Liquid chromatography–quadrupole orbitrap and liquid chromatography–tandem mass spectrometry system for rapid identification and quantitation of thirty nonsteroidal anti‐inflammatory drugs and acetaminophen in illegal products

Abstract

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 chromatographyquadrupole 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. | INTRODUCTIONWith the increasing consumption of dietary supplements, their sales are estimated to exceed $30 billion in the United States and $100 billion worldwide. 2 People who consume dietary supplements, foods, or herbal medicines to manage health conditions such as osteoarthritis believe that these products do not pose a significant health threat because they do not contain synthetic pharmaceuticals. 1 However, some unscrupulous dietary supplement manufacturers often intentionally mix and market synthetic pharmaceutical Hyoung-Joon Park and Hyeon Joo Ham contributed equally to this work.