Distinctly different solvation behaviors of poly(N,N-diethylacrylamide) gels in water/acetone and water/DMSO mixtures

The solvation behaviors and intermolecular interactions of a poly(N,N-diethylacrylamide) (PDEA) gel network in water/DMSO and water/acetone mixtures have been investigated by variable-temperature high-resolution 1H MAS NMR. Unlike decreasing volume phase transition temperature (VPTT) of the typical thermosensitive poly(N-isopropylacrylamide) (PNIPAM) gel induced by both acetone and DMSO in a water-rich region, distinct phase transition behaviors are revealed for the PDEA gel. That is, acetone is found to increase the VPTT of PDEA directly in the water-rich region while DMSO is also found to increase the VPTT of PDEA at a very low concentration but then decrease the VPTT as the concentration further increases. The above distinctly different VPTT shifts of PDEA are attributed to the different polymer-cosolvent interactions in water/acetone and water/DMSO systems. DMSO molecules with a strong water affinity are preferentially excluded by the PDEA gel network, and can promote the volume phase transition by favoring the collapse of the PDEA gel network, while acetone molecules preferentially adsorbed on the polymer interact with PDEA via non-specific van der Waals interaction, which favors the swollen state of the PDEA gel.