Thermally and pH-responsive gelation of nanoemulsions stabilized by weak acid surfactants

Nanoemulsions are widely used in applications such as in food products, pharmaceutical ingredients and cosmetics. Moreover, nanoemulsions have been a model colloidal system due to their ease of synthesis and the flexibility in formulations that allows one to engineer the inter-droplet potentials and thus to rationally tune the material microstructures and rheological properties. In this article, we study a nanoemulsion system in which the inter-droplet interactions are modulated by temperature and pH. We develop a nanoemulsion suspension in which the droplets are stabilized by weak acid surfactants whose charged state can be independently controlled by temperature and pH, leading to a responsive electrostatic repulsion. Moreover, the additional poly(ethylene glycol) segment (PEG) on the surfactant gives rise to a temperature responsive attraction between droplets via PEG-PEG association and ion-dipole interaction. The interplay of these three interactions gives rise to non-monotonic trends in material properties and structures as a function of temperature. The underlying mechanism resulting in these trends is obtained by carefully characterizing the nanoemulsion droplets and studying the molecular interactions. Such mechanistic understanding also provides guidance to modulate the inter-droplet potential using pH and ionic strength. Moreover, the molecular understanding of the weak acid surfactant also sheds light on the destabilization of the nanoemulsion droplets triggered by a switch in pH. The control of the competition of attractive and repulsive interactions using external stimuli opens up the possibility to design complex nanoemulsion-based soft materials with controllable structures and rheological properties.