Humans and animals can be exposed to Dioxins and Furans through ingestion of fatty food, skin contact, and breathing contaminated air. Resulting health problems include skin disease, immune problems, and cancers. Mana...Humans and animals can be exposed to Dioxins and Furans through ingestion of fatty food, skin contact, and breathing contaminated air. Resulting health problems include skin disease, immune problems, and cancers. Managing the release of these chemicals is therefore important. The Stockholm Convention on Persistent Organic Pollutants requires parties to adopt measures that reduce sources of these chemicals. Sierra Leone developed its National Implementation Plan (NIP) in 2008, in compliance with this requirement. However, no known further steps have been taken, particularly at community level. In 2013, the UNDP’s GEF/SGP funded a pilot project to manage the release of Dioxins and Furans from two dumpsites in Freetown, Sierra Leone. This work was sponsored with funds from that project. The work sought to delineate the exposure of communities within and around the Bormeh-Kingtom dumpsite (Kingtom, Kolleh town, Ascension town, Crab town, and Congo town) to the chemicals. The study considered sources of exposure, relative quantities generated per year, and the routes of exposure. This exposure study is a first step in managing the release from those sources. Enumerators deployed at the dumpsite every day, 7:00 AM to 6:00 PM, for three months, quantifying and recording source materials. The amount of source materials dumped per day informed calculation of Dioxin/Furan releases in grams toxicity equivalence per year. The results revealed a release of 128.914 g TEQ/year in air and residue. This implies that the communities are at high risk of inhalation and dermal exposure. Livestock, mainly pigs, are also exposed as they feed on the waste deposited in the dumpsite. Humans in turn feed on the livestock, a recipe for biomagnification. The project team has been working on developing Best Management Practices to suppress the release of the chemicals.展开更多
Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylate...Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.展开更多
Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramo...Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramolecular cyclization.DMSO acts as a solvent as well as a sulfur source and can also be replaced with DMSO-d_(6),enabling the incorporation of the SCD3 moiety of DMSO-d_(6) to the 3-position of the heterocyclic frameworks.展开更多
A magnetic nano-supported Cu(I)catalyst was prepared and showed high activity for cyclization of ene-yne-ketone to synthesize furans.The catalyst was easily recovered from the reaction by using external magnets and re...A magnetic nano-supported Cu(I)catalyst was prepared and showed high activity for cyclization of ene-yne-ketone to synthesize furans.The catalyst was easily recovered from the reaction by using external magnets and reused 8 times without significant loss of its catalytic activity.展开更多
We present here a facile and practical procedure for the synthesis of tetrasubstituted furans from alkynes catalyzed by palladium acetate together with cupric acetate in acetic acid,using atmospheric oxygen as a termi...We present here a facile and practical procedure for the synthesis of tetrasubstituted furans from alkynes catalyzed by palladium acetate together with cupric acetate in acetic acid,using atmospheric oxygen as a terminal oxidant.Various internal aromatic alkynes afforded the target furans in satisfactory yield.展开更多
Correction for‘Electrochemically-mediated C-H functionalization of allenes and 1,3-dicarbonyl compounds to construct tetrasubstituted furans’by Mu-Xue He et al.,Org.Chem.Front.,2022,DOI:10.1039/d1qo01458g.One of the...Correction for‘Electrochemically-mediated C-H functionalization of allenes and 1,3-dicarbonyl compounds to construct tetrasubstituted furans’by Mu-Xue He et al.,Org.Chem.Front.,2022,DOI:10.1039/d1qo01458g.One of the author names(Hai-Tao Tang)was spelled incorrectly in the published article;the corrected version is shown here.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.展开更多
C-H functionalization of allenes is an available strategy to construct heterocyclic compounds.Herein we propose a sus-tainable electrocatalytic C-H activation for the synthesis of novel highly functionalized tetrasubs...C-H functionalization of allenes is an available strategy to construct heterocyclic compounds.Herein we propose a sus-tainable electrocatalytic C-H activation for the synthesis of novel highly functionalized tetrasubstituted furans,which is accomplished by intermolecular cyclization of allenes and 1,3-dicarbonyl compounds.展开更多
A[3+2]cyclization reaction of acylacetonitriles and hydroxyacetone was developed by using Sc(OTf)_(3)as a catalyst to synthesize some furan derivatives.Bifunctional C2-based acetals,such asα-bromoacetaldehyde acetal,...A[3+2]cyclization reaction of acylacetonitriles and hydroxyacetone was developed by using Sc(OTf)_(3)as a catalyst to synthesize some furan derivatives.Bifunctional C2-based acetals,such asα-bromoacetaldehyde acetal,1,4-dithiane-2,5-diol and glycolaldehyde diethyl acetal,also reacted readily as alternative counterpart reagents to acylacetonitriles.The established reactions can be used to synthesize a well-known fungicide,fenfuram.Antifungal activity investigation against four common plant funguses indicated that some of the obtained furan products furnish general and high biological activities.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
Bio-based media, derived from cellulosic biomass depolymerisation or bioconversion processes, are composed of several chemicals and biochemicals. In this study, the main components of a hemicellulosic-based medium wer...Bio-based media, derived from cellulosic biomass depolymerisation or bioconversion processes, are composed of several chemicals and biochemicals. In this study, the main components of a hemicellulosic-based medium were analyzed using a dual detection HPLC method to separate and determine concentrations of the major monosaccharides (glucose, xylose, and arabinose), alcoholic and acidic components (ethanol, xylitol, and acetic acid) and furanic compounds (furfural and hydroxymethylfurfural (HMF)). The analyses, which employed a single stationary phase (Aminex HPX-87H) and two detection methods, were carried out under isocratic conditions and involved mobile phases consisting of 5 mM sulfuric acid and acetonitrile in different mix ratios from 0 to 0.061 mole fraction of acetonitrile. Based on the analysis run time and the chromatogram quality, the optimum condition was determined for the simultaneous quantification of the components.展开更多
Pringle Creek, identified as the source of dioxin/furan (PCDD/F) contamination to a Lake Ontario harbour was remediated in 2008. Surface sediment collected in 2013 near the floodplain remediation was no longer contami...Pringle Creek, identified as the source of dioxin/furan (PCDD/F) contamination to a Lake Ontario harbour was remediated in 2008. Surface sediment collected in 2013 near the floodplain remediation was no longer contaminated (∑<sub>17</sub>PCDD\Fs < 60 pg/g dw), but residual contamination extended downstream to the creek mouth (surface sediment maximum: ∑<sub>17</sub>PCDD\Fs 2900 pg/g dw). Nevertheless, sediment ∑<sub>17</sub>PCDD/F concentrations were lower in 2013 than pre-remediation suggesting that cleaner sediment was being deposited in the creek. Core data confirmed the decrease in sediment contamination through time since the most contaminated sediment was buried. Prior to the development of a remediation strategy for the harbour, the transport of bed-load and suspended sediment contaminated with PCDD/F was assessed. The challenge was the shallow water depth (0.6 m) throughout the creek thereby requiring non-standard sediment traps designed for this study. Suspended sediment collected in traps in 2014 showed residual contamination at the remediated site (∑<sub>17</sub>PCDD\Fs: 380 pg/g dw;TEQ (TEF fish) < 0.6 pg/g), with concentrations increasing with distance downstream mirroring surface sediment: mean ∑17PCDD\Fs concentration for suspended sediment at the creek mouth was 2200 pg/g (SD 260 pg/g dw) indicating PCDD/F contributions to the harbour. However, congener patterns in bottom sediment and suspended sediment near the remediated site and extending about 100 m downstream were similar to background upstream patterns consistent with atmospheric deposition as the source rather than the historical source which indicated that floodplain remedial actions were successful.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
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 content and the heat-treatment temperature were two important factors on the catalytic graphitization of furan resin carbon and the significant catalytic graphitization was achieved at 2400 ?C and 15 wt.% praseodymium.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, 13 C NMR, MS and EA had identified these new molecules. The important factors that...A series of compounds that contained furan skeletons were synthesized using 3,4\|bis(trimethylsilyl)furan as staring material. 1H NMR, 13 C 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
A novel phenanthro[2,3-b]furan 1,named(3-hydroxy-9-(4′-hydroxy-3′-methoxypheny1)-11-methoxy-5,6,9,10-tetrahydro- phenanthro[2,3-b]furan-10-yl)methyl acetate,and two known phenolic compounds were isolated from the tu...A novel phenanthro[2,3-b]furan 1,named(3-hydroxy-9-(4′-hydroxy-3′-methoxypheny1)-11-methoxy-5,6,9,10-tetrahydro- phenanthro[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
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
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
文摘Humans and animals can be exposed to Dioxins and Furans through ingestion of fatty food, skin contact, and breathing contaminated air. Resulting health problems include skin disease, immune problems, and cancers. Managing the release of these chemicals is therefore important. The Stockholm Convention on Persistent Organic Pollutants requires parties to adopt measures that reduce sources of these chemicals. Sierra Leone developed its National Implementation Plan (NIP) in 2008, in compliance with this requirement. However, no known further steps have been taken, particularly at community level. In 2013, the UNDP’s GEF/SGP funded a pilot project to manage the release of Dioxins and Furans from two dumpsites in Freetown, Sierra Leone. This work was sponsored with funds from that project. The work sought to delineate the exposure of communities within and around the Bormeh-Kingtom dumpsite (Kingtom, Kolleh town, Ascension town, Crab town, and Congo town) to the chemicals. The study considered sources of exposure, relative quantities generated per year, and the routes of exposure. This exposure study is a first step in managing the release from those sources. Enumerators deployed at the dumpsite every day, 7:00 AM to 6:00 PM, for three months, quantifying and recording source materials. The amount of source materials dumped per day informed calculation of Dioxin/Furan releases in grams toxicity equivalence per year. The results revealed a release of 128.914 g TEQ/year in air and residue. This implies that the communities are at high risk of inhalation and dermal exposure. Livestock, mainly pigs, are also exposed as they feed on the waste deposited in the dumpsite. Humans in turn feed on the livestock, a recipe for biomagnification. The project team has been working on developing Best Management Practices to suppress the release of the chemicals.
基金supported by NSFC(22371008),BNLMSLaboratory for Synthetic Chemistry and Chemical Biology of Health@InnoHK of ITC,HKSAR.
文摘Furans bearing alkynyl substituents are highly useful in organic synthesis.However,the methodologies to access these important furan derivatives are rather limited.We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes.This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups.Mechanistically,the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation.The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.
基金We acknowledge the National Natural Science Foundation of China(No.21472136)for financial support.
文摘Main observation and conclusion The reaction of 2-alkynylanisoles/sulfides with SOCl_(2) and DMSO was conducted to conveniently furnish the biologically interesting 3-(methylthio)-benzo[b]furans/thiophenes via intramolecular cyclization.DMSO acts as a solvent as well as a sulfur source and can also be replaced with DMSO-d_(6),enabling the incorporation of the SCD3 moiety of DMSO-d_(6) to the 3-position of the heterocyclic frameworks.
基金supported by the Natural Science Foundation of Guangdong Province(No.10151022501000033).
文摘A magnetic nano-supported Cu(I)catalyst was prepared and showed high activity for cyclization of ene-yne-ketone to synthesize furans.The catalyst was easily recovered from the reaction by using external magnets and reused 8 times without significant loss of its catalytic activity.
基金We thank Scientific and Technological Project of Zhanjiang City(No.2012C3106024)Guangdong Medical College(No.M2010006)for financial support.
文摘We present here a facile and practical procedure for the synthesis of tetrasubstituted furans from alkynes catalyzed by palladium acetate together with cupric acetate in acetic acid,using atmospheric oxygen as a terminal oxidant.Various internal aromatic alkynes afforded the target furans in satisfactory yield.
文摘Correction for‘Electrochemically-mediated C-H functionalization of allenes and 1,3-dicarbonyl compounds to construct tetrasubstituted furans’by Mu-Xue He et al.,Org.Chem.Front.,2022,DOI:10.1039/d1qo01458g.One of the author names(Hai-Tao Tang)was spelled incorrectly in the published article;the corrected version is shown here.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.
基金This work was supported by National Natural Science Foundation of China(22161008,21861006,22061003)Guangxi Natural Science Foundation of China(2021GXNSFFA220005)the Chunhui Program(GX2019001).
文摘C-H functionalization of allenes is an available strategy to construct heterocyclic compounds.Herein we propose a sus-tainable electrocatalytic C-H activation for the synthesis of novel highly functionalized tetrasubstituted furans,which is accomplished by intermolecular cyclization of allenes and 1,3-dicarbonyl compounds.
基金The authors thank the financial support of the Natural Science Foundation of Hubei Province(No.2020CFB717)the Youth Science Foundation of Hubei Academy of Agricultural Sciences(No.2021NKYJJ17)+2 种基金also gratefully acknowledge the partial support from the Program for Leading Talents of Hubei Academy of Agricultural Sciences(No.L2018031)Hubei Biopesticide Engineering Research Centre(Nos.HBERC-RC-202104 and HBERC-RC-202002)Gu thanks the National Natural Science Foundation of China of China(No.22072049).
文摘A[3+2]cyclization reaction of acylacetonitriles and hydroxyacetone was developed by using Sc(OTf)_(3)as a catalyst to synthesize some furan derivatives.Bifunctional C2-based acetals,such asα-bromoacetaldehyde acetal,1,4-dithiane-2,5-diol and glycolaldehyde diethyl acetal,also reacted readily as alternative counterpart reagents to acylacetonitriles.The established reactions can be used to synthesize a well-known fungicide,fenfuram.Antifungal activity investigation against four common plant funguses indicated that some of the obtained furan products furnish general and high biological activities.
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.
文摘Bio-based media, derived from cellulosic biomass depolymerisation or bioconversion processes, are composed of several chemicals and biochemicals. In this study, the main components of a hemicellulosic-based medium were analyzed using a dual detection HPLC method to separate and determine concentrations of the major monosaccharides (glucose, xylose, and arabinose), alcoholic and acidic components (ethanol, xylitol, and acetic acid) and furanic compounds (furfural and hydroxymethylfurfural (HMF)). The analyses, which employed a single stationary phase (Aminex HPX-87H) and two detection methods, were carried out under isocratic conditions and involved mobile phases consisting of 5 mM sulfuric acid and acetonitrile in different mix ratios from 0 to 0.061 mole fraction of acetonitrile. Based on the analysis run time and the chromatogram quality, the optimum condition was determined for the simultaneous quantification of the components.
文摘Pringle Creek, identified as the source of dioxin/furan (PCDD/F) contamination to a Lake Ontario harbour was remediated in 2008. Surface sediment collected in 2013 near the floodplain remediation was no longer contaminated (∑<sub>17</sub>PCDD\Fs < 60 pg/g dw), but residual contamination extended downstream to the creek mouth (surface sediment maximum: ∑<sub>17</sub>PCDD\Fs 2900 pg/g dw). Nevertheless, sediment ∑<sub>17</sub>PCDD/F concentrations were lower in 2013 than pre-remediation suggesting that cleaner sediment was being deposited in the creek. Core data confirmed the decrease in sediment contamination through time since the most contaminated sediment was buried. Prior to the development of a remediation strategy for the harbour, the transport of bed-load and suspended sediment contaminated with PCDD/F was assessed. The challenge was the shallow water depth (0.6 m) throughout the creek thereby requiring non-standard sediment traps designed for this study. Suspended sediment collected in traps in 2014 showed residual contamination at the remediated site (∑<sub>17</sub>PCDD\Fs: 380 pg/g dw;TEQ (TEF fish) < 0.6 pg/g), with concentrations increasing with distance downstream mirroring surface sediment: mean ∑17PCDD\Fs concentration for suspended sediment at the creek mouth was 2200 pg/g (SD 260 pg/g dw) indicating PCDD/F contributions to the harbour. However, congener patterns in bottom sediment and suspended sediment near the remediated site and extending about 100 m downstream were similar to background upstream patterns consistent with atmospheric deposition as the source rather than the historical source which indicated that floodplain remedial actions were successful.
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 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 content and the heat-treatment temperature were two important factors on the catalytic graphitization of furan resin carbon and the significant catalytic graphitization was achieved at 2400 ?C and 15 wt.% praseodymium.
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 series of compounds that contained furan skeletons were synthesized using 3,4\|bis(trimethylsilyl)furan as staring material. 1H NMR, 13 C 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A novel phenanthro[2,3-b]furan 1,named(3-hydroxy-9-(4′-hydroxy-3′-methoxypheny1)-11-methoxy-5,6,9,10-tetrahydro- phenanthro[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 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.
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.
