Organic-inorganic nanostructured multilayers for calcium phosphate biomineralization

The weak fixation of biomaterials within the bone structure is one of the major reasons of implants failures. Calcium phosphate (CaP) coatings are used in bone tissue engineering to improve implant osseointegration by enhancing cellular adhesion, proliferation and differentiation, leading to a tight and stable junction between implant and host bone. It has also been observed that materials compatible with bone tissue either have a CaP coating or develop such a calcified surface upon implantation. Thus, the development of bioactive coatings becomes essential for further improvement of integration with the surrounding tissue. However, most of current applied CaP coatings methods (e.g. physical vapor deposition), cannot be applied to complex shapes and porous implants, provide poor structural control over the coating and prevent incorporation of bioactive organic compounds (e.g. antibiotics, growth factors) because of the used harsh processing conditions. Layer-by-layer (LbL) is a versatile technology that permits the building-up of multilayered polyelectrolyte films in mild conditions based on the alternate adsorption of cationic and anionic elements that can integrate bioactive compounds. As it is recognized in natureâ s biomineralization process the presence of an organic template to induce mineral deposition, this work investigate a ion based biomimetic method where all the process is based on LbL methodology made of weak natural-origin polyelectrolytes. A nanostructured multilayer component, with 5 or 10 bilayers, was produced initially using chitosan and chondroitin sulphate polyelectrolyte biopolymers, which possess similarities with the extracellular matrix and good biocompatibility. The multilayers are then rinsed with a sequential passing of solutions containing Ca2+ and PO43- ions. The formation of CaP over the polyelectrolyte multilayers was confirmed by QCM-D, SEM and EDX. The outcomes show that 10 polyelectrolyte bilayer condition behaved as a  better site for initiating the formation of CaP as the precipitation occur at earlier stages than in 5 polyelectrolyte bilayers one. This denotes that higher number of bilayers could hold the CaP crystals more efficiently. This work achieved uniform coatings that can be applied to any surface with access to the liquid media in a low-temperature method, which potentiates the manufacture of effective bioactive biomaterials with great potential in orthopedic applications.

Seismic vulnerability of existing masonry buildings: Nonlinear parametric analysis

Existing masonry structures are usually associated to a high seismic vulnerability, mainly due to the properties of the materials, weak connections between floors and load-bearing walls, high mass of the masonry walls and flexibility of the floors. For these reasons, the seismic performance of existing masonry structures has received much attention in the last decades. This study presents the parametric analysis taking into account the deviations on features of the gaioleiro buildings - Portuguese building typology. The main objective of the parametric analysis is to compare the seismic performance of the structure as a function of the variations of its properties with respect to the response of a reference model. The parametric analysis was carried out for two types of structural analysis, namely for the non-linear dynamic analysis with time integration and for the pushover analysis with distribution of forces proportional to the inertial forces of the structure. The Young's modulus of the masonry walls, Young's modulus of the timber floors, the compressive and tensile non-linear properties (strength and fracture energy) were the properties considered in both type of analysis. Additionally, in the dynamic analysis, the influences of the vis-cous damping and of the vertical component of the earthquake were evaluated. A pushover analysis proportional to the modal displacement of the first mode in each direction was also carried out. The results shows that the Young's modulus of the masonry walls, the Young's modulus of the timber floors and the compressive non-linear properties are the pa-rameters that most influence the seismic performance of this type of tall and weak existing masonry structures. Furthermore, it is concluded that that the stiffness of the floors influences significantly the strength capacity and the collapse mecha-nism of the numerical model. Thus, a study on the strengthening of the floors was also carried out. The increase of the thickness of the timber floors was the strengthening technique that presented the best seismic performance, in which the reduction of the out-of-plane displacements of the masonry walls is highlighted.

Assessing the production of jet mix columns using alkali activated waste based on mechanical and financial performance and CO2 (eq) emissions

Recent research has proved the potential of alkaline activated fly-ash for soil stabilisation. However, such studies have not focused on the link between financial, mechanical and environmental aspects of this solution, but only on their absolute mechanical properties. The present paper characterises the mechanical behaviour of a large spectrum of activator-ash-soil combinations used to build jet mixing columns, analysing also the cost and CO2 (eq) emissions. The concern with these two vectors forced a decrease in the quantity of stabilising agent added to the soil, relatively to previous research, and the effects of such low quantities have not yet been published. However, the results clearly showed a significant improve in strength, still well above the average values expected when improving the stressstrain behaviour of a weak soil. Uniaxial compressive strength tests were used to assess the effects of the fly-ash percentage, the alkalieash ratio and the water content. The carbon calculator recently developed by the European Federation of Foundation Contractors and the Deep Foundations Institute was used to quantify the CO2 (eq) emissions associated with this technique. The financial cost was estimated based on the experience of a major Portuguese contractor. For comparison purposes, soil cement mixtures were also analysed, using similar conditions and tools used for the soil-ash analysis. Results showed that the cement and ash solutions are very similar in terms of overall performance, with some advantage of the former regarding financial cost, and a significant advantage of the latter regarding the CO2 (eq) emissions. This new grout, although it is in an embryonic stage, it has the potential for broader developments in the field.

Reflexão crítica sobre a redução das pensões no âmbito da convergência dos regimes da Caixa Geral de Aposentações e da Segurança Social

Dissertação de mestrado em Direito Tributário e Fiscal

Measurement of the forward-backward asymmetry of electron and muon pair-production in pp collisions at s√ = 7 TeV with the ATLAS detector

This paper presents measurements from the ATLAS experiment of the forward-backward asymmetry in the reaction pp→Z/γ∗→l+l−, with l being electrons or muons, and the extraction of the effective weak mixing angle. The results are based on the full set of data collected in 2011 in pp collisions at the LHC at s√ = 7 TeV, corresponding to an integrated luminosity of 4.8 fb−1. The measured asymmetry values are found to be in agreement with the corresponding Standard Model predictions. The combination of the muon and electron channels yields a value of the effective weak mixing angle of 0.2308±0.0005(stat.)±0.0006(syst.)±0.0009(PDF), where the first uncertainty corresponds to data statistics, the second to systematic effects and the third to knowledge of the parton density functions. This result agrees with the current world average from the Particle Data Group fit.

Recursos para la alfabetización mediática: investigación y propuestas para niños

Mucho se ha investigado sobre la educación en medios, su importancia y objetivos. Más allá de las Directivas, resoluciones o recomendaciones, la investigación en esta área ha permitido profundizar y solidificar sus fundamentos, al tiempo que ha facilitado el reconocimiento de sus puntos más débiles u omisiones. Uno de los puntos críticos destacados por la formación y por el trabajo de investigación que se ha desarrollado en la Universidad de Miño (Portugal) durante los últimos 20 años, es la inexistencia de recursos y materiales que puedan utilizarse para la promoción de la educación en los medios de comunicación en diferentes contextos. De esta forma, independientemente de los recursos y materiales, se genera la importancia de la transferencia de conocimientos a la práctica, la trascendencia de la mediación del conocimiento producido a su público. Esta preocupación fue la base principal del proyecto titulado «Recursos para la alfabetización mediática» llevado a cabo en el Centro de Estudios de Comunicación y Sociedad y financiado por Evens Foundation (Bélgica). Este trabajo presenta sucintamente los procesos de creación y los resultados generados por estos recursos, centrados en tres medios: televisión, videojuegos e Internet y redes sociales.

Antioxidant potential of two Apiaceae plant extracts: a comparative study focused on the phenolic composition

The present study aimed to characterize the extracts prepared from Pimpinella anisum L. (anise) and Coriandrum sativum L. (coriander) (Apiaceae plants) seeds in terms of phenolic composition, and to correlate the obtained profiles with the antioxidant activity. Anise gave the highest abundance in phenolic compounds (42.09± 0.11 mg/g extract), mainly flavonoids (28.08±0.17 mg/g extract) and phenolic acids (14.01±0.06 mg/g extract), and also the highest antioxidant potential, accessed for the ability to inhibit lipid peroxidation and -carotene bleaching, reducing power and free radical scavenger activity. Apigenin and luteolin derivatives, as also caffeoylquinic acid derivatives appear to be directly related with the higher in vitro antioxidant potential of the anise extract.. In contrast, the weak antioxidant potential of coriander seems to be due to their lower abundance in phenolic compounds (2.24±0.01 mg/g extract). Further studies are necessary to evaluate the in vivo antioxidant potential of the tested extracts, but the performed in vitro experiments highlight them as potential health promoters.

Social entrepreneurship: does institutional environment make a difference?

The purpose of this paper is to contribute to a better understanding of the link between social entrepreneurs and institutional environment in Portugal. A quantitative approach is used in the study, and primary data were collected through an online survey. A questionnaire was emailed to, both, Portuguese Non-Governmental organizations and projects available on the Portuguese social stock exchange. In the analysis of the data were used descriptive statistics, factorial analysis and t-student tests to validate (or not) the research hypotheses. The results show that a favorable institutional environment has a low importance in the decision to develop social initiatives. This conclusion supports the idea that many social entrepreneurs can emerge even in developing regions where the institutional environment is weak. Therefore, social entrepreneurship could be an instrument of regional development and contribute to attenuate the social and economic differences among Portuguese regions.

Characterization of dry-stack interlocking compressed earth blocks

Earth has been a traditional building material to construct houses in Africa. One of the most common techniques is the use of sun dried or kiln fired adobe bricks with mud mortar. Fired bricks are the main cause for deforestation in countries like Malawi. Although this technique is low-cost, the bricks vary largely in shape, strength and durability. This leads to weak houses which suffer considerable damage during floods and seismic events. One solution is the use of dry-stack masonry with stabilized interlocking compressed earth blocks (ICEB). This technology has the potential of substituting the current bricks by a more sustainable kind of block. This study was made in the context of the HiLoTec project, which focuses on houses in rural areas of developing countries. For this study, Malawi was chosen for a case study. This paper presents the experimental results of tests made with dry-stack ICEBs. Soil samples from Malawi were taken and studied. Since the experimental campaign could not be carried out in Malawi, a homogenization process of Portuguese soil was made to produce ICEBs at the University of Minho, Portugal. Then, the compression and tensile strength of the materials was determined via small cylinder samples. Subsequently, the compression and flexural strength of units were determined. Finally, tests to determine the compressive strength of both prisms and masonry wallets and to determine the initial shear strength of the dry interfaces were carried out. This work provides valuable data for low-cost eco-efficient housing

New self-assembled supramolecular hydrogels based on dehydropeptides

Supramolecular hydrogels rely on small molecules that self-assemble in water as a result of the cooperative effect of several relatively weak intermolecular interactions. Peptide-based low molecular weight hydrogelators have attracted enormous interest owing to the simplicity of small molecules combined with the versatility and biocompatibility of peptides. In this work, naproxen, a well known non-steroidal anti-inflammatory drug, was N-conjugated with various dehydrodipeptides to give aromatic peptide amphiphiles that resist proteolysis. Molecular dynamics simulations were used to obtain insight into the underlying molecular mechanism of self-assembly and to rationalize the design of this type of hydrogelators. The results obtained were in excellent agreement with the experimental observations. Only dehydrodipeptides having at least one aromatic amino acid gave hydrogels. The characterization of the hydrogels was carried out using transmission electron microscopy (TEM), circular dichroism (CD), fluorescence spectroscopy and also rheological assays.

Synthesis of new peptide derivatives that self-assemble into nanostructured hydrogels for biomedical applications

Tese de Doutoramento em Ciências (área de especialização em Química)

Closed hybrid hierarchical reservoirs based on the deconstruction of the cellular native microenvironment

The stem cell niche organization and dynamics provide valuable cues for the development of mimetic environments that could have potential to stimulate the regenerative process. We propose the use of biodegradable biomaterials to produce closed miniaturised structures able to encapsulate different cell types or bioactive molecules. In particular, capsules are fabricated using the so-called layer-by-layer technology, where the consecutive (nano-sized) layers are well stabilized by electrostatic interactions or other weak forces. Using alginate-based spherical templates containing cells or other elements (e.g. proteins, magnetic nanoparticles, microparticles) it is possible to produce liquefied capsules that may entrap the entire cargo under mild conditions. The inclusion of liquefied micropcapsules may be used to produce hierarchical compartmentalised systems for the delivery of bioactive agents. The presence of solid microparticles inside such capsules offers adequate surface area for adherent cell attachment increasing the biological performance of these hierarchical systems, while maintain both permeability and injectability. We demonstrated that the encapsulation of distinct cell types (including mesenchymal stem cells and endothelial cells) enhances the osteogenic capability of this system, that could be useful in bone tissue engineering applications.

Optimization of low-cost nutritional supplementation for lignocellulosic ethanol fermentation

[Excerpt] Bioethanol from lignocellulosic materials (LCM), also called second generation bioethanol, is considered a promising alternative to first generation bioethanol. An efficient production process of lignocellulosic bioethanol involves an effective pretreatment of LCM to improve the accessibility of cellulose and thus enhance the enzymatic saccharification. One interesting approach is to use the whole slurry from treatment, since allows economical and industrial benefits: washing steps are avoided, water consumption is lower and the sugars from liquid phase can be used, increasing ethanol concentration [1]. However, during the pretreatment step some compounds (such as furans, phenolic compounds and weak acids) are produced. These compounds have an inhibitory effect on the microorganisms used for hydrolysate fermentation [2]. To overcome this, the use of a robust industrial strain together with agro-industrial by-products as nutritional supplementation was proposed to increase the ethanol productivities and yields. (...)

Climate change research and policy in Portugal

This article offers a review of research and policy on climate change in Portugal and is organized into three main themes: scientific knowledge and assessment of climate change; policy analysis and evaluation; and public engagement. Modern scientific research on meteorology and climatology started in Portugal in the 1950s and a strong community of researchers in climate science, vulnerabilities, impacts, and adaptation has since developed, particularly in the last decade. Nevertheless, there are still many gaps in research, especially regarding the economic costs of climate change in Portugal and costs and benefits of adaptation. Governmental policies with a strong emphasis on mitigation were introduced at the end of the 1990s. As greenhouse gas emissions continued to rise beyond its Kyoto target for 2012, the country had to resort to the Kyoto Flexibility Mechanisms in order to comply. Climate change adaptation policies were introduced in 2010 but are far from being fully implemented. Regarding public engagement with climate change, high levels of concern contrast with limited understanding and rather weak behavioral dispositions to address climate change. Citizens display a heavy reliance on the media as sources of information, which are dominated by a techno-managerial discourse mainly focused on the global level. The final part of the article identifies research gaps and outlines a research agenda. Connections between policy and research are also discussed

In vivo imaging of glycol chitosan-based nanogel biodistribution

The preclinical development of nanomedicines raises several challenges and requires a comprehensive characterization. Among them is the evaluation of the biodistribution following systemic administration. In previous work, the biocompatibility and in vitro targeting ability of a glycol chitosan (GC) based nanogel have been validated. In the present study, its biodistribution in the mice is assessed, using near-infrared (NIR) fluorescence imaging as a tool to track the nanogel over time, after intravenous administration. Rapid whole body biodistribution of both Cy5.5 labeled GC nanogel and free polymer is found at early times. It remains widespreadly distributed in the body at least up to 6 h postinjection and its concentration then decreases drastically after 24 h. Nanogel blood circulation half-life lies around 2 h with the free linear GC polymer presenting lower blood clearance rate. After 24 h, the blood NIR fluorescence intensity associated with both samples decreases to insignificant values. NIR imaging of the organs shows that the nanogel had a body clearance time of 48 h, because at this time point a weak signal of NIR fluorescence is observed only in the kidneys. Hereupon it can be concluded that the engineered GC nanogel has a fairly long blood circulation time, suitable for biomedical applications, namely, drug delivery, simultaneously allowing efficient and quick body clearance.