Silver release from nanocomposite Ag/alginate hydrogels in the presence of chloride ions: experimental results and mathematical modeling

A stepwise experimental and mathematical modeling approach was used to assess silver release from nanocomposite Ag/alginate microbeads in wet and dried forms into water and into normal saline solution chosen as a simplified model for certain biological fluids (e.g., blood plasma, wound exudates, sweat, etc). Three phenomena were connected and mathematically described: diffusion of silver nanoparticles (AgNPs) within the alginate hydrogel, AgNP oxidation/dissolution and reaction with chloride ions, and diffusion of the resultant silver-chloride species. Mathematical modeling results agreed well with the experimental data with the AgNP diffusion coefficient estimated as 1.3 × 10⁻¹⁸ m² s⁻¹, while the first-order kinetic rate constant of AgNP oxidation/dissolution and diffusivity of silver-chloride species were shown to be inversely related. In specific, rapid rehydration and swelling of dry Ag/alginate microbeads induced fast AgNP oxidation/dissolution reaction with Cl⁻ and AgCl precipitation within the microbeads with the lowest diffusivity of silver-chloride species compared to wet microbeads in normal saline. The proposed mathematical model provided an insight into the phenomena related to silver release from nanocomposite Ca-alginate hydrogels relevant for use of antimicrobial devices and established, at the same time, a basis for further in-depth studies of AgNP interactions in hydrogels in the presence of chloride ions.