Abstract
Ca-alginate gels were studied by small-angle X-ray scattering and
rheology to determine relations between chemical composition and
concentrations of the alginate and the elasticity and structure of
the gels. The gels were prepared by in situ release of Ca2+ from
either Ca-EGTA or CaCO3 with total Ca2+ concentration in the range
5-30 mM. Alginates with low (39%), intermediate (50%), and high (68%)
fractions of alpha-L-GulA originating from the brown algae Ascophyllum
nodosum, Laminaria hyperborea leaf, and Laminaria hyperborea stipe,
respectively, were employed. Two to three different degrees of polymerization
for each chemical composition were used in the experiments. The excess
small-angle X-ray scattering for the alginates in solution yielded
linear cross-sectional Guinier plots, and the cross-sectional radius
of gyration, R-g,R-c, was determined to be 3.1-4.6 Angstrom. The
SAXS profiles of the alginate gels depended on the alginate concentration,
Ca2+ concentration, and the alginate composition. The SAXS data suggested
that dimerization of chain segments was the principal association
mode at low fractional Ca2+ saturation of guluronic acid of the alginate.
Increasing the fractional Ca2+ saturation of guluronic acid, either
by the concentrations or selection of alginate source, yielded coexisting
lateral association modes, as manifested in a curvature in the cross-sectional
plots. The coexisting junction zone multiplicities occur because
of a delicate balance between the block length distribution of the
alpha-L-GulA residues, polymer concentration, and Ca2+. These results
are quantitative extensions of the "egg-box" model used to describe
ionotropic gelation of alginate and hence enhance the understanding
of the structure-function relationship of alginate gels.
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