Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose: The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated. Methods: The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH 2 and 8. Results: The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid–base properties, point of zero charge—pHpzc). The solution pH influences both the sorbent’s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH 2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH 2 experimental data to which the Freundlich model fitted better. Conclusion: Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.

Solution enthalpies of 1,4-dioxane: Study of solvent effects through quantitative structure-property relationships

Solution enthalpies of 1,4-dioxane have been obtained in 15 protic and aprotic solvents at 298.15 K. Breaking the overall process through the use of Solomonov's methodology the cavity term was calculated and interaction enthalpies (Delta H-int) were determined. Main factors involved in the interaction enthalpy have been identified and quantified using a QSPR approach based on the TAKA model equation. The relevant descriptors were found to be pi* and beta, which showed, respectively, exothermic and endothermic contributions. The magnitude of pi* coefficient points toward non-specific solute-solvent interactions playing a major role in the solution process. The positive value of the beta coefficient reflects the endothermic character of the solvents' hydrogen bond acceptor (HBA) basicity contribution, indicating that solvent molecules engaged in hydrogen bonding preferentially interact with each other rather than with 1,4-dioxane. (C) 2013 Elsevier B.V. All rights reserved.

Utilização de metodologias multicritério de apoio à decisão como ferramenta de suporte numa empresa de serviços energéticos

Atualmente e devido às conjunturas sócio económicas que as empresas atravessam, é importante maximizar tanto os recursos materiais como humanos. Essa consciência faz com que cada vez mais as empresas tentem que os seus colaboradores possam desempenhar um papel importante no processo de decisão. Cada vez mais a diferença entre o sucesso e o fracasso depende da estratégia que cada empresa opte por envergar. Sendo assim cada atividade desempenhada por um seu colaborador deve estar alinhada com os objetivos estratégicos da empresa. O contexto em que a presente tese se insere tem por base uma pesquisa aos vários métodos multicritério existentes, de forma a que o serviço que seja adjudicado possa ser executado de forma transparente e eficiente, sem nunca descorar a sua otimização. O método de apoio à decisão escolhido foi o Analytic Hierarchy Process (AHP). A necessidade de devolver aos decisores/gestores a melhor solução resultante da aplicação de um método de apoio à decisão numa empresa de serviços energéticos foi a base para a escolha da tese. Dos resultados obtidos conclui-se que a aplicação do método AHP foi adequada, conseguindo responder a todos os objetivos inicialmente propostos. Foi também possível verificar os benefícios que advêm da sua aplicação, que por si só, ajudaram a perceber que é necessário haver uma maior entreajuda e consenso entre as decisões a tomar.

Deteção eletroquímica da norfloxacina e trimetoprim em amostras de urina utilizando polímero molecularmente impresso modificado e grafeno

A norfloxacina e o trimetoprim são dois antibióticos antibacterianos usados para o tratamento de infeções urinárias, intestinais e respiratórias. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabolitos é assim um controlo imperioso e em muitos casos regular no tratamento de um paciente. Neste trabalho desenvolveram-se dois sensores eletroquímicos para a deteção da norfloxacina (NFX) e do trimetoprim (TMP), usando como superfície de suporte o carbono vítreo. A busca de novos materiais que conferiram maior seletividade e sensibilidade aos sistemas de deteção e por outro lado apresentem menores riscos para o paciente quando usados em dispositivos que permitam uma análise point-of-care, é especialmente importante e pode ser uma parte crucial do processo de decisão clínica. Assim, os polímeros molecularmente impresos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais avaliado. A impressão molecular é uma tecnologia capaz de produzir polímeros que incorporam as moléculas do analito e que após remoção por solventes específicos, permitem dotá-los de locais específicos de reconhecimento estereoquímico. A seleção do pirrol como polímero molecularmente impresso (MIP) permitiu construir com sucesso os sensores para doseamento dos antibióticos. A fim de aumentar a sensibilidade do método incorporou-se grafeno na superfície do elétrodo. Este material tem vindo a ser largamente utilizado devido às suas propriedades: estrutura molecular, condutividade elétrica e aumento da superfície são algumas das características que mais despertam o interesse para a sua aplicação neste projeto. Os sensores desenvolvidos foram incorporados em sistemas eletroquímicos. Os métodos voltamétricos aplicados foram a voltametria cíclica, a voltametria de onda quadrada e ainda a impedância. As condições de análise foram otimizadas no que respeita à polimerização do pirrol (concentração do polímero, número de ciclos de eletropolimerização e respetivos potenciais aplicados, tempo de incubação, solvente de remoção do analito), ao pH da solução do fármaco, à gama de concentrações dos antibióticos e aos parâmetros voltamétricos dos métodos de análise. Para cada um dos antibióticos um elétrodo não-impresso foi também preparado, usando o procedimento de polimerização mas sem a presença da molécula do analito, e foi usado como controlo. O sensor desenvolvido para o trimetoprim foi usado no doseamento do fármaco em amostras de urina. As amostras foram analisadas sem qualquer diluição, apenas foram centrifugadas para remoção de proteínas e algum interferente. Os sensores construídos apresentaram comportamento linear na gama de concentrações entre 102 e 107 mol/L. Os resultados mostram boa precisão (desvios padrão inferiores a 11%) e os limites de deteção foram de 8,317 e 1,307 mol/L para a norfloxacina e o trimetoprim, respetivamente. Para validação do método foram ainda efetuados ensaios de recuperação tendo obtido valores superiores a 94%.

Sustainable waste recycling solution for the glass fibre reinforced polymer composite materials industry

In this paper the adequacy and the benefit of incorporating glass fibre reinforced polymer (GFRP) waste materials into polyester based mortars, as sand aggregates and filler replacements, are assessed. Different weight contents of mechanically recycled GFRP wastes with two particle size grades are included in the formulation of new materials. In all formulations, a polyester resin matrix was modified with a silane coupling agent in order to improve binder-aggregates interfaces. The added value of the recycling solution was assessed by means of both flexural and compressive strengths of GFRP admixed mortars with regard to those of the unmodified polymer mortars. Planning of experiments and data treatment were performed by means of full factorial design and through appropriate statistical tools based on analyses of variance (ANOVA). Results show that the partial replacement of sand aggregates by either type of GFRP recyclates improves the mechanical performance of resultant polymer mortars. In the case of trial formulations modified with the coarser waste mix, the best results are achieved with 8% waste weight content, while for fine waste based polymer mortars, 4% in weight of waste content leads to the higher increases on mechanical strengths. This study clearly identifies a promising waste management solution for GFRP waste materials by developing a cost-effective end-use application for the recyclates, thus contributing to a more sustainable fibre-reinforced polymer composites industry.

Avaliação de operadoras de saúde por usuários pelo método Analytic Hierarchy Process

OBJETIVO: Analisar a qualidade dos serviços oferecidos por empresas operadoras de planos de saúde, segundo a percepção de usuários. MÉTODOS: Estudo transversal com 360 usuários de sete operadoras de planos de saúde da cidade de Curitiba, PR, e região metropolitana em 2008. Foi aplicado questionário sobre as preferências dos usuários em relação a seis atributos (localização dos pontos de atendimento; efetividade da ação dos médicos, clínicas e hospitais; rapidez e amabilidade no atendimento; facilidade na liberação de guias; preço; abrangência da rede credenciada) de cada uma das empresas operadoras. Para a análise das respostas foi utilizado o método Analytic Hierarchy Process (AHP, ou Processo Analítico de Hierarquia), ferramenta de análise de decisão e planejamento de múltiplos critérios. RESULTADOS: O atributo mais valorizado pelos usuários foi "preço". As empresas foram agrupadas em dois conjuntos de preferências em relação aos atributos: dos sete planos de saúde, dois apresentaram menor preferência (entre 23% e 19%) e cinco, maior preferência (em torno de 10%). CONCLUSÕES: Com esse tipo de pesquisa, as empresas operadoras de planos de saúde poderiam reformular suas estruturas, processos, preços e redes credenciadas com o objetivo de melhorar seu posicionamento no mercado.

GTS allocation analysis in IEEE 802.15.4 for real-time wireless sensor networks

The IEEE 802.15.4 protocol proposes a flexible communication solution for Low-Rate Wireless Personal Area Networks including sensor networks. It presents the advantage to fit different requirements of potential applications by adequately setting its parameters. When enabling its beacon mode, the protocol makes possible real-time guarantees by using its Guaranteed Time Slot (GTS) mechanism. This paper analyzes the performance of the GTS allocation mechanism in IEEE 802.15.4. The analysis gives a full understanding of the behavior of the GTS mechanism with regards to delay and throughput metrics. First, we propose two accurate models of service curves for a GTS allocation as a function of the IEEE 802.15.4 parameters. We then evaluate the delay bounds guaranteed by an allocation of a GTS using Network Calculus formalism. Finally, based on the analytic results, we analyze the impact of the IEEE 802.15.4 parameters on the throughput and delay bound guaranteed by a GTS allocation. The results of this work pave the way for an efficient dimensioning of an IEEE 802.15.4 cluster.

The extended unsymmetric frontal solution for multiple-point constraints

The purpose of this paper is to discuss the linear solution of equality constrained problems by using the Frontal solution method without explicit assembling. Design/methodology/approach - Re-written frontal solution method with a priori pivot and front sequence. OpenMP parallelization, nearly linear (in elimination and substitution) up to 40 threads. Constraints enforced at the local assembling stage. Findings - When compared with both standard sparse solvers and classical frontal implementations, memory requirements and code size are significantly reduced. Research limitations/implications - Large, non-linear problems with constraints typically make use of the Newton method with Lagrange multipliers. In the context of the solution of problems with large number of constraints, the matrix transformation methods (MTM) are often more cost-effective. The paper presents a complete solution, with topological ordering, for this problem. Practical implications - A complete software package in Fortran 2003 is described. Examples of clique-based problems are shown with large systems solved in core. Social implications - More realistic non-linear problems can be solved with this Frontal code at the core of the Newton method. Originality/value - Use of topological ordering of constraints. A-priori pivot and front sequences. No need for symbolic assembling. Constraints treated at the core of the Frontal solver. Use of OpenMP in the main Frontal loop, now quantified. Availability of Software.

A remote engineering solution for automating a roller hearth kiln

Remote engineering (also known as online engineering) may be defined as a combination of control engineering and telematics. In this area, specific activities require computacional skills in order to develop projects where electrical devives are monitored and / or controlled, in an intercative way, through a distributed network (e.g. Intranet or Internet). In our specific case, we will be dealing with an industrial plant. Within the last few years, there has been an increase in the number of activities related to remote engineering, which may be connected to the phenomenon of the large extension experienced by the Internet (e.g. bandwith, number of users, development tools, etc.). This increase opens new and future possibilities to the implementation of advance teleworking (or e-working) positions. In this paper we present the architecture for a remote application, accessible through the Internet, able to monitor and control a roller hearth kiln, used in a ceramics industry for firing materials. The proposed architecture is based on a micro web server, whose main function is to monitor and control the firing process, by reading the data from a series of temperature sensors and by controlling a series of electronic valves and servo motors. This solution is also intended to be a low-cost alternative to other potential solutions. The temperature readings are obtained through K-type thermopairs and the gas flow is controlled through electrovalves. As the firing process should not be stopped before its complete end, the system is equipped with a safety device for that specific purpose. For better understanding the system to be automated and its operation we decided to develop a scale model (100:1) and experiment on it the devised solution, based on a Micro Web Server.

Human-robot teamwork: a knowledge-based solution

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Electrotécnica e de Computadores

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Reliability and availability in reconfigurable computing: a basis for a common solution

Dynamically reconfigurable SRAM-based field-programmable gate arrays (FPGAs) enable the implementation of reconfigurable computing systems where several applications may be run simultaneously, sharing the available resources according to their own immediate functional requirements. To exclude malfunctioning due to faulty elements, the reliability of all FPGA resources must be guaranteed. Since resource allocation takes place asynchronously, an online structural test scheme is the only way of ensuring reliable system operation. On the other hand, this test scheme should not disturb the operation of the circuit, otherwise availability would be compromised. System performance is also influenced by the efficiency of the management strategies that must be able to dynamically allocate enough resources when requested by each application. As those resources are allocated and later released, many small free resource blocks are created, which are left unused due to performance and routing restrictions. To avoid wasting logic resources, the FPGA logic space must be defragmented regularly. This paper presents a non-intrusive active replication procedure that supports the proposed test methodology and the implementation of defragmentation strategies, assuring both the availability of resources and their perfect working condition, without disturbing system operation.

Solution enthalpies of hydroxylic compounds

Solution enthalpies of adamantan-1-ol, 2-methyl- butan-2-ol, and 3-methylbutan-1-ol have been measured at 298.15 K, in a set of 16 protogenic and non-protogenic solvents. The identification and quantification of solvent effects on the solution processes under study were performed using quantitative-structure property relationships. The results are discussed in terms of solute-solvent-solvent interactions and also in terms of the influence of compound's size and position of its hydroxyl group.

Is the electric vehicle a solution for the wind power integration in the portuguese power system?

The integration of Plug-in electric vehicles in the transportation sector has a great potential to reduce oil dependency, the GHG emissions and to contribute for the integration of renewable sources into the electricity generation mix. Portugal has a high share of wind energy, and curtailment may occur, especially during the off-peak hours with high levels of hydro generation. In this context, the electric vehicles, seen as a distributed storage system, can help to reduce the potential wind curtailments and, therefore, increase the integration of wind power into the power system. In order to assess the energy and environmental benefits of this integration, a methodology based on a unit commitment and economic dispatch is adapted and implemented. From this methodology, the thermal generation costs, the CO2 emissions and the potential wind generation curtailment are computed. Simulation results show that a 10% penetration of electric vehicles in the Portuguese fleet would increase electrical load by 3% and reduce wind curtailment by only 26%. This results from the fact that the additional generation required to supply the electric vehicles is mostly thermal. The computed CO2 emissions of the EV are 92 g CO2/kWh which become closer to those of some new ICE engines.

Método AHP como optimização na selecção de fornecedores numa empresa de materiais de construção

Nos dias que correm cada vez mais a diferença entre o sucesso e o fracasso de uma empresa depende da estratégia que escolhem seguir, sendo de igual forma importante maximizar quer os recursos materiais quer os recursos humanos. Assim sendo, cada vez mais empresas optam por incentivar os seus colaboradores a desempenhar um papel importante no processo de decisão. Para isso a estratégia da empresa tem de estar alinhada com cada actividade desempenhada pelos seus colaboradores. Esta dissertação tem por base uma pesquisa de vários métodos multicritério existentes, tendo sido escolhido o método Analytic Hierarchy Process (AHP) para determinar o melhor fornecedor de cimento para a empresa Materiais de Construção da Minhoteira, Lda. Foi então necessário desenvolver um software tendo por base o Excel que permitisse fazer a análise das diversas alternativas perante os critérios mencionados. A aplicação informática “Make and Choice” procura contribuir da melhor forma para uma escolha potencialmente mais acertada. Conclui-se que “Make and Choice”, utilizando o método AHP, foi adequada para conseguir responder a todos os objectivos inicialmente propostos, foi ainda possível verificar os benefícios que advêm da sua aplicação. E desta forma, perceber que é possível ter o auxílio na tomada de decisão de ferramentas ou métodos que permitem obter a melhor solução.