Objective: To explore the mass spectral fragmentation patterns of the homologous secoiridiod glycosides(SIGs), and apply it to the chemical identification of the complex system. Methods: The mass spectral fragmentation behaviors of 4 standard SIGs, including gentiopicroside, swertiamarin, nuezhenoside and specnuezhenide, were studied in negative atmospheric pressure chemical ionization(APCI-) by UPLC-Q TOF MS/MS. An infinitylab poroshall 120 EC-C18 column(150 mm×2.1 mm, 2.7 μm) was used for separation of SIGs. The elution system consisted of acetonitrile and 0.1%(v/v) formic acid aqueous solution with gradient elution. The nebulizer and auxiliary gas pressure were both set at 345 kPa, and the curtain gas pressure was set at 241 kPa. The desolvation temperature was set at 550.0 ℃. The spray voltage was set at 5.5 kV, and the collision energy was set at 30 V. The spectra scan range was from m/z 50 to 1 000. Under those conditions, the fragmentation patterns of SIGs were summarized and applied to the structural characterization of the SIGs from Ligustri Lucidi Fructus. Results: In APCI- mass spectra, not only the frequently occurring neutral losses, such as glucosidic unit and H2O were detected, but also the characteristic retro Diels Alder (RDA) cleavage of the aglycon moiety were observed, based on accurate mass measurements and the elemental compositions of the product ions. Besides, 0,4A1- (m/z 119.0)、1,4A1- (m/z 89.0) and 2,4A1- (m/z 59.0) ions, and fragment ion of [glucose-H2O]- (m/z 161.0), [glucose-CH2O]- (m/z 149.1), [glucose-CH2O-H2O]- (m/z 131.1) were observed due to the ring cleavages of the sugar moieties. Based on the fragmentation patterns of these 4 reference substance SIGs, 16 SIGs, which contains 13 isomers in 5 groups, have been characterized in the extract of Ligustri Lucidi Fructus by UPLC-Q TOF MS/MS in negative ion mode. Conclusion: According to the mass spectral fragmentation patterns of the SIGs, it is more conducive to the material component study of such compounds in complex system.
LI Cun-man, HU Gao-shuang
. Identification of secoiridoid glycosides in Ligustri Lucidi Fructus extract by UPLC-Q TOF MS/MS in negtive ion mode[J]. Chinese Journal of Pharmaceutical Analysis, 2022
, 42(7)
: 1254
-1265
.
DOI: 10.16155/j.0254-1793.2022.07.20
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