Quenching of singlet oxygen by Trolox C, ascorbate, and amino acids: Effects of pH and temperature

The pH dependence of singlet oxygen quenching by histidine, N-acetyltyrosine ethyl ester (ATEE), ascorbic acid, Trolox C, and tryptophan has been observed using time-resolved infrared luminescence measurements in a D2O/acetonitrile (50:50 v/v) solvent. Deprotonation of ascorbic acid, the protonated imidazole ring of histidine and the phenolic group of ATEE leads to an increase in the quenching rate constants by between 2 and 3 orders of magnitude. Such changes appear to be the basis for wide variations in quoted literature values of singlet oxygen quenching constants for these and related compounds. It is estimated that these pH-dependent quenching rate constants predict a modest (approximately 2- to 3-fold) change in singlet oxygen lifetime between the extremes of cellular pH. Activation data for singlet oxygen quenching show that the enthalpies of activation are low in all cases (between 0 and 11 kJ mol(-1)) and that substantially negative entropies of activation (between -49 and -116 J K-1 mol(-1)) result in rate constants being much lower than the diffusion-controlled limit. In all cases the data are consistent with quenching via reversible formation of an exciplex, all reactions being at the preequilibrium limit over the available temperature range.