We demonstrate several examples of driving and steering of colloids when dispersed in nematic liquid crystals. The driving mechanism is based on the principle of nonlinear electrophoresis which is mediated by the asymmetry in the structure of the defects that the inclusions generate in the host elastic matrix. The steering mechanism originates in the photoactivation of the anchoring conditions of the nematic liquid crystal on one of the enclosing plates. As experimental realizations we first review a scenario of water microdroplets being phoretically transported for cargo release and chemical reaction. Steering is illustrated in terms of the reconfigurable assembly of colloidal particles, either in the form of asters or rotating-mills, commanded by predesigned patterns of illumination.
We study the electrophoretic flow of suspensions of charged colloids with a mesoscopic method that allows to model generic experimental conditions. We show that for highly charged colloids their electrophoretic mobility increases significantly and displays a mobility maximum on increasing the colloidal charge for all salt concentrations. The electrophoretic mobility of highly charged colloids is also enhanced significantly when ion advection is dominant, leading to a strong heterogeneity in the local electrophoretic response especially at low salt concentration, when ion diffuse layers overlap…
We propose a numerical method to simulate electrohydrodynamic phenomena in charged colloidal dispersions. This method enables us to compute the time evolutions of colloidal particles, ions, and host fluids simultaneously by solving Newton, advection-diffusion, and Navier--Stokes equations so that the electrohydrodynamic couplings can be fully taken into account. The electrophoretic mobilities of charged spherical particles are calculated in several situations. The comparisons with approximation theories show quantitative agreements for dilute dispersions without any empirical parameters, howev…
We analyze theoretically the dynamics of a single colloidal particle in an externally applied electric field. The thermal motions of microions lead to an anisotropic, nonequilibrium source of noise, pro- portional to the field, in the effective Langevin equation for the colloid. The fluctuation-dissipation ratio depends strongly on frequency, and the colloid if displaced from its steady-state position relaxes with a velocity not proportional to the gradient of the logarithm of the steady-state probability.
In this work we develop the first theory to model self assembling mixtures of single patch colloids and colloids with spherically symmetric attractions. In the development of the theory we restrict the interactions such that there are short ranged attractions between patchy and spherically symmetric colloids, but patchy colloids do not attract patchy colloids and spherically symmetric colloids do not attract spherically symmetric colloids. This results in the temperature, density and composition dependent reversible self assembly of the mixture into colloidal star molecules. This type of mixtu…
Electrophoresis is a motion of charged dispersed particles relative to a fluid in a uniform electric field. The effect is widely used to separate macromolecules, to assemble colloidal structures, to transport particles in nano- and micro-fluidic devices and displays. Typically, the fluid is isotropic (for example, water) and the electrophoretic velocity is linearly proportional to the electric field. In linear electrophoresis, only a direct current (DC) field can drive the particles. An alternate current (AC) field is more desirable because it allows one to overcome problems such as electrolys…
In this work we extend Wertheim's thermodynamic perturbation theory (TPT) to binary mixtures (species A and species B) of patchy colloids where each species has a single patch which can bond a maximum of twice (divalent). Colloids are treated as hard spheres with a directional conical asssociation site. We restrict the system such that only patches between unlike species share attractions; meaning there are AB attractions but no AA or BB attractions. The theory is derived in Wertheim's two density formalism for one site associating fluids. Since the patches are doubly bondable, associated chai…
We demonstrate a novel method to assemble and transport swarms of colloidal particles by combining liquid crystals enabled electrophoresis and photo-sensitive surface patterning. Colloidal particles are propelled in a nematic liquid crystal via application of an alternating current electric field. Swarms of particles are assembled into a rotating mill cluster, or moved as a whole along predefined paths photo-imprinted on chemically functionalized substrates. This technique represents an alternative approach to fluid based lab-on-a-chip technologies guiding the motion of large ensembles of micr…
We present experiments where anisometric colloidal microparticles dispersed in a nematic liquid crystal cell with homeotropic anchoring conditions are dynamically assembled by means of liquid-crystal-enabled electrophoresis (LCEEP) using an AC electric field perpendicular to the confining plates. A nematic host with negative dielectric anisotropy leads to a driving force parallel to the cell plates. We take advantage of the resulting gliding anchoring conditions and the degeneracy in the direction of particle motion to design reconfigurable trajectories using a photosensitive anchoring layer (…
In this paper we extend our previous theory [B. D. Marshall and W.G. Chapman, J. Chem. Phys. 139, 104904 (2013)] for mixtures of single patch colloids (p colloids) and colloids with spherically symmetric attractions (s colloids) to the case that the p colloids can have multiple patches. The theory is then applied to the case of a binary mixture of bi-functional p colloids which have an A and B type patch and s colloids which are not attracted to other s colloids and are attracted to only patch A on the p colloids. This mixture reversibly self assembles into both colloidal star molecules, where…
Concentrated solutions of monoclonal antibodies have attracted considerable attention due to their importance in pharmaceutical formulations, yet their tendency to aggregate and the resulting high solution viscosity has posed considerable problems. It remains a very difficult task to understand and predict the phase behavior and stability of such solutions. Here we present a systematic study of the concentration dependence of the structural and dynamic properties of monoclonal antibodies using a combination of different scattering methods and microrheological experiments. To interpret these da…
Many fascinating phenomena such as large-scale collective flows, enhanced fluid mixing and pattern formation have been observed in so-called active fluids, which are composed of particles that can absorb energy and dissipate it into the fluid medium. In order to investigate the role of hydrodynamic interactions in the collective behavior of an active fluid, we choose a model system: paramagnetic particles submerged in water and activated by an oscillating magnetic field. The magnetic field induces magnetic attractions among the paramagnetic particles, activating the particles, and injecting en…
In the Nernst-Planck equations in two or more dimensions, a non-Faradaic electric current can arise as a consequence of connecting patches with different liquid junction potentials. Whereas this current vanishes for binary electrolytes or one-dimensional problems, it is in general non-vanishing for example in crossed salt gradients. For a suspended colloidal particle, electrophoresis in the corresponding electrostatic potential gradient is generally vectorially misaligned with chemiphoresis in the concentration gradients, and diffusiophoresis (via electrophoresis) can occur in regions where th…
Different phoretic driving mechanisms have been proposed for the transport of solid or liquid microscopic inclusions in integrated chemical processes. However, the ability to reversibly address both the flow path, rate, and local reactant concentration has not yet been realized. Here we show that a substrate chemically modified with photosensitive self-assembled monolayers allows to directly command the assembly and transport of large ensembles of micron-size particles and drops dispersed in a thin layer of anisotropic fluid. Our strategy separates particle driving, realized via AC electrophor…
Depletion interactions arise from entropic forces, and their ability to induce aggregation and even ordering of colloidal particles through self-assembly is well established, especially for spherical colloids. We vary the size and concentration of penetrable hard sphere depletants in a system of cuboctahedra, and we show how depletion changes the preferential facet alignment of the colloids and thereby selects different crystal structures. Moreover, we explain the cuboctahedra phase behavior using perturbative free energy calculations. We find that cuboctahedra can form a stable simple cubic p…
We assemble charged colloidal spheres at deliberately chosen locations on a charged unstructured glass substrate utilizing ion exchange based electro-osmotic micro-pumps. Using microscopy, a simple scaling theory and Brownian Dynamics simulations, we systematically explore the control parameters of crystal assembly and the mechanisms through which they depend on the experimental boundary conditions. We demonstrate that crystal quality depends crucially on the assembly distance of the colloids. This is understood as resulting from the competition between inward transport by the electro-osmotic …
We propose and demonstrate a method to achieve large effective Soret coefficient in colloids by suitably mixing two different particles, e.g., silica beads and Fe3O4 nanoparticles. It is shown that the thermophoretic motion of Fe3O4 nanoparticles out of the heating region results in a large nonequlibrium depletion force for silica beads. Consequently, silica beads are driven quickly to the heating region, forming a three-dimensional crystal with few defects and dislocations. The binding of silica beads is so tight that a colloidal photonic crystal can be achieved after the complete evaporation…
Colloidal particles in a liquid crystal (LC) behave very differently from their counterparts in isotropic fluids. Elastic nature of the orientational order and surface anchoring of the director cause long-range anisotropic interactions and lead to the phenomenon of levitation. The LC environment enables new mechanisms of particle transport that are reviewed in this work. Among them the motion of particles caused by gradients of the director, and effects in the electric field: backflow powered by director reorientations, dielectrophoresis in LC with varying dielectric permittivity and LC-enable…
The self-assembly of colloidal diamond (CD) crystals is considered as one of the most coveted goals of nanotechnology, both from the technological and fundamental points of view. For applications, colloidal diamond is a photonic crystal which can open new possibilities of manipulating light for information processing. From a fundamental point of view, its unique symmetry exacerbates a series of problems that are commonly faced during the self-assembly of target structures, such as the presence of kinetic traps and the formation of crystalline defects and alternative structures (polymorphs). He…
DNA-coated colloids can self-assemble into an incredible diversity of crystal structures, but applications of this technology are limited by poor understanding and control over the dynamical crystallization pathways. To address this challenge, we use microfluidics to quantify the self-assembly dynamics of DNA-programmed colloidal crystals, from thermally-activated nucleation through reaction-limited and diffusion-limited phases of crystal growth. Our detailed measurements of the temperature and concentration dependence of the kinetics at all stages along the crystallization pathway provide a s…
Functionalizing colloids with reactive DNA linkers is a versatile way of programming self-assembly. DNA selectivity provides direct control over colloid-colloid interactions allowing the engineering of structures such as complex crystals or gels. However, self-assembly of localized and finite structures remains an open problem with many potential applications. In this work, we present a system in which functionalized surfaces initiate a cascade reaction between linkers leading to self-assembly of crystals with a controllable number of layers. Specifically, we consider colloidal particles funct…
