Ultrafast photooxidation of protein-bound anionic flavin radicals.
Anions
Catalytic Domain
/ physiology
Dinitrocresols
/ chemistry
Electron Transport
/ physiology
Flavin-Adenine Dinucleotide
/ metabolism
Flavins
/ metabolism
Flavoproteins
/ chemistry
Kinetics
Light
Models, Molecular
Molecular Dynamics Simulation
Oxidation-Reduction
Oxidoreductases
/ metabolism
Spectrophotometry
/ methods
electron transfer
flavoproteins
molecular modeling
ultrafast spectroscopy
Journal
Proceedings of the National Academy of Sciences of the United States of America
ISSN: 1091-6490
Titre abrégé: Proc Natl Acad Sci U S A
Pays: United States
ID NLM: 7505876
Informations de publication
Date de publication:
22 02 2022
22 02 2022
Historique:
accepted:
13
01
2022
entrez:
19
2
2022
pubmed:
20
2
2022
medline:
15
3
2022
Statut:
ppublish
Résumé
The photophysical properties of anionic semireduced flavin radicals are largely unknown despite their importance in numerous biochemical reactions. Here, we studied the photoproducts of these intrinsically unstable species in five different flavoprotein oxidases where they can be stabilized, including the well-characterized glucose oxidase. Using ultrafast absorption and fluorescence spectroscopy, we unexpectedly found that photoexcitation systematically results in the oxidation of protein-bound anionic flavin radicals on a time scale of less than ∼100 fs. The thus generated photoproducts decay back in the remarkably narrow 10- to 20-ps time range. Based on molecular dynamics and quantum mechanics computations, positively charged active-site histidine and arginine residues are proposed to be the electron acceptor candidates. Altogether, we established that, in addition to the commonly known and extensively studied photoreduction of oxidized flavins in flavoproteins, the reverse process (i.e., the photooxidation of anionic flavin radicals) can also occur. We propose that this process may constitute an excited-state deactivation pathway for protein-bound anionic flavin radicals in general. This hitherto undocumented photochemical reaction in flavoproteins further extends the family of flavin photocycles.
Identifiants
pubmed: 35181610
pii: 2118924119
doi: 10.1073/pnas.2118924119
pmc: PMC8872763
pii:
doi:
Substances chimiques
Anions
0
Dinitrocresols
0
Flavins
0
Flavoproteins
0
Flavin-Adenine Dinucleotide
146-14-5
4,6-dinitro-o-cresol
1604ZJR09T
Oxidoreductases
EC 1.-
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Informations de copyright
Copyright © 2022 the Author(s). Published by PNAS.
Déclaration de conflit d'intérêts
The authors declare no competing interest.
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