碳基纳米复合材料修饰电极的制备及其在药物分析中的应用

发布时间：2018-04-29 06:02

本文选题：纳米复合材料 + 修饰电极　；参考：《上海大学》2016年博士论文

【摘要】：药物分析是分析化学中的一个重要分支,随着药学的发展逐渐成为一门独立的学科。现代药物分析无论是分析领域,还是分析技术都己经大大拓展。电化学分析作为分析技术的一种,在药物分析领域中有着日益广泛的应用。而各种微电极、修饰电极、电化学传感器的问世,由于其具有灵敏度高、响应快、选择性好、操作简单等优点,为电化学分析在药物分析中的应用注入了新的活力。随着工作者对电化学分析的研究日益深入,电化学分析在科研、生产中的应用越来越广泛,并且在新药研发以及药品生产等方面扮演着重要的角色。本论文主要研究了新型碳基纳米材料复合修饰电极的制备,探索了不同药物在修饰电极上的电化学行为和电极反应机理,从而建立了一系列灵敏、简单、准确的药物定量分析方法。主要内容归纳如下:1、通过电化学方法将金属氧化物四氧化三钴(Co_3O_4)/石墨烯(GR)纳米材料电沉积在玻碳电极表面上,制备了一种新型的纳米复合电极(Co_3O_4/GR/GCE),成功地被用于测定异烟肼。通过扫描电镜对此修饰电极的表面形貌进行了表征,Co_3O_4纳米粒子和GR能够很好地修饰在玻碳电极表面。采用差分脉冲法(DPV)优化了异烟肼的测定条件,在最佳条件下,线性关系范围为0.5~160μM,最低检出限为0.17μM(S/N=3),实际药物和血清中的回收率良好,相对标准偏差均小于5%。该方法方便可行,结果满意,重复性好,实用性强。实验表明,相比于裸电极,此修饰电极获得了更好的电化学性能,可显著提高对异烟肼的电催化活性。2、在上述工作的基础上,以GR为基底,利用半胱氨酸氧化为磺基丙氨酸(Cysteic acid,CA)电化学反应及其在GR表面的吸附和聚合,制得石墨烯-磺基丙氨酸复合膜修饰玻碳电极(GR/CA/GCE),并应用于异烟肼含量的测定。在最佳条件下,线性关系范围扩大为0.1~200μM,最低检出限仅为0.03μM(S/N=3),具有很高的灵敏度和选择性。该方法用于药品中异烟肼的定量分析获得了满意的结果。3、运用一种温和而新颖的电化学技术制备了GR和纳米氧化锌(ZnO)复合物修饰电极(ZnO/GR/GCE)。实验表明,复合物修饰电极具有优异的电化学性能;与此同时,该复合物作为电极的增敏材料,氧氟沙星在该电极上的电催化性能得到了显著的提高。在最佳测定条件下,氧氟沙星的线性范围分1~100μM,对应的检测限和灵敏度分别为1.7μM和1399.86μA mM-1 cm-2。同时,该修饰电极在药品氧氟沙星的检测中表现出令人满意的应用结果。4、利用多壁碳纳米管(MWCNTs)的优良性能,构建了MWCNTs和维生素B12(VB12)复合膜修饰玻碳电极测定对羟基苯乙酮(p-Hyd)的电化学分析方法。傅里叶变换红外光谱和电化学阻抗谱实验表明,MWCNTs和VB12已经成功地修饰在玻碳电极表面。通过优化,选择pH 6.0的磷酸盐缓冲溶液、VB12电聚合15圈作为最佳优化条件,以方波伏安法检测p-Hyd。实验结果表明,与聚铬黑T修饰电极相比,p-Hyd的氧化电位负移了0.04 V,虽检测限没有改变,但在0.5~20μM和20~200μM范围内均有较好的线性关系。5、建立了聚铬黑T修饰玻碳电极方波伏安法测定p-Hyd的电化学方法。运用循环伏安法在含有0.5 mM铬黑T的0.1 M NaOH溶液中制备聚铬黑T膜,并使用扫描电镜、红外光谱、电化学阻抗等技术进行了表征。在优化的实验条件下,p-Hyd在0.91V(vs SCE)处的峰电流与其浓度在1~160μM范围内呈现良好的线性关系,检测限达到0.15μM(S/N=3),相对标准偏差小于2%。该方法简单易行,具有良好的重现性和稳定性。
[Abstract]:Drug analysis is an important branch of analytical chemistry. With the development of pharmacy, drug analysis has gradually become an independent subject. Modern drug analysis has been greatly expanded in both analytical and analytical techniques. As one of the analytical techniques, electrochemical analysis has been widely used in the domain of drug analysis. Because of its advantages of high sensitivity, quick response, good selectivity and simple operation, the electrochemical analysis has injected new vitality into the application of electrochemical analysis in the analysis of drugs. As the research of electrochemical analysis is deepening, the electrochemical analysis is becoming more and more widely used in scientific research and production. And it plays an important role in the research and development of new drugs and drug production. This paper mainly studies the preparation of a new carbon based nanocomposite modified electrode, and explores the electrochemical behavior and electrode reaction mechanism of different drugs on the modified electrode. Thus a sensitive, simple and accurate method for quantitative analysis of drugs is established. The main contents are summarized as follows: 1, a new type of nano composite electrode (Co_3O_4/GR/GCE) was prepared by electrodeposition of metal oxide four oxidation three cobalt (Co_3O_4) / graphene (GR) nanomaterials on the surface of glassy carbon electrode, which was successfully used for the determination of isoniazid. The Co_3O_4 nanoparticles and GR can be well modified on the surface of the glassy carbon electrode. The determination conditions of isoniazid are optimized by differential pulse (DPV). Under the optimum conditions, the linear range is 0.5~160 mu M, the minimum detection limit is 0.17 u M (S/N=3). The recovery rate in the actual drug and serum is good, and the relative standard deviation is less than 5%.. The method is convenient, satisfactory, reproducible and practical. The experiment shows that the electrochemical performance of the modified electrode is better than that of the bare electrode. The electrocatalytic activity of isoniazid can be improved significantly by.2. On the basis of the above work, GR is used as the base and the electrochemistry of Cysteic acid (CA) is oxidized by cysteine. The graphene sulfonyl alanine composite membrane modified glassy carbon electrode (GR/CA/GCE) was prepared by the study of the reaction and its adsorption and polymerization on the GR surface. It was applied to the determination of isoniazid content. Under the optimum conditions, the linear range was expanded to 0.1~200 mu M, the minimum detection limit was only 0.03 Mu M (S/N =3), with high sensitivity and selectivity. The method was used in this method. The quantitative analysis of isoniazid in the drug obtained a satisfactory result.3. GR and nano Zinc Oxide (ZnO) composite modified electrode (ZnO/GR/GCE) was prepared by a mild and novel electrochemical technique. The experiment showed that the composite modified electrode had excellent electrochemical performance. At the same time, the complex was used as an electrode sensitizing material, oxygen fluoride. The electrocatalytic performance of floxacin on this electrode has been greatly improved. Under the optimal determination conditions, the linear range of ofloxacin is 1~100 mu M, the corresponding detection limits and sensitivity are 1.7 mu M and 1399.86 A mM-1 cm-2. respectively. The modified electrode shows a satisfactory application result in the detection of ofloxacin, which is used for the use of.4. The excellent properties of multi wall carbon nanotube (MWCNTs) were obtained. The electrochemical analysis method of MWCNTs and vitamin B12 (VB12) composite membrane modified glassy carbon electrode for the determination of hydroxyacetophenone (p-Hyd) was constructed. The Fourier transform infrared spectroscopy and electrochemical impedance spectroscopy showed that MWCNTs and VB12 had been successfully modified on the surface of the glassy carbon electrode. The selection of pH by optimization was made. 6 phosphate buffer solution and VB12 electropolymerization 15 ring are the best optimization conditions. The test results of p-Hyd. test by square wave voltammetry show that the oxidation potential of p-Hyd is negatively shifted 0.04 V compared with the polychrome black T modified electrode. Although the detection limit is not changed, there is a good linear relationship between 0.5~20 mu M and 20~200 Muu enclosure, and the polychrome black T is established. The electrochemical method for the determination of p-Hyd by modified glassy carbon electrode by square wave voltammetry. The polychrome black T film was prepared by cyclic voltammetry in 0.1 M NaOH solution containing 0.5 mM chromium black T and characterized by scanning electron microscopy, infrared spectroscopy and electrochemical impedance techniques. The peak current and concentration of p-Hyd at 0.91V (vs SCE) at the optimum experimental conditions A good linear relationship is presented in the range of 1~160 mu M, the detection limit is 0.15 mu M (S/N=3), and the relative standard deviation is less than 2%.. The method is simple and easy, and has good reproducibility and stability.

【学位授予单位】：上海大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：O657.1;R917

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