1992 Fiscal Year Annual Research Report

生体関連金属錯体における多重相互作用と機能発現の研究

Research Project

Project/Area Number	04225102
Research Institution	Nagoya University
Principal Investigator	山内脩名古屋大学, 理学部, 教授 (70029643)
Co-Investigator(Kenkyū-buntansha)	松本和子早稲田大学, 理工学部, 教授 (60111457) 宗像惠近畿大学, 理工学部, 教授 (80090942) 鈴木晋一郎大阪大学, 教養部, 教授 (70116052) 杉浦幸雄京都大学, 化学研究所, 教授 (40025698)
Keywords	多重相互作用 / 分子間相互作用 / エチレンレセプター / 芳香環スタッキング / プテリン補酵素 / 転写因子Spl / 白金ブルー錯体 / アミン酸化酵素
Research Abstract	昨年度に引続いて生体関連金属錯体における多重相互作用と機能発現に果たす役割を明らかにすることを目的として、中心金属イオンとの結合様式、分子間相互作用、情報伝達の諸点を中心に研究を行った。 1.多重相互作用とモデル錯体生体系での特異的結合に関与するアミノ酸側鎖の相互作用について、水素結合と芳香環スタッキングが錯体の安定度と配位構造を左右することを、アミノ酸、ペプチド銅(II)錯体にて明らかにした。植物成長ホルモンのエチレンの受容体としてCu(I)を含むタンパク質を想定し、モデル錯体による研究を続けてきたが、目下、Ag(I)などをマーカーとしてこれと結合する分子を生体系で探索する段階に達した。 2.金属酵素・タンパク質関連錯体補酵素の役割について、銅含有フェニルアラニンヒドロキシラーゼのプテリン補酵素によるO_2の活性化とこれへの中心金属イオンの関与、アミン酸化酵素の補酵素と考えられるTOPAおよび類似のPQQの銅(II)錯体の合成とその活性の研究をそれぞれはじめて行い、酸化還元反応過程に関する新しい情報を得た。 3.金属錯体とDNAとの相互作用 DNA結合ドメインの亜鉛フィンガーを有する転写因子Splについて、DNA切断能を有するブレオマイシン誘導体などを用いて反応を行い、DNAとの相互作用様式と塩基認識での役割に関する重要な情報を植た。DNAに親和性を有する金属錯体に関しては、新しい白金ブルー錯体を各種開発し、ヌクレオチドとの反応様式を解析して、生成する白金(II)錯体の構造を明らかにし、反応メカニズムを追究した。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] Hideki Masuda: "Copper(II)-Thioether Bonding in Multidentate N,S-Donor Ligand Complexes.Structural Dependence of the Chemical Properties of the Copper(II) Complexes of 1,5-Bis(2-Pyridylmethylamino)-3-thiapentane and 2,6-Bis-(2,6-dithiaheptyl)Pyridine" Bull.Chem.Soc.Jpn.65. 786-793 (1992)
[Publications] Osamu Yamauchi: "Weak Interactions in Metal Complexes of Amino Acids with a Phospho-rylated Side Chain.Conversion of Aromatic Ring Stacking to Electro-static Bonding by Tyrosine Phosphorylation." Inorg.Chim.Acta. 198-200. 749-761 (1992)
[Publications] Osamu Yamauchi: "Copper-Pteridine Chemistry.Structures,Solution Equilibria,and Redox Reactions" J.Inorg.Biochem.47. 40 (1992)
[Publications] Akira Odani: "Pteridine-Containing Ternary and Quaternary Complexes as Models for Metalloenzyme-Pterin Coractor-Substrate Association.Structure of Ternary Copper(II)-2,2'-Bipyridine-Lumazine Complex and Successful Equilibrium Study of a Quatemary Copper(II)System" J.Am.Chem.Soc.114. 6294-6300 (1992)
[Publications] Hideki Masuda: "Structures and Stabilities of Ternary Copper(II) Complexes Containing an Acidic and a Basic Amino Acid.Evidence for Arginine Side Chain Involve-ment in Intermolecular Interactions and Its Biological Inplication" Inorg.Chem.32. (1993)
[Publications] M.Otsuka: "A Synthetic Model Approach to the Sugar Moiety of Bleomycin" Heterocycles. 33. 27-34 (1992)
[Publications] T.Owa: "Man-Designed Bleomycins:Significance of the Bind-ing Sites as Enzyme Models and of Stereochemistry of the Linker Moiety" Tetrahedron. 48. 1193-1208 (1992)
[Publications] A.Yonezawa: "Binding of Tachplesin I to DNA Revealed by Footpriting Analysis:Signifi-cant Contribution of Secondary Structure to DNA Binding and Inplication for Biological Action" Biochemistry. 31. 2998-3004 (1992)
[Publications] J.Kuwahara: "Binding and Cleavage Characteristics of DNA by Bleomycin-Vanadium Complex" Bull.Inst.Chem.Res.Kyoto Univ.69. 511-519 (1992)
[Publications] A.Ichikawa: "Activation of DNA Cleavage by Dynemicin A in a B-Z Conformational Junction" Biochemistry. 31. 6784-6787 (1992)
[Publications] N.Nakamura: "The First Topa-Contaning Copper(II) Complex,[Cu(DL-topa)(bpy)-(H_2O)]BF_4・3H_2O,as a Model for the Active Site in Copper-Containing Amine Oxidase" J.Am.Chem.Soc.114. 6550-6552 (1992)
[Publications] N.Nakamura: "Synthesis and Structure of a Topa-Containing Ternary Copper(II) Complex" J.Inorg.Biochem.47. 54 (1992)
[Publications] S.Suziki: "Effect of Type II Copper on Enzyme Activity of Copper-Contaning Nitrite Reductase" J.Inorg.Biochem.47. 59 (1992)
[Publications] S.Kitagawa: "Synthesis of the Novel InfInite-Sheet- and -Chain Copper(I) Complex Polymers,{[Cu(C_4H_4N_2)_3/_2(CH_3CN)](PF_6)・0.5C_3H_6O}∞ and {[Cu(C_8H_<12>N_2)_3](C1O_4)_2}∞ and Their X-ray Crystal Structures" Inorg.Chem.31. 1714-1717 (1992)
[Publications] K.Matsumoto: "Synthesis of Functionalized Pyridines:Aminolisis of 2, 6-Dichloropyridines" Chemistry Express. 7. 473-476 (1992)
[Publications] M.Munakata: "Synthesis,Structures and Formation Constants of Copper(I) Complexes with Alkynes and 1,10-Phenanthroline" J.Chem.Soc.,Dalton.Trans.2225-2230 (1992)
[Publications] M.Ochiai: "High-Presssure Functionalization of Diaza-Crown Ethers:New Synthesis of Ag^+Ion-Specific Binders" J.Org.Chem.57. 542-547 (1992)
[Publications] K.Matsumoto: "Syntheses,Crystal Structures.and Electronic,ESR,and X-Ray Photoelectron Spectra of Acetamidate-and 2-Fluoroacetamidate-Bridged Mixed-Valent Octanuclear Platinum Blues" J.Am.Chem.Soc.114. 8110-8118 (1993)

1992 Fiscal Year Annual Research Report

生体関連金属錯体における多重相互作用と機能発現の研究

Principal Investigator

山内 脩 名古屋大学, 理学部, 教授 (70029643)

Research Products

[Publications] Osamu Yamauchi: "Weak Interactions in Metal Complexes of Amino Acids with a Phospho-rylated Side Chain.Conversion of Aromatic Ring Stacking to Electro-static Bonding by Tyrosine Phosphorylation." Inorg.Chim.Acta. 198-200. 749-761 (1992)

[Publications] Osamu Yamauchi: "Copper-Pteridine Chemistry.Structures,Solution Equilibria,and Redox Reactions" J.Inorg.Biochem.47. 40 (1992)

[Publications] Hideki Masuda: "Structures and Stabilities of Ternary Copper(II) Complexes Containing an Acidic and a Basic Amino Acid.Evidence for Arginine Side Chain Involve-ment in Intermolecular Interactions and Its Biological Inplication" Inorg.Chem.32. (1993)

[Publications] M.Otsuka: "A Synthetic Model Approach to the Sugar Moiety of Bleomycin" Heterocycles. 33. 27-34 (1992)

[Publications] T.Owa: "Man-Designed Bleomycins:Significance of the Bind-ing Sites as Enzyme Models and of Stereochemistry of the Linker Moiety" Tetrahedron. 48. 1193-1208 (1992)

[Publications] A.Yonezawa: "Binding of Tachplesin I to DNA Revealed by Footpriting Analysis:Signifi-cant Contribution of Secondary Structure to DNA Binding and Inplication for Biological Action" Biochemistry. 31. 2998-3004 (1992)

[Publications] J.Kuwahara: "Binding and Cleavage Characteristics of DNA by Bleomycin-Vanadium Complex" Bull.Inst.Chem.Res.Kyoto Univ.69. 511-519 (1992)

[Publications] A.Ichikawa: "Activation of DNA Cleavage by Dynemicin A in a B-Z Conformational Junction" Biochemistry. 31. 6784-6787 (1992)

[Publications] N.Nakamura: "The First Topa-Contaning Copper(II) Complex,[Cu(DL-topa)(bpy)-(H_2O)]BF_4・3H_2O,as a Model for the Active Site in Copper-Containing Amine Oxidase" J.Am.Chem.Soc.114. 6550-6552 (1992)

[Publications] N.Nakamura: "Synthesis and Structure of a Topa-Containing Ternary Copper(II) Complex" J.Inorg.Biochem.47. 54 (1992)

[Publications] S.Suziki: "Effect of Type II Copper on Enzyme Activity of Copper-Contaning Nitrite Reductase" J.Inorg.Biochem.47. 59 (1992)

[Publications] S.Kitagawa: "Synthesis of the Novel InfInite-Sheet- and -Chain Copper(I) Complex Polymers,{[Cu(C_4H_4N_2)_3/_2(CH_3CN)](PF_6)・0.5C_3H_6O}∞ and {[Cu(C_8H_<12>N_2)_3](C1O_4)_2}∞ and Their X-ray Crystal Structures" Inorg.Chem.31. 1714-1717 (1992)

[Publications] K.Matsumoto: "Synthesis of Functionalized Pyridines:Aminolisis of 2, 6-Dichloropyridines" Chemistry Express. 7. 473-476 (1992)

[Publications] M.Munakata: "Synthesis,Structures and Formation Constants of Copper(I) Complexes with Alkynes and 1,10-Phenanthroline" J.Chem.Soc.,Dalton.Trans.2225-2230 (1992)

[Publications] M.Ochiai: "High-Presssure Functionalization of Diaza-Crown Ethers:New Synthesis of Ag^+Ion-Specific Binders" J.Org.Chem.57. 542-547 (1992)

[Publications] K.Matsumoto: "Syntheses,Crystal Structures.and Electronic,ESR,and X-Ray Photoelectron Spectra of Acetamidate-and 2-Fluoroacetamidate-Bridged Mixed-Valent Octanuclear Platinum Blues" J.Am.Chem.Soc.114. 8110-8118 (1993)

山内脩名古屋大学, 理学部, 教授 (70029643)