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

为了获得有关生物系统中金属复合物的基本信息，我们研究了生物分子离子相互作用的模式和所得复合物的结构。1。芳族环堆叠和配位配体之间的静电相互作用。含有组胺和苯丙氨酸或酪氨酸的三元铜（II）络合物的X射线晶体结构分析揭示了协调的咪唑和氨基酸的侧链芳香环之间的芳环堆叠。在未协调的吲哚和铜（II）1,10-苯磺烷氨基烷之间也检测到了芳环堆叠。分子内静电配体配体在三元铜（II）的配体中具有相对电荷侧链的配体的复合物（II）络合物，根据羧酸盐组和来自两个邻接分子组之间的固体状态以固体状态建立的分子间相互作用，在溶液中得出了溶液中的复合物的结论。坐标…铜（II） - 宾蛋白复合物的更多国家结构和特性。叶酸是一种翼龙辅助因子，已发现与铜（II）-2,2'-双吡啶反应，得出含有2,2'-二吡啶和翼龙-6-羧酸盐的三元络合物，作为Cu（ii） - 催化的氧化物的氧化物侧链链链链链链的链链链的链链链的链酸。 X射线分析揭示的复合物的结构表明，翼龙环通过n（5）原子与铜（II）坐标，其环垂直于配位平面。水分子占据等边的位置，发现咪唑很容易移动以产生第四纪络合物。这表明该位置可以是底物结合位点3。钯（II） - 吲哚和铂（II）复合物插座相互作用。四氯丙酸酯（II）与烷基丁物和吲哚-3-乙酸盐反应，使吲哚环坐标通过其3H-吲哚形式的氮与钯（II）产生复合物。与吲哚 - 3-乙酸酯等相互作用的铂（II）复合物形成加合物，其稳定性常数和热力学参数表明，加合物的形成主要是由于协同的芳族二氨基二胺和吲哚环之间的堆叠。较少的