食品科学 ›› 2019, Vol. 40 ›› Issue (2): 200-207.doi: 10.7506/spkx1002-6630-20171023-255

• 成分分析 • 上一篇    下一篇

紫胶桐酸对映体的HPLC-ELSD法分离及其手性拆分热力学

李坤,张雯雯,刘兰香,郑华,李凯,徐涓,张弘*   

  1. (中国林业科学研究院资源昆虫研究所,国家林业局特色森林资源工程技术研究中心,云南?昆明 650224)
  • 出版日期:2019-01-25 发布日期:2019-01-22
  • 基金资助:
    中央级公益性科研院所基本科研业务费专项(CAFYBB2017MA012;CAFYBB2018SY024)

Enantioseparation and Thermodynamic Properties of Aleuritic Acid by High Performance Liquid Chromatography with Evaporative Light-Scattering Detector (HPLC-ELSD)

LI Kun, ZHANG Wenwen, LIU Lanxiang, ZHENG Hua, LI Kai, XU Juan, ZHANG Hong*   

  1. (Engineering Research Centre of Characteristic Forest Resources, State Forestry Administration, Research Institute of Resources Insects, Chinese Academy of Forestry, Kunming 650224, China)
  • Online:2019-01-25 Published:2019-01-22

摘要: 建立紫胶桐酸对映体的色谱学拆分方法并探索其手性拆分的热力学规律。采用高效液相色谱-蒸发光散射检测器法,通过研究流动相组成、流动相比例、柱温等因素对拆分效果的影响,得到最佳分离条件:DAICEL CHIRAL PAK IF色谱柱(25?cm×0.46?cm?i.d.,5?μm),流速0.5?mL/min,流动相组成为0.1%甲酸-乙腈(40∶60,V/V),柱温30?℃;蒸发光散射检测器条件:蒸发室温度70?℃,漂移管温度60?℃,载气流速1.6?L/min。拆分及表征结果表明,强碱皂化法提取所得紫胶桐酸为苏式结构的混旋体,其对映体相对含量分别为65.5%和34.5%,ee值为31%。拆分热力学研究结果显示,lnα与1/T以及lnk与1/T均呈良好的线性关系,R2分别为0.997?2、0.995?1和0.998?0;2?个对映体焓变与熵变之差ΔΔH为-3?453.0?J/mol和ΔΔS为-7.677?6?J/mol,均为负值,紫胶桐酸的对映体拆分过程受热焓控制。

关键词: 紫胶桐酸, 对映体, 高效液相色谱-蒸发光散射检测器, 手性拆分, 热力学

Abstract: The purposes of this study were to establish an enantiomeric separation method for aleuritic acid by high performance liquid chromatography with evaporative light-scattering detection (HPLC-ELSD) and to explore the thermodynamic pattern of the chiral resolution process. The optimum chromatographic conditions were determined by investigated the effect of mobile phase composition and column temperature. The best separation was achieved on a DAICEL CHIRAL PAK IF column (25 cm × 0.46 cm i.d., 5 μm) held at 30 ℃ using a mobile phase composed of a mixture of 0.1% formic acid solution and acetonitrile (40:60, V/V) at a flow rate of 0.5 mL/min. The optimum parameters of ELSD were determined as 70 ℃, 60 ℃ and 1.6 L/min for evaporator temperature, drift tube temperature and carrier gas (high purity nitrogen) flow rate, respectively. The results showed that aleuritic acid obtained by strong alkali saponification was a mixture of two threo-enantiomers (65.5:34.5) with an enantiomeric excess (ee) value of 31%. Thermodynamic analysis indicated that there was a good linear relationship between lnα, lnk1 and lnk2 and 1/T with correlation coefficients (R2) of 0.997 2, 0.995 1 and 0.998 0, respectively. The difference of enthalpy change (ΔΔH) between two enantiomers was ?3 453.0 J/mol and the difference of entropy change (ΔΔS) was ?7.677 6 J/mol, suggesting that the resolution process was controlled by entropy change.

Key words: aleuritic acid, enantiomer, HPLC-ELSD, enantiomeric separation, thermodynamics

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