基于芦丁分子印迹壳聚糖-离子液体功能化石墨烯-碳纳米管的电化学传感器的制备及应用

Preparation and Application of a Rutin Electrochemical Sensor Based on Molecularly Imprinted Chitosan-Ionic Liquid Functionalized Graphene-Carbon Nanotubes Composite

以壳聚糖为功能单体,芦丁为模板分子,戊二醛为交联剂,离子液体功能化石墨烯-碳纳米管(GN-CNTs-IL)为掺杂材料,通过简单混合后滴加在玻碳电极表面,制备了芦丁分子印迹电化学传感器。利用扫描电镜、透射电镜及电化学技术对复合材料和印迹电极的表面形貌等进行了表征,结果发现分子印迹复合材料呈多孔结构,有良好的导电性,GN-CNTs-IL对芦丁电化学传感有明显的增敏作用。进一步对离子液体的用量、壳聚糖的浓度、壳聚糖与芦丁的质量比、溶液pH值等因素的影响进行了考察,并对制备和测试条件进行了优化。在所选条件下,所构建的电化学传感器对芦丁表现出良好的响应性能,不仅线性检测范围宽(0.01~200.0μmol/L)、检出限低(6 nmol/L),而且选择性较高、重现性好、稳定性佳。该传感器可用于荞麦茶、芦丁片等样品中芦丁的检测。

In this paper,a rutin imprinted composite modified GCE was prepared by simple dropping procedures,using chitosan as functional polymer,rutin as template molecule,glutaraldehyde as crosslinking agent and ionic liquid functionalized graphene-carbon nanotubes(GN-CNTs-IL)as doping material.The composite and imprinted electrode were characterized by scanning electron microscopy,transmission electron microscopy and electrochemical technique.The experimental results showed that the molecularly imprinted composite had a porous structure and high electrical conductivity,GN-CNTs-IL exhibited obvious sensitization effect on the electrochemical sensing of rutin.In addition,the influence of some factors such as the amount of ionic liquid,the concentration of chitosan,the mass ratio of chitosan to rutin,the coating amount,the solution pH and the elution time,was discussed,and the conditions for preparation and detection were optimized.Under the selected conditions,the obtained MIP/GN-CNTS-IL/GCE sensor presented good response to rutin,with a wide linear detection range(0.01-200.0μmol/L),a low detection limit(6 nmol/L),high selectivity,good reproducibility and stability.The application feasibility of the sensor was evaluated by detecting rutin in real samples,and satisfactory results were obtained.