Wetting Transition on Hydrophobic Surfaces Covered by Polyelectrolyte Brushes

International audienceWe study the wetting by water of complex “hydrophobic-hydrophilic” surfaces made of a hydrophobic substrate covered by a hydrophilic polymer brush. Polystyrene (PS) substrates covered with polystyrene-block-poly(acrylic acid) PS-b-PAA diblock copolymer layers were fabricated by Langmuir-Schaefer depositions and analyzed by atomic force microscopy (AFM) and ellipsometry. On bare PS substrate, we measured advancing angles θA ) 93 ( 1° and receding angles θR ) 81 ( 1°. On PS covered with poorly anchored PS-b-PAA layers, we observed large contact angle hysteresis, θA ≈ 90° and θR ≈ 0°, that we attributed to nanometric scale dewetting of the PS-b-PAA layers. On well-anchored PS-b-PAA layers that form homogeneous PAA brushes, a wetting transition from partial to total wetting occurs versus the amount deposited: both θA and θR decrease close to zero. A model is proposed, based on the Young-Dupre´ equation, that takes into account the interfacial pressure of the brush Π, which was determined experimentally, and the free energy of hydration of the polyelectrolyte monomers ΔGPAA hyd , which is the only fitting parameter. With ΔGPAA hyd ≈ -1300 J/mol, the model renders the wetting transition for all samples and explains why the wetting transition depends mainly on the average thickness of the brush and weakly on the length of PAA chains

Chemical analysis and aqueous solution properties of Charged Amphiphilic Block Copolymers PBA-b-PAA synthesized by MADIX

We have linked the structural and dynamic properties in aqueous solution of amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the physico-chemical characteristics of the samples. Despite product imperfections, the samples self-assemble in melt and aqueous solutions as predicted by monodisperse microphase separation theory. However, the PBA core are abnormally large; the swelling of PBA cores is not due to AA (the Flory parameter chiPBA/PAA, determined at 0.25, means strong segregation), but to h-PBA homopolymers (content determined by Liquid Chromatography at the Point of Exclusion and Adsorption Transition LC-PEAT). Beside the dominant population of micelles detected by scattering experiments, capillary electrophoresis CE analysis permitted detection of two other populations, one of h-PAA, and the other of free PBA-b-PAA chains, that have very short PBA blocks and never self-assemble. Despite the presence of these free unimers, the self-assembly in solution was found out of equilibrium: the aggregation state is history dependant and no unimer exchange between micelles occurs over months (time-evolution SANS). The high PBA/water interfacial tension, measured at 20 mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems are neither at thermal equilibrium nor completely frozen systems: internal fractionation of individual aggregates can occur.Comment: 32 pages, 16 figures and 4 tables submitted to Journal of Interface and Colloidal Scienc

Droplets in Microchannels: Dynamical Properties of the Lubrication Film

International audienceWe study the motion of droplets in a confined, micrometric geometry, by focusing on the lubrication film between droplet and wall. When capillary forces dominate, the lubrication film thickness evolves non linearly with the capillary number due to viscous dissipation between meniscus and wall. However, this film may become thin enough (tens of nanometers) that intermolecular forces come into play and affect classical scalings. Our experiments yield highly resolved topographies of the shape of the interface and allow us to bring new insights into droplet dynamics in microfluidics. We report the novel characterization of two dynamical regimes as the capillary number increases: (i) at low capillary numbers, the film thickness is constant and set by the disjoinging pressure, while (ii) above a critical capillary number, the interface behavior is well described by a viscous scenario. At a high surfactant concentration, structural effects lead to the formation of patterns on the interface , which can be used to trace the interface velocity that yield direct confirmation of boundary condition in viscous regime. The dynamics of a droplet confined between solid walls and pushed by a surrounding liquid is an old problem, however recent theories are still being developed to describe unexplored regimes and experimental characterizations are still lacking to shed light on these novel developments. A complete understanding of the droplet velocity calls for accurate knowledge of the dissipation mechanisms involved, particularly in the lubrication film. Our understanding of the lubrication properties of menisci travelling in confined geometries has been steadily refined since the pioneering work of Taylor & Saffman [1]. Notably, the influence of the lubrication film left along the wall by the moving meniscus was first taken into account by Bretherton, who investigated the motion of an inviscid bubble in a cylindrical tube [2]. Far from the meniscus, this dynamical film reaches a uniform thickness h ∞ , related to the bubble velocity through the capillary number Ca = µ f U d /γ, where U d is the bubble velocity , µ f the viscosity of the continuous phase, and γ the surface tension. When the capillary pressure dominates over the viscous stress, i.e. in the regime where Ca 1, the thickness of the film follows h Breth = 1.34 r Ca 2/3 , where r is the radius of the capillary tube. Besides bubbles , the case of viscous droplets remains however largely unexplored. A recent theoretical advance in the field by Hodges et al. [3] shows by numerical calculations of the whole flow pattern that significant corrections in the thickness of lubrication films can arise at very low Ca. Furthermore, the regime of the Bretherton theory is only valid for lubrication films thicker than the molecular sizes or than the range of interfacial interactions. The typical velocities and lengthscales involved in droplet-based microfluidics would lead to lubrication films h ∞ ∼

Naive T lymphocytes chemotax long distance to CCL21 but not to a source of bioactive S1P

Naive T lymphocytes traffic through the organism in search for antigen, alternating between blood and secondary lymphoid organs. Lymphocyte homing to lymph nodes relies on CCL21 chemokine sensing by CCR7 receptors, while exit into efferent lymphatics relies on sphingolipid S1P sensing by S1PR1 receptors. While both molecules are claimed chemotactic, a quantitative analysis of naive T lymphocyte migration along defined gradients is missing. Here, we used a reductionist approach to study the real-time single-cell response of naive T lymphocytes to CCL21 and serum rich in bioactive S1P. Using microfluidic and micropatterning ad hoc tools, we show that CCL21 triggers stable polarization and long-range chemotaxis of cells, whereas S1P-rich serum triggers a transient polarization only and no significant displacement, potentially representing a brief transmigration step through exit portals. Our in vitro data thus suggest that naive T lymphocyte chemotax long distances to CCL21 but not toward a source of bioactive S1P

The mechanism of force transmission at bacterial focal adhesion complexes

Various rod-shaped bacteria mysteriously glide on surfaces in the absence of appendages such as flagella or pili. In the deltaproteobacterium Myxococcus xanthus, a putative gliding motility machinery (the Agl–Glt complex) localizes to so-called focal adhesion sites (FASs) that form stationary contact points with the underlying surface. Here we show that the Agl–Glt machinery contains an inner-membrane motor complex that moves intracellularly along a right-handed helical path; when the machinery becomes stationary at FASs, the motor complex powers a left-handed rotation of the cell around its long axis. At FASs, force transmission requires cyclic interactions between the molecular motor and the adhesion proteins of the outer membrane via a periplasmic interaction platform, which presumably involves contractile activity of motor components and possible interactions with peptidoglycan. Our results provide a molecular model of bacterial gliding motility

Le diabète de type 2 à La Réunion (le poids de la tradition)

SAINT DENIS/REUNION-Droit Lettre (974112101) / SudocPARIS-BIUP (751062107) / SudocSudocFranceF

Charged diblock copolymers at interfaces: Micelle dissociation upon compression

We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are “frozen”. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters

New modeling of reflection interference contrast microscopy including polarization and numerical aperture effects: application to nanometric distance measurements and object profile reconstruction.

International audienceWe have developed a new and improved optical model of reflection interference contrast microscopy (RICM) to determine with a precision of a few nanometers the absolute thickness h of thin films on a flat surface in immersed conditions. The model takes into account multiple reflections between a planar surface and a multistratified object, finite aperture illumination (INA), and, for the first time, the polarization of light. RICM intensity I is typically oscillating with h. We introduce a new normalization procedure that uses the intensity extrema of the same oscillation order for both experimental and theoretical intensity values and permits us to avoid significant error in the absolute height determination, especially at high INA. We also show how the problem of solution degeneracy can be solved by taking pictures at two different INA values. The model is applied to filled polystyrene beads and giant unilamellar vesicles of radius 10-40 microm sitting on a glass substrate. The RICM profiles I(h) can be fitted for up to two to three oscillation orders, and extrema positions are correct for up to five to seven oscillation orders. The precision of the absolute distance and of the shape of objects near a substrate is about 5 nm in a range from 0 to 500 nm, even under large numerical aperture conditions. The method is especially valuable for dynamic RICM experiments and with living cells where large illumination apertures are required

Dynamics of 2D bubbles in a Hele-Shaw cell (presenter : Reichert)

International audienc