Ultrasonic assisted water-in-oil emulsions encapsulating macro-molecular polysaccharide chitosan: Influence of molecular properties, emulsion viscosity and their stability

An ultrasonic technique was applied to formulation of two-phase water-in-paraffin oil emulsions loading a high-molecular polysaccharide chitosan (CS) and stabilized by an oil-soluble surfactant (Span80) at different operational conditions. The influence of chitosan molecular properties, phase volume ratio (φ_w), Span80 volume fraction (φ_s) and ultrasonic processing parameters were systemically investigated on the basis of mean droplet diameter (MDD) and polydispersity index (PDI) of emulsions. It was observed that the molecular weight (M_w) of CS was an important influential factor to MDD due to the non-Newtonian properties of CS solution varying with M_w. The minimum MDD of 198.5 nm with PDI of 0.326 was obtained with ultrasonic amplitude of 32% for 15 min at an optimum φ_w of 35%, φ_s of 8%, probe position of 2.2 cm to the top of emulsion, while CS with M_w of 400 kDa and deacetylation degree of 84.6% was used. The rise of emulsion viscosity and the reduction of negative zeta potential at φ_w increasing from 5% to 35% were beneficial to obtain finer droplets and more uniform distribution of emulsions, and emulsion viscosity could be represented as a monotonically-decreasing power function of MDD at the same φ_w. FTIR analysis indicated that the molecular structure of paraffin oil was unaffected during ultrasonication. Moreover, the emulsions exhibited a good stability at 4 °C with a slight phase separation at 25 °C after 24 h of storage. By analyzing the evolution of MDD, PDI and sedimentation index (SI) with time, coalescence model showed better fitting results as comparison to Ostwald ripening model, which demonstrated that the coalescence or flocculation was the dominant destabilizing mechanism for such W/O emulsions encapsulating CS. This study may provide a valuable contribution for the application of a non-Newtonian macromolecule solution as dispersed phase to generate nano-size W/O emulsions via ultrasound, and widen knowledge and interest of such emulsions in the functional biomaterial field.