The activities of dimethyl carbonate and dimethyl sulfate as a methylation reagent were studied by density- functional theory (DFT). B3LYP/6-31G(d, p) methods were used to optimize the structures of dirnethyl carb...The activities of dimethyl carbonate and dimethyl sulfate as a methylation reagent were studied by density- functional theory (DFT). B3LYP/6-31G(d, p) methods were used to optimize the structures of dirnethyl carbonate and dimethyl sulfate and calculate theirs charge densities. Dimethyl sulfate is easier than dimethyl carbonate to react with a nucleophUic reagent. In dimethyl sulfate, the alkoxy carbons are the only reactive atomic nucleus because of steric hindrance. A nucleophilic reagent is more likely to react with carbonyl carbons than alkoxy carbons of dimethyl carbonate; in the presence of a Lewis acid, the phenyl nucleophilic reagent reacts with the Lewis acid first. Lewis acid increases the negative charge density of a nucleophUic reagent in polar solvent, and also incurs an accretion of steric hindrance. Polar solvent avails to ionize dimethyl carbonate and thus enables the reaction of methylation. The frequencies of transition state calculated by Gaussion 03 confirm the inferred reaction mechanism. The harvest rates of 4-methoxyphenol in the experiments of methylation reactions of hydroquinone with respectively dimethyl carbonate and dimethyl sulfate support the foregoing theortical conclusions.展开更多
TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracyc...TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.展开更多
Five kinds of carboxymethyl sulfochitosans with different regions such as N-carboxymethyl-O-sulfochitosan, O-carboxymethyl-N-sulfochitosan, O-carboxymethyl chitosan sulfate, N-carboxymethyl chitosan-6-sulfate, and N,O...Five kinds of carboxymethyl sulfochitosans with different regions such as N-carboxymethyl-O-sulfochitosan, O-carboxymethyl-N-sulfochitosan, O-carboxymethyl chitosan sulfate, N-carboxymethyl chitosan-6-sulfate, and N,O-carboxymethyl -N,O-sulfochitosan were prepared respectively by using differential carboxymethylation and sulfation methods, and their IR spectrum and 13C-NMR spectrum were measured.展开更多
The microwave absorbing characteristics of basic cobalt carbonate,cobalt oxide(Co3O4),and the mixture of basic cobalt carbonate and cobalt oxide were investigated by means of microwave cavity perturbation,their temper...The microwave absorbing characteristics of basic cobalt carbonate,cobalt oxide(Co3O4),and the mixture of basic cobalt carbonate and cobalt oxide were investigated by means of microwave cavity perturbation,their temperature increasing curves were measured,and their ability to absorb microwave energy was also assessed based on the temperature increasing behavior of the material exposed to microwave field.Analyses of spectrum attenuation and relative frequency shift show that basic cobalt carbonate has weak capability to absorb microwave energy,while cobalt oxide has very strong capability to absorb microwave energy.It is feasible to thermally decompose basic cobalt carbonate though addition of small amount of cobalt oxide in microwave fields.The capability to absorb microwave energy of sample increases with an increase in mixing ratio of Co3O4.展开更多
Studying urea formation by ammonolysis of propylene carbonate in a liquid phase showed that this process is two-stage, and proceeds through preferred formation of 2-hydroxypropyl carbamate, besides, the rate of the fi...Studying urea formation by ammonolysis of propylene carbonate in a liquid phase showed that this process is two-stage, and proceeds through preferred formation of 2-hydroxypropyl carbamate, besides, the rate of the first stage is much higher than the rate of the second stage (urea formation). With the aid of the HPLC and HPLC/MS methods found some other intermediate products and offered consecutive-parallel scheme of the process. The obtained results explain the composition of impurities obtained during the production of the 13C-urea for diagnostic breath tests.展开更多
An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation...An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation of alkynes was realized with CO_(2) radical anion in-situ generated from formate as both a carbonyl source and a reductant.The collaboration between photosensitizer and hydrogen atom transfer catalyst promoted the catalytic cycle to work smoothly,giving a broad substrate scope including terminal and internal alkynes.The Giese radical addition of CO_(2) radical anion to the C—C triple bond is the key step to initiate the reaction.展开更多
The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The...The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).展开更多
文摘The activities of dimethyl carbonate and dimethyl sulfate as a methylation reagent were studied by density- functional theory (DFT). B3LYP/6-31G(d, p) methods were used to optimize the structures of dirnethyl carbonate and dimethyl sulfate and calculate theirs charge densities. Dimethyl sulfate is easier than dimethyl carbonate to react with a nucleophUic reagent. In dimethyl sulfate, the alkoxy carbons are the only reactive atomic nucleus because of steric hindrance. A nucleophilic reagent is more likely to react with carbonyl carbons than alkoxy carbons of dimethyl carbonate; in the presence of a Lewis acid, the phenyl nucleophilic reagent reacts with the Lewis acid first. Lewis acid increases the negative charge density of a nucleophUic reagent in polar solvent, and also incurs an accretion of steric hindrance. Polar solvent avails to ionize dimethyl carbonate and thus enables the reaction of methylation. The frequencies of transition state calculated by Gaussion 03 confirm the inferred reaction mechanism. The harvest rates of 4-methoxyphenol in the experiments of methylation reactions of hydroquinone with respectively dimethyl carbonate and dimethyl sulfate support the foregoing theortical conclusions.
文摘TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.
基金supported by the Development Project of Science and Technology of Qingdao(02-1-Kchhh-58)National‘863’High Technology Project of China(819-07-03)
文摘Five kinds of carboxymethyl sulfochitosans with different regions such as N-carboxymethyl-O-sulfochitosan, O-carboxymethyl-N-sulfochitosan, O-carboxymethyl chitosan sulfate, N-carboxymethyl chitosan-6-sulfate, and N,O-carboxymethyl -N,O-sulfochitosan were prepared respectively by using differential carboxymethylation and sulfation methods, and their IR spectrum and 13C-NMR spectrum were measured.
基金Project(50734007) supported by the National Natural Science Foundation of ChinaProject(2007GA002) supported by Project of Scienceand Technology of Yunnan Province,ChinaProject(2008-16) supported by the Analysis and Testing Foundation of Kunming Universityof Science and Technology,China
文摘The microwave absorbing characteristics of basic cobalt carbonate,cobalt oxide(Co3O4),and the mixture of basic cobalt carbonate and cobalt oxide were investigated by means of microwave cavity perturbation,their temperature increasing curves were measured,and their ability to absorb microwave energy was also assessed based on the temperature increasing behavior of the material exposed to microwave field.Analyses of spectrum attenuation and relative frequency shift show that basic cobalt carbonate has weak capability to absorb microwave energy,while cobalt oxide has very strong capability to absorb microwave energy.It is feasible to thermally decompose basic cobalt carbonate though addition of small amount of cobalt oxide in microwave fields.The capability to absorb microwave energy of sample increases with an increase in mixing ratio of Co3O4.
文摘Studying urea formation by ammonolysis of propylene carbonate in a liquid phase showed that this process is two-stage, and proceeds through preferred formation of 2-hydroxypropyl carbamate, besides, the rate of the first stage is much higher than the rate of the second stage (urea formation). With the aid of the HPLC and HPLC/MS methods found some other intermediate products and offered consecutive-parallel scheme of the process. The obtained results explain the composition of impurities obtained during the production of the 13C-urea for diagnostic breath tests.
文摘An efficient and sustainable protocol for regioselective hydrocarboxylation of alkynes to construct diverse propionic acid derivatives is disclosed.Under photoinduced conditions,the anti-Markovnikov hydrocarboxylation of alkynes was realized with CO_(2) radical anion in-situ generated from formate as both a carbonyl source and a reductant.The collaboration between photosensitizer and hydrogen atom transfer catalyst promoted the catalytic cycle to work smoothly,giving a broad substrate scope including terminal and internal alkynes.The Giese radical addition of CO_(2) radical anion to the C—C triple bond is the key step to initiate the reaction.
基金financially Supported by the National Natural Science Foundation of China (20772084)
文摘The asymmetric allylic alkylation reaction of sulfonylimidates with various Morita-Baylis-Hillman (MBH) carbonates was accomplished by the catalysis of commercially available cinchona alkaloids catalyst (DHQD)2AQN.The corresponding allylic alkylation products were obtained in good yields with high stereoselectivities (up to 99% ee,89:11 dr).