Comparative study of gelatin cryogels reinforced with hydroxyapatites with different morphologies and interfacial bonding.

Gelatin cryogels are good candidate scaffolds for tissue engineering because of their interconnected macroporous structure. For bone regeneration, inorganic components are chosen to reinforce gelatin cryogels: (i) to mimic the compositions of natural bone tissue and (ii) to meet the mechanical requirements of bone repairing. Cryogels were prepared from methacrylated gelatin (GelMA) in this study, and hydroxyapatite nanorods (HANRs) with surface-grafted acrylate groups (D-HANRs) were synthesized to reinforce the cryogels, in which, the crosslinking between GelMA and D-HANRs was expected. In parallel, HANRs and hydroxyapatite nanowires (HANWs) were also composited with the GelMA cryogels to investigate the effects of filler morphology and interfacial bonding on the overall properties of the resulting composite cryogels comparatively. All these composite cryogels demonstrated potential as bone repairing materials by displaying excellent performances such as high porosity, appropriate water retention, shape recovery, and fast resilience features, as well as good biocompatibility and cell affinity. In comparison with the HANR composited GelMA cryogel, the HANWs were able to ameliorate the compression and the rheology performances of the resulting composite cryogels more efficiently due to the fact that the one-dimensional HANWs played a bridging role in the gelatin matrix. Among all the preparations, however, it was the D-HANRs that achieved the strongest reinforcement efficiency in mechanical properties because the double bonds on their surface could be photo-crosslinked with GelMA to form interfacial bonding. With these findings, we concluded that it was preferable for inorganic fillers designed for cryogel-type bone repairing materials to be in a one-dimensional morphology with surface functional groups to strengthen their interfacial bonding with the polymeric matrix.