TETHERED TRANSITION METAL PROBES FOR METALLOENZYMES

本项目的目标是利用细胞色素c过氧化物酶（CcP）的工程形式来引入快速生成氧化还原中间体的人工电子途径。本提案的第一部分将评估通过碳氢链连接到ru光敏剂的大范围底物与CcP空腔突变体结合的能力。这项工作将扩展到包括各种长度的碳氢化合物系索。第二部分涉及短肽链的合成，作为配体和ru光敏剂之间的连接。这有望增加系绳蛋白相互作用的范围。在第三部分，电子转移性质将被研究。Ru-光敏剂的光激发将导致电子从Ru中心通过碳氢化合物或肽链从空腔对接的配体转移到血红素铁。对传输速率的分析将允许研究电子传输的物理途径，作为电子耦合和干预介质的函数，从而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.