聚多巴胺类涂层毛细管的制备及其在毛细管电色谱手性分离中的应用

发布时间：2018-03-26 06:05

本文选题：开管毛细管电色谱　切入点：多巴胺　出处：《兰州大学》2017年硕士论文

【摘要】：手性是自然界的本质属性之一,手性化合物的分离一直是分离领域的一个研究热点和难点。近年来,聚多巴胺(Polydopamine,PDA)由于具有独特的物理粘附性、亲水性、稳定性及良好的生物相容性,已在分离科学领域特别是毛细管电泳中的应用引起了研究者的广泛关注。鉴于此,本学位论文在前人工作的基础上,围绕以新型聚多巴胺类物质为开管毛细管电色谱(Open Tubular Capillary Electrochromatography,OT-CEC)柱的涂层材料在手性分离中的应用,开展了以下创新性研究工作:1.在室温下,首次原位制备了β-环糊精和聚多巴胺复合材料(β-CD/PDA)涂层的开管毛细管柱,并以其为OT-CEC分离通道,实现了七对手性化合物的分离。2.在室温下,首次以CuSO_4/H_2O_2作为引发剂将聚左旋多巴胺(poly-(L-DOPA))通过物理沉积和吸附的方式成功地修饰在毛细管内壁上,制备了新型涂层毛细管柱。利用该涂层毛细管实现了十对手性化合物的分离。3.首次制备了L-组氨酸@聚左旋多巴胺(L-His/poly-(L-DOPA))涂层的开管毛细管柱,并考察了此柱对手性化合物的分离能力。本论文共分为四章:第一章简要介绍了近年来不同涂层技术在开管毛细管电色谱手性分离中的应用。第二章在室温下,首次通过聚多巴胺的粘附性质原位快速制备了β-CD/PDA涂层毛细管。利用扫描电子显微镜(SEM)、傅立叶红外光谱(FT-IR)、流动电势(SPs)、电渗流等对涂层毛细管进行了表征,表明β-CD/PDA被成功地修饰在毛细管内壁上。详细考察了背景电解质的种类、浓度和pH、有机添加剂、β-CD和多巴胺的用量以及聚合时间等对手性分离的影响。结果表明,当以β-CD和多巴胺的用量均为5.0 mg/mL、聚合时间为1.0 h时获得的涂层毛细管为分离通道时,可实现对特布他林、卡维地洛、维拉帕米、肾上腺素、去甲肾上腺素、异丙肾上腺素和色氨酸等对映异构体的分离。第三章在室温下,首次以CuSO_4(5 mM)/H_2O_2(19.6 mM)作为引发剂,原位快速制备了聚左旋多巴(poly-(L-DOPA))涂层毛细管,并将其作为分离通道用于对映异构体的分离。CuSO_4/H_2O_2可催化产生活性氧,从而加快左旋多巴的聚合和沉积。我们先用离线实验验证了用此方法制备poly-(L-DOPA)涂层毛细管的可行性,并用SEM、FI-IR、流动电势和电渗流对涂层毛细管进行了表征。进而,以三种手性胺类药物、三种胺类神经递质、四种氨基酸对映体为模型分析物,详细地考察了实验条件包括聚合时间等对涂层毛细管分离性能的影响。此涂层柱具有良好的稳定性和重现性,可连续使用250次而不引起分离效率的改变。第四章在第三章工作的基础上,首先原位制备了poly-(L-DOPA)涂覆的开口毛细管,再进一步将L-组氨酸修饰在毛细管内壁上,并考察了该涂层柱在手性分离中的应用。结果表明,L-组氨酸与poly-(L-DOPA)作为手性选择剂的协同作用,导致L-His/poly-(L-DOPA)涂层毛细管柱对色氨酸和卡维地洛对映体具有良好的手性分离效果。
[Abstract]:Chirality is one of the essential properties of nature. The separation of chiral compounds has been a hot and difficult point in the field of separation. In recent years, polydopamine polydopamine (PDAA) has been hydrophilic due to its unique physical adhesion. Stability and good biocompatibility have attracted wide attention in the field of separation science, especially in capillary electrophoresis. Based on the application of a novel polydopamine coating material used in chiral separation on Open Tubular Capillary ElectrochromatographyCcolumn, the following innovative research work was carried out at room temperature. The open tube capillary column of 尾 -cyclodextrin and polydopamine composite (尾 -CD / PDA) coating was prepared in situ for the first time and used as the OT-CEC separation channel to achieve the separation of seven chiral compounds at room temperature. Poly (L-DOPA) was successfully modified on the inner wall of capillary by physical deposition and adsorption with CuSO_4/H_2O_2 as initiator for the first time. A novel coated capillary column was prepared. The separation of ten chiral compounds was achieved by using the coated capillary column. For the first time, an open-tube capillary column with Lhistidine @ poly-L-histidine @ poly-L-DOPAP coating was prepared. The separation ability of chiral compounds on this column was also investigated. This thesis is divided into four chapters: chapter 1 briefly introduces the application of different coating techniques in chiral separation by capillary electrochromatography at room temperature in recent years, the second chapter is about the separation of chiral compounds by capillary electrochromatography at room temperature. The 尾 -CD-P / PDA coated capillary tubes were prepared by the adhesion properties of polydopamine for the first time. The coated capillaries were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), flow potential (FEP) and electroosmotic flow (EOF). The results showed that 尾 -CD / P PDA was successfully modified on the inner wall of capillary tube. The effects of background electrolytes, concentration and pH, organic additives, amounts of 尾 -CD and dopamine, and polymerization time on chiral separation were investigated in detail. When the amount of 尾 -CD and dopamine were 5.0 mg / mL and the coated capillary tubes obtained at 1.0 h were used as separation channels, p-terbutaline, carvedilol, verapamil, epinephrine and norepinephrine could be achieved. Separation of enantiomers such as isoproterenol and tryptophan. In chapter 3, CuSO_4(5 mM)/H_2O_2(19.6 mm was used as initiator for the first time in situ to prepare poly-L-DOPA-coated capillary tubes. It is used as a separation channel for separation of enantiomers. CuSOs 4 / H _ 2O _ 2 can catalyze the production of reactive oxygen species, thus accelerating the polymerization and deposition of levodopa. The coated capillary was characterized by SEMFI-IRI, flow potential and electroosmotic flow. Further, three chiral amines, three amine neurotransmitters and four amino acid enantiomers were used as model analytes. The effects of experimental conditions, including polymerization time, on the capillary separation performance of the coating were investigated in detail. The coating column has good stability and reproducibility. In chapter 4, on the basis of the work in chapter 3, the poly-L-DOPA-coated open capillary tube was prepared in situ, and the L-histidine was further modified on the inner wall of the capillary. The application of the coated column in chiral separation was also investigated. The results showed that the synergistic effect of L-histidine and poly-L-DOPA as chiral selector resulted in a good chiral separation of tryptophan and carvedilol on L-His-p-poly-L-DOPA-coated capillary column.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O652.6

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