Multivariate analysis for the classification and differentiation of Madeira wines according to main grape varieties

In order to differentiate and characterize Madeira wines according to main grape varieties, the volatile composition (higher alcohols, fatty acids, ethyl esters and carbonyl compounds) was determined for 36 monovarietal Madeira wine samples elaborated from Boal, Malvazia, Sercial and Verdelho white grape varieties. The study was carried out by headspace solid-phase microextraction technique (HS-SPME), in dynamic mode, coupled with gas chromatography–mass spectrometry (GC–MS). Corrected peak area data for 42 analytes from the above mentioned chemical groups was used for statistical purposes. Principal component analysis (PCA) was applied in order to determine the main sources of variability present in the data sets and to establish the relation between samples (objects) and volatile compounds (variables). The data obtained by GC–MS shows that the most important contributions to the differentiation of Boal wines are benzyl alcohol and (E)-hex-3-en-1-ol. Ethyl octadecanoate, (Z)-hex-3-en-1-ol and benzoic acid are the major contributions in Malvazia wines and 2-methylpropan-1-ol is associated to Sercial wines. Verdelho wines are most correlated with 5-(ethoxymethyl)-furfural, nonanone and cis-9-ethyldecenoate. A 96.4% of prediction ability was obtained by the application of stepwise linear discriminant analysis (SLDA) using the 19 variables that maximise the variance of the initial data set.

Heterocyclic acetals in Madeira wines

The maturation of Madeira wines usually involves exposure to relatively high temperatures which affect the aroma and flavour composition leading to the formation of the typical and characteristic bouquet of these wines. The formation of heterocyclic acetals (1,3-dioxanes and 1,3-dioxolanes) was investigated in order to determine levels and for possible use as indicators of wine age. The results show a linear correlation of the investigated acetals with wine age but suggest that the acetalization reaction is not particularly affected by the drastic oxidative conditions observed during maturation.

Varietal flavour compounds of four grape varieties producing Madeira wines

Boal, Malvasia, Sercial and Verdelho are the main white grape varieties used in Madeira wine production. To estimate the free fraction of varietal aroma compounds of these varieties, 39 samples of musts were analysed to determine their content of monoterpenols and C13 norisoprenoids (terpenoids), using dynamic headspace solid-phase microextraction coupled with gas chromatography–mass spectrometry. The r-values for linearity studies of the analytical method used, varied between 0.977 (nerolidol) and 0.999 (linalool). The repeatability for each compound varied between 2.5% (citronellol) and 11.8% (β-ionone). The mean values from three vintages (1998, 1999 and 2000) confirmed that these musts have differentiated contents of terpenoids. In opposition to Verdelho musts, Malvasia showed the highest free terpenoids content. In order to establish relations between the compounds and the varieties under investigation, principal component analysis and linear discriminant analysis were applied to the data, revealing a good separation and classification power between the four groups as a function of varietal origin.

3-Hydroxy-4, 5-dimethyl-2 (5 H)-furanone levels in fortified Madeira wines: Relationship to sugar content

The maturation of Madeira wines usually involves exposure to relatively high temperatures and humidity levels >70%, which affect the aroma and flavor composition and lead to the formation of the typical and characteristic bouquet of these wines. To estimate the levels of sotolon [3-hydroxy4,5-dimethyl-2(5 H )-furanone] and their behavior over time, 86 aged Madeira wines samples (1-25 years old), with different sugar concentrations, respectively, 90 g L-1 for Boal, 110 g L-1 for Malvazia, 25 g L -1 for Sercial, and 65 g L-1 for Verdelho varieties, were analyzed. Isolation was performed by liquid-liquid extraction with dichloromethane followed by chromatographic analysis by GC-MS. The reproducibility of the method was found to be 4.9%. The detection and quantification limits were 1.2 and 2.0 µgL-1, respectively. The levels of sotolon found ranged from not detected to 2000 µgL-1 for wines between 1 and 25 years old. It was observed that during aging, the concentration of sotolon increased with time in a linear fashion ( r ) 0.917). The highest concentration of sotolon was found in wines with the highest residual sugar contents, considering the same time of storage. The results show that there is a strong correlation between sotolon and sugar derivatives: furfural, 5-methylfurfural, 5-hydroxymethylfurfural, and 5-ethoxymethylfurfural. These compounds are also well correlated with wine aging. These findings indicate that the kinetics of sotolon formation is closely related with residual sugar contents, suggesting that this molecule may come from a component like sugar.

Comparative analysis of the volatile fraction from Annona cherimola Mill. cultivars by solid-phase microextraction and gas chromatography–quadrupole mass spectrometry detection

The analysis of volatile compounds in Funchal, Madeira, Mateus and Perry Vidal cultivars of Annona cherimola Mill. (cherimoya) was carried out by headspace solid-phase microextraction (HS-SPME) combined with gas chromatography–quadrupole mass spectrometry detection (GC–qMSD). HS-SPME technique was optimized in terms of fibre selection, extraction time, extraction temperature and sample amount to reach the best extraction efficiency. The best result was obtained with 2 g of sample, using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre for 30 min at 30 °C under constant magnetic stirring (800 rpm). After optimization of the extraction methodology, all the cherimoya samples were analysed with the best conditions that allowed to identify about 60 volatile compounds. The major compounds identified in the four cherimoya cultivars were methyl butanoate, butyl butanoate, 3-methylbutyl butanoate, 3-methylbutyl 3-methylbutanoate and 5-hydroxymethyl-2-furfural. These compounds represent 69.08 ± 5.22%, 56.56 ± 15.36%, 56.69 ± 9.28% and 71.82 ± 1.29% of the total volatiles for Funchal, Madeira, Mateus and Perry Vidal cultivars, respectively. This study showed that each cherimoya cultivars have 40 common compounds, corresponding to different chemical families, namely terpenes, esters, alcohols, fatty acids and carbonyl compounds and using PCA, the volatile composition in terms of average peak areas, provided a suitable tool to differentiate among the cherimoya cultivars.

Famílias com necessidades educativas especiais: lutos e perdas: um estudo na Região Autónoma da Madeira

Quando nasce um indivíduo com uma incapacidade ou a adquire ao longo do percurso de vida, a família lida de uma determinada forma com essa nova e indesejada notícia. O presente estudo teve como intuito verificar que impacto tem a presença de filhos portadores de incapacidade no ciclo vital da família. Pretende-se compreender a perda e o processo de luto inerente a estas famílias, nomeadamente os sentimentos e reações face à incapacidade dos filhos, mudanças na vida dos pais, momentos mais difíceis e relacionamento que os pais têm com os filhos com necessidades educativas especiais. Para a realização da investigação, recorreu-se às entrevistas semiestruturadas a 13 pais, 12 do género feminino e 1 do género masculino com idades compreendidas entre os 30 e 63 anos, com escolaridade desde a 4ª classe até o Doutoramento. Recorreu-se à Grounded Theory com o intuito de encontrar as categorias principais relacionadas com o impacto da presença de necessidades educativas especiais na família. As quatro categorias identificadas demonstram que o diagnóstico é um fator importante para o processo de aceitação do indivíduo com NEE. Os pais relatam sentimentos negativos perante a incapacidade do filho, falta de informação, falta de diversos apoios, nomeadamente o social, monetário, terapêutico, médico e psicológico. Falam também dos preconceitos existentes na sociedade e a falta de recursos para a inclusão do indivíduo com NEE. Os pais demonstram preocupação em relação às transições intrínsecas ao próprio ciclo de vida dos indivíduos com NEE, à inclusão na sociedade e à incerteza do futuro. Estas preocupações podem afetar a funcionalidade da família, constituindo as causas para diversas mudanças e reajustes no seio familiar, manifestando-se maioritariamente na mudança de rotinas. Podendo também ocorrer mudanças estruturais na família, como sendo o divórcio. A relação dos pais com os filhos pode ser considerada como boa, caracterizada por sentimentos positivos e amor incondicional.

Relatório de estágio apresentado à Universidade da Madeira para obtenção do grau de mestre em Educação Pré-Escolar e Ensino do 1º Ciclo do Ensino Básico

O percurso pedagógico de formação inicial docente, descrito ao longo do relatório apresentado, teve como epítome os estágios realizados na Escola Básica do 1.º Ciclo com Pré-Escolar do Lombo Segundo. As práticas enunciadas decorreram na turma do 4.ºA, entre outubro e dezembro de 2013, e na sala da Pré 2, com crianças com idades compreendidas entre os quatro e cinco anos, tendo iniciado em março de 2014 e findando em junho do mesmo ano. Logo, importa apresentar os pressupostos teóricos que sustentaram a ação pedagógica desenvolvida num contexto determinado por fatores económicos e socioculturais, e que determinaram a correlação entre a teoria e a prática, com repercussões diretas e constantes na competência reflexiva do aprendente – a estagiária. Neste sentido, existiram observações e registos diários para uma prática conducente às necessidades e potencialidades dos alunos e crianças. Em contexto de 1.ºCEB foi, portanto, desenvolvido um projeto de investigaçãoação com o propósito de se assinalarem aspetos que poderiam influenciar as aprendizagens. Surgiu, então, a seguinte questão: De que forma ampliar competências sociais através do trabalho cooperativo numa turma de 4.º ano?, que se tornou orientadora do estágio realizado no seio da turma do 4.ºA. O principal objetivo foi o de, pela valorização do outro e aumento de autoestima, criar oportunidades de aprenderem com o outro e, mais importante, aprenderem a estar com o outro, de forma a passarem para o conhecimento de conteúdos específicos das áreas curriculares e extracurriculares. À semelhança deste grupo, em educação pré-escolar, as situações que exigiam inter-relação também foram otimizadas, tendo em conta que a implicação nas tarefas surge quando as crianças se situam em níveis de bem-estar elevados, sempre consoante uma atitude democrática, pois as crianças eram verdadeiramente os principais agentes das suas aprendizagens, visto que a sala regia-se pelo modelo pedagógico do Movimento da Escola Moderna.

Impact of forced-aging process on Madeira Wine flavor

The aim of this study was to determine the optimal temperature and baking time to obtain a Madeira wine considered typical by an expert panel. For this purpose simultaneous descriptive analyses of typical Madeira wines were performed, and seven descriptors were selected: “dried fruit”, “nutty”, “musty”, “baked”, “oak”, “mushroom”, and “brown sugar”. Up to 10 odor-active zones were the most frequently cited by the members of the GC-olfactometry panel as corresponding to the panel’s descriptors. The odor importance of each of the zones reported by the GC-O analysis was ranked by AEDA. Three odor zones were identified as common to both Malvasia and Sercial wines and had retention indices (RI) of 1993 (“brown sugar” and “toasted”), 2151 (“brown sugar”), and 2174 (“nutty”, “driedfruits”);sotolonwasidentifiedasresponsibleforthislastaroma.Severalmoleculeswereselected to be quantified on baked wines on the basis of AEDA results and expected Maillard volatiles, such as sotolon, furfural, 5-methylfurfural, 5-ethoximethylfurfural, methional, and phenylacetaldehyde. It was observed that typicity scores were positively correlated with the concentrations of sotolon and sugar and baking time and negatively with the fermentation length.

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine

An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r2) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).

Content in metallic ions of wines from the Madeira and Azores archipelagos

This study determines for the first time Na, K, Ca, Mg, Fe, Cu, Zn, Mn, Sr, Li and Rb contents in wines from the archipelagos of Madeira and Azores (Portugal). The greater part of the mean content for the different parameters fell within the ranges described in the literature, except for sodium whose higher content may be due to the effect of marine spray. ANOVA was used to establish the metals with significant differences in mean content between the wines from both archipelagos, between table and liquor wines of Madeira, and between wines of Pico and Terceira Islands from the Azores archipelago. Principal component analysis shows differences in the wines according to the wine-making process and/or the equipment employed. Stepwise linear discriminant analysis achieves a good classification and validation of wines according to the archipelago of origin, and the island in the case of Azores wines.

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile: identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate – PA, 100 μm polydimethylsiloxane – PDMS, 65 μm polydimethylsiloxane/divinylbenzene – PDMS/DVB, 70 μm carbowax/divinylbenzene – CW/DVB and 85 μm carboxen/polydimethylsiloxane – CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography–quadrupole mass spectrometry (GC–qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.

In-depth search focused on furans, lactones, volatile phenols, and acetals as potential age markers of Madeira wines by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction

The establishment of potential age markers of Madeira wine is of paramount significance as it may contribute to detect frauds and to ensure the authenticity of wine. Considering the chemical groups of furans, lactones, volatile phenols, and acetals, 103 volatile compounds were tentatively identified; among these, 71 have been reported for the first time in Madeira wines. The chemical groups that could be used as potential age markers were predominantly acetals, namely, diethoxymethane, 1,1-diethoxyethane, 1,1-diethoxy-2-methyl-propane, 1-(1-ethoxyethoxy)-pentane, trans-dioxane and 2-propyl-1,3-dioxolane, and from the other chemical groups, 5-methylfurfural and cis-oak-lactone, independently of the variety and the type of wine. GC × GC-ToFMS system offers a more useful approach to identify these compounds compared to previous studies using GC−qMS, due to the orthogonal systems, that reduce coelution, increase peak capacity and mass selectivity, contributing to the establishment of new potential Madeira wine age markers. Remarkable results were also obtained in terms of compound identification based on the organized structure of the peaks of structurally related compounds in the GC × GC peak apex plots. This information represents a valuable approach for future studies, as the ordered-structure principle can considerably help the establishment of the composition of samples. This new approach provides data that can be extended to determine age markers of other types of wines.

O Visconde da Ribeira Brava na 1.ª República madeirense

A dissertação de mestrado com o título de O Visconde da Ribeira Brava na 1ª República Madeirense apresenta a vida e a acção política empreendida por Francisco Correia de Herédia, sob a égide da 1.ª República. Neste estudo é possível identificar as medidas empreendidas pelo ilustre político nas corporações administrativas locais da Junta Geral do Distrito do Funchal, da Junta Agrícola da Madeira, da Junta Autónoma das Obras do Porto do Funchal e da Santa Casa da Misericórdia. A acção parlamentar do Visconde da Ribeira Brava durante as legislaturas de 1911-15 e de 1915-17 constam, igualmente, da investigação. Os momentos mais carismáticos protagonizados pelo ilustre político e as homenagens a ele atribuídas em território nacional encerram o estudo, que teve como fontes principais os acervos documentais e jornalísticos existentes no Arquivo Regional da Madeira, no Arquivo Histórico Parlamentar da Assembleia da República e na Biblioteca Nacional de Portugal.

Durabilidade do betão: caracterização de amostras de betão recolhidas ao longo de dois túneis da Região Autónoma da Madeira

Na realização deste trabalho pretendeu-se caracterizar amostras de betão recolhidas ao longo de dois túneis da Região Autónomo da Madeira com o objetivo de traçar um perfil de composição e relacionar com a durabilidade. Para tal foram recolhidas amostras em dois túneis, o Túnel da Cruz Vermelha e o Túnel da Encumeada. De modo a caracterizar o betão foram realizados ensaios de carbonatação, determinação do teor de cloretos em profundidade em laboratório, termogravimétrica, análise macroestrutural e de difração raios X. Realizou-se uma previsão de quando é que as armaduras poderão deixar de estar passivadas devido a carbonatação (período de iniciação) e quando é que os túneis deverão ser alvos de reparações devido a corrosão (período de propagação). Tentou-se verificar a influência da carbonatação em altura no Túnel da Cruz Vermelha. Demonstrou-se que a fissuração é uma zona de fácil acesso para as substâncias agressivas penetrarem para o interior do betão, nomeadamente o dióxido de carbono relacionado com a carbonatação. Demonstrou-se também que é possível determinar a profundidade carbonatação através da difração de raios X. Verificou-se que o método (difração de Raio X) usado para determinar a composição do betão de ambos os túneis é viável. Constatou-se que praticamente todas as carotes apresentam pontos com valores de cloretos superiores aos permitidos pela norma atualmente em vigor (NP EN 206-1: 2007). Uma das possíveis razões para esses valores é o facto de na RAM, a areia utilizada no fabrico do betão ser de origem marítima. Em termos da profundidade de carbonatação verificou-se que praticamente em todas as amostras, o valor determinado ainda não tinha alcançado as armaduras e deste modo encontravam-se passivadas, com exceção a carote nº10 (Túnel Encumeada) em que a carbonatação já tinha ultrapassado o valor do recobrimento e a armadura já apresentava sinais de corrosão.