title: Oxidation of 2'-deoxyguanosine 5'-monophosphate photoinduced by pterin: type I versus type II mechanism.
abstract: UV-A radiation (320-400 nm) induces damage to the DNA molecule and its components through different photosensitized reactions. Among these processes, photosensitized oxidations may occur through electron transfer or hydrogen abstraction (type I) and/or the production of singlet molecular oxygen ((1)O2) (type II). Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitized oxidation of 2'-deoxyguanosine 5'-monophosphate (dGMP) by pterin (PT) in aqueous solution under UV-A irrradiation. Kinetic analysis was employed to evaluate the participation of both types of mechanism under different pH conditions. The rate constant of (1)O2 total quenching (k(t)) by dGMP was determined by steady-state analysis of the (1)O2 NIR luminescence, whereas the rate constant of the chemical reaction between (1)O2 and dGMP (k(r)) was evaluated from kinetic analysis of concentration profiles obtained by HPLC. The results show that the oxidation of dGMP photosensitized by PT occurs through two competing mechanisms that contribute in different proportions depending on the pH. The dominant mechanism in alkaline media involves the reaction of dGMP with (1)O2 produced by energy transfer from the PT triplet state to molecular oxygen (type II). In contrast, under acidic pH conditions, where PT and the guanine moiety of dGMP are not ionized, the main pathway for dGMP oxidation involves an initial electron transfer between dGMP and the PT triplet state (type I mechanism). The biological implications of the results obtained are also discussed.
authors.affiliation: Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICET, Casilla de Correo 16, Sucursal 4, (1900) La Plata, Argentina.
authors.forename: Gabriela
authors.initials: G
authors.lastname: Petroselli
authors.forename: M Laura
authors.initials: ML
authors.lastname: Dántola
authors.forename: Franco M
authors.initials: FM
authors.lastname: Cabrerizo
authors.forename: Alberto L
authors.initials: AL
authors.lastname: Capparelli
authors.forename: Carolina
authors.initials: C
authors.lastname: Lorente
authors.forename: Esther
authors.initials: E
authors.lastname: Oliveros
authors.forename: Andrés H
authors.initials: AH
authors.lastname: Thomas
mesh_terms: D003848:Deoxyguanine Nucleotides / Q000737:chemistry / Q000528:radiation effects; D004579:Electron Transport; D007700:Kinetics; D010084:Oxidation-Reduction; D010777:Photochemistry; D011622:Pterins / Q000737:chemistry / Q000528:radiation effects; D026082:Singlet Oxygen / Q000737:chemistry / Q000528:radiation effects; D013997:Time Factors; D014466:Ultraviolet Rays
chemical_list: D003848:Deoxyguanine Nucleotides; D011622:Pterins; D026082:Singlet Oxygen; C007257:2'-deoxyguanosine 5'-phosphate