Pickering emulsions stabilized by carboxylated nanodiamonds over a broad pH range

Abstract

[Hypothesis] Surfactants in emulsions sometimes do not provide adequate stability against coalescence, whereas Pickering emulsions often offer greater stability. In a search for stabilizers offering biocompatibility, we hypothesized that carboxylated nanodiamonds (ND) would impart stability to Pickering emulsions.

[Experiments] We successfully prepared Pickering emulsions of sunflower oil in water via two different methods: membrane emulsification and probe sonication. The first method was only possible when the pH of the aqueous ND suspension was ≤ 4.

[Findings] Pendant-drop tensiometry confirmed that carboxylated ND is adsorbed at the oil/water interface, with a greater decrease in interfacial tension found with increasing ND concentrations in the aqueous phase. The carboxylated ND become more hydrophilic with increasing pH, according to three-phase contact angle analysis, because of deprotonation of the carboxylic acid groups. Membrane emulsification yielded larger (about 30 µm) oil droplets, probe sonication produced smaller (sub-μm) oil droplets. The Pickering emulsions show high stability against mechanical vibration and long-term storage for one year. They remain stable against coalescence across a wide range of pH values. Sonicated emulsions show stability against creaming. In this first-ever systematic study of carboxylated ND-stabilized Pickering emulsions, we demonstrate a promising application in the delivery of β-carotene, as a model active ingredient.