Hydration‐mediated effects of saccharide stereochemistry on poly(N‐isopropylacrylamide) gel swelling

To shed new light on the mechanisms of saccharide stereochemistry effect on macromolecules in aqueous solutions, we studied the effect of three monosaccharide stereoisomers, glucose, galactose, and mannose, on the swelling of Poly(N‐isopropylacrylamide) (PNIPA) hydrogels. We equilibrated PNIPA hydrogels in sugar solutions of different concentrations at 25 °C, and determined gel volume and mass swelling ratios, and sugar concentration imbalance. The volume‐phase‐transition occurred at molal concentrations of 0.587 ± 0.004 (galactose), 0.724 ± 0.003 (glucose), and 0.846 ± 0.004 (mannose). The same order of sugars emerged for the gel‐swelling and the magnitude of the sugar concentration‐imbalance, which correlated with sugar isentropic molar compressibility and hydration number. The more hydrated the sugar, the worse a cosolvent it is for the polymer, hence the larger the deswelling and the more negative the sugar concentration imbalance. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011