Medium-chain furanic chemicals have outstanding practical potential,especially in the application of pharmaceuticals and polymers.Herein,we describe an eco-friendly and efficient heterogeneous sodium-doped porous sodi...Medium-chain furanic chemicals have outstanding practical potential,especially in the application of pharmaceuticals and polymers.Herein,we describe an eco-friendly and efficient heterogeneous sodium-doped porous sodium manganese oxide catalyst(Na-MnO_(x)) for oxidative cleavage of furanic 1,2-diols into medium-chain furanic aldehyde compounds.Subsequently,various high value-added chemicals(diacids and esters,diols,hydroxy acids,acrylics) were synthesized based on the widely applicable and highly selective catalytic approaches.The Na-MnO_(x) was prepared by the coprecipitation method and characterized by XRD,SEM,XPS and FT-IR,and TGA.XPS revealed that Mn species existed in the mixed oxidation states Mn~Ⅱ,Mn~Ⅲ and Mn~Ⅳ.When NaOH concentration up to 1.8 mol L^(-1) during the preparation process of the catalyst,the ratio of Mn^(4+) in the catalyst was the highest,and the yield of product(Furan-2-acrolein) in the model reaction is also optimal.Overall,this protocol developed a novel and general route for the preparation of medium-chain furanic compounds utilizing cellulose-derived platform molecules.展开更多
The cyclopentanone and derivatives are a class of crucial fine chemicals for various industries and currently produced by conventional petrochemical synthetic routes.Here,we demonstrated a new synthetic approach to di...The cyclopentanone and derivatives are a class of crucial fine chemicals for various industries and currently produced by conventional petrochemical synthetic routes.Here,we demonstrated a new synthetic approach to directly fabricate N-doped carbon nanotube(N-CNTs)networks with confined Co nanoparticles from Co^(2+)-impregnated bulk g-C_(3)N_(4) as high performance hydrogenation rearrangement(HR)catalyst to efficiently convert a wide spectrum of biomass-derived furanic aldehydes to the corresponding cyclopentanones in water under a record-low H2 pressure of 0.5 MPa and mild temperature.We unveiled a Co-catalysed bulk g-C_(3)N_(4) decomposition/carbonisation CNTs formation mechanism.A new HR pathway was also unveiled.展开更多
The evaluation of toxicity related to polychlorinated dibenzo-p-dioxins and furans(PCDD/Fs)and dioxin-like polychlorinated biphenyls(DL-PCBs)is crucial for a comprehensive risk assessment in real-world exposure scenar...The evaluation of toxicity related to polychlorinated dibenzo-p-dioxins and furans(PCDD/Fs)and dioxin-like polychlorinated biphenyls(DL-PCBs)is crucial for a comprehensive risk assessment in real-world exposure scenarios.This study employed a controlled feeding experiment to investigate the metabolic effects of dioxin-like compounds(DLCs)on laying hens via feed exposure.Diets enriched with two concentrations(1.17 and 5.13 pg toxic equivalents(TEQ)/g dry weight(dw))were administered over 14 days,followed by 28 days of clean feed.Metabolomics analyses of blood samples revealed significant metabolic variations between PCDD/Fs and DL-PCBs exposed groups and controls,reflecting the induced metabolic disruption.Distinct changes were observed in sphingosine,palmitoleic acid,linoleate,linolenic acid,taurocholic acid,indole acrylic acid,and dibutyl phthalate levels,implying possible connections between PCDD/Fs and DL-PCBs toxic effects and energy-neuronal imbalances,along with lipid accumulation and anomalous amino acid metabolism,impacting taurine metabolism.Moreover,we identified three differential endogenous metabolites—L-tryptophan,indole-3-acetaldehyde,and indole acrylic acid—as potential ligands for the aryl hydrocarbon receptor(AhR),suggesting their role inmediating PCDD/Fs and DL-PCBs toxicity.This comprehensive investigation provides novel insights into the metabolic alterations induced by PCDD/Fs and DL-PCBs in laying hens,thereby enhancing our ability to assess risks associated with their exposure in human populations.展开更多
Primary diamines play an important role in the chemical industry,where they are widely used as raw materials for the manufacture of pharmaceuticals and polymers.Currently,primary diamines are mainly derived from petro...Primary diamines play an important role in the chemical industry,where they are widely used as raw materials for the manufacture of pharmaceuticals and polymers.Currently,primary diamines are mainly derived from petroleum,while harsh or toxic conditions are often needed.Biomass is abundant and renewable,which serves as a promising alternative raw material to produce primary diamines.This review primarily focuses on the synthesis of 2,5-bis(aminomethyl)furan(BAMF),a bio-based diamine with potential as a biomonomer for polyamides and polyureas.Specifically,this review emphasizes the synthesis of BAMF fromthree biomass-derived alcohols and aldehydes,namely 5-hydroxymethylfurfural(HMF),2,5-bis(hydroxymethyl)furan(BHMF),and 2,5-diformylfuran(DFF).These are the key substrates to get BAMF and could be readily obtained from carbohydrates.Even though great effort has been put into the synthesis of BAMF,it remains a tough problem to obtain BAMF with a high yield at a low cost due to the inevitable side reactions,such as unwanted hydrogenation reactions and condensation reactions.Many strategies have been proposed to solve this problem,such as the hydrogen-borrowing strategy and stepwise reductive amination strategy.Herein,we will summarize the key advancements in this area,and discuss the challenges that need to be responded in the future,hoping to provide an insight into the design and development of a more efficient system for the production of biomass-derived diamines.展开更多
An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthrolin...An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.展开更多
The emerging biomass-based epoxy vitrimers hold great potential to fulfill the requirements for sustainable development of society.Since the existence of dynamic chemical bonds in vitrimers often reduces both the ther...The emerging biomass-based epoxy vitrimers hold great potential to fulfill the requirements for sustainable development of society.Since the existence of dynamic chemical bonds in vitrimers often reduces both the thermal and mechanical properties of epoxy resins, it is challenging to produce recyclable epoxy vitrimers with both excellent mechanical properties and good thermal stability. Herein, a monomer 4-(((5-(hydroxymethyl)furan-2-yl)methylene)amino)phenol(FCN) containing furan ring with potential to form high density of hydrogen bonding among repeating units is designed and copolymerized with glycerol triglycidyl ether to yield epoxy resin(FCN-GTE), which intrinsically has dual hydrogen bond networks, dynamic imine structure and resultant high performance. Importantly, as compared to the BPA-GTE, the FCN-GTE exhibits significantly improved mechanical properties owing to the increased density of hydrogen bond network and physical crosslinking interaction. Furthermore, density functional theory(DFT) calculation and in situ FTIR analysis is conducted to decipher the formation mechanism of hydrogen bond network. In addition, the FCN-GTE possesses superior UV shielding, chemical degradation, and recyclability because of the existence of abundant imine bonds. Notably, the FCN-GTE-based carbon fiber composites could be completely recycled in an amine solution.This study provides a facile strategy for synthesizing recyclable biomass-based high-performance epoxy vitrimers and carbon fiber composites.展开更多
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via ...This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis.These approaches exhibit high regioselectivity,atom econ-omy and broad functionality tolerance.展开更多
The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(...The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(2) and NO on the catalytic activity was studied.At 270℃,the MCFe oxide catalyst presents significant simultaneous removal efficiency of 75.25%and 100%for 1,2-DCB and furan,respectively.Brunauer-Emmett-Teller(BET)method(BET),X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR),H_2-temperature programmed reduction(H_(2)-TPR),NH_(3)-temperature programmed desorption(NH_3-TPD)and O_(2)-TPD were used to characterize the catalysts before and after the reaction.Competition tests suggest that the oxidation behavior of furan occurred prior to that of 1,2-DCB.According to the intermediate products detected by gas chromatography-mass spectrometry(GC-MS),the by-products include chlorinated hydrocarbons,long-chain hydrocarbons,ketone,etc.Possible catalytic oxidation reaction paths are proposed.展开更多
A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a ca...A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a cascade process including cross-coupling of the two reactants,[3,3]-sulfonium rearrangement,and 5-exo-dig heterocyclization,leading to tetrasubstituted furan products.The resultant α-alkylthio groups can be used for further functionalization,such as to introduce other alkyl/aryl groups.展开更多
Direct conversion of inexpensive biomass into value-added chemicals via furanic platform molecules is highly attractive.In this work,we present a straightforward chemobiocatalytic route for glucose valorization into 2...Direct conversion of inexpensive biomass into value-added chemicals via furanic platform molecules is highly attractive.In this work,we present a straightforward chemobiocatalytic route for glucose valorization into 2,5-bis(hydroxymethyl)furan(BHMF)in one pot,with no purification of the intermediate 5-hydroxymethylfurfural(HMF).Six candidate alcohol dehydrogenase(ADH)genes were located from Meyerozyma guilliermondii SC1103,based on comparative transcriptome analysis and real-time quantitative polymerase chain reaction.An ADH(MgADH1)was identified upon evaluation of catalytic performances of recombinant Saccharomyces cerevisiae harboring candidate ADHs in HMF reduction.Soluble expression of the enzyme in S.cerevisiae was greatly enhanced by its codon optimization,leading to improved HMF tolerance(up to 400 mM).In a fed-batch process,the desired product of approximately 473 mM(60.5 g/L)was produced within 30 h by recombinant S.cerevisiae_MgADH1.A chemobiocatalytic route toward BHMF was constructed by merging CaCl2-mediated isomerization and dehydration with biocatalytic reduction with an overall yield of approximately 42%,starting from glucose.This work may pave the way for green manufacture of valuable biobased chemicals.展开更多
Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processe...Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processes to decentralized,low-temperature conversions is achieved,which meets the requirement of sustainable energy generation.This approach provides an efficient,green,and additive-free strategy for biomass derivative valorization,in which product selectivity could be easily regulated by the applied potential and electrocatalyst utilized.However,a scale-up application is still far from being completed due to the inability of conversion rates and selectivity to meet the industrialization requirements.A better understanding of the reaction mechanism and the development of highefficiency and high-selectivity electrocatalysts are required to pave the path toward larger industrialization applications.Herein,we summarize the recent research progress in the electrocatalytic oxidation and hydrogenation of platform compounds such as furanic compounds and glycerol.In the literature,these three research areas are integrated to realize the scale-up application of the processes as mentioned above.The investigations of the mechanism are based on in situ techniques,theoretical calculations,and advanced electrocatalyst studies.Finally,the challenges and prospects in this topic are described.We expect that this review will provide the fundamental understanding and design guidelines to achieve efficient and high-selectivity catalysts and further facilitate the scale-up application of the electrocatalytic conversion of biomass derivatives.展开更多
Catalytic reduction systems of 2-furancarboxylic acid(FCA)and 2,5-furandicarboxylic acid(FDCA)with H 2 without reduction of the carboxyl groups are reviewed.FCA and FDCA are produced from furfural and 5-hydroxymethylf...Catalytic reduction systems of 2-furancarboxylic acid(FCA)and 2,5-furandicarboxylic acid(FDCA)with H 2 without reduction of the carboxyl groups are reviewed.FCA and FDCA are produced from furfural and 5-hydroxymethylfurfural which are important platform chemicals in biomass conversions.Furan ring hydrogenation to tetrahydrofuran-2-carboxylic acid(THFCA)and tetrahydrofuran-2,5-dicarboxylic acid(THFDCA)easily proceeds over Pd catalysts.Hydrogenolysis of one C–O bond in the furan ring produces 5-hydroxyvaleric acid(5-HVA)and 2-hydroxyadipic acid.2-Hydroxyvaleric acid is not produced in the reported systems.5-HVA can be produced as the lactone form(δ-valerolactone;DVL)or as the esters depending on the solvent.These reactions proceed over Pt catalysts with good yields(~70%)at optimized conditions.Hydrogenolysis of two C–O bonds in the furan ring produces valeric acid and adipic acid,the latter of which is a very important chemical in industry and its production from biomass is of high importance.Adipic acid from FDCA can be produced directly over Pt-MoO_(x) catalyst,indirectly via hydrogenation and hydrodeoxygenation as one-pot reaction using the combination of Pt and acid catalysts such as Pt/niobium oxide,or indirectly via two-step reaction composed of hydrogenation catalyzed by Pd and hydrodeoxygenation catalyzed by iodide ion in acidic conditions.Only the two-step method can give good yield of adipic acid at present.展开更多
In response to the awareness of limited fossil resources and environmental concerns,catalytic conversion of renewable lignocellulose biomass to value-added chemicals and fuels is of great significance and attractive f...In response to the awareness of limited fossil resources and environmental concerns,catalytic conversion of renewable lignocellulose biomass to value-added chemicals and fuels is of great significance and attractive for sustainable chemistry.Division of Biomass Conversion and Bio-Energy attached to Dalian National Laboratory for Clean Energy has devoted themselves to valorization of lignocellulose biomass since launched in 2011.Our research interests focus on breeding of biomass resources(inulin and microalgae),exploration of catalytic and biological technologies,and production of energy chemicals and fuels.Although lignocellulose biomass is renewable and abundant,the way of utilization should be reasonable according to its structural characteristics in view of efficiency and economy.In this review,to celebrate the DICP's 70 th anniversary,we will highlight the major fundamental advances in DICP about the conversion of lignocellulose to value-added chemicals and liquid fuels.Particular attention will be paid to the transformation of cellulose and its derivatives to glycols,acids and nitrogen-containing chemicals,hemicellulose-derived platform molecule furfural to jet fuels and lignin to aromatics using catalytic technologies.展开更多
A novel benzoxazine-based phenolic resin containing furan groups（PFB） was synthesized via simple two-step reactions and the structure of PFB was confirmed by FTIR and ~1H NMR spectra.Differential scanning calorimetr...A novel benzoxazine-based phenolic resin containing furan groups（PFB） was synthesized via simple two-step reactions and the structure of PFB was confirmed by FTIR and ~1H NMR spectra.Differential scanning calorimetry（DSC） showed that the polybenzoxazine cured from PFB had good heat resistance and lower polymerization temperature compared with that of benzoxazine-based phenolic resins.展开更多
2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following meth...2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods：（1） oxidation of 5-hydroxymethylfurfural（HMF） in the presence of complex biocatalyst or metallic catalyst;（2） conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly（ethylene furandicarboxylate）（PEF） of high quality in terms of high molecular weight and good appearance.展开更多
In this study,the 24 h tensile strength of new type acetone-urea-formaldehyde furan resin (nitrogen content 3%) was investigated by uniform design optimization.Four independent variables such as acetone:formaldehyde m...In this study,the 24 h tensile strength of new type acetone-urea-formaldehyde furan resin (nitrogen content 3%) was investigated by uniform design optimization.Four independent variables such as acetone:formaldehyde molar ratio (mol/mol),solution pH value,reaction temperature (℃) and reaction time (min) were considered in the experiments.U13(134) uniform design was employed and the equation of 24 h tensile strength model was obtained after 13 experimentations.The 24 h tensile strength was optimized by applying single factor experiments and stepwise non-linear regression analysis.Minitab (Minitab 15 trial version) and MATLAB (R2010a trial version) were used for data analysis.The t-value and p-value indicate that the major impact factors include the interaction effect of solution pH value and reaction temperature (X2X3),the linear terms of acetone:formaldehyde molar ratio (X1),reaction time (X4) followed by the square effects of acetone/formaldehyde molar ratio (X1X1).The optimized results were achieved with the acetone:formaldehyde molar ratio (mol/mol) at 3:1,solution pH value at 6.0,reaction temperature at 70℃,and reaction time at 140 min,respectively.This method can not only significantly reduce the number and cost of the tests,but also provide a good experimental design strategy for the development of furan resin.The investigation shows that the predicted results of 24 h tensile strength are consistent well with the experimental ones.展开更多
Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, ...Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.展开更多
We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman sp...We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman spectroscopy.The morphology of furan resin carbon was characterized by scanning electron microscopy.The effects of the praseodymium content and the heat-treatment temperature on the catalytic graphitization of furan resin carbon were also investigated.The results indicated that the praseodymium c...展开更多
A novel phenanthro [2,3-b] furan 1, named (3-hydroxy-9-(4′-hydroxy-3′-methoxyphenyl)-11-methoxy-5,6,9,10-tetrahydrophenanthro [2,3-b] furan-10-yl) methyl acetate, and two known phenolic compounds were isolated from ...A novel phenanthro [2,3-b] furan 1, named (3-hydroxy-9-(4′-hydroxy-3′-methoxyphenyl)-11-methoxy-5,6,9,10-tetrahydrophenanthro [2,3-b] furan-10-yl) methyl acetate, and two known phenolic compounds were isolated from the tubers of Pleione bulbocodioides (Franch.) Rolfe. Their structures were elucidated by spectroscopic methods.展开更多
In order to find better herbicidal activity and fungicidal activity of a-amino acid derivatives, we introduced furan rings and pyridyl groups to seven different a-amino acids to form a series of 14 novel a-amino acyla...In order to find better herbicidal activity and fungicidal activity of a-amino acid derivatives, we introduced furan rings and pyridyl groups to seven different a-amino acids to form a series of 14 novel a-amino acylamines derivatives via dicyclohexylcarbodiimide/4-dimethylaminopyridine（DCC/DMAP） coupling method. The structures of all the compounds prepared were confirmed by IR, LC/MS, IH NMR, and elemental analysis. The herbicidal and fungicidal results show that some compounds containing glycine and valine substrate have good activities.展开更多
基金supported by the National Key R&D Program of China (2018YFB1501604)the Strategic Priority Research Program of the CAS (XDA21060101)+2 种基金the Major Science and Technology Projects of Anhui Province (18030701157)the National Natural Science Foundation of China (51821006, 51961135104)the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N092)。
文摘Medium-chain furanic chemicals have outstanding practical potential,especially in the application of pharmaceuticals and polymers.Herein,we describe an eco-friendly and efficient heterogeneous sodium-doped porous sodium manganese oxide catalyst(Na-MnO_(x)) for oxidative cleavage of furanic 1,2-diols into medium-chain furanic aldehyde compounds.Subsequently,various high value-added chemicals(diacids and esters,diols,hydroxy acids,acrylics) were synthesized based on the widely applicable and highly selective catalytic approaches.The Na-MnO_(x) was prepared by the coprecipitation method and characterized by XRD,SEM,XPS and FT-IR,and TGA.XPS revealed that Mn species existed in the mixed oxidation states Mn~Ⅱ,Mn~Ⅲ and Mn~Ⅳ.When NaOH concentration up to 1.8 mol L^(-1) during the preparation process of the catalyst,the ratio of Mn^(4+) in the catalyst was the highest,and the yield of product(Furan-2-acrolein) in the model reaction is also optimal.Overall,this protocol developed a novel and general route for the preparation of medium-chain furanic compounds utilizing cellulose-derived platform molecules.
基金supported by the National Natural Science Foundation of China(Nos.51871209 and 51902311)the Postdoctoral Science Foundation of China(No.2019M652223).
文摘The cyclopentanone and derivatives are a class of crucial fine chemicals for various industries and currently produced by conventional petrochemical synthetic routes.Here,we demonstrated a new synthetic approach to directly fabricate N-doped carbon nanotube(N-CNTs)networks with confined Co nanoparticles from Co^(2+)-impregnated bulk g-C_(3)N_(4) as high performance hydrogenation rearrangement(HR)catalyst to efficiently convert a wide spectrum of biomass-derived furanic aldehydes to the corresponding cyclopentanones in water under a record-low H2 pressure of 0.5 MPa and mild temperature.We unveiled a Co-catalysed bulk g-C_(3)N_(4) decomposition/carbonisation CNTs formation mechanism.A new HR pathway was also unveiled.
基金supported by the National Key Research and Development Program of China (Nos.2018YFA0901101,2018YFA0901103,and 2017YFC1600301)the National Natural Science Foundation of China (Nos.22076216,21976201,and 21836004).
文摘The evaluation of toxicity related to polychlorinated dibenzo-p-dioxins and furans(PCDD/Fs)and dioxin-like polychlorinated biphenyls(DL-PCBs)is crucial for a comprehensive risk assessment in real-world exposure scenarios.This study employed a controlled feeding experiment to investigate the metabolic effects of dioxin-like compounds(DLCs)on laying hens via feed exposure.Diets enriched with two concentrations(1.17 and 5.13 pg toxic equivalents(TEQ)/g dry weight(dw))were administered over 14 days,followed by 28 days of clean feed.Metabolomics analyses of blood samples revealed significant metabolic variations between PCDD/Fs and DL-PCBs exposed groups and controls,reflecting the induced metabolic disruption.Distinct changes were observed in sphingosine,palmitoleic acid,linoleate,linolenic acid,taurocholic acid,indole acrylic acid,and dibutyl phthalate levels,implying possible connections between PCDD/Fs and DL-PCBs toxic effects and energy-neuronal imbalances,along with lipid accumulation and anomalous amino acid metabolism,impacting taurine metabolism.Moreover,we identified three differential endogenous metabolites—L-tryptophan,indole-3-acetaldehyde,and indole acrylic acid—as potential ligands for the aryl hydrocarbon receptor(AhR),suggesting their role inmediating PCDD/Fs and DL-PCBs toxicity.This comprehensive investigation provides novel insights into the metabolic alterations induced by PCDD/Fs and DL-PCBs in laying hens,thereby enhancing our ability to assess risks associated with their exposure in human populations.
基金financially supported by China Scholarship Council,Science and Technology Project of the State Administration for Market Regulation(2022MK111)the Fundamental Research Funds for the Central Universities.
文摘Primary diamines play an important role in the chemical industry,where they are widely used as raw materials for the manufacture of pharmaceuticals and polymers.Currently,primary diamines are mainly derived from petroleum,while harsh or toxic conditions are often needed.Biomass is abundant and renewable,which serves as a promising alternative raw material to produce primary diamines.This review primarily focuses on the synthesis of 2,5-bis(aminomethyl)furan(BAMF),a bio-based diamine with potential as a biomonomer for polyamides and polyureas.Specifically,this review emphasizes the synthesis of BAMF fromthree biomass-derived alcohols and aldehydes,namely 5-hydroxymethylfurfural(HMF),2,5-bis(hydroxymethyl)furan(BHMF),and 2,5-diformylfuran(DFF).These are the key substrates to get BAMF and could be readily obtained from carbohydrates.Even though great effort has been put into the synthesis of BAMF,it remains a tough problem to obtain BAMF with a high yield at a low cost due to the inevitable side reactions,such as unwanted hydrogenation reactions and condensation reactions.Many strategies have been proposed to solve this problem,such as the hydrogen-borrowing strategy and stepwise reductive amination strategy.Herein,we will summarize the key advancements in this area,and discuss the challenges that need to be responded in the future,hoping to provide an insight into the design and development of a more efficient system for the production of biomass-derived diamines.
文摘An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.
基金financially supported by the National Natural Science Foundation of China (Nos.51973118, 22175121,52003160 and 22001175)Key-Area Research and Development Program of Guangdong Province (Nos.2019B010941001 and2019B010929002)+7 种基金the Natural Science Foundation of Guangdong Province (No.2020A1515010644)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2019ZT08C642)Shenzhen Science and Technology Program (Nos.JCYJ20220818095810022, JSGGZD20220822095201003 and JCYJ20210324095412035)the start-up fund of Shenzhen University (No.000002110820)the Guangdong Natural Science Foundation (Nos.2022A1515011781 and2021A1515110086)Science and Technology Innovation Commission of Shenzhen,China (Nos.RCBS20200714114910141 and JCYJ20210324132816039)the Start-up Grant at Harbin Institute of Technology (Shenzhen),China (Nos.HA45001108 and HA11409049)Shenzhen Key Laboratory of Advanced Functional Carbon Materials Research and Comprehensive Application (No.ZDSYS20220527171407017)。
文摘The emerging biomass-based epoxy vitrimers hold great potential to fulfill the requirements for sustainable development of society.Since the existence of dynamic chemical bonds in vitrimers often reduces both the thermal and mechanical properties of epoxy resins, it is challenging to produce recyclable epoxy vitrimers with both excellent mechanical properties and good thermal stability. Herein, a monomer 4-(((5-(hydroxymethyl)furan-2-yl)methylene)amino)phenol(FCN) containing furan ring with potential to form high density of hydrogen bonding among repeating units is designed and copolymerized with glycerol triglycidyl ether to yield epoxy resin(FCN-GTE), which intrinsically has dual hydrogen bond networks, dynamic imine structure and resultant high performance. Importantly, as compared to the BPA-GTE, the FCN-GTE exhibits significantly improved mechanical properties owing to the increased density of hydrogen bond network and physical crosslinking interaction. Furthermore, density functional theory(DFT) calculation and in situ FTIR analysis is conducted to decipher the formation mechanism of hydrogen bond network. In addition, the FCN-GTE possesses superior UV shielding, chemical degradation, and recyclability because of the existence of abundant imine bonds. Notably, the FCN-GTE-based carbon fiber composites could be completely recycled in an amine solution.This study provides a facile strategy for synthesizing recyclable biomass-based high-performance epoxy vitrimers and carbon fiber composites.
基金support from the National Natural Science Foundation of China(Nos.21971107,22071101,22271147).
文摘This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis.These approaches exhibit high regioselectivity,atom econ-omy and broad functionality tolerance.
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China(LQ23E060002)the National Natural Science Foundation of China(51976192)。
文摘The Mn-Ce-Fe mixed oxide(MCFe)was prepared by co-precipitation and the catalytic performance was tested by using 1,2-dichlorobenzene(1,2-DCB)and furan as model molecules of PCDD/F.The effect of O_(2)concentration,SO_(2) and NO on the catalytic activity was studied.At 270℃,the MCFe oxide catalyst presents significant simultaneous removal efficiency of 75.25%and 100%for 1,2-DCB and furan,respectively.Brunauer-Emmett-Teller(BET)method(BET),X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR),H_2-temperature programmed reduction(H_(2)-TPR),NH_(3)-temperature programmed desorption(NH_3-TPD)and O_(2)-TPD were used to characterize the catalysts before and after the reaction.Competition tests suggest that the oxidation behavior of furan occurred prior to that of 1,2-DCB.According to the intermediate products detected by gas chromatography-mass spectrometry(GC-MS),the by-products include chlorinated hydrocarbons,long-chain hydrocarbons,ketone,etc.Possible catalytic oxidation reaction paths are proposed.
文摘A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a cascade process including cross-coupling of the two reactants,[3,3]-sulfonium rearrangement,and 5-exo-dig heterocyclization,leading to tetrasubstituted furan products.The resultant α-alkylthio groups can be used for further functionalization,such as to introduce other alkyl/aryl groups.
基金financially supported by the National Natural Science Foundation of China(22078110)the National Key Research and Development Program of China(2021YFC2102700).
文摘Direct conversion of inexpensive biomass into value-added chemicals via furanic platform molecules is highly attractive.In this work,we present a straightforward chemobiocatalytic route for glucose valorization into 2,5-bis(hydroxymethyl)furan(BHMF)in one pot,with no purification of the intermediate 5-hydroxymethylfurfural(HMF).Six candidate alcohol dehydrogenase(ADH)genes were located from Meyerozyma guilliermondii SC1103,based on comparative transcriptome analysis and real-time quantitative polymerase chain reaction.An ADH(MgADH1)was identified upon evaluation of catalytic performances of recombinant Saccharomyces cerevisiae harboring candidate ADHs in HMF reduction.Soluble expression of the enzyme in S.cerevisiae was greatly enhanced by its codon optimization,leading to improved HMF tolerance(up to 400 mM).In a fed-batch process,the desired product of approximately 473 mM(60.5 g/L)was produced within 30 h by recombinant S.cerevisiae_MgADH1.A chemobiocatalytic route toward BHMF was constructed by merging CaCl2-mediated isomerization and dehydration with biocatalytic reduction with an overall yield of approximately 42%,starting from glucose.This work may pave the way for green manufacture of valuable biobased chemicals.
基金supported by the National Key R&D Program of China(2020YFA0710000)the Fundamental Research Funds for the Central Universities(531118010127)+1 种基金the National Natural Science Foundation of China(22122901,21902047,21825201,and U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021RC3054).
文摘Electrocatalytic valorization of biomass derivatives can be powered by electricity generated from renewable sources such as solar and wind energy.A shift from centralized,high-temperature,and energy-intensive processes to decentralized,low-temperature conversions is achieved,which meets the requirement of sustainable energy generation.This approach provides an efficient,green,and additive-free strategy for biomass derivative valorization,in which product selectivity could be easily regulated by the applied potential and electrocatalyst utilized.However,a scale-up application is still far from being completed due to the inability of conversion rates and selectivity to meet the industrialization requirements.A better understanding of the reaction mechanism and the development of highefficiency and high-selectivity electrocatalysts are required to pave the path toward larger industrialization applications.Herein,we summarize the recent research progress in the electrocatalytic oxidation and hydrogenation of platform compounds such as furanic compounds and glycerol.In the literature,these three research areas are integrated to realize the scale-up application of the processes as mentioned above.The investigations of the mechanism are based on in situ techniques,theoretical calculations,and advanced electrocatalyst studies.Finally,the challenges and prospects in this topic are described.We expect that this review will provide the fundamental understanding and design guidelines to achieve efficient and high-selectivity catalysts and further facilitate the scale-up application of the electrocatalytic conversion of biomass derivatives.
基金This work was financially supported by New Energy and Industrial Technology Development Organization(NEDO)under the program of Extensive Support for Young Promising Researchers.
文摘Catalytic reduction systems of 2-furancarboxylic acid(FCA)and 2,5-furandicarboxylic acid(FDCA)with H 2 without reduction of the carboxyl groups are reviewed.FCA and FDCA are produced from furfural and 5-hydroxymethylfurfural which are important platform chemicals in biomass conversions.Furan ring hydrogenation to tetrahydrofuran-2-carboxylic acid(THFCA)and tetrahydrofuran-2,5-dicarboxylic acid(THFDCA)easily proceeds over Pd catalysts.Hydrogenolysis of one C–O bond in the furan ring produces 5-hydroxyvaleric acid(5-HVA)and 2-hydroxyadipic acid.2-Hydroxyvaleric acid is not produced in the reported systems.5-HVA can be produced as the lactone form(δ-valerolactone;DVL)or as the esters depending on the solvent.These reactions proceed over Pt catalysts with good yields(~70%)at optimized conditions.Hydrogenolysis of two C–O bonds in the furan ring produces valeric acid and adipic acid,the latter of which is a very important chemical in industry and its production from biomass is of high importance.Adipic acid from FDCA can be produced directly over Pt-MoO_(x) catalyst,indirectly via hydrogenation and hydrodeoxygenation as one-pot reaction using the combination of Pt and acid catalysts such as Pt/niobium oxide,or indirectly via two-step reaction composed of hydrogenation catalyzed by Pd and hydrodeoxygenation catalyzed by iodide ion in acidic conditions.Only the two-step method can give good yield of adipic acid at present.
基金supported by the National Natural Science Foundation of China(Projects 21790331,21603218,21703236 and 21872138)the Strategic Priority Research Program of the Chinese Academy of Sciences(Nos.XDB17020300 and XDA21030400)+1 种基金the Youth Innovation Promotion Association,CAS(2018219)DICP ZZBS201811
文摘In response to the awareness of limited fossil resources and environmental concerns,catalytic conversion of renewable lignocellulose biomass to value-added chemicals and fuels is of great significance and attractive for sustainable chemistry.Division of Biomass Conversion and Bio-Energy attached to Dalian National Laboratory for Clean Energy has devoted themselves to valorization of lignocellulose biomass since launched in 2011.Our research interests focus on breeding of biomass resources(inulin and microalgae),exploration of catalytic and biological technologies,and production of energy chemicals and fuels.Although lignocellulose biomass is renewable and abundant,the way of utilization should be reasonable according to its structural characteristics in view of efficiency and economy.In this review,to celebrate the DICP's 70 th anniversary,we will highlight the major fundamental advances in DICP about the conversion of lignocellulose to value-added chemicals and liquid fuels.Particular attention will be paid to the transformation of cellulose and its derivatives to glycols,acids and nitrogen-containing chemicals,hemicellulose-derived platform molecule furfural to jet fuels and lignin to aromatics using catalytic technologies.
基金supported by project of Hubei Provincial Department of Education,China(No.Q20083003)the Innovative Team of Huangshi Institute of Technology.
文摘A novel benzoxazine-based phenolic resin containing furan groups（PFB） was synthesized via simple two-step reactions and the structure of PFB was confirmed by FTIR and ~1H NMR spectra.Differential scanning calorimetry（DSC） showed that the polybenzoxazine cured from PFB had good heat resistance and lower polymerization temperature compared with that of benzoxazine-based phenolic resins.
基金financially supported by the National Natural Science Foundation of China(Nos.51373194 and 51503217)National Key Technology Support Program(No.2015BAD15B08)
文摘2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods：（1） oxidation of 5-hydroxymethylfurfural（HMF） in the presence of complex biocatalyst or metallic catalyst;（2） conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly（ethylene furandicarboxylate）（PEF） of high quality in terms of high molecular weight and good appearance.
文摘In this study,the 24 h tensile strength of new type acetone-urea-formaldehyde furan resin (nitrogen content 3%) was investigated by uniform design optimization.Four independent variables such as acetone:formaldehyde molar ratio (mol/mol),solution pH value,reaction temperature (℃) and reaction time (min) were considered in the experiments.U13(134) uniform design was employed and the equation of 24 h tensile strength model was obtained after 13 experimentations.The 24 h tensile strength was optimized by applying single factor experiments and stepwise non-linear regression analysis.Minitab (Minitab 15 trial version) and MATLAB (R2010a trial version) were used for data analysis.The t-value and p-value indicate that the major impact factors include the interaction effect of solution pH value and reaction temperature (X2X3),the linear terms of acetone:formaldehyde molar ratio (X1),reaction time (X4) followed by the square effects of acetone/formaldehyde molar ratio (X1X1).The optimized results were achieved with the acetone:formaldehyde molar ratio (mol/mol) at 3:1,solution pH value at 6.0,reaction temperature at 70℃,and reaction time at 140 min,respectively.This method can not only significantly reduce the number and cost of the tests,but also provide a good experimental design strategy for the development of furan resin.The investigation shows that the predicted results of 24 h tensile strength are consistent well with the experimental ones.
基金financially supported by the National Natural Science Foundation of China(Nos.21574144,51273209 and 51411140244)Zhejiang Provincial Natural Science Foundation of China(No.LR16B040002)+1 种基金CAS Interdisciplinary Innovation Team and Ningbo Municipal Science and Technology Innovative Research Team(Nos.2015B11002 and 2016B10005)Ningbo Natural Science Foundation(No.2016A610277)
文摘Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.
基金supported by the National Basic Research Program of China (2006CB600903)
文摘We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman spectroscopy.The morphology of furan resin carbon was characterized by scanning electron microscopy.The effects of the praseodymium content and the heat-treatment temperature on the catalytic graphitization of furan resin carbon were also investigated.The results indicated that the praseodymium c...
文摘A novel phenanthro [2,3-b] furan 1, named (3-hydroxy-9-(4′-hydroxy-3′-methoxyphenyl)-11-methoxy-5,6,9,10-tetrahydrophenanthro [2,3-b] furan-10-yl) methyl acetate, and two known phenolic compounds were isolated from the tubers of Pleione bulbocodioides (Franch.) Rolfe. Their structures were elucidated by spectroscopic methods.
基金Supported by the National Natural Science Foundation of China(No.20672073)Shanghai Leading Academic Discipline Project,China(No.T0402)
文摘In order to find better herbicidal activity and fungicidal activity of a-amino acid derivatives, we introduced furan rings and pyridyl groups to seven different a-amino acids to form a series of 14 novel a-amino acylamines derivatives via dicyclohexylcarbodiimide/4-dimethylaminopyridine（DCC/DMAP） coupling method. The structures of all the compounds prepared were confirmed by IR, LC/MS, IH NMR, and elemental analysis. The herbicidal and fungicidal results show that some compounds containing glycine and valine substrate have good activities.
