Optimization of Coated Blade Spray for Rapid Screening and Quantitation of 105 Veterinary Drugs in Biological Tissue Samples

Abstract

Rapid and efficient determination of contaminants at trace levels in tissue samples has become an unmet need around the globe. Coated blade spray (CBS) extraction/ionization is a technology capable of performing, with a single device, enrichment of analytes present in complex matrices, as well as the direct interface and introduction of said analytes into the mass spectrometer via electrospray ionization. To facilitate the challenging rapid tissue screening, we describe for the first time the use of a very thin layer of biocompatible polyacrylonitrile as a CBS device undercoating to make metal surface biocompatible. This add-on is meant to protect the portion of the uncoated stainless-steel of the blade that is normally exposed to the matrix, consequently becoming susceptible to adhesion of matrix macromolecules, cells, and fat. In addition, we present for the first time the use of CBS in negative ionization mode for quantitative purposes. The optimized CBS workflow allows for rapid and highthroughput screening and quantitation of 105 veterinary drugs in homogenized bovine tissue in both negative and positive ionization mode in one single run using a single CBS device with analysis times as short as 1 min per sample when 96 extractions are simultaneously conducted. While only two internal standards were used for correction, one per ionization mode, excellent accuracy and precision were achieved, with more than 90% of analytes falling within the 70−120% range of their true concentrations and yielding RSD ≤ 25% at three validation levels. The majority of analytes achieved linear correlation coefficients >0.99, and all 105 analytes were able to meet both Canadian and U.S. regulatory levels.

Analysis of food samples made easy by microextraction technologies directly coupled to mass spectrometry

“…Since its inception, the use of CBS has been primarily focused on bioanalysis 31 . Recently, the technology was shown to be also suitable for rapid food screening and quantitation by work that has set important breakthroughs, not only in food analysis but also in microextraction technology interfaces with MS instrumentation 28,29 . For instance, Kasperkiewicz et al proposed for the first time optimization of extraction time based on signal‐to‐noise ratios instead of mere instrumental signal.…”

“…Poole et al first demonstrated the suitability of the technique for the determination of a group of pharmaceuticals in environmental water samples 32 . Subsequently, Khaled et al investigated the potential of CBS‐MS/MS technology for effective monitoring of 105 veterinary drugs in homogenized bovine meat 29 . This work achieved for the first time the of use both negative and positive ionization modes in one single run with the same CBS device.…”

“…As expected with a direct‐to‐MS technology, matrix effects were observed because of the lack of a separation step. Yet the cleanup provided by the CBS device enabled satisfactory simultaneous quantitative analysis of most the targeted analytes 29 …”

“…Analytical workflow via CBS‐MS/MS toward rapid screening and quantitation of veterinary drugs in homogenized bovine samples. Reprinted with permission from Khaled et al 29 Copyright 2020 American Chemical Society…”

“…It is worth mentioning that in certain cases, matrix effects are also because of the amount of coextracted molecules that can intrinsically affect the ionization efficiency of the targeted analytes, as such matrix‐matched calibration strategies are always recommended. Likewise, the incorporation of deuterated analogs as internal standards remains the preferred option to deliver the most accurate quantitative results as long as these are available and/or not prohibitively expensive 12,28,29 . The optimization of SPME geometry enabled convenient coupling to already existing ion sources such as DART, 13 or the development of innovative technologies such as CBS 30 .…”