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Formation and Characterization of Metal-Phenoxyl Radical by Air Oxidation

Research Project

Project/Area Number 16K05716
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionIbaraki University

Principal Investigator

Yuichi Shimazaki  茨城大学, 理工学研究科(理学野), 准教授 (80335992)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords酸素分子 / 酸化反応 / フェノキシルラジカル / 銅 / ニッケル / 酸化 / 酸素 / ニッケル錯体 / 空気酸化 / 高原子価金属錯体
Outline of Final Research Achievements

Garactose oxidase (GO) is a single copper oxidase, which catalyzes oxidation of a primary alcohol to the corresponding aldehyde. The active form of GO is well-known to be a Cu(II)-phenoxyl radical, which can act as two electron oxidant for the primary alcohol oxidation to form a Cu(I)-phenol species. Reaction of the Cu(I)-phenol species with an oxygen molecule to reproduce the Cu(II)-phenoxyl radical, and therefore GO is possible to be fuctionalization as a catalyst. The purpose of this study was such the formation of the phenoxyl radical metal complexes by air oxidation. We have been successful to find out formation of the Cu(II)-phenoxyl radical complex by air-oxidation from the various investigation.

Academic Significance and Societal Importance of the Research Achievements

酸素分子は生命活動において不可欠であり、重要な分子である。しかし、基質の酸化反応においては、酸素分子よりも、過酸化水素などのポテンシャルの高い活性酸素種などを使用する場合が多く、酸素分子を直接触媒機構に導入することは難しいことが多い。前述のGOの活性型であるCu(II)-phenoxyl radicalの電子状態の詳細を調べるため多くの研究がされてきたが、酸素分子によるCu(II)-phenoxyl radicalの生成は未だ報告されていない。本研究結果は酸素分子を用いた生体内に見られ、無駄にエネルギーを消費せずに活性種が生成する初めての例である。

Report

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

    (16 results)

All 2019 2018 2017 2016 Other

All Int'l Joint Research (1 results) Journal Article (5 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 5 results,  Open Access: 5 results,  Acknowledgement Compliant: 1 results) Presentation (9 results) (of which Int'l Joint Research: 6 results,  Invited: 3 results) Book (1 results)

  • [Int'l Joint Research] Simon Fraser University(Canada)

    • Related Report
      2016 Research-status Report
  • [Journal Article] π‐π Stacking Interaction in an Oxidized CuII‐salen Complex with a Side Chain Indole Ring. An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase2019

    • Author(s)
      Oshita Hiromi、Suzuki Takashi、Kawashima Kyohei、Abe Hitoshi、Tani Fumito、Mori Seiji、Yajima Tatsuo、Shimazaki Yuichi
    • Journal Title

      Chemistry A European Journal

      Volume: 印刷中 Issue: 32 Pages: 7649-7658

    • DOI

      10.1002/chem.201900733

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex2018

    • Author(s)
      Linus Chiang, Erik C. Wasinger, Yuichi Shimazaki, Victor Young Jr., Tim Storr, T. Daniel P. Stack
    • Journal Title

      Inorganica Chimica Acta

      Volume: 印刷中

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Characterization of the one-electron oxidized Cu(II)-salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)-phenoxyl radical species2017

    • Author(s)
      Oshita Hiromi、Yoshimura Takayoshi、Mori Seiji、Tani Fumito、Shimazaki Yuichi、Yamauchi Osamu
    • Journal Title

      Journal of Biological Inorganic Chemistry

      Volume: 23 Issue: 1 Pages: 51-59

    • DOI

      10.1007/s00775-017-1508-6

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Characterization of Group 10-Metal-p-Substituted Phenoxyl Radical Complexes with Schiff Base Ligands.2017

    • Author(s)
      Oshita Hiromi、Kikuchi Misa、Mieda Kaoru、Ogura Takashi、Yoshimura Takayoshi、Tani Fumito、Yajima Tatsuo、Abe Hitoshi、Mori Seiji、Shimazaki Yuichi
    • Journal Title

      ChemistrySelect

      Volume: 2 Issue: 31 Pages: 10221-10231

    • DOI

      10.1002/slct.201701986

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electronic Structure Evaluation of an Oxidized Tris-Methoxy Ni Salen Complex2016

    • Author(s)
      Linus Chiang, Ryan M. Clarke, Khrystyna Herasymchuk, Mathew Sutherland, Yuichi Shimazaki, and Tim Storr
    • Journal Title

      Eur. J. Inorg. Chem

      Volume: - Issue: 1 Pages: 49-55

    • DOI

      10.1002/ejic.201501144

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Presentation] 2つのフェノラート基を有する三脚型配位子を用いたNi(II),Cu(II)-フェノキシルラジカルの生成と性質2019

    • Author(s)
      鈴木 崇・佐藤朱里・大下宏美・島崎優一
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Cu(II)-フェノラート錯体の空気酸化によるCu(II)-フェノキシルラジカル錯体の生成2019

    • Author(s)
      鈴木 崇・大下宏美・島崎優一
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] The electronic structures of M(II)-phenoxyl radical complexes with a side chain indole ring; the effect of π-π stacking interaction with indole ring2018

    • Author(s)
      H. Oshita, F. Tani, H. Abe, S. Mori, T. Yajima, Y. Shimazaki
    • Organizer
      14th European Biological Inorganic Chemistry Conference
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 側鎖基にインドールを有する金属-フェノキシルラジカル錯体の構造と性質;インドールの弱い相互作用が電子状態に及ぼす影響2018

    • Author(s)
      大下宏美、谷文都、矢島辰雄、島崎優一
    • Organizer
      第12回バイオ関連化学シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] Oxidation Chemistry of Nickel(II)- phenolate Complexes2017

    • Author(s)
      Y. Shimazaki
    • Organizer
      BIT’s 3rd Annual World Congress of Smart Materials
    • Place of Presentation
      Bangkok, Thailand
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] The Electronic Structure of oxidized NiII, CuII-Salen Complexes Containing an Indole Ring2017

    • Author(s)
      Hiromi Oshita, Yuichi Shimazaki
    • Organizer
      ISACS: Challenges in Inorganic Chemistry
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Electronic Structure of Metal (II) Methylthiophenoxyl Radical Complexes2017

    • Author(s)
      Yuichi Shimazaki
    • Organizer
      the 14th International Symposium on Applied Bioinorganic Chemistry (ISABC14)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Mechanistic study of alcohol oxidation by oxidized CuII salen-type complexes: Relationship between reactivity and the electronic structure of the complexes2017

    • Author(s)
      Yuichi Shimazaki
    • Organizer
      The 3rd International Conference on Organic & Inorganic Chemistry
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] X-ray crystal structures of the one-electron oxidized metal-phenolate complexes; geometric and electronic structures relationship2016

    • Author(s)
      Y. Shimazaki
    • Organizer
      International Conference on Applied Crystallography 2016
    • Place of Presentation
      Houston, USA
    • Year and Date
      2016-10-17
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Book] Recent Advances in the Field of Phenoxyl Radical-Metal Complexes in The Chemistry of Metal Phenolates2016

    • Author(s)
      Y. Shimazaki
    • Total Pages
      26
    • Publisher
      John Wiley & Sons, Ltd
    • Related Report
      2016 Research-status Report

URL: 

Published: 2016-04-21   Modified: 2020-03-30  

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