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In this study, we have constructed a ratiometric fluorescence sensor for sensitive sensing of α-glucosidase activity based on WS2 QDs/ CoOOH nanosheet system. In this system, as an oxidase-imimicking nanomaterial, CoOOH nanosheet could convert o-phenylenediamine into 2,3-diaminophenazine (DAP), which had a high fluorescence emission at 575 nm. The DAP subsequently could quench the fluorescence of WS2 QDs via the inner filter effect (IFE). L-Ascorbic acid-2-O-α-D-glucopyranose could be hydrolyzed by α-glucosidase to yield ascorbic acid. CoOOH nanosheet can be converted to Co2+ ions by ascorbic acid, leading to the fluorescence decrease of DAP and the fluorescence recovery of WS2 QDs. Therefore, a novel ratio fluorescence sensing strategy was established for α-glucosidase detection based on WS2 QDs/CoOOH nanosheet system. This WS2 QDs/CoOOH nanosheet system has a low detection limit of 0.009 U/mL for α-Glu assay. The proposed strategy succeeded in detecting α-Glu in human serum samples.

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In this study, a novel fluorescence sensor for tetracyclines (TCs) detection was designed using WS2 quantum dots (WS2 QDs). WS2 QDs could be quenched by TCs through the inner filter effect (IFE). The limit of detection of this proprosed method is 39 nM, 52 nM, and 28 nM for tetracycline (TC), doxycycline (DC), and oxytetracycline (OTC), respectively. The as-proposed strategy was successfully applied to detect TC in milk samples and human serum samples. The WS2 QDs were highly biocompatible and showed lower toxicity. Moreover, the WS2 QDs was successfully applied to imaging TC in HeLa cells owing to its excellent optical performance and great biocompatibility.

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Recent progress in the synthesis of highly stable, eco-friendly, cost-effective transition-metal dichalcogenide (TMDC) quantum dots (QDs) with their broadband absorption spectra and wavelength selectivity features have led to their increasing use in broadband photodetectors. With the solution-based processing, we demonstrate a superlarge (∼0.75 mm2), ultraviolet-visible (UV-vis) broadband (365-633 nm) phototransistor made of WS2 QDs-decorated chemical vapor deposited (CVD) graphene as the active channel with extraordinary stability and durability under ambient conditions (without any degradation of photocurrent until 4 months after fabrication). Here, colloidal zero-dimensional (0D) WS2 QDs are used as the photoabsorbing material, and graphene acts as the conducting channel. A high photoresponsivity (3.1 × 102 A/W), moderately high detectivity (∼8.9 × 108 Jones), and low noise equivalent power (∼9.7 × 10-11 W/Hz0.5) are obtained at a low bias voltage (Vds = 1 V) at an illumination of 365 nm with optical power as low as ∼0.8 µW/cm2, which can be further tuned by modulating the gate bias. While comparing the photocurrent between two different morphologies of WS2 [QDs and two-dimensional (2D) nanosheets], a significant enhancement of photocurrent is observed in the case of QD-based devices. Ab initio density functional theory (DFT)-based calculations further support our observation, revealing the role of quantum confinement in enhanced photoresponse. Our work reveals a strategy toward developing a scalable, cost-effective, high-performance hybrid mixed-dimensional (2D-0D) photodetector with graphene-WS2 QDs for next-generation optoelectronic applications.

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We document the fabrication and investigations of a novel photodetector based on a WS2 quantum dots and reduced graphene oxide (RGO) (WS2-QDs/RGO) heterostructure. The proposed photodetector is simple, scalable, cost-effective, and flexible and works in an ambient environment. An enhanced photodetection efficiency is observed due to the superior electronic properties of WS2-QDs and excellent electrical as well as thermal properties of the carrier transportation medium, RGO. For device fabrication, GO and WS2-QDs were separately synthesized via different chemistry followed by decorating WS2-QDs on RGO coated cotton textile. Characterization studies confirm the transformation of exfoliated WS2-2D flakes into WS2-0D quantum dots and graphene oxide (GO) to RGO. The optimized photodetection performance of WS2-QDs/RGO demonstrates its photoresponsivity of 5.22 mA W-1 at 1.4 mW mm-2 power density of a 405 nm illumination source. Other sensor parameters such as photosensitivity (∼20.2%), resolution (∼0.031 mW mm-2 µA-1), response time (1.57 s), recovery time (1.83 s), and specific detectivity (∼1.6 × 106 jones) are found for WS2-QDs/RGO sensor, and a few of these parameters are comparable and even superior to some of the devices as reported. Photosensing mechanism is explained in terms of charge transfer caused by appropriate band alignment across the interface between WS2-QDs and RGO, where dimensionality and quantum confinement of nanostructures synergistically enhance the overall performance of the heterostructure. The device flexibility is examined through bending, stretching, and twisting experiments and successfully demonstrated its potentiality. Sensor performance even after being soaked in water and subsequent drying shows the possibility of reuse. The attributes of flexibility, high sensitivity and responsivity, superior resolution, and cost-effectiveness of our novel flexible photodetector indicate its promising potential for flexible and wearable optical detectors operating in UV band. Although negative photoconductance of the WS2-QDs/RGO sensor is a major cause for not allowing the sensor to show its best performance, a trade-off is made with improved device design to qualify the expectations of being a competitive device, and this has been demonstrated with experimental facts.

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Based on WS2 quantum dots (QDs) as fluorescent signals and MnO2 nanosheets as second-order scattering (SOS) signals, a combination of fluorescence and scattered light was used to construct a ratio sensing platform for glutathione (GSH) detection. When MnO2 nanosheets are added to WS2 QDs, the fluorescence of WS2 QDs is quenched by MnO2 nanosheets through IFE. Large-sized MnO2 nanosheets increase the SOS of the system and gradually approach the fluorescence. After adding GSH to WS2 QDs-MnO2, the MnO2 nanosheets were decomposed into Mn2+. The disappearance of the characteristic absorption peak of the MnO2 nanosheets suppressed the IFE to WS2 QDs, resulting in the fluorescence recovery of WS2 QDs. The reduction in size of MnO2 nanosheets after decomposition results in a decrease in the SOS of the system. Therefore, the ratio detection of GSH is obtained through the fluorescence and SOS dual signal response. Under optimal experimental conditions, the value of F406/S648 is linearly related to the GSH concentration in the range 0 to 60 µM, and the limit of detection (LOD) of GSH is 0.12 µM. In addition, the system is also used for the determination of GSH in real water samples and human serum, with good analytical results. Graphical abstract Schematic principle of fluorescence/scattered light system based on WS2 QDs-MnO2 for GSH ratiometric detection.

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Herein, we investigate the origin of excitation wavelength dependent spectral features and high fluorescence quantum yield in fluorescent 2D tungsten disulfide (WS2) quantum dots (QDs) of average size 2.4 nm. The as-prepared WS2 QDs possess high optical bandgap and reasonably high fluorescence quantum yield ~15.4% in the green region without any functionalization. The broad photoluminescence (PL) spectrum consists of multiple peaks owing to emissions from excitonic transitions and surface defect-related transitions. The excitation wavelength-dependent spectral redshift and narrowing of line shape in the PL peak are analyzed carefully, and it is attributed to the selective excitation/recombination of carriers from different energy levels. The temperature-dependent PL analysis yields an exciton binding energy of ~301 meV in the QDs. Furthermore, we study the interaction between fluorescent WS2 QDs and single-walled carbon nanotubes (SWCNTs) and explore the mechanism of systematic quenching of PL of QDs by SWCNTs. The nature of the Stern-Volmer plot is found to be linear, and the time-resolved fluorescence measurements reveal that the quenching follows primarily the static behavior. Our study further reveals that defect sites in SWCNTs primarily act as the binding sites for WS2 QDs and form non-fluorescent complexes for effective quenching of the PL. The strong interaction between the WS2 QDs and the SWCNTs is evidenced from the spectral shift in the X-ray photoelectron spectroscopy and Raman peaks. Our study reveals the origin of excitation wavelength dependent PL emission from WS2 QDs and the nature of the interaction between WS2 QDs and SWCNTs, which are important for their applications in biomedical imaging and sensing, such as surface-enhanced Raman scattering, etc.

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A voltammetric method is described for the determination of chloroquine (CQ) and validated simultaneously by two techniques and in three different conditions. The WS2 quantum dots (WS2 QDs) were synthesized by a hydrothermal method and then placed on reduced graphene oxide (rGO) sheets. The resulting composite material was then deposited on a glassy carbon electrode (GCE) where it showed excellent electroactivity. The modified GCE responds to chloroquine at a typical potential maximum of 1.2 V (vs. AgCl/Ag). Techniques including cyclic voltammetry and differential pulse voltammetry were tested. Features of merit include (a) a wide linear response (in the 0.5 µM to 82 µM CQ concentration range), (b) an electrochemical sensitivity of 0.143-0.90 µA·µM-1·cm-2), and a 40-120 nM limit of detection (at S/N = 3). The sensor has excellent selectivity even in the presence of potentially interfering biological compounds. Responses were tested in phosphate buffer, human serum and pharmaceutical formulations, and no cross reactivity or matrix effects were found. In all the three cases, quite satisfactory recoveries were obtained. Graphical abstract Schematic representation of the mechanism for electro-oxidation of chloroquine on a glassy carbon electrode modified with an rGO@WS2 quantum dot composite. The sensor displays enhanced electrocatalytic activity towards chloroquine. The method was validated in biological samples and pharmaceutical formulations.

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Currently, researchers are looking for nanomaterials with peroxidase-like activity to replace natural peroxidase enzymes. For this purpose, WS2 quantum dots (WS2 QDs) were synthesized via a solvothermal method, which improved the mimetic behavior. The resulting WS2 QDs with a size of 1⁻1.5 nm had a high fluorescence emission, dependent on the excitation wavelength. WS2 QDs with uniform morphology showed a high catalytic effect in destroying H2O2. The peroxidase-like activity of synthesized nanostructures was studied in H2O2 chemical and electrochemical reduction systems. The mimetic effect of WS2 QDs was also shown in an H2O2⁻rhodamine B (RB) chemiluminescence system. For this aim, a stopped-flow chemiluminescence (CL) detection system was applied. Also, in order to confirm the peroxidase-like effect of quantum dots, colorimetry and electrochemical techniques were used. In the enzymatic reaction of glucose, H2O2 is one of the products which can be determined. Under optimum conditions, H2O2 can be detected in the concentration range of 0⁻1000 nmol·L-1, with a detection limit of 2.4 nmol·L-1. Using this CL assay, a linear relationship was obtained between the intensity of the CL emission and glucose concentration in the range of 0.01⁻30 nmol·L-1, with a limit of detection (3S) of 4.2 nmol·L-1.

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INTRODUCTION: The consolidation of different therapies into a single nanoplatform has shown great promise for synergistic tumor treatment. In this study, a multifunctional platform by WS2 quantum dots (WQDs)-coated doxorubicin (DOX)-loaded periodic mesoporous organosilicas (PMOs-DOX@WQDs) nanoparticles were fabricated for the first time, and which exhibits good potential for synergistic chemo-photothermal therapy. MATERIALS AND METHODS: The structure, light-mediated drug release behavior, photothermal effect, and synergistic therapeutic efficiency of PMOs-DOX@WQDs to HCT-116 colon cancer cells were investigated. The thioether-bridged PMOs exhibit a high DOX loading capacity of 66.7 µg mg-1. The gating of the PMOs not only improve the drug loading capacity but also introduce the dual-stimuli-responsive performance. Furthermore, the as-synthesized PMOs-DOX@WQDs nanoparticles can efficiently generate heat to the hyperthermia temperature with near infrared laser irradiation. RESULTS: It was confirmed that PMOs-DOX@WQDs exhibit remarkable photothermal effect and light-triggered faster release of DOX. More importantly, it was reasonable to attribute the efficient anti-tumor efficiency of PMOs-DOX@WQDs. CONCLUSION: The in vitro experimental results confirm that the fabricated nanocarrier exhibits a significant synergistic effect, resulting in a higher efficacy to kill cancer cells. Therefore, the WQD-coated PMOs present promising applications in cancer therapy.

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Modulating the dimensions and phases of transition metal dichalcogenides is of great interest to enhance their intrinsic properties or to create new physicochemical properties. Herein, we report an effective approach to synthesize 2H-WS2 quantum dots (QDs) via the dimension and phase engineering of 1T-WS2 nanosheets. The solvothermal reaction of chemically exfoliated 1T-WS2 nanosheets in N-methyl-2-pyrrolidone (NMP) under an N2 atmosphere induced their chopping and phase transition at lower temperature to produce 2H-WS2 QDs with a high quantum yield (5.5 ± 0.3%). Interestingly, this chopping and phase transition process showed strong dependency on solvent; WS2 QDs were not produced in other solvents such as 1,4-dioxane and dimethyl sulfoxide. Mechanistic investigations suggested that NMP radicals played a crucial role in the effective production of 2H-WS2 QDs from 1T-WS2 nanosheets. WS2 QDs were successfully applied for the selective, sensitive, and rapid detection of dopamine in human serum (4 min, as low as 23.8 nM). The intense fluorescence of WS2 QDs was selectively quenched upon the addition of dopamine and Au3+ ions due to fluorescence resonance energy transfer between WS2 QDs and the quickly formed Au nanoparticles. This new sensing principle enabled us to discriminate dopamine from dopamine-derivative neurotransmitters including epinephrine and norepinephrine, as well as other interference compounds.

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Two-dimensional WS2 materials have attracted wide attention in condensed physics and materials science due to its unique geometric and electronic structures. Particularly, WS2 shows extraordinary catalytic activities when its size decreases to ultrasmall, which provides potential opportunities for medical applications. In this work, WS2 quantum dots with strong catalytic properties were used for in vitro and in vivo protection from ionizing radiation induced cell damages. WS2 quantum dots possess unique optical properties of blue photoluminescence emission and excitation-wavelength dependent emission profiles. In vitro studies showed that cell viability can be considerably improved and cellular reactive oxygen species (ROS) can be removed by WS2 quantum dots. In vivo studies showed WS2 quantum dots can effectively protect the hematopoietic system and DNA from damages caused by high-energy radiation through removing whole-body excessive ROS. Furthermore, WS2 quantum dots showed nearly 80% renal clearance within 24 h post injection and did not cause any obvious toxicities in up to 30 days after treatment.

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Designing a multifunctional nanomedicine for integration of precise diagnosis and effective treatment of tumors is desirable but remains a great challenge. Here, we report a multifunctional nanomedicine based on WS2 quantum dots (QDs), which was prepared by a facile and "green" method through physical grinding and ultrasonication. The as-obtained WS2 QDs with small size (3 nm) possess not only significant X-ray computed tomography (CT)/photoaccoustic (PA) imaging signal enhancement but also remarkable photothermal therapy (PTT)/radiotherapy (RT) synergistic effect for tumor treatment. With CT/PA imaging and the synergistic effect between PTT and RT, the tumor could be accurately positioned and thoroughly eradicated in vivo after intravenous injection of WS2 QDs. Moreover, hematoxylin and eosin staining, blood hematology, and biochemistry analysis revealed no noticeable toxicity of WS2 QDs in vitro and in vivo, which confirmed that WS2 QDs possess good biocompatibility. This multifunctional nanoparticle could play an important role in facilitating simultaneously multimodal imaging and synergistic therapy between PTT and RT to achieve better therapeutic efficacy.

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