表面增强拉曼散射技术对白酒中克百威残留的定性检测
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摘要
建立表面增强拉曼散射(surface enhanced Raman scattering,SERS)技术对白酒中的克百威残留进行定性检测方法。制备金溶胶(Au nanoparticles,Au NPS)和不同Ag壳厚度的银包金纳米粒子(Au@Ag NPS),通过探测分子罗丹明B(R6G)比较Au NPS和不同Ag壳厚度Au@Ag NPS的SERS增强效果;碱性条件下,向克百威分子引入标记物2,6-二氯醌-4-氯亚胺,再与增强效果较好的NPS按比例混合进行拉曼测试,讨论SERS信号采集条件,并对拉曼谱峰进行比较和归属,计算克百威在Au@Ag NPS增强基底上的增强因子。结果表明:克百威、标记物和Au@Ag NPS的比例为1∶0.225∶7,约7 nm Ag壳厚度Au@Ag NPS效果最好,克百威的检测下限为1×10~(-16) mol/L,Au@Ag NPS增强因子为2×10~8,用此方法检测3种市售白酒中均含有微量的克百威,方法快速、简便、结果可靠。
In this paper, a surface-enhanced Raman scattering(SERS) method was established for the detection of carbofuran residues in Chinese liquor. Au nanoparticles(Au NPS) and Au-core/Ag-shell nanoparticles(Au@Ag NPS) with different thicknesses of Ag shell were prepared, and then their SERS performance were comparatively evaluated by the dye molecule rhodamine 6 G(R6 G). In alkaline solution, 2,6-dichloroquinone-4-chloroimide as a marker was introduced to carbofuran, and then mixed with the nanoparticles that had better SERS performance in a certain proportion. We optimized the conditions for SERS signal acquisition, compared and attributed the Raman peaks, and estimated the enhancement factor of carbofuran on NPS enhanced substrate. The results showed that Au@Ag NPS with a 7 nm thick Ag shell possessed the best SERS effect, and therefore could be used as the SERS substrate. The limit of detection of carbofuran was 1 × 10~(-16) mol/L and the enhancement factor of Au@Ag NPS was 2 × 10~8. Trace carbofuran in all three kinds of commercial Chinese liquor was detected rapidly, simply and reliably by this method.
In this paper, a surface-enhanced Raman scattering(SERS) method was established for the detection of carbofuran residues in Chinese liquor. Au nanoparticles(Au NPS) and Au-core/Ag-shell nanoparticles(Au@Ag NPS) with different thicknesses of Ag shell were prepared, and then their SERS performance were comparatively evaluated by the dye molecule rhodamine 6 G(R6 G). In alkaline solution, 2,6-dichloroquinone-4-chloroimide as a marker was introduced to carbofuran, and then mixed with the nanoparticles that had better SERS performance in a certain proportion. We optimized the conditions for SERS signal acquisition, compared and attributed the Raman peaks, and estimated the enhancement factor of carbofuran on NPS enhanced substrate. The results showed that Au@Ag NPS with a 7 nm thick Ag shell possessed the best SERS effect, and therefore could be used as the SERS substrate. The limit of detection of carbofuran was 1 × 10~(-16) mol/L and the enhancement factor of Au@Ag NPS was 2 × 10~8. Trace carbofuran in all three kinds of commercial Chinese liquor was detected rapidly, simply and reliably by this method.
引文
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[7]孙航,蒋煜峰,胡雪菲,等.添加生物炭对西北黄土吸附克百威的影响[J].环境科学学报,2016,36(3):1015-1020.DOI:10.13671/j.hjkxxb.2015.0572.
[8]郑彬,温宝英,苏立众,等.表面增强拉曼光谱快速检测尿液中的尿酸[J].光谱学与光谱分析,2017,37(6):1789-1792.DOI:10.3964/j.issn.1000-0593(2017)06-1789-04.
[9]左奇,陈瑶,石彩霞,等.表面增强拉曼散射光谱定量分析技术的研究进展[J].分析化学,2015(11):1656-1663.DOI:10.11895/j.issn.0253-3820.150597.
[10]徐晨曦,付大友,谭文渊,等.激光拉曼光谱法快速测定牛奶中三聚氰胺[J].分析实验室,2014,33(5):555-557.DOI:10.13595/j.cnki.issn1000-0720.2014.0128.
[11]陈小曼,雷皓宇,胡玉玲,等.固相萃取-表面增强拉曼光谱法测定奶粉中三聚氰胺[J].分析测试学报,2016,35(10):1343-1346.DOI:10.3969/j.issn.1004-4957.2016.10.022.
[12]黄梅英,李攻科,胡玉玲.表面增强拉曼光谱法定量检测食品中香豆素[J].分析化学研究报告,2015,43(8):1218-1221.DOI:10.11895/j.issn.0253-3820.141073.
[13]毛力军.表面增强拉曼光谱在偶氮染料检测中的研究进展[J].化学分析计量,2017,26(6):116-119.DOI:10.3969/j.issn.1008-6145.2017.06.028.
[14]张文强,李容,许文涛.农药残留的表面增强拉曼光谱快速检测技术研究现状与展望[J].农业工程学报,2017,33(24):269-276.DOI:10.11975/j.issn.1002-6819.2017.24.035.
[15]SUKMANEE T,WONGRAVEE K,EKGASIT S,et al.Facile and sensitive detection of carbofuran carbamate pesticide in rice and soybean using coupling reaction-based surface-enhanced Raman scattering[J].Analytical Sciences the International Journal of the Japan Society for Analytical Chemistry,2017,33(1):89-94.DOI:10.2116/analsci.33.89.
[16]褚幼萍,陈述,郑菊芳,等.氯化亚锡抑制吡啶分子表面增强拉曼光谱测定中的碳化现象[J].光谱学与光谱分析,2009,29(7):1892-1895.DOI:10.3964/j.issn.1000-0593(2009)07-1892-04.
[17]刘江美,严丽萍,刘文涵,等.表面增强拉曼光谱内标法测定亚胺硫磷农残含量[J].分析测试学报,2016,35(5):605-608.DOI:10.3969/j.issn.1004-4957.2016.05.019.
[18]PENG Y J,LIU M H,ZHAO J H,et al.Rapid determination of streptomycin residues in water using surface enhanced Raman spectroscopy with Au nanoparticles[J].Journal of Optoelectronics·Laser,2016,27(8):845-852.DOI:10.5772/intechopen.73086.
[19]贺昕,熊晓东,梁敬博,等.免疫检测用纳米胶体金的制备及粒径控制[J].稀有金属,2005,29(4):471-473.DOI:10.13373/j.cnki.cjrm.2005.04.021.
[20]李艳.金、银纳米粒子的合成以及表面光谱特征和应用[D].苏州:苏州大学,2013.DOI:10.3969/j.issn.1674-2869.2017.01.006.
[21]SAHA K,AGASTI S S,KIM C,et al.Gold nanoparticles in chemical and biological sensing[J].Chemical Reviews,2012,112(5):2739-2779.DOI:10.1021/cr2001178.
[22]LUO Q J,LI Y X,ZHANG M Q,et al.A highly sensitive,dualsignal assay based on rhodamine B covered silver nanoparticles for carbamate pesticides[J].Chinese Chemical Letters,2017,28:345-349.DOI:10.1016/j.cclet.2016.10.024.
[23]DAI Y P,WANG T,HU X Y,et al.Highly sensitive microcantileverbased immunosensor for the detection of carbofuran in soil and vegetable samples[J].Food Chemistry,2017,229:432-438.DOI:10.1016/j.foodchem.2017.02.093.
[24]董旭,刘晓云,周剑锋,等.以Au@Ag双金属纳米棒为核的热响应性核壳复合微凝胶的制备及性能表征[J].化学研究与应用,2015(6):836-841.DOI:10.3969/j.issn.1674-2869.2017.01.006.
[25]LIU M,GUYOT-SIONNEST P.Preparation and optical properties of silver chalcogenide coated gold nanorods[J].Journal of Materials Chemistry,2006,16(40):3942-3945.DOI:10.1039/B607106F.
[26]YANG B,CHEN X,LIU R,et al.Target induced aggregation of modified Au@Ag NPs for surface enhanced Raman scattering and its ultrasensitive detection of arsenic(III)in aqueous solution[J].RSCAdvances,2015,5(95):77755-77759.DOI:10.1039/c5ra15954g.
[27]曾崇毅,汤俊琪,满石清.大面积SiO2/Au核壳纳米粒子的制备及拉曼散射研究[J].合肥工业大学学报(自然科学版),2014(2):196-199.DOI:10.3969/j.issn.1003-5060.2014.02.017.
[28]SONG Y H,CHEN J Y,SUN M,et al.A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples[J].Journal of Hazardous Materials,2016,304:103-109.DOI:10.1016/j.jhazmat.2015.10.058.
[29]多林希F R,佛特利W G,本特利F F.有机化合物的特征拉曼频率[M].北京:中国化学会,1980:5-125.
[30]朱自莹,顾仁傲,陆天虹.拉曼光谱在化学中的应用[M].沈阳:东北大学出版社,1998:295-302.
[31]郭浩,戴树玺,张兴堂,等.银、金溶胶及银/金混合胶体的制备和拉曼增强特性的研究[J].河南大学学报(自然科学版),2011,41(3):246-250.DOI:10.3969/j.issn.1003-4978.2011.03.006.
[2]胡丽君.高效液相色谱在检测农产品氨基甲酸酯类农药残留量的应用[J].农产品加工,2015(3):44-46.DOI:10.3969/jissn.1671-9646(X).2015.02.013.
[3]黄双根,胡建平,刘木华,等.氨基甲酸酯类农药的密度泛函理论计算及拉曼光谱研究[J].光谱学与光谱分析,2017,37(3):766-771.DOI:10.3964/j.issn.1000-0593(2017)03-0766-06.
[4]王建,林秋萍,雷郑莉,等.气相色谱-质谱法测定蔬菜中有机磷杀虫剂和克百威的残留量[J].分析试验室,2002,21(2):27-30.DOI:10.3969/j.issn.1000-0720.2002.02.009.
[5]HAN Y T,SONG L,LIU S W,et al.Simultaneous determination of 124 pesticide residues in Chinese liquor and liquormaking raw materials(sorghum and rice hull)by rapid multiplug filtration cleanup and gas chromatography-tandem mass spectrometry[J].Food Chemistry,2018,241:258-267.DOI:10.1016/j.foodchem.2017.08.103.
[6]冯莎莎,梁春凤,梁顺超,等.二氧化钛分子印迹膜传感器光电流法检测克百威[J].分析测试学报,2017,36(5):684-688.DOI:10.3969/j.issn.1004-4957.2017.05.019.
[7]孙航,蒋煜峰,胡雪菲,等.添加生物炭对西北黄土吸附克百威的影响[J].环境科学学报,2016,36(3):1015-1020.DOI:10.13671/j.hjkxxb.2015.0572.
[8]郑彬,温宝英,苏立众,等.表面增强拉曼光谱快速检测尿液中的尿酸[J].光谱学与光谱分析,2017,37(6):1789-1792.DOI:10.3964/j.issn.1000-0593(2017)06-1789-04.
[9]左奇,陈瑶,石彩霞,等.表面增强拉曼散射光谱定量分析技术的研究进展[J].分析化学,2015(11):1656-1663.DOI:10.11895/j.issn.0253-3820.150597.
[10]徐晨曦,付大友,谭文渊,等.激光拉曼光谱法快速测定牛奶中三聚氰胺[J].分析实验室,2014,33(5):555-557.DOI:10.13595/j.cnki.issn1000-0720.2014.0128.
[11]陈小曼,雷皓宇,胡玉玲,等.固相萃取-表面增强拉曼光谱法测定奶粉中三聚氰胺[J].分析测试学报,2016,35(10):1343-1346.DOI:10.3969/j.issn.1004-4957.2016.10.022.
[12]黄梅英,李攻科,胡玉玲.表面增强拉曼光谱法定量检测食品中香豆素[J].分析化学研究报告,2015,43(8):1218-1221.DOI:10.11895/j.issn.0253-3820.141073.
[13]毛力军.表面增强拉曼光谱在偶氮染料检测中的研究进展[J].化学分析计量,2017,26(6):116-119.DOI:10.3969/j.issn.1008-6145.2017.06.028.
[14]张文强,李容,许文涛.农药残留的表面增强拉曼光谱快速检测技术研究现状与展望[J].农业工程学报,2017,33(24):269-276.DOI:10.11975/j.issn.1002-6819.2017.24.035.
[15]SUKMANEE T,WONGRAVEE K,EKGASIT S,et al.Facile and sensitive detection of carbofuran carbamate pesticide in rice and soybean using coupling reaction-based surface-enhanced Raman scattering[J].Analytical Sciences the International Journal of the Japan Society for Analytical Chemistry,2017,33(1):89-94.DOI:10.2116/analsci.33.89.
[16]褚幼萍,陈述,郑菊芳,等.氯化亚锡抑制吡啶分子表面增强拉曼光谱测定中的碳化现象[J].光谱学与光谱分析,2009,29(7):1892-1895.DOI:10.3964/j.issn.1000-0593(2009)07-1892-04.
[17]刘江美,严丽萍,刘文涵,等.表面增强拉曼光谱内标法测定亚胺硫磷农残含量[J].分析测试学报,2016,35(5):605-608.DOI:10.3969/j.issn.1004-4957.2016.05.019.
[18]PENG Y J,LIU M H,ZHAO J H,et al.Rapid determination of streptomycin residues in water using surface enhanced Raman spectroscopy with Au nanoparticles[J].Journal of Optoelectronics·Laser,2016,27(8):845-852.DOI:10.5772/intechopen.73086.
[19]贺昕,熊晓东,梁敬博,等.免疫检测用纳米胶体金的制备及粒径控制[J].稀有金属,2005,29(4):471-473.DOI:10.13373/j.cnki.cjrm.2005.04.021.
[20]李艳.金、银纳米粒子的合成以及表面光谱特征和应用[D].苏州:苏州大学,2013.DOI:10.3969/j.issn.1674-2869.2017.01.006.
[21]SAHA K,AGASTI S S,KIM C,et al.Gold nanoparticles in chemical and biological sensing[J].Chemical Reviews,2012,112(5):2739-2779.DOI:10.1021/cr2001178.
[22]LUO Q J,LI Y X,ZHANG M Q,et al.A highly sensitive,dualsignal assay based on rhodamine B covered silver nanoparticles for carbamate pesticides[J].Chinese Chemical Letters,2017,28:345-349.DOI:10.1016/j.cclet.2016.10.024.
[23]DAI Y P,WANG T,HU X Y,et al.Highly sensitive microcantileverbased immunosensor for the detection of carbofuran in soil and vegetable samples[J].Food Chemistry,2017,229:432-438.DOI:10.1016/j.foodchem.2017.02.093.
[24]董旭,刘晓云,周剑锋,等.以Au@Ag双金属纳米棒为核的热响应性核壳复合微凝胶的制备及性能表征[J].化学研究与应用,2015(6):836-841.DOI:10.3969/j.issn.1674-2869.2017.01.006.
[25]LIU M,GUYOT-SIONNEST P.Preparation and optical properties of silver chalcogenide coated gold nanorods[J].Journal of Materials Chemistry,2006,16(40):3942-3945.DOI:10.1039/B607106F.
[26]YANG B,CHEN X,LIU R,et al.Target induced aggregation of modified Au@Ag NPs for surface enhanced Raman scattering and its ultrasensitive detection of arsenic(III)in aqueous solution[J].RSCAdvances,2015,5(95):77755-77759.DOI:10.1039/c5ra15954g.
[27]曾崇毅,汤俊琪,满石清.大面积SiO2/Au核壳纳米粒子的制备及拉曼散射研究[J].合肥工业大学学报(自然科学版),2014(2):196-199.DOI:10.3969/j.issn.1003-5060.2014.02.017.
[28]SONG Y H,CHEN J Y,SUN M,et al.A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples[J].Journal of Hazardous Materials,2016,304:103-109.DOI:10.1016/j.jhazmat.2015.10.058.
[29]多林希F R,佛特利W G,本特利F F.有机化合物的特征拉曼频率[M].北京:中国化学会,1980:5-125.
[30]朱自莹,顾仁傲,陆天虹.拉曼光谱在化学中的应用[M].沈阳:东北大学出版社,1998:295-302.
[31]郭浩,戴树玺,张兴堂,等.银、金溶胶及银/金混合胶体的制备和拉曼增强特性的研究[J].河南大学学报(自然科学版),2011,41(3):246-250.DOI:10.3969/j.issn.1003-4978.2011.03.006.