Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Cape Verde hotspot from the upper crust to the top of the lower mantle

We investigate the crust, upper mantle and mantle transition zone of the Cape Verde hotspot by using seismic P and S receiver functions from several tens of local seismograph stations. We find a strong discontinuity at a depth of similar to 10 km underlain by a similar to 15-km thick layer with a high (similar to 1.9) Vp/Vs velocity ratio. We interpret this discontinuity and the underlying layer as the fossil Moho, inherited from the pre-hotspot era, and the plume-related magmatic underplate. Our uppermost-mantle models are very different from those previously obtained for this region: our S velocity is much lower and there are no indications of low densities. Contrary to previously published arguments for the standard transition zone thickness our data indicate that this thickness under the Cape Verde islands is up to similar to 30 km less than in the ambient mantle. This reduction is a combined effect of a depression of the 410-km discontinuity and an uplift of the 660-km discontinuity. The uplift is in contrast to laboratory data and some seismic data on a negligible dependence of depth of the 660-km discontinuity on temperature in hotspots. A large negative pressure-temperature slope which is suggested by our data implies that the 660-km discontinuity may resist passage of the plume. Our data reveal beneath the islands a reduction of S velocity of a few percent between 470-km and 510-km depths. The low velocity layer in the upper transition zone under the Cape Verde archipelago is very similar to that previously found under the Azores and a few other hotspots. In the literature there are reports on a regional 520-km discontinuity, the impedance of which is too large to be explained by the known phase transitions. Our observations suggest that the 520-km discontinuity may present the base of the low-velocity layer in the transition zone. (C) 2011 Elsevier B.V. All rights reserved.

A class of singular first order differential equations with applications in reaction-diffusion

Agências Financiadoras: FCT e MIUR

From the Bay of Biscay to the High Atlas: completing the anisotropic characterization of the upper mantle beneath the westernmost Mediterranean region

The knowledge of the anisotropic properties beneath the Iberian Peninsula and Northern Morocco has been dramatically improved since late 2007 with the analysis of the data provided by the dense TopoIberia broadband seismic network, the increasing number of permanent stations operating in Morocco, Portugal and Spain, and the contribution of smaller scale/higher resolution experiments. Results from the two first TopoIberia deployments have evidenced a spectacular rotation of the fast polarization direction (FPD) along the Gibraltar Arc, interpreted as an evidence of mantle flow deflected around the high velocity slab beneath the Alboran Sea, and a rather uniform N100 degrees E FPD beneath the central Iberian Variscan Massif, consistent with global mantle flow models taking into account contributions of surface plate motion, density variations and net lithosphere rotation. The results from the last Iberarray deployment presented here, covering the northern part of the Iberian Peninsula, also show a rather uniform FPD orientation close to N100 degrees E, thus confirming the previous interpretation globally relating the anisotropic parameters to the LPO of mantle minerals generated by mantle flow at asthenospheric depths. However, the degree of anisotropy varies significantly, from delay time values of around 0.5 s beneath NW Iberia to values reaching 2.0 sin its NE comer. The anisotropic parameters retrieved from single events providing high quality data also show significant differences for stations located in the Variscan units of NW Iberia, suggesting that the region includes multiple anisotropic layers or complex anisotropy systems. These results allow to complete the map of the anisotropic properties of the westernmost Mediterranean region, which can now be considered as one of best constrained regions worldwide, with more than 300 sites investigated over an area extending from the Bay of Biscay to the Sahara platform. (C) 2015 Elsevier B.V. All rights reserved.

Upper crustal structure of Madeira Island revealed from ambient noise tomography

We present the first image of the Madeira upper crustal structure, using ambient seismic noise tomography. 16 months of ambient noise, recorded in a dense network of 26 seismometers deployed across Madeira, allowed reconstructing Rayleigh wave Green's functions between receivers. Dispersion analysis was performed in the short period band from 1.0 to 4.0 s. Group velocity measurements were regionalized to obtain 20 tomographic images, with a lateral resolution of 2.0 km in central Madeira. Afterwards, the dispersion curves, extracted from each cell of the 2D group velocity maps, were inverted as a function of depth to obtain a 3D shear wave velocity model of the upper crust, from the surface to a depth of 2.0 km. The obtained 3D velocity model reveals features throughout the island that correlates well with surface geology and island evolution. (C) 2015 Elsevier B.V. All rights reserved.

Upper crustal structure of Madeira Island revealed from ambient noise tomography

We present the first image of the Madeira upper crustal structure, using ambient seismic noise tomography. 16 months of ambient noise, recorded in a dense network of 26 seismometers deployed across Madeira, allowed reconstructing Rayleigh wave Green's functions between receivers. Dispersion analysis was performed in the short period band from 1.0 to 4.0 s. Group velocity measurements were regionalized to obtain 20 tomographic images, with a lateral resolution of 2.0 km in central Madeira. Afterwards, the dispersion curves, extracted from each cell of the 2D group velocity maps, were inverted as a function of depth to obtain a 3D shear wave velocity model of the upper crust, from the surface to a depth of 2.0 km. The obtained 3D velocity model reveals features throughout the island that correlates well with surface geology and island evolution. (C) 2015 Elsevier B.V. All rights reserved.

Soliton-type and other travelling wave solutions for an improved class of nonlinear sixth-order Boussinesq equations

An improved class of nonlinear bidirectional Boussinesq equations of sixth order using a wave surface elevation formulation is derived. Exact travelling wave solutions for the proposed class of nonlinear evolution equations are deduced. A new exact travelling wave solution is found which is the uniform limit of a geometric series. The ratio of this series is proportional to a classical soliton-type solution of the form of the square of a hyperbolic secant function. This happens for some values of the wave propagation velocity. However, there are other values of this velocity which display this new type of soliton, but the classical soliton structure vanishes in some regions of the domain. Exact solutions of the form of the square of the classical soliton are also deduced. In some cases, we find that the ratio between the amplitude of this wave and the amplitude of the classical soliton is equal to 35/36. It is shown that different families of travelling wave solutions are associated with different values of the parameters introduced in the improved equations.

Exploiting the bin-class histograms for feature selection on discrete data

In machine learning and pattern recognition tasks, the use of feature discretization techniques may have several advantages. The discretized features may hold enough information for the learning task at hand, while ignoring minor fluctuations that are irrelevant or harmful for that task. The discretized features have more compact representations that may yield both better accuracy and lower training time, as compared to the use of the original features. However, in many cases, mainly with medium and high-dimensional data, the large number of features usually implies that there is some redundancy among them. Thus, we may further apply feature selection (FS) techniques on the discrete data, keeping the most relevant features, while discarding the irrelevant and redundant ones. In this paper, we propose relevance and redundancy criteria for supervised feature selection techniques on discrete data. These criteria are applied to the bin-class histograms of the discrete features. The experimental results, on public benchmark data, show that the proposed criteria can achieve better accuracy than widely used relevance and redundancy criteria, such as mutual information and the Fisher ratio.

Generation of high-affinity monoclonal antibodies of IgG class against native β-d-glucans from basidiomycete mushrooms

β-d-glucans from basidiomycete strains are powerful immunomodulatory agents in several clinical conditions. Therefore, their assay, purification and characterization are of great interest to understand their structure-function relationship. Hybridoma cell fusion was used to raise monoclonal antibodies (Mabs) against extracellular β-d-glucans (EBGs) from Pleurotus ostreatus. Two of the hybridoma clones (1E6-1E8-B5 and 3E8-3B4) secreting Mabs against EBGs were selected. This hybridoma cell line secreted Mabs of the IgG class which were then purified by hydroxyapatite chromatography to apparent homogeneity on native and SDS-PAGE. Mabs secreted by 1E6-1E8-B5 clone were found to recognize a common epitope on several β-d-glucans from different basidiomycete strains. This Mab exhibited high affinity constant (KA) for β-d-glucans from several mushroom strains in the range of 3.20 × 109 ± 3.32 × 103-1.51 × 1013 ± 3.58 × 107 L/mol. Moreover, they reacted to some heat-treated β-d-glucans in a different mode when compared with the native forms; these data suggest that this Mab binds to a conformational epitope on the β-d-glucan molecule. The epitope-binding studies of Mabs obtained from 1E6-1E8-B5 and 3E8-3B4 revealed that the Mabs bind to the same epitope on some β-d-glucans and to different epitopes in other antigen molecules. Therefore, these Mabs can be used to assay for β-d-glucan from basidiomycete mushrooms. © 2015 Elsevier Ltd. All rights reserved.