Structure analysis of poly(N-isopropylacrylamide) using near-infrared spectroscopy and generalized two-dimensional correlation infrared spectroscopy

Based on a detailed study of the fundamental vibrations in the mid-infrared (MIR) region and supported by NH-proton deuteration results, the assignment of the overtone and combination bands in the near-infrared (NIR) spectrum of poly(N-isopropylacrylamide) (PNIPAM) is presented. Variable-temperature experiments and two-dimensional correlation infrared spectroscopy are used to determine the chemical mechanism and changing sequence of groups in PNIPAM; we conclude that bonded NH groups turn into free NH groups during the heating process, while the CH groups on the side-chains change prior to those on the main chains. A heterospectral dynamical correlation between the NIR and MIR regions or H-included groups in both regions was also performed. The temperature-induced dissociation of the hydrogen-bonded NH groups is found to proceed earlier than the conformational changes in the hydrocarbon chains.