Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Extern Web-service-lösning vid SSAB Tunnplåt i Borlänge- för kommunikation med sina distributions lager

Detta examensarbete har utförts på SSAB- Tunnplåt i Borlänge under vårterminen 2004 och omfattar 10 veckors arbete.SSAB sköter idag sin kommunikation med distributionslagren via fax, telefon eller e-post. Eftersom detta är ett ganska tidskrävande kommunikationssätt, vill SSAB ha en smidigare och snabbare kommunikationslösning. Den lösning som SSAB vill ha är en extern Web-service-lösning för att upprätta en säker kommunikation med sina distributionslager.Parallellt med byggandet av Web-service-lösningen arbetades en förvaltningsmodell fram. Den beskriver hur förvaltningsorganisationen med dess rutiner kan se ut vid implementering av lösningen.För att skapa en säker förbindelse med Web-servicen skall en webbklient användas som i sin tur anropar en COM+ komponent. Detta för att kunna skicka med certifikatet ifrån webbklienten till webbservern där Web-servicen ligger. COM+ komponenten måste få tillgång till en användarprofil när den kommunicerar med Web-servicen. Detta för att kunna upprätta en SSL-förbindelse i det inledande skedet. SSL-förbindelsen skall läggas i den VPN-tunnel som mVPN tillhandahåller via WSSAL.

Kraftutveckling för manuella trädfällningsredskap : Force development for manual tree felling tools

The objective with this study has been to build general models of the mechanics in tree felling with chain-saw and to compare felling torque for different tools. The theoretical models are completed and validated with a comparative study. The study includes a great number of felling tools of which some are used with different methods. Felling torque was measured using a naturally like measuring arrangement where a tree is cut at about 3.7 m height and then anchored with a dynamometer to a tree opposite to the felling direction. Notch and felling cut was made as ordinary with exception that the hinge was made extra thin to reduce bending resistance. The tree was consequently not felled during the trials and several combinations of felling tools and individuals could be used on the same tree.The results show big differences between tools, methods and persons. The differences were, however, not general, but could vary depending on conditions (first of all tree diameters). Tools and methods that push or pull on the stem are little affected by the size of the tree, while tools that press on the stump are very much dependent of a large stump-diameter. Hand force asserted on a simple pole is consequently a powerful tool on small trees. For trees of medium size there are several alternative methods with different sizes and brands of felling levers and wedges. Larger and more ungainly tools and methods like tree pusher, winch, etc. develop very high felling torque on all tree sizes. On large trees also the felling wedge and especially the use of several wedges together develop very high felling torque.

Abstract types and distributions in independent private value auctions

In this note, in an independent private values auction framework, I discuss the relationship between the set of types and the distribution of types. I show that any set of types, finite dimensional or not, can be extended to a larger set of types preserving incentive compatibility constraints, expected revenue and bidder’s expected utilities. Thus for example we may convexify a set of types making our model amenable to the large body of theory in economics and mathematics that relies on convexity assumptions. An interesting application of this extension procedure is to show that although revenue equivalence is not valid in general if the set of types is not convex these mechanism have underlying distinct allocation mechanism in the extension. Thus we recover in these situations the revenue equivalence.

Localization strategies of multinationals in Brazil which characteristics of the Brazilian market force multinational companies to localize their marketing activities?

Uma vez que as perspectivas de crescimento económico nos países mais desenvolvidos, como a Europa, os EUA eo Japão estão diminuindo, os mercados emergentes têm se tornado cada vez mais importante para muitas empresas multinacionais. Brasil, Rússia, Índia e China (BRICs) são agora os principais mercados em crescimento em todo o mundo e as empresas estão buscando estratégias para explorar ao máximo o potencial de consumo promissor nessas regiões. Um dos modos mais elaborados de prosseguir essa estratégia é conhecida como "localização" - uma adaptação das práticas de negócios (ao longo de toda a cadeia de suprimentos) com as preferências e condições locais. Este artigo é projetado para analisar as atividades de localização de empresas multinacionais no Brasil. O foco da análise é o de investigar as características do mercado brasileiro, que induzem as multinacionais a localizar o seu marketing mix (composto de produto, preço, colocação e promoção). Em dois estudos de casos com a empresa Suiça Nestlé e a empresa Alemã Volkswagen vários padrões de localização foram no mercado consumidor brasileiro. Os quatro resultados mais significativos da análise são os diferentes padrões sociais o Brasil, que forçar as empresas a reformular certas funções do seu mix de marketing (por exemplo, a colocação no caso da Nestlé), a aceitação dos consumidores brasileiros a pagar preços relativamente elevados (por exemplo, taxas de Volkswagen até 100% mais por seus produtos em relação à Alemanha); o enorme tamanho do Brasil ea infra-estrutura deficiente, que exigem uma abordagem de distribuição localizada; eo caráter atualmente ainda menos exigente dos estratos de consumidores brasileiros emergentes, que permitem às empresas oferecer produtos menos sofisticados em comparação aos mercados europeus.

We're Chained: an analysis of systemic risk in finance

This dissertation presents two papers on how to deal with simple systemic risk measures to assess portfolio risk characteristics. The first paper deals with the Granger-causation of systemic risk indicators based in correlation matrices in stock returns. Special focus is devoted to the Eigenvalue Entropy as some previous literature indicated strong re- sults, but not considering different macroeconomic scenarios; the Index Cohesion Force and the Absorption Ratio are also considered. Considering the S&P500, there is not ev- idence of Granger-causation from Eigenvalue Entropies and the Index Cohesion Force. The Absorption Ratio Granger-caused both the S&P500 and the VIX index, being the only simple measure that passed this test. The second paper develops this measure to capture the regimes underlying the American stock market. New indicators are built using filtering and random matrix theory. The returns of the S&P500 is modelled as a mixture of normal distributions. The activation of each normal distribution is governed by a Markov chain with the transition probabilities being a function of the indicators. The model shows that using a Herfindahl-Hirschman Index of the normalized eigenval- ues exhibits best fit to the returns from 1998-2013.

Perceções acerca do impacto da prática desportiva: um estudo de caso com atletas de competição da escola Dragon Force Madeira

Este estudo inscreve-se no quadro de pesquisa da análise das perceções dos atletas de competição sub 13 da escola Dragon Force acerca do impacto das actividades desportivas sobre o rendimento escolar, relações entre pares e interpessoais, autoestima e autoconceito. Participaram neste estudo 14 atletas do género masculino com idades entre 11 e 13 anos. As metodologias utilizadas foram a quantitativa e a qualitativa. Os instrumentos utilizados foram: notas académicas, Registo de Empenho e Desenvolvimento Educativo (R.E.D.E.), Escala de Autoestima Global de Rosenberg (Rosenberg Self-Esteem Scale, RSES), Questionário de Motivação para as Atividades Desportivas (QMAD), e Escala de Autopercepção de Susan Harter para adolescentes (EAPH-A). Também foi utilizado o focus group. Parte dos dados foi inserida na base de dados do SPSS, versão 19.0, procedendo-se, igualmente, à análise de conteúdo do material resultante do focus group. Embora os resultados revelem que existem algumas diferenças de perceção, a maior parte dos atletas considera que a prática desportiva está associada à alegria e ao divertimento. Também entendem que esta prática influencia o rendimento escolar, a autoestima, o autoconceito, as relações entre pares e interpessoais.

Spatial Assessment of Indices for Characterizing the Erosive Force of Rainfall in El Salvador Republic

Soil erosion data in El Salvador Republic are scarce and there is no rainfall erosivity map for this region. Considering that rainfall erosivity is an important guide for planning soil erosion control practices, a spatial assessment of indices for characterizing the erosive force of rainfall in El Salvador Republic was carried out. Using pluviometric records from 25 weather stations, we applied two methods: erosivity index equation and the Fournier index. In all study area, the rainiest period is from May to November. Annual values of erosivity index ranged from 7,196 to 17,856 MJ mm ha(-1) h(-1) year(-1) and the Fournier index ranged from 52.9 to 110.0 mm. The erosivity map showed that the study area can be broadly divided into three major erosion risk zones, and the Fournier index map was divided into four zones. Both methods revealed that the erosive force is severe in all study area and presented significant spatial correlation with each other. The erosive force in the country is concentrated mainly from May to November.

Spontaneous Interblink Time Distributions in Patients with Graves' Orbitopathy and Normal Subjects

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spatial variations at different observational scales and the seasonal distributions of stream macroalgae in a Brazilian subtropical region

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mapping of adhesion forces on soil minerals in air and water by atomic force spectroscopy (AFS)

The adhesion force between an atomic force microscope (AFM) tip and sample surfaces, mica and quartz substrates, was measured in air and water. The force curves show that the adhesion has a strong dependence on both the surface roughness and the environmental conditions surrounding the sample. The variability of the adhesion force was examined in a series of measurements taken at the same point, as well as at different places on the sample surface. The adhesion maps obtained from the distribution of the measured forces indicated regions contaminated by either organic compounds or adsorbed water. Using simple mathematical expressions we could quantitatively predict the adhesion force behavior in both air and water. The experimental results are in good agreement with theoretical calculations, where the adhesion forces in air and water were mostly associated with capillary and van der Waals forces, respectively. A small long-range repulsive force is also observed in water due to the overlapping electrical double-layers formed on both the tip and sample surfaces.

Interaction of small amounts of bovine serum albumin with phospholipid monolayers investigated by surface pressure and atomic force microscopy

The influence of small amounts of bovine serum albumin (BSA) (nM concentration) on the lateral organization of phospholipid monolayers at the air-water interface and transferred onto solid substrates as one-layer Langmuir-Blodgett (LB) films was investigated. The kinetics of adsorption of BSA onto the phospholipid monolayers was monitored with surface pressure isotherms in a Langmuir trough, for the zwitterionic dipalmitoylphosphatidyl ethanolamine (N,N-dimethyl-PE) and the anionic dimyristoylphosphatidic acid (DMPA). A monolayer of N,N-dimethyl-PE or DMPA incorporating BSA was transferred onto a solid substrate using the Langmuir-Blodgett technique. Atomic force microscopy (AFM) images of one-layer LB films displayed protein-phospholipid domains, whose morphology was characterized using dynamic scaling theories to calculate roughness exponents. For DMPA-BSA films the surface is characteristic of self-affine fractals, which may be described with the Kardar-Parisi-Zhang (KPZ) equation. on the other hand, for N,N-dimethyl-PE-BSA films, the results indicate a relatively flat surface within the globule. The height profile and the number and size of globules varied with the type of phospholipid. The overall results, from kinetics of adsorption on Langmuir monolayers and surface morphology in LB films, could be interpreted in terms of the higher affinity of BSA to the anionic DMPA than to the zwitterionic N,N-dimethyl-PE. Furthermore, the effects from such small amounts of BSA in the monolayer point to a cooperative response of DMPA and N,N-dimethyl-PE monolayers to the protein. (c) 2005 Elsevier B.V. All rights reserved.

Direct observation of oxidative stress on the cell wall of Saccharomyces cerevisiae strains with atomic force microscopy

We imaged pores on the surface of the cell wall of three different industrial strains of Saccharomyces cerevisiae using atomic force microscopy. The pores could be enlarged using 10 mM diamide, an SH residue oxidant that attacks surface proteins. We found that two strains showed signs of oxidative damage via changes in density and diameter of the surface pores. We found that the German strain was resistant to diamide induced oxidative damage, even when the concentration of the oxidant was increased to 50 mM. The normal pore size found on the cell walls of American strains had diameters of about 200nm. Under conditions of oxidative stress the diameters changed to 400nm.This method may prove to be a useful rapid screening process (45-60 min) to determine which strains are oxidative resistant, as well as being able to screen for groups of yeast that are sensitive to oxidative stress. This rapid screening tool may have direct applications in molecular biology (transference of the genes to inside of living cells) and biotechnology (biotransformations reactions to produce chiral synthons in organic chemistry.