Dioxygen Activation by Nonheme Diiron Enzymes: Diverse Dioxygen Adducts, High-Valent Intermediates, and Related Model Complexes.
Dioxygen Activation by Nonheme Diiron Enzymes: Diverse Dioxygen Adducts, High-Valent Intermediates, and Related Model Complexes.
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DOI：
10.1021/acs.chemrev.7b00457
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发表时间：
2018-03-14
期刊：
影响因子：
62.1
通讯作者：
Que L Jr
中科院分区：
文献类型：
--
作者：
Jasniewski AJ;Que L Jr
越来越多的金属酶通过非血红素二铁活性位点激活二氧，以影响底物氧化，其范围从甲烷的羟基化和脂肪酸的去饱和到脂肪醛的去饱和以产生烷烃以及抗生素生物合成中氨基芳烃到硝基芳烃的六电子氧化。它们的反应机制的一个共同特征是形成O2加合物，这些加合物演变成更具反应性的衍生物，如二铁（II，III）-超氧、二铁（III）-过氧、二铁（III，IV）-氧和二铁（IV）-氧物种，它们执行特定的底物氧化任务。在这篇综述中，我们调查属于这个独特的子集和底物氧化进行的机制的各种酶。我们研究的活性中间体的性质，所揭示的X射线晶体学和各种光谱方法及其相关的反应性的应用。我们还讨论了模型复合物的结构和电子性质，已被发现模仿这些酶的活性位点的突出方面。在过去25年里，我们学到了很多东西，但关键问题仍有待回答。
A growing subset of metalloenzymes activates dioxygen with nonheme diiron active sites to effect substrate oxidations that range from the hydroxylation of methane and the desaturation of fatty acids to the deformylation of fatty aldehydes to produce alkanes and the six-electron oxidation of aminoarenes to nitroarenes in the biosynthesis of antibiotics. A common feature of their reaction mechanisms is the formation of O2 adducts that evolve into more reactive derivatives such as diiron(II,III)-superoxo, diiron(III)-peroxo, diiron(III,IV)-oxo, and diiron(IV)-oxo species, which carry out particular substrate oxidation tasks. In this review, we survey the various enzymes belonging to this unique subset and the mechanisms by which substrate oxidation is carried out. We examine the nature of the reactive intermediates, as revealed by X-ray crystallography and the application of various spectroscopic methods and their associated reactivity. We also discuss the structural and electronic properties of the model complexes that have been found to mimic salient aspects of these enzyme active sites. Much has been learned in the past 25 years, but key questions remain to be answered.
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甲烷酶氧化甲醇的酶促氧化中的关键物种的结构。
影响因子：
64.8
作者：
Banerjee, Rahul;Proshlyakov, Yegor;Lipscomb, John D.;Proshlyakov, Denis A.
通讯作者：
Proshlyakov, Denis A.
影响因子：
64.8
作者：
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通讯作者：
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影响因子：
15
作者：
Beauvais, LG;Lippard, SJ
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影响因子：
15
作者：
Brazeau, BJ;Wallar, BJ;Lipscomb, JD
通讯作者：
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影响因子：
4.6
作者：
ARMSTRONG, GD;SYKES, AG
通讯作者：
SYKES, AG