Structures and Properties of Metal Binding Sites in Biological and Model Systems

生物和模型系统中金属结合位点的结构和性质

• 批准号: 63430009
• 负责人: YAMAUCHI Osamu
• 金额: $ 13.76万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63430009/
• 关键词: Biological metal ions; Mixed ligand copper(II) complexes; Pterin-containing copper(II) complexes; Aromatic ring stacking; Intermolecular association; Solution equilibria of complexes; Copper(II) complex of folic acid; Electrostatic ligand-ligand in

With a view to obtaining basic information regarding the metal complex in biological systems, we investigated the modes of biomoleculemetal ion interactions and the structures of the resulting complexes.1. Aromatic Ring Stacking and Electrostatic Interactions between Coordinated Ligands. X-ray crystal structure analysis of ternary copper(II) complexes containing histamine and phenylalanine or tyrosine disclosed the aromatic ring stacking between coordinated imidazole and the side chain aromatic ring of the amino acids. Aromatic ring stacking has also been detected between uncoordinated indole and copper(II)-coordinated 1,10-phenanthroline. Intramolecular electrostatic ligand-ligand interactions in ternary copper(II) complexes of ligands with oppositely charged side chains were concluded for the complexes in solution on the basis of the intermolecular interactions established in the solid state between the carboxylate group and the guanidinium group from two adjacent molecules.2. Coordi … More nation Structures and Properties of Copper(II)-Pterin Complexes. Folic acid, a pterin cofactor, has been found to react with copper(II)-2,2'-bipyridine to give a ternary complex containing 2,2'-bipyridine and pterin-6-carboxylate as a result of the Cu(II)-catalyzed oxidative cleavage of the side chain of folic acid. The structure of the complex revealed by X-ray analysis shows that the pterin ring coordinates to copper(II) through the N(5) atom with its ring perpendicular to the coordination plane. An equatorial position is occupied by a water molecule, which was found to be easily displaced by imidazole to give a quaternary complex. This suggests that the position may be the substrate binding site.3. Palladium(II)-Indole and Platinum(II) Complex-Indole Interactions. Tetrachloropalladate(II) reacted with alkylindoles and indole-3-acetate to give complexes where the indole ring coordinates to palladium(II) through its nitrogen in the 3H-indole form. Platinum(II) complexes with coordinated aromatic diamines interacted with indole-3-acetate etc. to form adducts, whose stability constants and thermodynamic parameters showed that the adduct formation is mainly due to stacking between the coordinated aromatic diamine and the indole ring. Less

为了获得有关生物体系中金属配合物的基本信息，我们研究了生物分子金属离子相互作用的模式和所得配合物的结构。芳环堆积与配位配体间的静电相互作用。X-射线晶体结构分析的三元铜（II）配合物含有组胺和苯丙氨酸或酪氨酸披露之间的协调咪唑和侧链芳香环的氨基酸的芳香环堆积。芳环堆积也被检测到之间的非协调吲哚和铜（II）-协调的1，10-菲咯啉。基于固体状态下相邻两分子上的羧酸根和胍基之间的分子间相互作用，推导出溶液中带相反电荷侧链的三元铜（II）配合物中存在的分子内静电配体间相互作用.库尔迪 ...更多信息 铜（Ⅱ）-蝶呤配合物的结构与性质叶酸是一种蝶呤辅因子，它与铜（II）-2，2 '-联吡啶反应，生成含2，2'-联吡啶和蝶呤-6-羧酸的三元配合物，这是由于铜（II）催化叶酸侧链的氧化断裂所致。X射线衍射分析表明，配合物的结构是蝶呤环通过N（5）原子与铜（II）配位，且蝶呤环垂直于配位平面。赤道位置被一个水分子占据，发现它很容易被咪唑取代，得到一个四元配合物。这表明该位置可能是底物结合位点.钯（II）-吲哚和铂（II）络合物-吲哚相互作用。四氯钯（II）与烷基吲哚和吲哚-3-乙酸反应得到配合物，其中吲哚环通过3 H-吲哚形式的氮与钯（II）配位。芳香二胺与铂（II）配合物与吲哚-3-乙酸酯等形成加合物，其稳定常数和热力学参数表明，加合物的形成主要是芳香二胺与吲哚环之间的堆积作用。少

项目成果

Akira Odani: "Effects of Phosphorylation of Amino Acid Side Chains on the Formation of Ternary Copper(II)Complexes Intramolecular Electrostatic Ligand-Ligand Interactions between Phosphoester and Arginine or Lysine Side Groups" 発表予定.

Akira Odani：“氨基酸侧链磷酸化对三元铜 (II) 复合物形成的影响以及磷酸酯和精氨酸或赖氨酸侧基之间的分子内静电配体相互作用”。

Osamu Yamauchi, Akira Odani, Reiko Shimata, and Hideki Masuda: "Adduct Formation between Platinum DNA Intercalators and Mononucleotides through Noncovalent Interactions. Spectroscopic and Structural Studies"

Osamu Yamauchi、Akira Odani、Reiko Shimata 和 Hideki Masuda：“通过非共价相互作用在铂 DNA 嵌入剂和单核苷酸之间形成加合物。光谱和结构研究”

Helmut Sigel: "The Imidazole Group and Its Stacking Properties in Mixed Ligand Metal Ion Complexes" Comments on Inorganic Chemistry(in press). 8. (1990)

Helmut Sigel：“混合配体金属离子配合物中的咪唑基团及其堆积特性”对无机化学的评论（正在出版）。

Hideki Masuda, Akira Odani, and Osamu Yamauchi: "Structure of an L-Tyrosyl-L-histidine-Copper Complex Involving an Axial Copper(II)-Phenol OH Bonding. Implication for Substrate binding at the Active Site Tyrosinase" Inorganic Chemistry, 28, 624-625(1989).

Hideki Masuda、Akira Odani 和 Osamu Yamauchi：“涉及轴向铜 (II)-苯酚 OH 键合的 L-酪氨酰-L-组氨酸-铜复合物的结构。对酪氨酸酶活性位点的底物结合的影响”无机化学，28

Osamu Yamauchi: "Adduct Formation between Platinum DNA Intercalators and Mononucleotides through Noncovalent Interactions.Spectroscopic and Structural Studies"

Osamu Yamauchi：“通过非共价相互作用在铂 DNA 嵌入剂和单核苷酸之间形成加合物。光谱和结构研究”