The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts ...The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.展开更多
The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 ...The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 dimethyl γ butyrolactone,were obtained from diethyl malonate and 2,3 epoxybutane.2 Methyl octan 1 yl lithium reacted with 3,4 dimethyl γ butyrolactone to yield the ketoalcohol and then followed by Huang Minlong reduction to afford 3,7 dimethyl 2 tridecanol,acylated with acetic anhydide to give 3,7 dimethyl 2 tridecanyl acetate.展开更多
Nano-ZnO particle （nZnOp） reinforced polyethylene glycol （PEG）/polyethylene terephthalate （PET） （nZnOp/PEG/PET） copolymeric composites with different mass fractions and molecular weights of PEG are synthesized...Nano-ZnO particle （nZnOp） reinforced polyethylene glycol （PEG）/polyethylene terephthalate （PET） （nZnOp/PEG/PET） copolymeric composites with different mass fractions and molecular weights of PEG are synthesized via in-situ polymerization. The dispersion of nZnOp in copolymer matrixes and the effects of PEG and nZnOp particles on the crystallization behavior of the composites are studied by TEM, differential scanning calorimetry（DSC）, XRD and Fourier thansform infrared spectroscopy （FTIR ）. The results reveal that nZnOp particles are dispersed in the matrixes with nano-scale, and the addition of PEG induces more homogeneous dispersion of nZnOp. Simultaneously, these nanoparticles become nucleating centers during the crystallization of the matrixes. PEG segments can improve the flexibility of the PET molecular chain, resulting in the drop of the cold crystallization temperature and the rise of the crystallization rate of the composites. Furthermore, PEG （4 000） with the mass fraction of 10% can promote the crystallization rate of the composites. The mechanical properties show that the nano-particles strengthen and toughen the PET matrix, whereas PEG weakens these improve- ments.展开更多
Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ort...Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ortho and geminal positions via a concerted or stepwise pathway.For the concerted pathway,the calculated free energy barriers for the para,meta,ortho and geminal methylation reactions were 167,138,139 and 183 kJ/mol,respectively.For the stepwise pathway,the dehydration of methanol was found to be the rate-determining step with a free energy barrier of145 kj/mol,whereas the free energy barriers for the methylation of toluene at its para,meta,ortho and geminal positions were 127,105,106 and 114 kj/mol,respectively.Both pathways led to the formation of C8H11^＋ species as important intermediates,which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation.Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C8H11^＋ species to the carbon of the methyl group,with calculated energy barriers of 136,132 and134 kj/mol for the para,meta and ortho C8H11^＋ species,respectively.The calculated free energy barriers for the formation of para-,meta- and ortho-xylene indicated that the formation of the para-xylene had the highest energy barrier for both pathways.展开更多
A method for determination of lycopene concentration in dog plasma wasestablished. Methods RP-HPLC was used; the mobile phase consisted of methanol-acetonitrile-methylenechloride (40:30:30, V/V) , the wavelength of de...A method for determination of lycopene concentration in dog plasma wasestablished. Methods RP-HPLC was used; the mobile phase consisted of methanol-acetonitrile-methylenechloride (40:30:30, V/V) , the wavelength of detection was 472 nm, the column temperature wasambient temperature, and the flow rate was 1.0 mL·min^(-1). Results The standard curve was linearin the range from 0.012 4 to 0.496 μg·mL^(-1) with r=0.9992. The average extraction recovery was97.6% +-4.2%. The intra-day and inter-day RSD were 1.52% -4.95% and 2.31% -7.38%, respectively.Conclusion This method is sensitive, rapid, reproducible, and of good selectivity for the analysisof lycopene in dog plasma.展开更多
文摘The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.
基金Supported by Foundation for University Key Teacher by the Min-istry of Education
文摘The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 dimethyl γ butyrolactone,were obtained from diethyl malonate and 2,3 epoxybutane.2 Methyl octan 1 yl lithium reacted with 3,4 dimethyl γ butyrolactone to yield the ketoalcohol and then followed by Huang Minlong reduction to afford 3,7 dimethyl 2 tridecanol,acylated with acetic anhydide to give 3,7 dimethyl 2 tridecanyl acetate.
基金Supported by the Program of Jiangsu Development & Reform Commission(2005)the Industrial-ization Boosting Program of College Scientific Reserach Achievements of the Education Department of Jiangsu Province(JHB06-03)~~
文摘Nano-ZnO particle （nZnOp） reinforced polyethylene glycol （PEG）/polyethylene terephthalate （PET） （nZnOp/PEG/PET） copolymeric composites with different mass fractions and molecular weights of PEG are synthesized via in-situ polymerization. The dispersion of nZnOp in copolymer matrixes and the effects of PEG and nZnOp particles on the crystallization behavior of the composites are studied by TEM, differential scanning calorimetry（DSC）, XRD and Fourier thansform infrared spectroscopy （FTIR ）. The results reveal that nZnOp particles are dispersed in the matrixes with nano-scale, and the addition of PEG induces more homogeneous dispersion of nZnOp. Simultaneously, these nanoparticles become nucleating centers during the crystallization of the matrixes. PEG segments can improve the flexibility of the PET molecular chain, resulting in the drop of the cold crystallization temperature and the rise of the crystallization rate of the composites. Furthermore, PEG （4 000） with the mass fraction of 10% can promote the crystallization rate of the composites. The mechanical properties show that the nano-particles strengthen and toughen the PET matrix, whereas PEG weakens these improve- ments.
基金supported by the National Natural Science Foundation of China(21446003)the Specialized Research Fund for the Doctoral Program of Higher Education(20130074110018)~~
文摘Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ortho and geminal positions via a concerted or stepwise pathway.For the concerted pathway,the calculated free energy barriers for the para,meta,ortho and geminal methylation reactions were 167,138,139 and 183 kJ/mol,respectively.For the stepwise pathway,the dehydration of methanol was found to be the rate-determining step with a free energy barrier of145 kj/mol,whereas the free energy barriers for the methylation of toluene at its para,meta,ortho and geminal positions were 127,105,106 and 114 kj/mol,respectively.Both pathways led to the formation of C8H11^＋ species as important intermediates,which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation.Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C8H11^＋ species to the carbon of the methyl group,with calculated energy barriers of 136,132 and134 kj/mol for the para,meta and ortho C8H11^＋ species,respectively.The calculated free energy barriers for the formation of para-,meta- and ortho-xylene indicated that the formation of the para-xylene had the highest energy barrier for both pathways.
文摘A method for determination of lycopene concentration in dog plasma wasestablished. Methods RP-HPLC was used; the mobile phase consisted of methanol-acetonitrile-methylenechloride (40:30:30, V/V) , the wavelength of detection was 472 nm, the column temperature wasambient temperature, and the flow rate was 1.0 mL·min^(-1). Results The standard curve was linearin the range from 0.012 4 to 0.496 μg·mL^(-1) with r=0.9992. The average extraction recovery was97.6% +-4.2%. The intra-day and inter-day RSD were 1.52% -4.95% and 2.31% -7.38%, respectively.Conclusion This method is sensitive, rapid, reproducible, and of good selectivity for the analysisof lycopene in dog plasma.
