1992 年度実績報告書

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

研究課題

研究課題/領域番号	04225102
研究機関	名古屋大学
研究代表者	山内脩名古屋大学, 理学部, 教授 (70029643)
研究分担者	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)
キーワード	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
研究概要	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。

研究成果

(18件)

すべてその他

すべて文献書誌 (18件)

[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Osamu Yamauchi: "Copper-Pteridine Chemistry.Structures,Solution Equilibria,and Redox Reactions" J.Inorg.Biochem.47. 40 (1992)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] M.Otsuka: "A Synthetic Model Approach to the Sugar Moiety of Bleomycin" Heterocycles. 33. 27-34 (1992)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] J.Kuwahara: "Binding and Cleavage Characteristics of DNA by Bleomycin-Vanadium Complex" Bull.Inst.Chem.Res.Kyoto Univ.69. 511-519 (1992)
[文献書誌] A.Ichikawa: "Activation of DNA Cleavage by Dynemicin A in a B-Z Conformational Junction" Biochemistry. 31. 6784-6787 (1992)
[文献書誌] 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)
[文献書誌] N.Nakamura: "Synthesis and Structure of a Topa-Containing Ternary Copper(II) Complex" J.Inorg.Biochem.47. 54 (1992)
[文献書誌] S.Suziki: "Effect of Type II Copper on Enzyme Activity of Copper-Contaning Nitrite Reductase" J.Inorg.Biochem.47. 59 (1992)
[文献書誌] 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)
[文献書誌] K.Matsumoto: "Synthesis of Functionalized Pyridines:Aminolisis of 2, 6-Dichloropyridines" Chemistry Express. 7. 473-476 (1992)
[文献書誌] 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)
[文献書誌] M.Ochiai: "High-Presssure Functionalization of Diaza-Crown Ethers:New Synthesis of Ag^+Ion-Specific Binders" J.Org.Chem.57. 542-547 (1992)
[文献書誌] 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 年度 実績報告書

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

研究代表者

山内 脩 名古屋大学, 理学部, 教授 (70029643)

研究成果

[文献書誌] 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)

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

[文献書誌] 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)

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

[文献書誌] 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)

[文献書誌] 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)

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

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

[文献書誌] 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)

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

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

[文献書誌] 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)

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

[文献書誌] 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)

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

[文献書誌] 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 年度実績報告書

山内脩名古屋大学, 理学部, 教授 (70029643)