Structural variations and formation constants of first-row transition metal complexes of biologically active aroylhydrazones

Iron chelators of the 2-pyridinecarbaldehyde isonicotinoylhydrazone (HPCIH) class show high potential for the treatment of iron overload diseases. In the present study, selected first-row transition metal (from Mn to Zn) complexes with HPCIH and 2-pyridinecarbaldehyde (4'-aminobenzoyl)hydrazone (HPCAH) were synthesised and characterised. Crystallography reveals that HPCAH exclusively forms bis complexes with divalent transition metals, with each ligand coordinating meridionally through its pyridine-N, imine-N and carbonyl-O atoms, forming distorted octahedral cis-MN4O2 complexes. Complexes of HPCIH were more varied and unpredictable, with metal/ligand ratios of 1:1, 1:2, 2:2 and 3:2 obtained with different metal ions. The isonicotinoyl ring N-atom in HPCIH was found to be an effective ligand, and this resulted in the varied metal/ligand ratios observed. The formation constants of divalent metal complexes with HPCIH were determined by potentiometric titrations and the values obtained were consistent with similar tridentate ligands and with the Irving-Williams order. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Structural definition of the low-temperature phase transition of tris(ethane-1,2-diamine)zinc(II) dinitrate

The 93 K X-ray crystal structure of tris(ethane-1,2-diamine)zinc(II) dinitrate is reported. As predicted by the spectroscopic studies of other workers, there is a reversible phase transition of the structure at low temperature. We have determined this temperature to be 143 K. The structure at this temperature and below resembles that of the room temperature structure, except the crystallographic D-3 symmetry of the complex cation (296 K) is lowered to C-2 ( below 144 K) by subtle changes in cation-anion hydrogen bonding. No change in the conformation of the cation or its bond lengths and angles was found.

Prediction of multilayer adsorption and capillary condensation phenomena in cylindrical mesopores

MCM-41 periodic mesoporous silicates with a high degree of structural ordering are synthesized and used as model adsorbents to study the isotherm prediction of nitrogen adsorption. The nitrogen adsorption isotherm at 77 K for a macroporous silica is measured and used in high-resolution alpha(s)-plot comparative analysis to determine the external surface area, total surface area and primary mesopore volume of the MCM-41 materials. Adsorption equilibrium data of nitrogen on the different pore size MCM-41 samples (pore diameters from 2.40 to 4.92 nm) are also obtained. Based on the Broekhoff and de Boer' thermodynamic analysis, the nitrogen adsorption isotherms for the different pore size MCM-41 samples are interpreted using a novel strategy, in which the parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting only the multilayer region prior to capillary condensation for C-16 MCM-41. Subsequently the entire isotherm, including the phase transition, is predicted for all the different pore size MCM-41 samples without any fitting. The results show that the prediction of multilayer adsorption and total adsorbed amount are in good agreement with the experimental isotherms. The predictions of the relative pressure corresponding to capillary equilibrium (coexistence) transition agree remarkably with experimental data on the adsorption branch even for hysteretic isotherms, confirming that this is the branch appropriate for pore size distribution analysis. The impact of pore radius on the adsorption film thickness and capillary coexistence pressure is also investigated, and found to agree with the experimental data. (C) 2003 Elsevier Inc. All rights reserved.

Como reagimos e interpretamos os latidos dos cães de acordo com a variação acústica?

Os cães dividem o ambiente com os humanos há milhares de anos e essa relação se torna cada vez mais estreita. Estudos mostram que há comunicação intraespecífica entre os cães e interespecífica entre os cães e os humanos, tanto vocal quanto não-vocal. Os latidos se apresentam hipertrofiados nos cães e acredita-se que isso se deva ao processo de domesticação. Neste estudo, investigamos como os humanos percebem o conteúdo emocional dos latidos e como respondem aos latidos quanto ao grau de irritação percebido, em função das características acústicas de cada chamado. Sessenta participantes, divididos de acordo com a experiência com cães e com o sexo, ouviram 27 sequências de latidos gravadas anteriormente. As sequências de latidos foram montadas artificialmente e categorizadas de acordo com a frequência fundamental, harmonicidade e intervalo entre latidos. Os resultados confirmaram o pressuposto de que tais parâmetros acústicos são importantes para a percepção humana de um conteúdo emocional na vocalização de cães e que causam um impacto emocional em nós, a irritação. Os resultados também foram consistentes com as regras de estrutura-motivação de Morton (1977). Quanto mais baixa a frequência fundamental, maior a agressividade percebida e sons mais agudos e tonais estão relacionados ao medo e ao desespero; quanto mais baixa a harmonicidade, ou seja, quanto mais áspero ou rouco, maior a motivação agressiva. O intervalo entre latidos se mostrou significativo apenas na atribuição da agressividade, quanto mais curtos os intervalos, maior a agressividade percebida. A correlação entre o grau de irritação causado pelos latidos e a percepção das emoções mostrou que quanto maior a percepção de agressividade, medo e desespero, maior o grau de irritação e quanto maior a percepção de brincadeira e felicidade, menor o grau de irritação causado pelos latidos. Esses resultados sugerem que a irritação gerada pelos latidos dos cães está associada a emoções negativas. Quanto ao sexo, os homens obtiveram valores médios significativamente maiores do que as mulheres na avaliação da irritação, o que sugere que os homens possam ter uma menor tolerância com os chamados caninos. Os resultados deste estudo nos levam a concluir que os humanos são capazes de identificar os estados emocionais dos cães através de emissões sonoras. Isto sugere que há uma comunicação interespecífica entre estas espécies e que ambas dividem as mesmas regras acústicas de motivação-estrutural de Morton.

Análise numérico-experimental do comportamento da aderência aço-concreto

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Civil e Ambiental, 2016.

Evaluation of respiratory parameters in minimally processed lettuce grown under organic or conventional system

The increased preference for minimally processed vegetables has been attributed to the health benefits associated with fresh produce and the demand for ready-to-eat salads. In this paper, lettuce (Lactuca sativa L.) was evaluated for the effects of different cropping systems on the respiratory properties. Lettuce was packaged in low density polyethylene bags and stored in a refrigerator at 4 ºC. The concentration of carbon dioxide and oxygen inside the package was monitored during the storage at zero, three, six, eight, ten and twelve days by gas chromatography. Dry matter variation was measured gravimetrically up to day fourteen of storage. Values of respiratory rate for conventional lettuce increased from day 1 to 3 and remained low, while respiratory rate of the organic lettuce increased three-fold up to day 8, stabilizing at a high level. Variation in dry matter during storage also resulted from differences between the two cultivation systems. The highest content of dry matter was achieved by organic lettuce.

Fiber average size and distribution dependence on the electrospinning parameters of poly(vinylidene fluoride trifluoroethylene)) membranes for biomedical applications

Poly(vinylidene fluoride-trifluoethylene) electrospun membranes were obtained from a blend of dimethylformamide (DMF) and methylethylketone (MEK) solvents. The inclusion of the MEK to the solvent system promotes a faster solvent evaporation allowing complete polymer crystallization during the jet travelling between the tip and the grounded collector. Several processing parameters were systematically changed to study their influence on fiber dimensions. Applied voltage and inner needle diameter do not have large influence on the electrospun fiber average diameter but in the fiber diameter distribution. On the other hand, the increase of the distance between the needle tip to collector results in fibers with larger average diameter. Independently on the processing conditions, all mats are produced in the electroactive phase of the polymer. Further, MC-3T3-E1cell adhesion was not inhibited by the fiber mats preparation, indicating their potential use for biomedical applications.

Influence of electrospinning parameters on Poly(hydroxybutyrate) electrospun membranes fiber size and distribution

Poly(hydroxybutyrate) (PHB) obtained from sugar cane was dissolved in a blend of chloroform and dimethylformamide (DMF) and electrospun at 40 ºC. By adding DMF to the solution, the electrospinning process for the PHB polymer becomes more stable, allowing complete polymer crystallization during the jet travelling between the tip and the grounded collector. The influence of processing parameters on fiber size and distribution was systematically studied. It was observed that an increase of tip inner diameter promotes a decrease of the fiber average size and a broader distribution. On the other hand, an increase of the electric field and flow rate produces an increase of fiber diameter until a maximum of ~2.0 m, but for electric fields higher than 1.5 kV.cm-1, a decrease of the fiber diameter was observed. Polymer crystalline phase seems to be independent of the processing conditions and a crystallinity degree of 53 % was found. Moreover, thermal degradation of the as-spun membrane occurs in single step degradation with activation energy of 91 kJ/mol. Furthermore, MC-3T3-E1 cell adhesion was not inhibited by the fiber mats preparation, indicating their potential use for biomedical applications.

Parameters of electrostatic spraying and its influence on the application efficiency

When the electrostatic spraying is used correctly, it provides advantages over conventional systems, however many factors can affect the system efficiency. Therefore, the objective of this study was to evaluate the charge/mass ratio (Q/M) at different spraying distances (0, 1, 2, 3, 4 and 5 m), and the liquid deposition efficiency on the target. Evaluating the Q/M ratio the Faraday cage method was used and to evaluate the liquid deposition efficiency the artificial targets were positioned longitudinally and transversely to the spray jet. It was found that the spraying distance affects the Q/M ratio, consequently, the liquid deposition efficiency. For the closest distance to the target the Q/M ratio was 4.11 mC kg-1, and at distances of 1, 2, 3, 4 and 5 m, the ratio decreased to 1.38, 0.64, 0.31, 0.17 and 0.005 mC kg-1, respectively. For the liquid deposition, the electrostatic system was affected by the target orientation and spraying distance. The target transversely to the jet of liquid did not improve the liquid deposition, but longitudinally increased the deposition up to 3 meters of distance.

Effects of age on histological parameters of the sweat glands of Nellore cattle

The sweat glands are important in thermoregulation of cattle in a warm environment as they help dissipate heat through evaporation. Studies on gland histology are important to define its secretion potential and the capacity of perspiration and heat removal. The objective of this study was to determine, by histomorphometry, glandular epithelium height, the depth of the gland, length of the glandular portion and number of glands per cm2 of the sweat glands of the three age groups of Nellore cattle. Thirty females were used in this study. They were equally divided into calves, heifers and cows. Histological sections were obtained and analyzed by digital images in Trinocular BX40 Olympus microscope coupled to an Oly - 200 camera, connected to a computer. The images were obtained with microscope with 2x, 4x, 10x and 40x magnification objectives. The measurements were performed using HL Image 97 program. The height of glandular epithelium, depth of the glands, length and density of the glandular portion per cm2 , were all analyzed. The calves showed greater height of the glandular epithelium than heifers (P = 0.0024), and cows (P = 0.0191). The depth of the gland was not influenced by age. Cows had higher length of secretory portion than heifers (P = 0.0379) and calves (P = 0.0077). Heifers had a greater number of sweat glands per cm2 of skin than cows (P = 0.023). In cattle, the height of glandular epithelium and the density decreases as animals get older. On the other hand, the length of the secretor portion increases but with no changes in the depth of the sweat glands

Cristalização de Biomateriais Vitrocerâmicos e Mineralização em Meio Fisiológico Simulado

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content.

Radiological imaging in digital systems: the effect of exposure parameters in diagnostic quality and patient dose

Esta tese pretende contribuir para o estudo e análise dos factores relacionados com as técnicas de aquisição de imagens radiológicas digitais, a qualidade diagnóstica e a gestão da dose de radiação em sistema de radiologia digital. A metodologia encontra-se organizada em duas componentes. A componente observacional, baseada num desenho do estudo de natureza retrospectiva e transversal. Os dados recolhidos a partir de sistemas CR e DR permitiram a avaliação dos parâmetros técnicos de exposição utilizados em radiologia digital, a avaliação da dose absorvida e o índice de exposição no detector. No contexto desta classificação metodológica (retrospectiva e transversal), também foi possível desenvolver estudos da qualidade diagnóstica em sistemas digitais: estudos de observadores a partir de imagens arquivadas no sistema PACS. A componente experimental da tese baseou-se na realização de experiências em fantomas para avaliar a relação entre dose e qualidade de imagem. As experiências efectuadas permitiram caracterizar as propriedades físicas dos sistemas de radiologia digital, através da manipulação das variáveis relacionadas com os parâmetros de exposição e a avaliação da influência destas na dose e na qualidade da imagem. Utilizando um fantoma contraste de detalhe, fantomas antropomórficos e um fantoma de osso animal, foi possível objectivar medidas de quantificação da qualidade diagnóstica e medidas de detectabilidade de objectos. Da investigação efectuada, foi possível salientar algumas conclusões. As medidas quantitativas referentes à performance dos detectores são a base do processo de optimização, permitindo a medição e a determinação dos parâmetros físicos dos sistemas de radiologia digital. Os parâmetros de exposição utilizados na prática clínica mostram que a prática não está em conformidade com o referencial Europeu. Verifica-se a necessidade de avaliar, melhorar e implementar um padrão de referência para o processo de optimização, através de novos referenciais de boa prática ajustados aos sistemas digitais. Os parâmetros de exposição influenciam a dose no paciente, mas a percepção da qualidade de imagem digital não parece afectada com a variação da exposição. Os estudos que se realizaram envolvendo tanto imagens de fantomas como imagens de pacientes mostram que a sobreexposição é um risco potencial em radiologia digital. A avaliação da qualidade diagnóstica das imagens mostrou que com a variação da exposição não se observou degradação substancial da qualidade das imagens quando a redução de dose é efectuada. Propõe-se o estudo e a implementação de novos níveis de referência de diagnóstico ajustados aos sistemas de radiologia digital. Como contributo da tese, é proposto um modelo (STDI) para a optimização de sistemas de radiologia digital.

Evaluation of exposure parameters in plain radiography: a comparative study with european guidelines

Typical distribution of exposure parameters in plain radiography is unknown in Portugal. This study aims to identify exposure parameters that are being used in plain radiography in the Lisbon area and to compare the collected data with European references [Commission of European Communities (CEC) guidelines]. The results show that in four examinations (skull, chest, lumbar spine and pelvis), there is a strong tendency of using exposure times above the European recommendation. The X-ray tube potential values (in kV) are below the recommended values from CEC guidelines. This study shows that at a local level (Lisbon region), radiographic practice does not comply with CEC guidelines concerning exposure techniques. Further national/local studies are recommended with the objective to improve exposure optimisation and technical procedures in plain radiography. This study also suggests the need to establish national/local diagnostic reference levels and to proceed to effective measurements for exposure optimisation.

Dimensionamento de um passadiço pedonal em estrutura metálica, com fundações em betão armado

A elaboração deste projecto, integrado no âmbito do Trabalho Final de Mestrado, para a obtenção do grau de Mestre em Engenharia Civil, tem como objectivo o dimensionamento de um passadiço pedonal em estrutura metálica, com fundações em betão armado. Este documento inclui quase todos os elementos necessários ao projecto de execução da referida estrutura. Para o dimensionamento do passadiço pedonal procedeu-se à quantificação das acções e posteriormente à verificação da segurança de todos os elementos estruturais tendo por base os critérios e especificações técnicas preconizados nas Normas Europeias relativas ao projecto estrutural (Eurocódigos estruturais). Tratando-se de um passadiço destinado à circulação de peões e cuja estrutura metálica apresenta um certo grau de flexibilidade devido à esbelteza dos elementos estruturais, esta poderá estar sujeita a acções dinâmicas periódicas provocadas pelas pessoas quando percorrem o passadiço, podendo ocasionar certos níveis de vibração que sob o ponto de vista de segurança estrutural serão pouco relevantes, sendo no entanto excessivos do ponto de vista do conforto humano. Foi por isso efectuado um estudo dinâmico, com o objectivo de caracterizar a resposta dinâmica da estrutura quando solicitada a carregamentos de natureza periódica como é o caso da acção do peão, de modo a garantir que a utilização desta estrutura esteja dentro dos parâmetros de conforto aceitáveis. A modelação da estrutura e consequente discretização geral desta, foi feita recorrendo a programa de elementos finitos, SAP2000, versão 14.0.0. O dimensionamento das ligações constitui outros dos aspectos fundamentais no projecto desta estrutura metálica.

Thick dyke emplacement and internal flow: A structural and magnetic fabric study of the deep-seated dolerite dyke of Foum Zguid (southern Morocco)

Knowledge on forced magma injection and magma flow in dykes is crucial for the understanding of how magmas migrate through the crust to the Earth's surface. Because many questions still persist, we used the long, thick, and deep-seated Foum Zguid dyke (Morocco) to investigate dyke emplacement and internal flow by means of magnetic methods, structural analysis, petrography, and scanning electron microscopy. We also investigated how the host rocks accommodated the intrusion. Regarding internal flow: 1. Important variations of the rock magnetic properties and magnetic fabric occur with distance from dyke wall; 2. anisotropy of anhysteretic remanent magnetization reveals that anisotropy of magnetic susceptibility (AMS) results mainly from the superposition of subfabrics with distinct coercivities and that the imbrication between magnetic foliation and dyke plane is more reliable to deduce flow than the orientation of the AMS maximum principal axis; and 3. a dominant upward flow near the margins can be inferred. The magnetic fabric closest to the dyke wall likely records magma flow best due to fast cooling, whereas in the core the magnetic properties have been affected by high-temperature exsolution and metasomatic effects due to slow cooling. Regarding dyke emplacement, this study shows that the thick forceful intrusion induced deformation by homogeneous flattening and/or folding of the host sedimentary strata. Dewatering related to heat, as recorded by thick quartz veins bordering the dyke in some localities, may have also helped accommodating dyke intrusion. The spatial arrangement of quartz veins and their geometrical relationship with the dyke indicate a preintrusive to synintrusive sinistral component of strike slip.