NDDO MO calculations: isotropic hyperfine coupling constants and nuclear spin-spin coupling constants

The nonempirical NDDO MO method in its unrestricted form has been used to evaluate isotropic hyperfine coupling constants and nuclear spin-spin coupling constants. Satisfactory agreement with INDO and experimental results is obtained.     

Hölder norm estimates for elliptic operators on finite and infinite-dimensional spaces

We introduce a new method for proving the estimate

where solves the equation . The method can be applied to the Laplacian on . It also allows us to obtain similar estimates when we replace the Laplacian by an infinite-dimensional Ornstein-Uhlenbeck operator or other elliptic operators. These operators arise naturally in martingale problems arising from measure-valued branching diffusions and from stochastic partial differential equations.

     

NDDO MO calculations

Three valence-only schemes based on the Roby version of NDDO MO theory, which differ only in the core-valence treatment and the choice of the basis set, have been applied to the study of molecules containing first-row atoms. Orbital energies, charge distribution, dipole moments, field gradients, and a few other one-electron molecular properties are calculated to satisfactory accuracy. The schemes appear unreliable in the prediction of barriers to internal rotation in molecules, presumably due to errors in the core contribution to the total energy. An alternative treatment is suggested.     

Preparation, preservation and application of pure isotope-enriched phenyltin species

A method combining liquid/liquid extraction and chromatographic fractionation has been developed for the preparation of pure monophenyltin (MPhT), diphenyltin (DPhT), and triphenyltin (TPhT), synthesized from isotope-enriched Sn metal using phenylation of SnI₄ in diethylether (DEE) followed by quenching with HBr and water. After two successive extractions of the aqueous HBr phase with DEE, >99% of both DPhT and TPhT was recovered in the combined DEE phase and 94% of the MPhT remained in the aqueous phase. The MPhT in the aqueous phase was extracted into dichloromethane. The organic phases were vaporized and the PhTs were redissolved in MeOH/water/acetic acid/sodium acetate (59/30/6/8, v/v/v/w), which was also used as storing solution. Aliquots of the two solutions containing either DPhT and TPhT or MPhT were injected into a silica-based C₁₈ column for isolating and purifying single species. The yields of pure MPhT, DPhT, and TPhT, each synthesized from isotope-enriched ¹¹⁸Sn metal, ¹²²Sn metal, and ¹²⁴Sn metal, were better than 99%. After chromatographic separation, the single phenyltin compounds were mixed to prepare a spike for multiple-isotope species-specific isotope dilution (MI-SSID). MI-SSID was successfully used to determine phenyltin compounds in the certified reference material, mussel tissue BCR CRM-477. At −20 °C, all of the fractionated phenyltin species were stable in the storage solution for at least 197 days. When these standards were stored at 4 °C or 22 °C, 4–6% of the DPhT and TPhT degraded within 27 days. The degradation of DPhT and TPhT increased with the ionic strength and acidity of the storage solution.      

Ortho effect in the Bergman cyclization: electronic and steric effects in hydrogen abstraction by 1-substituted naphthalene 5,8-diradicals

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an sigma framework.     

Influence of Sm<Superscript>3+</Superscript> ion in structural,morphological, and electrochemical properties of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> synthesized by microwave calcination

LiSm_xMn_2–xO₄ samples were synthesized via co-precipitation technique. The structural properties of the synthesized materials were studied using X-ray diffraction analysis and it confirmed the cubic spinel structure for all the compounds. The lattice parameter of LiMn₂O₄ was observed to be 8.2347 Ǻ and it decreased with Sm³⁺ concentration, due to the shrinkage in cell volume aided by higher binding energy between Sm-O bond. The SEM micrographs were analyzed using Image processing software (Image-J) to ascertain the pore and grain properties. The microwave synthesis had been observed to control the bulk grain formation and had yielded lesser porous and nanoparticles. The particle size distributions obtained through photocross correlation laser diffraction analysis had shown that LiMn₂O₄ with 60 nm and Sm-doped compounds with ∼30 nm, respectively. The cyclic voltammetry studies had revealed the decrease in electrocatalytic behavior in the initial cycle for compounds doped with Sm³⁺ ion. The initial capacities of LiMn₂O₄, LiSm_0.05Mn_1.95O₄ and LiSm_0.10Mn_1.90O₄ substituted compounds were observed to be 134.87 mAhg⁻¹, 132.22 mAhg⁻¹ and 126.41 mAhg⁻¹, respectively. The cells were simulated using 1D model namely Dualfoil5.1 program. The simulated results coincide well with the measured results. The cycle life studies reveal 93% capacity retention of samarium-0.05-doped samples when compared with 78.4% of the LiMn₂O₄.     

Characterization of Phyllanthus amarus herb by inductively coupled plasma mass spectrometric (ICP-MS) analysis,optical absorption and electron paramagnetic resonance (EPR) spectroscopic methods

A powdered sample of Phyllanthus amarus herb of Kadapa district of Andhra Pradesh, India, is used in the present study. ICP-MS analysis indicates that copper is present in higher concentration when compared to other elements. Although the Pb is toxic, it is within the permissible limit. The evaluated soil and herb physico-chemical parameters indicate that the sample is acidic in nature in comparison with the soil. An EPR study on powdered sample confirms the presence of Fe(III), Mn(II) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. MIR results are due to carbonate fundamentals.     

Synthesis and Antimicrobial Activity of 1-Aryl-4-(arylimino)-6-iminohexahydro-1,3,5-triazine-2-thione Derivatives

Russian Journal of General Chemistry - A series of 6-imino-1-aryl-4-(arylimino)-1,3,5-triazinane-2-thione derivatives are synthesized by cyclization of 1-aryl-3-cyanoguanidine with aryl...     

Magneto-resistance above 300 K in nano-crystalline Co–Ag metastable solid solutions

A series of nano-crystalline Co_xAg_100−x solid solutions have been prepared by NaBH₄ reduction of the corresponding metal salts at room temperature in Ar gas flow. Alloys heat-treated at 600 °C in Ar/H₂ (5%) show the evolution of metastable fcc Co precipitates in Ag. Magnetic studies indicate that all the compositions are ferromagnetic with Curie temperatures >400 K. For a nominal composition of Co₆₀Ag₄₀, heat-treated at 600 °C, an effective negative magneto-resistance (MR) ratio of the order of ∼21% at 350 K, at 2 T is observed. This could arise from the influence of magnetic field on the electron–phonon scattering effects near to T_c and to the spin-mixing scattering by magnons.