Proposta de implementação de uma metodologia SMED numa metalomecânica

O presente trabalho é o resultado de um projecto experimental que teve como principal objetivo a redução dos tempos de setup, através da implementação da metodologia Single Minute Exchange of Die (SMED) em equipamentos de eletroerosão (EDM) por fio e penetração. Para garantir o sucesso da implementação, após uma revisão bibliográfica centrada no tema SMED, estabelece-se uma metodologia, numa lógica de melhoria contínua análoga a um ciclo PDCA. A metodologia estabelecida envolve as seguintes fases: caracterização da situação inicial, observação, recolha de dados, análise dos dados e implementação SMED. A caracterização da situação inicial visa qualificar a situação encontrada e identificar a zona de atuação - equipamentos em estudo. A observação do processo produtivo é suportada pela ferramenta fluxograma do processo, por sua vez, a recolha de dados visa a avaliação inicial e nessa perspectiva recorre-se à abordagem OEE. Na fase de análise dos dados são introduzidas as ferramentas de análise VSM e diagrama de causa e efeito que auxiliam a identificação de um conjunto de acções de melhoria, a realizar previamente à fase de implementação SMED, culminando assim uma fase PRÉ-SMED. Reunidas as condições ideais iniciou-se a implementação efectiva da metodologia SMED obtendo-se reduções do tempo total de setup superiores a 60%. O presente estudo permite concluir que podem surgir diferenças significativas em diversas aplicações SMED, enfatizando a importância de uma fase PRÉ-SMED de modo a potenciar os resultados alcançados com uma implementação SMED.

Modelo gerador de questões no reforço da aprendizagem das radiações e conteúdos de física moderna no ensino secundário

Os avanços e a disseminação do uso das Tecnologias de Informação e Comunicação (TIC) descortinam novas perspetivas para a educação com suporte em ambientes digitais de aprendizagem usados via internet (Fiolhais & Trindade, 2003). A plataforma usada no Projeto Matemática Ensino (PmatE) da Universidade de Aveiro (UA) é uma das ferramentas informáticas que suporta esses ambientes através da avaliação baseada no Modelo Gerador de Questões (MGQ), possibilitando a obtenção da imagem do progresso feito pelos alunos (Vieira, Carvalho & Oliveira, 2004). Reconhecendo a importância didática desta ferramenta, já demonstrada noutras investigações (por exemplo, Carvalho, 2011; Pais de Aquino, 2013; Peixoto, 2009), o presente estudo tem como objetivo geral desenvolver material didático digital de Física, no contexto do programa moçambicano de Física da 12ª classe, para alunos e professores sobre radiações e conteúdos da Física Moderna. Pretendeu-se, ainda, propor estratégias de trabalho com recurso às TIC para a melhoria da qualidade das aprendizagens nesta disciplina. O estudo assentou nas três seguintes questões de investigação: (a) Como conceber instrumentos de avaliação das aprendizagens baseadas no modelo gerador de questões para o estudo das radiações e conteúdos da Física Moderna, no contexto do programa moçambicano de Física da 12ª classe? (b) Que potencialidades e constrangimentos apresentam esses instrumentos quando implementados com alunos e professores? (c) De que forma o conhecimento construído pode ser mobilizado para outros temas da Física e para o ensino das ciências em geral? O estudo seguiu uma metodologia de Estudos de Desenvolvimento, de natureza mista, que compreendeu as fases da Análise, Design, Desenvolvimento e Avaliação, seguindo como paradigma um estudo de cariz exploratório, com uma vertente de estudo de caso. Assim, na Análise, foi discutido o contexto da educação em Moçambique e a problemática da abordagem das radiações e conteúdos de Física Moderna no ensino secundário no quadro desafiante que se coloca atualmente à educação científica. No Design foram avaliadas as abordagens dasTIC no ensino e aprendizagem da Física e das ciências em geral e construída a árvore de objetivos nos conteúdos referidos na fase anterior. Na fase do Desenvolvimento foram construídos os instrumentos de recolha de dados, elaborados os protótipos de MGQ e sua posterior programação, validação e testagem em formato impresso no estudo exploratório. Na Avaliação, foi conduzido o estudo principal com a aplicação dos modelos no formato digital e feita sua avaliação, o que incluiu a administração de inquéritos por questionário a alunos e professores. Os resultados indicam que na conceção de MGQ, a definição dos objetivos de aprendizagem em termos comportamentais é fundamental na formulação de questões e na análise dos resultados da avaliação com o objetivo de reajustar as estratégias didáticas. Apontam também que a plataforma do PmatE que suporta os MGQ, embora possua constrangimentos devido a sua dependência da internet e limitações de ordem didática, contribui positivamente na aprendizagem e na identificação das dificuldades e principais erros dos alunos, por um lado. Por outro, estimula através da avaliação os processos de assimilação e acomodação do conhecimento. O estudo recomenda a necessidade de mudanças nas práticas de ensino e de aprendizagem para que seja possível a utilização de conteúdos digitais como complemento à abordagem didática de conteúdos.

Volatile terpenoids and C13 norisoprenoids in wines: development of rapid methods of analysis and evaluation of the sesquiterpenoids biological potential

Vitis vinifera L., the most widely cultivated fruit crop in the world, was the starting point for the development of this PhD thesis. This subject was exploited following on two actual trends: i) the development of rapid, simple, and high sensitive methodologies with minimal sample handling; and ii) the valuation of natural products as a source of compounds with potential health benefits. The target group of compounds under study were the volatile terpenoids (mono and sesquiterpenoids) and C13 norisoprenoids, since they may present biological impact, either from the sensorial point of view, as regards to the wine aroma, or by the beneficial properties for the human health. Two novel methodologies for quantification of C13 norisoprenoids in wines were developed. The first methodology, a rapid method, was based on the headspace solid-phase microextraction combined with gas chromatography-quadrupole mass spectrometry operating at selected ion monitoring mode (HS-SPME/GC-qMS-SIM), using GC conditions that allowed obtaining a C13 norisoprenoid volatile signature. It does not require any pre-treatment of the sample, and the C13 norisoprenoid composition of the wine was evaluated based on the chromatographic profile and specific m/z fragments, without complete chromatographic separation of its components. The second methodology, used as reference method, was based on the HS-SPME/GC-qMS-SIM, allowing the GC conditions for an adequate chromatographic resolution of wine components. For quantification purposes, external calibration curves were constructed with β-ionone, with regression coefficient (r2) of 0.9968 (RSD 12.51 %) and 0.9940 (RSD of 1.08 %) for the rapid method and for the reference method, respectively. Low detection limits (1.57 and 1.10 μg L-1) were observed. These methodologies were applied to seventeen white and red table wines. Two vitispirane isomers (158-1529 L-1) and 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) (6.42-39.45 μg L-1) were quantified. The data obtained for vitispirane isomers and TDN using the two methods were highly correlated (r2 of 0.9756 and 0.9630, respectively). A rapid methodology for the establishment of the varietal volatile profile of Vitis vinifera L. cv. 'Fernão-Pires' (FP) white wines by headspace solid-phase microextraction combined with comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (HS-SPME/GCxGC-TOFMS) was developed. Monovarietal wines from different harvests, Appellations, and producers were analysed. The study was focused on the volatiles that seem to be significant to the varietal character, such as mono and sesquiterpenic compounds, and C13 norisoprenoids. Two-dimensional chromatographic spaces containing the varietal compounds using the m/z fragments 93, 121, 161, 175 and 204 were established as follows: 1tR = 255-575 s, 2tR = 0,424-1,840 s, for monoterpenoids, 1tR = 555-685 s, 2tR = 0,528-0,856 s, for C13 norisoprenoids, and 1tR = 695-950 s, 2tR = 0,520-0,960 s, for sesquiterpenic compounds. For the three chemical groups under study, from a total of 170 compounds, 45 were determined in all wines, allowing defining the "varietal volatile profile" of FP wine. Among these compounds, 15 were detected for the first time in FP wines. This study proposes a HS-SPME/GCxGC-TOFMS based methodology combined with classification-reference sample to be used for rapid assessment of varietal volatile profile of wines. This approach is very useful to eliminate the majority of the non-terpenic and non-C13 norisoprenic compounds, allowing the definition of a two-dimensional chromatographic space containing these compounds, simplifying the data compared to the original data, and reducing the time of analysis. The presence of sesquiterpenic compounds in Vitis vinifera L. related products, to which are assigned several biological properties, prompted us to investigate the antioxidant, antiproliferative and hepatoprotective activities of some sesquiterpenic compounds. Firstly, the antiradical capacity of trans,trans-farnesol, cis-nerolidol, α-humulene and guaiazulene was evaluated using chemical (DPPH• and hydroxyl radicals) and biological (Caco-2 cells) models. Guaiazulene (IC50= 0.73 mM) was the sesquiterpene with higher scavenger capacity against DPPH•, while trans,trans-farnesol (IC50= 1.81 mM) and cis-nerolidol (IC50= 1.48 mM) were more active towards hydroxyl radicals. All compounds, with the exception of α-humulene, at non-cytotoxic levels (≤ 1 mM), were able to protect Caco-2 cells from oxidative stress induced by tert-butyl hydroperoxide. The activity of the compounds under study was also evaluated as antiproliferative agents. Guaiazulene and cis-nerolidol were able to more effectively arrest the cell cycle in the S-phase than trans,trans-farnesol and α-humulene, being the last almost inactive. The relative hepatoprotection effect of fifteen sesquiterpenic compounds, presenting different chemical structures and commonly found in plants and plant-derived foods and beverages, was assessed. Endogenous lipid peroxidation and induced lipid peroxidation with tert-butyl hydroperoxide were evaluated in liver homogenates from Wistar rats. With the exception of α-humulene, all the sesquiterpenic compounds under study (1 mM) were effective in reducing the malonaldehyde levels in both endogenous and induced lipid peroxidation up to 35% and 70%, respectively. The developed 3D-QSAR models, relating the hepatoprotection activity with molecular properties, showed good fit (R2LOO > 0.819) with good prediction power (Q2 > 0.950 and SDEP < 2%) for both models. A network of effects associated with structural and chemical features of sesquiterpenic compounds such as shape, branching, symmetry, and presence of electronegative fragments, can modulate the hepatoprotective activity observed for these compounds. In conclusion, this study allowed the development of rapid and in-depth methods for the assessment of varietal volatile compounds that might have a positive impact on sensorial and health attributes related to Vitis vinifera L. These approaches can be extended to the analysis of other related food matrices, including grapes and musts, among others. In addition, the results of in vitro assays open a perspective for the promising use of the sesquiterpenic compounds, with similar chemical structures such as those studied in the present work, as antioxidants, hepatoprotective and antiproliferative agents, which meets the current challenges related to diseases of modern civilization.

Analysis of the organic matter associated to sea salt : definition of potential molecular markers based on the volatile composition and presence of glycosidic derivatives and polysaccharides

Sea salt is a natural product obtained from the evaporation of seawater in saltpans due to the combined effect of wind and sunlight. Nowadays, there is a growing interest for protection and re-valorisation of saltpans intrinsically associated to the quality of sea salt that can be evaluated by its physico-chemical properties. These man-made systems can be located in different geographical areas presenting different environmental surroundings. During the crystallization process, organic compounds coming from these surroundings can be incorporated into sea salt crystals, influencing their final composition. The organic matter associated to sea salt arises from three main sources: algae, surrounding bacterial community, and anthropogenic activity. Based on the hypothesis that sea salt contains associated organic compounds that can be used as markers of the product, including saltpans surrounding environment, the aim of this PhD thesis was to identify these compounds. With this purpose, this work comprised: 1) a deep characterisation of the volatile composition of sea salt by headspace solid phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME/GCGC–ToFMS) methodology, in search of potential sea salt volatile markers; 2) the development of a methodology to isolate the polymeric material potentially present in sea salt, in amounts that allow its characterisation in terms of polysaccharides and protein; and 3) to explore the possible presence of triacylglycerides. The high chromatographic resolution and sensitivity of GC×GC–ToFMS enabled the separation and identification of a higher number of volatile compounds from sea salt, about three folds, compared to unidimentional chromatography (GC–qMS). The chromatographic contour plots obtained revealed the complexity of marine salt volatile composition and confirmed the relevance of GC×GC–ToFMS for this type of analysis. The structured bidimentional chromatographic profile arising from 1D volatility and 2D polarity was demonstrated, allowing more reliable identifications. Results obtained for analysis of salt from two locations in Aveiro and harvested over three years suggest the loss of volatile compounds along the time of storage of the salt. From Atlantic Ocean salts of seven different geographical origins, all produced in 2007, it was possible to identify a sub-set of ten compounds present in all salts, namely 6-methyl-5-hepten-2-one, 2,2,6-trimethylcyclohexanone, isophorone, ketoisophorone, β-ionone-5,6-epoxide, dihydroactinidiolide, 6,10,14-trimethyl-2-pentadecanone, 3-hydroxy-2,4,4-trimethylpentyl 2-methylpropanoate, 2,4,4-trimethylpentane-1,3-diyl bis(2-methylpropanoate), and 2-ethyl-1-hexanol. These ten compounds were considered potential volatile markers of sea salt. Seven of these compounds are carotenoid-derived compounds, and the other three may result from the integration of compounds from anthropogenic activity as metabolites of marine organisms. The present PhD work also allowed the isolation and characterisation, for the first time, of polymeric material from sea salt, using 16 Atlantic Ocean salts. A dialysis-based methodology was developed to isolate the polymeric material from sea salt in amounts that allowed its characterisation. The median content of polymeric material isolated from the 16 salts was 144 mg per kg of salt, e.g. 0.014% (w/w). Mid-infrared spectroscopy and thermogravimetry revealed the main occurrence of sulfated polysaccharides, as well as the presence of protein in the polymeric material from sea salt. Sea salt polysaccharides were found to be rich in uronic acid residues (21 mol%), glucose (18), galactose (16), and fucose (13). Sulfate content represented a median of 45 mol%, being the median content of sulfated polysaccharides 461 mg/g of polymeric material, which accounted for 66 mg/kg of dry salt. Glycosidic linkage composition indicates that the main sugar residues that could carry one or more sulfate groups were identified as fucose and galactose. This fact allowed to infer that the polysaccharides from sea salt arise mainly from algae, due to their abundance and composition. The amino acid profile of the polymeric material from the 16 Atlantic Ocean salts showed as main residues, as medians, alanine (25 mol%), leucine (14), and valine (14), which are hydrophobic, being the median protein content 35 mg/g, i.e. 4,9 mg per kg of dry salt. Beside the occurrence of hydrophobic volatile compounds in sea salt, hydrophobic non-volatile compounds were also detected. Triacylglycerides were obtained from sea salt by soxhlet extraction with n-hexane. Fatty acid composition revealed palmitic acid as the major residue (43 mol%), followed by stearic (13), linolenic (13), oleic (12), and linoleic (9). Sea salt triacylglycerides median content was 1.5 mg per kg of dry salt. Both protein and triacylglycerides seem to arise from macro and microalgae, phytoplankton and cyanobacteria, due to their abundance and composition. Despite the variability resulting from saltpans surrounding environment, this PhD thesis allowed the identification of a sea salt characteristic organic compounds profile based on volatile compounds, polysaccharides, protein, and triacylglycerides.