TETHERED TRANSITION METAL PROBES FOR METALLOENZYMES

该项目的目标是利用酶细胞色素c过氧化物酶（CcP）的工程形式，引入人工电子途径快速生成氧化还原中间体。本提案的第一部分将评估通过烃系链与Ru-光敏剂连接的大范围底物与CcP的空腔突变体结合的能力。 这项工作将扩大到包括各种长度的碳氢化合物系链。 第二部分涉及短肽系链的合成作为配体和Ru-光敏剂之间的连接。 预计这将增加系链-蛋白质相互作用的范围。 在第三部分中，将研究电子转移性质。 Ru-光敏剂的光激发将导致电子经由烃或肽系链通过腔对接配体从Ru中心转移到血红素铁。 转移速率的分析将允许调查的物理路径的电子转移作为电子耦合和介入介质的函数，以允许进一步优化系留光敏剂。

The goal of this project is to utilize engineered forms of the enzyme cytochrome c peroxidase (CcP) to introduce an artificial electron pathway for rapid generation of redox intermediates. Part I of this proposal will evaluate the ability of a large range of substrates linked to Ru-photosensitizers by hydrocarbon tethers to bind to cavity mutants of CcP. This work will be expanded to include hydrocarbon tethers of various lengths. Part II involves the synthesis of short peptide tethers as linkages between the ligands and Ru-photosensitizer. This is expected to increase the range of tether-protein interactions. In Part III, electron transfer properties will be investigated. Photo- excitation of the Ru-photosensitizer will result in electron transfer from the Ru center to the heme iron through the cavity- docked ligands via the hydrocarbon or peptide tethers. Analysis of transfer rates will allow the investigation of the physical pathway of electron transfer as a function of electronic coupling and intervening medium to allow further optimization of tethered photosensitizers.