Photochemical addition of amino acids and peptides to DNA

The quantum yields for photochemical addition of twenty amino acids commonly occurring in proteins to denatured calf thymus DNA have been determined in deoxygenated phosphate buffer using a fluorescamine assay technique. Fifteen were found to be reactive, with cysteine, lysine, phenylalanine, tryptophan and tyrosine being the most reactive. Alanine, aspartic acid, glutamic acid, serine and threonine were unreactive. Analogous quantum yields for eighteen peptides of the form glycyl X (X being an amino acid) were also determined, along with the corresponding quantum yields for L-alanyl-L-tryptophan, L-seryl-L-seryl-L-serine, L-threonyl-L-threonyl-L-threonine, and L-cystine-bis-glycine. All of the peptides were found to be reactive. The modified amino acids Nsup(epsilon)-methyllysine, Nsup(epsilon), Nsup(epsilon), Nsup(epsilon)-trimethyllysine and Nsup(epsilon)-acetyllysine, all occurring in minor amounts in chromosomal proteins, were also reactive as was Nsup(α)-acetyllysine. In some cases higher quantum yields for photoaddition to denatured DNA are observed while in other cases the reverse is true. The effect of oxygen on the quantum yields for photoaddition of selected peptides to DNA was examined. While for most systems studied the amount of reaction in aerated systems was less than in deoxygenated systems, in the case of glycyl-L-phenylalanine the reverse was true. (author)