Multifunctional Shape-Memory Polyurethane/MnO₂ Composites for Postsurgical Osteosarcoma Adaptive Treatment

Treatment of postsurgical osteosarcoma remains one of the major challenges in orthopedic clinics. Conventional implants often fail to address complex pathological issues, including irregular bone defects, residual tumor cells, and delayed bone regeneration. Herein, this study reports a multifunctional shape-memory polyurethane (SMPU)/manganese dioxide (MnO₂) composite that provides adaptive support, antitumor activity, and osteogenic bioactivity. SMPU was synthesized by introducing 1,4-butanediol (BDO) and dimethylolpropionic acid (DMPA) as chain extenders at a specific ratio. Commercial MnO₂ nanoparticles were incorporated as both a photothermal agent and a bioactive component to achieve multifunctionality. As designed, a coordination system was formed between the polymer chains and MnO₂ nanoparticles within the composites. The influence of MnO₂ content was systematically investigated. Although increasing MnO₂ amounts improved photothermal and mechanical performance, excessive incorporation adversely affected the molecular structure and compromised the composite's biocompatibility. By adjusting the MnO₂ content, the composites were demonstrated to possess robust mechanical performance, good shape-memory behavior, and controllable Mn²⁺ release. Additionally, the composites exhibited tunable photothermal performance under near-infrared (NIR) irradiation. Furthermore, in vitro studies confirmed that the composites containing 4 wt% MnO₂ could eliminate tumor cells via photothermal effects and promote the osteogenic differentiation of human bone marrow-derived mesenchymal stem cells (hBMSCs). Overall, the SMPU/MnO₂ composites had superior multifunction for treating irregular bone defects following bone tumor surgery.