Multiple Water-in-Oil-in-Water Emulsion Gels Based on Self-Assembled Saponin Fibrillar Network for Photosensitive Cargo Protection

A gelled multiple water-in-oil-in-water (W-1/O/W-2) emulsion was successfully developed by the unique combination of emulsifying and gelation properties of natural glycyrrhizic acid (GA) nanofibrils, assembling into a fibrillar hydrogel network in the continuous phase. The multiple emulsion gels had relatively homogeneous size distribution, high yield (85.6-92.5%), and superior storage stability. The multilayer interfacial fibril shell and the GA fibrillar hydrogel in bulk can effectively protect the double emulsion droplets against flocculation, creaming, and coalescence, thus contributing to the multiple emulsion stability. Particularly, the highly viscoelastic bulk hydrogel had a high storage modulus, which was found to be able to strongly prevent the osmotic-driven water diffusion from the internal water droplets to the external water phase. We show that these multicompartmentalized emulsion gels can be used to encapsulate and protect photosensitive water-soluble cargos by loading them into the internal water droplets. These stable multiple emulsion gels based on natural, sustainable saponin nanofibrils have potential applications in the food, pharmaceutical, and personal care industries.