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
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
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
The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under...The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.展开更多
Two benzofuran derivatives were synthesized from 3,4-bis(trimethylsilyl) furan after a series of reactions. Their structures were identified by 1H NMR, 13C NMR, MS and EA.
The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. A...The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. Attempted Pummerer reaction of a furan sulfoxide derivative produced four interesting furan derivatives. Base promoted annulation between methyl 2-(phenylsulfinylmethyl)-3-furoate and 2-cyclohexenone proceeded to give dihydro naphtho[2,3-b]furanone derivative in a regiospecific manner.展开更多
Bread is still the most important food in Polish households. Staropolski and Pytlowy are two typical Polish breads, prepared with wheat and rye flour. The aim of this study was to examine the occurrence of volatile co...Bread is still the most important food in Polish households. Staropolski and Pytlowy are two typical Polish breads, prepared with wheat and rye flour. The aim of this study was to examine the occurrence of volatile contaminants such as furan and its derivatives, and present a volatile profile of the most common furan derivatives in the described products. To measure concentration of chemical compounds such as furan and furan derivatives, fast and effective solid-phase micro-extraction/gas chromatography/mass spectrometry （SPME/GC/MS） methods were adapted. This study showed the differences in furan occurrence between Pytlowy and Staropolski, however, the greater differences were observed between different times and temperatures of baking rather than between the bread types. Clearly, the higher concentrations were found in products prepared during the longest baking time period of 50 min, and temperatures of 230 ℃ and 240 ℃. The highest furan level was detected in Staropolski 28.89 ± 1.16/μg/kg, baked for 50 min at 230 ℃ in bread crust. The volatile fraction of bread crust was composed of 5-9 furan derivatives while crumb layer contained only furan-2-pentyl. It was concluded that furan is present in almost each type of bread and percentage of furan derivatives in all volatile fractions ranged from 0.5 % to 60.6% in crust of examined bars.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
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
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
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
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
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
Diterpenoid lactones(DLs),a group of furan-containing compounds found in Dioscorea bulbifera L.(DB),have been reported to be associated with hepatotoxicity.Different hepatotoxicities of these DLs have been observed in...Diterpenoid lactones(DLs),a group of furan-containing compounds found in Dioscorea bulbifera L.(DB),have been reported to be associated with hepatotoxicity.Different hepatotoxicities of these DLs have been observed in vitro,but reasonable explanations for the differential hepatotoxicity have not been provided.Herein,the present study aimed to confirm the potential factors that contribute to varied hepatotoxicity of four representative DLs(diosbulbins A,B,C,F).In vitro toxic effects were evaluated in various cell models and the interactions between DLs and CYP3 A4 at the atomic level were simulated by molecular docking.Results showed that DLs exhibited varied cytotoxicities,and that CYP3 A4 played a modulatory role in this process.Moreover,structural variation may cause different affinities between DLs and CYP3 A4,which was positively correlated with the observation of cytotoxicity.In addition,analysis of the glutathione(GSH)conjugates indicated that reactive intermediates were formed by metabolic oxidation that occurred on the furan moiety of DLs,whereas,GSH consumption analysis reflected the consistency between the reactive metabolites and the hepatotoxicity.Collectively,our findings illustrated that the metabolic regulation played a crucial role in generating the varied hepatotoxicity of DLs.展开更多
Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based （PBF backbone） graft （co）polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furar...Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based （PBF backbone） graft （co）polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furardmaleimide were synthesized. Atom transfer radical polymerization （ATRP） was used to synthesize graft copolymers with thermo-responsive transformation from graft copolymers to linear polymers with bimodal or wide MWD. The NMR measurements indicated that the Diels-Alder reaction and retro- Diels-Alder reaction occurred, depending on the change of the temperature, meaning that the side chains could be cleaved and reformed according to the variation of the temperature. GPC measurements demonstrated that the molecular weights of the polymers were thermo- responsive. Furthermore, three graft copolymers with various branching chains （PBF-g-PBA, PBF-g-P（BMA-co-MA） and PBF-g-PBMA） were compared to study the influence of compatibility between the backbone and the branching chain on the efficiency of Diels-Alder reaction after the cleavage of the DA linkage. The results showed that the ability of the side chains to come back to the main chain was strongly affected by the compatibility between the backbone and the side chains and the flexibility of the polymer chains.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
A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their...A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis （L） Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.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 electr...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 ~3TCBQ 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
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
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.
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The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.
文摘Two benzofuran derivatives were synthesized from 3,4-bis(trimethylsilyl) furan after a series of reactions. Their structures were identified by 1H NMR, 13C NMR, MS and EA.
文摘The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. Attempted Pummerer reaction of a furan sulfoxide derivative produced four interesting furan derivatives. Base promoted annulation between methyl 2-(phenylsulfinylmethyl)-3-furoate and 2-cyclohexenone proceeded to give dihydro naphtho[2,3-b]furanone derivative in a regiospecific manner.
文摘Bread is still the most important food in Polish households. Staropolski and Pytlowy are two typical Polish breads, prepared with wheat and rye flour. The aim of this study was to examine the occurrence of volatile contaminants such as furan and its derivatives, and present a volatile profile of the most common furan derivatives in the described products. To measure concentration of chemical compounds such as furan and furan derivatives, fast and effective solid-phase micro-extraction/gas chromatography/mass spectrometry （SPME/GC/MS） methods were adapted. This study showed the differences in furan occurrence between Pytlowy and Staropolski, however, the greater differences were observed between different times and temperatures of baking rather than between the bread types. Clearly, the higher concentrations were found in products prepared during the longest baking time period of 50 min, and temperatures of 230 ℃ and 240 ℃. The highest furan level was detected in Staropolski 28.89 ± 1.16/μg/kg, baked for 50 min at 230 ℃ in bread crust. The volatile fraction of bread crust was composed of 5-9 furan derivatives while crumb layer contained only furan-2-pentyl. It was concluded that furan is present in almost each type of bread and percentage of furan derivatives in all volatile fractions ranged from 0.5 % to 60.6% in crust of examined bars.
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.
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 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 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.
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supported by the National Natural Science Foundation of China(No.81773993)
文摘Diterpenoid lactones(DLs),a group of furan-containing compounds found in Dioscorea bulbifera L.(DB),have been reported to be associated with hepatotoxicity.Different hepatotoxicities of these DLs have been observed in vitro,but reasonable explanations for the differential hepatotoxicity have not been provided.Herein,the present study aimed to confirm the potential factors that contribute to varied hepatotoxicity of four representative DLs(diosbulbins A,B,C,F).In vitro toxic effects were evaluated in various cell models and the interactions between DLs and CYP3 A4 at the atomic level were simulated by molecular docking.Results showed that DLs exhibited varied cytotoxicities,and that CYP3 A4 played a modulatory role in this process.Moreover,structural variation may cause different affinities between DLs and CYP3 A4,which was positively correlated with the observation of cytotoxicity.In addition,analysis of the glutathione(GSH)conjugates indicated that reactive intermediates were formed by metabolic oxidation that occurred on the furan moiety of DLs,whereas,GSH consumption analysis reflected the consistency between the reactive metabolites and the hepatotoxicity.Collectively,our findings illustrated that the metabolic regulation played a crucial role in generating the varied hepatotoxicity of DLs.
基金financially supported by the National Natural Science Foundation of China(Nos.51233005,21374114,and21274152)
文摘Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based （PBF backbone） graft （co）polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furardmaleimide were synthesized. Atom transfer radical polymerization （ATRP） was used to synthesize graft copolymers with thermo-responsive transformation from graft copolymers to linear polymers with bimodal or wide MWD. The NMR measurements indicated that the Diels-Alder reaction and retro- Diels-Alder reaction occurred, depending on the change of the temperature, meaning that the side chains could be cleaved and reformed according to the variation of the temperature. GPC measurements demonstrated that the molecular weights of the polymers were thermo- responsive. Furthermore, three graft copolymers with various branching chains （PBF-g-PBA, PBF-g-P（BMA-co-MA） and PBF-g-PBMA） were compared to study the influence of compatibility between the backbone and the branching chain on the efficiency of Diels-Alder reaction after the cleavage of the DA linkage. The results showed that the ability of the side chains to come back to the main chain was strongly affected by the compatibility between the backbone and the side chains and the flexibility of the polymer chains.
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.
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.
基金financially supported by the National Natural Science Foundation of China (Nos.31171877,31571991,21372132)the International Science & Technology Cooperation Program of China (No.2014DFR41030)
文摘A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis （L） Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.
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 ~3TCBQ 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 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.
