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This work focuses on the temperature-dependent structural and rheological characterization of polystyrene- b-poly( n-butyl acrylate)- b-polystyrene triblock copolymers (PS- b-P nBA- b-PS) in the melt and, in particular, on their ability to show a lower disorder-to-order temperature (LDOT). To this aim, copolymers of varying block lengths, but keeping the P nBA block as a major component, were synthesized. Small-angle x-ray scattering revealed that the copolymers with short PS blocks (∼10 kg/mol) approach an LDOT but do not cross it. At room temperature, these copolymers exhibit higher moduli compared to a P nBA homopolymer due to the reinforcing effect of the PS but are flowing at temperatures above the glass transition of the PS. Increasing the PS and P nBA block length, to keep the same PS fraction, induces more profound changes in the structural and viscoelastic behaviors. Such a copolymer crosses the LDOT, leading to a microphase-separated and ordered state at high temperature. Contrary to the copolymers with short PS blocks, the flow regime was not reached, even at temperatures well above the glass transition of the PS. Instead, a low-frequency plateau was observed in rheology, showing the increased lifetime of the microphase-separated PS domains. ABA triblock copolymers exhibiting an LDOT behavior could, thus, be of interest for the design of thermoplastic elastomers or pressure-sensitive adhesives that can resist the flow at high temperatures.

Food transition requires the replacement in human diet of animal-based proteins by alternative sources of proteins including plant-based proteins. This calls for a detailed knowledge of the functional properties of plant-based proteins, including their surface activity. In this framework, we provide here a comparative study of the interfacial properties of two plant proteins, extracted respectively from wheat and sunflower. We combine time- and concentration-dependent measurements of the surface tension and the surface rheology, as measured with a pendant-drop set-up, and of the surface excess concentration, as measured by ellipsometry, of plant protein interfacial films. We demonstrate a time-concentration superposition principle for the surface pressure and surface excess concentration, showing that the kinetics for the building of the interfacial films is essentially governed by the diffusion of the proteins from the bulk to the interface. We find that the rheological and structural properties of the interfacial protein films show markedly different behaviors for the two classes of protein, which is encoded in the structural features of the individual proteins: wheat proteins are more surface active than sunflower proteins, are keen to compress and re-arrange at an air-water interface, whereas sunflower proteins do not. This work provides qualitative and quantitative analysis of the comparative interfacial behavior of flexible and rigid plant proteins extracted respectively from wheat and sunflower, and demonstrates that a combination of several experimental techniques is necessary to obtain insightful information on the interfacial properties of any species.

International audience; The adsorption of a sunflower protein extract at two air− water and oil−water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air−water interface, while it is mostly in the organic phase at the oil−water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius R H ∼ 80 nm, evidenced in equilibrium with hexameric globulins (R H ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.

Understanding the origin of the unique rheological properties of wheat gluten, the protein fraction of wheat grain, is crucial in bread-making processes and has raised questions of scientists for decades. Gluten is a complex mixture of two families of proteins, monomeric gliadins and polymeric glutenins. To better understand the respective role of the different classes of proteins in the supramolecular structure of gluten and its link to the material properties, we investigate here concentrated dispersions of gluten proteins in water with a fixed total protein concentration but variable composition in gliadin and glutenin. Linear viscoelasticity measurements show a gradual increase in the viscosity of the samples as the glutenin mass content increases from 7 to 66%. While the gliadin-rich samples are microphase-separated viscous fluids, homogeneous and transparent pre-gel and gels are obtained with the replacement of gliadin by glutenin. To unravel the flow properties of the gluten samples, we perform shear startup experiments at different shear-rates. In accordance with the linear viscoelastic signature, three classes of behavior are evidenced depending on the protein composition. As samples get depleted in gliadin and enriched in glutenin, distinctive features are measured: (i) viscosity undershoot suggesting droplet elongation for microphase-separated dispersions, (ii) stress overshoot and partial structural relaxation for near-critical pre-gels, and (iii) strain hardening and flow instabilities of gels. We discuss the experimental results by analogy with the behavior of model systems, including viscoelastic emulsions, branched polymer melts, and critical gels, and provide a consistent physical picture of the supramolecular features of the three classes of protein dispersions.

We use the impact of drops on a small solid target as a tool to investigate the behavior of viscoelastic fluids under extreme deformation rates. We study two classes of transient networks: semidilute solutions of supramolecular polymers and suspensions of spherical oil droplets reversibly linked by polymers. The two types of samples display very similar linear viscoelastic properties, which can be described with a Maxwell fluid model, but contrasting nonlinear properties due to different network structure. Upon impact, weakly viscoelastic samples exhibit a behavior qualitatively similar to that of Newtonian fluids: A smooth and regular sheet forms, expands, and then retracts. By contrast, for highly viscoelastic fluids, the thickness of the sheet is found to be very irregular, leading to instabilities and eventually formation of holes. We find that material rheological properties rule the onset of instabilities. We first provide a simple image analysis of the expanding sheets to determine the onset of instabilities. We then demonstrate that a Deborah number related to the shortest relaxation time associated to the sample structure following a high shear is the relevant parameter that controls the heterogeneities in the thickness of the sheet, eventually leading to the formation of holes. When the sheet tears-up, data suggest by contrast that the opening dynamics depends also on the expansion rate of the sheet., Comment: accepted for publication in Soft Matter

We investigate freely expanding viscoelastic sheets. The sheets are produced by the impact of drops on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation as a result of the cold Leidenfrost effect. The time evolution of the sheet is simultaneously recorded from top and side views using high-speed cameras. The investigated viscoelastic fluids are Maxwell fluids, which are characterized by low elastic moduli, and relaxation times that vary over almost two orders of magnitude, thus giving access to a large spectrum of viscoelastic and elastocapillary effects. For the purposes of comparison, Newtonian fluids, with viscosity varying over three orders of magnitude, are also investigated. In this study, $d_{\mathrm{max}}$, the maximal expansion of the sheets, and $t_{\mathrm{max}}$ the time to reach this maximal expansion from the time at impact, are measured as a function of the impact velocity. By using a generalized damped harmonic oscillator model, we rationalize the role of capillarity, bulk elasticity and viscous dissipation in the expansion dynamics of all investigated samples. In the model, the spring constant is a combination of the surface tension and the bulk dynamic elastic modulus. The time-varying damping coefficient is associated to biaxial extensional viscous dissipation and is proportional to the dynamic loss modulus. For all samples, we find that the model reproduces accurately the experimental data for $d_{\mathrm{max}}$ and $t_{\mathrm{max}}$., Accepted for publication in Soft Matter

International audience; Wheat gluten includes two major proteins classes, gliadin (25–60 kg/mol) and glutenin polymers (100 to > 2,000 kg/mol) each comprising several polypeptides routinely identified by size-exclusion chromatography and electrophoresis. Gluten proteins are rich in glutamine (30%) and contain several repeated sequences, linking them to the wide class of intrinsically disordered protein (IDP). Here we showed that an ethanol/water (EtOH/W, 50/50, v/v) extract of an industrial gluten, comprising 1/3 of glutenin polymers and 2/3 of gliadin, underwent liquid-liquid phase separation (LLPS) below 14 °C, leading to two coexisting phases, respectively rich and poor in protein. As the quenching depth increased, proteins of lower and lower molecular weight joined the rich phase, akin to what would have been obtained for a polydisperse polymer sample. Within the rich phase the mass ratio of glutenin over gliadin decreased from 2.5 to 0.5 as the temperature dropped from 14 °C to −0.8 °C. Concomitantly the concentration in glutenin polymers increased up to 143 ± 6 g/L (at 9 °C) and then stopped to evolve, suggesting that the binodal line intersected the gelation line below this temperature. Applying the Flory-Huggins (FH) lattice model for each gluten protein classes, we demonstrated that their partitioning in the coexisting phases followed a same temperature dependency. However, some gliadin species joined the rich phase above their critical temperature. Here, specific interactions with the glutenin polymers through weak forces were exemplified. The study demonstrated the relevance of the Flory-Huggins (FH) lattice model in predicting phase behavior even when applied to complex protein mixtures.

In this Special Issue, we celebrate the connection between the physics of fluids, food science and education. We received over 30 articles concerning all types of kitchen flows, from simple to complex, from small to large scale. They include research articles, short reviews, educational articles, methods papers and expert tutorials. In the remainder of this editorial, we will summarise these works and highlight some exciting new opportunities in this effervescently growing branch of science.

International audience; When a drop of fluid hits a small solid target of comparable size, it expands radially until reaching a maximum diameter and subsequently recedes. In this work, we show that the expansion process of liquid sheets is controlled by a combination of shear (on the target) and biaxial extensional (in the air) deformations. We propose an approach toward a rational description of the phenomenon for Newtonian and viscoelastic fluids by evaluating the viscous dissipation due to shear and extensional deformations, yielding a prediction of the maximum expansion factor of the sheet as a function of the relevant viscosity. For Newtonian systems, biaxial extensional and shear viscous dissipation are of the same order of magnitude. On the contrary, for thinning solutions of supramolecular polymers, shear dissipation is negligible compared to biaxial extensional dissipation and the biaxial thinning extensional viscosity is the appropriate quantity to describe the maximum expansion of the sheets. Moreover, we show that the rate-dependent biaxial extensional viscosities deduced from drop impact experiments are in good quantitative agreement with previous experimental data and theoretical predictions for various viscoelastic liquids.

We investigate the structure of gluten polymer-like gels in a binary mixture of water/ethanol, $50/50$ v/v, a good solvent for gluten proteins. Gluten comprises two main families of proteins, monomeric gliadins and polymer glutenins. In the semi-dilute regime, scattering experiments highlight two classes of behavior, akin to standard polymer solution and polymer gel, depending on the protein composition. We demonstrate that these two classes are encoded in the structural features of the proteins in very dilute solution, and are correlated with the presence of proteins assemblies of typical size tens of nanometers. The assemblies only exist when the protein mixture is sufficiently enriched in glutenins. They are found directly associated to the presence in the gel of domains enriched in non-exchangeable H-bonds and of size comparable to that of the protein assemblies. The domains are probed in neutron scattering experiments thanks to their unique contrast. We show that the sample visco-elasticity is also directly correlated to the quantity of domains enriched in H-bonds, showing the key role of H-bonds in ruling the visco-elasticity of polymer gluten gels., accepted for publication in Journal of Physics: Condensed Matter, Special issue on "Glasses and gels: a crossroad of molecular liquids, polymers and colloids"

We investigate the delayed rupture of biopolymer gels under a constant shear load by simultaneous dynamic light scattering and rheology measurements. We unveil the crucial role of normal stresses built up during gelation: all samples that eventually fracture self-weaken during the gelation process, as revealed by a partial relaxation of the normal stress concomitant to a burst of microscopic plastic rearrangements. Upon applying a shear stress, weakened gels exhibit in the creep regime distinctive signatures in their microscopic dynamics, which anticipate macroscopic fracture by up to thousands of seconds. The dynamics in fracturing gels are faster than those of non-fracturing gels and exhibit large spatio-temporal fluctuations. A spatially localized region with significant plasticity eventually nucleates, expands progressively, and finally invades the whole sample triggering macroscopic failure., Comment: accepted for publication in Physical Review Letters

International audience; Wheat gluten, one of the most complex viscoelastic protein networks in nature, is unique to get the specific texture of bread. Due to its complex protein composition, its insolubility in most solvents and the very high molar mass of half of the proteins (glutenin, the other half being gliadin), the architecture of the network is still not well understood. In this work, we have investigated model gluten protein extracts with contrasted compositions in glutenin and gliadin solubilized in a mild chaotropic solvent: ethanol/water (50/50 v/v). The samples display a liquid-liquid phase separation with an upper critical solution temperature that depends on the protein composition. The phase diagrams are consistent with the presence of supramolecular assemblies of proteins. To confirm the presence of these assemblies and fully characterize the objects dispersed in ethanol/water, we have used an asymmetrical flow field-flow fractionation (AsFlFFF) setup coupled with differential refractive index, multi-angle light scattering and dynamic light scattering detections to probe very dilute protein suspensions. We have identified three classes of objects, with distinctive molar mass, characteristic size and conformation: protein monomers, polymeric structures, and very loose protein assemblies with molar mass larger than 2.10 6 g/mol. A molecular characterization of the species by size exclusion chromatography in a denaturing solvent shows that polymers and assemblies are mainly composed of glutenin and ω-gliadin. The high content of ω-gliadin, devoid of cysteines, indicates the importance of non-covalent interactions involved in protein assemblies and might play a major role in gluten rheology

International audience; A novel and simple method for the measurement of cloud point temperatures of solutions is presented. Cloud point determination , which is currently used to establish the phase diagrams of protein solutions, is indicative of proteins interactions and constitutes a useful tool for food products engineering. We describe a novel experimental setup that allows screening of a large number of physical-chemical conditions in one measurement and the determination of cloud point temperatures both above and below ambient temperature. We use a simple method to avoid solvent evaporation and condensation, so that the setup can be used for solutions prepared with a volatile solvent. We present the operating parameter range and the precision of the measurement. The optical properties of the system are calibrated with solutions of known transmittance, and the determination of cloud point temperatures is validated on a standard non-ionic surfactant solution. Finally, we demonstrate the efficiency of the method by determining the phase diagram of a wheat protein extract, soluble in a water/ethanol mixture. Complemented with differential scanning calorimetry measurements, the liquid-liquid phase transition can be determined up to a protein concentration of 250 g/L, a range inaccessible with conventional methods for this protein extract.

International audience; Materials are the key roadblocks for the commercialization of energy conversion devices in fuel cells andsolar cells. Significant research has focused on tuning the intrinsic properties of materials at the nanometerscale. The soft template mediated controlled fabrication of advanced nanostructured materials isattracting considerable interest due to the promising applications of these materials in catalysis and electrocatalysis.Swollen hexagonal lyotropic liquid crystals (SLCs) consist of oil-swollen surfactant-stabilized1D, 2D or 3D nanometric assemblies regularly arranged in an aqueous solvent. Interestingly, the characteristicsize of the SLCs can be controlled by adjusting the volume ratio of oil to water. The non-polarand/or polar compartments of the SLCs can be doped with guest molecules and used as nanoreactorsfor the synthesis of various metals (Pt, Pd, Au, etc.), conducting polymers and composite nanostructureswith controlled size and shape. 1D, 2D and 3D mono- and bimetallic nanostructures of controlled compositionand porosity can also be fabricated. These materials have demonstrated impressive enhancementsof their electrochemical properties as compared to their bulk counterparts and have been identifiedas promising for further implementation in energy harvesting applications. In this review article,recent research materials are described regarding the development of functional materials with muchimproved performances for catalysis applications. This review addresses a brief overview of swollen hexagonalmesophases as nanoreactors, describes examples of nanostructured materials synthesized inthese nanoreactors, shows several examples of the energy conversion applications in solar light harvesting,fuel cells etc. and also summarizes the associated reaction mechanisms developed in the recent literaturefor enhanced catalytic activity.

International audience; Conjugated polymer nanostructures have recently emerged as a new class of very active photocatalysts under solar light. Poly(3-hexylthiophene) (P3HT) is one of the commonly used conjugated polymers for photovoltaics applications. P3HT nanostructures synthesized in soft templates provided by hexagonal mesophases show high photocatalytic activity for degradation of pollutants under both UV and visible light. These photocatalysts are very stable even after repeated cycling. Addition of scavengers and mechanistic studies show that O2•−is the main radical responsible for degradation of phenol taken as a model pollutant. P3HT nanostructures can be easily deposited on flat supports such as quartz for photocatalytic applications avoiding a separation step by centrifugation. Most interestingly, the photocatalytic activityof these P3HT nanostructures is highly enhanced when they are supported on a solid surface opening new perspectives in photocatalytic reactors and self-cleaning surfaces.

International audience; A single-drop experiment based on the collision of one drop of liquid on a small solid target is used to produce liquid sheets that are visualized with a fast camera. Upon impact, the drop flattens into a sheet that is bounded by a thicker rim and radially expanding in air. Emulsion-based liquid sheets are destabilized through the nucleation of holes that perforate the sheet during its expansion. The holes grow until they merge together and form a web of ligaments, which are then destabilized into drops. We propose the perforation mechanism as a sequence of two necessary steps. The emulsion oil droplets first enter the air/water interface, and then spread at the interface. We show that the formulation of the emulsion is a critical parameter to control the perforation as the addition of salt or amphiphilic copolymers can trigger or completely inhibit the perforation mechanism. We demonstrate that the entering of the droplets at the air/water interface is the limiting step of the mechanism. Thin-film forces such as electrostatic or steric repulsion forces stabilize the thin film formed between the interface and the approaching oil droplets, thus preventing the entering of droplets at the interface and in turn inhibiting the perforation process. We theoretically rationalize the successive steps in the approach and entering of an oil droplet at the film interface and the role of salt and amphiphilic polymer in the different steps.

We investigate freely expanding liquid sheets made of either simple Newtonian fluids or solutions of high molecular water-soluble polymer chains. A sheet is produced by the impact of a drop on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation thanks to an inverse Leidenfrost effect. The sheet expands radially until reaching a maximum diameter and subsequently recedes. Experiments indicate the presence of two expansion regimes: the capillary regime, where the maximum expansion is controlled by surface tension forces and does not depend on the viscosity, and the viscous regime, where the expansion is reduced with increasing viscosity. In the viscous regime, the sheet expansion for polymeric samples is strongly enhanced as compared to that of Newtonian samples with comparable zero-shear viscosity. We show that data for Newtonian and non-Newtonian fluids collapse on a unique master curve where the maximum expansion factor is plotted against the relevant effective biaxial extensional Ohnesorge number that depends on fluid density, surface tension and the biaxial extensional viscosity. For Newtonian fluids, this biaxial extensional viscosity is six times the shear viscosity. By contrast, for the non- Newtonian fluids, a characteristic Weissenberg number-dependent biaxial extensional viscosity is identified, which is in quantitative agreement with experimental and theoretical results reported in the literature for biaxial extensional flows of polymeric liquids., Comment: 10 pages, 9 figures, accepted for publication in Phys. Rev. Fluids

Green hydrogen production by photocatalytic water splitting offers a promising way to solve environment and energy issues. Conjugated polymer nanostructures (CPNs), with highly π-conjugated structures, have been demonstrated as a new class of photocatalysts. However, pristine CPNs show poor photocatalytic activity for hydrogen generation owing to fast charge carrier recombination and sluggish kinetics. The investigation of application of polypyrrole in photocatalytic hydrogen generation is also rare. Here, we report the surface modification of polypyrrole nanostructures (NSs) with Pt- and Ni-based nanoparticles for photocatalytic hydrogen evolution. PPy nanostructures (NSs) were synthesized using lamellar mesophases as soft templates. The PPy-NSs were modified with mono- and bimetallic (Pt, Ni, Pt–Ni) co-catalyst nanoparticles induced by radiolysis. The prepared Pt-PPy, Ni-PPy and PtNi-PPy exhibit excellent photocatalytic activity for H2 generation and a synergistic effect is obtained with co-modification with Pt and Ni. The effects of the nature of the metal precursors and the loading ratio were studied. We show that the loading rate of co-catalysts is crucial for H2 generation, and an excess of co-catalyst can drastically decrease the activity. The composite photocatalyst Pt-Ni-PPy nanostructures are very active and stable with cycling. Our results indicate that modified CPNs with mono- and bimetallic NPs are promising photocatalysts for hydrogen evolution.

We investigate the linear viscoelasticity of polymer gels produced by the dispersion of gluten proteins in water:ethanol binary mixtures with various ethanol contents, from pure water to 60% v/v ethanol. We show that the complex viscoelasticity of the gels exhibits a time/solvent composition superposition principle, demonstrating the self-similarity of the gels produced in different binary solvents. All gels can be regarded as near critical gels with characteristic rheological parameters, elastic plateau and characteristic relaxation time, which are related one to another, as a consequence of self-similarity, and span several orders of magnitude when changing the solvent composition. Thanks to calorimetry and neutron scattering experiments, we evidencea co-solvency effect with a better solvation of the complex polymer-like chains of the gluten proteins as the amount of ethanol increases. Overall the gel viscoelasticity can be accounted for by a unique characteristic length characterizing the crosslink density of the supramolecular network, which is solvent composition-dependent. On a molecular level, these findings could be interpreted as a transition of the supramolecular interactions, mainly H-bonds, from intra- to interchains, which would be facilitated by the disruption of hydrophobic interactions by ethanol molecules. This work provides new insight for tailoring the gelation process of complex polymer gels., Comment: Macromolecules. In press 2020

The mechanical properties of soft matter are of great importance in countless applications, in addition of being an active field of academic research. Given the relative ease with which soft materials can be deformed, their non-linear behavior is of particular relevance. Large loads eventually result in material failure. In this Perspective article, we discuss recent work aiming at detecting precursors of failure by scrutinizing the microscopic structure and dynamics of soft systems under various conditions of loading. In particular, we show that the microscopic dynamics is a powerful indicator of the ultimate fate of soft materials, capable of unveiling precursors of failure up to thousands of seconds before any macroscopic sign of weakening., 12 pages, 7 figures

International audience; Natural protein sources often display a huge complexity, being composed of a blend of polypeptides of various molecular weight, pHi and charge density. Gluten, the proteins extracted from wheat flour is one of such. Gluten is widely used for its viscoelastic properties as an improver of cereal products (bread, pastry, etc.). It is composed of two classes of proteins, named gliadin and glutenin, similar in their amounts in glutamine (30%) and proline (10%). The more than 25 different polypeptides belonging to the gliadin class are hard to fractionate into individual components because of high redundancy in the primary sequences. Glutenin are in the form of polymers made from several distinct polypeptides concatenated through inter-chain disulfide bonds. Their molecular weights are evenly distributed from 100 kg/mol to 7,000 kg/mol.While it is well established that gliadin confers viscosity to gluten whereas glutenin polymers are at the origin of its elastic resistance, the interactions existing between both classes of gluten protein remain unknown. We previously showed by SLS and multi-angle DLS that gluten proteins suspended in ethanol/water (50/50, v/v), a theta solvent, includes large proteins assemblies (26,000 kg/mol, Rh 100nm) displaying an internal dynamic1. To get a better insight of the composition of those assemblies, we combined biochemical and physicochemical approaches. On the one hand, gluten proteins suspended in ethanol/water were fractionated by Asymmetrical- Flow-Field-Flow Fractionation (A4F) coupled to UV, SLS and QELS detectors. On the other hand, gluten proteins were partitioned by liquid-phase decomposition in respect with temperature. Protein composition of partitioned phases and eluting fractions recovered from A4F were characterized by size-exclusion chromatography. A specific interaction between omega-gliadin and glutenin polymers was evidenced.This result strengthens a very recent study that demonstrates a significant positive correlation between glutenin polymeric proteins, the ω‐gliadin fraction, and dough properties.

International audience; We present a new light scattering setup coupled to a commercial rheometer operated in the plate-plate geometry. The apparatus allows the microscopic dynamics to be measured, discriminating between the contribution due to the affine deformation and additional mechanisms, such as plasticity. Light backscattered by the sample is collected using an imaging optical layout, thereby allowing the average flow velocity and the microscopic dynamics to be probed with both spatial and temporal resolution. We successfully test the setup by measuring the Brownian diffusion and flow velocity of diluted colloidal suspensions, both at rest and under shear. The potentiality of the apparatus are explored in the startup shear of a biogel. For small shear deformations, $\gamma \le 2\%$, the rheological response of the gel is linear. However, striking deviations from affine flow are seen from the very onset of deformation, due to temporally and spatially heterogeneous rearrangements bearing intriguing similarities with a stick-slip process.

We investigate the nucleation and propagation of cracks in self-assembled viscoelastic fluids, which are made of surfactant micelles reversibly linked by telechelic polymers. The morphology of the micelles can be continuously tuned, from spherical to rod-like to wormlike, thus producing transient double networks when the micelles are sufficiently long and entangled, and transient single networks otherwise. For a single network, we show that cracks nucleate when the sample deformation rate involved is comparable to the relaxation time scale of the network. For a double network, by contrast, significant rearrangements of the micelles occur as a crack nucleates and propagates. We show that birefringence develops at the crack tip over a finite length, $\xi$, which corresponds to the length scale over which micelles alignment occur. We find that $\xi$ is larger for slower cracks, suggesting an increase of ductility., Comment: 10 pages, 4 figures

We investigate by time-resolved Synchrotron ultra-small X-ray scattering the dynamics of liquid-liquid phase-separation (LLPS) of gluten protein suspensions following a temperature quench. Samples at a fixed concentration (237 mg/ml) but with different protein compositions are investigated. In our experimental conditions, we show that fluid viscoelastic samples depleted in polymeric glutenin phase-separate following a spinodal decomposition process. We quantitatively probe the late stage coarsening that results from a competition between thermodynamics that speeds up the coarsening rate as the quench depth increases, and transport that slows downs the rate. For even deeper quenches, the even higher viscoelasticity of the continuous phase leads to a "quasi" arrested phase separation. Anomalous phase-separation dynamics is by contrast measured for a gel sample rich in glutenin, due to elastic constraints. This work illustrates the role of viscoelasticity in the dynamics of LLPS in protein dispersions., Comment: accepted for publication in Soft Matter

International audience; Gliadins are edible wheat storage proteins well known for their surface active properties. In this paper, we present experimental results on the interfacial properties of acidic solutions of gliadin studied over 5 decades of concentrations, from 0.001 to 110 g/L. Dynamic pendant drop tensiometry reveals that the surface pressure  of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of collected at different bulk protein concentrations C can be merged onto a single master curve when  is plotted as a function of t where t is the time elapsed since the formation of the air/water interface and  is a shift parameter that varies with C as a power law with an exponent 2. The existence of such time-concentration superposition, which we evidence for the first time, indicates that the same mechanisms govern the surface tension evolution at all concentrations and are accelerated by an increase of the bulk concentration. The scaling of  with C is consistent with a kinetic of adsorption controlled by the diffusion of the proteins in the bulk. Moreover, we show that the proteins adsorption at the air/water interface is kinetically irreversible. Correlated evolutions of the optical and elastic properties of the interfaces, as probed by ellipsometry and surface dilatational rheology respectively, provide a consistent physical picture of the building up of the protein interfacial layer. A progressive coverage of the interface by the proteins occurs at low . This stage is followed, at higher , by conformational rearrangements of the protein film, which are identified by a strong increase of the dissipative viscoelastic properties of the film concomitantly with a peculiar evolution of its optical profile that we have rationalized. In the last stage, at even higher surface pressure, the adsorption is arrested; the optical profile is not modified while the elasticity of the interfacial layer dramatically increases with the surface pressure, presumably due to the film ageing.

Réf Journal: PNAS 115, 3587 (2018); International audience; Material failure is ubiquitous, with implications from geology to everyday life and material science. It often involves sudden, unpredictable events, with little or no macroscopically detectable precursors. A deeper understanding of the microscopic mechanisms eventually leading to failure is clearly required, but experiments remain scarce. Here, we show that the microscopic dynamics of a colloidal gel, a model network-forming system, exhibit dramatic changes that precede its macroscopic failure by thousands of seconds. Using an original setup coupling light scattering and rheology, we simultaneously measure the macroscopic deformation and the microscopic dynamics of the gel, while applying a constant shear stress. We show that the network failure is preceded by qualitative and quantitative changes of the dynamics, from reversible particle displacements to a burst of irreversible plastic rearrangements.

Power law rheology is of widespread occurrence in complex materials that are characterized by the presence of a very broad range of microstructural length and time scales. Although phenomenological models able to reproduce the observed rheological features exist, in general a well-established connection with the microscopic origin of this mechanical behavior is still missing. As a model system, this work focuses on a fractal colloidal gel. We thoroughly characterize the linear power law rheology of the sample and its age dependence. We show that at all sample ages and for a variety of rheological tests, the gel linear viscoelasticity is very accurately described by a fractional Maxwell (FM) model, characterized by a power law behavior. Thanks to a unique setup that couples small-angle static and dynamic light scattering to rheological measurements, we show that in the linear regime, shear induces reversible nonaffine rearrangements which might be at the origin of the power law rheology and we discuss the possible relationship between the FM model and the microscopic structure of the gel.Power law rheology is of widespread occurrence in complex materials that are characterized by the presence of a very broad range of microstructural length and time scales. Although phenomenological models able to reproduce the observed rheological features exist, in general a well-established connection with the microscopic origin of this mechanical behavior is still missing. As a model system, this work focuses on a fractal colloidal gel. We thoroughly characterize the linear power law rheology of the sample and its age dependence. We show that at all sample ages and for a variety of rheological tests, the gel linear viscoelasticity is very accurately described by a fractional Maxwell (FM) model, characterized by a power law behavior. Thanks to a unique setup that couples small-angle static and dynamic light scattering to rheological measurements, we show that in the linear regime, shear induces reversible nonaffine rearrangements which might be at the origin of the power law rheology and we discuss the ...

We investigate freely expanding sheets formed by ultrasoft gel beads, and liquid and viscoelastic drops, produced by the impact of the bead or drop on a silicon wafer covered with a thin layer of liquid nitrogen that suppresses viscous dissipation thanks to an inverse Leidenfrost effect. Our experiments show a unified behaviour for the impact dynamics that holds for solids, liquids, and viscoelastic fluids and that we rationalize by properly taking into account elastocapillary effects. In this framework, the classical impact dynamics of solids and liquids as far as viscous dissipation is negligible, appears as the asymptotic limits of a universal theoretical description. A novel material-dependent characteristic velocity that includes both capillary and bulk elasticity emerges from this unified description of the physics of impact., Comment: to appear in PRL

The collision of a liquid drop against a small target results in the formation of a thin liquid sheet that extends radially until it reaches a maximum diameter. The subsequent retraction is due to the air-liquid surface tension. We have used a time- and space-resolved technique to measure the thickness field of this class of liquid sheet, based on the grey level measurement of the image of a dyed liquid sheet recorded using a fast camera. This method enables a precise measurement of the thickness in the range $(10-450) \, \mathrm{\mu m}$, with a temporal resolution equal to that of the camera. We have measured the evolution with time since impact, $t$, and radial position, $r$, of the thickness, $h(r,t)$, for various drop volumes and impact velocities. Two asymptotic regimes for the expansion of the sheet are evidenced. The scalings of the thickness with $t$ and $r$ measured in the two regimes are those that were predicted in \citet{Rozhkov2004} fort the short-time regime and \citet{Villermaux2011} for the long time regime, but never experimentally measured before. Interestingly, our experimental data also evidence the existence of a maximum of the film thickness $h_{\rm{max}}(r)$ at a radial position $r_{\rm{h_{max}}}(t)$ corresponding to the crossover of these two asymptotic regimes. The maximum moves with a constant velocity of the order of the drop impact velocity, as expected theoretically. Thanks to our visualization technique, we also evidence an azimuthal thickness modulation of the liquid sheets., Comment: accepted for publication in Journal of Fluid Mechanics

International audience; Oil-swollen hexagonal mesophases resulting from the surfactant mediated self-assembly of a quaternarymixture of water, surfactant, co-surfactant, and oil, are versatile templates to synthesize anisotropicnanomaterials. Poly(diphenylbutadyine) (PDPB) polymer nanofibrous network structures were producedin the oil tubes of the mesophases by photo-induced radical polymerization using a chemical initiator orby gamma irradiation. The diameter of the nanofibers can be varied from 5 to 25 nm in a controlledfashion, and is directly determined by the diameter of the oil tube of the doped mesophases, proving thusa direct templating effect of the mesophase. The nanoIR technique allows chemical characterization andidentification of the polymer nanostructures simultaneously with morphological characterization. Cyclicvoltammetry has been used as an effective approach to evaluate both the energy level of the highestoccupied molecular orbital (HOMO) as well as the energy of the lowest unoccupied molecular orbital(LUMO) and the band gap of the PDPB. The conductivity of the PDPB nanostructures obtained by gammairradiation was estimated to be 0.1 S/cm, which is higher than the conductivity of PDPB nanostructurespreviously reported in the literature. The soft template approach allows size tunable synthesis of anisotropicpolymer structures with morphological homogeneity at the nanoscale with high conductivity, thus it appearsto be an attractive opportunity for electronic device applications.

International audience; Model gluten gels

Réf Journal: Journal of Rheology 61(6), 1267-1275, 2017; International audience; We study the fracture of reversible double transient networks, constituted of water suspensions of entangled surfactant wormlike micelles reversibly linked by various amounts of telechelic polymers. We provide a state diagram that delineates the regime of fracture without necking of the filament from the regime where no fracture or break-up has been observed. We show that filaments fracture when stretched at a rate larger than the inverse of the slowest relaxation time of the networks. We quantitatively demonstrate that dissipation processes are not relevant in our experimental conditions and that, depending on the density of nodes in the networks, fracture occurs in the linear viscoelastic regime or in a non-linear regime. In addition, analysis of the crack opening profiles indicates deviations from a parabolic shape close to the crack tip for weakly connected networks. We demonstrate a direct correlation between the amplitude of the deviation from the parabolic shape and the amount of non linear viscoelasticity.

We develop and thoroughly test a stress-controlled, parallel plates shear cell that can be coupled to an optical microscope or a small angle light scattering setup, for simultaneous investigation of the rheological properties and the microscopic structure of soft materials under an imposed shear stress. In order to minimize friction, the cell is based on an air bearing linear stage, the stress is applied through a contactless magnetic actuator, and the strain is measured through optical sensors. We discuss the contributions of inertia and of the small residual friction to the measured signal and demonstrate the performance of our device in both oscillating and step stress experiments on a variety of viscoelastic materials., 14 pages, 10 figures

National audience; NA

The plasma membrane-cytoskeleton interface is a dynamic structure involved in a variety of cellular events. Ezrin, a protein from the ERM family, provides a direct linkage between the cytoskeleton and the membrane via its interaction with phosphatidylinositol 4,5-bisphosphate (PIP2). In this paper, we investigate the interaction between PIP2 and ezrin in vitro using PIP2 dispersed in a unimolecular way in buffer. We compared the results obtained with full-length ezrin to those obtained with an ezrin mutant, which was previously found not to be localized at the cell membrane, and with the N-terminal membrane binding domain (FERM domain) of ezrin. We show that PIP2 induced a conformational change in full-length ezrin. PIP2 was also found to induce, in vitro, the formation of oligomers of wild-type ezrin, but not of mutant ezrin. These oligomers had previously been observed in vivo, but their role is yet to be clarified. Our finding hints at a possible role for PIP2 in the formation of ezrin oligomers.

Structuring wheat gluten proteins into gels with tunable mechanical properties would provide more versatility for the production of plant protein-rich food products. Gluten, a strongly elastic protein material insoluble in water, is hardly processable. We use a novel fractionation procedure allowing the isolation from gluten of a water/ethanol soluble protein blend, enriched in glutenin polymers at an unprecedented high ratio (50%). We investigate here the viscoelasticity of suspensions of the protein blend in a water/ethanol (50/50 v/v) solvent, and show that, over a wide range of concentrations, they undergo a spontaneous gelation driven by hydrogen bonding. We successfully rationalize our data using percolation models and relate the viscoelasticity of the gels to their fractal dimension measured by scattering techniques. The gluten gels display self-healing properties and their elastic plateaus cover several decades, from 0.01 to 10000 Pa. In particular very soft gels as compared to standard hydrated gluten can be produced., Comment: Food Hydrocolloids, in press

We investigate the dynamics of freely expanding liquid sheets prepared with fluids with different rheological properties, (i) viscous fluids with a zero-shear viscosity $\eta_0$ in the range $(1-1000) \, \mathrm{mPa.s}$ and (ii) viscoelastic Maxwell fluids whose elastic modulus, $G_0$, characteristic relaxation time, $\tau$, and zero-shear viscosity, $\eta_0=G_0 \tau$, can be tuned over several orders of magnitude. The sheets are produced by impacting a drop of fluid on a small cylindrical solid target. For viscoelastic fluids, we show that, when $\tau$ is shorter than the typical lifetime of the sheet ($\sim 10$ ms), the dynamics of the sheet is similar to that of Newtonian viscous liquids with equal zero-shear viscosity. In that case, for little viscous samples ($\eta_0, Comment: 10 pages, 9 figures

The structure of model gluten protein gels prepared in ethanol/water is investigated by small angle X-ray (SAXS) and neutrons (SANS) scattering. We show that gluten gels display radically different SAXS and SANS profiles when the solvent is (at least partially) deuterated. The detailed analysis of the SANS signal as a function of the solvent deuteration demonstrates heterogeneities of sample deuteration at different length scales. The progressive exchange between the protons (H) of the proteins and the deuteriums (D) of the solvent is inhomogeneous and 60 nm large zones that are enriched in H are evidenced. In addition, at low protein concentration, in the sol state, solvent deuteration induces a liquid/liquid phase separation. Complementary biochemical and structure analyses show that the denser protein phase is more protonated and specifically enriched in glutenin, the polymeric fraction of gluten proteins. These findings suggest that the presence of H-rich zones in gluten gels would arise from the preferential interaction of glutenin polymers through a tight network of non-exchangeable intermolecular hydrogen bonds., Comment: Soft Matter, Royal Society of Chemistry, 2016

We present real-time observations by confocal microscopy of the dynamic behavior of multilamellar vesicles (MLVs), composed of charged synthetic lipids, when put in contact with oppositely charged polyelectrolyte (PE) molecules. We find that the MLVs exhibit astonishing morphological transitions, which result from the discrete and progressive binding of the charged bilayers induced by a high PE concentration gradient. Our physical picture is confirmed by quantitative measurements of the fluorescence intensity as the bilayers bind to each other. The shape transitions lead eventually to the spontaneous formation of hollow capsules, whose thick walls are composed of lipid multilayers condensed with PE molecules. This class of objects may have some (bio)technological applications., Comment: to appear in JACS (2007)

Slow reduction of platinum salt in soft template made by direct hexagonal mesophases leads to Pt nanoballs with hexagonal cells formed by connected nanowires. The mesophases can be doped by high concentrations of platinum (up to 0.2 M) which leads to relatively large quantities of Pt nanostructures.

In this review we summarize some experimental investigations on the interactions between charged amphiphilic molecules and oppositely charged polyelectrolytes. We first present results on the formation, in bulk solutions, of polyelectrolyte/surfactant complexes of micrometric size. We show how the sample preparation procedure may affect the morphology of the complexes formed and how the kinetics influences the dynamics of their formation. The second and third parts are devoted to two-dimensional systems, namely a lipid bilayer attached to a polyelectrolyte multilayer cushion, on the one hand, and a lipid monolayer at the interface between air and a polyelectrolyte solution, on the other hand. We first demonstrate that, for lipids coupled to polyelectrolyte multilayers, the dynamics of the lipid is completely dominated by the electrostatic interactions with the polymer cushion. We finally investigate, by a combination of several techniques, how the interactions with a polyelectrolyte modify the properties of lipid monolayers and how ordering in an adsorption layer appears.

Complexes formed by a double-tail cationic surfactant, didodecyldimethyl ammonium bromide, and an anionic polyelectrolyte, an alternating copolymer of poly(styrene-alt-maleic acid) in its sodium salt form, were investigated with respect to variation in the charge ratio (x) between the polyelectrolyte negative charges and the surfactant positive charges. The morphology and microstructure of the complexes were studied by light microscopy and small-angle X-ray scattering for different preparation conditions. Independent of the sample preparation procedure and the charge ratio x, the X-ray results show that the microscopic structure of the complexes is a condensed lamellar phase. By contrast, the morphology of the complexes changes dramatically with the preparation procedure. The complexes formed by mixing a surfactant solution and a polyelectrolyte solution strongly depend on x and are always extremely heterogeneous in size and shape. Surprisingly, we show that, when the two solutions interdiffuse slowly, spherical complexes of micrometric and rather uniform size are systematically obtained, independently on the initial relative amount of surfactant and polyelectrolyte. The mechanism for the formation of these peculiar complexes is discussed.

Visible-light-responsive photocatalysts can directly harvest energy from solar light, offering a desirable way to solve energy and environment issues. Here, we show that one-dimensional poly(diphenylbutadiyne) nanostructures synthesized by photopolymerization using a soft templating approach have high photocatalytic activity under visible light without the assistance of sacrificial reagents or precious metal co-catalysts. These polymer nanostructures are very stable even after repeated cycling. Transmission electron microscopy and nanoscale infrared characterizations reveal that the morphology and structure of the polymer nanostructures remain unchanged after many photocatalytic cycles. These stable and cheap polymer nanofibres are easy to process and can be reused without appreciable loss of activity. Our findings may help the development of semiconducting-based polymers for applications in self-cleaning surfaces, hydrogen generation and photovoltaics.

The development of visible-light responsive photocatalysts would permit more efficient use of solar energy and thus would bring sustainable solutions to many environmental issues. Conductive polymers appear as a new class of very active photocatalysts under visible light. Among them poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most promising conjugated polymer with a wide range of applications. PEDOT nanostructures synthesized in soft templates via chemical oxidative polymerization demonstrate unprecedented photocatalytic activities for water treatment without the assistance of sacrificial reagents or noble metal co-catalysts and turn out to be better than TiO2 as benchmark catalyst. The PEDOT nanostructures exhibit a narrow band gap (E = 1.69 eV) and are characterized by excellent ability to absorb light in visible and near infrared region. The novel PEDOT-based photocatalysts are very stable with cycling and can be reused without appreciable loss of activity. Interestingly, hollow micrometric vesicular structures of PEDOT are not effective photocatalysts as compared to nanometric spindles suggesting size and shape dependent photocatalytic properties. The visible-light active photocatalytic properties of the polymer nanostructures present promising applications in solar light harvesting and broader fields.

We study the destabilization mechanism of thin liquid sheets expanding in air and show that dilute oil-in-water emulsion-based sheets disintegrate through the nucleation and growth of holes that perforate the sheet. The velocity and thickness fields of the sheet outside the holes are not perturbed by holes and hole opening follows a Taylor-Culick law. We find that a pre-hole, which widens and thins out the sheet with time, systematically precedes the hole nucleation. The growth dynamics of the pre-hole follows the law theoretically predicted for a liquid spreading on another liquid of higher surface tension due to Marangoni stresses. Classical Marangoni spreading experiments quantitatively corroborate our findings., Physical Review Letters in press

Réf Journal: Physical Review E, 92, 032307, 2015; International audience; We investigate how the microstructure of a colloidal polycrystal influences its linear viscoelasticity. We use thermosensitive copolymer micelles that arrange in water in a cubic crystalline lattice, yielding a colloidal polycrystal. The polycrystal is doped with a small amount of nanoparticles, of size comparable to that of the micelles, which behave as impurities and thus partially segregate in the grain boundaries. We show that the shear elastic modulus only depends on the packing of the micelles and does not vary neither with the presence of nanoparticles nor with the crystal microstructure. By contrast, we find that the loss modulus is strongly affected by the presence of nanoparticles. A comparison between rheology data and small-angle neutron scattering data suggests that the loss modulus is dictated by the total amount of nanoparticles in the grain boundaries, which in turn depends on the sample microstructure.

The supramolecular organization of wheat gluten proteins is largely unknown due to the intrinsic complexity of this family of proteins and their insolubility in water. We fractionate gluten in a water/ethanol (50/50 v/v) and obtain a protein extract which is depleted in gliadin, the monomeric part of wheat gluten proteins, and enriched in glutenin, the polymeric part of wheat gluten proteins. We investigate the structure of the proteins in the solvent used for extraction over a wide range of concentration, by combining X-ray scattering and multi-angle static and dynamic light scattering. Our data show that, in the ethanol/water mixture, the proteins display features characteristic of flexible polymer chains in a good solvent. In the dilute regime, the protein form very loose structures of characteristic size 150 nm, with an internal dynamics which is quantitatively similar to that of branched polymer coils. In more concentrated regimes, data highlight a hierarchical structure with one characteristic length scale of the order of a few nm, which displays the scaling with concentration expected for a semi-dilute polymer in good solvent, and a fractal arrangement at much larger length scale. This structure is strikingly similar to that of polymeric gels, thus providing some factual knowledge to rationalize the viscoelastic properties of wheat gluten proteins and their assemblies., Comment: to appear in Journal of Physical Chemistry B