基于石墨烯的电化学传感器的制备及应用
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摘要
本文以石墨烯为电极修饰材料,研究了其在电化学传感与其对亚铁血红素类蛋白质过氧化氢酶、血红蛋白的直接电化学影响,并成功的构建了NO的电化学传感器和氧化还原蛋白质/石墨烯修饰电极。实现了对一些生物分子如过氧化氢、葡萄糖等的生物传感。
全文共分为四章:(1)首先对石墨烯的结构、性质、制备方法与应用作了介绍,并对电化学传感器的分类与发展等方面做了综述,最后提出了论文设想。(2)用电化学还原的方法制备出了还原石墨烯修饰电极,并对NO有良好的电催化氧化响应,线性范围是7.20×10~(-7)～7.84×10~(-5) mol/L,相关系数为0.9986。当电极上修饰一层Nafion膜后,能实现对NO的选择性测定。(3)制备了壳聚糖(Cs)分散的化学还原的石墨烯(GR)修饰电极,然后经过浸泡,使过氧化氢酶吸附于Cs-GR修饰电极表面,利用电化学方法研究了过氧化氢酶的直接电子传递和对H_2O_2、葡萄糖的电催化还原性能。实验结果显示, H2O2浓度在1～39μmol/L范围内呈线性,检测限0.2μM;葡萄糖在2.0×10~(-6)～2.06×10~(-4)mol/L内呈线性,检测限2.7μM。
(4)将Cs-GR修饰电极浸泡于血红蛋白(Hb)溶液中,制备出了Hb/Cs-GR修饰电极,并研究了Hb的直接电化学行为,并发现其对NO有较好的电催化性能。
In this thesis, graphene was modified on the surface of substrate electrodes. Then we studied the application of graphene in electrochemical sensing. The biomolecules such as catalase, hemoglobin, were adsorbed on graphene modified electrode surface and their electrochemical characteristics were also investigated. NO electrochemical sensor and the redox protein/graphene modified electrodes were constructed. Thus, bio-sensing of a number of biological molecules such as hydrogen peroxide, glucose were achieved.
The thesis consisted of four chapters: (1) First, the structure, properties, preparation methods and applications of graphene are introduced. The classification and development of electrochemical sensors had been described. Then, the research proposal for this thesis was presented. (2) Graphene modified electrode was prepared through electrochemically reducing graphene oxide on the surface of glassy carbon electrode. The modified electrode owns strong catalytic activity towards the oxidation of nitric oxide. The linear range is from 7.2×10~(-7) to 7.84×10~(-5)mol/L,with a limit of detection of 2.0×10~(-7)mol/L.With further modification of Nafion, the determination is free from the interference of nitrite. (3) Catalase was adsorbed onto the surface of Cs-GR modified electrode by immersing the Cs-GR modified electrode in catalase’s PBS solution. Then the direct electron transfer between catalase and electrode was observed, and bioelectrocatalysis of catalase for H_2O_2 and glucose were investigated. Experimental results show that the linear range of H2O2 is 1-39μM with a detection limt of 0.2μM, and the glucose is from 2.0×10~(-6) to 2.06×10~(-4) mol/L with a limit detection of 2.7μM. (4) Hb/Cs-GR electrode was fabricated, then the direct electron transfer of Hb and its bioelectrocatalysis to NO was studied.
全文共分为四章:(1)首先对石墨烯的结构、性质、制备方法与应用作了介绍,并对电化学传感器的分类与发展等方面做了综述,最后提出了论文设想。(2)用电化学还原的方法制备出了还原石墨烯修饰电极,并对NO有良好的电催化氧化响应,线性范围是7.20×10~(-7)～7.84×10~(-5) mol/L,相关系数为0.9986。当电极上修饰一层Nafion膜后,能实现对NO的选择性测定。(3)制备了壳聚糖(Cs)分散的化学还原的石墨烯(GR)修饰电极,然后经过浸泡,使过氧化氢酶吸附于Cs-GR修饰电极表面,利用电化学方法研究了过氧化氢酶的直接电子传递和对H_2O_2、葡萄糖的电催化还原性能。实验结果显示, H2O2浓度在1～39μmol/L范围内呈线性,检测限0.2μM;葡萄糖在2.0×10~(-6)～2.06×10~(-4)mol/L内呈线性,检测限2.7μM。
(4)将Cs-GR修饰电极浸泡于血红蛋白(Hb)溶液中,制备出了Hb/Cs-GR修饰电极,并研究了Hb的直接电化学行为,并发现其对NO有较好的电催化性能。
In this thesis, graphene was modified on the surface of substrate electrodes. Then we studied the application of graphene in electrochemical sensing. The biomolecules such as catalase, hemoglobin, were adsorbed on graphene modified electrode surface and their electrochemical characteristics were also investigated. NO electrochemical sensor and the redox protein/graphene modified electrodes were constructed. Thus, bio-sensing of a number of biological molecules such as hydrogen peroxide, glucose were achieved.
The thesis consisted of four chapters: (1) First, the structure, properties, preparation methods and applications of graphene are introduced. The classification and development of electrochemical sensors had been described. Then, the research proposal for this thesis was presented. (2) Graphene modified electrode was prepared through electrochemically reducing graphene oxide on the surface of glassy carbon electrode. The modified electrode owns strong catalytic activity towards the oxidation of nitric oxide. The linear range is from 7.2×10~(-7) to 7.84×10~(-5)mol/L,with a limit of detection of 2.0×10~(-7)mol/L.With further modification of Nafion, the determination is free from the interference of nitrite. (3) Catalase was adsorbed onto the surface of Cs-GR modified electrode by immersing the Cs-GR modified electrode in catalase’s PBS solution. Then the direct electron transfer between catalase and electrode was observed, and bioelectrocatalysis of catalase for H_2O_2 and glucose were investigated. Experimental results show that the linear range of H2O2 is 1-39μM with a detection limt of 0.2μM, and the glucose is from 2.0×10~(-6) to 2.06×10~(-4) mol/L with a limit detection of 2.7μM. (4) Hb/Cs-GR electrode was fabricated, then the direct electron transfer of Hb and its bioelectrocatalysis to NO was studied.
引文
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