Phase transition of poly(N-isopropylacrylamide) in aqueous protic ionic liquids: kosmotropic versus chaotropic anions and their interaction with water.

We have investigated the influence of a series of triethylammonium-based protic ionic liquid-water solutions on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM). We find that kosmotropic anions lower the LCST of PNIPAM more dramatically when compared with chaotropic anions. In addition, we have probed the solvent properties of the hydrated protic ionic liquid solutions using (1)H NMR, polarity measurements, and solvatochromic analysis of the Kamlet-Taft parameters, β and π*. We find that the hydrogen bond character--more specifically, the interactions between water and pIL--is the dominant parameter responsible for lowering the LCST of PNIPAM. We have added choline dihydrogen phosphate (choline dhp) into this study on the basis of positive results from previously reported protein folding studies using this ionic liquid.