Effect of stacking interactions with poly(riboadenylic acid) on the triplet state properties of tryptophan.

Optically detected magnetic resonance (ODMR) signals of tryptophan (Trp) have been measured in L-lysyl-L-tryptophyl-L-lysine (Lys-Trp-Lys) and in its complex with poly(riboadenylic acid) [poly(rA)]. Measurements were made with optical narrow band detection through the Trp O-O band. Plots of [D] and [E] vs. lambda are distinctly different for Lys-Trp-Lys and its complex with poly(rA). A reduction of [D], in particular, is consistent with stacking of Trp with adenine in the complex, since this effect is expected from charge-transfer contributions in the excited triplet state. Triplet energy transfer from poly(rA) to Lys-Trp-Lys is nearly complete at 77 K, with a Trp:adenine ratio of 0.1. The energy transfer efficiency is considerably reduced at 4.2 K and below, probably resulting from reduction of the triplet mobility in the polymer. Analysis of the phosphorescence decays shows that the triplet states of poly(rA), Lys-Trp-Lys, and their complex decay nonexponentially. Binding of polylysine to poly(rA) has no effect on the phosphorescence spectrum, but the decay kinetics are changed.