Integration of cognitive tasks into artificial general intelligence test for large models.

During the evolution of large models, performance evaluation is necessary for assessing their capabilities. However, current model evaluations mainly rely on specific tasks and datasets, lacking a united framework for assessing the multidimensional intelligence of large models. In this perspective, we advocate for a comprehensive framework of cognitive science-inspired artificial general intelligence (AGI) tests, including crystallized, fluid, social, and embodied intelligence. The AGI tests consist of well-designed cognitive tests adopted from human intelligence tests, and then naturally encapsulates into an immersive virtual community. We propose increasing the complexity of AGI testing tasks commensurate with advancements in large models and emphasizing the necessity for the interpretation of test results to avoid false negatives and false positives. We believe that cognitive science-inspired AGI tests will effectively guide the targeted improvement of large models in specific dimensions of intelligence and accelerate the integration of large models into human society.

Reassessing the Quantum Yield and Reactivity of Triplet-State Dissolved Organic Matter via Global Kinetic Modeling.

Measuring the quantum yield and reactivity of triplet-state dissolved organic matter (3DOM*) is essential for assessing the impact of DOM on aquatic photochemical processes. However, current 3DOM* quantification methods require multiple fitting steps and rely on steady-state approximations under stringent application criteria, which may introduce certain inaccuracies in the estimation of DOM photoreactivity parameters. Here, we developed a global kinetic model to simulate the reaction kinetics of the hv/DOM system using four DOM types and 2,4,6-trimethylphenol as the probe for 3DOM*. Analyses of residuals and the root-mean-square error validated the exceptional precision of the new model compared to conventional methods. 3DOM* in the global kinetic model consistently displayed a lower quantum yield and higher reactivity than those in local regression models, indicating that the generation and reactivity of 3DOM* have often been overestimated and underestimated, respectively. The global kinetic model derives parameters by simultaneously fitting probe degradation kinetics under different conditions and considers the temporally increasing concentrations of the involved reactive species. It minimizes error propagation and offers insights into the interactions of different species, thereby providing advantages in accuracy, robustness, and interpretability. This study significantly advances the understanding of 3DOM* behavior and provides a valuable kinetic model for aquatic photochemistry research.

Unraveling Different Reaction Characteristics of Alkoxy Radicals in a Co(II)-Activated Peracetic Acid System Based on Dynamic Analysis of Electron Distribution.

Peracetic acid (PAA)-based advanced oxidation processes (AOPs) have shown broad application prospects in organic wastewater treatment. Alkoxy radicals including CH3COO• and CH3COOO• are primary reactive species in PAA-AOP systems; however, their reaction mechanism on attacking organic pollutants still remains controversial. In this study, a Co(II)/PAA homogeneous AOP system at neutral pH was constructed to generate these two alkoxy radicals, and their different reaction mechanisms with a typical emerging contaminant (sulfacetamide) were explored. Dynamic electron distribution analysis was applied to deeply reveal the radical-meditated reaction mechanism based on molecular orbital analysis. Results indicate that hydrogen atom abstraction is the most favorable route for both CH3COO• and CH3COOO• attacking sulfacetamide. However, both radicals cannot react with sulfacetamide via the radical adduct formation route. Interestingly, the single-electron transfer reaction is only favorable for CH3COO• due to its lower ESUMO. In comparison, CH3COOO• can react with sulfacetamide via a similar radical self-sacrificing bimolecular nucleophilic substitution (SN2) route owing to its high ESOMO and easy escape of unpaired electrons from n orbitals of O atoms in the peroxy bond. These findings can significantly improve the knowledge of reactivity of CH3COO• and CH3COOO• on attacking organic pollutants at the molecular orbital level.

Nucleus-Aware Self-Supervised Pretraining Using Unpaired Image-to-Image Translation for Histopathology Images.

Self-supervised pretraining attempts to enhance model performance by obtaining effective features from unlabeled data, and has demonstrated its effectiveness in the field of histopathology images. Despite its success, few works concentrate on the extraction of nucleus-level information, which is essential for pathologic analysis. In this work, we propose a novel nucleus-aware self-supervised pretraining framework for histopathology images. The framework aims to capture the nuclear morphology and distribution information through unpaired image-to-image translation between histopathology images and pseudo mask images. The generation process is modulated by both conditional and stochastic style representations, ensuring the reality and diversity of the generated histopathology images for pretraining. Further, an instance segmentation guided strategy is employed to capture instance-level information. The experiments on 7 datasets show that the proposed pretraining method outperforms supervised ones on Kather classification, multiple instance learning, and 5 dense-prediction tasks with the transfer learning protocol, and yields superior results than other self-supervised approaches on 8 semi-supervised tasks. Our project is publicly available at https://github.com/zhiyuns/UNITPathSSL.

[Determination of 14 perfluoroalkyl substances in Chinese mitten crab by multi-plug filtration cleanup coupled with ultra-performance liquid chromatography-tandem mass spectrometry].

Perfluoroalkyl substances (PFASs) have become a new food-safety problem. Dietary intake is a major pathway of human exposure to PFASs. Chinese mitten crab (Eriocheir sinensis) is a high-end aquaculture product popular among consumers in China. Conventional extraction methods for PFASs are cumbersome and time consuming, and result in incomplete purification; thus, this technique does not meet the requirements for PFAS detection. Herein, an analytical strategy was established for the rapid detection of 14 PFASs in Chinese mitten crab based on multi-plug filtration cleanup (m-PFC) and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The carbon-chain length of the 14 PFASs analyzed in this study ranged from 4 to 14, and they are perfluorobutanoic acid (PFBA), perfluoro-n-pentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluoro-1-butane sulfonic acid (PFBS), perfluoro-1-hexane sulfonic acid (PFHxS), perfluoro-1-octane sulfonic acid (PFOS), and perfluoro-1-decanesulfonate (PFDS). The m-PFC column was prepared using carboxy-based multiwalled carbon nanotubes, and used to reduce the interference of sample impurities. The samples were extracted with 5 mL of 0.1% formic acid aqueous solution, 15 mL of acetonitrile and extraction salt (2 g Na2SO4 and 2 g NaCl). The supernatant (10 mL) was purified using the m-PFC column, concentrated to near dryness under nitrogen, and then redissolved in 1 mL of methanol. Finally, the sample solution was filtered through a 0.22 µm polypropylene syringe filter for UPLC-MS/MS analysis. The target analytes were separated using a Shimadzu Shim-pack G1ST-C18 chromatographic column (100 mm×2.1 mm, 2 µm) using methanol (A) and 5 mmol/L ammonium acetate aqueous solution (B) as the mobile phases via gradient elution. The linear gradient program were as follows: 0-0.5 min, 10%A-35%A; 0.5-3 min, 35%A-60%A; 3-5 min, 60%A-100%A; 5-6.5 min, 100%A; 6.5-7 min, 100%A-10%A. The target analytes were analyzed using negative electrospray ionization in multiple-reaction monitoring mode, and quantitative analysis was performed using the internal standard method. In this study, we optimized the mobile-phase system as well as the extraction solvent, time, volume, and salt. The 14 PFASs exhibited good peak shapes and sensitivities when the 5 mmol/L ammonium acetate solution-methanol system was used as the mobile phase. Compared with acetonitrile or methanol alone, the extraction efficiencies of the 14 PFASs were significantly improved when 5 mL of 0.1% formic acid aqueous solution was added, followed by 15 mL of acetonitrile. The extraction efficiencies of the 14 PFASs did not differ significantly when the extraction time was within 3-15 min. The extraction salt (MgSO4, Na2SO4, NaCl, (NH4)2SO4, and Na2SO4+NaCl) significantly affected the extraction efficiencies of the 14 PFASs. The highest extraction efficiencies of the 14 PFASs, which ranged from 47.9% to 121.9%, were obtained when Na2SO4+NaCl was used as the extraction salt. Under the optimal experimental conditions, good linearities (R2=0.998-0.999) were obtained for seven PFASs (PFBS, PFHxA, PFHpA, PFHxS, PFDA, PFDoDA, PFTeDA) at 0.10-100 µg/L, and seven PFASs (PFBA, PFPeA, PFOA, PFOS, PFNA, PFUnDA, PFDS) at 0.50-100 µg/L. The average spiked recoveries for the 14 PFASs in Chinese mitten crabs at three levels ranged from 73.1% to 120%, with relative standard deviations (RSDs) in the range of 1.68%-19.5%(n=6). The limits of detection (LODs) and quantification (LOQs) of the 14 PFASs were in the range of 0.03-0.15 and 0.10-0.50 µg/kg, respectively. The developed method was applied to the analysis of crab samples collected from three farms in Shanghai, and PFASs with total concentrations of 3.52-37.77 µg/kg were detected in all samples. The detection frequencies for PFDA, PFUnDA, PFDoDA, PFTeDA, and PFOS were 100%. PFDA, PFUnDA, PFOS, and PFDoDA were the most abundant congeners, accounting for 31.2%, 30.6%, 15.0%, and 10.9%, respectively, of the 14 PFASs detected. The proposed method is simple, efficient, accurate, and suitable for the rapid analysis of 14 PFASs in Chinese mitten crabs.

Bone marrow mesenchymal stem cell-derived exosomal microRNA regulates microglial polarization.

Objective: This study aimed to explore the effects of bone marrow mesenchymal stem cell (BMSC)-derived exosomal miR-146a-5p on microglial polarization and the potential underlying mechanisms in oxygen-glucose deprivation (OGD)-exposed microglial cells. Methods: Exosomes were isolated from BMSCs, and their characteristics were examined. The effects of BMSC-derived exosomes on microglial polarization were investigated in OGD-exposed BV-2 cells. Differentially expressed miRNAs were identified and their biological function was explored using enrichment analyses. The regulatory role of miR-146a-5p in microglial polarization was studied via flow cytometry. Finally, the downstream target gene Traf6 was validated, and the role of the miR-146a-5p/Traf6 axis in modulating microglial polarization was investigated in OGD-exposed BV-2 cells. Results: BMSC-derived exosomes were successfully isolated and characterized. A total of 10 upregulated and 33 downregulated miRNAs were identified. Exosomal treatment resulted in significant changes in microglial polarization markers. miR-146a-5p was found to be significantly downregulated in OGD-exposed microglial cells treated with exosomes. Manipulation of miR-146a-5p expression modulated microglial polarization. Moreover, the miR-146a-5p/Traf6 axis regulated microglial polarization. Conclusion: Our findings demonstrate that BMSC-derived exosomal via miR-146a-5p modulates microglial polarization by targeting Traf6, providing a potential thermal target for the treatment of neurological diseases involving microglial activation.

Photo-transformation of wastewater effluent organic matter reduces the formation potential and toxicity of chlorinated disinfection byproducts.

Sunlight exposure can degrade and transform discharged wastewater effluent organic matter (EfOM) in aquatic systems, potentially enhancing the feasibility of reusing wastewater for drinking purposes. However, there remains a lack of comprehensive understanding regarding the sunlight-induced changes in the molecular-level composition, characteristics, and chlorine reactivity of EfOM. Herein, we investigated the impact of sunlight on the optical properties, chemical composition, and formation of disinfection byproducts of EfOM using multiple spectroscopic analyses, high-resolution mass spectrometry, chlorination experiments, and in vitro bioassays. Upon natural sunlight exposure, we observed significant decreases in ultraviolet-visible absorbance and fluorescence intensity of EfOM, indicating the destruction of chromophores and fluorophores. Photolysis generally yields products with lower molecular weight and aromaticity, and with higher saturation and oxidation levels. Moreover, a shift within the EfOM from condensed aromatic-like compounds to tannin-like components was observed. Furthermore, sunlight exposure reduced the reactivity of EfOM toward the formation of trihalomethanes and haloacetonitriles during chlorination, while there was a slight increase in the specific formation potential of haloketones. Importantly, the disinfection byproducts resulting from chlorination of the irradiated EfOM exhibited reduced microtoxicity. Overall, this study provides new insights into alterations in EfOM under sunlight exposure and aids in predicting the health risks of effluent discharge in water environments.

Dissipation, Bioconcentration and Dietary Risk Assessment of Thiamethoxam and Its Metabolites in Agaricus bisporus and Substrates under Different Application Methods.

In order to acquire scientific evidence for the application of thiamethoxam (TMX) in Agaricus bisporus cultivation, residue and dissipation experiments for field trials were performed with the application of TMX in compost and casing soil, respectively. An effective QuEChERS method was established to analyze TMX and its two metabolites, clothianidin (CLO) and thiamethoxam-urea (TMX-urea), in compost, casing soil, and fruiting bodies. The results indicated that the TMX dissipation half-lives (t1/2) at dosages of 10 and 50 mg kg-1 were 19.74 d (day) and 28.87 d in compost and 33.54 d and 42.59 d in casing soil, individually. TMX, CLO, and TMX-urea were observed after TMX application in compost and casing soil. For TMX applied to the casing soil, only TMX residues were detected in fruiting bodies with bioconcentration factors (BCFs) of 0.0003~0.0009. In addition, both the chronic risk quotient (RQ) and acute risk quotient (HQ) values of TMX in fruiting bodies were far less than 1, which means the dietary health risks to humans were acceptable. However, in the TMX application to the compost, these analytes were not detected in the fruiting bodies. This suggested that the application of TMX in compost was safer than in casing soil during A. bisporus cultivation.

Proton transfer triggered in-situ construction of C=N active site to activate PMS for efficient autocatalytic degradation of low-carbon fatty amine.

Removal of low-carbon fatty amines (LCFAs) in wastewater treatment poses a significant technical challenge due to their small molecular size, high polarity, high bond dissociation energy, electron deficiency, and poor biodegradability. Moreover, their low Brønsted acidity deteriorates this issue. To address this problem, we have developed a novel base-induced autocatalytic technique for the highly efficient removal of a model pollutant, dimethylamine (DMA), in a homogeneous peroxymonosulfate (PMS) system. A high reaction rate constant of 0.32 min-1 and almost complete removal of DMA within 12 min are achieved. Multi-scaled characterizations and theoretical calculations reveal that the in situ constructed C=N bond as the crucial active site activates PMS to produce abundant 1O2. Subsequently, 1O2 oxidizes DMA through multiple H-abstractions, accompanied by the generation of another C=N structure, thus achieving the autocatalytic cycle of pollutant. During this process, base-induced proton transfers of pollutant and oxidant are essential prerequisites for C=N fabrication. A relevant mechanism of autocatalytic degradation is unraveled and further supported by DFT calculations at the molecular level. Various assessments indicate that this self-catalytic technique exhibits a reduced toxicity and volatility process, and a low treatment cost (0.47 $/m3). This technology has strong environmental tolerance, especially for the high concentrations of chlorine ion (1775 ppm) and humic acid (50 ppm). Moreover, it not only exhibits excellent degradation performance for different amine organics but also for the coexisting common pollutants including ofloxacin, phenol, and sulforaphane. These results fully demonstrate the superiority of the proposed strategy for practical application in wastewater treatment. Overall, this autocatalysis technology based on the in-situ construction of metal-free active site by regulating proton transfer will provide a brand-new strategy for environmental remediation.

Dual role of soil-derived dissolved organic matter in the sulfamethoxazole oxidation by manganese dioxide.

Manganese dioxide (MnO2) can mediate organic pollutant oxidation in aquatic environments, which has been reported to be inhibited or promoted by dissolved organic matter (DOM) in different studies. It remains unresolved why conflicting results have been observed and whether such results depend on the type and concentration of DOM. Here, we used three types of well-characterized DOM derived from soil heated at 50, 250, or 400 °C (DOM_50, DOM_250, and DOM_400, respectively) to evaluate the impacts of DOM type and concentration and environmental pH on MnO2-mediated oxidation of sulfamethoxazole, a widely detected and ecotoxic emerging pollutant. We observed that the degradation rate of sulfamethoxazole was possibly promoted by DOM_250 (pH 6‒8), while it was generally inhibited by DOM_50 and DOM_400. Furthermore, it was initially inhibited and then promoted with increasing DOM concentrations and was consistently less inhibited at a higher pH. The inter-DOM variations of sulfamethoxazole degradation could be explained by the more enriched polyphenolics in DOM_250 than in DOM_50 and DOM_400, whereas the weak promoting effect of DOM_400 indicates that high DOM aromaticity may not necessarily promote pollutant degradation. Our results reconcile the debate on the role of DOM in the oxidation of sulfamethoxazole by MnO2 and highlight the decisiveness of the molecular composition and concentration of DOM and the reaction pH in the overall promoting or inhibiting role of DOM.

Transformation of dissolved organic matter during UV/peracetic acid treatment.

Peracetic acid combined ultraviolet (UV/PAA) process has garnered growing attention as a promising advanced oxidation process (AOP) for wastewater treatment, but the corresponding transformation of ubiquitous dissolved organic matter (DOM) under this AOP remains unknown. This study systematically investigated the changes in characteristics and composition of DOM under UV/PAA, as well as the underlying mechanisms by multiple spectroscopic analyses and Fourier transform ion cyclotron resonance mass spectrometry. UV/PAA treatment dramatically decreased aromaticity, apparent molecular weight, and fluorescent abundance of DOM with the production of more oxidized and saturated compounds. The reactive species (i.e., ·OH and CH3C(O)O·/CH3C(O)OO·) in UV/PAA contributed primarily to DOM changes but showed different reaction selectivity and mechanisms. ·OH reacts with DOM components and mainly yields oxygenation products via a radical addition pathway. Comparatively, the electron transfer route is more likely to occur in CH3C(O)O·/CH3C(O)OO·-induced DOM transformation. Aside from oxygenation products, electron transfer could exclusively generate decarboxylation products and distinguishes CH3C(O)O·/CH3C(O)OO·-based AOPs from ·OH-based AOPs. These findings significantly improve knowledge of DOM alterations under UV/PAA AOP at both the bulk and molecular levels.

Simultaneous Fractionation, Desalination, and Dye Removal of Dye/Salt Mixtures by Carbon Cloth-Modified Flow-electrode Capacitive Deionization.

The critical challenges of using electromembrane processes [e.g., electrodialysis and flow-electrode capacitive deionization (FCDI)] to recycle resources (e.g., water, salts, and organic compounds) from wastewater are the fractionation of dissolved ionic matter, the removal/recovery of organic components during desalination, and membrane antifouling. This study realized the simultaneous fractionation, desalination, and dye removal/recovery (FDR) treatment of dye/salt mixtures through a simple but effective approach, that is, using a carbon cloth-modified FCDI (CC-FCDI) unit, in which the carbon cloth layer was attached to the surface of each ion-exchange membrane (IEM). The IEMs and carbon-based flow-electrodes were responsible for the fractionation and desalination of dye and salt ions, while the carbon cloth layers contributed to the active membrane antifouling and dye removal/recovery by the electrosorption mechanism. Attributed to such features, the CC-FCDI unit accomplished the effective FDR treatment of dye/salt mixtures with wide ranges of salt and dye concentrations (5-20 g L-1 NaCl and 200-800 ppm methylene blue) and different dye components (cationic and anionic dyes) under various applied voltages (1.2-3.2 V). Moreover, the active membrane antifouling by virtue of the carbon cloth facilitated the excellent and sustainable FDR performance of CC-FCDI. The removal/recovery of dyes from the carbon cloth strongly depends on the characteristics of dye molecules, the surface properties of the carbon cloth, and the local pH at the IEM/CC interfaces. This study sheds light on the strategies of using multifunctional layer-modified FCDI units to reclaim resources from various high-salinity organic wastewater.

Accurate identification of radicals by in-situ electron paramagnetic resonance in ultraviolet-based homogenous advanced oxidation processes.

Accurate identification of radicals in advanced oxidation processes (AOPs) is important to study the mechanisms on radical production and subsequent oxidation-reduction reaction. The commonly applied radical quenching experiments cannot provide direct evidences on generation and evolution of radicals in AOPs, while electron paramagnetic resonance (EPR) is a cutting-edge technology to identify radicals based on spectral characteristics. However, the complexity of EPR spectrum brings uncertainty and inconsistency to radical identification and mechanism clarification. This work presented a comprehensive study on identification of radicals by in-situ EPR analysis in four typical UV-based homogenous AOPs, including UV/H2O2, UV/peroxodisulfate (and peroxymonosulfate), UV/peracetic acid and UV/IO4- systems. Radical formation mechanism was also clarified based on EPR results. A reliable EPR method using organic solvents was proposed to identify alkoxy and alkyl radicals (CH3C(=O)OO·, CH3C(=O)O· and ·CH3) in UV/PAA system. Two activation pathways for radical production were proposed in UV/IO4- system, in which the produced IO3·, IO4·, ·OH and hydrated electron were precisely detected. It is interesting that addition of specific organic solvents can effectively identify oxygen-center and carbon-center radicals. A key parameter in EPR spectrum for 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin adduct, AH, is ranked as: ·CH3 (23 G) >·OH (15 G) >IO3· (12.9 G) >O2·- (11 G) ≥·OOH (9-11 G) ≥IO4· (9-10 G) ≥SO4·- (9-10 G) >CH3C(=O)OO· (8.5 G) > CH3C(=O)O· (7.5 G). This study will give a systematic method on identification of radicals in AOPs, and shed light on the insightful understanding of radical production mechanism.

Hydrogen atom abstraction mechanism for organic compound oxidation by acetylperoxyl radical in Co(II)/peracetic acid activation system.

Peracetic acid (PAA) has been widely used as an alternative disinfectant in wastewater treatment, and PAA-based advanced oxidation processes (AOPs) have drawn increasing attention recently. Among the generated reactive species after PAA activation, acetylperoxyl radical (CH3CO3•) plays an important role in organic compounds degradation. However, little is known about the reaction mechanism on CH3CO3• attack due to the challenging of experimental analysis. In this study, a homogeneous PAA activation system was built up using Co(II) as an activator at neutral pH to generate CH3CO3• for phenol degradation. More importantly, reaction mechanism on CH3CO3•-driven oxidation of phenol is elucidated at the molecular level. CH3CO3• with lower electrophilicity index but much larger Waals molecular volume holds different phenol oxidation route compared with the conventional •OH. Direct evidences on CH3CO3• formation and attack mechanism are provided through integrated experimental and theoretical results, indicating that hydrogen atom abstraction (HAA) is the most favorable route in the initial step of CH3CO3•-driven phenol oxidation. HAA reaction step is found to produce phenoxy radicals with a low energy barrier of 4.78 kcal mol-1 and free energy change of -12.21 kcal mol-1. The generated phenoxy radicals will undergo further dimerization to form 4-phenoxyphenol and corresponding hydroxylated products, or react with CH3CO3• to generate catechol and hydroquinone. These results significantly promote the understanding of CH3CO3•-driven organic pollutant degradation and are useful for further development of PAA-based AOPs in environmental applications.

Maternally expressed 3 protects the intestinal barrier from cardiac arrest-induced ischemia/reperfusion injury via miR-34a-3p/sirtuin 1/nuclear factor kappa B signaling.

BACKGROUND: Cardiac arrest (CA), a common disease with a high mortality rate, is a leading cause of ischemia/reperfusion (I/R)-induced dysfunction of the intestinal barrier. Long non-coding RNAs (lncRNAs) play crucial roles in multiple pathological processes. However, the effect of the lncRNA maternally expressed 3 (MEG3) on intestinal I/R injury and the intestinal barrier has not been fully determined. Therefore, this study aimed to investigate the function of MEG3 in CA-induced intestinal barrier dysfunction. METHODS: The oxygen and glucose deprivation (OGD) model in the human colorectal adenocarcinoma Caco-2 cells and in vivo cardiac arrest-induced intestinal barrier dysfunction model in Sprague-Dawley (SD) rats were established. The effect and underlying mechanism of MEG3 on the intestinal barrier from cardiac arrest-induced ischemia/reperfusion injury were analyzed by methyl thiazolyl tetrazolium (MTT) assays, Annexin V-FITC/PI apoptosis detection kit, Terminal deoxynucleotidyl transferase-mediated dUTP nick end labelling (TUNEL) staining, quantitative polymerase chain reaction (qPCR) assays, Western blot analysis, luciferase reporter gene assays, transepithelial electrical resistance (TEER) measurements, immunofluorescence analysis, and enzyme-linked immunosorbent assay (ELISA) assays. RESULTS: Interestingly, we found that MEG3 could protect Caco-2 cells from oxygen-glucose deprivation (OGD)/reoxygenation-induced I/R injury by modulating cell proliferation and apoptosis. Moreover, MEG3 relieved OGD-induced intestinal barrier dysfunction in vitro, as demonstrated by its significant rescue effect on transepithelial electrical resistance and the expression of tight junction proteins such as occludin and claudin-1 (CLDN1), which were impaired in OGD-treated Caco-2 cells. Mechanistically, MEG3 inhibited the expression of inflammatory factors including interleukin (IL)-1ß, tumor necrosis factor (TNF)-α, interferon-gamma (IFN)-γ, inflammatory factors including interleukin (IL)-10, and transforming growth factor beta (TGFb)-1, as well as nuclear factor-kappa B (NF-κB) signaling. In response to OGD treatment in vitro, MEG3 also activated the expression of sirtuin 1 (SIRT1) by Caco-2 cells via sponging miR-34a-3p. Furthermore, MEG3 relieved CA-induced intestinal barrier dysfunction through NF-κB signaling in vivo. CONCLUSIONS: LncRNA MEG3 can protect the intestinal barrier from cardiac arrest-induced I/R injury via miR-34a-3p/SIRT1/NF-κB signaling. This finding provides new insight into the mechanism by which MEG3 restores intestinal barrier function following I/R injury, presenting it as a potential therapeutic candidate or strategy in intestinal injury.

Insights into catalytic activation of peroxymonosulfate for carbamazepine degradation by MnO2 nanoparticles in-situ anchored titanate nanotubes: Mechanism, ecotoxicity and DFT study.

Developing efficient pharmaceuticals and personal care products (PPCPs) degradation technologies is of scientifical and practical importance to restrain their discharge into natural water environment. This study fabricated and applied a composite material of amorphous MnO2 nanoparticles in-situ anchored titanate nanotubes (AMnTi) to activate peroxymonosulfate (PMS) for efficient degradation and mineralization of carbamazepine (CBZ). The degradation pathway and toxicity evolution of CBZ during elimination were deeply evaluated through produced intermediates identification and theoretical calculations. AMnTi with a composition of (0.3MnO2)•(Na1.22H0.78Ti3O7) offered high activation efficiency of PMS, which exhibited 21- and 3-times degradation rate of CBZ compared with the pristine TNTs and MnO2, respectively. The high catalytic activity can be attributed to its unique structure, leading to a lattice shrinkage and small pores to confine the PMS molecule onto the interface. Therefore, efficient charge transfer and catalytic activation through MnOTi linkage occurred, and a MnTi cycle mediating catalytic PMS activation was found. Both hydroxyl and sulfate radicals played key roles in CBZ degradation. Theoretical calculations, i.e., density functional theory (DFT) and computational toxicity calculations, combined with intermediates identification revealed that CBZ degradation pathway was hydroxyl addition and NC cleavage. CBZ degradation in this system was also a toxicity-attenuation process.

Photocatalytic transformation fate and toxicity of ciprofloxacin related to dissociation species: Experimental and theoretical evidences.

Chemical speciation of ionizable antibiotics greatly affects its photochemical kinetics and mechanisms; however, the mechanistic impact of chemical speciation is not well understood. For the first time, the impact of different dissociation species (cationic, zwitterionic and anionic forms) of ciprofloxacin (CIP) on its photocatalytic transformation fate was systematically studied in a UVA/LED/TiO2 system. The dissociation forms of CIP at different pH affected the photocatalytic degradation kinetics, transformation products (TPs) formation as well as degradation pathways. Zwitterionic form of CIP exhibited the highest degradation rate constant (0.2217 ± 0.0179 min-1), removal efficiency of total organic carbon (TOC) and release of fluoride ion (F-). Time-dependent evolution profiles on TPs revealed that the cationic and anionic forms of CIP mainly underwent piperazine ring dealkylation, while zwitterionic CIP primarily proceeded through defluorination and piperazine ring oxidation. Moreover, density functional theory (DFT) calculation based on Fukui index well interpreted the active sites of different CIP species. Potential energy surface (PES) analysis further elucidated the reaction transition state (TS) evolution and energy barrier (ΔEb) for CIP with different dissociation species after radical attack. This study provides deep insights into degradation mechanisms of emerging organic contaminants in advanced oxidation processes associated to their chemical speciation.

Cobalt/Peracetic Acid: Advanced Oxidation of Aromatic Organic Compounds by Acetylperoxyl Radicals.

Peracetic acid (PAA) is increasingly used as an alternative disinfectant and its advanced oxidation processes (AOPs) could be useful for pollutant degradation. Co(II) or Co(III) can activate PAA to produce acetyloxyl (CH3C(O)O•) and acetylperoxyl (CH3C(O)OO•) radicals with little •OH radical formation, and Co(II)/Co(III) is cycled. For the first time, this study determined the reaction rates of PAA with Co(II) (kPAA,Co(II) = 1.70 × 101 to 6.67 × 102 M-1·s-1) and Co(III) (kPAA,Co(III) = 3.91 × 100 to 4.57 × 102 M-1·s-1) ions over the initial pH 3.0-8.2 and evaluated 30 different aromatic organic compounds for degradation by Co/PAA. In-depth investigation confirmed that CH3C(O)OO• is the key reactive species under Co/PAA for compound degradation. Assessing the structure-activity relationship between compounds' molecular descriptors and pseudo-first-order degradation rate constants (k'PAA• in s-1) by Co/PAA showed the number of ring atoms, EHOMO, softness, and ionization potential to be the most influential, strongly suggesting the electron transfer mechanism from aromatic compounds to the acetylperoxyl radical. The radical production and compound degradation in Co/PAA are most efficient in the intermediate pH range and can be influenced by water matrix constituents of bicarbonate, phosphate, and humic acids. These results significantly improve the knowledge regarding the acetylperoxyl radical from PAA and will be useful for further development and applications of PAA-based AOPs.

Advanced Oxidation Process with Peracetic Acid and Fe(II) for Contaminant Degradation.

Fe(II) is an excellent promoter for advanced oxidation processes (AOPs) because of its environmental ubiquity and low toxicity. This study is among the first to characterize the reaction of peracetic acid (PAA) with Fe(II) ion and apply the Fe(II)/PAA AOP for degradation of micropollutants. PAA reacts with Fe(II) (k = 1.10 × 105-1.56 × 104 M-1 s-1 at pH 3.0-8.1) much more rapidly than H2O2 and outperforms the coexistent H2O2 for reaction with Fe(II). While PAA alone showed minimal reactivity with methylene blue, naproxen, and bisphenol-A, significant abatement (48-98%) of compounds was observed by Fe(II)/PAA at initial pH of 3.0-8.2. The micropollutant degradation by Fe(II)/PAA exhibited two kinetic phases (very rapid then slow) related to PAA and H2O2, respectively. Based on experimental evidence, formation of carbon-centered radicals (CH3C(O)O•, CH3C(O)•, and •CH3), •OH, and Fe(IV) reactive intermediate species from the PAA and Fe(II) reactions in the presence of H2O2 is hypothesized. The carbon-centered radicals and/or Fe(IV) likely played an important role in micropollutant degradation in the initial kinetic phase, while •OH was important in the second reaction phase. The transformation products of micropollutants showed lower model-predicted toxicity than their parent compounds. This study significantly advances the understanding of PAA and Fe(II) reaction and demonstrates Fe(II)/PAA to be a feasible advanced oxidation technology.