同位素比质谱方法检测内源性类固醇雄烯二酮

Isotope-ratio Mass Spectrometry Analysis for Detection of Endogenous Anabolic Androgenic Steroids—Androstenedione

采用高效液相色谱(HPLC)方法对尿样中内源性类固醇激素进行分离,收集的流出组分时间段为:睾酮和5β-雄烷-3α,17β-二醇(11.3~11.8 min);5α-雄烷-3α,17β-二醇(11.8~12.4 min);本胆烷醇酮和雄酮(13.0~14.0 min);孕二醇(14.5~15.0 min)。分离后的组分再经气相色谱/燃烧炉/同位素比质谱(GC/C/IRMS)方法检测其中类固醇及其代谢物的同位素比(δ值)。结果表明,阴性样品中的类固醇激素δ值为:-19.2‰^-21.5‰,服用雄烯二酮的阳性尿样中的睾酮及代谢物δ值为:-29.7‰^-32.7‰。提示,所建立的同位素比质谱方法可用于检测尿中类固醇兴奋剂的来源,适用于常规检测。

Preliminary purification for endogenous anabolic androgenic steroids was performed by using the HPLC. The collected fractions with HPLC were testosterone and 5β-androstane-3α, 17β-diol（ 11.3 ～ 11. 8 min）, 5α-androstane-3α, 17β-diol （ 11. 8 ～ 12.4 min）, etiocholanolone and androsterone （ 13.0 ～ 14.0 min） , pregnanediol （ 14.5 ～ 15.0 min）. Further separation and determination of the 3values for testosterone and other endogenous anabollc androgenic steroids metabolites could be achieved with Gas Chromatography/Combustion/Isotope Ratio Mass Spectrometry. The result showed that the 3values of steroid in negative urine sample ranged from -19. 2‰ to -21. 5‰, while that in positive urine sample ranged from -29.7‰ to - 32.7‰. It suggested that the source of steroids in urine could be detected by measuring theirδ values with the method presented in this paper. This method was suitable for routine work.