高效液相色谱串联质谱法同步检测大麦产品中唑啉草酯和炔草酯及解毒喹的残留量

摘要/Abstract

摘要： 摘要：本文旨在利用QuEChERS方法建立高效液相色谱-串联质谱法同时检测大麦中的除草剂唑啉草酯和炔草酯及解毒喹的残留检测方法。样品用乙腈提取，C18和N-丙基乙二胺（PSA）净化，在XBridge-C18 色谱柱上分离，以0.1%甲酸溶液和乙腈作为流动相进行梯度洗脱，ESI 正离子模式扫描，多反应监测（MRM）测定，基质匹配外标法定量分析。大麦粒中唑啉草酯、炔草酯和解毒喹在0.1-100 μg/L 浓度范围内呈线性关系，相关系数高于0.997；方法的检出限（LOD）分别为0.05、0.02和0.01μg/L。唑啉草酯、炔草酯和解毒喹的精密度试验中3个加标水平（含残留限量）平均回收率在76.87%-103.55%之间，相对标准偏差（RSD）在2.4%-9.2%（n=5）之间。采用该方法对当地市场的大麦麦粒和大麦苗粉中上述三种化合物的残留进行了应用性评价，该方法将为大麦产品中唑啉草酯等三种化合物的残留检测提供了技术支撑。

关键词: 关键词：大麦, 唑啉草酯, 炔草酯, 解毒喹, 高效液相色谱-串联质谱

Abstract: Abstract: A method for simultaneous determination of two herbicides, pinoxaden, Clodinafop-propargyl and its safety agent Cloquintocet-mexyl in barely?by high performance liquid chromatography-tandem mass spectrometry with QuEChERS. The samples was extracted -by acetonitrile, cleaned up with C18 and PSA . The analytes were separated by a reversed phase C18 column(XBridge-C18 column) , and gradiently eluted with 0.1% formic acid solution and acetonitrile as mobile phase.? The samples?were?analyzed under the multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI+) and quantified?by external standard with matrix matched method. The good linearity was obtained from pinoxaden, Clodinafop-?propargyl and Cloquintocet-mexyl in barely?at the concentration of 0.1-100 μ g / L, and the linear correlation coefficient was higher than 0.997. Respectively, the limit of detection (LOD) of the method was 0.05, 0.02 μg/L and 0.01 μg/ L. The pinoxaden average recoveries of the three concentration levels were 76.87%- 80.722%, the Clodinafop-propargyl average recoveries of the three concentration levels were 95.07%-99.15%, and the Cloquintocet -mexyl average recoveries of the three concentration levels were 96.73%- 103.55%. The repeatability expressed as relative standard deviations (RSD) was ranged from 2.4% to 9.2%(n = 5).?The method was used to evaluate the residue of the above three compounds in local market barley grain and seedling powder. And the method provides technical support for the determination of pinoxaden residues in barley products.

Key words: Keywords: Barley, pinoxaden, clodinafop-propargyl, cloquintocet-mexyl, high performance liquid chromatography -tandem mass spectrometry

中图分类号:

O657.63

韩何丹佘永新贺永娟何亚荟王猛强邵勇王淼王珊珊郑鹭飞曹振邵华金茂俊金芬王静高丽萍. 高效液相色谱串联质谱法同步检测大麦产品中唑啉草酯和炔草酯及解毒喹的残留量[J]. 食品科学, 0, (): 0-0.

参考文献

参考文献
[1] 康振生. 中国农作物病虫害防控科技的发展方向[J]. 植物保护,2010, 36(3): 9-12.
[2] 王霞. 新型麦田除草剂之唑啉草酯[J]. 山东农药信息, 2014(2):26-27.
[3]Mian Muhammad, Muhammad Rasul Jan, Jasmin Shah, et al. Evaluation and statistical analysis of the modified QuEChERS method for the extraction of pinoxaden from environmental and agricultural samples[J]. Journal of Analytical Science and Technology,2017,8(1).
[4] 张一宾，孙　晶. 国内外有机磷农药的概况及对我国有机磷农药发展的看法[J]. 农药，1999，38（7）：1-3.
[5] 俞发荣，李登楼. 有机磷农药对人类健康的影响及农药残留检测方法研究进展[J]. 生态科学，2015，34（3）：197-203.
[6]张敏恒. 农药品种手册精编. 北京：化学工业出版社，2012.12
[7]樊海安.2,4-DT 酯与百草敌复配防除麦田杂草试验[J].安徽农业科学,2008,36(13)：5516-551.
[8]WENBI GUAN,YONGQIANG MA, HONGYAN ZHANG. Dissipation of Clodinafop-Propargyl and Its Metabolite in Wheat Field Ecosystem[J]. Bulletin of Environmental Contamination and Toxicology,2013,90(6).
[9]S.H.E. HAMADA, M.F. ABDEL-LATEEF, A.E. ABDELMONEM, R.M.A, et al. Helalia. Efficiency of certain clodinafop - propargyl formulations in controlling annual grassy weeds in wheat[J]. Annals of Agricultural Sciences,2013,58(1).
[10]李成.炔草酯用量大会致麦苗受害[J].农家致富,2014(08):35.
[11] 张全国，杨利华，董金皋，等．解草酯及二氯丙烯胺对烟嘧磺隆和硝磺草酮药害的解毒效应研究 [J]．河北农业科学，2010，14(9)：63-65．
[12]D. V. DZARDANOV, L. S. ELINEVSKAYA, V. I. ROLDUGHIN. The influence of the nature of adjuvants on stability of herbicide emulsions based on fenoxaprop-P-ethyl and cloquintocet-mexyl[J]. Colloid Journal,2015,77(5).
[13]吕程程. 解草酯和解草酮的合成工艺研究[D].哈尔滨理工大学,2014.
[14] LAY M M, CASIDA J E, Dichloro-Acetamide Antidotes Enhance Thiocarba-mate Sulfoxide Detoxification by Eleuationom Root Glutafione Content Gluta- fione-S-Transferase activity [J]. Pestic Biochem Physio, 1996, (6): 442-456．
[15] STEPHENSON G R. Structure-Activity Relationships for EPTC Antidotes in Corn [J]. Journal of Agricultural and Food Chemistry, 1978, (26): 137-140．
[16] 郑伯霖．除草剂解毒剂的新进展[M]．农药译丛，1989，11(2)：17-24
[17]谢俊婷,刘欣恩,吴妍,张宏涛.炔草酯-唑啉草酯的高效液相色谱法研究[J].化工管理,2018(24):162-163.
[18]冯辉,王树杰,郜战宁,薛正刚,杨永乾,潘正茂.3种除草剂对大麦田杂草防除效果及产量效应[J].湖南农业科学, 2017 , (06):57-59+63.
[19]RAJENDER SINGH CHHOKAR, RAMESH KUMAR SHARMA, RAM KUMAR SINGH, et al.Ready mix combination of pinoxaden and clodinafop for efficient control of grass weeds in wheat[J]. Wheat and Barley Research, 2015,7(1):55-58.
[20]V. S. HOODA, MEENAKSHI SANGWAN, MEENA SEWHAG. Evaluation of Clodinafop-propargyl 15 WDG as a New Formulation against Weeds in Wheat [J]. Chem Sci Rev Lett 2017, 6(21): 315-318 .
[21] GB 2763-2016 食品安全国家标准食品中农药最大残留限量[S]. 北京:国家标准出版社. 2017,153-215.
[22] 谢艳红，邱立红，蒋家珍，等甲基二磺隆及比唑解草醋对不同品种小麦酶的影响农药学学报, 2004, 3(6): 81-84.
[23] 武鹏, 于荣. 5%唑啉草酯乳油高效液相色谱分析方法研究[J]. 农药科学与管理, 2016, 37 (4): 48-50.
[24]KAMLESH VISHWAKARMA,?BIPUL BEHARI SAHA,?SUNILKUMAR SING, et al. Method Development and Validation for Quantification of Active Content and Impurities of Clodinafop Propargyl and Its Enantiomeric Separation by High-Performance Liquid Chromatography[J]. International Scholarly and Scientific Research & Innovation, 2017,11(5) :1.
[25]Z SHEN,?W ZHU,?X XU, et al.?Direct chiral resolution of cloquintocet‐mexyl and its application to in vitro degradation combined with clodinafop‐propargyl[J]. Biomedical Chromatography,?2012?,?26?(9)?:1058-1061. DOI 10.1002/bmc.1745.
[26]李腾飞,赵风年,张超,江泽军,刘广洋,王静,刘海金,徐平,金茂俊,金芬,邵华,王珊珊,郑鹭飞,佘永新.高效液相色谱-三重四极杆质谱法同时测定番茄中水杨酸和赤霉酸[J].食品科学,2016,37(08):182-186.
[27]谢瑜杰,陈辉,彭涛,代汉慧,胡雪艳,范春林,呼秀智,薛占永.QuEChERS-高效液相色谱-串联质谱测定牛奶中6种玉米赤霉烯酮类毒素[J/OL].食品科学:1-11[2018-10-25].http://kns.cnki.net/kcms/detail/11.2206.TS.20180919.1316.022.html.
[28] ERIN C, DIANE MWD, ZILING L, et al. Systematic and comprehensive strategy for reducing matrix effects in LC/MS/MS analyses [J]. J Chromatogr B, 2007, 852: 22–34.
[29]向平, 沈敏, 卓先义. 液相色谱-质谱分析中的基质效应[J].分析测试学报, 2009, 28(6): 753–756.