The zinc finger protein DHHC09 S-acylates the kinase STRK1 to regulate H2O2 homeostasis and promote salt tolerance in rice.

Soil salinity results in oxidative stress and heavy losses to crop production. The S-acylated protein SALT TOLERANCE RECEPTOR-LIKE CYTOPLASMIC KINASE 1 (STRK1) phosphorylates and activates CATALASE C (CatC) to improve rice (Oryza sativa L.) salt tolerance, but the molecular mechanism underlying its S-acylation involved in salt signal transduction awaits elucidation. Here, we show that the DHHC-type zinc finger protein DHHC09 S-acylates STRK1 at Cys5, Cys10, and Cys14 and promotes salt and oxidative stress tolerance by enhancing rice H2O2-scavenging capacity. This modification determines STRK1 targeting to the plasma membrane or lipid nanodomains and is required for its function. DHHC09 promotes salt signaling from STRK1 to CatC via transphosphorylation, and its deficiency impairs salt signal transduction. Our findings demonstrate that DHHC09 S-acylates and anchors STRK1 to the plasma membrane to promote salt signaling from STRK1 to CatC, thereby regulating H2O2 homeostasis and improving salt stress tolerance in rice. Moreover, overexpression of DHHC09 in rice mitigates grain yield loss under salt stress. Together, these results shed light on the mechanism underlying the role of S-acylation in RLK/RLCK-mediated salt signal transduction and provide a strategy for breeding highly salt-tolerant rice.

CD44 splice isoform switching determines breast cancer stem cell state.

Although changes in alternative splicing have been observed in cancer, their functional contributions still remain largely unclear. Here we report that splice isoforms of the cancer stem cell (CSC) marker CD44 exhibit strikingly opposite functions in breast cancer. Bioinformatic annotation in patient breast cancer in The Cancer Genome Atlas (TCGA) database reveals that the CD44 standard splice isoform (CD44s) positively associates with the CSC gene signatures, whereas the CD44 variant splice isoforms (CD44v) exhibit an inverse association. We show that CD44s is the predominant isoform expressed in breast CSCs. Elimination of the CD44s isoform impairs CSC traits. Conversely, manipulating the splicing regulator ESRP1 to shift alternative splicing from CD44v to CD44s leads to an induction of CSC properties. We further demonstrate that CD44s activates the PDGFRß/Stat3 cascade to promote CSC traits. These results reveal CD44 isoform specificity in CSC and non-CSC states and suggest that alternative splicing provides functional gene versatility that is essential for distinct cancer cell states and thus cancer phenotypes.

The protein phosphatase PC1 dephosphorylates and deactivates CatC to negatively regulate H2O2 homeostasis and salt tolerance in rice.

Catalase (CAT) is often phosphorylated and activated by protein kinases to maintain hydrogen peroxide (H2O2) homeostasis and protect cells against stresses, but whether and how CAT is switched off by protein phosphatases remains inconclusive. Here, we identified a manganese (Mn2+)-dependent protein phosphatase, which we named PHOSPHATASE OF CATALASE 1 (PC1), from rice (Oryza sativa L.) that negatively regulates salt and oxidative stress tolerance. PC1 specifically dephosphorylates CatC at Ser-9 to inhibit its tetramerization and thus activity in the peroxisome. PC1 overexpressing lines exhibited hypersensitivity to salt and oxidative stresses with a lower phospho-serine level of CATs. Phosphatase activity and seminal root growth assays indicated that PC1 promotes growth and plays a vital role during the transition from salt stress to normal growth conditions. Our findings demonstrate that PC1 acts as a molecular switch to dephosphorylate and deactivate CatC and negatively regulate H2O2 homeostasis and salt tolerance in rice. Moreover, knockout of PC1 not only improved H2O2-scavenging capacity and salt tolerance but also limited rice grain yield loss under salt stress conditions. Together, these results shed light on the mechanisms that switch off CAT and provide a strategy for breeding highly salt-tolerant rice.

Nivolumab Combination Therapy in Advanced Esophageal Squamous-Cell Carcinoma.

BACKGROUND: First-line chemotherapy for advanced esophageal squamous-cell carcinoma results in poor outcomes. The monoclonal antibody nivolumab has shown an overall survival benefit over chemotherapy in previously treated patients with advanced esophageal squamous-cell carcinoma. METHODS: In this open-label, phase 3 trial, we randomly assigned adults with previously untreated, unresectable advanced, recurrent, or metastatic esophageal squamous-cell carcinoma in a 1:1:1 ratio to receive nivolumab plus chemotherapy, nivolumab plus the monoclonal antibody ipilimumab, or chemotherapy. The primary end points were overall survival and progression-free survival, as determined by blinded independent central review. Hierarchical testing was performed first in patients with tumor-cell programmed death ligand 1 (PD-L1) expression of 1% or greater and then in the overall population (all randomly assigned patients). RESULTS: A total of 970 patients underwent randomization. At a 13-month minimum follow-up, overall survival was significantly longer with nivolumab plus chemotherapy than with chemotherapy alone, both among patients with tumor-cell PD-L1 expression of 1% or greater (median, 15.4 vs. 9.1 months; hazard ratio, 0.54; 99.5% confidence interval [CI], 0.37 to 0.80; P<0.001) and in the overall population (median, 13.2 vs. 10.7 months; hazard ratio, 0.74; 99.1% CI, 0.58 to 0.96; P = 0.002). Overall survival was also significantly longer with nivolumab plus ipilimumab than with chemotherapy among patients with tumor-cell PD-L1 expression of 1% or greater (median, 13.7 vs. 9.1 months; hazard ratio, 0.64; 98.6% CI, 0.46 to 0.90; P = 0.001) and in the overall population (median, 12.7 vs. 10.7 months; hazard ratio, 0.78; 98.2% CI, 0.62 to 0.98; P = 0.01). Among patients with tumor-cell PD-L1 expression of 1% or greater, a significant progression-free survival benefit was also seen with nivolumab plus chemotherapy over chemotherapy alone (hazard ratio for disease progression or death, 0.65; 98.5% CI, 0.46 to 0.92; P = 0.002) but not with nivolumab plus ipilimumab as compared with chemotherapy. The incidence of treatment-related adverse events of grade 3 or 4 was 47% with nivolumab plus chemotherapy, 32% with nivolumab plus ipilimumab, and 36% with chemotherapy alone. CONCLUSIONS: Both first-line treatment with nivolumab plus chemotherapy and first-line treatment with nivolumab plus ipilimumab resulted in significantly longer overall survival than chemotherapy alone in patients with advanced esophageal squamous-cell carcinoma, with no new safety signals identified. (Funded by Bristol Myers Squibb and Ono Pharmaceutical; CheckMate 648 ClinicalTrials.gov number, NCT03143153.).

From virus to immune system: Harnessing membrane-derived vesicles to fight COVID-19 by interacting with biological molecules.

Emerging and re-emerging viral pandemics have emerged as a major public health concern. Highly pathogenic coronaviruses, which cause severe respiratory disease, threaten human health and socioeconomic development. Great efforts are being devoted to the development of safe and efficacious therapeutic agents and preventive vaccines to combat them. Nevertheless, the highly mutated virus poses a challenge to drug development and vaccine efficacy, and the use of common immunomodulatory agents lacks specificity. Benefiting from the burgeoning intersection of biological engineering and biotechnology, membrane-derived vesicles have shown superior potential as therapeutics due to their biocompatibility, design flexibility, remarkable bionics, and inherent interaction with phagocytes. The interactions between membrane-derived vesicles, viruses, and the immune system have emerged as a new and promising topic. This review provides insight into considerations for developing innovative antiviral strategies and vaccines against SARS-CoV-2. First, membrane-derived vesicles may provide potential biomimetic decoys with a high affinity for viruses to block virus-receptor interactions for early interruption of infection. Second, membrane-derived vesicles could help achieve a balanced interplay between the virus and the host's innate immunity. Finally, membrane-derived vesicles have revealed numerous possibilities for their employment as vaccines.

The PKA-CREB1 axis regulates coronavirus proliferation by viral helicase nsp13 association.

The COVID-19 pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has posed a worldwide threat in the past 3 years. Although it has been widely and intensively investigated, the mechanism underlying the coronavirus-host interaction requires further elucidation, which may contribute to the development of new antiviral strategies. Here, we demonstrated that the host cAMP-responsive element-binding protein (CREB1) interacts with the non-structural protein 13 (nsp13) of SARS-CoV-2, a conserved helicase for coronavirus replication, both in cells and in lung tissues subjected to SARS-CoV-2 infection. The ATPase and helicase activity of viral nsp13 were shown to be potentiated by CREB1 association, as well as by Protein kinase A (PKA)-mediated CREB1 activation. SARS-CoV-2 replication is significantly suppressed by PKA Cα, cAMP-activated protein kinase catalytic subunit alpha (PRKACA), and CREB1 knockdown or inhibition. Consistently, the CREB1 inhibitor 666-15 has shown significant antiviral effects against both the WIV04 strain and the Omicron strain of the SARS-CoV-2. Our findings indicate that the PKA-CREB1 signaling axis may serve as a novel therapeutic target against coronavirus infection. IMPORTANCE: In this study, we provide solid evidence that host transcription factor cAMP-responsive element-binding protein (CREB1) interacts directly with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) helicase non-structural protein 13 (nsp13) and potentiate its ATPase and helicase activity. And by live SARS-CoV-2 virus infection, the inhibition of CREB1 dramatically impairs SARS-CoV-2 replication in vivo. Notably, the IC50 of CREB1 inhibitor 666-15 is comparable to that of remdesivir. These results may extend to all highly pathogenic coronaviruses due to the conserved nsp13 sequences in the virus.

Metal bond strength regulation enables large-scale synthesis of intermetallic nanocrystals for practical fuel cells.

Structurally ordered L10-PtM (M = Fe, Co, Ni and so on) intermetallic nanocrystals, benefiting from the chemically ordered structure and higher stability, are one of the best electrocatalysts used for fuel cells. However, their practical development is greatly plagued by the challenge that the high-temperature (>600 °C) annealing treatment necessary for realizing the ordered structure usually leads to severe particle sintering, morphology change and low ordering degree, which makes it very difficult for the gram-scale preparation of desirable PtM intermetallic nanocrystals with high Pt content for practical fuel cell applications. Here we report a new concept involving the low-melting-point-metal (M' = Sn, Ga, In)-induced bond strength weakening strategy to reduce Ea and promote the ordering process of PtM (M = Ni, Co, Fe, Cu and Zn) alloy catalysts for a higher ordering degree. We demonstrate that the introduction of M' can reduce the ordering temperature to extremely low temperatures (≤450 °C) and thus enable the preparation of high-Pt-content (≥40 wt%) L10-Pt-M-M' intermetallic nanocrystals as well as ten-gram-scale production. X-ray spectroscopy studies, in situ electron microscopy and theoretical calculations reveal the fundamental mechanism of the Sn-facilitated ordering process at low temperatures, which involves weakened bond strength and consequently reduced Ea via Sn doping, the formation and fast diffusion of low-coordinated surface free atoms, and subsequent L10 nucleation. The developed L10-Ga-PtNi/C catalysts display outstanding performance in H2-air fuel cells under both light- and heavy-duty vehicle conditions. Under the latter condition, the 40% L10-Pt50Ni35Ga15/C catalyst delivers a high current density of 1.67 A cm-2 at 0.7 V and retains 80% of the current density after extended 90,000 cycles, which exceeds the United States Department of Energy performance metrics and represents among the best cathodic electrocatalysts for practical proton-exchange membrane fuel cells.

Sex hormones in COVID-19 severity: The quest for evidence and influence mechanisms.

Studies have reported variable effects of sex hormones on serious diseases. Severe disease and mortality rates in COVID-19 show marked gender differences that may be related to sex hormones. Sex hormones regulate the expression of the viral receptors ACE2 and TMPRSS2, which affect the extent of viral infection and consequently cause variable outcomes. In addition, sex hormones have complex regulatory mechanisms that affect the immune response to viruses. These hormones also affect metabolism, leading to visceral obesity and severe disease can result from complications such as thrombosis. This review presents the latest researches on the regulatory functions of hormones in viral receptors, immune responses, complications as well as their role in COVID-19 progression. It also discusses the therapeutic possibilities of these hormones by reviewing the recent findings of clinical and assay studies.

Genomic insights into Penicillium chrysogenum adaptation to subseafloor sedimentary environments.

BACKGROUND: Penicillium chrysogenum is a filamentous fungal species with diverse habitats, yet little is known about its genetics in adapting to extreme subseafloor sedimental environments. RESULTS: Here, we report the discovery of P. chrysogenum strain 28R-6-F01, isolated from deep coal-bearing sediments 2306 m beneath the seafloor. This strain possesses exceptional characteristics, including the ability to thrive in extreme conditions such as high temperature (45 °C), high pressure (35 Mpa), and anaerobic environments, and exhibits broad-spectrum antimicrobial activity, producing the antibiotic penicillin at a concentration of 358 µg/mL. Genome sequencing and assembly revealed a genome size of 33.19 Mb with a GC content of 48.84%, containing 6959 coding genes. Comparative analysis with eight terrestrial strains identified 88 unique genes primarily associated with penicillin and aflatoxins biosynthesis, carbohydrate degradation, viral resistance, and three secondary metabolism gene clusters. Furthermore, significant expansions in gene families related to DNA repair were observed, likely linked to the strain's adaptation to its environmental niche. CONCLUSIONS: Our findings provide insights into the genomic and biological characteristics of P. chrysogenum adaptation to extreme anaerobic subseafloor sedimentary environments, such as high temperature and pressure.

Tuning the Interfacial Reaction Environment for CO2 Electroreduction to CO in Mildly Acidic Media.

A considerable carbon loss of CO2 electroreduction in neutral and alkaline media severely limits its industrial viability as a result of the homogeneous reaction of CO2 and OH- under interfacial alkalinity. Here, to mitigate homogeneous reactions, we conducted CO2 electroreduction in mildly acidic media. By modulating the interfacial reaction environment via multiple electrolyte effects, the parasitic hydrogen evolution reaction is suppressed, leading to a faradaic efficiency of over 80% for CO on the planar Au electrode. Using the rotating ring-disk electrode technique, the Au ring constitutes an in situ CO collector and pH sensor, enabling the recording of the Faradaic efficiency and monitoring of interfacial reaction environment while CO2 reduction takes place on the Au disk. The dominant branch of hydrogen evolution reaction switches from the proton reduction to the water reduction as the interfacial environment changes from acidic to alkaline. By comparison, CO2 reduction starts within the proton reduction region as the interfacial environment approaches near-neutral conditions. Thereafter, proton reduction decays, while CO2 reduction takes place, as the protons are increasingly consumed by the OH- electrogenerated from CO2 reduction. CO2 reduction reaches its maximum Faradaic efficiency just before water reduction initiates. Slowing the mass transport lowers the proton reduction current, while CO2 reduction is hardly influenced. In contrast, appropriate protic anion, e.g., HSO4- in our case, and weakly hydrated cations, e.g., K+, accelerate CO2 reduction, with the former providing extra proton flux but higher local pH, and the latter stabilizing the *CO2- intermediate.

Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation.

Reactive metal-support interaction (RMSI) is an emerging way to regulate the catalytic performance for supported metal catalysts. However, the induction of RMSI by the thermal reduction is often accompanied by the encapsulation effect on metals, which limits the mechanism research and applications of RMSI. In this work, a gradient orbital coupling construction strategy was successfully developed to induce RMSI in Pt-carbide system without a reductant, leading to the formation of L12-PtxM-MCy (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) intermetallic electrocatalysts. Density functional theory (DFT) calculations suggest that the gradient coupling of the d(M)-2p(C)-5d(Pt) orbital would induce the electron transfer from M to C covalent bonds to Pt NPs, which facilitates the formation of C vacancy (Cv) and the subsequent M migration (occurrence of RMSI). Moreover, the good correlation between the formation energy of Cv and the onset temperature of RMSI in Pt-MCx systems proves the key role of nonmetallic atomic vacancy formation for inducing RMSI. The developed L12-Pt3Ti-TiC catalyst exhibits excellent acidic methanol oxidation reaction activity, with mass activity of 2.36 A mgPt-1 in half-cell and a peak power density of 187.9 mW mgPt-1 in a direct methanol fuel cell, which is one of the best catalysts ever reported. DFT calculations reveal that L12-Pt3Ti-TiC favorably weakens *CO absorption compared to Pt-TiC due to the change of the absorption site from Pt to Ti, which accounts for the enhanced MOR performance.

Introducing Electron Buffers into Intermetallic Pt Alloys against Surface Polarization for High-Performing Fuel Cells.

Surface polarization under harsh electrochemical environments usually puts catalysts in a thermodynamically unstable state, which strictly hampers the thermodynamic stability of Pt-based catalysts in high-performance fuel cells. Here, we report a strategy by introducing electron buffers (variable-valence metals, M = Ti, V, Cr, and Nb) into intermetallic Pt alloy nanoparticle catalysts to suppress the surface polarization of Pt shells using the structurally ordered L10-M-PtFe as a proof of concept. Operando X-ray absorption spectra analysis suggests that with the potential increase, electron buffers, especially Cr, could facilitate an electron flow to form a electron-enriched Pt shell and thus weaken the surface polarization and tensile Pt strain. The best-performing L10-Cr-PtFe/C catalyst delivers superb oxygen reduction reaction (ORR) activity (mass activity = 1.41/1.02 A mgPt-1 at 0.9 V, rated power density = 14.0/9.2 W mgPt-1 in H2-air under a total Pt loading of 0.075/0.125 mgPt cm-2, respectively) and stability (20 mV voltage loss at 0.8 A cm-2 after 60,000 cycles of accelerated durability test) in a fuel cell cathode, representing one of the best reported ORR catalysts. Density functional theory calculations reveal that the optimized surface strain by introducing Cr on L10-PtFe/C accounts for the enhanced ORR activity, and the durability enhancement stems from the charge transfer contribution of Cr to the Pt shells and the increased kinetic energy barrier for Pt dissolution/Fe diffusion.

Prognostic value of baseline neutrophil/lymphocyte ratio in HER2-positive metastatic breast cancer: exploratory analysis of data from the CLEOPATRA trial.

PURPOSE: This study aimed to evaluate the prognostic role of the baseline neutrophil/lymphocyte ratio (NLR) in HER2-positive metastatic breast cancer (MBC) patients treated with trastuzumab/pertuzumab. EXPERIMENTAL DESIGN: Data from 780 patients from the CLEOPATRA trial and 248 local patients were collected. Patients were divided into the low and high NLR subgroups by the NLR cutoff value. Propensity score matching (PSM) and inverse probability of treatment weighting (IPTW) methods were used to control bias. Associations between the NLR and progression-free survival (PFS) and overall survival (OS) were analyzed. RESULTS: The baseline characteristics of the subgroups were well balanced after PSM and IPTW. A low baseline NLR was associated with better PFS and OS in the trastuzumab and docetaxel (TH) group in the unadjusted, PSM and IPTW models. After IPTW, a low NLR, versus a high NLR, was associated with improved PFS (HR 1.35, 95% CI 1.07-1.70, P = 0.012) and OS (HR 1.47, 95% CI 1.12-1.94, P = 0.006) in the TH group. In patients undergoing treatment with trastuzumab and pertuzumab and docetaxel (THP), a low baseline NLR was also correlated with better PFS but not OS across the three models. After IPTW, a low NLR was associated with better PFS (HR 1.52, 95% CI 1.20-1.93, P = 0.001) than a high NLR in the THP group. Multivariate analyses showed that a low baseline NLR was a predictor for PFS and OS in the TH group and for PFS in the THP group in all three models. In the real-world setting, a low baseline NLR was a predictor of better PFS among patients treated with docetaxel plus trastuzumab without or with pertuzumab in the multivariate model (P = 0.015 and 0.008, respectively). CONCLUSIONS: A low baseline NLR is associated with better survival outcomes among HER2-positive MBC patients receiving docetaxel plus trastuzumab/pertuzumab as first-line therapy.

Unraveling the cross-talk between N6-methyladenosine modification and non-coding RNAs in breast cancer: Mechanisms and clinical implications.

In recent years, breast cancer (BC) has surpassed lung cancer as the most common malignant tumor worldwide and remains the leading cause of cancer death in women. The etiology of BC usually involves dysregulation of epigenetic mechanisms and aberrant expression of certain non-coding RNAs (ncRNAs). N6-methyladenosine (m6A), the most prevalent RNA modification in eukaryotes, widely exists in ncRNAs to affect its biosynthesis and function, and is an important regulator of tumor-related signaling pathways. Interestingly, ncRNAs can also regulate or target m6A modification, playing a key role in cancer progression. However, the m6A-ncRNAs regulatory network in BC has not been fully elucidated, especially the regulation of m6A modification by ncRNAs. Therefore, in this review, we comprehensively summarize the interaction mechanisms and biological significance of m6A modifications and ncRNAs in BC. Meanwhile, we also focused on the clinical application value of m6A modification in BC diagnosis and prognosis, intending to explore new biomarkers and potential therapeutic targets.

Portable Mass Spectrometry for On-site Detection of Hazardous Volatile Organic Compounds via Robotic Extractive Sampling.

Various hazardous volatile organic compounds (VOCs) are frequently released into environments during accidental events that cause many hazards to ecosystems and humans. Therefore, rapid, sensitive, and on-site detection of hazardous VOCs is crucial to understand their compositions, characteristics, and distributions in complex environments. However, manual handling of hazardous VOCs remains a challenging task, because of the inaccessible environments and health risk. In this work, we designed a quadruped robotic sampler to reach different complex environments for capturing trace hazardous VOCs using a needle trap device (NTD) by remote manipulation. The captured samples were rapidly identified by portable mass spectrometry (MS) within minutes. Rapid detection of various hazardous VOCs including toxicants, chemical warfare agents, and burning materials from different environments was successfully achieved using this robot-MS system. On-site detection of 83 typical hazardous VOCs was examined. Acceptable analytical performances including low detection limits (at subng/mL level), good reproducibility (relative standard deviation (RSD) < 20%, n = 6), excellent quantitative ability (R2 > 0.99), and detection speed (within minutes) were also obtained. Our results show that the robot-MS system has excellent performance including safety, controllability, applicability, and robustness under dangerous chemical conditions.

GMOIT: a tool for effective screening of genetically modified crops.

BACKGROUND: Advancement in agricultural biotechnology has resulted in increasing numbers of commercial varieties of genetically modified (GM) crops worldwide. Though several databases on GM crops are available, these databases generally focus on collecting and providing information on transgenic crops rather than on screening strategies. To overcome this, we constructed a novel tool named, Genetically Modified Organisms Identification Tool (GMOIT), designed to integrate basic and genetic information on genetic modification events and detection methods. RESULTS: At present, data for each element from 118 independent genetic modification events in soybean, maize, canola, and rice were included in the database. Particularly, GMOIT allows users to customize assay ranges and thus obtain the corresponding optimized screening strategies using common elements or specific locations as the detection targets with high flexibility. Using the 118 genetic modification events currently included in GMOIT as the range and algorithm selection results, a "6 + 4" protocol (six exogenous elements and four endogenous reference genes as the detection targets) covering 108 events for the four crops was established. Plasmids pGMOIT-1 and pGMOIT-2 were constructed as positive controls or calibrators in qualitative and quantitative transgene detection. CONCLUSIONS: Our study provides a simple, practical tool for selecting, detecting, and screening strategies for a sustainable and efficient application of genetic modification.

Establishing Ultralow Self-Discharge Zn-I2 Battery by Optimizing ZnSO4 Electrolyte Concentration.

As one of promising candidates for large-scale energy-storage systems, Zn-I2 aqueous battery exhibits multifaceted advantages including low cost, high energy/powder density, and intrinsic operational safety, but also suffers from fast self-discharge and short cycle/shelf lifespan associating with I3 - shuttle, Zn dendrite growth, and corrosion. In this paper, the battery's self-discharge rate is successfully suppressed down to an unprecedent level of 17.1% after an ultralong shelf-time of 1 000 h (i.e., 82.9% capacity retention after 41 days open-circuit storage), by means of manipulating solvation structures of traditional ZnSO4 electrolyte via simply adjusting electrolyte concentration. Better yet, the optimized 2.7 m ZnSO4 electrolyte further prolongs the cycle lifespan of the battery up to >10 000 and 43 000 cycles at current density of 1 and 5 A g-1, respectively, thanks to the synthetic benefits from reduced free water content, modified solvation structure and lowered I2 dissolution in the electrolyte. With both long lifespan and ultralow self-discharge, this reliable and affordable Zn-I2 battery may provide a feasible alternative to the centuries-old lead-acid battery.

1D/3D Heterogeneous Assembling Body of Cobalt Nitrides for Highly Efficient Overall Hydrazine Splitting and Supercapacitors.

Herein, the construction of a heterostructured 1D/3D CoN-Co2 N@NF (nickel foam) electrode used for thermodynamically favorable hydrazine oxidation reaction (HzOR), as an alternative to sluggish anodic oxygen evolution reaction (OER) in water splitting for hydrogen production, is reported. The electrode exhibits remarkable catalytic activities, with an onset potential of -0.11 V in HzOR and -71 mV for a current density of 10 mA cm-2 in hydrogen evolution reaction (HER). Consequently, an extraordinary low cell voltage of 53 mV is required to achieve 10 mA cm-2 for overall hydrazine splitting in a two-electrode system, demonstrating significant energy-saving advantages over conventional water splitting. The HzOR proceeds through the 4e- reaction pathway to release N2 while the 1e- pathway to emit NH3 is uncompetitive, as evidenced by differential electrochemical mass spectrometric measurements. The X-ray absorption spectroscopy, in situ Raman spectroscopy, and theoretical calculations identify cobalt nitrides rather than corresponding oxides/(oxy)hydroxides as catalytic species for HzOR and illustrate advantages of heterostructured CoN-Co2 N in optimizing adsorption energies of intermediates/reagents and promoting catalytic activities toward both HzOR and HER. The CoN-Co2 N@NF is also an excellent supercapacitive material, exhibiting an increased specific capacity (938 F g-1 at 1 A g-1 ) with excellent cycling stability (95.8%, 5000 cycles).

InCl3-Assisted Surface Defects Restoring to Enhance Lead-Free Cs2ZrCl6 Nanocrystals for X-Ray Imaging and Blue LED Applications.

As one type of recent emerging lead-free perovskites, Cs2ZrCl6 nanocrystals are widely concerned, benefiting from the eminent designability, high X-ray cutoff efficiency, and favorable stability. Improving the luminescence performance of Cs2ZrCl6 nanocrystals has great importance to cater for practical applications. In view of the surface defects frequently formed by the liquid phase method, the particle morphology and surface quality of this material are expected to be regulated if certain intervention is made in the synthesis process. In the work, differing from normal cell lattice modulation based on the ion doping, the grain size and surface morphology of Cs2ZrCl6 nanocrystals are optimized via adding a certain amount of InCl3 to the synthetic solution. The surface defects are restored to inhibit the defect-induced non-radiative transition, resulting in the improvement of the luminescence properties. Moreover, a flexible Cs2ZrCl6@polydimethylsiloxane film with excellent heat, water, and bending resistance and a light-emitting diode (LED) device are fabricated, exhibiting excellent application potential for X-ray imaging and blue LED.

Highly Curved Defect Sites: How Curvature Effect Influences Metal-Free Defective Carbon Electrocatalysts.

Topological defects are widely recognized as effective active sites toward a variety of electrochemical reactions. However, the role of defect curvature is still not fully understood. Herein, carbon nanomaterials with rich topological defect sites of tunable curvature is reported. The curved defective surface is realized by controlling the high-temperature pyrolytic shrinkage process of precursors. Theoretical calculations demonstrate bending the defect sites can change the local electronic structure, promote the charge transfer to key intermediates, and lower the energy barrier for oxygen reduction reaction (ORR). Experimental results convince structural superiority of highly-curved defective sites, with a high kinetic current density of 22.5 mA cm-2 at 0.8 V versus RHE for high-curvature defective carbon (HCDC), ≈18 times that of low-curvature defective carbon (LCDC). Further raising the defect densities in HCDC leads to the dual-regulated products (HCHDC), which exhibit exceptionally outstanding ORR activity in both alkaline and acidic media (half-wave potentials: 0.88 and 0.74 V), outperforming most of the reported metal-free carbon catalysts. This work uncovers the curvature-activity relationship in carbon defect for ORR and provides new guidance to design advanced catalysts via curvature-engineering.