硼掺杂分子印迹聚合物修饰电化学传感器测定水产品中孔雀石绿

职业与健康 ›› 2024, Vol. 40 ›› Issue (14): 1895-1899.

硼掺杂分子印迹聚合物修饰电化学传感器测定水产品中孔雀石绿

琚赛琴, 杨振兴, 梁万超, 覃明林

柳州市疾病预防控制中心理化检验所,广西柳州 545007

收稿日期:2024-03-19 修回日期:2024-04-07 发布日期:2026-03-17
通信作者: 杨振兴,副主任技师,E-mail：690621583@qq.com
作者简介:琚赛琴,女,主管技师,主要从事卫生理化检验工作。

Determination of malachite green in aquatic products by boron doped molecularly imprinted polysiloxanemer modified electrochemical sensor

JU Saiqin, YANG Zhenxing, LANG Wanchao, QIN Minglin

Physical and Chemical Laboratory, Liuzhou Center for Disease Control and Prevention, Liuzhou, Guangxi 545007, China

Received:2024-03-19 Revised:2024-04-07 Published:2026-03-17
Contact: YANG Zhenxing,Deputy chief technician,E-mail：690621583@qq.com

摘要/Abstract

摘要： 目的建立基于硼掺杂表面分子印迹聚合物（boron doped molecularly imprinted polysiloxanemer,BMIP）修饰碳糊电极（carbon paste electrode,CPE）构建的电化学传感器测定水产品中孔雀石绿（malachite green,MG）含量的检测方法。方法以苯基三甲氧基硅烷和甲基三甲氧基硅烷为功能单体,MG为模板分子,间氨基苯硼酸为掺杂剂,四乙氧基硅烷为交联剂合成BMIP,并用BMIP对CPE进行修饰,构建BMIP-CPE检测水产品中MG的含量。结果通过优化功能单体、掺杂剂、交联剂用量以及洗脱剂、富集时间等实验参数,在最佳条件下,采用差分脉冲伏安法测得水产品中MG的线性范围为0.2~60.0 μmol/L,相关系数为0.999 2,检测限为0.075 μmol/L,BMIP-CPE具有良好的稳定性和识别选择性,将本方法应用于市售鱼虾等水产品MG的检测,加标回收率为90.2%~97.8%,并与高效液相色谱法进行比较,结果差异无统计学意义（P>0.05）。结论硼掺杂分子印迹聚合物修饰电化学传感器测定水产品中的MG检测方法操作简单快捷,线性范围良好,特异性和准确度高,适用于水产品中MG的测定。

关键词: 水产品, 孔雀石绿, 硼掺杂表面分子印迹聚合物, 碳糊电极, 差分脉冲伏安法

Abstract: Objective To establish a new method for the determination of malachite green（MG） in aquatic products using the electrochemical sensor that was constructed by modifying carbon paste electrode（CPE） using boron doped molecularly imprinted polysiloxanemer（BMIP）. Methods BMIP was synthesized using phenyltrimethoxysilane and methyltrimethoxysilane as functional monomers, MG as template molecule,meta aminophenylboronic acid as dopant,and tetraethoxysilane as crosslinking agent. BMIP was used to modify CPE and construct electrochemical sensor（BMIP-CPE） for detecting MG content in aquatic products. Results By optimizing the dosage of functional monomers,dopants,crosslinking agents,eluents,enrichment time and other experimental parameters,under optimal conditions,the linear range of MG in aquatic products was determined to be 0.2-60.0 μmol/L using differential pulse voltammetry,with a correlation coefficient of 0.999 2 and a detection limit of 0.075 μmol/L. In addition,the BMIP-CPE showed enough stability and good reproducibility. This method was applied to the detection of MG in commercially available aquatic products such as fish and shrimp,with an acceptable recoveries of 90.2% to 97.8%. The results were compared with high performance liquid chromatography,and the difference was not statistically significant（P>0.05）. Conclusion The BMIP modified electrochemical sensor is a simple and fast method for detecting MG in aquatic products,with good linear range,high specificity and accuracy,and is suitable for the determination of MG in aquatic products.

Key words: Aquatic products, Malachite green, Boron doped molecularly imprinted polysiloxanemer, Carbon paste electrode, Differential pulse voltammetry

中图分类号:

R115

琚赛琴, 杨振兴, 梁万超, 覃明林. 硼掺杂分子印迹聚合物修饰电化学传感器测定水产品中孔雀石绿. [J]职业与健康, 2024, 40(14): 1895-1899.

JU Saiqin, YANG Zhenxing, LANG Wanchao, QIN Minglin. Determination of malachite green in aquatic products by boron doped molecularly imprinted polysiloxanemer modified electrochemical sensor. [J]OCCUPATION AND HEALTH, 2024, 40(14): 1895-1899.

参考文献

[1] HOJJATI-NAJAFABADI A,ESFAHANI P N,DAVAR F,et al.Adsorptive removal of malachite green using novel GO@ZnO-NiFe₂O₄-αAl₂O₃ nanocomposites[J].Chem Eng J,2023,471:144485.
[2] OPLATOWSKA M,CONNOLLY L,STEVENSON P,et al.Development and validation of a fast monoclonal based disequilibrium enzyme-linked immunosorbent assay for the detection of triphenylmethane dyes and their metabolites in fish[J].Anal Chim Acta,2011,698(1-2):51-60.
[3] NANJAPPA M D,JAYAPRAKASH G K.Some progress in voltammetric methods to detect malachite green in real samples using carbon electrodes[J].J Electrochem Sci En,2023,13(3):437-449.
[4] MITROWSKA K,POSYNIAK A,ZMUDZKI J.Determination of malachite green and leucomalachite green residues in water using liquid chromatography with visible and fluorescence detection and confirmation by tandem mass spectrometry[J].J Chromatogr A,2008,1207(1-2):94-100.
[5] CULP S J,BELAND F A.Malachite green a toxicological review[J].J Am Coll Toxicol,1996,15(3):219-238.
[6] ZHOU X H,ZHANG J R,PAN Z L,et al.Review of methods for the detection and determination of malachite green and leuco-malachite green in aquaculture[J].Crit Rev Anal Chem,2019,49(1):1-20.
[7] HURTAUD-PESSEL D,COUEDOR P,VERDON E.Liquid chromatography-tandem mass spectrometry method for the determination of dye residues in aquaculture products:Development and validation[J].J Chromatogr A,2011,1218(12):1632-1645.
[8] XU H Y,CHEN X L,GUO L,et al.Monoclonal antibody-based enzyme-linked immunosorbent assay for detection of total malachite green and crystal violet residues in fishery products[J].Int J Environ An Ch,2013,93(9):959-969.
[9] ZHANG Y,YANG J Y,LEI H T,et al.Development of chemiluminescent enzyme immunoassay for the determination of malachite green in seafood[J].Food Agr Immunol,2015,26(2):204-217.
[10] TSAI C H,LIN J D,LIN C H.Optimization of the separation of malachite green in water by capillary electrophoresis Raman spectroscopy (CE-RS)based on the stacking and sweeping modes[J].Talanta,2007,72(2):368-372.
[11] 梁高道,麦琦.气相色谱质谱法确认水产品中的孔雀石绿[J].公共卫生与预防医学,2009,20(6):69-71.
[12] 林功师. 超高效液相色谱-串联质谱法测定鱼肉中孔雀石绿及其代谢物的残留量[J].渔业研究,2018,40(4):295-301.
[13] 高晓敏,王琚钢,马智玲,等.快速滤过型净化法结合超高效液相色谱-串联质谱同时检测水产品中孔雀石绿和结晶紫残留量[J].分析与检测,2021,47(24):249-255.
[14] CHEN Y P,XIA S D,HAN X Q,et al.Simultaneous determination of malachite green,chloramphenicols,sulfonamides,and fluoroquinolones residues in fish by liquid chromatography-mass spectrometry[J].J Anal Methods Chem,2020,2020:3725618.
[15] 孟二琼,念琪循,李峰,等.磺酸化磁性氮化碳固相萃取-超高液相色谱-串联质谱筛检淡水鱼中孔雀石绿和隐色孔雀石绿[J].色谱,2023
41(8):673-682.
[16] 王权帅,孙卫明.虹鳟鱼中孔雀石绿、结晶紫及其代谢物残留量的超高效液相色谱-串联质谱测定法[J].职业与健康,2021,37(12):1627-1630.
[17] YUE X Y,FU L,LI Y,et al.Lanthanide bimetallic MOF-based fluorescent sensor for sensitive and visual detection of sulfamerazine and malachite[J].Food Chem,2023,410:135390.
[18] YUE X Y,LI Y,XU S,et al.A portable smartphone-assisted ratiometric fluorescence sensor for intelligent and visual detection of malachite green[J].Food Chem,2022,371:131164.
[19] 陈宏,靖玉,孙思阳,等.分子印迹电化学传感器检测水产品中孔雀石绿[J].化学研究与应用,2020,32(2):208-213.
[20] 韦寿莲,吴嘉喻,黄象金,等.孔雀石绿分子印迹电化学传感器的制备与应用[J].分析化学,2020,48(1):145-152.
[21] 谢春生,唐青,卢婕婕,等.孔雀石绿电化学传感器修饰材料研究进展[J].分析实验室,2022,41(8):977-983.
[22] 陈威风,李青静,刘志景,等.孔雀石绿分子印迹电化学传感器的制备与应用[J].食品安全质量检测学报,2021,12(22):8797-8803.
[23] HU C H,DENG J,ZHAO Y B,et al.A novel core-shell magnetic nano-sorbent with surface molecularly imprinted polymer coating for the selective solid phase extraction of dimetridazole[J].Food Chem,2014,158:366-373.
[24] JU S Q,DENG J,CHENG J L,et al.Determination of leucomalachite green,leucocrystal violet and their chromic forms using excitation-emission matrix fluorescence coupled with second-order calibration after dispersive liquid-liquid microextraction[J].Food Chem,2015,185:479-487.
[25] 琚赛琴. 水产品及环境水中三苯甲烷类染料检测新方法研究[D].衡阳:南华大学,2015.
[26] HE Y,LEE H K.Orthogonal array design experiments for optimizing the separation of various pesticides by cyclodextrin-modified micellar electrokinetic chromatography[J].J Chromatogr A,1998,793(2):331-340.