Aspects of tautomerism. Part II. Reactions of the pseudo-acid chloride of o-benzoylbenzoic acid with nucleophiles

Reactions of fourteen nucleophiles with the pseudo-acid chloride of o-benzoylbenzoic acid in two solvents have been studied. The nucleophiles that react primarily at the tetrahedral carbon atom to give pseudo derivatives, are weaker than those that react at the carbonyl carbon atom causing opening of the lactone ring. An explanation for this phenomenon is advanced.

Modeling of a reacting nanofilm on a composite substrate

This article provides a detailed computational analysis of the reaction of dense nanofilms and the heat transfer characteristics on a composite substrate. Although traditional energetic compounds based on organic materials have similar energy per unit weight, non-organic material in nanofilm configuration offers much higher energy density and higher flame speed. The reaction of a multilayer thin film of aluminum and copper oxide has been studied by varying the substrate material and thicknesses. The numerical analysis of the thermal transport of the reacting film deposited on the substrate combined a hybrid approach in which a traditional two-dimensional black box theory was used in conjunction with the sandwich model to estimate the appropriate heat flux on the substrate accounting for the heat loss to the surroundings. A procedure to estimate this heat flux using stoichiometric calculations is provided. This work highlights two important findings. One is that there is very little difference in the temperature profiles between a single substrate of silica and a composite substrate of silicon silica. Secondly, with increase in substrate thickness, the quenching effect is progressively diminished at a given speed. These findings show that the composite substrate is effective and that the average speed and quenching of flames depend on the thickness of the silica substrate, and can be controlled by a careful choice of the substrate configuration. (C) 2011 Elsevier Ltd. All rights reserved.

Role of PbO in lithium ion transport in Li2O-PbO-B2O3 glasses

Abstract: A wide range of compositions of grasses in the ternary Li2O-PbO-B2O3 glass system was prepared, and de and ac conductivity measurements were carried out on these glasses. The presence of lead leads to a decrease in de conductivities and an increase in the activation energies. This is likely to be due to the increase of the partial charges on the oxygen atoms and to the presence of the lone pair on the Pb atom; both of these factors impede lithium ion motion. The ac conductivity and dielectric behavior of these glasses support such a conjecture. (C) 2000 Elsevier Science Ltd.

A checking method for probabilistic seismic-hazard assessment: case studies on three cities

The conventional Cornell's source-based approach of probabilistic seismic-hazard assessment (PSHA) has been employed all around the world, whilst many studies often rely on the use of computer packages such as FRISK (McGuire FRISK-a computer program for seismic risk analysis. Open-File Report 78-1007, United States Geological Survey, Department of Interior, Washington 1978) and SEISRISK III (Bender and Perkins SEISRISK III-a computer program for seismic hazard estimation, Bulletin 1772. United States Geological Survey, Department of Interior, Washington 1987). A ``black-box'' syndrome may be resulted if the user of the software does not have another simple and robust PSHA method that can be used to make comparisons. An alternative method for PSHA, namely direct amplitude-based (DAB) approach, has been developed as a heuristic and efficient method enabling users to undertake their own sanity checks on outputs from computer packages. This paper experiments the application of the DAB approach for three cities in China, Iran, and India, respectively, and compares with documented results computed by the source-based approach. Several insights regarding the procedure of conducting PSHA have also been obtained, which could be useful for future seismic-hazard studies.

A convenient enantiospecific methodology for (-)-(1R,5S)-1,5-dimethylbicyclo[3.3.0]octa-2,7-dione: A formal total synthesis of (-)-ceratopicanol

An enantiospecific formal total synthesis of (-)-ceratopicanol starting from the readily and abundantly available monoterpene (R)-limonene is described. A combination of Claisen rearrangement-intramolecular diazo-ketone cyclopropanation-regiospecific reductive cyclopropane cleavage reactions are employed for the stereo- and regiospecific generation of the two vicinal ring junction quaternary carbon atoms.

Physics-Based Band Gap Model for Relaxed and Strained 100] Silicon Nanowires

In this paper, we propose a physics-based simplified analytical model of the energy band gap and electron effective mass in a relaxed and strained rectangular 100] silicon nanowires (SiNWs). Our proposed formulation is based on the effective mass approximation for the nondegenerate two-band model and 4 x 4 Luttinger Hamiltonian for energy dispersion relation of conduction band electrons and the valence band heavy and light holes, respectively. Using this, we demonstrate the effect of the uniaxial strain applied along 100]-direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] followed by a uniaxial one along the 100]-direction, respectively, on both the band gap and the transport and subband electron effective masses in SiNW. Our analytical model is in good agreement with the extracted data using the extended-Huckel-method-based numerical simulations over a wide range of device dimensions and applied strain.

Computational investigations on covalent dimerization/oligomerization of polyacenes: Is it relevant to soot formation?

We have postulated a novel pathway that could assist in the nucleation of soot particles through covalent dimerization and oligomerizations of a variety of PAHs. DFT calculations were performed with the objective of obtaining the relative thermal stabilities and formation probabilities of oligomeric species that exploit the facile dimerization that is known to occur in linear oligoacenes. We propose that the presence of small stretches of linear oligoacence (tetracene or longer) in extended PAH, either embedded or tethered, would be adequate for enabling the formation of such dimeric and oligomeric adducts; these could then serve as nuclei for the growth of soot particles. Our studies also reveal the importance of p-stacking interactions between extended aromatic frameworks in governing the relative stabilities of the oligomeric species that are formed. (c) 2012 Wiley Periodicals, Inc.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Physically Based, Hydrologic Model Results Based on Three Precipitation Products

The main objective of the study is to examine the accuracy of and differences among simulated streamflows driven by rainfall estimates from a network of 22 rain gauges spread over a 2,170 km2 watershed, NEXRAD Stage III radar data, and Tropical Rainfall Measuring Mission (TRMM) 3B42 satellite data. The Gridded Surface Subsurface Hydrologic Analysis (GSSHA), a physically based, distributed parameter, grid-structured, hydrologic model, was used to simulate the June-2002 flooding event in the Upper Guadalupe River watershed in south central Texas. There were significant differences between the rainfall fields estimated by the three types of measurement technologies. These differences resulted in even larger differences in the simulated hydrologic response of the watershed. In general, simulations driven by radar rainfall yielded better results than those driven by satellite or rain-gauge estimates. This study also presents an overview of effects of land cover changes on runoff and stream discharge. The results demonstrate that, for major rainfall events similar to the 2002 event, the effect of urbanization on the watershed in the past two decades would not have made any significant effect on the hydrologic response. The effect of urbanization on the hydrologic response increases as the size of the rainfall event decreases.

Modelling and analysis of new coolstreaming for P2P IPTV

Peer to peer networks are being used extensively nowadays for file sharing, video on demand and live streaming. For IPTV, delay deadlines are more stringent compared to file sharing. Coolstreaming was the first P2P IPTV system. In this paper, we model New Coolstreaming (newer version of Coolstreaming) via a queueing network. We use two time scale decomposition of Markov chains to compute the stationary distribution of number of peers and the expected number of substreams in the overlay which are not being received at the required rate due to parent overloading. We also characterize the end-to-end delay encountered by a video packet received by a user and originated at the server. Three factors contribute towards the delay. The first factor is the mean shortest path length between any two overlay peers in terms of overlay hops of the partnership graph which is shown to be O (log n) where n is the number of peers in the overlay. The second factor is the mean number of routers between any two overlay neighbours which is seen to be at most O (log N-I) where N-I is the number of routers in the internet. Third factor is the mean delay at a router in the internet. We provide an approximation of this mean delay E W]. Thus, the mean end to end delay in New Coolstreaming is shown to be upper bounded by O (log E N]) (log N-I) E (W)] where E N] is the mean number of peers at a channel.

MolBridge: a program for identifying nonbonded interactions in small molecules and biomolecular structures

Identification and analysis of nonbonded interactions within a molecule and with the surrounding molecules are an essential part of structural studies, given the importance of these interactions in defining the structure and function of any supramolecular entity. MolBridge is an easy to use algorithm based purely on geometric criteria that can identify all possible nonbonded interactions, such as hydrogen bond, halogen bond, cation-pi, pi-pi and van der Waals, in small molecules as well as biomolecules. The user can either upload three-dimensional coordinate files or enter the molecular ID corresponding to the relevant database. The program is available in a standalone form and as an interactive web server with Jmol and JME incorporated into it. The program is freely downloadable and the web server version is also available at http://nucleix.mbu.iisc.ernet.in/molbridge/index.php.

An estimate of the number of tropical tree species

The high species richness of tropical forests has long been recognized, yet there remains substantial uncertainty regarding the actual number of tropical tree species. Using a pantropical tree inventory database from closed canopy forests, consisting of 657,630 trees belonging to 11,371 species, we use a fitted value of Fisher's alpha and an approximate pantropical stem total to estimate the minimum number of tropical forest tree species to fall between similar to 40,000 and similar to 53,000, i.e., at the high end of previous estimates. Contrary to common assumption, the Indo-Pacific region was found to be as species-rich as the Neotropics, with both regions having a minimum of similar to 19,000-25,000 tree species. Continental Africa is relatively depauperate with a minimum of similar to 4,500-6,000 tree species. Very few species are shared among the African, American, and the Indo-Pacific regions. We provide a methodological framework for estimating species richness in trees that may help refine species richness estimates of tree-dependent taxa.