Functionalized MoS2: circular economy SERS substrate for label-free detection of bilirubin in clinical diagnosis.

A one-pot hydrothermal synthesis of Fe-doped MoS2 nanoflowers (Fe-MoS2 NFs) has been developed as a surface-enhanced Raman spectroscopy (SERS) substrate. The Fe-MoS2 NFs display high reproducibility, stability, and recyclability, which is beneficial for the development of the sustainable ecological environment. The SERS substrate provides a high enhancement factor of 105, which can be ascribed to the inducing defects by doping Fe that can improve the charge transfer between probe molecules and MoS2. The Fe-MoS2 NFs have been used to detect bilirubin in serum. The Fe-MoS2 NF SERS substrate exhibits a linear detection range from 10-3 to 10-9 M with a low limit of detection (LOD) of 10-8 M. The substrate displays an excellent selectivity to bilirubin in the presence of other potentially interfering molecules (dextrose and phosphate). These results provide a novel concept to synthesize ultra-sensitive SERS substrates and open up a wide range of possibilities for new applications of MoS2 in clinical diagnosis.

"Nano Killers" Activation by permonosulfate enables efficient anaerobic microorganisms disinfection.

The development of effective nanomaterials for killing anaerobic bacteria is essential for human health and economic development. Here, we propose a new bactericidal mechanism where theoretical calculations are in good agreement with experimental results. The "poison arrow-head" of MoS2 nanosheets enables the vigorous extraction of lipids from the cell membrane. Based on density functional calculations, oxidation active species (OAS) are generated due to the strong adsorption energy between S vacancies in MoS2 and chemical substrates (permonosulfate (PMS) and H2O). These OAS can be visualized as numerous moving "nano killers", constantly oxidizing the lipids around MoS2; thereby, re-releasing the surface of the sharp knife. The process of physical extraction collaborated with chemical oxidation not only precisely positions the cell membrane but also allows for continuous sterilization. This work digs into the mechanism of anaerobic bacterial sterilization, which sheds significant light on biological analysis, antibacterial, cancer therapy, and anti microbiologically influenced corrosion.

Toxicity assessment of two-dimensional nanomaterials molybdenum disulfide in Gallus gallus domesticus.

Recently two-dimensional nanomaterials, such as graphene and molybdenum disulfide (MoS2), have received much attention as adsorbent materials for the effective removal of organic contaminants. MoS2 is attracting attention, not only for its chemical-physical properties, but also for its wide availability in nature as a constituent of molybdenite. The aim of this investigation was to assess the effects of different MoS2 concentrations (5 × 10-1, 5 × 10-2 and 5 × 10-3 mg/ml) on the embryonated eggs of Gallus gallus domesticus, according to Beck method. We evaluated the toxic effect of the MoS2 powder purchased at Sigma-Aldrich indicated as "received" and MoS2 powder treated via mechanical milling indicated as "ball mille". Subsequently, the embryos were sacrificed at different times of embryonic development (11th, 15th and 19th day after incubation) in order to evaluate their embryotoxic and teratogenic effects. The alterations of the embryonic development were studied by morphological and immunohistochemical analysis of the tissues. The results obtained have shown the toxicity of both powders of MoS2 with a high percentage of deaths and growth delays. Moreover, the immunohistochemical analysis performed on several tissue sections showed a strong positivity to the anti-metallothionein1 antibody only for the erythrocytes.

Sensitive electrochemical sensor for nitrite ions based on rose-like AuNPs/MoS2/graphene composite.

Nitrite ions (NO2-) have been widely used in the food and drink industry as preservatives. However, the NO2- discharged into the environment is harmful to the ecosystem and human health. Due to its potential toxicity, selective and sensitive detection of nitrite is important. In this work, a rose-like Au nanoparticles/MoS2 nanoflower/graphene (AuNPs/MoS2/GN) composite was fabricated using a one-pot hydrothermal method without the addition of any extra reductant for use in nitrite detection. Graphene acts as an efficient matrix for the growth of MoS2 nanoflower (NF), and the edges of the MoS2 NF subsequently load AuNPs. The obtained AuNPs/MoS2/GN composite exhibits excellent electrooxidative activity toward nitrite ions, which is attributable to its large specific surface area, good conductivity, and the synergistic catalysis of each component. Accordingly, we propose a rapid, sensitive, and cost-effective electrochemical method for nitrite detection, which achieved a linear dynamic range of 5.0 µM to 5.0 mM with a detection limit of 1.0 µM. The present work provides not only a general one-pot synthesis method for a variety of noble-transition metal dichalcogenides nanohybrids, but also an example of the fabrication of an electrochemical nitrite sensor using a nanohybrid as an enhanced material, an approach that can easily be extended to other sensors.

A simple phosphorus determination in walnuts and assessment of the assimilable fraction.

In this work, a method for the determination of phosphorus in walnuts has been developed due to the fact that there is no specific method for this purpose. A closed-vessel microwave-assisted digestion of the samples was optimized and a modified molybdenum blue spectrophotometric method was carried out with excellent precision and selectivity. To differentiate assimilable and non-assimilable phosphorus, an easy extraction procedure using 1 M NH4Cl was used. FTIR spectra ensured that the phytate extraction was successful. A sampling of thirteen different walnuts available to consumers from different crops and geographical origin was performed. Comparative statistical tools to differentiate walnuts were also carried out. Significant differences based on total content of phosphorus were obtained. Finally, a correlation study between total phosphorus concentration and the non-assimilable fraction showed a non-linear relationship (R2 = 0.435). Therefore, in relation to consumer health the total phosphorus determination must be complemented with information about assimilable phosphorus.

Translocation, biotransformation-related degradation, and toxicity assessment of polyvinylpyrrolidone-modified 2H-phase nano-MoS2.

Nano-MoS2 has been extensively investigated in materials science and biomedicine. However, the effects of different methods of exposure on their translocation, biosafety, and biotransformation-related degradability remain unclear. In this study, we combined the advantages of synchrotron radiation (SR) X-ray absorption near-edge structure (XANES) and high-resolution single-cell SR transmission X-ray microscopy (SR-TXM) with traditional analytical techniques to investigate translocation, precise degraded species/ratio, and correlation between the degradation and toxicity levels of polyvinylpyrrolidone-modified 2H-phase MoS2 nanosheets (MoS2-PVP NSs). These NSs demonstrated different biodegradability levels in biomicroenvironments with H2O2, catalase, and human myeloperoxidase (hMPO) (H2O2 < catalase < hMPO). The effects of NSs and their biodegraded byproducts on cell viability and 3D translocation at the single-cell level were also assessed. Toxicity and translocation in mice via intravenous (i.v.), intraperitoneal (i.p.), and intragastric (i.g.) administration routes guided by fluorescence (FL) imaging were investigated within the tested dosage. After i.g. administration, NSs accumulated in the gastrointestinal organs and were excreted from feces within 48 h. After i.v. injection, NSs showed noticeable clearance due to their decreased accumulation in the liver and spleen within 30 days when compared with that in the i.p. group, which exhibited slight accumulation in the spleen. This work paves the way for understanding the biological behaviors of nano-MoS2 using SR techniques that provide more opportunities for future applications.

Electron-tracking Compton camera imaging of technetium-95m.

Imaging was conducted using an electron tracking-Compton camera (ETCC), which measures γ-rays with energies in the range of 200-900 keV from 95mTc. 95mTc was produced by the 95Mo(p, n)95mTc reaction on a 95Mo-enriched target. A method for recycling 95Mo-enriched molybdenum trioxide was employed, and the recycled yield of 95Mo was 70%-90%. Images were obtained with the gate of three energies. The results showed that the spatial resolution increases with increasing γ-ray energy, and suggested that the ETCC with high-energy γ-ray emitters such as 95mTc is useful for the medical imaging of deep tissue and organs in the human body.

Competitive adsorption and desorption of arsenate, vanadate, and molybdate onto the low-cost adsorbent materials alum water treatment sludge and bauxite.

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3 M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3-3.4% for V and As, and 11-20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.

Exfoliated molybdenum di-sulfide (MoS2) electrode for hydrogen production in microbial electrolysis cell.

The most widely reported catalyst in microbial electrochemical cells (MEC) cathodes is platinum (Pt). The disadvantages of Pt include its high cost and sensitivity to various molecules. In this research an exfoliated molybdenum di-sulfide (MoS2-EF) catalyst was synthesized. The size of the obtained particles was 200 ±â€¯50 nm, 50-fold smaller than the pristine MoS2 catalyst. The MoS2-EF Raman spectrum displays the E12g and A1g peaks at 373 cm-1 and 399 cm-1. Electrochemical characterization by linear sweep voltammetry (LSV) of a rotating disc electrode RDE showed that the current density of Pt in 0.5 M H2SO4 was 3.3 times higher than MoS2-EF. However, in phosphate buffer (pH-7) electrolyte this ratio diminished to 1.9. The polarization curve of Pt, MoS2-EF and the pristine MoS2 electrodes, at -1.3 V in MEC configuration in abiotic conditions exhibit current densities of 17.46, 12.67 and 3.09 mA cm-2, respectively. Hydrogen evolution rates in the same MEC with a Geobacter sulfurreducens anode and Pt, MoS2-EF and the pristine MoS2 cathodes were 0.106, 0.133 and 0.083 m3 d-1 m-3, respectively. The results in this study show that MoS2-EF led to highly purified hydrogen and that this catalyst can serve as an electrochemical active and cost-effective alternative to Pt.

Facile and Cost-Efficient Synthesis of Quasi-0D/2D ZnO/MoS2 Nanocomposites for Highly Enhanced Visible-Light-Driven Photocatalytic Degradation of Organic Pollutants and Antibiotics.

Nanoscale transition-metal dichalcogenide materials showed promising potential for visible-light responsive photocatalysis. Here, we report our investigations on the synthesis of heterodimensional nanostructures of two-dimensional (2D) ultrathin MoS2 nanosheets interspersed with ZnO nanoparticles by using a facile two-step method consisting of sonication-aided exfoliation technique followed by a wet chemical process. The photocatalytic activity of the nanocomposites was examined by studying the degradation of different organic dye pollutants and tetracycline, a common antibiotic, under visible-light irradiation. It is found that within 30 min more than 90 % of the model organic dye was photodegraded by the optimized quasi-0D/2D hybrid nanomaterial. The reaction rate of pollutant degradation is about five and eight times higher than those of the pristine MoS2 naonosheets and P25 photocatalysts, respectively. The outstanding photocatalytic activity of the heterodimensional hybrids can be attributed to a few beneficial features from the synergetic effects. Most importantly, the intimate junction between ZnO and MoS2 facilitates the separation of photogenerated carriers, leading to the enhancement of photocatalytic efficiency. A tentative photocatalytic degradation mechanism was proposed and tested. Overall, the present work provides valuable insights for the exploration of cost-effective nanoscale heterodimensional hybrids constructed from atomically thin layered materials.

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH3 temperature-programmed desorption (NH3-TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

Simultaneous determination of rutin and ascorbic acid in a sequential injection lab-at-valve system.

A green, simple, accurate and highly sensitive sequential injection lab-at-valve procedure has been developed for the simultaneous determination of ascorbic acid (Asc) and rutin using 18-molybdo-2-phosphate Wells-Dawson heteropoly anion (18-MPA). The method is based on the dependence of the reaction rate between 18-MPA and reducing agents on the solution pH. Only Asc is capable of interacting with 18-MPA at pH 4.7, while at pH 7.4 the reaction with both Asc and rutin proceeds simultaneously. In order to improve the precision and sensitivity of the analysis, to minimize reagent consumption and to remove the Schlieren effect, the manifold for the sequential injection analysis was supplemented with external reaction chamber, and the reaction mixture was segmented. By the reduction of 18-MPA with reducing agents one- and two-electron heteropoly blues are formed. The fraction of one-electron heteropoly blue increases at low concentrations of the reducer. Measurement of the absorbance at a wavelength corresponding to the isobestic point allows strictly linear calibration graphs to be obtained. The calibration curves were linear in the concentration ranges of 0.3-24mgL-1 and 0.2-14mgL-1 with detection limits of 0.13mgL-1 and 0.09mgL-1 for rutin and Asc, respectively. The determination of rutin was possible in the presence of up to a 20-fold molar excess of Asc. The method was applied to the determination of Asc and rutin in ascorutin tablets with acceptable accuracy and precision (1-2%).

Molybdenum Carbide Nanoparticles on Carbon Nanotubes and Carbon Xerogel: Low-Cost Cathodes for Hydrogen Production by Alkaline Water Electrolysis.

Low-cost molybdenum carbide (Mo2 C) nanoparticles supported on carbon nanotubes (CNTs) and on carbon xerogel (CXG) were prepared and their activity for the hydrogen evolution reaction (HER) was evaluated in 8 m KOH aqueous electrolyte at 25-85 °C. Measurements of the HER by linear scan voltammetry allowed us to determine Tafel slopes of 71 and 74 mV dec(-1) at 25 °C for Mo2 C/CNT and Mo2 C/CXG, respectively. Stability tests were also performed, which showed the steady performance of the two electrocatalysts. Moreover, the HER kinetics at Mo2 C/CNT was enhanced significantly after the long-term stability tests. The specific activity of both materials was high, and a higher stability was obtained for the activated Mo2 C/CNT (40 A g(-1) at -0.40 V vs. the reversible hydrogen electrode).

A novel high-throughput image based rapid Folin-Ciocalteau assay for assessment of reducing capacity in foods.

The aim of the presented work was to develop and validate a novel high-throughput rapid Folin-Ciocalteau assay for the quantification of reducing capacity of foods based on image scanner (Image-F-C assay). The original rapid F-C assay using a 96-well plate was improved by adding a neutralization step that stabilizes the formed color, enabling image acquisition using a flatbed scanner. Although the scanner has been already used in other analytical applications, no analysis has been reported regarding the effect of the scanner model, the plate orientation or the reaction volume. In the present study, we establish that the mentioned parameters do affect the linearity and precision of image based Folin-Ciocalteau assay, and provide the optimal scanning conditions for the analyzed scanner models. Euclidean distance calculated from R (Red), G (Green) and B (Blue) values was chosen, based on linearity and sensitivity, in order to quantify the reducing capacity. An in-house program using free ImageJ macro language was written to calculate automatically the RGB values of each well. The Image-F-C assay is linear within the range of 0-20 mg L(-1) of gallic acid (R(2)≥0.9939). We compared reducing capacity values from real samples quantified by the image F-C assay and by a microplate reader and an inter-day relative standard error<8% was observed. Bland-Altman and correlation analyzes showed that there were no significant differences between the two methods.

Exploration of Adiabatic Resonance Crossing Through Neutron Activator Design for Thermal and Epithermal Neutron Formation in (99)Mo Production and BNCT Applications.

A feasibility study was performed to design thermal and epithermal neutron sources for radioisotope production and boron neutron capture therapy (BNCT) by moderating fast neutrons. The neutrons were emitted from the reaction between (9)Be, (181)Ta, and (184)W targets and 30 MeV protons accelerated by a small cyclotron at 300 µA. In this study, the adiabatic resonance crossing (ARC) method was investigated by means of (207)Pb and (208)Pb moderators, graphite reflector, and boron absorber around the moderator region. Thermal/epithermal flux, energy, and cross section of accumulated neutrons in the activator were examined through diverse thicknesses of the specified regions. Simulation results revealed that the (181)Ta target had the highest neutron yield, and also tungsten was found to have the highest values in both surface and volumetric flux ratio. Transmutation in the (98)Mo sample through radiative capture was investigated for the natural lead moderator. When the sample radial distance from the target was increased inside the graphite region, the production yield had the greatest value of activity. The potential of the ARC method is a replacement or complements the current reactor-based supply sources of BNCT purposes.

Assessment of precipitation behavior in dental castings of a Co-Cr-Mo alloy.

This study investigated solute portioning and precipitation in dental castings of a Co-Cr-Mo alloy and discussed their effects on alloy performance, in particular, the mechanical properties. Samples of a commercial Co-29Cr-6Mo (mass%) alloy were prepared using a dental-casting machine. The precipitates formed owing to the partitioning behaviors of the alloying elements were investigated using scanning electron microscopy, electron backscatter diffraction analysis, electron probe microanalysis, and transmission electron microscopy. The prepared samples exhibited a very coarse face-centered-cubic γ-phase dendritic structure with an average grain size of a few millimeters. A large number of precipitates, which decomposed further into complex interdendritic constituents (σ- and M23C6 carbide phases) were observed in the interdendritic regions rich in Cr, Mo, Si, and C. A reaction between the σ-phase and carbon is probably responsible for the carbide M23C6; however, this reaction did not occur to completion in the current case in spite of slow cooling (i.e., long exposure to elevated temperatures) in dental casting. While these precipitates result in high strength (hardness) and/or brittleness, the properties can be improved further by optimizing the alloy composition and the manufacturing process. The results of this study shed light on the significance of precipitation control in dental castings of Co-Cr-Mo alloys and should aid in the design of novel biomedical Co-Cr-based dental alloys that exhibit better performances.

Implementation of a high-throughput ion chromatographic assay to assess glass degradation in drug product formulations.

UNLABELLED: The primary container for parenterals is usually composed of glass. Given the recent industry-wide spike in glass-related problems, assays capable of detecting glass degradation before glass-related particles are visible in solution have practical significance. A rapid, high-throughput ion chromatography method coupled with molybdate reaction is described here for detection and quantitation of silicic acid (soluble form of silica) in complex samples. The method involves ion exchange separation of the silicate anion at high pH followed by a post-column derivatization step with sodium molybdate reagent. The resulting molybdo-silicate complex is detected with high sensitivity in the visible wavelength range at 410 nm and correlates to the level of soluble silica in solution. This assay is high-throughput and amenable for implementation during the early phase of product development. The assay provides a direct measurement to assess potential incompatibility between the formulation and its glass container. The Si levels measured by this method showed a direct correlation to the vial surface morphology changes as monitored by differential interference contrast microscopy. LAY ABSTRACT: Recently, the pharmaceutical industry has been faced with glass quality challenges that have resulted in many products being recalled from the market. Monitoring levels of soluble silica in solution is critical because silica is the primary component of glass containers used in the pharmaceutical industry. Given this recent industry-wide increase in glass-related problems, assays capable of detecting glass degradation before glass-related particles are visible in solution have practical significance. A rapid assay to detect the soluble form of silica is presented here. The method presented will enable earlier detection of a formulation and container incompatibility instead of waiting until glass-related particles are visible in solution.

In vitro performance assessment of new beta Ti-Mo-Nb alloy compositions.

New ß-titanium based alloys with low Young's modulus are currently required for the next generation of metallic implant materials to ensure good mechanical compatibility with bone. Several of these are representatives of the ternary Ti-Mo-Nb system. The aim of this paper is to assess the in vitro biological performance of five new low modulus alloy compositions, namely Ti12Mo, Ti4Mo32Nb, Ti6Mo24Nb, Ti8Mo16Nb and Ti10Mo8Nb. Commercially pure titanium (cpTi) was used as a reference material. Comparative studies of cell activity exhibited by MC3T3-E1 pre-osteoblasts over short- and long-term culture periods demonstrated that these newly-developed metallic substrates exhibited an increased biocompatibility in terms of osteoblast proliferation, collagen production and extracellular matrix mineralization. Furthermore, all analyzed biomaterials elicited an almost identical cell response. Considering that macrophages play a pivotal role in bone remodeling, the behavior of a monocyte-macrophage cell line, RAW 264.7, was also investigated showing a slightly lower inflammatory response to Ti-Mo-Nb biomaterials as compared with cpTi. Thus, the biological performances together with the superior mechanical properties recommend these alloys for bone implant applications.

Diversification of 99Mo/99mTc separation: non­fission reactor production of 99Mo as a strategy for enhancing 99mTc availability.

This paper discusses the benefits of obtaining (99m)Tc from non-fission reactor-produced low-specific-activity (99)Mo. This scenario is based on establishing a diversified chain of facilities for the distribution of (99m)Tc separated from reactor-produced (99)Mo by (n,γ) activation of natural or enriched Mo. Such facilities have expected lower investments than required for the proposed chain of cyclotrons for the production of (99m)Tc. Facilities can receive and process reactor-irradiated Mo targets then used for extraction of (99m)Tc over a period of 2 wk, with 3 extractions on the same day. Estimates suggest that a center receiving 1.85 TBq (50 Ci) of (99)Mo once every 4 d can provide 1.48-3.33 TBq (40-90 Ci) of (99m)Tc daily. This model can use research reactors operating in the United States to supply current (99)Mo needs by applying natural (nat)Mo targets. (99)Mo production capacity can be enhanced by using (98)Mo-enriched targets. The proposed model reduces the loss of (99)Mo by decay and avoids proliferation as well as waste management issues associated with fission-produced (99)Mo.