Influence of Water and Enzyme on the Post-Transition State Bifurcation of NgnD-Catalyzed Ambimodal [6+4]/[4+2] Cycloaddition,Journal of the American Chemical Society

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Influence of Water and Enzyme on the Post-Transition State Bifurcation of NgnD-Catalyzed Ambimodal [6+4]/[4+2] Cycloaddition
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-12-01 , DOI: 10.1021/jacs.1c10760
Xin Wang _{1,

2} , Chun Zhang ₃ , Yaoyukun Jiang ₄ , Wen Wang ₅ , Yuan Zhou ₂ , Yu Chen ₁ , Bo Zhang ₅ , Ren Xiang Tan ₅ , Hui Ming Ge ₅ , Zhongyue J Yang _{4,

6,

7,

8} , Yong Liang ₁

Affiliation

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.

中文翻译：

水和酶对 NgnD 催化双峰 [6+4]/[4+2] 环加成后过渡态分岔的影响

NgnD 酶催化双峰环加成反应，该环加成反应分为 [6+4]- 和 [4+2]- 加合物。这两种产品都已在实验中分离出来，但酶和水如何影响飞秒时间尺度的分叉选择性仍然未知。在这里，我们通过整合量子力学/分子力学准经典动力学模拟和生化分析，研究了水和酶对 NgnD 催化的 [6+4]/[4+2] 环加成后过渡态分岔的影响。[6+4]/[4+2]产物的比例在气相、水和酶中显着不同。生化测定用于验证计算预测。该研究揭示了水和酶如何通过扰动飞秒时间尺度的反应动力学来影响分叉选择性，

更新日期：2021-12-15

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