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基于密度泛函理论和表面分子印迹技术构建高灵敏诺氟沙星电化学传感器
Construction of Norfloxacin Electrochemical Sensors Based on Density Functional Theory and Surface Molecularly Imprinting Technology
【摘要】 采用密度泛函理论(DFT)计算方法,对4种可能与诺氟沙星(NOR)发生相互作用的功能单体进行筛选,确定甲基丙烯酸为最优单体。以壳聚糖/多壁碳纳米管(CS-MWCNTs)为基质、NOR为模板分子、甲基丙烯酸为功能单体,采用“接枝聚合与交联印迹同步进行”的方法制备表面分子印迹聚合物(SMIP)-NOR@CS/MWCNTs,并利用扫描电子显微镜、红外光谱仪和X射线电子能谱仪对其结构和形貌进行表征,探究此印迹聚合物对NOR的吸附性能和吸附机理。采用滴涂法将SMIP-NOR@CS/MWCNTs修饰于玻碳电极(GCE)表面,构建了诺氟沙星分子印迹传感器(SMIP-NOR@CS/MWCNTs/GCE),通过循环伏安法(CV)、电化学阻抗谱(EIS)和差分脉冲伏安法(DPV)评价其电化学特性。结果表明,SMIP-NOR@CS/MWCNTs对NOR具有良好的结合亲和性,印迹因子为2.71, DPV电流响应变化值与NOR浓度在0.1~1.5 nmol/L和1.5~140 nmol/L两段范围内分别呈良好的线性关系,检出限为0.026 nmol/L。此传感器具有优良的选择识别性、稳定性、重复使用性和重现性,将其用于牛奶和自来水样品中NOR的检测,加标回收率为97.5%~103.3%,与高效液相色谱(HPLC)法的检测结果无显著性差异。
【Abstract】 Using density functional theory(DFT) for calculation, four kinds of functional monomers that might interact with norfloxacin(NOR) were screened, and methacrylic acid(MAA) was selected as the optimal functional monomer. By using chitosan/multiwalled carbon nanotubes(CS-MWCNTs) as matrix, NOR as template, MAA as functional monomer, surface molecularly imprinting polymer(SMIP)-NOR@CS/MWCNTs were prepared by“grafting polymerization synchronized with crosslinking/imprinting” method. The structure and morphology of polymer were characterized by scanning electron microscope, infrared spectroscopy and X-ray photoelectron spectrometer. The adsorption performance and mechanism of SMIP-NOR@CS/MWCNTs for NOR were explored.The SMIP-NOR@CS/MWCNTs modified glassy carbon electrode(SMIP-NOR@CS/MWCNTs/GCE) was constructed by drop-coating method. The electrochemical performance of the sensor was studied by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS) and differential pulse voltammetry(DPV). The results showed that SMIP-NOR@CS/MWCNTs had excellent binding affinity for NOR, and imprinting factor was2.71. The variation of DPV current response showed a good linear relationship with NOR concentration in the range of 0.1–1.5 nmol/L and 1.5–140 nmol/L, respectively, and with a detection limit of 0.026 nmol/L. The sensor exhibited excellent selectivity, stability, reusability and reproducibility. The method presented good practical application performance in detecting NOR in water and milk samples with recoveries of 97.5%–103.3%, and the results had no significant differences compared with those of high-performance liquid chromatography method.
【Key words】 Electrochemical sensor; Surface molecularly imprinting; Density functional theory; Norfloxacin;
- 【文献出处】 分析化学 ,Chinese Journal of Analytical Chemistry , 编辑部邮箱 ,2026年01期
- 【分类号】O657.1;TS207.3
- 【下载频次】57