Alkali metal cation adducts, [M+Alk](+), and [M-H](-) ions of four known glycosylated furofuran lignans, M-pinoresinol 4-O-beta-D-glucopyranoside, (+)-phylliroside, (+)-8-hydroxypinoresinol 4-O-beta-D-glucopyranoside, and (+)-8-hydroxypinoresinol 8-O-beta-D-glucopyranoside, recently isolated from Carex distachya, were generated by electrospray ionization and allowed to undergo collisionally activated dissociation (CAD) in a quadrupole ion trap (QIT) and in a triple quadrupole (TQ) mass spectrometer. CAD mass spectra of [M+Na](+) and [M+Li](+) adducts revealed the presence of structurally diagnostic product ions. CAD mass spectra of deprotonated glycosylated furofuran lignans showed the typical neutral loss of 162 Da when the glucose residue was bound to a phenolic oxygen atom. When glycosylation occurred at an alcoholic oxygen, as for (+)-8-hydroxypinoresinol 80-O-beta-D-glucopyranoside, a neutral loss of 180 Da represented the main fragmentation pathway. Selective hydrogen/deuterium (H/D) exchange of all the acidic hydrogen atoms of furofuran glycosides, performed by introducing lignan glycosides in D2O/CH3OD solutions, were employed to obtain information on the nature of the product ions generated during TQ/CAD processes. Energy-resolved TQ/CAD mass spectra of deprotonated lignan glycosides and their deprotonated aglycones were used in a qualitative way to infer information on the integrated energetic picture of CAD fragmentations and to investigate the mechanism of the predominant dissociation/isomerization processes. On the basis of the hypothesized fragmentation mechanisms, gas-phase features of the furofuran ring were derived. The presence of an OH substituent in the C8 position decreased the electron density in the adjacent C8' position, modifying the fragmentation pathway. Copyright (C) 2008 John Wiley & Sons, Ltd.

Furofuranic glycosylated lignans: a gas-phase ion chemistry investigation by tandem mass spectrometry / Pepi, Federico; Andreina, Ricci; Antonio, Fiorentino; Simona, Piccolella; Annunziata, Golino; Brigida, D'Abrosca; Marianna, Letizia; Pietro, Monaco. - In: RAPID COMMUNICATIONS IN MASS SPECTROMETRY. - ISSN 0951-4198. - 22:21(2008), pp. 3382-3392. [10.1002/rcm.3746]

Furofuranic glycosylated lignans: a gas-phase ion chemistry investigation by tandem mass spectrometry

PEPI, Federico;
2008

Abstract

Alkali metal cation adducts, [M+Alk](+), and [M-H](-) ions of four known glycosylated furofuran lignans, M-pinoresinol 4-O-beta-D-glucopyranoside, (+)-phylliroside, (+)-8-hydroxypinoresinol 4-O-beta-D-glucopyranoside, and (+)-8-hydroxypinoresinol 8-O-beta-D-glucopyranoside, recently isolated from Carex distachya, were generated by electrospray ionization and allowed to undergo collisionally activated dissociation (CAD) in a quadrupole ion trap (QIT) and in a triple quadrupole (TQ) mass spectrometer. CAD mass spectra of [M+Na](+) and [M+Li](+) adducts revealed the presence of structurally diagnostic product ions. CAD mass spectra of deprotonated glycosylated furofuran lignans showed the typical neutral loss of 162 Da when the glucose residue was bound to a phenolic oxygen atom. When glycosylation occurred at an alcoholic oxygen, as for (+)-8-hydroxypinoresinol 80-O-beta-D-glucopyranoside, a neutral loss of 180 Da represented the main fragmentation pathway. Selective hydrogen/deuterium (H/D) exchange of all the acidic hydrogen atoms of furofuran glycosides, performed by introducing lignan glycosides in D2O/CH3OD solutions, were employed to obtain information on the nature of the product ions generated during TQ/CAD processes. Energy-resolved TQ/CAD mass spectra of deprotonated lignan glycosides and their deprotonated aglycones were used in a qualitative way to infer information on the integrated energetic picture of CAD fragmentations and to investigate the mechanism of the predominant dissociation/isomerization processes. On the basis of the hypothesized fragmentation mechanisms, gas-phase features of the furofuran ring were derived. The presence of an OH substituent in the C8 position decreased the electron density in the adjacent C8' position, modifying the fragmentation pathway. Copyright (C) 2008 John Wiley & Sons, Ltd.
2008
01 Pubblicazione su rivista::01a Articolo in rivista
Furofuranic glycosylated lignans: a gas-phase ion chemistry investigation by tandem mass spectrometry / Pepi, Federico; Andreina, Ricci; Antonio, Fiorentino; Simona, Piccolella; Annunziata, Golino; Brigida, D'Abrosca; Marianna, Letizia; Pietro, Monaco. - In: RAPID COMMUNICATIONS IN MASS SPECTROMETRY. - ISSN 0951-4198. - 22:21(2008), pp. 3382-3392. [10.1002/rcm.3746]
File allegati a questo prodotto
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/47878
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? 3
  • Scopus 14
  • ???jsp.display-item.citation.isi??? 13
social impact