Multicameral voting cohesion games

This work links two research branches regarding cooperative games: multi-cameral games and a priori coalitions. Regarding the former, many parliaments are based on a bicameral system where bills have to be approved by both chambers. The parties’ power indices are affected by it. In fact one certain political party for one certain coalition can be crucial in one chamber and not in the other. Usually the problem can be solved by building a unified game, related to two or more chambers, where the global power indices can be calculated. Concerning cohesion games, some coalitions among parties might be possible, but have a low probability of materializing if the parties involved have very different ideologies. It is necessary to take this into consideration when we compute the relative power indices. In this work, a model is built that takes into consideration both topics. An automatic calculation algorithm is elaborated and is applied to the current situations in Belgium, the Czech Republic, France, Italy, the Netherlands, Poland and Romania, considering the location of the parties on the left-right axis. This model is then applied globally to the European Union. In this work the model is applied to Politics, but its applications are not limited to that field. For instance, in Finance it can be applied to describe agreements for debt restructuring and corporate mergers.     

Single and double pH-driven Cu2+ translocation with molecular rearrangement in alkyne-functionalized polyamino polyamido ligands

A new series of ligands, containing one (L1H(2)-L4H(2)) or two (L5H(4)-L6H(4)) 1,4,8,11-tetraaza-5,7-dione units and functionalized with a propargyl group on the C atom between the C=O moieties, has been synthesized. Protonation constants for the ligands and formation constants of their Cu(2+) complexes have been determined in water, and the coordination geometry of the complexes existing at various pH values has been investigated by coupled pH-metric and spectrophotometric titrations. Ligands capable of simple uptake of Cu(2+) with the formation of neutral, square-planar complexes containing the -2-charged diamino-diimido donor sets and ligands containing further coordinating groups (quinoline or pyridine) capable of single and double cation translocation have been investigated. The role of the substituents on the amino groups and the structural role played by the propargyl group have been examined as regards Cu(2+) complexation and translocation. In the double-translocating ligand L6H(4), when the two Cu(2+) ions move inside the diamino-diamido donor set, the slim propargyl group allows an unprecedented folding of the whole ligand with apical coordination of one pyridine to form a five-coordinate, square-pyramidal Cu(2+) ion. The crystal and molecular structures of this unusual [L6Cu(2)] complex have been determined by X-ray diffraction. Finally, oxidation of Cu(2+) to Cu(3+) has been studied by cyclic voltammetry in water, which revealed that the redox reaction occurs only when the copper cation is within the diamino-diimido compartment. Moreover, both functionalization of the primary amines with bulky substituents and apical coordination of Cu(2+) make access to the 3+ oxidation state more difficult and disrupt the reversibility of the electrochemical process.     

X-ray diffraction and theoretical studies for the quantitative assessment of intermolecular arene-perfluoroarene stacking interactions

The arene-perfluoroarene stacking interaction was studied by experimental and theoretical methods. A series of compounds with different possibilities for formation of this recognition motif in the solid state were synthesized, and their crystal structures determined by single-crystal X-ray diffraction. The crystal packing of these compounds, as well as the packing of related compounds retrieved from crystallographic databases, were analyzed with quantitative crystal potentials: total lattice energies and the cohesive energies of closest molecular pairs in the crystals were calculated. The arene-perfluoroarene recognition motif emerges as a dominant interaction in the non-hydrogen-bonding compounds studied here, to the point that asymmetric dimers formed over the stacking motif carry over to asymmetric units made of two molecules in the crystal both for pure compounds and for molecular complexes; however, inter-ring distances and angles range from 3.70 to 4.85 A and from 5 to 21 degrees , respectively. Pixel energy partitioning reveals that whenever aromatic rings stack, the largest cohesive energy contribution comes from dispersion, which roughly amounts to 20 kJ mol(-1) per phenyl ring, while the coulombic term is minor but significant enough to make a difference between the arene-arene or perfluoroarene-perfluoroarene interactions on the one hand, and arene-perfluoroarene interactions on the other, whereby the latter are favored by about 10 kJ mol(-1) per phenyl ring. No evidence of special interaction which can be attributed to HF confrontation was recognizable.     

Finite Anticlastic Bending of Hyperelastic Solids and Beams

This paper deals with the equilibrium problem in nonlinear elasticity of hyperelastic solids under anticlastic bending. A three-dimensional kinematic model, where the longitudinal bending is accompanied by the transversal deformation of cross sections, is formulated. Following a semi-inverse approach, the displacement field prescribed by the above kinematic model contains three unknown parameters. A Lagrangian analysis is performed and the compressible Mooney-Rivlin law is assumed for the stored energy function. Once evaluated the Piola-Kirchhoff stresses, the free parameters of the kinematic model are determined by using the equilibrium equations and the boundary conditions. An Eulerian analysis is then accomplished to evaluating stretches and stresses in the deformed configuration. Cauchy stress distributions are investigated and it is shown how, for wide ranges of constitutive parameters, the obtained solution is quite accurate. The whole formulation proposed for the finite anticlastic bending of hyperelastic solids is linearized by introducing the hypothesis of smallness of the displacement and strain fields. With this linearization procedure, the classical solution for the infinitesimal bending of beams is fully recovered.     

Analytic Hessian derivation for the quasi-one-dimensional Euler equations

The Hessian for the quasi-one-dimensional Euler equations is derived. A pressure minimization problem and a pressure matching inverse problem are considered. The flow sensitivity, adjoint sensitivity, gradient and Hessian are calculated analytically using a direct approach that is specific to the model problems. For the pressure minimization problem we find that the Hessian exists and it contains elements with significantly larger values around the shock location. For the pressure matching inverse problem we find at least one case for which the gradient as well as the Hessian do not exist. In addition, two formulations for calculating the Hessian are proposed and implemented for the given problems. Both methods can be implemented in industrial applications such as large scale aerodynamic optimization.     

Generalized recurrence plots for the analysis of images from spatially distributed systems

We propose a new method for the analysis of images showing patterns emerging from the evolution of spatially distributed systems. The generalized recurrence plot (GRP) and the generalized recurrence quantification analysis (GRQA) are exploited for the investigation of such patterns.We focus on snapshots of spatio-temporal processes such as the formation of Turing structures and traveling waves in the Belousov-Zhabotinsky reaction, satellite images of spatial chlorophyll distribution in seas and oceans (similar to turbulent flows), colonies of Dyctiostelium discoideum, fractals, and noise.The method is based on the GRP and GRQA and particularly on the measures determinism (DET) and entropy (ENT), providing a new criterion for the assessment and classification of images based on the simultaneous evaluation of their global and local structure.The DET-ENT diagram is introduced and compared with the classical image analysis entropy defined on the pixels’ values. The method proposed provides appealing performances in the case of images showing complex spatial patterns.     

Organic film thickness influence on the bias stress instability in?sexithiophene field effect transistors

In this paper, the dynamics of bias stress phenomenon in Sexithiophene (T6) Field Effect Transistors (FETs) has been investigated. T6 FETs have been fabricated by vacuum depositing films with thickness from 10 to 130 nm on Si/SiO₂ substrates. After the T6 film structural analysis by X-ray diffraction and the FET electrical investigation focused on carrier mobility evaluation, bias stress instability parameters have been estimated and discussed in the context of existing models. By increasing the film thickness, a clear correlation between the stress parameters and the structural properties of the organic layer has been highlighted. Conversely, the mobility values as a result are found to be almost thickness independent.     

Drug-anaesthetic interaction in phMRI: the case of the psychotomimetic agent phencyclidine

Pharmacological magnetic resonance imaging (phMRI) provides a powerful means to map the effects of drugs on brain activity, with important applications in pharmacological research. However, phMRI studies in preclinical species are often conducted under general anaesthesia as a means to avoid head motion and to minimise the stress induced by the procedure. Under these conditions, the phMRI response to the drug of interest may be affected by interactions with the anaesthetic agent, with consequences for the interpretation of the data. Here, we have investigated the phMRI response to phencyclidine (PCP), an NMDA receptor blocker, in the halothane-anaesthetised rat for varying levels of anaesthesia and different PCP challenge doses. PCP induces psychotic-like symptoms in humans and laboratory animals and is widely applied as a pharmacological model of schizophrenia. However, PCP possesses anaesthetic properties per se, and its interactions with halothane might result in significant effects on the phMRI activation patterns. We observed two qualitatively different patterns of phMRI response. At 0.5 mg/kg iv PCP and 0.8% halothane maintenance anaesthesia, the lowest doses explored, an activation of discrete cortico-limbo-thalamic structures was observed, consistent with neuroimaging studies in humans and 2-deoxyglucose functional mapping in conscious animal models. However, higher anaesthetic concentrations or higher PCP challenge doses resulted in complete abolition of the positive response and in a widespread cortical deactivation (negative response). In the intermediate regime, we observed a dichotomic behaviour, with individual subjects showing one pattern or the other. These findings indicate a dose-dependent drug-anaesthetic interaction, with a complete reversal of the effects of PCP at higher challenge doses or HT concentrations.     

The detection limit of a Gd3+-based T1 agent is substantially reduced when targeted to a protein microdomain

Simple low molecular weight (MW) chelates of Gd(3+) such as those currently used in clinical MRI are considered too insensitive for most molecular imaging applications. Here, we evaluated the detection limit (DL) of a molecularly targeted low MW Gd(3+)-based T(1) agent in a model where the receptor concentration was precisely known. The data demonstrate that receptors clustered together to form a microdomain of high local concentration can be imaged successfully even when the bulk concentration of the receptor is quite low. A GdDO3A-peptide identified by phage display to target the anti-FLAG antibody was synthesized, purified and characterized. T(1-)weighted MR images were compared with the agent bound to antibody in bulk solution and with the agent bound to the antibody localized on agarose beads. Fluorescence competition binding assays show that the agent has a high binding affinity (K(D)=150 nM) for the antibody, while the fully bound relaxivity of the GdDO3A-peptide/anti-FLAG antibody in solution was a relatively modest 17 mM(-1) s(-1). The agent/antibody complex was MR silent at concentrations below approximately 9 microM but was detectable down to 4 microM bulk concentrations when presented to antibody clustered together on the surface of agarose beads. These results provided an estimate of the DLs for other T(1)-based agents with higher fully bound relaxivities or multimeric structures bound to clustered receptor molecules. The results demonstrate that the sensitivity of molecularly targeted contrast agents depends on the local microdomain concentration of the target protein and the molecular relaxivity of the bound complex. A model is presented, which predicts that for a molecularly targeted agent consisting of a single Gd(3+) complex with bound relaxivity of 100 mM(-1) s(-1) or, more reasonably, four tethered Gd(3+) complexes each having a bound relaxivity of 25 mM(-1) s(-1), the DL of a protein microdomain is approximately 690 nM at 9.4 T. These experimental and extrapolated DLs are both well below current literature estimates and suggests that detection of low MW molecularly targeted T(1) agents is not an unrealistic goal.