Incompatible Liquids in Confined Conditions

In applications involving organic vapour, the performance of high surface area carbons is often challenged by water vapour in the atmosphere. Small angle neutron scattering (SANS), through its ability to distinguish between different components by means of contrast variation, is ideally suited to investigating the behaviour of adsorbed layers in simultaneous contact with a mixed vapour phase. Even at high relative humidity (RH), water alone forms a discontinuous film composed of clusters on the surface of the oxidized microporous carbon used for these studies. When toluene is also present, all the available carbon surface is wetted. Toluene and water adsorb as a single phase already at RH 11.5%, and the concentration of water present in the adsorbed phase is as high as 2.9 wt.%, far above its solubility in bulk toluene (0.033 wt.% at 25 deg C). At RH 87% the concentration of water in the adsorbed phase is four times higher, approximately 12 wt.%. The recently proposed mechanism of anchoring of the water by the aromatic molecules may provide an explanation for this phenomenon

Structure of Latex-Silica Nanocomposite Films: A Small Angle Neutron Scattering Study

We report on the synthesis and structure of silica filled latex films. The main stage of the synthesis consists in physico-chemical manipulations of colloidal solutions of nanosilica and nanolatex beads, followed by drying and filmification. Hence, no mechanical energy which might contribute to building or destruction of aggregates of silica beads is supplied to the samples. We have analyzed the structure of the resulting filled latex films by means of Small Angle Neutron Scattering. The scattered intensity varies enormously with the physico-chemical parameters, indicating considerable structural modifications. To rationalize these results, we present a unified description of the data which successfully accounts for the main characteristics of the scattered intensity: the form factor of beads at large q vectors, the position of the intra- and inter-aggregate structure factor peaks, the small-q upturn observed in some cases, and the overall intensity in absolute units. This allows us to quantify the degree of aggregation of the silica in the matrix. It is found that the latter can be varied in a systematic manner by changing pH, silica volume fraction and quantity of added salt. In one extreme case, e.g., the aggregation number changes by a factor of about 1000 at constant silica volume fraction

Primary and Secondary Hydration Forces between Interdigitated Membranes Composed of Bolaform Microbial Glucolipids

To better understand lipid membranes in living organisms, the study of intermolecular forces using the osmotic pressure technique applied to model lipid membranes has constituted the ground knowledge in the field since four decades. However, the study of intermolecular forces in lipid systems other than phospholipids, like glycolipids, has gained a certain interest only recently. Even in this case, the work generally focus on the study of membrane glycolipids, but little is known on new forms of non-membrane functional compounds, like pH-responsive bolaform glycolipids. This works explores, through the osmotic stress method involving an adiabatic humidity chamber coupled to neutron diffraction, the short-range (< 2 nm) intermolecular forces of membranes entirely composed of interdigitated glucolipids. Experiments are performed at pH 6, when the glucolipid is partially negatively charged and for which we explore the effect of low (16 mM) and high (100 mM) ionic strength. We find that this system is characterized by primary and secondary hydration regimes, respectively insensitive and sensitive to ionic strength and with typical decay lengths of λ_H1= 0.37 ± 0.12 nm and λ_H2=1.97 ± 0.78 nm

SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes

International audienceScattering functions of sodium sulfonated polystyrene (NaPSS) star-branched polyelectrolytes with high sulfonation degrees were measured from their salt-free aqueous solutions, using the Small Angle Neutron Scattering (SANS) technique. Whatever the concentration c, they display two maxima. The first, of abscissa q 1 *, is related to a position order between star cores and scales as q 1 * 9 c 1/3. The second, of abscissa q 2 *, is also observed in the scattering function of a semi-dilute solution of NaPSS linear polyelectrolytes. In the dilute regime (c < c*, non-overlapping stars), peak abscissa does not depend on concentration c and is just an intramolecular characteristic associated with the electrostatic repulsion between arms of the same star. In the semi-dilute regime, due to the star interpenetration, the scattering function – through the peak position, reflects repulsion between arms of the same star or of different stars. The c threshold between these distinct c-dependencies of q 2 * in the dilute and semi-dilute regimes is estimated as c*. Just as simple is the measurement of the geometrical radius R of the star obtained from the q 1 * value at c* through the relation 2R = 2π/q 1 *. By considering NaPSS stars of the same functionality with different degrees of polymerization per arm N a , we find R scaling linearly with N a , suggesting an elongated average conformation of the arms. This is in agreement with theoretical predictions and simulations. Meanwhile the value of q 2 * measured in the dilute regime does not allow any inhomogeneous counterion distribution inside the stars to be revealed

Water modulates the lamellar structure and interlayer correlation of poly(perfluorooctyl acrylate) films: a specular and off-specular neutron scattering study

Comb-like polymers with pendant-like perfluorocarbon side chains self-assemble into smectic lamellae and have been extensively used as water-repellent, hydrophobic coating materials characterized by large water contact angles (θ > 120°). As poly(perfluorooctyl acrylate) films are “apparently hydrophobic” (θ > 120°), the interaction of such materials and water molecules has been largely overlooked. To unravel the molecular-level interactions between water and apparently hydrophobic polymers, specular and off-specular neutron scattering experiments were conducted at defined osmotic pressure ΠH2O. The poly{2-[(perfluorooctylethyl)carbamate]ethyl} acrylate (PFAUr-C₈), which had a carbamate linker, transitioned to another lamellar phase at 89 °C. At T = 25 °C; the lamellar periodicity of PFAUr-C₈ slightly increased with decreasing osmotic pressure, while the vertical correlation length increased. However, the poly[(perfluorooctyl)ethyl] acrylate (PFA-C₈) that did not contain a carbamate linker directly transitioned to a disordered phase at 84 °C. The lamellar periodicity of PFA-C₈ was largely independent of the osmotic pressure, suggesting that PFA-C₈ was poorly hydrated. Remarkably, the vertical correlation length decreased with decreasing osmotic pressure. Because hydration facilitated by the linker modulated the smectic lamellae of the poly(perfluoroalkyl acrylate), water molecules could be used to optimize the self-assembly of apparently hydrophobic liquid crystalline polymers

Interplay of Trans- and Cis-Interactions of Glycolipids in Membrane Adhesion

Glycolipids mediate stable membrane adhesion of potential biological relevance. In this article, we investigate the trans- and cis-interactions of glycolipids in molecular dynamics simulations and relate these interactions to the glycolipid-induced average separations of membranes obtained from neutron scattering experiments. We find that the cis-interactions between glycolipids in the same membrane leaflet tend to strengthen the trans-interactions between glycolipids in apposing leaflets. The trans-interactions of the glycolipids in our simulations require local membrane separations that are significantly smaller than the average membrane separations in the neutron scattering experiments, which indicates an important role of membrane shape fluctuations in glycolipid trans-binding. Simulations at the experimentally measured average membrane separations provide a molecular picture of the interplay between glycolipid attraction and steric repulsion of the fluctuating membranes probed in the experiments

Lipid domain formation and non-lamellar structures associated with varied lysylphosphatidylglycerol analogue content in a model Staphylococcal plasma membrane

Dipalmitoyl-3-aza-dehydroxy-lysylphosphatidylglycerol (DP3adLPG), is a chemically stable synthetic analogue of the bacterial lipid lysylphosphatidylglycerol (LPG), designed as a substitute for the notoriously labile native lipid in biophysical investigations. In Staphylococcus aureus, LPG is known to play a role in resistance to antibiotics by altering membrane charge properties in response to environmental stress, but little is known about how LPG influences other bilayer physicochemical properties or lateral organisation, through the formation of complexes with lipids such as phosphatidylglycerol (PG). In this study we have investigated the different phases formed by biomimetic mixtures of 3adLPG and PG in different thermotropic states, using neutron diffraction and electron microscopy. In a DPPG/DP3adLPG 70:30 mol% mixture, two distinct lamellar phases were observed below the lipid melting transition: Lβ′ 1 and Lβ′ 2 with respective periodicities of 82 and 62 Å. Increasing the proportion of DP3adLPG to mimic the effects of environmental stress led to the disappearance of the Lβ′ 1 phase and the formation of an inverse hexagonal phase. The compositions of these different phases were identified by investigating the thermotropic properties of the two mixtures, and probing their interaction with the antimicrobial peptide magainin 2 F5W. We propose that the observed polymorphism results from the preferential formation of either triplet PG-3adLPG-PG, or paired PG-3adLPG complexes, dependent upon the mixing proportions of the two lipids. The relevance of these findings to the role native LPG in S. aureus, are discussed with respect to their influence on antibiotic resistance and lateral membrane organisation

Biophysical properties of glycerolipids and their impact on membrane architecture and biology

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Swelling of a lecithin lamellar phase induced by small carbohydrate solutes.

In this paper, we consider the effect of adding small carbohydrate solutes (small sugars) to DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) L(alpha) dispersions and the consequences on the force balance at zero osmotic pressure (maximal swelling). We show the importance of long incubations required to obtain samples at thermodynamic equilibrium where molecular diffusion has been completed. The monotonic increase of maximal swelling versus sugar content occurs as a combined effect of the screening of the van der Waals contribution and fluctuations in the lamellar stacks. According to this new approach, it is shown that changes in dielectric properties result in a much less pronounced effect than entropic forces (undulations) generated by the softening of the membranes at high sugar content. However, this sugar-induced swelling cannot be explained quantitatively by adding an entropic contribution to molecular interactions. Quantitative disagreement between the proposed mechanism and our observations is due either to nonadditivity of molecular interactions with entropic forces or to the relation used to account for the entropic contribution