The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in ...The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.展开更多
The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of ap...The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...展开更多
High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） a...High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） and diethyl ether （EE） （by volume 1：1） ＋ 0,05 mol L^-1 Bu4NBF4. The film formed can be peeled off the electrode into freestanding films, The addition of EE into BFEE can improve the solubility of monomer. P5CI films obtained from this medium showed excellent electrochemical behavior with conductivity of 10^-2 S cm^-1, Structural studies showed that the polymerization of 5-cyanoindole occurred at the 2,3 position. As-formed P5CI films were thoroughly soluble in strong polar organic solvent dimethyl sulfoxide （DMSO） while partly soluble in tetrahydrofuran （THF） or acetone. Fluorescence spectral studies indicated that P5CI was a good blue-ight emitter.展开更多
?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were c...?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were converted to lactones smoothly．展开更多
Regioselective addition reactions of silyl enolates to a, b-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This ...Regioselective addition reactions of silyl enolates to a, b-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg+.展开更多
Direct aldol condensation of various aromatic, heteroaromatic, α,β-unsaturated aldehydes and aliphatic aldehydes with acyldiazomethane was realized using Mgl2 etherate （Mgl2.（Et2O）n） as a promoter in the presenc...Direct aldol condensation of various aromatic, heteroaromatic, α,β-unsaturated aldehydes and aliphatic aldehydes with acyldiazomethane was realized using Mgl2 etherate （Mgl2.（Et2O）n） as a promoter in the presence of diisopropyl amine （DIPEA） in excellent yields in a short time under mild conditions with high chemoselectivity. Iodide counterion, and a non-coordinating less ploar reaction media （i.e., CH2C12） are among the critical factors for this unique reactivity.展开更多
Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and ...Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallowsurface soils,increasing evidence shows that these compounds can leach into the groundwater.Herein,we compare the leachabilities of PBDEs vs.PAHs from contaminated soils collected at an e-waste recycling site in Tianjin,China.Considerable amounts of BDE-209(0.3–2 ng/L)and phenanthrene(42–106 ng/L),the most abundant PBDE and PAH at the site,are detected in the effluents of columns packed with contaminated soils,with the specific concentrations varying with hydrodynamic and solution chemistry conditions.Interestingly,the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles,whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent,but showing essentially no correlation with the concentration of mineral particles.The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive,as PBDEs and PAHs often co-exist at e-waste recycling sites(particularly at the sites wherein incineration is being practiced)and share many similarities in terms of physicochemical properties.One possible explanation is that due to its extremely low solubility,BDE-209 predominantly exists in free-phase(i.e.,as solid(nano)particles),whereas the more soluble phenanthrene is mainly sorbed to soil organic matter.Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.展开更多
Polybromodiphenyl ethers(PBDEs),the widely used flame retardants,are common contaminants in surface soils at e-waste recycling sites.The association of PBDEs with soil colloids has been observed,indicating the potenti...Polybromodiphenyl ethers(PBDEs),the widely used flame retardants,are common contaminants in surface soils at e-waste recycling sites.The association of PBDEs with soil colloids has been observed,indicating the potential risk to groundwater due to colloid-facilitated transport.However,the extent to which soil colloidsmay enhance the spreading of PBDEs in groundwater is largely unknown.Herein,we report the co-transport of decabromodiphenyl ester(BDE-209)and soil colloids in saturated porous media.The colloids released froma soil sample collected at an e-waste recycling site in Tianjin,China,contain high concentration of PBDEs,with BDE-209 being the most abundant conger(320±30 mg/kg).The colloids exhibit relatively high mobility in saturated sand columns,under conditions commonly observed in groundwater environments.Notably,under all the tested conditions(i.e.,varying flow velocity,pH,ionic species and ionic strength),the mass of eluted BDE-209 correlates linearly with that of eluted soil colloids,even though the mobility of the colloids varies markedly depending on the specific hydrodynamic and solution chemistry conditions involved.Additionally,the mass of BDE-209 retained in the columns also correlates strongly with themass of retained colloids.Apparently,the PBDEs remain bound to soil colloids during transport in porous media.Findings in this study indicate that soil colloidsmay significantly promote the transport of PBDEs in groundwater by serving as an effective carrier.This might be the reason why the highly insoluble and adsorptive PBDEs are found in groundwater at some PBDE-contaminated sites.展开更多
A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones w...A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones with cyclic quaternary centers in moderate to good yields and>19∶1 dr.This catalysis enables the direct construction of two types of carboncyclic skeletons by adjusting the olefin types of 1,3-enyne acetates.When 1,3-enyne acetates bearing a cyclic alkene unit were used,5~6 fused bicarbocyclic products were diastereoselectively synthesized,whereas the reaction of acyclic 1,3-enyne acetates resulted in five-memebered carbocyclic framework.Notably,cyclic ether acetals are commonly used as protecting groups in traditional multistep organic syntheses,and in this reaction,such reagents serve as electrophilic cyclic ether precursors,achieving new uses for old reagents.The current method demonstrates good functional group compatibility,a broad substrate scope and high diastereoselectivity,providing a new synthetic strategy toward functionalized cyclopentenones.展开更多
The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Trehalase hydrolyzes trehalose to glucose to provide energy for insects or building blocks for chitin synthesis.Because trehalase is critical to insects but not to humans,it has long been considered a promising target...Trehalase hydrolyzes trehalose to glucose to provide energy for insects or building blocks for chitin synthesis.Because trehalase is critical to insects but not to humans,it has long been considered a promising target for green insecticides.However,the known trehalase inhibitors are mainly sugar derivatives with poor druggability.In this study,the trehalase from Ostrinia furnacalis(OfTreh)was expressed and characterized.By integrative computational strategies,diphenyl ether herbicides were discovered as the first non-carbohydrate inhibitors of insect trehalases.Bifenox and its more stable derivative,chlomethoxyfen,inhibited Of Treh with Ki values of 56 and 43μM,respectively.The oral administration of bifenox or chlomethoxyfen to locusts resulted in the inhibition of trehalose hydrolysis in vivo,leading to a mortality rate of 66%and server locomotion disorder in the survivors.This study not only established a platform for the development of insecticides targeting trehalase but also discovered a new mechanism for diphenyl ethers to kill insects as trehalase inhibitors.展开更多
The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of ...The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of dimethyl ether(DME),which is derived from fossil resources,represents a promising approach to producing high-concentration formaldehyde with low energy consumption.However,there is still a lack of catalysts achieving satisfactory conversion of DME with high selectivity for formaldehyde under mild conditions.In this work,an efficient iron-molybdate(FeMo)catalyst was developed for the selective oxidation of DME to formaldehyde.The DME conversion of 84% was achieved with a superior formaldehyde selectivity(77%)at 300℃,a performance that is superior to all previously reported results.In an approximately 550 h continuous reaction,the catalyst maintained a conversion of 64% and a formaldehyde selectivity of 79%.Combined X-ray diffraction(XRD),Transmission electron microscope(TEM),Ultraviolet-visible spectroscopy(UV-Vis),Hydrogen temperature-programmed reduction(H_(2)-TPR),Fourier transform infrared(FT-IR)analyses,along with density functional theory(DFT)calculations,demonstrated that the excellent FeMo catalyst was composed of active Fe_(2)(MoO_(4))_(3)and MoO_(3)phases,and there was an interaction between them,which contributed to the efficient DME dissociation and smooth hydrogen spillover,leading to a superior DME conversion.With the support of DME/O_(2)pulse experiments,in-situ Raman,in-situ Dimethyl ether infrared spectroscopy(DME-IR)and DFT calculation results,a Mars-van Krevelen(MvK)reaction mechanism was proposed:DME was dissociated on the interface between Fe_(2)(MoO_(4))_(3)and MoO_(3)phases to form active methoxy species firstly,and it dehydrogenated to give hydrogen species;the generated hydrogen species smoothly spilled over from Fe_(2)(MoO_(4))_(3)to MoO_(3)enhanced by the interaction between Fe_(2)(MoO_(4))_(3)and MoO_(3);then the hydrogen species was consumed by MoO_(3),leading to a reduction of MoO_(3),and finally,the reduced MoO_(3)was re-oxidized by O_(2),returning to the initial state.These findings offer valuable insights not only for the development of efficient FeMo catalysts but also for elucidating the reaction mechanism involved in the oxidation of DME to formaldehyde,contributing to the optimized utilization of DME derived from fossil resources.展开更多
The separation of lithium isotopes (^(6)Li and ^(7)Li) is of great importance for the nuclear industry.The lithium amalgam method is the only lithium isotopes separation process in industry,and the extensive use of me...The separation of lithium isotopes (^(6)Li and ^(7)Li) is of great importance for the nuclear industry.The lithium amalgam method is the only lithium isotopes separation process in industry,and the extensive use of mercury has raised concerns about its potential environmental hazards,which have prompted the search for more efficient and environmentally friendly alternatives.Crown ethers can bind lithium ions highly selectively and separate lithium isotopes effectively.A chemical exchange-based lithium isotopes separation method using crown ether decorated materials could be a viable and cost-effective alternative to the lithium amalgam method.In this review,we provide a systematic summary of the recent advances in lithium isotopes separation using crown ethers decorated materials.展开更多
Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild condition...Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild conditions.Here,we developed a photoinduced catalytic transfer hydrogenation(CTH)process for the efficient production of FEE through the reduction etherification of furfural(FF)using Na_(4)W_(10)O_(32)(NaDT),Pd/C,and ethanol as the hydrogen atom transfer(HAT)catalyst,hydrogenation catalyst,and the H donor,respectively.Notably,the introduction of brominated benzene(PhBr)as an additive significantly promoted the yield of FEE to 92.7%.A series of experiments and characterization results indicated that the attachment and detachment of Br atoms on Pd/C catalyst surface effectively regulate the balance between H^(+)sites and Pd sites in the NaDT+Pd/C catalytic system.The balance facilitates the preferential acetalization of FF catalyzed by H^(+)sites,followed by hydrogenation to efficiently produce FEE catalyzed by Pd sites.This photoinduced CTH process exhibits good stability and recyclability as well as universality for the transformation of various organic substrates under mild conditions.展开更多
The production of high-purity propylene glycol monomethyl ether acetate(PMA)through the transesterification of propylene glycol monomethyl ether(PM)and methyl acetate(MeOAc)is traditionally catalyzed by sodium methoxi...The production of high-purity propylene glycol monomethyl ether acetate(PMA)through the transesterification of propylene glycol monomethyl ether(PM)and methyl acetate(MeOAc)is traditionally catalyzed by sodium methoxide.However,the practical application of this method is significantly hindered by the inherent limitations of sodium methoxide,such as its high sensitivity to moisture and propensity for solid precipitation,which impede its effective use in continuous processes.This work proposed a continuous catalytic distillation(CD)process utilizing Amberlyst 15 cation exchange resin as the catalyst.A comprehensive series of reaction kinetic and CD experiments were conducted to evaluate the performance of the proposed process.The results demonstrate that under the optimal operating conditions,namely an ester-to-ether molar ratio of 6:1,a refluxratio of 5:1,a total feed rate of 0.92 g‧min^(-1),and an evaporation rate of 266.47 m^(3)‧m^(-2)‧h^(-1),the conversion rate of PM achieves 99.95%,and the PMA yield is 97.31%.Based on these findings,a process flowsheet for a continuous CD process tailored for the production of electronic-grade PMA is presented.This design incorporates light and heavy removal steps to ensure the production of PMA with a purity of 99.99%.Additionally,the process utilizes pressure swing distillation to recover MeOAc,thereby enhancing the overall efficiencyand sustainability of the production process.The proposed continuous CD process offers a highly efficient,cost-effective,and environmentally sustainable solution for the production of electronic-grade PMA.展开更多
Currently,triazole sulfonamide fungicide could be used to effectively control cucumber downy mildew(CDM),caused by Pseudoperonospora cubensis.In this study,a series of triazole sulfonamide derivatives containing diphe...Currently,triazole sulfonamide fungicide could be used to effectively control cucumber downy mildew(CDM),caused by Pseudoperonospora cubensis.In this study,a series of triazole sulfonamide derivatives containing diphenyl ether(DE)fragment were designed and synthesized.All target compounds were evaluated for their fungicidal activity against four oomycete diseases.Compound 10b showed the best activity against CDM with 40%control efficacy at 0.78 mg/L,which was the same as amisulbrom.Meanwhile,compounds 10d and 10h showed good inhibitory activity against Peronophythora litchii and compounds 10e,10f,10l and 10q showed good inhibitory activity against Phytophthora infestans.The results of computational chemistry showed that compound 10b had the same binding mode as amisulbrom and formed hydrogen bonds with the residues Gln9,His189 and Ash217.Compound 10b could be further investigated as a potential fungicide candidate.This study also provides a useful optimization strategy for the design of novel fungicides against CDM.展开更多
The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties o...The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties of various glycol dimethyl ethers are screened,and diglyme(G2)is selected as the sole solvent for the electrolyte.Lithium bis(fluorosulfonyl)imide(LiFSI),a highly dissociative salt,is used as the primary salt;while lithium nitrate(LiNO_(3))and lithium difluorophosphate(LiDFP),which have small ionic sizes and strong binding energies,are added as secondary salts.The resulting electrolyte can modulate the electric double layer structure by NO_(3)^(-) and DFP^(-) on the cathode side,leading to an increased Liþconcentration that is originally repelled by the cathode.Additionally,the oxidation stability of the electrolyte is improved and the formed electrode-electrolyte interphase is more uniform and stable,thereby enhancing the electrochemical performance of the cells.As a result,cells assembled with a total of 1 M ternary lithium salts in G2 solvent can operate at high voltage of 4.4 V.The LijjNCM811 cells maintain 80.2%capacity retention after 270 cycles at room temperature,with an average Coulombic efficiency of 99.5%,and exhibit 88.4%capacity retention after 200 cycles at -30℃.展开更多
基金This work was financially supported by the National Natural Science Foundation of China (No. 20564001)the Natural Science Foundation of Jiangxi Province (No. 050017)
文摘The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.
基金This work was financially supported by the Natural Science Foundation of China(Nos.50663001,20564001)Ministry of Education(No.2007-207058).
文摘The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...
基金This work was supported by the Jiangxi Research Center for Material Science & Engineering(No.ZX200401008)the Jiangxi Science and Technology Normal University.
文摘High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） and diethyl ether （EE） （by volume 1：1） ＋ 0,05 mol L^-1 Bu4NBF4. The film formed can be peeled off the electrode into freestanding films, The addition of EE into BFEE can improve the solubility of monomer. P5CI films obtained from this medium showed excellent electrochemical behavior with conductivity of 10^-2 S cm^-1, Structural studies showed that the polymerization of 5-cyanoindole occurred at the 2,3 position. As-formed P5CI films were thoroughly soluble in strong polar organic solvent dimethyl sulfoxide （DMSO） while partly soluble in tetrahydrofuran （THF） or acetone. Fluorescence spectral studies indicated that P5CI was a good blue-ight emitter.
文摘?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were converted to lactones smoothly．
基金We are grateful for the financial supports from the National Outstanding Youth Fund No.29925204)the Foundation for University Key Teacher by the Ministry of Education of Chinaa Visiting Fund of the National Laboratory of Applied Organic Chemistry.
文摘Regioselective addition reactions of silyl enolates to a, b-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg+.
基金the National Natural Science Foundation of China (Nos. 21372203 and 21272076)for the financial support
文摘Direct aldol condensation of various aromatic, heteroaromatic, α,β-unsaturated aldehydes and aliphatic aldehydes with acyldiazomethane was realized using Mgl2 etherate （Mgl2.（Et2O）n） as a promoter in the presence of diisopropyl amine （DIPEA） in excellent yields in a short time under mild conditions with high chemoselectivity. Iodide counterion, and a non-coordinating less ploar reaction media （i.e., CH2C12） are among the critical factors for this unique reactivity.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804202)the National Natural Science Foundation of China(Nos.22020102004 and 22125603)+1 种基金Tianjin Municipal Science and Technology Bureau(No.21JCZDJC00280)the Fundamental Research Funds for the Central Universities,and the Ministry of Education of China(No.T2017002).
文摘Polybrominated biphenyl ethers(PBDEs)and polycyclic aromatic hydrocarbons(PAHs)are commonly detected contaminants at e-waste recycling sites.Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallowsurface soils,increasing evidence shows that these compounds can leach into the groundwater.Herein,we compare the leachabilities of PBDEs vs.PAHs from contaminated soils collected at an e-waste recycling site in Tianjin,China.Considerable amounts of BDE-209(0.3–2 ng/L)and phenanthrene(42–106 ng/L),the most abundant PBDE and PAH at the site,are detected in the effluents of columns packed with contaminated soils,with the specific concentrations varying with hydrodynamic and solution chemistry conditions.Interestingly,the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles,whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent,but showing essentially no correlation with the concentration of mineral particles.The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive,as PBDEs and PAHs often co-exist at e-waste recycling sites(particularly at the sites wherein incineration is being practiced)and share many similarities in terms of physicochemical properties.One possible explanation is that due to its extremely low solubility,BDE-209 predominantly exists in free-phase(i.e.,as solid(nano)particles),whereas the more soluble phenanthrene is mainly sorbed to soil organic matter.Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804202)the National Natural Science Foundation of China(No.22020102004)+1 种基金the Tianjin Municipal Science and Technology Bureau(No.21JCZDJC00280)the Fundamental Research Funds for the Central Universities by the Ministry of Education of China(No.T2017002).
文摘Polybromodiphenyl ethers(PBDEs),the widely used flame retardants,are common contaminants in surface soils at e-waste recycling sites.The association of PBDEs with soil colloids has been observed,indicating the potential risk to groundwater due to colloid-facilitated transport.However,the extent to which soil colloidsmay enhance the spreading of PBDEs in groundwater is largely unknown.Herein,we report the co-transport of decabromodiphenyl ester(BDE-209)and soil colloids in saturated porous media.The colloids released froma soil sample collected at an e-waste recycling site in Tianjin,China,contain high concentration of PBDEs,with BDE-209 being the most abundant conger(320±30 mg/kg).The colloids exhibit relatively high mobility in saturated sand columns,under conditions commonly observed in groundwater environments.Notably,under all the tested conditions(i.e.,varying flow velocity,pH,ionic species and ionic strength),the mass of eluted BDE-209 correlates linearly with that of eluted soil colloids,even though the mobility of the colloids varies markedly depending on the specific hydrodynamic and solution chemistry conditions involved.Additionally,the mass of BDE-209 retained in the columns also correlates strongly with themass of retained colloids.Apparently,the PBDEs remain bound to soil colloids during transport in porous media.Findings in this study indicate that soil colloidsmay significantly promote the transport of PBDEs in groundwater by serving as an effective carrier.This might be the reason why the highly insoluble and adsorptive PBDEs are found in groundwater at some PBDE-contaminated sites.
文摘A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported,enabling highly diastereoselective access to cyclic etherified cyclopentenones with cyclic quaternary centers in moderate to good yields and>19∶1 dr.This catalysis enables the direct construction of two types of carboncyclic skeletons by adjusting the olefin types of 1,3-enyne acetates.When 1,3-enyne acetates bearing a cyclic alkene unit were used,5~6 fused bicarbocyclic products were diastereoselectively synthesized,whereas the reaction of acyclic 1,3-enyne acetates resulted in five-memebered carbocyclic framework.Notably,cyclic ether acetals are commonly used as protecting groups in traditional multistep organic syntheses,and in this reaction,such reagents serve as electrophilic cyclic ether precursors,achieving new uses for old reagents.The current method demonstrates good functional group compatibility,a broad substrate scope and high diastereoselectivity,providing a new synthetic strategy toward functionalized cyclopentenones.
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金the staff of the BL18U/BL19U1 Beamline of the National Facility for Protein Science,Shanghai,at the Shanghai Synchrotron Radiation Facility for assistance during data collectionthe National Key Research and Development Program of China(Grant No.2023YFD1700500,2022YFD1700200)the Project of Natural Science Foundation of Liaoning Province(2022-KF-15-02).
文摘Trehalase hydrolyzes trehalose to glucose to provide energy for insects or building blocks for chitin synthesis.Because trehalase is critical to insects but not to humans,it has long been considered a promising target for green insecticides.However,the known trehalase inhibitors are mainly sugar derivatives with poor druggability.In this study,the trehalase from Ostrinia furnacalis(OfTreh)was expressed and characterized.By integrative computational strategies,diphenyl ether herbicides were discovered as the first non-carbohydrate inhibitors of insect trehalases.Bifenox and its more stable derivative,chlomethoxyfen,inhibited Of Treh with Ki values of 56 and 43μM,respectively.The oral administration of bifenox or chlomethoxyfen to locusts resulted in the inhibition of trehalose hydrolysis in vivo,leading to a mortality rate of 66%and server locomotion disorder in the survivors.This study not only established a platform for the development of insecticides targeting trehalase but also discovered a new mechanism for diphenyl ethers to kill insects as trehalase inhibitors.
基金supported by the National Natural Science Foundation of China(U23A2088,22025206)the Dalian Innovation Support Plan for High Level Talents(2022RG13)+2 种基金DICP(Grant:DICP I202453,DICP I202234)the Fundamental Research Funds for the Central Universities(20720220008)support of the Liaoning Key Laboratory of Biomass Conversion for Energy and Material。
文摘The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of dimethyl ether(DME),which is derived from fossil resources,represents a promising approach to producing high-concentration formaldehyde with low energy consumption.However,there is still a lack of catalysts achieving satisfactory conversion of DME with high selectivity for formaldehyde under mild conditions.In this work,an efficient iron-molybdate(FeMo)catalyst was developed for the selective oxidation of DME to formaldehyde.The DME conversion of 84% was achieved with a superior formaldehyde selectivity(77%)at 300℃,a performance that is superior to all previously reported results.In an approximately 550 h continuous reaction,the catalyst maintained a conversion of 64% and a formaldehyde selectivity of 79%.Combined X-ray diffraction(XRD),Transmission electron microscope(TEM),Ultraviolet-visible spectroscopy(UV-Vis),Hydrogen temperature-programmed reduction(H_(2)-TPR),Fourier transform infrared(FT-IR)analyses,along with density functional theory(DFT)calculations,demonstrated that the excellent FeMo catalyst was composed of active Fe_(2)(MoO_(4))_(3)and MoO_(3)phases,and there was an interaction between them,which contributed to the efficient DME dissociation and smooth hydrogen spillover,leading to a superior DME conversion.With the support of DME/O_(2)pulse experiments,in-situ Raman,in-situ Dimethyl ether infrared spectroscopy(DME-IR)and DFT calculation results,a Mars-van Krevelen(MvK)reaction mechanism was proposed:DME was dissociated on the interface between Fe_(2)(MoO_(4))_(3)and MoO_(3)phases to form active methoxy species firstly,and it dehydrogenated to give hydrogen species;the generated hydrogen species smoothly spilled over from Fe_(2)(MoO_(4))_(3)to MoO_(3)enhanced by the interaction between Fe_(2)(MoO_(4))_(3)and MoO_(3);then the hydrogen species was consumed by MoO_(3),leading to a reduction of MoO_(3),and finally,the reduced MoO_(3)was re-oxidized by O_(2),returning to the initial state.These findings offer valuable insights not only for the development of efficient FeMo catalysts but also for elucidating the reaction mechanism involved in the oxidation of DME to formaldehyde,contributing to the optimized utilization of DME derived from fossil resources.
基金support from the National Natural Science Foundation of China (Grant No.U21B2094 and Grant No.U2067212)。
文摘The separation of lithium isotopes (^(6)Li and ^(7)Li) is of great importance for the nuclear industry.The lithium amalgam method is the only lithium isotopes separation process in industry,and the extensive use of mercury has raised concerns about its potential environmental hazards,which have prompted the search for more efficient and environmentally friendly alternatives.Crown ethers can bind lithium ions highly selectively and separate lithium isotopes effectively.A chemical exchange-based lithium isotopes separation method using crown ether decorated materials could be a viable and cost-effective alternative to the lithium amalgam method.In this review,we provide a systematic summary of the recent advances in lithium isotopes separation using crown ethers decorated materials.
文摘Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild conditions.Here,we developed a photoinduced catalytic transfer hydrogenation(CTH)process for the efficient production of FEE through the reduction etherification of furfural(FF)using Na_(4)W_(10)O_(32)(NaDT),Pd/C,and ethanol as the hydrogen atom transfer(HAT)catalyst,hydrogenation catalyst,and the H donor,respectively.Notably,the introduction of brominated benzene(PhBr)as an additive significantly promoted the yield of FEE to 92.7%.A series of experiments and characterization results indicated that the attachment and detachment of Br atoms on Pd/C catalyst surface effectively regulate the balance between H^(+)sites and Pd sites in the NaDT+Pd/C catalytic system.The balance facilitates the preferential acetalization of FF catalyzed by H^(+)sites,followed by hydrogenation to efficiently produce FEE catalyzed by Pd sites.This photoinduced CTH process exhibits good stability and recyclability as well as universality for the transformation of various organic substrates under mild conditions.
基金supported by the National Natural Science Foundation of China(22378065,22278077 and 22278076)the Key Program of Natural Science Foundation of Fujian Province of China(2022J02019).
文摘The production of high-purity propylene glycol monomethyl ether acetate(PMA)through the transesterification of propylene glycol monomethyl ether(PM)and methyl acetate(MeOAc)is traditionally catalyzed by sodium methoxide.However,the practical application of this method is significantly hindered by the inherent limitations of sodium methoxide,such as its high sensitivity to moisture and propensity for solid precipitation,which impede its effective use in continuous processes.This work proposed a continuous catalytic distillation(CD)process utilizing Amberlyst 15 cation exchange resin as the catalyst.A comprehensive series of reaction kinetic and CD experiments were conducted to evaluate the performance of the proposed process.The results demonstrate that under the optimal operating conditions,namely an ester-to-ether molar ratio of 6:1,a refluxratio of 5:1,a total feed rate of 0.92 g‧min^(-1),and an evaporation rate of 266.47 m^(3)‧m^(-2)‧h^(-1),the conversion rate of PM achieves 99.95%,and the PMA yield is 97.31%.Based on these findings,a process flowsheet for a continuous CD process tailored for the production of electronic-grade PMA is presented.This design incorporates light and heavy removal steps to ensure the production of PMA with a purity of 99.99%.Additionally,the process utilizes pressure swing distillation to recover MeOAc,thereby enhancing the overall efficiencyand sustainability of the production process.The proposed continuous CD process offers a highly efficient,cost-effective,and environmentally sustainable solution for the production of electronic-grade PMA.
基金the National Key Research and Development Program of China(2022YFD1700204)the Open Fund of State Key Laboratory of Green Pesticide by South China Agricultural University(gplscau202415)the National Natural Science Foundation of China(22477040).
文摘Currently,triazole sulfonamide fungicide could be used to effectively control cucumber downy mildew(CDM),caused by Pseudoperonospora cubensis.In this study,a series of triazole sulfonamide derivatives containing diphenyl ether(DE)fragment were designed and synthesized.All target compounds were evaluated for their fungicidal activity against four oomycete diseases.Compound 10b showed the best activity against CDM with 40%control efficacy at 0.78 mg/L,which was the same as amisulbrom.Meanwhile,compounds 10d and 10h showed good inhibitory activity against Peronophythora litchii and compounds 10e,10f,10l and 10q showed good inhibitory activity against Phytophthora infestans.The results of computational chemistry showed that compound 10b had the same binding mode as amisulbrom and formed hydrogen bonds with the residues Gln9,His189 and Ash217.Compound 10b could be further investigated as a potential fungicide candidate.This study also provides a useful optimization strategy for the design of novel fungicides against CDM.
文摘The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties of various glycol dimethyl ethers are screened,and diglyme(G2)is selected as the sole solvent for the electrolyte.Lithium bis(fluorosulfonyl)imide(LiFSI),a highly dissociative salt,is used as the primary salt;while lithium nitrate(LiNO_(3))and lithium difluorophosphate(LiDFP),which have small ionic sizes and strong binding energies,are added as secondary salts.The resulting electrolyte can modulate the electric double layer structure by NO_(3)^(-) and DFP^(-) on the cathode side,leading to an increased Liþconcentration that is originally repelled by the cathode.Additionally,the oxidation stability of the electrolyte is improved and the formed electrode-electrolyte interphase is more uniform and stable,thereby enhancing the electrochemical performance of the cells.As a result,cells assembled with a total of 1 M ternary lithium salts in G2 solvent can operate at high voltage of 4.4 V.The LijjNCM811 cells maintain 80.2%capacity retention after 270 cycles at room temperature,with an average Coulombic efficiency of 99.5%,and exhibit 88.4%capacity retention after 200 cycles at -30℃.
