固相萃取-同位素稀释/超高效液相色谱-串联质谱法测定蜂蜜中甲硝唑、二甲硝咪唑和洛硝哒唑

摘要/Abstract

摘要： 建立超高效液相色谱-串联质谱法测定蜂蜜中甲硝唑、二甲硝咪唑、洛硝哒唑残留量的方法。样品采用乙酸乙酯提取，同位素稀释，混合阳离子交换柱净化，经C18色谱柱（3.0 mm×100 mm,1.7μm）分离后，在多反应检测（multiple reaction monitoring, MRM）模式下测定，内标法定量。甲硝唑、二甲硝咪唑、洛硝哒唑在1.0-100.0ng/mL浓度范围内线性关系良好，测定结果相对标准偏差为1.6%～3.7%（n=6），平均加标回收率为95.0%～101.4%，能有效降低基质干扰。该方法操作简便，结果准确，普遍适用于蜂蜜中甲硝唑、二甲硝咪唑、洛硝哒唑的测定。

关键词: 甲硝唑, 二甲硝咪唑, 洛硝哒唑, 蜂蜜, 超高效液相色谱-串联质谱法(UPLC-MS), 固相萃取

Abstract: To establish a method for the determination of metronidazolem, dimetrIdazole and ronidazole in honey by ultra performance liquid chromatograph-tandem mass spectrometry (HPLC-MS/MS). The analytes were extracted from samples, decontaminated using a cation exchange cartridge, separated on a C18 (3.0mm×100mm,1.7μm) chromatographic column, scanned in the multiple reaction monitoring (MRM) mode, and quantitatively analyzed by internal standard method. Metronidazolem, dimetridazole and ronidazole were separated well and their calibration curves were linear in the concentration range of 1-100 ng/mL. The minimum detection limit was 1.0 μg/kg. The relative standard deviation of the determination results was 1.6%-3.7%(n=6), and the average recovery was 95.0%-101.4%. This method can effectively reduce matrix interference, and it is convenient, and efficient, and has a good accuracy. It is suitable for the determination of residues of metronidazolem, dimetridazole and ronidazole in different kinds of honey.

Key words: metronidazolem, dimetridazole, ronidazole, honey, uplc performance liquid chromatograph-tandem mass spectrometry (UPLC-MS), solid phase extraction

中图分类号:

550.1030

林浩刘川张阳阳肖全伟毛锐万渝平戴琴. 固相萃取-同位素稀释/超高效液相色谱-串联质谱法测定蜂蜜中甲硝唑、二甲硝咪唑和洛硝哒唑[J]. 食品科学, 0, (): 0-0.

Hao LIN. Determination of Metronidazolem, Dimetridazole and Ronidazole in Honey by UPLC-MS/MS with On-line Solid-phase Extraction and Isotope Dilution[J]. FOOD SCIENCE, 0, (): 0-0.

参考文献

[1] 陈迁, 梅和坤, 白楠, 等.硝基咪唑类药物在人体内代谢的研究进展[J]. 中国药学杂志, 2015, 50(14): 1169-1173.
[2] Tariq N, Basharat A, Khan D H, et al. Treatment for Symptomatic Bacterial Vaginosis: ARandomized Controlled Trial[J]. Journal of College of Physicians And Surgeons Pakistan, 2017, 27(11):686-689.
[3] Volpato A, Fortuoso B F, Campigotto G, et al. Secnidazole for control of giardiasis in dairy calves[J]. Experimental Parasitology, 2018:16-18. DOI: 10.1016/j.exppara.2018.04.008
[4] M Arias, O P Chevallier, S F Graham, et al. Metabolomics reveals novel biomarkers of illegal 5-nitroimidazole treatment in pigs. Further evidence of drug toxicity uncovered [J]. Food Chemistry, 2016, 199: 876-884. DOI:10.1016/j.foodchem.2015.12.075.
[5] HERNANDEZ-MESA M, CRUCES-BLANCO C, GARCIA-CAMPANA AM. Simple and rapid determination of 5-nitroimidazoles and metabolites in fish roe samples by salting-out assisted liquid-liquid extraction and UHPLC-MS/MS [J]. Food Chem, 2018, 252: 294-302. DOI:10.1016/j.foodchem.2018.01.101.
[6] European Commission． Council Regulation (EEC) No 2080/92 of 30．June 1992 instituting a Community aid sheme for forestry measures in agriculture［EB/OL］．https://www．researchgate．net/publication/260137992_Council_Regulation _EEC_No_208092_of_30_June_1992_instituting_a_Community_aid_sheme_for_forestry_measures_in_agriculture．
[7] 中华人民共和国农业农村部. GB 31650－2019 食品中兽药最大残留限量[S]. 北京: 中国标准出版社, 2019.
[8] 农业农村部. 中华人民共和国农业农村部公告第250号--食品动物中禁止使用的药品及其他化合物清单[Z]. 2019-12-27:,2019.
[9] 李珍珍, Maddili Swetha Kameswari, TangadanchuVijai Kumar Reddy, 等. 硝基咪唑杂环药物化学研究进展[J]. 中国科学: 化学, 2019, 49(02): 230-255.
[10] Azam A, Peerzada MN, Ahmad K. Parasitic diarrheal disease: drug development and targets [J]. Frontiers in Microbiology, 2015, 6:1183.
[11] Sackton K L, Dimova N, Xing Z, et al. Synergistic blockade of mitotic exit by two chemical inhibitors of the APC/C.[J]. Nature, 2014, 514(7524):646. DOI:10.1038/nature13660.
[12] GB/T 21318-2007, 动物源食品中硝基咪唑残留量检验方法[S].
[13] SN/T 1928-2007, 进出口动物源性食品中硝基咪唑残留量检测方法液相色谱-质谱/质谱法[S].
[14] SN/T 2624-2010, 动物源性食品中多种碱性药物残留量的检测方法液相色谱-质谱/质谱法[S].
[15] 上官苗苗. 动物源性食品中硝基咪唑类药物残留快速检测方法研究[D]. 浙江: 浙江工业大学, 2020: 2-4.
[16] 尹青春, 谭高好, 邓浩, 等. UPLC-MS/MS法测定鸡蛋中17种硝基咪唑类药物及代谢物[J]. 食品工业, 2021, 42(04): 483-487.
[17] 梁宇, 司露露, 汪文龙, 等. 高效液相色谱-串联质谱法和高效液相色谱法测定蜂蜜中氯虫苯甲酰胺残留量[J]. 食品安全质量检测学报, 2022, 13(02): 492-497. DOI:10.19812/j.cnki.jfsq11-5956/ts.2022.02.037.
[18] 张杰, 胡伟宏, 吉小凤, 等. 国内外蜂药使用现状调查[J]. 中国蜂业, 2021, 72(10): 26-29.
[19] 邢燕, 王敏, 高慧, 等. 山东省市售蜂蜜中氯霉素和甲硝唑监测及风险评估分析[J]. 现代预防医学, 2021, 48(01): 174-177.
[20] GB/T 23410-2009, 蜂蜜中硝基咪唑类药物及其代谢物残留量的测定　液相色谱-质谱/质谱法[S].
[21] 杨洪生, 张秋云, 谭秀慧, 等. 同位素稀释-液相色谱-串联质谱法同时测定水产品中13种镇静剂残留[J]. 食品安全质量检测学报, 2021, 12(15): 6017-6025.DOI:10.19812/j.cnki.jfsq11-5956/ts.2021.15.017.
[22] 周一卉, 李香月, 王涛, 等. 固相萃取-超高效液相色谱-串联质谱法测定鸡蛋中甲硝唑残留[J]. 食品安全质量检测学报, 2021, 12(12): 4831-4837.DOI:10.19812/j.cnki.jfsq11-5956/ts.2021.12.019.
[23] 刘宇尘, 周剑, 王敏, 等. 同位素稀释-超高效液相色谱-串联质谱法测定鸡蛋中3种类固醇激素[J]. 食品安全质量检测学报, 2021, 12(24): 9334-9341.DOI:10.19812/j.cnki.jfsq11-5956/ts.2021.24.005.
[24] 冯湘玲, 丁玉峰, 汪震, 等. 高效液相色谱-串联质谱法测定雷公藤制剂中5种有效成分的含量[J/OL]. 中国医院药学杂志: 1-9[2022-02-13].http://kns.cnki.net/kcms/detail/42.1204.R.20220110.1655.004.html.
[25] 侯嫔, 张瑜, 彭莲, 等. 焦化废水中痕量苯并（a）芘的固相萃取和GC-MS检测方法[J/OL]. 环境工程: 1-8[2022-02-14].http://kns.cnki.net/kcms/detail/11.2097.x.20220111.1143.012.html.
[26] 杨明, 伊鋆, 陈丹, 等. 氧化锌QuEChERS/高效液相色谱-串联质谱法测定蜂蜜中7种林可酰胺类与大环内酯类兽药残留[J]. 分析测试学报, 2020, 39(08): 974-979.
[27] Xian Y, Dong H, Wu Y, et al. QuEChERS-based purification method coupled to ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) to determine six quaternary ammonium compounds (QACs) in dairy products.[J]. Food Chemistry, 2016, 212(dec.1):96-103. DOI:10.1016/j.foodchem.2016.05.151.
[28] 刘洋帆,李绪鹏,冯阳,等.超高效液相色谱-串联质谱法测定鲣鱼中的生物胺[J/OL].食品与发酵工业:1-9[2022-02-13].DOI:10.13995/j.cnki.11-1802/ts.029408.
[29] 芦丽, 方方, 冯有龙, 等. 固相萃取净化-超高效液相色谱-三重四极杆/线性离子阱串联质谱法测定化妆品中16个卡因类组分[J]. 药物分析杂志, 2021, 41(12): 2178-2190.DOI:10.16155/j.0254-1793.2021.12.17.
[30] 覃弘毅, 刘小玲. 超高效液相色谱-串联质谱法结合全自动固相萃取测定螺蛳粉中5种罂粟壳生物碱[J]. 食品科技, 2021, 46(10): 284-289.DOI:10.13684/j.cnki.spkj.2021.10.045.