Neutral Fragment Filtering for Rapid Identification of New Diester-Diterpenoid Alkaloids in Roots of Aconitum carmichaeli by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap-Orbitrap Mass Spectrometry

Abstract

A rapid and effective method was developed for separation and identification of diester-diterpenoid alkaloids (DDA) in the roots of Aconitum carmichaeli by ultra-high-pressure liquid chromatography coupled with high resolution LTQ-Orbitrap tandem mass spectrometry (UHPLC-LTQ-Orbitrap-MSn). According to accurate mass measurement and the characteristic neutral loss filtering strategy, a total of 42 diester-diterpenoid alkaloids (DDA) were rapidly detected and characterized or tentatively identified. Meanwhile, the proposed fragmentation pathways and the major diagnostic fragment ions of aconitine, mesaconitine and hypaconitine were investigated to trace DDA derivatives in crude plant extracts. 23 potential new compounds were successfully screened and characterized in Aconitum carmichaeli, including 16 short chain fatty acyls DDA, 4 N-dealkyl DDA and several isomers of aconitine, mesaconitine and hypaconitine.

Rapid separation and characterization of diterpenoid alkaloids in processed roots of Aconitum carmichaeli using ultra high performance liquid chromatography coupled with hybrid linear ion trap‐Orbitrap tandem mass spectrometry

“…The UHPLC was coupled to a LTQ‐Orbitrap XL hybrid mass spectrometer (Thermo Electron, Bremen, Germany) via an ESI interface. Samples were analyzed in positive ion mode and the conditions of ESI source were set as the same with the previous study . The Orbitrap MS calibration was conducted prior to the experiments according to the manufacturer's guidelines using a standard solution mix of SDS, sodium taurocholate, the tetrapeptide MRFA acetate salt, and Ultramark.…”

“…The ion trap provides multistage MS n mass spectra using data‐dependent analysis and mass accuracies of <3 ppm would be obtained by the Orbitrap scan in an external calibration mode. In our previous work , a rapid method was developed for identification of DDA in Fuzi by UHPLC–LTQ‐Orbitrap MS n . The fragmentation rules of different substituents types by LTQ‐Orbitrap mass were summarized and 23 potential new DDA were tentatively identified.…”

Recent Advances in Ultra-High Performance Liquid Chromatography for the Analysis of Traditional Chinese Medicine

“…A total of forty-two diester-diterpenoid alkaloids were separated and identified in the roots of Aconitum carmichaeli by UHPLCLTQ-Orbitrap-MS n . This method has been demonstrated to be an effective tool for the analysis of TCMs (Zhang et al 2012). Thirty-three compounds, including catechin derivatives, flavanonols, phenolic acid derivatives, and phenylpropanoid glycosides were either identified or tentatively characterized in the rhizome of Smilacis glabrae (Li et al 2012).…”

“…The determination of many complex components of traditional Chinese preparations like Si-Jun-Zi-Tang, Samhwangsasim-tang, Xue Fu Zhu Yu and Dan-Lou tablets have also been achieved (Zhang et al 2011; Poudel et al 2013; Zhang et al 2012; Dong et al 2013). Liang et al combined a UHPLC with a tunable UV detector (UHPLCTUV) and a UHPLC-Q-TOF method for identification and quantification of the main constituents in Niu-Huang-Jie-Du tablets.…”

Clinical Aspects of Aconitum Preparations

“…ite preparation using trivial analytical equipment available in almost all analytical laboratories [13][14][15][16][17][18]. Also, the biological effects of different Aconitum sp.…”