高效液相色谱化学发光法检测鱼肉中三种四环素类药物

doi:10.14012/j.cnki.fjsc.2023.03.011

渔业研究 ›› 2023, Vol. 45 ›› Issue (3): 304-310.DOI: 10.14012/j.cnki.fjsc.2023.03.011

高效液相色谱化学发光法检测鱼肉中三种四环素类药物

王丽娟¹(), 张骊², 余颖¹, 姜琳琳¹, 刘海新¹, 田盟盟³

1.福建省水产研究所,福建省海洋生物增养殖与高值化利用重点实验室,福建厦门 361013
2.中国兽医药品监察所,北京海淀 100081
3.集美大学,福建厦门 361021

收稿日期:2022-08-22 出版日期:2023-06-25 发布日期:2023-06-16
作者简介:王丽娟(1980—),女,助理研究员,主要从事水产品质量安全和渔业环境监测研究。E-mail:wangguoqinli@163.com
基金资助:
福建省省属公益类科研院所基本科研专项(2020R10130013)

High-performance liquid chromatography with chemiluminescence determination of tetracyclines in the fish

WANG Lijuan¹(), ZHANG Li², YU Ying¹, JIANG Linlin¹, LIU Haixin¹, TIAN Mengmeng³

1. Key Laboratory of Cultivation and High-value Utilization of Marine Organisms in Fujian Province, Fisheries Research Institute of Fujian,Xiamen 361013,China
2. China Institute of Veterinary Drugs Control,Beijing 100081,China
3. Jimei University,Xiamen 361021,China

Received:2022-08-22 Online:2023-06-25 Published:2023-06-16

摘要/Abstract

摘要：

本文建立了可检测鱼肉中四环素类药物残留、既环保又低成本的高效液相色谱化学发光(HPLC-CL)方法。具有光致氧化性的纳米二氧化钛(TiO₂)与鲁米诺反应产生化学发光(CL)信号,经Fe²⁺催化增强,而四环素类药物与Fe²⁺的络合作用抑制信号,进而实现对四环素类药物的检测。本方法对四环素、金霉素和多西环素的定量限(LOQ)分别为10.0、30.0和10.0 mg/kg,并应用于鱼肉样品中四环素类药物的残留检测,满足检测要求。采用纳米TiO₂代替传统化学发光氧化剂,避免一些有毒试剂的应用和化学试剂污染,具有环保、价廉等优势。

关键词: 纳米, 二氧化钛(TiO₂), 化学发光, 四环素类药物, 鱼肉

Abstract:

The aims of the present study were to develop environmental and low cost methods for detection of tetracyclines (TCs) concentrations in the fish by high performance liquid chromatography with chemiluminescence.Luminol chemiluminescence (CL) could be generated by generated active oxygen species of photo-induced nano-titanium dioxide (TiO₂) instead of the traditional chemiluminescent oxidation reagents.Metal ions could catalyze this reaction.Based on the complexation between Fe²⁺ and TCs that remarkably decreased the Fe²⁺-catalyted luminol CL,the determination of TCs was proposed.The results indicated that the limit of quantitation for tetracycline,chloroteracycline and doxycycline were 10.0,30.0 and 10.0 mg/kg,respectively.The proposed method could be applied to the determination of the TCs in the fish,and meet the requirements of residue detection.Nano TiO₂ was used instead of traditional chemiluminescent oxidation reagents to avoid the application of some toxic reagents and chemical reagent pollution,and had the advantages of environmental protection and low price.

Key words: nano, titanium dioxide (TiO₂), chemiluminescence (CL), tetracyclines (TCs), fish

中图分类号:

S917.4

王丽娟, 张骊, 余颖, 姜琳琳, 刘海新, 田盟盟. 高效液相色谱化学发光法检测鱼肉中三种四环素类药物[J]. 渔业研究, 2023, 45(3): 304-310.

WANG Lijuan, ZHANG Li, YU Ying, JIANG Linlin, LIU Haixin, TIAN Mengmeng. High-performance liquid chromatography with chemiluminescence determination of tetracyclines in the fish[J]. Journal of Fisheries Research, 2023, 45(3): 304-310.

图/表 5

图1 UV-TiO2光催化反应器(a)和四环素类抗生素检测的流程图(b)

Fig.1 Schematic diagrams of UV-TiO2 photocatalytic reactor (a) and flow diagram of TCs (b)

图2 四环素类抗生素鱼肉空白样品色谱图(a)和加标后色谱分离图(b)

Fig.2 Typical chromatograms of a blank sample of fish (a), fish with addition of TCs (b)

表1 HPLC-nano TiO2-CL体系用于四环素类抗生素的分析参数

Tab.1 Analytical characteristic for the determination of tetracycline antibiotics by HPLC-nano TiO2-CL system

化合物Compounds	线性范围/(mg/L) Linear range	回归方程Regression equation	相关系数(R²)Correlation coefficient
四环素TC	0.5~50	Y=0.423 8x+1.635	0.991 3
金霉素CTC	0.5~50	Y=0.156 8x+0.416 8	0.995 6
多西环素DTC	0.5~50	Y=0.648 8x+4.268 8	0.992 1

表2 四环素类抗生素在鱼肉样品中的回收率(n=5)

Tab.2 Results of recovery test on tetracycline antibiotics determination for fish samples (n=5)

分析物 Compounds	添加浓度 /(mg/kg) Added concentration	平均回收率/% Average recovery	批内变异系数/% Coefficient of variation of intra-assay	批间变异系数/% Coefficient of variation of inter-assay	定量限 /(mg/kg) LOQ
四环素TC	10.0	72.6	5.4	12.7	10.0
	500	83.2	6.0
	1 000	95.6	5.7
金霉素CTC	30.0	73.7	5.9	10.6	30.0
	500	77.0	6.0
	1 000	89.4	7.0
多西环素DTC	10.0	77.3	7.1	14.7	10.0
	500	95.4	5.3
	1 000	107	5.1

图3 甲酸对化学发光信号的影响

Fig.3 Effect of formic acid on the decreased CL relative intensity

参考文献 18

[1]	Daghrir R, Drogui P. Tetracycline antibiotics in the environment:a review[J]. Environmental Chemistry Letters, 2013, 11 (3):209-227. DOI URL
[2]	廖碧钗. 盐酸土霉素在奥尼罗非鱼体内的药代动力学及残留研究[J]. 渔业研究, 2016, 38(2):89-95.
[3]	中华人民共和国国家标准.食品安全国家标准食品中兽药最大残留限量:GB 31650—2019[S]. 北京: 中国标准出版社, 2009.
[4]	Alanazi F, Almugbel R, Maher H M, et al. Determination of tetracycline,oxytetracycline and chlortetracycline residues in seafood products of Saudi Arabia using high performance liquid chromatography-photo diode array detection[J]. Saudi Pharmaceutical Journal, 2021, 29 (6):566-575. DOI URL
[5]	张青, 李慧素, 吴宁鹏, 等. 鸡组织中多西环素残留量测定的高效液相色谱法建立[J]. 中国兽药杂志, 2020, 54(10):1-9.
[6]	Guo M X, Gu X Y, Yang B Y, et al. Highly sensitive detection for tetracycline residues in water based on its decreasing effect on photocurrent of AgInS₂ quantum dots[J]. Journal of Environmental Chemical Engineering, 2022, 10 (3):107714. DOI URL
[7]	郑洁. 四环素类抗生素的柱前衍生化-HPLC分离-荧光增敏检测法[J]. 计量与测试技术, 2012, 39(2):69-71.
[8]	Zeng W S, Zhu C Y, Liu H C, et al. Ultrasensitive chemiluminescence of tetracyclines in the presence of MCLA[J]. Journal of Luminescence, 2017, 186:158-163. DOI URL
[9]	Li J, Wang S Z, Lai X J, et al. Selective and sensitive determination of tetracyclines by HPLC with chemiluminescence detection based on a cerium (Ⅳ)-methoxylated cypridina luciferin analogue system[J]. Journal of Separation Science, 2018, 41 (22):4115-4121. DOI URL
[10]	Fujishima A, Honda K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238:37-38. DOI
[11]	Fox M A, Dulay M T. Heterogeneous photocatalysis[J]. Chemical Reviews, 1993, 93:341-357. DOI URL
[12]	Nazeeruddin M K, Kay A, Rodicio I, et al. Conversion of light to electricity by cis-X₂bis(2,2’-bipyridyl-4,4’-dicarboxylate) ruthenium (Ⅱ) charge-transfer sensitizers (X = Cl^-,Br^-,I^-,CN^-,and SCN^-) on nanocrystalline titanium dioxide electrodes[J]. Journal of the American Chemical Society, 1993, 115:6382-6390. DOI URL
[13]	Horikoshi S, Watanabe N, Onishi H, et al. Photodecomposition of a nonylphenol polyethoxylate surfactant in a cylindrical photoreactor with TiO₂ immobilized fiberglass cloth[J]. Applied Catalysis B:Environmental, 2002, 37:117-129. DOI URL
[14]	Chen H, Gao Y, Su Y, et al. Photo-induced chemiluminescent method for determination of reducing sugars[J]. Luminescence, 2008, 23:287-291. DOI PMID
[15]	Hoffman A J, Carraway E R, Hoffmann M R. Photocatalytic production of H₂O₂ and organic peroxides on quantum-sized semiconductor colloids[J]. Environmental Science & Technology, 1994, 28:776-785. DOI URL
[16]	Saitoh K, Hasebe T, Teshima N, et al. Simultaneous flow-injection determination of iron(Ⅱ) and total iron by micelle enhanced luminol chemiluminescence[J]. Analytica Chimica Acta, 1998, 376:247-254. DOI URL
[17]	严保珍, 戴光智, 王德芳. 强力霉素与某些金属离子在水溶液中络合作用和稳定性的研究[J]. 四川医学院学报, 1983(1):26-30.
[18]	Serrano J M, Silva M. Rapid and sensitive determination of aminoglycoside antibiotics in water samples using a strong cation-exchange chromatography non-derivatisation method with chemiluminescence detection[J]. Journal of Chromatography A, 2006, 1117:176-183. PMID

高效液相色谱化学发光法检测鱼肉中三种四环素类药物

High-performance liquid chromatography with chemiluminescence determination of tetracyclines in the fish

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 18

相关文章 3

编辑推荐

Metrics

[1]	刘海新张农余颖姜琳琳李庐峰王艳君. 气相色谱-质谱法检测鱼肉中MS-222残留[J]. , 2013, 35(6): 441-447.
[2]	王福利. 纳米催化电气浮工艺对湖泊型水库原水中藻类的去除[J]. 福建水产, 2013, 35(5): 381-385.
[3]	王孝杉. 纳米催化微电解海水的杀菌效果及斜带石斑仔鱼对其适应性的研究[J]. 福建水产, 2013, 35(1): 22-26.