The synthesis of anti-radiation active organic phosphorus compounds is an important field in search of radioprotectors.In order to develop new protectors of low toxicity and high potency, more than thirty phosphorus c...The synthesis of anti-radiation active organic phosphorus compounds is an important field in search of radioprotectors.In order to develop new protectors of low toxicity and high potency, more than thirty phosphorus compounds such as dialkylphosphorocyanidates(1), tetraalkylmonothiopyrophosphates(2), N-substituted dialkylphosphoramidates(3) and aminoalkylthiophosphates (4)have been designed and synthesized.展开更多
A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR s...A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selec- tivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.展开更多
A sequential one-pot synthesis of N-sulfonylcyclothioureas from N-monosulfonyl diamines, CS2 and chloroace- tic acid at room temperature in water is described. In the absence of highly toxic thiophosgene and organic s...A sequential one-pot synthesis of N-sulfonylcyclothioureas from N-monosulfonyl diamines, CS2 and chloroace- tic acid at room temperature in water is described. In the absence of highly toxic thiophosgene and organic solvents, this method is environmentally benign. Simple reaction conditions, easy purification of the products, good yields and thioglycolic acid as the useful byproduct are also important attributes of this methodology. The plausible mechanism including tandem reactions is proposed.展开更多
A new route was described to synthesize Arg-Gly-Asp-X（RGDX,X=amino acid） tetrapeptide.To better understand the method,the tetrapeptide Arg-Gly-Asp-CySS（RGDCySS） was chosen as a model target for X.First,GDCySS was ...A new route was described to synthesize Arg-Gly-Asp-X（RGDX,X=amino acid） tetrapeptide.To better understand the method,the tetrapeptide Arg-Gly-Asp-CySS（RGDCySS） was chosen as a model target for X.First,GDCySS was obtained in four steps,comprising the chloroacetylation of L-aspartic acid（ClCH2COAsp）,synthesis of chloroacetyl L-aspartic acid anhydride[ClCH2COAsp（CO）2O],formation of ClCH2COAsp-CySS and ammonolysis of ClCH2COAsp-CySS.Second,preparation of Arg-NCA,which was coupled with GDCySS to synthesize RGDCySS by the NCA method（Leuchs＇ anhydrides method,NCA：N-carboxy-a-amino acid anhydride）.The purity of the product was analyzed by the high performance liquid chromatography（HPLC）.Molecular weights of the peptide products were confirmed by mass spectroscopy.In the developed approach,less protected amino acids were used compared to conventional solid-phase synthesis.The new route offers advantages of low cost,simplicity and rapid synthesis with a reasonable yield of 63.0％（calculated according to arginine content）.展开更多
为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X...为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X射线衍射(XRD)和扫描电镜(SEM)结果表明,NMP在[Zn4O(BDC)3]8孔道中的吸附力较DMF的弱,NMP分子更容易从框架中脱除;热重(TG)和热重-红外联用(TGA/FT-IR)结果表明,以DMF为溶剂合成的[Zn4O(BDC)3]8的热分解温度和热稳定性较高;氮气等温吸附实验(BET)发现,以NMP为溶剂合成的[Zn4O(BDC)3]8的气体吸附性能更强,兰缪尔比表面积高于用DMF合成的[Zn4O(BDC)3]8。调控介电常数设定溶剂分别为NMP和DMF,用COSMO溶剂化方法对溶剂分子与框架化合物基本结构单元Zn4O(BDC)3间相互作用模型进行几何优化计算,发现溶剂设定为NMP时Zn4O(BDC)3优化结构的总能量较溶剂设定为DMF时的高8.6405 k J/mol,这说明DMF分子与Zn4O(BDC)3间的结合力强于NMP分子的,溶剂化作用降低了Zn与O间的离子性;用DMol3在GGA-BLYP/DN水平计算了DMF、NMP或DEF溶剂分子在[Zn4O(BDC)3]8晶体孔道中的相互作用,与DMF相比,NMP在孔道中能量状态稳定性较差,在能量状态角度上NMP应最容易从框架材料孔道中脱除。研究结果说明NMP更有利于合成性质良好的[Zn4O(BDC)3]8,与DMF相比NMP与框架结构基元间的作用力较弱。展开更多
The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the ...The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the “flux”method,where the st arting materials are solved in a melt,which is usually formed by excess CuO and BaO or a KCl/NaCl mixture.The crystals are produced by slow cooling of the heate d solvent.This method,however,suffers from several disadvantages: (1) the crystals are contaminated with the crucible material, (2) the crystals are difficult to remove from the crucible, (3) the crystals contain flux inclusions.展开更多
文摘The synthesis of anti-radiation active organic phosphorus compounds is an important field in search of radioprotectors.In order to develop new protectors of low toxicity and high potency, more than thirty phosphorus compounds such as dialkylphosphorocyanidates(1), tetraalkylmonothiopyrophosphates(2), N-substituted dialkylphosphoramidates(3) and aminoalkylthiophosphates (4)have been designed and synthesized.
基金Project supported by the Science and Technology Ministry of China (No. 2001CCA02700).
文摘A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selec- tivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.
基金Project supported by the National Natural Science Foundation of China （No. 20802049）.
文摘A sequential one-pot synthesis of N-sulfonylcyclothioureas from N-monosulfonyl diamines, CS2 and chloroace- tic acid at room temperature in water is described. In the absence of highly toxic thiophosgene and organic solvents, this method is environmentally benign. Simple reaction conditions, easy purification of the products, good yields and thioglycolic acid as the useful byproduct are also important attributes of this methodology. The plausible mechanism including tandem reactions is proposed.
基金Supported by the National Natural Science Foundation of China（No.81271697）, the Science Foundation of Changchun City, China（No.09SF02）, the China Postdoctoral Science Foundation（No.20100481048）, the Specialized Research Fund for the Doctoral Program of Higher Education of China（No.20100061120077） and the Social Development Project of Science and Tech- nology Department of Jilin Province, China（Nos.20106031, 20120967, YYZX2012）.
文摘A new route was described to synthesize Arg-Gly-Asp-X（RGDX,X=amino acid） tetrapeptide.To better understand the method,the tetrapeptide Arg-Gly-Asp-CySS（RGDCySS） was chosen as a model target for X.First,GDCySS was obtained in four steps,comprising the chloroacetylation of L-aspartic acid（ClCH2COAsp）,synthesis of chloroacetyl L-aspartic acid anhydride[ClCH2COAsp（CO）2O],formation of ClCH2COAsp-CySS and ammonolysis of ClCH2COAsp-CySS.Second,preparation of Arg-NCA,which was coupled with GDCySS to synthesize RGDCySS by the NCA method（Leuchs＇ anhydrides method,NCA：N-carboxy-a-amino acid anhydride）.The purity of the product was analyzed by the high performance liquid chromatography（HPLC）.Molecular weights of the peptide products were confirmed by mass spectroscopy.In the developed approach,less protected amino acids were used compared to conventional solid-phase synthesis.The new route offers advantages of low cost,simplicity and rapid synthesis with a reasonable yield of 63.0％（calculated according to arginine content）.
基金Project(51104185)supported by the National Natural Science Foundation of ChinaProject(2010QZZD003)supported by the Key Project of Central South University of Fundamental Research Funds for the Central Universities of China
文摘为探究溶剂对合成有机金属框架化合物的影响机制,采用实验和DFT理论计算相结合的方法,研究溶剂N,N-二甲基甲酰胺(DMF)和N-甲基-2-吡咯烷酮(NMP)对溶剂热法合成有机金属框架材料[Zn4O(BDC)3]8的影响及溶剂与框架间的微观作用机制。粉末X射线衍射(XRD)和扫描电镜(SEM)结果表明,NMP在[Zn4O(BDC)3]8孔道中的吸附力较DMF的弱,NMP分子更容易从框架中脱除;热重(TG)和热重-红外联用(TGA/FT-IR)结果表明,以DMF为溶剂合成的[Zn4O(BDC)3]8的热分解温度和热稳定性较高;氮气等温吸附实验(BET)发现,以NMP为溶剂合成的[Zn4O(BDC)3]8的气体吸附性能更强,兰缪尔比表面积高于用DMF合成的[Zn4O(BDC)3]8。调控介电常数设定溶剂分别为NMP和DMF,用COSMO溶剂化方法对溶剂分子与框架化合物基本结构单元Zn4O(BDC)3间相互作用模型进行几何优化计算,发现溶剂设定为NMP时Zn4O(BDC)3优化结构的总能量较溶剂设定为DMF时的高8.6405 k J/mol,这说明DMF分子与Zn4O(BDC)3间的结合力强于NMP分子的,溶剂化作用降低了Zn与O间的离子性;用DMol3在GGA-BLYP/DN水平计算了DMF、NMP或DEF溶剂分子在[Zn4O(BDC)3]8晶体孔道中的相互作用,与DMF相比,NMP在孔道中能量状态稳定性较差,在能量状态角度上NMP应最容易从框架材料孔道中脱除。研究结果说明NMP更有利于合成性质良好的[Zn4O(BDC)3]8,与DMF相比NMP与框架结构基元间的作用力较弱。
文摘The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the “flux”method,where the st arting materials are solved in a melt,which is usually formed by excess CuO and BaO or a KCl/NaCl mixture.The crystals are produced by slow cooling of the heate d solvent.This method,however,suffers from several disadvantages: (1) the crystals are contaminated with the crucible material, (2) the crystals are difficult to remove from the crucible, (3) the crystals contain flux inclusions.
