Dual cross-linking systems of functionally photo-cross-linkable and thermoresponsive polyphosphazene hydrogels for biomedical applications.

Photo-cross-linkable, functionalized, and thermosensitive polyphosphazenes were synthesized to develop a dual cross-linking system with properties of mechanically suitable strength and controllable biodegradation for injectable biomedical applications. The aqueous solutions of the polymers exhibited sol-gel transition behaviors against temperature. The incorporated methacrylate groups were photo-cross-linked upon UV light under mild conditions, which resulted in the formation of compact three-dimensional networks. The thermoresponsive hydrophobic interactions at body temperature facilitated the rapid dual cross-linking accomplishment of the photo-cross-linking even under mild conditions. The characteristics of the polymers such as pore size and density showed that the inner three-dimensional networks depended on the degree of cross-linking of methacrylate units. Mechanical properties of the gel were also improved several folds after developing the photo-cross-linking in the network from the in vivo degradation studies. The results demonstrate that the photo-cross-linkable and thermoresponsive polyphosphazenes have great potential as injectable, biodegradable, and controllable carriers for various biomedical applications by tuning the mechanical gel property and the degradation rate.