Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

Internal structure of the nanogratings generated inside bulk fused sílica by ultrafast laser direct writing

The aim of the present work was to characterize the internal structure of nanogratings generated inside bulk fused silica by ultrafast laser processing and to study the influence of diluted hydrofluoric acid etching on their structure. The nanogratings were inscribed at a depth of 100 mu m within fused silica wafers by a direct writing method, using 1030 nm radiation wavelength and the following processing parameters: E = 5 mu J, tau = 560 fs, f = 10 kHz, and v = 100 mu m/s. The results achieved show that the laser-affected regions are elongated ellipsoids with a typical major diameter of about 30 mu m and a minor diameter of about 6 mu m. The nanogratings within these regions are composed of alternating nanoplanes of damaged and undamaged material, with an average periodicity of 351 +/- 21 nm. The damaged nanoplanes contain nanopores randomly dispersed in a material containing a large density of defects. These nanopores present a roughly bimodal size distribution with average dimensions for each class of pores 65 +/- 20 x 16 +/- 8 x 69 +/- 16 nm(3) and 367 +/- 239 x 16 +/- 8 x 360 +/- 194 nm(3), respectively. The number and size of the nanopores increases drastically when an hydrofluoric acid treatment is performed, leading to the coalescence of these voids into large planar discontinuities parallel to the nanoplanes. The preferential etching of the damaged material by the hydrofluoric acid solution, which is responsible for the pores growth and coalescence, confirms its high defect density. (C) 2014 AIP Publishing LLC.

Molecular mobility, composition and structure analysis in glycerol plasticised chitosan films

This study was developed with the purpose to investigate the effect of polysaccharide/plasticiser concentration on the microstructure and molecular dynamics of polymeric film systems, using transmission electron microscope imaging (TEM) and nuclear magnetic resonance (NMR) techniques. Experiments were carried out in chitosan/glycerol films prepared with solutions of different composition. The films obtained after drying and equilibration were characterised in terms of composition, thickness and water activity. Results show that glycerol quantities used in film forming solutions were responsible for films composition; while polymer/total plasticiser ratio in the solution determined the thickness (and thus structure) of the films. These results were confirmed by TEM. NMR allowed understanding the films molecular rearrangement. Two different behaviours for the two components analysed, water and glycerol were observed: the first is predominantly moving free in the matrix, while glycerol is mainly bounded to the chitosan chain. (C) 2013 Elsevier Ltd. All rights reserved.

Algebraic structure for the crossing of balanced and stair nested designs

Stair nesting allows us to work with fewer observations than the most usual form of nesting, the balanced nesting. In the case of stair nesting the amount of information for the different factors is more evenly distributed. This new design leads to greater economy, because we can work with fewer observations. In this work we present the algebraic structure of the cross of balanced nested and stair nested designs, using binary operations on commutative Jordan algebras. This new cross requires fewer observations than the usual cross balanced nested designs and it is easy to carry out inference.

Fabrication of the three-dimensional dendritic Ni-Co films by electrodeposition on stainless steel substrates

Co-deposition of nickel and cobalt was carried out on austenitic stainless steel (AISI 304) substrates by imposing a square waveform current in the cathodic region. The innovative procedure applied in this work allows creating a stable, fully developed, and open porous three-dimensional (3D) dendritic structure, which can be used as electrode for redox supercapacitors. This study investigates in detail the influence of the applied current density on the morphology, mass, and chemical composition of the deposited Ni-Co films and the resulting 3D porous network dendritic structure. The morphology and the physicochemical composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (W). The electrochemical behavior of the materials was evaluated by cyclic voltammetry (CV). The results highlight the mechanism involved in the coelectrodeposition process and how the lower limit current density tailors the film composition and morphology, as well as its electrochemical activity.

Constrains on the structure of Maio Island (Cape Verde) by a three-dimensional gravity model: Imaging partially exhumed magma chambers

We propose a 3-D gravity model for the volcanic structure of the island of Maio (Cape Verde archipelago) with the objective of solving some open questions concerning the geometry and depth of the intrusive Central Igneous Complex. A gravity survey was made covering almost the entire surface of the island. The gravity data was inverted through a non-linear 3-D approach which provided a model constructed in a random growth process. The residual Bouguer gravity field shows a single positive anomaly presenting an elliptic shape with a NWSE trending long axis. This Bouguer gravity anomaly is slightly off-centred with the island but its outline is concordant with the surface exposure of the Central Igneous Complex. The gravimetric modelling shows a high-density volume whose centre of mass is about 4500 m deep. With increasing depth, and despite the restricted gravimetric resolution, the horizontal sections of the model suggest the presence of two distinct bodies, whose relative position accounts for the elongated shape of the high positive Bouguer gravity anomaly. These bodies are interpreted as magma chambers whose coeval volcanic counterparts are no longer preserved. The orientation defined by the two bodies is similar to that of other structures known in the southern group of the Cape Verde islands, thus suggesting a possible structural control constraining the location of the plutonic intrusions.

Deep structure of crust and mantle beneath Iberia and Western Mediterranean from P and S Receiver functions and SKS Waveforms

We have conducted a P and S receiver functions [PRFs and SRFs] analysis for 19 seismic stations on the Iberia and western Mediterranean. In the transition zone [TZ] the PRFs analysis reveals a band [from Gibraltar to Balearic] increased by 10-20 km relative to the standard 250 km. The TZ thickness variations are strongly correlated with the P660s times in PRFs. We interpret the variable depth of the 660-km discontinuity as an effect of subduction. Over the anomalous TZ we found a reduced velocity zone in the upper mantle. Joint inversion of PRFs and SRFs reveals a subcrustal high S velocity lid and an underlying LVZ. A reduction of the S velocity in the LVZ is less than 10%. The Gutenberg discontinuity is located at 65±5 km, but in several models sampling the Mediterranean, the lid is missing or its thickness is reduced to ~30 km. In the Gibraltar and North Africa this boundary is located at ~100 km. The lid Vp/Vs beneath Betics is reduced relative to the standard 1.8. Another evidence of the Vp/Vs anomaly is provided by S410p phase late arrivals in the SRFs. The azimuthal anisotropy analysis with a new technology was conducted at 5 stations and at 2 groups of stations. The fast direction in the uppermost mantle layer is ~90º in Iberian Massif. In Balearic is in the azimuth of ~120º. At a depth of ~60 km the direction becomes 90º. Anisotropy in the upper layer can be interpreted as frozen, whereas anisotropy in the lower layer is active, corresponding to the present-day or recent flow. The effect of the asthenosphere in the SKS splitting is much larger than the effect of the subcrustal lithosphere.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - I. Gulf of Lion's margin

The conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) represents a unique natural laboratory for addressing fundamental questions about rifting due to its landlocked situation, its youth, its thick sedimentary layers, including prominent palaeo-marker such as the MSC event, and the amount of available data and multidisciplinary studies. The main goals of the SARDINIA experiment, were to (i) investigate the deep structure of the entire system within the two conjugate margins: the Gulf of Lion and West Sardinia, (ii) characterize the nature of the crust, and (iii) define the geometry of the basin and provide important constrains on its genesis. This paper presents the results of P-wave velocity modelling on three coincident near-vertical reflection multi-channel seismic (MCS) and wide-angle seismic profiles acquired in the Gulf of Lion, to a depth of 35 km. A companion paper [part II Afilhado et al., 2015] addresses the results of two other SARDINIA profiles located on the oriental conjugate West Sardinian margin. Forward wide-angle modelling of both data sets confirms that the margin is characterised by three distinct domains following the onshore unthinned, 33 km-thick continental crust domain: Domain I is bounded by two necking zones, where the crust thins respectively from 30 to 20 and from 20 to 7 km over a width of about 170 km; the outermost necking is imprinted by the well-known T-reflector at its crustal base; Domain II is characterised by a 7 km-thick crust with anomalous velocities ranging from 6 to 7.5 km/s; it represents the transition between the thinned continental crust (Domain I) and a very thin (only 4-5 km) "atypical" oceanic crust (Domain III). In Domain II, the hypothesis of the presence of exhumed mantle is falsified by our results: this domain may likely consist of a thin exhumed lower continental crust overlying a heterogeneous, intruded lower layer. Moreover, despite the difference in their magnetic signatures, Domains II and III present the very similar seismic velocities profiles, and we discuss the possibility of a connection between these two different domains.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - II. Sardinia's margin

Geophysical data acquired on the conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) is unique in its ability to address fundamental questions about rifting (i.e. crustal thinning, the nature of the continent-ocean transition zone, the style of rifting and subsequent evolution, and the connection between deep and surface processes). While the Gulf of Lion (GoL) was the site of several deep seismic experiments, which occurred before the SARDINIA Experiment (ESP and ECORS Experiments in 1981 and 1988 respectively), the crustal structure of the West Sardinia margin remains unknown. This paper describes the first modeling of wide-angle and near-vertical reflection multi-channel seismic (MCS) profiles crossing the West Sardinia margin, in the Mediterranean Sea. The profiles were acquired, together with the exact conjugate of the profiles crossing the GoL, during the SARDINIA experiment in December 2006 with the French R/V L'Atalante. Forward wide-angle modeling of both data sets (wide-angle and multi-channel seismic) confirms that the margin is characterized by three distinct domains following the onshore unthinned, 26 km-thick continental crust : Domain V, where the crust thins from 26 to 6 km in a width of about 75 km; Domain IV where the basement is characterized by high velocity gradients and lower crustal seismic velocities from 6.8 to 7.25 km/s, which are atypical for either crustal or upper mantle material, and Domain III composed of "atypical" oceanic crust.The structure observed on the West Sardinian margin presents a distribution of seismic velocities that is symmetrical with those observed on the Gulf of Lion's side, except for the dimension of each domain and with respect to the initiation of seafloor spreading. This result does not support the hypothesis of simple shear mechanism operating along a lithospheric detachment during the formation of the Liguro-Provencal basin.

Deep structure of the Santos basin-São Paulo plateau system, SE Brazil

The structure and nature of the crust underlying the Santos Basin-São Paulo Plateau System (SSPS), in the SE Brazilian margin, are discussed based on five wide-angle seismic profiles acquired during the Santos Basin (SanBa) experiment in 2011. Velocity models allow us to precisely divide the SSPS in six domains from unthinned continental crust (Domain CC) to normal oceanic crust (Domain OC). A seventh domain (Domain D), a triangular shape region in the SE of the SSPS, is discussed by Klingelhoefer et al. (2014). Beneath the continental shelf, a similar to 100km wide necking zone (Domain N) is imaged where the continental crust thins abruptly from similar to 40km to less than 15km. Toward the ocean, most of the SSPS (Domains A and C) shows velocity ranges, velocity gradients, and a Moho interface characteristic of the thinned continental crust. The central domain (Domain B) has, however, a very heterogeneous structure. While its southwestern part still exhibits extremely thinned (7km) continental crust, its northeastern part depicts a 2-4km thick upper layer (6.0-6.5km/s) overlying an anomalous velocity layer (7.0-7.8km/s) and no evidence of a Moho interface. This structure is interpreted as atypical oceanic crust, exhumed lower crust, or upper continental crust intruded by mafic material, overlying either altered mantle in the first two cases or intruded lower continental crust in the last case. The deep structure and v-shaped segmentation of the SSPS confirm that an initial episode of rifting occurred there obliquely to the general opening direction of the South Atlantic Central Segment.

Performance assessment of a wind energy conversion system using a hierarchical controller structure

This paper deals with a hierarchical structure composed by an event-based supervisor in a higher level and two distinct proportional integral (PI) controllers in a lower level. The controllers are applied to a variable speed wind energy conversion system with doubly-fed induction generator, namely, the fuzzy PI control and the fractional-order PI control. The event-based supervisor analyses the operation state of the wind energy conversion system among four possible operational states: park, start-up, generating or brake and sends the operation state to the controllers in the lower level. In start-up state, the controllers only act on electric torque while pitch angle is equal to zero. In generating state, the controllers must act on the pitch angle of the blades in order to maintain the electric power around the nominal value, thus ensuring that the safety conditions required for integration in the electric grid are met. Comparisons between fuzzy PI and fractional-order PI pitch controllers applied to a wind turbine benchmark model are given and simulation results by Matlab/Simulink are shown. From the results regarding the closed loop point of view, fuzzy PI controller allows a smoother response at the expense of larger number of variations of the pitch angle, implying frequent switches between operational states. On the other hand fractional-order PI controller allows an oscillatory response with less control effort, reducing switches between operational states. (C) 2015 Elsevier Ltd. All rights reserved.

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.