Application of LC–MS/MS and UHPLC‐Q‐Orbitrap methods for determining 54 steroids in illegal dietary supplements and other sample types

Abstract

Rationale With the development of the Internet and social network services, the public access to or use of illegal products has been increased via on/offline black markets. Steroids refer to the compounds yielding strong treatment effects on some diseases or muscle building, and are classified as the pharmaceutical compounds that are prohibited for personal use without a prescription. The prohibition is made for their potential risk to cause serious adverse effects along with their efficacies. Methods To monitor the distribution of illicit products containing steroids, a simple and reliable analytical method was established and validated, allowing rapid and simultaneous determination of 54 steroids in them. During the screening, LC‐Q‐Orbitrap/MS was performed first followed by quantitative analysis using LC–MS/MS. For the accurate and reliable analysis, the samples were extracted using QuEChERS to reduce the matrix effect. Results After the screening of 617 illegal samples advertised as being effective in alleviating various diseases or improving athletic performance with the established LC‐Q‐Orbitrap/MS method, the validated LC–MS/MS method was used to perform the quantitative analysis of the detected steroids. Of these, 142 samples were adulterated with steroids, and several samples with two or more steroids were detected. Due to the lack of previous studies on the toxicity of these illicit products, the side effects of consuming them are unpredictable and could be harmful. Conclusions The development of LC‐Q‐Orbitrap/MS method accompanied by LC–MS/MS could be successfully applied to the inspection of illegal steroid products for public health, enabling the rapid and accurate detection of analytes and incorporation of non‐analyte components.

Development, validation, and use of a monitoring method for fipronil and its metabolites in chicken eggs by QuEChERS with online‐SPE‐LC‐Q/Orbitrap analysis

“…5,18,30 Among these detection techniques, Q Exactive Orbitrap HRMS is ideal for biological sample analysis due to its high mass resolution, high mass accuracy, and high-performance quadrupole for selectivity. 31 Because of the high proportion of lipids and proteins in eggs, sample preparation for egg matrices is challenging. In previous reports, liquid-phase extraction (LPE) with acetonitrile (ACN) was mostly used for the extraction of fipronil and its metabolites from eggs.…”

“…Most analytical techniques are based on chromatographic techniques such as high‐performance liquid chromatography (HPLC), 13,23 liquid chromatography tandem mass spectrometry (LC–MS/MS), 14,24,25 liquid chromatography–high‐resolution mass spectrometry (LC‐HRMS), 26,27 gas chromatography (GC), 28,29 and gas chromatography tandem mass spectrometry (GC–MS or GC–MS/MS) 5,18,30 . Among these detection techniques, Q Exactive Orbitrap HRMS is ideal for biological sample analysis due to its high mass resolution, high mass accuracy, and high‐performance quadrupole for selectivity 31 …”