Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number ...Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promis展开更多
Deuterated compounds are valuable in synthetic,pharmaceutical,and analytical chemistry.The deuteration of halides is a widespread method for highly site-selective deuterium installation.However,the facile,efficient,an...Deuterated compounds are valuable in synthetic,pharmaceutical,and analytical chemistry.The deuteration of halides is a widespread method for highly site-selective deuterium installation.However,the facile,efficient,and economical deuterium incorporation remains challenging.In this work,we introduced a practical deuteration of(hetero)aryl halides through an electrochemical reduction method.This transformation proceeded smoothly at room temperature without metal catalysts,external reductants,or toxic or dangerous reagents.Remarkably,low-cost and chemically equivalent D2O was the sole deuterium source in this reaction.Professional electrosynthesis equipment was not essential because we demonstrated common batteries and electrodes were enough for this reaction.展开更多
A novel bisupporter bimetal catalyst PVP-PdCl2-SnCl4/MontK10-PEG400, using for dehalogenation of insoluable aromatic halides in aqueous system, has shown high dechlorination activity and selectivity, without any organ...A novel bisupporter bimetal catalyst PVP-PdCl2-SnCl4/MontK10-PEG400, using for dehalogenation of insoluable aromatic halides in aqueous system, has shown high dechlorination activity and selectivity, without any organic solvent or phase transfer catalyst. The conversion of aromatic chlorides can reach 100%. The catalyst is easy to prepare and has good reusability.展开更多
We herein report a simultaneous dehalogenation and hydrogenation(DHH)reaction in Sonogashira coupling involving hexahalogenobenzene C6X6(X=I,Br),in which a halogen on the aryl polyhalide substrate was substituted by a...We herein report a simultaneous dehalogenation and hydrogenation(DHH)reaction in Sonogashira coupling involving hexahalogenobenzene C6X6(X=I,Br),in which a halogen on the aryl polyhalide substrate was substituted by a hydrogen atom.First,a steric bulky terminal alkyne 5 was designed and synthesized to study the influence of the reaction conditions(e.g.,catalyst,solvent,temperature)and the halogens on the substrates C6X6 on the DHH reaction.Moreover,based on the optimized conditions,a terminal alkyne 6 with less steric hindrance was further synthesized to investigate the influence of alkyne on the DHH reaction.As a result,two aromatic polyynes 7 and 8 were were further studied and compared.The influence produced by the alkynes and aryl polyhalides substrate provide insights into Sonogashira coupling involving terminal alkyne with huge steric hindrance and polyhalogenated aromatic hydrocarbons.展开更多
A series of PVP-Pd-Sn/MontK10 catalysts were prepared by immobilization of PVP[poly(N-vinyl-2-pyrrolidone)] supported bimetallic catalyst using MontK10 as carrier. This catalyst has good catalytic activity for hydroge...A series of PVP-Pd-Sn/MontK10 catalysts were prepared by immobilization of PVP[poly(N-vinyl-2-pyrrolidone)] supported bimetallic catalyst using MontK10 as carrier. This catalyst has good catalytic activity for hydrogen transfer dehalogenation of aryl halides. The catalytic reaction was carried out in aqueous system in the presence of phase transfer catalyst and sodium formate as hydrogen source. The catalyst with loading Pd 0.19wt% and molar ratio of Pd/Dn 8:1 gives the highest activity and good stability. This catalyst is more reducible with NaBH4. It is also found that the catalyst is easily separated from the reaction system.展开更多
In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media....In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.展开更多
基金financially supported by the National Natural Science Foundation of China(22176059,21777042,and 22076045)the authors would also like to acknowledge support from the Science and Technology Commission of Shanghai Municipality’s Yangfan Special Project(23YF1408400)the Fundamental Research Funds for the Central Universities.
文摘Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promis
基金supported by the National Natural Science Foundation of China(no.21520102003)the Hubei Province Natural Science Foundation of China(no.2017CFA010)The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated.
文摘Deuterated compounds are valuable in synthetic,pharmaceutical,and analytical chemistry.The deuteration of halides is a widespread method for highly site-selective deuterium installation.However,the facile,efficient,and economical deuterium incorporation remains challenging.In this work,we introduced a practical deuteration of(hetero)aryl halides through an electrochemical reduction method.This transformation proceeded smoothly at room temperature without metal catalysts,external reductants,or toxic or dangerous reagents.Remarkably,low-cost and chemically equivalent D2O was the sole deuterium source in this reaction.Professional electrosynthesis equipment was not essential because we demonstrated common batteries and electrodes were enough for this reaction.
文摘A novel bisupporter bimetal catalyst PVP-PdCl2-SnCl4/MontK10-PEG400, using for dehalogenation of insoluable aromatic halides in aqueous system, has shown high dechlorination activity and selectivity, without any organic solvent or phase transfer catalyst. The conversion of aromatic chlorides can reach 100%. The catalyst is easy to prepare and has good reusability.
基金supported by the National Natural Science Foundation of China(Grant no.21801031)the Natural Science Foundation Project of Chongqing,Chongqing Science and Technology Commission,China(Grant nos.2023NSCQ-MSX3187 and cstc2019jcyjmsxmX0404)+1 种基金the Scientific and Technological Research Program of Chongqing Municipal Education Commission(Grant no.KJQN202301524)the Foundation of Chongqing University of Science&Technology(Grant no.ckrc202212053).
文摘We herein report a simultaneous dehalogenation and hydrogenation(DHH)reaction in Sonogashira coupling involving hexahalogenobenzene C6X6(X=I,Br),in which a halogen on the aryl polyhalide substrate was substituted by a hydrogen atom.First,a steric bulky terminal alkyne 5 was designed and synthesized to study the influence of the reaction conditions(e.g.,catalyst,solvent,temperature)and the halogens on the substrates C6X6 on the DHH reaction.Moreover,based on the optimized conditions,a terminal alkyne 6 with less steric hindrance was further synthesized to investigate the influence of alkyne on the DHH reaction.As a result,two aromatic polyynes 7 and 8 were were further studied and compared.The influence produced by the alkynes and aryl polyhalides substrate provide insights into Sonogashira coupling involving terminal alkyne with huge steric hindrance and polyhalogenated aromatic hydrocarbons.
文摘A series of PVP-Pd-Sn/MontK10 catalysts were prepared by immobilization of PVP[poly(N-vinyl-2-pyrrolidone)] supported bimetallic catalyst using MontK10 as carrier. This catalyst has good catalytic activity for hydrogen transfer dehalogenation of aryl halides. The catalytic reaction was carried out in aqueous system in the presence of phase transfer catalyst and sodium formate as hydrogen source. The catalyst with loading Pd 0.19wt% and molar ratio of Pd/Dn 8:1 gives the highest activity and good stability. This catalyst is more reducible with NaBH4. It is also found that the catalyst is easily separated from the reaction system.
基金the Guangdong Natural Science Foundation(No.8151063201000016)the National Natural Science Foundation of China(No.20672046) for financial support
文摘In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.
