Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide

In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the OFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide. (C) 2012 Elsevier B.V. All rights reserved.

CdSiO3:Pr3+ nanophosphor: Synthesis, characterization and thermoluminescence studies

A series of Pr3+ (1-9 mol%) doped CdSiO3 nanophosphors have been prepared for the first time by a low temperature solution combustion method using oxalyldihydrizide (ODH) as a fuel. The final product was characterized by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The average crystallite size was calculated using Debye-Scherrer's formula and Williamson-Hall (W-H) plots and found to be in the range 31-37 nm. The optical energy band gap (E-g) of undoped for Pr3+ doped samples were estimated from Tauc relation which varies from 5.15-5.36 eV. Thermoluminescence (TL) properties of Pr3+ doped CdSiO3 nanophosphor has been investigated using gamma-irradiation in the dose range 1-6 kGy at a heating rate of 5 degrees C s(-1). The phosphor shows a well resolved glow peak at similar to 171 degrees C along with shouldered peak at 223 degrees C in the higher temperature side. It is observed that TL intensity increase with increase of Pr3+ concentration. Further, the TL intensity at 171 degrees C is found to be increase linearly with increase in gamma-dose which is highly useful in radiation dosimetry. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics was estimated by Luschiks method and the results are discussed. (c) 2012 Elsevier B.V. All rights reserved.

The Structural Characterization of Folded Peptides Containing the Conformationally Constrained beta-Amino Acid Residue beta(2,2)Ac(6)c

Backbone alkylation has been shown to result in a dramatic reduction in the conformational space that is sterically accessible to a-amino acid residues in peptides. By extension, the presence of geminal dialkyl substituents at backbone atoms also restricts available conformational space for beta and ? residues. Five peptides containing the achiral beta 2,2-disubstituted beta-amino acid residue, 1-(aminomethyl)cyclohexanecarboxylic acid (beta 2,2Ac6c), have been structurally characterized in crystals by X-ray diffraction. The tripeptide Boc-Aib-beta 2,2Ac6c-Aib-OMe (1) adopts a novel fold stabilized by two intramolecular H-bonds (C11 and C9) of opposite directionality. The tetrapeptide Boc-Aib-beta 2,2Ac6c]2-OMe (2) and pentapeptide Boc-Aib-beta 2,2Ac6c]2-Aib-OMe (3) form short stretches of a hybrid a beta C11 helix stabilized by two and three intramolecular H-bonds, respectively. The structure of the dipeptide Boc-Aib-beta 2,2Ac6c-OMe (5) does not reveal any intramolecular H-bond. The aggregation pattern in the crystal provides an example of an extended conformation of the beta 2,2Ac6c residue, forming a polar sheet like H-bond. The protected derivative Ac-beta 2,2Ac6c-NHMe (4) adopts a locally folded gauche conformation about the C beta?Ca bonds (?=-55.7 degrees). Of the seven examples of beta 2,2Ac6c residues reported here, six adopt gauche conformations, a feature which promotes local folding when incorporated into peptides. A comparison between the conformational properties of beta 2,2Ac6c and beta 3,3Ac6c residues, in peptides, is presented. Backbone torsional parameters of H-bonded a beta/beta a turns are derived from the structures presented in this study and earlier reports.

Characterization and iodide adsorption behaviour of HDPY+ modified bentonite

Owing to its favourable physical, chemical and rheological properties, densely compacted bentonite or bentonite-sand mix is considered as a suitable buffer material in deep geological repositories to store high level nuclear waste. Iodine-129 is one of the significant nuclides in the high level waste owing to its long half life and poor sorption onto most geologic media. Bentonite by virtue of negatively charged surface has negligible affinity to retain iodide ions. As organo-bentonites are known to retain iodide ions, the present study characterizes hexadecylpyridinium chloride (HDPyCl.H2O) treated bentonite from Barmer India (referred as HDPy+B) for physico-chemical properties, engineering properties and the iodide adsorption behavior of the organo clay. Batch experiments revealed that HDPy+ ions are largely retained (94 % retention) via cation exchange; the ion-exchange process neutralizes the negative surface charge and bridges clay particles leading to reduction in Atterberg limits, clay content and sediment volume. The organo clay retains iodide by Coulombic attraction (at primary sites) and anion exchange (at secondary sites). The free-energy change (Delta G (o) = -25.5 kJ/mol) value indicated that iodide retention by organo clay is favored physical adsorption process. Iodide adsorption capacity of organo clay decreased significantly (85-100 %) on dilution with 50-80 % bentonite. On the other hand, dilution of bentonite with 50 % organo clay caused 58 % reduction in swell potential and 21 % reduction in swell pressure.

Synthesis and characterization of nickel/barium hexa-aluminate composite coatings

Electrodeposition of nickel/barium hexa-aluminate (Ni/BHA) composite coatings has been carried out from a Watt's bath on mild steel substrate. BHA powders with plate habit were synthesized by solution combustion synthesis followed by heat treatment to ensure complete conversion to the hexa-aluminate phase. Heat treated material was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with X-ray analysis. The dispersion behaviour and stability of BHA suspensions with cationic and anionic surfactants at room temperature were studied by dynamic light scattering under different pH. The influence of BHA concentration in the electrolytic bath, deposition temperature, pH, current density and duty cycle on particle incorporation in the coatings were studied and conditions for maximum particle incorporation were established. Coatings with a roughness of about 0 center dot 4 mu m were produced by using this technique. Effect of BHA content on microhardness was also investigated. A reasonably good thickness of the coatings was achieved in a given set of conditions.

Functional characterization, homology modeling and docking studies of beta-glucosidase responsible for bioactivation of cyanogenic hydroxynitrile glucosides from Leucaena leucocephala (subabul)

Glycosyl hydrolase family 1 beta-glucosidases are important enzymes that serve many diverse functions in plants including defense, whereby hydrolyzing the defensive compounds such as hydroxynitrile glucosides. A hydroxynitrile glucoside cleaving beta-glucosidase gene (Llbglu1) was isolated from Leucaena leucocephala, cloned into pET-28a (+) and expressed in E. coli BL21 (DE3) cells. The recombinant enzyme was purified by Ni-NTA affinity chromatography. The optimal temperature and pH for this beta-glucosidase were found to be 45 A degrees C and 4.8, respectively. The purified Llbglu1 enzyme hydrolyzed the synthetic glycosides, pNPGlucoside (pNPGlc) and pNPGalactoside (pNPGal). Also, the enzyme hydrolyzed amygdalin, a hydroxynitrile glycoside and a few of the tested flavonoid and isoflavonoid glucosides. The kinetic parameters K (m) and V (max) were found to be 38.59 mu M and 0.8237 mu M/mg/min for pNPGlc, whereas for pNPGal the values were observed as 1845 mu M and 0.1037 mu M/mg/min. In the present study, a three dimensional (3D) model of the Llbglu1 was built by MODELLER software to find out the substrate binding sites and the quality of the model was examined using the program PROCHEK. Docking studies indicated that conserved active site residues are Glu 199, Glu 413, His 153, Asn 198, Val 270, Asn 340, and Trp 462. Docking of rhodiocyanoside A with the modeled Llbglu1 resulted in a binding with free energy change (Delta G) of -5.52 kcal/mol on which basis rhodiocyanoside A could be considered as a potential substrate.

Synthesis and characterization of Fe- and Co-based ferrite nanoparticles and study of the T-1 and T-2 relaxivity of chitosan-coated particles

In pursuit of newer and more effective contrast agents for magnetic resonance imaging, we report in this article the use of biocompatible chitosan-coated ferrite nanoparticles of different kinds with a view to determine their potential applications as the contrast agents in the field of nuclear magnetic resonance. The single-phase ferrite particles were synthesized by chemical co-precipitation (CoFe2O4 and Fe3O4) and by applying ultrasonic vibration (CoFe2O4 and Co0.8Zn0.2Fe2O4). Although magnetic anisotropy of CoFe2O4 nanoparticle leads to finite coercivity even for nanoensembles, it has been reduced significantly to a minimum level by applying ultrasonic vibration. Fe3O4 synthesized by chemical co-precipitation yielded particles which already possess negligible coercivity and remanence. Substitution of Co by Zn in CoFe2O4 increases the magnetization significantly with a small increase in coercivity and remanence. Particles synthesized by the application of ultrasonic vibration leads to the higher values of T-2 relaxivities than by chemical coprecipitation. We report that the T-2 relaxivities of these particles are of two orders of magnitude higher than corresponding T-1 relaxivities. Thus, these particles are evidently suitable as contrast agent for T-2 weighted MR images.

Synthesis and structural characterization of two-dimensional hierarchical covellite nano-structures

We report a simple, template free and low-temperature hydrothermal reaction pathway using Cu(II) - thiourea complex (prepared in situ from copper (II) chloride and thiourea as precursors) and citric acid as complexing agent to synthesize two-dimensional hierarchical nano-structures of covellite (CuS). The product was characterized with the help of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis of X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS). The concentration of citric acid in the hydrothermal precursor solution was seen to have a profound effect on the nanostructure of the product generated. Based on the outcoming product nano-architecture at different concentration of the ionic surfactant in the hydrothermal precursor solution a possible mechanism suited for reaction and further nucleation is also discussed. (C) 2012 Elsevier B.V. All rights reserved.