FAM120A deficiency improves resistance to cisplatin in gastric cancer by promoting ferroptosis.

The occurrence of chemoresistance is an inescapable obstacle affecting the clinical efficacy of cisplatin in gastric cancer (GC). Exploring the regulatory mechanism of cisplatin resistance will help to provide potential effective targets for improving the prognosis of gastric cancer patients. Here, we find that FAM120A is upregulated in GC tissues and higher in cisplatin-resistant GC tissues, and its high expression is positively correlated with the poor outcome of GC patients. Functional studies indicate that FAM120A confers chemoresistance to GC cells by inhibiting ferroptosis. Mechanically, METTL3-induced m6A modification and YTHDC1-induced stability of FAM120A mRNA enhance FAM120A expression. FAM120A inhibits ferroptosis by binding SLC7A11 mRNA and enhancing its stability. FAM120A deficiency enhances cisplatin sensitivity by promoting ferroptosis in vivo. These results reveal the function of FAM120A in chemotherapy tolerance and targeting FAM120A is an effective strategy to alleviate cisplatin resistance in GC.

The lemon genome and DNA methylome unveil epigenetic regulation of citric acid biosynthesis during fruit development.

Citric acid gives lemons their unique flavor, which impacts their sensory traits and market value. However, the intricate process of citric acid accumulation during lemon fruit growth remains incompletely understood. Here, we achieved a chromosomal-level genome assembly for the 'Xiangshui' lemon variety, spanning 364.85 Mb across nine chromosomes. This assembly revealed 27 945 genes and 51.37% repetitive sequences, tracing the divergence from citron 2.85 million years ago. DNA methylome analysis of lemon fruits across different developmental stages revealed significant variations in DNA methylation. We observed decreased CG and CHG methylation but increased CHH methylation. Notably, the expression of RdDM pathway-related genes increased with fruit development, suggesting a connection with elevated CHH methylation, which is potentially influenced by the canonical RdDM pathway. Furthermore, we observed that elevated CHH DNA methylation within promoters significantly influenced the expression of key genes, critically contributing to vital biological processes, such as citric acid accumulation. In particular, the pivotal gene phosphoenolpyruvate carboxykinase (ClPEPCK), which regulates the tricarboxylic acid cycle, was strikingly upregulated during fruit development, concomitant with increased CHH methylation in its promoter region. Other essential genes associated with citric acid accumulation, such as the MYB transcription factor (ClPH1/4/5) and ANTHOCYANIN 1 (ClAN1), were strongly correlated with DNA methylation levels. These results strongly indicate that DNA methylation crucially orchestrates the metabolic synthesis of citric acid. In conclusion, our study revealed dynamic changes in DNA methylation during lemon fruit development, underscoring the significant role of DNA methylation in controlling the citric acid metabolic pathway.

Depletion of JunB increases adipocyte thermogenic capacity and ameliorates diet-induced insulin resistance.

The coexistence of brown adipocytes with low and high thermogenic activity is a fundamental feature of brown adipose tissue heterogeneity and plasticity. However, the mechanisms that govern thermogenic adipocyte heterogeneity and its significance in obesity and metabolic disease remain poorly understood. Here we show that in male mice, a population of transcription factor jun-B (JunB)-enriched (JunB+) adipocytes within the brown adipose tissue exhibits lower thermogenic capacity compared to high-thermogenic adipocytes. The JunB+ adipocyte population expands in obesity. Depletion of JunB in adipocytes increases the fraction of adipocytes exhibiting high thermogenic capacity, leading to enhanced basal and cold-induced energy expenditure and protection against diet-induced obesity and insulin resistance. Mechanistically, JunB antagonizes the stimulatory effects of PPARγ coactivator-1α on high-thermogenic adipocyte formation by directly binding to the promoter of oestrogen-related receptor alpha, a PPARγ coactivator-1α downstream effector. Taken together, our study uncovers that JunB shapes thermogenic adipocyte heterogeneity, serving a critical role in maintaining systemic metabolic health.

Sensitization of colon cancer cells to cisplatin by Fbxw7 via negative regulation of the Nox1-mTOR pathway.

Colorectal cancer (CRC) is a human malignancy which associates with high mortality rate and poor prognosis. Despite the initial effectiveness in clinical applications of chemotherapeutic agents, a fraction of patients develops chemoresistance. Fbxw7 is an F-box protein serving as a substrate recognition subunit of E3 ubiquitin ligase, leading to degradation of various oncoproteins. In this study, Fbxw7 was significantly downregulated in CRC tumors as well as CRC cells. Fbxw7 suppressed CRC cell proliferation and migration. Moreover, we observed Fbxw7 was positively associated with cisplatin sensitivity. Fbxw7 was significantly downregulated in cisplatin resistant CRC cells. Overexpression of Fbxw7 effectively increased the cisplatin sensitivity of cisplatin resistant CRC cells. Co-immunoprecipitation and GST pull-down assays showed Fbxw7 bond with Nox1 which was a superoxide-generating NADPH oxidase and showed oncogenic roles in colon cancer cells. Interestingly, Fbxw7 downregulated Nox1 through binding it to degrade Nox1 protein. We demonstrated that Fbxw7 negatively regulated mTOR activity through downregulation of Nox1. Finally, overexpression of Fbxw7 effectively increased the cisplatin sensitivity of CRC cells. This process could be further overturned by Nox1 restoration in Fbxw7-overexpressing colon cancer cells. In summary, these results unveiled that Fbxw7 targeted Nox1 for degradation, resulting in blocking the downstream Nox1-mTORC1 signaling to sensitize CRC cells to cisplatin. Our study potentiates that targeting the Fbxw7-Nox1-mTOR pathway could be an effective approach to overcome chemoresistance of colon cancer cells.

Heterogeneous Fenton water purification catalyzed by iron phosphide (FeP).

Heterogeneous Fenton reaction has a great application potential in water purification, but efficient catalysts are still lacking. Iron phosphide (FeP) has a higher activity than the conventional Fe-based catalysts for Fenton reactions, but its ability as a Fenton catalyst to directly activate H2O2 remains unreported. Herein, we demonstrate that the fabricated FeP has a lower electron transfer resistance than the typical conventional Fe-based catalysts, i.e., Fe2O3, Fe3O4, and FeOOH, and thus could active H2O2 to produce hydroxyl radicals more efficiently. In the heterogeneous Fenton reactions for sodium benzoate degradation, the FeP catalyst presents a superior activity with a reaction rate constant more than 20 times those of the other catalysts (i.e., Fe2O3, Fe3O4, and FeOOH). Moreover, it also exhibits a great catalytic activity in the treatment of real water samples and has a good stability in the cycling tests. Furthermore, the FeP could be loaded onto a centimeter-sized porous carbon support and the prepared macro-sized catalyst exhibits an excellent water treatment performance and can be well recycled. This work reveals a great potential of FeP as a catalyst for heterogeneous Fenton reactions and may inspire further development and practical application of highly efficient catalysts for water purification.

Epigenetically modified AP-2α by DNA methyltransferase facilitates glioma immune evasion by upregulating PD-L1 expression.

Programmed death-ligand 1 (PD-L1) ensures that tumor cells escape T-cell-mediated tumor immune surveillance. However, gliomas are characteristic of the low immune response and high-resistance therapy, it is necessary to understand molecular regulatory mechanisms in glioblastoma, especially the limited regulation of PD-L1 expression. Herein, we show that low expression of AP-2α is correlated with high expression of PD-L1 in high-grade glioma tissues. AP-2α binds directly to the promoter of the CD274 gene, not only inhibits the transcriptional activity of PD-L1 but enhances endocytosis and degradation of PD-L1 proteins. Overexpression of AP-2α in gliomas enhances CD8+ T cell-mediated proliferation, effector cytokine secretion, and cytotoxicity in vitro. Tfap2a could increase the cytotoxic effect of Cd8+ T cells in CT26, B16F10, and GL261 tumor-immune models, improve anti-tumor immunity, and promote the efficacy of anti-PD-1 therapy. Finally, the EZH2/H3K27Me3/DNMT1 complex mediates the methylation modification of AP-2α gene and maintains low expression of AP-2α in gliomas. 5-Aza-dC (Decitabine) treatment combines with anti-PD-1 immunotherapy to efficiently suppress the progression of GL261 gliomas. Overall, these data support a mechanism of epigenetic modification of AP-2α that contributes to tumor immune evasion, and reactivation of AP-2α synergizes with anti-PD-1 antibodies to increase antitumor efficacy, which may be a broadly applicable strategy in solid tumors.

Distinguishing homogeneous advanced oxidation processes in bulk water from heterogeneous surface reactions in organic oxidation.

Clarifying the reaction pathways at the solid-water interface and in bulk water solution is of great significance for the design of heterogeneous catalysts for selective oxidation of organic pollutants. However, achieving this goal is daunting because of the intricate interfacial reactions at the catalyst surface. Herein, we unravel the origin of the organic oxidation reactions with metal oxide catalysts, revealing that the radical-based advanced oxidation processes (AOPs) prevail in bulk water but not on the solid catalyst surfaces. We show that such differing reaction pathways widely exist in various chemical oxidation (e.g., high-valent Mn3+ and MnOX) and Fenton and Fenton-like catalytic oxidation (e.g., Fe2+ and FeOCl catalyzing H2O2, Co2+ and Co3O4 catalyzing persulfate) systems. Compared with the radical-based degradation and polymerization pathways of one-electron indirect AOP in homogeneous reactions, the heterogeneous catalysts provide unique surface properties to trigger surface-dependent coupling and polymerization pathways of a two-electron direct oxidative transfer process. These findings provide a fundamental understanding of catalytic organic oxidation processes at the solid-water interface, which could guide the design of heterogeneous nanocatalysts.

Integrated analysis reveals the microenvironment of non-small cell lung cancer and a macrophage-related prognostic model.

Background: In the treatment of non-small cell lung cancer (NSCLC), recent advances in immunotherapy have heralded a new era. Despite the success of immune therapy, a subset of patients persistently fails to respond. Therefore, to better improve the efficacy of immunotherapy and achieve the purpose of precision therapy, the research and exploration of tumor immunotherapy biomarkers have received much attention. Methods: Single-cell transcriptomic profiling was used to reveal tumor heterogeneity and the microenvironment in NSCLC. The Cell-type Identification by Estimating Relative Subsets of RNA Transcripts (CIBERSORT) algorithm was utilized to speculate the relative fractions of 22 infiltration immunocyte types in NSCLC. Univariate Cox and least absolute shrinkage and selection operator (LASSO) regression analyses were used for the construction of risk prognostic models and predictive nomograms of NSCLC. Spearman's correlation analysis was employed to explore the relationship between risk score and tumor mutation burden (TMB) and immune checkpoint inhibitors (ICIs). Screening of chemotherapeutic agents in the high- and low-risk groups was performed with the "pRRophetic" package in R. Intercellular communication analysis was conducted using the "CellChat" package. Results: We found that most tumor-infiltrating immune cells were T cells and monocytes. We also found that there was a significant difference in the tumor-infiltrating immune cells and ICIs across different molecular subtypes. Further analysis showed that M0 and M1 mononuclear macrophages were significantly different in different molecular subtypes. The risk prediction model was shown to have to ability to accurately predict the prognosis, immune cell infiltration, and chemotherapy efficacy of patients in the high and low-risk groups. Finally, we found that the carcinogenic effect of migration inhibitory factor (MIF) is mediated by binding to CD74, CXCR4, and CD44 receptors involved in MIF cell signaling. Conclusions: We have revealed the tumor microenvironment (TME) of NSCLC through single-cell data analysis and constructed a prognosis model of macrophage-related genes. These results could provide new therapeutic targets for NSCLC.

Pt/CeO2 coated with polyoxometallate chainmail to regulate oxidation of chlorobenzene without hazardous by-products.

Doping noble metal and acid functionalization were both valid approaches to facilitate oxidation of chlorobenzene on CeO2-based catalysts, but their promotion effects were influenced by different orders of modification process. Because of strong interaction between metal and support and proper redox nature of CeO2, Pt NPs were re-dispersed into single atoms on CeO2 surface via "ex-solution". Companied with Pt loading, the enhancement of oxidizing ability led to generation of polychlorinated by-products. Herein, CeO2-supported Pt was coated by HSiW chainmail to protect Pt from being exposed to Cl-contained atmosphere, and HSiW coating promoted activation of chlorobenzene. The as-prepared chainmail catalyst of HSiW/Pt/CeO2 displayed a remarkable performance in catalyzing oxidation of chlorobenzene without any dichlorobenzene at realistic condition. By comparison, other catalysts with exposed Pt suffered from production of toxic by-products.

Genome-Wide Analysis of the RNase T2 Family and Identification of Interacting Proteins of Four ClS-RNase Genes in 'XiangShui' Lemon.

S-RNase plays vital roles in the process of self-incompatibility (SI) in Rutaceae plants. Data have shown that the rejection phenomenon during self-pollination is due to the degradation of pollen tube RNA by S-RNase. The cytoskeleton microfilaments of pollen tubes are destroyed, and other components cannot extend downwards from the stigma and, ultimately, cannot reach the ovary to complete fertilisation. In this study, four S-RNase gene sequences were identified from the 'XiangShui' lemon genome and ubiquitome. Sequence analysis revealed that the conserved RNase T2 domains within S-RNases in 'XiangShui' lemon are the same as those within other species. Expression pattern analysis revealed that S3-RNase and S4-RNase are specifically expressed in the pistils, and spatiotemporal expression analysis showed that the S3-RNase expression levels in the stigmas, styles and ovaries were significantly higher after self-pollination than after cross-pollination. Subcellular localisation analysis showed that the S1-RNase, S2-RNase, S3-RNase and S4-RNase were found to be expressed in the nucleus according to laser confocal microscopy. In addition, yeast two-hybrid (Y2H) assays showed that S3-RNase interacted with F-box, Bifunctional fucokinase/fucose pyrophosphorylase (FKGP), aspartic proteinase A1, RRP46, pectinesterase/pectinesterase inhibitor 51 (PME51), phospholipid:diacylglycerol acyltransferase 1 (PDAT1), gibberellin receptor GID1B, GDT1-like protein 4, putative invertase inhibitor, tRNA ligase, PAP15, PAE8, TIM14-2, PGIP1 and p24beta2. Moreover, S3-RNase interacted with TOPP4. Therefore, S3-RNase may play an important role in the SI of 'XiangShui' lemon.

Proteomic analysis of ubiquitinated proteins in 'Xiangshui' lemon [Citrus limon (L.)] pistils after self- and cross-pollination.

'Xiangshui' lemon exhibits gametophyte self-incompatibility: after self-pollination, the growth of a pollen tube in the style is inhibited. The aim of this work was to study the effect of pollination on the ubiquitylome and proteome in 'Xiangshui' lemon pistil. Here, by using label-free quantification, enrichment by anti-diglycine lysine antibody conjugated agarose beads, high-resolution liquid chromatography tandem mass spectrometry (LC-MS/MS) and the method of shotgun proteomics, we investigated the quantitative proteome, ubiquitylome, and crosstalk between the two datasets in the 'Xiangshui' lemon pistil after pollination. In total, 4682 protein species, 1956 ubiquitinated protein species and 6922 ubiquitination sites were quantified. A principal component analysis revealed that there were some differences in the ubiquitylome and proteome of CK, self-pollination and cross-pollination. The results of the crosstalk showed that the proteome and ubiquitylome were negatively correlated. After self-pollination, the abundance of the ubiquitinated protein species related to programmed cell death, cell aging and sphingolipid metabolic pathways was changed. Furthermore, we analyzed the proteasome pathway in the pistil after self-pollination and further discussed the mechanism by which ubiquitination events affect S-RNase in the style. Overall, pollination greatly changed the ubiquitinated protein species abundance in the pistils of 'Xiangshui' lemon. Accordingly, our work provides a systematic analysis of the proteome and ubiquitylome in 'Xiangshui' lemon pistils under self-incompatibility and sheds light for future studies on the function and mechanism of ubiquitination during self-incompatibility in 'Xiangshui' lemon. SIGNIFICANCE: As a mechanism to prevent self-pollination, self-incompatibility (SI) exists widely in plant species. Although a large number of SI-related genes have been found in fruit trees, there are few studies on the PTMs that affect and are involved in fruit tree responses to SI. This study highlights the fact that the effects of pollination on proteome and ubiquitylome in the 'Xiangshui' lemon pistil, we discussed the correlation between transcriptome and proteome, ubiquitylome and proteome, and we analyzed the expression and the changes of ubiquitination levels of SI related proteins and pathway after self- and cross pollination, and the changes of ubiquitination level of 26S proteasome pathway after cross-pollination. This study provides new insights into the ubiquitination pathway of SI in 'Xiangshui' lemon.

Simultaneous nanocatalytic surface activation of pollutants and oxidants for highly efficient water decontamination.

Removal of organic micropollutants from water through advanced oxidation processes (AOPs) is hampered by the excessive input of energy and/or chemicals as well as the large amounts of residuals resulting from incomplete mineralization. Herein, we report a new water purification paradigm, the direct oxidative transfer process (DOTP), which enables complete, highly efficient decontamination at very low dosage of oxidants. DOTP differs fundamentally from AOPs and adsorption in its pollutant removal behavior and mechanisms. In DOTP, the nanocatalyst can interact with persulfate to activate the pollutants by lowering their reductive potential energy, which triggers a non-decomposing oxidative transfer of pollutants from the bulk solution to the nanocatalyst surface. By leveraging the activation, stabilization, and accumulation functions of the heterogeneous catalyst, the DOTP can occur spontaneously on the nanocatalyst surface to enable complete removal of pollutants. The process is found to occur for diverse pollutants, oxidants, and nanocatalysts, including various low-cost catalysts. Significantly, DOTP requires no external energy input, has low oxidant consumption, produces no residual byproducts, and performs robustly in real environmental matrices. These favorable features render DOTP an extremely promising nanotechnology platform for water purification.

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density.

Developing heterogeneous catalysts with atomically dispersed active sites is vital to boost peroxymonosulfate (PMS) activation for Fenton-like activity, but how to controllably adjust the electronic configuration of metal centers to further improve the activation kinetics still remains a great challenge. Herein, we report a systematic investigation into heteroatom-doped engineering for tuning the electronic structure of Cu-N4 sites by integrating electron-deficient boron (B) or electron-rich phosphorus (P) heteroatoms into carbon substrate for PMS activation. The electron-depleted Cu-N4/C-B is found to exhibit the most active oxidation capacity among the prepared Cu-N4 single-atom catalysts, which is at the top rankings of the Cu-based catalysts and is superior to most of the state-of-the-art heterogeneous Fenton-like catalysts. Conversely, the electron-enriched Cu-N4/C-P induces a decrease in PMS activation. Both experimental results and theoretical simulations unravel that the long-range interaction with B atoms decreases the electronic density of Cu active sites and down-shifts the d-band center, and thereby optimizes the adsorption energy for PMS activation. This study provides an approach to finely control the electronic structure of Cu-N4 sites at the atomic level and is expected to guide the design of smart Fenton-like catalysts.

Quantitative Coassembly for Precise Synthesis of Mesoporous Nanospheres with Pore Structure-Dependent Catalytic Performance.

Precise synthesis of porous materials is essential for their applications. Self-assembly is a widely used strategy for synthesizing porous materials, but quantitative control of the assembly process still remains a great challenge. Here, a quantitative coassembly approach is developed for synthesizing resin/silica composite and its derived porous spheres. The assembly behaviors of the carbon and silica precursors are regulated without surfactants and the growth kinetics of the composite spheres are quantitatively controlled. This assembly approach enables the precise control of the size and pore structures of the derived carbon spheres. These carbon spheres provide a good platform to explore the structure-performance relationships of porous materials, and demonstrate their pore structure-dependent performance in catalytic water decontamination. This work provides a simple and robust approach for precise synthesis of porous spheres and brings insights into function-oriented design of porous materials.

Rapid field testing of mercury pollution by designed fluorescent biosensor and its cells-alginate hydrogel-based paper assay.

With increasing industrial activities, mercury has been largely discharged into environment and caused serious environmental problems. The growing level of mercury pollution has become a huge threat to human health due to its significant biotoxicity. Therefore, the simple and fast means for on-site monitoring discharged mercury pollution are highly necessary to protect human beings from its pernicious effects in time. Herein, a "turn off" fluorescent biosensor (mCherry L199C) for sensing Hg2+ was successfully designed based on direct modification of the chromophore environment of fluorescent protein mCherry. For rapid screening and characterization, the designed variant of mCherry (mCherry L199C) was directly expressed on outer-membrane of  Escherichia coli cells by cell surface display technique. The fluorescent biosensor was characterized to have favorable response to Hg2+ at micromole level among other metal ions and over a broad pH range. Further, the cells of the fluorescent biosensor were encapsulated in alginate hydrogel to develop the cells-alginate hydrogel-based paper. The cells-alginate hydrogel-based paper could detect mercury pollution in 5 min with simple operation process and inexpensive equipment, and it could keep fluorescence and activity stable at 4 °C for 24 hr, which would be a high-throughput screening tool in preliminarily reporting the presence of mercury pollution in natural setting.

Interface-Promoted Direct Oxidation of p-Arsanilic Acid and Removal of Total Arsenic by the Coupling of Peroxymonosulfate and Mn-Fe-Mixed Oxide.

As one of the extensively used feed additives in livestock and poultry breeding, p-arsanilic acid (p-ASA) has become an organoarsenic pollutant with great concern. For the efficient removal of p-ASA from water, the combination of chemical oxidation and adsorption is recognized as a promising process. Herein, hollow/porous Mn-Fe-mixed oxide (MnFeO) nanocubes were synthesized and used in coupling with peroxymonosulfate (PMS) to oxidize p-ASA and remove the total arsenic (As). Under acidic conditions, both p-ASA and total As could be completely removed in the PMS/MnFeO process and the overall performance was substantially better than that of the Mn/Fe monometallic system. More importantly, an interface-promoted direct oxidation mechanism was found in the p-ASA-involved PMS/MnFeO system. Rather than activate PMS to generate reactive oxygen species (i.e., SO4·-, ·OH, and 1O2), the MnFeO nanocubes first adsorbed p-ASA to form a ligand-oxide interface, which improved the oxidation of the adsorbed p-ASA by PMS and ultimately enhanced the removal of the total As. Such a direct oxidation process achieved selective oxidation of p-ASA and avoidance of severe interference from the commonly present constituents in real water samples. After facile elution with dilute alkali solution, the used MnFeO nanocubes exhibited superior recyclability in the repeated p-ASA removal experiments. Therefore, this work provides a promising approach for efficient abatement of phenylarsenical-caused water pollution based on the PMS/MnFeO oxidation process.

Catalytic degradation of ciprofloxacin by a visible-light-assisted peroxymonosulfate activation system: Performance and mechanism.

Peroxymonosulfate (PMS) is extensively used as an oxidant to develop the sulfate radical-based advanced oxidation processes in the decontamination of organic pollutants and various PMS activation methods have been explored. Visible-light-assisted PMS activation to construct a Fenton-like process has shown a great potential for pollution control. In our work, BiVO4 nanosheets were prepared using a hydrothermal process and used to activate PMS under visible light. A rapid degradation of ciprofloxacin (CIP) was achieved by dosing PMS (0.96 g/L), BiVO4 (0.32 g/L) under visible light with a reaction rate constant of 77.72-fold higher than that in the BiVO4/visible light process. The electron spin resonance and free radical quenching experiments indicate that reactive species of •O2-, h+, •OH and SO4•- all worked, where h+, •OH and SO4•- were found as the dominant contributors to the CIP degradation. The spectroscopic analyses further demonstrate that the photoinduced electrons were directly involved in the PMS activation process. The generated •O2- was partially utilized to activate PMS and more •OH was produced because of the chain reactions between SO4•- and H2O/OH-. In this process, PMS acted as an electron acceptor to transfer the photo-induced charges from the conduction band of BiVO4 and PMS was successfully activated to yield the high-powered oxidative species. From the degradation intermediates of CIP detected by a liquid-chromatography-mass spectrometer, the possible degradation pathways were proposed. The substantially decreased toxicity of CIP after the reaction was also observed. This work might provide new insights into the visible-light-assisted PMS activation mechanisms and is useful to construct environmentally-friendly catalytic processes for the efficient degradation of organic pollutants.

Degradation of benzoic acid in an advanced oxidation process: The effects of reducing agents.

Fenton reaction is widely used for hazardous pollutant degradation. Reducing agents (RAs) have been proven to be efficient in promoting the generation of HO• in Fenton reaction by accelerating the redox cycle of Fe3+/Fe2+. However, the roles of different RAs in Fenton reaction remain unrevealed. In this work, the catalytic activity of three RAs, i.e., hydroxylamine (NH2OH), ascorbic acid (AA) and cysteine (Cys), on the degradation of benzoic acid (BA) and the hydroxyl radical formation in the Fenton-RAs system were investigated. Results show the catalytic performance of RAs in BA degradation by Fenton reaction followed an order of NH2OH > AA > Cys. Compared with the conventional Fenton system, the effective pH range in the Fenton-NH2OH system extended from 3.0 to 5.0, while the optimal pH in the Fenton-AA and Fenton-Cys systems ranged from 3.0 to 4.0. The Fenton-AA system exhibited a two-stage reaction toward BA degradation, which was different from the Fenton-NH2OH and Fenton-Cys systems. Furthermore, the dosing manner of AA was found to be a key factor governing its role in the Fenton-AA system. This observation suggests the different mechanisms behind the enhancement of the three RAs in Fenton system. Different from NH2OH and Cys, AA would inhibit the generation of HO•, especially at the fast stage of degradation process, where Fe3+ has not accumulated yet. In addition, the economic analysis using the electrical energy per order indicates Fenton-NH2OH system was economically feasible with the lowest energy input, compared to Fenton-AA and Fenton-Cys systems. These results are useful to better understand the roles of RAs in Fenton system, and also provide guidance about the selection and dosing manner of suitable RAs in the advanced oxidation processes.

Carbon-Based Catalyst Synthesized and Immobilized under Calcium Salt Assistance To Boost Singlet Oxygen Evolution for Pollutant Degradation.

Carbon-based materials are recognized as promising candidates for pollutant degradation because of their environmental benignity. Massive and cost-effective production and efficient recovery of carbon-based catalysts are crucial to apply this technology. However, various nanostructured carbons with different dimensions are usually utilized as precursors while not considering their complex preparation procedures and the high costs of ingredients. Moreover, catalyst separation and recovery are not given sufficient attention. In this work, a calcium salt-assisted pyrolysis strategy is proposed to tune the catalytic site formation of carbon-based catalysts. Results show that blending equal amounts of Ca2+ (calcium chloride) and organic precursors could greatly improve the catalytic activity of the carbonated product to activate peroxymonosulfate for pollutant degradation. In addition, the proposed synthetic strategy is universal to most of the readily accessed and cost-effective organic precursors. Singlet oxygen is identified as the main reactive oxidant for pollutant removal in the catalytic reaction. By cross-linking calcium ions and alginate as a hydrogel to immobilize the catalyst, the carbon material could be readily recovered. Furthermore, a long-term continuous-flow reactor test is conducted to validate the effectiveness of applying the immobilized catalyst to treat a synthetic wastewater with 0.5 mM bisphenol A. As a result, a green synthesis and immobilization strategy for persulfate catalysts is successfully established, and the prepared catalyst might be applied for wastewater treatment through using calcium salt in two purposes.

Ultrasensitive Fluorescence Detection of Peroxymonosulfate Based on a Sulfate Radical-Mediated Aromatic Hydroxylation.

Recently, peroxymonosulfate (PMS)-based advanced oxidation processes have exhibited broad application prospects in the environment field. Accordingly, a simple, rapid, and ultrasensitive method is highly desired for the specific recognition and accurate quantification of PMS in various aqueous solutions. In this work, SO4•--induced aromatic hydroxylation was explored, and based on that, for the first time, a novel fluorescence method was developed for the PMS determination using Co2+ as a PMS activator and benzoic acid (BA) as a chemical probe. Through a suite of spectral, chromatographic, and mass spectrometric analyses, SO4•- was proven to be the dominant radical species, and salicylic acid was identified as the fluorescent molecule. As a result, a whole radical chain reaction mechanism for the generation of salicylic acid in the BA/PMS/Co2+ system was proposed. This fluorescence method possessed a rapid reaction equilibrium (<1 min), an ultrahigh sensitivity (detection limit = 10 nM; quantification limit = 33 nM), an excellent specificity, and a wide detection range (0-100 µM). Moreover, it performed well in the presence of possible interfering substances, including two other peroxides (i.e., peroxydisulfate and hydrogen peroxide), some common ions, and organics. The detection results for real water samples further validated the practical utility of the developed fluorescence method. This work provides a new method for the specific recognition and sensitive determination of PMS in complex aqueous solutions.