Synthesis and crystal structure of copper (II) uracil ternary polymeric complex with 1,10-phenanthroline along with the Hirshfeld surface analysis of the metal binding sites for the uracil ligand

The study of models for ``metal-enzyme-substrate'' interaction has been a proactive area of research owing to its biological and pharmacological importance. In this regard the ternary copper uracil complex with 1,10-phenanthroline represents metal-enzyme-substrate system for DNA binding enzymes. The synthesis of the complex, followed by slow evaporation of the reaction mixture forms two concomitant solvatomorph crystals viz., {Cu(phen)(mu-ura)(H2O)](n)center dot H2O (1a)} and {Cu(phen)(mu-ura)(H2O)](n)center dot CH3OH (1b)}. Both complexes are structurally characterized, while elemental analysis, IR and EPR spectra were recorded for 1b (major product). In both complexes, uracil coordinates uniquely via N1 and N3 nitrogen atom acting as a bidentate bridging ligand forming a 1-D polymer. The two solvatomorphs were quantitatively analyzed for the differences with the aid of Hirshfeld surface analysis. (C) 2014 Elsevier B.V. All rights reserved.

Effect of Line Defects on the Electrical Transport Properties of Monolayer MoS2 Sheet

We present a computational study on the impact of line defects on the electronic properties of monolayer MoS2. Four different kinds of line defects with Mo and S as the bridging atoms, consistent with recent theoretical and experimental observations, are considered herein. We employ the density functional tight-binding (DFTB) method with a Slater-Koster-type DFTB-CP2K basis set for evaluating the material properties of perfect and the various defective MoS2 sheets. The transmission spectra are computed with a DFTB-non-equilibrium Green's function formalism. We also perform a detailed analysis of the carrier transmission pathways under a small bias and investigate the phase of the transmission eigenstates of the defective MoS2 sheets. Our simulations show a two to four fold decrease in carrier conductance of MoS2 sheets in the presence of line defects as compared to that for the perfect sheet.

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2 `-bipyridine

The synthesis of the heterobinuclear copper-zinc complex CuZn(bz)(3)(bpy)(2)]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 angstrom. The complex is normal paramagnetic having mu(eff) value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants A(av) = 63 x 10(-4) cm(-1), characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g(parallel to) = 2.254 and g(perpendicular to) =2.071 and A(parallel to) = 160 x 10(-4) cm(-1). The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution. (C) 2014 Elsevier B.V. All rights reserved.

An enolato-bridged dinuclear Cu(II) complex with a coumarin-assisted precursor: a spectral, magnetic and biological study

A new, phenoxo-bridged Cu-II dinuclear complex Cu-2(L)(2)(DMF)(2)] (1) has been obtained by employing the coumarin-assisted tridentate precursor, H2L, benzoic acid(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-ylmethylene)-hydrazide]. Complex 1 has been systematically characterized by FTIR, UV-Vis, fluorescence and PR spectrometry. The single crystal X-ray diffraction analysis of 1 shows that the geometry around each copper ion is square pyramidal, comprising two enolato oxygen atoms belonging to different ligands (which assemble the dimer bridging the two metal centers), one imine-N and one phenolic-O atoms of the Schiff base and one oxygen atom from the DMF molecule. The temperature dependent magnetic interpretation agrees with the existence of weak ferromagnetic interactions between the bridging dinuclear Cu(II) ions. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy towards M. tuberculosis H37Rv ATCC 27294 and M. tuberculosis H37Ra ATCC 25177 strains. The cytotoxicity study on human adenocarcinoma cell lines (MCF7) suggests that the ligand and complex 1 have potential anticancer properties. Molecular docking of H2L with the enoyl acyl carrier protein reductase of M. tuberculosis H37R(v) (PDB ID: 4U0K) is examined and the best docked pose of H2L shows one hydrogen bond with Thr196 (1.99 angstrom).

General framework for acoustic emission during plastic deformation

Despite the long history, so far there is no general theoretical framework for calculating the acoustic emission spectrum accompanying any plastic deformation. We set up a discrete wave equation with plastic strain rate as a source term and include the Rayleigh-dissipation function to represent dissipation accompanying acoustic emission. We devise a method of bridging the widely separated time scales of plastic deformation and elastic degrees of freedom. While this equation is applicable to any type of plastic deformation, it should be supplemented by evolution equations for the dislocation microstructure for calculating the plastic strain rate. The efficacy of the framework is illustrated by considering three distinct cases of plastic deformation. The first one is the acoustic emission during a typical continuous yield exhibiting a smooth stress-strain curve. We first construct an appropriate set of evolution equations for two types of dislocation densities and then show that the shape of the model stress-strain curve and accompanying acoustic emission spectrum match very well with experimental results. The second and the third are the more complex cases of the Portevin-Le Chatelier bands and the Luders band. These two cases are dealt with in the context of the Ananthakrishna model since the model predicts the three types of the Portevin-Le Chatelier bands and also Luders-like bands. Our results show that for the type-C bands where the serration amplitude is large, the acoustic emission spectrum consists of well-separated bursts of acoustic emission. At higher strain rates of hopping type-B bands, the burst-type acoustic emission spectrum tends to overlap, forming a nearly continuous background with some sharp acoustic emission bursts. The latter can be identified with the nucleation of new bands. The acoustic emission spectrum associated with the continuously propagating type-A band is continuous. These predictions are consistent with experimental results. More importantly, our study shows that the low-amplitude continuous acoustic emission spectrum seen in both the type-B and type-A band regimes is directly correlated to small-amplitude serrations induced by propagating bands. The acoustic emission spectrum of the Luders-like band matches with recent experiments as well. In all of these cases, acoustic emission signals are burstlike, reflecting the intermittent character of dislocation-mediated plastic flow.

Amine Functionalized polyaniline grafted to exfoliated graphite oxide: Synthesis, characterization and multi-element sensor studies

An amine functionalized polyaniline (AMPANI) derivative has been grafted onto exfoliated graphite oxide (EGO). The synthesis involved the in-situ chemical oxidative polymerization of functionalized aniline monomer in the presence of EGO with diaminobenzene acting as a bridging ligand to yield EGAMPANI. The synthesized compound was characterized by FT-IR and FT-Raman spectroscopy as well as thermogravimetric and X-ray diffraction analysis. The EGAMPANI was then used to modify a carbon paste electrode (CPE), which was applied for multi-elemental sensing of Pb2+, Cd2+ and Hg2+ ions using differential pulse anodic stripping voltammetty. The limits of detection achieved using the EGAMPANI modified CPE were 22 x 10(-6) M for Hg2+ ion, 1.2 x 10(-6) M for Cd2+ ion and 9.8 x 10(-7) M for Pb2+ ion. (C) 2015 Elsevier B.V. All rights reserved.

In-situ study of microscale fracture of diffusion aluminide bond coats: Effect of platinum

The influence of Pt layer thickness on the fracture behavior of PtNiAl bond coats was studied in situ using clamped micro-beam bend tests inside a scanning electron microscope (SEM). Clamped beam bending is a fairly well established micro-scale fracture test geometry that has been previously used in determination of fracture toughness of Si and PtNiAl bond coats. The increasing amount of Pt in the bond coat matrix was accompanied by several other microstructural changes such as an increase in the volume fraction of alpha-Cr precipitate particles in the coating as well as a marginal decrease in the grain size of the matrix. In addition, Pt alters the defect chemistry of the B2-NiAl structure, directly affecting its elastic properties. A strong correlation was found between the fracture toughness and the initial Pt layer thickness associated with the bond coat. As the Pt layer thickness was increased from 0 to 5 mu m, resulting in increasing Pt concentration from 0 to 14.2 at.% in the B2-NiAl matrix and changing alpha-Cr precipitate fraction, the initiation fracture toughness (K-IC) was seen to rise from 6.4 to 8.5 MPa.m(1/2). R-curve behavior was observed in these coatings, with K-IC doubling for a crack propagation length of 2.5 mu m. The reasons for the toughening are analyzed to be a combination of material's microstructure (crack kinking and bridging due to the precipitates) as well as size effects, as the crack approaches closer to the free surface in a micro-scale sample.

Covalent Postassembly Modification and Water Adsorption of Pd3 Self-Assembled Trinuclear Barrels

Three new ditopic imidazole ligands (2-4) were synthesized in high yields and characterized by various spectroscopic techniques. These ligands resulted in the formation of 3 + 6] self-assembled trinuclear barrels (5-7) in quantitative yields by stoichiometric combination of individual ligands and Pd(NO3)(2) in DMSO. All the three assemblies (5-7) were characterized by `H NMR and ESI-MS analysis, and subsequently, structures of the complexes 5 and 6 were confirmed by single-crystal X-ray diffraction studies. Structure analysis reveals the presence of NO3- counter anions in the intermolecular channels/pockets, which could potentially act as H-bonding sites between adsorbed water molecules within the channels. In fact, both the assemblies (5 and 6) showed water uptake (136.58, and 123.78 cm(3) g(-1), respectively) at ambient temperature under maximum allowable humidity. In addition, free aldehyde group present in the bridging ligand in complex 7 provides reactive site for postassembly modification. Herein, Knoevenagel condensation with Meldrum's acid was utilized under mild conditions by targeting aldehyde group appended in prefabricated complex 7 and transformed into a different complex (8) with altered functional group. Such postassembly functionalization enables incorporation of a new functional group without disrupting the integrity of the trifacial structure.

Mode I crack growth resistance of metallic foams

A Dugdale-type cohesive zone model is used to predict the mode I crack growth resistance (R-curve) of metallic foams, with the fracture process characterized by an idealized traction-separation law that relates the crack surface traction to crack opening displacement. A quadratic yield function, involving the von Mises effective stress and mean stress, is used to account for the plastic compressibility of metallic foams. Finite element calculations are performed for the crack growth resistance under small scale yielding and small scale bridging in plane strain, with K-field boundary conditions. The following effects upon the fracture process are quantified: material hardening, bridging strength, T-stress (the non-singular stress acting parallel to the crack plane), and the shape of yield surface. To study the failure behaviour and notch sensitivity of metallic foams in the presence of large scale yielding, a study is made for panels embedded with either a centre-crack or an open hole and subjected to tensile stressing. For the centre-cracked panel, a transition crack size is predicted for which the fracture response switches from net section yielding to elastic-brittle fracture. Likewise, for a panel containing a centre-hole, a transition hole diameter exists for which the fracture response switches from net section yielding to a local maximum stress criterion at the edge of the hole.

Scaling, Dimensional Analysis, and Indentation Measurements

We provide an overview of the basic concepts of scaling and dimensional analysis, followed by a review of some of the recent work on applying these concepts to modeling instrumented indentation measurements. Specifically, we examine conical and pyramidal indentation in elastic-plastic solids with power-law work-hardening, in power-law creep solids, and in linear viscoelastic materials. We show that the scaling approach to indentation modeling provides new insights into several basic questions in instrumented indentation, including, what information is contained in the indentation load-displacement curves? How does hardness depend on the mechanical properties and indenter geometry? What are the factors determining piling-up and sinking-in of surface profiles around indents? Can stress-strain relationships be obtained from indentation load-displacement curves? How to measure time dependent mechanical properties from indentation? How to detect or confirm indentation size effects? The scaling approach also helps organize knowledge and provides a framework for bridging micro- and macroscales. We hope that this review will accomplish two purposes: (1) introducing the basic concepts of scaling and dimensional analysis to materials scientists and engineers, and (2) providing a better understanding of instrumented indentation measurements.

The fracture energy of metal fibre reinforced ceramic composites (MFCs)

A model is presented for prediction of the fracture energy of ceramic-matrix composites containing dispersed metallic fibres. It is assumed that the work of fracture comes entirely from pull-out and/or plastic deformation of fibres bridging the crack plane. Comparisons are presented between these predictions and experimental measurements made on a commercially-available composite material of this type, containing stainless steel (304) fibres in a matrix predominantly comprising alumina and alumino-silicate phases. Good agreement is observed, and it's noted that there is scope for the fracture energy levels to be high (~20kJm-2). Higher toughness levels are both predicted and observed for coarser fibres, up to a practical limit for the fibre diameter of the order of 0.5mm. Other deductions are also made concerning strategies for optimisation of the toughness of this type of material. © 2010 Elsevier Ltd.

Propuesta educativa para la promoción de una cultura de donación de órganos

La escasez de órganos para donación y trasplante es un problema acuciante que involucra a toda la sociedad. Existen diversos prejuicios, racionales y emocionales, por los que muchas personas son reacias a donar sus órganos, sin saber o sin comprender que este gesto podría salvar vidas. El autor ahonda en esta problemática médico-social y plantea una propuesta para revertirla, comenzando con la educación desde el nivel primario y abarcando diferentes niveles educativos y ámbitos de la sociedad. Pone especial énfasis en la formación de los jóvenes, y su entorno social y familiar, quienes juegan un papel preponderante en el desarrollo de futuros programas educativos. Esta propuesta es integral y no implica controversias legales ni éticomorales, por lo que se presenta como una alternativa para derribar las barreras, conscientes e inconscientes, y la desinformación generadoras de una sociedad no donante que se niega una posibilidad de vida a sí misma.

Espectáculos cortesanos en la América española del siglo XVII : las fiestas como caso para el análisis de la relación entre la Corte y la Corte virreinal

La Corte madrileña de los Austrias, al igual que el resto de las monarquías europeas del siglo XVII, generó una variada gama de fiestas públicas y privadas, como por ejemplo teatro musical, mascaradas y procesiones callejeras en las que desfilaban carros alegóricos con danzantes y músicos. Estos espectáculos no eran un mero entretenimiento sino que estaban destinados a resaltar las virtudes del monarca y a hacer conscientes a los espectadores del lugar que les cabía ocupar en esa sociedad recurriendo para ello a un complejo discurso simbólico. Las Cortes virreinales de América trasladaron a sus territorios estas prácticas que valían, fundamentalmente, para hacer presente la figura del rey y mantener viva la lealtad a la corona. Analizamos dos ejemplos de fiesta, una mascarada celebrada en Pausa (Perú) y un intermedio dramáticomusical en Sucre, que nos revelan la forma de pensamiento, las conductas y la organización de la sociedad cortesana virreinal.

Construcciones científicas del teatro: la pregunta epistemológica en los estudios teatrales

Resumen: El artículo afirma que en la Teatrología argentina de los últimos años ha crecido la conciencia y la responsabilidad de los investigadores respecto de la pregunta epistemológica. Se llama base epistemológica para el estudio teatral a la elección de las condiciones de conocimiento que determinan los marcos, las capacidades y las limitaciones teóricas, metodológicas, historiológicas, analíticas, críticas y pedagógicas de un investigador ante su objeto de estudio. La determinación de la base epistemológica depende del posicionamiento consciente del investigador respecto de su relación científica con el teatro. El artículo afirma que diferentes líneas científicas construyen concepciones del teatro diferentes. Finalmente se describe la base epistemológica de la Filosofía del Teatro, disciplina de innovación en los estudios teatrales de la Argentina.

Aportes teóricos de la psicología cognitiva para la construcción de una nueva economía científica

Resumen: El presente ensayo teórico se orienta a revisar las concepciones de sujeto de uno de los sistemas teóricos de economía-política que han tenido mayor influencia hasta el presente. El padre del liberalismo (Adam Smith) sustentó una teoría de sujeto cartesiano (moderno), es decir, un verdadero sapiens sapiens racional y autoconsciente. A través de la psicología cognitiva, los Premios Nobel en economía Kanheman y Tversky presentan una nueva variante de homoeconomicus, enriquecida con aportes de la ciencia experimental, modificando sustancialmente aquella vieja concepción de hombre como ser racional que signó casi todo el pensamiento moderno. Dadas estas “recientes revisiones” teórico-metodológicas, gestadas a la luz de la denominada ciencia de la mente, es que se hace indispensable re-pensar las viejas nociones de sujeto que sirvieron de cimiento al sistema económico y político, antes citadas. Para tal fin, se propone efectuar una sinergia teórico-metodológica entre dos disciplinas científicas: la economía y la psicología. Dicho sincretismo podría proporcionar las bases para una nueva disciplina científica integradora, que muchos teóricos ya han denominado neuro-economía. Es por esto que en el presente trabajo se propone realizar una crítica fundamentada de una de las teorías económicas vigentes, haciendo principal hincapié en los supuestos psicológicos y antropológicos. Finalmente, se intenta re-pensar un nuevo modelo de homoeconomicus, articulando los principales supuestos de la economía actual con algunos de los aportes de la psicología cognitiva, la biología y las neurociencias cognitivas, que redunde en un nuevo paradigma integrador denominado psiconeuro- economía.