硫丹检测的分子印迹纳米聚合物压电传感技术研究
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摘要
分子印迹聚合物(Molecularly imprinted polymers,MIPs),是基于抗原.抗体反应原理而采用化学方法合成的高聚物。作为一种新型的吸附材料,MIPs具有从复杂样品中选择性识别目标分子或与其结构相近的某一类化合物的能力,因而被称为“人工抗体”。由于其化学性能稳定,目前已经广泛应用于样品分离、固相萃取、仿生传感器检测等领域。
本文首先对传统沉淀聚合制备微球的条件进行摸索,探讨聚合溶剂体积、模板、单体各组分比例,通氮气除氧时间和聚合时间对聚合物微球形貌和产量的影响,得出在乙腈中可以制备出纳米级别的印迹聚合物微球。选取硫丹分子为模板物质,采用沉淀聚合方法制备了分子印迹聚合物微球,通过扫描电镜观察产物颗粒均匀,分散性良好,粒径在200-300nm;采用静态吸附试验测定了分子印迹聚合物对模板分子的结合能力,并将聚合物微球用于环境介质中农药的吸附,取得较好的效果。
在此研究工作基础之上,还完成了硫丹印迹聚合物颗粒在压电石英晶体微天平上的固定化研究,以PVC(聚氯乙烯)为包埋材料,以THF(四氢呋喃)为溶剂,将硫丹分子印迹聚合物微球固定在压电石英晶体电极上,利用原子力显微镜分析了所构建的敏感层,敏感层中的MIPs微球分布均匀。对传感器检测条件进行优化设计和实验。传感器的应用进行了初步的应用实验,得出了部分样品的硫丹残留量的传感器检测结果。并对实验数据的可靠性进行了比对实验。农药硫丹浓度在10-1000ng/mL范围内,传感器响应方程为y=6.21+0.133,最低检测限为13.22 ng/mL。
本研究为制备可以应用现场的、实时的、快速的食品安全检测方法的样品快速处理和生物传感器方法建立提供理论依据和实际指导。
Molecularly imprinted polymers (MIPs) are polymers prepared in presence of a template that serves as a mould for the formation of template-complementary binding sites. Thus, MIPs can be created to recognize a target molecule with affinity and selectivity comparable to natural receptors and were called as "artificial antibody". And these materials can withstand much harsher conditions than antibodies, such as high temperature, pressure, extreme pH, and organic solvents. These properties have made them extremely attractive for solving problems in the fields of preparative chemical separations, purification and sensors, or for the removal of specific molecular targets from complex mixtures.
In this article, traditional precipitation polymerization was investigated in order to obtaine desired uniform microspheres. Endosulfan was used as templates to synthesize the molecularly imprinted polymers. The environmental scanning microscopy was used to describe the shape and the size of the obtained polymer microspheres, the results showed that the uniform, global nano-metric imprinted polymer microspheres were obtained, the size of the reaulted microspheres ranged from 200nm to 300nm.
It was studied that the endosulfan imprinted polymer microspheres was fixed on the quartz crystal electrode to fabricate the piezoelectric sensor, in this study the PVC and THF were used as embed pigment and solvent, respectively. The surface of the MIP microspheres coated quartz crystal electrodes was demonstrated by atomic force microscopy (AFM), the results showed that the distribution of the MIP microspheres is uniform. The detection conditions were optimized to analyze the real samples, The sensor developed exhibits a liner relationship between the frequency shift and endosulfan concentration in the range of 10 to 1000ng/mL (y= 6.21+0.133), and the detection limit was 13.22 ng/mL., But there are many environmental factors affecting the detection results, so further work was need to do to perfect the resulted sensor.
From above, this study gives me some help in theory and practice to realize the real time, on-spot, fast detection of and the samples preparation prior to analysis pesticide in foodstuff.
本文首先对传统沉淀聚合制备微球的条件进行摸索,探讨聚合溶剂体积、模板、单体各组分比例,通氮气除氧时间和聚合时间对聚合物微球形貌和产量的影响,得出在乙腈中可以制备出纳米级别的印迹聚合物微球。选取硫丹分子为模板物质,采用沉淀聚合方法制备了分子印迹聚合物微球,通过扫描电镜观察产物颗粒均匀,分散性良好,粒径在200-300nm;采用静态吸附试验测定了分子印迹聚合物对模板分子的结合能力,并将聚合物微球用于环境介质中农药的吸附,取得较好的效果。
在此研究工作基础之上,还完成了硫丹印迹聚合物颗粒在压电石英晶体微天平上的固定化研究,以PVC(聚氯乙烯)为包埋材料,以THF(四氢呋喃)为溶剂,将硫丹分子印迹聚合物微球固定在压电石英晶体电极上,利用原子力显微镜分析了所构建的敏感层,敏感层中的MIPs微球分布均匀。对传感器检测条件进行优化设计和实验。传感器的应用进行了初步的应用实验,得出了部分样品的硫丹残留量的传感器检测结果。并对实验数据的可靠性进行了比对实验。农药硫丹浓度在10-1000ng/mL范围内,传感器响应方程为y=6.21+0.133,最低检测限为13.22 ng/mL。
本研究为制备可以应用现场的、实时的、快速的食品安全检测方法的样品快速处理和生物传感器方法建立提供理论依据和实际指导。
Molecularly imprinted polymers (MIPs) are polymers prepared in presence of a template that serves as a mould for the formation of template-complementary binding sites. Thus, MIPs can be created to recognize a target molecule with affinity and selectivity comparable to natural receptors and were called as "artificial antibody". And these materials can withstand much harsher conditions than antibodies, such as high temperature, pressure, extreme pH, and organic solvents. These properties have made them extremely attractive for solving problems in the fields of preparative chemical separations, purification and sensors, or for the removal of specific molecular targets from complex mixtures.
In this article, traditional precipitation polymerization was investigated in order to obtaine desired uniform microspheres. Endosulfan was used as templates to synthesize the molecularly imprinted polymers. The environmental scanning microscopy was used to describe the shape and the size of the obtained polymer microspheres, the results showed that the uniform, global nano-metric imprinted polymer microspheres were obtained, the size of the reaulted microspheres ranged from 200nm to 300nm.
It was studied that the endosulfan imprinted polymer microspheres was fixed on the quartz crystal electrode to fabricate the piezoelectric sensor, in this study the PVC and THF were used as embed pigment and solvent, respectively. The surface of the MIP microspheres coated quartz crystal electrodes was demonstrated by atomic force microscopy (AFM), the results showed that the distribution of the MIP microspheres is uniform. The detection conditions were optimized to analyze the real samples, The sensor developed exhibits a liner relationship between the frequency shift and endosulfan concentration in the range of 10 to 1000ng/mL (y= 6.21+0.133), and the detection limit was 13.22 ng/mL., But there are many environmental factors affecting the detection results, so further work was need to do to perfect the resulted sensor.
From above, this study gives me some help in theory and practice to realize the real time, on-spot, fast detection of and the samples preparation prior to analysis pesticide in foodstuff.
引文
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