Modeling Equilibrium Clusters in Lysozyme Solutions

We present a combined experimental and numerical study of the equilibrium cluster formation in globular protein solutions under no-added salt conditions. We show that a cluster phase emerges as a result of a competition between a long-range screened Coulomb repulsion and a short-range attraction. A simple effective potential, in which only depth and width of the attractive part of the potential are optimized, accounts in a remarkable way for the wavevector dependence of the X-ray scattering structure factor.Comment: 4 pages, 4 figure

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 proteindense 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

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

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

Brownian dynamics of colloidal microspheres with tunable elastic properties from soft to hard

We study the Brownian thermal motion of a colloidal model system made by emulsifying hot liquid α-eicosene wax into an aqueous surfactant solution of sodium dodecyl sulfate (SDS). When this waxy oil-in-water emulsion is cooled below α- eicosene's melting point of Tc ≃ 25 °C, the microscale emulsion droplets solidify, effectively yielding a dispersed particulate system. So, the interiors of these wax droplets can be tuned from a viscous liquid to an elastic solid through very modest changes in absolute temperature. Using the multiple light scattering technique of diffusing wave spectroscopy (DWS), which is very sensitive to small-scale motion and shape fluctuations of dispersed colloidal objects, we show that the thermal fluctuations of the interfaces of these liquid droplets at higher temperature, seen in the DWS intensity–intensity correlation function at early times, effectively disappear when these droplets solidify at lower temperature. Thus, we show that the early-time behavior of this DWS correlation function can be used to probe mechanical properties of viscoelastic soft materials dispersed as droplets

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

Soft Nanotechnology – from Colloid Physics to Nanostructured Functional Materials

We demonstrate how we can tune the size, shape, surface functionality and properties of nanoparticles and use them as ideal model systems for fundamental investigations as well as for materials applications. In particular we describe ways to create functionalized core-shell particles with various degree of anisotropy and interesting magnetic properties. We show how we can use these particles in order to study the equilibrium and non-equilibrium phase behavior of colloidal suspensions with different interaction potentials and summarize our current understanding of the phenomenon of dynamical arrest, i.e. gel and glass formation. While different nanoparticles are vital for fundamental studies of various aspects of soft condensed matter, they also offer fascinating possibilities in materials science. We will demonstrate this with the example of nanocomposites made through an in situ polymerization reaction

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 (TPT) and the Derjaguin-Landau-Verwey-Overbeek (DLVO) 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.Comment: Manuscript accepted for publication in The Journal of Chemical Physic