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.

Specific Ion Effects at the Vapor-Formamide Interface: A Reverse Hofmeister Series in Ion Concentration Depth Profiles.

Employing neutral impact collision ion scattering spectroscopy (NICISS), we have directly measured the concentration depth profiles (CDPs) of various monovalent ions at the vapor-formamide interface. NICISS provides CDPs of individual ions by measuring the energy loss of neutral helium atoms backscattered from the solution interface. CDPs at the vapor-formamide interface of Cl-, Br-, I-, Na+, K+, and Cs+ are measured and compared to elucidate the interfacial specific ion trends. We report a reverse Hofmeister series in the presence of inorganic ions (anion and cation) at the vapor-formamide interface relative to the water-vapor interface, and the CDPs are found to be independent of the counterion for most ions studied. Thus, ions at the surface of formamide follow a "Hofmeister paradigm" where the counterion does not impact the ion series. These specific ion trends are complemented with surface tension and X-ray absorption near-edge structure (XANES) measurements on formamide electrolyte solutions.

Electrostatic Adsorption Behaviors of Polymer Plates to a Droplet.

Electrostatic transfer and adsorption of electrically conductive polymer-coated poly(ethylene terephthalate) plates from a particle bed to a water droplet were studied, with the influence of plate thickness and shape observed. After synthesis and confirmation of the particles' properties using stereo and scanning electron microscopies, elemental microanalysis, and water contact angle measurement, the electric field strength and droplet-bed separation distance required for transfer were measured. An electrometer and high-speed video footage were used to measure the charge transferred by each particle, and its orientation and adsorption behavior during transfer and at the droplet interface. The use of plates of consistent square cross section allowed the impact of contact-area-dependent particle cohesion and gravity on the electrostatic transfer of particles to be decoupled for the first time. The electrostatic force required to extract a plate was directly proportional to the plate mass (thickness), a trend very different from that previously observed for spherical particles of varied diameter (mass). This reflected the different relationship between mass, surface area, and cohesive forces for spherical and plate-shaped particles of different sizes. Thicker plates transferred more charge to the droplet, probably due to their remaining at the bed at higher field strengths. The impact of plate cross-sectional geometry was also assessed. Differences in the ease of transfer of square, hexagonal, and circular plates seemed to depend only on their mass, while other aspects of their comparative behavior are attributed to the more concentrated charge distribution present on particles with sharper vertices.

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.

A quantum chemical molecular dynamics repository of solvated ions.

The importance of ion-solvent interactions in predicting specific ion effects in contexts ranging from viral activity through to electrolyte viscosity cannot be underestimated. Moreover, investigations of specific ion effects in nonaqueous systems, highly relevant to battery technologies, biochemical systems and colloid science, are severely limited by data deficiency. Here, we report IonSolvR - a collection of more than 3,000 distinct nanosecond-scale ab initio molecular dynamics simulations of ions in aqueous and non-aqueous solvent environments at varying effective concentrations. Density functional tight binding (DFTB) is used to detail the solvation structure of up to 55 solutes in 28 different protic and aprotic solvents. DFTB is a fast quantum chemical method, and as such enables us to bridge the gap between efficient computational scaling and maintaining accuracy, while using an internally-consistent simulation technique. We validate the database against experimental data and provide guidance for accessing individual IonSolvR records.

Ion specificity in the measured concentration depth profile of ions at the Vapor-Glycerol interface.

HYPOTHESIS: Specific ion effects are manifest universally across many systems and solvents. Whilst broad understanding of these effects is emerging particularly for bulk effects, the perturbation introduced by the interfaces are generally not understood. We hypothesise that through a careful investigation of the distribution of ions at the glycerol-vapor interface we can better understand specific ion effects in this system and at interfaces. EXPERIMENTS: Neutral impact collision ion scattering spectroscopy (NICISS) is used to obtain and compare individual ion concentration depth profiles (CDP) for a range of monovalent inorganic anions and cations at 12 glycerol electrolyte solutions surfaces. FINDINGS: The distribution of ions at the vapor - glycerol interface is non-monotonic. Broadly, anions are concentrated at the outermost region of the interface and cations are depleted from the interface. The distribution of Cl- and I- is mostly independent of the counterion. However, for Br- ions the distribution depends on the counterion where Cs+, K+, and Na+ ions lead to a desorption of Br- ions from the interface. This is favoured by the large solvation energy of Br- ions and consistent with the law of matching effective ion sizes.

Understanding specific ion effects and the Hofmeister series.

Specific ion effects (SIE), encompassing the Hofmeister Series, have been known for more than 130 years since Hofmeister and Lewith's foundational work. SIEs are ubiquitous and are observed across the medical, biological, chemical and industrial sciences. Nevertheless, no general predictive theory has yet been able to explain ion specificity across these fields; it remains impossible to predict when, how, and to what magnitude, a SIE will be observed. In part, this is due to the complexity of real systems in which ions, counterions, solvents and cosolutes all play varying roles, which give rise to anomalies and reversals in anticipated SIEs. Herein we review the historical explanations for SIE in water and the key ion properties that have been attributed to them. Systems where the Hofmeister series is perturbed or reversed are explored, as is the behaviour of ions at the liquid-vapour interface. We discuss SIEs in mixed electrolytes, nonaqueous solvents, and in highly concentrated electrolyte solutions - exciting frontiers in this field with particular relevance to biological and electrochemical applications. We conclude the perspective by summarising the challenges and opportunities facing this SIE research that highlight potential pathways towards a general predictive theory of SIE.

Impact of surface free energy on electrostatic extraction of particles from a bed.

HYPOTHESIS: Electrostatic extraction of particles from a bed to a pendent droplet to form liquid marbles has previously been investigated with respect to particle conductivity, size and shape, however, interparticle forces have not been specifically interrogated. If cohesion is the dominant force within the particle bed, then particles will be more readily extracted with reduced surface free energy. EXPERIMENTS: Glass particles were surface-modified using various alkyltrichlorosilanes. The surface free energy was measured for each sample using colloid probe atomic force microscopy (AFM) and sessile drop measurements on similarly modified glass slides. The ease of electrostatic particle extraction of each particle sample to a pendent droplet was compared by quantifying the electric field force required for successful extraction as a function of the measured surface free energy. FINDINGS: Surface free energy calculated from sessile droplet measurements and AFM were not in agreement, as work of adhesion of a liquid droplet on a planar substrate is not representative of the contact between particles. Ease of electrostatic extraction of particles was observed to generally decrease as a function of AFM-derived surface free energy, confirming this is a critical factor in electrostatic delivery of particles to a pendent droplet. Roughness was also shown to inhibit particle extraction.

Interparticle Repulsion of Microparticles Delivered to a Pendent Drop by an Electric Field.

We report an unusually large spacing observed between microparticles after delivery to the surface of a pendent water droplet using a DC nonuniform electrostatic field, primarily via dielectrophoresis. The influence of particle properties was investigated using core particles, which were either coated or surface-modified to alter their wettability and conductivity. Particles that exhibited this spacing were both hydrophobic and possessed some dielectric material exposed to the external field, such as a coating or exposed dielectric core. The origin of this behavior is proposed to be the induced dipole-dipole repulsion between particles, which increases with particle size and decreases when the magnitude of the electric field is reduced. When the particles were no longer subjected to an external field, this large interparticle repulsion ceased and the particles settled to the bottom of the droplet under the force of gravity. We derive a simple model to predict this spacing, with the dipole-dipole repulsion balanced against particle weight. The external electric field was calculated using the existing electric field models. The spacing was found to be dependent on particle density and the induced dipole moment as well as the number of particles present on the droplet interface. As the number of particles increased, a decrease in interparticle spacing was observed.

Fractal-like R5 assembly promote the condensation of silicic acid into silica particles.

HYPOTHESIS: Despite advances in understanding the R5 (SSKKSGSYSGKSGSKRRIL) peptide-driven bio-silica process, there remains significant discrepancies regarding the physicochemical characterization and the self-assembling mechanistic driving forces of the supramolecular R5 template. This paper investigates the self-assembly of R5 as a function of monovalent (sodium chloride) and multivalent salt (phosphate) to determine if assembly is phosphate ion concentration dependent. Additionally, we hypothesize that the assembled R5 aggregates do not resemble a micelle or unimer structure as proposed in current literature. EXPERIMENTS: R5 peptides were synthesized, and aggregates evaluated for their size, morphology, and association state as a function of salt and ionic strength concentration via dynamic and static light scattering, small angle X-ray and neutron scattering and cryogenic transmission electron microscopy. Furthermore, we compare the proposed R5 template to precipitated silica by scanning electron microscopy. FINDINGS: R5 peptides assemble into large aggregates due to multivalence bridging and the decrease in electrostatic repulsion due to ionic strength. We elucidate the structure of R5 aggregates as mass-fractals composed of small spherical aggregates. Moreover, we discover that phosphate ions not only have a significant role in driving the growth of the R5 scaffold, but additionally in driving the polycondensation of silicic acid during the bio-silification process via electrostatic interactions.

The electrostatic origins of specific ion effects: quantifying the Hofmeister series for anions.

Life as we know it is dependent upon water, or more specifically salty water. Without dissolved ions, the interactions between biological molecules are insufficiently complex to support life. This complexity is intimately tied to the variation in properties induced by the presence of different ions. These specific ion effects, widely known as Hofmeister effects, have been known for more than 100 years. They are ubiquitous throughout the chemical, biological and physical sciences. The origin of these effects and their relative strengths is still hotly debated. Here we reconsider the origins of specific ion effects through the lens of Coulomb interactions and establish a foundation for anion effects in aqueous and non-aqueous environments. We show that, for anions, the Hofmeister series can be explained and quantified by consideration of site-specific electrostatic interactions. This can simply be approximated by the radial charge density of the anion, which we have calculated for commonly reported ions. This broadly quantifies previously unpredictable specific ion effects, including those known to influence solution properties, virus activities and reaction rates. Furthermore, in non-aqueous solvents, the relative magnitude of the anion series is dependent on the Lewis acidity of the solvent, as measured by the Gutmann Acceptor Number. Analogous SIEs for cations bear limited correlation with their radial charge density, highlighting a fundamental asymmetry in the origins of specific ion effects for anions and cations, due to competing non-Coulombic phenomena.

Competitive specific ion effects in mixed salt solutions on a thermoresponsive polymer brush.

HYPOTHESIS: Grafted poly(ethylene glycol) methyl ether methacrylate (POEGMA) copolymer brushes change conformation in response to temperature ('thermoresponse'). In the presence of different ions the thermoresponse of these coatings is dramatically altered. These effects are complex and poorly understood with no all-inclusive predictive theory of specific ion effects. As natural environments are composed of mixed electrolytes, it is imperative we understand the interplay of different ions for future applications. We hypothesise anion mixtures from the same end of the Hofmeister series (same-type anions) will exhibit non-additive and competitive behaviour. EXPERIMENTS: The behaviour of POEGMA brushes, synthesised via surface-initiated ARGET-ATRP, in both single and mixed aqueous electrolyte solutions was characterised with ellipsometry and neutron reflectometry as a function of temperature. FINDINGS: In mixed fluoride and chloride aqueous electrolytes (salting-out ions), or mixed thiocyanate and iodide aqueous electrolytes (salting-in ions), a non-monotonic concentration-dependent influence of the two anions on the thermoresponse of the brush was observed. A new term, δ, has been defined to quantitively describe synergistic or antagonistic behaviour. This study determined the specific ion effects imparted by salting-out ions are dependent on available solvent molecules, whereas the influence of salting-in ions is dependent on the interactions of the anions and polymer chains.

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.

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.

Influence of particle size on extraction from a charged bed - toward liquid marble formation.

The interactions between particles and the role of their physical properties are not well understood for the electrostatic formation of liquid marbles. Here we focus initially on the impact of increasing particle diameter (notionally 20 to 140 µm) on the ease of particle extraction from an advancing bed of charged particles beneath an earthed, suspended water droplet. A larger particle diameter increased the ease of extraction, due to decreased interparticle cohesion, with increased potential applied to the particle bed. Whilst particle extraction is a crucial step in liquid marble formation, transport to the droplet and subsequent coating and stabilisation of the liquid is also significant. Further investigation highlighted that the smaller particle diameters afforded increased liquid stabilisation due to increased coverage and smaller interstitial spaces between particles on the liquid surface. Optimal conditions for controllable liquid marble formation using electrostatics was postulated as a trade-off between drop-bed separation distance, applied potential and kinetics of coating when studying impact of particle size. Furthermore, preliminary modelling, utilising weakest-link statistics and fracture mechanics, of the experimental data was undertaken to focus on development of the relationship between particle properties and extractability in the presence of electrostatics. This model represents a step towards predicting the suitability of particles for use in the electrostatic formation of liquid marbles prior to undertaking experimental work.

Lewis Strength Determines Specific-Ion Effects in Aqueous and Nonaqueous Solvents.

An analysis of specific-ion effects in aqueous and nonaqueous solvents using energy decomposition analysis is presented. Specific-ion effects induce or influence physicochemical phenomena in a way that is determined by the identity of the ions present, and not merely by their charge or concentration. Such effects have been known since the seminal work of Hofmeister and are often categorized according to the well-known Hofmeister series. Examples of specific-ion effects are ubiquitous throughout chemistry and biology and are traditionally explained in terms of the influence ions have on the structure of water. However, this explanation is unsatisfactory because it is unable to adequately explain and predict frequently observed series reversals and anomalies. Further, recent experiments have shown that specific-ion effects are observed in nonaqueous solvents. By modeling solvated ion-N-isopropylacrylamide (NIPAM) complexes, we show here that specific-ion effects on ion-NIPAM interaction free energies are observed not only in water, but also in several nonaqueous solvents (methanol, acetonitrile, DMSO) in correspondence with the ions' Lewis Strengths. Interestingly, the same trends are observed in the absence of a solvent environment altogether. Counterion effects on ion-NIPAM interaction free energies are negligible for dissociated ion pairs but are evident in associated ion pairs because of the modulation of repulsive ion-NIPAM interactions. We propose a mechanism for explaining reversals in specific-ion effects, based on the competing strengths of the ion-solvent and ion-NIPAM interaction and their relative Lewis strengths. This extends existing theories regarding specific-ion effect reversals in aqueous solutions, as we show that solvent properties must also be taken in to account for specific-ion effects to be predicted in arbitrary solvent environments.

Poly(N-isopropylacrylamide) Response to Salt Concentration and Anion Identity: A Brush-on-Brush Study.

The stability of poly(N-isopropylacrylamide) (PNIPAM) brush-modified colloidal silica particles was compared to asymmetric and symmetric PNIPAM brush direct force measurements in the presence of 1, 10, and 500 mM aqueous salt solution of KCl, KNO3, and KSCN between 10 and 45 °C. Dynamic light scattering measurements highlighted subtle variations in the salt-mediated thermoresponse, while atomic force microscopy (AFM) force curves between a bare silica or PNIPAM brush-modified colloid probe and a planar PNIPAM brush elucidated differences in brush interactions. The AFM force curves in the presence of KCl primarily revealed steric interactions between the surfaces, while KNO3 and KSCN solutions exhibited electrosteric interactions on approach as a function of the chaotropic nature of the ion and the solution concentration. The symmetric PNIPAM brush interaction highlighted significant variations between KCl and KSCN at 1 and 500 mM concentrations, while the approach and retraction force curves were relatively similar at 10 mM concentration. The combination of these techniques enabled the stability of PNIPAM brush-modified colloidal dispersions in the presence of electrolyte to be better understood with specific ion binding and the solution Debye length playing a significant role.

Temperature dependent specific ion effects in mixed salt environments on a thermoresponsive poly(oligoethylene glycol methacrylate) brush.

The temperature induced swelling/collapse transition of poly(oligoethylene glycol methacrylate) (POEGMA) brushes has been investigated in electrolyte solutions comprised of multiple anions. The behaviour of a POEGMA brush in mixed salt environments of potassium acetate (KCH3COO, causes collapse) and thiocyanate (KSCN, causes swelling), two ions at opposite ends of the Hofmeister series, has been monitored with neutron reflectometry (NR) and quartz crystal microbalance with dissipation (QCM-D). These techniques revealed that the balance of the swelling/collapse influence of the two ions on the structure of the brush is temperature dependent. At low temperatures in mixed salt environments, the influence of the acetate and thiocyanate ions appears additive, antagonistic and approximately equal in magnitude, with brush thickness and dissipation similar to the brush in the absence of electrolyte. At higher temperatures, the influence of the acetate ion diminishes, resulting in an increase in the relative influence of the thiocyanate ion on the brush conformation. These temperature dependent specific ion effects are attributed to increased steric crowding in the brush, along with an increased affinity of the thiocyanate ion for the polymer at higher temperatures.