新型分子印迹整体柱的制备与评价

发布时间：2018-08-29 18:44

【摘要】：分子印迹整体柱联合了分子印迹与整体柱两者优势,具备操作简单,选择性好及传质阻力低的特点,有助于色谱分离,是一种十分具有应用前景的色谱固定相,因此得到了迅速发展。本论文我们发展了两种新的分子印迹整体柱的方法,并对制备方案,色谱条件和物理表征等进行了研究。具体如下:多面体低聚倍半硅氧烷(POSS)是由硅和氧组成有机-无机杂化的笼状结构,具备良好的热稳定性、溶解性和耐酸碱性,本研究我们首次将POSS引入分子印迹领域,制备了POSS基质的印迹整体柱。实验中我们以S-萘普生为模板分子,4-乙烯吡啶为功能单体,POSS为共聚单体,二甲基丙烯酸乙二醇酯为交联剂,二甲基亚砜/离子液体为致孔剂制备了分子印迹整体柱。并对影响整体柱分离效果的模板含量,交联剂含量,POSS含量,聚合时间等因素进行了考察。结果显示,在流动相为乙腈:缓冲盐(99:1,pH 3.6,50 mmol L-1)时,测得在含有POSS的分子印迹整体柱上S-萘普生的保留因子为11.50,而对应的空白柱仅为0.78,该方法表明,在合适的制备条件下加入POSS可以制备出具有高选择性的印迹聚合物。以金属离子为枢纽和大分子拥挤试剂可有效提高模板与功能单体形成的印迹预复合物比例,为目前新的改进印迹效率的方法,本论文将这两者结合起来,发展了新的基于金属离子为枢纽和大分子拥挤试剂的印迹整体柱新方法。本文以齐墩果酸为模板分子,二甲基丙烯酸乙二醇酯为交联剂,4-乙烯吡啶为功能单体,二甲基亚砜/离子液体为致孔剂,聚甲基丙烯酸甲酯/三氯甲烷为拥挤试剂,乙酸钴为金属离子制备了分子印迹整体柱。实验结果表明,齐墩果酸印迹整体柱的印迹因子达到2.20,而未加钴离子的印迹整体柱印迹因子仅为1.07,说明钴离子的加入增强了印迹整体柱的选择性和特异性识别性能,这可能得益于氢键、离子相互作用、疏水作用以及印迹位点与模板分子空间的匹配。此外,还对PMMA浓度进行了考察,其最佳浓度为150 mg mL~(-1)。
[Abstract]:The molecularly imprinted monolithic column combines the advantages of molecular imprinting and monolithic column. It has the advantages of simple operation, good selectivity and low mass transfer resistance. It is helpful for chromatographic separation and is a kind of chromatographic stationary phase with great application prospect. As a result, it has developed rapidly. In this paper, we have developed two new methods of molecularly imprinted monolithic columns and studied their preparation, chromatographic conditions and physical characterization. The results are as follows: polyhedron oligosilane (POSS) is an organic-inorganic hybrid cage structure composed of silicon and oxygen, which has good thermal stability, solubility and acid and alkali resistance. In this study, POSS was first introduced into the field of molecular imprinting. The imprinted monolithic column of POSS matrix was prepared. In the experiment, the molecularly imprinted monolithic column was prepared using Snaproxen as template molecule, polyvinyl pyridine as functional monomer, glycol dimethacrylate as crosslinking agent and dimethyl sulfoxide / ionic liquid as pore-inducing agent. The factors influencing the separation effect of monolithic column, such as template content, crosslinking agent content, POSS content and polymerization time, were investigated. The results showed that when the mobile phase was acetonitrile: buffer salt (99: 1 ~ (-1) pH 3.6 ~ (50) mmol ~ (-1), the retention factor of S- naproxen on the molecularly imprinted monolithic column containing POSS was 11.50, while that of the blank column was only 0.78. The imprinted polymers with high selectivity can be prepared by adding POSS under suitable preparation conditions. The ratio of imprinted precomplex formed by template and functional monomer can be effectively increased by using metal ions as hub and macromolecular crowding reagent, which is a new method to improve imprinting efficiency. A new method of imprinted monolithic column based on metal ions as hub and macromolecular crowding reagent was developed. In this paper, oleanolic acid was used as template molecule, ethylene glycol dimethacrylate as crosslinking agent, dimethyl sulfoxide / ionic liquid as pore-forming agent, poly (methyl methacrylate) / trichloromethane as crowding reagent. The molecularly imprinted monolithic column was prepared by using cobalt acetate as metal ion. The results showed that the imprinting factor of oleanolic acid imprinted monolithic column was 2.20, but that of the imprinted monolithic column without cobalt ion was only 1.07, which indicated that the addition of cobalt ion enhanced the selectivity and specificity of the imprinted monolithic column. This may be due to hydrogen bonds, ion interactions, hydrophobic interactions and the matching of imprinted sites with template molecular spaces. The optimum concentration of PMMA was 150 mg mL~ (-1).
【学位授予单位】：天津医科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3

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