Análise voltamétrica da ciprofloxacina – aplicação a medicamentos e a remediação

O presente trabalho tem como objectivo o desenvolvimento de um método analítico, baseado na voltametria de onda quadrada (SWV), para a análise de ciprofloxacina (CIP) em produtos farmacêuticos e em processos de remediação. Para o desenvolvimento do método voltamétrico foram utilizadas duas células voltamétricas: a célula clássica (utilizando um eléctrodo de trabalho de carbono vítreo - GCE) e um eléctrodo de carbono impresso (SPCE). Após a optimização dos parâmetros da SWV, pH (3,04), frequência (400Hz), incremento de potencial (6 mV) e amplitude do impulso de potencial (40 mV), procedeu-se a validação dos métodos, obtendo-se zonas lineares entre a concentração de CIP e a intensidade de corrente de pico de 5,0×10-6 a 6,0×10-5 mol/L (GCE) e de 1,0×10-5 a 4,0×10-5 mol/L (SPCE) e limites de detecção de 9,48×10-6 mol/L (GCE) e 2,13×10-6 mol/L (SPCE). Verificou-se que a sensibilidade, a precisão e a selectividade são superiores para o SPCE, sendo por isso esta a célula mais adequada para proceder à análise da CIP em produtos farmacêuticos. O SPCE foi aplicado com sucesso à análise de CIP num produto farmacêutico. Para o tratamento de soluções aquosas contendo a CIP foram testados dois oxidantes: o permanganato de potássio e o peróxido de hidrogénio. Para o peróxido de hidrogénio os resultados obtidos foram inconclusivos. No caso do permanganato de potássio, os resultados mostram que a degradação da ciprofloxacina depende da concentração do oxidante. Para uma concentração de CIP de 3,00×10-4 mol/L uma degradação rápida foi obtida com o uso de 6,00×10-3 mol/L de permanganato de potássio. Na aplicação do permanganato na remediação de solos verificou-se que no caso de solos húmicos a ciprofloxacina é adsorvida pelo solo, não sendo possível confirmar a ocorrência da reacção de degradação. No caso de solos arenosos verificou-se que a ciprofloxacina foi rapidamente degradada pelo permanganato de potássio.

Comparative study of amine solutions used in CO2 absorption/desorption cycles

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

Oxidative Leaching of metals from electronic waste with solutions based on quaternary ammonium salts

The treatment of electric and electronic waste (WEEE) is a problem which receives ever more attention. An inadequate treatment results in harmful products ending up in the environment. This project intends to investigate the possibilities of an alternative route for recycling of metals from printed circuit boards (PCBs) obtained from rejected computers. The process is based on aqueous solutions composed of an etchant, either 0.2 M CuCl2.2H2O or 0.2 M FeCl3.6H2O, and a quaternary ammonium salt (quat) such as choline chloride or chlormequat. These solutions are reminiscent of deep eutectic solvents (DES) based on quats. DES are quite similar to ionic liquids (ILs) and are used as well as alternative solvents with a great diversity of physical properties, making them attractive for replacement of hazardous, volatile solvents (e.g. VOCs). A remarkable difference between genuine DES and ILs with the solutions used in this project is the addition of rather large quantities of water. It is shown the presence of water has a lot of advantages on the leaching of metals, while the properties typical for DES still remain. The oxidizing capacities of Cu(II) stem from the existence of a stable Cu(I) component in quat based DES and thus the leaching stems from the activity of the Cu(II)/Cu(I) redox couple. The advantage of Fe(III) in combination with DES is the fact that the Fe(III)/Fe(II) redox couple becomes reversible, which is not true in pure water. This opens perspectives for regeneration of the etching solution. In this project the leaching of copper was studied as a function of gradual increasing water content from 0 - 100w% with the same concentration of copper chloride or iron(III) chloride at room temperature and 80ºC. The solutions were also tested on real PCBs. At room temperature a maximum leaching effect for copper was obtained with 30w% choline chloride with 0.2 M CuCl2.2H2O. The leaching effect is still stronger at 80°C, b ut of course these solutions are more energy consuming. For aluminium, tin, zinc and lead, the leaching was faster at 80ºC. Iron and nickel dissolved easily at room temperature. The solutions were not able to dissolve gold, silver, rhodium and platinum.

A Educação Positiva aplicada à Técnica de Dança Clássica do 3ºAno B da Escola de Dança do Conservatório Nacional

Relatório Final de Estágio apresentado à Escola Superior de Dança, com vista à obtenção do grau de Mestre em Ensino de Dança.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100 mg L−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4 mg g−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

A class of singular first order differential equations with applications in reaction-diffusion

Agências Financiadoras: FCT e MIUR

Detection and diagnosis solutions for fault-tolerant VSI

This paper presents solutions for fault detection and diagnosis of two-level, three phase voltage-source inverter (VSI) topologies with IGBT devices. The proposed solutions combine redundant standby VSI structures and contactors (or relays) to improve the fault-tolerant capabilities of power electronics in applications with safety requirements. The suitable combination of these elements gives the inverter the ability to maintain energy processing in the occurrence of several failure modes, including short-circuit in IGBT devices, thus extending its reliability and availability. A survey of previously developed fault-tolerant VSI structures and several aspects of failure modes, detection and isolation mechanisms within VSI is first discussed. Hardware solutions for the protection of power semiconductors with fault detection and diagnosis mechanisms are then proposed to provide conditions to isolate and replace damaged power devices (or branches) in real time. Experimental results from a prototype are included to validate the proposed solutions.

Overcoming the objectification of western classical music with the concept of music as a process

Dissertation to obtain the degree of Master in Music - Artistic Interpretation

Benchmark exact solutions for the static analysis of multi-layered piezoelectric composite using PVDF

The three-dimensional (3D) exact solutions developed in the early 1970s by Pagano for simply supported multilayered orthotropic composite plates and later in the 1990s extended to piezoelectric plates by Heyliger have been extremely useful in the assessment and development of advanced laminated plate theories and related finite element models. In fact, the well-known test cases provided by Pagano and by Heyliger in those earlier works are still used today as benchmark solutions. However, the limited number of test cases whose 3D exact solutions have been published has somewhat restricted the assessment of recent advanced models to the same few test cases. This work aims to provide additional test cases to serve as benchmark exact solutions for the static analysis of multilayered piezoelectric composite plates. The method introduced by Heyliger to derive the 3D exact solutions has been successfully implemented using symbolic computing and a number of new test cases are here presented thoroughly. Specifically, two multilayered plates using PVDF piezoelectric material are selected as test cases under two different loading conditions and considering three plate aspect ratios for thick, moderately thick and thin plate, in a total of 12 distinct test cases. (C) 2013 Elsevier Ltd. All rights reserved.

From cellulosic based liquid crystalline sheared solutions to 1D and 2D soft materials

Liquid crystalline cellulosic-based solutions described by distinctive properties are at the origin of different kinds of multifunctional materials with unique characteristics. These solutions can form chiral nematic phases at rest, with tuneable photonic behavior, and exhibit a complex behavior associated with the onset of a network of director field defects under shear. Techniques, such as Nuclear Magnetic Resonance (NMR), Rheology coupled with NMR (Rheo-NMR), rheology, optical methods, Magnetic Resonance Imaging (MRI), Wide Angle X-rays Scattering (WAXS), were extensively used to enlighten the liquid crystalline characteristics of these cellulosic solutions. Cellulosic films produced by shear casting and fibers by electrospinning, from these liquid crystalline solutions, have regained wider attention due to recognition of their innovative properties associated to their biocompatibility. Electrospun membranes composed by helical and spiral shape fibers allow the achievement of large surface areas, leading to the improvement of the performance of this kind of systems. The moisture response, light modulated, wettability and the capability of orienting protein and cellulose crystals, opened a wide range of new applications to the shear casted films. Characterization by NMR, X-rays, tensile tests, AFM, and optical methods allowed detailed characterization of those soft cellulosic materials. In this work, special attention will be given to recent developments, including, among others, a moisture driven cellulosic motor and electro-optical devices.

Positive radial solutions of the Dirichlet problem for the Minkowski-Curvature equation in a ball

We study the existence and multiplicity of positive radial solutions of the Dirichlet problem for the Minkowski-curvature equation { -div(del upsilon/root 1-vertical bar del upsilon vertical bar(2)) in B-R, upsilon=0 on partial derivative B-R,B- where B-R is a ball in R-N (N >= 2). According to the behaviour off = f (r, s) near s = 0, we prove the existence of either one, two or three positive solutions. All results are obtained by reduction to an equivalent non-singular one-dimensional problem, to which variational methods can be applied in a standard way.

Travelling wave profiles in some models with nonlinear diffusion

We study some properties of the monotone solutions of the boundary value problem (p(u'))' - cu' + f(u) = 0, u(-infinity) = 0, u(+infinity) = 1, where f is a continuous function, positive in (0, 1) and taking the value zero at 0 and 1, and P may be an increasing homeomorphism of (0, 1) or (0, +infinity) onto [0, +infinity). This problem arises when we look for travelling waves for the reaction diffusion equation partial derivative u/partial derivative t = partial derivative/partial derivative x [p(partial derivative u/partial derivative x)] + f(u) with the parameter c representing the wave speed. A possible model for the nonlinear diffusion is the relativistic curvature operator p(nu)= nu/root 1-nu(2). The same ideas apply when P is given by the one- dimensional p- Laplacian P(v) = |v|(p-2)v. In this case, an advection term is also considered. We show that, as for the classical Fisher- Kolmogorov- Petrovski- Piskounov equations, there is an interval of admissible speeds c and we give characterisations of the critical speed c. We also present some examples of exact solutions. (C) 2014 Elsevier Inc. All rights reserved.

On the HHT, its problems, and some solutions

Mechanical Systems and Signal Processing, Vol.22, Number 6

Recycling of pultrusion production waste into innovative concrete-polymer composite solutions

In this study, the added value resultant from the incorporation of pultrusion production waste into polymer based concretes was assessed. For this purpose, different types of thermoset composite scrap material, proceeding from GFRP pultrusion manufacturing process, were mechanical shredded and milled into a fibrous-powdered material. Resultant GFRP recyclates, with two different size gradings, were added to polyester based mortars as fine aggregate and filler replacements, at various load contents between 4% up to 12% in weight of total mass. Flexural and compressive loading capacities were evaluated and found better than those of unmodified polymer mortars. Obtained results highlight the high potential of recycled GFRP pultrusion waste materials as efficient and sustainable admixtures for concrete and mortar-polymer composites, constituting an emergent waste management solution.

On performance of distributed model predictive control in power system frequency regulation

This paper describes the implementation of a distributed model predictive approach for automatic generation control. Performance results are discussed by comparing classical techniques (based on integral control) with model predictive control solutions (centralized and distributed) for different operational scenarios with two interconnected networks. These scenarios include variable load levels (ranging from a small to a large unbalance generated power to power consumption ratio) and simultaneously variable distance between the interconnected networks systems. For the two networks the paper also examines the impact of load variation in an island context (a network isolated from each other).