scholarly journals Characteristic product ions of acetylene carotenoids by electrospray and nanospray ionization tandem mass spectrometry

2020 ◽  
Vol 34 (16) ◽  
Author(s):  
Fausto Carnevale Neto ◽  
Thais Guaratini ◽  
Pio Colepicolo ◽  
Paul J. Gates ◽  
Norberto Peporine Lopes
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Tandem Mass ◽  
Product Ions ◽  
Nanospray Ionization ◽  
Characteristic Product ◽  
Ionization Tandem Mass Spectrometry

scholarly journals Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry

2017 ◽  
Vol 2017 ◽  
pp. 1-9 ◽  
Author(s):  
Herbert Júnior Dias ◽  
Ricardo Stefani ◽  
José Carlos Tomaz ◽  
Ricardo Vessecchi ◽  
Antônio Eduardo Miller Crotti
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Electrospray Ionization ◽  
Sesquiterpene Lactones ◽  
Multiple Reaction Monitoring ◽  
Lone Pair ◽  
Fragmentation Pathway ◽  
Tandem Mass ◽  
Product Ions ◽  
Ionization Tandem Mass Spectrometry

We investigated the fragmentation of the eudesmanolide-type sesquiterpene lactones 1α-(4-hydroxymethacryloyloxy)-3α,4α-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (1) and 1α-(2,3-epoxyangeloyloxy)-4α,15-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (2) by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The elimination of the different ester substituent at C(1) directly from protonated 1 and 2 (A) led to the formation of two regioisomer product ions B (A − RCO2H). Further fragmentation of B resulted from consecutive eliminations of H2O and CO molecules. However, we identified four product ions that allowed for the differentiation between 3,4- and 4,15-epoxyeudesmanolides. The formation of these diagnostic ions was associated with the C(3)–O bond of compound 1, which propitiates the participation of the lone pair of the oxygen epoxide in the formation of B through a Grob-Wharton-type fragmentation, then resulting in an alternative fragmentation pathway. These data can be useful for the fast differentiation between epoxyeudesmanolide regioisomers directly from Dimerostemma extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS), as an alternative to NMR, or even for quantitation studies of these compounds using multiple reaction monitoring (MRM) scan.

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