柱前衍生-液相色谱-串联质谱法测定葡萄和樱桃中单氰胺残留
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摘要
建立了丹磺酰氯(DNS)柱前衍生-液相色谱-串联质谱(LC-MS/MS)测定葡萄和樱桃中单氰胺的方法。样品经破壁机匀浆,乙酸乙酯超声提取,无水硫酸钠除水,提取液经减压浓缩,在碱性条件下与丹磺酰氯进行衍生反应。色谱柱为岛津Shim-pack XR-ODS色谱柱(75 mm×2.0 mm,1.6μm),流动相为甲醇和含0.05%(体积分数)甲酸的2 mmol/L醋酸铵水溶液,梯度洗脱,采用电喷雾离子源正离子多反应监测模式进行质谱检测。单氰胺在0.01~1.0 mg/L范围内,峰面积与质量浓度之间线性关系良好,相关系数不小于0.999 0。在0.01、0.05和1.0 mg/kg的添加水平下,葡萄和樱桃中单氰胺的平均回收率为75%~81%,精密度为6.5%~9.8%,定量限为0.01 mg/kg。该方法简便、快速、可靠,可用于批量检测葡萄和樱桃中单氰胺残留。
A method was developed for the quantitative determination of cyanamide in grapes and cherries by liquid chromatography-tandem mass spectrometry(LC-MS/MS)coupled with dansyl chloride(DNS)precolumn derivatization. First,the samples were homogenized,and then extracted with ethyl acetate under ultrasonication. The water was removed using anhydrous sodium sulfate,and the extract was concentrated and derivatized with dansyl chloride under alkaline condition. The separation was performed on a Shimadzu Shim-pack XR-ODS column(75 mm×2. 0 mm,1. 6 μm)with the mobile phases of methanol and 2 mmol/L ammonium acetate aqueous solution(containing 0. 05%(v/v)formic acid)in a gradient elution mode. The identification and quantification of cyanamide were carried out by MS/MS in positive electrospray ionization(ESI+)and multiple reaction monitoring(MRM)mode. The calibration curves showed good linearities in the range of 0. 01-1. 0 mg/L with the correlation coefficients not less than 0. 999 0. The average recoveries of cyanamide spiked at 0. 01,0. 05 and 1. 0 mg/kg in cherries and grapes were between 75% and 81%,and the relative standard deviations(RSDs)were between 6. 5% and 9. 8%. Both the limits of quantification(LOQs)of the analytes were 0. 01 mg/kg. The method is simple,rapid,accurate and suitable for the confirmation and quantification of cyanamide in cherries and grapes.
A method was developed for the quantitative determination of cyanamide in grapes and cherries by liquid chromatography-tandem mass spectrometry(LC-MS/MS)coupled with dansyl chloride(DNS)precolumn derivatization. First,the samples were homogenized,and then extracted with ethyl acetate under ultrasonication. The water was removed using anhydrous sodium sulfate,and the extract was concentrated and derivatized with dansyl chloride under alkaline condition. The separation was performed on a Shimadzu Shim-pack XR-ODS column(75 mm×2. 0 mm,1. 6 μm)with the mobile phases of methanol and 2 mmol/L ammonium acetate aqueous solution(containing 0. 05%(v/v)formic acid)in a gradient elution mode. The identification and quantification of cyanamide were carried out by MS/MS in positive electrospray ionization(ESI+)and multiple reaction monitoring(MRM)mode. The calibration curves showed good linearities in the range of 0. 01-1. 0 mg/L with the correlation coefficients not less than 0. 999 0. The average recoveries of cyanamide spiked at 0. 01,0. 05 and 1. 0 mg/kg in cherries and grapes were between 75% and 81%,and the relative standard deviations(RSDs)were between 6. 5% and 9. 8%. Both the limits of quantification(LOQs)of the analytes were 0. 01 mg/kg. The method is simple,rapid,accurate and suitable for the confirmation and quantification of cyanamide in cherries and grapes.
引文
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[2]Wang L,Zhang C X,Xu W P,et al.Journal of Fruit Science,2016,33(6):709王磊,张才喜,许文平,等.果树学报,2016,33(6):709
[3]Wang X D,Wei Y X,Liu C,et al.China Fruits,2013(5):25王兴东,魏永详,刘成,等.中国果树,2013(5):25
[4]Schep L,Temple W,Beasley M.Clinical Toxicology,2009,47(1):58
[5]International Union of Pure and Applied Chemistry(IUPAC).The PPDB Pesticide Properties Database.[2017-08-05].http://sitem.herts.ac.uk/aeru/iupac/Reports/184.htm
[6]Ministry of Agriculture of the People’s Republic of China.National Agricultural Product Quality and Safety Risk Assessment Project Plan in 2015.[2017-08-05].http://www.moa.gov.cn/govpublic/ncpzlaq/201507/t20150727_4763827.htm中华人民共和国农业部.2015年度国家农产品质量安全风险评估项目计划.[2017-08-05].http://www.moa.gov.cn/govpublic/ncpzlaq/201507/t20150727_4763827.htm
[7]GB/T 2763-2016
[8]Li S Q,Wang X J,Guangdong Chemical,2012,39(14):153李淑琼,汪晓军.广东化工,2012,39(14):153
[9]Rust U.U.S.Patent,4692415.1987-09-08
[10]Reddy E G S,Rao T N,Prasad B G.Der Pharmacia Lettre,2015,7(4):240
[11]Zhang C T.[MS Dissertation].Tianjin:Nankai University,2010张春涛.[硕士学位论文].天津:南开大学,2010
[12]Cheng C,Di S S,Zhang W J,et al.Food Chem,2018,239:529
[13]Jin G W,Cai Y Q,Yu H J,et al.Chinese Journal of Chromatography,2010,28(11):1099金高娃,蔡友琼,于慧娟,等.色谱,2010,28(11):1099
[14]Yang H M,Hang L,Yang J G,et al.Chinese Journal of Analytical Chemistry,2016,44(3):462杨华梅,杭莉,杨建国,等.分析化学,2016,44(3):462
[15]Environmental Protection Agency(EPA).A High Performance Liquid Chromatographic Method for Measurement of Cyanamide Residues in Soil.[2017-07-08].https://archive.epa.gov/pesticides/methods/rammethods/web/pdf/1997_063m.pdf