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Establishing mass spectral fragmentation patterns for characterization of 1,2 -unsaturated pyrrolizidine alkaloids and N-oxides in Boraginaceae species from Macedonia using LC-ESI-MS/MS

Authors

  • Jasmina Petreska Stanoeva Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in Skopje, Macedonia
  • Elena Stefova Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in Skopje, Macedonia
  • Marinela Cvetanoska Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in Skopje, Macedonia
  • Jane Bogdanov Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in Skopje, Macedonia

DOI:

https://doi.org/10.20450/mjcce.2022.2491

Keywords:

pyrrolizidine alkaloids and N-oxides, tandem mass spectrometry, Boraginaceae

Abstract

Pyrrolizidine alkaloids (PAs) are secondary plant metabolites, and their 1,2-unsaturated derivatives, which contain the retronecine, heliotridine, or otonecine type of the necine base, have raised concern due to their ability to form hepatotoxic intermediates and exhibit serious toxic effects. Several hundred individual pyrrolizidine alkaloids and their N-oxides have been identified mostly using liquid chromatography coupled with mass spectrometry, although the number of available reference standards is limited.

In this work, characteristic fragment ions and their abundance in the mass spectra of different PAs were used to reveal typical fragmentation patterns for various classes of PAs that can be further employed to distinguish monoesters (retronecine, heliotridine type), open chain diesters and macrocyclic diesters, and corresponding N-oxides.

Fragment ions at m/z 120 and 138 were found in all types of PAs with a different relative abundance. Additional observation of fragment ions at m/z 94 and 156 was found to be typical for monoester PAs esterified at position C9 of the necin base, whereas fragment ions at m/z 111 and 172 were characteristic for monoester N-oxides. Fragment ions at m/z 180 and 220 were found to be typical for open chain diesters with esterification at C7 with acetic and angelic acid, respectively, whereas fragment ions at m/z 214 and 254 were characteristic for the respective N-oxides. For the 3ʹ-acetyl PA monoester or open chain diester derivatives, characteristic fragment ions were observed after loss of the acetyl moiety ([M+H]+–60), whereas for macrocyclic diesters and their N-oxides, fragment ions due to the neutral loss of CO were found ([M+H]+–28).

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Published

2022-06-19 — Updated on 2022-06-20

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How to Cite

Petreska Stanoeva, J., Stefova, E., Cvetanoska, M., & Bogdanov, J. (2022). Establishing mass spectral fragmentation patterns for characterization of 1,2 -unsaturated pyrrolizidine alkaloids and N-oxides in Boraginaceae species from Macedonia using LC-ESI-MS/MS. Macedonian Journal of Chemistry and Chemical Engineering, 41(1). https://doi.org/10.20450/mjcce.2022.2491 (Original work published June 19, 2022)

Issue

Vol. 41 No. 1 (2022)

Section

Natural Products

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Copyright (c) 2022 Jasmina Petreska Stanoeva, Elena Stefova, Marinela Cvetanoska, Jane Bogdanov

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