1991 年度実績報告書

生体関連金属錯体における多重相互作用と機能発現の研究

研究課題

研究課題/領域番号	03241101
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	杉浦幸雄京都大学, 化学研究所, 教授 (40025698) 松本和子早稲田大学, 理工学部, 教授 (60111457) 宗像惠近畿大学, 理工学部, 教授 (80090942) 鈴木晋一郎大阪大学, 教養部, 教授 (70116052)
キーワード	多重相互作用 / 分子間相互作用 / エチレンレセプタ- / 芳香環スタッキング / 銅(I)錯体 / 転写因子Spl / 白金ブル-錯体 / 亜硝酸還元酵素
研究概要	本研究は生体系金属イオン周辺での種々の相互作用の様式を生体系およびモデル系について検討し、銅酵素の活性中心構造、金属酵素ー基質相互作用、DNAー金属錯体相互作用に関する情報を集積して、これらが機能発現に果たす役割を明らかにすることを目的とした。 1.モデル錯体の構造と多重相互作用酵素ー基質相互作用などの特異性発現のための、中心金属イオン近傍でのアミノ酸側鎖官能基、核酸塩基などが関与する分子内および分子間の相互作用の様式とエネルギ-を明らかにした。植物ホルモンであるエチレンの受容体として、種々の銅(I)錯体の有効性を各種エチレン錯体の合成と構造解析ならびに錯体の安定度から明らかにした。これらの知見から、生体系においても銅タンパク質が最有力候補であると結論した。 2.金属酵素・タンパク質活性中心構造と反応メカニズム銅タンパク質について、亜硝酸還元酵素におけるタイプI,II銅の役割を結論づけ、マルチ銅酵素ラッカ-ゼとシトクロムcとの電子移動反応の際の相互作用様式を推定した。ブル-銅タンパク質シュ-ドアズリンについては、タンパク質の結晶化を行ない、X線結晶構造解析を進めている。 3.DNAー金属錯体相互作用分子認識の観点から,DNA塩基配列を認識して特異的に結合する転写因子Splの亜鉛フィンガ-を含むドメインを、クロ-ニングにより大腸菌中で産生させて亜鉛結合部位の性質を明らかにし、DNA結合能を調べた。一方、DNAの切断、変性を引き起こす白金ブル-錯体を合成し、ヌクレオチドとの反応性、反応生成物を明らかにした。

研究成果

(18件)

すべてその他

すべて文献書誌 (18件)

[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 Bactera,Methylobacterium extorquens AM1" J.Mol.Biol.218. 19-20 (1991)
[文献書誌] S.Kitagawa: "Crystal Structure of an Infinite Stair-type Chain Compound [{Cu_2(tc)_2(ClO_4)_2}_n](tc=thiochrome)" J.Chem.Soc.Dalton Trans.1717 (1991)
[文献書誌] M.Munakata,: "Synthesis,Characterization.and Molecular Structures of Binary and Ternary copper(I) Complexes with 1,5-Cyclooctadiene(cod),[Cu(cod)_2](ClO_4) and [Cu(cod)(2,2'-bipyridine)]PF_6" Inorg,Chem.30. 2610 (1991)
[文献書誌] H.Urata: "Synthesis,Crystal Structure and Solvolysis Reaction of a H-T 3,3-Dimethylglutarimidate-Bridged Binuclear Platinum(II) Complex,[Pt_2(NH_3)_4(C_7H_<10>NO_2)_2](NO_3)_2H_2O" Inorg.Chem.30. 3914-3919 (1991)
[文献書誌] R.Kuroda: "Tetranuclear Platinum Compounds with High Anititumour Activity:Solution Chemistry and DNA Binding Mode" J.Inorg.Biochem.43. 429 (1991)
[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 Chimca Acta. 200. (1992)
[文献書誌] K.Matsumoto: "A Tetranuclear Tervalent Platinum Complex with Pyrrolidonate and Deprotonated Ammine Bridging ligands,[(NO_3)(NH_3)_2Pt^<III>(D_4H_6NO)_2Pt^<III>-(NH_3)(μ-NH_2)]_2(NO_3)_4" Inorg.Chem.30. 3032-3034 (1991)
[文献書誌] K.Sakai: "Crystal Structure of 2-Fluoroacetamidato-Bridged Mixed-Valent Octanuclear Platinum Blue with Average Platinum oxidation State of 2.08,[Pt_8(NH_3)_<16>(CH_2FCONH)_8](NO_3)_<8.66>・4H_2O" Chem.Lett.1081-1084 (1991)
[文献書誌] K.Sakai: "Oxidation of benzene to phenol with hydrogen peroxide catalyzed by α-pyrrrolidonate-bridged mixed-valent tetranucleaar platinum complexes" J.Mol.Catal.67. 7-18 (1991)
[文献書誌] Y.Uesawa: "Heat-induced DNA cleavage by esperamicin antitumor antibiotics" Biochemistry. 30(38). 9242-9246 (1991)
[文献書誌] Y.Sugiura: "Reductive and nucleophilic activation products of dynemicin A with methyl thioglycolate.A rational mechanism for DNA cleavage of the thiol-activated dynemicin A" Biochemistry. 30(12). 2989-2992 (1991)
[文献書誌] M.Munakata: "「多核NMR入門ー状態分析へのアプロ-チ」" 講談社サイエンティフィク, 326 (1991)

1991 年度 実績報告書

生体関連金属錯体における多重相互作用と機能発現の研究

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] 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 Bactera,Methylobacterium extorquens AM1" J.Mol.Biol.218. 19-20 (1991)

[文献書誌] S.Kitagawa: "Crystal Structure of an Infinite Stair-type Chain Compound [{Cu_2(tc)_2(ClO_4)_2}_n](tc=thiochrome)" J.Chem.Soc.Dalton Trans.1717 (1991)

[文献書誌] M.Munakata,: "Synthesis,Characterization.and Molecular Structures of Binary and Ternary copper(I) Complexes with 1,5-Cyclooctadiene(cod),[Cu(cod)_2](ClO_4) and [Cu(cod)(2,2'-bipyridine)]PF_6" Inorg,Chem.30. 2610 (1991)

[文献書誌] H.Urata: "Synthesis,Crystal Structure and Solvolysis Reaction of a H-T 3,3-Dimethylglutarimidate-Bridged Binuclear Platinum(II) Complex,[Pt_2(NH_3)_4(C_7H_<10>NO_2)_2](NO_3)_2H_2O" Inorg.Chem.30. 3914-3919 (1991)

[文献書誌] R.Kuroda: "Tetranuclear Platinum Compounds with High Anititumour Activity:Solution Chemistry and DNA Binding Mode" J.Inorg.Biochem.43. 429 (1991)

[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 Chimca Acta. 200. (1992)

[文献書誌] K.Matsumoto: "A Tetranuclear Tervalent Platinum Complex with Pyrrolidonate and Deprotonated Ammine Bridging ligands,[(NO_3)(NH_3)_2Pt^<III>(D_4H_6NO)_2Pt^<III>-(NH_3)(μ-NH_2)]_2(NO_3)_4" Inorg.Chem.30. 3032-3034 (1991)

[文献書誌] K.Sakai: "Crystal Structure of 2-Fluoroacetamidato-Bridged Mixed-Valent Octanuclear Platinum Blue with Average Platinum oxidation State of 2.08,[Pt_8(NH_3)_<16>(CH_2FCONH)_8](NO_3)_<8.66>・4H_2O" Chem.Lett.1081-1084 (1991)

[文献書誌] K.Sakai: "Oxidation of benzene to phenol with hydrogen peroxide catalyzed by α-pyrrrolidonate-bridged mixed-valent tetranucleaar platinum complexes" J.Mol.Catal.67. 7-18 (1991)

[文献書誌] Y.Uesawa: "Heat-induced DNA cleavage by esperamicin antitumor antibiotics" Biochemistry. 30(38). 9242-9246 (1991)

[文献書誌] Y.Sugiura: "Reductive and nucleophilic activation products of dynemicin A with methyl thioglycolate.A rational mechanism for DNA cleavage of the thiol-activated dynemicin A" Biochemistry. 30(12). 2989-2992 (1991)

[文献書誌] M.Munakata: "「多核NMR入門ー状態分析へのアプロ-チ」" 講談社サイエンティフィク, 326 (1991)

1991 年度実績報告書

山内脩名古屋大学, 理学部, 教授 (70029643)