茚虫威对映体分离及手性拆分热力学研究  

Thermodynamic Study of Chiral Separation of Indoxacarb Enantiomers by High Performance Liquid Chromatography

作　　者：刘一平[1] 李晓刚[1] 胡昌弟[1,2] 杨琛[1] 柏连阳[1,3] 高必达[1] 黄可龙[4] 

机构地区：[1]湖南农业大学生物安全科学技术学院,湖南长沙410128 [2]湖南省农药检定所,湖南长沙410005 [3]湖南人文科技学院,湖南娄底417000 [4]中南大学功能材料与化学研究所,湖南长沙410083

出　　处：《分析测试学报》2010年第12期1130-1134,1142,共6页Journal of Instrumental Analysis

基　　金：中国博士后科学基金资助项目(20090461007);湖南省教育厅青年基金资助项目(08B035)

摘　　要：在纤维素-三-（3,5-二甲基苯基氨基甲酸酯）（Chiralcel OD-H）手性柱上对茚虫威对映体的分离进行了研究。考察了流动相中改性剂种类和浓度、流速及柱温对分离效果的影响,并对茚虫威对映体与固定相之间保留和分离的热力学机理进行了讨论。结果表明,以正己烷-异丙醇（85∶15）为流动相,柱温为25℃,流速1.0 mL.min^-1时,茚虫威对映体能获得基线分离,分离因子（α）和分离度（Rs）分别为1.50和3.49;分别以5种体积分数均为15%的醇改性正己烷,分离因子的变化顺序为：异丁醇〈异丙醇〈乙醇〈正丁醇〈正丙醇,正丙醇的分离因子为1.67,证明醇的极性和空间位阻同时影响拆分效果;在0.4-1.1 mL.min^-1的流速范围内,分离度（Rs）随着流速的增大而逐渐减小;当柱温为15-35℃时,分离因子随着温度的升高呈降低趋势,两对映体的lnα与1/T呈良好的线性关系,手性拆分过程受焓的控制。The chiral separation of indoxacarb enantiomers on a Chiralcel OD-H column（cellulose tris（3,5-dimethylphenylcarbamate））was studied by high-performance liquid chromatography（HPLC）.The effects of chromatographic conditions such as the mobile phase composition,concentration and type of alcohol modifier in hexane,flow rate and column temperature on chiral separation of indoxacarb enantiomers were investigated,and the thermodynamic process of the retention and separation between the indoxacarb enantiomers and chiral stationary phase was studied.The result showed that a good baseline separation of the indoxacarb enantiomers was obtained by using n-hexane-isopropanol（85∶15,by volume）as mobile phase with a flow rate of 1.0 mL·min^-1 at 25 ℃.The resolution factor（α） and the resolution（Rs）were 1.50 and 3.49,respectively.The effects of five alcohol modifiers including ethanol,n-propanol,iso-propanol,n-butanol and iso-butanol with a volume ratio of 15% in hexane on the separation were investigated.The variational ranking of their resolution factors were as follows：iso-butanol（1.41）iso-propanol（1.50）ethanol（1.54）n-butanol（1.58）n-propanol（1.67）.The results indicated that the polarities and steric hindrances of the alcohols would influence the chiral separation simultaneously.The resolution of indoxacarb was decreased as the flow rate increased from 0.4 mL·min^-1 to 1.1 mL·min^-1,and the resolution factor was decreased with the increase of column temperature from 15 ℃ to 35 ℃.The lnα-1/T plots for the two enantiomers were linear,and the chiral separation process was controlled by the enthalpy.

关 键 词：手性拆分 茚虫威 对映体 高效液相色谱 热力学机理 

分 类 号：O657.72[理学—分析化学] S482.3[理学—化学]