恩诺沙星分子印迹电化学传感器的制备及其在食品快速检测中的应用
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摘要
以恩诺沙星(ENRO)为模板分子,邻苯二胺(OPD)和邻氨基苯酚(OAP)为复合功能单体,在NaAc-HAc缓冲液中,采用电聚合法在玻碳电极表面制备了能够特异识别模板分子及其结构类似物的分子印迹电化学传感器。试验选用含1mol/L氯化钾及1mmol/L铁氰化钾的混合液作为表征溶液,采用循环伏安法和方波伏安法研究了传感器的电化学响应特性,并优化制备和检测条件。结果表明,在最佳条件下,恩诺沙星在2×10~(-6)mol/L～4×10~(-5)mol/L浓度范围内线性关系良好,检出限为7. 0×10~(-7)mol/L,该传感器具有良好的稳定性和重现性,对恩诺沙星以及结构类似物具有良好的选择性。采用该传感器对实际样品牛奶、鸡肉、猪肉和鸡蛋中的恩诺沙星进行检测,加标回收率在83. 2%～92. 7%之间,相对标准偏差(RSD)在1. 0%～4. 8%之间(n=5),该传感器选择性强、稳定性好、操作简便、检测快速灵敏、成本低、具有良好的应用前景。
A novel molecular imprinted electrochemical sensor was prepared by electro-polymerization on the surface of a glassy carbon electrode in NaAc-HAc buffer solution,and enrofloxacin was used as template molecular,o-phenylenediamine(OPD) and o-aminophenol(OAP) as composite functional monomer. The sensor could specifically recognize the template molecules and its analogues. In the experiment,1 mol/L KCl and 5 mmol/L K_3[Fe(CN)_6]was used as characterization solution,the electrochemical sensor response characteristics were researched,and the preparation and detection conditions of the sensor were optimized by square wave voltammetry(SWV) and cyclic voltammetry(CV). The results showed that under the optimal conditions,the linear relationship between SWV peak current difference and the concentrations of enrofloxacin was found in the range of 2 × 10~(-6)mol/L ～ 4 × 10~(-5)mol/L with the linear correlation coefficient (R~2) of 0. 9990,the detection limit was 7. 0 × 10~(-7)mol/L,and the sensor had good stability,repeatability and good selectivity to enrofloxacin and its analogues. Enrofloxacin in real samples,such as milk,egg,chicken and pork,was detected by the developed sensor,the average recoveries were between 83. 2% and 92. 7%,and the relative standard deviations(RSDs) were 1. 0%～4. 8%(n = 5). This sensor is simple,sensitive,low cost,and has good selectivity and stability,which provide it a good application prospect.
A novel molecular imprinted electrochemical sensor was prepared by electro-polymerization on the surface of a glassy carbon electrode in NaAc-HAc buffer solution,and enrofloxacin was used as template molecular,o-phenylenediamine(OPD) and o-aminophenol(OAP) as composite functional monomer. The sensor could specifically recognize the template molecules and its analogues. In the experiment,1 mol/L KCl and 5 mmol/L K_3[Fe(CN)_6]was used as characterization solution,the electrochemical sensor response characteristics were researched,and the preparation and detection conditions of the sensor were optimized by square wave voltammetry(SWV) and cyclic voltammetry(CV). The results showed that under the optimal conditions,the linear relationship between SWV peak current difference and the concentrations of enrofloxacin was found in the range of 2 × 10~(-6)mol/L ～ 4 × 10~(-5)mol/L with the linear correlation coefficient (R~2) of 0. 9990,the detection limit was 7. 0 × 10~(-7)mol/L,and the sensor had good stability,repeatability and good selectivity to enrofloxacin and its analogues. Enrofloxacin in real samples,such as milk,egg,chicken and pork,was detected by the developed sensor,the average recoveries were between 83. 2% and 92. 7%,and the relative standard deviations(RSDs) were 1. 0%～4. 8%(n = 5). This sensor is simple,sensitive,low cost,and has good selectivity and stability,which provide it a good application prospect.
引文
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[2]叶建美,吴康,吴洪丽,等.恩诺沙星抗菌效果及药代动力学研究进展.湖北农业科学,2015,54(23):5813-5816.Ye J M,Wu K,Wu H L,et al.Research progress of pharmacokinetics and pharmacodynamics of Enrofloxacin.Hubei Agricultural Sciences,2015,54(23):5813-5816.
[3]吕媛.氟喹诺酮类抗菌药(fluoroquinolones)研究进展//中国药理学会,第六届全国抗菌药物临床药理学术会议.北京,2006:466-467.Lv Y.Advances in research of fluoroquinolones//Chinese Pharmacological Society,The 6thNational Conference of Clinical Pharmaclogy on Antimicrobial Agents.Beijing,2006:466-467.
[4]包晓丽.食品中喹诺酮类抗菌药的分析方法比较研究.杭州:浙江工商大学,2009.Bao X L.Comparative analysis of quinolone antibacterials in food.Hangzhou:Zhejiang Gongshang University,2009.
[5]Choksi P,Shaikh F,Shah D A,et al.Development of liquid chromatographic method for simultaneous determination of bromhexine hydrochloride and enrofloxacin in formulations.Indian Drugs,2018,55(2):44-49.
[6]Joshi H,Shah A,Patel J,et al.Development and validation of analytical method for simultaneous estimation of bromhexine HCl and enrofloxacine in combined pharmaceutical dosage form.Eurasian Journal of Analytical Chemistry,2017,12(8):1631-1638.
[7]刘亚梅,闵盛.高效液相色谱法同时测定禽蛋中环丙沙星、达氟沙星和恩诺沙星的残留量.理化检验(化学分册),2016,52(3):305-307.Liu Y M,Min S.Simultaneous determination of the residues of ciprofloxacin,danofloxacin and enrofloxacin in eggs by HPLC.Physical Testing and Chemical Analysis Part B:Chemical Analysis,2016,52(3):305-307.
[8]赵晶,毕春娟,陈振楼,等.上海市崇明岛养殖场周边环境中氟喹诺酮类抗生素的含量特征.生态与农村环境学报,2017,33(2):120-126.Zhao J,Bi C J,Chen Z L,et al.Contents of fluoroquinolone-type antibiotics in the surroundings of livestock farms in Chongming island of Shanghai.Journal of Ecology&Rural Environment,2017,33(2):120-126.
[9]Ho Y B,Zakaria M P,Latif P A,et al.Occurrence of veterinary antibiotics and progesterone in broiler manure and agricultural soil in Malaysia.Science of the Total Environment,2014,488-489(1):261-267.
[10]高文惠,庞军,王姣姣,等.联苯三唑醇分子印迹电化学传感器的制备及识别性能研究.现代食品科技,2015,31(1):89,96-100.Gao W H,Pang J,Wang J J,et al.Preparation and recognition properties of a bitertanol electrochemical sensor based on molecular imprinting technology.Modern Food Science and technology,2015,31(1):89,96-100.
[11]赵玲钰,高林,庞军,等.胺菊酯分子印迹电化学传感器的制备及性能.食品科学,2017,38(8):283-289.Zhao L Y,Gao L,Pang J,et al.Preparation and application of molecularly imprinted electrochemical sensor for the detection of tetramethrin and its performance.Food Science,2017,38(8):283-289.
[12]宫倩倩.吲哚乙酸分子印迹电化学传感器的研究.无锡:江南大学,2012.Gong Q Q.Indole acetic acid molecular imprinted electrochemical sensor research.Wuxi:Jiangnan University,2012.
[13]汤万进,赵彤,周春红,等.复合功能单体法合成氧氟沙星分子印迹材料.兰州大学学报(自然科学版),2014(1):136-144.Tang W J,Zhao T,Zhou C H,et al.Preparation of a molecularly imprinted polymer of ofloxacin with combined functional monomers.Journal of Lanzhou university(natural sciences),2014(1):136-144..
[14]高杨,王伟,刘英姿,等.盐酸金霉素分子印迹电化学传感器的研制.分析化学,2015,43(2):212-217.Gao Y,Wang W,Liu Y Z,et al.Development of molecularly imprinted electrochemical sensor for chlortetracycline hydrochloride.Analytical Chemistry,2015,43(2):212-217.