纳米金属杂合碳材料电化学传感器的研制及其在中药分析中的应用研究

发布时间：2018-03-05 22:10

本文选题：碳纳米材料　切入点：电化学传感器　出处：《广东药科大学》2017年硕士论文　论文类型：学位论文

【摘要】：化学修饰电极(Chemically Modified Electrodes,CMEs)作为电化学传感的基础,是当前电化学、电分析化学方面十分最活跃的研究领域。自问世以来,已经成为药物分析领域中的一个重要的研究方向。在分析应用中,CMEs具有以下优点:(1)在电极表面上可根据需要修饰特定的功能基团,制得一系列不同类型和特殊功能的修饰电极;(2)基底电极材料可为金属、非金属、有机物,也可以是导体、半导体,为开拓新的电分析化学方法提供基础;(3)根据电极修饰的功能基团不同,修饰电极对溶液中存在的物质具有选择性响应;(4)修饰电极能增强电极反应的可逆性,为电极过程动力学的研究开辟新的途径;(5)修饰电极的灵敏度与裸电极相比要大得多,为痕量分析的进一步发展提供有力的手段。基于上述优点,CMEs在许多领域都具有广阔的应用前景。针对碳纳米管和石墨烯拥有高的比表面积、独特的空间结构、易于功能化和修饰等特点,以及纳米金属材料具有增强电子传递速率的特点,二者对电化学效应均有促进的作用。本研究构建了三种纳米金属杂合碳纳米材料修饰的电化学传感器,应用于中药成分分析。论文的内容主要分为以下三个部分:1.延胡索乙素在纳米镍杂合磺酸化石墨烯修饰的玻碳电极上的电化学行为及分析应用。实验制备了纳米金属镍/磺酸化石墨烯修饰的玻碳电极(NiNPs/SGS/GCE)。通过扫描电镜、能谱分析以及光电子能谱对修饰电极表面和金属性质进行表征,并用该修饰电极对延胡索乙素(Tetrahydropalmatine,THP)的电化学行为进行研究分析。研究表明磺酸化石墨对THP有良好的电化学效应,并且纳米镍能够进一步增强THP的氧化峰电流,促进其在修饰电极表面的电子转移效率。在最佳条件下THP氧化峰电流与浓度在5.0×10-7~2.0×10-5 mol/L呈线良好的线性关系,线性系数r为0.9988,检出限LOD(S/N=3)达到1.7×10-7 mol/L。该修饰电极成功应用在元胡止痛胶囊中THP的测定。2.芒果苷和淫羊藿苷在纳米金银合金-碳纳米管磺酸化石墨烯修饰玻碳电极上的电化学行为及其应用。实验通过滴涂的方法将碳纳米管磺酸化石墨烯混合分散液(MWNTs-SGSs)和金银纳米合金(Au-AgNPs)先后修饰在玻碳电极(GCE)表面,研制出了新电极。修饰电极结合了石墨烯的平面二维结构,碳纳米管的管状立体结构和纳米金属的的特殊电化学效应,不仅增加了修饰电极的有效表面积,也增强了电极表面的电子传递速率,可实现芒果苷(MIN)和淫羊藿苷(IIN)的同时分析。实验中通过扫描电子显微镜、红外对修饰电极的表面形态进行研究表征,用循环伏安法(CV)、差示脉冲伏安法(DPV)、计时库仑对MIN和IIN在修饰电极上的电化学行为进行考察。研究发现,Au-AgNPs/MWNTs-SGSs/GCE对MIN和IIN的电化学行为表现出优异的选择性和催化性。通过循环伏安法对修饰量,pH,扫描速率等条件进行优化,在最佳条件下循环伏安峰电位分别在0.56 V和0.95 V,MIN和IIN的氧化峰电流与浓度的线性范围分别是5.0×10-8~5.0×10-4 mol/L和5.0×10-8~1.0×10-4 mol/L,r分别为0.9995和0.9991,LOD均为1.7×10-8 mol/L(S/N=3)。在实际样品测定中,Au-AgNPs/MWNTs-SGSs/GCE可成功应用在知母、茵陈、淫羊藿叶的测定,结果令人满意。该方法具有试剂用量少、分析成本低、灵敏度高、重现性好等特点,是一种能同时测定药物有效成分芒果苷和淫羊藿苷的新方法。3.纳米金属银杂合羧基化碳纳米管修饰的玻碳电极对敌百虫的残留分析及应用研究。实验通过恒电位沉积的方法,在滴涂有羧基化碳纳米管(MWNTs-COOH)的玻碳电极上电沉积纳米金属银,成功研制出AgNPs/MWNTs-COOH/GCE。相比裸GCE,AgNPs/GCE,MWNTs-COOH/GCE,杂合材料修饰电极具有更强的电催化效应。实验中研制的AgNPs/MWNTs-COOH/GCE对敌百虫有更高的响应电流,并表现出良好的选择性、稳定性、重复性。在1.9×10-9~3.77×10-6 mol/L范围内呈现良好的线性关系,r为0.9991。该测定方法对敌百虫的LOD为6.2×10-10mol/L(S/N=3)。在测定实际样品(金银花和陈皮)中,结果表现出较高的灵敏度,回收率达到99.3%,在重复多次试验中RSD均低于5%,令人满意。
[Abstract]:Chemical modified electrode (Chemically Modified, Electrodes, CMEs) as the basis of electrochemical sensor, the electrochemical research field of electroanalytical chemistry is the most active. Since its inception, has become an important research direction in the field of drug analysis. In the analysis of application, CMEs has the following advantages: (1) in the electrode surface can be modified with specific functional groups, modified electrode prepared a series of different types and special functions; (2) material electrode substrate can be metal, nonmetal, organic matter, can also be a conductor, semiconductor, for the development of new electro analytical methods provide the basis; (3) according to the electrode modification of different functional groups, modified electrode has a selective response to solution in the presence of substances; (4) modified electrode can enhance the reversibility of electrode reaction, open up a new way to study the kinetics of electrode process; (5) modification The sensitivity of the electrodes is much larger compared with the bare electrode, provide a means for the further development of trace analysis. Based on the above advantages, CMEs has a broad application prospect in many fields. Based on carbon nanotubes and graphene have high surface area, unique structure, easy functionalization and modification etc. and the nano metal materials with enhanced characteristics of electron transfer rate, two on the electrochemical effect have promote role. This study constructed three kinds of nano metal complex electrochemical sensor and carbon nano materials modified and applied to the traditional Chinese medicine composition analysis. This thesis mainly consists of the following three parts: the electrochemical behavior and application of 1. Rhizoma Corydalis B in the glassy carbon electrode of nano nickel mixed sulfonated graphene modified glassy carbon electrode. The nano Ni / sulfonated graphene modified were prepared (NiNPs/SGS/ GCE) By scanning electron microscope, energy spectrum analysis and X-ray photoelectron spectroscopy were used to characterize the surface modification and properties of metals, and use the modified electrode to tetrahydropalmatine (Tetrahydropalmatine, THP) were analyzed. The results show that the electrochemical behavior of graphite has good electrochemical effect of sulfonic acid on THP, and can further enhance the oxidation peak of nano nickel the current THP, promote the electron transfer efficiency in the surface of the electrode. The oxidation peak current and the concentration of THP under the optimum conditions the linear relationship between the fine line in 5 * 10-7~2.0 * 10-5 mol/L, the linear coefficient of R is 0.9988, the detection limit of LOD (S/N=3) to 1.7 x 10-7 mol/L. electrochemical behavior of the modified electrode was successfully applied in the Yuanhuzhitong capsule THP.2. determination of mangiferin and icariin in nano silver alloys - carbon nanotubes sulfonated graphene modified glassy carbon electrode and its application. Through the experiment of drop The method of coated carbon nanotubes mixed sulfonated graphene dispersion (MWNTs-SGSs) and nano silver alloy (Au-AgNPs) has been modified on a glassy carbon electrode (GCE) surface, the development of new electrode. The modified electrode combined with the two-dimensional structure of Shi Moxi, carbon nanotubes and nano metal tubular structure special electrochemical effect that not only increases the effective surface area of electrode, but also enhance the electron transfer rate of the electrode surface, can realize the mangiferin (MIN) and icariin (IIN) at the same time. The experimental analysis by scanning electron microscopy, the surface morphology of modified electrode were studied by infrared characterization of cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronocoulometry were investigated on the electrochemical behavior of MIN and IIN on the modified electrode. The study found that electro chemical behavior of Au-AgNPs/MWNTs-SGSs/GCE on MIN and IIN show excellent choice And catalysis. By cyclic voltammetry on modification, pH, scan rate and other conditions were optimized. Under the optimal conditions of cyclic voltammetry peak potential was 0.56 V and 0.95 V, the linear range of the oxidation peak current and the concentration of MIN and IIN were 5 mol/L and 5 * 10-8~5.0 * 10-4 * 10-8~1.0 * 10-4 mol/L and R were 0.9995 and 0.9991, LOD was 1.7 * 10-8 mol/L (S/N=3). In practical samples, Au-AgNPs/MWNTs-SGSs/GCE can be successfully applied in the determination of Anemarrhena, wormwood, Epimedium leaves, with satisfactory results. This method has less reagent, analysis of low cost, high sensitivity and good reproducibility. Is the glassy carbon electrode is a new method for simultaneously determination of drug active ingredient icariin mango glycosides and.3. nano silver hybrid carboxylated carbon nanotubes modified to trichlorfon residue analysis and application research. The experiment by potentiostatic deposition In the drop, coated with carboxylated carbon nanotubes (MWNTs-COOH) electrodeposition of nano silver on the glassy carbon electrode, successfully developed AgNPs/MWNTs-COOH/GCE. compared with bare GCE, AgNPs/GCE, MWNTs-COOH/GCE, electro catalytic effect of hybrid material modified electrode has stronger. AgNPs /MWNTs-COOH/GCE developed the response current higher for trichlorfon, and performance good selectivity, stability and reproducibility. There was a good linear relationship in 1.9 * 10-9~3.77 * 10-6 mol/L range, R 0.9991. for the determination of trichlorfon LOD 6.2 * 10-10mol/L (S/N=3). In the determination of practical samples (honeysuckle and tangerine peel), the results showed high sensitivity, recovery rate in 99.3%, repeat the experiment in RSD were lower than 5%, satisfactory.

【学位授予单位】：广东药科大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;TP212.2

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