Effects of molecular weight and elastic segment flexibility on syneresis in Ca-alginate gels

Syneresis in Ca-alginate gels was studied as a function of the alginate molecular weight and the degree of flexibility of the elastic segments. Small angle X-ray scattering of alginate gels reveals an increased lateral association of junction zones when entering a Ca2+ regime giving syneresis. This suggests growth of junction zones to be the primary driving force for syneresis. Ca-alginate gels prepared from alginates with different molecular weights show a reduced syneresis with decreasing Mw. A reduced syneresis is also observed when fractions of a high Mw alginate is replaced by short alginate molecules enriched in guluronate residues. The effect of altering the monomer sequence of the elastic segments spanning the junction zones was studied by converting poly-mannuronate regions to alternating guluronate/mannuronate sequences by the mannuronan C5-epimerase AlgE4. This epimerisation reaction gives a more flexible elastic segment. The epimerased alginates yielded gels with larger syneresis compared to the non-epimerased, native alginate samples. Thus, both molecular weight and elastic segment flexibility are needed in a molecular model for describing syneretic behaviour in alginate gels. These parameters will to a large extent determine to which degree the non-equilibrium nature of the alginate gel is macroscopically expressed (syneresis).