Dynamic surface tension behavior in a photoresponsive surfactant system

The surface properties of a nonionic photoresponsive surfactant that incorporates the light-sensitive azobenzene group into its tail have been investigated. Cis-trans photoisomerization of this azobenzene group alters the ability of the surfactant to pack into adsorbed monolayers at an air/water interface or into aggregates in solution, thereby causing a significant variation in surface and bulk properties following a change in the illumination conditions. NMR studies indicate that a solution left in the dark for an extended period of time contains the trans isomer almost exclusively, whereas samples exposed to light of fixed wavelength eventually reach a photostationary equilibrium in which significant amounts of both isomers are present. At concentrations well above the cmc but under different illumination conditions (dark, UV light, visible light), freshly formed surfaces exhibit profoundly different surface tension trajectories as they approach essentially identical equilibrium states. This common equilibrium state corresponds to a surface saturated with the trans (more surface active) isomer. The dark sample shows a simple, single-step relaxation in surface tension after the creation of a fresh interface, whereas the UV and visible samples exhibit a more rapid initial decrease in tension, followed by a plateau of nearly constant tension, and finally end with a second relaxation to equilibrium. It is hypothesized that this behavior of the UV and visible samples is caused by competitive adsorption between the cis and trans isomers present in these mixtures. The cis surfactant reaches the interface more quickly, leading to an initially cis-dominated interface having a tension value corresponding to the intermediate plateau, but is ultimately displaced by the trans isomer. Fluorescence studies are used for cmc determination in the samples, and the results suggest that the two isomers segregate into distinct aggregate phases. The critical concentration associated with the formation of cis-rich aggregates is much larger than that of the trans-rich aggregates, which accounts for the faster diffusion of the cis isomer to a fresh interface. Models of the diffusion and adsorption of surfactant are developed. These consider the role of aggregates in the adsorption process by examining the limiting behavior of three aggregate properties: dissolution rate, mobility, and ability to incorporate into the interface. These models are used to analyze the surface tension relaxation of dark and UV samples, and the predictions are found to be in agreement with the observed characteristic relaxation time scales for these samples, though the results are inconclusive regarding the specific role of aggregates. High-intensity illumination focused on a surface saturated with surfactant is used to drive photoisomerization of the adsorbed surfactant, and rapid, substantial changes in surface tension result. These changes are consistent with proposed conformations of the adsorbed surfactant and with monolayer studies performed with a Langmuir film balance.