Mechanism of electron-transfer processes photoinduced by lumazine

M. PAULA DENOFRIO; M. LAURA DÁNTOLA; PATRICIA VICENDO; ESTHER OLIVEROS; ANDRÉS H. THOMAS; CAROLINA LORENTE

Photochemical and Photobiological Sciences

ROYAL SOC CHEMISTRY

Año: 2012 vol. 11 p. 409 - 417

1474-905X

ABSTRACT: UV-A (320-400 nm) and UV-B (280-320 nm) radiation causes damage to DNA and other biomolecules through reactions induced by different endogenous or exogenous photosensitizers. Lumazines are heterocyclic compounds present in biological systems as biosynthetic precursors and/or products of metabolic degradation. The parent and unsubstituted compound called lumazine (pteridine-2,4(1,3H)-dione; Lum) is able to act as photosensitizer through electron-transfer-initiated oxidations. To get further insight into the mechanisms involved, we have studied in detail the oxidation of 2 deoxyadenosine 5 monophosphate (dAMP) photosensitized by Lum in aqueous solution. After UV-A or UV-B excitation of Lum and formation of its triplet excited state (3Lum*), three reaction pathways compete for the deactivation of the latter: intersystem crossing to singlet ground state, energy transfer to O2, and electron transfer between dAMP and 3Lum* yielding the corresponding pair of radical ions (Lum•- and dAMP•+). In the following step, the electron transfer from Lum•- to O2 regenerates Lum and forms the superoxide anion (O2•-), which undergoes disproportionation into H2O2 and O2. Finally dAMP•+ participates in subsequent reactions to yield products.