化学
环加成
分叉
选择性
酶
分子力学
分子动力学
计算化学
酶催化
催化作用
飞秒
化学物理
非线性系统
有机化学
量子力学
物理
激光器
作者
Xin Wang,Chun Zhang,Yaoyukun Jiang,Wen Wang,Yuan Zhou,Yu Chen,Bo Zhang,Ren Xiang Tan,Hui Ge,Zhongyue Yang,Yong Liang
摘要
The enzyme NgnD catalyzes an ambimodal cycloaddition that bifurcates to [6+4]- and [4+2]-adducts. Both products have been isolated in experiments, but it remains unknown how enzyme and water influence the bifurcation selectivity at the femtosecond time scale. Here, we study the impact of water and enzyme on the post-transition state bifurcation of NgnD-catalyzed [6+4]/[4+2] cycloaddition by integrating quantum mechanics/molecular mechanics quasiclassical dynamics simulations and biochemical assays. The ratio of [6+4]/[4+2] products significantly differs in the gas phase, water, and enzyme. Biochemical assays were employed to validate computational predictions. The study informs how water and enzyme affect the bifurcation selectivity through perturbation of the reaction dynamics in the femtosecond time scale, revealing the fundamental roles of condensed media in dynamically controlling the chemical selectivity for biosynthetic reactions.
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