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Construction of in situ, time-resolved, and temperature-changeable spectrometry

Research Project

Project/Area Number 11554026
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Inorganic chemistry
Research InstitutionNagoya Institute of Technology

Principal Investigator

MASUDA Hideki  Nagoya Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (50209441)

Co-Investigator(Kenkyū-buntansha) TABATA Yuki  分光計器(株), 技術課, 課長
太幡 裕己  分光計器株式会社, 技術課, 課長
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥13,800,000 (Direct Cost: ¥13,800,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2000: ¥5,400,000 (Direct Cost: ¥5,400,000)
Fiscal Year 1999: ¥7,200,000 (Direct Cost: ¥7,200,000)
Keywordsoxygen activation / copper complex / iron complex / non-heme enzyme / epoxidation / nucleophilic reaction / oxygen cleavage / hydrogen peroxide / in situ 測定 / 時間分解 / 酸化反応 / 吸収スペクトル / 温度可変 / 酸素の可逆的脱着 / 非ヘム酸化酵素 / 反応中間体 / 小分子活性化 / 酸素錯体 / 金属錯体 / 特殊反応場 / 非共有性相互作用 / 非ヘム酵素モデル / 活性酸素
Research Abstract

In order to elucidate the mechanisms for the oxygen activation, O-O bond cleavage, oxidation, and so on, which are carried out in non-heme enzymes, in situ-observable, time-resolved, and temperature-changeable electronic absorption spectrometer has originally been constructed, and the following aspects have been found out. (I) The dinuclear iron complex modified by non-covalent interaction groups such as hydrogen bonding and hydrophobic sphere as hemerythrin model has been newly prepared, which exhibits a reversible reaction with dioxygen. (ii) The copper complex that has forced the geometry to four-coordinate square-pyramidal has originally been prepared. The reaction of the complex with hydrogen peroxide exhibited the formation of strong Cu(II)-hydroperoxide complex, which furthermore showed higher reactivity for substrates, (iii) The copper complexes that has forced the geometry to four-coordinate tetrahedral has been prepared using a new TACH ligand, whose di-μ-oxo-dicopper complex … More showed the highest reactivity among the copper complexes reported hitherto. In order to elucidate the mechanisms for the oxygen activation, O-O bond cleavage, oxidation, and so on , which are carried out in non-heme enzymes, in situ-observable, time-resolved, and temperature-changeable electronic absorption spectrometer has originally been constructed, and the following aspects have been found out. (I) The dinuclear iron complex modified by non-covalent interaction groups such as hydrogen bonding and hydrophobic sphere as hemerythrin model has been newly prepared, which exhibits a reversible reaction with dioxygen. (ii) The copper complex that has forced the geometry to four-coordinate square-pyramidal has originally been prepared. The reaction of the complex with hydrogen peroxide exhibited the formation of strong Cu(II)-hydroperoxide complex, which furthermore showed higher reactivity for substrates, (iii) The copper complexes that has forced the geometry to four-coordinate tetrahedral has been prepared using a new TACH ligand, whose di-μ-oxo-dicopper complex showed the highest reactivity among the copper complexes reported hitherto. Less

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] K.Jitsukawa: "A Substrate-Specific α-Hydroxylation of Dipeptides Mediated upon a Co(III)-terpyridine Complex : A Functional Model for Peptidylglycine α-Hydroxylating Monooxygenase"Chem. Lett.. 30-31 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "Reverse Reactivity in Hydroxylation of Adamantane and Epoxidation of Cyclohexene Catalyzed by the Mononuclear Ruthenium-oxo Complexes with 6-Substituted Tripodal Polypyridine Ligands"Tetrahedron Lett.. 42. 3467-3469 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "SOD Activities of the Copper Complexes with Tripodal polypyridylamine Ligands Having a Hvdrogen Bonding Site"Inorg. Chim. Acta. 324(1,2). 108-116 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] S.Ogo: "Biomimetic Intradiol-Cleavage of Catechols with Incorporation of Both Atoms of O_2: The Role of the Vacant Coordination Site on the Iron Center"Chem. Lett.. 1062-1063 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "Epoxidation activities of mononuclear ruthenium-oxo complexes with a square planar 6,6'-bis(benzoylamino)-2,2'-bipyridine and axial ligands"Tetrahedron Lett.. 43(8). 1491-1494 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Wada: "Reactivity for a Hydroperoxide Bound to Mononuclear Non-Heme Iron Site"Inorg. Chem.. 41(4). 616-618 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "A Substrate-Specific α-Hydroxylation of Dipeptides Mediated upon a Co(III)-terpyridine Complex: A Functional Model for Peptidylglycine α-Hydroxylating Monooxygenase"Chem. Lett.. 30-31 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "Reverse Reactivity in Hydroxylation of Adamantane and Epoxidation of Cyclohexene Catalyzed by the Mononuclear Ruthenium-oxo Complexes with 6-Substituted Tripodal Polypyridine Ligands"Tetrahedron Lett.. 41. 3467-3469

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "SOD Activities of the Copper Complexes with Tripodal Polypyridylamine Ligands Having a Hydrogen Bonding Site"Inorg.Chem.Acta. 324(1,2). 108-116 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] S.Ogo: "Biomimetic Intradiol-Cleavage of Catechols with Incorporation of Both Atoms of O_2: The Role of the Vacant Coordination Site on the Iron Center"Chem. Lett.. 1062-1063 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K.Jitsukawa: "Epoxidation activities of mononuclear ruthenium-oxo Complexes with a square planar 6,6'-bis(benzoylamino)-2,2'-bipyridine and axial ligands"Tetrahedron Lett.. 43(8). 1491-1494 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Wada: "Reactivity for a Hydroperoxide Bound to Mononuclear Non-Heme Iron Site"Inorg. Chem.. 41(4). 616-618 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] K. Jitsukawa: "A Substrate-Specific α-Hydroxylation of Dipeptides Mediated upon a Co(III)-terpyridine Complex : A Functional Model for Peptidylglycine α-Hydroxylating Monooxygenase"Chem. Lett.. 30-31 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K. Jitsukawa: "Reverse Reactivity in Hydroxylation of Adamantane and Epoxidation of Cyclohexene Catalyzed by the Mononuclear Ruthenium-oxo Complexes with 6-Substituted Tripodal Polypyridine Ligands"Tetrahedron Lett.. 42. 3467-3469 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K. Jitsukawa: "SOD Activities of the Copper Complexes with Tripodal Polypyridylamine Ligands Having a Hydrogen Bonding Site"Inorg. Chim. Acta. 324(1,2). 108-116 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S. Ogo: "Biomimetic Intradiol-Cleavage of Catechols with Incorporation of Both Atoms of O_2 : The Role of the Vacant Coordination Site on the Iron Center"Chem. Lett.. 1062-1063 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K. Jitsukawa: "Epoxidation activities of mononuclear ruthenium-oxo complexes with a square planar 6,6'-bis(benzoylamino)-2,2'-bipyridine and axial ligands"Tetrahedron Lett.. 43(8). 1491-1494 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Wada: "Reactivity for a Hydroperoxide Bound to Mononuclear Non-Heme Iron Site"Inorg. Chem.. 41(4). 616-618 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] R.Yamahara: "(Catecholato) iron (III) Complexes with Tetradentate Tripodal Ligands Containing Substituted Phenol and Pyridine Units as Structural and Functional Model Complexes for the Catechol-bound Intermediate of Intradiol-cleaving Catechol Dioxygenases"Inorg.Chim.Acta. 300-302. 587-596 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Arii: "A Novel Diiron Complex as a Functional Model for Hemerythrin"J.Inorg.Biochem. 82. 153-162 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Wada: "Reactivity for a Hydroperoxide Bound to Mononuclear Non-Heme Iron Site"Inorg.Chem.. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Wada: "Synthesis and Characterization of Novel Alkylperoxo Mononuclear Iron(III) Complexes with a Tripodal Pyridylamine Ligand : A Model for Peroxo Intermediates in Reactions Catalyzed by Non-Heme Iron Enzymes"Inorg.Chem. 38(16). 3592-3593 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Kobayashi: "High Activity of Binuclear Cobalt(II) Complex for Ethylene Evolution from 1-Aminocyclopropane-1-carboxylic Acid in the Presence of Hydrogen Peroxide"Z.Naturforsch.. 54. 534-541 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H.Takagi: "Synthesis and Structure of Tetrazols with Convergent and Divergent Array of Hydroxyl Groups"J.Chem.Soc.,Perkin Trans.1. 13. 1885-1892 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Wada: "Non-heme Iron Complexes as Oxidation Catalysts in Alkene Functionalization"J.Inorg.Biochem. 74. 331-331 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Sasaki: "Interaction between the Peroxide Ion and Acetato Moiety of the Ligand System in a Cobalt Complex with a Binucleating Ligand"Inorg.Chem.Commun.. 2. 244-246 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.Yamahara: "(Catecholato)iron(III) Complexes with Tetradentate Tripodal Ligands Containing Substituted Phenol and Pyridine Units as Structural and Functional Model Complexes for the Catechol-bound Intermediate of Intradiol-cleaving Catechol Dioxygenases"Inorg.Chim.Acta. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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