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

Can the jamming transition be described using equilibrium statistical mechanics?

When materials such as foams or emulsions are compressed, they display solid behaviour above the so-called `jamming' transition. Because compression is done out-of-equilibrium in the absence of thermal fluctuations, jamming appears as a new kind of a nonequilibrium phase transition. In this proceeding paper, we suggest that tools from equilibrium statistical mechanics can in fact be used to describe many specific features of the jamming transition. Our strategy is to introduce thermal fluctuations and use statistical mechanics to describe the complex phase behaviour of systems of soft repulsive particles, before sending temperature to zero at the end of the calculation. We show that currently available implementations of standard tools such as integral equations, mode-coupling theory, or replica calculations all break down at low temperature and large density, but we suggest that new analytical schemes can be developed to provide a fully microscopic, quantitative description of the jamming transition.Comment: 8 pages, 6 figs. Talk presented at Statphys24 (July 2010, Cairns, Australia

Under-expression Of Chemosensory Genes In Domiciliary Bugs Of The Chagas Disease Vector Triatoma Brasiliensis

In Latin America, the bloodsucking bugs Triatominae are vectors of Trypanosoma cruzi, the parasite that causes Chagas disease. Chemical elimination programs have been launched to control Chagas disease vectors. However, the disease persists because native vectors from sylvatic habitats are able to (re)colonize houses—a process called domiciliation. Triatoma brasiliensis is one example. Because the chemosensory system allows insects to interact with their environment and plays a key role in insect adaption, we conducted a descriptive and comparative study of the chemosensory transcriptome of T. brasiliensis samples from different ecotopes. Methodology/Principal Finding: In a reference transcriptome built using de novo assembly, we found transcripts encoding 27 odorant-binding proteins (OBPs), 17 chemosensory proteins (CSPs), 3 odorant receptors (ORs), 5 transient receptor potential channel (TRPs), 1 sensory neuron membrane protein (SNMPs), 25 takeout proteins, 72 cytochrome P450s, 5 gluthatione S-transferases, and 49 cuticular proteins. Using protein phylogenies, we showed that most of the OBPs and CSPs for T. brasiliensis had well supported orthologs in the kissing bug Rhodnius prolixus. We also showed a higher number of these genes within the bloodsucking bugs and more generally within all Hemipterans compared to the other species in the super-order Paraneoptera. Using both DESeq2 and EdgeR software, we performed differential expression analyses between samples of T. brasiliensis, taking into account their environment (sylvatic, peridomiciliary and domiciliary) and sex. We also searched clusters of co-expressed contigs using HTSCluster. Among differentially expressed (DE) contigs, most were under-expressed in the chemosensory organs of the domiciliary bugs compared to the other samples and in females compared to males. We clearly identified DE genes that play a role in the chemosensory system. Conclusion/Significance: Chemosensory genes could be good candidates for genes that contribute to adaptation or plastic rearrangement to an anthropogenic system. The domiciliary environment probably includes less diversity of xenobiotics and probably has more stable abiotic parameters than do sylvatic and peridomiciliary environments. This could explain why both detoxification and cuticle protein genes are less expressed in domiciliary bugs. Understanding the molecular basis for how vectors adapt to human dwellings may reveal new tools to control disease vectors; for example, by disrupting chemical communication. © 2016 Marchant et al.101

Phase Behavior of Polyelectrolyte Block Copolymers in Mixed Solvents

We have studied the phase behavior of the poly(n-butyl acrylate)-b-poly(acrylic acid) block copolymer in a mixture of two miscible solvents, water and tetrahydrofuran (THF). The techniques used to examine the different polymers, structures and phases formed in mixed solvents were static and dynamic light scattering, small-angle neutron scattering, nuclear magnetic resonance and fluorescence microscopy. By lowering the water/THF mixing ratio X, the sequence unimers, micron-sized droplets, polymeric micelles was observed. The transition between unimers and the micron-sized droplets occurred at X = 0.75, whereas the microstructuration into core-shell polymeric micelles was effective below X = 0.4. At intermediate mixing ratios, a coexistence between the micron-sized droplets and the polymeric micelles was observed. Combining the different aforementioned techniques, it was concluded that the droplet dispersion resulted from a solvent partitioning that was induced by the hydrophobic blocks. Comparison of poly(n-butyl acrylate) homopolymers and poly(n-butyl acrylate)-b-poly(acrylic acid) block copolymers suggested that the droplets were rich in THF and concentrated in copolymers and that they were stabilized by the hydrophilic poly(acrylic acid) moieties.Comment: 11 pages, 12 figures, to appear in Macromolecule

La recherche expérimentale en aérodynamique à l’ONERA – L’exemple du buffet transsonique

International audienceThe paper reviews research conducted at ONERA over the last thirty years on the transonic buffet. We first present the transonic buffet phenomenon and we explain its importance for aeronautical applications. Then, a distinction is made between the 2D buffet produced by an airfoil and the 3D buffet that characterizes swept wings of finite span. The 2D buffet amounts to a pure oscillation of the shock phase-locked with the detachment and reattachment of the boundary layer downstream, whereas the 3D buffet takes the form of a pocket of broadband perturbations located in a limitedportion of the wing. We recall that these mechanisms were first studied in the 1980s through a series of tests conducted in the transonic wind tunnel ONERA T2 at Toulouse and in the large transonic wind tunnel ONERA S2Ma at Modane. Since this pioneering work, progress in the measurement techniques has led to the constitution of a comprehensive database of the 2D buffet that we describe. This database, obtained in the wind tunnel ONERA S3Ch at Meudon, has been extensively used to validate various CFD tools, with the latter being used in turn to investigate the buffet physics. We illustrate this collaboration between simulation and physics by recalling that a linear stability analysis of accurate Reynolds-Averaged-Navier-Stokes (RANS) solutions made it possible to prove that the buffet on a 2D airfoil stems from a global instability mechanism.We also review more recent tests done in the case of a laminar airfoil, which reveal very distinct behaviors of the buffet flow. This illustrates how sensitive the buffet is to the nature of the boundary layer. The last section of the paper gives a short overview of advanced simulations for these different test cases. In the conclusion, we list research perspectives, which include some more general topics such as data assimilation.L'article passe en revue les recherches menées à l'ONERA au cours des trente dernières années sur le buffet transsonique. Nous présentons d'abord le phénomène du buffet transsonique et nous expliquons son importance pour les applications aéronautiques. On distingue ensuite le buffet 2D produit par une aile bidimensionnelle et le buffet 3D qui caractérise les ailes en flèches d’envergure finie. Le buffet 2D se présente sous la forme d’une oscillation d’ensemble de tout l’écoulement couplant un déplacement de l’onde de choc et le décollement de la couche limite en aval de ce choc. Le buffet 3D prend quant à lui la forme d'une poche de perturbations localisées dans une portion limitée de l'aile. Nous rappelons que ces mécanismes ont d'abord été étudiés à l’ONERA dans les années 80 à travers une série de tests réalisés dans la soufflerie transsonique T2 à Toulouse et dans la grande soufflerie transsonique S2 de Modane. Ces travaux pionniers ont ensuite été approfondis dans la soufflerie S3Ch de Meudon de manière à élaborer une base de données complète du buffet 2D sur une aile 2D en régime turbulent, que nous décrivons. Cette base de données a été utilisée de façon extensive, à l’ONERA et dans d’autres institutions pour valider différents outils de simulation, ces derniers étant alors utilisés à leur tour pour étudier la physique du buffet. Nous illustrons cette collaboration entre la simulation et la physique en rappelant qu'une analyse de stabilité linéaire de solutions précises des équations de Navier-Stokes moyennées au sens de Reynolds (RANS) a permis de prouver que le buffet 2D provient d'un mécanisme d'instabilité globale. Nous passons également en revue des essais plus récents réalisés dans la soufflerie S3Ch sur le cas d'une aile 2D laminaire qui révèlent des comportements très distincts par rapport au cas turbulent. Cela illustre la sensibilité du buffet à la nature de la couche limite. Le dernier paragraphe du document donne un bref aperçu des simulations avancées de ces différents cas tests. Dans la conclusion, nous énumérons les perspectives de recherche sur le sujet, qui incluent aussi des thématiques méthodologiques plus générales telles que l'assimilation de données

Quasi-static magnetohydrodynamic turbulence at high Reynolds number

We analyse the anisotropy of homogeneous turbulence in an electrically conducting fluid submitted to a uniform magnetic field, for low magnetic Reynolds number, in the quasi- static approximation. We interpret disagreeing previous predictions between linearized theory and simulations: in the linear limit, the kinetic energy of transverse velocity components, normal to the magnetic field, decays faster than the kinetic energy of the axial component, along the magnetic field (Moffatt (1967)); whereas many numerical studies predict a final state characterised by dominant energy of transverse velocity components. We investigate the corresponding nonlinear phenomenon using Direct Numerical Simulations of freely-decaying turbulence, and a two-point statistical spectral closure based on the Eddy Damped Quasi-Normal Markovian model. The transition from the three-dimensional turbulent flow to a "two-and-a-half-dimensional" flow (Montgomery & Turner (1982)) is a result of the combined effects of short-time linear Joule dissipation and longer time nonlinear creation of polarisation anisotropy. It is this combination of linear and nonlinear effects which explains the disagreement between predictions from linearized theory and results from numerical simulations. The transition is characterized by the elongation of turbulent structures along the applied magnetic field, and by the strong anisotropy of directional two-point correlation spectra, in agreement with experimental evidence. Inertial equatorial transfers in both DNS and the model are presented to describe in detail the most important equilibrium dynamics. Spectral scalings are maintained in high Reynolds number turbulence attainable only with the EDQNM model, which also provides simplified modelling of the asymptotic state of quasi-static MHD turbulence.Comment: Journal of Fluid Mechanics, 201

Interactions between Magnetic Nanowires and Living Cells : Uptake, Toxicity and Degradation

We report on the uptake, toxicity and degradation of magnetic nanowires by NIH/3T3 mouse fibroblasts. Magnetic nanowires of diameters 200 nm and lengths comprised between 1 {\mu}m and 40 {\mu}m are fabricated by controlled assembly of iron oxide ({\gamma}-Fe2O3) nanoparticles. Using optical and electron microscopy, we show that after 24 h incubation the wires are internalized by the cells and located either in membrane-bound compartments or dispersed in the cytosol. Using fluorescence microscopy, the membrane-bound compartments were identified as late endosomal/lysosomal endosomes labeled with lysosomal associated membrane protein (Lamp1). Toxicity assays evaluating the mitochondrial activity, cell proliferation and production of reactive oxygen species show that the wires do not display acute short-term (< 100 h) toxicity towards the cells. Interestingly, the cells are able to degrade the wires and to transform them into smaller aggregates, even in short time periods (days). This degradation is likely to occur as a consequence of the internal structure of the wires, which is that of a non-covalently bound aggregate. We anticipate that this degradation should prevent long-term asbestos-like toxicity effects related to high aspect ratio morphologies and that these wires represent a promising class of nanomaterials for cell manipulation and microrheology.Comment: 21 pages 12 figure

NOVIWAM : Five European countries together for improving water quality and water use efficiency

The European NOVIWAM (NOvel Integrated Water Management Systems for Southern European Regions, www.noviwam.eu) program aims to promote interregional co-operation in the field of water management tools and methods. One of its originality is to analyze in depth the relations between decision makers, stakeholders and researchers in order to disseminate know-how and technologies, and to tackle the compelling water management problems faced in the Euro-Mediterranean climate regions. In a first period, aiming at a good ecological and chemical state of waters and at a sustainable and efficient resource management, five European countries/regions (Albania, Cyprus, Poitou-Charentes in France, Northern Region in Portugal and Andalusia in Spain) are working together. The program will thus contribute to the objectives of the European Water Framework Directive. But additionally, the NOVIWAM program will establish a schedule for the implementation of a « Join action plan », trying to involve other countries into it, and generalize the conclusions of this three year work at a regional and international level.NOVIWAM (Grant Agreement nº 245460