Multifunctional Chiral Chemically-Powered Micropropellers for Cargo Transport and Manipulation.

Practical applications of synthetic self-propelled nano and microparticles for microrobotics, targeted drug delivery, and manipulation at the nanoscale are rapidly expanding. However, fabrication limitations often hinder progress, resulting in relatively simple shapes and limited functionality. Here, taking advantage of 3D nanoscale printing, chiral micropropellers powered by the hydrogen peroxide reduction reaction are fabricated. Due to their chirality, the propellers exhibit multifunctional behavior controlled by an applied magnetic field: spinning in place (loitering), directed migration in the prescribed direction, capture, and transport of polymer cargo particles. Design parameters of the propellers are optimized by computation modeling based on mesoscale molecular dynamics. It is predicted by computer simulations, and confirmed experimentally, that clockwise rotating propellers attract each other and counterclockwise repel. These results shed light on how chirality and shape optimization enhance the functionality of synthetic autonomous micromachines.

Self-propelled torus colloids.

Suspensions of chemically powered self-propelled colloidal particles are examples of active matter systems with interesting properties. While simple spherical Janus particles are often studied, it is known that geometry is important and recent experiments have shown that chemically active torus-shaped colloids behave differently from spherical colloids. In this paper, coarse-grained microscopic simulations of the dynamics of self-diffusiophoretic torus colloids are carried out in bulk solution in order to study how torus geometric factors influence their active motion. The concentration and velocity fields are key ingredients in self-diffusiophoretic propulsion, and the forms that these fields take in the colloid vicinity are shown to be strong functions of torus geometric parameters such as the torus hole size and thickness of the torus tube. This work utilizes a method where self-diffusiophoretic torus colloids with various geometric and dynamical characteristics can be built and studied in fluid media that include chemical reactions and fluid flows. The model can be used to investigate the collective properties of these colloids and their dynamics in confined systems, topics that are of general importance for applications that use colloidal motors with complex geometries.

Active rotational dynamics of a self-diffusiophoretic colloidal motor.

The dynamics of a spherical chemically-powered synthetic colloidal motor that operates by a self-diffusiophoretic mechanism and has a catalytic domain of arbitrary shape is studied using both continuum theory and particle-based simulations. The motor executes active rotational motion when self-generated concentration gradients and interactions between the chemical species and colloidal motor surface break spherical symmetry. Local variations of chemical reaction rates on the motor catalytic surface with catalytic domain sizes and shapes provide such broken symmetry conditions. A continuum theoretical description of the active rotational motion is given, along with the results of particle-based simulations of the active dynamics. From these results a detailed description of the factors responsible for the active rotational dynamics can be given. Since active rotational motion often plays a significant part in the nature of the collective dynamics of many-motor systems and can be used to control motor motion in targeted cargo transport, our results should find applications beyond those considered here.

From single particle motion to collective dynamics in Janus motor systems.

The single-particle and collective dynamics of systems comprising Janus motors, solvent, and reactive solute species maintained in nonequilibrium states are investigated. Reversible catalytic reactions with the solute species take place on the catalytic faces of the motors, and the nonequilibrium states are established either by imposing constant-concentration reservoirs that feed and remove reactive species or through out-of-equilibrium fluid phase reactions. We consider general intermolecular interactions between the Janus motor hemispheres and the reactive species. For single motors, we show that the reaction rate depends nonlinearly on an applied external force when the system is displaced far from equilibrium. We also show that a finite-time fluctuation formula derived for fixed catalytic particles describes the nonequilibrium reactive fluctuations of moving Janus motors. Simulation of the collective dynamics of small ensembles of Janus motors with reversible kinetics under nonequilibrium conditions is carried out, and the spatial and orientational correlations of dynamic cluster states are discussed. The conditions leading to the instability of the homogeneous motor distribution and the onset of nonequilibrium dynamical clustering are described.

Synthetic Nanomotors: Working Together through Chemistry.

Active matter, some of whose constituent elements are active agents that can move autonomously, behaves very differently from matter without such agents. The active agents can self-assemble into structures with a variety of forms and dynamical properties. Swarming, where groups of living agents move cooperatively, is commonly observed in the biological realm, but it is also seen in the physical realm in systems containing small synthetic motors. The existence of diverse forms of self-assembled structures has stimulated the search for new applications that involve active matter. We consider active systems where the agents are synthetic chemically powered motors with various shapes and sizes that operate by phoretic mechanisms, especially self-diffusiophoresis. These motors are able to move autonomously in solution by consuming fuel from their environment. Chemical reactions take place on catalytic portions of the motor surface and give rise to concentration gradients that lead to directed motion. They can operate in this way only if the chemical composition of the system is maintained in a nonequilibrium state since no net fluxes are possible in a system at equilibrium. In contrast to many other active systems, chemistry plays an essential part in determining the properties of the collective dynamics and self-assembly of these chemically powered motor systems. The inhomogeneous concentration fields that result from asymmetric motor reactions are felt by other motors in the system and strongly influence how they move. This chemical coupling effect often dominates other interactions due to fluid flow fields and direct interactions among motors and determines the form that the collective dynamics takes. Since we consider small motors with micrometer and nanometer sizes, thermal fluctuations are strong and cannot be neglected. The media in which the motors operate may not be simple and may contain crowding agents or molecular filaments that influence how the motors assemble and move. The collective motion is also influenced by the chemical gradients that arise from reactions in the surrounding medium. By adopting a microscopic perspective, where the motors, fluid environment, and crowding elements are treated at the coarse-grained molecular level, all of the many-body interactions that give rise to the collective behavior naturally emerge from the molecular dynamics. Through simulations and theory, this Account describes how active matter made from chemically powered nanomotors moving in simple and more complicated media can form different dynamical structures that are strongly influenced by interactions arising from cooperative chemical reactions on the motor surfaces.

Dynamics of Janus motors with microscopically reversible kinetics.

Janus motors with chemically active and inactive hemispheres can operate only under nonequilibrium conditions where detailed balance is broken by fluxes of chemical species that establish a nonequilibrium state. A microscopic model for reversible reactive collisions on a Janus motor surface is constructed and shown to satisfy detailed balance. The model is used to study Janus particle reactive dynamics in systems at equilibrium where generalized chemical rate laws that include time-dependent rate coefficients with power-law behavior are shown to describe reaction rates. While maintaining reversible reactions on the Janus catalytic hemisphere, the system is then driven into a nonequilibrium steady state by fluxes of chemical species that control the chemical affinity. The statistical properties of the self-propelled Janus motor in this nonequilibrium steady state are investigated and compared with the predictions of a fluctuating thermodynamics theory. The model has utility beyond the examples presented here, since it allows one to explore various aspects of nonequilibrium fluctuations in systems with self-diffusiophoretic motors from a microscopic perspective.

Microscopic and continuum descriptions of Janus motor fluid flow fields.

Active media, whose constituents are able to move autonomously, display novel features that differ from those of equilibrium systems. In addition to naturally occurring active systems such as populations of swimming bacteria, active systems of synthetic self-propelled nanomotors have been developed. These synthetic systems are interesting because of their potential applications in a variety of fields. Janus particles, synthetic motors of spherical geometry with one hemisphere that catalyses the conversion of fuel to product and one non-catalytic hemisphere, can propel themselves in solution by self-diffusiophoresis. In this mechanism, the concentration gradient generated by the asymmetric catalytic activity leads to a force on the motor that induces fluid flows in the surrounding medium. These fluid flows are studied in detail through microscopic simulations of Janus motor motion and continuum theory. It is shown that continuum theory is able to capture many, but not all, features of the dynamics of the Janus motor and the velocity fields of the fluid.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

A microscopic model for chemically-powered Janus motors.

Very small synthetic motors that make use of chemical reactions to propel themselves in solution hold promise for new applications in the development of new materials, science and medicine. The prospect of such potential applications, along with the fact that systems with many motors or active elements display interesting cooperative phenomena of fundamental interest, has made the study of synthetic motors an active research area. Janus motors, comprising catalytic and noncatalytic hemispheres, figure prominently in experimental and theoretical studies of these systems. While continuum models of Janus motor systems are often used to describe motor dynamics, microscopic models that are able to account for intermolecular interactions, many-body concentration gradients, fluid flows and thermal fluctuations provide a way to explore the dynamical behavior of these complex out-of-equilibrium systems that does not rely on approximations that are often made in continuum theories. The analysis of microscopic models from first principles provides a foundation from which the range of validity and limitations of approximate theories of the dynamics may be assessed. In this paper, a microscopic model for the diffusiophoretic propulsion of Janus motors, where motor interactions with the environment occur only through hard collisions, is constructed, analyzed and compared to theoretical predictions. Microscopic simulations of both single-motor and many-motor systems are carried out to illustrate the results.

Collective dynamics of diffusiophoretic motors on a filament.

A variety of uses has been proposed for synthetic chemically powered nanomotors that exploit their autonomous directed motion. The collective dynamics of these and other active particles display features that differ from their equilibrium analogs. We investigate the collective dynamics of chemically powered diffusiophoretic motors attached to a filament. Rotational Brownian motion is reduced substantially when a motor is attached to a filament and this improves motor performance. When many motors are attached to the filament, structural and dynamical correlations that may extend over long distances arise. While some features of these correlations are due to packing on the filament, there are nonequilibrium effects that are due to the local concentration gradients of reactive species produced by all motors. As the motor density on the filament increases beyond a critical value, the average motor velocity projected along motor internuclear axis switches from forward to backward directions. Knowledge of the collective dynamics of motors on filaments should prove useful when designing ensembles of synthetic motors to perform tasks such as cargo transport involving delivery of material to specific regions in complex media.

A catalytic oligomeric motor that walks along a filament track.

Most biological motors in the cell execute chemically powered conformational changes as they walk on biopolymer filaments in order to carry out directed transport functions. Synthetic motors that operate in a similar manner are being studied since they have the potential to perform similar tasks in a variety of applications. In this paper, a synthetic nanomotor that moves along a filament track, without invoking motor conformational changes, is constructed and its properties are studied in detail. The motor is an oligomer comprising three linked beads with specific binding properties. The filament track is a stiff polymer chain, also described by a linear chain of linked coarse-grained molecular groups modeled as beads. Reactions on the filament that are catalyzed by a motor bead and use fuel in the environment, in conjunction within the binding affinities of the motor beads to the filament beads, lead to directed motion. The system operates out of equilibrium due to the state of the filament and supply of fuel. The motor, filament, and surrounding medium are all described at microscopic level that permits a full analysis of the motor motion. A stochastic model that captures the main trends seen in the simulations is also presented. The results of this study point to some of the key features that could be used to construct nanomotors that undergo biased walks powered by chemical reactions on filaments.

Coarse-grain simulations of active molecular machines in lipid bilayers.

A coarse-grain method for simulations of the dynamics of active protein inclusions in lipid bilayers is described. It combines the previously proposed hybrid simulations of bilayers [M.-J. Huang, R. Kapral, A. S. Mikhailov, and H.-Y. Chen, J. Chem. Phys. 137, 055101 (2012)], based on molecular dynamics for the lipids and multi-particle collision dynamics for the solvent, with an elastic-network description of active proteins. The method is implemented for a model molecular machine which performs active conformational motions induced by ligand binding and its release after reaction. The situation characteristic for peripheral membrane proteins is considered. Statistical investigations of the effects of single active or passive inclusions on the shape of the membrane are carried out. The results show that the peripheral machine produces asymmetric perturbations of the thickness of two leaflets of the membrane. It also produces a local saddle in the midplane height of the bilayer. Analysis of the power spectrum of the fluctuations of the membrane midplane shows that the conformational motion of the machine perturbs these membrane fluctuations. The hydrodynamic lipid flows induced by cyclic conformational changes in the machine are analyzed. It is shown that such flows are long-ranged and should provide an additional important mechanism for interactions between active inclusions in biological membranes.

Nano-swimmers in biological membranes and propulsion hydrodynamics in two dimensions.

Active protein inclusions in biological membranes can represent nano-swimmers and propel themselves in lipid bilayers. A simple model of an active inclusion with three particles (domains) connected by variable elastic links is considered. First, the membrane is modeled as a two-dimensional viscous fluid and propulsion behavior in two dimensions is examined. After that, an example of a microscopic dynamical simulation is presented, where the lipid bilayer structure of the membrane is resolved and the solvent effects are included by multiparticle collision dynamics. Statistical analysis of data reveals ballistic motion of the swimmer, in contrast to the classical diffusion behavior found in the absence of active transitions between the states.

Coarse-grain model for lipid bilayer self-assembly and dynamics: multiparticle collision description of the solvent.

A mesoscopic coarse-grain model for computationally efficient simulations of biomembranes is presented. It combines molecular dynamics simulations for the lipids, modeled as elastic chains of beads, with multiparticle collision dynamics for the solvent. Self-assembly of a membrane from a uniform mixture of lipids is observed. Simulations at different temperatures demonstrate that it reproduces the gel and liquid phases of lipid bilayers. Investigations of lipid diffusion in different phases reveals a crossover from subdiffusion to normal diffusion at long times. Macroscopic membrane properties, such as stretching and bending elastic moduli, are determined directly from the mesoscopic simulations. Velocity correlation functions for membrane flows are determined and analyzed.