Prussian Blue/Chitosan Micromotors with Intrinsic Enzyme-like Activity for (bio)-Sensing Assays.

Prussian Blue (PB)/chitosan enzyme mimetic tubular micromotors are used here for on-the-fly (bio)-sensing assays. The micromotors are easily prepared by direct deposition of chitosan into the pores of a membrane template and in situ PB synthesis during hydrogel deposition. Under judicious pH control, PB micromotors display enzyme mimetic capabilities with three key functions on board: the autonomous oxygen bubble propulsion (with PB acting as a catalase mimic for hydrogen peroxide decomposition), 3,3',5,5'-tetramethylbenzidine (TMB) oxidation (with PB acting as a peroxidase mimic for analyte detection), and as a magnetic material (to simplify the (bio)-sensing steps). In connection with chitosan capabilities, these unique enzyme mimetic micromotors are further functionalized with acetylthiocholinesterase enzyme (ATChE) to be explored in fast inhibition assays (20 min) for the colorimetric determination of the nerve agent neostigmine, with excellent analytical performance in terms of quantification limit (0.30 µM) and concentration linear range (up to 500 µM), without compromising efficient micromotor propulsion. The new concept illustrated holds considerable potential for a myriad of (bio)-sensing applications, including forensics, where this conceptual approach remains to be explored. Micromotor-based tests to be used in crime scenes are also envisioned due to the reliable neostigmine determination in unpretreated samples.

Magnetic Hydrogel Microrobots as Insecticide Carriers for In Vivo Insect Pest Control in Plants.

The cost of insect pests to human society exceeds USD70 billion per year worldwide in goods, livestock, and healthcare services. Therefore, pesticides are needed to prevent insect damage despite the secondary effects of these chemical agents on non-target organisms. Chemicals encapsulation into carriers is a promising strategy to improve their specificity. Hydrogel-based microrobots show enormous potential as chemical carriers. Herein, hydrogel chitosan magnetic microrobots encapsulating ethyl parathion (EP)-CHI@Fe3 O4 are used to efficiently kill mealworm larvae (Tenebrio molitor). The mechanism takes advantage of pH-responsive chitosan degradation at Tenebrio molitor midgut pH to efficiently deliver pesticide into the mealworm intestinal tract in just 2 h. It is observed that under a transversal rotating magnetic field, mealworm populations show higher mortality after 30 min compared to free pesticide. This example of active pesticide carriers based on soft microrobots opens new avenues for microrobots applications in the agrochemical field as active chemical carriers.

Biocompatible micromotors for biosensing.

Micro/nanomotors are nanoscale devices that have been explored in various fields, such as drug delivery, environmental remediation, or biosensing and diagnosis. The use of micro/nanomotors has grown considerably over the past few years, partially because of the advantages that they offer in the development of new conceptual avenues in biosensing. This is due to their propulsion and intermixing in solution compared with their respective static forms, which enables motion-based detection methods and/or decreases bioassay time. This review focuses on the impacts of micro/nanomotors on biosensing research in the last 2 years. An overview of designs for bioreceptor attachment to micro/nanomotors is given. Recent developments have focused on chemically propelled micromotors using external fuels, commonly hydrogen peroxide. However, the associated fuel toxicity and inconvenience of use in relevant biological samples such as blood have prompted researchers to explore new micro/nanomotor biosensing approaches based on biocompatible propulsion sources such as magnetic or ultrasound fields. The main advances in biocompatible propulsion sources for micro/nanomotors as novel biosensing platforms are discussed and grouped by their propulsion-driven forces. The relevant analytical applications are discussed and representatively illustrated. Moreover, envisioning future biosensing applications, the principal advantages of micro/nanomotor synthesis using biocompatible and biodegradable materials are given. The review concludes with a realistic drawing on the present and future perspectives.

Multi-Light-Responsive Quantum Dot Sensitized Hybrid Micromotors with Dual-Mode Propulsion.

CdS quantum dots/C60 tubular micromotors with chemical/multi-light-controlled propulsion and "on-the-fly" acceleration capabilities are described. In situ growth of CdS quantum dots on the outer fullerene layer imparts this layer with light-responsive properties in connection to inner Pt, Pd or MnO2 layers. This is the first time that visible light is used to drive bubble-propelled tubular micromotors. The micromotors exhibit a broad absorption range from 320 to 670 nm and can be wirelessly controlled by modulating light intensity and peroxide concentration. The built-in accelerating optical system allows for the control of the velocity over the entire UV/Vis light spectra by modulating the catalyst surface chemistry. The light-responsive properties have been also exploited to accelerate the chemical dealloying and propulsion of micromotors containing a Cu/Pd layer. Such dual operated hybrid micromotors hold considerable promise for designing smart micromachines for on-demand operations, motion-based sensing, and enhanced cargo transportation.

Self-Propelled Micromotors for Naked-Eye Detection of Phenylenediamines Isomers.

Tubular micromotors composed of a hybrid single-wall carbon nanotube (SW)-Fe2O3 outer layer and powered by a MnO2 catalyst are used for phenylenediamines isomers detection and discrimination. Catalytic decomposition of H2O2 as fuel results in the production of oxygen bubbles and hydroxyl radicals for phenylenediamines dimerization to produce colorful solutions in colorimetric assays. The combination of Fe2O3 nanoparticles along with the irregular SW backbone results in a rough catalytic layer for enhanced hydroxyl radical production rate and improved analytical sensitivity. Such self-propelled micromotors act as peroxidase-like mobile platforms that offer efficient phenylenediamines detection and discrimination in just 15 min. Factors influencing the colorimetric assay protocol, such as the navigation time and number of motors, have been investigated. Low limits of detection (5 and 6 µM) and quantification (17 and 20 µM) were obtained for o-phenylenediamine and p-phenylenediamine, respectively. The magnetic properties of the outer SW-Fe2O3 hybrid layer allow the reusability of the micromotors in the colorimetric assay. Such attractive performance holds considerable promise for its application in sensing systems in a myriad of environmental, industrial, and health applications.

Soft Magnetic Microrobots for Photoactive Pollutant Removal.

"Soft" robotics based on hydrogels appears as an alternative to the traditional technology of "hard" robotics. Soft microrobots are employed for drug delivery and cell manipulation. This work develops magnetic hydrogel-based microrobots using chitosan (CHI) as the body of the micromotor and Fe3 O4 nanoparticles to allow for its magnetic actuation. In addition, ZnO nanoparticles are incorporated inside the CHI body of the microrobot to act as an active component for pollutants photodegradation. CHI@Fe3 O4 -ZnO microrobots are used for the efficient photodegradation of persistent organic pollutants (POPs). The high absorption of CHI hydrogel enhances the POP photodegradation, degrading it 75% in just 30 min. The adsorption-degradation and magnetic properties of CHI@Fe3 O4 -ZnO microrobots are used in five cycles while maintaining up to 60% photodegradation efficiency. The proof-of-concept present in this work represents a simple way to obtain soft microrobots with magnetic actuation and photodegradation functionalities for several water purification applications.

Nanostructured Hybrid BioBots for Beer Brewing.

The brewing industry will amass a revenue above 500 billion euros in 2022, and the market is expected to grow annually. This industrial process is based on a slow sugar fermentation by yeast (commonly Saccharomyces cerevisiae). Herein, we encapsulate yeast cells into a biocompatible alginate (ALG) polymer along Fe3O4 nanoparticles to produce magneto/catalytic nanostructured ALG@yeast-Fe3O4 BioBots. Yeast encapsulated in these biocompatible BioBots keeps their biological activity (growth, reproduction, and catalytic fermentation) essential for brewing. Catalytic fermentation of sugars into CO2 gas caused a continuous oscillatory motion of the BioBots in the solution. This BioBot motion is employed to enhance the beer fermentation process compared to static-free yeast cells. When the process is finished, magnetic actuation of BioBots is employed for their retrieval from the beer samples, which avoids the need of additional filtration steps. All in all, we demonstrate how an industrial process such as beer production can be benefited by miniaturized autonomous magneto/catalytic BioBots.

Graphene quantum dot based micromotors: a size matter.

Graphene quantum dots (GQDs) are used as advanced materials for the preparation of micromotors. The small size and large surface-volume ratio improve the solubility properties, resulting in superior synthesis yields and reproducibility. The unique properties associated with the distinct functionalities of GQDs are illustrated in environmental and sensing applications.