Nano/Microrobots Meet Electrochemistry

Artificial autonomous self‐propelled nano and microrobots are an important part of contemporary technology. They are typically self‐powered, taking chemical energy from their environment and converting it to motion. They can move in complex environments and channels, deliver cargo, perform nanosurgery, act as chemotaxis and perform sense‐and‐act actions. The electrochemistry is closely interwoven within this field. In the case of self‐electrophoretically driven nano/microrobots, electrochemical mechanism has been the basis of power, which translates chemical energy to motion. Electrochemistry is also a major tool for the fabrication of these micro and nanodevices. Electrochemistry and electric fields can be used for the directing of nanorobots and for detection of their positions. Ultimately, nano and microrobots can dramatically improve performances of electrochemical sensors and biosensors, as well as of the energy generating devices. Here, all aspects in the fundamentals and applications of electrochemistry in the realm of nano‐ and microrobots are reviewed.     

Triangular Elastomeric Stamps for Optical Applications: Near‐Field Phase Shift Photolithography, 3D Proximity Field Patterning,Embossed Antireflective Coatings,and SERS Sensing

The use of a decal transfer lithography technique to fabricate elastomeric stamps with triangular cross‐sections, specifically triangular prisms and cones, is described. These stamps are used in demonstrations for several prototypical optical applications, including the fabrication of multiheight 3D photoresist patterns with near zero‐width features using near‐field phase shift lithography, fabrication of periodic porous polymer structures by maskless proximity field nanopatterning, embossing thin‐film antireflection coatings for improved device performance, and efficient fabrication of substrates for surface‐enhanced Raman spectroscopic sensing. The applications illustrate the utility of the triangular poly(dimethylsiloxane) decals for a wide variety of optics‐centric applications, particularly those that exploit the ability of the designed geometries and materials combinations to manipulate light–matter interactions in a predictable and controllable manner.     

A Hybrid Carrier System Based on Origami Nanostrucutures and Layer‐by‐Layer Microparticles

Recent progress in DNA nanotechnology allows the fabrication of 3D structures that can be loaded with a large variety of molecular cargos and even be responsive to external stimuli. This makes the use of DNA nanostructures a promising approach for applications in nanomedicine and drug delivery. However, their low stability in the extra‐ and intracellular environment as well as low cellular uptake rates and release rates from endosomes into the cytoplasm hamper the efficient and targeted use of DNA nanostructures in medical applications. Here, such major obstacles are overcome by integrating DNA origami nanostructures into superordinated layer‐by‐layer based microparticles made from biopolymers. The modular assembly of the polymer layer allows a high‐density incorporation of the DNA structures at different depth. This enables controllable protection of the DNA nanostructures over extended durations in a broad range of extra‐ and intracellular conditions without compromising the cell viability. Furthermore, by producing protein‐complexed DNA nanostructures it is demonstrated that molecular cargo can be conveniently integrated into the developed hybrid system. This work provides the basis for a new multistage carrier system allowing for an efficient and protected transport of active agents inside responsive DNA nanostructures.     

Ferrofluid Droplets as Liquid Microrobots with Multiple Deformabilities

Developing microrobots with multiple deformabilities has become extremely challenging due to the lack of materials that are soft enough at the microscale level and the inability to be reconfigured after fabrication. In this study, it is aimed to prove that liquid microrobots composed of ferrofluid droplets are inherently deformable and they can be controlled, individually or in aggregate, with multiple programmable deformabilities. For example, the liquid‐microrobot monomer (LRM) can pass through narrow channels via elongation and achieve scaling via splitting and coalescence. LRMs can also reassemble into various kinds of functional liquid‐robot aggregates, such as microsticks, micropies, microtrains, microkayaks, and microrollingpins. Thus, they can respond to multi‐terrain surfaces or perform various complex tasks. Moreover, the authors' physics‐based theoretical model demonstrates dynamic self‐assembly and group behavior of a multiple LRM system, which is conducive to investigating the mechanisms behind it. These ferrofluid droplet robots provide novel solutions for some potential applications, such as untethered micromanipulation and targeted cargo delivery.     

Magnetic Actuation Methods in Bio/Soft Robotics

In recent years, magnetism has gained an enormous amount of interest among researchers for actuating different sizes and types of bio/soft robots, which can be via an electromagnetic-coil system, or a system of moving permanent magnets. Different actuation strategies are used in robots with magnetic actuation having a number of advantages in possible realization of microscale robots such as bioinspired microrobots, tetherless microrobots, cellular microrobots, or even normal size soft robots such as electromagnetic soft robots and medical robots. This review provides a summary of recent research in magnetically actuated bio/soft robots, discussing fabrication processes and actuation methods together with relevant applications in biomedical area and discusses future prospects of this way of actuation for possible improvements in performance of different types of bio/soft robots.     

Rotibot: Use of Rotifers as Self‐Propelling Biohybrid Microcleaners

Self‐propelled biohybrid microrobots, employing marine rotifers as their engine, named “rotibot,” are presented and their practical utility and advantages for environmental remediation are demonstrated. Functionalized microbeads are attached electrostatically within the rotifer mouth and aggregated inside their inner lip. The high fluid flow toward the mouth, generated by the strokes of rotifer cilia bands, forces an extremely efficient transport of the contaminated sample over the active surfaces of the functionalized microbeads. The reactive particles confined around the rotifer's lip are thus exposed to a high flow rate of the pollutant solution, resulting in dramatically accelerated decontamination processes, without external mixing or harmful fuels. Theoretical simulations, modeling the greatly enhanced fluid dynamic associated with such built‐in mixing effect, correlate well with the experimental observations. The rotibot thus proves to be an effective, versatile, and robust dynamic microcleaning platform for removing diverse environmental pollutants. Microbeads functionalized with lysozyme and organophosphorus hydrolase enzymes are shown to be extremely useful for enzymatic biodegradation of Escherichia coli and the nerve agent methyl paraoxon, respectively, while ligand (meso‐2,3‐dimercaptosuccinic acid) modified beads are used for removing heavy metal contaminants. Rotifer‐based biohybrid microrobots hold considerable promise as self‐propelling dynamic pumps for diverse large‐scale environmental remediation applications.     

Ant‐inspired level‐based congestion control for wireless mesh networks

The ever increasing presence of services over wireless networks utilizing large bandwidth necessitates the constant quest for developing efficient and dependable services, capable of providing support to a wide and variety of applications. Wireless mesh networks can provide such reliable and scalable solutions addressing the requirements of the services utilizing large bandwidth. The current focus is on the interesting and challenging issue of channel access for different services with assured bandwidth guarantees. The problem of bandwidth, constantly encountered by the wireless mesh networks, is studied in this paper with due thrust on the issues pertaining to congestion control mechanisms. A novel ant colony‐based approach called ant‐inspired level‐based congestion control (AILCC) is developed in order to effectively manage the issues of bandwidth. The versatility of the AILCC includes its capacity for service differentiation in addressing a range of requests, such as applications of real‐time and nonreal‐time. The primary focus of AILCC is on providing an efficient congestion control mechanism that can meet numerous bandwidth demands of various applications. The performance of AILCC in terms of the ratio of packet delivery and end‐to‐end delay is evaluated through relevant simulations. The results obtained demonstrate greater levels of performance of AILCC over the other methods in existence. Copyright © 2014 John Wiley & Sons, Ltd.     

Small Molecules in Light‐Emitting Electrochemical Cells: Promising Light‐Emitting Materials

Light‐emitting electrochemical cells (LECs) are solid‐state lighting devices that convert electric current to light within electroluminescent organic semiconductors, and these devices have recently attracted significant attention. Introduced in 1995, LECs are considered a great breakthrough in the field of light‐emitting devices for their applications in scalable and adaptable fabrication processes aimed at producing cost‐efficient devices. Since then, LECs have evolved through the discovery of new suitable emitters, understanding the working mechanism of devices, and the development of various fabrication methods. LECs are best known for their simple architecture and easy, low‐cost fabrication techniques. The key feature of their fabrication is the use of air stable electrodes and a single active layer consisting of mobile ions that enable efficient charge injection and transport processes within LEC devices. More importantly, LEC devices can be operated at low voltages with high efficiencies, contributing to their widespread interest. This review provides a general overview of the development of LECs and discusses how small molecules can be utilized in LEC applications by overcoming the use of traditional lighting materials like polymers and ionic transition metal complexes. The achievements of each study concerning small molecule LECs are discussed.     

Hollow‐Out Patterning Ultrathin Acoustic Metasurfaces for Multifunctionalities Using Soft fiber/Rigid Bead Networks

Acoustic metasurfaces that can manipulate and control sound waves at 2D subwavelength scales open new avenues to unusual applications, such as asymmetric transmission, super‐resolution imaging, and particle manipulation. However, the long‐standing goals of pushing frontier metamaterials research into real practice are still severely constrained by cumbersome configuration, large acoustic loss, and rigid structure of the existing metamaterials. An ultrathin metasurface (10–300 µm in thickness, up to ≈λ/650, λ the wavelength) that is capable of imparting sound wave with a nontrivial phase shift with high transmittance (>80%) in the range of 5–30 kHz is fabricated here. The metasurface is comprised of a porous network of soft polymer fiber/rigid beads that are physically equivalent to crosslinked spring‐mass resonators. Moreover, the traditional paper‐cutting art to carve the ultrathin metasurface into hollow‐out patterns is incorporated, resulting in a variety of remarkable functions, including acoustic vortex, focusing, and super‐resolution. The hollow‐out patterning approach innovates the traditional one‐step metadevice fabrication process into two separated steps: 1) fabrication of ultrathin metasurfaces; 2) hollow‐out patterning of metasurfaces. The strategy opens an avenue to mass production of acoustic metadevices, shedding light on the applications of the metamaterials in acoustic cloaking, acoustic positioning, and particle manipulation.     

Graphene Paper Doped with Chemically Compatible Prussian Blue Nanoparticles as Nanohybrid Electrocatalyst

Along with reduced graphene oxide (RGO), water soluble Prussian blue nanoparticles (PBNPs, around 6 nm) are synthesized and broadly characterized. These two types of highly stable, low‐cost and chemically compatible nanomaterials are exploited as building ingredients to prepare electrically enhanced and functionally endorsed nanohybrid electrocatalysts, which are further transformed into free‐standing graphene papers. PBNPs doped graphene papers show highly efficient electrocatalysis towards reduction of hydrogen peroxide and can be used alone as flexible chemical sensors for potential applications in detection of hydrogen peroxide or/and other organic peroxides. The as‐prepared PBNPs–RGO papers are further capable of biocompatible accommodation of enzymes for development of free‐standing enzyme based biosensors. In this regard, glucose oxidase is used as an example for electrocatalytic oxidation and detection of glucose. The present work demonstrates a facile and highly reproducible way to construct free‐standing and flexible graphene paper doped with electroactive catalyst. Thanks to high stability, low‐cost and efficient electrocatalytic characteristics, this kind of nanohybrid material has potential to be produced on a large scale, and offers a broad range of possible applications, particularly in the fabrication of flexible sensing devices and as a platform for electrocatalytic energy conversion.     

Carbonized Silk Nanofiber Membrane for Transparent and Sensitive Electronic Skin

Recent years have witnessed the explosive development of electronic skin. Highly sensitive pressure sensing is one of the primary abilities of electronic skin. To date, most of the reported skin‐like pressure sensors are based on nanomaterials and microstructured polydimethylsiloxane (PDMS) films, limiting their wide practical applications due to the unknown biotoxicity and the redundant fabrication procedure. A cost‐effective, large‐area‐capable, and biocompatible approach for fabrication of high‐performance skin‐like pressure sensors is highly desired. Silk fibroin (SF) is a natural protein that has recently drawn great attention due to its application as the substrate for flexible electronics. Here, the fabrication of skin‐like pressure sensors is demonstrated using SF‐derived active materials. Flexible and conformal pressure sensors can be fabricated using transparent carbonized silk nanofiber membranes (CSilkNM) and unstructured PDMS films through a cost‐effective and large‐scale capable approach. Due to the unique N‐doped carbon nanofiber network structure of CSilkNM, the obtained pressure sensor shows superior performance, including ultrahigh sensitivity (34.47 kPa^?1) for a broad pressure range, an ultralow detection limit (0.8 Pa), rapid response time (<16.7 ms), and high durability (>10 000 cycles). Based on its superior performance, its applications in monitoring human physiological signals, sensing subtle touch, and detecting spatial distribution of pressure are demonstrated.     

Multiarray Nanopattern Electronic Nose (E‐Nose) by High‐Resolution Top‐Down Nanolithography

An electronic nose (E‐nose) is an artificial sensing device that mimics the human olfactory system using a multiarray sensor system. However, since the design and fabrication of multiarray sensing channels are significantly limited because of the requirement of time‐consuming and nonuniversal processes, the development of commercializable and high‐throughput fabrication approaches are critically required. Herein, high‐resolution top‐down lithography is developed for E‐nose fabrication for the first time. Five different metal oxide semiconductor (MOS) nanopattern channels (NiO, CuO, Cr₂O₃, SnO₂, and WO₃) are fabricated into multiarray sensors with high‐throughput using a unique lithographic approach that utilizes the sputtering of grains of the metals via low‐energy ion plasma bombardment. The nanopattern channels show i) high‐resolutions (15 nm scale), ii) high‐aspect‐ratios (11; 14 nm width and 150 nm height), and iii) ultrasmall grains (5.1 nm) with uniformity on a cm² scale, resulting in high sensitivity toward the target analytes. The E‐nose system, which is composed of five MOS nanopattern channels, can successfully distinguish seven different hazardous analytes, including volatile organic compounds and nitrogen‐containing compounds. It is expected that this unique lithography approach can provide a simple and reliable method for commercializable channel fabrication, and the E‐noses can have further applications in real‐life situations.     

Ultrathin Transparent Au Electrodes for Organic Photovoltaics Fabricated Using a Mixed Mono‐Molecular Nucleation Layer

A rapid, solvent free method for the fabrication of highly transparent ultrathin (～8 nm) Au films on glass has been developed. This is achieved by derivatizing the glass surface with a mixed monolayer of 3‐mercaptopropyl(trim­ethoxysilane) and 3‐aminopropyl(trimethoxysilane) via co‐deposition from the vapor phase, prior to Au deposition by thermal evaporation. The mixed mono­layer modifies the growth kinetics, producing highly conductive films (～11 Ω per square) with a remarkably low root‐mean‐square roughness (～0.4 nm) that are exceptionally robust towards UV/O₃ treatment and ultrasonic agitation in a range of common solvents. As such, they are potentially widely applicable for a variety of large area applications, particularly where stable, chemically well‐defined, ultrasmooth substrate electrodes are required, such as in organic optoelectronics and the emerging fields of nanoelectronics and nanophotonics. By integrating microsphere lithography into the fabrication process, we also demonstrate a means of tuning the transparency by incorporating a random array of circular apertures into the film. The application of these nanostructured Au electrodes is demonstrated in efficient organic photovoltaic devices where it offers a compelling alternative to indium tin oxide coated glass.     

Superparamagnetic Twist‐Type Actuators with Shape‐Independent Magnetic Properties and Surface Functionalization for Advanced Biomedical Applications

Directed nanoparticle self‐organization and two‐photon polymerization are combined to enable three‐dimensional soft‐magnetic microactuators with complex shapes and shape‐independent magnetic properties. Based on the proposed approach, single and double twist‐type swimming microrobots with programmed magnetic anisotropy are demonstrated, and their swimming properties in DI‐water are characterized. The fabricated devices are actuated using weak rotating magnetic fields and are capable of performing wobble‐free corkscrew propulsion. Single twist‐type actuators possess an increase in surface area in excess of 150% over helical actuators with similar feature size without compromising the forward velocity of over one body length per second. A generic and facile combination of glycine grafting and subsequent protein immobilization exploits the actuator's increased surface area, providing for a swimming microrobotic platform with enhanced load capacity desirable for future biomedical applications. Successful surface modification is confirmed by FITC fluorescence.     

3D Printed Template-Assisted Casting of Biocompatible Polyvinyl Alcohol-Based Soft Microswimmers with Tunable Stability

The past decade has seen an upsurge in the development of small-scale magnetic robots for various biomedical applications. However, many of the reported designs comprise components with biocompatibility concerns. Strategies for fabricating biocompatible and degradable microrobots are required. In this study, polyvinyl alcohol (PVA)-based magnetic hydrogel microrobots with different morphologies and tunable stability are developed by combining a 3D printed template-assisted casting with a salting-out process. 3D sacrificial micromolds are prepared via direct laser writing to shape PVA-magnetic nanoparticle composite hydrogel microrobots with high architectural complexity. By adjusting the PVA composition and salting-out parameters, the hydrogel dissolubility can be customized. Due to their high mobility, tunable stability, and high biocompatibility, these PVA-based magnetic microrobots are suitable platforms for targeted drug and cell delivery.     

银杏花粉萌发生长与分枝式花粉管形成的观察

本研究采用半薄切片法和扫描电镜等技术对银杏（Ginkgo bilobaL.）花粉管的体内萌发与生长以及花粉的离体培养进行了观察,结果表明：（1）银杏花粉粒通过传粉滴收缩后到达胚珠珠孔处,并经珠孔道进入贮粉室内停留,约7 d后花粉粒开始萌发;（2）贮粉室内的花粉最初萌发出的花粉管与花粉粒的四细胞轴几乎垂直,表现出明显的侧向萌发特征。初始花粉管在贮粉室内的生长方向无规律,有的通过一定的贮粉室空间向较远的珠心组织细胞间隙生长,有的直接进到较近的珠心组织细胞间隙,花粉管的生长不损伤珠心组织细胞;（3）花粉离体培养过程中会迅速发生水合作用,花粉粒由船形变为圆球形。48 h后花粉外壁脱落,管细胞膨大,花粉管自管细胞膨大处萌发。随着花粉管的生长,管细胞核移动进入花粉管内,而生殖细胞仍留在花粉粒内。伸长的花粉管可分为淀粉粒区和透明区,花粉管末端易形成多种类型的分枝。花粉管内原生质呈喷泉状流动。     

Rapid Fabrication of Soft,Multilayered Electronics for Wearable Biomonitoring

Soft integrated electronics are key components for emerging applications in wearable biomonitoring, soft co‐robotics, and physical human–machine interaction. They are composed of soft and elastically deformable circuits and sensors that are combined with packaged microelectronics for signal processing, power regulation, and communication. While promising, widespread use of soft wearable electronics is currently limited by the lack of robust fabrication techniques to rapidly, efficiently, and precisely assemble soft and rigid components into multilayered systems. Here, an efficient digital fabrication approach is presented to create highly customizable wearable electronics through rapid laser machining and adhesion controlled soft materials assembly. Well aligned, multilayered materials are created from 2D and 3D elements that stretch and bend while seamlessly integrating with rigid components such as microchip integrated circuits, discrete electrical components, and interconnects. These techniques are applied using commercially available materials and components and the fabrication of thin, lightweight, customized sensor skins is demonstrated in under an hour. These fully integrated wireless devices conformably bond to the hand and are successfully used for monitoring hand gesture, pulse rate, and blood oxygenation. These materials and methods enable custom wearable electronics while offering versatility in design and functionality for a variety of applications through material selection and construction.     

Colloidal Occlusion Template Method for Micromanufacturing of Omniphobic Surfaces

An efficient strategy to produce forests of aligned nanowires and nail‐like micrometer‐sized structures, whose density can be tuned in a broad range, is reported in this study. It relies on a combination of two template‐assisted nanofabrication/patterning methods: electrochemical growth of metal nanowires in nanoporous sacrificial templates and partial masking of a surface with a self‐assembled colloidal monolayer. A great potential of this novel approach, termed here colloidal occlusion template method, is demonstrated on the example of the fabrication of omniphobic surfaces comprised of nickel micronails whose density is varied to approach highest possible contact angles. After chemical modification to reduce their surface tension, these microstructures with reentrant geometry support the non‐wetting Cassie state for both high‐surface‐tension water and low‐surface‐tension hexadecane. In particular, superhydrophobic behavior (contact angles exceeding 150°) is found for water, while oleophobicity (contact angles approaching 110°) is observed for hexadecane. The proposed approach can be exploited for the fabrication of a large variety of supported high‐aspect‐ratio nano/microstructures in applications where a surface density of features has to be several orders of magnitude lower than can be obtained with conventional template methods.     

Graphene‐Directed Supramolecular Assembly of Multifunctional Polymer Hydrogel Membranes

Polymer‐based nanoporous hydrogel membranes hold great potential for a range of applications including molecular filtration/separation, controlled drug release, and as sensors and actuators. However, to be of practical utility, polymer membranes generally need to be fabricated as ultrathin yet mechanically robust, have a large‐area yet be defect‐free and in some cases, their structure needs the capability to adapt to certain stimuli. These stringent and sometimes self‐conflicting requirements make it very challenging to manufacture such bulk nanostructures in a controllable, scalable and cost‐effective manner. Here, a versatile approach to the fabrication of multifunctional polymer‐based hydrogel membranes is demonstrated by a single step involving filtration of an aqueous dispersion containing chemically converted graphene (CCG) and a polymer. With CCG uniquely serving as a membrane‐ and pore‐forming directing agent and as a physical cross‐linker, a range of water soluble polymers can be readily processed into nanoporous hydrogel membranes through supramolecular interactions. With the interconnected CCG network as a robust and porous scaffold, the membrane nanostructure can easily be fine‐tuned to suit different applications simply by controlling the chemistry and concentration of the incorporated polymer. This work provides a simple and versatile platform for the design and fabrication of new adaptive supramolecular membranes for a variety of applications.     

Soft Microreactors for the Deposition of Conductive Metallic Traces on Planar,Embossed, and Curved Surfaces

Advanced manufacturing strategies have enabled large‐scale, economical, and efficient production of electronic components that are an integral part of various consumer products ranging from simple toys to intricate computing systems; however, the circuitry for these components is (by and large) produced via top‐down lithography and is thus limited to planar surfaces. The present work demonstrates the use of reconfigurable soft microreactors for the patterned deposition of conductive copper traces on flat and embossed two‐dimensional (2D) substrates as well as nonplanar substrates made from different commodity plastics. Using localized, flow‐assisted, low‐temperature, electroless copper deposition, conductive metallic traces are fabricated, which, when combined with various off‐the‐shelf electronic components, enabled the production of simple circuits and antennas with unique form factors. This solution‐phase approach to the patterned deposition of functional inorganic materials selectively on different polymeric components will provide relatively simple, inexpensive processing opportunities for the fabrication of 2D/nonplanar devices when compared to complicated manufacturing methods such as laser‐directed structuring. Further, this approach to the patterned metallization of different commodity plastics offers unique design opportunities applicable to the fabrication of planar and nonplanar electronic and interconnect devices, and other free‐form electronics with less structural “bloat” and weight (by directly coating support elements with circuitry).