Poly(vinylidene fluoride-trifluoroethylene) porous films: tailoring microstructure and physical properties by solvent casting strategies

A systematic study for the production of porous poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), films using solvent evaporation and non-solvent induced phase separation techniques is presented. Processing parameters such as copolymer volume fraction, solvent, preset exposure time to air before immersion, and non-solvent and temperature of the coagulation bath were varied and the corresponding sample morphology, hydrophobicity, thermal and mechanical properties were determined. Film morphologies including homogeneous pore distributions, micropores, microvoids, spherulites and non-porous films were obtained. The morphology variations strongly influence sample hydrophobicity and mechanical properties. All samples crystallize in the electroactive β-phase with a degree of crystallinity around 30 %.

Towards "green" smart materials for force and strain sensors: The case of polyaniline

Stress/strain sensors constitute a class of devices with a global ever-growing market thanks to their use in many fields of modern life. They are typically constituted by thin metal foils deposited on flexible supports. However, the low inherent resistivity and limited flexibility of their constituents make them inadequate for several applications, such as measuring large movements in robotic systems and biological tissues. As an alternative to the traditional compounds, in the present work we will show the advantages to employ a smart material, polyaniline (PANI), prepared by an innovative environmentally friendly route, for force/strain sensor applications wherein simple processing, environmental friendliness and sensitivity are particularly required.

In vitro mechanical fatigue behavior of poly-ε-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and subjected to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behaviour of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow’s criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles.

Dynamic piezoelectric stimulation enhances osteogenic differentiation of human adipose stem cells

This work reports on the influence of the substrate polarization of electroactive β-PVDF on human adipose stem cells (hASCs) differentiation under static and dynamic conditions. hASCs were cultured on different β-PVDF surfaces (non-poled and “poled -”) adsorbed with fibronectin and osteogenic differentiation was determined using a quantitative alkaline phosphatase assay. “Poled -” β-PVDF samples promote higher osteogenic differentiation, which is even higher under dynamic conditions. It is thus demonstrated that electroactive membranes can provide the necessary electromechanical stimuli for the differentiation of specific cells and therefore will support the design of suitable tissue engineering strategies, such as bone tissue engineering.

Hydrophobic/hydrophilic P(VDF-TrFE)/PHEA polymer blend membranes

Polymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co-continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride-co-trifluoroethylene) P(VDF-TrFE). To obtain the composites, in a first stage, P(VDF-TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF-TrFE)/PEO blend membranes were prepared by solvent casting at 70° followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF-TrFE) porous membrane. After removing of the PEO polymer, a P(VDF-TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium-ion battery separator membranes and/or biostable supports for cell culture in biomedical applications.

Erratum: Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (~400 ± 200 nm), morphology, electroactive -phase content (~80-85%) or the degree of crystallinity (Xc of 42 ± 2%), allowing to maintain the excellent physical-chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.

Gd2O3: Eu3+/PPO/POPOP/PS composites for digital imaging radiation detectors

Polymer based scintillator composites have been produced by combining polystyrene (PS) and Gd2O3:Eu3+ scintillator nanoparticles. Polystyrene has been used since it is a flexible and stable binder matrix, resistant to thermal and light deterioration and with suitable optical properties. Gd2O3:Eu3+ has been selected as scintillator material due to its wide band gap, high density and visible light yield. The optical, thermal and electrical characteristics of the composites were studied as a function of filler content, together with their performance as scintillator material. Additionally 1wt.% of 2,5 dipheniloxazol (PPO) and 0.01wt.% of (1,4-bis(2-(5-phenioxazolil))-benzol (POPOP) were introduced in the polymer matrix in order to strongly improve light yield, i.e. the measured intensity of the output visible radiation, under X-ray irradiation. Whereas increasing scintillator filler concentration (from 0.25wt.% to 7.5wt.%) increases scintillator light yield, decreases the optical transparency of the composite. The addition of PPO and POPOP, strongly increased the overall 2 transduction performance of the composite due to specific absorption and re-emission processes. It is thus shown that Gd2O3:Eu3+/PPO/POPOP/PS composites in 0.25 wt.% of scintillator content with fluorescence molecules is suitable for the development of innovate large area X-ray radiation detectors with huge demand from the industries.

Re-Design of ribbon for new applications

O conceito de qualidade de vida surge pela primeira vez em 1920, através do economista inglês Arthur Cecil Pigou, que utiliza este termo para descrever o impacto governamental sobre a vida das pessoas mais desfavorecidas. Com a instalação de uma era industrializada e com o fim da 2º Guerra Mundial, a sociedade mudou de paradigma e iniciou uma procura incessante de formas para melhorar a sua qualidade de vida. Este conceito desenvolve-se juntamente com o desenvolvimento do conceito de educação, saúde, habitação, transporte, trabalho e lazer, bem como indicadores do aumento da esperança de vida, a diminuição da mortalidade infantil e dos níveis de poluição. O avanço da tecnologia teve um papel fundamental para a evolução desses conceitos, bem como o Design na procura de soluções para aplicação dessas mesmas tecnologias. No caso concreto da indústria tèxtil, a tendência é o desenvolvimento de têxteis inteligentes envolvendo a engenharia electrónica no seu processo de conceptualização e de fabrico. A chamada tecnologia wearable abre novos horizontes para a criação de soluções inovadoras, abrindo novos nichos de mercado com elevado valor acrescentado. Existem atualmente vários produtos no mercado cuja funcionalidade e utilidade lhes conferiu um estatuto imutável ao longo dos anos, onde a evolução não avançou na tendência atual. Esse é o caso dos tecidos estreitos, cuja funcionalidade poderá adquirir novas capacidades e ser utilizada em diferentes componentes têxteis nas mais variadas áreas. Essas capacidades poderão ser acrescentadas pela incorporação de materiais com luminosidade (Led’s e L-Wire) nas suas estruturas. Neste estudo realizado o design de produtos com novas funcionalidades, adaptando as tecnologias até agora desenvolvidas em novas soluções e/ou novas recriações de produto.

The Warburg effect in mycobacterial granulomas is dependent on the recruitment and activation of macrophages by interferon-γ

Granulomas are the hallmark of mycobacterial disease. Here, we demonstrate that both the cell recruitment and the increased glucose consumption in granulomatous infiltrates during Mycobacterium avium infection are highly dependent on interferon-y (IFN-y). Mycobacterium avium-infected mice lacking IFN-y signalling failed to developed significant inflammatory infiltrations and lacked the characteristic uptake of the glucose analogue fluorine-18-fluorodeoxyglucose (FDG). To assess the role of macrophages in glucose uptake we infected mice with a selective impairment of IFN-y signalling in the macrophage lineage (MIIG mice). Although only a partial reduction of the granulomatous areas was observed in infected MIIG mice, the insensitivity of macrophages to IFN-y reduced the accumulation of FDG. In vivo, ex vivo and in vitro assays showed that macrophage activated by IFN-y displayed increased rates of glucose uptake and in vitro studies showed also that they had increased lactate production and increased expression of key glycolytic enzymes. Overall, our results show that the activation of macrophages by IFN-y is responsible for the Warburg effect observed in organs infected with M. avium.

Myeloid Sirtuin 2 expression does not impact long-term Mycobacterium tuberculosis control

Sirtuins (Sirts) regulate several cellular mechanisms through deacetylation of several transcription factors and enzymes. Recently, Sirt2 was shown to prevent the development of inflammatory processes and its expression favors acute Listeria monocytogenes infection. The impact of this molecule in the context of chronic infections remains unknown. We found that specific Sirt2 deletion in the myeloid lineage transiently increased Mycobacterium tuberculosis load in the lungs and liver of conditional mice. Sirt2 did not affect long-term infection since no significant differences were observed in the bacterial burden at days 60 and 120 post-infection. The initial increase in M. tuberculosis growth was not due to differences in inflammatory cell infiltrates in the lung, myeloid or CD4+ T cells. The transcription levels of IFN-?, IL-17, TNF, IL-6 and NOS2 were also not affected in the lungs by Sirt2-myeloid specific deletion. Overall, our results demonstrate that Sirt2 expression has a transitory effect in M. tuberculosis infection. Thus, modulation of Sirt2 activity in vivo is not expected to affect chronic infection with M. tuberculosis.

IL-17A promotes intracellular growth of Mycobacterium by inhibiting apoptosis of infected macrophages

The fate of infected macrophages is a critical aspect of immunity to mycobacteria. By depriving the pathogen of its intracellular niche, apoptotic death of the infected macrophage has been shown to be an important mechanism to control bacterial growth. Here, we show that IL-17 inhibits apoptosis of Mycobacterium bovis BCG- or Mycobacterium tuberculosis-infected macrophages thus hampering their ability to control bacterial growth. Mechanistically, we show that IL-17 inhibits p53, and impacts on the intrinsic apoptotic pathway, by increasing the Bcl2 and decreasing Bax expression, decreasing cytochrome c release from the mitochondria, and inhibiting caspase-3 activation. The same effect of IL-17 was observed in infected macrophages upon blockade of p53 nuclear translocation. These results reveal a previously unappreciated role for the IL-17/p53 axis in the regulation of mycobacteria-induced apoptosis and can have important implications in a broad spectrum of diseases where apoptosis of the infected cell is an important host defense mechanism.

The music of language: an ERP investigation of the effects of musical training on emotional prosody processing

Recent studies have demonstrated the positive effects of musical training on the perception of vocally expressed emotion. This study investigated the effects of musical training on event-related potential (ERP) correlates of emotional prosody processing. Fourteen musicians and fourteen control subjects listened to 228 sentences with neutral semantic content, differing in prosody (one third with neutral, one third with happy and one third with angry intonation), with intelligible semantic content (semantic content condition--SCC) and unintelligible semantic content (pure prosody condition--PPC). Reduced P50 amplitude was found in musicians. A difference between SCC and PPC conditions was found in P50 and N100 amplitude in non-musicians only, and in P200 amplitude in musicians only. Furthermore, musicians were more accurate in recognizing angry prosody in PPC sentences. These findings suggest that auditory expertise characterizing extensive musical training may impact different stages of vocal emotional processing.

O erro médico na imprensa portuguesa: quando os pacientes fazem parte da notícia

Esta investigação aborda a qualidade da produção noticiosa sobre o erro médico, como um fator essencial na construção do conhecimento público sobre o tema, com o objetivo de compreender que características definem tal produção e até que ponto poderão ser explicadas pela periodicidade e orientação editorial dos jornais; que conceito de erro médico é veiculado pela produção noticiosa sobre o tema; e quais são os protagonistas no discurso jornalístico sobre o erro médico. Foram analisadas as edições de três jornais portugueses, de 2008 a 2011, resultando num corpus de 266 (4,2%) artigos, que foram classificados de acordo com as seguintes variáveis: as fontes de informação citadas (o seu estatuto e especialidade, no caso dos médicos); os temas que são tratados; as características de enquadramento da informação publicada (tom, género jornalístico; e a presença e número de fontes de informação). Pela análise de conteúdo quantitativa, apurou-se que esse tema está em crescimento, essencialmente com notícias de tom negativo e fontes de informação habitualmente identificadas. Não há evidência para afirmar que a periodicidade e a orientação editorial expliquem as variações dessas características, a não ser relativamente ao número de fontes citadas. Vigoram as notícias centradas nos resultados dos erros (mortes ou lesões), provocados por "erros de omissão" e por "erros de comissão", envolvendo uma diversidade de protagonistas: são, tal como acontece na informação sobre saúde em geral, fontes oficiais e especializadas do campo da saúde. Destacam-se os médicos e os juristas e é dado relevo aos pacientes.

A cadeia produtiva de alimentos orgânicos no vale do rio Cuiabá

Dissertação de mestrado em Estudos de Gestão

Conformal symmetry of the critical 3D Ising model inside a sphere

We perform Monte-Carlo simulations of the three-dimensional Ising model at the critical temperature and zero magnetic field. We simulate the system in a ball with free boundary conditions on the two dimensional spherical boundary. Our results for one and two point functions in this geometry are consistent with the predictions from the conjectured conformal symmetry of the critical Ising model.