title: Identification and separation of saxitoxins using hydrophilic interaction liquid chromatography coupled to traveling wave ion mobility-mass spectrometry.
abstract: The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non-sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non-sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC-IM-MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non-sulphated analogues were separated in the IM-MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM-MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method.
authors.affiliation: Normandie Université, COBRA, UMR 6014 et FR 3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF,1 rue Tesnière, 76821, Mont-Saint-Aignan Cedex, France.
authors.forename: Salomé
authors.initials: S
authors.lastname: Poyer
authors.forename: Corinne
authors.initials: C
authors.lastname: Loutelier-Bourhis
authors.forename: Gaël
authors.initials: G
authors.lastname: Coadou
authors.forename: Florence
authors.initials: F
authors.lastname: Mondeguer
authors.forename: Julien
authors.initials: J
authors.lastname: Enche
authors.forename: Anne
authors.initials: A
authors.lastname: Bossée
authors.forename: Philipp
authors.initials: P
authors.lastname: Hess
authors.forename: Carlos
authors.initials: C
authors.lastname: Afonso
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D057927:Hydrophobic and Hydrophilic Interactions; D007536:Isomerism; D013058:Mass Spectrometry / Q000379:methods*; D015394:Molecular Structure; D012530:Saxitoxin / Q000031:analogs & derivatives / Q000032:analysis* / Q000737:chemistry / Q000302:isolation & purification; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D053719:Tandem Mass Spectrometry
chemical_list: D012530:Saxitoxin; C013007:gonyautoxins
keywords: HILIC; ion mobility-mass spectrometry; isomers; multidimensional separation; saxitoxin