Analyzing the Water Confined in Hydrogel Using Near-Infrared Spectroscopy

Analysis of the confined water in hydrogels is essential for understanding the chemical and physical properties. Methods to quantify the content and study the structure of water in hydrogel using near-infrared (NIR) spectroscopy were proposed. The NIR spectra of poly-N,N-dimethylacrylamide (PDMAA) hydrogel with different water contents were measured at different temperatures. A partial least squares (PLS) model was established using the spectra of the samples with water content (w) from 0.9 to 387.6%. Continuous wavelet transform (CWT) was adopted to calculate the resolution enhanced spectra from which the spectral features of water species with free OH (S₀) and with one or two hydrogen bonds (S₁ and S₂) was obtained. The variation of these water species with water content suggests the existence of the water molecules bonding to NH groups by one hydrogen bond (S_1NH) and hydrating the CH groups of the polymer network and bulk-like water. Moreover, the variation of water structures with temperature shows that the release of bulk-like water occurs in the phase transition of the hydrogel, but the S_1NH and the hydration water stay unchanged. The former explains the sudden volume shrinkage for the phase transition and the latter may be the reason for the shape memory effect in the repeated swelling and deswelling of hydrogels.