Correlation of soft magnetic properties with free volume and medium range ordering in metallic glasses probed by fluctuation microscopy and positron annihilation technique

Amorphous ribbons of different thicknesses of Co_64.5Fe_3.5Si₁₆B₁₄Ni₂ alloy were synthesized using the melt spinning technique by varying wheel speed. The effect of cooling rate on the ribbon thickness and their soft magnetic properties have been studied. The amorphous structure has been characterized in terms of structural free volume and medium range order (MRO) by positron annihilation spectroscopy and fluctuation electron microscopy techniques. Positron lifetime spectra of amorphous samples showed two lifetime components. The first component was found to be correlated with MRO whereas, the second lifetime component was found to be associated with nanovoid type of defects, and the second component was strongly dependent on processing conditions. It could be established that the coercivity of the amorphous samples produced by the rapid solidification technique mainly depends on the defects formed during processing rather than change induced in MRO.     

Quantifying the electronic effect of substituted phosphine ligands via molecular electrostatic potential

Values of the molecular electrostatic potential minimum (V(min)) corresponding to the lone pair region of several substituted phosphine ligands (PR(3)) have been determined at the DFT level. The V(min) value is proposed as a quantitative measure of the electronic effect of the PR(3) ligands. Good linear correlation between V(min) and Tolman electronic parameter of PR(3) has been obtained. V(min) is also proportional to the pK(a) values of the conjugate acids of PR(3), viz., [PR(3)H](+). Further, the DeltaE values of the reaction Ni(CO)(3) + PR(3) --> Ni(CO)(3)PR(3) and ScH(3) + PR(3) --> ScH(3)PR(3) are also linearly proportional to the V(min) values. However, if there is a strong metal to phosphorus pi-back-bonding, the DeltaE and V(min) do not fit to a line. It is also found that the standard reduction potential as well as the enthalpy change corresponding to the electrochemical couple eta-Cp(CO)(PR(3))(COMe)Fe(+)/eta-Cp(CO)(PR(3))(COMe)Fe(0) is linearly proportional to the V(min) values of PR(3). These correlations suggest that V(min) is a quantitative measure of the sigma-donating ability of the phosphine. It is hoped that, in phosphine-metal coordination chemistry, the V(min) based electronic parameter could be more advantageous than nu-CO and pK(a) based electronic parameters as it solely represents the inherent electronic property of the ligand.     

Comparative evaluation of three alpha-hydroxycarboxylic acids for the separation of lanthanides by dynamically modified reversed-phase high-performance liquid chromatography

The resolution for the three homologues of alpha-hydroxycarboxylic acids viz. lactic acid, alpha-hydroxyisobutyric acid (alpha-HIBA) and alpha-hydroxy-alpha-methylbutyric acid (alpha-H-alpha-MBA), was compared for the individual separation of 14 lanthanide elements under identical experimental conditions. Alpha-HIBA was found to be the best for separation of heavier lanthanides (Tb to Lu) while alpha-H-alpha-MBA led to a better separation for lighter lanthanides (La to Eu). All the 14 lanthanides were separated by gradient HPLC employing both alpha-HIBA and alpha-H-alpha-MBA so that there was reasonable resolution among all the peaks and the separation was completed in a short time.     

Accurate calculation of aromaticity of benzene and antiaromaticity of cyclobutadiene: new homodesmotic reactions

Newly designed homodesmotic reactions based on radical systems predict an absolute aromaticity of 29.13 kcal/mol for benzene and an absolute antiaromaticity of 40.28 kcal/mol for cyclobutadiene at the MP4(SDQ)/6-31G(d,p) level.     

On the parametrization of the toxicity of organic chemicals to Tetrahymena pyriformis. The problem of establishing a uniform activity

In this report we illustrate the importance of making an effort to ensure that all of the dependent variables in a QSAR are associated with one mechanism of action. If this cannot be established, it will not be possible to compare the QSAR with others acting on different biological systems. That is, such information cannot be used to develop a science of chemical-biological interactions. A study of the action of a large set of phenols acting on Tetrahymena pyriformis made by Cronin and Schultz is analyzed to illustrate the problem.     

Application of microgels as polymer supports for organic synthesis: preparation of a small phthalide library,a scavenger,and a borohydride reagent

Microgel polymers containing a series of functional groups have been prepared. These microgels were composed of cross-linked poly(styrene) and were prepared by radical polymerization in solution. The microgel polymers exhibit good solubility in an array of different organic solvents, and in addition, they can be efficiently precipitated by the addition of methanol and isolated by filtration. A nine-member phthalide library was synthesized using an aminomethyl-functionalized microgel 5. To further demonstrate the versatility of these microgel polymers, tris(2-aminoethyl)amino microgel 11 was examined as a scavenger reagent to remove unreacted isocyanate after a urea synthesis. Finally, a microgel-supported ammonium borohydride reagent 14 was successfully prepared and used as a reducing agent. Notable features of these microgels are that in all applications the progress of the reaction could be monitored by standard NMR techniques and their preparation is performed using common glassware and techniques found in all organic laboratories.     

The Osher scheme for non-equilibrium reacting flows

An extension of the Osher upwind scheme to non-equilibrium reacting flows is presented, Owing to the presence of source terms, the Riemann problem is no longer self-similar and therefore its approximate solution becomes tedious. With simplicity in mind, a linearized approach which avoids an iterative solution is used to define the intermediate states and sonic points. The source terms are treated explicitly. Numerical computations are presented to demonstrate the feasibility, efficiency and accuracy of the proposed method. The test problems include a ZND (Zeldovich-Neumann-Doring) detonation problem for which spurious numerical solutions which propagate at mesh speed have been observed on coarse grids. With the present method, a change of limiter causes the solution to change from the physically correct CJ detonation solution to the spurious weak detonation solution.     

Einstein<Emphasis Type="Italic">A</Emphasis>-coefficients for rotational transitions in the ring-chain isomer of C<Subscript>5</Subscript>H<Subscript>2</Subscript>

Laboratory formation of four isomers of C⁵H² molecule is reported and detection of the ring-chain isomer (isomer 1) of C₅H₂ in cosmic objects has been suggested. For identification of a molecule in cosmic objects, one of the required input data is EinsteinA-coefficients (radiative transition probabilities) for the molecule. Here, we report EinsteinA-coefficients for electric dipole transitions in the ring-chain isomer of C₅H₂ among the rotational levels of the ground electronic and ground vibrational states up to 21 cm⁻¹.     

Cubyl-caged systems: regiochemical steering of cationic rearrangements by distal groups

Novel carbonium ion rearrangements of substituted 1,3-bishomocubanones $\text{3}$ & $\text{4}$ to tricyclo(4.2.0.0^3,8)octane and bicyclo(3.2.1)octane ring systems are reported.