Impact of electrolyte on the structure and orientation of water at air/water-polyethylene glycol polymer interface

Polyethylene glycol (PEG) is a water soluble, non-ionic polymer with applications in drug delivery, protein precipitation, anti-biofouling, water-splitting, Li-ion batteries, and fuel cells. The interaction of PEG with water and electrolytes plays pivotal roles in such applications. Using interface-selective spectroscopy, heterodyne-detected vibrational sum frequency generation, and Raman difference spectroscopy with simultaneous curve fitting analysis, we show that water adopts different structures and orientations at the air/water-PEG interface, which depends on the molar mass of the PEG. At the air/water-PEG4000 (MW 4000u) interface, water is H-up oriented (i.e., water Hs are pointed away from the aqueous bulk) around 3200 cm-1 and H-down oriented (i.e., water Hs are pointed toward the aqueous bulk) around 3470 cm-1. Variation of the bulk concentration of PEG4000 does not change the dual orientation of interfacial water. The presence of an electrolyte (1.0M NaCl) selectively reduces the H-up oriented water without affecting the H-down oriented water at the air/water-PEG4000 interface. The selective reorganization of the interfacial water is assigned to the disruption of the asymmetric hydration around ether-oxygen of the surface-adsorbed PEG4000 by the Na+ ion of the electrolyte. Interestingly, in the case of low molar mass PEG (air/water-PEG200), the interfacial water neither shows the dual orientation nor is affected by 1.0M NaCl.