Biohybrid and Bioinspired Magnetic Microswimmers

Many motile microorganisms swim and navigate in chemically and mechanically complex environments. These organisms can be functionalized and directly used for applications (biohybrid approach), but also inspire designs for fully synthetic microbots. The most promising designs of biohybrids and bioinspired microswimmers include one or several magnetic components, which lead to sustainable propulsion mechanisms and external controllability. This Review addresses such magnetic microswimmers, which are often studied in view of certain applications, mostly in the biomedical area, but also in the environmental field. First, propulsion systems at the microscale are reviewed and the magnetism of microswimmers is introduced. The review of the magnetic biohybrids and bioinspired microswimmers is structured gradually from mostly biological systems toward purely synthetic approaches. Finally, currently less explored parts of this field ranging from in situ imaging to swarm control are discussed.     

Confined Bubble‐Propelled Microswimmers in Capillaries: Wall Effect,Fuel Deprivation,and Exhaust Product Excess

Self‐propelled autonomous nano/microswimmers are at the forefront of materials science. These swimmers are expected to operate in highly confined environments, such as between the grains of soil or in the capillaries of the human organism. To date, little attention is paid to the problem that in such a confined environment the fuel powering catalytic nano/microswimmers can be exhausted quickly and the space can be polluted with the product of the catalytic reaction. In addition, the motion of the nano/microswimmers may be influenced by the confinement. These issues are addressed here, showing the influence of the size of the capillary and length of the micromotor on the motion and the influence of the depletion of the fuel and excess of the exhaust products. Theoretical modeling is provided as well to bring further insight into the observations. This article shows challenges that these systems face and stimulates research to overcome them.     

Magnetically Powered Shape‐Transformable Liquid Metal Micromotors

Shape‐transformable liquid metal (LM) micromachines have attracted the attention of the scientific community over the past 5 years, but the inconvenience of transfer routes and the use of corrosive fuels have limited their potential applications. In this work, a shape‐transformable LM micromotor that is fabricated by a simple, versatile ice‐assisted transfer printing method is demonstrated, in which an ice layer is employed as a “sacrificial” substrate that can enable the direct transfer of LM micromotors to arbitrary target substrates conveniently. The resulting LM microswimmers display efficient propulsion of over 60 µm s^?1 (≈3 bodylength s^?1) under elliptically polarized magnetic fields, comparable to that of the common magnetic micro/nanomotors with rigid bodies. Moreover, these LM micromotors can undergo dramatic morphological transformation in an aqueous environment under the irradiation of an alternating magnetic field. The ability to transform the shape and efficiently propel LM microswimmers holds great promise for chemical sensing, controlled cargo transport, materials science, and even artificial intelligence in ways that are not possible with rigid‐bodies microrobots.     

Magnetically Powered Annelid‐Worm‐Like Microswimmers

A bioinspired magnetically powered microswimmer is designed and experimentally demonstrated by mimicking the morphology of annelid worms. The structural parameters of the microswimmer, such as the surface wrinkling, can be controlled by applying prestrain on substrate for the precise fabrication and consistent performance of the microswimmers. The resulting annelid‐worm‐like microswimmers display efficient propulsion under an oscillating magnetic field, reaching a peak speed of ≈100 µm s^?1. The speed and directionality of the microswimmer can be readily controlled by changing the parameters of the field inputs. Additionally, it is demonstrated that the microswimmers are able to transport microparticles toward a predefined destination, although the translation velocity is inevitably reduced due to the additional hydrodynamic resistance of the microparticles. These annelid‐worm‐like microswimmers have excellent mobility, good maneuverability, and strong transport capacity, and they hold considerable promise for diverse biomedical, chemical sensing, and environmental applications.     

Bio‐Hybrid Cell‐Based Actuators for Microsystems

As we move towards the miniaturization of devices to perform tasks at the nano and microscale, it has become increasingly important to develop new methods for actuation, sensing, and control. Over the past decade, bio‐hybrid methods have been investigated as a promising new approach to overcome the challenges of scaling down robotic and other functional devices. These methods integrate biological cells with artificial components and therefore, can take advantage of the intrinsic actuation and sensing functionalities of biological cells. Here, the recent advancements in bio‐hybrid actuation are reviewed, and the challenges associated with the design, fabrication, and control of bio‐hybrid microsystems are discussed. As a case study, focus is put on the development of bacteria‐driven microswimmers, which has been investigated as a targeted drug delivery carrier. Finally, a future outlook for the development of these systems is provided. The continued integration of biological and artificial components is envisioned to enable the performance of tasks at a smaller and smaller scale in the future, leading to the parallel and distributed operation of functional systems at the microscale.     

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 (Cu₂O) are developed, where each material occupies a distinct portion of the multiconstituent particles. Structured light‐activated microswimmers made from only TiO₂ or Cu₂O 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/Cu₂O 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.     

Autonomous Biohybrid Urchin‐Like Microperforator for Intracellular Payload Delivery

A magnetic urchin‐like microswimmer based on sunflower pollen grain (SPG) that can pierce the cancer cell membrane and actively deliver therapeutic drugs is reported. These drug loaded microperforators are fabricated on a large scale by sequentially treating the natural SPGs with acidolysis, sputtering, and vacuum loading. The microswimmers exhibit precise autonomous navigation and obstacle avoidance in complex environments via association with artificial intelligence. Assemblies of microswimmers can further enhance individual motion performance and adaptability to complicated environments. Additionally, the experimental results demonstrate that microswimmers with nanospikes can accomplish single‐cell perforation for direct delivery under an external rotating magnetic field. Drugs encapsulated in the inner cavity of the microperforators can be accurately delivered to a specific site via remote control. These dual‐action microswimmers demonstrate good biocompatibility, high intelligence, precision in single‐cell targeting, and sufficient drug loading, presenting a promising avenue for many varieties of biomedical applications.     

Reinforcement in Al Matrix Composites: A Review of Strengthening Behavior of Nano‐Sized Particles

Aluminum matrix composites (AMCs) reinforced with the nano‐sized particles are very important materials for the applications in industrial fields. These aluminum matrix composites consist of an aluminum matrix and nano‐sized particles, which own very different physical and mechanical properties from those of the matrix. Nano‐sized particles show a more obvious strengthening effect on the matrix than the micro‐sized particles do, because of the high specific surface area which is positive for the pinning effect during the deformation process. Thus, the nano‐sized particle‐reinforced AMCs usually exhibit a good ductility. The main issues of the fabrication methods are the low wettability between the nano‐sized particles and the molten aluminum alloys, which is fatal to the conventional casting methods, and the agglomeration of nano‐sized particles which happened easier than the larger particles. Several alternative processes have been presented in literature for the production of the nano‐sized particle‐reinforced aluminum composites. This paper is aimed at reviewing the feasible manufacturing techniques used for the fabrication of nano‐sized particle‐reinforced aluminum composites. More importantly, the strengthening mechanisms and models which are responsible for the improvement of mechanical properties of the nano‐sized particle‐reinforced aluminum composites have been reviewed.

     

3D DNA Origami Crystals

3D crystals assembled entirely from DNA provide a route to design materials on a molecular level and to arrange guest particles in predefined lattices. This requires design schemes that provide high rigidity and sufficiently large open guest space. A DNA‐origami‐based “tensegrity triangle” structure that assembles into a 3D rhombohedral crystalline lattice with an open structure in which 90% of the volume is empty space is presented here. Site‐specific placement of gold nanoparticles within the lattice demonstrates that these crystals are spacious enough to efficiently host 20 nm particles in a cavity size of 1.83 × 10⁵ nm³, which would also suffice to accommodate ribosome‐sized macromolecules. The accurate assembly of the DNA origami lattice itself, as well as the precise incorporation of gold particles, is validated by electron microscopy and small‐angle X‐ray scattering experiments. The results show that it is possible to create DNA building blocks that assemble into lattices with customized geometry. Site‐specific hosting of nano objects in the optically transparent DNA lattice sets the stage for metamaterial and structural biology applications.     

3D Fabrication of Fully Iron Magnetic Microrobots

Biocompatibility and high responsiveness to magnetic fields are fundamental requisites to translate magnetic small‐scale robots into clinical applications. The magnetic element iron exhibits the highest saturation magnetization and magnetic susceptibility while exhibiting excellent biocompatibility characteristics. Here, a process to reliably fabricate iron microrobots by means of template‐assisted electrodeposition in 3D‐printed micromolds is presented. The 3D molds are fabricated using a modified two‐photon absorption configuration, which overcomes previous limitations such as the use of transparent substrates, low writing speeds, and limited depth of field. By optimizing the geometrical parameters of the 3D molds, metallic structures with complex features can be fabricated. Fe microrollers and microswimmers are realized that demonstrate motion at ≈20 body lengths per second, perform 3D motion in viscous environments, and overcome higher flow velocities than those of “conventional 3D printed helical microswimmers.” The cytotoxicity of these microrobots is assessed by culturing them with human colorectal cancer (HCT116) cells for four days, demonstrating their good biocompatibility characteristics. Finally, preliminary results regarding the degradation of iron structures in simulated gastric acid liquid are provided.     

Anisotropic Excitation Polarization Response from a Single White Light‐Emitting β‐NaYF4:Yb3+,Pr3+ Microcrystal

Precise knowledge about optical and structural performance of individual rare earth (RE)‐doped particles is extremely important for the optimization of luminescent particles and for fully exploiting their capability as multifunctional probes for interdisciplinary applications. In this work, optical and structural anisotropy of individual particles through RE‐doped single fluoride microcrystals with controllable morphology is reported. Unique luminescent phenomena, for example, white light‐emission from Pr³⁺ at single particle level and different photoluminescent spectra variation dependence on excitation polarization orientation at different excitation direction are observed upon excitation with a 980 nm linearly polarized laser. Based on the analysis of local site symmetry and electron cloud distribution of REs in hexagonal structure by density functional theory calculations, an exciting mechanism of excitation polarization response anisotropy is given for the first time, providing a guidance for emission polarization simultaneously. The structural anisotropy is presented in Raman spectra with obvious differing Raman curves, revealing the reason why there are differences between powder groups. Taking advantage of anisotropic crystals, potential applications in microscopic multi‐information transportation are suggested for the optical and structural performance anisotropy from RE‐doped fluoride single nano/microcrystals to ordered nano/microcrystal arrays, such as local rate probing in a flowing liquid.     

Utilizing Iron's Attractive Chemical and Magnetic Properties in Microrocket Design,Extended Motion,and Unique Performance

All‐in‐one material for microrocket propulsion featuring acid‐based bubble generation and magnetic guidance is presented. Electrochemically deposited iron serves as both a propellant, toward highly efficient self‐propulsion in acidic environments, and as a magnetic component enabling complete motion control. The new microrockets display longer lifetime and higher propulsion efficiency compared to previously reported active metal zinc‐based microrockets due to the chemical properties of iron and the unique structure of the microrockets. These iron‐based microrockets also demonstrate unique and attractive cargo towing and autonomous release capabilities. The latter is realized upon loss of the magnetic properties due to acid‐driven iron dissolution. More interestingly, these bubble‐propelled microrockets assemble via magnetic interactions into a variety of complex configurations and train structures, which enrich the behavior of micromachines. Modeling of the magnetic forces during the microrocket assembly and cargo capture confirms these unique experimentally observed assembly and cargo‐towing behaviors. These findings provide a new concept of blending propellant and magnetic components into one, toward simplifying the design and fabrication of artificial micro/nanomachines, realizing new functions and capabilities for a variety of future applications.     

A Liquid‐Metal–Elastomer Nanocomposite for Stretchable Dielectric Materials

Stretchable high‐dielectric‐constant materials are crucial for electronic applications in emerging domains such as wearable computing and soft robotics. While previous efforts have shown promising materials architectures in the form of dielectric nano‐/microinclusions embedded in stretchable matrices, the limited mechanical compliance of these materials significantly limits their practical application as soft energy‐harvesting/storage transducers and actuators. Here, a class of liquid metal (LM)–elastomer nanocomposites is presented with elastic and dielectric properties that make them uniquely suited for applications in soft‐matter engineering. In particular, the role of droplet size is examined and it is found that embedding an elastomer with a polydisperse distribution of nanoscale LM inclusions can enhance its electrical permittivity without significantly degrading its elastic compliance, stretchability, or dielectric breakdown strength. In contrast, elastomers embedded with microscale droplets exhibit similar improvements in permittivity but a dramatic reduction in breakdown strength. The unique enabling properties and practicality of LM–elastomer nanocomposites for use in soft machines and electronics is demonstrated through enhancements in performance of a dielectric elastomer actuator and energy‐harvesting transducer.     

Vesicle‐Mediated Growth of Tubular Branches and Centimeter‐Long Microtubes from a Single Molecule

The mechanism by which small molecules assemble into microscale tubular structures in aqueous solution remains poorly understood, particularly when the initial building blocks are non‐amphiphilic molecules and no surfactant is used. It is here shown how a subnanometric molecule, namely p‐aminothiophenol (p‐ATP), prepared in normal water with a small amount of ethanol, spontaneously assembles into a new class of nanovesicle. Due to Brownian motion, these nanostructures rapidly grow into micrometric vesicles and start budding to yield macroscale tubular branches with a remarkable growth rate of ～20 μm s^?1. A real‐time visualization by optical microscopy reveals that tubular growth proceeds by vesicle walk and fusion on the apex (growth cone) and sides of the branches and ultimately leads to the generation of centimeter‐long microtubes. This unprecedented growth mechanism is triggered by a pH‐activated proton switch and maintained by hydrogen bonding. The vesicle fusion‐mediated synthesis suggests that functional microtubes with biological properties can be efficiently prepared with a mixture of appropriate diaminophenyl blocks and the desired macromolecule. The reversibility, timescale, and very high yield (90%) of this synthetic approach make it a valuable model for the investigation of hierarchical and structural transition between organized assemblies with different size scales and morphologies.     

A Representative volume model for a CNT composite material

The concept of a ‘Representative Volume Model’ is used in combination with ‘Equivalent Mechanical Strain’ or Aboudi's ‘Average Strain’ theorem to illustrate how a carbon nanotube reinforced composite material constitutive law for a nano‐composite material can be implemented into a finite element program for modeling structural applications. Current methods of modeling each individual composite layer to build up an element composed of carbon nanotube reinforced composite material may not be the best approach for modeling structural applications of this composite. The approach presented here is based upon presentations given at the National Science Foundation‐Civil and Mechanical Systems division workshop at John Hopkins University in 2004, which is referred to in this paper as the Williams‐Baxter approach. This approach is also used to demonstrate that damage modeling can be included as was suggested in this workshop. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

A Facile Method to Fabricate Anisotropic Hydrogels with Perfectly Aligned Hierarchical Fibrous Structures

Natural structural materials (such as tendons and ligaments) are comprised of multiscale hierarchical architectures, with dimensions ranging from nano‐ to macroscale, which are difficult to mimic synthetically. Here a bioinspired, facile method to fabricate anisotropic hydrogels with perfectly aligned multiscale hierarchical fibrous structures similar to those of tendons and ligaments is reported. The method includes drying a diluted physical hydrogel in air by confining its length direction. During this process, sufficiently high tensile stress is built along the length direction to align the polymer chains and multiscale fibrous structures (from nano‐ to submicro‐ to microscale) are spontaneously formed in the bulk material, which are well‐retained in the reswollen gel. The method is useful for relatively rigid polymers (such as alginate and cellulose), which are susceptible to mechanical signal. By controlling the drying with or without prestretching, the degree of alignment, size of superstructures, and the strength of supramolecular interactions can be tuned, which sensitively influence the strength and toughness of the hydrogels. The mechanical properties are comparable with those of natural ligaments. This study provides a general strategy for designing hydrogels with highly ordered hierarchical structures, which opens routes for the development of many functional biomimetic materials for biomedical applications.     

Molecular Imprinted BiVO4 Microswimmers for Selective Target Recognition and Removal

Analogous to photosynthetic systems, photoactive semiconductor-based micro/nanoswimmers display biomimetic features that enable unique light harvesting and energy conversion functions and interactions with their surroundings. However, these artificial swimmers are usually non-selective and provide ineffective target recognition, resulting in poor surface analyte binding that affects the overall reactivity and motion efficiency. Here, the surface engineering of light-driven BiVO₄ microswimmers by molecular imprinting polymerization is presented. After embedding surface recognition sites, the modified microswimmers can self-propel in a solution of a target molecule, without requiring toxic fuels, and degrade the target selectively in a pollutant mixture. These findings show that optimizing the design of semiconductor-based microswimmers with specific target recognition cavities on their surface is a promising strategy to achieve selective capture and degradation of organic pollutants, which is otherwise impossible because of the non-selective behavior of photogenerated reactive radicals. Moreover, this study provides a unique strategy to enhance the motion capabilities of single-component photocatalytic microswimmers in a specific chemical environment.     

Bioinspired Photonic Pigments from Colloidal Self‐Assembly

The natural world is a colorful environment. Stunning displays of coloration have evolved throughout nature to optimize camouflage, warning, and communication. The resulting flamboyant visual effects and remarkable dynamic properties, often caused by an intricate structural design at the nano‐ and microscale, continue to inspire scientists to unravel the underlying physics and to recreate the observed effects. Here, the methodologies to create bioinspired photonic pigments using colloidal self‐assembly approaches are considered. The physics governing the interaction of light with structural features and natural examples of structural coloration are briefly introduced. It is then outlined how the self‐assembly of colloidal particles, acting as wavelength‐scale building blocks, can be particularly useful to replicate coloration from nature. Different coloration effects that result from the defined structure of the self‐assembled colloids are introduced and it is highlighted how these optical properties can be translated into photonic pigments by modifications of the assembly processes. The importance of absorbing elements, as well as the role of surface chemistry and wettability to control structural coloration is discussed. Finally, approaches to integrate dynamic control of coloration into such self‐assembled photonic pigments are outlined.     

High‐Entropy Alloy (HEA)‐Coated Nanolattice Structures and Their Mechanical Properties

Nanolattice structure fabricated by two‐photon lithography (TPL) is a coupling of size‐dependent mechanical properties at micro/nano‐scale with structural geometry responses in wide applications of scalable micro/nano‐manufacturing. In this work, three‐dimensional (3D) polymeric nanolattices are initially fabricated using TPL, then conformably coated with an 80 nm thick high‐entropy alloy (HEA) thin film (CoCrFeNiAl_0.3) via physical vapor deposition (PVD). 3D atomic‐probe tomography (APT) reveals the homogeneous element distribution in the synthesized HEA film deposited on the substrate. Mechanical properties of the obtained composite architectures are investigated via in situ scanning electron microscope (SEM) compression test, as well as finite element method (FEM) at the relevant length scales. The presented HEA‐coated nanolattice encouragingly not only exhibits superior compressive specific strength of ≈0.032 MPa kg^?1 m³ with density well below 1000 kg m^?3, but also shows good compression ductility due to its composite nature. This concept of combining HEA with polymer lattice structures demonstrates the potential of fabricating novel architected metamaterials with tunable mechanical properties.