Metastable Phase Diagram of Nanocrystalline ZrO(2)-Sc(2)O(3) Solid Solutions

We have investigated the crystal structures and phase transitions of nanocrystalline ZrO(2)-1 to -13 mol % Sc(2)O(3) by synchrotron X-ray powder diffraction and Raman spectroscopy. ZrO(2)-Sc(2)O(3) nanopowders were synthesized by using a stoichiometric nitrate-lysine get-combustion route. Calcination processes at 650 and at 850 degrees C yielded nanocrystalline materials with average crystallite sizes of (10 +/- 1) and (25 +/- 2) nm, respectively. Only metastable tetragonal forms and the cubic phase were identified, whereas the stable monoclinic and rhombohedral phases were not detected in the compositional range analyzed in this work. Differently from the results of investigations reported in the literature for ZrO(2)-Sc(2)O(3) materials with large crystallite sizes, this study demonstrates that, if the crystallite sizes are small enough (in the nanometric range), the metastable t ``-form of the tetragonal phase is retained. We have also determined the t`-t `` and t ``-cubic compositional boundaries at room temperature and analyzed these transitions at high temperature. Finally, using these results, we built up a metastable phase diagram for nanocrystalline compositionally homogeneous ZrO(2)-Sc(2)O(3) solid solutions that strongly differs from that previously determined from compositionally homogeneous ZrO(2)-Sc(2)O(3), Solid solutions with much larger crystallite sizes.

NMR Chemical Shielding and Spin-Spin Coupling Constants of Liquid NH(3): A Systematic Investigation using the Sequential QM/MM Method

The NMR spin coupling parameters, (1)J(N,H) and (2)J(H,H), and the chemical shielding, sigma((15)N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard-Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the V(N,H) constants in the interval of -67.8 to -63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of -61.6 Hz. For the (2)J(H,H) coupling the theoretical results vary between -10.6 to -13.01 Hz. The indirect experimental result derived from partially deuterated liquid is -11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for (1)J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, U(15 N) Calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Delta sigma((15)N) is -25.2 ppm, in good agreement with the experimental value of -22.6 ppm.

Electric field gradients in (111)In-doped (Hf/Zr)(3)Al(2) and (Hf/Zr)(4)Al(3) mixed compounds: ab initio calculations, perturbed angular correlation measurements and site preference

The quadrupolar hyperfine interactions of in-diffused (111)In -> (111)Cd probes in polycrystalline isostructural Zr(4)Al(3) and Hf(4)Al(3) samples containing small admixtures of the phases (Zr/Hf)(3)Al(2) were investigated. A strong preference of (111)In solutes for the contaminant (Zr/Hf)(3)Al(2) minority phases was observed. Detailed calculations of the electric field gradient (EFG) at the Cd nucleus using the full-potential augmented plane wave + local orbital formalism allowed us to assign the observed EFG fractions to the various lattice sites in the (Zr/Hf)(3)Al(2) compounds and to understand the preferential site occupation of the minority phases by the (111)In atoms. The effects of the size of the supercell and relaxation around the oversized In and Cd probe atoms were investigated in detail.

X-ray spectrometry: a powerful tool for the measurement of complete fusion of weakly bound nuclei

We describe how the method of detection of delayed K x-rays produced by the electron capture decay of the residual nuclei can be a powerful tool in the investigation of the effect of the breakup process on the complete fusion (CF) cross-section of weakly bound nuclei at energies close to the Coulomb barrier. This is presently one of the most interesting subjects under investigation in the field of low-energy nuclear reactions, and the difficult experimental task of separating CF from the incomplete fusion (ICF) of one of the breakup fragments can be achieved by the x-ray spectrometry method. We present results for the fusion of the (9)Be + (144)Sm system. Copyright (c) 2008 John Wiley & Sons, Ltd.

Extended analysis of the Al-like argon spectrum

A new analysis of the aluminium-like five times ionized argon (Ar VI) spectrum in the vacuum ultraviolet region is reported in this paper. Two adjusted and 14 new energy levels and 68 new classified lines between the configurations 3s(2)3p, 3p(3), 3s3p3d, 3s(2)4p and 3s3p(2), 3s(2)(3d + 4d + 5d), 3s(2)5s, 3p(2)3d, 3s3d(2) were obtained. Atomic calculation using the HFR program was also used in the analysis.

Copper(II) and zinc(II) complexes with 2-formylpyridine-derived hydrazones

In the present work 2-formylpyridine-para-chloro-phenyl hydrazone (H2FopCIPh) and 2-formylpyridine-para-nitro-phenyl hydrazone (H2FopNO(2)Ph) were obtained, as well as their copper(II) and zinc(II) complexes [Cu(H2FopClPh)Cl(2)] (1), [Cu(2FopNO(2)Ph)Cl] (2), [Zn(H2FopClPh)Cl(2)] (3) and [Zn(H2FopNO(2)Ph)Cl(2)] (4). Upon re-crystallization in DMSO:acetone conversion of 2 into [Cu(2FopNO(2)Ph)Cl(DMSO)] (2a) and of 4 into [Zn(2FopNO(2)Ph)Cl(DMSO)] (4a) occurred. The crystal structures of 1, 2a, 3 and 4a were determined. (C) 2009 Elsevier Ltd. All rights reserved.

Structural studies on zinc(II) complexes with 2-benzoylpyridine-derived hydrazones

2-Benzoylpyridine-phenylhydrazone (H2BzPh), 2-benzoylpyridine-para-chloro-phenylhydrazone (H2BzpClPh), and 2-benzoylpyridine-para-nitro-phenyl (H2BzpNO(2)Ph) hydrazone were obtained and fully characterized, as well as their zinc(II) complexes [Zn(H2BzPh)Cl(2)] (1), [Zn(H2BzClPh)Cl(2)] (2) and [Zn(H2BzpNO(2)Ph)Cl(2)] (3). During the syntheses of complex 1 a second product crystallized, which was characterized as [Zn(2BzPh)(2)] (1a). Upon re-crystallization in 1: 9 DMSO: acetone conversion of 2 into [Zn(H2BzpClPh)Cl2] center dot H(2)O (2a) and of 3 into [Zn(2BzpNO(2)Ph)Cl(DMSO)] (3a) occurred. The crystal structures of 1a, 2a and 3a were determined. In 1a the two nearly perpendicular H2BzPh ligands give rise to a distorted octahedral environment around the metal. The 5-fold coordination around the metal is completed with two chloride ions in 2a and with one chloride and one oxygen atom from DMSO in 3a. (c) 2008 Elsevier B.V. All rights reserved.

Copper(II) and zinc(II) complexes with 2-benzoylpyridine-methyl hydrazone

2-Benzoylpyridine-methyl hydrazone (HBzMe) has been obtained as well as its copper(II) [Cu(HBzMe)Cl(2)] (1) and zinc(II) [Zn(HBzMe)Cl(2)] (2) complexes. Upon re-crystallization in 1 - 9 DMSO:acetone conversion of I into dimeric [Cu(BzMe)Cl](2) (1a) occurred. The crystal structures of HBzMe, 1, 1a, and 2 were determined. HBzMe adopts the ZE conformation in the solid. In all complexes the hydrazone adopts the E configuration to attach to the metal through the N(py)-N2-O chelating system. In 1 and 2 a neutral hydrazone coordinates to the metal center while in 1a deprotonation occurs with coordination of an anionic ligand. la presents a dimeric structure. having two copper(II) ions per asymmetric unit. Two chlorides are also present in the copper coordination sphere, which act as bridging ligands and connect the copper centers to each other. (C) 2008 Elsevier B.V. All rights reserved.

Religión y política entre los primeros cristianos : proyecciones de la nueva mentalidad en la patrística temprana

El artículo se compone de una introducción que examina el pasaje evangélico de Mc 12, 13-17 en relación con el pago de los impuestos, como la fuente sustancial de la arcaica problemática religioso-política cristiana. El tema de religión y política de intrínseca complejidad incluye el estudio de un documento gnóstico directo, el Tratado Tripartito (NHC I, 5), porque él encierra el vocabulario filosófico político usado por los primeros cristianos. El estudio del testimonio investigado es, además, de utilidad, porque permite analizar con superior tecnicismo la concepción político-religiosa de Pablo de Tarso y sus posibles aplicaciones a la cultura política cristiana en formación. Teniendo en cuenta este contexto es posible ir más a fondo en la captación del sentido del kath’ ékhon que aparece en la epístola deutero-paulina a los tesalonicenses (2 Tes. 2, 1-12) y la relación de este conjunto de conceptos político-religiosos con las ideas paralelas, aunque ambivalentes, acuñadas por los autores de las generaciones inmediatas, es decir, los Padres Apostólicos. Las conclusiones abordan las consecuencias que se pueden extraer de estos planteamientos antiguos que se han mantenido en el Medioevo, y su posible efectividad para el mejoramiento de la concepción cristiana actual de la política.

Análisis crítico de la controversia del uso de animales en las investigaciones científicas biomédicas

En los últimos años, se ha generado una enconada discusión por parte de grupos proteccionistas y entidades científicas vigentes respecto al uso de animales en el laboratorio. Si bien es cierto, que bajo la perspectiva actual la historia ha mostrado abusos y acciones denigrantes hacia los animales en la sociedad humana, el progreso de los conocimientos y el desarrollo de la bioética, ha generado actitudes más humanitarias con respecto a este tema. Los reclamos de estos grupos defensores de los animales han generado ideas distorsionadas respecto al uso de ellos en la investigación científica, en gran parte por el carácter dogmático de sus argumentos y por una visión limitada y en extremo estereotipada de la actividad científica de investigación. En la presente revisión, se consideran aspectos históricos de la relación hombre-animal; discusión del entorno y creencias de épocas remotas y su posterior evolución en el tiempo; análisis crítico de la publicación de Rusell y Burch como hito en la investigación científica humanizada a través de sus 3 R y la presentación de argumentos tan básicamente razonables que resulta hasta innecesaria cualquier justificación sobre la existencia de la actividad científica biológica en la humanidad.

Análisis bibliométrico de las publicaciones científicas argentinas en la categoría Agriculture, Multidisciplinary en la base de datos del Web of Science (1997-2009)

El propósito del trabajo ha sido caracterizar el área de Agriculture, Multidisciplinary en Argentina, revisándose a nivel institucional, a través de la base de datos Web of Science, los trabajos realizados por investigadores en Instituciones argentinas y publicados en revistas internacionales con factor de impacto entre 1997 y 2009. En el contexto deAmérica Latina, se han publicado 7795 trabajos de todos los tipos documentales y 7622 del tipo artículo o revisión en 49 revistas, y a nivel de Argentina se han encontrado 531 artículos o revisiones publicados en 31 revistas, la mayoría en inglés (80,23%), pero también en español (15,25%) y en portugués (4,33%). Por otro lado, se han analizado las Instituciones desde el punto de vista cuantitativo y cualitativo mediante diversos indicadores bibliométricos, como el Factor de Impacto Ponderado, el Factor de Impacto Relativo y la ratio número de citas frente a número de documentos, encontrándose que entre las instituciones más productivas destacan el Consejo Nacional de Investigaciones Científicas y Técnicas por el número de documentos y el Centro de Investigación y Desarrollo en Criotecnología de Alimentos por el Factor de Impacto Ponderado y por la ratio citas frente a documentos. Se observa una escasa colaboración internacional.