Research on Detection of Ultra-Low Concentration Anthrax Protective Antigen Using Graphene Field-Effect Transistor Biosensor.

BACKGROUND: Protective antigen (PA) is an important biomarker for the early diagnosis of anthrax, and the accurate detection of protective antigen under extremely low concentration conditions has always been a hot topic in the biomedical field. To complete the diagnosis of anthrax in a timely manner, it is necessary to detect PA at extremely low concentrations, as the amount of PA produced in the early stage of anthrax invasion is relatively small. Graphene field-effect transistor (Gr-FET) biosensors are a new type of material for preparing biosensors, with the advantages of a short detection time and ultra-low detection limit. METHODS: The effect of different concentrations of diluents on the affinity of PA monoclonal antibodies was determined via an ELISA experiment. Combined with the Debye equation, 0.01 × PBS solution was finally selected as the diluent for the experiment. Then, a PA monoclonal antibody was selected as the bio-recognition element to construct a Gr-FET device based on CVD-grown graphene, which was used to detect the concentration of PA while recording the response time, linear range, detection limit, and other parameters. RESULTS: The experimental results showed that the biosensor could quickly detect PA, with a linear range of 10 fg/mL to 100 pg/mL and a detection limit of 10 fg/mL. In addition, the biosensor showed excellent specificity and repeatability. CONCLUSIONS: By constructing a Gr-FET device based on CVD-grown graphene and selecting a PA monoclonal antibody as the bio-recognition element, a highly sensitive, specific, and repeatable Gr-FET biosensor was successfully prepared for detecting extremely low concentrations of anthrax protective antigen (PA). This biosensor is expected to have a wide range of applications in clinical medicine and biological safety monitoring.

Thickness-Tunable Growth of Composition-Controllable Two-Dimensional FexGeTe2.

Two-dimensional (2D) magnetic materials provide an ideal platform for investigating novel magnetism and spin behavior in low-dimensional systems while being restricted by the deficiency of accurate bottom-up synthesis. To overcome this difficulty, a facile and universal flux-assisted growth (FAG) method is proposed to synthesize the multicomponent FexGeTe2 (x = 3-5) with different Fe contents and even alloyed with hetero metal atoms. This one-to-one method ensures the stoichiometry consistency from the FexGeTe2 and MyFe5-yGeTe2 (M = Co, Ni) bulk crystal precursors to the 2D nanosheets, with controllable composition. Tuning the growth temperatures can provide thickness-tunable products. Changeable magnetic properties of FexGeTe2 and alloyed CoyFe5-yGeTe2 are substantiated by the superconducting quantum interference device and reflective magnetic circular dichroism. This method generates thickness-tunable high-crystallinity FexGeTe2 samples without phase separation and exhibits a high tolerance to different substrates and a large temperature window, providing a new avenue to synthesize and explore such multicomponent 2D magnets and even the alloyed ones.

Single atom catalysts in Van der Waals gaps.

Single-atom catalysts provide efficiently utilized active sites to improve catalytic activities while improving the stability and enhancing the activities to the level of their bulk metallic counterparts are grand challenges. Herein, we demonstrate a family of single-atom catalysts with different interaction types by confining metal single atoms into the van der Waals gap of two-dimensional SnS2. The relatively weak bonding between the noble metal single atoms and the host endows the single atoms with more intrinsic catalytic activity compared to the ones with strong chemical bonding, while the protection offered by the layered material leads to ultrahigh stability compared to the physically adsorbed single-atom catalysts on the surface. Specifically, the trace Pt-intercalated SnS2 catalyst has superior long-term durability and comparable performance to that of commercial 10 wt% Pt/C catalyst in hydrogen evolution reaction. This work opens an avenue to explore high-performance intercalated single-atom electrocatalysts within various two-dimensional materials.

Homogeneously niobium-doped MoS2 for rapid and high-sensitive detection of typical chemical warfare agents.

Rapid detection of Chemical Warfare Agents (CWAs) is of great significance in protecting civilians in public places and military personnel on the battlefield. Two-dimensional (2D) molybdenum disulfide (MoS2) nanosheets (NSs) can be integrated as a gas sensor at room temperature (25°C) due to their large specific surface area and excellent semiconductor properties. However, low sensitivity and long response-recovery time hinder the pure MoS2 application in CWAs gas sensors. In this work, we developed a CWAs sensor based on in-situ niobium-doped MoS2 NSs (Nb-MoS2 NSs) via direct chemical-vapor-deposition (CVD) growth. Characterization results show that the high content of Nb elements (7.8 at%) are homogeneously dispersed on the large-area 2D structure of MoS2. The Nb-MoS2 NSs-based CWAs sensor exhibits higher sensitivity (-2.09% and -3.95% to 0.05 mg/m3 sarin and sulfur mustard, respectively) and faster response speed (78 s and 30 s to 0.05 mg/m3 sarin and sulfur mustard, respectively) than MoS2 and other 2D materials at room temperature. And the sensor has certain specificity for sarin and sulfur mustard and is especially sensitive to sulfur mustard. This can be attributed to the improvement of adsorption properties via electronic regulation of Nb doping. This is the first report about CWAs detection based on two-dimensional (2D) transition metal dichalcogenides (TMDs) sensing materials, which demonstrates that the high sensitivity, rapid response, and low limit of detection of 2D TMDs-based CWAs sensor can meet the monitoring needs of many scenarios, thus showing a strong application potential.

Anomalous thickness dependence of Curie temperature in air-stable two-dimensional ferromagnetic 1T-CrTe2 grown by chemical vapor deposition.

The discovery of ferromagnetic two-dimensional van der Waals materials has opened up opportunities to explore intriguing physics and to develop innovative spintronic devices. However, controllable synthesis of these 2D ferromagnets and enhancing their stability under ambient conditions remain challenging. Here, we report chemical vapor deposition growth of air-stable 2D metallic 1T-CrTe2 ultrathin crystals with controlled thickness. Their long-range ferromagnetic ordering is confirmed by a robust anomalous Hall effect, which has seldom been observed in other layered 2D materials grown by chemical vapor deposition. With reducing the thickness of 1T-CrTe2 from tens of nanometers to several nanometers, the easy axis changes from in-plane to out-of-plane. Monotonic increase of Curie temperature with the thickness decreasing from ~130.0 to ~7.6 nm is observed. Theoretical calculations indicate that the weakening of the Coulomb screening in the two-dimensional limit plays a crucial role in the change of magnetic properties.

3D Artificial Solid-Electrolyte Interphase for Lithium Metal Anodes Enabled by Insulator-Metal-Insulator Layered Heterostructures.

Despite considerable efforts to prevent lithium (Li) dendrite growth, stable cycling of Li metal anodes with various structures remains extremely difficult due to the direct contact of the liquid electrolyte with Li. Rational design of solid-electrolyte interphase (SEI) for 3D electrodes is a promising but still challenging strategy for preventing Li dendrite growth and avoiding lithium-electrolyte side reactions in Li-metal batteries. Here, a 3D architecture is constructed with g-C3 N4 /graphene/g-C3 N4 insulator-metal-insulator sandwiched nanosheets to guide uniform Li plating/stripping in the van der Waals gap between the graphene and the g-C3 N4 , and the function of which can be regarded as a 3D artificial SEI. Li deposition on the surface of g-C3 N4 is suppressed due to its insulating nature. However, its uniform lithiophilic sites and nanopore channels enable homogeneous lithium plating between the graphene and the g-C3 N4 , prohibiting the direct contact of the electrolyte with the Li metal. The use of the g-C3 N4 -layer-modified 3D anode enables long-term Li deposition with a high Coulombic efficiency and stable cycling of full cells under high cathode loading, limited Li excess, and lean electrolyte conditions. The concept of a 3D artificial SEI will shed light on developing safe and stable Li-metal anodes.

Conversion of Intercalated MoO3 to Multi-Heteroatoms-Doped MoS2 with High Hydrogen Evolution Activity.

Lack of effective strategies to regulate the internal activity of MoS2 limits its practical application for hydrogen evolution reactions (HERs). Doping of heteroatoms without forming aggregation or an edge enrichment is still challenging, and its effect on the HER needs to be further explored. Herein, a two-step method is developed to obtain multi-metal-doped H-MoS2 , which includes intercalation of the layered MoO3 precursor with a following sulfurization. Benefiting from the capability of the intercalation method to uniformly and simultaneously introduce different elements into the van der Waals gap, this method is universal to obtain multi-heteroatoms co-doped MoS2 without forming clusters, phase separation, and an edge enrichment. It is demonstrated that the doping of adjacent cobalt and palladium monomers on MoS2 greatly enhances the HER catalytic activity. The overpotential at 10 mA cm-2 and Tafel slope of Co and Pd co-doped MoS2 is found to be 49.3 mV and 43.2 mV dec-1 , respectively, representing a superior acidic HER catalytic activity. This intercalation-assisted method also provides a new and general strategy to synthesize uniformly doped transition metal dichalcogenides for various applications.

In-Situ Formed Protecting Layer from Organic/Inorganic Concrete for Dendrite-Free Lithium Metal Anodes.

In this work, a separator modified by composite material of graphite fluoride nanosheets and poly(vinylidene difluoride) (GFNs-PVDF) is fabricated to in-situ construct a protective layer on Li metal anodes. The much-improved mechanical properties of this organic/inorganic protecting layer ensure efficient restriction on the growth of Li dendrites. The LiF and graphene nanosheets generated by the reaction of GFNs with lithium metal can not only provide fast transport channels for Li ions but also protect the Li metal anode from continuous corrosion of electrolytes. In addition, GFNs' lithiophilic nature guarantees the uniform Li nucleation site and perfect contact between li metal and the protecting layer without void space, leading to a low interfacial impedance and layer-by-layer lithium deposition. Together with the scalable method and cheap raw materials, this strategy provides new insights toward practical applications of Li metal batteries.

Transition-Metal Substitution-Induced Lattice Strain and Electrical Polarity Reversal in Monolayer WS2.

The physical and chemical properties of transition metal dichalcogenides can be effectively tuned by doping or alloying, which is essential for their practical applications. However, the microstructure evolutions and their effects on the physical properties induced by alloying from hetero-atoms with different outermost electronic structures are still unclear. Here, we synthesized Nb-substituted WS2 with various Nb concentrations showing unusual changes of optical behaviors and continuous electrical polarity reversal. The fully softened Raman mode, rapidly quenched photoluminescence, and severe electron scattering can be attributed to the combined effects of charge doping and lattice strain caused by atomic Nb doping. Three types of substitution modes of Nb atoms in the WS2 lattice were observed directly from atomic-resolution scanning transmission electron microscopy. Density functional theory calculations further confirm the role of lattice strain in the evolutions of optical and electrical characteristics. With increasing Nb concentration, n-type, ambipolar, and p-type field-effect transistors can be achieved, indicating the capacity of this doping method to engineer the properties of two-dimensional materials for future electronic applications.

Large-Scale Growth and Field-Effect Transistors Electrical Engineering of Atomic-Layer SnS2.

2D layers of metal dichalcogenides are of considerable interest for high-performance electronic devices for their unique electronic properties and atomically thin geometry. 2D SnS2 nanosheets with a bandgap of ≈2.6 eV have been attracting intensive attention as one potential candidate for modern electrocatalysis, electronic, and/or optoelectronic fields. However, the controllable growth of large-size and high-quality SnS2 atomic layers still remains a challenge. Herein, a salt-assisted chemical vapor deposition method is provided to synthesize atomic-layer SnS2 with a large crystal size up to 410 µm and good uniformity. Particularly, the as-fabricated SnS2 nanosheet-based field-effect transistors (FETs) show high mobility (2.58 cm2 V-1 s-1 ) and high on/off ratio (≈108 ), which is superior to other reported SnS2 -based FETs. Additionally, the effects of temperature on the electrical properties are systematically investigated. It is shown that the scattering mechanism transforms from charged impurities scattering to electron-phonon scattering with the temperature. Moreover, SnS2 can serve as an ideal material for energy storage and catalyst support. The high performance together with controllable growth of SnS2 endow it with great potential for future applications in electrocatalysis, electronics, and optoelectronics.