Biomimetic layer-by-layer templates for calcium phosphate biomineralization.

Carboxylated, sulfated and/or phosphorylated surfaces are admitted as potential optimal templates for biomimetic deposition of calcium phosphate (CaP) coatings in view of improving implants' osseointegration. Layer-by-layer films were built up consisting of anionic chondroitin sulfate (ChS), a biological carboxylated and sulfated polysaccharide and cationic poly(l-lysine) (PLL). The films were used as soft matrices to immobilize a model phosphoprotein, phosvitin (PhV). The respective roles of ChS, PLL and PhV terminal layers on the heterogeneous nucleation kinetics and the structure of CaP deposits obtained from supersaturated solutions were inspected. Critical supersaturation ratios and induction times preceding heterogeneous nucleation were precisely determined and interpreted within the framework of classical nucleation theory in order to derive the effective interfacial energies of CaP crystals. It was found that the potency of terminal layers toward CaP nucleation increased in the order: PLL<ChS<PhV. Beyond a supersaturation threshold, PhV-terminated films exerted unique influence on the nucleation kinetics, maintaining the induction time at a constant value owing to conformational change of the PhV molecules upon calcium bridging. Promisingly, all films templated the deposition of thin (a few micrometer thick) uniform coatings of octacalcium phosphate and possibly hydroxyapatite, the two most relevant biological phases of CaP.