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Photo and Magneto-Chemical Studies on Microstructure and Function of Active Sites

Research Project

Project/Area Number 01470050
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 InstitutionKyoto University

Principal Investigator

OHYA Hiroaki  Kyoto Univ., Fac. Science Ass. Professor, 理学部, 助教授 (00025389)

Co-Investigator(Kenkyū-buntansha) KOHNO Masahiro  Jeol Co. Ltd., Aite Div., Manager, 分析機器技術本部, 副課長
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥6,600,000 (Direct Cost: ¥6,600,000)
Fiscal Year 1990: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1989: ¥5,100,000 (Direct Cost: ¥5,100,000)
KeywordsEnzymatic Model / Enzynatic Reaction / Intermediate / ESR / ESRET / Multichannel Photometer / SOD / Peroxide Adduct / 三元錯体
Research Abstract

Photo- and magneto-chemical studies on microstructure and function of the active sites in typical enzymes have been carried out by using a simultaneous ESR and optical measurement apparatus (ESRET) developed by this project. 1) Fe (tpp) Cl was employed as a model complexes of heme-Fe^<3+> proteins. This complex showed a clear formation of a peroxide adduct of Fe (tpp)(OOR), which is a key intermediate to function as several enzymatic reaction. The ESR and absorption spectra exhibit characteristic features of its formation. 2) By using the Co^<3+>-polyamine and Co^<2+>-(SB)(SB : Shiff base) as models of dioxygenases we have examined reaction mechanisms of catechol dioxygenase reactions. The former complex formed a binary complex with catechols, followed by an addition of O_2 resulting in a ternary complex. In the latter O_2 first formed an oxygen adduct with the complex, and occurred an intramolecular electron transfer reaction. Secondly, catechol as a substrate was oxydized by the cobalt complex to semiquinone. 3) As a typical example of Fe-SOD model Fe^<3+>-EDTA and its analogs were reacted with active oxygen species. It was found by ESRET that two intermediates are formed : One is sideon type Fe^<3+>-O_2^<2-> and the other Fe^<2+>-O_2^-. By using these intermediates as probes of the recation, the reaction mechanism of the SOD was investigated.

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] K.Tajima,etal: "Direct Evidence of Hemeーtーbutyl Peroxide Adduct Formation Demonstrated by Simullaneous ESR and Optical Measurements" Inorg.Chem.28. 709-715 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Tajima etal: "Important Role of Fe(III)TPPーOxygenーSkatol Ternary Complex in Triptophane Dioxygenase Model Reaction System" Inorg.Chim Acta. 172. 83-91 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Fukui,H.OhyaーNishiguchi,N.Hirota: "The Relation between ZeroーField Splittings and Distortions along the Normal Coordinates in TransitionーMetal Complexes" Mol.Phys.71. 1269-1283 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Fukui,H.OhyaーNishiguchi,N.Hirota: "ESR and Magnetic Susceptibility Studies on HighーSpin Tetrahedral Cobalt(II)ーThiolate Complexes:Am Approach to RubredoxinーType Active Sites" Bull.Chem.Soc.Jpn.,. 64. 1201-1209 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S.Nakashima,H.OhyaーNishiguchi,N.Hirota,H.Fujii,I.Morishima: "Spin Coupling in Ferric Porphyrin and Chlorin radical Cation Complexes" norg.Chem.29. 5207-5211 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S.Fujii,H.OhyaーNishiguchi,N.Hirota: "EPR Evidence of Intermediate Peroxo Complexes Formed in a SOD Model System." Inorg.Chim.Acta. 175. 27-30 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 大矢 博昭、 山内 淳: "電子スピン共鳴ー素材のミクロキャラクタリゼ-ション" 構談社サイエンティフィク, 300 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] H.OhyaーNishiguchi etal: "LandoltーBernstein New Series “Magnetic Properties of Free Radicals" ed H.Fischer Vol.11/17h Chap 19" Springer Verlag AG., 63 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Ohya-Nishiguchi etal.: "Direct Evidence of Heme-t#butylteroxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements," Inorg. Chem.28. 709-715 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K. Tsjima, M. Yoshino, K. Mikami, T. Edo, K. Ishizu, and H. Ohya-Nishiguchi: "Important Role of Fe (111) TPP-Oxygen-Skatole Ternary Complex in Triptophane Dioxygenase Model Reaction System." Inorg. Chim. Acta. 172. 83-91 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K. Fukui, H. Ohya-Nishiguchi, and N. Hirota: "The Relation between Zero-Field Splittings and Distortions along the Normal Coordinates in Transition-Metal Complexes." Mol. Phys.71. 1269-1283 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K. Fukui, H. Ohya-Nishiguchi, and N. Hirota: "ESR and Magnetic Susceptibility Studies on High-Spin Tetrahedral cobalt (11)-Thiolate Complexes : An Approach to Rubredoxin-Type Active Sites," Bull. Chem. Soc. Jpn. 64. 0000 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Nakashima, H. Ohya-Nishiguchi, N. Hirota, H. Fujii, and I. Morishima: "Spin Coupling in Ferric porphyrin and Chlorin Radica Cation Complexes." Inorg. Chem.29. 5207-5211 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Fujii, H. Ohya-Nishiguchi, and N. Hirota: "EPR Evidence of Intermediate Peroxy Complexes Formed in a SOD Model System." Inorg. Chim. Acta. 175. 27-30 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] H. Ohya-Nishiguchi, Y. Yamauchi: "Electron Spin Resonance, Koudansha Scientific (1989)"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] H. Ohya-Nishiguchi, A. Terahara, K. Tajima, and K. Ishizu: ""Cation Radicals of Aromatic Hydrocarbons and their Derivatives and S-Heterocycles" in Landolt-Bern-stein New Series, "Magnetic Properties of Free Radicals", ed H. Fischer, Springer Verlag, Vol. 11/17h, Chap. 19 59-121 (1989)."

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Tajima,etal: "Direct Evidence of Hemeーtーbutyl Peroxide Adduct Formation Demonstrated by Simullaneous ESR and Optical Measurements" Inorg.Chem. 28. 709-715 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Tajima,etal: "Important Role of Fe(III)TPPーOxygenーSkatol Ternary Complex in Triptophane Dioxygenase Model Reaction System" Inorg.Chim Acta. 172. 83-91 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Fukui,H.OhyaーNishiguchi,N.Hirota.: "The Relation between ZeroーField Splittings and Distortions along the Normal Coordinates in TransitionMetal Complexes" Mol.Phys.71. 1269-1283 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Fukui,H.OhyaーNishiguchi,N.Hirota: "ESR and Magnetic Snsce ptibility Studies on HighーSpin Tetrahedral Cobalt(II)ーThiolate Complexes:An Approach to RubredoxinーType Active Sites" Bull.Chem.Soc.Jpn.,. 64. 1201-1209 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Nakashima,H.OhyaーNishiguchi,N.Hirota,H.Fujii,I.Morishima: "Spin Coupling in Ferric Porphyrin and Chlorin Radical Cation Complexes" Inorg.Chem.29. 5207-5211 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Fujii,H.OhyaーNishiguchi,N.Hirota: "EPR Evidence of Intermediate Peroxo Complexes Formed in a SOD Model System." Inorg.Chim.Acta. 175. 27-30 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 大矢 博昭、山内 淳: "電子スピン共鳴ー素材のミクロキャラクタリゼ-ション" 講談社サイエンティフィク, 300 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] H.OhyaーNishiguchi,etal: "LandoltーBernstein New Series “Magnetic Properties of Free Radicals" ed H.Fischer Vol.11/17h Chap 19" Springer Verlag AG., 63 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] H.Ohya-Nishiguchi et al: "Direct Evidonce of Heme-t-butylperoxide Adduct Formation Demonstrated by Simultaneous ESR and Optical Measurements." Inorg.Chem.28. 709-715 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] H.Fujita and H.Ohya-Nishiguchi: "Facile Formation of Radical Trianion of 4,7-Phenan-throline as studied by ESR" J.Chem. Soc.Chem commum.1989. 1091-1093 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] C.Miyake, M.Hirose and H.Ohya-Nishiguchi: "ESR and Magnetic Susceptibility Evidence of Thermally Accessible Electron Transfer between U^<5+>cl_5〔φ_3P〕and U^<4+>Cl_5〔φ_3P〕^+" Inorg Chim Acta. 165. 179-183 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Fukui etal: "Relevant Relation between the Zero-Field Splittings and the Distortion along the Normal Coordinates in Transition Metal complexes" Inorg.Chem.

    • Related Report
      1989 Annual Research Report
  • [Publications] S.Nakashima etal: "Quantitative Formation of Spin-Coupled Intermediate in a System Consisting of Co(III)tetramine Complex and Catechols" Inorg.Chim Acta.

    • Related Report
      1989 Annual Research Report
  • [Publications] 大矢博昭,山内淳: "電子スピン共鳴-素材のミクロキャラクタリゼ-ション" 講談社サイエンティフィク, 300 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] H.Ohya-Nishiguchi etal: "Landolt-Bernstein New Series,"Magnetic Properties of Free Radicals",ed H.Fischer Vo1.11/17h,chap.19" Springer Verlag AG, 63 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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