Search

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.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.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.

Structural characterisation of thermoresponsive polymer brushes in binary DMSO–water mixtures reveals both LCST and UCST behaviour.

Neutron reflectometry is the foremost technique for in situ determination of the volume fraction profiles of polymer brushes at planar interfaces. However, the subtle features in the reflectometry data produced by these diffuse interfaces challenge data interpretation. Historically, data analyses have used least-squares approaches that do not adequately quantify the uncertainty of the modeled profile and ignore the possibility of other structures that also match the collected data (multimodality). Here, a Bayesian statistical approach is used that permits the structural uncertainty and multimodality to be quantified for polymer brush systems. A free-form model is used to describe the volume fraction profile, minimizing assumptions regarding brush structure, while only allowing physically reasonable profiles to be produced. The model allows the total volume of polymer and the profile monotonicity to be constrained. The rigor of the approach is demonstrated via a round-trip analysis of a simulated system, before it is applied to real data examining the well characterized collapse of a thermoresponsive brush. It is shown that, while failure to constrain the interfacial volume and consider multimodality may result in erroneous structures being derived, carefully constraining the model allows for robust determination of polymer brush compositional profiles. This work highlights that an appropriate combination of flexibility and constraint must be used with polymer brush systems to ensure the veracity of the analysis. The code used in this analysis is provided, enabling the reproduction of the results and the application of the method to similar problems.

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.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.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 series of ionic liquids based on the 1-alkyl-3-methylimidazolium cations were examined as components of the solvent mixture for a bimolecular substitution process. The effects on both the rate coefficient of the process and the NMR spin-spin relaxation of the solvent components of changing either the alkyl chain length or the amount of ionic liquid in the reaction mixture were determined. At a constant mole fraction, a shorter alkyl chain length resulted in a greater rate coefficient enhancement and a longer relaxation time, with the opposite effects for a longer alkyl chain length. For a given ionic liquid, increasing the proportion of salt in the reaction mixture resulted in a greater rate coefficient and a shorter relaxation time. The microscopic origins of the rate coefficient enhancement were determined and a step change found in the activation parameters on increasing the alkyl chain length from hexyl to octyl, suggesting notable structuring in solution. Across a range of ionic liquids and solvent compositions, the relaxation time from NMR measurements was shown to relate to the reaction rate coefficient. The approach of using fast and simple NMR relaxation measurements to predict reaction outcomes was exemplified using a morpholinium-based ionic liquid.

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.

The nucleofugality of chloride has been measured in solvent mixtures containing ionic liquids for the first time, allowing reactivity in these solvents to be put in context with molecular solvents. Using well-described electrofuges, solvolysis rate constants were determined in mixtures containing different proportions of ethanol and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; the different solvent effects observed as the mixture changed could be explained using interactions of the ionic liquid with species along the reaction coordinate, determined using temperature dependent kinetic studies. The solvolysis data allowed determination of the nucleofugality of chloride in these mixtures, which varied with the proportion of salt in the reaction mixture, demonstrating quantitatively the importance of the amount of ionic liquid in the reaction mixture in determining reaction outcome. Nucleofugality data for chloride were determined in seven further ionic liquids, with the reactivity shown to vary over more than an order of magnitude. This outcome illustrates that the components of the ionic liquid are critical in determining reaction outcome. Overall, this work quantitatively extends the understanding of solvent effects in ionic liquids and demonstrates the potential for such information to be used to rationally select an ionic liquid to control reaction outcome.

HYPOTHESIS: Among other functions, mucins hydrate and protect biological interfaces from mechanical challenges. Mucins also attract interest as biocompatible coatings with excellent lubrication performance. Therefore, it is of high interest to understand the structural response of mucin films to mechanical challenges. We hypothesized that this could be done with Neutron Reflectometry using a novel sample environment where mechanical confinement is achieved by inflating a membrane against the films. EXPERIMENTS: Oral MUC5B mucin films were investigated by Force Microscopy/Spectroscopy and Neutron Reflectometry both at solid-liquid interfaces and under mechanical confinement. FINDINGS: NR indicated that MUC5B films were almost completely compressed and dehydrated when confined at 1 bar. This was supported by Force Microscopy/Spectroscopy investigations. Force Spectroscopy also indicated that MUC5B films could withstand mechanical confinement by means of steric interactions for pressures lower than ∼ 0.5 bar i.e., mucins could protect interfaces from mechanical challenges of this magnitude while keeping them hydrated. To investigate mucin films under these pressures by means of the employed sample environment for NR, further technological developments are needed. The most critical would be identifying or developing more flexible membranes that would still meet certain requirements like chemical homogeneity and very low roughness.

Rate constants for a bimolecular nucleophilic substitution (SN2) process in a range of ionic liquids are correlated with calculated parameters associated with the charge localisation on the cation of the ionic liquid (including the molecular electrostatic potential). Simple linear regression models proved effective, though the interdependency of the descriptors needs to be taken into account when considering generality. A series of ionic liquids were then prepared and evaluated as solvents for the same process; this data set was rationally chosen to incorporate homologous series (to evaluate systematic variation) and functionalities not available in the original data set. These new data were used to evaluate and refine the original models, which were expanded to include simple artificial neural networks. Along with showing the importance of an appropriate data set and the perils of overfitting, the work demonstrates that such models can be used to reliably predict ionic liquid solvent effects on an organic process, within the limits of the data set.

Complex fluids are widely used in formulated products to impart rheological properties like stability, performance, and aesthetics. Yield stress fluids are a particularly important example, enabling applications like particle suspension, surface coating, and therapeutic delivery. Recent work has shown that particle suspension in yield stress fluids can be a strong function of yielding and flow heterogeneities, especially in anisotropic fiber dispersions. This work uses a microbubble technique to study the deformation before and during yielding of microfibrous cellulose suspensions. We note significant variations in suspension performance as a result of fiber rearrangement and heterogeneities. Strong strain rate dependencies are found to vary local network yield strength, and confocal microscopy quantifies structural reinforcement and deformation rate effects. The observed behavior indicates a two-fluid interpretation may help interpret sparse network flow and suspension properties.

Microstructural effects on suspension and yielding are studied in aqueous dispersions of bacterial cellulose fibers using a small suspended air bubble as a sensitive probe particle. An external pressure field is used to control the applied stress and characterize very early stages of fluid yielding, as well as more developed flow. The bubble allows sensitive measurement of small yield stress values but also indicates a discrepancy between bulk and microscale yield stress values. Image analysis and flow visualization provide a measurement of the deformation, yielding, and flow of low-concentration microfiber dispersions at length scales comparable to that of the fibers. Tracking of trapped tracer particles indicates local restructuring occurs in fiber networks, driving heterogeneous yielding and flow. The observed heterogeneity effects decreased as fiber concentration increased, reducing network restructuring. The size of the yielded region in the gels varied inversely with fiber concentration, but did not fully account for the bulk-microscale discrepancies, indicating the gels are restructuring, responsive fluids. We suggest a two-fluid description of sparse fiber gels is necessary to fully account for the heterogeneity and suspension performance.

Wormlike micelles (WLMs) are vital components of many consumer products and industrial fluids, adding a shear-dependent viscous texture through their entanglement in solutions. It is now well accepted from experiments such as coupling rheology and scattering that, similar to many polymer solutions and dispersions of highly anisotropic particles, WLM behavior during shear arises from the alignment of the “worms” with the shear field, resulting in ordering that is rapidly lost in the cessation of shear. Most studies of such systems have been limited to dilute systems that are far below concentrations used industrially and commercially, due to the complexity of analyzing shear-induced many-body effects in high volume fraction dispersions. Here, we explore the shear alignment of concentrated WLM solutions comprising sodium laureth sulfate and cocamidopropyl betaine in 0.38 M aqueous sodium chloride. By analyzing only scattering data at high values of the scattering vector (i.e., correlations at short length scales that are dominant in such concentrated systems), we explore whether useful information can be obtained by naïvely approximating the WLMs as an ensemble of unconnected short rods representing sections of the worms. By taking this reductionist approach to analyzing the obtained two-dimensional scattering patterns from these systems under shear, we find that in this regime, such concentrated worms can be approximated as cylinders that become more aligned with the direction of shear as volume fraction and shear rate increase.

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.

Rate constants for a bimolecular nucleophilic substitution (SN2) process in a range of ionic liquids are correlated with calculated parameters associated with the charge localisation on the cation of the ionic liquid (including the molecular electrostatic potential). Simple linear regression models proved effective, though the interdependency of the descriptors needs to be taken into account when considering generality. A series of ionic liquids were then prepared and evaluated as solvents for the same process; this data set was rationally chosen to incorporate homologous series (to evaluate systematic variation) and functionalities not available in the original data set. These new data were used to evaluate and refine the original models, which were expanded to include simple artificial neural networks. Along with showing the importance of an appropriate data set and the perils of overfitting, the work demonstrates that such models can be used to reliably predict ionic liquid solvent effects on an organic process, within the limits of the data set.

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.

The refnx Python modules for neutron and X-ray reflectometry data analysis are introduced. A sample analysis illustrates a Bayesian approach using a Markov-chain Monte Carlo algorithm to understand the confidence in the fit parameters., refnx is a model-based neutron and X-ray reflectometry data analysis package written in Python. It is cross platform and has been tested on Linux, macOS and Windows. Its graphical user interface is browser based, through a Jupyter notebook. Model construction is modular, being composed from a series of components that each describe a subset of the interface, parameterized in terms of physically relevant parameters (volume fraction of a polymer, lipid area per molecule etc.). The model and data are used to create an objective, which is used to calculate the residuals, log-likelihood and log-prior probabilities of the system. Objectives are combined to perform co-refinement of multiple data sets and mixed-area models. Prior knowledge of parameter values is encoded as probability distribution functions or bounds on all parameters in the system. Additional prior probability terms can be defined for sets of components, over and above those available from the parameters alone. Algebraic parameter constraints are available. The software offers a choice of fitting approaches, including least-squares (global and gradient-based optimizers) and a Bayesian approach using a Markov-chain Monte Carlo algorithm to investigate the posterior distribution of the model parameters. The Bayesian approach is useful for examining parameter covariances, model selection and variability in the resulting scattering length density profiles. The package is designed to facilitate reproducible research; its use in Jupyter notebooks, and subsequent distribution of those notebooks as supporting information, permits straightforward reproduction of analyses.

The interfacial structures of a range of amphiphilic molecules are studied with both "soft" and "hard" hydrophobic substrates. Neutron reflection and quartz crystal microbalance with dissipation measurements highlight the differences between the adsorbed structures adopted by sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (C16TAB), and the "AM1" surface active peptide. At the soft siloxane/water interface, small molecular surfactants form loosely packed layers, with the hydrophobic tails penetrating into the oily layer, and an area per surfactant molecule that is significantly less than previously reported for the air/water interface. Neutron reflection measurements, supported by quartz crystal microbalance studies, indicate that for C16TAB, approximately 30 ± 8% of the alkyl tail penetrates into the poly(dimethylsiloxane) (PDMS) layer, whereas 20 ± 5% of the alkyl tail of SDS is located in the PDMS. For the engineered peptide surfactant AM1 (21 residues), it was found that one face of the α helix penetrated into the PDMS film. In contrast, penetration of the surfactant tails was not observed against hard solidlike hydrophobic surfaces made from octadecyltrichlorosilane (OTS) for any of the molecular species studied. At the OTS/water interface, C16TAB and SDS were seen to adsorb as larger aggregates and not as monolayers. Amphiphilic adsorption (amount, structural conformation) at the PDMS/water interface is shown to be different from that at both the air/water interface and the hard OTS/water interface, illustrating that interfacial structures cannot be predicted by the surfactant packing parameter alone. The bound PDMS layer is shown to be a useful proxy for the oil/water interface in surface and stabilization studies, with hydrophobic components of the molecules able to penetrate into the oily PDMS.

This work investigates synergistic and antagonistic effects of flotation reagents and salt on the air–liquid interface and stability of air bubbles under quasi-static conditions. Frothers of different families (aliphatic alcohol, polypropylene glycol and propylene glycol methyl ether), potassium amyl xanthate (PAX), a common collector used in the flotation of sulphide minerals, and sodium chloride (NaCl) were employed in the study. Adsorption of frother and collector molecules from individual and mixed solutions was studied through surface tension and Quartz Crystal Microbalance with Dissipation (QCM–D) measurements, while bubble stability was examined by the coalescence time of the bubble pairs in these solutions. The results show that NaCl enhanced the adsorption of frothers, while PAX's impact on the adsorption of the frother was found to be rather insignificant compared to the salt. The bubble coalescence time measurements, however, pointed to a significant synergistic effect between PAX and two frothers i.e., Methyl Iso Butyl Carbinol (MIBC) and Di Propylene Glycol (DPG) as reflected in the improvement of bubble stability. In the ternary solution systems (frother/NaCl/PAX), the concentration of salt in the MIBC mixture solution was found to have an opposite impact on the bubble lifetime in the DPG and DPM solutions. For instance, bubble lifetime increased with higher NaCl concentrations added to the DPG and DPM solutions, whereas it decreased in the MIBC solutions.

Plasma activated water (PAW) was used for surface treatments of beef meat. No significant reduction in vitamin B6, minerals and protein (% N and myoglobin) were observed with PAW treatment. PAW treatment did not significantly change L*and b* of beef sample with the observed reduction in a* comparable to that of the lactic acid treatment. No significant difference was found in oxymyoglobin, which correlates with the red appearance of meat. Furthermore, the extent of lipid oxidation was reduced with PAW treatment compared to water and lactic acid. Tenderness of raw beef increased after PAW treatment. When combined with vacuum packaging, the value of L* and b* in PAW treated beef are higher when compared to water treatment over the first 3 weeks, indicating good retention in colour over time. Effective inactivation was achieved with a 5.9 log reduction in Salmonella Typhimurium population and a 4 log reduction in E.coli population shown after exposure to PAW for up to 240 s and 300 s respectively. This study found that PAW treated beef retained, and in some cases improved, key quality parameters of importance for consumer acceptability such as limiting the extent of lipid oxidation and increasing beef tenderness.

The chemistry, antimicrobial efficacy and energy consumption of plasma-activated water (PAW) was optimized by altering the discharge frequency, ground-electrode configuration, gas flow rate and initial water conductivity for two reactor configurations, i.e., air pin-to-liquid discharge and air plasma-bubble discharge in water. The ratio of NO2− and NO3− formation was altered to optimise the antimicrobial effects of PAW, tested against two Gram-negative bacteria. An initial solution conductivity of 0.2 S·m−1 and 2000-Hz discharge frequency with the ground electrode positioned inside the pin reactor showed the highest antimicrobial effect resulting in a 3.99 ± 0.13-log10 reduction within 300 s against Escherichia coli and 5.90 ± 0.24-log10 reduction within 240 s for Salmonella Typhimurium. An excellent energy efficiency of reactive oxygen and nitrogen species (RONS) generation of 10.1 ± 0.1 g·kW−1·h−1 was achieved. Industrial relevance Plasma-activated water (PAW) is deemed as an eco-friendly alternative to chemical disinfection because its bactericidal activity is temporary. Optimizing the design and operation of PAW reactors to achieve high inactivation rates of more than 5-log10 reductions, as demonstrated in this work, will support the industrial application of this technology and the scaleup at industrial level.

Thermoresponsive ethylene glycol based comb-polymer brushes were studied as a function of copolymer composition in aqueous electrolyte solutions. Homopolymer poly oligo(ethylene glycol) methyl ether methacrylate (POEGMA 300 ) and statistical copolymer brushes with 60 mol% OEGMA 300 and 40 mol% (di(ethyleneglycol) methyl ether methacrylate) (MEO 2 MA) underwent a monotonic swollen to collapsed transition with increasing temperature. Neutron reflectometry and ellipsometry measurements showed that the higher ethylene glycol content of the homopolymer brush led to a higher degree of swelling for a given temperature, with the transition occurring over a wider temperature range than the copolymer brush. Dynamic atomic force microscopy force measurements revealed minimal impact of probe velocity on normal interaction forces for the homopolymer brush. In contrast, a significant increase in both repulsion and adhesion was observed for the copolymer brush. Exposure to potassium thiocyanate solutions increased the degree of swelling at any given temperature while potassium acetate showed the opposite behaviour for both brush compositions. However, the homopolymer brushes displayed a greater increase in swelling due to thiocyanate and reduced collapse due to acetate.

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 540A brush studied by ellipsometry, while the lower molecular weight ∼200A 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.

Soft polyhedral particles based on variations of the cubic symmetry group are produced from a precursor emulsion by extracting solvent to grow facets on the droplets. The droplets transform into liquid crystals with solid-like rheology and controlled size and shape. Small-angle X-ray scattering confirms a bicontinuous cubic liquid crystalline phase forms from aqueous glycerol monoolein and is responsible for the particle faceting observed. Different polyhedra are produced by varying face growth rates through control of precursor droplet size, system temperature, and solubilization and adsorption of guest molecules. More exotic faceted shapes can be formed by the soft particles by applying asymmetric solvent removal gradients and by deforming the precursor droplets into, for example, ellipsoids before crystallization. The method is a powerful means to produce soft polyhedra, using continuous microfluidic or other approaches, or to act as templates for hard polyhedral particle synthesis.

The conformation of a hydrophobic, weak cationic poly(2-diisopropylamino)ethyl methacrylate (PDPA) brush was studied using neutron reflectometry as a function of aqueous solution pH, ionic strength, and anion identity. In pH 4, 10 mM potassium nitrate the brush is highly charged, resulting in an extended, dilute conformation; at pH 9 the uncharged brush collapses to a single, dense layer. The brush response to added salt at constant pH (4.5) for varying concentrations of the potassium salts of acetate, nitrate, and thiocyanate revealed ion-specific conformations of the brush. At low ionic strength (0.1 mM) the brush was collapsed, independent of salt identity, while at higher ionic strengths (up to 500 mM) the conformation was dependent on counterion identity. The brush exhibited extended conformations in the presence of kosmotropic acetate counterions, while collapsed conformations were retained in the presence of strongly chaotropic thiocyanate counterions. The brush showed a richer set of behaviors in the solutions containing the weakly chaotropic nitrate anion, being similar to acetate (swollen) at intermediate concentrations but similar to thiocyanate (collapsed) at high salt concentrations. Numerical self-consistent field (nSCF) simulations indicate that the response of the brush to pH changes is dominated by the hydrophobicity of the polymer at pH values near the pKa. Furthermore, the simulations reveal that the addition of a single Flory–Huggins interaction parameter analogous to the hydrophilicity of the counterion is sufficient to replicate the observed specific anion response of a hydrophobic weak polyelectrolyte brush.

The effect of anion identity and temperature on the internal nanostructure of poly(N-isopropylacrylamide) brushes were investigated using neutron reflectometry (NR), atomic force microscopy (AFM), and quartz crystal microbalance with dissipation monitoring (QCM-D). NR and QCM-D measurements showed that addition of strongly kosmotropic acetate anions shifted the lower critical solution temperature (LCST) to lower temperatures relative to pure D2O/H2O, while strongly chaotropic thiocyanate anions shifted the LCST to higher temperatures. Polymer density profiles derived from NR showed direct evidence of vertical phase separation at temperatures around the LCST in all conditions. Results indicate that the density profiles were not simple modulations of structures observed in D2O to higher or lower temperatures, with both anion identity and ionic strength found to influence the qualitative features of the profiles. In particular, the presence of thiocyanate broadened the LCST transition which is attributed to ...

The effect of electrolyte identity on the conformation of homopolymer brushes of poly(2-(2-methoxyethoxy) ethyl methacrylate) (PMEO2MA) and poly(2-(diethylamino)ethyl methacrylate) (PDEA), as well as a P(MEO2MA-co-DEA) copolymer brush of 90:10 mol% composition has been examined. PMEO2MA is a thermoresponsive polymer with a lower critical solution temperature of ~28 °C, PDEA a weak polybase with an apparent pKa of ~7.5, while the copolymer brush exhibits both pH and temperature responsive behaviour. Brushes were synthesised using surface initiated ARGET ATRP. The effect of temperature at low and high pH in the presence of different electrolytes on the thickness of the P(MEO2MA-co-DEA) 90:10 mol% brush was tracked with ellipsometry and the polymer volume fraction profile was elucidated with neutron reflectometry. The effect of each electrolyte on the copolymer brush conformation as the temperature changes could be switched by changing the pH from low (charged DEA segments) to high (uncharged DEA segments). The overall behaviour of the copolymer in each salt was PDEA-like at low pH, and MEO2MA-like at high pH. At low pH a reverse Hofmeister effect was observed, while at high pH a direct Hofmeister effect was observed.

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.

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.

The confinement of soft materials between surfaces is central to the interactions that lead to adhesion, lubrication, and colloidal stability. Force measurements have long been able to describe the potential that exists between various coated surfaces, but it is only more recently that scattering techniques have permitted the detailed study of surface layers under confinement. By focusing on the characterization of interfacial layer structures, there is a growing understanding of the structural basis for the previously reported interaction potentials. Work to date has illustrated that the nanoscale confinement of adsorbed polymers, polymer brushes, polyelectrolyte multilayers, liquid crystals and lipid bilayers frequently leads to unexpected structural features. Approaches to probing interfacial structures with X-ray reflection and neutron reflection are described along with some of the advances in sample environment design that have facilitated these explorations.

A series of dumbbell-shaped nanocomposite materials of poly(dimethylsiloxanes) (PDMSs) and polyhedral oligomeric silsesquioxanes (POSSs) were synthesized through hydrosilylation reactions of allyl- and vinyl-POSS and hydride-terminated PDMS. The chemical structures of the dumbbell-shaped materials, so-called POSS-PDMS-POSS triblocks, were characterized by (1)H NMR and FT-IR spectroscopy. The molecular weights of the triblock polymers were determined by gel permeation chromatography (GPC). Their size was analyzed by small-angle neutron scattering (SANS) and pulsed-field gradient stimulated echo (PFG STE) NMR experiments. The impact of POSS on the molecular mobility of the PDMS middle chain was observed by using (1)H spin-spin (T2) relaxation NMR. In contrast to the PDMS melts, the triblocks showed an increase in mobility with increasing molecular weight over the range studied due to the reduced relative concentration of constraints imposed by the end-tethered nanoparticles. The triblock systems were used to compare the impact of tethered nanoparticles on the mobility of the linear component compared to the mobility of the polymer in conventional blended nanocomposites. The tethered nanoparticles were found to provide more reinforcement than physically dispersed particles especially at high molecular weights (low particle concentration). The physical blends showed an apparent percolation threshold behavior.

Solvent relaxation NMR has been used to estimate the surface areas and wettability of various types of nanostructured carbon materials in a range of solvents including water, ethanol, and tetrahydrofuran. We illustrate the application of the technique through several short case studies using samples including nanocarbon blacks, graphene oxide, nanographites, and porous graphenes. The technique is shown to give a good measure of surface area, correlating well with conventional surface area estimates obtained by nitrogen adsorption, transmission electron microscopy, or light scattering for the non-porous samples. NMR relaxation has advantages in terms of speed of analysis and being able to use concentrated, wet, and opaque samples. For samples that are porous, two distinct surface areas can be estimated assuming the two environments ('inner' and 'outer') have the same surface chemistry, and that there is a slow exchange of solvent molecules between them. Furthermore, we show that differences in wettability and dispersability between samples dispersed in water, ethanol, and cyclopentanone can be observed, along with changes to the surface chemistry of the interface. Copyright © 2015 John Wiley & Sons, Ltd.

The interactions between the strong polyelectrolyte sodium poly(styrenesulfonate), NaPSS, and the neutral polymer poly(vinylpyrrolidone), PVP, were investigated in bulk and at the silica/solution interface using a combination of diffusion nuclear magnetic resonance spectroscopy (NMR), small-angle neutron scattering (SANS), solvent relaxation NMR, and ellipsometry. We show for the first time that complex formation occurs between NaPSS and PVP in solution; the complexes formed were shown not to be influenced by pH variation, whereas increasing the ionic strength increases the complexation of NaPSS but does not influence the PVP directly. The complexes formed contained a large proportion of NaPSS. Study of these interactions at the silica interface demonstrated that complexes also form at the nanoparticle interface where PVP is added in the system prior to NaPSS. For a constant PVP concentration and varying NaPSS concentration, the system remains stable until NaPSS is added in excess, which leads to depletion flocculation. Surface complex formation using the layer-by-layer technique was also reported at a planar silica interface.

The adsorption of dopants at the surface of 5CB has been studied using neutron reflection. The dopants were versions of 11OCB with partly fluorinated chains, and the 5CB was interfaced with air or with silica treated with fluorocarbon or hydrocarbon coatings. At the air interface, the F17-11OCB adsorbed homeotropically, and the amount increased on cooling into the nematic phase of 5CB. At low temperatures, the adsorption from the nematic phase appeared to saturate at a bilayer. At the solid interfaces, there was some evidence for a thin planar layer at the surface, but most of the adsorbed dopant was in the form of diffuse layers. In both cases, an increase in dopant concentration caused higher adsorbed amounts. For F17-11OCB, the amount absorbed was much greater for a fluorinated coating as opposed to a hydrocarbon-coated surface. Also no adsorption of the F3-11OCB could be detected, suggesting that the adsorption process is driven by the oleophobic effect. The results demonstrate that it is possible to manipulate surface properties of liquid crystals using surfactant-like dopants.

The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly(acrylic acid), PAA, used to determine the effect of charge on the structure of a polymer brushes under confinement. Without confinement both PEO and PAA brushes are found to be highly swollen with water, >50% v/v, with the expected parabolic brush structure. Compression of the PEO brushes with as little as 0.5 bar of confinement is found experimentally to reduce the brush to a polymer block of uniform density that is significantly dehydrated

The stability of shapes formed by three viscoelastic droplets during their arrested coalescence has been investigated using micromanipulation experiments. Addition of a third droplet to arrested droplet doublets is shown to be controlled by the balance between interfacial pressures driving coalescence and internal elasticity that resists total consolidation. The free fluid available within the droplets controls the transmission of stress during droplet combination and allows connections to occur via formation of a neck between the droplets. The anisotropy of three-droplet systems adds complexity to the symmetric case of two-droplet aggregates because of the multiplicity of orientations possible for the third droplet. When elasticity dominates, the initial orientation of the third droplet is preserved in the triplet's final shape. When elasticity is dominated by the interfacial driving force, the final shape can deviate strongly from the initial positioning of droplets. Movement of the third droplet to a more compact packing occurs, driven by liquid meniscus expansion that minimizes the surface energy of the triplet. A range of compositions and orientations are examined and the resulting domains of restructuring and stability are mapped based on the final triplet structure. A geometric and a physical model are used to explain the mechanism driving meniscus-induced restructuring and are related to the impact of these phenomena on multiple droplet emulsions.

A nanocomposite consisting of reduced graphene oxide and zinc oxide nanoparticles (RGO/ZnO) with unique structural features was developed as an efficient, sustainable, amphiphilic, heterogeneous catalyst for the synthesis of various 3-substituted indoles in water. The catalyst was recycled six times without significant loss in catalytic activity. The higher environmental compatibility and sustainability factors such as smaller E-factor and higher atom economy make the present methodology a true green and sustainable process for the synthesis of various biologically important 3-substituted indoles.

The weak polyelectrolyte sodium polyacrylate, NaPA, and the neutral poly(vinyl pyrrolidone), PVP, were combined and the effects of complexation both in solution and at the nanoparticle interface were studied under basic pH conditions. Using a combination of SANS and PCS, we demonstrate that attractive inter-polymer interactions occur between PVP and NaPA in solution (for polymers with molecular weights equal to 40 K and 60 K respectively); typically, no attractive interactions between PVP and NaPA are reported above a critical pH of 4–5. Polymer interactions in the bulk are observed between the larger molecular weight polymers studied. The mass ratios of polymer also affect the interactions in the bulk, indicating that polymer interactions are influenced by the charges present in the system. The addition of NaPA to a silica dispersion with PVP previously adsorbed to the particles is shown to led to polymer desorption and the destabilisation of the system leading to particle aggregation or even flocculation. SANS data show that the interparticle potential changes from being repulsive with bare silica or PVP-coated silica to attractive on addition of NaPA. The molecular weight of PVP is seen to affect the amount of polymer desorbed, whereas the molecular weight of NaPA had an effect on the aggregation of particles.

The competition between poly(vinylpyrrolidone) and poly(ethylene oxide) for adsorption at the silica surface was studied by solvent relaxation nuclear magnetic resonance and small-angle neutron scattering. The additive nature of the NMR relaxation rate enhancement was used to observe changes in the train layer when the two polymers were in direct competition for an increasing weight percentage of silica. PVP is shown to displace preadsorbed PEO from the particle surface, and this was observed for a range of PVP molecular weights. SANS measurements were found to give detailed information on the adsorption of the polymers in the separate systems; however, only qualitative information on the adsorption of the polymers could be obtained from the mixed samples. At a total polymer concentration of 0.4% w/v with 1.1% w/v silica, the SANS data were consistent with PVP adsorbing at the surface and dPEO remaining in solution, in agreement with the NMR data.

We have developed a unique surface force type apparatus that allows direct measurements of the structure of a polymer layer under a confining pressure using neutron reflection. We have used this device to study the structure and the mechanical properties of a water swollen poly(styrenesulfonic acid) (PSSA) and poly(allylamine) PAH polyelectrolyte multilayer on silicon under confining pressures. A multilayer of 23 bilayers (60 nm) in thickness and terminated with a PAH layer swells to about 21% (v/v) of H2O. When the layer is then confined between a flexible plastic film and the silicon substrate, increased confining pressure gradually decreases the amount of water in the multilayer until, at 5 bar, only 10% of H2O remains. For a layer of the same number of bilayers but terminated with PSSA, the layer swells to about 28% of water, but between a confining pressure of 0–1, this is reduced to 16%, after which higher confining pressures do not lead to changes in hydration. The bulk salt concentration does not ...

The micellization of Pluronic triblock copolymers (P103, P123, and L43) in the presence of flurbiprofen at different pH was studied by small-angle neutron scattering (SANS), pulsed-field gradient stimulated-echo nuclear magnetic resonance (PFGSE-NMR), and surface tension measurements. Addition of flurbiprofen to the Pluronic at low pH leads to an increase in the fraction of micellization, aggregation number, and the core radius of the micelles. However, changing the pH to above the pKa of flurbiprofen in an ethanol/water mixture (∼6.5) reduces the fraction of micellization and results in a weaker interaction between the drug and micelles due to the increased drug solubility in aqueous solution.

The effects of a nonionic alcohol ethoxylate surfactant, C(13)E(7), on the interactions between PVP and SDS both in the bulk and at the silica nanoparticle interface are studied by photon correlation spectroscopy, solvent relaxation NMR, SANS, and optical reflectometry. Our results confirmed that, in the absence of SDS, C(13)E(7) and PVP are noninteracting, while SDS interacts strongly both with PVP and C(13)E(7) . Studying interfacial interactions showed that the interfacial interactions of PVP with silica can be manipulated by varying the amounts of SDS and C(13)E(7) present. Upon SDS addition, the adsorbed layer thickness of PVP on silica increases due to Coulombic repulsion between micelles in the polymer layer. When C(13)E(7) is progressively added to the system, it forms mixed micelles with the complexed SDS, reducing the total charge per micelle and thus reducing the repulsion between micelle and the silica surface that would otherwise cause the PVP to desorb. This causes the amount of adsorbed polymer to increase with C(13)E(7) addition for the systems containing SDS, demonstrating that addition of C(13)E(7) hinders the SDS-mediated desorption of an adsorbed PVP layer.

The surfactant-mediated desorption of adsorbed poly(vinylpyrrolidone), PVP, from anionic silica surfaces by sodium dodecyl sulfate, SDS, was observed. While photon correlation spectroscopy shows that the size of the polymer-surfactant-particle ensemble grows with added SDS, a reduction in the near-surface polymer concentration is measured by solvent relaxation NMR. Volume fraction profiles of the polymer layer extracted from small-angle neutron scattering experiments illustrate that the adsorbed polymer layer has become more diffuse and the polymer chains more elongated as a result of the addition of SDS. The total adsorbed amount is shown to decrease due to Coulombic repulsion between the surfactant-polymer complexes and between the complexes and the anionic silica surface.

Numerical self-consistent field theory is used to study the structural characteristics of a polymer brush consisting of end-grafted comb-polymers. A comb-polymer brush is shown to retain the parabolic density profile characteristic of the unbranched brush. Increasing either the number of branches or the length of the side-chains leads to an increase in the height (H) of the brush. This is partly because of the branched structure: it is more favorable to stretch the polymer backbone, while leaving the side-chains almost unstretched. The other reason for the increased stretching is simply because of the extra polymer in the brush due to the branches. We find that it does not matter how the side-chains are distributed along the backbone for the predicted density profile; it is only the total amount of polymer in the side-chains that is important. The effect of branching on the brush height can be captured in a simple scaling law: H ∼ Nb(NT/Nb)2/3, where Nb is the chain length of the polymer backbone, NT is the total chain length, thus including the side-chains, and their ratio NT/Nb is a measure for the amount of branching. The structure of the branched brush is less suitable for keeping away small particles from the grafted interface. It is, however, a good way of increasing the polymer density, and thus its antifouling properties, when the grafting density of the brush is limited.

Understanding the gelation of liquids by low molecular weight solutes at low concentrations gives an insight into many molecular recognition phenomena and also offers a simple route to modifying the physical properties of the liquid. Bis-(α,β-dihydroxy ester)s are shown here to gel thermoreversibly a wide range of solvents, raising interesting questions as to the mechanism of gelation. At gelator concentrations of 5–50 mg ml−1, gels were successfully formed in acetone, ethanol/water mixtures, toluene, cyclohexane and chloroform (the latter, albeit at a higher gelator concentration). A range of neutron techniques – in particular small-angle neutron scattering (SANS) – have been employed to probe the structure of a selection of these gels. The universality of gelation in a range of solvent types suggests the gelation mechanism is a feature of the bis-(α,β-dihydroxy ester) motif, with SANS demonstrating the presence of regular structures in the 30–40 Å range. A correlation between the apparent rodlike character of the structures formed and the polarity of the solvent is evident. Preliminary spin-echo neutron scattering studies (SESANS) indicated the absence of any larger scale structures. Inelastic neutron spectroscopy (INS) studies demonstrated that the solvent is largely unaffected by gelation, but does reveal insights into the thermal history of the samples. Further neutron studies of this kind (particularly SESANS and INS) are warranted, and it is hoped that this work will stimulate others to pursue this line of research.