One-Step Dynamic Imine Chemistry for Preparation of Chitosan-Stabilized Emulsions Using a Natural Aldehyde: Acid Trigger Mechanism and Regulation and Gastric Delivery

Chitosan is a polysaccharide widely used as a structuring agent in foods and other materials because of its positive charge (amino groups). At present, however, it is difficult to form and stabilize emulsions using chitosan due to its high hydrophilicity. In this study, oil-in-water emulsions were prepared using a one-pot green-chemistry method. The chitosan and aldehyde molecules were in situ interfacially conjugated during homogenization, which promoted the adsorption of chitosan onto the oil droplet surfaces where they created a protective coating. The universality of this method was verified by using chitosan with different molecular weights and four kinds of natural aldehydes [cinnamaldehyde (CA), citral (CT), citronella (CN), and vanillin (VL)]. Chitosan with higher molecular weight facilitated the formation of emulsions. By harnessing the dynamic covalent nature of imine bonds, chitosan emulsions with an imine link display dynamic behavior with acid-catalyzed hydrolysis. The aldehyde structure could control the pH point of trigger for breakdown of emulsions, which was 1.0, 3.0, 4.0, and 4.0 for CA emulsion, CT emulsion, CN emulsion, and VL emulsion, respectively. At pH 6.5, aldehyde helped to decrease the interfacial tension of chitosan to about 10 mN/m, while this value would increase if the pH decreased by adding acid during the measurement. Chemical kinetics studies indicated that the hydrophobicity and conjugation effect of the aldehyde together determined the trigger points and properties of the emulsion. Finally, we used the optimized emulsions to encapsulate and control the release of curcumin. The gastric release behavior of the curcumin depended on aldehyde structure: VL > CN > CT ≈ CA. Hence, a tailor-made trigger release emulsion system can be achieved by rational selection and design of aldehyde structure to control hydrophobicity and conjugation effect of aldehydes.