【作者】 刘敏；

【导师】 廖原；

【作者基本信息】 西北师范大学 ， 分析化学， 2022， 硕士

【摘要】 基于纳米复合材料构建传感器是当前电化学传感领域活跃的研究方向之一。由于其独特的物理和化学性质,纳米复合材料可以显著提高传感性能和分析复杂系统和实际样品的能力。基于化学修饰电极的新进展,构建了三种金属-有机聚合物传感系统。通过物理吸附和自组装的方法,利用几种碳纳米材料高效负载金属-有机聚合物构建电化学传感器。通过电化学分析方法,系统地研究了不同复合材料修饰电极的电化学传感机理。建立了一些具有高选择性、灵敏度和快速地新的电化学分析方法,用于检测复杂系统中的葡萄糖、对乙酰氨基酚和多巴胺。主要研究工作涉及以下几个方面:1.基于铜纳米颗粒修饰的硫基有机聚合物设计并构建了Cu@S-co-BIM/GCE电化学传感器用于葡萄糖的检测。S-co-BIM是通过反硫化方法合成的一种稳定的导电基质,表现出良好的导电性。电沉积铜纳米颗粒作为催化剂。结果表明,所构建的电化学传感器对葡萄糖的氧化表现出优良的电催化活性。在优化后的条件下,在1μM～3.3 m M浓度范围内,葡萄糖的氧化峰电流与浓度表现出良好的线性关系,检测限（LOD）为0.32μM。同时,该传感器在抗坏血酸（AA）、尿酸（UA）、果糖、木糖和麦芽糖等多种干扰物质存在下对葡萄糖氧化具有高选择性。所制备的Cu@S-co-BIM/GCE传感器表现出优异的重现性和长期稳定性,并已成功应用于人血清样品和商品葡萄糖口服液中葡萄糖的检测,结果令人满意。2.通过溶剂热法制备了铁基有机聚合物/羧基功能化的多壁碳纳米管复合材料（NH₂-MIL-101（Fe）/MWCNT-COOH）。基于该复合材料构建的电化学传感器NH₂-MIL-101（Fe）/MWCNT-COOH/GCE对对乙酰氨基酚（AP）具有优异的电催化活性。在优化后的条件下,在0.2～140μM浓度范围内,AP的氧化峰电流与浓度表现出良好的线性关系,LOD为0.08μM。该传感器在葡萄糖、UA、AA等干扰物质存在下,对AP具有高选择性。此外,该传感器的稳定性和重现性令人满意,并已成功应用于复方对乙酰氨基酚片中AP的定量分析。3.通过溶剂热法制备了铁基有机聚合物/有序介孔碳复合材料（NH₂-MIL-101（Fe）/OMCs）。基于NH₂-MIL-101（Fe）/OMCs复合材料构建的传感器对多巴胺（DA）表现出优异的电催化活性。在优化后的条件下,在0.5～750μM浓度范围内,DA的氧化峰电流与浓度表现出良好的线性关系,LOD为0.12μM。该传感器在K⁺、Na⁺、Ca²⁺、Cl^-、NO₃^-、葡萄糖、UA和AA等多种干扰物存在下,对多巴胺具有高选择性。此外,该传感器有希望应用于人血清样品中DA的检测。更多还原

【Abstract】 It is an active research trend in the domain of electrochemical sensing to construct sensors from nanocomposite materials.Due to their unique physical and chemical properties,nanocomposite materials can significantly improve the sensing performance and the ability to analyze complex systems and actual samples.Based on the new progresses chemically modified electrode,three metal-organic polymer sensing systems were structured.And several carbon-nanomaterials were used to efficiently load metal-organic polymer for the construction of the electrochemical sensors by physical adsorption and self-assembly methods.The mechanism of electrochemical sensing of modified electrodes with different composite materials were systematically investigated by using electrochemical analysis.Some new electrochemical analysis methods,with the highly selective,sensitivity and rapidity,will be established for the detection of glucose,acetaminophen,and dopamine in complex systems.The main research work involves the following aspects:1.A Cu@S-co-BIM/GCE electrochemical sensor was designed and constructed based on copper nanoparticles-modified sulfur-based organic polymers for glucose detection.S-co-BIM is a stable conductive matrix synthesized by an inverse sulfidation method and exhibits good electrical conductivity.Electrodeposited copper nanoparticles as catalysts.The results show that the electrochemical sensor thus constructed significantly improves the selectivity and sensitivity of glucose determination.Under the optimized conditions,in the concentration range of 1μM to 3.3 m M,the oxidation peak current of glucose showed a good linear relationship with the concentration,and the limit of detection（LOD）was 0.32μM.Meanwhile,the sensor exhibits high selectivity for glucose oxidation in the presence of various interfering substances such as ascorbic acid（AA）,uric acid（UA）,fructose,xylose,and maltose.The prepared Cu@S-co-BIM/GCE sensor exhibits excellent reproducibility and long-term stability,and has been successfully applied to the detection of glucose in human serum samples and commercial glucose oral solution with satisfactory results.2.Iron-based organic polymer/carboxyl-functionalized multi-walled carbon nanotube composites（NH₂-MIL-101（Fe）/MWCNT-COOH）were prepared by solvothermal method.The electrochemical sensor NH₂-MIL-101（Fe）/MWCNT-COOH/GCE constructed based on this composite exhibits excellent electrocatalytic activity for paracetamol（AP）.Under the optimized conditions,the oxidation peak current of AP showed a good linear relationship with the concentration in the concentration range of 0.2～140μM,and the LOD was 0.08μM.The sensor exhibits high selectivity for AP in the presence of interfering substances such as glucose,UA and AA.In addition,the stability and reproducibility of the sensor are satisfactory,and it has been successfully applied to the quantitative analysis of AP in compound acetaminophen tablets.3.Iron-based organic polymer/ordered mesoporous carbon composites（NH₂-MIL-101（Fe）/OMCs）were prepared by solvothermal method.The sensor constructed based on the NH₂-MIL-101（Fe）/OMCs composite exhibits excellent electrocatalytic activity towards dopamine（DA）.Under the optimized conditions,the oxidation peak current of DA showed a good linear relationship with the concentration in the concentration range of 0.5～750μM,and the LOD was 0.12μM.The sensor exhibits high selectivity for dopamine in the presence of various interferents such as K⁺,Na⁺,Ca²⁺,Cl^-,NO₃^-,glucose,UA and AA.Furthermore,the sensor is promising for the detection of DA in human serum samples.更多还原