A Single Enzyme Oxidative "Cascade" via a Dual-Functional Galactose Oxidase
A Single Enzyme Oxidative "Cascade" via a Dual-Functional Galactose Oxidase
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DOI：
10.1021/acscatal.8b00043
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发表时间：
2018-05-01
期刊：
影响因子：
12.9
通讯作者：
Turner, Nicholas J.
中科院分区：
文献类型：
--
作者：
Birmingham, William R.;Turner, Nicholas J.
半乳糖氧化酶（GOase）M3-5变体，以前设计用于（R）-仲醇的对映选择性氧化，现在显示催化取代的苄型和杂芳族苄型醇通过中间体醛连续四电子氧化为相应的羧酸。醛氧化已被证明发生在醛的水合（偕二醇）形式上，因此该第二氧化步骤的活性主要由取代基对芳环的影响决定。GOase用于将醇“通过氧化”成羧酸的证明代表了两种不同的铜自由基氧化酶（半乳糖氧化酶和乙二醛氧化酶）的活性融合成单个酶序列，其具有作为简化的氧化级联的潜在应用。
The galactose oxidase (GOase) M3-5 variant, previously engineered for enantioselective oxidation of (R)-secondary alcohols, is now shown to catalyze the sequential four-electron oxidation of substituted benzylic and heteroaromatic benzylic alcohols to the corresponding carboxylic acids via the intermediate aldehyde. Aldehyde oxidation has been shown to occur on the hydrated (gem-diol) form of the aldehyde, and hence the activity of this second oxidation step is primarily determined by the effects of substituents on the aromatic ring. The demonstration of GOase for "through oxidation" of alcohols to carboxylic acids represents a fusion of the activities of two distinct copper radical oxidases (galactose oxidase and glyoxal oxidase) into a single enzyme sequence with potential applications as an abbreviated oxidative cascade.