Advanced 1H solid-state NMR spectroscopy on hydrogels, 2 -: The formation of hydrogen bonds in hydrogels based on N-isopropylacrylamide (NiPAAm) and methacrylic acid (MAA)

Advanced H-1 solid-state NMR methods are applied for studying the hydrogen bond formation occurring in polymer hydrogels based on N-isopropylacrylamide (NIPAAm) and methacrylic acid (MAA). For P(NIPAAm-co-MAA) copolymers collapsed at low pH, two populations of water can be distinguished in H-1 magic-angle spinning (MAS) NMR spectra, one of which is probably situated near stable hydrogen-bonded regions, while the other behaves similarly to free water. The pH-induced polymer collapse can be followed in detail using 2D H-1-H-1 double quantum (DQ) MAS NMR experiments on dried samples. For collapsed copolymers as well as interpenetrating polymer networks, the appearance of characteristic signals shows that hydrogen bonding takes place between NIPAAm and MMA monomers. The temperature dependence of the DQ spectra indicates that acid-an-fide hydrogen bonds formed between both comonomers are more stable than the acid-acid hydrogen bonds formed among MAA moieties alone. Correspondingly, by analyzing H-1-H-1 DQ sideband patterns, a relatively short distance of 270 pm is found for the NIPAAm-MMA hydrogen bond. Finally, the pH dependence of the DQ spectra demonstrates that hydrogen bonding phenomena are directly related to the polymer collapse.