿ᭷ᶵศᏊࡢ໬Ꮫ✵㛫࡟ࡣࠊ1060 ࢆ㉸࠼ࡿೃ⿵ᵓ㐀ࡀᏑᅾࡍࡿ࡜ゝࢃࢀ࡚࠸ࡿࠋ᪂ᮦᩱࡢ◊✲㛤
Ⓨ࡛ࡣࠊࡇࡢࡼ࠺࡞ᗈ኱࡞᥈⣴✵㛫࠿ࡽᡤᮃࡢ≀ᛶࢆ᭷ࡍࡿศᏊࢆຠ⋡ⓗ࡟᥈⣴ࡍࡿࡇ࡜ࡀồࡵࡽࢀࡿࠋ
ᮏ◊✲࡛ࡣࠊࢹ࣮ࢱ⛉Ꮫ࡜ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ
⼥ྜᡭἲࢆ⏝࠸࡚ࠊࡇࡢၥ㢟࡟࢔ࣉ࣮ࣟࢳࡍࡿࠋࢹ࣮
ࢱゎᯒࡢ୍⯡ⓗ࡞࣮࣡ࢡࣇ࣮ࣟࡣࠊ㡰ၥ㢟࡜㏫ၥ㢟ࡢᙧᘧ࡟ᖐ╔ࡍࡿ㸦ᅗ 1㸧ࠋ㡰ၥ㢟࡛ࡣࠊほ࠸࡚ࠊศᏊᵓ㐀࠿ࡽ≀ᛶࢆணࢹ࣮ࢱࢆ⏝ࡍࡿ⤫ィࣔࢹࣝࢆᵓ⠏ࡍࡿࠋࡇࢀ࡟ᑐࡋ㏫ၥ㢟࡛ࡣࠊ࣋࢖ࢬ᥎ㄽࢆ㐺⏝ࡋࣔ
ࢹࣝࡢ㏫෗ീࢆồࡵ࡚ࠊᡤᮃࡢ≀ᛶ್ࢆ᭷ࡍࡿೃ⿵ศ
Ꮚࢆ⏕ᡂࡍࡿࠋࡉࡽ࡟ࠊ࣋࢖ࢬ᭱㐺໬࡟ᇶ࡙ࡁ≀ᛶィ⟬ࡢᑐ㇟ศᏊࢆ㑅ᐃࡋࠊእᤄ㡿ᇦ࡟ࢹ࣮ࢱࢆ㏣ຍࡋ࡞
ࡀࡽࠊࣔࢹࣝࡢண

ྍ⬟⠊ᅖࢆẁ㝵ⓗ࡟ᣑ኱ࡋ࡚࠸ࡃࠋ ᅗ 1.

ࡇࡢࢧ࢖ࢡࣝࢆ⧞ࡾ㏉ࡍࡇ࡜࡛ࠊእᤄ㡿ᇦ࡟Ꮡᅾࡍࡿ

࣋࢖ࢬ᥎ㄽ࡜ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿእ
ᤄⓗᮦᩱ᥈⣴

㠉᪂ⓗ࡞᪂ᮦᩱࢆྠᐃࡍࡿࠋ
ࡇࡇ࡛ࡢ኱ࡁ࡞ၥ㢟ࡣࠊ㧗ศᏊᮦᩱศ㔝࡛ࡣࢹ࣮ࢱࡀ࡞࠸࡜࠸࠺ࡇ࡜࡛࠶ࡿࠋ௚ࡢᮦᩱ⣔࡟ẚ࡭ࡿ࡜㧗ศᏊᮦᩱࡢࢹ࣮ࢱ㔞ࡣᅽಽⓗ࡟ᑡ࡞࠸ࠋ≉࡟ࠊࢹ࣮ࢱ㥑ືᆺ◊✲࡟㈨ࡍࡿࣞ࣋ࣝࡢ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࡣ
⌧᫬Ⅼ࡟࠾࠸࡚ᐇ㉁ⓗ࡟Ꮡᅾࡋ࡞࠸ࠋࡲࡓࠊ㠉᪂ⓗ࡞ᮦᩱࡢ࿘㎶࡟ࡣࢹ࣮ࢱࡣᏑᅾࡋ࡞࠸ࠋࢹ࣮ࢱ⛉Ꮫࡢணࡣࠊ୍⯡ⓗ࡟ෆᤄⓗ࡛࠶ࡾࠊࢹ࣮ࢱࡀᏑᅾࡋ࡞࠸ᮍ㋃㡿ᇦ࡟࠾࠸࡚ࡣࡑࡢ᭷ຠᛶࡣኻࢃࢀࡿࠋࡋࡓࡀࡗ࡚ࠊ

- 426 -

༢⣧࡞ࢹ࣮ࢱ㥑ື࡛ࡣཎ⌮ⓗ࡟ࡣ┿࡟㠉᪂ⓗ࡞ᮦᩱ࡟฿㐩࡛ࡁ࡞࠸ ࠋࡍ࡞ࢃࡕࠊၥ㢟ࡢᮏ㉁ࡣࢹ࣮ࢱࡀ࡞࠸
࡜࠸࠺ࡇ࡜࡛࠶ࡿࠋ
ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊ≀ᛶࡢ඲⮬ືィ⟬ࢩࢫࢸ࣒㸦RadonPy㸧
ࢆ㛤Ⓨࡋࠊ௬᝿ᐇ㦂࡟ࡼࡾࢹ࣮ࢱ㥑ືᆺ◊✲࡟㈨ࡍࡿໟᣓⓗ࡞㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠
ⓗ࡜ࡋࡓࠋ

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◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛㛤Ⓨࡋࡓ MD ィ⟬ࢆ⏝࠸ࡓ㧗ศᏊ≀ᛶ⮬ືィ⟬ࢩࢫࢸ࣒ RadonPy ࡢᴫせࢆᅗ 2 ࡟♧ࡋࡓࠋᮏࢩࢫࢸ࣒ࡣࠊ㟁Ꮚ≧ែィ⟬ࢯࣇࢺ࢙࢘࢔ Psi4 ࡜඲ཎ
Ꮚ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢯࣇࢺ࢙࢘࢔ LAMMPSࢆࢫࣃࢥࣥୖࡢ」ᩘࣀ࣮ࢻ࡛୪ิᐇ⾜ࡍࡿࡇ࡜ࢆ᝿
ᐃࡋ࡚㛤Ⓨࡉࢀࡓ Python ࣛ࢖ࣈ࡛ࣛࣜ࠶ࡿࠋ
ධຊࡣࠊ㧗ศᏊࡢ⧞ࡾ㏉ࡋࣘࢽࢵࢺࡢ SMILES㸦໬ྜ≀ࡢ㸯ḟᵓ㐀ࢆ⾲ࡍᩥᏐิ㸧ࡸ㔜ྜᗘࠊᗘ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㔜ྜᗘࡣ࣏࣐࣮ࣜ㙐ࡢཎᏊᩘࡀ⣙ 1ࠊ000 ࡟࡞ࡿࡼ࠺࡟ㄪᩚࡋࠊ300 K࣭1 atm ࡢ᮲௳࡛ィ⟬ࢆ⾜ࡗࡓࠋࣃ࢖ࣉࣛ࢖ࣥࡢ࣮࣡ࢡࣇ࣮ࣟࡣࠊḟࡢ㏻ࡾ࡛
࠶ࡿ㸸㸦1㸧❧య㓄ᗙ⏕ᡂ࢔ࣝࢦࣜࢬ࣒ࡢ ETKDG ἲࢆ⏝࠸⧞ࡾ㏉ࡋࣘࢽࢵࢺࡢ❧య㓄ᗙࢆ⏕ᡂࠊ㸦2㸧⧞ࡾ㏉ࡋࣘࢽࢵࢺࡢ Psi4 ࢆ⏝࠸ࡓ㟁Ⲵィ⟬ࠊ
㸦3㸧⧞ࡾ
㏉ࡋࣘࢽࢵࢺࢆ self-avoiding random walk ἲ࡟ࡼࡾ㐃ᅗ 2.

㧗ศᏊ≀ᛶ⮬ືィ⟬ࢩࢫࢸ࣒ᴫせ⤖ࡋࠊࣛࣥࢲ࣒ࢥ࢖ࣝ≧ࡢ㧗ศᏊ㙐ࢆ⏕ᡂࠊ㸦4㸧ࡇࡢ㧗ศᏊ㙐ࢆ 10 ᮏ」〇ࡋࠊ஫࠸࡟㔜࡞ࡽ࡞࠸ࡼ࠺ࣛࣥࢲ࣒࡟㓄⨨࣭ᅇ㌿ࡋࠊ࢔ࣔࣝࣇ࢓ࢫ㧗ศᏊࡢึᮇᵓ㐀ࢆ⏕ᡂࠊ㸦5㸧MD ィ⟬࡟ᚲせ࡞ຊሙࣃ࣓࣮ࣛࢱ㸦GAFF2㸧๭ࡾᙜ࡚࡜ィ⟬᮲௳ࡢࢭࢵࢺ࢔ࢵࣉࠊ
㸦6㸧Larsen ࡽࡢᡭἲ (G. Larsen et al., Macromolecules 44, 6944-6951 (2011)) ࢆ⏝࠸ࡓ⣔ࡢᵓ㐀⦆࿴ࡢࡓࡵࡢᖹ⾮໬ MD ࢆ
LAMMPS ࡟ࡼࡾᐇ⾜ࠊ㸦7㸧࢚ࢿࣝࢠ࣮ࡸᐦᗘ࡞࡝ࡢ཰᮰≧ἣ࠿ࡽᖹ⾮໬ MD ィ⟬ࡢ⤊஢ࢆ⮬ືⓗ࡟ุᐃࠊ㸦8㸧ᖹ⾮໬ MD ࡢ⤖ᯝ࠿ࡽᐦᗘࠊẚ⇕ࠊ⇕⭾ᙇಀᩘࠊయ✚ᙎᛶ⋡ࠊᒅᢡ⋡ࠊ㟼ⓗㄏ㟁⋡࡞࡝ࢆ⟬ฟࠊ
㸦9㸧ᖹ
⾮໬ᚋࡢᵓ㐀࡟ᑐࡋ࡚⇕ὶ᮰ࢆ㥑ືࡋࡓ㠀ᖹ⾮㸦⇕ఏᑟ㸧MD ࢆ LAMMPS ࡛ᐇ⾜ࡋࠊ⇕ఏᑟ⋡ࢆ⟬ฟࡋࡓࠋ

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◊✲ᡂᯝ
3.1

ࠕ㧗ศᏊ≀ᛶ⮬ືィ⟬࢔ࣝࢦࣜࢬ࣒࣭ࢯࣇࢺ࢙࢘࢔ࡢ㛤Ⓨࠖ ᖺᗘࡣ࢔ࣔࣝࣇ࢓ࢫ࣏࣐࣮ࣜࡢ  ≀ᛶࡢ⮬ືィ⟬ࢆᐇ⿦ࡋࠊࣉࣞࣉࣜࣥࢺࡢබ㛤࡜ 5DGRQ3\ ࡢࣇ࢓࣮ࢫࢺ࣮ࣜࣜࢫࢆ⾜ࡗࡓࠋ≀ᛶィ⟬್ࡢጇᙜᛶࡣࠊ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫ 3R/\,QIR㸦ᩥ⊩࠿ࡽᢳฟࡋࡓ≀ᛶ್ࢹ࣮ࢱ࣮࣋ࢫ㸧ࡢ  ࣏࣐࣮ࣜࡢ≀ᛶ್࡜ࡢ⣔⤫ⓗ࡞ẚ㍑᳨ド࡟ᇶ࡙࠸᳨࡚ドࡋࡓࠋϕϪϕϨϱφ࿨ ชʁ Y. Hayashi, J. Shiomi, J. Morikawa, R. Yoshida, "RadonPy: Automated Physical Property
Calculation using All-atom Classical Molecular Dynamics Simulations for Polymer Informatics ," arXiv:2203.1 4 09 0
(2022). '2, KWWSVGRLRUJDU;LY

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3.2

ࠕ㧗ศᏊ≀ᛶࢹ࣮ࢱ࣮࣋ࢫࡢ㛤Ⓨࠖᮏࣉࣟࢪ࢙ࢡࢺ࡛ࡣࠊ୺࡞ィ⟬ᑐ㇟ࢆ௬᝿࣏࣐࣮ࣜ࡟ᐃࡵࡿࠋ㧗ศᏊࡢ㦵᱁ࢆ௨ୗࡢ 20 ✀㢮࡟ศ㢮ࡋࠊᶵᲔᏛ⩦࢔ࣝࢦࣜࢬ࣒㸦Ikebata et al., J. Comput. Aided Mol. Des. 31(4):379-391 (2017)㸧࡛ྛ࣏࣐࣮ࣜࢡࣛࢫࡢศ
Ꮚ⏕ᡂࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࡇࡇ࡛ࠊ᪤Ꮡࡢ࣏࣐࣮ࣜࡢ໬Ꮫᵓ㐀ࢆ⏝࠸࡚ᶵᲔᏛ⩦ࡢࣔࢹࣝࢆカ⦎ࡋࠊ᪤Ꮡศ
Ꮚ࡟⌧ࢀࡿ㢖ฟࣃࢱ࣮ࣥ㸦ࣇࣛࢢ࣓ࣥࢺࡸ⤖ྜ࣮ࣝࣝ࡞࡝㸧ࢆᶍೌࡋࡓᵓ㐀⏕ᡂჾࢆᵓ⠏ࡋࡓࠋࡇࡢࡼ࠺࡟
ከᵝ࡞ศᏊ㦵᱁ࢆ᭷ࡍࡿィ 1,778,039 ಶࡢೃ⿵ศᏊ࠿ࡽ࡞ࡿໟᣓⓗ࡞௬᝿ࣛ࢖ࣈࣛࣜࢆస〇ࡋࡓ㸦ᅗ 3㸧ࠋᅗ 3.

ᶵᲔᏛ⩦࢔ࣝࢦࣜࢬ࣒࡟ࡼࡿ 20 ✀㢮ࡢศᏊ㦵᱁ࢆໟྵࡍࡿ࣏࣐࣮ࣜ௬᝿ࣛ࢖ࣈࣛࣜ

ࡇࡢ௬᝿ࣛ࢖ࣈࣛࣜࢆィ⟬ᑐ㇟࡜ࡋ࡚ࠊ࢔ࣔࣝࣇ࢓ࢫ࣏࣐࣮ࣜࡢ  ≀ᛶࡢ⮬ືィ⟬ࢆᐇ᪋ࡋࡓࠋ  ᖺᗘ୰࡟  ࣏࣐࣮ࣜࡢᖹ⾮໬ィ⟬ࡀ᏶஢ࡋࠊࡉࡽ࡟  ࣏࣐࣮ࣜࡢ⇕ఏᑟ⋡ィ⟬ࡀ᏶஢ࡋࡓࠋࡇࡢィ⟬࡟ࡼࡾࠊᅗ  ࡟♧ࡍࡼ࠺࡟ࠊ኱㔞ࡢ࣏࣐࣮ࣜࡢ」ᩘ≀ᛶࡢྠ᫬ศᕸࢆほࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡇࢀ࡟ࡼࡾࠊ

」ᩘ≀ᛶࡢࣃ࣮ࣞࢺ㠃ࡢ఩⨨ࡀ≉ᐃࡉࢀ࡚ࠊࣃ࣮ࣞࢺ㠃ࢆᵓᡂࡍࡿ࣏࣐࣮ࣜ⩌ࡢᵓ㐀ⓗ≉ᚩ࡟㛵ࡍࡿయ⣔ⓗ࡞▱ぢࢆᚓࡿ࡟⮳ࡗࡓࠋ⇕ఏᑟ⋡ࡢィ⟬࡛ࡣࠊࣃ࣮ࣞࢺቃ⏺ࢆ㉸࠼ࡿࡼ࠺࡞≉␗ⓗ࡞ศᏊ㦵᱁ࡀྠᐃࡉࢀࡓࠋ
㏻ᖖࡢ࢔ࣔࣝࣇ࢓ࢫ࣏࣐࣮ࣜࡢ⇕ఏᑟ⋡ࡣ㧗ࡃ࡚ࡶ :P. ࡯࡝࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊィ⟬ࡉࢀࡓ࣏࣐࣮ࣜࡢ୍㒊࡟⇕ఏᑟ⋡ࡀ :P. ࢆ㉸࠼ࡿࡼ࠺࡞ࡶࡢࡀྵࡲࢀ࡚࠸ࡓࠋࡇࢀࡽࡢ࣏࣐࣮ࣜࡢᵓ㐀ⓗ≉ᚩࢆゎᯒࡋࡓ⤖ᯝࠊ๛┤࡞ศᏊ㦵᱁ࢆᣢࡘ࣏࣐࣮࡛ࣜࡣඹ᭷⤖ྜࢆ௓ࡋࡓ⇕ఏᑟࡀࠊỈ⣲⤖ྜྍ⬟࡞ࣘࢽࢵࢺࡀ㧗ᐦᗘ࡛Ꮡᅾࡍࡿ࣏࣐࣮࡛ࣜࡣࠊỈ⣲⤖ྜࡸ GLSROHGLSROH ┦஫స⏝ࢆ௓ࡋࡓ⇕ఏᑟࡀ࢔ࣔࣝࣇ࢓ࢫ࣏ ࣜ ࣐ ࣮ࡢ㧗⇕ఏᑟ໬ࢆᐇ⌧ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦ㄽᩥᰝㄞ୰㸹ࣉࣞࣉࣜࣥࢺ +D\DVKLHW DO
DU;LY  㸧ࠋ- 428 -ᅗ 4.

」ᩘ≀ᛶࡢྠ᫬ศᕸ࡜ࣃ࣮ࣞࢺቃ⏺ࡢほⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬ᯘ៞ᾈ, Wu Stephen, 㔝ཱྀ⍱, ሷぢ῟୍㑻, ᳃ᕝ῟Ꮚ, ྜྷ⏣ு, ➨ 70 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦ཱྀ㢌Ⓨ⾲㸧,

2021 ᖺ 5 ᭶‫ۻ‬ᯘ៞ᾈ, ⤫ィᩘ⌮◊✲ᡤ ࣮࢜ࣉࣥࣁ࢘ࢫ㸦࣏ࢫࢱ࣮Ⓨ⾲㸧, 2021 ᖺ 6 ᭶‫ۻ‬ᯘ៞ᾈ, Wu Stephen, 㔝ཱྀ⍱, ሷぢ῟୍㑻, ᳃ᕝ῟Ꮚ, ྜྷ⏣ு, ➨ 70 ᅇ㧗ศᏊウㄽ఍㸦ཱྀ㢌Ⓨ⾲㸧, 2021 ᖺ9᭶‫ۻ‬ᯘ៞ᾈ, Wu Stephen, 㔝ཱྀ⍱, ሷぢ῟୍㑻, ᳃ᕝ῟Ꮚ, ྜྷ⏣ு, ➨ 42 ᅇ᪥ᮏ⇕≀ᛶࢩ࣏ࣥࢪ࣒࢘㸦ཱྀ㢌Ⓨ⾲㸧, 2021 ᖺ 10 ᭶‫ۻ‬ᯘ៞ᾈ, ➨ 13 ᅇᮦᩱ⣔࣮࣡ࢡࢩࣙࢵࣉ࣐ࠥࢸࣜ࢔ࣝ㠉᪂ຊᙉ໬࡟ྥࡅ࡚㸸ࠕᐩᓅࠖࡀᑟࡃ⏘ᐁᏛ"ඹ๰ࡢሙ"ᙧᡂࠥ㸦ཱྀ㢌Ⓨ⾲㸧, 2022 ᖺ 2 ᭶‫ۻ‬ᯘ៞ᾈ, ⤫ィᩘ⌮ࢭ࣑ࢼ࣮㸦ཱྀ㢌Ⓨ⾲㸧, 2022 ᖺ 3 ᭶‫ۻ‬ᯘ៞ᾈ, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕᐩᓅࠖᡂᯝ๰ฟຍ㏿ࣉࣟࢢ࣒ࣛ ࢩ࣏ࣥࢪ࣒࢘ࠕᐩᓅⓒᬒࠖ◊✲஺ὶ఍㸦࣏ࢫࢱ࣮Ⓨ⾲㸧, 2022 ᖺ 3 ᭶‫ۻ‬ᯘ៞ᾈ,ࠕᐩᓅࠖᡂᯝ๰ฟຍ㏿ࣉࣟࢢ࣒ࣛࠕࢹ࣮ࢱ㥑ືᆺ㧗ศᏊᮦᩱ◊✲ࢆኚ㠉ࡍࡿࢹ࣮ࢱᇶ┙๰ฟࠖබ㛤ࢭ࣑ࢼ࣮㸦ཱྀ㢌Ⓨ⾲㸧, 2022 ᖺ 3 ᭶ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Y. Hayashi, J. Shiomi, J. Morikawa, R. Yoshida, "RadonPy: Automated Physical Property Calculation using All -atom Classical Molecular Dynamics Simulations for Polymer Informatics ," arXiv:2203.14090 (2022), preprint.
‫ۻ‬ᯘ៞ᾈ, RadonPy version 0.2, https://github.com/RadonPy/RadonPy 㸦ࢯࣇࢺ࢙࢘࢔බ㛤㸧, 2022 ᖺ 3 ᭶- 429 -

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

◊✲┠ⓗ
┠ⓗࡢ SH2 ࢻ࣓࢖ࣥ࡟ᑐࡋ࡚≉␗ⓗ࡟⤖ྜࡍࡿࣜࣥ㓟໬࣌ࣉࢳࢻࡢ㛤Ⓨ࡛࠶ࡿࠋᡃࠎࡢ◊✲ࡢ኱ࡁ࡞┠ⓗࡣࠊ⮬ᅾ࡞⣽⬊㐠࿨ไᚚࢆྍ⬟࡜ࡍࡿேᕤཷᐜయࢆ㛤Ⓨࡍࡿࡇ࡜࡛࠶ࡿࠋ≉࡟ࠊ⾑⌫⣔⣽⬊ࡢቑṪࡸศ໬࡞࡝ࡢ⣽⬊㐠࿨ㄏᑟ࡟࡜ࡗ࡚㔜せ࡞ᶵ⬟ࢆᯝࡓࡍࠊཷᐜయᆺࢳࣟࢩࣥ࢟ࢼ࣮ࢮ㸦RTK㸧
ࡸϨᆺࢧ࢖ࢺ࢝࢖ࣥཷᐜయ࡞࡝ࡀάᛶ໬ࡍࡿࢩࢢࢼࣝఏ㐩⤒㊰ࢆࢱ࣮ࢤࢵࢺ࡜ࡍࡿࠋࡇࢀࡽࡢཷᐜయࡣ࠸ࡎ
ࢀࡶࠊࣜ࢞ࣥࢻ࡟ࡼࡿཷᐜయࡢάᛶ໬࡟ࡼࡾࠊཷᐜయࡢ⣽⬊ෆࢻ࣓࢖ࣥࡢࢳࣟࢩࣥṧᇶࡀࣜࣥ㓟໬ࢆཷࡅࠊ
ࡑࡇ࡟⣽⬊ෆࢩࢢࢼࣝఏ㐩ࢱࣥࣃࢡ㉁ࡢ࠺ࡕࠊSrc Homology 2 (SH2)ࢻ࣓࢖ࣥ࡜࠸࠺ඹ㏻ࢻ࣓࢖ࣥࢆᣢࡘศᏊ
ࡀࣜࢡ࣮ࣝࢺࡉࢀࠊάᛶ໬ࢆཷࡅࡿࡇ࡜࡛㛤ጞࡉࢀࡿࠋ
SH2 ࢻ࣓࢖ࣥࡣ୍⯡࡟ࠊཷᐜయࡢࣜࣥ㓟໬ࢳࣟࢩࣥࡢ࿘㎶㓄ิࡲ࡛ྵࡵ࡚ㄆ㆑ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ
๓ᚋ㸯㸮ṧᇶ⛬ᗘࡀぶ࿴ᛶ࡟኱ࡁࡃ㛵୚ࡋ࡚࠸ࡿࠋࡇࡢ࿘㎶㓄ิࡢࡇ࡜ࢆࢳࣟࢩࣥࣔࢳ࣮ࣇ࡜࿧ࡪࠋS㹆2 ࢻ࣓࢖ࣥࡣࡇࢀࡲ࡛࡟ࠊ121 ✀ࡢࣇ࢓࣑࣮ࣜࡀ☜ㄆࡉࢀ࡚࠾ࡾࠊ1 ࡘࡢࢳࣟࢩࣥࣔࢳ࣮ࣇ࡟ᑐࡋ࡚」ᩘࡢ S㹆2ࢻ࣓࢖ࣥࡀぶ࿴ᛶࢆ᭷ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊ㸯ࡘࡢ SH2 ࢻ࣓࢖ࣥࡶ」ᩘࡢ㓄ิ࡟ᑐࡋ࡚ぶ࿴ᛶࢆ᭷ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡓࡵࠊࡇࡢ┦஫స⏝ᵝᘧࡣ୍⯡࡟ከᑐከࡢ⌧㇟࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡑࡇ
࡛ᡃࠎࡢ┠ᶆࡣࠊ┠ⓗࡢࢩࢢࢼࣝఏ㐩ศᏊࠊ࡞࠸ࡋࡣ SH2 ࢻ࣓࢖ࣥࡢࡳ࡜⤖ྜࡍࡿࡼ࠺࡞ࢳࣟࢩࣥࣔࢳ࣮ࣇ
ࢆ᪂ࡓ࡟㛤Ⓨࡋࠊࡇࡢ㓄ิࢆ౑ࡗ࡚ேᕤཷᐜయࢆస〇ࡍࡿࡇ࡜࡛ࠊᮃࡳࡢάᛶ໬ࣃࢱ࣮ࣥࢆ᭷ࡍࡿཷᐜయࢆస〇ࡋࠊ᭱⤊ⓗ࡟ࡣ⮬ᅾ࡞⣽⬊㐠࿨ไᚚࢆྍ⬟࡟ࡍࡿࡇ࡜ࢆ┠ᶆ࡜ࡋ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲᙜึࠊࣇ࣮ࣜࢯࣇࢺࡢ Rosetta ࢆ⏝࠸ࡓࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࡸࠊGROMACS ࢆ⏝࠸ࡓศᏊືຊᏛィ⟬ࢆணᐃࡋ࡚࠸ࡓࡀࠊࡑࢀࡽࡢィ⟬ࢆ௒ᅇᐇ᪋ࡋ࡞࠿ࡗࡓࠋ



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ࡃ◊✲ࢆྠ᫬࡟㐍ࡵ࡚࠾ࡾࠊ◊✲ࣉࣟࢪ࢙ࢡࢺࡢ㐍⾜ࡢ㒔ྜୖࠊࡑࡕࡽ࡟኱ࡁࡃࣜࢯ࣮ࢫࢆ๭࠸ࡓࡇ࡜ࡀ⌮⏤࡜ࡋ࡚ᣲࡆࡽࢀࡿࠋࡋ࠿ࡋィ⟬࡟ࡼࡾࣔࢳ࣮ࣇࡢ⤖ྜᵝᘧࢆ≀⌮ⓗ࡟⌮ゎࡍࡿࡓࡵࡢ◊✲࡜ࠊࣂ࣮ࢳࣕࣝ
ࢫࢡ࣮ࣜࢽࣥࢢࡢᡭἲࡣࡑࢀࡒࢀࡇࢀ࠿ࡽࡶ᳨ウࢆ⥆ࡅ࡚࠸ࡁࡓ࠸࡜⪃࠼࡚࠸ࡿࠋ



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⁐፹ᴟᛶ࡜ ᗘ࡟ᛂ⟅ࡍࡿࢱࣥࣃࢡ㉁␯Ỉ࣏ࢣࢵࢺࡢືⓗᵓ㐀ኚ໬ࡢゎ᫂
Dynamic Structural Changes of Protein Hydrophobic Pocket in
Response to Solvent Polarity and Temperature‫ۑ‬ᱵ⃝ 㞞࿴㸦ᮾி⌮⛉኱Ꮫ㸧ࠊᮡ⏣ ᫀᓅ㸦ᮾிᕤᴗ኱Ꮫ㸧




◊✲┠ⓗ
⏕యෆࡢ୺せ࡞ࢱࣥࣃࢡ㉁ࡢ୍ࡘ࡛࠶ࡿ࢔ࣝࣈ࣑ࣥ㸦ศᏊ㔞 㸧࡟ேᕤⓗ࡟పศᏊ໬ྜ≀㸦⸆≀ࠊ⺯ගⰍ⣲㸧ࢆෆໟࡋ࡚ࢼࣀ⢏Ꮚ໬ࡋࠊ⸆≀㏦㐩 GUXJGHOLYHU\  ࡸ in vivo ࢖࣓࣮ࢪࣥࢢ࡟ᛂ⏝ࡋࡼ࠺࡜ࡍࡿ◊✲ࡀ㐍ࢇ࡛࠸ࡿ>@ࠋ࢔ࣝࣈ࣑ࣥ࡬ࡢపศᏊ໬ྜ≀ࡢෆໟࡸࡑࡇ࠿ࡽᚎᨺຠ⋡ࢆไᚚࡍࡿୖ࡛ࠊపศᏊ໬ྜ≀ࢆෆໟࡍࡿ࢔ࣝࣈ࣑ࣥࡢ❧యᵓ㐀ࠊ≉࡟␯Ỉ࣏ࢣࢵࢺࢆᵓᡂࡍࡿ␯Ỉᛶ࢔࣑ࣀṧᇶࣜࢵࢳ࡞ࢻ࣓࢖ࣥࡢᚤᑠ⎔ቃࢆไᚚࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋ⏦ㄳ⪅ࡽࡣ᭱㏆ࡢ◊✲࡟ࡼࡾࠊ࢔ࣝࣈ࣑ࣥࢆ⁐ゎࡍࡿ⁐፹࡟␯ỈᛶศᏊࢆຍ࠼ࡿࡇ࡜࡛ᴟᛶࢆኚ࠼ࡓࡾࠊ ᗘࢆ ࠥ. ࡜࠸࠺ẚ㍑ⓗ࿴࡞⠊ᅖ࡛ኚ࠼ࡓࡾࡋࡓሙྜ࡟ࠊ࢔ࣝࣈ࣑

ࣥ␯Ỉ࣏ࢣࢵࢺ࡬ࡢపศᏊ≀㉁ࡢෆໟຠ⋡ࡀኚࢃࡿࡇ࡜ࢆᐇドࡋࡓࠋࡋ࠿ࡋࠊ⁐ᾮࡢᴟᛶࡸ

ᗘࡢኚ໬࡟క

࠺࢔ࣝࣈ࣑ࣥศᏊࡢ␯Ỉ࣏ࢣࢵࢺࡢᚤᑠ⎔ቃࡢኚ໬ࢆࠊศᏊࡢ❧యᵓ㐀ࡢኚ໬࡜ࡋ࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣᐇ
㦂ⓗᡭἲࡢࡳ࠿ࡽ࡛ࡣᅔ㞴࡛࠶ࡗࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚⁐ᾮ᮲௳ࡢኚ໬࡟క࠺࢔ࣝࣈ࣑ࣥศᏊࡢ␯Ỉ࣏ࢣࢵࢺࡢᚤᑠ⎔ቃኚ໬ࢆྍど໬ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋලయⓗ࡟ࡣࠊ࢔ࣝࣈ࣑ࣥࢆ」ᩘࡢ

ᗘࠊ␗࡞ࡿ⁐፹⎔ቃ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࠊ␯Ỉ࣏ࢣࢵࢺࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡢẚ㍑

ࢆ⾜ࡗࡓࠋ
◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣᗘࠊ⁐፹⎔ቃࡢ㐪࠸࡟ࡼࡿ࢔ࣝࣈ࣑ࣥࡢᵓ㐀ኚ໬ࢆ☜ㄆࡍࡿࡓࡵ࡟Ỉ⁐ᾮࠊ࢔ࢭࢺࢽࢺࣜࣝ

ࠊ࢔ࢭࢺࢽࢺࣜࣝ ࢆྵࡴ⁐ᾮ࡟࠾࠸࡚࢔ࣝࣈ࣑ࣥ㸯ศᏊࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞ
ࢩࣙࣥࡢᡭἲ࡟ࡣ 5HSOLFD H[FKDQJH ZLWK VROXWH WHPSHULQJ ἲࢆ⏝࠸ࠊȣV ࡢィ⟬ࢆ⾜ࡗࡓࠋỈ⁐ᾮ୰ࡢ࢔ࣝࣈ
࣑ࣥࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ࡣࠊ ಶࡢࣞࣉࣜ࢝ࢆ⏝࠸ࠊ᭱኱ᗘࡣ . ࡜ࡋࡓࠋ࢔ࢭࢺࢽࢺࣜࣝ ࠊ࢔ࢭࢺࢽࢺࣜࣝ ࢆྵࡴ⁐ᾮ࡛ࡢィ⟬࡛ࡣ  ࣞࣉࣜ࢝ࡢ 5(67 ἲࢆ⏝࠸ࡿ࡜࢔ࣝࣈ࣑ࣥࡀ᏶඲࡟ኚᛶࡋ
࡚ࡋࡲࡗࡓࡓࡵࠊ᭱኱ᗘࡀ . ࡜࡞ࡿ  ࣞࣉ࡛ࣜ࢝ࡢィ⟬ࢆ⾜ࡗࡓࠋ⺮ⓑ㉁ࡢຊሙ࡟ࡣ II6% ࢆࠊỈศᏊࡢຊሙ࡟ࡣ 7,33 ࢆ⏝࠸ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢙࢘࢔ࡣ DPEHU ࢆ⏝࠸ࡓࠋ࢔ࢭࢺࢽࢺࣜࣝ࡟ࡣ *$))
ຊሙࢆ๭ࡾᙜ࡚ࠊ$0%&& ἲࢆ⏝࠸࡚㒊ศ㟁໬ࢆ௜ຍࡋࡓࠋ




◊✲ᡂᯝ
ᮏ◊✲࡛ࡣỈ⁐ᾮ࠾ࡼࡧࠊࠊࡢ࢔ࢭࢺࢽࢺࣜࣝ⁐ᾮ࡟ᑐࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ࢔ࣝࣈ࣑ࣥ

ࡢᵓ㐀ኚ໬ࢆほᐹࡋࡓࠋỈ⁐ᾮࠊ$&1ࠊ$&1 ࡢ 0' ࢺࣛࢪ࢙ࢡࢺࣜ࡟࠾ࡅࡿ࢔ࣝࣈ࣑ࣥࡢ URRWPHDQVTXDUHIOXFWXDWLRQ 506) ࢆィ⟬ࡋࠊᅗ  D ࡟♧ࡋࡓࠋỈ⁐ᾮ୰࡟࠾ࡅࡿ࢔ࣝࣈ࣑ࣥࡢᵓ㐀ࡣ࢔ࢭࢺࢽࢺࣜࣝࢆ
ྵࡴ⁐ᾮ୰ࡢᵓ㐀࡜ẚ㍑ࡋ࡚ 506) ࡢᑠࡉ࠸ᵓ㐀ࢆ࡜ࡗ࡚࠾ࡾࠊ࢔ࢭࢺࢽࢺࣜࣝࡢᏑᅾୗ࡜ẚ㍑ࡋ࡚ᅛࡃᏳ

- 437 -

ᐃࡋࡓᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ୍᪉ࠊ࢔ࢭࢺࢽࢺࣜࣝࢆྵࡴ⁐ᾮࡢࢹ࣮ࢱ࡛ࡣ 506) ࡢ್ࡀᖹᆒ
ⓗ࡟㧗ࡃࠊ」ᩘࡢ⟠ᡤ࡛ 506) ࡀ c ࢆ㉸࠼ࡿ㧗࠸್ࢆᣢࡘࡇ࡜ࡀ♧ࡉࢀࡓࠋᅗ  E ࡟࢔ࣝࣈ࣑ࣥࡢ⤖ᬗᵓ㐀ࢆ $&1ࡢࢺࣛࢪ࢙ࢡࢺࣜ࠿ࡽᚓࡽࢀࡓ 506) ࡢ್࡛Ⰽ௜ࡅࡋࡓࢹ࣮ࢱࢆ♧ࡋࡓࠋ㉥ࡸⓑ࡛Ⰽ௜ࡅࡉࢀ
ࡓ㡿ᇦࡢ 506) ࡢ㧗࠸㡿ᇦࡣ⁐ᾮ࡟᥋ゐࡍࡿ࢔ࣝࣈ࣑ࣥࡢᮎ➃㒊ศ࡟㞟୰ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡉࡽ࡟ࠊ
⺯ගᐃࢹ࣮ࢱࡢᏑᅾࡍࡿࠊ␯Ỉ࣏ࢣࢵࢺࢆᵓᡂࡍࡿṧᇶ࡛࠶ࡿ 753 ࿘ᅖࡢỈศᏊࡢ UDGLDO GLVWULEXWLRQIXQFWLRQ 5') ࢆᅗ  F ࡟♧ࡋࡓࠋ5') ࡢࢹ࣮ࢱ࠿ࡽࡣ࢔ࢭࢺࢽࢺࣜࣝࢆຍ࠼ࡓሙྜỈศᏊࡢ␯Ỉ࣏ࢣࢵࢺ࡬
ࡢ౵ධࡣⱝᖸቑຍࡍࡿࡶࡢࡢࠊ࣏ࢣࢵࢺࡢᵓ㐀⮬యࡣࡼࡃಖᏑࡉࢀ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᅗ 㸸 D ␗࡞ࡿ⁐ᾮ୰࡟࠾ࡅࡿ࢔ࣝࣈ࣑ࣥṧᇶࡢ 506)ࠋ E 506) ್࡛Ⰽ௜ࡅࡉࢀࡓ࢔ࣝࣈ࣑ࣥࡢ⤖ᬗᵓ㐀ࠋ F 753 ࿘ᅖࡢỈศᏊࡢ 5')ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ㸦ᮍᐃ㸧

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ㸦ᮍᐃ㸧ཧ⪃ᩥ⊩>@ .DULPL0HWDOExpert Opin. Drug Delivery >@/RPEDUGR'HWDOJ. Nanomater. - 438 -

཯ᛂ⮬ື᥈⣴ἲ࡟ࡼࡿ࣊ࢸࣟඖ⣲ࢆά⏝ࡋࡓ᪂཯ᛂࡢ๰ฟ࡜᪂ᮦᩱࡢ㛤Ⓨ
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8VLQJ$XWRPDWHG5HDFWLRQ3DWK6HDUFK0HWKRGV‫ۑ‬㛗⏣ ⿱ஓࠊ⛅ᒣ ୡ἞ࠊ㎷ ಙᘺࠊAmrutha Ammathnadu Sudhakar,
Ravindra Krushnaji Raut㸦໭ᾏ㐨኱Ꮫ ໬Ꮫ཯ᛂ๰ᡂ◊✲ᣐⅬ㸧



◊✲┠ⓗ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ୺࡜ࡋ࡚཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ฼⏝ࡋ࣊ࢸࣟඖ⣲ࢆά⏝ࡋࡓ᪂཯ᛂࡢ㛤Ⓨ࡜᪂ᮦᩱࡢ㛤Ⓨ࡟ྥࡅ᳨࡚ウࢆ⾜ࡗࡓࠋ๓⏣ࡽ࡟ࡼࡗ࡚㛤Ⓨࡉࢀࡓ཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ୍ࡘ࡛࠶ࡿேᕤຊㄏ㉳཯ᛂ
(AFIR)ἲࡣࠊ཯ᛂࢧ࢖ࢺྠኈࢆᢲࡋ௜ࡅࡿࠊࡲࡓࡣᘬࡁ㞳ࡍ࡜࠸࠺༢⣧࡞᧯స࡟ࡼࡗ࡚཯ᛂ⤒㊰ࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋAFIR ἲࡣẚ㍑ⓗ༢⣧࡞࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸ࡿࡇ࡜࠿ࡽࠊ」㞧࡞཯ᛂ࡬ࡢ㐺⏝ᛶࡀ㠀ᖖ࡟㧗ࡃࠊࡇࢀࡲ࡛࡟ᗈ⠊࡞໬Ꮫ཯ᛂ࡟㐺⏝ࡉࢀ࡚ࡁࡓࠋᮏ◊✲ㄢ㢟࡛ࡣࠊ୺࡟࣊ࢸࣟඖ⣲࡜ࡋ࡚࣍࢘⣲ࢆ฼⏝ࡋࡓ᪂཯ᛂࡢ㛤Ⓨ࡟ AFIR ἲࢆ㐺⏝ࡋࠊ᭷⏝࡞ศᏊኚ᥮ἲ࡜᪂つ໬ྜ≀ࡢ๰ฟࢆ┠ᣦࡋࡓࠋࡉࡽ࡟㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ⥙⨶ⓗ࡞ࢫࢡ࣮ࣜࢽࣥࢢ࡟ࡼࡿ෇೫ගᮦᩱࡢ㛤Ⓨ࡟ࡘ࠸࡚ࡶ᳨ウࢆ㐍ࡵࠊ㧗࠸㠀ᑐ⛠ᛶᅉᏊࢆ᭷ࡍࡿ᪂
ᮦᩱࡢ๰ฟࢆ┠ᣦࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 ࣃࣛ࣋ࣥࢨ࢖ࣥࢆ⏝࠸ࡓ࣊ࢸࣟඖ⣲ᑟධ཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウ㧗཯ᛂᛶ໬Ꮫ✀࡜ࡋ࡚ࣃࣛ࣋ࣥࢨ࢖ࣥ㢮࡟╔┠ࡋࠊ᪂つ࣍࢘⣲ᐁ⬟ᇶᑟධἲࡢ㛤Ⓨ࡟ࡘ࠸᳨࡚ウࡋࡓࠋึᮇ᳨ウ࡜ࡋ࡚ࠊ
ࢪ࢖ࣥ໬ྜ≀ࡢ Masamune–Bergman ⎔໬཯ᛂ࡟ࡼࡿࣃࣛ࣋ࣥࢨ࢖ࣥ㢮࡬ࡢኚ᥮࡟ࡘ࠸࡚ࠊ
AFIRἲࢆ⏝࠸࡚άᛶ໬࢚ࢿࣝࢠ࣮ࡢ᥎ᐃࢆ⾜ࡗࡓࠋGRRM ࣉࣟࢢ࣒ࣛ࡜ Gaussian 16 ࢆ⏝࠸ࠊMIN ィ⟬࡟ࡼࡗ࡚ேᕤຊࢆຍ࠼࡚཯ᛂ⤒㊰ࢆ᫂ࡽ࠿࡟ࡋࡓࡢࡕࠊLUP ィ⟬࡟ࡼࡗ࡚ேᕤຊࢆྲྀࡾ㝖ࡃࡇ࡜࡛㑄⛣≧ែࡢ࢚ࢿࣝ
ࢠ࣮ࢆồࡵࠊ✀ࠎࡢࢪ࢖ࣥ໬ྜ≀࠿ࡽࣃࣛ࣋ࣥࢨ࢖ࣥࢆ⏕ᡂࡍࡿ㝿ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋᮏ⣔ࡣ㛤Ẇ⣔ࡢ⏕ᡂ≀ࢆྵࢇ࡛࠾ࡾࠊࡲࡓ⥙⨶ⓗ࡞ࢫࢡ࣮ࣜࢽࣥࢢࢆ㧗㏿࡟⾜࠺ࡓࡵࠊUB3LYP/6-31G ࡛ࣞ࣋ࣝィ⟬ࢆ⾜ࡗࡓࠋึᮇ᳨ウ࡜ࡋ࡚ࠊ1,2-ࢪ࢚ࢳࢽࣝ࣋ࣥࢮࣥࡢᮎ➃࢔ࣝ࢟ࣥ㒊ศࢆ࣮ࣜࣥ࢝ᵓ㐀࡛⧅࠸ࡔᵓ㐀࡟ࡘ࠸᳨࡚ウࡋࠊ⥆࠸࡚ࠊ࣋ࣥࢮࣥ⎔㒊ศࢆ௚ࡢⰾ㤶⎔࡟௦࠼ࡓᵓ㐀࡟ࡘ࠸᳨࡚ウࢆ㐍ࡵࡓࠋᮏ◊✲ࡣி㒔኱Ꮫ≉ᐃ◊✲ဨࡢ୰ሯ᐀୍㑻༤ኈ࡜༠ຊࡋ࡚㐙⾜ࡋࡓࠋ
2.2 ⨨᥮[7]࣊ࣜࢭࣥࡢ෇೫ගⓎග≉ᛶ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウ᪂つ෇೫ගⓎගᮦᩱࡢ㛤Ⓨࢆ┠ⓗ࡜ࡋ࡚ẕ㦵᱁࡜ࡋ࡚[7]࣊ࣜࢭࣥ࡟╔┠ࡋࠊ✀ࠎࡢ⨨᥮ᇶࢆᑟධࡋࡓ㢮⦕యࡢ෇೫ගⓎග≉ᛶ࡟ࡘ࠸᳨࡚ウࢆ⾜࡞ࡗࡓࠋ[7]࣊ࣜࢭࣥ࡟ᑐࡋ࡚✀ࠎࡢ⨨᥮ᇶࢆ BIOVIA Materials Studio
Visualizer, Build Analogs Tool ࢆ⏝࠸࡚⮬ືⓗ࡟ᑟධࡋࠊ⨨᥮[7]࣊ࣜࢭࣥ㢮ࡢึᮇᵓ㐀ࢆ⥙⨶ⓗ࡟⏕ᡂࡋࡓࠋࡉ ࡽ ࡟ ࠊ Gaussian 16 (ȦB97X-D/6-31G(d) ࣞ ࣋ࣝ ) ࡟࡚ ᫬ 㛫 ౫ Ꮡ ᐦ ᗘ ỗ 㛵 ᩘἲ (Time-dependent densityfunctional theory, TDDFT ἲ) ࢆ⏝࠸࡚ S1 ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ㟁Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜☢Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࢆồࡵࡿࡇ࡜࡛ࠊ෇೫ගⓎග࡟࠾ࡅࡿ㠀ᑐ⛠ᛶᅉᏊࢆ᥎ᐃࡋࡓࠋࡉࡽ࡟ࠊᚓࡽࢀࡓ⤖ᯝࢆ㠀ᑐ⛠ᛶᅉᏊ࡟ᚑࡗ࡚⨨᥮[7]࣊ࣜࢭࣥ㢮ࢆࢯ࣮ࢺࡍࡿࡇ࡜࡛ࠊྜᡂᐇ㦂࡟࠾ࡅࡿඃඛ㡰఩௜ࡅࢆ⾜࡞ࡗࡓࠋ- 439 -



◊✲ᡂᯝ

3.1

ࣃࣛ࣋ࣥࢨ࢖ࣥࢆ⏝࠸ࡓ࣊ࢸࣟඖ⣲ᑟධ཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウࡲࡎึᮇ᳨ウ࡜ࡋ࡚ࠊ1,2-ࢪ࢚ࢳࢽࣝ࣋ࣥࢮࣥࡢᮎ➃࢔ࣝ࢟ࣥ㒊ศࢆ࣮࡛ࣜࣥ࢝⧅࠸ࡔᵓ㐀࡟ࡘ࠸࡚
Masamune–Bergman ⎔໬཯ᛂ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆồࡵࡿࡇ࡜࡛ࠊ࣊ࢸࣟඖ⣲ᑟධ཯ᛂ࡟㐺ࡋࡓ཯ᛂ
ᇶ㉁ࡢ᳨ウࢆ⾜࡞ࡗࡓ㸦ᅗ 1㸧ࠋ㸰ࡘࡢ࢚ࢳࢽࣝᇶࡢᮎ➃ᵓ㐀࡝࠺ࡋࡀ 3 ཎᏊࡢ࣮࡛ࣜࣥ࢝㐃⤖ࡉࢀࡓ 1a, 1b,
1c, 1e ࡛ࡣάᛶ໬࢚ࢿࣝࢠ࣮ࡀపࡃࠊᖖ

࡛ᐜ᫆࡟ Masamune–Bergman ⎔໬཯ᛂࢆ⤒ࡓศゎࢆ㉳ࡇࡍࡇ࡜ࡀ

ண᝿ࡉࢀࡓࠋ≉࡟ 1c ࡛ࡣάᛶ໬࢚ࢿࣝࢠ࣮ࡀᴟࡵ࡚పࡃࠊప

࡛ಖᏑࡋࡓ࡜ࡋ࡚ࡶ༶ᗙ࡟ศゎࡋ࡚ࡋࡲ࠺ࡇ

࡜ࡀண᝿ࡉࢀࠊࡇࢀࡽࡢᇶ㉁ࡣ཯ᛂ᳨ウ࡟୙㐺ᙜ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉࡛㸰ࡘࡢ࢚ࢳࢽࣝᇶࡢᮎ➃ᵓ㐀࡝࠺ࡋࡀ 5 ཎᏊࡲࡓࡣ 4 ཎᏊࡢ࣮࡛ࣜࣥ࢝㐃⤖ࡉࢀࡓ 1d, 1f ࡛ࡣᖖࡽ࡟ᐇ㊶ⓗ࡞཯ᛂ

࡛ࡣᏳᐃ࡟Ꮡᅾࡍࡿࡇ࡜ࡀ࡛ࡁࠊࡉ

ᗘ

㸦120~150 Υ㸧࡛ࣃࣛ࣋ࣥࢨ
࢖ࣥάᛶ✀ࢆ⏕ᡂྍ⬟࡛࠶ࡿࡇ࡜ࡀศ࠿ࡾࠊࡇࢀࡽࡢᇶ㉁ࡣᴟࡵ࡚᭷ᮃ࡛࠶ࡿࡇ࡜
ࡀศ࠿ࡗࡓࠋࡉࡽ࡟㸰ࡘࡢ࢚ࢳࢽࣝᇶࡢᮎ➃ᵓ㐀࡝࠺ࡋࢆ㛗࠸࣮࡛ࣜࣥ࢝㐃⤖ࡋࡓ
1g, 1f ࡛ࡣ཯ᛂⅬࡀ㐲ࡃ࡞ࡗ࡚ࡋࡲ࠺ࡓࡵάᛶ໬࢚ࢿࣝ
ࢠ࣮ࡀ㧗ࡃ࡞ࡗ࡚ࡋࡲ࠸ࠊᐇ
㊶ⓗ࡞཯ᛂᗘ࡛ࡣ཯ᛂࡋ

࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ௨ୖࡢ
⤖ᯝࢆ㋃ࡲ࠼ྜᡂୖࡢほⅬ࠿ࡽࠊ1,2-ࢪ࢚ࢳࢽࣝ࣋ࣥࢮ

ᅗ 1. ✀ࠎࡢ࣮ࣜࣥ࢝ࢆᑟධࡋࡓࢪ࢚ࢳࢽࣝ࣋ࣥࢮࣥㄏᑟయࡢ Masamune–ࣥࡢᮎ➃࢔ࣝ࢟ࣥ㒊ศࢆࣈ

Bergman ⎔໬཯ᛂ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ (UB3LYP/6-31G)

ࢳࣞࣥᇶ࡛㐃⤖ࡋࡓ 1f ࡀ཯ᛂᇶ㉁࡜ࡋ࡚᭷ᮃ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
⥆࠸࡚ࠊ1f ࡢⰾ㤶⎔㒊ศࢆኚ໬ࡉࡏࡓࢪ࢖ࣥ໬ྜ≀࡟ࡘ࠸࡚ྠᵝࡢ᪉ἲ࡛ Masamune–Bergman ⎔໬཯ᛂ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆồࡵࡓ㸦ᅗ 2㸧ࠋ࣋ࣥࢮࣥ⎔ࢆࢼࣇࢱࣞࣥ⎔࡟௦࠼ࡓ 2a ࡛ࡣάᛶ໬࢚ࢿࣝࢠ࣮ࡀ
㧗ࡃ࡞ࡾࠊ཯ᛂᛶࡀⴠࡕࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋồࡵࡓάᛶ໬࢚ࢿࣝࢠ࣮࠿ࡽ 10 ᫬㛫࡛ 99㸣཯ᛂࡍࡿࡓࡵࡢ཯
ᛂᗘࢆồࡵࡓሙྜ 185Υ࡜࡞ࡾࠊᐇ㝿࡟ᐇ㦂ࢆ⾜࠺ࡇ࡜ࡣᅔ㞴࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࣋ࣥࢮࣥ⎔ࢆࣆࣜࢪࣥ⎔࡟௦࠼ࡓ 2b ࡟࠾࠸࡚ࡶάᛶ໬࢚ࢿࣝࢠ࣮ࡀ㧗ࡃ࡞ࡗࡓࡶࡢࡢࠊࣆࣛࢪࣥ⎔࡟௦࠼ࡓ 2c ࡛ࡣ࣋ࣥࢮࣥ
⎔࡜ྠ➼ࡢάᛶ໬࢚ࢿࣝࢠ࣮࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ5 ဨ⎔ࡢ࣊ࢸࣟⰾ㤶⎔࡛࠶ࡿࠊࣇࣛࣥࠊࢳ࢜ࣇ࢙ࣥࠊ࢖
࣑ࢲࢰ࣮ࣝࢆᑟධࡋࡓ 2d, 2e, 2f ࡟ࡘ࠸࡚ࠊ࣋ࣥࢮࣥ⎔࡜ྠ➼ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ᭷ࡋ࡚࠾ࡾࠊ᭷ᮃ࡞ᇶ㉁ೃ⿵࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ࢔ࢭࢼࣇࢳࣞࣥᵓ㐀ࢆᑟධࡋࡓ 2g ࡛ࡣࡉࡽ࡟άᛶ໬࢚ࢿࣝࢠ࣮ࡀୗࡀࡾࠊྜ
ᡂ࣭ಖᏑࡢ㝿ࡢᏳᐃᛶࡀୗࡀࡿࡇ࡜ࡀண᝿ࡉࢀࠊᇶ㉁࡜ࡋ࡚ࡣ୙㐺ᙜ࡛࠶ࡿࡇ࡜ࡀண᝿ࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝ࡟ᇶ࡙࠸࡚ࠊᐇ㝿࡟ࢳ࢜ࣇ࢙ࣥ⎔ࢆ᭷ࡍࡿ 2e ࢆྜᡂࡋࡓࡀࠊ୙άᛶ㞺ᅖẼୗࠊᖖ࡛ศゎࡋ࡚ࡋࡲ࠺ࡇ࡜

ࡀศ࠿ࡗࡓࠋࡇࢀࡣࠊ௒ᅇ᳨ウࡋࡓ Masamune–Bergman ⎔໬཯ᛂࢆ⤒ࡓศゎ࡛ࡣ࡞ࡃࠊ㟁Ꮚ㇏ᐩ࡞ 3 㔜⤖ྜ- 440 -

㒊఩ࡀศᏊ㛫࡛཯ᛂࡋศゎࡋࡓࡶࡢ࡜⪃࠼࡚࠸ࡿࠋࡇࡢ
⤖ᯝ࠿ࡽᇶ㉁㑅ᢥࡢ㝿ࡢᣦ㔪࡜ࡋ࡚ࠊ㟁Ꮚ㇏ᐩ࡞ⰾ㤶⎔ࡢᑟධࡣ㑊ࡅࡓ࡯࠺ࡀⰋ࠸
ࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓᐇ㝿࡟
1f ࡜ࣅࢫ(ࣆࢼࢥ࣮ࣛࢺ)ࢪ
࣎ࣟࣥࢆ཯ᛂࡉࡏࡓ࡜ࡇࢁࠊ
ࣃࣛ࣋ࣥࢨ࢖ࣥάᛶ✀࡜࣍࢘⣲ヨ⸆ࡀ཯ᛂࡋࡓ⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ⌧ᅾࠊࡉࡽ࡟㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ཯ᛂ᮲௳ࡢ᭱㐺໬ࢆ⾜࠺ࡇ࡜࡛ࠊࡼࡾຠ⋡ࡢⰋ࠸࣍࢘⣲ᐁ⬟ᇶᑟධ཯ᛂ

ᅗ 2. ࢚ࢳࢽࣝᇶࡢᮎ➃ࢆࣈࢳࣞࣥᇶ࡛㐃⤖ࡋࡓ✀ࠎࡢࢪ࢖ࣥ໬ྜ≀ࡢࡢ㛤Ⓨࢆ㐍ࡵࡿணᐃ࡛࠶ࡿࠋ

Masamune–Bergman ⎔໬཯ᛂ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ (UB3LYP/6-31G)

2.2⨨᥮[7]࣊ࣜࢭࣥࡢ෇೫ගⓎග≉ᛶ࡟㛵ࡍࡿ⌮ㄽⓗ᳨ウ᪂つ෇೫ගⓎගᮦᩱࡢྜᡂࢆ┠ⓗ࡜ࡋ࡚ࠊẕ㦵᱁࡜ࡋ࡚[7]࣊ࣜ
ࢭࣥ࡟╔┠ࡋࠊ✀ࠎࡢ⨨᥮ᇶ㸦࣓ࢺ࢟ࢩᇶࠊࢩ࢔ࣀᇶࠊࢪ࣓ࢳࣝ
࢔࣑ࣀᇶࠊࢺࣜࣇ࣓ࣟࣟࢳࣝᇶ㸧ࢆ 3, 7, 12, 16 ఩࡟ᑟධࡋࡓ㢮⦕యࡢᵓ㐀࡟ࡘ࠸࡚෇೫ගⓎග≉ᛶ࡟ࡘ࠸᳨࡚ウࢆ⾜࡞ࡗࡓ㸦ᅗ3㸧
ࠋ[7]࣊ࣜࢭࣥ࡟ᑐࡋ࡚ୖ㏙ࡢ⨨᥮ᇶࢆ BIOVIA Materials Studio
Visualizer (Build Analogs Tool) ࢆ ⏝ ࠸ ࡚ ⥙ ⨶ ⓗ ࡟ ᑟ ධ ࡋ ࠊ
COMPASS II ຊሙࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜࠺ࡇ࡜࡛ࠊ⨨᥮[7]࣊ࣜ

ᅗ 3. ✀ࠎࡢ⨨᥮ᇶࢆᑟධࡋࡓ[7]࣊ࣜࢭࣥ

ࢭࣥ㢮ࡢึᮇᵓ㐀ࢆ⥙⨶ⓗ࡟⏕ᡂࡋࡓ (666 ศᏊ)ࠋᚓࡽࢀࡓึᮇ

ㄏᑟయࡢᵓ㐀

ᵓ㐀࡟ࡘ࠸࡚ࠊGaussian 16 (ȦB97X-D/6-31G(d) ࣞ࣋ࣝ) ࡟࡚ ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ (Time-dependent density-functional theory, TDDFT ἲ) ࢆ⏝࠸࡚ S1 ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ㟁Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺ࡜☢Ẽ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ࣋ࢡࢺࣝࢆࡑࢀࡒࢀồࡵࡓࠋᚓࡽࢀࡓ 2ࡘࡢ࣋ࢡࢺࣝࡢ኱ࡁࡉ࡜ࡑࢀࡽࡢ࡞ࡍゅ࠿ࡽ෇೫ග⺯ගⓎගࡢ㠀ᑐ⛠ᅉᏊࢆ⟬ฟࡋࡓࠋᚓࡽࢀࡓ⤖ᯝࢆᅗ 4 ࡟♧ࡋࡓࠋ3 ఩࡟ࢩ࢔ࣀᇶࢆ᭷ࡍࡿ[7]࣊ࣜࢭࣥࡣ᭱ࡶ኱ࡁ࡞ṇࡢ㠀ᑐ⛠ᛶᅉᏊ(glum)ࢆ
♧ࡋࠊࡑࡢ್ࡣ + 0.06250 ࡜ぢ✚ࡶࡽࢀࡓࠋ2 ␒┠࡟኱ࡁ࡞ glum ್ࢆ♧ࡋࡓ[7]࣊ࣜࢭࣥࡶ 3 ఩࡟ࢩ࢔ࣀᇶࢆ
᭷ࡋ࡚࠾ࡾࠊ16 ఩ࡢ࣓ࢳࣝᇶࡣ㟁Ꮚⓗ㸭❧యⓗຠᯝࡀᑠࡉ࠸࡜⪃࠼ࡽࢀࡿࡇ࡜࠿ࡽࠊ᭱ࡶ㧗࠸ glum ್ࢆᣢࡘ[7]࣊ࣜࢭࣥࡢᵓ㐀࡜ᴟࡵ࡚ఝࡓᵓ㐀࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ୍᪉࡛ࠊ3 ఩࡟ࢩ࢔ࣀᇶࠊ16 ఩࡟࣓ࢺ࢟ࢩᇶࢆ᭷
ࡍࡿ[7]࣊ࣜࢭࣥࡣࠊ௒ᅇ᳨ウࡋࡓ࣊ࣜࢭࣥ⩌ࡢ୰࡛᭱ࡶᑠࡉ࡞ glum ್ (-0.03542) ࢆ♧ࡋࡓࠋࡲࡓࠊḟ࡟ᑠࡉ࡞್ࢆ♧ࡋࡓ[7]࣊ࣜࢭࣥࡢᵓ㐀ࡣࠊ᭱ࡶᑠࡉ࡞ glum ್ࢆ♧ࡋࡓᵓ㐀࡟࣓ࢳࣝᇶࢆಟ㣭ࡋࡓࡶࡢ࡛࠶ࡾࠊᴟࡵ
࡚ఝࡓᵓ㐀࡛࠶ࡗࡓࠋࡍ࡞ࢃࡕࠊṇࡢ኱ࡁ࡞ glum ್ࢆ♧ࡍሙྜ࡟ࡣ[7]࣊ࣜࢭࣥࡢ 3 ఩࡟ᙉ࠸㟁Ꮚồᘬᛶ⨨᥮ᇶ࡛࠶ࡿࢩ࢔ࣀᇶࢆᑟධࡋࡓᵓ㐀ࡀ᭷฼࡛࠶ࡾࠊ㏫࡟㈇ࡢ⤯ᑐ್ࡢ኱ࡁ࡞ glum ್ࢆ♧ࡍሙྜ࡟ࡣࠊ3 ఩࡟ࢩ࢔- 441 -

ࣀᇶࢆᑟධࡋࠊ16 ఩࡟㟁Ꮚ౪୚ᛶ⨨᥮ᇶ࡛࠶ࡿ࣓ࢺ࢟ࢩᇶࢆᑟධࡍࡿࡇ࡜ࡀຠᯝⓗ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
ࡇࢀࡣࠊ[7]࣊ࣜࢭࣥࡢ୧ᮎ➃㛫࡛ࡢ㟼㟁ⓗ┦஫స⏝࡟ᐤ୚ࡋ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋࡲࡓ⯆࿡῝࠸ࡇ࡜࡟ࠊẕ㦵᱁࡜ࡋ࡚⏝࠸ࡓ[7]࣊ࣜࢭࣥࡢ⤯ᑐᵓ㐀ࡣࡍ࡭࡚ྠࡌ࡛࠶ࡿ࡟ࡶ㛵ࢃࡽࡎࠊ⨨᥮ᇶࡢᑟධ࡟ࡼࡗ࡚ᕥྑ୧᪉
ࡢ෇೫ග⺯ගࡀᚓࡽࢀࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ
୍⯡࡟࣊ࣜࢭࣥ㢮ࡣప࠸⺯ග㔞Ꮚ཰⋡ࢆ♧ࡍࡇ࡜ࡀከ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊᙉ࠸⺯ගࢆ♧ࡍ࣊ࣜࢭࣥ㢮ࡣᴟࡵ࡚㝈ࡽࢀ࡚࠸ࡿࠋ௒ᅇࡢ᳨ウ࡛ᚓࡽࢀࡓ෇೫ග⺯ගⓎගᮦᩱࡢೃ⿵⩌࡟ࡘ࠸࡚ࡶࠊࡉࡽ࡞ࡿ㔞Ꮚ໬Ꮫィ⟬࡜ᐇ㦂࡟ࡼࡿᐇドࢆ୪⾜ࡋ࡚㐍ࡵࡿࡇ࡜࡛ࠊ᭷⏝࡞ᮦᩱࡢ㛤Ⓨࡀྍ⬟࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ

ᅗ 4. ✀ࠎࡢ⨨᥮ᇶࢆᑟධࡋࡓ[7]࣊ࣜࢭࣥㄏᑟయࡢ㠀ᑐ⛠ᛶᅉᏊ(glum)࡜
⤯ᑐ್ࡢ኱ࡁ࠸ࠊࡲࡓࡣᑠࡉ࠸ glum ್ࢆ᭷ࡍࡿ[7]࣊ࣜࢭࣥㄏᑟయࡢᵓ㐀

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 442 -

จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲
Theoretical studies of relaxations and reaction dynamics
in condensed phase‫ۑ‬ᩧ⸨ ┿ྖࠊ⏥⏣ ಙ୍ࠊᯇᮧ ⚈ᏹࠊKALATHINGAL MahroofࠊZHU Zhe㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏᖺᗘࡣࠊ1. ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࠊ2. 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)ບ㉳࢚ࢿࣝࢠ࣮⛣ືᶵᵓࠊ3. ࣏ࣜࢭ࢜ࢼ࣑ࢻ B㸦pTB㸧ࡢ⭷ᤄධᶵᵓ࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ
1.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࢩ࢔ࣀࣂࢡࢸࣜ࢔ࡢᴫ᪥ࣜࢬ࣒ࡣ 3 ✀ࡢࢱࣥࣃࢡ㉁(KaiA, KaiB, KaiC)ࡢ┦஫స⏝࡟ࡼࡗ࡚⏕ࡌࡿࠋᦤືࡍ
ࡿ⎔ቃࡢ୰࡛యෆ᫬ィࡢ࿘ᮇࢆ୍ᐃ࡟ಖࡘࡇ࡜ࡣ⏕⌮ⓗ࡟㔜せ࡞ᶵ⬟࡛࠶ࡾࠊࡑࡢ࣓࢝ࢽࢬ࣒ࢆ▱ࡿ࡟ࡣࡲࡎ࿘ᮇࡢỴᐃᶵᵓࢆ▱ࡿᚲせࡀ࠶ࡿࠋ࿘ᮇࡣ㐜࠸㐣⛬࡟ࡼࡗ࡚୺࡟ᐃࡲࡿࠋࢩ࢔ࣀࣂࢡࢸࣜ࢔࡛ࡣ KaiB-KaiC
ࡢ」ྜయᙧᡂࡀࡦ࡜ࡘࡢ㐜࠸㐣⛬࡛࠶ࡿࠋࡇࡢ」ྜయᙧᡂࡣ KaiC ࡀࣜࣥ㓟໬ࡉࢀࡿ࡯࡝ຍ㏿ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ⌧㇟ࡣ⎔ቃᦤື㸦౛࠼ࡤ ᗘᦤື㸧࡟ᑐࡍࡿ࿘ᮇࡢ㡹೺ᛶ࡟ᐦ᥋࡞㛵ಀࡀ࠶ࡿྍ⬟ᛶࡀ࠶ࡿࠋ
ࡍ࡞ࢃࡕࠊKaiB-KaiC 」ྜయࡣ KaiC ࡢࣜࣥ㓟໬᣺ືࢆ⬺ࣜࣥ㓟໬᪉ྥ࡟┦ࢆ㌿᥮ࡉࡏࡿᙺ┠ࢆᣢࡘࡀࠊᦤື
࡟ࡼࡾ㐣๫࡟ࣜࣥ㓟໬ࡀ⏕ࡌࡓሙྜࠊKaiB-KaiC 」ྜయᙧᡂࡀຍ㏿ࡍࡿࡇ࡜࡛ࠊ㏿ࡸ࠿࡟⬺ࣜࣥ㓟໬࡟㌿ࡌࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿ࠿ࡽ࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊࡇࡢ」ྜయᙧᡂຍ㏿ࡢ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿࠋࡋ࠿ࡋࠊ᪤Ꮡࡢ཯ᛂࣔࢹ࡛ࣝࡣࠊKaiC ࡀࣜࣥ㓟໬ࡉࢀࡿ࡯࡝」ྜయᙧᡂࡣῶ㏿ࡋ࡚ࡋࡲࡗ࡚࠸ࡓࠋࡑࡇ
࡛ᮏ◊✲࡛ࡣࠊ᪤Ꮡࡢ཯ᛂࣔࢹࣝ࡟୙㊊ࡋ࡚࠸ࡓせ⣲ࢆ᫂ࡽ࠿࡟ࡋࡓୖ࡛ࠊKaiB-KaiC 」ྜయᙧᡂࡢ඲ㇺࢆグ㏙ࡍࡿࣔࢹࣝࢆ᪂ࡓ࡟ᥦ᱌ࡋࠊࡑࡢศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࠋ
1.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ගྜᡂ⣔ࡣᦂࡽࡂ࡟᫹ࡉࢀ࡚࠸ࡿ࡟ࡶ㛵ࢃࡽࡎࠊࡑࡢึᮇ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⟬ࡀᙉࡃồࡵࡽࢀࡿࠋ୍⯡࡟ࠊࡇࡢࡼ࠺࡞」㞧࡞⣔ࡢ୰ࡢ Chl ศᏊࡢ㟁Ꮚ≧ែࡢゎᯒ࡟ࡣࠊ(᫬㛫౫Ꮡ)ᐦᗘỗ㛵ᩘ⌮ㄽ㸦(TD)DFT㸧ィ⟬ࡀ⏝࠸ࡽࢀࡿࠋࡋ࠿ࡋࠊᶆ‽ⓗ࡟⏝࠸ࡽࢀ࡚࠸ࡿࣃ࣓࣮ࣛࢱ࡟ࡼࡿ(TD)DFT ィ⟬࡛ࡣࠊࡇࡢࡼ࠺࡞኱ࡁ࡞ศᏊࡢࢯࣝࣂࢺࢡ࣑ࣔࢬ࣒ࠊࡍ࡞ࢃࡕࠊ⁐፹ࡸᒁᡤ⎔ቃ࡟ࡼࡿບ㉳࢚ࢿࣝࢠ࣮ࡢኚ
໬ࢆ㐺ษ࡟グ㏙ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠸ࠋࡉࡽ࡟ࠊศᏊືຊᏛィ⟬࡛⏝࠸ࡿຊሙ࡛ࡣࠊⰍ⣲ศᏊࡢグ㏙ࡢ⢭ᗘࡀ୙༑ศ࡛࠶ࡾࠊࢫ࣌ࢡࢺࣝᐦᗘࡢ㐺ษ࡞グ㏙ࡀ࡛ࡁ࡞࠸ࠋࡋ࠿ࡋࠊ㟁Ꮚ≧ែィ⟬࠾ࡼࡧศᏊືຊᏛィ⟬ࡢᢪ࠼ࡿၥ㢟࡟ࡼࡾࠊィ⟬࡟࠾࠸࡚ࡶࡇࢀࡽࡢ㔞ࢆồࡵࡿࡇ࡜ࡣᐜ࡛᫆ࡣ࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ㟁Ꮚ≧ែ࡟㛵ࡍࡿၥ㢟ࡢゎỴࢆ┠ⓗ࡜ࡋࡓࠋ1.3 ࣏ࣜࢭ࢜ࢼ࣑ࢻ B㸦pTB㸧ࡢ⭷ᤄධᶵᵓ࡟㛵ࡍࡿ◊✲࣏ࣜࢭ࢜ࢼ࣑ࢻ B㸦pTB㸧ࡣ㠀ࢱࣥࣃࢡ㉁ᵓᡂ࢔࣑ࣀ㓟ࢆྵࡴ 48 ࢔࣑ࣀ㓟ṧᇶ࠿ࡽᵓᡂࡉࢀࡿ࣌ࣉࢳࢻ࡛ࠊ
D-, L-࢔࣑ࣀ㓟ࡀ஺஫࡟㓄ิࡋࡓ㸯ḟᵓ㐀ࢆᣢࡘࠋࡲࡓࠊpTB ࡣᾏ⥥࡟ඹ⏕ࡍࡿࣂࢡࢸࣜ࢔⏤᮶ࡢ ȕ-helix ᵓ- 443 -

㐀ࢆ࡜ࡿ⣽⬊ẘ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ⭷࡟ᐜ᫆࡟౵ධࡋ࢝ࢳ࢜ࣥ㑅ᢥⓗ࢖࢜ࣥࢳࣕࢿࣝࡢᶵ⬟ࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ࡢᐇ㦂࠿ࡽࠊpTB ࡣỴࡲࡗࡓ᪉ྥ࡛⭷࡟ᤄධࡉࢀࠊ⭷ࢆ㈏㏻ࡍࡿࢳࣕࢿࣝࢆ
ᙧᡂࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀ࡚࠸ࡿࠋ⭷㈏㏻ᆺ࣌ࣉࢳࢻࡢ⮬Ⓨⓗ࡞୍᪉ྥᤄධࡣࠊẘ⣲ࡸ࢘࢖ࣝࢫࡢస⏝ࡢࡓࡵࡢᇶᮏⓗ࡞⏕≀≀⌮Ꮫⓗࣉࣟࢭࢫ࡛࠶ࡿࡀࠊࡑࡢヲ⣽ࡣᮍࡔ࡟ゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ⡆༢࡞ᵓ㐀ࢆࡶࡘ pTB ࡢ⭷ᤄධࡀዴఱ࡟㐍ࡴ࠿ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
2.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࡲࡎࠊ᪤Ꮡࡢ཯ᛂࣔࢹࣝ࡟୙㊊ࡋ࡚࠸ࡓせ⣲ࢆ᫂ࡽ࠿࡟ࡋࡓୖ࡛ࠊKaiB-KaiC 」ྜయᙧᡂࡢ඲ㇺࢆグ㏙ࡍࡿࣔࢹࣝࢆ᪂ࡓ࡟ᥦ᱌ࡋࡓࠋලయⓗ࡟ࡣࠊKaiC ࡢከ㔞యᛶࢆ࠶ࡽࢃ࡟⪃࠼ࡿࡇ࡜ࠊKaiC ࡢ⤖ྜྍ⬟ᵓ㐀ࡣKaiB ⤖ྜ᫬࡟ึࡵ࡚Ᏻᐃ໬ࡉࢀࡿࡇ࡜ࠊKaiC ࡢ⤖ྜྍ⬟ᵓ㐀࡟࠾࠸࡚ ATP ຍỈศゎ࡛⏕ࡌࡓ ADP ࡣ࣮ࣜࣜࢫࡉࢀ࡟ࡃࡃ࡞ࡿࡇ࡜ࢆࣔࢹࣝ࡟᪂ࡓ࡟ྲྀࡾධࢀࡓࠋࡲࡓࠊKaiC ࡢᵓ㐀ኚ໬ࡢࣂ࢖ࣥࢻࡍࡿ ADP ᩘ౫Ꮡᛶࢆㄪ࡭ࡿࡓࡵ࡟ࠊᵓ㐀ኚ໬ࡢ㉳ࡇࡾࡸࡍࡉࢆኚ࠼ࡓ」ᩘࡢ཯ᛂࣔࢹࣝࢆ᳨ウࡋࡓࠋᮏ◊✲ࡣ୍᪉࡛ࠊࣔࢹࣝ
୰ࡢ཯ᛂ㏿ᗘᐃᩘࢆ࣋࢖ࢬ᥎ᐃࡢᯟ⤌ࡳ࡛᥎ᐃࡋࡓࠋࡇࡢ㝿ࠊཧ↷ࡍࡿᐇ㦂ࢹ࣮ࢱ࡜ࡋ࡚ࠊKaiB-KaiC 」ྜ
యᙧᡂࡢฟ∧῭ࡳᐇ㦂ࢹ࣮ࢱࢆ⏝࠸ࡓࠋࡲࡓࠊ཯ᛂ㏿ᗘᐃᩘࡣ࣐ࣝࢥࣇ㐃㙐ࣔࣥࢸ࢝ࣝࣟἲ࡛ࢧࣥࣉࣝࡋࡓࠋ
ࡑࡋ࡚ࠊᚓࡽࢀࡓ཯ᛂ㏿ᗘᐃᩘࡢศᕸࢆ⏝࠸࡚ࠊ」ྜయᙧᡂࡢศᏊᶵᵓࢆᐃ㔞ⓗ࡟㆟ㄽࡋࡓࠋ
2.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ගᤕ㞟࢔ࣥࢸࢼࡢ EET ࢲ࢖ࢼ࣑ࢡࢫࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡍࡿࡓࡵ࡟ࠊࡲࡎࠊࢡࣟࣟࣇ࢕ࣝ(Chl) a ࡜ Chl bࡢᇶᗏ࠾ࡼࡧບ㉳≧ែࢆ㐺ษ࡟グ㏙ࡍࡿࡇ࡜ࡀᚲせ࡜࡞ࡿࠋᮏ◊✲࡛ࡣࠊᡃࠎࡢࢢ࣮ࣝࣉࡢ௨๓ࡢ◊✲࡟ᇶ࡙ࡁࠊᮏ◊✲࡛ࡣࠊࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡢ⤖ᯝࢆࡶ࡜࡟ࠊCAM-B3LYP ỗ㛵ᩘࢆ౑⏝ࡍࡿࡇ࡜࡜ࡋࡓࠋ
࢚ࢱࣀ࣮ࣝࠊ࢔ࢭࢺࣥࠊࢪ࢚ࢳ࢚࣮ࣝࢸࣝࡢ 3 ✀㢮ࡢ⁐፹୰ࡢ Chl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࠊ
QM/MM ィ⟬࡟ࡼࡾບ㉳࢚ࢿࣝࢠ࣮࡞࡝ࢆ㐺ษ࡟෌⌧ࡍࡿ(TD)DFT ィ⟬ࡢ㊥㞳ศ㞳ࣃ࣓࣮ࣛࢱ ȝ ࢆỴᐃࡋࡓࠋࡉࡽ࡟ࠊChl a ࡜ Chl b ศᏊࡢ㟁Ꮚ≧ែࡀ ȝ ࡟ࡼࡾ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿࡟࡞࡝࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋ
2.3 ࣏ࣜࢭ࢜ࢼ࣑ࢻ B㸦pTB㸧ࡢ⭷ᤄධᶵᵓ࡟㛵ࡍࡿ◊✲ᮏ◊✲࡛ࡣࠊ඲ཎᏊ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ࡙ࡁࠊ0.15M ࡢ CsCl Ỉ⁐ᾮ୰ࡢ POPC ⭷࡬ࡢ pTB ࡢᤄධ㐣⛬ࢆゎᯒࡋࡓࠋpTB ࡢኳ↛࢔࣑ࣀ㓟࡟ࡣ AMBER ff14SB ຊሙࢆࠊ㠀ኳ↛࢔࣑ࣀ㓟ṧᇶ࡟ࡣ௨๓ࡢᡃࠎࡢ◊✲࡛Ỵᐃࡋࡓࣃ࣓࣮ࣛࢱࠊࡲࡓࠊPOPC ஧㔜⭷࡟ࡣ Lipid14 ຊሙࠊ࢖࢜ࣥ࡟ࡣ Joung ࡜ Cheatham ࡢࣃ࣓࣮ࣛ
ࢱࢆ⏝࠸ࡓࠋ1 ศᏊࡢ pTBࠊ200 ศᏊࡢ POPC ஧㔜⭷࡜ CsCl Ỉ⁐ᾮ࠿ࡽ࡞ࡿ~81Å×~81Å×~146Å ࡢࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࢭࣝࢆ⏝࠸ࠊpTB ࡢ N ᮎ➃࡜ࠊpTB ࠿ࡽ㐲࠸஧㔜⭷ࡢ POPC ࡢ P ࡢ㊥㞳ࢆ཯ᛂᗙᶆ࡜ࡋࡓࣞࣉࣜ࢝
஺᥮࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢἲ࡟ࡼࡿ⭷ᤄධ࡟㛵ࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊPOPC ஧㔜⭷࡬
ࡢ pTB ࡢ⮬Ⓨⓗᤄධࢆㄪ࡭ࡿࡓࡵࠊ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡛ồࡵࡽࢀࡓᤄධ࡟㛵ࡍࡿ TS ࡼࡾࡶ㐲࠸ᆅⅬ࠿ࡽࠊ
30 ᮏࡢ NPT ᮲௳ࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦ྛ MD ィ⟬ࡣ 1.5ȝs ௨ୖ㸧ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
3.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࡲࡎࠊᮏ◊✲࡛ᥦ᱌ࡋࡓ཯ᛂࣔࢹࣝ࡟ࡼࡾ」ྜయᙧᡂࡢຍ㏿⌧㇟ࡀㄝ࡛᫂ࡁࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡑࡋ࡚ࠊ

ᐃ㔞ⓗ࡞ゎᯒ࡟ࡼࡾࠊࡑࡢຍ㏿⌧㇟ࡢࡓࡵ࡟ࡣࠊKaiC ࡢከ㔞యᛶࡀᮏ㉁ⓗ࡟㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞

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ࡗࡓࠋࡲࡓࠊ཯ᛂ㏿ᗘᐃᩘࡢ࣋࢖ࢬ᥎ᐃࡢ⤖ᯝ࡜ࡋ࡚ࠊKaiC ࡢ⤖ྜྍ⬟ᵓ㐀࠿ࡽࡢ ADP ࣮ࣜࣜࢫ࠾ࡼࡧࡑ
ࢀ࡟ㄏᑟࡉࢀࡿ KaiB ࡢ㞳⬺ࡣᴟࡵ࡚㐜࠸ࡇ࡜ࡀண᝿ࡉࢀࡓࠋࡇࢀࡣཧ↷ࡋࡓ KaiB-KaiC 」ྜయᙧᡂ࡜ẚ㍑
ࡋ࡚ࡶ࠿࡞ࡾ㐜࠸ࡶࡢ࡛࠶ࡿࠋࡍ࡞ࢃࡕࠊࡇࢀࡣ࣋࢖ࢬ᥎ᐃ࡟ࡼࡾ㞃ࢀࡓ㐜࠸⌧㇟ࢆぢࡘࡅฟࡋࡓࡇ࡜࡟┦ᙜࡍࡿࠋ࡞࠾ࠊᮏ◊✲ࡣ PLOS Comput. Biol.ㄅ࡛ฟ∧ࡉࢀࡓࡀࠊࡇࡢᴟࡵ࡚㐜࠸ KaiB 㞳⬺㏿ᗘࡣᮏ◊✲ࡢᚋ
࡟Ⓨ⾲ࡉࢀࡓᐇ㦂◊✲࡟࠾࠸࡚ᐇドࡉࢀࡓ(Biophysics and Physicobiology (2022))ࠋࡇࢀࡣᮏ◊✲࡛ᥦ᱌ࡋࡓࣔ
ࢹࣝࡢጇᙜᛶࢆᙉࡃᨭᣢࡍࡿࡶࡢ࡛࠶ࡿࠋ
3.2 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲࢚ࢱࣀ࣮ࣝࠊ࢔ࢭࢺࣥࠊࢪ࢚ࢳ࢚࣮ࣝࢸࣝࡢ 3 ✀㢮ࡢ⁐፹୰ࡢ Chl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢィ⟬ࢆᐇ㦂್࡜ẚ㍑ࡋࠊChl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ෌⌧ࡍࡿ᭱㐺࡞㊥㞳ศ㞳ࣃ࣓࣮ࣛࢱ ȝ ࢆỴᐃࡋࡓࠋChl a
࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢ෌⌧࡟౑ࢃࢀࡓȣࡣࠊᶆ‽ⓗ࡟⏝࠸ࡽࢀ࡚࠸ࡿ ȝ㸦0.33㸧ࡼࡾࡶࠊࡉࡽ࡟ࠊ௨๓
ࡢ◊✲࡛Ỵᐃࡋࡓࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ㸦BChl㸧a ࡟ᑐࡍࡿ㊥㞳ศ㞳ࣃ࣓࣮ࣛࢱࡼࡾࡶᑠࡉ࠸ࡇ࡜ࡶ᫂ࡽ
࠿࡜࡞ࡗࡓࠋࡇࢀࡣ Chl a ࡜ Chl b ࡢඹᙺ㡿ᇦࡀ BChl a ࡼࡾ኱ࡁࡃࠊ㟁Ꮚࡢ㠀ᒁᅾᛶࡀቑࡋ࡚࠸ࡿࡇ࡜ࢆ཯
ᫎࡋ࡚࠸ࡿࠋࡲࡓࠊChl a ࡟ᑐࡋ࡚᭱㐺࡞ȣࡣ Chl b ࡢࡶࡢࡼࡾࢃࡎ࠿ᑠࡉ࠸ࡇ࡜ࡶࠊChl a ࡜ Chl b ࡢ㠀ᒁᅾᛶࡢ㐪࠸ࢆ཯ᫎࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊບ㉳࢚ࢿࣝࢠ࣮ࡢศᕸ࠿ࡽᚓࡽࢀࡓ Chl a ࡜ Chl b ࡢ෌㓄⨨࢚ࢿࣝࢠ࣮ࡣ PSII ୰ࡢᐇ㦂್࡜ྠᵝࡢ್㸦~30cm-1㸧࡜࡜ࡶ࡟ࠊ⥳Ⰽ◲㯤⣽⳦ࡢ FMO ࢱࣥࣃࢡ㉁ࡢ BChl aࡼࡾࡶᑠࡉ࠸ࡇ࡜ࡶศ࠿ࡗࡓࠋࡲࡓࠊ⁐ᾮࡢᴟᛶࡸỈ⣲⤖ྜ࡟ࡼࡾࠊChl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢపୗ
ࡸບ㉳࢚ࢿࣝࢠ࣮ศᕸࡢᗈࡀࡾࡀኚ໬ࡍࡿࡇ࡜ࡶ᫂ࡽ࠿࡟࡞ࡾࠊLHCII ୰࡟࠾ࡅࡿಶࠎࡢ Chl a ࡸ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡀ࡝ࡢࡼ࠺࡟ᦂࡽࡄࡢ࠿࡟ࡘ࠸࡚㠀ᖖ࡟⯆࿡ࡀࡶࡓࢀࡿࠋ࡞࠾ࠊ௒ᅇᚓࡽࢀࡓ ȝ ࡣࠊȝ ࡢ᭱㐺໬࡟⏝࠸࡚࠸࡞࠸ DMF ⁐ᾮ୰ࡢ Chl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡶ෌⌧ࡍࡿࠋࡍ࡞ࢃࡕࠊᮏ◊✲࡛Ỵᐃࡋࡓȝ ࡣࠊ᭱㐺໬࡟⏝࠸࡚࠸࡞࠸௚ࡢ⣔ࡢ Chl a ࡜ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢゎᯒ࡟ࡶ㐺⏝ྍ⬟࡛࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊChl a ࡸ Chl b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢ㐺ษ࡞グ㏙ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ
3.3 ࣏ࣜࢭ࢜ࢼ࣑ࢻ B㸦pTB㸧ࡢ⭷ᤄධᶵᵓ࡟㛵ࡍࡿ◊✲௨๓ࡢᡃࠎࡢ◊✲࡛♧ࡋࡓࡀࠊpTB ࡣỈ୰࡛ࡶ⭷୰࡜ྠࡌ ȕ-helix ᵓ㐀࡟ᙧᡂࡋ࡚࠾ࡾࠊࡲࡎࠊ⭷ᤄධ௨๓࡟ᙧᡂࡉࢀࡓᵓ㐀ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡍࡿࡇ࡜࡞ࡃࠊ⭷࡟ᤄධࡉࢀࡿࡇ࡜ࢆ♧ࡋࡓࠋከࡃࡢ࣌ࣉࢳࢻẘ⣲ࡀ⭷㈏㏻࣊ࣜࢵࢡࢫࡢ࢜ࣜࢦ࣐࣮໬࡟ࡼࡗ࡚ࢳࣕࢿࣝࢆᙧᡂࡍࡿࡇ࡜࠿ࡽࠊࡇࡢࡼ࠺࡞⭷ᤄධ㐣⛬ࡣ pTB ࡢ≉␗ⓗ࡞≉ᚩ࡛࠶ࡿࠋ⮬⏤࢚ࢿࣝࢠ࣮ࡢゎᯒ࠿ࡽࠊࣂࣝࢡỈ୰࠿ࡽ⭷⾲㠃࡟ pTB ࡀ᥋㏆ࡍࡿ࡟ᚑ࠸ࠊpTB ࡢ㓄ྥ⮬⏤ᗘࡀไ㝈ࡉࢀࠊ␯Ỉᛶṧᇶ㸦Mhe㸧ࢆࡶࡘ N ᮎ➃ഃࢆྥࡅ࡚⭷࡟᥋㏆ࡋ╔ᆅࡍࡿࠋࡑࡢ㝿ࠊ⣙ 4.3kcal/molࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࢆ᭷ࡋࠊࡑࡢᚋࠊMhe ṧᇶࢆඛ㢌࡟஧㔜⭷ࡢୖഃࡢ⭷࡟౵ධࡋࠊࡉࡽ࡟ୗഃࡢ⭷࡬࡜⭷ᤄධࡀ㐍⾜ࡋࠊ⭷㈏㏻ࡀ᏶஢ࡍࡿࠋ⭷ᤄධ㐣⛬࡟࠾࠸࡚ pTB ࡢ ȕ-helix ࡀኚᙧࡍࡿࡇ࡜࡞ࡃࠊ⭷㈏㏻ࡋࡓᵓ
㐀࡛ࡣ Mhe ࡣୗഃࡢ⭷ࡢഹ࠿ෆ㒊࡟఩⨨ࡋᏳᐃ໬ࡉࢀ࡚࠾ࡾࠊpTB ࡣ⣙ 17 ᗘഴ࠸࡚࠸ࡿࠋࡲࡓࠊpTB ࡢ୍᪉ྥᛶᤄධ࡟࠾࠸࡚ࠊ⭷࡬ࡢ╔ᆅ᫬ࠊ㐍ධ᫬࡟࠾ࡅࡿ Mhe ࡢᙺ๭ࡢ㔜せᛶࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡉࡽ࡟ࠊ⮬Ⓨⓗ⭷ᤄධࢆゎᯒࡍࡿࡓࡵࠊ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡢࡼ࠺࡞ࣂ࢖࢔ࢫࢆ࠿ࡅ࡞࠸ MD ィ⟬ࢆ⾜ࡗࡓࠋ⭷ᤄධࡢ㌶㊧ࢆゎᯒࡋࡓ⤖ᯝࠊpTB ⭷࡬ࡢᤄධ㐣⛬࡟࠾࠸࡚ࠊୖഃ࡜ୗഃࡢ⭷ࡢ㛫࡟ Mhe ࡀ㛗᫬㛫ࠕᤕᤊࡉࢀࡿᤄධࠖ࡜
ࠕᤕᤊࡉࢀ࡞࠸෇⁥࡞ᤄධࠖࡢ 2 ࡘࡢሙྜࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊ⭷ᤄධ࡜࠸࠺୍ぢ༢⣧࡞㐣⛬࡛࠶ࡿ࡟ࡶ㛵ࢃࡽࡎࠊpTB ࡜⭷࡜ࡢ┦஫స⏝ࡢ㐪࠸࡟ࡼࡾࠊ඲ࡃᵝ┦ࡢ␗࡞ࡿ⤒㊰࡛ᤄධ㐣⛬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊpTB ࡀ஧㔜⭷ࡢ⭷ཌ࡟㏆࠸඲㛗ࢆࡶࡕࠊᖹ⾮≧ែ࡟࠾࠸࡚ࡣ⭷࡟ᑐࡋ࡯ࡰᆶ
┤࡟ᤄධࡉࢀ࡚࠸ࡿࡓࡵࠊpTB ࡢᤄධ࡟ࡼࡿ⭷࡬ࡢᙳ㡪ࡣᒁᡤⓗ࡛㝈ᐃⓗ࡛࠶ࡿࡇ࡜࡞࡝ࡶ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

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4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ᩧ⸨┿ྖ, ͆ࢧ࢖ࢺ౫Ꮡࡺࡽࡂ࡟ࡼࡿ FMO ࢱࣥࣃࢡ㉁ࡢ⋡ⓗບ㉳࢚ࢿࣝࢠ࣮⛣ື͇, ྡྂᒇ኱Ꮫ໬Ꮫ⛉ࢭ࣑ࢼ࣮, ྡྂᒇ, Oct. 27 (2021).
‫ ۻ‬Zhu Zhe, ᮾ㞞኱ᩧ⸨┿ྖ㸪͆ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ࡼࡿ⁐ᾮ୰ࡢࢡࣟࣟࣇ࢕ࣝ D ࡜ E ࡢບ㉳࢚ࢿࣝࢠ࣮࡟
㛵ࡍࡿ⌮ㄽⓗ◊✲͇➨  ᅇศᏊ⛉Ꮫウㄽ఍ᮐᖠ, Sep. 19 (2021).
‫ ۻ‬S. Saito, "Excitation energy transfer in the Fenna-Matthews-Olson protein optimized by site-dependent
fluctuations", Symposium on Frontiers in quantum and classical molecular dynamics for complex systems, Pacifichem
2020, Honolulu, USA, Dec. 18 (2021).
‫ ۻ‬S. Saito, "Molecular mechanism of acceleration and retardation of collective orientation relaxation of watermolecules in aqueous solutions", Symposium on Structure and function of complex molecular clusters - challenges intheory and experiment, Pacifichem 2020, Honolulu, USA, Dec. 20 (2021).
‫ ۻ‬S. Saito, "Structure, dynamics, and thermodynamics of supercooled water", SNU Leaders in Chemistry
Symposium on Quantum and Statistical Fluctuations in Molecular Materials, Seoul National University, Seoul, Korea,
Feb. 8 (2022).
‫ ۻ‬S. Saito, "Structure, dynamics, and thermodynamics of supercooled water", Department of Physics, Stockholm
University, Stockholm, Sweden, March 18 (2022).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Y. Matsumura and S. Saito, Microscopic insights into dynamic disorder in the isomerization dynamics of theprotein BPTI, J. Chem. Phys. 154, 224113 (11 pages) (2021).
‫ ۻ‬Y.-W. Kuo, P.-H. Tang, H. Wang, T.-M. Wu, and S. Saito, Tetrahedral structure of supercooled water at ambientpressure and its influence on dynamic relaxation: Comparative study of water models, J. Mol. Liquids 341, 117269(2021).
I. Ohmine and S. Saito, Dynamical behavior of water; Fluctuation, reactions and phase transitions, Bull. Chem. Soc.
Jpn. 94, 2575-2601 (2021).
‫ ۻ‬M. Kalathingal, T. Sumikama, S. Oiki, and S. Saito, Vectorial insertion of a ȕ-helical peptide into membrane: A
theoretical study on polytheonamide B, Biophys. J. 120, 4786-4797 (2021).
‫ ۻ‬T. Inagaki and S. Saito, Hybrid Monte Carlo method with potential scaling for sampling from the canonicalmultimodal distribution and imitating the relaxation process, J. Chem. Phys. 156, 104111 (12 pages) (2022).
‫ ۻ‬S.-i. Koda and S. Saito, Multimeric structure enables the acceleration of KaiB-KaiC complex formation induced
by ADP/ATP exchange inhibition, PLoS Comput. Biol. 18, e1009243 (24 pages) (2022).
‫ ۻ‬Z. Zhu, M. Higashi, and S. Saito, Excited states of chlorophyll a and b in solution by time-dependent density
functional theory, J. Chem. Phys. (Special topic on Photosynthetic Light-Harvesting and Energy Conversion) 156,
124111 (13 pages) (2022).

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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㔠⃝ᝆ⣖ࠊ⩚㫽ᩔஓ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࠸ࡿࠋᮏᖺࡣࠊ1) ⓑ㔠㘒యࡢ⤖ᬗ≧ែ࡟࠾ࡅࡿจ㞟ㄏ㉳ࣜࣥගⓎග࡜ࡑࡢ⇕⪏ᛶࡢ㉳※ࠊ2) จ⦰┦㖟ࢼࣀࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ㏆㉥እࣜࣥගⓎග࡜ࡑࡢ㧗࠸Ⓨග㔞Ꮚ཰⋡ࡢ㉳※ࠊ3) CAu6 ࢡࣛࢫࢱ࣮ࡢ༢ᗙ㓄఩Ꮚ࡟ࡼࡿ㠀ᑐ⛠ᛶᑟධ㸸࢟ࣛࣝᵓ㐀ࡢᏳᐃᛶ࠾ࡼࡧ෇஧Ⰽᛶࡢ⌮ㄽゎᯒࠊ4) ᙉ┦㛵㟁Ꮚ⣔ࡢ㟁Ꮚඹ㬆≧ែ࡟㛵ࡍࡿ⌮ㄽゎᯒࠊ5) ࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡋࡓⓑ㔠ࢧࣈࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀࠾ࡼࡧ㓟⣲㑏ඖ཯ᛂάᛶ࡟㛵ࡍࡿ⌮ㄽゎᯒࠊ6) 㓟໬ࢳࢱࣥ࡟ࡼࡿ NO ࡢ NH3-SCR ගゐ፹཯ᛂࡢ⾲㠃౫Ꮡᛶ࡟ࡘ࠸࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 09 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ SAC-CI ἲ࡜ࡑࡢ㛤Ⓨ∧࠾ࡼࡧ CAP/SAC-CI ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋDFT ἲࡸTDDFT ἲࠊCCSD(T)ἲ࡟ࡼࡿィ⟬ࢆᐇ᪋ࡋࡓࠋ୺࡟ OpenMP ࡟ࡼࡿ SMP ୪ิィ⟬ࢆ⾜ࡗࡓࠋ3◊✲┠ⓗࠊෆᐜ

3.1. ⓑ㔠㘒యࡢ⤖ᬗ≧ែ࡟࠾ࡅࡿจ㞟ㄏ㉳ࣜࣥගⓎග࡜ࡑࡢ⇕⪏ᛶࡢ㉳※㔠ᒓ㘒య⤖ᬗࡢจ㞟ㄏ㉳Ⓨග(AIE)ࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣ㸪ᵝࠎ࡞ගᶵ⬟ᛶᮦᩱࢆ㛤Ⓨࡍࡿୖ࡛㔜せ࡞ㄢ㢟࡛࠶ࡿࠋࡇࢀࡲ࡛ᩘ༑ᖺ࡟ࢃࡓࡾ㸪AIE ࡢⓎගᶵᵓ࠾ࡼࡧᾘගᶵᵓࡀ◊✲ࡉࢀ࡚ࡁࡓࡀ㸪ᮍࡔ᏶඲࡟
ࡣゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣ㸪AIE άᛶ࡛࠶ࡿⓑ㔠㘒యࡢ⤖ᬗ≧ែ࡟࠾ࡅࡿࣜࣥගⓎග࡜ᾘගࡢ㟁Ꮚ㐣⛬ࢆ㸪⌮ㄽ࡜ᐇ㦂࡟ᇶ࡙࠸࡚◊✲ࡋࡓࠋࡇࢀࡽࡢ㘒యࡣ㸪⤖ᬗ≧ែ࡛㔠ᒓ-ࣜ࢞ࣥࢻ㛫ࡢ㟁Ⲵ⛣ືບ㉳≧ែ࠿ࡽࡢࣜࣥⓎගࢆ♧ࡍࡀ㸪ᵓ㐀࡟ࡼࡗ࡚Ⓨගࡢ⇕⪏ᛶࡀ␗࡞ࡿࠋ⤖ᬗᵓ㐀࡟ࡼࡿᵓ㐀⦆࿴ࡢไ㝈࠿ࡽ AIE Ⓨ⌧ࡢᶵᵓࢆゎ᫂ࡋࡓࠋࡲࡓ⇕⪏ᛶࡢ≉ᛶࡀ㸪S0 ≧ែ࡜ T1 ≧ែࡢ᭱ᑠ࢚ࢿࣝࢠ࣮஺ᕪⅬ(MECP)ࡢ఩⨨࡜ᴟࡵ࡚Ⰻࡃ┦㛵ࡍࡿࡇ࡜ࢆ♧ࡋࡓࠋࡉࡽ࡟㸪2 ࡘࡢ⌮ㄽࣔࢹࣝࡢ⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛㸪AIE ࡟࠾ࡅࡿ Pt-Pt ┦஫స⏝ࡢᙺ๭ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
3.2. จ⦰┦㖟ࢼࣀࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ㏆㉥እࣜࣥගⓎග࡜ࡑࡢ㧗࠸Ⓨග㔞Ꮚ཰⋡ࡢ㉳※㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢࣆࣜࢪࣥ⁐ᾮࢆග↷ᑕࡍࡿࡇ࡜࡟ࡼࡾ㸪㏆㉥እ㡿ᇦ㸦770nm㸧࡟ᙉ࠸ࣜࣥගⓎගࢆ♧ࡍࡇ࡜ࡀᐇ㦂࡛ぢฟࡉࢀࡓࠋࡇࡢ㏆㉥እ㡿ᇦࡢⓎග㔞Ꮚ཰⋡ࡣ 33㸣࡛࠶ࡾ㸪㔠ࢆࢻ࣮ࣉࡋࡓྜ㔠ࢼࣀࢡࣛࢫࢱ
࣮࡛ࡣ 800nm ࡟Ⓨගࡀࢩࣇࢺࡋ㸪ࡑࡢⓎග㔞Ꮚ཰⋡ࡣ 45%௨ୖࢆ♧ࡍࠋࡇࢀࡣ㔠ᒓࢼࣀࢡࣛࢫࢱ࣮࡛ࡣᴟࡵ࡚኱ࡁ࡞Ⓨග㔞Ꮚ཰⋡࡜ゝ࠼ࡿࠋ⌮ㄽィ⟬࡟ࡼࡗ࡚㸪㖟ࢼࣀࢡࣛࢫࢱ࣮࡜ࣆࣜࢪࣥࡢ㓄఩ᵓ㐀࠾ࡼࡧ㟁Ꮚ≧ែࢆゎᯒࡋ㸪ࡇࡢⓎග࡟ࡣບ㉳୕㔜㡯≧ែࡀ㛵୚ࡍࡿࡇ࡜㸪ග↷ᑕ࡟ࡼࡗ࡚ࢼࣀࢡࣛࢫࢱ࣮ࡢ㟁Ⲵᒁᅾ≧ែࡀㄏ㉳ࡉࢀ㸪㏆㉥እⓎගࢧ࢖ࢺࡀᙧᡂࡉࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

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3.3. CAu6 ࢡࣛࢫࢱ࣮ࡢ༢ᗙ㓄఩Ꮚ࡟ࡼࡿ㠀ᑐ⛠ᛶᑟධ㸸࢟ࣛࣝᵓ㐀ࡢᏳᐃᛶ࠾ࡼࡧ෇஧Ⰽᛶࡢ⌮ㄽゎᯒ㓄఩Ꮚ࡟ࡼࡿ㔠ᒓࢡࣛࢫࢱ࣮ࡢ㠀ᑐ⛠ᛶᑟධࡣࠊ࢟ࣛࣝ㌿෗ࡢᶵᵓࡸᵓ㐀ᏳᐃᛶࡢほⅬ࡛⯆࿡῝࠸ࠋCAu6ࢡࣛࢫࢱ࣮ࡣࠊⅣ⣲୰ᚰࢆ㔠ཎᏊࡀᅖࡴ㸴㠃యࡢᵓ㐀ࢆ᭷ࡍࡿࡀࠊᮏ◊✲࡛ࡣࠊN-࣊ࢸࣟ࢝ࣝ࣋ࣥࡢ༢ᗙ㓄఩Ꮚ࡟ࡼࡗ࡚ࠊ᤬ࡌࢀࡓᵓ㐀ࡢࢡࣛࢫࢱ࣮ࢆ⏕ᡂࡋࠊ࢟ࣛࣝ㌿෗࡟ึࡵ࡚ᡂຌࡋࡓࠋࡉࡽ࡟ࠊ࢟ࣛࣝศ๭ࢆ⾜࠸ࠊ⁐ᾮ୰࡛ࡶᏳᐃ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࠊX ⥺ᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋ⌮ㄽゎᯒ࡛ࡣࠊ࢟ࣛࣝᵓ㐀ࡢᏳᐃᛶࡸࠊ
㠀ᑐ⛠࡞ C-Au ⤖ྜ࠾ࡼࡧ Au-Au ⤖ྜ࡟㛵ࡋ࡚ヲ⣽࡞ゎᯒࢆᐇ᪋ࡋࡓࠋࡉࡽ࡟ࠊ྾཰ࢫ࣌ࢡࢺࣝࡸ෇஧Ⰽᛶ
ࢫ࣌ࢡࢺࣝࡢゎᯒࢆ⾜࠸ࠊ㧗࢚ࢿࣝࢠ࣮㡿ᇦࡲ࡛ᐃ㔞ⓗ࡞ᖐᒓࢆ⾜ࡗࡓࠋ㻌
3.4. ᙉ┦㛵㟁Ꮚ⣔ࡢ㟁Ꮚඹ㬆≧ែ࡟㛵ࡍࡿ⌮ㄽゎᯒඹ㬆≧ែࡣ‽Ᏻᐃ≧ែ࡛࠶ࡾ㸪㟁Ꮚ≧ែ࡛ࡣ‽Ᏻᐃ࢔ࢽ࢜ࣥ㸪ከ౯࢖࢜ࣥ㸪ෆẆ࣮࣍ࣝ≧ែ࡞࡝ࡀ࠶ࡿࠋ
ᡃࠎࡣ㸪㟁Ꮚඹ㬆≧ែࡢ⌮ㄽ࡜ࡋ࡚⊂⮬ࡢᑕᙳᆺ CAP/SAC-CI ἲࡸ ACCC SAC-CI ἲࢆ㛤Ⓨࡋࡓࠋᮏᖺᗘࡣ㸪ᙉ┦㛵㟁Ꮚ⣔࡛࠶ࡿ Be3-࠾ࡼࡧ Mg3-ࡢ㐣Ώⓗ࢔ࢽ࢜ࣥ≧ែࢆ㸪 CCSD(T), SAC-CI, NEVPT2 ἲ࡟ᇶ࡙ࡃゎᯒ᥋⥆⤖ྜ⌮ㄽ㸪࠾ࡼࡧᑕᙳᆺ CAP/XMS-CASPT2 ἲ࡟ࡼࡗ࡚ゎᯒࡋࡓࠋࡇࢀࡽ 2 ✀㢮ࡢࢡࣛࢫࢱ࣮ࡢ㸲ࡘࡢ㟁Ꮚඹ㬆≧ែࢆゎᯒࡋ㸪p-ı ࠾ࡼࡧ p-ʌ ≧ែ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓࠋඹ㬆ᖜࡣ 1.0㸫1.5 eV ࡜⊃ࡃ㸪㟁Ꮚඹ㬆≧ែ࡜ࡋ࡚༑ศほ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋࡉࡽ࡟ỈศᏊ࡜ࡢ┦஫స⏝࡛㐣Ώⓗ࢔ࢽ࢜ࣥ≧ែࡢᑑ࿨ࡀ㸰࣮࢜ࢲ࣮㛗ᑑ࿨࡟࡞ࡿࡇ࡜ࢆ♧ࡋࡓࠋ㻌
3.5. ࢢࣛࣇ࢙ࣥ࡟ᢸᣢࡋࡓⓑ㔠ࢧࣈࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀࠾ࡼࡧ㓟⣲㑏ඖ཯ᛂάᛶ࡟㛵ࡍࡿ⌮ㄽゎᯒ⇞ᩱ㟁ụࡢ㈇ᴟ࡟ࡣⓑ㔠㟁ᴟࡀ⏝࠸ࡽࢀ࡚࠸ࡿࡀࠊ㓟⣲㑏ඖ཯ᛂࡣ Pt ࢆࢼࣀ⢏Ꮚ໬ࡍࡿࡇ࡜࡟ࡼࡾάᛶ໬
ࡉࢀࡿࠋࡋ࠿ࡋࠊࢧ࢖ࢬ౫Ꮡᛶࡸάᛶࢧ࢖ࢺ࡟㛵ࡍࡿศᏊㄽⓗ⌮ゎࡣ༑ศ࡛ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊ࢞ࣛࢫ≧Ⅳ⣲࡟ᢸᣢࡋࡓ Pt ࢧࣈࢼࣀࢡࣛࢫࢱ࣮(Ptn, n=3-9)ࡀࠊỗ⏝ࡢ Pt/C 㟁ᴟࡼࡾࡶ㉁㔞ẚάᛶࡀᴟࡵ࡚㧗࠸ࡇ࡜ࢆぢฟࡋࠊ⌮ㄽゎᯒࢆᐇ᪋ࡋࡓࠋ⌮ㄽゎᯒ࡛ࡣࠊࢢࣛࣇ࢙ࣥୖࡢ Pt ࢡࣛࢫࢱ࣮(Ptn, n=4-8)ࡢᏳᐃᵓ㐀ࢆᩘ✀㢮ᥦ♧ࡋࠊXAFS ࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊPt ࢡࣛࢫࢱ࣮ࡢ྾╔Ᏻᐃᵓ㐀ࢆỴᐃࡋࡓࠋࡉࡽ࡟཯ᛂ
ࡢάᛶⅬࢆ㒊ศ≧ែᐦᗘ࠿ࡽ⌮ㄽⓗ࡟≉ᐃࡋࠊ㓟⣲㑏ඖ཯ᛂࡢ࢚ࢿࣝࢠ࣮࣭ࣉࣟࣇ࢓࢖ࣝࢆィ⟬ࡍࡿࡇ࡜࡟
ࡼࡗ࡚ࠊ㐣㟁ᅽ㸦overpotential㸧ࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡋࡓࠋ㻌
3.6. 㓟໬ࢳࢱࣥ࡟ࡼࡿ NO ࡢ NH3-SCR ගゐ፹཯ᛂࡢ⾲㠃౫Ꮡᛶ᭱㏆㸪㓟໬ࢳࢱࣥ࡟࠾ࡅࡿ NO ࡢ NH3-SCR ࡛ࡣ㸪ゐ፹ᛶ⬟࡟⾲㠃౫Ꮡᛶࡀ࠶ࡿࡇ࡜ࡀぢฟࡉࢀࡓࠋᮏ◊✲࡛ࡣ㸪㓟໬ࢳࢱࣥ(001)࠾ࡼࡧ(101)⾲㠃࡟࠾ࡅࡿ NO ࡢ NH3-SCR ཯ᛂࢆ㸪(001)⾲㠃ࡢ㧗࠸ᛶ⬟ࡢせᅉ࡟↔Ⅼࢆᙜ࡚㸪ࢫࣛࣈࣔࢹࣝᐦᗘỗ㛵ᩘ⌮ㄽࢆ⏝࠸࡚⣔⤫ⓗ࡟ㄪᰝࡋࡓࠋࡑࡢ⤖ᯝ㸪(001)㠃࡛ࡣ⾲㠃㓟⣲ࡢάᛶࢧ࢖ࢺࡀ཯ᛂ࡛㔜せ࡞ᙺ๭ࢆᯝࡍࡇ࡜ࡀ♧ࡉࢀ㸪⾲㠃㓟⣲ࡀ฼⏝ࡉࢀࡿ Mars van Krevelen ᶵᵓࡀᨭᣢࡉࢀࡓࠋ
᭱ࡶ᭷฼࡞⤒㊰࡛ࡣ㸪(001)㠃࡛ࡣ࢚ࢿࣝࢠ࣮ࣂࣜ࢔ࡀ 61 kJ/mol ࡜పࡃ㸪NH3 ࡢゎ㞳ࡀᚊ㏿ẁ㝵࡜࡞ࡿࡀ㸪(101)㠃࡛ࡣࣂࣜ࢔ࡣ 156 kJ/mol ࡜㧗ࡃ㸪NH2NO ࡢศゎࡀᚊ㏿࡜࡞ࡿࠋᮏ⤖ᯝࡣ㸪(001)㠃ࢆᣢࡘ TiO2 ࢼࣀࢩ࣮ࢺࡀ㸪(101)㠃ࢆᣢࡘ TiO2 ࢼࣀ⢏Ꮚࡼࡾࡶඃࢀࡓゐ፹ᛶ⬟ࢆ♧ࡍᐇ㦂⤖ᯝ࡟ᑐᛂࡋ࡚࠾ࡾ㸪ࡑࡢせᅉࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㻌

4Ⓨ⾲ᐇ⦼1) մM. Ehara, “Theoretical Chemistry for Complex Systems: Nanocluster and Heterogeneous Catalysts,” The
2nd IMS-SKKU-UJN symposium on Molecular Science, Okazaki (Zoom), Japan, October 5, 2021.

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2) մM. Ehara, “Theoretical Studies on Heterogeneous and Nanocluster Catalysts: Collaborations with
Experiment,” The 8th International Symposium of Institute for Catalysis: Novel Approaches for Next Generation
Catalysis, Sapporo (Zoom), Japan, August 5, 2021 (Keynote Talk).
3) մM. Ehara, “Theoretical Chemistry for Complex Systems: Pd-Au Nanocluster and Heterogeneous Catalysts,”
Pacifichem 2021: Symposium (#393) Triangle of Heterogeneous Catalysis, Surface Science, and Theory, On-line (Zoom),
December 19-20, 2021.

5

ฟ∧ᐇ⦼

1) J. Yin, M. Ehara, S. Sakaki, "Single Atom Alloys vs. Phase Separated Alloys in Cu, Ag, and Au atoms with Ni(111)
and Ni, Pd, and Pt atoms with Cu(111): A Theoretical Exploration", Phys. Chem. Chem. Phys. in press (2022).
2) X.-L. Pei, P. Zhao, H. Ube, Z. Lei, K. Nagata, M. Ehara, M. Shionoya, "Asymmetric Twisting of C-centered Octahedral
Gold(I) Clusters by Chiral N-heterocyclic Carbene Ligation", J. Am. Chem. Soc. 144, 2156–2163 (2022).
3) 䖩A. Ohnuma, K. Takahashi, H. Tsunoyama, T. Inoue, P. Zhao, A. Velloth, M. Ehara, N. Ichikuni, M. Tabuchi, A.
Nakajima, "Enhanced Oxygen Reduction Activity of Size-Selected Platinum Subnanocluster Catalysts: Ptn (n=3-9) ",Catal. Sci. Tech. 12, 1400–1407 (2022).
4) 䖩P. Zhao, M. Ehara, A. Satsuma, S. Sakaki, "Theoretical Study of the Propene Combustion Catalysis of Chromite
Spinels: Reaction Mechanism and Relation between the Activity and Electronic Structure of Spinels", J. Phys. Chem. C,
125, 25983–26002 (2021).
5) R. Inoue, T. Naota, M. Ehara, "Origin of the Aggregation-Induced Phosphorescence of Vaulted transbis(Salicylaldiminato) Platinum(II) Complexes: The role of the Metal–Metal Interactions on Emission Decay in the
Crystalline State", Chem. Asian J. 16, 3129–3140 (2021).
6) Y.-L. Shen, P. Zhao, J. Jin, J. Han, C. Liu, Z. Liu, M. Ehara, Y.-P. Xie, X. Lu, "A Comparative Study of[Ag11(iPrS)9(dppb)3]2+ and [Ag15S(sBuS)12(dppb)3]+: Templating effect on Structure and Photoluminescence", Dalton
Trans., 50, 10561–10566 (2021).
7) 䖩A. Junkaew, M. Ehara, L. Huang, S. Namuangruk, "Facet-Dependent Catalytic Activity of Anatase TiO2 for the
Selective Catalytic Reduction of NO with NH3: A Dispersion-Corrected Density Functional Theory Study", Appl. Catal.
A, 623, 118250 (2021).
8) 䖩J. Kodchasee, C. Chanloi, P. Khemthong, B. Uapipatanakul, M. Ehara, K. Bobuatong, "Catalytic Oxidation of
Benzyl Alcohol to Benzaldehyde on Au8 and Au6Pd2 Clusters: A DFT Study on the Reaction Mechanism", Catalysts, 11,
720–1–14 (2021).
9) W. Ishii, S. Katao, Y. Nishikawa, Y. Okajima, A. Hatori, M. Ehara, T. Kawai, T. Nakashima, "The Emergence of Intense
Near-infrared Photoluminescence by Photoactivation of Silver Nanoclusters", Chem. Commun., 57, 6483-6486 (2021).
10) J. U. Davis, Jr., Q.M. Phung, T. Yanai, M. Ehara, T. Sommerfeld, "Lifetimes of Be3ࡳ and Mg3ࡳ Cluster Dianions", J.
Phys. Chem. A, 125, 3579–3588 (2021).
11) Y. Morisawa, E. Tanimura, M. Ehara, H. Sato, "Attenuated Total Reflection-Far-Ultraviolet Spectroscopy and
Quantum Chemical Calculation Study of the Electronic Structure of Top Surface and Bulk of Polyethylenes with Different
Crystallinity", Appl. Spectrosc., 75, 971–979 (2021).

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ࢱࣥࣃࢡ㉁จ㞟࡜จ㞟㜼ᐖ๣ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
Molecular dynamics simulations of protein aggregation and its
aggregation inhibitors‫ۑ‬ዟᮧஂኈ㸪ఀ⸨ᬡ㸪㇂ᮏ຾୍㸪ᐑ⃝࿴ஂ㸪⚟ཎ኱㍤㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗ㸪ෆᐜ
ࢱࣥࣃࢡ㉁ࡣ㏻ᖖ㸪⏕యෆ࡛ࡑࢀࡒࢀࡀṇࡋࡃᢡࡾࡓࡓࡲࢀ㸪ࡑࡢᶵ⬟ࢆ⥔ᣢࡋ࡚࠸ࡿ㸬ࡋ࠿ࡋ㸪⪁໬࡞࡝ࡢ⌮⏤࡟ࡼࡾࡑࡢ⃰ᗘࡀ㧗ࡃ࡞ࡿ࡜จ㞟ࡋ㸪࢜ࣜࢦ࣐࣮ࡸ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆᙧᡂࡍࡿ㸬࢜ࣜࢦ࣐࣮ࡣ⌫≧㸪࢔࣑ࣟ࢖ࢻ⥺⥔ࡣ⥺⥔≧࡟จ㞟ࡋ࡚࡛ࡁࡓ≀㉁࡛࠶ࡿ㸬ࡇࢀࡽࡢࢱࣥࣃࢡ㉁ࡢจ㞟యࡣ⣙  ✀㢮ࡢࣄࢺࡢ⚄⤒ኚᛶ⑌ᝈ࡜㛵㐃ࡋ࡚࠸ࡿࠋ౛࠼ࡤ㸪࢔ࣝࢶࣁ࢖࣐࣮⑓ࡣ࢔࣑ࣟ࢖ࢻ ȕ㸦$ȕ㸧࣌ࣉࢳࢻࡢจ㞟యࡀཎᅉ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࢱࣥࣃࢡ㉁ࡸ࣌ࣉࢳࢻࡢจ㞟యࡀࡇࢀࡽࡢ⚄⤒ኚᛶ⑌ᝈࢆᘬࡁ㉳ࡇࡍᶵᵓࢆゎ᫂ࡍࡿࡓࡵ㸪ᡃࠎࡣࡇࢀࡲ࡛࡟ࢱࣥࣃࢡ㉁ࡸ࣌ࣉࢳࢻࡢจ㞟య࡟㛵ࡍࡿ࠸ࡃࡘ࠿ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࠋ௒ᖺ
ᗘࡣࢱࣥࣃࢡ㉁ࡸ࣌ࣉࢳࢻࡢจ㞟యࡢᵓ㐀ࢆຠ⋡ࡼࡃࢧࣥࣉࣝࡍࡿ᪂ࡋ࠸ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲ
ࠕࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢἲࠖࢆ㛤Ⓨࡋࡓࠋࡉࡽ࡟ࡑࢀࢆ $ȕ ࣇࣛࢢ࣓ࣥࢺࡸࡑࡢจ㞟㜼ᐖ๣࡟ᛂ⏝ࡋࡓࠋࡲࡓࠊ$ȕ ࣌ࣉࢳࢻ௨እࡢ࣌ࣉࢳࢻ࡜ࡋ࡚ࠊࣃ࣮࢟ࣥࢯࣥ⑓ࡢⓎ⑕࡟㛵ࢃࡿࢱࣥࣃࢡ㉁࡛࠶ࡿ Į ࢩࢾࢡࣞ࢖ࣥࡢࣇࣛࢢ࣓ࣥࢺࡢจ㞟㐣⛬ࢆゎ᫂ࡋࡓࠋ
ࡉࡽ࡟ࠊ᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫࡢ 51$ ࢆ」〇ࡍࡿࢱࣥࣃࢡ㉁࡛࠶ࡿ 51$ ౫Ꮡᛶ 51$ ࣏࣓࣮ࣜࣛࢮࡢ◊✲࡟ࡶྲྀࡾ⤌ࢇࡔࠋලయⓗ࡟ࡣࠊࡇࡢ 51$ ౫Ꮡᛶ 51$ ࣏࣓࣮ࣜࣛࢮ࡟ᑐࡍࡿ⸆๣ࡢస⏝ᶵᵓࢆศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎ᫂ࡋࡓࠋࡲࡓࠊ᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫ࡜㔜⑕ᛴᛶ࿧྾ჾ⑕ೃ⩌࢘࢖ࣝࢫࡢ 51$ ౫Ꮡᛶ 51$ ࣏࣓࣮ࣜࣛࢮࡢάᛶᕪࢆᘬࡁ㉳ࡇࡍᶵᵓࡶ᫂ࡽ࠿࡟ࡋࡓࠋ

ࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢἲࡢ㛤Ⓨ࡜࢔࣑ࣟ࢖ࢻ ȕ ࣇࣛࢢ࣓ࣥࢺ࡬ࡢᛂ⏝⏕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㛫࡛ᗘࢆ⨨᥮ࡍࡿࠋ

ᗘࢆୖୗࡉࡏࠊ⮬⏤࢚ࢿࣝࢠ࣮ᴟᑠ≧ែ࠿ࡽྛ⣔ࢆ⬺ฟࡉࡏࡿࠋࡇࡢ᪉ἲࡣ

ᗘࢆ஺᥮ࡍࡿࣞࣉࣜ࢝஺᥮ἲࡼࡾࡶᙉຊ࡞᪉ἲ࡛࠶ࡿࠋ୍᪉ࠊ᭱㏆ὀ┠ࡉࢀ࡚࠸ࡿ

ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࡢ୍ࡘ࡟ࣞࣉࣜ࢝஺᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢἲࡀ࠶ࡿࠋࡇࡢ᪉ἲ࡛ࡣ⁐㉁࡟㛵ࢃࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮࡟ࣃ࣓࣮ࣛࢱࢆᑟධࡋࠊࡑࡢࣃ࣓࣮ࣛࢱࢆࣞࣉࣜ࢝㛫࡛஺᥮ࡍࡿࠋᐇ㉁ⓗ࡟⁐㉁ࡢࡳࡢ
ᗘࢆ஺᥮ࡍࡿࡇ࡜࡟࡞ࡿࡓࡵࠊィ⟬ࢥࢫࢺࢆ኱ᖜ࡟ῶࡽࡍࡇ࡜ࡀ࡛ࡁࡿࠋࡑࡇ࡛ᡃࠎࡣࣞࣉࣜ࢝⨨᥮ἲ࡜ࣞࣉࣜ࢝஺᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢἲࢆᇶ࡟ィ⟬ࢥࢫࢺࢆ኱ᖜ࡟ῶࡽࡍࡇ࡜ࡢ࡛ࡁࡿࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣝࢺ
ࢸࣥࣃࣜࣥࢢἲࢆ㛤Ⓨࡋࡓࠋࡉࡽ࡟ࡇࡢᡭἲࢆ⏝࠸࡚ $ȕ ࣇࣛࢢ࣓ࣥࢺࡢจ㞟࡟క࠺ᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡋ
ࡓ㸦ᅗ 㸧ࠋ- 450 -

ࡲࡓࠊ$ȕ ࣌ࣉࢳࢻࡣ࣏ࣜࣇ࢙ࣀ࣮ࣝ࡟ࡼࡾࡑࡢจ㞟ࡀ㜼ᐖࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛  ᮏࡢ $ȕ
ࣇࣛࢢ࣓ࣥࢺ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝࢆྵࡴ⣔ࡢࣞࣉࣜ࢝⨨᥮ࢯ࣮ࣝࢺࢸࣥࣃࣜࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋ⌧ᅾࠊ$ȕ ࣇࣛࢢ࣓ࣥࢺࡢ  ḟᵓ㐀ᙧᡂ☜⋡࡞࡝ࡢゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ
ᅗ  $ȕ  ࣇࣛࢢ࣓ࣥࢺࡢ஧㔞య໬㐣⛬ࠋ$ȕ  ࣇࣛࢢ࣓ࣥࢺࡀ㏆௜ࡃ࡟ࡘࢀ࡚࣊ࣜࢵࢡࢫᵓ㐀ࡀῶᑡࡋࠊ཯ᖹ⾜ ȕ ࢩ࣮ࢺᵓ㐀ࡀᙧᡂࡉࢀࡿࠋࡇࡢ཯ᖹ⾜ ȕ ࢩ࣮ࢺᵓ㐀ࡣ . ࡜ ( ࡢ㛫ࡢ㟼㟁ᘬຊ࡛Ᏻᐃ໬ࡉࢀࡿࠋĮ ࢩࢾࢡࣞ࢖ࣥࣇࣛࢢ࣓ࣥࢺจ㞟ࡢࣞࣉࣜ࢝⨨᥮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࣃ࣮࢟ࣥࢯࣥ⑓ࡢⓎ⑕࡟ࡣ Į ࢩࢾࢡࣞ࢖ࣥࡢจ㞟యࡀ㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋĮ ࢩࢾࢡࣞ࢖ࣥࡢ  ␒┠࠿ࡽ  ␒┠ࡲ࡛ࡢ㠀࢔࣑ࣟ࢖ࢻ ȕ ᡂศ㸦1$&㸧ࡢ࠺ࡕࠊ1$&RUH ࡜࿧ࡤࢀࡿ  ṧᇶࡢࢭࢢ࣓ࣥࢺ
㸦*$997*97$9$㸧ࡣࠊ⥺⥔ᙧᡂ࡜⣽⬊ẘᛶࡢ୧᪉࡟ᚲ㡲࡞㡿ᇦ࡛࠶ࡿࠋ1$&RUH ࣌ࣉࢳࢻ༢⊂࡛ࡶจ㞟యࡸ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆᙧᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊจ㞟ࡸ⥺⥔໬ࡢ࣓࢝ࢽࢬ࣒ࡣ୙࡛᫂࠶ࡿࠋࡑࡇ࡛ࠊ
จ㞟࣭⥺⥔໬㐣⛬ࡢึᮇẁ㝵࡛࠶ࡿ 1$&RUH ࣌ࣉࢳࢻࡢ஧㔞య໬㐣⛬࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ ᮏࡢ 1$&RUH ࣌ࣉࢳࢻ࡟ࡘ࠸࡚ࠊຠ⋡ⓗ࡞ࢧࣥࣉࣜࣥࢢᡭἲࡢ୍ࡘ࡛࠶ࡿ➼࣭➼ᅽࣞࣉࣜ࢝⨨᥮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

ࢆỈ୰࡛ ȝV ࡟ࢃࡓࡗ࡚ᐇ᪋ࡋࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊᵝࠎ࡞஧㔞యᵓ㐀ࢆࢧࣥࣉࣜࣥࢢࡍࡿࡇ࡜࡟
ᡂຌࡋࡓࠋ஧ḟᵓ㐀ࡢゎᯒࡢ⤖ᯝࠊ1$&RUH ஧㔞యࡢከࡃࡣศᏊ㛫 ȕ ࣈࣜࢵࢪࢆᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
≉࡟ࠊᖹ⾜ ȕ ࣈࣜࢵࢪࡼࡾࡶ཯ᖹ⾜ ȕ ࣈࣜࢵࢪࡀከࡃほᐹࡉࢀࡓࠋࡲࡓࠊĮ ࣊ࣜࢵࢡࢫࡸ཯ᖹ⾜ ȕ ࣈࣜࢵࢪ࡞࡝ࡢศᏊෆ஧ḟᵓ㐀ࡣࠊ஧㔞య໬ࡍࡿ๓ࡢ≧ែ࡛Ᏻᐃ໬ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ࡟ࠊศᏊ㛫 ȕ ࣈࣜࢵࢪࡣࠊศᏊෆ ȕ ࣈࣜࢵࢪࢆ⤒⏤ࡏࡎ࡟ࠊ≉ᐃࡢᵓ㐀ࢆᣢࡓ࡞࠸ṧᇶࡢ㛫࡛┤᥋ᙧᡂࡉࢀࡿഴྥࡀ࠶ࡿࡇ
࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

$ȕ ࣇࣛࢢ࣓ࣥࢺ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫឤᰁ⑕࡟ᑐࡍࡿ἞⒪⸆࡜ࡋ࡚⌧ᅾ࣒ࣞࢹࢩࣅࣝࡸࣇ࢓ࣅࣆࣛࣅࣝ㸦ၟရྡ࢔ࣅ࢞ࣥ㸧ࡀὀ┠ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡣ᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫࡢ 51$ ౫Ꮡᛶ 51$ ࣏࣓࣮ࣜࣛࢮ࡟ᑐࡍࡿ 51$ 」〇㜼ᐖ๣࡜ࡋ࡚ᶵ⬟ࡍࡿ࡜ᮇᚅࡉࢀ࡚࠸ࡿࠋ51$ ࣏࣓࣮ࣜࣛࢮࡣ㏻ᖖ࢔ࢹࣀࢩࣥ୕ࣜࣥ㓟㸦$73㸧࡞࡝ࡢࢾࢡࣞ࢜
ࢳࢻࢆྲྀࡾ㎸ࢇ࡛ 51$ ࢆ」〇ࡍࡿࠋ࣒ࣞࢹࢩࣅࣝࠊࣇ࢓ࣅࣆࣛࣅࣝࡣ $73 ࡞࡝࡜➇ྜࡋ࡚ 51$ ࣏࣓࣮ࣜࣛ
ࢮ࡟ྲྀࡾ㎸ࡲࢀ࡚ 51$ ࡢ」〇ࢆ㜼ᐖࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᡃࠎࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࠊࡇࢀࡽࡢ⸆๣ࡸ $73 ࡢᣢࡘ୕ࣜࣥ㓟ࡢ㈇㟁Ⲵࡀ 51$ ࣏࣓࣮ࣜࣛࢮࡢ⤖ྜࢧ࢖ࢺ࡟࠶ࡿ 0J࢖࢜ࣥ࡟㟼㟁┦஫స⏝࡟ࡼࡾᘬࡁᐤࡏࡽࢀ࡚⤖ྜࡍࡿࡇ࡜ࢆゎ᫂ࡋࡓࠋࡲࡓࠊ51$ ࣏࣓࣮ࣜࣛࢮ࡟ࡣ⤖ྜࢧ࢖ࢺ࡟ྥ࠿ࡗ࡚
」ᩘࡢࣜࢪࣥࡀ୍ิ࡟୪ࢇ࡛࠾ࡾࠊࡇࡢࣜࢪࣥࡢṇ㟁Ⲵࡀࠕࣂࢣࢶ࣮ࣜࣞࠖࡢࡼ࠺࡟⸆๣ࡸ $73 ࢆ⤖ྜࢧ࢖
ࢺ࡟㍺㏦ࡋ࡚࠸ࡿࡇ࡜ࡶⓎぢࡋࡓ㸦ᅗ 㸧ࠋ௒ᅇࡢⓎぢ࡟ࡼࡾ 51$ ࣏࣓࣮ࣜࣛࢮ࡟ࡼࡿຠ⋡ⓗ࡞ࣜ࢞ࣥࢻㄆ

- 451 -

㆑ࡢ௙⤌ࡳࢆゎ᫂ࡋࡓࠋࡇࡢᡂᯝࡣ 1+. ࡸྛ✀࢖ࣥࢱ࣮ࢿࢵࢺࢽ࣮ࣗࢫ࡛ሗ㐨ࡉࢀࡓࠋ≉࡟࣐࢖ࢼࣅࢽ࣮ࣗ
ࢫ࡛ࡣ་⒪࣭ࣂ࢖࢜ศ㔝ࡢ㐌㛫ࢽ࣮ࣗࢫࣛࣥ࢟ࣥࢢ࡛  ఩࡟࡞ࡗࡓ㸦 ᖺ  ᭶㸧ࠋᅗ  ࣒ࣞࢹࢩࣅࣝ㸦⌫ࣔࢹ࡛ࣝ⾲♧㸧ࡀ」ᩘࡢࣜࢪࣥṧᇶ㸦Წࣔࢹ࡛ࣝ⾲♧㸧࡟ḟࠎ࡜ཷࡅΏࡉࢀ࡞ࡀ
ࡽ 51$ ࣏࣓࣮ࣜࣛࢮ㸦ࣜ࣎ࣥࣔࢹ࡛ࣝ⾲♧㸧ࡢ⤖ྜࢧ࢖ࢺ࡟࠶ࡿ  ಶࡢ 0J࢖࢜ࣥ㸦㯤⥳Ⰽࡢ⌫㸧࡟㐠ࡤࢀ࡚࠸ࡿᵝᏊࢆ♧ࡍࠋࣜࢪࣥṧᇶࡀ࠶ࡓ࠿ࡶࣂࢣࢶ࣮ࣜࣞࡢࡼ࠺࡟࣒ࣞࢹࢩࣅࣝࢆ㐠ࢇ࡛࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ

᪂ᆺࢥࣟࢼ࢘࢖ࣝࢫ࡜㔜⑕ᛴᛶ࿧྾ჾ⑕ೃ⩌࢘࢖ࣝࢫࡢ 51$ ౫Ꮡᛶ 51$ ࣏࣓࣮ࣜࣛ
ࢮࡢάᛶᕪࢆᘬࡁ㉳ࡇࡍᶵᵓ
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ຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ୧⪅ࡢືⓗ≉ᛶ࡟㐪࠸ࡀ࠶ࡿࡇ࡜ࢆⓎぢࡋࡓࠋලయⓗ࡟ࡣ 6$56&R9 ࡢ 51$
࣏࣓࣮ࣜࣛࢮ࡛ࡣάᛶ㒊఩ࢆᙧᡂࡍࡿࣔࢳ࣮ࣇ $̽* ࡀ᭱኱ 㸣᥋㏆ࡋ࡚࠸ࡿࡇ࡜ࠊࡲࡓ 6$56&R9 ࡢ 51$
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51$ ࣏࣓࣮ࣜࣛࢮࡢάᛶᕪࡢཎᅉ࡜⪃࠼ࡽࢀࡿࠋ

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SDJHV - 452 -

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SURWHLQYDULHVHQWUDQFHSURSHQVLW\GHSHQGLQJRQWKHDPLQRDFLGVHTXHQFH´-3K\V&KHP%126  ±
‫ۻ‬6 7DQLPRWR 6 * ,WRK DQG + 2NXPXUD ³³%XFNHW EULJDGH´ XVLQJ O\VLQH UHVLGXHV LQ 51$GHSHQGHQW 51$SRO\PHUDVHRI6$56&R9´%LRSK\V-120  ±
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51$SRO\PHUDVHVVWXGLHGE\PROHFXODUG\QDPLFVVLPXODWLRQV´&KHP3K\V/HWW778   SDJHV ‫ۻ‬. 0L\D]DZD 6 * ,WRK + :DWDQDEH 7 8FKLKDVKL 6 <DQDND 0 <DJL8WVXPL . .DWR . $UDNDZD DQG +
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86$ &KDSSS±
ዟᮧஂኈ㸸ࠕ࢔࣑ࣟ࢖ࢻ ȕ ± ࣌ࣉࢳࢻࡢจ㞟࡜จ㞟㜼ᐖ๣ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࠖࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ 40  ̽
ከ▱⿱ᖹ㸪ዟᮧஂኈ㸸ࠕ⢾㙐ࢡࣛࢫࢱ࣮࡜ࡢ⤖ྜ࡟ࡼࡿ࢔࣑ࣟ࢖ࢻșࡢᵓ㐀ኚ໬ࠖ⏕≀≀⌮ 61  ̽
- 453 -

ศᏊືຊᏛィ⟬࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᾮయࡢศᏊ㛫┦஫స⏝ࡢ◊✲
Molecular interactions in liquid phase studied by molecular dynamics
simulations and quantum chemical calculations‫ۑ‬㛗ᆏ ᑗᡂ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗᡃࠎࡣศᏊ◊ UVSOR-III ࡟࠾࠸࡚ᵝࠎ࡞⁐ᾮヨᩱࡢ㌾ X ⥺྾཰ศගᐃࢆ⾜ࡗ࡚ࡁࡓࠋࢫ࣌ࢡࢺࣝࡢ໬Ꮫ

ࢩࣇࢺࡣศᏊ㛫┦஫స⏝࡟⏤᮶ࡍࡿࡓࡵࠊ⁐ᾮࡢศᏊືຊᏛ(MD)ィ⟬࡜㔞Ꮚ໬Ꮫ࡟ᇶ࡙ࡃෆẆບ㉳ィ⟬ࢆ⾜࠸ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࡢᒁᡤᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋᮏᖺᗘࡣࢪ࣓ࢳࣝࢫࣝ࣍
࢟ࢩࢻ(DMSO)Ỉ⁐ᾮࡢศᏊ㛫┦஫స⏝ࡢ⃰ᗘ౫Ꮡᛶࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲMD ィ⟬ࡣ GROMACS 2019.6 ࢆ⏝࠸࡚⾜ࡗࡓࠋDMSO ࡢ࣏ࢸࣥࢩࣕࣝ࡟ࡣ OPLSAA ࢆࠊỈࡢ࣏ࢸࣥࢩࣕ

ࣝ࡟ࡣ TIP-5P ࢆ⏝࠸ࡓࠋศᏊ㓄⨨ࡣ 1 ps ࡈ࡜࡟཰㞟ࡍࡿࡢࢆ 100 ns ࡢ㛫⾜ࡗࡓࠋᚓࡽࢀࡓศᏊ㓄⨨࠿ࡽ⮬సࡢゎᯒࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊDMSO ࡜Ỉࡢ㛫ࡢືᚄศᕸ㛵ᩘ(RDF)ࢆồࡵࡓࠋ

3◊✲ᡂᯝ␗࡞ࡿࣔࣝẚ⋡ࡢ DMSO Ỉ⁐ᾮࡢ MD ィ⟬࠿ࡽࠊDMSO ࡜Ỉࡢ㛫ࡢ RDF ࢆồࡵࡓࠋᐇ㦂⤖ᯝ࡜ࡢẚ㍑࠿

ࡽࠊDMSO Ỉ⁐ᾮ୰ࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡣࠊDMSO ࡢ S=O ᇶ࡜Ỉࡢࢻࢼ࣮ࢧ࢖ࢺࡢ㛫ࡢỈ⣲⤖ྜࡔࡅ࡛
࡞ࡃࠊDMSO ࡢ◲㯤ཎᏊ࡜Ỉࡢ࢔ࢡࢭࣉࢱ࣮ࢧ࢖ࢺࡢ㛫ࡢ཮ᴟᏊ┦஫స⏝࡟ࡼࡾࠊỈྠኈࡢỈ⣲⤖ྜࡀษ᩿ࡉࢀࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫“ ۻ‬Soft X-ray absorption spectroscopy of liquids for understanding chemical processes in solution”, M. Nagasaka,
The International Chemical Congress of Pacific Basin Societies 2021 (Pacifichem-2021) “Frontiers of Higher Energy UVSpectroscopy”, Online Conference, 2021/12/18. (ᣍᚅㅮ₇)[2] ‫“ ۻ‬Molecular interactions in aqueous solutions probed by soft X-ray absorption spectroscopy”, M. Nagasaka andN. Kosugi, The International Chemical Congress of Pacific Basin Societies 2021 (Pacifichem-2021) “Frontiers in the
Structure, Properties, and Functions of Molecular Liquids and Solutions”, Online Conference, 2021/12/21.
[3] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿ⁐ᾮ཯ᛂࡢ࢜࣌ࣛࣥࢻほ ”, 㛗ᆏᑗᡂ, ᪥ᮏᏛ⾡᣺⯆఍ 69 ጤဨ఍ ➨ 2 ศ⛉఍(᪂⣲ᮦ㛵㐃ᢏ⾡) ➨ 74 ᅇ◊✲఍ࠕᶵ⬟ᮦᩱ㛤Ⓨࢆᨭ࠼ࡿࡑࡢሙ(In-situ)࣭ືస⎔ቃୗ(Operando)ィ

ᢏ⾡ࡢ᭱㏆ࡢ㐍ᒎࠖ, ࢜ࣥࣛ࢖ࣥ఍㆟, 2021/7/19. (ᣍᚅㅮ₇)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫“ ۻ‬Soft X-ray Absorption Spectroscopy for Observing Element-specific Intermolecular Interaction in Solution
Chemistry”, M. Nagasaka and N. Kosugi, Chem. Lett. 50, 956-964 (2021).

- 454 -

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సࡍࡿࡢ࠿ᐇ㦂࡟ࡼࡾㄪ࡭ࡿ࡜࠸࠺࢔ࣉ࣮ࣟࢳ࡟ࡼࡾ◊✲ࢆᐇ᪋ࡋ࡚࠸ࡿࠋࡇࢀࡲ࡛ࡢ◊✲࡟࠾࠸࡚ࠊᶵ⬟ᩚྜࡍࡿᒁᡤ࠾ࡼࡧ㠀ᒁᡤ┦஫స⏝࡟㛵ࡍࡿ୺㙐ᵓ㐀࣮ࣝࣝࢆⓎぢࡋࠊࡑࢀࡽࡢ࣮ࣝࣝࢆ⏝࠸ࡿࡇ࡜࡛ࠊᒁ
ᡤ࣭㠀ᒁᡤ┦஫స⏝ࡀᩚྜࡋ࡚ኳ↛ᵓ㐀ࢆᏳᐃ໬ࡍࡿࡼ࠺࡞ࢱࣥࣃࢡ㉁ᵓ㐀タィཎ⌮ࢆᵓ⠏ࡋ࡚࠸ࡿࠋලయ
ⓗ࡟ࡣࠊࡇࡢ୺㙐ᵓ㐀࣮ࣝࣝࢆ‶ࡓࡍࡼ࠺࡟タィࡋࡓ࠸ᵓ㐀ࡢ㸰ḟᵓ㐀ࡸ࣮ࣝࣉࡢ㛗ࡉࢆỴࡵࠊタィᅗࢆᥥࡁ୺㙐ᵓ㐀ࢆᵓ⠏ࡍࡿࠋࡑࡋ࡚ࠊᵓ⠏ࡋࡓ୺㙐ᵓ㐀ࢆᏳᐃ໬ࡍࡿࡼ࠺࡟ഃ㙐ᵓ㐀㸦࢔࣑ࣀ㓟㓄ิ㸧ࢆタィࡍࡿࠋࡇࡢ࡜ࡁࠊᒁᡤⓗ࡟ࡣタィᅗ࡛Ỵᐃࡋࡓ㸰ḟᵓ㐀ࡸ࣮ࣝࣉࢆᏳᐃ໬ࡍࡿࡼ࠺࡞ࠊ㠀ᒁᡤⓗ࡟ࡣ␯Ỉᛶ┦஫స⏝➼࡛㸱ḟᵓ㐀ࢆᏳᐃ໬ࡍࡿࡼ࠺࡞ࠊ࢔࣑ࣀ㓟㓄ิࢆタィࡍࡿࠋᵓ⠏ࡋࡓタィཎ⌮ࢆ⏝࠸ࡿࡇ࡜࡛ࠊᡃࠎ
ࡣ 4 ᮏࢫࢺࣛࣥࢻ࠿ࡽ࡞ࡿșࢩ࣮ࢺࢆᣢࡘ 100 ṧᇶ௨ୗࡢᵝࠎ࡞Șșᆺࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡢ๰ฟ࡟ᡂຌࡋ࡚
ࡁࡓࠋࡑࡇ࡛ᡃࠎࡣࠊࡼࡾ኱ࡁࡃ」㞧࡞ࢱࣥࣃࢡ㉁ᵓ㐀ࡢேᕤタィ࡟ࡶࠊᵓ⠏ࡋࡓタィཎ⌮ࡀ㐺⏝࡛ࡁࡿ࠿࡝࠺࠿ㄪ࡭ࡿࡓࡵ࡟ࠊ5 ᮏ࠶ࡿ࠸ࡣ 6 ᮏࢫࢺࣛࣥࢻ࠿ࡽ࡞ࡿșࢩ࣮ࢺࢆᣢࡘ 100 ṧᇶ௨ୖࡢࢧ࢖ࢬࡢȘșᆺ
ࢱࣥࣃࢡ㉁ࡢタィࢆヨࡳࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ᰾☢Ẽඹ㬆ศගἲ࡛Ỵᐃࡉࢀࡓᐇ㦂ᵓ㐀ࡣࠊィ⟬ᶵ࡛タィࡋࡓᵓ㐀࡜␗࡞ࡾࠊෆ㒊ࡢșࢫࢺࣛࣥࢻࡢ୪ࡧࡀධࢀ᭰ࢃࡗ࡚࠸ࡓ㸦ᅗ 1㸧ࠋᮏ◊✲ࡢ┠ⓗࡣࠊ࡞ࡐșࢫࢺࣛࣥࢻ
ࡢ୪ࡧࡀධࢀ᭰ࢃࡗࡓࡢ࠿ࢆ᫂ࡽ࠿࡟ࡋࠊ100 ṧᇶ௨ୖࡢࢧ࢖ࢬࡢȘșᆺࢱࣥࣃࢡ㉁ࡢタィࡍࡿࡓࡵࡢ᪂ࡓ
࡞ࢱࣥࣃࢡ㉁ᵓ㐀タィཎ⌮ࢆᵓ⠏ࡍࡿࡇ࡜࡛࠶ࡿࠋ

- 455 -ᅗ  ࡇࢀࡲ࡛࡟ᵓ⠏ࡋࡓࢱࣥࣃࢡ㉁ᵓ㐀タィཎ⌮ࡢ㝈⏺㸸 ᮏ࠾ࡼࡧ  ᮏࢫࢺࣛࣥࢻ࠿ࡽ࡞ࡿ  ṧᇶ௨ୖࡢࢧ࢖ࢬࡢ Șș ᆺࢱࣥࣃࢡ㉁ᵓ㐀ࡢேᕤタィ㸦࢔࣑ࣀ㓟ṧᇶᩘࡣࡑࢀࡒࢀ 㸧ࠋୖẁ࡟ィ⟬ᶵ࡛タィࡋࡓᵓ㐀ࢆ♧ࡋࠊୗẁ࡟᰾☢Ẽඹ㬆ศගἲ࡛ゎ࠸ࡓᐇ㦂ᵓ㐀ࢆ♧ࡍࠋࡑࢀࡒࢀࡢᵓ㐀ࡢྑ㞄ࡢ⤮࡟ࠊș ࢫࢺࣛࣥࢻ࠾ࡼࡧ Ș ࣊ࣜࢵࢡࢫࡢ  ḟඖⓗ࡞㓄⨨࠾ࡼࡧࠊࡑࢀࡽࡀ࡝ࡢࡼ࠺࡟࣮ࣝ
ࣉ࡛㐃⤖ࡉࢀ࡚࠸ࡿࡢ࠿ࢆᶍᘧⓗ࡟♧ࡋࡓࠋ1& ࡣ࢔࣑ࣀ㓟㓄ิࡢ 1& ᮎ➃ࢆ⾲ࡋࠊ୕ゅࡣ ș ࢫࢺࣛࣥࢻࠊ୸ࡣ Ș ࣊ࣜࢵࢡࢫࠊ┤⥺ࡣ࣮ࣝࣉࢆ⾲ࡍࠋィ⟬ᶵ࡛タィࡋࡓᵓ㐀࡜ẚ࡭࡚ࠊᐇ㦂ᵓ㐀࡛ࡣ㟷࡜⥳ࡢࢫࢺࣛࣥࢻࡢ఩⨨ࡀධࢀ᭰ࢃࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ィ⟬ᶵᵓ㐀ࡣ 5RVVPDQQ ࣇ࢛࣮ࣝࢻᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿࡢ࡟ᑐࡋ࡚ࠊᐇ㦂ᵓ㐀ࡣ 3ORRS ࣇ࢛࣮ࣝࢻࢆᙧᡂ㸧ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࡞ࡐșࢫࢺࣛࣥࢻࡢ୪ࡧࡀධࢀ᭰ࢃࡗࡓᵓ㐀࡟ᢡࡾ␚ࢇࡔࡢ࠿᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊࢱࣥࣃࢡ㉁タィࢯࣇࢺ࢙࢘࢔ Rosetta ࢆ⏝࠸ࡓᢡࡾ␚ࡳࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊࢹࢨ࢖ࣥࡋࡓࢱࣥࣃࢡ㉁ࡑࢀࡒࢀࡢタィᅗ࡟ᑐᛂࡍࡿ୺㙐ᵓ㐀࢔ࣥࢧࣥࣈࣝࢆ⏕ᡂࡋࡓࠋࡉࡽ࡟ࠊࡑࡢ୺㙐ᵓ㐀࢔ࣥࢧࣥࣈࣝࡀࠕȕ ࢩ࣮ࢺᙧᡂᗘࠖ࡜ࠕ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࡢࣃࢵ࢟ࣥࢢᗘࠖࡢ㸰ࡘࡢᣦᶆ࠿ࡽぢࡓ࡜ࡁ࡟ࠊ࡝ࡢ⛬ᗘࣇࣛࢫࢺ࣮ࣞࢩࣙࣥࢆᣢࡘࡢ࠿࡝࠺
࠿ࢆㄪ࡭ࡓࠋᅗ  ୺㙐࣮ࣝࣝ࡟ᇶ࡙࠸࡚సᡂࡋࡓィ⟬ᶵᵓ㐀㸦ᅗ  ୖẁ㸧ࡢタィᅗ࡜ࠊᐇ㦂ᵓ㐀㸦ᅗ  ୗẁ㸧࠿ࡽ᚟ඖࡋࡓタィᅗ タィᅗ࡟࠾࠸࡚ N, C ࡣ N, C ᮎ➃ࠊᅄゅࡣࢫࢺࣛࣥࢻṧᇶࠊ⣽㛗࠸㛗᪉ᙧࡣ࣊ࣜࢵࢡࢫࠊࡑࡢ୰
ࡢᩘᏐࡣ࣊ࣜࢵࢡࢫࡢṧᇶ㛗ࠊ᭤⥺ࡣ࣮ࣝࣉࢆ⾲ࡍࠋ3◊✲ᡂᯝୖグࡢィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊィ⟬ᶵ࡛タィࡋࡓᵓ㐀ࢆᵓ⠏ࡍࡿࡓࡵ࡟⏝࠸ࡓタィᅗࡣࠊᐇ㦂ᵓ㐀࠿ࡽ᚟ඖࡋ

ࡓタィᅗ࡜ẚ࡭࡚ࠊࢱࣥࣃࢡ㉁ᵓ㐀඲య࡟ࢃࡓࡿ୺㙐ᵓ㐀ࡢṍࡳࢆ⏕ࡌࡿࡓࡵ࡟ࠊࠕȕ ࢩ࣮ࢺᙧᡂᗘࠖ࠾ࡼࡧ
ࠕ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࡢࣃࢵ࢟ࣥࢢᗘࠖࡀప࠸ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 3㸧ࠋࡉࡽ࡟ࠊᵝࠎ࡞タィᅗࢆᥥ࠸࡚
ᢡࡾࡓࡓࡳࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࡑࢀࡒࢀࡢ୺㙐ᵓ㐀࢔ࣥࢧࣥࣈࣝࢆ⏕ᡂࡋࠊࡇࢀࡽ㸰ࡘࡢᣦᶆ࡟ࡘ࠸࡚
ㄪ࡭ࡓ࡜ࡇࢁࠊșࢫࢺࣛࣥࢻࡢ㛗ࡉࢆ▷ࡃࡍࡿࡇ࡜ࡸࠊșࢫࢺࣛࣥࢻ㛫ࡢ┦ᑐⓗ࡞఩⨨ࢆㄪᩚࡍࡿࡇ࡜࡛ࠊ
୺㙐ᵓ㐀ࡢṍࡳࢆᢚ࠼࡞ࡀࡽࠊȕ ࢩ࣮ࢺᙧᡂ࠾ࡼࡧ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࡢࣃࢵ࢟ࣥࢢᗘྜ࠸ࢆ㧗ࡵࡿࡇ࡜ࢆ
᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 㸧ࠋ

- 456 -

ᅗ 3. ᢡࡾ␚ࡳࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ᫂ࡽ࠿࡟ࡋࡓ୺㙐ᵓ㐀ṍࡳࠋ㸦a㸧タィᵓ㐀ࢆᵓ⠏ࡍࡿࡓࡵ࡟⏝࠸ࡓタィᅗ㸦ᅗ 3㸦a㸧ࡢタィᅗ 1 ࡜タィᅗ 4 ཧ↷㸧࡜ࠊᐇ㦂ᵓ㐀࠿ࡽ᚟ඖࡋࡓタィᅗࢆࡶ࡜࡟ᢡࡾ␚ࡳࢩ
࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ࡜ࡁࡢࠊࠕȕ ࢩ࣮ࢺᙧᡂᗘࠖ࡜ࠕ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࣃࢵ࢟ࣥࢢᗘࠖࢆ♧ࡍࠋྑୖ࡟࠸ࡃ࡯࡝ࠊ୺㙐ᵓ㐀ࡢṍࡳ↓ࡃࠊЎ ࢩ࣮ࢺ࡜୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࣃࢵ࢟ࣥࢢࡀᙧᡂࡉࢀࡿࡇ࡜
ࢆ⾲ࡍࠋ㸦b㸧タィᵓ㐀ࢆᵓ⠏ࡍࡿࡓࡵ࡟⏝࠸ࡓタィᅗࢆࡶ࡜࡟ᢡࡾ␚ࡳࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ࡜ࡁࡢᵓ㐀㸦5 ᮏࢫࢺࣛࣥࢻ ЍЎ ᵓ㐀㸧ࠋ୧ᮎ➃ࡢ࣊ࣜࢵࢡࢫ㛫㊥㞳ࡀࡦࡽࡁࠊ␯Ỉᛶࣃࢵ࢟ࣥࢢࢆᙧᡂ
࡛ࡁ࡞࠸ࠋ㸦c㸧タィᵓ㐀㸦5 ᮏࢫࢺࣛࣥࢻ ЍЎ ᵓ㐀㸧ࠋࣃࢵ࢟ࣥࢢࢆᙧᡂࡍࡿࡓࡵ࡟ࠊ
㸦b㸧࡜ẚ࡭࡚㟷Ⰽࡢ࣊ࣜࢵࢡࢫࡢ୺㙐ᵓ㐀ࡀ኱ࡁࡃṍࢇ࡛࠸ࡿࠋ

ᅗ 4. 㸦a㸧 5 ᮏ࠾ࡼࡧ 6 ᮏࢫࢺࣛࣥࢻࡢ Įȕ ᆺࢱࣥࣃࢡ㉁ࡢᵝࠎ࡞୺㙐ᵓ㐀タィᅗ࡜ࠊ㸦b㸧 ȕ ࢩ࣮ࢺᙧᡂᗘ࠾ࡼࡧ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࣃࢵ࢟ࣥࢢᗘࡢ㛵ಀࠋタィᅗ࡟࠾࠸࡚ N, C ࡣ N, C ᮎ➃ࠊᅄゅࡣࢫࢺࣛࣥࢻṧᇶࠊ⣽㛗࠸㛗᪉ᙧࡣ࣊ࣜࢵࢡࢫࠊࡑࡢ୰ࡢᩘᏐࡣ࣊ࣜࢵࢡࢫࡢṧᇶ㛗ࠊ᭤⥺ࡣ࣮ࣝࣉࢆ⾲ࡍࠋࢫࢺࣛࣥࢻࡢ㛗ࡉࡀ▷࠸࡯࡝ ȕ ࢩ࣮ࢺᙧᡂᗘࡀ㧗ࡃ࡞ࡿ㸦b ࡢᅗ୰ࡢタィᅗ 4 ࠿ࡽ 5 ࡢኚ໬࡟ᑐ
ᛂ㸧ࠋࡲࡓࠊȕ ࢫࢺࣛࣥࢻ㛫ࡢ┦ᑐⓗ࡞఩⨨ࢆኚ࠼ࡿࡇ࡜࡛ࠊȕ ࢩ࣮ࢺࡢ᭤⋡ࡀኚࢃࡾࠊ୧➃࣊ࣜࢵࢡࢫ㛫㊥㞳ࡀኚࢃࡾࠊ࣊ࣜࢵࢡࢫ㛫ࡢࣃࢵ࢟ࣥࢢᗘࡀኚ໬ࡍࡿ㸦b ࡢᅗ୰ࡢタィᅗ 1 ࠿ࡽ 2 ࡢኚ໬࡟ᑐ
ᛂࠊࡲࡓࡣ 1 ࠿ࡽ 3 ࡢኚ໬࡟ᑐᛂ㸧ࠋ- 457 -

ḟ࡟ࠊࡇࢀࡽࡢ▱ぢࢆᇶ࡟ࠊ5 ᮏ࠶ࡿ࠸ࡣ 6 ᮏࢫࢺࣛࣥࢻ࠿ࡽ࡞ࡿ 100 ṧᇶ௨ୖࡢࢧ࢖ࢬࡢ Įȕ ᆺࢱࣥࣃࢡ㉁ᵓ㐀ࡢேᕤタィࢆヨࡳࡓࠋࠕȕ ࢩ࣮ࢺᙧᡂᗘࠖ࠾ࡼࡧࠕ୧ᮎ➃࣊ࣜࢵࢡࢫ㛫ࣃࢵ࢟ࣥࢢᗘࠖࡀ㧗ࡃ࡞ࡿࡼ࠺࡟ࠊ
୺㙐ᵓ㐀ṍࡳࡢప࠸୺㙐ᵓ㐀タィᅗࢆᥥࡁ㸦ᅗ 4(a)ࡢタィᅗ 3 ࡜ 5㸧ࠊࡇࢀࡽタィᅗࢆᇶ࡟ィ⟬ᶵ࡟ࡼࡾ୺㙐ᵓ㐀ࢆᵓ⠏ࡋࡓᚋ࡟ࠊࡇࢀࡽ୺㙐ᵓ㐀ࢆᏳᐃ໬ࡍࡿࡼ࠺࡞࢔࣑ࣀ㓟㓄ิࢆᣢࡘࢱࣥࣃࢡ㉁ࢆタィࡋࡓࠋタィࡋࡓࢱࣥࣃࢡ㉁ࡢᐇ㦂ᵓ㐀ࢆ᰾☢Ẽඹ㬆ศගἲ࡟ࡼࡾỴᐃࡋࡓ࡜ࡇࢁࠊタィ㏻ࡾࡢࢫࢺࣛࣥࢻࡢ୪ࡧࢆᣢࡘ
3 ḟᵓ㐀࡟ᢡࡾ␚ࢇ࡛࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡾࠊ5 ᮏ࠾ࡼࡧ 6 ᮏࢫࢺࣛࣥࢻ࠿ࡽ࡞ࡿ Įȕ ᆺࢱࣥࣃࢡ㉁ࡢேᕤ
タィ࡟ᡂຌࡋࡓ㸦ᅗ 㸧ࠋ

ᅗ 5. ᅗ 4㸦a㸧ࡢタィᅗ 3 ࡜タィᅗ 5 ࢆ⏝࠸࡚ࠊேᕤタィࡋࡓ 5 ᮏ࠾ࡼࡧ 6 ᮏࢫࢺࣛࣥࢻࡢ ЍЎ ᆺࢱ
ࣥࣃࢡ㉁ࠋィ⟬ᶵᵓ㐀㸦ୖ㸧࡜᰾☢Ẽඹ㬆ศගἲ࡛ゎ࠸ࡓᐇ㦂ᵓ㐀㸦ୗ㸧
ࠋ 5 ᮏ࠾ࡼࡧ 6 ᮏࢫࢺࣛࣥࢻ
࠿ࡽ࡞ࡿ Įȕ ᆺࢱࣥࣃࢡ㉁ࡢ๰ฟ࡟ᡂຌࡋࡓࠋ

ᮏ◊✲࡟ࡼࡾࠊࡇࢀࡲ࡛࡟ᵓ⠏ࡋ࡚ࡁࡓࢱࣥࣃࢡ㉁ᵓ㐀タィཎ⌮࡟ຍ࠼࡚ࠊ୺㙐ᵓ㐀ࡢṍࡳࢆ⪃៖ࡍࡿࡇ࡜
࡛ࠊᚑ᮶ࡼࡾࡶ኱ࡁࡃ」㞧࡞ࢱࣥࣃࢡ㉁ᵓ㐀ࢆタィࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡗࡓࠋ኱ࡁࡃ」㞧࡞ࢱࣥࣃࢡ㉁ᵓ㐀ࢆ᪂つ࡟ேᕤタィࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡗࡓࡇ࡜࡛ࠊタィࡋࡓࢱࣥࣃࢡ㉁ᵓ㐀୰࡟ᶵ⬟㒊఩ࢆᵓ⠏࡛ࡁࡿྍ⬟ᛶࡀ㧗ࡲࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ

- 458 -

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

մ [1] ྂ㈡ಙᗣ, ๰ࡗ࡚⌮ゎࡍࡿ ⏕࿨⌧㇟ࢆࡘ࠿ࡉ࡝ࡿศᏊࠕࢱࣥࣃࢡ㉁ࠖ, ➨ 33 ᅇ⮬↛⛉Ꮫ◊✲ᶵᵓࢩ࣏ࣥࢪ࣒࢘ࠕᏱᐂ࡜ࠊศᏊ࡜ࠊ⚾ࡓࡕࠖ, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2022 ᖺ 3 ᭶.
մ [2] ᑠᮡ㈗ὒ ࢱࣥࣃࢡ㉁」ྜయࡢ༠ዌⓗᶵ⬟ࢆྜ⌮ⓗ࡟ไᚚࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚ ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍ ୰㛗ᮇࢸ࣮࣐ࢩ࣏ࣥࢪ࣒࢘ࠕḟୡ௦ศᏊࢩࢫࢸ࣒໬Ꮫࡢࣇࣟࣥࢸ࢕࢔༠ዌⓗᶵ⬟ࡢ๰ฟ࡜ィࠖ࢜ࣥࣛ࢖ࣥ㛤ദ㸪2022 ᖺ 3 ᭶.
մ [3] ᑠᮡ㈗ὒᅇ㌿ᆺ⏕యⓎືศᏊࢆྜ⌮ⓗ࡟ᨵ㐀ࡋ࡚ไᚚࡍࡿ᪂Ꮫ⾡㡿ᇦࠕⓎືศᏊ⛉ᏛࠖᏛ⾡ኚ㠉㡿ᇦࠕศᏊࢧ࢖ࣂࢿࢸ࢕ࢡࢫࠖඹദ࣮࣡ࢡࢩࣙࢵࣉ ࢜ࣥࣛ࢖ࣥ㛤ദ㸪2022 ᖺ 3 ᭶.
մ [4] ྂ㈡ಙᗣ, ᩚྜᛶཎ⌮࡜᪂つࢱࣥࣃࢡ㉁ࢹࢨ࢖ࣥ, ⮬↛⛉Ꮫ◊✲ᶵᵓ࣭ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣮࣡ࢡࢩࣙࢵࣉ 2021ࠕ⏕యศᏊࡢᵓ㐀࣭ᶵ⬟࣭ࢹࢨ࢖ࣥࡢィ⟬⛉Ꮫࠖ, ࢜ࣥࣛ࢖ࣥ㛤ദ㸪
2022 ᖺ 1 ᭶.
մ [5] ྂ㈡ಙᗣ, ⮬↛⏺࡟ほࡉࢀ࡞࠸ࢺ࣏ࣟࢪ࣮ࢆᣢࡘࢱࣥࣃࢡ㉁ࡢேᕤタィ, ExCELLS ࢩ࣏ࣥࢪ࣒࢘,࢜ࣥࣛ࢖ࣥ㛤ദ㸪2021 ᖺ 12 ᭶.
[6] ᑠᮡ㈗ὒRosetta ࠿ࡽぢࡓ AlphaFold2➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ ➨ 8 ᅇ఍ဨ⥲఍ࢩ࣏ࣥࢪ࣒࢘࢜
ࣥࣛ࢖ࣥ㛤ദ㸪2021 ᖺ 11 ᭶
մ [7] ྂ㈡ಙᗣ, Exploration of novel protein structures by de novo design, OIST Mini Symposium “New Protein by
Evolution and Engineering”, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2021 ᖺ 11 ᭶.
մ [8] ྂ㈡ಙᗣ , ྜ⌮タィ࡟ࡼࡿ᪂つࢱࣥࣃࢡ㉁㓄ิ✵㛫ࡢ᥈⣴, ᮾிᕤᴗ኱Ꮫ Cell Biology Center
Colloquium, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2021 ᖺ 10 ᭶.
մ [9] ྂ ㈡ ಙ ᗣ , De novo design of novel protein structures, Molecular Engine International Mini-workshop
ࠕMolecular Engine in Virtual or Real World?ࠖ, ࢜ࣥࣛ࢖ࣥ㛤ദ, 2021 ᖺ 3 ᭶.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

մ [1] S. MINAMI, N. KOBAYASHI, T. SUGIKI, T. NAGASHIMA, T. FUJIWARA, R. KOGA, G. CHIKENJI, N.
KOGA, "Exploration of novel Įȕ-protein folds through de novo design", bioRxiv, (2021).
մ [2] K. SAKUMA, N. KOBAYASHI, T. SUGIKI, T. NAGASHIMA, T. FUJIWARA, K. SUZUKI, N. KOBAYASHI,
T. MURATA, T. KOSUGI, R. KOGA, N. KOGA, "Design of complicated all-Įprotein structures", bioRxiv, (2021).
մ [3] ྂ㈡⌮ᜨ㸪ྂ㈡ಙᗣ, ࠕࢱࣥࣃࢡ㉁ࡢྜ⌮タィᢏ⾡㛤Ⓨࠖ, ໬Ꮫ࡜ᕤᴗ, 74(8), 576-578, 2021
մ [4] M. MITSUMOTO, K. SUGAYA, K. KAZAMA, R. NAKANO, T. KOSUGI, T. MURATA and N. KOGA, StateTargeting Stabilization of Adenosine A2AReceptor by Fusing a Custom-Made De Novo Designed Į-Helical Protein, Int.
J. Mol. Sci, 22, 12906, 2021.
մ [5] N. KOGA, R. KOGA, G. LIU, J. CASTELLANOS, G.T. MONTELIONE, D. BAKER, "Role of backbone strain
in de novo design of complex Įȕprotein structures", Nature Commun., 12(1), 3921, (2021).

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[6] H. MURATA, H. IMAKAWA, N. KOGA, G. CHIKENJI, "The register shift rules for ȕĮȕ-motifs for de novo protein
design", Plos one, 16(8), e0256895, (2021).
[7] A. NAKAMURA, N. KOBAYASHI, N. KOGA, R. IINO, "Positive charge introduction on the surface ofthermostabilized PET hydrolase facilitates PET binding and degradation", ACS Catalysis, 11, 8550-8564, (2021).
մ [8] 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, bioRxiv, (2020).
մ [9] R. KOGA, M. YAMAMOTO, T. KOSUGI, N. KOBAYASHI, T. SUGIKI, T. FUJIWARA, N. KOGA, "Robust
folding of a de novo designed ideal protein even with most of the core mutated to valine", Proc. Natl. Acad. Sci. U. S.
A., 117(49), 31149-31156, (2020).

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ᢠయࡢศᏊෆ┦஫స⏝ࢿࢵࢺ࣮࣡ࢡ࡜ᶵ⬟ࡢ㐃㛵ࡢゎ᫂Investigation of the intramolecular interaction network and function of
antibodies‫ۑ‬㇂୰ ෪Ꮚ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗ┿᰾⣽⬊⏕≀ࡢࢱࣥࣃࢡ㉁ࡣከࡃ࡟ࡣ⢾㙐ಟ㣭ࡀ᪋ࡉࢀ࡚࠸ࡿࠋ⢾㙐ࡣࠊ⣽⬊㛫᥋╔ࡸࢩࢢࢼࣝఏ㐩ࠊࢱ

ࣥࣃࢡ㉁ࡢᵓ㐀ไᚚ࡞࡝ࠊ⣽⬊㛫ࢥ࣑ࣗࢽࢣ࣮ࢩࣙࣥࡸ⣽⬊ෆ⛛ᗎ⥔ᣢ࡟୙ྍḞ࡞Ꮡᅾ࡛࠶ࡿࡇ࡜ࡀぢฟࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⢾㙐ࡣෆ㒊㐠ືࡢ⮬⏤ᗘ࡟ᐩࡴࡇ࡜࡟ຍ࠼࡚」㞧࡞ศᶵᵓ㐀ࢆࡶࡕࠊỈ⁐ᾮ୰࡛ᦂࡽ࠸࡛࠸ࡿ⢾㙐࡟ᑐࡋ࡚ศᏊ⛉Ꮫⓗ࡞࢔ࣉ࣮ࣟࢳࢆ⾜࠺ࡇ࡜ࡣᐜ࡛᫆ࡣ࡞࠸ࠋ⢾㙐ࡢ❧యᵓ㐀ࢆṇࡋࡃ⌮ゎࡍࡿࡓࡵ࡟ࡣࠊ㟼ⓗ࡞Ᏻᐃᵓ㐀ࢆᤊ࠼ࡿࡔࡅ࡛ࡣ࡞ࡃࠊ❧యᵓ㐀ࡢᦂࡽࡂࢆྵࡵࡓືែ࡜ࡋ࡚ࡢᥥീࡀồࡵࡽࢀࡿࠋࡇ࠺ࡋࡓ≧ἣࡢࡶ࡜ࠊᡃࠎࡣ⢾㙐ࡢ❧యᵓ㐀ࢆࡑࡢືⓗ࡞ᛶ㉁ࡶྵࡵ࡚ゎ᫂ࡍࡿࡓࡵ࡟ࠊィ⟬⛉Ꮫᡭἲ࡜≀⌮໬Ꮫィࢆ⤌ࡳྜࢃࡏࡓ⢾㙐ᵓ㐀ゎᯒἲࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࠋࡑࡢ⤖ᯝࠊ⢾ࢱࣥࣃࢡ㉁ࡢ⁐ᾮ୰࡛ࢲ࢖ࢼ࣑ࢵࢡ࡟ᵓ㐀ኚ໬ࡍࡿᥥീࡀ᫂ࡽ࠿࡜࡞ࡾࡘࡘ࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⢾ࢱࣥࣃࢡ㉁ࡢືⓗᵓ㐀ኚ໬ࡀᶵ⬟ࡢⓎື࡟⤖ࡧࡘࡃศᏊ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣ౫↛࡜ࡋ࡚୙࡛᫂࠶ࡿࠋ
ᮏ◊✲࡛ࡣࠊ⢾ࢱࣥࣃࢡ㉁ࡢືⓗᵓ㐀࡟ࣉࣟࢢ࣒ࣛࡉࢀࡓᶵ⬟ࢆㄞࡳゎࡃࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࡇࢀࡲ࡛ᡃࠎࡣ㐟㞳ࡢ⢾㙐ࡢືⓗ࡞❧యᵓ㐀࡟ࡘ࠸࡚ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜᰾☢Ẽඹ㬆ἲࢆ⏝࠸ࡓᵓ㐀ゎᯒᡭἲࢆ☜❧ࡋ࡚ࡁ࡚ࡁࡓࠋࡇࡢᡭἲࢆ⢾ࢱࣥࣃࢡ㉁࡟ᛂ⏝ࡋࠊ⢾ࢱࣥࣃࢡ㉁ࡢືⓗᵓ㐀ኚ໬ࡀᶵ⬟ࡢⓎື࡟⤖ࡧࡘࡃศᏊ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࠋ⢾ࢱࣥࣃࢡ㉁ࡢࣔࢹࣝศᏊ࡜ࡋ࡚ࠊච␿⣔࡟࠾࠸࡚୺せ࡞ᙺ๭ࢆᢸ࠸ࠊ⤖ᬗᵓ㐀᝟ሗࡀ㇏ᐩ࡟࠶ࡿᢠయࡢ Fc 㡿ᇦ࡟╔┠ࡍࡿࠋMD ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡿ」ᩘࡢࢥࣥࣇ࢛࣐࣮
ࢆ⪃៖ࡋࡓ❧యᵓ㐀ࣔࢹࣝࢆసᡂࡋࠊNMR ࡸ SAXS ࡞࡝ࡢィ࡟ࡼࡗ࡚ほࡉࢀࡿᵓ㐀᝟ሗࡢ⌮ㄽ್ࢆ⟬ฟࡍࡿࠋᢠయࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡣ AMBER ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࠾ࡼࡧ GLYCAM06 ຊሙࢆ฼⏝ࡍࡿࠋᢠయࡢ Fc 㡿ᇦࢆศᏊ⏕≀Ꮫᡭἲ࡟ࡼࡗ࡚ㄪ〇ࡋࠊศᏊ⛉Ꮫ◊✲ᡤࡢ㧗☢ሙ NMR ⿦⨨ࢆ฼⏝ࡋࡓከḟඖィ࡟ࡼࡗ࡚ࠊࡑࡢ❧యᵓ㐀᝟ሗࢆྲྀᚓࡍࡿࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓᐇ㦂್࡜⌮ㄽ್ࢆẚ㍑ࡍࡿࡇ࡜࡛ࠊ

ᵓ㐀ࢧࣥࣉࣜࣥࢢࡢ㐺ษࡉࢆホ౯ࡋࠊᢠయࡢ⢾㙐㒊ศ࡜ࢱࣥࣃࢡ㉁㒊ศ཮᪉ࡢ❧యᵓ㐀ࢆ⁐ᾮ୰࡛ࡢࢲ࢖ࢼ
࣑ࢡࢫࢆྵࡵ࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆヨࡳࡿࠋࡉࡽ࡟ᢠయࡢศᏊෆ┦஫స⏝ࢿࢵࢺ࣮࣡ࢡࢆゎᯒࡋࠊ࣑ࢡࣟ࡞
┦஫స⏝ࢿࢵࢺ࣮࣡ࢡ࡜࣐ࢡࣟ࡞ᅄḟᵓ㐀ኚ໬࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

3◊✲ᡂᯝච␿ࢢࣟࣈࣜࣥ G㸦IgG㸧ࡢ Fc 㡿ᇦ࡟⤖ྜࡋ࡚࠸ࡿ୍ᑐࡢ N ᆺ⢾㙐࡟╔┠ࡋࠊࡑࡢᵓ㐀ࣂ࢚࣮ࣜࢩࣙࣥ࡜

ศᏊᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫࠊࡦ࠸࡚ࡣᶵ⬟࡜ࡢ㐃㛵ࢆணࡍࡿࡇ࡜࡟ྲྀࡾ⤌ࢇࡔࠋศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊࢢࣛ࢖ࢥࣇ࢛࣮࣒ࢆᨵኚࡋࡓ୍㐃ࡢ Fc ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙ
ࣥ✵㛫᥈ᰝࢆ⾜࠸ࠊྛࢢࣛ࢖ࢥࣇ࢛࣮࣒࡟ࡘ࠸࡚ࡢືⓗᵓ㐀࢔ࣥࢧࣥࣈࣝࢆྲྀᚓࡋࡓࠋMD ࢩ࣑࣮ࣗࣞࢩࣙ

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ࣥࡢ⤖ᯝࡢጇᙜᛶࢆ㔞Ꮚࣅ࣮࣒⁐ᾮᩓ஘ࡸ᰾☢Ẽඹ㬆㸦NMR㸧ἲ࡞࡝ࡢᐇ㦂ⓗᡭἲ࡟ࡼࡾ᳨ドࡋࡓࠋ୍᪉࡛ࠊ⢾㙐ࢆࣔࢹࣝศᏊ࡜ࡋ࡚ࠊᵓ㐀࢔ࣥࢧࣥࣈࣝࢆໟᣓⓗ࡟ྲྀࡾᢅ࠺࢔ࣉ࣮ࣟࢳἲࢆ☜❧ࡋࡓࠋࡇࡢ
᪉ἲࢆᛂ⏝ࡋ࡚ࠊNMR ࢹ࣮ࢱ࡜ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࢆ⤫ྜࡋࠊFc ࡢศᏊᵓ㐀୰ࡢ⢾㙐-ࢱࣥࣃࢡ㉁ࡢ┦஫స⏝ࢿࢵࢺ࣮࣡ࢡࢆ᫂ࡽ࠿࡟ࡍࡿᇶ┙ࢆᵓ⠏ࡋࡓࠋࡇࢀ࡟ࡼࡾࠊFc ࡢࢢࣛ࢖ࢥࣇ࢛࣮࣒ࡢᨵኚࡢᙳ㡪ࢆศᏊෆ࡛࢔࣑ࣀ㓟ṧᇶ࡟ఏ᧛ࡍࡿࣁࣈ࡜࡞ࡿ⢾ṧᇶࡢᏑᅾࢆ✺ࡁṆࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
㇂୰෪Ꮚ࠙ᣍᚅㅮ₇ࠚ
ᢠయࡢ 3 ḟඖᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫ࡜┦஫స⏝ࡢࢲ࢖ࢼ࣑ࢡࢫࢆࡳࡿ
PPF2020/2021 ➨ 18 ᅇḟୡ௦ࢆᢸ࠺ⱝᡭࡢࡓࡵࡢࣇ࢕ࢪ࣭࢝ࣝࣇ࢓࣮࣐ࣇ࢛࣮࣒ࣛ
2021 ᖺ 9 ᭶ 14 ᪥࠙࢜ࣥࣛ࢖ࣥ㛤ദࠚ
㸹I-04.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ ௒ᚋࠊᮏㄢ㢟࡛ᚓࡽࢀࡓ◊✲ᡂᯝ࡟ࡘ࠸࡚ࡢཎⴭㄽᩥࢆฟ∧ࡍࡿணᐃ࡛࠶ࡿࠋ

- 462 -

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DE`ÀÓ»ÅÆl=^J4ËFRET -4<M=`¦ÅÆl=^J4Ë,±DS.^ÖZ^2`,¥ (AlphaFold2 ')I.1<^8`mf¤Ñd¬,Ç(<^
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!3.1 |ÌpT`=`F1-ATPase  *a{×S2F;R|ÌpT`=`F1-ATPase ATP sªpÊ0G[3`,ha{|Ì*pT`=`*
°foÄ%+ Fo T`=`')~{|Ì(+ ATP , ADP Z^Ó (y*Z
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Ë e +¤Ñ,*/=^J4Ë*®U<^9^5_DS.^&LDS.^>s+(DS.^Ö,eZ^2`_,>*É )ÂjI.1<^8`,Õ²*$h!Â,CY.-^D0Y`tt­³« A(+*qa«'*t­³«Õ²,W@2021 2 7 HÕ+c=^J4Ë¤Ñd¬M]5Y- 465 -

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 Kei-ichi Okazaki, “Multiscale simulations of conformational dynamics of transporter and membrane-remodelingproteins in function”, Symposium on Computer Simulations and Cryo-ET/EM of Complex Biomolecular Systems,
Online, 2021/11/18
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 Takuma Kikutsuji, Yusuke Mori, Kei-ichi Okazaki, Toshifumi Mori, Kang Kim, and Nobuyuki Matubayasi“Explaining reaction coordinates of alanine dipeptide isomerization obtained from deep neural networks using
Explainable Artificial Intelligence (XAI)”, J. Chem. Phys. 156, 154108 (2022); https://doi.org/10.1063/5.0087310

 Titouan Jaunet-Lahary, Tatsuro Shimamura, Masahiro Hayashi, Norimichi Nomura, Kouta Hirasawa,
Tetsuya Shimizu, Masao Yamashita, Keiichi Kojima, Yuki Sudo, Takashi Tamura, Hiroko Iwanari, Takao
Hamakubo, So Iwata, Kei-ichi Okazaki, Teruhisa Hirai, and Atsuko Yamashita “Structure and mechanismof oxalate transporter OxlT in an oxalate-degrading bacterium in the gut microbiota”, biorxiv, doi:
https://doi.org/10.1101/2021.11.15.468502- 466 -

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢖࢜ࣥᾮయࡢ◊✲Molecular Dynamics Study of Ionic Liquids‫ ⏣▼ۑ‬ᖸᇛ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ

ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊจ⦰⣔࡟࠾ࡅࡿ◊✲ᑐ㇟ࡢ࠺ࡕࠊ≉࡟࢖࢜ࣥᾮయ࡟ࡘ࠸࡚ࡢ⌮ㄽ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ
ලయⓗ࡟ࡣࠊ୺࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓゎᯒ࡜◊✲ࢆ⥆ࡅ࡚ࡁ࡚࠸ࡿࠋ௒ᖺᗘࡣ௨ୗࡢ㸰ࡘࡢ◊✲┠ⓗ࡟ἢࡗ࡚◊✲ࢆィ⏬࣭㐙⾜ࡋࡓࠋෆᐜ࡟ࡘ࠸࡚௨ୗ࡟ሗ࿌ࡍࡿࠋ
㸦㸯㸧࢖࢜ࣥᾮయࡣ㝧࣭㝜࢖࢜ࣥ࠿ࡽ࡞ࡾࠊᐊ

࡟࠾࠸࡚ᾮయࡢᣲືࢆ♧ࡍࠋ㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏ࡟

ࡼࡾᛶ㉁ࡢ␗࡞ࡿ✀㢮ࡢ࢖࢜ࣥᾮయࡀྜᡂ࡛ࡁࡿࡓࡵࠊᵝࠎ࡞⏝㏵࡟㐺ࡋࡓ࢖࢜ࣥᾮయࡢ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋ㸯ࡘࡢ౛࡜ࡋ࡚ᣲࡆࡽࢀࡿࡢࡀࢭ࣮ࣝࣟࢫ㧗ศᏊࡢࡼ࠺࡞Ỉࡸ᭷ᶵ⁐፹࡟㞴⁐࡞≀㉁࡟ᑐࡋࠊ፹㉁ࢆ
᭰࠼ࡿࡇ࡜࡟ࡼࡗ࡚⁐ゎ཯ᛂ᮲௳ࡢ㣕㌍ⓗ࡞ᨵၿࢆヨࡳࡿ◊✲࡛࠶ࡿࠋࢭ࣮ࣝࣟࢫࡢศゎ཯ᛂࢆ⏝࠸࡚ࢢࣝࢥ࣮ࢫ࡞࡝ࡢⅣ໬Ỉ⣲໬ྜ≀ࢆ‽ഛࡍࡿ㐣⛬ࡣ๓ฎ⌮㐣⛬࡜࿧ࡤࢀ࡚࠸ࡿࠋࡇࡢ㐣⛬ࢆ࠸࠿࡟ຠ⋡ࡼࡃ⾜࠺࠿ࡀࡑࢀ࡟⥆ࡃࣂ࢖࢜⇞ᩱྜᡂ࣭⢭〇࡟⨨࠸࡚㔜せ࡟࡞ࡿࠋࡇࢀࡲ࡛ࡢᐇ㦂◊✲࡟ࡼࡾࠊỈࡸᚑ᮶ࡢ᭷ᶵ⁐፹࡟ẚ࡭࡚࢖࢜ࣥᾮయࡣࢭ࣮ࣝࣟࢫྵ᭷ࡢࣂ࢖࣐࢜ࢫࡢ⁐ゎࢆ㣕㌍ⓗ࡟ಁ㐍ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀ࡚ࡁ࡚
࠸ࡿࠋࡋ࠿ࡋࠊ࢖࢜ࣥᾮయ࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢ⁐ゎ㐣⛬ࡀ࡝ࡢࡼ࠺࡞࣓࢝ࢽࢬ࣒࡛㉳ࡇࡗ࡚࠸ࡿࡢ࠿ࡣ᫂ࡽ
࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᚑࡗ࡚ࠊ࢖࢜ࣥᾮయࡢࡼ࠺࡞͆᪂ࡋ࠸ᾮయ͇࡜࿧ࡤࢀࡿ⁐፹࡟ࡘ࠸࡚ࠊᚑ᮶ࡢ௚ࡢ⁐፹࡟㛵ࡍࡿ▱ぢࢆά࠿ࡋࡓୖ࡛⌮ㄽ◊✲ࢆࡋ࡚࠸ࡃࡇ࡜ࡀࠊᐇ㦂࣭⌮ㄽ◊✲཮᪉࡬ࡢ㔜せ࡞ᶫΏࡋ࡜࡞ࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋ᫖ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡢィ⟬ᶵ฼⏝࡟ࡼࡿศᏊືຊᏛἲࢆ⏝࠸ࡓ◊✲࠿ࡽࠊ㧗ศᏊࢭ࣮ࣝࣟࢫ㛫࡟ാࡃࢭ࣮ࣝࣟࢫศᏊ㛫ࠊ࠾ࡼࡧศᏊෆỈ⣲⤖ྜࡣỈ୰࡟㍑࡭࡚࢖࢜ࣥᾮయ୰࡛ࡣ㝧࣭㝜࢖࢜ࣥࡢാࡁ࡟ࡼࡗ࡚ᙅࡵࡽࢀࠊࡇࡢࡇ࡜ࡀ࢖࢜ࣥᾮయ୰࡛ࢭ࣮ࣝࣟࢫࡢศゎࡀಁ㐍ࡉࢀࡸࡍ࠸ཎᅉࡢ㸯ࡘ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ㝜࢖࢜ࣥ࡟ࡼࡾಁ㐍ࡉࢀࡿศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡀศᏊ㛫Ỉ⣲⤖ྜࡢゎ㞳ࡼࡾࡶඃඛࡋ࡚࠾ࡇࡿࡇ࡜ࡀィ⟬⤖ᯝࡼࡾ♧ࡉࢀࠊᐇ㦂◊✲࡟ࡼࡿᣦ᦬࡜ࡶ୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋࡲࡓࠊ㝧࢖࢜ࣥࡢᙺ๭࡟ࡘ࠸࡚ࡶࠊゎ㞳ࡋࡓࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ࡢ࿘㎶࡟ศᏊ㛫┦஫స⏝㸦୺࡟ YDQGHU:DDOV┦஫స⏝㸧ࢆ௓ࡋ࡚Ꮡᅾࡋࠊ⁐ゎ㐣⛬࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㸦“Theoretical Investigation of
Dissolution and Decomposition Mechanisms of a Cellulose Fiber in Ionic Liquids”, Tateki Ishida, J. Phys. Chem. B
2020, 124, 3090-3102.㸧௒ᖺᗘࡣ◊✲ࢆࡉࡽ࡟㐍ࡵ࡚ࢭ࣮ࣝࣟࢫࡢᣲື࡜࢖࢜ࣥᾮయ࡜ࡢ┦஫స⏝ࢆゎᯒࡋࡓࠋຍ࠼࡚㝜࢖࢜ࣥࡢ✀㢮ࢆኚ࠼ࡓᩘ✀㢮ࡢ࢖࢜ࣥᾮయ࡟ࡘ࠸࡚㧗ศᏊࢭ࣮ࣝࣟࢫࡢ⁐ゎ࣭ศ㞳㐣⛬ࡢ㐪࠸ࢆ◊✲ࡋࠊᗘຠᯝ࡟ࡘ࠸࡚ࡶศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆィ⏬ࡋࠊᐇ⾜ࡋࡓࠋࡇࢀࡽࡢィ⟬⤖ᯝ࠿ࡽࠊࢭ࣮ࣝࣟࢫࡢ⁐ゎ࣭ศ㞳࡟㛵ࡋ࡚཯ᛂᛶࡢ㧗࠸࢖࢜ࣥᾮయࢆ᥈⣴ࡍࡿୖ࡛ࡢ᭱㐺࡞㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏࡢᣦᶆࢆィ⟬⤖ᯝ࠿ࡽᢳฟ
ࡍࡿẁ㝵࡟ࡲ࡛◊✲ࢆ㐍ࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ ຍ࠼࡚ࠊᐇ㝿ࡢࣂ࢖࣐࢜ࢫࡣࢭ࣮ࣝࣟࢫ࡟ຍ࠼࡚࣑࣊ࢭ࣮ࣝࣟࢫࡸࣜࢢࢽࣥ࡜࠸ࡗࡓ㧗ศᏊ࠿ࡽ࡞ࡿ」㞧

- 467 -

࡞ᵓ㐀ࢆᣢࡘࡇ࡜࡟╔┠ࡋࡓ◊✲࡬ࡢᒎ㛤ࡶጞࡵࡿࡇ࡜ࡀฟ᮶ࡓࠋලయⓗ࡟ࡣࠊᐇ㝿ࡢࣂ࢖࣐࢜ࢫ࡟㏆࠸ᵓ㐀ࢆᣢࡘࣔࢹࣝࣂ࢖࣐࢜ࢫ࡜ࡋ࡚ࢭ࣮ࣝࣟࢫ࡜࣑࣊ࢭ࣮ࣝࣟࢫ࠿ࡽ࡞ࡿࣔࢹࣝࣂ࢖࣐࢜ࢫ㧗ศᏊࣇ࢓࢖ࣂ࣮
ࢆᑐ㇟࡟㑅ࡧࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡢィ⟬ᶵ฼⏝࡟ࡼࡿ‽ഛィ⟬ࢆᐇ⾜ࡋࡓࠋ௒ᚋࡣࠊỈ୰࡟࠾ࡅࡿࢭ
࣮ࣝࣟࢫ࣭࣑࣊ࢭ࣮ࣝࣟࢫࡢ㓄⨨ᵓ㐀ࡀ࢖࢜ࣥᾮయ୰࡛ࡣ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿࡢ࠿ࢆㄪ࡭ࠊࡉࡽ࡟⁐ゎ࣭ศゎ㐣⛬࡟ࡘ࠸࡚ࡶゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ
㸰 ࢖࢜ࣥᾮయࡣ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ࣌࢔ࢆኚ࠼ࡿࡇ࡜࡛ከ✀ከᵝ࡞≀ᛶࡸ≀⌮໬Ꮫⓗᣲືࡀほᐹࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ≉࡟  ୡ⣖ึ㢌࠿ࡽከࡃࡢᐇ㦂◊✲࡟ࡼࡿሗ࿌ࡀ⾜ࢃࢀ࡚ࡁࡓࠋࡇࡢࡼ࠺࡞≧ἣࡢࡶ࡜ࠊ⌮ㄽ◊✲ࡢほⅬ࠿ࡽࡣከࡃࡢ࢖࢜ࣥᾮయࡀ♧ࡍ≀ᛶࡸ≀⌮໬Ꮫⓗᣲື࡟ඹ㏻ࡍࡿᛶ㉁ࢆぢฟࡋࠊ⣔⤫ⓗ࡟ゎᯒࡍࡿࡇ࡜ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋ ࢖࢜ࣥᾮయࡢከᵝ࡞≉ᛶࡢ㸯ࡘ࡟⦆࿴㐣⛬ࡸືⓗ୙ᆒ୍ᛶ࡞࡝ࡢືⓗ࡞ᣲືࡀ࠶ࡿࠋࡇࡢᣲື࡟ࡘ࠸࡚ࡣࠊ
㏆ᖺࠊከࡃࡢᐇ㦂ࡸ⌮ㄽ◊✲࡟ࡼࡿ⤖ᯝ࠿ࡽࠊ࢞ࣛࢫ࡞࡝࡟≉᭷ࡢືⓗ୙ᆒ୍ᛶࡀ࢖࢜ࣥᾮయ࡛ࡶ⌧ࢀࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚ࡣ࠸ࡿࡀࠊศᏊࣞ࣋ࣝ࡟࠾ࡅࡿヲ⣽࡟ࡘ࠸࡚ࡣࡲࡔࢃ࠿ࡗ࡚࠸࡞࠸ࠋ᫖ᖺᗘࡣィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ฼⏝ࡋࠊศᏊືຊᏛἲࢆ⏝࠸ࡓᩘⓒࢼࣀ⛊࣮࢜ࢲ࣮ࡢ㛗᫬㛫ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ◊✲ࢆ㐍ࡵࡓࠋ◊✲⤖ᯝࡼࡾࠊ࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀ࡀ࢖࢜ࣥᾮయࡢ୙ᆒ୍ᛶ࡟ࡼࡗ࡚኱ࡁࡃᙳ㡪ࡉࢀ࡚࠸ࡿ
ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋཎᅉࡢ୍ࡘ࡜ࡋ࡚ࠊ㝧࣭㝜࢖࢜ࣥ⮬㌟ࡢ✵㛫ⓗ࡞ศᕸ࡜୧࢖࢜ࣥࡢ㓄ྥࡀ኱ࡁࡃ㛵ಀࡋ࡚࠸ࡿࡇ࡜ࡀゎࡗࡓࠋࡲࡓࠊືⓗ୙ᆒ୍ᛶࢆᘬࡁ㉳ࡇࡍ㸯ࡘࡢཎᅉ࡜ࡋ࡚ࡢ㝧࣭㝜࢖࢜ࣥ⮬㌟ࡢ㐠ື㸦ศᏊෆ㐠ືࡶྵࡵࡓ㐠ື㸧ࡢኚ໬ࡀ⪃࠼ࡽࢀࠊ࢖࢜ࣥศᏊࡢ༠ྠ㐠ືࡀ኱ࡁࡃ㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
௒ᖺᗘࡣࠊ࢖࢜ࣥศᏊ⮬㌟ࡢᵓ㐀ࡢኚ໬ࡀ✵㛫ⓗ୙ᆒ୍ᛶࡢ㉳※࡟㛵ಀࡋ࡚࠾ࡾࠊ㟼ⓗᵓ㐀ࡢヲ⣽࡞ゎᯒࡀືⓗ୙ᆒ୍ᛶࡢ◊✲࡟ྥࡅ࡚ࠊ㠀ᖖ࡟᭷ຠ࡛࠶ࡿࡇ࡜ࢆㄪ࡭ࡿẁ㝵࡟ࡲ࡛ࡉࡽ࡟◊✲ࢆィ⏬࣭㐙⾜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ࢖࢜ࣥᾮయ୰࡛ࡢ㧗ศᏊࢭ࣮ࣝࣟࢫࡢྍ⁐໬࡟㛵ࡍࡿ◊✲࡟࠾࠸࡚ࡣศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ࢖࢜ࣥᾮ
య࡜Ỉ୰࡟࠾ࡅࡿ㧗ศᏊࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ㐣⛬ࡢゎᯒࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣ࢖࢜ࣥᾮయ࡟ࡣ཯ᛂຠ⋡ࡢࡼ࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ㸦>&PLP@>$FHWDWH@㸧࡟ຍ࠼࡚ࠊ㝜࢖࢜ࣥࢆ᭰࠼ࡓ࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2

+ 32@㸧࡜ࠊᐊ࡛ࡢ⢓ᛶࡀᑠࡉࡃ

཯ᛂᛶࡢ㧗࠸ูࡢ࢖࢜ࣥᾮయ㸦>&PLP@>+32@㸧ࡢ㸰✀㢮ࢆ㑅ࢇ࡛㧗ศᏊࢭ࣮ࣝࣟࢫࢆ⁐㉁࡜ࡋ࡚ࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࢆᐇ⾜ࡋࡓࠋ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ௨እࡢ㸰✀㢮ࡢ࢖࢜ࣥᾮయ࡟㛵ࡋ࡚ࡣຊሙࡢタᐃ㸦≉࡟㝜࢖࢜ࣥࡢྛཎᏊࢧ࢖ࢺୖࡢ㟁Ⲵࡢタᐃ㸧ࡀᚲせ࡟࡞ࡿࠋᚑࡗ࡚ࠊࡇࢀࡽࡢຊሙタᐃࡣࢭ࣮ࣝࣟࢫ
ࡢศゎ࣭⁐ゎࡀ⏕ࡌࡿ࠿࡝࠺࠿ࢆ☜ㄆࡋ࡞ࡀࡽཎᏊࢧ࢖ࢺୖࡢ㟁Ⲵࡢㄪᩚࢆࡋ࡞ࡀࡽ⾜ࡗࡓࠋ࢖࣑ࢲࢰࣜ࢘
࣒࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ࡜࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷࢖࢜ࣥᾮయࡢྛࠎ࡟ࡘ࠸࡚㸯㸮㸮Υࡢᗘୗ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐙⾜ࡋࡓࠋ㸯㸮ಶࡢࢢࣝࢥ࣮ࢫࢆྵࢇࡔ㧗ศᏊ㙐ࢆከᩘ⏝࠸࡚✚ᒙᵓ㐀࡟ࡋࡓ㧗ศᏊࢭࣝࣟ
࣮ࢫ࡟㛵ࡋ࡚㸰✀㢮ࡢ࢖࢜ࣥᾮయ୰࡛ࡢ⁐ゎ࣭ศゎ㐣⛬ࡢẚ㍑ࢆ⾜ࡗࡓࠋ≉࡟ࢭ࣮ࣝࣟࢫෆࠊཬࡧࢭ࣮ࣝࣟ

- 468 -

ࢫ㛫Ỉ⣲⤖ྜࡢษ᩿㐣⛬ࡀ㝜࢖࢜ࣥࡢ✀㢮ࢆኚ࠼ࡿ㸦ࡇࡢሙྜࡣ࢖࢜ࣥࡢ኱ࡁࡉ㸧ࡇ࡜࡛࡝ࡢࡼ࠺࡟ኚ໬ࡍ
ࡿ࠿ࢆㄪ࡭ࡓࠋࡉࡽ࡟ࢭ࣮ࣝࣟࢫศᏊෆ࣭㛫Ỉ⣲⤖ྜࡢษ᩿࡟కࡗ࡚㝧࣭㝜࢖࢜ࣥࡀ㧗ศᏊࣇ࢓࢖ࣂ࣮ෆ࡬
࡜౵ධࡋ࡚࠸ࡃ㐣⛬ࡀ㸰ࡘࡢ࢖࢜ࣥᾮయ࡛࡝ࡢࡼ࠺࡟␗࡞ࡿࡢ࠿ࢆゎᯒࡋࡓࠋࡲࡓࠊࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮
ࢆྲྀࡾᅖࡴࢭ࣑࣮࣊ࣝࣟࢫࡢ◊✲࡟㝿ࡋ࡚ࡣࢭ࣮ࣝࣟࢫ࡜࣑࣊ࢭ࣮ࣝࣟࢫ࠿ࡽ࡞ࡿࣔࢹࣝࣂ࢖࣐࢜ࢫࢆᵓ⠏ࡋࠊ⁐፹࡟ࡣỈࢆ㑅ࡧࠊ‽ഛィ⟬ࢆᐇ⾜ࡋࡓࠋ୍᪉ࠊ࢖࢜ࣥᾮయࡢືⓗᣲື࡟㛵ࡍࡿ◊✲࡛ࡣ࢖࣑ࢲࢰ࣒ࣜ࢘ᆺࡢ࢖࢜ࣥᾮయ࡟㛵ࡋ࡚࢔ࣝ࢟ࣝ㙐ࡢ㛗ࡉࢆኚ࠼࡚࠸ࡁࠊᩘ✀㢮ࡢ࢔ࢽ࢜ࣥ࡜⤌ࡳྜࢃࡏࡓ⣔࡟ᑐࡋ࡚ᐊ

࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿィ⟬ࢆᐇ⾜ࡋࡓࠋィ⟬⤖ᯝࢆ⏝࠸࡚ D 㝧࢖࢜ࣥศᏊෆࡢ࢔ࣝ࢟ࣝ㙐ࡢ㐠ືࡢᦂࡽࡂࡢ᫬㛫ࢫࢣ࣮ࣝ࡜࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀࡜✵㛫ⓗ୙ᆒ୍ᛶࡢ┦㛵㛵ಀࡢゎ᫂ࠊ㸦㹠㸧㝧࣭㝜୧࢖࢜ࣥศᏊࡢ㓄ྥࡀ࢖࢜ࣥศᏊࡢ✵㛫ⓗ࡞ศᕸ࡟୚
࠼ࡿᙳ㡪ࡢゎᯒࢆ⾜ࡗࡓࠋ඲࡚ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥィ⟬ࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ *520$&6 ࢆ⏝࠸࡚⾜ࡗࡓࠋ3◊✲ᡂᯝ࢖࢜ࣥᾮయ୰࡛ࡢ㧗ศᏊࢭ࣮ࣝࣟࢫࡢྍ⁐໬࡟㛵ࡍࡿ◊✲࡟ࡘ࠸࡚ࡣࠊỈࡸᚑ᮶ࡢ᭷ᶵ⁐፹࡟ẚ࡭࡚࢖࢜ࣥᾮయࡣࢭ࣮ࣝࣟࢫྵ᭷ࡢࣂ࢖࣐࢜ࢫࡢ⁐ゎࢆ㣕㌍ⓗ࡟ಁ㐍ࡍࡿࡇ࡜ࡀࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ◊✲⤖ᯝࡼࡾ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ࢖࢜ࣥᾮయ࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢ⁐ゎ㐣⛬ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡶࠊ㧗ศᏊࢭࣝࣟ
࣮ࢫ㛫ࡢศᏊ㛫Ỉ⣲⤖ྜࡣỈ୰࡟ẚ࡭࡚࢖࢜ࣥᾮయ୰࡛ࡣᙅࡃ࡞ࡿࡇ࡜ࡀ㔞Ꮚ໬Ꮫィ⟬࡜ศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ࡟᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢ⤖ᯝࡣ࢖࢜ࣥᾮయࡀ⏕య㧗ศᏊ୰ࡢỈ⣲⤖ྜษ᩿⬟ຊࡀ㧗࠸ࡇ࡜ࢆ♧ࡍࡶࡢ࡜ࡋ࡚㔜せ࡞ᡂᯝ࡛࠶ࡿࠋࡉࡽ࡟ࠊศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡀศᏊ㛫Ỉ⣲⤖ྜࡢゎ㞳ࡼࡾࡶඃඛࡋ࡚࠾ࡇ
ࡿࡇ࡜ࡀィ⟬⤖ᯝࡼࡾ♧ࡉࢀࠊᐇ㦂◊✲࡟ࡼࡿᣦ᦬࡜ࡶ୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋຍ࠼࡚ࠊࡇࡢศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡣ㝜࢖࢜ࣥ࡟ࡼࡗ࡚ᘬࡁ㉳ࡇࡉࢀ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊィ⟬⤖ᯝࡢヲ⣽࡞ゎᯒ࠿ࡽࠊ㝧࢖࢜ࣥࡢാࡁࡶ᫂ࡽ࠿࡟ࡉࢀࠊ㧗ศᏊ≧ែ࠿ࡽศ㞳ࡋࡓࢭ࣮ࣝࣟࢫ㙐ࡣࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫຊࢆ㏻ࡋ࡚㝧࢖࢜ࣥ࡟ࡼࡗ࡚Ᏻᐃ໬ࡉࢀࠊ࢖࢜ࣥᾮయ୰࡛ࡢ⁐ゎࡀಁ㐍ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽࡢ◊✲ᡂᯝࡣᏛ⾡ㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ㸦“Theoretical Investigation of Dissolution and Decomposition
Mechanisms of a Cellulose Fiber in Ionic Liquids”, Tateki Ishida, J. Phys. Chem. B 2020, 124, 3090-3102.㸧௒ᖺᗘࡣࡉࡽ࡟࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ㸦>&PLP@>$FHWDWH@㸧࡟ຍ࠼࡚ࠊ㝜࢖࢜ࣥࢆ᭰࠼ࡓ
࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2

+ 32@㸧࡜ࠊᐊ࡛ࡢ⢓ᛶࡀᑠࡉࡃ཯ᛂᛶࡢ㧗࠸ูࡢ࢖࢜ࣥᾮయ㸦>&PLP@>+32@㸧ࡢ㸰✀㢮ࢆ⁐፹࡜ࡋ࡚㑅ࢇࡔࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋィ⟬⤖ᯝ࠿ࡽࡣࣜࣥ㓟ࢆྵࡴ࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయࡢ᭷⏝ᛶࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋලయⓗ࡟ࡣࠊ࢔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࠿࡟࡞ࡗࡓࠋຍ࠼࡚ࠊ

- 469 -

ᗘኚ໬࡟ࡼࡿࣜࣥ㓟ྵ᭷࢖࢜ࣥᾮయ୰࡛ࡢศゎ㐣⛬ࡢ㐪࠸ࡢ◊✲ࢆ⌧ᅾ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࡀࠊ㏵୰ࡢゎᯒ⤖ᯝ࠿ࡽࡶ㸯㸮㸮Υࡢࡼ࠺࡞㧗࡛ࡣ࡞ࡃࠊ㸶㸮Υࠊࡶࡋࡃࡣ㸳㸮Υࡢᗘୗ࡛ࡶ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥᾮయ

࡟ẚ࡭࡚ຠ⋡ࡼࡃศゎࢆ㐍ࡵࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ◊✲ᡂᯝࡣࠊ࢖࢜ࣥᾮయࡢࡼ࠺࡞͆᪂ࡋ࠸
ᾮయ͇࡟㛵ࡋ࡚ᐇ㦂࣭⌮ㄽ◊✲཮᪉࡬ࡢ㔜せ࡞ᶫΏࡋ࡜࡞ࡾ࠺ࡿࠋ௒ᚋࠊ

ᗘኚ໬࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢศゎ㐣⛬ࡢ㐪࠸࡜ࡑࡢ㐣⛬࡟࠾ࡅࡿ㝧࣭㝜࢖࢜ࣥࡢᣲືࡢ㐪࠸ࢆゎᯒࡋ࡚࠸ࡃணᐃ࡛࠶ࡿࠋࡲࡓࠊࢭ࣮ࣝࣟࢫ࡜
࣑࣊ࢭ࣮ࣝࣟࢫ࠿ࡽ࡞ࡿࣔࢹࣝࣂ࢖࣐࢜ࢫࡢ‽ഛィ⟬࡟ࡼࡿ⤖ᯝ࠿ࡽࡣࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ෆࡢỈ⣲⤖ྜ࡬ࡢ⁐፹ࡢ᥋㏆ࢆ㜼ᐖࡍࡿࡼ࠺࡟࣑࣊ࢭ࣮ࣝࣟࢫࡣࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ࢆྲྀࡾᅖࡴࡼ࠺࡟㓄⨨ࡍࡿࡇ࡜ࡀ
ከ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀࡟㛵ࡍࡿ◊✲࡟࠾࠸࡚ࡣ࢖࢜ࣥศᏊࡢᵓ㐀ࡢศᕸ࡜✵㛫ⓗ࡞࢖࢜ࣥศᏊࡢศᕸࡢ୙
ᆒ୍ᛶࡢ┦㛵࡟㛵ࡋ࡚㔜せ࡞⤖ᯝࡀᚓࡽࢀࡓࠋ◊✲⤖ᯝࡼࡾࠊ࢖࢜ࣥᾮయ୰࡛ࡣ㝧࣭㝜࢖࢜ࣥศᏊࡣ࢖࢜ࣥ
ศᏊࡢᵓ㐀ࡢศᕸ࡟౫Ꮡࡋ࡚✵㛫ⓗ࡟୙ᆒ୍࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊ✵㛫ⓗ࡞࢖࢜ࣥࡢศ
ᕸࡣ㝧࣭㝜୧࢖࢜ࣥࡢ㓄ྥࡢ࠸ࡃࡘ࠿ࡢࣃࢱ࣮ࣥࡀせᅉ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᚓࡽࢀࡓ◊✲⤖ᯝ࠿ࡽ࢖࢜ࣥᾮయࡢ≀⌮ⓗࠊ໬Ꮫⓗᣲື࡟㛵ࡋ࡚ࡉࡽ࡟▱ぢࢆ῝ࡵ࡚࠸ࡃྍ⬟ᛶࡀ㛤࠿ࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

≉࡟࡞ࡋࠋ  5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫“ۻ‬Theoretical Investigation of Dissolution and Decomposition Mechanisms of a Cellulose Fiber in Ionic Liquids”,
Tateki Ishida, J. Phys. Chem. B 2020, 124, 3090-3102.

- 470 -

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O%'^C 9vE:O6HL PAW [33,34]+' e²ÛpÛg LDA +'(«~OF¦ OCKO5(216 9v+>! cubic L0+
s2.0& 3.4 g/cm3 0.2 3 9vy+OCKO5(%3   1fs Ç.OOL NVT +J(  300K
V 9000K  3ps Rf+Ç 9000K
 2ps RfV5000K& 9000K

 2ps i¤&  5000K  2ps [15000K& 300K  2ps 18 melt-quench 8:CV& 2ps Rf+ÇkV8=C6I<+Ö @#+.GLB-8ÖG;L(Ö @9v

(e

0.01eV/Å Y(ZÇlvc6

Ê phonopy  VASP  k*%'Ç§[|ª Allen-Feldman «ÑG
vc6Ê¿l&X&)D4<L+¬Ì¹Allen-Feldman «Ñ%(§[|ªÌ¹^ python Q%'Ç .GLB-8Ö©+d(h¢
Q68:O<GN7QÊ+ÇQ68:O<GN7QÌ¹ HomCloudQ7+d¬

3 -/$µ¸X&)ÖG;LßyU}y\y"È2.0, 2.4, 2.8,
3.2 g/cm3 ZX&)#+ Fig.¦a)|9v%g{'y%
%g4k sf(  16 *yÖ{§[|ª+Ì¹¿+ Fig.1b)|y \§[|ª ß K£rm)(¿<§[|ªy _Û` wq( { (- 472 -

2c a) ; #%!BZ#% b) 69 D+7F K^.GLB-8 (c6GQTq¯Ò+o(\?qgPqc6GQ
¤propagon¥Oq&¼.&(

GQ(diffuson)Oq(GQ(locon)cz?
(





Õ

J

(§[|+_#

propagon  diffuson (RÅ¯propagon GQv]y;@0Ó$W)%§`fª#-2 8QKO5+(¯cP+j(68:0 M
%B2?Ov]y+0w ¿propagon L+M)(K3.0g/cm3
y a-C §[|ªK£¯ 3.0 W/m.K }a rm)( µ¸Ì¹¿ 1.0 W/m.K 

() propagon LM)%(Â&)(

propagon nÞ%'!A68:0K£a+I.0w(B (J¯c(0w(§[|ªyÛ`¥+("ÖÊ+Ç/E¯Öam kÓ9v¿kcP+Ì¹-Çµ¸rm)(¿<kÓ9vy _u'¿kM ( 2
; C 9v%g+& sp2 ¿k sp3 ¿k& sp ¿k+9v4k+Ê¿
C§(¿ku+2J( a
2d 69 [,> K^1.8A +¬%g- 473 -

2 9v sp ¿k%g

3 9v sp2 ¿k%g ©9v sp3 ¿k+9v((2.4 g/cm3

YSy sp ¿k+9v ,  sp2, sp3 ¿k, +7"(sp3 4kyU _sp2 i _(2.4 g/cm3 Y sp2 ¿k sp3 ¿k4ksf $ 'sp ¿k ysN)YH(¿k]sf%ÖÛ`( +Ð ("ring statistics Ê#ÇRing statistics #¿ku2J a 1.8A +¬\y()ª
YS¡¦+ ringH  { 5,6,7 ¡¦ ring  sp2  sp3 rk%

U))YS¡¦g ring H5 sp ¿k 5*(%x(Â&)(SkÓ9vDO%g$ ring statistics \r+>!y(Ê¢&Q68:O<GN7QÌ¹+Çk#\yßyOCL
(¦n§nQ68:O<C+C¨|¦nQ68:O<C ( birth time ~0.6
Å2 ¢F#(cP yS (w( j)( birth time  C-C kÓ9v+ij(§nQ68:O<C¦n#
#birth-death timeM¢Fy ß

2e ('2 UPQA

- 474 -

cPz©Z

cP U(+= &)(&Q68:O<C &X&) persistent image vector {Vcc+Ç\yßyÖ+©Z&)\y((O^Ö<J+Ç¿ring statistics u 0KO5g H(+={(¿ X&)  persistent image vector +¬(§[|ª+AQ(UG;L ^ (#2)&¿Q68:O<GN7Q kÓ9vDO
%g$ ring statistics +k\r+'Ö¨+¿ (,)v(+|(4 *94 3//4'3/:'4/A:53/)9)'2+9/3;2':/545,:.+83'2:8'49658:'4*.+':-+4+8':/54/49+3/)54*;):/4-3':+8/'29B
')/,/).+3  +)    42/4+4</:+* 3//4'3/:'4/A(/4/:/568+*/):/5495,9;6+8)54*;):/</:?/42'?+8+*3':+8/'29B ')/,/).+3  +)  42/4+4</:+* 1X SR_4!'K).H JD GV T`I`"& (   

8

@ 

!' UPEYN5 "" %53+49=++1   

8@?'$']0=:WC 1X SR(%M< ?'$']0/aWC
#"./351'='5.21+$+*'"&;451/".'4454A/-.,/+2*96/44+3':/)9:':+/4"   97;'8+2'::/)+
,+8853'-4+: >'): */'-54'2/@':/54 9:;*? '4* 8+2':+* 4+= 56+495;8)+ 6')1'-+ !" B 4:+84':/54'2 54,+8+4)+ 54
!;'4:;3/7;/*8?9:'29  !    '? 42/4+659:+8#"./351'='A!;'4:;396/4952<+84+'89':;8':/54!"'4*/:9'662/)':/54:5./-.2?,8;9:8':+*96/49?9:+39B
'$'LO*f\43-UP !&' 

8 @  ?'$'=:WC#"./351'='A$4(/'9+*4;3+8/)'29:;*?5,:.+7;'4:;396/42/7;/*3':+8/'2'8B":':/9:/)'26.?9/)99+3/4'8
$4/<+89/:?5,#51?5  5<42/4+
 # "./351'=' A!;'4:;3 96/4 952<+8 4+'8 9':;8':/54 !" '4* /:9 '662/)':/54 :5 96/4 4+3':/) 9:;*?B;0/35:5
/@;9./3''(9+3/4'89'1'$4/<  ;- 42/4+

5)4



 1 b E. Minamitani, T. Shiga, M. Kashiwagi, I. Obayashi, “Relationship between local coordinates and thermal
conductivity in amorphous carbon”, J. Vac. Soc. Technol. A, 40, 033408 (2022)
2bE. Minamitani, “Ab initio analysis for the initial process of Joule heating in semiconductors”, Phys. Rev. B 108, 085282(2021)
3. T. Ichikawa, E. Minamitani, Y. Shigesato, M. Kashiwagi, T. Shiga, “How mass disorder affects heat conduction in
ternary amorphous alloys” AIP Adv. 11, 065026 (2021)
4. H. Ueda, S. Yunoki and T. Shimokawa, “Quantum spin solver near saturation: QS3”, Comp. Phys. Commun. 277,
108369 (2022).

- 475 -

ᶵ⬟ᛶ㛤ẆศᏊᮦᩱࡢᵓ㐀㸫≀ᛶ㸫㟁Ꮚ≧ែ┦㛵ࡢゎ᫂(OXFLGDWLRQRIUHODWLRQVKLSEHWZHHQVWUXFWXUHSURSHUW\HOHFWURQLFVWDWHV
LQIXQFWLRQDORSHQVKHOOPROHFXODUPDWHULDOV‫ⲡۑ‬ᮏ ဴ㑻ࠊᯇᒸ ுኴࠊ୰㈅ ᲈ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗ᭷ᶵࣛࢪ࢝ࣝࡸ☢ᛶ㔠ᒓ㘒య࡞࡝㛤Ẇ㟁Ꮚ≧ែࢆ᭷ࡍࡿศᏊࡣࠊ୙ᑐ㟁Ꮚ࡟ᇶ࡙ࡃ⯆࿡῝࠸㟁Ẽ≉ᛶࠊ☢

Ẽ≉ᛶࠊⓎග≉ᛶࢆ♧ࡍࠋᡃࠎࡣⓎගࣛࢪ࢝ࣝ࡞ࡽࡧ࡟Ⓨගࣛࢪ࢝ࣝ࡜㔠ᒓ࢖࢜ࣥ࠿ࡽᵓᡂࡉࢀࡿ㓄఩㧗ศᏊࢆ㛤Ⓨࡋࠊࡑࡢග≀ᛶࠊ☢Ẽ≀ᛶࠊ࡞ࡽࡧࡢ୧⪅ࡢ┦㛵ᶵ⬟ࡢ㛤ᣅ࡜ཎ⌮ゎ᫂ࢆ㐍ࡵ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ
DFT ἲ࡟ᇶ࡙ࡃ㟁Ꮚ≧ែィ⟬࡟ࡼࡾࠊ(A) ᭷ᶵࣛࢪ࢝ࣝ PyBTM ࡜ Ni ࠾ࡼࡧ Co ࠿ࡽ࡞ࡿ࣊ࢸࣟࢫࣆࣥ㔠ᒓ㘒య࡟࠾ࡅࡿ☢Ẽ┦஫స⏝ࢆゎ᫂ࡍࡿࡇ࡜ࠊ࡞ࡽࡧ࡟(B) ୕ゅᙧᆺࣛࢪ࢝ࣝ㓄఩Ꮚ trisPyM ࡜ Ni ࠿ࡽ࡞ࡿ஧
ḟඖ㓄఩㧗ศᏊࡢࣂࣥࢻᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࠊࡢ㸰Ⅼࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ(A)࡟㛵ࡍࡿィ⟬࡟ࡣ Gaussian 16, Revision C.01 ࢆ౑⏝ࡋࡓࠋྛࠎࡢศᏊࡢཎᏊᗙᶆࡣࠊ༢⤖ᬗ㹖⥺ᅇᢡᐇ㦂࡟ᇶ࡙ࡃᵓ㐀ゎᯒ࠿ࡽᚓࡽࢀࡓศᏊᵓ㐀ࢆඖ࡜ࡋࡓࠋࣛࢪ࢝ࣝ࡜㔠ᒓ࢖࢜ࣥ㛫࡟ാࡃ஺᥮┦஫స⏝ᐃᩘࡣ
Broken-symmetry ἲ࡟ࡼࡾ⟬ฟࡋࡓ[1]ࠋ(B)࡟㛵ࡍࡿィ⟬࡟ࡣ Quantum Espresso 6.5 ࢆ౑⏝ࡋࡓࠋ஺᥮࣭┦㛵ỗ㛵ᩘ࡟ࡣ GGA-PBE ࢆࠊᨃ࣏ࢸࣥࢩࣕࣝ࡟ࡣ࢘ࣝࢺࣛࢯࣇࢺᆺࡢࡶࡢࢆࡑࢀࡒࢀ⏝࠸ࡓࠋ┠ⓗ࡜ࡍࡿ≀㉁ࡢ
ཎᏊᗙᶆࡣ༢⤖ᬗ㹖⥺ᅇᢡᐇ㦂࡟ᇶ࡙ࡃᵓ㐀ゎᯒ࠿ࡽᚓࡽࢀࡓࡶࡢࢆཧ↷ࡋࡓࠋࣂࣥࢻᵓ㐀ィ⟬ࠊ≧ែᐦᗘィ⟬ࠊࢫࣆࣥᐦᗘィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ(A) ᭷ᶵࣛࢪ࢝ࣝ PyBTM ࡜ Ni ࠾ࡼࡧ Co ࠿ࡽ࡞ࡿ࣊ࢸࣟࢫࣆࣥ㔠ᒓ㘒య࡟࠾ࡅࡿ☢Ẽ┦஫స⏝ᅗ 1a ࡟♧ࡍ㔠ᒓ㘒య[M(hfac)2(PyBTM)2] (M= NiII, CoII; hfac = hexafluoroacetylacetonato, PyBTM= (3,5-dichloro-

4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical; ᅗ 1a)ࡢ㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋ[NiII(hfac)2(PyBTM)2]ࡢᇶᗏ≧ែࡣ 5 㔜㡯࡛࠶ࡿ࡜⟬ฟࡉࢀࡓࠋࢫࣆࣥᐦᗘศᕸࢆᅗ 1b ࡟♧ࡍࠋPyBTM ࡢ୰ᚰⅣ⣲ཎᏊୖࡢࢫࣆࣥᐦᗘ࡜
NiII ࢖࢜ࣥୖࡢࢫࣆࣥᐦᗘࡣྠ఩┦࡛࠶ࡾࠊࣛࢪ࢝ࣝࡢࢫࣆࣥ࡜ NiII ࡢࢫࣆࣥࡀᙉ☢ᛶⓗࢫࣆࣥ㓄⨨ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ⟬ฟࡉࢀࡓࣛࢪ࢝ࣝ㸫NiII 㛫஺᥮┦஫స⏝ᐃᩘ JNi-R ࡣࠊ஧✀㢮ࡢ⤖ᬗᏛⓗ࡟㠀➼౯࡞[NiII(hfac)2(PyBTM)2]࡟ᑐࡋࠊࡑࢀࡒࢀ JNi–R/kB = 27.9 K ࡜ 29.8 K ࡛࠶ࡾࠊ☢໬⋡ᐃ࠿ࡽぢ✚ࡶࡽࢀࡓ್

II

㸦21.8 K㸧ࢆ෌⌧ࡋࡓࠋྠᵝ࡟ࠊ[Co (hfac)2(PyBTM)2]ࡢᇶᗏ≧ែࡣ 6 㔜㡯࡛࠶ࡿ࡜⟬ฟࡉࢀࡓࠋࢫࣆࣥᐦᗘ
ࢆᅗ 1c ࡟♧ࡍࠋ஧✀㢮ࡢ⤖ᬗᏛⓗ࡟㠀➼౯࡞[CoII(hfac)2(PyBTM)2]࡟ᑐࡋࠊJCo–R/kB ࡣࡑࢀࡒࢀ 5.4 K ࡜ 4.8
K ࡜⟬ฟࡉࢀࠊࣛࢪ࢝ࣝࡢࢫࣆࣥ࡜ CoII ࡢࢫࣆࣥࡢ㛫࡟ᙉ☢ᛶⓗ࡞☢Ẽ┦஫స⏝ࡀാ࠸࡚ࡿ࡜࠸࠺⤖ᯝࡀᚓࡽࢀࡓࠋ⟬ฟࡉࢀࡓ JCo–R/kB ್ࡣᐇ㦂⤖ᯝ㸦JCo–R/kB = 11.8 K㸧ࢆࡼࡃ෌⌧ࡋࡓࠋ ࡇࢀࡽࡢ⤖ᯝࡣࠊࡇࡇ࡛⏝࠸࡚࠸ࡿィ⟬ᡭἲࡀࠊᮏ≀㉁⣔ࡢ☢Ẽ≀ᛶࢆᐃ㔞࣭ᐃᛶⓗ࡟෌⌧࣭ண᭷ຊ࡞᪉ἲ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ(B) ୕ゅᙧᆺࣛࢪ࢝ࣝ㓄఩Ꮚ trisPyM ࡜ Ni ࠿ࡽ࡞ࡿ஧ḟඖ㓄఩㧗ศᏊࡢ㟁Ꮚ≧ែ

- 476 -

ࡋ࠼ࡿᩥ⊩࡟グ㍕ࡢள㖄㘒యࡢ㢮⦕య࡜ࡋ࡚ࠊtrisPyM ࡜ Ni ࢖࢜ࣥ࠿ࡽ࡞ࡿ஧ḟඖ㓄఩㓄఩㧗ศᏊࡢࣂࣥࢻᵓ㐀࠾ࡼࡧࢫࣆࣥᐦᗘศᕸࢆィ⟬ࡋࡓࠋィ⟬࡟࠶ࡓࡾᙉ☢ᛶ≧ែࢆ௬ᐃࡋࡓࠋࣂࣥࢻィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ㔠ᒓⓗ࡞ࣂࣥࢻᵓ㐀ࡀ⟬ฟࡉࢀࡓࠋ⌧ᐇࡢ≀㉁ࡣ⤯⦕య࡛࠶ࡿࡓࡵࠊ≀㉁ࡢࣂࣥࢻᵓ㐀ࢆṇࡋࡃィ⟬࡛ࡁ࡚࠸࡞
࠸ྍ⬟ᛶࡀ࠶ࡿࠋ௒ᚋࡣࡼࡾᮏ≀㉁⣔࡟㐺ࡋࡓィ⟬ᡭἲ࣭᮲௳ࢆ᥈⣴ࡍࡿࠋ

ᅗ 1. (a) [M(hfac)2(PyBTM)2]ࡢ໬Ꮫᵓ㐀ࠋ(b) M = NiII ࡢࢫࣆࣥᐦᗘศᕸࠋ(c) M = CoII ࡢࢫࣆࣥᐦᗘศᕸࠋ(b), (c)࡛ࡣ⤖ᬗᏛⓗ࡟㠀➼౯࡞஧ศᏊࡢ࠺ࡕࡢ୍ࡘࢆ♧ࡋ࡚࠸ࡿࠋ

ཧ⪃ᩥ⊩[1] Ryota Matsuoka, Tatsuhiro Yoshimoto, Yasutaka Kitagawa, and Tetsuro Kusamoto "Structural and Magnetic Studies
on Nickel(II) and Cobalt(II) Complexes with Polychlorinated Diphenyl(4-pyridyl)methyl Radical Ligands" Molecules
2021, 26, 5596.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ࡇࡇ࡛ᚓࡽࢀࡓᡂᯝࡣࠊ௒ᚋࠊ᪥ᮏ໬Ꮫ఍ᖺ఍ࠊ㘒య໬Ꮫ఍ウㄽ఍ࠊICCC,

ACCC ࡞࡝ࡢᅜෆእࡢᏛ఍࡟

࡚Ⓨ⾲ࡍࡿணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) Tetsuro Kusamoto, Chie Ohde, Shiori Sugiura, Satoshi Yamashita, Ryota Matsuoka, Taichi Terashima, Yasuhiro
Nakazawa, Hiroshi Nishihara, and Shinya Uji "An Organic Quantum Spin Liquid with Triangular Lattice: Spinon
Fermi Surface and Scaling Behavior" Bull. Chem. Soc. Jpn. 2022, 95, 306-313.
(2) Yohei Hattori, Ryota Kitajima, Ryota Matsuoka, Tetsuro Kusamoto, Hiroshi Nishihara, and Kingo Uchida"Amplification of luminescence of stable radicals by coordination to NHC-gold(I) complex" Chem. Commun. 2022,
58, 2560-2563.
(3) ‫ۻ‬Ryota Matsuoka, Tatsuhiro Yoshimoto, Yasutaka Kitagawa, and Tetsuro Kusamoto "Structural and Magnetic
Studies on Nickel(II) and Cobalt(II) Complexes with Polychlorinated Diphenyl(4-pyridyl)methyl Radical Ligands"
Molecules 2021, 26, 5596.
(4) Tetsuro Kusamoto and Shun Kimura "Photostable Luminescent Triarylmethyl Radicals and Their Metal Complexes:
Photofunctions Unique to Open-shell Electronic States" Chem. Lett. 2021, 50, 1445-1459.
(5) Ryota Matsuoka, Shojiro Kimura, and Tetsuro Kusamoto "Solid-State Room-Temperature Near-Infrared
Photoluminescence of a Stable Organic Radical" ChemPhotoChem 2021, 5, 669-673.

- 477 -

3

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(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*
ChemRxiv 2022, DOI: 10.26434/chemrxiv-2022-jqvv2(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*
ChemRxiv 2021, DOI: 10.33774/chemrxiv-2021-7kd63(3)  Synthesis of a Möbius carbon nanobelt
Yasutomo Segawa,* Tsugunori Watanabe, Kotono Yamanoue, Motonobu Kuwayama, Kosuke Watanabe,
Kenichiro Itami*
ChemRxiv. 2021, DOI: 10.26434/chemrxiv-2021-w09lc(4) Photochromic Carbazolyl-Imidazolyl Radical Complex
Yasuki Kawanishi, Yasutomo Segawa, Katsuya Mutoh, Jiro Abe,* Yoichi Kobayashi*
Chem. Commun. 2022, 58, 4997-5000. DOI: 10.1039/D2CC01196D(5) Emerging Disordered Layered-Herringbone Phase in Organic Semiconductors Unveiled by Electron
Crystallography
Satoru Inoue,* Kiyoshi Nikaido, Toshiki Higashino, Shunto Arai, Mutsuo Tanaka, Reiji Kumai, Seiji
Tsuzuki, Sachio Horiuchi, Haruki Sugiyama, Yasutomo Segawa, Kiyofumi Takaba, Saori MakiYonekura, Koji Yonekura, Tatsuo Hasegawa*Chem. Mater. 2022, 34, 72-83. DOI: 10.1021/acs.chemmater.1c02793(6) Stepwise Generation of Mono-, Di-, and Triply-Reduced Warped Nanographenes: Charge-Dependent
Aromaticity, Surface Nonequivalence, Swing Distortion and Metal Binding Sites
Sarah N. Spisak, Zheng Zhou, Shuyang Liu, Qi Xu, Zheng Wei, Kenta Kato, Yasutomo Segawa,
Kenichiro Itami, Andrey Yu. Rogachev, Marina A. Petrukhina*
Angew. Chem. Int. Ed. 2021, 60, 25445-25453. DOI: 10.1002/anie.202110748- 481 -

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ᚤᑠ⟶ࡣ Į ࠾ࡼࡧ ȕ ࢳ࣮ࣗࣈࣜࣥࡢ஧㔞య⺮ⓑ㉁㸦abTUB㸧࠿ࡽᵓᡂࡉࢀࠊ୰✵ࡢ⟶ᵓ㐀ࢆᵓ⠏ࡋ࡚࠸ࡿ࠙ᅗ 1ࠚ
ࠋ

Ѝ Ў

ඏঘ؇

ʤ*'3݃߻‫ܗ‬ʥᚤᑠ⟶ࡢᙧᡂ࡟ࡣ abTUB ࡀᚤᑠ⟶ࡢ㔜ྜᮎ➃㸦㸩➃㸧࡟⤖ྜࡍЍ ЎαβοϣʖϔϨϱ್ྖର
ʤ*73݃߻‫ܗ‬ʥࡿࡇ࡜࡛㉳ࡇࡾࠊᚤᑠ⟶ࡢゎయ࡟ࡣ abTUB ࡀᚤᑠ⟶ࡢ⬺㔜ྜᮎ➃ᅗ 1.

㸦㸫➃㸧࠿ࡽゎ㞳ࡍࡿࡇ࡜࡛㉳ࡇࡿࠋ㸩➃࡟㔜ྜࡍࡿ abTUB ࡣᚤᑠ⟶ᵓ㐀ࡢᶍᘧᅗ

GTP ࡜⤖ྜࡋ࡚࠸ࡿ㸦GTP ⤖ྜᆺ㸧ࠋGTP ⤖ྜᆺ abTUB ࡣ㔜ྜᚋࠊᚤᑠ⟶ෆ࡛ GDP ࡟ຍỈศゎࡉࢀ࡚ GDP ⤖ྜᆺ࡜࡞ࡾࠊ㸫➃࠿ࡽゎ㞳ࡍࡿࠋࡇࡢ⤖ྜࢾࢡࣞ࢜ࢳࢻ≧ែ࡟ࡼࡗ࡚ᚤᑠ⟶ࡢᙧᡂ࠾ࡼࡧゎయࡢไᚚࡀ࡞ࡉࢀ࡚࠸ࡿࠋࡉࡽ࡟ࠊᚤᑠ⟶ࡢᙧᡂࡸゎయࡣ」ᩘࡢᚤᑠ⟶⤖ྜ
⺮ⓑ㉁࡟ࡼࡗ࡚ㄪ⠇ࡉࢀ࡚࠸ࡿࠋᚤᑠ⟶ࡢᙧᡂ࠾ࡼࡧゎయࠊᵓ㐀Ᏻᐃᛶࡢไᚚᶵᵓࢆゎ᫂ࡍࡿࡇ࡜࡛⏕࿨⌧㇟ࡢศᏊㄽⓗ࡞⌮ゎ࡟ࡘ࡞ࡀࡿࠋ
ᚤᑠ⟶⤖ྜ⺮ⓑ㉁ࡢࢱ࢘ࡣᚤᑠ⟶ࡢ㔜ྜಁ㐍࠾ࡼࡧᏳᐃ໬࡟ാ࠸࡚࠸ࡿࠋ≉࡟⚄⤒1ΦΫλϱ ϕϫϨϱϨρο྘Ү ᚤᑠ⟶⤖ྜ䝸䝢䞊䝖
5

5

5

5

441

㍈⣴ෆ࡟Ꮡᅾࡋ࡚࠾ࡾࠊࢱ࢘ࡢ␗ᖖࡣ⚄⤒ᅗ 2.

ኚᛶ࡟῝ࡃ㛵୚ࡋ࡚࠸ࡿࠋࢱ࢘ࡣ඲㛗 441

ࢱ࢘㓄ิࡢᶍᘧᅗ

࢔࣑ࣀ㓟࠿ࡽ࡞ࡾࠊC ᮎ➃ഃ࡟㐃⥆ࡋࡓᚤᑠ⟶⤖ྜࣜࣆ࣮ࢺ㸦R1㹼R4㸧ࢆྵࢇ࡛࠸ࡿ࠙ᅗ 2ࠚ
ࠋR1㹼R4 ࡢᚤᑠ⟶⤖ྜ㒊఩࡟ࡣṇ࡟Ⲵ㟁ࡋࡓሷᇶ࢔࣑ࣀ㓟ࢆከࡃྵࡴࠋࢱ࢘ࡢ࢔࢖ࢯࣇ࢛࣮࣒࡟ࡣࠊR1㹼R4 ࡍ࡭࡚ࢆྵࡴ
4 ࣜࣆ࣮ࢺᆺ㸦Tau4R㸧࠾ࡼࡧ 3 ࡘ㸦R1ࠊR3 ࡜ R4㸧ࢆྵࡴ 3 ࣜࣆ࣮ࢺᆺ㸦Tau3R㸧ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡲࡓࠊ
ࢱ࢘ࡣኳ↛ኚᛶ⺮ⓑ㉁࡛࠶ࡾࠊࡑࡢ❧యᵓ㐀ࡣ㐟㞳≧ែ࡟࠾࠸୍࡚ᐃࡢᵓ㐀࡟ᢡࡾࡓࡓࡲࢀࡿࡇ࡜࡞ࡃᏑᅾ
ࡋ࡚࠸ࡿࠋࢱ࢘࡜ᚤᑠ⟶ࡢ⤖ྜ≧ែ࡟࠾࠸࡚ࠊࢱ࢘ࡢ R2 ࡀᴟప㟁Ꮚ㢧ᚤ㙾࡟ࡼࡗ࡚ᵓ㐀Ỵᐃࡉࢀ࡚࠸ࡿ㸦PDB ID: 6CVN㸧
ࠋࡇࡇ࡛ᚤᑠ⟶ࡢ⏕≀✀࡟ࣈࢱࡀ⏝࠸ࡽࢀࠊࢱ࢘࡟ࡣࣄࢺࡢࡶࡢࡀ⏝࠸ࡽࢀ࡚࠸ࡿࠋ
abTUB ࡢྛࢳ࣮ࣗࣈࣜࣥ C ᮎ➃㡿ᇦ㸦C-Terminal Tail㸸CTT㸧ࡣኳ↛ኚᛶ㡿ᇦ࡛࠶ࡾࠊ୍ᐃࡢ❧యᵓ㐀࡟ࡣᢡࡾࡓࡓࡲࢀ࡚࠸࡞࠸ࠋĮ ࢳ࣮ࣗࣈࣜࣥ C ᮎ➃㡿ᇦ㸦aCTT㸧࠾ࡼࡧ ȕ ࢳ࣮ࣗࣈࣜࣥ C ᮎ➃㡿ᇦ㸦bCTT㸧ࡣ୧⪅࡜ࡶ㈇࡟Ⲵ㟁ࡋࡓ㓟ᛶ࢔࣑ࣀ㓟࡟ᐩࢇ࡛࠾ࡾࠊbCTT ࡢ᪉ࡀ aCTT ࡼࡾࡶ㛗࠸ࠋCTT ࡣᚤᑠ⟶ࡢṇᖖ࡞୰- 484 -

✵ࡢ⟶ᵓ㐀ᵓ⠏࡟ᚲせ࡞㒊఩࡛࠶ࡾࠊࡲࡓࠊᚤᑠ⟶⤖ྜ⺮ⓑ㉁࡜ࡢ┦஫స⏝㒊఩࡜ࡋ࡚▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿
ࡋ࡞ࡀࡽࠊCTT ࠾ࡼࡧࢱ࢘ࡣ࡜ࡶ࡟ኳ↛ኚᛶ㡿ᇦ࡛࠶ࡿࡓࡵࠊࡑࢀࡽࡢ┦஫స⏝࡟ࡘ࠸࡚❧యᵓ㐀ⓗ࡞ほⅬ࠿ࡽ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᡃࠎࡣ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐺⏝ࡍࡿࡇ࡜࡛ࠊࢱ࢘࡜
ࣄࢺᚤᑠ⟶࡟࠾ࡅࡿኳ↛ኚᛶ㡿ᇦ㛫ࡢศᏊ㛫┦஫స⏝ࢆゎᯒࡋࠊࢱ࢘⤖ྜ࡟క࠺ᚤᑠ⟶ᵓ㐀ࡢᏳᐃ໬ᶵᵓࡢ
ゎ᫂ࢆࡵࡊࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲᚤᑠ⟶⤖ྜ⺮ⓑ㉁ࢱ࢘ࡢᚤᑠ⟶Ᏻᐃ໬ᶵᵓࢆゎ᫂ࡍࡿࡓࡵࠊࢱ࢘Ꮡᅾୗ࠾ࡼࡧ㠀Ꮡᅾୗ࡟࠾ࡅࡿィ⟬⣔ࢆࣔࢹࣜࣥࢢࡋࡓࠋࡲࡓࠊĮȕ ࢳ࣮ࣗࣈࣜࣥ஧㔞య㸦abTUB㸧࠾ࡼࡧᚤᑠ⟶ࣔࢹࣝࢆࣔࢹࣜࣥࢢࡋࠊࡑࢀࡽ࡜ࢱ
࢘ࡢ⤖ྜ࡟ࡼࡿᵓ㐀ኚ໬ࢆゎᯒࡋࡓࠋᮏ◊✲࡟࠾࠸࡚ࠊabTUB ࡣࣄࢺ⬻࡛Ꮡᅾ๭ྜࡢ㧗࠸ Į1A ࢳ࣮ࣗࣈࣜࣥ
࡜ ȕ3 ࢳ࣮ࣗࣈࣜࣥࡢ஧㔞యࢆ⏝࠸ࡓࠋᚤᑠ⟶ࣔࢹࣝࡣ abTUB ࡀ⦪ 3 ࡘᶓ 3 ࡘ࡟㓄⨨ࡉࢀࡓ఍ྜయ㸦PDB ID:
5JCO㸧ࢆඖ࡟సᡂࡋࡓࠋࢳ࣮ࣗࣈࣜࣥ C ᮎ➃㡿ᇦ㸦CTT㸧ࢆྵࡴኳ↛ኚᛶ㡿ᇦࡣ⺮ⓑ㉁❧యᵓ㐀ࣔࢹࣜࣥࢢ
ࢯࣇࢺ Modeller ࢆ⏝࠸࡚ᵓ⠏ࡋࡓࠋᮏ◊✲࡛ࡣ 6 ࡘࡢィ⟬⣔ࢆ⏝ពࡋࡓࠋ
GTP ⤖ྜᆺ abTUBࠊGDP ⤖ྜᆺ abTUBࠊ
GTP ⤖ྜᆺ abTUB ࡜ࢱ࢘ R2 」ྜయࠊGDP

bCTT
Tau3R

⤖ྜᆺ abTUB ࡜ࢱ࢘ R2 」ྜయࠊGTP ⤖α1A
aCTT αβ3βྜᆺᚤᑠ⟶ࣔࢹࣝࠊGTP ⤖ྜᆺᚤᑠ⟶ࣔࢹ
ࣝ࡜ Tau3R 」ྜయ࡛࠶ࡿࠋGTP ⤖ྜᆺᚤᑠ⟶ࣔࢹࣝ࡜ Tau3R 」ྜయࡢึᮇᵓ㐀ࢆ
࠙ᅗ 3ࠚ࡟♧ࡍࠋࢱ࢘ࡢึᮇ㓄⨨ࡣᴟప㟁Ꮚ㢧ᚤ㙾࡟ࡼࡗ࡚Ỵᐃࡉࢀࡓᵓ㐀㸦PDBॐ๏޴

ID: 6CVNࠊ6CVJ㸧࡟ྜࢃࡏࡓࠋỈศᏊ࡜࢖࢜ࣥࢆ㓄⨨ࡋࠊึᮇᵓ㐀࡜ࡋࡓࠋᅗ 3.

6 ࡘࡢィ⟬⣔࡟ᑐࡋ࡚ࠊึᮇᵓ㐀ࡢ࢚ࢿᚤᑠ⟶ࣔࢹࣝ࡜ Tau3R 」ྜయ

ࣝࢠ࣮ᴟᑠ໬ィ⟬ࡢᚋࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋ࢚ࢿࣝࢠ࣮ᴟᑠ໬࠾ࡼࡧศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥࡢࢯࣇࢺ࢙࢘࢔ࡣ AMBER18 ࠾ࡼࡧ AMBER20 ࢆ⏝࠸ࡓࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣ 5 ẁ㝵࡟ศࡅ࡚ᐇ⾜ࡋࡓࠋ1 ẁ㝵┠ࡣ 10 ࢼࣀ⛊㸦ns㸧㛫࠿ࡅ࡚ 1K ࠿ࡽ 300K ࡬᪼ࠊ2 ẁ㝵┠ࡣ 10 ns 㛫 300K ࡢᗘᖹ⾮໬ࠊ3 ẁ㝵┠ࡣ 10 ns 㛫࠿ࡅ୍࡚ᐃᅽຊ 1 bar ୗ࡟࠾࠸࡚య✚⦆࿴ࠊ4 ẁ㝵┠ࡣ CTT 㡿ᇦࡢࡳ 800K
࠿ࡽ 300K ࡬ࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜࣥࢢࠊ5 ẁ㝵┠࡟ 500 ns 㛫࠿ࡅ࡚ࢧࣥࣉࣜࣥࢢࢆᐇ᪋ࡋࡓࠋࡇࡢ୍㐃ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆࠊึᮇ㏿ᗘࢆኚ᭦ࡋ࡚ࠊ12 ᅇ⧞ࡾ㏉ࡋ࡚ィ 6 ࣐࢖ࢡࣟ⛊ࡢࢧࣥࣉࣜࣥࢢࢆ
⾜࡞ࡗࡓࠋࡇࡇ࡛ࢧࣥࣉࣜࣥࢢࡉࢀࡓィ⟬ᵓ㐀ࢆḟࡢゎᯒ࡟⏝࠸ࡓࠋゎᯒࡣ AmberTools ࠾ࡼࡧ⮬సࣉࣟࢢ࣒ࣛ࡟࡚ᐇ⾜ࡋࡓࠋゎᯒෆᐜࡣࠊィ⟬ᵓ㐀࠿ࡽ CTT ᵓ㐀ࡢ✵㛫ᐦᗘศᕸࢆồࡵࡓࠋࢱ࢘ࡢᏑᅾ࡟ࡼࡗ࡚ CTT ᵓ㐀ศᕸࡀ࡝ࡢࡼ࠺࡞ᙳ㡪ࢆཷࡅࡿ࠿ࢆㄪ࡭ࡓࠋࡲࡓࠊᚤᑠ⟶ࣔࢹࣝࡢᏳᐃᛶࢆㄪ࡭ࡿࡓࡵࠊ㞄᥋ࡍࡿ 3 ࡘࡢ abTUB 㔜ᚰࡀ࡞ࡍゅᗘࢆィ⟬ࡋࡓࠋࡇࡢゅᗘࡢ᫬㛫ኚ໬ࢆㄪ࡭ࠊ
ࢱ࢘࡟ࡼࡿ abTUB ✵㛫㓄⨨࡬ࡢᙳ㡪ࢆㄪ࡭ࡓࠋ

- 485 -

◊✲ᡂᯝabTUB ࡟࠾ࡅࡿࢱ࢘ R2 ⤖ྜࡢᙳ㡪GDP ⤖ྜᆺ abTUB ࠾ࡼࡧ GTP ⤖ྜᆺ abTUB ࡟ࡘ࠸࡚ࠊࢱ࢘
R2 ⤖ྜ࡟ࡼࡿ CTT ࡢᵓ㐀ศᕸኚ໬ࢆゎᯒࡋࡓࠋGTP ⤖ྜᆺνΤΤR2

abTUB ࡢ bCTT ᵓ㐀ศᕸࡀࢱ࢘ R2 ⤖ྜ࡟ࡼࡿᙳ㡪ࢆཷࡅࡸࡍ࠸ࡇ࡜ࡀぢࡽࢀࡓ࠙ᅗ 4ࠚࠋࢱ࢘ R2 ⤖ྜ㒊఩ࡢ᪉࡬ bCTT ࡀᘬࡁ

bCTT‫ؔۯ‬෾ාᐤࡏࡽࢀࡿᵝᏊࡀ☜ㄆࡉࢀࡓࠋGTP ⤖ྜᆺࡢ᪉ࡀ GDP ⤖ྜᆺࡼ

νΤR2ໃ͢
νΤR2݃߻য়ସ

ࡾࡶࢱ࢘ R2 ⤖ྜࡢᙳ㡪ࡀ኱ࡁ࠸⌮⏤࡜ࡋ࡚ࠊࢱ࢘ R2 ࡢṇ㟁Ⲵ
࡜ bCTT ࡢ㈇㟁Ⲵࡢ㟼㟁ⓗᘬຊ࡟ຍ࠼࡚ GTP ࡜ bCTT ࡢ㟼㟁ⓗ

ᅗ 4.

GTP ⤖ྜᆺ abTUB ࡟࠾ࡅࡿࢱ࢘ R2 ⤖ྜ࡜ bCTT ᵓ㐀ศᕸ

࡞཯Ⓨࡀㄏᑟࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡿࠋ

ᚤᑠ⟶ࣔࢹࣝ࡟࠾ࡅࡿ Tau3R ⤖ྜࡢᙳ㡪ᚤᑠ⟶ࣔࢹࣝࡣ GTP ⤖ྜᆺ abTUB ࢆ⦪ 3 ࡘᶓ 3 ࡘ࡟㓄⨨ࡋࡓࠋTau3R ࡣ⦪᪉ྥ࡟୍ࡘࡎࡘ㓄⨨ࡋࠊ3 ࡘࡢ
Tau3R ࢆᚤᑠ⟶ࣔࢹࣝୖ࡟⤖ྜࡉࡏࡓ≧ែࢆศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࡚ゎᯒࡋࡓࠋTau3R ࡢ⤖ྜ࡟ࡼࡗ࡚ࠊbCTT ᵓ㐀ศᕸࡀ㸫➃ഃ࡬ᘬࡁᐤࡏࡽࢀࠊ㸩➃ഃࡢ bCTT ᵓ㐀ศᕸࡀῶᑡࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ࠙ᅗ
5ࠚ
ࠋCTT ࡣᚤᑠ⟶㔜ྜ࡟୙฼࡟ാࡃࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࢱ࢘ࡢ⤖ྜ࡟ࡼࡗ࡚ࠊ㸩➃ࡢ CTT ࡀᘬࡁࡣࡀࡉࢀ
ࡿࡇ࡜ࡀ㔜ྜಁ㐍࡟ᐤ୚ࡋ࡚࠸ࡿ♧၀ࡀᚓࡽࢀࡓࠋ
*73‫ܗ‬ඏঘ؇Ϡυϩʤ7DX5ໃ͢ʥ
aCTT*73‫ܗ‬ඏঘ؇Ϡυϩ7DX5݃߻য়ସ

bCTT

aCTT

ʷ୼

bCTT

ʶ୼ ʷ୼

ᅗ 5.

ʶ୼

ᚤᑠ⟶ࣔࢹࣝ࡟࠾ࡅࡿ Tau3R ⤖ྜ࡟క࠺ CTT ᵓ㐀ศᕸ⦪᪉ྥ࠾ࡼࡧᶓ᪉ྥ࡟㞄᥋ࡍࡿ abTUB ࡀ࡞ࡍゅᗘࢆゎᯒࡋࡓࠋTau3R ⤖ྜ࡟ࡼࡗ࡚ᶓ᪉ྥࡢゅᗘࡀ⥔ᣢࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓ࠙ᅗ 6ࠚࠋ⦪᪉ྥࡢゅᗘࡣ Tau3R ᭷↓࡟ࡼࡿ኱ࡁ࡞ᕪ␗ࡣࡳࡽࢀ࡞࠿ࡗࡓࠋࡼࡗ࡚ࠊTau3R*73‫ܗ‬ඏঘ؇Ϡυϩʤ7DX5ໃ͢ʥ

*73‫ܗ‬ඏঘ؇Ϡυϩ7DX5݃߻য়ସ

ॐ๏޴

ॐ๏޴

ֱౕʤ˅ʥ

ֱౕʤ˅ʥ

ࡀ⤖ྜࡍࡿࡇ࡜࡛ᚤᑠ⟶ࡣᶓ᪉ྥࡢゅᗘࢆ⥔ᣢ࡛ࡁࠊᚤᑠ⟶ᵓ㐀ࡢᏳᐃ໬࡟ാ࠸࡚࠸ࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋ

ԥ๏޴‫ؔ࣎ࢋܯ‬ʤQVʥ

ᅗ 6.

ԥ๏޴

‫ؔ࣎ࢋܯ‬ʤQVʥ

㞄᥋ࡍࡿ abTUB ࡀ࡞ࡍゅᗘࡢኚ໬- 486 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ◊✲ᡂᯝࡢ୍㒊ࡣࠊ➨ 59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍㸦2021 ᖺ 11 ᭶ 25-27 ᪥ࠊ࢜ࣥࣛ࢖ࣥ㸧࡟࡚㸰㢟ࡢ୍⯡Ⓨ⾲ࢆ⾜࡞ࡗࡓࠋ
1㸬 ‫ۻ‬₇㢟␒ྕ 3-03-1518ࠊ₇㢟㢟┠ Tubulin conformational ensemble in seam region of microtubule investigatedby all-atom molecular dynamics simulationࠊⓎ⾲⪅ྡ Koji Umezawa, Naoyuki Furuta, Takuma Todoroki
2㸬 ‫ۻ‬₇㢟␒ྕ 2-03-1612ࠊ₇㢟㢟┠ Tau Segment Affecting Conformations of Tubulin Heterodimers Including CTerminal Tails Revealed by Molecular Dynamics SimulationࠊⓎ⾲⪅ྡ Naoyuki Furuta, Takuma Todoroki, Koji
Umezawaฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ࡇࢀࡲ࡛ࡢ◊✲ᡂᯝ࡜ྜࢃࡏ࡚ࠊᮏ◊✲ㄢ㢟࡟ࡼࡗ࡚ᚓࡽࢀࡓᡂᯝࡣཎⴭㄽᩥ࡜ࡋ࡚ᑓ㛛㞧ㄅ࡟ᢞ✏ࢆணᐃࡋ࡚࠸ࡿࠋࡲࡓࠊᙜㄢ㢟ࡢྲྀ⤌⪅ࡣᮏᡂᯝࡢ୍㒊࡟࡚ಟኈᏛ఩ㄽᩥࢆ௙ୖࡆࡿࡇ࡜ࡀ࡛ࡁࡲࡋࡓࠋ㈗ࢭࣥ
ࢱ࣮ࡢィ⟬ᶵ㈨※ࢆ฼⏝ࡉࡏ࡚࠸ࡓࡔࡁࠊឤㅰ⏦ࡋୖࡆࡲࡍࠋ

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Functional and structural analysis of four dimensional MRI of the brain.
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 Koshiyama D, Fukunaga M, Okada N, Morita K, Nemoto K, Usui K, Yamamori H,Yasuda Y, Fujimoto M, Kudo N,
Azechi H, Watanabe Y, Hashimoto N, Narita H,Kusumi I, Ohi K, Shimada T, Kataoka Y, Yamamoto M, Ozaki N,
Okada G, Okamoto Y,Harada K, Matsuo K, Yamasue H, Abe O, Hashimoto R, Takahashi T, Hori T, NakatakiM,
Onitsuka T, Holleran L, Jahanshad N, van Erp TGM, Turner J, Donohoe G,Thompson PM, Kasai K, Hashimoto R;
COCORO. White matter microstructuralalterations across four major psychiatric disorders: mega-analysis study in
2937individuals. Mol Psychiatry. 25:883-895 2020 doi:10.1038/s41380-019-0553-7.
 Koshiyama D, Fukunaga M, Okada N, Morita K, Nemoto K, Yamashita F, YamamoriH, Yasuda Y, Matsumoto J,
Fujimoto M, Kudo N, Azechi H, Watanabe Y, Kasai K,Hashimoto R. Association between the superior
longitudinal fasciculus andperceptual organization and working memory: A diffusion tensor imaging
study.Neurosci Lett. 738:135349 2020 doi: 10.1016/j.neulet.2020.135349.
 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, Fisher SE, Fladby T, Frei O, Frouin V,
Fukunaga M, GareauT, Ge T, Glahn DC, Grabe HJ, Groenewold NA, Gústafsson Ó, Haavik J, Haberg AK,Hall J,
Hashimoto R, Hehir-Kwa JY, Hibar DP, Hillegers MHJ, Hoffmann P, HolleranL, Holmes AJ, Homuth G, Hottenga
JJ, Hulshoff Pol HE, Ikeda M, …, Sachdev PS, Sando SB, Schofield PR, SchorkAJ, Schumann G, Shin J,
Shumskaya E, Silva AI, Sisodiya SM, Steen VM, Stein DJ,Strike LT, Suzuki IK, Tamnes CK, Teumer A,
Thalamuthu A, Tordesillas-GutiérrezD, Uhlmann A, Ulfarsson MO, van 't Ent D, van den Bree MBM,
Vanderhaeghen P,Vassos E, Wen W, Wittfeld K, Wright MJ, Agartz I, Djurovic S, Westlye LT,Stefansson H,
Stefansson K, Jacquemont S, Thompson PM, Andreassen OA; 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.

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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
ᚋ㏙ࡢ Neuroscience ㄽᩥࠊ࠾ࡼࡧ Frontiers ㄽᩥ࡟࠾࠸࡚ࡣࠊmatlab runtime ࢆ౑⏝ࡋ࡚࠸ࡿࠋMatlab compilerࢆ⏝࠸࡚ࠊmatlab code ࢆࢥࣥࣃ࢖ࣝࡋࠊstand 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୚ᗘࢆ᥎ᐃࡍࡿࠋᮏ◊✲࡟࠾࠸࡚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⬟࣐ࢵࣉࢆసᡂࡍࡿࠋ
༢୍᫬Ⅼࡢ⬻άື࣐ࢵࣉࢆࡇࢀࡽࡢ࣐ࢵࣉ࡛ᅇᖐࡍࡿ࡜ࠊㄆ▱ᶵ⬟ࡢάືࣞ࣋ࣝ࡟㛵ࡍࡿ᫬⣔ิ᝟ሗࢆྲྀᚓ
ࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡿࠋࡇࡢ᪉ἲ࡛ྲྀᚓࡋࡓ᫬⣔ิ᝟ሗࡣࠊ่⃭ᥦ♧ࡢࢱ࢖࣑ࣥࢢࡸ⿕㦂⪅ࡢ཯ᛂ᝟ሗ࡜▩┪࡞࠸ࣃࢱ࣮࡛ࣥ࠶ࡗࡓୖ࡟ࠊಶேࡢㄆ▱⬟ຊࢆ཯ᫎࡋࡓࡶࡢ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᅗ㸯㸸ᚑ᮶ἲࡣࠊ༢୍⏬⣲ࡢάືࢆᅇᖐࡋࠊࡇࢀ
ࢆ඲࡚ࡢ⏬⣲࡛⧞ࡾ㏉ࡍࡇ࡜࡟ࡼࡾࠊ⬻ᶵ⬟࣐ࢵࣉࢆᚓࡿࠋ᪂つἲ࡛ࡣࠊ༢୍᫬Ⅼࡢάືࢆᅇᖐࡋࠊ
ࡇࢀࢆ඲࡚ࡢ᫬Ⅼ࡛⧞ࡾ㏉ࡍࡇ࡜࡟ࡼࡾࠊㄆ▱ᶵ⬟ࡢάືࣞ࣋ࣝࡢ᫬⣔ิࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋ

ࡉࡽ࡟ࠊࡇࡢᡭἲࢆⓎᒎࡉࡏࠊ⮬ᕫ➢ྕ໬ჾࢆ⏝࠸࡚ࠊㄆ▱ᶵ⬟࣐ࢵࣉࡢಶே᭱㐺໬࡜ࠊ⬻άືࡢ᫬⣔ิ᝟ሗࡢ᥎ᐃࢆྠ᫬࡟⾜࠺ゎᯒἲࡢ㛤Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋࡇࡕ
ࡽࡣࠊࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱࡀ㠀ᖖ࡟ከࡃࠊ࠿ࡘࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ㛫ࡢ┦஫౫Ꮡᛶࡀ㧗࠸ࡓࡵࠊgrid search ࡞࡝ࡢࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ᥈⣴ἲࡀ౑࠼࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊࣁ࢖ࣃ࣮ࣃ࣓࣮ࣛࢱ᥈⣴࡟࣋࢖ࢬ᭱㐺໬ࢆᑟධࡋ
ࡓ࡜ࡇࢁࠊᩘⓒ࢚࣏ࢵࢡ࡛ࠊ⤖ᯝࡢ཰᮰ࡀࡳࡽࢀࠊୖ㏙ࡢᅇᖐࢆ୺య࡟ࡋࡓゎᯒἲࡼࡾࡶ㧗࠸ goodness of fitࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢ⤖ᯝࡶㄽᩥ࡟ࡲ࡜ࡵ࡚Ⓨ⾲ࡍࡿࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋ

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3◊✲ᡂᯝᮏᖺᗘࡣࡇࢀࡲ࡛㐍ࡵ࡚࠸ࡓࣉࣟࢪ࢙ࢡࢺࡢᡂᯝࢆㄽᩥⓎ⾲ࡋࡓࠋࡲࡎࠊ኱Ꮫ㝔⏕ࡢྜྷᮏẶࢆᣦᑟࡋࠊᶵ⬟ⓗ MRI ࢹ࣮ࢱࢆゎᯒࡍࡿࡇ࡜࡛ࠊ๓㢌║❐㔝ࡢᶵ⬟࡟㛵ࡍࡿ㔜せ࡞▱ぢࢆᚓࡓࠋ๓㢌║❐㔝ࡣࠊ౯್᝟ሗฎ⌮࡟㛵㐃ࡍࡿ㔜せ࡞⬻㡿ᇦ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊࡇࡢ㡿
ᇦࡢᮏ㉁ⓗ࡞ᙺ๭࡟㛵ࡋ࡚ࡣࠊᮍࡔ᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋඛ⾜◊✲࠿ࡽࠊ๓㢌║❐㔝ࡀ⾜࠺᝟ሗฎ⌮࡜ࡋ࡚ࠊᑐ㇟ࡢྠ୍ᛶࡢㄆ▱ࠊ౯್ࡢ⟬ฟࠊ㉁ⓗ᝟ሗࡢ⾲㇟࡞࡝ࡀࠊᥦၐࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊඛ⾜◊✲ࡢ࡯࡜ࢇ࡝ࡀ୺࡟࣐࢘ࢫࢆᑐ㇟࡜ࡋࡓື≀ᐇ㦂࡟ࡼࡗ࡚⾜ࢃࢀ࡚࠾ࡾࠊࡇࢀࡽࢆᘚู࡛ࡁࡿࡼ࠺࡞」㞧࡞ᐇ㦂⣔ࡀ⤌ࡲࢀࡿࡇ࡜ࡣ࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣࠊࣄࢺࢆᑐ㇟࡟ࠊ㣗࡭≀࡟ᑐࡍࡿ୺ほⓗ౯್ࡀࠊᰤ㣴≧ែࡢኚ໬㸦✵⭡᫬ࠊࡲࡓࡣ‶⭡᫬㸧࡟ࡼࡗ࡚ࠊ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ࢆㄪ࡭ࡿ࡜࡜ࡶ࡟ࠊྠࡌ㣗࡭≀࡟ᑐࡋ࡚ࡶࠊᰤ㣴≧ែࡀኚ໬ࡍࡿࡇ࡜࡛⚄⤒⣔ࡢ཯ᛂࡀኚ໬ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ⤖ᯝࢆㄽᩥ࡟ࡲ࡜ࡵࠊNeuroscience
Research ㄅ࡟࡚ࠊⓎ⾲ࡋࡓ(Yoshimoto et al., 2022)ࠋ
ࡲࡓࠊAMED ࡢࣉࣟࢪ࢙ࢡࢺࡢ୍㒊࡜ࡋ࡚ࠊ⬻άື࡟࠾ࡅࡿࢺࢵࣉࢲ࢘ࣥ㸦㧗ḟ⬻㡿ᇦ࠿ࡽឤぬ㔝࡬ࡢಟ㣭㸧࠾ࡼࡧ࣎ࢺ࣒࢔ࢵࣉ㸦ឤぬ㔝࠿ࡽ㧗ḟ⬻㡿ᇦ࡬ࡢ᝟ሗఏ㐩㸧ಙྕࢆࠊゎᯒⓗ࡟㝖ཤࡍࡿᡭἲࡢ㛤Ⓨࢆ⾜ࡗࡓࠋࡇࡢ◊✲࡟࠾࠸࡚ࡣࠊHorikawa et al., 2016 ࡛㛤Ⓨࡉࢀࡓࠊ෗┿࠿ࡽ࢝ࢸࢦࣜࢆྠᐃࡍࡿேᕤ⚄⤒ᅇ㊰࡛⾲⌧ࡉࢀ࡚࠸ࡿ᝟ሗ࡜ࠊࣄࢺࡢどぬฎ⌮⤒㊰࡛⾲⌧ࡉࢀ࡚࠸ࡿ᝟ሗࡢᑐᛂࢆᣦᶆ࡜ࡋ࡚ࠊ⬻㡿ᇦ㛫ࡢఏ㐩ࡉࢀࡿ᝟ሗࡢෆᐜࢆ᫂ࡽ࠿࡟ࡍࡿᢏ⾡㛤Ⓨࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊ࠶ࡿ୍ࡘࡢ⬻㡿ᇦࢆ seed ࡜ࡋ࡚ࠊࡑࡇ࡜
⤖ྜࡋ࡚࠸ࡿูࡢ⬻㡿ᇦࢆ target ࡜ࡋࠊseed 㡿ᇦࡢ⬻άືࣃࢱ࣮ࣥ࠿ࡽ target 㡿ᇦࡢ⬻άືࣃࢱ࣮ࣥࢆ᥎ᐃࡍ
ࡿࠋࡇࡢࠊ᥎ᐃࡉࢀࡓࣃࢱ࣮ࣥࢆඖࡢ⬻άືࣃࢱ࣮ࣥ࠿ࡽᕪࡋᘬ࠸ࡓୖ࡛ࠊேᕤ⚄⤒ᅇ㊰࡜⬻㡿ᇦࡢᑐᛂࡢ
ᙉࡉࡢኚ໬ࢆィ⟬ࡍࡿࡇ࡜࡛ࠊ㡿ᇦ㛫࡛ඹ㏻ࡢ᝟ሗ㔞ࢆ᥎ᐃࡍࡿࠋࡇࡢᡭἲࢆ⏝࠸ࡿࡇ࡜࡛ࠊึᮇどぬ㔝࠿ࡽ㧗ḟどぬ㔝࡟㏦ࡽࢀࡿ᝟ሗࡣࠊഴࡁ࡞࡝ࡢపḟࡢどぬ≉ᚩ࡛࠶ࡿࡢ࡟ᑐࡋࠊ㧗ḟどぬ㔝࠿ࡽపḟどぬ㔝࡟
㏦ࡽࢀࡿ᝟ሗࡣࠊ࢝ࢸࢦࣜ᝟ሗ࡟㢮ఝࡋࡓ㧗ḟࡢࡼࡾᢳ㇟ⓗ࡞᝟ሗ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓࠋࡇࡢ◊✲ࡢᡂᯝࢆㄽᩥ࡟ࡲ࡜ࡵࠊFrontiers in human neuroscience ㄅ࡟ㄽᩥⓎ⾲ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃⓎ⾲ணᐃ‫ۻ‬㏆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∧ᐇ⦼˔Takaaki Yoshimoto, Shuntaro Okazaki, Motofumi Sumiya, Haruka K Takahashi, Eri Nakagawa, Takahiko Koike, Ryo
Kitada, Shiki Okamoto, Masanori Nakata, Toshihiko Yada, Hirotaka Kosaka, Norihiro Sadato, Junichi Chikazoe,“Coexistence of sensory qualities and value representations in human orbitofrontal cortex” Neuroscience Research (inpress).
˔Trung Quang Pham, Shota Nishiyama, Norihiro Sadato, Junichi Chikazoe, “Distillation of Regional Activity Reveals
Hidden Content of Neural Information in Visual Processing” Frontiers in human neuroscience, 727 (2021)

㸦ࢢࣛࣥࢺࢼࣥࣂ࣮ࡢグ㍕ࡀ₃ࢀ࡚࠾ࡾࡲࡋࡓࠋḟᅇ௨㝆ࠊ␃ព࠸ࡓࡋࡲࡍࠋ㸧- 491 -

㻞㻚䚷㻞㻜㻞㻝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
ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡣࠊᘬࡁ⥆ࡁࡇࡢ┠ⓗࢆ㐩ᡂࡍࡿࡓࡵࠊィ⟬㈨※ࡢᥦ౪ࡸィ⟬ᢏ⾡࣭ᡂᯝ࡟㛵ࡍࡿ᝟ሗ஺᥮࡞࡝ࢆ㏻ࡌ࡚ࠊィ⟬≀㉁⛉Ꮫࢆ୺࡞ࢸ࣮࣐࡜ࡍࡿ኱ᆺࣉࣟࢪ࢙ࢡࢺࡢ᥎㐍ࢆᨭ᥼ࡋ࡚࠸ࡁࡲࡍࠋ
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ࡋࡲࡍࠋࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ◊✲ㄢ㢟ྡㄢ㢟㈐௵⪅ྡ

◊✲ᢸᙜ⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᡤᒓ

YG㈗㔠ᒓࣇ࣮ࣜࡢỗ⏝ඖ⣲ࢼࣀ
ゐ፹࡟ྥࡅࡓ➨୍ཎ⌮ィ⟬

Ṋḟᚭஓ

Ṋḟᚭஓ


໭኱㝔
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YF

ࢼࣀ࣭ࣂ࢖࢜ศᏊ࡟࠾ࡅࡿ㹖⥺ㄏ㉳ゎ㞳ືຊᏛࡢᐇ᫬㛫࢖࣓࣮ࢪࣥࢢ⌮ㄽ

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Ⅼᩘ
㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 

⌮໬Ꮫ◊✲ᡤ

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≀㉁࣭ᮦᩱ
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

ᮾ኱㝔
᪂㡿ᇦ๰ᡂ⛉Ꮫ 㸭 

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

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

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ḟୡ௦஧ḟ㟁ụ࣭⇞ᩱ㟁ụ㛤Ⓨ࡟ࡼࡿ(7㠉࿨࡟ྥࡅࡓィ⟬࣭ࢹ࣮ࢱᮦᩱ⛉Ꮫ┬࢚ࢿࣝࢠ࣮ḟୡ௦༙ᑟయࢹ
ࣂ࢖ࢫ㛤Ⓨࡢࡓࡵࡢ㔞Ꮚㄽ࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥ

㤋ᒣెᑦ

ᢲᒣࠉ῟

- 492 - 㸭  㸭 



㈗㔠ᒓࣇ࣮ࣜࡢỗ⏝ඖ⣲ࢼࣀゐ፹࡟ྥࡅࡓ➨୍ཎ⌮ィ⟬Ab initio study toward abundant element nanocatalysts
with less precious metals‫ۑ‬Ṋḟ ᚭஓ㸪๓⏣ ⌮㸪ᑠᯘ ṇே㸪Lyalin Andrey㸪ᒾబ ㇦㸪㧗 ᩄ㸪ᑠ㔝 ࡺࡾᏊ㸦໭ᾏ㐨኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜⓑ㔠࡞࡝ࡢ㈗㔠ᒓࡣከࡃࡢ㔜せ࡞ሙ㠃࡛ゐ፹࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿࡀࠊ㧗౯࡛࠶ࡿࡇ࡜࡟ຍ࠼࡚⏘ฟᅜࡀ೫ࡗ࡚࠸ࡿࡓࡵࠊᣢ⥆ྍ⬟♫఍ࡢᐇ⌧࡟ྥࡅࡓᏳ౯࡛㇏ᐩ࡟Ꮡᅾࡍࡿඖ⣲࡟ࡼࡿ௦᭰ゐ፹ࡢ㛤Ⓨࡀᙉࡃᮇᚅ
ࡉࢀ࡚࠸ࡿࠋ୙άᛶ࡛࠶ࡿ㇏ᐩ㔠ᒓࡶࠊࢼࣀࢧ࢖ࢬ໬ࡸ࠶ࡿ࠸ࡣගࢆ᥼⏝ࡍࡿࡇ࡜࡛᪂ࡓ࡞ᶵ⬟ࢆⓎ⌧ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ㇏ᐩඖ⣲ࢆࢼࣀࢧ࢖ࢬ໬ࡋࡓࢡࣛࢫࢱ࣮ࡸⷧ⭷ࡢᵓ㐀࣭㟁Ꮚ≧ែ࣭Ᏻᐃᛶࠊ࠾ࡼࡧゐ፹ᶵ⬟࣭㟁ụᛶ⬟ࠊ࠶ࡿ࠸ࡣගࢆ᥼⏝ࡋࡓບ㉳≧ែ࡛ࡢ໬Ꮫ཯ᛂᶵᵓࢆゎ᫂ࡋࠊࡲࡓࡑࡢࡓࡵ
ࡢᇶ┙ᢏ⾡ࡸ⌮ㄽࢆᵓ⠏ࡍࡿࡇ࡜࡟ࡼࡾࠊᏳ౯࡛Ᏻᐃࡋࡓ౪⤥※ࢆᣢࡘỗ⏝ඖ⣲ࢆ฼⏝ࡋࡓࠊ㈗㔠ᒓ௦᭰ゐ፹㛤Ⓨ࡟ྥࡅࡓᇶ♏ⓗ࡞▱ぢ࠾ࡼࡧタィᣦ㔪ࢆ୚࠼ࡿࡇ࡜ࢆ┠ᣦࡍࠋ
௧࿴ 3 ᖺᗘࡣ≉࡟ࠊ(1)Ⅳ⣲ࢻ࣮ࣉࡋࡓභ᪉ᬗ❅໬࣍࢘⣲㸦h-BN㸧ࢆゐ፹࡜ࡋࡓศᏊ≧㓟⣲࡟ࡼࡿ㓟໬࣭࢚࣏࢟ࢩ໬཯ᛂࡢ⌮ㄽゎ᫂ࠊ(2)㔠ᒓ 4 㔞యࢡࣛࢫࢱ࣮ࡢ␗ᛶ໬཯ᛂ࡜ NO ゎ㞳཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲࡞࡝
ࢆ⾜ࡗࡓࠋ

2

◊✲᪉ἲࠊィ⟬᪉ἲ(1)࡛ࡣ㟁Ꮚ≧ែィ⟬࡟ Quantum ESPRESSO ࡢ PWSCF ࣉࣟࢢ࣒ࣛࢆ฼⏝ࡋࡓࠋỗ㛵ᩘ࡟ࡣ Wu-Cohen ࡢ

GGA ࢆ⏝࠸ࠊ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ 80 eV ࡜ࡋࡓࠋ཯ᛂ⤒㊰᥈⣴࡟ࡣ climbing image nudged elastic band
(CI-NEB)ἲࢆ⏝࠸ࡓࠋ(2)࡛ࡣࠊ㟁Ꮚ≧ែィ⟬ࡣ Turbomole ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ RI-BP86/def-SV(P)ࣞ࣋ࣝࡢ
DFT ィ⟬ࢆ⾜ࡗࡓࠋ㔠ᒓࢡࣛࢫࢱ࣮㸦Cu3NiࠊCu2Ni2ࠊCuNi3㸧ࡢᏳᐃᵓ㐀ࡣࠊGRRM ࣉࣟࢢ࣒ࣛࡢ༢ᡂศ㸦SC㸧
AFIR ἲࢆ⏝࠸࡚ồࡵࡓࠋᚓࡽࢀࡓᏳᐃᵓ㐀ࡢୖ࡛ NO ศᏊࡀゎ㞳ࡍࡿ⤒㊰ࡣࠊGRRM ࣉࣟࢢ࣒ࣛࡢከᡂศ
㸦MC㸧AFIR ἲࢆ⏝࠸࡚᥈⣴ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 Ⅳ⣲ࢻ࣮ࣉ h-BN ࢆゐ፹࡜ࡋࡓศᏊ≧㓟⣲࡟ࡼࡿ㓟໬࣭࢚࣏࢟ࢩ໬཯ᛂࡢ⌮ㄽゎ᫂༢ᒙࡢභ᪉ᬗ⣔ࡢ❅໬࣍࢘⣲㸦h-BN㸧ࡣࢢࣛࣇ࢙ࣥ࡟㢮ఝࡋࡓᗄఱᵓ㐀ࢆᣢࡘ஧ḟඖ≀㉁࡛࠶ࡿࡀࠊࢢࣛ
ࣇ࢙ࣥ࡜ࡣ␗࡞ࡾ⤯⦕య࡛࠶ࡿࡓࡵࠊᗈ࠸ࣂࣥࢻࢠࣕࢵࣉ࡜㧗࠸⇕Ᏻᐃᛶࢆ᭷ࡋ࡚࠸ࡿࠋᚑࡗ࡚ࠊ㏻ᖖ h-BNࡣ㧗࠸཯ᛂᛶࢆ♧ࡉ࡞࠸ࡀࠊ᭱㏆ࡢᡃࠎࡢ◊✲࡛ࠊB ཎᏊࡢࡦ࡜ࡘࢆ C ཎᏊ࡟⨨᥮ࡋࡓ CB@BN ࡣ⨨᥮఩⨨ࡢࡳ࡞ࡽࡎᗈᇦ࡛㓟⣲྾╔⬟ࢆᣢࡘࡼ࠺࡟࡞ࡾࠊゐ፹άᛶࢆ♧ࡍࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᮏ◊✲࡛ࡣࠊࢻ࣮
ࣉࡋࡓ C ཎᏊ࠿ࡽࡢ㊥㞳࡟ᑐࡋ࡚ࠊศᏊ≧㓟⣲ࢆ⏝࠸ࡓ CO ࡢ㓟໬࡜ C2H4 ࡢ࢚࣏࢟ࢩ໬࡜࠸࠺඾ᆺⓗ࡞㓟໬཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ࢆㄪ࡭ࡓࠋ
ࡲࡎࠊ⨨᥮఩⨨࡟᭱ࡶ㏆࠸ B ࡟ O2 ࡀ྾╔ࡋࡓࣔࢹࣝࢆ⏝࠸࡚ࠊCO 㓟໬཯ᛂ⤒㊰ࢆㄪ࡭ࡓ㸦ᅗ 1㸧
ࠋCO ࡢ- 493 -

㓟໬⤒㊰࡟ࡣࠊOCOO ࡜࠸࠺㐣㓟໬≀ⓗ୰㛫యࢆ⤒⏤ࡍࡿࠕ⮬ᕫಁ㐍⤒㊰ࠖ࡜ࠊCO ࡜ O2 ࡀ┤᥋཯ᛂࡋ࡚ CO2
ࢆ⏕ࡌࡿࠕ┤᥋⤒㊰ࠖࡀぢࡘ࠿ࡾࠊ࡝ࡕࡽࡶⓎ⇕ⓗ࡟㐍⾜ࡍࡿࡇ࡜ࡀࡗࡓࡀ୧⪅ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡢᕪࡣ
ࢃࡎ࠿࡛࠶ࡗࡓࠋḟ࡟ࠊࢻ࣮ࣉࡋࡓ C ࠿ࡽࡢ㊥㞳ࡀ␗࡞ࡿ 3 ࡘࡢ྾╔ࢧ࢖ࢺ࡟ᑐࡋ࡚ࠊ⮬ᕫಁ㐍⤒㊰࡜┤᥋⤒㊰࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆㄪᰝࡋࡓ㸦ᅗ 2㸧ࠋC ࠿ࡽࡢ㊥㞳ࡀ㞳ࢀࡿ࡟ࡘࢀ࡚ࠊ୰㛫యࡢ࢚ࢿࣝ
ࢠ࣮ࡢୖ᪼ࡀࢃࡎ࠿࡟ㄆࡵࡽࢀࡿࡶࡢࡢࠊάᛶ໬࢚ࢿࣝࢠ࣮࡟ࡣ࡯࡜ࢇ࡝ᕪࡀ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ࢚࣏࢟
ࢩ໬࡟ࡘ࠸࡚ࡣࠊC ࠿ࡽࡢ㊥㞳ࡀ㛗ࡃ࡞ࡿ࡜๪⏕ᡂ≀ࡢ࢔ࣝࢹࣄࢻ⏕ᡂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀపୗࡍࡿࡇ࡜
ࡀࢃ࠿ࡗࡓࠋ

ᅗ 1. (a)༢ᒙ CB@BN ࡢ CO 㓟໬ࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࠋ(b) 2 ࡘࡢ཯ᛂ⤒㊰࡟ᑐࡍࡿ࣑ࢡࣟ࢟ࢿࢸ࢕ࢵࢡ࣭
ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦300 K㸧
ࠋ(c)࡟ࡣ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ࡟ᑐᛂࡍࡿᵓ㐀ࡶ♧ࡋࡓࠋ
ᅗ2. (a)⮬ᕫಁ㐍⤒㊰ࠊ(b)┤᥋⤒㊰ࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡢ㓟⣲྾╔ࢧ࢖ࢺ౫ᏑᛶࠋC࠿ࡽࡢ㊥㞳ࡢ␗࡞ࡿ3ࡘࡢ㓟⣲྾╔ࢧ࢖ࢺࢆྑᅗ࡟♧ࡍࠋ- 494 -

3.2

㔠ᒓ 4 㔞యࢡࣛࢫࢱ࣮ࡢ␗ᛶ໬཯ᛂ࡜ NO ゎ㞳཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㔠ᒓཎᏊࢡࣛࢫࢱ࣮ࡣ⮬⏤ᗘࡀ㧗࠸ࡓࡵࠊከࡃࡢᵓ㐀␗ᛶయࢆᣢࡘࠋ㏻ᖖࡢ⌮ㄽ◊✲࡛ࡣࡑࡢ᭱Ᏻᐃᵓ㐀ࡢ᥈⣴࡜⥆ࡃ㟁Ꮚ≀ᛶゎᯒࡀ୺࡛࠶ࡗࡓࡀࠊ㏆ᖺࡢ⌮ㄽ໬Ꮫ࣭ィ⟬໬ᏛࡢⓎᒎ࡟ࡼࡾࠊᏳᐃᵓ㐀㛫ࡢ␗ᛶ໬཯ᛂࡸ␗ᛶయࢆྵࡵࡓゐ፹άᛶࡢ◊✲ࡀྍ⬟࡟࡞ࡗ࡚ࡁࡓ㸬ᮏ◊✲࡛ࡣࠊCu ࡜ Ni ྜ㔠ࢡࣛࢫࢱ࣮ࢆᑐ㇟࡜
ࡋ࡚ࠊᏳᐃᵓ㐀ࠊ␗ᛶ໬཯ᛂ⤒㊰ࠊ࠾ࡼࡧ NO ゎ㞳ࡢゐ፹཯ᛂ⤒㊰ࡢ᥈⣴ࢆ⾜࠸ࠊẚ㍑ࢆ⾜ࡗࡓࠋࡲࡎࠊCuNi ྜ㔠 4 ཎᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀᥈⣴ࢆ⾜࠸ࠊ␗ᛶ໬཯ᛂ࡟ࡘ࠸࡚ㄪᰝࡋࡓࠋ᭱Ᏻᐃᵓ㐀ࡣ࠸ࡎࢀࡶ⳻ᙧ࡛࠶ࡾࠊNi ࡢᩘ࡟ࡼࡿ㐪࠸ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ୍᪉࡛ࠊࢫࣆࣥ≧ែ࡟ࡘ࠸࡚ࡣ CuNi3 ࡛ࡣ㧗ࢫࣆࣥ≧ែࡀᏳᐃ໬ࡉࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡼࡾ㧗࠸ࢫࣆࣥ≧ែ࡟ࡼࡗ࡚౛࠼ࡤ㓟⣲࡞࡝ࡢ྾╔ࡀಁ㐍ࡉࢀࡿྍ⬟ᛶࡣ⪃࠼ࡽࢀࡿࠋ཯ᛂ㞀ቨ࡟ࡘ࠸࡚ࡣ Ni ࡀቑ࠼ࡿ࡜ࡼࡾ㧗ࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋNi ࡔࡅࡢࢡࣛࢫࢱ࣮࡛ࡣ
␗ᛶ໬཯ᛂࡢ㞀ቨࡀ 60 kJ/mol ࡜㧗࠸ࡀࠊࡑࡢᛶ㉁ࡀ㢧ⴭ࡟࡞ࡗ࡚ࡁ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ␗ᛶ໬཯ᛂࡀ㉳ࡇࡾࡸࡍࡅࢀࡤከࡃࡢ␗ᛶయ࡟㛵ࡍࡿゐ፹⤒㊰ࢆ⪃࠼ࡿᚲせࡀ࠶ࡿࡀࠊ௒ᅇࡢࢡࣛࢫࢱ࣮࡟࠾࠸࡚ࡣ㔠࡜㖟ࢆ㝖࠸࡚᭱Ᏻᐃᵓ㐀࠿ࡽᵓ㐀ኚ໬ࡍࡿࡓࡵ࡟ 50 kJ/mol ௨ୖࡢ࢚ࢿࣝࢠ࣮ࡀᚲせ࡛࠶ࡿࡓࡵࠊࡑࢀ࡯࡝␗ᛶయࡢ
ຠᯝࡣ኱ࡁࡃ࡞࠸ࡇ࡜ࡀᮇᚅ࡛ࡁࡿࠋ
ḟ࡟ࠊᅗ 2 ࡟ CuNi ྜ㔠 4 ཎᏊࢡࣛࢫࢱ࣮࡟ NO ࡀ྾╔ࡋࠊࡑࡢᚋゎ㞳ࡍࡿ཯ᛂ⤒㊰ࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ
࢓࢖ࣝࢆ♧ࡍࠋ㔠ࠊ㖟ࠊ㖡ࡢሙྜ㸦Kondo et al., J. Comput. Chem. Jpn. 2018㸧࡜ẚ㍑ࡍࡿ࡜ࠊNO ゎ㞳࡟ᑐࡋ࡚㔠࡜㖟ࡣ࠶ࡲࡾ᭷ᮃ࡞㔠ᒓ࡛ࡣ࡞࠸ࡀࠊ㖡ࡣ 200 kJ/mol ⛬ᗘ࡜ᗄศప࠸࢚ࢿࣝࢠ࣮࡛཯ᛂࡀ㐍⾜ࡍࡿࠋྜ㔠࡟╔┠ࡍࡿ࡜ࠊCu2Ni2 ࡢపࢫࣆࣥᵓ㐀㸦doublet ≧ែ㸧࡛ 250 kJ/mol ࡜㞀ቨࡀ㧗ࡃ࡞ࡿࡀࠊ㧗ࢫࣆࣥᵓ㐀㸦quartet≧ែ㸧࡛ࡣ 150 kJ/mol ࡜㞀ቨࡀୗࡀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋྜ㔠ࡣࢫࣆࣥ≧ែ࡛ࡑࡢ NO άᛶ⬟ࡀኚࢃࡿࡇ࡜࡜ࠊ
㧗ࢫࣆࣥ≧ែࢆᐇ⌧ࡍࡿࡇ࡜࡛཯ᛂ㞀ቨࢆୗࡆࡿຠᯝࡀぢ࡚ྲྀࢀࡓࠋ

ᅗ2. Cu3NiࠊCu2Ni2ࠊ࠾ࡼࡧCuNi3࡟྾╔ࡋࡓNOࡀゎ㞳ࡍࡿ཯ᛂ࡟ᑐࡍࡿGibbs࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1) ᑠᯘṇேࠕ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࢆά⏝ࡋࡓゐ፹࣭⾲㠃྾╔⣔ࡢィ⟬࣭ゎᯒ࣭ண

ࠖCSJ ໬Ꮫࣇ࢙ࢫࢱ ,2021.10.19-21, ࢜ࣥࣛ࢖ࣥ; (2) ᑠᯘṇேࠕࣃ࣮ࢩࢫࢸࣥࢺ࣭࣍ࣔࣟࢪ࣮ࢆ⏝࠸ࡓࢢ࣮ࣟࣂࣝ཯ᛂ⤒㊰ᆅᅗ࡟ᑐࡍࡿグ㏙Ꮚࡢ㛤ᣅࠖIQCE 㔞Ꮚ໬Ꮫ᥈⣴ㅮ₇఍ 2021, 2021.11.4, ᯽/࢜ࣥࣛ࢖ࣥ; (3) M. Kobayashi “Automated- 495 -

Reaction Path Search and Informatics” EU-Japan Workshop on HPC-Based Material Sciences, 2021.11.9, online; (4) T.
Taketsugu “On the fly molecular dynamics approach to the tunneling splitting due to intramolecular proton transfer”
2021 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021), 2021.12.16-21, online; (5) M.
Kobayashi “Surface Adsorption Model Calculation Database and Its Application to Activity Prediction of
Heterogeneous Catalysts” 2021 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021),
2021.12.16-21, online; (6) T. Iwasa “First principles studies for optical near-field spectroscopy and photochemistrybeyond the dipole approximation” 2021 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021),
2021.12.16-21, online; (7) ᒾబ㇦ࠕ㏆᥋ሙග࡜ศᏊࡢ┦஫స⏝㸸཮ᴟᏊ㏆ఝࢆ㉸࠼ࡓศᏊ⌮ㄽᡭἲࡢ㛤Ⓨ࡜ᛂ⏝ࠖࠕ⮬↛⛉Ꮫ࡟࠾ࡅࡿ㝵ᒙ࡜඲యࠖࢩ࣏ࣥࢪ࣒࢘, 2022.1.7, ࢜ࣥࣛ࢖ࣥ; (8) T. Taketsugu “Novel quantum
chemical approach to chemical reactions: reduced-dimensionality reaction space and natural reaction orbital” Hokkaido
University/ICReDD Five Attached Institutes Joint Symposium, 2022.3.7, online; (9) T. Taketsugu “Chemical reaction
analysis in terms of reduced-dimensional reaction route map and natural reaction orbital” 4th ICReDD International
Symposium, 2022.3.12-13, online.㸦௨ୖᣍᚅㅮ₇ࡢ୍㒊ࠊ௚ከᩘ㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ۻ‬S. Ebisawa, T. Tsutsumi, and T. Taketsugu, J. Comput. Chem. 42, 27-39 (2021); (2) ‫ۻ‬M. Takenaka, T.
Taketsugu, and T. Iwasa, J. Chem. Phys. 154, 024104 (2021); (3) ‫ۻ‬Y. Nitta, O. Schalk, H. Igarashi, S. Wada, T.
Tsutsumi, K. Saita, T. Taketsugu, and T. Sekikawa, J. Phys. Chem. Lett. 12, 674-679 (2021); (4) ‫ۻ‬T. Fujimori, M.
Kobayashi, and T. Taketsugu, J. Comput. Chem. 40, 620–629 (2021); (5) ‫ۻ‬ᑠᯘṇே㸪⸨᳃ಇ࿴㸪Ṋḟᚭஓ, J.
Comput. Chem. Jpn. 20, 48-59 (2021); (6) ‫ۻ‬M. Gao, B. Wang, T. Tsuneda, A. Lyalin, and T. Taketsugu, J. Phys. Chem.
C 125, 19219-19228 (2021); (7) ‫ۻ‬T. Tsutsumi, Y. Ono, and T. Taketsugu, Chem. Commun. 57, 11734-11750 (2021);(8) ‫ۻ‬S. Ebisawa, M. Hasebe, T. Tsutsumi, T. Tsuneda, and T. Taketsugu, Phys. Chem. Chem. Phys. 24, 3532-3545(2022); (9) ‫ۻ‬H. Takakura, S. Matsuhiro, M. Kobayashi, Y. Goto, M. Harada, T. Taketsugu, M. Ogawa, J. Photochem.
Photobiol. A Chem. 426, 113749 (2022); ‫ۻ‬T. Tsutsumi, Y. Ono, and T. Taketsugu, Top. Current Chem. 380, 19 (2022);(10) ‫ۻ‬K. Oda, T. Tsutsumi, S. Keshavamurthy, K. Furuya, P. B. Armentrout, and T. Taketsugu, ACS Phys. Chem. Au,
in press; (11) ‫ۻ‬M. Kobayashi, Y. Oba, T. Akama, and T. Taketsugu, J. Math. Chem., in press.

- 496 -

ࢼࣀ࣭ࣂ࢖࢜ศᏊ࡟࠾ࡅࡿ㹖⥺ㄏ㉳ゎ㞳ືຊᏛࡢᐇ᫬㛫࢖࣓࣮ࢪࣥࢢ⌮ㄽ
Realtime imaging theory for the x-ray induced fragmentation
dynamics of nano-/bio-molecules‫ۑ‬ᒣᓮ 㤾㸦⌮໬Ꮫ◊✲ᡤ㸧

1◊✲┠ⓗ㏆ᖺࡢࣇ࢙࣒ࢺ⛊ X ⥺ග※ࡢⓎ㐩࡟ࡼࡾ㸪᭷ᶵศᏊ࡟࠾ࡅࡿࣇ࢙࣒ࢺ⛊㹖⥺ග໬Ꮫ཯ᛂ㐣⛬ࡢᐇ᫬㛫㏣㊧ࡀᐇ⌧ࡋࡘࡘ࠶ࡿ[1]㸬ᮏᡭἲ࡜㐺ษ࡞⌮ㄽィ⟬ࢆ X ⥺᭷ᶵࢩࣥࢳ࣮ࣞࢱࡸࡀࢇ἞⒪⏝ X ⥺ቑឤ๣࡞࡝ࡢ X ⥺ᶵ⬟ᛶศᏊ[2]ࡢ X ⥺ග໬Ꮫ཯ᛂᶵᵓゎ᫂࡟㐺⏝ࡍࢀࡤ㸪X ⥺ᶵ⬟ᛶศᏊࡢᛶ⬟ྥୖ࡟⧅ࡀࡿ࡜ᮇᚅࡉࢀ
ࡿ㸬X ⥺ᶵ⬟ᛶศᏊࡢ㦵᱁ࢆ࡞ࡍⰾ㤶᪘ศᏊ㸦10 ཎᏊ௨ୖ㸧ࡢ X ⥺ග໬Ꮫ཯ᛂ࡛ࡣ㸪ෆẆ࢖࢜ࣥ໬࡜ Auger⦆࿴࠿ࡽ࡞ࡿ࢖࢜ࣥ໬㐣⛬࡛ 102-103 ࡢ㟁Ꮚບ㉳ dication ≧ែࡀ⏕ᡂࡋ㸪㠀᩿⇕㑄⛣ࡀ㛵୚ࡍࡿ໬Ꮫ཯ᛂࡀ
㏿ࡸ࠿࡟㉳ࡁࡿ㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ㸪ⰾ㤶᪘➼ࡢ᭷ᶵศᏊࡢ㹖⥺ㄏ㉳࢖࢜ࣥ໬࡜ dication ࡢ㠀᩿⇕཯ᛂࡢ ୧㐣⛬ࢆຠ⋡ࡼࡃィ⟬࡛ࡁࡿ㝵ᒙⓗືຊᏛ⌮ㄽࢆ㛤Ⓨࡋ㸪㠀࣋ࣥࢮࣀ࢖ࢻ⣔ⰾ㤶᪘ศᏊ Tropone㸦C7H6O,௨ୗ
Tr㸧࡟㐺⏝ࡋࡓ㸬

2◊✲᪉ἲࠊィ⟬᪉ἲศᏊ M ࡀ୍ගᏊෆẆ࢖࢜ࣥ໬ (㏿ᗘᐃᩘ kcore(t))࡜ Auger ⦆࿴(kAuger)࡟ࡼࡗ࡚ dication ࡬࡜࢖࢜ࣥ໬ࡉࢀ㸪ࡑࡢᚋ࡟㠀᩿⇕㑄⛣ࢆྵࡴ໬Ꮫ཯ᛂ(k)ࢆᘬࡁ㉳ࡇࡍ㐣⛬ࡢ㐃❧࣮ࣞࢺ᪉⛬ᘧࢆ⪃࠼ࡿ㸬ࡇࡢ࣮ࣞࢺ᪉⛬ᘧࢆ
Dication ࡢྛ≧ែ࡜཯ᛂ⏕ᡂ≀ࡢ ⃰ᗘ࣋ࢡࢺࣝ[M2+](t)࡟ࡘ࠸࡚ゎᯒⓗ࡟ゎࡃ࡜㸪
[M2+](t) = kcore(t) ‫>כ‬Ĭ t) [1 – H[S íkAugert)] exp(kt)] ή ȡ0

(1)

࡜, ࢖࢜ࣥ໬࡜㠀᩿⇕཯ᛂࡢ஧㐣⛬ࡀኚᩘศ㞳ࡉࢀࡓᙧ࡟᭩ࡅࡿࡓࡵ,ࡇࢀࡽࡢ㐣⛬ࡣ⊂❧ࡋࡓ㝵ᒙ࡜ࡋ࡚
ィ⟬࡛ࡁࡿࡇ࡜ࡀศ࠿ࡿ[a,b]㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ dication ࡟࠾ࡅࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃࡜᫬้ t = 0࡛▐᫬࡟࢖࢜ࣥ໬ࡉࢀࡓᴟ㝈࡟࠾ࡅࡿึᮇศᕸ ȡ0 (Auger ࢫ࣌ࢡࢺࣝ) ࢆࡍ࡭࡚ࡢ 2 ✵Ꮝ㟁Ꮚ㓄⨨ࢆ⪃៖ࡋࡓ㓄⨨㛫┦஫స⏝ἲ (ᇶᗏ㛵ᩘ㸸ANO-RCC-VTZP)࡟ࡼࡾࢥ࢔࣮࣍ࣝୖࡢ㟁Ꮚศᕸࡢ㛵ᩘ࡜ࡋ࡚ồࡵ[3,4]㸪
dication ࡢ㠀᩿⇕཯ᛂࢆ Linear vibronic Coupling ࣔࢹ࣏ࣝࢸࣥࢩࣕࣝᒁ㠃ୖ࡟࠾ࡅࡿ fewest-switching 㠀᩿⇕ศᏊືຊᏛἲ[5,6]࡛㏣㊧ࡋࡓ㸬㓄⨨㛫┦஫స⏝ἲ࡟ࡼࡿ㟁Ꮚ≧ែィ⟬࡟ࡣ OpenMolcas 18.09[7]ࢆ㸪㠀᩿⇕ ศᏊືຊᏛィ⟬࡟ࡣ Sharc 2.1[5,6]ࢆ⏝࠸ࡓ㸬 ࡉࡽ࡟㸪Tropone ࡟࠾ࡅࡿ㹖⥺໬Ꮫ཯ᛂ㏣㊧ࢆࣇ࢙࣒ࢺ⛊㹖⥺ 2 Ⰽ࣏ࣥࣉ࣭ࣉ࣮ࣟࣈศගἲ࡛㏣㊧ࡍࡿࡢ࡟㐺ࡋࡓ࣏ࣥࣉග࣭ࣉ࣮ࣟࣈගࡢගᏊ࢚ࢿࣝࢠ࣮࡜ࣆ࣮ࢡᙉᗘࢆ㸪MS-RASPT2 ἲ࡟ࡼࡿ C(1s) edge ཬࡧ O(1s)edge 㹖⥺ග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ㟁Ⲵ q (q= 0,1,2)౫Ꮡᛶ࡟㛵ࡍࡿ⌮ㄽィ⟬࡜㸪ከẁ㝵࢖࢜ࣥ໬ࣔࢹࣝ࡟ᇶ࡙ࡃ
࢖࢜ࣥ໬࣮ࣞࢺ᪉⛬ᘧἲ࡟ࡼࡾồࡵࡓ㸬MS-RASPT2 ィ⟬࡟࠾ࡅࡿάᛶ✵㛫࡟ࡣ Core-hole ࡀ⏕ᡂࡍࡿඖ⣲➃ࡢ 1s ㌶㐨ࡍ࡭࡚ࢆ RAS1 ✵㛫࡟࡜ࡾ㸪Tr ࡢᣢࡘ 4 ࡘࡢȧ㌶㐨࡜ȧ*㌶㐨ཬࡧ 1 ࡘࡢ n ㌶㐨ࢆ RAS2 ✵㛫࡟ྵࡵ㸪ࡇࢀࡽࡢ㌶㐨ࡀᣢࡘ㟁Ꮚ 10 – q 㟁Ꮚࡍ࡭࡚ࢆ⪃៖ࡋࡓ. ᇶᗏ㛵ᩘ࡟ࡣ Sapproro-2012-TZP ᇶᗏ[9]ࢆ C࣭OཎᏊ࡟㸪Sapproro-2012-DZP ᇶᗏ[9]ࢆ H ཎᏊ࡟⏝࠸ࡓ㸬ࡇࢀࡽࡢィ⟬࡟ࡣ㸪OpenMolcas 21.10 ࢆ⏝࠸ࡓ㸬

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3◊✲ᡂᯝᮏ㝵ᒙⓗືຊᏛ⌮ㄽࢆ Tr ࡟㐺⏝ࡋࡓ⤖ᯝࢆᅗ 1 ࡟♧ࡍ[d-g,i]㸬Tr ࡢ C(1s)㌶㐨࠿ࡽෆẆ࢖࢜ࣥ໬ࡍࡿ࡜㸪ʌ ㌶㐨࡜ ı ㌶㐨࡟ 1 ಶࡎࡘ✵Ꮝࢆᣢࡘ୍㔜㡯㟁Ꮚບ㉳ dication ≧ែ

(1ʌí1ıí1)࡬୺࡟㑄⛣ࡍࡿࡇ࡜ࡀ Augerࢫ࣌ࢡࢺࣝィ⟬࡛♧ࡉࢀࡓ㸬⏕ᡂࡋࡓບ㉳ dication (Tr2+)ࡣ 30㸫100 ≧ែࢆ⣙ 100 fs ࡛㏻㐣ࡍࡿ㉸ከẁ㝵 ↓㍽ᑕኻάࡢᚋ㸪 C࣭O ࡢ 2p ㌶㐨⏤᮶ࡢ౯㟁ᏊศᏊ㌶㐨࡟ 2 ࡘ✵Ꮝࢆᣢࡘ㟁Ꮚບ㉳≧ែࢆ⤒⏤ࡋ࡚ 10-100 fs
ࡢ᫬ᐃᩘ࡛ከయゎ㞳ࡍࡿࡇ࡜ࡀ㠀᩿⇕ศᏊືຊᏛィ⟬࠿ࡽ♧ࡉࢀࡓ㸬ࡲࡓ㸪䠴⥺ㄏ㉳㉸ከẁ㝵↓㍽ᑕኻά㐣⛬䛾 C䠄1s䠅 edge 䝫䞁䝥 O䠄1s䠅 pre-edge 䝥䝻䞊䝤 X ⥺㐣Ώ྾཰䝇䝨䜽䝖䝹䠄TR-XAS䠅䛾ィ⟬䛻ᡂຌ䛧䛯䠊䛭䛧䛶䠈TR-XAS 䛻ẁ㝵ⓗ↓㍽ᑕኻά㏿ᗘㄽ䝰䝕䝹䛻䜘䜛 Global Fitting ゎᯒ䜢⾜䛖䛣䛸䛷 Tr2䠇䛾㻌 㻌㉸ከẁ㝵↓㍽ᑕኻά㐣⛬䛾᫬ᐃᩘ䜢ᢳฟ䛷䛝䜛஦䜢♧䛧䛯䠊এॸথ३কঝग़ॿঝॠ‫( ش‬eV)

TrCH+

Auger
ĳ = 6 fs

1ȷ-1 Ĳ-1[
pre-edge probe

O

]

ৈஷ৿ཫକ
2p-2 ૾ଙ

FWHM = 10 fs
I 1013 W/cm2

Tr
20 fs
ৎ৑ t (fs)ᅗ 1㸸Tropone dication ࡟࠾ࡅࡿ㉸ከẁ㝵↓㍽ᑕኻά㐣⛬ࡢᶍᘧᅗࡑࡢ⤖ᯝ㸪࢖࢜ࣥ໬࡟ࡼࡿ྾཰➃ࡢ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺ[10]ࢆά⏝ࡍࡿḟࡢࢫ࣮࣒࢟㸦ᅗ 1㸧࡛㸪Tr2㸩ࡢ X ⥺㐣Ώ⣭ᩘࢫ࣌ࢡࢺࣝ㸦TR-XAS㸧࡟┦ᙜࡍࡿࢫ࣌ࢡࢺࣝࡢ

ᐃࢆ⾜࠼ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬(a) Tr ࡀ C(1s)ከ㔜ෆẆ࢖࢜ࣥ໬ࡋ࡞࠸Ἴ㛗ࡢ C(1s) edge ࣏ࣥࣉග࡛ Tr2㸩ࢆ⏕ᡂࡉࡏࡿ㸬(b) Tr2㸩ከẁ㝵↓㍽ᑕኻά୰࡟ Tr2㸩ࡢ O(1s)ෆẆ࢖࢜ࣥ໬࡜ Normal Auger ⦆࿴ࡀ㉳ࡁ࡞࠸Ἴ㛗ࡢ O(1s)pre-edge ࣉ࣮ࣟࣈගࢆ↷ᑕࡋ㸪 Tr3+ࢆ 1 ගᏊ࡛⏕ᡂࡉࡏࡿ㸬(c) Tr3+⏤᮶ࡢゎ㞳࢖࢜ࣥ✀ࡢ 2 య࣭3 య┦㛵ᐃࢩࢢࢼࣝࢆ㐜ᘏ᫬㛫࡜ࣉ࣮ࣟࣈἼ㛗ࡢ㛵ᩘ࡜ࡋ࡚ࡍࡿ㸬

- 498 -

ᐃ࡞࠾ࡇࡢ㝿࡟ࡣ㸪࣏ࣥࣉගࡢࣆ࣮ࢡᙉᗘ Ipu ࢆ 1015-1016 W/cm2 ࡟タᐃࡋ࡚㸪୺せ࡞ࣂࢵࢡࢢࣛ࢘ࣥࢻ࡜࡞ࡿ
࢖࢜ࣥ໬ࡉࢀ࡚࠸࡞࠸ Tr ࢆῶᑡࡉࡏࡿ࡜࡜ࡶ࡟㸪ࣉ࣮ࣟࣈගࡢࣆ࣮ࢡᙉᗘ Ipr ࢆ 1012-1013 W/cm2 ࡟タᐃࡋ࡚ከගᏊ࢖࢜ࣥ໬ࢆᢚไࡍࡿࡇ࡜ࡀ㧗 S/N ẚࡢᐃࢆ⾜࠺ୖࡢ㘽࡛࠶ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋࡓ㸬௨ୖࡢࡼ࠺࡟㸪㝵ᒙⓗືຊᏛ⌮ㄽ࡜ MS-RASPT2 ἲ࡞࡝ࡢ㧗⢭ᗘ㔞Ꮚ໬Ꮫィ⟬ἲࢆ࠺ࡲࡃ⤌ࡳྜࢃࡏ࡚ά⏝ࡍࡿࡇ࡜࡛㸪㹖⥺࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡿ㹖⥺ᶵ⬟ᛶศᏊࡸ⏕యศᏊࡢ㦵᱁ࢆ࡞ࡍⰾ㤶᪘ศᏊ㸦10 ཎᏊ௨ୖ㸧ࡢX ⥺ග໬Ꮫ཯ᛂࢆຠ⋡ࡼࡃ⌮ㄽィ⟬ࡍࡿ࡜࡜ࡶ࡟㸪ᐇ㦂ⓗ᳨ド࡟ᚲせ࡞ᐃἲࡸᐃ᮲௳࡞࡝ࡢᥦ᱌ࢆ ⾜࠼ࡿࡼ࠺࡟࡞ࡗࡓ㸬ཧ⪃ᩥ⊩[1] C. Liekhus-Schmaltz et al. Nat. Commun. 6, 8199(2015)[2] X. Wang et al., Nat. Photo. 15, 187, (2021)[3] M. Mitani et al., J. Electron Spectrosc. 128, 203 (2003)[4] L.

Inhester et al., J. Phys. Chem. Lett. 9, 1156 (2018)[5] S. May et al., WIREs Comput. Mol. Sci. 8, e1370 (2018)[6] F. Plasser et al., Phys. Chem. Chem. Phys. 21, 57 (2019)[7] F. Aquilante et al., J. Chem. Phys. 152, 214117 (2020)[8] R. Guichard et al., J. Phys. B 46, 164025 (2013)[9] T. Noro et al., Theor. Chem. Acc. 131, 1124 (2012)[10] I. Inoue et al., Phys. Rev. Lett. 127, 163903 (2021)[11] E. Kukk et al., Phys. Rev. Res. 3, 013221 (2021)

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[a] ‫ۻ‬ż K. Yamazaki, “Toward multiscale simulation on femtosecond x-ray absorption spectroscopy for x-ray
chemistry,” ➨ 7 ᅇ Q-Leap ࢔ࢺ⛊᠓ㄯ఍, ᣍᚅㅮ₇, 2021 ᖺ 4 ᭶ 20 ᪥㸪࢜ࣥࣛ࢖ࣥ㛤ദ[b] ‫ۻ‬żK. Yamazaki , K. Midorikawa, “X-ray induced femtosecond ionization kinetics of tropone (C7H6O) at
carbon K-edge” ➨ 36 ᅇ໬Ꮫ཯ᛂウㄽ఍, ᅜ㝿Ꮫ఍ཱྀ࣭㢌Ⓨ⾲ (1A01), 2021 ᖺ 6 ᭶ 2㸫4 ᪥㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬[c] ‫ۻ‬żᒣᓮ 㤾㸪⥳ᕝ ඞ⨾ ࠕTropone ஧౯࢝ࢳ࢜ࣥ(C7H6O2+)࡟࠾ࡅࡿ㹖⥺ㄏ㉳␗ᛶ໬࣭ゎ㞳⤒㊰ࡢࢫࣆࣥ≧ែ౫Ꮡᛶࠖ➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸦1A07㸧㸪2021 ᖺ 9 ᭶ 18㸫21 ᪥㸪࢜ࣥࣛ࢖ࣥ㛤ദ[d] ‫ۻ‬żᒣᓮ 㤾ࠕ㝵ᒙⓗືຊᏛ⌮ㄽ࡟ࡼࡿ᭷ᶵศᏊࡢࣇ࢙࣒ࢺ⛊㹖⥺ග໬Ꮫࠖィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍ 2021㸪
ཱྀ㢌Ⓨ⾲㸪2021 ᖺ 2 ᭶ 14-15 ᪥, ࢜ࣥࣛ࢖ࣥ㛤ദ㸬[e] ‫ۻ‬ż K. Yamazaki, K. Midorikawa, ͆Carbon KLL normal Auger induced femtosecond nonadiabatic reaction
dynamics in tropone dication (C7H6O2+)͇, ➨ 37 ᅇ໬Ꮫ཯ᛂウㄽ఍㸪ᅜ㝿Ꮫ఍ཱྀ࣭㢌Ⓨ⾲(1A2㸪Ⓨ⾲ணᐃ)㸪2022 ᖺ 6 ᭶ 1㸫3 ᪥㸪ᮾ໭኱Ꮫ∦ᖹ࢟ࣕࣥࣃࢫ㸬[f] ‫ۻ‬ż K. Yamazaki ,K. Midorikawa, ”Carbon KLL normal Auger induced femtosecond nonradiative decaycascade in tropone dication (C7H6O2+)” ,8th International Conference on Attosecond Science and Technology(ATTO VIII), ᅜ㝿Ꮫ఍࣭࣏ࢫࢱ࣮Ⓨ⾲࣭ᰝㄞ࠶ࡾ㸦ཷ⌮῭ࡳ࣭Ⓨ⾲ணᐃ㸧㸪2022 ᖺ 7 ᭶ 11㸫15 ᪥,- 499 -

University of Central Florida in Orlando, Florida USA.
[g] ‫ۻ‬żK. Yamazaki ,K. Midorikawa, “Carbon 1s Edge Induced Femtosecond Nonradiative Decays in Tropone
Dication (C7H6O2+)” , International Confrence on Ultrafast Phenomena, ᅜ㝿Ꮫ఍࣭࣏ࢫࢱ࣮Ⓨ⾲࣭ᰝㄞ࠶ࡾ㸦ཷ⌮῭ࡳ࣭Ⓨ⾲ணᐃ㸧㸪2022 ᖺ 7 ᭶ 18㸫22 ᪥㸪Hotel Bonaventure Montreal, Montreal Quebec
Canada㸬[h] ‫ۻ‬żᒣᒣᓮ 㤾㸪⥳ᕝ ඞ⨾ ࠕࣇ࢙࣒ࢺ⛊㹖⥺ㄏ㉳㠀᩿⇕཯ᛂ㐣⛬㏣㊧ࡢࡓࡵࡢ㹖⥺ 2 Ⰽ࣏ࣥࣉ࣭ࣉࣟ
࣮ࣈศගἲࠖ➨ 16 ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸦Ⓨ⾲ணᐃ㸧㸪2022 ᖺ 9 ᭶ 19㸫22 ᪥㸪៞᠕⩏ሿ኱Ꮫ▮ୖ࢟ࣕࣥࣃࢫ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[i] ‫ۻ‬K. Yamazaki, K. Midorikawa, to be submitted (2022)- 500 -

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◊✲᪉ἲࠊィ⟬᪉ἲ඲ᅛయ㟁ụྥࡅ㧗ᛶ⬟ᅛయ㟁ゎ㉁ࡢ⏺㠃ࡢ◊✲࡛ࡣࠊᅛయ⣔࡛࠶ࡿࡇ࡜࡜㑄⛣㔠ᒓࢆྵࡴࡇ࡜࠿ࡽ୺࡟

9$63 ࢆ⏝࠸ࡓィ⟬ᐇ⾜ࢆ⾜ࡗࡓࠋ5XGGOHVGHQ±3RSSHUWHWUDJRQDO 㸦L53W㸧ᵓ㐀ᅛయ㟁ゎ㉁᥈⣴ࡣ  ཎᏊ⣔࡜୰つᶍࢧ࢖ࢬ࡛ࡣ࠶ࡿࡀ  ௨ୖࡢ⤌ᡂࡢ➨୍ཎ⌮ィ⟬ࡀᚲせ࡜࡞ࡗࡓࠋ*DUQHW ᆺᅛయ㟁ゎ㉁⢏⏺ࡢ➨୍ཎ⌮ศᏊືຊᏛ㸦0'㸧ィ⟬ࡣ  ཎᏊ⣔௨ୖࡢࢫ࣮ࣃ࣮ࢭࣝࡢ㛗᫬㛫ࢧࣥࣉࣜࣥࢢ࡜࡞ࡿࢳࣕࣞࣥࢪࣥࢢ
࡞ィ⟬࡛࠶ࡿࡀࠊ㺀ᐩᓅ㺁࠾ࡼࡧ +3& ࢆ᭱኱㝈ά⏝ࡋ࡚ጇᙜ࡞⤫ィᛶࢆ☜ಖࡋࡓࠋ
㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụࡢ኱ᇦⓗ⏺㠃ᵓ㐀ࡢ◊✲࡛ࡣࠊ⊂⮬㛤Ⓨࡋࡓ /$0036 ࣮࣋ࢫ 5HG0RRQ ࢆ⏝࠸ࠊ㧗⃰ᗘ /L ሷ㟁ゎ㉁⁐ᾮࡣࣜࣥ㓟ࢺ࣓ࣜࢳࣝ㸦703㸧  ศᏊࠊࣜࢳ࣒࢘ࣅࢫࣇࣝ࢜ࣟࢫࣝ࣍ࢽࣝ࢔࣑ࢻ
㸦/L)6$㸧 ศᏊࠊ㟁ᴟⅣ⣲  ཎᏊศᏊ࠿ࡽ࡞ࡿ⣔࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋࡲࡓࠊ(& 㟁ゎᾮ⣔࡟࠾ࡅࡿᐃ㟁఩ࢩ࣑࣮ࣗࣞࢩࣙࣥࡣⅣ㓟࢚ࢳࣞࣥ㸦(&㸧  ศᏊࠊࣜࢳ࣒࢘࢖࢜ࣥ  ศᏊࠊ3)í ศᏊࠊ㟁ᴟⅣ⣲  ཎᏊศᏊࠊྜィ  ཎᏊ࠿ࡽ࡞ࡿ⣔࡛࠶ࡿࠋ
㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụࡢ࢖࢜ࣥఏᑟᗘࡢ㟁ゎᾮ⃰ᗘ౫Ꮡᛶࡢ◊✲࡛ࡣࠊ⣙  ཎᏊ࠿ࡽ࡞ࡿ 00ࡢ⃰ᗘࡢ /L%)(& 㟁ゎᾮࢆィ⟬ࣔࢹࣝ࡜ࡋࡓࠋྂ඾ 0' ィ⟬ࡣࠊࣃ࣓࣮ࣛࢱ᭱㐺໬ࡋࡓ $02(%$ ຊሙ࡜7,1.(5 ࢆ⏝࠸ࡓࠋ$02(%$ ຊሙࡢࣃ࣓࣮ࣛࢱ᭱㐺໬ࡣ 9$63 ࡜⊂⮬ᣑᙇࡋࡓ㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸ࡓࠋࢺ࣏ࣟࢪ࢝ࣝࢹ࣮ࢱゎᯒࡣ⊂⮬ᣑᙇࡋࡓ +RP&ORXG ࢆ⏝࠸ࡓࠋ

- 501 -

⇞ᩱ㟁ụࡢ ᗘࡸḞ㝗⃰ᗘ࡟ࡼࡿゐ፹άᛶࡢ◊✲࡛ࡣࠊ➨୍ཎ⌮ࣔࣥࢸ࢝ࣝࣟィ⟬࣭ᶵᲔᏛ⩦ࣔࢹࣝᵓ⠏࣭⇕ຊᏛࢧࣥࣉࣜࣥࢢ㐃ᦠࣇ࣮࣒࣮ࣞ࣡ࢡࢆᣢࡘ⊂⮬㛤Ⓨࡋࡓ࢔ࣉࣜ DE,&6 ࡜ᅛయ࣭⁐ᾮ⏺㠃ィ⟬⏝ࡢ (605,60 ࢆ⏝࠸ࡓࠋ ཎᏊ࠿ࡽ࡞ࡿᩘⓒ㏻ࡾࡢ⾲㠃ࢫࣛࣈࣔࢹࣝࡢ➨୍ཎ⌮ィ⟬࡜ᩘ༓ཎᏊ࠿ࡽ࡞ࡿᩘ୓
ࢫࢸࢵࣉࡢࣔࣥࢸ࢝ࣝࣟィ⟬ࢆ㺀ᐩᓅ㺁࠾ࡼࡧ +3& ࢆ฼⏝ࡋ࡚ᐇ᪋ࡋࡓࠋ
⇞ᩱ㟁ụࡢ㓟⣲㑏ඖ࣭&2 㓟໬཯ᛂᶵᵓࡢ◊✲࡛ࡣࠊ ಶࡢཎᏊ࠿ࡽ࡞ࡿࢢࣛࣇ࢙ࣥࣜ࣎ࣥࡢ࢚ࢵࢪ࡟
3W ༢ཎᏊࡀ⤖ྜࡋࡓ⣔࡟ࡘ࠸࡚ࠊ➨୍ཎ⌮㟁Ꮚ≧ែィ⟬࡜㐍໬ⓗ࢔ࣝࢦࣜࢬ࣒࠾ࡼࡧ࢞࢘ࢫ㐣⛬ᅇᖐࢆ⤌ࡳྜࢃࡏࡓ኱ᇦⓗᏳᐃᵓ㐀᥈⣴ᡭἲ࡟ࡼࡾᏳᐃᵓ㐀ࢆồࡵࠊ1 ཎᏊࢆࢻ࣮ࣉࡋࡓ⣔࡟ࡘ࠸࡚ࡶồࡵࡓࠋࡉࡽ࡟
ࡑࡇ࡬ࡢ &22++2 ࡞࡝ࡢ྾╔Ꮚࡢ྾╔≧ែ࡟ࡘ࠸࡚ィ⟬ࡋࡓࠋ⇞ᩱ㟁ụࡢ㟁ゎ㉁⭷ࣂࣝࢡ࡟࠾ࡅࡿ≀㉁㍺㏦࣑ࢡࣟᶵᵓࡢ◊✲࡛ࡣࠊ⌧ᐇ⣔ࢆ᱁Ꮚࣔࢹࣝ࡟⢒ど໬ࡋࠊ᱁Ꮚୖࡢ⢏Ꮚࡢᣑᩓ㐠ືࢆືⓗ 0& ἲ࡟ࡼࡗ࡚㏣㊧ࡋࠊࡑࡢ㌶㊧ࢆゎᯒࡍࡿ࡜࠸࠺ᡓ␎ࡢࡶ࡜ࠊ㟁ゎ㉁⭷ᇶᮏࢭࣝࡢ  ࣓ࢵࢩࣗ᱁Ꮚࣔࢹࣝࢆ᥇⏝ࡋࠊ኱つᶍ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦02'</$6㸧ࢆ㺀ᐩᓅ㺁࠾ࡼࡧ+3& ࢆ฼⏝ࡋ࡚ᐇ᪋ࡋࡓࠋ



◊✲ᡂᯝ



඲ᅛయ㟁ụྥࡅ㧗ᛶ⬟ᅛయ㟁ゎ㉁ࡢ⏺㠃࡟࠾ࡅࡿ཯ᛂ࣭࢖࢜ࣥ㍺㏦ᶵ⬟ࡢゎ᫂඲ᅛయ㟁ụࡢᐇ⏝໬࡟ྥࡅ࡚ࠊ㔜せ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࡢࡀࠊ
㸦㸯㸧ࡉࡽ࡞ࡿ㧗࠸࢖࢜ࣥఏᑟᗘࢆᣢࡘᅛయ
㟁ゎ㉁ᮦᩱࡢ㛤Ⓨ࡜ࠊ㸦㸰㸧⏺㠃࡟࠾ࡅࡿ㧗᢬ᢠ໬࣭ຎ໬ࡢᢚไ࡛࠶ࡿࠋࡇࢀࡲ࡛ࠊᡃࠎࡣ㸦㸰㸧ࡢゎᯒࡢࣈ࣮ࣞࢡࢫ࣮ࣝࢆ┠ᣦࡋࡓ⏺㠃ᵓ㐀⩌ࢧࣥࣉࣜࣥࢢᡭἲࠕ࣊ࢸࣟ⏺㠃 &$/<362 ἲࠖࢆ㛤Ⓨࡋࠊᵝࠎ࡞㟁ᴟ㸦㑄⛣㔠ᒓ㓟໬≀ṇᴟࠊ/L 㔠ᒓ㈇ᴟ㸧࡜ᅛయ㟁ゎ㉁⏺㠃ࡢ➨୍ཎ⌮⤫ィゎᯒࢆ⾜ࡗ࡚ࡁࡓࠋ
௧࿴㸱ᖺᗘࡣ㸦㸯㸧࡟ࡘ࠸࡚↔Ⅼࢆ࠶࡚ࠊ㧗࢖࢜ࣥఏᑟᗘ࡜Ᏻᐃᛶࢆවࡡഛ࠼ࡓᅛయ㟁ゎ㉁᥈⣴ࢆ⾜ࡗࡓࠋ᭱㏆ὀ┠ࡉࢀ࡚࠸ࡿ L53W ᵓ㐀࡟╔┠ࡋࠊᶵᲔᏛ⩦ᢏ⾡ࢆ⏝࠸࡚ᩘ୓✀㢮ࡢ⤌ᡂ࠿ࡽ  ✀㢮ࢆࡲࡎࢫࢡ࣮ࣜ
ࢽࣥࢢࡋࠊࡉࡽ࡟ࣁ࢖ࢫ࣮ࣝࣉࢵࢺ➨୍ཎ⌮ィ⟬࡟ࡼࡾ  ✀㢮ࡢ᭷ᮃᮦᩱࢆᢳฟࡋࡓࠋࡑࡢ୰࠿ࡽ➨୍ཎ⌮0' ィ⟬࡟ࡼࡿ /L ࢖࢜ࣥఏᑟᗘࡢィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊ/L2%U ࡀᏳᐃᛶ࡜㧗࠸࢖࢜ࣥఏᑟࢆවࡡഛ࠼ࡓᮦᩱ
࡜ࡋ࡚᭷ᮃ࡛࠶ࡿࡇ࡜ࢆᥦ᱌ࡋࡓ㸦ᅗ 㸧>@ࠋࡇࡢᥦ᱌ࢆཷࡅ࡚ࠊᐇ㦂ᐙࡀྜᡂࢆヨࡳࠊ࡯ࡰྠࡌ⤌ᡂࡢᮦᩱࡀᐇ㝿࡟ྜᡂࡉࢀࡿ࡟⮳ࡗࡓࠋᐃ㔞ᛶ࡟ࡘ࠸࡚ࡲࡔㄢ㢟ࡣṧࡿࡶࡢࡢࠊࡇࡢྜᡂᮦᩱࡶẚ㍑ⓗ㧗࠸࢖࢜ࣥఏ
ᑟᗘࢆ♧ࡋࠊィ⟬࣭ࢹ࣮ࢱ◊✲࠿ࡽᥦ᱌ࡋࡓೃ⿵ᮦᩱࡀᐇ㝿࡟ྜᡂࡉࢀ᭷ᮃ࡞ᮦᩱ࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ>@ࠋᮦᩱྜᡂࡣ㐃ᦠࡍࡿ -67 ࣉࣟࢪ࢙ࢡࢺࡢᯟ⤌ࡳ࡛ᐇ᪋ࡋ≉チฟ㢪ࡶ⾜ࡗ࡚࠸ࡿࠋᅗ 㸦ᕥ㸧L53W ᵓ㐀⩌࡟ᑐࡍࡿ➨୍ཎ⌮ィ⟬࡟ࡼࡿ⇕ຊᏛᏳᐃᛶ࣐ࢵࣉࠋ
㸦ྑ㸧➨୍ཎ⌮ 0' ィ⟬࡟ࡼࡾᚓࡽࢀࡓ᭷ᮃᮦᩱࡢ /L ࢖࢜ࣥఏᑟᗘࠋ

- 502 -

ୖグࡢᮦᩱィ⟬ࡣ⤖ᬗࢆ௬ᐃࡋ࡚࠸ࡿࡀࠊᐇ㝿ࡢᅛయ㟁ゎ㉁ᮦᩱ࡟ࡣከࡃࡢ⢏⏺ࡀྵࡲࢀࡿࠋࡑࡋ࡚ࡇࡢ
⢏⏺ࡀ࢖࢜ࣥఏᑟࡢ᢬ᢠᡂศ࡜ࡋ࡚⪃࠼ࡽࢀ࡚ࡁࡓࠋࡇࢀࢆᚤどⓗほⅬ࠿ࡽ☜ㄆࡍࡿࡓࡵ࡟ᡃࠎࡣ *DUQHW ᆺ/L/D=U2 㸦//=2㸧 ᅛయ㟁ゎ㉁ࡢ௦⾲ⓗ࡞⢏⏺࡟╔┠ࡋࠊࠕᐩᓅࠖ➼ࢆ฼⏝ࡋࡓ኱つᶍ➨୍ཎ⌮ 0' ィ⟬ࢆᐇ⾜ࡋ࢖࢜ࣥఏᑟᗘࢆぢ✚ࡶࡗࡓࠋࡑࡢ⤖ᯝ Ȉ  ⢏⏺࡜࠸࠺Ᏻᐃ࡞㸦ࡘࡲࡾ⌧ᐇⓗ࡟ከᩘᏑᅾࡋ࠺ࡿ㸧⢏⏺࡛ࡣࠊ࢖࢜ࣥఏᑟᗘࡣࣂࣝࢡ୪ࡳ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ࢖࢜ࣥఏᑟᗘࡀప࠸ Ȉ  ⢏⏺࡜ẚ㍑ࡍࡿࡇ
࡜࡟ࡼࡾࠊࡇࡢ㧗࠸ఏᑟᗘࡀࠊ/L/L 㛫ࡢ㊥㞳ࡀ㐺ษ࡟ಖࡓࢀ࡚࠸ࡿࡇ࡜ࡀ୍せᅉ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ 㸧>@ࠋࡇࡢࡼ࠺࡟ /L 㛫ࡢ┦㛵ࡀ࢖࢜ࣥఏᑟᗘ࡟኱ࡁࡃᐤ୚ࡍࡿ࡜࠸࠺⌮ㄽࡢᐇド࡟ࡶᮏ◊✲ࡣ኱ࡁࡃ㈉⊩ࡋ࡚࠸ࡿࠋᅗ 㸦D㸧➨୍ཎ⌮ 0' ࡟ࡼࡾồࡵࡽࢀࡓ *DUQHW ᆺᅛయ㟁ゎ㉁ /L/D=U2 ࡢࣂࣝࢡ࠾ࡼࡧ ȈࠊȈ ⢏⏺ࡢ /L ࢖࢜ࣥ⮬ᕫᣑᩓಀᩘࠋ
㸦EG㸧⢏⏺㏆ഐ࡛ࡢ /L ࢖࢜ࣥศᕸࠋ/L㸸⥳ࠊ/D㸸ᶳࠊ=U㸸⤃ࠊ2㸸㉥ 㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụࡢ኱つᶍ㟁ᴟ㸫㟁ゎ㉁⏺㠃ࣔࢹ࡛ࣝࡢ኱ᇦⓗ⏺㠃ᵓ㐀ࡢゎ᫂
/$0036 ࢆ࣮࣋ࢫ࡜ࡋࡓ 5HG0RRQ ࢔ࣉࣜࢣ࣮ࢩࣙࣥࢆ⏝࠸࡚ࠊ㧗⃰ᗘ /L ሷ㟁ゎ㉁⁐ᾮ⣔࡟ 5HG 0RRQ
㸦50㸧ἲࢆ㐺⏝ࡋ࡚ࠊᅛయ㟁ゎᾮᒙ㛫㸦6(,㸧⭷ࡢᘏᛶࢆ᭱㐺࡟ࡍࡿሷ⃰ᗘࡀ࠶ࡿ࡜࠸࠺⤖ᯝࢆᚓࡓࠋࡋ࠿
ࡋࠊሷ⃰ᗘࡀ㧗ࡃ࡞ࡿ࡜ࠊᶵᲔⓗᏳᐃᛶࡀపୗࡋࠊ/L ࢖࢜ࣥ㟁ụࡢᛶ⬟ຎ໬࡟ࡘ࡞ࡀࡿࡇ࡜ࡀண᝿ࡉࢀࡿࠋ
ࡇࢀࡣࠊሷ⃰ᗘࡀ㧗ࡃ࡞ࡿ࡜ࠊ↓ᶵ≀࡟ᐩࢇࡔ◳࠸ 6(, ᒙࡀᙧᡂࡉࢀࡿࡇ࡜࡟㉳ᅉࡍࡿࠋࡇࢀࡽࡢࡇ࡜࠿ࡽࠊ
/L)6$ ⣔㟁ゎᾮࡢ㐺ษ࡞ㄪᩚࡀࠊ/L ࢖࢜ࣥ㟁ụࡢ㧗ᛶ⬟໬࠾ࡼࡧ⪏ஂᛶྥୖ࡟୙ྍḞ࡛࠶ࡿ࡜ゝ࠼ࠊᐇ㦂⤖ᯝࢆ⿬௜ࡅࡿィ⟬⤖ᯝࢆᚓࡓࠋࡲࡓࠊ࢚ࢳ࣮ࣞࣥ࢝࣎ࢿ࣮ࢺ㸦(&㸧⣔㟁ゎᾮ࠿ࡽ࡞ࡿ /L ࢖࢜ࣥ㟁ụ࡟࠾࠸࡚ࠊᐇ㝿ࡢ඘㟁᪉ἲࡢ୍ࡘ࡛࠶ࡿᐃ㟁఩඘㟁࡟ᑐᛂࡍࡿ 6(, ⭷ᙧᡂ 50 ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ6(, ⭷ࡢᛶ㉁ࡢ඘㟁㟁఩౫Ꮡᛶࢆㄪᰝࡋࡓࠋ㟁఩ᕪ  ࠿ࡽ 9 ࡢ⠊ᅖ࡛ᙧᡂࡋࡓ 6(, ⭷࡛ࡣࠊ✵Ꮝ⋡ࡀ 9 ࡛᭱ᑠ࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ⌮⏤࡜ࡋ࡚ࠊ࢞ࢫศᏊ࡛࠶ࡿ࢚ࢳࣞࣥ㸦&+㸧ࡢ⏕ᡂ㔞ࡀ 9 ࡛᭱ᑡ࡜࡞ࡿ
ࡓࡵࡔ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ6(, ⭷ࡢཌࡉࡶ 9 ࡛᭱ࡶⷧࡃ࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸦ᅗ 㸧ࠋ6(, ⭷ࡀཌࡃ࡞ࡿせᅉ࡜ࡋ࡚ࡣࠊ࢞ࢫศᏊຠᯝ࡜ࢡ࣮ࣟࣥ཯Ⓨຠᯝࡢ஧ࡘࡀ⪃࠼ࡽࢀࡿࠋ࢚ࢳࣞࣥ㸦&+㸧ࡣ඘㟁ึᮇ࡟࠾࠸࡚㟁఩ᕪࡀᑠࡉ࠸࡯࡝ከࡃ⏕ᡂࡉࢀࡿࠋ࢚ࢳࣞࣥ㸦࢞ࢫศᏊ㸧ࡣ↓ᴟᛶ࡛᥹Ⓨᛶࡀ㧗࠸ࡓࡵࠊ㟁఩ᕪࡀᑠࡉ࠸࡯࡝࢞ࢫศᏊ࡟ࡼࡿ 6(, ⭷ࡢᵓ㐀◚ቯࢆᘬࡁ㉳ࡇࡍࠋ௚᪉ࠊ㈇࡟ᖏ㟁ࡋࡓ㑏ඖ⏕ᡂ≀ࡣ㟁఩ᕪࡀ኱- 503 -

ࡁ࠸࡯࡝ࠊࢡ࣮ࣟࣥ཯Ⓨ࡟ࡼࡗ࡚ᵓ㐀◚ቯࢆᘬࡁ㉳ࡇࡍࠋࡇࢀࡽ஧ࡘࡢ┦཯ࡍࡿຠᯝ࡟ࡼࡗ࡚ࠊ6(, ⭷ࡣ 9 ࡛᭱ࡶⷧࡃ࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋᐃ㟁఩ 50 ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ࠊ6(, ⭷ᙧᡂ࡟ࡣࡇࢀࡽࡢຠᯝࡀ㔜せ࡛࠶ࡿ࡜࠸࠺ᐃ㟁఩඘㟁ࡢ≉ᚩࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᅗ ྛ㟁఩ᕪ࡟࠾ࡅࡿ࢚ࢳࣞࣥ㸦&+㸧ࡢ⏕ᡂ㔞࡜⭷ཌࠋ&+ ࡢ⏕ᡂ㔞࡜⭷ཌඹ࡟㟁఩ᕪ 9 ࡢ࡜ࡁ࡟᭱ᑠ࡜࡞ࡿࠋ

㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụࡢ࢖࢜ࣥఏᑟᗘࡢ㟁ゎᾮ⃰ᗘ౫Ꮡᛶࡢゎ᫂௧࿴㸰ᖺᗘ࡟ᵓ⠏ࡋࡓᡭἲࢆ⏝࠸࡚ࠊ➨୍ཎ⌮ 0' ィ⟬ࢆཧ↷⣔࡜ࡋࡓ $02(%$ ຊሙࡢࣃ࣓࣮ࣛࢱ᭱㐺໬ࢆ⾜࠸ࠊ⣙  ཎᏊ࠿ࡽ࡞ࡿ 00 ࡢ⃰ᗘࡢ /L%)(& 㟁ゎᾮࢆᑐ㇟࡟ࠊྂ඾ 0' ィ⟬ࡢ⤖ᯝ࠿ࡽ㟁ゎᾮࡢ࢖࢜ࣥఏᑟᗘࢆホ౯ࡋࡓࠋྠ᫬࡟ࠊࢺ࣏ࣟࢪ࢝ࣝࢹ࣮ࢱゎᯒ㸦7'$㸧ࡢᡭἲࢆ⏝࠸࡚㟁ゎᾮࡢཎᏊᵓ
㐀ࡀᣢࡘᗄఱᏛⓗ≉ᚩࢆᐃ㔞໬㸦ᅗ 㸧ࡋࠊ୺ᡂศศᯒ㸦3&$㸧࡟ࡼࡗ࡚⃰ᗘࡢ㐪࠸ࡀ㟁ゎᾮࡢᵓ㐀ࡢ࡝ࡇ࡟⌧ࢀࡿࡢ࠿ࢆㄪ࡭ࡓࠋ⣔ࢆᵓᡂࡍࡿከᵝ࡞ཎᏊ✀ࡢ⤌ࡳྜࢃࡏ࡛ࡇࡢసᴗࢆ⧞ࡾ㏉ࡋࠊᵓ㐀せ⣲ࢆ㠀⤒㦂ⓗ࡟཰㞟ࡋ࡚ࠊ7'$ ࡜ 3&$ ࡟ࡼࡾ୺ᡂศ್࡜ࡋ࡚ᐃ㔞໬ࡋࡓ㸦ᅗ 㸧ࠋᅗ  㸦D㸧/L%)(& ⣔ࡢྂ඾ 0' ࡢࢫࢼࢵࣉࢩࣙࢵࢺ㸦/L㸸⥳ࠊ%㸸㟷ࠊ)㸸ⷧ⣸ࠊ2㸸㉥ࠊ&㸸Ⲕࠊ+㸸ⓑ㸧ࠋ㸦E㸧& ࡜ 2 ࡢཎᏊ఩⨨ࡢ 7'$ ࡛ᚓࡽࢀࡓ  ḟࡢࣃ࣮ࢩࢫࢸࣥࢺ
ᅗ㸦3'㸧ࠋ- 504 -ᅗ 㸦D㸧/L%)(& ⣔ࡢ࢖࢜ࣥఏᑟᗘࡢ⃰ᗘ౫Ꮡᛶ㸦‫ە‬㸸0' ィ⟬࠿ࡽホ౯ࡋࡓࡶࡢࠊ‫ڸ‬㸸ᐇ㦂್㸧ࠋ㸦E㸧ከࡃࡢࢫࢼࢵࣉࢩࣙࢵࢺ࡟ᑐࡍࡿ 3' ࡢ➨  ୺ᡂศ࡜➨  ୺ᡂศࡢࣉࣟࢵࢺ㸦Ⰽࡣ⃰ᗘࡢ㐪࠸ࢆ⾲ࡍ㸧ࠋ࢖࢜ࣥఏᑟᗘࢆ┠ⓗኚᩘࠊᵓ㐀せ⣲ࢆᐃ㔞໬ࡋࡓ୺ᡂศ್ࢆㄝ᫂ኚᩘ࡜ࡍࡿᅇᖐศᯒࢆ⾜ࡗ࡚ᐤ୚ࡢ኱ࡁ
࡞ㄝ᫂ኚᩘࢆࢫࢡ࣮ࣜࢽࣥࢢࡋࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢᒁᡤ⎔ቃ࡟ᑐᛂࡍࡿ୺ᡂศ್㸯ࡘࡎࡘ࠿ࡽ࡞ࡿ㸰ࡘࡢㄝ᫂ኚᩘ࡛ࠊᖜᗈ࠸⃰ᗘᇦࡢ࢖࢜ࣥఏᑟᗘࢆⰋዲ࡟㸦5 ࢫࢥ࢔ 㸧⥺ᙧᅇᖐ࡛ࡁࡓ㸦ᅗ 㸧ࠋࡑࡢ㉳※ࢆ
㏫ゎᯒࡋࡓ࡜ࡇࢁࠊᏙ❧࢖࢜ࣥࡸ㙐≧࢖࢜ࣥࢡࣛࢫࢱࡢᮎ➃࡟఩⨨ࡍࡿ࢖࢜ࣥࡢࡼ࠺࡟ࠊ㟁Ⲵࡢ㍺㏦ࢆᐇຠ
ⓗ࡟ᢸ࠺࢖࢜ࣥࡢᒁᡤ⎔ቃࢆᢳฟ࡛ࡁ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ1D ࡸ 0Jࠊ3) ࡸ 3&ࠊ㘒࢖࢜ࣥ➼ࡢせ⣲࡟ࡘ࠸࡚ࡶホ౯࡜ゎᯒࢆ㐍ࡵࠊ▱ぢࡢᖜࡀᗈࡀࡾࡘࡘ࠶ࡿ

ᅗ ࢖࢜ࣥఏᑟᗘࡢィ⟬್㸦ᶓ㍈㸸/L ࡜ %) ࡟ᑐᛂࡍࡿྛ✵Ὕࡢ୺ᡂศ್
࠿ࡽࡢண 㸧࡜ほ್㸦⦪㍈㸸0' ィ⟬࠿ࡽࡢ┤᥋ホ౯㸧ࠋ ⇞ᩱ㟁ụࡢḞ㝗ศᕸࢆ⪃៖ࡋࡓ኱つᶍィ⟬࡟ࡼࡿᗘࡸḞ㝗⃰ᗘ࡟ࡼࡿゐ፹άᛶ࡬ࡢᙳ㡪ࡢゎ᫂ⓑ㔠௦᭰ᮦᩱࢆ⏝࠸ࡓ㟁ᴟゐ፹ࡢྍ⬟ᛶࢆ㏣ồࡍࡿࡓࡵ࡟ᶓ὾ᅜ኱ࢆ௦⾲࡜ࡍࡿ኱ᆺᐇ㦂ࢢ࣮ࣝࣉ࡜㐃ᦠࡋ࡚ࠊ㓟໬≀㟁ᴟゐ፹㸦W=U2[1[㸧ࡢ⇞ᩱ㟁ụ཯ᛂ ≉࡟㓟⣲㑏ඖ཯ᛂ ࡢάᛶࢆㄪ࡭ࡓࠋᐇ㦂࠿ࡽࡣẕ≀㉁
㸦W=U2㸧࡟ᩘࡢ㓟⣲✵Ꮝ࡜ࡑࢀ࡜ྠᩘ⛬ᗘࡢ❅⣲࡞࡝ࡢ୙⣧≀ࢆᑟධࡍࡿࡇ࡜࡟ࡼࡾࠊⓑ㔠୪ࡳࡢ㛤ᅇ㊰㟁ᅽࡀฟ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࡓࡵࠊ⌮ㄽ࡛ࡣୖグḞ㝗ࡀ⾲㠃௜㏆࡛࡝ࡢࡼ࠺࡟ศᕸࡋ࡚࠸ࡿ࠿ࠊࡑࡢ⤖ᯝ࡝ࡢࡼ࠺࡞ᶵᵓ࡛㓟⣲㑏ඖ཯ᛂࡀ㉳ࡇࡿࡢ࠿ࠊࡑࡢάᛶࡀ࡝ࡢ⛬ᗘ࡛࠶ࡿࡇ࡜ࡀண᝿ࡉࢀࡿࡢ࠿ࠊ࡜࠸ࡗࡓ

- 505 -

ၥ࠸࡟⟅࠼ࡿࡓࡵࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ㟁Ꮚ≧ែࡀ」㞧࡞㓟໬≀⾲㠃࡟࠾࠸࡚୙⣧≀ศᕸࢆィ⟬ࡍࡿࡓࡵ࡟ࡣࠊ➨୍ཎ⌮ࣔࣥࢸ࢝ࣝࣟィ⟬ࢆ⾜ࢃ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋ༢⣧࡟ぢ✚ࡶࡿ࡜ሙྜࡢᩘࡣ൨ࢆࡣࡿ࠿
࡟㉸࠼ࠊ㧗ᗘ࡞ࣔࣥࢸ࢝ࣝࣟἲࢆ⏝࠸࡚ࡶᩘⓒ୓㏻ࡾࡢᏳᐃ㓄⨨ࢆồࡵࡿᚲせࡀ࠶ࡾࠊࡑࡢࡲࡲ࡛ࡣ㺀ᐩᓅ㺁ࢆ⏝࠸࡚ࡶィ⟬᫬㛫ࡀ㊊ࡾ࡞࠸ࠋࡑࡢࡓࡵᩘ༓㏻ࡾࡢᏳᐃ㓄⨨ࢆ➨୍ཎ⌮ࣔࣥࢸ࢝ࣝࣟィ⟬࠿ࡽồࡵࠊࡑࡢ⤖ᯝࢆᶵᲔᏛ⩦ࡋ࡚᭷ຠ࣏ࢸࣥࢩࣕࣝࢆᵓ⠏ࡋࠊ᭱⤊ⓗ࡟᭷㝈 ᗘ࡛ࡢ୙⣧≀㓄⨨ࢆồࡵࡿ᪉ἲࢆྲྀࡾࠊ㺀ᐩᓅ㺁࡛ᐇ⾜ྍ⬟࡞ࣞ࣋ࣝ࡟ィ⟬㔞ࢆῶࡽࡋࡓࠋࡇࢀࡽࡢィ⟬ࢆࡍࡿᶵ⬟ࡣ࢔ࣉࣜࢣ࣮ࢩࣙࣥ DE,&6 ࡟ྵࡵࡓ㸦ᅗ 㸧ࠋᅗ Ḟ㝗ࢆᣢࡘ㓟໬≀࡜㓟ᛶỈ⁐ᾮࡢィ⟬ࣔࢹࣝࠋᅛయഃࡢḞ㝗ศᕸࠊᾮయഃ
ࡢ࢖࢜ࣥศᕸࡣࡑࢀࡒࢀ DE,&6 ࡜ (605,60 ࡛ồࡵࡓࠋィ⟬ࡢ⤖ᯝࠊ㓟⣲✵Ꮝࡣᵓ㐀ࢆ᭷ࡋ࡚㓄⨨ࡍࡿ୍᪉ࠊ❅⣲୙⣧≀ࡣ⾲㠃➨஧ᒙࡼࡾࡶ῝࠸఩⨨࡟ࣛࣥࢲ࣒
࡟ศᕸࡍࡿࡇ࡜࡞࡝ᐇ㦂࡜ᩚྜᛶࢆᣢࡗࡓᙧ࡛㓄⨨ࡢ≉ᚩࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡉࡽ࡟ࠊࡇࡢ▱ぢࢆ཯ᫎࡉࡏ
࡚㟁ᴟ⾲㠃ࢆࣔࢹࣜࣥࢢࡋࠊ㓟⣲㑏ඖ཯ᛂࡢ୰㛫యࡢ྾╔࢚ࢿࣝࢠ࣮ࢆ➨୍ཎ⌮ィ⟬ࡋࠊ཯ᛂࡢ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࢆᚓࡓ㸦ᅗ 㸧ࠋࡇࡇ࡛ࡣࠊᵝࠎ࡞཯ᛂ୰㛫యࡢᵓ㐀ࢆ࡛ࡁࡿࡔࡅ⥙⨶ⓗ࡟ᚓࡿࡓࡵ࡟ࠊVLPXODWHG
DQQHDOLQJ ࢆྵࡴᵝࠎ࡞ᡭἲࢆ㐺⏝ࡋࡓ㸦ྜ⌮ⓗ⥙⨶ィ⟬㸧ࠋࡇࡢィ⟬࠿ࡽࡣࠊୖグ୙⣧≀ࢆᑟධࡏࡎ࡜ࡶⓑ㔠୪ࡳࡢప࠸άᛶ໬࢚ࢿࣝࢠ࣮ࢆ♧ࡍࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࡑࡢάᛶࡣࠊ୙⣧≀ࡀᏑᅾࡋ࡚ࡶィ⟬⢭ᗘࡢ⠊ᅖෆ࡛ኚ໬ࡀ࡞࠸ࡇ࡜ࡶศ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟኱つᶍ࡞ィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊᐇ㦂࡜୍ぢ୙ᩚྜࡍࡿࢹ࣮ࢱࡀᚓ
ࡽࢀࡓࠋࡇࡢ⤖ᯝࡣᐇ㦂ࢧ࢖ࢻ࡟ᥦ౪ࡋࠊᐇ㦂⤖ᯝࡢゎ㔘ࡢ෌⪃ࡸ㟁ᴟ㛤Ⓨࡢ᪉㔪ࡢ෌⪃࡞࡝ࢆಁࡋࡓࠋᅗ  㓟⣲㑏ඖ཯ᛂࠋ㸦ᕥ㸧DVVRFLDWLRQPHFKDQLVP ࡟ࡼࡿ཯ᛂ⤒㊰ࡢ୍ࡘࠋ㸦ྑ㸧ᑐᛂࡍࡿ཯ᛂࡢ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺㸦㯮㸧ࠋ㓟⣲ཎᏊࡢ⛣ືࡀ㜼ᐖࡉࢀ࡚࠸ࡿሙྜࡣ㉥⥺ࡢࡼ࠺࡞᭤⥺࡜࡞ࡿࠋ㓟໬≀㟁ᴟ࡛ࡢ㓟⣲㑏ඖ཯ᛂ⤒㊰ࡢ᥈⣴ィ⟬ࠋ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚㓟⣲㑏ඖ཯ᛂࡢ୰㛫యࡢᏳᐃᛶࢆ
ồࡵࠊάᛶ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࠋ- 506 -

 ⇞ᩱ㟁ụࡢࢢࣛࣇ࢙ࣥᢸᣢ༢ཎᏊ㟁ᴟ࡟࠾ࡅࡿ㓟⣲㑏ඖ࣭&2 㓟໬཯ᛂᶵᵓゎ᫂
༢ཎᏊ 3W ࢆࢢࣛࣇ࢙࢚ࣥࢵࢪ࡟⤖ྜࡋࡓᵓ㐀࡟ࡘ࠸࡚ࠊ➨୍ཎ⌮㟁Ꮚ≧ែィ⟬࡜㐍໬ⓗ࢔ࣝࢦࣜࢬ࣒ࠊ࢞
࢘ࢫ㐣⛬ᅇᖐ࡟ᇶ࡙ࡃ௦⌮ࣔࢹࣝࢆ⤌ࡳྜࢃࡏࡓᡭἲ࡟ࡼࡾࠊ኱ᇦⓗ࡟Ᏻᐃ࡞ᵓ㐀ࢆ᥈⣴ࡋࡓࠋồࡲࡗࡓᵓ㐀࡟㓟⣲㑏ඖ཯ᛂࡸ &2 㓟໬཯ᛂࡢ཯ᛂᛶࢆㄪ࡭ࡿୖ࡛㔜せ࡞྾╔Ꮚ࡛࠶ࡿ &2 ࡸ 2+ ࡞࡝ࡢ྾╔≧ែࢆㄪ࡭ࠊ྾╔࢚ࢿࣝࢠ࣮ࢆồࡵࡓ㸦ᅗ 㸧ࠋᅗ ࢢࣛࣇ࢙ࣥࣜ࣎ࣥࡢ࢚ࢵࢪ࡟⤖ྜࡋࡓ༢୍ 3W ཎᏊୖ࡬ࡢ &2 ࡜ +2 ࡢ྾╔ᵓ㐀㸦3W㸸⅊ࠊ&㸸㯮ࠊ2㸸㉥ࠊ+㸸ⓑ㸧ࠋ&2 ࡢ㓟໬཯ᛂࡣ௨ୗࡢ཯ᛂ⣲㐣⛬࡛㐍ࡴ࡜⪃࠼ࡽࢀࡿࠋ
 &2 ÅÆ&2 +2 ÅÆ+2  +2 ÅÆ2+ +H
 &2 2+   ÅÆ &2+Hࡇࢀࡽࡢ཯ᛂ⣲㐣⛬ࡢ཯ᛂ㏿ᗘㄽࡼࡾ཯ᛂ㏿ᗘ U ࡣ௨ୗࡢࡼ࠺࡟࡞ࡿࠋ
‫ ݌ݔ݁ ן ݎ‬൤െͳ௉௧ ሻ௉௧ ሻሽ൨
ሼሺ‫ܧ‬஼ை െ ‫ܧ‬஼ைെ ሺ‫ܧ‬ைு െ ‫ܧ‬ைு
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ࡇࡇ࡛ࠊ‫ܧ‬஼ை ǡ ‫ܧ‬஼ை
ࡣ &2 ࡢ 3W ༢ཎᏊゐ፹ࠊ࠾ࡼࡧࠊ3W 㔠ᒓ⾲㠃ୖ࡬ࡢ྾╔࢚ࢿࣝࢠ࣮࡛࠶ࡾࠊ‫ܧ‬ைு ǡ‫ܧ‬ைுࡣ

2+ ࡢ 3W ༢ཎᏊゐ፹ࠊ࠾ࡼࡧࠊ3W 㔠ᒓ⾲㠃ୖ࡬ࡢ྾╔࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋࡍ࡞ࢃࡕࠊ&2 ࡢ྾╔ࡀᙅࡃࠊ୍᪉
2+ ࡢ྾╔ࡀᙉ࠸᪉ࡀ &2 㓟໬཯ᛂࡢ཯ᛂ㏿ᗘࡣ㏿ࡃ࡞ࡿࠋ
ࡑࡇ࡛ࠊ➨୍ཎ⌮ィ⟬࡜㐍໬ⓗ࢔ࣝࢦࣜࢬ࣒ࠊ࢞࢘ࢫ㐣⛬ᅇᖐἲࢆ⤌ࡳྜࢃࡏ࡚ồࡵࡓ 3W ༢ཎᏊࡀࢢࣛࣇ
࢙࢚ࣥࢵࢪ࡟ᢸᣢࡋࡓᵓ㐀࡬ࡢ &2 ࡢ྾╔࢚ࢿࣝࢠ࣮ࠊ࠾ࡼࡧࠊ2+ ࡢ྾╔࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋࡉࡽ࡟ 3W
⾲㠃ୖ࡬ࡢࡑࢀࡒࢀࡢศᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࡶồࡵࠊࡑࡢᕪࢆồࡵࡿࡇ࡜࡟ࡼࡾࠊ཯ᛂᛶࢆぢ✚ࡶࡿࡇ࡜ࡀ
ྍ⬟࡛࠶ࡿࠋࡑࡢ್ࢆᶓ㍈࡟ྲྀ⌮ࠊ⦪㍈࡟ 3W ༢ཎᏊࡢࢢࣛࣇ࢙࢚ࣥࢵࢪ࡬ࡢ྾╔࢚ࢿࣝࢠ࣮ࢆࣉࣟࢵࢺࡍࡿ
࡜ࠊࢢࣛࣇࡢୗ࡟⾜ࡅࡤ⾜ࡃ࡯࡝Ᏻᐃ࡞ᵓ㐀࡛࠶ࡾࠊࡲࡓࠊᕥ࡟⾜ࡅࡤ࠸ࡃ࡯࡝཯ᛂᛶࡢ㧗࠸ᵓ㐀࡛࠶ࡿࠋࡍ࡞ࢃࡕࠊࢢࣛࣇࡢᕥୗࡀ᭱ࡶᏳᐃ࡛཯ᛂᛶࡶ㧗࠸ 3W ゐ፹࡛࠶ࡿ࡜ゝ࠼ࡿ㸦ᅗ 㸧ࠋࢢࣛࣇࡢᕥୗ࡟ࡣ࠸ࡃ
ࡘ࠿ᵓ㐀ࡀศᕸࡋ࡚࠾ࡾࠊࡇࢀࡽࡢᵓ㐀ࡣ᭱ࡶゐ፹࡜ࡋ࡚᭷ᮃ࡞ᵓ㐀࡛࠶ࡿ࡜࠸࠼ࡿࠋࡑࡇ࡛ࠊࡇࢀࡽࡢゐ፹ᵓ㐀࡟㛵ࡋ࡚ࠊࡉࡽ࡟ᐇ㝿࡟ &2 㓟໬཯ᛂ㐣⛬ࡢάᛶ໬㞀ቨ࡟ࡘ࠸࡚௒ᚋồࡵ࡚࠸ࡃணᐃ࡛࠶ࡿ

- 507 -ᅗ ࢢࣛࣇ࢙࢚ࣥࢵࢪ࡟⤖ྜࡋࡓ 3W ༢୍ཎᏊゐ፹ࡢ཯ᛂᛶ̺Ᏻᐃᛶᅗࠋ
ᶓ㍈ࡣ &2 㓟໬཯ᛂ࡟ᑐࡍࡿ 3W ༢ཎᏊゐ፹ࡢ཯ᛂᛶࠋ⦪㍈ࡣࢢࣛࣇ࢙
࢚ࣥࢵࢪ࡬ࡢ 3W ༢ཎᏊࡢ྾╔࢚ࢿࣝࢠ࣮ࠋ

⇞ᩱ㟁ụࡢ㟁ゎ㉁⭷ࣂࣝࢡ࡟࠾ࡅࡿ≀㉁㍺㏦࣑ࢡࣟᶵᵓࡢゎ᫂㧗ศᏊ㟁ゎ㉁⭷୰࡛࣑ࢡࣟ࡟┦ศ㞳ࡋ࡚࠸ࡿ㧗ศᏊ┦࡜Ỉ┦ࡢ୙ᆒ୍ᛶࡢ✵㛫ࢫࢣ࣮ࣝࡣ 㹼QP ࡛࠶ࡾࠊࡑࡇ࡛⏕ࡌࡿ࢚ࢿࣝࢠ࣮㞀ቨࢆ஌ࡾ㉺࠼࡚ࢭࣝࡢ➃࠿ࡽ➃ࡲ࡛ࡢ㐠ືࢆ㏣㊧ࡍࡿࡓࡵ࡟ࡣࠊȝV ࣮࢜ࢲ࣮ࡢ
ࢩ࣑࣮ࣗࣞࢩࣙࣥࡀせồࡉࢀࡿࠋࡇࢀࡣࠊ㺀ᐩᓅ㺁ࢆ⏝࠸࡚ࡶィ⟬ࡀᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡟࠾࠸࡚ࡣࠊ⌧ᐇ⣔ࢆ᱁Ꮚࣔࢹࣝ࡟⢒ど໬ࡋࠊ᱁Ꮚୖࡢ⢏Ꮚࡢᣑᩓ㐠ືࢆືⓗ 0& ἲ࡟ࡼࡗ
࡚㏣㊧ࡋࠊࡑࡢ㌶㊧ࢆゎᯒࡍࡿ࡜࠸࠺ᡓ␎ࢆ࡜ࡿࠋࡘࡲࡾࠊ୙ᆒ୍⣔ࢆ✵㛫ⓗ࡟⢒ど໬ࡋࡓୖ࡛ࠊ㐠ື࡟ࡘ࠸࡚ࡶ⢒ど໬ࢆ᪋ࡍࠋࡇࡢ‽ഛ࡜ࡋ࡚ࠊ௧࿴㸰ᖺᗘ࡟ࡣࡍ࡛࡟㟁ゎ㉁⭷ࡢᇶᮏࢭࣝࢆ࣓ࢵࢩࣗ࡟ศ๭ࡋ࡚఩
⨨࡟౫ᏑࡍࡿỈ⣲ࡢᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ࢆồࡵࡓࠋ✵㛫ࢆ⁥ࡽ࠿࡟グ㏙ࡍࡿࡓࡵ࡟ࡣࠊ ಶࡢ࣓ࢵࢩࣗࢆᚲせ࡜ࡋࡓࡀࠊ Ⅼࡢ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡣ㺀ᐩᓅ㺁࡞ࡽ࡛ࡣࡢࡶࡢ࡛࠶ࡿࠋ
௧࿴㸱ᖺᗘࡣࠊ⏕ᡂࡉࢀࡿ⢏Ꮚࡢ㌶㊧ࡀ࣏ࢸࣥࢩࣕࣝ࡜ᣑᩓಀᩘࡀ࡜ࡶ࡟఩⨨࡟౫Ꮡࡍࡿᣑᩓ᪉⛬ᘧࢆ‶ࡓࡍ࡜࠸࠺᪂ࡓ࡞ 0HWURSROLV ᆺࡢ㑄⛣☜⋡ࢆᑟฟࡋࠊࡇࢀࢆ⏝࠸࡚ືⓗ 0& ィ⟬ࢆᐇ᪋ࡋࡓࠋࡇࢀ࡟ࡼࡾࠊ
Ỉ⣲ศᏊࡢ㟁ゎ㉁⭷୰࡟࠾ࡅࡿ኱ᇦⓗ࡞ᣑᩓᣲືࡀゎᯒྍ⬟࡜࡞ࡾࠊᚓࡽࢀࡓᾐ㏱ಀᩘࡣᐇ㦂್࡜Ⰻ࠸୍⮴ࢆࡳࡓ㸦ᅗ 㸧>@ࠋᅗ ఩⨨࡟౫Ꮡࡍࡿᣑᩓಀᩘ࡜࣏ࢸࣥࢩࣕࣝ࠿ࡽ᪂つືⓗ 0& ἲ࡛ồࡵࡓ㧗ศᏊ㟁ゎ㉁⭷୰࡟࠾ࡅࡿỈ⣲ࡢࢡࣟࢫ࣮ࣜࢡ࡟㛵ࢃࡿ኱ᇦⓗ࡞ᣑᩓಀᩘ࡜ࠊ㏱㐣ಀ
ᩘࠋ㏱㐣ಀᩘࡢィ⟬್ࡣࠊᐇ㦂್࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ

- 508 -

ືⓗ 0& ィ⟬ࡢィ⟬㈇Ⲵࡣᴟࡵ࡚㍍ࡃࠊࡍ࡛࡟ᇶᮏࢭࣝࡢᕥ➃࠿ࡽྑ➃࡟⮳ࡿ  ௨ୖࡢỈ⣲ࡢᣑᩓ⤒㊰ࢆᚓ࡚࠾ࡾࠊ⌧ᅾࢹ࣮ࢱࢧ࢖࢚ࣥࢫⓗ࡞ゎᯒࢆ⾜ࡗ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫   ۻ‬ᮡ㔝 ಟ ࠕ%D/L R[\K\GULGH ࡟࠾ࡅࡿ㞟ᅋ㐠ືࡢゎᯒࠖ ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒
㸦3&R06㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍  ࢜ࣥࣛ࢖ࣥ 㤋ᒣ ెᑦࠕ඲ᅛయ㟁ụᮦᩱࡢ࢖࢜ࣥ㍺㏦ᶵᵓ࡟㛵ࡍࡿィ⟬ண ࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ 㛗ᒸ ṇ㝯ࠕ஧ḟ㟁ụࡢࡓࡵࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜≉ᛶゎᯒࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ ㉥ᮌ ࿴ேࠕᵓ㐀ⓗ≉ᚩ࡟ᇶ࡙ࡃ㟁ゎ㉁୰ࡢ࢖࢜ࣥఏᑟ࣓࢝ࢽࢬ࣒ࡢゎᯒࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ ᮡ㔝 ಟࠕ᪂ᆺ⇞ᩱ㟁ụࡢࡓࡵࡢ➨୍ཎ⌮≀㉁⛉Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ ᳃ᕝ Ⰻᛅࠕࢢࣛࣇ࢙ࣥᢸᣢ༢ཎᏊ㔠ᒓゐ፹࡟ࡼࡿ⇞ᩱ㟁ụ㟁ᴟゐ፹཯ᛂ࡟㛵ࡍࡿ◊✲ࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ ⸨ᮏ ࿴ኈ ࠕ02'</$6 ࡢ㛤Ⓨ࠾ࡼࡧ⇞ᩱ㟁ụ㧗ศᏊ㟁ゎ㉁⭷ࠊ㟁ᴟ⏺㠃ࡢ඲ཎᏊศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥࠖ 㺀ᐩᓅ㺁㟁ụㄢ㢟➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧 ࢜ࣥࣛ࢖ࣥ
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6X]XNL.HL6KLJHPDWVX7DNDIXPL<DPDPRWR5\RML.DQQR+HQD'DV<RVKLWDND7DWH\DPD0DVDNL$]XPD
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DQG R[\JHQ PROHFXOHV LQ SRO\PHU HOHFWURO\WH PHPEUDQHV ,QVLJKWLQWR GLIIXVLRQ SDWKV´ - &KHP 3K\V 
  '2,

- 509 -

┬࢚ࢿࣝࢠ࣮ḟୡ௦༙ᑟయࢹࣂ࢖ࢫ㛤Ⓨࡢࡓࡵࡢ㔞Ꮚㄽ࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥ
Quantum-theory-based multiscale simulation for the development of thenext-generation power devices‫ۑ‬ᢲᒣ῟ 1ࠊࣈ࢖ ࢩ࢚࢟࢘ ࣑ 1ࠊ஭ᮏᩥ⿱ 1ࠊ⨾㔛ຕኟ༡ 2ࠊᯇୗ㞝୍㑻 3ࠊᐮᕝ⩏⿱ 4ࠊ
ⲡሙᙲ 4ࠊᑠ㔝೔ஓ 5ࠊ᳜ᮏග἞ 5ࠊỤୖ႐ᖾ 6ࠊไ㔝࠿࠾ࡾ 1ྡྂᒇ኱Ꮫ ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤࠊ2 ኱㜰኱ᏛᕤᏛ◊✲⛉ࠊ3 ᮾிᕤᴗ኱Ꮫ≀㉁᝟ሗ
༟㉺◊✲㝔ࠊ4 ஑ᕞ኱Ꮫᛂ⏝ຊᏛ◊✲ᡤࠊ5 ⚄ᡞ኱ᏛᕤᏛ◊✲⛉ࠊ6 ໭ᾏ㐨኱ᏛᕤᏛ◊✲㝔

1

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◊✲┠ⓗ
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୺ࡓࡿᡭἲࡣࠊ
ᐦᗘỗ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㸧࡛࠶ࡿࠋྠࡌࡃᐇ✵㛫ᡭἲ࡛࠶ࡿ RSPACEࢥ࣮ࢻࡶే⏝ࡉࢀࡿࠋࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘ㸦NEGF: Non-Equilibrium Green’s
Function㸧ἲ࡟ࡼࡗ࡚ᐇ⾜ࡉࢀࡿࠋNEGF ࢥ࣮ࢻࡣ RSDFT ࢥ࣮ࢻ࡜⤫ྜࡉࢀ࡚࠸ࡿࠋ࠸ࡎࢀࡢࢥ࣮ࢻࡶᮏࢢ
࣮ࣝࣉ࡟࠾ࡅࡿ⊂⮬㛤Ⓨࡢࡶࡢ࡛࠶ࡿࠋࡲࡓ௒ᖺᗘࠊࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࢆά⏝ࡋࡓ࣮࢜ࢲ࣮N࣭orbitalfree DFT ࢥ࣮ࢻࡶ㛤Ⓨࡉࢀࡓࠋ

3

◊✲ᡂᯝ

SiC(0001)ᡂ㛗⾲㠃࡛ࡢ྾╔ཎᏊࡢᣑᩓᶵᵓࡢゎ᫂࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࠊ࡜ࡃ࡟ࢫࢸࢵࣉࣇ࣮࣭࣮ࣟࣔࢻ࡛ࡢᡂ㛗ࡢ⣲㐣⛬ࡣࠊi) Ẽ┦࠿ࡽᡂ㛗ᖹ㠃࡬ࡢ཯ᛂศᏊࡢ㣕᮶ࠊii) ཯ᛂศᏊࡢ⾲㠃ࢸࣛࢫୖ࡛ࡢศゎ཯ᛂࠊiii) ศゎ⏕ᡂ≀ࡢࢸࣛࢫୖ࠾ࡼࡧࢫࢸࢵࣉ➃㏆ഐ࡛
ࡢᣑᩓࠊiv) ࢫࢸࢵࣉ➃࠿ࡽࡢ⤖ᬗⷧ⭷࡬ࡢᵓᡂඖ⣲ࡢྲྀࡾ㎸ࡳࠊࡢ㸲ࡘࡢ㐣⛬࡟ศ㢮࡛ࡁࡿࠋ௒ᖺᗘࠊSiC
ࡢ CVD ᡂ㛗࡟࠾ࡅࡿ iii)ࡢᣑᩓࢆ DFT ィ⟬࡛ㄪ࡭ࡓࠋලయⓗ࡟ࡣࠊࡍ࡛࡟ᡃࠎࡢ DFT ィ⟬࡛᫂ࡽ࠿࡟࡞ࡗ
ࡓỈ⣲ཎᏊ࡟⿕そࡉࢀ࡚࠸࡞࠸ SiC(0001)⾲㠃ୖ࡛ࡢࠊ✲ᴟࡢศゎ཯ᛂ⏕ᡂ≀࡛࠶ࡿ SiࠊCࠊH ࢔ࢻཎᏊ㸦adatom㸧ࡢᣑᩓࢆㄪ࡭ࡓࠋ
ィ⟬ࡣ⾲㠃ࢆࢫࣛࣈᶍᆺ࡛ࢩ࣑࣮ࣗࣞࢺࡋࠊRSDFT ࢥ࣮ࢻࢆ⏝࠸࡚⾜ࡗࡓࠋᣑᩓ⤒㊰ࡢỴᐃ࡜ᑐᛂࡍࡿά

- 510 -

ᛶ໬࢚ࢿࣝࢠ࣮ࡢᑟฟࡣࠊྛ࢔ࢻཎᏊࡢ⾲㠃(x,y)ᗙᶆࢆᅛᐃࡋࠊ௚ࡢ⮬⏤ᗘࢆᵓ㐀⦆࿴ࡉࡏࠊᚓࡽࢀࡓ඲࢚
ࢿࣝࢠ࣮ࡢ➼㧗⥺ᅗ㸦landscape㸧࡟ࡼࡾ⾜ࢃࢀࡓ㸦ᅗ 1㸧ࠋ⾲㠃ࢸࣛࢫࡢཎᏊᵓ㐀ࡣ 3x4 ࡢࢫ࣮ࣃ࣮ࢭࣝᶍᆺ
࡛ࡢᏳᐃᵓ㐀ィ⟬࡟ࡼࡾࠊ2x1 ࡢ⾲㠃ཎᏊ buckled ᵓ㐀ࡀᚓࡽࢀࡓࡢ࡛ࠊࡑࢀࢆᵓ㐀ࣘࢽࢵࢺ࡜ࡋ࡚⏝࠸ࡓࠋࢫ ࢸࢵࣉᵓ㐀ࡣ௨๓ࡢᡃࠎࡢ DFT ィ⟬㸦Seino, Oshiyama: APEX, 2020; PRB 2020㸧ࡢ⤖ᯝࢆ⏝࠸ࡓࠋᅗ 1㸸SiC(0001)⾲㠃ࢸࣛࢫୖ࡛ࡢ SiࠊCࠊH ࢔ࢻཎᏊࡢ⾲㠃఩⨨࡟ᑐࡍࡿ඲࢚ࢿࣝࢠ࣮ࡢ➼㧗⥺ᅗࠋ࢚ࢿࣝࢠ࣮ࡢ༢఩ࡣ eVࠊ࢚ࢿࣝࢠ࣮ཎⅬࡣࡑࢀࡒࢀࡢ࢔ࢻཎᏊࡢ᭱Ᏻᐃ఩⨨࡛ࡢ྾╔࢚ࢿࣝࢠ࣮ࠋ
Ᏻᐃ྾╔఩⨨ T4ࠊH3 ࡀ♧ࡉࢀ࡚࠸ࡿࠋ

ᅗ 2㸸(a)SiC(0001)⾲㠃 Si2 ࢫࢸࢵࣉᵓ㐀ࡢഃ㠃ᅗࠋ㟷ࠊ⥳ࡣ Si ཎᏊࠊⲔࠊ㯤ࡣ C ཎᏊࢆ♧ࡍࠋ(b)Si2 ࢫࢸࢵࣉ㏆ഐ㸦ᕥࡀୖ᪉ࢸࣛࢫࠊྑࡀୗ᪉ࢸࣛࢫ㸧࡛ࡢ Si ࢔ࢻཎᏊࡢ㠃ෆ఩⨨࡟ᑐࡍࡿ඲࢚ࢿ
ࣝࢠ࣮ࡢ➼㧗⥺ᅗࠋ
ᅗ 1 ࡣࠊྛ࢔ࢻཎᏊ࡟ᑐࡍࡿ⾲㠃ࢸࣛࢫୖ࡛ࡢ඲࢚ࢿࣝࢠ࣮➼㧗⥺ᅗ࡛࠶ࡿࠋᏳᐃ࡞྾╔఩⨨࡜ࡋ࡚ࡣࠊ
T4 ࢧ࢖ࢺ㸦⾲㠃ୗ C ཎᏊࡢ┿ୖ㸧
ࠊH3 ࢧ࢖ࢺ㸦⾲㠃ཎᏊභゅᙧࡢ┿୰㸧ࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡿࠋSi ࢔ࢻཎᏊࡢ
᭱Ᏻᐃ఩⨨ࡣ T4(2)ࢧ࢖ࢺ࡛࠶ࡾ㸦࢝ࢵࢥෆࡢᩘᏐࡣ㣕ࡧฟࡓ⾲㠃 Si ཎᏊ࡜ࡢ࣎ࣥࢻࡢᩘࢆ♧ࡋ࡚࠸ࡿ㸧ࠊᚓࡽࢀࡓᣑᩓ⤒㊰ࡣࠊ[1-21]㸦භ᪉ᬗ࡛ࡣ[1-100]㸧᪉ྥ࡟ࡣ࣭࣭T4(2)࣭H3(2)࣭T4(1)࣭H3(1)࣭T4(2)࣭࣭ࠊ[10-1]㸦[1120]㸧᪉ྥ࡟ࡣ࣭࣭T4(2)࣭H3(1)࣭T4(2)࣭H3(1)࣭T4(2) ࣭࣭࡛࠶ࡿࠋᑐᛂࡍࡿᣑᩓࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡣ 0.65 eV
㹼 0.68 eV ࡛࠶ࡾࠊSi ࢔ࢻཎᏊࡢࢸࣛࢫୖ࡛ࡢᣑᩓࡣ➼᪉ⓗ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋC ࢔ࢻཎᏊࡢ྾╔఩⨨ࠊᣑᩓ⤒㊰ࡣ Si ࢔ࢻཎᏊ࡜ྠࡌ࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋᣑᩓࡀ➼᪉ⓗ࡛࠶ࡿࡇ࡜ࡶྠᵝ࡛࠶ࡿࠋࡋ࠿ࡋࡑࡢ࢚
ࢿࣝࢠ࣮ࡣ኱࠸࡟␗࡞ࡾࠊᣑᩓࡢάᛶ໬࢚ࢿࣝࢠ࣮1.45 eV ࡜ồࡵࡽࢀࡓࠋH ࢔ࢻཎᏊࡢ྾╔఩⨨ࡣ T1(1)࡜
T1(2)࡛࠶ࡾࠊᣑᩓάᛶ໬࢚ࢿࣝࢠ࣮ࡣ 1.15 eV㹼1.35 eV ࡜ồࡵࡽࢀࡓࠋࡇࡇ࡛ᚓࡽࢀࡓࢸࣛࢫୖ࡛ࡢᣑᩓ≉ᛶࡣࠊ࢟ࢿࢸ࢕ࢵࢡࢫ࡟ᑐࡍࡿ௒ᚋࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᅵྎ࡜࡞ࡿ࡛࠶ࢁ࠺ࠋ
ࢫࢸࢵࣉᵓ㐀࡟ࡘ࠸࡚ࡣࠊ௨๓ࡢᡃࠎࡢィ⟬࡛ヲ⣽࡞ᵓ㐀ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋࡲࡓࡑࡢ⏕ᡂ࢚ࢿࣝࢠ
࣮ࡶồࡵࡽࢀ࡚࠾ࡾࠊSi2 ࢫࢸࢵࣉ㸦ᅗ 2(a)ཧ↷㸧ࡀ᭱ࡶฟ⌧ࡋࡸࡍ࠸ᵓ㐀࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡑࡇ

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࡛ࡇࡢ Si2 ࢫࢸࢵࣉ㏆ഐ࡛ࡢ඲࢚ࢿࣝࢠ࣮➼㧗⥺ᅗࢆồࡵࠊᣑᩓ⤒㊰࡜άᛶ໬࢚ࢿࣝࢠ࣮ࢆㄪ࡭ࡓࠋ➼㧗⥺ᅗࡢ୍౛࡜ࡋ࡚ࠊSi ࢔ࢻཎᏊ࡟ᑐࡍࡿࡶࡢࢆᅗ 2(b)࡟♧ࡍࠋࢸࣛࢫୖ࡛ࡢ➼㧗⥺ᅗ㸦ᅗ 1㸧࡜ࡣ࠿࡞ࡾ㊃ࢆ␗࡟ࡋ࡚࠸ࡿࠋᅗ  ࡣỴᐃࡉࢀࡓᣑᩓ⤒㊰࡜ࡑࡢ⤒㊰࡟ἢࡗࡓ඲࢚ࢿࣝࢠ࣮ࡢኚ໬࡛࠶ࡿࠋࢫࢸࢵࣉ➃㏆ഐୖ᪉ࢸࣛࢫ࡛
ࡢᏳᐃ఩⨨࡜ࡋ࡚ࡣ H3uࠊT4uࠊT1u ࡞࡝ࡀ࠶ࡾࠊୗ᪉ࢸࣛࢫ࡛ࡣ H3d ࡀᏳᐃ࡛࠶ࡿࠋࡇࢀࡽࢆฟⓎⅬ࠶ࡿ࠸ࡣ฿㐩Ⅼ࡜ࡍࡿᣑᩓ⤒㊰ࡀᅗ 3 ࡟♧ࡉࢀ࡚࠸ࡿࠋSi ࢔ࢻཎᏊ࡟ࡘ࠸࡚ࡣࠊࢫࢸࢵࣉ㏆ഐ࡛ࡣࢸࣛࢫୖ࡟ẚ࡭ࠊ㢧ⴭ࡞άᛶ໬࢚ࢿࣝࢠ࣮ࡢቑຍࡀぢࡽࢀࡿࠋࡇࢀࡣᚑ᮶ࡢ⌧㇟ㄽ࡟࠾࠸࡚ࠊEhrlich-Schwoebel (ES)ຠᯝ࡜ࡋ࡚
ᑟධࡉࢀ࡚ࡁࡓࡶࡢ࡛࠶ࡾࠊࡑࡢ㔞Ꮚㄽィ⟬࡟ࡼࡿ⿬௜ࡅ࡜࡞ࡗ࡚࠸ࡿࠋࡋ࠿ࡋࠊC ࢔ࢻཎᏊ࡟ࡓ࠸ࡋ࡚ࡣ
ࡑࡢࡼ࠺࡞ ES ຠᯝࡣ࡯࡜ࢇ࡝ぢࡽࢀ࡞࠸ࡇ࡜ࡀึࡵ࡚ࢃ࠿ࡗࡓࠋ㏫࡟ࢃࡎ࠿࡛ࡣ࠶ࡿࡀࠊάᛶ໬࢚ࢿࣝࢠ࣮ࡢῶᑡࡶぢࡽࢀࠊ㏫ ES ຠᯝ࡜ࡶゝ࠼ࡿࠋ࠸ࡎࢀ࡟ࡋ࡚ࡶࠊ௒ᅇࡢィ⟬ุ࡛᫂ࡋࡓᣑᩓ⤒㊰άᛶ໬࢚ࢿࣝࢠ࣮
ࡢᐃ㔞ⓗỴᐃࡣࠊᡂ㛗⣲㐣⛬ࡢゎ᫂ࡢࣉࣟࢺࢱ࢖ࣉ࡜࡞ࡿࡶࡢ࡛࠶ࢁ࠺ࠋ

ᅗ 3㸸SiC(0001)⾲㠃 Si2 ࢫࢸࢵࣉ㏆ഐ࡛ࡢྛ࢔ࢻཎᏊࡢᣑᩓ⤒㊰㸦ୗᅗ㸧࡜ࡑࡢ⤒㊰࡟ἢࡗࡓ඲࢚
ࢿࣝࢠ࣮ࡢࣉࣟࣇ࢓࢖ࣝ㸦ୖᅗ㸧ࠋ

GaN/InN ᴟ➃࣑ࢫ࣐ࢵࢳ⏺㠃࡛ࡢ᪂ᵓ㐀Ⓨぢ᱁Ꮚ୙ᩚྜࡢ࣊ࢸࣟᵓ㐀⏺㠃࡛ࡣࠊ⏕ᡂࡉࢀࡓ⭷ࡢཌࡉࡀࠊ࠶ࡿ⮫⏺⭷ཌࢆ㉸࠼ࡿ࡜⏺㠃㉳ᅉࡢࢫࢺࣞ
ࢫࢆ⦆࿴ࡍࡿࡓࡵࡢ࣑ࢫࣇ࢕ࢵࢺ㌿఩ࡀ⏕ࡌࡿࡇ࡜ࡣࡼࡃ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ᱁Ꮚ୙ᩚྜࡀᴟࡵ࡚኱ࡁ
࠸ሙྜࠊ⏺㠃ᵓ㐀ࡀ࡝࠺࡞ࡿ࠿ࡣࢃ࠿ࡗ࡚࠸࡞࠸ࠋྡྂᒇ኱Ꮫᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤ஬༑ᔒࢢ࣮ࣝࣉ
࡛ࡣࠊ10%ࡢ᱁Ꮚ୙ᩚྜࡀᏑᅾࡍࡿ GaN/InN ࣊ࢸࣟᵓ㐀࡛ࠊ࣑ࢫࣇ࢕ࢵࢺ㌿఩ࡢᏑᅾࡋ࡞࠸ᖹᆠ࡞⏺㠃ࡀฟ⌧ࡍࡿࡇ࡜ࢆⓎぢࡋࡓࠋᖹ㠃㟁Ꮚ㢧ᚤ㙾෗┿࡛ࡣࠊ10%ࡢ࿘ᮇࡢ㐪࠸࡟ࡼࡿࣔ࢔ࣞ⦤ࡶほࡉࢀ࡚࠸ࡿࠋ

ཎᏊࢫࢣ࣮࡛ࣝ࡝ࡢࡼ࠺࡞ᵓ㐀࡟࡞ࡗ࡚࠸ࡿࡢ࠿ࠊᴟࡵ࡚⯆࿡῝࠸ࠋRSDFT ࢥ࣮ࢻࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡿᵓ㐀᥈⣴ࡢ⤖ᯝࠊᏳᐃᵓ㐀ࡀᚓࡽࢀࡓࠋᖹ㠃ᅗ࡛ࡣࣔ࢔ࣞ≧ࡢࣃࢱ࣮ࣥࡶᚓࡽࢀࡓࠋ᩿㠃㏱㐣㟁Ꮚ㢧ᚤ㙾෗┿㸦┬␎㸧࡜ィ⟬࡛ᚓࡽࢀࡓ᩿㠃࢖࣓࣮ࢪࡢẚ㍑ࡶⰋዲ࡛࠶ࡿࠋᚓࡽࢀࡓᡂᯝࡣㄽᩥ‽ഛ୰࡛࠶ࡿࠋ

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4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ᣍᚅㅮ₇㸦୍㒊㸧(1) A.

Oshiyama,“Computics

Approachto

Dislocation-Impurity

Complexes

andInterface

Characteristics of GaN Devices" The 31st Int Conf Defects in Semiconducotors (Oslo, Norway, July
26-30, 2021, online).
(2) (Plenary) A. Oshiyama, “Computics Approach in Science of Power Electronics" 1st Int Conf on
Computational Science and Data Analytics" COMDATA 2021 (November 21-24, 2021, Kuala Lumpur,
Malaysia).
(3) (Keynote) Akira Kusaba, Application of Machine Learning Methods to More Quantitative GaN
MOVPE Modeling, The 2nd International Symposium on Wide Gap Semiconductor Growth, Process
and Device Simulation, Nagoya (hybrid format), 2022.01.11-13.
(4) T. Ono, "DFT study on defects at SiC MOS interface: electronic structure and formation mechanism"
The 3rd International Workshop on Materials Science and Advanced Electronics Created by
Singularity (IWSingularity 2022)/The 2nd International Symposium on Wide Gap Semiconductor
Growth, Process and Device Simulation (ISWGPDs 2022) (January 11-13, 2022, Nagoya, Japan).
(5) K. M. Bui, K. Shiraishi, and A. Oshiyama, Density Functional Theory study of Step Flow Growth ofGallium Nitride, The 2nd International Symposium on Wide Gap Semiconductor Growth, Process
and Device Simulation, Nagoya (hybrid format), 2022.01.11-13.
(6) G. Mil'nikov and N. Mori, "Application of the R-matrix approach to large scale NEGF simulations"
Int Symp on Wide Gap Semiconductor Growth, Process and Device Simulation 2022 (January 11-12,
2022, online).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) մK. Seino and A. Oshiyama, “Microscopic mechanism of adatom diffusion on stepped SiC surfaces
revealed by first-principles calculations" Appl. Surf. Sci. 561, 149927 (2021).
(2) մK. Chokawa, K. Shiraishi and A. Oshiyama, “Defect-free interface between amorphous (Al2O3)1x(SiO2)x revealed by first-principle molecular dynamics simulations" Appl. Phys. Lett. 119, 011602(2021)(3) մF. Imoto, M. Imada and A. Oshiyama, “Order-N orbital-free density-functional calculations withmachine learning of functional derivatives for semiconductors and metals" Phys. Rev. Research 3,033198 (2021).
(4) A. Kusaba, Y. Kangawa, T. Kuboyama and A. Oshiyama, “Exploration of a large-scale reconstructedstructure on GaN(0001) surface by Bayesian optimization” Appl. Phys. Lett. 120, 021602 (2022).
(5) A. Kusaba, R. M. Kurniawan, P. Kempisty, Y. Kangawa, “DFT modeling of unintentional oxygen
incorporation enhanced by magnesium in GaN(0001) and AlN(0001) growth surfaces during metalorganic vapor-phase epitaxy”, Phys. Status Solidi B, 2022, 2100430. (in Press)(6) N. Mori, A. Komada, and G. Mil'nikov, "Comparison of linear and quadratic dispersion models forphonon transport in one-dimensional mass-disordered systems" APL Materials, 9, 08112 (2021).
(7) M. Uemoto, N. Komatsu, Y. Egami and T. Ono, "First-Principles Study on Structure and Anisotropyof High N-atom Density Layer in 4H-SiC" J. Phys. Soc. Jpn. 90, 124713 (2021).
(8) M. Tsunasaki, T. Ono, and M. Uemoto, "Theoretical investigation of vacancy related defects at 4HSiC(000-1)/SiO2 interface after wet oxidation" Jpn. J. Appl. Phys. 61, SH1001 (2022).

- 513 -

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1.

"Solvation shell dynamics of supercritical water–cyclohexane mixtures in relation to thetranslational and rotational dynamics as studied by molecular dynamics simulation"
Ken YOSHIDA and Haruka Yoshioka
AIP Advances, 11(7), 075219 (2021)

2.

"Temperature dependence of water cluster on functionalized graphite"
Toshihide Horikawa, Ryuto Yuasa, Ken YOSHIDA and D.D. Do
Carbon, 183, 380-389 (2021)

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Angew. Chem. Int. Ed., , anie.202108283 (2021)

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J. Am. Chem. Soc., 143(34), 13865-13877 (2021)

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"Derivation of coarse-grained force fields for buckling-induced topological defects of liquid
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Toshio Kubota and Tomohiro Agou
Polym Int (2021), https://doi.org/10.1002/pi.6291

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Inorganica Chimica Acta, 527, 120533 (2021)

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BCSJ, 94(7), 1815-1822 (2021)

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J. Chem. Phys., 155(11), 114503 (2021)
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Kazuhiro Sayama
ACS Sustainable Chem. Eng., 9(19), 6886-6893 (2021)- 515 -

15. "A computational study of a reduced dye and its O2 reduction: Implication on H2O2 production
with dye-sensitized photocathodes"
Hitoshi Kusama
Journal of Photochemistry and Photobiology A: Chemistry, 418, 113437 (2021)
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J Am Ceram Soc, 105(1), 700-711 (2021)
17. "Hydration-controlled excited-state relaxation in protonated dopamine studied by cryogenic ion
spectroscopy"
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J. Chem. Phys., 155(15), 151101 (2021)
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Chem. Sci., 12(42), 14281-14287 (2021)
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24. "Ab initio -based approach for the oxidation mechanisms at SiO2 /4H-6L&LQWHUIDFH,QWHUSOD\RI
dry and wet oxidants during interfacial reaction"
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Biophysical Journal, 120(21), 4786-4797 (2021)
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Angew. Chem. Int. Ed., 60(46), 24598-24604 (2021)
27. "Synthesis, characterization and biological evaluation of dipicolylamine sulfonamide derivatized
platinum complexes as potential anticancer agents"
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Chem. Sci., 12(43), 14570-14576 (2021)
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Chem. Commun., 57(98), 13246-13258 (2021)
31. "The effect of water exposure on FePc thin films grown on bismuth-covered Si(111) surfaces"
S. Ohno, K. Okanda and K. Takahashi
Surface Science, 716, 121953 (2022)
32. "Tardigrade Secretory-Abundant Heat-6ROXEOH3URWHLQ+DVD)OH[LEOHȕ-%DUUHO6WUXFWXUHLQ
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J. Phys. Chem. B, 125(32), 9145-9154 (2021)- 517 -

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J. Phys. Chem. B, 125(16), 4031-4045 (2021)
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Chem. Sci., 12(40), 13292-13300 (2021)
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replica-exchange method".HQJR7DNHPRWR<RVKLNL,VKLL+LWRVKL:DVKL]X.DQJ.LPDQG1REX\XNL0$78%$<$6,
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38. "Real-time observation of photoionization-induced water migration dynamics in 4methylformanilide–water by picosecond time-resolved infrared spectroscopy and ab initio
molecular dynamics simulations"
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Phys. Chem. Chem. Phys., 24(10), 5774-5779 (2022)
70. "Gas phase protonated nicotine is a mixture of pyridine- and pyrrolidine-protonated conformers:
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Org. Lett., 24(11), 2120-2124 (2022)
73. "Ab initio study for orientation dependence of nitrogen incorporation at 4H-6L&6L22 interfaces"
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74. %DQGJDSHQJLQHHULQJRIĮ-Ga2O3 by hydrostatic, uniaxial, and equibiaxial strain"
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Jpn. J. Appl. Phys., 61(2), 021005 (2022)
75. "Decomposition of nitric oxide by rhodium cluster cations at high temperatures"
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78. "Vibrational circular dichroism towards asymmetric catalysis: chiral induction in substrates
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Bull. Chem. Soc. Jpn., 95(6), 961-967 (2022)
108."Fragmentation pathways of methylbenzoate cations following core excitation: Theoretical
approach using graph theory"
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Chemical Physics Letters, 766, 138316 (2021)
109."X-ray emission spectroscopy: a genetic algorithm to disentangle core–hole-induced dynamics"/DUV*03HWWHUVVRQDQG2VDPX7DNDKDVKLTheor Chem Acc, 140(12), 162 (2021)
110."Physical and chemical imaging of adhesive interfaces with soft X-rays"+LUR\XNL<DPDQH0DVDNL2XUD2VDPX7DNDKDVKL7RPRNR,VKLKDUD1RULNR<DPD]DNL.RLFKL
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112."Remote steric control for undirected meta -VHOHFWLYH&–H activation of arenes"%RREDODQ5DPDGRVV<XVKX-LQ6REL$VDNRDQG/DXUHDQ,OLHV
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Phys. Chem. Chem. Phys., 23(38), 21512-21520 (2021)
116."A theoretical study on solvatofluorochromic asymmetric thiazolothiazole (TTz) dyes using
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Phys. Chem. Chem. Phys., 23(37), 21078-21086 (2021)
117."H/D isotope effect between adsorbed water (H2O, D2O, and HDO) and H2O- and D2O-ice
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122."Development of anharmonic vibrational structure theory using backflow transformation".LULNR,VKLL7RPRPL6KLPD]DNL0DVDQRUL7DFKLNDZDDQG<XNLXPL.LWD
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J. Phys. Chem. A, 126(1), 155-163 (2022)
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129."Synthesis, Structures, and Properties of Triskelion-6KDSHG)OXRURSKRUHV%HDULQJ&RXPDULQVZLWK1LWURJHQ-&RQWDLQLQJ'RQRU*URXSV
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131."Synthesis and crystal structure of a sulphur-bridged molecular hoop consisting of 5,7,12,14tetrathiapentacene"
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RSC Adv., 12(18), 10870-10874 (2022)
132.&KDOFRJHQDFDOL[>@GLWKLHQRVHOHQRSKHQH6\QWKHVLVDQG3URSHUWLHVRI&\FOLF7KLR- andSelenoether of Dithienoselenophene"
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the Solid State and in Solution"
Ryota Abe, Yoshitaka Tsuchido, Tomohito Ide, Take-aki Koizumi and Kohtaro Osakada
ACS Omega, 7(11), 9594-9601 (2022)
134."Reactions introducing 4-cyano-5-dicyanomethylene-2-oxo-3-pyrrolin-3-yl group to 4-ethynyl11-dialkylaniline derivatives and characterization of the resulting dyes"+DUXND.DWVX\DPD5LNR6XPLWD5\RKHL<DPDNDGRDQG6KXML2NDGD
Dyes and Pigments, 199, 110103 (2022)
135."Dianion complexes of pyrrole-EDVHGDQLRQUHFHSWRUV>@-Type complexes that form ionpairing assemblies"
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136.&RPSOH[HVRIWUDQVLWLRQ metal carbonyl clusters with tin(ii) phthalocyanine in neutral andradical anion states: methods of synthesis, structures and properties"
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Dalton Trans., 51(6), 2226-2237 (2021)
137."Free-6WDQGLQJ1DQRPHWHU-7KLFN&RYDOHQW2UJDQLF)UDPHZRUN)LOPVIRU6HSDUDWLQJ&22 and
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J. Am. Soc. Mass Spectrom., 32(8), 2144-2152 (2021)
139."Fragmentation efficiency of phenethylamines in electrospray ionization source estimated bytheoretical chemistry calculation"
Daiki Asakawa and Kazumi Saikusa
J Mass Spectrom  KWWSVGRLRUJMPV
140."Hot Hydrogen Atom Irradiation of Protonated/Deprotonated Peptide in an Ion Trap Facilitates
Fragmentation through Heated Radical Formation"
Daiki Asakawa, Hidenori Takahashi, Shinichi Iwamoto and Koichi Tanaka
J. Am. Chem. Soc., 144(7), 3020-3028 (2022)
141.6\QWKHVLVDQG,VRODWLRQRID.LQHWLFDOO\6WDELOL]HG&U\VWDOOLQH7ULDQJXOHQH
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J. Am. Chem. Soc., 143(46), 19599-19605 (2021)
142."Anthracene-%DVHG=ZLWWHULRQZLWKD6PDOO+202–/802(QHUJ\*DS
Akihiro Shimizu, Ryo Shintani and Ayane Kayama
Synthesis, 53(21), 4042-4047 (2021)
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J. Am. Chem. Soc., 144(5), 2218-2224 (2022)- 529 -

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SoftwareX, 16, 100879 (2021)
146."A boron-transfer mechanism mediating the thermally induced revival of frustrated carbene–
borane pairs from their shelf-stable adducts"<RLFKL+RVKLPRWR0DKLUR6DNXUDED7DNX\D.LQRVKLWD0DVDNL2KER0DQXVVDGD5DWDQDVDN-XQ-ya Hasegawa and Sensuke Ogoshi
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148.&R6LQJOH$WRPVLQ=U22 ZLWK,QKHUHQW2[\JHQ9DFDQFLHVIRU6HOHFWLYH+\GURJHQDWLRQRI&22
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150."A catalyzed E/Z isomerization mechanism of stilbene using para-benzoquinone as a triplet
sensitizer".DKR1DNDWDQL+LURIXPL6DWRDQG5\RLFKL)XNXGD
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151."An analysis of valence electronic structure from a viewpoint of resonance theory:
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J Comput Chem, 42(23), 1662-1669 (2021)
152.&KDUJH-transfer crystal with segregated packing structure constructed with hexaarylbenzene andtetracyanoquinodimethane"
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153."Synthesis of hydrosilylboronates via the monoborylation of a dihydrosilane Si–H bond and theirapplication for the generation of dialkylhydrosilyl anions"
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Crystal Growth & Design, 21(8), 4683-4689 (2021)
155.0HFKDQRFKHPLFDOV\QWKHVLVRIPDJQHVLXP-based carbon nucleophiles in air and their use inorganic synthesis"
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Org. Biomol. Chem., 19(47), 10444-10454 (2021)
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203."Steric effects on the intramolecular charge transfer fluorescence of benzo[b]thiophene-1,1dioxide bridged macrocages".HLWD1REXKDUD<XVXNH,QDJDNLDQG:DWDUX6HWDND
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㯮ෆࠉᐶ᫂
㣤᳃ࠉಇᩥ
⊁㔝ࠉ┤࿴
஭ᡭࠉᬛோ
ΎỈࠉ❶ᘯ
ఀ⸨ࠉ⫕
ᓥ⏣ࠉᩄᏹ
⠛⏣ࠉᜨᏊ
ᆏᮏࠉ㐨᫛
㯮⏣ࠉ኱♸
๓⏣ࠉ⌮
ఀໃᕝࠉ⨾✑
ᐑᓮࠉ⚽ಇ
㓇ᕳࠉ኱㍜
ᯘࠉ⪽Ꮚ
⁪⏣ࠉⰋ
ᒣඖࠉ῟ᖹ
ᙳᒣࠉⳀἋ
ᒣᓊࠉὒ
ᑠỮࠉె♸
℩㧗ࠉ΅
:0&6DPHHUD
୰ᮧࠉಟ୍
㕥ᮌࠉ㈼⣖
ᶓᕝ኱㍜
㕥ᮌࠉ῟ᕧ
⛅ᒣࠉⰋ
኱ᵳࠉᖾ⩏
⏣୰ࠉៅ୍㑻
㛗⏣ࠉᾈ୍
ỤᕝࠉὈᬸ
ᩧ⸨ࠉ❳⏨
ᮧ஭ࠉᚁྐ
㯮ᮌࠉᑲ
⋢⯓ࠉ▱ஓ

࣓ࣥࣂ࣮ᩘ








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

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
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- 543 -

ㄽᩥᩘ


ㄽᩥ␒ྕ



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

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




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ࢥ࣮ࢻ
IZ
IZ
IZ
IZ
IZ
IZ
IZ
IZ
I[
I[
I[
I[
I[
I\
I\
I\
I\
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I]
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JD
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JD
JD
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JE
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JF
JF
JF
JF
JF
JF
JF
JF
JG
JG
JG
JG

௦⾲⪅ྡ
ᡭᓥࠉṇ࿃
▼ᶫࠉᏕ❶
ᒸ⏣ࠉὒྐ
᳜⏣ࠉ୍ṇ
す㛗ࠉ஽
ᑠᮡࠉ೺ᩯ
ຍ⸨ࠉ೺ኴ
㉥஭ࠉ࿘ྖ
ᯇ⏣ࠉḠஅ
࿃㒓ࠉ཭ᏹ
ᒣᓮࠉ⚈Ꮚ
ᫍᮏࠉ㝧୍
ዟᒣࠉඞᙪ
୰ᒣࠉဴ
⠛⏣ࠉ΅
▼஭ࠉⰋᶞ
ኳ⬟ࠉ⢭୍㑻
ᖹ⏣ࠉᆂ♸
ᒣ㛛ࠉ㝠ᖹ
ྂᒇࠉ⚽ᓠ
ὸ㔝ࠉඃኴ
ᮎᯇࠉᏳ⏤⨾
Ⅳ❤ࠉாྖ
㧗▼ࠉ࿴ே
⯪᭥ࠉ୍ṇ
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୰ᮧࠉᾈ❶
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㕥ᮌࠉᗣ௓
ෆᒣࠉὒ௓
㧗ᮌࠉᖾ἞
ᮤࠉ⚽ᰤ
ᒣᮏࠉဴஓ
ಙ⏣ࠉᑦẎ
἟⏣ࠉ᐀඾
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すᮏࠉ⬟ᘯ
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ᑠᓥṇᐶ
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᳃ࠉಇᩥ⏥㈡ࠉ◊୍㑻
ᯘࠉ៞ᾈ
⏣ཱྀࠉ┿ᙪ
᱓ཎࠉ✨
㞵ኪࠉᚭ

࣓ࣥࣂ࣮ᩘ


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- 544 -

ㄽᩥᩘ

ㄽᩥ␒ྕ



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JI
JI
JI
JI
JI
JI
LD
LD
TF
YD
YE
YF
YF
YF
YG
YH

௦⾲⪅ྡ
⏣௦ࠉ┬ᖹ
Ἑཎࠉṇᾈ
୰ᮧࠉ㐩
᳜ᮧࠉ୍ᗈ
㟷ᮌࠉ኱㍜
ྜྷ⏣ࠉᝆ୍㑻
ᖹ஭ࠉ๛
ᑠἨࠉ೺୍
㯮⏣ࠉṇᏕ
㏆⸨ࠉ೺
Ύ㔝ࠉ῟ྖ
ྜྷ⏣ࠉᣑே
㧗᳚ࠉ฼ᖾ
㰺⸨ࠉ㣁
ᑠᯘࠉὒ୍
ඤ⋢ࠉᣅஓ
ᱵ⃝ࠉ㞞࿴
㛗⏣ࠉ⿱ஓ
㔜ගࠉಖ༤
ᒣᮏࠉᩔ
✀⏣ࠉᑗႹ
ග⸨ࠉ⪔୍
⚟Ọࠉ㞞႐
㏆ῧࠉ῟୍
ᱵ⃝ࠉබ஧
ᒸᓮࠉ㐍
ᢲᒣࠉ῟
㤋ᒣࠉెᑦ
ᒣᓮࠉ㤾
㛗ᒸࠉṇ㝯
Ṋḟࠉᚭஓ
ᮡ㔝ࠉಟ

࣓ࣥࣂ࣮ᩘ








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
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

- 545 -

ㄽᩥᩘ

ㄽᩥ␒ྕ















ࢭࣥࢱ࣮࣏࣮ࣞࢺ 22
2022 ᖺ 9 ᭶Ⓨ⾜(2021 ᖺ 4 ᭶㹼2022 ᖺ 3 ᭶)㸺⦅㞟࣭Ⓨ⾜㸼⮬↛⛉Ꮫ◊✲ᶵᵓ ᒸᓮඹ㏻◊✲᪋タィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮
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