Patching up dipoles: can dipolar particles be viewed as patchy colloids?

We investigate whether the liquid-vapour phase transition of strongly dipolar fluids can be understood using a model of patchy colloids. These consist of hard spherical particles with three short-ranged attractive sites (patches) on their surfaces. Two of the patches are of type A and one is of type B. Patches A on a particle may bond either to a patch A or to a patch B on another particle. Formation of an AA (AB) bond lowers the energy by epsilon AA (epsilon AB). In the limit [image omitted], this patchy model exhibits condensation driven by AB-bonds (Y-junctions). Y-junctions are also present in low-density, strongly dipolar fluids, and have been conjectured to play a key role in determining their critical behaviour. We map the dipolar Yukawa hard-sphere (DYHS) fluid onto this 2A + 1B patchy model by requiring that the latter reproduce the correct DYHS critical point as a function of the isotropic interaction strength epsilon Y. This is achieved for sensible values of epsilon AB and the bond volumes. Results for the internal energy and the particle coordination number are in qualitative agreement with simulations of DYHSs. Finally, by taking the limit [image omitted], we arrive at a new estimate for the critical point of the dipolar hard-sphere fluid, which agrees with extrapolations from simulation.

Synthesis, Antimicrobial and Antiproliferative Activity of Novel Silver(I) Tris(pyrazolyl)methanesulfonateand 1,3,5-Triaza-7-phosphadamantane Complexes

Five new silver(I) complexes of formulas [Ag(Tpms)] (1), [Ag(Tpms)-(PPh3)] (2), [Ag(Tpms)(PCy3)] (3), [Ag(PTA)][BF4] (4), and [Ag(Tpms)(PTA)] (5) {Tpms = tris(pyrazol-1-yl)methanesulfonate, PPh3 = triphenylphosphane, PCy3 = tricyclohexylphosphane, PTA = 1,3,5-triaza-7-phosphaadamantane) have been synthesized and fully characterized by elemental analyses, H-1, C-13, and P-31 NMR, electrospray ionization mass spectrometry (ESI-MS), and IR spectroscopic techniques. The single crystal X-ray diffraction study of 3 shows the Tpms ligand acting in the N-3-facially coordinating mode, while in 2 and 5 a N2O-coordination is found, with the SO3 group bonded to silver and a pendant free pyrazolyl ring. Features of the tilting in the coordinated pyrazolyl rings in these cases suggest that this inequivalence is related with the cone angles of the phosphanes. A detailed study of antimycobacterial and antiproliferative properties of all compounds has been carried out. They were screened for their in vitro antimicrobial activities against the standard strains Enterococcus faecalis (ATCC 29922), Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), Streptococcus pyogenes (SF37), Streptococcus sanguinis (SK36), Streptococcus mutans (UA1S9), Escherichia coli (ATCC 25922), and the fungus Candida albicans (ATCC 24443). Complexes 1-5 have been found to display effective antimicrobial activity against the series of bacteria and fungi, and some of them are potential candidates for antiseptic or disinfectant drugs. Interaction of Ag complexes with deoxyribonucleic acid (DNA) has been studied by fluorescence spectroscopic techniques, using ethidium bromide (EB) as a fluorescence probe of DNA. The decrease in the fluorescence of DNA EB system on addition of Ag complexes shows that the fluorescence quenching of DNA EB complex occurs and compound 3 is particularly active. Complexes 1-5 exhibit pronounced antiproliferative activity against human malignant melanoma (A375) with an activity often higher than that of AgNO3, which has been used as a control, following the same order of activity inhibition on DNA, i.e., 3 > 2 > 1 > 5 > AgNO3 >> 4.

Drug therapy complexity: the importance of pharmacotherapeutic follow-up

Nowadays, the phenomenon of population ageing represents an worldwide problem, which assumes particular significance in Portugal. As they get older, individuals present more comorbidities and consequently consume an increasing number of drugs, which contributes to a growing drug therapy complexity. The institutionalized elders are particularly affected by this occurrence. Drug therapy complexity is defined as the conciliator of several characteristics of the pharmacotherapy and can affect patient’s safety and medication adherence. It can be measured with Medication Regimen Complexity Index (MRCI). This study aims to determine the drug therapy complexity of institutionalized elders in order to assess the need of pharmacotherapeutic follow-up.

Arrow Plot: a new graphical tool for selecting up and down regulated genes and genes differentially expressed on samples subgroups

Background: A common task in analyzing microarray data is to determine which genes are differentially expressed across two (or more) kind of tissue samples or samples submitted under experimental conditions. Several statistical methods have been proposed to accomplish this goal, generally based on measures of distance between classes. It is well known that biological samples are heterogeneous because of factors such as molecular subtypes or genetic background that are often unknown to the experimenter. For instance, in experiments which involve molecular classification of tumors it is important to identify significant subtypes of cancer. Bimodal or multimodal distributions often reflect the presence of subsamples mixtures. Consequently, there can be genes differentially expressed on sample subgroups which are missed if usual statistical approaches are used. In this paper we propose a new graphical tool which not only identifies genes with up and down regulations, but also genes with differential expression in different subclasses, that are usually missed if current statistical methods are used. This tool is based on two measures of distance between samples, namely the overlapping coefficient (OVL) between two densities and the area under the receiver operating characteristic (ROC) curve. The methodology proposed here was implemented in the open-source R software. Results: This method was applied to a publicly available dataset, as well as to a simulated dataset. We compared our results with the ones obtained using some of the standard methods for detecting differentially expressed genes, namely Welch t-statistic, fold change (FC), rank products (RP), average difference (AD), weighted average difference (WAD), moderated t-statistic (modT), intensity-based moderated t-statistic (ibmT), significance analysis of microarrays (samT) and area under the ROC curve (AUC). On both datasets all differentially expressed genes with bimodal or multimodal distributions were not selected by all standard selection procedures. We also compared our results with (i) area between ROC curve and rising area (ABCR) and (ii) the test for not proper ROC curves (TNRC). We found our methodology more comprehensive, because it detects both bimodal and multimodal distributions and different variances can be considered on both samples. Another advantage of our method is that we can analyze graphically the behavior of different kinds of differentially expressed genes. Conclusion: Our results indicate that the arrow plot represents a new flexible and useful tool for the analysis of gene expression profiles from microarrays.

Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite

The hydrotris(pyrazol-1-yl)methane iron(II) complex [FeCl2{eta(3)-HC(pz)(3)}] (Fe, pz = pyrazol-1-yl) immobilized on commercial (MOR) or desilicated (MOR-D) zeolite, catalyses the oxidation of cyclohexane with hydrogen peroxide to cyclohexanol and cyclohexanone, under mild conditions. MOR-D/Fe (desilicated zeolite supported [FeCl2{eta(3)-HC(pz)(3)}] complex) provides an outstanding catalytic activity (TON up to 2.90 x 10(3)) with the concomitant overall yield of 38%, and can be easy recovered and reused. The MOR or MOR-D supported hydrotris(pyrazol-1-yl)methane iron(II) complex (MOR/Fe and MOR-D/Fe, respectively) was characterized by X-ray powder diffraction, ICP-AES, and TEM studies as well as by IR spectroscopy and N-2 adsorption at -196 degrees C. The catalytic operational conditions (e.g., reaction time, type and amount of oxidant, presence of acid and type of solvent) were optimized. (C) 2013 Elsevier B.V. All rights reserved.

Astaxanthin production using Photobioreactors, investigation and scale up and an integrated solution for eutrophic lakes

TRANSCREA, Convertir la investigación y el conocimiento en innovación, propiedad intelectual e industrial. Terceira, 16 e 17 Fevereiro, 2011.

Start-up circuit for low-power indoor light energy harvesting applications

A start-up circuit, used in a micro-power indoor light energy harvesting system, is described. This start-up circuit achieves two goals: first, to produce a reset signal, power-on-reset (POR), for the energy harvesting system, and secondly, to temporarily shunt the output of the photovoltaic (PV) cells, to the output node of the system, which is connected to a capacitor. This capacitor is charged to a suitable value, so that a voltage step-up converter starts operating, thus increasing the output voltage to a larger value than the one provided by the PV cells. A prototype of the circuit was manufactured in a 130 nm CMOS technology, occupying an area of only 0.019 mm(2). Experimental results demonstrate the correct operation of the circuit, being able to correctly start-up the system, even when having an input as low as 390 mV using, in this case, an estimated energy of only 5.3 pJ to produce the start-up.

Dosimetric effect by shallow air cavities in high energy electron beams

This study evaluates the dosimetric impact caused by an air cavity located at 2 mm depth from the top surface in a PMMA phantom irradiated by electron beams produced by a Siemens Primus linear accelerator. A systematic evaluation of the effect related to the cavity area and thickness as well as to the electron beam energy was performed by using Monte Carlo simulations (EGSnrc code), Pencil Beam algorithm and Gafchromic EBT2 films. A home-PMMA phantom with the same geometry as the simulated one was specifically constructed for the measurements. Our results indicate that the presence of the cavity causes an increase (up to 70%) of the dose maximum value as well as a shift forward of the position of the depthedose curve, compared to the homogeneous one. Pronounced dose discontinuities in the regions close to the lateral cavity edges are observed. The shape and magnitude of these discontinuities change with the dimension of the cavity. It is also found that the cavity effect is more pronounced (6%) for the 12 MeV electron beam and the presence of cavities with large thickness and small area introduces more significant variations (up to 70%) on the depthedose curves. Overall, the Gafchromic EBT2 film measurements were found in agreement within 3% with Monte Carlo calculations and predict well the fine details of the dosimetric change near the cavity interface. The Pencil Beam calculations underestimate the dose up to 40% compared to Monte Carlo simulations; in particular for the largest cavity thickness (2.8 cm).

Assesing multileaf collimator effect on the build-up region using Monte Carlo method

Previous Monte Carlo studies have investigated the multileaf collimator (MLC) contribution to the build-up region for fields in which the MLC leaves were fully blocking the openings defined by the collimation jaws. In the present work, we investigate the same effect but for symmetric and asymmetric MLC defined field sizes (2×2, 4×4, 10×10 and 3×7 cm2). A Varian 2100C/D accelerator with 120-leaf MLC is accurately modeled fora6MVphoton beam using the BEAMnrc/EGSnrc code. Our results indicate that particles scattered from accelerator head and MLC are responsible for the increase of about 7% on the surface dose when comparing 2×2 and 10×10 cm2 fields. We found that the MLC contribution to the total build-up dose is about 2% for the 2×2 cm2 field and less than 1% for the largest fields.

Nutritional status and overhydration: can bioimpedance spectroscopy be useful in haemodialysis patients?

Background: Protein-energy wasting (PEW), associated with inflammation and overhydration, is common in haemodialysis (HD) patients and is associated with high morbidity and mortality. Objective: Assess the relationship between nutritional status, markers of inflammation and body composition through bioimpedance spectroscopy (BIS) in HD patients. Methods: This observational, cross-sectional, single centre study, carried out in an HD centre in Forte da Casa (Portugal), involved 75 patients on an HD programme. In all participating patients, the following laboratory tests were conducted: haemoglobin, albumin, C-reactive protein (CRP) and 25-hydroxyvitamin D3 [25(OH)D3]. The body mass index of all patients was calculated and a modified version of subjective global assessment (SGA) was produced for patients on dialysis. Intracellular water (ICW) and extracellular water (ECW) were measured by BIS (Body Composition Monitor®, Fresenius Medical Care®) after the HD session. In statistical analysis, Spearman’s correlation was used for the univariate analysis and linear regression for the multivariate analysis (SPSS 14.0). A P value of <.05 was considered statistically significant. Results: PEW, inversely assessed through the ICW/body weight (BW) ratio, was positively related to age (P<.001), presence of diabetes (P=.004), BMI (P=.01) and CRP (P=.008) and negatively related to albumin (p=.006) and 25(OH)D3 (P=.007). Overhydration, assessed directly through the ECW/BW ratio, was positively related with CRP (P=.009) and SGA (P=.03), and negatively with 25(OH)D3 (P=.006) and BMI (P=.01). In multivariate analysis, PEW was associated with older age (P<.001), the presence of diabetes (P=.003), lower 25(OH)D3 (P=.008), higher CRP (P=.001) and lower albumin levels (P=.004). Over-hydration was associated with higher CRP (P=.001) and lower levels of 25(OH)D3 (P=.003). Conclusions: Taking these results into account, the ICW/BW and ECW/BW ratios, assessed with BIS, have proven to be good markers of the nutritional and inflammatory status of HD patients. BIS may be a useful tool for regularly assessing the nutritional and hydration status in these patients and may allow nutritional advice to be improved and adjusted.

PPO Reaction Scale-up

O óxido de polifenileno com a marca comercial PPO® é uma das resinas principais produzidas na SABIC IP e o ingrediente principal do plástico de engenharia com a marca registada, Noryl®. A equipa de tecnologia de processo de PPO® desenvolve uma série de novos produtos em reactores de pequena escala, tanto em Selkirk como em Bergen op Zoom. Para se efectuar uma transição rápida da escala laboratorial para a fábrica, é necessário um conhecimento completo do reactor. O objectivo deste projecto consiste em esboçar linhas gerais para o scale-up de novos produtos de PPO1, do laboratório para a escala industrial, baseado no estudo de um tipo de PPO, PPO 803. Este estudo pode ser dividido em duas fases. Numa primeira fase, as receitas e os perfis da reacção são comparados, de onde se retiram as primeiras conclusões. Posteriormente, com base nestas conclusões, é realizado um planeamento experimental. O estudo inicial sugeriu que a receita, a temperatura inicial do reactor e a velocidade do agitador poderiam influenciar o tempo da reacção bem como a queda da velocidade intrínseca do polímero (IV drop). As reacções experimentais mostraram que a receita é o principal factor que influencia, tanto o tempo de reacção, como a queda de viscosidade intrínseca. O tempo de reacção será tanto maior quanto menor a agitação devido à má dispersão do oxigénio na mistura. O uso de temperaturas iniciais elevadas conduz a uma queda maior da viscosidade intrínseca devido à desactivação do catalisador. O método experimental utilizado no laboratório de Bergen op Zoom é um bom exemplo, simulador, do procedimento utilizado na fábrica.

A importância do follow-up na auditoria interna em Portugal

Mestrado em Auditoria

Happiness, hope, and affection as predictors of quality of life and functionality of individuals with heart failure at three-month follow-up

The scientific evidence supporting the management of the chronically ill in a positive psychological perspective in opposition to traditional pathological approach is scarce. This study examines issues associated with recovery of health status in heart failure, in particular hope, affection, and happiness. We use a longitudinal study of 128 symptomatic patients who after medical intervention reported improved quality of life and function at 3-month follow-up. We evaluated the contribution of happiness, hope and affection, individually and as a whole, in the quality of life and functionality of individuals with heart failure. Happiness (Subjective Happiness Scale), Hope (HOPE Scale), and affection (PANAS (positive and negative affect schedule)) were determined before medical intervention. Individually, we found that happiness is correlated with the quality of life and functionality, hope to self-efficacy dimension of the quality of life scale, positive affect to functionality and negative affect with symptoms dimension, quality of life dimension, and overall sum of the quality of life scale. Overall, we found that happiness has a unique contribution to the quality of life, except in self-efficacy dimension where hope takes this contribution and positive affect has a unique contribution to the functionality in this short-term follow-up. The results highlight the importance of positive variables to health outcomes for people with heart failure and should be considered in intervention programs for this syndrome.

Colloidal dipolar interactions in 2D smectic-C films

We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as similar to D-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that, is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk.

Modelling and segmentation of the vocal tract during speech production by using deformable models in magnetic resonance images

The first and second authors would like to thank the support of the PhD grants with references SFRH/BD/28817/2006 and SFRH/PROTEC/49517/2009, respectively, from Fundação para a Ciência e Tecnol ogia (FCT). This work was partially done in the scope of the project “Methodologies to Analyze Organs from Complex Medical Images – Applications to Fema le Pelvic Cavity”, wi th reference PTDC/EEA- CRO/103320/2008, financially supported by FCT.