Comprehensive screening of multiclass illegal adulterants in herbal supplements and Spice-type drugs using specific MS/MS fragmentations by UHPLC-Q/TOF-MS

Abstract

In this study, a comprehensive screening method for 98 multi-class illegal adulterants (19 NSAIDS, 31 weight loss drugs, 35 psychotropic substances, and 13 cannabinoids) in dietary supplements and Spice drugs was suggested by UHPLC-Q/TOF-MS. After effective application of pH controlled liquid–liquid extraction from herbal supplements and Spice-type drugs, a broad range of 98 adulterants was successfully separated within 15 min on 1.7 μm fused-core C18 particles in a 100 × 2.1 mm column with gradient elution (mobile phase A: 0.1% formic acid in water; B: 0.1% formic acid in acetonitrile) and sensitively detected at sub-ng g⁻¹ levels by ESI in positive ion mode. From the MS/MS spectra of illegal adulterants, certain common ions were observed to reflect their structural characteristics: m/z 117 for phenethylamines, m/z 155 and 144 for synthetic cannabinoids, m/z 165 and 199 for opioid analogues and m/z 125 and 158 for sibutramine analogues. Specific neutral molecule loss fragments were also observed: H₂O, NH₃, or CO respectively for hydroxyl, amine, or carbonyl group containing adulterants. Phenylamide, C₇H₄O₃S, or C₂H₃NO molecule loss fragmentations were observed for heterocyclic compounds. Based on these specific fragmentations, extracted common ion chromatograms (ECICs) and neutral loss scans (NLSs) were effectively applied for rapid screening of illegal adulterants in herbal supplements and Spice-type drugs. The developed method can serve as a promising screening tool for confirmation and determination of illegal adulterants in various types of supplements, thus ensuring public safety.