Structural effects of sulfur-containing functional groups on apatite formation on Ca2+-modified copolymers in a simulated body environment

Chemical modification with specific functional groups has been the conventional method to develop bone-bonding bioactive organic–inorganic hybrids. These materials are attractive as bone substitutes because they are flexible and have a Young’s modulus similar to natural bone. Immobilization of sulfonic acid groups (−SO3H) onto the polymer chain is expected to produce such hybrids because these groups induce apatite formation in a simulated body fluid (SBF) and enhance the activity of osteoblast-like cells. Sulfinic acid groups (−SO2H), which are derivatives of −SO3H, can also induce apatite nucleation. However, the structural effects of such sulfur-containing functional groups on apatite formation have not been elucidated. In the present study, apatite formation on Ca2+-modified copolymers containing −SO2H or −SO3H was investigated in a simulated body environment. The copolymer containing Ca2+ and −SO3H promoted Ca2+ release into the SBF and formed apatite faster (1 day) than the copolymer containing Ca2+ and −SO2H (14 days). In contrast, when they were not modified with Ca2+, the copolymer containing only −SO2H deposited the apatite faster (7 days) than that containing only −SO3H (>7 days) in the solution with Ca2+ concentration 1.5 times that of SBF. The former adsorbed larger amounts of Ca2+ than the latter. The measured stability constant of the complex indicated that the interaction of −SO2–···Ca2+ was more stable than that of −SO3–···Ca2+. It was found that both the release and adsorption of Ca2+ governed by the stability played an important role in induction of the apatite formation and that the apatite-forming ability of sulfur-containing functional groups drastically changed by the coexistence of Ca2+