In this report, the dependence of pyrene photokinetics on sodium dodecyl sulfate (SDS) micelle concentration is investigated Via dynamic multidimensional fluorescence measurements. First, complex quantum yield matrices were constructed from steady-state spectra and multiple wavelength phase/modulation data. These matrices were then subjected to rank analysis in order to determine the number of spectrally distinct pyrene components. The consensus of these results is that there are three spectrally distinguishable pyrene components. Then, the emission spectra of the pyrene components, their relative initial concentrations, and the photokinetic transfer matrix, which describes their decay and interaction, are estimated without model assumptions. The characteristics of the fluorescence spectra and their dependence on the SDS concentration identify the three components as pyrene excimer, aggregates, and monomers. The results also indicate that pyrene decay kinetics in SDS micelles vary substantially with the SDS concentration. At low surfactant concentration, pyrene decays Via an irreversible 3-state mechanism. As the surfactant concentration is increased, the rate of the rate of the excimer dissociation reaction increases and the mechanism becomes reversible.
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