Cristina Barrocas Dias

Evaluation of carbamazepine uptake and metabolization by Typha spp., a plant with potential use in phytotreatment

Phytoremediation technologies such as constructed wetlands have shown higher efficiencies in removal of pharmaceuticals from wastewaters than conventional wastewater treatment processes, and plants seem to have an important role in the removal of some of those compounds. In this context, a study was conducted to assess tolerance, uptake, and metabolism of the epilepsy drug, carbamazepine, by the macrophyte Typha spp. This evaluation was conducted in hydroponic solutions with 0.5-2.0mg/L of this pharmaceutical for a maximum period of 21 days. The removal of carbamazepine from nutrient solutions by the plants reached values of 82% of the initial contents. Furthermore, a metabolite (10,11-dihydro-10,11-epoxycarbamazepine) was detected in leaf tissues indicating carbamazepine translocation and metabolism inside plants. Activities of antioxidant enzymes catalase, superoxide dismutase, and guaiacol peroxidase generally increase (after some mild initial inhibition in the case of the latter enzyme) as result of the abiotic stress caused by the exposure to carbamazepine, but ultimately Typha seemed able to cope with its toxicity. The results obtained in this study suggest the ability of Typha spp., to actively participate in the removal of carbamazepine from water when used in phytotreatment systems.

Extracting natural dyes from wool—an evaluation of extraction methods

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 Na2EDTA 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 Na2EDTA/DMF extraction of the wool embroidery samples and an LC-DAD-MS methodology. The effectiveness of the Na2EDTA/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.

Study on the use of Typha spp. for the phytotreatment of water contaminated with ibuprofen

Several studies on phytotoxic effects caused by organic xenobiotics and their removal from water by macrophytes have already been performed to evaluate the usefulness of these plants for phytoremediation technologies. In this context, a study was conducted to assess Typha spp.s ability to withstand and remove, from water, the non-steroidal anti-inflammatory drug ibuprofen. For an initial ibuprofen concentration of 20 µg L−1, Typha removed nearly 60% of it within the first 24 h, attaining over 99% removal by the end of the assay (21 days). Exposure to higher ibuprofen concentrations did affect Typhas growth but, by the end of the assays, plants’ growth as well as photosynthetic pigments approached normal values. An alteration in antioxidant enzymes activities (superoxide dismutase, catalase, guaiacol peroxidase) indicated that both roots and leaves were affected by the xenobiotic. Eventually, Typha seemed able to cope with ibuprofens induced oxidative damage suggesting its ability for phytotreatment of waters contaminated with ibuprofen.

Phenolic and furanic compounds of Portuguese chestnut and French, American and Portuguese oak wood chips

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.

Atenolol removal in microcosm constructed wetlands

Microcosm constructed wetland systems established with a matrix of light expanded clay aggregates (LECA) and Typha spp. or Phragmites australis were used to evaluate their ability to remove atenolol from wastewater. Combined with an efficient SPE concentration step, the use of HPLC-DAD yielded an analytical method for atenolol quantification with very low LOQ (9 ng mL−1) and high reproducibility (RSD < 4%). Overall removal efficiencies of 92.5% and 94.5% were achieved after a retention time of only 4 days with the microcosm systems planted with Phragmites australis and Typha spp., respectively. The removal kinetics was characterised by an initial fast step (removal of about 75% after just 24 h) which is mainly attributable to adsorption on the LECA matrix. Atenolol removal in LECA beds continues to increase in a steady pace up to the end of the assay (8 days) being nevertheless about 5–10% lower than those observed in the planted beds after the first 4 days. For the retention time of 4 days most of the atenolol is removed by the LECA matrix but an additional 12–14% of the overall removal efficiency can be attributed to the Typha and Phragmites plants, which is in agreement with other published reports. Despite the fact that further tests using larger-scale flowing systems are required to evaluate fully the atenolol behaviour in constructed wetlands, this study points to the possible application of these low-cost wastewater treatment systems to treat atenolol contaminated wastewater.

Material Characterization and Biodegradation Assessment of Mural Paintings: Renaissance Frescoes from Santo Aleixo Church, Southern Portugal

The aim of this work is the material characterization 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, scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS) and μ- X-ray diffraction (XRD) showed that the painting palette is composed of red and yellow ochers, malachite, azurite, and bone black. The pigments do not show signs of chemical deterioration, except for malachite, which transformed to black copper oxide (tenorite). The microbiological study allowed the identification of several bacterial strains (e.g., Gram+ cocci, Gram+ bacilli, Actinomycetes sp.), yeast strains, and filamentous fungi of the genera Penicillium, Cladosporium and Aspergillus, among others of the microflora present in the paintings. Their metabolic activity is primarily responsible for the physical disruption of paint layers and underlying mortars. The combined approach using SEM analysis and enzymatic dehydrogenase measurement allowed the evaluation of microflora proliferation and diagnosis of the biodeterioration of the mural paintings. Additionally, the effect of some commercial biocides was evaluated for the predominant strains in order to select the most efficient biocide.

On the Use of the Unusual Green Pigment Brochantite (Cu 4 (SO 4 )(OH) 6 ) in the 16th-Century Portuguese- Flemish Paintings Attributed to The Master Frei Carlos Workshop

This paper reports an unusual green pigment, brochantite (Cu4(SO4)(OH)6), on 16th-century Portuguese-Flemish paintings, attributed to the Master Frei Carlos workshop. This green mineral is usually identified as an impurity or alteration product in the green pigments verdigris (Cu(CH3COO)2 nCu(OH)2) or malachite (CuCO3 Cu(OH)2). However, after thorough investigation with a broad range of analytical techniques, it became clear that, in this case, brochantite was applied as a pigment. The abundance, pigment granulometry, and pigment morphology suggest intentional use by this Portuguese-Flemish Master as a natural pigment rather than its accidental use as an alteration product. This seems to be a distinguishable feature to other painters (Flemish and Portuguese) working in Portugal at the beginning of the 16th century. The multi-analytical study of these easel paintings was first performed by physical imaging techniques and material characterization was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and micro-X-ray diffraction analysis (XRD).

A perylene conductor with a gold cyanodithiocarbimate counterion: (Perylene)2Au(cdc)2

Abstract The synthesis, electrocrystallisation and characterisation of (Perylene) 2 Au(cdc) 2 single crystals, where cdc=cyanodithiocarbimate, are reported. The electrical conductivity and thermoelectric power exhibit metallic character at room temperature, with typical values σ RT =150 S. cm −1 and S =35μV.K −1 , respectively. Both resistivity and thermopower exhibit shallow minima in the range 100–150 K. Static magnetic susceptibility measurements show a Pauli-like behaviour ascribed to the perylene chains, with indication of a transition at ≈45 K. These properties are compared with those of other perylene conductors containing dithiolate complexes and the role of disorder is discussed.

Analytical characterization of the palette and painting techniques of Jorge Afonso, the great 16th century Master of Lisbon painting workshop

In this work, a study on a set of paintings from the most significant altarpiece assigned to Master Jorge Afonso (c. 1470-1540) painting workshop is presented. This altarpiece is composed by fourteen paintings made to the church of Convento de Jesus, in Setúbal, Portugal, and was made circa 1517-19/1530, according to art-history. This set of paintings is compared to one of the other most important Portuguese altarpieces from the 16th century: the panels of the Round Church of the Convento de Cristo, in Tomar, made circa 1510-1515. The aim of this study is to characterize the wooden support, pigments, ground layers materials and technique used in Jorge Afonso workshop by means of complementary analyses. A dendrochronological approach was made in order to corroborate (or not) the historical date initially assigned. Infrared photography (IRP) and reflectography (IRR) allowed the study of the underdrawing technique and macro photography (MP) was used to recognize overlapping layers technique. Cross-sections from the paintings were examined by optical microscopy (OM), and analyzed by μ-X-ray diffraction (μ-XRD), Energy Dispersive X-ray Fluorescence spectroscopy (EDXRF), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS), micro-Raman spectroscopy (μ-Raman), micro-Fourier Transform Infrared spectroscopy (μ-FTIR), Pyrolysis Gas Chromatography Mass Spectrometry (py-GC/MS). The characterization of the palette and ground layers and the study of the overlapping of paint layers brought a new insight of the adopted painting techniques by the most important group of painters working in Portugal in the 16th century - the Lisbon workshop, leaded by Master Jorge Afonso.

Effect of edible coatings with essential oils on the quality of red raspberries over shelf-life: Edible coatings with essential oils on the red raspberries

BACKGROUND The objective of the present work was to develop strategies for increasing the shelf-life of red raspberries (Rubus idaeus L.), by preventing microorganism growth. RESULTS Fruits coated with alginate plus lemon essential oil (0.2%) or orange essential oil (0.1%) after 15 days of storage had less red skin than the remaining samples. The less red color verified in these samples was also coincident with the lower concentration of anthocyanins at the end of the experiment as well as the lower capacity for scavenging ABTS free radicals or quenching singlet oxygen. Cyanidin and pelargonidin glucosides were found in raspberries fruits. The edible coatings supplemented with the essential oil of orange either at 0.1% or 0.2% were very efficient for controlling yeast and mold growth after 15 days of storage. To control the development of aerobic mesophilic bacteria the use of essential oil of lemon 0.2% and essential oil of orange 0.1% were the most efficient. CONCLUSION The application of the film improved post-harvest quality of raspberry, since the addition of essential oils of citrus films promoted to the inhibitory effect of fungi and bacteria growth after 15 days of storage, without changing quality parameters.