RESUMEN
Two species of red algae belonging to the genus Plocamium, P. hamatum from Moreton Bay, Queensland, and P. costatum, from Pandalowie Bay, South Australia, were investigated to assess their chemical variation and as potential sources of new halogenated monoterpenes. The hyphenated technique HPLC-UV-MS-SPE-NMR was used to assess the algal extracts and to determine its potential for accelerated identification of halogenated monoterpenes generally. A combination of the hyphenated and traditional chromatographic techniques resulted in the isolation and characterization of a total of 10 halogenated monoterpene metabolites, eight of which are reported for the first time. Their structures, including configurations, were determined through interpretation of their 1D and 2D NMR, mass spectrometric, infrared, and X-ray data. The two species of Plocamium produced different secondary metabolites and contained a significant number of new polyhalogenated monoterpenes. The investigation also showed the hyphenated technique HPLC-UV-MS-SPE-NMR to be useful for preliminary investigation of the chemical content of algal extracts.
Asunto(s)
Hidrocarburos Bromados/aislamiento & purificación , Hidrocarburos Clorados/aislamiento & purificación , Monoterpenos/aislamiento & purificación , Plocamium/química , Australia , Hidrocarburos Bromados/química , Hidrocarburos Clorados/química , Estructura Molecular , Monoterpenos/química , Resonancia Magnética Nuclear Biomolecular , Océanos y MaresRESUMEN
A rigid linear bis-bidentate quaterpyridine undergoes metal directed self-assembly with iron(ii) salts yielding M(4)L(6) host-guest complexes; selective anion binding for PF(6)(-) over BF(4)(-) is observed.
Asunto(s)
Compuestos Ferrosos/química , Aniones , Sitios de Unión , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Difracción de Rayos XRESUMEN
In a recent survey of paralytic shellfish poisoning (PSP) toxins in Gymnodinium catenatum Graham extracts, using LC with postcolumn oxidation and fluorescence detection, three novel saxitoxin analogues were revealed in isolates from several locations, including Australian waters. We have named them as G. catenatum toxins, GC1 (1), GC2 (2), and GC3 (3). The compounds were isolated from a culture of the Australian strain by LC-MS-guided fractionation employing a C18-silica column and hydrophilic interaction chromatography. The unusual structures of these novel compounds were characterized by low- and high-resolution MS, MS/MS, and NMR spectroscopy. GC3 (3) was found to be the 4-hydroxybenzoate ester derivative of decarbamoylsaxitoxin, while GC1 (1) and GC2 (2) are the epimeric 11-hydroxysulfate derivatives of GC3 (3).