Probing the Mechanism of Targeted Delivery of Molecular Surfactants Loaded into Nanoparticles after Their Assembly at Oil-Water Interfaces.

A targeted and controlled delivery of molecular surfactants at oil-water interfaces using the directed assembly of nanoparticles, NPs, is reported. The mechanism of NP assembly at the interface and the release of molecular surfactants is followed by laser scanning confocal microscopy and surface force spectroscopy. The assembly of positively charged polystyrene NPs at the oil-water interface was facilitated by the introduction of carboxylic acid groups in the oil phase (e.g., by adding 1 wt % stearic acid to hexadecane to produce a model oil). The presence of positively charged NPs consistently lowers the stiffness of the water-oil interface. The effect is lessened, when the NPs are present in a solution of NaCl or deionized water at pH 2, consistent with a less dense monolayer of NPs at the interface in the last two systems. In addition, the NPs reduce the interfacial adhesion (i.e., the "stickiness" of the interface or, put differently, the pull-off force experienced by the atomic force microscopy (AFM) tip during retraction). After the assembly, the NPs can release a previously loaded cargo of surfactant molecules, which then facilitate the formation of a much finer oil-water emulsion. As a proof of concept, we demonstrate the release of octadecyl amine, ODA, that has been incorporated into the NPs prior to the assembly. The release of ODA causes the NPs to detach from the interface altering the interfacial properties and leads to finer oil droplets. This approach can be exploited in applications in several fields ranging from pharmaceutical and cosmetics to hydrocarbon recovery and oil-spill remediation, where a targeted and controlled release of surfactants is wanted.