Temperature dependence of aggregation and dynamic surface tension in a photoresponsive surfactant system

The response of a nonionic photoresponsive surfactant system to changes in temperature is reported. This surfactant contains the light-sensitive azobenzene group, and when exposed to light, a solution of this surfactant contains a mixture of the cis and trans photoisomers of this group. The temperature of the surfactant solution has a strong impact on the time needed for the surfactant to diffuse and adsorb to a freshly formed interface. At surfactant concentrations that give rise to trans aggregates but not to cis aggregates, the transport of cis and of trans isomers to the surface of a pendant bubble have quite different temperature dependencies, owing largely to the difference in their aggregation states in bulk solution. Diffusion and adsorption of the cis isomer are described reasonably well by a simple diffusion model that accounts for the effect of temperature on the diffusion coefficient. The trans isomer, which was primarily bound in aggregates during these measurements, exhibits a stronger dependence of this adsorption time scale on the temperature of the solution. This temperature dependence of trans diffusion and adsorption is quantitatively consistent between samples containing only the trans isomer and samples containing a mixture of isomers. Fluorescence studies were done to determine the effect of temperature on the cmc of the surfactant. The critical concentration associated with the formation of cis-dominant aggregates increases modestly with increasing temperature. The cmc of the trans isomer also increases with increasing temperature, most significantly when the temperature exceeds about 35 degrees C. These trans cmc temperature-dependence data were incorporated into diffusion models that account for the potential roles of aggregates in the adsorption process. The observed temperature dependency of the trans adsorption time scale is consistent with a model that includes the effect of temperature on both the diffusivity and the supply of monomer via its effect on the cmc. Specifically, the results suggest that the dissolution of trans-dominant aggregates is important to the trans adsorption process. Further fluorescence studies were performed in which surfactant solutions containing aggregates were diluted rapidly, and the rate of dissolution of these aggregates was inferred from fluorescence decay. Aggregate breakup in colder trans samples is slower than in warmer samples, but these dissolution time scales are significantly shorter than those associated with the adsorption process. This is consistent with the assumption that aggregation kinetics do not contribute to the observed adsorption kinetics.