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两种多酚类化合物分子印迹整体柱的制备及其应用
王超
Thesis Advisor刘照胜、阿吉艾克拜尔·艾萨
2017-06-03
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Name硕士
Degree Discipline有机化学
Keyword柯里拉京 1,2,3,4,6-O-五没食子酰葡萄糖 多酚 分子印迹聚合物 固相萃取
Abstract

柯里拉京和1,2,3,4,6-O-五没食子酰葡萄糖(以下简称β-PGG)两种单体均属于多酚类化合物。二者广泛存在于天然植物中,具有多种生理学和药理学活性。因此,二者在医学、保健等诸多领域具有重要的应用价值。但由于二者在天然植物中的含量比较低,同时,由于天然植物提取物中的成分比较复杂,使得二者的分离纯化相对比较困难。因此,一种简单、快速、高效的分离纯化技术显得十分重要。本文利用原位聚合的方法,合成了柯里拉京和β-PGG两种多酚分子印迹整体柱,并以这两种多酚印迹聚合物作为固相萃取的吸附剂,实现了两种多酚化合物从天然植物粗提物中的纯化。主要结果如下: 1.合成了柯里拉京分子印迹整体柱,并将印迹聚合物应用于固相萃取,成功的从叶下珠粗提物中纯化出柯里拉京和没食子酸。具体过程如下:将模板柯里拉京溶解于三元致孔剂1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF4)/二甲亚砜(DMSO)/N’ N-二甲基甲酰胺(DMF)中,随后加入功能单体4-乙烯基吡啶(4-VP),交联剂乙二醇二甲基丙烯酸酯(EDMA)和引发剂偶氮二异丁腈(AIBN),得到预聚混合物。将预聚混合物超声,得到均一的混合物。然后将其装入不锈钢柱中,用生料带将不锈钢柱的两端进行密封,放入60 ℃水浴中反应18 h,便可制得柯里拉京分子印迹整体柱。最优化合成条件:n(柯里拉京): n(4-VP): n(EDMA)=1:10:40;所得整体柱对于柯里拉京的印迹因子可以达到9以上。另外,本文把柯里拉京分子印迹聚合物作为固相萃取的吸附剂,对叶下珠粗提物分离纯化条件进行了优化,最优化条件:?淋洗试剂:水-- 30 mL,接着乙腈/水(2/8, v/v)-- 20 mL;?洗脱试剂:乙腈/水(4/6, v/v)-- 40 mL。分离纯化结果:在保证柯里拉京和没食子酸的纯度均高于98%以上的前提下,二者的回收率分别为71.8%和94%。 2.合成了β-PGG分子印迹整体柱,并将该印迹聚合物作为固相萃取填料,成功的从白芍粗提物中纯化出β-PGG。具体过程如下:将模板β-PGG,功能单体4-VP,交联剂EDMA,桥接剂金属离子,亲水性大分子寡聚甲醚甲基丙烯酸酯(以下简称OEG),引发剂偶氮二异丁腈和三元致孔剂1-丁基-3甲基咪唑四氟硼酸盐/二甲亚砜/N’ N-二甲基甲酰胺混合,得到预聚混合物。将预聚混合物超声,得到均一的混合物。然后将其装入不锈钢柱中,用生料带将不锈钢柱的两端进行密封,放入60 ℃水浴中反应18h,便可制得β-PGG分子印迹整体柱。最优化合成条件:n(β-PGG): n(4-VP): n(EDMA)= 1:6:33,n(4-VP): n(镍离子): n(OEG)= 1:1:1,金属离子为镍离子,OEG分子量为300 g mol-1,所得整体柱对于β-PGG的印迹因子可以达到73以上。另外,本文把β-PGG分子印迹聚合物作为固相萃取的吸附剂,对白芍粗提物分离纯化条件进行了优化,最优化条件:?淋洗试剂:甲醇/水(7/3, v/v)-- 30 mL;?洗脱试剂:乙腈/水(9/1, v/v)-- 10 mL。分离纯化结果:在保证β-PGG的纯度高于98%以上的前提下,其回收率为74.1%。 关键词:柯里拉京 1,2,3,4,6-O-五没食子酰葡萄糖 多酚 分子印迹聚合物 固相萃取

Other Abstract

Corilagin (COR) and 1,2,3,4,6-penta-O-galloyl-beta-D-glucopyranose (β-PGG), which are polyphenols and widely found in natural plants, have a variety of physiological and pharmacological activities. Therefore, they have important applications among many fields, such as medicine, health care and so on. Because of their relatively low contents in natural plant and the complexity of the composition of natural products, however, the separation and purification of the two compounds is difficult. Therefore, a simple, fast and efficient separation and purification technology is urgently needed. In this paper, molecularly imprinted polymers were synthesized by in situ polymerization, and the imprinted polymers were used as the adsorbent for solid phase extraction(SPE). The separation and purification of two kinds of monomer compounds was realized. The main results are as follows: 1. COR-imprinted monolithic column was synthesized and imprinted polymer were applied to SPE. Corilagin and gallic acid were successfully purified from the crude extract of phyllanthus urinaria L.. The process is as follows: The template COR was dissolved in a ternary porogen 1-butyl-3-methylimidazolium tetrafluoroborate / dimethylsulfoxide / N’ N-dimethylformamide followed by the addition of functional monomer 4-vinylpyridine, crosslinking agent ethylene glycol dimethacrylate and initiator 2, 2’-Azobis (2-isobutyronitrile) to prepare a prepolymerized mixture. The prepolymerization mixture was ultrasounded and turned into a stainless steel column. Then the stainless steel column was sealed and placed in a water bath at 60 °C for 18 h to prepare a COR molecular imprinted monolithic column. Optimum synthesis conditions was n (COR): n (4-VP) : n (EDMA) = 1:10:40 and imprinting factor can be up to 9. In addition, the COR- molecularly imprinted polymer was used as the adsorbent for solid phase extraction, and the conditions of separation and purification of the crude extract were studied. The optimum conditions were as follows: elution condition: water -- 30 mL, then acetonitrile-water (2/8, v/v) --20 mL; elution conditions: acetonitrile - water (4/6, v/v) - 40 mL. The results showed that the recoveries of COR and gallic acid were 71.8% and 94%, respectively, with the purity higher than 98%. 2. β-PGG-imprinted monolithic column was synthesized and imprinted polymer were applied to SPE. β-PGG was successfully purified from the crude extract of Radix Paeoniae Alba.. The process is as follows: The template β-PGG, functional monomer 4-vinyl pyridine(4-VP), cross-linking agent ethylene glycol dimethacrylate(EDMA), bridging agent metal ions, oligomeric hydrophilic macromolecule methyl ether methacrylate (OEG), initiator 2, 2’-Azobis (2-isobutyronitrile) and ternary porogen N’ N-dimethylformamide/ dimethylsulfoxide / 1-butyl-3-methylimidazolium tetrafluoroborate were mixed to give birth to prepolymerization mixture. The prepolymerized mixture was ultrasounded and packed into a stainless steel column. The stainless steel column was then sealed and placed in a water bath at 60 ℃ for 18 h to prepare a β-PGG molecularly imprinted monolithic column. The optimum conditions were as follows: n(β-PGG): n(4-VP): n(EDMA) = 1:6:33, n (4-VP): n (nickel): n (OEG) = 1:1:1 , metal ion should be nickel ion. The imprinting factor can reach to more than 73. In addition, β-PGG molecularly imprinted polymer was used as the adsorbent for solid phase extraction, and the conditions of separation and purification of crude extract of Radix Paeoniae Alba. were optimized. The optimum conditions were as follows: methanol-water (7/3, v/v) -- 30 mL; elution conditions: acetonitrile - water (9/1, v/v) -- 10 mL. The results showed that the recoveries of β-PGG were 74.1% with the purity higher than 98%. Key words: Corilagin, 1,2,3,4,6-penta-O-galloyl-beta-D-glucopyranose, polyphenol, molecularly imprinted polymer, solid phase extraction

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/4947
Collection资源化学研究室
Recommended Citation
GB/T 7714
王超. 两种多酚类化合物分子印迹整体柱的制备及其应用[D]. 北京. 中国科学院大学,2017.
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