富勒烯衍生物的制备及其在毛细管电泳中的应用

发布时间：2018-08-05 13:23

【摘要】：上世纪80年代富勒烯作为碳的第三种同素异形体被发现,富勒烯分子具有独特的球状结构,类似足球,又被称为足球烯,因其独特的球形结构以及迷人物理化学性质,在材料科学、分析科学和生物医药等领域被广泛的研究。金属富勒烯作为富勒烯家族中的一员,因在碳笼内嵌入金属而具有不同于空心富勒烯的独特的性质,有关金属富勒烯的制备、功能化修饰仍是目前富勒烯研究的热点。本论文主要由三个工作组成：1、通过直流电弧法合成了含钇的内嵌金属富勒烯,使用N,N-二甲基甲酰胺选择性提取金属富勒烯,通过多步的HPLC分离,结合质谱及高效液相色谱对得到的金属富勒烯的纯度进行分析,得到高纯度的Y@C82的两种异构体,通过vir-NIR吸收光谱表征对碳笼对称性进行研究,并结合已报道的文献,初步判断为C2v和Cs两种异构体,其中Cs异构体目前尚未有报道。2、为了探究Y@Cs2中从未报道过的异构体的化学性质,将分纯的Y@Cs-C82与溴代丙二酸二乙酯进行Bingel-Hirsch反应,并对产物分纯后进行了质谱和可见光-近红外光谱的表征,最后通过单晶XRD确定了其中一个单加成产物的结构。本实验对研究Y@C82的结构及化学性质有重要意义。3、使用电弧法制备富勒烯(C60),并进行羧基衍生化得到水溶性富勒烯(C60CH-COOH)。然后以水溶性感光材料重氮树脂(DR)为连接试剂,利用层层自组装(LBL)技术,制备了DR/C60CH-COOH共价毛细管涂层柱,然后进行蛋白质毛细管电泳分离,成功实现了4种蛋白质的基线分离,且重现性和稳定性很好。本论文对钇金属富勒烯进行了制备、分离以及化学性质等方面的研究,实验结果发现钇金属的嵌入使得Y@C82的碳笼上碳原子的反应活性大大提高,本论文首次探究了Y@Cs-C82富勒烯的化学性质,并得到了其中一个单加成产物的结构,这对深入研究单金属富勒烯的化学活性、设计和合成新型功能分子都具有积极意义。本论文同时将功能化的碳材料C60CH-COOH修饰在毛细管内壁,利用C60独特的球状结构,有效的降低了蛋白质与毛细管内壁硅羟基的接触,同时增加涂层的润滑能力,有效的提高了蛋白质的分离效率,缩短分离时间。
[Abstract]:Fullerene was found in 80s in the last century as third homoisoforms of carbon. Fullerenes have a unique spherical structure, similar to football, and also known as football enes. Because of their unique spherical structure and attractive physical and chemical properties, the fullerenes have been widely studied in the fields of material science, analytical science and biological medicine. As a member of the fullerenes family, which is different from hollow fullerenes in carbon cage, the preparation and functional modification of metal fullerenes are still the focus of fullerene research. This paper consists of three tasks: 1, the embedded metal fullerenes containing yttrium are synthesized by direct current arc method. The metal fullerenes were selectively extracted with N, N- two methyl formamide, and the purity of the metal fullerenes was analyzed by multistep HPLC separation, mass spectrometry and high performance liquid chromatography, and two isomers of high purity Y@C82 were obtained. The symmetry of carbon cages was studied by vir-NIR absorption spectrum, and the reported literature was combined. The step is determined by two isomers of C2v and Cs, of which Cs isomers have not yet reported.2. In order to explore the chemical properties of the isomers that have never been reported in Y@Cs2, the pure Y@Cs-C82 and two ethyl bromide diacid are reacted with Bingel-Hirsch, and the properties of the products are characterized by the mass spectrum and the visible light near infrared spectroscopy. The single crystal XRD determines the structure of one of the single addition products. This experiment is important for the study of the structure and chemical properties of Y@C82,.3, the arc method is used to prepare fullerenes (C60), and the carboxyl derivatization is used to obtain water-soluble fullerenes (C60CH-COOH). Then the water-soluble photoreceptor diazonium resin (DR) is used as the connecting reagent and the layer self group is used. (LBL) technology, DR/C60CH-COOH covalent capillary coating column was prepared, then protein capillary electrophoresis was separated. The baseline separation of 4 kinds of proteins was successfully realized and the reproducibility and stability were very good. The preparation, separation and chemical properties of yttrium metal fullerenes were studied in this paper. The experimental results found yttrium metal The reaction activity of carbon atoms on the carbon cage of Y@C82 is greatly enhanced. The chemical properties of Y@Cs-C82 fullerenes are first explored in this paper, and the structure of one of the single addition products is obtained. This is of positive significance to the deep study of the chemical activity of the Monal fullerene, the design and synthesis of new functional molecules. The functionalized carbon material C60CH-COOH is modified on the inner wall of the capillary and uses the unique spherical structure of C60 to effectively reduce the contact between the protein and the silicon hydroxyl group on the inner wall of the capillary, and increase the lubricating ability of the coating, effectively improving the separation efficiency of the protein and shortening the separation time.
【学位授予单位】：青岛大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O613.71;O658.9

【相似文献】