Controlling the Speed of Light-Activated Colloids with a Constant, Uniform Magnetic Field.

It is demonstrated how the strength of activation for photocatalytic, self-propelled colloids can be enhanced with a constant, uniform magnetic field. When exposed to ultraviolet light and hydrogen peroxide, the titanium dioxide-based colloids become actively propelled. Due to the iron oxide core, a uniform field oriented perpendicular to the surface where motion takes place causes the asymmetrically shaped particles to rotate, which consequently leads to an increase in activity. The field-dependent dynamics of self-propulsion is quantified, and a qualitative description of how this effect arises is proposed. Since the application of the field is easily reversible, modulating the field on-and-off serves as a de facto "switch" that controls particle behavior.

Shape- and Material-Dependent Self-Propulsion of Photocatalytic Active Colloids, Interfacial Effects, and Dynamic Interparticle Interactions.

Active colloids powered by self-generated, local chemical concentration gradients exhibit dynamics that are a function of the particles' morphology and material properties. These characteristics also govern how the active colloids interact with surfaces, including other particles and nearby walls. Thus, by targeted design, the dynamic behavior, on average, can be engineered, despite a lack of "external" control such as an applied magnetic field. This allows for the development of new applications and the investigation of novel effects that arise when self-propelled active colloids have complex shapes and material composition. Here, we explore some of our recent work on this topic including the dynamics and interactions of photoactivated, self-propelled colloids with such multifaceted properties. We also delve into some special cases, such as a new variety of active particle-particle interaction that we recently developed, in which direct contact between the active colloids is forbidden, and the direction of propulsion for pairs of particles is correlated. The unifying theme of the work highlighted herein is the relationship between the physical, chemical, and material properties of active colloids and their motive behavior, the understanding of which opens up a wide range of new possibilities as we move toward the ultimate goal of realizing functional, man-made micro- and nanomachinery.

Shape-Dependent, Chiro-optical Response of UV-Active, Nanohelix Metamaterials.

We harness a synergy between morphology and the electromagnetic response of semiconducting material to engineer the chiro-optical properties of metamaterials that are active at ultraviolet (UV) wavelengths. Chiral metamaterials have recently ushered in new research directions in fundamental light-matter interactions, while simultaneously opening a range of promising photonics-based applications from polarization control to improved biosensing methods. Despite these recent advances, to date, very little attention has been focused upon engineered large UV-chiro-optical activity, where naturally occurring molecular optical activity bands are most typically encountered. Here, we systematically alter the morphology of titanium dioxide nanohelices, which make up the elements of the chiral metamaterials, to investigate how the nanoparticle shape affects chiro-optical activity across the UV spectrum. When the nanoscale critical dimensions fall within a particular size range, giant chiro-optical activity is observed, which is on the order of the strongest demonstrated in the UV to date and can be tuned by slight alterations of the nanohelices' morphology.

Light-Activated, Multi-Semiconductor Hybrid Microswimmers.

Using a dynamic fabrication process, hybrid, photoactivated microswimmers made from two different semiconductors, titanium dioxide (TiO2 ) and cuprous oxide (Cu2 O) are developed, where each material occupies a distinct portion of the multiconstituent particles. Structured light-activated microswimmers made from only TiO2 or Cu2 O are observed to be driven in hydrogen peroxide and water most vigorously under UV or blue light, respectively, whereas hybrid structures made from both of these materials exhibit wavelength-dependent modes of motion due to the disparate responses of each photocatalyst. It is also found that the hybrid particles are activated in water alone, a behavior which is not observed in those made from a single semiconductor, and thus, the system may open up a new class of fuel-free photoactive colloids that take advantage of semiconductor heterojunctions. The TiO2 /Cu2 O hybrid microswimmer presented here is but an example of a broader method for inducing different modes of motion in a single light-activated particle, which is not limited to the specific geometries and materials presented in this study.

Active Nanorheology with Plasmonics.

Nanoplasmonic systems are valued for their strong optical response and their small size. Most plasmonic sensors and systems to date have been rigid and passive. However, rendering these structures dynamic opens new possibilities for applications. Here we demonstrate that dynamic plasmonic nanoparticles can be used as mechanical sensors to selectively probe the rheological properties of a fluid in situ at the nanoscale and in microscopic volumes. We fabricate chiral magneto-plasmonic nanocolloids that can be actuated by an external magnetic field, which in turn allows for the direct and fast modulation of their distinct optical response. The method is robust and allows nanorheological measurements with a mechanical sensitivity of ∼0.1 cP, even in strongly absorbing fluids with an optical density of up to OD ∼ 3 (∼0.1% light transmittance) and in the presence of scatterers (e.g., 50% v/v red blood cells).

Rotational Analysis of Spherical, Optically Anisotropic Janus Particles by Dynamic Microscopy.

We analyze the rotational dynamics of spherical colloidal Janus particles made from silica (SiO2) with a hemispherical gold/palladium (Au/Pd) cap. Since the refractive index difference between the surrounding fluid and a two-faced, optically anisotropic Janus microsphere is a function of the particle's orientation, it is possible to observe its rotational dynamics with bright-field optical microscopy. We investigate rotational diffusion and constant rotation of single Janus microspheres which are partially tethered to a solid surface so they are free to rotate but show little or no translational motion. Also, since the metal cap is a powerful catalyst in the breakdown of hydrogen peroxide, H2O2, the particles can be activated chemically. In this case, we analyze the motion of coupled Janus dimers which undergo a stable rotary motion about a mutual center. The analysis of both experimental and simulation data, which are microscopy and computer-generated videos, respectively, is based upon individual particle tracking and differential dynamic microscopy (DDM). DDM, which typically requires ensemble averages to extract meaningful information for colloidal dynamics, can be effective in certain situations for systems consisting of single entities. In particular, when translational motion is suppressed, both rotational diffusion and constant rotation can be probed.

Self-propelling nanomotors in the presence of strong Brownian forces.

Motility in living systems is due to an array of complex molecular nanomotors that are essential for the function and survival of cells. These protein nanomotors operate not only despite of but also because of stochastic forces. Artificial means of realizing motility rely on local concentration or temperature gradients that are established across a particle, resulting in slip velocities at the particle surface and thus motion of the particle relative to the fluid. However, it remains unclear if these artificial motors can function at the smallest of scales, where Brownian motion dominates and no actively propelled living organisms can be found. Recently, the first reports have appeared suggesting that the swimming mechanisms of artificial structures may also apply to enzymes that are catalytically active. Here we report a scheme to realize artificial Janus nanoparticles (JNPs) with an overall size that is comparable to that of some enzymes ∼30 nm. Our JNPs can catalyze the decomposition of hydrogen peroxide to water and oxygen and thus actively move by self-electrophoresis. Geometric anisotropy of the Pt-Au Janus nanoparticles permits the simultaneous observation of their translational and rotational motion by dynamic light scattering. While their dynamics is strongly influenced by Brownian rotation, the artificial Janus nanomotors show bursts of linear ballistic motion resulting in enhanced diffusion.

Hybrid nanocolloids with programmed three-dimensional shape and material composition.

Tuning the optical, electromagnetic and mechanical properties of a material requires simultaneous control over its composition and shape. This is particularly challenging for complex structures at the nanoscale because surface-energy minimization generally causes small structures to be highly symmetric. Here we combine low-temperature shadow deposition with nanoscale patterning to realize nanocolloids with anisotropic three-dimensional shapes, feature sizes down to 20 nm and a wide choice of materials. We demonstrate the versatility of the fabrication scheme by growing three-dimensional hybrid nanostructures that contain several functional materials with the lowest possible symmetry, and by fabricating hundreds of billions of plasmonic nanohelices, which we use as chiral metafluids with record circular dichroism and tunable chiroptical properties.

Shape control in wafer-based aperiodic 3D nanostructures.

Controlled local fabrication of three-dimensional (3D) nanostructures is important to explore and enhance the function of single nanodevices, but is experimentally challenging. We present a scheme based on e-beam lithography (EBL) written seeds, and glancing angle deposition (GLAD) grown structures to create nanoscale objects with defined shapes but in aperiodic arrangements. By using a continuous sacrificial corral surrounding the features of interest we grow isolated 3D nanostructures that have complex cross-sections and sidewall morphology that are surrounded by zones of clean substrate.

Chiral colloidal molecules and observation of the propeller effect.

Chiral molecules play an important role in biological and chemical processes, but physical effects due to their symmetry-breaking are generally weak. Several physical chiral separation schemes which could potentially be useful, including the propeller effect, have therefore not yet been demonstrated at the molecular scale. However, it has been proposed that complex nonspherical colloidal particles could act as "colloidal molecules" in mesoscopic model systems to permit the visualization of molecular phenomena that are otherwise difficult to observe. Unfortunately, it is difficult to synthesize such colloids because surface minimization generally favors the growth of symmetric particles. Here we demonstrate the production of large numbers of complex colloids with glancing angle physical vapor deposition. We use chiral colloids to demonstrate the Baranova and Zel'dovich (Baranova, N. B.; and Zel'dovich, B. Y. Chem. Phys. Lett. 1978, 57, 435) propeller effect: the separation of a racemic mixture by application of a rotating field that couples to the dipole moment of the enantiomers and screw propels them in opposite directions. The handedness of the colloidal suspensions is monitored with circular differential light scattering. An exact solution for the colloid's propulsion is derived, and comparisons between the colloidal system and the corresponding effect at the molecular scale are made.

Self-organized multiconstituent catalytic nanomotors.

Self-organized catalytic nanomotors consisting of more than one individual component are presented. Tadpole-like catalytic nanomotors fabricated by dynamic shadowing growth (DSG) self-organize randomly to form two-nanomotor clusters (approximately 1-3% yield) that spin as opposed to circular motion exhibited by the individual structures. By introducing magnetic materials to another system, self-assembled "helicopter" nanomotors consisting of a V-shaped nanomotor and a microbead are formed with approximately 25% yield, showing a significantly higher yield than the control (0%). A flexible swimmer system that performs complex swimming, such as maneuvering around stationary objects, is also presented. These nanomotor systems are inherently more complex than those previously studied and may be the next step towards building sophisticated multifunctional nanomachinery systems.

Material-dependent performance of fuel-free, light-activated, self-propelling colloids.

Self-propelling, light-activated colloidal particles can be actuated in water alone. Here we study the effect of adding different amounts of a gold/palladium alloy to titanium dioxide-based, active colloids. We observe a correlation between alloy-thickness and the average speed of the particles, and we discover an intermediate thickness leads to the highest activity for this system. We argue that a non-continuous thin-film of the co-catalyst improves the efficiency of water-splitting at the surface of the particles, and in-turn, the performance of "fuel-free" self-propulsion.

Self-Phoretic Microswimmers Propel at Speeds Dependent upon an Adjacent Surface's Physicochemical Properties.

Self-phoretic colloids are emerging as critical components of programmable nano- and microscale active matter and may usher in a new area of complex, small-scale machinery. To date, most studies have focused upon active particles confined by gravity to a plane located just above a solid/liquid interface. Despite this ubiquity, little attention has been directed at how the physicochemical qualities of this interface might affect motion. Here, we show that both the chemical and physical properties of the solid, above which motion takes place, significantly influence the behavior of particles propelled by self-generated concentration gradients. More specifically, titania/silica (TiO2/SiO2) photoactive microswimmers move faster when the local osmotic flow over the stationary solid is diminished, which we demonstrate by reducing the magnitude of the surface's zeta potential or by increasing surface roughness. Our results suggest that consideration of surface properties is crucial for modeling self-phoretic active matter while simultaneously offering a new avenue for engineering the kinematic behavior of such systems.

Shape-Dependent Motion of Structured Photoactive Microswimmers.

We investigate the dynamics of structured photoactive microswimmers and show that morphology sensitively determines the swimming behavior. Particular to this study, a major portion of the light-activated particles' underlying structure is built from a photocatalytic material, made possible by dynamic physical vapor deposition (DPVD). We find that swimmers of this type exhibit unique shape-dependent autonomous swimming that is distinct from what is seen in systems with similar structural morphology but not fabricated directly from the catalyst. Notably, the direction of motion is a function of these parameters. Because the swimming behavior is strongly correlated with particle shape and material composition, DPVD allows for engineering small-scale propulsion by adjusting the fabrication parameters to match the desired performance.

Engineering Contactless Particle-Particle Interactions in Active Microswimmers.

Artificial self-propelled colloidal particles have recently served as effective building blocks for investigating many dynamic behaviors exhibited by nonequilibrium systems. However, most studies have relied upon excluded volume interactions between the active particles. Experimental systems in which the mobile entities interact over long distances in a well-defined and controllable manner are valuable so that new modes of multiparticle dynamics can be studied systematically in the laboratory. Here, a system of self-propelled microscale Janus particles is engineered to have contactless particle-particle interactions that lead to long-range attraction, short-range repulsion, and mutual alignment between adjacent swimmers. The unique modes of motion that arise can be tuned by modulating the system's parameters.

Dynamic stabilization of Janus sphere trans-dimers.

We experimentally investigated the self-assembly of chemically active colloidal Janus spheres into dimers. The trans-dimer conformation, in which the two active sites are oriented roughly in opposite directions and the particles are osculated at their equators, becomes dominant as the hydrogen peroxide fuel concentration increases. Our observations suggest high spinning frequency combined with little translational motion is at least partially responsible for the stabilization of the trans-dimer as activity increases.

Spiral diffusion of rotating self-propellers with stochastic perturbation.

Translationally diffusive behavior arising from the combination of orientational diffusion and powered motion at microscopic scales is a known phenomenon, but the peculiarities of the evolution of expected position conditioned on initial position and orientation have been neglected. A theory is given of the spiral motion of the mean trajectory depending upon propulsion speed, angular velocity, orientational diffusion, and rate of random chirality reversal. We demonstrate the experimental accessibility of this effect using both tadpole-like and Janus sphere dimer rotating motors. Sensitivity of the mean trajectory to the kinematic parameters suggest that it may be a useful way to determine those parameters.

Surface roughness-induced speed increase for active Janus micromotors.

We demonstrate a simple physical fabrication method to control surface roughness of Janus micromotors and fabricate self-propelled active Janus microparticles with rough catalytic platinum surfaces that show a four-fold increase in their propulsion speed compared to conventional Janus particles coated with a smooth Pt layer.

Nanohelices by shadow growth.

The helix has remarkable qualities and is prevalent in many fields including mathematics, physics, chemistry, and biology. This shape, which is chiral by nature, is ubiquitous in biology with perhaps the most famous example being DNA. Other naturally occurring helices are common at the nanoscale in the form of protein secondary structures and in various macromolecules. Nanoscale helices exhibit a wide range of interesting mechanical, optical, and electrical properties which can be intentionally engineered into the structure by choosing the correct morphology and material. As technology advances, these fabrication parameters can be fine-tuned and matched to the application of interest. Herein, we focus on the fabrication and properties of nanohelices grown by a dynamic shadowing growth method combined with fast wafer-scale substrate patterning which has a number of distinct advantages. We review the fabrication methodology and provide several examples that illustrate the generality and utility of nanohelices shadow-grown on nanopatterns.

Nanopropellers and their actuation in complex viscoelastic media.

Tissue and biological fluids are complex viscoelastic media with a nanoporous macromolecular structure. Here, we demonstrate that helical nanopropellers can be controllably steered through such a biological gel. The screw-propellers have a filament diameter of about 70 nm and are smaller than previously reported nanopropellers as well as any swimming microorganism. We show that the nanoscrews will move through high-viscosity solutions with comparable velocities to that of larger micropropellers, even though they are so small that Brownian forces suppress their actuation in pure water. When actuated in viscoelastic hyaluronan gels, the nanopropellers appear to have a significant advantage, as they are of the same size range as the gel's mesh size. Whereas larger helices will show very low or negligible propulsion in hyaluronan solutions, the nanoscrews actually display significantly enhanced propulsion velocities that exceed the highest measured speeds in Newtonian fluids. The nanopropellers are not only promising for applications in the extracellular environment but small enough to be taken up by cells.