Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

Análise funcional comparativa de algoritmos de aprendizagem por reforço

De entre todos os paradigmas de aprendizagem actualmente identificados, a Aprendizagem por Reforço revela-se de especial interesse e aplicabilidade nos inúmeros processos que nos rodeiam: desde a solitária sonda que explora o planeta mais remoto, passando pelo programa especialista que aprende a apoiar a decisão médica pela experiencia adquirida, até ao cão de brincar que faz as delícias da criança interagindo com ela e adaptando-se aos seus gostos, e todo um novo mundo que nos rodeia e apela crescentemente a que façamos mais e melhor nesta área. Desde o aparecimento do conceito de aprendizagem por reforço, diferentes métodos tem sido propostos para a sua concretização, cada um deles abordando aspectos específicos. Duas vertentes distintas, mas complementares entre si, apresentam-se como características chave do processo de aprendizagem por reforço: a obtenção de experiência através da exploração do espaço de estados e o aproveitamento do conhecimento obtido através dessa mesma experiência. Esta dissertação propõe-se seleccionar alguns dos métodos propostos mais promissores de ambas as vertentes de exploração e aproveitamento, efectuar uma implementação de cada um destes sobre uma plataforma modular que permita a simulação do uso de agentes inteligentes e, através da sua aplicação na resolução de diferentes configurações de ambientes padrão, gerar estatísticas funcionais que permitam inferir conclusões que retractem entre outros aspectos a sua eficiência e eficácia comparativas em condições específicas.

Synthesis, characterization and redox behaviour of benzoyldiazenido- and oxorhenium complexes bearing N,N- and S,S-type ligands

The reactions of [ReCl2{eta(2)-N2C(O)Ph}(PPh3)(2)](1) with 2-aminopyrimidine (H(2)Npyrm), 2,2'-bipyridine (bpy) and tetraethylthiuram disulfide (tds), in MeOH upon reflux, lead to the new eta(1)-(benzoyldiazenido)-rhenium(III) complexes [ReCl{eta(1)-N2C(O)Ph}(HNpyrm)(PPh3)(2)](2)and [ReCl2{eta(1)-N2C(O)Ph}(bpy)(PPh3)] (3), and the known oxo(diethyldithiocarbamato)dirhenium(v)complex [Re2O2(mu O){Et2NC(S)S}(4)](4), respectively. The Et2NC(S)S ligands in 4 result from S-S bond rupture of tds molecules. The obtained compounds have been characterized by IR, H-1, P-31{H-1} and C-13{H-1} NMR spectroscopies, FAB(+)-MS, elemental and single-crystal X-ray diffraction (for 2 and 4)analyses. Complex 2 represents the first structurally characterized Re compound derived from 2-aminopyrimidine. Besides, the redox behaviour of 2-4 in CH2Cl2 solution has been studied by cyclic voltammetry, and the Lever electrochemical ligand parameter (E-L)has been estimated, for the first time, for HNpyrm. The electrochemical results are discussed in terms of electronic properties of the Re centres and the ligands.

Computational evaluation of hydraulic system behaviour with entrapped air under rapid pressurization

The pressurization of hydraulic systems containing entrapped air is considered a critical condition for the infrastructure's security due to transient pressure variations often occurred. The objective of the present study is the computational evaluation of trends observed in variation of maximum surge pressure resulting from rapid pressurizations. The comparison of the results with those obtained in previous studies is also undertaken. A brief state of art in this domain is presented. This research work is applied to an experimental system having entrapped air in the top of a vertical pipe section. The evaluation is developed through the elastic model based on the method of characteristics, considering a moving liquid boundary, with the results being compared with those achieved with the rigid liquid column model.

Dynamical behaviour on the parameter space: new populational growth models proportional to beta densities

We present new populational growth models, generalized logistic models which are proportional to beta densities with shape parameters p and 2, where p > 1, with Malthusian parameter r. The complex dynamical behaviour of these models is investigated in the parameter space (r, p), in terms of topological entropy, using explicit methods, when the Malthusian parameter r increases. This parameter space is split into different regions, according to the chaotic behaviour of the models.

Computational evaluation of hydraulic system behaviour with entrapped air under rapid pressurization

The pressurization of hydraulic systems containing entrapped air is considered a critical condition for the infrastructure's security due to transient pressure variations often occurred. The objective of the present study is the computational evaluation of trends observed in variation of maximum surge pressure resulting from rapid pressurizations. The comparison of the results with those obtained in previous studies is also undertaken. A brief state of art in this domain is presented. This research work is applied to an experimental system having entrapped air in the top of a vertical pipe section. The evaluation is developed through the elastic model based on the method of characteristics, considering a moving liquid boundary, with the results being compared with those achieved with the rigid liquid column model.

Mathematical modeling of pressurized system behaviour with entrapped air

The presence of entrapped air in pressurized hydraulic systems is considered a critical condition for the infrastructure security, due to the transient pressure enhancement related with its dynamic behaviour, similar to non-linear spring action. A mathematical model for the assessment of hydraulic transients resulting from rapid pressurizations, under referred condition is presented. Water movement was modeled through the elastic column theory considering a moving liquid boundary and the entrapped air pocket as lumped gas mass, where the acoustic effects are negligible. The method of characteristics was used to obtain the numerical solution of the liquid flow. The resulting model is applied to an experimental set-up having entrapped air in the top of a vertical pipe section and the numerical results are analyzed.

Chromatographic behaviour of monoclonal antibodies against wild-type amidase from Pseudomonasaeruginosa on immobilized metal chelates

The aim of this work was to devise a one-step purification procedure for monoclonal antibodies (MAbs) of IgG class by immobilized metal affinity chromatography (IMAC). Therefore, several stationary phases were prepared containing immobilized metal chelates in order to study the chromatographic behaviour of MAbs against wild-type amidase from Pseudomonas aeruginosa. Such MAbs adsorbed to Cu(II), Ni(II), Zn(II) and Co(II)-IDA agarose columns. The increase in ligand concentration and the use of longer spacer arms and higher pH values resulted in higher adsorption of MAbs into immobilized metal chelates. The dynamic binding capacity and the maximum binding capacity were 1.33 +/- 0.015 and 3.214 +/- 0.021 mg IgG/mL of sedimented commercial matrix, respectively. A K(D) of 4.53 x 10(-7) M was obtained from batch isotherm measurements. The combination of tailor-made stationary phases of IMAC and the correct selection of adsorption conditions permitted a one-step purification procedure to be devised for MAbs of IgG class. Culture supernatants containing MAbs were purified by IMAC on commercial-Zn(II) and EPI-30-IDA-Zn(II) Sepharose 6B columns and by affinity chromatography on Protein A-Sepharose CL-4B. This MAb preparation revealed on SDS-PAGE two protein bands with M(r) of 50 and 22 kDa corresponding to the heavy and light chains, respectively. Copyright (C) 2011 John Wiley & Sons, Ltd.

Finite element studies of the mechanical behaviour of the diaphragm in normal and pathological cases

The diaphragm is a muscular membrane separating the abdominal and thoracic cavities, and its motion is directly linked to respiration. In this study, using data from a 59-year-old female cadaver obtained from the Visible Human Project, the diaphragm is reconstructed and, from the corresponding solid object, a shell finite element mesh is generated and used in several analyses performed with the ABAQUS 6.7 software. These analyses consider the direction of the muscle fibres and the incompressibility of the tissue. The constitutive model for the isotropic strain energy as well as the passive and active strain energy stored in the fibres is adapted from Humphrey's model for cardiac muscles. Furthermore, numerical results for the diaphragmatic floor under pressure and active contraction in normal and pathological cases are presented.

Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

Parental cognitive dimensions associated with preschool children’s eating habits: an intervention study

Childhood excessive weight and obesity are a major public health concern from early childhood. Early childhood is an important period of development for developing healthy eating habits, that may be associated with an adequate present/future BMI. There is extensive evidence that children’s food intake is shaped by early experiences, suggesting ways in which parenting practices may be promoting obesity. But what leads parents to endorse healthier or detrimental educational practices and routines needs further study. 1. Perception of children’s weight: parents of overweight or obese children often fail to correctly perceive their children as overweight; failing to recognize their children’s excessive weight may impeach parents from implementing the best educational practices. 2. Concern: relation between the adequacy of mothers perception of their children’s weight and the level of concern - parental concern is be associated with parental practices. 3. Attribution of control: also, if parents do not consider their children’s eating behavior at least partially controllable by them, they may relinquish some of their responsibility in this area. Self-efficacy: evidence linking parental self-efficacy to parent competence and to parenting practices and behaviors; low parental self-efficacy related to the control of everyday behavior of young children may lead parents to abandon more consistent health practices and endorse permissive and inconsistent strategies. We designed 2 sequential studies that aim to contribute to the understanding of cognitive determinants of children’s eating patterns.

What parental cognitive dimensions are important to understand children’s eating habits?

Obesidade é uma preocupação de saúde pública. Objetivos OMS - Redução a zero da taxa de crescimento da obesidade e uma redução em 10% na prevalência de atividade física insuficiente. Em Portugal, os estudos de prevalência apontam para valores entre 24% e os 34% de crianças e jovens pré-obesos e obesos. Extensa confirmação da obesidade infantil como preditor da obesidade na idade adulta. Em alguns países há indicadores de que a taxa de obesidade infantil começa a ter uma ligeira diminuição, provavelmente fruto de intervenções no macrosistema. Necessidade de intervenção direta nos microssistemas familiar e escolar da criança para uma intervenção mais abrangente e eficaz. Existe um ampla confirmação da influência parental nos comportamentos alimentares da criança. Os comportamentais parentais relacionados com a alimentação da criança são influenciados por variáveis cognitivas parentais. A maioria dos pais de crianças com excesso de peso subavalia o peso do seu filho, mas não de outras crianças. Os pais das crianças pré-escolares distorcem mais o peso do que os pais de crianças mais velhas. Os pais com uma perceção correta utilizam mais estratégias de restrição alimentar.

A realidade da obesidade infantil em Portugal: epidemiologia, determinantes e intervenção

A obesidade é apontada como o distúrbio nutricional mais frequente em crianças e adolescentes nos países desenvolvidos e a sua prevalência tem vindo a aumentar a nível mundial a um ritmo alarmante. Neste artigo, são apresentados três estudos que se coordenam entre si. No primeiro estudo, avalia-se a prevalência de pré-obesidade (22,6%) e de obesidade (7,8%) infantojuvenil em Portugal, apresentando valores superiores nos rapazes e nos adolescentes mais jovens. Em relação aos hábitos alimentares, verifica-se que o consumo de alimentos de características nutricionais de baixa qualidade é superior no grupo normoponderal. Em relação à atividade física, quanto maior o índice de atividade física menor o percentil de I.M.C. No estudo sobre determinantes parentais, salienta-se que a grande maioria dos pais das crianças com excesso de peso tendem a sub-avaliar o peso da criança. Outro aspeto relevante é a confirmação de que o conhecimento nutricional dos pais influencia claramente os hábitos alimentares das crianças. Por fim, é apresentado um projeto de intervenção que, intervindo nos determinantes parentais, visa a mudança das suas crenças e comportamentos, de modo a promoverem mudanças alimentares nos seus filhos.

Comportamento alimentar e excesso de peso em profissionais do sector da saúde: estratégias para a promoção de saúde no local de trabalho

Mestrado em Intervenção Sócio-Organizacional na Saúde - Área de especialização: Políticas de Administração e Gestão de Serviços de Saúde.

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.