HELICAL AND CAVITY MOTIFS ABOUT METAL IONS

这项拟议的研究的目的是调节微环境 (二次配位球)关于金属离子以引导其 化学反应。该方法利用了分子结构原理。 已被描述为金属蛋白的活性部位。新模块 已经设计和合成了非血红素配体系统，将 阐述了金属装订袋的结构和形态 影响金属络合物的功能和物理性质。这个 配体系统可以将官能团定位到定义良好的阵列中，以 创造特定的化学微环境。此外，弱对准和弱对准 金属-配体相互作用将被用来相对定向这些阵列 结合在一起的金属离子。一旦这些金属-配体体系被表征 在结构和物理上，它们将被用来解决多高 活性氧化和自由基中间体在生物中的调节 系统，以探索氧化催化中的结构-功能关系， 了解金属离子如何控制螺旋的自组装 图案。 金属蛋白执行尚未实现的化学反应 在合成系统中。这种化学物质的多样性至少在一定程度上是由 从蛋白质调节其金属反应性的能力 通过对其微环境的调整来控制中心。因此，函数和 对生物具有重要意义的金属蛋白的功能障碍可以在 它们微环境变化的背景。这种类型的分析 有必要进行基础反应性研究，在这些研究中，单一的 可以如在此描述的那样单独地分析组件。

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.