Substrate specificity of the Chamaerops excelsa palm tree peroxidase. A steady-state kinetic study

The steady state kinetic mechanism of the H(2)O(2)-supported oxidation of different organic substrates by peroxidase from leaves of Chamaerops excelsa palm trees (CEP) has been investigated. An analysis of the initial rates vs. H(2)O(2) and reducing substrate concentrations is consistent with a substrate-inhibited Ping-Pong Bi Bi reaction mechanism. The phenomenological approach expresses the peroxidase Ping-Pong mechanism in the form of the Michaelis-Menten equation and leads to an interpretation of the effects in terms of the kinetic parameters K(m)(H2O2)center dot K(m)(AH2)center dot k(cat)center dot K(SI)(AH2) and of the microscopic rate constants k(1) and k(3) of the shared three-step catalytic cycle of peroxidases. (C) 2011 Elsevier B.V. All rights reserved.

Efficiency of extrinsic and intrinsic charge-carrier photogeneration processes obtained from the steady-state photocurrent action spectra of poly(p-phenylene vinylene) derivatives

The efficiency of the charge-carrier photogeneration processes in poly(2,5-bis(3',7'-dimethyl-octyloxy)-1,4-phenylene vinylene) (OC(1)OC10-PPV) has been analyzed by the spectral response of the photocurrent of devices in ITO/polymer/Al structures. The symbatic response of the photocurrent action spectra of the OC1OC10-PPV devices, obtained for light-excitation through the ITO electrode and for forward bias, has been fitted using a phenomenological model which considers that the predominant transport mechanism under external applied electric field is the drift of photogenerated charge-carriers, neglecting charge-carrier diffusion. The proposed model takes into account that charge-carrier photogeneration occurs via intermediate stages of bounded pairs (excitonic states), followed by dissociation processes. Such processes result in two different contributions to the photoconductivity: The first one, associated to direct creation of unbound polaron pairs due to intrinsic photoionization; and the second one is associated to secondary processes like extrinsic photoinjection at the metallic electrodes. The results obtained from the model have shown that the intrinsic component of the photoconductivity at higher excitation energies has a considerably higher efficiency than the extrinsic one, suggesting a dependence on the photon energy for the efficiency of the photogeneration process.

Oxygen reduction reaction catalyzed by epsilon-MnO2: Influence of the crystalline structure on the reaction mechanism

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

Electronic Properties of Water in Liquid Environment. A Sequential QM/MM Study Using the Free Energy Gradient Method

There is a continuous search for theoretical methods that are able to describe the effects of the liquid environment on molecular systems. Different methods emphasize different aspects, and the treatment of both the local and bulk properties is still a great challenge. In this work, the electronic properties of a water molecule in liquid environment is studied by performing a relaxation of the geometry and electronic distribution using the free energy gradient method. This is made using a series of steps in each of which we run a purely molecular mechanical (MM) Monte Carlo Metropolis simulation of liquid water and subsequently perform a quantum mechanical/molecular mechanical (QM/MM) calculation of the ensemble averages of the charge distribution, atomic forces, and second derivatives. The MP2/aug-cc-pV5Z level is used to describe the electronic properties of the QM water. B3LYP with specially designed basis functions are used for the magnetic properties. Very good agreement is found for the local properties of water, such as geometry, vibrational frequencies, dipole moment, dipole polarizability, chemical shift, and spin-spin coupling constants. The very good performance of the free energy method combined with a QM/MM approach along with the possible limitations are briefly discussed.

A regional multirnodulus algorithm for blind equalization of QAM signals: Introduction and steady-state analysis

It is well known that constant-modulus-based algorithms present a large mean-square error for high-order quadrature amplitude modulation (QAM) signals, which may damage the switching to decision-directed-based algorithms. In this paper, we introduce a regional multimodulus algorithm for blind equalization of QAM signals that performs similar to the supervised normalized least-mean-squares (NLMS) algorithm, independently of the QAM order. We find a theoretical relation between the coefficient vector of the proposed algorithm and the Wiener solution and also provide theoretical models for the steady-state excess mean-square error in a nonstationary environment. The proposed algorithm in conjunction with strategies to speed up its convergence and to avoid divergence can bypass the switching mechanism between the blind mode and the decision-directed mode. (c) 2012 Elsevier B.V. All rights reserved.

Equilibrium topology for plasmas with reversed current density.

Actually, transition from positive to negative plasma current and quasi-steady-state alternated current (AC) operation have been achieved experimentally without loss of ionization. The large transition times suggest the use of MHD equilibrium to model the intermediate magnetic field configurations for corresponding current density reversals. In the present work we show, by means of Maxwell equations, that the most robust equilibrium for any axisymmetric configuration with reversed current density requires the existence of several nonested families of magnetic surfaces inside the plasma. We also show that the currents inside the nonested families satisfy additive rules restricting the geometry and sizes of the axisymmetric magnetic islands; this is done without restricting the equilibrium through arbitrary functions. Finally, we introduce a local successive approximations method to describe the equilibrium about an arbitrary reversed current density minimum and, consequently, the transition between different nonested topologies is understood in terms of the eccentricity of the toroidal current density level sets.

Stoichiometry, structure, and transport in the quasi-one-dimensional metal Li0.9Mo6O17

A correlation between lattice parameters, oxygen composition, and the thermoelectric and Hall coefficients is presented for single-crystal Li0.9Mo6O17, a quasi-one-dimensional (Q1D) metallic compound. The possibility that this compound is a compensated metal is discussed in light of a substantial variability observed in the literature for these transport coefficients.

Prevalence of Arterial Hypertension Among Seventh-Day Adventists of the Sao Paulo State Capital and Inner Area

Background: Inadequate life habits are known to favor hypertension, and Adventists recommend healthy life habits. Objective: To assess the prevalence of hypertension among Seventh-Day Adventists from the inner Sao Paulo state and Sao Paulo state capital. Methods: This study assessed 264 Adventists (mean age, 41.17 +/- 15.27 years; women, 59.8%) with a high religiosity level assessed by use of the Duke University Religion Index. Blood pressure was measured with a validated automatic device. The significance level adopted was p < 0.05. Results: The total prevalence of hypertension was 22.7% (27.4% in the inner state and 15% in the capital). The Adventists from the capital differed from those of inner state as follows (p < 0.05), respectively: higher education (62% vs 36.6%); employed by a third party (44%) vs self-employed (40.9%); family income (8.39 +/- 6.20 vs 4.59 +/- 4.75 minimum wages); individual income (4.54 +/- 5.34 vs 6.35 +/- 48; couple responsible for family income (35% vs 39.6%); vegetarianism (11% vs 3%); blood pressure (115.38 +/- 16.52/68.74 +/- 8.94 vs 123.66 +/- 19.62/74.88 +/- 11.85 mmHg); white ethnicity (65% vs 81.1%); married (53% vs 68.9%); lower tangible support in the social aspect (15.7 +/- 5.41 vs 16.9 +/- 4.32); and recalling the last time one's blood pressure was measured (65% vs 48.8%). On multivariate analysis, hypertension associated with the following: 1) vegetarianism (OR 0.051; 95% CI: 0.004-0.681); 2) educational level (OR 5.317; 95% CI: 1.674-16.893); 3) recalling the last time one's blood pressure was measured (OR 2.725; 95% CI: 1.275-5.821); 4) being retired (OR 8.846; 95% CI: 1.406-55.668); and 5) being responsible for family income (OR 0.422; 95% CI: 0.189-0.942). Conclusion: The prevalence of hypertension among Adventists was lower as compared with that reported in Brazilian studies, and it was lower in the Sao Paulo state capital as compared with that in the inner Sao Paulo state, possibly because of the better socioeconomic conditions and life habits of the former. (Arq Bras Cardiol 2012; 98(4): 329-337)

Fast detection of the magnetic easy axis on steel sheet using the continuous rotational Barkhausen method

The magnetic behaviour of most commercial ferromagnetic steels is usually anisotropic presenting a magnetic easy axis. Changes in the direction of this axis can be related to mechanical changes and anomalies that occur in the fabrication process. The present work describes a method that uses a device with permanent magnets to create a precise rotational magnetic field. The device measures continuous Magnetic Barkhausen Noise signals related to the angle of magnetization, in order to determine the direction of the macroscopic magnetic easy axis. It also offers the possibility of obtaining real time parameters that quantify the magnetic anisotropy of the sample. (C) 2011 Elsevier Ltd. All rights reserved.

Analysis Methodology for Vortex-Induced Motion (VIM) of a Monocolumn Platform Applying the Hilbert-Huang Transform Method

Vortex-induced motion (VIM) is a highly nonlinear dynamic phenomenon. Usual spectral analysis methods, using the Fourier transform, rely on the hypotheses of linear and stationary dynamics. A method to treat nonstationary signals that emerge from nonlinear systems is denoted Hilbert-Huang transform (HHT) method. The development of an analysis methodology to study the VIM of a monocolumn production, storage, and offloading system using HHT is presented. The purposes of the present methodology are to improve the statistics analysis of VIM. The results showed to be comparable to results obtained from a traditional analysis (mean of the 10% highest peaks) particularly for the motions in the transverse direction, although the difference between the results from the traditional analysis for the motions in the in-line direction showed a difference of around 25%. The results from the HHT analysis are more reliable than the traditional ones, owing to the larger number of points to calculate the statistics characteristics. These results may be used to design risers and mooring lines, as well as to obtain VIM parameters to calibrate numerical predictions. [DOI: 10.1115/1.4003493]

Epidemiology of Brazilian spotted fever in the Atlantic Forest, state of Sao Paulo, Brazil

The tick-borne bacterium Rickettsia rickettsii is the aetiological agent of Brazilian spotted fever (BSF). The present study evaluated tick infestations on wild and domestic animals, and the rickettsial infection in these animals and their ticks in 7 forest areas adjacent to human communities in the Sao Paulo Metropolitan Area (SPMA). The results were compared to ecological traits of each sampled area. Two main tick species, Amblyomma aureolatum and Rhipicephalus sanguineus, were collected from dogs. The major ticks found on small mammals and birds were Ixodes loricatus and Amblyomma longirostre, respectively. Both anti-R. rickettsii antibodies and R. rickettsii-infected ticks were detected on dogs from only 2 areas in the southern part of the SPMA, which were considered to be endemic for BSF; the remaining 5 areas were considered to be non-endemic. Ecologically, the BSF-endemic areas clearly differed from the non-endemic areas by the presence of significantly more degraded forest patches in the former. The present results corroborate historical observations that have indicated that all human cases of BSF in the SPMA were contracted in the southern part of this metropolitan area. However, not all forest patches in the southern part of the SPMA were shown to be associated with BSF endemism.

Quantum deformation of the angular distributions of synchrotron radiation. Emission from particles in the first excited state

The exact expressions for the characteristics of synchrotron radiation of charged particles in the first excited state are obtained in analytical form using quantum theory methods. We performed a detailed analysis of the angular distribution structure of radiation power and its polarization for particles with spin 0 and 1/2. It is shown that the exact quantum calculations lead to results that differ substantially from the predictions of classical theory.

CIRCULATION AND SALT INTRUSION IN THE PIACAGUERA CHANNEL, SANTOS (SP)

Analysis of thermohaline properties and currents sampled at an anchor station in the Piacaguera Channel (Santos Estuary) in the austral winter was made in terms of tidal (neap and spring tidal cycles) and non-tidal conditions, with the objective to characterize the stratification, circulation and salt transport due to the fortnightly tidal modulation. Classical methods of observational data analysis of hourly and nearly synoptic observations and analytical simulations of nearly steady-state salinity and longitudinal velocity profiles were used. During the neap tidal cycle the flood (v<0) and ebb (v>0) velocities varied in the range of -0.20 m/s to 0.30 m/s associated with a small salinity variation from surface to bottom (26.4 psu to 30.7 psu). In the spring tidal cycle the velocities increased and varied in the range of -0.40 m/s to 0.45 m/s, but the salinity stratification remained almost unaltered. The steady-state salinity and velocity profiles simulated with an analytical model presented good agreement (Skill near 1.0), in comparison with the observational profiles. During the transitional fortnightly tidal modulation period there was no changes in the channel classification (type 2a - partially mixed and weakly stratified), because the potential energy rate was to low to enhance the halocline erosion. These results, associated with the high water column vertical stability (RiL > 20) and the low estuarine Richardson number (RiE = 1.6), lead to the conclusions: i) the driving mechanism for the estuary circulation and mixing was mainly balanced by the fresh water discharge and the tidal forcing associated with the baroclinic component of the gradient pressure force; ii) there was no changes in the thermohaline and circulation characteristics due to the forthnigtly tidal modulation; and iii) the nearly steady-state of the vertical salinity and velocity profiles were well simulated with a theoretical classical analytical model.

Bifurcation analysis of an aeroelastic system with concentrated nonlinearities

Analytical and numerical analyses of the nonlinear response of a three-degree-of-freedom nonlinear aeroelastic system are performed. Particularly, the effects of concentrated structural nonlinearities on the different motions are determined. The concentrated nonlinearities are introduced in the pitch, plunge, and flap springs by adding cubic stiffness in each of them. Quasi-steady approximation and the Duhamel formulation are used to model the aerodynamic loads. Using the quasi-steady approach, we derive the normal form of the Hopf bifurcation associated with the system's instability. Using the nonlinear form, three configurations including supercritical and subcritical aeroelastic systems are defined and analyzed numerically. The characteristics of these different configurations in terms of stability and motions are evaluated. The usefulness of the two aerodynamic formulations in the prediction of the different motions beyond the bifurcation is discussed.

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

In this communication, we investigate the effect of different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP-K40) on the growth process of zinc molybdate (beta-ZnMoO4) microcrystals synthesized under hydrothermal conditions at 140 degrees C for 8 h. These microcrystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) measurements. XRD patterns proved that these crystals are monophasic and present a wolframite-type monoclinic structure. FE-SEM images revealed that the surfactants modified the crystal shapes, suggesting the occurrence of distinct crystal growth processes. The CTAB cationic surfactant promotes the hindrance of small nuclei that leads to the formation of rectangle-like crystals, SDS anionic surfactant induces a growth of irregular hexagons with several porous due to considerable size effect of counter-ions on the crystal facets, PVP-K40 non-ionic surfactant allows a reduction in size and thickness of plate-like crystals, while without surfactants have the formation of irregular plate-like crystals. Finally, the PL properties of beta-ZnMoO4 microcrystals were explained by means of different shape/size, surface defects and order-disorder into lattice. (C) 2011 Elsevier B.V. All rights reserved.