Instrumental Analytical Chemistry, University of Duisburg-Essen, Universitätsstrasse 5, 45141, Essen, Germany.
Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Stremayrgasse 9/II 8010, Graz, Austria.
Anal Bioanal Chem. 2023 Jul;415(17):3313-3325. doi: 10.1007/s00216-023-04713-8. Epub 2023 May 20.
Some aromatic amines (AA) have been classified as carcinogens to humans. After entering the body, mainly through tobacco smoke, they can be detected in urine. Thus, their trace analysis as biomarkers in biofluids is of high relevance and can be achieved with gas chromatography (GC-MS), usually after derivatization. This study compares three gas chromatographic methods for the analysis of ten iodinated derivatives of AA: GC-MS in single-ion monitoring (SIM) mode with (1) electron ionization (GC-EI-MS) and (2) negative chemical ionization (GC-NCI-MS), and (3) GC-EI-MS/MS in multiple reaction monitoring (MRM) mode using electron ionization. All methods and most analytes showed good coefficients of determination (R > 0.99) for broad linear ranges covering three to five orders of magnitude in the picogram-per-liter to nanogram-per-liter range, with one and two exceptions for (1) and (2) respectively. Excellent limits of detection (LODs) of 9-50, 3.0-7.3, and 0.9-3.9 pg/L were observed for (1), (2), and (3) respectively, and good precision was achieved (intra-day repeatability < 15% and inter-day repeatability < 20% for most techniques and concentration levels). On average, recoveries between 80 and 104% were observed for all techniques. Urine samples of smokers and non-smokers were successfully analyzed, and p-toluidine and 2-chloroaniline could be found at significantly (α = 0.05) higher concentrations among smokers.
一些芳香胺（AA）已被归类为人类致癌物。进入人体后，主要通过烟草烟雾，它们可以在尿液中被检测到。因此，它们作为生物流体中生物标志物的痕量分析具有重要意义，可以通过气相色谱（GC-MS）来实现，通常需要衍生化。本研究比较了三种气相色谱方法来分析十种碘代 AA 衍生物：（1）电子电离（GC-EI-MS）和（2）负化学电离（GC-NCI-MS）的单离子监测（SIM）模式下的 GC-MS，以及（3）使用电子电离的多重反应监测（MRM）模式下的 GC-EI-MS/MS。所有方法和大多数分析物在皮克/升至纳克/升范围内三个到五个数量级的宽线性范围内都表现出良好的决定系数（R > 0.99），除（1）和（2）外，各有一个和两个例外。（1）、（2）和（3）分别观察到 9-50、3.0-7.3 和 0.9-3.9 pg/L 的优异检测限（LOD），并且达到了良好的精密度（大多数技术和浓度水平的日内重复性<15%，日间重复性<20%）。平均而言，所有技术的回收率在 80%到 104%之间。成功分析了吸烟者和不吸烟者的尿液样本，并在吸烟者中发现了对甲苯胺和 2-氯苯胺的浓度明显（α=0.05）更高。
