An Account on BiVO4 as Photocatalytic Active Matter.

Photocatalytic materials are gaining popularity and research investment for developing light-driven micromotors. While most of the early work used highly stable TiO2 as a material to construct micromotors, mostly in combination with noble metals, other semiconductors offer a wider range of properties, including independence from high-energy UV light. This review focuses on our work with BiVO4 which has shown promise due to its small band gap and resulting ability to absorb blue light. Additionally, this salt's well-defined crystal structures lead to exploitable charge separation on different crystal facets, providing sufficient asymmetry to cause active propulsion. These properties have given rise to fascinating physical and chemical behaviors that show how rich and variable active matter can become. Here, we present the synthesis of different BiVO4 microparticles and their material properties that make them excellent candidates as active micromotors. A critical factor in understanding inherently asymmetric micromotors is knowledge of their flow fields. However, due to their small size and the need to use even smaller tracer particles to avoid perturbing the flow field, measuring flow fields at the microscale is a difficult task. We also present these first results, which allow us to demonstrate the correlation between chemical reactivity and the flow generated, leading to active motion. Due to the nontoxic nature of BiVO4, these visible-light-responsive microswimmers have been used to study the first steps toward applications, even in sensitive areas such as food technology. Although these initial tests are far from being realized, we have to face the fact that a single microswimmer will not be able to perform macroscale tasks. Therefore, we present the reader with the first simple studies of collective motion, hoping for many new contributions to the field. The one-step synthesis of BiVO4 clearly paves the way for studies requiring large numbers of particles. We predict that the combination of promising applications for a nontoxic material which is readily synthesized in large quantities will contribute pivotally to advance the field of active matter beyond the proof-of-concept stage.

Boosting the Efficiency of Photoactive Rod-Shaped Nanomotors via Magnetic Field-Induced Charge Separation.

Photocatalytic nanomotors have attracted a lot of attention because of their unique capacity to simultaneously convert light and chemical energy into mechanical motion with a fast photoresponse. Recent discoveries demonstrate that the integration of optical and magnetic components within a single nanomotor platform offers novel advantages for precise motion control and enhanced photocatalytic performance. Despite these advancements, the impact of magnetic fields on energy transfer dynamics in photocatalytic nanomotors remains unexplored. Here, we introduce dual-responsive rod-like nanomotors, made of a TiO2/NiFe heterojunction, able to (i) self-propel upon irradiation, (ii) align with the direction of an external magnetic field, and (iii) exhibit enhanced photocatalytic performance. Consequently, when combining light irradiation with a homogeneous magnetic field, these nanomotors exhibit increased velocities attributed to their improved photoactivity. As a proof-of-concept, we investigated the ability of these nanomotors to generate phenol, a valuable chemical feedstock, from benzene under combined optical and magnetic fields. Remarkably, the application of an external magnetic field led to a 100% increase in the photocatalytic phenol generation in comparison with light activation alone. By using various state-of-the-art techniques such as photoelectrochemistry, electrochemical impedance spectroscopy, photoluminescence, and electron paramagnetic resonance, we characterized the charge transfer between the semiconductor and the alloy component, revealing that the magnetic field significantly improved charge pair separation and enhanced hydroxyl radical generation. Consequently, our work provides valuable insights into the role of magnetic fields in the mechanisms of light-driven photocatalytic nanomotors for designing more effective light-driven nanodevices for selective oxidations.

Bubble-propelled micromotors for ammonia generation.

Micromotors have emerged as promising tools for environmental remediation, thanks to their ability to autonomously navigate and perform specific tasks at the microscale. In this study, we present the development of MnO2 tubular micromotors modified with laccase for enhanced oxidation of organic pollutants by providing an additional oxidative catalytic pathway for pollutant removal. These modified micromotors exhibit efficient ammonia generation through the catalytic decomposition of urea, suggesting their potential application in the field of green energy generation. Compared to bare micromotors, the MnO2 micromotors modified with laccase exhibit a 20% increase in rhodamine B degradation. Moreover, the generation of ammonia increased from 2 to 31 ppm in only 15 min, evidencing their high catalytic activity. To enable precise tracking of the micromotors and measurement of their speed, a deep-learning-based tracking system was developed. Overall, this work expands the potential applicability of bio-catalytic tubular micromotors in the energy field.

Exploring innovative designs and heterojunctions in photocatalytic micromotors.

Photocatalytic micromotors that convert light energy into mechanical energy have garnered increased interest due to their fast photoactivation, and potential for precise control and manipulation. This feature article provides key insights into the design of photocatalytic micromotors by using single semiconductors, and heterostructures. It also highlights the different strategies to develop efficient light-driven micromotors by minimizing electron-hole pair recombination and improving charge transfer among components. The remaining challenges and possible solutions are also discussed.

3D-Printed Organic Conjugated Trimer for Visible-Light-Driven Photocatalytic Applications.

Small molecule organic semiconductors (SMOSs) have emerged as a new class of photocatalysts that exhibit visible light absorption, tunable bandgap, good dispersion, and solubility. However, the recovery and reusability of such SMOSs in consecutive photocatalytic reactions is challenging. This work concerns a 3D-printed hierarchical porous structure based on an organic conjugated trimer, named EBE. Upon manufacturing, the photophysical and chemical properties of the organic semiconductor are maintained. The 3D-printed EBE photocatalyst shows a longer lifetime (11.7 ns) compared to the powder-state EBE (1.4 ns). This result indicates a microenvironment effect of the solvent (acetone), a better dispersion of the catalyst in the sample, and reduced intermolecular π-π stacking, which results in improved separation of the photogenerated charge carriers. As a proof-of-concept, the photocatalytic activity of the 3D-printed EBE catalyst is evaluated for water treatment and hydrogen production under sun-like irradiation. The resulting degradation efficiencies and hydrogen generation rates are higher than those reported for the state-of-the-art 3D-printed photocatalytic structures based on inorganic semiconductors. The photocatalytic mechanism is further investigated, and the results suggest that hydroxyl radicals (HO⋅) are the main reactive radicals responsible for the degradation of organic pollutants. Moreover, the recyclability of the EBE-3D photocatalyst is demonstrated in up to 5 uses. Overall, these results indicate the great potential of this 3D-printed organic conjugated trimer for photocatalytic 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.

Hybrid Photoresponsive/Biocatalytic Micro- and Nanoswimmers.

Micro/nano biomimetic systems that convert energy from the surroundings into mechanical motion have emerged as promising tools to enhance the efficiencies of different biomedical and environmental processes. The inclusion of multiple engines into the same device has become a promising strategy to achieve dual/triple stimuli responses. Such hybrid micro/nanoswimmers combining different propulsion forces exhibit advanced motion behaviors and different physical features that are interesting not only to achieve strong propulsion capabilities in complex environments but also to modulate their movement according to the intended use. The development of hybrid systems that can be actuated by both light and biocompatible fuels is of particular interest. This minireview covers the main types of photoactive/biocatalytic micro/nanoswimmers developed so far. Their main photoresponsive and enzymatic components are discussed along with the most representative designs. The applicability of such hybrid machines for analyte sensing, antibacterial and therapeutical uses is also described. The remaining challenges and opportunities are then explored.

Enzyme-Photocatalyst Tandem Microrobot Powered by Urea for Escherichia coli Biofilm Eradication.

Urinary-based infections affect millions of people worldwide. Such bacterial infections are mainly caused by Escherichia coli (E. coli) biofilm formation in the bladder and/or urinary catheters. Herein, the authors present a hybrid enzyme/photocatalytic microrobot, based on urease-immobilized TiO2 /CdS nanotube bundles, that can swim in urea as a biocompatible fuel and respond to visible light. Upon illumination for 2 h, these microrobots are able to remove almost 90% of bacterial biofilm, due to the generation of reactive radicals, while bare TiO2 /CdS photocatalysts (non-motile) or urease-coated microrobots in the dark do not show any toxic effect. These results indicate a synergistic effect between the self-propulsion provided by the enzyme and the photocatalytic activity induced under light stimuli. This work provides a photo-biocatalytic approach for the design of efficient light-driven microrobots with promising applications in microbiology and biomedicine.

Hybrid Inorganic-Organic Visible-Light-Driven Microrobots Based on Donor-Acceptor Organic Polymer for Degradation of Toxic Psychoactive Substances.

Light-driven microrobots based on organic semiconductors have received tremendous attention in the past few years due to their unique properties, such as ease of reactivity tunability, band-gap modulation, and low cost. However, their fabrication with defined morphologies is a very challenging task that results in amorphous microrobots with poor motion efficiencies. Herein, we present hybrid inorganic-organic photoactive microrobots with a tubular shape and based on the combination of a mesoporous silica template with an active polymer containing thiophene and triazine units (named as Tz-Th microrobots). Owing to their well-defined tubular structure, such Tz-Th microrobots showed efficient directional motion under fuel-free conditions. Depending on the accumulation of the polymer coating, these microdevices also exhibited stand-up and rotation motion. As a proof-of-concept, we use these hybrid microrobots for the capture and degradation of toxic psychoactive drugs commonly found in wastewater effluents such as methamphetamine derivatives. We found that the microrobots were able to decompose the drug into small organic fragments after 20 min of visible light irradiation, reaching total intermediates removal after 2 h. Therefore, this approach represents a versatile and low-cost strategy to fabricate structured organic microrobots with efficient directional motion by using inorganic materials as the robot chassis, thereby maintaining the superior photocatalytic performance usually associated with such organic polymers.

Epitope-preserving magnified analysis of proteome (eMAP).

Synthetic tissue-hydrogel methods have enabled superresolution investigation of biological systems using diffraction-limited microscopy. However, chemical modification by fixatives can cause loss of antigenicity, limiting molecular interrogation of the tissue gel. Here, we present epitope-preserving magnified analysis of proteome (eMAP) that uses purely physical tissue-gel hybridization to minimize the loss of antigenicity while allowing permanent anchoring of biomolecules. We achieved success rates of 96% and 94% with synaptic antibodies for mouse and marmoset brains, respectively. Maximal preservation of antigenicity allows imaging of nanoscopic architectures in 1000-fold expanded tissues without additional signal amplification. eMAP-processed tissue gel can endure repeated staining and destaining without epitope loss or structural damage, enabling highly multiplexed proteomic analysis. We demonstrated the utility of eMAP as a nanoscopic proteomic interrogation tool by investigating molecular heterogeneity in inhibitory synapses in the mouse brain neocortex and characterizing the spatial distributions of synaptic proteins within synapses in mouse and marmoset brains.

Nanostructured Photocatalysts for the Production of Methanol from Methane and Water.

The direct photocatalytic conversion of methane into methanol with water at room temperature and pressure has attracted particular attention in recent decades. Valuable insight has been obtained into the reaction mechanisms and the key descriptors that control photoactivity and selectivity. This Minireview highlights the different efforts that have been undergone on the design of nanostructured photocatalytic systems to enhance the selectivity to methanol. The effect of structural and electronic aspects, such as surface area, morphologies, crystal facets, redox properties, metal doping, and heterojunctions, on photocatalytic performance, are discussed. The roles of free hydroxyl radicals and/or hydroxy groups for methane activation on the photocatalyst surface are also presented. This Minireview aims to provide an insight into the optimal properties and configurations of the nanostructured photocatalytic materials for tuning their reactivity on the selective oxidation of CH4 to methanol with water. The remaining challenges and promising directions for bringing this technology a step closer to real-world application are also highlighted.

Smartdust 3D-Printed Graphene-Based Al/Ga Robots for Photocatalytic Degradation of Explosives.

Milli/micro/nanorobots are considered smart devices able to convert energy taken from different sources into mechanical movement and accomplish the appointed tasks. Future advances and realization of these tiny devices are mostly limited by the narrow window of material choices, the fuel requirement, multistep surface functionalization, rational structural design, and propulsion ability in complex environments. All these aspects call for intensive improvements that may speed up the real application of such miniaturized robots. 3D-printed graphene-based smartdust robots provided with a magnetic response and filled with aluminum/gallium molten alloy (Al/Ga) for autonomous motion are presented. These robots can swim by reacting with the surrounding environment without adding any fuel. Because their outer surface is coated with a hydrogel/photocatalyst (chitosan/carbon nitride, C3 N4 ) layer, these robots are used for the photocatalytic degradation of the picric acid as an explosive model molecule under visible light. The results show a fast and efficient degradation of picric acid that is attributed to a synergistic effect between the adsorption capability of the chitosan and the photocatalytic activity of C3 N4 particles. This work provides added insight into the large-scale fabrication, easy functionalization, and propulsion of tiny robots for environmental applications.

Microrobots in Brewery: Dual Magnetic/Light-Powered Hybrid Microrobots for Preventing Microbial Contamination in Beer.

Yeasts play a key role in the production of alcoholic beverages by fermentation processes. However, because of their continuous growth, they commonly cause spoilage of the final product. Herein, we introduce dual magnetic/light-responsive self-propelled microrobots that can actively move in a beer sample and capture yeast cells. The presence of magnetic nanoparticles on the surface of the microrobots enables their magnetic actuation under fuel-free conditions. In addition, their photoactivity under visible-light irradiation leads to an overall enhancement of their swimming and yeast removal capabilities. It was found that after the application of the microrobots into a real unfiltered beer sample, these micromachines were able to remove almost 100 % of residual yeasts. In addition, these microrobots could also be added at the initial step of the fermentation process without altering the final beer properties, such as alcohol level, color, and pH. This work demonstrates the potential of using externally actuated microrobots as an innovative and low-cost solution for avoiding yeast spoilage in complex liquid environments, such as alcoholic beverages. Therefore, these autonomous self-propelled microrobots open new avenues for future applications in the food industry.

Fuel-free light-driven micro/nanomachines: artificial active matter mimicking nature.

The recent advances in the micro/nanomotor field have shown great progress in the propulsion of such devices by fuel-free mechanisms. Light, as an abundant and natural source, has been demonstrated to be a promising external field to wirelessly induce the motion of these tiny micro/nanomachines, without the need of any toxic fuel or complex system set-up. This tutorial review covers the most representative examples of light-driven micro/nanomotors developed so far, which self-propelled exclusively under fuel-free conditions. Their different swimming behaviors triggered by light stimuli, divided into four main categories (schooling, phototaxis, gravitaxis and directional motion), are discussed along with their similarities with the motion modes of microorganisms. Moreover, the main parameters that influence the motion of light-driven photocatalytic-based micro/nanomotors as well as alternative strategies to develop more efficient systems are also discussed.

Visible-Light-Driven Single-Component BiVO4 Micromotors with the Autonomous Ability for Capturing Microorganisms.

Light-driven micro/nanomotors represent the next generation of automotive devices that can be easily actuated and controlled by using an external light source. As the field evolves, there is a need for developing more sophisticated micromachines that can fulfill diverse tasks in complex environments. Herein, we introduce single-component BiVO4 micromotors with well-defined micro/nanostructures that can swim both individually and as collectively assembled entities under visible-light irradiation. These devices can perform cargo loading and transport of passive particles as well as living microorganisms without any surface functionalization. Interestingly, after photoactivation, the BiVO4 micromotors exhibited an ability to seek and adhere to yeast cell walls, with the possibility to control their attachment/release by switching the light on/off, respectively. Taking advantage of the selective motor/fungal cells attachment, the fungicidal activity of BiVO4 micromotors under visible illumination was also demonstrated. The presented star-shaped BiVO4 micromotors, obtained by a hydrothermal synthesis, contribute to the potential large-scale fabrication of light-powered micromotors. Moreover, these multifunctional single-component micromachines with controlled self-propulsion, collective behavior, cargo transportation, and photocatalytic activity capabilities hold promising applications in sensing, biohybrids assembly, cargo delivery, and microbiological water pollution remediation.

Glutamate Receptors: Not Just for Excitation.

In this issue of Neuron, Fossati et al. (2019) report a new constellation of players regulating inhibitory synaptogenesis. They show that GluD1, through a non-canonical ionotropic-independent mechanism, controls GABAergic synapse formation via trans-synaptic interactions mediated by extracellular cerebellin-4. They identify ARHGEF12 and PPP1R12A as GluD1 intracellular interactors and downstream effectors.

ZnO/ZnO2/Pt Janus Micromotors Propulsion Mode Changes with Size and Interface Structure: Enhanced Nitroaromatic Explosives Degradation under Visible Light.

Self-motile mesoporous ZnO/Pt-based Janus micromotors accelerated by bubble propulsion that provide efficient removal of explosives and dye pollutants via photodegradation under visible light are presented. Decomposition of H2O2 (the fuel) is triggered by a platinum catalytic layer asymmetrically deposited on the nanosheets of the hierarchical and mesoporous ZnO microparticles. The size-dependent motion behavior of the mesoporous micromotors is studied; the micromotors with average size ∼1.5 µm exhibit enhanced self-diffusiophoretic motion, whereas the fast bubble propulsion is detected for micromotors larger than 5 µm. The bubble-propelled mesoporous ZnO/Pt Janus micromotors show remarkable speeds of over 350 µm s-1 at H2O2 concentrations lower than 5 wt %, which is unusual for Janus micromotors based on dense materials such as ZnO. This high speed is related to efficient bubble nucleation, pinning, and growth due to the highly active and rough surface area of these micromotors, whereas the ZnO/Pt particles with a smooth surface and low surface area are motionless. We discovered new atomic interfaces of ZnO2 introduced into the ZnO/Pt micromotor system, as revealed by X-ray diffraction (XRD), which contribute to enhance their photocatalytic activity under visible light. Such coupling of the rapid movement with the high catalytic performance of ZnO/Pt Janus micromotors provides efficient removal of nitroaromatic explosives and dye pollutants from contaminated water under visible light without the need for UV irradiation. This paves the way for real-world environmental remediation efforts using microrobots.

Metal-Free Visible-Light Photoactivated C3N4 Bubble-Propelled Tubular Micromotors with Inherent Fluorescence and On/Off Capabilities.

Photoactivated micromachines are at the forefront of the micro- and nanomotors field, as light is the main power source of many biological systems. Currently, this rapidly developing field is based on metal-containing segments, typically TiO2 and precious metals. Herein, we present metal-free tubular micromotors solely based on graphitic carbon nitride, as highly scalable and low-cost micromachines that can be actuated by turning on/off the light source. These micromotors are able to move by a photocatalytic-induced bubble-propelled mechanism under visible light irradiation, without any metal-containing part or biochemical molecule on their structure. Furthermore, they exhibit interesting properties, such as a translucent tubular structure that allows the optical visualization of the O2 bubble formation and migration inside the microtubes, as well as inherent fluorescence and adsorptive capability. Such properties were exploited for the removal of a heavy metal from contaminated water with the concomitant optical monitoring of its adsorption by fluorescence quenching. This multifunctional approach contributes to the development of metal-free bubble-propelled tubular micromotors actuated under visible light irradiation for environmental applications.

Micro- and Nanomotors as Active Environmental Microcleaners and Sensors.

The quest to provide clean water to the entire population has led to a tremendous boost in the development of environmental nanotechnology. Toward this end, micro/nanomotors are emerging as attractive tools to improve the removal of various pollutants. The micro/nanomotors either are designed with functional materials in their structure or are modified to target pollutants. The active motion of these motors improves the mixing and mass transfer, greatly enhancing the rate of various remediation processes. Their motion can also be used as an indicator of the presence of a pollutant for sensing purposes. In this Perspective, we discuss different chemical aspects of micromotors mediated environmental cleanup and sensing strategies along with their scalability, reuse, and cost associated challenges.