Densities and refractive indices for the ternary mixture methanol/propan-1-Ol/acetonitrile

Refractive indices, n(D), and densities, rho, at 298.15 K were measured for the ternary mixture methanol (MeOH)/propan-1-ol (1-PrOH)/acetonitrile (MeCN) for a total of 22 mole fractions, along with 18 mole fractions of each of the corresponding binary mixtures, methanol/propan-1-ol, propan-1-ol/acetonitrile and methanol/acetonitrile. The variation of excess refractive indices and excess molar volumes with composition was modeled by the Redlich-Kister polynomial function in the case of binary mixtures and by the Cibulka equation for the ternary mixture. A thermodynamic approach to excess refractive indices, recently proposed by other authors, was applied for the first time to ternary liquid mixtures. Structural effects were identified and interpreted both in the binary and ternary systems. A complex relationship between excess refractive indices and excess molar volumes was identified, revealing all four possible sign combinations between these two properties. Structuring of the mixtures was also discussed on the basis of partial molar volumes of the binary and ternary mixtures.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

Produção centralizada a biogás - análise do impacto a nível cooperativo

A utilização de energia renovável é hoje tema abordado em todo o mundo, devido à preocupação com a preservação do meio ambiente. Entre as energias renováveis, a biomassa destaca-se pela excelente disponibilidade que possui. Os dejetos bovinos são uma das mais abundantes, o qual tem grande potencial energético, se fermentado corretamente em biodigestores, obtendo como um dos produtos finais, o biogás. Esse gás é constituído na sua maior parte por gás metano (CH4) que é altamente inflamável. Neste trabalho pretende-se fazer a avaliação do potencial energético das propriedades de produção de leite na região do concelho de BRAGA aplicando uma tecnologia de queima de biogás e de produção de eletricidade utilizando um sistema de cogeração convencional e uma tecnologia mais recente, o Organic Rankine Cycle (ORC) e explicitando a respetiva análise económica. As opções por um sistema ORC na central em análise foram justificadas ponderando as vantagens e desvantagens deste ciclo em relação ao ciclo de vapor de água. O objetivo é a obtenção de energia elétrica e térmica e o aumento do rendimento global da instalação com o aproveitamento de todas as energias disponíveis, assim como a eliminação da toxidade dos dejetos para aproveitamento como biomassa. Partindo do levantamento bibliográfico e caraterização das diversas propriedades existentes no concelho, utilizando a tecnologia mais indicada e atual para este tipo de instalação. A biomassa utilizada foi uma mistura de dejetos bovinos com água. O biogás produzido foi convertido em energia elétrica e térmica, através da sua queima. Tem-se assim uma central que além de dar destino adequado aos dejetos animais, diminui a contaminação ambiental, evita a emissão de gás metano para a atmosfera e produz biogás. Efetua-se os cálculos económicos para dois cenários distintos, implementação de uma central de valorização de biogás em cada um dos oito maiores produtores de leite do núcleo de Penso e o aproveitamento dos dejetos produzidos pelos mesmos para implementação de uma central global de recolha dos mesmos, onde é feito o tratamento dos mesmos e a consequente produção de biogás. Na análise económica foram utilizados os seguintes critérios: o VAL (valor atual líquido), a TIR (taxa interna de rendibilidade) e o Período de Retorno Financeiro do Projeto.

Part I : Comparing derivatization methods for amino acids – one and two-step procedures using gas chromatography – flame ion detector (GC-FID) Part II: Story of an icon from its execution until its conservation

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro

Preliminary study of synthesis gas production from water electrolysis, using the ELECTROFUEL (R) concept

This paper describes preliminary work on the generation of synthesis gas from water electrolysis using graphite electrodes without the separation of the generated gases. This is an innovative process, that has no similar work been done earlier. Preliminary tests allowed to establish correlations between the applied current to the electrolyser and flow rate and composition of the generated syngas, as well as a characterisation of generated carbon nanoparticles. The obtained syngas can further be used to produce synthetic liquid fuels, for example, methane, methanol or DME (dimethyl ether) in a catalytic reactor, in further stages of a present ongoing project, using the ELECTROFUEL® concept. The main competitive advantage of this project lies in the built-in of an innovative technology product, from RE (renewable energy) power in remote locations, for example, islands, villages in mountains as an alternative for energy storage for mobility constraints.

Proposta metodológica para avaliação preliminar de jazigos de shale gas

O potencial de um reservatório de shale gas e influenciado por um grande número de fatores, tais como a sua mineralogia e textura, o seu tipo e maturação de querogénio, a saturação de fluidos, os mecanismos de armazenamento de gás, a profundidade do reservatório e a temperatura e pressão de poros. Nesse sentido, o principal objetivo desta tese foi estabelecer uma metodologia de avaliação preliminar de potenciais jazigos de shale gas (estudo de afloramentos com base numa litoestratigrafia de alta resolução), que foi posteriormente aplicada na Formação de Vale das Fontes (Bacia Lusitânica, Portugal). Esta tese tem a particularidade de contribuir, não só para o aprofundamento da informação a nível geoquímico do local, mas também na abordagem inovadora que permitiu a caracterização petrofísica da Formação de Vale das Fontes. Para a aplicação da metodologia estabelecida, foi necessária a realização dos seguintes ensaios laboratoriais: Rock-Eval 6, picnometria de gás hélio, ensaio de resistência a compressão simples, Darcypress e a difracção de raios-X, aplicando o método de Rietveld. Os resultados obtidos na análise petrofísica mostram uma formação rochosa de baixa porosidade que segundo a classificação ISRM, e classificada como ”Resistente”, para alem de revelar comportamento dúctil e elevado índice de fragilidade. A permeabilidade média obtida situa a Formação no intervalo correspondente as permeabilidades atribuídas aos jazigos de tigh gas, indicando a necessidade de fracturação hidráulica, no caso de uma eventual exploração de hidrocarbonetos, enquanto a difracção de raios-X destaca a calcite, o quartzo e os filossilicatos como os minerais mais presentes na Formação. Do ponto de vista geoquímico, os resultados obtidos mostram que apesar do considerável teor médio de carbono orgânico total, a natureza da matéria orgânica analisada e maioritariamente imatura, composta, principalmente, por querogénio do tipo IV, o que indica a incapacidade de a formação gerar hidrocarbonetos em quantidades economicamente exploráveis.

Lettuce (Lactuca sativa L.) leaf-proteome profiles after exposure to cylindrospermopsin and a microcystin-LR/cylindrospermopsin mixture: A concentration-dependent response

The intensification of agricultural productivity is an important challenge worldwide. However, environmental stressors can provide challenges to this intensification. The progressive occurrence of the cyanotoxins cylindrospermopsin (CYN) and microcystin-LR (MC-LR) as a potential consequence of eutrophication and climate change is of increasing concern in the agricultural sector because it has been reported that these cyanotoxins exert harmful effects in crop plants. A proteomic-based approach has been shown to be a suitable tool for the detection and identification of the primary responses of organisms exposed to cyanotoxins. The aim of this study was to compare the leaf-proteome profiles of lettuce plants exposed to environmentally relevant concentrations of CYN and a MC-LR/CYN mixture. Lettuce plants were exposed to 1, 10, and 100 lg/l CYN and a MC-LR/CYN mixture for five days. The proteins of lettuce leaves were separated by twodimensional electrophoresis (2-DE), and those that were differentially abundant were then identified by matrix-assisted laser desorption/ionization time of flight-mass spectrometry (MALDI-TOF/TOF MS). The biological functions of the proteins that were most represented in both experiments were photosynthesis and carbon metabolism and stress/defense response. Proteins involved in protein synthesis and signal transduction were also highly observed in the MC-LR/CYN experiment. Although distinct protein abundance patterns were observed in both experiments, the effects appear to be concentration-dependent, and the effects of the mixture were clearly stronger than those of CYN alone. The obtained results highlight the putative tolerance of lettuce to CYN at concentrations up to 100 lg/l. Furthermore, the combination of CYN with MC-LR at low concentrations (1 lg/l) stimulated a significant increase in the fresh weight (fr. wt) of lettuce leaves and at the proteomic level resulted in the increase in abundance of a high number of proteins. In contrast, many proteins exhibited a decrease in abundance or were absent in the gels of the simultaneous exposure to 10 and 100 lg/l MC-LR/CYN. In the latter, also a significant decrease in the fr. wt of lettuce leaves was obtained. These findings provide important insights into the molecular mechanisms of the lettuce response to CYN and MC-LR/CYN and may contribute to the identification of potential protein markers of exposure and proteins that may confer tolerance to CYN and MC-LR/CYN. Furthermore, because lettuce is an important crop worldwide, this study may improve our understanding of the potential impact of these cyanotoxins on its quality traits (e.g., presence of allergenic proteins).

Characterization of Pinus spp. needles by gas chromatography and mass spectrometry: Application to plant-insect interactions

Dissertação apresentada para obtenção do Grau de Doutor em Ciências do Ambiente pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecn

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Application of Continuous Wavelet Transform to the Analysis of the Modulus of the Fractional Fourier Transform Bands for Resolving Two Component Mixture

In this paper, the fractional Fourier transform (FrFT) is applied to the spectral bands of two component mixture containing oxfendazole and oxyclozanide to provide the multicomponent quantitative prediction of the related substances. With this aim in mind, the modulus of FrFT spectral bands are processed by the continuous Mexican Hat family of wavelets, being denoted by MEXH-CWT-MOFrFT. Four modulus sets are obtained for the parameter a of the FrFT going from 0.6 up to 0.9 in order to compare their effects upon the spectral and quantitative resolutions. Four linear regression plots for each substance were obtained by measuring the MEXH-CWT-MOFrFT amplitudes in the application of the MEXH family to the modulus of the FrFT. This new combined powerful tool is validated by analyzing the artificial samples of the related drugs, and it is applied to the quality control of the commercial veterinary samples.

Fatigue life assessment of exhaust systems for naval gas turbines

Dissertação para obtenção do Grau de Mestre em Engenharia Mecânica

Rat muscle opacity decrease due to the osmosis of a simple mixture

It is known that the fibrous structure of muscle causes light scattering. This phenomenon occurs due to the refractive index discontinuities located between muscle fibers and interstitial fluid. To study the possibility of reducing light scattering inside muscle, we consider its spectral transmittance evolution during an immersion treatment with an optical clearing solution containing ethanol, glycerol, and distilled water. Our methodology consists of registering spectral transmittance of muscle samples while immersed in that solution. With the spectral data collected, we represent the transmittance evolution for some wavelengths during the treatment applied. Additionally, we study the variations that the treatment has caused on the samples regarding tissue refractive index and mass. By analyzing microscopic photographs of tissue cross section, we can also verify changes in the internal arrangement of muscle fibers caused by the immersion treatment. Due to a mathematical model that we develop, we can explain the variations observed in the studied parameters and estimate the amount of optical clearing agent that has diffused into the tissue samples during the immersion treatment. At the end of the study, we observe and explain the improvement in tissue spectral transmittance, which is approximately 65% after 20 min.

Preparation of gas-filled porous microparticles (GPPs) and microbubbles (MBs) by PGSS method

Dissertation to obtain the Master Degree in Biotechnology

Gas emissions on rice culture and its importance on air quality

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil Gestão de Sistemas Ambientais