發(fā)布時(shí)間：2018-08-29 18:44

【摘要】：分子印跡整體柱聯(lián)合了分子印跡與整體柱兩者優(yōu)勢(shì),具備操作簡(jiǎn)單,選擇性好及傳質(zhì)阻力低的特點(diǎn),有助于色譜分離,是一種十分具有應(yīng)用前景的色譜固定相,因此得到了迅速發(fā)展。本論文我們發(fā)展了兩種新的分子印跡整體柱的方法,并對(duì)制備方案,色譜條件和物理表征等進(jìn)行了研究。具體如下:多面體低聚倍半硅氧烷(POSS)是由硅和氧組成有機(jī)-無(wú)機(jī)雜化的籠狀結(jié)構(gòu),具備良好的熱穩(wěn)定性、溶解性和耐酸堿性,本研究我們首次將POSS引入分子印跡領(lǐng)域,制備了POSS基質(zhì)的印跡整體柱。實(shí)驗(yàn)中我們以S-萘普生為模板分子,4-乙烯吡啶為功能單體,POSS為共聚單體,二甲基丙烯酸乙二醇酯為交聯(lián)劑,二甲基亞砜/離子液體為致孔劑制備了分子印跡整體柱。并對(duì)影響整體柱分離效果的模板含量,交聯(lián)劑含量,POSS含量,聚合時(shí)間等因素進(jìn)行了考察。結(jié)果顯示,在流動(dòng)相為乙腈:緩沖鹽(99:1,pH 3.6,50 mmol L-1)時(shí),測(cè)得在含有POSS的分子印跡整體柱上S-萘普生的保留因子為11.50,而對(duì)應(yīng)的空白柱僅為0.78,該方法表明,在合適的制備條件下加入POSS可以制備出具有高選擇性的印跡聚合物。以金屬離子為樞紐和大分子擁擠試劑可有效提高模板與功能單體形成的印跡預(yù)復(fù)合物比例,為目前新的改進(jìn)印跡效率的方法,本論文將這兩者結(jié)合起來(lái),發(fā)展了新的基于金屬離子為樞紐和大分子擁擠試劑的印跡整體柱新方法。本文以齊墩果酸為模板分子,二甲基丙烯酸乙二醇酯為交聯(lián)劑,4-乙烯吡啶為功能單體,二甲基亞砜/離子液體為致孔劑,聚甲基丙烯酸甲酯/三氯甲烷為擁擠試劑,乙酸鈷為金屬離子制備了分子印跡整體柱。實(shí)驗(yàn)結(jié)果表明,齊墩果酸印跡整體柱的印跡因子達(dá)到2.20,而未加鈷離子的印跡整體柱印跡因子僅為1.07,說(shuō)明鈷離子的加入增強(qiáng)了印跡整體柱的選擇性和特異性識(shí)別性能,這可能得益于氫鍵、離子相互作用、疏水作用以及印跡位點(diǎn)與模板分子空間的匹配。此外,還對(duì)PMMA濃度進(jìn)行了考察,其最佳濃度為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).
【學(xué)位授予單位】：天津醫(yī)科大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O631.3

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