有机磷农药残留的表面增强拉曼光谱快速检测
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摘要
农药残留严重影响人类身体健康与生命安全,故亟需建立一种简单高效的农药残留快速检测方法。本文以金纳米溶胶作为表面增强拉曼光谱(SERS)的增强基底,结合便携式拉曼光谱仪,实现了倍硫磷与对硫磷等常用有机磷农药的多靶标同时检测。结果表明倍硫磷和对硫磷分别在1053 cm~(-1),1216 cm~(-1)和857 cm~(-1),1112 cm~(-1)处具有特征拉曼谱峰,且两者互不干扰。同时进一步研究表明,倍硫磷和对硫磷的浓度与其特征拉曼谱峰强度线性相关,故可实现定量检测,其中倍硫磷检测限可达0.01μg/mL对硫磷检测限可达0.025μg/mL。同时,该SERS方法可直接用于菠菜实际样品中多种农药残留的多靶标快速检测,检测限达到0.05μg/mL。该SERS方法具有方便、快速、灵敏度高、多靶标同时检测等优点,有望实现农药残留的现场快速检测。
Pesticide residue is a significant problem in agriculture that greatly affects human health and life safety.Therefore,it is an urgent need to develop simple and effective method for the rapid detection of trace pesticide residue.In this work,combined with a portable Raman spectrometer,a surface-enhanced Raman spectroscopy(SERS)method was developed to achieve the rapid detection of trace organophosphorus pesticides including fenthion and parathion using gold sols as the SERS substrate.It was found that the characteristic Raman peaks of fenthion and parathion located at 1053 cm~(-1),1216 cm~(-1) and 857 cm~(-1),1112 cm~(-1),respectively,thus enabling the multi-target analysis simultaneously.The concentrations of fenthion and parathion display a linear relationship with their corresponding Raman intensities with a detection limit of fenthion can reach 0.01 μg/mL and parathion can reach 0.025 μg/mL.Furthermore,the SERS method developed here was successfully applied in the direct detection of fenthion and parathion residue on practical spinach samples with a detection limit of 0.05 μg/mL.This work demonstrates that SERS can be a convenient,rapid,sensitive and multi-target analysis method for the on-site detection of pesticide residues.
Pesticide residue is a significant problem in agriculture that greatly affects human health and life safety.Therefore,it is an urgent need to develop simple and effective method for the rapid detection of trace pesticide residue.In this work,combined with a portable Raman spectrometer,a surface-enhanced Raman spectroscopy(SERS)method was developed to achieve the rapid detection of trace organophosphorus pesticides including fenthion and parathion using gold sols as the SERS substrate.It was found that the characteristic Raman peaks of fenthion and parathion located at 1053 cm~(-1),1216 cm~(-1) and 857 cm~(-1),1112 cm~(-1),respectively,thus enabling the multi-target analysis simultaneously.The concentrations of fenthion and parathion display a linear relationship with their corresponding Raman intensities with a detection limit of fenthion can reach 0.01 μg/mL and parathion can reach 0.025 μg/mL.Furthermore,the SERS method developed here was successfully applied in the direct detection of fenthion and parathion residue on practical spinach samples with a detection limit of 0.05 μg/mL.This work demonstrates that SERS can be a convenient,rapid,sensitive and multi-target analysis method for the on-site detection of pesticide residues.
引文
[1] LI L,WU C,CHEN J,et al.Determination of organophosphorus pesticides residues in vegetables by gas chromatography using back-flush technique[J].Se Pu,2010,28(7):724-748.
[2] 张进平,刘文卫,周润,等.气相色谱法同时检测生活饮用水中的27种有机磷农药残留[J].中国卫生检验杂志,2009,20(3):527-528.(ZHANG Jinping,LIU Wenwei,ZHOU Run,et al.Simultaneous determination of 27 organophosphorus pesticides residues in drinking water by gas chromatography[J].Chinese Journal of Health Laboratory Technology,2010,20(3):527-528).
[3] HE L,LUO X,XIE H,et al.Ionic liquid-based dispersive liquid-liquid microextraction followed high-performance liquid organophosphorus pesticides in water sample[J].Analytica Chimica Acta,2009,655(12):59-62.
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[6] 李树平,解启文,杨良保,等.基于便携式拉曼光谱仪的疑似吸毒人员尿液中毒品的SERS快速检测[J].光散射学报,2018,30(2):116-119.(LI Shuping,XIE Qiwen,YANG Liangbao,et al.SERS Rapid Detection of Drugs in Urine of Suspected Drug Addicts Based on portable Raman spectrometer[J].The Journal of Light Scattering 2018,30(2):116-119).
[7] LI Z B,MENG G W,LI F D,et al.Ag Nanoparticle-Grafted PAN-Nanohump Array Films with 3D High-Density Hot Spots as Flexible and Reliable SERS Substrates[J].Small,2015,40(11):5452-5459.
[8] NOPPADON N,PITAK E,PONGPAN C,et al.Detection of methamphetamine amphetamine in human urine based on surface-enhanced Raman spectroscopy and acidulation treatments[J].Sens Actuators B,2017,239:139-146.
[9] VINESH R,Maria V,THOMAS K,et al.Surface-enhanced Raman spectroscopy for trace identification of controlled substances:morphine,codeine,and hydrocodone[J].Journal of Forensic Sciences,2011,56(3):201-205.
[10] WANG Y H,ZHANG Y J,Li J F,et al.Probing interfacial electronic and catalytic properties on well-defined surfaces using in situ Raman spectroscopy[J].Angewandte Chemie International Edition,2018,130(35):11427-11431.
[11] 周侠,张莉,杨良保,等.Au-Ag合金纳米海胆结构用于农药残留的SERS检测[J].光散射学报,2017,29(4):310-313.(ZHOU Xia,ZHANG Li,YANG Liangbao,et al.SERS Detection of Pesticide Residues by Au-Ag Alloy Nanourchin Structure[J].The Journal of Light Scattering,2017,29(4):310-313).
[12] 徐莹,杜一平,吴婷,等.修饰的氨基改性粉末多孔材料作为表面增强拉曼光谱基底用于检测有机磷农药的研究[J].光散射学报,2014,26(2):165-169.(XU Yin,DU Yiping,WU Ting,et al.Sliver decorated of amino-modified powdered porous material as SERS substrate for detection of organophosphorus pesticides[J].The Journal of Light Scattering,2014,26(2):165-169).
[13] 靳美会,宋宛营,蔡红星,等.农药草甘膦的拉曼光谱计算及分析[J].光散射学报,2013,25(2):164-169.(JIN Meihui,SONG Wanying,CAI Hongxing,et al.Raman spectrum calculation and analysis of pesticide glyphosate[J].The Journal of Light Scattering,2013,25(2):164-169).
[14] XU Q,GUO X Y,YANG H F,et al.Template-free synthesis of SERS-active gold nanopopcorn for rapid detection of chlorpyrifos residues[J].Sensors and Actuators B:Chemical,2017,241:1008-1013.
[15] LI X Z,ZHANG S,YANG T Y.Surface-enhanced Raman Spectroscopic analysis of phorate and fenthion pesticide in apple skin using sliver nanoparticles[J].Applied Spectroscopy,2014,68(4):483-487.
[16] CHEN J M,HUANG Y J,GUO L H,et al.Flexible and adhesive surface enhance Raman scattering active tape for rapid detection of pesticide residues in fruits and vegetables[J].Analytical Chemistry,2016,88:2149-2155.
[2] 张进平,刘文卫,周润,等.气相色谱法同时检测生活饮用水中的27种有机磷农药残留[J].中国卫生检验杂志,2009,20(3):527-528.(ZHANG Jinping,LIU Wenwei,ZHOU Run,et al.Simultaneous determination of 27 organophosphorus pesticides residues in drinking water by gas chromatography[J].Chinese Journal of Health Laboratory Technology,2010,20(3):527-528).
[3] HE L,LUO X,XIE H,et al.Ionic liquid-based dispersive liquid-liquid microextraction followed high-performance liquid organophosphorus pesticides in water sample[J].Analytica Chimica Acta,2009,655(12):59-62.
[4] HOU R,TONG M M,HE L L,et al.Investigation of degradation and penetration behaviors of dimethoate on and in spinach leaves using in situ SERS and LC-MS[J].Food Chemistry,2007,15:1760-1766.
[5] SHAMSIPUR M,YAZDANFAR N,GHAMBARIAN M.Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water,milk,honey and fruit juice[J].Food Chemistry,204:289-297.
[6] 李树平,解启文,杨良保,等.基于便携式拉曼光谱仪的疑似吸毒人员尿液中毒品的SERS快速检测[J].光散射学报,2018,30(2):116-119.(LI Shuping,XIE Qiwen,YANG Liangbao,et al.SERS Rapid Detection of Drugs in Urine of Suspected Drug Addicts Based on portable Raman spectrometer[J].The Journal of Light Scattering 2018,30(2):116-119).
[7] LI Z B,MENG G W,LI F D,et al.Ag Nanoparticle-Grafted PAN-Nanohump Array Films with 3D High-Density Hot Spots as Flexible and Reliable SERS Substrates[J].Small,2015,40(11):5452-5459.
[8] NOPPADON N,PITAK E,PONGPAN C,et al.Detection of methamphetamine amphetamine in human urine based on surface-enhanced Raman spectroscopy and acidulation treatments[J].Sens Actuators B,2017,239:139-146.
[9] VINESH R,Maria V,THOMAS K,et al.Surface-enhanced Raman spectroscopy for trace identification of controlled substances:morphine,codeine,and hydrocodone[J].Journal of Forensic Sciences,2011,56(3):201-205.
[10] WANG Y H,ZHANG Y J,Li J F,et al.Probing interfacial electronic and catalytic properties on well-defined surfaces using in situ Raman spectroscopy[J].Angewandte Chemie International Edition,2018,130(35):11427-11431.
[11] 周侠,张莉,杨良保,等.Au-Ag合金纳米海胆结构用于农药残留的SERS检测[J].光散射学报,2017,29(4):310-313.(ZHOU Xia,ZHANG Li,YANG Liangbao,et al.SERS Detection of Pesticide Residues by Au-Ag Alloy Nanourchin Structure[J].The Journal of Light Scattering,2017,29(4):310-313).
[12] 徐莹,杜一平,吴婷,等.修饰的氨基改性粉末多孔材料作为表面增强拉曼光谱基底用于检测有机磷农药的研究[J].光散射学报,2014,26(2):165-169.(XU Yin,DU Yiping,WU Ting,et al.Sliver decorated of amino-modified powdered porous material as SERS substrate for detection of organophosphorus pesticides[J].The Journal of Light Scattering,2014,26(2):165-169).
[13] 靳美会,宋宛营,蔡红星,等.农药草甘膦的拉曼光谱计算及分析[J].光散射学报,2013,25(2):164-169.(JIN Meihui,SONG Wanying,CAI Hongxing,et al.Raman spectrum calculation and analysis of pesticide glyphosate[J].The Journal of Light Scattering,2013,25(2):164-169).
[14] XU Q,GUO X Y,YANG H F,et al.Template-free synthesis of SERS-active gold nanopopcorn for rapid detection of chlorpyrifos residues[J].Sensors and Actuators B:Chemical,2017,241:1008-1013.
[15] LI X Z,ZHANG S,YANG T Y.Surface-enhanced Raman Spectroscopic analysis of phorate and fenthion pesticide in apple skin using sliver nanoparticles[J].Applied Spectroscopy,2014,68(4):483-487.
[16] CHEN J M,HUANG Y J,GUO L H,et al.Flexible and adhesive surface enhance Raman scattering active tape for rapid detection of pesticide residues in fruits and vegetables[J].Analytical Chemistry,2016,88:2149-2155.