Center for Advanced Analysis, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety, Cheongju-si, Republic of Korea.
College of Pharmacy, Kangwon National University, Chuncheon-si, Republic of Korea.
Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2021 Jul;38(7):1075-1086. doi: 10.1080/19440049.2021.1906954. Epub 2021 May 1.
Selective androgen receptor modulators (SARMs) are compounds with specific androgenic properties that have been investigated for the treatment of conditions such as muscle wasting disease. The reported androgenic properties have resulted in their use by athletes, and consequently they have been on the World Anti-Doping Agency prohibited list for more than a decade. To minimise the chance of an unattended positive doping test and to avoid potential serious health problems, adequate screening methods for the detection of a wide range of SARMs in these supplements is necessary. In this study, a rapid and accurate liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated simultaneously to screen and quantify six SARMs in dietary supplements, with confirmation by liquid chromatography-quadrupole-time of flight mass spectrometry (LC-Q-TOF/MS). The validated method was applied to 60 dietary supplements obtained by on-line and direct purchase from international vendors in 2020. Various SARMs were detected at high concentrations in 20 products which were advertised as having androgenic properties. For example, andarine was present at 7.2% in one product, and GW501516 was found at 3.49% in the another product. Furthermore, MK-677 and YK-11, not disclosed on the label, were detected in some products. YK-11 is easily hydrolysed in just a few hours. Although YK-11 is particularly unstable, such that the protonated ion [M + H] at m/z 431 for YK-11 was not detected, mass fragmentation, and a [M+ Na] ion at m/z 453.3 confirmed the presence of YK-11. Additionally, hydrolysed YK-11 under acidic conditions was confirmed by NMR spectral data, and H NMR and C NMR spectral data for YK-11 were in good agreement with literature data. This rapid and accurate LC-MS/MS method can therefore be successfully applied to screen and identify SARMs for the continuous control and supervision of dietary supplements.
选择性雄激素受体调节剂 (SARMs) 是具有特定雄激素特性的化合物，已被研究用于治疗肌肉消耗疾病等病症。据报道，这些化合物具有雄激素特性，因此被运动员使用，并且已经在世界反兴奋剂机构的禁用名单上超过十年。为了最大程度地减少无人值守的阳性兴奋剂检测的机会并避免潜在的严重健康问题，有必要使用适当的筛选方法来检测这些补充剂中的广泛的 SARMs。在这项研究中，开发并同时验证了一种快速准确的液相色谱-串联质谱 (LC-MS/MS) 方法，用于筛选和定量检测膳食补充剂中的六种 SARMs，并通过液相色谱-四极杆飞行时间质谱 (LC-Q-TOF/MS) 进行确认。该验证方法应用于 2020 年通过在线和直接从国际供应商处购买的 60 种膳食补充剂。在 20 种被宣传具有雄激素特性的产品中，以高浓度检测到各种 SARMs。例如，在一种产品中存在 7.2%的安非他命，在另一种产品中发现了 3.49%的 GW501516。此外，在一些产品中还检测到未在标签上披露的 MK-677 和 YK-11。YK-11 在短短几个小时内就很容易水解。尽管 YK-11 特别不稳定，以至于无法检测到 YK-11 的质子化离子 [M+H]+ 在 m/z 431 处，但通过质谱碎裂和 m/z 453.3 处的 [M+Na] 离子确认了 YK-11 的存在。此外，通过 NMR 谱数据确认了酸性条件下水解的 YK-11，并且 YK-11 的 1H NMR 和 13C NMR 谱数据与文献数据吻合良好。因此，这种快速准确的 LC-MS/MS 方法可成功用于筛选和鉴定 SARMs，以对膳食补充剂进行持续控制和监督。
