73 research outputs found

    Analysis of Code Blocks for Concern Detection in MATLAB Systems

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    It is known that the support provided by MATLAB for module decomposition is limited. Such limitations give rise to code symptoms, which can be explored for the development of techniques for the detection of concerns, namely unmodularised concerns. Recent work in the area of concern detection in MATLAB systems identified several recurring code patterns that can be associated to the presence of specific concerns. Some of the concerns detected proved to be unmodularised: they cut across the MATLAB system’s modular decomposition. The techniques already developed for detecting unmodularised concerns in MATLAB systems still lack precision and accuracy. As proposed in previous work, the techniques and tools for pinpointing and representing concern-detection patterns need maturing. This thesis contributes with a more accurate structure for representing MATLAB code bases in an intelligent repository for MATLAB code, developed prior to this work. It perfects the structure representing MATLAB code on which the repository is based, by refining the notion of code block, and collects code patterns found in previous publications aggregating them into a catalogue. Subsequently, a preliminary study is made on the application of codes of blocks for the detection of concerns, validating previous concern related patterns and evaluate the existence of new ones

    Síntese e aplicação de novos organocatalisadores de alcalóides de Cinchona em catálise assimétrica

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    Esta tese descreve o projeto, síntese e caracterização de novos derivados de cinchonidina e teve como objetivo central a sua aplicação como organocatalisadores enantiosseletivos em reações catalíticas assimétricas. Os alcalóides de Cinchona modificados com êxito através de metodologias simples, puderam ser agrupados em três famílias distintas, nomeadamente em 1,2,3-triazóis, aminoácidos híbridos e piridinacarboxamidas derivadas da cinchonidina. A capacidade organocatalítica destes compostos foi então estudada em reações assimétricas de Michael, de Biginelli, aldólicas e em hidrossililações de cetiminas, revelando-se um sucesso para os alcalóides modificados com aminoácidos e piridinacarboxamidas. Com estas estruturas foram alcançados bons rendimentos reacionais e elevadas enantiosseletividades em reações aldólicas e em hidrossililações de cetiminas, respetivamente. Destaca-se ainda a potencial e desejada aplicação destas estruturas na síntese enantiosseletiva de compostos biologicamente ativos num futuro próximo. Os bons resultados permitiram o estudo e aplicação dos novos organocatalisadores em diferentes suportes sólidos e a respetiva aplicação em catálise heterogénea assimétrica; Abstract: Synthesis and Application of Novel Organocatalysts Based on Cinchona Alkaloids for Asymmetric Catalysis This thesis describes the design, synthesis and characterization of novel derivatives of cinchonidine and the main goal was their application as organocatalysts in enantioselective catalytic asymmetric reactions. Cinchona alkaloids were successfully modified through simple methods and could be grouped into three distinct families, namely 1,2,3-triazoles, amino acids and pyridinecarboxamide-cinchonidine hybrids. The organocatalytic performance of these compounds was studied in asymmetric reactions such as: the Michael, Biginelli, aldol and ketimine hydrosilylation reactions. The amino acid and pyridinecarboxamide-cinchonidine hybrids were very successful in the ketimine and aldol reactions, showing good yields and high enantioselectivities, respectively. The potential of these organocatalysts for the enantioselective synthesis of biological active compounds in the near future was noted. These good results have subsequently allowed the immobilization of these organocatalysts to different solid supports and their application in heterogeneous asymmetric catalysis

    Cinchona-Derived Picolinamides: Effective Organocatalysts for Stereoselective Imine Hydrosilylation

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    Picolinamide-cinchona organocatalysts for the successful enantioselective reduction of ketomines were developed. For the first time, a new type of chiral Lewis base, a cationic species, is reported to efficiently organocatalyze the addition of trichlorosilane to imines. Excellent yields with good to high enantioselectivities (up to 91%) were obtained in the reduction of differently substituted substrates. Noteworthy, remarkably high turnover frequencies for the hydrosilylation of imines were observed; the catalyst of choice proved to be active even at a loading of only 1 mol-%. The loading was further reduced to 0.5 mol-%, and for very short reaction times (15 min) very impressive asymmetric catalyst efficiency speed values were reached

    Medieval Tuscan glasses from Miranduolo, Italy: A multi-disciplinary study

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    Twenty transparent glass fragments from Miranduolo were analysed by Variable Pressure - Scanning Electron Microscopy - Energy Dispersive System (VP-SEM-EDS), Particle Induced X-Ray Emission and Particle Induced Gamma-Ray Emission (PIXE/PIGE) and Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LAICP- MS). The fragments are dated from mid-13th to mid-14th century CE, when the first Tuscan glass-making workshops emerged. Miranduolo did not have an in situ glass-making workshop. Hence, the aim was to determine the glass production technology and raw material provenance. All the glasses are of plant ash (PA) sodalime- silica (Na-Ca-Si) composition, with eighteen being made with Levantine plant ash (LPA), one with Barilla plant ash (BPA), and one Na-Ca-Si glass with high magnesium and low potassium (HMg-LK). The production of LPA glasses can be distinguished according to the use of different sand typologies as former. It seems probable that glasses were produced regionally from multiple Tuscan glass factories

    Da intervenção da Santa Casa da Misericórdia de Évora: a qualidade das respostas sociais e satisfação percebida dos utentes internos da SCMÉ

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    O Relatório de estágio tem por desígnio, compreender e analisar, o statu quo das dimensões da satisfação (Contemplando o seu bem-estar pessoal e social) dos utentes das valências da Santa Casa da Misericórdia de Évora, por conseguinte, analisando e compreendendo a qualidade de vida desses mesmos utentes, debruçando-se, pois, sobre as potenciais e/ou evidentes necessidades institucionais por suprimir, e problemas sociais por erradicar. O levantamento da actual informação obteve-se através de dois instrumentos metodológicos de recolha de dados: inquérito por questionário de aplicação directa auto-administrada (utentes), e por intermédio de entrevistas semi-estruturadas (diretores técnicos das valências). Relativamente, aos métodos de tratamento de dados, no primeiro instrumento utilizou-se IBM SPSS 22, já no segundo análise de conteúdo. Após a detecção das necessidades existentes, procedeu-se a elaboração de uma proposta de intervenção sócio-organizacional, por forma a solucionar essas mesmas necessidades existentes. O presente documento estrutura-se em 4 eixos: o Eixo 1 – Componente teórica - ; o Eixo 2 – Componente metodológica - ; Eixo 3 – Componente dos resultados - ; Eixo 4 – Componente de intervenção sócio- organizacional; Abstract: Intervention of the Holy House of Mercy of Evora - The quality of the Social Responses and satisfaction perceived Internal SCME of users -. This work is to design, understand and analyze the status quo of the dimensions of satisfaction (Contemplating their personal and social welfare) of users of the valences of the Holy House of Mercy of Evora, therefore, analyzing and understanding the quality life of these same users, addressing therefore, on potential and / or obvious institutional needs to suppress and eradicate social problems. The survey of current information was obtained through two methodological tools for data collection: survey by self-administered direct application questionnaire (users), and through semi-structured interviews (technical directors of valences). With regard to the data processing methods, the first instrument was used SPSS 22, in the second content analysis. After detection of the needs, it proceeded to draw up a proposal for social and organizational intervention in order to solve these same existing needs. This document is divided into four axes: Axis 1 - Theoretical component -; Axis 2 - methodological component -; Axis 3 - Component of results -; Axis 4 - socio-organizational intervention component

    Mapeamento elementar por LA-ICP-MS em sulfuretos da Mina de Miguel Vacas. Resultados preliminares em pirite.

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    Abstract: The Miguel Vacas ancient mine is a copper vein deposit with supergenic enrichment. This site has been the target of exploration and research since 1925 and was exploited until the 80´s. With the aim of studying the mineralogy and mineral paragenesis, metallographic and geochemical methods were used. Firstly, the metallography allowed us to identify the mineral assemblage and its particularities, such as zoning in pyrite. The geochemistry was carried out using LA-ICP.MS (Laser Ablation – Inductively Coupled Plasma – Mass Spectroscopy), which allowed the analysis of minerals by the means of element mapping, for this a set of laser line runs were used. The obtained preliminary results show a distinct growth zones in pyrites, these growth zones present themselves as a chemical zoning. The obtained elemental maps allowed us to chemically distinguish between three different growth areas

    Multi-element profiles as a fingerprint to discriminate estuarine R. philippinarum populations.

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    Filter-feeder bivalves such as non-indigenous Ruditapes philippinarum absorb and accumulate metals, resulting in multi-element signatures. The goal of this study was to analyse if multi-element profiles of R. philippinarum can discriminate between spatial and temporal patterns of estuarine bivalves’ populations. Spatial and temporal variability patterns of chemical profiles were assessed by collecting samples of R. philippinarum and sediment at i) three sites with different environmental and physiological conditions of clams, ii) located within two Portuguese estuaries (Tagus and Sado estuaries) and iii) sampled at three different occasions (May 2018, January 2019, May 2019). This sampling design hypothesized that there are significant differences in the bivalves’ chemical profiles between estuaries, among sampling sites and among sampling occasions. The chemical elements were categorized according to the estuarine geomorphology sources (Se,Co, Ni and Cu), elements with function in metabolic processes of the clams (Mn, Fe, Zn and Cr) and elements derived from the anthropogenic inputs (As, Pb and Cd). The multielement concentrations of clams’ soft tissues and sediments were obtained using a powerful analytical technique, ICP-MS (inductively coupled plasma mass spectrometry). Multivariate differences were tested in multi-element concentrations of bivalves’ soft tissues and sediments. Results revealed that Zn, Co, Ni and Pb were the main contributors for the chemical signatures of Tagus estuary populations, whilst for the Sado estuary populations were Cu, Fe, Cr, As and Cd. These elements were representative of all elemental categories and proved to be spatial and temporal habitat discriminators of bivalves’ estuarine populations. The multi-element signatures of R. philippinarum as a natural tag derived from the physical and chemical conditions of its habitat can be considered as a potential rapid tool for ecological biomonitoring and habitat assessment, accounting for spatial and temporal habitat differences of estuarine populations

    New approaches for the study of faience using beads from Southern Portugal

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    A collection of 30 faience beads recovered from the Iron Age necropolis of Vinha das Caliças 4 (Beja, Portugal) was analyzed in order to identify their production technology and provide insights into their possible provenance. The multi-analytical approach employed, combining laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), variable pressure scanning electron microscope coupled with energy dispersive X-ray spectrometry (VP-SEM-EDS) and micro-X-ray diffraction (µ-XRD), highlights the difficulties that arise from the analysis of weathered faience objects, and which are augmented by their intrinsic heterogeneous nature. VP-SEM-EDS analysis and LA-ICP-MS mapping revealed that the disk-shaped faience beads were manufactured using the cementation glazing method. Copper, most likely in the form of bronze scrapings, was used to impart a blue-green hue to these beads. Micro-XRD also revealed that the disk-shaped beads were manufactured using feldspathic sand. On the other hand, the cubic-shaped bead, identified as an Egyptian blue frit by VP-SEM-EDS and μ-XRD, owes its vivid blue color to the tubular crystals of this well-known synthetic pigment. Trace element analysis suggests that all beads were manufactured in the Levant region using coastal sands. Ultimately, this study highlighted the importance of the use of a combination of microstructural and geochemical criteria in the identification of faience production technology and provenance. The importance of the selection of the sampling strategy in LA-ICP-MS analysis of weathered faience objects was also emphasized.info:eu-repo/semantics/publishedVersio

    Medieval Tuscan glasses from Miranduolo, Italy: A multi-disciplinary study

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    Twenty transparent glass fragments from Miranduolo were analysed by Variable Pressure - Scanning Electron Microscopy - Energy Dispersive System (VP-SEM-EDS), Particle Induced X-Ray Emission and Particle Induced Gamma-Ray Emission (PIXE/PIGE) and Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LAICP- MS). The fragments are dated from mid-13th to mid-14th century CE, when the first Tuscan glass-making workshops emerged. Miranduolo did not have an in situ glass-making workshop. Hence, the aim was to determine the glass production technology and raw material provenance. All the glasses are of plant ash (PA) sodalime- silica (Na-Ca-Si) composition, with eighteen being made with Levantine plant ash (LPA), one with Barilla plant ash (BPA), and one Na-Ca-Si glass with high magnesium and low potassium (HMg-LK). The production of LPA glasses can be distinguished according to the use of different sand typologies as former. It seems probable that glasses were produced regionally from multiple Tuscan glass factories

    GEOCHEMICAL EXPRESSION OF SPELEOTHEME GROWTH FROM XRFAND LA-ICP-MS: PALEOCLIMATIC IMPLICATIONS

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    Carbonate cave deposits have a widespread use in deciphering climatic signals from the past using several proxies (e.g. stable isotope compositions). In the western central part of Portugal, the Mesozoic sediments of the Lusitanian basin are particularly susceptible to dissolve by interaction with meteoric waters and to develop karstic caves, especially in the Lower and Middle Jurassic limestone and dolomitic limestone formations. A set of the existing caves from Sicó and Estremadura Carbonate Massifs (e.g. Soprador do Carvalho, Buraca Grande and Ourão Caves, as well as Vale do Pena and Algar do Pena Caves) were detailed study and several speleothem samples (stalagmites and flowstones) were collected aiming to contribute to the deciphering of the climatic evolution of this region. The selected cave stalagmite was collected in the main epiphreatic conduct of the Soprador do Carvalho Cave (an underground system located on the eastern border of the Sicó Massif) and was studied by handheld X-ray fluorescence to determine the major elements trends and by LA-ICP-MS for the analysis of the minor and trace-elements. The cave floor is covered by siliciclastic fine (clayey/sandy) and clast-supported conglomerate sediments carried into the cave from the adjacent areas by floodwater. As expected, the chemical composition of the speleothem is dominated by the presence of calcium with all samples presenting counts of the same magnitude for this element, although the older portion of the stalagmite has slightly lower counts than the rest of it. Iron is another remarkable element that present a subtle tendency to be more concentrated in the outer (younger) layers. With LA-ICP-MS several transects were made on the thin sections covering layers of distinct optical characteristics. The older layers, which exhibit a more hyaline aspect, have higher counts of elements such as sodium, uranium and lead and lower counts on rare-earth elements and yttrium. More, the analysed elements oscillate between high counts and low counts from layer to layer along the entire sample. The oscillatory character of the trace-element distribution in the stalagmite can be interpreted as the result of the seasonal variations of meteoric water input, and time of residence on the hanging-wall formations, with periods of more efficient dissolution of the percolating water alternating with periods of less efficiency. The more general evolution observed in the composition of older and younger sectors of the speleothem can be interpreted as being the evidence for a probable change in the paleoclimate conditions of the area and perhaps can be used to detect underground flood events during the Quaternary
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