Solvent-Modulated Specific Ion Effects: Poly(N-isopropylacrylamide) Brushes in Nonaqueous Electrolytes.

Pertinent to cryopreservation as well as energy storage and batteries, nonaqueous electrolytes and their mixtures with water were investigated. In particular, specific ion-induced effects on the modulation of a poly(N-isopropylacrylamide) (PNIPAM) brush were investigated in various dimethyl sulfoxide (DMSO)-water solvent mixtures. Spectroscopic ellipsometry and neutron reflectometry were employed to probe changes in brush swelling and structure, respectively. In water-rich solvents (i.e., pure water and 6 mol % DMSO), PNIPAM undergoes a swollen to collapsed thermotransition with increasing temperature, whereby a forward Hofmeister series was noted; K+ and Li+ electrolytes composed of SCN- and I- salted-in (stabilized) PNIPAM chains, and electrolytes of Cl- and Br- salted-out (destabilized) the polymer. The cation was seen to play a lesser role than that of the anion, merely modulating the magnitude of the anion effect. In 70 mol % DMSO, a collapsed to swollen thermotransition was noted for PNIPAM. Here, concentration-dependent specific ion effects were observed; a forward series was observed in 0.2 mol % electrolytes, whereas increasing the electrolyte concentration to 0.9 mol % led to a series reversal. While no thermotransition was observed in pure DMSO, a solvent-induced specific ion series reversal was noted; SCN- destabilized the brush and Cl- stabilized the brush. Both series reversals are attributed to the delicate balance of interactions between the solvent, solute (ion), and substrate (brush). Namely, the stability of the solvent clusters was hypothesized to drive polymer solvation.

Underscreening in concentrated electrolytes: re-entrant swelling in polyelectrolyte brushes.

Hypersaline environments are ubiquitous in nature and are found in myriad technological processes. Recent empirical studies have revealed a significant discrepancy between predicted and observed screening lengths at high salt concentrations, a phenomenon referred to as underscreening. Herein we investigate underscreening using a cationic polyelectrolyte brush as an exemplar. Poly(2-(methacryloyloxy)ethyl)trimethylammonium (PMETAC) brushes were synthesised and their internal structural changes and swelling response was monitored with neutron reflectometry and spectroscopic ellipsometry. Both techniques revealed a monotonic brush collapse as the concentration of symmetric monovalent electrolyte increased. However, a non-monotonic change in brush thickness was observed in all multivalent electrolytes at higher concentrations, known as re-entrant swelling; indicative of underscreening. For all electrolytes, numerical self-consistent field theory predictions align with experimental studies in the low-to-moderate salt concentration regions. Analysis suggests that the classical theory of electrolytes is insufficient to describe the screening lengths observed at high salt concentrations and that the re-entrant polyelectrolyte brush swelling seen herein is consistent with the so-called regular underscreening phenomenon.

From Hofmeister to hydrotrope: Effect of anion hydrocarbon chain length on a polymer brush.

HYPOTHESIS: Specific ion effects govern myriad biological phenomena, including protein-ligand interactions and enzyme activity. Despite recent advances, detailed understanding of the role of ion hydrophobicity in specific ion effects, and the intersection with hydrotropic effects, remains elusive. Short chain fatty acid sodium salts are simple amphiphiles which play an integral role in our gastrointestinal health. We hypothesise that increasing a fatty acid's hydrophobicity will manifest stronger salting-out behaviour. EXPERIMENTS: Here we study the effect of these amphiphiles on an exemplar thermoresponsive polymer brush system, conserving the carboxylate anion identity while varying anion hydrophobicity via the carbon chain length. Ellipsometry and quartz crystal microbalance with dissipation monitoring were used to characterise the thermoresponse and viscoelasticity of the brush, respectively, whilst neutron reflectometry was used to reveal the internal structure of the brush. Diffusion-ordered nuclear magnetic resonance spectroscopy and computational investigations provide insight into polymer-ion interactions. FINDINGS: Surface sensitive techniques unveiled a non-monotonic trend in salting-out ability with increasing anion hydrophobicity, revealing the bundle-like morphology of the ion-collapsed system. An intersection between ion-specific and hydrotropic effects was observed both experimentally and computationally; trending from good anti-hydrotrope towards hydrotropic behaviour with increasing anion hydrophobicity, accompanying a change in hydrophobic hydration.

Effect of surfactants on the thermoresponse of PNIPAM investigated in the brush geometry.

HYPOTHESIS: Anionic surfactants have been reported to interact with poly(N-isopropyl acrylamide) (PNIPAM), suppressing its thermoresponse. Scattering and NMR studies of the anionic sodium dodecylsulfate (SDS) system propose that the PNIPAM-surfactant interaction is purely hydrophobic. However, prior phenomenological investigations of a range of surfactant identities (anionic, cationic, nonionic) show that only anionic surfactants affect the thermoresponse and conformation of PNIPAM, implying that the hydrophilic head-group also contributes. Crucially, the phenomenological experiments do not measure the affinity of the tested surfactants to the polymer, only their effect on its behaviour. EXPERIMENTS: We study the adsorption of six surfactants within a planar PNIPAM brush system, elucidating the polymer conformation, thermoresponse, and surfactant adsorption kinetics using ellipsometry, neutron reflectometry (NR), optical reflectometry and the quartz crystal microbalance technique. NR is used to measure the distribution of surfactants within the brush. FINDINGS: We find that only anionic surfactants modify the structure and thermoresponse of PNIPAM, with the greater affinity of anionic surfactants for PNIPAM (relative to cationic and nonionic surfactants) being the primary reason for this behaviour. These results show that the surfactant head-group has a more critical role in mediating PNIPAM-surfactant interaction than previously reported. Taking inspiration from prior molecular dynamics work on the PEO-surfactant system, we propose an interaction mechanism for PNIPAM and SDS that reconciles evidence for hydrophobic interaction with the observed head-group-dependent affinity.

Polyelectrolyte Complex Hollow Fiber Membranes Prepared via Aqueous Phase Separation.

Hollow fiber (HF) membrane geometry is the preferred choice for most commercial membrane operations. Such fibers are conventionally prepared via the non-solvent-induced phase separation technique, which heavily relies on hazardous and reprotoxic organic solvents such as N-methyl pyrrolidone. A more sustainable alternative, i.e., aqueous phase separation (APS), was introduced recently that utilizes water as a solvent and non-solvent for the production of polymeric membranes. Herein, for the first time, we demonstrate the preparation of sustainable and functional HF membranes via the APS technique in a dry-jet wet spinning process. The dope solution comprising poly(sodium 4-styrenesulfonate) (PSS) and polyethyleneimine (PEI) at high pH along with an aqueous bore liquid is pushed through a single orifice spinneret into a low pH acetate buffer coagulation bath. Here, PEI becomes charged resulting in the formation of a polyelectrolyte complex with PSS. The compositions of the bore liquid and coagulation bath were systematically varied to study their effect on the structure and performance of the HF membranes. The microfiltration-type membranes (permeability ∼500 to 800 L·m-2·h-1·bar-1) with complete retention of emulsion droplets were obtained when the precipitation rate was slow. Increasing the concentration of the acetate buffer in the bath led to the increase in precipitation rate resulting in ultrafiltration-type membranes (permeability ∼12 to 15 L·m-2·h-1·bar-1) having molecular weight cut-offs in the range of ∼7.8-11.6 kDa. The research presented in this work confirms the versatility of APS and moves it another step closer to large-scale use.

Solvent and pH Stability of Poly(styrene-alt-maleic acid) (PSaMA) Membranes Prepared by Aqueous Phase Separation (APS).

In the single-polyelectrolyte aqueous phase separation (APS) approach, membranes are prepared by precipitating a weak polyelectrolyte from a concentrated aqueous solution using a pH switch. This has proven to be a versatile and more sustainable method compared to conventional approaches as it significantly reduces the use of organic solvents. Poly(styrene-alt-maleic acid) (PSaMA) is a polymer that has been extensively investigated for APS and has been the basis for both open and dense membranes with good performances. These membranes are chemically crosslinked and, in this work, we further investigated ultrafiltration (UF) and nanofiltration (NF) membranes prepared with PSaMA for their stability in various organic solvents and under different pH conditions. It was shown that these membranes had stable performances in both isopropanol (IPA) and toluene, and a slightly reduced performance in N-methyl-2-pyrollidone (NMP). However, PSaMA did not perform well as a selective layer in these solvents, indicating that the real opportunity would be to use the UF-type PSaMA membranes as solvent-stable support membranes. Additionally, the membranes proved to be stable in an acidic-to-neutral pH regime (pH 2-7); and, due to the pH-responsive nature of PSaMA, for the NF membranes, a pH-dependent retention of Mg2+ and SO42- ions was observed and, for the UF membranes, a strong responsive behavior was observed, where the pH can be used to control the membrane permeability. However, long-term exposure to elevated pH conditions (pH 8-10) resulted in severe swelling of the NF membranes, resulting in defect formation, and compaction of the UF membranes. For the UF membranes, this compaction did prove to be reversible for some but not all of the membrane samples measured. These results showed that in aqueous systems, membranes prepared with PSaMA had interesting responsive behaviors but performed best at neutral and acidic pH values. Moreover, the membranes exhibited excellent stability in the organic solvents IPA and toluene.

Tuning the charge of polyelectrolyte complex membranes prepared via aqueous phase separation.

In this work, polyelectrolyte mixing ratio is studied as a tuning parameter to control the charge, and thus the separation properties of polyelectrolyte complex (PEC) membranes prepared via Aqueous Phase Separation (APS). In this approach, various ratios of poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) are mixed at high salinity and the PEC-based membranes are then precipitated using low salinity coagulation baths. The monomeric ratio of PSS to PDADMAC is varied from 1.0 : 0.8 through to 1.0 : 1.2. Obtained membranes have an asymmetric structure and function as nanofiltration membranes with on average 1 L m-2 h-1 bar-1 pure water permeance and <400 Da molecular weight cut-off (MWCO); except for the 1.0 : 1.2 membrane, where the water permeance was much higher (>20 L m-2 h-1 bar-1) with a similarly low MWCO. For the first time, we report the formation of both negatively and positively charged PSS-PDADMAC based APS membranes, as determined by both streaming potential and salt retention measurements. We hypothesize that the salt type used in the APS process plays a key role in the observed change in membrane charge. The point where the membrane charge transitions from negative to positive is found to be between the 1.0 : 0.9 and 1.0 : 1.0 PSS : PDADMAC ratios. The polyelectrolyte ratio not only affects membrane charge, but also their mechanical properties. The 1.0 : 0.9 and 1.0 : 1.0 membranes perform the best amongst the membranes prepared in this study since they have high salt retentions (up to 90% Na2SO4 and 75% MgCl2, respectively) and better mechanical stability. The higher permeance of the more charged, and thus more swollen, 1.0 : 0.8 and 1.0 : 1.2 membranes provide a relevant new direction for the development of APS-based PEC membranes.

Enhancing the Separation Performance of Aqueous Phase Separation-Based Membranes through Polyelectrolyte Multilayer Coatings and Interfacial Polymerization.

The aqueous phase separation (APS) technique allows membrane fabrication without use of unsustainable organic solvents, while at the same time, it provides extensive control over membrane pore size and morphology. Herein, we investigate if polyelectrolyte complexation-induced APS ultrafiltration membranes can be the basis for different types of nanofiltration membranes. We demonstrate that APS membranes can be used as support membranes for functional surface coatings like thin polyelectrolyte multilayer (PEMs) and interfacial polymerization (IP) coatings. Three different PEMs were fabricated on poly(sodium 4-styrene sulfonate) (PSS) poly(allylamine hydrochloride) (PAH) APS ultrafiltration membranes, and only 4.5 bilayers were needed to create nanofiltration membranes with molecular weight cut-off (MWCO) values of 210-390 Da while maintaining a roughly constant water permeability (∼1.7 L·m-2·h-1·bar-1). The PEM-coated membranes showed excellent MgCl2 (∼98%), NaCl (∼70%), and organic micropollutant retention values (>90%). Similarly, fabricating thin polyamide layers on the ultrafiltration PSS-PAH APS membranes by IP resulted in nanofiltration membranes with MWCO values of ∼200 Da. This work shows for the first time that APS membranes can indeed be utilized as excellent support membranes for the application of functional coatings without requiring any form of pretreatment.

Effect of Solution Viscosity on the Precipitation of PSaMA in Aqueous Phase Separation-Based Membrane Formation.

Aqueous phase separation (APS) is a recently developed sustainable alternative to the conventional organic solvent based nonsolvent-induced phase separation (NIPS) method to prepare polymeric membranes. In APS, polyelectrolytes are precipitated from aqueous solutions through pH or salinity switches. Although APS differs from NIPS in the polymer and solvents, they share many tuning parameters. In this work, we investigate the APS-based preparation of membranes from poly(styrene-alt-maleic acid) (PSaMA) with a focus on acid concentration in the coagulation bath, and polymer and additive concentration in the casting solution. Nanofiltration membranes are prepared using significantly lower concentrations of acid: 0.3 M HCl compared to the 2 M of either acetic or phosphoric acid used in previous works. It is shown that higher polymer concentrations can be used to prevent defect formation in the top layer. In addition, acetic acid concentration also strongly affects casting solution viscosity and thus can be used to control membrane structure, where lower acetic acid concentrations can prevent the formation of macrovoids in the support structure. The prepared nanofiltration membranes exhibit a very low molecular weight cutoff (210 ± 40 dalton), making these sustainable membranes very relevant for the removal of contaminants of emerging concern. Understanding how the parameters described here affect membrane preparation and performance is essential to optimizing membranes prepared with APS towards this important application.

Structure and Hydration of Asymmetric Polyelectrolyte Multilayers as Studied by Neutron Reflectometry: Connecting Multilayer Structure to Superior Membrane Performance.

Porous membranes coated with so-called asymmetric polyelectrolyte multilayers (PEMs) have recently been shown to outperform commercial membranes for micropollutant removal. They consist of open support layers of poly(styrene sulfonate) (PSS)/poly(allylamine) (PAH) capped by denser and more selective layers of either PAH/poly(acrylic acid) (PAA) or PAH/Nafion. Unfortunately, the structure of these asymmetric PEMs, and thus their superior membrane performance, is poorly understood. In this work, neutron reflectometry (NR) is employed to elucidate the multilayered structure and hydration of these asymmetric PEMs. NR reveals that the multilayers are indeed asymmetric in structure, with distinct bottom and top multilayers when air-dried and when solvated. The low hydration of the top [PAH/Nafion] multilayer, together with the low water permeance of comparable [PAH/Nafion]-capped PEM membranes, demonstrate that it is a reduction in hydration that makes these separation layers denser and more selective. In contrast, the [PAH/PAA] capping multilayers are more hydrated than the support [PSS/PAH] layers, signifying that, here, densification of the separation layer occurs through a decrease in the mesh size (or effective pore size) of the top layer due to the higher charge density of the PAH/PAA couple compared to the PSS/PAH couple. The [PAH/PAA] and [PAH/Nafion] separation layers are extremely thin (∼4.5 and ∼7 nm, respectively), confirming that these asymmetric PEM membranes have some of the thinnest separation layers ever achieved.

Enrichment of Charged Monomers Explains Non-monotonic Polymer Volume Fraction Profiles of Multi-stimulus Responsive Copolymer Brushes.

Multi-stimulus responsive poly(2-(2-methoxyethoxy)ethyl methacrylate-co-2-(diethylamino)ethyl methacrylate) [P(MEO2MA-co-DEA)] 80:20 mol % copolymer brushes were synthesized on planar silica substrates via surface-initiated activators continuously regenerated via electron transfer atom transfer radical polymerization. Brush thickness was sensitive to changes in pH and temperature as monitored with ellipsometry. At low pH, the brush is charged and swollen, while at high pH, the brush is uncharged and more collapsed. Clear thermoresponsive behavior is also observed with the brush more swollen at low temperatures compared to high temperatures at both high and low pH. Neutron reflectometry was used to determine the polymer volume fraction profiles (VFPs) at various pH values and temperatures. A region of lower polymer content, or a depletion region, near the substrate is present in all of the experimental polymer VFPs, and it is more pronounced at low pH (high charge) and less so at high pH (low charge). Polymer VFPs calculated through numerical self-consistent field theory suggest that enrichment of DEA monomers near the substrate results in the experimentally observed non-monotonic VFPs. Adsorption of DEA monomers to the substrate prior to initiation of polymerization could give rise to DEA segment-enriched region proximal to the substrate.

New Method toward a Robust Covalently Attached Cross-Linked Nanofiltration Membrane.

As nanofiltration applications increase in diversity, there is a need for new fabrication methods to prepare chemically and thermally stable membranes with high retention performance. In this work, thio-bromo "click" chemistry was adapted for the fabrication of a robust covalently attached and ultrathin nanofiltration membrane. The selective layer was formed on a pre-functionalized porous ceramic surface via a novel, liquid-vapor interfacial polymerization method. Compared to the most common conventional interfacial polymerization procedure, no harmful solvents and a minimal amount of reagents were used. The properties of the membrane selective layer and its free-standing equivalent were characterized by complementary physicochemical analysis. The stability of the thin selective layer was established in water, ethanol, non-polar solvents, and up to 150 °C. The potential as a nanofiltration membrane was confirmed through solvent permeability tests (water, ethanol, hexane, and toluene), PEG-in-water molecular weight cut-off measurements (≈700 g mol-1), and dye retention measurements.

Polyelectrolyte Complex Membranes via Salinity Change Induced Aqueous Phase Separation.

Polymeric membranes are used on very large scales for drinking water production and kidney dialysis, but they are nearly always prepared by using large quantities of unsustainable and toxic aprotic solvents. In this study, a water-based, sustainable, and simple way of making polymeric membranes is presented without the need for harmful solvents or extreme pH conditions. Membranes were prepared from water-insoluble polyelectrolyte complexes (PECs) via aqueous phase separation (APS). Strong polyelectrolytes (PEs), poly(sodium 4-styrenesulfonate) (PSS), and poly(diallyldimethylammonium chloride) (PDADMAC) were mixed in the presence of excess of salt, thereby preventing complexation. Immersing a thin film of this mixture into a low-salinity bath induces complexation and consequently the precipitation of a solid PEC-based membrane. This approach leads to asymmetric nanofiltration membranes, with thin dense top layers and porous, macrovoid-free support layers. While the PSS molecular weight and the total polymer concentrations of the casting mixture did not significantly affect the membrane structure, they did affect the film formation process, the resulting mechanical stability of the films, and the membrane separation properties. The salt concentration of the coagulation bath has a large effect on membrane structure and allows for control over the thickness of the separation layer. The nanofiltration membranes prepared by APS have a low molecular weight cutoff (<300 Da), a high MgSO4 retention (∼80%), and good stability even at high pressures (10 bar). PE complexation induced APS is a simple and sustainable way to prepare membranes where membrane structure and performance can be tuned with molecular weight, polymer concentration, and ionic strength.

Interplay of Composition, pH, and Temperature on the Conformation of Multi-stimulus-responsive Copolymer Brushes: Comparison of Experiment and Theory.

Poly(2-(2-methoxyethoxy)ethyl methacrylate) (PMEO2MA), a thermoresponsive polymer with a lower critical solution temperature of ∼28 °C, and poly(2-(diethylamino)ethyl methacrylate) (PDEA), a weak polybase with an apparent pKa of ∼7.5, have been statistically copolymerized using activators continuously regenerated via electron transfer atom transfer radical polymerization to form multi-stimulus-responsive polymer brushes. The stimulus-responsive behavior of these brushes has been investigated with ellipsometry and numerical self-consistent field (nSCF) theory. The pH- and thermoresponsive behaviors of a PDEA homopolymer brush were investigated experimentally in order to benchmark the nSCF theory calculations. nSCF theory was able to reproduce the responsive behavior of PDEA and PMEO2MA homopolymer brushes. Three copolymer compositions (90:10, 70:30, and 50:50 mol % MEO2MA:DEA) were investigated experimentally with pH ramps performed at low and high temperatures and temperature ramps performed at low and high pH. A broader range of compositions were investigated with nSCF theory and compared to the experimental results, with the nSCF calculations able to capture the general behavior of the homopolymer and copolymer brushes. The responsive behavior of each brush to a given stimulus (temperature or pH) was dependent on both the polymer composition and environment (temperature or pH). The influence of pH on the brush increased with higher DEA mol % with a copolymer brush response transitioning from temperature-dominant to pH-dominant. The temperature response of PMEO2MA was completely masked at low and high pH values by the presence of at least 30 mol % polybase in the copolymer.

Ion specific effects on aqueous phase separation of responsive copolymers for sustainable membranes.

HYPOTHESIS: Salt identity and concentration affects the preparation of membranes via the aqueous phase separation approach. The phase inversion process and morphology of the resultant membranes is expected to vary as function of these two parameters. EXPERIMENTS: Polymeric membranes based on the responsive copolymer polystyrene-alt-maleic acid (PSaMA) are prepared using the aqueous phase separation approach and the influence of salt identity (Na2SO4, LiCl, NaCl, NaNO3, NH4Cl, MgCl2, CaCl2) and concentration on resultant membrane morphology and separation performance is investigated. Complementary stability experiments of PSaMA solutions are performed to help understand the intricate aqueous phase separation process. FINDINGS: Specific ion effects are observed during membrane formation by the aqueous phase separation approach. At equal ionic strengths, Na2SO4 and LiCl lead to the formation of more open membrane structures compared to NaCl, NaNO3, NH4Cl, and MgCl2, while CaCl2 results in membranes with dense top layers. These ion-specific effects are likely caused by a combination of ion mobility and interaction potential between the ion and the polyelectrolyte. Overall, from this work it becomes clear that salt identity and concentration are key parameters in the APS process, and they can be optimised to tune membrane structure from open microfiltration to dense nanofiltration membranes.

Aqueous Phase Separation of Responsive Copolymers for Sustainable and Mechanically Stable Membranes.

Membranes are often used in environmentally friendly applications and as a sustainable alternative to conventional processes. Unfortunately, the vast majority of polymeric membranes are produced via an unsustainable and environmentally unfriendly process that requires large amounts of harsh reprotoxic chemicals such as N-methyl-2-pyrrolidinone and dimethylformamide. In this work, we investigate an aqueous phase separation (APS) system that uses weak polyelectrolytes, whose charge is dependent on the pH (weak polyelectrolytes), to produce membranes. Specifically the copolymer polystyrene-alt-maleic acid (PSaMA) is used. PSaMA contains responsive monomers, required for APS, and also unresponsive hydrophobic monomers that provide mechanical stability to the resultant membranes. This work demonstrates that by controlling the precipitation of PSaMA, it is possible to prepare a wide range of membranes; from microfiltration membranes capable of treating oily waste water to dense nanofiltration-type membranes with excellent micropollutant retentions and high mechanical stability. While similar materials in prior work could only withstand 4 bar, the membranes presented here demonstrate stable operation up to 20 bar. The only solvents used in this APS system are water and the green solvent acetic acid, thus making our APS process significantly more sustainable and environmentally friendly as compared to the conventional membrane fabrication methods.

Stimuli-Responsive Membranes through Sustainable Aqueous Phase Separation.

Polymeric membranes are used on huge scales for kidney dialysis, wastewater treatment, and drinking water production. However, almost all polymeric membranes are fabricated by a process reliant on the use of unsustainable, expensive, and reprotoxic dipolar aprotic solvents. In this work, we propose an aqueous phase separation approach for preparing porous membrane films. Poly(4-vinylpyridine) (P4VP), a pH-responsive polymer, is first dissolved at low pH where the polymer is charged and subsequently cast as a thin film. Switching to a high pH where the polymer is uncharged and insoluble results in controlled phase separation and solidification of the polymer into porous membrane structures. This approach gives a large degree of control over membrane structure, leading to symmetric porous microfiltration membranes and asymmetric dense nanofiltration membranes. Moreover, the use of a pH-responsive polymer leads directly to a pH-responsive membrane, where the degree of responsive behavior can be tuned by the degree of cross-linking. Such responsive behavior allows effective cleaning of the membrane, without the use of harsh chemicals. This work outlines an approach toward preparing membranes in a more sustainable fashion-an approach that allows control over the membrane structure and one that naturally leads to advanced membranes with responsive properties.

Combined Experimental and Theoretical Study of Weak Polyelectrolyte Brushes in Salt Mixtures.

The swelling behavior of a hydrophobic poly(2diisopropylamino)ethyl methacrylate (PDPA) brush immersed in aqueous solutions of single and mixed salts has been investigated using ellipsometry and numerical self-consistent field (nSCF) theory. As a function of solution ionic strength, the osmotic and salted brush regimes of weak polyelectrolyte brushes as well as substantial specific anion effects in the presence of K+ salts of Cl-, NO3-, and SCN- are found. For solutions containing mixtures of NO3- and Cl-, the brush swelling is the same as one would expect on the basis of the concentration-weighted average of the brush behavior in the single salt solutions. However, in mixtures of SCN- and Cl-, the swelling response is more complicated and substantial divergence from ideal behavior is observed. Mean-field theory shows excellent qualitative agreement with the ellipsometry findings. nSCF reveals that for the SCN-/Cl- cases the swelling behavior of the PDPA brush most likely arises from the predominant localization of the weakly hydrated SCN- within the brush compared to the more strongly hydrated Cl-.

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.

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.