Hydroxyapatite–poly(l-lactide) nanohybrids via surface-initiated ATRP for improving bone-like apatite-formation abilities

It is important to improve the compatibility of hydroxyapatite (HA) nanoparticles in biodegradable polyesters to obtain desirable nanocomposites for bone tissue engineering applications. Polymer grafting has been proven an efficient way to get nanohybrids with good dispersibility in polymeric matrixes. In this paper, a new strategy to prepare HA–poly(l-lactide) (PLLA) nanohybrids was developed, where PLLA oligomers were grafted from HA nanoparticle surfaces via surface-initiated atom transfer radical polymerization (ATRP) of methylacrylate group terminated PLLA macromonomers (PLLA-MA). HA with the derived ATRP initiators was obtained by (1) preparation of HA from precursors in the presence of 3-aminopropyl-triethoxysilane (APTS) to produce the HA surface with terminal single bondNH2 groups (HA–NH2) and (2) reaction of the single bondNH2 groups of the HA–NH2 nanoparticles with 2-bromoisobutyryl bromide (BIBB) to produce the 2-bromoisobutyryl-immobilized nanoparticles (HA–Br). The obtained HA–PLLA nanohybrids demonstrated good dispersibility in chloroform. With the good dispersion of HA–PLLA nanohybrids in PLLA matrix, the resultant PLLA/HA–PLLA nanocomposites could much faster induce bone-like apatite-formation in simulated body fluids (SBF) than the PLLA/HA counterparts where the HA nanoparticles aggregated heavily. With the versatility of ATRP, properly, grafting oligomeric PLLA chains from HA nanoparticle surfaces is an effective means for the design of novel HA–polymer biohybrids for future bone tissue engineering applications.