Abstract
Fractionated samples of (1 --> 3),(1 --> 4)-beta-D-glucans from oat
aleurone ('oat bran') with a relatively narrow molecular weight distribution
were characterized by total intensity light scattering. Typical Zimm
plots showed that for each concentration the angular dependence could
be fitted with a straight line. For each angle, however, the concentration
dependence showed a distinctive curvature and the negative second
virial coefficient typical of a reversibly aggregating system. The
shape of the Zimm plots was the same at increased temperature (60-degrees-C)
in different solvents (1 mol/dm3 aqueous LiI, 4 mol/dm3 aqueous urea
and dimethylsulfoxide) and after ultracentrifugation (300 000 g for
4 h). The extrapolated data at zero concentration and zero angle
nevertheless yielded weight average molecular weights (M(w)) in the
same range as the osmometric number average molecular weights (M(n))
determined previously. The relationship between the root-mean-square
z-average radius of gyration (R(g)) and M(w) was found to be R(g)
(nm) = 0.03 x M(w)0.59 in good accord with expectation from polysaccharides
of similar structure and consistent with earlier realistic molecular
modeling of these beta-D-glucans. A cooperative, closed association
model is described, and it is shown that the apparent M(w) obtained
at different concentrations from the light scattering data at zero
angle can be closely fitted with the M(w) calculated from the model,
assuming that multimers consisting of 4-5 unimers are formed. This
model predicts-in contrast to experimental observation-a strongly
negative osmotic second virial coefficient. A refined aggregation
model in which only a fraction of the unimers are assumed capable
of involvement in association to form large, cooperatively stabilized
aggregates fits both the present light scattering and the earlier
osmotic pressure data quite satisfactorily.
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