Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Facile synthesis of freestanding Si nanowire arrays by one-step template-free electro-deoxidation of SiO2 in molten salt

This communication presents a novel kind of silicon nanomaterial: freestanding Si nanowire arrays (Si NWAs), which are synthesized facilely by one-step template-free electro-deoxidation of SiO2 in molten CaCl2. The self-assembling growth process of this material is also investigated preliminarily.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Adsorption kinetics of removal of yellow lanasol dyestuff using gallinaceous feathers

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.

Growth pressure dependence of Cu2ZnSnSe4 properties

In this work, we show a set of growth conditions, for the two step process, with which the growth of CZTSe is successful and reproducible. The properties of the best CTZSe thin films grown by this method were examined by SEM/EDS, XRD, Raman scattering, AFM/EFM, transmittance and reflectance measurements, photoluminescence (PL) measurements and hot point probe. A broad emission band was observed in the photoluminescence spectrum of the CZTSe thin film. The band gap energy was estimated to be around 1.05 eV at room temperature, using the transmittance and reflectance data, and CZTSe samples show p-type conductivity with the hot point probe. The different characterization techniques show that we could grow single phase CZTSe thin films with our optimized process conditions.

Implementação em hardware reconfigurável de método de separação de dados hiperespetrais

Relatório do Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Electrónica e Telecomunicações

Fractional dynamics of genetic algorithms using hexagonal space tessellation

The paper formulates a genetic algorithm that evolves two types of objects in a plane. The fitness function promotes a relationship between the objects that is optimal when some kind of interface between them occurs. Furthermore, the algorithm adopts an hexagonal tessellation of the two-dimensional space for promoting an efficient method of the neighbour modelling. The genetic algorithm produces special patterns with resemblances to those revealed in percolation phenomena or in the symbiosis found in lichens. Besides the analysis of the spacial layout, a modelling of the time evolution is performed by adopting a distance measure and the modelling in the Fourier domain in the perspective of fractional calculus. The results reveal a consistent, and easy to interpret, set of model parameters for distinct operating conditions.

Tensile behaviour of a structural adhesive at high temperatures by the extended finite element method

Component joining is typically performed by welding, fastening, or adhesive-bonding. For bonded aerospace applications, adhesives must withstand high-temperatures (200°C or above, depending on the application), which implies their mechanical characterization under identical conditions. The extended finite element method (XFEM) is an enhancement of the finite element method (FEM) that can be used for the strength prediction of bonded structures. This work proposes and validates damage laws for a thin layer of an epoxy adhesive at room temperature (RT), 100, 150, and 200°C using the XFEM. The fracture toughness (G Ic ) and maximum load ( ); in pure tensile loading were defined by testing double-cantilever beam (DCB) and bulk tensile specimens, respectively, which permitted building the damage laws for each temperature. The bulk test results revealed that decreased gradually with the temperature. On the other hand, the value of G Ic of the adhesive, extracted from the DCB data, was shown to be relatively insensitive to temperature up to the glass transition temperature (T g ), while above T g (at 200°C) a great reduction took place. The output of the DCB numerical simulations for the various temperatures showed a good agreement with the experimental results, which validated the obtained data for strength prediction of bonded joints in tension. By the obtained results, the XFEM proved to be an alternative for the accurate strength prediction of bonded structures.

Mathematical aspects of the Heisenberg uncertainty principle within local fractional Fourier analysis

In this paper, we discuss the mathematical aspects of the Heisenberg uncertainty principle within local fractional Fourier analysis. The Schrödinger equation and Heisenberg uncertainty principles are structured within local fractional operators.

Contributo para a determinação simultânea, por cromatografia líquida de alta resolução, de carotenoides, vitamina A e vitamina E em amostras compostas por diferentes matrizes alimentares

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Projecto de avaliação de interfaces – PAI

Para obtenção do grau de Doutor pela Universidade de Vigo com menção internacional Departamento de Informática

WCET analysis considering contention on memory bus in COTS-based multicores

The usage of COTS-based multicores is becoming widespread in the field of embedded systems. Providing realtime guarantees at design-time is a pre-requisite to deploy real-time systems on these multicores. This necessitates the consideration of the impact of the contention due to shared low-level hardware resources on the Worst-Case Execution Time (WCET) of the tasks. As a step towards this aim, this paper first identifies the different factors that make the WCET analysis a challenging problem in a typical COTS-based multicore system. Then, we propose and prove, a mathematically correct method to determine tight upper bounds on the WCET of the tasks, when they are co-scheduled on different cores.

Analysis of temperature time-series: embedding dynamics into the MDS method

Global warming and the associated climate changes are being the subject of intensive research due to their major impact on social, economic and health aspects of the human life. Surface temperature time-series characterise Earth as a slow dynamics spatiotemporal system, evidencing long memory behaviour, typical of fractional order systems. Such phenomena are difficult to model and analyse, demanding for alternative approaches. This paper studies the complex correlations between global temperature time-series using the Multidimensional scaling (MDS) approach. MDS provides a graphical representation of the pattern of climatic similarities between regions around the globe. The similarities are quantified through two mathematical indices that correlate the monthly average temperatures observed in meteorological stations, over a given period of time. Furthermore, time dynamics is analysed by performing the MDS analysis over slices sampling the time series. MDS generates maps describing the stations’ locus in the perspective that, if they are perceived to be similar to each other, then they are placed on the map forming clusters. We show that MDS provides an intuitive and useful visual representation of the complex relationships that are present among temperature time-series, which are not perceived on traditional geographic maps. Moreover, MDS avoids sensitivity to the irregular distribution density of the meteorological stations.