Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability...Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability of the triazine ring structure within cyanate ester(CE)crosslinked networks after molding posed significant challenges for both recycling,repairing,and degradation of resin.To address these obstacles,dynamic thiocyanate ester(TCE)bonds and photocurable group were incorporated into CE,obtaining the recyclable and 3D printable CE covalent adaptable networks(CANs),denoted as PTCE1.5.This material exhibits a Young's modulus of 810 MPa and a tensile strength of 50.8 MPa.Notably,damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment.Leveraging the solid-state plasticity,PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability,enabling its reconfigurable 4D printing.The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model,validating its potential application as a controllable component in the aerospace field.Moreover,printed PTCE1.5 can be fully degraded into thiol-modified intermediate products.Overall,this material not only enriches the application range of CE resin,but also provides a reliable approach to addressing environmental issue.展开更多
A trace analytical method based on solid-phase extraction gas chromatography-tandem mass spectrometry(SPE–GC–MS/MS)was developed for the rapid detection of 256 semi-volatile organic compounds(SVOCs),including 25 pol...A trace analytical method based on solid-phase extraction gas chromatography-tandem mass spectrometry(SPE–GC–MS/MS)was developed for the rapid detection of 256 semi-volatile organic compounds(SVOCs),including 25 polycyclic aromatic hydrocarbons(PAHs),70 polychlorinated biphenyls(PCBs),123 pesticides,20 phthalate esters(PAEs),4 organophosphate esters(OPEs),9 synthetic musks(SMs),and 5 UV filters(UVs)in water.No-tably,this method provided a decent linearity of calibration standards(R^(2)>0.999),excellent method limits of quantification(MLOQs)(0.12–11.41 ng/L),satisfactory matrix spiking recovery rates(60.4%–126%),and high precision(intra-day relative standard deviations(RSDs):1.0%–10.0%,inter-day RSDs:3.0%–15.0%,and inter-week RSDs:3.4%–15.7%),making it suitable for trace-level studies.Statistical analysis revealed that SVOCs with higher volatility exhibited enhanced recovery rates.Validation of the methodology involved analyzing SVOCs in real spring water and river water samples.Twenty-seven SVOCs were detected in spring water and 58 in river water,with an average concentration of 631.73 and 16,095 ng/L,respectively.Among the detected SVOCs,PAEs constituted the predominant proportion.This study underscored the presence of SVOCs contamination specifi-cally within the spring water,although SVOCs concentrations in river water were significantly greater than those found in spring water.In summary,this sensitive method based on SPE–GC–MS/MS was successfully developed and validated for the rapid analysis of a diverse array of 256 SVOCs at trace levels in water,including not only the traditional highly valued PAHs,PCBs,pesticides,and PAEs,but also the emerging OPEs,UVs,and SMs.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
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 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
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
To explore the multicenter characteristics of endocrine-like phthalate esters(PAEs)in household dust and propose effective control strategies for global indoor public health.An on-site observational investigation was ...To explore the multicenter characteristics of endocrine-like phthalate esters(PAEs)in household dust and propose effective control strategies for global indoor public health.An on-site observational investigation was conducted in nine Chinese cities from 2018 to 2019.A total of 246 household dust sampleswere collected and analyzed for ten PAE congeners using Gas Chromatography-Mass Spectrometry(GC-MS).Questionnaires were used to gather information on building conditions,indoor behaviors,and ventilation habits.In residential dust from the nine cities,the total concentrations of the ten PAE congeners(PAEs)ranged from 0.921 to 29097.297μg/g.Dicyclohexyl phthalate(DCHP)and di(2-ethylhexyl)phthalate(DEHP)were the dominant congeners inPAEs.Childhood exposure to PAEs through dust ingestion was four orders of magnitude higher than through inhalation,with a carcinogenic risk of 5.47×10^(−6) for DEHP exposure in household dust.HigherPAEs concentrations were associated with higher temperature,double glazing,wall paint usage,television and computer use,and indoor plant growth.This multicenter on-site investigation confirmed PAE pollution characteristics and uncovered the inacceptable risk of daily DEHP exposure in household dust under real living conditions.Effective mitigation measures based on household-related information,residential characteristics,decoration materials,and lifestyle should be taken to build a healthy household environment.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
An efficient synthesis of α-thioenamine compounds via a K_(2)S_(2)O_(8)-promoted cross-dehydrogenative coupling reaction between heterocyclic thiols and enamine esters in an aqueous medium has been developed.The reac...An efficient synthesis of α-thioenamine compounds via a K_(2)S_(2)O_(8)-promoted cross-dehydrogenative coupling reaction between heterocyclic thiols and enamine esters in an aqueous medium has been developed.The reaction showed good tolerance for enamine esters and heterocyclic thiols with various functional groups,producingα-thioenamine derivatives in moderate to high yields.Mechanistic studies revealed that heterocyclic thiols react with K_(2)S_(2)O_(8) in water to form reactive disulfides in situ,which then react with enamine esters to generate a series ofα-thioenamines.Building on the proposed mechanism,we developed a sulfenylation reaction of enamine esters with disulfides without the need for an oxidant.This oxidant-free approach has been successfully employed to synthesize DNA-taggedα-thioenamine,demonstrating its considerable potential for various synthetic applications.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
Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both...Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates,facilitating the synthesis of mono-,di-,tri-,and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions.Mechanistic investigations indicate that the in situ generated Ni(Ⅰ)complex might serve as the active species to react with propargylic esters,forming the allenyl-Ni(Ⅰ)complex under electroreductive conditions.A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ)complex on CO_(2) is likely involved in the formation of the desired 2,3-allenoic acids.展开更多
Contamination of microplastics(MPs)and their associated plastic additives in the marine environment is a global concern due to their widespread distribution and toxicity to aquatic life.Although polyvinyl chloride(PVC...Contamination of microplastics(MPs)and their associated plastic additives in the marine environment is a global concern due to their widespread distribution and toxicity to aquatic life.Although polyvinyl chloride(PVC)materials are commonly used in aquaculture environments,the potential risks of PVC MPs and the release of their additives in aquatic environments and organisms remain largely unknown.In this study,we investigated the leaching behaviors of phthalate esters(PAEs),including the mass and composition of PAEs in PVC MPs and their leaching kinetics,and evaluated the environmental risks of using PVC canvas in aquaculture activities.It was found that diethyl phthalate(DEP)was the most dominant PAE compound leached from PVC MPs(44.70±7.87 ng/g),followed by dimethyl phthalate(DMP,24.40±1.56 ng/g).The Elovich model was applied to simulate the leaching kinetics,and the simulated curves showed similar logarithmic trends that PAEs rapidly migrated from MPs to the water column at first and followed by a gradual increase over time.The different leaching kinetics of PAEs can be explained by their chemical properties,such as water solubility,molecular weight,and octanol-water partition coefficient.Compounds with lower solubility showed higher leaching coefficients,which are the constants of different PAEs in Elovich equation.Considering the potential joint toxicity of PVC leachates and the importance of food security,it is recommended to use PVC products responsibly and manage plastic waste properly.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
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
Aqueous zinc-ion batteries(AZIBs)have garnered significant attention owing to their intrinsic safety and the abundance of zinc resources.Traditional separators,such as glass fiber(GF),face challenges such as zinc dend...Aqueous zinc-ion batteries(AZIBs)have garnered significant attention owing to their intrinsic safety and the abundance of zinc resources.Traditional separators,such as glass fiber(GF),face challenges such as zinc dendrite penetration,inadequate mechanical strength,and excessive thickness,which results in increased internal resistance and diminished battery performance.In this study,we investigate the use of a mixed cellulose ester(MCE)filter membrane as a separator for AZIBs.The 110-μm-thick MCE separator exhibits a mechanical strength of 4.88 MPa,which is 12 times greater than that of the 325-μm-thick GF separator,and effectively resists zinc dendrite formation,even with a thinner design.Zn symmetric batteries utilizing the MCE separator exhibit a cycle time of 2700 h at 1 mA cm^(-2).The MCE separator,incorporating hydroxyl and nitrogen functional groups,promotes uniform zinc deposition and mitigates the formation of by-products on the zinc anode,thereby enhancing corrosion resistance.Zn‖MnO_(2) full batteries with the MCE separator demonstrate a specific capacity of 161 mAh g^(-1)at 1 A g^(-1),with a capacity retention of 80.1%after 500 cycles.Furthermore,Zn‖VO_(2) full cells employing the MCE separator exhibit excellent rate performance and cycling stability.At 0.25 A g^(-1),the Zn‖VO_(2)cell retains 86.9%of its capacity after 800 cycles,demonstrating a high capacity of 243 mAh g^(-1).This study offers novel insights into enhancing the performance of AZIBs through the selection of a low-cost,high-strength,and thin separator design.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
Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In ...Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In this study,IR104 from Streptomyces aureocirculatus was identified from 157 wild-type imine reductases for the synthesis of(S)-2-((R)-2-oxo-4-propylpyrrolidin-1-yl)butanamide(antiepileptic drug Brivaracetam)via dynamic kinetic resolution reductive amination from ethyl 3-formylhexanoate and(S)-2-aminobutylamide with high diastereoselectivity.To further improve the catalytic efficiency of IR104,its mutant D191E/L195I/E253S/M258A(M3)was identified by saturation mutagenesis and iterative combinatorial mutagenesis,which exhibited a 102-fold increase in the catalytic efficiency relative to that of wild-type enzyme and high diastereoselectivity(98:2 d.r.).Crystal structural analysis and molecular dynamics simulations provided some insights into the molecular basis for the improved activity of the mutant enzyme.The imine reductase identified in this study could accept chiral amino amides/esters as amino donors for the dynamic kinetic resolution reductive amination of racemicα-substituted aldehydo-esters,expanding the substrate scope of imine reductases in the dynamic kinetic resolution-reductive amination.Finally,IR104-M3 was successfully used for the preparation of Brivaracetam at gram scale.Using this mutant,various N-substituted amino amides/esters with two chiral centers were also synthesized with up to 99:1 d.r.and 96%yields and subsequently converted intoγ-andδ-lactams,providing an efficient protocol for the synthesis of these important compounds via enzymatic dynamic kinetic resolution-reductive amination from simple building blocks.展开更多
The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it ...The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52473080,52403167 and 52173079)the Fundamental Research Funds for the Central Universities(Nos.xtr052023001 and xzy012023037)+1 种基金the Postdoctoral Research Project of Shaanxi Province(No.2024BSHSDZZ054)the Shaanxi Laboratory of Advanced Materials(No.2024ZY-JCYJ-04-12).
文摘Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability of the triazine ring structure within cyanate ester(CE)crosslinked networks after molding posed significant challenges for both recycling,repairing,and degradation of resin.To address these obstacles,dynamic thiocyanate ester(TCE)bonds and photocurable group were incorporated into CE,obtaining the recyclable and 3D printable CE covalent adaptable networks(CANs),denoted as PTCE1.5.This material exhibits a Young's modulus of 810 MPa and a tensile strength of 50.8 MPa.Notably,damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment.Leveraging the solid-state plasticity,PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability,enabling its reconfigurable 4D printing.The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model,validating its potential application as a controllable component in the aerospace field.Moreover,printed PTCE1.5 can be fully degraded into thiol-modified intermediate products.Overall,this material not only enriches the application range of CE resin,but also provides a reliable approach to addressing environmental issue.
基金supported by the National Natural Science Foundation of China(No.51939009)Shenzhen Science and Technology Program(Nos.JCYJ20241202125905008 and GXWD20201231165807007-20200810165349001).
文摘A trace analytical method based on solid-phase extraction gas chromatography-tandem mass spectrometry(SPE–GC–MS/MS)was developed for the rapid detection of 256 semi-volatile organic compounds(SVOCs),including 25 polycyclic aromatic hydrocarbons(PAHs),70 polychlorinated biphenyls(PCBs),123 pesticides,20 phthalate esters(PAEs),4 organophosphate esters(OPEs),9 synthetic musks(SMs),and 5 UV filters(UVs)in water.No-tably,this method provided a decent linearity of calibration standards(R^(2)>0.999),excellent method limits of quantification(MLOQs)(0.12–11.41 ng/L),satisfactory matrix spiking recovery rates(60.4%–126%),and high precision(intra-day relative standard deviations(RSDs):1.0%–10.0%,inter-day RSDs:3.0%–15.0%,and inter-week RSDs:3.4%–15.7%),making it suitable for trace-level studies.Statistical analysis revealed that SVOCs with higher volatility exhibited enhanced recovery rates.Validation of the methodology involved analyzing SVOCs in real spring water and river water samples.Twenty-seven SVOCs were detected in spring water and 58 in river water,with an average concentration of 631.73 and 16,095 ng/L,respectively.Among the detected SVOCs,PAEs constituted the predominant proportion.This study underscored the presence of SVOCs contamination specifi-cally within the spring water,although SVOCs concentrations in river water were significantly greater than those found in spring water.In summary,this sensitive method based on SPE–GC–MS/MS was successfully developed and validated for the rapid analysis of a diverse array of 256 SVOCs at trace levels in water,including not only the traditional highly valued PAHs,PCBs,pesticides,and PAEs,but also the emerging OPEs,UVs,and SMs.
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.
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 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 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.21976169)the National Key Research and Development Program of China(No.2022YFC3702800).
文摘To explore the multicenter characteristics of endocrine-like phthalate esters(PAEs)in household dust and propose effective control strategies for global indoor public health.An on-site observational investigation was conducted in nine Chinese cities from 2018 to 2019.A total of 246 household dust sampleswere collected and analyzed for ten PAE congeners using Gas Chromatography-Mass Spectrometry(GC-MS).Questionnaires were used to gather information on building conditions,indoor behaviors,and ventilation habits.In residential dust from the nine cities,the total concentrations of the ten PAE congeners(PAEs)ranged from 0.921 to 29097.297μg/g.Dicyclohexyl phthalate(DCHP)and di(2-ethylhexyl)phthalate(DEHP)were the dominant congeners inPAEs.Childhood exposure to PAEs through dust ingestion was four orders of magnitude higher than through inhalation,with a carcinogenic risk of 5.47×10^(−6) for DEHP exposure in household dust.HigherPAEs concentrations were associated with higher temperature,double glazing,wall paint usage,television and computer use,and indoor plant growth.This multicenter on-site investigation confirmed PAE pollution characteristics and uncovered the inacceptable risk of daily DEHP exposure in household dust under real living conditions.Effective mitigation measures based on household-related information,residential characteristics,decoration materials,and lifestyle should be taken to build a healthy household environment.
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the financial support from the Key R&D Projects of Hainan Province(No.ZDYF2024SHFZ065)the Cultivation Research Foundation of Hainan Medical University(No.RZ2300002021 to Dulin Kong,No.RZ2400001591 to Guangkuan Zhao)the Postgraduate Innovation Project of Hainan Medical University(No.HYYB2023A07 to Wenyan Wei)。
文摘An efficient synthesis of α-thioenamine compounds via a K_(2)S_(2)O_(8)-promoted cross-dehydrogenative coupling reaction between heterocyclic thiols and enamine esters in an aqueous medium has been developed.The reaction showed good tolerance for enamine esters and heterocyclic thiols with various functional groups,producingα-thioenamine derivatives in moderate to high yields.Mechanistic studies revealed that heterocyclic thiols react with K_(2)S_(2)O_(8) in water to form reactive disulfides in situ,which then react with enamine esters to generate a series ofα-thioenamines.Building on the proposed mechanism,we developed a sulfenylation reaction of enamine esters with disulfides without the need for an oxidant.This oxidant-free approach has been successfully employed to synthesize DNA-taggedα-thioenamine,demonstrating its considerable potential for various synthetic applications.
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.22171090,21871090)National Key Research and Development Program of China(No.2020YFA0710200)+1 种基金the Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD37)the Fundamental Research Funds for the Central Universities are highly appreciated。
文摘Here,we report a novel nickel-catalyzed electrochemical carboxylation of propargylic esters with CO_(2),characterized by the regioselective synthesis of 2,3-allenoic acids rather than propargylic carboxylic acids.Both acyclic propargylic esters and cyclic propargylic carbonates serve as effective substrates,facilitating the synthesis of mono-,di-,tri-,and tetra-substituted 2,3-allenoic acids with broad substrate scope under mild conditions.Mechanistic investigations indicate that the in situ generated Ni(Ⅰ)complex might serve as the active species to react with propargylic esters,forming the allenyl-Ni(Ⅰ)complex under electroreductive conditions.A possible γ-selective nucleophilic attack of allenyl-Ni(Ⅰ)complex on CO_(2) is likely involved in the formation of the desired 2,3-allenoic acids.
基金Supported by the State Key Laboratory of Marine Pollution(SKLMP)in City University of Hong Kong,the Shenzhen Science and Technology Program(No.JCYJ20220530140813030 to Meng YAN)the Innovation and Technology Commission(ITC)of the Hong Kong SAR Government(No.9448002),which provides regular research funding support to SKLMP。
文摘Contamination of microplastics(MPs)and their associated plastic additives in the marine environment is a global concern due to their widespread distribution and toxicity to aquatic life.Although polyvinyl chloride(PVC)materials are commonly used in aquaculture environments,the potential risks of PVC MPs and the release of their additives in aquatic environments and organisms remain largely unknown.In this study,we investigated the leaching behaviors of phthalate esters(PAEs),including the mass and composition of PAEs in PVC MPs and their leaching kinetics,and evaluated the environmental risks of using PVC canvas in aquaculture activities.It was found that diethyl phthalate(DEP)was the most dominant PAE compound leached from PVC MPs(44.70±7.87 ng/g),followed by dimethyl phthalate(DMP,24.40±1.56 ng/g).The Elovich model was applied to simulate the leaching kinetics,and the simulated curves showed similar logarithmic trends that PAEs rapidly migrated from MPs to the water column at first and followed by a gradual increase over time.The different leaching kinetics of PAEs can be explained by their chemical properties,such as water solubility,molecular weight,and octanol-water partition coefficient.Compounds with lower solubility showed higher leaching coefficients,which are the constants of different PAEs in Elovich equation.Considering the potential joint toxicity of PVC leachates and the importance of food security,it is recommended to use PVC products responsibly and manage plastic waste properly.
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 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financially supported by Guangdong Major Project of Basic Research(No.2023B0303000002)Shenzhen Science and Technology Plan Project(No.SGDX20230116091644003)+1 种基金Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001)High level of special funds(No.G03034K001)
文摘Aqueous zinc-ion batteries(AZIBs)have garnered significant attention owing to their intrinsic safety and the abundance of zinc resources.Traditional separators,such as glass fiber(GF),face challenges such as zinc dendrite penetration,inadequate mechanical strength,and excessive thickness,which results in increased internal resistance and diminished battery performance.In this study,we investigate the use of a mixed cellulose ester(MCE)filter membrane as a separator for AZIBs.The 110-μm-thick MCE separator exhibits a mechanical strength of 4.88 MPa,which is 12 times greater than that of the 325-μm-thick GF separator,and effectively resists zinc dendrite formation,even with a thinner design.Zn symmetric batteries utilizing the MCE separator exhibit a cycle time of 2700 h at 1 mA cm^(-2).The MCE separator,incorporating hydroxyl and nitrogen functional groups,promotes uniform zinc deposition and mitigates the formation of by-products on the zinc anode,thereby enhancing corrosion resistance.Zn‖MnO_(2) full batteries with the MCE separator demonstrate a specific capacity of 161 mAh g^(-1)at 1 A g^(-1),with a capacity retention of 80.1%after 500 cycles.Furthermore,Zn‖VO_(2) full cells employing the MCE separator exhibit excellent rate performance and cycling stability.At 0.25 A g^(-1),the Zn‖VO_(2)cell retains 86.9%of its capacity after 800 cycles,demonstrating a high capacity of 243 mAh g^(-1).This study offers novel insights into enhancing the performance of AZIBs through the selection of a low-cost,high-strength,and thin separator design.
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.
文摘Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In this study,IR104 from Streptomyces aureocirculatus was identified from 157 wild-type imine reductases for the synthesis of(S)-2-((R)-2-oxo-4-propylpyrrolidin-1-yl)butanamide(antiepileptic drug Brivaracetam)via dynamic kinetic resolution reductive amination from ethyl 3-formylhexanoate and(S)-2-aminobutylamide with high diastereoselectivity.To further improve the catalytic efficiency of IR104,its mutant D191E/L195I/E253S/M258A(M3)was identified by saturation mutagenesis and iterative combinatorial mutagenesis,which exhibited a 102-fold increase in the catalytic efficiency relative to that of wild-type enzyme and high diastereoselectivity(98:2 d.r.).Crystal structural analysis and molecular dynamics simulations provided some insights into the molecular basis for the improved activity of the mutant enzyme.The imine reductase identified in this study could accept chiral amino amides/esters as amino donors for the dynamic kinetic resolution reductive amination of racemicα-substituted aldehydo-esters,expanding the substrate scope of imine reductases in the dynamic kinetic resolution-reductive amination.Finally,IR104-M3 was successfully used for the preparation of Brivaracetam at gram scale.Using this mutant,various N-substituted amino amides/esters with two chiral centers were also synthesized with up to 99:1 d.r.and 96%yields and subsequently converted intoγ-andδ-lactams,providing an efficient protocol for the synthesis of these important compounds via enzymatic dynamic kinetic resolution-reductive amination from simple building blocks.
基金financially supported by the National Natural Science Foundation of China(No.52377025)。
文摘The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.
