Detection of Carbendazim Residue in Apple Using Surface-Enhanced Raman Scattering Labeling Immunoassay
HUANG Xiao-wei1, ZHANG Ning1, LI Zhi-hua1, SHI Ji-yong1, SUN Yue1, ZHANG Xin-ai1, ZOU Xiao-bo1, 2*
1. School of Agricultural Engineering, School of Food and Biological Engineering, Jiangsu University，Zhenjiang 212013, China
2. International Joint Research Laboratory of Intelligent Agriculture and Agri-Products Processing, Jiangsu Education Department，Zhenjiang 212013, China
摘要： 多菌灵（Carbendazim，甲基-1H-2-苯并咪唑氨基甲酸酯）是一种内吸性广谱杀菌剂，广泛应用于苹果种植过程中的轮纹病和褐斑防治，若不合理使用会在苹果中残留危害消费者身体健康。采用表面增强拉曼光谱免疫分析技术（surface-enhance Raman spectroscopy combined immunoassay, SERSIA），以SERS高灵敏度和分子“指纹”图谱特性为基础，结合免疫特异选择性，实现苹果中多菌灵的微/痕量检测。制备核-分子-壳“三明治式”结构的Au@M@Ag 纳米SERS材料和结合抗原的SERS免疫探针，在包被抗体的Fe3O4磁性纳米材料可分离功能下，实现多菌灵的特异性检测。采用透射电镜（transmission electron microscope，TEM）、紫外-可见光谱和拉曼光谱等方法对制备的材料进行表征并优化了实验参数。研究表明多菌灵浓度与标记分子4-巯基苯甲腈的2 227 cm-1处特征峰强度值在0.5～300 nmol·L-1范围内具有良好的线性关系，同时该免疫探针信号具有良好的稳定性和重现性。对不同加标浓度的苹果实际样本进行检测，得到的平均回收率为95.6%～98.3%，相对标准偏差（relative standard deviation，RSD）为0.15%～0.99%。该方法操作简单，检测灵敏度高、选择性强、稳定性好，为苹果中痕量多菌灵的检测提供了新的方法。
关键词：表面增强拉曼光谱；免疫分析技术；多菌灵；苹果；快速检测
Abstract：Carbendazim (Methyl-1H-2-benzimidazole carbamate),a kind of broad-spectrum fungicide, is extensively used in the prevention and treatment of ring rot and brown spot in apple planting. However, excessive use and residue of Carbendazim induce toxic effects on humans.In order to rapidly and accurately detect Carbendazim in apples, the Surface-Enhance Raman Spectroscopy combined immunoassay (SERSIA) was used in this study. This method was based on SERS’s highly sensitive molecular “fingerprint” characteristics, combined with immunospecific selectivity. The core-molecule-shell “sandwich” structure of Au@M@Ag nano SERS material and SERS immune probe binding antigen were prepared. Combined with Fe3O4 magnetic nanomaterial coated antibody,the specific detection of Carbendazim was achieved with the separable function.Transmission electron microscopy (TEM), UV-Vis spectroscopy and Raman spectroscopy were used to characterize the material properties and optimize the experimental parameters.The results showed a good linear relationship between 0.5～300 nmol·L-1 carbendazim concentration and the intensity of Characteristic peak at 2 227 cm-1 of the labeled molecule 4-mercaptobenzonitrile. The average recovery of Carbendazim in apples with different spiked concentrations was 95.6%～98.3%, and the RSD value was 0.15%～0.99%. Itis a sensitive, selective and stable method for detecting Carbendazim in apples without complex pretreatment.
黄晓玮，张 宁，李志华，石吉勇，孙 悦，张新爱，邹小波. 基于SERS标记免疫分析技术苹果中多菌灵的检测方法[J]. 光谱学与光谱分析, 2023, 43(05): 1478-1484.
HUANG Xiao-wei, ZHANG Ning, LI Zhi-hua, SHI Ji-yong, SUN Yue, ZHANG Xin-ai, ZOU Xiao-bo. Detection of Carbendazim Residue in Apple Using Surface-Enhanced Raman Scattering Labeling Immunoassay. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(05): 1478-1484.
