Chlormequat selective electrodes: construction, evaluation and application at FIA systems

A flow injection analysis (FIA) system having a chlormequat selective electrode is proposed. Several electrodes with poly(vinyl chloride) based membranes were constructed for this purpose. Comparative characterization suggestedthe use of membrane with chlormequat tetraphenylborate and dibutylphthalate. On a single-line FIA set-up, operating with 1x10-2 mol L-1 ionic strength and 6.3 pH, calibration curves presented slopes of 53.6±0.4mV decade-1 within 5.0x10-6 and1.0x10-3 mol L-1, andsquaredcorrelation coefficients >0.9953. The detection limit was 2.2x10-6 mol L-1 and the repeatability equal to ±0.68mV (0.7%). A dual-channel FIA manifold was therefore constructed, enabling automatic attainment of previous ionic strength andpH conditions and thus eliminating sample preparation steps. Slopes of 45.5±0.2mV decade -1 along a concentration range of 8.0x10-6 to 1.0x10-3 mol L-1 with a repeatability ±0.4mV (0.69%) were obtained. Analyses of real samples were performed, and recovery gave results ranging from 96.6 to 101.1%.

Electrocatalytic evaluation of DNA damage by superoxide radical for antioxidant capacity assessment

The integrity of DNA purine bases was herein used to evaluate the antioxidant capacity. Unlike other DNA-based antioxidant sensors reported so far, the damaging agent chosen was the O 2 radical enzymatically generated by the xanthine/xanthine oxidase system. An adenine-rich oligonucleotide was adsorbed on carbon paste electrodes and subjected to radical damage in the presence/absence of several antioxidant compounds. As a result, partial damage on DNA was observed. A minor product of the radical oxidation was identified by cyclic voltammetry as a diimine adenine derivative also formed during the electrochemical oxidation of adenine/guanine bases. The protective efficiency of several antioxidant compounds was evaluated after electrochemical oxidation of the remaining unoxidized adenine bases, by measuring the electrocatalytic current of NADH mediated by the adsorbed catalyst species generated. A comparison between O 2 and OH radicals as a source of DNA lesions and the scavenging efficiency of various antioxidant compounds against both of them is discussed. Finally, the antioxidant capacity of beverages was evaluated and compared with the results obtained with an optical method.

Evaluation of the total antioxidant capacity of flavored water and electrochemical purine damage by sulfate radicals using a purine-based sensor

In this study, a method for the electrochemical quantification of the total antioxidant capacity (TAC) in beverages was developed. The method is based on the oxidative damage to the purine bases, adenine or guanine, that are immobilized on a glassy carbon electrode (GCE) surface. The oxidative lesions on the DNA bases were promoted by the sulfate radical generated by the persulfate/iron(II) system. The presence of antioxidants on the reactive system promoted the protection of the DNA bases immobilized on the GCE by scavenging the sulfate radical. Square-wave voltammetry (SWV) was the electrochemical technique used to perform this study. The efficiencies of five antioxidants (ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol) in scavenging the sulfate radical and, therefore, their ability to protect the purine bases immobilized on the GCE were investigated. These results demonstrated that the purine-based biosensor is suitable for the rapid assessment of the TAC in flavors and flavored water.

Towards a reliable technology for antioxidant capacity and oxidative damage evaluation: Electrochemical (bio)sensors

To counteract and prevent the deleterious effect of free radicals the living organisms have developed complex endogenous and exogenous antioxidant systems. Several analytical methodologies have been proposed in order to quantify antioxidants in food, beverages and biological fluids. This paper revises the electroanalytical approaches developed for the assessment of the total or individual antioxidant capacity. Four electrochemical sensing approaches have been identified, based on the direct electrochemical detection of antioxidant at bare or chemically modified electrodes, and using enzymatic and DNA-based biosensors.

Evaluation of ochratoxin A exposure degree in two Portuguese cities through wheat and maize bread consumption during the winter 2007

The occurrence of OTA in fresh and packed wheat and in maize bread and the evaluation of the exposure degree through their consumption in two Portuguese populations from Porto and Coimbra, during the winter of 2007, were studied. One hundred and sixty eight bread samples, 61 maize and 107 wheat, were analysed by liquid chromatography–fluorescence detection (LC–FD). The results showed that 84% of samples were contaminated, with a maximum level of 3.85 ng/g (above the EU maximum limit, 3 ng/g). Fresh wheat bread presented higher levels than packed wheat bread. Moreover, the traditional maize bread, in either city, was consistently more contaminated than wheat bread, 0.25 vs 0.19 ng/g, and 0.48 vs 0.34 ng/ g for Porto and Coimbra, respectively. Avintes maize bread showed the highest mean contamination and maximum levels. The higher estimated daily intake of OTA from both types of bread in the population of Coimbra compared to Porto reflects the higher average contamination of bread in the first city.

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production.

Hearing evaluation of portuguese school communities: school‑based audiology and hearing screening

Introduction: Hearing loss h sone raised impact in the development and academic progress of a child. In several developed countries, early detection is part of the national health plan through universal neonatal hearing screening (UNHS) and also with school hearing screening programs (SHSP), but only a few have published national data and revised protocols. Currently in Portugal, the UNHS is implemented in the main district hospitals but not the SHPS, as well we still do not make use of concrete data nor publication of studies on the national reality. Objectives: The incidence of the hearing loss and of otological problems was studied in school communities in the north of the country with 2550 participants between 3 and 17 years old. Methods: Statistical data collected within the schools with a standard auditory hearing screening protocol. All participants were evaluated with the same protocol, an audiological anamnesis, otoscopy and audiometric exam screening (500, 1000, 2000 and 4000 Hz) were fulfilled. Results: Different otological problems were identified and the audiometric screening exam counted auditory thresholds that outpointed uni and bilateral hearing loss in about 5.7% of the cases. Conclusions: The study has demonstrated that auditory school screening should take place as early as possible and be part of the primary health care to identify and direct children to appropriate rehabilitation, education and attendance. Thus, reducing high costs with late treatment.

Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicity

In 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.

Brewer's spent grain from different types of malt: Evaluation of the antioxidant activity and identification of the major phenolic compounds

The antioxidant activity and phenolic composition of brewer's spent grain (BSG) extracts obtained by microwave-assisted extraction from twomalt types (light and darkmalts) were investigated. The total phenolic content (TPC) and antioxidant activity among the light BSG extracts (pilsen, melano, melano 80 and carared)were significantly different (p b 0.05) compared to dark extracts (chocolate and black types), with the pilsen BSG showing higher TPC (20 ± 1 mgGAE/g dry BSG). In addition, the antioxidant activity assessed by 2,2-diphenyl- 1-picrylhydrazyl, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) and deoxyribose assays decreased as a result of increasing kilning temperatures in the following order: pilsen N melano N melano 80 N carared N chocolate N black. HPLC-DAD/ESI-MS/MS analysis indicated the presence of phenolic acids, such as ferulic, p-coumaric and syringic acids, as well as several isomeric ferulate dehydrodimers and one dehydrotrimer. Chocolate and black extracts, obtained frommalts submitted to the highest kilning temperatures, showed the lowest levels of ferulic and p-coumaric acids. These results suggested that BSG extracts from pilsen malt might be used as an inexpensive and good natural source of antioxidants with potential interest for the food, pharmaceutical and/or cosmetic industries after purification.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Orchestration of e-learning services for automatic evaluation of programming exercises

Managing programming exercises require several heterogeneous systems such as evaluation engines, learning objects repositories and exercise resolution environments. The coordination of networks of such disparate systems is rather complex. These tools would be too specific to incorporate in an e-Learning platform. Even if they could be provided as pluggable components, the burden of maintaining them would be prohibitive to institutions with few courses in those domains. This work presents a standard based approach for the coordination of a network of e-Learning systems participating on the automatic evaluation of programming exercises. The proposed approach uses a pivot component to orchestrate the interaction among all the systems using communication standards. This approach was validated through its effective use on classroom and we present some preliminary results.

Evaluation of distinct input methods of an intelligent wheelchair in simulated and real environments: a performance and usability study

This paper focuses on evaluating the usability of an Intelligent Wheelchair (IW) in both real and simulated environments. The wheelchair is controlled at a high-level by a flexible multimodal interface, using voice commands, facial expressions, head movements and joystick as its main inputs. A Quasi-experimental design was applied including a deterministic sample with a questionnaire that enabled to apply the System Usability Scale. The subjects were divided in two independent samples: 46 individuals performing the experiment with an Intelligent Wheelchair in a simulated environment (28 using different commands in a sequential way and 18 with the liberty to choose the command); 12 individuals performing the experiment with a real IW. The main conclusion achieved by this study is that the usability of the Intelligent Wheelchair in a real environment is higher than in the simulated environment. However there were not statistical evidences to affirm that there are differences between the real and simulated wheelchairs in terms of safety and control. Also, most of users considered the multimodal way of driving the wheelchair very practical and satisfactory. Thus, it may be concluded that the multimodal interfaces enables very easy and safe control of the IW both in simulated and real environments.

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.

Evaluation of dynamic pass-through of carbon prices into electricity prices – a cointegrated VECM analysis

This paper addresses the impact of the CO2 opportunity cost on the wholesale electricity price in the context of the Iberian electricity market (MIBEL), namely on the Portuguese system, for the period corresponding to the Phase II of the European Union Emission Trading Scheme (EU ETS). In the econometric analysis a vector error correction model (VECM) is specified to estimate both long–run equilibrium relations and short–run interactions between the electricity price and the fuel (natural gas and coal) and carbon prices. The model is estimated using daily spot market prices and the four commodities prices are jointly modelled as endogenous variables. Moreover, a set of exogenous variables is incorporated in order to account for the electricity demand conditions (temperature) and the electricity generation mix (quantity of electricity traded according the technology used). The outcomes for the Portuguese electricity system suggest that the dynamic pass–through of carbon prices into electricity prices is strongly significant and a long–run elasticity was estimated (equilibrium relation) that is aligned with studies that have been conducted for other markets.