Fenton-process is effective to remove recalcitrant micro-pollutants, like 2,4-dichlorophenol (2,4-DCP). However, traditional Fenton is associated with numerous limitations. In this study, two different aminopolycarboxylic acids (APCAs) ethylenediamine-N,N '-disuccinic acid (EDDS) and nitrilotriacetic acid (NTA) were selected to form Fe (III) complexes to enhance the traditional photo-Fenton process. Excellent removal rates and mineralization of 2,4-DCP were both achieved in the presence of Fe(III)-APCAs complexes. Such promotion effects could mainly be attributed to the enhancement of Fe(III)/Fe(II) redox and the decomposition of H2O2 in the presence of these complexes, resulting in the increased production of hydroxyl radicals (center dot OH), which was confirmed by scavenging experiments and ESR analysis. In addition, although the production pathway of center dot OH radicals in the two systems were similar, their rates and formation mechanisms quite different. Both superoxide radical (O2 center dot-) and photosensitive process played important roles, but their relative contributions were distinct between the systems. By the application of LC-MS analysis and Molecular orbital calculations, the degradation pathways and mechanisms of 2,4-DCP in APCAs promoted photo-Fenton process were proposed. Specifically, 2,4-DCP was found to undergo three different oxidation pathways including dechlorination, dehydrogenation and hydroxylation in both systems. This study will make a comprehensive research and specific comparison on the APCAs promoted photo-Fenton reactions.

Over the past 20 years, the iron-activated persulfate systems have been widely used for removing pharmaceuticals and personal care products (PPCPs) from water. However, slow Fe(III)/Fe(II) redox cycling and precipitation of iron, unless in very acidic conditions, were the main limitations. Thus, two ligand-assisted Fe(III)/persulfate systems, Fe(III)-acetohydroxamic acid (AHA)/peroxydisulfate (PDS) and Fe(III)-nitrilotriacetic acid (NTA)/peroxymonosulfate (PMS), were comparatively investigated for the degradation of atenolol (ATL) in this study. The experimental results showed that the Fe(III)-NTA/PMS system worked much better than the AHA system. However, the cost of PMS is higher than that of PDS, which should be considered. The primary advantage of the NTA system was its ability to overcome the pH limitations. It worked well over a wide pH range (3.0-10.0), whereas the AHA system could only be used in a narrower pH window (pH 2.4 to 6.5). The investigation of radicals that contributed to ATL degradation revealed that sulfate radicals (SO4 center dot-) were dominant in the NTA system, while hydroxyl radicals (center dot OH) and SO4 center dot- were the primary and secondary radicals in the AHA system. These results provided useful insight into the comparative behavior of two ligand-assisted Fe(III)/persulfate systems for ATL degradation, with the Fe(III)-NTA/PMS system showing clear potential under neutral or near-neutral conditions, while Fe(III)-AHA/PDS may still represent a lower-cost option under acidic conditions.

Catalytic ozonation is often limited by inefficient ozone utilization at gas–liquid–solid interfaces and sluggish mineralization of refractory oxidation intermediates. Here, we report a facile and potentially scalable molecular foaming strategy to construct macroporous Mn–Ce binary oxides (HP-MnCeO) that integrate interconnected diffusion pathways with coupled Mn2+/Mn3+/Mn4+ and Ce3+/Ce4+ redox cycles. The optimized HP-70MnCeO exhibited enhanced deep oxidation capability, achieving 68% total organic carbon removal during carbamazepine ozonation, while only moderately accelerating parent compound degradation compared with ozonation alone. Compared with mesoporous counterparts, HP-70MnCeO delivered a 1.7-fold higher apparent reaction rate and promoted more efficient transformation of refractory intermediates, despite its lower surface area. It also accelerated ozone decomposition by 6–12 times compared with single-metal oxides, demonstrating improved ozone activation and utilization. Finite element simulations indicate that macropores enhance O3 and pollutant transport, while density functional theory suggests preferential O3 adsorption at Mn–Ce bridge sites. HP-70MnCeO maintained stable activity with negligible Mn leaching (0.01 mg/L) during cycling tests and enabled continuous-flow treatment of real wastewater. This work provides a strategy for designing macroporous multimetal oxide catalysts with enhanced mineralization efficiency for practical ozone-based water purification.

The treatment of bacteria-infected wounds requires not only the rapid elimination of pathogens but also the timely promotion of wound healing to prevent progression to chronic infectious diseases. Given that the pH microenvironment at wound sites dynamically changes in response to bacterial proliferation, the development of pH-responsive nanozymes offers a promising strategy for both timely bacterial eradication and the promotion of wound healing. These nanozymes are capable of catalyzing H2O2 to produce reactive oxygen species under acidic conditions and O2 under neutral conditions, thereby enabling tailored therapeutic activity in accordance with the wound's pathological state. Nevertheless, the underlying mechanism of H2O2 decomposition by pH-responsive nanozymes has not been clearly elucidated. Herein, we design that doping Cu into MoO3-x induces its d-band center change, endowing it with significantly enhanced catalase (CAT)-like and peroxidase (POD)-like activities. Through rigorous theoretical calculations and experimental validation, we have elucidated the catalytic mechanism of Cu-doped MoO3-x and its pH-dependent pathway of H2O2 decomposition. Furthermore, Cu-MoO3-x hybrids demonstrated outstanding microenvironment-adaptive antibacterial and wound-healing properties both in vitro and in vivo. Under acidic conditions, these hybrids leveraged the enhanced POD-like activity to eradicate bacteria by disrupting cell membranes, proteins, and DNA. Conversely, under neutral conditions, the CAT-like activity of Cu-MoO3-x hybrids accelerated wound healing by promoting cell proliferation, upregulate angiogenic factors (VEGF, CD31), and suppressing hypoxia (HIF-1 alpha) and inflammation. By uncovering the synergistic effect of Cu doping and pH on the catalytic mechanism, this study offers a framework for the rational design and precise catalytic regulation of advanced pH-responsive nanozymes.

Background: The incidence of thyroid cancer has been increasing in recent years, with papillary thyroid carcinoma (PTC) accounting for the majority of cases. Accumulating studies have demonstrated that S100A10 acts as an oncogene in the progression of various malignancies. However, the function and specific mechanisms of S100A10 in thyroid cancer remain poorly defined. Methods: Single-cell RNA sequencing data of PTC from public databases were analyzed to screen differentially expressed genes (DEGs), among which S100A10 emerged as a potential biomarker associated with PTC metastasis and prognosis. The expression of S100A10 in tissues and cell lines were validated by RT-qPCR and western blot. Protein-protein interactions were confirmed using mass spectrometry analysis and co-immunoprecipitation. The subcellular localization of the protein was determined by immunofluorescence. Stable PTC cell lines overexpressing S100A10 were constructed and followed by transwell assays, wound-healing assays, and western blot for EMT capability detection. Results: S100A10 was found to play essential roles in tumor metastasis and was associated with unfavorable prognosis in patients with PTC. S100A10 was expressed higher in both PTC tissues and cells. Furthermore, both in vitro and in vivo experiments confirmed that S100A10 activates the PI3K/AKT signaling and promotes EMT in PTC cells, enhancing the invasive capabilities of tumors. S100A10 could interact with both RAN and EGFR intracellularly, forming a RAN-S100A10-EGFR regulatory axis. Finally, several potential drugs targeting S100A10 were identified for further in-depth research. Conclusion: These findings clarify the role of S100A10 and RAN in PTC progression and highlight their potential as therapeutic targets, linking EMT with PI3K/AKT signaling.

Carbon nitride-supported single-atom catalysts have shown considerable promise in activating peroxymonosulfate (PMS) for pollutant removal. However, constructing an ordered mesoporous structure to increase the accessible surface area and maximize the utilization of reactive species remains a challenge. In this study, a single-atom Fe catalyst confined in a mesoporous C3N4@N-C hybrid support (denoted as Fe-C3N4@N-C) was synthesized via a facile solvent-free nanocasting strategy. The catalyst comprises atomically dispersed Fe-N4 sites in C3N4@N-C hybrids with enhanced interfacial electron transfer. Faithful replication of the silica template imparted ordered mesoporous architecture with a high surface area (∼462 m2/g) and a large pore volume (0.46 cm3/g). The optimized catalyst exhibited superior performance in degrading bisphenol A (BPA), achieving nearly complete removal (>99%) within 20 min and a mineralization rate of ∼77% within 60 min. The degradation rate constant was 1 order of magnitude greater than that of the mesoporous Fe-C3N4 (prepared using Dicyandiamide as a precursor) and 2 orders of magnitude higher than that of a nonporous reference sample. Mechanistic studies revealed a nonradical degradation pathway dominated by singlet oxygen (1O2) and electron transfer, which conferred strong anti-interference capability, broad pH adaptability and excellent stability under continuous-flow conditions. Density functional theory calculation reveals that the Fe-N4 sites within the cavity of C3N4 serve as dominant active sites for PMS activation and the ordered mesoporous structure facilitates their accessibility.

In this work, adsorption-activation dual-site synergy in N-doped carbon catalysts for bisphenol A (BPA) degradation via peroxymonosulfate (PMS) activation was investigated. The catalysts were constructed by a sequential double-melting calcination strategy. They are made of N-doped mesoporous carbon nanosheets decorated with g-C3N4 nanodots, possessing dual sites and hierarchical macro-mesopores. The optimized sample presents superior performance in BPA removal (100 % degraded and similar to 90% mineralized from solution in 45 min), about an order of magnitude higher than the catalyst without g-C3N4 nanodots. The reaction follows a singlet oxygen (O-1(2)) pathway, possessing versatility for removing phenolic compounds, and good anti-interference and stability in flow operation. The BPA adsorption and PMS activation are determined by pyridinic/pyrrolic N sites and graphitic-N-doped carbon sites, respectively, while mesopores are essential for both. The BPA adsorption on pyrrolic N sites can lower the energy barrier of PMS decomposition on graphitic-N-doped carbon sites (the rate-limiting step) to generate O-1(2).

Transition metal compounds integrate with carbon nanomaterials can augment their inherently low conductivity and poor structural stability. However, the mechanism underlying the synergistic effect between carbon materials and metal compounds remains unclear. In this study, composites of ZnCoS and porous carbon are prepared through a hydrothermal process and applied as supercapacitor electrodes (ZnCoS/C). The porous carbon can influence the structural characteristics and properties of ZnCoS, which is examined using a blend of experimental approaches and theoretical calculations. The performances of ZnCoS/C are experimentally regulated by varying the content of porous carbon. Results indicate that the specific capacitance of ZnCoS/C-2 sample is 603.10 F g-1 (5 mV s-1), which holds 91 % for 10,000 cycles at 20 A g-1, demonstrating long cyclic life. Density Functional Theory (DFT) reveals that the incorporation of carbon materials benefits for the ZnCoS/C structure stability, reduces the band gap, and promotes the O-H ions' adsorption and desorption on electrode surface. These calculations explain the superior multipurpose performance, stable cycle life, and rapid reaction kinetics of the electrode. This study integrates experimental and computational approaches to explore the regulating effect of carbon material on composite structure, providing valuable insights into the design of high-performance supercapacitors.

TiO2-based materials have demonstrated significant potential for photocatalytic peroxymonosulfate (PMS) activation; however, the rational design of catalysts that maintain both high catalytic activity and long-term stability remains challenging. In this study, selective lattice doping of iron (Fe) in TiO2 nanoparticles is achieved via a solvothermal method using arginine as a complexing agent. The resulting Fe-doped TiO2 nano-particles exhibit an anatase-brookite bicrystalline phase, small particle size (<20 nm) and high specific surface area (>133 m(2)/g). Iron doping leads to exceptional performance in photocatalytic PMS activation for carbamazepine (CBZ) degradation, that is, similar to 78 % and 100 % CBZ can be removed in 5 and 20 min, respectively, which is improved by similar to 4.5 times compared with the iron-free sample. The composites demonstrate remarkable stability in both batch experiments and continuous-flow systems for at least 10 h with minimal iron leaching (<0.1 mg/L). Mechanistic studies reveal that the PMS activation is primarily enabled by photogenerated electrons and interfacial iron species, with HO center dot, SO4 center dot- and holes identified as the dominant reactive species. Notably, the Fe-doped TiO2 catalysts exhibit strong resistance to environmental interference and maintain high activity across a wide pH range (3-11). This work provides new insights into the design of robust lattice-confined metal-doped TiO2 nanoparticles and their sustainable application in PMS-based advanced oxidation processes.

Valorization of biomass wastes into carbon-based catalysts for water treatment is a clear paradigm of sustainability. This study systematically investigates the catalytic ozonation performance, structure-performance relationship and reaction mechanism of a series of biochar catalysts prepared via temperature-controlled pyrolysis of five waste biomasses, including coffee residue, pomelo peel, coconut shell, corn cob and mango kernel. The coffee-residue-derived biochar at 900 °C is identified as the best catalyst, showing rapid and 100% removal of oxalic acid (OA) and various other micropollutants, high effectiveness under various conditions, including different pH values, reaction temperatures, dosages of catalyst and ozone (O3), water matrices, and the presence of different anions, good stability under flow operation, as well as easy regeneration with nearly complete performance recovery by thermal treatment at 300 °C. Linear relationships between the key properties of the biochar catalysts (density of phenolic hydroxyl (OH) group, density of carbonyl (CO) groups and graphitization degree) and their performance parameters (O3 adsorption capacity, O3 decomposition rate, H2O2 formation rate and OA removal rate) are disclosed. Experimental and theoretical calculation results reveal a novel adsorption-electron transfer synergistic mechanism toward high performance. The phenolic OH and CO groups are the major and supplemental active sites, respectively, for O3 activation, while a high graphitization degree is essential to enable efficient electron transfer, cooperatively promoting O3 decomposition to produce rich hydroxyl radicals (•OH) for rapid pollutant degradation.

The pervasive use of thermoplastic polyurethane (TPU) poses significant environmental challenges, necessitating effective strategies for its high-value upcycling. Herein, a facile approach is developed to convert TPU into highperformance porous carbon electrodes via a graphene oxide (GO)-assisted coating and activation process. A small amount of GO effectively prevents polymer agglomeration while directing the formation of a hierarchical threedimensional porous structure. The optimized material (TPU-60) exhibits a high specific surface area and abundant heteroatom doping. Consequently, it delivers a superior specific capacitance of 381 F g- 1 at 1 A g- 1 in 1 M H2SO4 electrolyte. Furthermore, the assembled symmetric supercapacitor achieves an impressive maximum energy density of 7.95 Wh kg- 1 at a power density of 150 W kg-1, while retaining 6.59 Wh kg- 1 even at 1000 W kg- 1. The device also demonstrates remarkable long-term durability with 95% capacitance retention after 10,000 cycles. This study not only offers a scalable route for upcycling waste TPU but also provides insights into constructing efficient conductive frameworks for advanced energy storage systems.

Metal aggregation and insufficient site exposure are common issues in fabricating metal-nitrogen-carbon single-atom catalysts (SACs). Herein, a universal interface metal imprinting (IMI) strategy is proposed for surface-selective synthesis of nitrogen-doped ordered mesoporous carbon (NOMC) supported SACs. It involves constructing an intimate and full-coverage interface between a metal-atom-doped template (typically Fe-doped SBA-15) and a nanocast N-doped carbon, followed by metal migration from the template framework to the interface and imprinting onto the N-doped carbon surface. Density Functional Theory calculations and characterizations confirm the IMI process's thermodynamic feasibility and high efficiency. The resulting NOMC supported Fe SAC (Fesurf-NOMC) features ordered mesoporosity, high site density (1.71 & times; 1019 sites g-1), and excellent surface exposure. It exhibits superb oxygen reduction reaction performance with a half-wave potential of 0.92 V, a turnover frequency of 4.31 e site-1 s-1, and a high stability, outperforming counterparts prepared by co-nanocasting and post-loading. The aqueous zinc-air battery using Fesurf-NOMC as the cathode shows excellent performance with a peak power density of 194.7 mW cm-2 and a specific capacity of 807.8 mAh gZn -1. The IMI strategy is applicable to different templates and metals, providing a platform for fabricating ordered or disordered mesoporous surface-enriched SACs.

This review comprehensively summarizes the latest advancements in the synthesis and multifaceted applications of metal-organic frameworks (MOFs) for clean water. It systematically explores scalable synthesis methods, from solvothermal to green mechanochemical routes, and highlights the innovative transformation of waste into high-value MOFs. The article delves into the diverse functionalities of MOFs in water remediation, including the adsorptive and catalytic removal of heavy metals, organic pollutants, pharmaceuticals, PFASs, and micro/nano-plastics. Applications in sensing, radionuclide separation, oil-water separation, and advanced membrane technologies are also detailed. Furthermore, emerging roles in water capture, algal inhibition and resource recovery are discussed. Finally, the review provides a critical perspective on future challenges and opportunities, emphasizing sustainable synthesis, life-cycle assessment, and the integration of AI for the intelligent design of next-generation MOFs, paving the way for their transition from laboratory research to real-world water treatment solutions.

A novel heterostructure photocatalyst composed of Fe3O4/BiOI1/3Cl2/3 microspheres was fabricated via a facile coprecipitation method and comprehensively characterized by XRD, SEM, XPS, BET, DRS and zeta potential analysis. The photocatalytic performance of the Fe3O4/BiOI1/3Cl2/3 heterostructure for the tetracycline (TC) degradation with visible light irradiation (lambda > 420 nm) was evaluated, achieving a degradation efficiency of 91.3% after 60 mins. This performance was significantly better than Fe3O4/BiOCl reference. Moreover, Fe3O4/BiOI1/3Cl2/3 showed the best activity under neutral conditions (pH = 7). The exceptional photocatalytic efficiency of Fe3O4/BiOI1/3Cl2/3 might be attributed to its significant absorption in the visible spectrum, coupled with a reduced rate of recombination of electron-hole pairs. Furthermore, two main reactive oxidation species were identified, from which h(+) and O-2(center dot-) contributed to approximately 85.3% and 14.0%, respectively, to the TC degradation. The degradation byproducts were examined using liquid chromatography-mass spectrometry, and potential degradation pathways for TC were suggested. Toxicities of these products were also evaluated.

Papillary thyroid cancer (PTC) exhibits a high propensity for lymph node metastasis (LNM), significantly impacting postoperative recurrence and patient prognosis. The hypoxic microenvironment critically drives tumor progression by promoting PTC dedifferentiation. Through integrated bioinformatics analysis combining weighted gene co-expression network analysis and machine learning approaches on TCGA data, we identified TPM4 as a key hypoxia-responsive gene in PTC and validated its association with LNM using GEO datasets. Gene set enrichment analysis demonstrated that patients with high TPM4 expression in both TCGA and GEO databases showed significant enrichment in hypoxia and epithelial-mesenchymal transition (EMT) pathways. Single-cell pseudotime analysis revealed concurrent increases in hypoxia pathway enrichment, TPM4 expression, and EMT pathway activation during cell differentiation. Experimental validation using RT-qPCR and Western blot analyses confirmed that hypoxia-induced TPM4 upregulation activated EMT signaling. Functional assays demonstrated that TPM4 enhanced cellular invasion and migration capabilities. Our findings illuminate a novel mechanism whereby the hypoxic tumor microenvironment promotes lymph node metastasis in PTC through TPM4-mediated activation of EMT signaling, providing new insights into LNM of PTC.

Gamma-delta (γδ) T cells are a critical component of the tumor microenvironment and have been recognized as a promising biomarker and target for cancer therapy. Increasing evidence suggests that γδT cells play distinct roles in different cancers. However, the impact of γδT cells in breast cancer remains controversial. In this study, we investigated the role of γδT cells in breast cancer using a comprehensive approach, including bulk and single-cell sequencing, radiomics based on magnetic resonance imaging (MRI), genomic data, and immunohistochemistry. Single-cell RNA profiling was used to infer the potential lineage evolution of γδT cells and their interactions with other immune cells. Bulk RNA sequencing was included to uncover the heterogeneity in signaling pathways, as well as radiotherapy and immunotherapy responses, among patients with varying levels of γδT cell abundance. Genomic analysis was used to recognize the critical gene mutations with the infiltration of γδT cells. Immunohistochemistry was performed to validate the prognostic value of γδT cells in breast cancer patients. Lastly, radiomics was used to establish a correlation between the abundance of γδT cells and the features of MRI images. The γδT cell infiltration was closely associated with favorable prognosis in triple-negative breast cancer (TNBC) but not in other subtypes of breast cancer. γδT cells may exert antitumor effects through intrinsic lineage evolution or interact with antigen-presenting cells through ligand-receptor pairs. Patients with a high γδT cell abundance may benefit more from chemotherapy or radiotherapy alone than their combination. Additionally, patients with a high γδT cell abundance were more likely to benefit from immunotherapy. Finally, we established a radiomic model based on dynamic contrast-enhanced-MRI, which indicated the potential for estimating the γδT cell abundance for patients with TNBC. Our study provides novel insight and a theoretical basis for individualized therapy of patients with TNBC based on γδT cells.

Photocatalytic N2 fixation offers a sustainable method for NH3 production, requiring efficient and stable semiconductor catalysts. Here, we report that TiO2 materials with a 3D spherical mesoporous structure and rationally engineered oxygen vacancies (Ov) can efficiently activate N2 via promoting Ti 3d-N 2p orbital interactions. The Ov concentration in the mesoporous TiO2 can be precisely adjusted by controlling the hydrochloric acid concentration in the solvothermal precursor. The Ov-TiO2-500 is proven highly efficient for N2 chemisorption and activation and photo-generated charge separation. Its mesoporous structure and rough surface enhance light utilization and mass transfer. These synergistic effects enable superior NH3 production. Ov-TiO2-500 attains an excellent and stable NH3 production rate of 284 mu mol h- 1 g- 1. DFT calculation results reveal that the Ov in OvTiO2-500 enables a strong N2 activation via Ti 3d-N 2p orbital interactions for easy electron transfer and a low N2 to NH3 conversion energy barrier for facile hydrogenation.

Emergent literacy skills are essential for reading development, yet autistic students face a greater risk of reading difficulties. This qualitative-driven, mixed-methods study explored public preschool teachers' pedagogical content knowledge in teaching emergent literacy to autistic children. Findings from questionnaires and interviews with ten purposively selected, licensed public-school teachers revealed general knowledge of emergent literacy and autism but highlighted gaps in areas like phonemic awareness. Teachers acknowledged challenges in effectively teaching emergent literacy to autistic students and expressed a need for additional training. Notably, they lacked familiarity with research-supported instructional strategies for autistic learners and often prioritized social and behavioral skills over emergent literacy instruction. These findings emphasize the need for targeted professional development and further research to enhance emergent literacy instruction in preschool settings.

A novel heterostructure photocatalyst composed of Fe 3 O 4 /BiOI 1/3 Cl 2/3 microspheres was fabricated via a facile coprecipitation method and comprehensively characterized by XRD, SEM, XPS, BET, DRS and zeta potential analysis. The photocatalytic performance of the Fe 3 O 4 /BiOI 1/3 Cl 2/3 heterostructure for the tetracycline (TC) degradation with visible light irradiation (λ > 420 nm) was evaluated, achieving a degradation efficiency of 91.3% after 60 mins. This performance was significantly better than Fe 3 O 4 /BiOCl reference. Moreover, Fe 3 O 4 /BiOI 1/3 Cl 2/3 showed the best activity under neutral conditions (pH = 7). The exceptional photocatalytic efficiency of Fe 3 O 4 /BiOI 1/3 Cl 2/3 might be attributed to its significant absorption in the visible spectrum, coupled with a reduced rate of recombination of electron‐hole pairs. Furthermore, two main reactive oxidation species were identified, from which h + and O 2 •− contributed to approximately 85.3% and 14.0%, respectively, to the TC degradation. The degradation byproducts were examined using liquid chromatography‐mass spectrometry, and potential degradation pathways for TC were suggested. Toxicities of these products were also evaluated.