Effect of elongation of alternating sequences on swelling behavior and large deformation properties of natural alginate gels.

The physical properties of alginate gels correlate with alginate composition. Blocks of guluronic acid (G) strongly contribute to gel formation. Recently, the role of alternating sequences in calcium-alginate gels has been elucidated. The present contribution aimed at extending the analysis already reported (Donati, I.; Holtan S.; Morch, Y. A.; Borgogna, M.; Dentini, M.; Skjak-Braek, G. Biomacromolecules 2005, 6, 1031) and al explaining some apparent mismatch of experimental data. In the present work, calcium hydrogels from different alginate samples have been analyzed by means of uniaxial compression and puncture tests to evaluate their Young's modulus and work at break. The role of long MG blocks in mechanical deformations (small and large domains) as well as in swelling experiments was investigated with natural and MG-enriched (AlgE4 epimerized) alginate samples. Alginates with elongated alternating sequences displayed, upon treatment with saline solution, a notable increase in swelling behavior, which was not paralleled by increased mechanical properties (Young's modulus). This behavior was traced back to the disentanglement of MG/MG junctions which increased the local charge density, reducing the osmotic contribution to hydrogel swelling. The analyses of the large deformation curves for natural and epimerized alginates revealed an increase in the energy tc breakage in the latter case caused by the dissipation effect of "sliding" MG/MG junctions.