Biocompatibility improvement and controlled in vitro degradation of poly (lactic acid)-b-poly(lactide-co-caprolactone) by formation of highly oriented structure for orthopedic application.

Poly (lactic acid) (PLA) has been proposed as a promising orthopedic implant material, whereas insufficient mechanical strength, unsatisfied biocompatibility and inappropriate degradation rate restrict its further application. In this work, self-reinforced poly (lactic acid)-b-poly(lactide-co-caprolactone) (PLA-b-PLCL) block copolymer with long-chain branches was fabricated through two-stage orientation. Compared with smooth and hydrophobic PLA surface, the surface of PLA-b-PLCL presented micro-phase separated structure with improved hydrophilicity, and cells seeded on it showed improved adhesion/proliferation and high alkaline phosphatase (ALP) activity. After the 1st stage orientation at temperature higher than Tg1 (glass transition temperature of PLA phase), the amount of CH3 and CO groups on surface of PLA-b-PLCL increased, while "groove-ridge" structure formed, resulting in enhancement of surface hydrophobicity. After the 2nd stage orientation at Tg1  ~ Tg2 (glass transition temperature of PLCL phase), surface hydrophobicity/amount of CO groups further increased and "groove-ridge" structure became more significant. Due to suitable wettability and enhanced material-cell mechanical interlocking, cell proliferation/ALP activity were improved and a continuous cell layer formed on sample surface. During in vitro degradation in phosphate buffered saline solution, by introduction of PLCL segments, the crystallinity decreased and solution absorption increased, resulting in a rapid deterioration of mechanical properties. After the 1st stage orientation, a dense microfibrillar structure with high crystallinity formed, which hindered diffusion of solution and delay hydrolytic degradation. After the 2nd stage orientation, PLCL segments were arranged more closely, resulting in a further inhibition of degradation, which was helpful for controlling the strength decay rate of PLA as bone fixation materials.