A chemical vapor deposition method is developed for thickness‐controlled (one to four layers), uniform, and continuous films of both defective gallium(II) sulfide (GaS): GaS0.87 and stoichiometric ...GaS. The unique degradation mechanism of GaS0.87 with X‐ray photoelectron spectroscopy and annular dark‐field scanning transmission electron microscopy is studied, and it is found that the poor stability and weak optical signal from GaS are strongly related to photo‐induced oxidation at defects. An enhanced stability of the stoichiometric GaS is demonstrated under laser and strong UV light, and by controlling defects in GaS, the photoresponse range can be changed from vis‐to‐UV to UV‐discriminating. The stoichiometric GaS is suitable for large‐scale, UV‐sensitive, high‐performance photodetector arrays for information encoding under large vis‐light noise, with short response time (<66 ms), excellent UV photoresponsivity (4.7 A W–1 for trilayer GaS), and 26‐times increase of signal‐to‐noise ratio compared with small‐bandgap 2D semiconductors. By comprehensive characterizations from atomic‐scale structures to large‐scale device performances in 2D semiconductors, the study provides insights into the role of defects, the importance of neglected material‐quality control, and how to enhance device performance, and both layer‐controlled defective GaS0.87 and stoichiometric GaS prove to be promising platforms for study of novel phenomena and new applications.
A chemical vapor deposition method is developed for controlling defects in gallium(II) sulfide (GaS), and their influence on the UV photosensing response in devices is elucidated. Defects in GaS act as sites of photoinduced oxidation and degradation. High‐quality GaS 2D films show uniform UV photodetector response and defect tuning enables selective UV sensing.
Triangular nanovoids in 2D materials transition metal dichalcogenides have vertex points that cause stress concentration and lead to sharp crack propagation and failure. Here, the atomistic mechanics ...of back folding around triangular nanovoids in monolayer WS2 sheets is examined. Combining atomic‐resolution images from annular dark‐field scanning transmission electron microscopy with reactive molecular modelling, it is revealed that the folding edge formation has statistical preferences under geometric conditions based on the orientation mismatch. It is further investigated how loading directions and strong interlayer friction, interplay with WS2 lattice's crack preference, govern the deformation and fracture pattern around folding edges. These results provide fundamental insights into the combination of fracture and folding in flexible monolayer crystals and the resultant Moiré lattices.
Combining atomic‐resolution images from annular dark‐field scanning transmission electron microscopy with reactive molecular modelling, it is revealed that the folding edge formation has statistical preferences under geometric conditions based on the orientation mismatch. It is further investigated how loading directions and strong interlayer friction, interplay with WS2 lattice's crack preference, govern the deformation and fracture pattern around folding edges.
We show how an oxide passivating layer on the Cu surface before the growth of h-BN by chemical vapor deposition (CVD) can lead to increased domain sizes from 1 to 20 μm by reducing the nucleation ...density from 106 to 103 mm–2. The h-BN domains within each Cu grain are well-oriented, indicating an epitaxial relationship between the h-BN crystals and the Cu growth substrates that leads to larger crystal domains within the film of ∼100 μm. Continuous films are grown and show a high degree of monolayer uniformity. This CVD approach removes the need for low pressures, electrochemical polishing, and expensive substrates for large-area continuous films of h-BN monolayers, which is beneficial for industrial applications that require scalable synthesis.
It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS2 can be atomically sharp, where top and bottom layer GBs are located within sub‐nanometer ...distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic‐resolution annular dark‐field scanning transmission electron microscopy (ADF‐STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA′ stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF‐STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS2 layer, but the second WS2 layer has different dislocation structures not seen in freestanding monolayers, which have metal‐rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.
Long‐range atomically sharp dual tilt grain boundaries are found within bilayer WS2 2D layered crystals grown by chemical vapor deposition. In situ heating experiments within the electron microscope show they are stable to at least 800 °C. The dislocation cores needed for these bilayer interfaces are more complex than monolayer grain boundaries due to competing van der Waals interlayer forces.
The geochemical fractions of trace metals in the coastal sediments of the central western Taiwan were examined, employing the Tessier sequential extraction method, and the metals contamination status ...of the analyzed sediments were also evaluated in the present study. Based on the metal fraction present in sediments, trace metals can be divided into three groups: (1) Al, Cr, Fe, Ni and Zn; (2) Cu and Pb and (3) Mn. In group (1) metal, the metals’ total concentrations were chiefly dominated by the residual fraction, exceeding 80% of the total concentration pool. In group (2) metal, the metals’ total concentrations were dominated by three labile fractions, carbonate, Fe-Mn oxides and organic, accounting for nearly 65% of the total pool, and the residual fraction contributed 35% of the total concentrations. Over 90% of Mn total concentrations were shared by three fractions, carbonate, Fe-Mn oxides and the residual fraction. The statistic results indicated that the total organic carbon contents in sediments played a more important role in influencing the metals contents in sediments. The contamination assessment results suggested that the Mailiao coastal sediments were minorly contaminated by trace metals. Lead should be paid more concerns because Pb total concentrations at some sediments exceeded the value (46.7 mg/kg) of effect range low, USA, and Pb was mainly present in the labile fraction.
Cell sheet-mediated tissue regeneration is a promising approach for corneal reconstruction. However, the fragility of bioengineered corneal endothelial cell (CEC) monolayers allows us to take ...advantage of cross-linked porous gelatin hydrogels as cell sheet carriers for intraocular delivery. The aim of this study was to further investigate the effects of biopolymer concentrations (5-15 wt%) on the characteristic and safety of hydrogel discs fabricated by a simple stirring process combined with freeze-drying method. Results of scanning electron microscopy, porosity measurements, and ninhydrin assays showed that, with increasing solid content, the pore size, porosity, and cross-linking index of carbodiimide treated samples significantly decreased from 508±30 to 292±42 µm, 59.8±1.1 to 33.2±1.9%, and 56.2±1.6 to 34.3±1.8%, respectively. The variation in biopolymer concentrations and degrees of cross-linking greatly affects the Young's modulus and swelling ratio of the gelatin carriers. Differential scanning calorimetry measurements and glucose permeation studies indicated that for the samples with a highest solid content, the highest pore wall thickness and the lowest fraction of mobile water may inhibit solute transport. When the biopolymer concentration is in the range of 5-10 wt%, the hydrogels have high freezable water content (0.89-0.93) and concentration of permeated glucose (591.3-615.5 µg/ml). These features are beneficial to the in vitro cultivation of CECs without limiting proliferation and changing expression of ion channel and pump genes such as ATP1A1, VDAC2, and AQP1. In vivo studies by analyzing the rabbit CEC morphology and count also demonstrate that the implanted gelatin discs with the highest solid content may cause unfavorable tissue-material interactions. It is concluded that the characteristics of cross-linked porous gelatin hydrogel carriers and their triggered biological responses are in relation to biopolymer concentration effects.
Doping of two-dimensional materials provides them tunable physical properties and widens their applications. Here, we demonstrate the postgrowth doping strategy in monolayer and bilayer tungsten ...disulfide (WS2) crystals, which utilizes a metal exchange mechanism, whereby Sn atoms become substitutional dopants in the W sites by energetically favorable replacement. We achieve this using chemical vapor deposition techniques, where high-quality grown WS2 single crystals are first grown and then subsequently reacted with a SnS precursor. Thermal control of the exchange doping mechanism is revealed, indicating that a sufficiently high enough temperature is required to create the S vacancies that are the initial binding sites for the SnS precursor and metal exchange occurrence. This results in a better control of dopant distribution compared to the tradition all-in-one approach, where dopants are added during the growth phase. The Sn dopants exhibit an n-type doping behavior in the WS2 layers based on the decreased threshold voltage obtained from transistor device measurements. Annular dark-field scanning transmission electron microscopy shows that in bilayer WS2 the Sn doping occurs only in the top layer, creating vertical heterostructures with atomic layer doping precision. This postgrowth modification opens up ways to selectively dope one layer at a time and construct mixed stoichiometry vertical heterojunctions in bilayer crystals.
We examine the atomic structure of chemical vapour deposition grown multilayer WS2 pyramids using aberration corrected annular dark field scanning transmission electron microscopy coupled with an in ...situ heating holder. The stacking orders and specific types of defects after partial degradation by S and W atomic loss at high temperature are resolved layer-by-layer. Our study of an individual WS2 pyramid with at least six layers, reveals a mixed 2H and 3R polytype stacking. Etching occurred both top and bottom of the WS2 pyramid, which aids in determining the exact vertical layer stacking configurations in the thicker regions. We provide an extensive catalogue of the contrast profiles associated with defects in WS2 as a function of layer number and stacking type, as imaged using ADF-STEM. These results provide extensive details about the identification of a wide range of defects in S2 layers, and the unique ADF-STEM contrast patterns that arise from complex multilayer stacking.
Glucose control is an important aspect in managing critically ill patients. The goal of this study was to compare the effects of sequential feeding (SF) and continuous feeding (CF) on the blood ...glucose of critically ill patients.
A non-inferiority randomized controlled trial was adopted in this study. A total of 62 patients who were fed enteral nutritional suspension through gastric tubes were enrolled. After achieving 80% of the nutrition target calories (25 kcal·kg-1·day-1) through CF, the patients were then randomly assigned into SF and CF groups. In the SF group, the feeding/fasting time was reasonably determined according to the circadian rhythm of the human body as laid out in traditional Chinese medicine theory. The total daily dosage of the enteral nutritional suspension was equally distributed among three time periods of 7 to 9 o'clock, 11 to 13 o'clock, and 17 to 19 o'clock. The enteral nutritional suspension in each time period was pumped at a uniform rate within 2 h by an enteral feeding pump. In the CF group, patients received CF at a constant velocity by an enteral feeding pump throughout the study. Blood glucose values at five points (6:00/11:00/15:00/21:00/1:00) were monitored and recorded for seven consecutive days after randomization. Enteral feeding intolerance was also recorded. Non-inferiority testing was adopted in this study, the chi-square test or Fisher test was used for qualitative data, and the Mann-Whitney U test was used for quantitative data to determine differences between groups. In particular, a repeated measure one-way analysis of variance was used to identify whether changes in glucose value variables across the time points were different between the two groups.
There were no significant demographic or physiological differences between the SF and CF groups (P > 0.050). The average glucose level in SF was not higher than that in CF (8.8 7.3-10.3 vs. 10.7 9.1-12.1 mmol/L, Z = -2.079, P for non-inferiority = 0.019). Hyperglycemia incidence of each patient was more common in the CF group than that in the SF group (38.4 19.1-63.7% vs. 11.8 3.0-36.7%, Z = -2.213, P = 0.027). Hypoglycemia was not found in either group. Moreover, there was no significant difference during the 7 days in the incidence of feeding intolerance (P > 0.050).
In this non-inferiority study, the average blood glucose in SF was not inferior to that in CF. The feeding intolerance in SF was similar to that in CF. SF may be as safe as CF for critically ill patients.
ClinicalTrials.gov, NCT03439618; https://clinicaltrials.gov/ct2/show/record/NCT03439618.
The goal of this study was to clarify the protective role of the Wnt/β-catenin pathway agonist SKL2001 in a rat model of Caerulein-induced acute pancreatitis. AR42J cells and rats were divided into 4 ...groups: control, Caerulein, SKL2001 + Caerulein, and SKL2001 + control. Cell apoptosis was examined using flow cytometry. Hematoxylin–eosin staining was performed to observe pathological changes in pancreatic and small intestinal tissues. Inflammatory cytokines were detected by enzyme-linked immunosorbent assay (ELISA), while genes related to the Wnt/β-catenin pathway were quantified using quantitative real-time PCR. In vitro results showed that Caerulein promoted cell necrosis, inhibited the Wnt/β-catenin pathway, and increased the level of inflammatory cytokines. However, SKL2001 reduced cell necrosis and inflammatory cytokines and activated the Wnt/β-catenin pathway. Additionally, in vivo results demonstrated the accumulation of fluid (i.e., edema), hemorrhage, inflammation and necrosis of the pancreatic acini occurred 6 h after the final Caerulein induction, with the damage reaching a maximal level 12 h after the final Caerulein induction; meanwhile, the Wnt/β-catenin pathway was evidently inhibited with an enhanced level of inflammatory cytokines. The aforementioned damage was further aggravated 12 h later. Nevertheless, the pancreatic and small intestinal tissue damages were alleviated in Caerulein-induced rats treated with SKL2001. In conclusion, activation of the Wnt/β-catenin pathway could inhibit Caerulein-induced cell apoptosis and inflammatory cytokine release, thus improving pancreatic and intestinal damage in rats with acute pancreatitis.
PDF
