Nucleophilic attacks of 1,2-diaminoethane on MeCN ligands: synthesis, x-ray structure, and spectral and electrochemical properties of [Ru(.mu.-O)(.mu.-O2CAr)2[NH2CH2CH2NHC(Me)NH]2(PPh3)2](ClO4)2(Ar = C6H4-p-X; X = H, Me, OMe, Cl)

The diruthenium(III) complex [Ru2O(O2CAr)2(MeCN)4(PPh3)2](ClO4)2 (1), on reaction with 1,2-diaminoethane (en) in MeOH at 25-degrees-C, undergoes nucleophilic attacks at the carbon of two facial MeCN ligands to form [(Ru2O)-O-III(O2CAr)2-{NH2CH2CH2NHC(Me)NH}2(PPh3)2](ClO4)2 (2) (Ar = C6H4-p-X, X = H, Me, OMe, Cl) containing two seven-membered amino-amidine chelating ligands. The molecular structure of 2 with Ar = C6H4-p-OMe was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.942 (5) angstrom, b = 14.528 (2) angstrom, c = 21.758 (6) angstrom, alpha = 109.50 (2)-degrees, beta = 92.52 (3)-degrees, gamma = 112.61 (2)-degrees, V = 3759 (2) angstrom 3, and Z = 2. The complex has an {Ru2(mu-O)(mu-O2CAr2)2(2+)} core. The Ru-Ru and average Ru-O(oxo) distances and the Ru-O-Ru angle are 3.280 (2) angstrom, 1.887 [8] angstrom, and 120.7 (4)-degrees, respectively. The amino group of the chelating ligand is trans to the mu-oxo ligand. The nucleophilic attacks take place on the MeCN ligands cis to the mu-oxo ligand. The visible spectra of 2 in CHCl3 display an absorption band at 565 nm. The H-1 NMR spectra of 2 in CDCl3 are indicative of the formation of an amino-amidine ligand. Complex 2 exhibits metal-centered quasireversible one-electron oxidation and reduction processes in the potential ranges +0.9 to +1.0 V and -0.3 to -0.5 V (vs SCE), respectively, involving the Ru(III)2/Ru(III)Ru(IV) and Ru(III)2/Ru(II)Ru(III) redox couples in CH2Cl2 containing 0.1 M TBAP. The mechanistic aspects of the nucleophilic reaction are discussed.

Inverse surface melting in confined clusters: Ar-13 in zeolite L

Monte Carlo and molecular dynamics simulations on an Ar-13 cluster in zeolite L have been carried out at a series of temperatures to understand the rigid-nonrigid transition corresponding to the solid-liquid transition exhibited by the free Ar-13 cluster. The icosahedral geometry of the free cluster is no longer preferred when the cluster is confined in the zeolite. The root-mean-squared pair distance fluctuation, delta, exhibits a sharp, well-defined rigid-nonrigid transition at 17 K as compared to 27 K for the free cluster. Multiple peaks in the distribution of short-time averages of the guest-host interaction energy indicate coexistence of two phases.; It is shown that this transition is associated with the inner atoms becoming mobile at 17 K even while the outer layer atoms, which are in close proximity to the zeolitic wall, continue to be comparatively immobile. This may be contrasted with the melting of large free clusters of 40 or more atoms which exhibit surface melting. Guest-host interactions seem to play a predominant role in determining the properties of confined clusters. We demonstrate that the volume of the cluster increases rather sharply at 17 and 27 K respectively for the confined and the free cluster. Power spectra suggest that the motion of the inner atoms is generally parallel to the atoms which form the cage wall.

Microwave Spectroscopic and Atoms in Molecules Theoretical Investigations on the ArPropargyl Alcohol Complex: ArHO, Ar, and ArC Interactions

The structure of the Arpropargyl alcohol (ArPA) complex is determined from the rotational spectra of the parent complex and its two deuterated isotopologues, namely ArPA-D(OD) and ArPA-D(CD). The spectra confirm a geometry in which PA exists in the gauche form with Ar located in between OH and CCH groups. All a, b and c types of transitions show small splitting due to some large-amplitude motion dominated by COH torsion, as in the monomer. Splittings in a- and b-type transitions are of the order of a few kilohertz, whereas splitting in the c-type transitions is relatively larger (0.92.6 MHz) and decreases in the order ArPA>ArPA-D(CD)>ArPA-D(OD). The assignments are well supported by ab initio calculations. Atoms in molecules (AIM) and electrostatic potential calculations are used to explore the nature of the interactions in this complex. AIM calculations not only reveal the expected OHAr and Ar interactions in the Argauche-PA complex, but also novel CAr (of CH2OH group) and OHAr interactions in the Artrans-PA complex. Similar interactions are also present in the Armethanol complex.

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Performance study of a cesium iodide photocathode-based UV photon detector in Ar/CH4 mixture

The detection efficiency of a gaseous photomultiplier depends on the photocathode quantum efficiency and the extraction efficiency of photoelectrons into the gas. In this paper we have studied the performance of an UV photon detector with P10 gas in which the extraction efficiency can reach values near to those in vacuum operated devices. Simulations have been done to compare the percentage of photoelectrons backscattered in P10 gas as well as in the widely used neon-based gas mixture. The performance study has been carried out using a single stage thick gas electron multiplier (THGEM). The electron pulses and electron spectrum are recorded under various operating conditions. Secondary effects prevailing in UV photon detectors like photon feedback are discussed and its effect on the electron spectrum under different operating conditions is analyzed. (C) 2014 Chinese Laser Press

The cellular structure of a two-dimensional H2/O2/Ar detonation wave

In this paper, the cellular structure of a two-dimensional detonation wave in a low pressure H2/O2/Ar mixture calculated with a detailed chemical reaction model, high order scheme and high resolution grids is investigated. The regular cellular structure is produced about 1 ms after introducing perturbations in the reaction zone of a steady one-dimensional detonation wave. It is found from the present resolution study that the discrepancies concerning the structure type arising from the coarser grid employed can be resolved using a sufficiently fine grid size of 0.05 mm and below and shows a double-Mach-like strong-type configuration. During the structure evolution process, the structure configuration does not change much in the periods before and after the triple point collision. Through the triple point collision, three regular collision processes are observed and are followed by a quick change to the double-Mach-like configuration. The simulated structure tracks show that there are three different tracks associated with different triple points or the kink on the transverse wave. Comparisons with previous work and experiments indicate the presence of a strong structure for an ordinary detonation.

The Structure and Evolution of a Two-Dimensional H2/O2/Ar Cellular Detonation

This paper reports on two-dimensional numerical simulation of cellular detonation wave in a / / mixture with low initial pressure using a detailed chemical reaction model and high order WENO scheme. Before the final equilibrium structure is produced, a fairly regular but still non-equilibrium mode is observed during the early stage of structure formation process. The numerically tracked detonation cells show that the cell size always adapts to the channel height such that the cell ratio is fairly independent of the grid sizes and initial and boundary conditions. During the structural evolution in a detonation cell, even as the simulated detonation wave characteristics suggest the presence of an ordinary detonation, the evolving instantaneous detonation state indicates a mainly underdriven state. As a considerable region of the gas mixture in a cell is observed to be ignited by the incident wave and transverse wave, it is further suggested that these two said waves play an essential role in the detonation propagation.

Influencia de las condiciones del estrés salino sobre un cultivar resistente y un cultivar susceptible de Lotus tenuis al estado vegetativo

Resumen: Lotus tenuis es una leguminosa perenne, naturalizada en los campos bajos de la Cuenca del Salado. Es una especie alógama y presenta una alta variabilidad genética (Andrés A., and Rosso 2007), que le permite crecer y desarrollarse en distintas condiciones ambientales (Goldberg, E.E. et al 2010). Son pocas las especies de relevancia agrícola capaces de crecer bajo condiciones que combinan inundación y salinidad (Escaray 2007). Se ha demostrado la existencia de poblaciones de L. tenuis con diferentes niveles de tolerancia a distintos niveles de inundación y salinidad (Teakle, N.L. et al 2010; Striker et al. 2012). La tolerancia a la salinidad se define como la habilidad de una planta para crecer y completar su ciclo de vida en un medio que contiene altas concentraciones de sal. Debido a esto surgió mi interés por profundizar en el estudio de esta especie y su posible adaptación a suelos con problemas de salinidad. Se trabajo con dos familias de medios hermanos (FMH) de L. tenuis caracterizadas como tolerantes o susceptibles a salinidad provenientes del programa de mejoramiento genético del INTA Pergamino. Se utilizaron 550 plantas de cada genotipo que fueron sometidas a dos tratamientos salinos. Las plantas se colocaron de a cinco en macetas (20 cm. de diámetro) en invernáculo, se las dividió en: dosis 1 (9 repeticiones), fueron regadas con una solución 75mM de cloruro de sodio (NaCl), dosis 2 (9 repeticiones) regadas con una solución 150 mM NaCl, y un grupo testigo control para cada genotipo (4 repeticiones) regado sin NaCl. El tratamiento salino se aplicó durante 62 días hasta la aparición de la primera flor. Se determinó producción de biomasa de parte aérea (tallos mas hojas). También se determinó porcentaje de materia seca, por secado a 65ºC hasta peso constante de tallo más hojas, corona más raíz, longitud de tallo y raíz, y número de ramificaciones del tallo. Los resultados analizados muestran que la FMH 490 o tolerante posee mayor desarrollo en todas las variables analizadas y en todas las condiciones ensayadas excepto en longitud de raíz y corona. Pero, al sufrir el estrés los porcentajes de reducción en esta FMH que se observan son similares a los porcentajes de reducción observados en la FMH 2241 e incluso, para algunas variables el genotipo susceptible 2241 presentaba menores pérdidas frente al estrés recibido (MS por planta corona y raíz, Biomasa por planta corona y raíz, largo de tallo y Grs de tallo por planta.). El efecto de la salinidad fue igual o similar entre ambas isolíneas, por lo que la que presentaba mayor crecimiento produjo mayor biomasa en condiciones de estrés salino que la de menor crecimiento. La tolerancia al estrés salino fue similar en ambos genotipos, solo que una presentó más desarrollo que la otra. El análisis de las variables estudiadas mostró que en este ensayo el crecimiento de las plantas tiende a disminuir al aumentar la dosis de NaCl y que, a igualdad de dosis, los parámetros de crecimiento evaluados fueron mayores en el genotipo tolerante.

La urna (1911) de Enrique Banchs : un cancionero argentino del siglo XX

Integran este número de la revista ponencias presentadas en Studia Hispanica Medievalia VIII : Actas de las X Jornadas Internacionales de Literatura Española Medieval, 2011, y de Homenaje al Quinto Centenario del Cancionero General de Hernando del Castillo.

Una investigación sobre los principios económicos de Juan Bautista Alberdi y sus vinculaciones con la tradición de la escuela austríaca

Resumen: El Dr. Juan Bautista Alberdi, abogado, jurista, periodista, tratadista de derecho comparado, constitucionalista, economista, legislador y político, es considerado una figura insoslayable en la inspiración de las instituciones políticas, sociales y económicas de la organización nacional de la República Argentina durante el siglo XIX. De hecho se lo sindica como la fuente primaria, principal y casi excluyente de la constitución de la República Argentina que fuera aprobada por el Congreso de 1853, si se toma a sus trabajos de derecho comparado,. Complementariamente, concibió un tratado sobre “El sistema económico y rentístico” que aconsejaba adoptar a la Confederación, en el cual se encuentra una gran cantidad de puntos de vista económicos que se pueden considerar muy relevantes al sistema económico a adoptar por la nación. Con posterioridad, en diferentes fechas, e incluso en forma póstuma, se dieron a conocer más trabajos suyos en los que abordaba cuestiones económicas importantes. Dada su formación, que puede considerarse anterior a la del fundador de la Escuela Austriaca, (ya que, aunque en cierto aspectos fueron contemporáneos, la vida de Alberdi se inicia y termina unos 30 años antes que la de Menger), y considerando la barrera del idioma y otras cuestiones que pueden separarlos, la idea de este trabajo es tratar de investigar sobre los puntos de contacto entre ambas corrientes del pensamiento. La intención de esta investigación es doble: Por un lado, abrir un camino de estudio y dar a conocer a otros ámbitos, el pensamiento del Genial Tucumano, y su vigencia en el tiempo. Por otro lado, y ya, de una mayor complejidad y dando lugar a mayor controversia, analizar otro aspecto. Esto es, si dada la actual revalorización del pensamiento austriaco, especialmente en lo relativo a su teoría del ciclo económico, por un lado, y la proverbial inestabilidad mostrada por la economía argentina, al menos en los últimos 80 años, se puede intentar, retornando a los valores Alberdianos rescatar un ordenamiento institucional, que por encontrarse en la esencia de su pensamiento y por ende ser absolutamente compatible con el espíritu fundacional de nuestra constitución, permita además un fortalecimiento institucional del funcionamiento económico argentino.