在线净化/液相色谱-四极杆/静电场轨道阱高分辨质谱法快速筛查水产品中123种兽药残留

Rapid Screening and Confirmation of 123 Veterinary Drugs in Aquatic Products by On-line Cleanup/Liquid Chromatography-Quadrupole/Electrostatic Field Orbitrap High-resolution Mass Spectrometry

建立了快速筛查水产品中123种兽药残留的在线净化/液相色谱-四极杆/静电场轨道阱高分辨质谱检测方法,兽药涵盖15类123种(20种磺胺类、6种大环内酯类、16种喹诺酮类、12种β-激动剂、17种苯并咪唑类、4种四环素类、2种镇静剂、6种激素、4种β-内酰胺类、1种氨苯砜、2种抗球虫药、2种染料、24种糖皮质激素、1种氯霉素、6种雷索酸内酯类)。样品经乙腈-水(8∶2)提取,提取液经在线净化柱Cyclone^(TM) P(0.5 mm×50 mm)净化、富集后,将目标物洗脱转至Atlantis T3分析柱(100 mm×4.6 mm,3μm),经色谱分离后,采用四极杆/静电场轨道阱高分辨质谱,以全扫描/数据依赖二级扫描(Full Scan/dd⁃MS2)模式检测,外标法定量。结果表明,123种兽药在各自质量浓度范围内呈良好线性,相关系数(r^(2))均大于0.99,方法定量下限为0.1~50μg/kg,加标回收率为53.7%~129%,相对标准偏差(RSD)为2.7%~19%。该方法简便、准确、灵敏,适用于批量水产品中多种兽药残留的快速筛查。

A liquid chromatography-quadrupole/electrostatic field orbitrap high-resolution mass spectrometry with on-line cleanup was established for the rapid screening of 123 veterinary drug resi⁃dues in aquatic products,including fifteen types of 123 wide-range veterinary drugs,i.e.20 sulfon⁃amides,6 macrolides,16 quinolones,12β-agonists,17 benzimidazoles,4 tetracyclines,2 seda⁃tives,6 hormones,4β-lactams,1 dapsone,2 anticoccidials,2 dyes,24 glucocorticoids,1 chlor⁃amphenicols and 6 resorcylic acid lactones.The samples were extracted with acetonitrile-water(8∶2)by ultrasonic extraction,followed by an automated turbulent flow cyclone chromatography sample clean-up system.The online purification technology TurboFlow is mainly used to achieve the purpose of purification by means of diffusion and dissolution,size exclusion,etc.as it has more advantages than traditional solid phase extraction and matrix dispersion extraction.Sample extraction solution was purified and collected with a Cyclone^(TM) P column(0.5 mm×50 mm).The analytes were eluted from the extraction column and put into an Atlantis T3 analytical column(100 mm×4.6 mm,3μm)prior to chromatographic separation and detection in Full Scan/ddMS^(2) mode.The target compounds were monitored in both positive and negative full scan modes.The confirmatory analysis was carried out by determining the retention time and accurate masses of all compounds and fragment ions upon target MS/MS,and the external standard method was used for quantification.The total run time was within 18 min,including analytical chromatography and re-equilibration of the turboflow system.The optimization of different experimental parameters including extraction,separation and detection were evaluated separately in this paper.The developed method was validated,and good performing characteristics were obtained.The screening of analytes was performed by library searching.The method could be used for the rapid screening of 123 drugs in aquatic products by means of accurate mass of quasi-molecular ion,retention time and the secondary fragment ion spectra for confirmation.The results showed that the calibration curves of the 123 drugs were linear in their respective concen⁃tration ranges with correlation coefficients(r^(2))more than 0.99.The limits of quantitation were be⁃tween 0.1μg/kg and 50μg/kg.The spiked recoveries for the analytes ranged from 53.7%to 129%,with relative standard deviations of 2.7%-19%.The developed method exhibits a great potential in the routine laboratory analysis of large number of samples belonging to different classes of com⁃pounds.Meanwhile,in comparison to traditional procedures,the automated sample clean up could ensure the rapid,effective,simple and sensitive analysis of veterinary drugs for the screening of resi⁃dues in batches of aquatic products.