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1 6 12 Vol. 6 No Journal of Food Safety and Quality Dec., * 吴健, 朱峰, 吉文亮, 李放, 阮丽萍, 刘华良 (, ) 摘要 : 目的 14 - 方法 0.22 μm, (0.05%)+ -, Atlantis dc-c 18, (electro spray ion source, ESI) (multi-reaction monitoring, MRM) 结果 14, 5 ng/l~1000 ng/l, 10 ng/l~1000 ng/l, 20 ng/l~1000 ng/l, 50 ng/l~1000 ng/l, r , 83.9%~110.0%, 2.4%~15.4%, 1.0 ng/l~20 ng/l 结论, 关键词 : ; ; ; - Simultaneous determination of 14 quinolone residues in water by high performance liquid chromatography-tandem mass spectrometry WU Jian, ZHU Feng, JI Wen-Liang, LI Fang, RUAN Li-Ping, LIU Hua-Liang * (Jiangsu Provincial Center for Disease Prevention and Control, Nanjing , China) ABSTRACT: Objective To establish a rapid analytical method for the simultaneously screening and detection of 14 quinolone residues in water by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Methods After a high speed centrifugation, the samples were filtered 0.22 µm millipore filter and then were separated on an Atlantis dc-c18 column with the mobile phases of formic acid (0.05%) and methanol-acetonitrile. The electrospray ionization (ESI) source in positive ion mode was used for multiple reaction monitoring (MRM). Results The 14 quinolone chemical components showed a good linear relationship in their concentration ranges with the correlation coefficients more than 0.99 except ciprofloxacin. The linear relationship of ofloxacin, enrofloxacin, lomefloxacin, difloxacin, sarafloxacin, flumequine and gatifloxacin were 5 ng/l~1000 ng/l, ciprofloxacin, orbifloxacin, marbofloxacin and pefloxacin were 10 基金项目 : (BE ) (ZX201109) Fund: Supported by Jiangsu Provincial Science and Technology Support Project (BE ) and Jiangsu Provincial 12th Five-Year Health Development Project with Science and Education (ZX201109) * 通讯作者 :,,, *Corresponding author: LIU Hua-Liang, Associate Researcher, Jiangsu Provincial Center for Disease Control and Prevetion, No.172, Jiangsu Road, Nanjing , China.

2 12, : ng/l~1000 ng/l, fleroxacin and enoxacin were 20 ng/l~1000 ng/l, and danofloxacin was 50 ng/l~1000 ng/l. The recoveries were all of 83.9%~110.0% and the relative standard deviation (RSD) were all of 2.4%~15.4%. The limits of detection (LOD) were all of 1.0 ng/l~20 ng/l. Conclusion This method is rapid, simple, sensitive, and accurate, which provides a basis for the investigation and monitoring of the pollution level of antibiotics in water. KEY WORDS: quinolone residues; antibiotics; water; high performance liquid chromatography mass spectrometry mass spectrometry 1 引言 (Quinolones) [1],,,,, ( ) [2],,,,, [3] (capillary electrophoresis, CE) [4-8] (high performance liquid chromatography, HPLC) - [9-17] (high performance liquid chromatography mass spectrometry mass spectrometry, HPLC-MS/MS), 14 - (HPLC-MS/MS) -,,, 14 -,,, 2 材料与方法 2.1 仪器 试剂与材料 UHPLC LC 30A ( SHIMADZU ); Q-trap ( AB SCIEX ); ( Sigma ); ( Merck ); MS ( Fisher ) ( ) (fleroxacin) (lomefloxacin) (gatifloxacin) (danofloxacin), (enoxacin)sigma, (difloxacin) (pefloxacin) (ofloxacin) (sarafloxacin) (flumequine) (enrofloxacin) (marbofloxacin) (ciprofloxacin) Dr.Ehrenstorfer, (orbifloxacin) 2.2 标准溶液配制 (1.0 mg/ml): 0.01g, 10 ml, 1.0 mg/ml, 20 (1.0 μg/ml): 25 μl 25 ml,, 1.0 μg/ml, 4 :

3 ng/l 2.3 样品处理 15 min, 1.5 ml, rpm/min 5 min, 0.22 μm, 2.4 实验条件 : Atlantis dc-c18 (4.6 mm 150 mm, 5 µm, Waters); : A (0.05%), B - (4:6, V:V); : 20%B (0~3.0 min); 20%B 70%B (3.0~6.5 min); 70%B 90%B (6.5~9.0 min); 90%B 20%B (9.0~9.1 min); 20%B (9.1~11.0 min) 0.5 ml/min; 40 ; 20 μl : : (ESI); : ; : (MRM); : 550 ; Curtain Gas: 35 psi; Ion Source Gas1: 55 psi; Ion Source Gas2: 55 psi; : 5.5 kv; 1 表 1 14 种喹诺酮类药物残留的离子参数 Tbale 1 Ion parameters of the 14 quinolone residues (m/z) (m/z) (V) (V) * * * * * * * * * * * *

4 12, : (m/z) (m/z) (V) (V) 续表 * * : * 3 结果与讨论 3.1 质谱条件的优化, 100 ng/ml μl/min, (ESI + ) (ESI - Q1,, 14 ESI +,,, MRM DP CE,, 色谱条件的优化 [16] [M+H] +, ESI +,,, 0.05% 0.1% 0.5% -,, (6:4 5:5 4:6, V:V), 4:6,, 0.05% + - (4:6, V:V), 14,,, 目标化合物提取方法的选择, ng/l, [9,18] - μg/l,, ;,,, 15 min, 0.22 μm, ( μl),, 20 μl,, 3.4 方法的线性范围 相关系数 检出限 定量限和精密度, (Y) (X, ng/l), 5 ng/l~1000 ng/l, 10 ng/l~1000 ng/l, 20 ng/l~1000 ng/l, 50 ng/l~1000 ng/l; r 0.98, ; (S/N=3) (S/N=10), ng/l, 50 ng/l; 20 ng/l 100 ng/l 500 ng/l (n=6), 83.9%~110.0%, 2.4%~15.4% 实际样品的测定 17 (6 6 5 ), 17 14

5 4970 食品安全质量检测学报 Fig. 1 图 1 14 种喹诺酮类药物残留的多反应监测色谱图 Multiple reaction monitoring (MRM) chromatography of the 14 quinolone residues 第6卷

6 第 12 期 吴 Fig. 1 健, 等: 高效液相色谱-质谱联用法同时检测水体中 14 种喹诺酮类药物残留 续图 1 14 种喹诺酮类药物残留的多反应监测色谱图 Multiple reaction monitoring (MRM) chromatography of the 14 quinolone residues 4971

7 Table 2 表 2 14 种喹诺酮类药物残留的 LOD LOQ r 线性方程 回收率及 RSD LOD, LOQ, linear correlation coefficient(r), linear equation, recoveries and relative standard deviation(rsd) for 14 quinolone residues (ng/l) (ng/l) (r) /RSD(%, n=6) 20 ng/l 100 ng/l 500 ng/l Y = X Y = 174.4X Y = 221.7X Y = X Y = X Y = X Y = X Y = X Y = X Y = X Y = X Y = 733.2X Y = X Y = X

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