Synthesis, properties and crystal structures of diastereomeric areneruthenium(II) chiral Schiff-base complexes

Diastereomers (SRu,Sc)-1a and (RRu,Sc)-1b, in a ratio of 85: 15 and formulated as [Ru(η-MeC6H4Pri-p)Cl(L*)], have been prepared by treating [{Ru(η-MeC6H4Pri-p)Cl2}2] with the sodium salt of (S)-α-methylbenzylsalicylaldimine (HL*) in tetrahydrofuran at –70 °C. The reaction of 1(1a+1b) with AgClO4 in acetone followed by an addition of PPh3 or 4-methylpyridine (4Me-py) leads to the formation of adducts [Ru(η-MeC6H4Pri-p)(PPh3)(L*)]ClO42[(SRu,Sc)2a, (FRu,Sc)2b] and [Ru(η-MeC6H4Pri-p)(4Me-py)(L*)]ClO43[(SRu,Sc)3a, (RRu,Sc)3b] in the diastereomeric ratios (SRu,Sc) : (RRu,Sc) of 2 : 98 and 76 : 24, respectively. Complex 1 crystallises with equal numbers of 1a and 1b molecules in an asymmetric unit of monoclinic space group P21 with a= 10.854(1), b= 17.090(1), c= 12.808(4)Å, β= 110.51(1)°, and Z= 4. The structure was refined to R= 0.0552 and R′= 0.0530 with 2893 reflections having I[gt-or-equal] 1.5σ(I). The absolute configurations of the chiral centres in the optically pure single crystal of the PPh3 adduct have been obtained from an X-ray study. Crystals of formulation [Ru(η-MeC6H4Pri-p)-(PPh3)(L*)]2[ClO4][PF6]·1.5 CHCl3, obtained in presence of both ClO4 and PF6 anions, belong to the non-centric triclinic space group P1 with a= 10.852(2), b= 14.028(1), c= 15.950(2)Å, α= 91.51(1), β= 105.97(1), γ= 106.11(1)°, and Z= 2. The final residuals were R= 0.0713, R′= 0.0752 with 7283 reflections having I[gt-or-equal] 2.5σ(I). The crystal structures of 1a,1b, and the PPh3 adduct (2b,2b′) consist of a ruthenium(II) centre bonded to a η-p-cymene, a bidentate chelating Schiff base, and a unidentate ligand (Cl or PPh3). The chirooptical properties of the complexes have been studied using 1H NMR and CD spectral data. The presence of a low-energy barrier for the intermediate involved in these reactions, showing both retention as well as inversion of the metal configuration, is discussed.

Estimation of vapour pressure and partial pressure of subliming compounds by low-pressure thermogravimetry

A method for the estimation of vapour pressure and partial pressure of subliming compounds under reduced pressure, using rising temperature thermogravimetry, is described in this paper. The method is based on our recently developed procedure to estimate the vapour pressure from ambient pressure thermogravimetric data using Langmuir equation. Using benzoic acid as the calibration standard, vapour pressure temperature curves are calculated at 80, 160 and 1000 mbar for salicylic acid and vanadyl bis-2,4-pentanedionate, a precursor used for chemical vapour deposition of vanadium oxides. Using a modification of the Langmuir equation, the partial pressure of these materials at different total pressures is also determined as a function of temperature. Such data can be useful for the deposition of multi-metal oxide thin films or doped thin films by chemical vapour deposition (CVD).

Thermodynamics of NdRhO3 and phase relations in the system Nd-Rh-O

Phase equilibrium experiments indicate that NdRhO3 is the only ternary oxide in the system Nd-Rh-O at 1273 K; it has orthorhombically-distorted perovskite structure. By employing a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte, thermodynamic properties of NdRhO3 are determined. The standard Gibbs energy of formation of NdRhO3 from its component binary oxides in the temperature ranges from 900 to 1300 K can be expressed as: 1/2Rh(2)O(3) (ortho)+1/2Nd(2)O(3)(hex)=NdRhO3(ortho), Delta(f(o,x))G(0)/J mol(-1)( +/- 197) = - 66256+5.64 (T/K). The decomposition temperature of NdRhO3 computed from extrapolated thermodynamic data is 1803 (+/- 4) K in pure oxygen and 1692 (+/- 4) K in air at standard pressure. Oxygen partial pressure-composition diagram and three-dimensional chemical potential diagram at 1273 K are developed from thermodynamic data obtained in this study and auxiliary information from the literature. Equilibrium temperature-composition phase diagrams at constant oxygen partial pressures are also constructed. (C) 2013 Elsevier Ltd. All rights reserved.

Using intra-flock association patterns to understand why birds participate in mixed-species foraging flocks in terrestrial habitats

Bird species are hypothesized to join mixed-species flocks (flocks hereon) either for direct foraging or anti-predation-related benefits. In this study, conducted in a tropical evergreen forest in the Western Ghats of India, we used intra-flock association patterns to generate a community-wide assessment of flocking benefits for different species. We assumed that individuals needed to be physically proximate to particular heterospecific individuals within flocks to obtain any direct foraging benefit (flushed prey, kleptoparasitism, copying foraging locations). Alternatively, for anti-predation benefits, physical proximity to particular heterospecifics is not required, i.e. just being in the flock vicinity can suffice. Therefore, we used choice of locations within flocks to infer whether individual species are obtaining direct foraging or anti-predation benefits. A small subset of the bird community (5/29 species), composed of all members of the sallying guild, showed non-random physical proximity to heterospecifics within flocks. All preferred associates were from non-sallying guilds, suggesting that the sallying species were likely obtaining direct foraging benefits either in the form of flushed or kleptoparasitized prey. The majority of the species (24/29) chose locations randomly with respect to heterospecifics within flocks and, thus, were likely obtaining antipredation benefits. In summary, our study indicates that direct foraging benefits are important for only a small proportion of species in flocks and that predation is likely to be the main driver of flocking for most participants. Our findings apart, our study provides methodological advances that might be useful in understanding asymmetric interactions in social groups of single and multiple species.

Remarkable influence of secondary catalyst site on enantioselective desymmetrization of cyclopentenedione

An efficient, robust and highly enantioselective catalytic desymmetrization of 2,2-disubstituted cyclopentene-1,3-diones is developed via direct vinylogous nucleophilic addition of deconjugated butenolides. A remarkable influence of the secondary catalyst site on the enantioselectivity points towards an intriguing mechanistic scenario, possibly by triggering a change in catalyst conformation.

Influence of soil grading on the characteristics of cement stabilised soil compacts

The paper deals with experimental investigations aiming at specifying optimum soil grading limits for the production of cement stabilised soil bricks (CSSB). Wide range of soil grading curves encompassing both fine and coarse grained soils were considered. Strength, durability and absorption characteristics of CSSB were examined considering 14 different types of soil grading curves and three cement contents. The investigations show that there is optimum clay content for the soil mix which yields maximum compressive strength for CSSB and the optimum clay content is about 10 and 14 % for fine grained and coarse grained soils respectively. Void ratio of the compacted specimens is the lowest at the optimum clay content and therefore possesses maximum strength at that point. CSSB using fine grained soils shows higher strength and better durability characteristics when compared to the bricks using coarse grained soils.

Numerical Analysis on Intermittent Flow in a Longitudinal Section of Bingham Fluid along a Slope

The transition process of intermittent flow in a longitudinal section of Bingham fluid from initial distribution to fully developed state was numerically investigated in this paper. The influences of slope dimensionless runoff Q* and viscosity μ0* on the dimensionless surge speed U* were also presented in a wide range of parameters. By one typical example, the intermittent flow possessed wave characteristics and showed a supercritical flow conformation for a fully developed flow. The distributions of gravity and bed drag along the flow path and the velocity distribution of flow field were also analyzed.

Viscosity, Surface Tension, and Atomization of Water-Methanol and Diesel Emulsions

This article is the result of experimental studies of the rheologv, viscosities, surface tensions, and atomization of water-methanol and diesel emulsions. The Span 80 and Tween 60 are employed to make three emulsifying agents, Y01, Y02, and Y03, with viscosity of 1.32-1.5 Pa s and HLB values of 5.36, 4.83, and 4.51, respectively. In the water-in-oil emulsions, the aqueous phase is between 10% and 50%; the agent concentration added is 0.8-8.0%. The viscosity of the emulsions is 0.003-0.02 Pa s, and the surface tens ion is 0.04-0.1 N/m. The types and concentrations of agents significantly influence the viscosity of the emulsions, and the higher concentration of the aqueous phase (<50%) in creases the viscosities of the emulsions, especially for higher agent concentration. Interfacial membrane and HLB values of the agents can explain all these phenomena. Higher aqueous phase concentration and agent viscosity results in larger Sauter mean diameter.

Determinación del tamaño conglomerado de plantas para el muestreo de nematodos en café

Con el propósito de determinar un tamaño mínimo de muestras, que con cierto grado de precisión permita hacer una estimación confiable y con bajos costos para el productor cafetalero sobre la densidad de nematodos, se realizó un muestreo en 4 fincas del departamento de Carazo (Mª Auxiliadora, El Porvenir, San Marquitos y La Palmerita) En cada una de las fincas se seleccionó una hectárea tomando 15 plantas al azar, formando 5 conglomerados de 3 plantas cada uno, en cada planta se muestrearon 2 sitios a una distancia de 15 cm del pie de la planta y a una profundidad de 15cm en donde se recolectaron raíces simultáneamente se recolectaron muestras de raíces entre cada planta de tal manera que se formó una sola muestra por cada conglomerado a la cual nombramos " muestra compuesta". Por cada conglomerado de 3 plantas se recolectaron 3 muestras individuales y una muestra compuesta totalizando en las 4 fincas un total de 80 muestras de raices. Los géneros estudiados fueron: Meloidogyne sp., Pratylenchus sp y Rotylenchulus sp. Los resultados indican que la situación actual de la población de nematodos se encuentra agregada en el caso de los géneros Meloidogyne y Pratylenchus; mientras que en el caso del género Rotylenchulus sus poblaciones se encuentran de forma uniforme en las fincas muestreadas. La muestra individual arrojó mejores resultados que el tipo de muestra compuesta; se determinó que aceptando un 10% de error se hace necesario muestrear al azar 6 plantas(l00grs de raíz) distribuidas en 2 sitios por hectárea.

Evaluación, análisis y perspectivas de las principales plantaciones cocoteras (Cocus nuscifera L.) en la Región Autónoma del Atlántico Sur (R.A.A.S.)

La evaluación, análisis y perspectivas de las principales plantaciones cocoteras, (Cocus nuscifera, L.), se inició en 1995 y finalizó en Diciembre de 1996. La evaluación se realizó en las fincas: El Cocal, Tasbapounie, San Mariano y San Nicolás ubicadas en la Región Autónoma del Atlántico Sur (R.A.A.S). La metodología del estudio se basó en entrevistas, sondeos de opinión a técnicos y directores de Instituciones, vinculados al cultivo del cocotero en la región y visitas in situ a las plantaciones cocoteras. En cada finca se evaluó el manejo agronómico, el área y producción cocotera, aspectos socioeconómicos y se determinó la incidencia de cada uno de éstos factores, en la producción de cada una de las fincas estudiadas. El manejo agronómico y tecnología que cada finca aplica, la fertilidad marginal del suelo, el tipo de variedad de cocotero sembrado y la edad de las plantaciones inciden en el rendimiento que cada finca obtiene. La enfermedad del Anillo Rojo es la principal y única enfermedad importante, la cual es causado por el nemátodo Rhadinaphillenchus cocophillus C, que asociado con la principal plaga del cultivo el Picudo negro Rhinchosporum palmarum L, en San Nicolás y San Mariano, ha causando pérdidas anuales globales que superan los US$36,000 dólares. El Amarillamiento Letal del cocotero no está presente en la región. Respecto al año 1981, la totalidad del área del cocotero criollo Alto de Jamaica disminuyó en un 50%, mientras que el área del cocotero híbrido se incrementó en un 38% aproximadamente. La producción global de nueces del cocotero disminuyó un 50% aproximadamente durante el mismo período. La Finca San Nicolás registró el rendimiento más alto para cocotero híbrido y Tasbapounie el más bajo para cocotero criollo Alto de Jamaica. Las pérdidas anuales en términos de rendimiento real y poca comercialización de nueces, es superior a US$1,100,000.00. La diversificación en la modalidad de venta de nuez fresca transformada a copra, generaría en las fincas estudiadas, ingresos totales superiores a US$1,100,000.00 dólares. La falta de financiamiento, poca comercialización de nueces, bajos precios de compra y carestía del transporte son los principales factores socioeconómicos que inciden en el desarrollo del cultivo del cocotero. La finca San Nicolás, por su ubicación geográfica, eficiencia, productividad, experiencia y manejo del cultivo, es la de mayor perspectiva de inversión agro-industrial en la R.A.A.S.

Evolução das tarifas dos serviços públicos de água e esgotos

Consultor Legislativo - Área XI - Meio Ambiente e Direito Ambiental, Organização Territorial, Desenvolvimento Urbano e Regional.

Impact of cathode evaporation on a free-burning arc

A free-burning, high-intensity argon arc at atmospheric pressure was modelled during the evaporation of copper from the cathode. The effect of cathode evaporation on the temperature, mass flow, current flow and Cu concentration was studied for the entire plasma region. The copper evaporates from the tip of the cathode with an evaporation rate of 1 mg s-1. The copper vapour in the cathode region has a velocity of 210 m s-1 with a mass concentration of above 90% within 0.5 mm from the arc axis. The vapour passes from the cathode toward the anode with a slight diffusion in the argon plasma. Higher temperatures and current densities were calculated in the core of the arc caused by the cathode evaporation.

Mechanical and Chemical Control of Smooth Cordgrass in Waillapa Bay, Washington

We evaluated four methods to control smooth cordgrass (Spartina alterniflora Loisel), hereafter spartina, in Willapa Bay, Washington: mowing, mowing plus herbicide combination, herbicide only for clones, and aerial application of herbicide for meadows. (PDF has 7 pages.)

Recommendation domains for pond aquaculture: country case study: development and status of freshwater aquaculture in Cameroon

This report is an output of the project “Determination of high-potential aquaculture development areas and impact in Africa and Asia”. This monograph is the case study for Cameroon. Written in three parts, it describes the historical background, practices, stakeholder profiles, production levels, economic and institutional environment, policy issues, and prospects for aquaculture in the country. First, it documents the history and current status of the aquaculture in the country. Second, it assesses the technologies and approaches that either succeeded or failed to foster aquaculture development and discusses why. Third, it identifies the key reasons for aquaculture adoption.

Nova Lusitania : historia da guerra brasilica : a purissima alma e saudosa memoria do Serenissimo Principe Dom Theodosio, Principe de Portugal, e Principe do Brasil : por Francisco de Brito Freyre : decada primeira

Francisco de Brito Freire nasceu em Coruche, em 1625, e morreu em Lisboa, em 1692. Foi capitão de cavalaria da Província da Beira, governador da Praça de Juromenha, no Alentejo, e conselheiro de guerra, tendo sido, por duas vezes, almirante da armada portuguesa no Brasil. Foi governador de Pernambuco e assinou a capitulação dos holandeses em 1654. Como autor original, Brito Freire pôde observar pessoalmente os acontecimentos e relatá-los a seu modo. Os autores puristas do século XIX consideravam-no escritor de grande credibilidade. ‘Nova Lusitana, historia da guerra brasilica..’ que sempre foi considerado um clássico, é uma das melhores fontes sobre os eventos que o correram em Pernambuco, entre 1630 e 1638 . A condição de governador de Brito Freire possibilitou o seu acesso à ampla documentação, tanto portuguesa com o holandesa. permitindo-lhe formular uma opinião própria e narrar, em primeira mão, aqueles eventos. Rico em detalhes curiosos, corajoso nas críticas políticas, trata-se de um livro raro e procurado.