Gas-phase dissociation study of erythrinian alkaloids by electrospray ionization mass spectrometry and computational methods

J Mass Spectrom. 2017 Sep;52(9):571-579. doi: 10.1002/jms.3962.

Abstract

Alkaloids from plants of the genus Erythrina display important biological activities, including anxiolytic action. Characterization of these alkaloids by mass spectrometry (MS) has contributed to the construction of a spectral library, has improved understanding of their structures and has supported the proposal of fragmentation mechanisms in light of density functional calculations. In this study, we have used low-resolution and high-resolution MSn analyses to investigate the fragmentation patterns of erythrinian alkaloids; we have employed the B3LYP/6-31+G(d,p) model to obtain their reactive sites. To suggest the fragmentation mechanism of these alkaloids, we have studied their protonation sites by density functional calculation, and we have obtained their molecular electrostatic potential map and their gas-phase basicity values. These analyses have indicated the most basic sites on the basis of the proton affinities of the nitrogen and oxygen atoms. The protonated molecules were generated by two major fragmentations, namely, neutral loss of CH3 OH followed by elimination of H2 O. High-resolution analysis confirmed elimination of NH3 by comparison with the losses of H2 and •CH3 . NH3 was eliminated from compounds that did not bear a substituent on ring C. The benzylic carbocation initiated the dissociation mechanism, and the first reaction involved charge transfer from a lone pair of electrons in the oxygen atoms. The second reaction consisted of ring contraction with loss of a CO molecule. The presence of hydroxy and epoxy groups could change the intensity or the occurrence of the fragmentation pathways. Given that erythrinian alkaloids are applied in therapeutics and are promising leads for the development of new drugs, the present results could aid identification of several analogues of these alkaloids in biological samples and advance pharmacokinetic studies of new plant derivatives based on MSn and MS/MS analyses. Copyright © 2017 John Wiley & Sons, Ltd.

Keywords: natural products; proton affinity; protonation site; spirocyclic alkaloid.

MeSH terms

  • Alkaloids / analysis*
  • Alkaloids / chemistry
  • Amines / chemistry
  • Binding Sites
  • Carbon Monoxide / chemistry
  • Erythrina / chemistry*
  • Hydrogen / chemistry
  • Models, Chemical
  • Nitrogen / chemistry
  • Plant Extracts / analysis
  • Plant Extracts / chemistry
  • Protons
  • Spectrometry, Mass, Electrospray Ionization / methods*
  • Static Electricity
  • Tandem Mass Spectrometry / methods

Substances

  • Alkaloids
  • Amines
  • Plant Extracts
  • Protons
  • Carbon Monoxide
  • Hydrogen
  • Nitrogen