Comparative analysis of the gas-phase reactions of cylindrospermopsin and the difference in the alkali metal cation mobility.
Cylindrospermopsin (CYN) belongs to a group of toxins produced by several strains of freshwater cyanobacteria. It is a compact zwitterionic molecule composed of a uracil section and a tricyclic guanidinium portion with a primarily hepatotoxic effect. Using low multi-stage and high-resolution mass spectrometry, the gas-phase reactions of this toxin have been investigated. Our data show that collision-induced dissociation (CID) spectra of CYN are dominated by neutral losses, and three major initial fragmentation pathways are clearly distinguishable. Interestingly, comparative analysis of protonated and cationizated molecules showed a significant difference in the balance of the SO3 and terminal ring elimination. These data indicate that the differential ion mobility of H+, Li+, Na+ and K+ leads to different fragmentation pathways, giving rise to mass spectra with different profiles.
Universidade de São Paulo, Faculdade de Ciências Farmacêuticas, Departamento de Análises Clínicas e Toxicológicas, Av Professor Lineu Prestes, 580 CEP 05508-900, São Paulo-SP, Brazil.
Felipe Augusto
FA
Dörr
José Carlos
JC
Tomaz
Norberto Peporine
NP
Lopes
Ernani
E
Pinto
D000468:Alkalies / Q000737:chemistry; D000470:Alkaloids; D001427:Bacterial Toxins; D002412:Cations; D000458:Cyanobacteria / Q000302:isolation & purification* / Q000378:metabolism*; D000087522:Cyanobacteria Toxins; D005740:Gases / Q000737:chemistry; D008670:Metals / Q000737:chemistry; D044367:Phase Transition; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D014498:Uracil / Q000031:analogs & derivatives* / Q000032:analysis / Q000737:chemistry
D000468:Alkalies; D000470:Alkaloids; D001427:Bacterial Toxins; D002412:Cations; D000087522:Cyanobacteria Toxins; D005740:Gases; D008670:Metals; C089595:cylindrospermopsin; D014498:Uracil