Expansion of Ion Effects on Water Induced by a High Hydrophilic Surface of a Polymer Network

The spatial extent and anion-cation cooperativity of the ion effect on the structure and dynamics of water have long been debated but are still controversial. Previously, we experimentally demonstrated the extensive and cooperative effect of ions on water in a polyamide network by measuring the reflection wavelength (λ) on the ion sensor of poly(N-isopropylacrylamide) (PNIPAAm) hydrogel-immobilized photonic crystals. In the present study, we investigated the influence of the polymer surface on the ion effect by adopting a highly hydrophilic poly(N-isopropylacrylamide-co-N-acryloylaza-18-crown-6) hydrogel as a sensor matrix. In alkaline earth metal salt solutions, the copolymer hydrogel membrane sensor showed the redshift of λ for the specific combination of cations and anions, that is, Ca²⁺/Cl^- and Sr²⁺/NO₃^-, which resulted from the concerted binding of ion pairs to the copolymer receptor. In alkali metal salt solutions, the ion sensor showed the blueshift of λ originating from the osmotic dehydration suppressed by the salts. The strength of the ion effect was evaluated by the average osmotic pressure (Π_A) required for the salt-inhibited dehydration in the early stage of hydrogel contraction. From the calculation results of Π_A for the copolymer and PNIPAAm hydrogels, it was found that the high hydrophilic copolymer surface more significantly enhanced the ion effect of structure-making cations (i.e., Li⁺) compared with borderline (Na⁺) and structure-breaking (K⁺ and Cs⁺) cations. Furthermore, the ion effect exhibited the higher ion cooperativity in combination with chloride anions than with nitrate anions. The enhancement of the long-range cooperative ion effect is derived from the expansion of the interactions between ions, water molecules, and the hydrophilic polymer network.