Characterization of phenolic compounds in Erigeron breviscapus by liquid chromatography coupled to electrospray ionization mass spectrometry.

Erigeron breviscapus is an important herbal drug for the treatment of cardiovascular and cerebral vessel diseases. In this study, phenolic compounds were extracted from the whole plant of E. breviscapus and analyzed by high-performance liquid chromatography/electrospray ionization mass spectrometry. A total of 53 compounds were identified or tentatively characterized based on their UV and mass spectra. These compounds included caffeoylquinic acids (CQAs), CQA glucosides, malonyl-CQAs, acetyl-CQAs, caffeoyl-2,7-anhydro-3-deoxy-2-octulopyranosonic acids (CDOAs), caffeoyl-2,7-anhydro-2-octulopyranosonic acids (COAs), flavones, flavonols and flavonones. Most of them were reported for the first time from E. breviscapus and nineteen of them belonged to new compounds. The MS(n) spectra of CQA glucosides were similar to CQAs and they were discriminated by their retention times. No caffeic acid related ions (X(0) (-), Y(0) (-) and Z(0) (-)) were observed in MS(n) spectra of acyl-CQAs compared to those of CQAs. Fragment ions ((2,5)O(-), (3,6)O(-) and (4,6)O(-)) corresponding to ring cleavage were shown in MS(n) spectra of CDOAs and COAs, characteristic of this class of compounds. The 5,6,7-trihydroxyl-substituted flavones were dominant in E. breviscapus. Their [A--H](-) ions underwent the loss of a molecule of H(2)O, followed by the loss of CO, which was used to discriminate from other hydroxyl-substituted flavones. Our results are the first comprehensive analysis of E. breviscapus constituents and will be helpful for the quality control of the herb of E. breviscapus and its related preparations. Copyright (c) 2007 John Wiley & Sons, Ltd.