The tunable structure of silica-latex nanocomposites made of silica nanoparticles (radius ≈ 80 Å) and a copolymer of methyl methacrylate and butyl acrylate-latex beads (radius≈210 Å) has been studied by small-angle neutron scattering and transmission electron microscopy. An aggregation diagram as a function of the control parameters--silica volume fraction and precursor solution pH--has been established. In this aggregation diagram, isoaggregation lines have been identified. It was used to express the small-strain reinforcement factor measured with stress-strain isotherms as a function of volume fraction at fixed aggregation number in the range from 50 to 100. The large-strain properties have been rationalized using the energy needed to rupture samples, and this quantity has been found to present an optimum at intermediate volume fractions (15%). In order to understand the striking rheology of the system, a neutron contrast-matching study has been undertaken by adding deuterated polymer beads. The bead demixing kinetics during annealing has been used to characterize the dynamics in various environments defined by the hard silica structure. In particular, in nanocomposite samples containing 15 vol % of silica the dynamics is found to be blocked.

Mechanical instabilities that cause periodic wrinkling during compression of layered materials find applications in stretch- able electronics1-3 and microfabrication4-7 , but can also limit an application's performance owing to delamination or cracking under loading8 and surface inhomogeneities during swelling9. In particular, because of curvature localization, finite defor- mations can cause wrinkles to evolve into folds. The wrinkle- to-fold transition has been documented in several systems, mostly under uniaxial stress10-13. However, the nucleation, the spatial structure and the dynamics of the invasion of folds in two-dimensional stress configurations remain elusive. Here, using a two-layer polymeric system under biaxial compressive stress, we show that a repetitive wrinkle-to-fold transition generates a hierarchical network of folds during reorganization of the stress field. The folds delineate individual domains, and each domain subdivides into smaller ones over multiple gen- erations. By modifying the boundary conditions and geometry, we demonstrate control over the final network morphology. The ideas introduced here should find application in the many situa- tions where stress impacts two-dimensional pattern formation.

We present in this Rapid Communication experimental evidence of an acceleration of the zenithal easy-axis dynamics of a nematic liquid crystal (NLC) with the age of a NLC-polymer layer. The comparison with other hard alignment layers strongly indicates that the polymer softness and its ability to reorient in the nematic ordering field is at the origin of the measured dynamics. The unusual acceleration of the dynamics with the polymer age is discussed in terms of this unique coupling with the NLC order. The NLC behaves like a physical plasticizer as a result of the coupling between the NLC and the polymer orders.

RBCs are known to release ATP, which acts as a signaling molecule to cause dilation of blood vessels. A reduction in the release of ATP from RBCs has been linked to diseases such as type II diabetes and cystic fibrosis. Furthermore, reduced deformation of RBCs has been correlated with myocardial infarction and coronary heart disease. Because ATP release has been linked to cell deformation, we undertook a multiscale approach to understand the links between single RBC dynamics, ATP release, and macroscopic viscosity all at physiological shear rates. Our experimental approach included microfluidics, ATP measurements using a bioluminescent reaction, and rheology. Using microfluidics technology with high-speed imaging, we visualize the deformation and dynamics of single cells, which are known to undergo motions such as tumbling, swinging, tanktreading, and deformation. We report that shear thinning is not due to cellular deformation as previously believed, but rather it is due to the tumbling-to-tanktreading transition. In addition, our results indicate that ATP release is constant at shear stresses below a threshold (3 Pa), whereas above the threshold ATP release is increased and accompanied by large cellular deformations. Finally, performing experiments with well-known inhibitors, we show that the Pannexin 1 hemichannel is the main avenue for ATP release both above and below the threshold, whereas, the cystic fibrosis transmembrane conductance regulator only contributes to deformation-dependent ATP release above the stress threshold.

The culminating step of the intraerythrocytic development of Plasmodium falciparum, the causative agent of malaria, is the spectacular release of multiple invasive merozoites on rupture of the infected erythrocyte membrane. This work reports for the first time that the whole process, taking place in time scales as short as 400 milliseconds, is the result of an elastic instability of the infected erythrocyte membrane. Using high-speed differential interference contrast (DIC) video microscopy and epifluorescence, we demonstrate that the release occurs in 3 main steps after osmotic swelling of the infected erythrocyte: a pore opens in similar to 100 milliseconds, ejecting 1-2 merozoites, an outward curling of the erythrocyte membrane is then observed, ending with a fast eversion of the infected erythrocyte membrane, pushing the parasites forward. It is noteworthy that this last step shows slight differences when infected erythrocytes are adhering. We rationalize our observations by considering that during the parasite development, the infected erythrocyte membrane acquires a spontaneous curvature and we present a subsequent model describing the dynamics of the curling rim. Our results show that sequential erythrocyte membrane curling and eversion is necessary for the parasite efficient angular dispersion and might be biologically essential for fast and numerous invasions of new erythrocytes. (Blood. 2011;117(15):4118-4124)

The Watson-Crick binding of DNA single strands is a powerful tool for the assembly of nanostructures. Our objective is to develop polymer nanoparticles equipped with DNA strands for surface-patterning applications, taking advantage of the DNA technology, in particular, recognition and reversibility. A hybrid DNA copolymer is synthesized through the conjugation of a ssDNA (22-mer) with a poly(ethylene oxide)-poly(caprolactone) diblock copolymer (PEO-b-PCl). It is shown that, in water, the PEO-b-PCl-ssDNA(22) polymer forms micelles with a PCl hydrophobic core and a hydrophilic corona made of PEO and DNA. The micelles are thoroughly characterized using electron microscopy (TEM and cryoTEM) and small-angle neutron scattering. The binding of these DNA micelles to a surface through DNA recognition is monitored using a quartz crystal microbalance and imaged by atomic force microscopy. The micelles can be released from the surface by a competitive displacement event.

This work aims at demonstrating the interest of gradient copolymers in supercritical CO2 in comparison with block copolymers. Gradient copolymers exhibit a better solubility in supercritical CO2 than block copolymers, as attested by cloud point data. The self-assembly of gradient and block copolymers in dense CO2 has been characterized by Small-Angle Neutron Scattering (SANS) and it is shown that it is not fundamentally modified when changing from block copolymers to gradient copolymers. Therefore, gradient copolymers are advantageous thanks to their easier synthesis and their solubility at lower pressure while maintaining a good ability for self-organization in dense CO2.