Understanding How the Rate of C-H Bond Cleavage Affects Formate Oxidation Catalysis by a Mo-Dependent Formate Dehydrogenase.

ABSTRACT: Metal-dependent formate dehydrogenases (FDHs) catalyze the reversible conversion of formate into CO₂, a proton, and two electrons. Kinetic studies of FDHs provide key insights into their mechanism of catalysis, relevant as a guide for the development of efficient electrocatalysts for formate oxidation as well as for CO₂ capture and utilization. Here, we identify and explain the kinetic isotope effect (KIE) observed for the oxidation of formate and deuterioformate by the Mo-containing FDH from Escherichia coli using three different techniques: steady-state solution kinetic assays, protein film electrochemistry (PFE), and pre-steady-state stopped-flow methods. For each technique, the Mo center of FDH is reoxidized at a different rate following formate oxidation,

SUBMITTER: Robinson WE 

PROVIDER: S-EPMC7366381 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature