Long-chain acyl-CoA synthetase-4 regulates endometrial decidualization through a fatty acid ß-oxidation pathway rather than lipid droplet accumulation.

OBJECTIVE: Lipid metabolism plays an important role in early pregnancy, but its effects on decidualization are poorly understood. Fatty acids (FAs) must be esterified by fatty acyl-CoA synthetases to form biologically active acyl-CoA in order to enter the anabolic and/or catabolic pathway. Long-chain acyl-CoA synthetase 4 (ACSL4) is associated with female reproduction. However, whether it is involved in decidualization is unknown. METHODS: The expression of ACSL4 in human and mouse endometrium was detected by immunohistochemistry. ACSL4 levels were regulated by the overexpression of ACSL4 plasmid or ACSL4 siRNA, and the effects of ACSL4 on decidualization markers and morphology of endometrial stromal cells (ESCs) were clarified. A pregnant mouse model was established to determine the effect of ACSL4 on the implantation efficiency of mouse embryos. Modulation of ACSL4 detects lipid anabolism and catabolism. RESULTS: Through examining the expression level of ACSL4 in human endometrial tissues during proliferative and secretory phases, we found that ACSL4 was highly expressed during the secretory phase. Knockdown of ACSL4 suppressed decidualization and inhibited the mesenchymal-to-epithelial transition induced by MPA and db-cAMP in ESCs. Further, the knockdown of ACSL4 reduced the efficiency of embryo implantation in pregnant mice. Downregulation of ACSL4 inhibited FA ß-oxidation and lipid droplet accumulation during decidualization. Interestingly, pharmacological and genetic inhibition of lipid droplet synthesis did not affect FA ß-oxidation and decidualization, while the pharmacological and genetic inhibition of FA ß-oxidation increased lipid droplet accumulation and inhibited decidualization. In addition, inhibition of ß-oxidation was found to attenuate the promotion of decidualization by the upregulation of ACSL4. The decidualization damage caused by ACSL4 knockdown could be reversed by activating ß-oxidation. CONCLUSIONS: Our findings suggest that ACSL4 promotes endometrial decidualization by activating the ß-oxidation pathway. This study provides interesting insights into our understanding of the mechanisms regulating lipid metabolism during decidualization.

PDA-Fe3O4 decorated carbon felt anode enhancing electrochemical performance of microbial fuel cells: Effect of electrode materials on electroactive biofilm.

Anode modification is an effective strategy for enhancing the electrochemical performance of microbial fuel cell (MFC). However, the impacts of the modified materials on anode biofilm development during MFC operation have been less studied. We prepared a novel PDA-Fe3O4-CF composite anode by coating original carbon felt anode (CF) with polydopamine (PDA) and Fe3O4 nanoparticles. The composite anode material was characterized by excellent hydrophilicity and electrical conductivity, and the anodic biofilm exhibited fast start-up, higher biomass, and more uniform biofilm layer after MFC operation. The MFC reactor assembled with the composite anode achieved a maximum power density of 608 mW m-2 and an output voltage of 586 mV, which were 316.4% and 72.4% higher than the MFC with the original CF anode, respectively. Microbial community analysis indicated that the modified anode biofilm had a higher relative abundance of exoelectrogen species in comparison to the unmodified anode. The PICRUSt data revealed that the anodic materials may affect the bioelectrochemical performance of the biofilm by influencing the expression levels of key enzyme genes involved in biofilm extracellular polymer (EPS) secretion and extracellular electron transfer (EET). The growth of the anodic biofilm would exert positive or negative influences on the efficiency of electricity production and electron transfer of the MFCs at different operating stages. This work expands the knowledge of the role that anodic materials play in the development and electrochemical performance of anodic biofilm in MFCs.

The effects of the 45° semi-recumbent position on the clinical outcomes of mechanically ventilated patients: a systematic review and meta-analysis study.

BACKGROUND: A meta-analysis was conducted to investigate the effects of the 45° semi-recumbent position on the clinical outcomes of mechanically ventilated patients. METHODS: The PubMed, Embase, and Cochrane medical databases were searched using the keywords "45°", "head-of-bed elevation", and "semi-recumbent". All relevant randomized controlled trials (RCTs) published between 2005 and 2021 were obtained. The Cochrane system for randomized intervention was adopted and the RevMan 5.3.5 software was used to construct forest plots and funnel plots to assess the risk of bias for the included studies. RESULTS: A total of 128 literatures were initially screened for this meta-analysis, and 7 studies were finally included, with a total of 740 patients. Meta-analysis revealed that the incidence of ventilator-associated pneumonia (VAP) was significantly lower in patients in the 45° semi-recumbent position compared to patients in the 30° semi-recumbent position [odds ratio (OR) =0.48; 95% confidence interval (CI): 0.28 to 0.84; Z=2.59; P=0.009]. Furthermore, the incidence of gastric reflux was significantly lower in patients in the 45° semi-recumbent position compared to patients in the 30° semi-recumbent position (OR =0.50; 95% CI: 0.27 to 0.96; Z=2.09; P=0.04). Meta-analysis demonstrated that the incidence of pressure sores was significantly higher in patients in the 45° semi-recumbent position compared to patients in the 30° semi-recumbent position (OR =1.88; 95% CI: 1.05 to 3.36; Z=2.11; P=0.03). DISCUSSION: The 45° semi-recumbent position can reduce the incidence of VAP and gastric reflux in patients undergoing mechanical ventilation (MV), but it may also increase the risk of pressure sores. Thus, consideration should be made based on a comprehensive understanding of the patient's condition and physical state.

Photodegradation of Sulfamethoxypyridazine in UV/Co(II)/Peroxymonosulfate System: Kinetics, Influencing Factors, Degradation Pathways, and Toxicity Assessment.

Sulfonamides (SAs) including sulfamethoxypyridazine (SMP) are regarded as a new type of persistent pollutant at present due to their abuse. In this work, the direct photodegradation behavior of 11 SAs under simulated sunlight was first investigated, and the results indicated that the direct photolysis of SMP is the slowest among these SAs. Then the oxidation degradation of SMP in UV/Co(II)/peroxymonosulfate (PMS) system was systematically explored. Up to 95.2% removal of 0.071 mM SMP was observed after 20 min of reaction under the optimal condition with a molar ratio of 1:150:5 between SMP, PMS, and Co(II). The effects of some coexisting anions on degradation of SMP were investigated. It was found that Cl- and high concentrations of CO3 2- and HCO3 - have a significant inhibitory effect, while HPO4 2- has only a slight positive effect. Radical scavenger experiments indicated that hydroxyl radicals (HO•) are prevailing active species responsible for SMP removal in UV/Co(II)/PMS system. The degradation of SMP in UV/Co(II)/PMS system was accomplished mainly by hydroxylation of the aromatic ring, extrusion of SO2, oxidation of NH2 group, and N - S bond cleavage. Eight intermediates for SMP degradation were identified, and their toxicities to aquatic organisms were predicted by using the ECOSAR program based on the structure - activity relationships (SARs), which suggested that the chronic toxicities of SMP and its degradation intermediates are more significant than their acute toxicities. The present research indicates that UV/Co(II)/PMS system is applicable for SMP degradation in aqueous solutions and may be helpful to understand the transformation behavior of SAs. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11270-021-05351-5.

Recovery of ammonia nitrogen from landfill leachate using a biopolar membrane equipped electrodialysis system.

In this paper, a laboratory-scale electrodialysis reactor with five compartment cells separated by a bipolar membrane and ion exchange membrane was assembled to remove ammonia nitrogen from landfill leachate as a pretreatment process. The effects of humic acid, magnesium ions (Mg2+) and calcium ions (Ca2+) existing in leachate on the removal efficiency of ammonium (NH4 +) were investigated by using simulated wastewater. The results indicate that humic acid has little impact on ammonium in the presence of an electric field. High concentrations of Mg2+ and Ca2+ in solution have a substantial impact on the removal efficiency of ammonium, but the average migration rate of the three ions is NH4 + > Mg2+ > Ca2+ under the same current intensity, and NH4 + plays a major role in electromigration for mixture electrodialysis. Therefore, ammonia nitrogen can be separated from leachate and accumulated effectively. Meanwhile, the bipolar membrane near the cathode produces alkali that is released into the base cell to promote ammonia nitrogen transformation from accumulated ammonium, which creates in-site alkaline condition for ammonia nitrogen recovery by a further stripping process. When the actual leachate collected from a local municipal sanitary landfill was employed, the reactor reached 86.17% of ammonia nitrogen removal after 3.0 h reaction. Analysis of membrane scale suggests the inhibitory effect of Mg2+ on Ca2+ migration during the initial working period of the reaction can potentially slow down the membrane scaling of the cation exchange membrane. This study provides a promising technology for the removal and recovery of ammonia nitrogen from landfill leachate.

Stability of Nano-ZnO in simulated landfill leachate containing heavy metal ions.

As the presence of nanosized zinc oxide particles (nano-ZnO) in landfill leachate increases, their interaction with coexisting heavy metal ions (HMs) also increases. The interface interaction between nano-ZnO and HMs will influence nano-ZnO stability and therefore affect its bioavailability and environmental impact. In the present study, we investigated the effects of Cu(II), Cr(III), and Cr(VI) ions on the aggregation, sedimentation, and dissolution of nano-ZnO using batch experiments with a view to better understanding their co-effect on the environment. Dynamic light scattering and UV-Vis spectroscopy results show enhanced aggregation of nano-ZnO in the presence of Cr(VI) ions under fresh landfill leachate conditions, in addition to distinct sedimentation of nano-ZnO in the presence of Cr(III) ions in both fresh and aged landfill leachate. In fresh leachate, Cu(II) ions improved the concentration of dissolved Zn from nano-ZnO. However, the effects of Cu(II), Cr(III), and Cr(VI) ions on the aggregation and dissolution of nano-ZnO were markedly reduced in aged landfill leachate. Both acetic and humic acids in landfill leachate significantly affected the stability of nano-ZnO in the presence of HMs. According to the ATR-FTIR results, Cr(III) ions reacted with hydroxyl groups on nano-ZnO to form ZnO-O bonds, which induced chains of nano-ZnO and Cr(III) complexes, and hence the increased of nano-ZnO aggregates. ATR-FTIR shows merely electrostatic adsorption effects between nano-ZnO and Cu(II) or Cr(VI) ions. In brief, the mode of interactions between HMs and nano-ZnO influenced the stability via adsorption and binding effects. The results of the present research provide insight into the potential effects of nano-ZnO on the environment in the presence of HMs in landfill leachate.

Chemical fractions, diffusion flux and risk assessment of potentially toxic elements in sediments of Baiyangdian Lake, China.

The pollution of potentially toxic elements (PTEs) in Baiyangdian Lake (BYDL), the largest shallow lake in northern China, has been focused on since the construction of the Xiong'an New Area. However, research on the bioavailability and diffusive flux of PTEs in BYDL sediments has been still limited. Herein, sediment samples were collected from BYDL to systematically evaluate the pollution risk, bioavailability, and diffusion flux of PTEs using multiple methods, including the pollution indexes, risk assessment code, bioavailable metal index, the sequential extraction, and diffusive gradients in thin-films (DGT). The results showed that the average concentrations of PTEs (except for Cd) were similar to the local background. The spatial distribution of PTEs showed that their contents were higher in northern sediments than in southern sediments, and risk assessment results suggest that Cd is the priority pollutant in the BYDL. Most PTEs in the sediments were mainly present in the residue fractions; however, Cd was mainly present in the non-residue fraction. Further analysis of the Cd content and chemical fraction showed that Cd was not only abundant in the northern sediments, but also that the non-residual fraction of Cd was significantly higher than in the southern sediments. The diffusive fluxes of PTEs in the northern sediments were also investigated in comparison with their chemical fractions. Results suggest that Cd has the potential to diffuse from the sediment into the overlying water. Additionally, upon combining the DGT and chemical fractions analyses, it was found that the PTEs which mainly in non-residual fraction tend to diffuse upwards into the overlying water. But, the release tendency of PTEs does not fully depend on their non-residual content. Overall, PTEs did not significantly contaminate BYDL sediments; nevertheless, the potential ecological risk of Cd should be considered.

Structural Characterization and Digestibility of Curcumin Loaded Octenyl Succinic Nanoparticles.

Curcumin displays anti-cancer, anti-inflammatory and anti-obesity properties but its water insolubility limits the wholesome utility. In this study, curcumin has been encapsulated in an amphiphilic biopolymer to enhance its water solubility. This was accomplished through self-assembly of octenyl succinic anhydride-short glucan chains (OSA-SGC) and curcumin. The nanoparticles were prepared with the degree of substitution (DS) of 0.112, 0.286 and 0.342 of OSA. Thus prepared nanoparticles were in the range of 150-200 nm and display high encapsulation efficiency and high loading capacity of curcumin. The Fourier-transform infrared (FTIR) and X-ray diffraction analyses confirmed the curcumin loading in the OSA-SGC nanoparticles. The complexes possessed a V-type starch structure. The thermo gravimetric analysis (TGA) revealed the thermal stability of encapsulated curcumin. The OSA-SGC nanoparticles greatly improved the curcumin release and dissolution, and in-turn promoted the sustained release.

Formation of hydroxylated derivatives and coupling products from the photochemical transformation of polyfluorinated dibenzo-p-dioxins (PFDDs) on silica surfaces.

Polyfluorinated dibenzo-p-dioxins (PFDDs) are dioxin compounds that have been detected in industrial fluoroaromatic chemicals and can cause adverse effects to organisms. In this work, the photochemical behaviors of PFDDs congeners on silica was systematically investigated. The pseudo-first-order rate constants (k, h-1) of surface photolysis changed with the substitution number and position of fluorine atoms, and the tetra-fluorinated PFDDs tended to degrade more efficiently. Octafluorinated dibenzo-p-dioxin (OFDD) was selected as a representative to explore the reaction mechanisms. Product analysis showed that OFDD was decomposed into hydroxylated PFDDs (OH-PFDDs) and hydroxylated polyfluorinated diphenyl ethers (OH-PFDEs) via hydroxyl substitution and (OH radical mediated or direct) C-O bond cleavage. Coupling elimination reaction was also observed, resulting in the formation of three-membered and four-membered ring compounds. According to the extracted peak areas in mass spectra and the energy barrier in potential energy surface, direct homolysis of C-O bond occurs as the dominant reaction pathway. This work could provide some new insights into the environmental fate of dioxin compounds.

Improvement in Nutritional Attributes of Rice Starch with Dodecyl Gallate Complexation: A Molecular Dynamic Simulation and in Vitro Study.

To improve starch functionalities such as digestibility and antioxidant activity, rice starch was complexed with antioxidant dodecyl gallate (DG). Molecular dynamics simulation showed that the starch-DG inclusion complex was favorable, and in 50 ns, the dodecyl segment resided in the helix of the amylose cavities but the gallate tail left outside. This theoretical finding was validated by UV-vis spectroscopy, calorimetric, and crystalline measurements, indicating V-type crystalline structures containing type I and type II inclusion complexes can be formed after DG complexation. Meritedly, starch digestibility was mitigated by synchronously increasing slowly digestible starch (5.12-22.83%) and resistant starch content (8.69-14.17%), and the antioxidant activity was also significantly increased. Such inclusion complexes thereby acted as a carrier for targeting delivery of DG to the human lower gastrointestinal tract with potent antioxidant activity. Complexation with DG synergistically improved starch digestibility and antioxidant activity, favoring the intervention against chronic diseases, by ameliorating the postprandial glycemic response and oxidative stress.

Computational investigation of the atmospheric oxidation reactions of polybrominated dibenzo-p-dioxins initiated by OH radicals.

Density functional theory (DFT) method was used to study OH-initiated atmospheric oxidative reactions of some polybrominated dibenzo-p-dioxins (PBDDs). B3LYP functional and 6-311++G (2df,p) basis set were applied to optimize molecular structures of all stationary points involved in the investigated reactions. The rate constants for key elementary reactions were estimated by means of transition state theory. The computational results demonstrate that all addition reactions of PBDDs with OH radicals can occur spontaneously at standard conditions, however, the OH addition reactions are very slow due to low atmospheric concentration of OH radicals. Addition reactions occurring at γ-C position dominate in OH addition of all PBDDs. With the number of bromine atoms substituting at α-sites increases, the overall rate coefficients of OH addition decrease. The succeeding addition reactions of PBDD-OH adducts with O2 take place hardly both thermodynamically and kinetically. Abstraction reaction of H atoms by O2 is a governing route for PBDD-α(ß)-adducts without bromine atoms at the same site, while the fused-ring CO bond fission is a main reaction channel for PBDD-γ-adducts, which will produce substituted phenoxy radicals.

Ferrate(VI) oxidation of polychlorinated diphenyl sulfides: Kinetics, degradation, and oxidized products.

This paper presents oxidation of polychlorinated diphenyl sulfides (PCDPSs), dioxin-like compounds, by ferrate(VI) (FeVIO42-, Fe(VI)). Kinetics of the reactions of Fe(VI) with seventeen PCDPSs, differ in number and positions of chlorine atoms (from 2 to 7), were investigated at pH 8.0. The second-order rate constants (k, M-1 s-1) of the reactions varied with the numbers and positions of chlorine atoms and appeared to be related with standard Gibbs free energy of formation (ΔfG0) of PCDPSs. Degradation experiments in the presence of ions and humic acid demonstrated complete removal of PeCDPS by Fe(VI) in minutes. Pathways of the reaction were investigated by identifying oxidized products (OPs) of the reaction between Fe(VI) and 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) at pH 8.0. Pathways of oxidation involved major pathway of attack on sulfur(II) by Fe(VI) in steps to yield sulfoxide type products, and subsequent breakage of C-S bond with the formation of sulfonic acid-containing trichloro compound. Minor pathways were hydroxylation of benzene ring and substitution of chlorine atom with hydroxyl group. Estimation of toxicity of OPs of the oxidation of PeCDPS by Fe(VI) suggested the decreased toxicity from the parent contaminant.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel.

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.

An experimental and theoretical study of the adsorption removal of toluene and chlorobenzene on coconut shell derived carbon.

The adsorption performance of toluene and chlorobenzene on prepared coconut shell derived carbon (CDC) is investigated and compared with commercial activated carbon (CAC) by experiment and theory calculation. Textural properties of prepared adsorbents are characterized by N2 adsorption, infrared spectra (FT-IR), Raman spectra and X-ray photoelectron spectra (XPS). Adsorption isotherms of toluene and chlorobenzene are obtained and fitted using structure optimizations, Grand Canonical Monte Carlo (GCMC) simulation and thermodynamic models. The results indicate that CDC shows better volatile organic compounds (VOCs) removal performance than CAC, and chlorobenzene is easily adsorbed than toluene. On the aspect of textural characteristics, CDC possesses more micropores ratio and narrower pore size distribution than CAC. Furthermore, amounts of electron-withdrawing carbonyl groups on the CAC surface reduce the electron density of adsorbents, thus weakening the interaction between VOCs and adsorbents. On the aspect of model fitting, the Yoon and Nelson (Y-N) and Dubinin-Astakhov (D-A) models can well describe the dynamic adsorption and the adsorption equilibrium of toluene and chlorobenzene on CDC respectively. It is believed that substituent groups of adsorbates, making the charge distribution deviate, lead to adsorption potentials of chlorobenzene larger than toluene. In general, both the pore structure and the surface property of adsorbents affect the VOCs adsorption behaviors on CDC.

Surfactant-enhanced PEG-4000-NZVI for remediating trichloroethylene-contaminated soil.

In this study a NZVI was prepared by the liquid phase reduction method. The modified NZVI obtained was characterized by BET, TEM and XRD. The results showed that the iron in the PEG-4000 modified material is mainly zero-valent iron with a stable crystal structure. It has a uniform particle size, ranging from 20 to 80 nm, and a larger specific surface area than CTAB modified NZVI, SDS modified NZVI and commercial zero-valent iron. The two surfactants CTAB and SDS are also selected as solubilizers, the results showed that the two selected surfactants obviously solubilize trichloroethylene in soil. Compared with commercial zero-valent iron, PEG-4000 modified NZVI is better removed trichloroethylene from soil; Also, the optimal operational parameters were obtained. When the experimental conditions were: PEG-4000 modified NZVI dosage 1.0 g/L, CTAB/SDS concentration equal to the CMC, SDS concentration was 2.0 × CMC, CTAB was concentration 1.0 × CMC and the vibration speed 150 r/min, the removal efficiency of trichloroethylene in a soil-water system reached 100% after 4 h. Both NZVI combined with CTAB and NZVI combined with SDS followed fitted first order reaction kinetics during the removal of trichloroethylene and their reaction rate constant k was 0.6869 mg/(L·h) and 0.5659 mg/(L·h), respectively. According to the chloride ion detection test, the trichloroethylene degradation is mainly due to reductive dechlorination.

Solid surface-mediated photochemical transformation of decabromodiphenyl ether (BDE-209) in aqueous solution.

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants which have received considerable attention due to their global distribution, bioaccumulation potential, environmental persistence, and possible toxic effects. In this work, the photodegradation of decabromodiphenyl ether (BDE-209) in aqueous system was investigated by preloading it on the surface of various solid matrices. After 6 h of Xe lamp irradiation, almost complete degradation of BDE-209 was observed on silica gel (SG), with much slower degradation occurring in other adsorbents. The degradation of BDE-209 on SG sample followed pseudo-first-order kinetics, and the observed reaction rate constant was decreased by lowering pH, adding humic acid and increasing the initial BDE-209 concentration. In addition to direct photolysis, BDE-209 could be oxidized by hydroxyl radicals generated from SG, as confirmed by the electron paramagnetic resonance (EPR) technology. Product analysis showed that BDE-209 was mainly decomposed into lower brominated PBDEs, polybrominated dibenzofurans (PBDFs), hydroxylated PBDEs (OH-PBDEs), hydroxylated PBDFs (OH-PBDFs), bromophenols and bromide ions. Thus, consecutive debromination, intramolecular elimination of HBr, hydroxyl addition and the cleavage of ether bond were proposed as the degradation pathways. This study may help understanding the photochemical transformation of solid surface adsorbed BDE-209 in natural surface waters, which is important to evaluate the environmental fate of PBDEs.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C1∼4 and CA sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C1∼4 positions are kinetically comparable with those occurring at nonfluorinated C1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C1 position has more adverse effects than substitution at other sites. The succedent O2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (ΔrG≠). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols.

Catalytic Oxidation of NO over MnOx-CeO2 and MnOx-TiO2 Catalysts.

A series of MnOx-CeO2 and MnOx-TiO2 catalysts were prepared by a homogeneous precipitation method and their catalytic activities for the NO oxidation in the absence or presence of SO2 were evaluated. Results show that the optimal molar ratio of Mn/Ce and Mn/Ti are 0.7 and 0.5, respectively. The MnOx-CeO2 catalyst exhibits higher catalytic activity and better resistance to SO2 poisoning than the MnOx-TiO2 catalyst. On the basis of Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), and scanning transmission electron microscope with mapping (STEM-mapping) analyses, it is seen that the MnOx-CeO2 catalyst possesses higher BET surface area and better dispersion of MnOx over the catalyst than MnOx-TiO2 catalyst. X-ray photoelectron spectroscopy (XPS) measurements reveal that MnOx-CeO2 catalyst provides the abundance of Mn3+ and more surface adsorbed oxygen, and SO2 might be preferentially adsorbed to the surface of CeO2 to form sulfate species, which provides a protection of MnOx active sites from being poisoned. In contrast, MnOx active sites over the MnOx-TiO2 catalyst are easily and quickly sulfated, leading to rapid deactivation of the catalyst for NO oxidation. Furthermore, temperature programmed desorption with NO and O2 (NO + O2-TPD) and in situ diffuse reflectance infrared transform spectroscopy (in situ DRIFTS) characterizations results show that the MnOx-CeO2 catalyst displays much stronger ability to adsorb NOx than the MnOx-TiO2 catalyst, especially after SO2 poisoning.

Photodegradation of Polyfluorinated Dibenzo-p-Dioxins in Organic Solvents: Experimental and Theoretical Studies.

Eighteen polyfluorinated dibenzo-p-dioxins (PFDDs) were synthesized by pyrolysis of fluorophenols. Using a 500 W Xe lamp as the light source, the PFDDs photodegradation kinetics in n-hexane were investigated. The photolysis reactions obeyed the pseudo-first-order rate equation, and higher fluorinated PFDDs tended to photolyze more slowly. Theoretically calculated parameters reflecting the molecular structural properties were used to develop a new model of PFDDs photolysis rates. The results indicated that the substitution pattern for fluorine atoms and the C-O bond length were major factors in the photolysis of PFDDs. We selected octafluorinated dibenzo-p-dioxin (OFDD) as a representative PFDDs to explore the influence of solvent on the photolysis rate of PFDDs, and the results indicated that neither the polarity nor donor hydrogen of organic solvents are independent influencing factors. Mechanistic pathways for the photolysis of OFDD in n-hexane were first studied. The results indicated that photodegradation of OFDD produces octafluorinated dihydroxybiphenyls, octafluorinated phenoxyphenols, and fluorinated phenols. The major pathway for photodegradation of OFDD was C-O bond cleavage. Defluorination reactions did not occur during the photolysis process.

Influence of activated-carbon-supported transition metals on the decomposition of polychlorobiphenyls. Part II: Chemical and physical characterization and mechanistic study.

This paper studies the synergism between transition metals (TMs) and activated carbon (AC) as a catalyst support used in the catalytic decomposition of PCBs. A series of AC-supported TM catalysts was prepared according to two distinct methods: impregnation and ion exchange which were defined as LaTM-C and IRTM-C, respectively. The catalytic reactions between 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153) and AC-supported Fe, Ni, Cu and Zn catalysts were conducted under N2 atmosphere. Changes in the nature of the catalysts as well as the decomposition mechanism of PCB-153 are discussed. Important findings include: (i) a higher metal concentration and a better metal distribution on AC is realized using ion-exchange, despite a lower AC specific surface area, (ii) IRTM-C had better effects on the decomposition of PCB-153 than LaTM-C, (iii) the role of Ni, Cu, and Fe as electron donors in PCB dechlorination was evaluated vs. the stability of Zn, and (iv) both temperature and chemical composition of TM catalysts influenced the decomposition efficiency of PCBs.