1993 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 / 生体内反応過程 / 金属酵素モデル / 分子認識系 / 人工変異タンパク質 / 電子移動反応系
研究概要	生体系に存在する微量金属元素の役割の解明とその機能の化学モデルを意図して、3年間にわたり研究を行ってきた。本年度は特に最終年度であることをふまえて、(i)多重相互作用の生体系における意義(山内)、(ii)生体反応系における反応過程制御(森島)、(iii)生体反応系の精密解析(北川)、(iv)新反応系の機能(田中)、に焦点を絞り、研究を行った。また、知見をまとめ、公開シンポジウムにおいて公表した(鈴木)。この結果得られた成果をまとめると次の通りである: 1.金属イオン近傍での非共有性相互作用の存在様式についてモデル系で明らかにしたのち、ヒト転写因子によるDNAの特異的結合およびカルモジュリンのカルシウム結合部位構造と標的細胞との結合能との関係を解明した。また、認識による特異的反応を明らかにした。 2.ヘム酵素反応中間体としての酸素の結合様式と活性化をP450、変異ヘモグロビン等を用いて究明した。さらに、部位特異的にアミノ酸残基を置換したプラストシアニン、P450により、反応メカニズムの情報を得た。 3.マンガン含有カタラーゼ活性中心の精密モデル化を用い、反応メカニズムおよび光合成系におけるマンガンクラスターとの関連性に関する有力な情報を得た。シトクロム酸化酵素による酸素還元過程でのヘム鉄の反応の詳細を明らかにした。 4.電極表面での金属蛋白質との電子移動、硝酸の還元過程、芳香環の酸素化過程などの酸化還元を伴う反応系の構築を行った。 5.研究方針の設定等のため、総括班会議2回、研究目標達成のため全体会議2回をそれぞれ開催した。また、研究成果を2回の公開シンポジウム(吹田、東京にて開催)により公表した。

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] H.Masuda: "Structures and Stabilities of Ternary Copper(II)Complexes Containing an Acidic and a Basic Amino Acid.Evidence for Arginine Side Chain Involvement in Intermolecular Interactions and Its Biological Implication" Inorg.Chem.32. 1111-1118 (1993)
[文献書誌] Osamu Yamauchi: "Ternary Metal(II)Complexes with Tyrosine-Containing Dipeptides.Structures of Copper(II)and Palladium(II)Complexes Involving L-Tyrosylglycine and Stabilization of Copper(II)Complexes Due to Intramolecular Aromatic Ring Stacking." Inorg.Chem.32. 4951-4959 (1993)
[文献書誌] Akira Odani: "Structures and Properties of Ternary Copper(II)Complexes Involving a Halogen Substituted Phenylalanine and 2,2'-Bipyridine.Intermolecular Interactions between Halo and Organic Groups." Bull.Chem.Soc.Jpn.67. 131-137 (1994)
[文献書誌] Akira Odani: "Spectroscopic Evidence for the Redox Reaction between Copper(II)and a Pterin Cofactor Model,6,7-Dimethyl-5,6,7,8-tetrahydropterin." Chem.Lett.385-388 (1994)
[文献書誌] L.Lomozik: "Spectroscopic studies on complex formation and noncovalent interactions in ternary palladium(II)systems involving spermidine and 2,3-diaminopropionate of 2,4-diaminobutyrate." Inorg.Chim.Acta. 219. 107-114 (1994)
[文献書誌] S.Ozawa: "Spectroscopic Characterization of Peroxo-Iron(III)Chlorin Complexes.The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)
[文献書誌] T.Konno: "Transition State of an Unfolding Step in Human Cyanomet Myoglobin." Biochim.Biophys.Acta. 1162. 93-98 (1993)
[文献書誌] A.Togi: "Effects of Intra and Intersubunit Hydrogen Bonds on the R-T Transition in Hunman Hemoglobin As Studied with α42(C7)and β145(HC2)Mutations." Biochemistry. 32. 10165-10169 (1993)
[文献書誌] M.Hisamoto: "Site-Directed Mutagenesis in Hemoglobin:Functional and Structural Study of the Intersubunit Hydrogen Bond of Threonine-38(C3)α at the α1-β2 Interface in Human Hemoglobin." Biochemistry. 32. 13688-13695 (1993)
[文献書誌] S.Ozawa: "Spectroscopic Characterization of Peroxo-Iron(III)Chlorin Complexes.The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)
[文献書誌] S.Ozawa: "Preparation and Characterization of Oxoiron(IV)Chlorin Complexes as the First Models for a Reaction Intermediate in the Catalytic Cycle of Cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)
[文献書誌] K.Ishimori: "Site-Directed Mutagenesis in Hemoglobin:Functional and Structural Role of Penultimate Tyrosine." Biochemistry. 33(in press). (1994)
[文献書誌] T.Inoue: "Crystallization and Preliminary X-ray Studies on Pseudoazurin from Achromobacter cycloclastes IAM 1013." J.Biochem.114. 761-762 (1993)
[文献書誌] T.Kohzuma: "Direct Electrochemistry of Copper-Containing Nitrite Reductase from Achromobacter xylosoxidans NCIB 11015." Chem.Lett.12. 2029-2032 (1993)
[文献書誌] S.Itoh: "Pysicochemical Properties of 2-Methylthio-4-methylphenol,a Model Compound of the Novel Cofactor of Galactose Oxidase." Chem.Lett.12. 2099-2102 (1993)
[文献書誌] N.Nakamura: "Structure of a Tripotassium Pyrroloquinoline Quinone Salt." Acta Cryst.2093-2095 (1993)
[文献書誌] Y.Nakao: "Preparation and Properties of the Dinuclear Copper(II)Complexes Bridged by an Alkoxo and an Exogenous Bridging Ligand." Bull.Chem.Soc.Jpn.67. 260-262 (1994)
[文献書誌] T.Kohzuma: "Direct Electrochemistry of Nitrite Reductase from Achromobacter cycloclastes IAM 1013." Bull.Chem.Soc.Jpn.138-143 (1994)
[文献書誌] T.Ogura: "Time-Resolved Resonance Raman Elucidation of the Pathway for Dioxygen Reduction by Cytochrome c Oxidase." J.Am.Chem.Soc.115. 8527-8536 (1993)
[文献書誌] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)
[文献書誌] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)

1993 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] H.Masuda: "Structures and Stabilities of Ternary Copper(II)Complexes Containing an Acidic and a Basic Amino Acid.Evidence for Arginine Side Chain Involvement in Intermolecular Interactions and Its Biological Implication" Inorg.Chem.32. 1111-1118 (1993)

[文献書誌] Osamu Yamauchi: "Ternary Metal(II)Complexes with Tyrosine-Containing Dipeptides.Structures of Copper(II)and Palladium(II)Complexes Involving L-Tyrosylglycine and Stabilization of Copper(II)Complexes Due to Intramolecular Aromatic Ring Stacking." Inorg.Chem.32. 4951-4959 (1993)

[文献書誌] Akira Odani: "Structures and Properties of Ternary Copper(II)Complexes Involving a Halogen Substituted Phenylalanine and 2,2'-Bipyridine.Intermolecular Interactions between Halo and Organic Groups." Bull.Chem.Soc.Jpn.67. 131-137 (1994)

[文献書誌] Akira Odani: "Spectroscopic Evidence for the Redox Reaction between Copper(II)and a Pterin Cofactor Model,6,7-Dimethyl-5,6,7,8-tetrahydropterin." Chem.Lett.385-388 (1994)

[文献書誌] L.Lomozik: "Spectroscopic studies on complex formation and noncovalent interactions in ternary palladium(II)systems involving spermidine and 2,3-diaminopropionate of 2,4-diaminobutyrate." Inorg.Chim.Acta. 219. 107-114 (1994)

[文献書誌] S.Ozawa: "Spectroscopic Characterization of Peroxo-Iron(III)Chlorin Complexes.The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)

[文献書誌] T.Konno: "Transition State of an Unfolding Step in Human Cyanomet Myoglobin." Biochim.Biophys.Acta. 1162. 93-98 (1993)

[文献書誌] A.Togi: "Effects of Intra and Intersubunit Hydrogen Bonds on the R-T Transition in Hunman Hemoglobin As Studied with α42(C7)and β145(HC2)Mutations." Biochemistry. 32. 10165-10169 (1993)

[文献書誌] M.Hisamoto: "Site-Directed Mutagenesis in Hemoglobin:Functional and Structural Study of the Intersubunit Hydrogen Bond of Threonine-38(C3)α at the α1-β2 Interface in Human Hemoglobin." Biochemistry. 32. 13688-13695 (1993)

[文献書誌] S.Ozawa: "Spectroscopic Characterization of Peroxo-Iron(III)Chlorin Complexes.The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)

[文献書誌] S.Ozawa: "Preparation and Characterization of Oxoiron(IV)Chlorin Complexes as the First Models for a Reaction Intermediate in the Catalytic Cycle of Cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)

[文献書誌] K.Ishimori: "Site-Directed Mutagenesis in Hemoglobin:Functional and Structural Role of Penultimate Tyrosine." Biochemistry. 33(in press). (1994)

[文献書誌] T.Inoue: "Crystallization and Preliminary X-ray Studies on Pseudoazurin from Achromobacter cycloclastes IAM 1013." J.Biochem.114. 761-762 (1993)

[文献書誌] T.Kohzuma: "Direct Electrochemistry of Copper-Containing Nitrite Reductase from Achromobacter xylosoxidans NCIB 11015." Chem.Lett.12. 2029-2032 (1993)

[文献書誌] S.Itoh: "Pysicochemical Properties of 2-Methylthio-4-methylphenol,a Model Compound of the Novel Cofactor of Galactose Oxidase." Chem.Lett.12. 2099-2102 (1993)

[文献書誌] N.Nakamura: "Structure of a Tripotassium Pyrroloquinoline Quinone Salt." Acta Cryst.2093-2095 (1993)

[文献書誌] Y.Nakao: "Preparation and Properties of the Dinuclear Copper(II)Complexes Bridged by an Alkoxo and an Exogenous Bridging Ligand." Bull.Chem.Soc.Jpn.67. 260-262 (1994)

[文献書誌] T.Kohzuma: "Direct Electrochemistry of Nitrite Reductase from Achromobacter cycloclastes IAM 1013." Bull.Chem.Soc.Jpn.138-143 (1994)

[文献書誌] T.Ogura: "Time-Resolved Resonance Raman Elucidation of the Pathway for Dioxygen Reduction by Cytochrome c Oxidase." J.Am.Chem.Soc.115. 8527-8536 (1993)

[文献書誌] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)

[文献書誌] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)

1993 年度実績報告書

山内脩名古屋大学, 理学部, 教授 (70029643)