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首页> 外文期刊>ACS catalysis >Effect of Chemically Distinct Substrates on the Mechanism and Reactivity of a Highly Promiscuous Metallohydrolase
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Effect of Chemically Distinct Substrates on the Mechanism and Reactivity of a Highly Promiscuous Metallohydrolase

机译：化学上不同底物对高混杂金属水解酶的机理和反应性的影响

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In this DFT study, the substrate promiscuity of the binuclear [Fe(II)-Zn(II)] core containing glycerophosphodiesterase (GpdQ) from Enterobacter aerogenes has been investigated through the hydrolysis of three chemically diverse groups of substrates: i.e., phosphomono-, phosphodi-, and phosphotriesters. The hydrolysis of these substrates is studied by comparing stepwise, concerted, and substrate-assisted mechanisms. Both the stepwise and concerted mechanisms occur with similar barriers, while the energetics for the substrate-assisted mechanism are significantly less favorable. Irrespective of the mechanism, active site residue His217 plays a critical role, in agreement with structural, kinetics, and spectroscopic data, but the transition state of the reaction depends on the identity of the substrate (dissociative for the triester paraoxon, associative for the monoester 4-nitrophenyl phosphate (NPP), and in-between for the diesters glycerol-3-phosphoethanolamine (GPE) and bis(4-nitrophenyl)phosphate (BNPP)). In good agreement with available kinetic and spectrophotometric data, the calculations highlight the preference of GpdQ for diester substrates, followed by tri- and monoesters. For substrates with two different types of scissile bonds (paraoxon and GPE) a clear preference for the bond with the stronger electron withdrawing leaving group was observed. The extensive agreement between experimental data and DFT calculations enhances the understanding of the mechanism of GpdQ-catalyzed hydrolysis and paves the way for the rational design of optimized catalysts for the hydrolysis of different types of phosphoesters.
机译：在该DFT研究中，通过三种化学多样的底物的水解研究了来自肠杆菌空气的含有甘油磷酸酯酶（GPDQ）的甘油磷酸酯酶（GPDQ）的基核[Fe（II）-Zn（II）]核的底芯：即磷膦 - ，磷酸二磷酸和磷酸二磷酸酯。通过比较逐步，齐节和衬底辅助机构来研究这些基材的水解。逐步和齐齐的机制都发生在类似的障碍物中，而基板辅助机构的能量显着不太有利。无论机制如何，活性部位残留HIS217都与结构，动力学和光谱数据一致，但反应的过渡状态取决于基材的身份（分离用于Triester嫁接，单烯烃的联想磷酸二酯（NPP），与二酯甘油-3-磷乙醇胺（GPE）和双（4-硝基苯基）磷酸盐（BNPP））的磷酸二硝基苯酯。与可用动力学和分光光度法的良好一致性，计算突出了GPDQ对二酯基材的偏好，其次是三烯和单烯烃。对于具有两种不同类型的股键（律毒素和GPE）的底物，观察到与较强的吸电子粘合的粘合偏好。实验数据和DFT计算之间的广泛协议增强了对GPDQ催化水解机制的理解，并为不同类型磷酸酯的水解的优化催化剂的合理设计铺平了途径。

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