Frequency and temperature dependent dielectric studies of propylene glycol-sulfolane binary mixtures in the microwave frequency region.

The dielectric permittivity of propylene glycol/sulfolane binary mixtures have been determined at various temperatures in the frequency range of 0.02 ˂ν/GHz˂ 20 using open-ended coaxial probe method. The permitivity spectra of propylene glycol/sulfolane mixtures with an asymmetric shape is observed. The experimental dielectric permittivity, relaxation time values are used to obtain remaining excessive parameters such as excess permittivity (εE), deviation in refractive index (ΔnD) excess inverse relaxation time (1/τ)ε, Kirkwood effective correlation factor (geff) and active thermodynamic parameters. Redlich-Kister polynomial equation is used to fit the excessive dielectric parameters. The molecular interaction between propylene glycol and sulfolane binary mixtures is interpreted in terms of short and long-range interactions among the dipoles. The experimental dipole moment values are compared with the theoretical dipole moment values from DFT/B3LYP, MP2 methods. Natural bond orbital (NBO) analysis is performed on the optimized geometrical structure of the above system to understand molecular interaction between the binary mixtures in terms of hydrogen bonding. The chemical stability of the system is studied from the HOMO-LUMO calculations. The energy of H- bond interaction between propylene glycol and sulfolane binary mixture is calculated from the single point energy calculations, and the results are correlated.

Relaxation dynamics of l-alanine in water medium investigated by dielectric relaxation spectroscopy.

The complex dielectric permittivity of L-alanine in aqueous medium at different concentrations and different temperatures were measured in the microwave (0.02 < ν/GHz < 20) frequency region by using open-ended coaxial probe technique. From the reflection coefficient and impedance data, the real and imaginary part of the dielectric permittivity values is determined. It is observed that there is a decrease in the real part of the dielectric permittivity up to certain frequency and an increase in the imaginary part of the dielectric permittivity with increase in the molar concentration of L-alanine in water medium. Based on the experimental data the average relaxation time values are calculated and its behavior is analyzed in terms of bound water and free water molecules. The theoretical dipole moment of L-alanine is calculated at gaseous state as well as in aqueous medium by using PCM and IEFPCM model at HF, DFT/B3LYP and MP2 calculations using 6-311G* basis set. Analysis between experimentally determined parameters and computed dipole moments were discussed. The mean molecular polarizability is calculated from the Lippincott δ function potential model and compared with the Le Fèvre method of polarizability values.

A novel strategy for the manufacture of idelalisib: controlling the formation of an enantiomer.

A novel and scalable synthesis of 5-fluoro-3-phenyl-2-[(1S)-1-(9H-purin-6-ylamino)propyl]-4(3H)-quinazolinone, idelalisib 1, has been developed. This strategy controls the desfluoro impurity of 13 during reduction of nitro intermediate 4, and also arrests the formation of the enantiomer during cyclisation of diamide 17, without affecting the neighbouring chiral centre. This process is demonstrated on a larger scale in the laboratory and achieved good chemical and chiral purities coupled with good yields.

Primary leptomeningeal primitive neuroectodermal tumor: A difficult entity to diagnose.

A 25-year-old male presented with difficulty in walking, loss of vision, and seizures. A clinical possibility of craniospinal meningeal pathology was considered. On computed tomography (CT) scan and magnetic resonance imaging, there was an enhancement of leptomeninges with few ring-enhancing lesions in both frontal lobes and right frontoparietal region. He was evaluated for low backache and occipital headache 2½ years earlier and was found to have communicating hydrocephalus on CT scan. He underwent ventriculoperitoneal shunt and was followed up with CT scans. Meningeal biopsy was done in the present admission, and there was a diffusely infiltrating small round cell tumor. Immunohistochemistry was done, and the tumor cells were found to be negative for glial, mesenchymal, melanotic, and lymphoid markers. The cells were positive for neuron-specific enolase, chromogranin, and vimentin. A diagnosis of primitive neuroectodermal tumor involving the meninges was made. A possibility of primary leptomeningeal tumor extending to parenchyma was considered based on the clinical progression. Patient was treated with chemotherapy and radiotherapy. He improved partially and was stable at 3-year follow-up.

Microwave dielectric relaxation spectroscopy study of propylene glycol/ethanol binary mixtures: Temperature dependence.

Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02<ν/GHz<20. The dipole moment (µ), excess dipole moment (Δµ),excess permittivity (εE), excess inverse relaxation time(1/τ)E, Bruggeman parameter (fB), excess Helmholtz energy (ΔFE) are determined using experimental data. From the minimum energy based geometry optimization, dipole moments of individual monomers of propylene glycol and ethanol and their binary system have been evaluated theoretically at gaseous state as well as alcoholic medium by using PCM and IEFPCM solvation models from the Hatree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-311G* and 6-311G** basis sets. The obtained results have been interpreted in terms of the short and long range ordering of the dipoles, Kirkwood correlation factor (geff), thermodynamic parameters, mean molecular polarizability (αM) and interaction in the mixture through hydrogen bonding.

Structural phase transformation and microwave dielectric studies of SmNb(1-x)(Si(1/2)Mo(1/2))(x)O(4) compounds with fergusonite structure.

Temperature- and composition-induced phase transition in SmNbO4 was studied by differential scanning calorimetry, Raman spectroscopy and high-temperature powder X-ray diffraction measurements. In situ X-ray diffraction studies revealed that SmNbO4 possesses a monoclinic fergusonite crystal structure at ambient temperature and transforms to a tetragonal scheelite structure above the transition temperature (To ≥ 800 °C). The second-order nature of this transition was confirmed by observing a linear relationship between the spontaneous strain (es) of SmNbO4 and the Landau order parameter (η) around the phase transition temperature. We stabilized this high-temperature tetragonal scheelite phase at ambient temperature by substituting Si(4+) and Mo(6+) into the Nb site of SmNbO4. The SmNb1-x(Si1/2Mo1/2)xO4 (x = 0.0-0.69) ceramic compositions were prepared by the conventional solid-state reaction method. Rietveld refinement was carried out on all the compositions to examine the phase purity, and the compositions where x < 0.06 all formed a monoclinic fergusonite structure (I2/a space group, Z = 2). Both the X-ray diffraction and Raman spectroscopy measurements revealed that increasing the concentration of x transformed the structure from monoclinic fergusonite to tetragonal scheelite (I41/a space group, Z = 4) at a critical concentration (xc). Both the monoclinic and tetragonal phases coexisted in the composition range of 0.06 ≤ x < xc. The Hakki-Coleman and reflection cavity techniques were used to measure the dielectric constant and quality factor of these stabilized phases, respectively. The temperature coefficient of the resonant frequency was measured by using an invar cavity attached to a programmable hot plate. The high-density samples possessed good microwave dielectric properties.

Origin of magnetocapacitance in chemically homogeneous and inhomogeneous ferrites.

The present work mainly focuses on the magnetodielectric (MD) effect in polycrystalline Ni0.9-yCuyZn0.1Fe1.98O3.97 (y = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ferrite synthesized by a solid-state reaction method. Sintered samples showed the formation of CuO-rich grain boundary segregation for y≥ 0.2. The appearance of segregation made the present material chemically inhomogeneous and electrically heterogeneous. A negative MD response was observed in homogeneous ferrite for y = 0 and 0.1 due to lattice distortion (an intrinsic effect), whereas a positive MD response occurs in chemically inhomogeneous segregated ferrite (y≥ 0.2) due the collective effects of Maxwell-Wagner (MW) polarization with intrinsic magnetoresistance (an extrinsic effect).

Structural, Raman spectroscopic and microwave dielectric studies on Ni1-x(Zn1/2Zr1/2)xW1-xNbxO4 ceramic compounds with wolframite structure.

Ni1-x(Zn1/2Zr1/2)xW1-xNbxO4 (x = 0.0-1.0) compositions were synthesized via conventional solid-state reaction method. Structural and lattice vibrational characteristics of these compositions were studied with the help of powder X-ray diffraction and Raman spectroscopic measurements. Rietveld refinements confirm the formation of all these compositions in monoclinic wolframite structure with P2/c space group. When moving towards Ni(2+)-poor compositions, splitting in the X-ray reflections was observed and is explained with lattice parameter variation. With increasing value of x, Raman spectra show two additional Raman active modes and the possible reasons for observing these modes are discussed in terms of electronegativity difference of the randomly distributed cations in B-site of these compositions. X-ray photoelectron spectroscopic measurements were done to understand the chemical bonding states of different elements in these compositions. Surface morphology studies reveal that the average grain size increases with increasing x. Microwave dielectric properties such as dielectric constant and quality factor were measured using Hakki-Coleman and reflection cavity techniques and enhancement in these values with x is correlated with intrinsic parameters such as polarizability and 3d electrons present in the constituent ions of these compositions. Temperature coefficient of resonant frequency was measured using an invar cavity attached to a programmable hot plate and is explained with B-site octahedral distortion of these compositions. Well dense Ni1-x(Zn1/2Zr1/2)xW1-xNbxO4 (x = 0.0-1.0) compositions possess good microwave dielectric properties.

Temperature-dependent microwave dielectric relaxation studies of hydrogen bonded polar binary mixtures of propan-1-ol and propionaldehyde.

The molecular interaction between the polar systems of propan-1-ol and propionaldehyde for various mole fractions at different temperatures were studied by determining the frequency dependent complex dielectric permittivity by using the open-ended coaxial probe technique method in the microwave frequency range from 20 MHz to 20 GHz. The geometries are optimized at HF, B3LYP and MP2 with 6-311G and 6-311G+ basis sets. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method and compared with the theoretical results. Conformational analysis of the formation of hydrogen bond between the propan-1-ol and propionaldehyde is supported by the FT-IR and molecular polarizability calculations. The average relaxation times are calculated from their respective Cole-Cole plots. The activation entropy, activation enthalpy and Kirkwood correlation 'g' factor, excess permittivity (ε(E)), excess inverse relaxation time (1/τ)(E), Bruggeman parameter (f(B)) have also been determined for propan-1-ol and propionaldehyde and the results were correlated.

Doubly ortho-linked quinoxaline/diphenylfluorene hybrids as bipolar, fluorescent chameleons for optoelectronic applications.

The titled dipolar hybrids bearing a central quinoxaline-fused dibenzosuberene optoelectronic unit with functional C5 and C8 appendages and spiro-fluorene junction act as fluorescent bipolar OLED chameleons. The emission colors can be tuned from blue, green, yellow, to red with operation brightness of 205, 1268, 1542, and 1102 cd/m2, respectively, at 20 mA/cm2.

Refractometry as a tool in diabetic studies.

The refractive index as well as molar refraction, is the true index of purity of substance and plays a vital role in solution chemistry. A small addition of a foreign substance either in solid state of liquid form is going to effect the refractive index.As such the variation of refractive indices in pure glucose solution as a function of concentration is studied in detail and this principle is extended to the study of the refractive indices of urine solution of diabetic patients. The refractive indices are measured by spectrometry and abbe refractometry. A detailed study of variation of refractive indices of urine samples containing different sugar concentrations, of patients of different age groups revealed that the increase in refractive index follows a linear scale and can be explained by the equation, n=n(o) [l+0.00251og (a s)(1/4)] [l+0.031og0.011C]. These study provided an opportunity to project refractometry as an effective tool in diagnosing the diabetic level of a patient by making use of a simple calibration curve of increment in refractive index 'Δn, as a function of level of the disease.

Doubly ortho-linked quinoxaline/triarylamine hybrid as a bifunctional, dipolar electroluminescent template for optoelectronic applications.

The titled hybrid (Q-H) works as a clippable optoelectronic unit. Q-spacer-Q systems function as efficient orange emitters reaching EL intensities (L) of up to 6840 cd m-2 with etaext of 0.77% and operation efficiencies of 1.60 cd A-1 and 0.8 lm W-1. Notably, Q-An acts as a (bluish) green emitter, reaching L of 12347 cd m-2 with similar operational efficiency.

Bond and molecular polarizabilities in the reactivity studies of uracil and its substituents.

Bond and molecular polarizabilities of uracil and its substituents are determined by molecular vibration and quantum mechanical delta-function potential model. The longitudinal bond polarizability coefficients of C4-C5, C5-CH3 and C5-NO2 bonds confirm that position 5 is partially aromatic while position 4 is aliphatic with reference to the reactivity nature of carbon atoms in uracil. The results are discussed in relation to experimental and theoretical results.

Early differentiation of the Earth and the problem of mantle siderophile elements: a new approach.

The long-standing problem of the excess abundances of siderophile elements in the mantle can be resolved by considering an equilibrium core-mantle differentiation in the earth at 3000 to 3500 kelvin. This high-temperature differentiation results in mantle siderophile element abundances that closely match the observed values. Some lithophile (light) elements could enter the core in this process as is necessary to account for its low density. The abundances of siderophile elements in the mantle are consistent with the conclusion derived from the recent physical models that the earth was molten during accretion.

Optical polarizabilities and related properties of a few biomolecules by new dispersion relation.

As an extension of our studies on simple and macromolecules, the optical polarizabilities of some biomolecules (Glycine, L-alanine and folic acid) have been studied using new dispersion relation. Diamagnetic susceptibilities and electron ionization cross sections for these biomolecules have also been evaluated. The relative merits, feasibility and the limitations of the dispersion relation in relation to other reported methods are discussed critically. The use of the studies in this direction are also cited briefly.