ᚑくᄢቇℂᎿቇ⎇ⓥႎ๔
J. Fac. Sci. Tech., Seikei Univ.
Vol.47 No.1 (2010) pp.1-㧡C60 ࠢ࡜ࠬ࠲࡯৻ᰴࠗࠝࡦࠍ៞タߒߚ㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆⵝ⟎ߦࠃࠆ࿕ቯൻ࡝࠱࠴࠙ࡓߩᦨ⴫㕙᭴ㅧ⹏ଔᎿ⮮ ᱜඳ㧖㧘ട⮮ ାᒾ㧖㧘㕍ᩉ ㉿ᨐ㧖Surface Structural Analysis of Supported Lysozyme by Using Time of Flight
Secondary Ion Mass Spectrometer Equipped with a C60 Cluster Primary Ion Source
Masahiro KUDO㧖, Nobuhiko KATO㧖, Satoka AOYAGI㧖,ABSTRACT㧦The knowledge of the structural changes of proteins caused by chemical reactions or otherfactors such as pH conditions are of great importance in the development of various medical devices aswell as in the basic biomolecular studies of biopolymers. The direct analysis of such structural changes
with spectrometric approaches, however, is, in general, quite difficult or restricted. In this study,
time-of-flight secondary ion mass spectrometry (TOF-SIMS) with a C60 primary ion source, which iswell-known as an extremely sensitive surface structural analysis method, was applied for the study of thepartial structure of proteins. The model sample used is lysozyme supported on an aminosilanized
ITO-coated glass electrode. The newly developed data analysis method of TOF-SIMS spectra, which isbased on the information theory, revealed that the observed characteristic protein peaks are ejected froma specific surface portion of the protein molecule. These results show that TOF-SIMS can provide
information on the configuration of protein molecules on the substrate and can be used for the analysis of
the partial protein structure and its changes due to various chemical environments.
Keywords㧦TOF-SIMS, surface analysis, protein structure, C60 cluster primary ion, lysozyme
㧔Received March 25, 2010㧕ⴕᤨ㑆ဳ⾰㊂ಽᨆ⸘㧔TOF-MS㧕ߢᬌ಴ߔࠆ‫ߒߛߚޕ‬㧘㧝㧚ߪߓ߼ߦ

TOF-SIMS ߪ㧘หߓ TOF-MS ࠍ↪޿ࠆࡑ࠻࡝࠶ࠢࠬᡰ ࿕૕ߩᦨ⴫㕙ࠍ㜞ᗵᐲߦⷰኤߢ߈ࠆᚻᴺߩ߭ߣߟߣេ࡟࡯ࠩ࡯⣕㔌ࠗࠝࡦൻ㧔MALDI㧕ᴺߣߪ⇣ߥࠅ㧘࠲ߒߡ㧘㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺ㧔Time-of-Flightࡦࡄࠢ⾰ߩࠃ߁ߥᏂᄢಽሶߩ႐วߪ㧘ࠗࠝࡦൻߩ㓙ߦࡈߪ࡜ࠣࡔࡦ࠻ൻ߇ㆱߌࠄࠇߥ޿ߣ޿߁໧㗴ὐ߇޽ߞߚ‫⃻ޕ‬ߐ߹ߑ߹ߥ⹜ᢱߩ⹏ଔߦ↪޿ࠄࠇߡ޿ࠆ߇㧘․ߦේሶ㧘࿷ߢߪ㧘ਥᚑಽಽᨆ㧔 Principal Component Analysis:

Secondary Ion Mass Spectrometry: TOF-SIMS㧕1, 2)ಽሶ㧘ࡈ࡜ࠣࡔࡦ࠻ࠗࠝࡦߦ㑐ߔࠆᖱႎࠍ฽߻⾰㊂ࠬࡍࠢ࠻࡞ߣ㧘ߘࠇࠄߩಽᏓࠍࠨࡉࡒࠢࡠࡦࠬࠤ࡯࡞ߢ⴫ߔੑᰴࠗࠝࡦ௝ࠍᓧࠆߎߣ߇ߢ߈ࠆߚ߼㧘ࡃࠗࠝ࠺ࡃࠗࠬ߿ක≮↪᧚ᢱߦ೑↪ߐࠇࠆߎߣߩᄙ޿↢૕㜞ಽሶߩ᷹ቯ߳ߩᔕ↪ߦ߽ᄢ߈ߥᦼᓙ߇ነߖࠄࠇߡ޿ࠆ㧔࿑ 1㧕
‫ޕ‬PCA㧕3, 4) ߿ᖱႎࠛࡦ࠻ࡠࡇ࡯ߩᏅ㧔⋧੕ᖱႎ㊂㧕5, 6) ߥߤߩ᭽‫⸃࠲࡯࠺ߥޘ‬ᨆᴺ߇ TOF-SIMS ߦᔕ↪ߐࠇࠆࠃ߁ߦߥࠅ㧘ⶄ㔀ߥࡃࠗࠝ᧚ᢱߩ⸃ᨆߦ߽ TOF-SIMS ߩᔕ↪ 7, 8) ߇น⢻ߣߥߞߚ‫ߚ߹ޕ‬㧘TOF-SIMS ߢߪ⹜ᢱߩᦨ⴫㕙ᢙ࠽ࡁࡔ࡯࠻࡞ઃㄭߩൻቇ᭴ㅧᖱႎࠍᓧࠄࠇࠆߚ

TOF-SIMS ߢߪ㧘40nmޯ100nm ⒟ᐲߦ⛉ߞߚ৻ᰴࠗ߼㧘߅߽ߦ࠲ࡦࡄࠢ⾰ߩหቯߦ↪޿ࠄࠇࠆ MALDI ᴺߣࠝࡦࡆ࡯ࡓࠍ࿕૕⹜ᢱߦࠬࠠࡖࡦߒߥ߇ࠄᾖ኿ߒ㧘ߘߩߪ⇣ߥࠅ㧘࠺ࡃࠗࠬ਄ߩ࠲ࡦࡄࠢ⾰ߩᦨ⴫㕙ߩ᭴ㅧ߿㈩৻ᰴࠗࠝࡦߣߩⴣ⓭ߦࠃߞߡ⹜ᢱߩᦨ⴫㕙߆ࠄ᡼಴ߐࠇะᕈߦ⋥ធ㑐ଥߔࠆᖱႎ߇ᓧࠄࠇࠆ 6, 9, 10)‫ޕ‬ߐࠄߦ㧘Ꮒᄢಽሶߩ᷹ቯߦ᦭೑ߥ৻ᰴࠗࠝࡦḮߣߒߡ㧘ࠆࠗࠝࡦ㧔ੑᰴࠗࠝࡦ㧕ࠍ㜞ᗵᐲߥ⾰㊂ಽᨆ⸘ߢ޽ࠆ㘧ࠛࡀ࡞ࠡ࡯ࠍಽᢔߒߡਈ߃ࠄࠇࠆߚ߼㧘ࠃࠅⓏ๺ߥࠗࠝ㧖㧦ℂᎿቇㇱᢎ᝼(kudo@st.seikei.ac.jp)㧖㧦ℂᎿቇㇱഥᢎ㧖㧦ፉᩮᄢቇ↢‛⾗Ḯ⑼ቇㇱ࿾ၞ㐿⊒⑼ቇ⑼ࡦൻ߇ᦼᓙߐࠇࠆࠢ࡜ࠬ࠲࡯ࠗࠝࡦḮ 11, 12) ߇㐿⊒ߐࠇ㧘
㊄ࠢ࡜ࠬ࠲࡯ࠗࠝࡦḮ㧘ࡆࠬࡑࠬࠢ࡜ࠬ࠲࡯ࠗࠝࡦḮ㧘㧙㧙ߦኻߒߡ 3 ὐ㧘࡝࠱࠴࠙ࡓ࿕ቯൻ⹜ᢱߪห৻᧦ઙߢ૞⵾

ߒߚ 3 ᨎࠍฦ 2 ὐߩ⸘ 6 ὐ᷹ቯߒߚ‫ޕ‬㧟㧚⚿ᨐߣ⠨ኤ ࿑ 2 ߦ C60+ ࠍ৻ᰴࠗࠝࡦḮߣߒߡ᷹ቯߒ㧘ᓧࠄࠇߚTOF-SIMS ࠬࡍࠢ࠻࡞ߩઍ⴫଀ࠍ␜ߔ‫੹ޕ‬࿁ߩ᷹ቯ᧦ઙ
ߢߪ㧘m/z 300 ࠍ⿥߃ࠆੑᰴࠗࠝࡦߪ㜞ᒝᐲߦߪᬌ಴ߢ࿑  㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺߩේℂ߈ߥ߆ߞߚ‫ޕ‬࿑ 2 ߦ␜ߔ⾰㊂▸࿐ m/z 0~200 ߦෳᾖ⹜ᢱC60 ࠗࠝࡦḮߥߤ߇ㄭᐕ೑↪ߐࠇࠆࠃ߁ߦߥߞߚ‫ޕ‬ߣᲧセߒߡ㧘࡝࠱࠴࠙ࡓ࿕ቯൻ⹜ᢱߢ᣿ࠄ߆ߦᒝᐲ߇㜞 ᧄ⎇ⓥߢߪ㧘ࠢ࡜ࠬ࠲࡯ࠗࠝࡦߦࠃࠆ࠲ࡦࡄࠢ⾰⹜ᢱߊ㧘࠲ࡦࡄࠢ⾰↱᧪ߣ⠨߃ࠄࠇࠆੑᰴࠗࠝࡦࡇ࡯ࠢ߇޿⸘᷹ߩ᦭↪ᕈࠍᬌ⸛ߔࠆߚ߼ߦ㧘C60 ࠗࠝࡦḮࠍ৻ᰴࠗࠝߊߟ߆ᬌ಴ߐࠇߚ‫ࠇߎޕ‬એ਄ߩ⾰㊂▸࿐ߢߪ㧘੹࿁ߩ᷹ࡦߣߒߡ↪޿㧘࠻࡝ෆ⊕࡝࠱࠴࠙ࡓࠍ࿕ቯൻߒߚ⹜ᢱࠍቯ᧦ઙߢߪหቯน⢻ߥᒝᐲࠍᜬߟ࠲ࡦࡄࠢ⾰↱᧪ߩੑᰴ᷹ቯߒ㧘࡝࠱࠴࠙ࡓߩ㈩ะ⹏ଔࠍⴕߞߚ‫ߚ߹ޕ‬㧘એ೨ߦࠗࠝࡦࡇ࡯ࠢߪᬌ಴ߢ߈ߥ߆ߞߚߚ߼㧘ᧄ⎇ⓥߢߪߎߩ

㊄ࠢ࡜ࠬ࠲࡯ࠗࠝࡦḮߢ᷹ቯߒߚ⚿ᨐߣ߽Ყセᬌ⸛ 10)▸࿐ߩੑᰴࠗࠝࡦࠍኻ⽎ߣߒߡ㧘⸃ᨆߒߚ‫ޕ‬࿑ 2-2 ߆ࠄ2-5 ߢߪ㧘Ꮕ߇⷗ࠄࠇߚੑᰴࠗࠝࡦࡇ࡯ࠢ๟ㄝࠍ᜛ᄢߒ

ߒߚ‫ޕ‬ߡ␜ߔ‫ߚ߹ޕ‬㧘࿑ 2 ߪෳᾖ⹜ᢱ㧘࡝࠱࠴࠙ࡓ⹜ᢱߘࠇߙ

ࠇߩઍ⴫⊛ߥࠬࡍࠢ࠻࡞ࠍ␜ߔ߇㧘ઁߩࠬࡍࠢ࠻࡞ߢ߽㧞ታ㛎ᣇᴺ߶߷ห᭽ߩ⚿ᨐ߇ᓧࠄࠇߚ‫ޕ‬ ࿑ 2 ߦ␜ߒߚੑᰴࠗࠝࡦࡇ࡯ࠢࠍਛᔃߣߒߡ㧘੹࿁ߩ ⹜ᢱ૞⵾ ၮ᧼ߢ޽ࠆࠗࡦࠫ࠙ࡓ࡯ࠬ࠭㉄ൻ⤑㧔ITO㧕ࠦ࡯࠹ࠖ⸃ᨆߢᓧࠄࠇߚ࡝࠱࠴࠙ࡓߦ↱᧪ߔࠆߣ⠨߃ࠄࠇࠆੑᰴ

ࡦࠣࠬ࡜ࠗ࠼ࠟ࡜ࠬ㧔Sigma- Aldrich Co., St Louis, MO,USA㧕ࠍࠕࡒࡁࡊࡠࡇ࡞࠻࡝ࡔ࠻ࠠࠪࠪ࡜ࡦ㧔᧲੩ൻᚑ㧘ࠗࠝࡦࡇ࡯ࠢࠍ⴫ 1 ߦ␜ߔ‫ޕ‬ฦੑᰴࠗࠝࡦࡇ࡯ࠢߩหቯ
⚿ᨐ߆ࠄ㧘ฦੑᰴࠗࠝࡦ߇⿠࿃ߔࠆࠕࡒࡁ㉄߅ࠃ߮ࠕࡒ

᧲੩㧕ߢࠕࡒࡁࠪ࡜ࡦൻߒ㧘ࠣ࡞࠲࡞ࠕ࡞࠺ࡅ࠼㧔๺శࡁ㉄ߩ⚵ߺวࠊߖࠍ᳞߼ߚ‫ޕ‬࿕ቯൻ࡝࠱࠴࠙ࡓߩᦨ⴫㕙⚐⮎㧕ߢ᨞ᯅߒߚߩߜ㧘࠻࡝ෆ⊕࡝࠱࠴࠙ࡓ㧔 Sigma-ㇱಽߪ㧘ߎࠇࠄߩੑᰴࠗࠝࡦࡇ࡯ࠢߦ⿠࿃ߔࠆࠕࡒࡁ㉄Aldrich㧕ࠍ฽߻ pH7.4 ߩ࡝ࡦ㉄✭ⴣᶧਛߦ 30 ᤨ㑆ᶐߒ㧘ࠍ฽߻ㇱಽߣ⠨߃ࠄࠇࠆ‫ⶄޕ‬ᢙߩࠕࡒࡁ㉄߆ࠄߥࠆੑᰴ

࡝࠱࠴࠙ࡓߩǭ-ࠕࡒࡁၮㇱಽߣ౒᦭⚿วߐߖߡ࿕ቯൻࠗࠝࡦߪ㧘⊒↢႐ᚲ߇․ቯߐࠇࠆߚ߼㧘⴫㧝ߩਛߩⶄᢙߒߚ‫ޕ‬ෳᾖ⹜ᢱߣߒߡ㧘࠲ࡦࡄࠢ⾰࿕ቯൻ೨ߩࠕࡒࡁࠪߩࠕࡒࡁ㉄ߩ⊒↢႐ᚲࠍᦨೋߦᬌ⸛ߒߚ‫ޕ‬࡜ࡦൻ ITO ࠟ࡜ࠬࠍ↪ᗧߒߚ‫ߩߘޕ‬ᓟ㧘ోߡߩ⹜ᢱߪ㧘ಓ⚿ੇ῎ེ㧔VD-250F㧘࠲ࠗ࠹࠶ࠢ㧘ၯ₹㧕ߢಓ⚿ੇ῎࠻࡝ෆ⊕࡝࠱࠴࠙ࡓߩࠕࡒࡁ㉄㈩೉ߢ㧘⴫㧝ߩⶄᢙߩࠕࡒࡁ㉄߆ࠄߥࠆੑᰴࠗࠝࡦߩ⊒↢႐ᚲߣߥࠅᓧࠆ▎ᚲࠍਅ✢ߢਅ⸥ߦ␜ߔ‫ߚ߹ޕ‬㧘એ೨ߩ㊄ࠢ࡜ࠬ࠲࡯㧔Au3 㧕+ߒߚ‫ޕ‬ߦࠃࠆ᷹ቯ 10) ߢ␜ໂߐࠇߚੑᰴࠗࠝࡦ⊒↢႐ᚲࠍ[ 㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆ㧔61(5+/5㧕]ߢ␜ߔ‫ޕ‬ ৻ᰴࠗࠝࡦࠍ C60 ߣߔࠆ㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂+ߎࠇࠄߩ▎ᚲࠍᄙߊ฽߻㕙ࠍ࠻࡝ෆ⊕࡝࠱࠴࠙ࡓߩ┙૕᭴ㅧ㧔Protein Data Bank ID: 1DPW㧕߆ࠄតߒߚߣߎ

ಽᨆ⸘㧔TFS-2000㧘Physical Electronics, Eden Prairie,MN, USA㧕ࠍ↪޿ߡ㧘ᱜੑᰴࠗࠝࡦࠬࡍࠢ࠻࡞ࠍฦ⹜

ࠈ㧘࿑ 3 ߦ␜ߔ㕙߇਄ㅀߩ 6 ࠞᚲߩਅ✢ㇱಽߩ߁ߜ 4 ࠞᢱߦߟ޿ߡߘࠇߙࠇ᷹ቯߒߚ‫ޕ‬᷹ቯ▸࿐ߪ m/z 0~2000㧘

ᚲࠍ฽߻ࠨࠗ࠻ߢ޽ࠆߎߣ߇ಽ߆ߞߚ‫ߦߎߎޕ‬฽߹ࠇࠆห৻᧦ઙߢ㧘ෳᾖ⹜ᢱߪห৻᧦ઙߢ૞⵾ߒߚ 2 ᨎߩ⹜ᢱ130 ߦߪ TP (69, 70)㧘m/z 136 ߦߪ GC (126, 127)㧘GM

࡜ࠬ࠲࡯ࠨࠗ࠭ߪ 260µm㧘᷹ቯᤨ㑆ߪ 15 ಽ㑆ߣߒߚ‫ޕ‬ࠕࡒࡁ㉄ߩ⚵ߺวࠊߖࠍ⴫ 1 ߩࡇ࡯ࠢߣᾖวߔࠆߣ㧘m/z㧙㧙㧔1㧕m/z 0 ~ 200㧔2㧕㧦m/z 70 ઃㄭ          㧔3㧕m/z 110 ઃㄭ㧔4㧕m/z 130 ઃㄭ          㧔5㧕m/z 170 ઃㄭ࿑  ෳᾖ⹜ᢱ㧔%QPVTQN㧕࡝࠱࠴࠙ࡓ࿕ቯൻ⹜ᢱ㧔.[UQ\[OG㧕ߩઍ⴫⊛ߥ 61(5+/5 ࠬࡍࠢ࠻࡞

(104, 105)㧘CK (115, 116)㧘m/z 170ߦߪCK (115, 116)߇ኻ

߇ᧄ⎇ⓥߩ࿕ቯൻ࡝࠱࠴࠙ࡓߩᦨ⴫㕙ߣ⠨߃ࠄࠇࠆ‫߹ޕ‬ᔕߒ㧘߹ߚઁߩන⁛ߩࠕࡒࡁ㉄ㇱಽ߆ࠄ⊒↢ߒߚߣ⠨߃ߚ㧘ߎߩࠨࠗ࠻ߪ㧘㊄ࠢ࡜ࠬ࠲࡯ߢߩ᷹ቯ⚿ᨐߢ␜ໂߐࠄࠇࠆੑᰴࠗࠝࡦߩ⊒↢Ḯߣߥࠆࠕࡒࡁ㉄ߦߟ޿ߡ߽㧘ࠇߚᦨ⴫㕙㧔[GRC]㧘[RC]㧘[RGCR]ࠍ฽߻ࠨࠗ࠻㧕ߣ߽ฦੑᰴࠗࠝࡦࡇ࡯ࠢߦߟ޿ߡ1ߟએ਄߇ోߡߎߩࠨࠗ࠻߶߷৻⥌ߒ㧘ߎߩ⢛㕙ߪ࠲ࡦࡄࠢ⾰ߩၮ᧼ߣߩ⚿วߢㇱߦ฽߹ࠇࠆߎߣ߇ಽ߆ߞߚ‫ࠅ߹ߟޕ‬㧘ߎߩࠨࠗ࠻߆ࠄ㧘ಽߢ޽ࠆ࡝ࠪࡦ㧔ǭ-ࠕࡒࡁၮ㧕ㇱಽࠍ߽ߞߣ߽ᄙߊ฽߻࿕ቯൻ࡝࠱࠴࠙ࡓߦ․⇣⊛ߣㆬ߫ࠇߚోߡߩੑᰴࠗࠝࡦ㕙ߢ߽޽ࠆ‫ޕ‬߇⊒↢ߔࠆߎߣ߇น⢻ߢ޽ࠆ‫ߡߞ߇ߚߒޕ‬㧘ߎߩࠨࠗ࠻ ⚿ᨐߣߒߡ␜ໂߐࠇߚ㈩ะߪ߶߷╬ߒ޿߇㧘C60+ ߦࠃ㧙㧙ߞߡ㧘␜ໂߐࠇߚ࠲ࡦࡄࠢ⾰⹜ᢱߦ⿠࿃ߔࠆੑᰴࠗࠝࡦࡇ࡯ࠢߪ㧘㊄ࠢ࡜ࠬ࠲࡯ࠗࠝࡦࠃࠅᓧࠄࠇߚ⚿ᨐࠃࠅ߽⴫  ࠲ࡦࡄࠢ⾰↱᧪ੑᰴࠗࠝࡦࡇ࡯ࠢm/z⚵ᚑᑼ↱᧪ߔࠆࠕࡒࡁ㉄න⁛ߩ႐ว

70.07

82.04

84.05
84.08

86.10

110.07120.08C4H8N

C4H6N2C5H6O

C4H6NOC5H10NC2H14NS

㧔㈩೉਄ߩ

⚵วࠊߖ

୘ᢙ㧕

(㈩೉਄ߩ㗅ᐨ)V (6), L (8), I(6), K (6), P(2), R (11)H (1)V (6), L (8), I(6), K (6), P

ࡒࡁ㉄Q (3), E (2)᣿⏕ߢ޽ߞߚ‫ߩߘޕ‬ℂ↱ߪ㧘C60+ ߇㊄ࠢ࡜ࠬ࠲࡯ࠗࠝࡦ

L (8), I (6), K(6)ࠃࠅዊߐߥⴣ᠄ߢ࠲ࡦࡄࠢ⾰ಽሶࠍࠗࠝࡦൻߔࠆߚ߼㧘C (8)

L (8), I (6), KC2H16NSC (8)C8H10N࿑  ࡝࠱࠴࠙ࡓᦨ⴫㕙㧔࡝ࡏࡦ᭴ㅧ㧕ߣᬌ಴ߐࠇߚࠕ(2), R (11)

C5H12N

C5H8N3ⶄᢙߩ႐วߩ

ࠃࠅᦨ⴫㕙ߦᢅᗵߦ࠲ࡦࡄࠢ⾰ߩ᭴ㅧࠍᱷߒߚࡈ࡜ࠣࡔࡦ࠻ࠗࠝࡦߩ⊒↢ࠍน⢻ߣߔࠆߚ߼ߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬ߒߚ߇ߞߡ㧘ࠢ࡜ࠬ࠲࡯ࠗࠝࡦ C60+ ࠍ৻ᰴࠗࠝࡦḮߣߒ(6)ߡ↪޿ࠆߎߣߦࠃࠅ㧘࿕ቯൻ࠲ࡦࡄࠢ⾰ߩ㈩ะ⹏ଔ߅ࠃ

H (1), R (11)߮ㇱಽ᭴ㅧ⹏ଔࠍ⹦⚦ߦታ⃻ߔࠆน⢻ᕈ߇޽ࠆߎߣ߇␜

E (2), F(3), Yߐࠇߚ‫ߚ߹ޕ‬㧘ࠢ࡜ࠬ࠲࡯ࠗࠝࡦߦࠃࠆࠬࡄ࠶࠲࡝ࡦࠣ

(3)ߦࠃߞߡ㧘ಽሶౝㇱߩ᭴ㅧ߿᭴ㅧᄌൻ߽⹏ଔߢ߈ࠆน⢻130.07

C9H8N

W (6)

136.07

C4H12N2OS

M (2)GC (126, 127)㧠㧚⚿ ⸒

C5H14NOS

M (2)

LC (75, 76), 㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺߪࡃࠗࠝ⹜ᢱߩᦨ⴫

136.08170.06

C5H10N2O2

C8H10NOY (3)

C4H12N2O3

D (7), S (10),C7H8NO

W (6)C8H12NOSC6H8N3O3

ᕈ߇޽ࠅ㧘ߘߩᬌ⸛ߦߪߐࠄߥࠆ⎇ⓥ߇ᔅⷐߢ޽ࠆ‫ޕ‬TP (69, 70)

GM (104, 105),
CK (115, 116)

㕙 2nm એਅߩᖱႎࠍᓧࠆߎߣ߇ߢ߈ࠆ㜞ᗵᐲߥ⴫㕙ಽᨆᴺߢ޽ࠅ㧘․ߦ㧘C60+ ߥߤߩࠢ࡜ࠬ࠲࡯ࠗࠝࡦࠍ৻ᰴࠗࠝࡦߦ↪޿ࠆߣ࠲ࡦࡄࠢ⾰ߩࠃ߁ߥⶄ㔀ߥ↢૕㜞ಽሶߩᦨ⴫㕙᭴ㅧ߇⹦⚦ߦ᣿ࠄ߆ߣߥࠆน⢻ᕈ߇␜ߐࠇߚ‫ޕ‬T (7)ߎߩᚻᴺߪ㧘ࡃࠗࠝ࠺ࡃࠗࠬ਄ߩ࠲ࡦࡄࠢ⾰ߩ㈩ะ⹏ଔ
߿᭴ㅧᄌൻߩ⹏ଔߦᔕ↪ߢ߈ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬MK (12, 13),LC (75, 76),Q (3)CK (115, 116)⻢ ㄉ ߎߩ⎇ⓥߩ৻ㇱߪ㧘ᢥㇱ⑼ቇ⋭⑼ቇ⎇ⓥ⾌⧯ᚻ⎇ⓥ

KVF[GRC]ELAA AMKRHGLDNY RGYSLGNWVC

㧔B㧕ߩഥᚑ㧔⺖㗴⇟ภ 19710096㧕ࠍฃߌߡⴕࠊࠇߚ‫ޕ‬

RWWCNDGRTP GSRNLCNIPC SALLSSDITAෳ⠨ᢥ₂

QAWI[RGCR]L

1) J. C. Vickerman, D. Briggs, TOF-SIMS : Surface

AAKFESNFNT QATNRNTDGS TDYGILQINS

SVNCAKKIVS DGNGMNAWVA WRN[RC]KGTDV㧙㧙analysis by mass spectrometry, IM Publications,UK (2001)2) ੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺ㧘㧔ਣༀ㧕╙  ┨   3) M. S. Wagner and D. G. Castner, Langmuir 17,4649 (2001)

4) A. M. Belu, D. J. Graham, D. G. Castner,Biomaterials 24, 3635 (2003).

5) S. Aoyagi, M. Hayama. U. Hasegawa, K. Sakai, M.

Tozu, T. Hoshi and M. Kudo, e-J. Surf. Sci.
Nanotech, 1, 67 (2003)

6) Satoka Aoyagi, “Review of TOF-SIMS bioanalysis
using mutual information”, Surface and Interface
Analysis, 41(2) 136-142, (2009)7) Michel R, Castner D. G., 2006. Surf. Interface Anal.,
38, 1386-1392.

8) S. Aoyagi and M. Kudo, “Evaluation of Proteins onBio-Devices” (“Proteins at Solid-liquid Interfaces”

Edited by Philippe Dejardin) 2006 August,Springer Verlag, Berlin

9) S. Aoyagi, A. Rouleau and W. Boireau, “TOF-SIMS
structuralcharacterizationofself-assemblymonolayer of cytochrome b5 onto gold substrate”,
Applied Surface Science , 255,1071-1074 (2008)

10) K. Okada, S. Aoyagi, M. Dohi, N. Kato, M. Kudo,
M. Tozu, T. Miyayama, N. Sanada, “ Evaluation ofimmobilized-lysozyme by means of TOF-SIMS”,
Applied Surface Science, 255,1104-1106 (2008)

11) F. Kollmer, Appl. Surf. Sci., 231-232, 153 (2004)

12) Weibel D. E., Lockyer N., Vickerman J. C., 2004.
Appl. Sur. Sci., 231-232, 146-152

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