An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist o...An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist of inexpensive rose bengal as photocatalyst to prepare a series of alkyl substituted oxazolines in moderate to excellent yields. High regioselectivity, operational safety, mild conditions and excellent substrate generality give this protocol broad application prospects.展开更多
An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of th...An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of the reaction is the compatibility of diboron reagents with the electrochemical conditions. This reaction exhibits broad substrate scope, good functional group tolerability, and easy scalability.展开更多
We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT ca...We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT catalyst could act as a nucleophile to generate primary radicals via an S_(N)2 pathway.However,this reaction was limited to benzyl radicals.Herein,we reported a new catalytic property of the MPT catalyst.The photoexcited MPT catalyst(E(MPT^(+)/MPT^(*))=-1.60 V vs.Ag/AgCl in MeCN)could reduce NHPI esters through a single electron transfer process.Various carbon radicals,including benzyl radical,as well as primary,secondary and tertiary alkyl radicals,could be generated easily.Notably,amino acids,peptide,pharmaceuticals,and other biologically active mole cules could be modified by using this methodology showing the potential synthetic utility of this method.展开更多
The liquid phase oxidation of cyclohexylbenzene(CHB)is a new green synthetic approach to cyclohexylbenzene-1-hydroperoxide(CHBHP),a key intermediate for preparing phenol and cyclohexanone.In this work,aryl-substituted...The liquid phase oxidation of cyclohexylbenzene(CHB)is a new green synthetic approach to cyclohexylbenzene-1-hydroperoxide(CHBHP),a key intermediate for preparing phenol and cyclohexanone.In this work,aryl-substituted(Cl and Br)derivatives of N-hydroxyphthalimide(NHPI)were synthesized and their catalytic performances for CHB oxidation were studied.In addition,geometric optimization and transition state search were performed using DFT calculations.Both experimental and theoretical studies have proven that chloro-substitution on NHPI can significantly improve its catalytic effects on the oxidation of CHB by oxygen.Compared with NHPI,CHB conversion and selectivity of CHBHP over Cl;NHPI were increased by 10.47%and 13.24%.The strategy of aryl-substituting NHPI with halogen atoms proposed in this study would provide a potential way to the development of new NHPI-based catalysts for aerobic oxidation reactions.展开更多
A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loa...A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.展开更多
Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic fram...Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.展开更多
A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI)combined with acetylacetone cobatt(Ⅱ)(Co(acac)2)was developed,and the probable catalytic mechanism was proposed....A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI)combined with acetylacetone cobatt(Ⅱ)(Co(acac)2)was developed,and the probable catalytic mechanism was proposed.The influences of the reaction conditions on conversion of α-ionone and the selectivity of the major product(5-keto-α-ionone)were investigated,and the technical parameters for 5-keto-α-ionone were optimized.The results show that the primary product is 5-keto-α-ionone,and by-products include epoxy-α-ionone,as well as rearrangement products 4-keto-β-ionone and epoxy-β-ionone,which are characterized by infrared spectra,proton nuclear magnetic resonance spectra,mass spectra and elemental analysis.The selectivity of 5-keto-α-ionone and the conversion of α-ionone are 55.0% and 97.0%,respectively,when 30%(molar fraction)NHPI,1.0%(molar fraction)Co(acac)2 and no solvent are employed under O2 pressure of 1.0 MPa and the reaction temperature of 65℃for 11 h.The procedure shows good reproducibility in the parallel experiments.展开更多
The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-...The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.展开更多
Fifty agricultural soil samples collected from Fuzhou,southeast China,were first investigated for the occurrence,distribution,and potential risks of twelve organophosphate esters(OPEs).The total concentration of OPEs(...Fifty agricultural soil samples collected from Fuzhou,southeast China,were first investigated for the occurrence,distribution,and potential risks of twelve organophosphate esters(OPEs).The total concentration of OPEs(ΣOPEs)in soil ranged from 1.33 to 96.5 ng/g dry weight(dw),with an average value of 17.1 ng/g dw.Especially,halogenated-OPEs were the predominant group with amean level of 9.75 ng/g dw,and tris(1-chloro-2-propyl)phosphate(TCIPP)was the most abundant OPEs,accounting for 51.1%ofΣOPEs.The concentrations of TCIPP andΣOPEs were found to be significantly higher(P<0.05)in soils of urban areas than those in suburban areas.In addition,the use of agricultural plastic films and total organic carbon had a positive effect on the occurrence of OPE in this study.The positive matrix factorization model suggested complex sources of OPEs in agricultural soils from Fuzhou.The ecological risk assessment demonstrated that tricresyl phosphate presented a medium risk to land-based organisms(0.1≤risk quotient<1.0).Nevertheless,the carcinogenic and noncarcinogenic risks for human exposure to OPEs through soil ingestion and dermal absorption were negligible.These findings would facilitate further investigations into the pollution management and risk control of OPEs.展开更多
The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction tempera...The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.展开更多
Phthalic acid esters(PAEs)are a group of compounds widespread in the environment.To investigate the occurrence and accumulation characteristics of PAEs,surface water samples were collected from the Three Gorges Reserv...Phthalic acid esters(PAEs)are a group of compounds widespread in the environment.To investigate the occurrence and accumulation characteristics of PAEs,surface water samples were collected from the Three Gorges Reservoir area,China.The total concentrations of∑_(11)analyzed PAEs(11PAEs)in the collected water samples ranging from 197.7 to 1,409.3 ng/L(mean±IQR:583.1±308.4 ng/L).While DEHP was the most frequently detected PAE,DnBP and DnNP were the most predominant PAEs in the analyzed water samples with a mean contribution of 63.3%of the∑_(11)PAEs.The concentrations of the∑_(11)PAEs in the water samples from the upper reaches of the Yangtze River were significantly higher than those from themiddle reaches.To better understand the transport and fate of the PAEs,seven detected PAEs were modeled by Quantitative Water Air Sediment Interaction(QWASI).The simulated and measured values were close for most PAEs,and differences are within one order of magnitude even for the worst one.For all simulated PAEs,water and particle inflow were main sources in the reservoir,whereas water outflow and degradation in water were important removal pathways.The contribution ratios of different sources/losses varied fromPAEs,depending on their properties.The calculated risk quotients of DnNP in the Three Gorges Reservoir area whether based onmonitoring or simulating results were all far exceeded the safety threshold value,implying the occurrence of this PAE compound may cause potential adverse effects for the aquatic ecology of the Three Gorges Reservoir area.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
A visible-light-promoted[1+2]cycloaddition of gem-difluoroalkenes with aryl diazo esters provides an efficient and important route to 1,1-difluorocyclopropanes.The reaction conditions are mild,and the operation is ver...A visible-light-promoted[1+2]cycloaddition of gem-difluoroalkenes with aryl diazo esters provides an efficient and important route to 1,1-difluorocyclopropanes.The reaction conditions are mild,and the operation is very simple.A number of diazo esters and gem-difluoroalkenes are suitable for this reaction(36 examples),providing the desired products in good yields with excellent diastereoselectivity(>20∶1).展开更多
As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneou...As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.展开更多
An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones a...An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.展开更多
To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated th...To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated the in vitro antifungal activity of these compounds against six common plant pathogenic fungi.Among them,compounds B1-6,B1-17 and B2-6 displayed great in vitro activity against Rhizoctonia solani with EC50 values of 7.28,4.64,and 7.62μg/mL.The HOMO and LUMO calculations indicated that strong electronwithdrawing halogen elements exhibit better activity compared to electron-donating alkyl groups.Preliminary mechanistic studies,using SEM and TEM,indicated that compound B1-17 induced disordered entanglement of hyphae,shrinkage of hyphal surfaces,and vacuole swelling and rupture,which disrupted normal hyphal growth.Additionally,compound B1-17 induced the production and accumulation of ROS,disrupted MMP,and effectively inhibited the germination and formation of sclerotia in Rhizoctonia solani.These compounds hold potential as new antifungal agents for further research.展开更多
It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation...It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation but can also track the fouling process during operation.Herein,an aggregation-induced emission(AIE)-active polymer membrane was prepared by the interfacial polymerization of a cyclodextrin-based glycocluster(CD@Glucose)and a tetraphenylethylene derivative modified with boronic acid groups(TPEDB)on the surface of a polyacrylonitrile(PAN)ultrafiltration membrane.This interfacial polymerization method can be stacked layer-by-layer to regulate the hydrophilicity and pore structure of the membrane.With the increase in the number of polymer layers,the separation and antifouling properties of the membrane gradually improved.Owing to the AIE property of the crosslinking agent TPEDB,the occurrence of interfacial polymerization and the degree of fouling during membrane operation can be monitored by the fluorescence distribution and intensity.With the aggravation of membrane fouling,the fluorescence decreased gradually,but recovered after cleaning.Therefore,this AIE effect can be used for real-time monitoring of interfacial polymerization as well as membrane fouling.展开更多
Phthalic acid esters(PAEs)are widely released into the environment due to industrial and agricultural activities.This poses significant risks,not only to crops grown on contaminated soil but also to humans.PAEs enter ...Phthalic acid esters(PAEs)are widely released into the environment due to industrial and agricultural activities.This poses significant risks,not only to crops grown on contaminated soil but also to humans.PAEs enter the human body through the food chain,causing potential health hazards.Endophytic bacteria have demonstrated a significant potential as effective bioremediation agents,with specialized mechanisms of PAEs degradation.Endophytic bacteria such as Rhodococcus,Pseudomonas and Sphingomona recognize root exudates,adhere to and penetrate root surfaces,and ultimately colonize crops.They form symbiotic relationships with crops,obtaining nutrients and habitats from crops,meanwhile,promoting plant growth and health through hormone production,nutrient regulation,and the suppression of pathogenic microorganisms.Furthermore,endophytic bacteria efficiently degrade PAEs in soil-crop systems through synergistic interactions with indigenous rhizosphere microflora and regulatory effects on enzyme activity in crops.Here,we review the role of endophytic bacteria in the bioremediation of PAEs-contaminated crops and soils.In addition,we discuss the scarcity of endophytic bacterial strains with a confirmed ability to degrade PAEs,and underscore the lack of the research on the mechanisms of PAEs degradation by these bacteria.This review also points out that future study should investigate the molecular mechanisms underlying the interaction between endophytic bacteria and PAEs to offer novel insights and solutions for environmental protection and sustainable agricultural development.展开更多
Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,p...Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,phosphorous-containing 1-vinylimidazole salts(called VIDHP and VIDPP)were synthesized through the facile neutralization of the acid and 1-vinylimidazole.VIDHP and VIDPP were then applied as flame-retardant crosslinking agents of VERs,by which phosphorus-containing groups could be incorporated into the resin chain via ionic bonds.VIDHP/VER and VIDPP/VER showed a high curing activity and can be well cured in moderate temperatures.With 20 wt.%additions of VIDHP and VIDPP,VIDHP20/VER,and VIDPP20/VER presented a limiting oxygen index value of 29.7%and 28.4%,respectively,with the latter achieving a UL 94 V0 rating.In the cone calorimetric test,compared to the unmodified VERs,VIDPP20/VER exhibited large reductions in the peak heat release rate,total heat release rate,and total smoke release rate while VIDHP20/VER demonstrated comparatively inferior performance in terms of the heat release.VIDHP20/VER and VIDPP20/VER showed good thermal stability and presented a little lower glass transition temperature than the control sample.VIDPP with a low phosphorus oxidation state(+1)demonstrated high flame-retardant activities in the gaseous phase,whereas VIDHP with a high phosphorus oxidation state(+5)primarily exhibited efficacy in the condensed phase.展开更多
Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polyme...Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polymers has become an attractive subject.Herein,a new monomer of thiosalicylic methyl glycolide(TSMG)was synthesized using one-pot method and high molecular weight poly(thiosalicylic methyl glycolide)(PTSMG,M_(n) up to 300 kDa)can be obtained via the ring-opening polymerization(ROP)of TSMG.PTSMG exhibits good closed-loop recyclability and hydrolytic degradability,where PTSMG can generate pristine monomers through sublimation thermal depolymerization conditions due to the presence of thiophenol ester bond in the polymer chains,and can be degraded rapidly in aqueous solution,which provides a potential solution to the current plastic pollution problem.展开更多
基金supported by the National Natural Science Foundation of China (No. 22078299)Zhejiang Provincial Natural Science Foundation of China (Nos. LY21B060005, LQ20B060007)+1 种基金the College of Pharmaceutical Sciences, Zhejiang University of TechnologyCollaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals for the financial help。
文摘An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist of inexpensive rose bengal as photocatalyst to prepare a series of alkyl substituted oxazolines in moderate to excellent yields. High regioselectivity, operational safety, mild conditions and excellent substrate generality give this protocol broad application prospects.
基金supported by the National Natural Science Foundation of China (Nos. 21871074 and 21971051)the National Key R&D Program of China (No. 2018YFB1501604)+1 种基金the Fundamental Research Funds for the Central Universities (No. PA2020GDKC0021)the Key Research and Development Program Projects in Anhui Province (No. 201904a07020069)。
文摘An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of the reaction is the compatibility of diboron reagents with the electrochemical conditions. This reaction exhibits broad substrate scope, good functional group tolerability, and easy scalability.
基金supported by the National Natural Science Foundation of China(22102160)the"CUG Scholar"Scientific Research Funds at China University of Geosciences(Wuhan)(Project No.2022014)+1 种基金the Wuhan Talent Plan(Excellent Young Talents,No.20230350051)the Zhejiang Provincial Natural Science Foundation of China(No.LQ22B020004).
文摘We have developed a series of 1-methylpyridine-2(1H)-thione(MPT)analogues to be used as organocatalysts.The MPT catalysts are easily prepared and bench-stable.In our previous work,we found that the ground-state MPT catalyst could act as a nucleophile to generate primary radicals via an S_(N)2 pathway.However,this reaction was limited to benzyl radicals.Herein,we reported a new catalytic property of the MPT catalyst.The photoexcited MPT catalyst(E(MPT^(+)/MPT^(*))=-1.60 V vs.Ag/AgCl in MeCN)could reduce NHPI esters through a single electron transfer process.Various carbon radicals,including benzyl radical,as well as primary,secondary and tertiary alkyl radicals,could be generated easily.Notably,amino acids,peptide,pharmaceuticals,and other biologically active mole cules could be modified by using this methodology showing the potential synthetic utility of this method.
基金financially supported by the National Natural Science Foundation of China(21706240)。
文摘The liquid phase oxidation of cyclohexylbenzene(CHB)is a new green synthetic approach to cyclohexylbenzene-1-hydroperoxide(CHBHP),a key intermediate for preparing phenol and cyclohexanone.In this work,aryl-substituted(Cl and Br)derivatives of N-hydroxyphthalimide(NHPI)were synthesized and their catalytic performances for CHB oxidation were studied.In addition,geometric optimization and transition state search were performed using DFT calculations.Both experimental and theoretical studies have proven that chloro-substitution on NHPI can significantly improve its catalytic effects on the oxidation of CHB by oxygen.Compared with NHPI,CHB conversion and selectivity of CHBHP over Cl;NHPI were increased by 10.47%and 13.24%.The strategy of aryl-substituting NHPI with halogen atoms proposed in this study would provide a potential way to the development of new NHPI-based catalysts for aerobic oxidation reactions.
基金the financial support from the National Key R&D Program of China(No.2017YFB0306504)National Natural Science Foundation of China(No.22008094,22178154 and 21878133)+2 种基金Chinese Postdoctoral Science Foundation(No.2019M651743,2020M671364 and 2020M673039)Natural Science Foundation of Jiangsu Province(No.BK20190852)Natural Science Foundation for Jiangsu Colleges and Universities(No.19KJB530005)
文摘A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21978119,22202088)Key Research and Development Plan of Hainan Province(ZDYF2022SHFZ285)Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB636)。
文摘Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.
基金Project(50573019)supported by the National Natural Science Foundation of China
文摘A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI)combined with acetylacetone cobatt(Ⅱ)(Co(acac)2)was developed,and the probable catalytic mechanism was proposed.The influences of the reaction conditions on conversion of α-ionone and the selectivity of the major product(5-keto-α-ionone)were investigated,and the technical parameters for 5-keto-α-ionone were optimized.The results show that the primary product is 5-keto-α-ionone,and by-products include epoxy-α-ionone,as well as rearrangement products 4-keto-β-ionone and epoxy-β-ionone,which are characterized by infrared spectra,proton nuclear magnetic resonance spectra,mass spectra and elemental analysis.The selectivity of 5-keto-α-ionone and the conversion of α-ionone are 55.0% and 97.0%,respectively,when 30%(molar fraction)NHPI,1.0%(molar fraction)Co(acac)2 and no solvent are employed under O2 pressure of 1.0 MPa and the reaction temperature of 65℃for 11 h.The procedure shows good reproducibility in the parallel experiments.
基金supported by the National Natural Science Foundation of China(Grant No.20072025).
文摘The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.
基金supported by the Open Fund of the Laboratory for Earth Surface Processes,Ministry of Education,Peking University,Beijing,China,and the Cultivation Fund Program for Excellent Dissertation in Fujian Normal University,China(No.LWPYS202315)the Research Start-up Fund of Fujian Normal University,China(No.Y0720304X13).
文摘Fifty agricultural soil samples collected from Fuzhou,southeast China,were first investigated for the occurrence,distribution,and potential risks of twelve organophosphate esters(OPEs).The total concentration of OPEs(ΣOPEs)in soil ranged from 1.33 to 96.5 ng/g dry weight(dw),with an average value of 17.1 ng/g dw.Especially,halogenated-OPEs were the predominant group with amean level of 9.75 ng/g dw,and tris(1-chloro-2-propyl)phosphate(TCIPP)was the most abundant OPEs,accounting for 51.1%ofΣOPEs.The concentrations of TCIPP andΣOPEs were found to be significantly higher(P<0.05)in soils of urban areas than those in suburban areas.In addition,the use of agricultural plastic films and total organic carbon had a positive effect on the occurrence of OPE in this study.The positive matrix factorization model suggested complex sources of OPEs in agricultural soils from Fuzhou.The ecological risk assessment demonstrated that tricresyl phosphate presented a medium risk to land-based organisms(0.1≤risk quotient<1.0).Nevertheless,the carcinogenic and noncarcinogenic risks for human exposure to OPEs through soil ingestion and dermal absorption were negligible.These findings would facilitate further investigations into the pollution management and risk control of OPEs.
文摘The efficient hydrogenolysis of esters to alkanes is the key protocol for producing advanced biofuels from renewable plant oils or fats.Due to the low reactivity of the carbonyl group in esters,a high reaction temperature(>250℃)is the prerequisite to ensure high conversion of esters.Here,we report a highly dispersed MoO_(x)-Ru/C bimetallic catalyst for the efficient hydrogenolysis of esters to alkanes under 150°C.The optimal catalyst exhibits>99%conversion of methyl stearate and 99%selectivity to diesel-range alkanes,reaching a high rate of up to 2.0 mmol gcat^(–1)h^(–1),5 times higher than that of Ru/C catalyst(MoO_(x)/C is inert).Integrated experimental and theoretical investigations attribute the high performance to the abundant MoO_(x)-Ru interfacial sites on the catalyst surface,which offers high activity for the C–O cleavage of esters.Furthermore,the dispersed MoO_(x)species significantly weaken the hydrocracking activity of the metallic Ru for C–C bonds,thus yielding alkane products without carbon loss.This study provides a facile and novel strategy for the design of high-performance heterogeneous catalysts for the hydrodeoxygenation of biomass-derived esters to alkane products.
基金supported by the Innovation Fund of Nanjing Institute of Environmental Science,Ministry of Ecology and Environment,China(No.ZX2023QT003)the National Natural Science Foundation of China(No.22306130)+1 种基金Jiangsu Funding Program for Excellent Postdoctoral Talent(No.2022ZB789)the Ecological Environment Research Project of Jiangsu Province,China(No.2022014).
文摘Phthalic acid esters(PAEs)are a group of compounds widespread in the environment.To investigate the occurrence and accumulation characteristics of PAEs,surface water samples were collected from the Three Gorges Reservoir area,China.The total concentrations of∑_(11)analyzed PAEs(11PAEs)in the collected water samples ranging from 197.7 to 1,409.3 ng/L(mean±IQR:583.1±308.4 ng/L).While DEHP was the most frequently detected PAE,DnBP and DnNP were the most predominant PAEs in the analyzed water samples with a mean contribution of 63.3%of the∑_(11)PAEs.The concentrations of the∑_(11)PAEs in the water samples from the upper reaches of the Yangtze River were significantly higher than those from themiddle reaches.To better understand the transport and fate of the PAEs,seven detected PAEs were modeled by Quantitative Water Air Sediment Interaction(QWASI).The simulated and measured values were close for most PAEs,and differences are within one order of magnitude even for the worst one.For all simulated PAEs,water and particle inflow were main sources in the reservoir,whereas water outflow and degradation in water were important removal pathways.The contribution ratios of different sources/losses varied fromPAEs,depending on their properties.The calculated risk quotients of DnNP in the Three Gorges Reservoir area whether based onmonitoring or simulating results were all far exceeded the safety threshold value,implying the occurrence of this PAE compound may cause potential adverse effects for the aquatic ecology of the Three Gorges Reservoir area.
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A visible-light-promoted[1+2]cycloaddition of gem-difluoroalkenes with aryl diazo esters provides an efficient and important route to 1,1-difluorocyclopropanes.The reaction conditions are mild,and the operation is very simple.A number of diazo esters and gem-difluoroalkenes are suitable for this reaction(36 examples),providing the desired products in good yields with excellent diastereoselectivity(>20∶1).
基金National Nature Science Foundation of China(Nos.52025032,52103144 and 523B2026)for their financial supportsupported by the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(No.GZC20231544)。
文摘As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.
基金financial support from the National Natural Science Foundation of China (Nos. 21801087 and 22201089)。
文摘An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.
基金the Fundamental Research Funds for the Central Universities(KYCYXT2022011,KJYQ2024014)the National Key Research and Development Program of China(2021YFD1700102)for the generous financial support for our programs.
文摘To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated the in vitro antifungal activity of these compounds against six common plant pathogenic fungi.Among them,compounds B1-6,B1-17 and B2-6 displayed great in vitro activity against Rhizoctonia solani with EC50 values of 7.28,4.64,and 7.62μg/mL.The HOMO and LUMO calculations indicated that strong electronwithdrawing halogen elements exhibit better activity compared to electron-donating alkyl groups.Preliminary mechanistic studies,using SEM and TEM,indicated that compound B1-17 induced disordered entanglement of hyphae,shrinkage of hyphal surfaces,and vacuole swelling and rupture,which disrupted normal hyphal growth.Additionally,compound B1-17 induced the production and accumulation of ROS,disrupted MMP,and effectively inhibited the germination and formation of sclerotia in Rhizoctonia solani.These compounds hold potential as new antifungal agents for further research.
基金supported by the Fundamental Research Funds for Central Universities(No.30922010811).
文摘It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation but can also track the fouling process during operation.Herein,an aggregation-induced emission(AIE)-active polymer membrane was prepared by the interfacial polymerization of a cyclodextrin-based glycocluster(CD@Glucose)and a tetraphenylethylene derivative modified with boronic acid groups(TPEDB)on the surface of a polyacrylonitrile(PAN)ultrafiltration membrane.This interfacial polymerization method can be stacked layer-by-layer to regulate the hydrophilicity and pore structure of the membrane.With the increase in the number of polymer layers,the separation and antifouling properties of the membrane gradually improved.Owing to the AIE property of the crosslinking agent TPEDB,the occurrence of interfacial polymerization and the degree of fouling during membrane operation can be monitored by the fluorescence distribution and intensity.With the aggravation of membrane fouling,the fluorescence decreased gradually,but recovered after cleaning.Therefore,this AIE effect can be used for real-time monitoring of interfacial polymerization as well as membrane fouling.
基金supported by the National Natural Science Foundation of China(No.22161132011)Jiangsu Provincial Special Fund for S&T Innovation in Carbon Emission Peak and Neutrality(No.20220013)+1 种基金the National Key Research and Development Program of China(Nos.2023YFE0110800 and 2023YFC3708100)the Fundamental Research Funds for the Central Universities(No.QTPY2024001).
文摘Phthalic acid esters(PAEs)are widely released into the environment due to industrial and agricultural activities.This poses significant risks,not only to crops grown on contaminated soil but also to humans.PAEs enter the human body through the food chain,causing potential health hazards.Endophytic bacteria have demonstrated a significant potential as effective bioremediation agents,with specialized mechanisms of PAEs degradation.Endophytic bacteria such as Rhodococcus,Pseudomonas and Sphingomona recognize root exudates,adhere to and penetrate root surfaces,and ultimately colonize crops.They form symbiotic relationships with crops,obtaining nutrients and habitats from crops,meanwhile,promoting plant growth and health through hormone production,nutrient regulation,and the suppression of pathogenic microorganisms.Furthermore,endophytic bacteria efficiently degrade PAEs in soil-crop systems through synergistic interactions with indigenous rhizosphere microflora and regulatory effects on enzyme activity in crops.Here,we review the role of endophytic bacteria in the bioremediation of PAEs-contaminated crops and soils.In addition,we discuss the scarcity of endophytic bacterial strains with a confirmed ability to degrade PAEs,and underscore the lack of the research on the mechanisms of PAEs degradation by these bacteria.This review also points out that future study should investigate the molecular mechanisms underlying the interaction between endophytic bacteria and PAEs to offer novel insights and solutions for environmental protection and sustainable agricultural development.
基金supported by the National Natural Science Foundation of China(Grant Nos.51991351 and51903132)the Young Elite Scientist Sponsorship Program by CAST(No.2022QNRC001).
文摘Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,phosphorous-containing 1-vinylimidazole salts(called VIDHP and VIDPP)were synthesized through the facile neutralization of the acid and 1-vinylimidazole.VIDHP and VIDPP were then applied as flame-retardant crosslinking agents of VERs,by which phosphorus-containing groups could be incorporated into the resin chain via ionic bonds.VIDHP/VER and VIDPP/VER showed a high curing activity and can be well cured in moderate temperatures.With 20 wt.%additions of VIDHP and VIDPP,VIDHP20/VER,and VIDPP20/VER presented a limiting oxygen index value of 29.7%and 28.4%,respectively,with the latter achieving a UL 94 V0 rating.In the cone calorimetric test,compared to the unmodified VERs,VIDPP20/VER exhibited large reductions in the peak heat release rate,total heat release rate,and total smoke release rate while VIDHP20/VER demonstrated comparatively inferior performance in terms of the heat release.VIDHP20/VER and VIDPP20/VER showed good thermal stability and presented a little lower glass transition temperature than the control sample.VIDPP with a low phosphorus oxidation state(+1)demonstrated high flame-retardant activities in the gaseous phase,whereas VIDHP with a high phosphorus oxidation state(+5)primarily exhibited efficacy in the condensed phase.
基金supported by the National Key R&D Program of China(No.2023YFA1506804)the National Natural Science Foundation of China(Nos.22471110,22171111,22131007 and 22071093)+1 种基金the Science Foundation of Gansu Province of China(No.22JR5RA406)the Fundamental Research Funds for the Central Universities(No.lzujbky-2023-15)。
文摘Most commercial plastics cannot easily degrade,which raises a number of sustainability issues.To address the current problem of plastic pollution,the research and development of easily degradable and recyclable polymers has become an attractive subject.Herein,a new monomer of thiosalicylic methyl glycolide(TSMG)was synthesized using one-pot method and high molecular weight poly(thiosalicylic methyl glycolide)(PTSMG,M_(n) up to 300 kDa)can be obtained via the ring-opening polymerization(ROP)of TSMG.PTSMG exhibits good closed-loop recyclability and hydrolytic degradability,where PTSMG can generate pristine monomers through sublimation thermal depolymerization conditions due to the presence of thiophenol ester bond in the polymer chains,and can be degraded rapidly in aqueous solution,which provides a potential solution to the current plastic pollution problem.
