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.

Magnetic-stimuli responsive hydrogels are quickly becoming a promising class of materials across numerous fields, including biomedical devices, soft robotic actuators, and wearable electronics. Hydrogels are commonly fabricated by conventional methods that limit the potential for complex architectures normally required for rapidly changing custom configurations. Rapid prototyping using 3D printing provides a solution for this. Previous work has shown successful extrusion 3D printing of magnetic hydrogels; however, extrusion-based printing is limited by nozzle resolution and ink viscosity. VAT photopolymerization offers a higher control over resolution and build-architecture. Liquid photo-resins with magnetic nanocomposites normally suffer from nanoparticle agglomeration due to local magnetic fields. In this work, we develop an optimised method for homogenously infusing up to 2 wt % superparamagnetic iron oxide nanoparticles (SPIONs) with a 10 nm diameter into a photo-resin composed of water, acrylamide and PEGDA, with improved nanoparticle homogeneity and reduced agglomeration during printing. The 3D printed starfish hydrogels exhibited high mechanical stability and robust mechanical properties with a maximum Youngs modulus of 1.8 MPa and limited shape deformation of 10% when swollen. Each individual arm of the starfish could be magnetically actuated when a remote magnetic field is applied. The starfish could grab onto a magnet with all arms when a central magnetic field was applied. Ultimately, these hydrogels retained their shape post-printing and returned to their original formation once the magnetic field had been removed. These hydrogels can be used across a wide range of applications, including soft robotics and magnetically stimulated actuators.

A novel auto-catalytic reaction that utilizes both the redox properties of nanoceria and oxidoreductase properties of glucose oxidase to graft polymers on the surface of nanoceria in an open vessel to form double network hydrogel nanocomposites.

Hydrogels have progressed from single-network materials with low mechanical integrity to double-network hydrogels (DNHGs) with tough, tunable properties. In this work, we introduce a nanocomposite structure into the first network of a DNHG. Amine-functionalized silica nanoparticles (ASNPs) were covalently cross-linked by forming amide bonds through the carboxylic groups of polyacrylic acid (PAAc) in the first network. DNHGs with varying sizes of ASNPs (50, 100, and 150 nm) and varying concentrations (2.5, 10, 20, and 40 wt %) were explored and compared to a control without a nanocomposite structure. Compressive strengths improved from 0.10 MPa for the control to a maximum of 1.28 MPa for the PAAc/PAAm DNHGs. All hydrogels experienced increased resistance to strain with a maximum of 74% compared to 45% for the control. SEM images of freeze-dried gels showed that ASNPs were integrated into the gel mesh. Nanoparticle retention was calculated using thermal gravimetric analysis (TGA) with improved retention values for larger ASNPs. New DNHG composites have been formed with improved mechanical properties and a potential use in tissue engineering and biomaterial applications.

Nanocomposite hydrogels offer remarkable potential for applications in bone tissue engineering. They are synthesized through the chemical or physical crosslinking of polymers and nanomaterials, allowing for the enhancement of their behaviour by modifying the properties and compositions of the nanomaterials involved. However, their mechanical properties require further enhancement to meet the demands of bone tissue engineering. Here, we present an approach to improve the mechanical properties of nanocomposite hydrogels by incorporating polymer grafted silica nanoparticles into a double network inspired hydrogel (gSNP Gels). The gSNP Gels were synthesised via a graft polymerization process using a redox initiator. gSNP Gels were formed by grafting 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as the first network gel followed by a sequential second network acrylamide (AAm) onto amine functionalized silica nanoparticles (ASNPs). We utilized glucose oxidase (GOx) to create an oxygen-free atmosphere during polymerization, resulting in higher polymer conversion compared to argon degassing. The gSNP Gels showed excellent compressive strengths of 13.9 ± 5.5 MPa, a strain of 69.6 ± 6.4%, and a water content of 63.4% ± 1.8. The synthesis technique demonstrates a promising approach to enhance the mechanical properties of hydrogels, which can have significant implications for bone tissue engineering and other soft tissue applications.