Electrocatalytic nitrate reduction (NO3RR) provides a sustainable pathway for converting nitrate into ammonia (NH3); however, achieving a high NH3 yield while simultaneously enabling its efficient recovery remains challenging. Herein, we develop an exsolved high-entropy perovskite oxide, La0.9 (MnFeCoCuZn)0.2O3 (Ex-LMFCCZ), through in-situ exsolution of multimetallic nanoparticles. The exsolved nanoparticles, together with the enriched oxygen vacancies, create abundant active sites, resulting in an NH3 yield rate of 5.62 mg/cm2/h, which is 2.13 times higher than that of the pristine catalyst Pr-LMFCCZ at-0.4 V vs. RHE. DFT calculations indicate that the downshifted D-band center facilitates the desorption of reaction intermediates, while the enhanced charge polarization promotes electron transfer, thereby enhancing the activity. In addition, the produced NH3 from NO3RR can be effectively captured as solid struvite (MgNH4PO4 & sdot;6 H2O). A closed-loop electrochemical system was further constructed for struvite recovery, in which NH3 originated from NO3RR, and both anodic and cathodic solutions dissolved waste minerals to provide PO43-and Mg2+ without external reagents, yielding struvite with a purity of 57.9%. This integrated system achieves simultaneous nitrate removal, ammonia recovery, and nutrient recycling, offering a green and circular pathway for sustainable wastewater valorization.
Chromium and arsenic are widely used in key industrial sectors, with chromium in electroplating and leather tanning, and arsenic in non-ferrous mining, smelting, and legacy pesticide production. Their improper disposal causes serious pollution of soil and groundwater, endangering human health. However, for chromium and arsenic remediation in both soil and aqueous systems, traditional in situ/ex situ techniques (e.g., chemical reduction, coagulation, bioremediation) may face trade-offs in many cases, such as secondary pollution from Cr(III)-bearing sludge generated by chemical reduction, high costs associated with excavation and transport in ex situ remediation, and prolonged timeframes required for bioremediation, depending on site-specific conditions. Therefore, researchers are actively seeking long-term and effective stabilization materials. However, the effectiveness of Cr(VI) and arsenic stabilization is highly dependent on matrix (soil/water), speciation (Cr(VI)/Cr(III), As(III)/As(V)), and geochemistry, with key controlling mechanisms in co-contaminated systems incompletely resolved-including Cr(VI)-As redox coupling mediated by Fe/Mn oxides, phosphate/sulfate competitive adsorption, and Fe(III) oxide dissolution-driven As mobilization. Based on the research of various functional materials, this article summarizes the types of materials for chromium and arsenic pollution remediation—covering stabilization/immobilization in soils and adsorption-based removal in waters—and their applications in contaminated sites. The mechanism of stabilization materials on chromium and arsenic elements is emphasized. In addition, we discuss the impact of environmental factors on stabilization material properties, and evaluate potential environmental risks during material application. Finally, we summarize the major challenges and future research prospects of chromium and arsenic stabilization materials, to promote the remediation of heavy metal pollution in soil and groundwater.
Periodate (PI)-based advanced oxidation processes have attracted growing attention for generating various reactive oxygen and iodine species. Herein, a fluorine‑manganese co-doped carbon catalyst (C-F-Mn) was fabricated via one-step pyrolysis for efficient PI activation toward acetaminophen (APAP) degradation. The C-F-Mn/PI system achieved ultrafast and complete APAP removal within 3 min with kobs of 0.6934 min−1, markedly surpassing pristine carbon and single-doped counterparts (CF and CMn). DFT calculations on fluorine-doped carbon (FC) model reveal that the semi-ionic CF bond induces a substantial electron transfer of 0.55e from the carbon layer to fluorine, generating electron-deficient Cδ+ sites. This polarization enhances IO4− adsorption (Eads = −0.893 eV vs. -0.196 eV for pristine C) and promotes interfacial electron transfer (0.26e vs. 0.08e), as visualized by differential charge density analysis. In the C-F-Mn catalyst, the semi-ionic CF bond is proposed to serve as an electron-transfer bridge between Mn2+/Mn3+ redox centers and adsorbed PI (Mn → semi-ionic C-F → PI). Multiple reactive species, including •OH, O2•−, 1O2, IO3•, and high-valent MnIVO were identified. Quenching experiments revealed that APAP degradation proceeds through a synergistic oxidation involving •OH, 1O2, and electronic transfer in comparable proportions. This study highlights the critical role of semi-ionic CF bonds in mediating interfacial electron transfer, providing new insights into the rational design of heteroatom-metal dual-doped carbon catalysts for advanced oxidation processes.
Figure S3. Distribution of PRO-CTCAE scores at successive time points during active therapy and maximum score post-baseline without and with baseline adjustment
Modulating peroxydisulfate (PDS) activation pathway by designing and constructing catalysts is highly desirable for mitigating hazardous antibiotic contamination in complex water matrices. In this study, a calcium modified biomass derived carbon catalyst was constructed to regulate the interfacial microenvironment using an earth-abundant main-group element rather than conventional redox-active noble or transition metals. Surface-localized CaO nanoclusters generated a polarized electronic microenvironment on the carbon matrix, achieving 91.0% tetracycline removal with a 95.6% contribution from the electron-transfer process (ETP). Experimental evidence and density functional theory calculations revealed that the CaO nanoclusters were not direct redox-active sites, but functioned as electronic microenvironment modulators by strengthening PDS adsorption, facilitating interfacial charge redistribution, and enhancing electron polarization. These effects redirected PDS activation from radical oxidation to a nonradical ETP-dominated pathway, which displayed excellent resistance to background water constituents. The transformed intermediates showed reduced toxicity, and life-cycle assessment further demonstrated a lower environmental burden of the Ca-modified carbon/PDS system. These results deepen the understanding of how a main-group element regulates reaction pathways in PDS-based advanced oxidation processes and highlight a sustainable strategy for eliminating hazardous antibiotics from contaminated water.
Conventional Fenton-based processes suffer from a narrow pH operating range and poor efficiency under neutral conditions, which greatly limits their scalability in practical wastewater treatment. Herein, we report an innovative strategy to overcome these challenges by constructing a bipyridine-based covalent organic framework (TFB-Bpy COF) as a coordination platform to anchor cobalt atoms, forming a highly active Co@TFB-Bpy catalyst for a three-dimensional electro-Fenton (3D EF) system. The resulting EF/Co@TFB-Bpy system effectively broadens the pH applicability of traditional Fenton reactions, enabling efficient degradation and mineralization of the antibiotic florfenicol (FFC) under neutral conditions. Benefiting from the dispersed Co sites and the conductive COF structure, the system achieved a remarkable H2O2 generation rate of 74.36 mg L-1 h-1, 98.83 % FFC degradation, and 95.68 % total organic carbon (TOC) removal within 30 min. Electrochemical analyses and electron spin resonance (ESR) spectroscopy confirmed that hydroxyl radicals (center dot OH) were the dominant reactive species. Combined HPLC-MS analysis and theoretical calculations revealed three major degradation pathways involving dechlorination, C-S bond cleavage, and ring-opening. Moreover, ecological structure-activity relationship (ECOSAR) predictions demonstrated that most intermediates exhibited reduced toxicity, while the final products were essentially non-toxic. This work provides a new avenue for developing COF-based single-site catalysts to construct efficient, pH-independent electro-Fenton systems, offering promising potential for sustainable antibiotic wastewater remediation.
Treating low C/N ratio wastewater is challenging because heterotrophic denitrification often suffers from insufficient electron donors. This study investigated the use of conductive pyrite (FeS2) as an anode filler to enhance the electrochemical performance and nitrogen removal capacity of sediment microbial fuel cells (sMFCs) for such wastewater. Pyrite-amended (PG-sMFC) and quartz sand control (QG-sMFC) reactors were operated for 64 days and systematic characterized. Results showed that PG-sMFC achieved a maximum output voltage of 698.3 mV (1.8-fold of QG-sMFC) and a maximum power density of 44.8 mW/m2 (1.3-fold of QG-sMFC). Without exogenous carbon, PG-sMFC reached a total nitrogen (TN) removal efficiency of 96.0 ± 0.7% within 48 h and completed nitrate reduction 16 h earlier than QG-sMFC. Mechanistically, pyrite expanded the anodic electrochemical activity window, facilitated extracellular electron transfer (EET), and enriched exoelectrogens, with Geobacter abundance increased from 2.6% to 33.9%. This enhanced anodic electron flux triggered a cathodic cascade effect, which remodeled the extracellular polymeric substances (EPS) composition, up-regulated nitrogen metabolism enzyme activities, and optimized the microbial community for efficient simultaneous nitrification and denitrification (SND). This work provides a sustainable and electron-efficient strategy for the resource-oriented treatment of low C/N ratio wastewater, offering new insights into the application of mineral-amended bioelectrochemical systems.
In this study, a visible-light-responsive photocatalyst was synthesized by immobilizing Ni-doped TiO2 onto acid-activated kaolinite using a sol impregnation and vapor-thermal hydrolysis method. The resulting composite (NTSCK) was systematically characterized, revealing well-dispersed anatase TiO2 nanoparticles uniformly anchored on a porous silica-rich framework with enhanced specific surface area. The photocatalytic performance of NTSCK was evaluated through the degradation of Rhodamine B (RhB) under visible-light irradiation. The material achieved 91% degradation of RhB within 180 min, demonstrating significantly enhanced activity compared to unmodified TiO2. The improved performance is attributed to a synergistic mechanism: acid activation of kaolinite generates abundant Lewis acid sites that act as electron traps to suppress charge recombination, while Ni3+/Ni2+ redox centers in the TiO2 lattice narrow the bandgap for visible-light harvesting and serve as reversible charge-trapping sites. This work provides a rational strategy for designing high-performance visible-light-driven photocatalysts by combining transition metal doping with acid-activated clay supports, offering a promising pathway for developing cost-effective and efficient materials for environmental remediation.
Photocatalytic hydrogen evolution and pollutant degradation are both promising strategies for clean energy production and environmental remediation, yet their integration for synchronous wastewater-to-energy conversion is fundamentally hindered by inefficient charge utilization and severe interfacial redox competition. Herein, a quantum-dot-bridged dual-defect interface engineering strategy is developed to synchronize photocatalytic oxidation and hydrogen evolution for wastewater-to-energy conversion. As a result, a hierarchical S-type heterostructure was constructed by integrating Ti3C2 MXene quantum dots with electron-storage capability, sulfur-vacancy-rich MoS2, and oxygen-deficient CeO2 (TMMC), which effectively accelerated interfacial charge transport. The optimized catalyst achieves a hydrogen evolution rate of 12.17 mmol g-1 h-1 with 98.6% norfloxacin removal and maintains high stability under continuous operation. In pollutant-containing systems, hydrogen production reaches 274.35 μmol g-1 h-1 and further increases to 405.93 μmol g-1 h-1 upon low-dose peroxymonosulfate addition. Mechanistically, Ce-O-Mo interfacial coupling induces asymmetric charge redistribution and a built-in electric field for directional carrier separation, while spatially separated sulfur and oxygen vacancies regulate proton reduction and oxidant activation, respectively, mitigating interfacial redox competition. This work establishes defect-coordinated interfacial engineering as a general paradigm for regulating charge utilization and reaction selectivity in integrated photocatalytic systems.
Hsa_circ_0002111 is highly expressed in papillary thyroid carcinoma (PTC). We therefore investigated its role and underlying mechanism in promoting PTC progression. Q-RT-PCR, dual-luciferase reporter assays, AGO2-RIP, CCK-8, colony formation, wound healing, and Transwell assays were employed to dissect the circRNA/miRNA/mRNA axis interactions and their functional phenotypes. Results showed that silencing hsa_circ_0002111 significantly inhibited the viability, migration, and invasion of KTC-1 cells. Mechanistic studies demonstrated that hsa_circ_0002111 acted as a sponge for miR-432-5p, which in turn targeted the 3’UTR of CDKN2B and suppressed its expression. Functional assays revealed that either hsa_circ_0002111 knockdown or miR-432-5p overexpression inhibited migration and invasion, whereas inhibition of miR-432-5p reversed these cellular processes. Consistently, siRNA-mediated knockdown of CDKN2B phenocopied the motility defects observed upon hsa_circ_0002111 silencing, suggesting that CDKN2B is a functionally relevant downstream effector. Thus, the hsa_circ_0002111/miR-432-5p/CDKN2B axis is implicated in papillary thyroid carcinoma progression. These findings revealed a novel regulatory mechanism of hsa_circ_0002111 in KTC-1 cells and suggest its potential as a therapeutic target, offering new insights for future clinical applications and research directions in thyroid cancer.
Waste biomass upcycling into high-value functional materials is pivotal for sustainable environmental remediation, yet achieving efficient catalytic kinetics remains a formidable challenge. Here, we developed a 3D electro-catalytic platform by anchoring atomically dispersed Co-N4 sites onto herb-residue-derived Zn-modified carbon nanofibers (ZCF) to construct a high-performance Co-MOF@ZCF particle electrode. This 3D architecture strategically overcomes the intrinsic kinetic bottleneck of peroxymonosulfate (PMS) activation-the sluggish Co(III) to Co(II) reduction-by leveraging the synergy between nanoconfinement and electro-driven redox cycling. Specifically, the external electric field provides a persistent reductive driving force for the in-situ regeneration of active Co(II) sites, while the ZCF framework ensures rapid interfacialelectron flux. This synergistic system achieved a remarkable 98.89% removal of oxytetracycline (OTC) within 30 min (k = 0.152 min-1), outperforming the catalyst-free EO/PMS system. Mechanistic insights reveal that the nanoconfined environment within the 3D electrode enriches reactive species, with 1O2 and O2•⁻ contributing 69.1% to the degradation. Beyond OTC, the system demonstrated broad-spectrum activity against a diverse arrayof persistent pollutants, including PPCPs and perfluorinated compounds. Furthermore, the electrode maintained >85% efficiency over 120 h in real pharmaceutical wastewater treatment with negligible metal leaching. Combined with a low energy consumption (EE/O = 1.56 kWh m-3) and a net-negative life-cycle assessment (LCA), this work provides a transformative "waste-to-wealth" strategy for breaking the redox kinetic barriers in advanced oxidation processes via single-atom electro-catalysis.
Developing high-performance flow electrodes is critical for advancing flow-electrode capacitive deionization (FCDI) toward practical water treatment. Here, we present a single-atom Fe engineered polyaniline/activated carbon/MXene (FeSA-PAM) composite electrode that achieves simultaneous brackish water desalination and treatment of real electroplating wastewater. Through advanced characterization including AC-TEM, XANES and EXAFS, we confirm that atomically dispersed Fe sites are anchored within the composite, serving as highly active centers which significantly enhance charge transfer kinetics and provide specific redox activity for Cr(VI) reduction. The optimized FeSA-PAM electrode delivers a high salt removal rate of 125 mu gcm(-2)min(-1) (60 % improvement over conventional AC electrode) and maintains exceptional Cr(VI) removal efficiency of 85-92 % across a broad concentration range (5-120 mgL-1), achieving drinking water standards (<0.01 mgL-1) with ultralow energy consumption (0.006-0.072 kWhm(-3)) and high charge efficiency (ca. 92 %). The removal mechanism involves synergistic effects of electrostatic adsorption, ion intercalation, and Fe-mediated reduction, while the electrode also enables effective chromium recovery (ca. 60 % in electrolyte phase). Techno-economic and environmental assessments confirm its cost-effectiveness ($3.75 m(-3) treated water) and low carbon footprint (0.072 kg CO2 m(-3)), positioning FeSA-PAM as a scalable and environmentally sustainable flow electrode platform for water purification.
Abstract Background Polygenic risk scores (PRSs) strongly discriminate for prostate cancer risk at the population level. The role of these genetic scores in determining prostate cancer survival is unclear, potentially due to methodological issues. Methods We included 19,607 men from the Malmö Diet and Cancer Study (MDCS) and the Health Professionals Follow-up Study (HPFS) and analyzed 20-year incidence and mortality (from full cohort analyses) and survival (from case-only analyses) according to a 451-variant PRS. For most of the men included, early access to prostate-specific antigen (PSA) testing was limited. Results In full cohort analyses, a PRS at or above the median (vs. below the median) shows a strong association with prostate cancer incidence (hazard ratio (HR) 3.02, 95% CI 2.78-3.28) and, somewhat stronger, with prostate cancer mortality (HR 3.26, 95% CI 2.63-4.04). As expected, case-only survival analyses of prostate cancer death show a similar direction (HR 1.21, 95% CI 0.98-1.50), which becomes stronger when excluding variants linked to PSA (HR 1.25, 95% CI, 1.01-1.54), in particular in the age group 65-74 years at diagnosis (HR 1.72, 95% CI 1.21-2.45). In the other age groups, HRs are close to or below 1. This indicates that standard case-only survival estimates may not accurately reflect risk across age, consistent with age-dependent selection mechanisms, and further points to an influence from disease detection. Conclusions Overall, these findings support that inherited genetic risk captured by the 451-variant PRS may have an influence on prostate cancer survival.
Objective Lung cancer is the leading cause of cancer-related death. The percentage of people who have never smoked with lung cancer has risen recently, but alternative risk factors require further study. Our goal was to determine the impact of air quality on incidence of lung cancer in people who have smoked or never smoked. Methods The Cancer Registry from a large urban medical center was queried to include every new diagnosis of lung cancer from 2013 to 2021. Air quality and pollution data for the county were obtained from the United States Environmental Protection Agency from 1980 to 2018. Patient demographics, location of residence, smoking history and tumor stage were recorded. Bivariate comparison analyses were conducted in R. Results A total of 2,223 new cases of lung cancer were identified. Mean age was 69.2 years. There was a nonsmoking rate of 8.1 percent. A total of 37 percent of patients identified as a racial minority. People who have never smoked were more likely to be diagnosed at an advanced stage. When analyzing geographic distribution, incidence of lung cancer among people who have never smoked was more closely associated with highly polluted areas. People who have never smoked with lung cancer had significantly higher exposure levels of multiple pollutants. Conclusions Newly diagnosed lung cancer appears to be more related to poor air quality among people who have never smoked than people who have smoked. Future studies are needed to examine the associations of specific pollutants with lung cancer incidence.
Aim: The reprogramming of lipid metabolism can markedly enhance the nutritional adaptability of tumor cells to the glucose-deficient and hypoxic tumor microenvironment, which holds profound significance for the development and metastasis of liver cancer. Nevertheless, the alterations of lipid metabolism under stress conditions and the specific mechanisms remain ambiguous. The current study aimed to explore the molecular interaction between endoplasmic reticulum (ER) stress and lipid metabolism in hepatocellular carcinoma (HCC) using bioinformatics analysis, and further verify the role of core hub genes and offer potential targets for diagnosing and treating HCC. Methods: Differentially expressed lipid-related genes (DLRGs) were identified via cross-crossing differentially expressed genes (DEGs) in the TCGA-LIHC program and lipid metabolism-related genes in the Genecards database. Identification of hub genes was achieved by constructing a protein-protein interaction (PPI) network, gene ontology (GO), and Kyoto Encyclopedia of Genes and Genomes (KEGG). Disease correlation analysis was performed in the Comparison of Toxicology Database, receiver operating characteristic (ROC) curve and Kaplan-Meier curve analyses were performed for the hub genes, and the CIBERSORT algorithm was employed to assess immune infiltration. The role of acetyl-CoA carboxylase 1 (ACACA) in HCC was evaluated by Western blotting, polymerase chain reaction, immunohistochemistry, and CCK-8 assay. Results: In total, 131 DLRGs were identified, comprising 70 upregulated and 61 downregulated. PPI analysis identified 20 hub DLRGs, while ROC curve analysis and Kaplan-Meier analysis further revealed that ACACA, LCAT, APOC3, LPA and PON1 may hold diagnostic and prognostic value for HCC patients. More importantly, ACACA overexpression was related to unfavorable overall survival (OS) and adverse pathological characteristics in HCC patients. In addition, both free fatty acid (FFA) and tunicamycin (TM) could activate ER stress and enhance the expression of ACACA in HCC. Interestingly, inhibition of ER stress or fatty acid synthesis using 4-phenylbutyric acid (4-PBA) or fenofibrate significantly reduced the expression of ACACA, and fenofibrate inhibits HCC cell proliferation. Conclusion: The study identifies a novel core lipid metabolism-related gene called ACACA, which has prognostic and therapeutic potential for HCC. We also provide a deep understanding of lipid metabolism correlated with ER stress in the progression of HCC, offering new opportunities for the identification of biological targets and the development of drugs and treatments for HCC patients.
Despite advances in diagnosis and treatment, the prognosis of non-small cell lung cancer (NSCLC) remains poor. Therefore, it is urgent to identify potential molecular targets. In this study, we investigated the function and internal mechanism of CPNE3 in the malignant biological behaviour via RACK1/c-MET signalling in NSCLC, and explored the feasibility of the MET inhibitor in NSCLC treatment. The expression of CPNE3 in normal tissues and lung cancer tissues was compared using a public database. The function of CPNE3 was investigated using CCK-8 assays, clonogenic assays, EdU assays, Transwell assays and cell cycle analysis. Western blotting was used to detect the protein expression. The interaction between CPNE3 and RACK1 was examined by immunofluorescence staining and co-immunoprecipitation (co-IP). The in vitro and in vivo functions of the MET inhibitor JNJ-38877605 were investigated. CPNE3 is overexpressed in NSCLC and facilitates tumorigenesis and metastasis by interacting with RACK1 through the VWFA domain, which further induces the activation of MET signalling. Accordingly, this process could be suppressed by the MET inhibitor and RACK1 knockdown in vitro and in vivo. CPNE3 is highly expressed in NSCLC and can promote the proliferation and migration of tumour cells. CPNE3 could interact with RACK1 through the VWFA domain and activate MET signalling. These findings may provide new insights into the development of novel therapeutic strategies for NSCLC.