Jadu Samuel

Vibrational spectroscopic (FT-IR, FT-Raman, 1H NMR and UV) investigations and computational study of 5-nitro-2-(4-nitrobenzyl) benzoxazole

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-nitro-2-(4-nitrobenzyl) benzoxazole have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of the normal modes of vibrations was done using GAR2PED program. The energy and oscillator strength calculated by time dependent density functional theory almost compliments with experimental findings. Gauge-including atomic orbital (1)H NMR chemical shifts calculations were carried out by using B3LYP functional with 6-31G basis set. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization have been analyzed using NBO analysis. MEP was performed by the DFT method and the predicted infrared intensities and Raman activities have also been reported. The calculated geometrical parameters are in agreement with that of similar derivatives.

Synthesis, FT-IR investigation and computational study of 5-[(4-Bromophenyl)acetamido]-2-(4-tert-butylphenyl) benzoxazole

The synthesis and antimicrobial properties of 5-[(4-Bromophenyl)acetamido]-2-(4-tertbutylphenyl) benzoxazole are reported in the present work. The optimized molecular structure, (1)H NMR, vibrational frequencies, corresponding vibrational assignments of 5-[(4-Bromophenyl)acetamido]-2-(4-tert-butylphenyl) benzoxazole have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of the normal modes of vibrations was done using GAR2PED program. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. MEP was performed by the SDD method and the predicted infrared intensities have also been reported. The calculated geometrical parameters are in agreement with that of similar derivates. The first hyperpolarizability is high and the title compound is suitable for further NLO studies. Microbiological results indicated that the title compound possessed a broad spectrum activity against the tested Gram-positive, Gram-negative bacteria.

Spectroscopic (FT-IR, FT-Raman), first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis of 5-tert-Butyl-6-chloro- N-((4-(trifluoromethyl)phenyl)pyrazine-2-carboxamide

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 5-tert-Butyl-6-chloro-N-[(4-(trifluoromethyl)phenyl]pyrazine-2-carboxamide have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes of vibrations was done using GAR2PED program. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. From the NBO analysis it is evident that the increased electron density at the nitrogen, carbon atoms leads to the elongation of respective bond length and a lowering of the corresponding stretching wave number. The calculated geometrical parameters are in agreement with that of similar derivatives. The calculated first hyperpolarizability is high and the calculated data suggest an extended π-electron delocalization over the pyrazine ring and carboxamide moiety which is responsible for the nonlinearity of the molecule.

The effect of gamma-irradiation on the thermal decomposition of anhydrous cadmium nitrate

The thermal decomposition of γ-irradiated anhydrous cadmium nitrate was studied by dynamic thermogravimetry. The reaction order, activation energy, frequency factor and entropy of activation were calculated by the Coats-Redfern method and were compared with those of the unirradiated salt. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. The mechanism of the decomposition of unirradiated and irradiated anhydrous cadmium nitrate follows the Mampel equation: -ln(1-α) for g(α) and the rate-controlling process is random nucleation with the formation of a nucleus on every particle.

Quantum mechanical and spectroscopic (FT-IR, FT-Raman, 1H NMR and UV) investigations of 2-(p-nitrobenzyl) benzoxazole

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2(p-nitrobenzyl)benzoxazole have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of the normal modes of vibrations are done using GAR2PED program. The optimized geometrical parameters are in agreement with that of similar derivatives. The energy and oscillator strength calculated by Time Dependent Density Functional Theory results almost compliments with experimental findings. Gauge-including atomic orbital H NMR chemical shifts calculations were carried out by using B3LYP functional with 6-31G basis sets. The HOMO and LUMO analysis is used to determine the charge transfer with in the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. MEP was performed by the DFT method and the infrared and Raman intensities have also been reported. Mulliken’s net charges have been calculated and compared with the atomic natural charges. The calculated first hyperpolarizability of the title compound is 82.31 time that of the standard NLO material urea and hence is an attractive object for future studies of nonlinear optical properties. 2013 Elsevier B.V. All rights reserved.

Green synthesis of novel polyoxoanions of tungsten containing phosphorus as a heteroatom: characterization, non-isothermal decomposition kinetics and photocatalytic activity

Synthesis of cetylpyridinium phosphotungstate (CPW) nanospheres was carried out by using sodium tungstate and a structure directing cationic surfactant, cetyl pyridinium chloride (CPC), at room temperature by applying green chemistry principles. The composition and morphology of the nanospheres were established by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under a nitrogen atmosphere at four different heating rates 10, 15, 20 and 25 °C min−1. The thermal decomposition of CPW occurred in two stages. The activation energy values at each stage of thermal decomposition for all heating rates were calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. The invariant kinetic parameter (IKP) method and the master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of CPW. The photocatalytic water oxidation mechanism using a CPW catalyst in the presence of a platinum (Pt) co-catalyst enhances the H2 evolution, which was found to be 2.0 mmol g−1 h−1.

Annealing of chemical radiation damage in gamma irradiated anhydrous lanthanum nitrate

The annealing of gamma irradiation damage in anhydrous lanthanum nitrate at different temperatures in the range 383–423 K has been investigated from a viewpoint of reaction kinetics. The annealing data have been analyzed on the basis of models developed for vacancy-interstitial combination and also on the basis of conventional chemical kinetics. Thermal annealing is found to be a combination of a fast first-order process affecting a small proportion of the fragments, followed by a predominantly slow second-order process, with a higher energy of activation, governing the behaviour of the remainder.

Evaluation of kinetic parameters for the thermal decomposition of gamma-irradiated anhydrous lanthanum nitrate

The thermal decomposition of gamma-irradiated anhydrous lanthanum nitrate was studied by dynamic thermogravimetry. The decomposition proceeds via three consecutive stages characterized by different activation energies. The reaction order, activation energy, frequency factor and entropy of activation were calculated using the Coats–Redfern, Freeman–Carroll and Horowitz–Metzger methods and were compared with those of the unirradiated salt. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energies of all the three stages decrease on irradiation. The mechanism of the decomposition of unirradiated and irradiated anhydrous lanthanum nitrate follows the Mampel model equation,−ln(1−α) for g(α), and the rate-controlling process is random nucleation with the formation of a nucleus on every particle.

Green chemical incorporation of silicon into polyoxoanions of molybdenum: characterization, thermal kinetics study and their photocatalytic water splitting activity

Cetylpyridinium silicomolybdate (CSM) nanorods were successfully synthesized by applying green chemistry principles using sodium molybdate and a structure directing cationic surfactant, cetyl pyridinium chloride (CPC) at room temperature. The composition and morphology of the nanorods were established by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TG) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. The thermal decomposition kinetics of CSM nanorods were investigated by a non-isothermal thermogravimetric analyzer at various heating rates. The thermal decomposition of CSM occurred in two stages. The activation energies of the first and second stages of thermal decomposition for all heating rates have been estimated using the iso-conventional methods of Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) and the results are found to be in good agreement with each other. The invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of CSM. The photocatalytic water oxidation mechanism using the CSM catalyst in the presence of platinum (Pt) co-catalyst enhances the H2 evolution and was found to be 1.946 mmol g−1 h−1.