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Functional Model of Methane Generation Enzyme MCR Having Ni-containing F430 as a Cofactor

Research Project

Project/Area Number 18K19099
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
Research InstitutionOsaka University

Principal Investigator

Hayashi Takashi  大阪大学, 工学研究科, 教授 (20222226)

Project Period (FY) 2018-06-29 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2019: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2018: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords人工補因子 / F430 / ヘムタンパク質 / ニッケル錯体 / メタン生生 / メタン生成 / ミオグロビン
Outline of Final Research Achievements

In this study, focusing on methyl coenzyme M reductase (MCR) containing a nickel hydrocorfinoid cofactor F430 involved in methanogenesis, we prepared myoglobin reconstituted with an artificial cofactor, nickel monovalent tetradehydrocholine, as a functional model of the MCR protein. This reconstituted protein was found to react not only with methyl iodide but also with other methyl donors such as methyl p-toluenesulfonate and trimethylsulfonium iodide, and the catalytic methane generation was observed in an aqueous solution in the presence of dithionate. Furthermore, it was revealed that the reconstituted protein does not give any homocoupling product of the benzyl bromide derivatives and provides reductively a dehydrogenated product.

Academic Significance and Societal Importance of the Research Achievements

ニッケルヒドロコルフィノイド補因子F430を含むメチル補酵素Mレダクターゼ(MCR)は、嫌気性条件下での生物学的メタン生成に関与していることが知られている。しかしこの酵素は複雑かつ不安定であり、本研究を開始する時点では、化学の立場からの研究があまり進んでいなかった。今回、この複雑な酵素を理解するために、簡単な構造を有するミオグロビンを反応場として、補因子も単純化したニッケル錯体を複合化させることにより、温和な条件下でメタンを触媒的に発生させることを初めて達成した。ニッケル錯体を含むMCR触媒によるメタン生成の機構に対する理解に貢献している点で学術的意義が認められる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (16 results)

All 2021 2020 2019 2018 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results) Presentation (7 results) (of which Int'l Joint Research: 3 results,  Invited: 4 results) Remarks (1 results)

  • [Journal Article] Myoglobins engineered with artificial cofactors serve as artificial metalloenzymes and models of natural enzymes2021

    • Author(s)
      Oohora Koji、Hayashi Takashi
    • Journal Title

      Dalton Transactions

      Volume: 50 Issue: 6 Pages: 1940-1949

    • DOI

      10.1039/d0dt03597a

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Methane Generation and Reductive Debromination of Benzylic Position by Reconstituted Myoglobin Containing Nickel Tetradehydrocorrin as a Model of Methyl-coenzyme M Reductase2020

    • Author(s)
      Miyazaki Yuta、Oohora Koji、Hayashi Takashi
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 17 Pages: 11995-12004

    • DOI

      10.1021/acs.inorgchem.0c00901

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Myoglobin Reconstituted with Ni Tetradehydrocorrin as a Methane‐Generating Model of Methyl‐coenzyme M Reductase2019

    • Author(s)
      Oohora Koji、Miyazaki Yuta、Hayashi Takashi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 39 Pages: 13813-13817

    • DOI

      10.1002/anie.201907584

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Methane generation via intraprotein C-S bond cleavage in cytochrome b562 reconstituted with nickel didehydrocorrin2019

    • Author(s)
      Miyazaki Yuta、Oohora Koji、Hayashi Takashi
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 901 Pages: 120945-120945

    • DOI

      10.1016/j.jorganchem.2019.120945

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electrochemical CO2 reduction by a cobalt bipyricorrole complex: decrease of an overpotential value derived from monoanionic ligand character of the porphyrinoid species2019

    • Author(s)
      Ogawa Ayumu、Oohora Koji、Gu Wenting、Hayashi Takashi
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 4 Pages: 493-496

    • DOI

      10.1039/c8cc08876d

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Photoinduced electron transfer within supramolecular hemoprotein co-assemblies and heterodimers containing Fe and Zn porphyrins2019

    • Author(s)
      Kajihara Ryota、Oohora Koji、Hayashi Takashi
    • Journal Title

      Journal of Inorganic Biochemistry

      Volume: 193 Pages: 42-51

    • DOI

      10.1016/j.jinorgbio.2019.01.001

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Hemoproteins Reconstituted with Artificial Metal Complexes as Biohybrid Catalysts2019

    • Author(s)
      Oohora Koji、Onoda Akira、Hayashi Takashi
    • Journal Title

      Accounts of Chemical Research

      Volume: 52 Issue: 4 Pages: 945-954

    • DOI

      10.1021/acs.accounts.8b00676

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of meso-Substituted Cobalt Tetradehydrocorrin and Evaluation of Its Electrocatalytic Behavior Toward CO2 Reduction and H2 Evolution2018

    • Author(s)
      Ogawa Ayumu、Oohora Koji、Hayashi Takashi
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 23 Pages: 14644-14652

    • DOI

      10.1021/acs.inorgchem.8b02333

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] タンパク質マトリクスが形成する分子空間を反応場に利用した人工生体金属触媒の創製2020

    • Author(s)
      林 高史
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Hemoprotein Modification Toward Artificial Biocatalyst Generation2019

    • Author(s)
      Takashi Hayashi, Akira Onoda, Koji Oohora
    • Organizer
      Artzymes2.0
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] A Functional Model of Methyl-coenzyeme M Reductase Using Myoglobin Reconstituted with a Nickel Porphyrinoid Complex2019

    • Author(s)
      Takashi Hayashi, Yuta Miyazaki, and Koji Oohora
    • Organizer
      2019 Korea-Taiwan-Japan Biological Inorganic Chemistry Symposium
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Construction and Evaluation of Functional Models of Methane-producing Enzyme by Combining a Ni Corrinoid Complex with a Protein Matrix as a Reaction Scaffold2019

    • Author(s)
      Yuta Miyazaki, Koji Oohora, Takashi Hayashi
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Construction and Evaluation of a Protein-based Functional Model of Methane-producing Enzyme2018

    • Author(s)
      Yuta Miyazaki, Koji Oohora, Takashi Hayashi
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Methanogenesis from a Hemoprotein-based Functional Model of Methane-producing Enzyme2018

    • Author(s)
      Yuta Miyazaki, Koji Oohora, Takashi Hayashi
    • Organizer
      JSPS Japanese-German Graduate Externship International Symposium Biological and Chemical Methods for Selective Catalysis
    • Related Report
      2018 Research-status Report
  • [Presentation] Myoglobin Reconstituted with a Corrinoid Metal Complex2018

    • Author(s)
      Hayashi Takashi
    • Organizer
      9th Asian Biological Inorganic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] 大阪大学大学院工学研究科林研究室

    • URL

      http://www.chem.eng.osaka-u.ac.jp/~hayashiken/index.html

    • Related Report
      2018 Research-status Report

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Published: 2018-07-25   Modified: 2022-01-27  

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