Strong Cooperative Effect of Oppositely Charged Surfactant Mixtures on Their Adsorption and Packing at the Air-Water Interface and Interfacial Water Structure

Remarkable adsorption enhancement and packing of dilute mixtures of water-soluble oppositely-charged surfactants, sodium dodecyl sulfate (SDS) and dodecyl amine hydrochloride (DAN), at the air-water interface were observed by using sum frequency generation spectroscopy and tensiometry. The interfacial water structure was also observed to be significantly influenced by the SDS-DAH mixtures, differently from the synergy of the single surfactants. Most strikingly, the obtained spectroscopic evidence suggests that the interfacial hydrophobic alkyl chains of the binary mixtures assemble differently from those of single surfactants. This study highlights the significance of the cooperative interaction between the headgroups of oppositely charged binary surfactant systems and subsequently provides some insightful observations about the molecular structure of the air-aqueous interfacial water molecules and, more importantly, about the packing nature of the surfactant hydrophobic chains of dilute SDS-DAH mixtures of concentration below 1% of the CMC.