毛细管液相色谱柱的制备及应用
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摘要
毛细管液相色谱柱是一种新型色谱分离分析介质,是二十世纪后期发展起来的。与常规的色谱柱相比,具有渗透性好、样品消耗少、环境污染小、背压低、快速、高效等优点。本论文采用高压匀浆法制备手性色谱微柱,分离了多种手性化合物,并分别采用紫外光和微波引发,制备了以十八碳烯为功能单体的毛细管液相有机整体柱,并对其色谱性能进行了评价和应用探索。
正文共分六章：
第一章：毛细管液相色谱文献综述。
第二章：实验合成了纤维素三(3,5-二甲基苯基氨基甲酸酯)手性固定相,采用高压匀浆填充法制备了纤维素三(3,5-二甲基苯基氨基甲酸酯)手性微柱,自组装了毛细管液相色谱分离系统.选择了最佳涂敷量,考察了微柱的色谱性能,并利用该系统成功地拆分了5种手性化合物。结果表明,该制柱方法简便有效,微流系统搭建简单,成本较低,易于在实验室推广使用。
第三章：实验合成了L-脯氨酸键合硅胶手性固定相,采用所制备的L-脯氨酸键合硅胶毛细管液相色谱手性柱,在自组装的毛细管液相色谱仪上,分别对三种DL-α-氨基酸手性化合物进行了拆分。试验过程中采用了简单有效的Box-Bohnken实验设计方法,实现了分离条件的优化,得到了满意的拆分结果。分析过程中使用的流动相为硫酸铜水溶液,对环境无污染、绿色、环保而且分析成本较低,因此Box-Bohnken实验设计结合毛细管液相手性色谱法在DL-α-氨基酸的拆分中有广泛的应用前景,可以实现毛细管液相色谱对手性氨基酸的分析和检测。
第四章：采用紫外光原位聚合法制备了十八碳烯毛细管液相色谱整体柱,通过自组装的微流液相系统,考察了不同功能单体和交联剂的比例,二元流动相体积比变化、流速变化对选定模型化合物的柱效、分离度、保留时间等的影响,对柱内重现性、孔隙率等关键色谱参数进行了评价,并用其分离了苏丹红Ⅰ、苏丹红Ⅱ和苏丹红Ⅲ,三种酚类物质和四种菊酯类杀虫剂。
第五章：采用微波原位聚合法制备十八碳烯毛细管液相色谱整体柱。使用微波消解仪可以较准确的控制制柱过程的温度、时间、功率及压力等参数,可以提高制柱的重现性,微波聚合时间较短,与紫外光聚合和传统的水浴加热聚合相比,微波的聚合时间大大缩短了。传统的水浴加热聚合一般需要24小时,紫外光聚合也得需要1小时左右,而在本实验中仅需要180秒就可以完成制柱。实验通过自组装的毛细管液相系统,考察了不同流速、流动相的体积比对选定的模型化合物柱效、分离度、保留时间等的影响,对柱内重现性、孔隙率等关键色谱参数进行了评价,并用其成功分离了四种含嘧啶环的化合物。结果显示该制柱方法快速、简单,微流系统搭建简便,易于实现,值得实验室推广使用。
Capillary liquid column is a new separation medium which has developed since 1990s. Compared with the conventional chromatographic column, Capillary column has the following advantages:good permeability, small sample volume, less environmental pollution, low backpressure, fast and efficient. At present, researches on capillary column mostly focus on developing new monolithic and packing materials while only dabbling in techniques of preparing column.
In this thesis, the capillary chromatography chiral columns were prepared by high pressure slurry packing, which were used for some enantiomers separation. Meanwhile, the organic copolymer capillary chromatography micro-columns were prepared in situ polymerization, then the prepared columns was evaluated by the self-installed capillary liquid chromatography system.
This thesis consists of five chapters.
In chapter 1, a review on the capillary liquid chromatography was presented.
In chapter 2, we synthesized the cellulose tris (3,5-dimethylphenylcarbamate) chiral solid phase in the experiment. The cellulose tris (3,5-dimethylphenylcarbamate) chiral column was prepared by high pressure slurry packing. The best coated weight and chromatographic performance were achieved by capillary LC separation system. Five chiral analytes were separated. The results showed that this method of column prepared was fast, simple and easy to realize.
In the chapter 3, we synthesized the L-proline bonded silica gel chiral solid phase in the experiment. An L-proline bonded silica gel chiral column was prepared by the slurry packing technique. Threeα-amino acids were enantioseparated the self-installed capillary liquid chromatography. The simple and efficient Box-Behnken experimental design was used for the optimization. The optimum conditions of these variables were predicted by using a second-order polynomial model fitted to the results. this method has wide application prospect in separating DL-α-amino.
In the chapter 4, the 1-octadecene monolithic column was prepared by ultraviolet light initiation. The best percentage monomer and the key parameters such as column efficiency, column life, and column reproducibility were evaluated by means of capillary-LC. The results showed that this method of column prepared was fast, simple and easy to realize. Then, we separated SudanⅠ, SudanⅡ, SudanⅢ, three phenols and four chrysanthemum ester insecticide.
In the chapter 5, the 1-octadecene monolithic column was prepared by microwave irradiation. The key parameters of column preparation, such as temperature, time, pressure, microwave power, can be controlled accurately by using microwave dissolver. Microwave radiation shortens the polymerization time greatly. The results showed that this method of column prepared was fast, simple and easy to realize.
正文共分六章：
第一章：毛细管液相色谱文献综述。
第二章：实验合成了纤维素三(3,5-二甲基苯基氨基甲酸酯)手性固定相,采用高压匀浆填充法制备了纤维素三(3,5-二甲基苯基氨基甲酸酯)手性微柱,自组装了毛细管液相色谱分离系统.选择了最佳涂敷量,考察了微柱的色谱性能,并利用该系统成功地拆分了5种手性化合物。结果表明,该制柱方法简便有效,微流系统搭建简单,成本较低,易于在实验室推广使用。
第三章：实验合成了L-脯氨酸键合硅胶手性固定相,采用所制备的L-脯氨酸键合硅胶毛细管液相色谱手性柱,在自组装的毛细管液相色谱仪上,分别对三种DL-α-氨基酸手性化合物进行了拆分。试验过程中采用了简单有效的Box-Bohnken实验设计方法,实现了分离条件的优化,得到了满意的拆分结果。分析过程中使用的流动相为硫酸铜水溶液,对环境无污染、绿色、环保而且分析成本较低,因此Box-Bohnken实验设计结合毛细管液相手性色谱法在DL-α-氨基酸的拆分中有广泛的应用前景,可以实现毛细管液相色谱对手性氨基酸的分析和检测。
第四章：采用紫外光原位聚合法制备了十八碳烯毛细管液相色谱整体柱,通过自组装的微流液相系统,考察了不同功能单体和交联剂的比例,二元流动相体积比变化、流速变化对选定模型化合物的柱效、分离度、保留时间等的影响,对柱内重现性、孔隙率等关键色谱参数进行了评价,并用其分离了苏丹红Ⅰ、苏丹红Ⅱ和苏丹红Ⅲ,三种酚类物质和四种菊酯类杀虫剂。
第五章：采用微波原位聚合法制备十八碳烯毛细管液相色谱整体柱。使用微波消解仪可以较准确的控制制柱过程的温度、时间、功率及压力等参数,可以提高制柱的重现性,微波聚合时间较短,与紫外光聚合和传统的水浴加热聚合相比,微波的聚合时间大大缩短了。传统的水浴加热聚合一般需要24小时,紫外光聚合也得需要1小时左右,而在本实验中仅需要180秒就可以完成制柱。实验通过自组装的毛细管液相系统,考察了不同流速、流动相的体积比对选定的模型化合物柱效、分离度、保留时间等的影响,对柱内重现性、孔隙率等关键色谱参数进行了评价,并用其成功分离了四种含嘧啶环的化合物。结果显示该制柱方法快速、简单,微流系统搭建简便,易于实现,值得实验室推广使用。
Capillary liquid column is a new separation medium which has developed since 1990s. Compared with the conventional chromatographic column, Capillary column has the following advantages:good permeability, small sample volume, less environmental pollution, low backpressure, fast and efficient. At present, researches on capillary column mostly focus on developing new monolithic and packing materials while only dabbling in techniques of preparing column.
In this thesis, the capillary chromatography chiral columns were prepared by high pressure slurry packing, which were used for some enantiomers separation. Meanwhile, the organic copolymer capillary chromatography micro-columns were prepared in situ polymerization, then the prepared columns was evaluated by the self-installed capillary liquid chromatography system.
This thesis consists of five chapters.
In chapter 1, a review on the capillary liquid chromatography was presented.
In chapter 2, we synthesized the cellulose tris (3,5-dimethylphenylcarbamate) chiral solid phase in the experiment. The cellulose tris (3,5-dimethylphenylcarbamate) chiral column was prepared by high pressure slurry packing. The best coated weight and chromatographic performance were achieved by capillary LC separation system. Five chiral analytes were separated. The results showed that this method of column prepared was fast, simple and easy to realize.
In the chapter 3, we synthesized the L-proline bonded silica gel chiral solid phase in the experiment. An L-proline bonded silica gel chiral column was prepared by the slurry packing technique. Threeα-amino acids were enantioseparated the self-installed capillary liquid chromatography. The simple and efficient Box-Behnken experimental design was used for the optimization. The optimum conditions of these variables were predicted by using a second-order polynomial model fitted to the results. this method has wide application prospect in separating DL-α-amino.
In the chapter 4, the 1-octadecene monolithic column was prepared by ultraviolet light initiation. The best percentage monomer and the key parameters such as column efficiency, column life, and column reproducibility were evaluated by means of capillary-LC. The results showed that this method of column prepared was fast, simple and easy to realize. Then, we separated SudanⅠ, SudanⅡ, SudanⅢ, three phenols and four chrysanthemum ester insecticide.
In the chapter 5, the 1-octadecene monolithic column was prepared by microwave irradiation. The key parameters of column preparation, such as temperature, time, pressure, microwave power, can be controlled accurately by using microwave dissolver. Microwave radiation shortens the polymerization time greatly. The results showed that this method of column prepared was fast, simple and easy to realize.
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