Preparation of novel Fe-containing zeolite-A for KN-R decolorization by Fenton-like reaction.

Herein, novel catalysts of Fe-containing zeolite-A (Fe/zeolite-A) were synthesized by exchanging iron ions into zeolite-A framework, and short-chain organic acids (SCOAs) were employed as chelating agents. Reactive Brilliant Blue KN-R (KN-R) was used as a model pollutant to evaluate the performance of these catalysts based on the heterogeneous Fenton reaction. The results showed that Fe-OA/3A, which applied zeolite-3A as the supporter and oxalic as the chelating agent, presented the most prominent KN-R decolorization efficiency. Under the initial pH of 2.5, 0.4 mM KN-R could be totally decolorized within 20 min. However, the mineralization efficiency of KN-R was only 58.2%. Therefore, anthraquinone dyes were introduced to modify zeolite-3A. As a result, the mineralization efficiency of KN-R was elevated to 92.7% when using Alizarin Violet (AV) as the modifier. Moreover, the modified catalysts exhibited excellent stability, the KN-R decolorization efficiency could be maintained above 95.0% within 20 min after operating for nine cycles. The mechanism revealed that the Fe(II)/Fe(III) cycle was accelerated by AV-modified catalyst thus prompting the KN-R decolorization in Fenton-like system. These findings provide new insights for preparing catalysts with excellent activity and stability for dye wastewater treatment.

Novel Defluorination Pathways of Perfluoroether Compounds (GenX): α-Fe2O3 Nanoparticle Layer Retains Higher Concentrations of Effective Hydrated Electrons.

The development of efficient defluorination technology is an important issue because the kind of emerging pollutant of hexafluoropropylene oxide dimer acid (GenX) as an alternative to perfluorooctanoic acid (PFOA) has the higher environmental risks. In the UV/bisulfite system, we first developed a hydrophobic confined α-Fe2O3 nanoparticle layer rich in oxygen vacancies, which accelerated the enrichment of HSO3- and GenX on the surface and pores through electrostatic attraction and hydrophobic interaction, retaining more hydrated electrons (eaq-) and rapidly destroying GenX under UV excitation. Especially, under anaerobic and aerobic conditions, the degradation percentage of GenX obtain nearly 100%, defluorination of GenX to 88 and 57% respectively. It was amazed to find that the three parallel H/F exchange pathways triggered by the rapid reactions of eaq- and GenX, which were unique to anaerobic conditions, improved the efficiency of fluoride removal and weaken the interference of dissolved oxygen and H+. Therefore, this study provided an available material and mechanism for sustainable fluoride removal from wastewater in aerobic and anaerobic conditions.

Identification and validation of potential hypoxia-related genes associated with coronary artery disease.

Introduction: Coronary artery disease (CAD) is one of the most life-threatening cardiovascular emergencies with high mortality and morbidity. Increasing evidence has demonstrated that the degree of hypoxia is closely associated with the development and survival outcomes of CAD patients. However, the role of hypoxia in CAD has not been elucidated. Methods: Based on the GSE113079 microarray dataset and the hypoxia-associated gene collection, differential analysis, machine learning, and validation of the screened hub genes were carried out. Results: In this study, 54 differentially expressed hypoxia-related genes (DE-HRGs), and then 4 hub signature genes (ADM, PPFIA4, FAM162A, and TPBG) were identified based on microarray datasets GSE113079 which including of 93 CAD patients and 48 healthy controls and hypoxia-related gene set. Then, 4 hub genes were also validated in other three CAD related microarray datasets. Through GO and KEGG pathway enrichment analyses, we found three upregulated hub genes (ADM, PPFIA4, TPBG) were strongly correlated with differentially expressed metabolic genes and all the 4 hub genes were mainly enriched in many immune-related biological processes and pathways in CAD. Additionally, 10 immune cell types were found significantly different between the CAD and control groups, especially CD8 T cells, which were apparently essential in cardiovascular disease by immune cell infiltration analysis. Furthermore, we compared the expression of 4 hub genes in 15 cell subtypes in CAD coronary lesions and found that ADM, FAM162A and TPBG were all expressed at higher levels in endothelial cells by single-cell sequencing analysis. Discussion: The study identified four hypoxia genes associated with coronary heart disease. The findings provide more insights into the hypoxia landscape and, potentially, the therapeutic targets of CAD.

Role of biochar-derived DOM compositions in enhanced biodegradation of sulfamethoxazole and chloramphenicol.

In the study, we investigated the different compositions of biochar-derived dissolved organic matter (BDOM) that play a key role in the biodegradation of sulfamethoxazole (SMX) and chloramphenicol (CAP) by P. stutzeri and S. putrefaciens, and found that aliphatic compounds in Group 4, fulvic acid like in Region III, and solid microbial byproduct like in region IV are key common factors. The growth and antibiotic degradation efficiency of P. stutzeri and S. putrefaciens are positively correlated with the content of Group 4 and Region III, and negatively correlated with Region IV. This is consistent with the optimal biodegradation results of BDOM700 with the highest content of Group 4 and Region III. Additionally, the degradation efficiency of SMX by Pseudomonas stutzeri is negatively correlated with the percentage of polycyclic aromatics in Group 1, but not with CAP. Similarly, the percentage of fatty acids in S. putrefaciens was positively correlated with Group 1, whereas P. stutzeri did not. This indicates that some components of BDOM have varying effects on different bacteria or types of antibiotics. This study provides new insights into enhancing antibiotic biodegradation by controlling the composition of BDOM.

Construction of the panoptosis-related gene model and characterization of tumor microenvironment infiltration in hepatocellular carcinoma.

Hepatocellular carcinoma (HCC) is the most common fatal cancer worldwide, patients with HCC have a high mortality rate and poor prognosis. PANoptosis is a novel discovery of programmed cell death associated with cancer development. However, the role of PANoptosis in HCC remains obscure. In this study, we enrolled 274 PANoptosis-related genes (PANRGs) and screened 8 genes to set up a prognostic model. A previous scoring system calculated PANscore was utilized to quantify the individual risk level of each HCC patient, and the reliability of the prognostic model has been validated in an external cohort. Nomogram constructed with PANscore and clinical characteristics were used to optimize individualized treatment for each patient. Single-cell analysis revealed a PANoptosis model associated with tumor immune cell infiltration, particularly natural killer (NK) cells. Further exploration of hub genes and assessment of the prognostic role of these 4 hub genes in HCC by quantitative real-time PCR (qRT-PCR) and immunohistochemistry (IHC). In conclusion, we evaluated a PANoptosis-based prognostic model as a potential prognostic biomarker for HCC patients.

Review on arsenic environment behaviors in aqueous solution and soil.

Arsenic pollution in environment has always been an important environmental problem that has attracted wide attention in recent years. Adsorption is one of the main methods of treatment for arsenic in the aqueous solution and soil because of the advantages of high efficiency, low cost and wide application. Firstly, this report summarizes the commonly and widely used adsorbent materials such as metal-organic frameworks, layered bimetallic hydroxides, chitosan, biochar and their derivatives. The adsorption effects and mechanisms of these materials are further discussed, and the application prospects of these adsorbents are considered. Meanwhile, the gaps and deficiencies in the study of adsorption mechanism was pointed out. Then, this study comprehensively evaluated the effects of various factors on arsenic transport, including (i) the effects of pH and redox potential on the existing form of As; (ii) complexation mechanism of dissolved organic matter and As; (iii) factors affecting the plant enrichment of As. Finally, the latest scientific researches on microbial remediation of arsenic and the mechanisms were summarized. The review finally enlightens the subsequent development of more efficient and practical adsorption material.

Remediation of soil contaminated with PAHs and γ-HCH using Fenton oxidation activated by carboxymethyl cellulose-modified iron oxide-biochar.

The remediation of soil contaminated with hydrophobic organic pollutants has attracted great public concern. In the present study, a novel catalyst using biochar supported ferro ferric oxide modified by carboxymethyl cellulose (CMC-Fe3O4/BC) was developed to activate the Fenton reaction for hazardous hydrophobic organic pollutants, and the degradation mechanisms were analyzed in terms of free radicals, electron transfer pathways and degradation intermediates. The results showed that the CMC-Fe3O4/BC-activated H2O2 system degraded nearly 100% of pyrene in the aqueous system after a 1440-min reaction. The catalyst was also applied to remediate industrial field soil contaminated with PAHs and γ-HCH. The removal rate of the total pollutants reached 61.1% after a 10-day reaction, which was higher than that of Fe3O4/BC without modification. CMC enabled the Fe3O4 particles to more equably distribute on the BC surface, further effectively activating H2O2 to generate more ⋅OH and forming different degradation products compared to the Fe3O4/BC. Additionally, the CMC-Fe3O4/BC-activated H2O2 system obviously enhanced electron transfer on the BC surface. Thus, the PAHs and γ-HCH could be degraded via electron transfer pathways.

Efficient remediation of the field soil contaminated with PAHs by amorphous porous iron material activated peroxymonosulfate.

An amorphous porous iron material (FH) was firstly self-synthesized using a simple coprecipitation approach and then utilized to activate peroxymonosulfate (PMS) for the catalytic degradation of pyrene and remediation of PAHs contaminated soil on site. FH exhibited more excellent catalytic activity than traditional hydroxy ferric oxide and possessed stability at a pH range of 3.0-11.0. According to quenching studies and electron paramagnetic resonance (EPR) analyses, non-radicals (Fe(IV) = O and 1O2) were the major reactive oxygen species (ROS) in the FH/PMS system's degradation of pyrene. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) of FH before and after the catalytic reaction, as well as active site substitution experiments and electrochemical analysis all verified that PMS adsorbed on FH could produce more abundant bonded hydroxyl groups (Fe-OH) which dominated the radical and non-radical oxidation reactions. Then, a possible pathway for pyrene degradation was presented according to gas chromatography-mass spectrometry (GC-MS). Furthermore, the FH/PMS system exhibited excellent catalytic degradation in the remediation of PAH-contaminated soil at real sites. This work provides a remarkable potential remediation technology of persistent organic pollutants (POPs) in environmental and will contribute to understanding the mechanism of Fe-based hydroxides in advanced oxidation processes.

Highly-efficient degradation of organic pollutants by oxalic acid modified sludge biochar: Mechanism and pathways.

The application of sludge biochar (SC) materials as efficient catalysts for organic pollutants mineralization via advanced oxidation process meets the good strategy of "make waste profitable". The catalytic oxidations of methyl orange (MO) and pyrene by oxalic acid modified sludge biochar (SC-OA) with and without H2O2 were carried out. The analysis of Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), electronic paramagnetic resonance spectrometer (EPR) and free radical quenching experiment were performed and the definite relationships between persistent free radicals (PFRs) type and specific reactive oxygen species (ROS) were made clear. It is suggested for the first time that carbon-centered type PFRs in SC-OA without H2O2 could form O2•- and •OH from COOH groups, while oxygen-centered type PFRs induced H2O2 to produce •OH. The degradation intermediates of MO and pyrene were identified and the transformation pathways were proposed. SC-OA, possessing good sustainable utilization and clean catalytic property, is expected to be popularized and applied in the mineralization of organic pollutants, especially in the in-situ remediation of contaminated soil where is no continuous supply of H2O2.

Remediation of industrial site soil contaminated with PAHs using stage persulfate oxidation activated by Fe2+ chelated with sodium citrate.

The remediation for industrial site soil has attracted public concerns because of the hazardous and hydrophobic properties of organic pollutants existed in the soil. The persulfate oxidation activated by Fe2+ chelated with sodium citrate (PS/Fe2+/SC) was used to remediate different types of industrial site soils in the present study. The maximum removal rates of Σ16 PAHs in the Nanjing site soil (NJS) and Hefei site soil (HFS) were 73.6% and 85.8% after the second-stage oxidation, respectively. The late oxidation stages couldn't enhance the degradation efficiency of PAHs due to the increase of high crystalline Fe mineral phases both in the NJS and HFS, which significantly decreased the Fe2+/Fe3+ recycle and further inhibited the reactive oxygen species production during the remediation. The remediation using PS/Fe2+/SC could change the soil physicochemical properties, such as the functional groups, specific surface area (SSA), total pore volume (TPV) and some UV spectral parameters of soil particles. Additionally, the oxidation of PS/Fe2+/SC also altered the composition of soil dissolve organic matters, especially the fulvic acid, which further affected the Fe2+ oxidation. The study mainly discloses the mechanism of limitation using persulfate oxidation activated by Fe materials at late oxidation stage.

PPCPs and heavy metals from hydrothermal sewage sludge-derived biochar: migration in wheat and physiological response.

Once the sludge was directly used in the farmland, it will have a negative impact on human health through the food chain because sludge contains pollutants. Sewage sludge pyrolysis into biochar is an effective way to realize sludge harmless and resourceful utilization. This research used hydrothermal carbonization method to convert sludge into sludge biochar (SLBC) to reduce the types and contents of pharmaceuticals and personal care products (PPCPs) and available heavy metals. Furthermore, migration of the residual caffeine (Caf), acetaminophen (Ace), and heavy metals (Cr, Pb, Cu, Zn) released from the SLBC in the wheat was assessed. The results showed that the levels of Caf, Ace, Pb, Cu, and Zn accumulated in the shoots were lower than the limit regulated by Drug and Food Additive Use Standard in China (Caf: 150 mg/kg; Ace: 2.5 ~ 5 mg/kg; Pb: 0.3 mg/kg; Cu: 10 mg/kg; Zn: 20 mg/kg). The migration of Cr from roots to shoots was also significantly controlled by SBLC. SBLC delayed the germination time of wheat seeds with increasing in hydrothermal temperature, the germination rate and root length showed a decreasing trend. Evans blue and O2- fluorescence staining of root tips also confirmed this conclusion. When the wheat was exposed to the low temperature and dose of SLBC, the chlorophyll contents and growth of wheat can be significantly increased; the oxidative damage of cell plasma membrane and net photosynthetic rate were reduced. However, 0.8 g/L of SLBC made plants suffer abiotic stress and caused oxidative damage to plants, and decreased membrane system stability. The study provides some parameters for sludge to realize resource utilization in the agricultural system.

Earthworms' Degradable Bioplastic Diet of Polylactic Acid: Easy to Break Down and Slow to Excrete.

Microplastics (MPs) in soils may be ingested by terrestrial animals. While the application of bioplastics is increasing, the ingestion and excretion characteristics of bio-MPs by terrestrial animals are poorly understood as compared to fossil-MPs. Here, the approach-avoidance behavior of adult earthworms Eisenia fetida to MP-contaminated soil was assessed. Fossil-based poly(ethylene terephthalate) (PET) and bio-based poly(lactic acid) (PLA) MPs were found to be preferred by the earthworms, which might be due to the odor of polymer monomers. MPs in earthworm casts were analyzed by microscopy counting and liquid chromatography-tandem mass spectrometry. The amount of microscopically recognizable excreted PET and PLA was 553 and 261 items/g, respectively, while a higher proportion of smaller PLA particles also presented. Bio-based PLA is much easy to break down by earthworms than fossil-based PET. Submicron and nanocron PLA accounted for 57 and 13% of the excreted PLA on the 10th day of excretion. MP excretion was well described with the first-order kinetic model, and the elimination half-life was 9.3 (for PET) and 45 h (for PLA). A longer excretion period of PLA may be related to its potential to break down in the earthworms' digestive tract. This not only promotes the environmental degradation of PLA but also suggests the ecological risk caused by nanoparticles.

A novel chitosan-urea encapsulated material for persulfate slow-release to degrade organic pollutants.

A novel eco-friendly material (CS-U@PS) for persulfate slow-release to effectively degrade organic pollutants (methyl orange and pyrene) was synthesized using chitosan and urea as the encapsulated framework materials via an emulsion cross-linking method for the first time. The obtained CS-U@PS exhibits spherical shapes with a uniform size of approximately 2-3 µm according to the particle-size distribution and SEM image results. The slow-release mechanism was proposed through a kinetics model study and the Ritger-Peppas model fit well (r2 = 0.9699) to indicate that the slow-release process is non-Fickian diffusion. The influences of urea and PS dosages and oxidative conditions on methyl orange degradation were studied, and all the results suggested that urea played an important role in PS slow-release and can also catalyze the activation of PS by iron to further produce radicals and improve the removal efficiency of pollutants. A pyrene removal rate of 90.53% was achieved in aqueous solutions and an above 80% removal rate was obtained in weakly acidic or neutral soil environments by CS-U@PS activated by Fe2+ with citric acid as the chelating agent. Therefore, the fabricated slow-release oxidation materials exhibit application potential for the remediation of organic polluted groundwater and soil.

Effect of Arylmethylene Substitutions on Molecular Structure, Optoelectronic Properties and Photovoltaic Performance of Dithienocyclopentafluorene-Based Small-Molecule Acceptors.

Two dithienocyclopentafluorene-based small-molecule acceptors (SMAs) were developed that feature methylene-functionalized conjugated side chains, to study the effect of arylmethylene substitution and its number on structure, optoelectronic properties and device performance. Results showed that two SMAs have better absorption properties and planarity, lower bandgaps and higher LUMOs compared with the control SMA without conjugated side chains. The synthesized SMAs were tested in polymer solar cells for examples of their applicability. This work argues that the introduction of methylene-functionalized conjugated side chains has great potential in tuning molecular structure, optoelectronic properties, device physics and photovoltaic performance of SMAs.

Development and validation of a risk prediction model and nomogram for colon adenocarcinoma based on methylation-driven genes.

Evidence suggests that abnormal DNA methylation patterns play a crucial role in the etiology and pathogenesis of colon adenocarcinoma (COAD). In this study, we identified a total of 97 methylation-driven genes (MDGs) through a comprehensive analysis of the Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO) databases. Univariate Cox regression analysis identified four MDGs (CBLN2, RBM47, SLCO4C1, and TMEM220) associated with overall survival (OS) in COAD patients. A risk prediction model was then developed based on these four MDGs to predict the prognosis of COAD patients. We also created a nomogram that incorporated risk scores, age, and TNM stage to promote a personalized prediction of OS in COAD patients. Compared with the traditional TNM staging system, our new nomogram was better at predicting the OS of COAD patients. In cell experiments, we confirmed that the mRNA expression levels of CLBN2 and TMEM220 were regulated by the methylation of their promoter regions. Moreover, immunohistochemistry showed that CBLN2 and TMEM220 were potential prognostic biomarkers for COAD patients. In summary, we have established a risk prediction model and nomogram that might be effectively utilized to promote the prediction of OS in COAD patients.

A review: Application of tourmaline in environmental fields.

Heavy metals and organic pollutants could pose long-term threats to the ecosystem and human health, so it is urgent for us to find a friendly and efficient material to remove pollutants in environment. Since tourmaline is widely distributed in natural environment and has many excellent physical and chemical properties including radiating far infrared energy, permanently releasing negative ions, producing an electrostatic field, releasing rare microelements, and stimulating the growth and metabolism of microorganisms and plants, tourmaline had been conducted to alleviate environmental pollution. This review summarizes the application of tourmaline in aqueous solutions and soil polluted by heavy metals and organic pollutants, the factors that affect the removal of pollutants by tourmaline and the removal mechanisms. In addition, to ensure the safe use of tourmaline, this review also elaborates the environment risks of tourmaline through its toxicity indexes to soil and plant.

Effects of iron plaque and fatty acids on the transfer of BDE-209 from soil to rice under iron mineral Fenton-like oxidation condition.

To understand the effect mechanisms of iron plaque and fatty acids on the migration of PBDEs from soil to rice (Oryza sativa), pot experiments were conducted in the soil spiked with decabromodiphenyl ether (BDE-209) under the conditions of tourmaline and nano-goethite Fenton-like treatments. The results showed that iron mineral Fenton-like oxidation could effectively remove BDE-209 from rhizosphere soil, the highest removal rate obtained 89.29% with the addition of 0.4 mmol/L H2O2 and 8 g nano-goethite (G + 3H group). Iron mineral Fenton-like oxidation could produce iron plaque (IP) on rice roots and accumulate a part of contaminants on the surface of IP, further weakening BDE-209 uptake in the plants. Additionally, the occurrence of fatty acid variation induced by BDE-209 stress, iron mineral Fenton-like oxidation at high concentrations of H2O2 with 0.4 mmol/L affected the distribution of fatty acids in plant tissues, especially for C18:0 fatty acid. While the IP on rice roots prevented the BDE-209 into plant, it was also closely related to the distribution of fatty acids in rice, altering BDE-209 accumulation in the rice. To safely use the iron mineral Fenton-like oxidation in the agricultural soil remediation, the safety of plant cells treated by mineral Fenton-like oxidation was evaluated using the transmission electron microscopy (TEM) and enzyme activity determination, which indicated that iron mineral Fenton-like oxidation would destroy the inner structures of plant cells, especially for G + 3H group.

Circulating CTRP6 Levels are Increased in Overweight or Obese Chinese Individuals and Associated with Insulin Resistance Parameters: A Pilot Study.

AIMS: CTRP6, a newly discovered adipokine, has been found to be a regulator for energy homeostasis. However, the association between circulating CTRP6 and obesity in humans is still unclear. METHODS: 256 individuals, including 185 overweight/obese (OW/OB) and 71 normal weight adults, were recruited for this study. Circulating concentrations of CTRP6 and adiponectin (Adipoq) were examined by ELISA. RESULTS: Serum CTRP6 levels in obese individuals were significantly increased compared with those in healthy individuals (506.1±134.9 vs.363.3±80.5 ng/mL, P<0.01). Conversely, serum Adipoq concentrations in OW/OB individuals were markedly decreased compared with healthy controls [20.8 (12.1-29.3) vs. 14.1 ( 8.61-17.7) ; P<0.01]. Correlation analysis revealed that there was a positive relationship between circulating CTRP6 and age, BMI, Fat%, LDL-C, TG, WHR, TC, FBG, FIns, HOMA-IR and HbA1c, but there was an inverse correlation with Adipoq and HDL-C. Logistic regression analysis revealed that high serum CTRP6 levels are markedly associated with OW/OB. Finally, ROC curve analysis showed that the cut-off value for serum CTRP6 for prediction of IR is 518 ng/mL. CONCLUSIONS: CTRP6 may be a marker related to OW/OB.

Highly active Ni/Fe3O4/TiO2 nanocatalysts with tunable interfacial interactions for PH3 decomposition.

The mixed-metal oxide Ni/Fe3O4/TiO2 with two metal-oxide interfaces to catalyze sequential chemical reactions was first applied in the decomposition of phosphine gas for yellow phosphorus (P4) production. The catalyst was prepared with tunable Ni-Fe3O4 and Ni-TiO2 interactions via annealing and subsequent reduction. Ni/Fe3O4/TiO2 exhibited significantly effective activity and good stability in the PH3 decomposition, which were achieved by modulating the metal-support interaction. The characterizations by scanning electron microscopy(SEM), X-ray diffraction analysis(XRD), BET surface area measurement and X-ray photoelectron spectroscopy(XPS) were carried out. The enhancements of the Ni-Fe3O4 and Ni-TiO2 dual interactions by annealing and reduction were verified and the mechanism of PH3 decomposition over the modulated Ni/Fe3O4/TiO2 catalyst was investigated. NiOOH as an active catalytic intermediate species is produced by the synergistic catalytical dual interfaces. The catalytic reaction pathways of PH3 decomposition by the dual interfaces were firstly revealed. The results provide underlying insights in the way to promote the catalytic performance for synergistic catalysis in PH3 decomposition.

Interpretable Visual Understanding with Cognitive Attention Network.

While image understanding on recognition-level has achieved remarkable advancements, reliable visual scene understanding requires comprehensive image understanding on recognition-level but also cognition-level, which calls for exploiting the multi-source information as well as learning different levels of understanding and extensive commonsense knowledge. In this paper, we propose a novel Cognitive Attention Network (CAN) for visual commonsense reasoning to achieve interpretable visual understanding. Specifically, we first introduce an image-text fusion module to fuse information from images and text collectively. Second, a novel inference module is designed to encode commonsense among image, query and response. Extensive experiments on large-scale Visual Commonsense Reasoning (VCR) benchmark dataset demonstrate the effectiveness of our approach. The implementation is publicly available at https://github.com/tanjatang/CAN.