孤立ナノ空間を有する有機金属錯体での特異な光化学反応の分光解析

• Project Area: Molecular Science for Supra Functional Systems ? Development of Advanced Methods for Exploring Elementary Process
• Project/Area Number: 22018030
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Institute for Molecular Science
• Principal Investigator: 古谷 祐詞 分子科学研究所, 生命・錯体分子科学研究領域, 准教授 (80432285)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,000,000 (Direct Cost: ¥4,000,000); Fiscal Year 2011: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 2010: ¥2,000,000 (Direct Cost: ¥2,000,000)
• Keywords: 超分子 / 赤外分光法 / 光化学 / 生体分子 / 生物物理

Research Abstract

本研究では、実在高次系である蛋白質そのものを研究する一方で、その触媒反応の本質のみを取り出したモデル系の研究も重要と考え、自己組織化により形成された「かご状有機金属錯体」のナノ空間中での光化学反応を赤外および可視分光法により明らかにすることを目指している。
これまでにアダマンタンを内包したかご状錯体に対する低温赤外分光解析により、光電子移動によるアダマンタンおよびかご状錯体の構造変化を検出した(Y.Furutani et al.,J.Am.Chem.Soc.,2009)。このような構造変化を実時間で捉えるために、新たに時間分解赤外分光計測系を立ち上げた。かご状錯体のアダマンタンの光酸化反応は不可逆的であるため、繰り返し励起が可能な[Ru(bpy)_3]^<2+>」・2Cl^-を用いて計測条件の最適化を行った。50ナノ秒での光反応誘起赤外差スペクトルの計測が可能であることを確認した。
光受容タンパク質であるバクテリオロドプシンに対して行った時間分解赤外分光計測のデータをSVDやGlobal Fittingにより詳細に解析した。バクテリオロドプシンの内部結合水の0-D伸縮振動やレチナールシッフ塩基のN-D伸縮振動を帰属した。これらの赤外スペクトル変化はプロトン移動が行われる中間体状態でのタンパク質内部の水素結合構造の変化を捉えたものである。
カリウムイオンチャネルであるKcsAはアルカリ金属イオンであるK^+を選択的に透過するイオンチャネルである。そのイオン透過孔での配位構造を明らかにするため、全反射赤外分光解析による研究を平成20年度から継続して行っている。カリウム濃度依存的な赤外差スペクトルを解析することにより、アミドIに特徴的な変化が見られることを明らかにした。

Research Products

• [Journal Article] Protein-Bound Water Molecules in Primate Red- and Green-Sensitive Visual Pigments (2012)
  • Author(s): Katayama, et al
  • Journal Title: Biochemistry Volume: 51 Issue: 6 Pages: 1126-1133
  • DOI: 10.1021/bi201676y
  • Peer Reviewed
• [Journal Article] Chimeric microbial rhodopsins containing the third cytoplasmic loop of bovine rhodopsin (2011)
  • Author(s): A.Nakatsuma, T.Yamashita, K.Sasaki, A.Kawanabe, K.Inoue, Y.Furutani, Y.Shichida, H.Kandori
  • Journal Title: Biophys.J Volume: 100 Issue: 8 Pages: 1874-1882
  • DOI: 10.1016/j.bpj.2011.02.054
  • Peer Reviewed
• [Journal Article] Sensory rhodopsin-I as a Bidirectional Switch : Opposite conformational changes from the same photoisomerization (2011)
  • Author(s): J.Sasaki, H.Takahashi, Y.Furutani, H.Kandori, J.L.Spudich
  • Journal Title: Biophys.J. Volume: 100 Issue: 9 Pages: 2178-2183
  • DOI: 10.1016/j.bpj.2011.03.026
  • Peer Reviewed
• [Journal Article] 全反射赤外分光法による膜タンパク質の構造機能相関研究の現状と展望 (2011)
  • Author(s): 古谷祐詞
  • Journal Title: 化学と工業 Volume: 64 Pages: 694-695
  • NAID: 10029523383
• [Journal Article] Sodium or Lithium Ion-Binding-Induced Structural Changes in the K-ring of V-ATPase from Enterococcus hirae Revealed by ATR-FTIR Spectroscopy (2011)
  • Author(s): Yuji Furutani, et al.
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 2860-2863
  • Peer Reviewed
• [Journal Article] Low-Temperature FTIR Study of Gloeobacter Rhodopsin : Presence of Strongly Hydrogen-Bonded Water and Long-Range Structural Protein Perturbation upon Retinal Photoisomerization (2010)
  • Author(s): Kyohei Hashimoto, et al.
  • Journal Title: Biochemistry Volume: 49 Pages: 3343-3350
  • Peer Reviewed
• [Journal Article] Protein Fluctuations as the Possible Origin of the Thermal Activation of Rod Photoreceptors in the Dark (2010)
  • Author(s): Victor Lorenz Fonfria, et al.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 5693-5703
  • Peer Reviewed
• [Journal Article] An FTIR Study of the Photoreaction of Bovine Rhodopsin in the Presence of Hydroxylamine (2010)
  • Author(s): Kouta Katayama, et al.
  • Journal Title: J.Phys.Chem.B Volume: 114 Pages: 9039-9046
  • Peer Reviewed
• [Journal Article] Molecular insight into intrinsic heme distortion in ligand binding in hemoprotein (2010)
  • Author(s): Saburo Neya, et al.
  • Journal Title: Biochemistry Volume: 49 Pages: 5642-5650
  • Peer Reviewed
• [Presentation] 全反射赤外分光法によるMg^<2+>輸送体MgtEのイオン選択機構の解析 (2012)
  • Author(s): 木村哲就
  • Organizer: 2011年度日本生物物理学会中部支部講演会
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2012-03-19
• [Presentation] Time-resolved infrared study on the light-driven chloride ion pump protein (2012)
  • Author(s): Yuji Furutani
  • Organizer: 4th Japan-Korea Seminar on Biomolecular Sciences : Experiments and Simulations
  • Place of Presentation: 東大寺総合文化センター(奈良県)(招待講演)
  • Year and Date: 2012-01-10
• [Presentation] Ion-selective mechanism of Mg^<2+> transporter MgtE studied by attenuated total reflection FTIR spectroscopy (2012)
  • Author(s): Tetsunari Kimura
  • Organizer: 4th Japan-Korea Seminar on Biomolecular Sciences : Experiments and Simulations
  • Place of Presentation: 東大寺総合文化センター(奈良県)
  • Year and Date: 2012-01-10
• [Presentation] Surface-enhanced ATR FTIR difference spectroscopy from a halorhodopsin monolayer on gold : dependence of spectral features on film properties (2012)
  • Author(s): Hao Guo
  • Organizer: 5th International Symposium on Nanomedicine (ISNM2011)
  • Place of Presentation: 名古屋大学(愛知県)
• [Presentation] Stepwise conformational changes upon anion pumping during the pharaonis halorhodopsin photocycle revealed by H/D unexchangeable amide-A vibrations (2012)
  • Author(s): Tetsunari Kimura
  • Organizer: 5th International Symposium on Nanomedicine (ISNM2011)
  • Place of Presentation: 名古屋大学(愛知県)
• [Presentation] Surface-enhanced ATR-FTIR difference spectroscopy from a halorhodopsin monolayer on gold island films (2011)
  • Author(s): Hao Guo
  • Organizer: The 49th Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 兵庫県立大学(兵庫県)
  • Year and Date: 2011-09-18
• [Presentation] Ion-selective mechanism of Mg^<2+> transporter MgtE studied by attenuated total reflection FTIR spectroscopy (2011)
  • Author(s): Tetsunari Kimura
  • Organizer: The 49th Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 兵庫県立大学(兵庫県)
  • Year and Date: 2011-09-18
• [Presentation] Development of stopped-flow attenuated total reflection FTIR spectroscopy for detecting dynamic structural changes in ion transporters (2011)
  • Author(s): Yuji Furutani
  • Organizer: The 49th Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 兵庫県立大学(兵庫県)(招待講演)
  • Year and Date: 2011-09-17
• [Presentation] Ion-protein interactions studied by ATR-FTIR spectroscopy (2011)
  • Author(s): Yuji Furutani
  • Organizer: 14th Asian Chemical Congress
  • Place of Presentation: Queen Sirikit Convention Center (Bangkok, Thailand)(招待講演)
  • Year and Date: 2011-08-11
• [Presentation] 赤外分光法でみるV型ATPaseのイオン結合・解離に伴う構造変化 (2011)
  • Author(s): 古谷祐詞
  • Organizer: 平成22年度日本生物物理学会中部支部討論会
  • Place of Presentation: 名古屋大学野依学術交流センター(愛知)
  • Year and Date: 2011-03-31
• [Presentation] Ion-binding-induced Structural Changes in Membrane Proteins Studied by ATR-FTIR Spectroscopy (2011)
  • Author(s): Yuji Furutani
  • Organizer: Third Korea-Japan Seminars on Biomolecular Sciences : -Experiments and Simulations
  • Place of Presentation: Lotte Hotel, Jeju,(韓国)
  • Year and Date: 2011-02-27
• [Presentation] FTIR Studies of Membrane Proteins (2011)
  • Author(s): Yuji Furutani
  • Organizer: The Winter School of Sokendai/Asian CORE Program "Frontiers of Molecular Science-Life, Material, Energy, and Space"
  • Place of Presentation: 岡崎コンファレンスセンター(愛知)
  • Year and Date: 2011-02-21
• [Presentation] 全反射赤外分光法によるMg^<2+>輸送体MgtEのイオン選択機構の解析 (2011)
  • Author(s): 木村哲就
  • Organizer: 第11回日本蛋白質科学会年会
  • Place of Presentation: ホテル阪急エキスポパーク(大阪府)
• [Presentation] Spectroscopic Analysis of Specific Photochemical Reactions in an Isolated Nanospece Formed by a Well-Designed Organo-Metal Complex (2011)
  • Author(s): Yuji Furutani
  • Organizer: The 5^<th> Symposium Molecular Science for Supra Functional Systems-Development of Advanced Methods for Exploring Elementary Processes-
  • Place of Presentation: Royton Sapporo(北海道)
• [Presentation] SEIRA difference spectroscopy on a halorhodopsin monolayer tethered on gold surface (2011)
  • Author(s): Hao Guo
  • Organizer: 5th Asia and Oceania Conference on Photobiology
  • Place of Presentation: 奈良県新公会堂(奈良県)
• [Presentation] Modification of Gold Thin Film Suitable for Surface-enhanced Vibrational Spectroscopy on Membrane Proteins (2010)
  • Author(s): Hao Guo
  • Organizer: 4^<th> International Symposium on Nanomedicine (ISNM2010)
  • Place of Presentation: 岡崎コンファレンスセンター(愛知)
  • Year and Date: 2010-11-30
• [Presentation] 孤立ナノ空間を有する有機金属錯体での特異な光化学反応の分光解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: 特定領域研究「高次系分子科学」第4回公開シンポジウム
  • Place of Presentation: 東北大学片平さくらホール(宮城)
  • Year and Date: 2010-11-25
• [Presentation] 時間分解FTIR差スペクトル計測によるファラオニスハロロドプシンの陰イオン輸送過程での構造変化解析 (2010)
  • Author(s): 木村哲就
  • Organizer: 第36回日本生体エネルギー研究会&特定領域研究「革新的ナノバイオ」合同シンポジウム
  • Place of Presentation: 大阪大学銀杏会館(大阪)
  • Year and Date: 2010-11-19
• [Presentation] X-D伸縮振動領域を含めた時間分解赤外分光法によるバクテリオロドプシンの光誘起構造変化解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: 第36回日本生体エネルギー研究会&特定領域研究「革新的ナノバイオ」合同シンポジウム
  • Place of Presentation: 大阪大学銀杏会館(大阪)
  • Year and Date: 2010-11-18
• [Presentation] Modification of Gold Thin Film Suitable for Surface-enhanced Vibrational Spectroscopy on Membrane Proteins (2010)
  • Author(s): Hao Guo
  • Organizer: The Overseas Sokendai Lecture in Bangkok 2010
  • Place of Presentation: Chulalongkorn University, Bangkok,(タイ)
  • Year and Date: 2010-10-20
• [Presentation] Stimulus-Induced Difference Infrared Spectroscopy for Membrane Proteins ; Visual and Archaeal-type Rhodopsins, and Flagella Motor Protein (2010)
  • Author(s): Yuji Furutani
  • Organizer: Indo-Japan Joint Workshop on "New Frontiers of Molecular Spectroscopy ; from Gas Phase to Proteins"
  • Place of Presentation: Hotel Kitano Plaza Rokkoso(兵庫)
  • Year and Date: 2010-09-28
• [Presentation] Time-resolved FT-IR measurement of X-D stretching vibrations of Bacteriorhodopsin in micro- to mill- second time range (2010)
  • Author(s): Yuji Furutani
  • Organizer: The 48th Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 東北大学(宮城)
  • Year and Date: 2010-09-20
• [Presentation] Conformational Changes upon Chloride-ion Pumping During the pharaonis Halorhodopsin Photocycle Studied by Time-resolved FTIR Spectroscopy (2010)
  • Author(s): Tetsunari Kimura
  • Organizer: The 48th Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 東北大学(宮城)
  • Year and Date: 2010-09-20
• [Presentation] 時間分解赤外分光法によるバクテリオロドプシンのX-D伸縮振動の解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: 第4回分子科学討論会
  • Place of Presentation: 大阪大学(大阪)
  • Year and Date: 2010-09-15
• [Presentation] ロドプシン-KcsA融合蛋白質の発現とFTIRによる構造変化解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: 特定領域研究「高次系分子科学」第9回ミニ公開シンポジウム
  • Place of Presentation: サギセミナーセンター(広島)
  • Year and Date: 2010-08-30
• [Presentation] 赤外分光法によるイオン輸送蛋白質の構造変化解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: アドバンス生命理学特論:世話人;須藤雄気准教授(名大・院理)
  • Place of Presentation: 名古屋大学(愛知)
  • Year and Date: 2010-07-13
• [Presentation] 孤立ナノ空間を有する有機金属錯体での特異な光化学反応の分光解析 (2010)
  • Author(s): 古谷祐詞
  • Organizer: 特定領域研究「高次系分子科学」第5回合同班会議
  • Place of Presentation: 南淡路ロイヤルホテル(兵庫)
  • Year and Date: 2010-05-25
• [Presentation] Interaction between Membrane Proteins and Ions Studied by ATR-FTIR Spectroscopy : A Potential Tool for Drug Screening (2010)
  • Author(s): Yuji Furutani
  • Organizer: BIT's 1^<st> Annual International Conference of Medichem-2010
  • Place of Presentation: Beijing International Convention Center, Beijing,(中国)
  • Year and Date: 2010-05-19