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 <i>o</i>-phenylenediamine and <i>p</i>-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

Self-Propelled Enzyme-Based Motors for Smart Mobile Electrochemical and Optical Biosensing

A millimeter-sized tubular motor for mobile biosensing of H₂O₂ in environmental and relevant clinical samples is reported. The concept relies on the self-propelled motion by the Marangoni effect, where the asymmetric release of SDS surfactant induces fluid convection and rapid dispersion of horseradish peroxidase (HRP) enzyme into the sample solution. This efficient movement together with the continuous release of fresh enzyme leads to greatly accelerated enzymatic reaction processes without the need of external stirring or chemical and physical attachment of the enzyme as in common classical biosensing approaches. In this strategy, the use of a single millimeter-sized tubular motor during 120 s allows the reliable and accurate quantification of hydrogen peroxide in a set of different matrices such as tap and mineral waters, urine, plasma, and tumor cell cultures treated with antineoplasic Cisplatin without any previous sample preparation. Furthermore, detection can be performed electrochemically, optically, and via visual detection, which makes this approach a clear candidate as a point-of-care analytical tool

Self-Propelled Enzyme-Based Motors for Smart Mobile Electrochemical and Optical Biosensing

A millimeter-sized tubular motor for mobile biosensing of H₂O₂ in environmental and relevant clinical samples is reported. The concept relies on the self-propelled motion by the Marangoni effect, where the asymmetric release of SDS surfactant induces fluid convection and rapid dispersion of horseradish peroxidase (HRP) enzyme into the sample solution. This efficient movement together with the continuous release of fresh enzyme leads to greatly accelerated enzymatic reaction processes without the need of external stirring or chemical and physical attachment of the enzyme as in common classical biosensing approaches. In this strategy, the use of a single millimeter-sized tubular motor during 120 s allows the reliable and accurate quantification of hydrogen peroxide in a set of different matrices such as tap and mineral waters, urine, plasma, and tumor cell cultures treated with antineoplasic Cisplatin without any previous sample preparation. Furthermore, detection can be performed electrochemically, optically, and via visual detection, which makes this approach a clear candidate as a point-of-care analytical tool

Biosensing Strategy for Simultaneous and Accurate Quantitative Analysis of Mycotoxins in Food Samples Using Unmodified Graphene Micromotors

A high-performance graphene-based micromotor strategy for simultaneous, fast, and reliable assessment of two highly concerning mycotoxins (fumonisin B1 (FB1) and ocratoxin A (OTA)) has successfully been developed. The assay principle is based on the selective recognition from aptamers to the target mycotoxins and further “on-the-move” fluorescence <i>quenching</i> of the free aptamer in the outer layer of unmodified reduced graphene (rGO; sensing layer) micromotors. Template-prepared rGO/platinum nanoparticles (PtNPs) tubular micromotors were synthesized rapidly and inexpensively by the direct electrodeposition within the conical pores of a polycarbonate template membrane. The new wash-free approach offers using just 1 μL of sample, a simultaneous and rapid “on-the-fly” detection (2 min) with high sensitivity (limits of detection of 7 and 0.4 ng/mL for OTA and FB1, respectively), and high selectivity. Remarkable accuracy (<i>E</i>_r < 5%) during the mycotoxin determination in certified reference material as well as excellent quantitative recoveries (96–98%) during the analysis of food samples were also obtained. The excellent results obtained allow envisioning an exciting future for the development of novel applications of catalytic micromotors in unexplored fields such as food safety diagnosis

Biosensing Strategy for Simultaneous and Accurate Quantitative Analysis of Mycotoxins in Food Samples Using Unmodified Graphene Micromotors

A high-performance graphene-based micromotor strategy for simultaneous, fast, and reliable assessment of two highly concerning mycotoxins (fumonisin B1 (FB1) and ocratoxin A (OTA)) has successfully been developed. The assay principle is based on the selective recognition from aptamers to the target mycotoxins and further “on-the-move” fluorescence <i>quenching</i> of the free aptamer in the outer layer of unmodified reduced graphene (rGO; sensing layer) micromotors. Template-prepared rGO/platinum nanoparticles (PtNPs) tubular micromotors were synthesized rapidly and inexpensively by the direct electrodeposition within the conical pores of a polycarbonate template membrane. The new wash-free approach offers using just 1 μL of sample, a simultaneous and rapid “on-the-fly” detection (2 min) with high sensitivity (limits of detection of 7 and 0.4 ng/mL for OTA and FB1, respectively), and high selectivity. Remarkable accuracy (<i>E</i>_r < 5%) during the mycotoxin determination in certified reference material as well as excellent quantitative recoveries (96–98%) during the analysis of food samples were also obtained. The excellent results obtained allow envisioning an exciting future for the development of novel applications of catalytic micromotors in unexplored fields such as food safety diagnosis

Enzyme-Based Microfluidic Chip Coupled to Graphene Electrodes for the Detection of D‑Amino Acid Enantiomer-Biomarkers

An electrochemical microfluidic strategy for the separation and enantiomeric detection of d-methionine (d-Met) and d-leucine (d-Leu) is presented. These D-amino acids (D-AAs) act as biomarkers involved in relevant diseases caused by <i>Vibrio cholerae</i>. On a single layout microfluidic chip (MC), highly compatible with extremely low biological sample consumption, the strategy allowed the controlled microfluidic D-AA separation and the specific reaction between D-amino acid oxidase (DAAO) and each D-AA biomarker avoiding the use of additives (i.e., cyclodextrins) for enantiomeric separation as well as any covalent immobilization of the enzyme into the wall channels or on the electrode surface such as in the biosensor-based approaches. Hybrid polymer/graphene-based electrodes were end-channel coupled to the microfluidic system to improve the analytical performance. d-Met and d-Leu were successfully detected becoming this proof-of-the-concept a promising principle for the development of point-of-care (POC) devices for <i>in situ</i> screening of <i>V. cholerae</i> related diseases

Superhydrophobic Alkanethiol-Coated Microsubmarines for Effective Removal of Oil

We demonstrate the use of artificial nanomachines for effective interaction, capture, transport, and removal of oil droplets. The simple nanomachine-enabled oil collection method is based on modifying microtube engines with a superhydrophobic layer able to adsorb oil by means of its strong adhesion to a long chain of self-assembled monolayers (SAMs) of alkanethiols created on the rough gold outer surface of the device. The resultant SAM-coated Au/Ni/PEDOT/Pt microsubmarine displays continuous interaction with large oil droplets and is capable of loading and transporting multiple small oil droplets. The influence of the alkanethiol chain length, polarity, and head functional group and hence of the surface hydrophobicity upon the oil–nanomotor interaction and the propulsion is examined. No such oil–motor interactions were observed in control experiments involving both unmodified microengines and microengines coated with SAM layers containing a polar terminal group. These results demonstrate that such SAM-Au/Ni/PEDOT/Pt micromachines can be useful for a facile, rapid, and efficient collection of oils in water samples, which can be potentially exploited for other water–oil separation systems. The integration of oil-sorption properties into self-propelled microengines holds great promise for the remediation of oil-contaminated water samples and for the isolation of other hydrophobic targets, such as drugs

Acoustic Microcannons: Toward Advanced Microballistics

Acoustically triggered microcannons, capable of loading and firing nanobullets (Nbs), are presented as powerful microballistic tools. Hollow conically shaped microcannon structures have been synthesized electrochemically and fully loaded with nanobullets made of silica or fluorescent microspheres, and perfluorocarbon emulsions, embedded in a gel matrix stabilizer. Application of a focused ultrasound pulse leads to the spontaneous vaporization of the perfluorocarbon emulsions within the microcannon and results in the rapid ejection of the nanobullets. Such Nbs “firing” at remarkably high speeds (on the magnitude of meters per second) has been modeled theoretically and demonstrated experimentally. Arrays of microcannons anchored in a template membrane were used to demonstrate the efficient Nbs loading and the high penetration capabilities of the ejected Nbs in a tissue phantom gel. This acoustic-microcannon approach could be translated into advanced microscale ballistic tools, capable of efficient loading and firing of multiple cargoes, and offer improved accessibility to target locations and enhanced tissue penetration properties