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

基本信息

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

项目摘要

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

为了获得生物系统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。1．配位配体之间的芳环堆积和静电相互作用分析。含有组胺和苯丙氨酸或酪氨酸的三元铜(II)络合物揭示了配位咪唑和氨基酸侧链芳环之间的芳环堆积。在不配位吲哚和铜(II)配位1,10-菲咯啉之间也检测到了芳香环堆积。对于溶液中的配合物，得出了具有相反电荷侧链的配体三元铜(II)配合物中的分子内静电配体-配体相互作用。基于两个相邻分子的羧酸根基团和胍基团之间在固态下建立的分子间相互作用。2。铜(II)-蝶呤复合物的结构和性质叶酸（一种蝶呤辅助因子）已被发现与铜(II)-2,2'-联吡啶反应生成含有 2,2'-联吡啶和的三元复合物。蝶呤-6-羧酸酯是铜（II）催化叶酸侧链氧化裂解的结果。 X射线分析表明蝶呤环通过N(5)原子与铜(II)配位，其环垂直于配位面，赤道位置被水分子占据，发现水分子很容易被咪唑取代。得到四元络合物，这表明该位置可能是钯(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-乙酸酯反应生成络合物，其中吲哚环通过3H-吲哚形式的氮与钯(II)配位，并与配位的芳香族二胺与吲哚-3相互作用。 -乙酸盐等形成加合物，其稳定常数和热力学参数表明加合物的形成主要是由于配位之间的堆积芳香族二胺和吲哚环较少。