42-hydroxypalytoxin and palytoxin

The state of the art of LC-MS of palytoxin and its analogues is reported in the present review. MS data for palytoxin, 42-hydroxy-palytoxin, ostreocin-D, mascarenotoxins, and ovatoxins, obtained using different ionization techniques, namely fast-atom bombardment (FAB), matrix assisted laser desorption ionization (MALDI), and electrospray ionization (ESI), are summarized together with the LC-MS methods used for their detection. Application of the developed LC-MS methods to both plankton and seafood analysis is also reported, paying attention to the extraction procedures used and to limits of detection (LOD) and quantitation (LOQ) achieved. In a research setting, LC-MS has shown a good potential in determination of palytoxin and its analogues from various sources, but, in a regulatory setting, routine LC-MS analysis of palytoxins is still at a preliminary stage. The LOQ currently achieved in seafood analysis appears insufficient to detect palytoxins in shellfish extract at levels close to the tolerance limit for palytoxins (30 μg/kg) proposed by the European Food Safety Authority (EFSA, 2009). In addition, lacking of certified reference standard of palytoxins as well as of validation studies for the proposed LC-MS methods represent important issues that should be faced for future perspectives of LC-MS technique.

Topics: Acrylamides; Bridged Bicyclo Compounds, Heterocyclic; Chromatography, Liquid; Cnidarian Venoms; Food Safety; Limit of Detection; Mass Spectrometry; Molecular Structure; Pyrans; Seafood

Anecdotal reports exist of aquarium hobbyists that experienced severe respiratory distress and/or skin injury following cleaning operation of home aquaria containing Palythoa sp. soft corals. Hundreds of cases of respiratory illness and/or dermatitis have been recorded in proximity to the sea concomitantly with algal blooms of Ostreopsis spp. in the Mediterranean area. Both Palythoa spp. and Ostreopsis spp. contain congeners of palytoxin, a highly potent toxin whose inhalation hazard is however unknown. In this study, we demonstrate the presence of high levels of palytoxins (palytoxin and hydroxypalytoxin) in both soft coral and seawater from a home marine aquarium involved in the poisoning of a whole family. Due to the high toxin levels found in seawater, a procedure for a rapid and efficient determination of palytoxin in seawater was setup. A comparison of symptoms of Palythoa- and Ostreopsis-related inhalatory poisonings showed many similarities including fever, respiratory distress, nausea, and flu-like symptoms. From the chemical and symptomatological data reported herein it is reasonable to hold palytoxins responsible for respiratory disorders following inhalation. Although the exact mechanism through which palytoxin congeners exert their inhalatory toxicity is still unknown, this represents a step toward demonstrating that palytoxin congeners exert toxic effects through inhalation both in natural environments and in the surroundings of private and public aquaria.

Topics: Acrylamides; Administration, Inhalation; Adolescent; Adult; Animals; Anthozoa; Cnidarian Venoms; Dinoflagellida; Environmental Exposure; Humans; Pyrans; Seawater; Solid Phase Extraction

Palytoxin ranks among the most potent marine biotoxins. Its lethality was well known to native Hawaiians that used to smear a "moss" containing the toxin on their spears to cause instant death to their victims. Human intoxications due to exposure to palytoxin and to its many congeners have been reported worldwide. Currently, palytoxins constitute the main threat to public health across the Mediterranean Sea. In the present work we report on the isolation and stereostructural determination of a new palytoxin analogue from a Hawaiian Palythoa tuberculosa sample. This new toxin is a stereoisomer of 42-hydroxypalytoxin isolated from Palythoa toxica. The whole absolute configuration of this latter toxin is also reported in the paper. Interestingly, the two 42-hydroxypalytoxins do not share the same biological activity. The stereoisomer from P. tuberculosa showed cytotoxicity toward skin HaCaT keratinocytes approximately 1 order of magnitude lower than that of 42-hydroxypalytoxin from P. toxica and about 2 orders of magnitude lower than that of palytoxin itself. This finding holds the prospect of interesting structure-activity relationship evaluations in the future.

Topics: Acrylamides; Animals; Anthozoa; Chromatography, High Pressure Liquid; Cnidarian Venoms; Hawaii; Humans; Keratinocytes; Marine Toxins; Mediterranean Sea; Molecular Structure; Nuclear Magnetic Resonance, Biomolecular; Pyrans; Stereoisomerism; Structure-Activity Relationship

Marine pelagic diazotrophic cyanobacteria of the genus Trichodesmium (Oscillatoriales) are widespread throughout the tropics and subtropics, and are particularly common in the waters of New Caledonia. Blooms of Trichodesmium are suspected to be a potential source of toxins in the ciguatera food chain and were previously reported to contain several types of paralyzing toxins. The toxicity of water-soluble extracts of Trichodesmium spp. were analyzed by mouse bioassay and Neuroblastoma assay and their toxic compounds characterized using liquid chromatography coupled with tandem mass spectrometry techniques. Here, we report the first identification of palytoxin and one of its derivatives, 42-hydroxy-palytoxin, in field samples of Trichodesmium collected in the New Caledonian lagoon. The possible role played by Trichodesmium blooms in the development of clupeotoxism, this human intoxication following the ingestion of plankton-eating fish and classically associated with Ostreopsis blooms, is also discussed.

Topics: Acrylamides; Animals; Biological Assay; Cell Line, Tumor; Chromatography, Liquid; Cnidarian Venoms; Cyanobacteria; Female; Humans; Male; Mice; Neuroblastoma; Pyrans; Tandem Mass Spectrometry; Toxicity Tests

This paper reports on the analysis of the toxin content from Palythoa tuberculosa and Palythoa toxica samples collected off of the Hawaiian coast. Our work, based on in-depth high-resolution liquid chromatography-mass spectrometry analysis along with extensive NMR study, led us to structurally characterize 42-hydroxy-palytoxin, a new palytoxin congener. This toxin and palytoxin itself appeared to be the major components of toxic extract from a P. tuberculosa sample, while 42-hydroxy-palytoxin was proven by far to be the main palytoxin derivative in P. toxica. Functional studies on this new palytoxin-like compound suggest that the new palytoxin analogue and palytoxin itself present similar biological activities.

Topics: Acrylamides; Animals; Anthozoa; Cells, Cultured; Chromatography, High Pressure Liquid; Cnidarian Venoms; Hawaii; Magnetic Resonance Spectroscopy; Mice; Pyrans; Spectrometry, Mass, Electrospray Ionization; Stereoisomerism