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.

Evaluación productiva y reproductiva de la raza holstein friesian canadiense bajo explotación intensiva en el trópico seco de Nicaragua

El presente trabajo se realizó en base a los registros productivos y reproductivos del hato Holstein. Friesian Canadiense existente en el distrito tres de la Empresa Genética "Roberto Alvarado" (Chiltepe); ubicada en el Departamento de Managua, Nicaragua, a una latitud 12º 14' y una longitud de 86º 25' y a una elevación promedio de 49 msnm, con una temperatura promedio anual de 28.43°C, humedad relativa promedio anual 68.38% y una precipitación promedio anual de 87.72 mm. distribuida en dos épocas: Época lluviosa (Mayo - Octubre ) y época seca (Noviembre - Abril). A partir de la información proporcionada se evaluó el efecto de distintos factores ambientales : número de partos (NUMPA), época de parto (EPOCA) y año de parto (AP); sobre las variables productivas y reproductivas: producción de leche total (PLT), duración de la lactancia (DL), producción de leche diaria (PLD), intervalo entre partos (IEP) y producción de leche por día de intervalo entre partos (PLDIEP), las cuales resultaron todas altamente significativas (P < 0.01), considerando para la variable PLT el efecto de la covariable DL con Numpa. También se caracterizó el comportamiento productivo y reproductivo del hato, basado en el cálculo de los promedios de mínimos cuadrados de las características productivas y reproductivas en los diferentes niveles de cada uno de los factores estudiados, resultando promedios generales de: PLT 3,207.53 ± 54.37 Kg., DL 321.98 ± 3.89 días, PLD 10.67 ± 0.17 Kg., IEP 468;63 ± 4.29 días y PLDIEP 7.51 ± 0.14 Kg. Además se estimaron las correlaciones lineales fenotípicas entre las variables y los factores NUMPA y EPAR , resultando entre ellos los valores más altos para: EPAR -NUMPA (r= + 0.96), DL - IEP (r= + 0.80), PLD - PLDIEP (r= + 0.80), PLT - PLDIEP (r= + 0.76) y valores absolutos para r más bajos entre NUMPA - PLDIEP (r= + 0.18), NUMPA - PLT (r= -0.19), NUMPA - PLD (r= + 0.23) y EPAR - PLT (r= - 0.21).

Efecto de diferentes niveles de aplicación nitrogenada en la producción de semilla de pasto gamba (Andropogon gayanus kunth var, CIAT 621)

En la presente investigación se evaluó los efectos de cuatro diferentes niveles de fertilización nitrogenada (O; 25; 50; 75 y 100 Kg N/ha), sobre la producción de semilla de Andropogon gayanus Kunth como una alternativa para los productores de la zona de Masatepe. El ensayo se realizó de Junio a Diciembre de 1994, en la finca "Santa Juana" municipio de Masatepe departamento de Masaya. Localizada a 11° 53' latitud norte y 86° 08' longitud oeste, a 470 m.s.n.m., con una precipitación promedio anual de 1,849.3 mm, humedad relativa de 83.6% y una temperatura media anual de 24°C. Se utilizó un diseño experimental de Bloques Completos al Azar (BCA), con cuatro repeticiones. Las parcelas útiles fueron de 3 x 4m2 y como variable respuesta se determinó la producción de semilla cruda, semilla pura ajustada y porcentaje de germinación. Se realizó un corte de uniformidad dejando el pasto a una altura de 20 cm al raz del suelo. A los 20 días después se procedió a aplicar en una sola dosis, los diferentes niveles de fertilización. El tratamiento con 50 kg N/ha fue seleccionado por obtener los mayores beneficios en relación al gasto. Siendo por tal razón el más idóneo para la producción de semilla del Andropogon gayanus, para el sector evaluado, alcanzando 479.21 Kg/ha de semilla pura ajustada. La no significancia entre los tratamientos de fertilización se atribuyó, posiblemente a la heterogeneidad del suelo, el alto contenido de minerales y de materia orgánica. Sin embargo, el experimento demostró la adaptabilidad de Andropogon gayanus a las características del suelo, climatología de la zona.

Influencia de diferentes periodos de destete en conejas primiparas en el municipio de Diriamba, Departamento de Carazo, Nicaragua

Este trabajo fue realizado en la Quinta "Myriam", ubicada en el municipio de Diriamba, departamento de Carazo, Nicaragua, propiedad del Dr. Jorge Ferreira. La ubicación geográfica del municipio está comprendida entre los 11° 50' y 12° 00' de Latitud Norte y entre los 86° 00' y 86° 15' de Longitud Oeste, cuenta con una elevación de 551 m.s.n.m., los datos meteorológicos de la zona en los últimos cuatro años (90-93) en cuanto a temperatura, humedad relativa y precipitación promedio fueron: 23.8 °C, 84% y 1184,5 mm respectivamente, (INETER, Departamento de Estadística, 1993). En el presente ensayo, se utilizó un diseño estadístico completamente aleatorizado (DCA), mediante el cual se evaluó el efecto de 3 tratamientos (15, 30 y 45 días de destete) sobre las variables Peso de la Camada al Destete (PCD), Peso de la Madre al Destete (PMD), Peso de la Madre al Segundo Parto (PSP), Ganancia Media Diaria del Parto 1 al Parto 2 (GMDp 1.P2) , con 4 repeticiones por tratamiento, éstas repeticiones estuvieron constituidas por conejas primíparas, las cuales tuvieron un peso que osciló entre 3 - 3.18 kg. y edad homogénea de 7 meses. Las variables fueron sometidas a la prueba de Duncan para determinar la superioridad en rango por tratamiento. Mediante el análisis de varianza se encontró que el efecto de los tratamientos resultó ser altamente significativo sobre la variable Peso de la Camada al Destete (PCD) (P0.01), significativo sobre las variables Peso de la Madre al Segundo Parto (PSP) y Ganancia Media Diaria del Parto 1 al Parto 2 (GMD p 1.P2) (P0.1) y no significativo sobre la variable Peso de la Madre al Destete (PMD) (NS). El efecto de la covariable Peso al Primer Parto (P1P) resultó ser altamente significativo sobre las variables Peso de la Madre al Destete (PMD) y Peso de la Madre al Segundo Parto (PSP) (P0.01). Después de someter las variables a la prueba de DUNCAN se encontraron los siguientes promedios por tratamiento: Peso de la Camada al Destete (PCD) ; T.15 días 1.538 kg P.V.(C), T.30 días 3.360 kg P.V. (B), T.45 días 4.523 kg P.V. (A), Peso de la Madre al Destete (PMD); T.15 días 3.649 kg P.V. (A) T.30 días 3.549 kg P.V. (A), T.45 dias 3.493 kg P.V.(A). Peso de la Madre al Segundo Parto (PSP); T.15 días 3. 449 kg P.V. (B), T.30 días 3.628 kg P.V. (AB), T.45 días 3.777 kg P.V.(A). Ganancia Media Diaria del Parto 1 al Parto 2 (GMD p 1.P2) T .15 días (2.071 g (B), T.30 días 2.718 g (AB), T.45 días 2. 975 g (A). Los promedios y desviaciones standard para las variables Ganancia Media Diaria del Parto 1 al Destete 1 (GMDp1-D1)y Ganancia Media Diaria del Destete l al Parto 2 (GMDD1.P2) por tratamiento fueron: GMD P1-D1; T.l5 días 3.84 g ± 0.50 g, T.30 días 2.54 g ± 0.64 g, T.45 días 2.37 g ± 0.72 g. GMD D1-P2; T.l5 días 2.26 g ± 0.54 g, T.30 días 3.17 g ± 0.74 g, T.45 días 3.93 g ± 0.28 g. Se encontró que el alimento tipo único suministrado a los animales bajo experimentación, cumplió con los requerimientos nutricionales de la especie estudiada. Los costos encontrados por hembra, por tratamiento, fueron C$ 197.21 destete de 15 días, C$ 220.28 destete de 30 días, C$ 243 .1.4 destete de 45 días. Los costos por gazapo destetado fueron de C$ 5.48 destete de 15 días, C$ 6.12 destete de 30 días, C$ 8.10 destete de 45 días.