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

Reaction ⁶Li(p, Δ⁺⁺)⁶He At 1.04 GeV And The Δ−N Interaction

The reaction ⁶Li(p, Δ⁺⁺)⁶He has been studied at 1.04 GeV for transferred momenta ranging from 0.11 to 0.35 (GeV/c)2. An exponential decrease of the cross section is observed. A Glauber-type calculation is presented. The possibility of extracting information on σ(ΔN) and α(ΔN) is discussed

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

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

Microscopic theory of the jamming transition of harmonic spheres

We develop a microscopic theory to analyze the phase behaviour and compute correlation functions of dense assemblies of soft repulsive particles both at finite temperature, as in colloidal materials, and at vanishing temperature, a situation relevant for granular materials and emulsions. We use a mean-field statistical mechanical approach which combines elements of liquid state theory to replica calculations to obtain quantitative predictions for the location of phase boundaries, macroscopic thermodynamic properties and microstructure of the system. We focus in particular on the derivation of scaling properties emerging in the vicinity of the jamming transition occurring at large density and zero temperature. The new predictions we obtain for pair correlation functions near contact are tested using computer simulations. Our work also clarifies the conceptual nature of the jamming transition, and its relation to the phenomenon of the glass transition observed in atomic liquids.Comment: 31 pages, 18 figures; long version of arXiv:1011.563

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

Computational Model of the Insect Pheromone Transduction Cascade

A biophysical model of receptor potential generation in the male moth olfactory receptor neuron is presented. It takes into account all pre-effector processes—the translocation of pheromone molecules from air to sensillum lymph, their deactivation and interaction with the receptors, and the G-protein and effector enzyme activation—and focuses on the main post-effector processes. These processes involve the production and degradation of second messengers (IP3 and DAG), the opening and closing of a series of ionic channels (IP3-gated Ca2+ channel, DAG-gated cationic channel, Ca2+-gated Cl− channel, and Ca2+- and voltage-gated K+ channel), and Ca2+ extrusion mechanisms. The whole network is regulated by modulators (protein kinase C and Ca2+-calmodulin) that exert feedback inhibition on the effector and channels. The evolution in time of these linked chemical species and currents and the resulting membrane potentials in response to single pulse stimulation of various intensities were simulated. The unknown parameter values were fitted by comparison to the amplitude and temporal characteristics (rising and falling times) of the experimentally measured receptor potential at various pheromone doses. The model obtained captures the main features of the dose–response curves: the wide dynamic range of six decades with the same amplitudes as the experimental data, the short rising time, and the long falling time. It also reproduces the second messenger kinetics. It suggests that the two main types of depolarizing ionic channels play different roles at low and high pheromone concentrations; the DAG-gated cationic channel plays the major role for depolarization at low concentrations, and the Ca2+-gated Cl− channel plays the major role for depolarization at middle and high concentrations. Several testable predictions are proposed, and future developments are discussed

Genomic innovations, transcriptional plasticity and gene loss underlying the evolution and divergence of two highly polyphagous and invasive <i>Helicoverpa</i> pest species

BACKGROUND: Helicoverpa armigera and Helicoverpa zea are major caterpillar pests of Old and New World agriculture, respectively. Both, particularly H. armigera, are extremely polyphagous, and H. armigera has developed resistance to many insecticides. Here we use comparative genomics, transcriptomics and resequencing to elucidate the genetic basis for their properties as pests. RESULTS: We find that, prior to their divergence about 1.5 Mya, the H. armigera/H. zea lineage had accumulated up to more than 100 more members of specific detoxification and digestion gene families and more than 100 extra gustatory receptor genes, compared to other lepidopterans with narrower host ranges. The two genomes remain very similar in gene content and order, but H. armigera is more polymorphic overall, and H. zea has lost several detoxification genes, as well as about 50 gustatory receptor genes. It also lacks certain genes and alleles conferring insecticide resistance found in H. armigera. Non-synonymous sites in the expanded gene families above are rapidly diverging, both between paralogues and between orthologues in the two species. Whole genome transcriptomic analyses of H. armigera larvae show widely divergent responses to different host plants, including responses among many of the duplicated detoxification and digestion genes. CONCLUSIONS: The extreme polyphagy of the two heliothines is associated with extensive amplification and neofunctionalisation of genes involved in host finding and use, coupled with versatile transcriptional responses on different hosts. H. armigera's invasion of the Americas in recent years means that hybridisation could generate populations that are both locally adapted and insecticide resistant