Targeted analysis of multiple pharmaceuticals, plant toxins and other secondary metabolites in herbal dietary supplements by ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry.
In this study, an ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry (UHPLC-Q-orbitrap MS) method was developed and validated for simultaneous determination of 96 pharmaceuticals, plant toxins, and other plant secondary metabolites in herbal dietary supplements. Target analytes were extracted from samples using the QuEChERS (quick easy cheap effective rugged safe) procedure. The instrument was operated in full MS-data dependent tandem mass spectrometry (full MS-dd-MS/MS) acquisition mode which enabled collection of quantitative high resolution (HR) full mass spectral data and confirmatory HR MS/MS data in a single run. The method provided excellent selectivity in both full MS and dd-MS/MS mode. Under optimized collision energy settings, product ion spectra containing both precursor and two or more product ions were obtained for most of the analytes. Limits of detection (LODs) and limits of quantification (LOQs) for the method differed significantly for the examined matrices. LODs≤10μg kg(-1) and LOQs≤50μg kg(-1) were obtained for 48 to 81% of target compounds across five different matrices. With the exception of highly polar analytes, the optimized QuEChERS extraction procedure provided acceptable recoveries in the range 70%-120%. The precision of the method, characterized as the relative standard deviation (RSD, n=5), was ≤25% and ≤18% at spiking concentrations of 50μg kg(-1) and 500μg kg(-1), respectively. Because of variations in matrix effects in extracts of herbal dietary supplements that differed in composition, the method of standard additions and an approach based on dilution of matrix components followed by quantification using solvent standards were applied for quantification. The procedure was used to examine commercial dietary supplements for the 96 analytes of interest. To the best of our knowledge, this is the first report of an integrated analysis and quantification of this wide range of compounds.
U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, Office of Regulatory Science, 5100 Paint Branch Parkway, HFS-717, College Park, MD 20740, USA. Electronic address: Lukas.Vaclavik@fda.hhs.gov.
Lukas
L
Vaclavik
U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, Office of Regulatory Science, 5100 Paint Branch Parkway, HFS-717, College Park, MD 20740, USA.
Alexander J
AJ
Krynitsky
U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, Office of Regulatory Science, 5100 Paint Branch Parkway, HFS-717, College Park, MD 20740, USA.
Jeanne I
JI
Rader
D002851:Chromatography, High Pressure Liquid; D019587:Dietary Supplements / Q000032:analysis*; D004364:Pharmaceutical Preparations / Q000032:analysis*; D028321:Plant Preparations / Q000737:chemistry* / Q000378:metabolism*; D010947:Plants, Toxic / Q000737:chemistry*; D064210:Secondary Metabolism; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry; D014118:Toxins, Biological / Q000032:analysis*
D004364:Pharmaceutical Preparations; D028321:Plant Preparations; D014118:Toxins, Biological
Dietary supplements; Pharmaceuticals; Plant toxins; Quadrupole-orbitrap mass spectrometer; Ultra-high performance liquid chromatography