Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of ...graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS
monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.
The emergence of two-dimensional electronic materials has stimulated proposals of novel electronic and photonic devices based on the heterostructures of transition metal dichalcogenides. Here we ...report the determination of band offsets in the heterostructures of transition metal dichalcogenides by using microbeam X-ray photoelectron spectroscopy and scanning tunnelling microscopy/spectroscopy. We determine a type-II alignment between MoS2 and WSe2 with a valence band offset value of 0.83 eV and a conduction band offset of 0.76 eV. First-principles calculations show that in this heterostructure with dissimilar chalcogen atoms, the electronic structures of WSe2 and MoS2 are well retained in their respective layers due to a weak interlayer coupling. Moreover, a valence band offset of 0.94 eV is obtained from density functional theory, consistent with the experimental determination.
Due to its high carrier mobility, broadband absorption, and fast response time, the semi-metallic graphene is attractive for optoelectronics. Another two-dimensional semiconducting material ...molybdenum disulfide (MoS2) is also known as light- sensitive. Here we show that a large-area and continuous MoS2 monolayer is achievable using a CVD method and graphene is transferable onto MoS2. We demonstrate that a photodetector based on the graphene/MoS2 heterostructure is able to provide a high photogain greater than 10(8). Our experiments show that the electron-hole pairs are produced in the MoS2 layer after light absorption and subsequently separated across the layers. Contradictory to the expectation based on the conventional built-in electric field model for metal-semiconductor contacts, photoelectrons are injected into the graphene layer rather than trapped in MoS2 due to the presence of a perpendicular effective electric field caused by the combination of the built-in electric field, the applied electrostatic field, and charged impurities or adsorbates, resulting in a tuneable photoresponsivity.
Neoadjuvant concurrent chemoradiotherapy (CCRT), followed by radical proctectomy, is the standard treatment for locally advanced rectal cancer. However, a poor response and therapeutic resistance ...continue to occur despite this treatment. In this study, we analyzed the microarray datasets (GSE68204) of rectal cancer from the Gene Expression Omnibus database, and identified CHD4 as one of the most significantly up-regulated genes among all subunits of the nucleosome remodeling and histone deacetylation (NuRD) complex, in non-responders to CCRT, among locally advanced rectal cancer (LARC) patients. We confirmed the predictive and prognostic significance of CHD4 expression in CCRT treatment, and its correlation with other clinicopathological features, such as tumor regression grade (TRG), therapeutic response, and patient survival. This was carried out by immunohistochemical studies on endoscopic biopsy tissues from 172 rectal cancer patients, receiving neoadjuvant concurrent chemoradiotherapy (CCRT). A high expression of CHD4 was significantly associated with pre-treatment tumor status (
< 0.001) and lymph node metastasis (
< 0.001), post-treatment tumor status (
< 0.001), and lymph node metastasis (
< 0.001), vascular invasion (
= 0.042), and tumor regression grade (
= 0.001). A high expression of CHD4 could also predict poor disease-specific survival and metastasis-free survival (log-rank test,
= 0.0373 and
< 0.0001, respectively). In multivariate Cox proportional-hazards regression analysis, CHD4 overexpression was an independent factor of poor prognosis for metastasis-free survival (HR, 4.575; 95% CI, 1.717-12.192;
= 0.002). By in vitro studies, based on cell line models, we also demonstrated that, the overexpression of CHD4 induced radio-resistance in microsatellite instability-high (MSI-H) colorectal cells (CRCs). On the contrary, the knockdown of CHD4 enhanced radiosensitivity in microsatellite stable (MSS) CRCs. Altogether, we have identified CHD4 as an important regulator of radio-resistance in both MSI-H and MSS CRC cell lines.
Contact engineering has been the central issue in the context of high-performance field-effect transistors (FETs) made of atomic thin transition metal dichalcogenides (TMDs). Conventional metal ...contacts on TMDs have been made on top via a lithography process, forming a top-bonded contact scheme with an appreciable contact barrier. To provide a more efficient pathway for charge injection, an end-bonded contact scheme has been proposed, in which covalent bonds are formed between the contact metal and channel edges. Yet, little efforts have been made to realize this contact configuration. Here, we bridge this gap and demonstrate seeded growth of end-bonded contact with different TMDs by means of chemical vapor deposition (CVD). Monolayer WSe2 FETs with a CVD-grown channel and end contacts exhibit improved performance metrics, including an on-current density of 30 μA/μm, a hole mobility of 90 cm2/V·s, and a subthreshold swing of 94 mV/dec, an order of magnitude superior than those of top-contact FET counterparts that share the same channel material. A fundamental NOT logic gate constructed using top-gated and end-bonded WSe2 and MoS2 FETs is also demonstrated. Calculations using density functional theory indicate that the superior device performance stems mainly from the stronger metal–TMD hybridization and substantial gap states in the end-contact configuration.
We recently reported that the chondrocyte-specific knockout of discoidin domain receptors 1 (Ddr1) delayed endochondral ossification (EO) in the growth plate by reducing the chondrocyte hypertrophic ...terminal differentiation, and apoptosis. The biologic and phenotypic changes in chondrocytes in the articular cartilage with osteoarthritis (OA) are similar to the phenomena observed in the process of EO. Additionally, autophagy can promote chondrocyte survival and prevent articular cartilage from degradation in OA. On this basis, we explored the effect of Ddr1 inhibition on OA prevention and further investigated the roles of autophagy in treating OA with a Ddr1 inhibitor (7 rh). The anterior cruciate ligament transection (ACLT)-OA model was used to investigate the role of 7 rh in vivo. Forty 8-week-old mice were randomly assigned to four groups, including the sham group, ACLT group, and two treated groups (ACLT with 7 rh 6.9 nM or 13.8 nM). According to the study design, normal saline or 7 rh were intra-articular (IA) injected into studied knees 3 times per week for 2 weeks and then once per week for 4 weeks. The results showed that 7 rh treatment significantly improved the functional performances (the weight-bearing ability and the running endurance), decreased cartilage degradation, and also reduced the terminal differentiation markers (collagen type X, Indian hedgehog, and matrix metalloproteinase 13). Moreover, 7 rh decreased chondrocyte apoptosis by regulating chondrocyte autophagy through reducing the expression of the mammalian target of rapamycin and enhancing the light chain 3 and beclin-1 expression. These results demonstrated that the IA injection of 7 rh could reduce the chondrocyte apoptosis and promote chondrocyte autophagy, leading to the attenuation of cartilage degradation. Our observations suggested that the IA injection of 7 rh could represent a potential disease-modifying therapy to prevention OA progression.
Band structure by design in 2D layered semiconductors is highly desirable, with the goal to acquire the electronic properties of interest through the engineering of chemical composition, structure, ...defect, stacking, or doping. For atomically thin transition metal dichalcogenides, substitutional doping with more than one single type of transition metals is the task for which no feasible approach is proposed. Here, the growth of WS2 monolayer is shown codoped with multiple kinds of transition metal impurities via chemical vapor deposition controlled in a diffusion‐limited mode. Multielement embedment of Cr, Fe, Nb, and Mo into the host lattice is exemplified. Abundant impurity states thus generate in the bandgap of the resultant WS2 and provide a robust switch of charging/discharging states upon sweep of an electric filed. A profound memory window exists in the transfer curves of doped WS2 field‐effect transistors, forming the basis of binary states for robust nonvolatile memory. The doping technique presented in this work brings one step closer to the rational design of 2D semiconductors with desired electronic properties.
Multielement codoped monolayer WS2 is synthesized using chemical vapor deposition. No dopant clustering and phase segregation occur and WS2 retains n‐type semiconducting properties. Substantial and stable impurities states are introduced near the conduction band minimum. Through the charging/discharging of the impurity states, the doped WS2 functions as a nonvolatile memory with long charge‐retention time.
Semiconductor heterostructures have played a critical role as the enabler for new science and technology. The emergence of transition‐metal dichalcogenides (TMDs) as atomically thin semiconductors ...has opened new frontiers in semiconductor heterostructures either by stacking different TMDs to form vertical heterojunctions or by stitching them laterally to form lateral heterojunctions via direct growth. In conventional semiconductor heterostructures, the design of multijunctions is critical to achieve carrier confinement. Analogously, successful synthesis of a monolayer WS2/WS2(1−x)Se2x/WS2 multijunction lateral heterostructure via direct growth by chemical vapor deposition is reported. The grown structures are characterized by Raman, photoluminescence, and annular dark‐field scanning transmission electron microscopy to determine their lateral compositional profile. More importantly, using microwave impedance microscopy, it is demonstrated that the local photoconductivity in the alloy region can be tailored and enhanced by two orders of magnitude over pure WS2. Finite element analysis confirms that this effect is due to the carrier diffusion and confinement into the alloy region. This work exemplifies the technological potential of atomically thin lateral heterostructures in optoelectronic applications.
The successful synthesis of a monolayer lateral heterostructure with multijunctions WS2/WS2(1−x)Se2x/WS2 (x ≈ 0.15) by chemical vapor deposition is reported. The grown structures are characterized by Raman and photoluminescence. Using light‐assisted microwave impedance microscopy, the multijunctions demonstrate that the local photoconductivity in the alloy region can be tailored and enhanced by two orders of magnitude over pure WS2.
Chondrocytes in growth plates are responsible for longitudinal growth in long bones during endochondral ossification. Discoidin domain receptor 1 (Ddr1) is expressed in chondrocytes, but the ...molecular mechanisms by which DDR1 regulates chondrocyte behaviors during the endochondral ossification process remain undefined. To elucidate Ddr1‐mediate chondrocyte functions, we generated chondrocyte‐specific Ddr1 knockout (CKOΔDdr1) mice in this study. The CKOΔDdr1 mice showed delayed development of the secondary ossification center and increased growth plate length in the hind limbs. In the tibial growth plate in CKOΔDdr1 mice, chondrocyte proliferation was reduced in the proliferation zone, and remarkable downregulation of Ihh, MMP13, and Col‐X expression in chondrocytes resulted in decreased terminal differentiation in the hypertrophic zone. Furthermore, apoptotic chondrocytes were reduced in the growth plates of CKOΔDdr1 mice. We concluded that chondrocytes with Ddr1 knockout exhibit decreased proliferation, terminal differentiation, and apoptosis in growth plates, which delays endochondral ossification and results in short stature. We also demonstrated that Ddr1 regulates the Ihh/Gli1/Gli2/Col‐X pathway to regulate chondrocyte terminal differentiation. These results indicate that Ddr1 is required for chondrocytes to regulate endochondral ossification in skeletal development.
Leukocyte esterase (LE) is a useful marker that can be used in establishing a diagnosis of urinary tract infections (UTIs). The development of a UTI diagnostic method with quantitative determinations ...of biomarkers across all age groups is becoming more important. In this report, microfluidic resistance sensors based on silver ink (Ag ink) and silver ink mixed with ZnO nanoparticles (Ag-ZnO ink) were synthesized and coated on cellulose paper, namely LE-Ag-μPADs and LE-Ag-ZnO-μPADs, respectively, for the sensitive detection of LE. The microfluidic design increases the precision of data and further allows for quantitative determination and early detection of LE in human urine. The quantification of LE relies on the change in the resistance readout coating with Ag ink as well as Ag-ZnO ink in the detection zone. A mixture of 3-(N-tosyl-l-alaninyloxy)-5-phenylpyrrole (PE) and 1-diazo-2-naphthol-4-sulfonic acid (DAS) was deposited in the sample zone to selectively recognize LE, and the resulting nonconductive products, i.e., azo compounds, further reacted with the Ag ink and Ag-ZnO ink to increase resistance. The quantitative detectable LE concentrations between 2 to 32 (×5.2 U mL-1), i.e. ≈12 to 108 μg L-1, cover the commercial dipstick range of trace, +1 and +2. The minimum detectable concentration of LE in urine was 1 (×5.2 U mL-1). The lower concentrations of LE detectable by LE-Ag-μPADs (1-8 × 5.2 U mL-1) are below the value achieved with the ELISA LE kit. Urine samples from inpatients with indwelling urinary catheters were used, and the LE levels measured by the present device were highly correlated with those determined by a commercial urine analyser.
PDF
