Pyrene-viologen complexes in SDS micelles: quenching parameters and use as probes of aggregation numbers

Through a formal-kinetic treatment, we rigorously derive the micellar occupations in the presence of fluorophore-quencher ground-state complexes and the resulting expressions for the time-dependent and stationary observables in the case of combined static and dynamic quenching. We present a protocol for data analysis that effectively isolates the processes, thereby ensuring rapid fit convergence and unique parameter sets. By this approach, we interpret time-resolved fluorescence measurements on pyrene quenched by a homologous series of viologens in SDS micelles. The dynamic intramicellar quenching is diffusion limited; and the formation of the ground-state complexes is entropy driven, with a constant increment per methylene group in the viologen sidechains. The micellar aggregation numbers are obtained with a precision comparable to neutron scattering, including their temperature dependence.