Specific Anion Effects on Charged-Neutral Random Copolymers: Interplay between Different Anion-Polymer Interactions.

The study of ion specificities of charged-neutral random copolymers is of great importance for understanding specific ion effects on natural macromolecules. In the present work, we have investigated the specific anion effects on the thermoresponsive behavior of poly([2-(methacryloyloxy)ethyl trimethylammonium chloride]-co-N-isopropylacrylamide) [P(METAC-co-NIPAM)] random copolymers. Our study demonstrates that the anion specificities of the P(METAC-co-NIPAM) copolymers are dependent on their chemical compositions. The specific anion effects on the copolymers with high mole fractions of poly(N-isopropylacrylamide) (PNIPAM) are similar to those on the PNIPAM homopolymer. As the mole fraction of PNIPAM decreases to a certain value, a V-shaped anion series can be observed in terms of the anion-specific cloud point temperature of the copolymer, as induced by the interplay between different anion-polymer interactions. Our study also suggests that both the direct and the indirect anion-polymer interactions contribute to the anion specificities of the copolymers. This work would improve our understanding of the relationship between the ion specificities and the ion-macromolecule interactions for naturally occurring macromolecules.