基于金属离子枢纽的分子印迹整体柱的制备及评价

发布时间：2018-01-07 02:25

  本文关键词：基于金属离子枢纽的分子印迹整体柱的制备及评价　出处：《天津医科大学》2016年硕士论文　论文类型：学位论文

  更多相关文章： 离子液体 分子印迹整体柱 亲水性单体 金属离子枢纽 固相萃取

【摘要】：本文的第一部分制备了金属离子桥接的18β-甘草次酸印迹整体柱,实验中以1-丁基-3-甲基咪唑四氟硼酸盐、二甲基亚砜、N,N-二甲基甲酰胺([BMIM]BF4/DMSO/DMF)为三元致孔剂,4-乙烯基吡啶和二甲基丙烯酸乙二醇酯分别为单体和交联剂,钴离子为金属桥接剂,18β-甘草次酸为模板,通过原位聚合的方法合成整体柱。通过合成条件和色谱条件的优化,获得的最佳制备条件为模板:单体:交联剂的摩尔比例是1:4:20,最佳的金属离子是钴离子。此时制备的整体柱拥有最强的识别性和选择性,印迹因子为3.50。而在相同条件下,不加金属离子的分子整体柱印迹因子仅有1.52。研究证明了金属离子钴的加入增强了MIPs对18β-甘草次酸的保留和特异性识别,以较强的金属螯合作用替代了较弱的氢键作用。将所制备的MIP作为固相萃取的萃取剂,可分离纯化甘草次酸粗提液,最终获得样品的回收率为91.1%,纯度为93.8%。由此可见,以离子液体为致孔剂,金属离子作为桥接剂制备的分子印迹聚合物为天然产物甘草次酸的分离纯化提供了新途径。本文的第二部分制备了一种新型金属离子桥接的分子印迹整体柱用来提高水溶性模板分子的印迹效果。OEG(乙二醇和甲基丙烯酸的共聚物)是一种结构中包含一个寡甘醇侧链的亲水大分子单体,将其集成在基于金属离子枢纽MIP基质中可增强印迹空穴的选择性并且降低空穴的疏水性。实验中以离子液体([BMIM]BF4)/DMSO/DMF为三元致孔剂,4-乙烯基吡啶为功能单体,二甲基丙烯酸乙二醇酯为交联剂,水溶性没食子酸为模板,金属镍离子为桥接剂制备了高孔隙率和良好渗透性的印迹整体柱。实验中考察了OEG/4-VP的摩尔比例,交联度以及模板/金属离子的摩尔比例对整体柱印迹效果的影响。在最佳的合成条件和色谱条件下,该印迹整体柱的印迹因子为8.63。此外,通过Freundlich拟合分析,相比于不含分子单体OEG或是不含镍离子的整体柱,金属离子桥接的OEG整体柱具有较高的不均一系数,即该MIP的结合位点是非常均一的。总之,组合金属离子和亲水性大分子单体为制备高选择性和低疏水性的水溶性模板分子印迹整体柱提供了行之有效的方法。
[Abstract]:The first part of this paper was prepared by metal ion bridging 18 beta glycyrrhetinic acid imprinted monolithic column, in the experiment of 1- butyl -3- methylimidazolium tetrafluoroborate, two dimethyl sulfoxide, two N, N- dimethylformamide ([BMIM]BF4/DMSO/DMF) for three yuan of porogen, 4- vinyl pyridine and two methacrylic acid ethylene glycol ester was a monomer and a cross-linking agent, cobalt ion as metal bridging agent, 18 beta glycyrrhetinic acid as template and synthesized via in-situ polymerization monolithic columns. By optimizing the synthesis conditions and chromatographic conditions, the optimum conditions for preparation of template monomer: 1:4:20 is the mole ratio of cross-linking agent, metal the best is cobalt ion ion recognition and selectivity. The prepared monolithic column has the strongest, the imprinting factor for 3.50. in the same condition, the molecular without metal ion imprinted monolithic column factor only 1.52. research proved that adding cobalt metal ions The MIPs to identify the retention and specificity of 18 beta glycyrrhetinic acid, with metal chelation instead of strong hydrogen bonding is weak. The prepared MIP as extraction agent for solid phase extraction, separation and purification of glycyrrhetinic acid crude extracts, obtained the sample recovery rate was 91.1% and the purity. 93.8%. thus, using ionic liquid as porogen, molecular imprinted polymer metal ions as bridging agent preparation provide a new way for the separation and purification of natural products of glycyrrhetinic acid. The second part of this paper, the preparation of.OEG molecularly imprinting effect of a new type of metal ion bridging the whole column to improve the water solubility the template molecule (copolymer of ethylene glycol and methacrylic acid) is a hydrophilic macromolecular structure containing a oligoethylene glycol side chain monomer, which is integrated in the metal ion MIP hub matrix can enhance the selectivity of the imprinted cavity based on And reduce the hydrophobicity of the hole. In the experiment of ionic liquid ([BMIM]BF4) /DMSO/DMF for three yuan porogen, 4- vinylpyridine as functional monomers, two ethylene glycol dimethacrylate as crosslinking agent, water soluble gallic acid as template and nickel ion were prepared with high porosity and good permeability of imprinting the whole column as bridging agent. The effects of molar ratio of OEG/4-VP, influence of crosslinking degree and template / mole ratio of metal ions on the monolithic column. The imprinting effect in the best synthesis conditions and chromatographic conditions, the imprinted monolithic column imprinted factor is 8.63. Freundlich in addition, through fitting analysis, compared to the free monomeric OEG or column without nickel ion, not uniformity coefficient of OEG monolithic column has high metal ion bridging, namely binding sites of the MIP is very uniform. In a word, the combination of metal ions and water molecules The monomer provides an effective method for the preparation of highly selective and low hydrophobic water soluble template molecularly imprinted monolithic columns.

【学位授予单位】：天津医科大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.3
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本文编号：1390593