Structural studies of analgesics and their interactions. Part 4. Crystal structures of phenylbutazone and a 2 : 1 complex between phenylbutazone and piperazine

The X-ray crystal structures of 4-butyl-1,2-diphenylpyrazolidine-3,5-dione (phenylbutazone)(I). and its 2 : 1 complex (II) with piperazine have been determined by direct methods and the structures refined to R 0.096 (2 300 observed reflections measured by diffractometer) and 0.074 (2 494 observed reflections visuallyestimated). Crystals are monoclinic, space group P21/c; for (I)a= 21.695(4), b= 5.823(2), c= 27.881(4)Å, = 108.06 (10)°, Z= 8, and for (II)a= 8.048(4), b= 15.081(4), c= 15.583(7)Å, = 95.9(3)°, Z= 2. The two crystallographically independant molecules in the structure of (I) are similar except for the conformation of the butyl group, which is disordered in one of the molecules. In the pyrazolidinedione group, the two C–C bonds are single and the two C–O bonds double. The two nitrogen atoms in the five-membered ring are pyramidal with the attached phenyl groups lying on the opposite sides of the mean plane of the ring. The phenylbutazone molecule in (II) exists as a negative ion owing to deprotonation of C-4. C-4 is therefore trigonal and the orientation of the Bu group with respect to the pyrazolidinedione group is considerably different from that in (I); there is also considerable electron delocalization along the C–O and C–C bonds. These changes in geometry and electronic structure may relate to biological activity. The doubly charged cationic piperazine molecule exists in the chair form with the nitrogen atoms at the apices. The crystal structure of (II) is stabilized by ionic interactions and N–H O hydrogen bonds.

Tris(methyl 3-oxobutanoato-kappa O-2,O `)aluminium(III)

In the title compound, [Al(C5H7O3)(3)],three acac-type ligands(methyl 3-oxobutanoate anions) chelate to the aluminium(III)cation in a slightly distorted AlO6 octahedral coordination geometry.Electron delocalization occurs within the chelating rings.

A direct borohydride fuel cell employing Prussian Blue as mediated electron-transfer hydrogen peroxide reduction catalyst

A direct borohydride-hydrogen peroxide fuel cell employing carbon-supported Prussian Blue (PB) as mediated electron-transfer cathode catalyst is reported. While operating at 30 °C, the direct borohydride-hydrogen peroxide fuel cell employing carbon-supported PB cathode catalyst shows superior performance with the maximum output power density of 68 mW cm−2 at an operating voltage of 1.1 V compared to direct borohydride-hydrogen peroxide fuel cell employing the conventional gold-based cathode with the maximum output power density of 47 mW cm−2 at an operating voltage of 0.7 V. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray Analysis (EDAX) suggest that anchoring of Cetyl-Trimethyl Ammonium Bromide (CTAB) as a surfactant moiety on carbon-supported PB affects the catalyst morphology. Polarization studies on direct borohydride-hydrogen peroxide fuel cell with carbon-supported CTAB-anchored PB cathode exhibit better performance with the maximum output power density of 50 mW cm−2 at an operating voltage of 1 V than the direct borohydride-hydrogen peroxide fuel cell with carbon-supported Prussian Blue without CTAB with the maximum output power density of 29 mW cm−2 at an operating voltage of 1 V.

Electron-electron interaction in percolative network of polymer-amorphous carbon composites

The polymer-amorphous carbon composites show a negative magnetoconductance which varies as B-2 at low fields which changes to B-1/2 at sufficiently high fields. The magnetoconductance gives the evidence of electron-electron interaction in composites whose conductivity follows thermal fluctuation induced tunneling and falls in the critical regime. (c) 2006 Elsevier B.V. All rights reserved.

Electron paramagnetic resonance studies on multiferroic DyMnO3 and Dy0.5Sr0.5MnO3

Electron paramagnetic resonance (EPR) studies and magnetic measurements were carried out on single crystals of multiferroic DyMnO3 in hexagonal as well as orthorhombic structures. The interesting effect of strontium dilution on the frustrated antiferromagnetism of DyMnO3 is also probed using EPR. The line shapes are fitted to broad Lorentzian in the case of pure DyMnO3 and to modified Dysonian in the case of Dy0.5Sr0.5MnO3. The linewidth, integrated intensity, and geff derived from the signals are analyzed as a function of temperature. The results of magnetization measurements corroborate with EPR results. Our study clearly reveals the signature of frustrated magnetism in pure DyMnO3 systems. It is found that antiferromagnetic correlations in these systems persist even above the transition. Moreover, a spin-glass-like behavior in Dy0.5Sr0.5MnO3 is indicated by a steplike feature in the EPR signals at low fields.

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7 BaO-Bi(2)O3-Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 - x)Li2B4O7-x (BaO-Bi2O3-Nb2O5) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi2Nb2O9 phase in the glassy matrix of Li2B4O7 (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated. (c) 2007 Elsevier B.V. All rights reserved.

1-[5-Acetyl-4-(4-bromophenyl)-2,6-dimethyl-1,4-dihydropyridin-3-yl]eth anone monohydrate

The 1,4-dihydropyridine ring in the title hydrate, C17H18BrNO2 center dot H2O, has a flattened-boat conformation, and the benzene ring is occupies a position orthogonal to this [dihedral angle: 82.19 (16)degrees]. In the crystal packing, supramolecular arrays mediated by N-H center dot center dot center dot O-water and O-water-H center dot center dot center dot O-carbonyl hydrogen bonding are formed in the bc plane. A highly disordered solvent molecule is present within a molecular cavity defined by the organic and water molecules. Its contribution to the electron density was removed from the observed data in the final cycles of refinement and the formula, molecular weight and density are given without taking into account the contribution of the solvent molecule.

The generalized anomeric effect in the 1,3-thiazolidines: Evidence forboth sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the. C-2-N and C-2-S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were similar to 0.04 angstrom for C-2-N-3, S-1-C-2, and similar to 0.08 angstrom for N-3-C-6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr2 complex. (The sulphur atom appears to be sp(2) hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins. (c) 2006 Elsevier B.V. All rights reserved.

Anomalous temperature dependence of Fermi-edge singularity in modulation-doped AlGaAs/InGaAs/GaAs hetero-structures

The temperature and power dependence of Fermi-edge singularity (FES) in high-density two-dimensional electron gas, specific to pseudomorphic AlxGa1-xAs/InGa1-yAs/GaAs heterostructures is studied by photoluminescence (PL). In all these structures, there are two prominent transitions E-11 and E-21 considered to be the result of electron-hole recombination from first and second electron sub-bands with that of first heavy-hole sub-band. FES is observed approximately 5-10 meV below the E-21 transition. At 4.2 K, FES appears as a lower energy shoulder to the E-21 transition. The PL intensity of all the three transitions E-11, FES and E-21 grows linearly with excitation power. However, we observe anomalous behavior of FES with temperature. While PL intensity of E-11 and E-21 decrease with increasing temperature, FES transition becomes stronger initially and then quenches-off slowly (till 40K). Though it appears as a distinct peak at about 20 K, its maximum is around 7 - 13 K.

Studies on oxovanadium (IV) oxalate hydrates

The oxalato complexes, VOC2O4·2H2O and VOC2O4·4H2O, are described. Their magnetic moments correspond to one unpaired electron showing the tetravalency of vanadium. They are monomeric in aqueous solution. Thermal studies suggest VO2 formation when the compounds are decomposed. Infrared spectra reveal covalent bonding between the vanadium and the oxalate group and the coordinated water. The tetrahydrate has also some lattice held water. The weak band at 780 mμ and a shoulder at 600 mμ are due to d ↔ d transitions and the absorption in the ultra violet is due to charge transfer within the VO2+ group. The dihydrate is assigned a stable five co-ordinated pyramidal structure; while the tetrahydrate, a distorted octahedron with one water molecule loosely bound along the V---O axis and the other outside the co-ordination sphere.

Electron spin resonance in cupric acid fluoride

The electron spin resonance in undiluted single crystals of cupric acid fluoride has been investigated at room temperature with microwaves of frequency 9625 Mc/s. The anisotropy in the g value has been measured in three orthogonal planes. The principal g values gave gshort parallel = 2.410 ± 0.010, gperpendicular = 2.090 ± 0.010. The linewidth shows anisotropy with orientation. The exchange frequency has been estimated to be approximately 0.08 cm-1.The powdered specimen shows asymmetry in the line shape.

Electron-hole recombination in cobalt-doped p-type germanium

The recombination properties of cobalt centers in p-type germanium containing cobalt in the concentration range 1014 to 1016 atoms/cm3 have been investigated. The measurement of lifetime has been carried out by steady-state photoconductivity and photo-magneto-electric methods in the temperature range 145 to 300°K. The cross-sections Sno (electron capture cross-section at neutral centers). Sn- (electron capture cross-section at singly negatively charged centers) and their temperature variations have been estimated by the analysis of the lifetime data on the basis of Sah-Shockley's multi-level formula. The value of Sno is (15±5).10-16 cm2 and is temperature independent. The value of Sn- is ≈4·10-16 cm2 around 225°K and it increases with increase of temperature. The possible mechanisms for capture at neutral and repulsive centers are discussed and a summary of the capture cross-sections for cobalt centers is given. A comparison of the cross-section values of cobalt and their temperature variations with those of the related impurities-manganese, iron and nickel-in germanium has been made.

Electron-metallographic studies of precipitation in an aluminium-zinc-magnesium alloy

The mechanism of sub-microscopic precipitation in an Al-Zn-Mg alloy selected for its maximum response to ageing has been studied by a standardized oxide-replica technique in a 100 kV. Philips Electron Microscope. Contrary to earlier conclusions, examination of the oxide replicas has been shown to reveal details of the precipitation process almost as clearly as the thin-foil transmission technique. The reported formation of spherical Guinier-Preston zones followed by the development of a Widmanstaetten pattern of precipitated platelets has been confirmed. The zones have, however, been shown to grow into the platelets and not to dissolve in the matrix as reported earlier. The precipitation process has been correlated with the Hardness/Ageing Time curve and the structure of the precipitates has also been discussed.

Quantum kinematics of Fermi-Dirac vacuum-plus-one-electron problem

Following Weisskopf, the kinematics of quantum mechanics is shown to lead to a modified charge distribution for a test electron embedded in the Fermi-Dirac vacuum with interesting consequences.