Unveiling Corrosion Pathways of Sn Nanocrystals through High-Resolution Liquid Cell Electron Microscopy.

Unveiling materials' corrosion pathways is significant for understanding the corrosion mechanisms and designing corrosion-resistant materials. Here, we investigate the corrosion behavior of Sn@Ni3Sn4 and Sn nanocrystals in an aqueous solution in real time by using high-resolution liquid cell transmission electron microscopy. Our direct observation reveals an unprecedented level of detail on the corrosion of Sn metal with/without a coating of Ni3Sn4 at the nanometric and atomic levels. The Sn@Ni3Sn4 nanocrystals exhibit "pitting corrosion", which is initiated at the defect sites in the Ni3Sn4 protective layer. The early stage isotropic etching transforms into facet-dependent etching, resulting in a cavity terminated with low-index facets. The Sn nanocrystals under fast etching kinetics show uniform corrosion, and smooth surfaces are obtained. Sn nanocrystals show "creeping-like" etching behavior and rough surfaces. This study provides critical insights into the impacts of coating, defects, and ion diffusion on corrosion kinetics and the resulting morphologies.

Study on the Recognition of Coal Miners' Unsafe Behavior and Status in the Hoist Cage Based on Machine Vision.

The hoist cage is used to lift miners in a coal mine's auxiliary shaft. Monitoring miners' unsafe behaviors and their status in the hoist cage is crucial to production safety in coal mines. In this study, a visual detection model is proposed to estimate the number and categories of miners, and to identify whether the miners are wearing helmets and whether they have fallen in the hoist cage. A dataset with eight categories of miners' statuses in hoist cages was developed for training and validating the model. Using the dataset, the classical models were trained for comparison, from which the YOLOv5s model was selected to be the basic model. Due to small-sized targets, poor lighting conditions, and coal dust and shelter, the detection accuracy of the Yolov5s model was only 89.2%. To obtain better detection accuracy, k-means++ clustering algorithm, a BiFPN-based feature fusion network, the convolutional block attention module (CBAM), and a CIoU loss function were proposed to improve the YOLOv5s model, and an attentional multi-scale cascaded feature fusion-based YOLOv5s model (AMCFF-YOLOv5s) was subsequently developed. The training results on the self-built dataset indicate that its detection accuracy increased to 97.6%. Moreover, the AMCFF-YOLOv5s model was proven to be robust to noise and light.

Fcγ receptor-mediated phagocytosis pathway was involved in phagocytosis of mIgM+ B lymphocytes from largemouth bass (Micropterus salmoides).

The potential for phagocytosis has been proven in teleost B cells, but the research on the regulatory mechanism of phagocytosis remains lacking. In this study, three largemouth bass (Micropterus salmoides) (15 ± 5 g) were injected intraperitoneally with Nocardia seriolae (105 CFU/100 µl/fish) in vivo, and their spleen was collected at 72 h post-infection for mRNA-seq. After the de novo assembly of the paired-end reads, 73,622 unigenes were obtained. Gene expression profiling revealed that 2043 unigenes were differentially expressed after N. seriolae infection, comprising 1285 upregulated and 758 downregulated unigenes (q-value <0.05, log2FC > |2|) of which 181 genes were involved in phagocytosis. The Kyoto Encyclopaedia of Genes and Genomes (KEGG) analysis demonstrated that 12 differentially expressed genes (DEG) associated with phagocytosis were enriched in the Fcγ receptor-mediated phagocytosis signalling pathway. In vitro, the phagocytic ability of mIgM+ B lymphocytes was validated using indirect immunofluorescence assay (IIFA) and fluorescence activating cell sorter (FACS), and the phagocytosis rates of the mIgM+ B lymphocytes incubated with a Lyn inhibitor had decreased from 18.533 ± 6.00% to 11.610 ± 4.236% compared with the unblocked group. These results suggested that the Fcγ receptor-mediated phagocytosis signalling pathway had participated in the phagocytosis of B cells and provide further insight into the role of B cells in innate immunology.

Analysis of phagocytosis by mIgM+ lymphocytes depending on monoclonal antibodies against IgM of largemouth bass (Micropterus salmoides).

The phagocytic actives of B cells in fish have been proven in recent years. In this study, five positive hybridomas secreting monoclonal antibodies (MAbs) against largemouth bass IgM were produced. Indirect immunofluorescence assay (IFA) demonstrated that five MAbs could specifically recognize membrane-bound IgM (mIgM) molecule of largemouth bass. Indirect ELISA and Western blotting analysis showed that all the five MAbs had no cross-reactions with the other two teleost IgMs. Flow cytometry analysis (FCM) revealed that the percentages of largemouth bass mIgM+ lymphocytes in head kidney, peripheral blood and spleen were 51.66 ± 0.608%, 16.5 ± 1.235% and 42.92 ± 1.091%, respectively. In addition, the phagocytosis rates of mIgM + lymphocytes ingesting Nocardia seriolae from head kidney, peripheral blood and spleen were calculated to be 5.413 ± 0.274%, 16.6 ± 0.289% and 26.3 ± 0.296%, respectively. The qPCR results of sorted cells indicated that most inflammatory cytokines (IFNγ, IL-1ß, IL-2, IL-12ß, IL-34, IL-10), chemokine (CXCL12), chemokines receptors (CXCR2, CXCR4) and genes (FcγRⅠa, NCF1, CFL, ARP2/3, CD45, Syk, MARCKS) related to FcγR-mediated phagocytic signaling pathway in phagocytic mIgM+ lymphocytes were up-regulated significantly (P < 0.05). Taken together, the results suggested that the MAb (MM06H) produced in this paper could be used as a tool to study mIgM+ lymphocytes of largemouth bass, and FcγR may participate in the phagocytosis of mIgM+ lymphocytes, which is helpful to further study the role of mIgM+ lymphocytes in innate immunity.

Higher superconducting transition temperature by breaking the universal pressure relation.

By investigating the bulk superconducting state via dc magnetization measurements, we have discovered a common resurgence of the superconducting transition temperatures (Tcs) of the monolayer Bi2Sr2CuO6+δ (Bi2201) and bilayer Bi2Sr2CaCu2O8+δ (Bi2212) to beyond the maximum Tcs (Tc-maxs) predicted by the universal relation between Tc and doping (p) or pressure (P) at higher pressures. The Tc of underdoped Bi2201 initially increases from 9.6 K at ambient to a peak at 23 K at 26 GPa and then drops as expected from the universal Tc-P relation. However, at pressures above 40 GPa, Tc rises rapidly without any sign of saturation up to 30 K at 51 GPa. Similarly, the Tc for the slightly overdoped Bi2212 increases after passing a broad valley between 20 and 36 GPa and reaches 90 K without any sign of saturation at 56 GPa. We have, therefore, attributed this Tc resurgence to a possible pressure-induced electronic transition in the cuprate compounds due to a charge transfer between the Cu 3[Formula: see text] and the O 2p bands projected from a hybrid bonding state, leading to an increase of the density of states at the Fermi level, in agreement with our density functional theory calculations. Similar Tc-P behavior has also been reported in the trilayer Br2Sr2Ca2Cu3O10+δ (Bi2223). These observations suggest that higher Tcs than those previously reported for the layered cuprate high-temperature superconductors can be achieved by breaking away from the universal Tc-P relation through the application of higher pressures.

Functional Characterization of Largemouth Bass (Micropterus salmoides) Soluble FcγR Homolog in Response to Bacterial Infection.

Fc receptors (FcRs) are key players in antibody-dependent cellular phagocytosis (ADCP) with their specific recognition of the Fc portion of an immunoglobulin. Despite reports of FcγR-mediated phagocytosis in mammals, little is known about the effects of soluble FcγRs on the immune response. In this study, FcγRIα was cloned from the largemouth bass (Micropterus salmoides) (MsFcγRIα). Without a transmembrane segment or a cytoplasmic tail, MsFcγRIα was identified as a soluble form protein and widely distributed in the spleen, head kidney, and intestine. The native MsFcγRIα was detected in the serum of Nocardia seriolae-infected largemouth bass and the supernatants of transfected HEK293 cells. Additionally, it was verified that the transfected cells' surface secreted MsFcRIα could bind to largemouth bass IgM. Moreover, the expression changes of MsFcγRIα, Syk, and Lyn indicated that MsFcγRIα was engaged in the acute phase response to bacteria, and the FcγR-mediated phagocytosis pathway was activated by Nocardia seriolae stimulation. Furthermore, recombinant MsFcγRIα could enhance both reactive oxygen species (ROS) and phagocytosis to Nocardia seriolae of leukocytes, presumably through the interaction of MsFcγRIα with a complement receptor. In conclusion, these findings provided a better understanding of the function of soluble FcγRs in the immune response and further shed light on the mechanism of phagocytosis in teleosts.

Social networks and cognitive function in older adults: findings from the HAPIEE study.

BACKGROUND: Social networks are associated with better cognitive health in older people, but the role of specific aspects of the social network remains unclear. This is especially the case in Central and Eastern Europe. This study examined associations between three aspects of the social network (network size of friends and relatives, contact frequency with friends and relatives, and social activity participation) with cognitive functions (verbal memory, learning ability, verbal fluency, processing speed, and global cognitive function) in older Czech, Polish, and Russian adults. METHODS: Linear regression estimated associations between baseline social networks and cognitive domains measured at both baseline and follow-up (mean duration of follow-up, 3.5 ± 0.7 years) in 6691 participants (mean age, 62.2 ± 6.0 years; 53.7% women) from the Health, Alcohol and Psychosocial factors In Eastern Europe (HAPIEE) study. RESULTS: Cross-sectional analyses, adjusted for country, age, and sex, showed positive associations of global cognitive function with social activity participation and network size of friends and relatives, but not with contact frequency in either network. Further adjustment for sociodemographic, behavioural, and health characteristics attenuated the associations with network size of relatives (P-trend = 0.074) but not with network size of friends (P-trend = 0.036) or social activities (P-trend< 0.001). In prospective analyses, network size and social activity participation were also linked with better cognition in simple models, but the associations were much stronger for social activities (P-trend< 0.001) than for network size of friends (P-trend = 0.095) and relatives (P-trend = 0.425). Adjustment for baseline cognition largely explained the prospective associations with network size of friends (P-trend = 0.787) and relatives (P-trend = 0.815), but it only slightly attenuated the association with social activities (P-trend< 0.001). The prospective effect of social activities was largely explained by sociodemographic, health behavioural, and health covariates (P-trend = 0.233). Analyses of specific cognitive domains generally replicated the cross-sectional and prospective findings for global cognitive function. CONCLUSIONS: Older Central and Eastern European adults with larger social networks and greater social activities participation had better cognitive function, but these associations were stronger at baseline than over the short-term follow-up.

Pocketlike Active Site of Rh1/MoS2 Single-Atom Catalyst for Selective Crotonaldehyde Hydrogenation.

Selective hydrogenation of unsaturated aldehydes to unsaturated alcohols is a valuable but challenging task for synthesizing fine chemicals. We report that single Rh atoms anchored to the edges of 2D MoS2 sheets can efficiently convert crotonaldehyde to crotyl alcohol with 100% selectivity via a steric confinement effect of pocketlike active sites. Characterization results suggest that the synthesized Rh1/MoS2 single-atom catalysts (SACs) possess a unique geometric and electronic configuration, which confines the adsorption mode of the reactant molecule by a steric effect. The DFT calculations suggest that the MoS2 sheets terminate with oxidized Mo edges and the Rh1 stably anchors at the Mo cation vacancy site, which can facilely dissociate H2 to H atoms. The dissociated H atoms spill over to react with the edge O atoms to form OH species and create an HO-Mo-Rh1-Mo-OH configuration, resembling a pocketlike active site, which confines the adsorption mode of the crotonaldehyde due to steric effects. Such specific adsorption configuration yields 100% selectivity. The strategy of constructing pocketlike active centers with single metal atoms and 2D nanosheets opens new approaches to designing highly selective SACs for specific classes of catalytic transformations.

Stable and Active Oxidation Catalysis by Cooperative Lattice Oxygen Redox on SmMn2O5 Mullite Surface.

The correlation between lattice oxygen (O) binding energy and O oxidation activity imposes a fundamental limit in developing oxide catalysts, simultaneously meeting the stringent thermal stability and catalytic activity standards for complete oxidation reactions under harsh conditions. Typically, strong O binding indicates a stable surface structure, but low O oxidation activity, and vice versa. Using nitric oxide (NO) catalytic oxidation as a model reaction, we demonstrate that this conflicting correlation can be avoided by cooperative lattice oxygen redox on SmMn2O5 mullite oxides, leading to stable and active oxide surface structures. The strongly bound neighboring lattice oxygen pair cooperates in NO oxidation to form bridging nitrate (NO3-) intermediates, which can facilely transform into monodentate NO3- by a concerted rotation with simultaneous O2 adsorption onto the resulting oxygen vacancy. Subsequently, monodentate NO3- species decompose to NO2 to restore one of the lattice oxygen atoms that act as a reversible redox center, and the vacancy can easily activate O2 to replenish the consumed one. This discovery not only provides insights into the cooperative reaction mechanism but also aids the design of oxidation catalysts with the strong O binding region, offering strong activation of O2, high O activity, and high thermal stability in harsh conditions.

Polarity governs atomic interaction through two-dimensional materials.

The transparency of two-dimensional (2D) materials to intermolecular interactions of crystalline materials has been an unresolved topic. Here we report that remote atomic interaction through 2D materials is governed by the binding nature, that is, the polarity of atomic bonds, both in the underlying substrates and in 2D material interlayers. Although the potential field from covalent-bonded materials is screened by a monolayer of graphene, that from ionic-bonded materials is strong enough to penetrate through a few layers of graphene. Such field penetration is substantially attenuated by 2D hexagonal boron nitride, which itself has polarization in its atomic bonds. Based on the control of transparency, modulated by the nature of materials as well as interlayer thickness, various types of single-crystalline materials across the periodic table can be epitaxially grown on 2D material-coated substrates. The epitaxial films can subsequently be released as free-standing membranes, which provides unique opportunities for the heterointegration of arbitrary single-crystalline thin films in functional applications.

Quantum Transport and Band Structure Evolution under High Magnetic Field in Few-Layer Tellurene.

Quantum Hall effect (QHE) is a macroscopic manifestation of quantized states that only occurs in confined two-dimensional electron gas (2DEG) systems. Experimentally, QHE is hosted in high-mobility 2DEG with large external magnetic field at low temperature. Two-dimensional van der Waals materials, such as graphene and black phosphorus, are considered interesting material systems to study quantum transport because they could unveil unique host material properties due to the easy accessibility of monolayer or few-layer thin films at the 2D quantum limit. For the first time, we report direct observation of QHE in a novel low-dimensional material system, tellurene. High-quality 2D tellurene thin films were acquired from recently reported hydrothermal method with high hole mobility of nearly 3000 cm2/(V s) at low temperatures, which allows the observation of well-developed Shubnikov-de Haas (SdH) oscillations and QHE. A four-fold degeneracy of Landau levels in SdH oscillations and QHE was revealed. Quantum oscillations were investigated under different gate biases, tilted magnetic fields, and various temperatures, and the results manifest the inherent information on the electronic structure of Te. Anomalies in both temperature-dependent oscillation amplitudes and transport characteristics were observed that are ascribed to the interplay between the Zeeman effect and spin-orbit coupling, as depicted by the density functional theory calculations.

Quantum-Confined Electronic States Arising from the Moiré Pattern of MoS2-WSe2 Heterobilayers.

A two-dimensional (2D) heterobilayer system consisting of MoS2 on WSe2, deposited on epitaxial graphene, is studied by scanning tunneling microscopy and spectroscopy at temperatures of 5 and 80 K. A moiré pattern is observed, arising from lattice mismatch of 3.7% between the MoS2 and WSe2. Significant energy shifts are observed in tunneling spectra observed at the maxima of the moiré corrugation, as compared with spectra obtained at corrugation minima, consistent with prior work. Furthermore, at the minima of the moiré corrugation, sharp peaks in the spectra at energies near the band edges are observed for spectra acquired at 5 K. The peaks correspond to discrete states that are confined within the moiré unit cells. Conductance mapping is employed to reveal the detailed structure of the wave functions of the states. For measurements at 80 K, the sharp peaks in the spectra are absent, and conductance maps of the band edges reveal little structure.

Efficient Synthesis of Furfural from Biomass Using SnCl4 as Catalyst in Ionic Liquid.

Furfural is a versatile platform molecule for the synthesis of various chemicals and fuels, and it can be produced by acid-catalyzed dehydration of xylose derived from renewable biomass resources. A series of metal salts and ionic liquids were investigated to obtain the best combination of catalyst and solvent for the conversion of xylose into furfural. A furfural yield of 71.1% was obtained at high xylose loading (20 wt%) from the single-phasic reaction system whereby SnCl4 was used as catalyst and ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIMBr) was used as reaction medium. Moreover, the combined catalyst consisting of 5 mol% SnCl4 and 5 mol% MgCl2 also produced a high furfural yield (68.8%), which was comparable to the furfural yield obtained with 10 mol% SnCl4. The water⁻organic solvent biphasic systems could improve the furfural yield compared with the single aqueous phase. Although these organic solvents could form biphasic systems with ionic liquid EMIMBr, the furfural yield decreased remarkably compared with the single EMIMBr phase. Besides, the EMIMBr/SnCl4 system with appropriate water was also efficient to convert xylan and lignocellulosic biomass corn stalk into furfural, obtaining furfural yields as high as 57.3% and 54.5%, respectively.

First principles study of the Mn-doping effect on the physical and chemical properties of mullite-family Al2SiO5.

Transition metal (TM) modification is a common strategy for converting an earth-abundant mineral into a cost-effective catalyst for industrial applications. Among a variety of minerals, Al2SiO5, which has three phases, andalusite, sillimanite and kyanite, is emerging as a promising candidate for new catalyst development. In this paper, we use Mn to demonstrate the rationale of 3d TM doping at the Al sites in each of these three phases through first-principles calculations and the cluster expansion method. The results of cluster expansion show that Mn has a strong site preference for the six-coordinated Al octahedral chains in the andalusite and sillimanite phases, while distributing randomly in the kyanite phase. Moreover, Mn can only replace Al in sillimanite and kyanite in low concentrations; however, higher concentrations of Mn can replace Al in andalusite. We found that the concentration sensitivity is due to the Jahn-Teller distortion and 3d orbital splitting. This finding can also explain the low doping concentrations of other 3d TMs (Fe, Cr and V) in Al2SiO5 compounds. Based on the calculated Helmholtz free energy, we constructed a (MnxAl1-x)AlSiO5 temperature-composite phase diagram, which explains the physical mechanisms behind the results for 3d transition metal doping and phase transitions in Al2SiO5. This work could shed light on the related physics, chemistry, and geoscience of (MnxAl1-x)AlSiO5, and more importantly, a design rationale for the engineering of cheap catalysts.

Theoretical Demonstration of the Ionic Barristor.

In this Letter, we use first-principles simulations to demonstrate the absence of Fermi-level pinning when graphene is in contact with transition metal dichalcogenides (TMDs). We find that formation of either an ohmic or Schottky contact is possible. Then we show that, due to the shallow density of states around its Fermi level, the work function of graphene can be tuned by ion adsorption. Finally we combine work function tuning of graphene and an ideal contact between graphene and TMDs to propose an ionic barristor design that can tune the work function of graphene with a much wider margin than current barristor designs, achieving a dynamic switching among p-type ohmic contact, Schottky contact, and n-type ohmic contact in one device.

Swap motion-directed twinning of nanocrystals.

Twinning frequently occurs in nanocrystals during various thermal, chemical, or mechanical processes. However, the nucleation and propagation mechanisms of twinning in nanocrystals remain poorly understood. Through in situ atomic resolution transmission electron microscopy observation at millisecond temporal resolution, we show the twinning in Pb individual nanocrystals via a double-layer swap motion where two adjacent atomic layers shift relative to one another. The swap motion results in twin nucleation, and it also serves as a basic unit of movement for twin propagation. Our calculations reveal that the swap motion is a phonon eigenmode of the face-centered cubic crystal structure of Pb, and it is enhanced by the quantum size effect of nanocrystals.

Defect-mediated ripening of core-shell nanostructures.

Understanding nanostructure ripening mechanisms is desirable for gaining insight on the growth and potential applications of nanoscale materials. However, the atomic pathways of nanostructure ripening in solution have rarely been observed directly. Here, we report defect-mediated ripening of Cd-CdCl2 core-shell nanoparticles (CSN) revealed by in-situ atomic resolution imaging with liquid cell transmission electron microscopy. We find that ripening is initiated by dissolution of the nanoparticle with an incomplete CdCl2 shell, and that the areas of the Cd core that are exposed to the solution are etched first. The growth of the other nanoparticles is achieved by generating crack defects in the shell, followed by ion diffusion through the cracks. Subsequent healing of crack defects leads to a highly crystalline CSN. The formation and annihilation of crack defects in the CdCl2 shell, accompanied by disordering and crystallization of the shell structure, mediate the ripening of Cd-CdCl2 CSN in the solution.

Honeycombed Au@C-TiO2-Xcatalysts for enhanced photocatalytic mineralization of Acid red 3R under visible light.

The mineralization of organic pollutants under visible light is challenging, limiting the practical application of photocatalytic technology in wastewater treatment. To achieve the efficient mineralization of Acid red 3R (AR3R), a series of honeycombed catalysts (TiO2, C-TiO2-X, Au@TiO2 and Au@C-TiO2-X) were prepared via a facile in situ synthetic method and characterized by XRD, TEM, BET, XPS and DRS, respectively. The introduction of C and Au species promote the simultaneous generation of •O2- and •OH over Au@C-TiO2-X under visible light radiation. The Au@C-TiO2-X catalyst showed superior performance for the deep mineralization of AR3R, affording a TOC removal rate larger than 90 % within 240 min under visible light (> 420 nm). The photocatalytic degradation mechanism of AR3R is proposed according to UV-vis and in situ DRIFTS analysis. The superior photocatalytic activity of Au@C-TiO2-X is attributed to the synergistic effect of •O2- and •OH owing to C doping and Au deposition.

Publisher Correction: Alloying conducting channels for reliable neuromorphic computing.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Alloying conducting channels for reliable neuromorphic computing.

A memristor1 has been proposed as an artificial synapse for emerging neuromorphic computing applications2,3. To train a neural network in memristor arrays, changes in weight values in the form of device conductance should be distinct and uniform3. An electrochemical metallization (ECM) memory4,5, typically based on silicon (Si), has demonstrated a good analogue switching capability6,7 owing to the high mobility of metal ions in the Si switching medium8. However, the large stochasticity of the ion movement results in switching variability. Here we demonstrate a Si memristor with alloyed conduction channels that shows a stable and controllable device operation, which enables the large-scale implementation of crossbar arrays. The conduction channel is formed by conventional silver (Ag) as a primary mobile metal alloyed with silicidable copper (Cu) that stabilizes switching. In an optimal alloying ratio, Cu effectively regulates the Ag movement, which contributes to a substantial improvement in the spatial/temporal switching uniformity, a stable data retention over a large conductance range and a substantially enhanced programmed symmetry in analogue conductance states. This alloyed memristor allows the fabrication of large-scale crossbar arrays that feature a high device yield and accurate analogue programming capability. Thus, our discovery of an alloyed memristor is a key step paving the way beyond von Neumann computing.