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Relaxation mechanism of nucleobases and their derivatives in aqueous solution

Research Project

Project/Area Number 22K14647
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 32010:Fundamental physical chemistry-related
Research InstitutionKyoto University

Principal Investigator

Karashima Shutaro  京都大学, 理学研究科, 特定助教 (40890926)

Project Period (FY) 2022-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2023: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2022: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords光電子分光 / 光反応ダイナミクス / フェムト秒レーザー / 超高速光電子分光 / 反応ダイナミクス / 極端紫外光
Outline of Research at the Start

DNA/RNAの光受容部分である核酸塩基の光反応ダイナミクスの研究は、生命科学・物理科学の両面において重要である。本研究では水溶液内における核酸塩基や誘導体の超高速光化学反応について時間分解光電子分光法で研究する。検出光に極端紫外光を応用することで、従来の実験では検出不可能であったエネルギー領域まで観測し、ππ*状態に励起された核酸塩基の緩和過程の全体像を捉えることを目指す。

Outline of Final Research Achievements

We performed extreme ultraviolet photoelectron spectroscopy on the photoreaction dynamics of the nucleobase molecules and their derivatives in liquid water. The results show that only a few tens of percent at most remain in the electronically excited state on the picosecond scale, and most quickly relax to the electronic ground state. In addition, the reaction dynamics of molecules in the gas phase were studied. It has found that coordination to the 5-carbon atom has a critical effect on the efficiency of electronic relaxation by comparing the results of uracil, thymine (5-methyluracil), and 6-methyluracil.

Academic Significance and Societal Importance of the Research Achievements

DNAやRNAの光化学反応は損傷や変異といった生命維持への脅威につながるため、光を吸収するアンテナ的役割を担う核酸塩基分子の光反応ダイナミクスの解明は非常に重要である。従来とは異なる実験手法(極端紫外光電子分光法)で研究することで、光反応過程における各電子状態の電子束縛エネルギー推移や反応収率を明らかとした。一方で過渡吸収分光法による過去研究結果との間では、反応収率において一部整合していない点も見られた。今後も検討・議論を重ねることで、核酸塩基分子の光反応機構の解明に向けて研究のさらなる発展が望まれる。

Report

(3 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • Research Products

    (14 results)

All 2024 2023 2022

All Journal Article (7 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 7 results,  Open Access: 2 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 1 results)

  • [Journal Article] Vibrational Motions in Ultrafast Electronic Relaxation of Pyrazine2024

    • Author(s)
      Karashima Shutaro、Humeniuk Alexander、Suzuki Toshinori
    • Journal Title

      Journal of the American Chemical Society

      Volume: - Pages: 11067-1071

    • DOI

      10.1021/jacs.4c02886

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Charge transfer reaction at gas-liquid interface of aqueous tetrabutylammonium iodide solution: influence of ions on dynamical response of solvent2023

    • Author(s)
      Shutaro Karashima; Yoshi-Ichi Suzuki; Yo-ichi Yamamoto; Toshinori Suzuki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 97 Issue: 1

    • DOI

      10.1093/bulcsj/uoad012

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Extreme Ultraviolet Laser Photoelectron Spectroscopy of Flat Liquid Jet Generated Using Microfluidic Device2023

    • Author(s)
      Yamamoto, Y.-I.; Yano, H.; Karashima, S.; Uenishi, R.; Orimo, N.; Nishitani, J.; Suzuki, T.
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 96 Issue: 9 Pages: 938-942

    • DOI

      10.1246/bcsj.20230151

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ultrafast Ring Closure Reaction of Gaseous <i>cis</i>-Stilbene from S<sub>1</sub>(ππ*)2023

    • Author(s)
      Karashima Shutaro、Miao Xincheng、Kanayama Akio、Yamamoto Yo-ichi、Nishitani Junichi、Kavka Nikita、Mitric Roland、Suzuki Toshinori
    • Journal Title

      Journal of the American Chemical Society

      Volume: 145 Issue: 6 Pages: 3283-3288

    • DOI

      10.1021/jacs.2c12266

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Formation of Long-Lived Dark States during Electronic Relaxation of Pyrimidine Nucleobases Studied Using Extreme Ultraviolet Time-Resolved Photoelectron Spectroscopy2023

    • Author(s)
      Yuta Miura, Yo-ichi Yamamoto, Shutaro Karashima, Natsumi Orimo, Ayano Hara, Kanae Fukuoka, Tatsuya Ishiyama, and Toshinori Suzuki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 145 Issue: 6 Pages: 3369-3381

    • DOI

      10.1021/jacs.2c09803

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ultrafast Electronic Relaxation in 6-Methyluracil and 5-Fluorouracil in Isolated and Aqueous Conditions: Substituent and Solvent Effects2023

    • Author(s)
      Natsumi Orimo, Yo-ichi Yamamoto, Shutaro Karashima, Alexie Boyer, and Toshinori Suzuki
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 14 Issue: 11 Pages: 2758-2763

    • DOI

      10.1021/acs.jpclett.3c00195

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ultrafast Photoisomerization of Ethylene Studied Using Time-Resolved Extreme Ultraviolet Photoelectron Spectroscopy2022

    • Author(s)
      Karashima Shutaro、Humeniuk Alexander、Glover William J.、Suzuki Toshinori
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 126 Issue: 24 Pages: 3873-3879

    • DOI

      10.1021/acs.jpca.2c02468

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Ultrafast ring closure reaction of gaseous cis-stilbene2023

    • Author(s)
      Shutaro Karashima, Xincheng Miao, Akio Kanayama, Yo-ichi Yamamoto, Junichi Nishitani, Nikita Kavka, Roland Mitric and Toshinori Suzuk
    • Organizer
      化学反応討論会
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Tetrabutylammonium Iodide水溶液の気液界面における電荷移動反応2023

    • Author(s)
      唐島 秀太郎, 鈴木 喜一, 山本 遥一, 鈴木 俊法
    • Organizer
      分子科学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] シス-スチルベン分子の超高速光閉環反応2023

    • Author(s)
      唐島 秀太郎,Miao Xincheng,金山 明央,山本 遥一,西谷 純一,Kavka Nikita,Mitric Roland,鈴木 俊法
    • Organizer
      分子科学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 超高速極端紫外光電子分光による有機分子の気相光化学反応機構の研究2023

    • Author(s)
      唐島 秀太郎
    • Organizer
      原子衝突学会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Ultrafast photoelectron spectroscopy of photoisomerization reaction of ethylene2022

    • Author(s)
      Karashima Shutaro、Humeniuk Alexander、Glover J. William、Suzuki Toshinori
    • Organizer
      34th International Symposium on Free Radicals
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] エチレンの光異性化反応の超高速光電子分光2022

    • Author(s)
      唐島 秀太郎、 Humeniuk Alexander、 Glover William J.、鈴木 俊法
    • Organizer
      原子衝突学会第47回年会
    • Related Report
      2022 Research-status Report
  • [Presentation] エチレンの光異性化反応の超高速光電子分光2022

    • Author(s)
      唐島 秀太郎、 Humeniuk Alexander、 Glover William J、鈴木 俊法
    • Organizer
      第16回分子科学討論会
    • Related Report
      2022 Research-status Report

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Published: 2022-04-19   Modified: 2025-01-30  

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