Expanding reaction horizons: evidence of the 5‐deazaflavin radical through photochemically induced dynamic nuclear polarization

Abstract: Deazaflavins are important analogues of the naturally occurring flavins: riboflavin, flavin mononucleotide (FMN), and flavin adenine dinucleotide (FAD). The use of 5-deazaflavin as a replacement coenzyme in a number of flavoproteins has proven particularly valuable in unraveling and manipulating their reaction mechanisms. It was frequently reported that one-electron-transfer reactions in flavoproteins are impeded with 5-deazaflavin as the cofactor. Based on these findings, it was concluded that the 5-deazaflavin radical is significantly less stable compared to the respective flavin semiquinone and quickly re-oxidizes or undergoes disproportionation. The long-standing paradigm of 5-deazaflavin being solely a two-electron/hydride acceptor/donor—“a nicotinamide in flavin clothing”—needs to be re-evaluated now with the indirect observation of a one-electron-reduced (paramagnetic) species using photochemically induced dynamic nuclear polarization (photo-CIDNP) 1H nuclear magnetic resonance (NMR) under biologically relevant conditions

Location
Deutsche Nationalbibliothek Frankfurt am Main
Extent
Online-Ressource
Language
Englisch
Notes
Angewandte Chemie. International Edition. - 62, 43 (2023) , e202309334, ISSN: 1521-3773

Classification
Chemie

Event
Veröffentlichung
(where)
Freiburg
(who)
Universität
(when)
2023
Creator

DOI
10.1002/anie.202309334
URN
urn:nbn:de:bsz:25-freidok-2396880
Rights
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Last update
25.03.2025, 1:53 PM CET

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Associated

Time of origin

  • 2023

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