亲水作用色谱的固定相设计及盐效应研究

发布时间：2018-06-09 05:02

本文选题：亲水作用色谱 + 磺酸甜菜碱　；参考：《宁夏大学》2017年硕士论文

【摘要】：本文以色谱硅胶为基质,采用原子转移自由基聚合(ATRP)技术将合成的N,N-二甲基-N-丙烯酰氧乙基-N-丙基磺酸铵(DMAEAPS)和N-乙烯基咪唑-N-丙磺酸盐(VIMPS)两种两性离子功能单体分别键合到Sil-Br基质材料表面,制备出含DMAEAPS和VIMPS的两种不同的磺酸甜菜碱型两性离子Sil-DMAEAPS和Sil-VIMPS色谱填料,通过考察极性溶质在自制色谱固定相上的保留行为,研究其色谱性能。同时考察了盐效应对不同极性溶质在硅胶柱(Kinetex silica)、氨基柱(Luna NH2)、烷基甜菜碱型两性离子柱(ZIC(?)-HILIC)、磷酰胆碱改性硅胶柱(ZIC(?)-cHILIC)四种商品柱上保留行为的影响,得到了一些有价值的结论。如以下几个部分:1.以丙烯酸二甲氨基乙酯(DMAEA)和1,3-丙磺酸内酯为原料,合成了含磺酸甜菜碱型两性离子的功能单体NN-二甲基-N-丙烯酰氧乙基-N-丙基磺酸铵(DMAEAPS),通过ATRP技术将其接枝到Sil-Br表面,制备出含DMAEAPS功能单体的Sil-DMAEAPS磺酸甜菜碱型两性离色谱固定相。研究了该固定相对安息香、维生素B6、芸香叶苷、对香豆酸和咖啡酸5种极性溶质的亲水作用色谱分离性能,发现极性溶质在典型的亲水作用色谱条件下(乙腈:水0.7,v/v),其保留主要由静电作用和亲水作用控制,而在典型的反相色谱条件下(乙腈:水0.2,v/v),则表现出反相柱的分离特征,极性溶质在该固定相上的保留是亲水色谱与反相色谱相结合的混合机理。与ZIC(?)-HILIC商品柱进行对比,发现自制色谱柱对溶质表现出不同的分离选择性。将自制色谱柱用于芦丁片中芸香叶苷以及当归、升麻中阿魏酸含量的测定,操作方法简单,为极性样品的分离提供了新方法。2.在冰浴磁力搅拌条件下以N-乙烯基咪唑和1,3-丙磺酸内酯为原料反应8 h,合成了N-乙烯基咪唑-N-丙磺酸盐两性离子(VIMPS)功能单体,采用1H-NMR及FT-IR对功能单体进行了表征。通过ATRP技术将VIMPS功能单体接枝到Sil-Br引发剂上,制备出含VIMPS功能单体的磺酸甜菜碱型两性离子(Sil-VIMPS)色谱固定相,通过元素分析,得知成功制备出Sil-VIMPS色谱填料。选取维生素B1、安息香、维生素B6、葛根素、阿魏酸、对香豆酸、咖啡酸、绿原酸8种酸碱性不同的极性溶质,以乙腈/甲酸铵缓冲盐为流动相,通过调节流动相甲酸铵缓冲盐浓度、乙腈含量、pH值,考察了极性溶质在该色谱固定相上的保留情况,实验结果表明所合成的Sil-VIMPS色谱固定相呈现出较优的亲水性及静电作用,对强碱性及酸性溶质均有良好的分离选择性。3.盐效应对改变HILIC的选择性有重要作用,通过改变缓冲盐种类、盐浓度等条件,系统地研究了尿嘧啶、尿嘧啶核苷、腺嘌呤、腺嘌呤核苷、胞嘧啶、胞嘧啶核苷、安息香、青霉素、维生素B6、阿魏酸、烟酸、咖啡酸和绿原酸等极性溶质组分在Kinetex silica、Luna NH2、ZIC(?)-HILIC、ZIC(?)-cHILIC上的保留行为。结果发现,甲酸铵缓冲盐浓度对极性溶质保留的影响较大,而硫酸铵缓冲盐的浓度对极性溶质的保留影响较小。
[Abstract]:In this paper, N, N- two methyl -N- acryl -N- propyl -N- propyl sulfonate (DMAEAPS) and N- vinyl imidazole -N- propane sulfonate (VIMPS) two kinds of amphoteric ionic functional monomers were bonded to the surface of Sil-Br matrix material by atomic transfer radical polymerization (ATRP), and two species containing DMAEAPS and VIMPS were prepared. The chromatographic performance of different sulfonated betaine type amphoteric ions Sil-DMAEAPS and Sil-VIMPS chromatography was investigated by investigating the retention behavior of polar solute on the homemade chromatographic stationary phase. At the same time, the effect of salt effect on different polar solutes in silica gel column (Kinetex silica), amino column (Luna NH2), alkyl betaine type amphoteric ion column (ZIC (?)) was investigated. HILIC), some valuable conclusions were obtained from the influence of the retention behavior of four kinds of silica gel column (ZIC (?) -cHILIC) on the silica gel column (ZIC (?) -cHILIC). For example, the functional monomer NN- two methyl -N- acryl containing sulfonate betaine type amphoteric ions was synthesized by using two methylamino ethyl acrylate (DMAEA) and 1,3- propionate lactate as raw materials. Oxygen ethyl -N- propyl sulfonic acid (DMAEAPS) was grafted onto the surface of Sil-Br by ATRP technology to prepare a Sil-DMAEAPS sulfonic acid betaine type separation chromatographic stationary phase containing DMAEAPS functional monomers. The hydrophilic chromatographic separability of the fixed relative benzoin, vitamin B6, rutin, and 5 polar solutes of coumaric acid and caffeic acid were studied. It is found that the polar solute is under the typical hydrophilic interaction chromatography (acetonitrile: water 0.7, v/v), and its retention is controlled mainly by electrostatic action and hydrophilic action, while the typical reverse phase chromatography (acetonitrile: water 0.2, v/v) shows the separation characteristics of the reverse phase column, and the retention of polar solute on the stationary phase is the hydrophilic and reverse phase chromatography Compared with the ZIC (?) -HILIC column, it was found that the homemade chromatographic column showed different separation selectivity for the solute. The homemade chromatographic column was used for the determination of the rutoside and Angelica in Rutinum Tablets, the determination of ferulic acid content in the cohosh, simple operation method, and a new method,.2. in the ice bath magnetic force for the separation of polar samples. The N- vinyl imidazole -N- propanosulfonate amphoteric ion (VIMPS) functional monomer was synthesized with N- vinyl imidazole and 1,3- propionate as raw material under stirring conditions, and the functional monomers were characterized by 1H-NMR and FT-IR. The sulfonium containing VIMPS functional monomers was grafted onto Sil-Br initiator by ATRP technology, and the sulfonated monomers containing the VIMPS functional monomer were prepared. Acid betaine type amphoteric ion (Sil-VIMPS) chromatography fixed phase, through the element analysis, the Sil-VIMPS chromatographic packing was successfully prepared. Vitamin B1, benzoin, vitamin B6, puerarin, ferulic acid, and 8 kinds of acid and alkali solute with different acids and alkalinity of coumaric acid, caffeic acid and chlorogenic acid, acetonitrile / ammonium formate buffer salt was used as the mobile phase, through regulating flow. The concentration of ammonium formate buffer salt, the content of acetonitrile, pH value, and the retention of polar solute on this chromatographic stationary phase were investigated. The experimental results showed that the synthesized Sil-VIMPS chromatographic stationary phase showed better hydrophilic and electrostatic effect, and good separation and selective.3. salt efficiency for strong alkaline and acidic solutes should be selected to deal with the selection of HILIC. Selectivity has an important role in the systematic study of uracil, uracil, adenine, adenine, adenine, cytosine, cytosine, cytosine, cytosine, cytosine, cytosine, vitamin B6, ferulic acid, nicotinic acid, chlorogenic acid and chlorogenic acid in Kinetex silica, Luna NH2, ZIC (?) -HILIC, ZIC. (?) retention behavior on -cHILIC. It is found that the concentration of ammonium formate buffer salt has great influence on the retention of polar solute, while the concentration of ammonium sulfate buffer salt has little effect on the retention of polar solute.
【学位授予单位】：宁夏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O652.6

【参考文献】