Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Nonmonotonic Magnetic Susceptibility of Dipolar Hard-Spheres at Low Temperature and Density

We investigate, via numerical simulations, mean field, and density functional theories, the magnetic response of a dipolar hard sphere fluid at low temperatures and densities, in the region of strong association. The proposed parameter-free theory is able to capture both the density and temperature dependence of the ring-chain equilibrium and the contribution to the susceptibility of a chain of generic length. The theory predicts a nonmonotonic temperature dependence of the initial (zero field) magnetic susceptibility, arising from the competition between magnetically inert particle rings and magnetically active chains. Monte Carlo simulation results closely agree with the theoretical findings. DOI: 10.1103/PhysRevLett.110.148306

Branching points in the low-temperature dipolar hard sphere fluid

In this contribution, we investigate the low-temperature, low-density behaviour of dipolar hard-sphere (DHS) particles, i.e., hard spheres with dipoles embedded in their centre. We aim at describing the DHS fluid in terms of a network of chains and rings (the fundamental clusters) held together by branching points (defects) of different nature. We first introduce a systematic way of classifying inter-cluster connections according to their topology, and then employ this classification to analyse the geometric and thermodynamic properties of each class of defects, as extracted from state-of-the-art equilibrium Monte Carlo simulations. By computing the average density and energetic cost of each defect class, we find that the relevant contribution to inter-cluster interactions is indeed provided by (rare) three-way junctions and by four-way junctions arising from parallel or anti-parallel locally linear aggregates. All other (numerous) defects are either intra-cluster or associated to low cluster-cluster interaction energies, suggesting that these defects do not play a significant part in the thermodynamic description of the self-assembly processes of dipolar hard spheres. (C) 2013 AIP Publishing LLC.

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Relação entre função ventricular esquerda e os índices de captação miocárdio/pulmão em estudos Gated-SPECT

Introdução – A tomografia de emissão de fotão simples sincronizada com o sinal eletrocardiográfico (Gated-SPECT) é essencial para a avaliação conjunta da perfusão e da função ventricular esquerda (VE) do miocárdio. Objetivo – Investigar a relação entre a função VE e o índice de captação (IC) miocárdio/pulmão direito (M/PD) e M/P esquerdo (M/PE) nos estudos Gated-SPECT com 99mTc-Tetrofosmina. Metodologia – Amostra de 32 pacientes que realizaram estudos Gated-SPECT por indicação clínica, sendo subdividida em dois grupos: Grupo I (GI) – pacientes com a informação clínica de enfarte agudo do miocárdio (EAM); Grupo II (GII) – pacientes com a informação clínica de isquemia. Por cada paciente adquiriram-se imagens estáticas torácico-abdominais e dois estudos Gated-SPECT do miocárdio (protocolo de um dia esforço/repouso). Nas imagens estáticas definiram-se regiões de interesse (Regions of interest – ROI) para calcular os IC. Nos estudos Gated-SPECT utilizou-se o software Quantitative Gated SPECT/Quantitative Perfusion SPECT para calcular a Fração de Ejeção do Ventrículo Esquerdo (FEVE). Efetuou-se análise estatística descritiva para caracterização da amostra. Aplicou-se o teste de Spearman para avaliar a correlação entre a FEVE e os IC por grupo de pacientes. O Teste de Willcoxon foi usado para comparar FEVE em repouso e em esforço. Resultados – Nos estudos Gated-SPECT em esforço não se verificou correlação estatisticamente significativa entre a FEVE e os IC, para GI e GII; em repouso existe correlação positiva estatisticamente significativa entre a FEVE e os IC, para GI; para GII não se verificou correlação. Na comparação dos valores de FEVE em esforço e repouso nos dois grupos constatou-se a existência de diferenças estatisticamente significativas, sendo a FEVE em Esforço

Avaliação ecocardiográfica da insuficiência mitral concomitante, na substituição valvular aórtica isolada: é possível prevê-la?

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Ramo de especialização: Ultrassonografia 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.

Aurícula direita: mecânica e sobrecarga de volume

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Ramo de especialização: Ultrassonografia Cardiovascular

Avaliação da função diastólica no ventrículo esquerdo em mulheres hipertensas com excesso de peso ou obesidade

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Ramo de especialização: Ultrassonografia Cardiovascular

Avaliação da função ventricular esquerda por ecocardiografia bidimensional com VVI em indivíduos hipertensos voluntários

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Ramo de especialização: Ultrassonografia Cardiovascular

A criação de valor no sector da pasta, papel e cartão : caso Portucel Soporcel

Mestrado em Gestão e Empreendedorismo

The influence of number of counts in the myocardium in the determination of reproducible functional parameters in gated-SPECT studies simulated with GATE

Myocardial perfusion gated-single photon emission computed tomography (gated-SPECT) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV) function. The aim of this study is to analyze the influence of counts/pixel and concomitantly the total counts in the myocardium for the calculation of myocardial functional parameters. Material and methods: Gated-SPECT studies were performed using a Monte Carlo GATE simulation package and the NCAT phantom. The simulations of these studies use the radiopharmaceutical 99mTc-labeled tracers (250, 350, 450 and 680MBq) for standard patient types, effectively corresponding to the following activities of myocardium: 3, 4.2, 5.4-8.2MBq. All studies were simulated using 15 and 30s/projection. The simulated data were reconstructed and processed by quantitative-gated-SPECT software, and the analysis of functional parameters in gated-SPECT images was done by using Bland-Altman test and Mann-Whitney-Wilcoxon test. Results: In studies simulated using different times (15 and 30s/projection), it was noted that for the activities for full body: 250 and 350MBq, there were statistically significant differences in parameters Motility and Thickness. For the left ventricular ejection fraction (LVEF), end-systolic volume (ESV) it was only for 250MBq, and 350MBq in the end-diastolic volume (EDV), while the simulated studies with 450 and 680MBq showed no statistically significant differences for global functional parameters: LVEF, EDV and ESV. Conclusion: The number of counts/pixel and, concomitantly, the total counts per simulation do not significantly interfere with the determination of gated-SPECT functional parameters, when using the administered average activity of 450MBq, corresponding to the 5.4MBq of the myocardium, for standard patient types.

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.

Cooperative effects in the detection of a nitroaliphatic liquid explosive and na explosive taggant in the vapor phase by calix[4]arene-based carbazole-containing conjugated polymers

Two fluorescent molecular receptor based conjugated polymers were used in the detection of a nitroaliphatic liquid explosive (nitromethane) and an explosive taggant (2,3-dimethyl-2,3-dinitrobutane) in the vapor phase. Results have shown that thin films of both polymers display remarkably high sensitivity and selectivity toward these analytes. Very fast, reproducible, and reversible responses were found. The unique behavior of these supramolecular host systems is ascribed to cooperativity effects developed between the calix[4] arene hosts and the phenylene ethynylene-carbazolylene main chains. The calix[4]-arene hosts create a plethora of host-guest binding sites along the polymer backbone, either in their bowl-shaped cavities or between the outer walls of the cavity, to direct guests to the area of the transduction centers (main chain) at which favorable photoinduced electron transfer to the guest molecules occurs and leads to the observed fluorescence quenching. The high tridimensional porous nature of the polymers imparted by the bis-calixarene moieties concomitantly allows fast diffusion of guest molecules into the polymer thin films.

Surface morphology and phase transformations of femtosecond laser-processed saphire

The morphological and structural modifications induced in sapphire by surface treatment with femtosecond laser radiation were studied. Single-crystal sapphire wafers cut parallel to the (0 1 2) planes were treated with 560 fs, 1030 nm wavelength laser radiation using wide ranges of pulse energy and repetition rate. Self-ordered periodic structures with an average spatial periodicity of similar to 300 nm were observed for fluences slightly higher than the ablation threshold. For higher fluences the interaction was more disruptive and extensive fracture, exfoliation, and ejection of ablation debris occurred. Four types of particles were found in the ablation debris: (a) spherical nanoparticles about 50 nm in diameter; (b) composite particles between 150 and 400 nm in size; (c) rounded resolidified particles about 100-500 nm in size; and (d) angular particles presenting a lamellar structure and deformation twins. The study of those particles by selected area electron diffraction showed that the spherical nanoparticles and the composite particles are amorphous, while the resolidified droplets and the angular particles, present a crystalline a-alumina structure, the same of the original material. Taking into consideration the existing ablation theories, it is proposed that the spherical nanoparticles are directly emitted from the surface in the ablation plume, while resolidified droplets are emitted as a result of the ablation process, in the liquid phase, in the low intensity regime, and by exfoliation, in the high intensity regime. Nanoparticle clusters are formed by nanoparticle coalescence in the cooling ablation plume. (C) 2013 Elsevier B.V. All rights reserved.