1992 年度実績報告書

生物無機化学における構造と特異機能の研究

研究課題

研究課題/領域番号	04225101
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	鈴木晋一郎大阪大学, 教養部, 教授 (70116052) 北川禎三岡崎国立共同研究機構分子科学研究所, 教授 (40029955) 田中晃二岡崎国立共同研究機構分子科学研究所, 教授 (00029274) 森島績京都大学, 工学部, 教授 (50026093)
キーワード	生体関連金属錯体 / 多重相互作用 / DNA塩基認識 / 金属酵素モデル / 銅酵素 / 人工変異ヘムタンパク質 / 光合成系マンガン錯体 / 二酸化炭素固定
研究概要	本研究は、生体系における微量元素、とくに鉄、銅、亜鉛、モリブデンなどの遷移金属元素と生体物質との錯形成反応、錯体の構造と機能、反応メカニズムを分子レベルで解明し、さらに新しい精密化学反応系を構築する事を目的とした。このため、多重相互作用(山内)、反応過程制御(森島)、精密モデル化(北川)、新反応系(田中)、データ解析(鈴木)について、次の諸点を明らかにした: 1.多重相互作用アミノ酸側鎖の水素結合と芳香環スタッキングによる錯体の配位構造の固定、亜硝酸還元酸素中のタイプI,IIの銅の役割、フェニルアラニンヒドロキシラーゼモデルの開発、DNA結合タンパク質Sp1による塩基認識への各フィンガー役割。2.反応過程制御人工変異ミオグロビン等による鉄の軸配位子の違いの反応特性への影響、ヘム酵素P450の触媒作用へのアミノ酸残基の効果。3.精密モデル化シトクロム酸化酵素によるO_2の還元過程、亜鉛酵素アルコールデヒドロゲナーゼ活性中心モデルの開発と触媒能、マンガン酵素モデル錯体の合成と反応性。4.新反応系炭酸ガスを固体しメタノールへの還元能を有する錯体の開発と反応生成物の同定、銅錯体を用いる亜硝酸還元酵素モデルおよび鉄錯体によるSODモデル、モノオキシゲナーゼモデルの開発の反応活性。研究遂行上、微量成分の精密解析のための電子天秤、データ解析用のパーソナルコンピューターをそれぞれ購入して、研究に役立てた。研究目的達成のため全体会議3回、公開シンポジウム2回(名古屋、京都)を開催した。

研究成果

(21件)

すべてその他

すべて文献書誌 (21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 Phosphorylated Side Chain.Conversion of Aromatic Ring Stacking to Electrostatic 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 Cofactor-Substrate Association Structure of Ternary Copper(II)-2,2'-Bipyridine-Lumazine Complex and Successful Equilibrium Study of a Quaternary 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 Implication" Inorg.Chem.32. (1993)
[文献書誌] S.Ozawa: "NMR Studeis of Iron(II) Nitrosyl π-Cation Radicals of Octaethylchlorin and Octaethylisobacteriochlorin as Models for Reaction Intermediate of Nitrite Reductase" J.Am.Chem.Soc.114. 1548 (1992)
[文献書誌] K.Ishimori: "SiteDircted Mutagenesis in Hemoglobin: Functional and Structural Role of Inter-and Intrasubunit Hydrogen Bonds As Studied With 37β Mutations" Biochemistry. 31. 3256 (1992)
[文献書誌] K.Ishimori: "Sturcture and Ligand Binding Properties of Leucine 29(B10) Mutants of Human Myoglobin" Biochemistry. 267. 12614 (1992)
[文献書誌] K.Yamaguchi: "Push Effects on the Heterolytic O-O Bond Cleavage of Peroxoiron(III) Porphyrin Adducts" Inorg.Chem.31. 156 (1992)
[文献書誌] K.Yamaguchi: "Low-Valent Iron Porphyrins.NMR Evidence for π-Anion-Radical Character in Two-Electron-Reduced Iron(III) Meso-or β-Pyrrole-Substituted Porphyrins" Inorg.Chem.31. 3216 (1992)
[文献書誌] S.Sato: "Time-Resolved Resonance Raman Spectra of Free-Bace Octaethylporphyrin in the S_1 and T_1 States" Chem.Phys.Lett.189. 443-447 (1992)
[文献書誌] N.Kitajima: "A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structrue of the μ-η^2:η^2 Peroxo Dinuclear Copper(II) Complexes,[Cu(HB(3,5-R_2pz)_3)]_2(O_2)(R=iPr and Ph)" J.Am.Chem.Soc.114. 1227-1291 (1992)
[文献書誌] S.Kaminaka: "Time-Resolved UV Resonance Raman Study on Bohr Effects of Hemoglobin" J.Am.Chem.Soc.114. 3256-3260 (1992)
[文献書誌] K.Ishimori: "Site Dircted Mutagenesis in Hemoglobin: Functional and Structural Role of Inter-and Intrasubunit Hydrogen Bonds as Studied With 37β and 145β Mutations" Biochemistry. 31. 3256-3265 (1992)
[文献書誌] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. 3625-3630 (1992)
[文献書誌] H.Tanaka: "Synthesis and Characterization of Bis (2,2'-bipyridyl) Nitro-Corbonylruthenium(II)Hexafluorophosphate" Inorg.Chem.31. 1971-1973 (1992)
[文献書誌] H.Tanaka: "Crystal Structure of cis-(Carbon Monoxide)(η^1-Carboon Dioxide)bis(2,2-bipyridyl)Ruthenium,an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-" Organometallics. 11. 1450-1451 (1992)
[文献書誌] H.Kambayashi: "Crystal Structure of (Ph_4As)_2[Fe_4S_4(SAD)_4]and Stabiliozation of [Fe_4S_4(SAD)_4]^- State in Aqueous Media." Chem.Lett.919-922 (1992)
[文献書誌] S.Suzuki: "The First topa-Containing 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] S.Suzuki: "Synthesis and Structure of a topa-Containing Ternary Copper(II)Complex" J.Inorg.Biochem.47. 54 (1992)
[文献書誌] S.Suzuki: "Effect of Type II Copper on Enzyme Activity of Copper-Containing Nitrite Reductase" J.Inorg.Biochem.47. 59 (1992)

1992 年度 実績報告書

生物無機化学における構造と特異機能の研究

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 Phosphorylated Side Chain.Conversion of Aromatic Ring Stacking to Electrostatic 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 Implication" Inorg.Chem.32. (1993)

[文献書誌] S.Ozawa: "NMR Studeis of Iron(II) Nitrosyl π-Cation Radicals of Octaethylchlorin and Octaethylisobacteriochlorin as Models for Reaction Intermediate of Nitrite Reductase" J.Am.Chem.Soc.114. 1548 (1992)

[文献書誌] K.Ishimori: "SiteDircted Mutagenesis in Hemoglobin: Functional and Structural Role of Inter-and Intrasubunit Hydrogen Bonds As Studied With 37β Mutations" Biochemistry. 31. 3256 (1992)

[文献書誌] K.Ishimori: "Sturcture and Ligand Binding Properties of Leucine 29(B10) Mutants of Human Myoglobin" Biochemistry. 267. 12614 (1992)

[文献書誌] K.Yamaguchi: "Push Effects on the Heterolytic O-O Bond Cleavage of Peroxoiron(III) Porphyrin Adducts" Inorg.Chem.31. 156 (1992)

[文献書誌] K.Yamaguchi: "Low-Valent Iron Porphyrins.NMR Evidence for π-Anion-Radical Character in Two-Electron-Reduced Iron(III) Meso-or β-Pyrrole-Substituted Porphyrins" Inorg.Chem.31. 3216 (1992)

[文献書誌] S.Sato: "Time-Resolved Resonance Raman Spectra of Free-Bace Octaethylporphyrin in the S_1 and T_1 States" Chem.Phys.Lett.189. 443-447 (1992)

[文献書誌] N.Kitajima: "A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structrue of the μ-η^2:η^2 Peroxo Dinuclear Copper(II) Complexes,[Cu(HB(3,5-R_2pz)_3)]_2(O_2)(R=iPr and Ph)" J.Am.Chem.Soc.114. 1227-1291 (1992)

[文献書誌] S.Kaminaka: "Time-Resolved UV Resonance Raman Study on Bohr Effects of Hemoglobin" J.Am.Chem.Soc.114. 3256-3260 (1992)

[文献書誌] K.Ishimori: "Site Dircted Mutagenesis in Hemoglobin: Functional and Structural Role of Inter-and Intrasubunit Hydrogen Bonds as Studied With 37β and 145β Mutations" Biochemistry. 31. 3256-3265 (1992)

[文献書誌] N.Komeda: "Electrochemical Carbon Dioxide Fixation to Thioesters Catalyzed by [Mo_2Fe_6S_8(SEt)_9]^<3->" J.Am.Chem.Soc.114. 3625-3630 (1992)

[文献書誌] H.Tanaka: "Synthesis and Characterization of Bis (2,2'-bipyridyl) Nitro-Corbonylruthenium(II)Hexafluorophosphate" Inorg.Chem.31. 1971-1973 (1992)

[文献書誌] H.Tanaka: "Crystal Structure of cis-(Carbon Monoxide)(η^1-Carboon Dioxide)bis(2,2-bipyridyl)Ruthenium,an Active Species in Catalytic CO_2 Reduction Affording CO and HCOO^-" Organometallics. 11. 1450-1451 (1992)

[文献書誌] H.Kambayashi: "Crystal Structure of (Ph_4As)_2[Fe_4S_4(SAD)_4]and Stabiliozation of [Fe_4S_4(SAD)_4]^- State in Aqueous Media." Chem.Lett.919-922 (1992)

[文献書誌] S.Suzuki: "The First topa-Containing 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] S.Suzuki: "Synthesis and Structure of a topa-Containing Ternary Copper(II)Complex" J.Inorg.Biochem.47. 54 (1992)

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

1992 年度実績報告書

山内脩名古屋大学, 理学部, 教授 (70029643)