@article{fdi:010066219,
  title = {{A}nalysis and fragmentation mechanisms of hirsutinolide-type sesquiterpene lactones by ultra-high-performance liquid chromatography/electrospray ionization linear ion trap {O}rbitrap mass spectrometry},
  author = {{G}irardi, {C}. and {J}ullian, {V}al{\'e}rie and {H}addad, {M}ohamed and {V}ansteelandt, {M}. and {C}abanillas, {B}. {J}. and {K}apanda, {C}. {N}. and {H}erent, {M}. {F}. and {Q}uetin-{L}eclercq, {J}. and {F}abre, {N}icolas},
  editor = {},
  language = {{ENG}},
  abstract = {{R}ationale{H}irsutinolide-type sesquiterpene lactones ({SL}s) are natural biologically active compounds mainly found in the genus {V}ernonia. {V}ery few studies have been published about the fragmentation mechanisms of {SL}s generally and none about hirsutinolides, although they have drawn attention through their biological and taxonomical interest. {T}his work aims to propose a mass spectrometry fragmentation pattern for hirsutinolides in order to detect and to identify them in a botanical extract. {M}ethods{T}he fragmentation pathways of six pure hirsutinolides isolated from {P}seudelephantopus spiralis were established by positive ion electrospray high-resolution linear ion trap {O}rbitrap tandem mass spectrometry ({ESI}(+)-{HRMS}n). {A} resolutive, hyphenated ultra-high-performance liquid chromatography ({UHPLC}) coupled to diode array detection ({DAD}) and {ESI}(+)-{HRMS}n method was then implemented to separate and analyze them. {T}he ionization behaviour and diagnostic product ions were investigated by both methods. {T}he {UHPLC}/{DAD}-{ESI}-{HRMS}n method was applied for the dereplication of a plant extract. {R}esults{F}or the six standard compounds, the main fragmentation pattern consists first in the loss of the side chain in the {C}-8 position followed by the loss of the substituent in the {C}-13 position. {UHPLC}/{HRMS} analyses of hirsutinolides mainly produced sodiated molecules or [{M}+{H}-{H}2{O}](+) ions. {T}he high-abundance product ions at m/z 299 and 259 were established to be the characteristic diagnostic ions of the hirsutinolide core. {T}he analysis of a {P}. spiralis extract further led to the identification of two putative hirsutinolides. {C}onclusions{T}he {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 {SL}s.},
  keywords = {{PEROU}},
  booktitle = {},
  journal = {{R}apid {C}ommunications in {M}ass {S}pectrometry},
  volume = {30},
  numero = {5},
  pages = {569--580},
  ISSN = {0951-4198},
  year = {2016},
  DOI = {10.1002/rcm.7473},
  URL = {https://www.documentation.ird.fr/hor/fdi:010066219},
}