原子层沉积法制备硅胶基质分离载体及其应用

发布时间：2018-05-11 03:12

本文选题：原子层沉积法 + 强阳离子交换　；参考：《天津大学》2010年硕士论文

【摘要】：硅胶基质分离载体具有机械强度好,孔结构和表面积易于人为控制,较好的化学稳定性和热稳定性,表面具有足够的可反应硅羟基等优点,因此成为各种分离载体的理想基质材料,目前硅胶基质分离载体已经被广泛用于色谱、催化和环境科学等领域。硅胶表面修饰的方法主要有液相反应法、自组装法、超临界流体反应法和原子层沉积法。与其他方法相比,原子层沉积法避免了价格昂贵且污染环境的有机溶剂或超临界流体等反应介质的使用,同时具有反应耗时短,易于扩大生产及有机功能基团键合量高等优势。为硅胶基质分离载体的生产开辟了一条节能降耗,环境友好的绿色途径。本论文从硅胶基质的表面修饰出发,通过原子层沉积法,制备了苯基键合硅胶,环氧丙基键合硅胶,并在此基础上制备了强阳离子交换色谱填料、新型限进介质固相萃取剂。论文主要内容如下: 以多孔球形硅胶为基质,通过原子层沉积法,制备了苯基键合硅胶,并通过磺化得到苯磺酸基键合硅胶,用于原料乳中三聚氰胺的快速检测,针对常规丙磺酸基键合硅胶不能实现杂质峰和三聚氰胺峰基线分离,从而严重影响三聚氰胺定量检测的弊端,本课题自主开发的苯磺酸基键合硅胶实现了二者的有效分离,而且与液相反应法相比,原子层沉积法制备的苯磺酸基键合硅胶由于苯磺酸基键合量高,三聚氰胺保留时间更长,杂质峰和三聚氰胺峰分离度更大,体现了原子层沉积法制备化学键合型硅胶填料的优势。以多孔球形硅胶为基质,通过原子层沉积法,制备环氧丙基键合多孔硅胶,并在此基础上首次制备了一种孔内键合间氨基苯硼酸,孔外键合二醇基的新型限进介质固相萃取剂,这种材料合适的孔径保证了蛋白质等生物大分子不能进入孔内,且表面亲水性的二醇基保证了生物大分子在吸附剂的外表面不会发生不可逆的变性和吸附。同时,孔内键合的间氨基苯硼酸能特异性的吸附顺式二羟基化合物。以牛血清白蛋白作为蛋白质模型,以三种儿茶酚胺类药物作为顺式二羟基化合物模型,通过系统实验验证了这种新型限进介质固相萃取剂的限进性能和对顺式二羟基化合物的特异性吸附性能。在此基础上,以Fe_3O_4-SiO_2复合磁性微球为基质,首次制备了新型磁性限进介质固相萃取剂。该材料既具有限进介质固相萃取剂的优点,又具有磁性材料操作简便,易于自动化,可靶向控制的优点。从而提高了效率,创新了固相萃取的操作模式,为生物样品中小分子化合物的固相萃取开辟了一条高效快捷的途径。
[Abstract]:The silica gel matrix carrier has the advantages of good mechanical strength, easy artificial control of pore structure and surface area, better chemical stability and thermal stability, and sufficient reactivity of silica hydroxyl group on the surface. Therefore, silica gel matrix has been widely used in chromatography, catalysis and environmental science. The methods of surface modification of silica gel mainly include liquid phase reaction method, self-assembly method, supercritical fluid reaction method and atomic layer deposition method. Compared with other methods, the atomic layer deposition method avoids the use of expensive and polluting organic solvents or supercritical fluids, and has the advantages of short reaction time, easy to expand production and high bond quantity of organic functional groups. It opens up a green way of energy saving and environment friendly for the production of silica gel matrix separation carrier. In this paper, phenyl bonded silica gel and epoxy propyl bonded silica gel were prepared by atomic layer deposition from the surface modification of silica gel matrix. On this basis, strong cationic exchange chromatographic fillers and a new type of solid phase extractant with restricted medium were prepared. The main contents of the thesis are as follows: Phenyl-bonded silica gel was prepared by atomic layer deposition with porous spherical silica gel as the matrix. Benzene sulfonic acid bonded silica gel was obtained by sulfonation, which was used for rapid detection of melamine in raw milk. In view of the fact that the baseline separation of impurity peak and melamine peak can not be realized by conventional propyl sulfonic acid bonded silica gel, which seriously affects the quantitative detection of melamine, the self-developed benzenesulfonic acid bonded silica gel has realized the effective separation of the two compounds. Compared with the liquid phase reaction method, the benzene sulfonic acid bonded silica gel prepared by atomic layer deposition method has longer retention time and greater separation degree between the impurity peak and the melamine peak due to the higher binding amount of benzene sulfonic acid group. The advantage of preparing chemically bonded silica gel filler by atomic layer deposition is demonstrated. Epoxy propyl bonded porous silica gel was prepared by atomic layer deposition with porous spherical silica gel as the matrix. A new type of solid-phase extractant was prepared for the first time, in which m-aminophenoboric acid was bonded intrapore and diol group was bonded outside the pore. The suitable pore size of this material ensures that protein and other biological macromolecules cannot enter the pore, and the hydrophilic diol group on the surface ensures that there will not be irreversible denaturation and adsorption of the biomolecules on the external surface of the adsorbent. At the same time, I-aminophenoboric acid can specifically adsorb cis-dihydroxyl compounds. Bovine serum albumin (BSA) was used as protein model and catecholamines as cis-dihydroxyl compound model. The limited performance and the specific adsorption of cis-dihydroxyl compounds were verified by systematic experiments. On this basis, a new magnetic limiting medium solid phase extractant was prepared by using Fe_3O_4-SiO_2 composite magnetic microspheres as the matrix for the first time. The material not only has the advantages of solid phase extractant, but also has the advantages of simple operation, easy automation and target control of magnetic material. Thus, the efficiency is improved, the operation mode of solid phase extraction is innovated, and a high efficient and fast way is opened up for the solid phase extraction of small molecular compounds in biological samples.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2010
【分类号】：O657.7

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