Interfacial Steric and Molecular Bonding Effects Contributing to the Stability of Neutrally Charged Nanoemulsions

In cosmetic, pharmaceutical, and food applications, many active ingredients have limited bioavailability in an aqueous environment, and in that context, nanoemulsions provide a mechanism for encapsulation, protection, and transport. These dispersed oil droplets are on the order of 100s of nanometers in diameter and owe their long-term stability to emulsifiers that are commonly charged. More recently, applications have been utilizing nonionic species as stabilizing agents due to their enhanced biosafety. DLVO (named after Derjaguin, Landau, Verwey, and Overbeek) theory has been central in the description of colloid stability, which emphasizes repulsive electrostatic forces, while extended DLVO theory also accounts for steric effects. Past studies of nanoemulsions have largely employed charged surfactants and polyelectrolytes, making it difficult to decouple electrostatic and steric effects as they relate to droplet stability. To better understand steric and molecular factors contributing to the stability of "uncharged" droplets, we have created nanoemulsions with sodium dodecyl sulfate (SDS) and poly(N-vinylacetamide) (PNVA). Though SDS is anionic, with PNVA coating the droplet surfaces, the ζ-potentials of these nanoemulsions are ∼0 mV. Despite minimizing electrostatic contributions, these nanoemulsions are stable for upward of a month with interesting dynamics. By employing dynamic light scattering, vibrational sum frequency scattering spectroscopy, and calculating interaction pair potentials using extended DLVO theory, we learn that the thickness of the PNVA layer plays a critical role in stabilizing these "uncharged" nanoemulsions. Beyond the sterics, the molecular conformation of the PNVA strands also contributes to the droplet stability. The adsorbed PNVA strands are shown to form stratified, rigid polymer networks that prevent the nanoemulsions from rapid destabilization.