OXIDATION REACTIVITY IN SMALL METAL COMPLEXES

该子项目是利用NIH/NCRR资助的中心赠款提供的资源的许多研究子项目之一。子项目和研究者（PI）可能从另一个NIH来源获得主要资金，因此可以在其他CRISP条目中表示。所列机构为中心，不一定是研究者所在机构。运动的独特的生物催化反应性的小合成分子，而一个艰巨的挑战，是一个非常有趣的和翔实的奋进，提供关键的见解到本地的反应性。我们的研究的广泛和长期的目标是阐明在生物单核，双核和三核Cu-网站和随后的表征其氧化反应性的Cu-双氧物种的结构和电子性质。进一步的研究是针对了解单核铁和锰的酶，氧化有机底物。该方法是合成的类似物的方法的活性位点的金属生物分子，从而低分子量的复合物的合成和检查在小分子水平的细节，以揭示从蛋白质基质的影响解偶联的金属复合物的固有特性。我们的前提是，生物中间体的形成和随后的反应性应该是可重现的小的合成复合物，如果适当的连接环境工程，如果有害的双分子反应的活性中间体被避免。最终目标是建立光谱一致的功能模型，以便在小分子水平上详细研究所提出的生物学机制的特定方面。

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.