Identification of putative peroxide intermediates of peroxidases by electronic structure and spectra calculations
Identification of putative peroxide intermediates of peroxidases by electronic structure and spectra calculations
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通过电子结构和光谱计算鉴定过氧化物酶的假定过氧化物中间体
DOI：
10.1021/ja9617247
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发表时间：
1996
影响因子：
15
通讯作者：
G. Loew
中科院分区：
文献类型：
--
作者：
D. Harris;G. Loew
用INDO/ROHF/CI量子化学方法计算了两个过氧化物中间体的电子结构和光谱。在这个氧化代谢血红素蛋白家族的酶促循环中，需要过氧化氢将铁静止状态转化为催化活性的铁基FeO化合物I。虽然过氧化物络合物已被提出作为该反应中的关键中间体，但该中间体物种太短暂，迄今为止尚未被明确表征。在H2 O2与辣根过氧化物酶C（HRP-C）的野生型和R38 L突变体反应期间在化合物I形成之前观察到的电子光谱已归因于该中间体。然而，在300 - 450 nm区域，这些光谱存在显著的质的差异，在一个中观察到“hyper-Soret”，在另一个中观察到正常Soret，与静息状态没有很大区别。在没有任何其他信息的情况下，...
The INDO/ROHF/CI quantum chemical method has been used to calculate the electronic structure and spectra of two candidate peroxide intermediates of model peroxidases. In the enzymatic cycle of this family of oxidative metabolizing heme proteins, hydrogen peroxide is required to transform the ferric resting state to the catalytically active, ferryl FeO, compound I species. While a peroxide complex has been proposed as a key intermediate in this reaction, this intermediate species is too transient to have thus far been definitively characterized. Electronic spectra observed prior to compound I formation during the reaction of H2O2 with both wild type and the R38L mutant of horseradish peroxidase C (HRP-C) have been attributed to this intermediate. There are, however, significant qualitative differences in these spectra in the 300−450-nm region, with a “hyper-Soret” observed in one and a normal Soret, not very different from the resting state, found in the other. In the absence of any additional information,...