7 6 Vol. 7 No. 6 2016 6 Journal of Food Safety and Quality Jun., 2016 李芳 *, 陈莹, 李献刚, 李雪梅, 于凤娇 (,, 118300) 摘要 : 2006,,,,, - (HPLC-UV) - (LC-MS) - (LC-MS/MS) (ELISA),,,,, 关键词 : ; ; ; Progress on determination of nitrofuran and their metabolites in animal-derived food LI Fang *, CHEN Ying, LI Xian-Gang, LI Xue-Mei, YU Feng-Jiao (National Key Laboratory of Pesticide and Veterinary Drug Residue and Marine Biotonix Detection, Donggang Entry-Exit Inspection & Quarantine Bureau, Donggang 118300, China) ABSTRACT: Crabs carcinogenic event, as one of the top ten food safety incident had aroused concern in 2006. Although it was proved to be exaggerated later, the methods for detection of nitrofuran metabolites were still caused the attention in testing industry. The related nature of nitrofuran and their metabolites, limited requirements, test standards, detection methods and detection limit of nitrofuran and their metabolites were described in this article. Drugs of furan cannot be detected easily as they were rapidly metabolized in edible animal tissues, but nitrofuran metabolites could be kept for a long time in edible animal tissues. So, nitrofuran metabolites were chosen as the target analytes. High performance liquid chromatography-uv (HPLC-UV), liquid chromatography-mass spectrometry (LC-MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS) and enzyme-linked immunosorbent assay (ELISA) were common detection methods in many countries, besides, spectrophotometry and atomic absorption method were used by others. Advantages and disadvantages of various methods in practical application were compared, and some precautions in testing, including conditions and environment of derivation were suggested in this article. * 通讯作者 :,, E-mail: fanglee_4125@163.com *Corresponding author: LI Fang, Intermediate Engineer, Technical Center of Donggang Entry-Exit Inspection & Quarantine Bureau, No.22, Yinhe Road, China. E-mail: fanglee_4125@163.com
6, : 2321 KEY WORDS: nitrofuran; nitrofuran metabolites; determination method; limit 1 硝基呋喃类药物危害,,,, ( ),,, [1],, [2],,,, (zero tolerance),, 17%, [3] ; 3.93%(29/737), [4] ;,, [5],,,, 2 硝基呋喃类药物限量介绍 (furazolidone, 3- -2- 噁, AOZ) (furaltadone, 5- -3- -2- 噁, AMOZ) (nitrofurazone,, SEM) (furantoin, 1- -2-, AHD) 4 1 Fig. 1 1 4 Structures of 4 kinds of nitrofurans and their metabolites
2322 7,,,,, 1990 7 2377/90/EEC, A, 1.0 μg/kg [6], 1995, 1997 (EU) 2004 FDA 11 [7] 21CFR530.41 : 2002 EEC2377/90 ( ) [8,9] [2002]1 [7] 3 硝基呋喃类代谢物的检测,,,, (HPLC) - (HPLC-MS/MS), (EU)N0807/2001, (HPLC) GB/T 21311-2007 [10] GB/T 20752-2006 - [11] 781-4-2006 - [12] SN/T 2061-2008 - [13] SN/T 1627-2005 - [14], - (HPLC-MS/MS), - (HPLC-MS) - (HPLC-UV) (ELISA) 3.1 硝基呋喃代谢物的衍生化 3 : (1),,,, (C 18 -SPE),,, ; (2) -,, [15],,, 1.0 μg/kg; (3),,,,, -NH 2, 2- (2-NBA), 2,4-2- -5- [7], 2 2-37, 16 h,,,,,,, - (LC-UV) - (LC-MS) - (LC-MS/MS), 3.2 硝基呋喃类代谢物衍生化后的提取净化,, [16,17] 3.2.1 液液萃取, ( ),,,,,,, [18,19],, Piatkowska [20] 8, 85 Dasenaki [21] 143, Freitas [22] Storey [23], Robert [24] UHPLC-MS/MS
6, : 2323 Fig. 2 2 Structures of 4 kinds of nitrofurans and their derivatives, 4 160 [25] 16 120,,,,,, 3.2.2 固相萃取,,,,, [26],,,,, [16], [27], C 18 EN HLB C 18 HLB,, π-π - [28] EN HLB,,,,, HLB,,,, [29],, 3.3 注意事项探讨, [30],,, 25, ; ;, [31],, [32],, ph,, (HCN) [28],,, D 4 -AOZ D 5 -AMOZ 13 C-AHD 13 C 15 N-SEM,
2324 7,, ph, ph 7~7.5, AOZ AMOZ AHD SEM 4,, ph, 4 [33] 3.4 硝基呋喃代谢物的检测方法 3.4.1 高效液相色谱 - 紫外检测法 (HPLC-UV),,,,,,, 2001 11 1 [2001]138 - (HPLC-UV),, 4, 0.25 mg/kg, 0.12 mg/kg [34],,,,,,, -, [35] HPLC 22 3.4.2 高效液相色谱 - 串联质谱法 (HPLC-MS/MS) -,,,,,, HPLC-MS/MS,,, - (HPLC-MS/MS),,,,, [36],, 10,, HPLC-MS/MS, HPLC-MS/MS,, HPLC-MS, HPLC-MS/MS [37] LC-MS/MS,, 0.25 μg/kg,, 3.4.3 酶联免疫法 (ELISA) LC-UV LC-MS/MS,,,, (ELISA), AOZ AMOZ SEM AHD,,,, 0.1 μg/kg,,, ELISA,, 2004, Cooper [38] (AOZ), AOZ AOZ AOZ 3- CPAOZ,, AOZ 2- NPAOZ, AOZ NPAOZ ELISA, NPAOZ AOZ, Cooper [39] (SEM) CPSEM, CPSEM NPSEM SEM, 0.21 µg/kg Pimpitak [40] (AMOZ), AMOZ,, CPAMOZ AMOZ, CPAMOZ 23, ELISA AMOZ, 0.16 µg/kg 2012, Jiang [41] (AHD), CPAHD, NPAHD, AHD ELISA, 0.2 µg/kg,,,,,, 2012, Yan [42] AMOZ
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