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
5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated...5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.展开更多
Lead(Pb) and furan are toxic agents, and persistent exposure may impair human and animal reproductive function. We therefore explored the effects of Pb and furan on male rat hypothalamic-pituitary-gonadal reproductive...Lead(Pb) and furan are toxic agents, and persistent exposure may impair human and animal reproductive function. We therefore explored the effects of Pb and furan on male rat hypothalamic-pituitary-gonadal reproductive status, oxidative stress, inflammation, and genomic integrity. We found that co-exposure to Pb and furan reduced the activities of testicular function enzymes, endogenous antioxidant levels, total sulfhydryl group,and glutathione. Sperm abnormality, biomarkers of oxidative stress, inflammation, and p53 expression were increased in a dose-dependent manner by treatment with furan and Pb. Typical rat gonad histoarchitecture features were also damaged. Conclusively, co-exposure to Pb and furan induced male reproductive function derangement by decreasing the antioxidant defences in rats, increasing abnormalities in spermatozoa morphology, and reducing reproductive hormone in circulation. These pathophysiological alterations, if persistent, might provide a permissive environment for potentiating reproductive dysfunction and infertility.展开更多
Recently,increasing evidence suggests that DNA methylation plays a crucial role in fruit ripening.However,the role of DNA methylation in regulating specific traits,such as flavor,remains unclear.Here,we report a role ...Recently,increasing evidence suggests that DNA methylation plays a crucial role in fruit ripening.However,the role of DNA methylation in regulating specific traits,such as flavor,remains unclear.Here,we report a role of DNA methylation in affecting furanone biosynthesis in strawberry.Strawberry quinone oxidoreductase(FaQR)is a key enzyme in furanone biosynthesis.There are four FaQR homologs in strawberry cultivar‘Yuexin’,and one of them,FaQR3,contributes∼50%of FaQR transcripts,indicating a major role of FaQR3 in furanone biosynthesis.Through characterization of levels of DNA methylation and FaQR3 transcript and furanone contents during fruit ripening and after the application of DNA methylation inhibitor,we found that the DNA methylation level of the FaQR3 promoter was negatively correlated with FaQR3 expression and furanone accumulation,suggesting that DNA methylation may be involved in furanone biosynthesis through adjusting FaQR3 expression,and responded to different temperatures consistently.In addition,transient expression of a gene in the RNA-directed DNA methylation(RdDM)pathway,FaAGO4,and enrichment analysis of the 24-nucleotide siRNAs suggested that DNA methylation in the FaQR3 promoter is mediated by the RdDM pathway.Transient RNA interference(RNAi)of FaDML indicated that the demethylation pathway may be involved in regulating furanone accumulation.These findings provide new insights into the role of DNA methylation and demethylation in affecting flavor quality in strawberry during fruit ripening.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
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
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
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
A series of compounds that contained furan skeletons were synthesized using 3,4-bis(trimethylsilyl) furan as staring material.1H NMR,13C NMR, MS and EA had identified these new molecules. The important factors that in...A series of compounds that contained furan skeletons were synthesized using 3,4-bis(trimethylsilyl) furan as staring material.1H NMR,13C NMR, MS and EA had identified these new molecules. The important factors that influenced reactions were discussed, and the new furan intermediates could be used in various organic syntheses.展开更多
Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential elec...Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to;TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.展开更多
At present, furan resin is the largest selling no-bake system of moulding sands. The most commonly used furan no-bake binders(FNB) are condensation products of furfuryl alcohol(FA) urea, formaldehyde and phenol. They ...At present, furan resin is the largest selling no-bake system of moulding sands. The most commonly used furan no-bake binders(FNB) are condensation products of furfuryl alcohol(FA) urea, formaldehyde and phenol. They are generally cured by exposure to organic sulfonic acids. FNB provide excellent mold and core strength, cure rapidly and allow the sand to be reclaimed at fairly high yields, generally 75%-80%, especially in applications where due allowance is made for the need to keep total sulfur content below 0.1%. However, due to probable carcinogenic properties of furfuryl alcohol, the EU Directive limits the content of this substance(in a monomer form in resin) to 25%. The classification of furfuryl alcohol and the resulting furan resin products has changed from "harmful" to "toxic by inhalation". The aim of this study was to determine the effect of free furfuryl alcohol content in the resin on the emission of harmful substances from the BTEX(Benzene Toluene Ethylbenzene & Xylene) and PAHs(polycyclic aromatic hydrocarbon) group exposed to high temperature and how it affects the emissions allowance of reclaimed sand in the matrix. Three resins from a leading manufacturer were examined, which contain a free furfuryl alcohol content of 71%-72%, about 50% and < 25%, respectively. The hardener for each resin was 65% aqueous solution of paratoluenesulfonic acid. Tests were carried out in semi-industrial conditions where liquid cast-iron was poured into sample sand mold at 1,350 °C. The matrix of the studied sands was reclaimed in the amount of 0, 50%, 100%, respectively.With the increase of free furfuryl alcohol content, the volume of evolved gases decreased. For all resins the main component from the BTEX group dominating in the emitted gases was benzene; however toluene also appeared in the amount of a few percentages. In contrast, ethylbenzene and xylenes occurred only in the gases emitted from resin-bonded sands with the largest furfuryl alcohol content. The increase in the share of reclaimed sands resulted in very significant increase in the volume of gas generated and participation of benzene in these gases. In terms of emission of compounds from the PAHs group virtually for all resins, the total content of these substances was comparable(within the limits of error). The main components were: fluoranthene, pyrene and benzo(a) anthracene.展开更多
The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catal...The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.展开更多
Peptide mimics derived with close structure to peptide have vast utility because they are expected to interfere with biological targets while having superior drug-like properties if compared to peptides. In this work,...Peptide mimics derived with close structure to peptide have vast utility because they are expected to interfere with biological targets while having superior drug-like properties if compared to peptides. In this work, novel vinyl dipeptides which are different in a double bond between the α-carbon of peptide and C1 of its side chain. Added to that, suitable substituents were selected to harness drug-like properties. The compounds were found to have moderate activities when tested against MCF-7 breast cancer cell line. For instance, the adamantyl analogue 2-(benzoylamino)-3-(2-furyl)-N-(1-adamantyl) propenamide (1c) and the heterocyclic analogue 2-(Benzoylamino)-3-(2-furyl)-N-[2-(5-cyanothia-zol-2-yl)] propenamide (1o) exhibited inhibition potency at 27.4 and 37.8 μM, respectively.展开更多
The authors have studied the Diels-Alder reactions between furan derivatives and maleimide derivatives in an ionic liquid and have found that higher reactivity can be obtained in a protic ionic liquid [Mim]Tf2N than i...The authors have studied the Diels-Alder reactions between furan derivatives and maleimide derivatives in an ionic liquid and have found that higher reactivity can be obtained in a protic ionic liquid [Mim]Tf2N than in the conventional organic solvent. Furthermore, in the Diels-Alder reactions of 2- and 2,5-alkylfurans with N-alkylma- leimide, the reactivity increases by extending the alkyl chain length of N-alkylmaleimide. In addition, it was demon- strated that endo-selectivity increases when 2,5-disubstituted furans are used. These results will be explained by comparing the stability of the Diels-Alder adduct with that of the products obtained from the reactions of 2-substituted furans and 2,5-disubstituted furans.展开更多
Eight new furan derivatives,irpexins A‒H(1‒8),two new polyketides,irpexins I and J(9 and 10),together with nine known compounds were isolated from the fermentation of Irpex lacteus.The structures and absolute configur...Eight new furan derivatives,irpexins A‒H(1‒8),two new polyketides,irpexins I and J(9 and 10),together with nine known compounds were isolated from the fermentation of Irpex lacteus.The structures and absolute configurations were elucidated on the basis of extensive spectroscopic methods and Mosher ester reaction.All compounds shows no cytotoxicity to human MCF-7 and Hela cancer cell lines at the concentration of 10μM.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financially supported by the National Key R&D Program of China 2021YFC2101604)the National Natural Science Foundation of China(22278339,21978248)+1 种基金the Guangdong Provincial Key Research and Development Program(2020B0101070001)the Natural Science Foundation of Fujian Province of China(2019J06005)。
文摘5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.
文摘Lead(Pb) and furan are toxic agents, and persistent exposure may impair human and animal reproductive function. We therefore explored the effects of Pb and furan on male rat hypothalamic-pituitary-gonadal reproductive status, oxidative stress, inflammation, and genomic integrity. We found that co-exposure to Pb and furan reduced the activities of testicular function enzymes, endogenous antioxidant levels, total sulfhydryl group,and glutathione. Sperm abnormality, biomarkers of oxidative stress, inflammation, and p53 expression were increased in a dose-dependent manner by treatment with furan and Pb. Typical rat gonad histoarchitecture features were also damaged. Conclusively, co-exposure to Pb and furan induced male reproductive function derangement by decreasing the antioxidant defences in rats, increasing abnormalities in spermatozoa morphology, and reducing reproductive hormone in circulation. These pathophysiological alterations, if persistent, might provide a permissive environment for potentiating reproductive dysfunction and infertility.
文摘Recently,increasing evidence suggests that DNA methylation plays a crucial role in fruit ripening.However,the role of DNA methylation in regulating specific traits,such as flavor,remains unclear.Here,we report a role of DNA methylation in affecting furanone biosynthesis in strawberry.Strawberry quinone oxidoreductase(FaQR)is a key enzyme in furanone biosynthesis.There are four FaQR homologs in strawberry cultivar‘Yuexin’,and one of them,FaQR3,contributes∼50%of FaQR transcripts,indicating a major role of FaQR3 in furanone biosynthesis.Through characterization of levels of DNA methylation and FaQR3 transcript and furanone contents during fruit ripening and after the application of DNA methylation inhibitor,we found that the DNA methylation level of the FaQR3 promoter was negatively correlated with FaQR3 expression and furanone accumulation,suggesting that DNA methylation may be involved in furanone biosynthesis through adjusting FaQR3 expression,and responded to different temperatures consistently.In addition,transient expression of a gene in the RNA-directed DNA methylation(RdDM)pathway,FaAGO4,and enrichment analysis of the 24-nucleotide siRNAs suggested that DNA methylation in the FaQR3 promoter is mediated by the RdDM pathway.Transient RNA interference(RNAi)of FaDML indicated that the demethylation pathway may be involved in regulating furanone accumulation.These findings provide new insights into the role of DNA methylation and demethylation in affecting flavor quality in strawberry during fruit ripening.
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...
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.
基金The financial support for this study by National Natural Science Foundation of China(No.30960242)National Basic Research Program of China(973 program)(No.2012CB720805)Training Project of Young Scientists of Jiangxi Province(Stars of Jing gang)is gratefully acknowledged.
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.
文摘A series of compounds that contained furan skeletons were synthesized using 3,4-bis(trimethylsilyl) furan as staring material.1H NMR,13C NMR, MS and EA had identified these new molecules. The important factors that influenced reactions were discussed, and the new furan intermediates could be used in various organic syntheses.
文摘Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to;TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.
基金supported by the National Centre for Research and Development(PolandNo PBS2/A5/30/2013)
文摘At present, furan resin is the largest selling no-bake system of moulding sands. The most commonly used furan no-bake binders(FNB) are condensation products of furfuryl alcohol(FA) urea, formaldehyde and phenol. They are generally cured by exposure to organic sulfonic acids. FNB provide excellent mold and core strength, cure rapidly and allow the sand to be reclaimed at fairly high yields, generally 75%-80%, especially in applications where due allowance is made for the need to keep total sulfur content below 0.1%. However, due to probable carcinogenic properties of furfuryl alcohol, the EU Directive limits the content of this substance(in a monomer form in resin) to 25%. The classification of furfuryl alcohol and the resulting furan resin products has changed from "harmful" to "toxic by inhalation". The aim of this study was to determine the effect of free furfuryl alcohol content in the resin on the emission of harmful substances from the BTEX(Benzene Toluene Ethylbenzene & Xylene) and PAHs(polycyclic aromatic hydrocarbon) group exposed to high temperature and how it affects the emissions allowance of reclaimed sand in the matrix. Three resins from a leading manufacturer were examined, which contain a free furfuryl alcohol content of 71%-72%, about 50% and < 25%, respectively. The hardener for each resin was 65% aqueous solution of paratoluenesulfonic acid. Tests were carried out in semi-industrial conditions where liquid cast-iron was poured into sample sand mold at 1,350 °C. The matrix of the studied sands was reclaimed in the amount of 0, 50%, 100%, respectively.With the increase of free furfuryl alcohol content, the volume of evolved gases decreased. For all resins the main component from the BTEX group dominating in the emitted gases was benzene; however toluene also appeared in the amount of a few percentages. In contrast, ethylbenzene and xylenes occurred only in the gases emitted from resin-bonded sands with the largest furfuryl alcohol content. The increase in the share of reclaimed sands resulted in very significant increase in the volume of gas generated and participation of benzene in these gases. In terms of emission of compounds from the PAHs group virtually for all resins, the total content of these substances was comparable(within the limits of error). The main components were: fluoranthene, pyrene and benzo(a) anthracene.
文摘The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.
文摘Peptide mimics derived with close structure to peptide have vast utility because they are expected to interfere with biological targets while having superior drug-like properties if compared to peptides. In this work, novel vinyl dipeptides which are different in a double bond between the α-carbon of peptide and C1 of its side chain. Added to that, suitable substituents were selected to harness drug-like properties. The compounds were found to have moderate activities when tested against MCF-7 breast cancer cell line. For instance, the adamantyl analogue 2-(benzoylamino)-3-(2-furyl)-N-(1-adamantyl) propenamide (1c) and the heterocyclic analogue 2-(Benzoylamino)-3-(2-furyl)-N-[2-(5-cyanothia-zol-2-yl)] propenamide (1o) exhibited inhibition potency at 27.4 and 37.8 μM, respectively.
文摘The authors have studied the Diels-Alder reactions between furan derivatives and maleimide derivatives in an ionic liquid and have found that higher reactivity can be obtained in a protic ionic liquid [Mim]Tf2N than in the conventional organic solvent. Furthermore, in the Diels-Alder reactions of 2- and 2,5-alkylfurans with N-alkylma- leimide, the reactivity increases by extending the alkyl chain length of N-alkylmaleimide. In addition, it was demon- strated that endo-selectivity increases when 2,5-disubstituted furans are used. These results will be explained by comparing the stability of the Diels-Alder adduct with that of the products obtained from the reactions of 2-substituted furans and 2,5-disubstituted furans.
基金This work was financially supported by the joint research project from the National Natural Science Foundation of China(Grant No.21961142008)Thailand Research Fund(Grant No.DBG6280008).
文摘Eight new furan derivatives,irpexins A‒H(1‒8),two new polyketides,irpexins I and J(9 and 10),together with nine known compounds were isolated from the fermentation of Irpex lacteus.The structures and absolute configurations were elucidated on the basis of extensive spectroscopic methods and Mosher ester reaction.All compounds shows no cytotoxicity to human MCF-7 and Hela cancer cell lines at the concentration of 10μM.