Palytoxin (C129H223N3O54) and its analogues (ovatoxins and ostreocins) fall into the same group of marine biotoxins considered highly dangerous for human health through ingestion, skin contact and/or inhalation [1]. They were found in several marine organisms: zoanthids belonging to the genus Palythoa [2] as well as in the sub-tropical microalga Ostreopsis spp, mainly O. cf. ovata [3] which has recently spread across the Mediterranean and Southern-Atlantic coasts of Europe, and in marine cyanobacterium Trichodesmium spp. [4]. Several cases of inhalatory poisonings and/or skin injuries have been reported in beachgoers concomitantly with massive blooms of O. cf. ovata [5] as well as in aquarium hobbyists from incidental contact with palytoxin-producing Palythoa spp. [1]. Symptom similarities between Ostreopsis- and Palythoa-related poisonings suggest that the etiological agent is the same. From a chemical standpoint, all palytoxin congeners share the same long polyhydroxylated aliphatic chain with the parent compound and differ little in structural details – generally number, position and/or stereochemistry of a few methyl, methylene and/or hydroxyl groups. Interestingly, for this group of toxins a characteristic LC-HRMS and MS/MS behavior has been identified: all of them form a wide variety of multiply charged ions, including protonated ions, adducts with cations, and ions due to multiple subsequent water losses. Furthermore, these molecules share also the same fragmentation behavior: they undergo fragmentation at several sites of their backbone, generating diagnostic multiply charged ions each one accompanied by several water losses. HR LC-MS and MS/MS spectra of palytoxins can be used as fingerprints for their confident identification directly in the crude extracts even at ng/mL levels. Since natural extracts are usually contaminated by a complex mixture of congeners, this approach revealed effective for preliminary structural characterization of unknown minor congeners present at levels too low for NMR studies.

Structural investigation of not-derivatized palytoxins in crude extracts by a new HR LC-MS/MS-based approach

Luciana Tartaglione
;
Carmela Dell’Aversano;Martino Forino;Patrizia Ciminiello
2016

Abstract

Palytoxin (C129H223N3O54) and its analogues (ovatoxins and ostreocins) fall into the same group of marine biotoxins considered highly dangerous for human health through ingestion, skin contact and/or inhalation [1]. They were found in several marine organisms: zoanthids belonging to the genus Palythoa [2] as well as in the sub-tropical microalga Ostreopsis spp, mainly O. cf. ovata [3] which has recently spread across the Mediterranean and Southern-Atlantic coasts of Europe, and in marine cyanobacterium Trichodesmium spp. [4]. Several cases of inhalatory poisonings and/or skin injuries have been reported in beachgoers concomitantly with massive blooms of O. cf. ovata [5] as well as in aquarium hobbyists from incidental contact with palytoxin-producing Palythoa spp. [1]. Symptom similarities between Ostreopsis- and Palythoa-related poisonings suggest that the etiological agent is the same. From a chemical standpoint, all palytoxin congeners share the same long polyhydroxylated aliphatic chain with the parent compound and differ little in structural details – generally number, position and/or stereochemistry of a few methyl, methylene and/or hydroxyl groups. Interestingly, for this group of toxins a characteristic LC-HRMS and MS/MS behavior has been identified: all of them form a wide variety of multiply charged ions, including protonated ions, adducts with cations, and ions due to multiple subsequent water losses. Furthermore, these molecules share also the same fragmentation behavior: they undergo fragmentation at several sites of their backbone, generating diagnostic multiply charged ions each one accompanied by several water losses. HR LC-MS and MS/MS spectra of palytoxins can be used as fingerprints for their confident identification directly in the crude extracts even at ng/mL levels. Since natural extracts are usually contaminated by a complex mixture of congeners, this approach revealed effective for preliminary structural characterization of unknown minor congeners present at levels too low for NMR studies.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11588/737505
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