Femtosecond time-resolved X-ray measurement of metal complexes

• Project Area: Non-equilibrium-state molecular movies and their applications
• Project/Area Number: 19H05782
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Complex systems
• Research Institution: High Energy Accelerator Research Organization
• Principal Investigator: 足立 伸一 大学共同利用機関法人高エネルギー加速器研究機構, その他部局等, 理事 (60260220)
• Co-Investigator(Kenkyū-buntansha): 片山 哲夫 公益財団法人高輝度光科学研究センター, XFEL利用研究推進室, 主幹研究員 (90648073)
• Project Period (FY): 2019-06-28 – 2022-03-31
• Project Status: Discontinued (Fiscal Year 2021)
• Budget Amount: ¥85,540,000 (Direct Cost: ¥65,800,000、Indirect Cost: ¥19,740,000); Fiscal Year 2021: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2020: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2019: ¥16,380,000 (Direct Cost: ¥12,600,000、Indirect Cost: ¥3,780,000)
• Keywords: 放射光 / X線 / 金属錯体 / 時間分解計測 / X線自由電子レーザー / 物理化学 / 反応ダイナミクス / 時間分解 / 超高速ダイナミクス / 放射光X線

Outline of Research at the Start

溶液中で進行する光化学反応の計測には、これまで主に赤外から紫外域における時間分解分光法が用いられてきたが、これらの時間分解分光法は特定の元素（例えば、金属タンパク質の活性中心である金属元素）に注目した元素選択的な計測には適していない。このような元素選択的な計測には、原子の内殻励起を通じて金属原子の電子状態や金属原子周辺の構造を検出するX線分光計測が最も適した手法である。本研究では光反応性金属タンパク質の活性中心モデルとしての金属錯体を主な対象として、その分子構造と電子状態の時間発展をフェムト秒の時間分解能で精密に計測・解析することにより、金属元素を含む生体分子の機能発現メカニズムを解明に迫る。

Outline of Annual Research Achievements

本新学術領域では、生体高分子のみに留まらず、生体高分子の中に取り込まれて活性中心を構成する金属錯体についても、重要な研究ターゲットの一つである。本計画班(B01班)では、「金属錯体のフェムト秒時間分解分子構造・電子状態計測」という目標を掲げ、主に時間分解X線分光・X線散乱の計測手法を用いて、フェムト秒オーダーで現れる金属錯体の過渡的な分子構造および電子状態の解明を目指している。さらに、A01班における天然の光合成反応を模倣した人工光合成反応の開発研究とも連携し、光触媒機能を示す金属錯体をターゲットとして、その光エネルギー変換のメカニ ズムを時間分解X線計測を駆使して明らかにすることも目指している。 従来の溶液中で進行する光化学反応の計測には、主に赤外から紫外域における時間分解分光法が用いられてきたが、これらの時間分解分光法は分子構造に関する間接的な情報を与えるものの、直接的に分子構造情報を与えない。分子構造の直接情報を得るためには、X線散乱法が最も適した手法である。2021年度は、二酸化炭素の光還元反応を触媒するレニウム錯体の光励起された中間体について時間分解EXAFS法により構造解析を行い、時間分解赤外分光法および理論計算を合わせて、レニウム錯体における電子状態と反応性について議論を行なった。また、光反応性を示す金属錯体を抗体タンパク質に結合させた実験系について積極的に検討を進めた。

Research Progress Status

令和3年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和3年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] KAIST/POSTECH(韓国)
• [Int'l Joint Research] Lund University/University of Gothenburg/Uppsala University(スウェーデン)
• [Int'l Joint Research] Technical University of Denmark(デンマーク)
• [Int'l Joint Research] European XFEL/DESY(ドイツ)
• [Int'l Joint Research] EPFL/Paul Scherrer Institute(スイス)
• [Int'l Joint Research]
• [Int'l Joint Research] KAIST/POSTECH(韓国)
• [Int'l Joint Research] DESY(ドイツ)
• [Journal Article] Determining Excited-State Structures and Photophysical Properties in Phenylphosphine Rhenium(I) Diimine Biscarbonyl Complexes Using Time-Resolved Infrared and X-ray Absorption Spectroscopies (2021)
  • Author(s): Yuushi Shimoda, Kiyoshi Miyata, Masataka Funaki, Takumi Ehara, Tatsuki Morimoto, Shunsuke Nozawa, Shin-ichi Adachi, Osamu Ishitani, Ken Onda
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 11 Pages: 7773-7784
  • DOI: 10.1021/acs.inorgchem.1c00146
  • Peer Reviewed / Open Access
• [Journal Article] New Visible-Light-Driven H2- and O2-Evolving Photocatalysts Developed by Ag(I) and Cu(I) Ion Exchange of Various Layered and Tunneling Metal Oxides Using Molten Salts Treatments (2020)
  • Author(s): Watanabe Kenta、Iwashina Katsuya、Iwase Akihide、Nozawa Shunsuke、Adachi Shin-ichi、Kudo Akihiko
  • Journal Title: Chemistry of Materials Volume: 32 Issue: 24 Pages: 10524-10537
  • DOI: 10.1021/acs.chemmater.0c03461
  • Peer Reviewed / Open Access
• [Journal Article] Mapping the emergence of molecular vibrations mediating bond formation (2020)
  • Author(s): Kim J. G., Nozawa S., Kim H., Choi E. H., Sato T., Kim T. W., Kim K. H., Ki H., Kim J., Choi M., Lee Y., Heo J., Oang K. Y., Ichiyanagi K., Fukaya R., Lee J. H., Park J., Eom I., et al.
  • Journal Title: Nature Volume: 582 Issue: 7813 Pages: 520-524
  • DOI: 10.1038/s41586-020-2417-3
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tracking the Local Structure Change during the Photoabsorption Processes of Photocatalysts by the Ultrafast Pump-Probe XAFS Method (2020)
  • Author(s): Uemura Yohei、Yokoyama Toshihiko、Katayama Tetsuo、Nozawa Shunsuke、Asakura Kiyotaka
  • Journal Title: Applied Sciences Volume: 10 Issue: 21 Pages: 7818-7818
  • DOI: 10.3390/app10217818
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Charge Trapping Process in Photoexcited Nitrogen-Doped Titanium Oxides (2020)
  • Author(s): Sato Kosuke、Yamanaka Ken-ichi、Nozawa Shunsuke、Fukuzawa Hironobu、Katayama Tetsuo、Morikawa Takeshi、Nonaka Takamasa、Dohmae Kazuhiko、Ueda Kiyoshi、Yabashi Makina、Asahi Ryoji
  • Journal Title: Inorganic Chemistry Volume: 59 Issue: 15 Pages: 10439-10449
  • DOI: 10.1021/acs.inorgchem.0c00696
  • Peer Reviewed
• [Journal Article] Femtosecond X-ray emission study if the spin cross-over dynamics in haem proteins (2020)
  • Author(s): D. Linschel et al, and T. Suzuki
  • Journal Title: Nature Communication Volume: 11 Issue: 1 Pages: 4145-4145
  • DOI: 10.1038/s41467-020-17923-w
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering (2020)
  • Author(s): Panman Matthijs R.、Katayama Tetsuo、Westenhoff Sebastian他
  • Journal Title: Physical Review Letters Volume: 125 Issue: 22 Pages: 226001-226001
  • DOI: 10.1103/physrevlett.125.226001
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Anisotropic X-Ray Scattering of Transiently Oriented Water (2020)
  • Author(s): Kim Kyung Hwan、Katayama Tetsuo、Nilsson Anders、Perakis Fivos他
  • Journal Title: Physical Review Letters Volume: 125 Issue: 7 Pages: 076002-076002
  • DOI: 10.1103/physrevlett.125.076002
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Supramolecular copolymerization driven by integrative self-sorting of hydrogen-bonded rosettes (2020)
  • Author(s): Aratsu Keisuke、Takeya Rika、Pauw Brian R.、Hollamby Martin J.、Kitamoto Yuichi、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Yagai Shiki
  • Journal Title: Nature Communications Volume: 11 Issue: 1 Pages: 1623-1623
  • DOI: 10.1038/s41467-020-15422-6
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photoinduced anisotropic distortion as the electron trapping site of tungsten trioxide by ultrafast W L1-edge X-ray absorption spectroscopy with full potential multiple scattering calculations (2019)
  • Author(s): Koide Akihiro, Hatada Keisuke et al.
  • Journal Title: Physical Chemistry Chemical Physics Volume: 19 Issue: 5 Pages: 1-7
  • DOI: 10.1039/c9cp01332f
  • NAID: 120006957263
  • Peer Reviewed
• [Journal Article] Tracking multiple components of a nuclear wavepacket in photoexcited Cu(I)-phenanthroline complex using ultrafast X-ray spectroscopy (2019)
  • Author(s): T. Katayama, T. Northey, W. Gawelda, C. J. Milne, G. Vanko, F. A. Lima, R. Bohinc, Z. Nemeth, S. Nozawa, T. Sato, D. Khakhulin, J. Szlachetko, T. Togashi, S. Owada, S. Adachi, C. Bressler, M. Yabashi, and T. J .Penfold
  • Journal Title: Nature Communications Volume: 10 Issue: 1 Pages: 3606-3606
  • DOI: 10.1038/s41467-019-11499-w
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Microstructural deformation process of shock-compressed polycrystalline aluminum (2019)
  • Author(s): Ichiyanagi Kouhei、Takagi Sota、Kawai Nobuaki、Fukaya Ryo、Nozawa Shunsuke、Nakamura Kazutaka G.、Liss Klaus-Dieter、Kimura Masao、Adachi Shin-ichi
  • Journal Title: Scientific Reports Volume: 9 Issue: 1 Pages: 7604-7604
  • DOI: 10.1038/s41598-019-43876-2
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] One-shot preparation of topologically chimeric nanofibers via a gradient supramolecular copolymerization (2019)
  • Author(s): Kitamoto Yuichi、Pan Ziyan、Prabhu Deepak D.、Isobe Atsushi、Ohba Tomonori、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Yagai Shiki
  • Journal Title: Nature Communications Volume: 10 Issue: 1 Pages: 12815-12824
  • DOI: 10.1038/s41467-019-12654-z
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Formation of a Ruthenium(V)-Imido Complex and the Reactivity in Substrate Oxidation in Water through the Nitrogen Non-Rebound Mechanism (2019)
  • Author(s): Tomoya Ishizuka, Taichi Kogawa, Misaki Makino, Yoshihito Shiota, Kazuaki Ohara, Hiroaki Kotani, Shunsuke Nozawa, Shin-ichi Adachi, Kentaro Yamaguchi, Kazunari Yoshizawa, Takahiko Kojima
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 19 Pages: 12815-12824
  • DOI: 10.1021/acs.inorgchem.9b01781
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Topological Impact on the Kinetic Stability of Supramolecular Polymers (2019)
  • Author(s): Suzuki Atsuhito、Aratsu Keisuke、Datta Sougata、Shimizu Nobutaka、Takagi Hideaki、Haruki Rie、Adachi Shin-ichi、Hollamby Martin、Silly Fabien、Yagai Shiki
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 33 Pages: 13196-13202
  • DOI: 10.1021/jacs.9b06029
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CH2I2 (2019)
  • Author(s): Fukuzawa Hironobu、Takanashi Tsukasa、Kukk Edwin、Motomura Koji、Wada Shin-ichi、Nagaya Kiyonobu、Ito Yuta、Nishiyama Toshiyuki、Christophe Nicolas 6, Yoshiaki Kumagai、Iablonskyi Denys、Mondal Subhendu、Tachibana Tetsuya、You Daehyun、Yamada Syuhei、Sakakibara Yuta、Asa Kazuki、Sato Yuhiro、Sakai Tsukasa、et al.
  • Journal Title: Nature Communications Volume: － Issue: 1 Pages: 2186-2186
  • DOI: 10.1038/s41467-019-10060-z
  • NAID: 120006634627
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Kinetics of a Phonon-Mediated Laser-Driven Structural Phase Transition in Sn2P2Se6 (2019)
  • Author(s): M.Kubli、M.Savoini、E.Abreu、B.Burganov、G.Lantz、L.Huber、M.Neugebauer、L.Boie、V.Esposito、E.Bothschafter、S.Parchenko 、S.Grubel、M.Porer、J.Rittmann 、P.Beaud、U.Staub、M.Yabashi、Y.Tanaka、T.Katayama、T.Togashi、A.Kohutych、Y.Vysochanskii、S.Johnson
  • Journal Title: Applied Sciences Volume: 9 Issue: 3 Pages: 525-525
  • DOI: 10.3390/app9030525
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Ultrafast Structural Dynamics of Nanoparticles in Intense Laser Fields (2019)
  • Author(s): Nishiyama Toshiyuki、Kumagai Yoshiaki、Niozu Akinobu、Fukuzawa Hironobu、Motomura Koji、Bucher Maximilian、Ito Yuta、Takanashi Tsukasa、Asa Kazuki、Sato Yuhiro、You Daehyun、Li Yiwen、Ono Taishi、Kukk Edwin、Miron Catalin、Neagu Liviu、Katayama Tetsuo、他17名
  • Journal Title: Physical Review Letters Volume: 123 Issue: 12 Pages: 123201-123201
  • DOI: 10.1103/physrevlett.123.123201
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Early time dynamics of laser-ablated silicon using ultrafast grazing incidence X-ray scattering (2019)
  • Author(s): Hull C.、Raj S.、Lam R.、Katayama T.、Pascal T.、Drisdell W.S.、Saykally R.、Schwartz C.P.
  • Journal Title: Chemical Physics Letters Volume: 736 Pages: 136811-136811
  • DOI: 10.1016/j.cplett.2019.136811
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Arrival timing diagnostics at a soft X-ray free-electron laser beamline of SACLA BL1 (2019)
  • Author(s): Owada Shigeki、Nakajima Kyo、Togashi Tadashi、Katayama Tetsuo、Yumoto Hirokatsu、Ohashi Haruhiko、Yabashi Makina
  • Journal Title: Journal of Synchrotron Radiation Volume: 26 Issue: 3 Pages: 887-890
  • DOI: 10.1107/s1600577519002315
  • Peer Reviewed
• [Journal Article] Polarization control with an X-ray phase retarder for high-time-resolution pump-probe experiments at SACLA (2019)
  • Author(s): Kubota Y.、Suzuki M.、Katayama T.、Yamamoto K.、Tono K.、Inubushi Y.、Seki T.、Takanashi K.、Wadati H.、Yabashi M.
  • Journal Title: Journal of Synchrotron Radiation Volume: 26 Issue: 4 Pages: 1139-1143
  • DOI: 10.1107/s1600577519006222
  • Peer Reviewed / Open Access
• [Journal Article] A versatile experimental system for tracking ultrafast chemical reactions with X-ray free-electron lasers (2019)
  • Author(s): Katayama Tetsuo、Nozawa Shunsuke、Umena Yasufumi、Lee SungHee、Togashi Tadashi、Owada Shigeki、Yabashi Makina
  • Journal Title: Structural Dynamics Volume: 6 Issue: 5 Pages: 054302-054302
  • DOI: 10.1063/1.5111795
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] X-ray optics for advanced ultrafast pump-probe X-ray experiments at SACLA (2019)
  • Author(s): T. Katayama,T. Hirano, Y. Morioka, Y. Sano, T. Osaka, S. Owada, T. Togashi, M. Yabashi
  • Journal Title: Journal of Synchrotron Radiation Volume: 26 Issue: 2 Pages: 333-338
  • DOI: 10.1107/s1600577518018362
  • Peer Reviewed / Open Access
• [Journal Article] Ultrafast demagnetization of Pt magnetic moment in L10-FePt probed by magnetic circular dichroism at a hard x-ray free electron laser (2019)
  • Author(s): Yamamoto Kohei、Kubota Yuya、Suzuki Motohiro、Hirata Yasuyuki、Carva Karel、Berritta Marco、Takubo Kou、Uemura Yohei、Fukaya Ryo、Tanaka Kenta、Nishimura Wataru、Ohkochi Takuo、Katayama Tetsuo、他8名
  • Journal Title: New Journal of Physics Volume: 21 Issue: 12 Pages: 123010-123010
  • DOI: 10.1088/1367-2630/ab5ac2
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Selective Reduction Mechanism of Graphene Oxide Driven by the Photon Mode versus the Thermal Mode (2019)
  • Author(s): M. Hada, K. Miyata, S. Ohmura, Y. Arashida, K. Ichiyanagi, I. Katayama, T. Suzuki, W. Chen, S. Mizote, T. Sawa, T. Yokoya, T. Seki, J. Matsuo, T. Tokunaga, C. Itoh, K. Tsuruta, R. Fukaya, S. Nozawa, S. Adachi, J. Takeda, K. Onda, S. Koshihara, Y. Hayashi, Y. Nishina
  • Journal Title: ACS Nano Volume: 13 Issue: 9 Pages: 10103-10112
  • DOI: 10.1021/acsnano.9b03060
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] フェムト秒時間分解X線散乱法による励起分子構造解析 (2021)
  • Author(s): 足立伸一
  • Organizer: 日本顕微鏡学会 第77回学術講演会
  • Invited
• [Presentation] Ultrafast molecular structural dynamics studies with time-resolved X-ray methods (2020)
  • Author(s): 足立伸一
  • Organizer: 2020年web光化学討論会
  • Invited
• [Presentation] Ultrafast time-resolved X-ray experiments at SACLA (2020)
  • Author(s): Tetsuo Katayama
  • Organizer: QCrOM2020
  • Int'l Joint Research / Invited
• [Presentation] XFELを用いたフェムト秒X線溶液散乱による光化学反応中の反応経路の可視化 (2020)
  • Author(s): 野澤俊介
  • Organizer: 第34回日本放射光学会年会・放射光科学合同シンポジウム
  • Invited
• [Presentation] Complementarity of SR and XFEL sources for tracking chemical reactions in solution with ultrashort X-ray pulses (2019)
  • Author(s): Shin-ichi Adachi
  • Organizer: Time-Resolved Chemistry and APS-U
  • Int'l Joint Research / Invited
• [Presentation] Complementarity of SR and XFEL sources for tracking chemical reactions in solution with ultrashort X-ray pulses (2019)
  • Author(s): Shin-ichi Adachi
  • Organizer: International Young Researchers Workshop on Synchrotron Radiation Science 2019 (YRSR2019)
  • Int'l Joint Research / Invited
• [Presentation] Capturing structural dynamics of photocatalyst by ultrafast X-ray spectroscopy (2019)
  • Author(s): Shin-ichi Adachi
  • Organizer: The 5th International Conference on Ultrafast Structural Dynamics (ICUSD)
  • Int'l Joint Research / Invited
• [Presentation] Tracking Chemical Reactions in Solution with Ultrashort X-ray Pulses (2019)
  • Author(s): Shin-ichi Adachi
  • Organizer: The 1st Workshop of Reaction Infography (R-ing) Unit
  • Int'l Joint Research / Invited
• [Presentation] Tracking ultrafast chemical reaction with X-ray free electron laser (2019)
  • Author(s): Tetsuo Katayama
  • Organizer: International workshop on science at x-ray free electron lasers: Chemical physics and materials science in extreme x-rays light and extreme fields
  • Int'l Joint Research / Invited
• [Book] Ｘ線分光 (2019)
  • Author(s): 日本化学会、福本 恵紀、野澤 俊介、足立 伸一
  • Total Pages: 126
  • Publisher: 共立出版
  • ISBN: 9784320044722
• [Remarks] 新学術領域「高速分子動画」研究者紹介
  • URL: http://www.molmovies.med.kyoto-u.ac.jp/member/