This paper studies the dye-sensitized photooxidation of tyrosine (tyr) and tyr di- and tripeptides (tyr-tyr and tyr-tyr-tyr) mediated by singlet molecular oxygen (O2[1 delta g]) in alkaline media. Photooxidation quantum efficiencies (phi r) were obtained by determining the overall and reactive rate constants of interaction with the oxidative species, employing the time-resolved O2(1 delta g) phosphorescence detection method and static-photolysis actinometric method, respectively. The interaction of O2(1 delta g)-tyr derivatives occurs through an intermediate encounter complex with polar character. Ionization of the phenolic OH group of tyr derivatives and the polarity of the solvent favors the overall interaction. Nevertheless, phi r values decrease when changing from water to MeCN-water medium. This indicates that the reactive deactivation of the encounter complex, probably an entropy-controlled step, may be affected by solvent polarity in the same way as those processes in which charges are neutralized along the reaction pathway. Photooxidation quantum efficiencies indicate that the contribution to O2(1 delta g) physical quenching (a second alternative deactivation route for the encountered complex [O2(1 delta g)-tyr derivatives]) increases with the complexity of the peptide. As a result, the selfprotection of the peptidic entity against physical quenching also increases. The information obtained from the fractional consumption mol O2/mol tyr derivative (in tyr, the di- and tripeptides and the respective methyl ester of tyr and the tripeptide), together with the evolution (either consumption and/or generation) of primary amino groups upon photosensitized irradiation of the same compounds clearly indicates that the photooxidation of di- and tri-tyr peptides proceeds with the breakage of peptidic bonds. As a consequence, in the final balance each tyr unity behaves as an independent photooxidizable target.
The role of quinones and hydroxyquinones as sensitizers and as quenchers in Type II photooxygenations has been examined. The second aspect is discussed here, through a systematic study, for the first time in the open literature. Quinonic compounds are excellent generators of O2(1Δg) in aprotic solvents (excluding those quinones possessing substituents in positions adjacent to the carbonyl groups, in the case of anthraquinone derivatives). Benzoquinones, anthraquinones, and hydroxy derivatives are good O2(1Δg) quenchers upon dye-sensitized photoirradiation. The excited oxygen species is deactivated with rate constants in the range 106–107 M−1 s−1 depending on the solvent employed. The quenching process deactivates O2(1Δg) without further destruction of the quinone. The main interaction with O2(1Δg) is driven by the quinone moiety, in spite of the presence of potentially active nuclear substituents. The quenching mechanism could involve a reversible charge transfer intermediate, with the quinonic compound acting as an electron donor. Keywords: photooxidation, quenching, quinones, rose bengal, singlet oxygen.
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