Hydration-Shell Transformation of Thermosensitive Aqueous Polymers.

Although water plays a key role in the coil-globule transition of polymers and biomolecules, it is not clear whether a change in water structure drives or follows polymer collapse. Here, we address this question by using Raman multivariate curve resolution (Raman-MCR) spectroscopy to investigate the hydration shell structure around poly(N-isopropylacrylamide) (PNIPAM) and poly(propylene oxide) (PPO), both below and above the cloud point temperature at which the polymers collapse and form mesoscopic polymer-rich aggregates. We find that, upon clouding, the water surrounding long PNIPAM chains transforms to a less ordered and more weakly hydrogen bonded structure, while the water surrounding short PNIPAM and PPO chains remains similar above and below the cloud point. Furthermore, microfluidic temperature jump studies demonstrate that the onset of clouding precedes the hydration-shell structural transformation, and thus the observed water structural transformation is associated with ripening of aggregates composed of long-chain polymers, on a time scale that is long compared to the onset of clouding.