Synthesizing 2-deoxyglycosides,prevalent motifs in bioactive molecules,presents significant challenges in stereocontrol and functional group tolerance.We report a metal-free,photo-induced O-glycosylation of glycals us...Synthesizing 2-deoxyglycosides,prevalent motifs in bioactive molecules,presents significant challenges in stereocontrol and functional group tolerance.We report a metal-free,photo-induced O-glycosylation of glycals using acridinium salts under visible light.This method effectively couples diverse glycals with both carboxylic acids and alcohols,providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility.The protocol exhibits highα-stereoselectivity with carboxylic acids and moderateα-selectivity with alcohols,enabling late-stage functionalization of complex molecules,including amino acids,peptides,and drugs.Mechanistic experiments implicate the possible involvement of radical intermediates,potentially operating via a chain reaction.Notably,2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro.This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.展开更多
The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids rema...The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids remains a central objective in peptide chemistry[1].Significant efforts have led to the discovery of numerous coupling agents,including both single-component and combined reagent systems.However,challenges such as high cost,limited commercial availability,un-desired racemization/epimerization,and potential safety hazards continue to hinder ideal peptide synthesis[2].展开更多
The carboxylation of alkynes with CO2 has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of ...The carboxylation of alkynes with CO2 has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of active supports,particularly the oxygen vacancy(Ov),in modulating C-H bond carboxylation remains unknown.Herein,ultra-small silver clusters and morphologically engineered CeO2 support(nanorods,nanocubes,and nano particles)were employed to construct Ag cluster/Ov synergistic catalyst,which exhibits variations in Oy concentration by an in situ auto-reduction method.The 0.197%Ag/CeO2-NR catalyst exhibited a high reaction rate for the phenylacetylene carboxylation reaction and the maximal silver utilization efficiency.The characterization and DFT calculations demonstrated that vacancies enhanced CO2 adsorption via polarization-induced molecular bending and C-O bond elongation.Positively charged Ag clusters induced by metal-support interactions serve as deprotonation activation centers for alkynes.This synergistic interplay between dual active sites efficiently facilitates the C(sp)-H carboxylation with CO2.These findings offer critical insights for the rational selection of active supports in designing efficient C-H carboxylation catalysts.展开更多
Under the background of the dual carbon strategy,upgrading CO2 electroreduction from C1 products to high-value C3 esters is an important direction for realizing its resource utilization and valorization.In this wor...Under the background of the dual carbon strategy,upgrading CO2 electroreduction from C1 products to high-value C3 esters is an important direction for realizing its resource utilization and valorization.In this work,Cu100In50 bimetallic catalysts supported on carboxylated carbon nanotubes were prepared,and a membrane-free paired electrolytic cell cascade system was constructed to achieve the directional conversion of CO2→CO→dimethyl carbonate(DMC).The catalyst exhibits enhanced CO supply and interfacial mass transfer capability,with the number of CO adsorption sites increased by 1.8 times and the methanol contact angle reduced from 22°to 8°.Electrochemical measurements show that the catalyst achieves a CO Faraday efficiency(FECO)of 60.9%at−1.8 V versus Ag/AgCl,whereas the FEH2 remains as low as 2.1%.In the cascade reaction,the FEDMC reaches 52.3%at−2.2 V and remains at 49.6%after 5 cycles.The system can also be extended to the electrosynthesis of diethyl carbonate(DEC),giving a FEDEC of 27.8%.In situ Raman spectroscopy combined with DFT calculations reveals that In doping shifts the d-band center of Cu by 0.38 eV,regulates the adsorption behavior of key intermediates,and suppresses HER,whereas carboxyl groups optimize the interfacial electronic structure and mass transfer behavior.This work provides an efficient catalytic strategy and mechanistic insight for the cascade valorization of CO2 into high-value carbonates.展开更多
In this study,electrochemical C-H carboxylation of benzylamines with CO2 was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mi...In this study,electrochemical C-H carboxylation of benzylamines with CO2 was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.展开更多
Weathered rare earth ores are an important strategic mineral resource in China,and they are the primary source of medium and heavy rare earths(MHRE).The efficient recovery of MHRE is of great significance from an indu...Weathered rare earth ores are an important strategic mineral resource in China,and they are the primary source of medium and heavy rare earths(MHRE).The efficient recovery of MHRE is of great significance from an industrial standpoint.In this study,fulvic acid(FA) was employed as a precipitant to investigate the precipitation of rare earth(RE).The results indicate that the precipitation rates(w) of RE range from89.69 wt% to 99.86 wt% with the pH of 9,the molar ratio of 2,and the temperature of 40℃,except for Lu3+,the w reaches 97.33 wt% with the pH of 9,the molar ratio of 3,and the temperature of 25 ℃.The w of RE in the ammonium acetate rare earth leaching solution ranges from 95.99 wt% to 98.54 wt%,with the MH/L of the rare earth distribution after precipitation increasing from 0.77 to 0.80.The use of FA as a precipitant is demonstrated to yield effective precipitation of RE,particularly those of MHRE.FA complexes with RE3+,where deprotonation of COO-increases the surface electron density of oxygen atoms,creating additional active sites for electron-deficient RE3+.The mechanism provides a theoretical basis for using carboxylic acid compounds as new precipitants.Further,a novel technology for FA complexation precipitation of RE from lignite extract is proposed.展开更多
The corrosion protection effect of aromatic carboxylates(benzoate,phthalate,isophthalate,terephthalate,1,2,4-benzoate,trimesate,and 1,2,4,5-benzenetetracarboxylate)in NaCl solution on AZ31 alloy has been investigated....The corrosion protection effect of aromatic carboxylates(benzoate,phthalate,isophthalate,terephthalate,1,2,4-benzoate,trimesate,and 1,2,4,5-benzenetetracarboxylate)in NaCl solution on AZ31 alloy has been investigated.The results reveal that the inhibition mechanism is attributed to the effect of the studied molecules on the protective properties of a thin inhibitor-Mg(OH)2/MgO layer formed on the Mg surface.Both the number and position of carboxylate groups on the benzene ring influence the inhibition efficiencies of these inhibitors.A flat-lying molecular configuration more effectively shields the Mg surface from corrosive media.The findings confirm that the inhibitor-stabilized Mg(OH)2/MgO layer effectively blocks Cl−ingress and ensures strong corrosion protection for AZ31 alloy.展开更多
Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis.Among the various strategies,metathesis reactions have emerged as powerful tools for constructing new molecular a...Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis.Among the various strategies,metathesis reactions have emerged as powerful tools for constructing new molecular architectures due to their well-established mechanisms.However,these reactions have largely been limited to the same types of covalent bonds,such asσ-σorπ-πbonds,leavingσ-πcross-metathesis reactions unexplored.Perhaps the bond redistribution between theσandπbonds is highly difficult due to the lack of p orbital inσbonds.Herein,we report the first example of a transition metal-freeσ-πcross-metathesis reaction that converts methyl ketones into the corresponding carboxylic acids along with the formation of 11H-benzo[b]fluoren-11-one.A comprehensive mechanistic investigation,supported by DFT calculations,was conducted to elucidate the unique reaction pathway.This study not only provides compelling evidence for the firstσ-πcross-metathesis reaction but also demonstrates the formation of a key oxetan-2-olate intermediate and its utility in organic transformations.This novel concept and strategy expand the scope of traditional metathesis reactions,offering new possibilities for selective C-C bond activation in a redox-neutral manner.展开更多
The generation of transient radical species via carbon–metal bond homolysis is extremely useful,which can be harnessed to promote useful and selective radical-type transformations by the combination of transition met...The generation of transient radical species via carbon–metal bond homolysis is extremely useful,which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis.We herein establish a carbon–metal bond homolysisecombination model for the formation of enantiomerically enriched carbon-metal species,which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2.Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0),forming a racemic benzyl Ni(Ⅱ)intermediate.Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical,followed by a dynamic rotation along C–C·bond and radical recombination forming another more thermodynamically favored enantiomer.Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer.After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2process,the desired enantiomerically enriched carboxylic acid product is generated.ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state,thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation.The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation,highlighting significant potential for broad applications in synthetic organic chemistry.展开更多
Flexible perovskite solar cells(f-PSCs)hold great promise for next-generation wearable electronics,portable power sources and even space power systems.However,these applications are fundamentally limited by optoelectr...Flexible perovskite solar cells(f-PSCs)hold great promise for next-generation wearable electronics,portable power sources and even space power systems.However,these applications are fundamentally limited by optoelectronic degradation under mechanical strain.Although incorporating continuous polymeric networks enhances mechanical robustness,these insulating dielectric materials inevitably introduce carrier-transport barriers,leading to severe charge accumulation and a compromised fill factor(FF).Herein,we introduce 50-nm carboxyl-functionalized polymethyl methacrylate nanospheres(CPNs)to fundamentally decouple mechanical stress dissipation from interfacial carrier transport kinetics in inverted f-PSCs.Unlike continuous dielectric buffer layers,the CPNs self-assemble into a discontinuous nano-island network at the buried interface,maintaining unobstructed conductive pathways for efficient cross-interfacial charge transfer.Mechanically,the elastic nano-islands modulate the local strain field to efficiently dissipate mechanical and thermal stresses.Furthermore,the localized electrostatic field induced by the negatively charged carboxyl groups spatially repels electrons and accelerates hole extraction,profoundly suppressing non-radiative interfacial recombination.Consequently,the optimized f-PSCs achieve a power conversion efficiency exceeding 26%with a remarkably high FF of 0.845.The devices demonstrate outstanding structural and operational stability,exhibiting negligible degradation after 5,000 bending cycles at a 6-mm radius and retaining 96.3%of their initial efficiency after 200 thermal cycles(−60 to+80℃).This work provides a robust micromechanical and optoelectronic strategy for highly reliable flexible photovoltaics.展开更多
In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using at...In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOHf)and hydrogen-bonded carboxyl(COOHHB,were directly correlated with the polar component of surface energy(γs,p).By decomposing theγs,pvalues of the PAA thin films as a sum of the contributions of COOHfand COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)s,p*)was quantified for the first time as 8.34 mN/m,significantly lower than that of COOHf(γfs,p*=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγs,p,providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm-2,COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.展开更多
Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron d...Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron donor because it can be generated from renewable resources,including lignocellulosic biomass and protein wastes.Here,propanol was proven in detail to be an efficient electron donor,enhancing the production of odd medium-chain carboxylates during chain elongation.By exploring various electron acceptors,reactor conditions,and electron donor/electron acceptor mol ratios,our study highlights that acetate is the most suitable electron acceptor for the production of both odd-and even-chain carboxylates.The optimal conditions for propanol-based chain elongation were 30℃ and pH 6,achieving 82.8%selectivity for odd-chain carboxylates.Another critical insight from our work is that a propanol/acetate mol ratio of 1:1 can minimize the inhibitory effect of propanol and maximize the yield of medium-chain carboxylates,with the highest concentration of n-heptanoate reaching 124.5 mmol C/L.This was further illustrated by 16S rRNA amplicon sequencing,which elucidated that the community composition and keystone species in a propanol-based reactor closely resembled that of the ethanol one.The dominant phylum of the propanol-based reactor,Firmicutes showed a significant positive correlation with the concentrations of n-caproate and n-valerate.Additionally,the co-occurrence of Clostridium sensu stricto 12 and Oscillibacter,known as typical chain elongators,was identified within the propanol-based reactor.These findings enhance our understanding of propanolbased chain elongation,offer guiding principles for reactor microbiota assembly,and support efficient odd medium-chain carboxylate production.展开更多
A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO2 with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assig...A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO2 with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO2.The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβn(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔEint(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.展开更多
The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed...The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed to investigate the neuroprotective effect of overexpressed CHIP on Alzheimer’s disease.We used an adeno-associated virus vector that can cross the blood-brain barrier to mediate CHIP overexpression in APP/PS1 mouse brain.CHIP overexpression significantly ameliorated the performance of APP/PS1 mice in the Morris water maze and nest building tests,reduced amyloid-βplaques,and decreased the expression of both amyloid-βand phosphorylated tau.CHIP also alleviated the concentration of microglia and astrocytes around plaques.In APP/PS1 mice of a younger age,CHIP overexpression promoted an increase in ADAM10 expression and inhibitedβ-site APP cleaving enzyme 1,insulin degrading enzyme,and neprilysin expression.Levels of HSP70 and HSP40,which have functional relevance to CHIP,were also increased.Single nuclei transcriptome sequencing in the hippocampus of CHIP overexpressed mice showed that the lysosomal pathway and oligodendrocyte-related biological processes were up-regulated,which may also reflect a potential mechanism for the neuroprotective effect of CHIP.Our research shows that CHIP effectively reduces the behavior and pathological manifestations of APP/PS1 mice.Indeed,overexpression of CHIP could be a beneficial approach for the treatment of Alzheimer’s disease.展开更多
Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C12(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca2+)in THF/H2O soluti...Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C12(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca2+)in THF/H2O solution.The assembly and fluorescence behavior of PDI-COOH/Ca2+were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca2+,we proposed the fluorescence emission mechanism of PDI-COOH/Ca2+in THF/H2O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.展开更多
Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidate...Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidated.Under optimal conditions,the addition of AEC-9Na with a mass fraction of 0.03% can enhance the leaching rate by 5.2% and reduce the leaching cycle.Kinetic analysis demonstrates that the leaching process follows the model of internal diffusion control.The analysis of the mass transfer process reveals that the addition of AEC-9Na results in a decrease in the height equivalent to a theoretical plate(HETP)and an improvement in mass transfer efficiency.The addition of AEC-9Na can reduce the thickness of the water layer adsorbed on particles during leaching,which in turn reduces hydration and facilitates penetration of the leaching solution into ore body pores.This improves mass transfer concentration differences during leaching,and facilitates desorption of rare earth ions.Periodic density functional theory(DFT)calculations show that the adsorption of AEC-9Na onto the surface of kaolinite(001)enhances the hydrophilicity of the mineral surface and improves its permeability efficiency.Simultaneously,AEC-9Na forms complexes with hydrated rare earth ions on the kaolinite(001)surface,thereby reducing their adsorption strength on clay minerals.This promotes the exchange and desorption process of magnesium ions to hydrated rare earth ions,ultimately enhancing the mass transfer process for leaching rare earth elements.展开更多
This research investigated the acidogenic fermentation(AF)of sugar cane molasses in an up-flow anaerobic sludge blanket(UASB)reactor for the production of carboxylates.The first step was to assess the optimum process ...This research investigated the acidogenic fermentation(AF)of sugar cane molasses in an up-flow anaerobic sludge blanket(UASB)reactor for the production of carboxylates.The first step was to assess the optimum process temperature(25,35 or 55℃)using two different granular inocula,one from a brewery company(BGS)and other from a paper plant company(PGS).These experiments determined that the most suitable temperature for carboxylates production was 25℃,obtaining higher bioconversions(27.3±0.3%using PGS and 39.2±0.2%using BGS),despite the low pH value recorded(4.0-4.2).Then,both inocula were tested in UASB reactors.As a consequence of the operational conditions(25℃,pH=5.5-6,organic loading rate(OLR)=3 gCOD·L-1·d-1 and hydraulic retention time(HRT)=10 d),the microbial communities changed from those typical for biogas production to those specialised in the production of volatile fatty acids(VFAs).Indeed,the highest bioconversion efficiency(70.1%)was obtained with BGS,where uncultured Eubacteriaceae family microorganisms(56.0%)prevailed,enhancing the production of butyric acid(59.5±2.4%w/w).Consequently,this inoculum was used to further identify the OLR threshold that should not be exceeded to attain optimal carboxylates production.OLR of 6 gCOD·L-1·d-1 resulted in a decrease in bioconversion efficiency(59.5%).The VFAs pool was dominated by butyric acid(63.0±1.4%w/w at an OLR of 4.5 gCOD·L-1·d-1 and 52.8±2.2%w/w at 6 gCOD·L-1·d-1).The microbial community became even more specialised,increasing the presence of Firmicutes and Actinobacteriota phyla,proving that the imposed conditions favoured the production of VFAs when operating semicontinuously fed UASB reactors.展开更多
An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acylox...An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.展开更多
Molecular structures of polycarboxylate(PCE) superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic dens...Molecular structures of polycarboxylate(PCE) superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P(PEG1-AA6) possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.展开更多
As an attractive C1 synthon,carbon dioxide(CO2)has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones ...As an attractive C1 synthon,carbon dioxide(CO2)has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones has been developed under transition-metal-free conditions.All the cinnamic acids and the derivatives are obtained selectively in the E-configuration.Besides,arylpropiolates also can be produced from alkynyl sulfones.展开更多
基金financial support from the National Natural Science Foundation of China(No.22171231)Zhejiang Provincial Key Laboratory Construction Project+1 种基金Zhejiang Provincial Natural Science Foundation of China(No.XHD23B0101)National Natural Science Foundation of China(No.82471531)。
摘要Synthesizing 2-deoxyglycosides,prevalent motifs in bioactive molecules,presents significant challenges in stereocontrol and functional group tolerance.We report a metal-free,photo-induced O-glycosylation of glycals using acridinium salts under visible light.This method effectively couples diverse glycals with both carboxylic acids and alcohols,providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility.The protocol exhibits highα-stereoselectivity with carboxylic acids and moderateα-selectivity with alcohols,enabling late-stage functionalization of complex molecules,including amino acids,peptides,and drugs.Mechanistic experiments implicate the possible involvement of radical intermediates,potentially operating via a chain reaction.Notably,2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro.This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
摘要The formation of peptide bonds is a crucial step in peptide synthesis and their long-term application across diverse fields.Therefore,identifying effective coupling reagents to activate carboxylic and amino acids remains a central objective in peptide chemistry[1].Significant efforts have led to the discovery of numerous coupling agents,including both single-component and combined reagent systems.However,challenges such as high cost,limited commercial availability,un-desired racemization/epimerization,and potential safety hazards continue to hinder ideal peptide synthesis[2].
基金financially supported by the National Natural Science Foundation of China(22102194)the Science and Technology Plan of Gansu Province(24JRRA067,23ZDFA016)the Youth Innovation Promotion Association of CAS(2022427)。
摘要The carboxylation of alkynes with CO2 has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of active supports,particularly the oxygen vacancy(Ov),in modulating C-H bond carboxylation remains unknown.Herein,ultra-small silver clusters and morphologically engineered CeO2 support(nanorods,nanocubes,and nano particles)were employed to construct Ag cluster/Ov synergistic catalyst,which exhibits variations in Oy concentration by an in situ auto-reduction method.The 0.197%Ag/CeO2-NR catalyst exhibited a high reaction rate for the phenylacetylene carboxylation reaction and the maximal silver utilization efficiency.The characterization and DFT calculations demonstrated that vacancies enhanced CO2 adsorption via polarization-induced molecular bending and C-O bond elongation.Positively charged Ag clusters induced by metal-support interactions serve as deprotonation activation centers for alkynes.This synergistic interplay between dual active sites efficiently facilitates the C(sp)-H carboxylation with CO2.These findings offer critical insights for the rational selection of active supports in designing efficient C-H carboxylation catalysts.
基金financially supported by the National Natural Science Foundation of China(Grant 52360003).
摘要Under the background of the dual carbon strategy,upgrading CO2 electroreduction from C1 products to high-value C3 esters is an important direction for realizing its resource utilization and valorization.In this work,Cu100In50 bimetallic catalysts supported on carboxylated carbon nanotubes were prepared,and a membrane-free paired electrolytic cell cascade system was constructed to achieve the directional conversion of CO2→CO→dimethyl carbonate(DMC).The catalyst exhibits enhanced CO supply and interfacial mass transfer capability,with the number of CO adsorption sites increased by 1.8 times and the methanol contact angle reduced from 22°to 8°.Electrochemical measurements show that the catalyst achieves a CO Faraday efficiency(FECO)of 60.9%at−1.8 V versus Ag/AgCl,whereas the FEH2 remains as low as 2.1%.In the cascade reaction,the FEDMC reaches 52.3%at−2.2 V and remains at 49.6%after 5 cycles.The system can also be extended to the electrosynthesis of diethyl carbonate(DEC),giving a FEDEC of 27.8%.In situ Raman spectroscopy combined with DFT calculations reveals that In doping shifts the d-band center of Cu by 0.38 eV,regulates the adsorption behavior of key intermediates,and suppresses HER,whereas carboxyl groups optimize the interfacial electronic structure and mass transfer behavior.This work provides an efficient catalytic strategy and mechanistic insight for the cascade valorization of CO2 into high-value carbonates.
基金Financial support from National Key R&D Program of China (No.2023YFA1507203)National Natural Science Foundation of China (Nos.22371149 and 22188101)+3 种基金the Fundamental Research Funds for the Central Universities (No.63224098)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206)Nankai University are gratefully acknowledgedthe Haihe Laboratory of Sustainable Chemical Transformations for financial support。
摘要In this study,electrochemical C-H carboxylation of benzylamines with CO2 was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.
基金Project supported by the National Natural Science Foundation of China (52222405,92475206,92162109,52074195)the Natural Science Foundation Innovation Group Project of Hubei Province (2023AFA044)
摘要Weathered rare earth ores are an important strategic mineral resource in China,and they are the primary source of medium and heavy rare earths(MHRE).The efficient recovery of MHRE is of great significance from an industrial standpoint.In this study,fulvic acid(FA) was employed as a precipitant to investigate the precipitation of rare earth(RE).The results indicate that the precipitation rates(w) of RE range from89.69 wt% to 99.86 wt% with the pH of 9,the molar ratio of 2,and the temperature of 40℃,except for Lu3+,the w reaches 97.33 wt% with the pH of 9,the molar ratio of 3,and the temperature of 25 ℃.The w of RE in the ammonium acetate rare earth leaching solution ranges from 95.99 wt% to 98.54 wt%,with the MH/L of the rare earth distribution after precipitation increasing from 0.77 to 0.80.The use of FA as a precipitant is demonstrated to yield effective precipitation of RE,particularly those of MHRE.FA complexes with RE3+,where deprotonation of COO-increases the surface electron density of oxygen atoms,creating additional active sites for electron-deficient RE3+.The mechanism provides a theoretical basis for using carboxylic acid compounds as new precipitants.Further,a novel technology for FA complexation precipitation of RE from lignite extract is proposed.
基金partially supported by AI2.Eyesight to AI:Discovery of efficient corrosion modulators via predictive machine learning models,2020-2023(Funded by HGF)Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)-project number 535656357,OPTIMA(Identification of optimal corrosion inhibitors for bare and PEO coated magnesium alloy by combining machine learning and robotic testing)China Scholarship Council for the award of fellowship and funding,correspondingly No.202008410217,No.202106050030,and 202406820008.
摘要The corrosion protection effect of aromatic carboxylates(benzoate,phthalate,isophthalate,terephthalate,1,2,4-benzoate,trimesate,and 1,2,4,5-benzenetetracarboxylate)in NaCl solution on AZ31 alloy has been investigated.The results reveal that the inhibition mechanism is attributed to the effect of the studied molecules on the protective properties of a thin inhibitor-Mg(OH)2/MgO layer formed on the Mg surface.Both the number and position of carboxylate groups on the benzene ring influence the inhibition efficiencies of these inhibitors.A flat-lying molecular configuration more effectively shields the Mg surface from corrosive media.The findings confirm that the inhibitor-stabilized Mg(OH)2/MgO layer effectively blocks Cl−ingress and ensures strong corrosion protection for AZ31 alloy.
基金financial support from the National Natural Science Foundation of China(No.22061012)the Guizhou Provincial Excellent Young Talents Plan(No.YQK[2023]030)+2 种基金the Excellent Young Talents Plan of Guizhou Medical University(Nos.[2023]105,[2022]102)GMU Training Program of National Natural Science Foundation of China(No.22NSFCP13)the support from National-Local Joint Engineering Research Center for Innovative&Generic Chemical Drug&Guizhou Province Innovation Base of Common Major Chronic Disease Pathogenesis and Drug Development and Application(No.[2021]4029)。
摘要Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis.Among the various strategies,metathesis reactions have emerged as powerful tools for constructing new molecular architectures due to their well-established mechanisms.However,these reactions have largely been limited to the same types of covalent bonds,such asσ-σorπ-πbonds,leavingσ-πcross-metathesis reactions unexplored.Perhaps the bond redistribution between theσandπbonds is highly difficult due to the lack of p orbital inσbonds.Herein,we report the first example of a transition metal-freeσ-πcross-metathesis reaction that converts methyl ketones into the corresponding carboxylic acids along with the formation of 11H-benzo[b]fluoren-11-one.A comprehensive mechanistic investigation,supported by DFT calculations,was conducted to elucidate the unique reaction pathway.This study not only provides compelling evidence for the firstσ-πcross-metathesis reaction but also demonstrates the formation of a key oxetan-2-olate intermediate and its utility in organic transformations.This novel concept and strategy expand the scope of traditional metathesis reactions,offering new possibilities for selective C-C bond activation in a redox-neutral manner.
基金supported by the National Key R&D Program of China(No.2024YFA1509703)National Natural Science Foundation of China(Nos.22473081 and 22201027)+3 种基金Fundamental Research Funds from Sichuan University(No.2020SCUNL102)Sichuan Science and Technology Program(No.2025ZNSFSC0911)Sichuan University Interdisciplinary Innovation Fundthe Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University。
摘要The generation of transient radical species via carbon–metal bond homolysis is extremely useful,which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis.We herein establish a carbon–metal bond homolysisecombination model for the formation of enantiomerically enriched carbon-metal species,which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2.Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0),forming a racemic benzyl Ni(Ⅱ)intermediate.Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical,followed by a dynamic rotation along C–C·bond and radical recombination forming another more thermodynamically favored enantiomer.Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer.After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2process,the desired enantiomerically enriched carboxylic acid product is generated.ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state,thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation.The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation,highlighting significant potential for broad applications in synthetic organic chemistry.
基金supported by the National Natural Science Foundation of China(Grant Nos.U24A6003,52361145847,52227803)`the Beijing Natural Science Foundation-Huairou Innovation Joint Funding(Grant No.L245005).
摘要Flexible perovskite solar cells(f-PSCs)hold great promise for next-generation wearable electronics,portable power sources and even space power systems.However,these applications are fundamentally limited by optoelectronic degradation under mechanical strain.Although incorporating continuous polymeric networks enhances mechanical robustness,these insulating dielectric materials inevitably introduce carrier-transport barriers,leading to severe charge accumulation and a compromised fill factor(FF).Herein,we introduce 50-nm carboxyl-functionalized polymethyl methacrylate nanospheres(CPNs)to fundamentally decouple mechanical stress dissipation from interfacial carrier transport kinetics in inverted f-PSCs.Unlike continuous dielectric buffer layers,the CPNs self-assemble into a discontinuous nano-island network at the buried interface,maintaining unobstructed conductive pathways for efficient cross-interfacial charge transfer.Mechanically,the elastic nano-islands modulate the local strain field to efficiently dissipate mechanical and thermal stresses.Furthermore,the localized electrostatic field induced by the negatively charged carboxyl groups spatially repels electrons and accelerates hole extraction,profoundly suppressing non-radiative interfacial recombination.Consequently,the optimized f-PSCs achieve a power conversion efficiency exceeding 26%with a remarkably high FF of 0.845.The devices demonstrate outstanding structural and operational stability,exhibiting negligible degradation after 5,000 bending cycles at a 6-mm radius and retaining 96.3%of their initial efficiency after 200 thermal cycles(−60 to+80℃).This work provides a robust micromechanical and optoelectronic strategy for highly reliable flexible photovoltaics.
摘要In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOHf)and hydrogen-bonded carboxyl(COOHHB,were directly correlated with the polar component of surface energy(γs,p).By decomposing theγs,pvalues of the PAA thin films as a sum of the contributions of COOHfand COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)s,p*)was quantified for the first time as 8.34 mN/m,significantly lower than that of COOHf(γfs,p*=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγs,p,providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm-2,COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.
基金supported by the National Key R&D Program of China(No.2022YFC2105301)the National Natural Science Foundation of China(No.52270096).
摘要Microbial consortia that catalyze chain elongation processes have been enriched using different selection strategies,for which the electron donor is an essential one.Propanol is an extraordinarily promising electron donor because it can be generated from renewable resources,including lignocellulosic biomass and protein wastes.Here,propanol was proven in detail to be an efficient electron donor,enhancing the production of odd medium-chain carboxylates during chain elongation.By exploring various electron acceptors,reactor conditions,and electron donor/electron acceptor mol ratios,our study highlights that acetate is the most suitable electron acceptor for the production of both odd-and even-chain carboxylates.The optimal conditions for propanol-based chain elongation were 30℃ and pH 6,achieving 82.8%selectivity for odd-chain carboxylates.Another critical insight from our work is that a propanol/acetate mol ratio of 1:1 can minimize the inhibitory effect of propanol and maximize the yield of medium-chain carboxylates,with the highest concentration of n-heptanoate reaching 124.5 mmol C/L.This was further illustrated by 16S rRNA amplicon sequencing,which elucidated that the community composition and keystone species in a propanol-based reactor closely resembled that of the ethanol one.The dominant phylum of the propanol-based reactor,Firmicutes showed a significant positive correlation with the concentrations of n-caproate and n-valerate.Additionally,the co-occurrence of Clostridium sensu stricto 12 and Oscillibacter,known as typical chain elongators,was identified within the propanol-based reactor.These findings enhance our understanding of propanolbased chain elongation,offer guiding principles for reactor microbiota assembly,and support efficient odd medium-chain carboxylate production.
基金the National Key R&D Program of China(No.2022YFB4101900)National Natural Science Foundation of China(Nos.22278305,U21B2096)Natural Science Foundation of Tianjin City(No.23JCZDJC00040)。
摘要A strategy for copper-catalyzed and biphosphine ligand controlled boracarboxylation of 1,3-dienes and CO2 with 3,4-selectivity was developed.The Cu Cl coupled with DPPF(1,1-bis(diphenylphosphino)ferrocene)was assigned to be the best catalyst,with 84%yield and exclusive3,4-selectivity.The ligand effect on both catalytic activity and regioselectivity of boracarboxylation was disclosed,which is rarely reported in any copper catalyzed boracarboxylation.The borocupration process is revealed to be a vital step for the biphosphine participated boracarboxylation of 1,3-dienes with CO2.The minimal substrate distortion occurring in 3,4-borocupration favors the 3,4-regioselectivity of boracarboxylation.The“pocket”confinement and suitableβn(92°–106°)of bisphosphine ligands are demonstrated to be in favour of the interaction between LCu-Bpin complex(the catalytic precursor)and1,3-diene substrate to decrease their interaction energyΔEint(ζ)in 3,4-borocupration,thus promoting the 3,4-boracarboxylation.
基金supported by the National Natural Science Foundation of China,Nos.91849115 and U1904207(to YX),81974211 and 82171247(to CS)Non-profit Central Research Institute Fund of Chinese Academy of Medical Sciences,No.2020-PT310-01(to YX).
摘要The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed to investigate the neuroprotective effect of overexpressed CHIP on Alzheimer’s disease.We used an adeno-associated virus vector that can cross the blood-brain barrier to mediate CHIP overexpression in APP/PS1 mouse brain.CHIP overexpression significantly ameliorated the performance of APP/PS1 mice in the Morris water maze and nest building tests,reduced amyloid-βplaques,and decreased the expression of both amyloid-βand phosphorylated tau.CHIP also alleviated the concentration of microglia and astrocytes around plaques.In APP/PS1 mice of a younger age,CHIP overexpression promoted an increase in ADAM10 expression and inhibitedβ-site APP cleaving enzyme 1,insulin degrading enzyme,and neprilysin expression.Levels of HSP70 and HSP40,which have functional relevance to CHIP,were also increased.Single nuclei transcriptome sequencing in the hippocampus of CHIP overexpressed mice showed that the lysosomal pathway and oligodendrocyte-related biological processes were up-regulated,which may also reflect a potential mechanism for the neuroprotective effect of CHIP.Our research shows that CHIP effectively reduces the behavior and pathological manifestations of APP/PS1 mice.Indeed,overexpression of CHIP could be a beneficial approach for the treatment of Alzheimer’s disease.
摘要Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C12(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca2+)in THF/H2O solution.The assembly and fluorescence behavior of PDI-COOH/Ca2+were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca2+,we proposed the fluorescence emission mechanism of PDI-COOH/Ca2+in THF/H2O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.
基金Project supported by the National Natural Science Foundation Regional Innovation Development Joint Fund(U24A2096)。
摘要Surfactant sodium alcohol ether carboxylate(AEC-9Na)was added to the magnesium sulfate solution in order to enhance the leaching efficiency of ionic rare earth ore,and the mechanism of action for AEC-9Na was elucidated.Under optimal conditions,the addition of AEC-9Na with a mass fraction of 0.03% can enhance the leaching rate by 5.2% and reduce the leaching cycle.Kinetic analysis demonstrates that the leaching process follows the model of internal diffusion control.The analysis of the mass transfer process reveals that the addition of AEC-9Na results in a decrease in the height equivalent to a theoretical plate(HETP)and an improvement in mass transfer efficiency.The addition of AEC-9Na can reduce the thickness of the water layer adsorbed on particles during leaching,which in turn reduces hydration and facilitates penetration of the leaching solution into ore body pores.This improves mass transfer concentration differences during leaching,and facilitates desorption of rare earth ions.Periodic density functional theory(DFT)calculations show that the adsorption of AEC-9Na onto the surface of kaolinite(001)enhances the hydrophilicity of the mineral surface and improves its permeability efficiency.Simultaneously,AEC-9Na forms complexes with hydrated rare earth ions on the kaolinite(001)surface,thereby reducing their adsorption strength on clay minerals.This promotes the exchange and desorption process of magnesium ions to hydrated rare earth ions,ultimately enhancing the mass transfer process for leaching rare earth elements.
基金supported by the grant PRE2020-094485 funded by MCIN/AEI/10.13039/501100011033 and by“ESF Investing in your future.”。
摘要This research investigated the acidogenic fermentation(AF)of sugar cane molasses in an up-flow anaerobic sludge blanket(UASB)reactor for the production of carboxylates.The first step was to assess the optimum process temperature(25,35 or 55℃)using two different granular inocula,one from a brewery company(BGS)and other from a paper plant company(PGS).These experiments determined that the most suitable temperature for carboxylates production was 25℃,obtaining higher bioconversions(27.3±0.3%using PGS and 39.2±0.2%using BGS),despite the low pH value recorded(4.0-4.2).Then,both inocula were tested in UASB reactors.As a consequence of the operational conditions(25℃,pH=5.5-6,organic loading rate(OLR)=3 gCOD·L-1·d-1 and hydraulic retention time(HRT)=10 d),the microbial communities changed from those typical for biogas production to those specialised in the production of volatile fatty acids(VFAs).Indeed,the highest bioconversion efficiency(70.1%)was obtained with BGS,where uncultured Eubacteriaceae family microorganisms(56.0%)prevailed,enhancing the production of butyric acid(59.5±2.4%w/w).Consequently,this inoculum was used to further identify the OLR threshold that should not be exceeded to attain optimal carboxylates production.OLR of 6 gCOD·L-1·d-1 resulted in a decrease in bioconversion efficiency(59.5%).The VFAs pool was dominated by butyric acid(63.0±1.4%w/w at an OLR of 4.5 gCOD·L-1·d-1 and 52.8±2.2%w/w at 6 gCOD·L-1·d-1).The microbial community became even more specialised,increasing the presence of Firmicutes and Actinobacteriota phyla,proving that the imposed conditions favoured the production of VFAs when operating semicontinuously fed UASB reactors.
摘要An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.
基金the State Key Laboratory of Silicate Materials for Architectures(SYSJJ2018-09)the Shaanxi Provincial High Performance Concrete Engineering Laboratory(SHPC201701)
摘要Molecular structures of polycarboxylate(PCE) superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P(PEG1-AA6) possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.
基金Financial support from the National Natural Science Foundation of China(No.21901041)the Fuzhou University(No.0041/511095)。
摘要As an attractive C1 synthon,carbon dioxide(CO2)has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones has been developed under transition-metal-free conditions.All the cinnamic acids and the derivatives are obtained selectively in the E-configuration.Besides,arylpropiolates also can be produced from alkynyl sulfones.