Article,

LIGHT-SCATTERING REVEALS MICELLE-LIKE AGGREGATION IN THE (1-3),(1-4)-BETA-D-GLUCANS FROM OAT ALEURONE

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Food Hydrocolloids, 5 (6): 497 -- 511 (February 1992)

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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