Acoustically Powered Nano- and Microswimmers: From Individual to Collective Behavior.

Micro- and nanoscopic particles that swim autonomously and self-assemble under the influence of chemical fuels and external fields show promise for realizing systems capable of carrying out large-scale, predetermined tasks. Different behaviors can be realized by tuning swimmer interactions at the individual level in a manner analogous to the emergent collective behavior of bacteria and mammalian cells. However, the limited toolbox of weak forces with which to drive these systems has made it difficult to achieve useful collective functions. Here, we review recent research on driving swimming and particle self-organization using acoustic fields, which offers capabilities complementary to those of the other methods used to power microswimmers. With either chemical or acoustic propulsion (or a combination of the two), understanding individual swimming mechanisms and the forces that arise between individual particles is a prerequisite to harnessing their interactions to realize collective phenomena and macroscopic functionality. We discuss here the ingredients necessary to drive the motion of microscopic particles using ultrasound, the theory that describes that behavior, and the gaps in our understanding. We then cover the combination of acoustically powered systems with other cross-compatible driving forces and the use of ultrasound in generating collective behavior. Finally, we highlight the demonstrated applications of acoustically powered microswimmers, and we offer a perspective on the state of the field, open questions, and opportunities. We hope that this review will serve as a guide to students beginning their work in this area and motivate others to consider research in microswimmers and acoustic fields.

Three-Dimensionally Complex Phase Behavior and Collective Phenomena in Mixtures of Acoustically Powered Chiral Microspinners.

The process of dynamic self-organization of small building blocks is fundamental to the emergent function of living systems and is characteristic of their out-of-equilibrium homeostasis. The ability to control the interactions of synthetic particles in large groups could lead to the realization of analogous macroscopic robotic systems with microscopic complexity. Rotationally induced self-organization has been observed in biological systems and modeled theoretically, but studies of fast, autonomously moving synthetic rotors remain rare. Here, we report switchable, out-of-equilibrium hydrodynamic assembly and phase separation in suspensions of acoustically powered chiral microspinners. Semiquantitative modeling suggests that three-dimensionally (3D) complex spinners interact through viscous and weakly inertial (streaming) flows. The interactions between spinners were studied over a range of densities to construct a phase diagram, which included gaseous dimer pairing at low density, collective rotation and multiphase separation at intermediate densities, and ultimately jamming at high density. The 3D chirality of the spinners leads to self-organization in parallel planes, forming a three-dimensionally hierarchical system that goes beyond the 2D systems that have so far been modeled computationally. Dense mixtures of spinners and passive tracer particles also show active-passive phase separation. These observations are consistent with recent theoretical predictions of the hydrodynamic coupling between rotlets generated by autonomous spinners and provide an exciting experimental window to the study of colloidal active matter and microrobotic systems.

Geometric and Scaling Effects in the Speed of Catalytic Enzyme Micropumps.

Self-powered, biocompatible pumps in the nanometer to micron length scale have the potential to enable technology in several fields, including chemical analysis and medical diagnostics. Chemically powered, catalytic micropumps have been developed but are not able to function well in biocompatible environments due to their intolerance of salt solutions and the use of toxic fuels. In contrast, enzymatically powered catalytic pumps offer good biocompatibility, selectivity, and scalability, but their performance at length scales below a few millimeters, which is important to many of their possible applications, has not been well tested. Here, urease-based enzyme pumps of millimeter and micrometer dimensions were fabricated and studied. The scaling of the pumping velocity was measured experimentally and simulated by numerical modeling. Pumping speeds were analyzed accurately by eliminating Brownian noise from the data using enzyme patches between 5 mm and 350 µm in size. Pumping speeds of microns per second could be achieved with urease pumps and were fastest when the channel height exceeded the width of the catalytic pump patch. In all cases, pumping was weak when the dimensions of the patch were 100 µm or less. Experimental and simulation results were consistent with a density-driven pumping mechanism at all sizes studied and served as a framework for the in silico study of more complex two-dimensional (2D) and three-dimensional (3D) geometries. Attempts to create directional flow by juxtaposing inward and outward pumps were unsuccessful because of the symmetry of convection rolls produced by millimeter-size pump patches and the slow speeds of smaller pumps. However, simulations of a corrugated ratchet structure showed that directional pumping could be achieved with pump patches in the millimeter size range.

Wafer-Scale Fabrication of Micro- to Nanoscale Bubble Swimmers and Their Fast Autonomous Propulsion by Ultrasound.

Fuel-free, biocompatible swimmers with dimensions smaller than one micrometer have the potential to revolutionize the way we study and manipulate microscopic systems. Sub-micrometer, metallic Janus particles can be propelled rapidly and autonomously by acoustically induced fluid streaming, but their operation at acoustic pressure nodes limits their utility. In contrast, bubble-based microswimmers have an "on board" resonant cavity that enables them to operate far from the source of acoustic power. So far, they have been fabricated by direct writing techniques that limit both their minimum dimensions and the number that can be produced. Consequently, the size scaling of the properties of bubble swimmers has not been explored experimentally. Additionally, 3D autonomous motion has not yet been demonstrated for this type of swimmer. We describe here a method for fabricating bubble swimmers in large numbers (>109) with sizes ranging from 5 µm to 500 nm without direct writing or photolithographic tools. These swimmers follow a previously proposed scaling theory and reveal useful phenomena that enable their propulsion in different modes in the same experiment: with magnetic steering, autonomously in 3D, and in frequency-specific autonomous modes. These interesting behaviors are relevant to possible applications of autonomously moving micro- and nanorobots.

2-Aminobenzenethiol-Functionalized Silver-Decorated Nanoporous Silicon Photoelectrodes for Selective CO2 Reduction.

A molecularly thin layer of 2-aminobenzenethiol (2-ABT) was adsorbed onto nanoporous p-type silicon (b-Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2-ABT alters the balance of the CO2 reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO2 to CO. The 2-ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X-ray photoelectron spectroscopy (XPS) of the 2-ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2-ABT via Ag-S bonds. Under visible light illumination, the onset potential for CO2 reduction was -50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2-ABT. The adsorption of 2-ABT lowers the overpotentials for both CO2 reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2-ABT is to anchor the NH2 group near the Ag surface, where it serves to bind CO2 and also to assist in proton transfer.

3D steerable, acoustically powered microswimmers for single-particle manipulation.

The ability to precisely maneuver micro/nano objects in fluids in a contactless, biocompatible manner can enable innovative technologies and may have far-reaching impact in fields such as biology, chemical engineering, and nanotechnology. Here, we report a design for acoustically powered bubble-based microswimmers that are capable of autonomous motion in three dimensions and selectively transporting individual synthetic colloids and mammalian cells in a crowded group without labeling, surface modification, or effect on nearby objects. In contrast to previously reported microswimmers, their motion does not require operation at acoustic pressure nodes, enabling propulsion at low power and far from an ultrasonic transducer. In a megahertz acoustic field, the microswimmers are subject to two predominant forces: the secondary Bjerknes force and a locally generated acoustic streaming propulsive force. The combination of these two forces enables the microswimmers to independently swim on three dimensional boundaries or in free space under magnetical steering.

Synthesis of the tricyclic indole alkaloids, dilemmaones A and B.

Dilemmaones A-C are naturally occurring tricyclic indole alkaloids possessing a unique hydroxymethylene or methoxymethylene substituent at the C2 position of the indole core and a C6-C7 fused cyclopentanone. Dilemmaone B has been prepared in 5 steps from 5-methylindan-1-one, and dilemmaone A has been prepared in 3 steps from a common precursor, 6-bromo-5-methyl-7-nitroindan-1-one. In both syntheses, key steps include a Kosugi-Migita-Stille cross coupling and a reductive cyclization using hydrogen gas and a transition metal catalyst.