7‐keto‐DHEA (3β‐hydroxy‐androst‐5‐ene‐7,17‐dione) is included in section S1 of the World Antidoping Agency (WADA) List of Prohibited Substances. The detection of its misuse in sports needs special attention, since it is naturally present in urine samples. The main goal of this study is to investigate the in vivo metabolism of 7‐keto‐DHEA after a single administration to healthy volunteers and to better describe the relationship between arimistane (androst‐5‐ene‐7,17‐dione) and 7‐keto‐DHEA after the application of the common routine procedures to detect anabolic steroids in WADA accredited antidoping laboratories. Free, glucuro‐, and sulpho‐conjugated steroids extracted from urine samples obtained before and after the administration of 7‐keto‐DHEA were analyzed by different gas chromatographic (GC)–mass spectrometric (MS) techniques. Gas chromatography coupled to tandem MS to study the effect on the endogenous steroid profile, coupled to isotope ratio mass spectrometry (IRMS) to investigate the potential formation of androgens derived from DHEA and coupled to high resolution accurate mass spectrometry (HRMS) to investigate new diagnostic metabolites. The analysis by IRMS confirmed that there is no formation of DHEA from 7‐keto‐DHEA. Ten proposed metabolites, not previously reported, were described. These include reduced and hydroxylated structures that are not considered part of the steroid profile in antidoping analyses. They showed considerable responses in all fractions analyzed. Some deoxidation reactions (including arimistane formation) were found and most probably can be linked to the sample preparation or instrumental analysis. This is important when interpreting the results after the application of procedures to detect steroids in urine currently used in antidoping laboratories. 7‐keto‐DHEA metabolism in humans for antidoping purposes was studied and unexpected results were found. This could lead to a misinterpretation of the data, depending on the procedure applied and the analytical instrumentation used.

中文翻译：

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人类中的7-酮-DHEA代谢。在解释反掺杂领域的分析结果时存在陷阱。

世界反兴奋剂机构（WADA）禁止物质清单的S1部分包括7-酮-DHEA（3β-羟基-雄甾烯5-烯-7,17-二酮）。由于在尿液样本中自然存在滥用，因此在运动中滥用的检测需要特别注意。这项研究的主要目的是研究对健康志愿者进行单次给药后7-酮-DHEA的体内代谢，并更好地描述阿里敏烷（雄甾烯5-烯-7,17-二酮）与7-酮-DHEA之间的关系。在WADA认可的反兴奋剂实验室采用通用常规程序检测合成代谢类固醇后，使用keto-DHEA。使用不同的气相色谱（GC）-质谱（MS）技术分析了从服用7-酮-DHEA之前和之后获得的尿液样品中提取的游离，葡萄糖醛和硫磺结合的类固醇。气相色谱与串联质谱联用，研究对内源性类固醇激素谱的影响，与同位素比质谱法（IRMS）结合，研究源自DHEA的雄激素的潜在形成，与高分辨率精密质谱法（HRMS）结合，研究新的诊断方法代谢产物。IRMS的分析证实，从7-酮-DHEA不会形成DHEA。描述了十种拟议的代谢物，以前没有报道过。这些包括还原和羟基化的结构，这些结构在反掺杂分析中不被视为类固醇概况的一部分。在所分析的所有部分中，它们均显示出可观的响应。发现了一些脱氧反应（包括形成阿米斯丁烷），并且很可能与样品制备或仪器分析有关。在应用反兴奋剂实验室当前使用的检测尿液中类固醇的程序后解释结果时，这一点很重要。研究了用于反兴奋剂目的的人类7-酮-DHEA代谢，发现了出乎意料的结果。根据所应用的程序和所使用的分析仪器，这可能导致对数据的误解。