SPE-UPLC-MS/MS法测定烟草及烟草制品中抑芽丹残留量
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摘要
为准确测定烟草及烟草制品中抑芽丹的残留量,建立了一种固相萃取-超高效液相色谱-串联质谱(SPE-UPLC-MS/MS)方法。烟草样品经盐酸溶液加热回流提取、石墨化炭黑(GCB)SPE柱净化后在多反应监测负离子模式下测定,采用氘代抑芽丹同位素内标法定量。结果表明:(1)使用石墨化炭黑SPE柱可有效净化萃取液,除去盐酸后的洗脱液pH近中性,适合于质谱分析;(2)抑芽丹定量限为0.47 mg/kg,回收率为94.2%~102.1%,相对标准偏差(RSD)小于6%;(3)采用该方法检测了13个烟草样品中的抑芽丹残留量,并与采用YC/T 405.5—2011标准方法的测定值进行比较,结果显示两组数据的一致性较好。该方法灵敏度高,稳定性和准确性好,适用于烟草样品中抑芽丹残留量的测定。
To determine the maleic hydrazide residues in tobacco and tobacco products, an SPE-UPLC-MS/MS method was developed by adopting solid phase extraction cartridges(SPE) for sample clean-up and ultra-performance liquid chromatography coupled with tandem mass spectrometry(UPLC-MS/MS) for detection.Tobacco samples were extracted with hydrochloric acid under heating and refluxing, and further purified by solid-phase clean-up with graphitized carbon black(GCB) column. The ESI source in negative ion mode was used for qualitative and quantitative analyses under multiple reaction monitoring(MRM) mode with d2-maleic hydrazide as the internal standard. The results showed that: 1) After the purification by GCB column, the p H value of the eluent was near neutral after removing hydrochloric acid. 2) The limit of quantification was 0.47 mg/kg, and recoveries ranged from 94.2% to 102.1% with relative standard deviation(RSD) less than 6%.3) The maleic hydrazide residues in 13 tobacco samples were detected by this method and compared with those determined by the standard method described in YC/T 405.5—2011, the data using the two methods agreed with each other very well. This method is sensitive, stable, accurate and suitable for determining the maleic hydrazide residues in tobacco samples.
To determine the maleic hydrazide residues in tobacco and tobacco products, an SPE-UPLC-MS/MS method was developed by adopting solid phase extraction cartridges(SPE) for sample clean-up and ultra-performance liquid chromatography coupled with tandem mass spectrometry(UPLC-MS/MS) for detection.Tobacco samples were extracted with hydrochloric acid under heating and refluxing, and further purified by solid-phase clean-up with graphitized carbon black(GCB) column. The ESI source in negative ion mode was used for qualitative and quantitative analyses under multiple reaction monitoring(MRM) mode with d2-maleic hydrazide as the internal standard. The results showed that: 1) After the purification by GCB column, the p H value of the eluent was near neutral after removing hydrochloric acid. 2) The limit of quantification was 0.47 mg/kg, and recoveries ranged from 94.2% to 102.1% with relative standard deviation(RSD) less than 6%.3) The maleic hydrazide residues in 13 tobacco samples were detected by this method and compared with those determined by the standard method described in YC/T 405.5—2011, the data using the two methods agreed with each other very well. This method is sensitive, stable, accurate and suitable for determining the maleic hydrazide residues in tobacco samples.
引文
[1]Renaud J M,Keller I,Vuillaume G.Determination of maleic hydrazide residues in cured tobacco by gas chromatography[J].Journal of Chromatography A,1992,604(2):243-246.
[2]Newsome W H.A method for the determination of maleic hydrazide and its beta-D-glucoside in foods by high-pressure anion-exchange liquid chromatography[J].Journal of Agricultural and Food Chemistry,1980,28(2):270-272.
[3]Marcano L,Carruyo I,Del Campo A,et al.Cytotoxicity and mode of action of maleic hydrazide in root tips of Allium cepa L.[J].Environmental Research,2004,94(2):221-226.
[4]Dias A I,Duncan H J.Residues of free and bound maleic hydrazide in potato tubers[J].Potato Research,1999,42(1):89-93.
[5]Yang S S.Determination of maleic hydrazide in tobacco by micellar liquid chromatography[J].Journal of Chromatography A,1992,595(1/2):346-350.
[6]杨昀,刘玉林.烟叶和土壤中抑芽丹残留分析方法及应用研究[J].分析化学,2004,32(3):410.YANG Yun,LIU Yulin.Determination of maleic hydrazide residue in tobacco leaves and soil by high performance liquid chromatography[J].Chinese Journal of Analytical Chemistry,2004,32(3):410.
[7]张洪非,边照阳,唐纲岭,等.HPLC法测定烟草及烟草制品中马来酰肼残留[J].烟草科技,2011(12):47-51.ZHANG Hongfei,BIAN Zhaoyang,TANG Gangling,et al.Determination of maleic hydrazide residue in tobacco and tobacco products with high performance liquid chromatography[J].Tobacco Science&Technology,2011(12):47-51.
[8]Wang L J,Fei T,Qi D W,et al.Development of microwave-assisted extraction and liquid chromatographytandem mass spectrometry for determination of maleichydrazide residues in tobacco[J].Analytical Methods,2015,7(12):5103-5107.
[9]陈晓水,朱书秀,蒋佳磊,等.高效液相色谱-串联质谱法测定烟草中马来酰肼残留量[J].质谱学报,2017,38(2):234-238.CHEN Xiaoshui,ZHU Shuxiu,JIANG Jialei,et al.Determination of maleic hydrazide residue in tobacco by HPLC-MS/MS[J].Journal of Chinese Mass Spectrometry Society,2017,38(2):234-238.
[10]张威,唐纲岭,刘惠民,等.烟草中抑芽丹残留量的测定[J].烟草科技,2006(7):43-45.ZHANG Wei,TANG Gangling,LIU Huimin,et al.Determination of maleic hydrazide residues in tobacco[J].Tobacco Science&Technology,2006(7):43-45.
[11]潘广文,赵增运,胡忠阳,等.高效离子排斥色谱法测定蔬菜中的马来酰肼[J].色谱,2010,28(7):712-715.PAN Guangwen,ZHAO Zengyun,HU Zhongyang,et al.Determination of maleic hydrazide in vegetables by high performance ion-exclusion chromatography[J].Chinese Journal of Chromatography,2010,28(7):712-715.
[12]Nagami H.Residues of maleic hydrazide and chlorpropham in potato chips[J].Bulletin of Environmental Contamination and Toxicology,1997,58(5):764-768.
[13]Morenoa M C,Stadlera T,Silva A A,et al.Determination of maleic hydrazide residues in garlic bulbs by HPLC[J].Talanta,2012,89(2):369-376.
[14]Lewis D J,Barnes K A,Wilkinson K,et al.Extraction of maleic hydrazide residues from potato crisps and their determination using high-performance liquid chromatography with UV and atmospheric pressure chemical ionisation mass spectrometric detection[J].Journal of Chromatography A,1996,750(1/2):391-396.
[15]Kubilius D T,Bushway R J.Determination of maleic hydrazide in potatoes and onions by fluorescence high performance liquid chromatography[J].Journal of Liquid Chromatography and Related Technologies,1999,22(4):593-601.
[16]汤健华,李儒发.马来酰肼的示波极谱法测定[J].昆明医科大学学报,1990,11(1):38-43.TANG Jianhua,LI Rufa.Oscillopolarographic determination of maleic hydrazide[J].Journal of Kunming Medical University,1990,11(1):38-43.
[17]李莉,周敏,房彦军,等.高碘酸钾-鲁米诺后化学发光法测定马来酰肼[J].食品科技,2008,33(3):223-225.LI Li,ZHOU Min,FANG Yanjun,et al.Flow-injection post-chemiluminescence determination of maleic hydrazide in luminol-potassium periodate reaction[J].Food Science and Technology,2008,33(3):223-225.
[18]邱萍,倪永年.抑芽丹的电化学行为及其测定[J].广西师范大学学报(自然科学版),2003,21(4):160-161.QIU Ping,NI Yongnian.Electrochemical behaviour of maleic hydrazide and its determination[J].Journal of Guangxi Normal University(Natural Science),2003,21(4):160-161.
[19]YC/T 31—1996烟草及烟草制品试样的制备和水分测定烘箱法[S].YC/T 31—1996 Tobacco and tobacco products—Preparation of test sample and determination of water content—Oven method[S].
[20]阮丽萍,沈东旭,吉文亮,等.采用HPLC-MS/MS方法同时测定花生中的马来酰肼和丁酰肼[J].江苏农业学报,2012,28(1):228-230.RUAN Liping,SHEN Dongxu,JI Wenliang,et al.Simultaneous determination of maleic hydrazide and daminozide in peanut by high performance liquid chromatography-tandem mass spectrometry[J].Jiangsu Journal of Agricultural Sciences,2012,28(1):228-230.
[21]吴成,赵志强.液相色谱质谱测定中甲醇乙腈对农药响应的影响[J].分析试验室,2015,34(6):711-716.WU Cheng,ZHAO Zhiqiang.Influence of methanol and acetonitrile on pesticides response by liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Analysis Laboratory,2015,34(6):711-716.
[2]Newsome W H.A method for the determination of maleic hydrazide and its beta-D-glucoside in foods by high-pressure anion-exchange liquid chromatography[J].Journal of Agricultural and Food Chemistry,1980,28(2):270-272.
[3]Marcano L,Carruyo I,Del Campo A,et al.Cytotoxicity and mode of action of maleic hydrazide in root tips of Allium cepa L.[J].Environmental Research,2004,94(2):221-226.
[4]Dias A I,Duncan H J.Residues of free and bound maleic hydrazide in potato tubers[J].Potato Research,1999,42(1):89-93.
[5]Yang S S.Determination of maleic hydrazide in tobacco by micellar liquid chromatography[J].Journal of Chromatography A,1992,595(1/2):346-350.
[6]杨昀,刘玉林.烟叶和土壤中抑芽丹残留分析方法及应用研究[J].分析化学,2004,32(3):410.YANG Yun,LIU Yulin.Determination of maleic hydrazide residue in tobacco leaves and soil by high performance liquid chromatography[J].Chinese Journal of Analytical Chemistry,2004,32(3):410.
[7]张洪非,边照阳,唐纲岭,等.HPLC法测定烟草及烟草制品中马来酰肼残留[J].烟草科技,2011(12):47-51.ZHANG Hongfei,BIAN Zhaoyang,TANG Gangling,et al.Determination of maleic hydrazide residue in tobacco and tobacco products with high performance liquid chromatography[J].Tobacco Science&Technology,2011(12):47-51.
[8]Wang L J,Fei T,Qi D W,et al.Development of microwave-assisted extraction and liquid chromatographytandem mass spectrometry for determination of maleichydrazide residues in tobacco[J].Analytical Methods,2015,7(12):5103-5107.
[9]陈晓水,朱书秀,蒋佳磊,等.高效液相色谱-串联质谱法测定烟草中马来酰肼残留量[J].质谱学报,2017,38(2):234-238.CHEN Xiaoshui,ZHU Shuxiu,JIANG Jialei,et al.Determination of maleic hydrazide residue in tobacco by HPLC-MS/MS[J].Journal of Chinese Mass Spectrometry Society,2017,38(2):234-238.
[10]张威,唐纲岭,刘惠民,等.烟草中抑芽丹残留量的测定[J].烟草科技,2006(7):43-45.ZHANG Wei,TANG Gangling,LIU Huimin,et al.Determination of maleic hydrazide residues in tobacco[J].Tobacco Science&Technology,2006(7):43-45.
[11]潘广文,赵增运,胡忠阳,等.高效离子排斥色谱法测定蔬菜中的马来酰肼[J].色谱,2010,28(7):712-715.PAN Guangwen,ZHAO Zengyun,HU Zhongyang,et al.Determination of maleic hydrazide in vegetables by high performance ion-exclusion chromatography[J].Chinese Journal of Chromatography,2010,28(7):712-715.
[12]Nagami H.Residues of maleic hydrazide and chlorpropham in potato chips[J].Bulletin of Environmental Contamination and Toxicology,1997,58(5):764-768.
[13]Morenoa M C,Stadlera T,Silva A A,et al.Determination of maleic hydrazide residues in garlic bulbs by HPLC[J].Talanta,2012,89(2):369-376.
[14]Lewis D J,Barnes K A,Wilkinson K,et al.Extraction of maleic hydrazide residues from potato crisps and their determination using high-performance liquid chromatography with UV and atmospheric pressure chemical ionisation mass spectrometric detection[J].Journal of Chromatography A,1996,750(1/2):391-396.
[15]Kubilius D T,Bushway R J.Determination of maleic hydrazide in potatoes and onions by fluorescence high performance liquid chromatography[J].Journal of Liquid Chromatography and Related Technologies,1999,22(4):593-601.
[16]汤健华,李儒发.马来酰肼的示波极谱法测定[J].昆明医科大学学报,1990,11(1):38-43.TANG Jianhua,LI Rufa.Oscillopolarographic determination of maleic hydrazide[J].Journal of Kunming Medical University,1990,11(1):38-43.
[17]李莉,周敏,房彦军,等.高碘酸钾-鲁米诺后化学发光法测定马来酰肼[J].食品科技,2008,33(3):223-225.LI Li,ZHOU Min,FANG Yanjun,et al.Flow-injection post-chemiluminescence determination of maleic hydrazide in luminol-potassium periodate reaction[J].Food Science and Technology,2008,33(3):223-225.
[18]邱萍,倪永年.抑芽丹的电化学行为及其测定[J].广西师范大学学报(自然科学版),2003,21(4):160-161.QIU Ping,NI Yongnian.Electrochemical behaviour of maleic hydrazide and its determination[J].Journal of Guangxi Normal University(Natural Science),2003,21(4):160-161.
[19]YC/T 31—1996烟草及烟草制品试样的制备和水分测定烘箱法[S].YC/T 31—1996 Tobacco and tobacco products—Preparation of test sample and determination of water content—Oven method[S].
[20]阮丽萍,沈东旭,吉文亮,等.采用HPLC-MS/MS方法同时测定花生中的马来酰肼和丁酰肼[J].江苏农业学报,2012,28(1):228-230.RUAN Liping,SHEN Dongxu,JI Wenliang,et al.Simultaneous determination of maleic hydrazide and daminozide in peanut by high performance liquid chromatography-tandem mass spectrometry[J].Jiangsu Journal of Agricultural Sciences,2012,28(1):228-230.
[21]吴成,赵志强.液相色谱质谱测定中甲醇乙腈对农药响应的影响[J].分析试验室,2015,34(6):711-716.WU Cheng,ZHAO Zhiqiang.Influence of methanol and acetonitrile on pesticides response by liquid chromatography-tandem mass spectrometry[J].Chinese Journal of Analysis Laboratory,2015,34(6):711-716.