Active Colloids Research Articles

Self-Generated Ions Modify the Pair Interaction and the Phase Separation of Chemically Active Colloids.

Chemically active colloids that release/consume ions are an important class of active matter, and exhibit interesting collective behaviors such as phase separation, swarming, and waves. Key to these behaviors is the pair-wise interactions mediated by the concentration gradient of self-generated ions. This interaction is often simplified as a pair-wise force decaying at 1/r2, where r is the interparticle distance. Here, we show that this simplification fails for isotropic and immotile active colloids with net ion production, such as Ag colloids in H2O2. Specifically, the production of ions on the surface of the Ag colloids increases the local ion concentration, c, and attenuates the pair-wise interaction force that scales with ∇c/c. As a result, the attractive force between an Ag colloid and its neighbor (active or passive) decays at 1/r or 1/r2 for small or large r, respectively. In a population, the attraction of a colloid by a growing cluster also scales with ∇c/c, so that medium-sized clusters grow fastest, and that the cluster coarsening slows with time. These results, supported by finite element and Brownian dynamic simulations, highlight the important role of self-generated ions in shaping the collective behavior of chemically active colloids.

Self‐organized Patterns in Non‐reciprocal Active Droplet Systems

Non‐equilibrium patterns are widespread in nature and often arise from the self‐organization of constituents through nonreciprocal chemotactic interactions. In this study, we demonstrate how active oil‐in‐water droplet mixtures with predator‐prey interactions can result in a variety of self‐organized patterns. By manipulating physical parameters, the droplet diameter ratio and number ratio, we identify distinct classes of patterns within a binary droplet system, rationalize the pattern formation, and quantify motilities. Experimental results are recapitulated in numerical simulations using a minimal computational model that solely incorporates chemotactic interactions and steric repulsion among the constituents. The time evolution of the patterns is investigated and chemically explained. We also investigate how patterns vary with differing interaction strength by altering surfactant composition. Leveraging insights from the binary droplet system, the framework is extended to a ternary droplet mixture composed of multiple chasing droplet pairs to create chemically directed hierarchical organization. Our findings demonstrate how rationalizable, self‐organized patterns can be programmed in a chemically minimal system and provide the basis for exploration of emergent organization and higher order complexity in active colloids.

Self-Organized Patterns in Non-Reciprocal Active Droplet Systems.

Non-equilibrium patterns are widespread in nature and often arise from the self-organization of constituents through nonreciprocal chemotactic interactions. In this study, we demonstrate how active oil-in-water droplet mixtures with predator-prey interactions can result in a variety of self-organized patterns. By manipulating physical parameters, the droplet diameter ratio and number ratio, we identify distinct classes of patterns within a binary droplet system, rationalize the pattern formation, and quantify motilities. Experimental results are recapitulated in numerical simulations using a minimal computational model that solely incorporates chemotactic interactions and steric repulsion among the constituents. The time evolution of the patterns is investigated and chemically explained. We also investigate how patterns vary with differing interaction strength by altering surfactant composition. Leveraging insights from the binary droplet system, the framework is extended to a ternary droplet mixture composed of multiple chasing droplet pairs to create chemically directed hierarchical organization. Our findings demonstrate how rationalizable, self-organized patterns can be programmed in a chemically minimal system and provide the basis for exploration of emergent organization and higher order complexity in active colloids.

Active string fluids and gels formed by dipolar active Brownian particles in 3D.

Self-propelled particles possessing permanent magnetic dipole moments occur naturally in magnetotactic bacteria and can be built into man-made systems such as active colloids or micro-robots. Yet, the interplay between self-propulsion and anisotropic dipole-dipole interactions on dynamic self-assembly in three dimensions (3D) remains poorly understood. We conduct Brownian dynamics simulations of active dipolar particles in 3D, focusing on the low-density regime, where dipolar hard spheres tend to form chain-like aggregates and percolated networks with increasing dipolar coupling strength. We find that strong active forces override dipolar attractions, effectively inhibiting chain-like aggregation and network formation. Conversely, activating particles with low to moderate forces results in a fluid composed of active chains and rings. At strong dipolar coupling strengths, this active fluid transitions into an active gel, consisting of a percolated network of active chains. Although the overall structure of the active gel remains interconnected, the network experiences more frequent configurational rearrangements due to the reduced bond lifetime of active dipolar particles. Consequently, particles exhibit enhanced translational and rotational diffusion within the active fluid of strings and active gels compared to their passive counterparts. We quantify the influence of activity on aggregate topology as they transition from branched structures to unconnected chains and rings. Our findings are summarized in a state diagram, delineating the impact of dipolar coupling strength and active force magnitude on the system.

Chemical Auxiliary for Photocatalytic Active Colloids.

Active colloids with the ability to self-propel and collectively organize are emerging as indispensable elements in microrobotics and soft matter physics. For chemically powered colloids, their activity is often induced by gradients of chemical species in the particle's vicinity. The direct manipulation of these gradients, however, presents a considerable challenge, thereby limiting the extent to which active colloids can be controlled. Here, we introduce a series of rationally designed molecules, denoted as chemical auxiliary (CA), that intervene with specific chemical gradients and thus unveil new capabilities for regulating the behaviors of photocatalytic active colloids. We show that CA can alter the diffusiophoretic and osmotic interactions between active colloids and their subsequent self-organization. Also, CA can tune the self-propulsion of active particles, enabling a record high propulsion speed of over 100 μm/s and endowing high salt tolerance. Furthermore, CA is instrumental in establishing dynamic, competing gradients around active particles, which signifies an in situ, noninvasive, and reversible strategy for reconfiguring between modes of colloidal activity.

Impact of nanoparticle movement on oil mobilization: Particles adsorbed at the oil–water interface versus particles dispersed in bulk fluid

Active colloid particles have been used in many fields due to their good performance in enhancing mass transport or modifying interfacial energy. Previous studies have shown that both nanoparticles adsorbed at oil–water interface and those dispersed in bulk fluid could enhance oil recovery during the oil production process. It is challenge to directly compare these results and clarify the effect of nanoparticle’s location on oil detachment from rock surface because different kinds of nanofluids were used in those work. Herein, the oil mobilization performance by nanoparticles adsorbed at oil–water interface and dispersed in the bulk phase were investigated from the pore-scale to core-scale by using one material. Two fluorescent quantum nanodots with different affinities for oil and water phases were synthesized using the same materials but with different compositions and solvents. Their locations were observed under the laser confocal microscopy. The nanoparticles adsorbed at the oil–water interface not only presented a lower interface tension, but also demonstrated a notable capability to change the wettability from oil-wet to water-wet due to its strong tendency to rock surface. The particles-laden interface can also increase the stability and shear viscosity of formed emulsions. Furthermore, it featured a larger swept area of 6.6 % in microfluidic flooding and a higher displacement efficiency of 1.7 % in the core flooding experiments. All these findings indicate that the particle-adsorbed at the oil–water interface is more favorable for enhanced oil recovery.

Accelerating and breaking adaptive nano-colloids (

Unlike conventional colloids showing random mobility because of Brownian motion, active colloids contain nanomotors that translate chemical or physical triggers into directed movement. Whereas the acceleration of such particles works well, it is difficult to decelerate them by request. Compared to the existing literature on microscaled swimmers/robots, the main question of the current paper is whether nanoscaled colloids (<100 nm) can also be actively controlled despite the stronger relevance of rotational diffusion at such dimensions. We developed nanoparticles comprising two independent mechanisms for propulsion: a chemical engine associated with a Janus-type modification of organosilica nanoparticles and physical locomotion because of a superparamagnetic core inside these particles. Both triggers can be used independently to initiate the particles' directed and anisotropic movement. The magnetic forces can be tuned, most importantly concerning the angle defining the chemical acceleration. Superposition and a boost state are adopted for a parallel alignment. However, when the magnetic field acting on the particles is turned to an antiparallel orientation, a rapid deceleration can be observed, and the colloids halt.

Direct measurement of self-diffusiophoretic force generated by active colloids of different patch coverage using optical tweezers

Hypothesis: Synthetic micro/nanomotors are gaining extensive attention for various biomedical applications (especially in drug delivery) due to their ability to mimic the motion of biological micro/nanoscale swimmers. The feasibility of these applications relies on tight control of propulsion speed, direction, and type of motion (translation, circular, etc.) along with the exerted self-propulsive force. We propose to exploit the variation of both self-propulsion speed and force of active colloids with different patch coverages (with and without supporting layer) for engineering diffusiophoretic micro/nanomotors.Experiments: The microswimmers were designed at various patch coverages (10°, 30°, and 90°) with (Ti/Pt) and without (Pt) an adhesion layer for the catalytic patch through glancing angle metal deposition (GLAD) technique. Mean-square displacement (MSD) analysis was performed to obtain the self-propulsion parameters like speed and angular speed. Using optical tweezers (OT), the self-propulsive force was measured from the force power spectral density.Findings: The findings of our experiments suggest the non-requirement of any adhesion layer preceding the catalyst deposition since the Pt 10° colloidal batch had the maximal self-propulsion speed (4.61±0.3μm/s) and force (345±57fN) for 5% w/v H2O2 fuel concentration. Moreover, the self-propulsion speed and force decreased with increasing patch size, contrary to theoretical estimates. Also, the self-propulsive force obtained from MSD is 2 to 4 times lower in magnitude than the OT based force values. We believe that the self-propelling motion of the micromotors is possibly hindered due to interactions with the surface of the quartz cuvette during the optical microscopic analysis. Further, the MSD is limited to the self-propulsive motion in two dimensions. On the other hand, OT based force measurement involve trapping the particles in the bulk of the solution entirely avoiding the particle–substrate interactions. Hence, OT based force measurements are better than the propulsion velocity based stokes drag force estimates. We believe that this study can lay the foundation in designing efficient micro/nanomotors for translational biomedical applications.

Anomalous Fluctuations in a Droplet of Chemically Active Colloids or Enzymes.

Chemically active colloids or enzymes cluster into dense droplets driven by their phoretic response to collectively generated chemical gradients. Employing Brownian dynamics simulation techniques, our study of the dynamics of such a chemically active droplet uncovers a rich variety of structures and dynamical properties, including the full range of fluidlike to solidlike behavior, and non-Gaussian positional fluctuations. Our work sheds light on the complex dynamics of the active constituents of metabolic clusters, which are the main drivers of nonequilibrium activity in living systems.

Nonreciprocal collective dynamics in a mixture of phoretic Janus colloids

A multicomponent mixture of Janus colloids with distinct catalytic coats and phoretic mobilities is a promising theoretical system to explore the collective behavior arising from nonreciprocal interactions. An active colloid produces (or consumes) chemicals, self-propels, drifts along chemical gradients, and rotates its intrinsic polarity to align with a gradient. As a result the connection from microscopics to continuum theories through coarse-graining couples densities and polarization fields in unique ways. Focusing on a binary mixture, we show that these couplings render the unpatterned reference state unstable to small perturbations through a variety of instabilities including oscillatory ones which arise on crossing an exceptional point or through a Hopf bifurcation. For fast relaxation of the polar fields, they can be eliminated in favor of the density fields to obtain a microscopic realization of the Nonreciprocal Cahn–Hilliard model for two conserved species with two distinct sources of non-reciprocity, one in the interaction coefficient and the other in the interfacial tension. Our work establishes Janus colloids as a versatile model for a bottom-up approach to both scalar and polar active mixtures.

Discovering dynamic laws from observations: The case of self-propelled, interacting colloids.

Active matter spans a wide range of time and length scales, from groups of cells and synthetic self-propelled colloids to schools of fish and flocks of birds. The theoretical framework describing these systems has shown tremendous success in finding universal phenomenology. However, further progress is often burdened by the difficulty of determining forces controlling the dynamics of individual elements within each system. Accessing this local information is pivotal for the understanding of the physics governing an ensemble of active particles and for the creation of numerical models capable of explaining the observed collective phenomena. In this work, we present ActiveNet, a machine-learning tool consisting of a graph neural network that uses the collective motion of particles to learn active and two-body forces controlling their individual dynamics. We verify our approach using numerical simulations of active Brownian particles, active particles undergoing underdamped Langevin dynamics, and chiral active Brownian particles considering different interaction potentials and values of activity. Interestingly, ActiveNet can equally learn conservative or nonconservative forces as well as torques. Moreover, ActiveNet has proven to be a useful tool to learn the stochastic contribution to the forces, enabling the estimation of the diffusion coefficients. Therefore, all coefficients of the equationof motion of Active Brownian Particles are captured. Finally, we apply ActiveNet to experiments of electrophoretic Janus particles, extracting the active and two-body forces controlling colloids' dynamics. On the one side, we have learned that the active force depends on the electric field and area fraction. On the other side, we have also discovered a dependence of the two-body interaction with the electric field that leads us to propose that the dominant force between active colloids is a screened electrostatic interaction with a constant length scale. We believe that the proposed methodological tool, ActiveNet, might open a new avenue for the study and modeling of experimental suspensions of active particles.

Chemical herding as a multiplicative factor for top-down manipulation of colloids.

Colloidal particles can create reconfigurable nanomaterials, with applications such as color-changing, self-repairing, and self-regulating materials and reconfigurable drug delivery systems. However, top-down methods for manipulating colloids are limited in the scale they can control. We consider here a new method for using chemical reactions to multiply the effects of existing top-down colloidal manipulation methods to arrange large numbers of colloids with single-particle precision, which we refer to as chemical herding. Using simulation-based methods, we show that if a set of chemically active colloids (herders) can be steered using external forces (i.e., electrophoretic, dielectrophoretic, magnetic, or optical forces), then a larger set of colloids (followers) that move in response to the chemical gradients produced by the herders can be steered using the control algorithms given in this paper. We also derive bounds that predict the maximum number of particles that can be steered in this way, and we illustrate the effectiveness of this approach using Brownian dynamics simulations. Based on the theoretical results and simulations, we conclude that chemical herding is a viable method for multiplying the effects of existing colloidal manipulation methods to create useful structures and materials.

A Conceptual Framework to Understand the Self-Assembly of Chemically Active Colloids.

Colloids that generate chemicals, or "chemically active colloids", can interact with their neighbors and generate patterns via forces arising from such chemical gradients. Examples of such assemblies of chemically active colloids are abundant in the literature, but a unified theoretical framework is needed to rationalize the scattered results. Combining experiments, theory, Brownian dynamics, and finite element simulations, we present here a conceptual framework for understanding how immotile, yet chemically active, colloids assemble. This framework is based on the principle of ionic diffusiophoresis and diffusioosmosis and predicts that a chemically active colloid interacts with its neighbors through short- and long-range interactions that can be either repulsive or attractive, depending on the relative diffusivity of the released cations and anions, and the relative zeta potential of a colloidal particle and the planar surface on which it resides. As a result, 4 types of pairwise interactions arise, leading to 4 different types of colloidal assemblies with distinct patterns. Using short-range attraction and long-range attraction (SALR) systems as an example, we show quantitative agreement between the framework and experiments. The framework is then applied to rationalize a wide range of patterns assembled from chemically active colloids in the literature exhibiting other types of pairwise interactions. In addition, the framework can predict what the assembly looks like with minimal experimental information and help infer ionic diffusivity and zeta potential values in systems where these values are inaccessible. Our results represent a solid step toward building a complete theory for understanding and controlling chemically active colloids, from the molecular level to their mesoscopic superstructures and ultimately to the macroscopic properties of the assembled materials.

Characterizing the Janus colloidal particles in AC electric field and a step towards label-free cargo manipulation

In recent years, researchers have been exploring Janus particles, a unique type of colloidal system, which has gained enormous attention across diverse fields, from soft matter physics to biology. These particles, possessing an asymmetric surface, can be manipulated in the fluid using external energy sources. This versatility makes them suitable for mimicking biological systems and applications like cargo transportation, drug delivery, biosensing, and environmental cleanup. The study focuses on the response of metal-dielectric (Ti-PMMA) Janus spheres in the AC field, created through the Physical Vapor Deposition (PVD) technique. When subjected to a uniform AC electric field, these particles exhibit different dynamic behaviors at various frequency ranges. The particles show diverse responses from induced-charge electrophoresis (ICEP: 500 Hz-80 kHz) to reversed motion (r: ICEP:100 kHz-1 MHz) and linear chain formation (1 MHz). Additionally, they randomly cluster near the lower characteristic frequency (800 Hz) of the ICEP, whereas they exhibit the 3D motion at frequencies (100 Hz) below this lower characteristic value. The mechanisms behind these dynamic phenomena could be explained by considering the concept of electric double layer (EDL), self-dielectrophoresis (sDEP), dipolar interactions, hydrodynamic interactions, and electrothermal effects. These active Janus Colloids are further leveraged to manipulate 1 µm diameter PMMA passive microparticles and E. coli bacteria at 1 kHz, showcasing their potential applications in cargo delivery under various microfluidic research areas. The manipulation of payloads could be explained based on dielectrophoretic trapping due to locally generated field gradients around the surface of the Janus sphere. Therefore, the present work offers an unprecedented opportunity to study such out-of-equilibrium complex active matter systems and create novel functional materials. Moreover, it could also be extended as a fuel-free microrobotics system for various biomedical applications such as sensing and on-demand drug or cargo delivery inside the microfluidics chamber.

Pair Interactions of Self-Propelled SiO2-Pt Janus Colloids: Chemically Mediated Encounters.

Driven by the necessity to achieve a thorough comprehension of the bottom-up fabrication process of functional materials, this experimental study investigates the pairwise interactions or collisions between chemically active SiO2-Pt Janus colloids. These collisions are categorized based on the Janus colloids' orientations before and after they make physical contact. In addition to the hydrodynamic interactions, the Janus colloids are also known to affect each other's chemical field, resulting in chemophoretic interactions, which depend on the degree of surface anisotropy in reactivity of Janus colloid and the solute-surface interaction at play. Our study reveals that these interactions lead to a noticeable decrease in particle speed and changes in orientation that correlate with the contact duration and yield different collision types. Distinct configurations of contact during collisions were found, whose mechanisms and likelihood are found to be dependent primarily on the chemical interactions. Such estimates of collision and their characterization in dilute suspensions shall have a key impact in determining the arrangement and time scales of dynamical structures and assemblies of denser suspensions and potentially the functional materials of the future.

Dynamically reconfigurable complex liquid crystal emulsions

ABSTRACT Complex emulsions, containing liquid crystals (LCs) and immiscible oils such as fluorocarbon or silicone oils, present innovative functionalities in soft materials. These emulsions exhibit dynamic reconfiguration in droplet morphology and internal LC organisation, expanding applications in optics, sensing, and active matter. This review highlights the evolution and potential of LC-containing complex emulsions. Emphasis is placed on emulsions featuring dynamic and reversible morphological transformations and LC reorganisation, underpinning their suitability for tunable micro-lenses, chemical sensing, and biosensing. Nematic LCs within complex emulsions allow for topological defect-driven functionalization, attaching antibodies to induce substantial changes in the LC director field upon interfacial recognition events. This feature may facilitate the development of ultrasensitive chemical and biological sensors. Moreover, cholesteric LCs, through their selective reflection, enable the rapid and sensitive detection of foodborne pathogens. The controlled assembly of magnetic nanoparticles at interfaces illustrates advancements towards magnetic field-responsive and active colloids. Future perspectives include exploiting these properties for intelligent colloidal systems capable of autonomous behaviour, and furthering applications in dynamic photonic devices, high-security identification tags, and responsive lens systems.

Chemical Logic Gates on Active Colloids.

Recent studies have shown that active colloidal motors using enzymatic reactions for propulsion hold special promise for applications in fields ranging from biology to material science. It will be desirable to have active colloids with capability of computation so that they can act autonomously to sense their surroundings and alter their own dynamics. It is shown how small chemical networks that make use of enzymatic chemical reactions on the colloid surface can be used to construct motor-based chemical logic gates. The basic features of coupled enzymatic reactions that are responsible for propulsion and underlie the construction and function of chemical gates are described using continuum theory and molecular simulation. Examples are given that show how colloids with specific chemical logic gates, can perform simple sensing tasks. Due to the diverse functions of different enzyme gates, operating alone or in circuits, the work presented here supports the suggestion that synthetic motors using such gates could be designed to operate in an autonomous way in order to complete complicatedtasks.

How to steer active colloids up a vertical wall

An important challenge in active matter lies in harnessing useful global work from entities that produce work locally, e.g., via self-propulsion. We investigate here the active matter version of a classical capillary rise effect, by considering a non-phase separated sediment of self-propelled Janus colloids in contact with a vertical wall. We provide experimental evidence of an unexpected and dynamic adsorption layer at the wall. Additionally, we develop a complementary numerical model that recapitulates the experimental observations. We show that an adhesive and aligning wall enhances the pre-existing polarity heterogeneity within the bulk, enabling polar active particles to climb up a wall against gravity, effectively powering a global flux. Such steady-state flux has no equivalent in a passive wetting layer.

Chemical Micromotors Move Faster at Oil-Water Interfaces.

Many real-world scenarios involve interfaces, particularly liquid-liquid interfaces, that can fundamentally alter the dynamics of colloids. This is poorly understood for chemically active colloids that release chemicals into their environment. We report here the surprising discovery that chemical micromotors─colloids that convert chemical fuels into self-propulsion─move significantly faster at an oil-water interface than on a glass substrate. Typical speed increases ranged from 3 to 6 times up to an order of magnitude and were observed for different types of chemical motors and interfaces made with different oils. Such speed increases are likely caused by faster chemical reactions at an oil-water interface than at a glass-water interface, but the exact mechanism remains unknown. Our results provide valuable insights into the complex interactions between chemical micromotors and their environments, which are important for applications in the human body or in the removal of organic pollutants from water. In addition, this study also suggests that chemical reactions occur faster at an oil-water interface and that micromotors can serve as a probe for such an effect.

Energy Density Boosted Vanadium Colloid Flow Batteries Realized by a Reversible Nanoparticle Suspension‐Dissolution Strategy

AbstractVanadium redox flow batteries (VRFBs) hold great promise for large‐scale energy storage, but their performance requires further improvement. Herein, a design is proposed for vanadium colloid flow batteries (VCFBs) that integrates the redox chemistry of polyvalent vanadium‐based colloid suspensions with dispersed conductive agents into traditional vanadium electrolytes. The redox‐active colloids combine the advantages of nanoparticle suspensions and dissolved electrolytes, exhibiting good dispersibility, fluidity, conductivity, redox reversibility, and electrochemical kinetics. By leveraging a reversible dissolution/suspension process of high‐concentration vanadium‐based colloids, the VCFBs achieved an energy density of 48 Wh L−1, nearly double that of conventional VRFBs. This work presents a rational design for homologous active material colloids to enhance the energy density of aqueous redox flow batteries, thereby advancing the potential for grid‐scale and renewable energy storage.