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A Study of Electron-Transfer Pathways in the Electron-Transfer Reactions of Metal Complexes and Hemoproteins

Research Project

Project/Area Number 03453049
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionNara Women's University

Principal Investigator

TSUKAHARA Keiichi  Nara Women's University Department of Chemistry Assistant Professor, 理学部, 助教授 (70112117)

Co-Investigator(Kenkyū-buntansha) KATO Masako  Nara Women's University Department of Chemistry Research Associate, 理学部, 助手 (80214401)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥6,900,000 (Direct Cost: ¥6,900,000)
Fiscal Year 1992: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1991: ¥5,500,000 (Direct Cost: ¥5,500,000)
KeywordsElectron-Transfer Reaction / Electron-Transfer Pathway / Hemoprotein / Chemically Modified Myoglobin / Zinc Myoglobin / Porphyrins / Photoinduced Electron-Transfer Reaction / Intramolecular Electron Transfer
Research Abstract

1) Role of the Heme Propionates in the Reduction of Metmyoglobin-It is suggested that the heme propionates have an important role in the reductions of metmyoglobins by using the dimethylester hemins and octaethylhemin which has no propionates in the heme.
2) Redox Behavior of Viologen Attached Metmyoglobin-Metmyoglobin whose lysine residue was modified with viologen was newly prepared and reduced by dithionite ions faster than native metmyoglobin. It is suggested that the viologen attached to myoglobin is reduced, following the rapid intramolecular electron-transfer reaction from the viologen radical cation to the iron(III) center.
3) Syntheses and Characterizations of a New Type of Viologen-Linked N-Alkylporphyrin and Its Zinc(II) Complex-New type of viologen-linked tetraphenylporphyrin and its zinc(II) complex containing an N-trimethylene bridge were synthesized and characterized by a two dimensional ^1H-NMR spectroscopy. The decay of the porphyrin-based fluorescence was fitted by two … More exponentials, suggesting the presence of two conformers with respect to the orientation of viologen.
4) Photoinduced Electron-Transfer Reactions of Zinc and Magnesium Myoglobins-Both photoinduced electron-transfer and thermal backward electron-transfer reactions of zinc and magnesium myoglobins with cationic quenchers were bimolecular steps and the reaction rates were insensitive to the driving force of reactions, suggesting that the reactions are controlled by conformational changes of myoglobins. The intramolecular photoinduced electrontransfer was observed in a zinc myoglobin-hexacyanoferrate(III) complex, which forms by electrostatic interactions, and was inhibited in addition of poly-L-lysine by forming a stable complex of poly-L-lysine and hexacyanoferrate(III) ions.
5) Syntheses and Characterizations of Optical Active Viologens-Optical acitive viologens (OAV^<2+>) were newly synthesized and characterized. The stereoselectivity was found for the formation of the charge-transfer complex of OAV^<2+> with an L-ascorbate ion and for the ion-pair formation between OAV^<2+> and poly-L-glutamate ion. Less

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] Keiichi Tsukahara,Kazuyo Ishida: "Kinetics and Mechanism of Reduction of Metmyoglobin by Dithionite.Role of the Heme Propionates" Bull.Chem.Soc.Jpn.64. 2378-2382 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara,Satoko Asami: "Photoinduced Electron-Transfer Reaction in a Zinc Myoglobin-hexacyanoferrate(III)Complex" Chem.Lett.1337-1340 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara: "Electron-Transfer Reactions of Metal Complexes and Iron Proteins with Viologen Radicals" Trends in Inorganic Chemistry. 2. 17-32 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara,Hiromi Todorobaru: "Effect of the Chemical Modification by Viologen on the Reduction of Metmyoglobin" Chem.Lett.1181-1184 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara,Mihoko Okada: "Electron-Transfer Quenching and Thermal Backward Electron-Transfer Reactions of Zinc Myoglobin Controlled by Conformational Change" Chem.Lett.1543-1546 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara,Satoko Asami,Mihoko Okada,Takeshi Sakurai: "Kinetics and Mechanisms of Photoinduced Electron-Transfer Reaction of Zinc Myoglobin.Intracomplex vs Intermolecular Quenching Controlled by Conformational Change Associated with Charge and Steric Bulk of Quenchers"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara and Kazuyo Ishida: "Kinetics and Mechanism of Reduction of Metmyoglobin by Dithionite. Role of the Heme Propionates" Bull. Chem. Soc. Jpn.64. 2378-2382 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara and Satoko Asami: "Photoinduced Electron-Transfer Reaction in a Zinc Myoglobin-hexacyanoferrate(III) Complex" Chem. Lett.1337-1340 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara: "Electron-Transfer Reactions of Metal Complexes and Iron Proteins with Viologen Radicals" Trends Inorg. Chem.2. 17-32 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara and Hiromi Todorobaru: "Effect of the Chemical Modification by Viologen on the Reduction of Metmyoglobin" Chem. Lett.1181-1184 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara and Mihoko Okada: "Electron-Transfer Quenching and Thermal Backward Electron-Transfer Reactions of Zinc Myoglobin Controlled by Conformational Change" Chem. Lett.1543-1546 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Keiichi Tsukahara Hiromi Todorobaru: "Effect of the Chemical Modification by Viologen on the Reduction of Metmyoglobin" Chem.Lett.1181-1184 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Keiichi Tsukahara Mihoko Okada: "Electron-Transfer Quenching and Thermal Backward Electron-Transfer Reactions of Zinc Myoglobin Controlled by Conformational Change" Chem.Lett.1543-1546 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Keiichi Tsukahara,Satoko Asami Mihoko Okada,Takeshi Sakurai: "Kinetics and Mechanisms of Photoinduced Electron--Transfer Reaction of Zinc Myoglobin. Intracomplex vs Intermolecular Quenching Controlled by Conformational Change Associated with Charge and Steric Bulk of Quenchers"

    • Related Report
      1992 Annual Research Report
  • [Publications] Keiichi Tsukahara;Kazuyo Ishida: "Kinetics and Mechanism of Reduction of Metmyoglobin by Dithionite. Role of the Heme Propionates" Bull. Chem. Soc. Jpn.64. 2378-2382 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Keiichi Tsukahara;Satoko Asami: "Photoinduced ElectronーTransfer Reaction in a Zinc MyoglobinーHexacyanoferrate(III)Complex" Chem. Lett.1337-1340 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Keiichi Tsukahara: "ElectronーTransfer Reactions of Metal Complexes and Iron Proteins with Viologen Radicals" Trends in Inorganic Chemistry. 2. 17-32 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Keiichi Tsukahara;Satoko Asami;Mihoko Okada: "Kinetics and Mechanisms of Photoinduced ElectronーTransfer Reaction of Zinc Myoglobin. Intracomplex vs Intermolecular Quenching Controlled by Conformational Gating"

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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