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DOI | 10.1038/s41586-019-1050-5 |
In-crystal reaction cycle of a toluene-bound diiron hydroxylase | |
Acheson, Justin F.1; Bailey, Lucas J.1; Brunold, Thomas C.2; Fox, Brian G.1 | |
2019-03-27 | |
发表期刊 | NATURE
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ISSN | 0028-0836 |
EISSN | 1476-4687 |
出版年 | 2017 |
卷号 | 544期号:7649页码:191-+ |
文章类型 | Article |
语种 | 英语 |
国家 | USA |
英文摘要 | Electrophilic aromatic substitution is one of the most important and recognizable classes of organic chemical transformation. Enzymes create the strong electrophiles that are needed for these highly energetic reactions by using O-2, electrons, and metals or other cofactors. Although the nature of the oxidants that carry out electrophilic aromatic substitution has been deduced from many approaches, it has been difficult to determine their structures. Here we show the structure of a diiron hydroxylase intermediate formed during a reaction with toluene. Density functional theory geometry optimizations of an active site model reveal that the intermediate is an arylperoxo Fe2+/Fe3+ species with delocalized aryl radical character. The structure suggests that a carboxylate ligand of the diiron centre may trigger homolytic cleavage of the O-O bond by transferring a proton from a metal-bound water. Our work provides the spatial and electronic constraints needed to propose a comprehensive mechanism for diiron enzyme arene hydroxylation that accounts for many prior experimental results. |
领域 | 地球科学 ; 气候变化 ; 资源环境 |
收录类别 | SCI-E |
WOS记录号 | WOS:000398897900029 |
WOS关键词 | XYLENE MONOOXYGENASE HYDROXYLASE ; REDUCED METHANE MONOOXYGENASE ; ACTIVE-SITE CLUSTERS ; AROMATIC HYDROXYLATION ; DEOXYHYPUSINE HYDROXYLASE ; DIOXYGEN ACTIVATION ; 4-MONOOXYGENASE ; INTERMEDIATE ; MECHANISM ; COMPLEX |
WOS类目 | Multidisciplinary Sciences |
WOS研究方向 | Science & Technology - Other Topics |
URL | 查看原文 |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/203044 |
专题 | 地球科学 资源环境科学 气候变化 |
作者单位 | 1.Univ Wisconsin, Dept Biochem, Madison, WI 53706 USA; 2.Univ Wisconsin, Dept Chem, Madison, WI 53706 USA |
推荐引用方式 GB/T 7714 | Acheson, Justin F.,Bailey, Lucas J.,Brunold, Thomas C.,et al. In-crystal reaction cycle of a toluene-bound diiron hydroxylase[J]. NATURE,2019,544(7649):191-+. |
APA | Acheson, Justin F.,Bailey, Lucas J.,Brunold, Thomas C.,&Fox, Brian G..(2019).In-crystal reaction cycle of a toluene-bound diiron hydroxylase.NATURE,544(7649),191-+. |
MLA | Acheson, Justin F.,et al."In-crystal reaction cycle of a toluene-bound diiron hydroxylase".NATURE 544.7649(2019):191-+. |
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