PMMA-co-calcium methacrylic phyllosilicate hybrid bone cements induce biomimetic mineralization

Poly(methyl methacrylate) (PMMA) remains a clinical standard in orthopedic procedures due to its reliable primary fixation. However, its inherent lack of bioactivity and poor osseointegration limit long-term success. While bioactive additives can improve biological response, they frequently compromise structural integrity, challenging the effective design of load-bearing implants. This study introduces calcium methacrylic phyllosilicate (CaMP) as a novel bioactive comonomer, designed to induce osteogenic activity in PMMA bone cements. Chemical characterization confirms the successful synthesis of CaMP, which is covalently incorporated into the PMMA matrix via radical copolymerization (up to 15 wt%) without compromising the structural integrity of the bone cements. Surface analysis after biomimetic mineralization reveals a significant increase in the calcium and phosphorus content on the surface of the samples, demonstrating induced calcium nucleation. Deconvolution of Raman and XPS spectra confirms the template-driven upregulation of the calcium phosphate mineralization, promoting the transition from amorphous phases into poorly crystalline apatite-like deposits. Moreover, the hybrid bone cements elicit sustained calcium release governed by Fickian diffusion, which validates the ability of the material to induce osteogenic differentiation, endogenous biomimetic mineralization, and long-term apatitic crystal maturation. Consequently, the in situ functionalization of PMMA bone cements via CaMP copolymerization provides a robust pathway for developing mechanically stable, bioactive hybrid implants for load-bearing applications.