Spin-orbit coupling effects in O 2 activation by cofactor-independent 2,4-dioxygenase

B. F. Minaev, R. R. Valiev

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)


The O 2 (dioxygen) is paramagnetic molecule with two non-paired electron spins and triplet ground state (S = 1) while majority of organic molecules are diamagnetic species; they have all electron spins paired and the singlet ground state with the total spin S = 0. Oxygenases catalyze a concerted insertion of the triplet dioxygen into organic (diamagnetic) molecules in a strictly spin-forbidden process and this puzzle is not solved so far in modern enzymology. Many oxidases and oxygenases utilize the π-conjugated organic cofactor (like flavins, pterins) in a singlet ground state and reaction of cofactor with O 2 is still spin-forbidden. It is clear that the protein environment in the enzyme active-site “helps” in some way to overcome spin prohibition, but this environment is definitely diamagnetic and the spin-puzzle still exists. Some oxidases and oxygenases use paramagnetic metal ions as a cofactor; in this case the spin prohibition is formally reduced. In recent years, a numbers of oxidative enzymes are discovered which do not contain any cofactor. In the present work, we considered a rather popular cofactor-free bacterial 2,4-dioxygenase and its oxygenolytic reactions with 2-n-alkyl-3-hydroxy-4(1H)-quinolones (AHQ’s). We presented results of quantum-chemical calculations of intermediate diradical proposed recently for direct reaction of dioxygen with AHQ substrate and made conclusion about the mechanism of spin-catalysis.

Original languageEnglish
Pages (from-to)38-46
Number of pages9
JournalUkrainian biochemical journal
Issue number1
Publication statusPublished - 1 Jan 2019
Externally publishedYes


  • 2-methyl-3-hy-droxy-4(1H)-quinolone
  • Bacterial 1-H-3-hydroxy-4-oxoquinaldine 2,4-dioxygenase
  • Cofactor-independent oxygenases
  • Dioxygen
  • Radical pair
  • Spin-orbit coupling
  • Superoxide anion
  • Triplet-singlet transition

ASJC Scopus subject areas

  • Biochemistry

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