叶菜中多类农药残留的SERS快速无损检测
|
摘要
有机磷、有机硫和烟碱类农药常应用于叶菜的种植和生产中,常规的检测方法前处理复杂、检测时间长、成本高等特点,难以满足快速检测的需求,为了实现农药残留的在线检测,本文提出一个基于SERS技术进行定量和定性分析叶菜中农药残留的检测方法,选取农药的特征拉曼峰作为校正峰,制定农药残留的浓度与校正峰强度的线性校准方程,将最低检测限对应SERS光谱的校正峰的强度代入线性校准方程,计算出定量检测限。研究表明,小白菜中亚胺硫磷农药的检测限能达到0.5mg/kg以下,相关系数R~2为0.95273,标准偏差为2.89%～13.63%,回收率为96.00%～121.33%;大白菜中福美双农药残留的检测限能达到0.5mg/kg以下,相关系数R~2为0.8905,标准偏差为3.90%～8.39%,回收率为88.80%～112.44%;空心菜中啶虫脒农药残留的检测限能达到1mg/kg以下,相关系数R~2为0.93858,标准偏差为2.12%～9.29%,回收率为87.67%～107.17%。这些结果说明,基于SERS技术进行定量和定性分析叶菜中农药残留的检测方法是一种有效的方法,可以实现叶菜农药残留的快速无损检测。
Three kinds of pesticides, organic phosphorus, organosulfur and neonicotinoids were used widely in the cultivation and production of leaf vegetables. The chromatographic methods are difficult to realize in situ detection. In this work, a surface-enhanced Raman scattering(SERS) approach for qualitative and quantitative detection pesticide residues in leaf vegetables was developed. The characteristic Raman peaks of pesticides were selected as correction peaks. The linear calibration equations were established with pesticide residues concentration and correction peak intensity. The limit of quantitation(LOQ) was calculated by substituting the correction peak intensity of SERS spectrum corresponding to the limit of detection(LOD) into the linear calibration equation. The results showed that the LOD for phosmet residues in pakchoi reached below 0.5 mg/kg with the correction Raman peak of 604 cm~(-1), and the correlation coefficient R~2 was 0.95273, and the standard deviation(SD) was 2.89%～13.63%, the recovery rate was 96.00%～121.33%. The LOD for thiram residues in Chinese cabbage reached below 0.5 mg/kg with the correction Raman peak of 1385 cm~(-1), and R~2 was 0.8905, and SD was 3.90%～8.39%, the recovery rate was 88.80%～112.44%. The LOD for acetamiprid residues in swamp cabbage reached below 1 mg/kg with the correction Raman peak of 1111 cm~(-1),and R~2 was 0.93858, and SD was 2.12%～9.29%, the recovery rate was 87.67%～107.17%. These showed that the SERS method might be an effective method for the rapid and reliable detection of pesticide residues in leaf vegetables.
Three kinds of pesticides, organic phosphorus, organosulfur and neonicotinoids were used widely in the cultivation and production of leaf vegetables. The chromatographic methods are difficult to realize in situ detection. In this work, a surface-enhanced Raman scattering(SERS) approach for qualitative and quantitative detection pesticide residues in leaf vegetables was developed. The characteristic Raman peaks of pesticides were selected as correction peaks. The linear calibration equations were established with pesticide residues concentration and correction peak intensity. The limit of quantitation(LOQ) was calculated by substituting the correction peak intensity of SERS spectrum corresponding to the limit of detection(LOD) into the linear calibration equation. The results showed that the LOD for phosmet residues in pakchoi reached below 0.5 mg/kg with the correction Raman peak of 604 cm~(-1), and the correlation coefficient R~2 was 0.95273, and the standard deviation(SD) was 2.89%～13.63%, the recovery rate was 96.00%～121.33%. The LOD for thiram residues in Chinese cabbage reached below 0.5 mg/kg with the correction Raman peak of 1385 cm~(-1), and R~2 was 0.8905, and SD was 3.90%～8.39%, the recovery rate was 88.80%～112.44%. The LOD for acetamiprid residues in swamp cabbage reached below 1 mg/kg with the correction Raman peak of 1111 cm~(-1),and R~2 was 0.93858, and SD was 2.12%～9.29%, the recovery rate was 87.67%～107.17%. These showed that the SERS method might be an effective method for the rapid and reliable detection of pesticide residues in leaf vegetables.
引文
[1]李朝静,李培培,陈敏,等.高效液相色谱-荧光法同时检测葡萄汁中3种苯并咪唑类农药[J].食品科学,2016,37(12):192-196LI Chao-jing,LI Pei-pei,CHEN Min,et al.Simultaneous determination of three benzimidazole fungicide residues in grape juice by high performance liquid chromatography with fluorescence detector[J].Food Science,2016,37(12):192-196
[2]李丽春,刘书贵,尹怡,等.气相色谱法检测水产品中拟除虫菊酯类农药的基质效应研究[J].现代食品科技,2018,34(4):270-280LI Li-chun,LIU Shu-gui,YIN Yi,et al.Matrix effects of pyrethroid pesticides in aquatic products using gas chromatography[J].Modern Food Science and Technology,2018,34(4):270-280
[3]Santos Elias De Barros,Lima Elaine Cristina Nogueira Lopes,Oliveira Cristine Santos De,et al.Fast detection of paracetamol on a gold nanoparticle-chitosan substrate by SERS[J].Analytical Methods,2014,6(11):3564-3658
[4]TrouvéPascal,Calvez Marie-Laure,Moisan Stéphanie,et al.Rapid detection of the mature form of cystic fibrosis transmembrane regulator by surface plasmon resonance[J].Anal.Methods,2015,7(1):226-236
[5]Satheeshkumar Elumalai,Karuppaiya Palaniyandi,Sivashanmugan Kundan,et al.Biocompatible 3D SERSsubstrate for trace detection of amino acids and melamine[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2017,181:91-97
[6]Liou Polly,Nayigiziki Francois Xavier,Kong Fanbin,et al.Cellulose nanofibers coated with silver nanoparticles as a SERS platform for detection of pesticides in apples[J].Carbohydrate Polymers,2017,157:643-650
[7]Wang Kehui,Huang Meizhen,Chen Jie,et al.A“drop-wipe-test”SERS method for rapid detection of pesticide residues in fruits[J].Journal of Raman Spectroscopy,2018,49(3):493-498
[8]Clauson Susan L.,Sylvia James M.,Arcury Thomas A.,et al.Detection of pesticides and metabolites using surface-enhanced Raman spectroscopy(SERS):Acephate[J].Applied Spectroscopy,2015,69(7):785-793
[9]Liou Polly,Nayigiziki Francois Xavier,Kong Fanbin,et al.Cellulose nanofibers coated with silver nanoparticles as a SERS platform for detection of pesticides in apples[J].Carbohydrate Polymers,2017,157:643-650
[10]Clauson Susan L.,Sylvia James M.,Arcury Thomas A.,et al.Detection of pesticides and metabolites using surface-enhanced Raman spectroscopy(SERS):Acephate[J].Applied Spectroscopy,2015,69(7):785-793
[11]Sivashanmugan Kundan,Lee Han,Syu Chiu-Hua,et al.Nanoplasmonic Au/Ag/Au nanorod arrays as SERS-active substrate for the detection of pesticides residue[J].Journal of the Taiwan Institute of Chemical Engineers,2017,75:287-291
[12]Wang Mingli,Shi Guochao,Zhu Yanying,et al.Au-decorated dragonfly wing bioscaffold arrays as flexible surface-enhanced Raman scattering(SERS)substrate for simultaneous determination of pesticide residues[J].Nanomaterials,2018,8(5):289
[13]王晓彬,吴瑞梅,刘木华,等.叶菜中噻菌灵农药的SERS快速检测研究[J].核农学报,2014,28(10):1874-1879WANG Xiao-bin,WU Rui-mei,LIU Mu-hua,et al.Rapid detection of thiabendazole residues in vegetable leaves by surface-enhanced Raman spectroscopy[J].Journal of Nuclear Agricultural Sciences,2014,28(10):1874-1879
[14]Hou Ruyan,Pang Shintaro,He Lili.In situ SERS detection of multi-class insecticides on plant surfaces[J].Anal.Methods,2015,7(15):6325-6330
[15]黄双根,吴燕,胡建平,等.大白菜中马拉硫磷农药的表面增强拉曼光谱快速检测[J].农业工程学报,2016,6:296-301HUANG Shuang-gen,WU Yan,HU Jian-ping,et al.Rapid detection of malathion residuesin chinese cabbage by surface enhanced Raman spectroscopy[J].Transactions of the Chinese Society of Agricultural Engineering,2016,6:296-301
[16]Zhu Yiqun,Li Minqiang,Yu Daoyang,et al.A novel paper rag as‘D-SERS’substrate for detection of pesticide residues at various peels[J].Talanta,2014,128:117-124
[17]Tao Wenyu,Zhao Aiwu,Sun Henghui,et al.Periodic silver nanodishes as sensitive and reproducible surface-enhanced Raman scattering substrates[J].RSC Adv.,2014,4(7):3487-3493
[2]李丽春,刘书贵,尹怡,等.气相色谱法检测水产品中拟除虫菊酯类农药的基质效应研究[J].现代食品科技,2018,34(4):270-280LI Li-chun,LIU Shu-gui,YIN Yi,et al.Matrix effects of pyrethroid pesticides in aquatic products using gas chromatography[J].Modern Food Science and Technology,2018,34(4):270-280
[3]Santos Elias De Barros,Lima Elaine Cristina Nogueira Lopes,Oliveira Cristine Santos De,et al.Fast detection of paracetamol on a gold nanoparticle-chitosan substrate by SERS[J].Analytical Methods,2014,6(11):3564-3658
[4]TrouvéPascal,Calvez Marie-Laure,Moisan Stéphanie,et al.Rapid detection of the mature form of cystic fibrosis transmembrane regulator by surface plasmon resonance[J].Anal.Methods,2015,7(1):226-236
[5]Satheeshkumar Elumalai,Karuppaiya Palaniyandi,Sivashanmugan Kundan,et al.Biocompatible 3D SERSsubstrate for trace detection of amino acids and melamine[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2017,181:91-97
[6]Liou Polly,Nayigiziki Francois Xavier,Kong Fanbin,et al.Cellulose nanofibers coated with silver nanoparticles as a SERS platform for detection of pesticides in apples[J].Carbohydrate Polymers,2017,157:643-650
[7]Wang Kehui,Huang Meizhen,Chen Jie,et al.A“drop-wipe-test”SERS method for rapid detection of pesticide residues in fruits[J].Journal of Raman Spectroscopy,2018,49(3):493-498
[8]Clauson Susan L.,Sylvia James M.,Arcury Thomas A.,et al.Detection of pesticides and metabolites using surface-enhanced Raman spectroscopy(SERS):Acephate[J].Applied Spectroscopy,2015,69(7):785-793
[9]Liou Polly,Nayigiziki Francois Xavier,Kong Fanbin,et al.Cellulose nanofibers coated with silver nanoparticles as a SERS platform for detection of pesticides in apples[J].Carbohydrate Polymers,2017,157:643-650
[10]Clauson Susan L.,Sylvia James M.,Arcury Thomas A.,et al.Detection of pesticides and metabolites using surface-enhanced Raman spectroscopy(SERS):Acephate[J].Applied Spectroscopy,2015,69(7):785-793
[11]Sivashanmugan Kundan,Lee Han,Syu Chiu-Hua,et al.Nanoplasmonic Au/Ag/Au nanorod arrays as SERS-active substrate for the detection of pesticides residue[J].Journal of the Taiwan Institute of Chemical Engineers,2017,75:287-291
[12]Wang Mingli,Shi Guochao,Zhu Yanying,et al.Au-decorated dragonfly wing bioscaffold arrays as flexible surface-enhanced Raman scattering(SERS)substrate for simultaneous determination of pesticide residues[J].Nanomaterials,2018,8(5):289
[13]王晓彬,吴瑞梅,刘木华,等.叶菜中噻菌灵农药的SERS快速检测研究[J].核农学报,2014,28(10):1874-1879WANG Xiao-bin,WU Rui-mei,LIU Mu-hua,et al.Rapid detection of thiabendazole residues in vegetable leaves by surface-enhanced Raman spectroscopy[J].Journal of Nuclear Agricultural Sciences,2014,28(10):1874-1879
[14]Hou Ruyan,Pang Shintaro,He Lili.In situ SERS detection of multi-class insecticides on plant surfaces[J].Anal.Methods,2015,7(15):6325-6330
[15]黄双根,吴燕,胡建平,等.大白菜中马拉硫磷农药的表面增强拉曼光谱快速检测[J].农业工程学报,2016,6:296-301HUANG Shuang-gen,WU Yan,HU Jian-ping,et al.Rapid detection of malathion residuesin chinese cabbage by surface enhanced Raman spectroscopy[J].Transactions of the Chinese Society of Agricultural Engineering,2016,6:296-301
[16]Zhu Yiqun,Li Minqiang,Yu Daoyang,et al.A novel paper rag as‘D-SERS’substrate for detection of pesticide residues at various peels[J].Talanta,2014,128:117-124
[17]Tao Wenyu,Zhao Aiwu,Sun Henghui,et al.Periodic silver nanodishes as sensitive and reproducible surface-enhanced Raman scattering substrates[J].RSC Adv.,2014,4(7):3487-3493