Thermally Induced Acyl Migration in Salicylamides. 1. Structures of the Reactants, O-Acetylsalicylamide and O-Benzoylsalicylamide

O-Acetylsalicylamide (Ia), C9H9NO3, M r =179.18, monoclinic, P2Jc, a=8.155(5), b=8.571 (2), c= 13.092 (3)A, fl=99.54 (5) ° , V= 902.4(6)A 3, Z=4, Dm=l.31, Dx=l.319gcm -3, 2(Mo Ka) = 0.71069 A,/~ = 1.08 cm -1, F(000) = 376, T = 295 K, R = 0.076 for 1604 reflections. O-Benzoylsalicylamide (Ib), C14HtlNO 3, M,=241.2, monoclinic, P2t/e, a=9.423(1), b=5.116(1), e= 26.424 (2) A, fl= 103.97 (1)% V= 1236.2 (3)/~3, Z= 4, D~ = 1.28, D x = 1.296 gcm -3, ,;L(Cu Ks) = 1.5418 A, p = 7.71 cm-', F(000) = 504, T= 295 K, R =0.050 for 2115 reflections. The dihedral angles between the amide group and the benzene ring are 39.9 ° (Ia) and 37.9 ° (Ib), whereas between the acyl group and the benzene ring they are 78.1 ° (Ia) and 93.4 ° (Ib). The differences in the packing of the two structures are brought out in terms of the observed hydrogen-bonding patterns. Based on the crystallographic results, an intramolecular mechanism for the migration of the acyl group from the O to the N position is suggested in both compounds.

Biosynthesis of cytoplasmic subunits of cytochrome C oxidase in rat liver

The biosynthesis of the cytoplasmic subunits of cytochrome oxidase from rat liver has been studied in vitro by translating liver poly (A)-containing RNA in the wheat germ cell-free system and immunoprecipitating the products with anti-cytochrome oxidase antibody. Analysis of the labelled immunoprecipitate on SDS-gels does not reveal the presence of a polyprotein precursor. On the other hand discrete products which are either slightly bigger or closely similar to the mature subunits present in purified cytochrome oxidase have been detected.

Deformation processing of an aluminum alloy containing particles: Studies on AI-5 pct Si alloy 4043

Al-5 wt pct Si alloy is processed by upset forging in the temperature range 300 K to 800 K and in the strain rate range 0.02 to 200 s−1. The hardness and tensile properties of the product have been studied. A “safe” window in the strain rate-temperature field has been identified for processing of this alloy to obtain maximum tensile ductility in the product. For the above strain rate range, the temperature range of processing is 550 K to 700 K for obtaining high ductility in the product. On the basis of microstructure and the ductility of the product, the temperature-strain rate regimes of damage due to cavity formation at particles and wedge cracking have been isolated for this alloy. The tensile fracture features recorded on the product specimens are in conformity with the above damage mechanisms. A high temperature treatment above ≈600 K followed by fairly fast cooling gives solid solution strengthening in the alloy at room temperature.

Cl-35 NQR study of cation polarizability in metal salts of monochloro acetic acid

Various metal salts (Na, K, Rb, and NH4) of monochloro acetic acid were prepared and the Cl-35 nuclear quadrupole resonance frequencies were measured at room temperature. A comparative study of nuclear quadrupole resonance frequencies of monochloro acetic acid and its metal salts is carried out. The frequency shifts obtained in the respective metal chloroacetates are used to estimate the changes in the ionicity of C-Cl bond. Further, the changes in the ionicity of C-Cl bond were used to estimate the percentage of intra-molecular charge transfer between respective cation-anion of the metal salts of chloro acetic acid. The nuclear quadrupole resonance frequency is found to decrease with increasing ionicity of the alkali metal ion.

Lattice vibrations and specific heat of zinc blende

The dispersion relations, frequency distribution function and specific heat of zinc blende have been calculated using Houston's method on (1) A short range force (S. R.) model of the type employed in diamond by Smith and (2) A long range model assuming an effective charge Ze on the ions. Since the elastic constant data on ZnS are not in agreement with one another the following values were used in these calculations: {Mathematical expression}. As compared to the results on the S. R. model, the Coulomb force causes 1. A splitting of the optical branches at (000) and a larger dispersion of these branches; 2. A rise in the acoustic frequency branches the effect being predominant in a transverse acoustic branch along [110]; 3. A bridging of the gap of forbidden frequencies in the S. R. model; 4. A reduction of the moments of the frequency distribution function and 5. A flattening of the Θ- T curve. By plotting (Θ/Θ0) vs. T., the experimental data of Martin and Clusius and Harteck are found to be in perfect coincidence with the curve for the short range model. The values of the elastic constants deduced from the ratio Θ0 (Theor)/Θ0 (Expt) agree with those of Prince and Wooster. This is surprising as several lines of evidence indicate that the bond in zinc blende is partly covalent and partly ionic. The conclusion is inescapable that the effective charge in ZnS is a function of the wave vector {Mathematical expression}.

Search for new transparent conductors: Effect of Ge doping on the conductivity of Ga2O3, In2O3 and Ga1.4In0.6O3

Only a small amount (<= 3.5 mol%) of Ge can be doped in Ga2O3, Ga1.4In0.6O3 and In2O3 by means of solid state reactions at 1400 degrees C. All these samples are optically transparent in the visible range, but Ge-doped Ga2O3 and Ga1.4In0.6O3 are insulating. Only Ge-doped In2O3 exhibits a significant decrease in resistivity, the resistivity decreasing further on thermal quenching and H-2 reduction.The resistivity of 2.7% Ge-doped In2O3 after H-2 reduction shows a metallic behavior, and a resistivity of similar to 1 m Omega cm at room temperature, comparable to that of Sn-doped In2O3. (C) 2010 Elsevier Ltd. All rights reserved.

Electron donor-acceptor complex of ICl with diethyl ether - He I photoelectron spectroscopy and ab initio molecular orbital study

The He I photoelectron spectrum of the diethyl ether-ICl complex has been obtained. The oxygen orbitals are shifted to higher binding energies and that of ICl to lower binding energies owing to complex formation. Ab initio molecular orbital (MO) calculations of the complex molecule showed that the bonding is between the sigma-type lone pair of oxygen and the I atom and that the complex has C-2v symmetry. The binding energy of the complex is computed to be 8.06 kcal mol(-1) at the MP2/3-21G* level. The orbital energies obtained from the photoelectron spectra of the complex are compared and assigned with orbital energies obtained by MO calculations. Natural bond orbital analysis (NBO) shows that charge transfer is from the sigma-type oxygen lone pair to the iodine atom and the magnitude of charge transfer is 0.0744 e.

Enantioselective synthesis of both (+)- and (-)-derivatives of bicyclo[4.3.0]nonan-8-one and 3,8-diones from R-carvone

Enantioselective synthesis of both the enantiomeric forms of the hydrindane derivatives mentioned in the title, potential chiral precursors in terpenoid synthesis, starling from R-carvone employing two different cyclopentannulation methodologies is described.

Total Synthesis of Gabosine H

Stereoselective total synthesis and assignment of the absolute configuration of the keto carba sugar gabosine H is presented. Pivotal reactions in the sequence include desymmetrization of the dimethylamide of tartaric acid and ring-closing metathesis.

Study of local environment of Ag in Ag/CeO2 catalyst by EXAFS

The combustion synthesized Ag/CeO2 catalysts have been characterized by Extended Xray Absorption Fine Structure (EXAFS) spectroscopy at the Ag K-edge. It has been found that Ag+ like species is present in 1% Ag/CeO2 catalyst, whereas mostly Ag metal clusters are found in 3% Ag/CeO2. The analysis of EXAFS spectra indicates that about one oxygen atom is coordinated to Ag central atom at a distance of 2.19 Angstrom in 1% Ag/CeO2 catalyst along with eight coordinated Ag-Ag bond at 2.86 Angstrom. The Ag-O bond is absent in 3% Ag/CeO2. (C) 2002 Elsevier Science Ltd. All rights reserved.

Robust Approach for Identification of Bad Data in State Estimation Using SLP Technique

This paper proposes a new approach for solving the state estimation problem. The approach is aimed at producing a robust estimator that rejects bad data, even if they are associated with leverage-point measurements. This is achieved by solving a sequence of Linear Programming (LP) problems. Optimization is carried via a new algorithm which is a combination of “upper bound optimization technique" and “an improved algorithm for discrete linear approximation". In this formulation of the LP problem, in addition to the constraints corresponding to the measurement set, constraints corresponding to bounds of state variables are also involved, which enables the LP problem more efficient in rejecting bad data, even if they are associated with leverage-point measurements. Results of the proposed estimator on IEEE 39-bus system and a 24-bus EHV equivalent system of the southern Indian grid are presented for illustrative purpose.

Tailoring the Magnetic and Optical Characteristics of Nanocrystalline BiFeO3 by Ce Doping

The Ce-doped BiFeO3 (BFO) nanoparticles (NPs) were synthesized using a facile solgel route with varying Ce concentrations in the range of 15 mol%. Ferroelectric transition temperature was found to shift from 723 degrees C +/- 5 degrees C for pristine BFO NPs to 534 degrees C +/- 3 degrees C for 5 mol% Ce-doped BFO NPs. UVVis absorption spectra of BFO NPs showed a significant blue shift of similar to 100 nm on Ce doping. The Fourier transformed infrared (FTIR) spectrum centered similar to 550 cm(-1) becomes considerably broadened on Ce doping which is due to additional closely spaced vibrational peaks as revealed by the second derivative FTIR analysis. High-frequency EPR measurements indicated that clustering occurs at high dopant levels, and that Fe is present as Fe(3+)corroborating Mossbauer measurements. The values of saturation and remanent magnetization for 3% Ce-doped BFO NPs are 3.03 and 0.49 emu/g, respectively, which are quite significant at room temperature, making it more suitable for technological applications.

High precision Mg isotope measurements of meteoritic samples by secondary ion mass spectrometry

The possibility of establishing an accurate relative chronology of the early solar system events based on the decay of short-lived Al-26 to Mg-26 (half-life of 0.72 Myr) depends on the level of homogeneity (or heterogeneity) of Al-26 and Mg isotopes. However, this level is difficult. to constrain precisely because of the very high precision needed for the determination of isotopic ratios, typically of +/- 5 ppm. In this study, we report for the first time a detailed analytical protocol developed for high precision in situ Mg isotopic measurements ((25)mg/(24)mg and (26)mg/Mg-24 ratios, as well as Mg-26 excess) by MC-SIMS. As the data reduction process is critical for both accuracy and precision of the final isotopic results, factors such as the Faraday cup (FC) background drift and matrix effects on instrumental fractionation have been investigated. Indeed these instrumental effects impacting the measured Mg-isotope ratios can be as large or larger than the variations we are looking for to constrain the initial distribution of Al-26 and Mg isotopes in the early solar system. Our results show that they definitely are limiting factors regarding the precision of Mg isotopic compositions, and that an under- or over-correction of both FC background instabilities and instrumental isotopic fractionation leads to important bias on delta Mg-25, delta(26)mg and Delta Mg-26 values (for example, olivines not corrected for FC background drifts display Delta Mg-26 values that can differ by as much as 10 ppm from the truly corrected value). The new data reduction process described here can then be applied to meteoritic samples (components of chondritic meteorites for instance) to accurately establish their relative chronology of formation.

Bilateral smoothing of gradient vector field and application to image segmentation

Medical image segmentation finds application in computer-aided diagnosis, computer-guided surgery, measuring tissue volumes, locating tumors, and pathologies. One approach to segmentation is to use active contours or snakes. Active contours start from an initialization (often manually specified) and are guided by image-dependent forces to the object boundary. Snakes may also be guided by gradient vector fields associated with an image. The first main result in this direction is that of Xu and Prince, who proposed the notion of gradient vector flow (GVF), which is computed iteratively. We propose a new formalism to compute the vector flow based on the notion of bilateral filtering of the gradient field associated with the edge map - we refer to it as the bilateral vector flow (BVF). The range kernel definition that we employ is different from the one employed in the standard Gaussian bilateral filter. The advantage of the BVF formalism is that smooth gradient vector flow fields with enhanced edge information can be computed noniteratively. The quality of image segmentation turned out to be on par with that obtained using the GVF and in some cases better than the GVF.