National Center for Natural Products Research, School of Pharmacy, The University of Mississippi, University, MS, 38677, USA.
Consortium for Health and Military Performance, Department of Military and Emergency Medicine, Uniformed Services University, 4301 Jones Bridge Road, Bethesda, MD, 20814, USA.
J Pharm Biomed Anal. 2019 Apr 15;167:74-82. doi: 10.1016/j.jpba.2018.12.045. Epub 2019 Feb 1.
A previously unidentified purported botanical ingredient was found in dietary supplements marketed for anabolic benefits. In an attempt to assess the 'naturalness' of a group of steroid-like compounds called laxogenins, a UHPLC-QToF method was developed. Several dietary supplements claim to contain 5α-hydroxy laxogenin, which is a derivative of a naturally occurring spirostane-type steroid, laxogenin. Although laxogenin has been isolated from the rhizomes of Smilax sieboldii, 5α-hydroxy laxogenin has not been isolated or reported from any natural source. These derivatives of laxogenins have untested anabolic properties. Due to the low UV absorbance of the spirostanes, a mass spectrometric method in positive ion mode was developed for unambiguous identification of laxogenin and closely related compounds. To show the utility of the developed method, twelve dietary supplements labeled to contain 5α-hydroxy laxogenin or laxogenin as 5α-hydroxy laxogenin were analyzed as a proof-of-concept. Five supplements did not contain any 5α-hydroxy laxogenin, whereas in the remaining seven samples, spirostane-type contaminants were identified along with the labeled 5α-hydroxy laxogenin. The identity of some of these contaminants was established based on reference standards along with mass fragmentation patterns. One of the unlabeled contaminants was identified as the phytosteroid saponin, diosgenin, a common starting precursor of several steroidal drugs. Several synthetic derivatives of diosgenin were identified in the eight products. These findings indicate that the labeled 5α-hydroxy laxogenin along with other spirostanes found in supplements are synthetic and signify a lack of quality controls. Additionally, an unlabeled, anabolic androgenic steroid, arimistane, an aromatase inhibitor, was also identified in one product. Laxogenin, was not detected in any of the samples analyzed during this investigation.
一种先前未被识别的植物成分在宣传具有合成代谢益处的膳食补充剂中被发现。为了评估一组被称为 laxogenins 的类固醇样化合物的“天然性”,开发了一种 UHPLC-QToF 方法。几种膳食补充剂声称含有 5α-羟基 laxogenin,它是 laxogenin 的一种天然存在的螺甾烷型类固醇的衍生物。尽管 laxogenin 已从 Smilax sieboldii 的根茎中分离出来,但 5α-羟基 laxogenin 尚未从任何天然来源中分离或报道过。这些 laxogenins 的衍生物具有未经测试的合成代谢特性。由于螺甾烷类物质的紫外吸收率较低,因此开发了一种正离子模式的质谱方法,用于明确鉴定 laxogenin 和密切相关的化合物。为了展示所开发方法的实用性,以概念验证的方式分析了十二种标签为含有 5α-羟基 laxogenin 或 laxogenin 的膳食补充剂。五种补充剂不含任何 5α-羟基 laxogenin,而在其余七种样品中,除了标记的 5α-羟基 laxogenin 外,还鉴定出了螺甾烷型污染物。基于参考标准和质量碎片模式,确定了其中一些污染物的身份。其中一种未标记的污染物被鉴定为植物甾醇皂苷薯蓣皂苷元,它是几种甾体药物的常见起始前体。在八种产品中还鉴定出了几种薯蓣皂苷元的合成衍生物。这些发现表明,标签为 5α-羟基 laxogenin 的补充剂中与其他螺甾烷一起发现的是合成的,表明缺乏质量控制。此外,一种未标记的合成代谢雄激素类固醇,芳香酶抑制剂阿那曲唑,也在一种产品中被鉴定出来。在本研究中分析的任何样品中均未检测到 laxogenin。