Integrating chemistry, fluid flow, and mechanics to drive spontaneous formation of three-dimensional (3D) patterns in anchored microstructures.

Enzymatic reactions in solution drive the convection of confined fluids throughout the enclosing chambers and thereby couple the processes of reaction and convection. In these systems, the energy released from the chemical reactions generates a force, which propels the fluids' spontaneous motion. Here, we use theoretical and computational modeling to determine how reaction-convection can be harnessed to tailor and control the dynamic behavior of soft matter immersed in solution. Our model system encompasses an array of surface-anchored, flexible posts in a millimeter-sized, fluid-filled chamber. Selected posts are coated with enzymes, which react with dissolved chemicals to produce buoyancy-driven fluid flows. We show that these chemically generated flows exert a force on both the coated (active) and passive posts and thus produce regular, self-organized patterns. Due to the specificity of enzymatic reactions, the posts display controllable kaleidoscopic behavior where one regular pattern is smoothly morphed into another with the addition of certain reactants. These spatiotemporal patterns also form "fingerprints" that distinctly characterize the system, reflecting the type of enzymes used, placement of the enzyme-coated posts, height of the chamber, and bending modulus of the elastic posts. The results reveal how reaction-convection provides concepts for designing soft matter that readily switches among multiple morphologies. This behavior enables microfluidic devices to be spontaneously reconfigured for specific applications without construction of new chambers and the fabrication of standalone sensors that operate without extraneous power sources.

Self-Propelling Macroscale Sheets Powered by Enzyme Pumps.

Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano- and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self-propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter-scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.

Interlinking spatial dimensions and kinetic processes in dissipative materials to create synthetic systems with lifelike functionality.

Biological systems spontaneously convert energy input into the actions necessary to survive. Motivated by the efficacy of these processes, researchers aim to forge materials systems that exhibit the self-sustained and autonomous functionality found in nature. Success in this effort will require synthetic analogues of the following: a metabolism to generate energy, a vasculature to transport energy and materials, a nervous system to transmit 'commands', a musculoskeletal system to translate commands into physical action, regulatory networks to monitor the entire enterprise, and a mechanism to convert 'nutrients' into growing materials. Design rules must interconnect the material's structural and kinetic properties over ranges of length (that can vary from the nano- to mesoscale) and timescales to enable local energy dissipations to power global functionality. Moreover, by harnessing dynamic interactions intrinsic to the material, the system itself can perform the work needed for its own functionality. Here, we assess the advances and challenges in dissipative materials design and at the same time aim to spur developments in next-generation functional, 'living' materials.

Engineering confined fluids to autonomously assemble hierarchical 3D structures.

The inherent coupling of chemical and mechanical behavior in fluid-filled microchambers enables the fluid to autonomously perform work, which in turn can direct the self-organization of objects immersed in the solution. Using theory and simulations, we show that the combination of diffusioosmotic and buoyancy mechanisms produce independently controlled, respective fluid flows: one generated by confining surfaces and the other in the bulk of the solution. With both flows present, the fluid can autonomously join 2D, disconnected pieces to a chemically active, "sticky" base and then fold the resulting layer into regular 3D shapes (e.g. pyramids, tetrahedrons, and cubes). Here, the fluid itself performs the work of construction and thus, this process does not require extensive external machinery. If several sticky bases are localized on the bottom surface, the process can be parallelized, with the fluid simultaneously forming multiple structures of the same or different geometries. Hence, this approach can facilitate the relatively low-cost, mass production of 3D micron to millimeter-sized structures. Formed in an aqueous solution, the assembled structures could be compatible with biological environments, and thus, potentially useful in medical and biochemical applications.

Chemically Driven Multimodal Locomotion of Active, Flexible Sheets.

The inhibitor-promoter feedback loop is a vital component in regulatory pathways that controls functionality in living systems. In this loop, the production of chemical A at one site promotes the production of chemical B at another site, but B inhibits the production of A. In solution, differences in the volumes of the reactants and products of this reaction can generate buoyancy-driven fluid flows, which will deform neighboring soft material. To probe the intrinsic interrelationship among chemistry, hydrodynamics, and fluid-structure interactions, we model a bio-inspired system where a flexible sheet immersed in solution encompasses two spatially separated catalytic patches, which drive the A-B inhibitor-promotor reaction. The convective rolls of fluid generated above the patches can circulate inward or outward depending on the chemical environment. Within the regime displaying chemical oscillations, the dynamic fluid-structure interactions morph the shape of the sheet to periodically "fly", "crawl", or "swim" along the bottom of the confining chamber, revealing an intimate coupling between form and function in this system. The oscillations in the sheet's motion in turn affect the chemical oscillations in the solution. In the regime with non-oscillatory chemistry, the induced flow still morphs the shape of the sheet, but now, the fluid simply translates the sheet along the length of the chamber. The findings reveal the potential for enzymatic reactions in the body to generate hydrodynamic behavior that modifies the shape of neighboring soft tissue, which in turn modifies both the fluid dynamics and the enzymatic reaction. The findings indicate that this non-linear dynamic behavior can be playing a critical role in the functioning of regulatory pathways in living systems.

Light-Powered, Fuel-Free Oscillation, Migration, and Reversible Manipulation of Multiple Cargo Types by Micromotor Swarms.

Through experiments and simulations, we show that fuel-free photoactive TiO2 microparticles can form mobile, coherent swarms in the presence of UV light, which track the subsequent movement of an irradiated spot in a fluid-filled microchamber. Multiple concurrent propulsion mechanisms (electrolyte diffusioosmotic swarming, photocatalytic expansion, and photothermal migration) control the rich collective behavior of the swarms, which provide a strategy to reversely manipulate cargo. The active swarms can autonomously pick up groups of inert particles, sort them by size, and sequentially release the sorted particles at particular locations in the microchamber. Hence, these swarms overcome three obstacles, limiting the utility of self-propelled particles. Namely, they can (1) undergo directed, long-range migration without the addition of a chemical fuel, (2) perform diverse collective behavior not possible with a single active particle, and (3) repeatedly and controllably isolate and deliver specific components of a multiparticle "cargo". Since light sources are easily fabricated, transported, and controlled, the results can facilitate the development of portable devices, providing broader access to the diagnostic and manufacturing advances enabled by microfluidics.

Self-Generated Convective Flows Enhance the Rates of Chemical Reactions.

In chemical solutions, the products of catalytic reactions can occupy different volumes compared to the reactants and thus give rise to local density variations in the fluid. These density variations generate solutal buoyancy forces, which are exerted on the fluid and thus "pump" the fluid to flow. Herein, we examine if the reaction-induced pumping accelerates the chemical reaction by transporting the reactants to the catalyst at a rate faster than passive diffusion. Using both simulations and experiments, we show a significant increase in reaction rate when reaction-generated convective flow is present. In effect, through a feedback loop, catalysts speed up reactions not only by lowering the energy barrier but also by increasing the collision frequency between the reactants and the catalyst.

Solutal-buoyancy-driven intertwining and rotation of patterned elastic sheets.

The intertwining of strands into 3D spirals is ubiquitous in biology, enabling functions from information storage to maintenance of cell structure and directed locomotion. In synthetic systems, entwined fibers can provide superior mechanical properties and act as artificial muscle or structural reinforcements. Unlike structures in nature, the entwinement of synthetic materials typically requires application of an external stimulus, such as mechanical actuation, light, or a magnetic field. Herein, we use computational modeling to design microscale sheets that mimic biology by transducing chemical energy into mechanical action, and thereby self-organize and interlink into 3D spirals, which spontaneously rotate. These flexible sheets are immersed in a fluid-filled microchamber that encompasses an immobilized patch of catalysts on the bottom wall. The sheets themselves can be passive or active (coated with catalyst). Catalytic reactions in the solution generate products that occupy different volumes than the reactants. The resulting density variations exert a force on the fluid (solutal buoyancy force) that causes motion, which in turn drives the interlinking and collective swirling of the sheets. The individual sheets do not rotate; rotation only occurs when the sheets are interlinked. This level of autonomous, coordinated 3D structural organization, intertwining, and rotation is unexpected in synthetic materials systems operating without external controls. Using physical arguments, we identify dimensionless ratios that are useful in scaling these ideas to other systems. These findings are valuable for creating materials that act as "machines", and directing soft matter to undergo self-sustained, multistep assembly that is governed by intrinsic chemical reactions.

Resonant amplification of enzymatic chemical oscillations by oscillating flow.

Using theory and simulation, we analyzed the resonant amplification of chemical oscillations that occur due to externally imposed oscillatory fluid flows. The chemical reactions are promoted by two enzyme-coated patches located sequentially on the inner surface of a pipe that transports the enclosed chemical solution. In the case of diffusion-limited systems, the period of oscillations in chemical reaction networks is determined by the rate of the chemical transport, which is diffusive in nature and, therefore, can be effectively accelerated by the imposed fluid flows. We first identify the natural frequencies of the chemical oscillations in the unperturbed reaction-diffusion system and, then, use the frequencies as a forcing input to drive the system to resonance. We demonstrate that flow-induced resonance can be used to amplify the amplitude of the chemical oscillations and to synchronize their frequency to the external forcing. In particular, we show that even 10% perturbations in the flow velocities can double the amplitude of the resulting chemical oscillations. Particularly, effective control can be achieved for the two-step chemical reactions where during the first half-period, the fluid flow accelerates the chemical flux toward the second catalytic patch, while during the second half-period, the flow amplifies the flux to the first patch. The results can provide design rules for regulating the dynamics of coupled reaction-diffusion processes and can facilitate the development of chemical reaction networks that act as chemical clocks.

Chemical pumps and flexible sheets spontaneously form self-regulating oscillators in solution.

The synchronization of self-oscillating systems is vital to various biological functions, from the coordinated contraction of heart muscle to the self-organization of slime molds. Through modeling, we design bioinspired materials systems that spontaneously form shape-changing self-oscillators, which communicate to synchronize both their temporal and spatial behavior. Here, catalytic reactions at the bottom of a fluid-filled chamber and on mobile, flexible sheets generate the energy to "pump" the surrounding fluid, which also transports the immersed sheets. The sheets exert a force on the fluid that modifies the flow, which in turn affects the shape and movement of the flexible sheets. This feedback enables a single coated (active) and even an uncoated (passive) sheet to undergo self-oscillation, displaying different oscillatory modes with increases in the catalytic reaction rate. Two sheets (active or passive) introduce excluded volume, steric interactions. This distinctive combination of the hydrodynamic, fluid-structure, and steric interactions causes the sheets to form coupled oscillators, whose motion is synchronized in time and space. We develop a heuristic model that rationalizes this behavior. These coupled self-oscillators exhibit rich and tunable phase dynamics, which depends on the sheets' initial placement, coverage by catalyst and relative size. Moreover, through variations in the reactant concentration, the system can switch between the different oscillatory modes. This breadth of dynamic behavior expands the functionality of the coupled oscillators, enabling soft robots to display a variety of self-sustained, self-regulating moves.

Achieving Independent Control over Surface and Bulk Fluid Flows in Microchambers.

To fully realize the potential of microfluidic platforms as useful diagnostic tools, the devices must be sufficiently portable that they function at the point-of-care, as well as remote and resource-poor locations. Using both modeling and experiments, here we develop a standalone fluidic device that is driven by light and operates without the need for external electrical or mechanical pumps. The light initiates a photochemical reaction in the solution; the release of chemical energy from the reaction is transduced into the spontaneous motion of the surrounding fluid. The generated flow is driven by two simultaneously occurring mechanisms: solutal buoyancy that controls the motion of the bulk fluid and diffusioosmosis that regulates motion near the bottom of the chamber. Consequently, the bulk and surface fluid flows can be directed independently of one another. We demonstrate that this exceptional degree of spatiotemporal control provides a new method for autonomously transporting different-sized particles in opposite directions within the chamber. Thus, one device can be used to both separate the particles and drive them to different locations for further processing or analysis. This property is particularly useful for analyzing fluids that contain multiple contaminants or disease agents. Because this system relies on intrinsic hydrodynamic interactions initiated by a portable, small-scale source of light, the device provides the desired level of mobility vital for the next generation of functional fluidic platforms.

Effects of an Imposed Flow on Chemical Oscillations Generated by Enzymatic Reactions.

Using analytical and computational models, we determine how externally imposed flows affect chemical oscillations that are generated by two enzyme-coated patches within a fluid-filled millimeter sized channel. The fluid flow affects the advective contribution to the flux of chemicals in the channel and, thereby, modifies the chemical reactions. Here, we show that changes in the flow velocity permit control over the chemical oscillations by broadening the range of parameters that give rise to oscillatory behavior, increasing the frequency of oscillations, or suppressing the oscillations all together. Notably, simply accelerating the flow along the channel transforms time-independent distributions of reagents into pronounced chemical oscillations. These findings can facilitate the development of artificial biochemical networks that act as chemical clocks.

Light-Induced Dynamic Control of Particle Motion in Fluid-Filled Microchannels.

The design of remotely programmable microfluidic systems with controlled fluid flow and particle transport is a significant challenge. Herein, we describe a system that harnesses the intrinsic thermal response of a fluid to spontaneously pump solutions and regulate the transport of immersed microparticles. Irradiating a silver-coated channel with ultraviolet (UV) light generates local convective vortexes, which, in addition to the externally imposed flow, can be used to guide particles along specific trajectories or to arrest their motion. The method provides the distinct advantage that the flow and the associated convective patterns can be dynamically altered by relocating the source of UV light. Moreover, the flow can be initiated and terminated "on-demand" by turning the light on or off.

Controlling the Spatiotemporal Transport of Particles in Fluid-Filled Microchambers.

The development of microscale devices that autonomously perform multistep processes is vital to advancing the use of microfluidics in industrial applications. Such advances can potentially be achieved through the use of "chemical pumps" that transduce the energy from inherent catalytic reactions into fluid flow within microchambers, without the need for extraneous external equipment. Using computational modeling, we focus on arrangements of multiple chemical pumps that are formed by anchoring patches of different enzymes onto the floor of a fluid-filled chamber. With the addition of the appropriate reactants, only one of the enzymatic patches is activated and thereby generates fluid flow centered about that patch. These flows drive the self-assembly of microparticles in the solution and localize the particles onto the activated patches. By varying the spatial arrangement of the enzymatic patches, and the sequence in which the appropriate reactants are added to the solution, we realize spatiotemporal control over the fluid flow and the sequential transport of microparticles from one patch to another. The order in which the particles visit the different patches can be altered by varying the sequence in which the reactants are added to the solution. By harnessing catalytic cascade reactions, where the product of one reaction is the reactant for the next, we achieve directed transport between the patches with the addition of just one reactant, which initiates the catalytic cascade. Through these studies, we show how the trajectory of the particles' motion among different "stations" can be readily regulated through intrinsic catalytic reactions and thus, provide guidelines for creating fluidic devices that perform multistep reactions in an autonomous, self-sustained manner.

Fight the flow: the role of shear in artificial rheotaxis for individual and collective motion.

To navigate in complex fluid environments, swimming organisms like fish or bacteria often reorient their bodies antiparallel or against the flow, more commonly known as rheotaxis. This reorientation motion enables the organisms to migrate against the fluid flow, as observed in salmon swimming upstream to spawn. Rheotaxis can also be realized in artificial microswimmers - self-propelled particles that mimic swimming microorganisms. Here we study experimentally and by computer simulations the rheotaxis of self-propelled gold-platinum nanorods in microfluidic channels. We observed two distinct modes of artificial rheotaxis: a high shear domain near the bottom wall of the microfluidic channel and a low shear regime in the corners. Reduced fluid drag in the corners promotes the formation of many particle aggregates that rheotax collectively. Our study provides insight into the biomimetic functionality of artificial self-propelled nanorods for dynamic self-assembly and the delivery of payloads to targeted locations.

Collaboration and competition between active sheets for self-propelled particles.

Biological species routinely collaborate for their mutual benefit or compete for available resources, thereby displaying dynamic behavior that is challenging to replicate in synthetic systems. Here we use computational modeling to design microscopic, chemically active sheets and self-propelled particles encompassing the appropriate synergistic interactions to exhibit bioinspired feeding, fleeing, and fighting. This design couples two different mechanisms for chemically generating motion in fluid-filled microchambers: solutal buoyancy and diffusiophoresis. Catalyst-coated sheets, which resemble crabs with four distinct claws, convert reactants in solution into products and thereby create local variations in the density and chemical composition of the fluid. Via the solutal buoyancy mechanism, the density variations generate fluid flows, which modify the shape and motility of the crabs. Concomitantly, the chemical variations propel the motion of the particles via diffusiophoresis, and thus, the crabs' and particles' motion becomes highly interconnected. For crabs with restricted lateral mobility, these two mechanisms can be modulated to either drive a crab to catch and appear to feed on all of the particles or enable the particles to flee from this sheet. Moreover, by adjusting the sheet's size and the catalytic coating, two crabs can compete and fight over the motile, diffusiophoretic particles. Alternatively, the crabs can temporally share resources by shuttling the particles back and forth between themselves. With completely mobile sheets, four crabs can collaborate to perform a function that one alone cannot accomplish. These findings provide design rules for creating chemically driven soft robotic sheets that significantly expand the functionality of microfluidic devices.

Light-Induced Convective Segregation of Different Sized Microparticles.

Using computational modeling, we design a facile method for sorting particles of different sizes in a fluid-filled microchamber. The microchamber is inclined at an angle with respect to the horizontal direction and contains suspended gold nanoparticles as well as the microparticles. With the application of ultraviolet light, the heat generated by illuminating the gold nanoparticles gives rise to thermal buoyancy effects, which drive the flow of the fluid in the chamber. This thermally driven, convective flow can be tailored by varying the intensity of the imposed light and the concentration of the gold nanoparticles in the solution. The competition between the drag force imposed by the fluid flows and the gravitational forces acting on the different sized particles produces the separation of the particles along the chamber's bottom, inclined wall. The separation distance between the particles can be increased by increasing the angle of inclination and the relative difference in the particle sizes. This system provides a label-free, membrane-less, and low-cost approach for sorting particles vital to a wide range of applications.

Self-Organization of Fluids in a Multienzymatic Pump System.

The nascent field of microscale flow chemistry focuses on harnessing flowing fluids to optimize chemical reactions in microchambers and establish new routes for chemical synthesis. With enzymes and other catalysts anchored to the surface of microchambers, the catalytic reactions can act as pumps and propel the fluids through the containers. Hence, the flows not only affect the catalytic reactions, but these reactions also affect the flows. Understanding this dynamic interplay is vital to enhancing the accuracy and utility of flow technology. Through experiments and simulation, we design a system of three different enzymes, immobilized in separate gels, on the surface of a microchamber; with the appropriate reactants in the solution, each enzyme-filled gel acts as a pump. The system also exploits a reaction cascade that controls the temporal interactions between two pumps. With three pumps in a triangular arrangement, the spatio-temporal interactions among the chemical reactions become highly coordinated and produce well-defined fluid streams, which transport chemicals and form a fluidic "circuit". The circuit layout and flow direction of each constituent stream can be controlled through the number and placement of the gels and the types of catalysts localized in the gels. These studies provide a new route for forming self-organizing and bifurcating fluids that can yield fundamental insight into nonequilibrium, dynamical systems. Because the flows and fluidic circuits are generated by internal chemical reactions, the fluids can autonomously transport cargo to specific locations in the device. Hence, the findings also provide guidelines to facilitate further automation of microfluidic devices.

Organization of Particle Islands through Light-Powered Fluid Pumping.

The field of active matter holds promise for applications in particle assembly, cargo and drug delivery, and sensing. In pursuit of these capabilities, researchers have produced a suite of nanomotors, fluid pumps, and particle assembly strategies. Although promising, there are many challenges, especially for mechanisms that rely on chemical propulsion. One way to circumvent these issues is by the use of external energy sources. Herein, we propose a method of using freely suspended nanoparticles to generate fluid pumping towards desired point sources. The pumping rates are dependent on particle concentration and light intensity, making it highly controllable. Using these directed flows, we further demonstrate the ability to reversibly construct and move colloidal crystals.