Bulk structures of PtO and PtO(2) from density functional calculations

Platinum plays an important role in catalysis and electrochemistry, and it is known that the direct interaction of oxygen with Pt surfaces can lead to the formation of platinum oxides (PtO(x)), which can affect the reactivity. To contribute to the atomistic understanding of the atomic structure of PtO(x), we report a density functional theory study of the atomic structure of bulk PtO(x) (1 <= x <= 2). From our calculations, we identified a lowest-energy structure (GeS type, space group Pnma) for PtO, which is 0.181 eV lower in energy than the structure suggested by W. J. Moore and L. Pauling [J. Am. Chem. Soc. 63, 1392 (1941)] (PtS type). Furthermore, two atomic structures were identified for PtO(2), which are almost degenerate in energy with the lowest-energy structure reported so far for PtO(2) (CaCl(2) type). Based on our results and analysis, we suggest that Pt and O atoms tend to form octahedron motifs in PtO(x) even at lower O composition by the formation of Pt-Pt bonds.

Crystallisation behaviour and glass-forming ability in Al-La-Ni system

The crystallisation behaviour for alloys in the Al-rich corner in the Al-La-Ni system is reported in this paper Alloys were selected based on the topological instability criterion (lambda criterion) calculated from the alloy composition and metallic radii of the alloying elements and aluminum Amorphous ribbons were produced by melt-spinning and the crystallisation reactions were analysed by X-ray diffraction and calorimetry The results showed that increasing the values of lambda from 0.072 to 0.16 resulted in the following changes in the crystallisation behaviour, as predicted by the lambda criterion (a) nanocrystallisation of alpha-Al for the alloy composition corresponding to lambda = 0 072 and (b) detection of the glass transition temperature, T(g), for the alloys with composition close to lambda approximate to 0.1 line. For compositions corresponding to both ends of the lambda approximate to 0 1 line (near the binaries lines) T(g) could be detected only in the ""intermediary"" central region, and the alloy we produced in this region was considered the best glass former for the Al-rich corner Also, except for the alloys with the highest NI content, crystallisation proceeded by two distinct exothermic peaks which are typical of nanocrystallisation transformation. These behaviours are discussed in terms of compositional (lambda parameter) and topological aspects to account for cluster formation in the amorphous phase. Crown Copyright (C) 2009 Published by Elsevier B V All rights reserved

Crystallisation behaviours of Al-based metallic glasses: Compositional and topological aspects

The different types of thermal crystallisation behaviours observed during continuous heating of M-based metallic glasses have been successfully associated with the topological instability. criterion, which is simply calculated from the alloy composition and metallic radii of the alloying elements and aluminium. In the present work, we report on new results evidencing the correlation between the values of X and the crystallisation behaviours in Al-based alloys of the Al-Ni-Ce system and we compare the glass-forming abilities of alloys designed with compositions corresponding to the same topological instability condition. The results are discussed in terms of compositional and topological aspects emphasizing the relevance of the different types of clusters in the amorphous phase in defining the stability of the glass and the types of thermal crystallisation. (C) 2008 Elsevier B.V. All rights reserved.

Evolutionary conservation of the membrane fusion machine

Recent structural studies of proteins mediating membrane fusion reveal intriguing similarities between diverse viral and mammalian systems. Particularly striking is the close similarity between the transmembrane envelope glycoproteins from the retrovirus HTLV-1 and the filovirus Ebola. These similarities suggest similar mechanisms of membrane fusion. The model that fits most currently available data suggests fusion activation in viral systems is driven by a symmetrical conformational change triggered by an activation event such as receptor binding or a pH change. The mammalian vesicle fusion mediated by the SNARE protein complex most likely occurs by a similar mechanism but without symmetry constraints.

Recent advances in the preparation and utilization of carbon nanotubes for hydrogen storage

Recent progress in the production, purification, and experimental and theoretical investigations of carbon nanotubes for hydrogen storage are reviewed. From the industrial point of view, the chemical vapor deposition process has shown advantages over laser ablation and electric-arc-discharge methods. The ultimate goal in nanotube synthesis should be to gain control over geometrical aspects of nanotubes, such as location and orientation, and the atomic structure of nanotubes, including helicity and diameter. There is currently no effective and simple purification procedure that fulfills all requirements for processing carbon nanotubes. Purification is still the bottleneck for technical applications, especially where large amounts of material are required. Although the alkali-metal-doped carbon nanotubes showed high H-2 Weight uptake, further investigations indicated that some of this uptake was due to water rather than hydrogen. This discovery indicates a potential source of error in evaluation of the storage capacity of doped carbon nanotubes. Nevertheless, currently available single-wall nanotubes yield a hydrogen uptake value near 4 wt% under moderate pressure and room temperature. A further 50% increase is needed to meet U.S. Department of Energy targets for commercial exploitation. Meeting this target will require combining experimental and theoretical efforts to achieve a full understanding of the adsorption process, so that the uptake can be rationally optimized to commercially attractive levels. Large-scale production and purification of carbon nanotubes and remarkable improvement of H-2 storage capacity in carbon nanotubes represent significant technological and theoretical challenges in the years to come.

ITO/SiOx/Si optical sensor with internal gain

A visible/near-infrared optical sensor based on an ITO/SiOx/n-Si structure with internal gain is presented. This surface-barrier structure was fabricated by a low-temperature processing technique. The interface properties and carder transport were investigated from dark current-voltage and capacitance-voltage characteristics. Examination of the multiplication properties was performed under different light excitation and reverse bias conditions. The spectral and pulse response characteristics are analysed. The current amplification mechanism is interpreted by the control of electron current by the space charge of photogenerated holes near the SiOx/Si interface. The optical sensor output characteristics and some possible device applications are presented.

Femtosecond laser ablation of dentin

The surface morphology, structure and composition of human dentin treated with a femtosecond infrared laser (pulse duration 500 fs, wavelength 1030 nm, fluences ranging from 1 to 3 J cm(-2)) was studied by scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The average dentin ablation threshold under these conditions was 0.6 +/- 0.2 J cm(-2) and the ablation rate achieved in the range 1 to 2 mu m/pulse for an average fluence of 3 J cm(-2). The ablation surfaces present an irregular and rugged appearance, with no significant traces of melting, deformation, cracking or carbonization. The smear layer was entirely removed by the laser treatment. For fluences only slightly higher than the ablation threshold the morphology of the laser-treated surfaces was very similar to the dentin fracture surfaces and the dentinal tubules remained open. For higher fluences, the surface was more porous and the dentin structure was partially concealed by ablation debris and a few resolidified droplets. Independently on the laser processing parameters and laser processing method used no sub-superficial cracking was observed. The dentin constitution and chemical composition was not significantly modified by the laser treatment in the processing parameter range used. In particular, the organic matter is not preferentially removed from the surface and no traces of high temperature phosphates, such as the beta-tricalcium phosphate, were observed. The achieved results are compatible with an electrostatic ablation mechanism. In conclusion, the high beam quality and short pulse duration of the ultrafast laser used should allow the accurate preparation of cavities, with negligible damage of the underlying material.

Selected configuration interaction with truncation energy error and application to the Ne atom

Selected configuration interaction (SCI) for atomic and molecular electronic structure calculations is reformulated in a general framework encompassing all CI methods. The linked cluster expansion is used as an intermediate device to approximate CI coefficients BK of disconnected configurations (those that can be expressed as products of combinations of singly and doubly excited ones) in terms of CI coefficients of lower-excited configurations where each K is a linear combination of configuration-state-functions (CSFs) over all degenerate elements of K. Disconnected configurations up to sextuply excited ones are selected by Brown's energy formula, ΔEK=(E-HKK)BK2/(1-BK2), with BK determined from coefficients of singly and doubly excited configurations. The truncation energy error from disconnected configurations, Δdis, is approximated by the sum of ΔEKS of all discarded Ks. The remaining (connected) configurations are selected by thresholds based on natural orbital concepts. Given a model CI space M, a usual upper bound ES is computed by CI in a selected space S, and EM=E S+ΔEdis+δE, where δE is a residual error which can be calculated by well-defined sensitivity analyses. An SCI calculation on Ne ground state featuring 1077 orbitals is presented. Convergence to within near spectroscopic accuracy (0.5 cm-1) is achieved in a model space M of 1.4× 109 CSFs (1.1 × 1012 determinants) containing up to quadruply excited CSFs. Accurate energy contributions of quintuples and sextuples in a model space of 6.5 × 1012 CSFs are obtained. The impact of SCI on various orbital methods is discussed. Since ΔEdis can readily be calculated for very large basis sets without the need of a CI calculation, it can be used to estimate the orbital basis incompleteness error. A method for precise and efficient evaluation of ES is taken up in a companion paper

Association with {beta}-COP regulates the trafficking of the newly synthesized Na,K-ATPase.

Plasma membrane expression of the Na,K-ATPase requires assembly of its α- and β-subunits. Using a novel labeling technique to identify Na,K-ATPase partner proteins, we detected an interaction between the Na,K-ATPase α-subunit and the coat protein, β-COP, a component of the COP-I complex. When expressed in the absence of the Na,K-ATPase β-subunit, the Na,K-ATPase α-subunit interacts with β-COP, is retained in the endoplasmic reticulum, and is targeted for degradation. In the presence of the Na,K-ATPase β-subunit, the α-subunit does not interact with β-COP and traffics to the plasma membrane. Pulse-chase experiments demonstrate that in cells expressing both the Na,K-ATPase α- and β-subunits, newly synthesized α-subunit associates with β-COP immediately after its synthesis but that this interaction does not constitute an obligate intermediate in the assembly of the α- and β-subunits to form the pump holoenzyme. The interaction with β-COP was reduced by mutating a dibasic motif at Lys(54) in the Na,K-ATPase α-subunit. This mutant α-subunit is not retained in the endoplasmic reticulum and reaches the plasma membrane, even in the absence of Na,K-ATPase β-subunit expression. Although the Lys(54) α-subunit reaches the cell surface without need for β-subunit assembly, it is only functional as an ion-transporting ATPase in the presence of the β-subunit.

Resonating-valence-bond theory for the square-planar lattice

The short-range resonating-valence-bond (RVB) wave function with nearest-neighbor (NN) spin pairings only is investigated as a possible description for the Heisenberg model on a square-planar lattice. A type of long-range order associated to this RVB Ansatz is identified along with some qualitative consequences involving lattice distortions, excitations, and their coupling.

Computadores em educação química: estrutura atômica e tabela periódica

In this paper we discuss an approach for two initial topics in Chemistry: atomic structure and periodic table. The focus of this approach is the use of educational software resources in the perspective of teacher's formation.

Crescimento de cristais de rubi e safira pelo método do fluxo

This work reports the growth of corundum crystals by the flux method. The main objective was the evaluation of versatility, effectiveness and real possibilities of the flux method to the synthesis and doping of monocrystals with impurities of particular interest. In this work the chosen impurities were i) Cr and ii) Fe and Ti, aiming the synthesis of rubies and sapphires, respectively. The crystals were grown by heating a mixture of Al2O3:Cr or Al2O3:Fe:Ti and flux (MoO3). The maximum crystal size obtained was 1.0 mm, all transparent, presenting well developed faces, bipiramidal hexagonal shape, and showing a typical red (ruby) and/or light blue (sapphire) color. EDX and XPD experiments were performed in order to characterize some of the synthesized crystals. All crystallized specimens presented the α-alumina atomic structure.

Os químicos ocultos e sua extraordinária jornada ao mundo dos átomos

At the end of the XIX century, a group of chemists and theosophists called the Occult Chemists suggested it would be possible "to see" atoms by clairvoyance. In a meditative situation, a skilled person in contact with a substance would thus be able to see magnified atoms and molecules, as well as its internal structure. Annie Besant was the leader of this group and, together with Curuppumullage Jinarajadasa, Charles Leadbeater and Bertram Keightley, they devised an extraordinary atomic theory in which atoms consisted of smaller, indivisible units of energy called anu. In this paper, we present the fundamental principles of this unusual theory.

Structural modelling of liquid ZrO2 and glassy B2O3 by using AB INITIO Molecular Dynamics method

Atomic structure of ZrO2 and B2O3 was investigated in this work. New data under extreme conditions (T = 3100 K) was obtained for the liquid ZrO2 structure. A fractional number of boron was investigated for glassy structure of B2O3. It was shown that it is possible to obtain an agreement for the fractional number between NMR and DFT techniques using a suitable initial configuration.

Aurapten, a coumarin with growth inhibition against Leishmania major promastigotes

Several natural compounds have been identified for the treatment of leishmaniasis. Among them are some alkaloids, chalcones, lactones, tetralones, and saponins. The new compound reported here, 7-geranyloxycoumarin, called aurapten, belongs to the chemical class of the coumarins and has a molecular weight of 298.37. The compund was extracted from the Rutaceae species Esenbeckia febrifuga and was purified from a hexane extract starting from 407.7 g of dried leaves and followed by four silica gel chromatographic fractionation steps using different solvents as the mobile phase. The resulting compound (47 mg) of shows significant growth inhibition with an LD50 of 30 µM against the tropical parasite Leishmania major, which causes severe clinical manifestations in humans and is endemic in the tropical and subtropical regions. In the present study, we investigated the atomic structure of aurapten in order to determine the existence of common structural motifs that might be related to other coumarins and potentially to other identified inhibitors of Leishmania growth and viability. This compound has a comparable inhibitory activity of other isolated molecules. The aurapten is a planar molecule constituted of an aromatic system with electron delocalization. A hydrophobic side chain consisting of ten carbon atoms with two double bonds and negative density has been identified and may be relevant for further compound synthesis.