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.

A first-principles alternative to empirical solvent parameters.

The use of solvents is ubiquitous in chemistry. Empirical parameters, such as the Kamlet-Taft parameters and Gutmann donor/acceptor numbers, have long been used to predict and quantify the effects solvents have on chemical phenomena. Collectively however, such parameters are unsatisfactory, since each describes ultimately the same non-covalent solute-solvent and solute-solute interactions in completely disparate ways. Here we hypothesise that empirical solvent parameters are essentially proxy measures of the electrostatic terms that dominate solvent-solute interactions. On the basis of this hypothesis, we develop a new fundamental descriptor of these interactions, , and show that it is a self-consistent, probe-free, first principles alternative to established empirical solvent parameters.

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.

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.

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.

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.

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.

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.

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.

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.

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-.

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.

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.

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.

Formation of Liquid Marbles Using pH-Responsive Particles: Rolling vs Electrostatic Methods.

Aqueous dispersions of micrometer-sized, monodisperse polystyrene (PS) particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) colloidal stabilizer on their surfaces were dried under ambient conditions at pH 3.0 and 10.0. The resulting dried cake-like particulate materials were ground into powders and used as a stabilizer to fabricate liquid marbles (LMs) by rolling and electrostatic methods. The powder obtained from pH 3.0 aqueous dispersion consisted of polydisperse irregular-shaped colloidal crystal grains of densely packed colloids which had hydrophilic character. On the other hand, the powder obtained from pH 10.0 aqueous dispersion consisted of amorphous and disordered colloidal aggregate grains with random sizes and shapes, which had hydrophobic character. Reflecting the hydrophilic-hydrophobic balance of the dried PDEA-PS particle powders, stable LMs were fabricated with distilled water droplets by rolling on the powders prepared from pH 10.0, but the water droplets were adsorbed into the powders prepared from pH 3.0. In the electrostatic method, where an electric field assists transport of powders to a droplet surface, the PDEA-PS powders prepared from pH 3.0 jumped to an earthed pendant distilled water droplet to form a droplet of aqueous dispersion. Conversely the larger powder aggregates prepared from pH 10.0 did not jump due to cohesion between the hydrophobic PDEA chains on the PS particles, resulting in no LM formation.

Effect of morphology on interactions between nanoparticle-stabilised air bubbles and oil droplets.

High-speed video analysis has enabled the interaction between a pair of millimetre-sized air bubbles to be studied in aqueous solution. The bubbles were grown in the presence of either poly(glycerol monomethacrylate)-poly(benzyl methacrylate) (PGMA-PBzMA) diblock copolymer spheres or poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) (PGMA-PHPMA-PBzMA) triblock copolymer worms prepared by polymerisation-induced self-assembly (PISA). A reduction in interfacial tension relative to air bubbles grown in the absence of nanoparticles indicated the adsorption of nanoparticles at the air-water interface. A concentration of 0.01% w/v PGMA-PBzMA spheres conferred air bubble stability after just 30 s interfacial ageing with stirring, whereas 300 s ageing was required for worms to prevent coalescence at the same copolymer concentration. However, longer coalescence times with interfacial age suggested greater worm adsorption on the air bubbles during this period. In striking contrast, although stable millimetre-sized n-dodecane droplets were obtained in the presence of 0.01% w/v copolymer worms, the copolymer spheres did not prevent coalescence at this low concentration. Finally, the multiphase interaction and stability of immiscible fluids in the presence of either spheres or worms was assessed. More specifically, an n-dodecane oil droplet and an air bubble were grown separately in the presence of either the spheres or worms and then brought into contact. In the absence of any nanoparticles, aqueous film drainage resulted in the formation of a compound droplet consisting of an air lens on the oil droplet. In the presence of 0.01% w/v nanoparticles, ageing times of either 30 s or 120 s were required to prevent formation of compound droplets when using spheres and worms, respectively. Moreover, this asymmetric system required much shorter ageing times in the presence of adsorbed nanoparticles to gain stability compared to either the symmetric air bubble or oil droplet systems. This stability is attributed to a bridging nanoparticle monolayer between the oil droplet and the air bubble.

Influence of molecular weight on PNIPAM brush modified colloidal silica particles.

The effect of molecular weight and temperature on the phase transition and internal structure of poly(N-isopropylacrylamide) brush modified colloidal silica particles was investigated using dynamic light scattering (DLS) and small angle neutron scattering (SANS) between 15 and 45 °C. Dry particle analysis utilising transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) all confirmed the thickness of the polymer brush shell increased as a function of polymerisation time. Hydrodynamic diameter and electrophoretic mobility results revealed that the brush modified particles transitioned from swollen shells to a collapsed conformation between 15 and 35 °C. The dispersions were electrosterically stabilised over the entire temperature range investigated, with minimal thermal hysteresis recorded. Modelling of the hydrodynamic diameter enabled the calculation of a lower critical solution temperature (LCST) which increased as a function of brush thickness. The internal structure determined via SANS showed a swollen brush at low temperatures (18 and 25 °C) which decayed radially away from the substrate, while a collapsed block-like conformation with 60% polymer volume fraction was present at 40 °C. Radial phase separation was evident at intermediate temperatures (30 and 32.5 °C) with the lower molecular weight sample having a greater volume fraction of polymer in the dense inner region at these temperatures.

Giant Pickering Droplets: Effect of Nanoparticle Size and Morphology on Stability.

The interaction between a pair of millimeter-sized nanoparticle-stabilized n-dodecane droplets was analyzed using a high-speed video camera. The droplets were grown in the presence of either poly(glycerol monomethacrylate)-poly(benzyl methacrylate) (PGMA-PBzMA) diblock copolymer spheres or poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(benzyl methacrylate) (PGMA-PHPMA-PBzMA) triblock copolymer worms prepared by polymerization-induced self-assembly. The effect of nanoparticle morphology on droplet coalescence was analyzed by comparing 22 nm spheres to highly anisotropic worms with a mean worm width of 26 nm and comparable particle contact angle. Both morphologies lowered the interfacial tension, providing direct evidence for nanoparticle adsorption at the oil-water interface. At 0.03 w/v % copolymer, an aging time of at least 90 s was required to stabilize the n-dodecane droplets in the presence of the worms, whereas no aging was required to produce stable droplets when using the spheres, suggesting faster diffusion of the latter to the surface of the oil droplets. The enhanced stability of the sphere-coated droplets is consistent with the higher capillary pressure in this system as the planar interfaces approach. However, the more strongly adsorbing worms ultimately also confer stability. At lower copolymer concentrations (≤0.01 w/v %), worm adsorption promoted droplet stability, whereas the spheres were unable to stabilize droplets even after longer aging times. The effect of mean sphere diameter on droplet stability was also assessed while maintaining an approximately constant particle contact angle. Small spheres of either 22 or 41 nm stabilized n-dodecane droplets, whereas larger spheres of either 60 or 91 nm were unable to prevent coalescence when the two droplets were brought into contact. These observations are consistent with the greater capillary pressure stabilizing the oil-water interfaces coated with the smaller spheres. Addition of an oil-soluble polymeric diisocyanate cross-linker to either the 60 or the 91 nm spheres produced highly stable colloidosomes, thus confirming adsorption of these nanoparticles.

Behavior of Bubble Interfaces Stabilized by Particles of Different Densities.

Stability of bubbles laden with particles of different densities was investigated. Capillary-held bubbles were produced and coated with particles across the density range of 1.2-3.6 g·cm(-3). The materials used were poly(methyl methacrylate) (PMMA), glass, and anatase. The interaction of the bubbles, once brought into contact, was monitored using high-speed video recording. Visual inspection indicated that denser particles were more easily displaced during the contact of the bubbles and therefore the PMMA particles provided a particle barrier more resistant to coalescence. The coalescence events yielded information on the surface properties of the bubble and the detachment of particles. The attached particles commonly dampen the oscillation of the coalesced bubbles through viscous drag and change in the surface properties (e.g., area-exclusion principle). The dampening of the oscillation generally leads to a reduced mass of particles detaching from the bubble surface. It was found that the different materials investigated did not offer clear evidence of the effect of particle detachment on the bubble surface properties in the present systems. On the other hand, the detachment of different particle materials seemed to be consistent with one another when comparing the attachment and detachment forces exerted on the particles based on their density, size, and hydrophobicity. It was concluded that particles of lower density are more effective in stabilizing interfaces, and thus particle density is an important parameter in the selection of materials for the handling of dispersions.

Giant pH-responsive microgel colloidosomes: preparation, interaction dynamics and stability.

The interactions of two oil droplets grown in the presence of swollen, lightly cross-linked cationic poly(tert-butylamino)ethyl methacrylate (PTBAEMA) microgels was monitored using a high-speed video camera. Three oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. Adsorption of the swollen microgel particles was confirmed by interfacial tension, interfacial elasticity and dilational viscosity measurements on single pendant oil droplets, and assessment of the oscillatory dynamics for coalescing droplet pairs. Like the analogous bulk emulsions, particle adsorption alone did not prevent coalescence of pairs of giant Pickering emulsion droplets. However, prior addition of surface-active PPG-TDI cross-linker to the oil phase results in the formation of highly stable microgel colloidosomes via reaction with the secondary amine groups on the PTBAEMA chains. Colloidosome stability depended on the age of the oil-water interface. This reflects a balance between the adsorption kinetics of the PPG-TDI cross-linker and the microgel particles, each of which must be present at the interface to form a stable colloidosome. Colloidosome formation was virtually instantaneous in n-dodecane, but took up to 120 s in the case of isopropyl myristate. The impact of an acid-induced latex-to-microgel transition on the interaction of giant colloidosomes (originally prepared at pH 10 using isopropyl myristate) was also studied. This acid challenge did not result in coalescence, which is consistent with a closely-related study (A. J. Morse et al., Langmuir, 2014, 30(42), 12509-12519). No evidence was observed for inter-colloidosome cross-linking, which was attributed to retention of an aqueous film between the adjacent pair of colloidosomes.