Quenching and dequenching of pyrene fluorescence by nucleotide monophosphates in cationic micelles

The fluorescence behavior of pyrene solubilized in the hexadecyltrimethylammonium bromide aqueous micellar solution in the presence of adenosine 5'-monophosphate (AMP) and uridine 5'-monophosphate (UMP) was investigated. AMP and UMP were found to influence oppositely the fluorescence of micellized pyrene. UMP acts as quencher, while AMP acts as dequencher. Both effects saturate at high nucleotide concentration (about 40 mM). Dequenching of micellized pyrene fluorescence is induced also by addition of disodium hydrogen orthophosphate (Na 2HPO 4), while loading with sodium bromide (NaBr) quenches the fluorescence. Furthermore, in absence of micelles, pyrene fluorescence depends on the UMP, according to the Stern-Volmer relation, but is unaffected by AMP. Dynamic light scattering experiments showed that the size and shape of aggregates is not affected by different types of nucleotide loaded into the solution; thus, we conclude that the opposite photophysical effect exploited by AMP and UMP are uncorrelated to any change in micellar microstructure. The whole fluorescence data set was successfully accounted for by assuming that the anionic nucleotides compete with the surfactant counterion (bromide) for the surface of the micelle. Accordingly, substitution of bromide with the more effective quencher UMP results in a strong decrease of the pyrene fluorescence, while the substitution of bromide with the nonquencher AMP results in an increase in the pyrene fluorescence.