High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Protein-polysaccharide viscoelastic matrices: synergic effects of amylose on lysozyme physical gelation in aqueous dimethylsulfoxide

A synergic effect of amylose on rheological characteristics of lysozyme physical gels evolved out of dimethylsulfoxide-water was verified and analyzed. The dynamics of the gels were experimentally approached by oscillatory rheology. The synergic effect was characterized by a decrease in the threshold DMSO volume fraction required for lysozyme gelation, and by a significant strengthening of the gel structure at over-critical solvent and protein concentrations. Drastic changes in the relaxation and creep curve patterns for systems in the presence of amylose were verified. Complex viscosity dependence on temperature was found to conform to an Arrhenius-like equation, allowing the determination of an activation energy term (Ea, apparent) for discrimination of gel rigidity. A dilatant effect was found to be induced by temperature on the flow behavior of lysozyme dispersions in DMSO-H(2)O in sub-critical conditions for gelation, which was greatly intensified by the presence of amylose in the samples. That transition was interpreted as reflecting a change from a predominant colloidal flow regime, where globular components are the prevailing structural elements, to a mainly fibrillar, polymeric flow behavior.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Understanding the Influences of Spatial Patterns on N Availability Within the Brazilian Amazon Forest

Nitrogen variations at different spatial scales and integrated across functional groups were addressed for lowland tropical forests in the Brazilian Amazon as follows: (1) how does N availability vary across the region over different spatial scales (regional x landscape scale); ( 2) how are these variations in N availability integrated across plant functional groups ( legume 9 non-legume trees). Leaf N, P, and Ca concentrations as well the leaf N isotope ratios (delta(15)N) from a large set of legume and non-legume tree species were measured. Legumes had higher foliar N/Ca ratios than non-legumes, consistent with the high energetic costs in plant growth associated with higher foliar P/Ca ratios found in legumes than in non-legumes. At the regional level, foliar delta(15)N decreased with increasing rainfall. At the landscape level, N availability was higher in the forests on clayey soils on the plateau than in forests on sandier soils. The isotope as well as the non-isotope data relationships here documented, explain to a large extent the variation in delta(15)N signatures across gradients of rainfall and soil. Although at the regional level, the precipitation regime is a major determinant of differences in N availability, at the landscape level, under the same precipitation regime, soil type seems to be a major factor influencing the availability of N in the Brazilian Amazon forest.

Evidences of turbulent mixing in multi-pumping flow systems

Multi-pumping flow systems exploit pulsed flows delivered by Solenoid pumps. Their improved performance rely on the enhanced radial mass transport inherent to the pulsed flow, which is a consequence of the establishment of vortices thus a tendency towards turbulent mixing. This paper presents several evidences of turbulent mixing in relation to pulsed flows. such as recorded peak shape, establishment of fluidized beds, exploitation of flow reversal, implementation of relatively slow chemical reactions and/or heating of the reaction medium. In addition, Reynolds number associated with the GO period of a pulsed flow is estimated and photographic images of dispersing samples flowing under laminar regime and pulsed flow conditions are presented. (C) 2009 Elsevier B.V. All rights reserved.

Multifractal regime transition in a modified minority game model

The search for more realistic modeling of financial time series reveals several stylized facts of real markets. In this work we focus on the multifractal properties found in price and index signals. Although the usual minority game (MG) models do not exhibit multifractality, we study here one of its variants that does. We show that the nonsynchronous MG models in the nonergodic phase is multifractal and in this sense, together with other stylized facts, constitute a better modeling tool. Using the structure function (SF) approach we detected the stationary and the scaling range of the time series generated by the MG model and, from the linear (non-linear) behavior of the SF we identified the fractal (multifractal) regimes. Finally, using the wavelet transform modulus maxima (WTMM) technique we obtained its multifractal spectrum width for different dynamical regimes. (C) 2009 Elsevier Ltd. All rights reserved.

TOPOGRAPHIC REGISTERS OF PALEO-VALLEYS ON THE SOUTHEASTERN BRAZILIAN CONTINENTAL SHELF

The evolution of paleo-incised-valleys in the Sao Paulo State region of the southeastern Brazilian continental shelf is presented in this study in relation to the post Last Glacial Maximum (LGM) sea-level rises based on the submarine topography modeled by a detailed Digital Elevation Model and evidences noted in high resolution seismic profiles. The hypothesis that has guided this study is that the set of paleo-valley characteristics (i.e. the fluvial parameters of modern coastal drainage systems, the topographical shape and dimensions of the valleys and of the subsurface channels) may indicate aspects of the relation between the influence of the fluvial and the eustatic variation regime in geomorphological-stratigraphic registers. Models described in the literature sustain the view that faster marine transgressions tend to increase erosion in estuaries, which may explain the lack of registers of paleo-drainage both in topography and the sub-surface in areas with wider shelves. On the other hand, on narrower shelves, with a higher slope angle, the transgression process can preserve, or even enhance, the incised valley registers during shoreface retreat. In the area studied, we observed that the dimensions and form of the continental shelf varies from the northern to the southern part of the area, affecting aspects of the geomorphological registers of the submerged incised valleys.

Political Systems and the Perspective on Nursing Education during the Spanish Transition (from the Franco Regime to Democracy). A Contribution based on Nursing History

The aim of this study is to describe the changes in nursing education during the process prior to and after the establishment of democracy in Spain. It begins with the hypothesis that differences in social and political organization influenced the way the system of nursing education evolved, keeping it in line with neopositivistic schemes and exclusively technical approaches up until the advent of democracy. The evolution of a specific profile for nursing within the educational system has been shaped by the relationship between the systems of social and political organization in Spain. To examine the insertion of subjects such as the anthropology of healthcare into education programs for Spanish nursing, one must consider the cultural, intercultural and transcultural factors that are key to understanding the changes in nursing education that allowed for the adoption of a holistic approach in the curricula. Until the arrival of democracy in 1977, Spanish nursing education was solely technical in nature and the role of nurses was limited to the tasks and procedures defined by the bureaucratic thinking characteristic of the rational-technological paradigm. Consequently, during the long period prior to democracy, nursing in Spain was under the influence of neopositivistic and technical thinking, which had its effect on educational curricula. The addition of humanities and anthropology to the curricula, which facilitated a holistic approach, occurred once nursing became a field of study at the university level in 1977, a period that coincided with the beginnings of democracy in Spain.

Annealing effects on microstructure and coercive field of ferritic-martensitic ODS Eurofer steel

Oxide dispersion strengthened reduced-activation ferritic-martensitic steels are promising candidates for applications in future fusion power plants. Samples of a reduced activation ferritic-martensitic 9 wt.%Cr-oxide dispersion strengthened Eurofer steel were cold rolled to 80% reduction in thickness and annealed in vacuum for 1 h from 200 to 1350 degrees C to evaluate its thermal stability. Vickers microhardness testing and electron backscatter diffraction (EBSD) were used to characterize the microstructure. The microstructural changes were also followed by magnetic measurements, in particular the corresponding variation of the coercive field (H(c)), as a function of the annealing treatment. Results show that magnetic measurements were sensitive to detect the changes, in particular the martensitic transformation, in samples annealed above 850 degrees C (austenitic regime). (C) 2010 Elsevier B.V. All rights reserved.

Analysis of the E-J Curve of HTS Tapes Under DC and AC Magnetic Fields at 77 K

The evaluation of the electrical characteristics of technical HTS tapes are of the key importance in determining the design and operational features of superconducting power apparatuses as well as to understand the external factors which affect the superconducting performance. In this work we report the systematic measurements of the electric field versus current density, E-J relation of short samples for three commercial HTS tapes (BSCCO-2223 tapes, with and without steel reinforcement, and YBCO-coated conductor) at 77 K. In order to get sensitive and noiseless voltage signals the measurements were carried out with DC transport current and subjecting the broad surface tape to DC (0-300 mT) and AC (0-62 mT, 60 Hz) magnetic fields. The voltage is measured by a sensitive nanovoltmeter and the applied magnetic field is monitored by a Hall sensor placed on the tape broad surface. The comparison between the results obtained from the three tapes was done by fitting a power-law equation for currents in the vicinity of the critical current. For the current regime below the critical one a linear correlation of the electric field against the current density is observed. The BSCCO samples presented the same behavior, i.e., a decreasing of n-index with the increasing DC and AC magnetic field strength. Under AC field the decreasing slope of n-index is steeper as compared to DC field. The n-index curve for the YBCO tape showed similar behavior for AC field, however under DC field in the 0-390 mT range exhibited a slight decreasing of the n-index.

On the accuracy of two-fluid model predictions for a particular gas-solid riser flow

Literature presents a huge number of different simulations of gas-solid flows in risers applying two-fluid modeling. In spite of that, the related quantitative accuracy issue remains mostly untouched. This state of affairs seems to be mainly a consequence of modeling shortcomings, notably regarding the lack of realistic closures. In this article predictions from a two-fluid model are compared to other published two-fluid model predictions applying the same Closures, and to experimental data. A particular matter of concern is whether the predictions are generated or not inside the statistical steady state regime that characterizes the riser flows. The present simulation was performed inside the statistical steady state regime. Time-averaged results are presented for different time-averaging intervals of 5, 10, 15 and 20 s inside the statistical steady state regime. The independence of the averaged results regarding the time-averaging interval is addressed and the results averaged over the intervals of 10 and 20 s are compared to both experiment and other two-fluid predictions. It is concluded that the two-fluid model used is still very crude, and cannot provide quantitative accurate results, at least for the particular case that was considered. (C) 2009 Elsevier Inc. All rights reserved.

Buckling and post-buckling of extensible rods revisited: A multiple-scale solution

An exact non-linear formulation of the equilibrium of elastic prismatic rods subjected to compression and planar bending is presented, electing as primary displacement variable the cross-section rotations and taking into account the axis extensibility. Such a formulation proves to be sufficiently general to encompass any boundary condition. The evaluation of critical loads for the five classical Euler buckling cases is pursued, allowing for the assessment of the axis extensibility effect. From the quantitative viewpoint, it is seen that such an influence is negligible for very slender bars, but it dramatically increases as the slenderness ratio decreases. From the qualitative viewpoint, its effect is that there are not infinite critical loads, as foreseen by the classical inextensible theory. The method of multiple (spatial) scales is used to survey the post-buckling regime for the five classical Euler buckling cases, with remarkable success, since very small deviations were observed with respect to results obtained via numerical integration of the exact equation of equilibrium, even when loads much higher than the critical ones were considered. Although known beforehand that such classical Euler buckling cases are imperfection insensitive, the effect of load offsets were also looked at, thus showing that the formulation is sufficiently general to accommodate this sort of analysis. (c) 2008 Elsevier Ltd. All rights reserved.

Modeling and simulation of severe slugging in air-water pipeline-riser systems

A mathematical model, numerical simulations and stability and flow regime maps corresponding to severe slugging in pipeline riser systems, are presented. In the simulations air and water were used as flowing fluids. The mathematical model considers continuity equations for liquid and gas phases, with a simplified momentum equation for the mixture, neglecting inertia. A drift-flux model, evaluated for the local conditions in the riser, is used as a closure law. The developed model predicts the location of the liquid accumulation front in the pipeline and the liquid level in the riser, so it is possible to determine which type of severe slugging occurs in the system. The numerical procedure is convergent for different nodalizations. A comparison is made with experimental results corresponding to a catenary riser, showing very good results for slugging cycle and stability and flow regime maps. (c) 2010 Elsevier Ltd. All rights reserved.

Mild and severe wear of steels and cast irons in sliding abrasion

This paper presents the results obtained in pin-on-disk test apparatus using glass and alumina as abrasive materials, showing the rates and mechanisms of abrasive wear of 1070 and 52100 steels, and ductile and white cast irons. The test conditions were selected in order to obtain wear rates that correspond to mild and severe abrasion, using different metal hardness-to-abrasive hardness ratios(H/H(A)) and 0.2 or 0.06 mm abrasive grains. The use of bulk Vickers hardness, instead of microhardness, allows a better description of the different abrasion regions. Under severe abrasion, the microcutting mechanism of wear prevailed together with friction coefficients larger than 0.4. On the other hand, when relatively soft abrasives are tested, indentation of abrasive particles followed by its fragmentation, and a creation of a thin deformed layer were the main damage mechanisms, with the friction coefficient lying below 0.4. The abrasive particle size under mild regime is able to change the wear rates in an order of magnitude. (C) 2009 Elsevier B.V. All rights reserved.

Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.