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基于分子拥挤效应的三种化合物的印迹聚合物的制备及应用研究
贾曼
Thesis Advisor刘照胜
2018-06-02
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Name博士
Degree Discipline有机化学
Keyword安石榴苷 原花青素b2 秦皮乙素 分子印迹 分子拥挤环境
Abstract

新疆特色植物资源丰富,多酚类化合物是一类具有生理活性的化合物,其中安石榴苷具有多种药理活性,原花青素B2是至今为止被认为活性最高的抗氧化剂,秦皮乙素作为抗癌药物以及优秀的合成中间体逐渐受到人们的青睐。目前,传统纯化多酚类化合物的方法主要包括柱色谱、液相色谱和逆流色谱。由于缺乏特异选择性,这些方法通常具有时耗长、溶剂消耗量大、操作繁琐等缺点。因此,新型高效的多酚类化合物纯化技术的开发显得至关重要。分子印迹是一种根据特定目标化合物(又称“模板”)合成具有特异选择性填料的技术。然而经典的分子印迹技术难以解决模板分子溶解度太小的问题,模板消耗量较大,选择性不高等缺点,限制了分子印迹材料在分离纯化植物多酚的工作中的应用,其次,当模板分子为酸性分子时传统的功能单体在制备印迹聚合物时不具有优势,且在质子溶剂环境下无法形成高印迹因子的聚合材料,本文通过模拟生物细胞中的“大分子拥挤效应”,分别以安石榴苷,原花青素B2和秦皮乙素为模板,探索了非均匀拥挤环境对提高印迹因子的作用,质子溶剂环境下离子液体型分子印迹材料的合成,以及新的致孔剂体系的开发。成功开发了三种选择性高,模板消耗量少的分子印迹聚合物并用于新疆特色植物中多酚固相萃取。具体实施情况如下:1.以安石榴苷为模板,以丙烯酰胺为功能单体、二甲基丙烯酸乙二醇酯为交联剂、PEG-THF-甲苯为联合致孔剂,在拥挤环境下偶氮二异丁腈为引发剂,混合后装入不锈钢柱管中,密封,在水浴55℃条件下反应24 h,得到安石榴苷印迹整体柱。最优的合成条件是:模板/单体物质的量比为1:60;PEG浓度40mg/mL,得到最高的印迹因子为10.60。把安石榴苷印迹材料和固相萃取技术结合,通过优化萃取条件,得到最优化的条件为:以甲醇-水混合溶液(60 : 40,v/v)为上样试剂;乙腈为淋洗试剂;乙腈-水混合溶液(50 : 50 v/v)为洗脱试剂;得到纯度为97.7%的安石榴苷,回收率为85%。2.以原花青素B2为模板,以丙烯酰胺为功能单体,二甲基丙烯酸乙二醇酯为交联剂、PEG-PS-THF为三元致孔剂,聚苯乙烯为线性大分子致孔剂,在非均匀拥挤环境下偶氮二异丁腈为引发剂,混合后装入不锈钢柱管中,密封水浴55℃反应24 h,得到原花青素B2的分子印迹整体。最优的合成条件:单体/模板的物质的量比为16:1,聚苯乙烯的浓度为40 mg/mL,制备了通透性良好的分子印迹整体柱,原花青素B2最大的印迹因子为5.13。将分子印迹材料与固相萃取技术相结合,通过优化固相萃取条件得出:甲醇/水(5:5, v/v)为上样试剂,甲醇/水(8:2, v/v)为淋洗试剂,乙腈/水(9:1, v/v)作为洗脱试剂,得到了原花青素B2单体化合物 ,纯度>90%,回收率为87%。3.以秦皮乙素为模板,以离子液体1-乙烯基-3-乙基四氟硼酸盐为功能单体,二甲基丙烯酸乙二醇酯为交联剂、PEG-PS-THF为三元致孔剂,聚苯乙烯为线性大分子致孔剂,在拥挤环境下偶氮二异丁腈为引发剂,混合后装入不锈钢柱管中,密封水浴55℃反应24 h,得到秦皮乙素的分子印迹整体。最优的合成条件:单体:模板为4.8:1,聚苯乙烯的浓度为40 mg/mL,制备了通透性良好的分子印迹整体柱,对秦皮乙素最大的选择因子为11.83。为了进一步证明在质子溶剂环境下的,以离子液体作为功能单体仍能表现出很好印迹效果,分别以环境污染物三氯生和杀虫剂吡虫啉为模板分子,两者的分子印迹材料也表现出了良好的印迹效果,分子印迹材料结合固相萃取技术优化固相萃取条件,最优的处理条件:甲醇为上样试剂,乙腈为淋洗试剂,甲醇作为洗脱试剂,得到纯度大于92%的秦皮乙素,回收率为80%。

Other Abstract

There are characteristic of plant resources in XinJiang,The punicalaginhas various pharmacological activities, procyanidin B2 is considered the highest antioxidant activity as so far, aesculetin gets gradually the favour of people due to theanticancer activities and excellent intermediates.At present, the methods of traditional purification of polyphenols mainly include column chromatography, liquid chromatography and countercurrent chromatography. These methods usually have disadvantages such as long time consumption, large solvent consumption and cumbersome operation due to the lack of specific selectivity.Therefore, itis very important to developa new and efficient technology of purificationof polyphenolic compound.Molecular imprinting is a technique for synthesizing selective fillers based on specific target compounds (also known as "templates"). However, the classic molecular imprinting technology is difficult to solve the problem of some template molecules which is difficult to dissolve in the selution. The classic molecular imprinting technology has some disadvantages such asimprinting cost is higherdue to template consumption is large, the shortcoming of lowselectivity, which limited the application of the molecularly imprinted materials in the purification of plant polyphenols, this paper is aim to simulate the biological cells "macromolecular crowding effect". The punicalagin, procyanidin B2 and aesculetin are used as templates, we successfully developed three types of molecularly imprinted polymer which possessed high selectivity, less consumption template.Those molecularly imprinted polymers were used as the solid phase extraction for Uighur classic plant polyphenols.The specific implementation is as follows:1. Punicalagin was uesed as the template, acrylamide was used as the functional monomer, ethylene glycol methacrylate was a crosslinking agent, PEG - THF - toluene was used as a porogen in the crowded environment, 2,2’-Azobis (2-isobutyronitrile) was used as initiator, the mixture was blend in stainless steel tube, seal, the reaction under the condition of the water bath 55 ℃ for 24 h. The optimum synthesis condition: the ratio of the template/monomer was 1:60; the concentration of PEG was 40mg/mL; the highest imprinted factor was 10.60.The punicalagin-molecularly imprinted materials combined with solid phase extraction, by optimizing the extraction conditions, the optimal condition: methanol-water mixture (60:40, v/v) was as the reagent on sample; Acetonitrile was used as leaching reagent; Acetonitrile-water mixture solution (50:50 v/v) was eluting reagent. The optimal MIPs can be used as solid-phase extraction sorbents for purification of punicalatin with a recovery of 85% and a purity of 97.7% .2. Procyanidins B2 was uesed as the template, acrylamide was used as the functional monomer, ethylene glycol methacrylate was a crosslinking agent, PEG - THF -PS was used as joint porogen, in the crowded environment, azodiisobutyronitrile was used as initiator, the mixture was blend in stainless steel tube, seal, the reaction under the condition of the water bath 55 ℃ for 24 h. The optimum synthesis condition: the ratio of the template/monomer material is 1:16;PEG concentration 40mg/mL, the highest imprinted factor was5.13. The Procyanidins B2-molecularly imprinted materials combined with solid phase extraction, by optimizing the extraction conditions, we got optimal condition: Methanol/water (5:5, v/v) was used as the reagent on the samples, methanol/water (8:2, v/v) was usedas the washing reagent, acetonitrile/water (9:1, v/v) was used the elution reagent. The optimal MIPs can be used as solid-phase extraction sorbents for purification of Procyanidins B2 with a recovery of 80% and a purity of 90% .3.In this study, an ionic liquid (1-vinyl-3-ethylimidazolium tetrafluoroborate [VEIm][BF4]) was employed as the functional monomer and aesculetin was employed as template molecule in a crowding surrounding, which was made up of a THF solution of polystyrene (PS). Ethylene glycol methacrylate was as the crosslinking agent, polystyrene was as the linear macromolecules porogen, in the crowded environment, azodiisobutyronitrile was as initiator, the mixture was blend in stainless steel tube, seal in water bath 55 ℃ for 24 h. The optimal synthesis condition: monomer: the template is 4.8:1, the concentration of polystyrene is 40 mg/mL, and the whole column of well-permeable molecular imprinting was prepared, the highest imprinted factor was 11.83. In order to further illustrate the existence condition of the proton reagent, with ionic liquids as functional monomer can still showed very good imprinting effect, environmental pollutants triclosan and pesticide imidacloprid were used as template molecule respectively, molecularly imprinted materials of the environmental pollutants triclosan and pesticide imidacloprid also showed good effect of imprinting, molecularly imprinted materials combined with solid phase extraction technology, the optimization of solid phase extraction, methanol reagent for the samples, acetonitrile was as washing reagents, methanol was employedas elution reagent, and got the high purity of aesculetin (> 92%), and recovery of 80%。

Pages96
Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/5459
Collection资源化学研究室
Recommended Citation
GB/T 7714
贾曼. 基于分子拥挤效应的三种化合物的印迹聚合物的制备及应用研究[D]. 北京. 中国科学院大学,2018.
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