Chiral aromatic alcohols are the key chiral building block for many important enantiopure pharmaceu-ticals. In this work,we studied asymmetric reduction of prochiral aromatic ketone to produce the corresponding chiral...Chiral aromatic alcohols are the key chiral building block for many important enantiopure pharmaceu-ticals. In this work,we studied asymmetric reduction of prochiral aromatic ketone to produce the corresponding chiral alcohol using vegetables as the biocatalyst. Acetophenone was chosen as the model substrate. The results in-dicate that acetophenone can be reduced to the corresponding chiral alcohols with high enantioselectivity by the chosen vegetables,i.e. apple(Malus pumila),carrot(Daucus carota),cucumber(Cucumis sativus),onion(Allium cepa),potato(Soanum tuberosum),radish(Raphanus sativus),and sweet potato(Ipomoea batatas) . In the reaction,R-1-phenylethanol is produced with apple,sweet potato and potato as the catalyst,while S-1-phenylethanol is the product with the other vegetables as the catalyst. In term of the enantioselectivity and reaction yield,carrot(D. ca-rota) is the best catalyst for this reaction. Furthermore,the reaction characteristics were studied in detail using car-rot(D. carota) as the biocatalyst. The effects of various factors on the reaction were investigated and the optimal reaction conditions were determined. Under the optimal reaction conditions(reaction time 50 h,substrate concen-tration 20 mmol·L-1,reaction temperature 35 °C and pH 7),95% of e.e.(to S-1-phenylethanol) and 85% chemical yield can be obtained. This work extends the biocatalyst for the asymmetric reduction reaction of prochiral aromatic ketones,and provides a novel potential route to produce enantiopure aromatic alcohols.展开更多
Oxygen reduction reaction(ORR)plays a crucial role in many energy storage and conversion devices.Currently,the development of inexpensive and high-performance carbon-based non-precious-metal ORR catalysts in alkaline ...Oxygen reduction reaction(ORR)plays a crucial role in many energy storage and conversion devices.Currently,the development of inexpensive and high-performance carbon-based non-precious-metal ORR catalysts in alkaline media still gains a wide attention.In this paper,the mesoporous Fe-N/C catalysts were synthesized through SiO2-mediated templating method using biomass soybeans as the nitrogen and carbon sources.The SiO2 templates create a simultaneous optimization of both the surface functionalities and porous structures of Fe-N/C catalysts.Detailed investigations indicate that the Fe-N/C3 catalyst prepared with the mass ratio of SiO2 to soybean being 3:4 exhibits brilliant electrocatalytic performance,excellent long-term stability and methanol tolerance for the ORR,with the onset potential and the half-wave potential of the ORR being about 0.890 V and 0.783 V(vs RHE),respectively.Meanwhile,the desired 4-electron transfer pathway of the ORR on the catalysts can be observed.It is significantly proposed that the high BET specific surface area and the appropriate pore-size,as well as the high pyridinic-N and total nitrogen loadings may play key roles in enhancing the ORR performance for the Fe-N/C3 catalyst.These results suggest a feasible route based on the economical and sustainable soybean biomass to develop inexpensive and highly efficient non-precious metal electrochemical catalysts for the ORR.展开更多
The use of biocatalysts is attracting an increasing amount of attention in chemical catalysis.Here,we have shown that bovine serum albumin(BSA),a ubiquitous,inexpensive,non-enzymatic transport protein,can serve as a...The use of biocatalysts is attracting an increasing amount of attention in chemical catalysis.Here,we have shown that bovine serum albumin(BSA),a ubiquitous,inexpensive,non-enzymatic transport protein,can serve as an efficient,retrievable catalyst in the one-pot four-component reaction of aryl aldehydes,malononitrile,hydrazine hydrate,and ethyl acetoacetate for the synthesis of pyrano[2,3-c]pyrazoles under mild reaction conditions.The BSA biocatalyst also displayed a high catalytic affinity for acyclic/cyclic ketones to yield the corresponding pyrano[2,3-c]pyrazoles or their spirocyclic variants.The BSA could be used for at least five cycles without serious loss of catalytic activity.This novel,efficient protocol has the merits of high yield,operational simplicity,and a relatively benign environmental impact.Moreover,the method extends the promiscuity of BSA as a biocatalyst.展开更多
Sodium silicate and that calcined at 400℃ for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate (CSS) catalyst exhibited much higher catalytic activity and ...Sodium silicate and that calcined at 400℃ for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate (CSS) catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9~ was achieved at methanol/oil mole ratio of 12:1, reaction temperature 65℃, reaction time 3.0 h, and CSS/oil mass ratio of 2 Wffo. After 7 consecutive reactions without any treatment, biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported on 0 rings was prepared for continuous transesterification. The maximum yield was 99.1% under optimum conditions (reaction temperature 55 ~C, methanol velocity 1 ml. rain- 1, oil velocity 3 ml- rain- 1, and 5 tower sec- tions). These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.展开更多
The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and...The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller(BET)surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.展开更多
Autothermal steam reforming (ATR) of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effec...Autothermal steam reforming (ATR) of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effective production of hydrogen through ATR of bio-oil was performed at lower temperature with NiCuZnAl catalyst. The highest hydrogen yield from bio-oil reached 64.3% with a nearly complete bio-oil conversion at 600℃, the ratio of steam to carbon fed (S/C) of 3 and the oxygen to carbon ratio (O/C) of 0.34. The reaction conditions in ATR including temperature, O/C, S/C and weight hourly space velocity can be used to control both hydrogen yield and products distribution. The comparison between the ATR and common steam reforming of bio-oil was studied. The mechanism of the ATR of bio-oil was also discussed.展开更多
Polymeric biosurfactants were prepared by the transesterification reaction between vinyl laurate (VILA) and carboxymethylcellulose (CMC). The reaction was performed in two different reaction media ((A) DMF/pTSA...Polymeric biosurfactants were prepared by the transesterification reaction between vinyl laurate (VILA) and carboxymethylcellulose (CMC). The reaction was performed in two different reaction media ((A) DMF/pTSA and (B) DMF/K2CO3) at various reaction conditions and using microwave radiation with controlled power as heating source. The obtained water-soluble VILA-CMC derivatives were characterized by FT-IR spectroscopy and their surface-active properties evaluated. All derivatives showed a very low esterification extent and moderate surface tension lowering effect. Nevertheless, they exhibited significant emulsifying efficiency comparable to that of the synthetic surfactant, Tween 20. The results suggested that suitable surface-active VILA-CMC derivatives can be prepared under microwave heating at low microwave power and reaction times in the range of few minutes, which represents a great advantage in comparison to transesterification reactions lasting up to 6 h at conventional heating.展开更多
The direct asymmetric aldol reaction of aromatic aldehydes with cyclic or acyclic ketones was catalyzed by proteinase from Aspergillus melleus (AMP) in acetonitrile in the presence of water. A wide range of substrates...The direct asymmetric aldol reaction of aromatic aldehydes with cyclic or acyclic ketones was catalyzed by proteinase from Aspergillus melleus (AMP) in acetonitrile in the presence of water. A wide range of substrates could be transformed into the corresponding aldol products in yields up to 89%, enantioselectivities up to 91% ee and diastereoselectivities up to >99:1 (anti/syn). This work provided an example of enzyme catalytic promiscuity that widens the applicability of this biocatalyst in organic synthesis without the need for additional cofactors or special equipment.展开更多
Enzymes are biological catalysts that can convert substrates into products in biochemical reactions.In 1926,the first enzyme,urease,was determined to be a protein by James B.Sumner who won the Nobel Prize in 1946.Sinc...Enzymes are biological catalysts that can convert substrates into products in biochemical reactions.In 1926,the first enzyme,urease,was determined to be a protein by James B.Sumner who won the Nobel Prize in 1946.Since then,enzymes have been considered to be proteins,which allows them to achieve their high catalytic activity with high specific activity under mild conditions.However,in general,the enzyme activity of proteins is lost after exposure to extremes of p H and high temperature,and proteins are also susceptible to digestion by proteases in the environment,which dramatically hinders their practical applications in展开更多
基金Supported by the Natural Science Foundation of Hubei Province(2008CDB354) Wuhan Youth Scientist Dawn Foundation(200750731288)
文摘Chiral aromatic alcohols are the key chiral building block for many important enantiopure pharmaceu-ticals. In this work,we studied asymmetric reduction of prochiral aromatic ketone to produce the corresponding chiral alcohol using vegetables as the biocatalyst. Acetophenone was chosen as the model substrate. The results in-dicate that acetophenone can be reduced to the corresponding chiral alcohols with high enantioselectivity by the chosen vegetables,i.e. apple(Malus pumila),carrot(Daucus carota),cucumber(Cucumis sativus),onion(Allium cepa),potato(Soanum tuberosum),radish(Raphanus sativus),and sweet potato(Ipomoea batatas) . In the reaction,R-1-phenylethanol is produced with apple,sweet potato and potato as the catalyst,while S-1-phenylethanol is the product with the other vegetables as the catalyst. In term of the enantioselectivity and reaction yield,carrot(D. ca-rota) is the best catalyst for this reaction. Furthermore,the reaction characteristics were studied in detail using car-rot(D. carota) as the biocatalyst. The effects of various factors on the reaction were investigated and the optimal reaction conditions were determined. Under the optimal reaction conditions(reaction time 50 h,substrate concen-tration 20 mmol·L-1,reaction temperature 35 °C and pH 7),95% of e.e.(to S-1-phenylethanol) and 85% chemical yield can be obtained. This work extends the biocatalyst for the asymmetric reduction reaction of prochiral aromatic ketones,and provides a novel potential route to produce enantiopure aromatic alcohols.
基金Project(21406273)supported by the National Natural Science Foundation of China
文摘Oxygen reduction reaction(ORR)plays a crucial role in many energy storage and conversion devices.Currently,the development of inexpensive and high-performance carbon-based non-precious-metal ORR catalysts in alkaline media still gains a wide attention.In this paper,the mesoporous Fe-N/C catalysts were synthesized through SiO2-mediated templating method using biomass soybeans as the nitrogen and carbon sources.The SiO2 templates create a simultaneous optimization of both the surface functionalities and porous structures of Fe-N/C catalysts.Detailed investigations indicate that the Fe-N/C3 catalyst prepared with the mass ratio of SiO2 to soybean being 3:4 exhibits brilliant electrocatalytic performance,excellent long-term stability and methanol tolerance for the ORR,with the onset potential and the half-wave potential of the ORR being about 0.890 V and 0.783 V(vs RHE),respectively.Meanwhile,the desired 4-electron transfer pathway of the ORR on the catalysts can be observed.It is significantly proposed that the high BET specific surface area and the appropriate pore-size,as well as the high pyridinic-N and total nitrogen loadings may play key roles in enhancing the ORR performance for the Fe-N/C3 catalyst.These results suggest a feasible route based on the economical and sustainable soybean biomass to develop inexpensive and highly efficient non-precious metal electrochemical catalysts for the ORR.
基金supported by the National Natural Science Foundation of China(21372099,21072077)the the Natural Science Foundation of Guangdong Province(10151063201000051,8151063201000016)~~
文摘The use of biocatalysts is attracting an increasing amount of attention in chemical catalysis.Here,we have shown that bovine serum albumin(BSA),a ubiquitous,inexpensive,non-enzymatic transport protein,can serve as an efficient,retrievable catalyst in the one-pot four-component reaction of aryl aldehydes,malononitrile,hydrazine hydrate,and ethyl acetoacetate for the synthesis of pyrano[2,3-c]pyrazoles under mild reaction conditions.The BSA biocatalyst also displayed a high catalytic affinity for acyclic/cyclic ketones to yield the corresponding pyrano[2,3-c]pyrazoles or their spirocyclic variants.The BSA could be used for at least five cycles without serious loss of catalytic activity.This novel,efficient protocol has the merits of high yield,operational simplicity,and a relatively benign environmental impact.Moreover,the method extends the promiscuity of BSA as a biocatalyst.
基金Supported by the National Natural Science Foundation of China(21306088)National Key Technologies R&D Program of China(2015BAD15B07)+1 种基金State Key Laboratory of Chemical Engineering(SKL-Ch E-13A01,Tsinghua University,China)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,China)
文摘Sodium silicate and that calcined at 400℃ for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate (CSS) catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9~ was achieved at methanol/oil mole ratio of 12:1, reaction temperature 65℃, reaction time 3.0 h, and CSS/oil mass ratio of 2 Wffo. After 7 consecutive reactions without any treatment, biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported on 0 rings was prepared for continuous transesterification. The maximum yield was 99.1% under optimum conditions (reaction temperature 55 ~C, methanol velocity 1 ml. rain- 1, oil velocity 3 ml- rain- 1, and 5 tower sec- tions). These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.
文摘The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller(BET)surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.
文摘Autothermal steam reforming (ATR) of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effective production of hydrogen through ATR of bio-oil was performed at lower temperature with NiCuZnAl catalyst. The highest hydrogen yield from bio-oil reached 64.3% with a nearly complete bio-oil conversion at 600℃, the ratio of steam to carbon fed (S/C) of 3 and the oxygen to carbon ratio (O/C) of 0.34. The reaction conditions in ATR including temperature, O/C, S/C and weight hourly space velocity can be used to control both hydrogen yield and products distribution. The comparison between the ATR and common steam reforming of bio-oil was studied. The mechanism of the ATR of bio-oil was also discussed.
文摘Polymeric biosurfactants were prepared by the transesterification reaction between vinyl laurate (VILA) and carboxymethylcellulose (CMC). The reaction was performed in two different reaction media ((A) DMF/pTSA and (B) DMF/K2CO3) at various reaction conditions and using microwave radiation with controlled power as heating source. The obtained water-soluble VILA-CMC derivatives were characterized by FT-IR spectroscopy and their surface-active properties evaluated. All derivatives showed a very low esterification extent and moderate surface tension lowering effect. Nevertheless, they exhibited significant emulsifying efficiency comparable to that of the synthetic surfactant, Tween 20. The results suggested that suitable surface-active VILA-CMC derivatives can be prepared under microwave heating at low microwave power and reaction times in the range of few minutes, which represents a great advantage in comparison to transesterification reactions lasting up to 6 h at conventional heating.
基金2011 Select Project in Scientific and Technological Activities for Returned Scholars of Chongqing Personnel Bureau, and the Doctoral Foundation ofSouthwest University (SWU112019)
文摘The direct asymmetric aldol reaction of aromatic aldehydes with cyclic or acyclic ketones was catalyzed by proteinase from Aspergillus melleus (AMP) in acetonitrile in the presence of water. A wide range of substrates could be transformed into the corresponding aldol products in yields up to 89%, enantioselectivities up to 91% ee and diastereoselectivities up to >99:1 (anti/syn). This work provided an example of enzyme catalytic promiscuity that widens the applicability of this biocatalyst in organic synthesis without the need for additional cofactors or special equipment.
文摘Enzymes are biological catalysts that can convert substrates into products in biochemical reactions.In 1926,the first enzyme,urease,was determined to be a protein by James B.Sumner who won the Nobel Prize in 1946.Since then,enzymes have been considered to be proteins,which allows them to achieve their high catalytic activity with high specific activity under mild conditions.However,in general,the enzyme activity of proteins is lost after exposure to extremes of p H and high temperature,and proteins are also susceptible to digestion by proteases in the environment,which dramatically hinders their practical applications in