HYDROGEN BONDING CAVITY MOTIFS ABOUT METAL IONS

关于金属离子的氢键腔模式

基本信息

批准号：
6179732
负责人：
Andrew S. Borovik
金额：
$ 17.08万
依托单位：
UNIVERSITY OF KANSAS LAWRENCE
依托单位国家：
美国
项目类别：
财政年份：
1994
资助国家：
美国
起止时间：
1994-04-01 至 2003-03-31
项目状态：
已结题

项目摘要

The aim of this proposed research is to regulate the microenvironments (secondary coordination spheres) about metal ions to direct their chemistry. The approach utilizes the principles of molecular architecture that have been found in the active sites of metalloproteins. New modular tripodal ligands have been developed that create cavities around vacant binding sites in coordinatively unsaturated metal complexes. These ligands can position functional groups within the cavities to create specific chemical microenvironments about metal ions. We will investigate how cavity structure influences the functional and physical properties of metal complexes. Particular emphasis will be placed on studying the effects of the hydrogen bonds and the size of the cavities in directing chemistry at metal centers. Once these cavity-containing metal complexes are characterized both structurally and physically, they will be used to address how non-heme metalloproteins regulate dioxygen binding and activation, and utilize highly oxidized or radical intermediates in catalysis. Long term goals of this research include developing structure-function relationships in metal-assisted oxidative biomimetic catalysis. The systems outlined in this proposal offer an approach to designing new biomimetic metal complexes that have H-bonding cavities. The control of the molecular components that define the cavity structure permits the development of systems whose activity can be tailored to a particular reaction and class of substrates. The ability to fine-tune the molecular design of the external ligand binding site by varying the size and H-bonding groups is beneficial for regulating the microenvironment about active species. This allows for the systematic study of structure-function relationships that can lead to a fundamental understanding of metallobiochemical processes.

这项拟议的研究的目的是调节有关金属离子的微环境（次要配位球），以指导其化学。该方法利用在金属蛋白的活性位点发现的分子结构原理。已经开发了新的模块化三座配体，该配体在协调不饱和金属络合物中的空置结合位点周围产生了空腔。这些配体可以将功能组定位在空腔中，以创建有关金属离子的特定化学微环境。我们将研究腔结构如何影响金属复合物的功能和物理性质。特别重点将放在研究氢键和腔体大小指导金属中心的作用上。一旦这些含腔的金属络合物在结构和物理上都被表征，它们将被用来解决非血红素金属蛋白如何调节二恶英的结合和激活，并利用催化中的高度氧化或自由基中间体。这项研究的长期目标包括在金属辅助氧化仿生催化中发展结构功能关系。该提案中概述的系统提供了一种设计具有H键空腔的新仿生金属配合物的方法。定义腔结构的分子成分的控制允许其活性可以根据特定反应和底物等级定制的系统的发展。通过改变大小和H键组来微调外配体结合位点的分子设计的能力对调节有关活性物种的微环境有益。这允许对结构功能关系的系统研究，这可以导致对金属生物化学过程的基本理解。