Hydration mediated interfacial transitions on mixed hydrophobic/hydrophilic nanodroplet interfaces

Interfacial phase transitions are of fundamental importance for climate, industry, and biological processes. In this work, we observe a hydration mediated surface transition in supercooled oil nanodroplets in aqueous solutions using second harmonic and sum frequency scattering techniques. Hexadecane nanodroplets dispersed in water freeze at a temperature of ∼15 °C below the melting point of the bulk alkane liquid. Addition of a trimethylammonium bromide (CTA) type surfactant with chain length equal to or longer than that of the alkane causes the bulk oil droplet freezing transition to be preceded by a structural interfacial transition that involves water, oil, and the surfactant. Upon cooling, the water loses some of its orientational order with respect to the surface normal, presumably by reorienting more parallel to the oil interface. This is followed by the surface oil and surfactant alkyl chains losing some of their flexibility, and this chain stretching induces alkyl chain ordering in the bulk of the alkane phase, which is then followed by the bulk transition occurring at a 3 °C lower temperature. This behavior is reminiscent of surface freezing observed in planar tertiary alkane/surfactant/water systems but differs distinctively in that it appears to be induced by the interfacial water and requires only a very small amount of surfactant.