Active interaction switching controls the dynamic heterogeneity of soft colloidal dispersions

We employ Reactive Dynamical Density Functional Theory R DDFT and Reactive Brownian Dynamics R BD simulations to investigate the dynamics of a suspension of active soft Gaussian colloids with binary interaction switching, i.e., a one component colloidal system in which every particle stochastically switches at predefined rates between two interaction states with different mobility. Using R DDFT we extend a theory previously developed to access the dynamics of inhomogeneous liquids [Archer et al., Phys. Rev. E Stat., Nonlinear, Soft Matter Phys., 2007, 75, 040501] to study the influence of the switching activity on the self and distinct part of the Van Hove function in bulk solution, and determine the corresponding mean squared displacement of the switching particles. Our results demonstrate that, even though the average diffusion coefficient is not affected by the switching activity, it significantly modifies the non equilibrium dynamics and diffusion coefficients of the individual particles, leading to a crossover from short to long times, with a regime for intermediate times showing anomalous diffusion. In addition, the self part of the van Hove function has a Gaussian form at short and long times, but becomes non Gaussian at intermediates ones, having a crossover between short and large displacements. The corresponding self intermediate scattering function shows the two step relaxation patters typically observed in soft materials with heterogeneous dynamics such as glasses and gels. We also introduce a phenomenological Continuous Time Random Walk CTRW theory to understand the heterogeneous diffusion of this system. R DDFT results are in excellent agreement with R BD simulations and the analytical predictions of CTRW theory, thus confirming that R DDFT constitutes a powerful method to investigate not only the structure and phase behavior, but also the dynamical properties of non equilibrium active switching colloidal suspension

Direct measurements of the effects of salt and surfactant on interaction forces between colloidal particles at water-oil interfaces

The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and of the surfactant sodium dodecylsulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of three-body interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.Comment: Submitted to Langmui

Swelling of ionic microgel particles in the presence of excluded volume interactions a density functional approach

In this work a new density functional theory framework is developed to predict the salt-concentration dependent swelling state of charged microgels and the local concentration of monovalent ions inside and outside the microgel.</p

Cosolute Partitioning in Polymer Networks Effects of Flexibility and Volume Transitions

We study the partitioning of cosolute particles in a thin film of a semi-flexible polymer network by a combination of coarse-grained (implicit-solvent) stochastic dynamics simulations and mean-field theory. We focus on a wide range of solvent qualities and cosolute-network interactions for selected polymer flexibilities. Our investigated ensemble (isothermal-isobaric) allows the network to undergo a volume transition from extended to collapsed state while the cosolutes can distribute in bulk and network, correspondingly. We find a rich topology of equilibrium states of the network and transitions between them, qualitatively depending on solvent quality, polymer flexibility, and cosolute-network interactions. In particular, we find a novel `cosolute-induced' collapsed state, where strongly attractive cosolutes bridge network monomers albeit the latter interact mutually repulsive. Finally, the cosolutes' global partitioning `landscape', computed as a function of solvent quality and cosolute-network interactions, exhibits very different topologies depending on polymer flexibility. The simulation results are supported by theoretical predictions obtained with a two-component mean-field approximation for the Helmholtz free energy that considers the chain elasticity and the particle interactions in terms of a virial expansion. Our findings have implications on the interpretation of transport processes and permeability in hydrogel films, as realized in filtration or macromolecular carrier systems.Comment: Macromolecules (2017