不斉材料界面構造の評価と構築

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 24108701
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 叶 深 北海道大学, 触媒化学研究センター, 准教授 (40250419)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000); Fiscal Year 2013: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2012: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: キラリティ / 界面構造 / 生体分子 / 非線形分光 / 不斉構造 / 脂質二分子膜 / 酵素反応 / 立体選択性 / 不斉界面

Research Abstract

生体分子の殆どはキラルな構造･配置を持ち，その機能性発現に重要な役割を果たしている．触媒反応に極めて重要である表面や界面のキラリティに着目し，和周波発生(SFG)振動分光法によって実現することを目指す．本研究ではキラリティ測定のためにブロードバンドSFG計測システムの最適化を行った．これまでに以下の二つの分子系について検討してきた．
(1　)ビナフトール系（BN）キラル分子：キャスト法で作製されたBN薄膜から強いキラルSFG信号を観測したが，薄膜の表面とバルクの両方から発生されるものと考える．偏光制御でアキラルSFG信号との干渉により，R体とS体のBN分子のキラリティも区別できたことから，SFG測定によりキラリティを検出できることが分かった．一方，チオール結合を含むビナフトール誘導体を新規に合成し，金表面に自訴組織化単分子膜として修飾した．単分子膜レベルの界面キラリティの高感度に検出を試みたが，金基板からの非共鳴信号の影響が大きく，現時点では十分なS/NのキラルSFG信号が得られなかった．
(2)　リン脂質系キラル分子：細胞膜の骨格構造となる(L)または(D)のジパルミトイルホスファチジルコリン(DPPC)の脂質分子を，キャスト法またはLB法により超薄膜を研究対象とした．L体とD体のDPPCのキャスト膜から強いキラルSFG信号が観測できたと同時に，そのサインを区別することもできた．LB法で作製した単分子膜からのキラルSFG信号も得られるようになった．従来の円二色性や振動円二色性分光法などの線形キラル分光法より優れていることを示す．いま，その安定検出にさらに努めている．さらに，脂質分子の不斉炭素に接するエステル結合の加水分解反応を触媒するホスホリパーゼの酵素反応の速度論と反応機構について，L体とD体のからなるDPPC二分子膜を持って詳しく調べた．

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] The Structure of Lipid Bilayers Adsorbed on Activated Carboxy Terminated Monolayers Investigated by Sum Frequency Generation Spectroscopy (2014)
  • Author(s): Casford, M.; Ge, A.; Kett, P.; Ye, S.; Davies, P.
  • Journal Title: J. Phys. Chem. B Volume: 118 Issue: 12 Pages: 3335-3345
  • DOI: 10.1021/jp410401z
  • Peer Reviewed
• [Journal Article] The redox reaction of hydrogen peroxide at an Au(100) electrode: Implications for oxygen reduction kinetics. (2014)
  • Author(s): Zheng, Y.; Mei D.; Chen Y.X.; Ye, S.
  • Journal Title: Electrochem. Commun Volume: 39 Pages: 19-21
  • Peer Reviewed
• [Journal Article] Electrochemical and infrared spectroscopic study of the self-assembled monolayer of a cyano-bridged dimeric triruthenium complex on gold surface (2014)
  • Author(s): Zhang, H.; Sasaki, Y.; Abe, M.; Zhang, Y.; Ye, S.; Osawa, M.; Uosaki, K.
  • Journal Title: J. Electroanal. Chem. Volume: 714-715 Pages: 51-55
  • DOI: 10.1016/j.jelechem.2013.12.012
  • Peer Reviewed
• [Journal Article] 和周波発生(SFG)振動分光法（最新表面科学講座） (2014)
  • Author(s): 叶深，葛愛民
  • Journal Title: 色材協会誌， Volume: 87 Pages: 64-71
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of the Cyano Complex of Oxo-Centered Triruthenium Core [Ru3(μ3-O)(μ-CH3COO)6(pyridine)2(CN)] (2013)
  • Author(s): Zhang, H.; Sasaki, Y.; Zhang, Y.; Ye, S.; Osawa, M.; Abe, M.; Uosaki, K.
  • Journal Title: Inorg. Chem. Volume: 53 Issue: 3 Pages: 1288-1294
  • DOI: 10.1021/ic4012197
  • Peer Reviewed
• [Journal Article] Effect of Functional Group on the Monolayer Structures of Biodegradable Quaternary Ammonium Surfactants. (2013)
  • Author(s): Ge, A.; Peng, Q.; Wu, H.; Liu, H.; Tong, Y.; Nishida, T.; Yoshida, N.; Suzuki, K.; Sakai, T.; Osawa, M.; Ye, S.
  • Journal Title: Langmuir Volume: 29 Issue: 47 Pages: 14411-14420
  • DOI: 10.1021/la403502k
  • Peer Reviewed
• [Journal Article] Structure and Stability Studies of Mixed Monolayers of Saturated and Unsaturated Phospholipids under Low-level Ozone (2013)
  • Author(s): Qiao, L.; Ge, A.; Osawa, M.; Ye, S.
  • Journal Title: Phys. Chem. Chem. Phys., Volume: 15 Issue: 41 Pages: 17775-17785
  • DOI: 10.1039/c3cp52484a
  • Peer Reviewed
• [Journal Article] Proton-Coupled Electron Transfer and Lewis Acid Recognition at Self-Assembled Monolayers of an Oxo-Bridged Diruthenium (III) Complex Functionalized with Two Disulfide Anchors (2013)
  • Author(s): Zhang，H.; Abe, M.; Zhang, Y.; Li, G.; Ye, S.; Osawa, M.; Sasaki, Y.
  • Journal Title: Langmuir Volume: 29 Issue: 32 Pages: 10110-10119
  • DOI: 10.1021/la401736f
  • Peer Reviewed
• [Journal Article] Preferential Adsorption of Solvents on Cathode Surface of Li-ion Batteries (2013)
  • Author(s): Yu, L.; Liu, H.; Wang, Y.; Kuwata, N.; Osawa, M.; Kawamura, J.; Ye, S.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Issue: 22 Pages: 5753-5756
  • DOI: 10.1002/anie.201209976
  • Peer Reviewed
• [Journal Article] Structure and Lateral Interaction in Mixed Monolayers of Dioctadecyldimethyl Ammonium Chloride (DOAC) and Stearyl Alcohol (2013)
  • Author(s): Ge, A.; Wu, H.; Darwish, T.; James, M.; Osawa, M.; Ye, S.
  • Journal Title: Langmuir Volume: 29 Issue: 18 Pages: 5407-5417
  • DOI: 10.1021/la400143k
  • Peer Reviewed
• [Journal Article] Structures of Zn-Porphyrin on TiO2 in Dye-Sensitized Solar Cells Studied by Sum Frequency Generation Vibrational Spectroscopy and Ultrafast Spectroscopy (2013)
  • Author(s): Ye, S.; Kathiravan, A.; Hayashi, H.; Tong, Y.; Infahsaeng, Y.; Chabera, P.; Pascher, T.; Yartsev, A.; Isoda, S.; Imahori, H.; Sundstrum, V.
  • Journal Title: J. Phys. Chem. C Volume: 117 Issue: 12 Pages: 6066-6080
  • DOI: 10.1021/jp400336r
  • Peer Reviewed
• [Journal Article] Enzyme-Catalyzed Hydrolysis of the Phospholipid Bilayers Studied by Atomic Force Microscopy (2013)
  • Author(s): Wu, H.; Yu, L.; Tong, Y.; Ge, A.; Yau, Y.; Osawa, M.; Ye, S.
  • Journal Title: Biochimica et Biophysica Acta (BBA) - Biomembranes Volume: 1828 Issue: 2 Pages: 642-651
  • DOI: 10.1016/j.bbamem.2012.09.010
  • Peer Reviewed
• [Journal Article] Preparation of Hydrophobic Metal Oxide Films (2013)
  • Author(s): Yoshida, N.; Yokonishi, R.; Imai, T.; Nakamura, Y.; Kadokura, R.; Tong, Y.; Ye, S.; Watanabe, T.; Okura, T.
  • Journal Title: Journal of the Society of Inorganic Materials, Japan Volume: 20 Pages: 275-281
  • Peer Reviewed
• [Journal Article] Probing the Effect of the Solution Environment around Redox-Active Moieties Using Rigid Anthraquinone Terminated Molecular Rulers. (2012)
  • Author(s): Darwish, N.
  • Journal Title: J. Am. Chem. Soc. Volume: 134 Issue: 44 Pages: 18401-18409
  • DOI: 10.1021/ja307665k
  • Peer Reviewed
• [Journal Article] Characterizing the Photoinduced Switching Process of Nitrospiropyran Self-Assembled Monolayer Using In Situ Sum Frequency Generation Spectroscopy. (2012)
  • Author(s): Darwish, T.
  • Journal Title: Langmuir Volume: 28 Issue: 39 Pages: 13852-13860
  • DOI: 10.1021/la302204f
  • Peer Reviewed
• [Journal Article] Structure of adsorbed molecular layer on fused quartz surface determined sequentially in sodium stearate solution, dry Ar, pure water, and dry Ar by sum frequency generation spectroscopy (2012)
  • Author(s): Y. Zhang, H. Noguchi, S. Ye, K. Uosaki,
  • Journal Title: Surface Science Volume: 607 Pages: 92-96
  • DOI: 10.1016/j.susc.2012.08.017
  • Peer Reviewed
• [Presentation] Enzyme Catalyzed Hydrolysis of the Supported Lipid Bilayers (2014)
  • Author(s): 叶深
  • Organizer: The 3rd International Conference on the MEXT Project of Integrated Research on Chemical Synthesis“Synergy of Theory and Molecular Transformation”
  • Place of Presentation: Kyusyu University (Fukuoka)
  • Invited
• [Presentation] 非線形振動分光法による界面構造研究 (2014)
  • Author(s): 叶深
  • Organizer: 東北大学・理学研究科・化学専攻セミナー
  • Place of Presentation: 東北大学（仙台）
  • Invited
• [Presentation] Enzyme Catalyzed Hydrolysis of the Supported Lipid Bilayers Probed by Sum Frequency Generation (SFG) and Atomic Force Microscopy (AFM) (2013)
  • Author(s): Ye, S.
  • Organizer: CRC International Symposium on New Challenges on the Bio-interface
  • Place of Presentation: 北海道大学（札幌市）
  • Year and Date: 2013-02-05
  • Invited
• [Presentation] Phospholipase A2 (PLA2) Enzyme Catalyzed Hydrolysis of the Supported Lipid Bilayers Probed by SFG and AFM (2013)
  • Author(s): Ye, S.
  • Organizer: Japanese-German Workshop, “Structure and Control of Interfaces”
  • Place of Presentation: Magnus-Haus (Germany)
  • Year and Date: 2013-01-08
• [Presentation] 非線形振動分光法による界面分子構造の研究 (2013)
  • Author(s): 叶深
  • Organizer: 第53回分子科学若手の会
  • Place of Presentation: 分子科学研究所（岡崎）
  • Invited
• [Presentation] 低濃度オゾン中における脂質単分子膜の構造と安定性 (2013)
  • Author(s): 喬琳，葛愛民，大澤雅俊，叶深
  • Organizer: 第7回分子科学討論会
  • Place of Presentation: 京都テルサ（京都）
• [Presentation] 固体表面における有機薄膜の界面分子構造ー和周波発生（SFG）振動分光法による検討 (2013)
  • Author(s): 葛愛民, 喬琳, 彭奇齢, 大澤雅俊，叶深
  • Organizer: 2013年電気化学秋季大会
  • Place of Presentation: 東京工業大学（東京）
• [Presentation] 気液界面における脂質単分子膜の構造及びその安定性 (2013)
  • Author(s): 喬琳，葛愛民，大澤雅俊，叶深
  • Organizer: 2013年電気化学秋季大会
  • Place of Presentation: 東京工業大学（東京）
• [Presentation] "Enzyme-catalyzed Hydrolysis of Supported Lipid Bilayer Investigated by Atomic Force Microscopy (AFM)" (2012)
  • Author(s): Ye, S.
  • Organizer: 3rd Kanazawa BioAFM Workshop
  • Place of Presentation: 金沢KKRホテル（金沢市）
  • Year and Date: 2012-11-05
• [Presentation] Molecular Study on the Lipid Membrane Surface Probed by Sum Frequency Generation (SFG) (2012)
  • Author(s): Ye, S.
  • Organizer: Vibrations at Surfaces 14
  • Place of Presentation: ニチイ学館神戸ポートアイランドセンター（神戸市）
  • Year and Date: 2012-09-23
  • Invited
• [Presentation] Enzyme Reaction on Phospholipid Bilayers Probed by Sum Frequency Generation (SFG) and Atomic Force Microscope (AFM) (2012)
  • Author(s): Ye, S.
  • Organizer: CRC-FHI Joint Meeting“Complex Surfaces in Material Science”
  • Place of Presentation: FHI (Germany)
  • Year and Date: 2012-09-19
• [Presentation] Solvent Adsorption on the LiCoO2 Electrode Surface Probed by Nonlinear Vibrational Spectroscopy (2012)
  • Author(s): Ye, S.
  • Organizer: Spectroelectrochemistry 2012
  • Place of Presentation: DORMERO Hotel Konigshof Dresden (Germany)
  • Year and Date: 2012-08-26
  • Invited
• [Presentation] in situ AFM and SFG Studies on the Hydrolysis Reaction of Supported Lipid Bilayer Catalyzed by Phospholipase A2 (2012)
  • Author(s): Ye, S.
  • Organizer: 244th ACS, "Structure, Dynamics, and Reactivity at Charged Interfaces" Symposium
  • Place of Presentation: Philadelphia Conference Center (USA)
  • Year and Date: 2012-08-19
  • Invited
• [Presentation] Hydrolysis of Lipid Bilayer Catalyzed by PLA2 Enzyme ─ in situ SFG and AFM Studies ─ (2012)
  • Author(s): Ye, S.
  • Organizer: IACIS 2012
  • Place of Presentation: 仙台国際センター（仙台市）
  • Year and Date: 2012-05-13