23 resultados para BLOCK POLYELECTROLYTE SOLUTIONS

em Universidade do Minho


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The layer-by-layer (LbL) deposition method was used to build up alternating layers (five) of different polyelectrolyte solutions (alginate, zein-carvacrol nanocapsules, chitosan and chitosan-carvacrol emulsions) on an aminolysed/charged polyethylene terephthalate (A/C PET) film. These nanolaminated films were characterised by contact angle measurements and through the determination of water vapour (WVTR) and oxygen (O2TR) transmission rates. The effect of active nanolaminated films against the Alternaria sp. and Rhizopus stolonifer was also evaluated. This procedure allowed developing optically transparent nanolaminated films with tuneable water vapour and gas properties and antifungal activity. The water and oxygen transmission rate values for the multilayer films were lower than those previously reported for the neat alginate or chitosan films. The presence of carvacrol and zein nanocapsules significantly decreased the water transmission rate (up to 40 %) of the nanolaminated films. However, the O2TR behaved differently and was only improved (up to 45 %) when carvacrol was encapsulated, i.e. nanolaminated films prepared by alternating alginate with nanocapsules of zein-carvacrol layers showed better oxygen barrier properties than those prepared as an emulsion of chitosan and carvacrol. These films containing zein-carvacrol nanocapsules also showed the highest antifungal activity (30 %), which did not significantly differ from those obtained with the highest amount of carvacrol, probably due to the controlled release of the active agent (carvacrol) from the zein-carvacrol nanocapsules. Thus, this work shows that nanolaminated films prepared with alternating layers of alginate and zein-carvacrol nanocapsules can be considered to improve the shelf-life of foodstuffs.

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Dissertação de mestrado integrado em Engenharia Civil

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Tese de Doutoramento em Engenharia Civil

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Musculoskeletal diseases are one of the leading causes of disability worldwide. Tendon injuries are responsible for substantial morbidity, pain and disability. Tissue engineering strategies aim at translating tendon structure into biomimetic materials. The main goal of the present study is to develop microengineered hydrogel fibers through the combination of microfabrication and chemical interactions between oppositely charged polyelectrolytes. For this, methacrylated hyaluronic acid (MeHA) and chondroitin sulfate (MeCS) were combined with chitosan (CHT). Hydrogel fibers were obtained by injecting polymer solutions (either MeHA or MeHA/MeCS and CHT) in separate microchannels that join at a y-junction, with the materials interacting upon contact at the interface. To evaluate cell behavior, human tendon derived cells (hTDCs) were isolated from tendon surplus samples during orthopedic surgeries and seeded on top of the fibers. hTDCs adhered to the surface of the fibers, remaining viable, and were found to be expressing CD44, the receptor for hyaluronic acid. The synthesis of hydrogel fibers crosslinkable through both physical and chemical mechanisms combined with microfabrication technology allows the development of biomimetic structures with parallel fibers being formed towards the replication of tendon tissue architecture.

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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.

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Implantable devices must exhibit mechanical properties similar to native tissues to promote appropriate cellular behavior and regeneration. Herein, we report a new membrane manufacture method based on the synthesis of polyelectrolyte complexes (PECs) that exhibit saloplasticity, i.e. variable physical-chemistry using salt as a plasticizer. This is a Green Chemistry approach, as PECs generate structures that are stabilized solely by reversible electrostatic interactions, avoiding the use of harmful crosslinkers completely. Furthermore, natural polyelectrolytes - chitosan and alginate - were used. Upon mixing them, membranes were obtained by drying the PECs at 37ºC, yielding compact PECs without resorting to organicsolvents. The plasticizing effect of salt after synthesis was shown by measuring tensile mechanical properties, which were lower when samples were immersed in high ionic strength solutions.Salt was also used during membrane synthesis in different quan- tities (0 M, 0.15 M and 0.5 M in NaCl) yielding structures with no significant differences in morphology and degradation (around 15% after 3 months in lysozyme). However, swelling was higher (about 10x) when synthesized in the presence of salt. In vitro cell studies using L929 fibroblasts showed that cells adhered and proliferated preferentially in membranes fabricated in the presence of salt (i.e. the membranes with lower tensile strength). Structures with physical-chemical properties controlled with precision open a path to tissue engineering strategies depending on fine tuning mechanical properties and cellular adhesion simply by changing ionic strength during membrane manufacture

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The regeneration of soft biological tissues requires new substitutes that exhibit mechanical properties similar to the native tissue. Herein, thin saloplastic membranes with tunable physical properties are prepared by complexation of chitosan and alginate solutions containing different concentrations of sodium chloride. Polyelectrolyte complexes (PECs) are transferred to flat Petri dishes for compaction into membrane shapes by sedimentation and solvent evaporation. All membranes are resistant to degradation by lysozyme and are stable in solutions with pH values between 1 and 13. Immersing the different membranes in new doping solutions of increasing salt concentrations triggers the typical saloplastic behavior, with a high water absorption and decrease of the rigidity and ultimate tensile strength. The range of such variations is tuned by the sodium chloride amount used in the synthesis: high salt concentrations increase water uptake and tensile moduli, while decreasing the ultimate strength. Cellular assays demonstrate high proliferation rates and viability of L929 fibroblasts seeded onto the most rigid membranes. The results validate the use of saloplastic membranes as soft tissue substitutes for future biomedical applications.

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Electric Vehicles (EVs) are increasingly used nowadays, and different powertrain solutions can be adopted. This paper describes the control system of an axial flux Permanent Magnet Synchronous Motor (PMSM) for EVs powertrain. It is described the implemented Field Oriented Control (FOC) algorithm and the Space Vector Modulation (SVM) technique. Also, the mathematical model of the PMSM is presented. Both, simulation and experimental, results with different types of mechanical load are presented. The experimental results were obtained using a laboratory test bench. The obtained results are discussed.

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Since concrete is the most widely utilized construction material, several solutions are currently being developed and investigated for enhancing the sustainability of cementitious materials. One of these solutions is based on producing Recycled Concrete Aggregates (RCA) from existing concrete members resulting by either industrial processes or demolitions of existing structures as a whole. Moreover, waste resulting from industrial processes other than the building construction (i.e., tire recycling, production of steel, powders resulting from other depuration processes) are also being considered as possible low-impact constituents for producing structural concrete and Fiber-Reinforced Cementitious Composites (FRCC). Furthermore, the use of natural fibers is another option for producing environmentally-friendly and cost-effective materials, depending on the local availability of raw materials. To promote the use of concretes partially composed of recycled constituents, their influence on the mechanical and durability performance of these concretes have to be deeply investigated and correlated. This was the main goal of the EnCoRe Project (www.encore-fp7.unisa.it), a EU-funded initiative, whose activities and main findings are summarized in this paper.

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The structural analysis involves the definition of the model and selection of the analysis type. The model should represent the stiffness, the mass and the loads of the structure. The structures can be represented using simplified models, such as the lumped mass models, and advanced models resorting the Finite Element Method (FEM) and Discrete Element Method (DEM). Depending on the characteristics of the structure, different types of analysis can be used such as limit analysis, linear and non-linear static analysis and linear and non-linear dynamic analysis. Unreinforced masonry structures present low tensile strength and the linear analyses seem to not be adequate for assessing their structural behaviour. On the other hand, the static and dynamic non-linear analyses are complex, since they involve large time computational requirements and advanced knowledge of the practitioner. The non-linear analysis requires advanced knowledge on the material properties, analysis tools and interpretation of results. The limit analysis with macro-blocks can be assumed as a more practical method in the estimation of maximum load capacity of structure. Furthermore, the limit analysis require a reduced number of parameters, which is an advantage for the assessment of ancient and historical masonry structures, due to the difficult in obtaining reliable data.

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IP networks are currently the major communication infrastructure used by an increasing number of applications and heterogeneous services, including voice services. In this context, the Session Initiation Protocol (SIP) is a signaling protocol widely used for controlling multimedia communication sessions such as voice or video calls over IP networks, thus performing vital functions in an extensive set of public and enter- prise solutions. However, the SIP protocol dissemination also entails some challenges, such as the complexity associated with the testing/validation processes of IMS/SIP networks. As a consequence, manual IMS/SIP testing solutions are inherently costly and time consuming tasks, being crucial to develop automated approaches in this specific area. In this perspective, this article presents an experimental approach for automated testing/validation of SIP scenarios in IMS networks. For that purpose, an automation framework is proposed allowing to replicate the configuration of SIP equipment from the pro- duction network and submit such equipment to a battery of tests in the testing network. The proposed solution allows to drastically reduce the test and validation times when compared with traditional manual approaches, also allowing to enhance testing reliability and coverage. The automation framework comprises of some freely available tools which are conveniently integrated with other specific modules implemented within the context of this work. In order to illustrate the advantages of the proposed automated framework, a real case study taken from a PT Inovação customer is presented comparing the time required to perform a manual SIP testing approach with the one time required when using the proposed auto- mated framework. The presented results clearly corroborate the advantages of using the presented framework.

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This work provides analytical and numerical solutions for the linear, quadratic and exponential Phan–Thien–Tanner (PTT) viscoelastic models, for axial and helical annular fully-developed flows under no slip and slip boundary conditions, the latter given by the linear and nonlinear Navier slip laws. The rheology of the three PTT model functions is discussed together with the influence of the slip velocity upon the flow velocity and stress fields. For the linear PTT model, full analytical solutions for the inverse problem (unknown velocity) are devised for the linear Navier slip law and two different slip exponents. For the linear PTT model with other values of the slip exponent and for the quadratic PTT model, the polynomial equation for the radial location (β) of the null shear stress must be solved numerically. For both models, the solution of the direct problem is given by an iterative procedure involving three nonlinear equations, one for β, other for the pressure gradient and another for the torque per unit length. For the exponential PTT model we devise a numerical procedure that can easily compute the numerical solution of the pure axial flow problem

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Doctoral Thesis Civil Engineering

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Thermoplastic elastomers based on a triblock copolymer styrene-butadiene-styrene (SBS) with different butadiene/styrene ratios, block structure and carbon nanotube (CNT) content were submitted to accelerated weathering in a Xenontest set up, in order to evaluate their stability to UV ageing. It was concluded that ageing mainly depends on butadiene/styrene ratio and block structure, with radial block structures exhibiting a faster ageing than linear block structures. Moreover, the presence of carbon nanotubes in the SBS copolymer slows down the ageing of the copolymer. The evaluation of the influence of ageing on the mechanical and electrical properties demonstrates that the mechanical degradation is higher for the C401 sample, which is the SBS sample with the largest butadiene content and a radial block structure. On the other hand, a copolymer derivate from SBS, the styrene-ethylene/butadiene-styrene (SEBS) sample, retains a maximum deformation of ~1000% after 80 h of accelerated ageing. The hydrophobicity of the samples decreases with increasing ageing time, the effect being larger for the samples with higher butadiene content. It is also verified that cytotoxicity increases with increasing UV ageing with the exception of SEBS, which remains not cytotoxic up to 80 h of accelerated ageing time, demonstrating its potential for applications involving exposition to environmental conditions.

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The Portuguese housing sector experienced a significant growth throughout the 20th century, particularly in the last quarter, after the democratic revolution in 1974. In fact, the number of buildings built between 1970 and 1990 is more than one third of the buildings actually existing in Portugal. Therefore most of them were built before the publication of the first regulation concerning the energy efficiency in buildings. Regarding this scenario, it would be expected that rehabilitation activities would represent most of the current construction activities. However, given some remaining barriers from old social policies, this situation is not observed; actually building retrofitting is the least significant sector, accentuating the degradation level of major part of the Portuguese housing stock. Several studies show that the main problems are found in the buildings envelope elements, such as roofs and façades. Based on this context, the aim of this paper is to introduce some examples of building retrofitting systems that, adapted to the Portuguese main needs and requirements may represent sustainable solutions to overcome the identified needs of Portuguese buildings' envelope.