A Biodegradable Chitosan-Polyurethane Cryogel with Switchable Shape Memory

Cryogels are matrices that are formed in moderately frozen solutions of monomeric or polymeric precursors. They have the advantages of interconnected macropores, structural stability, and compressibility. Meanwhile, thermally induced shape memory is an attractive feature of certain functional materials. Although there have been several studies concerning shape-memory cryogels, little work has been conducted on shape-memory cryogels with biodegradability. In this study, a water-based biodegradable difunctional polyurethane with a shape-memory property was synthesized and used as the nanoparticulate crosslinker to react with chitosan to form a shape-memory cryogel. The thermally induced shape-memory mechanism was clarified using in situ wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) during the shape-memory process. The in situ WAXS showed the changes of crystallinity in the crosslinker and the cryogel during the shape fixation and recovery processes. The in situ SAXS revealed the orientation of crystallinity of the crosslinker and the cryogel as the mechanism for shape memory. The strip-shape cryogel was deformed at 50 °C to U-shape and fixed at - 20 °C, which was squeezable at 25 °C and returned to the strip-shape at 50 °C in air. The shape recovery was further tested in water at two different temperatures. The injected cryogel recovered the U-shape in 4 °C water, representing elastic recovery, and transformed to a long strip in 37 °C water, representing the switchable shape memory. Moreover, the shape-memory cryogel sheet with a large dimension (10 mm × 10 mm × 1.1 mm cryogel sheet) or with complex structures (N, T, and U shapes) could be fixed as a rod, injected through a 16 G needle, and return to its original shape in 37 °C water, all of which could not be achieved by the conventional cryogel. Human mesenchymal stem cells grown in the shape-memory cryogel scaffolds displayed long-term proliferation and chondrogenic potential. Their unique injectability and cytocompatibility suggested potential applications of shape-memory cryogels as injectable and expandable templates for tissue engineering and minimally invasive surgery.