Interactions of counterions with dextran sulfate in aqueous solutions

Counterion activity coefficients in solutions of dextran sulfate with and without added salts were determined potentiometrically by using a cation-exchange membrane and a sodium glass electrode. Dextran sulfate was shown to interact with monovalent cations in the order of preference: K⁺ > Cs⁺ > Na⁺ > Li⁺, whereas no specificity was found for bivalent cations. On the basis of light-scattering measurements, the expansion of the dextran sulfate polyion in solutions of alkali metal salts was found to fall in the same order as the counterion activity coefficients in salt-free solutions. It was also shown that the dextran sulfate polyion assumes a more extended conformation in magnesium chloride solution than in calcium chloride. These results were substantiated by measurements of solution viscosities.