Multi-Class Determination of 64 Illicit Compounds in Dietary Supplements Using Liquid Chromatography–Tandem Mass Spectrometry

Abstract

In this work, liquid chromatography–tandem mass spectrometry (LC-MS/MS) method was developed and validated for screening and confirmation of 64 illicit compounds in dietary supplements. The target compounds were illegally used pharmaceutical drugs, prohibited compounds, and not authorized ingredients for different therapeutics (sexual enhancement, weight loss, muscular strengthening, and relaxing products). The validation procedure was performed to evaluate selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision according to the Association of Official Analytical Chemists guidelines. The linearity was >0.98 in the range of 0.5–200 µg L−1. The LOQs were in the range 1–10 µg kg−1 for all target compounds. The accuracy (expressed as recovery) was 78.5–114%. The precision (expressed as the relative standard deviation) was below 9.15%. The developed method was applied for the determination of illicit compounds in dietary supplements collected from websites. As a result, the total detection rate was 13.5% (27 samples detected in 200 samples). The concentrations of detected samples ranged from 0.51 to 226 mg g−1. The proposed methodology is suitable for monitoring the adulteration of illicit compounds in dietary supplements.

Adulteration of Brain Health (Cognitive, Mood, and Sleep Enhancement) Food Supplements by the Addition of Pharmaceutical Drugs: A Comprehensive Review of Analytical Approaches and Trends

“…Shin et al [ 77 ] opted for a multi-class LC-MS/MS method targeting 64 pharmaceutical drugs utilized for various therapeutic purposes. Depending on their function, these targeted compounds might be found in supplements designed for purposes ranging from sexual enhancement and weight loss to muscular strengthening and relaxation products.…”

“…Of the 11 relaxation products evaluated, 1 contained kavain (18.8 mg/g), 1 melatonin (6.74 mg/g), and 4 were found to contain 5-HTP (56.6–226 mg/g). Kavain, magnoflorine, and picamilon were also analyzed by HPLC-MS/MS in dietary supplements, together with asarone (a natural compound found in Acorus calamus , traditionally used as a herbal remedy for anxiety and insomnia, and studied for its neuroprotective effects [ 91 ]) and other seven drugs for weight loss or sexual enhancement [ 77 ]. The validated method was applied to monitor 115 samples, resulting in the detection of kavain and magnoflorine in 2 samples.…”

“…As far as the literature consulted, data on the consumption prevalence of supplements to improve mood or sleep are still scarce or non-existent. However, the U.S. National Poll on Healthy Aging (NPHA) survey, targeting a community of older adults that included 1065 community-dwelling adults (aged [65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80], showed that about 35% suffered from sleep-specific difficulties and resorted to the use of sleep improvement products, namely 21.9% use over the counter sleep products, 12.5% consume herbal-containing products, and 8.3% use prescription medication [55]. In addition, it was recently reported that in the U.S., the use of melatonin, a key regulator of the circadian rhythm purportedly involved in sleep disorders and frequently added as an ingredient in PFS, has increased from 0.4% in 1999-2000 to 2.1% in 2017-2018 [56].…”

Development and Validation of the LC–MS/MS Method for Determination of 130 Natural and Synthetic Cannabinoids in Cannabis Oil

“…In studies of dietary supplements, these types of spectrometers are often combined with a liquid chromatograph (LC–MS/MS). They are frequently used for the analysis of dietary supplements supporting weight loss and for physically active people, usually in the form of stimulants and substances with anorexic, diuretic, or laxative effects [ 11 , 12 , 13 , 14 ].…”