手性支撑乳状液膜拆分酰胺类除草剂的识别机理及传质模型研究

The chiral supported emulsion liquid membrane will be used to separate racemic amide herbicides. It is a new technology which utilizes the special reaction of amide herbisides and chiral carrier, and integrates advantages of hollow fiber supported liquid membrane and emulsion liquid membrane. The chiral emulsion liquid membrane will be achieved by dissolving chiral carrier into organic solvents, and then the solution of amide herbicides and chiral emulsion liquid membranes continuous flow in the tube side and shell side and made as feed phase and stripping phase respectively. It can extract the herbicides from the sample solution to the stripping phase, and the enantioseparation of racemic amide herbicides will be achieved according to the difference of special reaction of different enantiomers with the chiral carrier. The chiral recognition mechanism of enantiomeric amide herbicides molecules with chiral carrier molecules will be studied and stereoselective chiral carrier be screened; The principle of the formation of chiral supported emulsion liquid membrane system will also be studied and the corresponding mathematical model will be established and a series of stable chiral support emulsion liquid membrane system will be achieved; The effects of various factors on extraction performance will be investigated and appropriate conditions will be established. A mathematical model will be presented for analyzing the transport mechanism of the chiral herbicides in the hollow fiber supported emulsion liquid membrane. Theoretical calculations of the mass transfer process will be conducted by chemical engineering calculation software and mathematical tools. The experimental data will be used to test the mathematical model and the result will be used to optimize the conditions of the separation process under the guidance of theories and the model. This study will provide a scientific basis and theoretical support for enantioseparation of chiral pesticide, and help to develop single chiral pesticides of high efficacy, more safe to the crop and the environmental ecology and high market competitiveness.

本项目拟利用能与酰胺类药物特异性结合的手性载体,提出手性支撑乳状液膜拆分酰胺类除草剂的新技术，它整合了支撑液膜与乳状液膜各自的优点。其实现途径为：将手性载体溶解于有机溶剂制备手性乳状液膜，酰胺类除草剂溶液与手性乳状液膜分别作为原料相和提取相在中空纤维管件的管程和壳程连续流动，利用不同的对映体与手性载体特异性结合的差异性而实现分离。利用三维定量构效关系和分子对接研究酰胺类除草剂对映体分子与手性载体分子间的手性识别机理，筛选出立体选择性高的手性载体；研究手性支撑乳状液膜体系的形成原理，制备稳定高效的支撑乳状液膜；考察各种因素对支撑乳状液膜分离过程的影响，并探索其分离机理，建立相应的传质过程数学模型，以指导分离条件的优化和工业放大过程。本课题的研究将为手性农药的制备性分离技术提供科学依据和理论支持，有助于开发具有药效高、对作物和环境生态安全和成本低等优点的单一手性农药。

本研究采用薄层色谱、高效液相色谱、旋光仪等鉴别手段和能与萘草胺特异性结合的手性载体,建立萘草胺对映体以下拆分方法与分析方法：（1）结合手性金属骨架有机材料和碳纳米材料的薄层色谱法或柱层色谱法拆分萘草胺对映体；（2）手性乳状液膜、手性配体交换乳状液膜、手性离子液体、手性中空纤维膜拆分萘草胺对映体；（3）优化手性固定相和手性流动相，实现萘草胺对映体的正相、反相高效液相色谱分析。研究采用手性支撑乳状液膜分离苯丙氨酸对映体，得到了可以分析和预测乳状液膜手性拆分过程传质模型并与实验结果吻合。上述结果证实，我们提出“将手性载体溶解于有机溶剂制备手性乳状液膜，酰胺类除草剂溶液与手性乳状液膜分别作为原料相和提取相在中空纤维管件的管程和壳程连续流动，利用不同的对映体与手性载体特异性结合的差异性而实现分离”的途径和建立其传质模型是可行的，有助于开发具有药效高、对作物和环境生态安全和成本低等优点的单一手性农药。