Colloidal bubble propulsion mediated through viscous flows.

Bubble-propelled catalytic colloids stand out as a uniquely efficient design for artificial controllable micromachines, but so far lack a general theoretical framework that explains the physics of their propulsion. Here we develop a combined diffusive and hydrodynamic theory of bubble growth near a spherical catalytic colloid, that allows us to explain the underlying mechanism and the influence of environmental and material parameters. We identify two dimensionless groups, related to colloidal activity and the background fluid, that govern a saddle-node bifurcation of the bubble growth dynamics, and calculate the generated flows analytically for both slip and no slip boundary conditions on the bubble. We finish with a discussion of the assumptions and predictions of our model in the context of existing experimental results, and conclude that some of the observed behaviour, notably the ratchet-like gait, may stem from peculiarities of the experimental setup rather than fundamental physics of the propulsive mechanism.

Self-propulsion in 2D confinement: phoretic and hydrodynamic interactions.

Chemically active Janus particles generate tangential concentration gradients along their surface for self-propulsion. Although this is well studied in unbounded domains, the analysis in biologically relevant environments such as confinement is scarce. In this work, we study the motion of a Janus sphere in weak confinement. The particle is placed at an arbitrary location, with arbitrary orientation between the two walls. Using the method of reflections, we study the effect of confining planar boundaries on the phoretic and hydrodynamic interactions, and their consequence on the Janus particle dynamics. The dynamical trajectories are analyzed using phase diagrams for different surface coverage of activity and solute-particle interactions. In addition to near wall states such as 'sliding' and 'hovering', we demonstrate that accounting for two planar boundaries reveals two new states: channel-spanning oscillations and damped oscillations around the centerline, which were characterized as 'scattering' or 'reflection' by earlier analyses on single wall interactions. Using phase-diagrams, we highlight the differences in inert-facing and active-facing Janus particles. We also compare the dynamics of Janus particles with squirmers for contrasting the chemical interactions with hydrodynamic effects. Insights from the current work suggest that biological and artificial swimmers sense their surroundings through long-ranged interactions, that can be modified by altering the surface properties.

Alignment and scattering of colliding active droplets.

Active droplets emit a chemical solute at their surface that modifies their local interfacial tension. They exploit the nonlinear coupling of the convective transport of solute to the resulting Marangoni flows in order to self-propel. Such swimming droplets are by nature anti-chemotactic and are repelled by their own chemical wake or their neighbours. The rebound dynamics resulting from pairwise droplet interactions was recently analysed in detail for purely head-on collisions using a specific bispherical approach. Here, we extend this analysis and propose a reduced model of a generic collision to characterise the alignment and scattering properties of oblique droplet collisions and their potential impact on collective droplet dynamics. A systematic alignment of the droplets' trajectories is observed for symmetric collisions, when the droplets interact directly, and arises from the finite-time rearrangement of the droplets' chemical wake during the collision. For more generic collisions, complex and diverse dynamical regimes are observed, whether the droplets interact directly or through their chemical wake, resulting in a significant scattering.

High-Throughput Measurements of Intra-Cellular and Secreted Cytokine from Single Spheroids Using Anchored Microfluidic Droplets.

While many single-cell approaches have been developed to measure secretions from anchorage-independent cells, these protocols cannot be applied to adherent cells, especially when these cells require to be cultured in 3D formats. Here, a platform to measure secretions from individual spheroids of human mesenchymal stem cells, cultured within microfluidic droplets is introduced. The platform allows to quantify the secretions from hundreds of individual spheroids in each device, by using a secondary droplet to bring functionalized micro-beads in proximity to each spheroid. Vascular endothelial growth factor (VEGF-A) is measured on and a broad distribution of secretion levels within the population of spheroids is observed. The intra-cellular level of VEGF-A on each spheroid, measured through immuno-staining, correlates well with the extra-cellular measurement, indicating that the heterogeneities observed at the spheroid level result from variations at the intra-cellular level. Further, the molecular accumulation within the droplets is modeled and it is found that physical confinement is crucial for measurements of protein secretions. The model predicts that the time to achieve a measurement scales with droplet volume. These first measurements of secretions from individual spheroids provide several new biological and technological insights.

Spontaneous onset of convection in a uniform phoretic channel.

Phoretic mechanisms, whereby gradients of chemical solutes induce surface-driven flows, have recently been used to generate directed propulsion of patterned colloidal particles. When the chemical solutes diffuse slowly, an instability further provides active isotropic particles with a route to self-propulsion by spontaneously breaking the symmetry of the solute distribution. Here we show theoretically that, in a mechanism analogous to Bénard-Marangoni convection, phoretic phenomena can create spontaneous and self-sustained wall-driven mixing flows within a straight, chemically-uniform active channel. Such spontaneous flows do not result in any net pumping for a uniform channel but greatly modify the distribution and transport of the chemical solute. The instability is predicted to occur for a solute Péclet number above a critical value and for a band of finite perturbation wavenumbers. We solve the perturbation problem analytically to characterize the instability, and use both steady and unsteady numerical computations of the full nonlinear transport problem to capture the long-time coupled dynamics of the solute and flow within the channel.

Orientational instability and spontaneous rotation of active nematic droplets.

In experiments, an individual chemically-active liquid crystal (LC) droplet submerged in the bulk of a surfactant solution may self-propel along a straight, helical, or random trajectory. In this paper, we develop a minimal model capturing all three types of self-propulsion trajectories of a drop in the case of a nematic LC with homeotropic anchoring at the LC-fluid interface. We emulate the director field within the drop by a single preferred polarization vector that is subject of two reorientation mechanisms, namely, the internal flow-induced displacement of the hedgehog defect and the droplet's rotation. Within this reduced-order model, the coupling between the nematic ordering of the drop and the surfactant transport is represented by variations of the droplet's interfacial properties with nematic polarization. Our analysis reveals that a novel mode of orientational instability emerges from the competition of the two reorientation mechanisms and is characterized by a spontaneous rotation of the self-propelling drop responsible for helical self-propulsion trajectories. In turn, we also show that random trajectories in isotropic and nematic drops alike stem from the advection-driven transition to chaos. The succession of the different propulsion modes is consistent with experimentally-reported transitions in the shape of droplet trajectories as the drop size is varied.

Universal optimal geometry of minimal phoretic pumps.

Unlike pressure-driven flows, surface-mediated phoretic flows provide efficient means to drive fluid motion on very small scales. Colloidal particles covered with chemically-active patches with nonzero phoretic mobility (e.g. Janus particles) swim using self-generated gradients, and similar physics can be exploited to create phoretic pumps. Here we analyse in detail the design principles of phoretic pumps and show that for a minimal phoretic pump, consisting of 3 distinct chemical patches, the optimal arrangement of the patches maximizing the flow rate is universal and independent of chemistry.

Nonlinear dynamics of a chemically-active drop: From steady to chaotic self-propulsion.

Individual chemically active drops suspended in a surfactant solution were observed to self-propel spontaneously with straight, helical, or chaotic trajectories. To elucidate how these drops can exhibit such strikingly different dynamics and "decide" what to do, we propose a minimal axisymmetric model of a spherical active drop, and show that simple and linear interface properties can lead to both steady self-propulsion of the droplet as well as chaotic behavior. The model includes two different mobility mechanisms, namely, diffusiophoresis and the Marangoni effect, which convert self-generated gradients of surfactant concentration into the flow at the droplet surface. In turn, surface-driven flow initiates surfactant advection that is the only nonlinear mechanism and, thus, the only source of dynamical complexity in our model. Numerical investigation of the fully coupled hydrodynamic and advection-diffusion problems reveals that strong advection (e.g., large droplet size) may destabilize a steadily self-propelling drop; once destabilized, the droplet spontaneously stops and a symmetric extensile flow emerges. If advection is strengthened even further in comparison with molecular diffusion, the droplet may perform chaotic oscillations. Our results indicate that the thresholds of these instabilities depend heavily on the balance between diffusiophoresis and the Marangoni effect. Using linear stability analysis, we demonstrate that diffusiophoresis promotes the onset of high-order modes of monotonic instability of the motionless drop. We argue that diffusiophoresis has a similar effect on the instabilities of a moving drop.

Phoretic and hydrodynamic interactions of weakly confined autophoretic particles.

Phoretic particles self-propel using self-generated physico-chemical gradients at their surface. Within a suspension, they interact hydrodynamically by setting the fluid around them into motion and chemically by modifying the chemical background seen by their neighbours. While most phoretic systems evolve in confined environments due to buoyancy effects, most models focus on their interactions in unbounded flows. Here, we propose a first model for the interaction of phoretic particles in Hele-Shaw confinement and show that in this limit, hydrodynamic and phoretic interactions share not only the same scaling but also the same form, albeit in opposite directions. In essence, we show that phoretic interactions effectively reverse the sign of the interactions that would be obtained for swimmers interacting purely hydrodynamically. Yet, hydrodynamic interactions cannot be neglected as they significantly impact the magnitude of the interactions. This model is then used to analyse the behavior of a suspension. The suspension exhibits swirling and clustering collective modes dictated by the orientational interactions between particles, similar to hydrodynamic swimmers, but here governed by the surface properties of the phoretic particle; the reversal in the sign of the interaction tends to slow down the swimming motion of the particles.

Clustering-induced self-propulsion of isotropic autophoretic particles.

Self-diffusiophoretic particles exploit local concentration gradients of a solute species in order to self-propel at the micron scale. While an isolated chemically- and geometrically-isotropic particle cannot swim, we show that it can achieve self-propulsion through interactions with other individually-non-motile particles by forming geometrically-anisotropic clusters via phoretic and hydrodynamic interactions. This result identifies a new route to symmetry-breaking for the concentration field and to self-propulsion, that is not based on an anisotropic design, but on the collective dynamics of identical and homogeneous active particles. Using full numerical simulations as well as theoretical modelling of the clustering process, the statistics of the propulsion properties are obtained for arbitrary initial arrangement of the particles. The robustness of these results to thermal noise, and more generally the effect of Brownian motion of the particles, is also discussed.

Corrigendum: Monitoring the orientation of rare-earth-doped nanorods for flow shear tomography.

This corrects the article DOI: 10.1038/nnano.2017.111.

Monitoring the orientation of rare-earth-doped nanorods for flow shear tomography.

Rare-earth phosphors exhibit unique luminescence polarization features originating from the anisotropic symmetry of the emitter ion's chemical environment. However, to take advantage of this peculiar property, it is necessary to control and measure the ensemble orientation of the host particles with a high degree of precision. Here, we show a methodology to obtain the photoluminescence polarization of Eu-doped LaPO4 nanorods assembled in an electrically modulated liquid-crystalline phase. We measure Eu3+ emission spectra for the three main optical configurations (σ, π and α, depending on the direction of observation and the polarization axes) and use them as a reference for the nanorod orientation analysis. Based on the fact that flowing nanorods tend to orient along the shear strain profile, we use this orientation analysis to measure the local shear rate in a flowing liquid. The potential of this approach is then demonstrated through tomographic imaging of the shear rate distribution in a microfluidic system.

Geometric tuning of self-propulsion for Janus catalytic particles.

Catalytic swimmers have attracted much attention as alternatives to biological systems for examining collective microscopic dynamics and the response to physico-chemical signals. Yet, understanding and predicting even the most fundamental characteristics of their individual propulsion still raises important challenges. While chemical asymmetry is widely recognized as the cornerstone of catalytic propulsion, different experimental studies have reported that particles with identical chemical properties may propel in opposite directions. Here, we show that, beyond its chemical properties, the detailed shape of a catalytic swimmer plays an essential role in determining its direction of motion, demonstrating the compatibility of the classical theoretical framework with experimental observations.

Universal microfluidic platform for bioassays in anchored droplets.

In spite of the large number of droplet-based microfluidic tools that have appeared in recent years, their penetration into non-specialist labs remains limited to a small number of applications. This is partly due to the lack of a generic platform that integrates all of the necessary operations for end-users, and partly to the increasing complexity that emerges as several operations are combined together. Here we report the development of a platform that provides the capabilities of multiwell plates in a two-dimensional array of nanoliter droplets: encapsulation, time-resolved monitoring and variation of well contents, as well as the ability to selectively extract the contents of any of the wells. We demonstrate these capabilities by encapsulating thousands of individual bacterial cells in droplets that are stored on a two-dimensional array of surface-energy anchors. Bacterial culture can be performed either in liquid or hydrogel droplets, both of which allow precise quantification using either standard measurements or digital enumeration. Using hydrogels allows the removal of the external oil that surrounds the aqueous drops, for instance in order to apply a gradient of antibiotics across the droplet population. This defines a protocol to obtain an antibiogram in a single experiment. Finally, the liquid to gel transition provides a robust way to selectively extract any droplet from the array, by melting it with a focused laser. When combined with further off-chip culture or genotyping, this platform provides a unique culturing environment to relate phenotype and genotype measurements on monoclonal colonies.

Stresslets Induced by Active Swimmers.

Active particles disturb the fluid around them as force dipoles, or stresslets, which govern their collective dynamics. Unlike swimming speeds, the stresslets of active particles are rarely determined due to the lack of a suitable theoretical framework for arbitrary geometry. We propose a general method, based on the reciprocal theorem of Stokes flows, to compute stresslets as integrals of the velocities on the particle's surface, which we illustrate for spheroidal chemically active particles. Our method will allow tuning the stresslet of artificial swimmers and tailoring their collective motion in complex environments.

A regularised singularity approach to phoretic problems.

An efficient, accurate, and flexible numerical method is proposed for the solution of the swimming problem of one or more autophoretic particles in the purely diffusive limit. The method relies on successive boundary element solutions of the Laplacian and the Stokes flow equations using regularised Green's functions for swift, simple implementations, an extension of the well-known method of "regularised stokeslets" for Stokes flow problems. The boundary element method is particularly suitable for phoretic problems, since no quantities in the domain bulk are required to compute the swimming velocity. For time-dependent problems, the method requires no re-meshing and simple boundaries such as a plane wall may be added at no increase to the size of the linear system through the method of images. The method is validated against two classical examples for which an analytical or semi-analytical solution is known, a two-sphere system and a Janus particle, and provides a rigorous computational pipeline to address further problems with complex geometry and multiple bodies.

Flow distribution in parallel microfluidic networks and its effect on concentration gradient.

The architecture of microfluidic networks can significantly impact the flow distribution within its different branches and thereby influence tracer transport within the network. In this paper, we study the flow rate distribution within a network of parallel microfluidic channels with a single input and single output, using a combination of theoretical modeling and microfluidic experiments. Within the ladder network, the flow rate distribution follows a U-shaped profile, with the highest flow rate occurring in the initial and final branches. The contrast with the central branches is controlled by a single dimensionless parameter, namely, the ratio of hydrodynamic resistance between the distribution channel and the side branches. This contrast in flow rates decreases when the resistance of the side branches increases relative to the resistance of the distribution channel. When the inlet flow is composed of two parallel streams, one of which transporting a diffusing species, a concentration variation is produced within the side branches of the network. The shape of this concentration gradient is fully determined by two dimensionless parameters: the ratio of resistances, which determines the flow rate distribution, and the Péclet number, which characterizes the relative speed of diffusion and advection. Depending on the values of these two control parameters, different distribution profiles can be obtained ranging from a flat profile to a step distribution of solute, with well-distributed gradients between these two limits. Our experimental results are in agreement with our numerical model predictions, based on a simplified 2D advection-diffusion problem. Finally, two possible applications of this work are presented: the first one combines the present design with self-digitization principle to encapsulate the controlled concentration in nanoliter chambers, while the second one extends the present design to create a continuous concentration gradient within an open flow chamber.

Geometric pumping in autophoretic channels.

Many microfluidic devices use macroscopic pressure differentials to overcome viscous friction and generate flows in microchannels. In this work, we investigate how the chemical and geometric properties of the channel walls can drive a net flow by exploiting the autophoretic slip flows induced along active walls by local concentration gradients of a solute species. We show that chemical patterning of the wall is not required to generate and control a net flux within the channel, rather channel geometry alone is sufficient. Using numerical simulations, we determine how geometric characteristics of the wall influence channel flow rate, and confirm our results analytically in the asymptotic limit of lubrication theory.

Autophoretic locomotion from geometric asymmetry.

Among the few methods which have been proposed to create small-scale swimmers, those relying on self-phoretic mechanisms present an interesting design challenge in that chemical gradients are required to generate net propulsion. Building on recent work, we propose that asymmetries in geometry are sufficient to induce chemical gradients and swimming. We illustrate this idea using two different calculations. We first calculate exactly the self-propulsion speed of a system composed of two spheres of unequal sizes but identically chemically homogeneous. We then consider arbitrary, small-amplitude, shape deformations of a chemically homogeneous sphere, and calculate asymptotically the self-propulsion velocity induced by the shape asymmetries. Our results demonstrate how geometric asymmetries can be tuned to induce large locomotion speeds without the need of chemical patterning.

Self-propulsion of pure water droplets by spontaneous Marangoni-stress-driven motion.

We report spontaneous motion in a fully biocompatible system consisting of pure water droplets in an oil-surfactant medium of squalane and monoolein. Water from the droplet is solubilized by the reverse micellar solution, creating a concentration gradient of swollen reverse micelles around each droplet. The strong advection and weak diffusion conditions allow for the first experimental realization of spontaneous motion in a system of isotropic particles at sufficiently large Péclet number according to a straightforward generalization of a recently proposed mechanism [S. Michelin, E. Lauga, and D. Bartolo, Phys. Fluids 25, 061701 (2013); S. Michelin and E. Lauga, J. Fluid Mech. 747, 572 (2014)]. Experiments with a highly concentrated solution of salt instead of water, and tetradecane instead of squalane, confirm the above mechanism. The present swimming droplets are able to carry external bodies such as large colloids, salt crystals, and even cells.