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Studies on the Molecular Engineering of Functional Regulations of Synthetic Pigment Substituted Hemoproteins

Research Project

Project/Area Number 61470079
Research Category

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

Allocation TypeSingle-year Grants
Research Field 工業物理化学
Research InstitutionKyoto University

Principal Investigator

MORISHIMA Isao  Kyoto University, Faculty of Engineering, Associate Prof., 工学部, 助教授 (50026093)

Co-Investigator(Kenkyū-buntansha) YONEZAWA Teijiro  Kyoto University , Faculty of Engineering, Professor, 工学部, 教授 (20025787)
SHIRO Yoshitsugu  Postdoctoral Fellow of JSPS, 特別研究員
城 宜嗣  日本学術振興会, 特別研究員
Project Period (FY) 1986 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 1987: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1986: ¥5,700,000 (Direct Cost: ¥5,700,000)
KeywordsMetal-substituted Hemoproteins / Molybdenum and Tungusten-substituted Hemoproteins / タングステン置換ヘムタンパク質 / ニッケル置換ミオグロビン / ルテンウム置換ヘモグロビン / グリーンヘムタンパク質 / クロクン含有ヘムタンパク質 / ヘムタンパク質 / 金属置換ヘム / ルテニウムヘム / モリブデンヘム / グリーンヘム蛋白 / 機能制御 / 分子工学
Research Abstract

We have studied the structures and functions of hemoprotein derivatives reconstituted with a variety of metal-substituted hemes and iron-chlorin derivatives. Molybdenum (Mo) and tungustem (W) substituted myoglobin (Mb) and horseradish peroxidase (HRP) (where the heme iron is replaced by Mo=0 or w=0) were prepared. It was found that Mb favors the reduced state (+4), while HRP stabilizes in the oxidized state (+5). Nickel(II)-substituted Mb, Hb and HRP were oxidized with iridate to examine whether porphyrin <pi>-cation radical is formed or not in these hemoproteins. It was found that Ni(II)-porphyrin <pi>-cation radical is formed in all of these hemoproteins, although it is less stable in Mb and Hb than in HRP. Tese results are discussed in relation to the different features of higher oxidation states of native Mb and HRP. Diruthenium-substituted Ru-Fe hybrid Hbs were synthesized by heme substitution from protoheme to Ru(II)CO-deuteroporphyrin in the <alpha> or <beta> subunits. The proton NMR spectra of the intersubunit hydrogen-bonded protons showed that the quaternary structures of the two complementary hybrids both remain in the "T-like-state" at low pH, suggesting that the T to R structural conversion is induced by ligation of the third ligand molecule. E have also studied hemoproteins containing iron-chlorin prosthetic groups and their model chlorin complexes.

Report

(2 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] 森島績: BIOCHEMISTRY. 25. 3576-3584 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 城宣嗣: J. Am. Chem. Soc.(1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 森島績: Biochem. Biophys. Res. Commun.(1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 石森浩一郎: BIOCHEMISTRY. (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Isao Morishima, Yoshitsugu Shiro and Keizo Nakajima: "Nuclear Magnetic Resonance Studies of Porphyrin <pi>-Cation Radical in Ruthenium(II) Substituted Horseradish Peroxidase" BIOCHEMISTRY. 25. 3576-3584 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yoshitsugu Shiro, Motoru Takeda and Isao Morishima: "A Study on the Molybdenum and Tungusten-Substituted Hemoproteins. Models for the High Valent Iron-Porphyrin in Myoglobin and Horseradish Peroxidase" J. Am. Chem. Soc.(1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Isao Morishima, Motoru Takeda and Kikuo Takatera: "Formation of Porphyrin <pi>-Cation Radical in Myoglobin. A Study on One Electron Oxidation Products of Nickel(II)-Substituted Hemoproteins" Biochem. Biophys. Res. Commun.(1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Koichiro Ishimori and Isao Morishima: "Ru-Fe Hybrid Hemoglobins As Model for Partially Liganded Hemoglobin" BIOCHEMISTRY. (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 森島績: Biochemistry(UsA). 25. 3576-3584 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 石森浩一郎: J.Biol Chem.

    • Related Report
      1986 Annual Research Report
  • [Publications] 森島績: "高分解能NMR-基礎と新しい展開-(現代化学増刊,第7章タンパク質-金属酵素)" 東京化学同人, (1987)

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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