Contact Ion Pairs in the Bulk Affect Anion Interactions with Poly(N-isopropylacrylamide)

Salt effects on the solubility of uncharged polymers in aqueous solutions are usually dominated by anions, while the role of the cation with which they are paired is often ignored. In this study, we examine the influence of three aqueous metal iodide salt solutions (LiI, NaI, and CsI) on the phase transition temperature of poly(N-isopropylacrylamide) (PNIPAM) by measuring the turbidity change of the solutions. Weakly hydrated anions, such as iodide, are known to interact with the polymer and thereby lead to salting-in behavior at low salt concentration followed by salting-out behavior at higher salt concentration. When varying the cation type, an unexpected salting-out trend is observed at higher salt concentrations, Cs⁺ > Na⁺ > Li⁺. Using molecular dynamics simulations, it is demonstrated that this originates from contact ion pair formation in the bulk solution, which introduces a competition for iodide ions between the polymer and cations. The weakly hydrated cation, Cs⁺, forms contact ion pairs with I^- in the bulk solution, leading to depletion of CsI from the polymer-water interface. Microscopically, this is correlated with the repulsion of iodide ions from the amide moiety.