Universidade Federal do Rio de Janeiro, Instituto de Química, LAB DOP-LADETEC, Avenida Athos da Silveira Ramos, 149, 21941-909 Rio de Janeiro, RJ, Brazil.
J Chromatogr A. 2013 Jul 12;1298:76-85. doi: 10.1016/j.chroma.2013.05.016. Epub 2013 May 13.
The detection of 11 sympathomimetic alkylamines in urine was presented with a focus on human doping control is proposed using liquid chromatography tandem mass spectrometry (LC-QqQ) and high resolution mass spectrometry (LC-HRMS) as a screening tool after a dilute-and-shoot (DS) approach. For the LC-HRMS analyses, several compounds exhibited better limits of detection (L.O.D.) than the LC-QqQ. However, due to their small differences in structure, co-elution among the alkylamines was observed. Therefore, the chemical conversion of the alkylamines into an appropriate derivative for the confirmation analyses using gas chromatography-mass spectrometry (GC-MS) was evaluated. Five derivatization approaches were evaluated in an attempt to increase the analytical response and the confidence of the identification. The choice of the appropriated derivative for each alkylamine makes their spectra more easily interpretable, fulfills the WADA's rather strict identification criteria and enables the unequivocal identification of alkylamines in urine.
提出了一种使用液相色谱串联质谱（LC-QqQ）和高分辨质谱（LC-HRMS）作为筛选工具，结合稀释和进样（DS）方法，检测尿液中 11 种拟交感胺烷基胺的方法，重点关注人体兴奋剂控制。对于 LC-HRMS 分析，一些化合物的检测限（LOD）优于 LC-QqQ。然而，由于它们在结构上的微小差异，烷基胺之间存在共洗脱。因此，评估了将烷基胺化学转化为适当的衍生化合物，用于使用气相色谱-质谱（GC-MS）进行确认分析。评估了五种衍生化方法，试图提高分析响应和鉴定的可信度。选择适当的衍生化合物对于每种烷基胺都能使其谱图更易于解释，满足世界反兴奋剂机构（WADA）相当严格的鉴定标准，并能够明确鉴定尿液中的烷基胺。
