Optimizing the Electronic Structure of Atomically Dispersed Ru Sites with CoP for Highly Efficient Hydrogen Evolution in both Alkaline and Acidic Media.

Developing efficient and stable electrocatalysts for hydrogen evolution reaction (HER) over a wide pH range and industrial large-scale hydrogen production is critical and challenging. Here, a tailoring strategy is developed to fabricate an outstanding HER catalyst in both acidic and alkaline electrolytes containing high-density atomically dispersed Ru sites anchored in the CoP nanoparticles supported on carbon spheres (NC@RuSA -CoP). The obtained NC@RuSA -CoP catalyst exhibits excellent HER performance with overpotentials of only 15 and 13 mV at 10 mA cm-2 in 1 m KOH and 0.5 m H2 SO4 , respectively. The experimental results and theoretical calculations indicate that the strong interaction between the Ru site and the CoP can effectively optimize the electronic structure of Ru sites to reduce the hydrogen binding energy and the water dissociation energy barrier. The constructed alkaline anion exchange membrane water electrolyze (AAEMWE) demonstrates remarkable durability and an industrial-level current density of 1560 mA cm-2 at 1.8 V. This strategy provides a new perspective on the design of Ru-based electrocatalysts with suitable intermediate adsorption strengths and paves the way for the development of highly active electrocatalysts for industrial-scale hydrogen production.

High-Performance Sliding Ferroelectric Transistor Based on Schottky Barrier Tuning.

Sliding ferroelectricity associated with interlayer translation is an excellent candidate for ferroelectric device miniaturization. However, the weak polarization gives rise to the poor performance of sliding ferroelectric transistors with a low on/off ratio and a narrow memory window, which restricts its practical application. To address the issue, we propose a facile strategy by regulating the Schottky barrier in sliding ferroelectric semiconductor transistors based on γ-InSe, in which a high performance with a large on/off ratio (106) and a wide memory window (4.5 V) was ultimately acquired. Additionally, the memory window of the device can be further modulated by electrostatic doping or light excitation. These results open up new ways for designing novel ferroelectric devices based on emerging sliding ferroelectricity.

The correlation between the influencing factors and efficacy of immune checkpoint inhibitor therapy: an umbrella meta-analysis of randomized controlled trials.

OBJECTIVE: We performed an umbrella meta-analysis to explore the factors that influence the efficacy of immune checkpoint inhibitor (ICI) therapy. MATERIALS AND METHODS: We systematically searched three databases (PubMed, Web of Science and Embase) up to 20 February 2023. Extracting the effect size and 95% confidence intervals for overall survival (OS), progression-free survival (PFS) and the objective response rate (ORR). RESULTS: A total of 65 articles were included. We identified the following factors that benefit ICI therapy: smoking status (PFS: 0.72 [0.62, 0.84], p < .001), chemotherapy (PFS: 0.68 [0.58, 0.79], p < .001), expression of programmed cell death ligand 1(PD-L1) (≥1%, ≥5%, or ≥10%) (≥1%: 0.76 [0.71,0.82], p < .001; ≥5%: 0.62 [0.52, 0.74], p < .001; ≥10%: 0.42 [0.30, 0.59], p < .001). We also identified three adverse factors: epidermal growth factor receptor mutations (OS: 1.57 [1.06, 2.32], p = .02), with liver metastases (OS: 1.16 [1.02,1.32], p = .02) and antibiotics (OS: 3.13 [1.25,7.84], p < .001; PFS: 2.54 [1.38, 4.68], p = .003). CONCLUSION: The results of this umbrella meta-analysis first supported pre-existing understandings of the relationship between beneficial and adverse factors with the efficacy of ICI therapy. In addition, the overexpression of PD-L1 may adversely affect patients.

The umbrella meta-analysis first supported pre-existing understandings of the relationship between beneficial and adverse factors with the efficacy of immune checkpoint inhibitor therapy.This study found three factors that are not conducive to the efficacy of immune checkpoint inhibitor: epidermal growth factor receptor mutations, with liver metastases and antibiotics.We found the overexpression of PD-L1 may adversely affect patients.

Silica nanoparticles induce pulmonary damage in rats via VEGFC/D-VEGFR3 signaling-mediated lymphangiogenesis and remodeling.

Silica nanoparticles (SiNPs) are widely used as drug carriers for improving drug delivery and retention. The lungs are highly sensitive to the toxicity of SiNPs entering the respiratory tract. Furthermore, pulmonary lymphangiogenesis, which is the growth of lymphatic vessels observed during multiple pulmonary diseases, plays a vital role in promoting the lymphatic transport of silica in the lungs. However, more research is required on the effects of SiNPs on pulmonary lymphangiogenesis. We investigated the effect of SiNP-induced pulmonary toxicity on lymphatic vessel formation in rats and evaluated the toxicity and possible molecular mechanisms of 20-nm SiNPs. Saline containing 3.0, 6.0, and 12.0mg/kg of SiNPs was instilled intrathecally into female Wistar rats once a day for five days, then sacrificed on day seven. Lung histopathology, pulmonary permeability, pulmonary lymphatic vessel density changes, and the ultrastructure of the lymph trunk were investigated using light microscopy, spectrophotometry, immunofluorescence, and transmission electron microscopy. CD45 expression in lung tissues was determined using immunohistochemical staining, and protein expression in the lung and lymph trunk was quantified using western blotting. We observed increased pulmonary inflammation and permeability, lymphatic endothelial cell damage, pulmonary lymphangiogenesis, and remodeling with increasing SiNP concentration. Moreover, SiNPs activated the VEGFC/D-VEGFR3 signaling pathway in the lung and lymphatic vessel tissues. SiNPs caused pulmonary damage, increased permeability and resulted in inflammation-associated lymphangiogenesis and remodeling by activating VEGFC/D-VEGFR3 signaling. Our findings provide evidence for SiNP-induced pulmonary damage and a new perspective for the prevention and treatment of occupational exposure to SiNPs. DATA AVAILABILITY: The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.

Development and application of lateral flow strip with three test lines for detection of deoxynivalenol in wheat.

Lateral flow strip was widely used and their qualitative and quantitative performance was in continuous improvement. However, the traditional strip was in a single-test-line format, which restricted operators to making a semi-quantitative judgment around a desired threshold concentration. Herein, a single strip with three test lines (TTLS) was developed for the semi-quantitative and quantitative determination of deoxynivalenol (DON). Four visual detection thresholds were obtained under optimized conditions and 35 wheat samples with DON content from 45 µg/kg to 2841 µg/kg were used to verify the method. The detection results were compared with that of the traditional strip and UPLC-MS/MS. In a three-test-line format, TTLS could reveal at least 200, 500, 1000, and 2000 µg/kg DON existed in different samples by the naked eye. The agreement analysis and statistical results indicated the new TTLS can be used as a useful tool for quantitative detection of DON with wide dynamic range.

Disorder-tuned conductivity in amorphous monolayer carbon.

Correlating atomic configurations-specifically, degree of disorder (DOD)-of an amorphous solid with properties is a long-standing riddle in materials science and condensed matter physics, owing to difficulties in determining precise atomic positions in 3D structures1-5. To this end, 2D systems provide insight to the puzzle by allowing straightforward imaging of all atoms6,7. Direct imaging of amorphous monolayer carbon (AMC) grown by laser-assisted depositions has resolved atomic configurations, supporting the modern crystallite view of vitreous solids over random network theory8. Nevertheless, a causal link between atomic-scale structures and macroscopic properties remains elusive. Here we report facile tuning of DOD and electrical conductivity in AMC films by varying growth temperatures. Specifically, the pyrolysis threshold temperature is the key to growing variable-range-hopping conductive AMC with medium-range order (MRO), whereas increasing the temperature by 25 °C results in AMC losing MRO and becoming electrically insulating, with an increase in sheet resistance of 109 times. Beyond visualizing highly distorted nanocrystallites embedded in a continuous random network, atomic-resolution electron microscopy shows the absence/presence of MRO and temperature-dependent densities of nanocrystallites, two order parameters proposed to fully describe DOD. Numerical calculations establish the conductivity diagram as a function of these two parameters, directly linking microstructures to electrical properties. Our work represents an important step towards understanding the structure-property relationship of amorphous materials at the fundamental level and paves the way to electronic devices using 2D amorphous materials.

Catalytically active atomically thin cuprate with periodic Cu single sites.

Rational design and synthesis of catalytically active two-dimensional (2D) materials with an abundance of atomically precise active sites in their basal planes remains a great challenge. Here, we report a ligand exchange strategy to exfoliate bulk [Cu4(OH)6][O3S(CH2)4SO3] cuprate crystals into atomically thin 2D cuprate layers ([Cu2(OH)3]+). The basal plane of 2D cuprate layers contains periodic arrays of accessible unsaturated Cu(II) single sites (2D-CuSSs), which are found to promote efficient oxidative Chan-Lam coupling. Our mechanistic studies reveal that the reactions proceed via coordinatively unsaturated CuO4(II) single sites with the formation of Cu(I) species in the rate-limiting step, as corroborated by both operando experimental and theoretical studies. The robust stability of 2D-CuSSs in both batch and continuous flow reactions, coupled with their recyclability and good performance in complex molecule derivatization, render 2D-CuSSs attractive catalyst candidates for broad utility in fine chemical synthesis.

Heteroepitaxy of 2D CuCr2 Te4 with Robust Room-temperature Ferromagnetism.

Magnetic materials in 2D have attracted widespread attention for their intriguing magnetic properties. 2D magnetic heterostructures can provide unprecedented opportunities for exploring fundamental physics and novel spintronic devices. Here, the heteroepitaxial growth of ferromagnetic CuCr2 Te4 nanosheets is reported on Cr2 Te3 and mica by chemical vapor deposition. Magneto-optical Kerr effect measurements reveal the thickness-dependent ferromagnetism of CuCr2 Te4 nanosheets on mica, where a decrease of Curie temperature (TC ) from 320 to 260 K and an enhancement of perpendicular magnetic anisotropy with reducing thickness are observed. Moreover, lattice-matched heteroepitaxial ultrathin CuCr2 Te4 on Cr2 Te3 exhibits an enhanced robust ferromagnetism with TC up to 340 K due to the interfacial charge transfer. Stripe-type magnetic domains and single magnetic domain are discovered in this heterostructure with different thicknesses. The work provides a way to construct robust room-temperature 2D magnetic heterostructures for functional spintronic devices.

Targeting LAYN inhibits colorectal cancer metastasis and tumor-associated macrophage infiltration induced by hyaluronan oligosaccharides.

The accumulation of hyaluronan oligosaccharides (oHA) in colorectal cancer (CRC) is closely related to tumor metastasis, but the underlying mechanism remains unclear. In this study, we first described that LAYN, a novel HA receptor, was upregulated in CRC tissue. Aberrant LAYN expression correlated with CRC metastasis and poor prognosis and positively correlated with tumor-associated macrophage (TAM) infiltration and M2 macrophage polarization in the tumor environment. Both in vitro and in vivo studies demonstrated that LAYN is activated by oHA and subsequently induces CRC metastasis and macrophage infiltration. Mechanistic studies demonstrated that oHA activates LAYN by binding to the 60-68th amino acid region of the extracellular segment. oHA-induced LAYN activation promoted metastasis and CCL20 secretion through the NF-kB pathway in CRC cells. Furthermore, targeting LAYN using a blocking antibody prevented oHA-mediated tumor metastasis, TAM infiltration and M2 polarization. This study revealed the LAYN activation mechanism and identified a potential target for the treatment of CRC tumor exhibiting high oHA levels.

A general thermodynamics-triggered competitive growth model to guide the synthesis of two-dimensional nonlayered materials.

Two-dimensional (2D) nonlayered materials have recently provoked a surge of interest due to their abundant species and attractive properties with promising applications in catalysis, nanoelectronics, and spintronics. However, their 2D anisotropic growth still faces considerable challenges and lacks systematic theoretical guidance. Here, we propose a general thermodynamics-triggered competitive growth (TTCG) model providing a multivariate quantitative criterion to predict and guide 2D nonlayered materials growth. Based on this model, we design a universal hydrate-assisted chemical vapor deposition strategy for the controllable synthesis of various 2D nonlayered transition metal oxides. Four unique phases of iron oxides with distinct topological structures have also been selectively grown. More importantly, ultra-thin oxides display high-temperature magnetic ordering and large coercivity. MnxFeyCo3-x-yO4 alloy is also demonstrated to be a promising room-temperature magnetic semiconductor. Our work sheds light on the synthesis of 2D nonlayered materials and promotes their application for room-temperature spintronic devices.

Atomically Unveiling an Atlas of Polytypes in Transition-Metal Trihalides.

Transition-metal trihalides MX3 (M = Cr, Ru; X = Cl, Br, and I) belong to a family of novel two-dimensional (2D) magnets that can exhibit topological magnons and electromagnetic properties, thus affording great promises in next-generation spintronic devices. Rich magnetic ground states observed in the MX3 family are believed to be strongly correlated to the signature Kagome lattice and interlayer van der Waals coupling raised from distinct stacking orders. However, the intrinsic air instability of MX3 makes their direct atomic-scale analysis challenging. Therefore, information on the stacking-registry-dependent magnetism for MX3 remains elusive, which greatly hinders the engineering of desired phases. Here, we report a nondestructive transfer method and successfully realize an intact transfer of bilayer MX3, as evidenced by scanning transmission electron microscopy (STEM). After surveying hundreds of MX3 thin flakes, we provide a full spectrum of stacking orders in MX3 with atomic precision and calculated their associated magnetic ground states, unveiled by combined STEM and density functional theory (DFT). In addition to well-documented phases, we discover a new monoclinic C2/c phase in the antiferromagnetic (AFM) structure widely existing in MX3. Rich stacking polytypes, including C2/c, C2/m, R3̅, P3112, etc., provide rich and distinct magnetic ground states in MX3. Besides, a high density of strain soliton boundaries is consistently found in all MX3, combined with likely inverted structures, allowing AFM to ferromagnetic (FM) transitions in most MX3. Therefore, our study sheds light on the structural basis of diverse magnetic orders in MX3, paving the way for modulating magnetic couplings via stacking engineering.

Ultrathin quantum light source with van der Waals NbOCl2 crystal.

Interlayer electronic coupling in two-dimensional materials enables tunable and emergent properties by stacking engineering. However, it also results in significant evolution of electronic structures and attenuation of excitonic effects in two-dimensional semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a van der Waals crystal, niobium oxide dichloride (NbOCl2), featuring vanishing interlayer electronic coupling and monolayer-like excitonic behaviour in the bulk form, along with a scalable second-harmonic generation intensity of up to three orders higher than that in monolayer WS2. Notably, the strong second-order nonlinearity enables correlated parametric photon pair generation, through a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as about 46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in two-dimensional layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources as well as high-performance photon modulators in both classical and quantum optical technologies1-4.

Ultrastrong Optical Harmonic Generations in Layered Platinum Disulfide in the Mid-Infrared.

Nonlinear optical activities (e.g., harmonic generations) in two-dimensional (2D) layered materials have attracted much attention due to the great promise in diverse optoelectronic applications such as nonlinear optical modulators, nonreciprocal optical device, and nonlinear optical imaging. Exploration of nonlinear optical response (e.g., frequency conversion) in the infrared, especially the mid-infrared (MIR) region, is highly desirable for ultrafast MIR laser applications ranging from tunable MIR coherent sources, MIR supercontinuum generation, and MIR frequency-comb-based spectroscopy to high harmonic generation. However, nonlinear optical effects in 2D layered materials under MIR pump are rarely reported, mainly due to the lack of suitable 2D layered materials. Van der Waals layered platinum disulfide (PtS2) with a sizable bandgap from the visible to the infrared region is a promising candidate for realizing MIR nonlinear optical devices. In this work, we investigate the nonlinear optical properties including third-and fifth-harmonic generation (THG and FHG) in thin layered PtS2 under infrared pump (1550-2510 nm). Strikingly, the ultrastrong third-order nonlinear susceptibility χ(3)(-3ω;ω,ω,ω) of thin layered PtS2 in the MIR region was estimated to be over 10-18 m2/V2, which is about one order of that in traditional transition metal chalcogenides. Such excellent performance makes air-stable PtS2 a potential candidate for developing next-generation MIR nonlinear photonic devices.

Sliding induced multiple polarization states in two-dimensional ferroelectrics.

When the atomic layers in a non-centrosymmetric van der Waals structure slide against each other, the interfacial charge transfer results in a reversal of the structure's spontaneous polarization. This phenomenon is known as sliding ferroelectricity and it is markedly different from conventional ferroelectric switching mechanisms relying on ion displacement. Here, we present layer dependence as a new dimension to control sliding ferroelectricity. By fabricating 3 R MoS2 of various thicknesses into dual-gate field-effect transistors, we obtain anomalous intermediate polarization states in multilayer (more than bilayer) 3 R MoS2. Using results from ab initio density functional theory calculations, we propose a generalized model to describe the ferroelectric switching process in multilayer 3 R MoS2 and to explain the formation of these intermediate polarization states. This work reveals the critical roles layer number and interlayer dipole coupling play in sliding ferroelectricity and presents a new strategy for the design of novel sliding ferroelectric devices.

New Folding 2D-Layered Nitro-Oxygenated Carbon Containing Ultra High-Loading Copper Single Atoms.

The discoveries of 2D nanomaterials have made huge impacts on the scientific community. Their unique properties unlock new technologies and bring significant advances to diverse applications. Herein, an unprecedented 2D-stacked material consisting of copper (Cu) on nitro-oxygenated carbon is disclosed. Unlike any known 2D stacked structures that are usually constructed by stacking of separate 2D layers, this material forms a continuously folded 2D-stacked structure. Interestingly, advanced characterizations indicate that Cu atoms inside the structure are in an atomically-dispersed form with extraordinarily high Cu loading up to 15.9 ± 1.2 wt.%, which is among the highest reported metal loading for single-atom catalysts on 2D supports. Facile exfoliation results in thin 2D nanosheets that maximize the exposure of the unique active sites (two neighboring Cu single atoms), leading to impressive catalytic performance, as demonstrated in the electrochemical oxygen reduction reaction.

NCQDs active sites as effective collectors of charge carriers towards enhanced photocatalytic activity of porous Co3O4.

In this work, different proportions of N-doped carbon quantum dots/porous Co3O4 (NCQDs/p-Co3O4) NCQDs/Co3O4 composite photocatalysts were prepared by a simple self-assembly method. It was demonstrated by a series of characterizations that 50% NCQDs/Co3O4 has a good visible light response and low electrochemical impedance. The photocatalytic degradation of TC was investigated by the 50% NCQDs/p-Co3O4 composite photocatalyst, and the results showed that the degradation effect of TC reached 81.2% within 120 min. The higher photocatalytic activity of 50% NCQDs/p-Co3O4 was analyzed probably because NCQDs can improve the separation efficiency of photogenerated electron-hole pairs and p-Co3O4 can provide a larger specific surface area and thus has more active sites. This study provides a new strategy for improving the photodegradation activity of Co3O4 photocatalysts.

Composition-Controllable Syntheses and Property Modulations from 2D Ferromagnetic Fe5 Se8 to Metallic Fe3 Se4 Nanosheets.

Exploring new-type 2D magnetic materials with high magnetic transition temperature and robust air stability has attracted wide attention for developing innovative spintronic devices. Recently, intercalation of native metal atoms into the van der Waals gaps of 2D layered transition metal dichalcogenides (TMDs) has been developed to form 2D non-layered magnetic TMDs, while only succeeded in limited systems (e.g., Cr2 S3 , Cr5 Te8 ). Herein, composition-controllable syntheses of 2D non-layered iron selenide nanosheets (25% Fe-intercalated triclinic Fe5 Se8 and 50% Fe-intercalated monoclinic Fe3 Se4 ) are firstly reported, via a robust chemical vapor deposition strategy. Specifically, the 2D Fe5 Se8 exhibits intrinsic room-temperature ferromagnetic property, which is explained by the change of electron spin states from layered 1T'-FeSe2 to non-layered Fe-intercalated Fe5 Se8 based on density functional theory calculations. In contrast, the ultrathin Fe3 Se4 presents novel metallic features comparable with that of metallic TMDs. This work hereby sheds light on the composition-controllable synthesis and fundamental property exploration of 2D self-intercalation induced novel TMDs compounds, by propelling their application explorations in nanoelectronics and spintronics-related fields.

Ultrathin Metal-Organic Framework Nanosheets Exhibiting Exceptional Catalytic Activity.

Two-dimensional (2D) metal-organic framework nanosheets (MONs) or membranes are classes of periodic, crystalline polymeric materials that may show unprecedented physicochemical properties due to their modular structures, high surface areas, and high aspect ratios. Yet preparing 2D MONs from multiple components and two different types of polymerization reaction remains challenging and less explored. Here, we report the synthesis of MOF films via interfacial polymerization, which involves three active monomers for simultaneous polycondensation and polycoordination taking place in a confined interface. The well-defined lamellar structure of the MOF films allowed feasible and scalable exfoliation to produce free-standing 2D MONs with high aspect ratio up to 2000:1 and ultrathin thickness (∼1.7 nm). The pore structure was revealed by high-resolution TEM images with near-atomic precision. The imide-linkage of MONs provided superior thermal (up to 530 °C) and good chemical stability in the pH range from 3 to 12. More importantly, the MONs exhibited exceptional catalytic activity and superior reusability for the hydroboration reactions of alkynes, in which the turnover frequency (TOF) reached 41734 h-1, which is 2-4 orders of magnitude greater than that reported for homogeneous and heterogeneous catalysts.

Epitaxial growth of inch-scale single-crystal transition metal dichalcogenides through the patching of unidirectionally orientated ribbons.

Two-dimensional (2D) semiconductors, especially transition metal dichalcogenides (TMDs), have been envisioned as promising candidates in extending Moore's law. To achieve this, the controllable growth of wafer-scale TMDs single crystals or periodic single-crystal patterns are fundamental issues. Herein, we present a universal route for synthesizing arrays of unidirectionally orientated monolayer TMDs ribbons (e.g., MoS2, WS2, MoSe2, WSe2, MoSxSe2-x), by using the step edges of high-miller-index Au facets as templates. Density functional theory calculations regarding the growth kinetics of specific edges have been performed to reveal the morphological transition from triangular domains to patterned ribbons. More intriguingly, we find that, the uniformly aligned TMDs ribbons can merge into single-crystal films through a one-dimensional edge epitaxial growth mode. This work hereby puts forward an alternative pathway for the direct synthesis of inch-scale uniform monolayer TMDs single-crystals or patterned ribbons, which should promote their applications as channel materials in high-performance electronics or other fields.