Joshua D. Willott

Critical Salt Effects in the Swelling Behavior of a Weak Polybasic Brush

The swelling behavior of poly(2-(diethylamino)ethyl methacrylate) (PDEA) brushes in response to changes in solution pH and ionic strength has been investigated. The brushes were synthesized by ARGET ATRP methodology at the silica-aqueous solution interface via two different surface-bound initiator approaches: electrostatically adsorbed cationic macroinitiator and covalently anchored silane-based ATRP initiator moieties. The pH-response of these brushes is studied as a function of the solvated brush thickness in a constant flow regime that elucidates the intrinsic behavior of polymer brushes. In situ ellipsometry equilibrium measurements show the pH-induced brush swelling and collapse transitions are hysteretic in nature. Furthermore, high temporal resolution kinetic studies demonstrate that protonation and solvent ingress during swelling occur much faster than the brush charge neutralization and solvent expulsion during collapse. This hysteresis is attributed to the formation of a dense outer region or skin during collapse that retards solvent egress. Moreover, at a constant pH below its pKa, the PDEA brush exhibited a critical conformational change in the range 0.5-1 mM electrolyte, a range much narrower than predicted by the theory of the osmotic brush regime. This behavior is attributed to the hydrophobicity of the collapsed brush. The swelling and collapse kinetics for this salt-induced transition are nearly identical. This is in contrast to the asymmetry in the rate of the pH-induced response, suggesting an alternative mechanism for the two processes dependent on the nature of the environmental trigger.

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 in situ 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.

Specific ion modulated thermoresponse of poly(N-isopropylacrylamide) brushes.

The influence of specific anions on the equilibrium thermoresponse of poly(N-isopropylacrylamide) (pNIPAM) brushes has been studied using in situ ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 °C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 °C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 °C. In the presence of the kosmotropic acetate anions, the measured lower critical solution temperature (LCST) by the three techniques was very similar and decreased linearly as a function of ionic strength. Conversely, increasing the concentration of the chaotropic thiocyanate anions raised the LCST of the pNIPAM brushes with variation in the measured LCST between the three techniques increasing with ionic strength. The thickness of the pNIPAM brush was seen to progressively increase with increasing thiocyanate concentration at all temperatures. It is proposed that specific ion binding of the chaotropic thiocyanate anion with pNIPAM amide moieties increases the electrostatic intra- and intermolecular repulsion within and between pNIPAM chains. This allows the brush to begin to swell at higher temperatures and to an overall greater extent.

Effect of colloidal substrate curvature on pH-responsive polyelectrolyte brush growth

Coatings consisting of polymer brushes are an effective way to modify solid interfaces. Polymer brush-modified hybrid particles have been prepared by surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP) of 2-(diethylamino)ethyl methacrylate (DEA) on silica particles. We have optimized the synthesis with respect to changing the reducing agent, temperature, and reaction solvent from an aqueous ethanol mixture to an aqueous methanol mixture. Our flexible electrostatically adsorbed macroinitiator approach allows for the modification of a variety of surfaces. Polybasic brushes have been grown on silica particles of different sizes, from 120 to 840 nm in diameter, as well as on wafers, and a comparison of the products has allowed the effect of surface curvature to be elucidated. An examination of the thickness of the dry brush and the aqueous hydrodynamic brush at both pH 7 and at 4 demonstrated that growth increased substantially with substrate curvature for particles with a diameter below 450 nm. This is attributed to the increasing separation between active chain ends, reducing the rate of termination. This is believed to be the first time that this effect has been demonstrated experimentally. Furthermore, we have seen that polymer brush growth on planar wafers was significantly reduced when the reaction mixture was stirred.

Enhanced specific ion effects in ethylene glycol-based thermoresponsive polymer brushes

The thermoresponse of poly(di(ethyleneglycol) methyl ether methacrylate) (PMEO2MA) brushes has been investigated in the presence of monovalent anions at either end of the Hofmeister series using ellipsometry, neutron reflectometry (NR) and colloid probe atomic force microscopy (AFM). NR measurements in deuterium oxide showed no evidence of vertical phase separation perpendicular to the grafting substrate with a gradual transition between a block-like, dense structure at 45°C and an extended, dilute conformation at lower temperatures. All three techniques revealed a shift to a more collapsed state for a given temperature in kosmotropic potassium acetate solutions, while more swollen structures were observed in chaotropic potassium thiocyanate solutions. No difference was observed between 250mM and 500mM thiocyanate for a 540Å brush studied by ellipsometry, while the lower molecular weight ∼200Å brushes used for NR and AFM measurements continued to respond with increasing salt concentration. The effect of thiocyanate on the temperature response was greatly enhanced relative to PNIPAM with the shift in temperature response at 250mM being five times greater than a PNIPAM brush of similar thickness and grafting density.

Behavior of Weak Polyelectrolyte Brushes in Mixed Salt Solutions

Hydrophilic and hydrophobic weak polybasic brushes immersed in aqueous solutions of mixed salt counterions are considered using a mean-field numerical self-consistent field approach. On top of the solvent quality of the polymer, the counterion–solvent interactions are accounted for by implementing Flory–Huggins interaction parameters. We show that ion specificity within the brush can bring about large changes in conformation. It is found that the collapse transition of hydrophobic, weak polyelectrolyte brushes features an intermediate two-phase state wherein a subset of chains are collapsed in a dense layer at the substrate, while the remainder of chains are well-solvated and strongly stretched away from the it. Besides pH and ionic strength, solvent quality of counterions and the composition of ions in the solvent are important control parameters for the behavior of polyelectrolyte brushes. Increasingly hydrophobic counterions penetrate deeper within the brush and stabilize the collapsed region, while hydrophilic counterions do the opposite.