Hyphenated LC-ICP-MS/ESI-MS Identification of Halogenated Metabolites in South African Marine Ascidian Extracts

Extracts of 13 species of marine ascidian collected in Algoa Bay were analyzed by LC-ICP-MS/ESI-MS. This technique allows parallel analysis of the molecular species and the presence of certain elements. The LC-ICP-MS/ESI-MS technique was used to target iodinated metabolites in this study. Three ascidian species afforded the known 3,5-diiodo-4-methoxyphenethylamine (12), which was confirmed by the isolation of this metabolite from Aplidium monile. MS also suggested the presence of the known 3,5-datromo-4-methoxyphenethylamine (10) and the new 3-bromo-5-iodo-4-methoxyphenethylamine (11) in the A. monile extract. The presence of the known 3,5-dibromotetramethyltyrosine (21) and the new 3-iodotetramethyltyrosine (23) in extracts of an unidentified Didemnum species was similarly proposed from MS evidence. This is the first report of the occurrence of iodinated metabolites in South African marine invertebrates.