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Structures and Reactivities of Quaternary Metal Complexes as Enzyme Models

Research Project

Project/Area Number 02453039
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 InstitutionNagoya University

Principal Investigator

YAMAUCHI Osamu  Nagoya University, School of Science, Professor, 理学部, 教授 (70029643)

Co-Investigator(Kenkyū-buntansha) MASUDA Hideki  Nagoya University, School of Science, Research Associate, 理学部, 助手 (50209441)
ODANI Akira  Nagoya University, School of Science, Research Associate, 理学部, 助手 (60143913)
TAKANI Masako  Kanazawa University, Faculty of Pharmaceutical Sciences, Assistant Professor, 薬学部, 講師 (40019667)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥4,300,000 (Direct Cost: ¥4,300,000)
KeywordsEnzyme model metal complex / Quaternary metal complex / Ligand-ligand interaction / Aromatic ring stacking / Pterin-Cu (II) complex / Tetrahydropterin / Pt (II) complex containing an aromatic ring / DNA-intercalator adduct model / 四元錯体形成反応 / 安定度定数 / プテリン含有銅(II)錯体 / X線結晶構造解析
Research Abstract

With a view to elucidating the structures and reaction mechanisms of metalloenzyme-cofactor-substrate intermediate complexes, we investigated the structures, stabilities, and reactivities of ternary and quaternary complex systems as biological models.
1. Aromatic ring stacking in ternary Cu (II) complexes, [Cu (bpy) (L-Trp) ClO_4]and[Cu (bpy) (L-Tyr)ClO_4]・2H_2O (bpy = 2, 2'-bipyridine ; Trp =tryptophan ; Tyr = tyrosine), has been established in the solid state between bpy and the side chain aromatic ring of Trp and Tyr, respectively, by X-ray crystal structure analysis. Upon phosphorylation of the Tyr phenol OH group, the phenol ring is involved in electrostatic interactions with the charged side group of arginine or lysine coordinated to the same Cu (II) ion. The result suggests the possibility that Tyr phosphorylation in proteins causes the change in the mode of interactions between the side chain groups of amino acid residues and thus gives rise to protein conformational changes.
2. … More Adduct formation between platinum DNA intercalators[Pt (L) (en)] (L = bpy, 1, 10-phenanthroline (plien), 3, 4, 7, 8tetramethyl-1, 10-phenanthroline (Me_4phen) ) and mononucleotides (NMP = AMP, GMP, CMP) has been studied by spectroscopic methods. [pt (Me_4phen) (en)]with the largest hydrophobic area has been found to form the most stable adducts with NMP mainly through the stacking between L and the base moiety of NMP. It was concluded that the electrostatic interactions between the NMP phosphate group and Pt^<2+> or the coordinated en NH_2 group contribute to the adduct stability.
3. Structures and stabilities of ternary and quaternary Cu (II) complexes involving a pterin cofactor model have been investigated by spectroscopic methods and potentiometry. Cu (bpy) (PC) (PC pterin-6-carboxylate) as a phenylalanine hydroxylase active site model was found to form quaternary complexes with L = imidazole (im), NH_3, or N_3^-, and the stability constants for the Cu (bpy) (PC) (im) system were successfully detemined by pH titrations at 25゚C and I = 0.1 M (KNO_3). The redox reactions between Cu (bpy)^<2+> and a tetrahydropterin were followed by spectroscopic and chromatographic methods, which revealed that the pterin is oxided to the dihydro form with, consumption of dioxygen. Less

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (29 results)

All Other

All Publications (29 results)

  • [Publications] Hideki Masuda: "Structural Evidence for the Intramolecular Charge-Transfer Interaction Involving an Indole Ring in Ternary Copper(II) Complexes with L-Tryptophan and Aromatic Diamines." Inorg.Chim.Acta. 180. 73-79 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Akira Odani: "Platinum DNA Intercalator-Mononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorganic Chemistry. 30. 2133-2138 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Osamu Yamauchi: "Activation of Dioxygen through Redox Reactions between a Copper(II)Complex and Reduced Pterins." J.Pharmacobio-Dyn.14. s-122 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Helmut Sigel: "Comments on Potentiometric pH Titrations and the Relationship between pH-meter Reading and Hydrogen Ion Concentration." Anal.Chim.Acta. 255. 63-72 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Osamu Yamauchi: "Weak Interactions in Metal Complexes of Amino Acids with a Phosphorylated Side Chain.Conversion of Aromatic Ring Stacking to Electrostatic Bonding by Tyrosine Phosphorylation" inorg.Chim.Acta. 200. (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Akira Odani: "Pteridine-Containing Ternary and Quaternary Complexes as Models for Metalloenzyme-Pterin Cofactor-Substate Association.Structure of Ternary Cu(2,2'-bipyridine)-(lumazine)Complex and Successful Equilibrium Study of a Quaternary Copper(II)System"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Helmut Sigel: "The Imidazole Group and Its Stacking Properties in Mixed Ligand Metal Ion Complexes" Comments on Inorganic Chemistry. 9. 305-330 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Osamu Yamauchi: "Indole Nitrogen-Palladium(II)Bonding.Chemical and Structural Characterization of Palladium(II)Complexes of Alkylindoles and Intermediacy of the 3H-Indole Ring" Inorganic Chemistry. 29. 1856-1860 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 小谷 明: "薬学の機器分析" 広川書店, 20 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 山内 脩: "「生体と金属イオン」" 学会出版, 21 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Masuda, T. Sugimori, A. Odani, and O. Yamauchi: "Structural Evidence for the Intramolecular Charge-Transfer Interaction Involving an Indole Ring in Ternary Copper (II) Complexes with L-Tryptophan and Aromatic Diamines." Inorg. Chim. Acta,. 180. 73-79 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Odani, R. Shimata, H. Masuda, and O. yamauchi: "Platinum DNA Intercalator-Mononucleotide Adduct Formation. Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorg. Chem.30. 2133-2138 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] O. Yamauchi, A. Odani, M. Hayashi, and H. Masuda: "Activation of Dioxygen through Redox Reactions between a Copper (II) Complex and Reduced Pterins." J. Pharmacobio-Dyn.14. S-122 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Sigel, A. Zuberbuhler, and O. Yamauchi: "Comments on Potentiometric pH Titrations and the Pelationship between pH-meter Reading and Hydrogen Ion Concentration." Anal. Chim. Acta. 255. 63-72 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] O. Yamauchi, A. Odani, and H. Masuda: "Weak Interactions in Metal Complexes of Amino Acids with a Phosphorylated Side Chain. Conversion of Aromatic Ring Stacking to Electrostatic Bonding by Tyrosine Phosphorylation" Inorg. Chim. Acta. 200.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] A. Odani, H. Masuda, K. Inukai, and O. Yamauchi: "Pteridine-Containing Ternary and Quaternary Complexes as Models for Metalloenzyme-Pterin Cofactor-Substrate Association. Structure of Ternary Cu (2, 2'-biphridine) - (lumazine) Complex and Successful Equilibrium Study of a Quaternary Copper (II) system"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Masuda, A. Odani, T. Yamazaki, T. Yajima, and O. Yamauchi: "Structural and Thermodynamic Characterization of Ternary Copper (II) Complexes Containing an Acidic and Basic Amino Acid. Arginine Side Chain Involvement in Intermolecular Bonding and Its Biological Implication"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Hideki Masuda: "Structural Evidence for the Intramolecular ChargeーTransfer Interaction Involving an Indole Ring in Ternary Copper(II)Complexes with LーTryptophan and Aromatic Diamines." Inorg.Chim.Acta. 180. 73-79 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Akira Odani: "Platinum DNA IntercalatorーMononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorganic Chemistry. 30. 2133-2138 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Osamu Yamauchi: "Activation of Dioxygen through Redox Reactions between a Copper(II)Complex and Reduced Pterins." J.PharmacobioーDyn.14. S-122 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Helmut Sigel: "Comments on Potentiometric pH Titrations and the Relationship between pHーmeter Reading and Hydrogen Ion Concentration." Anal.Chim.Acta. 255. 63-72 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Osamu Yamauchi: "Weak Interactions in Metal Complexes of Amino Acids with a Phosphorylated Side Chain. Conversion of Aromatic Ring Stacking to Electrostatic Bonding by Tyrosine Phosphorylation" Inorg.Chim.Acta. 200. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Akira Odani: "PteridineーContaining Ternary and Quaternary Complexes as Models for MetalloenzymeーPterin CofactorーSubstrate Association. Structure of Ternary Cu(2,2^´ーbipyridine)ー(lumazine)Complex and Successful Equilibrium Study of a Quaternary Copper(II)System" Submitted for publication.

    • Related Report
      1991 Annual Research Report
  • [Publications] 小谷 明: "薬学の機器分析" 広川書店, 20 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 山内 脩: "「生体と金属イオン」" 学会出版, 21 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Helmut Sigel: "The Imidazole Group and Its Stacking Properties in Mixed Ligand Metal Ion Complexes" Comments on Inorganic Chemistry. 9. 305-330 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Osamu Yamauchi: "Indole NitrogenーPalladium(II) Bonding.Chemical and Structural Characterization of Palladium(II) Complexes of Alkylindoles and Intermediacy of the 3HーIndole Ring" Inorganic Chemistry. 29. 1856-1860 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Hideki Masuda: "Structural Evidence for the Intramolecular ChargeーTransfer Interaction Involving an Indole Ring in Ternary Copper(II) Complexes with LーTryptophan and Aromatic Diamines" Inorganica Chimica Acta. 179. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Akira Odani: "Platinum DNA IntercalatorーMononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorganic Chemistry. 30. (1991)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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