通过低分辨率气相色谱-质谱仪对化合物进行统计鉴定:催泪瓦斯喷雾剂中催泪剂的鉴定。

IF 5.6 1区 化学 Q1 CHEMISTRY, ANALYTICAL
Talanta Pub Date : 2025-01-01 Epub Date: 2024-10-18 DOI:10.1016/j.talanta.2024.127061
Pedro A S Salgueiro, Bettencourt da Silva Ricardo J N
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引用次数: 0

摘要

气相色谱与低分辨率质谱联用是一种非常灵活的工具,可以经济高效地识别和定量复杂基质中的挥发性化合物。在某些分析领域,校准物和样品中分析物的保留时间和质谱之间的一致性标准是根据对这些参数性能的一般理解来确定的。然而,由于这种协调并非基于针对特定气相色谱-质谱条件和分析物观察到的实验性能,因此会导致错误的鉴定。本研究提出了一种新颖、稳健的工具,可利用实验数据为通过气相色谱-质谱和液相色谱-质谱鉴定化合物确定合理的统计标准。利用蒙特卡洛法(MCM)模拟分析物质谱特征离子的相关丰度,可以模拟分析物在校准物和样品中的丰度比差异,用于进行可靠的统计鉴定。通过对 MCM 模拟的离子丰度协方差矩阵进行 Cholesky 分解,可以在鉴定中可靠地使用多种离子丰度比。所开发的方法已在用户友好型 Excel 电子表格中实施,并应用于催泪瓦斯喷剂中催泪瓦斯剂的鉴定。将 SANTE 确定的食品中农药残留鉴定标准与开发的工具进行了比较。计算工具和 SANTE 工具的交叉验证结果表明,保留时间和质谱的统计控制符合规定的置信水平。另一方面,SANTE 标准由于过于严格地考虑了信号的分散性,可能会产生高达 92% 的错误鉴定。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Statistically sound identification of compounds by low-resolution GC-MS: Identification of tear agents in tear gas sprays.

Gas-chromatography hyphenated with low-resolution mass spectrometry is a very flexible tool for the cost-effective identification and quantification of volatile compounds in complex matrices. In some analytical fields, criteria for the agreement between retention time and mass spectra of the analyte in calibrators and samples are defined based on the general understanding of the performance of these parameters. However, since this harmonisation is not based on experimental performance observed for specific GC-MS conditions and analyte it leads to false identifications. This research proposes a novel and robust tool for defining statistically sound criteria for the identification of compounds by GC-MS and LC-MS using experimental data. The Monte Carlo Method (MCM) simulation of the correlated abundance of characteristic ions of analyte mass spectrum allows simulating the abundance ratio difference of the analyte in a calibrator and sample used for statistically sound identifications. The Cholesky decomposition of the covariance matrix of ion abundances for MCM simulations allows the reliable use of many ion abundance ratios in identifications. The developed methodology was implemented in a user-friendly Excel spreadsheet and applied to the identification of tear gas agents in tear gas sprays. Criteria defined by SANTE for identifying pesticide residues in foodstuffs were compared with the developed tool. The cross-validation of computational and SANTE tools allowed concluding that the statistical control of retention time and mass spectra performs according to the defined confidence level. On the other hand, the SANTE criteria can produce up to 92 % false identifications for being too strict considering signal dispersion.

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来源期刊
Talanta
Talanta 化学-分析化学
CiteScore
12.30
自引率
4.90%
发文量
861
审稿时长
29 days
期刊介绍: Talanta provides a forum for the publication of original research papers, short communications, and critical reviews in all branches of pure and applied analytical chemistry. Papers are evaluated based on established guidelines, including the fundamental nature of the study, scientific novelty, substantial improvement or advantage over existing technology or methods, and demonstrated analytical applicability. Original research papers on fundamental studies, and on novel sensor and instrumentation developments, are encouraged. Novel or improved applications in areas such as clinical and biological chemistry, environmental analysis, geochemistry, materials science and engineering, and analytical platforms for omics development are welcome. Analytical performance of methods should be determined, including interference and matrix effects, and methods should be validated by comparison with a standard method, or analysis of a certified reference material. Simple spiking recoveries may not be sufficient. The developed method should especially comprise information on selectivity, sensitivity, detection limits, accuracy, and reliability. However, applying official validation or robustness studies to a routine method or technique does not necessarily constitute novelty. Proper statistical treatment of the data should be provided. Relevant literature should be cited, including related publications by the authors, and authors should discuss how their proposed methodology compares with previously reported methods.
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