Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Energy absorbed by electronic body protectors from kicks in a taekwondo competition

Objective: Although some scientific information on electronic body protectors in taekwondo is available, no research has been done to assess the impact of kicks in a competitive situation. The purpose of this study, then, was to assess the energy absorbed by these protectors from kicks performed in an actual taekwondo competition. Methods: Subjects consisted of junior (14-17 years) and senior (>= 18 years) male taekwondo-in, who participated in an open tournament. Data on the energy imparted by valid kicks in Joules (1) were collected from a public visual electronic monitor. Results: Energy was higher for the seniors: 264.31 +/- 56.63 J versus 224.38 +/- 48.23 J for the juniors (eta(2) = 0.121). The seniors scored lower in percent impact but the effect was trivial: 123.46 +/- 24.77% versus 136.70 +/- 26.33% (eta(2) = 0.087). Conclusions: The difference between senior and junior taekwondo-in in absolute energy generated was small, while the difference in relative energy impact was trivial in favour of the junior taekwondo athletes.

Electronic properties and hyperfine fields of nickel-related complexes in diamond

We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.

ELECTRONIC GOVERNMENT POLICIES IN BRAZIL: CONTEXT, ICT MANAGEMENT AND OUTCOMES

The State Reform processes combined with the emergence and use of Information and Communication Technology (ICT) originated electronic government policies and initiatives in Brazil. This paper dwells on Brazilian e-government by investigating the institutional design it assumed in the state's public sphere, and how it contributed to outcomes related to e-gov possibilities. The analyses were carried out under an interpretativist perspective by making use of Institutional Theory. From the analyses of interviews with relevant actors in the public sphere, such as state secretaries and presidents of public ICT companies, conclusions point towards low institutionalization of e-gov policies. The institutional design of Brazilian e-gov limits the use of ICT to provide integrated public services, to amplify participation and transparency, and to improve public policies management.

Electrochemical Evidence of Strong Electronic Interaction of PtRu on Carbon Nanotubes with High Density of Defects

We show that carbon nanotubes (CNTs) with high density of defects can present a strong electronic interaction with nanoparticles of Pt-Ru with average particle size of 3.5 +/- 0.8 nm. Depending on the Pt-Ru loading on the CNTs, CO and methanol oxidation reactions suggest there is a charge transfer between Pt-Ru that in turn provokes a decrease in the electronic interaction taking place between Ru and Pt in the PtRu alloy. The CO stripping potentials were observed at about 0.65 and 0.5 V for Pt-Ru/CNT electrodes with Pt-Ru loadings of 10 and 20, and 30 wt %, respectively. (C) 2008 The Electrochemical Society. [DOI: 10.1149/1.2990222] All rights reserved.

Clinical outcomes of long-acting injectable risperidone in patients with schizophrenia: six-month follow-up from the Electronic Schizophrenia Treatment Adherence Registry in Latin America

Background: Risperidone long-acting injection (RLAI) has been shown to be efficacious, improve compliance, and increase long-term retention rate on therapy. The aim of this work was to determine the effect of RLAI on clinical outcome and hospitalization rate in patients with schizophrenia or schizoaffective disorder enrolled in the electronic Schizophrenia Treatment Adherence Registry in Latin America. Methods: Data were collected at baseline, retrospectively for the 12 months prior to baseline, and prospectively every three months for 24 months. Hospitalization prior to therapy was assessed by a retrospective chart review. Efficacy and functioning were evaluated using Clinical Global Impression of Illness Severity (CGI-S), Personal and Social Performance (PSP), and Global Assessment of Functioning (GAF) scores. Relapse and treatment were also registered. Results: Patients were recruited in Mexico (n = 53), Brazil (n = 11), and Colombia (n = 15). Sixty-five percent (n = 52) were male, and mean age was 32.9 years. Patients were classified as having schizophrenia (n = 73) or schizoaffective disorder (n = 6). The mean dose of RLAI at six months was 34.1 mg (standard deviation = 10.2 mg). The percentage of hospitalized patients before treatment was 28.2% and 5.1% at six months after initiating RLAI (P < 0.001). Significant changes were registered on CGI-S, GAF, and PSP scores. Conclusions: RLAI was associated with an improvement in clinical symptoms and functioning, and a greater reduction in hospitalization.

Transverse momentum dependence of J/psi polarization at midrapidity in p plus p collisions at root s=200 GeV

We report the measurement of the transverse momentum dependence of inclusive J/psi polarization in p + p collisions at root s = 200 GeV performed by the PHENIX Experiment at the Relativistic Heavy Ion Collider. The J/psi polarization is studied in the helicity, Gottfried-Jackson, and Collins-Soper frames for p(T) < 5 GeV/c and vertical bar y vertical bar < 0.35. The polarization in the helicity and Gottfried-Jackson frames is consistent with zero for all transverse momenta, with a slight (1.8 sigma) trend towards longitudinal polarization for transverse momenta above 2 GeV/c. No conclusion is allowed due to the limited acceptance in the Collins-Soper frame and the uncertainties of the current data. The results are compared to observations for other collision systems and center of mass energies and to different quarkonia production models.

The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7 +/- 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm. (C) 2008 American Institute of Physics.

Continuum-continuum coupling and polarization potentials for weakly bound systems

We investigate the influence of couplings among continuum states in collisions of weakly bound nuclei. For this purpose, we compare cross sections for complete fusion, breakup, and elastic scattering evaluated by continuum discretized coupled channel (CDCC) calculations, including and not including these couplings. In our study, we discuss this influence in terms of the polarization potentials that reproduces the elastic wave function of the coupled channel method in single channel calculations. We find that the inclusion of couplings among continuum states renders the real part of the polarization potential more repulsive, whereas it leads to weaker absorption to the breakup channel. We show that the noninclusion of continuum-continuum couplings in CDCC calculations may lead to qualitative and quantitative wrong conclusions.

Local approximations for polarization potentials

We discuss the derivation of an equivalent polarization potential independent of angular momentum l for use in the optical Schrodinger equation that describes the elastic scattering of heavy ions. Three different methods are used for this purpose. Application of our theory to the low energy scattering of light heavy-ion systems at near-barrier energies is made. It is found that the notion of an l-independent polarization potential has some validity but cannot be a good substitute for the l-dependent local equivalent Feshbach polarization potential.

Evidence for zero-differential resistance states in electronic bilayers

We observe zero-differential resistance states at low temperatures and moderate direct currents in a bilayer electron system formed by a wide quantum well. Several regions of vanishing resistance evolve from the inverted peaks of magneto-intersubband oscillations as the current increases. The experiment, supported by a theoretical analysis, suggests that the origin of this phenomenon is based on instability of homogeneous current flow under conditions of negative differential resistivity, which leads to formation of current domains in our sample, similar to the case of single-layer systems.

Optical third-harmonic spectroscopy of the magnetic semiconductor EuTe

EuTe possesses the centrosymmetric crystal structure m3m of rocksalt type in which the second-harmonic generation is forbidden in electric dipole approximation but the third-harmonic generation (THG) is allowed. We studied the THG spectra of this material and observed several resonances in the vicinity of the band gap at 2.2-2.5 eV and at higher energies up to 4 eV, which are related to four-photon THG processes. The observed resonances are assigned to specific combinations of electronic transitions between the ground 4f(7) state at the top of the valence band and excited 4f(6)5d(1) states of Eu(2+) ions, which form the lowest energy conduction band. Temperature, magnetic field, and rotational anisotropy studies allowed us to distinguish crystallographic and magnetic-field-induced contributions to the THG. A strong modification of THG intensity for the 2.4 eV band and suppression of the THG for the 3.15 eV band was observed in applied magnetic field. Two main features of the THG spectra were assigned to 5d(t(2g)) and 5d(e(g)) subbands at 2.4 eV and 3.15 eV, respectively. A microscopic quantum-mechanical model of the THG response was developed and its conclusions are in qualitative agreement with the experimental results.

Optical second harmonic generation in the centrosymmetric magnetic semiconductors EuTe and EuSe

The magnetic europium chalcogenide semiconductors EuTe and EuSe are investigated by the spectroscopy of second harmonic generation (SHG) in the vicinity of the optical band gap formed by transitions involving the 4f and 5d electronic orbitals of the magnetic Eu(2+) ions. In these materials with centrosymmetric crystal lattice the electric-dipole SHG process is symmetry forbidden so that no signal is observed in zero magnetic field. Signal appears, however, in applied magnetic field with the SHG intensity being proportional to the square of magnetization. The magnetic field and temperature dependencies of the induced SHG allow us to introduce a type of nonlinear optical susceptibility determined by the magnetic-dipole contribution in combination with a spontaneous or induced magnetization. The experimental results can be described qualitatively by a phenomenological model based on a symmetry analysis and are in good quantitative agreement with microscopic model calculations accounting for details of the electronic energy and spin structure.

Unraveling effects of disorder on the electronic structure of SiO(2) from first principles

We present a first-principles systematic study of the electronic structure of SiO(2) including the crystalline polymorphs alpha quartz and beta cristobalite, and different types of disorder leading to the amorphous phase. We start from calculations within density functional theory and proceed to more sophisticated quasiparticle calculations according to the GW scheme. Our results show that different origins of disorder have also different impact on atomic and electronic-density fluctuations, which affect the electronic structure and, in particular, the size of the mobility gap in each case.

Spin filtering and disorder-induced magnetoresistance in carbon nanotubes: Ab initio calculations

Nitrogen-doped carbon nanotubes can provide reactive sites on the porphyrin-like defects. It is well known that many porphyrins have transition-metal atoms, and we have explored transition-metal atoms bonded to those porphyrin-like defects inN-doped carbon nanotubes. The electronic structure and transport are analyzed by means of a combination of density functional theory and recursive Green's function methods. The results determined the heme B-like defect (an iron atom bonded to four nitrogens) is the most stable and has a higher polarization current for a single defect. With randomly positioned heme B defects in nanotubes a few hundred nanometers long, the polarization reaches near 100%, meaning they are effective spin filters. A disorder-induced magnetoresistance effect is also observed in those long nanotubes, and values as high as 20 000% are calculated with nonmagnectic eletrodes.