Spermidine; Ions; Imidoesters; Chromatography, Liquid; Spectrometry, Mass, Electrospray Ionization/methods; Tandem Mass Spectrometry/methods; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry; Analytical Chemistry; Molecular Medicine; Pharmacology; Pharmaceutical Science; Drug Discovery; Complementary and Alternative Medicine; Organic Chemistry
Abstract :
[en] Phenolamides are abundant specialized metabolites found in nature and consist of hydroxycinnamic acids mono- or polyconjugated with polyamines. Their participation in flower development is well-documented, and their presence in pollen raises the question of their role in pollen/pollinator interactions. The structural characterization of phenolamides is complicated by the presence of positional isomers and stereoisomers. Liquid chromatography coupled to tandem mass spectrometry in the positive ionization mode is becoming very popular in phenolamide structural characterization. However, collision-induced transamidation processes that cause the swapping of side chains have been detected, making it difficult to distinguish regioisomers with this technique. In the present report, we explore the dissociation processes undergone by the [M - H]- ions of spermidine-based phenolamides as model compounds. We describe two original competitive dissociation routes, namely, the phenolate and imidate pathways, to account for the observed fragmentation reactions undergone by collisional activated standard phenolamide anions. Whereas the phenolate pathway is regioselective at the central position for spermidine, the imidate pathway, requiring a deprotonated amide, only occurs at the extremities. Tandem mass spectrometry experiments on negatively charged phenolamide ions may then outperform their positive ionization mode counterparts for the distinction between phenolamide regioisomers and globally for the identification of phenolamides in natural extracts.
Disciplines :
Entomology & pest control Chemistry Pharmacy, pharmacology & toxicology
Author, co-author :
Semay, Irène ; Université de Mons - UMONS > Faculté des Sciences > Service de Synthèse et spectrométrie de masse organiques
S836 - Synthèse et spectrométrie de masse organiques S817 - Chimie des matériaux nouveaux S869 - Zoologie M136 - Chimie thérapeutique et Pharmacognosie
Research institute :
R100 - Institut des Biosciences R400 - Institut de Recherche en Science et Ingénierie des Matériaux R550 - Institut des Sciences et Technologies de la Santé
Funding text :
This work was a part of the ARC ‘Actions de Recherche Concertées’ project ‘METAFLORE, 2019–2023’. The PhD grant of I.S. is supported by the ARC project METAFLORE. A.G. is supported by a F.R.S.-FNRS PhD grant “Aspirant”.
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