中国乳业 ›› 2025, Vol. 0 ›› Issue (8): 94-101.doi: 10.12377/1671-4393.25.08.15

• 质量安全 • 上一篇    下一篇

高效液相色谱-质谱联用仪检测牛奶中17 种喹诺酮类药物残留量的研究

王克超1, 秦思文1, 宋鸽1, 李慧娟1,*, 张昊2, 李慧2, 王慧2, 孙宏娜2   

  1. 1 蒙牛乳业（沈阳）有限责任公司,辽宁沈阳 110122;
    2 内蒙古蒙牛乳业（集团）股份有限公司,内蒙古呼和浩特 011517
  • 出版日期:2025-08-25 发布日期:2025-09-10
  • 通讯作者: *李慧娟（1978-）,女,内蒙古呼和浩特人,硕士,高级工程师,研究方向为食品质量安全检测。
  • 作者简介:王克超（1994-）,男,辽宁营口人,本科,工程师,研究方向为食品质量安全检测;秦思文（1986-）,女,辽宁辽阳人,硕士,工程师,研究方向为食品质量安全检测;宋鸽（1983-）,女,黑龙江哈尔滨人,硕士,高级工程师,研究方向为食品质量安全检测;张昊（1996-）,男,内蒙古呼和浩特人,本科,助理工程师,研究方向为食品质量安全检测;李慧（1981-）,女,内蒙古呼和浩特人,本科,高级工程师,研究方向为食品质量安全检测;王慧（1982-）,女,内蒙古呼和浩特人,本科,高级工程师,研究方向为食品质量安全检测。孙宏娜（1984-）女,内蒙古呼和浩特人,本科,工程师,研究方向为食品质量安全检测。
  • 基金资助:
    呼和浩特科技计划资助项目（2021-农-重-1）

Study on the Detection of 17 Quinolone Drug Residues in Milk by High Performance Liquid Chromatography-mass Spectrometry

WANG Kechao1, QIN Siwen1, SONG Ge1, LI Huijuan1,*, ZHANG Hao2, LI Hui2, WANG Hui2, SUN Hongna2   

  1. 1 Mengniu Dairy（Shenyang）Co.,Ltd.,Shenyang Liaoning 110122;
    2 Inner Mongolia Mengniu Dairy（Group）Co.,Ltd.,Hohhot Inner Mongolia 011517
  • Online:2025-08-25 Published:2025-09-10

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摘要： [目的]作为富含营养的日常食品,牛奶的质量安全备受关注。喹诺酮类药物因其抗菌谱广、成本低等特性,常被用于奶牛疾病的防治。然而,不合理使用易导致其在牛奶中残留,对人体健康构成潜在威胁。现有检测方法存在样品处理步骤繁琐、检测项目有限、检测干扰多等问题,难以满足高效、准确检测牛奶中多种喹诺酮类药物残留量的需求。基于此,建立一种高效液相色谱-质谱联用法,同时检测17 种喹诺酮类药物残留量,为保障牛奶质量安全提供有力技术支持。[方法]采用乙腈和磷酸盐缓冲液提取样品中的喹诺酮类药物,经HLB固相萃取柱净化,5%氨化甲醇洗脱,以甲醇-甲酸水溶液作为流动相,经C18色谱柱分离,质谱采用电喷雾正离子模式（ESI+）,多反应监测（MRM）,利用UPLC-MS（Waters UPLC-TQD）进行检测,外标法定量,增强可重复性。[结果]17 种喹诺酮类药物均在6 min内出峰且峰型良好,方法检出限范围0.005~0.228 μg/kg,方法定量限范围0.017~0.759 μg/kg,样品加标回收率为60.0%~118.0%,RSD为1.4%~19.9%,符合《GB 5009.295—2023 食品安全国家标准 化学分析方法验证通则》中4.1.5、4.1.6的要求。[结论]该方法操作简便、稳定性好、准确度高,适用于牛奶中17 种喹诺酮类药物残留量的检测。

关键词: 高效液相色谱-质谱联用仪, 喹诺酮, 分析方法

Abstract: [Objective] As a nutritious daily food,the safety and quality of milk is highly concerned.Quinolone drugs are widely used in the prevention and treatment of diseases in dairy cows due to their broad-spectrum antibacterial properties and low cost.However,irrational use may lead to its residues in milk,which poses potential threats to human health.The existing detection methods have problems such as complicated sample processing steps,limited detection items,and multiple detection interferences,which cannot meet the needs of efficient and accurate detection of multiple quinolone drugs in milk.Therefore,a high performance liquid chromatography-tandem mass spectrometry method was established to simultaneously detect the residues of 17 quinolone drugs,providing strong technical support for ensuring the safety and quality of milk.[Method] Quinolone drugs in the sample were extracted with acetonitrile and phosphate buffer,purified by HLB solid phase extraction column,eluted with 5% ammoniated methanol,separated by C18 chromatographic column with methanol-formic acid aqueous solution as the mobile phase. The mass spectrometry using electrospray positive ion mode（ESI+） and multiple reaction monitoring（MRM）. Detection was carried out using UPLC-MS（Waters UPLC-TQD）,and quantification was performed using the external standard method to enhance repeatability.[Result] All 17 quinolone drugs elminated within 6 minutes with good peak shapes,and the detection limit range of the method was 0.005~0.228 μg/kg,the quantitation limit range was 0.017~0.759 μg/kg,the recovery rate of the sample spiked was 60.0%~118.0%,and the RSD was 1.4%~19.9%. It meets the requirements of 4.1.5 and 4.1.6 in the“GB 5009.295—2023 National Food Safety Standard - General Rules for Validation of Chemical Analysis Methods”.[Conclusion] This method is easy to operate,has good stablility and high accuracy.It is suitable for the detection of 17 quinolone drugs residues in milk.

Key words: High performance liquid chromatography-mass spectrometry, quinolone, analysis method

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