Fragmentation Study of Daphniphyllum Alkaloids by Electrospray Ionization Quadrupole Time-of-flight Mass Spectrometry

Title:Fragmentation Study of Daphniphyllum Alkaloids by Electrospray Ionization Quadrupole Time-of-flight Mass Spectrometry

Volume: 12 Issue: 3

Author(s): Min-Min Cao, Dan Wang, Hao Zhang, Dong-Mei Fang, Hong-Ping He, Xiao-Jiang Hao, Guo-Lin Zhang and Zhi-Jun Wu

Affiliation:

Keywords: Daphniphyllum alkaloids, electrospray, ESI-QTOF, six-member H rearrangement, fragmentation, isomers.

Abstract: A series of 16 Daphniphyllum alkaloids isolated from Daphniphyllum macropodum were investigated by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESIQTOF- MS/MS) in positive-ion mode. Deuterium labeling experiments were carried out to identify the major product ions. Although compounds have similar structures, the profiles of their MS/MS spectra vary greatly. For compounds 1 and 2, abundant product ions both in high and low mass range can be detected. A six-member H rearrangement and the cleavage of C1-C2 bond connecting rings A, C and D play an important role in providing the product ions in low mass range. For compounds 3-9, the relative abundance of product ions in low mass range is low. This may result from the loss of HCOOCH3 occurring readily because C4-C5 double bond prevents six-member H rearrangement. Main fragmentation patterns of compounds 10-14 are the loss of the different side-chain groups and the cleavage of pyrrol and pyridine rings. A series of ion clusters detected in low mass range are characteristic ions for compounds 10-14. Fragmentation patterns of compounds 15 and 16 were elucidated. Four groups of isomers in these compounds were distinguished by characteristic product ions or fragmentation patterns.

Cite this article as:

Cao Min-Min, Wang Dan, Zhang Hao, Fang Dong-Mei, He Hong-Ping, Hao Xiao-Jiang, Zhang Guo-Lin and Wu Zhi-Jun, Fragmentation Study of Daphniphyllum Alkaloids by Electrospray Ionization Quadrupole Time-of-flight Mass Spectrometry, Current Pharmaceutical Analysis 2016; 12 (3) . https://dx.doi.org/10.2174/1573412911666151022203917