Rapid and sensitive screening and characterization of phenolic acids, phthalides, saponins and isoflavonoids in Danggui Buxue Tang by rapid resolution liquid chromatography/diode‐array detection coupled with time‐of‐flight mass spectrometry

Abstract

A novel rapid resolution liquid chromatography (RRLC) method coupled with diode-array detection (DAD) and time-of-flight mass spectrometry (TOFMS) in both positive and negative modes has been developed for quick and sensitive identification of the major compounds in Danggui Buxue Tang (DBT) preparation. Significant advantages of the use of RRLC with 1.8-microm porous particles include the much higher speed of chromatographic separation and great enhancement in sensitivity, compared with the conventional high-performance liquid chromatography (HPLC). With dynamic adjustment of the key role as fragmentor voltage in TOFMS, an efficient transmission of the ions was achieved to obtain the best sensitivity for providing the molecular formula for each analyte, and abundant fragment ions for structural information. The structural characterization of the major compounds in DBT was elucidated with authentic standards by DAD-TOF/MS, including phenolic acids, phthalides, saponins and isoflavonoids. The targets were rapidly screened from the complicated DBT matrix using a narrow mass window of 0.01 Da to restructure extracted ion chromatograms. By accurate mass measurements within 3 ppm error for each molecular ion and subsequent fragment ions, ten phenolic acids and phthalides including three groups of isomers, thirteen major saponins with a 20,24-epoxy-9,19-cyclolanostane-3,6,16,25-tetrol skeleton, sixteen isoflavonoids, corresponding glycosides, malonylglycosides, and acetylglycosides were identified in DBT preparation. The appropriate fragmentation pathways for them were also proposed based on definite elemental composition of the fragment ions.

Fragmentation study of iridoid glycosides and phenylpropanoid glycosides in Radix Scrophulariae by rapid resolution liquid chromatography with diode‐array detection and electrospray ionization time‐of‐flight mass spectrometry

“…Therefore, the development of simple and rapid methods for the analysis of complex compositions is of great signifi cance in the quality control of herbal medicine. Nowadays, high-performance liquid chromatography (HPLC) coupled with mass spectrometry (MS) has been proved to be a very useful tool applied to the characterization of constituents in medicinal herbs (Qi et al, 2008;Li et al, 2008;Es-Safi et al, 2007). The systematic structural characterization of the compounds in Radix Scrophulariae with mass spectrometric method has, to our knowledge, not been examined, and is thus interesting from a phytochemical and analytical point of view.…”

Identification of metabolites of Danggui Buxue Tang in rat urine by liquid chromatography coupled with electrospray ionization time‐of‐flight mass spectrometry

“…24,[26][27][28] Furthermore, the use of insource fragmentation via alternate stepping of the skimmer cone voltage provides a convenient and sensitive approach to generate fragment ions from LC-separated biomolecules for structural identification. 21,29,30 Although these characteristics do not replace the analytical merits of tandem mass spectrometry (MS/MS) of specific precursor ions, the current capabilities of TOFMS instruments provide valuable structural insights for the characterization of drug metabolites. Previously, we analyzed the chemical information of an ethanol extract of DBT, and identified 39 major constituents.…”

Chromatographic Fingerprint Analysis and Characterization of Constituents in Shenqi Fuzheng Injection by HPLC-DAD-ELSD and UFLC-DAD-Q-TOF Tandem Mass Spectrometry Techniques

“…The other components were tentatively identified according to their MS fragmentation pattern, and also by studying their UV spectral characteristics and reported literatures. Accordingly, the peaks were ascribed to cytidine (1) [27,28], uracil (2) [29,30], guanosine (4) [31,32], adenine nucleoside (6) [17,18], syringoside (7) [33,34] (10) [35], isomucronulatol-7,2′-di-O-glucoside (11) [36], biochanin-7-glucoside (12) [37,38], 9,10-dimethoxypterocarpan-3-O-xylosylglucoside (15) [39], 9,10-dimethoxypterocarpan-3-O-β-D-glucoside (16) [39], isomucronulatol-7-O-glucoside (17) [36,40], astragaloside VI (1′) [26,39,41], astragaloside VII (2′) [26,39,41], and astragaloside II (4′) [39,[41][42][43]. However, they still need to be further confirmed with the reference compounds and structural analysis by nuclear magnetic resonance (NMR) method.…”