Aix-Marseille Univ, CNRS, Centrale Marseille, iSm2 UMR CMRS 7313, Aix-Marseille Université, Pôle de l'Etoile Avenue Escadrille Normandie Niemen, 13397, Marseille, France.
Biocatalysis and Bioprocessing Group, Department of Biological and Chemical Engineering, Aarhus University, Gustav Wieds Vej 10, Aarhus, 8000 Aarhus C, Denmark.
Chembiochem. 2022 Aug 3;23(15):e202200293. doi: 10.1002/cbic.202200293. Epub 2022 Jun 16.
Temperature is a crucial parameter for biological and chemical processes. Its effect on enzymatically catalysed reactions has been known for decades, and stereo- and enantiopreference are often temperature-dependent. For the first time, we present the temperature effect on the Baeyer-Villiger oxidation of rac-bicyclo[3.2.0]hept-2-en-6-one by the type II Bayer-Villiger monooxygenase, 2,5-DKCMO. In the absence of a reductase and driven by the hydride-donation of a synthetic nicotinamide analogue, the clear trend for a decreasing enantioselectivity at higher temperatures was observed. "Traditional" approaches such as the determination of the enantiomeric ratio (E) appeared unsuitable due to the complexity of the system. To quantify the trend, we chose to use the 'Shape Language Modelling' (SLM), a tool that allows the reaction to be described at all points in a shape prescriptive manner. Thus, without knowing the equation of the reaction, the substrate ee can be estimated that at any conversion.
温度是生物和化学过程的关键参数。几十年来，人们已经知道温度对酶催化反应的影响，并且立体和对映选择性通常是温度依赖性的。我们首次研究了在没有还原酶的情况下，由 II 型拜耳-维利格单加氧酶 2,5-DKCMO 催化 rac-双环[3.2.0]庚-2-烯-6-酮的 Baeyer-Villiger 氧化反应的温度效应。在合成烟酰胺类似物供氢的驱动下，观察到随着温度的升高，对映选择性呈下降趋势。由于系统的复杂性，“传统”方法，如对映体比（E）的测定似乎不合适。为了量化这种趋势，我们选择使用“形状语言建模”（SLM），这是一种允许以形状规定的方式描述反应在所有点的工具。因此，无需知道反应的方程，就可以估计任何转化率下的底物 ee。
