Echo speckle imaging of dynamic processes in soft materials.

We present a laser-speckle imaging technique, termed Echo speckle imaging (ESI), that quantifies the local dynamics in biological tissue and soft materials with a noise level around or below 10% of the measured signal without affecting the spatial resolution. We achieve this through an unconventional speckle beam illumination that creates changing, statistically independent illumination conditions and substantially increases the measurement accuracy. Control experiments for dynamically homogeneous and heterogeneous soft materials and tissue phantoms illustrate the performance of the method. We show that this approach enables us to precision-monitor purely dynamic heterogeneities in turbid soft media with a lateral resolution of 100 µm and better.

Structure of marginally jammed polydisperse packings of frictionless spheres.

We model the packing structure of a marginally jammed bulk ensemble of polydisperse spheres. To this end we expand on the granocentric model [Clusel et al., Nature (London) 460, 611 (2009)], explicitly taking into account rattlers. This leads to a relationship between the characteristic parameters of the packing, such as the mean number of neighbors and the fraction of rattlers, and the radial distribution function g(r). We find excellent agreement between the model predictions for g(r) and packing simulations, as well as experiments on jammed emulsion droplets. The observed quantitative agreement opens the path towards a full structural characterization of jammed particle systems for imaging and scattering experiments.

The jamming elasticity of emulsions stabilized by ionic surfactants.

Oil-in-water emulsions composed of colloidal-scale droplets are often stabilized using ionic surfactants that provide a repulsive interaction between neighboring droplet interfaces, thereby inhibiting coalescence. If the droplet volume fraction is raised rapidly by applying an osmotic pressure, the droplets remain disordered, undergo an ergodic-nonergodic transition, and jam. If the applied osmotic pressure approaches the Laplace pressure of the droplets, then the jammed droplets also deform. Because solid friction and entanglements cannot play a role, as they might with solid particulate or microgel dispersions, the shear mechanical response of monodisperse emulsions can provide critical insight into the interplay of entropic, electrostatic, and interfacial forces. Here, we introduce a model that can be used to predict the plateau storage modulus and yield stress of a uniform charge-stabilized emulsion accurately if the droplet radius, interfacial tension, surface potential, Debye screening length, and droplet volume fraction are known.

Accounting for inertia effects to access the high-frequency microrheology of viscoelastic fluids.

We study the Brownian motion of microbeads immersed in water and in a viscoelastic wormlike micelles solution by optical trapping interferometry and diffusing wave spectroscopy. Through the mean-square displacement obtained from both techniques, we deduce the mechanical properties of the fluids at high frequencies by explicitly accounting for inertia effects of the particle and the surrounding fluid at short time scales. For wormlike micelle solutions, we recover the 3/4 scaling exponent for the loss modulus over two decades in frequency as predicted by the theory for semiflexible polymers.

Effect of glycerol and dimethyl sulfoxide on the phase behavior of lysozyme: theory and experiments.

Salt, glycerol, and dimethyl sulfoxide (DMSO) are used to modify the properties of protein solutions. We experimentally determined the effect of these additives on the phase behavior of lysozyme solutions. Upon the addition of glycerol and DMSO, the fluid-solid transition and the gas-liquid coexistence curve (binodal) shift to lower temperatures and the gap between them increases. The experimentally observed trends are consistent with our theoretical predictions based on the thermodynamic perturbation theory and the Derjaguin-Landau-Verwey-Overbeek model for the lysozyme-lysozyme pair interactions. The values of the parameters describing the interactions, namely the refractive indices, dielectric constants, Hamaker constant and cut-off length, are extracted from literature or are experimentally determined by independent experiments, including static light scattering, to determine the second virial coefficient. We observe that both, glycerol and DMSO, render the potential more repulsive, while sodium chloride reduces the repulsion.

Cluster-driven dynamical arrest in concentrated lysozyme solutions.

We present a detailed experimental and numerical study of the structural and dynamical properties of salt-free lysozyme solutions. In particular, by combining small-angle X-ray scattering (SAXS) data with neutron spin echo (NSE) and rheology experiments, we are able to identify that an arrest transition takes place at intermediate densities, driven by the slowing down of the cluster motion. Using an effective pair potential among proteins, based on the combination of short-range attraction and long-range repulsion, we account remarkably well for the peculiar volume fraction dependence of the effective structure factor measured by SAXS. We show that a transition from a monomer to a cluster-dominated fluid happens at volume fractions larger than ϕ ≳ 0.05 where the close agreement between NSE measurements and Brownian dynamics simulations confirms the transient nature of the clusters. Clusters even stay transient above the geometric percolation found in simulation at ϕ > 0.15, though NSE reveals a cluster lifetime that becomes increasingly large and indicates a divergence of the diffusivity at ϕ ≃ 0.26. Macroscopic measurements of the viscosity confirm this transition where the long-lived-nature of the clusters is at the origin of the simultaneous dynamical arrest at all length scales.

Interplay between spinodal decomposition and glass formation in proteins exhibiting short-range attractions.

We investigate the competition between spinodal decomposition and dynamical arrest using aqueous solutions of the globular protein lysozyme as a model system for colloids with short-range attractions. We show that quenches below a temperature Ta lead to gel formation as a result of a local arrest of the protein-dense phase during spinodal decomposition. The rheological properties of these gels allow us to use centrifugation experiments to determine the local densities of both phases and to precisely locate the gel boundary and the attractive glass line close to and within the unstable region of the phase diagram.

A small-angle scattering study on equilibrium clusters in lysozyme solutions.

We use small-angle scattering experiments to investigate the structural properties of aqueous lysozyme solutions under conditions where the existence of equilibrium clusters has recently been demonstrated (Nature 2004, 432, 492). We also discuss the possible emergence of a low angle scattering contribution, which recently attracted interest due to its appearance in solutions of various proteins. We demonstrate that in lysozyme solutions under our experimental conditions such rising low q intensities can only be observed under special circumstances and can thus not be attributed to the existence of a universal long-range attraction. We then focus on the structural properties of the equilibrium clusters as a function of protein concentration, temperature, and ionic strength. We show that the experimental structure factors obtained from the scattering measurements exhibit the typical cluster-cluster peak q(c) reflecting the mean distance between charged clusters as well as a monomer-monomer peak q(m), which represents the nearest neighbor shell of monomers within a single cluster. The underlying principle for the formation of these structures is the coexistence of two opposing forces, a short-range attraction and a long-range repulsion due to residual charges. We can quantitatively analyze our scattering data by applying a simple equilibrium cluster model and calculate an average cluster aggregation number, N(c). The thus obtained cluster aggregation number increases linearly with volume fraction. We also observe an increasing N(c) as temperature decreases and as the screening of residual charges increases. We point out the importance of the existence of equilibrium clusters and the universality of this phenomenon for self-assembling processes observed in nature. Finally, we discuss the limitations of our simple globular cluster model in view of recent findings from computer simulations.

Equilibrium cluster formation in concentrated protein solutions and colloids.

Controlling interparticle interactions, aggregation and cluster formation is of central importance in a number of areas, ranging from cluster formation in various disease processes to protein crystallography and the production of photonic crystals. Recent developments in the description of the interaction of colloidal particles with short-range attractive potentials have led to interesting findings including metastable liquid-liquid phase separation and the formation of dynamically arrested states (such as the existence of attractive and repulsive glasses, and transient gels). The emerging glass paradigm has been successfully applied to complex soft-matter systems, such as colloid-polymer systems and concentrated protein solutions. However, intriguing problems like the frequent occurrence of cluster phases remain. Here we report small-angle scattering and confocal microscopy investigations of two model systems: protein solutions and colloid-polymer mixtures. We demonstrate that in both systems, a combination of short-range attraction and long-range repulsion results in the formation of small equilibrium clusters. We discuss the relevance of this finding for nucleation processes during protein crystallization, protein or DNA self-assembly and the previously observed formation of cluster and gel phases in colloidal suspensions.