Water Properties in a Novel Thermoswelling Poly(vinyl alcohol) Derivative Hydrogel as Studied by Nuclear Magnetic Resonance and Fourier Transform Infrared Spectroscopy

Water properties in a novel thermoswelling hydrogel, which was prepared from poly(vinyl alcohol)-trimellitate (PVA-T) by a simple chemical cross-linking and swollen in 0.1-1.0 M Li(2)SO(4) solutions, were investigated through nuclear magnetic resonance and Fourier transform infrared (FTIR) spectroscopies. The spin-spin relaxation of the water proton in the hydrogel was measured at 5-35 degrees C, and the results were analyzed with a two-component model to obtain a long T(2) and a short T(2) as well as their fractions (f(short) = 1 - f(long)). The f(short) values thus obtained proved to be a linear function of the gel swelling ratio, and all of the data, except for an upper deviation at 1.0 M Li(2)SO(4), were found to be on an almost same line irrespective of the temperature and the salt concentration. This dependency of f(short), on the swelling degree strongly suggests that the temperature increment has an equivalent effect as that of the SO(4)(2-) concentration; namely, scission of inter(intra-)molecular hydrogen bonding (H B) between the COOHs on the side group must be responsible for the observed thermoswelling in the sulfate salt solutions. The upper deviation of f(short) at 1.0 M from the master line was reasonably interpreted in terms of the salting-out effect by the concentrated sulfate anion. On the other hand, attenuated total reflection-FTIR measurements for a gel plate revealed that an appreciable dissociation of the carboxyl group occurred only in the 1.0 M Li(2)SO(4) system. This finding, in turn, means that gel swelling with an increase in the salt concentration up to 0.5 M is not caused by the ionization of the gel and supports the scission of the intermolecular HB. Hydrophobic hydration around the main chain was investigated via a peak shift of the stretching vibration of -CH(2)- and the slight red shift observed only at 1.0 M suggested that the salting-out effect onto the hydrophobic hydration is rather limited and the hydration around the main chain still remained even with the significant deswelling at 1.0 M.