Role of Counterions in Controlling the Properties of Ultrasonically Generated Chitosan-Stabilized Oil-in-Water Emulsions

An oil-in-water emulsion was ultrasonically prepared in aqueous chitosan solutions containing different counterions. Tetradecane was used as the oil phase in order to mimic nonpolar substances used in food processes. Various acids were used to dissolve chitosan, and we found that conjugate bases of the acids used, which act as counterions to neutralize the positive charges of ammonium ions present in the chitosan backbone, played a significant role in controlling the size, size distribution, and stability of chitosan-encapsulated tedradecane emulsion droplets (microspheres). The counterion effect is also found to be strongly dependent upon tetradecane (TD)/chitosan (CS) ratio and ultrasonic power. Key observations are: (i) for a given TD/CS ratio, the size and size distribution decrease when the acid is varied from nitric acid to benzenesulfonic acid at high TD/CS ratio, and the effect becomes less significant at low TD/CS ratio; (ii) for a given acid, the size and size distribution increase with an increase in TD/CS ratio; and (iii) at low TD/CS ratio the size and size distribution are significantly influenced by the viscosity of the system. A possible mechanism for the observed counterion effect is proposed. The role of counterions, solution viscosity, and ultrasonic power in controlling the physical and functional properties of ultrasonically generated chitosan-stabilized tetradecane microspheres is discussed in detail. The key new finding of this study is that it is possible to form stable emulsions without the addition of external emulsifiers and stabilizers, but only using chitosan with different acids to dissolve chitosan. This strategy could be used in the generation of stable food emulsions.