Control of neuronal signalling pathways by CYP46A1, an enzime involved in brain cholesterol homeostasis

Tese de doutoramento, Farmácia (Biologia Celular e Molecular), Universidade de Lisboa, Faculdade de Farmácia, 2016

Chromatographic fractionation of bitumen from sediments and presence of glycerol ethers in immature sediments (Table 2)

Alkanes having unusual saturated isoprenoidal and methyl-branched structures have been isolated from the bitumen of several sediments. The methanogenic biomarkers 2,6,10,15,19-pentamethyleicosane and squalane were found in sediments which also contained bacteriogenic glycerol ethers. However, in one ether-containing sediment, 2,6,10,13,17,21-hexamethyldocosane was tentatively identified and this compound was found in place of the established alkane biomarkers. Other hydrocarbons found were regular C21 and C23 isoprenoid alkanes, compounds which cannot be derived from phytol; two isoprenoids of the type 3,7,11.-polymethylalkane, previously reported only in petroleums; 8-methylheptadecane, a probable biomarker for cyanobacteria and a number of its homologs and other methyl-branched alkanes. Ubiquitous branched-chain alkylbenzenes and a homology of trimethylalkylbenzenes were also isolated. Most, or all, of the compounds reported here are probably not catagenetic products but may represent direct algal or bacterial bioinputs.

Age determination and paleotemperatures of sediment cores TTR17-1_384B and TTR17-1_436B in the Alboran Sea

Climate conditions in the westernmost Mediterranean (Alboran Sea basin) over the last two millennia have been reconstructed through integration of molecular proxies applied for the first time in this region at such high resolution. Two temperature proxies, one based on isoprenoid membrane lipids of marine Thaumarchaeota (TEXH86-tetraether index of compounds consisting of 86 carbons) and the other on alkenones produced by haptophytes (UK'37 ratio) were applied to reconstruct sea surface temperature (SST). Both records reveal a progressive long term decline in SST over the last two millennia and an increased rate of warming during the second half of the twentieth century. This is in accord with previous temperature reconstructions for the Northern Hemisphere. TEXH86 temperature values are higher than those inferred from UK'37, probably due to differences in the bloom season of haptophytes and Thaumarchaeota, and reflect summer SST. The branched vs. isoprenoid tetraether index (BIT index) suggests a low contribution of soil organic matter (OM) to the sedimentary OM. The stable carbon isotopic composition of long chain n-alkanes indicates a predominant C3 plant contribution, with no major change in vegetation over the last 2000 yr. The distribution of long chain 1,14-diols (most likely sourced by Proboscia species in this setting) provided insight into variation in upwelling conditions during the last 2000 yr and depicts a correlation with the North Atlantic Oscillation (NAO) index, providing evidence of enhanced wind induced upwelling during periods of a persistent positive mode of the NAO.

Biomarkers of early Aptian sediments of the Shatsky Rise

This study investigates organic-rich sedimentary sequences deposited during the early Aptian Oceanic Anoxic Event (OAE1a) at Sites 1207 and 1213 on Shatsky Rise (ODP Leg 198) in the west-central Pacific. Biomarker analyses provide evidence of the algal and bacterial origin of organic matter (OM) in these sediments where the abundance of steroidal components, particularly sterenes and sterones, suggests that the OM includes major contributions from eukaryotic sources in an environment characterized by high phytoplankton productivity. The presence of alkenones at Site 1213B is diagnostic of OM derived from representatives of haptophyte algae among the calcareous nannoplankton and their d13C values (average -31.6 per mil) are consistent with those expected during elevated pCO2. The occurrence and prominence of 2b-methylhopanes and 2b-methylhopanones indicates significant contributions to the OM from cyanobacteria, which are also likely contributors of hopanoids based on their d13C compositions. These biomarker data suggest that oceanic conditions, perhaps nitrate- or iron-limited, were conducive to cyanobacteria production during OAE1a, which appears to distinguish this event from other Cretaceous OAE.

Some parameters of distribution of hydrocarbon paraffin fraction in bottom sediments of the Kara Sea and the Yenisey estuary

During Cruise 49 of R/V Dmitry Mendeleev in the Kara Sea (August-September, 1993) chemical-bitumenological studies of bottom sediments were carried out. Hydrocarbons were analyzed by gas-liquid chromatography. It was found on the basis of distribution of n-alkanes and isoprenoids (pristan and phytan) that organic matter is mainly terrigenous consisting of higher plant remains.

Biomarker proxies on ODP Holes 151-912A and 151-912B

A novel and promising biomarker proxy for reconstruction of Arctic sea ice conditions was developed and is based on the determination of a highly branched isoprenoid with 25 carbons (IP25). IP25 records have been restricted to the last 150 kyr BP. We present a biomarker record from Ocean Drilling Program (ODP) Site 912, going back to the Pliocene-Pleistocene boundary and indicating that sea ice of variable extent occurred in the Fram Strait/southern Yermak Plateau area at least since about 2.2 Ma. Furthermore, our data support the idea that a combination of IP25 and open water, phytoplankton biomarker data ("PIP25 index") may give a more reliable and quantitative estimate of past sea ice cover (at least for the study area). The study reveals that the novel IP25/PIP25 biomarker approach has potential for semi-quantitative paleo-sea ice studies covering the entire Quaternary and could motivate further detailed high resolution research on ODP/IODP material using this proxy.

Biomarker distributions in surface sediments from the Kara and Laptev Seas (Arctic Ocean)

Studies of spatial and temporal changes in modern and past sea-ice occurrence may help to understand the processes controlling the recent decrease in Arctic sea-ice cover. Here, we determined concentrations of IP25, a novel biomarker proxy for sea ice developed in recent years, phytoplankton-derived biomarkers (brassicasterol and dinosterol) and terrigenous biomarkers (campesterol and ß-sitosterol) in the surface sediments from the Kara and Laptev seas to estimate modern spatial (seasonal) sea-ice variability and organic-matter sources. C25-HBI dienes and trienes were determined as additional paleoenvironmental proxies in the study area. Furthermore, a combined phytoplankton-IP25 biomarker approach (PIP25 index) is used to reconstruct the modern sea-ice distribution more quantitatively. The terrigenous biomarkers reach maximum concentrations in the coastal zones and estuaries, reflecting the huge discharge by the major rivers Ob, Yenisei and Lena. Maxima in phytoplankton biomarkers indicating increased primary productivity were found in the seasonally ice-free central part of the Kara and Laptev seas. Neither IP25 nor PIP25, however, show a clear and simple correlation with satellite sea-ice distribution in our study area due to the complex environmental conditions in our study area and the transportation process of sea-ice diatom in the water column. Differences in the diene/IP25 and triene/IP25 ratios point to different sources of these HBIs and different environmental conditions. The diene/IP25 ratio seems to correlate positively with sea-surface temperature, while negatively with salinity distributions.

Discovery of genes associated with fruit ripening in Carica papaya using expressed sequence tags

To identify genes involved in papaya fruit ripening, a total of 1171 expressed sequence tags (ESTs) were generated from randomly selected clones of two independent fruit cDNA libraries derived from yellow and red-fleshed fruit varieties. The most abundant sequences encoded: chitinase, 1-aminocyclopropane- 1-carboxylic acid (ACC) oxidase, catalase and methionine synthase, respectively. DNA sequence comparisons identified ESTs with significant similarity to genes associated with fruit softening, aroma and colour biosynthesis. Putative cell wall hydrolases, cell membrane hydrolases, and ethylene synthesis and regulation sequences were identified with predicted roles in fruit softening. Expressed papaya genes associated with fruit aroma included isoprenoid biosynthesis and shikimic acid pathway genes and proteins associated with acyl lipid catabolism. Putative fruit colour genes were identified due to their similarity with carotenoid and chlorophyll biosynthesis genes from other plant species. © 2005 Elsevier Ireland Ltd. All rights reserved.

Occurrence and distribution of novel botryococcene hydrocarbons in freshwater wetlands of the Florida Everglades

A high abundance of isoprenoid hydrocarbons, the botryococcenes, with carbon numbers from 32 to 34 were detected in the Florida Everglades freshwater wetlands. These compounds were present in varying amounts up to 106 μg/gdw in periphyton, 278 μg/gdw in floc, and 46 μg/gdw in soils. Their structures were determined based on comparison to standards, interpretation of their mass spectra and those of their hydrogenation products, and comparison of Kovats indexes to those reported in the literature. A total of 26 cyclic and acyclic botryococcenes with 8 skeletons were identified, including those with fewer degrees of unsaturation, which are proposed as early diagenetic derivatives from the natural products. This is the first report that botryococcenes occur in the Everglades freshwater wetlands. Their potential biogenetic sources from green algae and cyanobacteria were examined, but neither contained botryococcenes. Thus, the source implication of botryococcenes in this ecosystem needs further study.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

(Table 1) TOC, d13C, and preservation factors of turbidite sediments

In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 ?m). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.