多功能分离介质的合成和应用
发布时间：2018-07-21 16:32
【摘要】：分离科学是自然科学中很重要的一个研究方向。近年来,随着食品科学、生物医药、环境科学、化工生产等学科的快速发展,对这些行业中相关目标分析物的分离和纯化提出了更高的要求。基于此,各种分离纯化方法得到了快速发展。高效液相色谱法(High performance liquid chromatography, HPLC)作为经典的分离方法,是分离各类化合物的重要选择。而磁固相萃取(Magnetic solid phase extraction, MSPE)相较于传统固相萃取(Solid phase extraction, SPE),具有操作简单、快速高效等优点,近年来也得到了迅速发展。分离方法的核心是分离介质。为了提高分离介质的分离效果,新型分离介质的合成一直是分离科学中最有活力的工作。由于实际样品分析中样品的多样性和复杂性,新型分离介质的设计必须结合实际样品分离分析的需要,所合成的分离介质除了对目标分析物要有很好的选择性之外,还要具有优秀的稳定性、重现性以及实际可操作性。除此之外,新型分离介质的合成要尽可能操作简单,制备周期短,以及经济环保。鉴于此,本论文开发了多种新的分离介质合成方法,所提出的合成方法操作简单实用、普适性高、重现性好。基于所开发的合成方法制备了一系列新型分离介质,包括一种混合模式硅胶基质填充柱,两种混合模式毛细管整体柱,以及两种磁分离材料,并将这些新型分离介质应用于不同类别分析物的分离,取得了很好的效果。具体内容如下所示：一、将RAFT/click chemistry串联接枝法应用于聚合物接枝色谱固定相的合成,基于此方法合成了一种内嵌酰胺基聚苯乙烯接枝的反相弱阴离子交换(Reverse phase/weak anionic exchange chromatography, RP/WAX)硅胶固定相,所制固定相展现出很好的硅羟基屏蔽效果,在纯水做流动相时稳定性良好。二、将双键改性POM作为新的功能单体,利用共聚法制备了一种新的POM修饰聚合物整体柱。加入POM后制备的整体柱具有强阳离子交换性质,柱效和渗透性得到了明显的提升,对于极性带电化合物展现出很好的分离效果。三、开发了一种新的“一锅法”用来制备混合模式有机-硅胶杂化整体柱。基于此方法,我们制备了一种键合有辛基和膦酸基的反相阳离子交换(Reverse phase/cationic exchange chromatography, RP/CEC)有机-硅胶杂化整体柱。以此整体柱为分离柱构建了纳升液相色谱-质谱联用(Nanoliter-liquid chromatography-mass spectrometry, nano-LC-MS)平台,结合移液枪头固相萃取(Pipette tip-solid phase extraction, PT-SPE)与衍生化方法,对5 mg水稻叶片中的内源性赤霉素进行了定量分析。四、成功的在纳米Fe3O4表面固载纳米线结构的钛-甘油(Titanium-glycerol, TiGly)复合物或锆-甘油复合物(Zirconium-glycerol, ZrGly),所合成的Fe3O4@TiGly和Fe3O4@ZrGly形貌均一,比表面明显提高。在MSPE模式下,将这两种材料应用于生物体液中核糖核苷和磷酸化多肽的萃取。结果表明Fe3O4@ZrGly对核糖核苷具有更好的富集纯化效果,而Fe3O4@TiGly对磷酸化多肽具有更好的富集纯化效果。
[Abstract]:Separation science is a very important research direction in natural science. In recent years, with the rapid development of food science, biological medicine, environmental science, chemical production and other disciplines, the separation and purification of related target analytes in these industries is higher. Based on this, various separation and purification methods have been developed rapidly. High performance liquid chromatography (HPLC), as a classic separation method, is an important choice for the separation of all kinds of compounds. The magnetic solid phase extraction (Magnetic solid phase extraction, MSPE) has the advantages of simple operation, fast efficiency and so on. In recent years, the phase of Magnetic solid phase extraction (MSPE) has the advantages of simple operation, rapid and efficient. The core of the separation method is the separation medium. In order to improve the separation effect of the separation medium, the synthesis of the new separation medium has been the most active work in the separation science. Because of the diversity and complexity of the samples in the actual sample analysis, the design of the new separation medium must be combined with the needs of the actual sample separation and analysis. In addition to the excellent stability, reproducibility and practical maneuverability of the synthesized separation medium, in addition to the good selectivity of the target analyte, the synthesis of the new separation medium should be simply operated, the preparation period is short, and the economic ring is guaranteed. In view of this, this paper has developed a variety of new separation media. The synthetic method is simple and practical, high universality and good reproducibility. A series of new separation mediums are prepared based on the synthetic method developed, including a mixed mode silica gel matrix filling column, two mixed mode capillary monolithic columns, and two magnetic separation materials, and the new separation medium is applied to the new separation medium. The separation of different types of analytes has achieved good results. The specific contents are as follows: first, the RAFT/click Chemistry Series grafting method is applied to the synthesis of polymer graft chromatography stationary phase, and a kind of Reverse phase/weak anionic exchang graft with embedded amidyl polystyrene (phase/weak anionic exchang) is synthesized by this method. E chromatography, RP/WAX) silica gel fixed phase, the fixed phase showed a good silicon hydroxyl shielding effect, in pure water as a mobile phase stability. Two, the double bond modified POM as a new functional monomer, the use of copolymerization to prepare a new POM modified polymer monolithic column. The whole column after the addition of POM has strong cation exchange. A new kind of "one pot method" was developed for the preparation of mixed mode organic silica hybrid monolithic column. Based on this method, a kind of reverse phase cation exchange (Revers) bonded with octyl and phosphonic acid (Revers) was prepared. E phase/cationic exchange chromatography, RP/CEC) organic silica gel hybrid monolithic column. A Nanoliter-liquid chromatography-mass spectrometry (nano-LC-MS) platform was constructed by using the monolithic column as separation column, and the solid phase extraction (Pipette tip-solid phase) and derivatization were combined with the pipette. The quantitative analysis of endogenous gibberellin in 5 mg rice leaves was made. Four, successfully loaded nanowires on the surface of nanoscale Fe3O4 (Titanium-glycerol, TiGly) complex or zirconium glycerol complex (Zirconium-glycerol, ZrGly), the morphology of the synthesized Fe3O4@TiGly and Fe3O4@ZrGly was homogeneous, and the surface was significantly higher than that of the surface. In MSPE model, these two kinds of materials were applied to the extraction of ribonucleoside and phosphorylated polypeptide in biological fluid. The results showed that Fe3O4@ZrGly had better enrichment and purification effect on ribonucleoside, while Fe3O4@TiGly had better enrichment and purification effect on phosphorylated polypeptide.
【学位授予单位】：武汉大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TQ028
[Abstract]:Separation science is a very important research direction in natural science. In recent years, with the rapid development of food science, biological medicine, environmental science, chemical production and other disciplines, the separation and purification of related target analytes in these industries is higher. Based on this, various separation and purification methods have been developed rapidly. High performance liquid chromatography (HPLC), as a classic separation method, is an important choice for the separation of all kinds of compounds. The magnetic solid phase extraction (Magnetic solid phase extraction, MSPE) has the advantages of simple operation, fast efficiency and so on. In recent years, the phase of Magnetic solid phase extraction (MSPE) has the advantages of simple operation, rapid and efficient. The core of the separation method is the separation medium. In order to improve the separation effect of the separation medium, the synthesis of the new separation medium has been the most active work in the separation science. Because of the diversity and complexity of the samples in the actual sample analysis, the design of the new separation medium must be combined with the needs of the actual sample separation and analysis. In addition to the excellent stability, reproducibility and practical maneuverability of the synthesized separation medium, in addition to the good selectivity of the target analyte, the synthesis of the new separation medium should be simply operated, the preparation period is short, and the economic ring is guaranteed. In view of this, this paper has developed a variety of new separation media. The synthetic method is simple and practical, high universality and good reproducibility. A series of new separation mediums are prepared based on the synthetic method developed, including a mixed mode silica gel matrix filling column, two mixed mode capillary monolithic columns, and two magnetic separation materials, and the new separation medium is applied to the new separation medium. The separation of different types of analytes has achieved good results. The specific contents are as follows: first, the RAFT/click Chemistry Series grafting method is applied to the synthesis of polymer graft chromatography stationary phase, and a kind of Reverse phase/weak anionic exchang graft with embedded amidyl polystyrene (phase/weak anionic exchang) is synthesized by this method. E chromatography, RP/WAX) silica gel fixed phase, the fixed phase showed a good silicon hydroxyl shielding effect, in pure water as a mobile phase stability. Two, the double bond modified POM as a new functional monomer, the use of copolymerization to prepare a new POM modified polymer monolithic column. The whole column after the addition of POM has strong cation exchange. A new kind of "one pot method" was developed for the preparation of mixed mode organic silica hybrid monolithic column. Based on this method, a kind of reverse phase cation exchange (Revers) bonded with octyl and phosphonic acid (Revers) was prepared. E phase/cationic exchange chromatography, RP/CEC) organic silica gel hybrid monolithic column. A Nanoliter-liquid chromatography-mass spectrometry (nano-LC-MS) platform was constructed by using the monolithic column as separation column, and the solid phase extraction (Pipette tip-solid phase) and derivatization were combined with the pipette. The quantitative analysis of endogenous gibberellin in 5 mg rice leaves was made. Four, successfully loaded nanowires on the surface of nanoscale Fe3O4 (Titanium-glycerol, TiGly) complex or zirconium glycerol complex (Zirconium-glycerol, ZrGly), the morphology of the synthesized Fe3O4@TiGly and Fe3O4@ZrGly was homogeneous, and the surface was significantly higher than that of the surface. In MSPE model, these two kinds of materials were applied to the extraction of ribonucleoside and phosphorylated polypeptide in biological fluid. The results showed that Fe3O4@ZrGly had better enrichment and purification effect on ribonucleoside, while Fe3O4@TiGly had better enrichment and purification effect on phosphorylated polypeptide.
【学位授予单位】：武汉大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TQ028
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