Computational Evidence for the Enzymatic Transformation of 2-Hydroxypropylphosphonate to Methylphosphonate
Computational Evidence for the Enzymatic Transformation of 2-Hydroxypropylphosphonate to Methylphosphonate
复制标题
2-羟丙基膦酸酯酶促转化为甲基膦酸酯的计算证据
DOI：
10.1021/acsearthspacechem.8b00070
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发表时间：
2018
影响因子：
3.4
通讯作者：
Wang W.
中科院分区：
文献类型：
--
作者：
Li Y.;Wang X.;Zhang R.;Wang J.;Yang Z.;Du L.;Tang X.;Zhang Q.;Wang W.
了解海洋中温室气体甲烷的来源具有重要的环境意义，特别是对于全球气候变化和地球表面系统内的碳流动。2-羟乙基膦酸酯双加氧酶（HEPD）突变体E176 H催化2-羟丙基膦酸酯（2-HEP）转化为甲基膦酸酯（MPn），后者在海洋微生物C-P裂解酶的作用下可转化为甲烷。在这里，HEPD E176 H催化的2-HEP转化为MPn在分子水平上使用量子力学/分子力学方法进行了研究。结果表明，2-HEP转化为MPn的过程包括5个基本步骤：H的夺取、O-O键的断裂、H的转移、C-C键的断裂和MPn的形成。氢提取被认为是速率决定步骤，能量势垒为17.8千卡/摩尔，这是合理的根据实验确定的r。
Understanding the origins of greenhouse gas methane in the ocean is of great environmental importance, especially for global climate change and the flow of carbon within the earth surface system. A mutant (E176H) of 2-hydroxyethylphosphonate dioxygenase (HEPD) has been reported to catalyze the transformation of 2-hydroxypropylphosphonate (2-HEP) to methylphosphonate (MPn), a compound that can be easily transformed to methane by C–P lyase in a marine microbe. Here, the HEPD E176H-catalyzed transformation of 2-HEP to MPn was investigated at the molecular level using the quantum mechanics/molecular mechanics method. The results evidenced the feasibility of the transformation of 2-HEP to MPn and highlighted that the transformation contains five elementary steps: H abstraction, O–O bond cleavage, H transfer, C–C bond cleavage, and MPn formation. H abstraction was found to be the rate-determining step with an energy barrier of 17.8 kcal/mol, which is in reasonable accordance with the experimentally determined r...