Location of Polyelectrolytes in Swollen Lipid Oligobilayers.

Osteoarthritis is caused by degeneration of the cartilage, which covers the bone ends of the joints and is decorated with an oligolamellar phospholipid (PL) bilayer. The gap between the bone ends is filled with synovial fluid mainly containing hyaluronic acid (HA). HA and PLs are supposed to reduce friction and protect the cartilage from wear in joint movement. However, a detailed understanding of the molecular mechanisms of joint lubrication is still missing. Previously, we found that aqueous solutions of HA and poly(allylamine hydrochloride) (PAH), the latter serving as a polymeric analogue to HA, adsorb onto the headgroups of surface-bound 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) oligobilayers and significantly enhance their stability with respect to shear forces, typically occurring in joint movement. We now investigated the precise location of PAH chains across the lipid films in neutron reflectivity measurements, as bridging of the oligobilayers by polyelectrolytes (PEs) might be the cause for their improved mechanical stability. In a first set of experiments, we used hydrogenated PAH and chain-deuterated DMPC (DMPC-d54) to improve the contrast between the lipids and potentially intruding PAH. However, due to difficulties in distinguishing between incorporation of water and PAH, penetration into the lipid chain region could hardly be proven quantitatively. Therefore, we designed a more elaborate experiment based on mixed films of DMPC-d54 and hydrogenated DMPC, which is insensitive to water penetration into the films. Beside facilitating a detailed structural characterization of the oligolamellar system, this elaborate approach showed that PAH adsorbs to the DMPC heads and penetrates the lipid tail strata. No PAH was found in the lipid head strata, which excludes bridging of several lipid bilayers by the PE chains. The data are consistent with the assumption that PAH bridges are formed between the headgroups of two adjacent bilayers and contribute to the enhanced mechanical stability.

Photo-Responsive Control of Adsorption and Structure Formation at the Air-Water Interface with Arylazopyrazoles.

Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air-water interfaces. Surface tensiometry, vibrational sum-frequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyl- and H-terminal groups at air-water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S-O (head group) and C-H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

Effects of Charge Density on Spread Hyperbranched Polyelectrolyte/Surfactant Films at the Air/Water Interface.

The interfacial structure and morphology of films spread from hyperbranched polyethylene imine/sodium dodecyl sulfate (PEI/SDS) aggregates at the air/water interface have been resolved for the first time with respect to polyelectrolyte charged density. A recently developed method to form efficient films from the dissociation of aggregates using a minimal quantity of materials is exploited as a step forward in enhancing understanding of the film properties with a view to their future use in technological applications. Interfacial techniques that resolve different time and length scales, namely, ellipsometry, Brewster angle microscopy, and neutron reflectometry, are used. Extended structures of both components are formed under a monolayer of the surfactant with bound polyelectrolytes upon film compression on subphases adjusted to pH 4 or 10, corresponding to high and low charge density of the polyelectrolyte, respectively. A rigid film is related to compact conformation of the PEI in the interfacial structure at pH 4, while it is observed that aggregates remain embedded in mobile films at pH 10. The ability to compact surfactants in the monolayer to the same extent as its maximum coverage in the absence of polyelectrolyte is distinct from the behavior observed for spread films involving linear polyelectrolytes, and intriguingly evidence points to the formation of extended structures over the full range of surface pressures. We conclude that the molecular architecture and charge density can be important parameters in controlling the structures and properties of spread polyelectrolyte/surfactant films, which holds relevance to a range of applications, such as those where PEI is used, including CO2 capture, electronic devices, and gene transfection.

Vertically Heterogeneous 2D Semi-Interpenetrating Networks Based on Cellulose Acetate and Cross-Linked Polybutadiene.

This work reports the feasibility of polybutadiene (PB) cross-linking under UV irradiation in the presence of a linear polymer, cellulose acetate (CA), to form semi-interpenetrating polymer networks at the air-water interface. The thermodynamic properties and the morphology of two-dimensional (2D) CA/PB blends are investigated after UV irradiation and for a wide range of CA volume fractions. A contraction of the mixed Langmuir films is observed independent of the composition, in agreement with that recorded for the individual PB monolayer after cross-linking. The PB network formation is demonstrated by in situ sum-frequency generation spectroscopy on the equivolumic CA/PB mixed film. From Brewster angle microscopy observations, the PB network synthesis does not induce any morphology change at the mesoscopic scale, and all of the mixed films remain homogeneous laterally. In situ neutron reflectometry is used to probe the effect of PB cross-linking on the vertical structure of CA/PB mixed films. For all studied compositions, significant thickening of the films is evidenced, consistent with their contraction ratio. This thickening is accompanied by a partial expulsion of the PB toward the film-air interface, which is attributed to the hydrophobic character of the PB. This phenomenon is stronger for films rich in PB. In particular, the structure of the PB-rich film undergoes a transition from vertically homogeneous to inhomogeneous along the depth. 2D semi-interpenetrating polymer networks can thus be synthesized at the air-water interface with a morphology that is strongly influenced by the polymer-polymer and polymer-environment interactions.

Surface Pressure-Induced Interdiffused Structure Evidenced by Neutron Reflectometry in Cellulose Acetate/Polybutadiene Langmuir Films.

Binary blends of water-insoluble polymers are a versatile strategy to obtain nanostructured films at the air-water interface. However, there are few reported structural studies of such systems in the literature. Depending on the compatibility of the polymers and the role of the air-water interface, one can expect various morphologies. In that context, we probed Langmuir monolayers of cellulose acetate (CA), of deuterated and postoxidized polybutadiene (PBd) and three mixtures of CA/PBd at various concentrations by coupling surface pressure-area isotherms, Brewster angle microscopy (BAM), and neutron reflectometry at the air-water interface to determine their thermodynamic and structural properties. The homogeneity of the films in the vertical direction, averaged laterally over the spatial coherence length of the neutron beam (∼5 µm), was assessed by neutron reflectometry measurements using D2O/H2O subphases contrast-matched to the mixed films. At 5 mN/m, the whole mixed films can be described by a single slightly hydrated thin layer. However, at 15 mN/m, the fit of the reflectivity curves requires a two-layer model consisting of a CA/PBd blend layer in contact with the water, interdiffused with a PBd layer at the interface with air. At intermediate surface pressure (10 mN/m), the determined structure was between those obtained at 5 and 15 mN/m depending on film composition. This PBd enrichment at the air-film interface at high surface pressure, which leads to the PBd depletion in the blend monolayer at the water surface, is attributed to the hydrophobic character of this polymer compared with the predominantly hydrophilic CA.

Stability of Fluid Ultrathin Polymer Films in Contact with Solvent-Loaded Gels for Cultural Heritage.

The removal of ultrathin amorphous polymer films in contact with an aqueous gelled solution containing small amounts of good solvent is addressed by means of specular and off-specular neutron reflectometry. The distribution of heavy water and benzyl alcohol is revealed inside Laropal A81, often employed as a protective varnish layer for Culture Heritage in the restoration of easel paintings. The swelling kinetics, interface roughness, and film morphologies were recorded as a function of temperature and increasing benzyl alcohol concentration in the dispersion of Pemulen TR-2, a hydrophobically modified acrylic acid copolymer. The addition of small amounts of good solvent results in the appearance of water-filled cavities inside the varnish, which grow with time. It is shown that while increasing the solvent concentration greatly enhances the hole growth kinetics, an increase in temperature above the glass transition temperature does not have such a big effect on the kinetics.

Swelling, dewetting and breakup in thin polymer films for cultural heritage.

The removal of ultrathin amorphous polymer films in contact with nonsolvent/solvent binary mixtures is addressed by means of neutron reflectometry and atomic force microscopy. The high resolution of neutron scattering makes it possible to resolve the distribution profiles of heavy water and benzyl alcohol inside Laropal®A81, often employed as a protective varnish layer for Culture Heritage in restoration of easel paintings. The swelling kinetics and distribution profiles were recorded as a function of time and increasing benzyl alcohol concentration in water. The varnish film swells by penetration of the good solvent. At higher concentrations water-filled cavities appear inside the varnish and grow with time. Contrary to homogeneous dissolution dewetting is observed at late stages of exposure to the liquid which leads to the Breakup of the film. The high resolution measurements are compared to bulk behaviour characterized by the ternary phase diagram and the Flory-Huggins interaction parameters are calculated and used to predict the swelling and solvent partition in the films. Distinct differences of the thin film to bulk behaviour are found. The expectations made previously for the behaviour of solvent/non-solvent mixtures on the removal of thin layers in the restoration of easel paintings should be revised in view of surface interactions.

Potassium, Calcium, and Magnesium Bridging of AOT to Mica at Constant Ionic Strength.

The bridging effect of a series of common cations between the anionic mica surface and the AOT anion has been studied in a condition of constant ionic strength and surfactant concentration. It was found that sodium ions did not show any bridging effect in this system; however, calcium, magnesium, and potassium all caused adsorption of the organic to the mica surface. The concentrations at which bridging occurred was probed, revealing that only a very low bridging cation concentration was required for binding. The bridged layer stability was also investigated, and the interaction was shown to be a weak one, with the bound layer in equilibrium with the species in the bulk and easily removed. Even maintaining ionic strength and bridging ion concentration was not sufficient to retain the layer when the free organic in solution was removed.

The viscoelastic signature underpinning polymer deformation under shear flow.

Entangled polymers are deformed by a strong shear flow. The shape of the polymer, called the form factor, is measured by small angle neutron scattering. However, the real-space molecular structure is not directly available from the reciprocal-space data, due to the phase problem. Instead, the data has to be fitted with a theoretical model of the molecule. We approximate the unknown structure using piecewise straight segments, from which we derive an analytical form factor. We fit it to our data on a semi-dilute entangled polystyrene solution under in situ shear flow. The character of the deformation is shown to lie between that of a single ideal chain (viscous) and a cross-linked network (elastic rubber). Furthermore, we use the fitted structure to estimate the mechanical stress, and find a fairly good agreement with rheology literature.

Determination of PMMA Residues on a Chemical-Vapor-Deposited Monolayer of Graphene by Neutron Reflection and Atomic Force Microscopy.

Chemical vapor deposition (CVD) is now a well-established method for creating monolayer graphene films. In this method, poly(methyl methacrylate) (PMMA) films are often coated onto monolayer graphene films to make them mechanically robust enough for transfer and further handling. However, it is found that PMMA is hard to remove entirely, and any residual polymers remaining can affect graphene's properties. We demonstrate here a method to determine the amount of PMMA remaining on the graphene sheet fabricated from CVD by a combined study of Raman scattering, atomic force microscopy, and neutron reflection. Neutron reflectivity is a powerful technique which is particularly sensitive to any interfacial structure, so it is able to investigate the density profile of the residual PMMA in the direction perpendicular to the graphene film surface. After the standard process of PMMA removal by acetone-IPA cleaning, we found that the remaining PMMA film could be represented as a two-layer model: an inner layer with a thickness of 17 Å and a roughness of 1 Å mixed with graphene and an outer diffuse layer with an average thickness of 31 Å and a roughness of 4 Å well mixed with water. On the basis of this model analysis, it was demonstrated that the remaining PMMA still occupied a significant fraction of the graphene film surface.

Dynamical structure of entangled polymers simulated under shear flow.

The non-linear response of entangled polymers to shear flow is complicated. Its current understanding is framed mainly as a rheological description in terms of the complex viscosity. However, the full picture requires an assessment of the dynamical structure of individual polymer chains which give rise to the macroscopic observables. Here we shed new light on this problem, using a computer simulation based on a blob model, extended to describe shear flow in polymer melts and semi-dilute solutions. We examine the diffusion and the intermediate scattering spectra during a steady shear flow. The relaxation dynamics are found to speed up along the flow direction, but slow down along the shear gradient direction. The third axis, vorticity, shows a slowdown at the short scale of a tube, but reaches a net speedup at the large scale of the chain radius of gyration.

Neutron Reflectometry of an Anionic Surfactant at the Solid-Liquid Interface under Shear.

Neutron reflectometry with in situ rheology is used to measure the shear response of an adsorbed anionic surfactant (sodium bis(2-ethylhexyl) sulfosuccinate, AOT) at the alumina-water interface. A low surfactant concentration is measured where a single bilayer adsorbs at the interface as well as a higher concentration where a multilamellar structure forms. The low concentration structure does not change with the imposed shear (oscillatory or steady). However, the lamellar phase shows a loss of structure under both steady and oscillatory shear. There are differences between the steady and oscillatory cases, which are discussed, with both showing a strong dependence on the strain amplitude.

An Anionic Surfactant on an Anionic Substrate: Monovalent Cation Binding.

Neutron reflectometry has been used to study the adsorption of the anionic surfactant bis(2-ethylhexyl) sulfosuccinate cesium salt on the anionic surface of mica. Evidence of significant adsorption is reported. The adsorption is reversible and changes little with pH. This unexpected adsorption behavior of an anionic molecule on an anionic surface is discussed in terms of recent models for surfactant adsorption such as cation bridging, where adsorption has been reported with the divalent ion calcium but not previously observed with monovalent ions.

Shear Alignment of Bola-Amphiphilic Arginine-Coated Peptide Nanotubes.

The bola-amphiphilic arginine-capped peptide RFL4RF self-assembles into nanotubes in aqueous solution. The nanostructure and rheology are probed by in situ simultaneous rheology/small-angle scattering experiments including rheo-SAXS, rheo-SANS, and rheo-GISANS (SAXS: small-angle X-ray scattering, SANS: small-angle neutron scattering, GISANS: grazing incidence small-angle neutron scattering). Nematic alignment of peptide nanotubes under shear is observed at sufficiently high shear rates under steady shear in either Couette or cone-and-plate geometry. The extent of alignment increases with shear rate. A shear plateau is observed in a flow curve measured in the Couette geometry, indicating the presence of shear banding above the shear rate at which significant orientation is observed (0.1-1 s-1). The orientation under shear is transient and is lost as soon as shear is stopped. GISANS shows that alignment at the surface of a cone-and-plate cell develops at sufficiently high shear rates, very similar to that observed in the bulk using the Couette geometry. A small isotope effect (comparing H2O/D2O solvents) is noted in the CD spectra indicating increased interpeptide hydrogen bonding in D2O, although this does not influence nanotube self-assembly. These results provide new insights into the controlled alignment of peptide nanotubes for future applications.

The Search for Nanobubbles by Using Specular and Off-Specular Neutron Reflectometry.

We apply specular and off-specular neutron reflection at the hydrophobic silicon/water interface to check for evidence of nanoscopic air bubbles whose presence is claimed after an ad hoc procedure of solvent exchange. Nanobubbles and/or a depletion layer at the hydrophobic/water interface have long been discussed and generated a plethora of controversial scientific results. By combining neutron reflectometry (NR), off-specular reflectometry (OSS), and grazing incidence small angle neutron scattering (GISANS), we studied the interface between hydrophobized silicon and heavy water before and after saturation with nitrogen gas. Our specular reflectometry results can be interpreted by assuming a submolecular sized depletion layer and the off-specular measurements show no change with nitrogen super saturated water. This picture is consistent with the assumption that, following the solvent exchange, no additional nanobubbles are introduced at significant concentrations (if present at all). Furthermore, we discuss the results in terms of the maximum surface coverage of nanobubbles that could be present on the hydrophobic surface compatibly with the sensitivity limit of these techniques.

Simulation of entangled polymer solutions.

We present a computer simulation of entangled polymer solutions at equilibrium. The chains repel each other via a soft Gaussian potential, appropriate for semi-dilute solutions at the scale of a correlation blob. The key innovation to suppress chain crossings is to use a pseudo-continuous model of a backbone which effectively leaves no gaps between consecutive points on the chain, unlike the usual bead-and-spring model. Our algorithm is sufficiently fast to observe the entangled regime using a standard desktop computer. The simulated structural and mechanical correlations are in fair agreement with the expected predictions for a semi-dilute solution of entangled chains.

Polarized Neutron Reflectometry of Nickel Corrosion Inhibitors.

Polarized neutron reflectometry has been used to investigate the detailed adsorption behavior and corrosion inhibition mechanism of two surfactants on a nickel surface under acidic conditions. Both the corrosion of the nickel surface and the structure of the adsorbed surfactant layer could be monitored in situ by the use of different solvent contrasts. Layer thicknesses and roughnesses were evaluated over a range of pH values, showing distinctly the superior corrosion inhibition of one negatively charged surfactant (sodium dodecyl sulfate) compared to a positively charged example (dodecyl trimethylammonium bromide) due to its stronger binding interaction with the surface. It was found that adequate corrosion inhibition occurs at significantly less than full surface coverage.

Neutron reflection study of the adsorption of the phosphate surfactant NaDEHP onto alumina from water.

The adsorption of a phosphorus analogue of the surfactant AOT, sodium bis(2-ethylhexyl) phosphate (NaDEHP), at the water/alumina interface is described. The material is found to adsorb as an essentially water-free bilayer from neutron reflection measurements. This is similar to the behavior of AOT under comparable conditions, although AOT forms a thicker, more hydrated layer. The NaDEHP shows rather little variation with added salt, but a small thickening of the layer on increasing the pH, in contrast to the behavior of AOT.

Self assembly of magnetic nanoparticles at silicon surfaces.

Neutron reflectometry was used to study the assembly of magnetite nanoparticles in a water-based ferrofluid close to a silicon surface. Under three conditions, static, under shear and with a magnetic field, the depth profile is extracted. The particles have an average diameter of 11 nm and a volume density of 5% in a D2O-H2O mixture. They are surrounded by a 4 nm thick bilayer of carboxylic acid for steric repulsion. The reflectivity data were fitted to a model using a least square routine based on the Parratt formalism. From the scattering length density depth profiles the following behavior is concluded: the fits indicate that excess carboxylic acid covers the silicon surface and almost eliminates the water in the densely packed wetting layer that forms close to the silicon surface. Under constant shear the wetting layer persists but a depletion layer forms between the wetting layer and the moving ferrofluid. Once the flow is stopped, the wetting layer becomes more pronounced with dense packing and is accompanied by a looser packed second layer. In the case of an applied magnetic field the prolate particles experience a torque and align with their long axes along the silicon surface which leads to a higher particle density.

Measurement of molecular mixing at a conjugated polymer interface by specular and off-specular neutron scattering.

Measurements have been performed on thermally equilibrated conjugated-polymer/insulating-polymer bilayers, using specular and off-specular neutron reflectivity. While specular reflectivity is only sensitive to the structure normal to the sample, off-specular measurements can probe the structure of the buried polymer/polymer interface in the plane of the sample. Systematic analysis of the scattering from a set of samples with varying insulating-polymer-thickness, using the distorted-wave Born approximation (DWBA), has allowed a robust determination of the intrinsic width at the buried polymer/polymer interface. The quantification of this width (12 Å ± 4 Å) allows us to examine aspects of the conjugated polymer conformation at the interface, by appealing to self-consistent field theory (SCFT) predictions for equilibrium polymer/polymer interfaces in the cases of flexible and semi-flexible chains. This analysis enables us to infer that mixing at this particular interface cannot be described in terms of polymer chain segments that adopt conformations similar to a random walk. Instead, a more plausible explanation is that the conjugated polymer chain segments become significantly oriented in the plane of the interface. It is important to point out that we are only able to reach this conclusion following the extensive analysis of reflectivity data, followed by comparison with SCFT predictions. It is not simply the case that conjugated polymers would be expected to adopt this kind of oriented conformation at the interface, because of their relatively high chain stiffness. It is the combination of a high stiffness and a relatively narrow intrinsic interfacial width that results in a deviation from flexible chain behaviour.