Ni(II)-doped CsCdBrCl2: Variation of spectral and structural properties via mixed-halide coordination

A new addition to the family of single-molecule magnets is reported: an Fete cage stabilized with benzoate and pyridonate ligands. Monte Carlo methods have been used to derive exchange parameters within the cage, and hence model susceptibility behavior.

Interactive expectations

In modeling expectation formation, economic agents are usually viewed as forming expectations adaptively or in accordance with some rationality postulate. We offer an alternative nonlinear model where agents exchange their opinions and information with each other. Such a model yields multiple equilibria, or attracting distributions, that are persistent but subject to sudden large jumps. Using German Federal Statistical Office economic indicators and German IFO Poll expectational data, we show that this kind of model performs well in simulation experiments. Focusing upon producers' expectations in the consumption goods sector, we also discover evidence that structural change in the interactive process occurred over the period of investigation (1970-1998). Specifically, interactions in expectation formation seem to have become less important over time.

Behavior of argon gas release from manganese oxide minerals as revealed by Ar-40/Ar-39 laser incremental heating analysis

Manganese oxides in association with paleo-weathering may provide significant insights into the multiple factors affecting the formation and evolution of weathering profiles, such as temperature, precipitation, and biodiversity. Laser probe step-heating analysis of supergene hollandite and cryptomelane samples collected from central Queensland, Australia, yield well-defined plateaus and consistent isochron ages, confirming the feasibility, dating very-fined supergene manganese oxides by Ar-40/(39) Ar technique. Two distinct structural sites hosting Ar isotopes can be identified in light of their degassing behaviors obtained by incremental heating analyses. The first site, releasing its gas fraction at the laser power 0.2-0.4 W, yields primarily Ar-40(atm), Ar-38(atm), and Ar-36(atm), (atmospheric Ar isotopes). The second sites yield predominantly Ar-40* (radiogenic Ar-40), Ar-39(K), and Ar-38(K) (nucleogenic components), at similar to0.5-1.0 W. There is no significant Ar gas released at the laser power higher than 1.0 W, indicating the breakdown of the tunnel sites hosting the radiogenic and nucleogenic components. The excellent match between the degassing behaviors of Ar-40*, Ar-39(K), and Ar-38(K) suggests that these isotopes occupy the same crystallographic sites and that Ar-39(K) loss from the tunnel site by recoil during neutron irradiation and/or bake-out procedure preceding isotopic analysis does not occur. Present investigation supports that neither the overwhelming atmospheric Ar-40 nor the very-fined nature of the supergene manganese oxides poses problems in extracting meaningful weathering geo-chronological information by analyzing supergene manganese oxides minerals.

Consumer behavior and profile in cross border tourism destinations

Tourism is a phenomenon that moves millions of people around the world, taking as a major driver of the global economy. Such relevance is reflected in the proliferation of studies in the overall area known as tourism, under various perspectives and backgrounds. In the light of such multitude of insights our study aims at gaining a deeper understanding of customer profiling and behavior in cross-border tourism destinations. Previous studies conducted in such contexts suggest that cross-border regions (CBRs) are an attractive and desirable idea, yet requiring further theoretical and empirical research. The new configuration of many CBRs calls for a debate on issues concerning its development, raising up important dimensions, such as, organization and planning of common tourism destinations. There is still a gap in the understanding of destination management in CBRs and the customer profile and motivations. Overall this research aims at attaining a deeper understanding of the profile and behavior of consumers in tourism settings, addressing the predisposition for the destination. The study addresses the following research question: “What factors influence customer behavior and attitudes in a CBRs tourism destination?” To address our question we will take an interdisciplinary perspective bringing together inputs from marketing, tourism and local economics. When addressing consumer behavior in tourism previous studies considered the following constructs: involvement, place attachment, satisfaction and destination loyalty. In order to establish the causal relationships in our theoretical model, we intend to develop a predominant quantitative design, yet we plan to conduct exploratory interviews. In the analysis and discussion of results, we intend to use Structural Equation Modeling. It will further allow understanding how the constructs in the research model relate to each other in the specified context. Results are also expected to have managerial implications. Consequently our results may assist decision makers in developing their local policies.

Mixed-integer nonlinear approach for the optimal scheduling of a head-dependent hydro chain

This paper is on the problem of short-term hydro scheduling (STHS), particularly concerning a head-dependent hydro chain We propose a novel mixed-integer nonlinear programming (MINLP) approach, considering hydroelectric power generation as a nonlinear function of water discharge and of the head. As a new contribution to eat her studies, we model the on-off behavior of the hydro plants using integer variables, in order to avoid water discharges at forbidden areas Thus, an enhanced STHS is provided due to the more realistic modeling presented in this paper Our approach has been applied successfully to solve a test case based on one of the Portuguese cascaded hydro systems with a negligible computational time requirement.

Biochemical and structural characterization of β-lactamases tem-180 and tem-201

With the constant development of new antibiotics, selective pressure is a force to reckon when investigating antibiotic resistance. Although advantageous for medical treatments, it leads to increasing resistance. It is essential to use more potent and toxic antibiotics. Enzymes capable of hydrolyzing antibiotics are among the most common ways of resistance and TEM variants have been detected in several resistant isolates. Due to the rapid evolution of these variants, complex phenotypes have emerged and the need to understand their biological activity becomes crucial. To investigate the biochemical properties of TEM-180 and TEM-201 several computational methodologies have been used, allowing the comprehension of their structure and catalytic activity, which translates into their biological phenotype. In this work we intent to characterize the interface between these proteins and the several antibiotics used as ligands. We performed explicit solvent molecular dynamics (MD) simulations of these complexes and studied a variety of structural and energetic features. The interfacial residues show a distinct behavior when in complex with different antibiotics. Nevertheless, it was possible to identify some common Hot Spots among several complexes – Lys73, Tyr105 and Glu166. The structural changes that occur during the Molecular Dynamic (MD) simulation lead to the conclusion that these variants have an inherent capacity of adapting to the various antibiotics. This capability might be the reason why they can hydrolyze antibiotics that have not been described until now to be degraded by TEM variants. The results obtained with computational and experimental methodologies for the complex with Imipenem have shown that in order to this type of enzymes be able to acylate the antibiotics, they need to be capable to protect the ligand from water molecules.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

Derivative-free optimization and filter methods to solve nonlinear constrained problems

In real optimization problems, usually the analytical expression of the objective function is not known, nor its derivatives, or they are complex. In these cases it becomes essential to use optimization methods where the calculation of the derivatives, or the verification of their existence, is not necessary: the Direct Search Methods or Derivative-free Methods are one solution. When the problem has constraints, penalty functions are often used. Unfortunately the choice of the penalty parameters is, frequently, very difficult, because most strategies for choosing it are heuristics strategies. As an alternative to penalty function appeared the filter methods. A filter algorithm introduces a function that aggregates the constrained violations and constructs a biobjective problem. In this problem the step is accepted if it either reduces the objective function or the constrained violation. This implies that the filter methods are less parameter dependent than a penalty function. In this work, we present a new direct search method, based on simplex methods, for general constrained optimization that combines the features of the simplex method and filter methods. This method does not compute or approximate any derivatives, penalty constants or Lagrange multipliers. The basic idea of simplex filter algorithm is to construct an initial simplex and use the simplex to drive the search. We illustrate the behavior of our algorithm through some examples. The proposed methods were implemented in Java.

Análise estática não linear de um edifício em betão armado

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil

Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Exciting dynamical behavior in a network of two coupled rings of Chen oscillators

We study exotic patterns appearing in a network of coupled Chen oscillators. Namely, we consider a network of two rings coupled through a “buffer” cell, with Z3×Z5 symmetry group. Numerical simulations of the network reveal steady states, rotating waves in one ring and quasiperiodic behavior in the other, and chaotic states in the two rings, to name a few. The different patterns seem to arise through a sequence of Hopf bifurcations, period-doubling, and halving-period bifurcations. The network architecture seems to explain certain observed features, such as equilibria and the rotating waves, whereas the properties of the chaotic oscillator may explain others, such as the quasiperiodic and chaotic states. We use XPPAUT and MATLAB to compute numerically the relevant states.

Modelação e reforço de vigas de betão armado com laminados de fibra de carbono

Com o atual estado da construção em Portugal, a reabilitação urbana é uma realidade. Com muitos dos edifícios a necessitarem de reforço, procurou-se abordar o comportamento real das estruturas, indo além da típica análise linear elástica. Desta forma, pretendeu-se aumentar o conhecimento acerca da modelação numérica não-linear de estruturas de betão armado, expondo modelos de cálculo relativamente simples e de fácil compreensão, com o objetivo de servir de base a uma avaliação da capacidade de carga de um elemento estrutural. O modelo de cálculo foi validado com recurso ao trabalho experimental de Bresler e Scordelis (1963). Analisou-se o comportamento até à rotura de três vigas ensaiadas à flexão. Posteriormente, foi realizado um estudo paramétrico de algumas propriedades do betão com vista à discussão do melhor de ajuste. Em seguida, já no campo do reforço estrutural, simulou-se numericamente vigas reforçadas com CFRP, com recurso à técnica EBR e NSM. Comparam-se os resultados numéricos com os ensaios experimentais de Cruz et al. (2011a). Avaliou-se ainda o desempenho de soluções alternativas com variações na área e comprimento dos laminados. Para finalizar, foi desenvolvida uma campanha experimental com diferentes áreas de reforço. Conceberam-se e executaram-se três vigas de betão armado sobre as quais se instalaram laminados de CFRP. Os resultados experimentais são apresentados e discutidos à luz dos resultados do respetivo modelo numérico. No cômputo geral, o presente trabalho permitiu aferir a validade de modelos não-lineares na previsão do comportamento efetivo das estruturas até à rotura. Assinala-se a concordância em vários resultados experimentais analisados. Ficaram também patentes os principais fenómenos ligados ao reforço de vigas com CFRP, focados nos respetivos modelos de cálculo e nos resultados experimentais apresentados.

Simulation of masonry out-of-plane failure modes by multi-body dynamics

The seismic assessment of the local failure modes in existing masonry buildings is currently based on the identification of the so-called local mechanisms, often associated with the out-of-plane wall behavior, whose stability is evaluated by static force-based approaches and, more recently, by some displacement-based proposals. Local mechanisms consist of kinematic chains of masonry portions, often regarded as rigid bodies, with geometric nonlinearity and concentrated nonlinearity in predefined contact regions (unilateral no-tension behavior, possible sliding with friction). In this work, the dynamic behavior of local mechanisms is simulated through multi-body dynamics, to obtain the nonlinear response with efficient time history analyses that directly take into account the characteristics of the ground motion. The amplification/filtering effects of the structure are considered within the input motion. The proposed approach is validated with experimental results of two full-scale shaking-table tests on stone masonry buildings: a sacco-stone masonry façade tested at Laboratório Nacional de Engenharia Civil and a two-storey double-leaf masonry building tested at European Centre for Training and Research in Earthquake Engineering (EUCENTRE).

Assessment by doppler ultrasound of entheseal lesions in spondyloarthritis : a longitudial study to determine structural damage and disease activity lesions

RESUMO: Enthesitis is the hallmark of spondyloarthritis (SpA), and is observed in all subtypes. Wide information on SpA abnormalities, including synovitis, tendinitis and enthesitis, can be efficiently perceived by Doppler ultrasound. Furthermore, several studies on imaging of enthesis showed that imaging techniques are better than clinical examination to detect enthesis alterations; and vascularized enthesitis detected by Doppler ultrasound appears to be a valuable diagnostic tool to confirm SpA diagnosis. However, data published until now concerning entheseal elementary alterations that characterize SpA enthesitis (enthesis inflammatory activity) or enthesopathy (permanent structural changes) reflect rather the authors’ empiric opinion than a methodological validation process. In this sense it seems crucial to identify elementary entheseal lesions associated with activity or damage, in order to improve monitoring and treatment response in SpA patients. The development of better assessment tools is today a challenge and a need in SpA. The first study of this thesis focused on the analysis of the reliability of inter-lector and inter-ultrasonography equipment of Madrid sonography enthesitis index (MASEI). Fundamental data for the remaining unrolling project validity. In the second and third studies we concerned about two entheseal elemental lesions: erosions and bursa. In literature erosions represent a permanent structural damage, being useful for monitoring joint injury, disease activity and therapeutic response in many rheumatic diseases; and to date, this concept has been mostly applied in rheumatoid arthritis (RA). Unquestionably, erosion is a tissue-related damage and a structural change. However, the hypothesis that we decided to test was if erosions represent a permanent structural change that can only grow and worsen over time, as occurs in RA, or a transitory alteration. A longitudinal study of early SpA patients was undertaken, and the Achilles enthesis was used as a model. Our results strongly suggested that previously detected erosions could disappear during the course of the disease, being consistent with the dynamic behavior of erosion over time. Based on these striking results it seems reasonable to suggest that the new-bone formation process in SpA could be associated with the resolution of cortical entheseal erosion over time. These results could also be in agreement with the apparent failure of anti-tumor necrosis factor (TNF) therapies to control bone proliferation in SpA; and with the relation of TNF-α, Dickkopf-related protein 1 (Dkk-1) and the regulatory molecule of the Wnt signaling pathway in the bone proliferation in SpA. In the same model, we then proceeded to study the enthesis bursa. Interestingly, the Outcome Measures in Rheumatology Clinical Trials (OMERACT) enthesopathy definition does not include bursa as an elementary entheseal lesion. Nonetheless, bursa was included in 46% of the enthesis studies in a recently systematic literature review, being in agreement with the concept of “synovio-entheseal complex” that includes the link between enthesitis and osteitis in SpA. It has been clarified in recent data that there is not only a close functional integration of the enthesis with the neighboring bone, but also a connection between enthesitis and synovitis. Therefore, we tried to assess the prevalence and relevance of the bursa-synovial lesion in SpA. Our findings showed a significant increase of Achilles bursa presence and thickness in SpA patients compared to controls (healthy/mechanical controls and RA controls). These results raise awareness to the need to improve the enthesopathy ultrasonographic definition. In the final work of this thesis, we have explored new perspectives, not previously reported, about construct validity of enthesis ultrasound as a possible activity outcome in SpA. We performed a longitudinal Achilles enthesis ultrasound study in patients with early SpA. Achilles ultrasound examinations were performed at baseline, six- and twelve-month time periods and compared with clinical outcome measures collected at basal visit. Our results showed that basal erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) are higher in patients with Doppler signal in enthesis, and even that higher basal ESR, CRP and Ankylosing Spondylitis Disease Activity Score (ASDAS) predicted a higher Doppler signal (an ultrasound alteration accepted as representative of inflammation) six months later. Patients with very high disease activity assessed by ASDAS (>3.5) at baseline had significantly higher Achilles total ultrasound score verified at the same time; and ASDAS <1.3 predicted no Doppler signal at six and twelve months. This seems to represent a connection between classical biomarkers and clinical outcomes associated with SpA activity and Doppler signal, not only at the same time, but also for the following months. Remarkably, patients with inactive disease (ASDAS < 1.3) at baseline had no Doppler signal at six and twelve months. These findings reinforce the potential use of ultrasound related techniques for disease progression assessment and prognosis purposes. Intriguingly, Ankylosing Spondylitis Disease Activity Index (BASDAI) didn’t show significant differences between different cut-offs concerning ultrasound lesions or Doppler signal, while verified with ASDAS. These results seem to indicate that ASDAS reflects better than BASDAI what happens in the enthesis. The work herein discussed clearly shows the potential utility of ultrasound in enthesis assessment in SpA patients, and can be important for the development of ultrasound activity and structural damage scores for diagnosis and monitoring purposes. Therefore, local promotion of this technique constitutes a medical intervention that is worth being tested in SpA patients for diagnosis, monitoring and prognosis purposes.