Anion-Specific Effects on the Behavior of pH-Sensitive Polybasic Brushes

The anion-specific solvation and conformational behavior of weakly basic poly­(2-dimethylamino)­ethyl methacrylate (poly­(DMA)), poly­(2-diethylamino)­ethyl methacrylate (poly­(DEA)), and poly­(2-diisopropylamino)­ethyl methacrylate (poly­(DPA)) brushes, with correspondingly increasing inherent hydrophobicity, have been investigated using <i>in situ</i> ellipsometric and quartz crystal microbalance with dissipation (QCM-D) measurements. In the osmotic brush regime, as the initial low concentration of salt is increased, the brushes osmotically swell by the uptake of solvent as they become charged and the attractive hydrophobic inter- and intrachain interactions are overcome. With increased ionic strength, the brushes move into the salted brush regime where they desolvate and collapse as their electrostatic charge is screened. Here, as the brushes collapse, they transition to more uniform and rigid conformations, which dissipate less energy, than similarly solvated brushes at lower ionic strength. Significantly, in these distinct regimes brush behavior is not only ionic strength dependent but is also influenced by the nature of the added salt based on its position in the well-known Hofmeister or lyotropic series, with potassium acetate, nitrate, and thiocyanate investigated. The strongly kosmotropic acetate anions display low affinity for the hydrophobic polymers, and largely unscreened electrosteric repulsions allow the brushes to remain highly solvated at higher acetate concentrations. The mildly chaotropic nitrate and strongly chaotropic thiocyanate anions exhibit a polymer hydrophobicity-dependent affinity for the brushes. Increasing thiocyanate concentration causes the brushes to collapse at lower ionic strength than for the other two anions. This study of weak polybasic brushes demonstrates the importance of all ion, solvent, and polymer interactions