Hydrogen bonding regulation on phase change in stimuli responsive copolymer aqueous solution

Hydrogen bonding (HB) is vital for the phase transition and physical properties of stimuli responsive copolymers. However, the governing mechanism remains unclear. Herein, we investigated the HB dynamics in a representative thermo-responsive copolymer (PNIPAM-AM) aqueous solution. Three types of HB were identified: polymer-polymer chain (C=O:H-N), polymer chain-water molecule (C=O:H-O) and water -water molecules (H-O:H-O) by vibrational spectroscopy. Increasing polymer concentration, the H-O:H-O softened and C=O:H-O stiffened, leading to the destruction of HB network in water -water clusters. Upon increasing solution temperature, C=O:H-O softened while C=O:H-N stiffened, resolving the dehydration and cross-linking of polymer chains. Confinement of water molecules in the "cages" (similar to tens to hundreds of micrometers) after sol -gel phase transition was visualized, disclosing the mechanism of water holding capacity of PNIPAM-AM. The correlation of molecule vibration and copolymer microscopic structure was established, contributing to the fundamental understanding of phase behavior and physical properties regulations in stimuli responsive copolymer aqueous solution.