Nanostructured 3D‐Printed Hybrid Scaffold Accelerates Bone Regeneration by Photointegrating Nanohydroxyapatite

Nanostructured biomaterials that replicate natural bone architecture are expected to facilitate bone regeneration. Here, nanohydroxyapatite (nHAp) with vinyl surface modification is acquired by silicon‐based coupling agent and photointegrated with methacrylic anhydride‐modified gelatin to manufacture a chemically integrated 3D‐printed hybrid bone scaffold (75.6 wt% solid content). This nanostructured procedure significantly increases its storage modulus by 19.43‐fold (79.2 kPa) to construct a more stable mechanical structure. Furthermore, biofunctional hydrogel with biomimetic extracellular matrix is anchored onto the filament of 3D‐printed hybrid scaffold (HGel‐g‐nHAp) by polyphenol‐mediated multiple chemical reactions, which contributes to initiate early osteogenesis and angiogenesis by recruiting endogenous stem cells in situ. Significant ectopic mineral deposition is also observed in subcutaneously implanted nude mice with storage modulus enhancement of 25.3‐fold after 30 days. Meanwhile, HGel‐g‐nHAp realizes substantial bone reconstruction in the rabbit cranial defect model, achieving 61.3% breaking load strength and 73.1% bone volume fractions in comparison to natural cranium 15 weeks after implantation. This optical integration strategy of vinyl modified nHAp provides a prospective structural design for regenerative 3D‐printed bone scaffold.