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1.
Nat Mater ; 23(4): 460-469, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38561520

RESUMO

Non-layered transition metal carbides (TMCs) and layered transition metal dichalcogenides (TMDs) are two well-studied material families that have individually received considerable attention over the past century. In recent years, with the shift towards two-dimensional materials and heterostructures, a field has emerged that is focused on the structure and properties of TMC/TMD heterostructures, which through chemical conversion exhibit diverse types of heterostructure configuration that host coupled 2D-3D interfaces, giving rise to exotic properties. In this Review, we highlight experimental and computational efforts to understand the routes to fabricate TMC/TMD heterostructures. Furthermore, we showcase how controlling these heterostructures can lead to emergent electronic transport, optical properties and improved catalytic properties.

2.
Proc Natl Acad Sci U S A ; 119(23): e2118836119, 2022 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-35653572

RESUMO

Rapid identification of newly emerging or circulating viruses is an important first step toward managing the public health response to potential outbreaks. A portable virus capture device, coupled with label-free Raman spectroscopy, holds the promise of fast detection by rapidly obtaining the Raman signature of a virus followed by a machine learning (ML) approach applied to recognize the virus based on its Raman spectrum, which is used as a fingerprint. We present such an ML approach for analyzing Raman spectra of human and avian viruses. A convolutional neural network (CNN) classifier specifically designed for spectral data achieves very high accuracy for a variety of virus type or subtype identification tasks. In particular, it achieves 99% accuracy for classifying influenza virus type A versus type B, 96% accuracy for classifying four subtypes of influenza A, 95% accuracy for differentiating enveloped and nonenveloped viruses, and 99% accuracy for differentiating avian coronavirus (infectious bronchitis virus [IBV]) from other avian viruses. Furthermore, interpretation of neural net responses in the trained CNN model using a full-gradient algorithm highlights Raman spectral ranges that are most important to virus identification. By correlating ML-selected salient Raman ranges with the signature ranges of known biomolecules and chemical functional groups­for example, amide, amino acid, and carboxylic acid­we verify that our ML model effectively recognizes the Raman signatures of proteins, lipids, and other vital functional groups present in different viruses and uses a weighted combination of these signatures to identify viruses.


Assuntos
Aprendizado de Máquina , Redes Neurais de Computação , Vírus , Surtos de Doenças , Pandemias , Sorogrupo , Vírus/classificação
3.
Small ; 20(24): e2308684, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38174613

RESUMO

Porous carbon has been widely focused to solve the problems of low coulombic efficiency (ICE) and low multiplication capacity of Sodium-ion batteries (SIBs) anodes. The superior energy storage properties of two-dimensional(2D) carbon nanosheets can be realized by modulating the structure, but be limited by the carbon sources, making it challenging to obtain 2D structures with large surface area. In this work, a new method for forming carbon materials with high N/S doping content based on combustion activation using the dual activation effect of K2SO4/KNO3 is proposed. The synthesized carbon material as an anode for SIBs has a high reversible capacity of 344.44 mAh g-1 at 0.05 A g-1. Even at the current density of 5 Ag-1, the capacity remained at 143.08 mAh g-1. And the ICE of sodium-ion in ether electrolytes is ≈2.5 times higher than that in ester electrolytes. The sodium storage mechanism of ether/ester-based electrolytes is further explored through ex-situ characterizations. The disparity in electrochemical performance can be ascribed to the discrepancy in kinetics, wherein ether-based electrolytes exhibit a higher rate of Na+ storage and shedding compared to ester-based electrolytes. This work suggests an effective way to develop doubly doped carbon anode materials for SIBs.

4.
Small ; 20(39): e2307410, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-38778499

RESUMO

The detection of monoamine neurotransmitters is of paramount importance as the neurotransmitters are the chemical messengers regulating the gut-brain axis (GBA). It requires real-time, ultrasensitive, and selective sensing of the neurotransmitters in the gastric/intestinal fluid. However, multi-components present in the gastric/intestinal fluid make sensing challenging to achieve in terms of ultra-high sensitivity and selectivity. Herein, an approach is introduced to utilize vanadium single atom catalytic (SAC) centers in van der Waals MoS2 (V-MoS2) to selectively detect real-time serotonin (5-HT) in artificial gastric/intestinal fluid. The synergetic effect of V-SACs and the surface S-bonds on the MoS2 surface, enables an extremely wide range of 5-HT detection (from 1 pM to 100 µM), with optimum selectivity and interference resistance. By combining density functional theory calculations and scanning transmission electron microscopy, it is concluded that the V-SACs embedded in the MoS2 network create active sites that greatly facilitate the charge exchange between the material and the 5-HT molecules. This result allows the 5-HT detection in GBA studies to be more reliable, and the material tunability provides a general platform to achieve real-time and multi-component detection of other monoamine neurotransmitters in GBA such as dopamine and norepinephrine.


Assuntos
Encéfalo , Dissulfetos , Molibdênio , Neurotransmissores , Serotonina , Vanádio , Neurotransmissores/metabolismo , Dissulfetos/química , Molibdênio/química , Encéfalo/metabolismo , Serotonina/metabolismo , Serotonina/química , Vanádio/química
5.
Small ; : e2405434, 2024 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-39377370

RESUMO

2D dilute magnetic semiconductors (DMS) based on transition metal dichalcogenides (TMD) offer an innovative pathway for advancing spintronic technologies, including the potential to exploit phenomena such as the valley Zeeman effect. However, the impact of magnetic ordering on the valley degeneracy breaking and on the enhancement of the optical transitions g-factors of these materials remains an open question. Here, a giant effective g-factors ranging between ≈-27 and -69 for the bound exciton at 4 K in vanadium-doped WSe2 monolayers, obtained through magneto-photoluminescence (PL) experiments is reported. This giant g-factor disappears at room temperature, suggesting that this response is associated with a magnetic ordering of the vanadium impurity states at low temperatures. Ab initio calculations for the vanadium-doped WSe2 monolayer confirm the existence of magnetic ordering of the vanadium states, which leads to degeneracy breaking of the valence bands at K and K'. A phenomenological analysis is employed to correlate this splitting with the measured enhanced effective g-factor. The findings shed light on the potential of defect engineering of 2D materials for spintronic applications.

6.
Inorg Chem ; 63(36): 16815-16823, 2024 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-39196768

RESUMO

NbTe4 is an important material because of its fundamental low-temperature electronic behavior and its potential interest for thermoelectric, catalytic, and phase-change applications, especially as nano- and microscale particles. As a tellurium-rich group V transition metal telluride, bulk NbTe4 is typically synthesized through high-temperature solid-state or metal flux reactions and NbTe4 films can be made by sputtering and annealing, but NbTe4 is generally not amenable to the lower-temperature solution-based syntheses that yield small particles. Here, we demonstrate a solvothermal route to NbTe4 particles that is based on mainstream colloidal nanoparticle synthesis. We find that the reaction proceeds in situ through a multistep pathway that begins by first forming elemental tellurium needles. NbTe4 then deposits on the surface of the tellurium needles through a diffusion-based process. Time-point studies throughout the reaction reveal that crystallographic relationships between Te and NbTe4 define how the diffusion-based reaction proceeds and help to rationalize the morphology of the resulting NbTe4 particles. As synthesized, NbTe4 particles exhibit a surface consisting of predominantly Nb-Te and reduced NbOx species, but after storage, surface oxidation transforms these species to primarily Nb2O5 and TeO2, while the NbTe4 remains unchanged. These synthetic capabilities and reaction pathway insights for NbTe4, made using a solvothermal method, will help to advance future studies on the properties and applications of this and related tellurides.

7.
Nano Lett ; 23(21): 9803-9810, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37879099

RESUMO

Two-dimensional exciton-polaritons in monolayer transition metal dichalcogenides (TMDs) exhibit practical advantages in valley coherence, optical nonlinearities, and even bosonic condensation owing to their light-emission capability. To achieve robust exciton-polariton emission, strong photon-exciton couplings are required at the TMD monolayer, which is challenging due to its atomic thickness. High-quality (Q) factor optical cavities with narrowband resonances are an effective approach but typically limited to a specific excitonic state of a certain TMD material. Herein, we achieve on-demand exciton-polariton emission from a wide range of TMDs at room temperature by hybridizing excitons with broadband Mie resonances spanning the whole visible spectrum. By confining broadband light at the TMD monolayer, our one type of Mie resonator on different TMDs enables enhanced light-matter interactions with multiple excitonic states simultaneously. We demonstrate multi-Rabi splittings and robust polaritonic photoluminescence in monolayer WSe2, WS2, and MoS2. The hybrid system also shows the potential to approach the ultrastrong coupling regime.

8.
Small ; 19(41): e2302289, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37310414

RESUMO

The field of photovoltaics is revolutionized in recent years by the development of two-dimensional (2D) type-II heterostructures. These heterostructures are made up of two different materials with different electronic properties, which allows for the capture of a broader spectrum of solar energy than traditional photovoltaic devices. In this study, the potential of vanadium (V)-doped WS2 is investigated, hereafter labeled V-WS2 , in combination with air-stable Bi2 O2 Se for use in high-performance photovoltaic devices. Various techniques are used to confirm the charge transfer of these heterostructures, including photoluminescence (PL) and Raman spectroscopy, along with Kelvin probe force microscopy (KPFM). The results show that the PL is quenched by 40%, 95%, and 97% for WS2 /Bi2 O2 Se, 0.4 at.% V-WS2 /Bi2 O2 Se, and 2 at.% V-WS2 /Bi2 O2 Se, respectively, indicating a superior charge transfer in V-WS2 /Bi2 O2 Se compared to pristine WS2 /Bi2 O2 Se. The exciton binding energies for WS2 /Bi2 O2 Se, 0.4 at.% V-WS2 /Bi2 O2 Se and 2 at.% V-WS2 /Bi2 O2 Se heterostructures are estimated to be ≈130, 100, and 80 meV, respectively, which is much lower than that for monolayer WS2 . These findings confirm that by incorporating V-doped WS2 , charge transfer in WS2 /Bi2 O2 Se heterostructures can be tuned, providing a novel light-harvesting technique for the development of the next generation of photovoltaic devices based on V-doped transition metal dichalcogenides (TMDCs)/Bi2 O2 Se.

9.
Small ; 19(6): e2205800, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36587989

RESUMO

The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS2 , it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS2 monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.

10.
Small ; 19(39): e2302583, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37236201

RESUMO

The slow solid diffusion dynamics of sodium ions and the side-reaction of sodium metal plating at low potential in the hard carbon anode of sodium ion batteries (SIBs) pose significant challenges to the safety manipulation of high-rate batteries. Herein, a simple yet powerful fabricating method is reported on for "egg puff"-like hard carbon with few N doping using rosin as a precursor via liquid salt template-assisted and potassium hydroxide dual activation. The as-synthesized hard carbon delivers promising electrochemical properties in the ether-based electrolyte especially at high rates, based on the absorption mechanism of fast charge transfer. The optimized hard carbon exhibits a high specific capacity of 367 mAh g-1 at 0.05 A g-1 and 92.9% initial coulombic efficiency (ICE), 183 mAh g-1 at 10 A g-1 , and ultra-long cycle stability of reversible discharge capacity of 151 mAh g-1 after 12,000 cycles at 5 A g-1 with the average coulombic efficiency of ≈99% and the decay of 0.0026% per cycle. These studies will undoubtedly provide an effective and practical strategy for advanced hard carbon anode of SIBs based on adsorption mechanism.

11.
Inorg Chem ; 62(11): 4550-4557, 2023 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-36882119

RESUMO

Ion exchange reactions of colloidal nanoparticles post-synthetically modify the composition while maintaining the morphology and crystal structure and therefore are important for tuning properties and producing otherwise inaccessible and/or metastable materials. Reactions involving anion exchange of metal chalcogenides are particularly interesting, as they involve the replacement of the sublattice that defines the structure while also requiring high temperatures that can be disruptive. Here, we show that the tellurium anion exchange of weissite Cu2-xSe nanoparticles using a trioctylphosphine-tellurium complex (TOP═Te) yields weissite Cu2-xSe1-yTey solid solutions, rather than complete exchange to weissite Cu2-xTe, with compositions that are tunable based on the amount of TOP═Te used. Upon storage at room temperature in either solvent or air, tellurium-rich Cu2-xSe1-yTey solid solution nanoparticles transform, over the span of several days, to a selenium-rich Cu2-xSe1-yTey composition. The tellurium that is expelled from the solid solution during this process migrates to the surface and forms a tellurium oxide shell, which correlates with the onset of particle agglomeration due to the change in surface chemistry. Collectively, this study demonstrates tunable composition during tellurium anion exchange of copper selenide nanoparticles along with unusual post-exchange reactivity that transforms the composition, surface chemistry, and colloidal dispersibility due to the apparent metastable nature of the solid solution product.

12.
Proc Natl Acad Sci U S A ; 117(2): 895-901, 2020 01 14.
Artigo em Inglês | MEDLINE | ID: mdl-31882450

RESUMO

Emerging and reemerging viruses are responsible for a number of recent epidemic outbreaks. A crucial step in predicting and controlling outbreaks is the timely and accurate characterization of emerging virus strains. We present a portable microfluidic platform containing carbon nanotube arrays with differential filtration porosity for the rapid enrichment and optical identification of viruses. Different emerging strains (or unknown viruses) can be enriched and identified in real time through a multivirus capture component in conjunction with surface-enhanced Raman spectroscopy. More importantly, after viral capture and detection on a chip, viruses remain viable and get purified in a microdevice that permits subsequent in-depth characterizations by various conventional methods. We validated this platform using different subtypes of avian influenza A viruses and human samples with respiratory infections. This technology successfully enriched rhinovirus, influenza virus, and parainfluenza viruses, and maintained the stoichiometric viral proportions when the samples contained more than one type of virus, thus emulating coinfection. Viral capture and detection took only a few minutes with a 70-fold enrichment enhancement; detection could be achieved with as little as 102 EID50/mL (50% egg infective dose per microliter), with a virus specificity of 90%. After enrichment using the device, we demonstrated by sequencing that the abundance of viral-specific reads significantly increased from 4.1 to 31.8% for parainfluenza and from 0.08 to 0.44% for influenza virus. This enrichment method coupled to Raman virus identification constitutes an innovative system that could be used to quickly track and monitor viral outbreaks in real time.


Assuntos
Técnicas Microbiológicas/métodos , Virologia/métodos , Viroses/diagnóstico , Vírus/isolamento & purificação , Humanos , Vírus da Influenza A/isolamento & purificação , Técnicas Microbiológicas/instrumentação , Microtecnologia/métodos , Nanotubos de Carbono , Infecções Respiratórias/diagnóstico , Infecções Respiratórias/virologia , Respirovirus/isolamento & purificação , Rhinovirus/isolamento & purificação , Sensibilidade e Especificidade , Dióxido de Silício , Análise Espectral Raman/métodos , Coloração e Rotulagem , Vírion , Virologia/instrumentação , Viroses/virologia , Vírus/genética
13.
Proc Natl Acad Sci U S A ; 117(33): 19685-19693, 2020 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-32727904

RESUMO

Stacking layers of atomically thin transition-metal carbides and two-dimensional (2D) semiconducting transition-metal dichalcogenides, could lead to nontrivial superconductivity and other unprecedented phenomena yet to be studied. In this work, superconducting α-phase thin molybdenum carbide flakes were first synthesized, and a subsequent sulfurization treatment induced the formation of vertical heterolayer systems consisting of different phases of molybdenum carbide-ranging from α to γ' and γ phases-in conjunction with molybdenum sulfide layers. These transition-metal carbide/disulfide heterostructures exhibited critical superconducting temperatures as high as 6 K, higher than that of the starting single-phased α-Mo2C (4 K). We analyzed possible interface configurations to explain the observed moiré patterns resulting from the vertical heterostacks. Our density-functional theory (DFT) calculations indicate that epitaxial strain and moiré patterns lead to a higher interfacial density of states, which favors superconductivity. Such engineered heterostructures might allow the coupling of superconductivity to the topologically nontrivial surface states featured by transition-metal carbide phases composing these heterostructures potentially leading to unconventional superconductivity. Moreover, we envisage that our approach could also be generalized to other metal carbide and nitride systems that could exhibit high-temperature superconductivity.

14.
Acc Chem Res ; 54(6): 1517-1527, 2021 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-33662209

RESUMO

ConspectusLayered transition-metal dichalcogenides (TMDs) are intriguing two-dimensional (2D) compounds where metal and chalcogen atoms are covalently bonded in each monolayer, and the monolayers are held together by weak van der Waals forces. Distinct from graphene, which is chemically inert, layered TMDs exhibit a wide range of electronic, optical, catalytic, and magnetic properties dependent upon their compositions, crystal structures, and thicknesses, which make them fundamentally and technologically important. TMD nanostructures are traditionally synthesized using gas-phase chemical deposition methods, which are typically limited to small-scale samples of substrate-bound planar materials. Colloidal synthesis has emerged as an alternative synthesis approach to enable the scalable synthesis of free-standing TMDs. The judicious selection of precursors, solvents, and capping ligands together with the optimization of synthesis parameters such as concentrations and temperatures leads to the fabrication of colloidal TMD nanostructures exhibiting tunable properties. In addition, understanding the formation and transformation of TMD nanostructures in solution contributes to the discovery of important structure-function relationships, which may be extendable to other anisotropic systems.In this Account, we summarize recent progress in the colloidal synthesis, characterization, and applications of TMD nanostructures with tunable compositions, structures, and thicknesses. On the basis of the preparation of Mo- and W-based disulfide, diselenide, and ditelluride nanostructures, we discuss examples of phase engineering where various metastable TMD compounds can be directly accessed at low temperatures in solution. We also analyze the chemistry involved in broadly tuning the composition across the MoSe2-WSe2, WS2-WSe2, and MoTe2-WTe2 solid solutions as well as atomic-level microscopic characterization and the resulting composition-tunable properties. We then highlight how the high densities of defects in the colloidally synthesized TMD nanostructures enable unique catalytic properties, including their ability to facilitate the selective hydrogenation of substituted nitroarenes using molecular hydrogen. Finally, using this library of colloidal TMD nanostructures as substrates, we discuss the pathways by which noble metals deposit onto them in solution. We highlight the importance of the relative strengths of the interfacial metal-chalcogen bonds in determining the sizes and morphologies of the deposited noble metal components. These synthesis capabilities for colloidal TMD nanostructures, which have been generalized to a library of composition-tunable phases, enable new systematic studies of structure-property relationships and chemical reactivity in this important class of 2D materials.

15.
Small ; 17(1): e2004827, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33283441

RESUMO

Light-weight and flexible supercapacitors with outstanding electrochemical performances are strongly desired in portable and wearable electronics. Here, ultralight nitrogen-doped carbon macrotube (N-CMT) sponges with 3D interconnected macroporous structures are fabricated and used as substrate to grow nickel ferrite (NiFe2 O4 ) nanoparticles by vapor diffusion-precipitation and in situ growth. This process effectively suppresses the agglomeration of NiFe2 O4 , enabling good interfacial contact between N-CMT sponges and NiFe2 O4 . More remarkably, the as-synthesized NiFe2 O4 /N-CMT composite sponges can be directly used as electrodes without additional processing that could cause agglomeration and reduction of active sites. Benefiting from the tubular structure and the synergetic effect of NiFe2 O4 and N-CMT, the NiFe2 O4 /N-CMT-2 exhibits a high specific capacitance of 715.4 F g-1 at a current density of 1 A g-1 , and 508.3 F g-1 at 10 A g-1 , with 90.9% of capacitance retention after 50 000 cycles at 1 A g-1 in an alkaline electrolyte. Furthermore, flexible supercapacitors are fabricated, yielding areal specific capacitances of 1397.4 and 1041.2 mF cm-2 at 0.5 and 8 mA cm-2 , respectively. They also exhibit exceptional cycling performance with capacitance retention of 92.9% at 1 mA cm-2 after 10 000 cycles under bending. This work paves a new way to develop flexible, light-weight, and high-performance energy storage devices.

16.
Nano Lett ; 20(5): 3113-3121, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-32134680

RESUMO

Numerous theoretically proposed devices and novel phenomena have sought to take advantage of the intense pseudogauge fields that can arise in strained graphene. Many of these proposals, however, require fields to oscillate with a spatial frequency smaller than the magnetic length, while to date only the generation and effects of fields varying at a much larger length scale have been reported. Here, we describe the creation of short wavelength, periodic pseudogauge-fields using rippled graphene under extreme (>10%) strain and study of its effects on Dirac electrons. Combining scanning tunneling microscopy and atomistic calculations, we find that spatially oscillating strain generates a new quantization different from the familiar Landau quantization. Graphene ripples also cause large variations in carbon-carbon bond length, creating an effective electronic superlattice within a single graphene sheet. Our results thus also establish a novel approach of synthesizing effective 2D lateral heterostructures by periodically modulating lattice strain.

17.
Nano Lett ; 20(1): 284-291, 2020 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-31794217

RESUMO

One-dimensional defects in two-dimensional (2D) materials can be particularly damaging because they directly impede the transport of charge, spin, or heat and can introduce a metallic character into otherwise semiconducting systems. Current characterization techniques suffer from low throughput and a destructive nature or limitations in their unambiguous sensitivity at the nanoscale. Here we demonstrate that dark-field second harmonic generation (SHG) microscopy can rapidly, efficiently, and nondestructively probe grain boundaries and edges in monolayer dichalcogenides (i.e., MoSe2, MoS2, and WS2). Dark-field SHG efficiently separates the spatial components of the emitted light and exploits interference effects from crystal domains of different orientations to localize grain boundaries and edges as very bright 1D patterns through a Cerenkov-type SHG emission. The frequency dependence of this emission in MoSe2 monolayers is explained in terms of plasmon-enhanced SHG related to the defect's metallic character. This new technique for nanometer-scale imaging of the grain structure, domain orientation and localized 1D plasmons in 2D different semiconductors, thus enables more rapid progress toward both applications and fundamental materials discoveries.

18.
Nanotechnology ; 32(9)2020 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-33232946

RESUMO

Doping of two-dimensional (2D) semiconductors has been intensively studied toward modulating their electrical, optical, and magnetic properties. While ferromagnetic 2D semiconductors hold promise for future spintronics and valleytronics, the origin of ferromagnetism in 2D materials remains unclear. Here, we show that substitutional Fe-doping of MoS2and WS2monolayers induce different magnetic properties. The Fe-doped monolayers are directly synthesized via chemical vapor deposition. In both cases, Fe substitutional doping is successfully achieved, as confirmed using scanning transmission electron microscopy. While both Fe:MoS2and Fe:WS2show PL quenching and n-type doping, Fe dopants in WS2monolayers are found to assume deep-level trap states, in contrast to the case of Fe:MoS2, where the states are found to be shallow. Usingµm- and mm-precision local NV-magnetometry and superconducting quantum interference device, we discover that, unlike MoS2monolayers, WS2monolayers do not show a magnetic phase transition to ferromagnetism upon Fe-doping. The absence of ferromagnetism in Fe:WS2is corroborated using density functional theory calculations.

19.
Inhal Toxicol ; 32(1): 24-38, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-32028803

RESUMO

Objective: In this study, we compared in vitro and in vivo bioactivity of nitrogen-doped multi-walled carbon nanotubes (NDMWCNT) to MWCNT to test the hypothesis that nitrogen doping would alter bioactivity.Materials and Methods: High-resolution transmission electron microscopy (TEM) confirmed the multilayer structure of MWCNT with an average layer distance of 0.36 nm, which was not altered by nitrogen doping: the nanomaterials had similar widths and lengths. In vitro studies with THP-1 cells and alveolar macrophages from C57BL/6 mice demonstrated that NDMWCNT were less cytotoxic and stimulated less IL-1ß release compared to MWCNT. For in vivo studies, male C57BL/6J mice received a single dose of dispersion medium (DM), 2.5, 10 or 40 µg/mouse of NDMWCNT, or 40 µg/mouse of MWCNT by oropharyngeal aspiration. Animals were euthanized between 1 and 7 days post-exposure for whole lung lavage (WLL) studies.Results and Discussion: NDMWCNT caused time- and dose-dependent pulmonary inflammation. However, it was less than that caused by MWCNT. Activation of the NLRP3 inflammasome was assessed in particle-exposed mice by determining cytokine production in WLL fluid at 1 day post-exposure. Compared to DM-exposed mice, IL-1ß and IL-18 were significantly increased in MWCNT- and NDMWCNT-exposed mice, but the increase caused by NDMWCNT was less than MWCNT. At 56 days post-exposure, histopathology determined lung fibrosis in MWCNT-exposed mice was greater than NDMWCNT-exposed mice.Conclusions: These data indicate nitrogen doping of MWCNT decreases their bioactivity, as reflected with lower in vitro and in vivo toxicity inflammation and lung disease. The lower activation of the NLRP3 inflammasome may be responsible. Abbreviations: NDMWCNT: nitrogen-doped multi-walled carbon nanotubes; MWCNT: multi-walled carbon nanotubes; TEM: transmission electron microscopy; HRTEM: high resolution transmission electron microscopy; IL-1ß: interleukin-1ß; DM: dispersion medium; WLL: whole lung lavage; IL-18: interleukin-18; GSD: geometric standard deviation; XPS: X-ray photoelectron spectroscopy; SEM: standard error of the mean; PMA: phorbol 12-myristate 13-acetate; LPS: lipopolysacharride; LDH: lactate dehydrogenase; AM: alveolar macrophage; PMN: polymorphonuclear leukocyte.


Assuntos
Exposição por Inalação/efeitos adversos , Pulmão/efeitos dos fármacos , Macrófagos Alveolares/efeitos dos fármacos , Nanotubos de Carbono/toxicidade , Nitrogênio/toxicidade , Pneumonia/induzido quimicamente , Animais , Líquido da Lavagem Broncoalveolar/química , Citocinas/análise , Relação Dose-Resposta a Droga , Humanos , Inflamassomos/imunologia , Inflamassomos/metabolismo , Pulmão/imunologia , Pulmão/patologia , Macrófagos Alveolares/imunologia , Macrófagos Alveolares/patologia , Masculino , Camundongos Endogâmicos C57BL , Nanotubos de Carbono/química , Nitrogênio/química , Tamanho da Partícula , Pneumonia/imunologia , Pneumonia/patologia , Propriedades de Superfície , Células THP-1 , Fatores de Tempo
20.
Small ; 15(31): e1900982, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31183956

RESUMO

Strong spatial confinement and highly reduced dielectric screening provide monolayer transition metal dichalcogenides with strong many-body effects, thereby possessing optically forbidden excitonic states (i.e., dark excitons) at room temperature. Herein, the interaction of surface plasmons with dark excitons in hybrid systems consisting of stacked gold nanotriangles and monolayer WS2 is explored. A narrow Fano resonance is observed when the hybrid system is surrounded by water, and the narrowing of the spectral Fano linewidth is attributed to the plasmon-enhanced decay of dark K-K excitons. These results reveal that dark excitons in monolayer WS2 can strongly modify Fano resonances in hybrid plasmon-exciton systems and can be harnessed for novel optical sensors and active nanophotonic devices.

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