Ice-templating of Chitosan/agarose Porous Composite Hydrogel with Adjustable Water-sensitive Shape Memory Property and Multi-staged Degradation Performance

Water-induced shape memory polymers (SMPs) may have important applications in the fields of tissue engineering and biomedicine. However, most of the ideal candidates often suffer from non-biodegradation, weak mechanical strength and random macro-porous structure, which do limit the creativity and dynamism of water-sensitive SPMs. To address above issue, in this study, by incorporating the pH-responsive chitosan (CHIT) into a thermoplastic elastomer agarose (Agar) matrix and ice-templating, a novel dual-responsive interpenetrating polymer network hydrogel with highly porous structure was facilely prepared, which has a ultra-high porosity (>95 %) and water-induced shape recovery ratio (>90 %, response time <1 min). Results showed that such shape memory property is erasable and pH-dependent which achieves a great shape memory property at high pH and then can be erased in acidic condition. In vitro dissolution test indicates the great possibility of programming the multi-staged degradation of such composites in response to sequential pH or thermal stimuli. Based on the porous internal structure, we also demonstrate some potential applications of the hydrogels for assembly of nanomaterials, such as Au nanorods for remote sensing system and model protein of insulin for drug controlled release. Moreover, the process proved to be versatile, allowing the use of most natural polymer including gelatin, alginate, and so on. Thus, coupling of such straightforward fabrication approach, multifunctionality and biodegradable prerequisite feature indicates great potential for use in the minimally invasive surgery.