DFT/6-31G^＊ calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by （S）-proline. Four transition states associated with the stereo-controlling step, corresp...DFT/6-31G^＊ calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by （S）-proline. Four transition states associated with the stereo-controlling step, corresponding to syn and anti arrangements of methylene moiety related to the carboxylic acid group in enamine intermediate and re and si attacks to the aldehyde carbonyl carbon have been obtained. The solvent effect of DMSO was investigated with polarized continuum model. The computed energies of transition states reveal the stereo-selectivity of the reaction.展开更多
The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above a...The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.展开更多
Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiat...Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiator. Theblock copolymers were characterized in detail by methods Of size exclusion chromatography (SEC ) , 1H - Nab, FT - IR, dynamic mechanical analysis(Daal ) and WAXD.展开更多
The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and etha...The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and ethane in ethylene hydroformylation.展开更多
Ethylene oxide （EO） is a sold-out intermediate material for producing various chemicals.Major chemical companies are interested in whether new EO plant can create profit.This research is undertaken to investigate th...Ethylene oxide （EO） is a sold-out intermediate material for producing various chemicals.Major chemical companies are interested in whether new EO plant can create profit.This research is undertaken to investigate the economic feasibility of EO production.Direct oxidation of ethylene using silver on alpha-A12O3 catalyst type is adapted to produce EO of 60 000 t/year.We conduct the conceptual design.Firstly,we synthesize the optimal structure and then determine optimal conditions and the size of the equipments.Feasibility study shows that profit and loss turning point turns out to be 3.2 years based on the present market price.In addition,we conducts the economic analysis to prepare the risk of raw material market price variation ranging from 70％ to 130％.展开更多
Foxtail millet(Setaria italica)growth was inhibited because of waterlogging stress,which has caused yield reduc-tion.ERF family plays an important role to plant adversity tolerance.In our study,we obtained 19,819 diff...Foxtail millet(Setaria italica)growth was inhibited because of waterlogging stress,which has caused yield reduc-tion.ERF family plays an important role to plant adversity tolerance.In our study,we obtained 19,819 differential expressed genes(DEGs)between the two treatments based on the RNA-seq sequencing of foxtail millet of water-logging stress.Furthermore,a total of 28 ERF family members were obtained,which have a complete open read-ing frame.We studied the evolution and function of SiERF family and how they affected the waterlogging tolerance.It was found that SiERF1A/B/C(GenBank ID:OR775217,OR775219,OR775218)and SiRAP2-12(GenBank ID:OR775216)have similar functions to the known waterlogging tolerance genes of other plants.Among them,the SiRAP2-12 expression was obviously significantly up-regulated in foxtail millet after 5d water-logging stress.After SiRAP2-12 was silenced,the activity of defense enzymes in millet decreased significantly.In details,superoxide dismutase(SOD),catalase(CAT)and peroxidase(POD),the osmotic regulator proline(Pro),and the activity of the anaerobic respiratory enzyme alcohol dehydrogenase(ADH)content were decreased by 78.61%,29.52%,79.95%,19.41%and 54.77%,respectively.In contrast,the relative electrical conductivity contents(REC),malondialdehyde(MDA),and hydrogen peroxide(H_(2)O_(2))of the foxtail millet subjected to virus-induced gene silencing clearly increased by 1.03-fold,36.09%,and 15.21%,respectively.The content of sodium(Na^(+))in the SiRAP2-12-silenced foxtail millet also increased,but that of potassium(K^(+))decreased.Interestingly,we found that ethylene content was significantly reduced.Further,the SiAOC1 expression,an essential gene for ethylene synthesis,was inhibited in SiRAP2-12-silenced foxtail millet after waterlogging stress.Taken together,we hypothesized that SiRAP2-12 might be a positive regulator of millet tolerance to waterlogging stress.展开更多
The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nick...The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.展开更多
A series of half-titanocene chloride 2-（benzimidazol-2-yl）quinolin-8-olates C1-C6 were synthesized by treating the lithium salts of the ligand with CpTiCI3. All the complexes were characterized by 1H-NMR, 13C-NMR an...A series of half-titanocene chloride 2-（benzimidazol-2-yl）quinolin-8-olates C1-C6 were synthesized by treating the lithium salts of the ligand with CpTiCI3. All the complexes were characterized by 1H-NMR, 13C-NMR and elemental analyses, and the crystal structure of C3 and C6 was measured by X-ray. These half-titanocene complexes showed moderate catalytic activities toward ethylene polymerization （up to 1840 kg·mol-1（Ti）·h-1） when activated with MMAO, affording the high molecular weight polymers. And they also exhibited good activity for copolymerization of ethylene and a-olefin with low content of co-monomer.展开更多
A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = B...A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.展开更多
DFT-B3LYP calculations were carried out to study the enantioselectivity of the （S）-4-hydroxylproline-catalyzed direct aldol reaction between acetone and 4-nitrobenzaldehyde. Four transition structures associated wit...DFT-B3LYP calculations were carried out to study the enantioselectivity of the （S）-4-hydroxylproline-catalyzed direct aldol reaction between acetone and 4-nitrobenzaldehyde. Four transition structures associated with the stereo-controlling step of the reaction have been determined. They are corresponding to the anti and syn arrangements of the methylene moiety related to the carboxylic acid group in enamine intermediate and the si and re attacks to the aldehyde carbonyl carbon. The effect of DMSO solvent on the stereo-controlling step was investigated with polarized continuum model （PCM）. The computed energies of the transition states reveal the moderate enantioselectivity of the reaction.展开更多
The reaction of a series of 1-（3-pyridyl）-2,2-di-substituted ethylenes with 1-benzyl-1,4-dihydronicotinamide （BNAH） in deaerated acetonitrile produces the corresponding 1-（3-pyridyl）-2,2-di-substituted ethanes i...The reaction of a series of 1-（3-pyridyl）-2,2-di-substituted ethylenes with 1-benzyl-1,4-dihydronicotinamide （BNAH） in deaerated acetonitrile produces the corresponding 1-（3-pyridyl）-2,2-di-substituted ethanes in contrast to benzylidenemalononitrile （BM） which does not react with BNAH under the same conditions.展开更多
Cr2O3 nanotubes with diameters of 80 nm and lengths of 550 nm were synthesized in a solvothermal reduction system at 180 ℃. The acetyl acetone (AcAc) and ethylene glycol (EG) were used as the chelate agent and the re...Cr2O3 nanotubes with diameters of 80 nm and lengths of 550 nm were synthesized in a solvothermal reduction system at 180 ℃. The acetyl acetone (AcAc) and ethylene glycol (EG) were used as the chelate agent and the reductant respectively in the system. An intermediate compound-Cr(C5H7O2)3 was formed to force Cr2O3 to crystallize along one direction.展开更多
基金This project was supported by the Research Foundation of Key Laboratory of Organic Synthesis of Jiangsu Province (No. JSK010)
文摘DFT/6-31G^＊ calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by （S）-proline. Four transition states associated with the stereo-controlling step, corresponding to syn and anti arrangements of methylene moiety related to the carboxylic acid group in enamine intermediate and re and si attacks to the aldehyde carbonyl carbon have been obtained. The solvent effect of DMSO was investigated with polarized continuum model. The computed energies of transition states reveal the stereo-selectivity of the reaction.
基金Supported by the Foundation of Educational Ministry of China.
文摘The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.
文摘Well - defined diblock copolymers Of styrene (St ) and ethylene oxide (EO )have been prepared by sequential living anionic polymerization of the twocomonomers in THF. Diphenyl methyl potassium has been used as initiator. Theblock copolymers were characterized in detail by methods Of size exclusion chromatography (SEC ) , 1H - Nab, FT - IR, dynamic mechanical analysis(Daal ) and WAXD.
文摘The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and ethane in ethylene hydroformylation.
基金The MSIP(Ministry of Science,ICT&Future Planning),Korea,under the Convergence-ITRC(Convergence Information Technology Research Center)support program(NIPA-2013-H0401-13-1004)supervised by the NIPA(National IT Industry Promotion Agency)
文摘Ethylene oxide （EO） is a sold-out intermediate material for producing various chemicals.Major chemical companies are interested in whether new EO plant can create profit.This research is undertaken to investigate the economic feasibility of EO production.Direct oxidation of ethylene using silver on alpha-A12O3 catalyst type is adapted to produce EO of 60 000 t/year.We conduct the conceptual design.Firstly,we synthesize the optimal structure and then determine optimal conditions and the size of the equipments.Feasibility study shows that profit and loss turning point turns out to be 3.2 years based on the present market price.In addition,we conducts the economic analysis to prepare the risk of raw material market price variation ranging from 70％ to 130％.
基金This research was supported by the China Agricultural Research System(CARS-06-14.5-A23)HAAFS Basic Science and Technology Contract Project(Grant No.HBNKY-BGZ-02)Technical System of Foxtail Millet Industry in Hebei Province.
文摘Foxtail millet(Setaria italica)growth was inhibited because of waterlogging stress,which has caused yield reduc-tion.ERF family plays an important role to plant adversity tolerance.In our study,we obtained 19,819 differential expressed genes(DEGs)between the two treatments based on the RNA-seq sequencing of foxtail millet of water-logging stress.Furthermore,a total of 28 ERF family members were obtained,which have a complete open read-ing frame.We studied the evolution and function of SiERF family and how they affected the waterlogging tolerance.It was found that SiERF1A/B/C(GenBank ID:OR775217,OR775219,OR775218)and SiRAP2-12(GenBank ID:OR775216)have similar functions to the known waterlogging tolerance genes of other plants.Among them,the SiRAP2-12 expression was obviously significantly up-regulated in foxtail millet after 5d water-logging stress.After SiRAP2-12 was silenced,the activity of defense enzymes in millet decreased significantly.In details,superoxide dismutase(SOD),catalase(CAT)and peroxidase(POD),the osmotic regulator proline(Pro),and the activity of the anaerobic respiratory enzyme alcohol dehydrogenase(ADH)content were decreased by 78.61%,29.52%,79.95%,19.41%and 54.77%,respectively.In contrast,the relative electrical conductivity contents(REC),malondialdehyde(MDA),and hydrogen peroxide(H_(2)O_(2))of the foxtail millet subjected to virus-induced gene silencing clearly increased by 1.03-fold,36.09%,and 15.21%,respectively.The content of sodium(Na^(+))in the SiRAP2-12-silenced foxtail millet also increased,but that of potassium(K^(+))decreased.Interestingly,we found that ethylene content was significantly reduced.Further,the SiAOC1 expression,an essential gene for ethylene synthesis,was inhibited in SiRAP2-12-silenced foxtail millet after waterlogging stress.Taken together,we hypothesized that SiRAP2-12 might be a positive regulator of millet tolerance to waterlogging stress.
基金supported by the National Key R&D Program of China(2021YFA1501700)Fundamental Research Funds for the Central Universities(WK9990000142).
文摘The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.
基金supported by NSFC (No. 20904059)Key Project of 863 Program of China(No. 2009AA034605)
文摘A series of half-titanocene chloride 2-（benzimidazol-2-yl）quinolin-8-olates C1-C6 were synthesized by treating the lithium salts of the ligand with CpTiCI3. All the complexes were characterized by 1H-NMR, 13C-NMR and elemental analyses, and the crystal structure of C3 and C6 was measured by X-ray. These half-titanocene complexes showed moderate catalytic activities toward ethylene polymerization （up to 1840 kg·mol-1（Ti）·h-1） when activated with MMAO, affording the high molecular weight polymers. And they also exhibited good activity for copolymerization of ethylene and a-olefin with low content of co-monomer.
文摘A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.
文摘DFT-B3LYP calculations were carried out to study the enantioselectivity of the （S）-4-hydroxylproline-catalyzed direct aldol reaction between acetone and 4-nitrobenzaldehyde. Four transition structures associated with the stereo-controlling step of the reaction have been determined. They are corresponding to the anti and syn arrangements of the methylene moiety related to the carboxylic acid group in enamine intermediate and the si and re attacks to the aldehyde carbonyl carbon. The effect of DMSO solvent on the stereo-controlling step was investigated with polarized continuum model （PCM）. The computed energies of the transition states reveal the moderate enantioselectivity of the reaction.
基金Project supported by the National Natural Science Foundation of China （No. 20072036） and the Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘The reaction of a series of 1-（3-pyridyl）-2,2-di-substituted ethylenes with 1-benzyl-1,4-dihydronicotinamide （BNAH） in deaerated acetonitrile produces the corresponding 1-（3-pyridyl）-2,2-di-substituted ethanes in contrast to benzylidenemalononitrile （BM） which does not react with BNAH under the same conditions.
文摘Cr2O3 nanotubes with diameters of 80 nm and lengths of 550 nm were synthesized in a solvothermal reduction system at 180 ℃. The acetyl acetone (AcAc) and ethylene glycol (EG) were used as the chelate agent and the reductant respectively in the system. An intermediate compound-Cr(C5H7O2)3 was formed to force Cr2O3 to crystallize along one direction.
