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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Mechanisms for Flavin-Mediated Oxidation: Hydride or Hydrogen-Atom Transfer?

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Author(s):
Curtolo, Felipe [1] ; Arantes, Guilherme M. [1]
Total Authors: 2
Affiliation:
[1] Univ Sao Paulo, Inst Quim, Dept Biochem, BR-05508900 Sao Paulo, SP - Brazil
Total Affiliations: 1
Document type: Journal article
Source: JOURNAL OF CHEMICAL INFORMATION AND MODELING; v. 60, n. 12, p. 6282-6287, DEC 28 2020.
Web of Science Citations: 0
Abstract

Flavins are versatile biological cofactors which catalyze proton-coupled electron transfers (PCET) with varying number and coupling of electrons. Flavin-mediated oxidations of nicotinamide adenine dinucleotide (NADH) and of succinate, initial redox reactions in cellular respiration, were examined here with multiconfigurational quantum chemical calculations and a simple analysis of the wave function proposed to quantify electron transfer along the proton reaction coordinate. The mechanism of NADH oxidation is a prototypical hydride transfer, with two electrons moving concerted with the proton to the same acceptor group. However, succinate oxidation depends on the elimination step and can proceed through the transfer of a hydride or hydrogen atom, with proton and electrons moving to different groups in both cases. These results help to determine the mechanism of fundamental but still debated biochemical reactions and illustrate a new diagnostic tool for electron transfer that can be useful to characterize a broad class of PCET processes. (AU)

FAPESP's process: 16/23525-0 - Computer simulations of the reaction mechanisms in quinol:fumarate reductases
Grantee:Felipe Curtolo
Support type: Scholarships in Brazil - Master
FAPESP's process: 16/24096-5 - Computer simulation of metalloenzymes and of flexible proteins
Grantee:Guilherme Menegon Arantes
Support type: Regular Research Grants
FAPESP's process: 17/26109-0 - Computer simulations of reactivity and electron transfer in respiratory complex II
Grantee:Felipe Curtolo
Support type: Scholarships in Brazil - Doctorate (Direct)
FAPESP's process: 19/21856-7 - Computational molecular bioenergetics
Grantee:Guilherme Menegon Arantes
Support type: Regular Research Grants