A theoretical and mass spectrometry study of the fragmentation of mycosporine-like amino acids

In the present study, the mycosporine-like amino acids (MAAs) were isolated from the marine red alga Gracilaria tenuistipitata and analysed by high-resolution accurate-mass sequential mass spectrometry (MSn). In addition to the proposed fragmentation mechanism based on the MSn analysis, it is clearly demonstrated that the elimination of mass 15 is a radical processes taking place at the methoxyl substituent of the double bond. This characteristic loss of a methyl radical was studied by theoretical calculations and the homolytic cleavage of the O-C bond is suggested to be dependent on the bond weakening. The protonation site of the MAAs was indicated by analysis of the Fukui functions and the relative Gibbs energies of the several possible protonated forms. (C) 2008 Elsevier B.V. All rights reserved.

Cytotoxic and genotoxic effects of tambjamine D, an alkaloid isolated from the nudibranch Tambja eliora, on Chinese hamster lung fibroblasts

Marine organisms have been shown to be potential sources of bioactive compounds with pharmaceutical applications. Previous chemical investigation of the nudibranch Tambja eliora led to the isolation of the alkaloid tambjamine D. Tambjamines have been isolated from marine sources and belong to the family of 4-methoxypyrrolic-derived natural products, which display promising immunosuppressive and cytotoxic properties. Their ability to intercalate DNA and their pro-oxidant activity may be related to some of the biological effects of the 4-methoxypyrrolic alkaloids. The aim of the present investigation was to determine the cytotoxic, pro-oxidant and genotoxic properties of tambjamine D in V79 Chinese hamster lung fibroblast cells. Tambjamine D displayed a potent cytotoxic effect in V79 cells (IC50 1.2 mu g/mL) evaluated by the MTT assay. Based on the MTT result, V79 cells were treated with different concentrations of tambjamine D (0.6. 1.2. 2.4 and 4.8 mu g/mL). After 24 h, tambjamine D reduced the number of viable cells in a concentration-dependent way at all concentrations tested. assessed by the trypan blue dye exclusion test. The hemolytic assay showed that the cytotoxic activity of tambjamine D was not related to membrane disruption (EC50 > 100 mu g/mL). Tambjamine D increased the number of apoptotic cells in a concentration-dependent manner at all concentrations tested according to acridine orange/ethidium bromide staining, showing that the alkaloid cytotoxic effect was related to the induction of apoptosis. MTT reduction was stimulated by tambjamine D, which may indicate the generation of reactive oxygen species. Accordingly, treatment of cells with tambjamine D increased nitrite/nitrate at all concentrations and TBARS production starting at the concentration corresponding to the IC50. Tambjamine D, also, induced DNA strand breaks and increased the micronucleus cell frequency as evaluated by comet and micronucleus tests, respectively, at all concentrations evaluated. showing a genotoxic risk induced by tambjamine D. (C) 2008 Elsevier Ireland Ltd. All rights reserved.

Potencial terapêutico de um heparinóide isolado do invertebrado marinho Litopenaeus vannamei

The occurrence of bioactive compounds in marine organisms comes awaking the interest of the pharmaceutical industry. Heparin, a sulfated polysaccharide which presence was already identified in several marine invertebrates, is very attractive due its remarkable functional versatility. Besides to intervene in blood coagulation, this molecule has a great anti-inflammatory potential. However, its strong anticoagulant activity difficult the clinical exploitation of its anti-inflammatory properties. Thus, the aims of this work were to evaluate the effect of a heparin-like compound (heparinoid), isolated from the cephalotorax of the Litopenaeus vannamei shrimp, on the inflammatory response, hemostasia and synthesis of antithrombotic heparan sulfate by endothelial cells, besides studying some aspects concerning its structure. The purified heparinoid was structurally characterized following an analytical boarding, involving electrophoresis and chromatography. The structural analysis have shown that this compound possess a high content of glucuronic acid residues and disulfated disaccharide units. In contrast to mammalian heparin, the heparinoid was incapable to stimulate the synthesis of heparan sulfate by endothelial cells in the tested concentrations, beyond to show reduced anticoagulant activity and hemorrhagic effect. In a model of acute inflammation, the compound isolated from the shrimp reduced more than 50% of the cellular infiltration. Besides reduce the activity of MMP-9 and proMMP-2 of the peritoneal lavage of inflamed animals, the heparinoid also reduced the activity of MMP-9 secreted by activated human leukocytes. These results demonstrate the potential of heparinoid from L. vannamei to intervene in the inflammatory response. For possessing reduced anticoagulant activity and hemorrhagic effect, this compound can serve as a structural model to direct the development of more specific therapeutical agents to the treatment of inflammatory diseases

Bioprospecção química da esponja callyspongia vaginalis (Callyspongiidae)

Recently, marine organisms have attracted attention because of the complexity and potent biological activity from your secondary metabolites. Our planet has 80% it surface covered by oceans and seas, therefore, housing a wide number of different forms of life, among them, the sponges. These sessile and filtrating animals, according to numerous researches, come showing like true chemistry factories. The substances from these animals, sometimes show as news targets to therapeutics agents, and some countries has already use them for treatment of some diseases. Further of the secondary metabolites, the polysaccharides of marine origin also have been target of studies, because the presence of the sulfates groups in its molecules. Polysaccharides with differents biological activities have been related in a large number of researches. Actually, many studies show the sponges as source of promising medicine. These studies inspire new researches, because the few number of sponges species studied until now. Because of that, the present work shows the chemistry prospection of the sponge Callyspongia vaginalis. Chromatographic methods in silica gel allowed the isolations of two secondary metabolites: the known β- sitosterol and a ceramide, no reported in the genus Callyspongia, previously. The analysis of the their lipid extracts show different kinds of fatty acids with a variety of chain length (saponifiable fraction), and others metabolites like Lupenone and stigmasterol, also unprecedented in the genus. The Polysaccharide characterization and the elucidation of the secondary metabolites acquired through of chromatography analysis (CC, molecular exclusion) and spectrometric (NMR 1H and 13C, mass, IR), respectively and comparison with literature data

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Tropical biodiversity: has it been a potential source of secondary metabolites useful for medicinal chemistry?

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação dos efeitos dos polissacarídeos sulfatados de macroalgas marinhas sobre a Fosfolipase A2 de Crotalus durissus terrificus

Pós-graduação em Biologia Geral e Aplicada - IBB

Potencial anti-inflamatório de Pyrenocine A isolada do Penicillium paxilli: abordagem profilática e terapêutica

Pós-graduação em Biociências e Biotecnologia Aplicadas à Farmácia - FCFAR

Variação espaço-temporal do microfitoplâncton na região da foz do rio Guamá (estuário amazônico), Belém, PA

O sistema hidrográfico de Belém é constituído por dois grandes corpos hídricos: a baía do Guajará e o rio Guamá, cujo divisor de águas é quase imperceptível. A importância do rio Guamá para a cidade de Belém deve-se ao fato de que esse juntamente com os lagos Água Preta e Bolonha, faz parte do Complexo Hídrico do Utinga, manancial que abastece a cidade. O estudo visou caracterizar a variação espaço-temporal da comunidade microfitoplanctônica nessa região, durante um ciclo anual, em período de maior e menor precipitação pluviométrica, em cinco estações de coleta. As amostras qualitativas foram coletadas com rede de plâncton de 20 μm. Para o estudo quantitativo, foram coletadas diretamente na sub-superfície da água com frascos de polietileno de 250 ml. O material biológico foi fixado com solução Transeau. Simultaneamente, foram registrados os parâmetros abióticos na superfície da água. Os fatores hidrológicos não apresentaram variações relevantes entre as estações e os períodos sazonais. Foram identificadas 173 espécies, destacando-se as diatomáceas como grupo de maior densidade e que caracteriza o ambiente. Não foram observadas espécies dominantes durante o período estudado. Através da abundância relativa, constatou-se que a maioria dos organismos foi considerada rara. A diversidade específica variou de muito baixa a alta, sendo observados baixos índices de diversidade no período menos chuvoso, destacando-se a ocorrência das espécies Aulacoseira granulata (Ehrenb.) Ralfs, Actinoptychus sp. e Cyclotella sp. Já a densidade fitoplanctônica apresentou variação temporal definida, sendo registrados os maiores florescimentos durante o período mais chuvoso. Quanto à variação espacial, não houve um padrão em relação aos períodos sazonais. As euglenofíceas foram pouco freqüentes ou esporádicas e se restringiram ao período menos chuvoso, já os dinoflagelados estiveram presentes nos dois períodos, embora considerados organismos marinhos, foram registradas duas espécies do gênero Peridinium. A comunidade fitoplanctônica não apresentou diferenças significativas entre as estações de coleta, provavelmente devido à hidrodinâmica e à forte drenagem fluvial do rio Guamá.

Eventos biológicos da Formação Pirabas (Mioceno Inferior)

Este trabalho trata sobre a identificação dos eventos biológicos globais, regionais e locais da Formação Pirabas, sob a luz dos modernos conceitos de análise e evolução geobiológica de bacias sedimentares, integrando os processos geológicos crustais do Neógeno com as respostas adaptativas e filogenéticas das biotas marinhas. Foram caracterizados bioeventos globais de inovação e radiação entre os moluscos e sirênios e,bioeventos regionais de radiação e dispersão biogeográfica de biválvios, gastrópodes, crustáceos decápodes, equinóides, corais escleractíneos, briozoários, ostracodes e foraminíferos, assim como de extinção da espécie Orthaulax pugnax. Também foram reconhecidos bioeventos locais de expansão biogeográfica da flórula, de uma comunidade estenobiôntica, bem como variações ecofenotípicas nas espécies também registradas nas demais áreas da Província Biogeográfica Caribeana.

Mithracinae (Decapoda: Brachyura) from the Brazilian coast: review of the geographical distribution and comments on the biogeography of the group

The geographical distribution of marine organisms, as a result of complex natural processes through geological time, has been changed, sometimes drastically, by species introductions. Instances of species introduction have been recorded worldwide, and the Brazilian coast is no exception. The present review provides an update of the geographical distribution of members of the brachyuran subfamily Mithracinae along the Brazilian coast. Of the 30 species of this subfamily recorded from Brazilian waters, the known geographical limits of more than 17 have been extended in recent decades. The records compiled here demonstrate the great importance of the Amazon River outflow on the geographical distribution of members of Mithracinae, acting as a biogeographical barrier for some species.

Estudos metabolômicos entre interações da rizosfera de Senna spectabilis e rizobacterias associadas

Pós-graduação em Química - IQ

Environmental factors modulating the abundance and distribution of Callinectes danae (Decapoda: Portunidae) from two areas of the southeastern coast of Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A cunha do ciclo de fácies do Grupo Guatá (Eopermiano) na margem sub-aflorante do norte paranaense

A wedge facies cycle it‟s a body of sedimentary rock, bounded above and below by unconformity and which represents a transgressive-regressive cycle of deposition. This cycle is formed by the following succession of facies: non-marine (N), transitional-coarse texture, and marine-fine texture; The objective of this study have been members of the sandstones and Triumph Siderópolis, seconded by rare calcareous sandstones and very thin limb Paraguaçu. Through analysis of facies in wells testified by CPRM, it was possible to group on facies successions and set the standard stacking. The Triunfo Member consists of three cycles of facies, lithology whose standard indicates a vertical arrangement ''type'' tuning up, other words, a component sandy bottom in the form of '' box'', followed by components sandy-clayey and clayey-carbonaceous (1st and 2nd cycle) and / or shale and limestone (3rd cycle), represented by the base member Paraguaçu. The first cycle only occurs on NF-5 wells and NF-6 in the form of Onlap channel dug in post-Itararé group. The cycle II also reaches wells NF-4 and NF-3 to the north, while the cycle III reaches the southern area, well NF-9. The member Paraguaçu, well PP-25 is predominantly clay-síltico, also stand out limestones and sandstones. The limestones are not coastal marine organisms probably connected with the algae and cyanobacteria, the sandstones are fine-textured, very thin and coastal deposition environment. The member Siderópolis, well NF-2 consists of a sandstone fluvial-estuarine deployed in the valley section, and succeeded by sandstones and siltstones bioturbed, they have linked the transgression of the Fm. Palermo