Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada.
Anal Chem. 2020 Apr 21;92(8):5937-5943. doi: 10.1021/acs.analchem.0c00093. Epub 2020 Mar 31.
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 high-throughput 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.
快速有效地测定组织样品中痕量污染物已成为全球未满足的需求。涂层刀片喷雾(CBS)提取/离子化技术能够用单一设备对复杂基质中存在的分析物进行浓缩,以及通过电喷雾离子化将所述分析物直接接口和引入质谱仪。为了便于进行具有挑战性的快速组织筛选,我们首次描述了使用非常薄的生物相容性聚丙烯腈作为 CBS 设备底层涂覆物,以使金属表面具有生物相容性。这种附加物旨在保护通常暴露于基质的刀片未涂覆不锈钢部分,从而容易受到基质大分子、细胞和脂肪的粘附。此外,我们首次提出在负离子模式下使用 CBS 进行定量目的。优化的 CBS 工作流程允许在单一运行中使用单个 CBS 设备在负离子和正离子模式下同时进行 96 次提取,在 1 分钟内对均质牛组织中的 105 种兽药进行快速高通量筛选和定量。虽然仅使用了两个内标进行校正,每个电离模式一个,但仍实现了出色的准确性和精密度,超过 90%的分析物在其真实浓度的 70-120%范围内,在三个验证水平下的 RSD≤25%。大多数分析物的线性相关系数>0.99,所有 105 种分析物均能够达到加拿大和美国的监管水平。