1991 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	03241102
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) 森島積京都大学, 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 / 反応速度制御 / 金属酵素モデル / 銅酵素 / 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、生体系に存在する金属錯体の構造と特異機能を分子レベルで解明し、これに基づいて新しい錯体による精密化学反応系を構築することを目的とした。このため、生体関連低分子錯体、高分子錯体、およびモデル錯体について、(1)多重相互作用、(2)反応過程制御、(3)精密モデル化、(4)新反応系、の諸点について、重点的に研究を行った。 1.多重相互作用酵素ー基質、タンパク質ー核酸、ホルモンー受容体などの特異的結合の解明のため、中心金属周辺でのアミノ酸側鎖基の関与する非共有性相互作用、植物ホルモン受容体モデル銅(I)錯体、銅酵素の活性中心構造、DNA結合性タンパク質(亜鉛フィンガ-)などの研究を行い、それぞれ生体系の理解に重要な知見を得た。2.反応過程制御ヘムタンパク質のミオグロビン、ヘモグロビン、シトクロムPー450の活性中心ヘム近傍のアミノ酸を部位特異的に変換し、反応過程への影響を調べた。また、電子伝達体ルブレドキシンにおけるNーH…S水素結合が、電子伝達過程に重要な働きをすることを結論した。3.精密モデル化シトクロム酸化酵素の酸素還元過程を時間分解ラマン分光法で追求し、反応中間体を特徴づけた。また、本酵素の結晶化とX線結晶解析を進めた。光合成過程における水分解酵素のマンガン部位モデル錯体その他の精密モデル錯体の合成を行った。4.新反応系鉄ー硫黄クラスタ-を触媒として二酸化炭素固定によるケト酸の合成を行った.細胞毒ス-パ-オキシド不均化酵素モデル鉄錯体を開発し、その有効性を明らかにした。さらに,鉄,銅の錯体による酵素分子の活性化と有機化合物の酵素化反応を詳細に調べた。以上の成果をあげるため、全体会議、班長会議で情報連絡を緊密に行い、さらに公開シンポジウム(第1回)を東京にて開催した。購入したコンピュ-タ-により研究成果を集積し、ニュ-スレタ-で公表した。

研究成果

(17件)

すべてその他

すべて文献書誌 (17件)

[文献書誌] Akira Odani: "Thermodynamic Nucleic Base Specificity in Nucleotide-Metallointercalator Association.Structure-Stability Relationship Showing Significant Contribution of the Amino Group to Aromatic Ring Stacking" Inorg.Chem.30. 4484-4486 (1991)
[文献書誌] Sigel Helmut: "Comments on potentiometric pH titrations and the relationship between pH-meter reading and hydrogen ion concentration" Anal.Chim.Acta,. 255. 63-72 (1991)
[文献書誌] Akira Odani: "Platinum DNA Intercalator-Mononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorg.Chem.30. 2133-2138 (1991)
[文献書誌] Hideki Masuda: "Structural Evidence for the Intramolecular Charge-Transfer Interaction Involving an Indole Ring in Ternary Copper(II) Complexes with L-Tryptophan and Aromatic Diamines" Inorg.Chim.Acta.180,. 173-79 (1991)
[文献書誌] Hideki Masuda: "Copper(II)-Thioether Bondings in Multidentate N,S-Donor Ligand Complexes.Structural Dependance 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.(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" Inorganica Chimica Acta. 200. (1992)
[文献書誌] K.Yamaguchi: "Push Effect on the Heterolytic O-O Bond Cleavage of Peroxo-Fe(III)-porphyrin Adducts." Inorg.Chem.31. 156-157 (1992)
[文献書誌] S.Adachi: "Alteration of Human Myoglobin Proximal Histidine to Cysteine or Tyrosine by Site-Directed Mutagenesis:Characterization and Their Catalytic Activities." Biochem.Biophys.Res.Commun.180. 138-144 (1991)
[文献書誌] M.Unno: "Pressure Effects on the Carbon Monoxide Rebinding to the Isolated a and b Chains of human Hemoglobin." Biochemistry. 30. 10679-10685 (1991)
[文献書誌] Y.Watanabe: "Remarkable Solvent Effect on the Shape-Selective Oxidation of Olefins Catalyzed by Iron(III) Porphyrins." Inorg.Chem.30. 2581-2582 (1991)
[文献書誌] K.Imai: "Site-Directed Mutagenesis in Hemoglobin.Functional Role of Tyrosine-42-(C7)α at the α1-β2 Interface." J.Mol.Biol.218. 769-781 (1991)
[文献書誌] Ogura,T.: "Time-resolved resonance Raman investigation of cytochrome oxidase catalysis:Observation of a new oxygen-isotope sensitive Raman band" Bull.Chem.Soc.Jpn.64. 2901-2907 (1991,)
[文献書誌] Nagai,M.: "Unusual CO binding geometry in abnormal subunits of hemoglobin M Boston and Hb M Saskatoon (1991,Biochemistry,30,6495-6503)Observation of the O-O stretching Raman band for cytochrome P-450_<cam> under catalytic conditions" J.Biol.Chem.266. 10246-10248 (1991)
[文献書誌] H.Nagao: "Carbon Dioxide Fixation Competed with Proton Addition to Methyl Acrylate." Chem.Lett.323-326 (1991)
[文献書誌] Hidekazu IWASAKI: "Spectral Properties of Achromobacter xylosoxidans Cytochrome c' and Their NO Complexes" Biochim.Biophys.Acta. 1058. 79-82 (1991)
[文献書誌] Tsuyoshi INOUE: "Preliminary Crystallographic Study of a Pseudoazurin from Methylotrophic Bacteria,Methlobacterium extorquens AMI" J.Mol.Biol.218. 19-20 (1991)
[文献書誌] S.Ozawa: "NMR Studies of Iron(II) Nitrosyl π-Cation Radicals of Octaethylchlorin and Octaethylisobacteriochlorin as Models for Reaction Intermediate of Nitrite Reductase." J.Am.Chem.Soc.(1991)

1991 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] Akira Odani: "Thermodynamic Nucleic Base Specificity in Nucleotide-Metallointercalator Association.Structure-Stability Relationship Showing Significant Contribution of the Amino Group to Aromatic Ring Stacking" Inorg.Chem.30. 4484-4486 (1991)

[文献書誌] Sigel Helmut: "Comments on potentiometric pH titrations and the relationship between pH-meter reading and hydrogen ion concentration" Anal.Chim.Acta,. 255. 63-72 (1991)

[文献書誌] Akira Odani: "Platinum DNA Intercalator-Mononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorg.Chem.30. 2133-2138 (1991)

[文献書誌] Hideki Masuda: "Structural Evidence for the Intramolecular Charge-Transfer Interaction Involving an Indole Ring in Ternary Copper(II) Complexes with L-Tryptophan and Aromatic Diamines" Inorg.Chim.Acta.180,. 173-79 (1991)

[文献書誌] Hideki Masuda: "Copper(II)-Thioether Bondings in Multidentate N,S-Donor Ligand Complexes.Structural Dependance 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.(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" Inorganica Chimica Acta. 200. (1992)

[文献書誌] K.Yamaguchi: "Push Effect on the Heterolytic O-O Bond Cleavage of Peroxo-Fe(III)-porphyrin Adducts." Inorg.Chem.31. 156-157 (1992)

[文献書誌] S.Adachi: "Alteration of Human Myoglobin Proximal Histidine to Cysteine or Tyrosine by Site-Directed Mutagenesis:Characterization and Their Catalytic Activities." Biochem.Biophys.Res.Commun.180. 138-144 (1991)

[文献書誌] M.Unno: "Pressure Effects on the Carbon Monoxide Rebinding to the Isolated a and b Chains of human Hemoglobin." Biochemistry. 30. 10679-10685 (1991)

[文献書誌] Y.Watanabe: "Remarkable Solvent Effect on the Shape-Selective Oxidation of Olefins Catalyzed by Iron(III) Porphyrins." Inorg.Chem.30. 2581-2582 (1991)

[文献書誌] K.Imai: "Site-Directed Mutagenesis in Hemoglobin.Functional Role of Tyrosine-42-(C7)α at the α1-β2 Interface." J.Mol.Biol.218. 769-781 (1991)

[文献書誌] Ogura,T.: "Time-resolved resonance Raman investigation of cytochrome oxidase catalysis:Observation of a new oxygen-isotope sensitive Raman band" Bull.Chem.Soc.Jpn.64. 2901-2907 (1991,)

[文献書誌] Nagai,M.: "Unusual CO binding geometry in abnormal subunits of hemoglobin M Boston and Hb M Saskatoon (1991,Biochemistry,30,6495-6503)Observation of the O-O stretching Raman band for cytochrome P-450_<cam> under catalytic conditions" J.Biol.Chem.266. 10246-10248 (1991)

[文献書誌] H.Nagao: "Carbon Dioxide Fixation Competed with Proton Addition to Methyl Acrylate." Chem.Lett.323-326 (1991)

[文献書誌] Hidekazu IWASAKI: "Spectral Properties of Achromobacter xylosoxidans Cytochrome c' and Their NO Complexes" Biochim.Biophys.Acta. 1058. 79-82 (1991)

[文献書誌] Tsuyoshi INOUE: "Preliminary Crystallographic Study of a Pseudoazurin from Methylotrophic Bacteria,Methlobacterium extorquens AMI" J.Mol.Biol.218. 19-20 (1991)

[文献書誌] S.Ozawa: "NMR Studies of Iron(II) Nitrosyl π-Cation Radicals of Octaethylchlorin and Octaethylisobacteriochlorin as Models for Reaction Intermediate of Nitrite Reductase." J.Am.Chem.Soc.(1991)

1991 年度実績報告書

山内脩名古屋大学, 理学部, 教授 (70029643)