Using Chemical Pumps and Motors To Design Flows for Directed Particle Assembly.

Mechanical and electrical pumps are conventionally used to drive fluid flow in microfluidic devices; these pumps require external power supplies, thus limiting the portability of the devices. Harnessing catalytic reactions in solution allows pumping to be shifted into the chemical realm and alleviates the need for extraneous equipment. Chemical "pumps" involve surface-bound catalytic patches that decompose dissolved reagents into the products of the reaction. The catalytic reactions thereby produce chemical gradients that in turn generate pronounced flow fields. Such chemically-generated flows can be harnessed to transport particles in the solution and regulate their self-organization into complex structures within confined chambers. The challenge, however, is determining the reactions and conditions that will yield "programmable" flows, which permit control over the structure formation. In this Account, we review our modeling efforts to design chemical pumps (and "motors") to regulate the motion and assembly of microscopic particles in solution. In the first scenario, microcapsules release reagents in a microchamber with stationary catalytic patches and thereby act as "fuel" for the microcapsules' self-sustained motion. As the reagent is consumed, the capsules aggregate into "colonies" on the catalyst-covered sites. The shape of the assembled colonies can be tailored by patterning the distribution of the catalyst on the surface. Hence, these chemical pumps can be utilized to regulate the autonomous motion and targeted delivery of microcarriers in microfluidic devices. Notably, this fundamental physicochemical mechanism could have played a role in the self-organization of early biological cells (protocells). In the second example, the catalysts are localized on mobile, active particles, which are called "motors". Reactants dispersed in the solution are decomposed at the surface of the motors and produce a convective flow that transports both the active particles and nearby passive, non-coated particles. Depending on the numbers of active and passive particles and the structure of the self-organized cluster, these assemblies can translate or spin and thus act as self-assembled "conveyor belts" or gears in the microchamber. The latter examples involve the formation of two-dimensional structures. In the final scenario, we devise a mechanism for assembling three-dimensional towerlike structures using microcapsules in solution. Here, chemicals diffusing from a central patch on a surface generate a radially directed flow along the surface toward the center. This toroidal roll of fluid lifts the capsules above the patch and draws out the cluster into a tower, whose structure can be tailored by varying the attractive capsule-capsule and capsule-surface interaction strengths. Hence, our method of flow-directed assembly can permit the growth of reconfigurable 3D structures from simple subunits. Taken together, these findings facilitate the fabrication of stand-alone microfluidic devices that autonomously perform multistage chemical reactions and assays for portable biomedical applications and act as small-scale factories to autonomously build microscale components.