Low potential enzymatic hydride transfer via highly cooperative and inversely functionalized flavin cofactors.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
06 05 2019
06 05 2019
Historique:
received:
25
01
2019
accepted:
12
04
2019
entrez:
8
5
2019
pubmed:
8
5
2019
medline:
14
6
2019
Statut:
epublish
Résumé
Hydride transfers play a crucial role in a multitude of biological redox reactions and are mediated by flavin, deazaflavin or nicotinamide adenine dinucleotide cofactors at standard redox potentials ranging from 0 to -340 mV. 2-Naphthoyl-CoA reductase, a key enzyme of oxygen-independent bacterial naphthalene degradation, uses a low-potential one-electron donor for the two-electron dearomatization of its substrate below the redox limit of known biological hydride transfer processes at E°' = -493 mV. Here we demonstrate by X-ray structural analyses, QM/MM computational studies, and multiple spectroscopy/activity based titrations that highly cooperative electron transfer (n = 3) from a low-potential one-electron (FAD) to a two-electron (FMN) transferring flavin cofactor is the key to overcome the resonance stabilized aromatic system by hydride transfer in a highly hydrophobic pocket. The results evidence how the protein environment inversely functionalizes two flavins to switch from low-potential one-electron to hydride transfer at the thermodynamic limit of flavin redox chemistry.
Identifiants
pubmed: 31061390
doi: 10.1038/s41467-019-10078-3
pii: 10.1038/s41467-019-10078-3
pmc: PMC6502838
doi:
Substances chimiques
Bacterial Proteins
0
Coenzymes
0
Flavins
0
Naphthalenes
0
Recombinant Proteins
0
naphthalene
2166IN72UN
Oxidoreductases
EC 1.-
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
2074Subventions
Organisme : Deutsche Forschungsgemeinschaft (German Research Foundation)
ID : RTG 1976
Pays : International
Organisme : Deutsche Forschungsgemeinschaft (German Research Foundation)
ID : SPP 1927
Pays : International
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