High throughput and very specific screening of anabolic-androgenic steroid adulterants in healthy foods based on stable isotope labelling and flow injection analysis-tandem mass spectrometry with simultaneous monitoring proton adduct ions and chloride adduct ions

【作者】Chen, Di; Wang, Zi-Han; Cui, Wei-Qi; Zhang, Jing-Xian; Zhang, Jun-Wei; Wu, De-Qiao; Wang, Zi-Yue; Yu, Xin-Rui; Luo, Yan-Bo; Hussain, Dilshad; Xu, Xia*

【期刊名】Journalof Chromatography A

【影响因子】2021年: 4.601

【作者单位】Key Laboratory of Targeting Therapy and Diagnosis for Critical Diseases of Henan Province, School of Pharmaceutical Sciences, Zhengzhou University, 100 Kexue Avenue, Zhengzhou 450001, PR China

【年，卷(期)：页码】2022, 1667: 462891

【关键词】Anabolic-androgenic steroidsStable isotope labelling Flow injection analysis-mass spectrometry3-nitrophenylhydrazine

【摘要】In this work, a stable isotope labelling-flow injection analysis-tandem mass spectrometry (SIL-FIA-MS/MS) with simultaneous monitoring [M+H]+ and [M+Cl]− method was developed for very specific and high throughput screening of anabolic-androgenic steroids (AAS) illegally added to healthy foods. Initially, a simple centrifugation step was carried out for liquid samples, and for solid samples, a solid-liquid extraction step was conducted. Afterwards, batch chemical derivatization was carried out. After adding a certain amount of 13C6-3-NPH labelled AAS standards as the internal standards, it can be directly transferred for FIA-MS/MS analysis based on the no MS response characteristics of 3-NPH. The 3-NPH labelled AAS showed dual-polarity property, observing chloride adduct ion ([M+Cl]−) in negative ion mode and proton adduct ion ([M+H]+) in positive ion mode. The average time cost for pretreatment of each sample was less than 1 min by carrying out batch processing. The subsequent FIA-MS/MS detection enabled rapid and high throughput detection. The addition of 13C6-3-NPH-labelled AAS as internal standards can correct the matrix effect to achieve accurate quantitative analysis. The detection sensitivity was also improved by 2–5 folds after 3-NPH labelling. The limits of detection (LODs) in positive MRM mode were in ranges of 0.1–0.3 ng/mL. The validated method with simultaneous monitoring [M+H]+ and [M+Cl]− was validated in the range of 6.0–1000 ng/mL with the linear coefficient (R2) greater than 0.997. Satisfactory recoveries were found to be in ranges of 93.0–108.7%. The intra-day and inter-day RSDs were in the range of 3.5–9.9% and 5.1–14.1%, respectively. No changes in detection sensitivity of the mass spectrometry and no carry-over effects were found after numerous consecutive injections of AAS derivates. Compared with previously reported methods, the proposed method proved accurate, very specific, high throughput with good sensitivity.

【全文链接】https://doi.org/10.1016/j.chroma.2022.462891