Demystification of luminescence properties and the near imperceptible thermal quenching of Sm3+-doped tungstate phosphors.

Ultra-high thermally stable Ca2MgWO6:xSm3+ (x = 0.5, 0.75, 1, 1.25, and 1.5 mol%) double perovskite phosphors were synthesized through solid-state reaction method. Product formation was confirmed by comparing the X-ray diffraction (XRD) patterns of the phosphors with the standard reference file. The structural, morphological, thermal, and optical properties of the prepared phosphor were examined in detail using XRD, Fourier transform infrared spectra, scanning electron microscopy, diffused reflectance spectra, thermogravimetric analysis (TGA), photoluminescence emission, and temperature-dependent PLE (TDPL). It was seen that the phosphor exhibited emission in the reddish region for the near-ultraviolet excitation with moderate Colour Rendering Index values and high colour purity. The optimized phosphor (x = 1.25 mol%) was found to possess a direct optical band gap of 3.31 eV. TGA studies showed the astonishing thermal stability of the optimized phosphor. Additionally, near-zero thermal quenching was seen in TDPL due to elevated phonon-assisted radiative transition. Furthermore, the anti-Stokes and Stokes emission peaks were found to be sensitive toward the temperature change and followed a Boltzmann-type distribution. All these marked properties will make the prepared phosphors a suitable candidate for multifield applications and a fascinating material for further development.

Physicomechanical, morphological and tribo-deformation characteristics of lightweight WC/AZ31B Mg-matrix biocomposites for hip joint applications.

Exploring high strength materials with a higher concentration of reinforcements in the alloy proves to be a challenging task. This research has explored magnesium-based composites (AZ31B alloy) with tungsten carbide reinforcements, enhancing strength for medical joint replacements via league championship optimisation. The primary objective is to enhance medical joint replacement biomaterials employing magnesium-based composites, emphasising the AZ31B alloy with tungsten carbide reinforcements. The stir casting method is utilised in the manufacture of magnesium matrix composites (MMCs), including varied percentages of tungsten carbide (WC). The mechanical characteristics, such as micro-hardness, tensile strength, and yield strength, have been assessed and compared with computational simulations. The wear studies have been carried out to analyse the tribological behaviour of the composites. Additionally, this study investigates the prediction of stress and the distribution of forces inside bone and joint structures, therefore offering significant contributions to the field of biomedical research. This research contemplates the use of magnesium-based MMCs for the discovery of biomaterials suitable for medical joint replacement. The study focuses on the magnesium alloy AZ31B, with particles ranging in size from 40 to 60 microns used as the matrix material. Moreover, the outcomes have revealed that when combined with MMCs based on AZ31B-magnesium matrix, the WC particle emerges as highly effective reinforcements for the fabrication of lightweight, high-strength biomedical composites. This study uses the league championship optimisation (LCO) approach to identify critical variables impacting the synthesis of Mg MMCs from an AZ31B-based magnesium alloy. The scanning electron microscopy (SEM) images are meticulously analysed to depict the dispersion of WC particulates and the interface among the magnesium (Mg) matrix and WC reinforcement. The SEM analysis has explored the mechanisms underlying particle pull-out, the characteristics of inter-particle zones, and the influence of the AZ31B matrix on the enhancement of the mechanical characteristics of the composites. The application of finite element analysis (FEA) is being used in order to make predictions regarding the distribution of stress and the interactions of forces within the model of the hip joint. This study has compared the physico-mechanical and tribological characteristics of WC to distinct combinations of 0%, 5%, 10% and 15%, and its impact on the performance improvements. SEM analysis has confirmed the findings' improved strength and hardness, particularly when 10%-15% of WC was incorporated. Following the incorporation of 10% of WC particles within Mg-alloy matrix, the outcomes of the study has exhibited enhanced strength and hardness, which furthermore has been evident by utilising SEM analysis. Using ANSYS, structural deformation and stress levels are predicted, along with strength characteristics such as additional hardness of 71 HRC, tensile strength of 140-150 MPa, and yield strength closer to 100-110 MPa. The simulations yield significant insights into the behaviour of the joint under various loading conditions, thus enhancing the study's significance in biomedical environments.

Plasmonic Imaging of Single DNA with Charge Sensitive Monolayer WS2.

Imaging the surface charge of biomolecules such as proteins and DNA, is crucial for comprehending their structure and function. Unfortunately, current methods for label-free, sensitive, and rapid imaging of the surface charge of single DNA molecules are limited. Here, we propose a plasmonic microscopy strategy that utilizes charge-sensitive single-crystal monolayer WS2 materials to image the local charge density of a single λ-DNA molecule. Our study reveals that WS2 is a highly sensitive charge-sensitive material that can accurately measure the local charge density of λ-DNA with high spatial resolution and sensitivity. The consistency of the surface charge density values obtained from the single-crystal monolayer WS2 materials with theoretical simulations demonstrates the reliability of our approach. Our findings suggest that this class of materials has significant implications for the development of label-free, scanning-free, and rapid optical detection and charge imaging of biomolecules.

Fabrication of pure Bi2WO6 and Bi2WO6/MWCNTs nanocomposite as potential antibacterial and anticancer agents.

An essential research area for scientists is the development of high-performing, inexpensive, non-toxic antibacterial materials that prevent the transfer of bacteria. In this study, pure Bi2WO6 and Bi2WO6/MWCNTs nanocomposite were prepared by hydrothermal method. A series of characterization results by using XRD FTIR, Raman, FESEM, TEM, and EDS analyses, reveal the formation of orthorhombic nanoflakes Bi2WO6 by the addition of NaOH and pH adjustment to 7. Compared to pure Bi2WO6, the Bi2WO6/MWCNTs nanocomposite exhibited that CNTs are efficiently embedded into the structure of Bi2WO6 which results in charge transfer between metal ion electrons and the conduction or valence band of Bi2WO6 and MWCNTs and result in shifting to longer wavelength as shown in UV-visible and PL. The results confirmed that MWCNTs are stuck to the surface of the microflowers, and some of them embedded inside the Bi2WO6 nanoflakes without affecting the structure of Bi2WO6 nanoflakes as demonstrated by TEM. In addition, Pure Bi2WO6 and the Bi2WO6/MWCNTs nanocomposite were tested against P. mirabilis and S. mutans., confirming the effect of addition MWCNTs materials had better antibacterial activity in opposition to both bacterial strains than pure Bi2WO6. Besides, pure Bi2WO6 and the Bi2WO6/MWCNTs nanocomposite tested for cytotoxicity against lung MTT test on Hep-G2 liver cancer cells, and flow-cytometry. Results indicated that pure Bi2WO6 and the Bi2WO6/MWCNTs nanocomposite have significant anti-cancer efficacy against Hep-G2 cells in vitro. In addition, the findings demonstrated that Bi2WO6 and Bi2WO6/MWCNTs triggered cell death via increasing ROS. Based on these findings, it appears that pure Bi2WO6 and the Bi2WO6/MWCNTs nanocomposite have the potential to be developed as nanotherapeutics for the treatment of bacterial infections, and liver cancer.

Oxygen-Independent Radiodynamic Therapy: Radiation-Boosted Chemodynamics for Reprogramming the Tumor Immune Environment and Enhancing Antitumor Immune Response.

Radiodynamic therapy (RDT) has emerged as a promising modality for cancer treatment, offering notable advantages such as deep tissue penetration and radiocatalytic generation of oxygen free radicals. However, the oxygen-dependent nature of RDT imposes limitations on its efficacy in hypoxic conditions, particularly in modulating and eliminating radioresistant immune suppression cells. A novel approach involving the creation of a "super" tetrahedron polyoxometalate (POM) cluster, Fe12-POM, has been developed for radiation boosted chemodynamic catalysis to enable oxygen-independent RDT in hypoxic conditions. This nanoscale cluster comprises four P2W15 units functioning as energy antennas, while the Fe3 core serves as an electron receptor and catalytic center. Under X-ray radiation, a metal-to-metal charge transfer phenomenon occurs between P2W15 and the Fe3 core, resulting in the valence transition of Fe3+ to Fe2+ and a remarkable 139-fold increase in hydroxyl radical generation compared to Fe12-POM alone. The rapid generation of hydroxyl radicals, in combination with PD-1 therapy, induces a reprogramming of the immune environment within tumors. This reprogramming is characterized by upregulation of CD80/86, downregulation of CD163 and FAP, as well as the release of interferon-γ and tumor necrosis factor-α. Consequently, the occurrence of abscopal effects is facilitated, leading to significant regression of both local and distant tumors in mice. The development of oxygen-independent RDT represents a promising approach to address cancer recurrence and improve treatment outcomes.

WS2 nanosheets-based electrochemical biosensor for highly sensitive detection of tumor marker miRNA-4484.

In this paper, a few-layer WS2 nanosheets-based electrochemical biosensor was fabricated for the highly sensitive detection of breast cancer tumor marker miRNA-4484. Firstly, few-layer WS2 nanosheets were prepared by shear stripping and characterized by SEM, TEM, AFM and UV spectrophotometer. After modification of few-layer WS2 nanosheets on the electrode surface, the miRNA probe was fixed on the few-layer WS2 nanosheets by polycytosine (PolyC). Then short-chain miRNA containing PolyC was used as the blocking agent to close the excess active sites on the surface of WS2 nanosheets to complete the fabrication of the sensor biosensing interface. Finally, the current changes caused by the specific binding of miRNA-4484 to the probe were analyzed by differential pulse voltammetry (DPV). The results showed that the sensor had a good linear relationship for the detection of miRNA-4484 in the concentration range of 1 aM-100 fM, and the detection limit was as low as 1.61 aM. In addition, the electrochemical sensor had excellent selectivity, stability and reproducibility. The artificial sample tests indicated that the developed biosensors have the potential for clinical application in the future.

The Effect of Water Coolant and Bur Type on Pulp Temperature When Removing Tooth Structure and Restorative Dental Materials.

OBJECTIVE: The aim was to compare intrapulp temperature (IPT) changes when flat-fissure diamond burs and pear-shaped tungsten carbide burs were used to cut tooth structure, amalgam, and composite resin with and without water coolant. METHODS: Thermocouples were inserted into the pulp chamber of extracted intact mandibular molars. The thermocouples were connected to an electronic thermometer that detects temperature every second to an accuracy of 0.1°C. IPT changes were recorded while using a high-speed handpiece during MOD cavity preparations (n=40), composite resin removal (n=40), and amalgam removal (n=40). A two-way ANOVA was used for each procedure to test for the effect of bur (pear-shaped tungsten carbide vs flat-fissured diamond) and water coolant (on vs off), with significant main effects (α=0.05) further analyzed using Tukey's multiple comparison test. RESULTS: During MOD cavity preparation, water coolant reduced changes in IPT (0.03±0.27°C) compared to no water coolant (1.27±0.29°C) when tungsten carbide burs were used (p<0.05) but not when diamond burs were used. During composite resin removal, tungsten carbide burs had less changes in IPT (0.55±0.18°C) compared to diamond burs (1.66±0.50°C) with no water coolant (p<0.05). Water coolant also reduced changes in IPT (0.09±0.14°C) compared to no water coolant (1.66±0.50°C) when diamond burs were used (p<0.01). Water coolant did not significantly affect IPT when tungsten carbide burs were used. During amalgam removal, tungsten carbide burs had lower changes in IPT (0.56±0.15°C) compared to diamond burs (1.88±0.43°C) with no water coolant (p<0.05). Water coolant also significantly reduced changes in IPT (0.71±0.2°C) compared to no water coolant (1.88±0.43°C) when diamond burs were used (p<0.05) but not when tungsten carbide burs were used. CONCLUSIONS: Water coolant reduced IPT changes when drilling tooth structure with tungsten carbide burs, but not when removing amalgam or composite. Conversely, water coolant reduced IPT changes when drilling with flat fissure diamond burs to remove amalgam and composite, but not when removing tooth structure. When amalgam and composite were removed without water coolant, the tungsten carbide burs resulted in lower IPT changes than when flat fissure diamond burs were used in the same way.

Combined Experimental and Computational Study of V-Substituted Lindqvist Polyoxotungstate: Screening by Docking for Potential Antidiabetic Activity.

In the current work, a novel vanadotungstate compound, (C6H9N2)4[V2W4O19]·2H2O (1), is isolated by a simple stepwise synthesis method and characterized by a combined experimental and computational study. Molecular docking is conducted for the first time for this kind of substituted Lindqvist polyoxometalates to elucidate for potential antidiabetic activity. Hence, the modeling results revealed a significant docking score of the reported compound to bind to the active sites of α-glucosidase with the lowest binding energy of -5.7 kcal/mol, where the standard drug acarbose (ACB) had -4.6 kcal/mol binding energy. The stability of binding was enhanced by strong H-bonding, van der Waals, and electrostatic interactions occurring in the three-dimensional (3D) supramolecular network of polyanionic vanadotungstate subunits templated with organic moieties as shown by X-ray diffraction and Hirshfeld analyses. Furthermore, density functional theory (DFT) calculations supported with photophysical measurements are also discussed to predict the most chemical and biological reactivity. In this view, the complete description of electronic and biological features of (1) is enhanced by determination of the highest occupied molecular orbital (HOMO)/least unoccupied molecular orbital (LUMO) energy, electronic density, ionization potential, electron affinity, etc. These chemical descriptors, intermolecular interactions, docking score, and binding free energy estimation are essential in understanding the reactivity of this bioactive compound offering potential inhibition of the α-glucosidase enzyme.

Reactivity of a Dithiocarbamate-Ligated [WVI≡S] Complex with Hydride Donors: Toward a Synthetic Mimic of Formate Dehydrogenase.

Formate dehydrogenase (FDH) enzymes catalyze redox interconversion of CO2 and HCO2-, with a key mechanistic step being the transfer of H- from HCO2- to an oxidized active site featuring a [MVI≡S] group in a sulfur-rich environment (M = Mo or W). Here, we report reactivity studies with HCO2- and other reducing agents of a synthetic [WVI≡S] model complex ligated by dithiocarbamate (dtc) ligands. Reactions of [WVIS(dtc)3][BF4] (1) conducted in MeOH solvent generated [WVIS(S2)(dtc)2] (2) and [WVS(µ-S)(dtc)]2 (3) products by a solvolysis pathway that was accelerated by the presence of [Me4N][HCO2] but did not require it. Under MeOH-free conditions, the reaction of 1 with [Et4N][HCO2] produced some [WIV(µ-S)(µ-dtc)(dtc)]2 (4), but predominantly [WV(dtc)4]+ (5), along with stoichiometric CO2 detected by headspace gas chromatography (GC) analysis. Stronger hydride sources such as K-selectride generated the more reduced analogue, 4, exclusively. The reaction of 1 with the electron donor, CoCp2, also produced 4 and 5 in varying amounts depending on reaction conditions. These results indicate that formates and borohydrides act as electron donors rather than hydride donors toward 1, an outcome that diverges from the behavior of FDHs. The difference is ascribed to the more oxidizing potential of [WVI≡S] complex 1 when supported by monoanionic dtc ligands that allows electron transfer to outcompete hydride transfer, as compared to the more reduced [MVI≡S] active sites supported by dianionic pyranopterindithiolate ligands in FDHs.

Exploiting Interactions between Polyoxometalates and Proteins for Applications in (Bio)chemistry and Medicine.

The specific interactions of anionic metal-oxo clusters, known as polyoxometalates (POMs), with proteins can be leveraged for a wide range of analytical and biomedical applications. For example, POMs have been developed as selective catalysts that can induce protein modifications and have also been shown to facilitate protein crystallization, both of which are instrumental in the structural characterization of proteins. POMs can also be used for selective protein separation and enzyme inhibition, which makes them promising therapeutic agents. Hence, understanding POM-protein interactions is essential for the development of POM-based materials and their implementation in several fields. In this Review we summarize in detail the key insights that have been gained so far on POM-protein interactions. Emphasis is also given to hybrid POMs functionalized with organic ligands to prompt further research in this direction owing to the promising recent results on tuning POM-protein interactions through POM functionalization.

Performance and mechanism of a novel S-scheme heterojunction sonocatalyst CuS/BaWO4 for degradation of bisphenol A by ultrasonic activation.

A novel CuS/BaWO4 heterojunction catalyst was prepared and characterized. Taking bisphenol A as the target pollutant for catalytic degradation, the sonocatalytic activity of CuS/BaWO4 composite was evaluated, and the combination with persulfate improved the sonocatalytic degradation of bisphenol A. The results showed that CuS/BaWO4 composite had good sonocatalytic degradation activity for bisphenol A, and the degradation rate was 70.99% ± 1.46%. After combined with persulfate, the degradation rate was further increased to 95.34% ± 0.10%, and the reaction time was relatively shortened. The results of the trapping experiment and calculated energy band positions showed that the formation of S-scheme heterojunction and the formation of hydroxyl radicals and holes were the key to the catalytic degradation of bisphenol A by CuS/BaWO4 composite. In this study, a new CuS/BaWO4 heterojunction sonocatalyst was synthesized. The catalyst can efficiently remove bisphenol A from the water environment and can be used as a potential solution for endocrine disruptor pollution in the water environment.

Self-assembly of a novel multicomponent polyoxometalate-based tetrahedral supercluster with high catalytic activity for thioether oxidation.

A glamorous polyoxometalate (POM)-based macromolecule containing a tetrahedral supercluster (Hbiz)12[(P2Co2MoV4O8)2(P2MoV2O8)4(Pb⊂P6Co2MoV2MoVI14O73)4]·ca.129H2O (1) was in situ self-assembled from three novel components, [Pb⊂P6Co2Mo16O73]8- (P6Co2Mo16), [P2MoV2O8]4+ (P2Mo2) and [P2Co2MoV4O8]18+ (P2Co2Mo4), respectively. To our knowledge, 1 represents the first tetrahedral supercluster containing the basket-like POM structure. Besides, macromolecule 1 exhibits high catalytic activity and reusability for the oxidation of thioethers to sulfoxides.

Two Polyoxometalate-Encapsulated Two-Fold Interpenetrating dia Metal-Organic Frameworks for the Detection, Discrimination, and Degradation of Phenolic Pollutants.

Phenols are widely used for commercial production, while they pose a hazard to the environment and human health. Thus, investigation of convenient and efficient methods for the detection, discrimination, and degradation of phenols becomes particularly important. Herein, two new polyoxometalate (POM)-based compounds, [Co2(btap)4(H2O)4][SiW12O40] (Co-POM) and [Ni2(btap)4(H2O)4][SiW12O40] (Ni-POM) (btap = 3,5-bis(triazol-1-yl)pyridine), are prepared via a hydrothermal synthesis method. The compounds show a fascinating structural feature of a POM-encapsulated twofold interpenetrating dia metal-organic framework. More importantly, besides the novel structures, the compound Co-POM realizes three functions, namely, the simultaneous detection, discrimination, and degradation of phenols. Specifically, Co-POM shows an excellent colorimetric detection performance toward phenol with a detection limit (LOD) ca. 1.32 µM, which is lower than most reported colorimetric detectors for phenol. Also, a new colorimetric sensor system based on Co-POM can discriminate phenol, 4-chlorophenol, and o-cresol with ease. Further, Co-POM exhibits a photocatalytic degradation property for 4-chlorophenol under irradiation of visible light with the highest degradation rate at 62% after irradiation for 5 h. Therefore, this work provides the first example of a POMs-based multifunctional material for achieving the detection, discrimination, and degradation of phenolic pollutants.

A Water-Soluble Antimony-Rich Polyoxometalate with Broad-Spectrum Antitumor Activities.

Herein, a giant Sb-rich polyoxometalate (POM) {Sb21 Tb7 W56 } is reported, which contains the largest number of Sb atoms in a POM so far. The Sb-rich POM has many interesting structural features and is a rare example of a soluble and water-stable giant POM. Biomedical studies indicate that the Sb-rich POM exhibits broad-spectrum antitumor activity against various cancer cell lines by reactivating the P53-dependent apoptotic processes and disrupting the mitochondrial membrane. In addition, this Sb-rich POM was capable of suppressing the growth and metastasis of a breast cancer in vivo. This work demonstrates that Sb-rich POMs are promising candidates for the development of new anticancer drugs.

Promising application of polyoxometalates in the treatment of cancer, infectious diseases and Alzheimer's disease.

As shown in studies conducted in recent decades, polyoxometalates (POMs), as inorganic metal oxides, have promising biological activities, including antitumor, anti-infectious and anti-Alzheimer's activities, due to their special structures and properties. However, some side effects impede their clinical applications to a certain extent. Compared with unmodified POMs, POM-based inorganic-organic hybrids and POM-based nanocomposite structures show significantly enhanced bioactivity and reduced side effects. In this review, we introduce the biological activities of POMs and their derivatives and highlight the side effects of POMs on normal cells and organisms and their possible mechanisms of action. We then propose a development direction for overcoming their side effects. POMs are expected to constitute a new generation of inorganic metal drugs for the treatment of cancer, infectious diseases, and Alzheimer's disease.Graphical abstract.

Factors influencing stoichiometry and stability of polyoxometalate - peptide complexes.

In the pursuit of understanding the factors guiding interactions between polyoxometalates (POMs) and biomolecules, several complexes between Keggin phosphomolybdate and diglycine have been produced at different acidity and salinity conditions, leading to difference in stoichiometry and in crystal structure. Principal factors determining how the POM and dipeptide interact appear to be pH, ionic strength of the medium, and the molar ratio of POM to peptide. An important effect turned out to be even the structure-directing role of the sodium cations coordinating carbonyl functions of the peptide bond. Given the interest in applying POMs in biological systems, these factors are highly relevant to consider. In the view of recent interest in using POMs as nano catalysts in peptide hydrolysis also the potential Keggin POM transformation in phosphate buffered saline medium was investigated leading to insight that nanoparticles of zirconium phosphate (ZrP) can be actual catalysts for breakdown of the peptide bond.

Polyoxometalate-based materials in extraction, and electrochemical and optical detection methods: A review.

Polyoxometalates (POMs) as metal-oxide anions have exceptional properties like high negative charges, remarkable redox abilities, unique ligand properties and availability of organic grafting. Moreover, the amenability of POMs to modification with different materials makes them suitable as precursors to further obtain new composites. Due to their unique attributes, POMs and their composites have been utilized as adsorbents, electrodes and catalysts in extraction, and electrochemical and optical detection methods, respectively. A survey of the recent progress and developments of POM-based materials in these methods is therefore desirable, and should be of great interest. In this review article, POM-based materials, their properties as well as their identification methods, and analytical applications as adsorbents, electrodes and catalysts, and corresponding mechanisms of action, where relevant, are reviewed. Some current issues of the utilization of these materials and their future prospects in analytical chemistry are discussed.

Polyoxometalate-polypeptide nanoassemblies as peroxidase surrogates with antibiofilm properties.

Developing artificial metalloenzymes that possess a superior performance to their natural counterparts is an attractive concept. Polyoxometalates (POMs) are a class of anionic molecular metal-oxides with excellent redox properties and bioactivity. We have recently introduced "POMlymers" - covalently conjugated POM-peptide hybrid materials - where the polypeptide chain is obtained through a ring-opening polymerisation (ROP) of α-amino acid N-carboxyanhydrides (NCA) on an inorganic POM scaffold. Attracted by the idea of preparing artificial metalloenzymes, here we report the supramolecular self-assembly of POMlymer hybrids into nanoparticles where an optimal environment for catalysis is created. Our results demonstrate that the self-assembly of covalent POMlymers, enhances the peroxidase-like activity of the parent POM anion whereas, in contrast, the catalytic activity for nanoparticles obtained by ionic self-assembly of the same peptide and POM components practically disappears. Furthermore, POMlymer nanoparticles also present antimicrobial and antibiofilm activity against the skin bacterium Staphylococcus epidermidis; whereas, ionic POM-peptide hybrids significantly increase biofilm production and endogenous production of reactive oxygen species. In summary, we present the self-assembly of POMlymer hybrids into nanoparticles and a combination of peroxidase activity and microbiology assays that show that the POM-peptide covalent bond is essential for the stability of the self-assembled nanoparticles and therefore for their catalytic and biological activity.

Paper-Based Electrodes Conjugated with Tungsten Disulfide Nanostructure and Aptamer for Impedimetric Detection of Listeria monocytogenes.

In this study, we report on a novel aptasensor based on an electrochemical paper-based analytical device (ePAD) that employs a tungsten disulfide (WS2)/aptamer hybrid for the detection of Listeria monocytogenes. Listeria is a well-known causative pathogen for foodborne diseases. The proposed aptasensor signifies many lucrative features which include simple, cost-effective, reliable, and disposable. Furthermore, the use of an aptamer added more advantageous features in the biosensor. The morphological, optical, elemental composition, and phase properties of the synthesized tungsten disulfide (WS2) nanostructures were characterized by field-emission scanning electron microscopy (FESEM), RAMAN spectroscopy, photoluminescence (PL), and X-ray diffraction (XRD), while electrochemical impedance spectroscopy was performed to corroborate the immobilization of aptamer and to assess the L. monocytogenes sensing performance. The limit of detection (LoD) and limit of quantification (LoQ) of the aptasensor was found to be 10 and 4.5 CFU/mL, respectively, within a linear range of 101-108 CFU/mL. The proposed sensor was found to be selective solely towards Listeria monocytogenes in the presence of various bacterial species such as Escherichia coli and Bacillus subtilis. Validation of the aptasensor operation was also evaluated in real samples by spiking them with fixed concentrations (101, 103, and 105) of Listeria monocytogenes, thereby, paving the way for its potential in a point-of-care scenario.

Chalcogen Bonding in the Molecular Dimers of WCh2 (Ch = S, Se, Te): On the Basic Understanding of the Local Interfacial and Interlayer Bonding Environment in 2D Layered Tungsten Dichalcogenides.

Layered two-dimensional transition metal dichalcogenides and their heterostructures are of current interest, owing to the diversity of their applications in many areas of materials nanoscience and technologies. With this in mind, we have examined the three molecular dimers of the tungsten dichalcogenide series, (WCh2)2 (Ch = S, Se, Te), using density functional theory to provide insight into which interactions, and their specific characteristics, are responsible for the interfacial/interlayer region in the room temperature 2H phase of WCh2 crystals. Our calculations at various levels of theory suggested that the Te···Te chalcogen bonding in (WTe2)2 is weak, whereas the Se···Se and S···S bonding interactions in (WSe2)2 and (WS2)2, respectively, are of the van der Waals type. The presence and character of Ch···Ch chalcogen bonding interactions in the dimers of (WCh2)2 are examined with a number of theoretical approaches and discussed, including charge-density-based approaches, such as the quantum theory of atoms in molecules, interaction region indicator, independent gradient model, and reduced density gradient non-covalent index approaches. The charge-density-based topological features are shown to be concordant with the results that originate from the extrema of potential on the electrostatic surfaces of WCh2 monomers. A natural bond orbital analysis has enabled us to suggest a number of weak hyperconjugative charge transfer interactions between the interacting monomers that are responsible for the geometry of the (WCh2)2 dimers at equilibrium. In addition to other features, we demonstrate that there is no so-called van der Waals gap between the monolayers in two-dimensional layered transition metal tungsten dichalcogenides, which are gapless, and that the (WCh2)2 dimers may be prototypes for a basic understanding of the physical chemistry of the chemical bonding environments associated with the local interfacial/interlayer regions in layered 2H-WCh2 nanoscale systems.