V.P. de Freitas

Moisture migration in building walls—Analysis of the interface phenomena

Abstract The study of moisture migration in materials and building elements is of great importance for the characterization of their behaviour, and affects their durability, waterproofing, degradation and thermal performance. The different mechanisms of moisture transport in building walls and the analysis of interface phenomena have been investigated. Based on the theory proposed by Luikov and Philip—De Vries, a computer program has been developed. The comparison of calculated and measured values obtained by using gamma-ray equipment to measure water content profiles, is considered satisfactory.

Mechanistic approach by which polysaccharides inhibit α-amylase/procyanidin aggregation.

The present work studies the inhibition of aggregation of α-amylase and procyanidin fractions by different polysaccharides (arabic gum, β-cyclodextrin, and pectins). Several analytical approaches, namely, fluorescence quenching, nephelometry, and dynamic light scattering (DLS), were used. In general, nephelometry showed that the presence of the polysaccharides in solution reduced the formation of insoluble aggregates. The fluorescence quenching measurements showed two effects: arabic gum and β-cyclodextrin reduce the quenching effect of procyanidin fractions on α-amylase fluorescence, whereas pectins do not affect the quenching of α-amylase fluorescence by procyanidin fractions. DLS measurements have revealed that the polysaccharides studied induce a decrease in aggregates size, which probably is due to the formation of smaller aggregates resulting from the disruption and reorganization of the procyanidin fractions/α-amylase aggregates. Overall, the results obtained for arabic gum and β-cyclodextrin strongly suggest that the main mechanism by which these two compounds inhibit protein/polyphenol aggregation is by molecular association between these polysaccharides and polyphenols, competing with protein aggregation. In the case of pectins, the results obtained provide evidence that the main mechanism by which they reduce protein/polyphenol aggregation is by forming a protein/polyphenol/polysaccharide complex, enhancing its solubility in aqueous medium.

Red wine antioxidants protect hippocampal neurons against ethanol-induced damage: a biochemical, morphological and behavioral study.

Chronic ethanol consumption increases oxidative stress, which accounts for the striking neurological changes seen in this condition. Notwithstanding, there is well-documented evidence that polyphenols, present in grape skin and seeds, exhibit a strong antioxidant activity. As red wine is rich in polyphenols, the aim of the present work was to evaluate their putative protective effects on the hippocampal formation by applying biochemical, morphological and behavioral approaches. Six-month old male Wistar rats were fed with red wine (ethanol content adjusted to 20%) and the results were compared with those from ethanol-treated (20%) rats and pair-fed controls. Biochemical markers of oxidative stress (lipid peroxidation, glutathione levels and antioxidant enzyme activities) were assessed on hippocampal homogenates. Lipofuscin pigment, an end product of lipid peroxidation, was quantified in hippocampal cornu ammonis 1 and 3 (CA1 and CA3) pyramidal neurons using stereological methods. All animals were behaviorally tested on the Morris water maze in order to assess their spatial learning and memory skills. In red wine-treated rats, lipid peroxidation was the lowest while presenting the highest levels of reduced glutathione and an induction of antioxidant enzyme activities. Morphological findings revealed that, contrary to ethanol, red wine did not increase lipofuscin deposition in CA1 and CA3 pyramidal neurons. Besides, red wine-treated animals learned the water maze task at a higher rate than ethanol group and had better performance scores by the end of the training period and on a probe trial. Actually, no significant differences were found between pair-fed controls and red wine-treated rats in morphological and behavioral data. Thus, our findings demonstrate that chronic consumption of red wine, unlike the ethanol solution alone, does not lead to a decline in hippocampal-dependent spatial memory. This may be due to the ability of red wine polyphenols to improve the antioxidant status in the brain and to prevent free radical-induced neuronal damage.

The phenolic chemistry and spectrochemistry of red sweet wine-making and oak-aging.

A natural sweet wine (NSW) was made with dried grapes from Vitis vinifera L. cv Garnacha Tintorera. A fortified sweet wine (FSW) was also obtained: the maceration-alcoholic fermentation of Garnacha Tintorera must was stopped by addition of ethanol 96% (v/v). UV/Vis spectrophotometry and HPLC/DAD-ESI/MS were applied to determine, respectively, the evolution of colour and phenolic compounds in Garnacha Tintorera based-sweet wines during aging. In sweet wines, aging decreased a(∗) (red/green), colour saturation and lightness and increased b(∗) (yellow/blue), and hue angle. Most of the phenolic compounds determined, such as anthocyanins, esters of hydroxycinnamic acids, flavan-3-ols monomers, oligomers and polymers decreased in both sweet wines during aging. On the contrary, hydroxybenzoic and hydroxycinnamic acids and vitisins increased after one year of aging. Despite that both terminal and extension subunit compositions show very small changes, mean degree of polymerisation of proanthocyanidins decline slightly as aging progressed in both sweet wines.

Enzymatic Hemisynthesis of Metabolites and Conjugates of Anthocyanins

This work aims to study the phase II metabolization of anthocyanins that is likely to occur in vivo. Anthocyanins (delphinidin, cyanidin, and malvidin-3-glucosides) were incubated with phase II enzymes in the presence of activated cofactors in order to obtain glutathionyl conjugates, methylated and glucuronydated compounds. Overall, the three anthocyanins tested were metabolized in vitro. Two compounds were detected by HPLC after incubation of human liver cytosolic fraction with cyanidin-3-glucoside and one compound with delphinidin-3-glucoside. These compounds were identified as monomethylated products. LC-MS analysis yielded mass data that fit with the anthocyanin structures bearing an additional methyl group in ring B. Several compounds were detected by HPLC after incubation of human liver microsomes with malvidin, cyanidin, and delphinidin-3-glucosides. These compounds were identified as monoglucuronides products after HPLC analysis. Conjugation with glutathione also occurred as proved by the mass data obtained. However, in this case, two anthocyanin equilibrium forms (flavylium and chalcone or water adducts) conjugated with glutathione were detected. Overall, the data of the present work shows the feasibility of the in vitro enzymatic hemisynthesis of metabolites and glutathione conjugates of anthocyanins. This first experimental approach may further allow the achievement of new purified forms of anthocyanins, some of which do not occur in nature, and also the determination of whether these compounds are the bioactive forms responsible for some of the biological activities reported for anthocyanins.

Rapid screening and identification of new soluble tannin-salivary protein aggregates in saliva by mass spectrometry (MALDI-TOF-TOF and FIA-ESI-MS).

Astringency is mainly attributed to the interaction between tannins and salivary proteins. Proline-rich proteins, histatins, and statherins are supposed to be the most reactive salivary proteins. This study aims to contribute to the knowledge of the tannin-protein binding process in saliva. It was identified for the first time in several soluble tannin-human salivary protein aggregates. A rapid mass spectrometry analytical method (MALDI-TOF and FIA-ESI-MS) was developed to identify new soluble tannin-human salivary protein aggregates. Three different tannins--procyanidin B3 (B3), procyanidin B2 gallate (B2G), and pentagalloylglucoside (PGG)--were tested to elucidate the tannin selectivity toward histatins, proline-rich proteins, and statherins in human saliva. A greater number of aggregates with a higher molecular weight was found when PGG was tested while no difference in the number and molecular mass range was observed in B3 or B2G salivary protein aggregates. This study confirms for the first time the bilateral selectivity of tannins and protein to yield soluble tannin-human salivary protein complexes. The results confirm that B3 and B2G are more selective than PGG. Furthermore, the families of proteins involved in the majority of B3-salivary protein soluble aggregates were primarly histatins, followed by basic proline-rich proteins and statherins. When B2G was tested, basic proline-rich proteins were involved in a greater number of aggregates, followed by histatines and statherins. Basic proline-rich proteins were also the family of proteins that formed a greater number of PGG-salivary protein aggregates followed by statherins and histatins. Acidic proline-rich proteins and glucosilated proline-rich proteins formed fewer soluble aggregates regardless of the tannin tested. The aggregation process was also found to be influenced by tannin and protein polarity. Indeed, the protein/tannin ratio of soluble aggregates increased with the tannin polarity. On the other hand, the only amphiphilic salivary proteins studied (histatins) formed a greater number of aggregates with the least polar tannin tested (B3).

Can moisture buffer performance be estimated from sorption kinetics

This article describes the research on the moisture buffering effect of building materials. A set of experiments on samples of current building materials are conducted under transient conditions of relative humidity (RH). The results obtained are then analyzed using kinetics models. The experimental settings are based on the moisture buffer value (MBV) test method currently under study by Nordic researchers. The main result from these tests is the MBV number that can be used to characterize the moisture buffer performance of a material or a system. The application of kinetics models to the experimental results is explored and several parameters are retrieved. A proposal for the use of these parameters is presented and its practical use is discussed.

Screening of portisins (vinylpyranoanthocyanin pigments) in port wine by LC/DAD-MS

Samples of a two-year-old Port red wine were fractionated by Toyopearl gel column chromatography yielding different coloured fractions. Anthocyanin-derived compounds were tentatively identified by LC/DAD-MS in the different eluted fractions. Several pigments were found to correspond to a recently reported family of pyranoanthocyanin compounds named portisins, supposedly arising from the reaction between anthocyanin-pyruvic acid adducts and flavanols in the presence of acetaldehyde. These pigments present a structure in which pyranoanthocyanins are linked to flavanols (catechins or procyanidin dimers) through a vinyl linkage. These pigments showed a UV-visible spectrum with a λmax batochromically shifted from that of genuine anthocyanins, thereby contributing to a more bluish hue.

Analysis and Monitoring of the Drying Process of a Hygro-Regulated Wall Base Ventilation System Implemented in a Historical Church to Control Rising Damp

Treating rising damp in the walls of historic buildings is a very complex procedure and the traditional techniques currently used to minimize rising damp are not effective or too expensive, in particular when dealing with walls of considerable thickness and heterogeneous materials. This work presents the results of an in situ application of the hygro-regulated wall base ventilation system to control rising damp in a historical church located in northern Portugal. The main purpose is to validate the wall base ventilation technology for treating rising damp in very thick and heterogeneous walls. The analytical model used well describes the observed features of rising damp in building walls, verified by in-field tests, which contributed to simple sizing of the hygro-regulated wall base ventilation system to be implemented in historical buildings.

Isolation and structural characterization of anthocyanin-furfuryl pigments.

Condensation reactions of malvidin-3-glucoside with two representative oak wood furanic aldehydes (furfural and methylfurfural) were conducted in wine-like model solutions. Methylfurfural led to the formation of malvidin-3-glucoside-methylfurfural (603 m/z), whereas furfural led to the formation of malvidin-3-glucoside-furfural (589 m/z). The latter was structurally characterized by 1D and 2D NMR, allowing an elucidation of the formation mechanism of these anthocyanin-furanic aldehyde adducts in the absence of flavanols.