Studies on Bioactive Metal Complex in Dynamic Processes

动态过程中生物活性金属配合物的研究

基本信息

批准号：
09045032
负责人：
YAMAUCHI Osamu
金额：
$ 2.94万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

Noncovalent interactions are important for molecular recognition, specificity of reactions, and biological activity. We have been studying ternary Cu (II) complex formation involving various weak interactions between two functional groups of coordinated ligands such as aromatic rings and charged groups.With a view to constructing molecular adducts and elucidating the factor affecting self-assembling, we studied weak intermolecular interactions between a small biomolecule as a guest and a planar Pt (L) (A) complex involving a coordinated aromatic ring (L) and a basic amino acid (A) by the thermodynamic, X-ray diffraction, and spectroscopic methods. The features of the adduct through aromatic ring stacking in a system involving a metal ion, such as Pt (phen) (en) ・・・indoleacetate, are (1) unusually high stability constants due to dominant -ΔH゜and (2) appearance of the charge transfer band and (3) Pt-195 NMR downfield shifts consistently proportional to the -ΔH゜ values. Some additional polar interactions have been indicated in the systems containing [Pt (L) (A)] and nucleotide monophosphates, DNA, or aromatic carboxylates as guests by further enhancement of ΔH゜, adduct formation constant K, and Pt-195 KMR shifts. The solid state structure of [Pt (phen) (en) ・・・indoleacetate]・ClOィイD24ィエD2, [Pt (2, 2'-bipyrimidine) (glycine and L-alanine)・・・indoleacetate] revealed aromatic ring stacking and intramolecular hydrogen bonding. Pt (2, 2'-bypyrimidine) (L-arginine) ・・・indoleacetate showed hydrogen bonding involving arginine guanidinium group. These findings clearly show that the metal ion regulates the interaction with the coordinating ligand to stabilizes the intermolecular interactions. Calorimetric results revealed these noncovalent interactions and were more informative.

非共价相互作用对于分子识别，反应的特异性和生物学活性很重要。我们一直在研究三元铜（II）复合物的形成涉及两个配位配体的功能组之间的各种弱相互作用，例如芳香环和充电组。与我们研究了构建分子加合物的观点，并阐明了我们影响自组装的因素，我们研究了我们在平面和平面群体之间的弱分子之间的弱分子互动（（L）和碱性氨基酸（A）通过热力学，X射线衍射和光谱方法。通过涉及金属离子的系统中加合的特征，例如PT（phn）（eN）・・・凹酸，是（1）由于电荷传递带的显性-ΔH゜和（2）出现电荷传递带和（3）PT -195 NMR下场的稳定性异常高的稳定性常数是 - 稳定性。通过进一步增强ΔH゜，添加剂形成常数k和pt-195 kmr移位，在包含[PT（L）（a）]和核氧化的单磷酸盐，DNA或芳族羧酸盐的系统中已指出了一些其他极性相互作用。 [pt（phen）（en）...乳化酸性]的固态结构cloII D24IE D2，[Pt（2，2'-二吡啶胺）（甘氨酸和L-丙氨酸）・・吲哚酸乳酸盐】显示了芳族环的堆叠和内部杂菌内氢粘合剂。 pt（2，2'-二甲酰胺）・・吲哚乙酸乳化型含有精氨酸鸟嘌呤组的氢键。这些发现清楚地表明，金属离子调节与配位配体的相互作用以稳定分子间相互作用。量热的结果揭示了这些非共价相互作用，并且更具信息性。