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高效液相色谱直接光学拆分手性农药(英文)
引用本文:李晓刚,刘一平,胡昌弟,柏连阳,高必达,黄可龙.高效液相色谱直接光学拆分手性农药(英文)[J].中国化学工程学报,2011,19(4):603-609.
作者姓名:李晓刚  刘一平  胡昌弟  柏连阳  高必达  黄可龙
作者单位:1. College of Bio-safety Science & Technology, Hunan Agricultural University, Changsha 410128, China;2. Hunan Institute for the Control of Agrochemicals, Changsha 410005, China;3. Hunan Institute of Humanities, Science and Technology, Loudi 417000, China;4. Institute of Functionalized Materials & Chemistry, Central South University, Changsha 410083, China
基金项目:Supported by China Postdoctoral Science Fund (20090461007); Postdoctoral Research Funding Special Plans of Hunan(2010RC4025); Graduate Innovation Research Project of Hunan (CX2010B295)
摘    要:Enantiomer separation is one of the most important prerequisites for the investigation of environmental enantioselective behavior for chiral pesticides.The enantiomeric separation of three chiral pesticides,indoxacarb,lambda-cyhalothrin,and simeconazole,were studied on cellulose tris-(3,5-dimethylphenyl-carbamate)-coated chiral stationary phase(CDMPC-CSP) using high-performance liquid chromatography under normal phase condition.The effects of chromatographic conditions,such as the mobile phase composition including the concentration and type of alcohol modifiers in hexane,flow rate and column temperature,on enantiomer separation were examined.The thermodynamical mechanism of enantioseparation and chiral recognition mechanism were discussed.Better separation were achieved using 20% n-propanol for indoxacarb,2% iso-butanol for lambda-cyhalothrin,and 20% iso-propanol for simeconazole as modifiers in hexane at 25℃ with the selectivity factor(a) of 1.69,1.82 and 1.70,respectively.The resolution factor(Rs) decreased as the flow rate increased from 0.4 to 1.1 ml·min-1.The retention factor(k’) and selectivity factor for the enantiomers of analytes decreased as temperature increased.The lna-1/T plots for racemic chiral pesticides were linear in the range of 15-35℃ in hexane/iso-propanol and the chiral separation was controlled by enthalpy.Hydrogen bonding,π-π and dipole-dipole interactions between enantiomers and CDMPC-CSP play an important role in chiral identification,and the fitting of the asymmetric portion of solutes in a chiral cavity or channel of the CSP is also important.

关 键 词:高效液相色谱法  手性农药  光学分辨率  高效氯氟氰菊酯  对映体分离  手性识别机理  偶极相互作用  CDMPC
收稿时间:2010-11-17
修稿时间:2011-6-23  

Direct Optical Resolution of Chiral Pesticides by High Performance Liquid Chromatography
Xiaogang LI,Yiping LIU,Changdi HU,Lianyang BAI,Bida GAO,Kelong HUANG.Direct Optical Resolution of Chiral Pesticides by High Performance Liquid Chromatography[J].Chinese Journal of Chemical Engineering,2011,19(4):603-609.
Authors:Xiaogang LI  Yiping LIU  Changdi HU  Lianyang BAI  Bida GAO  Kelong HUANG
Affiliation:1. College of Bio-safety Science & Technology, Hunan Agricultural University, Changsha 410128, China;2. Hunan Institute for the Control of Agrochemicals, Changsha 410005, China;3. Hunan Institute of Humanities, Science and Technology, Loudi 417000, China;4. Institute of Functionalized Materials & Chemistry, Central South University, Changsha 410083, China
Abstract:Enantiomer separation is one of the most important prerequisites for the investigation of environmental enantioselective behavior for chiral pesticides. The enantiomeric separation of three chiral pesticides, indoxacarb, lambda-cyhalothrin, and simeconazole, were studied on cellulose tris-(3,5-dimethylphenyl-carbamate)-coated chiral stationary phase (CDMPC-CSP) using high-performance liquid chromatography under normal phase condition. The effects of chromatographic conditions, such as the mobile phase composition including the concentration and type of alcohol modifiers in hexane, flow rate and column temperature, on enantiomer separation were examined. The thermodynamical mechanism of enantioseparation and chiral recognition mechanism were discussed. Better separation were achieved using 20% n-propanol for indoxacarb, 2% iso-butanol for lambda-cyhalothrin, and 20% iso-propanol for simeconazole as modifiers in hexane at 25 °C with the selectivity factor (a) of 1.69, 1.82 and 1.70, respectively. The resolution factor (Rs) decreased as the flow rate increased from 0.4 to 1.1 ml·min?1. The retention factor (k') and selectivity factor for the enantiomers of analytes decreased as temperature increased. The lna–1/T plots for racemic chiral pesticides were linear in the range of 15-35 °C in hexane/iso-propanol and the chiral separation was controlled by enthalpy. Hydrogen bonding, π-π and dipole-dipole interactions between enantiomers and CDMPC-CSP play an important role in chiral identification, and the fitting of the asymmetric portion of solutes in a chiral cavity or channel of the CSP is also important.
Keywords:chiral resolution  high-performance liquid chromatography  indoxacarb  lambda-cyhalothrin  simeconazole  thermodynamical mechanism
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