Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding

One hundred complexes have been investigated exhibiting D-X center dot center dot center dot A interactions, where X = H, Cl or Li and DX is the `X bond' donor and A is the acceptor. The optimized structures of all these complexes have been used to propose a generalized `Legon-Millen rule' for the angular geometry in all these interactions. A detailed Atoms in Molecules (AIM) theoretical analysis confirms an important conclusion, known in the literature: there is a strong correlation between the electron density at the X center dot center dot center dot A bond critical point (BCP) and the interaction energy for all these interactions. In addition, we show that extrapolation of the fitted line leads to the ionic bond for Li-bonding (electrostatic) while for hydrogen and chlorine bonding, it leads to the covalent bond. Further, we observe a strong correlation between the change in electron density at the D-X BCP and that at the X center dot center dot center dot A BCP, suggesting conservation of the bond order. The correlation found between penetration and electron density at BCP can be very useful for crystal structure analysis, which relies on arbitrary van der Waals radii for estimating penetration. Various criteria proposed for shared-and closed-shell interactions based on electron density topology have been tested for H/Cl/Li bonded complexes. Finally, using the natural bond orbital (NBO) analysis it is shown that the D-X bond weakens upon X bond formation, whether it is ionic (DLi) or covalent (DH/DCl) and the respective indices such as ionicity or covalent bond order decrease. Clearly, one can think of conservation of bond order that includes ionic and covalent contributions to both D-X and X center dot center dot center dot A bonds, for not only X = H/Cl/Li investigated here but also any atom involved in intermolecular bonding.

ADAPTATION OF MW LEVEL NATURAL GAS LEAN BURN ENGINE FOR PRODUCER GAS OPERATION A GRID CONNECTED POWER PLANT

Availability of producer gas engines at MW being limited necessitates to adapt engine from natural gas operation. The present work focus on the development of necessary kit for adapting a 12 cylinder lean burn turbo-charged natural gas engine rated at 900 kWe (Waukesha make VHP5904LTD) to operate on producer and set up an appropriate capacity biomass gasification system for grid linked power generation in Thailand. The overall plant configuration had fuel processing, drying, reactor, cooling and cleaning system, water treatment, engine generator and power evacuation. The overall project is designed for evacuation of 1.5 MWe power to the state grid and had 2 gasification system with the above configuration and 3 engines. Two gasification system each designed for about 1100 kg/hr of woody biomass was connected to the engine using a producer gas carburetor for the necessary Air to fuel ratio control. In the use of PG to fuel IC engines, it has been recognized that the engine response will differ as compared to the response with conventional fueled operation due to the differences in the thermo-physical properties of PG. On fuelling a conventional engine with PG, power de-rating can be expected due to the lower calorific value (LCV), lower adiabatic flame temperature (AFT) and the lower than unity product to reactant more ratio. Further the A/F ratio for producer gas is about 1/10th that of natural gas and requires a different carburetor for engine operation. The research involved in developing a carburetor for varying load conditions. The patented carburetor is based on area ratio control, consisting of a zero pressure regulator and a separate gas and air line along with a mixing zone. The 95 litre engine at 1000 rpm has an electrical efficiency of 33.5 % with a heat input of 2.62 MW. Each engine had two carburetors designed for producer gas flow each capable of handling about 1200 m3/hr in order to provide similar engine heat input at a lower conversion efficiency. Cold flow studies simulating the engine carburetion system results showed that the A/F was maintained in the range of 1.3 +/- 0.1 over the entire flow range. Initially, the gasification system was tested using woody biomass and the gas composition was found to be CO 15 +/- 1.5 % H-2 22 +/- 2% CH4 2.2 +/- 0.5 CO2 11.25 +/- 1.4 % and rest N-2, with the calorific value in the range of 5.0 MJ/kg. After initial trials on the engine to fine tune the control system and adjust various engine operating parameter a peak load of 800 kWe was achieved, while a stable operating conditions was found to be at 750 kWe which is nearly 85 % of the natural gas rating. The specific fuel consumption was found to be 0.9 kg of biomass per kWh.

Selective localisation of multi walled carbon nanotubes in polypropylene/natural rubber blends to reduce the percolation threshold

Polypropylene and natural rubber blends with multiwalled carbon nanotube (PP/NR + MWCNT nanocomposites) were prepared by melt mixing. The melt rheological behaviour of neat PP and PP/NR blends filled with different loadings (1, 3, 5, 7 wt%) of MWCNT was studied. The effect of PP/NR blends (with compositions, 80/20,50/50, 20/80 by wt) on the rheological percolation threshold was investigated. It was found that blending PP with NR (80/20 and 50/50 composition) reduced the rheological percolation threshold from 5 wt% to 3 wt% MWCNT. The melt rheological behaviour of the MWCNT filled PP/NR blends was correlated with the morphology observations from high resolution transmission electron microscopic (HRTEM) images. In predicting the thermodynamically favoured location of MWCNT in PP/NR blend, the specific interaction of phospholipids in NR phase with MWCNTs was considered quantitatively. The MWCNTs were selectively localised in the NR phase. The percolation mechanism in MWCNT filled PP/NR blends was discussed and for each blend composition, the percolation mechanism was found to be different. (C) 2015 Elsevier Ltd. All rights reserved.

Enantio sensing property of helicin, the derivative of a natural product: Discrimination of amines and amino alcohols

The chiral sensing property of helicin (the derivative of natural product obtained by partial oxidation of salicin, extracted from willow tree (Salix helix)) is reported. The use of helicin as a chiral derivatizing agent for the discrimination of amines and amino alcohols is convincingly established using H-1 NMR spectroscopy. The large chemical shift separation achieved between the discriminated peaks facilitated the accurate quantification of enantiomeric composition. The consistent trend observed in the shifting of imine proton peak (Delta delta) of helicin in all the derivatized molecules might aid the determination of spatial configuration. (C) 2015 Elsevier B.V. All rights reserved.

Enantio sensing property of helicin, the derivative of a natural product: Discrimination of amines and amino alcohols

The chiral sensing property of helicin (the derivative of natural product obtained by partial oxidation of salicin, extracted from willow tree (Salix helix)) is reported. The use of helicin as a chiral derivatizing agent for the discrimination of amines and amino alcohols is convincingly established using H-1 NMR spectroscopy. The large chemical shift separation achieved between the discriminated peaks facilitated the accurate quantification of enantiomeric composition. The consistent trend observed in the shifting of imine proton peak (Delta delta) of helicin in all the derivatized molecules might aid the determination of spatial configuration. (C) 2015 Elsevier B.V. All rights reserved.

Enantio sensing property of helicin, the derivative of a natural product: Discrimination of amines and amino alcohols

The chiral sensing property of helicin (the derivative of natural product obtained by partial oxidation of salicin, extracted from willow tree (Salix helix)) is reported. The use of helicin as a chiral derivatizing agent for the discrimination of amines and amino alcohols is convincingly established using H-1 NMR spectroscopy. The large chemical shift separation achieved between the discriminated peaks facilitated the accurate quantification of enantiomeric composition. The consistent trend observed in the shifting of imine proton peak (Delta delta) of helicin in all the derivatized molecules might aid the determination of spatial configuration. (C) 2015 Elsevier B.V. All rights reserved.

Quercetin, a Natural Flavonoid Interacts with DNA, Arrests Cell Cycle and Causes Tumor Regression by Activating Mitochondrial Pathway of Apoptosis

Naturally occurring compounds are considered as attractive candidates for cancer treatment and prevention. Quercetin and ellagic acid are naturally occurring flavonoids abundantly seen in several fruits and vegetables. In the present study, we evaluate and compare antitumor efficacies of quercetin and ellagic acid in animal models and cancer cell lines in a comprehensive manner. We found that quercetin induced cytotoxicity in leukemic cells in a dose-dependent manner, while ellagic acid showed only limited toxicity. Besides leukemic cells, quercetin also induced cytotoxicity in breast cancer cells, however, its effect on normal cells was limited or none. Further, quercetin caused S phase arrest during cell cycle progression in tested cancer cells. Quercetin induced tumor regression in mice at a concentration 3-fold lower than ellagic acid. Importantly, administration of quercetin lead to -5 fold increase in the life span in tumor bearing mice compared to that of untreated controls. Further, we found that quercetin interacts with DNA directly, and could be one of the mechanisms for inducing apoptosis in both, cancer cell lines and tumor tissues by activating the intrinsic pathway. Thus, our data suggests that quercetin can be further explored for its potential to be used in cancer therapeutics and combination therapy.

Effects of heat-treatment processes on the electroless Ni-B coating and its natural aging mechanism

A Ni-B coating was prepared with EN using potassium borohydride reducing agent. The as-plated micro-structure of the coating was confirmed from XRD to be a mixture of amorphous and supersaturated solid solution. Three kinds of phase transformation were observed from the DSC curve. Different from the previous works, the formation of Ni4B3 and Ni2B was found during some transformation processes. The key factors which influence the variation of micro-hardness and micro-structure in deposits are the formation, the size and amount of Ni3B, Ni4B3 and Ni2B. Aging of the deposits treated under some heat treatment conditions occurred at room temperature. Changes of the micro-hardness indicated aging phenomena evidently. the natural aging phenomena are concerned with various kinds of decomposition of borides, especially with Ni4B3 phase. The extent of natural aging depends on the formation and the quantity of Ni(4)B3 and Ni2B.

Numerical Simulation of Nox Formation in Coal Combustion with Inlet Natural Gas Burning

A full two-fluid model of reacting gas-particle flows and coal combustion is used to simulate coal combustion with and without inlet natural gas added in the inlet. The simulation results for the case without natural gas burning is in fair agreement with the experimental results reported in references. The simulation results of different natural gas adding positions indicate that the natural gas burning can form lean oxygen combustion enviroment at the combustor inlet region and the NOz concentration is reduced. The same result can be obtained from chemical equilibrium analysis.

Experimental investigation on the chaotic phenomena in the wake of a natural thermal convection flow

Chaotic phenomena in the wake of thermal convection flow fields above a heating flat plate were investigated experimentally. A newly developed electron beam fluorescence technique (EBF) was used to simultaneously measure density fluctuation at 7 points in a cross section above the plate. Correlation dimensions, intermittence coefficients, Fourier spectrum have been obtained for different Grashof numbers. Spatial distribution of correlation dimensions are presented. The experimental result shows that there is a certain relationship between the density fluctuation and the Gr number. And time-spacial characteristic of chaos evolution is also given.

Comparación de parámetros reproductivos bajo inseminación artificial y monta natural en cerdas, (Cofradia, G.E.P.)

Este experimento se realizó en la Granja Experimental Porcina (G.E.P), Cofradía, Masaya, con 82 cerdas del cuarto parto, 30 servidas a través de inseminación artificial (I.A) y 52 cerdas por monta natural (M.N); iniciando en mayo de 1,995 hasta mayo de 1,996 con el objetivo de evaluar los parámetros reproductivos y económicos en ambos sistemas de monta. Los dos grupos de cerdas reproductoras estaban compuestos por las razas LANDRACE, YORKSHIRE y DUROC. Las variables evaluadas fueron: Tasa de concepción (T.C) y tasa de parición (T.P), números de crías por partos (N.C.P), peso vivo promedio del lechón en la camada al nacer (P.V.L.C), relación beneficio-costo (B-C). Los resultados finales comprobados al 5% de significancia estadísticas fueron: T.P en I.A con 56.66% menor que en M.N con 76.92%, en N.C.P para I.A con 7.06, menor que en M.N de 8.725, P.V.L.C en I.A de 1.85 kg, similar a 1.74 kg, en MN. Para la relación B-C en I.A fue de 0.53 córdobas y para M.N de 0.56 córdobas.

Comparación de índices productivos y reproductivos de monta natural e inseminación artificial con semen congelado en cerdos

El presente trabajo de tesis se realizó en la granja experimental porcina MAGFOR-Misión China de la república de Taiwán, ubicada en Cofradía. El estudio consistió en la evaluación de los parámetros reproductivos en grupos de cerdas obtenidos por inseminación artificial y grupos obtenidos a través de la monta natural, también se aborda el tema de la consanguinidad y sus consecuencias como un factor negativo en la fijación de caracteres indeseables, esto sucede en las poblaciones en las que existe una alta homocigosis debido al origen común del material genético (padres emparentados). Las variables evaluadas en el presente trabajo fueron: tamaño de la camada al nacimiento, peso promedio de los lechones al nacimiento, peso promedio de los lechones al destete e intervalo parto parto. para el análisis estadístico se elaboraron tablas de contingencias por cada una de las variables con base en los promedios. Para la variable tamaño de la camada al nacimiento se obtuvo para el tratamiento inseminación artificial un promedio de 9.16 lechones y para la monta natural un promedio de 9.89 lechones al contrastar las medias de los dos tratamientos se obtuvo un valor de t de 0.88 que comparado con el valor tabulado al 5% resulto no significativo al observar el comportamiento de las diferentes razas ,la yorkshire obtuvo los mayores promedios en inseminación el caso especifico de esta habían muy pocos ejemplares 6 . Se trabajo en condiciones normales de producción lo cual pudo influir en estos resultados debido al tamaiio de la muestra en esta raza. Los resultados para la variable peso promedio de los lechones al nacimiento, arrojaron un promedio de 1.76 Kg. para las camadas obtenidas por inseminación artificial y 1.67kg para las obtenidas por el método de monta natural en las observaciones de los promedios por razas, se obtuvo el mayor peso a favor de la raza Landrace con 1.99 Kg. seguido de la raza duroc con 1.85 Kg. en el tratamiento de inseminación artificial, y para la monta natural el menor peso lo obtuvo la raza duroc con 1.44 Kg. y elmayor peso fue también la raza Landrace. la raza Yorkshire mostró un comportamiento similar tanto en inseminacion artificial, como en monta natural. Para la variable peso promedio de los lechones al destete, se obtuvo un peso promedio de 7.39 Kg. para los lechones obtenidos por el método de inseminacion artificial y un peso promedio de 6.71 Kg. en el caso de lechones obtenidos por monta natural al evaluar las razas, la raza Landrace obtuvo el mayor peso al destete con 8.01 Kg. como era de esperar al obtener los mayores promedios en peso al nacimiento esto fue para las camadas obtenidas por inseminacion artificial. en el caso. de los lechones obtenidos mediante la monta natural el mayor peso correspondió a la raza Hampshire pudiendo haber influido el numero de lechones, ya que esta fue la que presento el menor numero la raza Yorkshire tuvo en este caso un comportamiento similar en los dos tratamientos. Para la variable intervalo parto-parto, en el caso de las cerdas servidas por el método de inseminacion artificial presentaron un IPP de 5.52 meses o sea 167 días y las cerdas servidas por monta natural obtuvieron un IPP de5.01 meses o 152 días. En la prueba de hipótesis tanto como el contraste de varianza, los resultados fueron significativos y una diferencia de 15 días vacíos en una hembra eleva los costos de producción de una manera considerable por esta razón un IPP como el de la inseminación artificial solo se justifica en la granja experimental porcina en un numero especifico de cerdas elite y como apoyo al mejoramiento genético del hato porcino de esta así como del hato nacional.

Effects of Natural Convection on the Characteristics of a Long Laminar Argon Plasma Jet Issuing Horizontally into Ambient Air

Three-dimensional modeling results show that the appearance of the long laminar plasma jet is less influenced by natural convection even as it is issuing into ambient air horizontally. However, plasma parameter distributions may deviate from axi-symmetry