BINUCLEATING TETRAPYRROLE MACROCYCLE:OXYGENASE CHEMISTRY

两个活性中心的结构杂化 突出的生物氧活化催化剂：双核 能力(就像在许多铜蛋白中一样)，以及一个四氢吡咯酸 骨架(如在血红素铁蛋白中)，被认为是一种加氧酶 模仿。在进化过程中，两个系统，亚铁血红素 铁和铜蛋白，一直与 在功能方面；铜和血红素铁位置都是 例如，已知同时存在于细胞色素氧化酶中。 因此，对这些平行关系的综合影响进行了考察 相互交织的系统是一个令人兴奋的更好的前景 了解过去和潜在未来的运作方式 进化过程。重点将放在电子和 吡咯和双核组合的结构意义 环系对加氧酶活性的影响。将检查的系统将 包括金属离子铜、钴、铁和Ru 烷烃和烯烃底物。将进行的具体研究 将承担的工作包括X射线晶体结构 活性催化剂和中间物种的测定， 金属离子络合物的电化学和磁学研究 和氧气摄取量的测量与隔离 以及含氧物种的特征。

A structural hybrid melding aspects of the active sites of two prominent biological oxygen activation catalysts: binuclear capabilities (as in many cuproproteins), and a tetraphyrrolic framework (as in heme iron proteins), is proposed as an oxygenase mimic. During the evolutionary process the two systems, heme iron and copper proteins, have been closely associated with respect to function; and both copper and heme iron sites are known to occur together in cytochrome oxidase, for example. Thus an examination of the combined influence of these parallel and intertwined systems is an exciting prospect for better understanding the workings of past and potentially future evolutionary processes. Focus will be on the electronic and structural implications of the combined pyrrolic and binuclear ring system on oxygenase activity. Systems to be examined will include the metal ions copper, cobalt, iron, and ruthenium with alkane and olefin substrates. The specific studies to be undertaken will include X-ray crystallographic structural determinations of active catalysts and intermediate species, electrochemical and magnetic studies of the metal ion complexes, and oxygen uptake measurements in conjunction with the isolation and characterization of oxygenated species.