Repulsive, but sticky - Insights into the non-ionic foam stabilization mechanism by superchaotropic nano-ions.

HYPOTHESIS: The superchaotropic Keggin polyoxometalate α-SiW12O404- (SiW) was recently shown to stabilize non-ionic surfactant (C18:1E10) foams owing to electrostatic repulsion that arises from the adsorption of SiW-ions to the foam interfaces. The precise mechanism of foam stabilization by SiW however remained unsolved. EXPERIMENTS: Imaging and conductimetry were used on macroscopic foams to monitor the foam collapse under free drainage and small angle neutron scattering (SANS) at a given foam height allowed for the tracking of the evolution of film thickness under quasi-stationary conditions. Thin film pressure balance (TFPB) measurements enabled to quantify the resistance of single foam films to external pressure and to identify intra-film forces. FINDINGS: At low SiW/surfactant ratios, the adsorption of SiW induces electrostatic repulsion within foam films. Above a concentration threshold corresponding to an adsorption saturation, excess of SiW screens the electrostatic repulsion that leads to thinner foam films. Despite screened electrostatics, the foam and single foam films remain very stable caused by an additional steric stabilizing force consistent with the presence of trapped micelles inside the foam films that bridge between the interfaces. These trapped micelles can serve as a surfactant reservoir, which promotes self-healing of the interface leading to much more resilient foam films in comparison to bare surfactant foams/films.

When Bulk Matters: Disentanglement of the Role of Polyelectrolyte/Surfactant Complexes at Surfaces and in the Bulk of Foam Films.

Foam films display exciting systems as on one hand they dictate the performance of macroscopic foams and on the other hand they allow studies of surface forces. With regard to surface forces, we attempt to disentangle the effect of the foam film surfaces and the foam film bulk. For that, we study the influence of salt (LiBr) on foam films formed by mixtures of oppositely charged polyelectrolyte and surfactant: anionic monosulfonated polyphenylene sulfone (sPSO2-220) and cationic tetradecyltrimethylammonium bromide (C14TAB). Adding a small amount of salt (≤10-3 M) decreases the foam film stability due to a weakened electrostatic net repulsion. In contrast, a large amount of salt (10-2 M) unexpectedly increases the foam film stability. Disjoining pressure isotherms reveal that the increased stability is due to an additional steric stabilization, which is attributed to sPSO2-220/C14TAB complexes in the film bulk. These bulk complexes also contribute to the measured apparent surface potential between the two air/water interfaces. We find, for the first time, the formation of Newton black films for mixtures of anionic polyelectrolytes and cationic surfactants.

A new model to describe small-angle neutron scattering from foams.

The modelling of scattering data from foams is very challenging due to the complex structure of foams and is therefore often reduced to the fitting of single peak positions or feature mimicking. This article presents a more elaborate model to describe the small-angle neutron scattering (SANS) data from foams. The model takes into account the geometry of the foam bubbles and is based on an incoherent superposition of the reflectivity curves arising from the foam films and the small-angle scattering (SAS) contribution from the plateau borders. The model is capable of describing the complete scattering curve of a foam stabilized by the standard cationic surfactant tetradecyltrimethylammonium bromide (C14TAB) with different water contents, i.e. different drainage states, and provides information on the thickness distribution of liquid films inside the foam. The mean film thickness decreases with decreasing water content because of drainage, from 28 to 22 nm, while the polydispersity increases. These results are in good agreement with the film thicknesses of individual horizontal foam films studied with a thin-film pressure balance.

Insights into Extended Structures and Their Driving Force: Influence of Salt on Polyelectrolyte/Surfactant Mixtures at the Air/Water Interface.

This paper addresses the effect of polyelectrolyte stiffness on the surface structure of polyelectrolyte (P)/surfactant (S) mixtures. Therefore, two different anionic Ps with different intrinsic persistence length lP are studied while varying the salt concentration (0-10-2 M). Either monosulfonated polyphenylene sulfone (sPSO2-220, lP ∼20 nm) or sodium poly(styrenesulfonate) (PSS, lP ∼1 nm) is mixed with the cationic surfactant tetradecyltrimethylammonium bromide (C14TAB) well below its critical micelle concentration and studied with tensiometry and neutron reflectivity experiments. We kept the S concentration (10-4 M) constant, while we varied the P concentration (10-5-10-3 M of the monomer, denoted as monoM). P and S adsorb at the air/water interface for all studied mixtures. Around the bulk stoichiometric mixing point (BSMP), PSS/C14TAB mixtures lose their surface activity, whereas sPSO2-220/C14TAB mixtures form extended structures perpendicular to the surface (meaning a layer of S with attached P and additional layers of P and S underneath instead of only a monolayer of S with P). Considering the different P monomer structures as well as the impact of salt, we identified the driving force for the formation of these extended structures: compensation of all interfacial charges (P/S ratio ∼1) to maximize the gain of entropy. By increasing the flexibility of P, we can tune the interfacial structures from extended structures to monolayers. These findings may help improve applications based on the adsorption of P/S mixtures in the fields of cosmetic or oil recovery.

Gold nanoparticle distribution in polyelectrolyte brushes loaded at different pH conditions.

Composites made of polymer brushes with inclusions of gold nanoparticles (AuNPs) combine the responsive nature of polymer brushes with the optical properties of the AuNPs, which offers the possibility to be used as colorimetric sensors. To this end, it is crucial to know how AuNPs are distributed inside the brush. Here, this distribution was elucidated by neutron reflectometry with contrast variation and a self-consistent reflectivity analysis based on the analytical parameterization of the volume fraction profiles of all chemical components. In contrast to former studies, this analysis allows the determination of the spatial distribution of components separately from each other: polyelectrolyte, AuNP, and water. Cationic poly-[2-(Methacryloyloxy) ethyl] trimethylammonium chloride (PMETAC) brushes were loaded with 5 nm AuNPs, which were coated with a pH-sensitive capping. The pH was varied during the incubation of the brush in the AuNP suspension. At a lower pH, AuNPs form aggregates in suspension and are attached to the brush periphery. They adsorb into the brush but do not fully penetrate it due to their bulkiness. At a higher pH, AuNP suspensions are electrostatically stabilized and the AuNPs penetrate the brush entirely. However, the AuNP distribution over the brush is not homogeneous but decreases gradually toward the substrate. Penetration of the AuNPs leads to a more extended conformation of the brush. According to the results of the detailed analysis of all components, an increase in water content could be excluded as a reason for brush swelling but replacement of water by the AuNP was observed.

Introduction of Non-Vitamin K Antagonist Anticoagulants Strongly Increased the Rate of Anticoagulation in Hospitalized Geriatric Patients with Atrial Fibrillation.

BACKGROUND: The benefit of anticoagulative treatment to prevent thromboembolism has been established in patients with atrial fibrillation and flutter of all age groups. Traditionally, anticoagulation was underused in geriatric patients with atrial fibrillation and flutter. OBJECTIVE: The aim of this study was to assess whether the broad introduction of non-vitamin K antagonist oral anticoagulants into clinical medicine has changed the rate of older patients treated with anticoagulants for atrial fibrillation and flutter. METHODS: Hospitalized geriatric patients treated in 2015 were retrospectively studied for the presence of atrial fibrillation and flutter and the use or non-use of anticoagulation. The risk of stroke and the indication for permanent anticoagulation were assessed using the CHA2DS2-VASc score. RESULTS: Five hundred and twelve of 1320 patients showed a clear indication for therapeutic anticoagulation (38.8%). Of these, 431 patients (84.2%) had long-standing persistent (> 1 year)/permanent atrial fibrillation and flutter or paroxysmal/persistent (> 7 days) atrial fibrillation and flutter as well as CHA2DS2-VASc scores of ≥ 2 in men and ≥ 3 in women. In this group, 378 patients (87.7%) received anticoagulative treatment. Of all patients anticoagulated for atrial fibrillation and flutter, 221 received non-vitamin K antagonist oral anticoagulants (58.5%), 176 received apixaban (46.6%), 32 received rivaroxaban (8.5%), and 13 received dabigatran (3.4%). One hundred and seven patients received the vitamin K antagonist phenprocoumon (28.3%) and 50 patients received high-dose low-molecular-weight heparins (13.2%). In 21 patients (5.6% of all anticoagulated patients with atrial fibrillation and flutter), hemorrhagic complications were documented. Eleven complications (52.4; 5.0% of all patients treated with non-vitamin K antagonist oral anticoagulants) occurred during treatment with non-vitamin K antagonist oral anticoagulants, four (19.0%) during anticoagulation with phenprocoumon and six (28.6%) during treatment with low-molecular-weight heparins. No intracranial hemorrhages and no fatal bleeding events occurred. CONCLUSION: The introduction of non-vitamin K antagonist oral anticoagulants and an increased awareness of their benefits led to an increased use of anticoagulation from 52.8% (2011) to 87.7% (2015) in geriatric patients with atrial fibrillation and flutter at our institution.

Polymers and surfactants at fluid interfaces studied with specular neutron reflectometry.

This review addresses the advances made with specular neutron reflectometry in studies of aqueous mixtures of polymers and surfactants at fluid interfaces during the last decade (or so). The increase in neutron flux due to improvements in instrumentation has led to routine measurements at the air/water interface that are faster and involve samples with lower isotopic contrast than in previous experiments. One can now resolve the surface excess of a single deuterated component on the second time scale and the composition of a mixture on the minute time scale, and information about adsorption processes and dynamic rheology can also be accessed. Research areas addressed include the types of formed equilibrium surface structures, the link to foam film stability and the range of non-equilibrium effects that dominate the behavior of oppositely charged polyelectrolyte/surfactant mixtures, macroscopic film formation in like-charged polymer/surfactant mixtures, and the properties of mixtures of bio-polymers with surfactants and lipids.