Substrate Modification at Redox Active Copper Centers

描述（由申请人提供）：本提案中概述的研究旨在了解多巴胺β羟化酶和肽甘氨酸α羟化单加氧酶铜中心发生的基本化学反应。这两种酶都含有两个结构上分离的和光谱上不同的铜中心，并使用分子氧作为唯一的氧化剂催化烃底物的羟基化。合成模型将模仿这两个中心。将制备的一系列模型是旨在模拟金属中心的反应性质的单核铜中心，所述金属中心被提议为烃羟基化通过假定的CuII-过氧化氢中间体发生的位点。将进行研究以阐明该铜中心模拟物的底物氧化机制。双核模型将包含模拟两个铜的城市，研究与双核配合物将旨在了解如何在两个中心协同工作，以产生CuII-氢过氧物种。

DESCRIPTION (provided by applicant): The research outlined in this proposal is aimed at understanding the fundamental chemistry taking place at the copper-centers of Dopamine Beta Hydroxylase and Peptideglycine alpha Hydroxylating Monooxygenase. Both enzymes contain two structurally isolated and spectroscopically distinct copper centers and catalyze the hydroxylation of hydrocarbon substrates using dioxygen as the sole oxidant. Synthetic models will be made to mimic both of these centers. One series of models that will be prepared is a mononuctear copper center aimed at mimicking the reactive properties of the metal-center that is proposed to be the site where hydrocarbon hydroxylation takes place through a supposed CuII-hydroperoxo intermediate. Studies will be performed to elucidate the mechanism of substrate oxidation by this copper-center mimic. Dinuclear models will be made containing mimics for both copper-cites, Studies with the dinuclear complexes will be aimed at understanding how the two centers work in concert to generate the CuII-hydroperoxo species.