顺式-3-氯丙烯酸脱卤酶的反应机理：一项理论研究。
Reaction mechanism of cis-3-chloroacrylic acid dehalogenase: a theoretical study.
作者信息
Sevastik Robin, Whitman Christian P, Himo Fahmi
机构信息
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.
出版信息
Biochemistry. 2009 Oct 13;48(40):9641-9. doi: 10.1021/bi900879a.
Abstract
The reaction mechanism of cis-3-chloroacrylic acid dehalogenase (cis-CaaD) is studied using the B3LYP density functional theory method. This enzyme catalyzes the hydrolytic dehalogenation of cis-3-chloroacrylic acid to yield malonate semialdehyde and HCl. The uncatalyzed reaction is first considered, and excellent agreement is found between the calculated barrier and the measured rate constant. The enzymatic reaction is then studied with an active site model consisting of 159 atoms. The results suggest an alternative mechanism for cis-CaaD catalysis and different roles for some active site residues in this mechanism.
摘要
采用B3LYP密度泛函理论方法研究了顺式-3-氯丙烯酸脱卤酶（cis-CaaD）的反应机理。该酶催化顺式-3-氯丙烯酸的水解脱卤反应，生成丙二酸半醛和HCl。首先考虑了无催化反应，计算得到的势垒与实测速率常数之间具有良好的一致性。然后用一个由159个原子组成的活性位点模型研究了酶促反应。结果表明了cis-CaaD催化的另一种机制以及该机制中一些活性位点残基的不同作用。
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