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
The rare ginsenoside Compound K (C-K) is attracting more attention because of its good physiological activity and urgent need. There are many pathways to obtain ginsenoside C-K, including chemical and biological met...The rare ginsenoside Compound K (C-K) is attracting more attention because of its good physiological activity and urgent need. There are many pathways to obtain ginsenoside C-K, including chemical and biological methods. Among these, the conversion of PPD-type ginsenosides by enzymatic hydrolysis is a trend due to its high efficiency and mild conditions. For effectively extracting from the other panaxadiol saponins, the conversion process for ginsenoside C-K was investigated using snailases in this study. The univariate experimental design and response surface methodology were used to determine the optimal hydrolysis conditions for the conversion of ginsenoside Rbl into ginsenoside C-K by snailases. The optimum conditions were as follows: pH 5,12, temperature 51 ℃, ratio of snailase/substrate 0.21, and reaction time 48 h. On the basis of these parameters, the addition of 1.0 mmol· L- 1 ferric ion was found to significantly improve the enzymolysis ofsnailases for the first time. With the above conditions, the maximum conversion rate reached 89.7%, suggesting that the process can obviously increase the yield of ginsenoside C-K. The bioassay tests indicated that the ginsenoside C-K showed anti-tumor activity in a series of tumor cell lines. Based on these results, we can conclude that the process of rare ginsenoside C- K production by enzymolysis with snailase is feasible, efficient, and suitable for the industrial production and application.展开更多
With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase compos...With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.展开更多
The biodegradability of wastewater containing priority pollutant pesticideVydine or triadimenol(C14H18CLN3O2) in different bio-reactor configurations was investigated.Two laboratory scale biological reactors were em...The biodegradability of wastewater containing priority pollutant pesticideVydine or triadimenol(C14H18CLN3O2) in different bio-reactor configurations was investigated.Two laboratory scale biological reactors were employed:one reactor under aerobic condition and the other under anaerobic condition.The aerobic reactor was operated at an ambient temperature(22±2) °C,while the anaerobic reactor was run in the lower mesophilic range(30±2) °C.The effect of pesticide concentration,hydraulic retention time(HRT) ,and co-substrate on the treatment process was explored,using glucose as a supplemental carbon substrate.More than 96%pesticide was removed after an acclimation period of approximately 172 d(aerobic) and 230 d(anaerobic) .The aerobic reactor achieved complete Vydine utilization at feed concentrations up to 25 mg·L^-1 .On the other hand,the anaerobic reactor was able to degrade 25 mg·L^-1 of Vydine.Moreover,glucose was consumed first throughout the experiment in a sequential utilization pattern.The combination of anaerobic and aerobic biological processes yielded higher biomass concentration and lower retention time than individual units.The biomass in the combined reactors was first acclimated with the corresponding pesticide.Then,the target pesticide,at a concentration of 25 mg·L^-1,was sequentially treated in a semi batch mode in the reactors.HRT studies showed that 24 h HRT of aerobic and 12 h HRT of anaerobic were the optimum combination for the treatment of simulated wastewater containing Vydine,which produced Vydine effluent at concentration below 0.1 mg·L^-1 .The optimum ratio of substrate(Vydine) to co-substrate(glucose) was 1︰100.展开更多
The synthesis of inorganic materials with special morphologies with the assistance of biological molecules is a potential development in the field of controllable growth and assembly of nanomaterials. In this paper, B...The synthesis of inorganic materials with special morphologies with the assistance of biological molecules is a potential development in the field of controllable growth and assembly of nanomaterials. In this paper, BaF2 nanocrystals in patterns of well-defined linear and erythrocyte-shaped structure were synthesized with the assistance of Escherichia coil DNA. Morphology and the arrangement of BaF2 particles on DNA were controllable by altering the reaction condition. Square nanoparticles arranged in linear chains were gained with the assistance of normal DNA; while, erythrocyte-shaped BaF2 nanospheres were synthesized with the assistance of denatured DNA. Besides, the influences of solvent, reaction temperature, concentration of reactants and the heating time on the morphology of the BaF2 particles were studied.展开更多
Organic pollution is a serious environmental problem in coastal areas and it is important to establish quantitative methods for monitoring this pollution. This study screened a series of sensitive biomarkers to constr...Organic pollution is a serious environmental problem in coastal areas and it is important to establish quantitative methods for monitoring this pollution. This study screened a series of sensitive biomarkers to construct an integrated biomarker response (IBR) index using Mytilus edulis. Mussels were exposed to the polycyclic aromatic hydrocarbon anthracene trader controlled laboratory conditions and the activities of components of the glutathione antioxidant system, and the concentrations of oxidative-damage markers, were measured in the gills and digestive glands. Anthracene exposure resulted in increased levels of malondialdehyde (MDA) and superoxide radicals (O2-·), indicating that oxidative damage had occurred. Correspondingly, anthracene exposure induced increased activities of glutathione S-transferase (GST), glutathione peroxidase (GPx) and reduced glutathione (GSH) in digestive glands, and GPx and glutathione reductase (GR) in gills, consistent with stimulation of the antioxidant system. A field experiment was set up, in which mussels from a relatively clean area were transplanted to a contaminated site. One month later, the activities of GST, GPx and GR had increased in several tissues, particularly in the digestive glands. Based on the laboratory experiment, an IBR, which showed a positive relationship with anthracene exposure, was constructed. The IBR is suggested to be a potentially useful tool for assessing anthracene pollution.展开更多
Due to their structural diversity and variety of biological activities, marine natural products have been the subject of extensive study. These compounds, especially phospholipid polycyclic aromatic hydrocarbons, have...Due to their structural diversity and variety of biological activities, marine natural products have been the subject of extensive study. These compounds, especially phospholipid polycyclic aromatic hydrocarbons, have a wide range of pharmacological applications, including embedded DNA and central nervous system, anti-tumor, anti-virus, anti-parasite, anti-bacterial, and antithrombotic effects. Unfortunately, the insufficient drug sources have limited the development of these compounds. In this study, we isolated salinpostin compounds from a fermentation solution of marine-derived Salinospora sp., which has a common bicyclic enol-phosphotriester core framework, as well as potent and selective antimalarial activities against P. falciparum with EC_(50)=50 nmolL^(-1). The chemical synthesis of these compounds in greater quantities is necessary for their use in bioactivity studies. Thus we explored a short route with high yields and mild reaction conditions, which can generate combinatorial libraries for drug discovery and lead optimization. We developed a new total synthesis method for six cyclic enol-phosphotriester salinipotin compounds and their diastereomers. For the total synthesis of cyclipostin P, we prepared cyclic enol-phosphotriester salinipostin compounds in 10 steps from a readily accessible starting material, 1,3-dihydroxyacetone, and obtained an overall yield of 1.29%. We fully characterized these compounds by proton nuclear magnetic resonance(~1H-NMR), carbon-13 NMR(^(13)C-NMR), and high-resolution mass spectrometry(HRMS) analyses, and found they coincide absolutely with the same compounds reported previously.展开更多
The discovery of the novel reactivity of conjugated enynes,mediated by readily available halogenation reagents,opens a broad range of mechanistically unique pathways for the synthesis of highly functionalized chiral a...The discovery of the novel reactivity of conjugated enynes,mediated by readily available halogenation reagents,opens a broad range of mechanistically unique pathways for the synthesis of highly functionalized chiral allene derivatives.Bromoallenyl pyrrolidines can be synthesized via 1,4-addition of sulfonamide nitrogen nucleophiles and halogens to conjugated enynes.This process can lead to simultaneous formation of a highly functionalized axially chiral allene and a stereogenic center under economical and environmentally friendly reaction conditions.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Supported by the National Natural Science Foundation of China(21476182,21776227,21776228)Shaanxi Key Laboratory of Degradable Biomedical Materials Program(2014SZS07-K04,2014SZS07-P05,15JS106,2014SZS07-Z01,2014SZS07-Z02,2016SZSj-35,2014SZS07-K03)Shaanxi R&D Center of Biomaterials and Fermentation Engineering Program(2015HBGC-04)
文摘The rare ginsenoside Compound K (C-K) is attracting more attention because of its good physiological activity and urgent need. There are many pathways to obtain ginsenoside C-K, including chemical and biological methods. Among these, the conversion of PPD-type ginsenosides by enzymatic hydrolysis is a trend due to its high efficiency and mild conditions. For effectively extracting from the other panaxadiol saponins, the conversion process for ginsenoside C-K was investigated using snailases in this study. The univariate experimental design and response surface methodology were used to determine the optimal hydrolysis conditions for the conversion of ginsenoside Rbl into ginsenoside C-K by snailases. The optimum conditions were as follows: pH 5,12, temperature 51 ℃, ratio of snailase/substrate 0.21, and reaction time 48 h. On the basis of these parameters, the addition of 1.0 mmol· L- 1 ferric ion was found to significantly improve the enzymolysis ofsnailases for the first time. With the above conditions, the maximum conversion rate reached 89.7%, suggesting that the process can obviously increase the yield of ginsenoside C-K. The bioassay tests indicated that the ginsenoside C-K showed anti-tumor activity in a series of tumor cell lines. Based on these results, we can conclude that the process of rare ginsenoside C- K production by enzymolysis with snailase is feasible, efficient, and suitable for the industrial production and application.
基金the financial support from the National Natural Science Foundation of China (No. 21266022, No. 21466022)the National High Technology Research and Development Program 863 (2014AA022002, 2012AA101800-03, 2012AA021205-6, 2012AA021704)+1 种基金the Key Programs of the National Laboratory (No. SKLFZZB-201312)the International Science & Technology Cooperation Program of China (2014DFA61040)
文摘With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.
文摘The biodegradability of wastewater containing priority pollutant pesticideVydine or triadimenol(C14H18CLN3O2) in different bio-reactor configurations was investigated.Two laboratory scale biological reactors were employed:one reactor under aerobic condition and the other under anaerobic condition.The aerobic reactor was operated at an ambient temperature(22±2) °C,while the anaerobic reactor was run in the lower mesophilic range(30±2) °C.The effect of pesticide concentration,hydraulic retention time(HRT) ,and co-substrate on the treatment process was explored,using glucose as a supplemental carbon substrate.More than 96%pesticide was removed after an acclimation period of approximately 172 d(aerobic) and 230 d(anaerobic) .The aerobic reactor achieved complete Vydine utilization at feed concentrations up to 25 mg·L^-1 .On the other hand,the anaerobic reactor was able to degrade 25 mg·L^-1 of Vydine.Moreover,glucose was consumed first throughout the experiment in a sequential utilization pattern.The combination of anaerobic and aerobic biological processes yielded higher biomass concentration and lower retention time than individual units.The biomass in the combined reactors was first acclimated with the corresponding pesticide.Then,the target pesticide,at a concentration of 25 mg·L^-1,was sequentially treated in a semi batch mode in the reactors.HRT studies showed that 24 h HRT of aerobic and 12 h HRT of anaerobic were the optimum combination for the treatment of simulated wastewater containing Vydine,which produced Vydine effluent at concentration below 0.1 mg·L^-1 .The optimum ratio of substrate(Vydine) to co-substrate(glucose) was 1︰100.
基金Supported by the National Natural Science Foundation of China(Nos.21371149,21671168)the Natural Science Foundation of Hebei Province(Nos.B2016203498,GCC2014009)
文摘The synthesis of inorganic materials with special morphologies with the assistance of biological molecules is a potential development in the field of controllable growth and assembly of nanomaterials. In this paper, BaF2 nanocrystals in patterns of well-defined linear and erythrocyte-shaped structure were synthesized with the assistance of Escherichia coil DNA. Morphology and the arrangement of BaF2 particles on DNA were controllable by altering the reaction condition. Square nanoparticles arranged in linear chains were gained with the assistance of normal DNA; while, erythrocyte-shaped BaF2 nanospheres were synthesized with the assistance of denatured DNA. Besides, the influences of solvent, reaction temperature, concentration of reactants and the heating time on the morphology of the BaF2 particles were studied.
基金Supported by the Joint Funds of National Natural Science Foundation of ChinaMarine Science Research Center of the People’s Government of Shandong Province(No.U1406403)
文摘Organic pollution is a serious environmental problem in coastal areas and it is important to establish quantitative methods for monitoring this pollution. This study screened a series of sensitive biomarkers to construct an integrated biomarker response (IBR) index using Mytilus edulis. Mussels were exposed to the polycyclic aromatic hydrocarbon anthracene trader controlled laboratory conditions and the activities of components of the glutathione antioxidant system, and the concentrations of oxidative-damage markers, were measured in the gills and digestive glands. Anthracene exposure resulted in increased levels of malondialdehyde (MDA) and superoxide radicals (O2-·), indicating that oxidative damage had occurred. Correspondingly, anthracene exposure induced increased activities of glutathione S-transferase (GST), glutathione peroxidase (GPx) and reduced glutathione (GSH) in digestive glands, and GPx and glutathione reductase (GR) in gills, consistent with stimulation of the antioxidant system. A field experiment was set up, in which mussels from a relatively clean area were transplanted to a contaminated site. One month later, the activities of GST, GPx and GR had increased in several tissues, particularly in the digestive glands. Based on the laboratory experiment, an IBR, which showed a positive relationship with anthracene exposure, was constructed. The IBR is suggested to be a potentially useful tool for assessing anthracene pollution.
基金supported by the National Natural Science Foundation of China (No. 81373322)the Innovation Project from Qingdao National Laboratory for Marine Science and Technology (No. 2015ASKJ02)the Taishan Scholar Project Fund of Shandong Province
文摘Due to their structural diversity and variety of biological activities, marine natural products have been the subject of extensive study. These compounds, especially phospholipid polycyclic aromatic hydrocarbons, have a wide range of pharmacological applications, including embedded DNA and central nervous system, anti-tumor, anti-virus, anti-parasite, anti-bacterial, and antithrombotic effects. Unfortunately, the insufficient drug sources have limited the development of these compounds. In this study, we isolated salinpostin compounds from a fermentation solution of marine-derived Salinospora sp., which has a common bicyclic enol-phosphotriester core framework, as well as potent and selective antimalarial activities against P. falciparum with EC_(50)=50 nmolL^(-1). The chemical synthesis of these compounds in greater quantities is necessary for their use in bioactivity studies. Thus we explored a short route with high yields and mild reaction conditions, which can generate combinatorial libraries for drug discovery and lead optimization. We developed a new total synthesis method for six cyclic enol-phosphotriester salinipotin compounds and their diastereomers. For the total synthesis of cyclipostin P, we prepared cyclic enol-phosphotriester salinipostin compounds in 10 steps from a readily accessible starting material, 1,3-dihydroxyacetone, and obtained an overall yield of 1.29%. We fully characterized these compounds by proton nuclear magnetic resonance(~1H-NMR), carbon-13 NMR(^(13)C-NMR), and high-resolution mass spectrometry(HRMS) analyses, and found they coincide absolutely with the same compounds reported previously.
基金the University of Wisconsin-Madison and the American Chemical Society Petroleum Research Fund (48092-G) for funding
文摘The discovery of the novel reactivity of conjugated enynes,mediated by readily available halogenation reagents,opens a broad range of mechanistically unique pathways for the synthesis of highly functionalized chiral allene derivatives.Bromoallenyl pyrrolidines can be synthesized via 1,4-addition of sulfonamide nitrogen nucleophiles and halogens to conjugated enynes.This process can lead to simultaneous formation of a highly functionalized axially chiral allene and a stereogenic center under economical and environmentally friendly reaction conditions.