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2018 Fiscal Year Annual Research Report

Geometry changes by photoinduced charge-separations in flavoproteins

Research Project

Project/Area Number 16H04097
Research InstitutionKobe University

Principal Investigator

小堀 康博  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
Keywordsクリプトクロム / 光電荷分離 / 時間分解電子スピン共鳴 / 電子的相互作用 / 立体配置 / 運動性
Outline of Annual Research Achievements

本研究では時間分解EPR法(TREPR)を用いて、野生型Xenopus laevis CRY-DASHに異なる温度で生成する二つの電荷分離状態を観測した。得られた信号の帰属を行うため、末端トリプトファンであるW324をフェニルアラニンに置換した変異体と、W377をフェニルアラニンに置換した変異体のTREPR測定を行った。測定結果より、温度240 KではW324とFADの電荷分離状態(FAD- W400 W377 W324+)が、温度120 KではW377とFADの電荷分離状態(FAD- W400W377+W324)が生成していることが分かった。各電荷分離状態について、
スピン緩和と電荷再結合の影響を受けた量子コヒーレンスや量子分布および、マイクロ波による電子スピンの横方向磁化の時間発展を、一重項(S)および3つの三重項(T)スピン関数を基底とする回転座標系の確率Liouville方程式で解析した。
(FAD- W400 W377+W324)の電荷分離においては、交換相互作用(J)の値が時間変化とともに減少する様子が観測された。これは、ラジカル間の電子軌道の重なりがこの時間領域で徐々に減少するように分子がわずかな構造変化を起こすことを示している。このような低温領域におけるアミノ酸残基の再配向運動は室温領域では高速化されることが期待される。このため室温領域で観測されたFAD- W400 W377 W324+の生成には、前駆状態FAD-W400W377+W324におけるW377+の再配向運動が高速な電荷解離に重要な役割を果たすものと結論付けた。
また、各電荷分離状態のシミュレーションパラメータを用いて電子スピン分極イメージング図を作成し立体構造解析を行った。インタースピンベクトル(d)の向きや、超微細相互作用の異方性を画像に反映することでTREPR測定から分子配向を含めた電荷分離構造の詳細を得ることができた。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

  • Research Products

    (18 results)

All 2019 2018 Other

All Int'l Joint Research (2 results) Journal Article (9 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 9 results,  Open Access: 1 results) Presentation (7 results) (of which Int'l Joint Research: 5 results,  Invited: 7 results)

  • [Int'l Joint Research] フライブルク大学/ザーランド大学(ドイツ)

    • Country Name
      GERMANY
    • Counterpart Institution
      フライブルク大学/ザーランド大学
  • [Int'l Joint Research] 帝国大学ロンドン/Queen Mary University of London(英国)

    • Country Name
      UNITED KINGDOM
    • Counterpart Institution
      帝国大学ロンドン/Queen Mary University of London
  • [Journal Article] Mechanistic Insights into Photochemical Reactions on CH3NH3PbBr3 Perovskite Nanoparticles from Single-Particle Photoluminescence Spectroscopy2019

    • Author(s)
      Kimura Yuki、Karimata Izuru、Kobori Yasuhiro、Tachikawa Takashi
    • Journal Title

      ChemNanoMat

      Volume: 5 Pages: 340~345

    • DOI

      doi.org/10.1002/cnma.201800569

    • Peer Reviewed
  • [Journal Article] Charge-Transfer Character Drives M?bius Antiaromaticity in the Excited Triplet State of Twisted [28]Hexaphyrin2018

    • 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 Pages: 2685~2690

    • DOI

      10.1021/acs.jpclett.8b00740

    • Peer Reviewed
  • [Journal Article] Multiexciton Dynamics Depending on Intramolecular Orientations in Pentacene Dimers: Recombination and Dissociation of Correlated Triplet Pairs2018

    • 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 Pages: 3354~3360

    • DOI

      10.1021/acs.jpclett.8b01184

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Time-Resolved EPR Study on Singlet-Fission Induced Quintet Generation and Subsequent Triplet Dissociation in TIPS-Phenyl-Tetracene Aggregates2018

    • Author(s)
      Nagashima Hiroki、Kawaoka Shuhei、Matsui Yasunori、Tachikawa Takashi、Ikeda Hiroshi、Kobori Yasuhiro
    • Journal Title

      Journal of Photopolymer Science and Technology

      Volume: 31 Pages: 163~167

    • DOI

      10.2494/photopolymer.31.163

    • Peer Reviewed
  • [Journal Article] UVA- and Visible-Light-Mediated Generation of Carbon Radicals from Organochlorides Using Nonmetal Photocatalyst2018

    • Author(s)
      Matsubara Ryosuke、Yabuta Tatsushi、Md Idros Ubaidah、Hayashi Masahiko、Ema Fumitoshi、Kobori Yasuhiro、Sakata Ken
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Pages: 9381~9390

    • DOI

      10.1021/acs.joc.8b01306

    • Peer Reviewed
  • [Journal Article] Singlet-Fission-Born Quintet State: Sublevel Selections and Trapping by Multiexciton Thermodynamics2018

    • 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 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 Perovskites2018

    • Author(s)
      Karimata Izuru、Ohta Kaoru、Kobori Yasuhiro、Tachikawa Takashi
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 10 Pages: 37057~37066

    • DOI

      10.1021/acsami.8b13346

    • Peer Reviewed
  • [Journal Article] Identifying triplet pathways in dilute pentacene films2018

    • 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 Pages: 4222~4222

    • DOI

      10.1038/s41467-018-06330-x

    • 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 Dimer2018

    • Author(s)
      Nakamura Shunta、Sakai Hayato、Nagashima Hiroki、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
    • Journal Title

      ACS Energy Letters

      Volume: 4 Pages: 26~31

    • DOI

      10.1021/acsenergylett.8b01964

    • Peer Reviewed / Int'l Joint Research
  • [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 Mechanisms2019

    • 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 Dynamics2018

    • 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 Films2018

    • 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 Thermodynamics2018

    • 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 Cryptochrome2018

    • 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 Photosynthesis2018

    • Author(s)
      Yasuhiro Kobori
    • Organizer
      第56回日本生物物理学会年会
    • Invited

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Published: 2019-12-27  

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