Exploration of steroselective cleavage of 4, 5-epoycholestane-3, 6-diols and stero controlled epoxidation of cholest-4-en-3 β, 6β-diol-6-acetate

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Estudio químico y evaluación de la actividad antifouling del octocoral caribeño Eunicea laciniata

The bioassay guided purification of the octocoral Eunicea laciniata organic extract, collected at Santa Marta bay, Colombia, allowed the isolation of the new compound (-)-3β-pregna-5,20-dienyl-β-D-arabinopyranoside (1), along with the known compounds 1(S*),11(R*)-dolabell-3(E),7(E),12(18)-triene (2), 13-keto-1(S),11(R)-dolabell-3(E ),7(E),12(18)-triene (3), cholest- 5,22-dien-3β-ol (4), cholesterol (5), y brassicasterol (6). The structure and absolute configuration of 1 was determined on based spectroscopic analyses (NMR and CD). The extract showed antifouling activity against five strains of marine bacteria associated to heavy fouled surfaces. Also showed activity against the cypris of the cosmopolitan barnacle Balanus amphitrite, and low toxicity in Artemia salina test.

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Monomolecular films of cholesterol oxidase and S-Layer proteins

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Compilation of scientific results of the OASIS project

Seamounts are of great interest to science, industry and conservation because of their potential role as 'stirring rods' of the oceans, their enhanced productivity, their high local biodiversity, and the growing exploitation of their natural resources. This is accompanied by rising concern about the threats to seamount ecosystems, e.g. through over-fishing and the impact of trawling. OASIS described the functioning characteristics of seamount ecosystems. OASIS' integrated hydrographic, biogeochemical and biological information. Based on two case studies. The scientific results, condensed in conceptual and mass balanced ecosystem models, were applied to outline a model management plan as well as site-specific management plans for the seamounts investigated. OASIS addressed five main objectives: Objective 1: To identify and describe the physical forcing mechanisms effecting seamount systems Objective 2: To assess the origin, quality and dynamics of particulate organic material within the water column and surface sediment at seamounts. Objective 3: To describe aspects of the biodiversity and the ecology of seamount biota, to assess their dynamics and the maintenance of their production. Objective 4: Modelling the trophic ecology of seamount ecosystems. Objective 5: Application of scientific knowledge to practical conservation.

Organic geochemistry of sediment cores from the Arbian Sea

Two deep-sea sediment cores from the northeastern and the southeastern Arabian Sea were studied in order to reconstruct the palaeoenvironments of the past glacial cycles. Core 136KL was recovered from the high-productivity area off Pakistan within the modern oxygen-minimum zone (OMZ). By contrast, modern primary productivity at the site of MD900963 close to Maldives is moderate and bottom waters are today well oxygenated. For both cores, we reconstructed the changes in palaeoproductivity using a set of biomarkers (alkenones, dinosterol and brassicasterol); the main result is that primary productivity is enhanced during glacial stages and lowered during interstadials. The proxies associated with productivity show a 23 kyr cyclicity corresponding to the precession-related insolation cycle. Palaeoredox conditions were studied in both cores using a new organic geochemical parameter (C35/C31-n-alkane ratio) developed by analysing surface sediments from a transect across the OMZ off Pakistan. The value of this ratio in core 136KL shows many variations during the last 65 kyr, indicating that the OMZ was not stable during this time: it disappeared completely during Heinrich- and the Younger Dryas events, pointing to a connection between global oceanic circulation and the stability of the OMZ. The C35/C31 ratio determined in sediments of core MD900963 shows that bottom waters remained rather well oxygenated over the last 330 kyr, which is confirmed by comparison with authigenic metal concentrations in the same sediments. A zonally averaged, circulation-biogeochemical ocean model was used to explore how the intermediate Indian Ocean responds to a freshwater flux anomaly at the surface of the North Atlantic. As suggested by the geochemical time series, both the abundance of Southern Ocean Water and the oxygen concentration are significantly increased in response to this freshwater perturbation.

Organic geochemistry of two sediment cores from the Kara Sea

Within the Russian-German research project on "Siberian River Run-off (SIRRO)" devoted to the freshwater discharge and its influence on biological, geochemical, and geological processes in the Kara Sea, sedimentological and organic-geochemical investigations were carried-out on two well-dated sediment cores from the Yenisei Estuary area. The main goal of this study was to quantify the terrigenous organic carbon accumulation based on biomarker and bulk accumulation rate data, and its relationship to Yenisei river discharge and climate change through Holocene times. The biomarker data at both cores clearly indicate the predominance of terrigenous organic matter, reaching 70 to 100% and 50 to 80% of the total organic carbon within and directly north of the estuary, respectively. During the last about 9 Cal. kyrs. BP represented in the studied sediment section, siliciclastic sediment and (terrigenous) organic carbon input was strongly influenced by postglacial sea-level rise and climate-related changes in river discharge. The mid-Holocene Climatic Optimum is documented by maximum river discharge between 8.2 and 7.3 Cal. kyrs. BP. During the last 2000 years river discharge probably became reduced, and accumulation of both terrigenous and marine organic carbon increased due to increased coagulation of fine-grained material.

Biomarker proxies on sediment cores in the central Arctic Ocean

Although the permanently to seasonally ice-covered Arctic Ocean is a unique and sensitive component in the Earth's climate system, the knowledge of its long-term climate history remains very limited due to the restricted number of pre-Quaternary sedimentary records. During Polarstern Expedition PS87/2014, we discovered multiple submarine landslides over a distance of >350 km along Lomonosov Ridge. Removal of younger sediments from steep headwalls has led to exhumation of Miocene to early Quaternary sediments close to the seafloor, allowing the retrieval of such old sediments with gravity cores. Multi-proxy biomarker analyses of these gravity cores reveal for the first time that the late Miocene central Arctic Ocean was relatively warm (4-7°C) and ice-free during summer, whereas sea ice occurred during spring and autumn/winter. A comparison of our proxy data with Miocene climate simulations seems to favour relatively high late Miocene atmospheric CO2 concentrations. These new findings from the Arctic region provide new benchmarks for groundtruthing global climate reconstructions and modeling.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Moleculare composition of sediments from ODP Hole 116-717C

We describe the molecular composition of a portion of the solvent-soluble organic material (lipid extract), from three organic rich muds (samples 116-717C-22X-1, 80-86 cm, 116-717C-34X-3, 130-135 cm, and 116-717C-55X-1, 65-70 cm). These samples were taken from Hole 717C, located on the Bengal Fan at a position of 0°55.8'S and 81°23.4'E. Both the palaeoenvironmental and digenetic significance of these lipid distributions have been assessed and found to be consistent with their suspected origins, i.e., turbidites from the upper slope of the western Bay of Bengal and the Ganges-Brahmaputra delta.

Hydrocarbons, sterols and alkenones at time series station KERFIX

Hydrocarbons, sterols and alkenones were analyzed in samples collected from a 10 month sediment trap time series deployed in the Indian Ocean sector of the Southern Ocean. Fluxes and within-class distributions varied seasonally. During higher mass and organic carbon (OC) flux periods, which occurred in austral summer and fall, fresh marine inputs were predominant. Vertical fluxes were most intense in January, but limited to one week in duration. They were, however, low compared with other oceanic regions. In contrast, low mass and OC flux periods were characterized by a strong unresolved complex mixture (UCM) in the hydrocarbon fraction and a high proportion of stanols as a result of zooplanktonic grazing. Terrigenous inputs were not detectable. The alkenone compositions were consistent with previous data on suspended particles from Antarctic waters. However, UK'37 values diverged from the linear and exponential fits established by Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) in the low temperature range. The seasonal pattern of alkenone production implied that IPT (integrated production temperature) is likely to be strongly imprinted by austral summer and fall SST (sea surface temperature).