Simultaneous analysis of 23 illegal adulterated aphrodisiac chemical ingredients in health foods and Chinese traditional patent medicines by ultrahigh performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry

Abstract

This paper presents an application of ultra high-performance liquid-chromatography-quadrupole-TOF high resolution mass spectrometry (UHPLC-Q-TOF HRMS) for simultaneous analysis of 23 illegal adulterated aphrodisiac type chemical ingredients in health foods and Chinese Traditional Patent Medicines (CTPMs). The mass spectrometer was operated in Information Dependent Acquisition (IDA) mode, which provides crucial information for the elemental composition analysis, structure elucidation and quantitative analysis simultaneously. Quantitative analysis was performed using the peak areas of the precursor ions in the XICs. The method validation included assessment of selectivity, sensitivity, calibration curve, accuracy, precision, recovery, matrix effect and stability. The results show good linear relationship with the concentrations of the analytes over wide concentration ranges (e.g., 0.05-10 μg/g for sildenafil) as all the fitting coefficients of determination r are >0.9984. The detection limits (LODs) were in the range of 0.002-0.1 μg/g. The recoveries were able to reach 82.5-103.6%, while the matrix effects ranged from 87.7 to 109.3%. The intra- and inter-day accuracies were in the range of 82.3-113.8%, while the intra- and inter-day precision ranged from 0.4 to 13.6%. Among 40 batches of health foods and 32 batches of CTPMs (including 28 capsules, 32 tablets, 10 liquid and 2 pills) samples, 28 batches of heath foods were positive. The detected chemical ingredients involved sildenafil, tadalafil, aildenafil and sulfoaildenafil. This method can be used for the screening, identification and quantification of illegal adulterated aphrodisiac chemical ingredients in health foods and CTPMs. Moreover, the LC-Q-TOF MS is very useful to structural elucidation of unknown compound.

Simultaneous determination of succinylcholine and its metabolite in animal‐derived foods by solid‐phase extraction combined with ultra‐performance liquid chromatography/mass spectrometry

“…The linearity of the calibration curve was assessed by the coefficient of determination. The matrix effect and recovery were assessed through a comparison between the responses obtained by the given concentration prepared in blank matrix and in solvent at the same concentration for three levels 18 . The matrix effect was calculated by the following equation: (peak areas obtained from neat solution standards/corresponding peak areas of standards spiked after extraction from matrix) × 100.…”

Screening of Phosphodiesterase-5 Inhibitors and Their Analogs in Dietary Supplements by Liquid Chromatography–Hybrid Ion Trap–Time of Flight Mass Spectrometry

“…The retention times and mass errors of all analytes are listed in Table 1, and the extracted ion chromatograms are depicted in Figure 1. (6), piperidinohongdenafil (7), homosildenafil (8), dimethylsildenafil (9), udenafil (10), cyclopentinafil (11), thiosildenafil (12), hydroxythiohomosildenafil (13), thiohomosildenafil (14), dimethylthiosildenafil (15), oxohongdenafil (16), benzylsildenafil (17), hydroxychlorodenafil (18), chlorodenafil (19), nitrodenafil (20), nor-neosildenafil (21), dichlorodenafil (22), vardenafil (23), acetylvardenafil (24), hydroxyvardenafil (25), nor-neovardenafil (26), desulfovardenafil (27), pseudovardenafil (28), tadalafil (29), aminotadalafil (30), acetaminotadalafil (31), demethyltadalafil (32), chloropretadalafil (33), N-octyltadalafil (34), yohimbine (35), mirodenafil (36), thioquinapiperifil (37), xanthoanthrafil (38), and phenolphthalein (39). * indicated the analytes among multiple peaks in the EIC.…”

“…In this regard, various spectrometric and chromatographic methods have been adopted to analyze the illegally added drugs in complex matrices [ 3 , 4 , 5 , 9 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. High-performance liquid chromatography with diode array detection (HPLC–DAD) and liquid chromatography with mass spectrometry (LC–MS) have been previously used to detect PDE-5 inhibitors and their analogs [ 3 , 5 , 7 , 8 , 9 , 10 , 16 , 17 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ]. When the standards of PDE-5 inhibitors and their analogs are available, HPLC with a UV spectrometer is a simple method for quantitative analysis [ 11 ].…”

“…Further, QqQ MS can only be used for the quantitative analysis of known compounds and not for screening purposes. Therefore, other spectroscopic methods such as high-resolution mass spectrometry (HRMS) based on Fourier transform ion cyclotron resonance (FT-ICR) [ 31 ], time of flight (TOF) [ 24 , 25 , 28 , 29 , 33 ], orbitrap [ 8 , 12 , 26 , 27 ], and nuclear magnetic resonance spectrometry [ 4 , 6 , 7 , 9 , 30 , 34 , 35 , 36 , 37 , 38 ] must be applied to clarify the structure of the analytes. In particular, hybrid ion trap (IT)–HRMS, including IT–TOF and Orbitraps (LTQ–Orbitrap and Orbitrap Fusions), is one of the most effective tools for screening and identification of unknown compounds owing to its high-resolution and multistage tandem MS (MS n ) ability.…”

A Mass Spectrometry Based Metabolite Profiling Workflow for Selecting Abundant Specific Markers and Their Structurally Related Multi-Component Signatures in Traditional Chinese Medicine Multi‐Herb Formulae

“…These SSDMC methods address the limitations encountered with quality controls (QC) restricted to a single marker per herbal drug. These limitations have been highlighted by cases of adulteration and falsification, which concern all types of herbal preparations, including TCMs (Wang et al, 2018), and even more so, the huge market of food supplements (Abdel-Tawab, 2018). By being limited to a single marker or to the total amount of a given class of components, cases of falsification by adding the said marker have been reported, for example involving extracts of Ginkgo biloba leaves (Czigle et al, 2018).…”