The effect of valence on the ion-exchange process: theoretical and experimental aspects on compound binding/release.

The effect of valence of mobile counter-ions (extracting electrolytes), mobile co-ions, and drug-like compounds was evaluated on drug binding/release in ion-exchange fibers. The experimental results support the Donnan theory and suggest that incorporation of monovalent salicylic acid (SA) and divalent 5-hydroxyisophthalic acid (di-COOH) into the anion-exchange fibers was attained mainly as a result of electrostatic (ionic) interaction, with additional contribution of non-electrostatic interactions. Increasing the capacity of ion-exchanger increased the molar amount of compound loading. More efficient release of model anions was observed at increasing valence or concentration of the extracting counter-ion. Potency to release the compounds decreased in the order of citrate (-3) > sulfate (-2) > chloride (-1). The valence of co-ions (sodium (+1) vs. calcium (+2)) in the external solution had only a slight effect on the release. Due to dual site binding (two ionized carboxylate groups), the amount of di-COOH bound into the fibers was half of that of monovalent SA. Also the release was significantly reduced, as the electrostatic interaction was stronger in the case of divalent compound. Simulations on the effect of valence on the Donnan potential and theoretical modeling of the release efficiencies by the external ions supported successfully the conclusions above.

Effect of ion-exchange fiber structure on the binding and release of model salicylates.

Salicylates were used as model anions to evaluate the effect of the structure (framework and ion-exchange groups) of fibrous anion-exchangers on the extent and mechanism(s) of compound binding and release. Binding was affected by the physicochemical properties of both the salicylates and the ion-exchange fibers. The highest molar amount of binding was obtained with the most lipophilic salicylate (5-chlorosalicylic acid) and the weak base (vinylpyridine) anion-exchange fibers. However, when the ion-exchange capacity was taken into account, higher binding was obtained in fibers of poly(ethylene) framework compared to the viscose-based fibers. The extent of salicylate release into NaCl solution(s) was dependent on the physicochemical characteristics of both the fiber and the bound model salicylate as well as on the amount of extracting ions. With strong base fibers (trimethylammonium), the viscose framework released the salicylates more efficiently than the poly(ethylene) framework. In the case of weak base fibers, the poly(ethylene) framework released the salicylates to a higher extent than the viscose framework. Calculated equilibrium constants (K) of the ion-exchange reactions illustrated that in addition to electrostatic interactions (pure ion-exchange mechanism), non-electrostatic interactions (hydrophobic interactions and/or hydrogen bonding) were also involved. However, the release of the salicylates was efficiently modified by the amount of extracting electrolyte, demonstrating that ion-exchange was the prevalent release mechanism.