HYDROGEN BONDING CAVITY MOTIFS ABOUT METAL IONS

关于金属离子的氢键腔模式

• 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
• 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
• 来源: https://reporter.nih.gov/project-details/6179732
• 关键词: X ray crystallography; active sites; binding sites; catalyst; chemical models; coulometry; free radical oxygen; hydrogen bond; infrared spectrometry; interferometry; intermolecular interaction; ions; ligands; metal complex; metalloproteins; molecular assembly /self assembly; nuclear magnetic resonance spectroscopy; protein structure; protein structure function

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.

这项研究的目的是调节金属离子周围的微环境（次级配位球），以指导它们的化学反应。 该方法利用了在金属蛋白活性位点中发现的分子结构原理。 已经开发了新的模块化三脚架配体，其在配位不饱和金属络合物中的空结合位点周围产生空腔。 这些配体可以将官能团定位在空腔内，以产生关于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配合物的功能和物理性质。 特别强调的是将放在研究的影响，氢键和空腔的大小，在金属中心的化学指导。一旦这些含有空腔的金属络合物的结构和物理特征，它们将被用来解决非血红素金属蛋白如何调节双氧结合和激活，并利用高度氧化或自由基催化中间体。 本研究的长期目标包括开发金属辅助氧化仿生催化的结构-功能关系。该提案中概述的系统提供了一种设计具有氢键空腔的新型仿生金属络合物的方法。 控制定义腔结构的分子组分允许开发其活性可以针对特定反应和底物类别定制的系统。 通过改变大小和H-键合基团来微调外部配体结合位点的分子设计的能力有利于调节活性物质周围的微环境。 这使得结构-功能关系的系统研究，可以导致金属生物化学过程的基本理解。