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Neutrophilic asthma is a persistent and severe inflammatory lung disease characterized by neutrophil activation and the mechanisms of which are not completely elucidated. Ubiquitin D (UBD) is a ubiquitin-like modifier participating in infections, immune responses, and tumorigenesis, while whether UBD involves in neutrophilic asthma needs further study. In this study, we initially found that UBD expression was significantly elevated and interleukin 17 (IL-17) signaling was enriched in the endobronchial biopsies of severe asthma along with neutrophils increasing by bioinformatics analysis. We further confirmed that UBD was upregulated in the lung tissues of neutrophilic asthma mouse model. UBD overexpression promoted IL-17 signaling activation. Knockdown of UBD suppressed the activation of IL-17 signaling. UBD interacted with TRAF2 and reduced the total and the K48-linked ubiquitination of TRAF2. However, IL-17 A stimulation increased both the total and the K48-linked ubiquitination of TRAF2. Together, these findings indicated that UBD was upregulated and played a critical role in IL-17 signaling which contributed to a better understanding of the complex mechanisms in neutrophilic asthma., Competing Interests: Declaration of competing interest The authors declare that there are no conflicts of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is necessary to control its content in aquatic environments. Electrochemical and thermally-activated persulfates have been successfully used to degrade HFPO-DA, but UV-activated persulfates cannot degrade the compound. Given that research on degradation mechanisms is still incomplete and lacks kinetic research, the mechanism and kinetic calculations of oxidative degradation were studied in detail using DFT calculations. And the toxicity of HFPO-DA degradation intermediates and products was evaluated to reveal the feasibility of using advanced oxidation process (AOP) technology based on persulfate to degrade HFPO-DA in wastewater. The results showed that the committed step of HFPO-DA degradation was initiated by the electron transfer reaction of SO 4 •- radicals. This reaction is not spontaneous at room temperature and requires sufficient electrical or thermal energy to be absorbed from the external environment. The perfluoroalcohol produced during this reaction can subsequently undergo four possible reactions: H atom abstraction from alcohol groups by an OH radical; H atom abstraction by SO 4 •- ; direct HF removal; and HF removal with water as the catalyst. The final degradation products of HFPO-DA mainly include CO 2 , CF 3 CF 2 COOH, CF 3 COOH, FCOOH and HF, which has been identified through previous experimental analysis. Ecotoxicity assessment indicates that degradation does not produce highly toxic intermediates, and that the final products are non-toxic, supporting the feasibility of persulfate-based AOP technologies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Corneal alkali burn is one of the most devastating ophthalmic emergencies correlated with remarkable morbidity resulting in severe visual impairment. Appropriate intervention in the acute phase determines the eventual outcome for later corneal restoration treatment. Since the epithelium plays an essential role in inhibiting inflammation and promoting tissue repair, sustained anti-matrix metalloproteinases (MMPs) and pro-epithelialization are the prior remedies during the first week. In this study, a drug-loaded collagen membrane (Dox-HCM/Col) that could be sutured to overlay the burned cornea was developed to accelerate the early reconstruction. Doxycycline (Dox), a specific inhibitor of MMPs, was encapsulated in collagen membrane (Col) through hydroxypropyl chitosan microspheres (HCM) to develop Dox-HCM/Col, affording a preferable pro-epithelialization microenvironment and an in-situ controlled release. Results showed that loading HCM into Col prolonged the release time to 7 days, and Dox-HCM/Col could significantly suppress the expression of MMP-9 and -13 in vitro and in vivo. Furthermore, the membrane accelerated the corneal complete re-epithelialization and promoted early reconstruction within the first week. Overall, Dox-HCM/Col was a promising biomaterial membrane for treating alkali-burned cornea in the early stage, and our attempt may provide a clinically feasible method for the ocular surface reconstruction., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2023. Published by Elsevier B.V.)

Combination drugs have been used for several diseases for many years since they produce better therapeutic effects. However, it is still a challenge to discover candidates to form a combination drug. This study aimed to investigate whether using a comprehensive in silico approach to identify novel combination drugs from a Chinese herbal formula is an appropriate and creative strategy. We, therefore, used Toujie Quwen Granules for the main protease (M pro ) of SARS-CoV-2 as an example. We first used molecular docking to identify molecular components of the formula which may inhibit M pro . Baicalein (HQA004) is the most favorable inhibitory ligand. We also identified a ligand from the other component, cubebin (CHA008), which may act to support the proposed HQA004 inhibitor. Molecular dynamics simulations were then performed to further elucidate the possible mechanism of inhibition by HQA004 and synergistic bioactivity conferred by CHA008. HQA004 bound strongly at the active site and that CHA008 enhanced the contacts between HQA004 and M pro . However, CHA008 also dynamically interacted at multiple sites, and continued to enhance the stability of HQA004 despite diffusion to a distant site. We proposed that HQA004 acted as a possible inhibitor, and CHA008 served to enhance its effects via allosteric effects at two sites. Additionally, our novel wavelet analysis showed that as a result of CHA008 binding, the dynamics and structure of M pro were observed to have more subtle changes, demonstrating that the inter-residue contacts within M pro were disrupted by the synergistic ligand. This work highlighted the molecular mechanism of synergistic effects between different herbs as a result of allosteric crosstalk between two ligands at a protein target, as well as revealed that using the multi-ligand molecular docking, simulation, free energy calculations and wavelet analysis to discover novel combination drugs from a Chinese herbal remedy is an innovative pathway., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Author(s).)

The proliferation of modern vegetable plastic greenhouses (VPGS) supplies more and more vegetables for food all over the world. The airborne bacteria and fungi induce more exposure opportunities for workers toiling in confined plastic greenhouses. Culture-independent approaches by qPCR and high-throughput sequencing technology were used to study the airborne particulates microbiota in typic VPGS in Shandong, a large base of vegetables in China. The result revealed the mean airborne bacteria concentrations reached 1.67 × 10 3 cells/m 3 (PM 2.5 ) and 2.38 × 10 3 cells/m 3 (PM 10 ), and the mean airborne fungal concentrations achieved 1.49 × 10 2 cells/m 3 (PM 2.5 ) and 3.19 × 10 2 cells/m 3 (PM 10 ) in VPGS. The predominant bacteria in VPGS included Ralstonia, Alcanivorax, Pseudomonas, Bacillus, and Acinetobacter. Botrytis, Alternaria, Fusarium, Sporobolomyces, and Cladosporium were frequently detected fungal genera in VPGS. A higher Chao1 of bacteria in PM 10 was significantly different from PM 2.5 in VPGS. The potential pathogens in VPGS include Raltonia picketti, Acinetobacter lwoffii, Bacillus anthracis, Botrytis cinerea, and Cladosporium sphaerospermum. The network analysis indicated that airborne microbiota was associated with soil microbiota which was affected by anthropologic activities. The predicted gene functions revealed that bacterial function mainly involved metabolism, neurodegenerative diseases, and fungal trophic mode dominated by Pathotroph-Saprotroph in VPGS. These findings unveiled airborne microbiomes in VPGS so that a strategy for improving air quality can be applied to safeguard health and vegetation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The conjunctiva covers the largest area of ocular surface and is responsible for tear balance and clear vision. After trauma or surgery, the conjunctiva is prone to scarring and contracture. Transplantation with suture often implies numerous complications, such as inflammation, suture erosion, granuloma. And the suture needs to be removed, which means a secondary trauma. In this study, a bioadhesive hydrogel (GMO) for sutureless conjunctival transplantation was developed based on a semi-interpenetrating polymer network (sIPN) consisting of gelatin methacrylate (GelMA) and oxidized hyaluronic acid (OHA). The maximum adhesion strength was 157 ± 17 kPa, and the burst pressure was 357 ± 29 kPa, which was 15 times higher than the human intraocular pressure (IOP). GMO bioadhesive hydrogel significantly improved surgical efficiency and secured the collagen scaffold firmly to a rabbit conjunctival defect. The sutureless transplantation approach revealed the promoted tissue repair without scar. In conclusion, GMO bioadhesive may be an attractive alternative to suture for ocular surface reconstruction by avoiding suture-related complications and improving clinical outcome. STATEMENT OF SIGNIFICANCE: Conjunctival tissue is prone to scarring and contracture after trauma, and surgery with sutures often implies numerous complications. In this study, the ocular surface reconstruction was achieved by sutureless transplantation of conjunctival scaffold using bioadhesive hydrogel. The prepared GMO bioadhesive based on the semi-interpenetrating network of gelatin methacrylate (GelMA) and oxidized hyaluronic acid (OHA) had favorable adhesion and mechanical properties. The sutureless transplantation approach significantly improved the operation efficiency, avoided suture-related complications, and promoted the regeneration of conjunctiva. This study highlights the great potential of the sutureless repair strategy for clinical application in ocular surface reconstruction., Competing Interests: Declaration of Competing Interest There are no conflicts of interest in this work., (Copyright © 2022. Published by Elsevier Ltd.)

Nuclear factor-κB (NF-κB) signaling participates in many biologic processes including immunity, inflammation, and cancer. Here we reported that tripartite motif-containing protein 56 (TRIM56), an E3 ligase enzyme, participated in TNFα-induced NF-κB signaling by interacting with TAK1. Overexpression of TRIM56 potentiated the activation of TNFα-induced NF-κB signaling, whereas knockdown of TRIM56 had an opposite effect. TRIM56 enhanced the ubiquitination of TAK1, specifically enhanced the M1-linked polyubiquitin chains to TAK1, leading to the tight interactions of the TAK1-IKKα complex. Consequently, the stimulation of TNFa and TRIM56 strengthened the interaction with TAK1. Furthermore, we found that the C terminal (CT) domain was the binding region of TRIM56, and the RING domain of TRIM56 was the E3 enzyme activity region which was important to the ubiquitination of TAK1. Together, these results reveal that TRIM56 positively regulates TNFα-induced NF-κB signaling by heightening the ubiquitination of TAK1 and provide new insight into the complicated mechanisms of the inflammatory and immune response., Competing Interests: Declaration of competing interest The authors declare that there are no conflicts of interest., (Copyright © 2022. Published by Elsevier B.V.)

Benzophenone-3 (BP-3) is a widespread emerging organic pollutant. However, little is known about the synergistic effect of various reactive oxygen species (ROS) in natural waters and wastewater treatment plants on its transformation. In this study, the indirect photochemical behavior of BP-3 in the natural aquatic environments and the degradation process in the AOPs system were investigated by theoretical chemistry calculations. Besides the potential eco-toxicity effects, health effects, and bioaccumulation of the transformation products were assessed by computational toxicology. Results of transformation mechanism and kinetics showed that OH· and 1 O 2 are the keys to the transformation of BP-3, whereas the role of HO 2 · and O 3 can be ignored. AOPs based on OH· and 1 O 2 could lead to the rapid transformation of BP-3, while the transformation of BP-3 in natural waters is slow, and even environmental persistence can be observed. However, dissolved organic matter (DOM) promotes the indirect phototransformation of BP-3 in natural waters. A variety of transformation products are generated under the synergistic effects of ROS, H 2 O, and 3 O 2 . Assessments of environmental risks indicated that the potential eco-toxicity and health effects of the main products are significantly lower than that of the parent BP-3. More importantly, low bioaccumulation of transformation products would not enlarge their eco-toxicity and health effects. This study not only gives valuable insights into the indirect phototransformation of BP-3 in natural waters but also provides theoretical support for the feasibility of BP-3 degradation in industrial wastewater by AOPs based on OH· and 1 O 2 ., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Butylated hydroxyanisole (BHA) is one of important phenolic antioxidants and its fate in the environment has attracted much attention in recent years. In this study, the initial reactions of BHA with OH radicals, including 8 abstraction reactions and 6 addition reactions, were calculated. The lowest energy barrier of 3.20 kcal mol -1 was found from the abstraction reaction on phenolic hydroxyl group. The reaction barriers of addition paths are in the range of 5.48-9.28 kcal mol -1 , which are lower than those of the abstraction paths. The reaction rate constants were calculated by using transition state theory, and the rate constants are 8.12 × 10 7 M -1 s -1 and 4.76 × 10 7 M -1 s -1 for the H-abstraction and OH-addition reactions, respectively. Through the calculation of the subsequent reactions of the abs-H 0 -TS 1 and add-C 4 -M 1 it was found that BHA would be further transformed into 2-tert-Butyl-1,4-benzoquinone (TBQ), tert-butylhydroquinone (TBHQ) etc. in the aqueous phase, and the eco-toxicities of these transformed products of BHA in the aqueous phase were significantly increased comparing with that of the BHA and they are toxic to aquatic organism., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Corneal transplantation is an effective treatment for corneal blindness. However, it brings risk factors for the occurrence of bacterial keratitis, which can affect the repair effect and even lead to transplantation failure. The difficulty in re-epithelialization is also a main problem faced by corneal transplantation. Herein, a collagen-GelMA composite membrane containing lysozyme (CGL) was developed as an antibacterial corneal implant to fill stromal defect and support re-epithelialization. Characterizations of physicochemical properties and in vitro biocompatibility revealed that the composite membranes have proper water content, light transmittance and mechanical strength as well as good biocompatibility. Particularly, the cell adhesion force and adhesion-related genes expression were evaluated and exhibited an improvement after the addition of GelMA. Furthermore, the formed CGL membrane could continuously release lysozyme and exhibited a bactericidal rate of 96% and 64% after 2 h and 72 h, respectively. The results demonstrated that this CGL membrane has promising application in corneal repair., (Copyright © 2021. Published by Elsevier B.V.)

1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), as an emerging brominated flame retardant (EBFR) pollutant, has been often observed in the air, and to comprehend its fate in the environment is still challenging due to the diversity of its stereoisomers. In this work, the environmental transformation behavior and potential toxicological implications of TBECH stereoisomers under the oxidation of OH· in the gas phase were investigated by computational chemistry. Our results indicate the complexity of the TBECH transformation reactions and the diversity of its transformation products in the atmosphere. Although the reactions of TBECH enantiomers with OH· exhibit highly consistency, it is obvious that the reactions of the four diastereoisomers of TBECH with OH· and their subsequent reactions have both specificity and similarity. The dehydrogenation intermediates produced by H-abstraction of OH· in the initial reactions may undergo oxidative debromination, hydroxylation and decomposition reactions, leading to the transformation into low bromine and monohydroxy substituted compounds, as well as debrominated or unbrominated unsaturated fatty ketones. The toxicity assessments show that all transformation products are less toxic to aquatic organisms than TBECH, but some of them are still classified at toxic or harmful levels. More importantly, some transformation products still exhibit carcinogenic and teratogenic activity. To our knowledge, this study provides, for the first time, a deep insight into the transformation mechanism, kinetics, and environmental impacts of atmospheric TBECH by theoretical calculations., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Bioaccumulation of perfluoroalkyl and polyfluoroalkyl substances (PFASs) is an important indicator of their hazard. Partitioning to membrane phospholipids is one of the pathways for their bioaccumulation. However, the molecular mechanism on PFASs uptake into membrane phospholipids is not yet to be fully understood. In this work, we used molecular dynamics (MD) simulations to study the uptake processes of PFOS and its alternatives (6:2 Cl-PFESA and OBS) into DPPC bilayers, and to evaluate their interaction with DPPC bilayers and their effect on properties of DPPC bilayers. The result of free energy changes shows that a barrier of 2-3 kcal mol -1 exists when these adsorbed PFASs on the surface are absorbed into DPPC bilayers. After incorporating into DPPC bilayers, three DPPC molecules interact with and thus stabilize a PFOS (or 6:2 Cl-PFESA or OBS) molecule. And another role of the three DPPC molecules is to shield these PFASs from exposure to water environment. These PFASs have the similar condensing effect on the model membrane. The molecular-level study is beneficial for understanding the bioaccumulation and toxicity of PFOS and its alternatives., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background and Aims: Obesity is characterized as overall or regional adiposity accumulation. However, the metabolic status underlying fat accumulation was not well understood. We sought to identify metabolite profiles based on their correlations with body mass index (BMI), body fat percentage (BFP), waist circumference (WC), and visceral adiposity index (VAI) in young Chinese adults (19-37 years old), and their associations with dietary consumption were also explored., Methods and Results: A total of 86 plasma samples were analyzed using untargeted lipidomics and metabolomics approaches. Metabolite profiles of adiposity indices were identified using random forest modelling. Ridge regression was used to generate metabolite scores. Overall, 30, 46, 30, and 20 metabolites correlated with BMI, BFP, WC, and VAI, respectively, which resulted in metabolite scores for each index. Top three enriched categories of the identified metabolites were glycerophospholipids, glycerolipids, and sphingolipids, with some specific metabolites (such as phosphatidylserine (37:2), phatidylethanolamine (42:4), and ceramide (40:0)) exclusively associated with overall adiposity, and some other metabolites exclusively associated with abdominal adiposity indices, e.g., triradylglycerol (45:0, 52:4, and 35:0) and diacylglycerol (38:4, 36:3, and 36:5). Moreover, metabolite scores were negatively associated with the intake of food rich in protein or fiber, while they were positively associated with food rich in carbohydrate, with similar results for adiposity indices., Conclusion: We observed unique metabolite profiles of regional or overall fat deposition in young adults. Glycerophospholipids, glycerolipids, or sphingolipids may be involved in the regulation of adiposity accumulation, affected by dietary exposures., Competing Interests: Declaration of competing interest The authors declared no conflict of interest., (Copyright © 2021 The Italian Diabetes Society, the Italian Society for the Study of Atherosclerosis, the Italian Society of Human Nutrition and the Department of Clinical Medicine and Surgery, Federico II University. Published by Elsevier B.V. All rights reserved.)

Fenpiclonil is an agricultural phenylpyrrole fungicide, which raise the concern about its ecotoxicological effects. In this paper, we investigate the indirect photochemical transformation mechanisms, environmental persistence and eco-toxicity of fenpiclonil initiated by various active oxidants ( 1 O 2 , •OH and SO 4 •‾) in aquatic environments. The results shown that 1 O 2 can react with pyrrole ring by cycloaddition pathways to form the endo-peroxides. In addition, •OH and SO 4 •‾ initial mechanisms are calculated, suggesting that •OH-initiated mechanisms play a dominant role in the degradation process of fenpiclonil at high rate constants (2.26 ×10 9 M -1 s -1 , at 298 K). The kinetic calculation results indicate that high temperature is more favorable for the degradation of fenpiclonil. To better understand the adverse effects of the transformation products formed during the subsequent reaction of •OH-adduct IM10, the computational toxicology has been used for the toxicity estimation. The results show that aquatic toxicity of these products decrease with degradation process, especially the decomposition products (TP3 and TP4). However, TP1 and TP2 are still toxic and developmental toxicant. The study provides guidance for further experimental research and industrial application of fungicide degradation from the perspective of theoretical calculation., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Mental retardation, X-linked 21/34 (MRX21/34), is a rare intellectual disability disease caused by mutations in the IL1RAPL1 (Interleukin-1 Receptor Accessory Protein-Like 1) gene. Using Sendai virus-mediated reprogramming, we established an induced pluripotent stem cell (iPSC) line from PBMCs collected from a ten-year-old boy with MRX21/34. The iPSCs showed stable amplification, expressed pluripotent genes, displayed a normal karyotype, and had characteristics of trilineage differentiation potential in an in vitro differentiation assay., (Copyright © 2021. Published by Elsevier B.V.)

Floating-harbor syndrome, are mainly caused by heterozygous truncating mutations in SRCAP. To our best knowledge, the mutation (c.452_453del) located in the fifth exon of SRCAP, has not been reported yet. Herein, an induced pluripotent stem cell (iPSC) line was generated from the peripheral blood mononuclear cells of an infant with floating-harbor syndrome accompanied with dilated cardiomyopathy through Sendaivirus-mediated reprogramming. These iPSCs have excellent cellular features, including stable amplification, pluripotent markers expression, and spontaneous differentiation into three germ layers, and a normal karyotype. These iPSCs provide a suitable cell model to study the mechanism of Floating-harbor syndrome., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

CTNNA3, first reported in association with arrhythmogenic right ventricular cardiomyopathy in 2003, is an unique component of both desmosomes and adherens junctions. Using Sendaivirus-mediated reprogramming, we generated an induced pluripotent stem cell (iPSC) line from the peripheral blood mononuclear cells of a child with arrhythmia. The iPSCs exhibited stable amplification, expressed pluripotent markers, and differentiated spontaneously into three germ layers in vitro. Additionally, this iPSC line was found to maintain a normal karyotype and retain the pathogenic mutation in CTNNA3, facilitating a platform to study the disease mechanisms of arrhythmia and dysfunctions related to CTNNA3 mutations., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

P-nitrophenol (p-NP) is a recalcitrant organic compound attracted great environmental attention, but its degradation mechanism is indeterminacy, which challenges its treatment, migration, transformation and ecological impact in the environment. In the present study, the aqueous-phase decomposition process of p-NP initiated by O 3 has been investigated by a theoretical calculation method. The detailed possible reaction pathways for the oxidative degradation of p-NP by ozone have been proposed. The chemical reaction thermodynamics results show that the reaction barriers of all ozone-initiated pathways are below 15 kcal·mol -1 , indicating that ozone can completely initiate the oxidation of p-NP under natural conditions. However, the kinetic results show that the initiation reaction of p-NP by ozone alone is relatively slow compared to the reaction by OH. Interestingly, under ultraviolet (UV) radiation, the dissolved ozone interacts with water and produces two active radicals: OH and HO 2 . The reaction rate of p-NP initiated with OH is much higher than that with ozone, implying that the OH produced in the photochemical process can improve the removal efficiency of p-NP. The intermediates generated in the ozone-initiated reaction have been found to decompose into small molecule organic acids, aldehydes and ketones. The potential carcinogenicities and teratogenicities of the transformation products have also been studied, and some of them still have carcinogenic activity, which deserve further attention. In addition, to our knowledge, this may be the first computational chemistry study on the degradation of p-NP initiated by HO 2 . All the results provide a new fundamental understanding for the migration and transformation of p-NP in water environment, and indicate that further assessment is needed for the impact of p-NP and especially its transformation products on the ecological environment in a significant way., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Aims: The reversible protein S-glutathionylation (PSSG) modification of Fas augments apoptosis, which can be reversed by the cytosolic deglutathionylation enzyme glutaredoxin-1 (Grx1), but its roles in alcoholic liver injury remain unknown. Therefore, the objective of this study was to investigate the impact of genetic ablation of Grx1 on Fas S-glutathionylation (Fas-SSG) in regulating ethanol-induced injury., Materials and Methods: We evaluated the Grx1 activity and oxidative damage, hepatic injury related indicators, Fas-SSG, we also assess the nuclear factor-κB (NF-κB) signaling, its downstream signal, and Akt signaling cascades, Furthermore, the number of Kupffer cells and related proinflammatory cytokines between WT and Grx1- groups after alcohol exposure., Key Findings: Ethanol-fed mice had increased Grx1 activity and oxidative damage in the liver. Grx1-deficient mice had more serious liver damage when exposed to ethanol compared to that of wild-type mice, accompanied by increased alanine aminotransferase and aspartate aminotransferase levels, Fas-SSG, cleaved caspase-3 and hepatocyte apoptosis. Grx1 ablation resulted in the suppression of ethanol-induced NF-κB signaling, its downstream signal, and Akt signaling cascades, which are required for protection against Fas-mediated apoptosis. Accordingly, blocking NK-κB prevented Fas-induced apoptosis in WT mice but not Grx1-/- mice. Furthermore, the number of Kupffer cells and related proinflammatory cytokines, including Akt, were lower in Grx1-/- livers than those of the controls., Significance: Grx1 is essential for adaptation to alcohol exposure-induced oxidative injury by modulating Fas-SSG and Fas-induced apoptosis., (Copyright © 2020. Published by Elsevier Inc.)

Recent research has shown that the complexation of metals-organics plays an important role in atmospheric particulate matter, whose health effects should be taken into account. This work investigates the interactions between catechols (CAs), i.e., 4-nitrocatechol (4NC) and 4-methylcatechol (4MC), and transition metals (i.e., Fe) in the aqueous phase dark reaction. The formation of Fe/CAs complexes and secondary organics products are analyzed by UV-Vis spectroscopy, stopped-flow spectroscopy, high-resolution mass spectrometry and Raman spectroscopy, while the insoluble particulate matter formed from the CAs/Fe mixtures are characterized by the FTIR, X-ray photoelectron spectroscopy (XPS) and thermogravimetric-quadrupole-mass spectrometry (TG-Q-MS). On the basis of the density functional theory (DFT) calculation and experimental results, the possible formation pathways for the complexes of Fe(III) with 4NC (a proxy for organics) are proposed. The Fe/CAs complexes and organics products perhaps have significant sources of light absorption which play an important role in influencing the intensity of atmospheric radiation and particulate phase photochemistry. Besides, the cytotoxicity is tested as a function of concentrations for CAs/Fe mixtures in BEAS-2B cells. Our results show that CAs/Fe mixtures have strong association with cytotoxicity, indicating the mixtures have potential influence to human health., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Background: Mitochondrial DNA depletion syndrome-13 (MTDPS13) is caused by mutations in FBXL4 (F-box and leucine-rich repeat protein 4), a nuclear gene encoding an F-box protein that plays a role in maintaining mtDNA integrity and stability., Methods: We identified a novel homozygous FBXL4 gene mutation, c.993dupA (p.L332Tfs*3), in a 1-year-old girl of Han Chinese descent. We performed three-dimensional protein structural analysis and targeted mtDNA next-generation sequencing. We analysed FBXL4 expression and mitochondrial DNA level, and reviewed mutations reported in FBXL4-related literature., Results: This mutation resulted in premature termination of translation and loss of 288 amino acids from C-terminus. A three-dimensional structural analysis revealed that conserved LRR domains were lost in mutant FBXL4 protein, which likely affected its ability to form protein-protein interactions. There were no differences in FBXL4 mRNA expression levels between the patient and her parents. There were no mtDNA mutations in either the patient or her parents. However, ND1/GAPDH ratio in lymphocytes and urine, which represents mtDNA/nuclear DNA ratio, showed that the number of mitochondrial genomes was significantly lower in the patient than in her parents or wild-type subjects., Conclusion: Homozygous FBXL4 gene mutation, c.993dupA, can cause mitochondrial dysfunction, and LRR region is especially important for FBXL4 protein function., (Copyright © 2020 The Author(s). Published by Elsevier B.V. All rights reserved.)

Allan-Herndon-Dudley syndrome (AHDS) is a rare, X-chromosome-linked inherited disorder that affects brain development and is caused by a mutation in SLC16A2. Herein, we generated an induced pluripotent stem cell (iPSC) line from the peripheral blood mononuclear cells of a one-year-old male infant with AHDS using Sendai-virus-mediated reprogramming. These iPSCs exhibited stable amplification, expressed pluripotent markers, and differentiated spontaneously into three germ layers in vitro. Additionally, this iPSC line was found to maintain a normal karyotype and retain the pathogenic mutation in SLC16A2, facilitating the study of disease mechanisms and development of new therapies of AHDS., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Fludioxonil has been proven valuable as a broad-spectrum fungicide. However, there are concerns about its risk posed to non-target organisms in aquatic environments. In this paper, the mechanism, photoproducts transformation and eco-toxicity of fludioxonil during •OH/ 1 O 2 -initiated process were systematically studied using quantum chemistry and computational toxicology. The results indicate that the two favorable pathways of •OH/ 1 O 2 -initiated reactions are both occurred in pyrrole ring. It can conclude that the rate constants of •OH and 1 O 2 are 1.23 × 10 10 and 3.69 × 10 7  M -1  s -1 at 298K, respectively, which results in half-lives of <2 days in surface waters under sunlit near-surface conditions. Based on toxicity assessments, these photoproducts showed a decreased aquatic toxicity but the majority products are still toxic. This study gives more insight into the chemical transformation mechanism of fludioxonil in aquatic environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Mediator complex subunit 12 (MED12)-related disorders are recessive-X-linked intellectual disabilities present primarily in male patients. We came across a female patient with a heterozygous mutation (c.1249-1G > C) related to MED12-related syndrome. MED12 expression was significantly lower than that in her parents, and another X chromosome was inactive. We established an induced pluripotent stem cell (iPSC) line from peripheral blood mononuclear cells (PBMCs) of a 1-year old Chinese girl with a heterozygous mutation (c.1249-1G > C) in MED12. PBMCs were reprogrammed using nonintegrative Sendai viral vectors. The iPSCs showed stable amplification, pluripotency-related gene expression, trilineage differentiation potential, and a normal karyotype., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Dnmt1, Dnmt3a and Dnmt3b are main genes encoding DNA methyltransferases (Dnmts) which catalyze DNA methylation and regulate gene expression without changing DNA sequence. Our previous study disclosed that double knockout of Dnmt1 and Dnmt3a in forebrain excitatory neurons impaired synaptic plasticity and led to hippocampus-dependent learning and memory deficits, however the underlying synaptic mechanisms remain uncertain. In this study, we selectively knocked down the expression of Dnmt1 and Dnmt3a in primary cultured hippocampal neurons derived from embryonic Dnmt1,3a 2flox/2flox mice by transfection with Cre-expressing virus, to study the effect of Dnmts and mediated DNA methylation on synaptogenesis and synaptic function. We found that the hippocampal neurons at 15 days in vitro (DIV15) exhibited similar size of cell body, but longer dendrites with reduced number of branches and lower density of excitatory synapses formation after virus-mediated Dnmt1 and Dnmt3a deletion. Supportively, cultured neurons with Dnmt1 and Dnmt3a deficiency displayed reduced frequency and amplitude of miniature excitatory postsynaptic currents (mEPSCs), indicating that both pre- and post-synaptic dysfunction are involved. In addition, our Ca 2+ -image study with Rhod-3AM revealed suppression of glutamate-evoked elevation of cytoplasmic [Ca 2+ ] after Dnmt1 and Dnmt3a deletion. Altogether our findings provide new evidence that normal expression of Dnmt1 and Dnmt3a in hippocampal neurons are essential for excitatory synaptogenesis and synaptic function., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Mitochondrial DNA depletion syndrome-13 (MTDPS13) is a rare autosomal recessive mitochondrial disease caused by mutations in the FBXL4 (F-box and leucine-rich repeat protein 4) gene. Using Sendai virus-mediated reprogramming, we established an induced pluripotent stem cell (iPSC) line from PBMCs collected from a one-year-old female patient with MTDPS13. The iPSCs were stable during amplification, expressed pluripotent genes, maintained a normal karyotype, and showed characteristics of the three germs layers in an in vitro differentiation assay., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Introduction: Because greed is associated with various destructive outcomes, understanding the developmental precursors to dispositional greed in adolescence is of great importance. However, there are few empirical studies on this topic. The current study aimed to examine the relationship between childhood socioeconomic status (CSES) and adolescent greed and the moderating effect of family size. Two competing hypotheses were proposed. One is the scarcity hypothesis, which claims that CSES may be negatively related to adolescent greed. Another is the luxury hypothesis, which proposes that the richer the environment one grew up in, the more likely one is to develop dispositional greed., Method: A cross-sectional sample of 3,200 adolescents (11-19 years old, 1,712 females, 1,356 males, and 132 of unknown gender) from North, Northwest, Middle and South China completed the questionnaire sets. A hierarchical multiple regression analysis was conducted., Results: CSES was positively correlated with dispositional greed, and the moderating effect of family size was significant., Conclusion: The current study provides evidence supporting the luxury hypothesis over the scarcity hypothesis. In addition, adolescent dispositional greed increases with an increase in CSES when there is only one child in the family, while this is not the case for children with siblings. The theoretical and practical implications of the current study results as well as future research directions are discussed., (Copyright © 2019. Published by Elsevier Ltd.)

Sulfate radical (SO 4 - ) and hydroxyl radical (OH) generated from persulfate or peroxymonosulfate in AOPs have been widely used in contaminant degradation. Anthracene (ANT) can be decomposed by SO 4 - and OH. The processes of ANT decomposition were investigated using theoretical calculations in this paper. The initiation reactions of ANT, anthrone, anthraquinone (ATQ) and 1-hydroxylanthraquinone (1-hATQ) by two radicals are studied. The highest free energy barriers of initiation reactions are 22.30 kcal mol -1 in ATQ + SO 4 - reaction and 6.84 kcal mol -1 in ATQ + OH reaction. Comparing the rate constants of initiation reaction through the two radicals at 273-373 K, it can be concluded that SO 4 - and OH both play important roles on the initiation of ANT and anthrone at lower pH. For ATQ and 1-hATQ, OH is more important than SO 4 - in the initiation process, which indicates that the indirect influence of SO 4 - are more significant in the degradation processes of ATQ and 1-hATQ. This study provides theoretical confirmations for the mechanisms of reactions of ANT with SO 4 - and OH, and evaluates the importance of SO 4 - and OH according to the reaction rates. The work can give more insight into the degradation of PAHs by radicals., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Methanesulfinic acid (MSIA), an organic sulfur compound, is mainly produced in the oxidation process of dimethyl sulfide in the atmosphere. The properties of MSIA at the air-water interface were studied using molecular dynamics (MD) simulations. The result shows that the lowest system free energy is located at the interface. Because the free energy difference between the interface and water phase is 3.2 kJ mol -1 , the MSIA molecule can easily get out of the free energy well and travel to water phase by the thermal motion, leading to only a 21% probability of its occurrence at the interface. The MSIA molecule tends to tilt at the interface with the sulfino group (-S(O)-OH) pointing toward the water phase. The feature of hydration status at the air-water interface may be favorable to the heterogeneous oxidation of MSIA., (Copyright © 2019. Published by Elsevier B.V.)

A silk fibroin/collagen/hyaluronic acid (SF/COL/HA) composite scaffold was prepared via admixing, crosslinking, and lyophilizing processes. We studied its physicochemical and biological properties, such as water absorption, porosity, weight loss, and biocompatibility. The optimal ratio of SF/COL/HA scaffold was 3:6.5:0.5. Then, the optimal ratio of scaffold incorporating pilose antler polypeptides (PAPs)-PLGA microspheres was prepared, and their compatibility was studied. PAP-SF/COL/HA scaffold had favorable adhesion and proliferation. A rabbit cartilage defect model was established. The repair effect of cartilage defects was observed and evaluated among PAP-SF/COL/HA, SF/COL/HA, and sham operation groups. The defects were almost completely repaired after 13 weeks in the PAP-SF/COL/HA group, thereby indicating that the PAP-SF/COL/HA composite had a favorable effect on articular cartilage repair., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Soil is the largest organic carbon (C) pool in terrestrial ecosystems. Periodic changes in environmental temperature occur diurnally and seasonally; yet, the response of soil organic matter (SOM) decomposition to varying temperatures remains unclear. In this study, we conducted a modified incubation experiment using soils from 16 forest ecosystems in China with periodically and continuously varying incubation temperature to investigate how heterotrophic respiration (R h ) responds to different temperature patterns (both warming and cooling temperature ranging between 5 and 30°C). Our results showed a pronounced asymmetric response of R h to temperature warming and cooling among the soils of all forest ecosystems, with R h increasing more rapidly during the warming phase compared to the cooling phase. This asymmetric response of R h to warming and cooling temperatures was widespread in all soils. In addition, the amplitude of this asymmetric response differed among different forest ecosystems, with subtropical and warm-temperate forest ecosystems exhibiting greater asymmetric responses. Path analyses showed that soil pH and the microbial community explained most of the variation in this asymmetric response. Furthermore, the widespread asymmetric response of R h to warming and cooling temperatures suggests that accumulated SOM decomposition might be overestimated on average by 20% for warming alone when compared with admix warming and cooling. These findings provide new insights on the responses of R h to natural shifts in temperature, emphasizing the need to consider this widespread asymmetric response of R h to warming and cooling phases to predict C-climate feedback with great accuracy, especially under future non-uniform warming scenarios., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Hexachloro-1,3-butadiene (HCBD) is a persistent organic pollutant in the environment. When its samples were collected and observed, the levels of HCBD in its source and high mountains are higher than in urban cities, oil factories and countryside. The density functional theory is applied to the degradation mechanism of HCBD with Cl, NO 3 , HO 2 , OH and O 3 . Those reactions are optimized and calculated at two carbon sites of double bonds, and then the subsequent reactions of the OH-initiated intermediates with O 2 and NO are taken as examples. Ozonization reactions of HCBD including the formation of primary and secondary ozonides are investigated. The Criegee intermediates created in the ozonization reactions can react with O 2 , SO 2 , NO 2 and H 2 O. Reaction rate constants of the Cl, NO 3 , HO 2 , OH and O 3 initiated reactions with HCBD are calculated within 200 to 400 K with the transition state theory method, and the rate constants of the Cl, NO 3 , HO 2 , OH and O 3 at 298.15 K are 4.51 × 10 -13 , 1.32 × 10 -20 , 4.33 × 10 -29 , 6.33 × 10 -16 , 5.80 × 10 -27  cm 3 molecule -1  s -1 , respectively. The reactions of OH and Cl radicals with HCBD are more important than those of NO 3 , HO 2 and O 3 according to the reaction rate branching ratio. Both the temperature and reaction rate could change with the height., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Advanced oxidation processes (AOPs) are widely used in wastewater treatment of pharmaceutical and personal care products (PPCPs). In this work, the OH-initiated transformation as well as the hydrolysis of a typical PPCPs, aspirin, was investigated using density functional theory (DFT) calculations and laboratory experiments. For DFT calculations, the frontier electron densities and bond dissociation energies were analyzed. Profiles of the potential energy surface were constructed, and all the possible pathways were discussed. Additionally, rate constants for each pathway were calculated with transition state theory (TST) method. UV/H 2 O 2 experiments of aspirin were performed and degradation intermediates were identified by UPLC-MS-MS analysis. Different findings from previous experimental works were reported that the H-abstraction pathways at methyl position were dominated and OH-addition pathways on benzene ring were also favored. Meantime, hydroxyl ASA was confirmed as the main stable intermediate. Moreover, it was the first time to use DFT method to investigate the hydrolysis mechanisms of organic ester compound., (Copyright © 2017 Elsevier B.V. All rights reserved.)

For cartilage repair, ideal scaffolds should mimic natural extracellular matrix (ECM) exhibiting excellent characteristics, such as biocompatibility, suitable porosity, and good cell affinity. This study aimed to prepare a collagen/silk fibroin composite scaffold incorporated with poly-lactic-co-glycolic acid (PLGA) microsphere that can be applied in repairing cartilage. To obtain optimum conditions for manufacturing a composite scaffold, a scaffold composed of different collagen-to-silk fibroin ratios was evaluated by determining porosity, water absorption, loss rate in hot water, and cell proliferation. Results suggested that the optimal ratio of collagen and silk fibroin composite scaffold was 7:3. The microstructure and morphological characteristics of the obtained scaffold were also examined through scanning electron microscopy and Fourier transform infrared spectroscopy. The results of in vitro fluorescence staining of bone marrow stromal cells revealed that collagen/silk fibroin composite scaffold enhanced cell proliferation without eliciting side effects. The prepared composite scaffold incorporated with PLGA microsphere was implanted in fully thick articular cartilage defects in rabbits. Collagen/silk fibroin composite scaffold with PLGA microspheres could enhance articular cartilage regeneration and integration between the repaired cartilage and the surrounding cartilage. Therefore, this composite will be a promising material for cartilage repair and regeneration., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Matrine is the major bioactive alkaloid found in certain Sophora plants and has been used for the treatment of liver diseases and protection of liver function. The aim of this study was to investigate the human liver uptake mechanism of matrine by using HepG2 cells as the in vitro model. Matrine was transported into HepG2 cells in a time- and temperature-dependent manner. The cellular uptake was saturable and was significantly reduced by the metabolic inhibitors, such as sodium azide and rotenone. Furthermore, the uptake of matrine was found to be regulated by a protonophore (carbonyl cyanide 4-(trifluoromethoxy)phenylhydrazone) and pH, indicating that this influx transporter may be a proton-coupled antiporter. The uptake of matrine was sensitive to inhibition by the cationic drugs including pyrilamine, quinidine, verapamil, amantadine, diphenhydramine, and cimetidine but insensitive to other typical substrates or inhibitors of well-known organic cation transport systems. The present study reveals that, for the first time, in HepG2 cells, the existence of a proton-coupled organic cation antiporter that contributes substantially to the hepatic uptake of matrine., (Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.)

The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ(13)C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ(13)C and the isotopic composition of source CO2 (δ(13)CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ(13)C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ(13)C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83±14.11% and 86.84±12.27% and that natural gas had average contributions of 16.17±14.11% and 13.16±12.27%, respectively. The δ(13)C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ(13)C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Long-term phosphorus (P) and nitrogen (N) applications may seriously affect soil microbial activity. A long-term field fertilizer application trial was established on reddish paddy soils in the subtropical region of southern China in 1998. We assessed the effects of swine manure and seven different rates or ratios of NPK fertilizer treatments on (1) the absolute and specific enzyme activities per unit of soil organic carbon (SOC) or microbial biomass carbon (MBC) involved in C, N, and P transformations and (2) their relationships with soil environmental factors and soil microbial community structures. The results showed that manure applications led to increases in the absolute and specific activities of soil β-1,4-glucosidase(βG), β-1,4-N-acetylglucosaminidase (NAG), and leucine aminopeptidase (LAP). The absolute and specific acid phosphatase (AP) activities decreased as mineral P fertilizer application rates and ratios increased. Redundancy analysis (RDA) showed that there were negative correlations between absolute and specific AP activities, pH, and total P contents, while there were positive correlations between soil absolute and specific βG, NAG, and LAP enzyme activities, and SOC and total N contents. RDA showed that the contents of actinomycete and Gram-positive bacterium PLFA biomarkers are more closely related to the absolute and specific enzyme activities than the other PLFA biomarkers (P<0.01). Our results suggest that both the absolute and specific enzyme activities could be used as sensitive soil quality indicators that provide useful linkages with the microbial community structures and environmental factors. To maintain microbial activity and to minimize environmental impacts, P should be applied as a combination of inorganic and organic forms, and total P fertilizer application rates to subtropical paddy soils should not exceed 44 kg P ha(-1) year(-1)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

To understand the heterogeneous reactions between NO2 and sea salt particles in the atmosphere of coastal areas, the absorption of an NO2 molecule on the NaCl(100) surface, the dimerization of NO2 molecules and the hydrolysis of N2O4 isomers at the (100) surface of NaCl are investigated by density functional theory. Calculated results show that the most favorable adsorption geometry of isolated NO2 molecule is found to reside at the bridge site (II-1) with the adsorption energy of -14.85 kcal/mol. At the surface of NaCl(100), three closed-shell dimers can be identified as sym-O2N-NO2, cis-ONO-NO2 and trans-ONO-NO2. The reactions of H2O with sym-O2N-NO2 on the (100) surface of NaCl are difficult to occur because of the high barrier (33.79 kcal/mol), whereas, the reactions of H2O with cis-ONONO2 and trans-ONONO2 play the key role in the hydrolysis process. The product, HONO, is one of the main atmospheric sources of OH radicals which drive the chemistry of the troposphere., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Haze episodes often hit urban cities in China recently. Here, we present several continuous haze episodes with extremely high PM2.5 levels that occurred over several weeks in early 2013 and extended across most parts of the northern and eastern China-far exceeding the Beijing-Tianjin-Hebei region. Particularly, the haze episode covered ~1 million km(2) on January 14, 2013 and the daily averaged PM2.5 concentration exceeded 360 μg m(-3) in Ji'nan. The observed maximum hourly PM2.5 concentration in urban Ji'nan reached 701 μg m(-3) at 7:00 am (local time) in January 30. During these haze episodes, several fog events happened and the concurrent fog water was found to be seriously polluted. For the fog water collected in Ji'nan from 10:00 pm in January 14 to 11:00 am in January 15, sulfate, nitrate, and ammonium were the major ions with concentrations of 1.54 × 10(6), 8.98 × 10(5), and 1.75 × 10(6) μeq L(-1), respectively, leading to a low in-situ pH of 3.30. The sulfate content in the fog sample was more than 544 times as high as those observed in other areas. With examination of the simultaneously observed data on PM2.5 and its chemical composition, the fog played a role in scavenging and removing fine particles from the atmosphere during haze episodes and thus was seriously contaminated. However, the effect was not sufficient to obviously cleanse air pollution and block haze episodes., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Growing attention has been devoted to understanding the formation and destruction of polyfluorinated dibenzo-p-dioxins (PFDDs). High-accuracy molecular orbital calculations have been performed to investigate the tropospheric oxidation reaction of 2,3,7,8-tetrafuorinated dibenzo-p-dioxin (TFDD) initiated by OH radical, NO3 radical and O3. The rate constant of TFDD reaction triggered by the OH radical, NO3 radical and O3 is about 2.30 × 10(-11)cm(3) molecule(-l) s(-l), 3.18 × 10(-13)cm(3) molecule(-l) s(-l), and 3.30 × 10(-19)cm(3) molecule(-l) s(-l), respectively. OH radical is the major gas phase tropospheric sink for TFDD. Once TFDD-OH intermediates are produced in the initial reactions, they can react with tropospheric O2 subsequently to generate peroxy radical isomers. The TFDD-OH-O2 can further react with tropospheric NO via isomerization or combination, resulting that the dioxin ring will be ruptured completely. This study can serve as a template for tropospheric degradation of the gaseous PFDDs, which is beneficial for assessing their tropospheric behaviors., (© 2013 Elsevier B.V. All rights reserved.)

High-accuracy molecular orbital calculation has been performed to investigate the atmospheric oxidation reaction of 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TeCDF) initiated by the OH radical in the presence of O(2) and NO/H(2)O. The possible channels involved in the reaction are discussed, and the favorable reaction pathways are revealed. The degradation occurs easily once the OH radical initiates the reaction. Two aspects need to be mentioned: one is that H(2)O in atmosphere is a source of OH radical which will initiate a new round of degradation and improve the degradation efficiency; the other is that the furan ring of 2,3,7,8-TeCDF can be turned into dioxin ring, which may explain the experimental hypothesis that polychlorodibenzofurans can be transformed to polychlorodibenzo-p-dioxins. Rate constants of the elementary reactions are calculated over a temperature range of 250-400K. Arrhenius formulas are fitted and the atmospheric lifetimes of reaction species in the troposphere are discussed for the first time, which can be applied to the study on the model simulation and the management of the hazardous materials., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The study shows that H abstraction reaction from the CH(3) group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH(3)O)(2)POOH (P1), CCl(3)CHOHPOOH(OCH(3)) (P2), CH(3)OPO(2) (P3), CCl(3)COPO(OCH(3))(2) (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A detailed understanding of the degradation mechanism of polychlorinated dibenzo-p-dioxins (PCDDs) is of great necessity. In wastewater treatment, an important degradation process of PCDDs ascribes to its reaction with the photo-Fenton reagent. In this paper, the reaction of 2,3,7,8-TeCDD with OH radicals has been studied using high level molecular orbital theory. The profile of the potential energy surface is constructed. A complete description of the possible degradation mechanism in solution is provided. Two degradation mechanisms are proposed: ring-opening and adducting mechanism, adducting and ring-opening mechanism. The main products obtained are 4,5-dichlorinate-o-dihydroxybenzene and 4,5-dichlorinate-o-quinone. The study on the quantitative structure-activity relationship of these PCDDs is performed. The structure-activity model has been constructed, in which three structural parameters, RO5-C12, RO5-C13 and QC14, are found to be positively correlated to the degradation activities.