两种催化多功能铁(II)-和α-酮戊二酸依赖酶的机制阐明:羟基化以外的情况

IF 3.8 3区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Comments on Inorganic Chemistry Pub Date : 2018-07-04 DOI:10.1080/02603594.2018.1509856

Wei‐chen Chang, Pinghua Liu, Yisong Guo

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引用次数: 6

摘要

铁(II)-和α-酮戊二酸依赖(Fe/αKG)酶催化大量的反应。虽然这些酶催化的羟基化反应已经进行了详细的研究，其中铁基(FeIV=O)是一个关键的反应中间体。除羟基化作用外，其他反应的机制仍是未知的。采用生物化学、生物有机和光谱相结合的方法，研究了两种新发现的Fe/αKG酶FtmOx1(内过氧化物酶)和AsqJ(去饱和酶/环氧化酶)的反应机制，揭示了它们控制反应性的策略，即铁中心附近氧化还原/极性残基的影响、底物的电子性质以及铁基中间体的内在反应性。

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Mechanistic Elucidation of Two Catalytically Versatile Iron(II)- and α-Ketoglutarate-Dependent Enzymes: Cases Beyond Hydroxylation

Iron(II)- and α-ketoglutarate-dependent (Fe/αKG) enzymes catalyze a large array of reactions. Although hydroxylation reaction catalyzed by these enzymes has been investigated in great details, involving the ferryl (FeIV=O) as a key reactive intermediate. The mechanisms of reactions other than hydroxylation are still largely unknown. By using a combined biochemical, bio-organic, and spectroscopic approach, we have studied the mechanisms of two newly discovered Fe/αKG enzymes, FtmOx1 (endoperoxidase) and AsqJ (desaturase/epoxidase), revealing their strategies in controlling reactivity, namely the effect of redox/polar residues near the iron center, the electronic properties of the substrate, and the intrinsic reactivity of the ferryl intermediate.

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来源期刊

Comments on Inorganic Chemistry 化学-无机化学与核化学

CiteScore

9.00

自引率

1.90%

发文量

审稿时长

>12 weeks

期刊介绍： Comments on Inorganic Chemistry is intended as a vehicle for authoritatively written critical discussions of inorganic chemistry research. We publish focused articles of any length that critique or comment upon new concepts, or which introduce new interpretations or developments of long-standing concepts. “Comments” may contain critical discussions of previously published work, or original research that critiques existing concepts or introduces novel concepts. Through the medium of “comments,” the Editors encourage authors in any area of inorganic chemistry - synthesis, structure, spectroscopy, kinetics and mechanisms, theory - to write about their interests in a manner that is both personal and pedagogical. Comments is an excellent platform for younger inorganic chemists whose research is not yet widely known to describe their work, and add to the spectrum of Comments’ author profiles, which includes many well-established inorganic chemists.