We report the development and characterization of boron‐releasing highly porous three‐dimensional bioactive glass ( BG ) scaffolds fabricated by the foam replica technique. Three types of bioactive glasses with (wt%) 0.2%, 12.5%, 25% B ₂ O ₃ , and related varying SiO ₂ contents (wt%): 50%, 37.5%, and 25%, were investigated. The well‐known 13‐93 (silicate) and 13‐93B3 (borate) (in wt% – 56.6% B ₂ O ₃ , 5.5% Na ₂ O, 11.1% K ₂ O, 4.6% MgO, 18.5% CaO, 3.7% P ₂ O ₅ ) BG s were used as controls to study the influence of the presence of boron on the mechanical properties, surface reactivity, and cytotoxicity of scaffolds. Surface morphology and surface properties of the BG scaffolds were measured. X‐ray diffraction ( XRD ) analyses showed that the scaffolds of all five compositions were amorphous. The scaffolds with 12.5 wt% B ₂ O ₃ exhibited satisfactory compressive strength in the range of 1–2 MPa. A dissolution study in cell culture medium was carried out, and ion release profiles, and apatite formation of the scaffolds were assessed. The cytotoxicity of the scaffolds was evaluated using a stromal cell line ( ST 2). Cells were found to attach and spread well on the scaffolds' surfaces. We conclude that borosilicate scaffolds containing 12.5 wt% B ₂ O ₃ provide the best combination of properties, including relatively high mechanical strength, apatite formation, and cytocompatibility, and thus, they are promising candidates for bone tissue engineering.

The efficient healing of critical-sized bone defects using synthetic biomaterial-based strategies is promising but remains challenging as it requires the development of biomaterials that combine a 3D porous architecture and a robust biological activity. Bioactive glasses (BGs) are attractive candidates as they stimulate a biological response that favors osteogenesis and vascularization, but amorphous 3D porous BGs are difficult to produce because conventional compositions crystallize during processing. Here, we rationally designed a porous, strontium-releasing, bioactive glass-based scaffold (pSrBG) whose composition was tailored to deliver strontium and whose properties were optimized to retain an amorphous phase, induce tissue infiltration and encourage bone formation. The hypothesis was that it would allow the repair of a critical-sized defect in an ovine model with newly-formed bone exhibiting physiological matrix composition and structural architecture. Histological and histomorphometric analyses combined with indentation testing showed pSrBG encouraged near perfect bone-to-material contact and the formation of well-organized lamellar bone. Analysis of bone quality by a combination of Raman spectral imaging, small-angle X-ray scattering, X-ray fluorescence and focused ion beam-scanning electron microscopy demonstrated that the repaired tissue was akin to that of normal, healthy bone, and incorporated small amounts of strontium in the newly formed bone mineral. These data show the potential of pSrBG to induce an efficient repair of critical-sized bone defects and establish the importance of thorough multi-scale characterization in assessing biomaterial outcomes in large animal models.

Conventional composites often do not represent true synergy of their constituent materials. This is particularly evident in biomaterial applications where devices must interact with cells, resist cyclic loads and biodegrade safely. Here we propose a new hybrid system, with co-networks of organic and inorganic components, resulting in unprecedented mechanical properties, including “bouncy” elasticity and intrinsic ability to self-heal autonomously. They are also developed as new ‘inks’ that can be directly 3D printed. A hybrid is different from a nanocomposite because the components are indistinguishable from each other at the nanoscale and above. The properties are generated by a novel methodology that combines in situ cationic ring-opening polymerisation with sol–gel, creating silica/poly(tetrahydrofuran)/poly(ε-caprolactone) hybrids with molecular scale interactions and covalent links. Cartilage is notoriously difficult to repair and synthetic biomaterials have yet to mimic it closely. We show that 3D printed hybrid scaffolds with pore channels of ∼200 μm mimic the compressive behaviour of cartilage and provoke chondrocytes to produce markers integral to articular cartilage-like matrix. The synthesis method can be applied to different organic sources, leading to a new class of hybrid materials.

We report that 3-D printed scaffold channel size can direct bone marrow derived stem cell differentiation. Treatment of articular cartilage trauma injuries, such as microfracture surgery, have limited success because durability is limited as fibrocartilage forms. A scaffold-assisted approach, combining microfracture with biomaterials has potential if the scaffold can promote articular cartilage production and share load with cartilage. Here, we investigated human bone marrow derived stromal cell (hBMSC) differentiation in vitro in 3-D printed silica/poly(tetrahydrofuran)/poly(ε-caprolactone) hybrid scaffolds with specific channel sizes. Channel widths of ∼230 μm (210 ± 22 μm mean strut size, 42.4 ± 3.9% porosity) provoked hBMSC differentiation down a chondrogenic path, with collagen Type II matrix prevalent, indicative of hyaline cartilage. When pores were larger (∼500 μm, 229 ± 29 μm mean strut size, 63.8 ± 1.6% porosity) collagen Type I was dominant, indicating fibrocartilage. There was less matrix and voids in smaller channels (∼100 μm, 218 ± 28 μm mean strut size, 31.2 ± 2.9% porosity). Our findings suggest that a 200–250 μm pore channel width, in combination with the surface chemistry and stiffness of the scaffold, is optimal for cell–cell interactions to promote chondrogenic differentiation and enable the chondrocytes to maintain their phenotype.