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  • Molybdenum (Mo) is a crucial microelement for both, humans and plants. The use of agronomic biofortification techniques can be an alternative method to enhance Mo content in vegetables. Concomitantly, arbuscular mycorrhizal fungi (AMF) application is a valuable strategy to enhance plant performances and overcome plant abiotic distresses such as microelement overdose. The aim of this research was to estimate the direct and/or indirect effects of Mo supply at four doses [0.0, 0.5 (standard dose), 2.0 or 4.0 μmol L], alone or combined with AMF inoculation, on plant performances. In particular, plant height and first flower truss emission, productive features (total yield, marketable yield and average marketable fruit weight) and fruit qualitative characteristics (fruit dry matter, soluble solids content, titratable acidity, ascorbic acid, lycopene, polyphenol, nitrogen, copper, iron and molybdenum) of an established cherry tomato genotype cultivated in soilless conditions were investigated. Moreover, proline and malondialdehyde concentrations, as well as Mo hazard quotient (HQ) in response to experimental treatments were determined. A split-plot randomized experimental block design with Mo dosages as plots and +AMF or -AMF as sub-plots was adopted. Data revealed that AMF inoculation enhanced marketable yield (+50.0 %), as well as some qualitative traits, such as fruit soluble solids content (SSC) (+9.9 %), ascorbic acid (+7.3 %), polyphenols (+2.3 %), and lycopene (+2.5 %). Molybdenum application significantly increased SSC, polyphenols, fruit Mo concentration (+29.0 % and +100.0 % in plants biofortified with 2.0 and 4.0 μmol Mo L compared to those fertigated with the standard dose, respectively) and proline, whereas it decreased N (-25.0 % and -41.6 % in plants biofortified with 2.0 and 4.0 μmol Mo L compared to those fertigated with the standard dose, respectively). Interestingly, the application of AMF mitigated the detrimental effect of high Mo dosages (2.0 or 4.0 μmol L). A pronounced advance in terms of plant height 45 DAT, fruit lycopene concentration and fruit Fe, Cu and Mo concentrations was observed when AMF treatment and Mo dosages (2.0 or 4.0 μmol Mo L) were combined. Plants inoculated or not with AMF showed an improvement in the hazard quotient (HQ) in reaction to Mo application. However, the HQ - for a consumption of 200 g day of biofortified cherry tomato - remained within the safety level for human consumption. This study suggests that Mo-implementation (at 2.0 or 4.0 μmol L) combined with AMF inoculation could represent a viable cultivation protocol to enhance yield, produce premium quality tomato fruits and, concomitantly, improve Mo dose in human diet. In the light of our findings, further studies on the interaction between AMF and microelements in other vegetable crops are recommended.

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  • Transition Metal Dichalcogenides (TMDs) are a unique class of materials that exhibit attractive electrical and optical properties which have generated significant interest for applications in microelectronics, optoelectronics, energy storage, and sensing. Considering the potential of these materials to impact such applications, it is crucial to develop a reliable and scalable synthesis process that is compatible with modern industrial manufacturing methods. Metal-organic chemical vapor deposition (MOCVD) offers an ideal solution to produce TMDs, due to its compatibility with large-scale production, precise layer control, and high material purity. Optimization of MOCVD protocols is necessary for effective TMD synthesis and integration into mainstream technologies. Additionally, improvements in metrology are necessary to measure the quality of the fabricated samples more accurately. In this work, we study MOCVD of wafer-scale molybdenum disulfide (MoS) utilizing two common chalcogen precursors, HS and DTBS. We then develop a metrology platform for wafer scale samples quality assessment. For this, the coalesced films were characterized using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Kelvin probe force microscopy. We then correlate the structural analysis of these grown films with electrical performance by using aerosol jet printing to fabricate van der Pauw test structures and assess sheet resistance.

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  • Constrained patterning of orientated metal chalcogenide nanowires and their growth mechanism.

    One-dimensional metallic transition-metal chalcogenide nanowires (TMC-NWs) hold promise for interconnecting devices built on two-dimensional (2D) transition-metal dichalcogenides, but only isotropic growth has so far been demonstrated. Here we show the direct patterning of highly oriented MoTe NWs in 2D molybdenum ditelluride (MoTe) using graphite as confined encapsulation layers under external stimuli. The atomic structural transition is studied through in-situ electrical biasing the fabricated heterostructure in a scanning transmission electron microscope. Atomic resolution high-angle annular dark-field STEM images reveal that the conversion of MoTe NWs from MoTe occurs only along specific directions. Combined with first-principles calculations, we attribute the oriented growth to the local Joule-heating induced by electrical bias near the interface of the graphite-MoTe heterostructure and the confinement effect generated by graphite. Using the same strategy, we fabricate oriented NWs confined in graphite as lateral contact electrodes in the 2H-MoTe FET, achieving a low Schottky barrier of 11.5 meV, and low contact resistance of 43.7 Ω µm at the metal-NW interface. Our work introduces possible approaches to fabricate oriented NWs for interconnections in flexible 2D nanoelectronics through direct metal phase patterning.

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  • Methanogens often inhabit sulfidic environments that favor the precipitation of transition metals such as iron (Fe) as metal sulfides, including mackinawite (FeS) and pyrite (FeS). These metal sulfides have historically been considered biologically unavailable. Nonetheless, methanogens are commonly cultivated with sulfide (HS) as a sulfur source, a condition that would be expected to favor metal precipitation and thus limit metal availability. Recent studies have shown that methanogens can access Fe and sulfur (S) from FeS and FeS to sustain growth. As such, medium supplied with FeS should lead to higher availability of transition metals when compared to medium supplied with HS. Here, we examined how transition metal availability under sulfidic (i.e., cells provided with HS as sole S source) versus non-sulfidic (cells provided with FeS as sole S source) conditions impact the metalloproteome of Fusaro. To achieve this, we employed size exclusion chromatography coupled with inductively coupled plasma mass spectrometry and shotgun proteomics. Significant changes were observed in the composition and abundance of iron, cobalt, nickel, zinc, and molybdenum proteins. Among the differences were alterations in the stoichiometry and abundance of multisubunit protein complexes involved in methanogenesis and electron transport chains. Our data suggest that utilizes the minimal iron-sulfur cluster complex and canonical cysteine biosynthesis proteins when grown on FeS but uses the canonical Suf pathway in conjunction with the tRNA-Sep cysteine pathway for iron-sulfur cluster and cysteine biosynthesis under sulfidic growth conditions.IMPORTANCEProteins that catalyze biochemical reactions often require transition metals that can have a high affinity for sulfur, another required element for life. Thus, the availability of metals and sulfur are intertwined and can have large impacts on an organismismal biochemistry. Methanogens often occupy anoxic, sulfide-rich (euxinic) environments that favor the precipitation of transition metals as metal sulfides, thereby creating presumed metal limitation. Recently, several methanogens have been shown to acquire iron and sulfur from pyrite, an abundant iron-sulfide mineral that was traditionally considered to be unavailable to biology. The work presented here provides new insights into the distribution of metalloproteins, and metal uptake of Fusaro grown under euxinic or pyritic growth conditions. Thorough characterizations of this methanogen under different metal and sulfur conditions increase our understanding of the influence of metal availability on methanogens, and presumably other anaerobes, that inhabit euxinic environments.

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  • Over the past two decades, following the discovery of the important biological roles of carbon monoxide (CO), metal carbonyl complexes have been intensively studied as CO-releasing molecules (CORMs) for therapeutic applications. To improve the properties of "bare" low molecular weight CORMs, attention has been drawn to conjugating CORMs with macromolecular and inorganic scaffolds to produce CO-releasing materials (CORMAs) capable of storing and delivering large payloads of the gasotransmitter. A significant obstacle is to obtain CORMAs that retain the beneficial features of the parent CORMs. In the present work, a crystalline metal-organic framework (MOF) formulated as Mo(CO)(4,4'-bipyridine) (), with a structure based on Mo(CO) metallic nodes and bipyridine linkers, has been prepared in near quantitative yield by a straightforward reflux method, and found to exhibit CO-release properties that mimic those typically observed for molybdenum carbonyl CORMs. was characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR, FT-Raman and diffuse reflectance (DR) UV-vis spectroscopies, and C{H} cross-polarization (CP) magic-angle spinning (MAS) NMR. The release of CO from was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. liberates CO upon contact with a physiological buffer in the dark, leading to a maximum released amount of 1.3-1.5 mmol g, after 1.5 h at 37 °C, with half-lives of 0.5-1.0 h (time to transfer 0.5 equiv. of CO to Mb). In the solid-state and under open air, undergoes complete decarbonylation over a period of 42 days, corresponding to a theoretical CO-release of 7.25 mmol g.

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  • The rapid and reliable detection of triethylamine (TEA), a toxic, explosive, volatile organic compound at room temperature, is highly significant for food safety, environmental, and human health monitoring. This manuscript reports a layered molybdenum disulfide (MoS) nanosheet-coated polypyrrole (PPy) nanorod-based heterostructure sensor (MsPy) which offers superior sensing properties toward TEA at room temperature (25 °C). Herein, different MsPy nanocomposites were synthesized, followed by a controlled sulfidation reaction through dissolution, diffusion, and regrowth mechanisms. Optimizing the ratio of the precursor of molybdenum trioxide (MoO/PPy) is crucial for achieving effective deposition of a layered MoS nanosheet on the PPy surface. The as-prepared MoS nanosheet-coated PPy sensor (MsPy_40) enables one to selectively detect trace TEA vapor at 25 °C with a detection lower limit of 0.5 ppm. The MsPy_40 sensor exhibits 17 times higher response than the pristine MoS nanosheet to 50 ppm TEA, with rapid response (∼3.9 s) and recovery (∼19.6 s), along with better stability, good selectivity, and remarkable repeatability. The significantly enhanced sensing performance is attributed to the unique surface morphology of the layered MoS nanosheet-coated PPy nanorod and the formation of a p-n heterojunction between PPy and MoS.

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  • 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 (MoS) layers. Ca 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 MoS layers. The alginate films exhibit strain-sensitive triboelectricity, confirming the presence of abundant mobile Ca ions, which enables them to be active components of 2D MoS field-effect transistors (FETs) functioning as electrolyte top-gates. The alginate-integrated 2D MoS 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.

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  • The optimal disinfection protocol that controls adverse effects and promotes effective antimicrobial action on removable prostheses is unclear.

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  • Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K[Fe(CN)] show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS/SGCN modified glassy carbon electrode (MoS/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 μM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10 s. The results of this study confirm that the MoS/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.

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  • Molybdenum is an essential micronutrient, but because of its toxicity at high concentrations, its accumulation in living organisms has not been widely demonstrated. In this study, we report that the marine sponge accumulates exceptionally high levels of molybdenum (46,793 micrograms per gram of dry weight) in a wide geographic distribution from the northern Red Sea to the reefs of Zanzibar, Indian Ocean. The element is found in various sponge body fractions and correlates to selenium. We further investigated the microbial composition of the sponge and compared it to its more studied congener, . Our analysis illuminates the symbiotic bacterium sp. and its role in molybdenum accumulation. Through microscopic and analytical methods, we provide evidence of intracellular spheres within sp. that exhibit high molybdenum content, further unraveling the intricate mechanisms behind molybdenum accumulation in this sponge species and its significance in the broader context of molybdenum biogeochemical cycling.

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