Mycosporine-Like Amino Acids: Relevant Secondary Metabolites. Chemical and Ecological Aspects

Taxonomically diverse marine, freshwater and terrestrial organisms have evolved the capacity to synthesize, accumulate and metabolize a variety of UV-absorbing substances called mycosporine-like amino acids (MAAs) as part of an overall strategy to diminish the direct and indirect damaging effects of environmental ultraviolet radiation (UVR). Whereas the enzymatic machinery to synthesize MAAs was probably inherited from cyanobacteria ancestors via the endosymbionts hypothesis, metazoans lack this biochemical pathway, but can acquire and metabolize these compounds by trophic transference, symbiotic or bacterial association. In this review we describe the structure and physicochemical properties of MAAs, including the recently discovered compounds and the modern methods used for their isolation and identification, updating previous reviews. On this basis, we review the metabolism and distribution of this unique class of metabolites among marine organism

Palythine-threonine, a major novel mycosporine-like amino acid (MAA) isolated from the hermatypic coral Pocillopora capitata

Using a high-resolution reverse-phase liquid chromatography method we found that the tissues of the hermatypic coral Pocillopora capitato (collected in Santiago Bay, Mexico) contain a high diversity of primary and secondary mycosporine-like amino acids (MAAs) typical of some reef-building coral species: mycosporine-glycine, shinorine, porphyra-334, mycosporine-methylamine-serine, mycosporine-methylamine-threonine, palythine-serine, palythine and one additional novel predominant MAA, with an absorbance maximum of 320 nm. Here we document the isolation and characterization of this novel MAA from the coral A capitata. Using low multi-stage mass analyses of deuterated and non deuterated compounds, high-resolution mass analyses (Time of Flight, TOF) and other techniques, this novel compound was characterized as palythine-threonine. Palythine-threonine was also present in high concentrations in the corals Pocillopora eydouxi and Stylophora pistillata indicating a wider distribution of this MAA among reef-building corals. From structural considerations we suggest that palythine-threonine is formed by decarboxylation of porphyra-334 followed by demethylation of mycosporine-methylamine-threonine. (C) 2008 Elsevier B.V. All rights reserved.CNPq-Instituto do Milenio and Fapesp from BrazilCNPq-Instituto do MilenioFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CONICET from ArgentinaCONICET from Argentina[PIP 5009]INIDEP[1535]INIDE

Toxic strains of the Alexandrium ostenfeldii complex in southern South America (Beagle Channel, Argentina)

During phytoplankton monitoring in the Beagle Channel (≈54°52′ S, 67°32′ W) a previously undetected Alexandrium species was observed in coincidence with mouse bioassay toxicity. Detailed thecal plates analysis using epifluorescence and scanning electron microscopy revealed the presence of the Alexandrium ostenfeldii species complex, showing a mixture of the diagnostic features usually used to discriminate between the morphospecies A. ostenfeldii and A. peruvianum. Cells of the A. ostenfeldii complex were commonly observed during spring after the main annual diatom bloom, when temperatures and salinities were respectively around 7.5–10 °C and 30–30.5 psu, and nutrients showed a seasonal decrease. Toxin analysis by liquid chromatography–mass spectrometry revealed the production of 13-desmethyl spirolide C and 20-methyl spirolide G in cell cultures. The cellular contain of spirolides during exponential phase growth was 0.5906 ± 0.0032 and 0.1577 ± 0.0023 pg cell−1 for 13-desMe-C and 20-Me-G, respectively. A third unknown compound, with a structure resembling that of spirolides was also detected in culture. Moreover, an additional compound with a similar m/z (692) than that of 13-desMe-C but presenting a higher retention time (Rt = 40.5 min) was found in high proportions in mussel samples. PSP toxins were present at low concentration in mussels but were not detected in cultures. These results extend the world-wide distribution of toxic strains of the A. ostenfeldii complex to the Beagle Channel (southern South America), where toxic events have been traditionally linked to the presence of Alexandrium catenella. This is the first confirmed occurrence of spirolides in mussels and plankton from Argentina, which highlights the importance of monitoring these toxins and their producing organisms to protect public health and improve the management of shellfish resources.Fil: Almandoz, Gaston Osvaldo. Universidad Nacional de la Plata. Facultad de Ciencias Naturales y Museo. Division Ficología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Montoya, Nora Gladys. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Hernando, Marcelo Pablo. Comisión Nacional de Energía Atómica; ArgentinaFil: Benavides, Hugo R.. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Carignan, Mario O.. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Ferrario, Martha Elba. Universidad Nacional de la Plata. Facultad de Ciencias Naturales y Museo. Division Ficología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Environmental and biological factors controlling the spring phytoplankton bloom at the Patagonian shelf-break front - Degraded fucoxanthin pigments and the importance of microzooplankton grazing

The aim of this study was to investigate the biotic and abiotic factors controlling the spring phytoplankton blooms at the Patagonian shelf-break front (PSBF). Using a CHEMTAX analysis of HPLC pigment data and other methods, the biomass and spatial variability of plankton communities were studied in four sections (39-48°S) across the PSBF during October 2005. Environmental factors and the biomass and composition of plankton communities exhibited a marked spatial heterogeneity. The latitudinal and cross-shelf progression in the timing of the spring bloom initiation and the nutritive properties of the water masses (Subantarctic Shelf Waters and Malvinas Current Waters) seemed to be the key factors. Three plankton regions were distinguished: (a) Outer shelf (OS), (b) Shelf-break front (SBF) and (c) Malvinas Current (MC). At the highly stratified OS region, the post-bloom community showed low-biomasshigh-phytoplankton diversity formed mainly by small cells (haptophytes 30-62%, diatoms 17-49%, chlorophytes 0-34%, and prasinophytes 0-21% of total Chl a). High amounts of degraded fucoxanthin were found associated with the heterotrophic dinoflagellate, Protoperidinium capurroi. Grazing by this microheterotroph on the diatom population seemed to be the most important factor for the spring bloom decay at the OS. A remarkable quasi monospecific bloom (~90%) of a nanodiatom (Thalassiosira bioculata var. raripora) associated with high Chl a (up to 20 mg m-3) occurred along (~1000 km) the SBF and in the most northern extension of the MC. In the southern region, the bloom was developed under absent or incipient density stratification, increasing solar irradiance, high nitrate and phosphate availability, and low numbers of phytoplankton grazers. The average mixedlayer PAR irradiance (<2.0 mol quanta PAR m-2 d-1) and Si:N ratios (<0.2) were low, suggesting a diatom population limited by light and under progressive silicate limitation. The more stratified northern region of the SBF showed a later stage of the bloom development, but the large population of diatoms under Si limitation was not in senescence and losses from microzooplankton grazing were minor. The observed high proportion of Chl a below a shallow upper mixed layer (up to 85%) could directly reach the bed, favoring the development of epibenthic communities and the formation of seed diatom banks and organic iron-rich sediments. The upwelling along the SBF provides a large source of macronutrients and probably the dissolved iron needed to sustain the intense diatom bloom, but also diatom resting stages that could act as seeds for the next spring bloom. The macronutrient-rich MC region showed low chlorophyll (Chl a < 0.8 mg m-3) and a highly diverse phytoplankton community, mainly composed of small cells (diatoms 20-70%, haptophytes 20-40%, chlorophytes 2-25%, prasinophytes 2-18%, and cryptophytes 3-12% of total Chl a).Fil: Carreto Iraurgui, Jose Ignacio. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Montoya, Nora Gladys. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Carignan, Mario O.. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Akselman Cardella, Rut. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Acha, Eduardo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; Argentina. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Derisio, Carla María. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Instituto Nacional de Investigaciones y Desarrollo Pesquero; Argentin

Analyses of photoprotective compounds in red algae from the Brazilian coast

Qualitative and quantitative studies of mycosporine-like amino acids (MAAs) in three species of the genus Gracilaria Greville (G. birdiae, G. domingensis and G. tenuistipitata) were performed. A simple and efficient extraction procedure based on ethanol was described. HPLC, UV and mass spectrometry experiments revealed different profiles between extracts obtained from one species cultivated in the laboratory (G. tenuistipitata) and two species collected in their natural environment (G. birdiae and G. domingensis). The levels detected in the latter two species were approximately 150 times higher than in the species cultivated in vitro. This study revealed that G. birdiae and G. domingensis present a potential source for economical exploration of MAAs

Photochemistry and Photophysics of Shinorine Dimethyl Ester

The photostability and photophysical properties of the dimethyl ester of the mycosporine-like amino acid shinorine have been experimentally evaluated in aqueous solution and in the presence of direct micelles prepared with a cationic or an anionic detergent, respectively. In comparison with shinorine, the ester molecule increases the photostability, the fluorescence quantum yield and the fluorescence lifetime in water as well as in the micellar solutions. The effects are more pronounced in sodium dodecyl sulfate solutions and suggest that the electrostatic attractions with the micellar interface contribute to limit the movement of the molecules and influence the relative rate of their deactivation channels. However, the predominance of the nonradiative decay is maintained together with the UV photoprotective ability of this atypical mycosporine species.Fil: Orallo, Dalila Elisabet. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Fangio, Maria Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata; ArgentinaFil: Poblet, Martín. Universidad Nacional de Mar del Plata; ArgentinaFil: Carignan, Mario O.. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Bernal, Luis. Universidad Nacional de Mar del Plata; ArgentinaFil: Carreto Iraurgui, Jose Ignacio. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto; ArgentinaFil: Churio, Maria Sandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata; Argentin

Physical and biological effects on the carbonate system during summer in the Northern Argentine Continental Shelf (Southwestern Atlantic)

The Argentine shelf and its shelf-break (Southwestern Atlantic Ocean) are known for their high biological productivity, and as an important CO2 sink region. However, many aspects of the carbonate system dynamics in the area, especially those related to the biological activity, deserve further study. Here we investigated the mechanisms affecting the carbonate system distributions, using in situ physical, chemical and biological observations collected along a section (COSTAL-AR) on the Northern Argentine Continental Shelf during two summer cruises in 2019. Our main goal was to evaluate the role of the microbial communities on the modulation of the carbonate system in the area. For that, we characterized (i) the distribution of the thermohaline properties, chlorophyll a, dissolved oxygen, carbonate system (pH, total alkalinity, dissolved inorganic carbon and high resolution underway CO2 fugacity, fCO2), dissolved inorganic nutrients, and (ii) the microbial communities (bacterioplankton, phytoplankton, and protozooplankton). Our results show that the COSTAL-AR section was likely an important CO2 sink and presented high seawater fCO2 spatial variability in both middle (272–430 μatm) and early (211–365 μatm) summer conditions. Phytoplankton played a key role in modulating the CO2 uptake and carbonate system spatial variability during summer, especially in the middle and outer shelf. The main contribution to CO2 fixation was given by small cells, since the microbial community was dominated by autotrophic picoplankton (<2 μm; e.g. Synechococcus sp. and coccal picophytoeukaryotes). Moreover, the influence of the Shelf-break front in ruling both the seawater fCO2 distribution and biological processes was evident. These findings provide new insights on the connection between the biology and the carbonate system in this sparsely sampled area of the Southwestern Atlantic Ocean.•Biogeochemical mechanisms affecting the carbonate system of the Argentine shelf were analyzed.•The study region was likely an important CO2 sink during summer.•The CO2 dynamics of the Argentine Shelf were affected by biological mechansms during summer.•Small phytoplankton (<2–3 μm) played a key role in modulating the CO2 uptake

Harmful phytoplankton in the Beagle Channel (South America) as a potential threat to aquaculture activities

The Beagle Channel is a remote subantarctic environment where mussel aquaculture initiatives have existedsince the early 1990s. Here we analyze phytoplankton biomass and composition, and the occurrence of harmfulmicroalgae species and their toxins at three sites during the period 2015?2016. The occurrence of potentiallyharmful algae was observed throughout the study period, including toxigenic dinoflagellates such asAlexandrium catenella (Group I of the A. tamarense complex), A. ostenfeldii, Dinophysis acuminata, Gonyaulaxspinifera, Azadinium sp., and the diatoms Pseudo-nitzschia australis and P. fraudulenta. Toxic dinoflagellates weredetected in low densities whereas a Pseudo-nitzschia bloom was observed in late February. Isolates of A. catenellaand P. delicatissima sensu stricto were phylogenetically characterized. The toxin profile of A. catenella wasdominated by GTX4, while P. delicatissima sensu stricto showed no production of the neurotoxin domoic acid inculture conditions. The results provide base-line information for the management of harmful algal blooms in thislittle explored subantarctic area.Fil: Almandoz, Gaston Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Ficología; ArgentinaFil: Cefarelli, Adrián Oscar. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro de Investigaciones y Transferencia Golfo San Jorge. Centro de Investigaciones y Transferencia Golfo San Jorge: Sede Caleta Olivia - Santa Cruz | Universidad Nacional de la Patagonia Austral. Centro de Investigaciones y Transferencia Golfo San Jorge. Centro de Investigaciones y Transferencia Golfo San Jorge: Sede Caleta Olivia - Santa Cruz | Universidad Nacional de la Patagonia "san Juan Bosco". Centro de Investigaciones y Transferencia Golfo San Jorge. Centro de Investigaciones y Transferencia Golfo San Jorge: Sede Caleta Olivia - Santa Cruz; Argentina. Universidad Nacional de la Patagonia "San Juan Bosco". Instituto de Desarrollo Costero; ArgentinaFil: Diodato, Soledad Lorena. Universidad Nacional de Tierra del Fuego, Antártida e Islas del Atlántico Sur. Instituto de Ciencias Polares, Ambientales y Recursos Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Austral de Investigaciones Científicas; ArgentinaFil: Montoya, Nora Gladys. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Benavides, Hugo R.. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Carignan, Mario Osvaldo. Instituto Nacional de Investigaciones y Desarrollo Pesquero; ArgentinaFil: Hernando, Marcelo Pablo. Comisión Nacional de Energía Atómica; ArgentinaFil: Fabro Cerreia Fus, Elena Ines. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Ficología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Metfies, Katja. Alfred-Wegener-Institut, Helmholtz-Zentrum für Polar- und Meeresforschung; AlemaniaFil: Lundholm, Nina. Universidad de Copenhagen; DinamarcaFil: Schloss, Irene Ruth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Austral de Investigaciones Científicas; Argentina. Universidad Nacional de Tierra del Fuego; Argentina. Ministerio de Relaciones Exteriores, Comercio Interno y Culto. Dirección Nacional del Antártico. Instituto Antártico Argentino; ArgentinaFil: Álvarez, Marcela. Instituto Nacional de Investigaciones y Desarrollo Pesquero. Dirección de Pesquerías Demersales. Programa Pesquerías de Peces Demersales Costeros; ArgentinaFil: Ferrario, Martha Elba. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Ficología; Argentin