Effect of alkyl chain spacer length between the charged groups (CSL) in zwitterionic poly(sulfobetaine) (PSB) brushes on the hydration state was investigated. PSB brushes with ethyl (PMAES), propyl (PMAPS), or butyl (PMABS) CSL were prepared by surface-initiated atom transfer radical polymerization on silicon wafers. Hydration states of the PSB brushes in aqueous solutions and/or humid vapor were investigated by contact angle measurement, infrared spectroscopy, AFM observation, and neutron reflectivity. The PSB brushes are swollen in humid air and deionized water due to the hydration of the charged groups leading to the reduction of hydrated PSB brushes/water interfacial free energy. The hydrated PSB brushes exhibit clear interface with low interfacial roughness due to networking of the PSB brush chains through association of the SBs. The hydrated PSB brushes produce diffusive swollen layer in the presence of NaCl because of the charge screening followed by SB dissociation by the bound ions. The ionic strength sensitivity in the hydration got more significant with increasing the CSL in SBs because of the augmentation in partial charge by charged group separation.

The ion-specific hydration states of zwitterionic poly­(3-(N-2-meth­acryl­oyl­oxy­ethyl-N,N-di­methyl)­ammonato­propane­sulfonate) (PMAPS) brushes in various aqueous solutions were investigated by neutron reflectivity (NR) and atomic force microscopy (AFM). The asymmetric hydration state of the PMAPS brushes was verified from the NR scattering-length density profiles, while the variation in their swollen thickness was complementary as determined from AFM topographic images. PMAPS brushes got thicker in any salt solutions, while the extent of swelling and the dimensions of swollen chain structure were dependent on the ion species and salt concentration in the solutions. Anion specificity was clearly observed, whereas cations exhibited weaker modulation in ion-specific hydration states. The anion specificity could be ascribed to ion-specific interactions between the quaternary ammonium cation in sulfobetaine and the anions. The weak cation specificity was attributed to the intrinsically weak cohesive interactions between the weakly hydrated sulfonate anion in sulfobetaine and the strongly hydrated cations. The ion-specific hydration of PMAPS brushes was largely consistent with the ion-specific aggregation state of the PMAPS chains in aqueous solutions.

Water existing in the vicinity of polyelectrolytes exhibits unique structural properties, which demonstrate key roles in chemistry, biology, and geoscience. In this study, X-ray absorption and emission spectroscopy was employed to observe the local hydrogen-bonding structure of water confined in a charged polyelectrolyte brush. Even at room temperature, a majority of the water molecules confined in the polyelectrolyte brush exhibited one type of hydrogen-bonding configuration: a slightly distorted, albeit ordered, configuration. The findings from this study provide new insight in terms of the correlation between the function and local structure of water at the interface of biological materials under physiological conditions.

While polyelectrolyte brushes have received extensive attention due to their particular surface properties, the ion-specific hydration states remain largely unknown. Here, we report the counteranion-specific hydration states of cationic poly­[2-(methacryloyloxy)­ethyltrimethylammonium] (PMTA) brushes in salt-free water. The water droplet contact angle on the PMTA brushes depends on the counteranion species, and the order is consistent with the Hofmeister series. Weakly hydrated chaotropic counteranions are strongly bound to weakly hydrated quaternary ammonium (QA+) cations in the PMTA brush chains, which induces a reduction in the ζ-potential, dehydration, and collapse of the PMTA brushes. The PMTA brushes with strongly hydrated chloride counteranions produce a more diffuse tail and less swollen bound layer under salt-free deuterium oxide than brushes with weakly hydrated thiocyanate counteranions. Ion pairing disturbs the ordering of hydrated water in the PMTA brushes. Our work enhances the understanding of the ion specificity in the hydration states of polyelectrolyte brushes and encourages the rational design of charged polymer materials.

A highly effective aqueous lubrication strategy employing electrostatic assembly of a negatively charged ultrahigh molecular weight natural polysaccharide named "sacran" and a p o s i t i v e l y c h a r g e d p o l y [ 2 -( m e t h a c r y l o y l o x y )ethyltrimethylammonium chloride] (PMTAC) brush was investigated. The PMTAC brush was compressed through the adsorption of sacran to produce the layered structure of a PMTAC brush/sacran hybrid bottom layer and a poorly hydrated sacran top layer. The dynamic friction coefficients of the PMTAC brush were drastically reduced in salt-free sacran aqueous solutions, and the lubrication mode transition from the brush-lubrication regime to hydrodynamic lubrication was promoted. The electrostatic assembly was inhibited by the addition of NaCl into the lubricant solutions, leading to the loss of the lubrication effect. The hydrodynamic lubrication would be encouraged by the local viscosity enhancement at the friction boundary due to the poorly hydrated and highly viscous PMTAC brush/sacran hybrid film produced by the spontaneous electrostatic assembly.