Infrared studies of the phase transitions of alkylammonium halides, RNH3X, and bis-(alkylammonium) tetrahalogenometallates(II), (RNH3)2MX4, (R = alkyl, M = metal, X = Cl or Br)

Internal vibration modes of bis-(alkylammonium) tetrachlorometallates(II) and the corresponding alkylammonium chlorides have been studied through their phase transitions using infrared spectroscopy. The studies show that the vibrational states of alkylammonium ions change markedly through the phase transitions. Spectra of the analogous tetrabromometallates and alkylammonium bromides also confirm this behaviour. There is appreciable motion of the alkylammonium ions in the high-temperature phases; thus, CH3NH+3 ions are essentially undistorted in these phases. The low-temperature, ordered phases show evidence of stronger hydrogen bonding of the cations and for the presence of C—N torsional modes.

Unique Utilization of a Phosphoprotein Phosphatase Fold by a Mammalian Phosphodiesterase Associated with WAGR Syndrome

Metallophosphoesterase-domain-containing protein 2 (MPPED2) is a highly evolutionarily conserved protein with orthologs found from worms to humans. The human MPPED2 gene is found in a region of chromosome 11 that is deleted in patients with WAGR (Wilms tumor, aniridia, genitourinary anomalies, and mental retardation) syndrome, and MPPED2 may function as a tumor suppressor. However, the precise cellular roles of MPPED2 are unknown, and its low phosphodiesterase activity suggests that substrate hydrolysis may not be its prime function. We present here the structures of MPPED2 and two mutants, which show that the poor activity of MPPED2 is not only a consequence of the substitution of an active-site histidine residue by glycine but also due to binding of AMP or GMP to the active site. This feature, enhanced by structural elements of the protein, allows MPPED2 to utilize the conserved phosphoprotein-phosphatase-like fold in a unique manner, ensuring that its enzymatic activity can be combined with a possible role as a scaffolding or adaptor protein. (C) 2011 Elsevier Ltd. All rights reserved.

Multicomponent solids of lamotrigine with some selected coformers and their characterization by thermoanalytical, spectroscopic and X-ray diffraction methods

The present study investigates the structural and pharmaceutical properties of different multicomponent crystalline forms of lamotrigine (LTG) with some pharmaceutically acceptable coformers viz. nicotinamide (1), acetamide (2), acetic acid (3), 4-hydroxy-benzoic acid (4) and saccharin (5). The structurally homogeneous phases were characterized in the solid state by DSC/TGA, FT-IR and XRD (powder and single crystal structure analysis) as well as in the solution phase. Forms 1 and 2 were found to be cocrystal hydrate and cocrystal, respectively, while in forms 3, 4 and 5, proton transfer was observed from coformer to drug. The enthalpy of formation of multicomponent crystals from their components was determined from the enthalpy of solution of the cocrystals and the components separately. Higher exothermic values of the enthalpy of formation for molecular complexes 3, 4 and 5 suggest these to be more stable than 1 and 2. The solubility was measured in water as well as in phosphate buffers of varying pH. The salt solvate 3 exhibited the highest solubility of the drug in water as well as in buffers over the pH range 7-3 while the cocrystal hydrate 1 showed the maximum solubility in a buffer of pH 2. A significant lowering of the dosage profile of LTG was observed for 1, 3 and 5 in the animal activity studies on mice.

Preparation, characterization and magnetic studies of Bi0.5X0.5(X=Ca,Sr)MnO3 nanoparticles

Nanoparticles (dia ~ 5 - 7 nm) of Bi0.5X0.5(X=Ca,Sr)MnO3 are prepared by polymer assisted sol-gel method and characterized by various physico-chemical techniques. X-ray diffraction gives evidence for single phasic nature of the materials as well as their structures. Mono dispersed to a large extent, isolated nanoparticles are seen in the transmission electron micrographs. High resolution electron microscopy shows the crystalline nature of the nanoparticles. Superconducting quantum interferometer based magnetic measurements from 10K to 300K show that these nanomanganites retain the charge ordering nature unlike Pr and Nd based nanomanganites. The CO in Bi based manganites is thus found to be very robust consistent with the observation that magnetic field of the order of 130 T are necessary to melt the CO in these compounds. These results are supported by electron magnetic resonance measurements.

Cold model study of local liquid holdup in the dropping zone using x-ray

It is important to know and to quantify the liquid holdups both dynamic and static at local levels as it will lead to understand various blast furnace phenomena properly such as slag/metal.gas.solid reactions, gas flow behaviour and interfacial area between the gas/solid/liquid. In the present study, considering the importance of local liquid holdup and non-availability of holdup data in these systems, an attempt has been made to quantify the local holdups in the dropping and around raceway zones in a cold model study using a non-wetting packing for liquid. In order to quantify the liquid holdups at microscopic level, a previously developed technique, X-ray radiography, has been used. It is observed that the liquid flows in preferred paths or channels which carry droplets/rivulets. It has been found that local holdup in some regions of the packed bed is much higher than average at a particular flow rate and this can have important consequences for the correct modelling of such systems.

Crystallization and preliminary X-ray diffraction studies of sortase A from Streptococcus pneumoniae

Sortases are cell-membrane-anchored cysteine transpeptidases that are essential for the assembly and anchoring of cell-surface adhesins in Gram-positive bacteria. Thus, they play critical roles in virulence, infection and colonization by pathogens. Sortases have been classified into four types based on their primary sequence and the target-protein motifs that they recognize. All Gram-positive bacteria express a class A housekeeping sortase (SrtA). Sortase A from Streptococcus pneumoniae (NP_358691) has been crystallized in two crystal forms. Diamond-shaped crystals of Delta N(59)SrtA diffracted to 4.0 angstrom resolution and belonged to a tetragonal system with unit-cell parameters a = b = 122.8, c = 86.5 angstrom, alpha = beta = gamma = 90 degrees, while rod-shaped crystals of Delta N(81)SrtA diffracted to 2.91 angstrom resolution and belonged to the monoclinic space group P2(1) with unit-cell parameters a = 66.8, b = 103.47, c = 74.79 angstrom, alpha = gamma = 90, beta = 115.65 degrees. The Matthews coefficient (V(M) = 2.77 angstrom(3) Da(-1)) with similar to 56% solvent content suggested the presence of four molecules in the asymmetric unit for Delta N(81)SrtA. Also, a multi-copy search using a monomer as a probe in the molecular-replacement method resulted in the successful location of four sortase molecules in the asymmetric unit, with statistics R = 41.61, R(free) = 46.44, correlation coefficient (CC) = 64.31, CC(free) = 57.67.

Oxygen content of liquid cobalt in equilibrium with CoO.(1+x)Al2O3 and -Al2O3

The oxygen concentration of liquid cobalt in equilibrium with cobalt aluminate and a-alumina has been measured by suction sampling and crucible quenching techniques at temperatures between 1770 and 1975 K. Experiments were made with cobalt of high and low initial oxygen contents, and with and without the addition of cobalt aluminate. The effect of temperature on the equilibrium oxygen content is represented by the equation, log (at.% 0) = -10,4001T(K) + 4.64 (±0.008). The composition of the spinel phase, CoO.(1+x)AI20 3, saturated with alumina, has been determined by electron probe microanalysis. The values of x are 0.22 at 1770 Kand 0.28 at 1975 K. The oxygen potential corresponding to the three-phase equilibrium between cobalt, aluminate and alumina, and the standard Gibbs' energy of formation of nonstoichiometric cobalt aluminate are evaluated by combining the results of this study with recently published data on the activity of oxygen in liquid cobalt. Implications of the present results to aluminium deoxidation of liquid cobalt are discussed.

Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

X-ray structure of a galactose-specific lectin from Spatholobous parviflorous

A galactose-specific seed lectin from Spatholobous parviflorus (SPL) has been purified, crystallized and its X-ray structure solved. It is the first lectin purified and crystallized from the genus Spatholobus (family: Fabaceae). The crystals belong to the space group P1, with a = 60.792 angstrom, b = 60.998 angstrom, c = 78.179 angstrom, alpha = 78.68 degrees, beta = 88.62 degrees, gamma = 104.32 degrees. The data were collected at 2.04 angstrom resolution under cryocondition, on a MAR image-plate detector system, mounted on a rotating anode X-ray generator. The coordinates of Dolichos biflorus lectin (1lu1) were successfully used for the structure solution by molecular replacement method. The primary structure of the SPL was not known earlier and it was unambiguously visible in the electron density. S. parviflorus lectin is a hetero-dimeric-tetramer with two alpha and two beta chains of 251 and 239 residues respectively. SPL has two metal ions, Ca(2+) and Mn(2+), bound to a loop region of each chain. The SPL monomers are in jelly roll form. (C) 2011 Elsevier B.V. All rights reserved.

Phase equilibria in the Co Ni F system and activities in (CoxNi1 x)F2 solid solutions at 1373 K

The tie-lines delineating equilibria between CoF2-NiF2 and Co-Ni solid solutions in the ternary Co-Ni-F system at 1373 K have been determined by electron microprobe and EDAX point count analysis of the equilibrated phases. Activities in the fluoride solid solution have been derived from the knowledge of activitycomposition relation in the metallic solid solution and tie-line data,using a modified form of the Gibbs-Duhem integration. The fluorine potentials corresponding to the tie-line compositions have been calculated.The excess Gibbs' energy of mixing for the fluoride solid solution derived from the present data can be represented by the expression