Active Colloids Research Articles

Helical and oscillatory microswimmer motility statistics from differential dynamic microscopy

The experimental characterisation of the swimming statistics of populations of micro-organisms or artificially propelled particles is essential for understanding the physics of active systems and their exploitation. Here, we construct a theoretical framework to extract information on the three-dimensional motion of micro-swimmers from the intermediate scattering function (ISF) obtained from differential dynamic microscopy (DDM). We derive theoretical expressions for the ISF of helical and oscillatory breaststroke swimmers, and test the theoretical framework by applying it to video sequences generated from simulated swimmers with precisely-controlled dynamics. We then discuss how our theory can be applied to the experimental study of helical swimmers, such as active Janus colloids or suspensions of motile microalgae. In particular, we show how fitting DDM data to a simple, non-helical ISF model can be used to derive three-dimensional helical motility parameters, which can therefore be obtained without specialised 3D microscopy equipment. Finally, we discus how our results aid the study of active matter and describe applications of biological and ecological importance.

Active Janus colloids at chemically structured surfaces.

If catalytically active Janus particles are dispersed in certain liquid solutions, they can create a gradient in the chemical composition of this solution along their surfaces, as well as along any nearby confining surfaces. This gradient drives self-propulsion via a self-phoretic mechanism, while the compositional gradient along a wall gives rise to chemiosmosis, which additionally contributes to self-motility. In this study, we analyze theoretically the dynamics of an active colloid near chemically patterned walls. We use a point-particle approximation combined with a multipole expansion in order to discuss the effects of pattern geometry and chemical contrast on the particle trajectories. In particular, we consider planar walls patterned with chemical steps and stripes. We investigate in detail the changes in the topology of the corresponding phase portraits upon varying the chemical contrast and the stripe width.

Rapid and Quantitative Determination of Sildenafil in Cocktail Based on Surface Enhanced Raman Spectroscopy.

Sildenafil (SD) and its related compounds are the most common adulterants found in herbal preparations used as sexual enhancer or man’s virility products. However, the abuse of SD threatens human health such as through headache, back pain, rhinitis, etc. Therefore, it is important to accurately detect the presence of SD in alcoholic beverages. In this study, the Opto Trace Raman 202 (OTR 202) was used as a surface-enhanced Raman spectroscopy (SERS) active colloids to detect SD. The results demonstrated that the limit of detection (LOD) of SD was found to be as low as 0.1 mg/L. Moreover, 1235, 1401, 1530, and 1584 cm−1 could be qualitatively determined as SD characteristic peaks. In a practical application, SD in cocktail could be easily detected using SERS based on OTR 202. Also, there was a good linear correlation between the intensity of Raman peaks at 1235, 1401, 1530, and 1584 cm−1 and the logarithm of SD concentration in cocktail was in the range of 0.1–10 mg/L (0.9822 < R2 < 0.9860). The relative standard deviation (RSD) was less than 12.7% and the recovery ranged from 93.0%–105.8%. Moreover, the original 500–1700 cm−1 SERS spectra were pretreated and the partial least squares (PLS) was applied to establish the prediction model between SERS spectra and SD content in cocktail and the highest determination coefficient (Rp2) reached 0.9856. In summary, the SD in cocktail could be rapidly and quantitatively determined by SERS, which was beneficial to provide a rapid and accurate scheme for the detection of SD in alcoholic beverages.

Gold Nanoparticles for Qualitative Detection of Deltamethrin and Carbofuran Residues in Soil by Surface Enhanced Raman Scattering (SERS).

The residues of deltamethrin (DM) and carbofuran (CBF) in soil is becoming an intractable problem causing soil hardening and environmental pollution. This paper reports a very simple method via improved reduction of chloroauric acid by the trisodium citrate method for fabricating gold nanoparticles (AuNPs), which were used as a surface enhanced Raman scattering (SERS) active colloids with the advantages of ultrasensitivity, reproducibility and chemical stability. The results demonstrated that the limits of detection (LODs) of the DM and CBF were found to be as low as 0.01 mg/L. The SERS intensity showed a good linear relationship with DM (R2 = 0.9908) and CBF (R2 = 0.9801) concentration from 0.01 to 10 mg/L. In a practical application, DM and CBF residues in soil were easily detected by SERS with the flexible AuNPs colloids, and the LODs of DM and CBF were found to be as low as 0.056 mg/kg and 0.053 mg/kg, respectively. Moreover, DM in soil could be qualitatively detected by the characteristic peaks at 560 and 1000 cm−1, and CBF in soil could be qualitatively detected by the characteristic peaks at 1000 and 1299 cm−1. The determination coefficient (R2p) for DM and CBF reached 0.9176 and 0.8517 in partial least squares (PLS) model. Overall, it is believed that the prepared AuNPs can provide technical support for the accurate detection of pesticide residues in soil by SERS technique.

Self-Assembled Phage-Based Colloids for High Localized Enzymatic Activity.

Catalytically active colloids are model systems for chemical motors and active matter. It is desirable to replace the inorganic catalysts and the toxic fuels that are often used with biocompatible enzymatic reactions. However, compared to inorganic catalysts, enzyme-coated colloids tend to exhibit less activity. Here, we show that the self-assembly of genetically engineered M13 bacteriophages that bind enzymes to magnetic beads ensures high and localized enzymatic activity. These phage-decorated colloids provide a proteinaceous environment for directed enzyme immobilization. The magnetic properties of the colloidal carrier particle permit repeated enzyme recovery from a reaction solution, while the enzymatic activity is retained. Moreover, localizing the phage-based construct with a magnetic field in a microcontainer allows the enzyme-phage-colloids to function as an enzymatic micropump, where the enzymatic reaction generates a fluid flow. This system shows the fastest fluid flow reported to date by a biocompatible enzymatic micropump. In addition, it is functional in complex media including blood, where the enzyme-driven micropump can be powered at the physiological blood-urea concentrations.

Transition from Linear to Circular Motion in Active Spherical-Cap Colloids.

Nonspherical self-propelling colloidal particles offer many possibilities for creating a variety of active motions. In this work, we report on the transition from linear to circular motion of active spherical-cap particles near a substrate. Self-propulsion is induced by self-diffusiophoresis by catalytic decomposition of hydrogen peroxide (H2O2) on one side of the particle. Asymmetric distribution of reaction products combined with the asymmetric shape of the particle gives rise to two types of motions depending upon the relative orientation of the particle with respect to the underlying substrate. At a low concentration of H2O2, linear active motion is observed, whereas increasing the H2O2 concentration leads to persistent circular motion. However, the speed of self-propulsion is nearly independent of the size of the particle. The study demonstrates the use of nonspherical particles to create linear and circular motion by varying the fuel concentration.

Which interactions dominate in active colloids?

Despite mounting evidence that the same gradients, which active colloids use for swimming, induce important cross-interactions (phoretic interactions), they are still ignored in most many-body descriptions, perhaps to avoid complexity and a zoo of unknown parameters. Here we derive a simple model, which reduces phoretic far-field interactions to a pair-interaction whose strength is mainly controlled by one genuine parameter (swimming speed). The model suggests that phoretic interactions are generically important for autophoretic colloids (unless effective screening of the phoretic fields is strong) and should dominate over hydrodynamic interactions for the typical case of half-coating and moderately nonuniform surface mobilities. Unlike standard minimal models, but in accordance with canonical experiments, our model generically predicts dynamic clustering in active colloids at a low density. This suggests that dynamic clustering can emerge from the interplay of screened phoretic attractions and active diffusion.

Engineering the Dynamics of Active Colloids by Targeted Design of Metal–Semiconductor Heterojunctions

AbstractSelf‐propelled colloids are primed to become scaled up, nano‐ and microscale inorganic analogues of molecular motors and machines. In order to advance toward the ambitious goal of employing such active particles to form genuine man‐made small scale machinery, a significantly diversified library of particle types, capable of a wide range of motive behaviors, must be available. Here, it is shown that the dynamics of photoactivated, self‐phoretic particles can be engineered by targeted design of metal–semiconductor heterojunctions. This effect is demonstrated with three different microswimmers consisting of an elongated semiconducting tail made from anatase titanium dioxide; all three of which would otherwise be identical absent vapor‐deposited coatings of gold at different locations on the tails. The specific location of the heterojunction determines the swimming behavior for each type. Although here only one shape and material combination is focused upon, engineering active particles with site‐specific metal–semiconductor heterojunctions is a general technique for achieving desired kinematic behavior in active colloidal matter.

Dynamic Coupling at Low Reynolds Number.

Collective and emergent behaviors of active colloids provide useful insights into the statistical physics of out-of-equilibrium systems. Colloidal suspensions containing microscopic active swimmers have been intensively studied to understand the principles of energy transfer at low Reynolds number conditions. Studies on active enzymes and Ångström-sized organometallic catalysts have demonstrated that energy can even be transferred by molecules to their surroundings, thereby influencing the overall dynamics of the systems substantially. By monitoring the diffusion of non-reacting tracers in active solutions, it has been shown that the nature of energy transfer in systems containing different swimmers is surprisingly similar-irrespective of their size, modes of energy transduction, and propulsion strategies. This Review discusses research results obtained so far in this direction, highlighting the common features observed in the dynamic coupling of swimmers with their surroundings.

Rheological implications of embedded active matter in colloidal gels.

Colloidal gels represent an important class of soft matter, in which networks formed due to strong, short-range interactions display solid-like mechanical properties, such as a finite low-frequency elastic modulus. Here we examine the effect of embedded active colloids on the linear viscoelastic moduli of fractal cluster colloidal gels. We find that the autonomous, out-of-equilibrium dynamics of active colloids incorporated into the colloidal network decreases gel elasticity, in contrast to observed stiffening effects of myosin motors in actin networks. Fractal cluster gels are formed by the well-known mechanism of aggregating polystyrene colloids through addition of divalent electrolyte. Active Janus particles with a platinum hemisphere are created from the same polystyrene colloids and homogeneously embedded in the gels at dilute concentration at the time of aggregation. Upon addition of hydrogen peroxide - a fuel that drives the diffusiophoretic motion of the embedded Janus particles - the microdynamics and mechanical rheology change in proportion to the concentration of hydrogen peroxide and the number of active colloids. We propose a theoretical explanation of this effect in which the decrease in modulus is mediated by active motion-induced softening of the inter-particle attraction. Furthermore, we characterize the failure of the fluctuation-dissipation theorem in the active gels by identifying a discrepancy between the frequency-dependent macroscopic viscoelastic moduli and the values predicted by microrheology from measurement of the gel microdynamics. These findings support efforts to engineer gels for autonomous function by tuning the microscopic dynamics of embedded active particles. Such reconfigurable gels, with multi-state mechanical properties, could find application in materials such as paints and coatings, pharmaceuticals, self-healing materials, and soft robotics.

Hydrodynamic self-assembly of active colloids: chiral spinners and dynamic crystals.

Active colloids self-organise into a variety of collective states, ranging from highly motile "molecules" to complex 2D structures. Using large-scale simulations, we show that hydrodynamic interactions, together with a gravity-like aligning field, lead to tunable self-assembly of active colloidal spheres near a surface. The observed structures depend on the hydrodynamic characteristics: particles driven at the front, pullers, form small chiral spinners consisting of two or three particles, whereas those driven at the rear, pushers, assemble into large dynamic aggregates. The rotational motion of the puller spinners, arises from spontaneous breaking of the internal chirality. Our results show that the fluid flow mediates chiral transfer between neighbouring spinners. Finally we show that the chirality of the individual spinners controls the topology of the self-assembly in solution: homochiral samples assemble into a hexagonally symmetric 2D crystal lattice while racemic mixtures show reduced hexatic order with diffusion-like dynamics.

Phototaxis of active colloids by self-thermophoresis.

Phototaxis usually refers to the ability of a motile micoorganism to move directionally within a light gradient, which is important for microorganisms to gain energy or avoid damage. Here, we show that an active Janus particle driven by self-thermophoresis from light heating is able to exhibit significant phototactic motion by means of mesoscale dynamics simulation. Depending on the particle-fluid interactions, the active particle can move along or against the light gradient, corresponding to positive or negative phototaxis, respectively. We find that the phototaxis of the active colloid is determined by various mechanisms, including alignment (polarization) of the particle to the light gradient, orientation-dependent motility and spatially inhomogeneous motility. Our results shed light on the phototactic behavior of artificial active colloids and open up a new possibility to design photo-responsive micromachines.

Propagating density spikes in light-powered motility-ratchets.

Combining experiments and computer simulations, we use a spatially periodic and flashing light-field to direct the motion of phototactic active colloids. Here, the colloids self-organize into a density spike pattern, which resembles a shock wave and propagates over long distances, almost without dispersing. The underlying mechanism involves a synchronization of the colloids with the light-field, so that particles see the same intensity gradient each time the light-pattern is switched on, but no gradient in between (for example). This creates pulsating transport whose strength and direction can be controlled via the flashing protocol and the self-propulsion speed of the colloids. Our results might be useful for drug delivery applications and can be used to segregate active colloids by their speed.

Thermodynamic costs of dynamic function in active soft matter

Living matter combines complex structures and dissipative processes to achieve dynamic functions that rely on material organization in space and time. In this Review, we discuss recent progress in creating synthetic material systems capable of four such functions–keeping time, powering motion, building structures, and making copies. Chemical oscillators coordinate the temporal activity of material assemblies; molecular motors and active colloids convert chemical energy into mechanical forces and motions; chemical activation of self-assembling components provides temporal control over dissipative structures; information-rich nanomaterials replicate their structures in exponential fashion. These and other dynamic functions cannot be achieved at thermodynamic equilibrium but instead require flows of energy and matter to create and maintain spatiotemporal order. Such systems are captured within the framework of stochastic thermodynamics, which describes the fluctuating thermodynamic quantities of driven systems. Even far from equilibrium, these quantities obey universal relations, which establish fundamental trade-offs between the rate of energy dissipation and performance metrics such as precision, efficiency, and speed. For each function considered, we present a simple kinetic model that offers general insights that inform the design and creation of dissipative material systems capable of dynamic functions. Overall, we aim to bridge experimental efforts in active soft matter and theoretical advances from stochastic thermodynamics to inform future research on material systems inspired by living matter.

Effective squirmer models for self-phoretic chemically active spherical colloids

.Various aspects of self-motility of chemically active colloids in Newtonian fluids can be captured by simple models for their chemical activity plus a phoretic-slip hydrodynamic boundary condition on their surface. For particles of simple shapes (e.g., spheres) --as employed in many experimental studies-- which move at very low Reynolds numbers in an unbounded fluid, such models of chemically active particles effectively map onto the well studied so-called hydrodynamic squirmers (S. Michelin and E. Lauga, J. Fluid Mech. 747, 572 (2014)). Accordingly, intuitively appealing analogies of “pusher/puller/neutral” squirmers arise naturally. Within the framework of self-diffusiophoresis we illustrate the above-mentioned mapping and the corresponding flows in an unbounded fluid for a number of choices of the activity function (i.e., the spatial distribution and the type of chemical reactions across the surface of the particle). We use the central collision of two active particles as a simple, paradigmatic case for demonstrating that in the presence of other particles or boundaries the behavior of chemically active colloids may be qualitatively different, even in the far field, from the one exhibited by the corresponding “effective squirmer”, obtained from the mapping in an unbounded fluid. This emphasizes that understanding the collective behavior and the dynamics under geometrical confinement of chemically active particles necessarily requires to explicitly account for the dependence of the hydrodynamic interactions on the distribution of chemical species resulting from the activity of the particles.Graphical abstract

Effective Interactions between Chemically Active Colloids and Interfaces.

Chemically active colloids can achieve force- and torque-free motility ("self-propulsion") via the promotion, on their surface, of catalytic chemical reactions involving the surrounding solution. Such systems are valuable both from a theoretical perspective, serving as paradigms for nonequilibrium processes, as well as from an application viewpoint, according to which active colloids are envisioned to play the role of carriers ("engines") in novel lab-on-a-chip devices. The motion of such colloids is intrinsically connected with a "chemical field", i.e., the distribution near the colloid of the number densities of the various chemical species present in the solution, and with the hydrodynamic flow of the solution around the particle. In most of the envisioned applications, and in virtually all reported experimental studies, the active colloids operate under spatial confinement (e.g., within a microfluidic channel, a drop, a free-standing liquid film, etc.). In such cases, the chemical field and the hydrodynamic flow associated with an active colloid are influenced by any nearby confining surfaces, and these disturbances couple back to the particle. Thus, an effective interaction with the spatial confinement arises. Consequently, the particle is endowed with means to perceive and to respond to its environment. Understanding these effective interactions, finding the key parameters which control them, and designing particles with desired, preconfigured responses to given environments, require interdisciplinary approaches which synergistically integrate methods and knowledge from physics, chemistry, engineering, and materials science. Here we review how, via simple models of chemical activity and self-phoretic motion, progress has recently been made in understanding the basic physical principles behind the complex behaviors exhibited by active particles near interfaces. First, we consider the occurrence of "interface-bounded" steady states of chemically active colloids near simple, nonresponsive interfaces. Examples include particles "sliding" along, or "hovering" above, a hard planar wall while inducing hydrodynamic flow of the solution. These states lay the foundations for concepts like the guidance of particles by the topography of the wall. We continue to discuss responsive interfaces: a suitable chemical patterning of a planar wall allows one to bring the particles into states of motion which are spatially localized (e.g., within chemical stripes or along chemical steps). These occur due to the wall responding to the activity-induced chemical gradients by generating osmotic flows, which encode the surface-chemistry of the wall. Finally, we discuss how, via activity-induced Marangoni stresses, long-ranged effective interactions emerge from the strong hydrodynamic response of fluid interfaces. These examples highlight how in this context a desired behavior can be potentially selected by tuning suitable parameters (e.g., the phoretic mobility of the particle, or the strength of the Marangoni stress at an interface). This can be accomplished via a judicious design of the surface chemistry of the particle and of the boundary, or by the choice of the chemical reaction in solution.

Experimental Study of the Motion of Patchy Particle Swimmers Near a Wall

In this work, we demonstrate our ability to precisely tailor the surface activity of self-propelled active colloids by varying the size of the active area. The quasi two-dimensional autonomous motion of spherical patchy particle swimmers is studied in a chemical environment in the vicinity of a solid boundary. Oxidative decomposition of hydrogen peroxide into oxygen and water occurs only on a well-defined Pt-coated section of the polystyrene particle surface. The asymmetric distribution of product molecules interacting with the particle leads to the autonomous motion, which is characterized as the patch size varies from 11 to 25 to 50% of the particle surface area. The phoretic motion of patchy particle swimmers is analytically predicted by a model developed by Popescu et al. and shows good agreement with the experimentally observed velocities when the influence of the wall on the preferential rotational motion of the particles near the solid boundary is considered. The study illustrates the potential to precisely engineer the motion of particles by controlling their properties rather than depending on changes in the environment.

Sedimentation of self-propelled Janus colloids: polarization and pressure

We study experimentally—using Janus colloids—and theoretically—using Active Brownian Particles—the sedimentation of dilute active colloids. We first confirm the existence of an exponential density profile. We show experimentally the emergence of a polarized steady state outside the effective equilibrium regime, i.e. when the sedimentation speed vs is not much smaller than the propulsion speed v0. The experimental distribution of polarization is very well described by the theoretical prediction with no fitting parameter. We then discuss and compare three expressions which have been proposed to measure the pressure of sedimenting particles: the weight of particles above a given height, the flux of momentum and active impulse, and the force density measured by pressure gauges.

Artificial Chemotaxis of Self-Phoretic Active Colloids: Collective Behavior

Microorganisms use chemotaxis, regulated by internal complex chemical pathways, to swim along chemical gradients to find better living conditions. Artificial microswimmers can mimic such a strategy by a pure physical process called diffusiophoresis, where they drift and orient along the gradient in a chemical density field. Similarly, for other forms of taxis in nature such as photo- or thermotaxis the phoretic counterpart exists. In this Account, we concentrate on the chemotaxis of self-phoretic active colloids. They are driven by self-electro- and diffusiophoresis at the particle surface and thereby acquire a swimming speed. During this process, they also produce nonuniform chemical fields in their surroundings through which they interact with other colloids by translational and rotational diffusiophoresis. In combination with active motion, this gives rise to effective phoretic attraction and repulsion and thereby to diverse emergent collective behavior. A particular appealing example is dynamic clustering in dilute suspensions first reported by a group from Lyon. A subtle balance of attraction and repulsion causes very dynamic clusters, which form and resolve again. This is in stark contrast to the relatively static clusters of motility-induced phase separation at larger densities. To treat chemotaxis in active colloids confined to a plane, we formulate two Langevin equations for position and orientation, which include translational and rotational diffusiophoretic drift velocities. The colloids are chemical sinks and develop their long-range chemical profiles instantaneously. For dense packings, we include screening of the chemical fields. We present a state diagram in the two diffusiophoretic parameters governing translational, as well as rotational, drift and, thereby, explore the full range of phoretic attraction and repulsion. The identified states range from a gaslike phase over dynamic clustering states 1 and 2, which we distinguish through their cluster size distributions, to different types of collapsed states. The latter include a full chemotactic collapse for translational phoretic attraction. Turning it into an effective repulsion, with increasing strength first the collapsed cluster starts to fluctuate at the rim, then oscillates, and ultimately becomes a static collapsed cloud. We also present a state diagram without screening. Finally, we summarize how the famous Keller-Segel model derives from our Langevin equations through a multipole expansion of the full one-particle distribution function in position and orientation. The Keller-Segel model gives a continuum equation for treating chemotaxis of microorganisms on the level of their spatial density. Our theory is extensible to mixtures of active and passive particles and allows to include a dipolar correction to the chemical field resulting from the dipolar symmetry of Janus colloids.

Directional mode-locking of driven two-dimensional active magnetized colloids with periodic pinning centers

We investigate the directional mode-locking of driven two-dimensional active magnetized colloids on the substrate with periodically distributed point-like pinning centers. The active magnetized colloids are modeled as Janus particles, which interact with each other through repulsive magnetic dipole and attractive electric dipole potentials. The movements of the depinning colloidal particles are found to be locked collectively in some symmetric directions of the substrate pinning potential. As a result, there form directional mode-locking steps in the driving force direction dependence of the average velocity of colloidal particles. The deviations of some colloidal particles from the mode-locking directions are also observed clearly. Our results provide guidance for continuous separation of different kinds of active microscopic particles, including macroscopic molecule and biological cells.