Biocompatible and bioactive scaffolds with multiscale porosity, shape memory effect and drug delivery performance are highly promising in bone tissue engineering applications within the approach of minimally invasive surgical implantation. In this study, we report an effective method to fabricate multiscale porous bioactive (MPB) scaffolds with shape memory effect by freeze drying of 3D printed high internal phase Pickering emulsion (Pickering HIPE) templates stabilized by hydrophobically modified hydroxyapatite and silica nanoparticles. MPB scaffolds containing a shape memory polymer matrix of poly(D,L-lactideco-trimethylene carbonate) display high porosity and fully interconnected filament networks with multiscale pore structures. The in vitro biomineralization study verifies that MPB scaffolds are bioactive with the apatite formation ability. The thermal property testing shows that the glass transition temperature of MPB scaffolds is easily tuned to fall between 45.9 and 49.1°C by varying the HIPE composition. Moreover, MPB scaffolds exhibit observable shape memory properties with fast shape recovery. The antibacterial drug enrofloxacin can be efficiently loaded into MPB scaffolds and then released in a sustained manner displaying effective antimicrobial effect. Furthermore, cell culture assays confirm that MPB scaffolds could sustain the cell growth, proliferation and osteogenic differentiation, indicating the cytocompatibility and osteoinduction activity of MPB scaffolds. Therefore, combining freeze drying with 3D printing Handling Editor: Annela M. Seddon.

In this work, the near‐infrared (NIR) light‐responsive shape memory scaffolds with hierarchical porous structures are designed and facilely formed by freeze drying of 3D printed viscous gel‐like pickering emulsions, which are stabilized by hydrophobically modified graphene oxide (g‐GO) and silica nanoparticles, and contain thermo‐responsive poly(d, l‐lactic acid‐co‐trimethylene carbonate) (PLMC) in the oil phase. The prepared scaffolds display an interconnected filament structure with hierarchical pores and high porosity. The incorporation of g‐GO nanoparticles into PLMC matrix prompts that the scaffold shape memory can be triggered by NIR light with fast shape recovery. Moreover, the in vitro mineralization experiment shows that the scaffolds have biological activity, and the drug release study demonstrates that the scaffolds can be used as drug carriers with efficient drug release capacity. Furthermore, cell culture assays based on mouse bone mesenchymal stem cells exhibit that the scaffolds own good cytocompatibility. Therefore, the facile preparation and remote activation of the shape memory nanocomposite scaffolds with hierarchical porous structure and multifunctionality represents a highly attractive candidate as minimally invasive implantation scaffolds for bone tissue engineering applications.

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