HELICAL AND CAVITY MOTIFS ABOUT METAL IONS

这项研究的目的是调节微环境 （二次配位球）围绕金属离子， 化学.该方法利用分子结构的原理 已经被描述为金属蛋白的活性位点。新的模块化 已经设计和合成了非血红素配体系统， 解决金属装订口袋的结构和形态 影响金属络合物的功能和物理性质。的 配体系统可以将官能团定位到明确的阵列中， 创造特定的化学微环境。此外，弱内配体和 金属-配体相互作用将被用来使这些阵列相对于 结合的金属离子。一旦这些金属配体系统被表征 在结构和物理上，它们将被用来解决如何高度 活性氧化和自由基中间体在生物学中受到调节， 系统，以探测氧化催化中的结构-功能关系， 并了解金属离子如何控制螺旋的自组装， 图案 金属蛋白进行化学反应， 在合成系统中。这种化学多功能性至少部分地遵循 从蛋白质调节金属反应性的能力 通过调整他们的微环境。因此，函数和 生物学上重要的金属蛋白的功能障碍可以理解为 微观环境的变化。这种类型的分析 需要进行基本的反应性研究，其中单一的 可以如本文所述单独分析组分。

The aim of this proposed research is to modulate the microenvironments (secondary coordination spheres) about metal ions to direct their chemistry. The approach utilizes the principles of molecular architecture that have been delineated for active sites of metalloproteins. New modular non-heme ligand systems have been designed and synthesized that will address how the structure and morphology of metal binding pockets influence the functional and physical properties of metal complexes. The ligand systems can position functional groups into well-defined arrays to create specific chemical microenvironments. Moreover, weak intraligand and metal-ligand interactions will be employed to orient these arrays relative to the bound metal ions. Once these metal-ligand systems are characterized structurally and physically, they will be used to address how highly reactive oxidized and radical intermediates are regulated in biological systems, to probe structure-function relationships in oxidative catalysis, and understand how metal ions can control the self assembly of helical motifs. Metalloproteins perform chemical reactions that have not yet been achieved in synthetic systems. This chemical versatility follows at least in part from the ability of the proteins to regulate the reactivity of their metal centers by adjustment of their microenvironments. Thus the function and disfunction of biologically-important metalloproteins can be understood in the context of changes in their microenvironments. This type of analysis necessitates basic reactivity studies in which the effects of single components can be analyzed individually as described herein.