MoSBOTs: Magnetically Driven Biotemplated MoS2 -Based Microrobots for Biomedical Applications.

2D layered molybdenum disulfide (MoS2 ) nanomaterials are a promising platform for biomedical applications, particularly due to its high biocompatibility characteristics, mechanical and electrical properties, and flexible functionalization. Additionally, the bandgap of MoS2 can be engineered to absorb light over a wide range of wavelengths, which can then be transformed into local heat for applications in photothermal tissue ablation and regeneration. However, limitations such as poor stability of aqueous dispersions and low accumulation in affected tissues impair the full realization of MoS2 for biomedical applications. To overcome such challenges, herein, multifunctional MoS2 -based magnetic helical microrobots (MoSBOTs) using cyanobacterium Spirulina platensis are proposed as biotemplate for therapeutic and biorecognition applications. The cytocompatible microrobots combine remote magnetic navigation with MoS2 photothermal activity under near-infrared irradiation. The resulting photoabsorbent features of the MoSBOTs are exploited for targeted photothermal ablation of cancer cells and on-the-fly biorecognition in minimally invasive oncotherapy applications. The proposed multi-therapeutic MoSBOTs hold considerable potential for a myriad of cancer treatment and diagnostic-related applications, circumventing current challenges of ablative procedures.

Graphdiyne Micromotors in Living Biomedia.

Graphdiyne (GDY), a new kind of two-dimensional (2D) material, was combined with micromotor technology for "on-the-fly" operations in complex biomedia. Microtubular structures were prepared by template deposition on membrane templates, resulting in functional structures rich in sp and sp2 carbons with highly conjugated π networks. This resulted in a highly increased surface area for a higher loading of anticancer drugs or enhanced quenching ability over other 2D based micromotors, such as graphene oxide (GO) or smooth tubular micromotors. High biocompatibility with almost 100 % cell viability was observed in cytotoxicity assays with moving micromotors in the presence of HeLa cells. On a first example, GDY micromotors loaded with doxorubicin (DOX) were used for pH responsive release and HeLa cancer cells killing. The use of affinity peptide engineered GDY micromotors was also illustrated for highly sensitive and selective fluorescent OFF-ON detection of cholera toxin B through specific recognition of the subunit B region of the target toxin. The new developments illustrated here offer considerable promise for the use of GDY as part of micromotors in living biosystems.

Magnetic Fields Enhanced the Performance of Tubular Dichalcogenide Micromotors at Low Hydrogen Peroxide Levels.

Propulsion at the microscale has attracted significant research interest. In this work, a numerical simulation to explain the speed boost of up to 34 % experienced by transition metal dichalcogenides (TMD) based micromotors under the effect of applied magnetic fields is described. The simulations show that, when an external magnetic field is applied, the flow regime changes from turbulent to laminar. This causes an increase in the residence time of the fuel over the catalyst surface, which enhances the oxygen production. The more efficient generation and growth of the bubbles lead to an increase of the capillary force exerted by them. Interestingly, the effect is more pronounced as the level of fuel decrease. The validity of the model is also proven by comparing both theoretical and experimental results. Interestingly, the speed enhancement in magnetic mode depends on geometrical factors only, as a similar phenomenon was observed in a variety of microjets with a variable surface roughness. The understanding of such phenomena will open new avenues for understanding and controlling the motion behavior of high-towing-force catalytic micromotors.

Photoresponsive MoS2 and WS2 microflakes as mobile biocide agents.

A fuel-free strategy for the eradication of Escherichia coli and Staphylococcus aureus biofilms using WS2 and MoS2 photophoretic microflakes is described. The microflakes were prepared by liquid-phase exfoliation of the materials. Under electromagnetic irradiation at 480 or 535 nm, the microflakes experience a fast collective behavior at speeds of over 300 µm s-1 due to photophoresis. Simultaneously to their motion, reactive oxygen species are generated. The fast microflake schooling into multiple moving swarms results in a highly efficient "collision" platform that disrupts the biofilm, enhancing radical oxygen species' contact with the bacteria for their inactivation. As such, removal biofilm mass rates of over 90% and 65% are achieved using the MoS2 and WS2 microflakes in the treatment of Gram-negative E. coli and Gram-positive S. aureus biofilms after 20 min. Much lower removal biofilm mass rates (30%) are obtained under static conditions, revealing the crucial role of microflake movement and radical generation in the active eradication of biofilms. Much higher removal efficiencies are observed in biofilm deactivation as compared with the use of free antibiotics, which are not able to destroy the densely packed biofilms. The new moving microflakes hold considerable promise for the treatment of antibiotic-resistant bacteria.

Photoactive Au@MoS2 Micromotors for Dynamic Surface-Enhanced Raman Spectroscopy Sensing.

Photophoretic Au@MoS2 micromotors are used as smart mobile substrates for dynamic surface-enhanced Raman spectroscopy (SERS) sensing. The photophoretic capabilities and swarming-like propulsion of the micromotors allow for their schooling and accumulation in the measuring spot, increasing the density of SERS-active gold nanoparticles for Raman mapping and, simultaneously, the preconcentration of the target analyte. The generation of "hot-microflake spots" directly in the Raman irradiation point results in a 15-18-fold enhancement in the detection of crystal violet without the requirement for additional external sources for propulsion. Moreover, the reproducible collective micromotor motion does not depend on the exact position of the laser spot concerning individual micromotors, which greatly simplifies the experimental setup, avoiding the requirements of sophisticated equipment. The strategy was further applied for the detection of malachite green and paraquat with a good signal enhancement. The new on-the-move-based SERS strategy holds great promise for on-site detection with portable instrumentation in a myriad of environmental monitoring and clinical applications.

On-board smartphone micromotor-based fluorescence assays.

Herein, we describe the design of a portable device integrated with micromotors for real-time fluorescence sensing of (bio)markers. The system comprises a universal 3D printed platform to hold a commercial smartphone, which is equipped with an external magnification optical lens (20-400×) and tailor-made emission filters directly attached to the camera, an adjustable sample holder to accommodate a glass slide and laser excitation sources. On a first approach, we illustrate the suitability of the platform using magnetic Janus micromotors modified with fluorescent ZnS@CdxSe1-x quantum dots for real-time ON-OFF mercury detection. On a second approach, graphdiyne tubular catalytic micromotors modified with a rhodamine labelled affinity peptide are used for the OFF-ON detection of cholera toxin B. The micromotor-based smartphone for fluorescence sensing approach was compared to a high-performance optical microscope, and similar analytical features were obtained. This versatility allows for easy integration of micromotor fluorescence sensing strategies based on different propulsion mechanisms, allowing for its future use with a myriad of biomarkers and even multiplexed schemes.

Near infrared-light responsive WS2 microengines with high-performance electro- and photo-catalytic activities.

Tungsten disulfide (WS2)-based micromotors with enhanced electrochemical and photo-catalytic activities are synthesized using a greatly simplified electrochemical deposition protocol at room temperature involving exclusively tungstic acid and sulfate as metal and sulfur sources without further building chemistry. The WS2-based micromotors exhibit dual electrochemical and photo-catalytic behavior in the inner and outer layers, respectively, due to the combination of the unique properties of the sp2 hybridized WS2 outer layer with highly reactive WS2-induced inner catalytic layers, accounting for this material's exclusive enhanced performances. A rough inner Pt-Ni layer allows tailoring the micromotor propulsion, with a speed increase of up to 1.6 times after external control of the micromotor with a magnetic field due to enhanced fuel accessibility. Such a coupling of the attractive capabilities of WS2 with enhanced micromotor movement holds considerable promise to address the growing energy crisis and environmental pollution concerns.

Identification and determination of synthetic cannabinoids in herbal products by dry film attenuated total reflectance-infrared spectroscopy.

A new procedure has been developed for the identification and quantitative determination of synthetic cannabinoids in illicit herbal preparations. The methodology is based on the use of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) measurement of sample extracts with 2-propanol drying 5µL of the extracts onto the ATR crystal. The qualitative identification was carried out on the 2-propanol extract after identification of the herbal matrix, followed by its subtraction and using a cut-off criterion of 75%. Quantitative determination was made by univariate calibration using the absorbance of the band located at 1520cm-1 of the spectrum. Four different cannabinoids, RCS-4, JWH-210, UR-144 and JWH-081 were used as test analytes and the ATR-FTIR method provided limits of quantification from 14 till 79mgL-1. Sized blank market samples were successfully identified and UR-144 quantified.