Because of consuming energy to drive their motion, systems of active colloids are intrinsically out of equilibrium. In the past decade, a variety of intriguing dynamic patterns have been observed in systems of active colloids, and they offer a new platform for studying non-equilibrium physics, in which computer simulation and analytical theory have played an important role. Here we review the recent progress in understanding the dynamic assembly of active colloids by using numerical and analytical tools. We review the progress in understanding the motility induced phase separation in the past decade, followed by the discussion on the effect of shape anisotropy and hydrodynamics on the dynamic assembly of active colloids.
The assembly of colloids in nematic liquid crystals via topological defects has been extensively studied for spherical particles, and investigations of other colloid shapes have revealed a wide array of new assembly behaviors. We show, using Landau-de Gennes numerical modeling, that nematic defect configurations and colloidal assembly can be strongly influenced by fine details of colloid shape, in particular the presence of sharp edges. For cylinder, microbullet, and cube colloid geometries, we obtain the particles' equilibrium alignment directions and effective pair interaction potentials as …
Review paper. Chapter 6 in Janus Particles Synthesis, Self-Assembly, and Applications pages 108-137, Edited by Steve Granick and Shan Jiang (RCS Publishing 2012) http://www.rsc.org/Shop/books/2012/9781849734233.asp
Colloidal molecules are designed to mimic their molecular analogues through their anisotropic shape and interactions. However, current experimental realizations are missing the structural flexibility present in real molecules thereby restricting their use as model systems. We overcome this limitation by assembling reconfigurable colloidal molecules from silica particles functionalized with mobile DNA linkers in high yields. We achieve this by steering the self-assembly pathway towards the formation of finite-sized clusters by employing high number ratios of particles functionalized with comple…
Spherical microparticles dispersed in nematic liquid crystals have been extensively investigated in the past years. Here, we report experimental studies on the elastic deformation, colloidal interaction and self-assembly of hematite microcubes with homeotropic surface anchoring in a nematic liquid crystal. We demonstrate that the colloidal interaction and self-assembly of cubic colloids are orientation dependent. In a notable departure from the conventional microspheres, the microcubes stabilise diverse structures, such as bent chains, branches, kinks and closed-loops. The microcubes reorient …
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 …
In directed assembly, small building clocks are assembled into an organized structures under the influence of guiding fields. Capillary interactions provide a versatile route for structure formation. Colloids adsorbed on fluid interfaces distort the interface, which creates an associated energy field. When neighboring distortions overlap, colloids interact to minimize interfacial area. Contact line pinning, particle shape and surface chemistry play important roles in structure formation. Interface curvature acts like an external field; particles migrate and assemble in patterns dictated by cur…
In this review we discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field with a specific focus on dry active matter. We explore this phenomenology through the lens of the complexity of the colloidal building blocks. We begin by considering the behavior of isotropic spherical particles. We then discuss the case of amphiphilic and dipolar Janus particles. Finally, we show how the geometry of the colloids and/or the directionality of their interactions can be used to control the physical properties of the as…
Self-assembly of colloidal particles is poised to become a powerful composite material fabrication technique, but remains challenged by a limited control over the ensuing structures. We develop a new breed of nematic colloids that are physical analogs of a mathematical surface with boundary, interacting with the molecular alignment field without inducing defects when flat. However, made from a thin nanofoil, they can be shaped to prompt formation of self-compensating defects that drive pre-programmed elastic interactions mediated by the nematic host. To show this, we wrap the nanofoil on all t…
Designing protocols to dynamically direct the self-assembly of colloidal particles has become an important direction in soft matter physics because of the promising applications in fabrication of dynamic responsive functional materials. Here using computer simulations, we found that in the mixture of passive colloids and eccentric self-propelled active particles, when the eccentricity and self-propulsion of active particles are high enough, the eccentric active particles can push passive colloids to form a large dense dynamic cluster, and the system undergoes a novel dynamic demixing transitio…
We study the behavior of negatively charged colloids with two positively charged polar caps close to a planar patterned surface. The competition between the different anisotropic components of the particle-particle interaction patterns is able by itself to give rise to a rich assembly scenario: colloids with charged surface patterns form different crystalline domains when adsorbed to a homogeneously charged substrate. Here we consider substrates composed of alternating (negative/neutral, positive/neutral and positive/negative) parallel stripes and, by means of Monte Carlo simulations, we inves…
We study the formation of bands of colloidal particles driven by periodic external fields. Using Brownian dynamics, we determine the dependence of the band width on the strength of the particle interactions and on the intensity and periodicity of the field. We also investigate the switching (field-on) dynamics and the relaxation times as a function of the system parameters. The observed scaling relations were analyzed using a simple dynamic density-functional theory of fluids.
We report experimental and simulation studies of the structure of a monolayer of indented ("lock and key") colloids, on a planar surface. On adding a non-absorbing polymer with prescribed radius and volume fraction, depletion interactions are induced between the colloids, with controlled range and strength. For spherical particles, this leads to crystallisation, but the indented colloids crystallise less easily than spheres, in both simulation and experiment. Nevertheless, simulations show that indented colloids do form plastic (rotator) crystals. We discuss the conditions under which this occ…
A heterogeneous and dilute suspension of catalytically active colloids is studied as a non-equilibrium analogue of ionic systems, which has the remarkable feature of action-reaction symmetry breaking. Symmetrically coated colloids are found to join up to form self-assembled molecules that could be inert or have spontaneous activity in the form of net translational velocity and spin depending on their symmetry properties and their constituents. The type of activity can be adjusted by changing the surface chemistry and ambient variables that control the surface reactions and the phoretic drift.
We demonstrate a novel route of spatially organizing the colloid arrangements on the polymer-grafted substrate by use of self-consistent field and density functional theories. We find that grafting of polymers onto a substrate can effectively control spatial dispersions of deposited colloids as a result of the balance between colloidal settling force and entropically elastic force of brushes, and colloids can form unexpected ordered structures on a grafting substrate. The depositing process of colloidal particles onto the elastic "soft" substrate includes two steps: brush-mediated one-dimensio…
Colloidal particles grafted with single-stranded DNA (ssDNA) chains can self-assemble into a number of different crystalline structures, where hybridization of the ssDNA chains creates links between colloids stabilizing their structure. Depending on the geometry and the size of the particles, the grafting density of the ssDNA chains, and the length and choice of DNA sequences, a number of different crystalline structures can be fabricated. However, understanding how these factors contribute synergistically to the self-assembly process of DNA-functionalized nano- or micro-sized particles remain…
Colloidal particles can self-assemble into various ordered structures in fluid flows that have potential applications in biomedicine, materials synthesis and encryption. These dynamic processes are also of fundamental interest for probing the general principles of self-assembly in non-equilibrium conditions. Here, we report a simple microfluidic experiment, where charged colloidal particles self-assemble into flow-aligned 1D strings with regular particle spacing near a solid boundary. Using high-speed confocal microscopy, we systematically investigate the influence of flow rates, electrostatic…
Patchy colloids are promising candidates for building blocks in directed self-assembly. To be successful the surface patterns need to both be simple enough to be synthesized, while feature-rich enough to cause the colloids to self-assemble into desired structures. Achieving this is a challenge for traditional synthesis methods. Recently it has been suggested that the surface pattern themselves can be made to self-assemble. In this paper we show that a wide range of functional structures can be made to self-assemble using this approach. More generally we present a design path for hierarchical t…
Within the framework of a discrete Gaussian model, we present analytical results for the interaction induced by a lamellar phase between small embedded colloids. We consider the two limits of particles strongly adherent to the adjacent membranes and of particles impenetrable to the membranes. Our approach takes into account the finite size of the colloids, the discrete nature of the layers, and includes the Casimir-like effect of fluctuations, which is very important for dilute phases. Monte Carlo simulations of the statistical behavior of the membrane-interacting colloids account semi-quantit…
We study the assembly of colloids in a two phase water-water system that provides an environment that can sustain bacteria, providing a new structure with rich potential to confine and structure living colloids. The water-water system, formed via phase separation of a casein and xanthan mixture, forms a 3-D structure of coexisting casein-rich and xanthan-rich phases. Fluorescent labelling and confocal microscopy reveal the attachment of these living colloids, including Escherichia coli and Pseudomonas aeruginosa, at the interface between the two phases. Inert colloids also become trapped at th…
Magnetic nanoparticles in a colloidal solution self-assemble in various aligned structures, which has a profound influence on the flow behavior. However, the precise role of the microstructure in the development of the rheological response has not been reliably quantified. We investigate the self-assembly of dipolar colloids in simple shear using hybrid molecular dynamics and multi-particle collision dynamics simulations with explicit coarse-grained hydrodynamics; conduct simulated rheometric studies and apply micromechanical models to produce master curves, showing evidence of the universalit…
The rapid progress in precisely designing the surface decoration of patchy colloidal particles offers a new, yet unexperienced freedom to create building entities for larger, more complex structures in soft matter systems. However, it is extremely difficult to predict the large variety of ordered equilibrium structures that these particles are able to undergo under the variation of external parameters, such as temperature or pressure. Here we show that, by a novel combination of two theoretical tools, it is indeed possible to predict the self-assembly scenario of patchy colloidal particles: on…
Particle shape is a critical parameter that plays an important role in self-assembly, for example, in designing targeted complex structures with desired properties. In the last decades an unprecedented range of monodisperse nanoparticle systems with control over the shape of the particles have become available. In contrast, the choice of micron-sized colloidal building blocks of particles with flat facets, i.e., particles with polygonal shapes, is significantly more limited. This can be attributed to the fact that, contrary to nanoparticles, the larger colloids are significantly harder to synt…
Self-assembly is traditionally described as the process through which an initially disordered system relaxes towards an equilibrium ordered phase only driven by local interactions between its building blocks. However, This definition is too restrictive. Nature itself provides examples of amorphous, yet functional, materials assembled upon kinetically arresting the pathway towards the ground state. Kinetic self-assembly is intrinsically more flexible and reliable than its equilibrium counterpart, allowing control over the morphology of the final phase by tuning both the interactions and the the…
The role of particle shape in self-assembly processes is a double-edged sword. On the one hand, particle shape and particle elongation are often considered the most fundamental determinants of soft matter structure formation. On the other hand, structure formation is often highly sensitive to details of shape. Here we address the question of particle shape sensitivity for the self-assembly of hard pear-shaped particles, by studying two models for this system: a) the pear hard Gaussian overlap (PHGO) and b) hard pears of revolution (HPR) model. Hard pear-shaped particles, given by the PHGO mode…
We simulate colloids (radius $R \sim 1μ$m) trapped at the interface between a cholesteric liquid crystal and an immiscible oil, at which the helical order (pitch p) in the bulk conflicts with the orientation induced at the interface, stabilizing an ordered array of disclinations. For weak anchoring strength W of the director field at the colloidal surface, this creates a template, favoring particle positions eitheron top of or midway between defect lines, depending on $α= R/p$. For small $α$, optical microscopy experiments confirm this picture, but for larger $α$ no templating is seen. This ma…
Using extensive Monte Carlo (MC) simulations of colloids immersed in a nematic liquid crystal we compute an effective interaction potential via the local nematic director field and its associated order parameter. The effective potential consists of a local Landau-de Gennes (LdG) and a Frank elastic contribution. Molecular expressions for the LdG expansion coefficients are obtained via classical density functional theory (DFT). The DFT result for the LdG parameter $A$ is improved by locating the phase transition through finite-size scaling theory. We consider effective interactions between a pa…
A new theory is developed to describe the equilibrium adsorption and self-assembly of patchy colloids in microchannels. The adsorption theory is developed in classical density functional theory, with the adsorbed phase and fluid phase modeled using thermodynamic perturbation theory. In this work we propose that the introduction of patches on the colloids greatly enhances the temperature dependent and reversible adsorption of colloids in microchannels. It is shown how bulk fluid density, patch size, temperature and channel diameter can be manipulated to achieve the adsorption and self-assembly …
Catalytically active colloids maintain non-equilibrium conditions in which they produce and deplete chemicals and hence effectively act as sources and sinks of molecules. While individual colloids that are symmetrically coated do not exhibit any form of dynamical activity, the concentration fields resulting from their chemical activity decay as $1/r$ and produce gradients that attract or repel other colloids depending on their surface chemistry and ambient variables. This results in a non-equilibrium analogue of ionic systems, but with the remarkable novel feature of action-reaction symmetry b…
We study the inverse problem of tuning interaction parameters between charged colloidal particles interacting with a hard-core repulsive Yukawa potential, so that they assemble into specified crystal structures. Here, we target the body-centered-cubic (bcc) structure which is only stable in a small region in the phase diagram of charged colloids and is, therefore, challenging to find. In order to achieve this goal, we use the statistical fluctuations in the bond orientational order parameters to tune the interaction parameters for the bcc structure, while initializing the system in the fluid p…
We exploit the long-ranged elastic fields inherent to confined nematic liquid crystals to assemble colloidal particles trapped at the liquid crystal interface into reconfigurable structures with complex symmetries and packings. Spherical colloids with homeotropic anchoring trapped at the interface between air and the nematic liquid crystal 5CB create quadrupolar distortions in the director field causing particles to repel and consequently form close-packed assemblies with a triangular habit. Here we report on complex, open structures organized via interactions with defects in the bulk. Specifi…
Motivated by recent experimental findings in chemical synthesis of colloidal particles, we draw an analogy between self-assembly processes occurring in biological systems (e.g. protein folding) and a new exciting possibility in the field of material science. We consider a self-assembly process whose elementary building blocks are decorated patchy colloids of various types, that spontaneously drive the system toward a unique and predetermined targeted macroscopic structure. To this aim, we discuss a simple theoretical model -- the Kern-Frenkel model -- describing a fluid of colloidal spherical …
Light-activated colloidal assembly and swarming can act as model systems to explore non-equilibrium state of matter. In this context, creating new experimental platforms to facilitate and control two-dimensional assembly of colloidal crystals are of contemporary interest. In this paper, we present an experimental study of assembly of colloidal silica microparticles in the vicinity of a single-crystalline gold microplate evanescently excited by a 532 nm laser beam. The gold microplate acts as a source of heat and establishes a thermal gradient in the system. The created optothermal potential as…
The dynamics and pair trajectory of two self-propelled colloids are reported. The autonomous motions of the colloids are due to a catalytic chemical reaction taking place asymmetrically on their surfaces that generates a concentration gradient of interactive solutes around the particles and actuate particle propulsion. We consider two spherical particles with symmetric catalytic caps extending over the local polar angles $θ^1_{cap}$ and $θ^2_{cap}$ from the centers of active sectors in an otherwise quiescent fluid. A combined analytical-numerical technique was developed to solve the coupled ma…
Grafting linkers with open ends of complementary single-stranded DNA makes a flexible tool to tune interactions between colloids,which facilitates the design of complex self-assembly structures. Recently, it has been proposed to coat colloids with mobile DNA linkers, which alleviates kinetic barriers without high-density grafting, and also allows the design of valency without patches.However, the self-assembly mechanism of this novel system is poorly understood.Using a combination of theory and simulation, we obtain phase diagrams forthe system in both two and three dimensional spaces, and fin…
We investigate the behavior of a mixture of asymmetric colloidal dumbbells and emulsion droplets by means of kinetic Monte Carlo simulations. The evaporation of the droplets and the competition between droplet-colloid attraction and colloid-colloid interactions leads to the formation of clusters built up of colloid aggregates with both closed and open structures. We find that stable packings and hence complex colloidal structures can be obtained by changing the relative size of the colloidal spheres and/or their interfacial tension with the droplets.
We report on the self-assembly of inverse patchy colloids (IPC) using Monte Carlo simulations in two-dimensions. The IPC model considered in this work corresponds to either bipolar colloids or colloids decorated with complementary DNA on their surfaces, where only patch and non-patch parts attract. The patch coverage is found to be a dominant factor in deciding equilibrium self-assembled structures. In particular, both regular square and triangular crystals are found to be stable at 0.5 patch coverage. Upon decreasing the patch coverage to 0.33, the regular square crystal is destablized; inste…
We study structural phase transition of polymer-grafted colloidal particles by Monte Carlo simulations on hard spherical particles. The interaction potential, which has a weak repulsive step outside the hard core, was validated with use of the self-consistent field calculations. With this potential, canonical Monte Carlo simulations have been carried out in two and three dimensions using the Metropolis algorithm. At low temperature and high density, we find that the particles start to self-assemble and finally align in strings. By analyzing the cluster size distribution and string length distr…
Open structures can display a number of unusual properties, including a negative Poisson's ratio, negative thermal expansion, and holographic elasticity, and have many interesting applications in engineering. However, it is a grand challenge to self-assemble open structures at the colloidal scale, where short-range interactions and low coordination number can leave them mechanically unstable. In this paper we discuss the self-assembly of open structures using triblock Janus particles, which have two large attractive patches that can form multiple bonds, separated by a band with purely hard-sph…
Extreme deformation of soft matter is central to our understanding of the effects of shock, fracture, and phase change in a variety of systems. Yet, despite, the increasing interest in this area, far-from-equilibrium behaviours of soft matter remain challenging to probe. Colloidal suspensions are often used to visualise emergent behaviours in soft matter, as they offer precise control of interparticle interactions, and ease of visualisation by optical microscopy. However, previous studies have been limited to deformations that are orders of magnitude too slow to be representative of extreme de…
Self-organization phenomena in ensembles of self-propelled particles open pathways to the synthesis of new dynamic states not accessible by traditional equilibrium processes. The challenge is to develop a set of principles that facilitate the control and manipulation of emergent active states. Here, we report that dielectric rolling colloids energized by a pulsating electric field self-organize into alternating square lattices with a lattice constant controlled by the parameters of the field. We combine experiments and simulations to examine spatiotemporal properties of the emergent collective…
We explore the self-assembly process of colloidal structures immersed in active baths. By considering low-valence particles we numerically investigate the irreversible aggregation dynamics originated by the presence of run-and-tumble swimmers. We observe the formation of long closed chains -- vesicles -- densely filled by active swimmers. On the one hand the active bath drives the self-assembly of closed colloidal structures, and on the other hand the vesicles formation fosters the self-trapping of swimmers, suggesting new ways both to build structured nanomaterials and to trap microorganisms.
In this paper, we develop a thermodynamic perturbation theory to describe the self-assembly of patchy colloids which exhibit both patch-patch attractions as well as patch / non-patch attractions. That is, patches attract other patches as well as the no patch region. In general these attractions operate on different energy scales, which allows for controlled self-assembly as well as anomalous phase behavior. As an application we apply the model to the study of liquid water.
Machines enabled the Industrial Revolution and are central to modern technological progress: A machine's parts transmit forces, motion, and energy to one another in a predetermined manner. Today's engineering frontier, building artificial micromachines that emulate the biological machinery of living organisms, requires faithful assembly and energy consumption at the microscale. Here, we demonstrate the programmable assembly of active particles into autonomous metamachines using optical templates. Metamachines, or machines made of machines, are stable, mobile and autonomous architectures, whose…
We consider depletion effects of a pear-shaped colloidal particle in a hard-sphere solvent, for two different model realisations of the pear-shaped colloidal particle. The two models are the pear hard Gaussian overlap (PHGO) particles and the hard pears of revolution (HPR). The motivation for this study is to provide a microscopic understanding for the substantially different mesoscopic self-assembly properties of these pear-shaped colloids, in dense suspensions, that have been reported in the first part of this series. This is done by determining the differing depletion attraction via MC simu…
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…
Thanks to a constant energy input, active matter can self-assemble into phases with complex architectures and functionalities such as living clusters that dynamically form, reshape and break-up, which are forbidden in equilibrium materials by the entropy maximization (or free energy minimization) principle. The challenge to control this active self-assembly has evoked widespread efforts typically hinging on engineering of the properties of individual motile constituents. Here, we provide a different route, where activity occurs as an emergent phenomenon only when individual building blocks bin…
We study the depletion-induced self-assembly of indented colloids. Using state-of-the-art Monte Carlo simulation techniques that treat the depletant particles explicitly, we demonstrate that colloids assemble by a lock-and-key mechanism, leading to colloidal polymerization. The morphology of the chains that are formed depends sensitively on the size of the colloidal indentation, with smaller values additionally permitting chain branching. In contrast to the case of spheres with attractive patches, Wertheim's thermodynamic perturbation theory fails to provide a fully quantitative description of…
We study the self-assembly of branching-chain networks and crystals in a binary colloidal system with tunable interactions. The particle positions are extracted from microscope images and order parameters are extracted by image processing and statistical analysis. With these, we construct phase diagrams with respect to particle density, ratio and interaction. In order to draw a more complete picture, we complement the experiments with computer simulations. We establish a region in the phase diagram, where bead ratios and interactions are symmetric, promoting percolated structures.
We have developed Norland Optical Adhesive (NOA) flow focusing devices, making use of the excellent solvent compatibility and surface properties of NOA to generate micron scale oil-in-water emulsions with polydispersities as low as 5%. While current work on microfluidic oil-in-water emulsification largely concerns the production of droplets with sizes on the order of 10s of micrometres, large enough that Brownian motion is negligible, our NOA devices can produce droplets with radii ranging from 2 μm to 12 μm. To demonstrate the utility of these emulsions as colloidal model systems we produce f…
Here, we describe a method for the enhanced self-assembly of triblock Janus colloids targeted to form a kagome lattice. Using computer simulations, we demonstrate that the formation of this elusive structure can be significantly improved by self-propelling or activating the colloids along the axis connecting their hydrophobic hemispheres. The process by which metastable aggregates are destabilized and transformed into the favored kagome lattice is quite general, and we argue this active approach provides a systematic pathway to improving the self-assembly of a large number of colloidal structu…
Steering Active-Colloid Assembly by Biasing Dissipation
University of Science and Technology of China（中国科学技术大学）；Rice University（莱斯大学）；Hefei National Research Center for Physical Sciences at the Microscale（合肥微尺度物质科学国家研究中心）
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…
Effective colloid-colloid interactions can be tailored through the addition of a complex cosolute. Here we investigate the case of a cosolute made by self-assembling patchy particles. Depending on the valence, these particles can form either polymer chains or branched structures. We numerically calculate the effective potential $V_{eff}$ between two colloids immersed in a suspension of reversible patchy particles, exploring a wide region of the cosolute phase diagram and the role of valence. In addition to well-known excluded volume and depletion effects, we find that, under appropriate condit…
We simulate structural phase behavior of polymer-grafted colloidal particles by molecular Monte Carlo technique. Interparticle potential, which has a finite repulsive square-step outside a rigid core of the colloid, was previously confirmed via numerical self-consistent field calculation. This model potential is purely repulsive. We simulate these model colloids in the canonical ensemble in 2 dimensions and find that these particles containing no interparticle attraction self-assemble and align in a string-like assembly, at low temperature and high density. This string-like colloidal assembly …
