Interactions between a Series of pyrene end-labeled poly(ethylene oxide)s and sodium dodecyl sulfate in aqueous solution probed by fluorescence

The interactions between a series of poly(ethylene oxide)s covalently labeled at both ends with pyrene pendants (PEO(X)-Py, where X represents the number-average molecular weight of the PEO chains and equals 2K, 5K, 10K, and 16.5K) and an ionic surfactant, namely, sodium dodecyl sulfate (SDS), in water were investigated at a fixed pyrene concentration of 2.5 μM corresponding to polymer concentrations smaller than 21 mg/L and with an SDS concentration range between 5 × 10 and 0.02 M, thus encompassing the 8 mM critical micelle concentration (CMC) of SDS in water. The steady-state fluorescence spectra showed that the I/I ratio decreased from 1.73 ± 0.06 for SDS concentration smaller than 2 mM where pyrene was exposed to water to 1.43 ± 0.03 for SDS concentration greater than 6 mM where pyrene was incorporated inside SDS micelles. The ratio of excimer-to-monomer emission intensities (the I/I ratio) of all PEO(X)-Py samples remained constant at low SDS concentrations, then increased, passed through a maximum at the same SDS concentration of 4 mM before decreasing to a plateau value that is close to zero for PEO(10K)-Py and PEO(16.5K)-Py but nonzero for PEO(2K)-Py and PEO(5K)-Py. The pyrene end groups of these two latter samples could not bridge two different micelles due to the short PEO chain, and excimer was formed by intramolecular diffusion inside the same SDS micelle. Time-resolved fluorescence decays of the pyrene monomer and excimer of the PEO(X)-Py samples were acquired at various SDS concentrations and globally fitted according to the "Model Free" analysis over the entire range of SDS concentration. The molar fractions of various excited pyrene species and the rate constant of pyrene excimer formation retrieved from the analysis of fluorescence decays were obtained as a function of SDS concentration. Interactions between SDS and PEO could not be detected by isothermal titration calorimetry, potentiometry with a surfactant selective electrode, and conductance measurements.