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The effectiveness of four different reagents, glutaraldehyde (GTA), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC), poly(ethyelene glycol) diglycidyl ether (EX 810), and divinyl sulfone (DVS) as crosslinkers for cast hyaluronic acid (HA) films has been evaluated. Films were prepared by casting from solution and exposed to solutions of the crosslinkers in acetone-water solution. Swelling in water and in phosphate buffered saline (PBS) was then used to assess the effectiveness of the crosslinkers. GTA-crosslinked films were found to be of low stability compared with those treated with EDC, EX 810, and DVS. Results suggest that instability in GTA-crosslinked materials arises in part from residual acid catalyst. The effects of polymer molecular weight are not uniform.With GTA-crosslinked film produced from higher molecular weight HA swells more, and this is attributed to reduced diffusion of the crosslinker, but with EDC, the opposite effect is observed, implying some additional molecular weight dependent mechanism. Differential scanning calorimetry and dynamic mechanical thermal analysis results suggest that there are no significant structural difference between the gels for each crosslinker system and only the crosslink density and moisture content alters the transitions.

In order to improve the mechanical properties and control the degradation rate of hyaluronic acid (HA) an investigation of the structural and mechanical properties of the hydrogels crosslinked using divinyl sulfone (DVS), glutaraldehyde (GTA) and freeze-thawing, or autocrosslinking has been carried out. The thermal and mechanical properties of the gels were characterised by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and compression tests. The solution degradation products of each system have been analysed using size exclusion chromatography (SEC) and the Zimm-Stockmayer theory applied. Autocrosslinked gels swell the most quickly, whereas the GTA crosslinked gels swell most slowly. The stability of the autocrosslinked gels improves with a reduction in solution pH, but is still poor. GTA and DVS crosslinked gels are robust and elastic when water swollen, with glass transition values around 20 degrees C. SEC results show that the water soluble degradation products of the gels show a reduction in the radius of gyration at any particular molecular weight and this is interpreted as indicating increased hydrophobicity arising from chemical modification.

Hyaluronic acid (HA) has been crosslinked in solution with glutaraldehyde (GTA), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC), poly(ethylene glycol) diglycidylether (EX 810), and divinyl sulfone (DVS) to form hydrogels. Flory-Rehner calculations were used to determine molecular weight between crosslinks (M c ), the crosslink density (V e ), and mesh size (e) of crosslinked hydrogels after 24-h swelling in distilled water. Generally, lower molecular weight films gave rise to decreased molecular weights between crosslinks as well as increased effective crosslink densities and decreased mesh size. The effects of pH and salt concentration were evaluated. Use of lower molecular weight HA gave rise to decreased molecular weights between crosslinks as well as increased effective crosslink densities and decreased mesh size. Water diffusion coefficients were measured for DVS and GTA hydrogels and were found to be 1.4 3 10 210 and 1.8 3 10 210 m 2 s 21 . Autocrosslinked and HA polyethyleneimine gels were also produced but had very limited stabilities compared with the covalently crosslinked materials.