Shelf-Ocean material exchange influencing the Atlantic chemical composition off NW Iberian margin since the last glaciation

Rivers are the main conduit of sediment to the shelf. The basin geology, the drainage area and the discharge rate are the major factors that determine their sediment load (Milliman and Syvistski, 1992). Besides suspended particles, dissolved components may also give some information on the eroded crust. Sr isotopes in carbonate shells of biological organisms have been used to study, in the geological record, the influence exerted by the chemical weathering of the continental crust on the seawater composition (Macdougall, 1991). In this work, Sr isotope ratios obtained in tests of foraminifera representing the last 40 ka are presented and discussed in the scope of the palaeogeographical evolution of NW Iberia. This work aims to present and discuss the results of Sr isotope analyses (performed, by TIMS, in the Isotope Geology Laboratory of the University of Aveiro) of tests of two species of foraminifera, from nine samples taken along the OMEX core KC 024-19 (181 cm; 42°08’98’’N, 10°29´96’’W, and 2765m), collected in the Galicia Bank area, off Galicia. Taking into account that Sr contained in the carbonate tests is usually considered as preserving the signature of the contemporaneous seawater, one planktonic species (Globigerina bulloides) and one benthic species (Cibicides wuellerstorfi) were selected in order to try to detect Sr isotope variations both through time and between two different levels of the water column. The core age model, which records the last 40 ka, is based on a combination of oxygen isotope stratigraphy, eight AMS 14C datings and the synchronisation of the last four Heinrich Events in the Iberian Margin sedimentary records. As a whole, the obtained 87Sr/86Sr ratios vary between 0.709209 and 0.709108, with a mean 2σ error of 0.000025. These values lie within the range of modern marine Sr isotope ratios (0.70910-0.70922), as previously defined using analyses of both seawater and marine carbonates (see compilation by Faure and Mensing, 2005). Despite their small variation, the 87Sr/86Sr ratios obtained in G. bulloides seem to indicate that Sr dissolved in seawater at the KC 024-19 core site became slightly less radiogenic after the Last Glacial Maximum (LGM). This decrease is concomitant with diminishing amounts of the detrital components in the sediments (Fig. 1). Therefore, both the composition of dissolved Sr, as revealed by results on tests of planktonic foraminifera, and the proportions of suspended terrigenous particulate material arriving at the KC 024-19 site point to a decreasing importance of the contribution of the erosion of the Iberian Variscan crust since the Last Glacial Maximum and in the Holocene. The 87Sr/86Sr ratios measured in tests of benthic foraminifera (C. wuellerstorfi) are more erratic and no correlation can be established with palaeogeographical/palaeoclimatic constraints. The difference between the behaviour of Sr compositions in G. bulloides and C. wuellerstorfi may indicate that whilst the planktonic foraminifera should reproduce very closely the seawater composition, the benthic organisms should, in addition to the major role of seawater, also be affected by some sort of interaction with the sediments. As such, planktonic foraminifera are probably more reliable indicators of seawater composition in studies involving very small periods and corresponding very slight variations of the 87Sr/86Sr ratios. Taking into account that G. bulloides is a common planktonic species (living mostly in the first 50m of the water column), whose tests seem to be in equilibrium with sea water composition, variations in its 87Sr/86Sr ratios can be related with changes in the chemical composition of the water of the Atlantic Ocean off NW Iberian Margin. The highest 87Sr/86Sr values are contemporaneous with a period of low sea level (about -140 m; Dias et al., 2000) during the LGM. According to Dias et al. (2000) at 18 ka BP the shoreline was close to the shelf break. The summital parts of the Gerês and Estrela mountains were covered by local glaciers and close to the coast freezing occurred frequently. The river catchments, which extended far to the shelf, received more rainfall due to a longer, compared to present day conditions, wet season, which promoted both physical and chemical weathering. Higher pluviosity combined with the effect of spring ice melting maintained high river discharge and consequently caused very important sediment supply to the coastal zone. The extremely narrow shelf was a very energetic environment due to sea bottom inclination and very limited long wave refraction. Therefore, at that time, a long wet season and very competent rivers should have caused important erosion of the Variscan basement in NW Iberia. Additionally, then, the shoreline was much closer to the KC 024-19 site. The combination of all these factors favoured an important deposition of terrigenous sediments and the local slight enrichment in radiogenic Sr of the seawater. With sea level rise, after the deglaciation and during the Holocene, the river estuaries became progressively far away from the shelf break. Their competence of transport also became progressively reduced and the offshore transport of detrital sediments became progressively lower. Conversely the biogenic carbonate proportion in the sediments increased, due to lower dilution by the terrigenous particles. Simultaneously, the values of 87Sr/86Sr in the seawater at the KC 024-19 site became lower, as a consequence of a complete homogenization with the ocean global composition, which was now more effective with the increasing distance towards shoreline

Supramolecular dehydropeptide hydrogels: synthesis, properties and biomedical applications

Self-assembled low molecular weight peptide hydrogels have emerged in recent years as the new paradigm in biomaterials research due to their high water content; fully organic struc-ture; intrinsic nontoxicity and biocompatibility and fibrillar nanostructure indicative of the ex-tracellular matrix.1 The properties of peptide hydrogels can be tuned by design and there is a large variety of possible hydrogelator structures using proteinogenic and non proteinogenic aminoacids. Our research group has recently described a series of self-assembled hydrogels based on dehydrodipeptides N-protected with an aromatic moiety. The C-terminal dehy-droaminoacid residue (dehydrophenylalanine, dehydroaminobutyric acid and dehydroalanine) is prone to make the peptide resistant to prote-olysis and restrains the conformational freedom of the peptide.2 In this work the preparation and characterization of the new hydrogelators as well as the corresponding hydrogels will be presented together with some biomedical appli-cations of the new biomaterials prepared name-ly as drug delivery systems or as plataforms for theragnostics.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding of CQUM (UID/QUI/00686/2016) and CF-UM-UP (UID/FIS/04650/2013 and UID/FIS/04650/ 2019), FEDER, PORTUGAL2020 and COMPETE2020 are also acknowledged for funding under the research projects PTDC/QUI-QFI/28020/2017 (POCI-01-0145-FEDER-028020) and PTDC/QUI-QOR/29015/ 2017 (POCI-01-0145-FEDER-029015)

Synthesis of 2,6-bis-(oxazolyl)pyridine ligands for luminescent Ln(III) complexes

Submitted to the European Journal of Organic ChemistryNew bis-(oxazolyl)pyridine ligands for Ln(III) ions were prepared using a expeditious methodology from threonine and dipicolinic acid chloride. The synthetic strategy includes a dehydration step to give a bis-dehydroaminobutyric acid derivative followed by bromination and cyclization with DBU. Photophysical studies of Eu(III) and Tb(III) complexes of these ligands showed that the 2,6-bis-(oxazolyl)pyridine moiety acts as an effective sensitizer for lanthanide luminescence and indicate the formation of 3:1 complexes [Ln-(bis-(oxazole)pyridine)3]3+.Fundação para a Ciência e Tecnologia (FCT), QREN, FEDER/E

Impact of microphallid trematodes on the survivorship, growth, and reproduction of an isopod (Cyathura carinata)

Crustaceans are second intermediate hosts to several microphallid species (Trematoda). Some of these parasites are potentially pathogenic or manipulative. A laboratory experiment was performed to assess the impact of microphallids on the survival, growth and fecundity of Cyathura carinata, a protogynous hermaphroditic isopod, widespread within European estuaries. For nearly 12 weeks, experimental populations of infected and non-infected isopods were kept at 25 °C. C. carinata carrying microphallid cysts showed higher mortality rates than non-infected specimens and were not able to produce embryos. The reduced fecundity of infected isopods could be caused by parasite-induced castration and/or by mating failure due to behavioural modifications in one of the sexes. It might also be associated with lower growth rates and lower moulting frequencies, since infected C. carinata were significantly smaller than the non-infected after 9 weeks. This may imply a setback for the isopods to achieve sexual maturity (which may also affect the population sex ratio) and for females to lay their eggs in the marsupia. Regardless of the mechanisms involved, microphallids may have severe consequences for their host populations, through negative effects on survival, growth and fecundity. For species with direct development, such as C. carinata, parasite-induced reproduction failure may contribute to temporal fluctuations of abundance. Based on the present results, it is recommended to include parasites as an important factor influencing host populations from shallow-water ecosystems.http://www.sciencedirect.com/science/article/B6T8F-4FFNBXG-2/1/9ad5e11a8a6dbb35f5d593f82562194

New magnetogels based on manganese ferrite nanoparticles and self-assembled peptide hydrogels as drug nanocarriers

In this work, superparamagnetic manganese ferrite (MnFe2O4) nanoparticles were successfully incorporated in self-assembled peptide-derived hydrogels. The new magnetogels were tested as nanocarriers for two fluorescent drugs, curcumin (an anticancer and neuroprotective drug) and a new antitumor thienopyridine derivative. Fluorescence-based techniques (fluorescence emission, FRET and fluorescence anisotropy) were used to assess incorporation of these drugs in the magnetogels and their transport towards models of biological membranes. It can be observed that the drug moves to the model membranes upon interaction of the drug-loaded magnetogels with membranes.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding of CF-UM-UP (UID/FIS/04650/2013) and of CQ-UM (UID/QUI/00686/2013). FCT, POPH-QREN and FSE are acknowledged for the PhD grant of A.R.O. Rodrigues (SFRH/BD/90949/2012) and for financial support to MAP-Fis Joint Doctoral Programme.info:eu-repo/semantics/publishedVersio

A reaction-diffusion model for the growth of avascular tumor

A nutrient-limited model for avascular cancer growth including cell proliferation, motility and death is presented. The model qualitatively reproduces commonly observed morphologies for primary tumors, and the simulated patterns are characterized by its gyration radius, total number of cancer cells, and number of cells on tumor periphery. These very distinct morphological patterns follow Gompertz growth curves, but exhibit different scaling laws for their surfaces. Also, the simulated tumors incorporate a spatial structure composed of a central necrotic core, an inner rim of quiescent cells and a narrow outer shell of proliferating cells in agreement with biological data. Finally, our results indicate that the competition for nutrients among normal and cancer cells may be a determinant factor in generating papillary tumor morphology.Comment: 9 pages, 6 figures, to appear in PR

Avaliação dos produtos químicos aplicados nas sementes de arroz irrigado-safra 2009/2010

bitstream/item/78787/1/Boletim-161.pd

Synthesis and preliminary biological evaluation of new phenolic and catecholic dehydroamino acid derivatives

A library of N-phenolic and N-catecholic dehydroamino acid derivatives was prepared using an innovative synthetic strategy that involves mild reaction conditions and simple work-up procedures. The method comprises coupling of phenolic or catecholic acids with β-hydroxyamino acids followed by tert-butyloxycarbonylation of all hydroxyl groups using tert-butyldicarbonate and 4-dimethylaminopyridine as catalyst. Treatment of these amino acids with N,N,N’,N’-tetramethylguanidine affords the corresponding O-tert-butyloxycarbonyldehydro-amino acid derivative. Deprotection of the aromatic hydroxyl groups is carried out with trifluoroacetic acid. This synthetic strategy can be applied in a one-pot procedure and yields compounds that can be easily inserted into peptides or other biomolecules after cleavage of the C-protecting group. Preliminary studies of cell viability show that these new compounds display very low or no toxicity. These dehydroamino acids with a phenolic or catecholic moiety can have intrinsic biological activity or used to prepare new hydrogels that mimic mussel adhesive proteins.This work received financial support from the Foundation for Science and Technology (FCT, Portugal), through projects UID/QUI/00686/2013, UID/QUI/00686/2016 (CQUM) and UID/QUI/50006/2013-POCI-01-0145-FEDER-007265, co-financed by European Union (FEDER under the Partnership Agreement PT2020), and from Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF) (project NORTE-010145-FEDER-24).info:eu-repo/semantics/publishedVersio