Dietary patterns suggest that dark chocolate intake may have an inhibitory effect on oral cancer: a Mendelian randomization study.

Background: Previous studies reported that variations in dietary intake patterns substantially impact human health, specifically tumorigenesis. However, confounding factors in previous cohort studies have obscured the relationship between dietary differences and the risk of oral cancer (OC). Materials and methods: We developed an outcome dataset from genome-wide association studies (GWAS) data on three OCs within the GAME-ON project, using GWAS-META merging. We extracted 21 dietary exposures, including 10 dietary patterns, 6 vitamins, and 5 micronutrients, from the UK Biobank database, using the inverse variance weighting method as the primary statistical method. Sensitivity analysis was conducted to detect heterogeneity and pleiotropy. Serum metabolite concentrations were adjusted using multivariate Mendelian randomization. Results: Of the 10 analyzed dietary patterns, 8 showed no significant association with the risk of developing OC. Consumption of dark chocolate (inverse variance weighted [IVW]: Odds ratio (OR) = 0.786, 95% confidence interval [CI]: 0.622-0.993, p = 0.044) and sweet pepper exhibited an inverse relationship with OC risk (IVW: OR = 0.757, 95% CI: 0.574-0.997, p = 0.048). Reverse MR analysis revealed no reverse causality. Furthermore, no significant correlation was observed between the intake of 6 vitamins and 5 micronutrients and the risk of developing OC. After using multivariable MR to adjust for serum caffeine, linoleate, theophylline, and theobromine metabolism levels, consuming dark chocolate was unrelated to a decreased risk of OC. After adjusting each serum metabolite individually, the observed p-values deviated from the original values to varying degrees, indicating that the components of dark chocolate could have different effects. Among these components, theophylline demonstrated the most significant inhibitory effect. Conclusion: This study demonstrated a causal relationship between the intake of dark chocolate and sweet peppers and a lower risk of OC. The components of dark chocolate could have different effects.

Hierarchical NiCo2Se4 Arrays Composed of Atomically Thin Nanosheets: Simultaneous Improvements in Thermodynamics and Kinetics for Electrocatalytic Water Splitting in Neutral Media.

The inefficiency of electrocatalysts for water splitting in neutral media stems from a comprehensive impact of poor intrinsic activity, a limited number of active sites, and inadequate mass transport. Herein, hierarchical ultrathin NiCo2Se4 nanosheets are synthesized by the selenization of NiCo2O4 porous nanoneedles. Theoretical and experimental investigations reveal that the intrinsic hydrogen evolution reaction (HER) activity primarily originate from the NiCo2Se4, whereas the high oxygen evolution reaction (OER) performance is related to the NiCoOOH due to the structural reconstruction. The abundant Se and O vacancies introduced by atomically thin nanostructure modulate the electronic structure of NiCo2Se4 and NiCoOOH, thereby improving the intrinsic HER and OER activities, respectively. COMSOL simulation demonstrate the edges of extended nanosheets from the main body significantly promote the charge aggregation, boosting the reduction and oxidation current during HER/OER process. This charge aggregation effect notably exceeds the tip effect for the nanoneedle, highlighting the unique advantage of the hierarchical nanosheet structure. Benefiting from abundant vacancies and unique nanostructure, the hierarchical ultrathin nanosheet simultaneously improve the thermodynamics and kinetics of the electrocatalyst. The optimized samples display an overpotential of 92 mV for HER and 214 mV for OER at 100 mA cm-2, significantly surpassing the performance of currently reported HER/OER catalysts in neutral media.

Removal of Al3+ and Mg2+ ions in wet-process phosphoric acid via the formation of aluminofluoride complexes.

With the decrease in the phosphate rock grade, the minor element ratios (MER) [(Fe2O3 wt% + Al2O3 wt% + MgO wt%)/P2O5 wt%] of wet-process phosphoric acid (WPA) exhibits a linear upward trend. This can lead to a huge challenge for the high-quality production of feed calcium phosphate salt (FCPS). In the present study, we proposed a novel and economical strategy to precipitate Al3+ and Mg2+ via the formation of aluminofluoride complexes (NaMgAlF6·H2O) with the anhydrous sodium sulfate (Na2SO4) and hydrofluoric acid (HF) as precipitation agents. Because of the low solubility of the complexes in WPA, the removal efficiencies of Al3+ and Mg2+ ions could reach 99.5% and 64.8%, respectively. The maximum mass loss of P2O5 was less than 0.5%. The precipitates could be separated and converted into the HF and Na2SO4 for reuse, thus further decreasing the cost of WPA purification.

SLOGAN: Handwriting Style Synthesis for Arbitrary-Length and Out-of-Vocabulary Text.

Large amounts of labeled data are urgently required for the training of robust text recognizers. However, collecting handwriting data of diverse styles, along with an immense lexicon, is considerably expensive. Although data synthesis is a promising way to relieve data hunger, two key issues of handwriting synthesis, namely, style representation and content embedding, remain unsolved. To this end, we propose a novel method that can synthesize parameterized and controllable handwriting S tyles for arbitrary-Length and O ut-of-vocabulary text based on a G enerative A dversarial N etwork (GAN), termed SLOGAN. Specifically, we propose a style bank to parameterize specific handwriting styles as latent vectors, which are input to a generator as style priors to achieve the corresponding handwritten styles. The training of the style bank requires only writer identification of the source images, rather than attribute annotations. Moreover, we embed the text content by providing an easily obtainable printed style image, so that the diversity of the content can be flexibly achieved by changing the input printed image. Finally, the generator is guided by dual discriminators to handle both the handwriting characteristics that appear as separated characters and in a series of cursive joins. Our method can synthesize words that are not included in the training vocabulary and with various new styles. Extensive experiments have shown that high-quality text images with great style diversity and rich vocabulary can be synthesized using our method, thereby enhancing the robustness of the recognizer.

Rapid microwave-assisted synthesis of Ni2P nanosheets from black phosphorus.

The high dielectric loss tangent value of black phosphorus nanosheets enables them to be selectively heated under microwave radiation to realize the in situ surface reaction of BP with Ni2+ to prepare thermodynamically unstable two-dimensional Ni2P.

UCP1 and AOX1a contribute to regulation of carbon and nitrogen metabolism and yield in Arabidopsis under low nitrogen stress.

Nitrogen (N) availability is a critical factor for plant development and crop yield, and it closely correlates to carbon (C) metabolism. Uncoupling protein (UCP) and alternative oxidase (AOX) exhibit a strong correlation with N and C metabolism. Here, we investigated the functions of UCP1 and AOX1a using their mutants and complementation lines in Arabidopsis adaptation to low N. Low N markedly increased AOX1a and UCP1 expression, alternative pathway capacity and UCP activity. Eight-day-old aox1a/ucp1 seedlings were more sensitive to low N than Col-0 and single mutants, exhibiting lower primary root length and higher anthocyanin accumulation. The net photosynthetic rate, electron transport rate, PSII actual photochemical efficiency, stomatal conductance and carboxylation efficiency were markedly decreased in ucp1 and aox1a/ucp1 compared to those in Col-0 and aox1a under low N stress; comparatively, chlorophyll content and non-photochemical quenching coefficient were the lowest and highest in aox1a/ucp1, respectively. Nitrate acquisition rate was accelerated in aox1a/ucp1, but its transport activity was decreased, which resulted in low nitrate content and nitrate reductase activity under low N condition. The C/N ratio in seeds, but not in leaves, is higher in aox1a/ucp1 than that in Col-0, aox1a and ucp1 under low N condition. RNA-seq analysis revealed that many genes involved in photosynthesis and C/N metabolism were markedly down-regulated in aox1a/ucp1 under low N stress. These results highlight the key roles of UCP1 and AOX1a in modulating photosynthetic capacity, C/N assimilation and distribution under low N stress.

Ionothermal-Transformation Strategy to Synthesize Hierarchically Tubular Porous Single-Iron-Atom Catalysts for High-Performance Zinc-Air Batteries.

Inexpensive carbon-based nitrogen-coordinated iron single-atom catalysts (CN-FeSACs) have been recently demonstrated as the most promising platinum substitutions for boosting the sluggish oxygen electrode performance in fuel cells and metal-air batteries. However, it is still a great challenge to develop economical and effective CN-FeSACs satisfying the needs of high output power. Herein, an ionothermal-transformation strategy is proposed to synthesize hierarchically tubular porous CN-FeSACs with an ultrahigh special surface area of 2500 m2 g-1 to host abundant single-atom iron sites with an attempt to simultaneously boost sluggish oxygen reduction reaction (ORR) kinetics and mass transport. Benefiting from the unique feature, the final obtained material shows an ORR half-wave potential of 0.885 V, higher than that of benchmark Pt/C (0.850 V). When assembled into zinc-air battery, a large peak power density of 208 mW cm-2 is achieved, which is far superior to that of Pt/C (119 mW cm-2). This work provides an economical and feasible strategy to prepare hierarchically porous CN-FeSACs for energy conversion.

Reaction Behavior of Porous TiAl3 Intermetallics Fabricated by Thermal Explosion with Different Particle Sizes.

Porous TiAl3 intermetallics were prepared by the thermal explosion (TE) and space holder method with different particle sizes of Ti and Al powders, and their reaction behaviors were investigated. The results showed that with the increase in the particle size of the Ti and Al powders, the interfacial contact between the particles decreased, resulting in low interfacial energy and reaction activity, making the process difficult to initiate. Meanwhile, the heat flow rose from 358.37 J/g to 730.17 J/g and 566.74 J/g due to the extension of the solid-liquid diffusion time. The TiAl3 structures obviously expanded, and the formation of connected pore channels promoted the porosity. Only when the Ti and Al particle sizes were both small did the solid-solid diffusion significantly appear. At the same time, the TE reaction weakened, so the product particles had no time to fully grow. This indicates that the particle size of the raw materials controlled the TE reaction process by changing the solid-liquid diffusion reaction time and the degree of solid-phase diffusion.

The Wear Behavior of the Laser Cladded Ti-Al-Si Composite Coatings on Ti-6Al-4V Alloy with Additional TiC.

In this study, the Ti-Al-Si + xTiC (x = 0, 2, 6, 10 wt.%) composite coatings, each with a different content of TiC were fabricated on a Ti-6Al-4V alloy by laser surface cladding. The microstructure of the prepared coatings was analyzed by the scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The microhardness and the wear resistance of these coatings were also evaluated. The results show that α-Ti, Ti3Al, Ti5Si3, TiAl3, TiAl, Ti3AlC2 and TiC particles can be found in the composites. The microstructure can obviously be refined by increasing the content of TiC particles, while the microhardness increases and the coefficient of friction decreases. The Ti-Al-Si-6TiC composite shows the best wear resistance, owing to its relatively fine microstructure and high content of TiC particles. The microhardness of this coating is 5.3 times that of the substrate, while the wear rate is only 0.43 times. However, when the content of TiC was up to 10 wt.%, the original TiC could not be dissolved completely during the laser cladding process, leading to formation of cracks on the coatings.

Facile synthesis of iron oxide supported on porous nitrogen doped carbon for catalytic oxidation.

Iron oxide (FexOy) supported on porous nitrogen doped carbon is synthesized by a facile pyrolysis method. SiO2 and NaNO3 are used as the template and activation agent respectively for porous structure generation and large specific surface area (SSA) creation. The obtained materials show superior catalytic oxidation ability and can activate peroxymonosulfate (PMS) in a wide pH range (3-9) to degrade organic pollutants. The degradation process is a two-stage reaction, including a rapid initial decay and a following slow reaction stage. According to the free radical quenching experiments, electron paramagnetic resonance (EPR) spectroscopy analysis, and electrochemical tests, the superoxide radical (O2-) and singlet oxygen (1O2) are proved to play crucial roles in organics degradation. The high SSA (773 m2 g-1), abundant of structural defects, and synergistic effect between FexOy and the nitrogen doped carbon are the key factors for the enhanced activity. The catalysts in this study can be synthesized easily and contain no toxic metals, thus should have great potential in the wastewater remediation.

A palladium doped 1T-phase molybdenum disulfide-black phosphorene two-dimensional van der Waals heterostructure for visible-light enhanced electrocatalytic hydrogen evolution.

The electrocatalytic hydrogen evolution reaction (HER) is a green chemistry route for sustainable energy production. Compared to 2H-phase molybdenum disulfide (MoS2), the 1T-phase MoS2 (1T-MoS2) has higher theoretical activity and faster charge transfer kinetics, but the HER performance of 1T-MoS2 is commonly hindered by limited active edge/defect as well as poor structural stability. Herein, we synthesize a well-defined 2D vdW heterostructure composed of Pd doped 1T-MoS2 and black phosphorus (BP) nanosheets via electrostatic self-assembly. The spontaneous Pd doping under mild reaction conditions could introduce catalytically active sulfur vacancies in MoS2 without triggering a wide range of 1T to 2H phase transformation. The hetero-interfacial charge transfer from BP to Pd-1T-MoS2 can effectively improve the intrinsic activity of Pd-1T-MoS2 with a relatively low S vacancy concentration and simultaneously stabilize the 1T-phase structure. Due to the wide-range light absorption of BP nanosheets and the high carrier mobilities of 2D materials, the HER activity of the obtained Pd-1T-MoS2/BP could be further enhanced under ≥420 nm visible light illumination.

Enterovirus 71 induces autophagy in mice via mTOR inhibition and ERK pathway activation.

AIMS: Enterovirus 71 (EV71) is one of the main viruses that cause hand-foot-mouth disease; however, its pathogenic mechanism remains unclear. This study characterized the relationship between EV71 infection and autophagy in vivo and explored the molecular mechanism underlying EV71-induced autophagy. MATERIALS AND METHODS: A mouse model of EV71 infection was prepared by intraperitoneally injecting one-day-old BALB/c suckling mice with 30 µL/g of EV71 virus stock solution for 3 days. The behavior, fur condition, weight, and mice mortality were monitored, and disease scores were calculated. The pathological damage to the brain, lung, and muscle tissues after the viral infection was assessed by hematoxylin and eosin staining. Western blot and immunofluorescence analyses were used to detect the expression levels of viral protein 1, Beclin-1, microtubule-associated protein light chain 3B, mammalian target of rapamycin (mTOR), phosphorylated (p)-mTOR, extracellular signal-regulated protein kinase (ERK) 1/2, and p-ERK. KEY FINDINGS: EV71 infection can trigger autophagy in the brains, lungs, and muscles of infected mice. The autophagy response triggered by EV71 is achieved by the simultaneous mTOR inhibition and the ERK pathway activation. Blocking the mTOR pathway may aggravate autophagy, whereas ERK inhibition alleviates autophagy but cannot completely prevent it. SIGNIFICANCE: EV71 infection can induce autophagy in mice, involving mTOR and ERK signaling pathways. These two signaling pathways are independent and do not interfere with each other.

Carbon-Supported Single Metal Site Catalysts for Electrochemical CO2 Reduction to CO and Beyond.

The electrochemical CO2 reduction reaction (CO2 RR) is a promising strategy to achieve electrical-to-chemical energy storage while closing the global carbon cycle. The carbon-supported single-atom catalysts (SACs) have great potential for electrochemical CO2 RR due to their high efficiency and low cost. The metal centers' performance is related to the local coordination environment and the long-range electronic intercalation from the carbon substrates. This review summarizes the recent progress on the synthesis of carbon-supported SACs and their application toward electrocatalytic CO2 reduction to CO and other C1 and C2 products. Several SACs are involved, including MNx catalysts, heterogeneous molecular catalysts, and the covalent organic framework (COF) based SACs. The controllable synthesis methods for anchoring single-atom sites on different carbon supports are introduced, focusing on the influence that precursors and synthetic conditions have on the final structure of SACs. For the CO2 RR performance, the intrinsic activity difference of various metal centers and the corresponding activity enhancement strategies via the modulation of the metal centers' electronic structure are systematically summarized, which may help promote the rational design of active and selective SACs for CO2 reduction to CO and beyond.

Easily Regenerated CuO/γ-Al2O3 for Persulfate-Based Catalytic Oxidation: Insights into the Deactivation and Regeneration Mechanism.

In this work, γ-Al2O3-supported CuO (c-CuO/Al2O3) materials are successfully synthesized using a novel impregnation-precipitation-decomposition method. The obtained c-CuO/Al2O3 catalyst shows excellent catalytic activities for bisphenol A (BPA) degradation with sodium persulfate (PDS) as an oxidant. Radical quenching tests and electron paramagnetic resonance (EPR) studies indicate that PDS activation is a combined mechanism involving both free radical and nonfree radical pathways. In a continuous large-scale degradation process, about 1.78 L of 20 ppm BPA can be completely removed within 480 min. Although c-CuO/Al2O3 can be deactivated after several reaction cycles, the catalytic activity can be regenerated after simple aerobic calcination. X-ray photoelectron spectroscopy (XPS) and Raman analysis confirm that the deactivation of c-CuO/Al2O3 should be attributed to the conversion of Cu(II) to Cu(I). The aerobic calcination could oxidize Cu(I) back to Cu(II), thus recovering the catalytic activity. In addition, the density functional technology (DFT) and temperature-programmed oxidation (TPD) results reveal that γ-Al2O3 can not only serve as a carrier to anchor the CuO particles but also can adsorb and activate PDS by introducing more basic sites on the surface. c-CuO/Al2O3 has high activity and can be regenerated easily, thus having great potential applications for wastewater treatment.

Synergistic Effects of Black Phosphorus/Boron Nitride Nanosheets on Enhancing the Flame-Retardant Properties of Waterborne Polyurethane and Its Flame-Retardant Mechanism.

We applied black phosphorene (BP) and hexagonal boron nitride (BN) nanosheets as flame retardants to waterborne polyurethane to fabricate a novel black phosphorus/boron nitride/waterborne polyurethane composite material. The results demonstrated that the limiting oxygen index of the flame-retarded waterborne polyurethane composite increased from 21.7% for pure waterborne polyurethane to 33.8%. The peak heat release rate and total heat release of the waterborne polyurethane composite were significantly reduced by 50.94% and 23.92%, respectively, at a flame-retardant content of only 0.4 wt%. The superior refractory performances of waterborne polyurethane composite are attributed to the synergistic effect of BP and BN in the gas phase and condensed phase. This study shows that black phosphorus-based nanocomposites have great potential to improve the fire resistance of polymers.

An efficient and environmentally friendly process for the reduction of SO2 by using waste phosphate mine tailings as adsorbent.

The emission of SO2 and the disposal of waste phosphate mine tailings are generally regarded as two major environmental issues in phosphorus chemical activities. In this paper, an environmentally friendly and efficient route for removing SO2 from phosphorus chemical processes by using waste phosphate mine tailings as adsorbent was proposed. It was indicated that the desulfurization performance of the waste phosphate mine tailings was better than that of its raw ore. The characterization analysis illustrated that higher content of CaMg(CO3)2 was shown on the waste phosphate mine tailings, which played a dominant role in determining the better desulfurization activity. In contrast, the accumulation of PO43- and H+ ions resulted from the dissolution of Ca5(PO4)3F on the raw ore caused negative effect on SO2 removal. In the typical desulfurization system, the produced sulfuric acid from desulfurization process was used to decompose phosphate mine tailings, and these spent tailings can be subsequently applied as raw materials for the production of phosphorus products. As a result, the present approach can achieve the dual goal of reducing the cost of desulfurization process and recycling the waste tailings, which is of great environmental and economic significance.

N-Butyllithium-Treated Ti3C2Tx MXene with Excellent Pseudocapacitor Performance.

MXenes, a family of two-dimensional (2D) transition-metal carbide and nitride materials, are supposed to be promising pseudocapacitive materials because of their high electronic conductivity and hydrophilic surfaces. MXenes, prepared by removing the "A" elements of their corresponding MAX phases by hydrofluoric acid (HF) or LiF-HCl etching, possess abundant terminal groups like -F, -OH, and -O groups. It has been proven that the MXenes with fewer -F terminal groups and more -O groups showed a higher pseudocapacitor performance. In organic reactions, -OH and -X (X = halogen) groups could turn to ether groups in strong nucleophilic reagent. Inspired by that, herein, we report an n-butyllithium-treated method to turn the -F and -OH terminal groups to -O groups on the Ti3C2Tx MXenes. Two types of Ti3C2Tx MXenes prepared by either HF or LiF-HCl etching were systematically investigated, and a comparison with the traditional KOH/NaOH/LiOH-treated method was also carried out. It is found that most of the -F terminal groups on the Ti3C2Tx MXenes can be successfully removed by n-butyllithium, and abundant -O terminal groups were formed. The n-butyllithium-treated Ti3C2Tx MXenes show promising applications in high-performance pseudocapacitors. A record high capacitance of 523 F g-1 at 2 mV s-1 was obtained for the n-butyllithium-treated Ti3C2Tx MXenes, and 96% capacity can remain even after 10 000 cycles.

Review on Applications of Black Phosphorus in Catalysis.

As emerging non-metallic semiconductors, black phosphorus (BP) and few-layered BP (phosphorene) have exhibited unique physicochemical properties and promising application prospect for catalysis related fields. In this review, we first introduced the intriguing properties of BP, including high carrier mobility, a wide optical absorption range and tunable direct band gap. We then summarized the recent research progress about the applications of BP as catalysts, mainly focus on photocatalytic water splitting, photocatalytic degradation of organic pollutants and electrocatalytic H2 and O2 evolution. The recent works about other catalytic applications were also introduced.

Reversible intercalation and exfoliation of layered covalent triazine frameworks for enhanced lithium ion storage.

We report that layered covalent triazine frameworks (CTF-1) can be rapidly and reversibly intercalated with either an oxidizing or a non-oxidizing acid based on the acid-base driven mechanism. The obtained CTF-1 intercalated compounds can be readily reacted with nitronium ions and spontaneously exfoliated into 1-2 layered functionalized CTF-1 nanosheets (f-CTF-1) with a high yield of 42%. The f-CTF-1 shows a 2.5 to 3.8 times increase in specific capacitance and much better rate performance when used as an LIB anode.

Partially Etched Ti3 AlC2 as a Promising High-Capacity Lithium-Ion Battery Anode.

MXenes, a family of two-dimensional transition-metal carbide and nitride materials, are thought to be promising materials in energy storage because of their high electronic conductivity, hydrophilic surfaces, and low diffusion barriers. MXenes are generally prepared by removing the "A" elements (A=Al, Si, Sn, etc.) from their corresponding MAX phases by using hydrofluoric acid (HF) and other etching agents, although these "A" elements usually have great volumetric and gravimetric capacities. In a study of the etching progress of Ti3 AlC2 and evaluation of their anode performance in lithium-ion batteries, a partially etched sample (0.5 h-pe Ti3 C2 Tx ) is found to have much higher capacity (160 mAh g-1 , 331.6 mAh cm-3 at 1C) when compared with the fully etched Ti3 C2 Tx (110 mAh g-1 , 190.3 mAh cm-3 at 1C). Moreover, a 99 % capacity retention was observed even after 1000 cycles in the 0.5 h-pe Ti3 C2 Tx anode. This interesting result can be explained, at least in part, by the alloying of the residual Al during lithiation.