Water-borne synthesis of multi-responsive and biodegradable chitosan-crosslinked microgels: Towards self-assembled films with adaptable properties

The present study aims in the synthesis of new biodegradable stimuli-responsive microgels with controllable microstructure and with the ability to form cohesive films. Such self-assembled films by water evaporation at ambient conditions without any chemicals but just physical entanglements between soft colloid shell, present adaptable mechanical, adhesive and mechano-electrical properties. For that, oligo(ethylene glycol)-based stimuli-responsive microgels have been synthesized using biodegradable chitosan-methacrylates (Chi-MAs) with different degree of substitution (DS) as unique cross-linking agents by precipitation polymerization in water, for the first time. In all the cases, the microgels present thermo-responsiveness with hysteresis between heating and cooling cycles. However, this behavior is tuned and controlled using different types and amounts of Chi-MAs. In addition, the type of Chi-MA used can control microgels' microstructure as well as their enzymatic biodegradation. In addition, spontaneous cohesive films formation from colloidal aqueous dispersion with sol-gel transition is demonstrated. The films present tunable mechanical and adhesive properties through microgels' microstructure and enhanced mechano-electrical properties triggered by simple finger pressure (10-15 N). As self-supported films are able to encapsulate different types of active molecules, this study paves the way for suitable self-assembled microgel films for skincare applications as transdermal delivery systems.