RESUMO
Developing high-efficiency electrocatalysts for nitrate-to-ammonia transformation holds significant promise for the production of ammonia, a crucial component in agricultural fertilizers and as a carbon-free energy carrier. In this study, we propose a viable strategy involving sulfur doping to modulate both the microstructure and electronic properties of CoSe2 for nitrate reduction. This approach remarkably enhances the conversion of nitrate to ammonia by effectively regulating the adsorption capability of nitrogenous intermediates. Specifically, sulfur-doped CoSe2 nanowires (S-CoSe2 NWs) exhibit a peak faradaic efficiency of 93.1% at -0.6 V vs. RHE and achieve the highest NH3 yield rate of 11.6 mg h-1 cm-2. Mechanistic investigations reveal that sulfur doping facilitates the creation of highly charged active sites, which enhance the adsorption of nitrite and subsequent hydrogenation, leading to improved selectivity towards ammonia production.
RESUMO
EMT dysfunction is a dominant mechanisms of hypospadias. Thus, identification of EMT-related lncRNAs based on transcriptome sequencing data of hypospadias might provide novel molecular markers and therapeutic targets for hypospadias. First, the microarray data related to hypospadias were downloaded from Gene Expression Omnibus (GEO). Besides, the differentially expressed lncRNAs and messenger RNAs (mRNAs) related to EMT were screened to construct lncRNA-mRNA co-expression interaction pairs. In addition, the microRNA (miRNA) prediction analysis was performed through bioinformatics methods to construct a ceRNA network. Moreover, function prediction and function enrichment and pathway analyses were also performed. Finally, the core EMT-related lncRNAs were verified based on mRNA expression changes and cell functions. A total of 6 EMT-related lncRNAs were identified and 123 mRNA-lncRNA co-expression interaction pairs were screened in this study. Additionally, a ceRNA regulatory network comprising 17 mRNAs, 4 lncRNAs, and 28 miRNAs was constructed based on the prediction of hypospadias-related miRNAs. The validation results of the dataset GSE121712 revealed that only BEX1 was positively correlated with the expression of the lncRNA GNAS-AS1 (r = 0.874, P < 0.01), both of which had high expression. The cell experiment results demonstrated that interfering with the expression of GNAS-AS1 significantly promoted the proliferation, migration, and EMT of cells. Importantly, it was confirmed that GNAS-AS1 can serve as a ceRNA and play an important role in the EMT of hypospadias. Hence, it may be considered as a potential target in the treatment of this disease.
Assuntos
Transição Epitelial-Mesenquimal , Hipospadia , RNA Longo não Codificante , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , Hipospadia/genética , Hipospadia/patologia , Transição Epitelial-Mesenquimal/genética , Humanos , Masculino , Redes Reguladoras de Genes , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , MicroRNAs/genética , MicroRNAs/metabolismo , Biologia Computacional , Perfilação da Expressão GênicaRESUMO
A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.
RESUMO
OBJECTIVE: This study aims to screen the differentially expressed long non-coding RNAs (DELncRNAs) related to the regulation of epithelial-mesenchymal transition (EMT) in hypospadias in mesenchymal stem cell-derived exosomes (MSC-Exons) and explore the potential mechanism of these lncRNAs for the EMT in hypospadias. METHODS: In this study, the microarray data related to MSC-Exos and hypospadias were downloaded from Gene Expression Omnibus (GEO). Besides, the lncRNAs highly expressed in MSC-Exos and the differentially expressed mRNAs and lncRNAs in children with hypospadias were screened, respectively. In addition, the lncRNAs enriched in MSC-Exos and differentially expressed lncRNAs in hypospadias were intersected to obtain the final DElncRNAs. Moreover, the co-expression interaction pairs of differentially expressed lncRNAs and mRNAs were analyzed to construct a Competing Endogenous RNA (ceRNA) network. Finally, the candidate lncRNAs in exosomes were subjected to in vitro cell function verification. RESULTS: In this study, a total of 4 lncRNAs were obtained from the microarray data analysis. Further, a ceRNA regulatory network of MSC-Exo-derived lncRNAs related to the regulation of EMT in hypospadias was constructed, including 4 lncRNAs, 2 mRNAs, and 6 miRNAs. The cell function verification results indicated that the exosomes secreted by MSCs may transport HLA complex group 18 (HCG18) into target cells, which promoted the proliferation, migration, and EMT of these cells. CONCLUSION: MSC-Exo-derived lncRNA HCG18 can enter target cells, and it may be involved in the regulation of EMT in hypospadias through the ceRNA network.
Assuntos
Hipospadia , MicroRNAs , RNA Longo não Codificante , Masculino , Criança , Humanos , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , MicroRNAs/genética , Transdução de Sinais , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , Transição Epitelial-Mesenquimal/genética , Redes Reguladoras de GenesRESUMO
Objective: This study was conducted to explore the risk factors for the prognosis and recurrence of ureteropelvic junction obstruction (UPJO). Methods: The correlation of these variables with the prognosis and recurrence risks was analyzed by binary and multivariate logistic regression. Besides, a nomogram was constructed based on the multivariate logistic regression calculation. After the model was verified by the C-statistic, the ROC curve was plotted to evaluate the sensitivity of the model. Finally, the decision curve analysis (DCA) was conducted to estimate the clinical benefits and losses of intervention measures under a series of risk thresholds. Results: Preoperative automated peritoneal dialysis (APD), preoperative urinary tract infection (UTI), preoperative renal parenchymal thickness (RPT), Mayo adhesive probability (MAP) score, and surgeon proficiency were the high-risk factors for the prognosis and recurrence of UPJO. In addition, a nomogram was constructed based on the above 5 variables. The area under the curve (AUC) was 0.8831 after self cross-validation, which validated that the specificity of the model was favorable. Conclusion: The column chart constructed by five factors has good predictive ability for the prognosis and recurrence of UPJO, which may provide more reasonable guidance for the clinical diagnosis and treatment of this disease.
RESUMO
Tebuconazole is a chiral triazole fungicide used globally in agriculture as a racemic mixture, but its enantiomers exhibit significant enantioselective dissimilarities in bioactivity and environmental behaviors. The steric hindrance caused by the tert-butyl group makes it a great challenge to synthesize tebuconazole enantiomers. Here, we designed a simple chemoenzymatic approach for the asymmetric synthesis of (R)-tebuconazole, which includes the biocatalytic resolution of racemic epoxy-precursor (2-tert-butyl-2-[2-(4-chlorophenyl)ethyl] oxirane, rac-1a) by Escherichia coli/Rpeh whole cells expressed epoxide hydrolase from Rhodotorula paludigensis (RpEH), followed by a one-step chemocatalytic synthesis of (R)-tebuconazole. It was observed that (S)-1a was preferentially hydrolyzed by E. coli/Rpeh, whereas (R)-1a was retained with a specific activity of 103.8 U/g wet cells and a moderate enantiomeric ratio (E value) of 13.4, which was remarkably improved to 43.8 after optimizing the reaction conditions. Additionally, a gram-scale resolution of 200 mM rac-1a was performed using 150 mg/mL E. coli/Rpeh wet cells, resulting in the retention of (R)-1a in a 97.0% ees, a 42.5% yields, and a 40.5 g/L/d space-time yield. Subsequently, the synthesis of highly optical purity (R)-tebuconazole (>99% ee) was easily achieved through the chemocatalytic ring-opening of the epoxy-precursor (R)-1a with 1,2,4-triazole. To elucidate insight into the enantioselectivity, molecular docking simulations revealed that the unique L-shaped substrate-binding pocket of RpEH plays a crucial role in the enantioselective recognition of bulky 2,2-disubstituted oxirane 1a.
Assuntos
Biocatálise , Epóxido Hidrolases , Proteínas Fúngicas , Fungicidas Industriais , Rhodotorula , Triazóis , Rhodotorula/enzimologia , Rhodotorula/química , Rhodotorula/metabolismo , Triazóis/química , Triazóis/metabolismo , Fungicidas Industriais/química , Fungicidas Industriais/metabolismo , Fungicidas Industriais/síntese química , Epóxido Hidrolases/metabolismo , Epóxido Hidrolases/química , Estereoisomerismo , Proteínas Fúngicas/química , Proteínas Fúngicas/metabolismo , Simulação de Acoplamento Molecular , Escherichia coli/enzimologia , Escherichia coli/metabolismoRESUMO
Developing catalysts with high catalytic activity and stability in acidic media is crucial for advancing hydrogen production in proton exchange membrane water electrolyzers (PEMWEs). To this end, a self-supported WO3@RuO2 nanowire structure was grown in situ on a titanium mesh using hydrothermal and ion-exchange methods. Despite a Ru loading of only 0.098 wt %, it achieves an overpotential of 246 mV for the oxygen evolution reaction (OER) at a current density of 10 mA·cm-2 in acidic 0.5 M H2SO4 while maintaining excellent stability over 50 h, much better than that of the commercial RuO2. After the establishment of the WO3@RuO2 heterostructure, a reduced overpotential of the rate-determining step from M-O* to M-OOH* is confirmed by the DFT calculation. Meanwhile, its enhanced OER kinetics are also greatly improved by this self-supported system in the absence of the organic binder, leading to a reduced interface resistance between active sites and electrolytes. This work presents a promising approach to minimize the use of noble metals for large-scale PEMWE applications.
RESUMO
Wilms tumor (WT) is the most common malignancy of the genitourinary system in children. Currently, the Integration of single-cell RNA sequencing (scRNA-Seq) and Bulk RNA sequencing (RNA-Seq) analysis of heterogeneity between different cell types in pediatric WT tissues could more accurately find prognostic markers, but this is lacking. RNA-Seq and clinical data related to WT were downloaded from the Therapeutically Applicable Research to Generate Effective Treatments (TARGET) database. Small nucleolar RNA host gene 15 (SNHG15) was identified as a risk signature from the TARGET dataset by using weighted gene co-expression network analysis, differentially expressed analysis and univariate Cox analysis. After that, the functional mechanisms, immunological and molecular characterization of SNHG15 were investigated at the scRNA-seq, pan-cancer, and RNA-seq levels using Gene ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), ESTIMATE, and CIBERSORT. Based on scRNA-seq data, we identified 20 clusters in WT and annotated 10 cell types. Integration of single-cell and spatial data mapped ligand-receptor networks to specific cell types, revealing M2 macrophages as hubs for intercellular communication. In addition, in vitro cellular experiments showed that siRNAs interfering with SNHG15 significantly inhibited the proliferation and migration of G401 cells and promoted the apoptosis of G401 cells compared with the control group. The effect of siRNAs interfering with SNHG15 on EMT-related protein expression was verified by Western blotting assay. Thus, our findings will improve our current understanding of the pathogenesis of WT, and they are potentially valuable in providing novel prognosis markers for the treatment of WT.
RESUMO
Seawater electrolysis for hydrogen production is a sustainable and economical approach that can mitigate the energy crisis and global warming issues. Although various catalysts/electrodes with excellent activities have been developed for high-efficiency seawater electrolysis, their unsatisfactory durability, especially for anodes, severely impedes their industrial applications. In this review, attention is paid to the factors that affect the stability of anodes and the corresponding strategies for designing catalytic materials to prolong the anode's lifetime. In addition, two important aspects-electrolyte optimization and electrolyzer design-with respect to anode stability improvement are summarized. Furthermore, several methods for rapid stability assessment are proposed for the fast screening of both highly active and stable catalysts/electrodes. Finally, perspectives on future investigations aimed at improving the stability of seawater electrolysis systems are outlined.
RESUMO
Although hydrogen gas (H2 ) storage might enable offshore renewable energy to be stored at scale, the commercialization of technology for H2 generation by seawater electrolysis depends upon the development of methods that avoid the severe corrosion of anodes by chloride (Cl- ) ions. Here, it is revealed that the stability of an anode used for seawater splitting can be increased by more than an order of magnitude by loading Ag nanoparticles on the catalyst surface. In experiments, an optimized NiFe-layered double hydroxide (LDH)@Ag electrode displays stable operation at 400 mA cm-2 in alkaline saline electrolyte and seawater for over 5000 and 2500 h, respectively. The impressive long-term durability is more than 20 times that of an unmodified NiFe-LDH anode. Meticulous characterization and simulation reveals that in the presence of an applied electric field, free Cl- ions react with oxidized Ag nanoparticles to form stable AgCl species, giving rise to the formation of a Cl- -free layer near the anode surface. Because of its simplicity and effectiveness, it is anticipated that the proposed strategy to immobilize chloride ions on the surface of an anode has the potential to become a crucial technology to control corrosion during large-scale electrolysis of seawater to produce hydrogen.
RESUMO
Currently, the process of an acidic oxygen evolution reaction (OER) necessitates the use of Iridium dioxygen (IrO2), which is both expensive and incredibly scarce on Earth. Ruthenium dioxygen (RuO2) offers high activity for acidic OERs and presents a potential substitution for IrO2. Nevertheless, its practical application is hindered by its relatively poor stability. In this study, we have developed Mn-doped RuO2 (Mn-RuO2) nanoarrays that are anchored on a titanium (Ti) mesh utilizing a two-step methodology involving the preparation of MnO2 nanoarrays followed by a subsequent Ru exchange and annealing process. By precisely optimizing the annealing temperature, we have managed to attain a remarkably low overpotential of 217 mV at 10 mA cm-2 in a 0.5 M H2SO4 solution. The enhanced catalytic activity of our Mn-RuO2 nanoarrays can be attributed to the electronic modification brought about by the high exposure of active sites, Mn dopant, efficient mass transfer, as well as the efficient transfer of electrons between the Ti mesh and the catalyst arrays. Furthermore, these self-supported Mn-RuO2 nanoarrays demonstrated excellent long-term stability throughout a chronoamperometry test lasting for 100 h, with no discernible changes observed in the Ru chemical states.
RESUMO
Water electrolysis is currently a major technique to produce clean hydrogen, which is regarded as a promising and sustainable energy carrier. The efficiency of water electrolysis is highly dependent on the oxygen evolution reaction (OER) on the anode. The evaluation of an OER electrocatalyst is frequently carried out on a three-electrode system in a container of electrolyte. Herein, we found that the electrode positions in the electrolyte container could significantly affect the data acquisition of OER performance. After a detailed investigation, we reveal that the difference of the OER activity of an electrocatalyst at a different position is originated from their different iRu drop and the gas diffusion resistance. For the first time, this work evokes concerns on the accurate evaluation of electrocatalysts regarding the electrode position. For fair comparisons and reliable results, it is strongly suggested to keep the electrode position unchanged in the electrochemical measurements. In addition, the establishment of a standard electrolyzer setup for electrocatalysis evaluation in the electrochemical community is also called for.
RESUMO
Water electrolysis is a compelling method for the production of environmentally friendly hydrogen, minimizing carbon emissions. The electrolysis of water heavily relies on an effective and steady oxygen evolution reaction (OER) taking place at the anode. Herein, we introduce a highly promising catalyst for OER called CoSe2@NiFeOOH arrays, which are supported on nickel foam. This catalyst, referred to as CoSe2@NiFeOOH/NF, is fabricated through a two-step process involving the selenidation of a Co-based porous metal organic framework and subsequent electrochemical deposition on nickel foam. The CoSe2@NiFeOOH/NF catalyst demonstrates outstanding activity for the OER in an alkaline electrolyte. It exhibits a low overpotential (η) of 254 mV at 100 mA cm-2, a small Tafel slope of 73 mV dec-1, and excellent high stability. The good performance of CoSe2@NiFeOOH/NF can be attributed to the combination of the high conductivity of the inner layer and the synergistic effect between CoSe2 and NiFeOOH. This study offers an effective method for the fabrication of highly efficient catalysts for an OER.
RESUMO
The corrosive anions (e.g., Cl-) have been recognized as the origins to cause severe corrosion of anode during seawater electrolysis, while in experiments it is found that natural seawater (~0.41 M Cl-) is usually more corrosive than simulated seawater (~0.5 M Cl-). Here we elucidate that besides Cl-, Br- in seawater is even more harmful to Ni-based anodes because of the inferior corrosion resistance and faster corrosion kinetics in bromide than in chloride. Experimental and simulated results reveal that Cl- corrodes locally to form narrow-deep pits while Br- etches extensively to generate shallow-wide pits, which can be attributed to the fast diffusion kinetics of Cl- and the lower reaction energy of Br- in the passivation layer. Additionally, for the Ni-based electrodes with catalysts (e.g., NiFe-LDH) loading on the surface, Br- causes extensive spalling of the catalyst layer, resulting in rapid performance degradation. This work clearly points out that, in addition to anti-Cl- corrosion, designing anti-Br- corrosion anodes is even more crucial for future application of seawater electrolysis.
RESUMO
The reuse of powdered activated carbon (PAC) vitally determines the economics and security of the PAC-based adsorption process, while state-of-the-art PAC regeneration technologies are usually unsatisfactory. Here, it is demonstrated that isolated Fe sites anchored on commercial PAC enable fast H2 O2 activation to produce Fe-based reactive oxygen species for highly efficient PAC regeneration at room temperature. Taking rhodamine B as a representative pollutant, PAC decorated with isolated Fe sites realize H2 O2 based regeneration with negligible adsorption capacity degradation for 10 cycles. Moreover, in terms of the PAC loss rate, this technology is greatly superior to traditional Fenton-based regeneration technology. Further operando experiments and theoretical calculations reveal that the high regeneration performance can be attributed to the isolated HOFeO motifs, which activate H2 O2 via a nonradical reaction pathway. These findings provide a very promising strategy toward reducing the cost of H2 O2 -based PAC regeneration technology.
RESUMO
The catalytic ozonation-based advanced oxidation process (AOP) is applied to remove nondegradable chemical oxygen demand (COD), while the application in industry is limited by the economics and activity of catalysts. In this study, we demonstrate that by taking atrazine (ATZ) as a model pollutant, the removal rates of catalytic ozonation were negatively correlated with the interlayer water content of metal-modified montmorillonite (Mx@MMT), instead of the loadings metals. Among the modified MMT, Zn0.1@MMT achieved 83.2% degradation of ATZ within 15 min, and corresponding removal rates of COD and total organic carbon (TOC) reached 40.3% and 46.5%, respectively. Detailed EPR and quenching experiments identified that hydroxyl radicals (HOâ¢) were the main reactive oxygen species and QTOF/MS/MS analysis helped to propose a possible degradation pathway of ATZ. Moreover, the catalytic performance of Zn0.1@MMT under different conditions was also systematically evaluated.
Assuntos
Atrazina , Ozônio , Poluentes Químicos da Água , Purificação da Água , Atrazina/química , Bentonita , Catálise , Metais , Ozônio/química , Espectrometria de Massas em Tandem , Água , Poluentes Químicos da Água/análiseRESUMO
Tandem catalysis provides an economical and energy-efficient process for the production of fine chemicals. In this work, we demonstrate that a rationally synthesized carbon-based catalyst with atomically dispersed dual Fe-Al sites (ADD-Fe-Al) achieves superior catalytic activity for the one-pot oxidative carboxylation of olefins (conversion â¼97%, selectivity â¼91%), where the yield of target product over ADD-Fe-Al is at least 62% higher than that of monometallic counterparts. The kinetic results reveal that the excellent catalytic performance arises from the synergistic effect between Fe (oxidation site) and Al sites (cycloaddition site), where the efficient CO2 cycloaddition with epoxides in the presence of Al sites (3.91 wt %) positively shifts the oxidation equilibrium to olefin epoxidation over Fe sites (0.89 wt %). This work not only offers an advanced catalyst for oxidative carboxylation of olefins but also opens up an avenue for the rational design of multifunctional catalysts for tandem catalytic reactions in the future.
RESUMO
BACKGROUND: TIR domain containing adaptor molecule 1 (TICAM1) is a coding gene participating in immune and inflammation responses to malignant cells. However, the role of TICAM1 in Wilms tumor (WT) is rarely known. MATERIALS AND METHODS: The expression level of TICAM1 was calculated in the WT TARGET cohort and validated using the GSE66405 cohort. The Kaplan-Meier method was employed to investigate the potential clinical value of TICAM1 and the association between its expression level and clinical features. The influence of TICAM1 on immune infiltration was examined by ESTIMATE, CIBERSORT and MCPcounter algorithms. IC50 of chemotherapeutic drugs was calculated by "pRRophetic" R package. RESULTS: TICAM1 was downregulated in WT patients with worse prognosis and a more advanced clinical stage. Moreover, a low expression level of TICAM1 contributed to less immune cell infiltration, few protective immune cells and more antitumor immune cells. CONCLUSIONS: TICAM1 exerts a significant impact on the prognosis, progression and immune infiltration condition of WT.
Assuntos
Neoplasias Renais , Tumor de Wilms , Proteínas Adaptadoras de Transporte Vesicular/genética , Proteínas Adaptadoras de Transporte Vesicular/metabolismo , Biomarcadores , Biomarcadores Tumorais/genética , Biomarcadores Tumorais/metabolismo , Humanos , Tolerância Imunológica , Estimativa de Kaplan-Meier , Neoplasias Renais/patologia , Prognóstico , Tumor de Wilms/genética , Tumor de Wilms/patologiaRESUMO
The lack of characterizations of the adsorption capability toward intermediates during reactions causes difficulties in determining the structural optimization principle of the catalysts for the 2-electron oxygen reduction reaction (2e- ORR). Here, a Tafel-θ method is proposed to evaluate the surface coverage (θ) of important intermediates (*OOH and *OH) on the material surface and further help optimize the catalyst. With the assistance of Tafel-θ analysis, a Zn nanoparticle incorporated oxygen-doped carbon (ZnNP-O-C) catalyst with high 2e- ORR performance (onset of â¼0.57 V and selectivity of >90.4%) in neutral media was achieved. Both the theoretical calculation and characterization results are consistent with the Tafel-θ deduction, revealing that an appropriate ratio of Zn nanoparticles and bridging O can optimize the *OOH adsorption/desorption strength of the adjacent carbon site. This study not only provides an advanced ZnNP-O-C catalyst for electrochemical H2O2 production but also proposes a fast and precise method for the comprehensive assessment of future catalysts.
RESUMO
Defects in solid materials vitally determine their physicochemical properties; however, facile regulation of the defect density is still a challenge. Herein, we demonstrate that the ligand defect density of metal-organic frameworks (MOFs) with a UiO-66 structural prototype is precisely regulated by tuning the linker groups (X = OMe, Me, H, F). Detailed analyses reveal that the ligand defect concentration is positively correlated with the electronegativity of linker groups, and Ce-UiO-66-F, constructed by F-containing ligands and Ce-oxo nodes, possesses the superior ligand defect density (>25%) and identifiable irregular periodicity. The increase in ligand defect density results in the reduction of the valence state and the coordination number of Ce sites in Ce-UiO-66-X, and this merit further validates the relationship between the defective structure and catalytic performance of CO2 cycloaddition reaction. This facile, efficient, and reliable strategy may also be applicable to precisely constructing the defect density of porous materials in the future.