Balcells Georgina, Gómez Cristina, Garrostas Lorena, Pozo Óscar J, Ventura Rosa
Bioanalysis Research Group, IMIM, Hospital del Mar Medical Research Institute, Barcelona, Spain.
Department of Experimental and Health Sciences, Universitat Pompeu Fabra, Barcelona, Spain.
Drug Test Anal. 2017 Jul;9(7):983-993. doi: 10.1002/dta.2101. Epub 2016 Oct 24.
Sulfate metabolites have been described as long-term metabolites for some anabolic androgenic steroids (AAS). 4-chlorometandienone (4Cl-MTD) is one of the most frequently detected AAS in sports drug testing and it is commonly detected by monitoring metabolites excreted free or conjugated with glucuronic acid. Sulfation reactions of 4Cl-MTD have not been studied. The aim of this work was to evaluate the sulfate fraction of 4Cl-MTD metabolism by liquid chromatography-tandem mass spectrometry (LC-MS/MS) to establish potential long-term metabolites valuable for doping control purposes. 4Cl-MTD was administered to two healthy male volunteers and urine samples were collected up to 8 days after administration. A theoretical selected reaction monitoring (SRM) method working in negative mode was developed. Ion transitions were based on ionization and fragmentation behaviour of sulfate metabolites as well as specific neutral losses (NL of 15 Da and NL of 36 Da) of compounds with related chemical structure. Six sulfate metabolites were detected after the analysis of excretion study samples. Three of the identified metabolites were characterized by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). Results showed that five out of the six identified sulfate metabolites were detected in urine up to the last collected samples from both excretion studies. Copyright © 2016 John Wiley & Sons, Ltd.
硫酸代谢物已被描述为某些合成代谢雄性类固醇（AAS）的长期代谢物。4-氯甲基睾酮（4Cl-MTD）是在运动药物检测中最常检测到的AAS之一，通常通过监测游离排泄或与葡萄糖醛酸结合排泄的代谢物来检测。4Cl-MTD的硫酸化反应尚未得到研究。这项工作的目的是通过液相色谱-串联质谱（LC-MS/MS）评估4Cl-MTD代谢的硫酸盐部分，以确定对兴奋剂检测有价值的潜在长期代谢物。将4Cl-MTD给予两名健康男性志愿者，并在给药后长达8天收集尿液样本。开发了一种在负模式下工作的理论选择反应监测（SRM）方法。离子跃迁基于硫酸盐代谢物的电离和碎片化行为以及具有相关化学结构的化合物的特定中性损失（15 Da的中性损失和36 Da的中性损失）。在对排泄研究样本进行分析后，检测到六种硫酸代谢物。其中三种已鉴定的代谢物通过液相色谱-串联质谱（LC-MS/MS）和气相色谱-串联质谱（GC-MS/MS）进行了表征。结果表明，在两项排泄研究的最后收集样本之前，在尿液中检测到了六种已鉴定的硫酸代谢物中的五种。版权所有© 2016 John Wiley & Sons, Ltd.
