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直接进样高效液相色谱-数据非依赖采集质谱联用技术用于蜂蜜中抗生素的筛查。

Direct injection high performance liquid chromatography coupled to data independent acquisition mass spectrometry for the screening of antibiotics in honey.

机构信息

Department of Food Science and Agricultural Chemistry, McGill University, Canada.

Calgary Laboratory, Canadian Food Inspection Agency (CFIA), Calgary, AB, Canada.

出版信息

J Food Drug Anal. 2019 Jul;27(3):679-691. doi: 10.1016/j.jfda.2018.12.013. Epub 2019 Jan 29.

Abstract

The targeted analysis of veterinary drug residues in honey traditionally involves a series of extraction and purification steps prior to quantification with high performance liquid chromatography coupled to high resolution or tandem mass spectrometry. These steps, designed to separate the target analytes from interferences, are generally time-consuming and costly. In addition, traditional cleanup steps are likely to eliminate other compounds whose analysis could prove decisive in current or future assessment of the honey sample. Alternatively, direct injection without complex sample preparation steps has been introduced for the fast analysis of trace compounds in environmental and food matrices. The aim of this study was to develop a rapid method for the targeted analysis of 7 key veterinary drug residues in honey based on direct injection high performance liquid chromatography coupled to quadrupole time-of-flight, while simultaneously recording data-independent MS/MS (e.g. All Ions MS/MS data) for future re-examination of the data for other purposes. The new method allowed for the detection of the target residues at levels approximately 20-100 times lower than current regulatory limits, for a total analysis time of about 45 min. The recoveries (103-119%), the linearity (R ≥ 0.996) and the repeatability (RSD ≤ 7%) were satisfactory. The method was then applied to 35 honey samples from the Canadian market. Residues of tylosin A, tylosin B, sulfamethazine and sulfadimethoxine were detected in 6, 9, 6 and 23% of the samples respectively, at levels below the regulatory limits in Canada. The possibility of adding a hydrolysis step to study sulfonamides in honey was tested, which provided good results for this family of compounds but lead to degradation of some of the other analytes. Finally, the non-targeted identification of several compounds was demonstrated as a proof of concept of future re-examination of All Ions MS/MS data. This paper illustrates the capacity of this novel method to combine targeted and non-targeted screening of chemical residues in honey.

摘要

传统上,蜂蜜中兽药残留的靶向分析需要经过一系列的提取和净化步骤,然后使用高效液相色谱与高分辨率或串联质谱联用进行定量分析。这些步骤旨在将目标分析物与干扰物分离,通常既耗时又昂贵。此外,传统的净化步骤可能会消除其他化合物,而这些化合物的分析对于当前或未来对蜂蜜样品的评估可能是决定性的。或者,已经引入了无需复杂样品制备步骤的直接进样,用于快速分析环境和食品基质中的痕量化合物。本研究旨在开发一种基于直接进样高效液相色谱与四极杆飞行时间联用,同时同时记录数据非依赖性 MS/MS(例如全离子 MS/MS 数据)的快速方法,用于未来为其他目的重新检查数据。新方法允许在大约 45 分钟的总分析时间内,以比当前监管限量低约 20-100 倍的水平检测到目标残留。回收率(103-119%)、线性(R≥0.996)和重复性(RSD≤7%)均令人满意。然后将该方法应用于来自加拿大市场的 35 个蜂蜜样品。在 6、9、6 和 23%的样品中分别检测到泰乐菌素 A、泰乐菌素 B、磺胺嘧啶和磺胺二甲氧嘧啶残留,残留水平低于加拿大的监管限量。测试了添加水解步骤以研究蜂蜜中磺胺类药物的可能性,这为该化合物家族提供了良好的结果,但导致了其他一些分析物的降解。最后,证明了通过非靶向鉴定几种化合物的可能性,这是未来重新检查全离子 MS/MS 数据的概念验证。本文说明了该新方法能够结合蜂蜜中化学残留物的靶向和非靶向筛选的能力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5090/9307035/1ee018618d19/jfda-27-03-679f1.jpg

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