Water mobility and structure in poly[2-hydroxyethylmethacrylate] hydrogels by means of the pulsed field gradient NMR technique.

The translational mobility of water in poly[2-hydroxyethylmethacrylate] (pHEMA) hydrogels, cross-linked with ethyleneglycoldimethacrylate, was studied by means of the pulsed field gradient (PFG) nuclear magnetic resonance (NMR) technique, which offers the opportunity to study the molecular displacements directly under well-defined equilibrium conditions, resulting in a determination of the self-diffusion coefficient. It is possible to check whether coexisting water phases with different mobilities (on a timescale of ca. 10 ms) are present. The dependence of the diffusion coefficient of water on the degree of hydration and the cross-linker concentration was measured. Magnetic interaction is found to cause cross-relaxation between the protons of water and those of the polymer matrix. This affects the data, rendering the evaluation by the standard equation invalid. An equation taking cross-relaxation into account has been derived. Amplitude measurements have shown that all the water in the gels contributes to the NMR signal. The PFG measurements have shown that the total water phase in a gel diffuses as one homogeneous phase, which can be characterized by a diffusion coefficient. The self-diffusion coefficient is strongly dependent on the degree of hydration of the gel; the cross-linker concentration has no measurable effect. The strong dependence of the diffusion of water on its concentration in the gel has consequences for the modelling of the swelling and drug-release dynamics of pHEMA and necessitates a revision of the present models describing these processes.

Physico-chemical properties of aqueous solutions of xanthan: an n.m.r. study.

The conformations of xanthan in aqueous solution as a function of temperature have been studied. Measurements of optical activity indicate that the conformational transition, induced by varying the polymer concentration, is analogous to that induced by changes in ionic strength and pH. Within a certain range of concentrations, the low-temperature conformation has a molecular-weight-dependent stability, which shows the usual sigmoidal melting profile with increase in temperature. The 13C-n.m.r. data reflect the increase of the mobility of C-1 and the side-chain carbon atoms in the transition-temperature region. The 23Na relaxation behaviour changes on melting the ordered xanthan conformation. At least two correlation times are needed in order to describe the field-strength dependence of the longitudinal and transverse 23Na relaxation. At 25 degrees, a value of 6.8 ns is obtained for the largest correlation time for the fluctuation of the electric-field gradient. The high-temperature conformation also generates correlation times of the order of ns. From 17O relaxation measurements, a reduction of the mobility of water molecules in the presence of xanthan chains is also observed.

Counter-ion dynamics in crosslinked poly(styrene sulfonate) systems studied by NMR.

The field dependence of the longitudinal and transverse nuclear magnetic relaxation rates of 23Na+ in aqueous crosslinked Na-poly(styrene sulfonate) (PSS) systems (ion exchange resins) has been obtained as a function of the degree of crosslinking. The relaxation is considerably enhanced relative to solutions of non-crosslinked NaPSS at equal ionizable group concentration. This is due to the dynamic constraints of the polymer chains, which render the averaging of the counter-ion chain interaction less efficient. The field dependence of the relaxation rates in the crosslinked NaPSS systems reveals two processes that are out of the extreme narrowing limit. This is in contrast to the relaxation behavior found in non-crosslinked NaPSS systems. To characterize these processes their correlation times were combined with constants of selfdiffusion to estimate the distances diffused by an ion in order to average the electric field gradient at its nucleus. These two distances are interpreted as characteristic length scales in the network. At all degrees of crosslinking it was found that the smallest of these length scales is roughly equal to the distance between two neighbouring crosslinks. The largest characteristic distance extends over several crosslinks and reflects inhomogeneities in the crosslink concentration. These conclusions were also reached from similar experiments on 7Li+ in LiPSS systems.

Nuclear magnetic relaxation of water in hydrogels.

Nuclear magnetic relaxation was used to investigate the dynamic behaviour of water molecules in p(HEMA) gels. Results indicate that the rotational mobility of water in p(HEMA) gels is significantly reduced compared to that in pure water. The rotational mobility was mainly determined by total degree of swelling of the gels, and not by cross-linker content. No indications were found for the presence of dynamically different types of water in these gels on a timescale of milliseconds.