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Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g. ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction to value‐added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu‐based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g. ethylene and ethanol). In this work, we develop sulfur‐doped Cu2O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2O‐electrolyte interface, and S‐doped Cu2O undergoes in situ surface reconstruction to generate active S‐adsorbed metallic Cu sites during the CO2 reduction reaction (CO2RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S‐adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2‐to‐formate conversion during the electrochemical CO2RR. [ABSTRACT FROM AUTHOR]

As an essential micronutrient element in organisms, copper controls a host of fundamental cellular functions. Recently, copper-dependent cell growth and proliferation have been defined as "cuproplasia". Conversely, "cuproptosis" represents copper-dependent cell death, in a nonapoptotic manner. So far, a series of copper ionophores have been developed to kill cancer cells. However, the biological response mechanism of copper uptake has not been systematically analyzed. Based on quantitative proteomics, we revealed the crosstalk between copper stress and cuproptosis in cancer cells, and also explored the feasibility of curcumin as anticancer copper ionophore. Copper stress not only couples with cuproptosis, but also leads to reactive oxygen species (ROS) stress, oxidative damage and cell cycle arrest. In cancer cells, a feedback cytoprotection mechanism involving cuproptosis mediators was discovered. During copper treatment, the activation of glutamine transporters and the loss of Fe–S cluster proteins are the facilitators and results of cuproptosis, respectively. Through copper depletion, glutathione (GSH) blocks the cuproptosis process, rescues the activation of glutamine transporters, and prevents the loss of Fe–S cluster proteins, except for protecting cancer cells from apoptosis, protein degradation and oxidative damage. In addition, the copper ionophore curcumin can control the metabolisms of lipids, RNA, NADH and NADPH in colorectal cancer cells, and also up-regulates positive cuproptosis mediators. This work not only established the crosstalk between copper stress and cuproptosis, but also discolored the suppression and acceleration of cuproptosis by GSH and curcumin, respectively. Our results are significant for understanding cuproptosis process and developing novel anticancer reagents based on cuproptosis. This work not only established the crosstalk between copper stress and cuproptosis, but also discolored the suppression and acceleration of cuproptosis by glutathione and curcumin, respectively. [Display omitted] • The crosstalk between copper stress and cuproptosis was disclosed. • Copper stress also leads to ROS stress, oxidative damage and cell cycle arrest. • GSH blocks the cuproptosis process, along with multiply cytoprotective mechanisms. • Curcumin controls the metabolisms of lipids, RNA, NADH and NADPH. • Curcumin up-regulates positive cuproptosis mediators in colorectal cancer cells. [ABSTRACT FROM AUTHOR]

A growing number of clinical and animal studies suggest that the nucleus accumbens (NAc), especially the shell, is involved in the pathogenesis of temporal lobe epilepsy (TLE). However, the role of parvalbumin (PV) GABAergic neurons in the NAc shell involved in TLE is still unclear. In this study, we induced a spontaneous TLE model by intrahippocampal administration of kainic acid (KA), which generally induce acute seizures in first 2 h (acute phase) and then lead to spontaneous recurrent seizures after two months (chronic phase). We found that chemogenetic activation of NAc shell PV neurons could alleviate TLE seizures by reducing the number and period of focal seizures (FSs) and secondary generalized seizures (sGSs), while selective inhibition of PV exacerbated seizure activity. Ruby-virus mapping results identified that the hippocampus (ventral and dorsal) is one of the projection targets of NAc shell PV neurons. Chemogenetic activation of the NAc-Hip PV projection fibers can mitigate seizures while inhibition has no effect on seizure ictogenesis. In summary, our findings reveal that PV neurons in the NAc shell could modulate the seizures in TLE via a long-range NAc-Hip circuit. All of these results enriched the investigation between NAc and epilepsy, offering new targets for future epileptogenesis research and precision therapy. • Chemogenetic activation of PV (+) neurons in the NAc shell attenuates seizures. • Chemogenetic inhibition of NAc shell PV (+) neurons aggravates seizures. • The ventral and dorsal hippocampus is innervated by the NAc PV projections. • Chemogenetic activation of the NAc-Hippocampal PV projection fibers also has an antiepileptic effect. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction to value‐added chemicals/fuels provides a promising way to mitigate CO2 emission and alleviate energy shortage. CO2‐to‐CO conversion involves only two‐electron/proton transfer and thus is kinetically fast. Among the various developed CO2‐to‐CO reduction electrocatalysts, transition metal/N‐doped carbon (M‐N‐C) catalysts are attractive due to their low cost and high activity. In this work, recent progress on the development of M‐N‐C catalysts for electrochemical CO2‐to‐CO conversion is reviewed in detail. The regulation of the active sites in M‐N‐C catalysts and their related adjustable electrocatalytic CO2 reduction performance is discussed. A visual performance comparison of M‐N‐C catalysts for CO2 reduction reaction (CO2RR) reported over the recent years is given, which suggests that Ni and Fe‐N‐C catalysts are the most promising candidates for large‐scale reduction of CO2 to produce CO. Finally, outlooks and challenges are proposed for future research of CO2‐to‐CO conversion. [ABSTRACT FROM AUTHOR]

It is widely accepted that single Ni atoms coordinated with N can highly efficiently promote CO2 electroreduction to CO. Very recently, probably due to limited access to high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) techniques, a misleading conclusion that nitrogen‐doped carbon‐encapsulated Ni nanoparticles (NPs) possess activity similar to that of single Ni atoms was reported and was quickly followed by several similar reports. The current contribution aims to end this misleading conclusion by performing well‐designed experiments and solid theoretical analyses. For this purpose, a series of Ni/nitrogen‐doped graphite (Ni‐NG) catalysts with different dominant Ni species (single Ni atom, nitrogen‐doped carbon‐encapsulated Ni NPs, or both) are fabricated and comparatively studied for CO2 electroreduction to CO. Two previous studies that reported nitrogen‐doped carbon‐encapsulated Ni NPs catalysts are reinvestigated, and the existence of single Ni atoms is confirmed by HAADF‐STEM. In addition, after leaching out most of the Ni NPs by a strong acid, the activity of those catalysts does not decrease but increases slightly. Density functional theory results suggest that nitrogen‐doped carbon‐encapsulated Ni NPs are highly selective for the hydrogen evolution reaction (HER) rather than for CO2‐to‐CO conversion. Overall, both systematic experimental and theoretical analyses clearly reveal that the nitrogen‐doped carbon‐encapsulated Ni NPs are not active for CO2 electroreduction. [ABSTRACT FROM AUTHOR]

Dramatically increased CO2 concentration from several point sources is perceived to cause severe greenhouse effect towards the serious ongoing global warming with associated climate destabilization, inducing undesirable natural calamities, melting of glaciers, and extreme weather patterns. CO2 capture and utilization (CCU) has received tremendous attention due to its significant role in intensifying global warming. Considering the lack of a timely review on the state-of-the-art progress of promising CCU techniques, developing an appropriate and prompt summary of such advanced techniques with a comprehensive understanding is necessary. Thus, it is imperative to provide a timely review, given the fast growth of sophisticated CO2 capture and utilization materials and their implementation. In this work, we critically summarized and comprehensively reviewed the characteristics and performance of both liquid and solid CO2 adsorbents with possible schemes for the improvement of their CO2 capture ability and advances in CO2 utilization. Their industrial applications in pre- and post-combustion CO2 capture as well as utilization were systematically discussed and compared. With our great effort, this review would be of significant importance for academic researchers for obtaining an overall understanding of the current developments and future trends of CCU. This work is bound to benefit researchers in fields relating to CCU and facilitate the progress of significant breakthroughs in both fundamental research and commercial applications to deliver perspective views for future scientific and industrial advances in CCU. [ABSTRACT FROM AUTHOR]

Reactive species, such as.PO2 and HOPO, are considered of upmost importance in flame inhibition and catalytic combustion processes of fuels. However, the underlying chemistry of their formation remains speculative due to the unavailability of suitable analytical techniques that can be used to identify the transient species which lead to their formation. This study elucidates the reaction mechanisms of the formation of phosphoryl species from dimethyl methyl phosphonate (DMMP) and dimethyl methyl phosphoramidate (DMPR) under well‐defined oxidative conditions. Photoelectron photoion coincidence techniques that utilized vacuum ultraviolet synchrotron radiation were applied to isomer‐selectively detect the elusive key intermediates and stable products. With the help of in situ recorded spectral fingerprints, different transient species, such as PO2 and triplet O radicals, have been exclusively identified from their isomeric components, which has helped to piece together the formation mechanisms of phosphoryl species under various conditions. It was found that.PO2 formation required oxidative conditions above 1070 K. The combined presence of O2 and H2 led to significant changes in the decomposition chemistry of both model phosphorus compounds, leading to the formation of.PO2. The reaction.PO+O2→.PO2+O: was identified as the key step in the formation of.PO2. Interestingly, the presence of O2 in DMPR thermolysis suppresses the formation of PN‐containing species. In a previous study, PN species were identified as the major species formed during the pyrolysis of DMPR. Thus, the findings of this study has shed light onto the decomposition pathways of organophosphorus compounds, which are beneficial for their fuel additive and fire suppressant applications. [ABSTRACT FROM AUTHOR]

Increasing the amount of accessible active sites to reactants is an effective way to enhance electrocatalytic activity. Although single-atom catalysts are claimed to be capable of achieving 100% atomic utilization, there may be abundant single-atom sites buried and inaccessible to reactants in practice. Herein, two Ni, N-doped carbon catalysts with Ni-N x atomic sites are comparatively studied for CO 2 electroreduction. In contrast to the Ni-N x /Carbon nanosheets with Ni loading of 2.42 wt%, the Ni-N x /Carbon black with lower Ni loading of 0.16 wt% excitingly exhibits higher activity for CO production. The atomically dispersed Ni-Nx sites over carbon black surface benefit the exposure and utilization of single-atom sites, leading to a significant increase of TOF from 2140 to 100,347 h−1 at − 0.8 V. Particularly, an extraordinarily high current density up to 300 mA cm−2 with CO selectivity of ∼100 % are achieved for Ni-N x /CB in the flow cell. This work demonstrates the significance of increasing single-atom site utilization. [Display omitted] • Ni-Nx/CNS and Ni-Nx/CB catalysts with Ni-Nx sites are synthesized for CO2RR. • Ni-Nx/CB catalyst exhibits high CO selectivity and TOF for CO2 conversion. • Ni-Nx/CB catalyst with low Ni loading exhibits high single-Ni-atoms utilization. • High current density of > 300 mA cm-2 is achieved in the flow cell. [ABSTRACT FROM AUTHOR]

This paper focuses on the development of a work analysis support system for distribution processing and presents a case study of work analysis at a retail clothing order fulfillment center. The system comprises ultrasonic sensors for measuring a worker's flow line and a smartphone for measuring the worker's dominant hand acceleration. Models for estimating the worker's motion were derived from the data obtained. Candidate estimation models were the statistical models linear discriminant function, decision tree, and k-nearest neighbor algorithm, and we used generalization error by crossvalidation as an index for choosing the optimal estimation model. The system was applied to the example of analyzing order picking in a clothing distribution center. The k coefficient obtained indicated the degree of matching between the results of video analysis and tracking by our system to be 0.6 or more, which confirmed the validity of our system. [ABSTRACT FROM AUTHOR]

Macrophage polarization serves an important role in immune regulation that is regulated by T-cell immunoglobulin-mucin-3 (Tim-3). The objective of the present study was to explore the role of 1,25-dihydroxy-vitamin D3 [1,25(OH)2D3] in macrophage polarization. Plasmid transfection techniques were applied to prepare RAW264.7 cells with silenced or overexpressed Tim-3 gene. ELISAs were used to examine the level of inflammatory factors secreted by macrophages. Proteins levels were determined by western blot analysis. mRNAs expression levels were assessed using reverse transcription quantitative polymerase chain reaction. It was identified that 1,25(OH)2D3 upregulated Tim-3 levels and promoted the secretion of interleukin (IL)-10. 1,25(OH)2D3 was also observed to increase the level of transforming growth factor-β and to inhibit tumor necrosis factor-α and IL-6. The results also suggested that Tim-3 gene silencing induced macrophages polarization to classically activated macrophages (M1), and that overexpression of the Tim-3 gene induced macrophage polarization to alternatively activated macrophages (M2). 1,25(OH)2D3 treatment upregulated the expression level of Tim-3 in macrophages, which promoted cell polarization to M2 and inhibited polarization to M1. The data from the present study indicated that Tim-3 may induce macrophage polarization to M2, and that 1,25(OH)2D3 produced immunosuppressive effects by upregulating Tim-3. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) nanosheets (NSs) have shown significant promise as nanofillers in mixed-matrix membranes (MMMs) for overcoming the trade–off between permeability and selectivity. However, the effective regulation of the interlayer spacing of 2D NSs on the separation performance of MMMs remains a challenge. In this study, we adjusted the interlayer spacing of 2D NSs by intercalating layered double hydroxide (LDH) with different anions. The LDH NSs were embedded in a commercial polyether–block–amide (PEBAX 1657) to form MMMs for CO 2 separation. The results of our study indicated that increasing the interlayer spacing and intercalated carboxyl groups of the LDH NSs facilitated the fast permeation of CO 2 through the membranes. The prepared PEBAX/LDH MMMs (P–LDH series) exhibited promising CO 2 permeability, accompanied by good CO 2 /N 2 and CO 2 /CH 4 selectivities. In addition, we demonstrated that methanol enabled the microstructure optimization of the prepared PEBAX/LDH MMMs. The synergistic effects of the intercalated LDH NSs and methanol post–treatment were studied to improve CO 2 separation. The prepared MMMs were subjected to scanning electron microscopy (SEM), X-ray diffraction (XRD), FTIR, thermogravimetric analysis (TG), time-lag, positron annihilation lifetime spectroscopy (PALS), and mechanical tests. Methanol-treated MMMs (M–P–LDH series) showed significantly improved CO 2 permeability, outstanding CO 2 /N 2 selectivity, and excellent stability for long-term operation under harsh conditions, surpassing Robeson's 2008 upper-bound limit. [Display omitted] • Construction of specific LDH transport channels for improved CO 2 diffusion. • Enhancement of the CO 2 permeability and CO 2 /N 2 selectivity by post-treated methanol. • Separation performance surpassing the 2008 Robeson's upper bound for CO 2 /N 2 gas pair. [ABSTRACT FROM AUTHOR]

The thermal behavior of organophosphorus compounds is intricate and poorly understood but crucial for understanding gas-phase flame inhibition, syntheses of thermally active phosphorus-based reactive precursors, catalytic combustion, incineration of toxic nerve gases, and astrochemistry. In this work, the pyrolysis of dimethyl phosphoramidate was investigated using photoion photoelectron coincidence spectroscopy in combination with vacuum ultraviolet synchrotron radiation. This technique enables isomer-selective detection of reactive intermediates, which are crucial in the understanding of the decomposition process. Combined with quantum chemical calculations, the experimental results permit the formulation of a comprehensive pyrolysis reaction pathway for dimethyl phosphoramidate, consisting of several reactive phosphorus species on four possible decomposition pathways. Compared to the decomposition of dimethyl methyl phosphonate, which leads exclusively to the formation of PO radicals, substitution of the methyl with an amino group most notably yields phosphorus nitride (P≡N). This mostly favored reaction pathway involves the subsequent loss of methanol and formaldehyde to yield three PONH2 tautomers, which eliminate water to generate P≡N. The thermally induced production of PN species and its possible role in flame inhibition has not previously been reported. In addition, the adiabatic ionization energy of O=P(OCH3)2NH2 was determined to be 9.79±0.02 eV. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bimetallic catalysts for CO 2 hydrogenation to methanol are critically reviewed. • Strategies to enhance the performance of Ni, Cu, Pd-based bimetallic systems. • The CO 2 hydrogenation mechanism for bimetallic catalysts is summarized. • Future prospectives on the design of bimetallic catalysts are proposed. The continuous growth in carbon dioxide (CO 2) emissions has caused serious environmental issues. To solve this problem, catalytic hydrogenation of CO 2 to methanol by efficient catalysts supplies a promising method to reduce the greenhouse effect and produce value-added chemicals and fuels. The tunability provided by the formation of bimetallic compounds helps to develop catalysts with superior activity, selectivity, and stability to single metals. Thus, bimetallic catalysts have been arising as a promising candidate for methanol production recently, and a timely review is highly desired. Herein, we mainly discussed the advances of the bimetallic catalysts (Ni, Cu, and Pd-based bimetallic system) for methanol production in recent years and summarized the various strategies to enhance the catalytic activity, including regulating the active species, nanoparticles size, and catalysts support. Mechanistic insights for methanol production over the bimetallic catalysts are also included, which commonly proceed via the formate or CO pathway. This review summarizes progress in these aspects and provides ideas for the future design of bimetallic catalysts with high CO 2 conversion and methanol selectivity. [ABSTRACT FROM AUTHOR]

In this work we report synthesis and flame retardant application of novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) based phosphonamidates. Two mono and one bis DOPO-phosphonamidates were synthesized and incorporated in polyether based polyurethane (PU) manufacturing process. For the comparison of fire performance of these DOPO-phosphonamidates, we have chosen commercially available flame retardants (TCPP, DOPO and Exolit ® OP 560) commonly used in flexible PU foam manufacturing. UL94 HBF fire results of various PU foam formulations indicate that DOPO-phosphonamidates exhibit superior fire performance as compared to the commercial flame retardants. 6,6′-(ethane-1,2-diylbis-(azanediyl)-bis-(6H-dibenzo[c,e][1,2]-oxaphosphine-6-oxide (EDAB-DOPO))/foam formulations exhibit the best fire performance as compared to other DOPO-phosphonamidate/foam formulations. A concentration of only 5% EDAB-DOPO on wt. of polyol is needed to achieve a HF1 rating. Thermal decomposition studies of the DOPO-phosphonamidate/foam formulations indicate their limited condensed phase interaction. In TGA experiments, a very small residue (<5%) was observed at 800 °C for all PU formulations. Additionally EDAB-DOPO showed evidence of intermediate condensed phase interaction in the first stage of PU foam decomposition. Direct insertion probe (DIP) – MS studies indicate that mono DOPO-phosphonamidates volatilize primarily in the first stage of thermal decomposition of PU foams whereas the EDAB-DOPO, being thermally more stable is only detected in gas phase in the second stage. Like in case of TCPP/PU foam formulation, the increase in the CO/CO 2 ratio in the cone calorimeter experiments for the DOPO-phosphonamidate/foam formulation further proves the gas phase activity (flame inhibition) of these DOPO-phosphonamidates. EDAB-DOPO being thermally more stable seems to offer more sustained gas phase activity during the entire burning stage of PU foams in cone calorimeter experiments. Higher thermal stability of EDAB-DOPO may explain its superior flame retardant efficacy among all the DOPO-phosphonamidates investigated in this study. [ABSTRACT FROM AUTHOR]

The production of phosphoryl species (PO, PO2, HOPO) is believed to be of great importance for efficient flame-retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO2 is absent. It can be concluded that the formation of PO2 needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates OPCH3, H2CPOH, and H2CP(O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP. [ABSTRACT FROM AUTHOR]

Highlights: [•] Flame retardant application areas and application technologies. [•] Traditional flame retardant coatings. [•] Development in flame retardant chemistry for application in coatings. [ABSTRACT FROM AUTHOR]

In this study, we have investigatedthe structure–flame-retardant(FR) efficacy relationships of phosphoramidates (PRs) on flexiblepolyurethane foam (FPUF). FPUFs that contain model monosubstitutedsecondary PRs, monosubstituted tertiary PRs, and trisubstituted secondaryPRs were prepared and evaluated for FR efficacy and thermal decompositioncharacteristics. The fire test results indicate that methyl esterPRs exhibit better FR behavior, compared to analogous phenyl esterderivatives at equal weight percentage in polyurethane (PU) foams.Within the same class of PRs, the monoallyl derivatives exhibitedthe highest level of flame retardancy. The multiallyl PR derivativesdid not offer any advantage, in terms of improved flame retardancy.Evolved gas analysis from the thermal degradation of PU foams indicatesthat the PRs are volatilized in the first stage of thermal decompositionand are primarily active in the gas phase with the exception of thetriallyl-PR derivative, which is primarily active in the condensedphase. [ABSTRACT FROM AUTHOR]

Abstract: In this study the structural effect of different phosphorus compounds on the flame retardant (FR) properties of flexible polyurethane foams (FPUF) was investigated. A series of organophosphorus compounds (phosphonates, phosphates and phosphoramidates) with systematical structure variations were synthesized and incorporated into the flexible foam during its polymerization process. The flame-retarding efficiency of these phosphorus compounds was subsequently evaluated by subjecting their corresponding flame-retarded foams to standard fire tests such as limiting oxygen index (LOI), BKZ-vertical burning test and UL 94-horizontal burning test for foamed materials. It was observed that the synthesized phosphonates and analogous phosphoramidates were more effective than the corresponding phosphates. The presence of an allyl moiety within the molecular structure further improved the FR efficacy of the phosphonate and phosphoramidate compounds, whereas a benzyl group reduced the flame retardant efficiency significantly. The thermogravimetric (TGA) analysis and pyrolysis combustion flow calorimetry (PCFC) results for the FPUF indicated that the most effective FRs might act predominantly in gas phase and exhibit lower condensed phase action (i.e. catalyze the decomposition of FPUF to happen at lower temperatures). Mass spectrometric analysis of FRs indicates that phosphonate and phosphoramidate derivatives appear to support the phosphoryl radical formation more than the investigated phosphate compounds. [Copyright &y& Elsevier]

The membrane Electrode Assemblies (MEAs) electrolyzers are the most attractive systems for the electrolytic conversion of CO 2 into commodity chemicals and fuels at commercially relevant current densities. Suppressing the hydrogen evolution reaction (HER) is vital to the highly efficient electrochemical CO 2 reduction reaction (CO 2 RR). However, little attention has been paid to the HER. Herein, polybenzimidazole (PBI) Janus membranes with significant hydrophobic/hydrophilic asymmetric surface wettability were constructed for regulating the HER in CO 2 RR. The HER was modulated by adjusting the microstructure and surface hydrophobicity of the membrane as well as the CO 2 feeding method. The p-PBI-HCF MEA showed a significant suppression of HER and a 6-fold improvement in CO selectivity over p-PBI MEA. The p-PBI-HCF exhibited superior CO 2 RR performance in MEA compared to commercial membranes (FAA-3-50 and Nafion115). At 2.0–3.0 V, the CO Faraday efficiency (FE CO) of the p-PBI-HCF MEA electrolyzer remained above 92%. The optimal energy efficiency range was between 2.0 and 2.4 V when the FE CO was close to 100%. The p-PBI-HCF provided 92% FE CO and a current density of 225 mA cm−2 at 3 V. This work provides guidelines for the development of viable PBI membranes and MEAs for CO 2 RR. [Display omitted] • HER was regulated by microstructure and surface hydrophobicity as well as by the humidified or dry state of CO 2. • HER was significantly suppressed and the CO selectivity was improved by 6 times after the regulatory measures were applied. • Controlling the local microenvironment at the cathode is vital to avoid high HER. • The FE CO approached 100% at 2.0–2.4 V while demonstrating the best efficiency range. [ABSTRACT FROM AUTHOR]

Segmenting the irregular pancreas and inconspicuous tumor simultaneously is an essential but challenging step in diagnosing pancreatic cancer. Current deep-learning (DL) methods usually segment the pancreas or tumor independently using mixed image features, which are disrupted by surrounding complex and low-contrast background tissues. Here, we proposed a deep causal learning framework named CausegNet for pancreas and tumor co-segmentation in 3D CT sequences. Specifically, a causality-aware module and a counterfactual loss are employed to enhance the DL network's comprehension of the anatomical causal relationship between the foreground elements (pancreas and tumor) and the background. By integrating causality into CausegNet, the network focuses solely on extracting intrinsic foreground causal features while effectively learning the potential causality between the pancreas and the tumor. Then based on the extracted causal features, CausegNet applies a counterfactual inference to significantly reduce the background interference and sequentially search for pancreas and tumor from the foreground. Consequently, our approach can handle deformable pancreas and obscure tumors, resulting in superior co-segmentation performance in both public and real clinical datasets, achieving the highest pancreas/tumor Dice coefficients of 86.67%/84.28%. The visualized features and anti-noise experiments further demonstrate the causal interpretability and stability of our method. Furthermore, our approach improves the accuracy and sensitivity of downstream pancreatic cancer risk assessment task by 12.50% and 50.00%, respectively, compared to experienced clinicians, indicating promising clinical applications. [ABSTRACT FROM AUTHOR]

Hydrazine non-enzymatic electrochemical determination is regarded as a promising and simple approach which shows great significance in the field of environmental monitoring and medical analysis. By employment of Co 3 O 4 /N-doped carbon nanocomposites as electrochemical sensor, the goal of constructing highly sensitive non-enzymatic determination of hydrazine in low concentration level can be achieved. In this work, chitosan is utilized as the nitrogen and carbon source to prepare Co 3 O 4 /N-doped carbon nanocomposites via a precipitation method and subsequent thermal treatment. The chemical composition and morphology of Co 3 O 4 /N-doped carbon are explored via Raman spectroscopy, XPS, XRD, FESEM and HRTEM. The electrochemical performances of Co 3 O 4 /N-doped carbon modified electrode towards hydrazine detection are studied via cyclic voltammetry and amperometry techniques. The fabricated Co 3 O 4 /N-doped carbon based sensor exhibited a rather wide linear range from 0.50 to 977.40 μM, an excellent sensitivity of 56.63 μA mM−1 and a very low detection limit of 0.11 μM (S/N = 3). The fabricated sensor also possessed good repeatability, reproducibility, electivity, as well as pretty good stability. • Co 3 O 4 /N-doped carbon composite was prepared as efficient electron mediator. • The N-doped carbon promotes the conductivity of Co 3 O 4. • It exhibited excellent sensitivity, selectivity, repeatability, and reproducibility. • Very low detection limit (0.11 μM) for the detection of N 2 H 4 was obtained. [ABSTRACT FROM AUTHOR]

Self‐renewal and differentiation of embryonic stem cells (ESCs) are influenced by protein O‐linked β‐N‐acetylglucosamine (O‐GlcNAc) modification, but the underlying mechanism remains incompletely understood. Herein, we report the identification of 979 O‐GlcNAcylated proteins and 1340 modification sites in mouse ESCs (mESCs) by using a chemoproteomics method. In addition to OCT4 and SOX2, the third core pluripotency transcription factor (PTF) NANOG was found to be modified and functionally regulated by O‐GlcNAc. Upon differentiation along the neuronal lineage, the O‐GlcNAc stoichiometry at 123 sites of 83 proteins—several of which were PTFs—was found to decline. Transcriptomic profiling reveals 2456 differentially expressed genes responsive to OGT inhibition during differentiation, of which 901 are target genes of core PTFs. By acting on the core PTF network, suppression of O‐GlcNAcylation upregulates neuron‐related genes, thus contributing to mESC fate determination. [ABSTRACT FROM AUTHOR]

Self‐renewal and differentiation of embryonic stem cells (ESCs) are influenced by protein O‐linked β‐N‐acetylglucosamine (O‐GlcNAc) modification, but the underlying mechanism remains incompletely understood. Herein, we report the identification of 979 O‐GlcNAcylated proteins and 1340 modification sites in mouse ESCs (mESCs) by using a chemoproteomics method. In addition to OCT4 and SOX2, the third core pluripotency transcription factor (PTF) NANOG was found to be modified and functionally regulated by O‐GlcNAc. Upon differentiation along the neuronal lineage, the O‐GlcNAc stoichiometry at 123 sites of 83 proteins—several of which were PTFs—was found to decline. Transcriptomic profiling reveals 2456 differentially expressed genes responsive to OGT inhibition during differentiation, of which 901 are target genes of core PTFs. By acting on the core PTF network, suppression of O‐GlcNAcylation upregulates neuron‐related genes, thus contributing to mESC fate determination. [ABSTRACT FROM AUTHOR]

In this study, for the first time, we report a straightforward one-pot method to obtain ZnS with multiple vacancies (V+V−–ZnS). It is found that two new defect energy levels are formed by Zn vacancies and S vacancies, which are close to the valence band (VB) top and conduction band (CB) bottom, respectively. The newly formed energy levels in V+V−–ZnS greatly enhance light absorption: 480 nm and 2.44 eV (V+V−–ZnS) vs. 399 nm and 3.24 eV (ZnS). Moreover, V+V−–ZnS exhibits an evidently improved charge separation efficiency. Thus, V+V−–ZnS shows a high visible-light activity, while ZnS has no response to visible light. This method is simple, and could be extended to mass production. [ABSTRACT FROM AUTHOR]

In this work, we mainly investigate the adsorption properties of the simulated single and mixture wastewaters over porous Bi 2 MoO 6 @BiOCl@MOF-199 (BMO@BOC@MOF-199), including methylene blue (MB), rhodamine blue (RhB), methyl orange (MO) and chromium (VI). It is found that BMO@BOC@MOF-199 has a high adsorption capacity for MB, but a poor adsorption capacity for MO. Specifically, for single MB solution, 67%, 80% and 96% of MB are adsorbed by BMO@BOC, MOF-199 and BMO@BOC@MOF-199, respectively. The higher adsorption capacity of BMO@BOC@MOF-199 could be due to its higher surface area and larger pore volume. For single MO solution, nevertheless, only 16%, 13% and 7% of MO are adsorbed by BMO@BOC, MOF-199 and BMO@BOC@MOF-199, respectively. The different adsorption efficiency for MB and MO could be relative to their different molecular structures, which have different electrostatic interactions with adsorbent surface. For single RhB and single Cr(VI) solution, BMO@BOC@MOF-199 has adsorbed 30% RhB and 10% Cr(VI). In RhB-MO mixture solution, 32% RhB and 9% MO can be adsorbed by BMO@BOC@MOF-199, while in Cr(VI)–RhB-MO mixture solution, 7% Cr(VI), 3% RhB and 42% MO can be adsorbed by BMO@BOC@MOF-199. It is seen that in RhB-MO mixture solution, the adsorption efficiencies of RhB and MO by BMO@BOC@MOF-199 do not obviously change as compared to single RhB and single MO solution, while in Cr(VI)–RhB-MO mixture solution, the adsorption efficiency of MO has increased by 5 times, compared to single MO solution; but the adsorption efficiency of RhB has decreased by 9.7 times as compared to single RhB solution, and the adsorption efficiency of Cr(VI) has decreased slightly, compared to single Cr(VI) solution. The results are mainly attributed to the competitive adsorption on the adsorbent surface. This work can help us to understand the adsorption process for practical wastewater. [Display omitted] • Bi 2 MoO 6 @BiOCl@MOF-199 is got via a one-pot solvothermal method. • BMO@BOC@MOF-199 shows a higher adsorption capacity for MB than MO. • All adsorption process follows the nonlinear pseudo-first and pseudo second order kinetics. • This research work favors to understand adsorption processes for practical wastewater. [ABSTRACT FROM AUTHOR]

High-electron-affinity fluorine and as-resultant surface oxygen vacancies efficiently promote charge separation, thus the synergistic effect of both fluorine substitution and surface fluorine adsorption greatly enhances visible-light activity of BiVO 4. • A simple post-synthesis fluorination method is used to improve the activity of BiVO 4. • Fluorine substitution results in formation of oxygen vacancy. • Surface oxygen vacancies can capture and activate oxygen to form O2−. • As electron traps, surface oxygen vacancies and adsorbed fluorine improve charge separation. • Fluorine substitution and surface adsorption greatly synergistically enhance activity of BiVO 4. Herein, a straightforward fluorination method is employed to enhance the photocatalytic performances of BiVO 4. Compared with untreated BiVO 4 , the visible light activity of treated BiVO 4 sample (0.15F-BiVO 4 , obtained with 0.15 g NH 4 F) has increased by about 1.4 and 4 times for degrading methylene blue (MB) and Rhodamine B (RhB), respectively. The activity enhancement is mainly due to the promoted charge transfer and separation by fluorine substitution for oxygen and surface fluorine adsorption. On one hand, fluorine substitution nearly does not change valence band (VB, 2.71 eV), but upshift conduction band (CB) position (0.23 eV/F-BiVO 4 vs. 0.36 eV/BiVO 4), resulting in an obvious blue shift for light absorption (525 nm/F-BiVO 4 vs. 545 nm/BiVO 4). On the other hand, fluorine substitution results in the formation of oxygen vacancy. Because of the high electron affinity, surface adsorbed fluorine, as well as surface oxygen vacancies as electron traps, have improved charge separation effectively. Moreover, oxygen can easily be captured by surface oxygen vacancies to form O2− species, thus changing reaction pathway. In addition, surface adsorbed fluorine facilitates interfacial charge transfer between dye molecules and photocatalyst. [ABSTRACT FROM AUTHOR]