Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives - Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies

The compounds [mPTA][CoCl4] (1, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [CoCl(H2O)(DION)(2)][BF4] (2, DION = 1,10-phenanthroline-5,6-dione), [Zn(DION)(2)]Cl-2 (3) and [ZnCl(O-PTA=O)(DION)][BF4] (4) were synthesized by reaction of CoCl2 with [mPTA]I or DION and ZnCl2 with DION or 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTA=O) and DION, respectively. All complexes are water soluble and have been characterized by IR, far-IR, H-1, C-13 and P-31{H-1} NMR spectroscopy, ESI-MS, elemental analyses and single-crystal X-ray diffraction structural analysis (for 1). They were screened against the human tumour cell lines HCT116, HepG2 and MCF7. Complexes 2 and 3 exhibit the highest in vitro cytotoxicity and show lower cytotoxic activities in normal human fibroblast cell line than in HCT116 tumour cell line, which demonstrates their slight specificity for this type of tumour cell.

Effect of oxidative stress upon absorption of glucose by the human placenta: in vitro studies with BeWo cells

Pregnancy is a dynamic state and the placenta is a temporary organ that, among other important functions, plays a crucial role in the transport of nutrients and metabolites between the mother and the fetus, which is essential for a successful pregnancy. Among these nutrients, glucose is considered a primary source of energy and, therefore, fundamental to insure proper fetus development. Several studies have shown that glucose uptake is dependent on several morphological and biochemical placental conditions. Oxidative stress results from the unbalance between reactive oxygen species (ROS) and antioxidants, in favor of the first. During pregnancy, ROS, and therefore oxidative stress, increase, due to increased tissue oxygenation. Moreover, the relation between ROS and some pathological conditions during pregnancy has been well established. For these reasons, it becomes essential to understand if oxidative stress can compromise the uptake of glucose by the placenta. To make this study possible, a trophoblastic cell line, the BeWo cell line, was used. Experiments regarding glucose uptake, either under normal or oxidative stress conditions, were conducted using tert-butylhydroperoxide (tBOOH) as an oxidative stress inducer, and 3H-2-deoxy-D-glucose (3H-DG) as a glucose analogue. Afterwards, studies regarding the involvement of glucose facilitative transporters (GLUT) and the phosphatidylinositol 3-kinases (PI3K) and protein kinase C (PKC) pathways were conducted, also under normal and oxidative stress conditions. A few antioxidants, endogenous and from diet, were also tested in order to study their possible reversible effect of the oxidative effect of tBOOH upon apical 3H-DG uptake. Finally, transepithelial studies gave interesting insights regarding the apical-to-basolateral transport of 3H-DG. Results showed that 3H-DG uptake, in BeWo cells, is roughly 50% GLUT-mediated and that tBOOH (100 μM; 24h) decreases apical 3H-DG uptake in BeWo cells by about 33%, by reducing both GLUT- (by 28%) and non-GLUT-mediated (by 40%) 3H-DG uptake. Uptake of 3H-DG and the effect of tBOOH upon 3H-DG uptake are not dependent on PKC and PI3K. Moreover, the effect of tBOOH is not associated with a reduction in GLUT1 mRNA levels. Resveratrol, quercetin and epigallocatechin-3-gallate, at 50 μM, reversed, by at least 45%, the effect of tBOOH upon 3H-DG uptake. Transwell studies show that the apical-to-basolateral transepithelial transport of 3H-DG is increased by tBOOH.In conclusion, our results show that tBOOH caused a marked decrease in both GLUT and non-GLUT-mediated apical uptake of 3H-DG by BeWo cells. Given the association of increased oxidative stress levels with several important pregnancy pathologies, and the important role of glucose for fetal development, the results of this study appear very interesting.

Synthesis, characterization, electrochemical behavior and in vitro protein tyrosine kinase inhibitory activity of the cymene-halogenobenzohydroxamato [Ru(eta(6)-cymene)(bha)Cl] complexes

The ruthenium(II)-cymene complexes [Ru(eta(6)-cymene)(bha)Cl] with substituted halogenobenzohydroxamato (bha) ligands (substituents = 4-F, 4-Cl, 4-Br, 2,4-F-2, 3,4-F-2, 2,5-F-2, 2,6-F-2) have been synthesized and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, cyclic voltammetry and controlled-potential electrolysis, and density functional theory (DFT) studies. The compositions of their frontier molecular orbitals (MOs) were established by DFT calculations, and the oxidation and reduction potentials are shown to follow the orders of the estimated vertical ionization potential and electron affinity, respectively. The electrochemical E-L Lever parameter is estimated for the first time for the various bha ligands, which can thus be ordered according to their electron-donor character. All complexes exhibit very strong protein tyrosine kinase (PTK) inhibitory activity, even much higher than that of genistein, the clinically used PTK inhibitory drug. The complex containing the 2,4-difluorobenzohydroxamato ligand is the most active one, and the dependences of the PTK activity of the complexes and of their redox potentials on the ring substituents are discussed. (C) 2012 Elsevier B.V. All rights reserved.

Basic dyestuffs removal from textile effluents using feathers: equilibrium, kinetic and column studies

This research work has been focused in the study of gallinaceous feathers, a waste that may be valorised as sorbent, to remove the Dark Blue Astrazon 2RN (DBA) from Dystar. This study was focused on the following aspects: optimization of experimental conditions through factorial design methodology, kinetic studies into a continuous stirred tank adsorber (at pH 7 and 20ºC), equilibrium isotherms (at pH 5, 7 and 9 at 20 and 45ºC) and column studies (at 20ºC, at pH 5, 7 and 9). In order to evaluate the influence of the presence of other components in the sorption of the dyestuff, all experiments were performed both for the dyestuff in aqueous solution and in real textile effluent. The pseudo-first and pseudo-second order kinetic models were fitted to the experimental data, being the latter the best fit for the aqueous solution of dyestuff. For the real effluent both models fit the experimental results and there is no statistical difference between them. The Central Composite Design (CCD) was used to evaluate the effects of temperature (15 - 45ºC) and pH (5 - 9) over the sorption in aqueous solution. The influence of pH was more significant than temperature. The optimal conditions selected were 45ºC and pH 9. Both Langmuir and Freundlich models could fit the equilibrium data. In the concentration range studied, the highest sorbent capacity was obtained for the optimal conditions in aqueous solution, which corresponds to a maximum capacity of 47± 4 mg g-1. The Yoon-Nelson, Thomas and Yan’s models fitted well the column experimental data. The highest breakthrough time for 50% removal, 170 min, was obtained at pH 9 in aqueous solution. The presence of the dyeing agents in the real wastewater decreased the sorption of the dyestuff mostly for pH 9, which is the optimal pH. The effect of pH is less pronounced in the real effluent than in aqueous solution. This work shows that feathers can be used as sorbent in the treatment of textile wastewaters containing DBA.

Preparatory and field work phases in the qualitative empirical research process in management: the case studies approach

Purpose: The aim of this paper is to promote qualitative methodology within the scientific community of management. The specific objective is oriented to propose an empirical research process based on case study method. This is to ensure rigor in the empirical research process, that future research may follow a similar procedure to that is proposed. Design/methodology/approach: Following a qualitative methodological approach, we propose a research process that develops according to four phases, each with several stages. This study analyses the preparatory and field work phases and their stages. Findings: The paper shows the influence that case studies have on qualitative empirical research process in management. Originality/value:. Case study method assumes an important role within qualitative research by allowing for the study and analysis of certain types of phenomena that occur inside organisations, and in respect of which quantitative studies cannot provide an answer.

Validade da escala de depressão do Center for Epidemiological Studies entre idosos brasileiros

OBJETIVO: Obter validade interna, de construto e de critério para a escala Center for Epidemiological Studies - Depression, em idosos. MÉTODOS: O instrumento foi aplicado a 903 idosos residentes em Juiz de Fora, Estado de Minas Gerais, entre os anos de 2002-2003. Os resultados foram comparados com a versão brasileira da Geriatric Depression Scale, aplicado a uma subamostra de 446 respondentes. A consistência interna das duas escalas foi aferida pelo coeficiente alfa de Cronbach, calculado para os itens em sua totalidade e para os itens de cada fator obtido para o instrumento avaliado. Para avaliar a validade de construto, seus 20 itens foram submetidos à análise fatorial exploratória a fim de conhecer o padrão de variação conjunta dos itens e a variância explicada por cada fator. RESULTADOS: O instrumento revelou índices satisfatórios de validade interna (alfa=0,860), sensibilidade (74,6%) e especificidade (73,6%), para nota de corte >11. Entretanto, apontou freqüência relativamente alta de falsos positivos em comparação à Geriatric Depression Scale: de 33,8% vs. 15%. A análise fatorial exploratória do instrumento gerou estrutura fatorial com três fatores: afetos negativos, dificuldades de iniciar comportamentos e afetos positivos. CONCLUSÕES: O instrumento mostrou-se psicometricamente adequado para uso entre idosos. Entretanto, estudos adicionais de natureza longitudinal e transversal, desenvolvidos em diferentes contextos, poderão esclarecer os efeitos de variáveis somáticas e situacionais sobre os resultados desse instrumento em pessoas idosas.

The genus Corallina (Corallinaceae, Corallinales, Rhodophyta) in the Azores (NE Atlantic): character expression and taxonomic evaluation

Morphological and anatomical characters used for segregating species within the genus Corallina (Corallinaceae, Rhodophyta) have been compiled and evaluated in 120 specimens collected in the Azores. The morphological, anatomical and statistical evaluation of the thirty four segregating characters for the genus Corallina performed in the present study revealed no species segregation, either showing no differences across the whole lot of specimens or being highly variable within sets of plants. This suggests that all studied material belongs to one species, so far Ellisolandia elongata (formely Corallina elongata), thus reinforcing old proposed synonyms. A morphological and anatomical account is provided for this species, considering the whole set of studied specimens.

A new multiplexed microsatellite tool for metapopulation studies in the overexploited endemic limpet Patella aspera (Röding, 1798)

Patellid limpets are ecologically important keystone grazers having a long history of overexploitation in the Macaronesian Archipelagos (NE Atlantic islands), where some species, such as Patella aspera, are under serious risk.[1, 2] Patella aspera is a protandric sequential hermaphrodite species with external fertilization, in which individuals start off as males but may undergo a sex reversal with age.[3] Hence, exploitation tends to focus on the larger females in the population as larger limpets (predominantly females) are selectively removed. Despite conservation legislation in Canaries, Madeira and Azores, limpets are under severe pressure and few individuals survive long enough to become females, a phenomenon that severely restricts the effective population size.[4] New conservation actions for the protection and sustainable use of limpets in Macaronesian Archipelagos are urgently needed and should be based on a multidisciplinary framework based on knowledge of the population dynamics and connectivity of this species.

O feminino na obra de Uanhenga Xitu

Interessa-nos para este artigo perscrutar as representações da vida social em narrativas do escritor angolano Uanhenga Xitu, mormente no que diz respeito à personagem feminina e ao papel da mulher nas sociedades tradicionais angolanas. Nas narrativas cujas ações se passam no interior de Angola, as representações sociais da mulher revelam um modus vivendi diferenciado daquele experimentado por mulheres que migram para a capital, Luanda, espaço em que a noção de vida comunitária, tão significativa nas sociedades tradicionais, perde seu significado. Os trabalhos lá executados, por exemplo, serão em favor do colono, como os dos empregados domésticos, e não para a coletividade. Já nos espaços interiores, mais distantes da mão pesada do colonizador, as representações da vida social dos angolanos são mais expressivas e essa diferenciação revela que a migração do campo para a cidade, no caso de um país dominado pela colonização, metaforiza o abandono de um tipo de (con)vivência social em favor de outro. Como a política colonial portuguesa foi assimilacionista, essa migração será sinônimo de busca de adesão ao modus vivendi do outro, muitas vezes para sofrer menos os efeitos da dominação. Para essa discussão, não é por livre escolha que se tratará das personagens femininas na obra de Xitu, posto que as mulheres em seus textos ganham vez e voz para a expressão do proprium angolano, como se o autor as quisesse homenagear em sinal do reconhecimento de sua importância na construção e preservação da memória, que é capaz de criar laços identitários entre as milenares gerações passadas e as futuras, como esboçaremos (Esta reflexão teve origem no estudo desenvolvido no doutoramento, intitulado Entre dois contares: o espaço da tradição na escrita de Uanhenga Xitu, defendida em 1996 na FFLCH-USP, e orientada pela Dra. Maria Aparecida Santilli, falecida em março de 2008).

Copper, nickel and zinc removal by peanut hulls: batch and column studies in mono, tri-component systems and with real effluent

The main goal of this research study was the removal of Cu(II), Ni(II) and Zn(II) from aqueous solutions using peanut hulls. This work was mainly focused on the following aspects: chemical characterization of the biosorbent, kinetic studies, study of the pH influence in mono-component systems, equilibrium isotherms and column studies, both in mono and tri-component systems, and with a real industrial effluent from the electroplating industry. The chemical characterization of peanut hulls showed a high cellulose (44.8%) and lignin (36.1%) content, which favours biosorption of metal cations. The kinetic studies performed indicate that most of the sorption occurs in the first 30 min for all systems. In general, a pseudo-second order kinetics was followed, both in mono and tri-component systems. The equilibrium isotherms were better described by Freundlich model in all systems. Peanut hulls showed higher affinity for copper than for nickel and zinc when they are both present. The pH value between 5 and 6 was the most favourable for all systems. The sorbent capacity in column was 0.028 and 0.025 mmol g-1 for copper, respectively in mono and tri-component systems. A decrease of capacity for copper (50%) was observed when dealing with the real effluent. The Yoon-Nelson, Thomas and Yan’s models were fitted to the experimental data, being the latter the best fit.

A new fluorescent double-cavity calix[4]arene: synthesis and complexation studies toward nitroanilines

Agência Financiadora: Fundação para a Ciência e a Tecnologia/MCTES (Portugal) - PEst-OE/EQB/UI0702/2012

Copper and lead removal by peanut hulls: equilibrium and kinetic studies

This research work aims to study the use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3–5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 ± 0.03 and 0.18 ± 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78% and 58% removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems.

Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies

In this work three natural waste materials containing chitin were used as adsorbents for textile dyestuffs, namely the Anodonta (Anodonta cygnea) shell, the Sepia (Sepia officinalis) and the Squid (Loligo vulgaris) pens. The selected dyestuffs were the Cibacron green T3G-E (CI reactive green 12), and the Solophenyl green BLE 155% (CI direct green 26), both from CIBA, commonly used in cellulosic fibres dyeing, the most used fibres in the textile industry. Batch equilibrium studies showed that the materials’ adsorption capacities increase after a simple and inexpensive chemical treatment, which increases their porosity and chitin relative content. Kinetic studies suggested the existence of a high internal resistance in both systems. Fixed bed column experiments performed showed an improvement in adsorbents’ behaviour after chemical treatment. However, in the column experiments, the biodegradation was the main mechanism of dyestuff removal, allowing the materials’ bioregeneration. The adsorption was strongly reduced by the pore clogging effect of the biomass. The deproteinised Squid pen (grain size 0.500–1.41 mm) is the adsorbent with highest adsorption capacity (0.27 and 0.037 g/g, respectively, for the reactive and direct dyestuffs, at 20ºC), followed by the demineralised Sepia pen and Anodonta shell, behaving like pure chitin in all experiments, but showing inferior performances than the granular activated carbon tested in the column experiments.

A influência do local de estimulação ventricular na incidência de taquiarritmias auriculares em doentes com pacemaker permanente

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular

The influence of count's number in myocardium in the determination of reproducible parameters in Gated-SPECT studies simulated with GATE

Myocardial Perfusion Gated Single Photon Emission Tomography (Gated-SPET) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV). The purpose of this study is to evaluate the influence of the total number of counts acquired from myocardium, in the calculation of myocardial functional parameters using routine software procedures. Methods: Gated-SPET studies were simulated using Monte Carlo GATE package and NURBS phantom. Simulated data were reconstructed and processed using the commercial software package Quantitative Gated-SPECT. The Bland-Altman and Mann-Whitney-Wilcoxon tests were used to analyze the influence of the number of total counts in the calculation of LV myocardium functional parameters. Results: In studies simulated with 3MBq in the myocardium there were significant differences in the functional parameters: Left ventricular ejection fraction (LVEF), end-systolic volume (ESV), Motility and Thickness; between studies acquired with 15s/projection and 30s/projection. Simulations with 4.2MBq show significant differences in LVEF, end-diastolic volume (EDV) and Thickness. Meanwhile in the simulations with 5.4MBq and 8.4MBq the differences were statistically significant for Motility and Thickness. Conclusion: The total number of counts per simulation doesn't significantly interfere with the determination of Gated-SPET functional parameters using the administered average activity of 450MBq to 5.4MBq in myocardium.