O2 Reduction to H2O by the multicopper oxidases

O2 Reduction to H2O by the multicopper oxidases
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DOI:
10.1039/b800799c
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发表时间:
2008-01-01
影响因子:
4
通讯作者:
Yoon, Jungjoo
Yoon, Jungjoo
中科院分区:
化学2区
文献类型:
--
作者:
Solomon, Edward I.;Augustine, Anthony J.;Yoon, Jungjoo

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在自然界中,O(2)到H(2)O的四电子还原是由细胞色素c氧化酶(CcO)和多铜氧化酶(MCOs)完成的。在前者中,细胞色素c提供电子用于泵送质子以产生ATP合成的梯度,而在MCO中,功能是氧化底物,无论是有机离子还是金属离子。在MCO中,O(2)的还原是在三核Cu簇(TNC)上进行的。氧中间体已被捕获,表现出独特的光谱特征,反映了新的几何和电子结构。这些中间体都有完整的和裂解的O-O键,允许还原裂解的O-O键进行详细的研究实验和计算。这些研究表明,TNC的拓扑结构提供了独特的几何和电子结构,特别适合在自然界中进行这一关键反应。
In nature the four electron reduction of O(2) to H(2)O is carried out by Cytochrome c oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O(2) is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in nature.