Geometry changes by photoinduced charge-separations in flavoproteins

• Project/Area Number: 16H04097
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Kobe University
• Principal Investigator: Kobori Yasuhiro 神戸大学, 分子フォトサイエンス研究センター, 教授 (00282038)
• Co-Investigator(Kenkyū-buntansha): 岩田 達也 東邦大学, 薬学部, 准教授 (20569917)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000); Fiscal Year 2018: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2017: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2016: ¥10,920,000 (Direct Cost: ¥8,400,000、Indirect Cost: ¥2,520,000)
• Keywords: 光電荷分離 / 立体構造 / 電子的相互作用 / アミノ酸残基 / クリプトクロム / 時間分解電子スピン共鳴法 / 電子スピン分極 / 時間分解電子スピン共鳴 / 立体配置 / 運動性 / 生物物理 / シグナル伝達 / 進化 / 光エネルギー変換 / 電子スピン共鳴 / 電子スピン共鳴法

Outline of Final Research Achievements

To understand the mechanism of navigating the Earth magnetic field by animals, we have clarified atomic-scale conformation changes in oxidized tryptophan residue in photoinduced charge-separated (CS) state in cryptochrome by using time-resolved electron paramagnetic resonance measurements with applying site directed mutagenesis for Xenopus laevis cryptochrome (Xcry) DASH. The intermediate charge-separated state as the secondary radical ion pair between reduced flavin adenine dinucleotide (FAD-) and the tryptophan377 (W377+) was characterized together with the terminal radical pair of FAD--W324+. The relative position and the orientation of the charges were precisely determined by our recently developed tool of the electron spin polarization imaging derived by the magnetophotoselection measurement at low temperature. We have clarified that the conformation changes in W377+ play important role for the hole-transfer reaction from the secondary intermediate of FAD--W377+.

Academic Significance and Societal Importance of the Research Achievements

分子動力学計算による予測(Solov’yov et al. Sci. Rep.2014)では二段階目の電荷分離に伴うタンパク質構造変化の重要性が示唆されていた。このような運動が、静電相互作用を乗り越える発熱的な電荷解離を引き起こしていることが仮説として提示される。今回、アミノ酸残基や水分子の運動が特異的な溶媒和を引き起こすことで、有効な反応場を提供していることが実証された学術的意義は大きい。本研究はタンパク質の特定のアミノ酸による環境場が分子論的にどのように効率のよいエネルギー変換機能を決定づけるかについて実証するものであり、数十億年に渡る生命進化の謎を解き明かす糸口になる。

Research Products

• [Int'l Joint Research] フライブルク大学/ザーランド大学(ドイツ)
• [Int'l Joint Research] 帝国大学ロンドン/Queen Mary University of London(英国)
• [Int'l Joint Research] Imperial College London/University College London/Oxford University(英国)
• [Int'l Joint Research] University of Freiburg(ドイツ)
• [Int'l Joint Research] フライブルク大学(ドイツ)
• [Int'l Joint Research]
• [Journal Article] Mechanistic Insights into Photochemical Reactions on CH3NH3PbBr3 Perovskite Nanoparticles from Single-Particle Photoluminescence Spectroscopy (2019)
  • Author(s): Kimura Yuki、Karimata Izuru、Kobori Yasuhiro、Tachikawa Takashi
  • Journal Title: ChemNanoMat Volume: 5 Issue: 3 Pages: 340-345
  • DOI: 10.1002/cnma.201800569
  • NAID: 120006599192
  • Peer Reviewed
• [Journal Article] Time-Resolved EPR Study on Singlet-Fission Induced Quintet Generation and Subsequent Triplet Dissociation in TIPS-Phenyl-Tetracene Aggregates (2018)
  • Author(s): Nagashima Hiroki、Kawaoka Shuhei、Matsui Yasunori、Tachikawa Takashi、Ikeda Hiroshi、Kobori Yasuhiro
  • Journal Title: Journal of Photopolymer Science and Technology Volume: 31 Issue: 2 Pages: 163-167
  • DOI: 10.2494/photopolymer.31.163
  • NAID: 130007481537
  • ISSN: 0914-9244, 1349-6336
  • Year and Date: 2018-06-25
  • Peer Reviewed / Open Access
• [Journal Article] Charge-Transfer Character Drives Mobius Antiaromaticity in the Excited Triplet State of Twisted [28]Hexaphyrin (2018)
  • Author(s): Ema Fumitoshi、Tanabe Mana、Saito Shohei、Yoneda Tomoki、Sugisaki Kenji、Tachikawa Takashi、Akimoto Seiji、Yamauchi Seigo、Sato Kazunobu、Osuka Atsuhiro、Takui Takeji、Kobori Yasuhiro
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 9 Issue: 10 Pages: 2685-2690
  • DOI: 10.1021/acs.jpclett.8b00740
  • Peer Reviewed / Open Access
• [Journal Article] Multiexciton Dynamics Depending on Intramolecular Orientations in Pentacene Dimers: Recombination and Dissociation of Correlated Triplet Pairs (2018)
  • Author(s): Sakai Hayato、Inaya Ryutaro、Nagashima Hiroki、Nakamura Shunta、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 9 Issue: 12 Pages: 3354-3360
  • DOI: 10.1021/acs.jpclett.8b01184
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] UVA- and visible light-mediated generation of carbon radicals from organochlorides using non-metal photocatalyst (2018)
  • Author(s): R. Matsubara, T. Yabuta, U. Md Idros, M. Hayashi, F. Ema, Y. Kobori, K. Sakata
  • Journal Title: J. Org. Chem. Volume: 83 Issue: 16 Pages: 9381-9390
  • DOI: 10.1021/acs.joc.8b01306
  • Peer Reviewed
• [Journal Article] Singlet-Fission-Born Quintet State: Sublevel Selections and Trapping by Multiexciton Thermodynamics (2018)
  • Author(s): Nagashima Hiroki、Kawaoka Shuhei、Akimoto Seiji、Tachikawa Takashi、Matsui Yasunori、Ikeda Hiroshi、Kobori Yasuhiro
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 9 Issue: 19 Pages: 5855-5861
  • DOI: 10.1021/acs.jpclett.8b02396
  • Peer Reviewed
• [Journal Article] Several Orders of Magnitude Difference in Charge-Transfer Kinetics Induced by Localized Trapped Charges on Mixed-Halide Perovskites (2018)
  • Author(s): Karimata Izuru、Ohta Kaoru、Kobori Yasuhiro、Tachikawa Takashi
  • Journal Title: ACS Applied Materials & Interfaces Volume: 10 Issue: 43 Pages: 37057-37066
  • DOI: 10.1021/acsami.8b13346
  • NAID: 120006541927
  • Peer Reviewed
• [Journal Article] Identifying triplet pathways in dilute pentacene films (2018)
  • Author(s): Lubert-Perquel Daphn?、Salvadori Enrico、Dyson Matthew、Stavrinou Paul N.、Montis Riccardo、Nagashima Hiroki、Kobori Yasuhiro、Heutz Sandrine、Kay Christopher W. M.
  • Journal Title: Nature Communications Volume: 9 Issue: 1 Pages: 4222-4222
  • DOI: 10.1038/s41467-018-06330-x
  • NAID: 120006532038
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Quantitative Sequential Photoenergy Conversion Process from Singlet Fission to Intermolecular Two-Electron Transfers Utilizing Tetracene Dimer (2018)
  • Author(s): Nakamura Shunta、Sakai Hayato、Nagashima Hiroki、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
  • Journal Title: ACS Energy Letters Volume: 4 Issue: 1 Pages: 26-31
  • DOI: 10.1021/acsenergylett.8b01964
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Time-Resolved EPR Study on Photoinduced Charge-Transfer Trap State in Thiophene-Thiazolothiazole Copolymer Film (2017)
  • Author(s): Yuta Yamamoto, Takumi Ako, Takashi Tachikawa, Itaru Osaka, Yasuhiro Kobori
  • Journal Title: Journal of Photopolymer Science and Technology Volume: 30 Issue: 5 Pages: 551-555
  • DOI: 10.2494/photopolymer.30.551
  • NAID: 130005950302
  • ISSN: 0914-9244, 1349-6336
  • Peer Reviewed / Open Access
• [Journal Article] Topotactic Epitaxy of SrTiO3 Mesocrystal Superstructures with Anisotropic Construction for Efficient Overall Water Splitting (2017)
  • Author(s): Peng Zhang, Tomoya Ochi, Mamoru Fujitsuka, Yasuhiro Kobori, Tetsuro Majima, Takashi Tachikawa
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 19 Pages: 5299-5303
  • DOI: 10.1002/anie.201702223
  • NAID: 120006406709
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Direct Observation of Charge Collection at Nanometer-Scale Iodide-Rich Perovskites during Halide Exchange Reaction on CH3NH3PbBr3 (2017)
  • Author(s): Izuru Karimata, Yasuhiro Kobori, Tachikawa Tachikawa
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 8 Issue: 8 Pages: 1724-1728
  • DOI: 10.1021/acs.jpclett.7b00482
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Regulated Electron Tunneling of Photoinduced Primary Charge-Separated State in the Photosystem II Reaction Center (2017)
  • Author(s): M. Hasegawa, H. Nagashima, R. Minobe, T. Tachikawa, *H. Mino and *Y. Kobori
  • Journal Title: J. Phys. Chem. Lett. Volume: 8 Issue: 6 Pages: 11791184-11791184
  • DOI: 10.1021/acs.jpclett.7b00044
  • NAID: 120006305568
  • Peer Reviewed
• [Journal Article] Switching of the pi-electronic conjugations in the reduction of a dithienylethene-fused p-benzoquinone (2017)
  • Author(s): E. Saito, T. Ako, *Y. Kobori and *A. Tsuda
  • Journal Title: RSC Adv. Volume: 7 Issue: 5 Pages: 24032406-24032406
  • DOI: 10.1039/c6ra27001h
  • Peer Reviewed / Open Access
• [Journal Article] Self-Assembled Molecular Gear: A 4:1 Complex of Rh(III)Cl Tetraarylporphyrin and Tetra(p-pyridyl)cavitand (2016)
  • Author(s): M. Nakamura, K. Kishimoto, *Y. Kobori, T. Abe, K. Yoza, *K. Kobayashi
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 38 Pages: 1256412577-1256412577
  • DOI: 10.1021/jacs.6b07284
  • Peer Reviewed
• [Journal Article] Morphology Effect on Geometry of Photoinduced Charge-Separated State in P3HT:PCBM Blend Films as Studied by Time-Resolved EPR Spectroscopy (2016)
  • Author(s): T. Miura, T. Tachikawa, *Y. Kobori
  • Journal Title: Journal of Photopolymer Science and Technology Volume: 29 Issue: 4 Pages: 561-564
  • DOI: 10.2494/photopolymer.29.561
  • NAID: 130005261775
  • ISSN: 0914-9244, 1349-6336
  • Peer Reviewed
• [Journal Article] Photoinduced Charge-Transfer State of 4-Carbazolyl-3-(trifluoro-methyl)benzoic Acid: Photophysical Property and Application to Reduction of Carbon-Halogen Bonds as a Sensitizer (2016)
  • Author(s): R. Matsubara, T. Shimada, *Y. Kobori, T. Yabuta, T. Osakai, M. Hayashi
  • Journal Title: Chem-Asian J. Volume: 11 Issue: 14 Pages: 20062010-20062010
  • DOI: 10.1002/asia.201600538
  • Peer Reviewed
• [Journal Article] Time Resolved EPR Study on the Photoinduced Long-Range Charge-Separated State in Protein: Electron Tunneling Mediated by Arginine Residues in Human Serum Albumin (2016)
  • Author(s): M. Fuki, H. Murai, T. Tachikawa, Y. Kobori
  • Journal Title: J. Phys. Chem. B Volume: - Issue: 19 Pages: 43654372-43654372
  • DOI: 10.1021/acs.jpcb.6b01072
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Geometries, Electronic Couplings, and Hole Dissociation Dynamics of Photoinduced Electron-Hole Pairs in Polyhexylthiophene-Fullerene Dyads Rigidly Linked by Oligophenylenes (2016)
  • Author(s): T. Miura, R. Tao, S. Shibata, T. Umeyama, T. Tachikawa, H. Imahori, Y. Kobori
  • Journal Title: J. Am. Chem. Soc. Volume: - Issue: 18 Pages: 5879-5885
  • DOI: 10.1021/jacs.5b13414
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Crystal-Face-Dependent Charge Dynamics on a BiVO4 Photocatalyst Revealed by Single-Particle Spectroelectrochemistry (2016)
  • Author(s): Takashi Tachikawa, Tomoya Ochi, Yasuhiro Kobori
  • Journal Title: ACS Catalysis Volume: 6 Issue: 4 Pages: 2250-2256
  • DOI: 10.1021/acscatal.6b00234
  • NAID: 120005842518
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 時間分解電子スピン共鳴法を用いた光エネルギー変換初期過程の観測 (2019)
  • Author(s): Yasuhiro Kobori
  • Organizer: 第19回分子分光研究会
  • Invited
• [Presentation] Three-Dimension Visualizations of Electron Spin Polarization for Elucidating Photo- Energy Conversion Mechanisms (2019)
  • Author(s): Yasuhiro Kobori
  • Organizer: The 6th OCU International Workshop on Quantum Chemistry/Quantum Chemical Calculations on Quantum Computers: Quantum Algorithms
  • Int'l Joint Research / Invited
• [Presentation] Time-Resolved EPR Study on Singlet Fission and Subsequent Triplet Dissociation Dynamics (2018)
  • Author(s): Yasuhiro Kobori
  • Organizer: The 35th International Conference of Photopolymer Science and Technology Materials & Processes for Advanced Microlithography, Nanotechnology and Phototechnology
  • Int'l Joint Research / Invited
• [Presentation] Time Resolved EPR Study on Photoinduced Charge-Transfer Trap States in Thiophene-Thiazolothiazole Copolymers Films (2018)
  • Author(s): Yasuhiro Kobori
  • Organizer: 233rd ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Singlet-Fission-Born Quintet State: Sublevel Selections and Trapping by Multiexciton Thermodynamics (2018)
  • Author(s): Yasuhiro Kobori
  • Organizer: Spin Physics, Spin Chemistry, Spin Technology (SPCT2018)
  • Int'l Joint Research / Invited
• [Presentation] Geometry and motion of seconddary charge-separated states in Cryptochrome (2018)
  • Author(s): Yasuhiro Kobori
  • Organizer: 4th Kanto Area Spin Chemistry Meeting (4th KASC)
  • Int'l Joint Research / Invited
• [Presentation] Electron Spin Polarization Imaging Analyses of Primary Charge Separations in Photosynthesis (2018)
  • Author(s): Yasuhiro Kobori
  • Organizer: 第56回日本生物物理学会年会
  • Invited
• [Presentation] Time Resolved EPR Study on Photoinduced Charge-Separations in Thin Films of Thiophene-Thiazolothiazole Copolymer (2017)
  • Author(s): Yasuhiro Kobori
  • Organizer: The 34th International Conference of Photopolymer Science and Technology Materials & Processes for Advanced Microlithography, Nanotechnology and Phototechnology
  • Int'l Joint Research / Invited
• [Presentation] Time-Resolved EPR Study on Charge Dynamics of Electron-Hole Pairs in Lead Iodide Perovskite Thin Film (2017)
  • Author(s): Yasuhiro Kobori
  • Organizer: 231st ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] "Electron spin polarization imaging applied to primary charge separation in the PSII Yasuhiro Kobori" (2017)
  • Author(s): Yasuhiro Kobori
  • Organizer: The 5th Awaji International Workshop on Electron Spin Science & Technology (AWEST2017)
  • Int'l Joint Research / Invited
• [Presentation] Electron Spin Polarization Imaging of Photoinduced Primary Charge-Separated States in PSII (2017)
  • Author(s): Yasuhiro Kobori
  • Organizer: Spin Chemistry Meeting 2017
  • Int'l Joint Research / Invited
• [Presentation] Time-Resolved EPR Study on Photoinduced Charge-Transfer Trap States in Thiophene-Thiazolothiazole Copolymer Films (2017)
  • Author(s): Yasuhiro Kobori
  • Organizer: 11th Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
  • Int'l Joint Research / Invited
• [Presentation] 光合成初期反応の電子スピン画像解析 (2017)
  • Author(s): 小堀康博
  • Organizer: 第四回森野デスカッション
  • Invited
• [Presentation] Primary Charge-Separation Mechanism in the Photosynthetic Reaction Center Studied by Time-Resolved EPR Spectroscopy (2016)
  • Author(s): Yasuhiro Kobori
  • Organizer: Electron Donor Acceptor Interactions Gordon Research Conference
  • Place of Presentation: Salve Regina University, Newport RI United States
  • Year and Date: 2016-08-07
  • Int'l Joint Research / Invited
• [Presentation] Dynamics of Photoinduced Electron-Hole Pairs in Polyhexylthiophene-Fullerene Dyads Rigidly Linked by Oligophenylenes (2016)
  • Author(s): ○Yasuhiro Kobori;Taku Miura;Ran Tao;Sho Shibata;Tomokazu Umeyama;Takashi Tachikawa;Hiroshi Imahori
  • Organizer: 4th Awaji International Workshop on “Electron Spin Science & Technology: Biological and Materials Science Oriented Applications
  • Place of Presentation: Awaji Yumebutai International Conference Center
  • Year and Date: 2016-06-19
  • Int'l Joint Research / Invited
• [Presentation] Morphology Effect on the Geometry of the Photoinduced Charge-Separated State in P3HT:PCBM Brend Films as Studied by Time-Resolved EPR Spectroscopy (2016)
  • Author(s): Taku Miura;Takashi Tachikawa;○Yasuhiro Kobori
  • Organizer: The 33rd International Conference of Photopolymer Science and Technology
  • Place of Presentation: 幕張メッセ
  • Int'l Joint Research