Photocrosslinkable nanocomposite ink for printing strong, biodegradable and bioactive bone graft

Abstract

3D printing is known as a cost-effective technique that shows huge potential in fabrication of graft substitutes for bone tissue regeneration. However, the tradeoff between 3D printability, mechanical strength and bioactivity of the printed materials (i.e., inks) remains a challenge. In this work, we present a novel photocrosslinkable nanocomposite ink composed of tri-block poly (lactide-co-propylene glycol-co-lactide) dimethacrylate (PmLnDMA, m and n respectively represent the unit length of propylene glycol and lactide) and hydroxyethyl methacrylate (HEMA)-functionalized hydroxyapatite nanoparticles (nHAMA). The reactive HEMA-conjugated nHAMA, is designed to covalently crosslink with the surrounding polymer matrix to further increase the interfacial bonding between them. We find that the nHAMA can rapidly interact with PmLnDMA upon light exposure within 140 s and form an inorganic-organic co-crosslinked nanocomposite network, further enhancing the nanofiller-matrix interfacial compatibility. Notably, our nanocomposites possess significantly improved mechanical performances compared to the polymer, with compressive modulus increasing by nearly 10 times (from ⁓40 to ⁓400 MPa). Moreover, thanks to the low exothermic heat generation (<37 °C) during photocrosslinking, our nanocomposite ink enables facile encapsulation and long-term release of heat-labile biomolecules like bone morphogenic protein-2 (BMP-2). Furthermore, it demonstrates a readily tunable rheological property, wettability, degradation, and printability as a 3D bone scaffold. Together with its superior osteogenic ability both in vitro and in vivo, we envision that our nanocomposite ink holds great promise in 3D printing of bone grafts.