非水毛细管电泳—电化学发光检测在药物分析中的应用研究

发布时间：2018-06-15 20:42

本文选题：非水毛细管电泳 + 电化学发光　；参考：《郑州大学》2014年硕士论文

【摘要】：非水毛细管电泳(NACE)是指在有机溶剂中进行的电泳操作，与水相毛细管电泳(CE)相比，电泳电流低，样品处理简单，与电化学检测器兼容性更好。NACE能够用来分离在水相中不能分离的中性物质、难溶于水的物质以及在水中不稳定的物质。电化学发光(ECL)是指通过施加电压，电极表面的物质发生反应，产生电子转移，产生发光的现象。其中，三联吡啶钌发光试剂不论在水相还是有机相中都具有溶解性好、性质稳定、发光试剂可循环利用等优点，在电化学发光（ECL）中的应用最广泛。本文将NACE与ECL检测相联用，检测含三级胺结构的药物： 1、合成高氯酸根型Ru(bpy)3(ClO4)2发光试剂替代传统的氯离子型Ru(bpy)3Cl2发光试剂，并其应用于NACE-ECL技术中，克服氯离子对发光信号的干扰，得到非常强的ECL信号，我们用三丙胺(TPrA)来表征乙腈相中Ru(bpy)3(ClO4)2的静态ECL信号。当加入1mM TPrA后，ECL信号明显增强，大约为不加时信号的400倍。实验中使用有机溶剂替代水溶液，Pt工作电极表面不容易产生氧化膜，无需活化处理，ECL信号的重现性非常好。将此发光试剂应用于毛细管电泳柱端检测中，对于提高分析物的检测效果具有潜在的应用价值。 2、利用NACE-ECL联用检测技术分析检测TPrA。研究发现：在5×10-9~1×10-5mol/L范围内ECL信号与TPrA浓度呈良好的线性关系，相关系数r=0.9992，最低检测限为5×10-9mol/L。由于可以施加了分离电压和使用短的毛细管柱（33cm），此方法可实现对TPrA快速分析检测。 3、将NACE-ECL联用技术应用于琥珀酸多西拉敏、马来酸非尼拉敏及其混合物的分析检测，同时考察分离溶剂对这两种药物的分离效果。结果发现，当混合溶剂DMF:ACN体积为40:60时，分离效果最好。本文使用EC法在玻碳电极(GC)表面沉积不同的形态的Cu2O晶体，，有超级八面体、八面体和微球体结构。将微球结构的Cu2O-GC应用于葡萄糖传感器中，表现出良好的电催化性能。
[Abstract]:Non-aqueous capillary electrophoresis (NACE) refers to electrophoretic operation in organic solvents. Compared with aqueous capillary electrophoresis (CEE), the electrophoretic current is lower and sample handling is simple. NACE can be used to separate neutral, insoluble and unstable substances in water. Electrochemiluminescence (ECL) refers to the phenomenon of electron transfer and luminescence by applying voltage to the material on the electrode surface. Among them, tripyridine ruthenium luminescence reagents have many advantages, such as good solubility, stable properties and recycling of luminescence reagents, both in aqueous and organic phases, so they are widely used in electrochemical luminescence (ECL). In this paper, NACE was combined with ECL to detect drugs with tertiary amine structure. 1. The synthesis of perchlorate type RubpyN 3CIO 4 O 4 O 2 luminescent reagent instead of the traditional chlorine ion type RubpyN 3Cl 2 luminescent reagent was applied in NACE-ECL technology. A very strong ECL signal was obtained by overcoming the interference of chloride ions to the luminescent signal. The static ECL signal of RunbpyN _ 3CIO _ 4N _ 2 in acetonitrile phase was characterized by tripropylamine (TPRA). When 1 mm TPrA was added, the ECL signal was obviously enhanced, which was about 400 times of that of the undelayed signal. In the experiment, it is not easy to produce oxide film on the surface of Pt electrode by using organic solvent instead of aqueous solution, and the reproducibility of ECL signal without activation is very good. The application of the luminescent reagent in capillary electrophoresis column end detection has potential application value for improving the detection effect of the analyte. 2. The detection of TPrA by NACE-ECL is carried out by using NACE-ECL. It is found that there is a good linear relationship between ECL signal and TPRA concentration in the range of 5 脳 10 ~ (-9) mol / L ~ (-1) 脳 10 ~ (-5) mol / L, the correlation coefficient is 0.9992, and the detection limit is 5 脳 10 ~ (-9) mol / L. Because the separation voltage can be applied and a short capillary column can be used to detect TPrA, this method can be used for the rapid analysis and detection of TPrA. 3. The NACE-ECL technique was applied to the analysis and detection of doxillamine succinate, fenilamine maleate and its mixture. At the same time, the separation effect of separation solvent on these two drugs was investigated. The results show that the separation efficiency is the best when the volume of DMF: ACN is 40:60. In this paper, different forms of Cu2O crystals have been deposited on the surface of glassy carbon electrode (GC) by EC method, with super octahedron, octahedron and microsphere structure. Cu2O-GC with microsphere structure was applied to glucose sensor and showed good electrocatalytic performance.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R917

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