1993 Fiscal Year Annual Research Report

生物無機化学における構造と特異機能の研究

Research Project

Project/Area Number	04225101
Research Institution	Nagoya University
Principal Investigator	山内脩名古屋大学, 理学部, 教授 (70029643)
Co-Investigator(Kenkyū-buntansha)	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)
Keywords	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
Research Abstract	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。

Research Products
(21 results)

All Other

All Publications (21 results)

[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] T.Konno: "Transition State of an Unfolding Step in Human Cyanomet Myoglobin." Biochim.Biophys.Acta. 1162. 93-98 (1993)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] K.Ishimori: "Site-Directed Mutagenesis in Hemoglobin:Functional and Structural Role of Penultimate Tyrosine." Biochemistry. 33(in press). (1994)
[Publications] T.Inoue: "Crystallization and Preliminary X-ray Studies on Pseudoazurin from Achromobacter cycloclastes IAM 1013." J.Biochem.114. 761-762 (1993)
[Publications] T.Kohzuma: "Direct Electrochemistry of Copper-Containing Nitrite Reductase from Achromobacter xylosoxidans NCIB 11015." Chem.Lett.12. 2029-2032 (1993)
[Publications] 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)
[Publications] N.Nakamura: "Structure of a Tripotassium Pyrroloquinoline Quinone Salt." Acta Cryst.2093-2095 (1993)
[Publications] 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)
[Publications] T.Kohzuma: "Direct Electrochemistry of Nitrite Reductase from Achromobacter cycloclastes IAM 1013." Bull.Chem.Soc.Jpn.138-143 (1994)
[Publications] 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)
[Publications] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)
[Publications] K.D.Karlin: "Bioinorganic Chemistry of Copper" Copper(II)-Pteridine Chemistry.Structures,Properties,and Phenylalanine Hydroxylase Models., (1993)

1993 Fiscal Year Annual Research Report

生物無機化学における構造と特異機能の研究

Principal Investigator

山内 脩 名古屋大学, 理学部, 教授 (70029643)

Research Products

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

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

[Publications] 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)

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

[Publications] 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)

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

[Publications] 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)

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

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

山内脩名古屋大学, 理学部, 教授 (70029643)