Boosting Urea-Assisted Natural Seawater Electrolysis in 3D Leaf-Like Metal-Organic Framework Nanosheet Arrays Using Metal Node Engineering.

Metal node engineering, which can optimize the electronic structure and modulate the composition of poor electrically conductive metal-organic frameworks, is of great interest for electrochemical natural seawater splitting. However, the mechanism underlying the influence of mixed-metal nodes on electrocatalytic activities is still ambiguous. Herein, a strategic design is comprehensively demonstrated in which mixed Ni and Co metal redox-active centers are uniformly distributed within NH2-Fe-MIL-101 to obtain a synergistic effect for the overall enhancement of electrocatalytic activities. Three-dimensional mixed metallic MOF nanosheet arrays, consisting of three different metal nodes, were in situ grown on Ni foam as a highly active and stable bifunctional catalyst for urea-assisted natural seawater splitting. A well-defined NH2-NiCoFe-MIL-101 reaches 1.5 A cm-2 at 360 mV for the oxygen evolution reaction (OER) and 0.6 A cm-2 at 295 mV for the hydrogen evolution reaction (HER) in freshwater, substantially higher than its bimetallic and monometallic counterparts. Moreover, the bifunctional NH2-NiCoFe-MIL-101 electrode exhibits eminent catalytic activity and stability in natural seawater-based electrolytes. Impressively, the two-electrode urea-assisted alkaline natural seawater electrolysis cell based on NH2-NiCoFe-MIL-101 needs only 1.56 mV to yield 100 mA cm-2, much lower than 1.78 V for alkaline natural seawater electrolysis cells and exhibits superior long-term stability at a current density of 80 mA cm-2 for 80 h.

Recent Progress on Copper-Based Bimetallic Heterojunction Catalysts for CO2 Electrocatalysis: Unlocking the Mystery of Product Selectivity.

Copper-based bimetallic heterojunction catalysts facilitate the deep electrochemical reduction of CO2 (eCO2RR) to produce high-value-added organic compounds, which hold significant promise. Understanding the influence of copper interactions with other metals on the adsorption strength of various intermediates is crucial as it directly impacts the reaction selectivity. In this review, an overview of the formation mechanism of various catalytic products in eCO2RR is provided and highlight the uniqueness of copper-based catalysts. By considering the different metals' adsorption tendencies toward various reaction intermediates, metals are classified, including copper, into four categories. The significance and advantages of constructing bimetallic heterojunction catalysts are then discussed and delve into the research findings and current development status of different types of copper-based bimetallic heterojunction catalysts. Finally, insights are offered into the design strategies for future high-performance electrocatalysts, aiming to contribute to the development of eCO2RR to multi-carbon fuels with high selectivity.

Dopant-Induced Charge Redistribution on the 3D Sponge-like Hierarchical Structure of Quaternary Metal Phosphides Nanosheet Arrays Derived from Metal-Organic Frameworks for Natural Seawater Splitting.

Dopant-induced electron redistribution on transition metal-based materials has long been considered an emerging new electrocatalyst that is expected to replace noble-metal-based electrocatalysts in natural seawater electrolysis; however, their practical applications remain extremely daunting due to their sluggish kinetics in natural seawater. In this work, we developed a facile strategy to synthesize the 3D sponge-like hierarchical structure of Ru-doped NiCoFeP nanosheet arrays derived from metal-organic frameworks with remarkable hydrogen evolution reaction (HER) performance in natural seawater. Based on experimental results and density functional theory calculations, Ru-doping-induced charge redistribution on the surface of metal active sites has been found, which can significantly enhance the HER activity. As a result, the 3D sponge-like hierarchical structure of Ru-NiCoFeP nanosheet arrays achieves low overpotentials of 52, 149, and 216 mV at 10, 100, and 500 mA cm-2 in freshwater alkaline, respectively. Notably, the electrocatalytic activity of the Ru-NiCoFeP electrocatalyst in simulated alkaline seawater and natural alkaline seawater is nearly the same as that in freshwater alkaline. This electrocatalyst exhibits superior catalytic properties with outstanding stability under a high current density of 85 mA cm-2 for more than 100 h in natural seawater, which outperforms state-of-the-art 20% Pt/C at high current density. Our work provides valuable guidelines for developing a low-cost and high-efficiency electrocatalyst for natural seawater splitting.

Correction: Establishment and application of a quadruple real-time RT-PCR for detecting avian metapneumovirus.

[This corrects the article DOI: 10.1371/journal.pone.0270708.].

Single-Atom-Based Oxygen Reduction Reaction Catalysts for Proton Exchange Membrane Fuel Cells: Progress and Perspective.

Single-atom catalysts (SACs) are regarded as promising non-noble-metal alternatives for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells due to their high atom utilization efficiency and excellent catalytic properties. However, the insufficient long-term stability issues of SACs under the working conditions seriously hinder their practical application. In this perspective, the recent progress of SACs with optimized ORR catalytic activity is first reviewed. Then, the possible degradation mechanisms of SACs in the ORR process and effective strategies for improving their ORR durability are summarized. Finally, some challenges and opportunities are proposed to develop stable single-atom-based ORR electrocatalysts in the future.

Highly Efficient and Stable Hydrogen Evolution from Natural Seawater by Boron-Doped Three-Dimensional Ni2P-MoO2 Heterostructure Microrod Arrays.

The rational design of highly active and stable electrocatalysts toward the hydrogen evolution reaction (HER) is highly desirable but challenging in seawater electrolysis. Herein we propose a strategy of boron-doped three-dimensional Ni2P-MoO2 heterostructure microrod arrays that exhibit excellent catalytic activity for hydrogen evolution in both alkaline freshwater and seawater electrolytes. The incorporation of boron into Ni2P-MoO2 heterostructure microrod arrays could modulate the electronic properties, thereby accelerating the HER. Consequently, the B-Ni2P-MoO2 heterostructure microrod array electrocatalyst exhibits a superior catalyst activity for HER with low overpotentials of 155, 155, and 157 mV at a current density of 500 mA cm-2 in 1 M KOH, 1 M KOH + NaCl, and 1 M KOH + seawater, respectively. It also exhibits exceptional performance for HER in natural seawater with a low overpotential of 248 mV at 10 mA cm-2 and a long-lasting lifetime of over 100 h.

Promoting High-Oxidation-State Metal Active Sites in a Hollow Ternary Metal Fluoride Nanoflake Array for Urea Electrolysis.

The adsorption ability of hydrogen, hydroxide, and oxygenic intermediates plays a crucial role in electrochemical water splitting. Electron-deficient metal-active sites can prompt electrocatalytic activity by improving the adsorption ability of intermediates. However, it remains a significant challenge to synthesize highly abundant and stable electron-deficient metal-active site electrocatalysts. Herein, we present a general approach to synthesizing a hollow ternary metal fluoride (FeCoNiF2) nanoflake array as an efficient and robust bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). We find that the F anion withdraws electrons from the metal centers, inducing an electron-deficient metal center catalyst. The rationally designed hollow nanoflake array exhibits the overpotential of 30 mV for HER and 130 mV for UOR at a current density of 10 mA cm-2 and superior stability without decay events over 150 h at a large current density of up to 100 mA cm-2. Remarkably, the assembled urea electrolyzer using a bifunctional hollow FeCoNiF2 nanoflake array catalyst requires cell voltages of only 1.352 and 1.703 V to afford current densities of 10 and 100 mA cm-2, respectively, which are 116 mV less compared with that required for overall water splitting.

Perfluorooctane sulfonate and perfluorooctanoic acid inhibit progesterone-responsive capacitation through cAMP/PKA signaling pathway and induce DNA damage in human sperm.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are two persistent organic pollutants harmful to human health. They induce negative effects on male reproduction by influencing male hormones, spermatogenesis, and sperm quality. However, their effects and mechanisms on human sperm capacitation and fertilization remain unclear. Here, human sperm were incubated with different concentrations of PFOS or PFOA with progesterone during capacitation. Both PFOS and PFOA inhibited human sperm hyperactivation, sperm acrosome reaction, and protein tyrosine phosphorylation levels. PFOS and PFOA decreased intracellular Ca2+ concentration in the presence of progesterone, and subsequently decreased cAMP level, and PKA activity. PFOS and PFOA increased reactive oxygen species production and sperm DNA fragmentation during the only 3 h capacitation incubation. Conclusively, PFOA and PFOS may inhibit human sperm capacitation via the Ca2+-mediated cAMP/PKA signaling pathway in the presence of progesterone, and induce sperm DNA damage through increased oxidative stress, which is not conducive to fertilization.

The genetic and biological characterization of the first avian paramyxovirus serotype 14 isolated from chicken in China.

In October 2020, an avian paramyxovirus serotype 14 (APMV-14)-designated chicken/Fujian/2160/2020 (FJ2160) was isolated from tracheal and cloacal swab sample of chicken collected from live bird market in Fujian province in China during the active surveillance program. The complete genome of FJ2160 comprised 15,444 nucleotides (nt) complying with the paramyxovirus "rule of six" and encoded six non-overlapping structural proteins in the order of 3'-NP-P-M-F-HN-L-'5. The complete genome sequence analysis showed that FJ2160 had the highest identity (90.0%) with the APMV-14 isolated from Japan, while the nucleotide sequence identities of FJ2160 and other APMVs ranged from 42.4 to 51.1%. The F protein cleavage site was TREGR↓L, which resembled a lentogenic strain of APMV-1. Phylogenetic analysis revealed that the FJ2160 closest relative was APMV-14. The intracerebral pathogenicity index (ICPI) tests indicated that the virus was lentogenic. This is the first report of APMV-14 in China. These results provide evidence that APMV-14 could infect chickens and reveal the genetic characteristics and biological properties of the virus, which can help to better understand this new emerging APMV-14.

Hierarchically Porous Carbons with Highly Curved Surfaces for Hosting Single Metal FeN4 Sites as Outstanding Oxygen Reduction Catalysts.

Iron-nitrogen-carbon (FeNC) materials have emerged as a promising alternative to platinum-group metals for catalyzing the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells. However, their low intrinsic activity and stability are major impediments. Herein, an FeN-C electrocatalyst with dense FeN4 sites on hierarchically porous carbons with highly curved surfaces (denoted as FeN4 -hcC) is reported. The FeN4 -hcC catalyst displays exceptional ORR activity in acidic media, with a high half-wave potential of 0.85 V (versus reversible hydrogen electrode) in 0.5 m H2 SO4 . When integrated into a membrane electrode assembly, the corresponding cathode displays a high maximum peak power density of 0.592 W cm-2 and demonstrates operating durability over 30 000 cycles under harsh H2 /air conditions, outperforming previously reported Fe-NC electrocatalysts. These experimental and theoretical studies suggest that the curved carbon support fine-tunes the local coordination environment, lowers the energies of the Fe d-band centers, and inhibits the adsorption of oxygenated species, which can enhance the ORR activity and stability. This work provides new insight into the carbon nanostructure-activity correlation for ORR catalysis. It also offers a new approach to designing advanced single-metal-site catalysts for energy-conversion applications.

Primary cervical meningeal melanocytoma with a dumbbell shape: Case report and review of the literature.

RATIONALE: Meningeal melanocytoma is a rare benign pigmented tumor originat from leptomeningeal melanocytes. Here, we report the case of a female who presented with numbness and weakness of the limbs for approximately 6 months. PATIENT CONCERNS: We report the case of a 60-year-old Chinese female who presented with numbness and weakness of the limbs for approximately 6 months. computed tomography (CT) and magnetic resonance imaging (MRI) revealed a dumbbell-shaped tumor inside and outside the cervical (C) spinal canal. DIAGNOSES: The patient was using CT and MRI. Subsequently, the patient underwent surgery, and low-grade melanocytoma was diagnosed pathologically. INTERVENTIONS: Subsequently, the patient underwent a surgery, and the tumor was completely removed. OUTCOMES: The tumor did not recur after 6 months. CONCLUSION: This case suggested 2 "take-away" lessons: first, spinal meningeal melanocytomas may be dumbbell-shaped; and second, melanocytoma could appear as hyperintense, isointense, or hypointense on T2-weighted MRI.

Iberiotoxin and clofilium regulate hyperactivation, acrosome reaction, and ion homeostasis synergistically during human sperm capacitation.

Potassium channels play essential roles in the regulation of male fertility. However, potassium channels mediating K+ currents in human sperm (IKSper ) remain controversial. Besides SLO3, the SLO1 potassium channel is a potential candidate for human sperm KSper. This study intends to elucidate the function of SLO1 potassium channel during human sperm capacitation. Human sperm were treated with iberiotoxin (IbTX, a SLO1 specific inhibitor) and clofilium (SLO3 inhibitor) separately or simultaneously during in vitro capacitation. A computer-assisted sperm analyzer was used to assess sperm motility. The sperm acrosome reaction (AR) was analyzed using fluorescein isothiocyanate-conjugated Pisum sativum agglutinin staining. Sperm protein tyrosine phosphorylation was studied using western blotting. Intracellular Ca2+ , K+ , Cl- , and pH were analyzed using ion fluorescence probes. Independent inhibition with IbTX or clofilium decreased the sperm hyperactivation, AR, and protein tyrosine phosphorylation, and was accompanied by an increase in [K+ ]i , [Cl- ]i , and pHi , but a decrease in [Ca2+ ]i . Simultaneously inhibition with IbTX and clofilium lower sperm hyperactivation and AR more than independent inhibition. The increase in [K+ ]i , [Cl- ]i , and pHi , and the decrease in [Ca2+ ]i were more pronounced. This study suggested that the SLO1 potassium channel may have synergic roles with SLO3 during human sperm capacitation.

Coupling Amorphous Ni Hydroxide Nanoparticles with Single-Atom Rh on Cu Nanowire Arrays for Highly Efficient Alkaline Seawater Electrolysis.

Exploring efficient catalysts for alkaline seawater electrolysis is highly desired yet challenging. Herein, coupling single-atom rhodium with amorphous nickel hydroxide nanoparticles on copper nanowire arrays is designed as a new active catalyst for the highly efficient alkaline seawater electrolysis. We found that an amorphous Ni(OH)2 nanoparticle is an effective catalyst to accelerate the water dissociation step. In contrast, the single-atom rhodium is an active site for adsorbed hydrogen recombination to generate H2. The NiRh-Cu NA/CF catalyst shows superior electrocatalytic activity toward HER, surpassing a benchmark Pt@C. In detail, the NiRh-Cu NA/CF catalyst exhibits HER overpotentials as low as 12 and 21 mV with a current density of 10 mA cm-2 in fresh water and seawater, respectively. At high current density, the NiRh-Cu NA/CF catalyst also exhibits an outstanding performance, where 300 mA cm-2 can be obtained at an overpotential of 155 mV and shows a slight fluctuation in the current density over 30 h.

Reverse transcription recombinase-aided amplification assay for H5 subtype avian influenza virus.

BACKGROUND: The H5 subtype avian influenza virus (AIV) has caused huge economic losses to the poultry industry and is a threat to human health. A rapid and simple test is needed to confirm infection in suspected cases during disease outbreaks. METHODS: In this study, we developed a reverse transcription recombinase-aided amplification (RT-RAA) assay for the detection of H5 subtype AIV. Assays were performed at a single temperature (39 °C), and the results were obtained within 20 min. RESULTS: The assay showed no cross-detection with Newcastle disease virus or infectious bronchitis virus. The analytical sensitivity was 103 RNA copies/µL at a 95% confidence interval according to probit regression analysis, with 100% specificity. Compared with published reverse transcription quantitative real-time polymerase chain reaction assays, the κ value of the RT-RAA assay in 420 avian clinical samples was 0.983 (p < 0.001). The sensitivity for avian clinical sample detection was 97.26% (95% CI, 89.56-99.52%), and the specificity was 100% (95% CI, 98.64-100%). CONCLUSIONS: These results indicated that our RT-RAA assay may be a valuable tool for detecting H5 subtype AIV.

A molecular, epidemiological and pathogenicity analysis of pigeon paramyxovirus type 1 viruses isolated from live bird markets in China in 2014-2021.

To expand our understanding of the epidemiology of pigeon paramyxovirus type 1 (PPMV-1) in China, risk-based active surveillance was undertaken with pigeon swabs collected from live bird markets in 2014-2021. Seventy-six PPMV-1 strains were isolated from 12 provinces (60%) of the 20 provinces surveyed, and the positive rates of PPMV-1 varied from 0.50% to 3.19% annually. The complete genomic sequences of 18 representative viruses were analyzed, revealing a genome of 15,192 nucleotides, with the gene order 3'-NP-P-M-F-HN-L-5'. All isolates contained the 112RRQKRF117 cleavage site in the fusion (F) protein, a characteristic generally associated with virulent Newcastle disease viruses (NDVs), and the intracerebral pathogenicity index values (1.05-1.41) of four isolates indicated their virulence. A challenge experiment also demonstrated that all four isolates are pathogenic to pigeons, with morbidity rates of 60-100% and mortality rates of 0-30%. A further analysis of the functional domains of the F and HN proteins revealed several mutations in the fusion peptide, signal peptide, neutralizing epitopes, heptad repeat region, and transmembrane domains, and the substitution of cysteine residue 25 (C25Y) and substitutions in the HRb region (V287I) of the F protein and the transmembrane domain (V45A) of the HN protein may play important roles in PPMV-1 virulence. In a phylogenetic analysis based on the complete sequences of the F gene, all eighteen isolates all clustered into sub-genotype VI.2.1.1.2.2 (VIb) in class II, and shared high nucleotide sequence identity, indicating that the PPMV-1 strains in sub-genotype VI.2.1.1.2.2 are the predominant PPMV-1 viruses in pigeons in China and that the variations in these viruses have been relatively stable over the past 8 years. This study identifies the genetic and pathogenicity characteristics of the PPMV-1 strains prevalent in China and extends our understanding of the prevalence of this virus in China.

Establishment and application of a quadruple real-time RT-PCR for detecting avian metapneumovirus.

In order to develop an appropriate method for high-throughput detection of avian metapneumovirus, a quadruple real-time reverse-transcription polymerase chain reaction assay was established with four pairs of specific primers and four specific probes based on the G or M gene of aMPV-A, aMPV-B, aMPV-C and aMPV-D. Its specificity and sensitivity were evaluated, and clinical samples were tested by the method. The results showed that all the four subgroups of avian metapneumovirus can be detected in the quadruple real-time RT-PCR assay simultaneously, with a detection limit of 100-1000 cRNA copies/reaction. The other common poultry viruses were negative. In the avian clinical sample detection, 39 out of 1920 clinical samples collected from 8 provinces were positive. Compared with published RT-PCR assays, the κ value of the quadruple real-time RT-PCR assay in 1920 avian clinical samples was 1.000 (P < 0.001). The established method could be used for the rapid detection of the four subgroups of avian metapneumovirus with high specificity and high sensitivity.

Continuous surveillance revealing a wide distribution of class I Newcastle disease viruses in China from 2011 to 2020.

The risk-based active surveillance for Newcastle disease virus (NDV) was carried out in China from 2011 to 2020. A total of 110,018 swabs were collected from 28 provinces. 2,389 class I NDVs were isolated and identified by RT-PCR and sequencing. The average annual positivity rate of class I NDVs from 2011 to 2020 was 2.17%. In the last 10 years, the positivity rate was highest in 2011 (4.76%), and has since decreased. Most viruses were isolated from chickens, while others were collected from ducks, geese and pigeons, as well as from the environment. The positivity rates for class I NDVs in poultry ranged from 0.55% to 2.40%. The viruses were isolated from 373 sampling sites in 24 provinces, mainly in East, Central, South and Southwest China. The positivity rates of NDVs in wholesale markets (51.58%) and retail markets (42.83%) were much higher than those in poultry farms (7.14%) and slaughterhouses (3.85%). Phylogenetic analyses showed that most isolates belonged to sub-genotype 1.1.2, while only 22 viruses belonged to sub-genotype 1.2, indicating the viruses in sub-genotype 1.1.2 were the predominant strains in China. The F and HN genes of six strains in the two sub-genotypes were sequenced and analyzed. The cleavage sites of F protein in the six viruses were 112ERQER/L117, 112ERQGR/L117 or 112GRQERL117, which were typical of low virulence NDV. Several mutations were identified in the functional domains of F and HN proteins, including fusion peptide, heptad repeat region, transmembrane domains and neutralizing epitopes. This study revealed the distribution, genetic and phylogenetic characteristics of class I NDVs in China, and could help us to better understand the epidemiological context of class I NDVs in China.

Microstructure Evolution and Dynamic Recrystallization Behavior of Mg-Gd-Y-Zn-Zr Alloy during Rotating Backward Extrusion.

Rotating backward extrusion (RBE) is one of severe plastic deformation (SPD) methods used to produce cylindrical components with a very large strain by a single pass. In this study, the microstructure and texture evolution in the different regions of Mg-12Gd-4Y-2Zn-0.5Zr (wt.%) alloys via RBE process were investigated by using optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron back-scatter diffraction (EBSD). The results showed that the cup-shaped sample formed by RBE process exhibited typical gradient microstructure expanding from its inner wall to outer wall along the radial direction (RD). The average grain size of the RBEed sample decreased when the radius decreased from the edge region to the center region along the RD, which was attributed to the different strains and strain rates in the different regions. It also could be observed that the center region showed highest deformation and the edge region exhibited the lowest deformation in the RBEed sample along the RD. In addition, the grain refinement mechanisms of the experimental alloy containing long-period stacking ordered (LPSO) phases after RBE with 100 N were continuous dynamic recrystallization (CDRX), discontinuous dynamic recrystallization (DDRX) and particle stimulated nucleation (PSN).

Selectively Regulating the Chiral Morphology of Amino Acid-Assisted Chiral Gold Nanoparticles with Circularly Polarized Light.

Chiral nanomaterials have attracted increasing attention due to their versatile optical properties. Although circularly polarized (CP) light can serve as an inducer, it has negligible effects because of the short lifetime of the plasmonic states. Here, we propose that the site-selective chirality regulation on the morphology of cysteine (cys) amino acid-assisted chiral gold nanoparticles (cys-chiral AuNPs) can be realized through CP light irradiation. This can result in the increased or decreased circular dichroism (CD) signal intensity. The site-selective growth mechanism of the cys-chiral AuNPs is elucidated with light-matter interactions through the opposite rotation of right(R)/left(L) CP light. The site-selective chirality growth of the cys-chiral AuNPs is ascribed to the morphology evolution induced by the synergy of cys and R/L-CP light, which is clearly analyzed and elucidated with high CD intensities. This work provides a promising alternative strategy to produce high-chirality nanomaterials that can be applied in biomedicine and enantiomer photocatalytic reaction.

Interfacial Microenvironment Modulation Enhancing Catalytic Kinetics of Binary Metal Sulfides Heterostructures for Advanced Water Splitting Electrocatalysts.

Interfacial microenvironment modulation has been proven to be a promising route to fabricate highly efficient catalysts. In this work, the lattice defect-rich NiS2 /MoS2 nanoflakes (NMS NFs) electrocatalysts are successfully synthesized by a simple strategy. Benefiting from the abundant lattice defects and modulated interfacial microenvironment between NiS2 and MoS2 , the prepared NMS NFs show superior catalytic activity for water splitting. Particularly, the optimized NMS NFs (the molar ratio of Ni:Mo = 5:5) exhibit remarkable catalytic activity toward overall water splitting with a voltage of 1.60 V at 10 mA cm-2 in alkaline media, which is lower than that of the noble-metal-based electrocatalysts (1.68 V at 10 mA cm-2 ). The NMS NFs electrocatalysts also show exceptional long-term stability (>50 h) for overall water splitting. The density functional theory results demonstrate that the injection of NiS2 into MoS2 can greatly optimize the catalytic kinetics and reduce the energy barrier for hydrogen/oxygen evolution reactions. The work does not only offer a promising candidate for a highly efficient water splitting electrocatalyst but also highlights that interfacial microenvironment modulation is a potential strategy to optimize the catalytic kinetics.