Contrasting Electronic Requirements for C-H Binding and C-H Activation in d(6) Half-Sandwich Complexes of Rhenium and Tungsten

A computational study of the interaction half-sandwich metal fragments (metal=Re/W, electron count=d(6)), containing linear nitrosyl (NO+), carbon monoxide (CO), trifluorophosphine (PF3), N-heterocyclic carbene (NHC) ligands with alkanes are conducted using density functional theory employing the hybrid meta-GGA functional (M06). Electron deficiency on the metal increases with the ligand in the order NHC < CO < PF3 < NO+. Electron-withdrawing ligands like NO+ lead to more stable alkane complexes than NHC, a strong electron donor. Energy decomposition analysis shows that stabilization is due to orbital interaction involving charge transfer from the alkane to the metal. Reactivity and dynamics of the alkane fragment are facilitated by electron donors on the metal. These results match most of the experimental results known for CO and PF3 complexes. The study suggests activation of alkane in metal complexes to be facile with strong donor ligands like NHC. (C) 2015 Wiley Periodicals, Inc.

Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

An elastic organic crystal, 2,6-dichlorobenzylidine-4-fluoro-3-nitroaniline (DFNA), which also shows thermosalient behavior, is studied. The presence of these two distinct properties in the same crystal is unusual and unprecedented because they follow respectively from isotropy and anisotropy in the crystal packing. Therefore, while both properties lead from the crystal structure, the mechanisms for bending and thermosalience are quite independent of one another. Crystals of the low-temperature (a) form of the title compound are bent easily without any signs of fracture with the application of deforming stress, and this bending is within the elastic limit. The crystal structure of the a-form was determined (P2(1)/c, Z = 4, a = 3.927(7) angstrom, b = 21.98(4) angstrom, c = 15.32(3) angstrom). There is an irreversible phase transition at 138 degrees C of this form to the high-temperature beta-form followed by melting at 140 degrees C. Variable-temperature X-ray powder diffraction was used to investigate the structural changes across the phase transition and, along with an FTIR study, establishes the structure of the beta-form. A possible rationale for strain build-up is given. Thermosalient behavior arises from anisotropic changes in the three unit cell parameters across the phase transition, notably an increase in the b axis parameter from 21.98 to 22.30 angstrom. A rationale is provided for the existence of both elasticity and thermosalience in the same crystal. FTIR studies across the phase transition reveal important mechanistic insights: (i) increased pi...pi repulsions along 100] lead to expansion along the a axis; (ii) change in alignment of C-Cl and NO2 groups result from density changes; and (iii) competition between short-range repulsive (pi...pi) interactions and long-range attractive dipolar interactions (C-Cl and NO2) could lie at the origin of the existence of two distinctive properties.

Halogen Bonding and Chalcogen Bonding in 4,7-Dibromo-5, 6-dinitro-2,1,3-benzothiadiazole

An organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole, has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystallizing in a non-centrosymmetric space group (Z' = 1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (Z' = 2). Topological analysis based on QTAIM clearly brings out the dominance of the chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms.

Synthesis of Novel Benzofuran-Gathered C-2,4,6-substituted Pyrimidine Derivatives Conjugated by Sulfonyl Chlorides: Orally Bioavailable, Selective, Effective Antioxidants and Antimicrobials Drug Candidates

In the present study, we have made an effort to develop the novel synthetic antioxidants and antimicrobials with improved potency. The novel benzofuran-gathered C-2,4,6-substituted pyrimidine derivatives 5a, 5b, 5c, 5d, 5e, 5f, 6a, 6b, 6c, 6d, 6e, 6f, 7a, 7b, 7c, 7d, 7e, 7f, 8a, 8b, 8c, 8d, 8e, 8f, 9a, 9b, 9c, 9d, 9e, 9f were synthesized by simple and efficient four-step reaction pathway. Initially, o-alkyl derivative of salicylaldehyde readily furnish corresponding 2-acetyl benzofuran 2 in good yield, upon the treatment with potassium tertiary butoxide in the presence of molecular sieves. Further, Claisen-Schmidt condensation with aromatic aldehydes via treatment with thiourea followed by coupling reaction with different sulfonyl chlorides afforded target compounds. The structures of newly synthesized compounds were confirmed by IR, H-1 NMR, C-13 NMR, mass, and elemental analysis and further screened for their antioxidant and antimicrobial activities. The results showed that the synthesized compounds 8b, 8e, 9b, and 9e produced significant antioxidant activity with 50% inhibitory concentration higher than that of reference, whereas compounds 7d and 7c produced dominant antimicrobial activity at concentrations 1.0 and 0.5mg/mL compared with standard Gentamicin and Nystatin, respectively.

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.

Synthesis and unexpected reactivity of Ru(eta(6)-cymene)Cl-2(PPh2Cl)], leading to Ru(eta(6)-cymene)Cl-2(PPh2H)] and Ru(eta(6)-cymene)Cl-2(PPh2OH)] complexes

The reaction of Ru(eta(6)-cymene)Cl-2](2) and PPh2Cl in the ratio 1:2 gives a stable Ru(h(6)-cymene) Cl-2(PPh2Cl)] complex. Attempts to make the cationic Ru(eta(6)-cymene)Cl(PPh2Cl)(2)]Cl with excess PPh2Cl and higher temperatures led to adventitious hydrolysis and formation of Ru(eta(6)-cymene)Cl-2(PPh2OH)]. Attempts to make a phosphinite complex by reacting Ru(eta(6)-cymene)Cl-2](2) with PPh2Cl in the presence of an alcohol results in the reduction of PPh2Cl to give Ru(eta(6)-cymene)Cl-2(PPh2H)] and the expected phosphinite. The yield of the hydride complex is highest when the alcohol is 1-phenyl-ethane-1,2-diol. All three half-sandwich complexes are characterized by X-ray crystallography. Surprisingly, the conversion of chlorodiphenylphosphine to diphenylphosphine is mediated by 1-phenyl-ethane-1,2-diol even in the absence of the ruthenium half-sandwich precursor.

The 2014 M-w 6.1 Bay of Bengal, Indian Ocean, Earthquake: A Possible Association with the 85 degrees E Ridge

Oceanic intraplate earthquakes are known to occur either on active ridge-transform structures or by reactivation of their inactive counterparts, generally referred to as fossil ridges or transforms. The Indian Ocean, one of the most active oceanic intraplate regions, has generated large earthquakes associated with both these types of structures. The moderate earthquake that occurred on 21 May 2014 (M-w 6.1) in the northern Bay of Bengal followed an alternate mechanism, as it showed no clear association either with active or extinct ridge-transform structures. Its focal depth of >50 km is uncommon but not improbable, given the similar to 90 Ma age of the ocean floor with 12-km-thick overlying sediments. No tectonic features have been mapped in the near vicinity of its epicenter, the closest being the 85 degrees E ridge, located similar to 100 km to its west, hitherto regarded as seismically inactive. The few earthquakes that have occurred here in the past are clustered around its southern or northern limits, and a few are located midway, at around 10 degrees N. The 2014 earthquake, sourced close to the northern cluster, seems to be associated with a northwest-southeast-oriented fracture, located on the eastern flanks of the 85 degrees E ridge. If this causal association is possible, we believe that reactivation of fossil hotspot trails could be considered as another mechanism for oceanic intraplate seismicity.

Direct Numerical Simulation of a Spatially Evolving Supersonic Turbulent Boundary Layer at Ma=6

Direct numerical simulation is carried out for a spatially evolving supersonic turbulent boundary layer at free-stream Mach number 6. To overcome numerical instability, the seventh-order WENO scheme is used for the convection terms of Navier-Stokes equations, and fine mesh is adopted to minimize numerical dissipation. Compressibilty effects on the near-wall turbulent kinetic energy budget are studied. The cross-stream extended self-similarity and scaling exponents including the near-wall region are studied. In high Mach number flows, the coherence vortex structures are arranged to be smoother and streamwised, and the hair-pin vortices are less likely to occur.

The Effect of Conical Flowfields on the Performance of Waveriders at Mach 6

The performance of 23 kinds of waveriders, derived from different conical flowfields, is analyzed by the numerical computation under the conditions of fight speed of Mach 6, attack angle of 0° and flight altitude of 30 km. These results indicate that the performance is influenced by the shapes and the width to height ratios (W/H ) of generating cones. The geometrical parameter and the lift coefficient are proportional to W/H, while the drag coefficient and the lift to drag ratio (L/D ) have extreme values. Considering the base drag and the computation errors, the waverider with the highest L/D is cut from the elliptical cone’s flowfield (W/H = 1.5―1.618), and the configuration with the lowest drag can also be obtained at W/H = 1:1.5. Accordingly, good suggestions are proposed for practical design based on these computational results.

Estudio epidemiológico de la prevalencia e identificación de parásitos gastrointestinales en terneros de 2 a 6 meses de edad del municipio de San Pedro de Lóvago - Chontales

El presente estudio se realizó con el objetivo determinar la prevalencia e identificación de los principales parásitos gastrointestinales en terneros de 2 a 6 meses de edad en las fincas del Municipio de San Pedro de Lóvago – Chontales, El municipio se localiza entre las coordenadas 12º 07 ́ latitud norte y 85º07 ́ latitud oeste. La altitud promedio es de 340 msnm. La temperatura promedio anual oscila entre los 25 y 26ºC; su precipitación pluvial varía entre los 1,200 y 1,400mm al año. Para determinar el tamaño de la muestra se utilizó la formula de Martinet al.(1987) y Trusfield, (1995) donde plantean que N = 1,962* p *q / L 2, donde p es la prevalencia, q = 1–p y L especifica el límite deseado de error de la prevalencia. Se espera que la prevalencia (p) de 50% sea usada en combinación con él límite deseado de error de 14%, si la prevalencia en la población entera es desconocida. El tamaño requerido de la muestra de éste trabajo, fue de 84 fincas examinando el 20% de los terneros de cada población de toda la zona en estudio. Los resultados obtenidos, se identificaron dos géneros de parásitos. De los cuales 1 es de La Clase Protozoario y 1 de La Clase Nematodo, entre ellos se encontró al género Strongyloides spp y Coccideas spp, por orden de importancia y presentación. De un total de 84 fincas estudiadas, se examinaron 646 animales, obteniéndose 183 animales positivos representando el 28.3 % de prevalencia y 463 negativos para un 71.7% respectivamente. De los 183 animales que resultaron positivos se encontró que 27 animales presentaban el género Coccideas spp representando un nivel medio de infestacion 405 hpg y 156 animales con el género Strongyloides spp representando un nivel medio de infestacion de 385hpg.

Efecto de diferentes niveles de nitrógeno, fraccionamientos y momentos de aplicación sobre el crecimiento y rendimiento del maíz (Zea mays L.) var. NB-6

Con la finalidad de determinar le influencia de dos niveles de nitrógeno (50 y 100 kilogramos por hectárea), dos fraccionamientos (25-75 y 50-50 por ciento del fertilizante aplicado) y dos momentos de aplicación (0-16 y 0-32 días después de la siembra) sobre el crecimiento y rendimiento del maíz (Zea Mays L.) var NB-6, se realizó de Junio a Octubre de 1989 un experimento utilizando el diseño trifactorial más un testigo absoluto en arreglo de Bloques Completos al Azar con cinco repeticiones en le hacienda “Las Mercedes”, Managua, cuyos suelos pertenecen e la serie ”La Calera" y poseen un drenaje pobre, son negros y superficiales, además tienen lenta permeabilidad. Los resultados obtenidos demuestran que la aplicación de los diferentes niveles de nitrógeno y fraccionamientos no produjeron diferencies significativas sobre el rendimiento y sus componentes principales, sin embargo los momentos de aplicación analizados muestran efecto significativos sobre el rendimiento y algunos de sus principales Componentes El efecto de las interacciones fue no significativo sobre el rendimiento, no obstante se determinó que el rendimiento era mayor utilizando un nivel de 50 kilogramos de nitrógeno por hectárea, fraccionado en un 25 por ciento al momento de la siembra, y 75 por ciento 32 días después de la misma

Evaluación de diferentes niveles de rastrojo, métodos y densidades de siembra, en el cultivo del maiz (Zea mays L.) variedad NB-6

El presente estudio se estableció en terrenos del Centro Experimental La Compañía, ubicado en el municipio de San Marcos departamento de Carazo a una altura de 480 msnm a 11”51 latitud norte y 86”11 latitud Oeste, durante la época de primera que comprende desde el mes de Junio hasta el mes de octubre de 1996, con precipitaciones promedios de 1 400 mm anuales y temperaturas promedio de 24 grados Celcius (INETER, 1996). Esto con el objetivo de evaluar la sembradora combinada PROMECH con el arado egipcio en dos densidades de siembra (50 mil y 65 mil plantas por hectárea), y tres niveles de rastrojo (0.3 y 5 toneladas por hectárea), en el cultivo de maíz (Zea mays, L.) variedad NB-6, se utilizó un diseño de Bloques completamente al azar (BCA), en tres repeticiones. De los resultados obtenidos se observó que el mayor número de plántulas emergió en los tratamientos donde se trabajó con 5 t/ha de rastrojo, con el uso de la Sembradora Combinada y con densidad poblacional de 65 000 plantas /ha con un promedio de 64 291 plantas /ha, el mayor diámetro del tallo se encontró en los tratamientos donde se trabajó con niveles de 3 t/ha de rastrojo, utilizando la sembradora combinada y con densidad poblacional de 50 000 plantas /ha, con un promedio de 2,88 cm de diámetro, el menor número de plantas acamadas se encontró en los tratamientos donde se aplicó 3 t/ha de rastrojo, la sembradora Combinada y densidad poblacional de 50 000 plantas/ha, con un promedio de 2 519 plantas acamadas por hectárea, el mayor número de mazorcas cosechadas se obtuvo con la aplicación de 3 t/ha de rastrojo, utilizando la sembradora combinada y con densidad poblacional de 65 000 plantas /ha, con un promedio de 58 772 mazorcas/ha; la mayor cantidad de biomasa seca (5 41 t/ha), se obtuvo en los tratamientos con aplicación de 3 t/ha de rastrojo, usando la sembradora combinada y con densidad poblacional de 65 000 plantas/ha, el mayor rendimiento (1 439.6 kg/ha) se obtuvo en la tratamientos donde se aplicó la interacción 3 t/ha de rastrojo, usando la sembradora combinada y con densidad poblacional de 50 000 plantas/ha

GaN-based LEDs grown on 6-inch diameter Si (111) substrates by MOVPE

The issues and challenges of growing GaN-based structures on large area Si substrates have been studied. These include Si slip resulting from large temperature non-uniformities and cracking due to differential thermal expansion. Using an A1N nucleation layer in conjunction with an AlGaN buffer layer for stress management, and together with the interactive use of real time in-situ optical monitoring it was possible to realise flat, crack-free and uniform GaN and LED structures on 6-inch Si (111) substrates. The EL performance of processed LED devices was also studied on-wafer, giving good EL characteristics including a forward bias voltage of ∼3.5 V at 20 mA from a 500 μm × 500 μm device. © 2009 SPIE.

Efecto de tres niveles de nitrógeno y tres densidades poblacionales sobre el crecimiento, desarrollo y rendimiento en el cultivo de maiz (Zea mays L) Var. NB-6

El presente estudio se estableció durante la época de postrera de 1998, en la hacienda experimental El "Plantel" ubicado a 200 msnm, 12' 03' Latitud Norte y 86° 06' Longitud Oeste, con el objetivo de determinar el efecto de tres niveles de nitrógeno (60, 90, 120 kg/ha) y tres densidades de siembra (56 000, 71 000 y 85000 plantas/ha) sobre el crecimiento, desarrollo y rendimiento del cultivo de maíz (Zea mays L). Var. NB-6. El diseño experimental utilizado fue un bifactorial con arreglo de bloques completamente al azar (BCA), cuatro repeticiones realizando un análisis de varianza (ANDEVA) y separación de medias por Duncan con a= 0.05. Los resultados demuestran que hubo diferencia significativa para los factores en estudio en las variables de crecimiento (altura y diámetro del tallo). El factor nitrógeno presento diferencia significativa para la variable de rendimiento de grano obteniéndose los mejores resultados con los niveles de 90 y 120 kg/ha alcanzando promedios de 6 378 y 6 672.40 kg/ha, también el factor densidad mostró diferencia significativa en él número de plantas cosechadas y mazorcas cosechadas que son un componente importante para el rendimiento del cultivo. Los resultados del análisis económico demuestran que la mejor tasa de retomo marginal es de 539.15 % y se obtuvo con el tratamiento (90 kg/N. ha y 71 000 plantas /ha).