Bifunctionalized allenes. Part XXIV. Competitive electrophilic cyclization of 5-(dimethoxyphosphoryl)-alka-3,4-dienoates leading to 2,5-dihydro-1, 2-oxaphospholes and 5,6-dihydro-2H-pyranes

Abstract

We report herein a study on the competitive electrophilic cyclization of 5-(dimethoxyphosphoryl)-alka-3,4-dienoates involving 5-endo-trig and 6-endo-trig mode cyclizations. Reaction with electrophiles produces mixtures of the 2-(2-oxo-2,5-dihydro-1,2-oxaphosphol-5-yl)-alkanoates and (6-oxo-5,6-dihydro-2H-pyran-2-yl)-phosphonates by competitive electrophilic cyclization due to the participation of the neighboring phosphonate and carboxylate groups.     

Molecular dynamics simulation of gas adsorption on defected graphene

Gas sensing is one of the most promising applications for graphene. Using molecular dynamics simulation method, adsorption isotherm of xenon (Xe) gas on defected and perfect graphene is studied in order to investigate sensing properties of graphene for Xe gas. In this method, first generation of Brenner many-body potential is used to simulate the interaction of carbon–carbon (C) atoms in graphene, and Lennard–Jones two-body potential is used to simulate interaction of Xe–Xe and Xe–C atoms. In the simulated systems, adsorption coverage, radial distribution function, heat of adsorption, binding energy and specific heat capacity at constant volume are calculated for several temperatures between 90 K and 130 K, and various pressures. It was found that both of the defected and perfect graphene could be introduced as very good candidates for adsorption of Xe gas.     

Nuclear-Electron Overhauser Effect in MC800 Liquid Asphalt Solutions

Experimental results on the extrapolated ultimate enhancement factors of o-, m-, and p-xylene protons at 1.53 mT are obtained for MC800 asphalt solutions. The ultimate enhancement factors are found such as ?26.9, ?25.7, and ?11.7 for o-, m-, and p-xylene, respectively. These results show that the solvent proton Overhauser effect cannot reach the extrapolated enhancement of ?330 in the extreme narrowing case because of occurrence of small scalar interactions in addition to the dipole–dipole interactions between solvent protons and asphalt electrons. The ortho, meta, and para positions of the –CH₃ group change the nature of the interactions. The nuclear magnetic resonance (NMR) signal enhancements exhibit a sensitive behavior depending on the chemical environment differing from isomer to isomer. The solvation or association of asphalt in xylene isomers at room temperature is revealed. Quantum chemical calculations for the xylene isomers with the electronic and optical properties; absorption wavelengths, excitation energy, atomic charges, dipole moment and frontier molecular orbital energies, molecular electrostatic potential; are carried out using the density functional theory (DFT) method (B3LYP) with the 6-311G(d,p) basis set by the standard Gaussian 09 software package program. The relative importance of scalar and translational dipolar interaction parameters determined in dynamic nuclear polarization experiments is explained by the electronic structure of HOMO–LUMO of the xylene isomers.     

Tabu search for graph partitioning

In this paper, we develop a tabu search procedure for solving the uniform graph partitioning problem. Tabu search, an abstract heuristic search method, has been shown to have promise in solving several NP-hard problems, such as job shop and flow shop scheduling, vehicle routing, quadratic assignment, and maximum satisfiability. We compare tabu search to other heuristic procedures for graph partitioning, and demonstrate that tabu search is superior to other solution approaches for the uniform graph partitioning problem both with respect to solution quality and computational requirements.     

Characteristics of high energy interactions II. Production spectra of Gamma-rays in graphite

Twenty high energy nuclear interactions produced in the graphite units of an emulsion chamber were recorded. The emulsion chamber was exposed to cosmic rays at an atmospheric depth of 10 g cm⁻² for about 7 hr over Hyderabad, India. Fourteen interactions which radiated energyΣ E _r⩾1000 GeV in the form ofγ-rays were analysed in detail. The median energy 〈Σ E _r〉 of the interactions was 1600 GeV. Results concerning the multiplicity, the transverse and longitudinal momentum distributions, and the fractional energy distribution ofγ-rays in these interactions are presented. The average transverse momentum ofπ ⁰—mesons <pt _π ⁰> is found to increase very slowly with the primary energyE ₀ and it can be approximated by the function <pt _π ⁰>=0·238E ₀ ^0.06 .     

Characteristics of high energy interactions I. High energy gamma-ray spectra near the top of the atmosphere

An emulsion chamber was used to study the characteristics of high energy nuclear interactions from the production spectra ofγ-rays. The emulsion chamber, which comprised of two parts, namely the detector and the graphite producer unit, was exposed to cosmic rays for about 7 hr at an atmospheric depth of 10 g cm⁻² at Hyderabad (geomagnetic latitude 7·6°N). 720 electromagnetic cascades due toγ-rays were recorded in the detector. These cascades were classified into three groups; (a)γ-rays from nuclear interactions in the detector (b)γ-rays from nuclear interactions in the producer unit and (c)γ-rays of atmospheric origin. The energies of the cascades were determined using photometric method. The spectra ofγ-rays from groups (a) and (c) were determined and compared with similar spectra obtained at greater atmospheric depths. The spectra were found to obey a power law. The spectrum ofγ-rays of atmospheric origin was found to steepen at high energies,E _r>2200 GeV.     

Optical characterization of the silicon photodiodes for the establishment of national radiometric standards

Optical properties of the silicon photodiodes are investigated in the visible spectral regime. Non-linearity measurement standard was established by using Hamamatsu S1337-11 type windowless silicon photodiode whose non-linearity value was found to be better than 6×10⁻⁵ at photocurrent level of 10⁻⁹ to 10⁻⁴ A. Temperature effects on the spectral responsivity for S1337-11, S1337-1010BQ and S1227-1010BQ type photodiodes were analyzed between 20°C and 40°C at 488.1, 514.7 and 632.8 nm vacuum wavelengths. The spatial uniformities of the responsivity for three type photodiodes are performed with a laser beam having 1 mm diameter by using home made two-axis micro translation system. Results of the reflectance measurements for three elements of reflection-based trap detectors were compared with the predicted values obtained from Fresnel equations.