Journal
FREE RADICAL BIOLOGY AND MEDICINE
Volume 49, Issue 6, Pages 1014-1022Publisher
ELSEVIER SCIENCE INC
DOI: 10.1016/j.freeradbiomed.2010.06.011
Keywords
Pterins; Photoinduced electron transfer; Superoxide anion; Free radicals
Funding
- Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) [PIP 6301/05]
- Agencia de Promocion Cientifica y Tecnologica [PICT 33919, PICT 06-01482]
- Universidad Nacional de La Plata
- Ministerio de Ciencia, Tecnologia, e Innovacion Productiva (Argentina)
- ECOS-Sud (France) [A07E07]
- CONICET
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Pterins (Pt) are heterocyclic compounds widespread in living systems. They participate in relevant biological processes, such as metabolic redox reactions, and can photoinduce the oxidation of biomolecules through electron-transfer mechanisms. We have investigated the electron-transfer pathways initiated by excited states of pterin (Ptr) and 6-methylpterin (Mep), selected as model compounds. The experiments were carried out in aqueous solutions under continuous UV-A irradiation, in the presence and in the absence of ethylenediaminetetraacetic acid (EDTA), used as an electron donor. The reactions were followed by UV/Vis spectrophotometry, HPLC, and an enzymatic method for H2O2 determination. The formation of the superoxide anion (O-2(center dot-)) was investigated by electron paramagnetic resonance-spin trapping. The triplet excited states of Ptr and Mep are efficient electron acceptors, able to oxidize a Pt molecule in its ground state. The resulting radical anion (Pt center dot-) reacts with dissolved O-2 to yield O-2(center dot-), regenerating the pterin. In the presence of EDTA, this reaction competes efficiently with the anaerobic reaction between Pt center dot- and EDTA(center dot+),, yielding the corresponding stable dihydroderivatives H2Pt. The effects of EDTA and dissolved 02 concentrations on the efficiencies of the different competing pathways were analyzed. (C) 2010 Elsevier Inc. All rights reserved.
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