Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flo...Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).展开更多
The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the react...The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.展开更多
To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment usin...To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguiUicaudatus) as experimental fish was performed. Larval loaches were kept in net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied, the mean concentration of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE 209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE 209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.展开更多
Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecycla...Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM_(3-6) and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content(less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMM_n were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMM_n from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.展开更多
This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample...This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample with a tuneable acidity has been proposed as the catalytic system,being tested in a stirred reactor under different etherification conditions.Although a reaction temperature as high as 200℃resulted to be beneficial in terms of glycerol conversion(-90%),only by operating at milder conditions the product selectivity to glycerol-ethers can be better controlled,in order to obtain a bio-fuel complying with the requirements for mixing with fossil diesel or biodiesel,without any need of purification from large amount of by-products.A comprehensive identification of all the compounds formed during the reaction was performed by a GC-MS analysis,on the basis of the complex network of consecutive and parallel reaction paths leading not only to the desired ethers,but also to many side products not detected in similar acid-catalyzed reactions in liquid phase and not available in the most used mass-spectra libraries.展开更多
Alcohols are selectively and efficiently protected as their tetrahydropranyl ethers in the presence of a catalytic amount of Fe(HSO4)3 in good to high yields. All reactions are performed under mild and completely he...Alcohols are selectively and efficiently protected as their tetrahydropranyl ethers in the presence of a catalytic amount of Fe(HSO4)3 in good to high yields. All reactions are performed under mild and completely heterogeneous reaction conditions.展开更多
Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functiona...Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functional Materials by Ma group,discovered that strong coordination force could be founded between 15-Crown-5 ether(15-C-5) and Li+,which facilitates the crown ether(15-C-1) to participate in the solvation structure of Li+ in the electrolyte for the same purpose.Such a novel strategy might impact the design of highperformance and safe lithium metal batteries(LMB s).展开更多
We measured 39 polybrominated diphenyl ethers (PBDEs) in the muscle tissue of three species of fish (Sciaenops ocellatus,Sparus macrocephalus,and Lateolabrax japonicus) and four species of shellfish (Tegillarca g...We measured 39 polybrominated diphenyl ethers (PBDEs) in the muscle tissue of three species of fish (Sciaenops ocellatus,Sparus macrocephalus,and Lateolabrax japonicus) and four species of shellfish (Tegillarca granosa,Cyclina sinensis,Sinonovacula constricta,and Ostrea cucullata) that were collected downstream of electronic-waste recycling plants in Taizhou,China.A total of 24 PBDE congeners (PBDE 24) in the samples were detected.The PBDE 24 (total PBDE) ranged from 545.4 to 1688.7 ng/kg ww (wet weight).The mean PBDE 24 concentration was 1382.6 ng/kg ww in fish and 858.1 ng/kg ww in shellfish.The lower brominated congeners were detected at relatively high concentrations in all species.The penta-products,produced from e-waste,were found at relatively low levels.A principal component analysis suggested a significant correlation among di-,tri-,tetra-,and hepta-BDEs for the three species of fish.Similarly,we found a significant correlation between mono-and tri-BDEs in the shellfish.Our results suggested that the processes of PBDE metabolism and elimination were similar in both fish and shellfish.In addition,the primary source of PBDEs appeared to be from the debromination of high brominated PBDEs.展开更多
Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 42 hal...Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 42 halogenated anisoles at the HF/6-31 G^* level. A number of statistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.展开更多
This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers(PBDEs)in atmospheric particulate matter using selective pressurized liquid e...This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers(PBDEs)in atmospheric particulate matter using selective pressurized liquid extraction(SPLE)and gas chromatography–mass spectrometry with a negative chemical ionization(GC-NCI-MS).Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70℃ using hexane/dichloromethane(50:50,v/v)as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ng·mL^-1 for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pg·m^-3.展开更多
Objective:To investigate the metabolites of polybrominated diphenyl ether 99(BDE-99)and its related cytochrome P450s in an in vitro system.Methods:Rat primary hepatocytes were isolated and treated with BDE-99 for ...Objective:To investigate the metabolites of polybrominated diphenyl ether 99(BDE-99)and its related cytochrome P450s in an in vitro system.Methods:Rat primary hepatocytes were isolated and treated with BDE-99 for 24-72 h.Metabolites were then extracted from the hepatocytes and media,and detected by GC/MS.Several mRNAs of metabolic enzymes were also extracted from the same cells and the gene expression levels were determined using quantitative real-time PCR.In addition,selected recombinant cytochrome P450s(CYPs) were expressed in a bacurovirus/sf9 system,and these were further used to explore the metabolism of BDE-99 in vitro.The parent depletion approach was used for screening the ability of CYPs to eliminate BDE-99.Results: A reductively debrominated metabolite,BDE-47,and three oxidative metabolites,2,4,5-tribromophenol,5-OH-BDE-47,and 5'-OH-BDE-99,were identified from the BDE-99-treated rat hepatocytes,whereas no MeO metabolite was detected in the system.RT-PCR analysis showed that CYP 3A23/3A1,1A2,and 2B1/2 were induced by BDE-99.Furthermore,using the heterological expressed CYP proteins in in vitro BDE-99 metabolism experiments we found that CYP1A2 and CYP3A4 showed the highest metabolic efficiency for BDE-99,with the metabolic clearance rates of CYP1A2 and CYP3A4 being 30.3%and 27.7%,respectively.CYP1A1 and CYP2A6 displayed relatively low clearance rates,while CYP2E1 seemed not to be associated with the BDE-99 metabolism.Conclusions:In our in vitro rat primary hepatocyte metabolism system,four metabolites of BDE-99 were identified,and CYP3A4 and CYP1A2 were demonstrated to be involved in the BDE-99 metabolism.展开更多
Four cellulose ethers(CEs) were compared for their effects on the pore structure of cement paste using mercury intrusion porosimetry. The experimental results show that the total pore volume and porosity of cement p...Four cellulose ethers(CEs) were compared for their effects on the pore structure of cement paste using mercury intrusion porosimetry. The experimental results show that the total pore volume and porosity of cement pastes containing the four cellulose ethers are significantly higher than that of the pure cement pastes and the total pore volume and porosity of cement pastes containing HEC(hydroxyethyl cellulose ether) or low viscosity cellulose ethers are low in four CEs. By changing the surface tension and viscosity of liquid phase and the strengthening of liquid film between air voids in cement pastes, CEs affect the formation, diameter evolution and upward movement of air voids and the pore structure of hardening cement paste. For the four CEs, the pore volume of cement pastes containing HEC or low viscosity cellulose ethers is higher with the diameter of 30-70 nm while lower with the diameter larger than 70 nm. CEs affect the pore structure of cement paste mainly through their effects on the evolvement of the small air voids into bigger ones when the pore diameter is below 70 nm and their effects on the entrainment and stabilization of air voids when the pore diameter is above 70 nm.展开更多
A simple, green and efficient method for the DHP protection of various alcohols and phenols and the subsequent removal of the corresponding protective group in the presence of a catalytic amount of the activated carbo...A simple, green and efficient method for the DHP protection of various alcohols and phenols and the subsequent removal of the corresponding protective group in the presence of a catalytic amount of the activated carbon supported H2SO4 is described.展开更多
Nine new gastrodin derivatives,including seven p-hydroxybenzyl-modified gastrodin ethers(1-7),6′-O-acetylgastrodin(8),and 4-[α-d-glucopyranosyl-(1→6)-β-d-glucopyranosyloxy]benzyl alcohol(9),together with seven kno...Nine new gastrodin derivatives,including seven p-hydroxybenzyl-modified gastrodin ethers(1-7),6′-O-acetylgastrodin(8),and 4-[α-d-glucopyranosyl-(1→6)-β-d-glucopyranosyloxy]benzyl alcohol(9),together with seven known derivatives,were isolated from an aqueous extract of Gastrodia elata(“tian ma”)rhizomes.Their structures were determined by spectroscopic and chemical methods as well as single crystal X-ray diffraction.Compounds 1-4,7,10,and 11 were also isolated from a reaction mixture by refluxing gastrodin and p-hydroxybenzyl alcohol in H2O.As both gastrodin and p-hydroxybenzyl alcohol exist in the plant,the reaction results provide evidence for the production and increase/decrease of potential effective/toxic components when“tian ma”is decocted solely or together with ingredients in Chinese traditional medicine formulations,though the isolates were inactive in the preliminarily cell-based assays at concentrations of 10μM.Moreover,using ultra-performance liquid chromatography high-resolution electrospray ionization mass spectrometry(UPLC-HRESIMS),4,7,10,and 11,as well as component variations,were detectable in the freshly prepared extracts of different types of samples,including the freeze-dried fresh G.elata rhizomes.展开更多
Acetophenone oxime and benzaldehyde oxime were converted to oxime ethers in the presence of alkyl halide or methyl sulfate and KOH in aqueous DMSO in 5 to 70 min. The yields of oxime ethers were 70 - 96%.
Using the molecular electronegativity distance vector descriptors derived directly from the molecular topological structures, the relative retention time (RRT) of polybrominated diphenyl ethers (PBDEs) were predic...Using the molecular electronegativity distance vector descriptors derived directly from the molecular topological structures, the relative retention time (RRT) of polybrominated diphenyl ethers (PBDEs) were predicted. A four-variable regression model (M30) with the correlation coefficient of 0.9816 and the root mean square errors of 0.061 was developed using a training set including 30 PBDEs. The correlation coefficient of 0.9841 and the root mean square errors of 0.054 between the values of RRT predicted by M30 and the RRT observed for 16 external PBDEs show a good predictive potential of M30. The descriptors included in the M30 represent four interactions between four pairs of atom types, i.e., atom -C= and -C=, -C= and 〉C=, 〉C= and 〉C=, -C= and -Br.展开更多
文摘Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).
基金supported by the National Natural Science Foundation of China(NSFC,No.21203220 and 21133011)China Postdoctoral Science Foundation(No.2014M551674)+1 种基金Jiangsu Planned Projects for Postdoctoral Research Funds(No.1302070C)the National Basic Research Program of China(973 Program,No.2011CB201404)
文摘The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.
基金supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(No. KZCX2-YW-420-3)the National Basic Research Program (973) of China (No. 2003CB415005)the National Natural Science Foundation of China (No.20437020, 20677074)
文摘To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguiUicaudatus) as experimental fish was performed. Larval loaches were kept in net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied, the mean concentration of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE 209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE 209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.
文摘Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM_(3-6) and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content(less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMM_n were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMM_n from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.
文摘This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample with a tuneable acidity has been proposed as the catalytic system,being tested in a stirred reactor under different etherification conditions.Although a reaction temperature as high as 200℃resulted to be beneficial in terms of glycerol conversion(-90%),only by operating at milder conditions the product selectivity to glycerol-ethers can be better controlled,in order to obtain a bio-fuel complying with the requirements for mixing with fossil diesel or biodiesel,without any need of purification from large amount of by-products.A comprehensive identification of all the compounds formed during the reaction was performed by a GC-MS analysis,on the basis of the complex network of consecutive and parallel reaction paths leading not only to the desired ethers,but also to many side products not detected in similar acid-catalyzed reactions in liquid phase and not available in the most used mass-spectra libraries.
文摘Alcohols are selectively and efficiently protected as their tetrahydropranyl ethers in the presence of a catalytic amount of Fe(HSO4)3 in good to high yields. All reactions are performed under mild and completely heterogeneous reaction conditions.
文摘Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functional Materials by Ma group,discovered that strong coordination force could be founded between 15-Crown-5 ether(15-C-5) and Li+,which facilitates the crown ether(15-C-1) to participate in the solvation structure of Li+ in the electrolyte for the same purpose.Such a novel strategy might impact the design of highperformance and safe lithium metal batteries(LMB s).
基金supported by the Wenling Science and Technology Bureau of Zhejiang Province (No. 2007-35)
文摘We measured 39 polybrominated diphenyl ethers (PBDEs) in the muscle tissue of three species of fish (Sciaenops ocellatus,Sparus macrocephalus,and Lateolabrax japonicus) and four species of shellfish (Tegillarca granosa,Cyclina sinensis,Sinonovacula constricta,and Ostrea cucullata) that were collected downstream of electronic-waste recycling plants in Taizhou,China.A total of 24 PBDE congeners (PBDE 24) in the samples were detected.The PBDE 24 (total PBDE) ranged from 545.4 to 1688.7 ng/kg ww (wet weight).The mean PBDE 24 concentration was 1382.6 ng/kg ww in fish and 858.1 ng/kg ww in shellfish.The lower brominated congeners were detected at relatively high concentrations in all species.The penta-products,produced from e-waste,were found at relatively low levels.A principal component analysis suggested a significant correlation among di-,tri-,tetra-,and hepta-BDEs for the three species of fish.Similarly,we found a significant correlation between mono-and tri-BDEs in the shellfish.Our results suggested that the processes of PBDE metabolism and elimination were similar in both fish and shellfish.In addition,the primary source of PBDEs appeared to be from the debromination of high brominated PBDEs.
基金This work was supported by the National Natural Science Foundation of China (No. 20502022) and the Ph.D. Fund of Ningbo ( No. 2004A610010)
文摘Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 42 halogenated anisoles at the HF/6-31 G^* level. A number of statistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.
基金supported by the National Natural Science Foundation of China(41325010)
文摘This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers(PBDEs)in atmospheric particulate matter using selective pressurized liquid extraction(SPLE)and gas chromatography–mass spectrometry with a negative chemical ionization(GC-NCI-MS).Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70℃ using hexane/dichloromethane(50:50,v/v)as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ng·mL^-1 for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pg·m^-3.
基金supported by 973 program(No.2009CB941701)NSFC grant(No.30972508)MOE Foundation for PhD Program(No 20093234110002)
文摘Objective:To investigate the metabolites of polybrominated diphenyl ether 99(BDE-99)and its related cytochrome P450s in an in vitro system.Methods:Rat primary hepatocytes were isolated and treated with BDE-99 for 24-72 h.Metabolites were then extracted from the hepatocytes and media,and detected by GC/MS.Several mRNAs of metabolic enzymes were also extracted from the same cells and the gene expression levels were determined using quantitative real-time PCR.In addition,selected recombinant cytochrome P450s(CYPs) were expressed in a bacurovirus/sf9 system,and these were further used to explore the metabolism of BDE-99 in vitro.The parent depletion approach was used for screening the ability of CYPs to eliminate BDE-99.Results: A reductively debrominated metabolite,BDE-47,and three oxidative metabolites,2,4,5-tribromophenol,5-OH-BDE-47,and 5'-OH-BDE-99,were identified from the BDE-99-treated rat hepatocytes,whereas no MeO metabolite was detected in the system.RT-PCR analysis showed that CYP 3A23/3A1,1A2,and 2B1/2 were induced by BDE-99.Furthermore,using the heterological expressed CYP proteins in in vitro BDE-99 metabolism experiments we found that CYP1A2 and CYP3A4 showed the highest metabolic efficiency for BDE-99,with the metabolic clearance rates of CYP1A2 and CYP3A4 being 30.3%and 27.7%,respectively.CYP1A1 and CYP2A6 displayed relatively low clearance rates,while CYP2E1 seemed not to be associated with the BDE-99 metabolism.Conclusions:In our in vitro rat primary hepatocyte metabolism system,four metabolites of BDE-99 were identified,and CYP3A4 and CYP1A2 were demonstrated to be involved in the BDE-99 metabolism.
基金the National Natural Science Foundation of China(Nos.51461135001 and 51741804)the Natural Science Foundation of Hunan Province,China(No.2017JJ2066)the Scientific Research Project of Education Department,Hunan Province,China(No.17A054)
文摘Four cellulose ethers(CEs) were compared for their effects on the pore structure of cement paste using mercury intrusion porosimetry. The experimental results show that the total pore volume and porosity of cement pastes containing the four cellulose ethers are significantly higher than that of the pure cement pastes and the total pore volume and porosity of cement pastes containing HEC(hydroxyethyl cellulose ether) or low viscosity cellulose ethers are low in four CEs. By changing the surface tension and viscosity of liquid phase and the strengthening of liquid film between air voids in cement pastes, CEs affect the formation, diameter evolution and upward movement of air voids and the pore structure of hardening cement paste. For the four CEs, the pore volume of cement pastes containing HEC or low viscosity cellulose ethers is higher with the diameter of 30-70 nm while lower with the diameter larger than 70 nm. CEs affect the pore structure of cement paste mainly through their effects on the evolvement of the small air voids into bigger ones when the pore diameter is below 70 nm and their effects on the entrainment and stabilization of air voids when the pore diameter is above 70 nm.
基金the special research project of the National 973 Foundation of China(No.2006CB708606)the National Natural Science Foundation of China(No.20562010)
文摘A simple, green and efficient method for the DHP protection of various alcohols and phenols and the subsequent removal of the corresponding protective group in the presence of a catalytic amount of the activated carbon supported H2SO4 is described.
基金Financial support from the National Natural Science Foundation of China(81630094,81502942,and 81730093)CAMS Innovation Fund for Medical Science of China(2016-I2M-1-004,2017-I2M-3-010,and 2016-I2M-1-010)Drug Innovation Major Project(2018ZX09711001-001-001,China)is gratefully acknowledged.
文摘Nine new gastrodin derivatives,including seven p-hydroxybenzyl-modified gastrodin ethers(1-7),6′-O-acetylgastrodin(8),and 4-[α-d-glucopyranosyl-(1→6)-β-d-glucopyranosyloxy]benzyl alcohol(9),together with seven known derivatives,were isolated from an aqueous extract of Gastrodia elata(“tian ma”)rhizomes.Their structures were determined by spectroscopic and chemical methods as well as single crystal X-ray diffraction.Compounds 1-4,7,10,and 11 were also isolated from a reaction mixture by refluxing gastrodin and p-hydroxybenzyl alcohol in H2O.As both gastrodin and p-hydroxybenzyl alcohol exist in the plant,the reaction results provide evidence for the production and increase/decrease of potential effective/toxic components when“tian ma”is decocted solely or together with ingredients in Chinese traditional medicine formulations,though the isolates were inactive in the preliminarily cell-based assays at concentrations of 10μM.Moreover,using ultra-performance liquid chromatography high-resolution electrospray ionization mass spectrometry(UPLC-HRESIMS),4,7,10,and 11,as well as component variations,were detectable in the freshly prepared extracts of different types of samples,including the freeze-dried fresh G.elata rhizomes.
文摘Acetophenone oxime and benzaldehyde oxime were converted to oxime ethers in the presence of alkyl halide or methyl sulfate and KOH in aqueous DMSO in 5 to 70 min. The yields of oxime ethers were 70 - 96%.
基金the National Basic Research Program of China(2003CB415002)the National Natural Science Foundation of China(No.20377022) the Guangxi Natural Science Fund(No.0236063)for their financial supports.
文摘Using the molecular electronegativity distance vector descriptors derived directly from the molecular topological structures, the relative retention time (RRT) of polybrominated diphenyl ethers (PBDEs) were predicted. A four-variable regression model (M30) with the correlation coefficient of 0.9816 and the root mean square errors of 0.061 was developed using a training set including 30 PBDEs. The correlation coefficient of 0.9841 and the root mean square errors of 0.054 between the values of RRT predicted by M30 and the RRT observed for 16 external PBDEs show a good predictive potential of M30. The descriptors included in the M30 represent four interactions between four pairs of atom types, i.e., atom -C= and -C=, -C= and 〉C=, 〉C= and 〉C=, -C= and -Br.