Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

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.

Chemoenzymatic Asymmetric Synthesis of Chiral Triazole Fungicide (R)-Tebuconazole in High Optical Purity Mediated by an Epoxide Hydrolase from Rhodotorula paludigensis.

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.

Self-Supported WO3@RuO2 Nanowires for Electrocatalytic Acidic Water Oxidation.

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.

The construction of a nomogram to predict the prognosis and recurrence risks of UPJO.

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.

Identification and analysis of MSC-Exo-derived LncRNAs related to the regulation of EMT in hypospadias.

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.

Nephroblastoma-specific dysregulated gene SNHG15 with prognostic significance: scRNA-Seq with bulk RNA-Seq data and experimental validation.

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.

Progress in Anode Stability Improvement for Seawater Electrolysis to Produce Hydrogen.

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.

Ag Nanoparticle-Induced Surface Chloride Immobilization Strategy Enables Stable Seawater Electrolysis.

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.

Self-Supporting Mn-RuO2 Nanoarrays for Stable Oxygen Evolution Reaction in Acid.

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.

Concerns on the Effects of Electrode Positions in Electrolyte Container for the Oxygen Evolution Reaction.

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.

MOF-Derived CoSe2@NiFeOOH Arrays for Efficient Oxygen Evolution Reaction.

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.

Concerning the stability of seawater electrolysis: a corrosion mechanism study of halide on Ni-based anode.

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.

Cost-Effective H2 O2 -Regeneration of Powdered Activated Carbon by Isolated Fe Sites.

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.

The effect of interlayer water of metal-modified montmorillonite for catalytic ozonation.

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 (HO•) 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.

Atomically Dispersed Dual Metal Sites Boost the Efficiency of Olefins Epoxidation in Tandem with CO2 Cycloaddition.

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 ∼97%, selectivity ∼91%), 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.

Downregulated TICAM1 is a prognostic biomarker and associated with immune tolerance of Wilms tumor patients.

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.

Tafel Analysis Guided Optimization of ZnNP-O-C Catalysts for the Selective 2-Electron Oxygen Reduction Reaction in Neutral Media.

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 ∼0.57 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.

Ligand Defect Density Regulation in Metal-Organic Frameworks by Functional Group Engineering on Linkers.

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.

Atomically Dispersed High-Density Al-N4 Sites in Porous Carbon for Efficient Photodriven CO2 Cycloaddition.

Highly active catalysts that can directly utilize renewable energy (e.g., solar energy) are desirable for CO2 value-added processes. Herein, aiming at improving the efficiency of photodriven CO2 cycloaddition reactions, a catalyst composed of porous carbon nanosheets enriched with a high loading of atomically dispersed Al atoms (≈14.4 wt%, corresponding to an atomic percent of ≈7.3%) coordinated with N (AlN4 motif, Al-N-C catalyst) via a versatile molecule-confined pyrolysis strategy is reported. The performance of the Al-N-C catalyst for catalytic CO2 cycloaddition under light irradiation (≈95% conversion, reaction rate = 3.52 mmol g-1 h-1 ) is significantly superior to that obtained under a thermal environment (≈57% conversion, reaction rate = 2.11 mmol g-1 h-1 ). Besides the efficient photothermal conversion induced by the carbon matrix, both experimental and theoretical analysis reveal that light irradiation favors the photogenerated electron transfer from the semiconductive Al-N-C catalyst to the epoxide reactant, facilitating the formation of a ring-opened intermediate through the rate-limiting step. This study not only provides an advanced Al-N-C catalyst for photodriven CO2 cycloaddition, but also furnishes new insight for the rational design of superior photocatalysts for diverse heterogeneous catalytic reactions in the future.

Organic wastewater treatment by a single-atom catalyst and electrolytically produced H2O2.

The presence of organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Although advanced oxidation processes that rely on highly reactive radicals to destroy organic contaminants are appealing treatment options, substantial energy and chemical inputs limit their practical applications. Here we demonstrate that Cu single atoms incorporated in graphitic carbon nitride can catalytically activate H2O2 to generate hydroxyl radicals at pH 7.0 without energy input, and show robust stability within a filtration device. We further design an electrolysis reactor for the on-site generation of H2O2 from air, water and renewable energy. Coupling the single-atom catalytic filter and the H2O2 electrolytic generator in tandem delivers a wastewater treatment system. These findings provide a promising path toward reducing the energy and chemical demands of advanced oxidation processes, as well as enabling their implementation in remote areas and isolated communities.