Structural and Microanalytical Studies of CrO2 Thin Films on c-Sapphire by High Resolution Electron Microscopy Methods

Chromium dioxide (CrO2) has been extensively used in the magnetic recording industry. However, it is its ferromagnetic half-metallic nature that has more recently attracted much attention, primarily for the development of spintronic devices. CrO2 is the only stoichiometric binary oxide theoretically predicted to be fully spin polarized at the Fermi level. It presents a Curie temperature of ∼ 396 K, i.e. well above room temperature, and a magnetic moment of 2 mB per formula unit. However an antiferromagnetic native insulating layer of Cr2O3 is always present on the CrO2 surface which enhances the CrO2 magnetoresistance and might be used as a barrier in magnetic tunnel junctions.

Modelling of n-stage Blumlein stacked lines for bipolar pulse generation

A Blumlein line is a particular Pulse Forming Line, PFL, configuration that allows the generation of high-voltage sub-microsecond square pulses, with the same voltage amplitude as the dc charging voltage, into a matching load. By stacking n Blumlein lines one can multiply in theory by n the input dc voltage charging amplitude. In order to understand the operating behavior of this electromagnetic system and to further optimize its operation it is fundamental to theoretically model it, that is to calculate the voltage amplitudes at each circuit point and the time instant that happens. In order to do this, one needs to define the reflection and transmission coefficients where impedance discontinuity occurs. The experimental results of a fast solid-state switch, which discharges a three stage Blumlein stack, will be compared with theoretical ones.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Biochemical and structural characterization of β-lactamases tem-180 and tem-201

With the constant development of new antibiotics, selective pressure is a force to reckon when investigating antibiotic resistance. Although advantageous for medical treatments, it leads to increasing resistance. It is essential to use more potent and toxic antibiotics. Enzymes capable of hydrolyzing antibiotics are among the most common ways of resistance and TEM variants have been detected in several resistant isolates. Due to the rapid evolution of these variants, complex phenotypes have emerged and the need to understand their biological activity becomes crucial. To investigate the biochemical properties of TEM-180 and TEM-201 several computational methodologies have been used, allowing the comprehension of their structure and catalytic activity, which translates into their biological phenotype. In this work we intent to characterize the interface between these proteins and the several antibiotics used as ligands. We performed explicit solvent molecular dynamics (MD) simulations of these complexes and studied a variety of structural and energetic features. The interfacial residues show a distinct behavior when in complex with different antibiotics. Nevertheless, it was possible to identify some common Hot Spots among several complexes – Lys73, Tyr105 and Glu166. The structural changes that occur during the Molecular Dynamic (MD) simulation lead to the conclusion that these variants have an inherent capacity of adapting to the various antibiotics. This capability might be the reason why they can hydrolyze antibiotics that have not been described until now to be degraded by TEM variants. The results obtained with computational and experimental methodologies for the complex with Imipenem have shown that in order to this type of enzymes be able to acylate the antibiotics, they need to be capable to protect the ligand from water molecules.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Elastically restrained Bernoulli-Euler beams applied to rotary machinery modelling

Facing the lateral vibration problem of a machine rotor as a beam on elastic supports in bending, the authors deal with the free vibration of elastically restrained Bernoulli-Euler beams carrying a finite number of concentrated elements along their length. Based on Rayleigh's quotient, an iterative strategy is developed to find the approximated torsional stiffness coefficients, which allows the reconciliation between the theoretical model results and the experimental ones, obtained through impact tests. The mentioned algorithm treats the vibration of continuous beams under a determined set of boundary and continuity conditions, including different torsional stiffness coefficients and the effect of attached concentrated masses and rotational inertias, not only in the energetic terms of the Rayleigh's quotient but also on the mode shapes, considering the shape functions defined in branches. Several loading cases are examined and examples are given to illustrate the validity of the model and accuracy of the obtained natural frequencies.

Ruthenium(II) Arene Complexes Bearing Tris(pyrazolyl)methanesulfonate Capping Ligands.Electrochemistry, Spectroscopic, and X-ray Structural Characterization

Novel [Ru(L)(Tpms)]Cl and [Ru(L)(Tpms(Ph))]Cl complexes (L = p-cymene, benzene, or hexamethylbenzene, Tpms = tris(pyrazolyl)-methanesulfonate, Tpms(Ph) = tris(3-phenylpyrazoly)methanesulfonate) have been prepared by reaction of [Ru(L)(mu-Cl)(2)](2) with Li[Tpms] and Li[Tpms(Ph)], respectively. [Ru(p-cymene)(Tpms)]BF4 has been synthesized through a metathetic reaction of [Ru(p-cymene)(Tpms)]Cl with AgBF4. [RuCl(cod)(Tpms)] (cod = 1,5-cyclooctadiene) and [RuCl(cod)(Tpms(Ph))] are also reported, being obtained by reaction of [RuCl2(cod)(MeCN)(2)] with Li[Tpms] and Li[Tpms(Ph)], respectively. The structures of the complexes and the coordination modes of the ligands have been established by IR, NMR, and single-crystal X-ray diffraction (for [RuL(Tpms)]X (L = p-cymene or HMB, X = Cl; L = p-cymene, X = BF4)) studies. Electrochemical studies showed that each complex undergoes a single-electron R-II -> R-III oxidation at a potential measured by cyclic voltammetry, allowing to compare the electron-donor characters of the tris(pyrazolyl)methanesulfonate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for Tmps(Ph), HMB, and cod.

Modelling real solar cell using PSCAD/MATLAB

This paper presents the development of a solar photovoltaic (PV) model based on PSCAD/EMTDC - Power System Computer Aided Design – including a mathematical model study. An additional algorithm has been implemented in MATLAB software in order to calculate several parameters required by the PSCAD developed model. All the simulation study has been performed in PSCAD/MATLAB software simulation tool. A real data base concerning irradiance, cell temperature and PV power generation was used in order to support the evaluation of the implemented PV model.

Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

Structural characterization and immunogenicity in wildtype and immune tolerant mice of degraded recombinant human interferon alpha2b

Purpose - To study the influence of protein structure on the immunogenicity in wildtype and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods - RhIFNα2b was degraded by metal catalyzed oxidation (M), crosslinking with glutaraldehyde (G), oxidation with hydrogen peroxide (H) and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reversed-phase HPLC, SDS-PAGE, Western blotting and mass spectrometry. The immunogenicity of the products was evaluated in wildtype mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by ELISA or surface plasmon resonance. Results - M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Native (N) rhIFNα2b was immunogenic in the wildtype mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The antirhIFNα2b antibody levels in the wildtype mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ~ N-rhIFNα2b >> B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions - RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Structural characterization and immunogenicity in wild-type and immune tolerant mice of degraded recombinant human interferon Alpha2b

Purpose: This study was conducted to study the influence of protein structure on the immunogenicity in wild-type and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods: RhIFNα2b was degraded by metal-catalyzed oxidation (M), cross-linking with glutaraldehyde (G), oxidation with hydrogen peroxide (H), and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reverse-phase high-pressure liquid chromatography, sodium dodecyl sulfate polyacrylamide gel electrophoresis, Western blotting, and mass spectrometry. The immunogenicity of the products was evaluated in wild-type mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by enzyme-linked immunosorbent assay or surface plasmon resonance. Results: M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Nontreated (N) rhIFNα2b was immunogenic in the wild-type mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The anti-rhIFNα2b antibody levels in the wild-type mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ∼ N-rhIFNα2b ≫ B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions: RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Modelling group decision simulation through argumentation

Group decision making plays an important role in today’s organisations. The impact of decision making is so high and complex, that rarely the decision making process is made individually. In Group Decision Argumentation, there is a set of participants, with different profiles and expertise levels, that exchange ideas or engage in a process of argumentation and counter-argumentation, negotiate, cooperate, collaborate or even discuss techniques and/or methodologies for problem solving. In this paper, it is proposed a Multi-Agent simulator for the behaviour representation of group members in a decision making process. Agents behave depending on rational and emotional intelligence and use persuasive argumentation to convince and make alternative choices.

A model updating technique based on FRFs for damped structures

Model updating methods often neglect that in fact all physical structures are damped. Such simplification relies on the structural modelling approach, although it compromises the accuracy of the predictions of the structural dynamic behaviour. In the present work, the authors address the problem of finite element (FE) model updating based on measured frequency response functions (FRFs), considering damping. The proposed procedure is based upon the complex experimental data, which contains information related to the damped FE model parameters and presents the advantage of requiring no prior knowledge about the damping matrix structure or its content, only demanding the definition of the damping type. Numerical simulations are performed in order to establish the applicability of the proposed damped FE model updating technique and its results are discussed in terms of the correlation between the simulated experimental complex FRFs and the ones obtained from the updated FE model.

Purification and structural characterization of compounds isolated from Cystoseira abies-marina

6th Spanish-Portuguese-Japanese Organic Chemistry Symposium, Lisboa, de 18 a 20 de Julho de 2012 (Poster Communication).

Structural Color and Iridescence in Transparent Sheared Cellulosic Films

Shear transparent cellulose free-standing thin films can develop iridescence similar to that found in petals of the tulip Queen of the Night. The iridescence of the film arises from the modulation of the surface into bands periodically spread perpendicular to the shear direction. Small amounts of nanocrystalline cellulose (NCC) rods in the precursor liquid-crystalline solutions do not disturb the optical properties of the solutions but enhance the mechanical characteristics of the films and affects their iridescence. Smaller bands periodicity, not affected by the NCC rods, slightly deviated from the shear direction is also observed. NCCs are crucial to tune and understand the film's surface features formation. Our findings could lead to new materials for application in soft reflective screens and devices.