Abstract
Transport of monovalent cations was studied in solutions of biological polyelectrolytes, the sodium (or potassium) salts of anionic polysaccharides ι-, κ-, λ-carrageenan, dextran sulfate, and chondroitin sulfate, by steady-state voltammetric reduction of the probe ions Tl+ and H+ at mercury film and platinum disc microelectrodes, respectively. Diffusion coefficients of the electroactive probe ion are determined rapidly and precisely from steady-state, transport-limited current at microelectrodes in solutions with large excess and without supporting electrolyte over a wide range of polyelectrolyte and probe ion concentrations. Electrostatic interactions between polysaccharide anion and probe ion decrease the value of the diffusion coefficient of the probe ion with respect to the value without the polyelectrolyte, with the most pronounced effect in solutions without electrolyte. These interactions are quantified by the transport ratio, D/D0, of the diffusion coefficient of the probe ion with polyelectrolyte...
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