Photoresponsive arylazopyrazole surfactant/PDADMAC mixtures: reversible control of bulk and interfacial properties

In many applications of polyelectrolyte/surfactant (P/S) mixtures, it is difficult to fine-tune them after mixing the components without changing the sample composition, e.g. pH or the ionic strength. Here we report on a new approach where we use photoswitchable surfactants to enable drastic changes in both the bulk and interfacial properties. Poly(diallyldimethylammonium chloride) (PDADMAC) mixtures with three alkyl-arylazopyrazole butyl sulfonates (CAAP) with -H, -butyl and -octyl tails are applied and E/Z photoisomerization of the surfactants is used to cause substantially different hydrophobic interactions between the surfactants and PDADMAC. These remotely controlled changes affect significantly the P/S binding and allows for tuning both the bulk and interfacial properties of PDADMAC/CAAP mixtures through light irradiation. For that, we have fixed the surfactant concentrations at values where they exhibit pronounced surface tension changes upon E/Z photoisomerization with 365 nm UV light (Z) and 520 nm green (E) light and have varied the PDADMAC concentration. The electrophoretic mobility can be largely tuned by photoisomerisation of CAAP surfactants and P/S aggregates, which can even exhibit a charge reversal from negative to positive values or vice versa. In addition, low colloidal stability at equimolar concentrations of PDADMAC with CAAP surfactants in the E configuration lead to the formation of large aggregates in the bulk which can be broken up by irradiation with UV light when the surfactant's alkyl chain is short enough (C₀AAP). Vibrational sum-frequency generation (SFG) spectroscopy reveals changes at the interface similar to the bulk, where the charging state at air-water interfaces can be modified with light irradiation. Using SFG spectroscopy, we interrogated the O-H stretching modes of interfacial H₂O and provide qualitative information on surface charging that is complemented by neutron reflectometry, from which we resolved the surface excesses of PDADMAC and CAAP at the air-water interface, independently.