Short-time dynamics of lysozyme solutions with competing short-range attraction and long-range repulsion: Experiment and theory.

Recently, atypical static features of microstructural ordering in low-salinity lysozyme protein solutions have been extensively explored experimentally and explained theoretically based on a short-range attractive plus long-range repulsive (SALR) interaction potential. However, the protein dynamics and the relationship to the atypical SALR structure remain to be demonstrated. Here, the applicability of semi-analytic theoretical methods predicting diffusion properties and viscosity in isotropic particle suspensions to low-salinity lysozyme protein solutions is tested. Using the interaction potential parameters previously obtained from static structure factor measurements, our results of Monte Carlo simulations representing seven experimental lysoyzme samples indicate that they exist either in dispersed fluid or random percolated states. The self-consistent Zerah-Hansen scheme is used to describe the static structure factor, S(q), which is the input to our calculation schemes for the short-time hydrodynamic function, H(q), and the zero-frequency viscosity η. The schemes account for hydrodynamic interactions included on an approximate level. Theoretical predictions for H(q) as a function of the wavenumber q quantitatively agree with experimental results at small protein concentrations obtained using neutron spin echo measurements. At higher concentrations, qualitative agreement is preserved although the calculated hydrodynamic functions are overestimated. We attribute the differences for higher concentrations and lower temperatures to translational-rotational diffusion coupling induced by the shape and interaction anisotropy of particles and clusters, patchiness of the lysozyme particle surfaces, and the intra-cluster dynamics, features not included in our simple globular particle model. The theoretical results for the solution viscosity, η, are in qualitative agreement with our experimental data even at higher concentrations. We demonstrate that semi-quantitative predictions of diffusion properties and viscosity of solutions of globular proteins are possible given only the equilibrium structure factor of proteins. Furthermore, we explore the effects of changing the attraction strength on H(q) and η.

Clustering and dynamics of particles in dispersions with competing interactions: theory and simulation.

Dispersions of particles with short-range attractive and long-range repulsive interactions exhibit rich equilibrium microstructures and a complex phase behavior. We present theoretical and simulation results for structural and, in particular, short-time diffusion properties of a colloidal model system with such interactions, both in the dispersed-fluid and equilibrium-cluster phase regions. The particle interactions are described by a generalized Lennard-Jones-Yukawa pair potential. For the theoretical-analytical description, we apply the hybrid Beenakker-Mazur pairwise additivity (BM-PA) scheme. The static structure factor input to this scheme is calculated self-consistently using the Zerah-Hansen integral equation theory approach. In the simulations, a hybrid simulation method is adopted, combing molecular dynamics simulations of colloids with the multiparticle collision dynamics approach for the fluid, which fully captures hydrodynamic interactions. The comparison of our theoretical and simulation results confirms the high accuracy of the BM-PA scheme for dispersed-fluid phase systems. For particle attraction strengths exceeding a critical value, our simulations yield an equilibrium cluster phase. Calculations of the mean lifetime of the appearing clusters and the comparison with the analytical prediction of the dissociation time of an isolated particle pair reveal quantitative differences pointing to the importance of many-particle hydrodynamic interactions for the cluster dynamics. The cluster lifetime in the equilibrium-cluster phase increases far stronger with increasing attraction strength than that in the dispersed-fluid phase. Moreover, significant changes in the cluster shapes are observed in the course of time. Hence, an equilibrium-cluster dispersion cannot be treated dynamically as a system of permanent rigid bodies.

Ultrafiltration of charge-stabilized dispersions at low salinity.

We present a comprehensive study of cross-flow ultrafiltration (UF) of charge-stabilized suspensions, under low-salinity conditions of electrostatically strongly repelling colloidal particles. The axially varying permeate flux, near-membrane concentration-polarization (CP) layer and osmotic pressure profiles are calculated using a macroscopic diffusion-advection boundary layer method, and are compared with filtration experiments on aqueous suspensions of charge-stabilized silica particles. The theoretical description based on the one-component macroion fluid model (OCM) accounts for the strong influence of surface-released counterions on the renormalized colloid charge and suspension osmotic compressibility, and for the influence of the colloidal hydrodynamic interactions and electric double layer repulsion on the concentration-dependent suspension viscosity η, and collective diffusion coefficient Dc. A strong electro-hydrodynamic enhancement of Dc and η, and likewise of the osmotic pressure, is predicted theoretically, as compared with their values for a hard-sphere suspension. We also point to the failure of generalized Stokes-Einstein relations describing reciprocal relations between Dc and η. According to our filtration model, Dc is of dominant influence, giving rise to an only weakly developed CP layer having practically no effect on the permeate flux. This prediction is quantitatively confirmed by our UF measurements of the permeate flux using an aqueous suspension of charged silica spheres as the feed system. The experimentally detected fouling for the largest considered transmembrane pressure values is shown not to be due to filter cake formation by crystallization or vitrification.

Elasticity of polymeric nanocolloidal particles.

Softness is an essential mechanical feature of macromolecular particles such as polymer-grafted nanocolloids, polyelectrolyte networks, cross-linked microgels as well as block copolymer and dendrimer micelles. Elasticity of individual particles directly controls their swelling, wetting, and adsorption behaviour, their aggregation and self-assembly as well as structural and rheological properties of suspensions. Here we use numerical simulations and self-consistent field theory to study the deformation behaviour of a single spherical polymer brush upon diametral compression. We observe a universal response, which is rationalised using scaling arguments and interpreted in terms of two coarse-grained models. At small and intermediate compressions the deformation can be accurately reproduced by modelling the brush as a liquid drop, whereas at large compressions the brush behaves as a soft ball. Applicable far beyond the pairwise-additive small-strain regime, the models may be used to describe microelasticity of nanocolloids in severe confinement including dense disordered and crystalline phases.

Short-time dynamics in dispersions with competing short-range attraction and long-range repulsion.

Dynamic clustering of globular Brownian particles in dispersions exhibiting competing short-range attraction and long-range repulsion (SALR) such as low-salinity protein solutions has gained a lot of interest over the past few years. While the structure of the various cluster phases has been intensely explored, little is known about the dynamics of SALR systems. We present the first systematic theoretical study of short-time diffusion and rheological transport properties of two-Yukawa potential SALR systems in the single-particle dominated dispersed-fluid phase, using semi-analytic methods where the salient hydrodynamic interactions are accounted for. We show that the dynamics has unusual features compared to reference systems with pure repulsion or attraction. Results are discussed for the hydrodynamic function characterizing short-time diffusion that reveals an intermediate-range-order (cluster) peak, self-diffusion and sedimentation coefficients, and high-frequency viscosity. As important applications, we discuss the applicability of two generalized Stokes-Einstein relations, and assess the wavenumber range required for the determination of self-diffusion in a dynamic scattering experiment.

Dynamics of suspensions of hydrodynamically structured particles: analytic theory and applications to experiments.

We present an easy-to-use analytic toolbox for the calculation of short-time transport properties of concentrated suspensions of spherical colloidal particles with internal hydrodynamic structure, and direct interactions described by a hard-core or soft Hertz pair potential. The considered dynamic properties include self-diffusion and sedimentation coefficients, the wavenumber-dependent diffusion function determined in dynamic scattering experiments, and the high-frequency shear viscosity. The toolbox is based on the hydrodynamic radius model (HRM) wherein the internal particle structure is mapped on a hydrodynamic radius parameter for unchanged direct interactions, and on an existing simulation data base for solvent-permeable and spherical annulus particles. Useful scaling relations for the diffusion function and self-diffusion coefficient, known to be valid for hard-core interaction, are shown to apply also for soft pair potentials. We further discuss extensions of the toolbox to long-time transport properties including the low-shear zero-frequency viscosity and the long-time self-diffusion coefficient. The versatility of the toolbox is demonstrated by the analysis of a previous light scattering study of suspensions of non-ionic PNiPAM microgels [Eckert et al., J. Chem. Phys., 2008, 129, 124902] in which a detailed theoretical analysis of the dynamic data was left as an open task. By the comparison with Hertz potential based calculations, we show that the experimental data are consistently and accurately described using the Verlet-Weis corrected Percus-Yevick structure factor as input, and for a solvent penetration length equal to three percent of the excluded volume radius. This small amount of solvent permeability of the microgel particles has a significant dynamic effect at larger concentrations.