Phenolic compounds are the major bioactive constituents of Forsythia suspensa, an important Chinese herbal medicine used for the treatment of various infectious diseases. Fragmentation behaviors of the phenolic compounds in F. suspensa were investigated by using a high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS(n)) method. For common phenylethanoid glycosides, the loss of the caffeoyl moiety was the first fragmentation step, then sequential losses of rhamnose, hexose and water were observed in further fragmentations. If a substituent group presented in the beta position, the fragmentation was triggered by initial loss of a substituent group to form structures such as suspensaside A. Then it underwent the common fragmentation pathways as mentioned above, or eliminated characteristic residues of masses 134 or 152 Da, respectively. The latter pathway is reported here for the first time. The fragmentation behaviors of furofuran lignans displayed a typical cleavage of the tetrahydrofuran ring. However, the presence of a hydroxyl group at C-1 led to the successive loss of 30 Da. Neutral loss of CO(2) and benzyl cleavage were characteristic for lignans with a 2,3-dibenzylbutyrolactone skeleton. A neutral loss of 30 Da was also observed in the fragmentation pattern of flavonols. These fragmentation rules were implemented to analyze phenolic compounds in the fruits of F. suspensa. A total of 51 compounds, including 24 phenylethanoid glycosides, 21 lignans and 6 flavonols, were identified or tentatively characterized based on their retention times, UV spectra and MS fragmentation patterns.

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Triterpenoids extracted from Ganoderma lucidum (Leyss. ex Fr.) Karst were separated and characterized using optimized reversed-phase liquid chromatography with diode array detection and electrospray ion trap tandem mass spectrometry (HPLC-DAD-ESI-MS n ). They could be classified into five types depending on the fragmentation behavior. second alcohol at C-15 were oxidized to ketone, the prominent cleavage would occur at C-ring and produce a group of ions of a; if C-7 were oxidized to ketone, transference of two hydrogen atoms would occur during the cleavage of rings and a list of ions about a ϩ 2 and/or b ϩ 2 would appear instead. The above fragmentations and regularities in fragmentation pathways were reported for the first time, and were implemented for the analysis of triterpenoids in G. lucidum. The chloroform extract was separated on a Zorbax SB-C 18 column, eluting with an acetonitrile-0.2% acetic acid gradient. A total of 32 triterpenoids, including six new ones, were identified or tentatively characterized based on the tandem mass spectra of the HPLC peaks. (J Am Soc Mass Spectrom 2007, 18, 927-939)

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