Forced Interactions: Ionic Polymers at Charged Surfactant Interfaces

Characterizing electrostatic interactions at heterogeneous interfaces is critical for developing a fundamental description of the dynamic processes at charged interfaces. Water-in-oil reverse micelles (RMs) offer a high degree of tunability across composition, polarity, and temperature, making them ideal systems for studying interactions at heterogeneous liquid–liquid interfaces. In the present study, we use a combination of ultrafast two-dimensional infrared spectroscopy and molecular dynamics (MD) simulations to determine the picosecond interfacial dynamics in RMs containing binary compositions of sorbitan monostearate and anionic or cationic cosurfactants, which are used to tune the ratio of charged to nonionic surfactants at the interface. The positively charged polyethylenimine (PEI) polymer is encapsulated within the RMs, and the carbonyl stretching mode of sorbitan monostearate reports on the interfacial hydrogen-bond populations and dynamics. The results show that hydrogen-bond populations are altered through the inclusion of both negatively and positively charged cosurfactants. Charged surfactants increase interfacial water penetration into the surfactant layer, and the surface localization of polymers decreases water penetration. Local hydrogen-bond dynamics undergo a slowdown with the inclusion of charged surfactants, and the encapsulation of polymers results in similar effects, irrespective of the charge.