Anomalous ionic transport in tunable angstrom-size water films on silica.

Liquid and ionic transport through nanometric structures is central to many phenomena, ranging from cellular exchanges to water resource management or green energy conversion. While pushing down toward molecular scales progressively unveils novel transport behaviors, reaching ultimate confinement in controlled systems remains challenging and has often involved 2D Van der Waals materials. Here, we propose an alternative route which circumvents demanding nanofabrication steps, partially releases material constraints, and offers continuously tunable molecular confinement. This soft-matter-inspired approach is based on the spontaneous formation of a molecularly thin liquid film onto fully wettable substrates in contact with the vapor phase of the liquid. Using silicon dioxide substrates, water films ranging from angstrom to nanometric thicknesses are formed in this manner, and ionic transport within the film can then be measured. Performing conductance measurements as a function of confinement in these ultimate regimes reveals a one-molecule thick layer of fully hindered transport nearby the silica, above which continuum, bulk-like approaches account for experimental results. Overall, this work paves the way for future investigations of molecular scale nanofluidics and provides insights into ionic transport nearby high surface energy materials such as natural rocks and clays, building concretes, or nanoscale silica membranes used for separation and filtering.

Effects of salinity on the flow of dense colloidal suspensions.

We experimentally study the effects of salt concentration on the flowing dynamics of dense suspensions of micrometer-sized silica particles in microfluidic drums. In pure water, the particles are fully sedimented under their own weight, but do not touch each other due to their negative surface charges, which results in a "frictionless" dense colloidal suspension. When the pile is inclined above a critical angle θc ∼ 5° a fast avalanche occurs, similar to what is expected for classical athermal granular media. When inclined below this angle, the pile slowly creeps until it reaches flatness. Adding ions in solution screens the repulsive forces between particles, and the flowing properties of the suspension are modified. We observe significant changes in the fast avalanche regime: a time delay appears before the onset of the avalanche and increases with the salt concentration, the whole dynamics becomes slower, and the critical angle θc increases from ∼5° to ∼20°. In contrast, the slow creep regime does not seem to be heavily modified. These behaviors can be explained by considering an increase in both the initial packing fraction of the suspension Φ0, and the effective friction between the particles µp. These observations are confirmed by confocal microscopy measurements to estimate the initial packing fraction of the suspensions, and AFM measurements to quantify the particles surface roughness and the repulsion forces, as a function of the ionic strength of the suspensions.

Drying Drops of Paint Suspension: From "Fried Eggs" to Quasi-Homogeneous Patterns.

Drying of multicomponent sessile drops is a complex phenomenon involving intricate mechanisms. Here, we study the evaporation of drops made of paint suspension and investigate the influence of the substrate temperature and suspension concentration on the resulting deposit patterns. At low concentrations and temperatures, the pigments appear highly concentrated in a narrow area at the center of the drop, a morphology we call "fried eggs". Increasing the temperature or concentration leads to more homogeneous patterns. From a top-view camera used for monitoring the whole evaporative process, we identify three mechanisms responsible for the final pattern: inward/outward flows that convect the pigments, gelation of the paint suspension where pigments accumulate, and final drying of the drop that freezes the location of the pigments onto the substrate. The relative kinetics of these three mechanisms upon concentration and temperature govern the deposit growth and the morphology of the final pattern. These observations are quantitatively supported by rheological measurements highlighting a strong increase of the viscosity with concentration, consistent with the gelation mechanism. Finally, we show that the kinetics of drop drying is controlled by the substrate temperature.

Giant osmotic energy conversion measured in a single transmembrane boron nitride nanotube.

New models of fluid transport are expected to emerge from the confinement of liquids at the nanoscale, with potential applications in ultrafiltration, desalination and energy conversion. Nevertheless, advancing our fundamental understanding of fluid transport on the smallest scales requires mass and ion dynamics to be ultimately characterized across an individual channel to avoid averaging over many pores. A major challenge for nanofluidics thus lies in building distinct and well-controlled nanochannels, amenable to the systematic exploration of their properties. Here we describe the fabrication and use of a hierarchical nanofluidic device made of a boron nitride nanotube that pierces an ultrathin membrane and connects two fluid reservoirs. Such a transmembrane geometry allows the detailed study of fluidic transport through a single nanotube under diverse forces, including electric fields, pressure drops and chemical gradients. Using this device, we discover very large, osmotically induced electric currents generated by salinity gradients, exceeding by two orders of magnitude their pressure-driven counterpart. We show that this result originates in the anomalously high surface charge carried by the nanotube's internal surface in water at large pH, which we independently quantify in conductance measurements. The nano-assembly route using nanostructures as building blocks opens the way to studying fluid, ionic and molecule transport on the nanoscale, and may lead to biomimetic functionalities. Our results furthermore suggest that boron nitride nanotubes could be used as membranes for osmotic power harvesting under salinity gradients.

Nanoroughness Strongly Impacts Lipid Mobility in Supported Membranes.

In vivo lipid membranes interact with rough supramolecular structures such as protein clusters and fibrils. How these features whose size ranges from a few nanometers to a few tens of nanometers impact lipid and protein mobility is still being investigated. Here, we study supported phospholipid bilayers, a unique biomimetic model, deposited on etched surfaces bearing nanometric corrugations. The surface roughness and mean curvature are carefully characterized by AFM imaging using ultrasharp tips. Neutron specular reflectivity supplements this surface characterization and indicates that the bilayers follow the large-scale corrugations of the substrate. We measure the lateral mobility of lipids in both the fluid and gel phases by fluorescence recovery after patterned photobleaching. Although the mobility is independent of the roughness in the gel phase, it exhibits a 5-fold decrease in the fluid phase when the roughness increases from 0.2 to 10 nm. These results are interpreted with a two-phase model allowing for a strong decrease in the lipid mobility in highly curved or defect-induced gel-like nanoscale regions. This suggests a strong link between membrane curvature and fluidity, which is a key property for various cell functions such as signaling and adhesion.

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

Two-dimensional micromodels for studying the convective dissolution of carbon dioxide in 2D water-saturated porous media.

Convective dissolution is a perennial trapping mechanism of carbon dioxide in geological formations saturated with an aqueous phase. This process, which couples dissolution of supercritical CO2, convection of the liquid containing the dissolved CO2, and mixing of the latter within the liquid, has so far not been studied in two-dimensional porous media. In order to do so, two-dimensional (2D) porous micromodels (patterned Hele-Shaw cells) have been fabricated from UV-curable NOA63 glue. NOA63 is used instead of PDMS, which is permeable to CO2 and does not allow for a controlled no flux boundary condition at the walls. The novel fabrication protocol proposed here, based on the bonding of a patterned photo-lithographed NOA63 layer on a flat NOA63 base, shows good reproducibility regardless of the patterns' typical size, and allows for easy filling of the cell despite the small value of the gap. A pressure chamber allows pressurizing the CO2 and outside of the flow cell up to 10 bars. Experiments were performed in 11 different porous media geometries. As expected, a gravitational fingering instability is observed upon injection of gaseous carbon dioxide in the cell, resulting in the downwards migration of dissolved CO2 plumes through the 2D porous structure. The initial wavelength of the fingers is larger in the presence of a hexagonal lattice of pillars. This effect can be correctly predicted from the theory for the gravitational instability in a Hele-Shaw cell devoid of pillars, provided that the permeability of the hexagonal porous medium is considered in the theory instead of that of the Hele-Shaw cell. Fluctuations around the theoretical prediction observed in the data are mostly attributed to a hitherto unknown weak locking of the wavelength on the distance between closest pillars.

Indium Tin Oxide devices for amperometric detection of vesicular release by single cells.

The microfabrication and successful testing of a series of three ITO (Indium Tin Oxide) microsystems for amperometric detection of cells exocytosis are reported. These microdevices have been optimized in order to simultaneously (i) enhance signal-to-noise ratios, as required electrochemical monitoring, by defining appropriate electrodes geometry and size, and (ii) provide surface conditions which allow cells to be cultured over during one or two days, through apposite deposition of a collagen film. The intrinsic electrochemical quality of the microdevices as well as the effect of different collagen treatments were assessed by investigating the voltammetric responses of two classical redox systems, Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(3-/4-). This established that a moderate collagen treatment does not incur any significant alteration of voltammetric responses or degradation of the excellent signal-to-noise ratio. Among these three microdevices, the most versatile one involved a configuration in which the ITO microelectrodes were delimited by a microchannel coiled into a spiral. Though providing extremely good electrochemical responses this specific design allowed proper seeding and culture of cells permitting either single cell or cell cluster stimulation and analysis.