Novel Heterogeneous Hydrogel with Dual-Responsive Shape Programmability and Good Biocompatibility

Shape memory polymers (SMPs) responsive to various external stimuli can realize a complex shape transformation process and have attracted extensive attention. However, integrating multiple stimulus-responsive mechanisms in one material often requires a complex molecular design and synthesis procedure. In this work, we designed a novel dual-responsive heterogeneous hydrogel (PU-PAM/Alg/PDA), which was manufactured through in situ free radical polymerization of acrylamide (AM) in the presence of alginate (Alg) and polydopamine (PDA) in a porous polycaprolactone-based polyurethane foam (PU-foam). The PU-PAM/Alg/PDA hydrogel could achieve thermal responsiveness through melting-crystallization transformation of polycaprolactone (PCL), while the metallo-supramolecular interactions between Alg and Fe³⁺ could provide ion responsiveness for this hydrogel. This dual-programmable feature endowed the heterogeneous hydrogel with a complex shape-morphing behavior and also a reconfiguration ability for the permanent shape. Meanwhile, the strong hydrogen bondings between PDA and polyurethane chains enhanced the interfacial adhesions, resulting in the structural integrity and excellent mechanical property of PU-PAM/Alg/PDA. The in vitro and in vivo tests revealed the good biocompatibility of the heterogeneous hydrogel, and the potential of the heterogeneous hydrogel as an esophageal stent was evaluated in vitro as conceptual proof.