OXIDATION REACTIVITY IN SMALL METAL COMPLEXES

这个子项目是利用由NIH/NCRR资助的中心拨款提供的资源的许多研究子项目之一。子项目和调查员(PI)可能从另一个NIH来源获得了主要资金，因此可能会出现在其他CRISE条目中。列出的机构是针对中心的，而不一定是针对调查员的机构。将独特的生物催化反应性转移到合成小分子上，虽然是一项艰巨的挑战，但却是一项极其有趣和信息丰富的努力，为了解天然的反应性提供了关键的见解。我们研究的长期目标是阐明生物单核、双核和三核铜中心中形成的铜氧物种的结构和电子性质，并随后表征它们的氧化反应活性。更多的研究旨在了解含有氧化有机底物的单核铁和锰的酶。这种方法是对金属生物分子活性中心的合成模拟方法，通过合成低分子络合物并在小分子细节水平上进行检测，以揭示不受蛋白质基质影响的金属络合物的内在性质。我们的前提是，如果设计了合适的连接环境，如果避免了有害的双分子反应，生物中间体的形成和随后的反应活性应该可以在小的合成络合物中重现。创建光谱上一致的功能模型是最终目标，这样就可以在小分子细节水平上研究所提出的生物机制的具体方面。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. Movement of unique biological catalytic reactivity to small synthetic molecules, while a formidable challenge, is an extremely intriguing and informative endeavor providing critical insights into the native reactivity. The broad and long-term objective of our research is elucidation of the structural and electronic properties of Cu-dioxygen species formed in biological mononuclear, binuclear and trinuclear Cu-sites and subsequent characterization of their oxidative reactivity. Additional studies are directed to understand the mononuclear iron and manganese containing enzymes that oxidize organic substrates. The methodology is that of the synthetic analog approach to the active sites of metallobiomolecules, whereby low molecular weight complexes are synthesized and examined at a small molecule level of detail to reveal intrinsic properties of the metal complexes uncoupled from the influences of the protein matrix. Our premise is that the formation and subsequent reactivity of biological intermediates should be reproducible in small synthetic complexes if appropriate ligation environments are engineered, and if deleterious bimolecular reactions of the reactive intermediates are avoided. Creation of spectroscopically congruent, functional models is the ultimate goal so that specific aspects of proposed biological mechanisms may be investigated at a small molecule level of detail.