New approaches to the visualization, quantification and explanation of acid-induced water loss from Ca-alginate hydrogel beads

The water loss of Ca-alginate hydrogels at pHs below 4.0 was visualized with 1HNMR-imaging by covering a single alginate bead with cyclohexane-d12 in a specially equipped NMR-tube and adding propionic acid at defined concentrations. The exact amount of water expelled from the beads was calculated from their weight loss and correlated with the acid concentrations and pHs within the hydrogel matrix. The maximum water loss of 52% (w w) occurred at pH 1.0, while only 5% (w w) of the initial water content were lost at pH 3.6. The analysis of the water collected from several alginate beads for Ca2+-ions and free polysaccharides led to the assumption that, due to the acid-induced protonation of the carboxyl functions, the ionotropic network is gradually converted to an alginic acid gel structured by H-bonds. This contradicts existing theories explaining the pH-induced water loss by a lower solubility of the alginate chains and decreased repulsion between protonated carboxyl functions, but explains previously reported pH-dependent alterations of mass transport and drug retention of Ca-alginate gels. Thus, the presented experiments enable a more precise and complete view of the acid-induced process within Ca-alginate hydrogels. The transfer to the characterization of other hydrogels is possible and should be advantageous, especially if a calibration of the NMR-measurement could be achieved.