Integrated molybdenum single atom array sensors with multichannels for nitrite detection in foods.

Nitrite (NO2-) is present in a variety of foods, but the excessive intake of NO2- can indirectly lead to carcinogenic, teratogenic, mutagenicity and other risks to the human body. Therefore, the detection of NO2- is crucial for maintaining human health. In this study, an integrated array sensor for NO2- detection is developed based on molybdenum single atom material (IMSMo-SAC) using high-resolution electrohydrodynamic (EHD) printing technology. The sensor comprises three components: a printed electrode array, multichannels designed on polydimethylsiloxane (PDMS) and an electronic signal process device with bluetooth. By utilizing Mo-SAC to facilitate electron transfer during the redox reaction, rapid and efficient detection of NO2- can be achieved. The sensor has a wide linear range of 0.1 µM-107.8 mM, a low detection limit of 33 nM and a high sensitivity of 0.637 mA-1mM-1 cm-2. Furthermore, employing this portable array sensor allows simultaneously measurements of NO2- concentrations in six different foods samples with acceptable recovery rates. This array sensor holds great potential for detecting of small molecules in various fields.

Biomass hydrothermal carbonization solution-assisted synthesis of intercalation-expanded core-shell structured molybdenum disulfide for efficient adsorption of Cr (VI) in electroplating wastewater treatment.

Cr (VI) is a common heavy metal pollutant in electroplating wastewater. This study introduces the liquid-phase product from the hydrothermal reaction of coffee grounds (CGHCL) into the synthesis process of molybdenum disulfide, assisting in the fabrication of an intercalated, expanded core-shell structured molybdenum disulfide adsorbent (C-MoS2), designed for the adsorption and reduction of Cr (VI) from electroplating wastewater. The addition of CGHCL significantly enhances the adsorption performance of MoS2. Furthermore, C-MoS2 exhibits exceedingly high removal efficiency and excellent regenerative capability for Cr (VI)-containing electroplating wastewater. The core-shell structure effectively minimizes molybdenum leaching to the greatest extent, while the oleophobic interface is unaffected by oily substances in water, and the expanded interlayer structure ensures the long-term stability of C-MoS2 in air (90 days). This study provides a viable pathway for the resource utilization of biomass and the application of molybdenum disulfide-based materials in wastewater treatment.

Molybdenum Complexes Derived from 2-Hydroxy-5-nitrobenzaldehyde and Benzhydrazide as Potential Oxidation Catalysts and Semiconductors.

This study aimed to synthesize molybdenum complexes coordinated with an aroyl hydrazone-type ligand (H2L), which was generated through the condensation of 2-hydroxy-5-nitrobenzaldehyde with benzhydrazide. The synthesis yielded two types of mononuclear complexes, specifically [MoO2(L)(MeOH)] and [MoO2(L)(H2O)], as well as a bipyridine-bridged dinuclear complex, [(MoO2(L))2(4,4'-bpy)]. Those entities were thoroughly characterized using a suite of analytical techniques, including attenuated total reflectance infrared spectroscopy (IR-ATR), elemental analysis (EA), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction (SCXRD). Additionally, solid-state impedance spectroscopy (SS-IS) was employed to investigate the electrical properties of these complexes. The mononuclear complexes were tested as catalysts in the epoxidation of cyclooctene and the oxidation of linalool. Among these, the water-coordinated mononuclear complex, [MoO2(L)(H2O)], demonstrated superior electrical and catalytic properties. A novel contribution of this research lies in establishing a correlation between the electrical properties, structural features, and the catalytic efficiency of the complexes, marking this work as one of the pioneering studies in this area for molybdenum coordination complexes, to the best of our knowledge.

TiO2 nanorod decorated with MoS2 nanospheres: An efficient dual-functional photocatalyst for antibiotic degradation and hydrogen production.

The design and preparation of dual-functional photocatalysts for simultaneously realizing photocatalytic wastewater purification and hydrogen energy generation pose significant challenges. This article presents the engineering of a binary heterostructured photocatalyst by combining TiO2 (nanorods) and MoS2 nanosphere using a straightforward solvothermal method and the assessment of the phase structures, morphologies, and optical properties of the resulting nanocomposites using diverse analytical techniques. The TiO2(Rod)/MoS2 composite exhibits remarkable efficacy in degrading ciprofloxacin, achieving 93% removal rate within 1 h, which is four times higher than that of bare TiO2. Moreover, the optimized TiO2(Rod)/MoS2 presents an outstanding hydrogen production rate of 7415 µmol g-1, which is ∼24 times higher than that of pristine TiO2. Under UV-visible light irradiation, the TiO2(Rod)/MoS2 heterojunction displays an exceptional photocatalytic performance in terms of both photodegradation and hydrogen production, surpassing the performance of TiO2 particle/MoS2. The study findings demonstrate that TiO2(Rod)/MoS2 nanocomposites exhibit considerably improved photocatalytic degradation and hydrogen generation activities. Based on the experimental results, a possible mechanism is proposed for the transfer and separation of charge carriers in Z-scheme heterojunctions.

The Fabrication and Property Characterization of a Ho2YSbO7/Bi2MoO6 Heterojunction Photocatalyst and the Application of the Photodegradation of Diuron under Visible Light Irradiation.

A novel photocatalytic nanomaterial, Ho2YSbO7, was successfully synthesized for the first time using the solvothermal synthesis technique. In addition, a Ho2YSbO7/Bi2MoO6 heterojunction photocatalyst (HBHP) was prepared via the hydrothermal fabrication technique. Extensive characterizations of the synthesized samples were conducted using various instruments, such as an X-ray diffractometer, a Fourier transform infrared spectrometer, a Raman spectrometer, a UV-visible spectrophotometer, an X-ray photoelectron spectrometer, and a transmission electron microscope, as well as X-ray energy dispersive spectroscopy, photoluminescence spectroscopy, a photocurrent test, electrochemical impedance spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance. The photocatalytic activity of the HBHP was evaluated for the degradation of diuron (DRN) and the mineralization of total organic carbon (TOC) under visible light exposure for 152 min. Remarkable removal efficiencies were achieved, with 99.78% for DRN and 97.19% for TOC. Comparative analysis demonstrated that the HBHP exhibited markedly higher removal efficiencies for DRN compared to Ho2YSbO7, Bi2MoO6, or N-doped TiO2 photocatalyst, with removal efficiencies 1.13 times, 1.21 times, or 2.95 times higher, respectively. Similarly, the HBHP demonstrated significantly higher removal efficiencies for TOC compared to Ho2YSbO7, Bi2MoO6, or N-doped TiO2 photocatalyst, with removal efficiencies 1.17 times, 1.25 times, or 3.39 times higher, respectively. Furthermore, the HBHP demonstrated excellent stability and reusability. The mechanisms which could enhance the photocatalytic activity remarkably and the involvement of the major active species were comprehensively discussed, with superoxide radicals identified as the primary active species, followed by hydroxyl radicals and holes. The results of this study contribute to the advancement of efficient heterostructural materials and offer valuable insights into the development of sustainable remediation strategies for addressing DRN contamination.

Frustrated Lewis pairs created by Ce-doped Bi2MoO6: A universal strategy to promote efficient utilization of H2O2 for Fenton-like photodegradation.

Photo-Fenton-like technology based on H2O2 is considered as an ideal strategy to generate reactive oxygen species (ROS) for antibiotic degradation, but O2 overflow in the process severely limits the utilization efficiency of H2O2. Herein, we fabricate Bi2MoO6 (BMO) photocatalyst modified with Frustrated Lewis pairs (FLPs) as a Fenton catalyst model for enhancing reuse of spilled O2. The FLPs created by the introduction of cerium and oxygen vacancy were found to contribute to regulate the electronic structure of BMO and further improve the acidic and basic properties of photocatalyst surface. More importantly, the frustrated acid and base sites can enhance the H2O2 and O2 interfacial adsorption process and provide an Ce4+-Ov-O2- active site on the surface of Ce-BMO nanosheets, which can promote O2/•O2-/1O2/H2O2 redox cycles to achieve high H2O2 utilization efficiency. Specifically, in the experiment using tetracycline as a photocatalytic degradation object, the degradation activity of Ce-BMO was 2.15 times higher than that of BMO pure phase. Quenching experiments and EPR assays also confirmed that 1O2 and •O2- were the dominant oxidative species. This study systematically reveals the design of Fenton photocatalytic active sites at the atomic scale and provides new insights into constructing FLPs photocatalysts with high H2O2 utilization efficiency.

Cobalt molybdate nanoflowers decorated bio-waste derived porous activated carbon nanocomposite: A high performance electrode material for supercapacitors.

In this work, we report a supercapacitor electrode material based on nano-flower like cobalt molybdate decorated on porous activated carbon derived from waste onion peels (ß-CoMoO4-POAC). The obtained POAC exhibits highly porous structure and after the hydrothermal treatment with salts of cobalt and molybdenum, we observed a uniform distribution of ß-cobalt molybdate (ß-CoMoO4) as nano-flowers on the surface of POAC. The chemical composition, morphology and porosity of the materials were thoroughly analyzed using field emission scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, infrared spectroscopy and Brunauer-Emmet-Teller surface area measurement. Due to its flower like and highly porous morphology, ß-CoMoO4@POAC exhibits a high specific capacitance of 1110.72 F/g at a current density of 1 mA/cm2 with superior cyclic retention of 96.03% after 2000 cycles. The best electrochemical performance exhibited by ß-CoMoO4@POAC is mainly due to its high surface area and porous nature of the material which assists in active transport of ions. This study reveals the exceptional electrochemical properties of ß-CoMoO4@POAC which could be considered as a potential material for advanced energy storage devices.

Nitrodopamine modified MnO2 NS-MoS2QDs hybrid nanocomposite for the extracellular and intracellular detection of glutathione.

We have developed a highly sensitive and reliable fluorescence resonance energy transfer (FRET) probe using nitro-dopamine (ND) and dopamine (DA) coated MnO2 nanosheet (ND@MnO2 NS and DA@MnO2 NS) as an energy acceptor and MoS2 quantum dots (QDs) as an energy donor. By employing surface-modified MnO2 NS, we can effectively reduce the fluorescence intensity of MoS2 QDs through FRET. It can reduce MnO2 NS to Mn2+ and facilitate the fluorescence recovery of the MoS2 QDs. This ND@MnO2 NS@MoS2 QD-based nanoprobe demonstrates excellent sensitivity to GSH, achieving an LOD of 22.7 nM in an aqueous medium while exhibiting minimal cytotoxicity and good biocompatibility. Moreover, our sensing platform shows high selectivity to GSH towards various common biomolecules and electrolytes. Confocal fluorescence imaging revealed that the nanoprobe can image GSH in A549 cells. Interestingly, the ND@MnO2 NS nanoprobe demonstrates no cytotoxicity in living cancer cells, even at concentrations up to 100 µg mL-1. Moreover, the easy fabrication and eco-friendliness of ND@MnO2 NS make it a rapid and simple method for detecting GSH. We envision the developed nanoprobe as an incredible platform for real-time monitoring of GSH levels in both extracellular and intracellular mediums, proving valuable for biomedical research and clinical diagnostics.

Separation of inorganic anions on reversed-phase C18 columns with a phosphomolybdate mobile phase.

Reversed-phase high performance liquid chromatography (RP-HPLC) is the most widely used chromatographic method. In addition to hydrophobic interactions, additional interactions such as electrostatic interactions may participate in the retention behaviour of an analyte. This makes it possible to use RP-HPLC for many types of analyte. We describe a simple method for separating inorganic anions on a C18 column, in which retention of inorganic anions is almost entirely due to electrostatic interactions. This leads to rapid separations as well as higher theoretical plate numbers. We used 2 mM phosphoric acid containing a low concentration of disodium molybdate as the mobile phase, which allows UV detection of non-UV-absorbing anions. With this method, we determined eight inorganic anions including several non-UV-absorbing anions photometrically at 220 nm. The detection limits of the examined eight inorganic anions calculated at a signal-to-noise ratio of 3 were between 0.3 and 10 µM. The detector response was linear over three orders of magnitude of inorganic anion concentration. The proposed RP-HPLC/UV method was successfully applied to determine inorganic anions in some water samples.

Iron-carbon dots embedded in molybdenum single-atom nanoflowers as multifunctional nanozyme for dual-mode detection of hydrogen peroxide and uric acid.

Single-atom catalysts (SACs) have attracted extensive attention in the field of catalysis due to their excellent catalytic ability and enhanced atomic utilization, but the multi-mode single-atom nanozymes for biosensors remain a challenging issue. In this work, iron-doped carbon dots (Fe CDs) were loaded onto the edges and pores of Mo SACs with nanoflower morphology; accordingly, a composite material Fe CDs/Mo SACs was prepared successfully, which improves the catalytic performance and develops a fluorescence mode without changing the original morphology. The steady-state kinetic data indicates that the material prepared have better affinity for substrates and faster reaction rates under optimized conditions. The specific kinetic parameters Km and Vmax were calculated as 0.39 mM and 7.502×10-7 M·s-1 respectively. The excellent peroxidase-like activity of Fe CDs/Mo SACs allows H2O2 to decompose into •OH, which in turn oxidizes colorless o-phenylenediamine (OPD) to yellow 2,3-diaminophenazine (DAP). At the same time, the fluorescence signal of Fe CDs/Mo SACs quenches obviously by DAP at 460 nm through internal filtration effect (IFE), while the characteristic fluorescence response of DAP gradually increases at 590 nm. Based on this sensing mechanism, a sensitive and accurate dual-mode (colorimetric and ratiometric fluorescent) sensor was constructed to detect H2O2 and uric acid, and the rate of recovery and linearity were acceptable for the detection of UA in human serum and urine samples. This method provides a new strategy for rapid and sensitive detection of UA, and also broadens the development of SACs in the field of biosensors.

Hydrolysis-dominated catalytic system: Hydrogen-free hydrogenolysis of lignin from Pd-MoOx/TiO2.

Lignin is continuously investigated by various techniques for valorization due to its high content of oxygen-containing functional groups. Catalytic systems employing hydrolysis­hydrogenolysis, leveraging the synergistic effect of redox metal sites and acid sites, exhibit efficient degradation of lignin. The predominance of either hydrolysis or hydrogenolysis reactions hinges upon the relative activity of acid and metal sites, as well as the intensity of the reductive atmosphere. In this study, the Pd-MoOx/TiO2 catalyst was found to primarily catalyze hydrolysis in the lignin depolymerization process, attributed to the abundance of moderate acidic sites on Pd and the redox-assisted catalysis of MoOx under inert conditions. After subjecting the reaction to 240 °C for 30 h, a yield of 48.22 wt% of total phenolic monomers, with 5.90 wt% consisting of diphenols, was achieved. Investigation into the conversion of 4-propylguaiacol (4-PG), a major depolymerized monomer of corncob lignin, revealed the production of ketone intermediates, a phenomenon closely linked to the unique properties of MoOx. Dehydrogenation of the propyl is a key step in initiating the reaction, and 4-PG could be almost completely transformed, accompanied by an over 97 % of 4-propylcatechol selectivity. This distinctive system lays a new theoretical groundwork for the eco-friendly valorization of lignin.

Detecting Hachimoji DNA: An Eight-Building-Block Genetic System with MoS2 and Janus MoSSe Monolayers.

In the pursuit of personalized medicine, the development of efficient, cost-effective, and reliable DNA sequencing technology is crucial. Nanotechnology, particularly the exploration of two-dimensional materials, has opened different avenues for DNA nucleobase detection, owing to their impressive surface-to-volume ratio. This study employs density functional theory with van der Waals corrections to methodically scrutinize the adsorption behavior and electronic band structure properties of a DNA system composed of eight hachimoji nucleotide letters adsorbed on both MoS2 and MoSSe monolayers. Through a comprehensive conformational search, we pinpoint the most favorable adsorption sites, quantifying their adsorption energies and charge transfer properties. The analysis of electronic band structure unveils the emergence of flat bands in close proximity to the Fermi level post-adsorption, a departure from the pristine MoS2 and MoSSe monolayers. Furthermore, leveraging the nonequilibrium Green's function approach, we compute the current-voltage characteristics, providing valuable insights into the electronic transport properties of the system. All hachimoji bases exhibit physisorption with a horizontal orientation on both monolayers. Notably, base G demonstrates high sensitivity on both substrates. The obtained current-voltage (I-V) characteristics, both without and with base adsorption on MoS2 and the Se side of MoSSe, affirm excellent sensing performance. This research significantly advances our understanding of potential DNA sensing platforms and their electronic characteristics, thereby propelling the endeavor for personalized medicine through enhanced DNA sequencing technologies.

Insights into mechanism of peroxymonosufate activation by Mo single-atom catalysts: Singlet oxygen evolution and role of Mo-N coordination.

Recently, the Fenton-like reaction using peroxymonosulfate (PMS) has been acknowledged as a potential method for breaking down organic pollutants. In this study, we successfully synthesized a highly efficient and stable single atom molybdenum (Mo) catalyst dispersed on nitrogen-doped carbon (Mo-NC-0.1). This catalyst was then utilized for the first time to activate PMS and degrade bisphenol A (BPA). The Mo-NC-0.1/PMS system demonstrated the ability to completely degrade BPA within just 20 min. Scavenging tests and density functional theory (DFT) calculations have demonstrated that the primary reactive oxygen species was singlet oxygen (1O2) produced by Mo-N4 sites. The self-cycling of Mo facilitated PMS activation and the transition from a free radical activation pathway to a non-radical pathway mediated by 1O2. Simultaneously, the nearby pyridinic N served as adsorption sites to immobilize BPA and PMS molecules. The exceptionally high catalytic activity of Mo-NC-0.1 derived from its unique Mo-N coordination, which markedly reduced the distance for 1O2 to migrate to the BPA molecules. The Mo-NC-0.1/PMS system effectively reduced the acute toxicity of BPA and exhibited excellent cycling stability with minimal leaching. This study presented a new catalyst with high selectivity for 1O2 generation and provided valuable insights for the application of single atom catalysts in PMS-based AOPs.

Molybdenum disulfide nanosheets promote the plasmid-mediated conjugative transfer of antibiotic resistance genes.

The environmental safety of nanoscale molybdenum disulfide (MoS2) has attracted considerable attention, but its influence on the horizontal migration of antibiotic resistance genes and the ecological risks entailed have not been reported. This study addressed the influence of exposure to MoS2 at different concentrations up to 100 mg/L on the conjugative transfer of antibiotic resistance genes carried by RP4 plasmids with two strains of Escherichia coli. As a result, MoS2 facilitated RP4 plasmid-mediated conjugative transfer in a dose-dependent manner. The conjugation of RP4 plasmids was enhanced as much as 7-fold. The promoting effect is mainly attributable to increased membrane permeability, oxidative stress induced by reactive oxygen species, changes in extracellular polymer secretion and differential expression of the genes involved in horizontal gene transfer. The data highlight the distinct dose dependence of the conjugative transfer of antibiotic resistance genes and the need to improve awareness of the ecological and health risks of nanoscale transition metal dichalcogenides.

A photo-responsive self-healing hydrogel loaded with immunoadjuvants and MoS2 nanosheets for combating post-resection breast cancer recurrence.

Tumor recurrence after surgical resection remains a significant challenge in breast cancer treatment. Immune checkpoint blockade therapy, as a promising alternative therapy, faces limitations in combating tumor recurrence due to the low immune response rate. In this study, we developed an implantable photo-responsive self-healing hydrogel loaded with MoS2 nanosheets and the immunoadjuvant R837 (PVA-MoS2-R837, PMR hydrogel) for in situ generation of tumor-associated antigens at the post-surgical site of the primary tumor, enabling sustained and effective activation of the immune response. This PMR hydrogel exhibited potential for near-infrared (NIR) light response, tissue adhesion, self-healing, and sustained adjuvant release. When implanted at the site after tumor resection, NIR irradiation triggered a photothermal effect, resulting in the ablation of residual cancer cells. The in situ-generated tumor-associated antigens promoted dendritic cell (DC) maturation. In a mouse model, PMR hydrogel-mediated photothermal therapy combined with immune checkpoint blockade effectively inhibited the recurrence of resected tumors, providing new insights for combating post-resection breast cancer recurrence.

In-situ growth of MOF-derived Co3S4@MoS2 heterostructured electrocatalyst for the detection of furazolidone.

The over-exploitation of antibiotics in food and farming industries ruined the environmental and human health. Consequently, electrochemical sensors offer significant advantages in monitoring these compounds with high accuracy. Herein, MOF-derived hollow Co3S4@MoS2 (CS@MS) heterostructure has been prepared hydrothermally and applied to fabricate an electrochemical sensor to monitor nitrofuran class antibiotic drug. Various spectroscopic methodologies have been employed to elucidate the structural and morphological information. Our prepared electrocatalyst has better electrocatalytic performance than bare and other modified glassy carbon electrodes (GCE). Our CS@MS/GCE sensor exhibited a highly sensitive detection by offering a low limit of detection, good sensitivity, repeatability, reproducibility, and stability results. In addition, our sensor has shown a good selectivity towards the target analyte among other potential interferons. The practical reliability of the sensor was measured by analyzing various real-time environmental and biological samples and obtaining good recovery values. From the results, our fabricated CS@MS could be an active electrocatalyst material for an efficient electrochemical sensing application.

Chondroitin sulphate modified MoS2 nanoenzyme with multifunctional activities for treatment of Alzheimer's disease.

Nano-MoS2 exhibit oxidoreductase-like activities, and has been shown to effectively eliminate excessive intracellular ROS and inhibit Aß aggregation, thus demonstrating promising potential for anti-Alzheimer's disease (anti-AD) intervention. However, the low water dispersibility and high toxicity of nano-MoS2 limits its further application. In this study, we developed a chondroitin sulphate (CS)-modified MoS2 nanoenzyme (CS@MoS2) by harnessing the excellent biocompatibility of CS and the exceptional activities of nano-MoS2 to explore its potential in anti-AD research. Promisingly, CS@MoS2 significantly inhibited Aß1-40 aggregation and prevented toxic injury in SH-SY5Y cells caused by Aß1-40. In addition, CS@MoS2 protected these cells from oxidative stress damage by regulating ROS production, as well as promoting the activities of SOD and GSH-Px. CS@MoS2 also modulated the intracellular Ca2+ imbalance and downregulated Tau hyperphosphorylation by activating GSK-3ß. CS@MoS2 suppressed p-NF-κB (p65) translocation to the nucleus by inhibiting MAPK phosphorylation, and modulated the expression of downstream anti- and proinflammatory cytokines. Owing to its multifunctional activities, CS@MoS2 effectively improved spatial learning, memory, and anxiety in D-gal/AlCl3-induced AD mice. Taken together, these results indicate that CS@MoS2 has significant potential for improving the therapeutic efficacy of the prevention and treatment of AD, while also presenting a novel framework for the application of nanoenzymes.

Solution NMR chemical shift assignment of apo and molybdate-bound ModA at two pHs.

ModA is a soluble periplasmic molybdate-binding protein found in most gram-negative bacteria. It is part of the ABC transporter complex ModABC that moves molybdenum into the cytoplasm, to be used by enzymes that carry out various redox reactions. Since there is no clear analog for ModA in humans, this protein could be a good target for antibacterial drug design. Backbone 1H, 13C and 15N chemical shifts of apo and molybdate-bound ModA from E. coli were assigned at pHs 6.0 and 4.5. In addition, side chain atoms were assigned for apo ModA at pH 6.0. When comparing apo and molybdate-bound ModA at pH 6.0, large chemical shift perturbations are observed, not only in areas near the bound metal, but also in regions that are distant from the metal-binding site. Given the significant conformational change between apo and holo ModA, we might expect the large chemical shift changes to be more widespread; however, since they are limited to specific regions, the residues with large perturbations may reveal allosteric sites that could ultimately be important for the design of antibiotics that target ModA.