Flavored waters: influence of ingredients on antioxidant capacity and terpenoid profile by HS-SPME/GC-MS

The antioxidant profiles of 39 water samples (29 flavored waters based on 10 natural waters) and 6 flavors used in their formulation (furnished by producers) were determined. Total phenol and flavonoid contents, reducing power, and DPPH radical scavenging activity were the optical techniques implemented and included in the referred profile. Flavor extracts were analyzed by HS-SPME/GC-MS to obtain the qualitative and quantitative profiles of the volatile fraction of essential oils. Results pointed out a higher reducing power (0.14 11.8 mg of gallic acid/L) and radical scavenging activity (0.29 211.5 mg Trolox/L) of flavored waters compared with the corresponding natural ones, an interesting fact concerning human health. Bioactive compounds, such as polyphenols, were present in all samples (0.5 359 mg of gallic acid/L), whereas flavonoids were not present either in flavored waters or in flavors. The major components of flavor extracts were monoterpenes, such as citral, R-limonene, carveol, and R-terpineol.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

Assessment of guanylin peptides system in type 2 diabetes

Os doentes com diabetes mellitus tipo 2 apresentam predisposição para a retenção de sódio e são frequentemente hipertensos. No entanto, os mecanismos implicados na dificuldade do rim diabético em mobilizar o sódio são, ainda, pouco compreendidos. Os peptídeos da família das guanilinas estão envolvidos na regulação do transporte de electrólitos e água nos epitélios intestinal e renal, através da activação do receptor guanilato ciclase-C (GC-C) e subsequente libertação intracelular de GMPc. O objectivo do presente estudo foi a avaliação da actividade do sistema dos peptídeos das guanilinas (SPG) e do seu papel na regulação do balanço de sódio num modelo animal de diabetes tipo 2. Ratinhos machos C57BL/6 foram submetidos a uma dieta com alto teor de gordura e rica em hidratos de carbono simples (ratinhos diabéticos) ou a uma dieta normal (ratinhos controlo). A expressão renal e intestinal da guanilina (GN), uroguanilina (UGN) e do receptor GC-C assim como os níveis de GMPc na urina e plasma foram avaliados nos ratinhos controlo e diabéticos, durante a ingestão de dietas normo (NS) e hiper-salina (HS). Nos ratinhos diabéticos, durante a dieta NS verificou-se um aumento significativo da pressão arterial que foi acompanhado de redução da expressão do ARNm da GN, UGN e do GC-C no intestino e de aumento da expressão de ARNm da UGN no rim. A dieta HS induziu um aumento da expressão do ARNm da UGN no jejuno dos ratinhos controlo mas não nos diabéticos. Os ratinhos diabéticos apresentaram níveis urinários de GMPc inferiores aos controlos, em condições de dieta NS. Em conclusão, os nossos resultados sugerem que na diabetes tipo 2 ocorre uma redução da actividade intestinal do SPG que é acompanhada por um aumento compensatório da actividade renal do SPG. A diminuição da actividade do SPG intestinal na diabetes tipo 2 deve-se não só a uma redução da expressão dos peptídeos GN e UGN, mas também a uma redução da expressão do seu receptor, GC-C. Estes resultados sugerem que o SPG pode contribuir para a sensibilidade ao sódio na diabetes.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Avaliação de compostos halogenados em água e ar de piscinas

A procura de piscinas para a prática de atividades desportivas, recreativas e/ou terapêuticas tem sofrido um aumento gradual ao longo do tempo. No entanto, nas piscinas existem vários perigos associados à sua utilização. Relativamente aos perigos químicos, a utilização de desinfetantes à base de cloro, bromo ou compostos derivados vai, por um lado, inativar microrganismos patogénicos mas, por outro, dar origem a subprodutos ao reagir com compostos orgânicos presentes na água. Os trihalometanos são um exemplo de subprodutos que se podem formar e, entre os compostos principais, estão o clorofórmio (TCM), bromodiclorometano (BDCM), clorodibromometano (CDBM) e bromofórmio (TBM). Este trabalho teve como objetivo o desenvolvimento de uma metodologia analítica para a determinação de trihalometanos em água e ar de piscinas e a sua aplicação a um conjunto de amostras. Para a análise dos compostos, foi utilizada a microextração em fase sólida no espaço de cabeça (HS-SPME) com posterior quantificação dos compostos por cromatografia gasosa com detetor de captura eletrónica (GC-ECD). Foi realizada uma otimização das condições de extração dos compostos em estudo em amostras de água, através da realização de dois planeamentos experimentais. As condições ótimas são assim obtidas para uma temperatura de extração de 45ºC, um tempo de extração de 25 min e um tempo de dessorção de 5 min. Foram analisadas amostras de águas de piscina cedidas pelo Centro de Estudos de Águas, sendo avaliada a aplicação da técnica HS-SPME e o efeito de matriz. O modo como se manuseiam as soluções que contêm os compostos em estudo influencia os resultados devido ao facto destes serem bastante voláteis. Concluiu-se também que existe efeito de matriz, logo a concentração das amostras deverá ser determinada através do método de adição de padrão. A caraterização da água de piscinas interiores permitiu conhecer a concentração de trihalometanos (THMs). Foram obtidas concentrações de TCM entre 4,5 e 406,5 μg/L sendo que apenas 4 das 27 amostras analisadas ultrapassam o valor limite imposto pelo Decreto-Lei nº306/2007 (100 μg/L) no que diz respeito a águas de consumo humano e que é normalmente utilizado como valor indicativo para a qualidade das águas de piscina. Relativamente à concentração obtida no ar de uma piscina interior, foi detetada uma concentração média de 224 μg/m3 de TCM, valor muito abaixo dos 10000 μg/m3 impostos pelo Decreto-lei nº24/2012, como valor limite para exposição profissional a agentes químicos.

Formação alternativa no ISCAP

O Ensino Superior Politécnico deve aproveitar o Processo de Bolonha para assumir um papel de relevo na resposta às necessidades do mercado de trabalho, seja através da adequação dos planos curriculares das suas licenciaturas e mestrados às reais necessidades dos empregadores, seja através da realização de formações que permitam aos trabalhadores no activo ou no desemprego aumentar, actualizar, diversificar e aprofundar os seus conhecimentos, para melhorarem a sua empregabilidade e melhor competirem a nível nacional e internacional, de modo a constituirem uma mais valia para as organizações onde trabalham. O ISCAP tentou já essa via com sucesso, com a oferta de dois cursos, um na área da contabilidade e fiscalidade e outro na área da tradução.

Simultaneous distillation–extraction of high-value volatile compounds from Cistus ladanifer L.

The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation–extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%). The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 µm polyacrylate fiber for a 60 min headspace extraction at 40ºC with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g−1 of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g−1 of extract), borneol (3.0 mg g−1 of extract) and bornyl acetate (3.9 mg g−1 of extract) were identified in the SDE extracts obtained from the fresh plant material.

Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction–headspace solid phase microextraction and gas chromatography–tandem mass spectrometry

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Classification Performance of Multilayer Perceptrons with Different Risk Functionals

In the present paper we assess the performance of information-theoretic inspired risks functionals in multilayer perceptrons with reference to the two most popular ones, Mean Square Error and Cross-Entropy. The information-theoretic inspired risks, recently proposed, are: HS and HR2 are, respectively, the Shannon and quadratic Rényi entropies of the error; ZED is a risk reflecting the error density at zero errors; EXP is a generalized exponential risk, able to mimic a wide variety of risk functionals, including the information-thoeretic ones. The experiments were carried out with multilayer perceptrons on 35 public real-world datasets. All experiments were performed according to the same protocol. The statistical tests applied to the experimental results showed that the ubiquitous mean square error was the less interesting risk functional to be used by multilayer perceptrons. Namely, mean square error never achieved a significantly better classification performance than competing risks. Cross-entropy and EXP were the risks found by several tests to be significantly better than their competitors. Counts of significantly better and worse risks have also shown the usefulness of HS and HR2 for some datasets.

O alisamento dos resultados numa empresa: o caso do Grupo SONANGOL

Dissertação de Mestrado apresentada ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças sob orientação de Professor Doutor Adalmiro Alvaro Malheiro de Castro Andrade Pereira

Strength and damage analysis of composite-aluminium adhesively-bonded single-lap joints

With the need to find an alternative way to mechanical and welding joints, and at the same time to overcome some limitations linked to these traditional techniques, adhesive bonds can be used. Adhesive bonding is a permanent joining process that uses an adhesive to bond the components of a structure. Composite materials reinforced with fibres are becoming increasingly popular in many applications as a result of a number of competitive advantages. In the manufacture of composite structures, although the fabrication techniques reduce to the minimum by means of advanced manufacturing techniques, the use of connections is still required due to the typical size limitations and design, technological and logistical aspects. Moreover, it is known that in many high performance structures, unions between composite materials with other light metals such as aluminium are required, for purposes of structural optimization. This work deals with the experimental and numerical study of single lap joints (SLJ), bonded with a brittle (Nagase Chemtex Denatite XNRH6823) and a ductile adhesive (Nagase Chemtex Denatite XNR6852). These are applied to hybrid joints between aluminium (AL6082-T651) and carbon fibre reinforced plastic (CFRP; Texipreg HS 160 RM) adherends in joints with different overlap lengths (LO) under a tensile loading. The Finite Element (FE) Method is used to perform detailed stress and damage analyses allowing to explain the joints’ behaviour and the use of cohesive zone models (CZM) enables predicting the joint strength and creating a simple and rapid design methodology. The use of numerical methods to simulate the behaviour of the joints can lead to savings of time and resources by optimizing the geometry and material parameters of the joints. The joints’ strength and failure modes were highly dependent on the adhesive, and this behaviour was successfully modelled numerically. Using a brittle adhesive resulted in a negligible maximum load (Pm) improvement with LO. The joints bonded with the ductile adhesive showed a nearly linear improvement of Pm with LO.