Transport properties of some cationic polysaccharides 2. Charge density effect.

The charge density effect on the behavior of some cationic polysaccharides in aqueous and nonaqueous (methanol) solutions was studied by viscometric and conductometric measurements. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-alkyl-N,N-dimethyl-2-hydroxypropylene ammonium chloride, attached to a dextran backbone. This new class of polyelectrolytes has various linear charge density parameters, xi, located below and above the critical threshold value of counterions condensation, xi(c)=1(xi=0.25-3.18). The viscometric data revealed that all copolymers exhibit a polyelectrolyte behavior and were plotted in the terms of Rao equation. The conductometric measurements of solutions of these copolymers were presented as a function of polymer concentration and charge density. The results were analyzed within the Manning's theory and lower experimental values of the equivalent conductivity than the theoretical ones were found. Possible reasons of this discrepancy have been discussed. The interaction parameters were evaluated and these were found to depend on both the polymer concentration and the charge density. The conductometric behavior of these cationic polysaccharides has shown that counterion condensation is not a threshold phenomenon, their association to the charged groups of the polyions taking place for xi>1 as well as xi<1.