ISEP - GRAQ - Grupo de Reacção de Análises Químicas
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O GRAQ é uma equipa pluridisciplinar de investigadores cuja missão é a investigação no domínio da Engenharia Química e da Química Verde, contribuindo para a criação, aplicação e divulgação de conhecimento e promover a inovação. O GRAQ está integrado no Laboratório Associado para a Química Verde - REQUIMTE.
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- 3D-nanostructured Au electrodes for the event-specific detection of MON810 transgenic maizePublication . Barroso, M. Fátima; Freitas, Maria; Oliveira, M. Beatriz P.P.; de-los-Santos-Álvarez, Noemí; Lobo-Castañón, María Jesús; Delerue-Matos, CristinaIn the present work, the development of a genosensor for the event-specific detection of MON810 transgenic maize is proposed. Taking advantage of nanostructuration, a cost-effective three dimensional electrode was fabricated and a ternary monolayer containing a dithiol, a monothiol and the thiolated capture probe was optimized to minimize the unspecific signals. A sandwich format assay was selected as a way of precluding inefficient hybridization associated with stable secondary target structures. A comparison between the analytical performance of the Au nanostructured electrodes and commercially available screen-printed electrodes highlighted the superior performance of the nanostructured ones. Finally, the genosensor was effectively applied to detect the transgenic sequence in real samples, showing its potential for future quantitative analysis.
- Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicityPublication . Morais, Sérgio Alberto; Delerue-Matos, Cristina; Gabarrell, XavierIn life cycle impact assessment (LCIA) models, the sorption of the ionic fraction of dissociating organic chemicals is not adequately modeled because conventional non-polar partitioning models are applied. Therefore, high uncertainties are expected when modeling the mobility, as well as the bioavailability for uptake by exposed biota and degradation, of dissociating organic chemicals. Alternative regressions that account for the ionized fraction of a molecule to estimate fate parameters were applied to the USEtox model. The most sensitive model parameters in the estimation of ecotoxicological characterization factors (CFs) of micropollutants were evaluated by Monte Carlo analysis in both the default USEtox model and the alternative approach. Negligible differences of CFs values and 95% confidence limits between the two approaches were estimated for direct emissions to the freshwater compartment; however the default USEtox model overestimates CFs and the 95% confidence limits of basic compounds up to three orders and four orders of magnitude, respectively, relatively to the alternative approach for emissions to the agricultural soil compartment. For three emission scenarios, LCIA results show that the default USEtox model overestimates freshwater ecotoxicity impacts for the emission scenarios to agricultural soil by one order of magnitude, and larger confidence limits were estimated, relatively to the alternative approach.
- Acetylated cashew gum-based nanoparticles for the incorporation of alkaloid epiisopiloturinePublication . Rodrigues, Jessica do Amaral; Araújo, Alyne Rodrigues de; Pitombeira, Nadia Aline; Plácido, Alexandra; Almeida, Miguel Peixoto de; Veras, Leiz Maria Costa; Delerue-Matos, Cristina; Lima, Filipe Camargo Dalmatti Alves; Neto, Augusto Batagin; Paula, Regina Célia Monteiro de; Feitosa, Judith Pessoa Andrade; Eaton, Peter; Leite, José Roberto Souza A.; Silva, Durcilene Alves daThe natural alkaloid epiisopiloturine has recently become the focus of study for various medicinal properties, particularly for its anti-inflammatory and antischistosomal effect. The incorporation of active molecules in natural polymeric matrices has garnered increasing interest during recent decades. A new derivative of cashew gum successfully obtained by gum acetylation has shown great potential as a carrier in controlled drug release systems. In this work, epiisopiloturine was encapsulated in acetylated cashew gum nanoparticles in order to increase solubility and allow slow release, whereas the morphology results were supported by computer simulations. The particles were produced under a variety of conditions, and thoroughly characterized using light scattering and microscopic techniques. The particles were spherical and highly stable in solution, and showed drug incorporation at high levels, up to 55% efficiency. Using a dialysis-based in vitro assay, these particles were shown to release the drug via a Fickian diffusion mechanism, leading to gradual drug release over approximately 6 h. These nanoparticles show potential for the use as drug delivery system, while studies on their potential anti-inflammatory action, as well as toxicity and efficacy assays would need to be performed in the future to confirm their suitability as drug delivery candidates.
- Acid-base treated vermiculite as high performance adsorbent: Insights into the mechanism of cationic dyes adsorption, regeneration, recyclability and stability studiesPublication . Stawiński, Wojciech; Węgrzyn, Agnieszka; Dańko, Tomasz; Freitas, Olga; Figueiredo, Sónia; Chmielarz, LucjanAdditional treatment with NaOH of acid activated vermiculite results in even higher increase in the adsorption capacity in comparison to samples modified only in acidic solution (first step of activation) with respect to raw material. Optimization of treatment conditions and adsorption capacity for two cationic dyes (methylene blue (MB) and astrazon red (AR)), also as binary mixture, was evaluated. The capacity, based on column studies, increased from 48 ± 2 to 203 ± 4 mg g-1 in the case of methylene blue and from 51 ± 1 to 127 ± 2 mg g-1 in the case of astrazon red on starting and acid-base treated material, respectively. It was shown that adsorption mechanism changes for both cationic dyes after NaOH treatment and it results in decrease of adsorption rate. In binary mixtures methylene blue is bound stronger by adsorbent and astrazon red may be removed in initial stage of adsorption. Extensive studies on desorption/regeneration process proved high efficiency in recyclable use of all materials. Although cation exchange capacity decreases due to acid treatment, after base treatment exchange properties are used more efficiently. On the other hand, increased specific surface area has less significant contribution into the adsorption potential of studied materials. Obtained adsorbents worked efficiently in 7 adsorption-regeneration cycles and loss of adsorption capacity was observed only in two first cycles.
- Adding value [valorization] to tannery fleshings: part II – effect of protein hydrolysates on leather dyeingPublication . Bragança, Idalina; Nouws, Henri P. A.; Crispim, AlfredoThe tanning industry generates a high quantity of solid wastes. Therefore, there is a need to create valorization [added value] options for these wastes. The main objective of the present work was to study the effect of protein hydrolysates (HP) prepared from fleshings on leather dyeing. During previous studies it was found that the application of HP products, obtained from fleshings, in leather retannage intensified the colour of crust leather. In this work the CIELAB colour system was used to evaluate the effect of HP on retannage processes. The main conclusions of this study were: (i) HP can be used instead of a dicyanodiamide resin (Fortan DC) if the colour parameters of the standard procedure are to be maintained, and (ii) the replacement of an acrylic resin (Fortan A40) by glutaraldehyde-modified HP (GHP) results in a darker skin, and can therefore be interesting for the reduction of the quantity of dye used.
- Adipose tissue dysfunction as a central mechanism leading to dysmetabolic obesity triggered by chronic exposure to p,p’-DDEPublication . Pestana, Diogo; Teixeira, Diana; Meireles, Manuela; Marques, Cláudia; Norberto, Sónia; Sá, Carla; Fernandes, Virgínia; Correia-Sá, Luísa; Faria, Ana; Guardão, Luísa; Guimarães, João T.; Cooper, Wendy N.; Sandovici, Ionel; Domingues, Valentina; Delerue-Matos, Cristina; Monteiro, Rosário; Constância, Miguel; Calhau, ConceiçãoEndocrine-disrupting chemicals such as p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), are bioaccumulated in the adipose tissue (AT) and have been implicated in the obesity and diabetes epidemic. Thus, it is hypothesized that p,p'-DDE exposure could aggravate the harm of an obesogenic context. We explored the effects of 12 weeks exposure in male Wistar rats' metabolism and AT biology, assessing a range of metabolic, biochemical and histological parameters. p,p'-DDE -treatment exacerbated several of the metabolic syndrome-accompanying features induced by high-fat diet (HF), such as dyslipidaemia, glucose intolerance and hypertension. A transcriptome analysis comparing mesenteric visceral AT (vAT) of HF and HF/DDE groups revealed a decrease in expression of nervous system and tissue development-related genes, with special relevance for the neuropeptide galanin that also revealed DNA methylation changes at its promoter region. Additionally, we observed an increase in transcription of dipeptidylpeptidase 4, as well as a plasmatic increase of the pro-inflammatory cytokine IL-1β. Our results suggest that p,p'-DDE impairs vAT normal function and effectively decreases the dynamic response to energy surplus. We conclude that p,p'-DDE does not merely accumulate in fat, but may contribute significantly to the development of metabolic dysfunction and inflammation. Our findings reinforce their recognition as metabolism disrupting chemicals, even in non-obesogenic contexts.
- Adsorption behavior of α-cypermethrin on cork and activated carbonPublication . Domingues, Valentina F.; Priolo, Giuseppe; Alves, Arminda; Cabral, Miguel; Delerue-Matos, CristinaStudies were undertaken to determine the adsorption behavior of α-cypermethrin [R)-α-cyano-3-phenoxybenzyl(1S)-cis- 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α-cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α-cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (qm) (303 μg/g); followed by GAC (186 μg/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α-cypermethrin adsorption phenomena on GAC, while α-cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α-cypermethrin from water.
- Adsorption equilibrium studies of a simulated textile effluent containing a wool reactive dye on gallinaceous feathersPublication . Freitas, Olga M.; Moura, Lilita M.; Figueiredo, Sónia A.; Amorim, Maria T. Pessoa deGallinaceous feathers (from Gallus gallus domesticus, strains Cobb 500 and Label) were used as adsorbent for colour removal from a simulated textile effluent containing a wool reactive dye, the Yellow Lanasol 4G (CI Reactive Yellow 39). A brief chemical and physical characterisation of feathers was performed. Equilibrium studies at different selected temperatures, in the range 10–60 °C, were carried out. The equilibrium data were analysed using the Freundlich and Langmuir isotherm models. Adsorption capacity strongly increases with temperature. A maximum adsorption capacity of around 300 mg g-1 was obtained for Gallus gallus feathers, strain Cobb 500, at 60 °C, while for strain Label, 200 mg g-1 was obtained at 50 °C. For each type of feather a generalised model, valid for a given temperature range, was obtained. The isosteric heat of adsorption calculated was positive, so the mechanism involved in the adsorption process should correspond to endothermic chemisorption. This study provides important information concerning the use of gallinaceous feathers without any chemical treatment for colour removal from real textile wastewaters. The results in this study indicated that gallinaceous feathers, when compared with activated carbon, open promising perspectives concerning their utilisation for colour removal from textile effluent discharged at high temperatures; moreover, it would be an alternative for the valorisation of this waste.
- Adsorption kinetics of removal of yellow lanasol dyestuff using gallinaceous feathersPublication . Figueiredo, Sónia Adriana; Freitas, Olga M.Gallinaceous feathers are an abundant solid waste from the poultry processing industries, which poses disposal problems. A kinetic study dealing with the adsorption process of wool reactive dye, Yellow Lanasol 4G (CI Reactive Yellow 39), on gallinaceous (Gallus gallus, Cobb 500) feathers was carried out. The main research goals of this work were to evaluate the viability of using this waste as adsorbent and to study the kinetics of the adsorption process, using a synthetic effluent. The characterization of feathers was performed by scanning electron microscopy, mercury porosimetry and B.E.T. method. The study of several factors (stirring, particles size, initial dye concentration and temperature) showed their influence over the adsorption process. An adapted version of the Schumckler and Goldstein´s unreacted core model fitted the experimental data. The best fit was obtained when the rate-limiting step was the diffusion through the reacted layer, which was expected considering the size of the dyestuff molecules. The comparison with the granular activated carbon (GAC) Sutcliffe GAC 10-30 indicate that in spite of the high adsorption capacities shown by feathers the GAC presented higher values, the values obtained were respectively 150 and 219 mg g-1, for an initial concentration of 500 mg L-1. The results obtained might open future perspectives both to the valorization of feathers and to the economical treatment of textile wastewaters.
- Adsorption of Fluoxetine and Venlafaxine onto the Marine Seaweed Bifurcaria bifurcataPublication . Silva, Andreia; Stawiński, Wojciech; Romacho, Juan; Santos, Lúcia H.M.L.M.; Figueiredo, Sónia; Freitas, Olga; Delerue-Matos, CristinaMarine macroalga Bifurcaria bifurcata was investigated as sorbent for two environmental emerging pollutants, the pharmaceuticals venlafaxine (VLF) and fluoxetine (FLX), from aqueous solutions, both in mono and bicomponent batch systems. The alga was characterized by means of IR spectroscopy, allowing to identify the most important groups for biosorption, carboxylic, sulfonic and hidroxile. The point of zero charge was determined, being 6.4. Adsorption of FLX follows a pseudo first order kinetics and kinetic constants are higher for FLX than for VLF. Its adsorption better represented by the pseudo second order model. For both pharmaceuticals, the equilibrium was reached within *100 min. Adsorption studies reveal that the process was more efficient at lower pH range and followed the Langmuir–Freundlich’s model for VLF and Langmuir’s model for FLX. Maximum adsorption capacities reached a level of 12 – 3 and 22 – 4 lmol/g for VLF and FLX, respectively, in the mono-component system. The difference was attributed to the presence of various functional groups of varying polarity within the adsorbates’ molecules that affected their interactions with the adsorbent surface. The Langmuir–Freundlich’s extended model was applied to the adsorption data of the bicomponent system and no changes in the maximum adsorption capacities were found (14 – 2 and 20 – 3 lmol/g for VLF and FLX, respectively), there is no evidence of competition between the adsorbates.