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.

Two {CuI[P4Mo6]2}-Based Coordination Polymers Incorporating In Situ Converted Tetrapyridyl Ligands for Trace Analysis of Nitrofuran Antibiotics.

Nitrofurans are important synthetic broad-spectrum antibacterial drugs with the basic structure of 5-nitrofuran. Due to their toxicity, it is essential to develop a sensitive sensor with strong anti-interference capabilities for their detection. In this work, two {P4Mo6O31}12--based compounds, [H4(HPTTP)]2{CuI[Mo12O24(OH)6(PO4)3(HPO4)(H2PO4)4]}·xH2O (x = 13 for (1), 7 for (2); HPTTP = 4,4',4″,4‴-(1H-pyrrole-2,3,4,5-tetrayl)tetrapyridine), exhibiting similar coordination but distinct stacking modes. Both compounds were synthesized and used for the electrochemical detection of nitrofuran antibiotics. The tetrapyridine-based ligand was generated in situ during assembly, and its potential mechanism was discussed. Composite electrode materials, formed by mixing graphite powder with compounds 1-2 and physically grinding them, proved to be highly effective in the electrochemical trace detection of furazolidone (FZD) and furaltadone hydrochloride (FTD·HCl) under optimal conditions. Besides, the possible electrochemical detection mechanisms of two nitro-antibiotics were studied.

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.

Effect of humic substances on the fraction of heavy metal and microbial response.

Contamination of soils by Molybdenum (Mo) has raised increasing concern worldwide. Both fulvic acid (FA) and humic acid (HA) possess numerous positive properties, such as large specific surface areas and microporous structure that facilitates the immobilization of the heavy metal in soils. Despite these characteristics, there have been few studies on the microbiology effects of FA and HA. Therefore, this study aimed to assess the Mo immobilization effects of FA and HA, as well as the associated changes in microbial community in Mo-contaminated soils (with application rates of 0%, 0.5% and 1.0%). The result of the incubation demonstrated a decrease in soil pH (from 8.23 ~ 8.94 to 8.05 ~ 8.77). Importantly, both FA and HA reduced the exchangeable fraction and reducible fraction of Mo in the soil, thereby transforming Mo into a more stable form. Furthermore, the application of FA and HA led to an increase in the relative abundance of Actinobacteriota and Firmicutes, resulting in alterations to the microbial community structure. However, it is worth noting that due to the differing structures and properties of FA and HA, these outcomes were not entirely consistent. In summary, the aging of FA and HA in soil enhanced their capacity to immobilization Mo as a soil amendment. This suggests that they have the potential to serve as effective amendments for the remediation of Mo-contaminated soils.

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.

A Ce2MgMoO6 double perovskite decorated on a functionalized carbon nanofiber nanocomposite for quantification of ciprofloxacin in milk and honey samples: Density functional theory interpretation.

In this study, a novel Ce2MgMoO6/CNFs (cerium magnesium molybdite double perovskite decorated on carbon nanofibers) nanocomposite was developed for selective and ultra-sensitive detection of ciprofloxacin (CFX). Physical characterization and analytical techniques were used to explore the morphology, structure, and electrocatalytic characteristics of the Ce2MgMoO6/CNFs nanocomposite. The sensor has a wide linear range (0.005-7.71 µM and 9.75-77.71 µM), a low limit of detection (0.012 µM), high sensitivity (0.807 µA µM-1 cm-2 nM), remarkable repeatability, and an appreciable storage stability. Here, we used density functional theory to investigate CFX and oxidized CFX as well as the locations of the energy levels and electron transfer sites. Furthermore, the Ce2MgMoO6/CNFs-modified electrode was successfully tested in food samples (milk and honey), indicating an acceptable response with a recovery percentage and relative standard deviation of less than 4%, which is comparable to that of GC-MS. Finally, the developed sensor exhibited high selectivity and stability for CFX detection.

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.

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.

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.

NiAlFe LTH /MoS2 p-n junction heterostructure composite as an effective visible-light-driven photocatalyst for enhanced degradation of organic dye under high alkaline conditions.

Designing of an effectual heterostructure photocatalyst for catalytic organic pollutant exclusion has been the subject of rigorous research intended to resolve the related environmental aggravation. Fabricating p-n junctions is an effective strategy to promote electron-hole separation of semiconductor photocatalysts as well as enhance the organic toxin degradation performance. In this study, a series of n-type NiAlFe-layered triple hydroxide (LTH) loaded with various ratios of p-type MoS2 was synthesized for forming a heterostructure LTH/MoS2 (LMs) by an in situ hydrothermal strategy. The photocatalysts were characterized by XRD, SEM&EDX, TEM, FT-IR, XPS, as well as UV-vis DRS. The photoactivity of photocatalysts was tested by the degradation of Indigo Carmine (IC) dye. The optimized catalyst (LM1) degrades 100% of indigo dye in high alkaline pH under UV light for 100 min. Besides, the degradation rate of LM1 is 15 times higher than that of pristine NiAlFe-LTH. The enhanced photoactivity is attributed to the synergistic effect between NiAlFe-LTH and MoS2 as well as the p-n junction formation.

ZnMo-MOF as anti-CO hydrogen electrocatalyst enhance microbial electrosynthesis for CO/CO2 conversion.

Microbial electrosynthesis (MES) is an electrically driven technology that can be used for converting CO/CO2 into chemicals. The unique electronic and substrate properties of CO make it an important research target for MES. However, CO can poison the cathode and increase the overpotential of hydrogen evolution reaction (HER), thus reducing the electron transfer rate via H2. This work evaluated the effect of an anti-CO HER catalyst on the performance of MES for CO/CO2 conversion. ZnMo-metal-organic framework (MOF) materials with different calcination temperatures were synthesized. ZnMo-MOF-800 with Mo2C nanoparticles as active centers exhibited excellent resistance to CO toxicity. It also obtained the highest hydrogen evolution and enhanced electron transfer rate in CO atmosphere. MES with ZnMo-MOF-800 cathode and Clostridium ljungdahlii as biocatalyst obtained 0.31 g L-1 d-1 acetate yield, 0.1 g L-1 d-1 butyrate yield, and 0.09 g L-1 d-1 2,3-butanediol yield in CO/CO2, while Pt/C only get 0.076 g L-1 d-1 acetate yield, 0.05 g L-1 d-1 butyrate yield and 0.02 g L-1 d-1 2,3-butanediol yield. ZnMo-MOF-800 was conducive to biofilm formation, enabling it to better resist CO toxicity. This work provides new opportunities for constructing a highly efficient cathode with an anti-CO hydrogen evolution catalyst to enhance CO/CO2 conversion in MES.

Synthesis of ultrathin hybrid membranes via the co-polymerization of acrylic acid, styrene and molybdenum disulfide and their high adsorption selectivity for lead(II) in the mixture of metal ions.

Lead(II) is a potential carcinogen of heavy-metal ions (HIs). With the wide application of Pb-bearing products including lead alloy products, and new-energy lead-ion batteries, lead pollution has become a tricky problem. To solve such a difficulty, novel ultrathin MoS2-vinyl hybrid membranes (MVHMs) with a "spring" effect were synthesized via co-polymerization of acrylic acid, styrene and molybdenum disulfide (MoS2) and their adsorptions for HIs were explored. The "spring" effect derived from the interaction between the tendency of the short polyacrylic acid (PAA) chain connected with MoS2 to spread outward and the coulomb force between layers from MoS2 (s-MoS2), which enlarge the spacing of MoS2 layers without changing the number of layers after membrane formation, which changes the swelling membrane to a dense membrane and reduces the original thickness from 0.5 cm to 0.011 mm in the thickness direction. The adsorption experiment revealed that these MVHMs had super adsorption performance and high selectivity for Pb2+ by comparison with other five metal ions: Cu2+, Cd2+, Ni2+, Cr3+ and Zn2+. Especially, the adsorption quantity of MVHMs for Pb2+ could approach 2468 mg/g and the maximum adsorption ratio of qe[Pb2+]/qe[Cu2+] can reach 10.909. These values were much larger than the data obtained with the adsorbents reported in the last decade. A variety of models are applied to evaluate the effect of ionic groups. It was confirmed that -COOH plays a key role in adsorption of HIs and s-MoS2 also has a certain contribution. Conversely, ion exchange plays only a minor role during the period of adsorption process. Effective diffusion coefficient (Deff) of Pb(II) had the largest values among these metal ions. Hence, these hybrid membranes are promising adsorbents for the removal of Pb2+ from water containing various ions.

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.

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.

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.

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.

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.