纳米锆化合物修饰碳糊电极在药物分析中的应用

发布时间：2018-11-22 14:32

【摘要】：碳糊电极是一种利用碳粉与黏合剂所组成的碳糊,挤压进入电极管中,制备的新型电极,由于其残余电流小,制备简单,无毒,电极表面易于更新,使用寿命长等优点,在电分析化学中发挥着重要的作用。但目前来看,单纯的碳糊电极的应用比较有限,需要对其进行化学修饰,以提高其性能。本论文的工作主要是构筑灵敏的化学修饰碳糊电极伏安传感器,实现对药物小分子的灵敏准确、简便快速的测定。主要包括以下三个方面的内容:1.鉴于ZrO_2纳米粒子繁琐的制备过程,以及可以以ZrOCl_2为前驱体,通过电沉积的方式将ZrO_2沉积在电极表面,本实验将ZrOCl_2掺入碳糊电极中,对电极进行类似电沉积方法的电化学预处理后,电极表面的Zr OCl_2转化成了ZrO_2纳米粒子,得到电化学处理Zr OCl_2掺杂的碳糊电极,即ET-ZrOCl_2-CPE。利用扫描电镜(SEM)及电化学方法对该电极的表面形貌及电化学性能进行表征。该电极对中药活性成分黄豆苷元具有很好的响应,进而研究了黄豆苷元的反应过程,计算了相关的反应动力学参数,并建立了黄豆苷元的分析测定方法,线性范围为3.0×10-8~2.0×10-6 mol L-1。2.在第一个体系中,处理前后电极表面的纳米粒子的数量本该相同,但SEM表明,电化学处理之后,纳米粒子的数量有所减少。这说明处理过程中有部分ZrOCl_2或电化学处理产物脱落。为此,该体系在电极制备过程中引入能够起到吸附固定作用的β-环糊精(β-CD)。实验结果表明,与单独掺杂ZrOCl_2然后经电化学处理的电极相比,将β-CD与ZrOCl_2同时掺入电极中,经电化学处理后,纳米粒子数量有明显增加。利用该修饰电极系统的研究了中药活性成分川芎嗪的电化学反应机理,计算了动力学参数,并建立了分析测定方法。3.为了引入比表面积大且导电性好的石墨烯材料,同时增强ZrO_2纳米粒子在电极表面的稳定性,利用ZrO_2纳米粒子与含氧官能团之间的相互作用力,以及氧化石墨烯(GO)大的比表面积和丰富的含氧官能团,将GO作为ZrO_2纳米粒子生长的基体,以Zr OCl_2为前驱体,制备了ZrO_2/Gr复合材料。SEM表征可以看到,ZrO_2纳米粒子均匀地分散在Gr表面。该复合材料修饰的碳糊电极(ZrO_2/Gr-CPE)对药物曲克芦丁具有灵敏的响应,进而系统地研究了曲克芦丁的电极反应过程,并建立了灵敏的分析测定方法,线性范围为2.0×10-9~3.0×10-7mol L-1。
[Abstract]:Carbon paste electrode is a new type of electrode which is made up of carbon powder and binder and extruded into the electrode tube. Because of its small residual current, simple preparation, non-toxic, easy renewal of electrode surface, long service life, etc. It plays an important role in electroanalytical chemistry. However, the application of simple carbon paste electrode is limited, so it is necessary to modify it chemically to improve its performance. The main work of this paper is to construct a sensitive chemical modified carbon paste electrode voltammetry sensor to achieve sensitive, accurate, simple and rapid determination of small drug molecules. Mainly includes the following three aspects: 1. In view of the tedious preparation of ZrO_2 nanoparticles and the fact that ZrO_2 can be deposited on the electrode surface by electrodeposition with ZrOCl_2 as precursor, ZrOCl_2 was doped into the carbon paste electrode in this experiment. After electrochemical pretreatment of the electrode by similar electrodeposition method, the Zr OCl_2 on the electrode surface was converted into ZrO_2 nanoparticles, and the carbon paste electrode doped with Zr OCl_2 was obtained by electrochemical treatment, that is, ET-ZrOCl_2-CPE.. The surface morphology and electrochemical properties of the electrode were characterized by scanning electron microscope (SEM) (SEM) and electrochemical method. The electrode has a good response to daidzein, the reaction process of daidzein has been studied, the kinetic parameters of the reaction have been calculated, and a method for the determination of daidzein has been established. The linear range is 3.0 脳 10-8 mol L-1.2. In the first system, the number of nanoparticles on the electrode surface was supposed to be the same before and after treatment, but SEM showed that the number of nanoparticles decreased after electrochemical treatment. This indicates that some ZrOCl_2 or electrochemical products fall off during the treatment. Therefore, 尾 -cyclodextrin (尾-CD).) was introduced into the system during the preparation of the electrode. The experimental results show that compared with the electrode doped with ZrOCl_2 alone and then treated by electrochemical treatment, 尾-CD and ZrOCl_2 are doped into the electrode at the same time, and the number of nanoparticles increases obviously after electrochemical treatment. The electrochemical reaction mechanism of ligustrazine, an active component of traditional Chinese medicine, was studied by using the modified electrode system. The kinetic parameters were calculated and the analytical method was established. In order to introduce graphene materials with large specific surface area and good electrical conductivity, and to enhance the stability of ZrO_2 nanoparticles on the electrode surface, the interaction force between ZrO_2 nanoparticles and oxygen functional groups was used. The large specific surface area and abundant oxygen functional groups of graphene oxide (GO) were used to prepare ZrO_2/Gr composites by using GO as the matrix of ZrO_2 nanoparticles and Zr OCl_2 as precursor. ZrO_2 nanoparticles are uniformly dispersed on the surface of Gr. The composite modified carbon paste electrode (ZrO_2/Gr-CPE) was sensitive to the drug troxerutin, and the electrode reaction process of troxerutin was studied systematically, and a sensitive analytical method was established. The linear range is 2.0 脳 10 ~ (-9) 10-7mol L ~ (-1).
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.1;TQ460.72

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