Molecular Hydrophobicity Signature in Charged Bidimensional Clay Materials.

The unraveling of the hydrophobicity/hydrophilicity molecular signature of nanometric bidimensional confined systems represents a challenging task with repercussions in environmental transport processes. Swelling clay minerals represent an ideal model system, as hydrophobicity can be modified during material synthesis by substituting hydroxyls by fluorine in the structure, without additional surface treatment. This following work presents a combined approach, integrating experimental inelastic neutron scattering spectroscopy and ab initio molecular dynamics simulations, with the objective of advancing our understanding of the role of surface hydroxylation/fluorination and the extent of confinement on water properties.

Correlating Substrate Reactivity at Electrified Interfaces with the Electrolyte Structure in Synthetically Relevant Organic Solvent/Water Mixtures.

Optimizing electrosynthetic reactions requires fine tuning of a vast chemical space, including charge transfer at electrocatalyst/electrode surfaces, engineering of mass transport limitations, and complex interactions of reactants and products with their environment. Hybrid electrolytes, in which supporting salt ions and substrates are dissolved in a binary mixture of organic solvent and water, represent a new piece of this complex puzzle as they offer a unique opportunity to harness water as the oxygen or proton source in electrosynthesis. In this work, we demonstrate that modulating water-organic solvent interactions drastically impacts the solvation properties of hybrid electrolytes.

Crystalline restacking of 2D-materials from their nanosheets suspensions.

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials HMSbPO, (where M = Li, Na, K, Rb, Cs and 0 ≤ ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. HSbPO aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors.

Ion specific tuning of nanoparticle dispersion in an ionic liquid: a structural, thermoelectric and thermo-diffusive investigation.

Dispersions of charged maghemite nanoparticles (NPs) in EAN (ethylammonium nitrate) a reference Ionic Liquid (IL) are studied here using a number of static and dynamical experimental techniques; small angle scattering (SAS) of X-rays and of neutrons, dynamical light scattering and forced Rayleigh scattering. Particular insight is provided regarding the importance of tuning the ionic species present at the NP/IL interface. In this work we compare the effect of Li, Na or Rb ions.

Electrical surface properties of nanoporous alumina membranes: influence of nanochannels' curvature, roughness and composition studied electrokinetic experiments.

Among classical nanoporous oxide membranes, anodic aluminum oxide (AAO) membranes, made of non-connected, parallel and ordered nanochannels, are very interesting nanoporous model systems widely used for multiple applications. Since most of these applications involve local phenomena at the nanochannel surface, the fine description of the electrical surface behavior in aqueous solution is thus of primordial interest. Here, we use an original experimental approach combining several electrokinetic techniques (tangential and transverse streaming potential as well as electrophoretic mobility experiments) to measure the -potential and determine the surface isoelectric points (IEPs) of several AAOs having different characteristic sizes and compositions.

Rheo-SAXS characterization of lead-treated oils: Understanding the influence of lead driers on artistic oil paint's flow properties.

From the 15 century onwards, painters began to treat their oils with lead compounds before grinding them with pigments. Such a treatment induces the partial hydrolysis of the oil triglycerides and the formation of lead soaps, which significantly modify the rheological properties of the oil paint. Organization at the supramolecular scale is thus expected to explain these macroscopic changes.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential.

Advanced design of a x-ray absorption spectroscopy setup for measuring transition metals speciation in molten carbonates, hydroxides and hydrogenosulfates.

Battery recycling is currently becoming a crucial issue. One possible treatment path involves the use of molten salts. A mechanistic understanding of the underlying processes requires being able to analyze in situ speciation in molten salts at various temperatures.

Innovative pressure environment combining hydrostatic pressure gradient and mechanical compression for structural investigations of nanoporous soft films.

The development of a new sample environment enabling X-ray scattering measurements at small and large angles under mechanical compression and hydraulic flow is presented. The cell, which is adapted for moderate pressures, includes beryllium windows, and allows applying simultaneously a compressive pressure up to 2.5 kbar in the perpendicular direction to the flow and either a hydrostatic pressure up to 300 bar or a pressure gradient of the same amplitude.

Fine tuning the structural colours of photonic nanosheet suspensions by polymer doping.

Aqueous suspensions of nanosheets are readily obtained by exfoliating low-dimensional mineral compounds like HSbPO. The nanosheets self-organize, at low concentration, into a periodic stack of membranes, a lamellar liquid-crystalline phase. Due to the dilution, this stack has a large period of a few hundred nanometres, it behaves as a 1-dimensional photonic material and displays structural colours.

Gold-clay nanocomposite colloids with liquid-crystalline and plasmonic properties.

Imparting liquid-crystal (LC) materials with the plasmonic properties of metal nanoparticles is actively pursued for applications. We achieved this goal by synthetizing gold nanoparticles onto clay nanosheets, leading to nematic nanocomposite suspensions. Optical observations and structural analysis show the growth of the gold nanoparticles without altering the LC properties of the nanosheets.

Organisation of clay nanoplatelets in a polyelectrolyte-based hydrogel.

We investigate the organisation of clay nanoplatelets within a hydrogel based on modified ionenes, cationic polyelectrolytes forming physically crosslinked hydrogels induced by hydrogen bonding and π-π stacking. Combination of small angle X-ray and neutron scattering (SAXS, SANS) reveals the structure of the polyelectrolyte network as well as the organisation of the clay additives. The clay-free hydrogel network features a characteristic mesh-size between 20 and 30 nm, depending on the polyelectrolyte concentration.

Destabilization of the Nematic Phase of Clay Nanosheet Suspensions by Polymer Adsorption.

Complex aqueous mixtures comprised of swelling clays and hydrosoluble polymers naturally occur in soils and play a major role in pedogenesis. They are also very often used for formulating oil-well drilling fluids, paints, and personal-care products. The suspensions of some natural clays, thanks to their large nanoparticle aspect ratio, spontaneously form nematic liquid-crystalline phases where the particles align parallel to each other, which affects their flow properties.

Green Earth pigments aqueous dispersions: NMR relaxation rates dataset.

The data presented here are related to the research paper entitled "Green Earth pigments dispersions: water dynamics at the interfaces". The nuclear magnetic resonance (NMR) relaxometry data are provided for various aqueous Green Earth (GE) pigments dispersions with volume fraction spanning approximately from 0.1 to 0.

Green earth pigments dispersions: Water dynamics at the interfaces.

Hypothesis: The objective is to elucidate the multiscale dynamics of water within natural mixtures of minerals, green earth pigments that are mainly composed of phyllosilicates containing large amount of iron. In particular, the interaction of water with the different kinds of surfaces has to be probed. One issue is to examine the influence of surface type, basal or edge, on the dispersion quality.

Aggregating ability of ferric chloride in the presence of phosphate ligand.

Complexing anions such as phosphate or silicate play an ambivalent role in the performance of hydrolyzing metal coagulants: On one hand, they significantly interfere with the hydrolytic pathway of conventional iron or aluminum coagulants, the associated destabilization mechanism remaining rather elusive; on the other hand, they have been shown to be key ingredients in the formulation of innovative coagulant solutions exhibiting improved removal efficiency, their action mechanism at the molecular scale being presently poorly understood. In this paper, we explore the effect of small additions of phosphate ligand on the chemical coagulation of silica nanoparticles with ferric chloride. Transmission Electron Microscopy-Energy Dispersed X-ray Spectroscopy (TEM-EDXS) combined with Extended X-ray absorption Fine Structure Spectroscopy (EXAFS) at the Fe K-edge are used to provide an insight into the nature of coagulant species, whereas jar-tests, laser diffraction, Small Angle X-ray Scattering (SAXS), and electrophoretic mobility, are used to investigate the aggregation dynamics of silica particles in the presence of phosphate ligand.

Aggregation of Plate-like Colloids Induced by Charged Polymer Chains: Organization at the Nanometer Scale Tuned by Polymer Charge Density.

We study the aggregation of charged plate-like colloids, Na-montmorillonite clays, in the presence of ionenes, oppositely charged polymer chains. The choice of the charged polymer allows tuning its linear charge density to match/mismatch the average charge separation on the clay surfaces. We assess the nanoscale structure of the aggregates formed by small-angle X-ray and neutron scattering.

How do Nucleotides Adsorb Onto Clays?

Adsorption of prebiotic building blocks is proposed to have played a role in the emergence of life on Earth. The experimental and theoretical study of this phenomenon should be guided by our knowledge of the geochemistry of the habitable early Earth environments, which could have spanned a large range of settings. Adsorption being an interfacial phenomenon, experiments can be built around the minerals that probably exhibited the largest specific surface areas and were the most abundant, i.

One Step up the Ladder of Prebiotic Complexity: Formation of Nonrandom Linear Polypeptides from Binary Systems of Amino Acids on Silica.

Evidence for the formation of linear oligopeptides with nonrandom sequences from mixtures of amino acids coadsorbed on silica and submitted to a simple thermal activation is presented. The amino acid couples (glutamic acid+leucine) and (aspartic acid+valine) were deposited on a fumed silica and submitted to a single heating step at moderate temperature. The evolution of the systems was characterized by X-ray diffraction, infrared spectroscopy, thermosgravimetric analysis, HPLC, and electrospray ionization mass spectrometry (ESI-MS).

Resistance to gastrointestinal nematodes in dairy sheep: Genetic variability and relevance of artificial infection of nucleus rams to select for resistant ewes on farms.

Breeding sheep for enhanced resistance to gastrointestinal parasites is a promising strategy to limit the use of anthelmintics due to the now widespread resistance of parasites to these molecules. This paper reports the genetic parameters estimated for parasite resistance and resilience traits in the Blond-faced Manech dairy sheep breed and the putative impacts of the selection for resistance to gastrointestinal nematodes (GIN) on farms. Two datasets were used.

Soft X-ray Heterogeneous Radiolysis of Pyridine in the Presence of Hydrated Strontium-Hydroxyhectorite and its Monitoring by Near-Ambient Pressure Photoelectron Spectroscopy.

The heterogeneous radiolysis of organic molecules in clays is a matter of considerable interest in astrochemistry and environmental sciences. However, little is known about the effects of highly ionizing soft X-rays. By combining monochromatized synchrotron source irradiation with in situ Near Ambient Pressure X-ray Photoelectron Spectroscopy (in the mbar range), and using the synoptic view encompassing both the gas and condensed phases, we found the water and pyridine pressure conditions under which pyridine is decomposed in the presence of synthetic Sr-hydroxyhectorite.