Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands

Four cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(PPh3)(2)](+), with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b; 4,3-b'] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells).

Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbers

In this work, SnxSy thin films have been grown on soda-lime glass substrates by sulphurization of metallic precursors in a nitrogen plus sulphur vapour atmosphere. Different sulphurization temperatures were tested, ranging from 300 °C to 520 °C. The resulting phases were structurally investigated by X-Ray Diffraction and Raman spectroscopy. Composition was studied using Energy Dispersive Spectroscopy being then correlated with the sulphurization temperature. Optical measurements were performed to obtain transmittance and reflectance spectra, from which the energy band gaps, were estimated. The values obtained were 1.17 eV for the indirect transition and for the direct transition the values varied from 1.26 eV to 1.57 eV. Electrical characterization using Hot Point Probe showed that all samples were p-type semiconductors. Solar cells were built using the structure: SLG/Mo/SnxSy/CdS/ZnO:Ga and the best result for solar cell efficiency was 0.17%.

Photoelectron spectroscopy of nitrogen containing molecules of biological and industrial interest

A thesis submitted for the degree of Ph. D. in Physics

Valorization of grape pomace residues integrating hot compressed water with biotechnology

Dissertação para obtenção do grau de Mestre em Biotecnologia

Fate of nitrogen in bioreactor landfills: lab-scale in situ aeration in well decomposed MSW

Dissertação para obtenção do Grau de Mestre em Engenharia do ambiente, perfil de engenharia sanitária

Dissolved organic nitrogen behaviour during denitrification with suspended and attached biomass

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente, perfil Engenharia Sanitária

Experimental Gravimetric Adsorption Equilibrium of n-Alkanes and Alkenes, Carbon Dioxide and Nitrogen in MIL-53(Al) and Zeolite 5A

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Nitrogen (N) : from science to society. A science communication project

O Azoto (N): da ciência para a sociedade é um projecto de comunicação de ciência que tem por objecNvo consciencializar os jovens para as ameaças que o azoto (N) em excesso traz para a humanidade. Pode ser dividido em duas partes. Uma, de invesNgação, sobre a análise de resultados de uma consulta pública realizada entre professores, usando o método qualitaNvo do focus group, para compreender a sua sensibilidade e propostas de solução para minimizar o excesso de N no ambiente. Os resultados obNdos foram instrumentais para o desenvolvimento da segunda parte. Esta segunda parte é uma proposta de projecto a submeter ao Horizon 2020, no âm-­‐ bito da “Science with and for Society “. Nela se propõe uma abordagem educaNva trans-­‐disciplinar, conseguida através da interacção entre docentes do secundário, e do ensino superior, associação de pais e organizações cívicas não governamentais, com vista à consciencialização dos jovens para as ameaças do N em excesso no meio ambiente, fazendo o enquadramento cien@fico e fornecendo abordagens tecnológi-­‐ cas. A inovação desta proposta baseia-­‐se: (i) no acompanhamento e desenvolvimen-­‐ to profissional dos docentes do secundário, (ii) na moNvação dos estudantes a de-­‐ senvolver o seu próprio estudo e pesquisa com a tutoria dos docentes, da escola e do ensino superior, e (iii) no desenvolvimento de capacidades de comunicação dos jo-­‐ vens para exercer uma cidadania acNva em prol da minimização das ameaças do N.

Traduzir Teatro no Estado Novo: Gata em Telhado de Zinco Quente (1959), tradução de Sérgio Guimarães, do original Cat on a Hot Tin Roof (1955), de Tennessee Williams

À luz da viragem cultural dos Estudos de Tradução ocorrida nos anos 80 e tendo em conta a interdisciplinaridade abordada nos campos literário, cultural e histórico pela Manipulation School (Lefevere, Bassnett, Lambert, Hermans e Toury), na esteira de Itamar Even-Zohar com a Teoria dos Polissistemas (1979), a presente dissertação pretende analisar a tradução portuguesa da peça Cat on a Hot Tin Roof (1955), da autoria de Tennessee Williams, intitulada Gata em Telhado de Zinco Quente (1959), de Sérgio Guimarães. Este pode ser um caso representativo de como a tradução para teatro actua na cultura receptora numa perspectiva diatópica, antevendo a dimensão intercultural da tradução para o palco. É ao tradutor que cabe a tarefa de transferir a peça de um sistema linguístico e cultural para outro, conhecendo, se possível, o grau de representabilidade da mesma e o contexto cultural de chegada. Deste modo, é evidenciada a competência artístico-criativa do tradutor teatral que trabalha com o intuito de manter, fidus interpres, as intenções do autor da obra original. No período em que Cat on a Hot Tin Roof foi escrita, ensombrado pelo controlo sociopolítico do Macartismo nos E.U.A. e o contexto em que a tradução foi concretizada, sob a vigência da Ditadura de Salazar, a (auto)censura desempenha um papel fundamental ao moldar a produção literária nos dois sistemas culturais. Numa época em que, mais do que nos dias de hoje, traduzir consistia numa actividade subserviente e secundária, Vasco Morgado, detentor do monopólio de teatros em Lisboa encomendou a Sérgio Guimarães a tradução de uma peça de Tennessee Williams. Com base na teoria desenvolvida por Lawrence Venuti em The Translator’s Invisibility (1995), não é despiciente problematizar, neste estudo de caso, a invisibilidade do tradutor/mediador entre o texto e a representação, abordando simultaneamente as estratégias então necessárias para a peça ser aprovada e posta em cena.

Impact of carbon/nitrogen feeding strategy on polyhydroxyalkanoates production using mixed microbial cultures

Polyhydroxyalkanoates (PHA) production using mixed microbial cultures (MMC) requires a multi-stage process involving the microbial selection of PHA-storing microorganisms, typically operated in sequencing batch reactors (SBR), and an accumulation reactor. Since low-cost renewable feedstocks used as process feedstock are often nitrogen-deficient, nutrient supply in the selection stage is required to allow for microbial growth. In this context, the possibility to uncouple nitrogen supply from carbon feeding within the SBR cycle has been investigated in this study. Moreover, three different COD:N ratios (100:3.79, 100:3.03 and 100:2.43) were tested in three different runs which also allowed the study of COD:N ratio on the SBR performance. For each run, a synthetic mixture of acetic and propionic acids at an overall organic load rate of 8.5 gCOD L-1 d-1 was used as carbon feedstock, whereas ammonium sulfate was the nitrogen source in a lab-scale sequence batch reactor (SBR) with 1 L of working volume. Besides, a sludge retention time (SRT) of 1 d was used as well as a 6 h cycle length. The uncoupled feeding strategy significantly enhanced the selective pressure towards PHA-storing microorganisms, resulting in a two-fold increase in the PHA production (up to about 1.3 gCOD L-1). A high storage response was observed for the two runs with the COD:N ratios (gCOD:gN) of 100:3.79 and 100:3.03, whereas the lowest investigated nitrogen load resulted in very poor performance in terms of polymer production. In fact, strong nitrogen limitation caused fungi to grow and a very poor storage ability by microorganisms that thrived in those conditions. The COD:N ratio also affected the polymer composition, indeed the produced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) showed a variable HV content (1-20 %, w/w) among the three runs, lessening as the COD:N increased. This clearly suggests the possibility to use the COD:N ratio as a tool for tuning polymer properties regardless the composition of the feedstock.

Valorization of grape pomace through hot compressed water extraction/hydrolysis

The world energy consumption is expected to increase strongly in coming years, because of the emerging economies. Biomass is the only renewable carbon resource that is abundant enough to be used as a source of energy Grape pomace is one of the most abundant agro-industrial residues in the world, being a good biomass resource. The aim of this work is the valorization of grape pomace from white grapes (WWGP) and from red grapes (RWGP), through the extraction of phenolic compounds with antioxidant activity, as well as through the extraction/hydrolysis of carbohydrates, using subcritical water, or hot compressed water (HCW). The main focus of this work is the optimization of the process for WWGP, while for RWGP only one set of parameters were tested. The temperatures used were 170, 190 and 210 °C for WWGP, and 180 °C for RWGP. The water flow rates were 5 and 10 mL/min, and the pressure was always kept at 100 bar. Before performing HCW assays, both residues were characterized, revealing that WWGP is very rich in free sugars (around 40%) essentially glucose and fructose, while RWGP has higher contents of structural sugars, lignin, lipids and protein. For WWGP the best results were achieved at 210 °C and 10 mL/min: higher yield in water soluble compounds (69 wt.%), phenolics extraction (26.2 mg/g) and carbohydrates recovery (49.3 wt.% relative to the existing 57.8%). For RWGP the conditions were not optimized (180 °C and 5 mL/min), and the values of the yield in water soluble compounds (25 wt.%), phenolics extraction (19.5 mg/g) and carbohydrates recovery (11.4 wt.% relative to the existing 33.5%) were much lower. The antioxidant activity of the HCW extracts from each assay was determined, the best result being obtained for WWGP, namely for extracts obtained at 210 °C (EC50=20.8 μg/mL; EC50 = half maximum effective concentration; EC50 = 22.1 μg/mL for RWGP, at 180 ºC).

Seasonal changes of leaf Nitrogen content in trees of Amazonian floodplains

In Amazonian floodplains the trees are exposed to extreme flooding of up to 230 days a year. Waterlogging of the roots and stems affects growth and metabolic activity of the trees. An increased leaf fall in the aquatic period and annual increment rings in the wood indicate periodical growth reductions. The present study aims at documenting seasonal changes of metabolism and vitality of adult trees in the annual cycle as expressed by changes of leaf nitrogen content. Leaves of six tree species common in floodplains in Central Amazonia and typical representants of different growth strategies were collected every month between May 1994 and June 1995 in the vicinity of Manaus, Brazil. Mean leaf nitrogen content varied between 1.3% and 3.2% in the non-flooded trees. Three species showed significantly lower Ν content in the flooded period (p=0.05, 0.001, 0.001), the difference ranging 20-25% lower than in the non-flooded period. Two species showed no significant difference while Nectandra amazonum showed 32% more Ν in the flooded season (p=0.001). Leaf nitrogen content was generally high when new leaves were flushed (in the flooded period) and decreased continuously thereafter in all species. Three species showed an additional peak of nitrogen during the first month of the terrestrial phase, in leaves which had flushed earlier, indicating that flooding may disturb nitrogen uptake.

Fertilization and cover crop effects on soil nitrogen and plant nutrition in a young guarana plantation

Fruit tree production is gaining an increasing importance in the central Amazon and elsewhere in the humid tropics, but very little is known about the nutrient dynamics in the soil-plant system. The present study quantified the effects of fertilization and cover cropping with a legume (Pueraria phaseoloides (Roxb.) Benth.) on soil nitrogen (N) dynamics and plant nutrition in a young guarana plantation (Paullinia cupana Kunth. (H.B. and K.) var. sorbilis (Mart.) Ducke) on a highly weathered Xanthic Ferralsol. Large subsoil nitrate (NO3-) accumulation at 0.3-3 m below the guarana plantation indicated N leaching from the topsoil. The NO3- contents to a depth of 2 m were 2.4 times greater between the trees than underneath unfertilized trees (P<0.05). The legume cover crop between the trees increased soil N availability as shown by elevated aerobic N mineralization and lower N immobilization in microbial biomass. The guarana N nutrition and yield did not benefit from the N input by biological fixation of atmospheric N2 by the legume cover (P>0.05). Even without a legume intercrop, large amounts of NO3- were found in the subsoil between unfertilized trees. Subsoil NO3- between the trees could be utilized, however, by fertilized guarana. This can be explained by a more vigorous growth of fertilized trees which had a larger nutrient demand and exploited a larger soil volume. With a legume cover crop, however, more mineral N was available at the topsoil which was leached into the subsoil and consequently accumulated at 0.3-3 m depth. Fertilizer additions of P and K were needed to increase subsoil NO3- use between trees.

Does nitrogen availability have greater control over the formation of tropical heath forests than water stress?A hypothesis based on nitrogen isotope ratios

Global scale analyses of soil and foliage δ15N have found positive relationships between δ15N and ecosystem N loss (suggesting an open N cycle) and a negative relationship between δ15N and water availability. We show here that soils and leaves from tropical heath forests are depleted in 15N relative to 'typical' forests suggesting that they have a tight N cycle and are therefore limited by N rather than by, often suggested, water availability.