Construção de conhecimento em ambientes virtuais : influência das relações interpessoais

A presente investigação foi conduzida no ambiente virtual imersivo 3D Second Life®, com o suporte de ferramentas Web 2.0 como complemento a aulas presenciais - numa lógica de sala de aula estendida. Teve como pressuposto que a socialização é um fator-chave para as aprendizagens colaborativas e para a construção de conhecimento. O estudo tem por objetivo identificar as variáveis que poderão influenciar a partilha de conhecimento em contextos de aprendizagem com recurso a ambientes virtuais; com a finalidade de contribuir para a melhoria das situações de aprendizagem com recurso a ferramentas online. Esta investigação é de carácter exploratório e enquadra-se no campo dos estudos fenomenológicos. O estudo foi implementado, em duas fases, com quatro turmas de ensino superior, duas turmas diurnas (regime geral) e duas turmas de ensino noturno (regime de maiores de 23). Todas seguindo o mesmo curso e a mesma unidade curricular. Concluímos que nos espaços virtuais os estudantes tendem a sentir-se mais confiantes, abertos, participativos, criativos, compreensivos e parecem participar nas sessões de formação online porque estão, de facto, interessados em aprender. Por outro lado, a possibilidade de providenciar sessões de tutória online permite chegar a um maior número de estudantes. Estas sessões online podem ser estabelecidas numa hora e local (virtual) livre de restrições e que pode ser adaptado, permitindo uma participação mais efetiva por parte dos estudantes. Assim, e com base nas observações retiradas do estudo implementado, pode ainda referir-se que os contrastes de comportamento verificados entre os alunos do regime diurno e do regime noturno, no que concerne ao empenhamento com as ferramentas online, parecem ser em função do nível de maturidade, do nível de independência enquanto alunos, da motivação intrínseca.

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.

A integração e compreensão do desenho na modelação 3D : enquadramento académico

Na medida em que os produtos e os processos de criação são cada vez mais mediados digitalmente, existe uma reflexão recente acerca da relação entre as imagens e as ferramentas usadas para a sua produção. A relação natural e estreita entre a dimensão conceptual e a dimensão física abre a discussão ao nível da semântica e dos processos da projetação e manipulação das imagens, nas quais estão naturalmente incluídas as ferramentas CAD. Tendo o desenho um papel inequívoco e fundamental no exercício da projetação e da modelação 3D é pertinente perceber a relação e a articulação entre estas duas ferramentas. Reconhecendo o desenho como uma ferramenta de domínio físico capaz de expressar o pensamento que opera a transformação de concepções abstratas em concepções concretas, reconhecê-lo refletido na dimensão virtual através de um software CAD 3D não é trivial, já que este, na generalidade, é processado através de um pensamento cujo contexto é distante da materialidade. Metodologicamente, abordaremos esta questão procurando a verificação da hipótese através de uma proposta de exercício prático que procura avaliar o efeito que as imagens analógicas poderão ter sobre o reconhecimento e operatividade da ferramenta Blender num enquadramento académico. Pretende-se, pois, perceber como o desenho analógico pode integrar o processo de modelação 3D e qual a relação que mantém com quem elas opera. A articulação do desenho com as ferramentas de produção de design, especificamente CAD 3D, permitirá compreender na especialidade a articulação entre ferramentas de diferentes naturezas tanto no processo da projetação quanto na criação de artefactos visuais. Assim como poderá lançar a discussão acerca das estratégias pedagógicas de ensino do desenho e do 3D num curso de Design.

Random path sampling applied to vector models of magnetism

The recently reported Monte Carlo Random Path Sampling method (RPS) is here improved and its application is expanded to the study of the 2D and 3D Ising and discrete Heisenberg models. The methodology was implemented to allow use in both CPU-based high-performance computing infrastructures (C/MPI) and GPU-based (CUDA) parallel computation, with significant computational performance gains. Convergence is discussed, both in terms of free energy and magnetization dependence on field/temperature. From the calculated magnetization-energy joint density of states, fast calculations of field and temperature dependent thermodynamic properties are performed, including the effects of anisotropy on coercivity, and the magnetocaloric effect. The emergence of first-order magneto-volume transitions in the compressible Ising model is interpreted using the Landau theory of phase transitions. Using metallic Gadolinium as a real-world example, the possibility of using RPS as a tool for computational magnetic materials design is discussed. Experimental magnetic and structural properties of a Gadolinium single crystal are compared to RPS-based calculations using microscopic parameters obtained from Density Functional Theory.