Ciguatoxins (CTX)
are potent marine neurotoxins, which can bioaccumulate
in seafood, causing a severe and prevalent human illness known as
ciguatera poisoning (CP). Despite the worldwide impact of ciguatera,
effective disease management is hindered by a lack of knowledge regarding
the movement and biotransformation of CTX congeners in marine food
webs, particularly in the Caribbean and Western Atlantic. In this
study we investigated the hepatic biotransformation of C-CTX across
several fish and mammalian species through a series of in vitro metabolism
assays focused on phase I (CYP P450; functionalization) and phase
II (UGT; conjugation) reactions. Using liquid chromatography high-resolution
mass spectrometry to explore potential C-CTX metabolites, we observed
two glucuronide products of C-CTX-1/-2 and provided additional evidence
from high-resolution tandem mass spectrometry to support their identification.
Chemical reduction experiments confirmed that the metabolites were
comprised of four distinct glucuronide products with the sugar attached
at two separate sites on C-CTX-1/-2 and excluded the C-56 hydroxyl
group as the conjugation site. Glucuronidation is a novel biotransformation
pathway not yet reported for CTX or other related polyether phycotoxins,
yet its occurrence across all fish species tested suggests that it
could be a prevalent and important detoxification mechanism in marine
organisms. The absence of glucuronidation observed in this study for
both rat and human microsomes suggests that alternate biotransformation
pathways may be dominant in higher vertebrates.
Dimethylsulfoniopropionate (DMSP) is produced by many species of marine phytoplankton and has been reported to provide a variety of beneficial functions including osmoregulation. Dinoflagellates are recognized as major DMSP producers; however, accumulation has been shown to be highly variable in this group. We explored the effect of hyposaline transfer in Gambierdiscus belizeanus between ecologically relevant salinities (36 and 31) on DMSP accumulation, Chl a, cell growth, and cell volume, over 12 d. Our results showed that G. belizeanus maintained an intracellular DMSP content of 16.3 pmol cell−1 and concentration of 139 mM in both salinities. Although this intracellular concentration was near the median reported for other dinoflagellates, the cellular content achieved by G. belizeanus was the highest reported of any dinoflagellate thus far, owing mainly to its large size. DMSP levels were not significantly affected by salinity treatment but did change over time during the experiment. Salinity, however, did have a significant effect on the ratio of DMSP:Chl a, suggesting that salinity transfer of G. belizeanus induced a physiological response other than DMSP adjustment. A survey of DMSP content in a variety of Gambierdiscus species and strains revealed relatively high DMSP concentrations (1.0–16.4 pmol cell−1) as well as high intrageneric and intraspecific variation. We conclude that, although DMSP may not be involved in long‐term (3–12 d) osmoregulation in this species, G. belizeanus and other Gambierdiscus species may be important contributors to DMSP production in tropical benthic microalgal communities due to their large size and high cellular content.
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