Aromaticities of azines relative to benzene; a theoretical approach through the dimethyldihydropyrene probe

The aromaticities of azines relative to benzene have been estimated by fusion with 15,16‐dimethyldihydropyrene. Chemical shift data for the azine‐fused dihydropyrenes (calculated at GIAO HF/6‐31G*//B3LYP/6‐31 + G*) were used to estimate the reduction in the dihydropyrene nucleus aromaticity. Choice of the saturated reference model was quite crucial in reliable estimation of aromaticity. Reference models with partial unsaturation at azine (21,23,25–32) gave better estimate of aromaticity than the parent dimethyldihydropyrene. Aromaticities of azines through chemical shift data and geometric parameter analysis were found to be 90–100% to that of benzene, highly consistent with the aromaticity estimation by nucleus independent chemical shift_(0)πzz calculations. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactions with heterocyclic diazonium salts: New routes for the synthesis of pyrazolo[1,5-c]-1,2,4-triazoles and pyrazolo[1,5-c]-as-triazines

3-Phenylpyrazole-5-(liazonium chloride ( 1 ) couples with α-chloro derivatives of acetylacetone, ethyl acetoacetate and aceto-o-anisidine to yield the corresponding pyrazole-5-yl hydrazonyl chloride derivatives 2a-c . Compounds 2a,b were cyclised to yield either the pyrazolo[1,5-c]-1,2,4-triazole derivatives 3a,b or the pyrazolo[1,5-c]-as-triazines 4a,b depending on the applied reaction conditions. Compound 2c cyclised only into 3c under different cyclization conditions. The pyrazolo[1,5-c]-as-triazine derivatives 4c-e could be prepared via condensation of 2a with potassium cyanide. Compound 2d reacted with aromatic thioles and with sodium benzene-sulphonate to yield the pyrazolo[1,5-c]-as-triazine derivatives 6a-d . Compound 1 reacted with activated double bond systems to yield pyrazolo[1,5-c]-as-triazines 8a,b and 9 .     

Structural,optical and electrical characterization of HgxCd1‐xTe polycrystalline films fabricated by two‐source evaporation technique

Two‐source thermal evaporation technique was used to prepare Hg_xCd_1‐xTe thin films onto scratch free transparent glass substrates. The structural investigations revealed that thin films were polycrystalline in nature. Transmittance measurements in the wavelength range (500‐2700 nm) were used to calculate optical constants. The analysis of the optical absorption data showed that the optical band gap was of indirect type. In the composition range 0.05 < x < 0.25 the films exhibited an optical band gap between 1.29 and 0.98 eV. In the same composition range the films were p‐type and exhibited a resistivity, which varied between 10² and 10^‐1 Ω‐cm. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Superabsorbent Copolymers by Pulsed Corona Discharges in Water

Pulsed corona discharges have been utilized for plasma polymerization in aqueous solution for the first time. Superabsorbent copolymers, i.e., poly(acrylamide-co-acrylic acid) hydrogels, were synthesized by aqueous solution polymerization using free radicals produced by pulsed corona discharges as initiator and N,N-methylene-bis-acrylamide as cross-linking agent. Acrylic acid contents in the monomers varied from 0% to 50%. The copolymers thus formed adsorbed 30–1100 g H₂O/g of copolymer. The FTIR spectra of the copolymers are comparable with the published FTIR spectra of the corresponding copolymers synthesized by a conventional chemical method and by -ray technique.     

Improvement in precision of extremely low <Superscript>236</Superscript>U/<Superscript>238</Superscript>U isotope ratio determination by using mass spectrometer with narrow dynamic range

The precision in measurement of trace level uranium isotopic ratio, i.e., ²³⁶U/²³⁸U or ²³⁴U/²³⁸U, on single Faraday detector with narrow dynamic range is very hard to achieve. this is mainly due to the narrow dynamic range of a single detector systems. A significant improvement in mass spectrometric determination of ²³⁶U/²³⁸U ratio has been achieved by employing an alternate method using a single Faraday detector of narrow dynamic range. The method makes use of the precise measurements of the ²³⁶U/²³⁴U ratio, ²³⁴U/²³⁵U ratio and ²³⁵U/²³⁸U ratio, which are used to calculate the ²³⁶U/²³⁸U ratio using the equation ²³⁶U/²³⁸U=²³⁶U/²³⁴Uײ³⁴U/²³⁵Uײ³⁵U/²³⁸U. Despite the fact that correlation of the data tends to increase the uncertainty in the result, our results show a significant improvement, i.e., more than 8 times better precision in measuring the ²³⁶U/²³⁸U ratio with this method (σ=3.98×10⁻⁰⁸) as compared to direct measurement of ²³⁶U/²³⁸U (σ=3.104×10⁻⁰⁷). The method widens the applicability of the single collector system with narrow dynamic range and it will potentially be helpful to improve the precision in the case of the static multi-collector system also. The objective of the present study was to compare the results of the same sample analyzed with the present alternate method and the direct method for precision.     

The reaction of nitriles with mercaptoacetic acid. A new synthesis of thiazole derivatives

The reaction of mercaptoacetic acid with nitriles was investigated. Whereas 4-hydroxythiazole derivative could be obtained from the reaction of benzoylacetonitrile and of ethyl cyanoacetate with mercaptoacetic acid, a bithiazole derivative was obtained on treatment of benzonitrile with the same reagent. The behaviour of the synthesised thiazole derivatives towards aromatic aldehydes and hydrazines is reported.     

Radiometric analysis of rock and soil samples of Leepa Valley; Azad Kashmir, Pakistan

In this article, we present results obtained from a radiometric survey that was conducted in the Leepa Valley of Azad Jammu & Kashmir, Pakistan. The purpose of current study is to appraise the radioactivity levels and the associated health hazards due to the terrestrial radionuclide in soil and rock samples. In this regard, 16 soil and 17 rock samples were collected from different locations of the Leepa Valley. After processing the samples, activity concentrations of primordial (²³²Th, ²²⁶Ra and ⁴⁰K) and anthropogenic (¹³⁷Cs) radionuclides were determined using a P-type coaxial high purity germanium detector. From the results obtained the mean activity concentrations of radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K in the soil samples were found to be 31.25 ± 0.46, 44.1 ± 1.07 and 575 ± 8.89 Bq kg^?1 respectively. Whilst, in rock samples ²²⁶Ra, ²³²Th and ⁴⁰K mean activities were found as 28.46 ± 0.45, 48.63 ± 1.12 and 666.7 ± 9.39 Bq kg^?1, respectively. The ¹³⁷Cs concentration level in soil and rock samples is found to be 15.04 ± 0.29 and 5.7 ± 0.16 Bq kg^?1, respectively. The average radium equivalent activity (R _aeq) was found as 143.16 and 142.93 Bq kg^?1 in soil and rock samples, respectively. These findings are less than the recommended safe value of 370 Bq kg^?1 as given in OECD report (1979). The values of external (H _ex) and internal hazard index (H _in) are also less than unity. Mean value of absorbed dose rate was found as 69.78 nGy h^?1 for the soil samples, which is in good agreement with the world wide average value (70 nGy h^?1). Mean value of absorbed dose rate from rock samples was found as 70.01 nGy h^?1. Mean values of the annual effective dose is also lower than the values reported for different other countries of the world.     

Syntheses, X-ray structures and CVD studies of diorganoalkoxogallanes

Structural studies by X-ray crystallography have been carried out for a range of diorganoalkoxogallanes incorporating donor-functionalized ligands. The compounds [Et₂Ga(μ-OR)]₂ (1, R = CH₂CH₂NMe₂; 2, R = CH(CH₃)CH₂NMe₂; 3, C(CH₃)₂CH₂OMe; 4, R = CH(CH₂NMe₂)₂) adopt dimeric structures with a planar Ga₂O₂ ring, and each gallium atom is coordinated in a distorted trigonal bipyramidal geometry. Low pressure chemical vapor deposition (CVD) of 2 and 4 resulted in the formation of oxygen deficient gallium oxide thin films on glass. However, the reaction of Et₃Ga and ROH (R = CH₂CH₂NMe₂, CH(CH₃)CH₂NMe₂, C(CH₃)₂CH₂OMe, CH(CH₂NMe₂)₂) in toluene under aerosol assisted (AA)CVD conditions afforded stoichiometric Ga₂O₃ thin films on glass. This CVD technique offers a rapid, convenient route to Ga₂O₃, which involves the in situ formation of diethylalkoxogallanes, of the type [Et₂Ga(μ-OR)]₂, the structures of which are described in this paper. The gallium oxide films were deposited at 450 °C and analyzed by scanning electron microscopy (SEM), X-ray powder diffraction, wavelength dispersive analysis of X-rays (WDX), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.     

Intermolecular/interionic interactions in l-isoleucine-, l-proline-, and l-glutamine-aqueous electrolyte systems

Speed of sound and density values for ternary systems (amino acid + salt + water): l-isoleucine/l-proline/l-glutamine in aqueous solutions of 1.5 M KCl, 1 M KNO₃, and 0.5 M K₂SO₄ have been measured for several concentrations of amino acids at different temperatures (303.15, 308.15, 313.15, 318.15, and 323.15 K). Using speed of sound and density data, the thermodynamic parameters such as isentropic compressibility (κ_s), change in isentropic compressibility (Δκ_s) and relative change (Δκ_s/κ₀) in isentropic compressibility have been computed. The isentropic compressibility values decrease with increase in the amino acid concentration as well as with temperature. The decrease in κ_s values with increase in concentration of l-isoleucine/l-proline/l-glutamine in 1.5 M KCl, 1 M KNO₃, and 0.5 M K₂SO₄ has been ascribed to an increase in the number of incompressible zwitterions in solutions, and the formation of ‘zwitterions-ions’ and ‘zwitterions-water dipole’ entities in solutions. The decrease in κ_s values with increase in temperature has been attributed to the corresponding decrease of κ_relax (a relaxational part of compressibility), which is dominant over the corresponding increase of κ_∞ (an instantaneous part of compressibility). The trends of variation of Δκ_s and Δκ_s/κ₀ with variations in solute concentration and temperature have also been discussed in terms of solute-solute and solute-solvent intermolecular/interionic interactions operative in the systems.