Ishii Hideaki, Shibuya Mariko, Kusano Kanichi, Sone Yu, Kamiya Takahiro, Wakuno Ai, Ito Hideki, Miyata Kenji, Sato Fumio, Kuroda Taisuke, Yamada Masayuki, Leung Gary Ngai-Wa
Drug Analysis Department, Laboratory of Racing Chemistry, 1731-2 Tsuruta-machi, Utsunomiya, Tochigi, 320-0851, Japan.
Department of Pharmaceutical Sciences, Tohoku University Hospital, 1-1 Seiryo-machi, Aoba-ku, Sendai, Miyagi, 980-8574, Japan.
Anal Bioanal Chem. 2022 Nov;414(28):8125-8142. doi: 10.1007/s00216-022-04347-2. Epub 2022 Oct 1.
In drug metabolism studies in horses, non-targeted analysis by means of liquid chromatography coupled with high-resolution mass spectrometry with data-dependent acquisition (DDA) has recently become increasingly popular for rapid identification of potential biomarkers in post-administration biological samples. However, the most commonly encountered problem is the presence of highly abundant interfering components that co-elute with the target substances, especially if the concentrations of these substances are relatively low. In this study, we evaluated the possibility of expanding DDA coverage for the identification of drug metabolites by applying intelligently generated exclusion lists (ELs) consisting of a set of chemical backgrounds and endogenous substances. Daprodustat was used as a model compound because of its relatively lower administration dose (100 mg) compared to other hypoxia-inducible factor stabilizers and the high demand in the detection sensitivity of its metabolites at the anticipated lower concentrations. It was found that the entire DDA process could efficiently identify both major and minor metabolites (flagged beyond the pre-set DDA threshold) in a single run after applying the ELs to exclude 67.7-99.0% of the interfering peaks, resulting in a much higher chance of triggering DDA to cover the analytes of interest. This approach successfully identified 21 metabolites of daprodustat and then established the metabolic pathway. It was concluded that the use of this generic intelligent "DDA + EL" approach for non-targeted analysis is a powerful tool for the discovery of unknown metabolites, even in complex plasma and urine matrices in the context of doping control.
在马的药物代谢研究中,液相色谱与具有数据依赖采集(DDA)功能的高分辨率质谱联用进行非靶向分析,最近在给药后生物样品中潜在生物标志物的快速鉴定方面越来越受欢迎。然而,最常见的问题是存在与目标物质共洗脱的高丰度干扰成分,尤其是当这些物质的浓度相对较低时。在本研究中,我们评估了通过应用由一组化学背景和内源性物质组成的智能生成排除列表(ELs)来扩大DDA覆盖范围以鉴定药物代谢物的可能性。达泊西汀被用作模型化合物,因为与其他缺氧诱导因子稳定剂相比,其给药剂量相对较低(100 mg),并且在预期的较低浓度下对其代谢物的检测灵敏度有较高要求。结果发现,在应用ELs排除67.7 - 99.0%的干扰峰后,整个DDA过程可以在单次运行中有效地鉴定出主要和次要代谢物(标记超过预设的DDA阈值),从而大大提高触发DDA覆盖感兴趣分析物的机会。该方法成功鉴定出达泊西汀的21种代谢物,进而建立了代谢途径。得出的结论是,即使在反兴奋剂控制背景下的复杂血浆和尿液基质中,使用这种通用的智能“DDA + EL”方法进行非靶向分析也是发现未知代谢物的有力工具。