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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活性都很重要。为了构建分子加合物和阐明影响自组装的因素，我们用热力学、X射线衍射和光谱等方法研究了以生物小分子为客体的铂(L)(A)配合物与含配位芳环(L)和碱性氨基酸(A)的平面配合物之间的弱相互作用。在含金属离子的体系中，通过芳环堆积形成的加合物的特征是：(1)由于主要的-ΔH゜而具有高的稳定常数；(2)出现电荷转移带；(3)铂-195核磁共振的下场位移与-ΔH゜值成正比。通过ΔH゜、加合物形成常数K和铂-195KMR位移的进一步增强，在以[铂(L)(A)]和核苷酸单磷酸、脱氧核糖核酸或芳香族羧酸盐为客体的体系中发现了一些额外的极性相互作用。[Pt(Phen)(En)···吲哚乙酸酯]·ClOィイD24ィエD2，[Pt(2，2‘-联嘧啶)(甘氨酸和L丙氨酸)···吲哚乙酸酯]的固态结构显示出芳环堆积和分子内氢键。PT(2，2‘-联嘧啶)(L-精氨酸)···吲哚乙酸酯与精氨酸基团形成氢键。这些结果清楚地表明，金属离子调节与配位配体的相互作用，以稳定分子间的相互作用。量热结果揭示了这些非共价相互作用，并提供了更多的信息。