Analysis and fragmentation mechanisms of hirsutinolide‐type sesquiterpene lactones by ultra‐high‐performance liquid chromatography/electrospray ionization linear ion trap Orbitrap mass spectrometry

Abstract

The UHPLC/DAD-HRMS(n) method combining characteristic fragmentation patterns and the profiles of the product ions generated in the MS and MS/MS spectra is an effective technique for characterizing hirsutinolide-type SLs.

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na+/H+ adducts interactions in complex mixture

“…The set of fragments m/z 277, m/z 259, m/z 241, and m/z 231 were observed in fragmentation patterns of both hirsutinolide and glaucolide skeletons regardless the precursor ion ([M+H] + or [M+Na] + ). Similar peaks were previously reported and suggested as diagnostic ions for the characterization of both SL‐subtypes. In fact, our findings partially corroborate the results of Girardi and coworkers, which proposed m/z 299 and m/z 259 as diagnostic ions to hirsutinolide core, based on a fragmentation pathway different from our proposal.…”

“…Few LC‐MS methods were developed and reported for hirsutinolide and glaucolide characterization and have not been yet conducted to extensively explore their fragmentation mechanism and to quickly differentiate these two skeletal isomers in a mixture. Because the nuclear magnetic resonance (NMR) analysis for hirsutinolides and glaucolides requires peculiarities (such as high‐ or low‐temperature experiments) and the difficulties in LC‐MS dereplication of isomers, a rapid approach for these two SL‐subtype differentiation in a complex mixture is very useful.…”

Chemical Constituents, Antiproliferative and Antioxidant Activities of Vernonanthura nudiflora (Less.) H. Rob. Aerial Parts

“…The identification was established on the basis of the fragmentation pattern of their main ion by MS/MS analysis, and compared to those already described in literature from hirsutinolides. 40,[55][56][57] Compounds 18-22 and 25-26 were previously reported from V. nudiflora, 23 whereas compounds 23 and 24 are being described herein for the first time for this species.…”

Análise metabolômica aplicada à quimiotaxonomia de espécies do gênero <i>Vernonia sensu lato</i> (Vernonieae)

“…As lactonas sesquiterpênicas identificadas pertencem principalmente às classes dos hirsutinolidos e dos glaucolidos. Os hirsutinolidos apresentam absorção máxima no UV em cerca de 280 nm a 290 nm, enquanto que os glaucolidos apresentam absorção máxima no UV em aproximadamente 210 nm a 220 nm (BARDÓN et al, 1990;GIRARDI et al, 2016;KOTOWICZ et al, 1998;WILLIAMS et al, 2005;YOUN et al, 2014 (BARDON et al, 1988;CARTAGENA et al, 2000;KHAN et al, 2004). Os espectros de massas e de UV são apresentados no Apêndice 60.…”

“…361(perda de uma molécula de água), m/z 279 (perda da unidade tiglato) e m/z 261 (perda de uma molécula de água a partir de m/z 279), conforme o relatado na literatura(GIRARDI et al, 2016). Os espectros de massas e de UV são apresentados no…”