化学学报 ›› 2013, Vol. 71 ›› Issue (02): 221-226.DOI: 10.6023/A12100831 上一篇    下一篇

研究论文

表面增强拉曼光谱检测鱼肉中禁用和限用药物研究

李春颖, 赖克强, 张源园, 裴鹭, 黄轶群   

  1. 上海海洋大学食品学院 上海 201306
  • 投稿日期:2012-10-28 发布日期:2013-01-04
  • 通讯作者: 黄轶群 E-mail:yqhuang@shou.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 61250002, 31250006);上海市浦江人才计划(No. 09PJ1405200)和上海市科学技术委员会部分地方院校能力建设(No. 09320503800)资助.

Use of Surface-enhanced Raman Spectroscopy for the Test of Residuals of Prohibited and Restricted Drugs in Fish Muscle

Li Chunying, Lai Keqiang, Zhang Yuanyuan, Pei Lu, Huang Yiqun   

  1. College of Food Science and Technology, Shanghai Ocean University, Shanghai 201306
  • Received:2012-10-28 Published:2013-01-04
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 61250002, 31250006), Science and Technology Commission of Shanghai Municipality (Nos. 09PJ1405200, 09320503800).

应用表面增强拉曼光谱(surface-enhanced Raman spectroscopy, SERS)技术, 结合化学计量学方法对水产品中常被检出的禁用或限用药物, 包括孔雀石绿(0.5~50 μg/L)、结晶紫(5~100 μg/L)、氯霉素(50~5.0×103 μg/L)和磺胺甲基嘧啶(500~5.0×103 μg/L)进行检测. 采用偏最小二乘回归法(partial least squares regression, PLSR)对谱图进行分析处理, 建立定量分析模型. 结果表明运用SERS技术对染料类渔药, 孔雀石绿和结晶紫的分析效果较好, 对于其标准溶液的最低检测浓度分别为0.8和10 μg/L; 对抗生素药物, 氯霉素和磺胺甲基嘧啶的最低检测浓度分别为50和500 μg/L. 4种药物的PLSR模型的预测值与实际值的R2为0.865~0.954. 运用SERS技术最低能检测到鱼肉中孔雀石绿和结晶紫的含量分别为1.0和20 μg/kg, 显示出SERS技术对食品中痕量药物残留检测的巨大潜力.

关键词: 孔雀石绿, 结晶紫, 氯霉素, 磺胺甲基嘧啶, 表面增强拉曼光谱, 鱼肉

The objective of this study was to investigate the feasibility of applying surface-enhanced Raman spectroscopy (SERS) coupled with partial least squares regression (PLSR) to detect and determine prohibited or restricted residual fish drugs including malachite green, crystal violet, chloramphenicol and sulfamerazine. Standard solutions of malachite green (0.5~50 μg/L), crystal violet (5~100 μg/L), chloramphenicol (50~5.0×103 μg/L) and sulfamerazine (500~5.0×103 μg/L) were used to determine the sensibility of the SERS method as well as the accuracy of the PLSR models for quantitative analyses of the fish drugs. In addition, fish muscles artificially contaminated with malachite green (0.5~50 μg/kg) or crystal violet (10~100 μg/kg) were used for the study. Two different types of commercial gold-coated SERS substrates were used to acquire SERS spectra (400~2000 cm-1) of standard solutions or fish extracts. Then, laser source (633 and 780 nm) and laser power (5 and 10 mW) were varied for optimum results to collect spectra of different drugs. PLSR was applied for quantitative analysis of the tested fish drugs. The results indicated that SERS technology is a sensitive method for analyzing industrial dyes, which could detect malachite green and crystal violet at concentration levels as low as 0.8 and 10 μg/L, respectively. For chloramphenicol and sulfamerazine, the lowest concentrations could be detected were 50 and 500 μg/L, respectively. The PLSR models for four standard solutions yielded R2 of 0.865 to 0.954. For malachite green and crystal violet extracts from fish, the lowest concentrations detected were 1.0 and 20 μg/kg, respectively, which indicated great potential of applying SERS in determination of residual prohibited or restricted fish drugs in food system.

Key words: malachite green, crystal violet, chloramphenicol, sulfamerazine, surface-enhanced Raman spectroscopy, fish muscle