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Sulfide-modified microscale zero-valent iron (S-mFe0) was applied to activate peroxymonosulfate (PMS) to degrade sulfamethoxazole (SMX), a typical sulfonamide bacteriostatic antibiotic. In this work, the effects of S/Fe molar ratio, S-mFe0 dosage, PMS dosage, different initial pH value, dissolved oxygen, SMX concentration and inorganic ions on SMX removal by S-mFe0/PMS system were investigated, respectively. Besides, the role of sulfur species (including the FeS, SO32?, S2?) was studied. In contrast to mFe0/PMS system, the removal efficiency of SMX obtained by S-mFe0 /PMS system was increased by 29.4%. Radical quenching and Electron Paramagnetic Resonance spectroscope (EPR) tests identified that both [rad]OH and SO4[rad]? were committed to degrading SMX, and SO4[rad]? was proven to be the dominant one. The electrochemical analysis of S-mFe0 and bare mFe0, implying a better electron transfer ability of S-mFe0 due to the formation of FeS. Furthermore, the activation of S2? for PMS could be ruled out by EPR tests results. Conversely, SO32? could effectively activate PMS to generate reactive oxygen species (ROS). The catalytic mechanisms of S-mFe0/PMS system were clarified by SEM-EDS, XRD, XPS, radical quenching and EPR tests. Based on the detected intermediates via LC-TOF-MS/MS, the degradation pathways of SMX by S-mFe0/PMS system were proposed. Overall, the work suggests that S-mFe0/PMS system has a good potential for the elimination of micropollutants in the aquatic environment.

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4-Hydroxy-N-<5-(hydroxymethyl)-3-isoxazolyl>-2-methyl-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide (2), the major oxidative human metabolite of isoxicam (1), and <(5-methyl-3-isoxazolyl)amino>oxoacetic acid (3), the major rat metabolite of isoxicam (1), were synthesized. 2 was synthesized by condensation of the known benzothiazine ester 8 with the isoxazolamine 9b. 9b was synthesized via a nine-step sequence starting with 5-methyl-3-isoxazolecarboxylic acid (14).NBS bromination of 14 gave 5-(bromomethyl)-3-isoxazolecarboxylic acid, which was coverted to the carbamate ester via a Curtius rearrangement of the acid azide.Displacement of bromine with silver acetate gave the acetoxy compound 21.Hydrolysis of 21 gave the unstable 3-isoxazolamine derivative 9a, which was converted to the OSiMe3 derivative 9b.The compound 3 was synthesized by reaction of ethyl oxalyl chloride with 5-methyl-3-isoxazolamine followed by base hydrolysis.

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In this study, fabrication of manganese-incorporated iron oxide-graphene nanocomposite (rGO-FMBO) was reported for the efficient activation of CaO2 and generation of reactive radicals for the degradation of sulfamethoxazole (SMX). The effects of different systems, catalyst dosage, oxidant dosage, different pH and different reaction time on the degradation of SMX by rGO-APTMS-FMBO/CaO2 as well as the production of free radicals were also studied. Electron paramagnetic resonance (EPR) technique was used to detect and identify the radical species in this oxidation system and these radicals were further confirmed by scavenging studies with the addition of isopropanol (IPA) and methyl viologen (MV2+). The results indicated that the CaO2 could be activated by rGO-APTMS-FMBO efficiently for the effective degradation of SMX at neutral pH (P ? 0.01). The mechanism of the activation of CaO2 by rGO-APTMS-FMBO was that carbon dioxide radicals (CO2[rad]?) generated by rGO-APTMS-FMBO could activate the CaO2 to produce more hydroxyl radicals (HO[rad]), which favored the SMX degradation. EPR studies showed that three types of free radicals HO[rad], CO2[rad]?, and CH3[rad] were generated and the radical intensities were much higher in rGO-APTMS-FMBO/CaO2 system. Both increased pH and reaction time led to the production of more CO2[rad]?, which activated the CaO2 to give more HO[rad] to degrade SMX. Transformation products/intermediates of SMX were determined and potential mechanism and degradation pathway were proposed. The findings of this study provide new insights into the mechanism of heterogeneous catalysis based on CaO2 activated by rGO-APTMS-FMBO and the reactivity of this oxidation system toward environmental contaminants.

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Due to the increase of emerging contaminants in water, how to use new treatment technology to make up for the defects of traditional wastewater treatment method has become one of the research hotspots at present. Intimate coupling of photocatalysis and biodegradation (ICPB) as a novel wastewater treatment method, which combines the advantages of biological treatment and photocatalytic reactions, has shown a great potential as a low-cost, environmental friendly and sustainable treatment technology. The system mainly consists of photocatalytic materials, porous carriers and biofilm. The key principle of ICPB is to transform bio-recalcitrant pollutants into biodegradable products by photocatalysis on the surface of porous carriers. The biodegradable products were mineralized simultaneously through the biofilm inside the carriers. Because of the protection of the carriers, the microorganism can remain active even under the UV-light, the mechanical force of water flow or the attack of free radicals. ICPB breaks the traditional concept that photocatalytic reaction and biodegradation must be separated in different reactors, improves the purification capacity of sewage and saves the cost. This review summarizes the recent advances of ICPB photocatalysts, carriers and biofilm being applied, and focuses on the mechanisms and reactor configurations which is particularly novel. Furthermore, the possible ongoing researches on ICPB are also put forward. This review will provide a valuable insight into the design and application of ICPB in environment and energy field.

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Degradation of sulfapyridine as a representative sulfonamide by the UV/chlorine process was investigated. Kinetic experiments revealed that aniline and sulfonamide moieties were sulfapyridine’s main reaction sites with ?OH, and the aniline moiety was the preferable site for Cl? attack. Effects of four influence factors (pH; humic acid, HA; HCO3 – Cl-) on the degradation kinetics were explored by response surface methodology, and it was found that pH and HA have the highest level influence (81%) among all influence variables (linear, quadratic, and interactive terms), and low pH and concentrations of HA were beneficial for degradation. Approximately 70% of sulfapyridine degradation was observed within 60 min in the UV/chlorine system (pH = 5) without HA. A kinetic model considering steady-state concentrations of reactive radicals and their second-order rate constants is suitable for predicting sulfapyridine degradation, elucidating that ?OH and Cl? are major radicals for sulfapyridine degradation in freshwater, and ?OH and Cl2? are responsible for the degradation in coastal seawater.

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A new series of alpha-aminophosphonates have been synthesized by a one-pot three-component reaction of 2,3-dihydrobenzo[b][1,4]dioxine-6- carbaldehyde, various amines, and dimethyl phosphite by using nano-TiO 2 as a catalyst under solvent-free conditions at 50C. The major advantages of the present method are high yields, short reaction times, recyclable catalyst, and solvent-free reaction conditions. Among these new structurally diversified set of alpha-aminophosphonates, dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(3-nitrophenylamino) methylphosphonate and dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(4-fluoro-3-nitro-phenyl-amino) methylphosphonate have shown higher antioxidant activity in diphenyl picryl hydrazyl (DPPH) scavenging, reducing power assay, and lipid peroxidation methods.

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The contents of issues 3 and 4 of Structural Chemistry from the calendar year 2017 are summarized in the present review. A brief thermochemical commentary and recommendations for future research have been added to the summary of each paper.

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Constructed wetlands (CWs) could achieve high removal efficiency of antibiotics, but probably stimulate the spread of antibiotic resistance genes (ARGs). In this study, four CWs were established to treat synthetic wastewater containing sulfamethoxazole (SMX). SMX elimination efficiencies, SMX degradation mechanisms, dynamic fates of ARGs, and bacterial communities were evaluated during the treatment period (360 day). Throughout the whole study, the concentration of SMX in the effluent gradually increased (p < 0.05), but in general, the removal efficiency of SMX remained at a very high level (>98%). In addition, the concentration of SMX in the bottom layer was higher compared with that in the surface layer. The main byproducts of SMX degradation were found to be 4-amino benzene sulfinic acid, 3-amino-5-methylisoxazole, benzenethiol, and 3-hydroxybutan-1-aminium. Temporally speaking, an obvious increase of sul genes was observed, along with the increase of SMX concentration in the bottom and middle layers of CWs. Spatially speaking, the concentration of sul genes increased from the surface layer to the bottom layer.

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In this study, nitrogen, sulfur and oxygen co-doped carbon armored cobalt sulfide (Co/Co9S8@N-S-O-C) composite was synthesized, characterized and used to activate peroxymonosulfate (PMS) for the degradation of sulfamethoxazole (SMX). SMX (0.04 mM) can be completely degraded within 20 min in the presence of 0.8 mM PMS and 0.1 g/L Co/Co9S8@N-S-O-C composite. The first-order kinetics constant of SMX degradation was 0.307 min-1, and the mineralization of SMX was 30.1 %. The Quenching experiments of the free radicals and the identification of degradation products demonstrated that sulfate radicals played a dominant role in SMX degradation. The degradation rate of SMX increased with temperature, and activation energy was calculated to be 48.6 kJ/mol. The degradation rate of SMX increased firstly then decreased with increase of pH. Chloridion and humic acid decreased the degradation rate of SMX no matter what their initial concentration was. The effect of carbonate on SMX degradation depended on its initial concentration. Co/Co9S8@N-S-O-C composite showed good stability, the removal efficiency of SMX was 98.4 % in the fifth experiment. Based on the characterization results of the catalyst before and after use, it was concluded that cobalt, sulfur, pyridnic N and graphitic N were responsible for PMS activation.

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The key intermediates, 3-(5-methyl-3-isoxazolyl)-2-arylimino-1,3-thiazolan- 4-ones (3), were obtained from 3-amino-5-methylisoxazole (1) by reaction with chloroacetyl chloride followed by treatment with aryl isothiocyanates. Cyclocondensation of 3 with mercapto acetic acid furnished novel isoxazolyl 1,6-dithia-4,9-diazaspiro[4,4]nonane-3,8-diones (4). Cycloaddition of 3 with benzonitrile oxides afforded novel isoxazolyl 1-oxa-6-thia-2,4,9-triazaspiro[4, 4]non-2-ene-8-ones (5).

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