Molecular insights into the hydration of zwitterionic polymers†

Preventing ice formation and accumulation on solid surfaces has been a great challenge to address for various engineering and technological applications. Recently, the new development of zwitterionic polymer coatings attracted a lot of attention due to their excellent anti-icing performance (i.e., effectively reducing ice formation and adhesion), making them ideal material candidates for anti-icing coating applications. In this study, we employ density functional theory (DFT) to explore the hydration behaviors of two representative zwitterionic polymers, i.e., poly(sulfobetaine-methacrylate) (polySB) and poly(2-methacryloxoethyl-phosphorylcholine) (polyMPC). Through detailed bonding analysis by crystal orbital Hamilton populations (COHP), our results indicate strong interaction and covalent-nature bonds between the hydrogen atoms in water molecules and polymers' oxygen atoms of the anionic group of the polymer. Electron partial density of states (PDOS), Bader charge analysis, and energy calculations further demonstrate the physical and chemical nature of the water–polymer bonds. Interestingly, our modeling results also reveal that the addition of more water molecules will decrease the bonding stability of the bond between adsorbed water molecules to the polymer. Such induced bond instability, along with the polymer's hydrophilic character, suggests that continuous association and dissociation of bonded water molecules serve as the key mechanism which explains the inhibition of water clustering of the hydration layer. Our findings provide valuable insights into the physiochemical nature of water–polymer interaction by unveiling the molecular mechanism of hydration behavior, paving the way for design of next-generation anti-icing materials.