A Theoretical Study of the Catalytic Mechanism of Formate Dehydrogenase

Abstract

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The mechanism of formate oxidation by metal-dependent formate dehydrogenases

“…-dependent Fdhs catalyze the transfer of a hydride to the NAD ? cofactor to produce an NADH [40]. Our results indicate that this fundamental difference results from the nature of the group that accepts the hydrogen ion from the substrate, i.e., a nucleophilic selenide anion versus a NAD ?…”

“…All geometry optimizations were performed with Gaussian 03 [27], applying DFT methods and the 6-31G(d) basis set. Becke's [28] three-parameter exchange functional was used together with the functional of Lee et al [29] (B3LYP) as implemented in Gaussian [30,31].…”

“…Zero-point corrections, thermal effects, and entropic effects (T = 310.15 K, P = 1 bar) were added to all calculated energies with the 6-31G(d) basis set [26]. To estimate solvation effects of the rest of the enzyme, single-point calculations on the optimized geometries were performed with the conductor-like polarizable continuum model, as implemented in Gaussian 03 [27], with the B3LYP/6-311? ?G (3df,2pd) level.…”

Light‐Driven Highly Selective Conversion of CO2 to Formate by Electrosynthesized Enzyme/Cofactor Thin Film Electrode

“…[ 18 ] In the proposed system, NADH and FDH as electron mediator and reaction catalyst enzyme, respectively, participate in the functional fi lm on the electrode without covalent linkage. Negatively charged PDA at neutral pH as a result of deprotonation of phenolic group gives favorable for keeping NAD + within the PDA fi lm.…”

Nuclear quantum effects and kinetic isotope effects in enzyme reactions

“…A non-exhaustive list of such enzyme studies includes dihydrofolate reductase (DHFR) [41,46,56,90,102,[110][111][112][113][114], alcohol dehydrogenase (ADH) [50,83,115,116], lipoxygenase [55,59,[117][118][119], methylamine dehydrogenase [115,[120][121][122][123][124], thymidylate synthase [125,126], chorismate mutase [127][128][129], several decarboxylases [43,100,101,130], methylmalonyl-CoA mutase [131,132], alanine racemase [39,100,133], formate dehydrogenase [42,134], nitroalkane oxidase [8,108,135], morphinone reductase [116], and glyoxalase [134,136]. In the following we will focus on some examples of work performed in our group, with which ...…”