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International audience; Aggregation mechanisms of amyloid β peptides depend on multiple intrinsic and extrinsic physicochemical factors (e.g., peptide chain length, truncation, peptide concentration, pH, ionic strength, temperature, metal concentration, etc.). Due to this high number of parameters, the formation of oligomers and their propensity to aggregate make the elucidation of this physiopathological mechanism a challenging task. From the analytical point of view, up to our knowledge, few techniques are able to quantify, in real time, the proportion and the size of the different soluble species during the aggregation process. This work aims at demonstrating the efficacy of the modern Taylor dispersion analysis (TDA) performed in capillaries (50 μm i.d.) to unravel the speciation of β-amyloid peptides in low-volume peptide samples (∼100 μL) with an analysis time of ∼3 min per run. TDA was applied to study the aggregation process of Aβ(1-40) and Aβ(1-42) peptides at physiological pH and temperature, where more than 140 data points were generated with a total volume of ∼1 μL over the whole aggregation study (about 0.5 μg of peptides). TDA was able to give a complete and quantitative picture of the Aβ speciation during the aggregation process, including the sizing of the oligomers and protofibrils, the consumption of the monomer, and the quantification of different early- and late-formed aggregated species.

Multiple speckle diffusing wave spectroscopy (MSDWS) can be applied to measure spatially heterogeneous mechanical behavior in soft solids, with high sensitivity to deformation and both spatial and temporal resolution. In this paper, we discuss the mathematical approach behind the quantification of the deformation rate from MSDWS data and provide guidelines for optimizing the selection of experimental parameters in measurements. After validating the method in extensional tests on an elastomer, we provide an example of the potentiality of MSDWS by measuring the spatial distribution of the deformation rate during shear debonding of adhesive tapes. We quantitatively characterize the deformation rate distribution related to shearing and peeling under loading. A highly heterogeneous deformation rate distribution is observed, and time-dependent measurements reveal an increase in deformation localization hundreds of seconds before full debonding. This behavior, previously predicted by theory and simulation, is demonstrated here experimentally for the first time.

Mucus is a biological gel covering the surface of several tissues and insuring key biological functions, including as a protective barrier against dehydration, pathogens penetration, or gastric acids. Mucus biological functioning requires a finely tuned balance between solid-like and fluid-like mechanical response, insured by reversible bonds between mucins, the glycoproteins that form the gel. In living organisms, mucus is subject to various kinds of mechanical stresses, e.g. due to osmosis, bacterial penetration, coughing and gastric peristalsis. However, our knowledge of the effects of stress on mucus is still rudimentary and mostly limited to macroscopic rheological measurements, with no insight into the relevant microscopic mechanisms. Here, we run mechanical tests simultaneously to measurements of the microscopic dynamics of pig gastric mucus. Strikingly, we find that a modest shear stress, within the macroscopic rheological linear regime, dramatically enhances mucus reorganization at the microscopic level, as signalled by a transient acceleration of the microscopic dynamics, by up to two orders of magnitude. We rationalize these findings by proposing a simple yet general model for the dynamics of physical gels under strain and validate its assumptions through numerical simulations of spring networks. These results shed new light on the rearrangement dynamics of mucus at the microscopic scale, with potential implications in phenomena ranging from mucus clearance to bacterial and drug penetration., To appear in PNAS

The septin collar of budding yeast is an ordered array of septin filaments that serves a scaffolding function for the cytokinetic machinery at the bud neck and compartmentalizes the membrane between mother and daughter cell. How septin architecture is aided by septin-binding proteins is largely unknown. Syp1 is an endocytic protein that was implicated in the timely recruitment of septins to the newly forming collar through an unknown mechanism. Using advanced microscopy and in vitro reconstitution assays, we show that Syp1 is able to align laterally and tightly pack septin filaments, thereby forming flat bundles or sheets. This property is shared by the Syp1 mammalian counterpart FCHo2, thus emphasizing conserved protein functions. Interestingly, the septin-bundling activity of Syp1 resides mainly in its intrinsically disordered region. Our data uncover the mechanism through which Syp1 promotes septin collar assembly and offer another example of functional diversity of unstructured protein domains.

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

Non-aqueous Taylor dispersion analysis (TDA) was used for the size-characterization of natural and synthetic polyisoprenes (4 × 103–2 × 106 g/mol molar mass). Not only the weight-average hydrodynamic radius (Rh), but also the probability distribution of the hydrodynamic radius, were both derived from the Taylorgrams by a simple integration of the elution profile and by a more sophisticated constrained regularized linear inversion of the Taylorgram, respectively. Results in terms of size characterization (hydrodynamic radii between 2 and 100 nm) were compared to size exclusion chromatography coupled to a refractive index-based mass detector. Multimodal size distributions were resolved by TDA for industrial and natural polyisoprenes, with the advantage over the chromatographic technique that, in TDA, there is no abnormal elution of microaggregates (hydrodynamic radii ∼ 40–50 nm). Considering the importance and the difficulty of characterizing polyisoprene microaggregates, TDA appears as a promising and simple technique for the characterization of synthetic and natural rubber. (Resume d'auteur)

We use space-resolved dynamic light scattering in the highly multiple scattering regime (Photon Correlation Imaging Diffusing Wave Spectroscopy, PCI-DWS) to investigate temperature-induced phase transitions in polymorphic materials. We study paraffin wax as a simple model system and chocolate, a prototypical example of fat-based products exhibiting complex, history-dependent phase transitions. We find that microscopic dynamics measured using PCI-DWS show remarkable, non-monotonic behavior upon heating: they transiently accelerate when crossing phase transition and slow down above the transition temperature. Sub-micron resolution measurements of the local drift of the sample surface reveal that the speed-up of the dynamics is due to the strain field induced by the change in density at transition temperature. The transition temperatures obtained from PCI-DWS are found to be in excellent agreement with those inferred from complementary differential scanning calorimetry and X-ray scattering experiments, thereby validating PCI-DWS as a new, powerful tool for the characterization of phase transitions in complex soft matter. Finally, we demonstrate the unique possibilities afforded by space-resolved DWS by investigating the spatially heterogeneous response of poorly manufactured or composite chocolate samples.

International audience; We investigate the spontaneous restructuring andaging behavior of pig gastric mucus gels by combining rheology andnonconventional static and dynamic light scattering. We find that themucus elasticity weakens over time, concomitantly to structuralevolution toward a locally more compact configuration and the onsetof large scale density fluctuations. We interpret this behavior asstemming from an arrested phase separation, as observed in manygel-forming polymer systems. This scenario is confirmed by spaceandtime-resolved dynamic light scattering data, showing that the gelrestructuring is due to intermittent bursts of spatially correlatedrearrangements, leading to ballistic dynamics.

We exploit the deformation of drops spinning in a denser background fluid to investigate the effective interfacial tension (EIT) between miscible molecular fluids. We find that for sufficiently low interfacial tension, spinning drops develop dumbbell shapes, with two large heads connected by a thinner central body. We show that this shape depends not only on the density and viscosity contrast between the drop and background fluids, but also on the fluid molecular structure, and hence on the stresses developing at their interface due to different molecular interaction. We systematically investigate the dynamics of dumbbell-shaped drops of water-glycerol mixtures spinning in a pure glycerol reservoir. By developing a model for the deformation based on the balance of the shear stress opposing the deformation, the imposed normal stress on the drop and an effective interfacial tension, we exploit the time evolution of the drop shape to measure the EIT. Our results show that the EIT in water-glycerol systems is orders of magnitude lower than that reported in previous experimental measurements, and in excellent agreement with values calculated via the phase field model proposed in [Phys. Rev. X 6, 041057, 2016]., Comment: 11 pages, 6 figures

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; Taylor dispersion analysis (TDA) is a powerful sizing technique very well suited for (macro)molecules between angstroms and submicrons (typically up to 200 nm). However, new detection modes are required for non-UV-absorbing (macro)molecules such as most of the polysaccharides, including starches. In this work, two different detection modes were compared, backscattering interferometry (BSI) and UV-photooxidation detection (UV-POD). TDA-BSI measures the relative change of the refractive index between eluent and sample (water as eluent in this work), whereas TDA-UV-POD detects the UV-absorbing photo-oxidized products of polysaccharides/starches in strong alkaline media (130 mM NaOH or 1 M KOH). TDA-UV-POD detection was evaluated for linearity and sensitivity at two wavelengths, 214 and 266 nm. The mass-average hydrodynamic radius (Rh) obtained by TDA-BSI and TDA-UV-POD was found to be in excellent agreement, whereas higher average Rh values were obtained by batch dynamic light scattering (DLS) under the same conditions, because of the higher sensitivity of DLS to large-size solutes and aggregates. The hydrodynamic radius distributions obtained by TDA and DLS are intrinsically different but both techniques were found to be complementary, providing useful information on sample dispersity. Owing to the absence of the stationary phase, low sample consumption with straightforward sample preparation (no filtration), and no calibration, TDA is anticipated to become a method of choice for the size-based characterization of polysaccharides, including starches.

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.

Understanding the microscopic origin of the rheological behavior of soft matter is a long-lasting endeavour. While early efforts concentrated mainly on the relationship between rheology and structure, current research focuses on the role of microscopic dynamics. We present in two companion papers a thorough discussion of how Fourier space-based methods may be coupled to rheology to shed light on the relationship between the microscopic dynamics and the mechanical response of soft systems. In this first companion paper, we report a theoretical, numerical and experimental investigation of dynamic light scattering coupled to rheology. While in ideal solids and simple viscous fluids the displacement field under a shear deformation is purely affine, additional non-affine displacements arise in many situations of great interest, for example in elastically heterogeneous materials or due to plastic rearrangements. We show how affine and non-affine displacements can be separately resolved by dynamic light scattering, and discuss in detail the effect of several non-idealities in typical experiments., 13 pages, 7 figures. First paper of a series of two companion papers. The second companion paper will be posted shortly

We report on the extensional dynamics of spinning drops in miscible and immiscible background fluids following a rotation speed jump. Two radically different behaviours are observed. Drops in immiscible environments relax exponentially to their equilibrium shape, with a relaxation time that does not depend on the centrifugal forcing. We find an excellent quantitative agreement with the relaxation time predicted for quasi-spherical drops by Stone and Bush (Q. Appl. Math. 54, 551 (1996)), while other models proposed in the literature fail to capture our data. By contrast, drops immersed in a miscible background fluid do not relax to a steady shape: they elongate indefinitely, their length following a power-law $l(t)\sim t^{\frac{2}{5}}$ in very good agreement with the dynamics predicted by Lister and Stone (J. Fluid Mech. 317, 275 (1996)) for inviscid drops. Our results strongly suggest that low compositional gradients in miscible fluids do not give rise to an effective interfacial tension measurable by spinning drop tensiometry., Comment: 31 pages, 6 figures

We discuss in two companion papers (arXiv:1802.03737 and the present manuscript) how Fourier-space measurements may be coupled to rheological tests in order to elucidate the relationship between mechanical properties and microscopic dynamics in soft matter. In this second companion paper, we focus on Differential Dynamic Microscopy (DDM) under shear. We highlight the analogies and the differences with Dynamic Light Scattering coupled to rheology, providing a theoretical approach and practical guidelines to separate the contributions to DDM arising from the affine and the non-affine part of the microscopic displacement field. We show that in DDM under shear the coherence of the illuminating source plays a key role, determining the effective sample thickness that is probed. Our theoretical analysis is validated by experiments on 2D samples and 3D gels., This is a companion paper to the manuscript arXiv:1802.03737

We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.

International audience; This work aims at demonstrating the interest ofmodern Taylor dispersion analysis (TDA), performed in narrow internal diameter capillary, for monitoring biopolymer degradations. Hydrolytic and enzymatic degradations ofdendrigraft poly-L-lysine taken as model compounds havebeen performed and monitored by TDA at differentdegradation times. Different approaches for the dataprocessing of the taylorgrams are compared, including simpleintegration of the taylorgram, curve fitting with a finite numberof Gaussian peaks, cumulant-like method and ConstrainedRegularized Linear Inversion approach. Valuable informationon the kinetics of the enzymatic/hydrolytic degradation reactions and on the degradation process can be obtained by TDA.

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 ...

HTRC is a new ligth scattering technique that measures by holography the field amplitude scattered by a sample, and analyze its spatial correlations. HTRC outperforms other light scattering techniques like DLS, DWS and TRC.

The interfacial tension between immiscible fluids is responsible for a wealth of every-day phenomena, from the spherical shape of small drops and bubbles to the ability to walk on water of many insects. More than a century ago, physicist and mathematician D. Korteweg postulated the existence of an effective interface tension for miscible fluids, whenever a composition gradient exists, as encountered, e.g., in many flow geometries. In this mini-review, we discuss experimental work performed in the last decades that demonstrates the existence of a positive effective interface tension in a variety of systems, from molecular, near-critical liquids to complex fluids such as polymer solutions and colloidal suspensions. The various experimental strategies that have been deployed are discussed, together with their advantages and limitations. Finally, some of the key theoretical questions still open are outlined.

Hydrodynamic instabilities in miscible fluids are ubiquitous, from natural phenomena up to geological scales, to industrial and technological applications, where they represent the only way to control and promote mixing at low Reynolds numbers, well below the transition from laminar to turbulent flow. As for immiscible fluids, the onset of hydrodynamic instabilities in miscible fluids is directly related to the physics of their interfaces. The focus of this review is therefore on the general mechanisms driving the growth of disturbances at the boundary between miscible fluids, under a variety of forcing conditions. In the absence of a regularizing mechanism, these disturbances would grow indefinitely. For immiscible fluids, interfacial tension provides such a regularizing mechanism, because of the energy cost associated to the creation of new interface by a growing disturbance. For miscible fluids, however, the very existence of interfacial stresses that mimic an effective surface tension is debated. Other mechanisms, however, may also be relevant, such as viscous dissipation. We shall review the stabilizing mechanisms that control the most common hydrodynamic instabilities, highlighting those cases for which the lack of an effective interfacial tension poses deep conceptual problems in the mathematical formulation of a linear stability analysis. Finally, we provide a short overview on the ongoing research on the effective, out of equilibrium interfacial tension between miscible fluids., Comment: 9 figures

International audience; Interfacial tension between immiscible phases is a well-known phenomenon, which manifests itself in everyday life, from the shape of droplets and foam bubbles to the capillary rise of sap in plants or the locomotion of insects on a water surface. More than a century ago, Korteweg generalized this notion by arguing that stresses at the interface between two miscible fluids act transiently as an effective, nonequilibrium interfacial tension, before homogenization is eventually reached. In spite of its relevance in fields as diverse as geosciences, polymer physics, multiphase flows, and fluid removal, experiments and theoretical works on the interfacial tension of miscible systems are still scarce, and mostly restricted to molecular fluids. This leaves crucial questions unanswered, concerning the very existence of the effective interfacial tension, its stabilizing or destabilizing character, and its dependence on the fluid's composition and concentration gradients. We present an extensive set of measurements on miscible complex fluids that demonstrate the existence and the stabilizing character of the effective interfacial tension, unveil new regimes beyond Korteweg's predictions, and quantify its dependence on the nature of the fluids and the composition gradient at the interface. We introduce a simple yet general model that rationalizes nonequilibrium interfacial stresses to arbitrary mixtures, beyond Korteweg's small gradient regime, and show that the model captures remarkably well both our new measurements and literature data on molecular and polymer fluids. Finally, we briefly discuss the relevance of our model to a variety of interface-driven problems, from phase separation to fracture, which are not adequately captured by current approaches based on the assumption of small gradients.

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

To investigate the interplay between microscopic dynamics and macroscopic rheology in soft matter, we couple a stress-controlled-rheometer equipped with a Couette cell to a light scattering setup in the imaging geometry, which allows us to measure both the deformation field and the microscopic dynamics. To validate our setup, we test two model systems. For an elastic solid sample, we recover the expected deformation field within 1 micron. For a pure viscous fluid seeded with tracer particles, we measure the velocity profile and the dynamics of the tracers, both during shear and at rest. The velocity profile is acquired over a gap of 5 mm with a temporal and spatial resolution of 1 s and 100 microns, respectively. At rest, the tracer dynamics have the expected diffusive behavior. Under shear, the microscopic dynamics corrected for the average drift due to solid rotation scale with the local shear rate, demonstrating that our setup captures correctly the relative motion of the tracers due to the affine deformation., 17 pages, 12 figures

International audience; Scattering techniques can average over many more particles than can direct methods and thus often provide much better quantitative measurements of the average structural and dynamical properties of materials. Scattering techniques generally work best when the wavelength of the radiation is about the same as the size of the structures that scatter the radiation. The basic principle underlying light scattering can be grasped by considering the intensity of the light scattered by two particles within the scattering volume. Dynamic light scattering (DLS) takes note of particular fact and uses the time dependence of the flickering speckles to quantitatively characterize the underlying motion of the scatterers. Scattering methods based on imaging geometries have been developed, such as Photon Correlation Imaging and Near Field Scattering. In differential dynamic microscopy (DDM), one takes again advantage of a differential algorithm.

We couple a laser-based, space-resolved dynamic light scattering apparatus to a universal testing machine for mechanical extensional tests. We perform simultaneous optical and mechanical measurements on polyether ether ketone, a semi-crystalline polymer widely used in the industry. Due to the high turbidity of the sample, light is multiply scattered by the sample and the diffusing wave spectroscopy (DWS) formalism is used to interpret the data. Space-resolved DWS yields spatial maps of the sample strain and of the microscopic dynamics. An excellent agreement is found between the strain maps thus obtained and those measured by a conventional stereo-correlation bench. The microscopic dynamics reveals both affine motion and plastic rearrangements. Thanks to the extreme sensitivity of DWS to displacements as small as 1 nm, plastic activity and its spatial localization can be detected at an early stage of the sample deformation, making the technique presented here a valuable complement to existing material characterization methods., 9 pages, 5 figures

We introduce a new estimator of particle size polydispersity for dynamic light scattering data, which quantifies the relative width of the intensity-weighted distribution of diffusion coefficients. Simulated dynamic light scattering data are analyzed to (i) compare the accuracy and precision of the new polydispersity indicator to polydispersity measurements from standard cumulant and moment analysis (MA) fits and (ii) establish for each method the optimum data range for fitting. Although MA is preferable at low polydispersity, the new estimator is the most accurate and precise at intermediate and large polydispersities. Finally, we successfully apply the method proposed here to real data from colloidal particles, microgels, and polymer solutions.

Journal: Soft Matter: 6, 3030-3037 (2010); International audience; Foams are ideal model systems to study stress-driven dynamics, as stress-imbalances within the system are continuously generated by the coarsening process, which unlike thermal fluctuations, can be conveniently quantified by optical means. However, the high turbidity of foams generally hinders the detailed study of the temporal and spatial distribution of rearrangement events, such that definite assessments regarding their contribution to the overall dynamics could not be made so far. In this paper, we use novel light scattering techniques to measure the frequency and position of events within a large sample volume. As recently reported (A. S. Gittings and D. J. Durian, Phys. Rev. E, 2008, 78, 066313), we find that the foam dynamics is determined by two distinct processes: intermittent bubble rearrangements of finite duration and a spatially homogeneous quasicontinuous process. Our experiments show that the convolution of these two processes determines the age-dependence of the mean dynamics, such that relations between intermittent rearrangements and coarsening process can not be established by considering means. By contrast the use of the recently introduced photon correlation imaging technique (A. Duri, D. A. Sessoms, V. Trappe, and L. Cipelletti, Phys. Rev. Lett., 2009, 102, 085702) enables us to assess that the event frequency is directly determined by the strain-rate imposed by the coarsening process. Surprisingly, we also find that, although the distribution of successive events in time is consistent with a random process, the spatial distribution of successive events is not random: rearrangements are more likely to occur within a recently rearranged zone. This implies that a topological rearrangement is likely to lead to an unstable configuration, such that a small amount of coarsening-induced strain is sufficient to trigger another event.

We use Photon Correlation Imaging, a recently introduced space-resolved dynamic light scattering method, to investigate the spatial correlation of the dynamics of a variety of jammed and glassy soft materials. Strikingly, we find that in deeply jammed soft materials spatial correlations of the dynamics are quite generally ultra-long ranged, extending up to the system size, orders of magnitude larger than any relevant structural length scale, such as the particle size, or the mesh size for colloidal gel systems. This has to be contrasted with the case of molecular, colloidal and granular ``supercooled'' fluids, where spatial correlations of the dynamics extend over a few particles at most. Our findings suggest that ultra long range spatial correlations in the dynamics of a system are directly related to the origin of elasticity. While solid-like systems with entropic elasticity exhibit very moderate correlations, systems with enthalpic elasticity exhibit ultra-long range correlations due to the effective transmission of strains throughout the contact network., Comment: To appear in Soft Matter

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.

International audience; We use dynamic light scattering to investigate the effects of charge polydispersity and chargeresidence time on the dynamics of a micellar system. While in the corresponding uncharged system onlyone exponential relaxation is observed, two relaxation modes are seen when charging the micelles byadding charged co-surfactant molecules with a long residence time. We attribute the existence of thesetwo relaxation modes to the combined effect of size polydispersity and charge polydispersity, i.e. frozenfluctuations of the number of charges per micelle. Further support to this scenario is provided by controlexperiments on a similar charged system, but where the charge residence time is short compared to thetime scales probed by dynamic light scattering. Here, charge polydispersity is effectively suppressed dueto the rapid exchange of charged molecules between micelles and only one single relaxation mode is seen,thereby demonstrating the key role of frozen charge fluctuations in the complex dynamics of our micellarsystem.

We use time-resolved dynamic light scattering to investigate the slow dynamics of a colloidal gel. The final decay of the average intensity autocorrelation function is well described by $g\_2(q,\tau)-1 \sim \exp[-(\tau/\tau\_\mathrm{f})^p]$, with $\tau\_\mathrm{f} \sim q^{-1}$ and $p$ decreasing from 1.5 to 1 with increasing $q$. We show that the dynamics is not due to a continuous ballistic process, as proposed in previous works, but rather to rare, intermittent rearrangements. We quantify the dynamical fluctuations resulting from intermittency by means of the variance $\chi(\tau,q)$ of the instantaneous autocorrelation function, the analogous of the dynamical susceptibility $\chi\_4$ studied in glass formers. The amplitude of $\chi$ is found to grow linearly with $q$. We propose a simple --yet general-- model of intermittent dynamics that accounts for the $q$ dependence of both the average correlation functions and $\chi$., Comment: Revised and improved, to appear in Europhys. Lett

A new type of hybrid material is prepared through sol-gel processing by the polycondensation of (MeO)3Si–R–Si(OMe)3 units containing a rigid organic anisotropic group R. The hybrid covalently bounded organic-inorganic gel shows an unexpected structural birefringence Δn (Δn = 2 × 10−3). This birefringence is induced by a strain field anisotropy during gel aging as revealed by simultaneous dynamic light scattering and birefringence measurements. To better address the role of the strain field, we use a free interface sol-gel/air to control strain anisotropy and to measure the gel optical axis and its birefringence. We find that the birefringence is associated to a long-range orientational order of organic moieties induced by the strain anisotropy during the gel aging.

We explore the influence of particle softness and internal structure on both the bulk and interfacial rheological properties of colloidal suspensions. We probe bulk stresses by conventional rheology, by measuring the flow curves, shear stress vs strain rate, for suspensions of soft, deformable microgel particles and suspensions of near hard-sphere-like silica particles. A similar behavior is seen for both kind of particles in suspensions at concentrations up to the random close packing volume fraction, in agreement with recent theoretical predictions for sub-micron colloids. Transient interfacial stresses are measured by analyzing the patterns formed by the interface between the suspensions and their own solvent, due to a generalized Saffman-Taylor hydrodynamic instability. At odd with the bulk behavior, we find that microgels and hard particle suspensions exhibit vastly different interfacial stress properties. We propose that this surprising behavior results mainly from the difference in particle internal structure (polymeric network for microgels vs compact solid for the silica particles), rather than softness alone., Comment: 20 pages, 8 figures

We present extensive experimental and theoretical investigations on the structure, phase behavior, dynamics and rheology of model soft–hard colloidal mixtures realized with large, multiarm star polymers as the soft component and smaller, compact stars as the hard one. The number and length of the arms in star polymers control their softness, whereas the size ratio, the overall density and the composition are additional parameters varied for the mixtures. A coarse-grained theoretical strategy is employed to predict the structure of the systems as well as their ergodicity properties on the basis of mode coupling theory, for comparison with rheological measurements on the samples. We discovered that dynamically arrested star–polymer solutions recover their ergodicity upon addition of colloidal additives. At the same time the system displays demixing instability, and the binodal of the latter meets the glass line in a way that leads, upon addition of a sufficient amount of colloidal particles, to an arrested phase separation and reentrant solidification. We present evidence for a subsequent solid-to-solid transition well within the region of arrested phase separation, attributed to a hard-sphere-mixture type of glass, due to osmotic shrinkage of the stars at high colloidal particle concentrations. We systematically investigated the interplay of star functionality and size ratio with glass melting and demixing, and rationalized our findings by the depletion of the big stars due to the smaller colloids. This new depletion potential in which, contrary to the classic colloid–polymer case, the hard component depletes the soft one, has unique and novel characteristics and allows the calculation of phase diagrams for such mixtures. This work covers a broad range of soft–hard colloidal mixture compositions in which the soft component exceeds the hard one in size and provides general guidelines for controlling the properties of such complex mixtures.

We introduce a temporal scheme for data sampling, based on a variable delay between two successive data acquisitions. The scheme is designed so as to reduce the average data flow rate, while still retaining the information on the data evolution on fast time scales. The practical implementation of the scheme is discussed and demonstrated in light scattering and microscopy experiments that probe the dynamics of colloidal suspensions using CMOS or CCD cameras as detectors., Comment: Submitted to J. Phys.: Cond. Matter. 11 pages, 5 figures + Supporting Data (Python software to implement the method described in the manuscript)

We introduce a new scheme for investigating temporally heterogeneous dynamics, which is termed time-resolved correlation (TRC). TRC is applied to data obtained by diffusing wave spectroscopy probing the slow dynamics of a strongly aggregated colloidal gel. Other examples of TRC data, collected for different jammed materials in single and multiple scattering, are provided to demonstrate the wide range of applicability of this method. In all cases we find evidence that the slow dynamics results from a series of discrete steps rather than from a continuous motion, suggesting temporal heterogeneities to be a general feature of slow dynamics in jammed systems.

Attractive colloidal particles can exhibit a fluid to solid phase transition if the magnitude of the attractive interaction is sufficiently large, if the volume fraction is sufficiently high, and if the applied stress is sufficiently small. The nature of this fluid to solid transition is similar for many different colloid systems, and for many different forms of interaction. The jamming phase transition captures the common features of these fluid to solid translations, by unifying the behavior as a function of the particle volume fraction, the energy of interparticle attractions, and the applied stress. This paper describes the applicability of the jamming state diagram, and highlights those regions where the fluid to solid transition is still poorly understood. It also presents new data for gelation of colloidal particles with an attractive depletion interaction, providing more insight into the origin of the fluid to solid transition.

Slow dynamics and aging effects in disordered, out-of-equilibrium systems are a rich and fascinating topic, yet still poorly understood. Recent developments in light scattering methods, such as the multispeckle technique, combined with new theoretical approaches that underline the analogies between different glassy materials are bringing a better understanding of these phenomena.

Optical tracer-microrheology has been applied to study the rheological properties of a concentrated surfactant solution. Under the chosen conditions these surfactants self-assemble to form giant polymer-like micelles, resulting in a strongly viscoelastic liquid. A novel approach to the analysis of the local dynamic properties of tracer particles is presented, based on a combination of single- and multi-speckle diffusing wave spectroscopy (DWS). With this technique we could significantly extend the accessible frequency range to the key rheological properties as given by the loss and storage modulus, G''(ω) and G'(ω). A study of the high-frequency range, not accessible to standard techniques, shows good overall agreement with conventional models. However, we find a distinct temperature dependence of the characteristic modulus G0 incompatible with the simple picture of a single relaxation process.

Taylor dispersion analysis is an increasingly popular characterization method that measures the diffusion coefficient, and hence the hydrodynamic radius, of (bio)polymers, nanoparticles or even small molecules. In this work, we describe an extension to current data analysis schemes that allows size polydispersity to be quantified for an arbitrary sample, thereby significantly enhancing the potentiality of Taylor dispersion analysis. The method is based on a cumulant development similar to that used for the analysis of dynamic light scattering data. Specific challenges posed by the cumulant analysis of Taylor dispersion data are discussed, and practical ways to address them are proposed. We successfully test this new method by analyzing both simulated and experimental data for solutions of moderately polydisperse polymers and polymer mixtures., 41 pages (including Supporting Information), 5 figures (+ 7 figs. in the Supporting Information)

We study the effect of isopropyl alcohol (IPA) and various salts (sodium chloride, sodium thiocyanate, sodium carbonate, and urea) on the rheological behavior and the conformation of aqueous guar solutions. Ultralow angle light scattering, conventional light scattering, and neutron scattering are used to probe the structure of guar over length scales spanning 5 decades, from a few angstroms to several tens of microns. Although both IPA and salts worsen solvent conditions, their effect is very different. Isopropyl alcohol promotes the formation of a network of large-scale structures via intermolecular associations, thus increasing dramatically the elastic response of guar solutions. Salts, on the contrary, affects guar on a local scale, leading to a more collapsed chain configuration, thus to a lower effective volume fraction and to reduced viscosity.

We examine the structure of guar as a function of concentration in both H2O and D2O using several different scattering techniques. The range of scattering vectors spans 5 decades (143 cm-1 < q < 10.3 × 106 cm-1), providing insight into the supramolecular and local organization of the chains. This allows us to directly characterize the large-scale aggregate structure of the guar, which can be on the order of 100 μm. The aggregates are most likely loosely interconnected with single chains and other aggregates, and the structure and organization are critical in determining solution viscoelastic properties. The solubility is poorer in D2O, as evidenced by larger aggregates, higher scattering intensities, a slightly higher fractal dimension, and a sublinear concentration dependence of the intensity. Aggregates were found in dilute neutral guar solutions as well as in cationic guar solutions (in H2O), whether screened or unscreened. The presence of aggregates at all concentrations for neutral and charged guar i...