功能化石墨烯表面分子印迹电化学传感器的构筑及应用

发布时间：2018-05-24 22:09

本文选题：分子印迹 + 石墨烯　；参考：《郑州大学》2017年硕士论文

【摘要】：分子印迹电化学传感是将分子印迹聚合物对目标物的特异性识别和电化学传感技术结合为一体的一种现代电化学分析方法,灵敏度高、选择性好、设备简单。表面分子印迹是在特殊载体表面进行的分子印迹物合成技术,可以大大增加印迹位点的暴露面,加快识别位点与目标分子之间的传质作用,避免传统分子印迹识别位点包埋的种种弊端,日益成为研究者们的关注热点。基于表面分子印迹和电化学传感的优势,本论文以不同功能化石墨烯修饰的电极为载体,邻苯二胺为功能单体,通过电聚合条件的控制,在修饰电极表面合成分子印迹膜,构筑了功能化石墨烯表面分子印迹电化学传感器,实现了分子印迹聚合物合成和电化学传感器的一体化构筑;研究了传感器对目标物的识别性能和传感性能;并通过实际样品的分析检测,探讨了传感器在实际样本检测中的应用可行性。所获结果对于新的分子印迹电化学传感器的构建和应用提供了方法学的参考和依据。具体内容如下:1.基于聚苯乙烯磺酸钠功能化石墨烯(PSS-GR)的大豆苷元分子印迹电化学传感器的构建及应用。基于聚苯乙烯磺酸钠(PSS)与氧化石墨烯(GO)之间的非共价作用,通过水合肼一步还原法合成PSS功能化的石墨烯(PSS-GR);采用紫外,红外、透射电镜、对PSS-GR进行了表征;通过滴涂修饰技术,制备了PSS-GR修饰电极(PSS-GR/GCE);利用PSS-GR与功能单体邻苯二胺和模板分子大豆苷元之间的非共价作用,在PSS-GR/GCE界面上,通过电聚合条件的控制优化,制备了大豆苷元分子印迹膜,探讨了聚合物反应中单体与模板分子比例、聚合浓度、聚合介质条件及聚合强度的影响,确定了分子印迹膜的制备条件,构筑了大豆苷元分子印迹电化学传感器;以[Fe(CN)6]3-/[Fe(CN)6]4-为探针,研究了传感器对目标物大豆苷元的识别性能和传质过程;研究表明,该传感器在11 min内,即可完成大豆苷元在电极表面的饱和富集;在0.1 mol/L的NaOH溶液中,15 min即可完成目标分子的洗脱;相对于结构相似的葛根素、槲皮素、染料木素、白杨素,构筑的传感器对大豆苷元的印迹效率高达5.25,表现出了较快的传质过程和较好的选择识别性。在优化的实验条件下,大豆苷元在分子印迹膜上的识别响应与其浓度在1×10-9~2×10-8 mol/L成线性,检测限为8×10-10 mol/L。该方法可用于实际血样中和葛根提取液中大豆苷元的检测。2.基于聚苯乙烯磺酸钠功能化石墨烯(PSS-GR)的2,4-二氯酚电化学传感器的构建及应用。在第一章研究的基础上,依据PSS-GR对2,4-二氯酚和邻苯二胺强烈的非共价相互作用,在PSS-GR/GCE界面上,以邻苯二胺为功能单体,2,4-二氯酚为模板分子,采用循环伏安扫描电聚合制备了2,4-二氯酚的分子印迹电化学传感器,探讨了聚合物反应中单体与模板分子比例、聚合浓度、聚合介质条件及聚合强度的影响;以[Fe(CN)6]3-/[Fe(CN)6]4-为探针,研究了传感器的电化学行为和对目标物2,4-二氯酚的识别性能和传质过程。研究表明,该传感器在14 min内,即可完成大豆苷元在电极表面的饱和富集;在0.1 mol/L的NaOH溶液中,10 min即可完成目标分子的洗脱;相对于结构相似的氯酚类化合物,构筑的传感器对大豆苷元的印迹效率高达7.83,表现出了较快的传质过程和优异的选择性。在优化的实验条件下,传感器对2,4-二氯酚检测的线性范围为5×10-9~8×10-8mol/L,检测限为1×10-9 mol/L。该方法可以用于实际水样(湖水、自来水和雨水)中2,4-DCP的检测。3.基于聚多巴胺功能化石墨烯(PDA-rGO)的2,4-二氯酚分子印迹电化学传感器的构建及应用。基于多巴胺的弱还原性和碱性条件下自聚合的性质,一步法合成了聚多巴胺功能化石墨烯(PDA-rGO)。通过通过紫外-可见吸收光谱、红外光谱、扫描电镜、透射电镜、X射线衍射对PDA-rGO进行了表征。利用滴涂修饰技术,制备了PDA-rGO修饰电极(PDA-rGO/GCE);利用PDA-rGO与功能单体邻苯二胺和模板分子2,4-DCP之间的非共价作用,在PDA-rGO界面上,通过电聚合条件的控制优化,制备了2,4-DCP分子印迹膜;以[Fe(CN)6]3-/[Fe(CN)6]4-为探针,研究了构筑传感器的电化学行为和对目标物的传质和识别性能;研究表明,该传感器在6 min内即可完成2,4-二氯酚在电极表面的饱和富集;在乙醇溶液中8min即可完成目标分子的洗脱;相对于结构相似的2-氯酚,三氯酚,五氯酚,邻氨基苯酚和邻苯二酚,印迹因子分别为上述干扰物的3.67、4.02、4.63、5.77和25倍,印迹效率为15.5,表现出了更快的传质过程和优异的选择性。该传感器可以成功应用于水样中2,4-二氯酚检测
[Abstract]:Molecularly imprinted electrochemical sensing is a modern electrochemical analysis method, which combines the specific recognition of the molecularly imprinted polymer and the electrochemical sensing technology of the target. The sensitivity is high, the selectivity is good, and the equipment is simple. The surface molecular imprinting is a molecularly imprinted matter synthesis technology on the surface of the special carrier, which can greatly increase the printing On the basis of the advantages of surface molecularly imprinting and electrochemical sensing, the electrode of different functional fossils as the carrier, o-benzene two, is becoming the focus of attention of the researchers. Amines, as functional monomers, synthesized molecular imprinted membranes on the surface of modified electrodes by the control of electropolymerization conditions, constructed a Molecularly Imprinted Electrochemical Sensor on the surface of functionalized fossils, realized the synthesis of molecularly imprinted polymers and the integration of electrochemical sensors, and studied the recognition and sensing properties of the sensor. Through the analysis and detection of the actual samples, the feasibility of the application of the sensor in the actual sample detection is discussed. The results will provide a reference and basis for the construction and application of the new molecularly imprinted electrochemical sensor. The specific contents are as follows: 1. the daidzein molecule based on the PSS-GR of polystyrene sulfonate function fossils The construction and application of the imprinted electrochemical sensor. Based on the non covalent interaction between PSS and GO, PSS functionalized graphene (PSS-GR) was synthesized by one step reduction method of hydrazine hydrate, and PSS-GR was characterized by UV, IR, transmission electron microscopy, and PSS-GR modified electricity was prepared by coating modification. Polar (PSS-GR/GCE); with the non covalent interaction between PSS-GR and functional monomers of benzyl two amine and formwork daidzein, a daidzein molecularly imprinted membrane was prepared on the PSS-GR/GCE interface through the control of electropolymerization conditions. The proportion of monomers and template molecules, polymerization concentration, polymerization medium conditions and polymerization in the polymer reaction were discussed. The preparation conditions of the molecularly imprinted membrane were determined by strength, and a daidzein Molecularly Imprinted Electrochemical sensor was constructed. The identification performance and mass transfer process of the sensor to daidzein were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as a probe. The study showed that the sensor could finish the Daidzein on the surface of the electrode in 11 min. Saturated enrichment; in the 0.1 mol/L NaOH solution, 15 min can complete the elution of the target molecule; compared to the structure similar puerarin, quercetin, genistein and poplar, the imprinting efficiency of the daidzein is up to 5.25, showing a faster mass transfer process and better selection recognition. Under the optimized experimental conditions, The recognition response of Daidzein on molecular imprinting membrane is linear with its concentration of 1 x 10-9~2 x 10-8 mol/L, and the detection limit is 8 x 10-10 mol/L.. The method can be used for the detection of Daidzein in the actual blood sample and pueraria extract. The construction of 2,4- two chlorophenol electrochemical sensor based on the PSS-GR of sodium sulfonate (PSS-GR) and the construction of.2. On the basis of the study in the first chapter, on the basis of the strong non covalent interaction between 2,4- two Chlorophenol and phthalamines on the basis of PSS-GR, the molecular imprinting electrochemical sensor of 2,4- two chlorophenol was prepared by cyclic voltammetric scanning electropolymerization on the PSS-GR/GCE interface, with phthalic two amine as functional monomer and 2,4- two chlorophenol as the template molecule. The effects of the proportion of the monomers and the template molecules, the concentration of the polymerization, the conditions of the polymerization medium and the polymerization strength were investigated. The electrochemical behavior of the sensor and the identification performance and mass transfer process of the target 2,4- two chlorophenol were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as a probe. The results showed that the sensor could complete the daidzein in the electrode in 14 min. The surface saturation enrichment; in the 0.1 mol/L NaOH solution, 10 min can complete the elution of the target molecule; compared with the structure similar chlorophenols, the imprinting efficiency of the constructed sensor to daidzein is up to 7.83, showing a rapid mass transfer process and excellent selection. Under the optimized experimental conditions, the sensor is to 2,4- two chlorine. The linear range of phenol detection is 5 x 10-9~8 x 10-8mol/L and the detection limit is 1 x 10-9 mol/L.. The method can be used for the detection of 2,4-DCP in real water samples (lake water, tap water and rainwater)..3. based on the 2,4- two chlorophenol Molecularly Imprinted Electrochemical Sensor Based on the dopamine functional fossil Mo (PDA-rGO) and its application. The property of self polymerization under alkaline conditions, polydopamine functionalized fossil mo (PDA-rGO) was synthesized by one step method. PDA-rGO was characterized by UV visible absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X ray diffraction. The PDA-rGO modified electrode (PDA-rGO/GCE) was prepared by the coating modification technique; and PDA-rGO and function were used. The non covalent interaction between the mono two amine and the template molecule 2,4-DCP was used to prepare the 2,4-DCP molecularly imprinted membrane on the PDA-rGO interface through the control of the electropolymerization conditions. The electrochemical behavior of the sensor and the mass transfer and recognition performance of the target were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as the probe. The saturated enrichment of 2,4- chlorophenol on the surface of the electrode can be completed in 6 min, and the elution of the target molecule can be completed in the ethanol solution; compared with the structure similar 2- chlorophenol, three chlorophenol, pentachlorophenol, O aminophenol and catechol, the imprinting factor is 3.67,4.02,4.63,5.77 and 25 times of the interferon, and the imprinting efficiency is 15.5. A faster mass transfer process and excellent selectivity has been achieved. The sensor can be successfully applied to the detection of 2,4- two chlorophenol in water samples.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.1

【参考文献】