The efficiency of eight different procedures used for the extraction of natural dyes was evaluated using contemporary wool samples dyed with cochineal, madder, woad, weld, brazilwood and logwood. Comparison was made based on the LC-DAD peak areas of the natural dye's main components which had been extracted from the wool samples. Among the tested methods, an extraction procedure with Na 2 EDTA in water/DMF (1:1, v/v) proved to be the most suitable for the extraction of the studied dyes, which presented a wide range of chemical structures. The identification of the natural dyes used in the making of an eighteenth century Arraiolos carpet was possible using the Na 2 EDTA/DMF extraction of the wool embroidery samples and an LC-DAD-MS methodology. The effectiveness of the Na 2 EDTA/DMF extraction method was particularly observed in the extraction of weld dye components. Nine flavone derivatives previously identified in weld extracts could be identified in a single historical sample, confirming the use of this natural dye in the making of Arraiolos carpets. Indigo and brazilwood were also identified in the samples, and despite the fact that these natural dyes were referred in the historical recipes of Arraiolos dyeing, it is the first time that the use of brazilwood is confirmed. Mordant analysis by ICP-MS identified the widespread use of alum in the dyeing process, but in some samples with darker hues, high amounts of iron were found instead.
Wines from different grape varieties, geographical zones, soil types, foliar N application, SO addition and oak ageing were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). For this purpose, ICP-MS methodology was optimized. The elements which allowed differentiate wines from studied grape varieties were Sr, Ca, Mg and Mn. Geographical zones were classified according to Sr, Ba, Ni, and Cu. Cs and Pb were the main elements to discriminate the wines from the 3 soil types. Wines from several N foliar doses application were classified by Pb, Ni, Mn and Zn. The content of Cs, Mg, Cu and Pb in wines characterized the SO addition. Finally, wines storage in barrels were differentiate by Na and Cs concentration. The discriminant functions classify 100% of the wines, with the exception of grape variety (97.0%) and oak ageing (95.8%). Consequently, ICP-MS can be applied to classified wines according to viticultural and oenological factors.
Botanical species used on aging process must be wisely and judiciously chosen, and for this selection, a basic knowledge of the chemical composition of woods is warranted. Aiming to contribute to extend the knowledge of the chemical composition of several wood species useful for enological purposes, we have focused our studies on Portuguese chestnut and French, American and Portuguese oak chips. The profile of low molecular weight phenolic composition of these chips was achieved, using an optimized extraction method based on pressurized liquid extraction, followed by the quantification of phenolic acids, phenolic aldehydes and furanic derivatives by high-performance liquid chromatography (HPLC-DAD). The identification of those compounds was also confirmed by LC-DAD/ESI-MS. This study allowed the determination of the low molecular phenolic composition of Portuguese chestnut and French, American and Portuguese oak wood. According to our results, the influence of the botanical species seems to be more relevant than the geographic origin of the wood species.
This study integrates bone collagen stable isotope data (carbon, nitrogen and sulphur) from 33 human adult tibiae (15 females; 18 males) and 13 faunal remains from Tomar, while it was under the Military Orders domain (eleventh-seventeenth centuries). Historical literature indicates that the amount of meat consumption amongst Templars was lower than in individuals with similar social status. In Medieval times, these Military Orders had total control of towns and angling and fishing rights, but their influence on the general population diet remains unknown. While no statistically significant differences (p > 0.05) were found between sexes, social status, or for bone collagen δ 13 C and δ
34Sbetween age groups, δ 15 N did differ significantly with age, which may be related to tooth loss in old individuals. Additionally, the human samples have higher stable isotope differences, in comparison with faunal samples, than would be expected within the food web, particularly for δ 13 C. This human bone collagen δ 13 C enrichment may reflect a diet rich in aquatic protein intake, which is also supported by δ 34 S archived in human and faunal samples, and the presence of oysters and cockles shells at the excavation. The religious diet restrictions might have led to a higher intake of aquatic protein when meat consumption was not allowed.
The aim of this work was the material characterisation of wall paintings and biodegradation assessment, including the analysis of microbial growth and the effect of microbial proliferation, in view of their conservation. The methodology was applied to the study of frescoes dated from 1531, located in the ancient parish church of Santo Aleixo, Southern Portugal. The combined use of optical microscopy, SEM-EDS and A-XRD showed that the painting palette is composed of red and yellow ochres, malachite, azurite and bone black. The pigments do not show signs of chemical deterioration, except malachite that punctually have transformed to black copper oxide (tenorite). The microbiological study allowed the identification of several bacterial strains (eg Gram+ cocci, Gram+ bacilli, Actinomycetes sp.), yeast strains and filamentous fungi of the genera Penicillium, Cladosporium, Aspergillus among others the microflora present in the paintings.Their metabolic activity is the main responsible for the physical disruption of paint layers and underneath mortars. The combined approach using SEM analysis and enzymatic dehydrogenase measurement allowed the evaluation of microflora proliferation and the biodeterioration diagnosis of the mural paintings. Additionally, the effect of some commercial biocides was evaluated for the main predominant strains in order to select the most efficient biocide.
Honey is a natural food product very famous for its health benefits for being an important source of antioxidant and phenolic compounds. Euphorbia honeys obtained from different regions of Morocco were evaluated for their ability to inhibit acetylcholinesterase, lipoxygenase, tyrosinase and xanthine oxidase activities. Their antioxidant properties were evaluated using the: 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity, nitric oxide scavenging activity (NO) and scavenging ability of superoxide anion radical. Then, the phenolic extracts of the same entire honey samples were evaluated by liquid chromatography coupled to diode array detection and mass spectrometry (LC-DAD-MS) and tested for the biological activities previously evaluated on the entire honeys, in order to conduct a comparative study between both (honey and phenolic extracts). The chromatographic profiles for the studied Euphorbia honey extracts were different. Phenolic compounds gallic acid, 4-hydroxybenzoic acid and p-coumaric acid were detected in all samples, whereas kampferol was only present in two samples. Physicochemical parameters and total phenolic content were also determined. Entire honey that recorded the highest rate of phenols was sample M6 (E. resinifera) = 69.25 mg GAE/100 g. On the other hand, the phenolic extracts had better antioxidant and enzyme inhibitory activities than the entire honeys, regardless the monofloral honey type. In conclusion, the studied Euphorbia honeys may have a great potential as antioxidant, anti-inflammatory and anti-tyrosinase sources for pharmaceutical and cosmetic applications.
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