Trifunctional Microgel-Mediated Preparation and Toughening of Printable High-Performance Chitosan Hydrogels for...

Natural and biocompatible chitosan has demonstrated wide applications. However, rapidly fabricating high-performance chitosan hydrogels in one-step controllable processes is still a challenge for some advanced applications. Here, we report a trifunctional microgel-mediated photochemical (TMMP) strategy to achieve the fabrication of printable tough chitosan-based hydrogels (PTCHs) in seconds. Such microgels help the slow release of persulfate anions and their uniform dispersion in an aqueous solution of cationic chitosan. The released persulfates are available for preparing multiple networks of phenolic coupling of modified chitosan and radical polymerization of Pluronic F127 via orthogonal tris(bipyridine)ruthenium(II)-based photochemistry, respectively. Trifunctional microgels have reversible Ca²⁺-crosslinked networks that further improve the hydrogels' mechanical properties and toughness. The maximum stress and toughness increase by >20 folds compared to the chitosan and F127 hydrogels with single network structures. Moreover, these microgels enable the precursor to have a good shearing-thinning property and benefit the controllable preparation of PTCHs in a short time, as low as ∼4 s under visible light irradiation. It, therefore, is compatible with standard printing techniques to make complex structures. Strain sensors based on structured PTCHs have stable mechanical and responsive properties in the water, which are applied for real-time underwater communications (<0.4 s). It is anticipated that this one-step TMMP strategy opens new horizons for designing advanced chitosan hydrogels.