Delicate Analysis of Interacting Proteins and Their Assemblies by Flow Field-Flow Fractionation Techniques.

We study the efficiency of several asymmetrical flow field-flow fractionation (AF4) techniques to investigate self-associating wheat gluten proteins. We compare the use of a denaturing buffer including sodium dodecyl sulfate (SDS) and a mild chaotropic solvent, water/ethanol, as the eluent, on a model gluten sample. Through a thorough analysis of the data obtained from coupled light scattering detectors and with the identification of molecular composition of the eluted protein, we evidence coelution events in several conditions. We show that the focus step used in conventional AF4 with the SDS buffer leads to the formation of aggregates that coelute with monomeric proteins. By contrast, a frit-inlet device enables the fractionation of individual wheat proteins in the SDS buffer. Interestingly conventional AF4, using water/ethanol as eluent, is an effective method for fractionating gluten proteins and their complex dynamic assemblies, which involve weak forces and are composed of both monomeric and polymeric proteins.

Scaling Properties of Gelling Systems in Nonlinear Shear Experiments.

We study model near-critical polymer gelling systems made of gluten protein dispersions stabilized at different distances from the gel point. We impose different shear rates and follow the time evolution of the stress. For sufficiently large shear rates, an intermediate stress overshoot is measured before reaching the steady state. We evidence self-similarity of the stress overshoot as a function of the applied shear rate for samples with various distances from the gel point, which is related to the elastic energy stored by the samples, as for dense systems close to the jamming transition. In concordance with the findings for glassy and jammed systems, we also measure that the stress after flow cessation decreases as a power law with time, with a characteristic relaxation time that depends on the shear rate previously imposed. These features revealed in nonlinear rheology could be the signature of a mesoscopic dynamics, which would depend on the extent of gelation.

A double rigidity transition rules the fate of drying colloidal drops.

The evaporation of drops of colloidal suspensions plays an important role in numerous contexts, such as the production of powdered dairies, the synthesis of functional supraparticles, and virus and bacteria survival in aerosols or drops on surfaces. The presence of colloidal particles in the evaporating drop eventually leads to the formation of a dense shell that may undergo a shape instability. Previous works propose that, for drops evaporating very fast, the instability occurs when the particles form a rigid porous solid, constituted of permanently aggregated particles at random close packing. To date, however, no measurements could directly test this scenario and assess whether it also applies to drops drying at lower evaporation rates, severely limiting our understanding of this phenomenon and the possibility of harnessing it in applications. Here, we combine macroscopic imaging and space- and time-resolved measurements of the microscopic dynamics of colloidal nanoparticles in drying drops sitting on a hydrophobic surface, measuring the evolution of the thickness of the shell and the spatial distribution and mobility of the nanoparticles. We find that, above a threshold evaporation rate, the drop undergoes successively two distinct shape instabilities, invagination and cracking. While permanent aggregation of nanoparticles accompanies the second instability, as hypothesized in previous works on fast-evaporating drops, we show that the first one results from a reversible glass transition of the shell, unreported so far. We rationalize our findings and discuss their implications in the framework of a unified state diagram for the drying of colloidal drops sitting on a hydrophobic surface.

Instabilities in freely expanding sheets of associating viscoelastic fluids.

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 structures. Upon impact, the 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 to the formation of holes. We find that the rheological properties of the material 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 the Deborah number related to the shortest relaxation time associated with 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.

Viscoelasticity and elastocapillarity effects in the impact of drops on a repellent surface.

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, dmax, the maximal expansion of the sheets, and tmax 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 dmax and tmax.

Sunflower Proteins at Air-Water and Oil-Water Interfaces.

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 RH ∼ 80 nm, evidenced in equilibrium with hexameric globulins (RH ∼ 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.

Impact of the protein composition on the structure and viscoelasticity of polymer-like gluten gels.

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.

Role of Normal Stress in the Creep Dynamics and Failure of a Biopolymer Gel.

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 nonfracturing gels and exhibit large spatiotemporal fluctuations. A spatially localized region with significant plasticity eventually nucleates, expands progressively, and finally invades the whole sample, triggering macroscopic failure.

Microscopic precursors of failure in soft matter.

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.

Phase separation dynamics of gluten protein mixtures.

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-1) 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 down 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.

Multistep building of a soft plant protein film at the air-water interface.

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 Π of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of Π collected at different bulk protein concentrations C can be merged onto a single master curve when Π is plotted as a function of αt where t is the time elapsed since the formation of the air/water interface and α 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 α 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 Π. This stage is followed, at higher Π, 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.

Microscopic dynamics and failure precursors of a gel under mechanical load.

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.

Swollen hexagonal liquid crystals as smart nanoreactors: implementation in materials chemistry for energy applications.

Materials are the key roadblocks for the commercialization of energy conversion devices in fuel cells and solar cells. Significant research has focused on tuning the intrinsic properties of materials at the nanometer scale. The soft template mediated controlled fabrication of advanced nanostructured materials is attracting 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-stabilized 1D, 2D or 3D nanometric assemblies regularly arranged in an aqueous solvent. Interestingly, the characteristic size of the SLCs can be controlled by adjusting the volume ratio of oil to water. The non-polar and/or polar compartments of the SLCs can be doped with guest molecules and used as nanoreactors for the synthesis of various metals (Pt, Pd, Au, etc.), conducting polymers and composite nanostructures with controlled size and shape. 1D, 2D and 3D mono- and bimetallic nanostructures of controlled composition and porosity can also be fabricated. These materials have demonstrated impressive enhancements of their electrochemical properties as compared to their bulk counterparts and have been identified as promising for further implementation in energy harvesting applications. In this review article, recent research materials are described regarding the development of functional materials with much improved performances for catalysis applications. This review addresses a brief overview of swollen hexagonal mesophases as nanoreactors, describes examples of nanostructured materials synthesized in these 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 literature for enhanced catalytic activity.

Playing with Emulsion Formulation to Control the Perforation of a Freely Expanding Liquid Sheet.

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.

Rearrangement Zone around a Crack Tip in a Double Self-Assembled Transient Network.

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 rodlike 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, ξ, which corresponds to the length scale over which micelle alignment occurs. We find that ξ is larger for slower cracks, suggesting an increase of ductility.

Visible-light active conducting polymer nanostructures with superior photocatalytic activity.

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.

Bursting of Dilute Emulsion-Based Liquid Sheets Driven by a Marangoni Effect.

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 the Taylor-Culick law. We find that a prehole, which widens and thins out the sheet with time, systematically precedes the hole nucleation. The growth dynamics of the prehole 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.

Viscoelasticity of colloidal polycrystals doped with impurities.

We investigate how the microstructure of a colloidal polycrystal influences its linear visco-elasticity. 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 varies 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.

Conducting polymer nanostructures for photocatalysis under visible light.

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.

Plasticity of a colloidal polycrystal under cyclic shear.

We use confocal microscopy and time-resolved light scattering to investigate plasticity in a colloidal polycrystal, following the evolution of the network of grain boundaries as the sample is submitted to thousands of shear deformation cycles. The grain boundary motion is found to be ballistic, with a velocity distribution function exhibiting nontrivial power law tails. The shear-induced dynamics initially slow down, similarly to the aging of the spontaneous dynamics in glassy materials, but eventually reach a steady state. Surprisingly, the crossover time between the initial aging regime and the steady state decreases with increasing probed length scale, hinting at a hierarchical organization of the grain boundary dynamics.