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  本文關(guān)鍵詞：基于金屬離子樞紐的分子印跡整體柱的制備及評價　出處：《天津醫(yī)科大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 離子液體 分子印跡整體柱 親水性單體 金屬離子樞紐 固相萃取

【摘要】：本文的第一部分制備了金屬離子橋接的18β-甘草次酸印跡整體柱,實驗中以1-丁基-3-甲基咪唑四氟硼酸鹽、二甲基亞砜、N,N-二甲基甲酰胺([BMIM]BF4/DMSO/DMF)為三元致孔劑,4-乙烯基吡啶和二甲基丙烯酸乙二醇酯分別為單體和交聯(lián)劑,鈷離子為金屬橋接劑,18β-甘草次酸為模板,通過原位聚合的方法合成整體柱。通過合成條件和色譜條件的優(yōu)化,獲得的最佳制備條件為模板:單體:交聯(lián)劑的摩爾比例是1:4:20,最佳的金屬離子是鈷離子。此時制備的整體柱擁有最強(qiáng)的識別性和選擇性,印跡因子為3.50。而在相同條件下,不加金屬離子的分子整體柱印跡因子僅有1.52。研究證明了金屬離子鈷的加入增強(qiáng)了MIPs對18β-甘草次酸的保留和特異性識別,以較強(qiáng)的金屬螯合作用替代了較弱的氫鍵作用。將所制備的MIP作為固相萃取的萃取劑,可分離純化甘草次酸粗提液,最終獲得樣品的回收率為91.1%,純度為93.8%。由此可見,以離子液體為致孔劑,金屬離子作為橋接劑制備的分子印跡聚合物為天然產(chǎn)物甘草次酸的分離純化提供了新途徑。本文的第二部分制備了一種新型金屬離子橋接的分子印跡整體柱用來提高水溶性模板分子的印跡效果。OEG(乙二醇和甲基丙烯酸的共聚物)是一種結(jié)構(gòu)中包含一個寡甘醇側(cè)鏈的親水大分子單體,將其集成在基于金屬離子樞紐MIP基質(zhì)中可增強(qiáng)印跡空穴的選擇性并且降低空穴的疏水性。實驗中以離子液體([BMIM]BF4)/DMSO/DMF為三元致孔劑,4-乙烯基吡啶為功能單體,二甲基丙烯酸乙二醇酯為交聯(lián)劑,水溶性沒食子酸為模板,金屬鎳離子為橋接劑制備了高孔隙率和良好滲透性的印跡整體柱。實驗中考察了OEG/4-VP的摩爾比例,交聯(lián)度以及模板/金屬離子的摩爾比例對整體柱印跡效果的影響。在最佳的合成條件和色譜條件下,該印跡整體柱的印跡因子為8.63。此外,通過Freundlich擬合分析,相比于不含分子單體OEG或是不含鎳離子的整體柱,金屬離子橋接的OEG整體柱具有較高的不均一系數(shù),即該MIP的結(jié)合位點是非常均一的�？傊�,組合金屬離子和親水性大分子單體為制備高選擇性和低疏水性的水溶性模板分子印跡整體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.

【學(xué)位授予單位】：天津醫(yī)科大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O631.3
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本文編號：1390593