AIM:To explore the influence of ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate(TPOL)on cell apoptosis and its potential mechanism.METHODS:HEK293T cells sensitive to TPOL were treated with different concentrations of T...AIM:To explore the influence of ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate(TPOL)on cell apoptosis and its potential mechanism.METHODS:HEK293T cells sensitive to TPOL were treated with different concentrations of TPOL with or without exposure to light radiation,before treatment with various inhibitors,N-acetyl-Lcysteine(NAC),pifithrin-αand Z-DVED-FMK.Cell viability was measured by CCK-8 assay.Annexin V/propidium iodide staining was used to count the number of apoptotic cells.DCFH-DA staining was used to detect reactive oxygen species(ROS)levels,and JC-1 staining was used to assess mitochondrial membrane potential by flow cytometry.The expression of apoptosis-related proteins and cell cycle-regulated molecules was measured by Western blot.RESULTS:TPOL enhanced the apoptosis of HEK293T cells in a dose-dependent manner(P<0.05),with a decrease in Bcl-2 and increases in Bax and cytochrome C(Cyto C),followed by up-regulation of activated caspase-9 and caspase-3,and the cleavage of PARP(P<0.05).The TPOL-enhanced cleavage of caspase-3 and PARP was rescued by Z-DVED-FMK(P<0.01).TPOL also led to a rapid increase in ROS,a reduction in mitochondrial membrane potential,and the release of Cyto C(P<0.01),all of which could be reversed by the ROS scavenger NAC.Moreover,the TPOL-caused alterations in p21,p27,Rb,and CDK2 were also recovered by the p53 inhibitor pifithrin-α(P<0.05).The TPOL-induced changes in Bax,Bcl-2,cleaved caspase-9,activated caspase-3,and cleaved PARP were subsequently rescued by pretreatment with pifithrin-α(P<0.05).CONCLUSION:TPOL can induce cellular apoptosis with ROS-mediated mitochondrial membrane damage through the activation of a ROS-dependent p53/p21/p27/Rb/Bax/Cyto C/caspase-mediated signal axis.展开更多
Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. Aft...Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. After hydrolyzation, decarboxylation, and demethylation, we obtained trans-3, 4′, 5-trihydroxystilbene （resveratrol）, which can be converted to its cis-isomer by photochemical isomerization. Results Starting from 3 and 4, trans and cis-3, 4′, 5-trihydroxystilbene were synthesized, respectively. Conclusion A facile method for the synthesis of trans and cis-hydroxystilbenes from readily available materials was established.展开更多
The kinetics of ozonation reactions of trichloroethylene (TCE) and benzene in gas and liquid phases at 101.3 kPa and 298 K was investigated in this paper. The ozonation of TCE is first order with respect to the ozone ...The kinetics of ozonation reactions of trichloroethylene (TCE) and benzene in gas and liquid phases at 101.3 kPa and 298 K was investigated in this paper. The ozonation of TCE is first order with respect to the ozone concentration and one and half order to TCE in the gas phase with the average rate constant 57.30 (mol·L-1)-1.5·s-1, and the TCE ozonation in aqueous medium is first order with respect to both ozone and trichloroethylene with the average rate constant 6.30 (mol·L-1)-1·-1. The ozonation of benzene in the gas phase is first order in ozone but independent of the benzene concentration with the average reaction rate constant 0.0011s-1. The overall kinetics of reaction between ozone and benzene in aqueous solution is found to be first order with one-half order in both ozone and bezene, with the average reaction rate constant 2.67s-1. It is found that the ozonation rate of pallutants is much quicker than that of self-decomposition of ozone in both gas and aqueous phase.展开更多
Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichlo...Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.展开更多
The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlo...The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.展开更多
(S)-3,5-bistrifluoromethylphenyl ethanol is a key chiral intermediate for the synthesis of NK-1 receptor antagonists. Enantioselective synthesis of (S)-3,5-bistrifluoromethylphenyl ethanol was successfully performed i...(S)-3,5-bistrifluoromethylphenyl ethanol is a key chiral intermediate for the synthesis of NK-1 receptor antagonists. Enantioselective synthesis of (S)-3,5-bistrifluoromethylphenyl ethanol was successfully performed in high enantiomeric excess (e.e.) through asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone catalyzed by Candida tropicalis 104 cells. The influence of some key reaction parameters such as substrate concentration, co-substrate and its concentration, biomass and reaction time was examined, respectively. The results showed that these factors obviously influence the yield, but the optical purity of the prepared product remains intact. The opti-mum conditions for the preparation of (S)-3,5-bistrifluoromethylphenyl ethanol were found to be as follows: sub-strate concentration 50 mmol?L?1; 50 g·L-1 of maltose as co-substrate; wet cell concentration 300 g·L-1; reaction for 30 h. Under above optimal conditions, the maximum yield for (S)-3,5-bistrifluoromethylphenyl ethanol reached 70.3% with 100% of product e.e.展开更多
Critical temperature (Tc) and critical pressure (pc) of the ternary mixture of ethylene+benzene+ethylbenzene (the mole ratio of ethylbenzene to benzene was fixed at 0.95:0.05) were measured by using a high=pressure vi...Critical temperature (Tc) and critical pressure (pc) of the ternary mixture of ethylene+benzene+ethylbenzene (the mole ratio of ethylbenzene to benzene was fixed at 0.95:0.05) were measured by using a high=pressure view cell with direct visual observation.The interaction coefficients obtained from the critical properties of the relevant binary systems were used to predict the critical properties (Tc,pc) of the ternary mixture.The agreement between the prediction and experiments is satisfactory.展开更多
A lattice fluid model, Sanchez-Lacombe equation, is used to predict the phase behavior for a styrene/CO2/polystyrene ternary sys-tem. The binary parameters involved in the equation were optimized using experimental da...A lattice fluid model, Sanchez-Lacombe equation, is used to predict the phase behavior for a styrene/CO2/polystyrene ternary sys-tem. The binary parameters involved in the equation were optimized using experimental data. Phase diagrams and the distribution coefficients of styrene between polymer phase and fluid phase are obtained over a wide range of pressure, temperature and composition. The analysis of ter-nary phase diagrams indicates that this system at relatively high pressure or low temperature may display two-phase equilibrium, and at low pressures or high temperatures three-phase equilibrium may appear. The distribution coefficients of styrene between the fluid phase and the polymer phase increase asymptotically to unity when the concentration of styrene increases. The results provide thermodynamic knowledge for further exploitation of supercritical carbon dioxide assisted devolatilization and impregnation.展开更多
The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface...The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface physical and chemical properties of Ph3Sn SBA were characterized using inductively coupled plasma-atomic emission spectroscopy(ICP-AES),13C,119Sn and29Si solid-state nuclear magnetic resonance(NMR)spectroscopy in situ pyridine infrared spectroscopy(Py-IR),N2adsorption–desorption isotherms,X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17%(by mass)for Ph3Sn SBA.The elemental analysis and solid-state NMR results for Ph3Sn SBA were consistent with grafting of triphenyltin on SBA-15.The N2adsorption–desorption,XRD and TEM analyses showed that Ph3Sn SBA retained an ordered hexagonal mesoporous structure,resulting in decreases in the surface area,pore size and mesopore volume,and an increase in acidity as compared with SBA-15.The Hammett acidity function(H0)value and the number of acid sites for Ph3Sn SBA,obtained by the Hammett methods,were 2.77–3.30 and 2.07 mmol·g-1,respectively.The Friedel–Crafts acylation of toluene and acetic anhydride over Ph3Sn SBA was investigated.The yield of methylacetophenone(MAP)and the selectivity for 4-methylacetophenone(PMAP)were 79.56%and 97.12%,respectively,when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6%(by mass)catalyst,and heating under reflux for 5 h.The PMAP selectivity still reached 93.11%when Ph3Sn SBA was used for the fifth time under the same reaction conditions.展开更多
A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were ...A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were achieved using aminobenzoic acids as additive. Moreover, the use of 4-aminobenzoic acid led to significantly superior enhancement in both catalytic activity and selectivity among the tested aminobenzoic acids. Indeed, 100% conversion of styrene and 98.4% selectivity in favor of the β-adduct were obtained. Additionally, hydrosilylations of various alkenes with a variety of platinum catalysts have also been tested, and in each case the conversion of substrate and the selectivity of the β-adduct were promoted by using 4-aminobenzoic acid as additive.展开更多
Gas-phase thermolysis of 1-ethoxycarbonyl-benzotriazole under static, FVP and microwaves condition yielded N^1 and NZ-ethylbenzotriazole, 2-ethoxy-1,3-benzooxazole, biphenylene and oxazolidin-2-one. On the other hand,...Gas-phase thermolysis of 1-ethoxycarbonyl-benzotriazole under static, FVP and microwaves condition yielded N^1 and NZ-ethylbenzotriazole, 2-ethoxy-1,3-benzooxazole, biphenylene and oxazolidin-2-one. On the other hand, direct condensation and pyrolysis of naphtho[1,8-de][1,2,3]triazine with ethylisocyanate, phenylisocyanate and their isothiocayanates, benzoylisothiocyanate and thiourea at 150-160 ℃ or under microwaves irradiation produced the corresponding naphthopyrimidin-2-one derivatives.展开更多
Vapor-liquid equilibrium (VLE) for a ternary system of methyldichlorosilane + methylvinyldichlorosi-lane + toluene and constituent binary systems were measured at 101.3kPa using a new type of magnetical pump-ebulliome...Vapor-liquid equilibrium (VLE) for a ternary system of methyldichlorosilane + methylvinyldichlorosi-lane + toluene and constituent binary systems were measured at 101.3kPa using a new type of magnetical pump-ebulliometer. The equilibrium compositions of the vapor phase of binary systems were calculated indirectly from the total pressure-temperature-liquid composition (pTx). The experimental data were correlated with the Wilson and NRTL(non-random two liquid) equations. The parameters of the Wilson model were employed to predict the ternary VLE data. The calculated boiling points were in good agreement with the experimental ones.展开更多
Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proc...Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proceeded under simple,green,and mild conditions.The peptide nanofibers were used as recyclable supports in the coupling reactions.This approach is the first to use hydroxybenzotriazole as a phenylating agent.展开更多
Sixteen surface sediment samples were collected and analysed to evaluate the residues of organochlorine pesticides （OCPs） from intertidal fiat in Jiangsu Province. Overall, 22 OCPs were detected with total concentra...Sixteen surface sediment samples were collected and analysed to evaluate the residues of organochlorine pesticides （OCPs） from intertidal fiat in Jiangsu Province. Overall, 22 OCPs were detected with total concentrations of OCPs ranging widely from 0.96 to 12.14 ng/g （dry wt）. Total hexachlorocyclohexane （HCH） and total dichlorodiphenyltrichloroethane （DDT） levels varied from 〈0.01 to 0.67 ng/g and from 0.23 to 4.85 ng/g, respectively. DDTs were the predominant compounds. The dominance of β-HCH indicated a history of HCH pollution. According to the ratios of （p,p＇-DDD＋p,p＇-DDE）/p,p＇DDT and o,p＇-DDT/p,p＇- DDT, new input of DDTs did not occur in most sites, and the main sources were historical usage of technical DDTs. OCPs such as dieldrin, endrin, p,p＇-DDD, and p,p＇-DDT exceeded the effects range low, showing adverse biological effects that would occasionally occur at some sites of the study area.展开更多
The amount of ethylene in refinery off-gas is high with a mass fraction of 20%,but the refinery off-gas is usually used as fuel gas in most refineries.The separation and recovery of ethylene is of remarkable significa...The amount of ethylene in refinery off-gas is high with a mass fraction of 20%,but the refinery off-gas is usually used as fuel gas in most refineries.The separation and recovery of ethylene is of remarkable significance for saving energy and reducing carbon dioxide emission.The aim of this paper is to use a novel absorbent mesitylene for the ethylene absorption process and assess its application feasibility through the ethylene + mesitylene vapor-liquid equilibrium data measurement and its binary interaction parameter correlation,as well as the simulation for ethylene separation process.展开更多
Gamma-ray radiation has always been a convenient and effective way to modify the inter- facial properties in polymer blends. In this work, a small amount of trimethylolpropane triacrylate （TMPTA） was incorporated in...Gamma-ray radiation has always been a convenient and effective way to modify the inter- facial properties in polymer blends. In this work, a small amount of trimethylolpropane triacrylate （TMPTA） was incorporated into poly（ethylene terephthalate） （PET）/random terpolymer elastomer （ST2000） blends by melt-blending. The existence of TMPTA would induce the crosslinking of PET and ST2000 molecular chains at high temperatures of blend- ing, resulting in the improvement in the impact strength but the loss in the tensile strength. When the PET/ST2000 blends were irradiated by gamma-ray radiation, the integrated me- chanical properties could be enhanced significantly at a high absorbed dose. The irradiated sample at a dose of 100 kGy even couldn＇t be broken under the impact test load, and at the same time, has nearly no loss of tensile strength. Based on the analysis of the impact- fractured surface morphologies of the blends, it can be concluded that gamma-ray radiation at high absorbed dose can further in situ enhance the interfacial adhesion by promoting the crosslinking reactions of TMPTA and polymer chains. As a result, the toughness and strength of PET/ST2000 blend could be dramatically improved. This work provides a facial and practical way to the fabrication of polymer blends with high toughness and strength.展开更多
The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe)...The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.展开更多
基金Supported by the National Natural Science Foundation of China(No.81172824)。
文摘AIM:To explore the influence of ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate(TPOL)on cell apoptosis and its potential mechanism.METHODS:HEK293T cells sensitive to TPOL were treated with different concentrations of TPOL with or without exposure to light radiation,before treatment with various inhibitors,N-acetyl-Lcysteine(NAC),pifithrin-αand Z-DVED-FMK.Cell viability was measured by CCK-8 assay.Annexin V/propidium iodide staining was used to count the number of apoptotic cells.DCFH-DA staining was used to detect reactive oxygen species(ROS)levels,and JC-1 staining was used to assess mitochondrial membrane potential by flow cytometry.The expression of apoptosis-related proteins and cell cycle-regulated molecules was measured by Western blot.RESULTS:TPOL enhanced the apoptosis of HEK293T cells in a dose-dependent manner(P<0.05),with a decrease in Bcl-2 and increases in Bax and cytochrome C(Cyto C),followed by up-regulation of activated caspase-9 and caspase-3,and the cleavage of PARP(P<0.05).The TPOL-enhanced cleavage of caspase-3 and PARP was rescued by Z-DVED-FMK(P<0.01).TPOL also led to a rapid increase in ROS,a reduction in mitochondrial membrane potential,and the release of Cyto C(P<0.01),all of which could be reversed by the ROS scavenger NAC.Moreover,the TPOL-caused alterations in p21,p27,Rb,and CDK2 were also recovered by the p53 inhibitor pifithrin-α(P<0.05).The TPOL-induced changes in Bax,Bcl-2,cleaved caspase-9,activated caspase-3,and cleaved PARP were subsequently rescued by pretreatment with pifithrin-α(P<0.05).CONCLUSION:TPOL can induce cellular apoptosis with ROS-mediated mitochondrial membrane damage through the activation of a ROS-dependent p53/p21/p27/Rb/Bax/Cyto C/caspase-mediated signal axis.
文摘Aim To synthesize trans and cis-3, 4′, 5-trihydroxystilbene by a new convenient route. Methods The reaction of 3, 5-dimethoxybenzaldehyde （3） and 4-methoxy phenylacetonitrile （4） formed the stilbene skeleton. After hydrolyzation, decarboxylation, and demethylation, we obtained trans-3, 4′, 5-trihydroxystilbene （resveratrol）, which can be converted to its cis-isomer by photochemical isomerization. Results Starting from 3 and 4, trans and cis-3, 4′, 5-trihydroxystilbene were synthesized, respectively. Conclusion A facile method for the synthesis of trans and cis-hydroxystilbenes from readily available materials was established.
基金Supported by Guangdong Province Natural Science Foundation(No.970457).
文摘The kinetics of ozonation reactions of trichloroethylene (TCE) and benzene in gas and liquid phases at 101.3 kPa and 298 K was investigated in this paper. The ozonation of TCE is first order with respect to the ozone concentration and one and half order to TCE in the gas phase with the average rate constant 57.30 (mol·L-1)-1.5·s-1, and the TCE ozonation in aqueous medium is first order with respect to both ozone and trichloroethylene with the average rate constant 6.30 (mol·L-1)-1·-1. The ozonation of benzene in the gas phase is first order in ozone but independent of the benzene concentration with the average reaction rate constant 0.0011s-1. The overall kinetics of reaction between ozone and benzene in aqueous solution is found to be first order with one-half order in both ozone and bezene, with the average reaction rate constant 2.67s-1. It is found that the ozonation rate of pallutants is much quicker than that of self-decomposition of ozone in both gas and aqueous phase.
基金The authors thank the financial support of the Natural Science Foundation of Fujian Province (No. E0110010)
文摘Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.
文摘The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.
基金Supported by the National＇Natural Science Foundation of China （21076193） and Foundation of Zhejiang Key Developing Discipline of Pharmacy （20100609）.
文摘(S)-3,5-bistrifluoromethylphenyl ethanol is a key chiral intermediate for the synthesis of NK-1 receptor antagonists. Enantioselective synthesis of (S)-3,5-bistrifluoromethylphenyl ethanol was successfully performed in high enantiomeric excess (e.e.) through asymmetric reduction of 3,5-bis(trifluoromethyl) acetophenone catalyzed by Candida tropicalis 104 cells. The influence of some key reaction parameters such as substrate concentration, co-substrate and its concentration, biomass and reaction time was examined, respectively. The results showed that these factors obviously influence the yield, but the optical purity of the prepared product remains intact. The opti-mum conditions for the preparation of (S)-3,5-bistrifluoromethylphenyl ethanol were found to be as follows: sub-strate concentration 50 mmol?L?1; 50 g·L-1 of maltose as co-substrate; wet cell concentration 300 g·L-1; reaction for 30 h. Under above optimal conditions, the maximum yield for (S)-3,5-bistrifluoromethylphenyl ethanol reached 70.3% with 100% of product e.e.
基金Supported by the National Natural Science Foundation of China(Project No. 20025618).
文摘Critical temperature (Tc) and critical pressure (pc) of the ternary mixture of ethylene+benzene+ethylbenzene (the mole ratio of ethylbenzene to benzene was fixed at 0.95:0.05) were measured by using a high=pressure view cell with direct visual observation.The interaction coefficients obtained from the critical properties of the relevant binary systems were used to predict the critical properties (Tc,pc) of the ternary mixture.The agreement between the prediction and experiments is satisfactory.
基金Supported by the National Natural Science Foundation of China (No. 29676037).
文摘A lattice fluid model, Sanchez-Lacombe equation, is used to predict the phase behavior for a styrene/CO2/polystyrene ternary sys-tem. The binary parameters involved in the equation were optimized using experimental data. Phase diagrams and the distribution coefficients of styrene between polymer phase and fluid phase are obtained over a wide range of pressure, temperature and composition. The analysis of ter-nary phase diagrams indicates that this system at relatively high pressure or low temperature may display two-phase equilibrium, and at low pressures or high temperatures three-phase equilibrium may appear. The distribution coefficients of styrene between the fluid phase and the polymer phase increase asymptotically to unity when the concentration of styrene increases. The results provide thermodynamic knowledge for further exploitation of supercritical carbon dioxide assisted devolatilization and impregnation.
基金Supported by the National Science Foundation of Heilongjiang Province(B201010)the Education Department of Heilongjiang Province(12511595)
文摘The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface physical and chemical properties of Ph3Sn SBA were characterized using inductively coupled plasma-atomic emission spectroscopy(ICP-AES),13C,119Sn and29Si solid-state nuclear magnetic resonance(NMR)spectroscopy in situ pyridine infrared spectroscopy(Py-IR),N2adsorption–desorption isotherms,X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17%(by mass)for Ph3Sn SBA.The elemental analysis and solid-state NMR results for Ph3Sn SBA were consistent with grafting of triphenyltin on SBA-15.The N2adsorption–desorption,XRD and TEM analyses showed that Ph3Sn SBA retained an ordered hexagonal mesoporous structure,resulting in decreases in the surface area,pore size and mesopore volume,and an increase in acidity as compared with SBA-15.The Hammett acidity function(H0)value and the number of acid sites for Ph3Sn SBA,obtained by the Hammett methods,were 2.77–3.30 and 2.07 mmol·g-1,respectively.The Friedel–Crafts acylation of toluene and acetic anhydride over Ph3Sn SBA was investigated.The yield of methylacetophenone(MAP)and the selectivity for 4-methylacetophenone(PMAP)were 79.56%and 97.12%,respectively,when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6%(by mass)catalyst,and heating under reflux for 5 h.The PMAP selectivity still reached 93.11%when Ph3Sn SBA was used for the fifth time under the same reaction conditions.
基金Supported by the National High Technology Research and Development Program of China (2006AA03A134)Zhejiang Province Program (2008C14041)
文摘A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were achieved using aminobenzoic acids as additive. Moreover, the use of 4-aminobenzoic acid led to significantly superior enhancement in both catalytic activity and selectivity among the tested aminobenzoic acids. Indeed, 100% conversion of styrene and 98.4% selectivity in favor of the β-adduct were obtained. Additionally, hydrosilylations of various alkenes with a variety of platinum catalysts have also been tested, and in each case the conversion of substrate and the selectivity of the β-adduct were promoted by using 4-aminobenzoic acid as additive.
文摘Gas-phase thermolysis of 1-ethoxycarbonyl-benzotriazole under static, FVP and microwaves condition yielded N^1 and NZ-ethylbenzotriazole, 2-ethoxy-1,3-benzooxazole, biphenylene and oxazolidin-2-one. On the other hand, direct condensation and pyrolysis of naphtho[1,8-de][1,2,3]triazine with ethylisocyanate, phenylisocyanate and their isothiocayanates, benzoylisothiocyanate and thiourea at 150-160 ℃ or under microwaves irradiation produced the corresponding naphthopyrimidin-2-one derivatives.
基金Supported by the Natural Science Foundation of Jiangxi Province(No.0020019).
文摘Vapor-liquid equilibrium (VLE) for a ternary system of methyldichlorosilane + methylvinyldichlorosi-lane + toluene and constituent binary systems were measured at 101.3kPa using a new type of magnetical pump-ebulliometer. The equilibrium compositions of the vapor phase of binary systems were calculated indirectly from the total pressure-temperature-liquid composition (pTx). The experimental data were correlated with the Wilson and NRTL(non-random two liquid) equations. The parameters of the Wilson model were employed to predict the ternary VLE data. The calculated boiling points were in good agreement with the experimental ones.
基金the Research Facility of Ilam University,Ilam,Iran,for financial support of this research project
文摘Peptide nanofibers decorated with palladium nanoparticles catalyzed direct coupling of aryl halides with hydroxybenzotriazole to afford the corresponding biaryls in good to excellent yields.The coupling reactions proceeded under simple,green,and mild conditions.The peptide nanofibers were used as recyclable supports in the coupling reactions.This approach is the first to use hydroxybenzotriazole as a phenylating agent.
基金Supported by the National Natural Science Foundation of China(Nos.40871216,41271466)
文摘Sixteen surface sediment samples were collected and analysed to evaluate the residues of organochlorine pesticides （OCPs） from intertidal fiat in Jiangsu Province. Overall, 22 OCPs were detected with total concentrations of OCPs ranging widely from 0.96 to 12.14 ng/g （dry wt）. Total hexachlorocyclohexane （HCH） and total dichlorodiphenyltrichloroethane （DDT） levels varied from 〈0.01 to 0.67 ng/g and from 0.23 to 4.85 ng/g, respectively. DDTs were the predominant compounds. The dominance of β-HCH indicated a history of HCH pollution. According to the ratios of （p,p＇-DDD＋p,p＇-DDE）/p,p＇DDT and o,p＇-DDT/p,p＇- DDT, new input of DDTs did not occur in most sites, and the main sources were historical usage of technical DDTs. OCPs such as dieldrin, endrin, p,p＇-DDD, and p,p＇-DDT exceeded the effects range low, showing adverse biological effects that would occasionally occur at some sites of the study area.
基金Supported by the National Natural Science Foundation of China （50890184） the National Basic Research Program of China （2011CB201306）
文摘The amount of ethylene in refinery off-gas is high with a mass fraction of 20%,but the refinery off-gas is usually used as fuel gas in most refineries.The separation and recovery of ethylene is of remarkable significance for saving energy and reducing carbon dioxide emission.The aim of this paper is to use a novel absorbent mesitylene for the ethylene absorption process and assess its application feasibility through the ethylene + mesitylene vapor-liquid equilibrium data measurement and its binary interaction parameter correlation,as well as the simulation for ethylene separation process.
文摘Gamma-ray radiation has always been a convenient and effective way to modify the inter- facial properties in polymer blends. In this work, a small amount of trimethylolpropane triacrylate （TMPTA） was incorporated into poly（ethylene terephthalate） （PET）/random terpolymer elastomer （ST2000） blends by melt-blending. The existence of TMPTA would induce the crosslinking of PET and ST2000 molecular chains at high temperatures of blend- ing, resulting in the improvement in the impact strength but the loss in the tensile strength. When the PET/ST2000 blends were irradiated by gamma-ray radiation, the integrated me- chanical properties could be enhanced significantly at a high absorbed dose. The irradiated sample at a dose of 100 kGy even couldn＇t be broken under the impact test load, and at the same time, has nearly no loss of tensile strength. Based on the analysis of the impact- fractured surface morphologies of the blends, it can be concluded that gamma-ray radiation at high absorbed dose can further in situ enhance the interfacial adhesion by promoting the crosslinking reactions of TMPTA and polymer chains. As a result, the toughness and strength of PET/ST2000 blend could be dramatically improved. This work provides a facial and practical way to the fabrication of polymer blends with high toughness and strength.
文摘The complex [Et4N][(Ph3P)2{CuS2WS2Fe} Br2] (1 ), C44, H50NBr2CuFeP2S4W, M4= 1246. 13, has been obtained by reaction of [Et4N]2[WS4] andFeBr2 with Cu (Ph3P )3I in MeCN/CH2Cl2. Crystal data for [Et4N][(Ph3P)2{CuS2WS2Fe) Br2] (1): triclinic, P1, Z = 2, a= 13. 495 (7), b = 15. 322 (5), c =12. 361 (4), a=105. 32(3), β=93. 19(4), γ=101. 35(4) and V=2401. 2 The bond lengths of W-Fe bond and the W-Cu distance are 2. 793(2) A and 2. 823(2), respectively. Three kind metal atoms of the title structure [Et4N][(Ph3P)2{CuS2WS2Fe}Br2] (1) are nearly distributed along a line, and along which three metalatoms (W, Cu, Fe) are approximately tetrahedral coordination.
