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. 2018 Nov 30;23(12):3143.
doi: 10.3390/molecules23123143.

Systematic Profiling of the Multicomponents and Authentication of Erzhi Pill by UHPLC/Q-Orbitrap-MS Oriented Rapid Polarity-Switching Data-Dependent Acquisition and Selective Monitoring of the Chemical Markers Deduced from Fingerprint Analysis

Li Jia  1   2 , Lingling Fu  3   4 , Xiaoyan Wang  5   6 , Wenzhi Yang  7   8 , Hongda Wang  9   10 , Tiantian Zuo  11   12 , Chunxia Zhang  13   14 , Ying Hu  15   16 , Xiumei Gao  17 , Lifeng Han  18   19
Affiliations

Systematic Profiling of the Multicomponents and Authentication of Erzhi Pill by UHPLC/Q-Orbitrap-MS Oriented Rapid Polarity-Switching Data-Dependent Acquisition and Selective Monitoring of the Chemical Markers Deduced from Fingerprint Analysis

Li Jia et al. Molecules. .

Abstract

The analytical platform UHPLC/Q-Orbitrap-MS offers a solution to quality investigation of TCM with high definiteness. Using Erzhi Pill (EZP) as a case, we developed UHPLC/Q-Orbitrap-MS based approaches to achieve systematic multicomponent identification and rapid authentication. Comprehensive multicomponent characterization of EZP was performed by negative/positive switching data-dependent high-energy collision-induced dissociation-MS² (HCD-MS²) after 25 min chromatographic separation. By reference compounds comparison, elemental composition analysis, fragmentation pathways interpretation, and retrieval of an in-house library, 366 compounds were separated and detected from EZP, and 96 thereof were structurally characterized. The fingerprints of two component drugs (Ligustri Lucidi Fructus, LLF; Ecliptae Herba, EH) for EZP were analyzed under the same LC-MS condition by full scan in negative mode. In combination with currently available pharmacological reports, eight compounds were deduced as the 'identity markers' of EZP. Selective ion monitoring (SIM) of eight marker compounds was conducted to authenticate six batches of EZP samples. Both LLF and EH could be detected from all EZP samples by analyzing the SIM spectra, which could indicate their authenticity. Conclusively, UHPLC/Q-Orbitrap-MS by rapid polarity switching could greatly expand the potency of untargeted profiling with high efficiency, and SIM of multiple chemical markers rendered a practical approach enabling the authentication of TCM formulae.

Keywords: Erzhi Pill; UHPLC/Q-Orbitrap-MS; authentication; identity marker; polarity-switching data-dependent acquisition; selective ion monitoring.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Chemical structures of 30 reference compounds, representative of seven different categories of plant secondary metabolites that were ever reported from Ligustri Lucidi Fructus and Ecliptae Herba.
Figure 2
Figure 2
Annotation of the HCD-MS2 data for reference compounds 2 (Iridoid) and 7 (Triterpenoid) obtained in both negative and positive ESI modes.
Figure 3
Figure 3
Annotation of the HCD-MS2 data for reference compounds 24 (Flavonoid) and 13 (Phenylethanol) obtained in both negative and positive ESI modes.
Figure 4
Figure 4
Fragmentation pathway analysis of four unknown compounds (4#: iridoid; 88#: triterpenoid; 55#: flavonoid; 14#: phenylethanol) profiled from EZP based on the negative and positive HCD-MS2 data.
Figure 5
Figure 5
Overlapped fingerprints of two component drugs Ligustri Lucidi Fructus (LLF) and Ecliptae Herba (EH) under the same UHPLC/Q-Orbitrap MS condition (full scan in ESI− mode; A) and the SIM spectra of six batches of commercial EZP samples (B).
See this image and copyright information in PMC

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