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The consumption of food and drugs adulterated with female sex hormones can have an extremely adverse effect on human health. Therefore, developing appropriate monitoring methods for the identification of various exogenous female sex hormones is crucial for minimizing and eliminating the related health risks. Herein, 17 female hormones categorized into two groups: estrogen and progestin, were analyzed using reversed-phase liquid chromatography coupled to Orbitrap or triple quadrupole mass spectrometry. The fragmentation patterns for all compounds were discovered, and fragmented structures were also derived from them through liquid chromatography-high-resolution mass spectrometry followed by qualitative sample analysis. In addition, a quantitative analysis of 67 samples of illicit drugs and dietary supplements was performed using the validated liquid chromatography-tandem mass spectrometry method. Female hormone components were detected in two samples of an unauthorized injectable solution and a tablet-type drug. Medroxyprogesterone was detected in the samples in the range of 96.4-206 ng/g. Notably, eight components similar in structure to steroids were simultaneously detected as male sex hormones by confirming their fragmentation ion patterns using liquid chromatography-high-resolution mass spectrometry. The developed methods thus offer a dependable and practically applicable approach for the screening and detection of exogenous female sex hormones in real food and drug samples to ensure public health., (© 2023 Wiley-VCH GmbH.)

Rationale: As the public interest in healthcare increases, illegal dietary supplements, foods, and drugs containing unauthorized pharmaceutical ingredients, including nonsteroidal anti-inflammatory drugs (NSAIDs) and acetaminophen, have been identified. Excessive and unintentional consumption is toxic to the gastrointestinal tract, kidneys, and liver; therefore, these pharmaceuticals must be monitored using analytical methods., Methods: A rapid and reliable analysis system involving liquid chromatography-quadrupole orbitrap mass spectrometry (LC-Q-Orbitrap/MS) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) was established and validated to identify and quantify 30 NSAIDs and acetaminophen. In addition, we obtained the MS 2 spectrum for each component with the proposed structure of the fragment ions., Results: The analytical method was applied to 505 samples of illicitly distributed dietary supplements, foods, and pharmaceuticals. Non-steroidal analgesics were detected in 126 samples. Carbamazepine (42.9%) and diclofenac (30.2%) were the most detected components in the samples; other pharmaceutical adulterants were also detected in some cases. Additionally, we present the identification of an unknown component, dexamethasone (799 μg/g), using LC-Q-Orbitrap/MS in a sample containing the unknown component with meloxicam (15.4 mg/g)., Conclusions: The developed analysis system, consisting of qualitative analysis using LC-Q-Orbitrap/MS and quantitative analysis using LC/MS/MS, can rapidly and accurately identify and quantify NSAIDs and acetaminophen while also identifying non-analytical components., (© 2022 John Wiley & Sons Ltd.)

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., (© 2022 John Wiley & Sons Ltd.)

In order to effectively and quickly monitor such illegal food and drugs, simultaneous screening and quantitative analysis for multiple compounds are needed. In this study, we established a method of identifying fragmentation ions of 45 compounds for weight loss using liquid chromatography and high-resolution mass spectrometry and developed a quantitation method through liquid chromatography and tandem mass spectrometry. Note that, 656 samples selected as health functional food, food, and illegal drug were applied. The detection rate of banned weight loss compounds in health functional food, food, and illegal drug was showed as 19.2, 27.3, 40.7%, respectively. Among them, sibutramine, sennoside A and B, ephedrine were most frequently detected in 237 samples that contained weight loss compounds. The detection range about sibutramine was 0.03-159.3 mg/g, sennoside was 0.1-97.6 mg/g, and ephedrine was 0.1-587.7 mg/g in the detected 237 samples. In addition, the unknown compounds not included in our simultaneous analysis method in some samples were identified as furosemide and chlorpheniramine. High selectivity of high resolution mass spectrometry combined with these fragmentation pathways and tandem mass spectrometry methods can be successfully applied to screening and identifying 45 weight loss compounds for continuous blocking and supervision of illegally distributed health functional food, food, and illegal drug., (© 2022 Wiley-VCH GmbH.)

Natural-derived steroids and their analogues are present in various plants and insects. To minimize the chance of missing a positive doping test and avoiding potentially serious health problems, adequate screening methods are necessary for the detection of a wide range of natural-derived steroids and their analogues in dietary supplements. In this study, an accurate and simple liquid-chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated to determine and quantify the natural-derived steroids and their analogues according to the International Conference on Harmonization of technical Requirements for Registration of Pharmaceuticals for Human Use guidelines. The validation results indicating excellent extraction efficiency and low matrix effects show that the LC-MS/MS method is reliable for the detection of natural-derived steroids and their analogues. In addition, we established the ion fragmentation of turkesterone and ion fragmentation of four natural-derived steroids and their analogues. The validated method was applied to 60 dietary supplements purchased online and in person from international vendors in 2020. Ecdysterone and 5α-hydroxylaxogenin were detected respectively in 3 and 14 of 60 dietary supplements. Especially, a high amount of 5α-hydroxylaxogenin, an FDA-unapproved ingredient, was detected in two of dietary supplements (44.4 and 32.3 mg/g). This component should be controlled since it may cause unexpected side effects if administered excessively. Thus, this method will be helpful for the continuous control and supervision of unlicensed dietary supplements containing natural-derived steroids and their analogues.