Diblock bottlebrush polymer in a non-polar medium: Self-assembly, surface forces, and superlubricity.

Whilst bottlebrush polymers have been studied in aqueous media for their conjectured role in biolubrication, surface forces and friction mediated by bottlebrush polymers in non-polar media have not been previously reported. Here, small-angle neutron scattering (SANS) showed that a diblock bottlebrush copolymer (oligoethyleneglycol acrylate/ethylhexyl acrylate; OEGA/EHA) formed spherical core-shell aggregates in n-dodecane (a model oil) in the polymer concentration range 0.1-2.0 wt%, with a radius of gyration Rg âˆ¼ 7 nm, comprising 40-65 polymer molecules per aggregate. The surface force apparatus (SFA) measurements revealed purely repulsive forces between surfaces bearing inhomogeneous polymer layers of thickness L âˆ¼ 13-23 nm, attributed to adsorption of a mixture of polymer chains and surface-deformed micelles. Despite the surface inhomogeneity, the polymer layers could mediate effective lubrication, demonstrating superlubricity with the friction coefficient as low as µ ∼ 0.003. The analysis of velocity-dependence of friction using the Eyring model shed light on the mechanism of the frictional process. That is, the friction mediation was consistent with the presence of nanoscopic surface aggregates, with possible contributions from a gel-like network formed by the polymer chains on the surface. These unprecedented results, correlating self-assembled polymer micelle structure with the surface forces and friction the polymer layers mediate, highlight the potential of polymers with the diblock bottlebrush architecture widespread in biological living systems, in tailoring desired surface interactions in non-polar media.

Racial/Ethnic Discrimination and Food Consumption: Examination in Diverse Samples.

BACKGROUND: Racial/ethnic discrimination has been linked to poor health outcomes. Effects of discrimination on health behaviors, including patterns of food consumption, may contribute to health outcomes. PURPOSE: We examined relations of discrimination to consumption of healthy and unhealthy foods in two diverse samples. Structural equation modeling was used to examine variations in associations of discrimination to consumption by the timing and type of discrimination, for healthy vs. unhealthy food, and by sample. METHODS: Study 1 included a racially and ethnically diverse sample of adults from New York City (NYC: N = 157); Study 2 included a sample of American Indian and Alaska Native (AI/AN) adults from the Denver metro area (N = 303), many of whom also identified with other racial/ethnic groups. Participants completed self-report measures of racial/ethnic discrimination, food consumption, life stressors, and sociodemographic variables. RESULTS: Structural equation models indicated discrimination was associated with food consumption. Tests of model invariance indicated that the model of discrimination to food consumption can be applied to both samples. Discrimination within the past-week was associated with more frequent consumption of both unhealthy and healthy foods, whereas lifetime discrimination was associated with more frequent consumption only of unhealthy foods. CONCLUSIONS: The data were limited to self-report measures and only the frequency of consumption was assessed. The findings suggest discrimination may contribute to health disparities through effects on food consumption. Differential effects for past-week and lifetime discrimination suggest that multiple mechanisms may be involved.

Experiencing racial discrimination may undermine health through effects on health behavior, including patterns of food consumption. In two studies, we tested whether racial discrimination was linked with food consumption, specifically the frequency with which people ate healthy and unhealthy foods. We investigated both lifetime exposure to discrimination as well as more recent (past-week) exposure as predictors of food consumption. Study 1 focused on racially and ethnically diverse adults from New York City (NYC); Study 2 focused on American Indian and Alaska Native (AI/AN) adults from the Denver metro area. Overall, we found that higher levels of discrimination were associated with more frequent consumption of both unhealthy and healthy food. The timing of discrimination mattered. Higher levels of discrimination within the past-week were associated with more frequent consumption of healthy and unhealthy foods. In contrast, higher levels of lifetime discrimination were associated only with more frequent consumption of unhealthy food. The links between discrimination and food consumption remained significant controlling for socioeconomic status. The relations of discrimination to food consumption were similar across the diverse sample from NYC and the AI/AN sample from Denver. These findings may help researchers understand how discrimination may contribute to health disparities.

The discovery of the depletion force.

This Editorial reports how the depletion force theory was originally developed by Sho Asakura and Fumio Oosawa and how their one-page paper was "rediscovered" about 20 years after the paper was published. The first part of this Editorial is mostly based on the lecture by Oosawa and his autobiographies, and the second part is written by one of two scientists who found the paper. The aim of this Editorial is to record the background of the discovery of the depletion force. We believe that this Editorial presents an interesting story showing how science develops. The story reminds us of the importance of basic education and continuous interests in unknown phenomena and interactions between people of different disciplines, although they are sometimes considered as separate elements of research.

McBain and the centenary of the micelle.

In 1913, J.W. McBain introduced the word "micelle" into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.

Early (pre-DLVO) studies of particle aggregation.

The history of colloid science, from its modern foundations in the mid-nineteenth century, has been strongly concerned with studies of the aggregation of colloidal particles. It was Thomas Graham (1861) who defined the word "colloid" (from the Greek word for glue) for those materials which could not pass through membranes, unlike smaller, truly-dissolved materials. Subsequently, Graham (1864), following earlier studies, principally by Selmi and Faraday, described "the power possessed by salts for destroying colloidal solutions". Although numerous, quantitative studies of particle aggregation were made in the years that followed, in particular, the determination of minimum electrolyte concentrations for the onset of particle aggregation and aggregation rates, no general theoretical framework emerged to account for these quantitative findings until the middle of the twentieth century. It was during and immediately following the Second World War that two sets of authors, Derjaguin and Landau, in Russia, and Verwey and Overbeek, in the Netherlands, independently came up with the theory that is now universally referred to as the DLVO theory of particle interactions and aggregation. All modern developments of the theory of particle aggregation use the DLVO theory as the keystone. However, the DLVO theory itself was based on a large body of experimental data in regard to particle aggregation obtained over the previous hundred years or so. This article is an attempt to review that body of experimental data and to show how this guided the DLVO authors in their thinking.

Photo-responsive properties of poly(NIPAM-co-AAc) microgel particles with absorbed, hydrophobically modified organic salts.

The absorption of two hydrophobically modified organic salts (HMOSs), containing azobenzene units, into poly(N-isopropylacrylamide-co-acrylic acid) microgel particles has been studied at pH 8 and 20 °C. These dispersions were then irradiated with UV light (wavelength 365 nm) for 10 min to observe the effect on the microgel particle properties, such as the adsorbed amount of the HMOS, the particle size, and the electrophoretic mobility. We show that irradiation of these dispersions with UV light can lead to induced, partial desorption of the HMOS molecules, with concomitant changes in the size and electrophoretic mobility of the microgel particles. This is due to a conformational switch (trans-form to cis-form) in the HMOS molecules, which reduces the strength of the hydrophobic interaction between the HMOS molecules and the isopropyl moieties within the microgel network. Moreover, the original absorbed amounts, size, and electrophoretic mobility values can be largely restored after storage in the dark for extended periods.

Electrically induced colloidal clusters for generating shear mixing and visualizing flow in microchannels.

When aqueous suspensions of 1 µm, negatively charged polystyrene particles are subject to a 1 kHz alternating electric field of strength greater than 7 kV(rms) m(-1), dynamic elliptical clusters of particles spontaneously form. With potential applications in microchannel fluidics in mind, we characterize how cluster formation and particle circulation, driven by induced dipole-dipole interactions, is critically dependent on time, field strength, electrolyte concentration, and cell thickness. Logarithmic growth of cluster size is observed, and particle velocity within the clusters is found to be proportional to cluster length. Increasing cell thickness from 10 to 60 µm increases the projected cluster area but decreases cluster aspect ratio as the result of changing particle dispersal rates. Clusters are shown to generate significant fluid shear suitable for microchannel mixing applications. These clusters are observed to distort under transverse fluid flow and, above a critical flow rate, to undergo a transition to form regularly spaced particle streams, which may be suitable for two-dimensional visualization of fluid flow.

Effect of chain length on the interaction between modified organic salts containing hydrocarbon chains and poly(N-isopropylacrylamide-co-acrylic acid) microgel particles.

A series of four hydrophobically modified, diphenylazo-based organic salts have been prepared and characterized. To achieve this a C(x) (x = 4, 6, 8, or 10) hydrocarbon chain was inserted between the diphenylazo moiety and the quaternary ammonium headgroup of the salt. The absorption of each of the four modified organic salts into anionic microgel particles of poly(N-isopropylacrylamide-co-acrylic acid) has been studied at pH 8. In addition, the hydrodynamic diameters and electrophoretic mobilities of the microgel particles have been studied as a function of the organic salt concentration, also at pH 8. In addition to the electrostatic attraction between the quaternary ammonium head groups of the organic salts and the anionic groups within the microgel particles, hydrophobic association between the chains of the organic salts within the microgel particles plays a role, with this effect increasing strongly from x=4 to 10. Desorption of the x=4 and 6 organic salts occurs readily on changing, in situ, the pH from 8 to 2.5 (and thereby eliminating the electrostatic interaction) but is only partially achieved for the x=8 and 10 organic salts. Indeed, for the x=10 organic salt, only about 80% of the organic salt is desorbed upon dilution of the microgel particles into a large excess of water.

Two-stage phase separation in ternary colloid-polymer mixtures.

Whilst binary colloid-polymer mixtures have been studied in detail over the past few decades, here the first results are presented on a ternary mixture involving two particle sizes. Novel and unusual phase separation kinetics are found, with a liquid phase separating from an aggregate phase.

MiS-MALDI: microgel-selected detection of protein biomarkers by MALDI-ToF mass spectrometry.

Intensified efforts to decipher the origin of disease at the molecular level stimulate the emergence of more efficient proteomic technologies. To complement this, attempts are being made to identify new predictive biomarkers for building more reliable biomarker patterns. As biomarker research gathers pace an immediate interest becomes focused on platforms, which although based on mainstream approaches, are more amenable to specialist tasks. Particularly relevant this is for disease-specific biomarkers, which are present at very low concentrations in multicomponent biological fluids and require depletion protocols enabling their separation from high-abundance components. In this report, we describe a new strategy allowing the rapid detection of target protein biomarkers by MALDI-ToF mass spectrometry. The approach relies on selective sequestering of target proteins from complex media by engineered microgels, which select proteins by their size (<30 kDa) and isoelectric points (protein pI <6.5). Subsequently, biomarker-loaded microgels are subjected to direct mass-spectrometric analysis without the need for preceding protein extraction. Exemplified by a natural protein-folding motif, coiled-coil, the monitoring of hierarchical folding-dependent macromolecular systems by the approach is also shown. The described strategy offers a general rationale for versatile platforms for high throughput proteomics and holds promise for proteome fingerprinting of biomolecular interactions.

Interaction between lysozyme and colloidal poly(NIPAM-co-acrylic acid) microgels.

The interaction between lysozyme and colloidal poly(NIPAM-co-acrylic acid) microgels is investigated in aqueous solutions at neutral pH. Lysozyme binding isotherms, obtained within the ionic strength range 10-220 mM, indicate that the maximum uptake at 10 mM is 2.4 g lysozyme per gram dry gel, and that the uptake capacity decreases with increasing ionic strength to approximately 0 at 220 mM. Swelling isotherms, obtained from photon correlation spectroscopy measurements, show that the binding is accompanied by a substantial deswelling of the microgels. The microgel suspension is stable up to a protein-to-polymer charge ratio in the microgels of about 0.6, largely independent of ionic strength, whereas flocculation/sedimentation occurs at higher charge ratios. The charge ratio 0.6 corresponds to a zeta-potential of about -6 mV, as obtained from measurements of electrophoretic mobility. Binding and swelling isotherms are analyzed in detail and compared with predictions of theoretical model calculations. The influence of protein-protein attraction is highlighted, as well as the interplay between electrostatic interactions and network elasticity.

The phase behavior of dispersions of silica particles in mixtures of polystyrene and dimethylformamide.

Depletion-induced phase separation in mixtures of charged silica particles and nonadsorbing polymer near theta conditions (polystyrene in dimethylformamide) was studied. The colloid-polymer size ratio q was varied through the particle size and the electrical double layer thickness (kappa(-1)) through addition of lithium chloride (LiCl). The dependence of the phase boundaries, and the nature of the separated phases, on q and kappa is reported and is found to be in good agreement with recent theoretical predictions (Gogelein, C.; Tuinier, R. Eur. Phys. J., E 2008, 27, 171-184).

Organic-inorganic double shell composite microcapsules.

Here we present novel double shell composite microcapsules (melamine formaldehyde (MF) polymer inner shell and ripened CaCO(3) nanoparticle outer shell) prepared using a method based on in situ polymerisation to form a MF polymer shell inside the ripened CaCO(3) nanoparticulate microcapsules wall.

The interaction between multi-charged organic salts and poly(vinylpyridine) microgel particles.

The interaction between negatively charged organic salts, with one two and three sulfonate groups respectively, and positively charged poly(2-vinylpyridine) microgel particles has been investigated. Absorption isotherms are used to describe the uptake of organic salt into the microgel network and the particle size and electrophoretic mobility of the dispersions have been discussed in terms of the electrostatic attraction between the organic salts and microgel network. The results suggest that all organic salts interact weakly with the microgel particles, and there is a tendency towards more noticeable changes in the microgel dispersion properties at lower concentration as the number of sulfonate groups within the organic salts increases.

Aqueous dispersions of silica shell/water-core microcapsules.

The preparation is described of water-core/silica-based shell particles, from W/O emulsion droplets, by adding alkoxysilanes to the oil-continuous phase, to form the shell by an interfacial condensation reaction at the W/O interface. In order to form relatively thick (and hence stronger) shells, it is found necessary to use a mixture of tetraethoxysilane (TEOS) and diethoxydimethylsilane (DEODMS), rather than TEOS alone. It is suggested that, in the former case, trans-shell diffusion of the alkoxysilane monomers (from the oil side) and water molecules (from the aqueous side) can continue, as a result of the higher permeability of the shells to these small molecules, thus allowing the interfacial condensation reaction to continue, even when the reaction would have ceased for a harder shell, having a much lower permeability, as occurs when TEOS alone is used. A successful method of transferring the water-core/silica-based shell particles from oil into water is described, based on the direct centrifugation of the particles from an upper oil phase (containing the dispersed particles initially) into a lower aqueous phase placed beneath, which contains a surfactant capable of adsorbing onto the particles and making them water-wetted.

The uptake and release of cationic surfactant from polyampholyte microgel particles in dispersion and as an adsorbed monolayer.

The use of novel polyampholyte microgel particles for the controlled absorption and release of a cationic surfactant has been investigated. The addition of cetylpyridinium chloride (CPC) to aqueous dispersions of poly(2-diethylamino)ethyl methacrylate-co-methacrylic acid (DEAEM-co-MAAc) microgel particles has been studied with respect to CPC concentration and solution pH. CPC was found to absorb into the polyampholyte microgel particles, resulting in reduced hydrodynamic diameter and electrophoretic mobility, when added to microgel dispersion at pH 11. Strong desorption could be induced by switching the pH from 11 to 3, with most of the desorption occurring in the region of the isoelectric pH of the particles. The properties of surface-adsorbed monolayers of polyampholyte microgel particles were also investigated, both in the presence and absence of CPC. The substrate surface charge was found to influence the swelling profile of the adsorbed microgel monolayers. The interaction of CPC surfactant with monolayers of adsorbed microgel particles shows strong correlations with the interaction of CPC surfactant with microgel particles in dispersion.

Silica-shell/oil-core microcapsules with controlled shell thickness and their breakage stress.

The encapsulation of one material by another, to form core-shell particles (microcapsules), has many applications, principally the containment, protection, and distribution of an active material. This work describes the development of core-shell particles with silicone oil cores and solid silica-like shells of controlled thickness. Oligomeric polydimethylsiloxane (PDMS) emulsions are employed as the core templates for the formation of the solid shells. The core templates are prepared by the surfactant-free, condensation polymerization of diethoxydimethylsilane (DEODMS) that leads to the formation of monodisperse silicone oil/water emulsions. Solid silica-like, composite shells were formed through condensation of tetraethoxysilane (TEOS) and DEODMS onto the core templates. The shell thickness may be controlled by manipulation of relative TEOS and DEODMS concentrations or by quenching the shell development step. It is possible to incorporate a dye into the core prior to shell formation, which does not seem to permeate the shell. The coated PDMS particles were subjected to a controlled compression stress using a micromanipulation technique. The capsule breaking force was found to be proportional to the shell thickness, as quantified using scanning electron microscopy (SEM) ultramicrotomy.

Simple models for two-dimensional tunable colloidal crystals in rotating ac electric fields.

We compare the behavior of a new two-dimensional aqueous colloidal model system with a simple numerical treatment. To the first order the attractive interaction between the colloids induced by an in-plane rotating ac electric field is dipolar, while the charge stabilization leads to a shorter ranged, Yukawa-like repulsion. In the crystal-like "rafts" formed at sufficient field strengths, we find quantitative agreement between experiment and Monte Carlo simulation, except in the case of strongly interacting systems, where the well depth of the effective potential exceeds 250 times the thermal energy. The "lattice constant" of the crystal-like raft is located approximately at the minimum of the effective potential, resulting from the sum of the Yukawa and dipolar interactions. The experimental system has display applications, owing to the possibility of tuning the lattice spacing with the external electric field. Limitations in the applied field strength and relative range of the electrostatic interactions of the particles result in a reduction in tunable lattice spacing for small and large particles, respectively. The optimal particle size for maximizing the lattice spacing tunability was found to be around 1000 nm.