Precise Vibrational Analysis of B-X System of BiI

The bands of the B-X system of BiI have been photographed in the second order of a 35 ft concave grating spectrograph (with a dispersion of 0.33 Åing;/mm and resolution 2 × 180,000). A precise vibrational analysis of this system has been carried out and the vibrational constants WeYe and WeZe for the upper and lower states have been evaluated for the first time.     

Sensitive and selective methods for determination of antipsychotic drug olanzapine in pharmaceuticals

Two simple and sensitive spectrophotometric methods have been developed for analysis of the antipsychotic drug olanzapine in pharmaceuticals. Method A is based on liberation of iodine by reaction between the drug and potassium iodate, followed by reaction with leuco crystal violet (LCV), the color of oxidized LCV being measured at 598 nm. Method B is based on oxidation of olanzapine with chloramine-T (CAT) in acidic medium, the unconsumed CAT being determined with rhodamine B, measuring the absorbance at 550 nm. Calibration graphs were linear over the ranges of 0.05–2.0 and 0.1–1.6 μg mL^?1 olanzapine for method A and B, respectively. The molar absorptivity, Sandell’s sensitivity, detection limit, and quantitation limit were found to be 1.59 × 10⁵, 0.00132, 0.038, and 0.117, respectively, for method A and 0.953 × 10⁵, 0.00221, 0.064, and 0.192, respectively, for method B. The optimum conditions and other analytical parameters were evaluated. The proposed methods have been applied successfully for analysis of olanzapine in pure form and its dosage forms, and no interference was observed from common excipients present in pharmaceutical formulations.     

Spectrophotometric analysis of trichloroethylene in various environmental and biological samples

A simple sensitive extractive spectrophotometric method for determination of trichloroethylene is proposed. Trichloroethylene is treated with pyridine to form glutaconic aldehyde by heterolytic cleavage of the pyridine ring. Glutaconic aldehyde is further coupled with 4-aminoacetanilide to form an orange–red dye which is extractable in 3-methyl-1-butanol. The extracted dye shows absorption maximum at 520 nm. The system obeys Beer’s law in the range of 0.05–0.8 μg mL^?1. Important analytical parameters such as time, temperature, reagent concentration, acidity etc. have been optimized for complete colour reaction. Sandell’s sensitivity and molar absorptivity for the system were found to be 0.001 μg cm^?2 and 1.2 × 10⁵ L mol^?1 cm^?1, respectively. The proposed method is satisfactorily applied to micro-level determination of trichloroethylene in various environmental and biological samples.     

Concentration‐dependent Raman study of noncoincidence effect in the NH2 bending and CO stretching modes of HCONH2 in the binary mixture (HCONH2 + CH3OH)

The isotropic and anisotropic parts of the Raman spectra of NH₂ bending and ν(CO) stretching modes of HCONH₂ in a hydrogen‐bonding solvent, methanol, at different concentrations have been analyzed carefully in order to study the noncoincidence effect (NCE). In neat HCONH₂, the experimentally measured values of noncoincidence Δν_nc are ∼11 and ∼18 cm⁻¹ for the NH₂ bending and ν(CO) stretching modes, which reduce to 0.45 and 1.14 cm⁻¹, respectively at the concentration of HCONH₂ in mole fraction, χ_m = 0.1. The experimental results have been explained on the basis of two models, namely, the microscopic prediction of Logan and the macroscopic model of Mirone and Fini. The relative success of the two models in explaining the experimental data for both the modes have been discussed. It has been observed that in case of the ν(CO) stretching vibrational mode the Logan model can reproduce the experimental data rather precisely, whereas in the case of the NH₂ bending mode, Mirone and Fini model yields more accurate results. Copyright © 2006 John Wiley & Sons, Ltd.     

Improper hydrogen bonding and motional narrowing in binary mixtures of 2‐ and 3‐bromopyridine in methanol probed by polarized Raman study and DFT calculations

A concentration‐dependent Raman study of the ν(C Br) stretching and trigonal bending modes of 2‐ and 3‐Br‐pyridine (2Br‐p and 3Br‐p) in CH₃OH was performed at different mole fractions of the reference molecule, 2Br‐p/3Br‐p, from 0.1 to 0.9 in order to understand the origin of blue/red wavenumber shifts of the vibrational modes due to hydrogen‐bond formation. The appearance of additional Raman bands in these binary systems at ∼617 cm⁻¹in the case of 2Br‐p and at ∼618 cm⁻¹ in the case of 3Br‐p compared to neat bromopyridine derivatives were attributed to specific hydrogen‐bonded complexes formed in the mixtures. The interpretation of experimental results is supported by density functional calculations on optimized geometries and vibrational wavenumbers of 2Br‐p and 3Br‐p and a series of hydrogen‐bonded complexes with methanol. The parameters obtained from these calculations were used for a qualitative explanation of the blue/red shifts. The wavenumber shifts and linewidth changes for the ν(C Br) stretching and trigonal bending modes as a function of concentration reveal that the caging effects leading to motional narrowing and diffusion‐causing line broadening are simultaneously operative, in addition to the blue shift caused due to hydrogen bonding. Copyright © 2007 John Wiley & Sons, Ltd.     

Magnetization and structural studies of Mn doped ZnO nanoparticles: Prepared by reverse micelle method

Single phase Mn (2.5 at%) doped ZnO nanocrystalline samples were synthesized by reverse micelle method as characterized by Rietveld refinement analysis of X-ray diffraction data, high resolution transmission electron microscopy and selected area electron diffraction analyses. The X-ray photoelectron spectroscopy and electron paramagnetic resonance (EPR) studies indicated that manganese exist as Mn²⁺ in ZnO lattice. DC magnetization measurements as a function of field and temperature, of 2.5 at% Mn doped ZnO nanoparticles annealed at 675 K, showed room temperature ferromagnetism (RTF). This observation is further confirmed by the EPR spectrum of the sample, which shows a distinct ferromagnetic resonance signal at room temperature. These results indicate that the observed RTF in Mn-doped ZnO may be attributed to the substitutional incorporation of Mn at Zn sites.     

Vibrational spectra of 2 (3H) benzofuranone studied by Raman,IR spectroscopy and AM1 semiempirical molecular orbital calculations

Raman spectra of 2 (3H) benzofuranone have been recorded in the region 400-3200 cm(-1) and the IR spectra have been recorded in the region 200-4000 cm(-1). Vibrational frequencies for the fundamental modes of this bicyclic heteroatomic molecule have also been calculated using Austin method 1 (AM1) semiempirical molecular orbital method. Vibrational assignments have been made for the fundamental modes and the observed combination and overtone bands are also assigned. A splitting in the carbonyl group (C=O stretching) frequency observed at 1640-1660 cm(-1) in both Raman and IR spectra, is explained as Fermi-resonance. Net atomic charges for each atom of this molecule along with its heat of formation were also calculated. It is evident from the calculations that the 2 (3H) benzofuranone is more stable than the 3 (2H) benzofuranone in contrast to earlier estimates.     

Metal exchange kinetics: uncatalyzed replacement of Ni(II) from tetramethylenediaminetetraacetatonickel(II) complex by Cu(II)

The kinetics of metal exchange between copper(II) and tetramethylenediaminetetraacetatonickel(II), [Ni(TMDTA)] has been studied between pH 3.4 and 4.8 at an ionic strength of 1.25 M (NaClO₄) and a temperature of 25.0 ± 0.1 °C. The reaction is first order in [Ni(TMDTA)]. The reaction order in [Cu²⁺] varies from first to zero and then back to first as [Cu²⁺] is increased. At low copper concentration, the first-order rate constant is pH independent and represents the attack of copper on the nickel complex through a pathway in which TMDTA is partially uncoordinated before reaction with copper. Evidence is presented for a stepwise dechelation mechanism followed by attack of copper to give a dinuclear intermediate. The zero-order rate is pH dependent. At higher [Cu²⁺], the swing back to first order is due to the formation of a weak copper-tetramethylenediaminetetraacetatonickelate complex which then converts to products through a dinuclear intermediate. A plausible mechanism, consistent with all the kinetic data, is presented.     

Photomagnetism of a sym‐cis‐Dithiocyanato Iron(II) Complex with a Tetradentate N,N′‐Bis(2‐pyridylmethyl)1,2‐ethanediamine Ligand

A comprehensive study of the magnetic and photomagnetic behaviors of cis‐[Fe(picen)(NCS)₂] (picen=N,N′‐bis(2‐pyridylmethyl)1,2‐ethanediamine) was carried out. The spin‐equilibration was extremely slow in the vicinity of the thermal spin‐transition. When the cooling speed was slower than 0.1 K min^?1, this complex was characterized by an abrupt thermal spin‐transition at about 70 K. Measurement of the kinetics in the range 60–70 K was performed to approach the quasi‐static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin‐state‐trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well‐known light‐induced excited spin‐state‐trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light‐induced excitation, was studied. Single‐crystal X‐ray diffraction as a function of speed‐cooling and light conditions at 30 K revealed the mechanism of the spin‐crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin‐crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin‐transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect.