超高效液相色谱-串联质谱法测定4种浆果中5-硝基邻甲氧基苯酚钠和对硝基苯酚钠残留量
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摘要
【目的】为了测定浆果类水果(蓝莓、树莓、草莓及车厘子)中5-硝基对甲氧基苯酚钠(Sodium 5-nitroguaiacolate, 5NG)和对硝基苯酚钠(Sodium para-nitrophenolate, SD2)残留量,建立了快速测定5NG和SD2的超高效液相色谱-串联质谱(UPLC-MS/MS)检测方法。【方法】样品用乙腈提取,无需富集浓缩等特殊净化步骤,以CAPCELL PKA-C18色谱柱分离,采用电喷雾(ESI~-)-多反应监测模式(MRM)检测,基质匹配标准溶液外标法定量。【结果】在0.02～2.00 mg/kg范围内,5NG和SD2的质量浓度与对应的峰面积间线性关系良好,相关系数均大于0.9968。5-硝基对甲氧基苯酚钠和对硝基苯酚钠在浆果类水果(蓝莓、树莓、草莓及车厘子)中的检出限(LOD)别为0.28～0.73μg/kg,定量限(LOQ)为0.93～2.43μg/kg。在4个添加水平下,样品添加回收试验的平均回收率为91.75%～112.67%,相对标准偏差为1.07%～5.76%(n=6)。【结论】该方法简单快捷,灵敏度高,定量准确,可用于同时检测蓝莓、树莓、草莓及车厘子中5NG和SD2的残留量。
【Objective】 In order to determine the 5-nitroguaiacolate(5 NG) and sodium para-nitrophenolate residues(SD2) in berries(blueberry, raspberry, strawberry and cherry), a rapid method for analyzing 5 NG and SD2 by ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry(UPLC-ESI-MS/MS) was developed. 【Method】 The sample was extracted with acetonitrile, and no moreclean-up procedures were needed.Successful separation and detection were achieved on a CAPCELL PKA-C18 column and multiple reaction monitoring(MRM) in negative electrospray ionization(ESI~-) mode was used. 【Result】 Quantification was performed by peak area external standard methods using matrix-matched calibration curves, which were linear in the range of 0.02-2.00 mg/kg with good linear relationships.The correlation coefficients were all above 0.9968. The limits of detection(LOD) and limits of quantification(LOQ)for 5 NG and SD2 were 0.28-0.73 and 0.93-2.43 μg/kg, respectively.At four spiked levels, the average recoveries ranged from 91.75 % to 112.67 %, and the relative standard deviation(n=6) was in the range of 1.07 %-5.76 %. 【Conclusion】 The method was quick,easy, sensitive, accurate and could be applied in the determination of 5 NG and SD2 residues in berries(blueberry, raspberry, strawberry and cherry).
【Objective】 In order to determine the 5-nitroguaiacolate(5 NG) and sodium para-nitrophenolate residues(SD2) in berries(blueberry, raspberry, strawberry and cherry), a rapid method for analyzing 5 NG and SD2 by ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry(UPLC-ESI-MS/MS) was developed. 【Method】 The sample was extracted with acetonitrile, and no moreclean-up procedures were needed.Successful separation and detection were achieved on a CAPCELL PKA-C18 column and multiple reaction monitoring(MRM) in negative electrospray ionization(ESI~-) mode was used. 【Result】 Quantification was performed by peak area external standard methods using matrix-matched calibration curves, which were linear in the range of 0.02-2.00 mg/kg with good linear relationships.The correlation coefficients were all above 0.9968. The limits of detection(LOD) and limits of quantification(LOQ)for 5 NG and SD2 were 0.28-0.73 and 0.93-2.43 μg/kg, respectively.At four spiked levels, the average recoveries ranged from 91.75 % to 112.67 %, and the relative standard deviation(n=6) was in the range of 1.07 %-5.76 %. 【Conclusion】 The method was quick,easy, sensitive, accurate and could be applied in the determination of 5 NG and SD2 residues in berries(blueberry, raspberry, strawberry and cherry).
引文
[1]SHI X M, JIN F, HUANG Y T, et al. Simultaneous determination of five plant growth regulators in fruits by modified Quick, Easy, Cheap, Effective, Rugged, and Safe(QuEChERS) extraction and liquid chromatography?tandem mass spectrometry[J]. Journal of Agricultural and Food Chemistry, 2012, 60: 60.
[2]牟艳莉,郭德华,丁卓平,等. 高效液相色谱-串联质谱法测定瓜果中11种植物生长调节剂的残留量[J]. 分析化学,2013,41(11):1640.
[3]唐莉娟,谭婷,万益群. 超声波提取-高效液相色谱-电喷雾离子化质谱法测定白萝卜中植物生长调节剂[J]. 食品科学,2012,33(14):136.
[4]胡玫,乔桂芳,刘惠婉,等. 2.85 %硝钠·萘乙酸钠水剂高效液相色谱分析[J]. 农药,2015,54(6):422.
[5]杨晶,曹立冬,王胜翔,等. 复硝酚钠原药中3种有效成分的高效液相色谱分析[J]. 农药学学报,2013,15(4):439.
[6]邢丽红,冷凯良,孙伟红,等. 气相色谱法检测鱼和虾中复硝酚钠残留量[J]. 中山大学学报,2013,52(6):104.
[7]MAN Y R, SHU M, WANG D, et al. Determination of 6-benzylaminopurine in bean sproutsby capillary electrophoresis compared with HPLC[J]. Food Analytical Methods, 2016(9): 3025.
[8]DANEZIS G P, ANAGNOSTOPOULOS C J, LIAPIS K, et al. Multi-residue Analysis of Pesticides, Plant Hormones, Veterinary Drugs and Mycotoxins using HILIC Chromatography-MS/MS in Various Food Matrices[J]. Analytica Chimica Acta, 2016, 942: 121.
[9]CAO S R, ZHOU X, XI C X, et al. Cleaning up vegetable samples using a modified ‘QuEChERS' procedure for the determination of 17 plant growth regulator residues by ultra high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry[J]. Food Analytical Methods, 2016(9): 2097.
[10]PU C H, LIN S K, CHUANG W C, et al. Modified QuEChERS method for 24 plant growth regulators in grapes using LC-MS/MS[J]. Journal of Food and Drug Analysis, 2018, 26: 637.
[11]中华人民共和国卫生部,中华人民共和国农业部. GB2763-2012食品中农药药最大残留限量[S]. 2012.
[12]高丽丽,亚森江,库那洪,等. 紫外可见光谱谱峰归一校正法检测对硝基苯酚[J]. 环境科学与技术,2011,34(2):111.
[13]孟磊,郑先福,王永珊,等. 高效液相色谱法测定工业废水中的硝基酚[J]. 光谱实验室,2007,24(5):868.
[14]YANG Q, CHEN, X Q, JIANG X Y. Liquid-liquid microextraction ofnitrophenols using supramolecular solvent and their determinationby HPLC with UV detection[J]. Chromatographia, 2013, 76: 1641.
[15]SARAJI M, MARZBAN M. Determination of 11 priority pollutant phe?nols in waste water using dispersive liquid-liquid microextractionfollowed by high-performance liquid chromatography-diode-arraydetection[J]. Analytical and Bioanalytical Chemistry, 2010, 396(7): 2685.
[16]CHOKWE T B, OOONKWO J O, SIBALI L L, et al. Optimization and Simultaneous Determination of AlkylPhenol Ethoxylates and Brominated Flame Retardantsin Water after SPE and Heptafluorobutyric AnhydrideDerivatization followed by GC/MS[J]. Chroma-graphia, 2012, 75: 1165.
[17]LI C M, JIN F, YU Z Y, et al. Rapid determination of chlormequat in meat by dispersivesolid-phase extraction and hydrophilic interaction liquidchromatography (HILIC) electrospray tandem mass spectrometry[J]. Journal of Agricultural and Food Chemistry, 2012, 60: 6816.
[18]WANG X F, MAO X J, YAN A P, et al. Simultaneous determination of nine plant growth regulatorsin navel oranges by liquid chromatography-triple quadrupoletandem mass spectrometry[J]. Food Analytical Methods, 2016(9): 3268.
[19]DANEZIS G P, ANAGNOSTOPOULOS C J, LIAPIS K, et al. Multi-residue analysis of pesticides, plant hormones, veterinary drugsand mycotoxins using HILIC chromatography-MS/MS in various foodmatrices[J]. Analytica Chimica Acta, 2016, 942: 121.
[20]张海燕. 超高效液相色谱-串联质谱法测定番茄(酱)及香梨中矮壮素和缩节胺残留量[J]. 农药学学报,2016,18(5):619.
[21]黄何何,张缙,徐敦明,等. QuEChERS-高效液相色谱-串联质谱法同时测定水果中21种植物生长调节剂的残留量[J]. 色谱,2014,32(7):707.
[22]DU P Q, LIU X G, GU X J, et al. Rapid residue analysis of pyriproxyfen, avermectins anddiflubenzuron in mushrooms by ultra-performanceliquid chromatography coupled with tandem massspectrometry[J]. Analytical Methods, 2013(5): 6741.
[23]黄宝勇,肖志勇,陈丹,等. 农药残留检测方法中关于基质效应补偿的相关问题探讨[J]. 农药科学与管理,2010,31(3):39.
[24]MATUSZEWSKI B K, CONSTANZER M L, CHAVEZENG C M. Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS[J]. Analytical Chemistry, 2003, 75(13): 3019.
[25]齐沛沛,范旭,周莉,等. 基于超高效液相色谱-串联质谱快速测定草莓中典型杀菌剂[J]. 浙江农业科学,2015,56(6):871.
[2]牟艳莉,郭德华,丁卓平,等. 高效液相色谱-串联质谱法测定瓜果中11种植物生长调节剂的残留量[J]. 分析化学,2013,41(11):1640.
[3]唐莉娟,谭婷,万益群. 超声波提取-高效液相色谱-电喷雾离子化质谱法测定白萝卜中植物生长调节剂[J]. 食品科学,2012,33(14):136.
[4]胡玫,乔桂芳,刘惠婉,等. 2.85 %硝钠·萘乙酸钠水剂高效液相色谱分析[J]. 农药,2015,54(6):422.
[5]杨晶,曹立冬,王胜翔,等. 复硝酚钠原药中3种有效成分的高效液相色谱分析[J]. 农药学学报,2013,15(4):439.
[6]邢丽红,冷凯良,孙伟红,等. 气相色谱法检测鱼和虾中复硝酚钠残留量[J]. 中山大学学报,2013,52(6):104.
[7]MAN Y R, SHU M, WANG D, et al. Determination of 6-benzylaminopurine in bean sproutsby capillary electrophoresis compared with HPLC[J]. Food Analytical Methods, 2016(9): 3025.
[8]DANEZIS G P, ANAGNOSTOPOULOS C J, LIAPIS K, et al. Multi-residue Analysis of Pesticides, Plant Hormones, Veterinary Drugs and Mycotoxins using HILIC Chromatography-MS/MS in Various Food Matrices[J]. Analytica Chimica Acta, 2016, 942: 121.
[9]CAO S R, ZHOU X, XI C X, et al. Cleaning up vegetable samples using a modified ‘QuEChERS' procedure for the determination of 17 plant growth regulator residues by ultra high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry[J]. Food Analytical Methods, 2016(9): 2097.
[10]PU C H, LIN S K, CHUANG W C, et al. Modified QuEChERS method for 24 plant growth regulators in grapes using LC-MS/MS[J]. Journal of Food and Drug Analysis, 2018, 26: 637.
[11]中华人民共和国卫生部,中华人民共和国农业部. GB2763-2012食品中农药药最大残留限量[S]. 2012.
[12]高丽丽,亚森江,库那洪,等. 紫外可见光谱谱峰归一校正法检测对硝基苯酚[J]. 环境科学与技术,2011,34(2):111.
[13]孟磊,郑先福,王永珊,等. 高效液相色谱法测定工业废水中的硝基酚[J]. 光谱实验室,2007,24(5):868.
[14]YANG Q, CHEN, X Q, JIANG X Y. Liquid-liquid microextraction ofnitrophenols using supramolecular solvent and their determinationby HPLC with UV detection[J]. Chromatographia, 2013, 76: 1641.
[15]SARAJI M, MARZBAN M. Determination of 11 priority pollutant phe?nols in waste water using dispersive liquid-liquid microextractionfollowed by high-performance liquid chromatography-diode-arraydetection[J]. Analytical and Bioanalytical Chemistry, 2010, 396(7): 2685.
[16]CHOKWE T B, OOONKWO J O, SIBALI L L, et al. Optimization and Simultaneous Determination of AlkylPhenol Ethoxylates and Brominated Flame Retardantsin Water after SPE and Heptafluorobutyric AnhydrideDerivatization followed by GC/MS[J]. Chroma-graphia, 2012, 75: 1165.
[17]LI C M, JIN F, YU Z Y, et al. Rapid determination of chlormequat in meat by dispersivesolid-phase extraction and hydrophilic interaction liquidchromatography (HILIC) electrospray tandem mass spectrometry[J]. Journal of Agricultural and Food Chemistry, 2012, 60: 6816.
[18]WANG X F, MAO X J, YAN A P, et al. Simultaneous determination of nine plant growth regulatorsin navel oranges by liquid chromatography-triple quadrupoletandem mass spectrometry[J]. Food Analytical Methods, 2016(9): 3268.
[19]DANEZIS G P, ANAGNOSTOPOULOS C J, LIAPIS K, et al. Multi-residue analysis of pesticides, plant hormones, veterinary drugsand mycotoxins using HILIC chromatography-MS/MS in various foodmatrices[J]. Analytica Chimica Acta, 2016, 942: 121.
[20]张海燕. 超高效液相色谱-串联质谱法测定番茄(酱)及香梨中矮壮素和缩节胺残留量[J]. 农药学学报,2016,18(5):619.
[21]黄何何,张缙,徐敦明,等. QuEChERS-高效液相色谱-串联质谱法同时测定水果中21种植物生长调节剂的残留量[J]. 色谱,2014,32(7):707.
[22]DU P Q, LIU X G, GU X J, et al. Rapid residue analysis of pyriproxyfen, avermectins anddiflubenzuron in mushrooms by ultra-performanceliquid chromatography coupled with tandem massspectrometry[J]. Analytical Methods, 2013(5): 6741.
[23]黄宝勇,肖志勇,陈丹,等. 农药残留检测方法中关于基质效应补偿的相关问题探讨[J]. 农药科学与管理,2010,31(3):39.
[24]MATUSZEWSKI B K, CONSTANZER M L, CHAVEZENG C M. Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS[J]. Analytical Chemistry, 2003, 75(13): 3019.
[25]齐沛沛,范旭,周莉,等. 基于超高效液相色谱-串联质谱快速测定草莓中典型杀菌剂[J]. 浙江农业科学,2015,56(6):871.