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Development of Mononucelar Copper-oxyl Radical Species

Research Project

Project/Area Number 16K13963
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

Itoh Shinobu  大阪大学, 工学研究科, 教授 (30184659)

Research Collaborator MORIMOTO Yuma  
Sugimoto Hideki  
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords単核銅錯体 / 活性酸素錯体 / オキシラジカル錯体 / 酸化反応 / 金属酵素 / 錯体触媒 / 反応機構 / 酸化活性種 / 銅含有酸化酵素
Outline of Final Research Achievements

The mononuclear copper(II)-superoxide complex has been involved as a key reactive intermediate in a variety of oxidation reactions catalyzed by copper-containing metalloenzymes and several types of copper model complexes. However, little was known about the physicochemical properties and reactivity. In this study, the reactions of copper complexes supported by our functional ligands and peroxides have been investigated in detail to demonstrate possible contribution of such a mononuclear copper(II)-superoxide species in the oxidation reactions.

Academic Significance and Societal Importance of the Research Achievements

単核銅(II)-オキシラジカル種は、銅含有金属酵素や各種銅錯体が触媒する種々の酸化反応に含まれる重要な酸化活性種である。しかし、その詳細な構造や物性、および反応性に関する情報は全くなく、それらの解明は、生物無機化学や触媒化学の分野における重要な研究課題となっている。本研究で得られた成果は、この様な銅-活性酸素錯体の反応性に関して重要な情報を提供するものであり、生体反応や各種酸化反応の機構解明につながるものとして学術的意義は大きい。また、新しい錯体触媒の開発に対しても有用な指針を提供するものであり、錯体化学や触媒化学の発展に大きく寄与するものである。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (25 results)

All 2019 2018 2017 2016 Other

All Int'l Joint Research (4 results) Journal Article (9 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 9 results,  Open Access: 1 results,  Acknowledgement Compliant: 1 results) Presentation (9 results) (of which Int'l Joint Research: 8 results,  Invited: 9 results) Book (2 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] University of Heidelberg(ドイツ)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] 大連工科大学(中国)

    • Related Report
      2017 Research-status Report
  • [Int'l Joint Research] ハイデルベルグ大学(ドイツ)

    • Related Report
      2017 Research-status Report
  • [Int'l Joint Research] University of California, Irvine(米国)

    • Related Report
      2016 Research-status Report
  • [Journal Article] Cupric-superoxide complex that induces a catalytic aldol reaction-type C-C bond formation2019

    • Author(s)
      T. Abe, Y. Hori, Y. Shiota, T. Ohta, Y. Morimoto, H. Sugimoto, T. Ogura, K. Yoshizawa, and S. Itoh
    • Journal Title

      Communications Chemistry

      Volume: 2 Issue: 1 Pages: 1-7

    • DOI

      10.1038/s42004-019-0115-6

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dioxygen Activation Mechanism by Copper Monooxygenases2018

    • Author(s)
      伊東 忍、藤枝伸宇
    • Journal Title

      生化学

      Volume: 90 Issue: 3 Pages: 320-327

    • DOI

      10.14952/SEIKAGAKU.2018.900320

    • ISSN
      0037-1017
    • Year and Date
      2018-06-25
    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structure and Reactivity of Copper Complexes Supported by a Bulky Tripodal N4 Ligand: Copper(I)/Dioxygen Reactivity and Formation of a Hydroperoxide Copper(II) Complex2018

    • Author(s)
      S. Paria, T. Ohta, Y. Morimoto, H. Sugimoto, T. Ogura, and S. Itoh
    • Journal Title

      Zeitschrift fur Anorganische und Allgemeine Chemie

      Volume: 644 Issue: 14 Pages: 780-790

    • DOI

      10.1002/zaac.201800083

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 2-(2-Pyridyl)ethylamine (Pye) Ligands in Copper(I)-dioxygen Chemistry2018

    • Author(s)
      Shinobu Itoh, Tsukasa Abe, Yuma Morimoto, and Hideki Sugimoto
    • Journal Title

      Inorg. Chim. Acta

      Volume: 印刷中 Pages: 38-46

    • DOI

      10.1016/j.ica.2017.09.017

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper(I)-Dioxygen Reactivity in an Isolated Cavity of Nanoscale Molecular Architecture2018

    • Author(s)
      Sayantan Paria, Yuma Morimoto, Takehiro Ohta, Hideki Sugimoto, Nobutaka Fujieda, Takashi Ogura, and Shinobu Itoh*
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2018 Issue: 19 Pages: 1976-1983

    • DOI

      10.1002/ejic.201800029

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Copper-Catalyzed Selective Oxygenation of Methyl and Benzyl Substituents in Pyridine with O22017

    • Author(s)
      阿部司、田中真司、小川敦子、田村正則、佐藤一彦、伊東忍
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 3 Pages: 348-350

    • DOI

      10.1246/cl.161074

    • NAID

      130005436660

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Dioxygenation of Flavonol Catalyzed by CuII-complexes Supported by Carboxylate-containing Ligands. Structural and Functional Models of Quercetin 2,4-Dioxygenase (2,4-QD)2017

    • Author(s)
      Ying-Ji Sun,* Pei Li, Qian-Qian Huang, Jian-Jun Zhang, and Shinobu Itoh*
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2017 Issue: 13 Pages: 1845-1854

    • DOI

      10.1002/ejic.201601371

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Geometric Effects on O-O Bond Scission of Copper(II)-alkylperoxide Complexes2017

    • Author(s)
      Tsukasa Abe, Yuma Morimoto, Kaoru Mieda, Hideki Sugimoto, Nobutaka Fujieda, Takashi Ogura, and Shinobu Itoh*
    • Journal Title

      J. Inorg. Biochem.

      Volume: 177 Pages: 375-383

    • DOI

      10.1016/j.jinorgbio.2017.08.016

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tetrahedral Copper(II) Complexes with a Labile Coordination Site Supported by a tris-Tetramethylguanidinato Ligand2017

    • Author(s)
      Ikuma Shimizu, Yuma Morimoto, Dieter Faltermeier, Marion Kerscher, Sayantan Paria, Tsukasa Abe, Hideki Sugimoto, Nobutaka Fujieda, Kaori Asano, Takeyuki Suzuki, Peter Comba,* and Shinobu Itoh*
    • Journal Title

      Inorg. Chem.

      Volume: 56 Issue: 16 Pages: 9634-9645

    • DOI

      10.1021/acs.inorgchem.7b01154

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Versataile Reactivity of Mononuclear Copper(II)-Superoxide Complexes2018

    • Author(s)
      Shinobu Itoh
    • Organizer
      CuBICS 2018 (Copper Bioinorganic Chemistry Symposium)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Reactivity of Mononuclear Copper(II)-Superoxide Complexes2018

    • Author(s)
      Shinobu Itoh
    • Organizer
      Korea-Taiwan-Japan Bioinorganic Chemistry Symposium 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Unprecedented Reactivity of Mononuclear Copper(II)-superoxide Complexes2018

    • Author(s)
      Shinobu Itoh
    • Organizer
      14th European Biological Inorganic Chemistry Conference (EuroBIC 14)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] New Insights into Tyrosinase Mechanis2018

    • Author(s)
      Shinobu Itoh
    • Organizer
      9th Asian Biological Inorganic Chemistry Conference (AsBIC-9)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] O2-activation and Aliphatic Hydroxylation by Copper Monooxygenase Models2017

    • Author(s)
      Shinobu Itoh
    • Organizer
      5th Symposium on Advanced Biological Inorganic Chemistry (SABIC2017)
    • Related Report
      2017 Research-status Report 2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Copper-Dioxygen Chemistry. -From Modeling Studies to Enzymatic Reactions-2017

    • Author(s)
      Shinobu Itoh
    • Organizer
      18th International Conference on Biological Inorganic Chemistry (ICBIC18)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Oxygen Activation Mechanism by Copper Monooxygenases. From Modeling Studies to Enzymatic Reactions2017

    • Author(s)
      Shinobu Itoh
    • Organizer
      第26回金属の関与する生体関連反応シンポジウム(SRM2017)
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] Mononuclear Copper Reaction Center for Oxygen Activation2016

    • Author(s)
      Shinobu Itoh
    • Organizer
      42th International Conference on Coordination Chemistry (ICCC-42)
    • Place of Presentation
      University of Brest, Brest, France
    • Year and Date
      2016-07-03
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Activation at A Mononuclear Copper Reaction Center2016

    • Author(s)
      Shinobu Itoh
    • Organizer
      Telluride Woekshop on Activation of Small Molecules
    • Place of Presentation
      Telluride, Cororado, USA
    • Year and Date
      2016-06-21
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Book] Encyclopedia of Inorganic and Bioinorganic Chemistry2017

    • Author(s)
      Nobutaka Fujieda and Shinobu Itoh
    • Total Pages
      500
    • Publisher
      John Wiley & Sons
    • ISBN
      9781119159834
    • Related Report
      2017 Research-status Report
  • [Book] フロンティア生物無機化学2016

    • Author(s)
      伊東 忍
    • Total Pages
      550
    • Publisher
      三共出版
    • Related Report
      2016 Research-status Report
  • [Patent(Industrial Property Rights)] ホルミルピリジン類の製造方法2016

    • Inventor(s)
      伊東 忍他
    • Industrial Property Rights Holder
      伊東 忍他
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2016-116314
    • Filing Date
      2016-06-10
    • Related Report
      2016 Research-status Report

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Published: 2016-04-21   Modified: 2022-02-16  

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