Molecular Adsorption and Physicochemical Properties at Liquid/Liquid Nanoemulsion Soft Interfaces: Effect of Charge and Hydrophobicity.

Contrary to the popular adage, "Oil and water do not mix", evidence of mixtures comprising the two "immiscible" liquids is universal. In the presence of an emulsifier, oil and water mix to form a colloidal suspension known as emulsion. Their utility in many areas such as food chemistry, biomedical health sectors, catalysis, and the petroleum industry is well recognized. While their application in our society is pervasive, tantalizing fundamental questions regarding the chemistry that takes place at the oil/water soft interface still linger. For instance, do organic compounds show proclivity for this molecularly thin boundary and, if so, what forces, hydrophobic or pure electrostatic among others, drive the molecular interactions? The focus of this Article is on molecular adsorption at the interface of oil-in-water (O/W) nanoemulsion (NE) droplets. The effect of the interfacial surfactant charge (positive, negative, zwitterionic, and neutral) on the affinity of aromatic organic compounds on the O/W NEs has been studied. Using a second harmonic generation (SHG), a nonlinear light scattering technique, we have explored the adsorption equilibrium of charged and neutral organic dyes. By variation of the surfactant functional group and thereby the interfacial charge properties, the source of the adsorption interaction, if any, has been deduced. The population of surfactants containing a charged functional group at the O/W interface is found to be sparse, yet adsorption at some of these interfaces has been observed. A purely electrostatic Coulomb interaction plays a key role, but the presence of a charged interface does not necessitate molecular adsorption. Hydrophobic interactions are not a major driving force of adsorption for the SHG dyes studied. However, a possible pi-interaction is likely in explaining the accumulation of neutral aromatic compounds at the O/W NE interface. These intricate adsorption features are discussed in the context of NE interfacial charge properties and their stability upon molecular adsorption.