Magnetic Microrobot Swarms with Polymeric Hands Catching Bacteria and Microplastics in Water.

The forefront of micro- and nanorobot research involves the development of smart swimming micromachines emulating the complexity of natural systems, such as the swarming and collective behaviors typically observed in animals and microorganisms, for efficient task execution. This study introduces magnetically controlled microrobots that possess polymeric sequestrant "hands" decorating a magnetic core. Under the influence of external magnetic fields, the functionalized magnetic beads dynamically self-assemble from individual microparticles into well-defined rotating planes of diverse dimensions, allowing modulation of their propulsion speed, and exhibiting a collective motion. These mobile microrobotic swarms can actively capture free-swimming bacteria and dispersed microplastics "on-the-fly", thereby cleaning aquatic environments. Unlike conventional methods, these microrobots can be collected from the complex media and can release the captured contaminants in a second vessel in a controllable manner, that is, using ultrasound, offering a sustainable solution for repeated use in decontamination processes. Additionally, the residual water is subjected to UV irradiation to eliminate any remaining bacteria, providing a comprehensive cleaning solution. In summary, this study shows a swarming microrobot design for water decontamination processes.

Band Engineering versus Catalysis: Enhancing the Self-Propulsion of Light-Powered MXene-Derived Metal-TiO2 Micromotors To Degrade Polymer Chains.

Light-powered micro- and nanomotors based on photocatalytic semiconductors convert light into mechanical energy, allowing self-propulsion and various functions. Despite recent progress, the ongoing quest to enhance their speed remains crucial, as it holds the potential for further accelerating mass transfer-limited chemical reactions and physical processes. This study focuses on multilayered MXene-derived metal-TiO2 micromotors with different metal materials to investigate the impact of electronic properties of the metal-semiconductor junction, such as energy band bending and built-in electric field, on self-propulsion. By asymmetrically depositing Au or Ag layers on thermally annealed Ti3C2Tx MXene microparticles using sputtering, Janus structures are formed with Schottky junctions at the metal-semiconductor interface. Under UV light irradiation, Au-TiO2 micromotors show higher self-propulsion velocities due to the stronger built-in electric field, enabling efficient photogenerated charge carrier separation within the semiconductor and higher hole accumulation beneath the Au layer. On the contrary, in 0.1 wt % H2O2, Ag-TiO2 micromotors reach higher velocities both in the presence and absence of UV light irradiation, owing to the superior catalytic properties of Ag in H2O2 decomposition. Due to the widespread use of plastics and polymers, and the consequent occurrence of nano/microplastics and polymeric waste in water, Au-TiO2 micromotors were applied in water remediation to break down polyethylene glycol (PEG) chains, which were used as a model for polymeric pollutants in water. These findings reveal the interplay between electronic properties and catalytic activity in metal-semiconductor junctions, offering insights into the future design of powerful light-driven micro- and nanomotors with promising implications for water treatment and photocatalysis applications.

Reconfigurable self-assembly of photocatalytic magnetic microrobots for water purification.

The development of artificial small-scale robotic swarms with nature-mimicking collective behaviors represents the frontier of research in robotics. While microrobot swarming under magnetic manipulation has been extensively explored, light-induced self-organization of micro- and nanorobots is still challenging. This study demonstrates the interaction-controlled, reconfigurable, reversible, and active self-assembly of TiO2/α-Fe2O3 microrobots, consisting of peanut-shaped α-Fe2O3 (hematite) microparticles synthesized by a hydrothermal method and covered with a thin layer of TiO2 by atomic layer deposition (ALD). Due to their photocatalytic and ferromagnetic properties, microrobots autonomously move in water under light irradiation, while a magnetic field precisely controls their direction. In the presence of H2O2 fuel, concentration gradients around the illuminated microrobots result in mutual attraction by phoretic interactions, inducing their spontaneous organization into self-propelled clusters. In the dark, clusters reversibly reconfigure into microchains where microrobots are aligned due to magnetic dipole-dipole interactions. Microrobots' active motion and photocatalytic properties were investigated for water remediation from pesticides, obtaining the rapid degradation of the extensively used, persistent, and hazardous herbicide 2,4-Dichlorophenoxyacetic acid (2,4D). This study potentially impacts the realization of future intelligent adaptive metamachines and the application of light-powered self-propelled micro- and nanomotors toward the degradation of persistent organic pollutants (POPs) or micro- and nanoplastics.

Smart micro- and nanorobots for water purification.

Less than 1% of Earth's freshwater reserves is accessible. Industrialization, population growth and climate change are further exacerbating clean water shortage. Current water-remediation treatments fail to remove most pollutants completely or release toxic by-products into the environment. The use of self-propelled programmable micro- and nanoscale synthetic robots is a promising alternative way to improve water monitoring and remediation by overcoming diffusion-limited reactions and promoting interactions with target pollutants, including nano- and microplastics, persistent organic pollutants, heavy metals, oils and pathogenic microorganisms. This Review introduces the evolution of passive micro- and nanomaterials through active micro- and nanomotors and into advanced intelligent micro- and nanorobots in terms of motion ability, multifunctionality, adaptive response, swarming and mutual communication. After describing removal and degradation strategies, we present the most relevant improvements in water treatment, highlighting the design aspects necessary to improve remediation efficiency for specific contaminants. Finally, open challenges and future directions are discussed for the real-world application of smart micro- and nanorobots.

Magnetically Driven Self-Degrading Zinc-Containing Cystine Microrobots for Treatment of Prostate Cancer.

Prostate cancer is the most commonly diagnosed tumor disease in men, and its treatment is still a big challenge in standard oncology therapy. Magnetically actuated microrobots represent the most promising technology in modern nanomedicine, offering the advantage of wireless guidance, effective cell penetration, and non-invasive actuation. Here, new biodegradable magnetically actuated zinc/cystine-based microrobots for in situ treatment of prostate cancer cells are reported. The microrobots are fabricated via metal-ion-mediated self-assembly of the amino acid cystine encapsulating superparamagnetic Fe3 O4 nanoparticles (NPs) during the synthesis, which allows their precise manipulation by a rotating magnetic field. Inside the cells, the typical enzymatic reducing environment favors the disassembly of the aminoacidic chemical structure due to the cleavage of cystine disulfide bonds and disruption of non-covalent interactions with the metal ions, as demonstrated by in vitro experiments with reduced nicotinamide adenine dinucleotide (NADH). In this way, the cystine microrobots served for site-specific delivery of Zn2+ ions responsible for tumor cell killing via a "Trojan horse effect". This work presents a new concept of cell internalization exploiting robotic systems' self-degradation, proposing a step forward in non-invasive cancer therapy.

Radiopaque Nanorobots as Magnetically Navigable Contrast Agents for Localized In Vivo Imaging of the Gastrointestinal Tract.

Magnetic nanorobots offer wireless navigation capability in hard-to-reach areas of the human body for targeted therapy and diagnosis. Though in vivo imaging is required for guidance of the magnetic nanorobots toward the target areas, most of the imaging techniques are inadequate to reveal the potential locomotion routes. This work proposes the use of radiopaque magnetic nanorobots along with microcomputed tomography (microCT) for localized in vivo imaging applications. The nanorobots consist of a contrast agent, barium sulfate (BaSO4 ), magnetized by the decoration of magnetite (Fe3 O4 ) particles. The magnetic features lead to actuation under rotating magnetic fields and enable precise navigation in a microfluidic channel used to simulate confined spaces of the body. In this channel, the intrinsic radiopacity of the nanorobots also provides the possibility to reveal the internal structures by X-ray contrast. Furthermore, in vitro analysis indicates nontoxicity of the nanorobots. In vivo experiments demonstrate localization of the nanorobots in a specific part of the gastrointestinal (GI) tract upon the influence of the magnetic field, indicating the efficient control even in the presence of natural peristaltic movements. The nanorobots reported here highlight that smart nanorobotic contrast agents can improve the current imaging-based diagnosis techniques by providing untethered controllability in vivo.

Self-Propelled Magnetic Dendrite-Shaped Microrobots for Photodynamic Prostate Cancer Therapy.

Photocatalytic micromotors that exhibit wireless and controllable motion by light have been extensively explored for cancer treatment by photodynamic therapy (PDT). However, overexpressed glutathione (GSH) in the tumor microenvironment can down-regulate the reactive oxygen species (ROS) level for cancer therapy. Herein, we present dendrite-shaped light-powered hematite microrobots as an effective GSH depletion agent for PDT of prostate cancer cells. These hematite microrobots can display negative phototactic motion under light irradiation and flexible actuation in a defined path controlled by an external magnetic field. Non-contact transportation of micro-sized cells can be achieved by manipulating the microrobot's motion. In addition, the biocompatible microrobots induce GSH depletion and greatly enhance PDT performance. The proposed dendrite-shaped hematite microrobots contribute to developing dual light/magnetic field-powered micromachines for the biomedical field.

Trapping and detecting nanoplastics by MXene-derived oxide microrobots.

Nanoplastic pollution, the final product of plastic waste fragmentation in the environment, represents an increasing concern for the scientific community due to the easier diffusion and higher hazard associated with their small sizes. Therefore, there is a pressing demand for effective strategies to quantify and remove nanoplastics in wastewater. This work presents the "on-the-fly" capture of nanoplastics in the three-dimensional (3D) space by multifunctional MXene-derived oxide microrobots and their further detection. A thermal annealing process is used to convert Ti3C2Tx MXene into photocatalytic multi-layered TiO2, followed by the deposition of a Pt layer and the decoration with magnetic γ-Fe2O3 nanoparticles. The MXene-derived γ-Fe2O3/Pt/TiO2 microrobots show negative photogravitaxis, resulting in a powerful fuel-free motion with six degrees of freedom under light irradiation. Owing to the unique combination of self-propulsion and programmable Zeta potential, the microrobots can quickly attract and trap nanoplastics on their surface, including the slits between multi-layer stacks, allowing their magnetic collection. Utilized as self-motile preconcentration platforms, they enable nanoplastics' electrochemical detection using low-cost and portable electrodes. This proof-of-concept study paves the way toward the "on-site" screening of nanoplastics in water and its successive remediation.

Light-Propelled Nanorobots for Facial Titanium Implants Biofilms Removal.

Titanium miniplates are biocompatible materials used in modern oral and maxillofacial surgery to treat facial bone fractures. However, plate removal is often required due to implant complications. Among them, a biofilm formation on an infected miniplate is associated with severe inflammation, which frequently results in implant failure. In light of this, new strategies to control or treat oral bacterial biofilm are of high interest. Herein, the authors exploit the ability of nanorobots against multispecies bacterial biofilm grown onto facial commercial titanium miniplate implants to simulate pathogenic conditions of the oral microenvironment. The strategy is based on the use of light-driven self-propelled tubular black-TiO2 /Ag nanorobots, that unlike traditional ones, exhibit an extended absorption and motion actuation from UV to the visible-light range. The motion analysis is performed separately over UV, blue, and green light irradiation and shows different motion behaviors, including a fast rotational motion that decreases with increasing wavelengths. The biomass reduction is monitored by evaluating LIVE/DEAD fluorescent and digital microscope images of bacterial biofilm treated with the nanorobots under motion/no-motion conditions. The current study and the obtained results can bring significant improvements for effective therapy of infected metallic miniplates by biofilm.

Shape-Controlled Self-Assembly of Light-Powered Microrobots into Ordered Microchains for Cells Transport and Water Remediation.

Nature presents the collective behavior of living organisms aiming to accomplish complex tasks, inspiring the development of cooperative micro/nanorobots. Herein, the spontaneous assembly of hematite-based microrobots with different shapes is presented. Autonomous motile light-driven hematite/Pt microrobots with cubic and walnut-like shapes are prepared by hydrothermal synthesis, followed by the deposition of a Pt layer to design Janus structures. Both microrobots show a fuel-free motion ability under light irradiation. Because of the asymmetric orientation of the magnetic dipole moment in the crystal, cubic hematite/Pt microrobots can self-assemble into ordered microchains, contrary to the random aggregation observed for walnut-like microrobots. The microchains exhibit different synchronized motions under light irradiation depending on the mutual orientation of the individual microrobots during the assembly, which allows them to accomplish multiple tasks, including capturing, picking up, and transporting microscale objects, such as yeast cells and suspended matter in water extracted from personal care products, as well as degrading polymeric materials. Such light-powered self-assembled microchains demonstrate an innovative cooperative behavior for small-scale multitasking artificial robotic systems, holding great potential toward cargo capture, transport, and delivery, and wastewater remediation.

Self-Propelled Multifunctional Microrobots Harboring Chiral Supramolecular Selectors for "Enantiorecognition-on-the-Fly".

Herein, a general procedure for the synthesis of multifunctional MRs, which simultaneously exhibit i) chiral, ii) magnetic, and iii) fluorescent properties in combination with iv) self-propulsion, is reported. Self-propelled Ni@Pt superparamagnetic microrockets have been functionalized with fluorescent CdS quantum dots carrying a chiral host biomolecule as ß-cyclodextrin (ß-CD). The "on-the-fly" chiral recognition potential of MRs has been interrogated by taking advantage of the ß-CD affinity to supramolecularly accommodate different chiral biomolecules (i.e., amino acids). As a proof-of-concept, tryptophan enantiomers have been discriminated with a dual-mode (optical and electrochemical) readout. This approach paves the way to devise intelligent cargo micromachines with "built-in" chiral supramolecular recognition capabilities to elucidate the concept of "enantiorecognition-on-the-fly", which might be facilely customized by tailoring the supramolecular host-guest encapsulation.

Photo-Fenton Degradation of Nitroaromatic Explosives by Light-Powered Hematite Microrobots: When Higher Speed Is Not What We Go For.

Self-powered micromachines are considered a ground-breaking technology for environmental remediation. Light-powered Janus microrobots based on photocatalytic semiconductors asymmetrically covered with metals have recently received great interest as they can exploit light to move and contemporarily degrade pollutants in water. Although various metals have been explored and compared to design Janus microrobots, the influence of the metal layer thickness on motion behavior and photocatalytic properties of microrobots have not been investigated yet. Here, light-driven hematite/Pt Janus microrobots are reported and fabricated by depositing Pt layers with different thickness on hematite microspheres produced by hydrothermal synthesis. It has been demonstrated that the thicker the metal layer the higher the microrobots speed. However, when employed for the degradation of nitroaromatic explosives pollutants through the photo-Fenton mechanism, higher rate of H2 O2 consumption leads to higher propulsion speed of microrobots and lower pollutants degradation efficiencies owing to less H2 O2 involved in the photo-Fenton reaction. This work presents new insights into the motion behavior of light-powered Janus micromotors and demonstrates that high speed is not what really matters for water purification via photo-Fenton reaction, which is important for the future environmental applications of micromachines.

Nickel Sulfide Microrockets as Self-Propelled Energy Storage Devices to Power Electronic Circuits "On-Demand".

Miniaturized energy storage devices are essential to power the growing number and variety of microelectronic technologies. Here, a concept of self-propelled microscale energy storage elements that can move, reach, and power electronic circuits is reported. Microrockets consisting of a nickel sulfide (NiS) outer layer and a Pt inner layer are prepared by template-assisted electrodeposition, and designed to store energy through NiS-mediated redox reactions and propel via the Pt-catalyzed decomposition of H2 O2 fuel. Scanning electrochemical microscopy allows visualizing and studying the energy storage ability of a single microrocket, revealing its pseudocapacitive nature. This proves the great potential of such technique in the field of micro/nanomotors. On-demand delivery of energy storage units to electronic circuits has been demonstrated by releasing microrockets on an interdigitated array electrode as an example of electronic circuit. Owing to their self-propulsion ability, they reach the active area of the electrode and, in principle, power its functions. These autonomously moving energy storage devices will be employed for next-generation electronics to store and deliver energy in previously inaccessible locations.

Optimization of Oxygen Evolution Reaction with Electroless Deposited Ni-P Catalytic Nanocoating.

The low efficiency of water electrolysis mostly arises from the thermodynamic uphill oxygen evolution reaction. The efficiency can be greatly improved by rationally designing low-cost and efficient oxygen evolution anode materials. Herein, we report the synthesis of Ni-P alloys adopting a facile electroless plating method under mild conditions on nickel substrates. The relationship between the Ni-P properties and catalytic activity allowed us to define the best conditions for the electroless synthesis of highperformance Ni-P catalysts. Indeed, the electrochemical investigations indicated an increased catalytic response by reducing the thickness and Ni/P ratio in the alloy. Furthermore, the Ni-P catalysts with optimized size and composition deposited on Ni foam exposed more active sites for the oxygen evolution reaction, yielding a current density of 10 mA cm-2 at an overpotential as low as 335 mV, exhibiting charge transfer resistances of only a few ohms and a remarkable turnover frequency (TOF) value of 0.62 s-1 at 350 mV. The present study provides an advancement in the control of the electroless synthetic approach for the design and large-scale application of high-performance metal phosphide catalysts for electrochemical water splitting.

Severe Corneal Morphological Alterations after Excimer Laser Surface Ablation for a High Astigmatism.

We report long-term alterations of anterior corneal stroma after excimer laser surface ablation for a high astigmatism. The patient claimed progressive visual loss in his right eye (RE) during the last 3 years after bilateral laser-assisted subepithelial keratectomy (LASEK) surgery. His examination comprised visual acuity (UDVA and CDVA), slit-lamp examination, corneal topography and tomography, AS-OCT, and confocal microscopy. The UDVA was 0.1 in his RE and 1.0 in the left eye. The CDVA in the RE was 0.8. The slit-lamp examination showed a stromal lesion in the inferior paracentral corneal zone, with multiple vertical tissue bridges and severe thinning. Corneal topography and tomography showed central flattening with inferior steepening and severe alteration in elevation maps. AS-OCT showed void areas in the anterior stroma with thinning of the underlying tissue, and confocal images were not specific. In this case, progressive corneal steepening and thinning that manifest topographically as inferior ectasia occurred in correspondence to the singular stromal alterations after LASEK.

Gas sensing materials roadmap.

Gas sensor technology is widely utilized in various areas ranging from home security, environment and air pollution, to industrial production. It also hold great promise in non-invasive exhaled breath detection and an essential device in future internet of things. The past decade has witnessed giant advance in both fundamental research and industrial development of gas sensors, yet current efforts are being explored to achieve better selectivity, higher sensitivity and lower power consumption. The sensing layer in gas sensors have attracted dominant attention in the past research. In addition to the conventional metal oxide semiconductors, emerging nanocomposites and graphene-like two-dimensional materials also have drawn considerable research interest. This inspires us to organize this comprehensive 2020 gas sensing materials roadmap to discuss the current status, state-of-the-art progress, and present and future challenges in various materials that is potentially useful for gas sensors.

Role of Substrate in Au Nanoparticle Decoration by Electroless Deposition.

Decoration of nanostructures is a promising way of improving performances of nanomaterials. In particular, decoration with Au nanoparticles is considerably efficient in sensing and catalysis applications. Here, the mechanism of decoration with Au nanoparticles by means of low-cost electroless deposition (ELD) is investigated on different substrates, demonstrating largely different outcomes. ELD solution with Au potassium cyanide and sodium hypophosphite, at constant temperature (80 °C) and pH (7.5), is used to decorate by immersion metal (Ni) or semiconductor (Si, NiO) substrates, as well as NiO nanowalls. All substrates were pre-treated with a hydrazine hydrate bath. Scanning electron microscopy and Rutherford backscattering spectrometry were used to quantitatively analyze the amount, shape and size of deposited Au. Au nanoparticle decoration by ELD is greatly affected by the substrates, leading to a fast film deposition onto metallic substrate, or to a slow cluster (50-200 nm sized) formation on semiconducting substrate. Size and density of resulting Au clusters strongly depend on substrate material and morphology. Au ELD is shown to proceed through a galvanic displacement on Ni substrate, and it can be modeled with a local cell mechanism widely affected by the substrate conductivity at surface. These data are presented and discussed, allowing for cheap and reproducible Au nanoparticle decoration on several substrates.

Ultrasensitive Electrochemical Impedance Detection of Mycoplasma agalactiae DNA by Low-Cost and Disposable Au-Decorated NiO Nanowall Electrodes.

Nanostructured electrodes detecting bacteria or viruses through DNA hybridization represent a promising method, which may be useful in on-field applications where PCR-based methods are very expensive, time-consuming, and require trained personnel. Indeed, electrochemical sensors combine disposability, fast response, high sensitivity, and portability. Here, a low-cost and high-surface-area electrode, based on Au-decorated NiO nanowalls, demonstrates a highly sensitive PCR-free detection of a real sample of Mycoplasma agalactiae (Ma) DNA. NiO nanowalls, synthesized by aqueous methods, thermal annealing, and Au decoration, by electroless deposition, ensure a high-surface-area platform for successful immobilization of Ma thiolated probe DNA. The morphological, chemical, and electrochemical properties of the electrode were characterized, and a reproducible detection of synthetic Ma DNA was observed and investigated by impedance measurements. Electrochemical impedance spectroscopy (EIS) ascribed the origin of impedance signal to the Ma DNA hybridization with its probe immobilized onto the electrode. The electrode successfully discriminates between DNA extracted from healthy and infected sheep milk, showing the ability to detect Ma DNA in concentrations as low as 53 ± 2 copy number µL-1. The Au-decorated NiO nanowall electrode represents a promising route toward PCR-free, disposable, rapid, and molecular detection.

Disposable and Low-Cost Electrode Based on Graphene Paper-Nafion-Bi Nanostructures for Ultra-Trace Determination of Pb(II) and Cd(II).

There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5-100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

New Synthetic Route for the Growth of α-FeOOH/NH2-Mil-101 Films on Copper Foil for High Surface Area Electrodes.

A novel metal organic framework (MOF)-based composite was synthesized on a Cu substrate via a two-step route. An amorphous iron oxide/hydroxide layer was first deposited on a Cu foil through a sol-gel process; then, Fe-NH2-Mil-101 was grown using both the iron oxide/hydroxide matrix, which provided the Fe3+ centers needed for MOF formation, and 2-aminoterephthalic acid ethanol solution. This innovative synthetic strategy is a convenient approach to grow metal oxide/hydroxide and MOF composite films. Structural, chemical, and morphological characterizations suggest that the obtained composite is made up of both the α-FeOOH goethite and the NH2-Mil-101 phases featuring a hybrid heterostructure. The electrochemical features of the composite structure were investigated using electrochemical impedance spectroscopy. The impedance behavior of the α-FeOOH/NH2-Mil-101 films indicates that they can be used as efficient high surface area metal hydroxide/MOF-based electrodes for applications such as energy storage and sensing.