Analysis of the traditional medicine YiGan San by the fragmentation patterns of cadambine indole alkaloids using HPLC coupled with high‐resolution MS

Abstract

YiGan San (YGS) has long been used in traditional Japanese and Chinese folk medicine and serves as a potent and novel therapeutic agent to treat Alzheimer's disease. In the present study, a rapid and sensitive method based on HPLC coupled with diode-array detection and quadrupole TOF MS (Q-TOF-MS) was designed to reveal the chemical constituents of YGS. Thirty-six compounds were identified and assigned in YGS, including 14 alkaloids, nine γ-lactones, six flavonoids, three triterpenoid saponinares, two small molecular organic acids, and two other types of compounds. In addition, the accurate fragment weight and MS/MS fragmentation reactions of a subtype indole alkaloid in Uncariae ramulus cum uncis were summarized for the first time to realize rapid identification without reference substances. For the first time, 11 major constituents were comprehensively quantified with a HPLC coupled with triple-quadrupole MS method. A three-section switch was used to realize such multicomponent identification. The contents of saikosaponin B2 and isoliquiritin, which produce anti-inflammatory and antidepressant-like effects, were extremely different, up to 700 times, in two sources of YGS. The developed qualitative and quantitative method was proved to be precise, accurate, and reproducible.

UFLC-PDA-MS/MS Profiling of Seven Uncaria Species Integrated with Melatonin/5-Hydroxytryptamine Receptors Agonistic Assay

“…In the MS 2 spectra, the identical fragmentation at m/z 385 (C 21 H 24 N 2 O 5 ) and 367 (C 21 H 22 N 2 O 4 ) suggested closely related structures. In accordance with the previous reports, 3α-dihydrocadambine, 3β-dihydrocadambine, and 3β-isodihydrocadambine were reasonably suggested [19]. Peak 15 showing a molecular formula of C 38 H 50 N 2 O 19 was deduced from the [M+H] + ion at m/z 839.3054.…”

An integrated strategy for the systematic characterization and discovery of new indole alkaloids from Uncaria rhynchophylla by UHPLC/DAD/LTQ-Orbitrap-MS

“…On the basis of our current knowledge of the chemistry of UR, a filter (mass range 302-433 Da; mass defect 128-244 mDa) was set to sieve the free alkaloids from the total ion current (TIC) chromatogram of UR extracts. In addition, NLF by 162.05 Da (C 6 H 10 O 5 ) was employed to filter the glucosides of alkaloids, since glucose (Glc) is characterized by the neutral elimination of C 6 H 10 O 5 (162.05 Da) during ESI-MS n fragmentation [29].…”

“…Notably, the fragmentation of tMINs with reference standards was reported for the first time, to the best of our knowledge.Glycosides of pMIA The ESI-MS n fragmentation behaviors of two pMIA glycosides (T13: vincosamide; T14: 3α-dihydrocadambine) were investigated. Upon MS/MS fragmentation, a neutral fragment of mass 162.05 Da, corresponding to a Glc residue, was lost from both of them[29]. Further MS 3 fragmentation of the obtained aglycone portions generated very different product ions that were correlated with their structural differences.…”

Simultaneous quantitative analysis of nine triterpenoid saponins for the quality control of Stauntonia obovatifoliola Hayata subsp. intermedia stems

“…An HPLC coupled with diode array detection (DAD) method was developed for the simultaneous quantification of triterpenoid glycosides in Fatsia japonica Decne. & Planch, including fatsioside A, hederoside I, and staunoside A ; HPLC coupled with evaporative light scattering detection was used to determine triterpenoid saponins in Folium Ilicis Purpureae , including pedunculoside, 23‐hydroxytormentic acid, rutundic acid, and ilexoside B ; LC–MS/MS methods were applied for the determination of three triterpenoid saponins in the traditional medicine formula YiGan San and the pharmacokinetic studies of uralsaponin C, uralsaponin F, 22β‐acetoxyl‐glycyrrhizin, 24‐hydroxy‐licorice‐saponin E2, licorice‐saponin G2, licorice‐saponin E2, glycyrrhizic acid, and licorice‐saponin J2 . However, the target analytes of interest in the present study have different structures and physico‐chemical properties from those triterpenoid saponins mentioned above.…”