1991 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	03241102
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) 森島積京都大学, 工学部, 教授 (50026093)
Keywords	生体関連金属錯体 / 多重相互作用 / 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
Research Abstract	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。

Research Products
(17 results)

All Other

All Publications (17 results)

[Publications] 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)
[Publications] 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)
[Publications] Akira Odani: "Platinum DNA Intercalator-Mononucleotide Adduct Formation.Cooperativity between Aromatic Ring Stacking and Electrostatic Interactions" Inorg.Chem.30. 2133-2138 (1991)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] K.Yamaguchi: "Push Effect on the Heterolytic O-O Bond Cleavage of Peroxo-Fe(III)-porphyrin Adducts." Inorg.Chem.31. 156-157 (1992)
[Publications] 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)
[Publications] M.Unno: "Pressure Effects on the Carbon Monoxide Rebinding to the Isolated a and b Chains of human Hemoglobin." Biochemistry. 30. 10679-10685 (1991)
[Publications] Y.Watanabe: "Remarkable Solvent Effect on the Shape-Selective Oxidation of Olefins Catalyzed by Iron(III) Porphyrins." Inorg.Chem.30. 2581-2582 (1991)
[Publications] 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)
[Publications] 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,)
[Publications] 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)
[Publications] H.Nagao: "Carbon Dioxide Fixation Competed with Proton Addition to Methyl Acrylate." Chem.Lett.323-326 (1991)
[Publications] Hidekazu IWASAKI: "Spectral Properties of Achromobacter xylosoxidans Cytochrome c' and Their NO Complexes" Biochim.Biophys.Acta. 1058. 79-82 (1991)
[Publications] Tsuyoshi INOUE: "Preliminary Crystallographic Study of a Pseudoazurin from Methylotrophic Bacteria,Methlobacterium extorquens AMI" J.Mol.Biol.218. 19-20 (1991)
[Publications] 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 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] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

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

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

[Publications] 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)

[Publications] 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,)

[Publications] 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)

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

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

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

[Publications] 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)

山内脩名古屋大学, 理学部, 教授 (70029643)