Structural studies of analgesics and their interactions. VII. Stereoisomerism and disorder in the structure of oxyphenbutazone monohydrate

Oxyphenbutazone, C19H20N203, a metabolite and perhaps the active form of phenylbutazone, is a widely used non-narcotic analgesic and anti-inflammatory pyrazolidinedione derivative. The monohydrate of the compound crystallizes in the triclinic space group Pi with two molecules in a unit cell of dimensions a -- 9.491 (4), b = 10.261 (5), c = 11.036 (3)A and ¢~ = 72.2 (1), fl = 64.3 (1), 7 = 73.0 (1) °. The structure was solved by direct methods and refined to an R value of 0.107 for 1498 observed reflections. The butyl group in the molecule is disordered. The hydroxyl group occupies two sites with unequal occupancies. On account of the asymmetry at the two N atoms and one of the C atoms in the central five-membered ring, the molecule can exist in eight isomeric states, of which four are sterically unfavourable. The disorder in the position of the hydroxyl group can be readily explained on the basis of the existence, with unequal abundances, of all four sterically favourable isomers.The bond lengths and angles in the molecule are similar to those in phenylbutazone. The crystal structure is stabilized by van der Waals interactions, and O-H... O hydrogen bonds involving the carbonyl and the hydroxyl groups as well as a water molecule.

Studies on crystalline complexes involving amino acids. V. The structure of L-serine-L-ascorbic acid

L-Serine-L-ascorbic acid, C3HTNOa. C6HsO6, a 1:1 complex between the amino acid serine and the vitamin ascorbic acid, crystallizes in the orthorhombic space group P2~2~2~ with four formula units in a cell of dimensions a = 5.335(3), b = 8.769(2), c = 25.782 (5) A. The structure was solved by direct methods and refined by full-matrix least squares to an R of 0.036 for 951 observed reflections. Both molecules are neutral in the structure. The conformation of the serine molecule is different from that observed in the crystal structures of L-serine, DL-serine and L-serine monohydrate. The enediol group in the ascorbic acid molecule is planar, whereas significant departures from planarity are observed in the lactone group. The conformation of this molecule is similar to that observed in arginine ascorbate. The unlike molecules aggregate into separate columns in the crystal structure. The columns are held together by hydrogen bonds. Among these, a pair of hydrogen bonds between the enediol group of ascorbic acid and the carboxylate group of serine provides a possible model for a specific interaction between ascorbic acid and a carboxylate ion.

Dielectric, pyroelectric and ferroelectric properties of Bi4Ti2.98Nb0.01Ta0.01O12 ceramics

The electrical conductivity and electrical relaxation for ferroelectric Bi4Ti2.98Nb0.01Ta0.01O12 (BTNT) ceramics have been reported in the frequency range 0.1 Hz to 1 MHz and in the 300-550 degrees C temperature range. The electrical data was analyzed in the framework of the dielectric as well as the electric modulus formalisms. The bulk dc conductivity at various temperatures was extracted from the electrical relaxation data. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 0.93 +/- 0.03 eV, close to that of the activation energy for dc conductivity (1.03 +/- 0.02 eV). It suggests that the movements of oxygen ions are responsible for both ionic conduction as well as the relaxation process. The pyroelectric coefficient was found to be 12 mu C m(-2) K-1 at room temperature which is higher than that of the reported value of pyroelectric coefficient for undoped Bi4Ti3O12 ceramics. (C) 2010 Elsevier B.V. All rights reserved.

Urey-Bradley potential function for the in-plane vibrations of boric acid

The Urey-Bradley force constants for the in-plane vibrations of the boric acid molecule are calculated using the Wilson's F-G matrix method. They are as follows: KO-H=5·23, KB-O=4·94, HBOH=0·36, {Mathematical expression}, F00=0·68 and FBH=0·98 in units of 105 dynes/cm. Using the force constants, the frequencies are recalculated and the calculated values agree with the observed values satisfactorily. The in-plane vibrational frequencies of deuterated boric acid are also calculated and again satisfactory agreement with the observed values is found.

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.

Unified large and small signal non-quasi-static model for long channel symmetric DG MOSFET

We propose a unified model for large signal and small signal non-quasi-static analysis of long channel symmetric double gate MOSFET. The model is physics based and relies only on the very basic approximation needed for a charge-based model. It is based on the EKV formalism Enz C, Vittoz EA. Charge based MOS transistor modeling. Wiley; 2006] and is valid in all regions of operation and thus suitable for RF circuit design. Proposed model is verified with professional numerical device simulator and excellent agreement is found. (C) 2010 Elsevier Ltd. All rights reserved.

Crystal and molecular structure of l-valyl-l-lysine hydrochloride

l-Valyl-l-lysine hydrochloride, C11N3O3H23 HCl, rystallizes in the monoclinic space group P2, with a = 5.438(5), b = 14.188(5), c = 9.521(5) Å, β= 95.38(2)° and Z = 2. The crystal structure, solved by direct methods, refined to R = 0.036, using full matrix least-squares method. The peptide exists in a zwitterionic form, with the N atom of the lysine side-chain protonated. The two γ-carbons of the valine side-chain have positional disorder, giving rise to two conformations, χ111= -67.3 and 65.9°, one of which (65.9°) is sterically less favourable and has been found to be less popular amongst residues branching at β-C. The lysine side-chain has the geometry of g− tgt, not seen in crystal structures of the dipeptides reported so far. Interestingly, χ32 (63.6°) of lysine side-chain has a gauche+ conformation unlike in most of the other tructures, where it is trans. The neighbouring peptide molecules are hydrogen bonded in a head-to-tail fashion, a rather uncommon interaction in lysine peptide structures. The structure shows considerable similarity with that of l-Lys-l-Val HO in conformational angles and H-bond interactions [4].

Organometallic derivatives of diphosphazanes. 2. Seven-coordinated Group 6 metal tricarbonyl complexes of diphosphazane ligands. X-ray crystal structure of [WI2(CO)3{P(OPh)2}2NPh]

The reactions of the complexes [MI2(CO)3-(NCMe)2] (M = Mo, W) with the diphosphazane ligands RN{P(OPh)2}2 (R = Me, Ph) in CH2Cl2 at room temperature afford new seven-coordinated complexes of the type [MI2(CO)3{P(OPh)2}2NR]. The molybdenum complexes are sensitive to air oxidation even in the solid state, whereas the tungsten complexes are more stable in the solid state and in solution. The structure of the tungsten complex [WI2(CO)3{P(OPh)2}2NPh] has been determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system with the space group Pna 2(1), a = 19.372 (2) angstrom, b = 11.511 (1) angstrom, c = 15.581 (1) angstrom, and Z = 4. Full-matrix least-squares refinement with 3548 reflections (I > 2.5-sigma-(I)) led to final R and R(w) values of 0.036 and 0.034, respectively. The complex adopts a slightly distorted pentagonal-bypyramidal geometry rarely observed for such a type of complexes; two phosphorus atoms of the diphosphazane ligand, two iodine atoms, and a carbonyl group occupy the equatorial plane, and the other two carbonyl groups, the apical positions.

Biomimetic synthesis of silver nanoparticles by Citrus limon (lemon) aqueous extract and theoretical prediction of particle size

In the present study silver nanoparticles were rapidly synthesized at room temperature by treating silver ions with the Citrus limon (lemon) extract The effect of various process parameters like the reductant con centration mixing ratio of the reactants and the concentration of silver nitrate were studied in detail In the standardized process 10(-2) M silver nitrate solution was interacted for 411 with lemon Juice (2% citric acid concentration and 0 5% ascorbic acid concentration) in the ratio of 1 4(vol vol) The formation of silver nanoparticles was confirmed by Surface Plasmon Resonance as determined by UV-Visible spectra in the range of 400-500 nm X ray diffraction analysis revealed the distinctive facets (1 1 1 200 220 2 2 2 and 3 1 1 planes) of silver nanoparticles We found that citric acid was the principal reducing agent for the nanosynthesis process FT IR spectral studies demonstrated citric acid as the probable stabilizing agent Silver nanoparticles below 50 nm with spherical and spheroidal shape were observed from transmission electron microscopy The correlation between absorption maxima and particle sizes were derived for different UV-Visible absorption maxima (corresponding to different citric acid concentrations) employing MiePlot v 3 4 The theoretical particle size corresponding to 2% citric acid concentration was corn pared to those obtained by various experimental techniques like X ray diffraction analysis atomic force microscopy and transmission electron microscopy (C) 2010 Elsevier B V All rights reserved

Thermodynamic Properties of Niobium Oxides

Thermodynamic properties of three oxides of niobium have been measured using solid state electrochemical cells incorporating yttria-doped thoria (YDT) as the electrolyte in the temperature range T = (1000 to 1300) K. The standard Gibbs energies of formation of NbO, NbO2, and NbO2.422 from the elements can be expressed as: Delta(f)G(NbO)(o) +/- 547/J . mol(-1) = -414 986 + 86.861(T/K) Delta(f)G(NbO2)(o) +/- 548/J . mol(-1) = -779 864 + 164.438(T/K) Delta(f)G(NbO2.422)(o) +/- 775/J . mol(-1) = -911 045 + 197.932(T/K) The results are discussed in comparison with thermodynamic data reported in the literature. The new results refine data for NbO and NbO2 presented in standard data compilations. There are no data in thermodynamic compilations for NbO2.422 (Nb12O29). In the absence of the heat capacity and enthalpy of formation measurements, only the Gibbs energy of formation of NbO2.422 can be assessed. The free energy of formation of stoichiometric Nb2O5 is evaluated on the basis of measurements on NbO2.422 and information available in the literature on phase boundary compositions and isothermal variation of nonstoichiometric parameter with oxygen potential for Nb2O5-x. The results suggest a minor revision of data for Nb2O5. A minimum in the Gibbs energy of mixing for the system Nb-O occurs in the nonstoichiometric domain of Nb2O5-x with x = 0.036.

X-ray studies on crystalline complexes involving amino acids and peptides XIX. Effects of change in chirality in the complexes of succinic acid with dl- and l-arginine

Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.

Strong nonlocalization induced by small scale parameter on terahertz flexural wave dispersion characteristics of a monolayer graphene

This paper presents the strong nonlocal scale effect on the flexural wave propagation in a monolayer graphene sheet. The graphene is modeled as an isotropic plate of one atom thick. Nonlocal governing equation of motion is derived and wave propagation analysis is performed using spectral analysis. The present analysis shows that the flexural wave dispersion in graphene obtained by local and nonlocal elasticity theories is quite different. The nonlocal elasticity calculation shows that the wavenumber escapes to infinite at certain frequency and the corresponding wave velocity tends to zero at that frequency indicating localization and stationary behavior. This behavior is captured in the spectrum and dispersion curves. The cut-off frequency of flexural wave not only depend on the axial wavenumber but also on the nonlocal scaling parameter. The effect of axial wavenumber on the wave behavior in graphene is also discussed in the present manuscript. (C) 2010 Elsevier B.V. All rights reserved.

Anti-malarial herbal remedies of northeast India, Assam: An ethnobotanical survey

Ethnopharmacological relevance: Malaria is a serious public health problem in the north-eastern region of India including Assam, in view of development of chloroquine resistant Plasmodium falciparum. There is need for alternative and affordable therapy. Aim of the study: This study was conducted to document indigenous knowledge, usage customs and practices of medicinal plant species traditionally used by the residents of Sonitpur district of Tezpur, Assam to treat malaria and its associated symptoms. Materials and methods:A total of 50 randomly selected sampling represented by male (38.76%) and female respondents (12.24%) were interviewed using a semi-structured questionnaire. Results: The present ethno-botanical survey revealed 22 species of plants belonging to 17 botanical families were reported to be used exclusively in this region for the treatment of malaria. Verbenaceae (three species), Menispermaceae (two species), and Acanthaceae (two species) botanical families represented the species that are most commonly cited in this survey work and the detailed use of plants has been collected and described. Conclusions: The most serious threat to the existing knowledge and practice on traditional medicinal plants included cultural change, particularly the influence of modernization and lack of interests shown by the next younger generations were the main problems reported by the informants during the field survey. Hence, the proper documentation of traditional medicinal plants being used as anti-malarial agents and related indigenous knowledge held by the tribal community is an important approach to control the spread of vector-borne diseases like malaria reported in this survey work. (C) 2010 Elsevier Ireland Ltd. All rights reserved.

One-dimensional zinc phosphates with linear chain structure

Three one-dimensional zinc phosphates, [C5N2H14][Zn(HPO4)2], I, [C10N4H26][Zn(HPO4)2].2H2O II, and [C4N2H6]2[Zn(HPO4)], III, have been prepared employing hydro/solvothermal methods in the presence of organic amines. While I and II consist of linear chains of corner-shared four-membered rings, III is a polymeric wire where the amine molecule is directly bonded to the metal center. The wire, as well as the chain in these structures, are held together by hydrogen bond interactions involving the amine and the framework oxygens. The polymeric zinc phosphate with wire-like architecture, III, is only the second example of such architecture. Crystal data: I, monoclinic, P21/c (no. 14), a=8.603(2), b=13.529(2), c=10.880(1) Å, β=94.9(1)°, V=1261.6(1) Å3, Z=4, ρcalc.=1.893 gcm−3, μ(MoKα)=2.234 mm−1, R1=0.032, wR2=0.086, [1532 observed reflections with I>2σ(I)], II, orthorhombic, Pbca (no. 61), a=8.393(1), b=15.286(1), c=22.659(1) Å, V=2906.9(2) Å3, Z=8, ρcalc.=1.794 gcm−3, μ(MoKα)=1.957 mm−1, R1=0.055, wR2=0.11, [1565 observed reflections with I>2σ(I) and III, monoclinic, P21/c (no. 14), a=8.241(1), b=13.750(2), c=10.572(1) Å, β=90.9(1)°, V=1197.7(2) Å3, Z=4, ρcalc.=1.805 gcm−3, μ(MoKα)=2.197 mm−1, R1=0.036, wR2=0.10, [1423 observed reflections with I>2σ(I)].

Effective thermal conductivity of a heat generating rod bundle dissipating heat by natural convection and radiation

A numerical study of conjugate natural convection and surface radiation in a horizontal hexagonal sheath housing 19 solid heat generating rods with cladding and argon as the fill gas, is performed. The natural convection in the sheath is driven by the volumetric heat generation in the solid rods. The problem is solved using the FLUENT CFD code. A correlation is obtained to predict the maximum temperature in the rod bundle for different pitch-to-diameter ratios and heat generating rates. The effective thermal conductivity is related to the heat generation rate, maximum temperature and the sheath temperature. Results are presented for the dimensionless maximum temperature, Rayleigh number and the contribution of radiation with changing emissivity, total wattage and the pitch-to-diameter ratio. In the simulation of a larger system that contains a rod bundle, the effective thermal conductivity facilitates simplified modelling of the rod bundle by treating it as a solid of effective thermal conductivity. The parametric studies revealed that the contribution of radiation can be 38-65% of the total heat generation, for the parameter ranges chosen. Data for critical Rayleigh number above which natural convection comes into effect is also presented. (C) 2011 Elsevier B.V. All rights reserved.