An outbreak of food poisoning in Canada during autumn 1987 was traced to cultured blue mussels (Mytilus edulis) from the Cardigan Bay region of eastern Prince Edward Island (P.E.I.). The toxin, identified as domoic acid, had not previously been found in any shellfish and this outbreak represents the first known occurrence of human poisoning by this neurotoxin. A plankton bloom at the time of the outbreak consisted almost entirely of the pennate diatom, Nitzschia pungens f. multiseries, and a positive correlation was found between the number of N. pungens cells and the concentration of domoic acid in the plankton. Nitzschia pungens f. multiseries isolated from Cardigan Bay produced domoic acid in culture at levels (1 to 20 pg∙cell−1) comparable with values estimated for N. pungens in the plankton samples. Isolates of several Cardigan Bay phytoplankton, including the closely related species Nitzschia seriata, failed to produce domoic acid. Other Nitzschia spp. and two Amphora coffeaeformis isolates also failed to produce domoic acid. We conclude that N. pungens was the major source of the domoic acid in toxic mussels in eastern P.E.I. The recurrence, in November 1988, of a monospecific bloom of N. pungens and the presence of domoic acid in plankton and mussels reinforced this conclusion.
We examine the use of external standards for quantitative measurement by 1H NMR of solution concentrations of natural products and other low molecular weight, hydrogen-containing compounds and show that precision and accuracy ca. 1% is obtainable with a commercial 11.7 T spectrometer when standards and analytes are contained in separate but identical sealed precision glass NMR tubes. Numerous factors contributing to the intensity of the NMR signals are evaluated. Precise measurements of 360 degrees pulse lengths for each sample provide direct corrections for variations in probe Q-factor that enable samples in different solvents to be compared, provided single-coil excitation and detection is used throughout. Samples need not be prepared in deuterated solvents if the 1H spectra of the solvents are simple enough for peak suppression by presaturation. The approach is particularly suitable for hazardous materials kept in sealed tubes and for the preparation of certified calibration solution reference materials for use with LC-MS and other techniques where deuterated solvents should be avoided.
13C nuclear magnetic resonance spectra of diastereomeric C-24 alkyl sterols have been assigned. Differences in the chemical shifts of side-chain carbons permitted the determination of the absolute configuration at C-24 in several sterols since these chemical shifts are insensitive to structural changes remote from the asymmetric centre. An unknown sterol from Tetraselmissuecica has been identified as (24R)-24-methylcholest-5-en-3β-ol and the configuration assigned from 1H nmr data to the sterol from Phaeodoctylumtricornutum has been confirmed. The utility and potential of this method in characterising new sterols and their biological precursors is discussed.
Two polar lipid-soluble macrocycles 1 and 2, containing a spiro-linked tricyclic ether ring system and an unusual seven-membered spiro-linked cyclic iminium moiety, have been isolated from the digestive glands of mussels (Mytilus edulis) and scallops (Placopecten magellanicus).During chemical investigations of polar bioactive molecules from microalgae and shellfish,' we isolated from the digestive glands of both mussels (Mytilus edulis) and scallops (Placopecten magellanicus), a family of novel macrocycles which we have named spirolides A-D. Here we report the structural elucidation of the two major components, spirolides B and D.Spirolide B 1 and D 2 (Fig. 1) were purified from methanolic extracts of frozen digestive glands of shellfish collected from sites along the eastern shore of Nova Scotia.? High resolution LSIMS determined the molecular formulae for 1 and 2 to be C42H63N07 (MH+ 694.4651, 6 4.5) and C ~~H G ~N O ~
Three additional marine toxins, spirolides A (1), C (3), and 13-desmethyl-C (7), were isolated from contaminated scallops and phytoplankton collections obtained from a Nova Scotian aquaculture site, as well as from batch cultures of the dinoflagellate Alexandrium ostenfeldii obtained as a single-cell isolate from these phytoplankton assemblages. The structures of these new spirolide derivatives, characterized by mass spectrometry and NMR, indicate a close relationship with spirolides B (2) and D (4) isolated previously from contaminated shellfish in the same area. All of these compounds display "fast-acting" toxicity in the traditional bioassay used for monitoring shellfish, and this is related to the presence of a cyclic imine function in all these compounds. Those spirolides containing a vicinal dimethyl group in the seven-membered ring are resistant to oxalic acid hydrolysis, whereas those that do not are readily hydrolyzed. These observations suggest that the extra methyl group on the seven-membered imine ring of 3, 4, and 7 appears to block the process of imine hydrolysis perhaps by stereochemical interference.
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