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Articular cartilage is a viscoelastic tissue whose structural integrity is important in maintaining joint health. To restore the functionality of osteoarthritic joints it is vital that regenerative strategies mimic the dynamic loading response of cartilage and bone. Here, a rotating simplex model was employed to optimise the composition of agarose and gellan hydrogel constructs structured with hydroxyapatite (HA) with the aim of obtaining composites mechanically comparable to human cartilage in terms of their ability to dissipate energy. Addition of ceramic particles was found to reinforce both matrices up to a critical concentration (< 3w/v%). Beyond this, larger agglomerates were formed, as evidenced by micro computed tomography data, which acted as stress risers and reduced the ability of composites to dissipate energy demonstrated by a reduction in tan δ values. A maximum compressive modulus of 450.7±24.9 kPa was achieved with a composition of 5.8w/v% agarose and 0.5w/v% HA. Interestingly, when loaded dynamically (1-20Hz) this optimised formulation did not exhibit the highest complex modulus instead a sample with a higher concentration of mineral was identified (5.8w/v% agarose and 25w/v% HA). Thus, demonstrating the importance of examining the mechanical behaviour of biomaterials under conditions representative of physiological environments. While the complex moduli of the optimised gellan (1.0 ± 0.2MPa at 1Hz) and agarose (1.7 ± 0.2MPa at 1Hz) constructs did not match the complex moduli of healthy human cartilage samples (26.3 ± 6.5MPa at 1Hz), similar tan δ values were observed between 1 and 5Hz. This is promising since these frequencies represent the typical heel strike time of the general population. In summary, this study demonstrates the importance of considering more than just the strength of biomaterials since tissues like cartilage play a more complex role.

Alginate hydrogels are commonly used in biomedical applications such as scaffolds for tissue engineering, drug delivery, and as a medium for cell immobilization. Multivalent cations are often employed to create physical crosslinks between carboxyl and hydroxyl moieties on neighbouring polysaccharide chains, creating hydrogels with a range of mechanical properties. This work describes the manufacture and characterisation of sodium alginate hydrogels using the divalent cations Mg2+, Ca2+ and Sr2+ to promote gelation via non-covalent crosslinks. The gelation time and Young’s modulus are characterised as a function of cation and alginate concentrations. The implications of this work towards the use of environmental elasticity to control stem cell differentiation are discussed.

In order to produce hydrogel cell culture substrates that are fit for the purpose, it is important that the mechanical properties are well understood not only at the point of cell seeding but throughout the culture period. In this study the change in the mechanical properties of three biopolymer hydrogels alginate, low methoxy pectin and gellan gum have been assessed in cell culture conditions. Samples of the gels were prepared encapsulating rat bone marrow stromal cells which were then cultured in osteogenic media. Acellular samples were also prepared and incubated in standard cell culture media. The rheological properties of the gels were measured over a culture period of 28 days and it was found that the gels degraded at very different rates. The degradation occurred most rapidly in the order alginate > Low methoxy pectin > gellan gum. The ability of each hydrogel to support differentiation of bone marrow stromal cells to osteoblasts was also verified by evidence of mineral deposits in all three of the materials. These results highlight that the mechanical properties of biopolymer hydrogels can vary greatly during in vitro culture, and provide the potential of selecting hydrogel cell culture substrates with mechanical properties that are tissue specific.

The rheological properties of synovial fluid (SF) are crucial to the performance of joint prostheses. During the development of joint prostheses, wear tests are performed, which simulate joint movements in diluted solutions (usually between 25 and 33% v/v) of bovine serum which has very different rheological properties compared with native SF, where rheology is maintained by hyaluronan. Consequently, there is a need to develop a more suitable artificial SF. In this study, we used rheological techniques to understand SF flow properties which provided an insight into the mechanical behaviour required of a practical SF analogue. Steady-shear viscosity measurements were performed to reveal changes as a function of shear rate. To analyse the viscoelastic properties small deformation oscillatory measurements of storage modulus (G') loss modulus (G″) and complex viscosity ( η ⁎ ) were made. The rheological properties of the SF where compared with those of the polysaccharides sodium alginate, gellan gum and mixtures of both polymers. Initial results revealed classic shear thinning behaviour for the SF with a small Newtonian plateau at low shear rates with a gradual reduction in viscosity with increasing shear rate. Viscoelasticity measurements also showed that at low frequencies of oscillation there was a viscous response with G″ greater than G' and at higher frequencies there was an elastic response. Rheological properties were found to be similar to that of a 50:50 mix of 2% w/v high molecular weight alginate and 0.75% w/v gellan gum. Importantly, the lubricating behaviour of the serum differed significantly from the biopolymer blend over a full range of sliding velocities. The biopolymer blend was shown to lubricate the opposing surfaces more effectively. This difference was attributed to the more rapid alignment of the polysaccharide during shear when compared with the bovine albumin (the most abundant protein in serum), which typically exhibits a globular structure and has a tendency for self-association. These results suggest that polysaccharide solutions with bio-relevant rheology maybe be suitable as lubricants for in vitro orthopaedic prosthetic wear tests.

Biopolymers such as alginates have been widely researched for clinical use. Their clinical application, however, have been limited due to their unpredictable and often rapid degradation rates. Here we show that the degradation of an alginate hydrogel can be tailored through the addition of orthosilicic acid (OSA). On immersion in aqueous media a negligible quantity of orthosilicic acid was released from the gel matrix. The presence of the OSA within the gel was shown to significantly slow degradation of the alginate hydrogel when immersed in a potent calcium chelator (EDTA) when compared with the control group. Sample degradation was associated with a significant calcium release from the non-modified gel; however, the orthosilicic acid modified gel did not release detectable levels of calcium over the same period. This suggests that the orthosilicic acid inhibits degradation of the gel by forming an interaction with the calcium cross-links. A rapid reduction in the storage modulus G', was observed in alginate made without OSA, however, the G'exhibited by the orthosilicic acid modified alginate did not reduce significantly (p

Wear resistance is still perceived to be one of the most important limiting factors in the long-term performance of dental restorations. Consequently, a range of different materials have been used as filler particles to reduce the rate of wear, particularly in posterior restorations. In this study, novel bioactive glass–ceramic powders exhibiting different nominal calcium–mica to fluorapatite ratios were used as fillers for light-cured dental composites. Wear tests on the resulting samples were undertaken using a micro-tribometer with a linear reciprocating ball-on-flat geometry using lubrication from artificial saliva. The surfaces of the worn composites were then evaluated using optical microscopy. In order to enhance matrix bonding, the surfaces of the different particulates were treated using hydrofluoric acid to provide a porous surface and the resulting surface morphology was evaluated using scanning electron microscopy. Although in the case of the samples containing low fluorapatite contents (20 wt%; A2), surface etching enhanced the wear resistance of the composite, etching reduced the wear resistance of materials containing 50 wt% fluorapatite (A5). The reduction in wear resistance was attributed to the friability of the A5 particles following surface treatment. This suggests that in order to optimize wear resistance, it is important to find a critical balance between surface roughness and porosity and the strength of individual particles.