Gradients in temperature, concentration or electrostatic potential cannot exert forces on a bulk fluid; they can, however, exert forces on a fluid in a microscopic boundary layer surrounding a (nano)colloidal solute, resulting in so-called phoretic flow. Here we present a simulation study of phoretic flow around a spherical colloid held fixed in a concentration gradient. We show that the resulting flow velocity depends non-monotonically on the strength of the colloid-fluid interaction. The reason for this non-monotonic dependence is that solute particles are effectively trapped in a shell around the colloid and cannot contribute to diffusio-phoresis. We also observe that the flow depends sensitively on the anisotropy of solute-colloid interaction.
We characterize the electro-phoretic motion of charged sphere suspensions in the presence of substantial electro-osmotic flow using a recently introduced small angle super-heterodyne dynamic light scattering instrument (ISASH-LDV). Operation in integral mode gives access to the particle velocity distribution over the complete cell cross-section. Obtained Doppler spectra are evaluated for electro-phoretic mobility, wall electro-osmotic mobility and particle diffusion coefficient. Simultaneous measurements of differing electro-osmotic mobilities leading to asymmetric solvent flow are demonstrate…
The influence of a fluid-fluid interface on self-phoresis of chemically active, axially symmetric, spherical colloids is analyzed. Distinct from the studies of self-phoresis for colloids trapped at fluid interfaces or in the vicinity of hard walls, here we focus on the issue of self-phoresis close to a fluid-fluid interface. In order to provide physically intuitive results highlighting the role played by the interface, the analysis is carried out for the case that the symmetry axis of the colloid is normal to the interface; moreover, thermal fluctuations are not taken into account. Similarly t…
In this article, we study numerically the dispersion of colloids in a two-dimensional cellular flow in the presence of an imposed mean salt gradient. Owing to the additional scalar, the colloids do not follow exactly the Eulerian flow field, but have a (small) extra-velocity proportional to the salt gradient, $\mathbf{v}_\mathrm{dp}=α\nabla S$, where $α$ is the phoretic constant and $S$ the salt concentration. We study the demixing of an homogenous distribution of colloids and how their long-term mean velocity $\mathbf{V_m}$ and effective diffusivity $D_\mathrm{eff}$ are influenced by the phor…
Chemotaxis of enzymes in response to gradients in the concentration of their substrate has been widely reported in recent experiments, but a basic understanding of the process is still lacking. Here, we develop a microscopic theory for chemotaxis, valid for enzymes and other small molecules. Our theory includes both non-specific interactions between enzyme and substrate, as well as complex formation through specific binding between the enzyme and the substrate. We find that two distinct mechanisms contribute to enzyme chemotaxis: a diffusiophoretic mechanism due to the non-specific interaction…
Active colloids are microscopic particles, which self-propel through viscous fluids by converting energy extracted from their environment into directed motion. We first explain how articial microswimmers move forward by generating near-surface flow fields via self-phoresis or the self-induced Marangoni effect. We then discuss generic features of the dynamics of single active colloids in bulk and in confinement, as well as in the presence of gravity, field gradients, and fluid flow. In the third part, we review the emergent collective behavior of active colloidal suspensions focussing on their …
Fluid flow along microchannels can be induced by keeping opposite walls at different temperatures, and placing elongated tilted pillars inside the channel. The driving force for this fluid motion arises from the anisotropic thermophoretic effect of the elongated pillars that generates a force parallel to the walls, and perpendicular to the temperature gradient. The force is not determined by the thermophilic or thermophobic character of the obstacle surface, but by the geometry and the thermophoretic anisotropy of the obstacle. Via mesoscale hydrodynamic simulations, we investigate the pumping…
We propose a model for the nonequilibrium enhancement of colloidal self-diffusion in an externally imposed shear flow in charged systems. The enhancement of diffusion is calculated in terms of the electrostatic, two--body interactions between the particles in the shear flow. In the high shear rate, low volume fraction limit in which our model is valid, we compare these calculations to the experiments of Qiu et al. [Phys. Rev. Lett. 61, 2554 (1988)].
It has been recently shown that a colloidal monolayer, e.g., formed at a fluid interface or by means of a suitable confining potential, exhibits anomalous collective diffusion. This is a consequence of the hydrodynamic interactions mediated by the three-dimensional (3D) ambient fluid when the particles are confined to reside on a two-dimensional (2D) manifold. We study theoretically and with numerical simulations the crossover from normal to anomalous diffusion as the particles are, in real systems, confined by a 3D external potential and thus have the possibility to fluctuate out of the 2D ma…
When a liquid film of colloidal solution consisting of particles of different sizes is dried on a substrate, the colloids often stratify, where smaller colloids are laid upon larger colloids. This phenomenon is counter intuitive because larger colloids which have smaller diffusion constant are expected to remain near the surface during the drying process, leaving the layer of larger colloids on top of smaller colloids. Here we show that the phenomenon is caused by the interaction between the colloids, and can be explained by the diffusion model which accounts for the interaction between the co…
We study the layer-to-layer diffusion in smectic-A liquid crystals of colloidal hard rods with different length-to-diameter ratios using computer simulations. The layered arrangement of the smectic phase yields a hopping-type diffusion due to the presence of permanent barriers and transient cages. Remarkably, we detect stringlike clusters composed of inter-layer rods moving cooperatively along the nematic director. Furthermore, we find that the structural relaxation in equilibrium smectic phases shows interesting similarities with that of out-of-equilibrium supercooled liquids, although there …
Colloidal spheres with a partial platinum surface coating perform auto-phoretic motion when suspended in hydrogen peroxide solution. We present a theoretical analysis of the self-propulsion velocity of these particles using a continuum multi-component, self-diffusiophoretic model. With this model as a basis, we show how the slip-layer approximation can be derived and in which limits it holds. First, we consider the differences between the full multi-component model and the slip-layer approximation. Then the slip model is used to demonstrate and explore the sensitive nature of the particle's ve…
The controlled transport of colloids in dead-end structures is a key capability that can enable a wide range of applications, such as bio-chemical analysis, drug delivery and underground oil recovery. This letter presents a new trapping mechanism that allows the fast (i.e., within a few minutes) and reversible accumulation of sub-micron particles within dead-end micro-grooves by means of parallel streams with different salinity level. For the first time, particle focusing in dead-end structures is achieved under steady-state gradients. Confocal microscopy analysis and numerical investigations …
Under partial confinement, the motion of colloidal particles is restricted to a plane but their dynamics is influenced by hydrodynamic interactions mediated by the unconfined, three--dimensional flow of the embedding fluid. We demonstrate that this dimensionality mismatch induces a characteristic divergence in the two--dimensional collective diffusion coefficient of the colloidal monolayer. This result, independent from the specific interparticle forces in the monolayer, is solely due to the kinematical constraint on the colloidal particles, and it is different from the known divergence of tra…
We have developed a microfluidic tool to measure the diffusion coefficient $D$ of solutes in an aqueous solution, by following the temporal relaxation of an initially steep concentration gradient in a microchannel. Our chip exploits multilayer soft lithography and the opening of a pneumatic microvalve to trigger the interdiffusion of pure water and the solution initially separated in the channel by the valve, the so-called free interface diffusion technique. Another microvalve at a distance from the diffusion zone closes the channel and thus suppresses convection. Using this chip, we have meas…
Enskog theory is extended for the description of the self-diffusion coefficient of patchy colloidal fluid in disordered porous media. The theory includes the contact values of fluid-fluid and fluid-matrix pair distribution functions that are modified to include the dependence from the so-called probe particle porosity, $ϕ$, in order to correctly describe the effects of trapping the fluid particles by a matrix. The proposed expressions for the modified contact values of fluid-fluid and fluid-matrix pair distribution functions include three terms. Namely, a hard sphere contribution obtained by u…
In the simplest realization of Brownian motion, a colloidal sphere moves randomly in an isotropic fluid; its mean squared displacement (MSD) grows linearly with time $\textitτ$. Brownian motion in an orientationally ordered fluid, a nematic, is anisotropic, with the MSD being larger along the axis of molecular orientation, called the director. We show that at short time scales, the anisotropic diffusion in a nematic becomes also anomalous, with the MSD growing slower (subdiffusion) and faster (superdiffusion) than $\textitτ$. The anomalous diffusion occurs at time scales that correspond to the…
Colloidal diffusiophoresis in crossed electrolyte gradients: experimental demonstration of an 'action at a distance' effect predicted by the Nernst-Planck equations
The stochastic dynamics of colloidal particles with surface activity--in the form of catalytic reaction or particle release--and self-phoretic effects is studied analytically. Three different time scales corresponding to inertial effects, solute redistribution, and rotational diffusion are identified and shown to lead to a plethora of different regimes involving inertial, propulsive, anomalous, and diffusive behaviors. For symmetric active colloids, a regime is found where the mean-squared displacement has a super-diffusive $t^{3/2}$ behavior. At the longest time scales, an effective diffusion…
We study the thermal diffusion coefficient DT of a charged colloid in a temperature gradient, and find that it is to a large extent determined by the thermoelectric response of the electrolyte solution. The thermally induced salinity gradient leads in general to a strong increase with temperature. The difference of the heat of transport of coions and counterions gives rise to a thermoelectric field that drives the colloid to the cold or to the warm, depending on the sign of its charge. Our results provide an explanation for recent experimental findings on thermophoresis in colloidal suspension…
We introduce a representative minimal model for phoretically interacting active colloids. Combining kinetic theory, linear stability analyses, and a general relation between self-propulsion and phoretic interactions in auto-diffusiophoretic and auto-thermophoretic Janus colloids collapses the parameter space to two dimensions: area fraction and Péclet number. This collapse arises when the lifetime of the self-generated phoretic fields is not too short, and leads to a universal phase diagram showing that phoretic interactions {\it generically} induce pattern formation in typical Janus colloids,…
By applying a hybrid Molecular dynamics and mesoscopic simulation technique, we study the classic convection-diffusion problem of Taylor dispersion for colloidal discs in confined flow. We carefully consider the time and length-scales of the underlying colloidal system. These are, by computational necessity, altered in the coarse-grained simulation method, but as long as this is carefully managed, the underlying physics can be correctly interpreted. We find that when the disc diameter becomes non-negligible compared to the diameter of the pipe, there are important corrections to the original T…
The dynamics of active colloids is very sensitive to the presence of boundaries and interfaces which therefore can be used to control their motion. Here we analyze the dynamics of active colloids adsorbed at a fluid-fluid interface. By using a mesoscopic numerical approach which relies on an approximated numerical solution of the Navier-Stokes equation, we show that when adsorbed at a fluid interface, an active colloid experiences a net torque even in the absence of a viscosity contrast between the two adjacent fluids. In particular, we study the dependence of this torque on the contact angle …
Combining experiments and theory, we address the dynamics of self-propelled particles in crowded environments. We first demonstrate that motile colloids cruising at constant speed through random lattices undergo a smooth transition from diffusive, to subdiffusive, to localized dynamics upon increasing the obstacle density. We then elucidate the nature of these transitions by performing extensive simulations constructed from a detailed analysis of the colloid-obstacle interactions. We evidence that repulsion at a distance and hard-core interactions both contribute to slowing down the long-time …
In this letter, we characterize experimentally the diffusiophoretic motion of colloids and lambda- DNA toward higher concentration of solutes, using microfluidic technology to build spatially- and temporally-controlled concentration gradients. We then demonstrate that segregation and spatial patterning of the particles can be achieved from temporal variations of the solute concentration profile. This segregation takes the form of a strong trapping potential, stemming from an osmotically induced rectification mechanism of the solute time-dependent variations. Depending on the spatial and tempor…
We report results from the molecular dynamics simulations of a binary colloidal mixture subjected to an external potential barrier along one of the spatial directions at low volume fraction, ϕ = 0.2. The variations in the asymmetry of the external potential barrier do not change the dynamics of the smaller particles, showing Arrhenius diffusion. However, the dynamics of the larger particles shows a crossover from sub-Arrhenius to super-Arrhenius diffusion with the asymmetry in the external potential at the low temperatures and low volume fraction. Super-Arrhenius diffusion is generally observe…
The dynamics of particles interacting by key-lock binding of attached biomolecules are studied theoretically. Experimental realizations of such systems include colloids grafted with complementary single-stranded DNA (ssDNA), and particles grafted with antibodies to cell-membrane proteins. Depending on the coverage of the functional groups, we predict two distinct regimes. In the low coverage localized regime, there is an exponential distribution of departure times. As the coverage is increased the system enters a diffusive regime resulting from the interplay of particle desorption and diffusio…
Electro- and diffusio- phoresis of particles correspond respectively to the transport of particles under electric field and solute concentration gradients. Such interfacial transport phenomena take their origin in a diffuse layer close to the particle surface, and the motion of the particle is force-free. In the case of electrophoresis, it is further expected that the stress acting on the moving particle vanishes locally as a consequence of local electroneutrality. But the argument does not apply to diffusiophoresis, which takes its origin in solute concentration gradients. In this paper we in…
Efficient mixing of colloids, particles or molecules is a central issue in many processes. It results from the complex interplay between flow deformations and molecular diffusion, which is generally assumed to control the homogenization processes. In this work we demonstrate on the contrary that despite fixed flow and self-diffusion conditions, the chaotic mixing of colloidal suspensions can be either boosted or inhibited by the sole addition of trace amount of salt as a co-mixing species. Indeed, this shows that local saline gradients can trigger a chemically-driven transport phenomenon, diff…
We study analytically the joint dispersion of Gaussian patches of salt and colloids in linear flows, and how salt gradients accelerate or delay colloid spreading by diffusiophoretic effects. Because these flows have constant gradients in space, the problem can be solved almost entirely for any set of parameters, leading to predictions of how the mixing time and the Batchelor scale are modified by diffusiophoresis. We observe that the evolution of global concentrations, defined as the inverse of the patches areas, are very similar to those obtained experimentally in chaotic advection. They are …
We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as function of a dimensionless parameter. This parameter depends on the electrostatic properties and …
The motion of active colloids is generally achieved through their anisotropy, as exemplified by Janus colloids. Recently, there was a growing interest in the propulsion of isotropic colloids, which requires some local symmetry breaking. Although several mechanisms for such propulsion were proposed, little is known about the role played by the interactions within the environment of the colloid, which can have a dramatic effect on its propulsion. Here, we propose a minimal model of an isotropic colloid in a bath of solute particles that interact with each other. These interactions lead to a spon…
Real time visualization and tracking of colloidal particles with 3D resolution is essential for probing the local structure and dynamics in complex fluids. Although tracking translational motion of spherical colloids is well-known, accessing rotational dynamics of such particles remains a great challenge. Here, we report a novel approach of using fluorescently labeled raspberry-like colloids with an optical anisotropy to concurrently track translational and rotational dynamics in 3 dimensions. The raspberry-like particles are coated by a silica layer of adjustable thickness, which allows tunin…
Using Brownian dynamics (BD) simulations we investigate the impact of shear flow on structural and dynamical properties of a system of charged colloids confined to a narrow slit pore. Our model consists of spherical microions interacting through a Derjaguin-Landau-Verwey-Overbeek (DLVO) and a soft-sphere potential. The DLVO parameters were chosen according to a system of moderately charged silica particles (with valence Z$\sim$35) in a solvent of low ionic strength. At the confinement conditions considered, the colloids form two well-pronounced layers. In the present study we investigate shear…
We study a mesoscopic model of a chemically active colloidal particle which on certain parts of its surface promotes chemical reactions in the surrounding solution. For reasons of simplicity and conceptual clarity, we focus on the case in which only electrically neutral species are present in the solution and on chemical reactions which are described by first order kinetics. Within a self-consistent approach we explicitly determine the steady state product and reactant number density fields around the colloid as functionals of the interaction potentials of the various molecular species in solu…
In the past decade, classical dynamical density functional theory (DDFT) has been developed and widely applied to the Brownian dynamics of interacting colloidal particles. One of the possible derivation routes of DDFT from the microscopic dynamics is via the Mori-Zwanzig-Forster projection operator technique with slowly varying variables such as the one-particle density. Here, we use the projection operator approach to extend DDFT into various directions: first, we generalize DDFT toward mixtures of $n$ different species of spherical colloidal particles. We show that there are in general nontr…
