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Abstract
The broad applications and mechanism explorations of traditional Chinese medicine prescriptions (TCMPs) require a clear understanding of TCMP chemical constituents. In the present study, we describe an efficient and universally applicable analytical approach based on ultra-performance liquid chromatography coupled to electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) with the MSE (E denotes collision energy) data acquisition mode, which allowed the rapid separation and reliable determination of TCMP chemical constituents. By monitoring diagnostic ions in the high energy function of MSE, target peaks of analogous compounds in TCMPs could be rapidly screened and identified. “Re-Du-Ning” injection (RDN), a eutherapeutic traditional Chinese medicine injection (TCMI) that has been widely used to reduce fever caused by viral infections in clinical practice, was studied as an example. In total, 90 compounds, including five new iridoids and one new sesquiterpene, were identified or tentatively characterized by accurate mass measurements within 5 ppm error. This analysis was accompanied by MS fragmentation and reference standard comparison analyses. Furthermore, the herbal sources of these compounds were unambiguously confirmed by comparing the extracted ion chromatograms (EICs) of RDN and ingredient herbal extracts. Our work provides a certain foundation for further studies of RDN. Moreover, the analytical approach developed herein has proven to be generally applicable for profiling the chemical constituents in TCMPs and other complicated mixtures.
Highlights
Traditional Chinese medicine prescriptions (TCMPs), which are combinations of several medicinal herbs, have been widely employed for thousands of years in China and other Asian countries
Due to its significant advantages in analytical speed and detection sensitivity, ultra-performance liquid chromatography coupled with electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) has become an irreplaceable technique for the on-line structural elucidation of multiple components in mixtures, especially for complex TCMs/TCMPs, biological samples and pesticide residues [5,6,7,8,9]
By virtue of UPLC-ESI-Q/TOF-MS and optimized MSE method, diagnostic fragment ions can be used as invaluable evidence for the detection of both expected and unexpected chemical constituents within TCMPs
Summary
Traditional Chinese medicine prescriptions (TCMPs), which are combinations of several medicinal herbs, have been widely employed for thousands of years in China and other Asian countries. UPLC coupled with MSE (E represents collision energy) technology provides an automated strategy to decrease analysis time and maximize duty cycles by using parallel alternating scans at low collision energy in the collision cell to obtain precursor ion information or at high collision energy to obtain accurate full-scan mass fragment, precursor ion and neutral loss information. Both precursor and fragmentation data in exact mass mode were collected in a single run; this method has provided excellent chromatographic and MS efficiencies for the rapid structural elucidation of multiple constituents in complex mixtures [10,11,12]. This novel approach is expected to be widely applied for analyzing other TCMPs and complex mixtures
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