Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

Complex structural phase transitions in slightly Ca modified Na0.5Bi0.5TiO3

A temperature dependent neutron powder diffraction study, in conjunction with dielectric and ferroelectric characterization, of slightly Ca modified Na0.5Bi0.5TiO3 (NBT) revealed an instability with regard to a non-polar orthorhombic (Pbnm) distortion above room temperature. This intermediate orthorhombic phase has earlier been reported for unmodified NBT by electron diffraction studies, but has never been captured by global (x-ray/neutron) diffraction techniques. Calcium substitution seems to amplify the magnitude of this intermediate orthorhombic distortion thereby making the corresponding superlattice reflections become visible in the neutron diffraction pattern. The study revealed the following sequence of very complex structural evolution with temperature: Cc -> Cc + Pbnm -> Pbnm + P4/mbm -> P4/mbm -> Pm (3) over barm.

In situ structural studies on orthorhombic SnS micro-crystals

In situ powder X-ray diffraction (XRD) studies on 3D micro-crystalline tin (II) sulfide (SnS) were carried out at different temperatures. While increasing temperature, the crystal structure of SnS remains stable as orthorhombic, whereas its lattice parameters and unit-cell volume are considerably varied. Further, these 3D micro-crystalline structures have showed a negative thermal expansion along the a-axis and positive expansion along the b- and c-axes. However, the overall drop along the a-axis of SnS crystals is nearly equal to their expansion along the c-axis. The observed changes in the structural properties of SnS micro-crystallites with temperature are discussed and reported.

Efficient Algorithms for Linear Summed Error Structural SVMs

Structural Support Vector Machines (SSVMs) have become a popular tool in machine learning for predicting structured objects like parse trees, Part-of-Speech (POS) label sequences and image segments. Various efficient algorithmic techniques have been proposed for training SSVMs for large datasets. The typical SSVM formulation contains a regularizer term and a composite loss term. The loss term is usually composed of the Linear Maximum Error (LME) associated with the training examples. Other alternatives for the loss term are yet to be explored for SSVMs. We formulate a new SSVM with Linear Summed Error (LSE) loss term and propose efficient algorithms to train the new SSVM formulation using primal cutting-plane method and sequential dual coordinate descent method. Numerical experiments on benchmark datasets demonstrate that the sequential dual coordinate descent method is faster than the cutting-plane method and reaches the steady-state generalization performance faster. It is thus a useful alternative for training SSVMs when linear summed error is used.

Stabilization and Structural Alteration of the G-Quadruplex DNA Made from the Human Telomeric Repeat Mediated by Troger's Base Based Novel Benzimidazole Derivatives

Ligand-induced stabilization of the G-quadruplex DNA structure derived from the single-stranded 3'-overhang of the telomeric DNA is an attractive strategy for the inhibition of the telomerase activity. The agents that can induce/stabilize a DNA sequence into a G-quadruplex structure are therefore potential anticancer drugs. Herein we present the first report of the interactions of two novel bisbenzimidazoles (TBBz1 and TBBz2) based on Troger's base skeleton with the G-quadruplex DNA (G4DNA). These Troger's base molecules stabilize the G4DNA derived from a human telomeric sequence. Evidence of their strong interaction with the G4DNA has been obtained from CD spectroscopy, thermal denaturation, and UV-vis titration studies. These ligands also possess significantly higher affinity toward the G4DNA over the duplex DNA. The above results obtained are in excellent agreement with the biological activity, measured in vitro using a modified TRAP assay. Furthermore, the ligands are selectively more cytotoxic toward the cancerous cells than the corresponding noncancerous cells. Computational studies suggested that the adaptive scaffold might allow these ligands to occupy not only the G-quartet planes but also the grooves of the G4DNA.

Influence of growth ambience and doping on the structural properties of multiferroic DyMnO3

We report on the single crystal growth of 50% Sr and Y doped multiferroic DyMnO3 using optical floating zone technique. A comparison of the effect of growth ambience and of chemical substitution on the crystal structure of DyMnO3 is attempted. It is observed that DyMnO3 adopts Pm3m cubic structure with 50% Sr doping whereas with 50% Y doping, the crystal structure is hexagonal P6(3)cm. Orthorhombic Pnma structure is adopted by DyMnO3 when grown in air, whereas hexagonal P6(3)cm structure is obtained when grown under the ambience of argon. The structural polymorphism is discussed in terms of difference in ionic sizes of Sr, Y and Dy, comparable Gibbs free energies and coordination schemes of surrounding oxygens for hexagonal and orthorhombic structures of DyMnO3. (C) 2012 Elsevier B.V. All rights reserved.

Indentation size effect and shear transformation zone size in a bulk metallic glass in two different structural states

The existence of an indentation size effect (ISE) in the onset of yield in a Zr-based bulk metallic glass (BMG) is investigated by employing spherical-tip nanoindentation experiments. Statistically significant data on the load at which the first pop-in in the displacement occurs were obtained for three different tip radii and in two different structural states (as-cast and structurally relaxed) of the BMG. Hertzian contact mechanics were employed to convert the pop-in loads to the maximum shear stress underneath the indenter. Results establish the existence of an ISE in the BMG of both structural states, with shear yield stress increasing with decreasing tip radius. Structural relaxation was found to increase the yield stress and decrease the variability in the data, indicating ``structural homogenization'' with annealing. Statistical analysis of the data was employed to estimate the shear transformation zone (STZ) size. Results of this analysis indicate an STZ size of similar to 25 atoms, which increases to similar to 34 atoms upon annealing. These observations are discussed in terms of internal structure changes that occur during structural relaxation and their interaction with the stressed volumes in spherical indentation of a metallic glass. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

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.

Influence of Side-Chain on Structural Order and Photophysical Properties in Thiophene Based Diketopyrrolopyrroles: A Systematic Study

In this work, we have synthesized a series of TDPP derivatives with different alkyl groups such as n-hexyl (-C6H13) 3a, 2-ethylhexyl (-(2-C2H5)C6H12) 3b, triethylene glycol mono methyl ether (-(CH2CH2O)(3c)H-3, TEG) 3c, and octadodecyl (-(8-C8H17)C12H22) 3d. N,N dialkylation of Othiophene-diketopyrrolopyrrole (TDPP, 1) strongly influences its solubility, solid state packing, and structural order. These materials allow us to explicitly study the influence of alkyl chain on solid state packing and photophysical properties. TDPP moiety containing two different alkyl groups 3e (TEG and 2-ethylhexyl) and 3f (TEG and n-hexyl) were synthesized for the first time. The absorption spectra of all derivatives exhibited a red shift in solid state when compared to their solution spectra. The type of alkyl chains leads to change in the optical band gaps in solid state. The fluorescence study reveals that TDPP derivatives have strong pi-pi interaction in the solid state and the extent of bathochromic shift is due to combination of intramolecular interaction and formation of aggregates in solid state. This behavior strongly depends on the nature of alkyl chain. The presence of strong C-H center dot center dot center dot O inter chain interactions and CH-pi interactions in solid state exhibits strong influence on the photophysical properties of TDPP chromophore.

Structural and molecular basis of interaction of HCV non-structural protein 5A with human casein kinase 1 alpha and PKR

Background: Interaction of non-structural protein 5A (NS5A) of Hepatitis C virus (HCV) with human kinases namely, casein kinase 1 alpha (ck1 alpha) and protein kinase R (PKR) have different functional implications such as regulation of viral replication and evasion of interferon induced immune response respectively. Understanding the structural and molecular basis of interactions of the viral protein with two different human kinases can be useful in developing strategies for treatment against HCV. Results: Serine 232 of NS5A is known to be phosphorylated by human ck1 alpha. A structural model of NS5A peptide containing phosphoacceptor residue Serine 232 bound to ck1 alpha has been generated using the known 3-D structures of kinase-peptide complexes. The substrate interacting residues in ck1 alpha has been identified from the model and these are found to be conserved well in the ck1 family. ck1 alpha - substrate peptide complex has also been used to understand the structural basis of association between ck1 alpha and its other viral stress induced substrate, tumour suppressor p53 transactivation domain which has a crystal structure available. Interaction of NS5A with another human kinase PKR is primarily genotype specific. NS5A from genotype 1b has been shown to interact and inhibit PKR whereas NS5A from genotype 2a/3a are unable to bind and inhibit PKR efficiently. This is one of the main reasons for the varied response to interferon therapy in HCV patients across different genotypes. Using PKR crystal structure, sequence alignment and evolutionary trace analysis some of the critical residues responsible for the interaction of NS5A 1b with PKR have been identified. Conclusions: The substrate interacting residues in ck1 alpha have been identified using the structural model of kinase substrate peptide. The PKR interacting NS5A 1b residues have also been predicted using PKR crystal structure, NS5A sequence analysis along with known experimental results. Functional significance and nature of interaction of interferon sensitivity determining region and variable region 3 of NS5A in different genotypes with PKR which was experimentally shown are also supported by the findings of evolutionary trace analysis. Designing inhibitors to prevent this interaction could enable the HCV genotype 1 infected patients respond well to interferon therapy.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Synthesis, structural analysis and solvatochromic behaviour of 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile mesogen

In this communication, we report the synthesis and characterisation of a new luminescent liquid crystalline material, 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile (3). We have confirmed its structure by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy, elemental analysis and X-ray single crystal diffraction studies. The newly synthesised compound crystallises in a monoclinic system with the space group C2/c and its cell parameters are found to be a?=?25.181(4) angstrom, b?=?15.651(4)angstrom, c?=?12.703(19) angstrom, V?=?4880.4 (16) angstrom, Z?=?8. The results indicate that the presence of weak CH center dot center dot center dot O and CH center dot center dot center dot N hydrogen bonding as short-range intermolecular interactions are responsible for the formation of its crystal assembly. The measured torsion angle shows the existence of a distorted structure for the molecule wherein 4-butoxyphenylene ring substituent at the fourth position of the central pyridine ring forms a torsion angle chiC(4), C(3), C(10), C(19)] of 40.55 degrees. Its liquid crystalline behaviour was investigated with the aid of polarised optical microscopy and differential scanning calorimetry. The study reveals that the compound displays a broad nematic phase in the range of 78112 degrees C. Further, solution phase optical studies indicate that it is a blue light emitter in different non-polar and polar organic solvents at a concentration of 10-5M.

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.

Synthon Modularity in 4-Hydroxybenzamide-Dicarboxylic Acid Cocrystals

A family of 4-hydroxybenzamide-dicarboxylic acid cocrystals has been designed and subsequently isolated and characterized. The design strategy follows from an understanding of synthon modularity in crystal structures of monocomponent crystals such as gamma-quinol, 4,4'-biphenol and 4-hydroxybenzoic acid. These monocomponent structures contain infinite O-H center dot center dot center dot O-H center dot center dot center dot O-H center dot center dot center dot cooperative synthons linked with molecular connectors such as phenyl and biphenyl, and supramolecular connectors such as the acid dimer in 4-hydroxybenzoic acid. The cocrystal design was influenced by the anticipation that dicarboxylic acids can form a supramolecular connector mediated by acid-amide synthons with 4-hydroxybenzamide, which can then form the phenol O-H center dot center dot center dot O-H center dot center dot center dot O-H center dot center dot center dot infinite synthon. Effectively, the acid-amide and phenol synthons are insulated. The short axis of such a structure will be around 5.12 angstrom and this is borne out in 2:1 cocrystals of 4-hydroxybenzamide with oxalic, succinic, fumaric, glutaric (two forms) and pimelic acids. Hydrated variations of this structure type are seen in the cocrystals obtained with adipic and sebacic acids.