Extremely Long-Range Light-Driven Repulsion of Porous Microparticles.

The repulsive surface forces, such as electrostatic or steric, acting between particles explain why they remain well separated in aqueous electrolyte solutions and are responsible for the stability of colloidal dispersions. However, the effective range of these interactions is always well below hundreds of nanometers and typically can be controlled by advanced manipulations such as tuning the electrolyte concentration or modifying the particle surface or, in some more specific cases, via subjecting the suspension to an external electric or magnetic field. Here we employ solutions with small additives of a photosensitive ionic surfactant to investigate if a repulsive interaction of microsized particles sedimented at the solid surface can be remotely controlled simply by illuminating it with an appropriate wavelength. We show that interactions of conventional impermeable particles remain practically unaffected by light, but, in contrast, for porous particles, we observe a long-range repulsion, several orders of magnitude longer than any conceivable equilibrium surface force. This repulsion emerges due to the diffusio-osmotic flow generated near the porous particles that in this scenario are playing a role of micropumps. The diffusio-osmotic repulsion of porous particles can be used for a remote control of their two-dimensional assemblies at the solid wall, and in particular, we demonstrate that by simply using two different illumination wavelengths it is possible to reversibly switch the state of porous particle dispersion from densely packed surface aggregates to a periodic lattice of particles separated by distances on the order of tens of micrometers.

Ionic equilibria and swelling of soft permeable particles in electrolyte solutions.

We discuss osmotic equilibria between soft permeable particles, of radius R and volume charge density ρ, and bulk electrolyte solutions of inverse Debye length κ. Existing models are based on a simplified assumption of weakly charged particles. Here we derive analytical approximations for the distribution of potentials, ions and pressure in a system, suitable even when ρ is quite large. Our theory is valid not only for "large" particles (κR≫ 1), where the central part is fully screened, but also for weakly screened "small" particles (κR≤ 1) with overlapping inner diffuse layers. Besides, we present novel coarse-grained simulations to validate the analysis and illustrate the variation of potential/ion profiles in response to changes in κR and ρ. Our simulations also allow us to argue that swelling of both "large" and "small" particles is uniform, although their inner non-uniform local pressure profiles are essentially and qualitatively different. These results are directly relevant for a variety of permeable charged objects, from polymer micro- and nanogels to more rigid porous colloids.

Star polymers as unit cells for coarse-graining cross-linked networks.

Reducing the complexity of cross-linked polymer networks by preserving their main macroscale properties is key to understanding them, and a crucial issue is to relate individual properties of the polymer constituents to those of the reduced network. Here we study polymer networks in a good solvent, by considering star polymers as their unit elements, and first quantify the interaction between their centers of masses. We then reduce the complexity of a network by replacing sets of its bridged star polymers by equivalent effective soft particles with dense cores. Our coarse graining allows us to approximate complex polymer networks by much simpler ones, keeping their relevant mechanical properties, as illustrated in computer experiments.

Continuous electroosmotic sorting of particles in grooved microchannels.

We propose a novel microfluidic fractionation concept suitable for neutrally buoyant micron-sized particles. This approach takes advantage of the ability of grooved channel walls oriented at an angle to the direction of an external electric field to generate a transverse electroosmotic flow. Using computer simulations, we first demonstrate that the velocity of this secondary transverse flow depends on the distance from the wall, so neutrally buoyant particles, depending on their size and initial location, will experience different lateral displacements. We then optimize the geometry and orientation of the surface texture of the channel walls to maximize the efficiency of particle fractionation. Our method is illustrated in a full scale computer experiment where we mimic the typical microchannel with a bottom grooved wall and a source of polydisperse particles that are carried along the channel by the forward electroosmotic flow. Our simulations show that the particle dispersion can be efficiently separated by size even in a channel that is only a few texture periods long. These results can guide the design of novel microfluidic devices for efficient sorting of microparticles.

Electrophoresis of Janus particles: A molecular dynamics simulation study.

In this work, we use molecular dynamics and lattice-Boltzmann simulations to study the properties of charged Janus particles in an electric field. We show that for a relatively small net charge and a thick electrostatic diffuse layer, mobilities of Janus particles and uniformly charged colloids of the same net charge are identical. However, for higher charges and thinner diffuse layers, the Janus particles always show lower electrophoretic mobility. We also demonstrate that the Janus particles align with the electric field and the angular deviation from the field's direction is related to their dipole moment. We show that the latter is affected by the thickness of electrostatic diffuse layer and strongly correlates with the electrophoretic mobility.