Strong self-association of chitosan microgels at interface mediated high stabilities in Pickering emulsion

The spontaneous self-organization of naturally-occurring polysaccharide particles into a thick and robust gel network at interface in Pickering emulsion is challenging. Inspired by the phenomenon that chitosan microgels (CSMs) with a certain size could self-associate into a solidified gel phase upon freezing, here we tentatively used CSMs to construct a highly-stable Pickering emulsion. CSMs can form a stable Langmuir's layer at the water/oil interface through the network deformation and re-arrangement of dangling chains, while the subsequent negative polymer coating can avoid the bridging resulting from the cross-association for CSMs on different emulsion droplets upon freezing. The experimental results indicated that the emulsion showed excellent features, including the wide pH range stability (3-12), long-term storage stability (> 3 months), thermal stability (121 °C, 30 min). Moreover, CSMs could self-associate into a reliable gel layer around the oil droplet in freezing, leading to the better freeze-thaw stability (1-3 cycles). The negative coating not only facilitates the formation of interfacial gel network around each emulsion droplet, but also produces huge steric hindrance and electrostatic repulsion to suppress the coalescence. This work provides a different way to modulate the interfacial structure, thus developing a more stable polysaccharide-based Pickering emulsion.