Bonding and magnetic response properties of several toroid structures. Insights of the role of Ni2S2 as a building block from relativistic density functional theory calculations

Relativistic density functional calculations were carried out on several nickel toroid mercaptides of the general formula [Ni(μ-SR)(2)](n), with the aim to characterize and analyze their stability and magnetic response properties, in order to gain more insights into their stabilization and size-dependent behavior. The Ni-ligand interaction has been studied by means projected density of states and energy decomposition analysis, which denotes its stabilizing character. The graphical representation of the response to an external magnetic field is applied for the very first time taking into account the spin-orbit term. This map allows one to clearly characterize the magnetic behavior inside and in the closeness of the toroid structure showing the prescence of paratropic ring currents inside the Ni(n) ring, and by contrast, diatropic currents confined in each Ni(2)S(2) motif denoting an aromatic behavior (in terms of magnetic criteria). The calculated data suggests that the Ni(2)S(2) moiety can be regarded as a stable constructing block, which can afford several toroid structures of different nuclearities in agreement with that reported in the experimental literature. In addition, the effects of the relativistic treatment over the magnetic response properties on these lighter compounds are denoted by comparing nonrelativistic, scalar relativistic, and scalar plus spin-orbit relativistic treatments, showing their acting, although nonpronunced, role.     

Isotherm Theoretical Study of the AlxGa1−xAsySb1−y Quaternary Alloy Using the Regular Solution Approximation for Its Possible Growth via Liquid-Phase Epitaxy at Low Temperatures

This work presents the theoretical calculation of isotherm diagrams for quaternary alloys of III–V semiconductor compounds with the form III_xIII_1−xV_yV_1−y. In particular, the isotherm diagrams for the Al_xGa_1−xAs_ySb_1−y quaternary alloy at low temperatures were calculated (500 °C, 450 °C, 400 °C, and 350 °C). The Al_xGa_1−xAs_ySb_1−y quaternary alloy was formed from four binary compounds such as GaAs, AlAs, AlSb, and GaSb, all with direct bandgaps. The regular solution approximation was used to find the quaternary isotherm diagrams, represented in four linearly independent equations, which were solved using Parametric Technology Corporation Mathcad 14.0 software for different arsenic and antimony atomic fractions. The results support the possible growth of layers via liquid-phase epitaxy in a range of temperatures from 500 °C to 350 °C, where the crystalline quality could be improved at low temperatures. These semiconductor layers could have applications for optoelectronic devices in photonic communications, thermophotovoltaic systems, and microwave devices with good crystalline quality.     

Pllans–II Induces Cell Death in Cervical Cancer Squamous Epithelial Cells via Unfolded Protein Accumulation and Endoplasmic Reticulum Stress

Due to the lack of chemotherapeutic drugs that selectively affect cervical cancer cells, natural sources such as snake venom are currently being investigated for molecules with antitumor potential. Pllans–II, a phospholipase A₂ type–Asp49 from Porthidium lansbergii lansbergii snake venom, induced cell death in a cervical cancer cell line—Ca Ski—related to dysfunction in the ability to resolve endoplasmic reticulum stress, evidenced by sub–expression of genes such as PERK, ERO1 PDIs, HSP70, and CHOP. Western blot analysis validated the last two genes′ sub–expression at the protein level. In addition, Pllans–II presented a dose–dependent cytotoxic effect on cancer cells and an insignificant effect on healthy endothelial cells (HUVEC). Additionally, Pllans–II inhibited cancer cells′ adhesion and migration capacity, induced cell cycle arrest in the G2/M phase, and induced apoptosis stimulated possibly by the extrinsic route. These results demonstrate for the first time that Pllans–II has an antitumor effect on a squamous epithelial cervical cancer cell line and represents a possible biotechnological tool for designing a prominent antitumor agent.     

Consecutive palladium-catalyzed Hiyama-Heck reactions in aqueous media under ligand-free conditions

Symmetric and asymmetric (E)-1,2-diarylethenes are synthesized from aryl bromides by consecutive one-pot Hiyama-Heck reactions carried out in water and under air; the only additives required are sodium hydroxide, palladium acetate and poly(ethylene glycol), and the products are isolable in many cases by simple filtration of the water solution.     

Comparison of haemodynamics in cerebral aneurysms of different sizes located in the ophthalmic artery

Haemodynamics plays an important role in the progression and rupture of cerebral aneurysms. The temporal and spatial variations of the wall shear stress in the aneurysmal sac are hypothesized to be correlated with its growth and rupture. In addition, the assessment of the velocity field in the aneurysm dome and neck is important for the correct placement of endovascular coils. This work describes the flow dynamics in patient‐specific models of saccular aneurysms of different sizes located in the ophthalmic artery. The models were obtained from three‐dimensional rotational angiography image data and blood flow dynamics was studied under physiologically representative waveform of inflow. The three‐dimensional continuity and momentum equations for unsteady laminar flow were solved with commercial software using nonstructured fine grid sizes. The intra‐aneurysmal flows show complex vortex structures that change during one pulsatile cycle. A relation between the aneurysm aspect ratio and the mean wall shear stress on the aneurysmal sac is showed. Copyright © 2006 John Wiley & Sons, Ltd.     

Testing for cointegration using induced-order statistics

In this paper we explore the usefulness of induced-order statistics in the characterization of integrated series and of cointegration relationships. We propose a non-parametric test statistic for testing the null hypothesis of two independent random walks against wide cointegrating alternatives including monotonic nonlinearities and certain types of level shifts in the cointegration relationship. We call our testing device the induced-order Kolmogorov–Smirnov cointegration test (KS), since it is constructed from the induced-order statistics of the series, and we derive its limiting distribution. This non-parametric statistic endows the test with a number of desirable properties: invariance to monotonic transformations of the series, and robustness for the presence of important parameter shifts. By Monte Carlo simulations we analyze the small sample properties of this test. Our simulation results show the robustness of the induced order cointegration test against departures from linear and constant parameter models. This paper is an extension of the work of Aparicio and Granger (1995) and Aparicio and Escribano (1998).     

Electrochemistry and chromatographic detection of monosaccharides,disaccharides, and related compounds at an electrocatalytic chemically modified electrode

Many carbohydrate compounds undergo electro-oxidation at modest positive potentials at chemically modified electrodes (CMEs) made by adding cobalt phthalocyanine (CoPC) electrocatalyst to a conventional carbon paste mixture. The active carbohydrates which were oxidized at the CME at +0.4 to 0.5 V vs. Ag/AgCl under the very basic pH conditions required, included not only monosaccharides but also oligosaccharides, deoxy sugars, and even simple polyalcohols such as glycerol. When used for carbohydrate detection after liquid chromatography, the CoPC CME yielded detection limits in the 10–50 pmol range. Electrode stability and selectivity was such that no sample preparation other than dilution and particulate filtration was required for carbohydrate determinations in sample matrices including food products and physiological fluids.     

Synthesis of heterocyclic compounds IV1 pyrazol-1′-ylpyridines2

2-Pyrazol-1-ylpyridines were synthesized by condensation of pyridylhydrazines with 1,3-dicarbonyl compounds or by theUllmann arylation of pyrazoles with halopyridines.Taken in part from the Master's thesis ofA. A. A. Pinto, Instituto Militar de Engenharia, Rio de Janeiro, 1978.