J. D. Tassin, R. Borkman
Nov 1, 1980
Citations
0
Influential Citations
40
Citations
Journal
Photochemistry and Photobiology
Abstract
We have measured the relative rates of photolysis of free tryptophan (trp), the dipeptides Gly‐Trp, Trp‐Gly, Leu‐Trp, and Trp‐Leu, and the tripeptides Gly‐Trp‐Gly and Leu‐Trp‐Leu. The photolyses were performed in neutral 0.1 mM aqueous solutions at 25°C using monochromatic 290 nm Xe arc radiation. Tryptophan loss was monitored by absorption, fluorescence and phosphorescence spectroscopy. The rate of tryptophan fluorescence loss was found to be different in the di‐and tripeptides than in tryptophan monomer. These rate differences depended on both the identity of the neighboring amino acid (gly or leu) and on the nature of the linkage, e.g., the rate of Gly‐Trp photolysis was more than 10 times greater than the rate of Trp‐Gly photolysis. Degassing was found to markedly reduce (factor of 8) the photolysis rates of Trp, Trp‐Gly, and Trp‐Leu, but degassing only slightly reduced (less than a factor of 2) the photolysis rates of the other di‐and tri‐peptides. Photochemical product structures were not determined, but absorption and fluorescence spectra were obtained and products could be inferred in some cases by comparison with data of previous workers. The products appeared to differ greatly among the various peptides studied; Trp, Trp‐Gly, and Trp‐Leu gave oxidation products, while Gly‐Trp and Leu‐Trp apparently gave ring closure products, not requiring oxygen.