Wide-Scope Screening of Illegal Adulterants in Dietary and Herbal Supplements via Rapid Polarity-Switching and Multistage Accurate Mass Confirmation Using an LC-IT/TOF Hybrid Instrument

Abstract

A new analytical strategy was developed that integrates a generic sample preparation into a liquid chromatography-multistage ion trap/time-of-flight mass spectrometry (LC-IT(MS(n))/TOF), allowing for large-scale screening and qualitative confirmation of wide-scope illegal adulterants in different food matrices. Samples were pretreated by a fast single-tube multifunction extraction for accurate multistage mass measurement on the hybrid LC-IT/TOF system. A qualitative validation performed for over 500 analyte-matrix pairs showed the method can reduce most of the matrix effects and achieve a lower limit of confirmation at 0.1 mg/kg for 73% of the target compounds. A unique combination of dual-polarity detection, retention time, isotopic profile, and accurate MS(n) spectra enables more comprehensive and precise confirmation, based on the multiparameter matching by automated library searching against the user-created database. Finally, the applicability of this LC-IT(MS(n))/TOF-based screening procedure for discriminating coeluting isobars, identifying nontarget adulterants, and even tentatively elucidating unexpected species in real samples is demonstrated.

Investigation of signaling molecules and metabolites found in crustacean hemolymph via in vivo microdialysis using a multifaceted mass spectrometric platform

“…We utilized the automated combination of positive and negative ionization modes mass spectra derived from fast polarity switching that has been widely used in lipidomics and drug metabolomics area . This extension enables detection of metabolites in complex biological samples and provided complementary identification of untargeted metabolomics . Owing to fast polarity switching approach, two total ion chromatograms as well as averaged mass spectrum clearly revealed its benefit of complementary recognition gained from the integration of two ionization modes as shown in Fig.…”

Discovery of Anthocyanin Biosynthetic Pathway in Cosmos caudatus Kunth. Using Omics Analysis

“…The structure of these anthocyanidins and the 11 observed anthocyanins in the C. caudatus extracts are illustrated in Table 4, along with their molecular weights. The high-resolution time-of-flight (TOF) mass spectrometer (HRMS) with mass-resolving power of ≥10,000 at the full width at half maximum (FWHM) of a peak, sub-ppm (parts per million) mass measurement error, and characteristic sensitive full-spectrum scanning allowed the calculation of accurate elemental formulae and the elucidation of the anthocyanin identities in the C. caudatus extracts [58][59][60]. The generated molecular formulae were then compared to previous reports on anthocyanins, as listed in Table 5.…”

Simultaneous screening of dietary supplements for 25 anti‐hyperlipidemic substances using ultra‐performance liquid chromatography and liquid chromatography/electrospray ionization tandem mass spectrometry

“…Common adulterants include erectile dysfunction, anti‐hypertensive, anti‐diabetic, and anti‐obesity drugs 10–13 . In addition, in recent years, lovastatin, lovastatin acid and bezafibrate have been found unexpectedly in red yeast rice supplements 14–16 . This adulteration presents a serious threat to consumer health because of a lack of data or inaccurate safety data, as well as the potential for undesirable side effects 16,17 .…”

“…Previously, Fukiqake et al reported an ultra‐performance liquid chromatography (UPLC) method using an ultraviolet (UV) detector for the simultaneous determination of 12 statins in dietary supplements 14 . Guo et al reported an LC/ion trap time‐of‐flight mass spectrometry method for the screening of various drug compounds including five statins and two fibrates in dietary supplements 15 . In addition, Cohen et al reported a method for the determination of lovastatin in dietary supplements using an UPLC system equipped with a diode‐array detector and a quadrupole time‐of‐flight mass spectrometer 16 Recently, Di Donna et al analyzed lovastatin‐containing dietary supplements using LC/tandem mass spectrometry (LC/MS/MS) 19 .…”

“…[10][11][12][13] In addition, in recent years, lovastatin, lovastatin acid and bezafibrate have been found unexpectedly in red yeast rice supplements. [14][15][16] This adulteration presents a serious threat to consumer health because of a lack of data or inaccurate safety data, as well as the potential for undesirable side effects. 16,17 Recently, the German Federal Institute for Risk Assessment (Bundesinstitut für Risikobewertung (BfR)) advised consumers to refrain from taking dietary supplements containing red yeast rice or to take them only after consulting with their doctors because of their possible lovastatin content.…”