Photo-oxidation of methionine-containing peptides by the 4-carboxybenzophenone triplet state in aqueous solution. Competition between intramolecular two-centered three-electron bonded (S...S)+ and (S...N)+ formation.

Abstract

Quantum yields for the formation of transients were measured following the quenching of triplet 4-carboxy-benzophenone (3CB*) by methionine-containing peptides in aqueous solutions. Ketyl radicals (CBH.), ketyl radical anions (CB.-) and various sulfur radical cations were identified following the triplet-quenching events. The presence of these intermediates indicated that the triplet-quenching mechanism can be characterized as mainly electron-transfer in nature. The quenching rate constants were of the order of 2 x 10(9) M-1 s-1. There were small, but significant, differences in the triplet-quenching rate constants, and these trends indicate the existence of multiple sulfur targets in the quenchers. The absorption of the transient products was followed in detail by using spectral-resolution analysis. From the absorption data, quantum yields were estimated for the formation of the various transients. There were differences found in the yields of the transient products between the experiments, where the quenchers were the "mixed" stereoisomers of methionylmethionine (L,D and D,L) and experiments where the quenchers were L,L and D,D stereoisomers. Triplet-quenching data from several other methionine-containing small oligopeptides were analyzed in an analogous manner. Systematic variations were observed, and these patterns were discussed in terms of competitive donation of protons to the CB.- within the charge-transfer complex. The competition was between protons on carbons adjacent to the sulfur-radical center and protons on the protonated amino groups of the radical cation. In addition, there was a competition between the two intramolecular two-centered, three-electron bonded species (S therefore S)+ and (S therefore N)+ that play roles in the secondary kinetics.