Systematic design analysis and risk management on engineered nanoparticles occupational exposure

The production of nanotechnology-based products is increasing, along with the conscience of the possible harmful effects of some nanomaterials. The “safety-by-design” approaches are getting attention as helpful tools to develop safer products and production processes. The Systematic Design Analysis Approach could help to identify the solutions to control the workplace risks by defining the emission and exposure scenarios and the possible barriers to interrupt them. By applying this approach in a photocatalytic ceramic tiles development project it was possible to identify relevant nanoparticles emission scenarios and related barriers, and defining possible ways to reduce it.

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

Literacias na educação de adultos

[Excerpt] Apesar de muitas evidências em contrário (GRAFF, 1979; CARRINGTON; LUKE, 1997), nas sociedades contemporâneas está fortemente enraizada a convicção de que a prosperidade dos países depende de ‘níveis de literacia’ das populações. Com efeito, as “perspetivas económicas da literacia”, adotadas por muitos organismos e não apenas pelo discurso corrente, assumem que um dos indicadores de progresso é a literacia (por exemplo, UNESCO, 2006; DATAANGEL POLICY RESEARCH INCORPORATED, 2009). Na medida em que esta crença tende também a posicionar os indivíduos, sem ou com pouca escolarização, quase “como marginais” e “socialmente excluídos” (HAMILTON; PITT, 2011, p. 350), a sua “falta de literacia” constitui uma preocupação de políticas públicas dos governos, por exemplo da área da OCDE, traduzidas em mecanismos de monitorização, medidas e programas. Também a UNESCO (2006) tem assumido que o desafio que as questões de literacia colocam aos países só pode ser enfrentado se se aumentar a qualidade da educação primária e secundaria e se se intensificarem os programas explicitamente orientados para a literacia de jovens e adultos (UNESCO, 2006, p. 17). (...)

Photolabile protection for amino acids: studies on the release from novel benzoquinolone cages

The synthesis of a novel fused nitrogen heterocycle, benzoquinolone, for evaluation as a photocleavable protecting group is described for the first time, by coupling to model amino acids (alanine, phenylalanine and glutamic acid). Conversion of the phenylalanine ester conjugate to the thionated derivative was accomplished by reaction with Lawesson’s reagent. Photocleavage studies of the carbonyl and thiocarbonyl benzoquinolone conjugates in various solvents and at different wavelengths (300, 350 and 419 nm) showed that the most interesting result was obtained at 419 nm for the thioconjugate, revealing that the presence of the thiocarbonyl group clearly improved the photolysis rates, giving practicable irradiations times for the release of the amino acids (less than 1 minute).

Aminobenzocoumarinylmehtyl esters as photoactive precursors for the release of butyric acid

The evaluation of the photorelease of a carboxylic acid drug, using butyric acid as a representative model, was carried out by using 7-amino-4-chloromethyl-2-oxo-2Hnaphtho[1,2-b] pyran, an aminobenzocoumarin, and its mono- and di-methylated or ethylated derivatives. This study was intended to improve the release of butyric acid from benzocoumarins by the addition of an amino group to the heterocycle by applying the knowledge of second-generation coumarinylmethyl-based photoremovable protecting groups. Photolysis studies were performed on the resultant ester cages by irradiation in a photochemical reactor at 254, 300, 350 and 419 nm, using methanol/HEPES buffer 80:20 solutions as solvent. The data obtained showed that these new fluorescent aminobenzocoumarins are superior to all the previously tested benzocoumarins with the same or different ring fusions. As well as the photolysis, the photophysics of the compounds were characterised by both steady state and time-resolved methods.

Photoactivation of butyric acid from 6-aminobenzocoumarin cages

A new benzocoumarin bearing an amino group is proposed as a photocleavable protecting group for carboxylic acids. The novel heterocycle, 6-amino-4-chloromethyl-2-oxo-2H-naphtho[1,2-b]pyran was used in the preparation of ester conjugates of butyric acid, and of the corresponding mono- and di-methylated or ethylated derivatives. The photolability of the ester conjugates was studied by irradiation at selected wavelengths in methanol/HEPES buffer (80:20) solutions, and the release of butyric acid was followed with HPLC/UV and 1H NMR monitoring. Release of the carboxylic acid was faster for the monoalkylated derivatives (approximately within 20 min), at the longer wavelengths of irradiation (350 and 419 nm). The photophysics of the heterocyclic conjugates was also evaluated by both steady state and time-resolved methods.

Multi-stacks of epitaxial GeSn self-assembled dots in Si: Structural analysis

We report on the growth and structural and morphologic characterization of stacked layers of self-assembled GeSn dots grown on Si (100) substrates by molecular beam epitaxy at low substrate temperature T = 350 °C. Samples consist of layers (from 1 up to 10) of Ge0.96Sn0.04 self-assembled dots separated by Si spacer layers, 10 nm thick. Their structural analysis was performed based on transmission electron microscopy, atomic force microscopy and Raman scattering. We found that up to 4 stacks of dots could be grown with good dot layer homogeneity, making the GeSn dots interesting candidates for optoelectronic device applications.

Eco-friendly luminescent hybrid materials based on EuIII and LiI co-doped chitosan

Biopolymer-based materials have been of particular interest as alternatives do synthetic polymers due to their low toxicity, biodegradability and biocompatibility. Among them, chitosan is one of the most studied ones and has recently been investigated for the application as solid state polymer electrolytes. Furthermore, it can serve as a host for luminescent species such as rare earth ions, giving rise to materials with increased functionality, of particular interest for electrochemical devices. In this study, we investigate chitosan based luminescent materials doped wit Eu3+ and Li+ triflate salts from the structural, photophysical and conductivity points of view. Because the host presents a broad emission band in the blue to green, while Eu3+ emits in the red, fine tuning of emission colour and/or generation of white light is possible by optimizing composition and excitation scheme. Europium lifetimes (5D0) are in the range 270 – 350 µs and quantum yields are as high as 2%. Although Li+ does not interfere with the luminescent properties, it grants ion-conducting properties to the material suggesting that a combination of both properties could be further explored in multifunctional device.

Pró-fármacos fotoativáveis do péptido AAPV: síntese e avaliação da libertação controlada por luz

Dissertação de mestrado em Bioquímica Aplicada (área de especialização em Biomedicina)

Libertação fotocontrolada de moléculas bioativas a partir de conjugados de cumarinas

Dissertação de mestrado em Química Medicinal

Efeito da adição de Zr no endurecimento de ligas Al-Sc

Dissertação de mestrado integrado em Engenharia de Materiais

Influence of emphysema distribution on pulmonary function parameters in COPD patients

Objective: To evaluate the impact that the distribution of emphysema has on clinical and functional severity in patients with COPD. Methods: The distribution of the emphysema was analyzed in COPD patients, who were classified according to a 5-point visual classification system of lung CT findings. We assessed the influence of emphysema distribution type on the clinical and functional presentation of COPD. We also evaluated hypoxemia after the six-minute walk test (6MWT) and determined the six-minute walk distance (6MWD). Results: Eighty-six patients were included. The mean age was 65.2 ± 12.2 years, 91.9% were male, and all but one were smokers (mean smoking history, 62.7 ± 38.4 pack-years). The emphysema distribution was categorized as obviously upper lung-predominant (type 1), in 36.0% of the patients; slightly upper lung-predominant (type 2), in 25.6%; homogeneous between the upper and lower lung (type 3), in 16.3%; and slightly lower lung-predominant (type 4), in 22.1%. Type 2 emphysema distribution was associated with lower FEV1 , FVC, FEV1 /FVC ratio, and DLCO. In comparison with the type 1 patients, the type 4 patients were more likely to have an FEV1 < 65% of the predicted value (OR = 6.91, 95% CI: 1.43-33.45; p = 0.016), a 6MWD < 350 m (OR = 6.36, 95% CI: 1.26-32.18; p = 0.025), and post-6MWT hypoxemia (OR = 32.66, 95% CI: 3.26-326.84; p = 0.003). The type 3 patients had a higher RV/TLC ratio, although the difference was not significant. Conclusions: The severity of COPD appears to be greater in type 4 patients, and type 3 patients tend to have greater hyperinflation. The distribution of emphysema could have a major impact on functional parameters and should be considered in the evaluation of COPD patients.

Aplicação do paradigma Lean em processos clínicos do Centro Hospitalar do Alto Ave

Dissertação de mestrado em Engenharia Industrial