In situ synthesis of bilayered gradient poly(vinyl alcohol)/hydroxyapatite composite hydrogel by directional freezing-thawing and electrophoresis method

Bilayered poly(vinyl alcohol) (PVA)/hydroxyapatite (HA) composite hydrogels with anisotropic and gradient mechanical properties were prepared by the combination of directional freezing-thawing (DFT) and electrophoresis method. Firstly, PVA hydrogels with aligned channel structure were prepared by the DFT method. Then, HA nanoparticles were in situ synthesized within the PVA hydrogels via electrophoresis. By controlling the time of the electrophoresis process, a bilayered gradient hydrogel containing HA particles in only half of the gel region was obtained. The PVA/HA composite hydrogel exhibited gradient mechanical strength depending on the distance to the cathode. The gradient initial tensile modulus ranging from 0.18 MPa to 0.27 MPa and the gradient initial compressive modulus from 0.33 MPa to 0.51 MPa were achieved. The binding strength of the two regions was relatively high and no apparent internal stress or defect was observed at the boundary. The two regions of the bilayered hydrogel also showed different osteoblast cell adhesion properties.