Highly Sustainable h-BN Encapsulated MoS2 Hydrogen Evolution Catalysts.

Despite the importance of the stability of the 2D catalysts in harsh electrolyte solutions, most studies have focused on improving the catalytic performance of molybdenum disulfide (MoS2) catalysts rather than the sustainability of hydrogen evolution. In previous studies, the vulnerability of MoS2 crystals is reported that the moisture and oxygen molecules can cause the oxidation of MoS2 crystals, accelerating the degradation of crystal structure. Therefore, optimization of catalytic stability is crucial for approaching practical applications in 2D catalysts. Here, it is proposed that monolayered MoS2 catalysts passivated with an atomically thin hexagonal boron nitride (h-BN) layer can effectively sustain hydrogen evolution reaction (HER) and demonstrate the ultra-high current density (500 mA cm⁻2 over 11 h) and super stable (64 h at 150 mA cm⁻2) catalytic performance. It is further confirmed with density functional theory (DFT) calculations that the atomically thin h-BN layer effectively prevents direct adsorption of water/acid molecules while allowing the protons to be adsorbed/penetrated. The selective penetration of protons and prevention of crystal structure degradation lead to maintained catalytic activity and maximized catalytic stability in the h-BN covered MoS2 catalysts. These findings propose a promising opportunity for approaching the practical application of 2D MoS2 catalysts having long-term stability at high-current operation.

Calcium Alginate as an Active Device Component for Light-Triggered Degradation of 2D MoS2-Based Transient Electronics.

Transient electronics technology has enabled the programmed disintegration of functional devices, paving the way for environmentally sustainable management of electronic wastes as well as facilitating the exploration of novel device concepts. While a variety of inorganic and/or organic materials have been employed as media to introduce transient characteristics in electronic devices, they have been mainly limited to function as passive device components. Herein, we report that calcium (Ca) alginate, a natural biopolymer, exhibits multifunctionalities of introducing light-triggered transient characteristics as well as constituting active components in electronic devices integrated with two-dimensional (2D) molybdenum disulfide (MoS2) layers. Ca2+ ions-based alginate electrolyte films are prepared through hydrolysis reactions and are subsequently incorporated with riboflavin, a natural photosensitizer, for the light-driven dissolution of 2D MoS2 layers. The alginate films exhibit strain-sensitive triboelectricity, confirming the presence of abundant mobile Ca2+ ions, which enables them to be active components of 2D MoS2 field-effect transistors (FETs) functioning as electrolyte top-gates. The alginate-integrated 2D MoS2 FETs display intriguing transient characteristics of spontaneous degradation upon ultraviolet-to-visible light illumination as well as water exposure. Such transient characteristics are demonstrated even in ambient conditions with natural sunlight, highlighting the versatility of the developed approach. This study emphasizes a relatively unexplored aspect of combining naturally abundant polymers with emerging near atom-thickness semiconductors toward realizing unconventional and transformative device functionalities.

Quasi-Solid-State Electrolyte Induced by Metallic MoS2 for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are a promising high-energy-density technology for next-generation energy storage but suffer from an inadequate lifespan. The poor cycle life of Li-S batteries stems from their commonly adopted catholyte-mediated operating mechanism, where the shuttling of dissolved polysulfides results in active material loss on the sulfur cathode and surface corrosion on the lithium anode. Here, we report in situ formation of a quasi-solid-state electrolyte (QSSE) on the metallic 1T phase molybdenum disulfide (MoS2) host that extends the lifetime of Li-S batteries. We find that the metallic 1T phase MoS2 host is able to initiate the ring-opening polymerization of 1,3-dioxolane (DOL), forming an integrated QSSE inside batteries. Nuclear magnetic resonance analysis reveals that the QSSE consists of ∼13% liquid DOL in a solid polymer matrix. The QSSE efficiently mediates sulfur redox reactions through dissolution-conversion chemistry while simultaneously suppressing polysulfide shuttling. Therefore, while ensuring high sulfur utilization, it avoids degradation of both electrodes, as well as the concomitant electrolyte consumption, leading to enhanced cycling stability. Under a practical lean electrolyte condition (electrolyte-to-sulfur ratio = 2 µL mg-1), Li-S pouch cell batteries with the QSSE demonstrate a capacity retention of 80.7% after 200 cycles, much superior to conventional liquid electrolyte cells that fail within 70 cycles. The QSSE also enables Li-S pouch cell batteries to operate across a wider temperature range (5 to 45 °C), together with improved safety under mechanical damage.

Unlocking the Potential of 2D MoS2 Cathodes for High-Performance Aqueous Al-Ion Batteries: Deciphering the Intercalation Mechanisms.

In recent years, there have been significant advancements in Al-ion battery development, resulting in high voltage and capacity. Traditionally, only carbon-based materials with layered structures and strong bonding capabilities can deliver superior performance. However, most other materials exhibited low discharge voltages of 1.4 V, especially in aqueous Al-ion battery systems lacking anion intercalation. Thus, the development of high-voltage cathode materials has become crucial. This study introduces 2D MoS2 as a high-performance cathode for aqueous Al-ion batteries. The material's interlayer structure enables the intercalation of AlCl4 - anions, resulting in high-voltage intercalation. The resulting battery achieved a high voltage of 1.8 V with a capacity of 750 mAh g-1 , contributing to a high energy density of 890 Wh kg-1 and an impressive retention rate of ≈100% after 200 cycles. This research not only sheds light on the high-voltage anion-intercalation mechanism of MoS2 but also paves the way for the further development of advanced cathode materials in the field of Al-ion batteries. By demonstrating the potential of using 2D MoS2 as a cathode material, this finding can lead to the development of more efficient and innovative energy storage technologies, ultimately contributing to a sustainable and green energy future.

In Situ Synthesis of Crystalline MoS2@ZIF-67 Nanocomposite for the Efficient Removal of Methyl Orange Dye from Aqueous Media.

The zeolitic imidazolate framework-67 (ZIF-67) adsorbent and its composites are known to effectively remove organic dyes from aqueous environments. Here, we report a unique crystalline MoS2@ZIF-67 nanocomposite adsorbent for the efficient removal of methyl orange (MO) dye from an aqueous medium. In situ synthetic techniques were used to fabricate a well-crystalline MoS2@ZIF-67 nanocomposite, which was then discovered to be a superior adsorbent to its constituents. The successful synthesis of the nanocomposite was confirmed using XRD, EDX, FTIR, and SEM. The MoS2@ZIF-67 nanocomposite exhibited faster adsorption kinetics and higher dye removal efficiency compared with its constituents. The adsorption kinetic data matched well with the pseudo-second-order model, which signifies that the MO adsorption on the nanocomposite is a chemically driven process. The Langmuir model successfully illustrated the MO dye adsorption on the nanocomposite through comparing the real data with adsorption isotherm models. However, it appears that the Freundlich adsorption isotherm model was also in competition with the Langmuir model. According to the acquired thermodynamics parameters, the adsorption of MO on the MoS2@ZIF-67 nanocomposite surface was determined to be spontaneous and exothermic. The findings of this research open an avenue for using the MoS2@ZIF-67 nanocomposite to efficiently remove organic dyes from wastewater efflux.

Salt-Induced High-Density Vacancy-Rich 2D MoS2 for Efficient Hydrogen Evolution.

Emerging non-noble metal 2D catalysts, such as molybdenum disulfide (MoS2 ), hold great promise in hydrogen evolution reactions. The sulfur vacancy is recognized as a key defect type that can activate the inert basal plane to improve the catalytic performance. Unfortunately, the method of introducing sulfur vacancies is limited and requires costly post-treatment processes. Here, a novel salt-assisted chemical vapor deposition (CVD) method is demonstrated for synthesizing ultrahigh-density vacancy-rich 2H-MoS2 , with a controllable sulfur vacancy density of up to 3.35 × 1014  cm-2 . This approach involves a pre-sprayed potassium chloridepromoter on the growth substrate. The generation of such defects is closely related to ion adsorption in the growth process, the unstable MoS2 -K-H2 O triggers the formation of sulfur vacancies during the subsequent transfer process, and it is more controllable and nondestructive when compared to traditional post-treatment methods. The vacancy-rich monolayer MoS2 exhibits exceptional catalytic activity based on the microcell measurements, with an overpotential of ≈158.8 mV (100 mA cm-2 ) and a Tafel slope of 54.3 mV dec-1 in 0.5 m H2 SO4 electrolyte. These results indicate a promising opportunity for modulating sulfur vacancy defects in MoS2 using salt-assisted CVD growth. This approach represents a significant leap toward achieving better control over the catalytic performances of 2D materials.

The Effectiveness of Cyrene as a Solvent in Exfoliating 2D TMDs Nanosheets.

The pursuit of environmentally friendly solvents has become an essential research topic in sustainable chemistry and nanomaterial science. With the need to substitute toxic solvents in nanofabrication processes becoming more pressing, the search for alternative solvents has taken on a crucial role in this field. Additionally, the use of toxic, non-economical organic solvents, such as N-methyl-2 pyrrolidone and dimethylformamide, is not suitable for all biomedical applications, even though these solvents are often considered as the best exfoliating agents for nanomaterial fabrication. In this context, the success of producing two-dimensional transition metal dichalcogenides (2D TMDs), such as MoS2 and WS2, with excellent captivating properties is due to the ease of synthesis based on environment-friendly, benign methods with fewer toxic chemicals involved. Herein, we report for the first time on the use of cyrene as an exfoliating agent to fabricate monolayer and few-layered 2D TMDs with a versatile, less time-consuming liquid-phase exfoliation technique. This bio-derived, aprotic, green and eco-friendly solvent produced a stable, surfactant-free, concentrated 2D TMD dispersion with very interesting features, as characterized by UV-visible and Raman spectroscopies. The surface charge and morphology of the fabricated nanoflakes were analyzed using ς-potential and scanning electron microscopy. The study demonstrates that cyrene is a promising green solvent for the exfoliation of 2D TMD nanosheets with potential advantages over traditional organic solvents. The ability to produce smaller-sized-especially in the case of WS2 as compared to MoS2-and mono/few-layered nanostructures with higher negative surface charge values makes cyrene a promising candidate for various biomedical and electronic applications. Overall, the study contributes to the development of sustainable and environmentally friendly methods for the production of 2D nanomaterials for various applications.

Synergistic Photon Management and Strain-Induced Band Gap Engineering of Two-Dimensional MoS2 Using Semimetal Composite Nanostructures.

2D MoS2 attracts increasing attention for its application in flexible electronics and photonic devices. For 2D material optoelectronic devices, the light absorption of the molecularly thin 2D absorber would be one of the key limiting factors in device efficiency, and conventional photon management techniques are not necessarily compatible with them. In this study, we show two semimetal composite nanostructures deposited on 2D MoS2 for synergistic photon management and strain-induced band gap engineering: (1) the pseudo-periodic Sn nanodots, (2) the conductive SnOx (x < 1) core-shell nanoneedle structures. Without sophisticated nanolithography, both nanostructures are self-assembled from physical vapor deposition. Optical absorption enhancement spans from the visible to the near-infrared regime. 2D MoS2 achieves >8× optical absorption enhancement at λ = 700-940 nm and 3-4× at λ = 500-660 nm under Sn nanodots, and 20-30× at λ = 700-900 nm under SnOx (x < 1) nanoneedles. The enhanced absorption in MoS2 results from strong near-field enhancement and reduced MoS2 band gap due to the tensile strain induced by the Sn nanostructures, as confirmed by Raman and photoluminescence spectroscopy. Especially, we demonstrate that up to 3.5% biaxial tensile strain is introduced to 2D MoS2 using conductive nanoneedle-structured SnOx (x < 1), which reduces the band gap by ∼0.35 eV to further enhance light absorption at longer wavelengths. To the best of our knowledge, this is the first demonstration of a synergistic triple-functional photon management, stressor, and conductive electrode layer on 2D MoS2. Such synergistic photon management and band gap engineering approach for extended spectral response can be further applied to other 2D materials for future 2D photonic devices.

An ultrasensitive FET biosensor based on vertically aligned MoS2 nanolayers with abundant surface active sites.

Molybdenum disulfide (MoS2) nanolayers are one of the most promising two-dimensional (2D) nanomaterials for constructing next-generation field-effect transistor (FET) biosensors. In this article, we report an ultrasensitive FET biosensor that integrates a novel format of 2D MoS2, vertically-aligned MoS2 nanolayers (VAMNs), as the channel material for label-free detection of the prostate-specific antigen (PSA). The developed VAMNs-based FET biosensor shows two distinctive advantages. First, the VAMNs can be facilely grown using the conventional chemical vapor deposition (CVD) method, permitting easy fabrication and potential mass device production. Second, the unique advantage of the VAMNs for biosensor development lies in its abundant surface-exposed active edge sites that possess a high binding affinity with thiol-based linkers, which overcomes the challenge of molecule functionalization on the conventional planar MoS2 nanolayers. The high binding affinity between 11-mercaptoundecanoic acid and the VAMNs was demonstrated through experimental surface characterization and theoretical calculations via density functional theory. The FET biosensor allows rapid (within 20 min) and ultrasensitive PSA detection in human serum with simple operations (limit of detection: 800 fg mL-1). This FET biosensor offers excellent features such as ultrahigh sensitivity, ease of fabrication, and short assay time, and thereby possesses significant potential for early-stage diagnosis of life-threatening diseases.

Unveiling the Collaborative Effect at the Cucurbit[8]uril-MoS2 Hybrid Interface for Electrochemical Melatonin Determination.

Host-guest interactions are of paramount importance in supramolecular chemistry and in a wide range of applications. Particularly well known is the ability of cucurbit[n]urils (CB[n]) to selectively host small molecules. We show that the charge transfer and complexation capabilities of CB[n] are retained on the surface of 2D transition metal dichalcogenides (TMDs), allowing the development of efficient electrochemical sensing platforms. We unveil the mechanisms of host-guest recognition between the MoS2 -CB[8] hybrid interface and melatonin (MLT), an important molecular regulator of vital constants in vertebrates. We find that CB[8] on MoS2 organizes the receptor portals perpendicularly to the surface, facilitating MLT complexation. This advantageous adsorption geometry is specific to TMDs and favours MLT electro-oxidation, as opposed to other 2D platforms like graphene, where one receptor portal is closed. This study rationalises the cooperative interaction in 2D hybrid systems to improve the efficiency and selectivity of electrochemical sensing platforms.

Polygonal gold nanocrystal induced efficient phase transition in 2D-MoS2for enhancing photo-electrocatalytic hydrogen generation.

Plasmonic nanocrystals (NCs) assisted phase transition of two-dimensional molybdenum disulfide (2D-MoS2) unlashes numerous opportunities in the fields of energy harvesting via electrocatalysis and photoelectrocatalysis by enhancing electronic conductivity, increasing catalytic active sites, lowering Gibbs free energy for hydrogen adsorption and desorption, etc. Here, we report the synthesis of faceted gold pentagonal bi-pyramidal (Au-PBP) nanocrystals (NC) for efficient plasmon-induced phase transition (from 2 H to 1 T phase) in chemical vapor deposited 2D-MoS2. The as-developed Au-PBP NC with the increased number of corners and edges showed an enhanced multi-modal plasmonic effect under light irradiations. The overpotential of hydrogen evolution reaction (HER) was reduced by 61 mV, whereas the Tafel slope decreased by 23.7 mV/dec on photoexcitation of the Au-PBP@MoS2hybrid catalyst. The enhanced performance can be attributed to the light-induced 2H to 1 T phase transition of 2D-MoS2, increased active sites, reduced Gibbs free energy, efficient charge separation, change in surface potential, and improved electrical conductivity of 2D-MoS2film. From density functional theory (DFT) calculations, we obtain a significant change in the electronic properties of 2D-MoS2(i.e. work function, surface chemical potential, and the density of states), which was primarily due to the plasmonic interactions and exchange-interactions between the Au-PBP nanocrystals and monolayer 2D-MoS2, thereby enhancing the phase transition and improving the surface properties. This work would lay out finding assorted routes to explore more complex nanocrystals-based multipolar plasmonic NC to escalate the HER activity of 2D-MoS2and other 2D transition metal dichalcogenides.

A Stable Rechargeable Aqueous Zn-Air Battery Enabled by Heterogeneous MoS2 Cathode Catalysts.

Aqueous rechargeable zinc (Zn)−air batteries have recently attracted extensive research interest due to their low cost, environmental benignity, safety, and high energy density. However, the sluggish kinetics of oxygen (O2) evolution reaction (OER) and the oxygen reduction reaction (ORR) of cathode catalysts in the batteries result in the high over-potential that impedes the practical application of Zn−air batteries. Here, we report a stable rechargeable aqueous Zn−air battery by use of a heterogeneous two-dimensional molybdenum sulfide (2D MoS2) cathode catalyst that consists of a heterogeneous interface and defects-embedded active edge sites. Compared to commercial Pt/C-RuO2, the low cost MoS2 cathode catalyst shows decent oxygen evolution and acceptable oxygen reduction catalytic activity. The assembled aqueous Zn−air battery using hybrid MoS2 catalysts demonstrates a specific capacity of 330 mAh g−1 and a durability of 500 cycles (~180 h) at 0.5 mA cm−2. In particular, the hybrid MoS2 catalysts outperform commercial Pt/C in the practically meaningful high-current region (>5 mA cm−2). This work paves the way for research on improving the performance of aqueous Zn−air batteries by constructing their own heterogeneous surfaces or interfaces instead of constructing bifunctional catalysts by compounding other materials.

Large-area vertically aligned 2D MoS2layers on TEMPO-cellulose nanofibers for biodegradable transient gas sensors.

Crystallographically anisotropic two-dimensional (2D) molybdenum disulfide (MoS2) with vertically aligned (VA) layers is attractive for electrochemical sensing owing to its surface-enriched dangling bonds coupled with extremely large mechanical deformability. In this study, we explored VA-2D MoS2layers integrated on cellulose nanofibers (CNFs) for detecting various volatile organic compound gases. Sensor devices employing VA-2D MoS2/CNFs exhibited excellent sensitivities for the tested gases of ethanol, methanol, ammonia, and acetone; e.g. a high response rate up to 83.39% for 100 ppm ethanol, significantly outperforming previously reported sensors employing horizontally aligned 2D MoS2layers. Furthermore, VA-2D MoS2/CNFs were identified to be completely dissolvable in buffer solutions such as phosphate-buffered saline solution and baking soda buffer solution without releasing toxic chemicals. This unusual combination of high sensitivity and excellent biodegradability inherent to VA-2D MoS2/CNFs offers unprecedented opportunities for exploring mechanically reconfigurable sensor technologies with bio-compatible transient characteristics.

Mechanistic Study on Enhanced Electrocatalytic Nitrogen Reduction Reaction by Mo Single Clusters Supported on MoS2.

The electrocatalytic N2 reduction reaction (eNRR) at ambient conditions is an appealing method for NH3 synthesis. It has attracted broad research interest in eNRR catalysts. In this work, by a theoretical study based on density functional calculations, we attributed the higher eNRR activity of defective MoS2 than pure MoS2 to the exposed Mo atom with unsaturated coordination sites in the interlayer of defective MoS2. The finding inspired us to explore the eNRR performance of Mo single atom/clusters with one/more active Mo sites supported on MoS2 [Mon@MoS2 (n = 1∼11)] and the corresponding catalytic mechanism. All considered Mon@MoS2 irrespective of N2 or H adsorption selectivity can achieve higher eNRR activity with lower overpotential and lower NH3 desorption free energy than defective MoS2. The competitive hydrogen evolution reaction can be well suppressed on Mon@MoS2 when n = 2∼10. In particular, Mo9@MoS2 with N2 adsorption selectivity exhibits excellent eNRR activity (η = 0.19 V) and high eNRR selectivity, and it can efficiently desorb the produced NH3 with a low desorption free energy (0.50 eV) to achieve a high ammonia yield with the aid of the produced ammonia molecule in the first eNRR process, which is coadsorbed on the Mo9 single cluster during the later eNRR process. The high eNRR activity of Mon@MoS2 can be attributed to its inherent properties of excellent electrical conductivity, electron accessibility, and multiple exposed Mo active sites available for N-containing species coadsorption. The results demonstrate the significance of H preadsorption, the additional N2 adsorption, and the adsorbed product ammonia in the prior eNRR process in enhancing the overall eNRR performance of different-size single-cluster catalysts. Our work provides a guidance for future study of single-cluster catalysts.

Superparamagnetic Nickel Nanocluster-Embedded MoS2 Nanosheets for Gram-Selective Bacterial Adhesion and Antibacterial Activity.

Ever increasing infectious diseases caused by pathogenic bacteria are creating one of the greatest health problems. The extensive use of numerous antibiotics and antimicrobial agents has prompted the growth of multidrug-resistant bacterial strains. The ancient biomedical application of metals and the recent advancement in the field of nanotechnology have encouraged us to explore the antimicrobial activity of nanomaterials. Herein, we have synthesized a magnetically separable superparamagnetic nickel nanocluster-loaded two-dimensional molybdenum disulfide nanocomposite (Ni@2D-MoS2). It can selectively bind with Gram-positive bacteria such as methicillin-resistant Staphylococcus aureus (MRSA) and Enterococcus faecalis over Gram-negative bacteria such as Escherichia coli and Pseudomonas aeruginosa. After the functionalization of Ni@2D-MoS2 with a positively charged ligand, it showed an excellent Gram-selective antibacterial activity toward MRSA and E. faecalis. Furthermore, the superparamagnetic property of the synthesized material can be used for the simultaneous removal and killing of the microbes and recycled for further use. This study demonstrates strategies to develop hybrid antimicrobial nanomaterial systems for selective antibacterial activity with recyclability.

Rapid Discrimination of Bacterial Drug Resistivity by Array-Based Cross-Validation Using 2D MoS2.

The precise discrimination of microbes based on family, class and drug resistivity is essential for the early diagnosis of infectious diseases. Information about the type and strength of drug resistivity can help the analyst to prescribe a suitable antibiotic at the proper dosage to completely eradicate microbes without giving them a chance to gain further resistance. Herein, we propose a sensor array based on the use of cationic two-dimensional MoS2 units and green fluorescence protein as building blocks. Cationic surfaces of receptors with various functionality were suitable for tunable interaction with anionic surfaces of microbes. The array successfully discriminates six different bacterial strains. The versatile ability of the receptors to bind with the wild-type as well as the corresponding ampicillin-resistant strain contributed significantly to rapid detection with high sensitivity. The optimized array was able to classify five different types and three different extents of drug-resistant variants of Escherichia coli by using bacteria cells and lysates. Finally, we have introduced the cross identification method using both bacteria cells and lysates and we found a great enhancement of detection in sensitivity and accuracy. This is the first report of this approach, which can be extended to many other methods for better accuracy in array-based detection.

Magnetic Order, Electrical Doping, and Charge-State Coupling at Amphoteric Defect Sites in Mn-Doped 2D Semiconductors.

Two-dimensional (2D) dilute magnetic semiconductors (DMSs) are attractive material platforms for applications in multifunctional nanospintronics due to the prospect of embedding controllable magnetic order within nanoscale semiconductors. Identifying candidate host material and dopant systems requires consideration of doping formation energies, magnetic ordering, and the tendency for dopants to form clustered domains. In this work, we consider the defect thermodynamics and the dilute magnetic properties across charge states of 2D-MoS2 and 2D-WS2 with Mn magnetic dopants as candidate systems for 2D-DMSs. Using hybrid density functional calculations, we study the magnetic and electronic properties of these systems across configurations with thermodynamically favorable defects: 2D-MoS2 doped with Mn atoms at sulfur site (MnS), at two Mo sites (2MnMo), on top of a Mo atom (Mn-top), and at a Mo site (MnMo). While the majority of the Mn-defect complexes provide trap states, MnMo and MnW are amphoteric, although previously predicted to be donor defects. The impact of cluster formation of these amphoteric defects on magnetic ordering is also considered; both MnMo-MnMo (2Mn2Mo) and MnW-MnW (2Mn2W) clusters are found to be stable in ferromagnetic (FM) ordering. Interestingly, we observed the defect charge state dependent magnetic behavior of 2Mn2Mo and 2Mn2W clusters in 2D-TMDs. We investigate that the FM coupling of 2Mn2Mo and 2Mn2W clusters is stable in only a neutral charge state; however, the antiferromagnetic (AFM) coupling is stable in the +1 charge state. 2Mn2Mo clusters provide shallow donor levels in AFM coupling and deep donor levels in FM coupling. 2Mn2W clusters lead to trap states in the FM and AFM coupling. We demonstrate the AFM to FM phase transition at a critical electron density nce = 3.5 × 1013 cm-2 in 2D-MoS2 and 2D-WS2. At a 1.85% concentration of Mn, we calculate the Curie temperature of 580 K in the mean-field approximation.

MoS2/PPy Nanocomposite as a Transducer for Electrochemical Aptasensor of Ampicillin in River Water.

We report the design of an electrochemical aptasensor for ampicillin detection, which is an antibiotic widely used in agriculture and considered to be a water contaminant. We studied the transducing potential of nanostructure composed of MoS2 nanosheets and conductive polypyrrole nanoparticles (PPyNPs) cast on a screen-printed electrode. Fine chemistry is developed to build the biosensors entirely based on robust covalent immobilizations of naphthoquinone as a redox marker and the aptamer. The structural and morphological properties of the nanocomposite were studied by SEM, AFM, and FT-IR. High-resolution XPS measurements demonstrated the formation of a binding between the two nanomaterials and energy transfer affording the formation of heterostructure. Cyclic voltammetry and electrochemical impedance spectroscopy were used to analyze their electrocatalytic properties. We demonstrated that the nanocomposite formed with PPyNPs and MoS2 nanosheets has electro-catalytic properties and conductivity leading to a synergetic effect on the electrochemical redox process of the redox marker. Thus, a highly sensitive redox process was obtained that could follow the recognition process between the apatamer and the target. An amperometric variation of the naphthoquinone response was obtained regarding the ampicillin concentration with a limit of detection (LOD) of 10 pg/L (0.28 pM). A high selectivity towards other contaminants was demonstrated with this biosensor and the analysis of real river water samples without any treatment showed good recovery results thanks to the antifouling properties. This biosensor can be considered a promising device for the detection of antibiotics in the environment as a point-of-use system.

Electrochemical detection of matrix metalloproteinase-7 using an immunoassay on a methylene blue/2D MoS2/graphene oxide electrode.

Methylene blue (MB) adsorption onto a two-dimensional molybdenum disulfide (2D MoS2)/graphene oxide (GO) nanocomposite sitting on a screen-printed carbon electrode (SPCE) is used to develop a new sensitive label-free electrochemical immunosensor for the detection of matrix metalloproteinase-7 (MMP-7) cancer biomarkers. The 2D MoS2/GO nanocomposite deposited onto an SPCE provides a large specific surface area, fast electron transfer, and exceptional electrical conductivity. Furthermore, MB adsorbed onto the 2D MoS2/GO nanocomposite architecture can be used for signal amplification in electrochemical immunosensors. Moreover, an immunosensor platform was fabricated by the adsorption of anti-MMP-7 capture antibodies onto the MB/2D MoS2/GO nanocomposite surface via electrostatic interactions for the detection of the MMP-7 immunocomplex. Under optimum conditions, the label-free immunosensor exhibits a decrease in the current response for MB corresponding to the MMP-7 concentration. The sensor affords a linear logarithmic range of 0.010-75 ng mL-1 with a limit of detection (LOD) of 0.007 ng mL-1. The developed electrochemical immunosensor provides high selectivity, good reproducibility, and excellent stability. Furthermore, the proposed immunosensor can be applied for the detection of MMP-7 in human serum samples with good recovery. Thus, this device can be applied for the early clinical diagnosis of pancreatic and colorectal cancers.

Co-Delivery of Doxorubicin and Chloroquine by Polyglycerol Functionalized MoS2 Nanosheets for Efficient Multidrug-Resistant Cancer Therapy.

2D MoS2 has shown a great potential in biomedical applications, due to its superior loading capacity, photothermal property, and biodegradation. In this work, polyglycerol functionalized MoS2 nanosheets with photothermal and pH dual-stimuli responsive properties are used for the co-delivery of doxorubicin and chloroquine and treatment of multidrug-resistant HeLa (HeLa-R) cells. The polyglycerol functionalized MoS2 nanosheets with 80 nm average size show a high biocompatibility and loading efficiency (≈90%) for both drugs. The release of drugs from the nanosheets at pH 5.5 is significantly promoted by laser irradiation leading to efficient destruction of incubated HeLa-R cells. In vitro evaluation shows that the designed nanoplatform has a high ability to kill HeLa-R cells. Confocal experiments demonstrate that the synthesized drug delivery system enhances the cellular uptake of DOX via folic acid targeting ligand. Taking advantage of the combined properties including biocompatibility and targeting ability as well as high loading capacity and photothermal release, this multifunctional nanosystem is a promising candidate for anticancer therapy.