A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

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.

Nonlinear optimization method for short-term hydro scheduling considering head-dependency

This paper is on the problem of short-term hydro scheduling, particularly concerning head-dependent reservoirs under competitive environment. We propose a new nonlinear optimization method to consider hydroelectric power generation as a function of water discharge and also of the head. Head-dependency is considered on short-term hydro scheduling in order to obtain more realistic and feasible results. The proposed method has been applied successfully to solve a case study based on one of the main Portuguese cascaded hydro systems, providing a higher profit at a negligible additional computation time in comparison with a linear optimization method that ignores head-dependency.

A method to analyse the alignment of core values in collaborative networked organisations

Since collaborative networked organisations are usually formed by independent and heterogeneous entities, it is natural that each member holds his own set of values, and that conflicts among partners might emerge because of some misalignment of values. In contrast, it is often stated in literature that the alignment between the value systems of members involved in collaborative processes is a prerequisite for successful co-working. As a result, the issue of core value alignment in collaborative networks started to attract attention. However, methods to analyse such alignment are lacking mainly because the concept of 'alignment' in this context is still ill defined and shows a multifaceted nature. As a contribution to the area, this article introduces an approach based on causal models and graph theory for the analysis of core value alignment in collaborative networks. The potential application of the approach is then discussed in the virtual organisations' breeding environment context.

Variation of magnetic properties in sedimentary rocks hosting the Foum Zguid dyke (southern Morocco): Combined effects of re-crystallization and Fe-metasomatism

The effects of dyke intrusion on the magnetic properties of host sedimentary rocks are still poorly understood. Therefore, we have evaluated bulk magnetic parameters of standard palaeomagnetic samples collected along several sections across the sediments hosting the Foum Zguid dyke in southern Morocco. The study has been completed with the evaluation of the magnetic fabric after laboratory application of sequential heating experiments. The present study shows that: (1) close to Fourn Zguid dykes, the variations of the bulk magnetic parameters and of the magnetic fabric is strongly related with re-crystallization and Fe-metasomatism intensity. (2) The thermal experiments on AMS of samples collected farther from the dyke and, thus, less affected by heating during dyke emplacement, indicate that 300-400 degrees C is the minimum experimental temperature necessary to trigger appreciable transformations of the pre-existing magnetic fabrics. For temperatures higher than ca. 580 degrees C, the magnetic fabric transformations are fully realized, with complete transposition of the initial fabric to a fabric similar to that of samples collected close to the dyke. Therefore, measured variations of the magnetic fabric can be used to evaluate re-crystallization temperatures experienced by the host sedimentary rock during dyke emplacement. The distinct magnetic behaviour observed along the cross-sections strongly suggests that samples collected farther from the dyke margins did not experience thermal episodes with temperatures higher than 300 degrees C after dyke emplacement. (3) AMS data shows a gradual variation of the magnetic fabric with distance from the dyke margin, from sub-horizontal K-3 away from the dyke to vertical K3 close to the dyke. Experimental heating shows that heat alone can be responsible for this strong variation. Therefore, such orientation changes should not be unequivocally interpreted as the result of a stress field (resulting from the emplacement of the dyke, for instance). (4) Magnetic studies prove to be a very sensitive tool to assess rock magnetic transformations, thermally and chemically induced by dyke intrusion in hosting sediments.

Matrix Converter-Based Unified Power-Flow Controllers: Advanced Direct Power Control Method

This paper presents a direct power control (DPC) for three-phase matrix converters operating as unified power flow controllers (UPFCs). Matrix converters (MCs) allow the direct ac/ac power conversion without dc energy storage links; therefore, the MC-based UPFC (MC-UPFC) has reduced volume and cost, reduced capacitor power losses, together with higher reliability. Theoretical principles of direct power control (DPC) based on sliding mode control techniques are established for an MC-UPFC dynamic model including the input filter. As a result, line active and reactive power, together with ac supply reactive power, can be directly controlled by selecting an appropriate matrix converter switching state guaranteeing good steady-state and dynamic responses. Experimental results of DPC controllers for MC-UPFC show decoupled active and reactive power control, zero steady-state tracking error, and fast response times. Compared to an MC-UPFC using active and reactive power linear controllers based on a modified Venturini high-frequency PWM modulator, the experimental results of the advanced DPC-MC guarantee faster responses without overshoot and no steady-state error, presenting no cross-coupling in dynamic and steady-state responses.

Synthesis of optimization of [11C] Pittsburgh compound B by the captive solvent method

Mestrado em Medicina Nuclear.

Determination of chitin content in fungal cell wall: an alternative flow cytometric method

The conventional methods used to evaluate chitin content in fungi, such as biochemical assessment of glucosamine release after acid hydrolysis or epifluorescence microscopy, are low throughput, laborious, time-consuming, and cannot evaluate a large number of cells. We developed a flow cytometric assay, efficient, and fast, based on Calcofluor White staining to measure chitin content in yeast cells. A staining index was defined, its value was directly related to chitin amount and taking into consideration the different levels of autofluorecence. Twenty-two Candida spp. and four Cryptococcus neoformans clinical isolates with distinct susceptibility profiles to caspofungin were evaluated. Candida albicans clinical isolate SC5314, and isogenic strains with deletions in chitin synthase 3 (chs3Δ/chs3Δ) and genes encoding predicted Glycosyl Phosphatidyl Inositol (GPI)-anchored proteins (pga31Δ/Δ and pga62Δ/Δ), were used as controls. As expected, the wild-type strain displayed a significant higher chitin content (P < 0.001) than chs3Δ/chs3Δ and pga31Δ/Δ especially in the presence of caspofungin. Ca. parapsilosis, Ca. tropicalis, and Ca. albicans showed higher cell wall chitin content. Although no relationship between chitin content and antifungal drug susceptibility phenotype was found, an association was established between the paradoxical growth effect in the presence of high caspofungin concentrations and the chitin content. This novel flow cytometry protocol revealed to be a simple and reliable assay to estimate cell wall chitin content of fungi.

Novel method using a laser scanning cytometer for detection of Mycobacteria in clinical samples

In order to evaluate the capacity of laser scanning cytometry (LSC) to detect acid-fast bacilli directly on clinical samples, a comparison between Kinyoun-stained smears analyzed under light microscopy and propidium iodide-auramine-stained smears analyzed by LSC was performed. The results were compared with those for culture on BACTEC MGIT 960. LSC is a new, reliable methodology to detect Mycobacteria.

Determination of stresses around a cylindrical single pile caused by horizontal movements of soils with the finitive element method

This study was carried out with the aim of modeling in 2D, in plain strain, the movement of a soft cohesive soil around a pile, in order to enable the determination of stresses resulting along the pile, per unit length. The problem in study fits into the large deformations problem and can be due to landslide, be close of depth excavations, to be near of zones where big loads are applied in the soil, etc. In this study is used an constitutive Elasto-Plastic model with the failure criterion of Mohr-Coulomb to model the soil behavior. The analysis is developed considering the soil in undrained conditions. To the modeling is used the finite element program PLAXIS, which use the Updated Lagrangian - Finite Element Method (UL-FEM). In this work, special attention is given to the soil-pile interaction, where is presented with some detail the formulation of the interface elements and some studies for a better understand of his behavior. It is developed a 2-D model that simulates the effect of depth allowing the study of his influence in the stress distribution around the pile. The results obtained give an important base about how behaves the movement of the soil around a pile, about how work the finite element program PLAXIS and how is the stress distribution around the pile. The analysis demonstrate that the soil-structure interaction modeled with the UL-FEM and interface elements is more appropriate to small deformations problems.

Analysis of functionally graded sandwich plate structures with piezoelectric skins, using B-spline finite strip method

Functionally graded materials are composite materials wherein the composition of the constituent phases can vary in a smooth continuous way with a gradation which is function of its spatial coordinates. This characteristic proves to be an important issue as it can minimize abrupt variations of the material properties which are usually responsible for localized high values of stresses, and simultaneously providing an effective thermal barrier in specific applications. In the present work, it is studied the static and free vibration behaviour of functionally graded sandwich plate type structures, using B-spline finite strip element models based on different shear deformation theories. The effective properties of functionally graded materials are estimated according to Mori-Tanaka homogenization scheme. These sandwich structures can also consider the existence of outer skins of piezoelectric materials, thus achieving them adaptive characteristics. The performance of the models, are illustrated through a set of test cases. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of new Fe(II) and Ru(II) eta(5)-monocyclopentadienyl compounds showing significant second order NLO properties

A series of new ruthenium(II) complexes of the general formula [Ru(eta(5)-C5H5)(PP)(L)][PF6] (PP = DPPE or 2PPh(3), L = 4-butoxybenzonitrile or N-(3-cyanophenyl)formamide) and the binuclear iron(II) complex [Fe(eta(5)-C5H5)(PP)(mu-L)(PP)(eta(5)-C5H5)Fe][PF6](2) (L = (E)-2-(3-(4-nitrophenyl)allylidene)malononitrile, that has been also newly synthesized) have been prepared and studied to evaluate their potential in the second harmonic generation property. All the new compounds were fully characterized by NMR, IR and UV-Vis spectroscopies and their electrochemistry behaviour was studied by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of three of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at fundamental wavelength of 1500 nm and the calculated static beta(0) values are found to fall in the range 65-212 x 10(-30) esu. Compound presenting beta(0) = 212 x 10(-30) esu has revealed to be 1.2 times more efficient than urea standard in the second harmonic generation (SHG) property, measured in the solid state by Kurtz powder technique, using a Nd:YAG laser (1064 nm). (C) 2013 Elsevier B.V. All rights reserved.

Optimal design for active damping in sandwich structures using the Direct MultiSearch method

This paper addresses the problem of optimal positioning of surface bonded piezoelectric patches in sandwich plates with viscoelastic core and laminated face layers. The objective is to maximize a set of modal loss factors for a given frequency range using multiobjective topology optimization. Active damping is introduced through co-located negative velocity feedback control. The multiobjective topology optimization problem is solved using the Direct MultiSearch Method. An application to a simply supported sandwich plate is presented with results for the maximization of the first six modal loss factors. The influence of the finite element mesh is analyzed and the results are, to some extent, compared with those obtained using alternative single objective optimization. (C) 2013 Elsevier Ltd. All rights reserved.

Assesing multileaf collimator effect on the build-up region using Monte Carlo method

Previous Monte Carlo studies have investigated the multileaf collimator (MLC) contribution to the build-up region for fields in which the MLC leaves were fully blocking the openings defined by the collimation jaws. In the present work, we investigate the same effect but for symmetric and asymmetric MLC defined field sizes (2×2, 4×4, 10×10 and 3×7 cm2). A Varian 2100C/D accelerator with 120-leaf MLC is accurately modeled fora6MVphoton beam using the BEAMnrc/EGSnrc code. Our results indicate that particles scattered from accelerator head and MLC are responsible for the increase of about 7% on the surface dose when comparing 2×2 and 10×10 cm2 fields. We found that the MLC contribution to the total build-up dose is about 2% for the 2×2 cm2 field and less than 1% for the largest fields.

A New Method to Determine the Density and Water Absorption of Fine Recycled Aggregates

The construction industry keeps on demanding huge quantities of natural resources, mainly minerals for mortars and concrete production. The depletion of many quarries and environmental concerns about reducing the dumping of construction and demolition waste in quarries have led to an increase in the procuring and use of recycled aggregates from this type of waste. If they are to be incorporated in concrete and mortars it is essential to know their properties to guarantee the adequate performance of the end products, in both mechanical and durability-related terms. Existing regulated tests were developed for natural aggregates, however, and several problems arise when they are applied to recycled aggregates, especially fine recycled aggregates (FRA). This paper describes the main problems encountered with these tests and proposes an alternative method to determine the density and water absorption of FRA that removes them. The use of sodium hexametaphosphate solutions in the water absorption test has proven to improve its efficiency, minimizing cohesion between particles and helping to release entrained air.