Magnetic and Mechanical Anisotropy in a Manganese 2-Methylsuccinate Framework Structure

Hybrid inorganic-organic framework materials exhibit unique properties that can be advantageously tuned through choice of the inorganic and organic components and by control of the crystal structure. We present a new hydrothermally prepared 3D hybrid framework, [Mn(2-methylsuccinate)](n) (1), comprising alternating 2D manganese oxide sheets and isolated MnO(6) octahedra, pillared via syn, anti-syn carboxylates. Powder magnetic characterization shows that the compound is a homospin Mn(II) ferrimagnet below 2.4 K. The easy-axis is revealed by single-crystal magnetic susceptibility studies and a magnetic structure is proposed. Anisotropic elastic moduli and hardness, observed through nanoindentation on differing crystal facets, were correlated with specific structural features. Such measurements of anisotropy are not commonly undertaken, yet allow for a more comprehensive understanding of structure-property relationships.

Cellular proliferation, cellular viability, and biocompatibility of HA-ZnO composites

One of the important issues in the development of hydroxyapatite (HA)-based biomaterials is the prosthetic infection, which limits wider use of monolithic HA despite superior cellular response. Recently, we reported that ZnO addition to HA can induce bactericidal property. It is therefore important to assess how ZnO addition influences the cytotoxicity property and cell adhesion/proliferation on HA-ZnO composite surfaces in vitro. In the above perspective, the objective of this study is to investigate the cell type and material composition dependent cellular proliferation and viability of pressureless sintered HA-ZnO composites. The combination of cell viability data as well as morphological observations of cultured human osteoblast-like SaOS2 cells and mouse fibroblast L929 cells suggests that HA-ZnO composites containing 10 Wt % or lower ZnO exhibit the ability to support cell adhesion and proliferation. Both SaOS2 and L929 cells exhibit extensive multidirectional network of actin cytoskeleton and cell flattening on the lower ZnO containing (=10 Wt %) HA-ZnO composites. The in vitro results illustrate how variation in ZnO content can influence significantly the cell vitality, as evaluated using MTT biochemical assay. Also, the critical statistical analysis reveals that ZnO addition needs to be carefully tailored to ensure good in vitro cytocompatibility. The underlying reasons for difference in biological properties are analyzed. It is suggested that surface wettability as well as dissolution of ZnO, both contribute to the observed differences in cellular viability and proliferation. (C) 2011 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2012.

Synthesis and Antileukemic Activity of Novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl)piper idin-1-yl)ethanone Derivatives

A series of novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl) piperidin-1-yl)ethanone derivatives 9(ae) and 10(ag) were synthesized and characterized by 1H NMR, IR, mass spectral, and elemental analysis. These novel compounds were evaluated for their antileukemic activity against two human leukemic cell lines (K562 and CEM) by using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide assay. Some of the tested compounds showed good antiproliferative activity with IC50 values ranging from 1.6 to 8.0 mu m. Compound 9c, 9e, and 10f with an electron-withdrawing halogen substituent at the para position on the phenyl ring showed excellent in vitro potency against tested human leukemia cells (K562 and CEM).

Testing concordance in species boundaries using acoustic, morphological, and molecular data in the field cricket genus Itaropsis (Orthoptera: Grylloidea, Gryllidae: Gryllinae)

In most taxa, species boundaries are inferred based on differences in morphology or DNA sequences revealed by taxonomic or phylogenetic analyses. In crickets, acoustic mating signals or calling songs have species-specific structures and provide a third data set to infer species boundaries. We examined the concordance in species boundaries obtained using acoustic, morphological, and molecular data sets in the field cricket genus Itaropsis. This genus is currently described by only one valid species, Itaropsis tenella, with a broad distribution in western peninsular India and Sri Lanka. Calling songs of males sampled from four sites in peninsular India exhibited significant differences in a number of call features, suggesting the existence of multiple species. Cluster analysis of the acoustic data, molecular phylogenetic analyses, and phylogenetic analyses combining all data sets suggested the existence of three clades. Whatever the differences in calling signals, no full congruence was obtained between all the data sets, even though the resultant lineages were largely concordant with the acoustic clusters. The genus Itaropsis could thus be represented by three morphologically cryptic incipient species in peninsular India; their distributions are congruent with usual patterns of endemism in the Western Ghats, India. Song evolution is analysed through the divergence in syllable period, syllable and call duration, and dominant frequency.

Nanocatalysis and Prospects of Green Chemistry

Designing and developing ideal catalyst paves the way to green chemistry. The fields of catalysis and nanoscience have been inextricably linked to each other for a long time. Thanks to the recent advances in characterization techniques, the old technology has been revisited with a new scope. The last decade has witnessed a flood of research activity in the field of nanocatalysis, with most of the studies focusing on the effect of size on catalytic properties. This led to the development of much greener catalysts with higher activity, selectivity and greater ease of separation from the reaction medium. This Minireview describes the emerging trends in the field of nanocatalysis with implications towards green chemistry and sustainability.

Full spin and spatial symmetry adapted technique for correlated electronic hamiltonians: Application to an icosahedral cluster

One of the long standing problems in quantum chemistry had been the inability to exploit full spatial and spin symmetry of an electronic Hamiltonian belonging to a non-Abelian point group. Here, we present a general technique which can utilize all the symmetries of an electronic (magnetic) Hamiltonian to obtain its full eigenvalue spectrum. This is a hybrid method based on Valence Bond basis and the basis of constant z-component of the total spin. This technique is applicable to systems with any point group symmetry and is easy to implement on a computer. We illustrate the power of the method by applying it to a model icosahedral half-filled electronic system. This model spans a huge Hilbert space (dimension 1,778,966) and in the largest non-Abelian point group. The C60 molecule has this symmetry and hence our calculation throw light on the higher energy excited states of the bucky ball. This method can also be utilized to study finite temperature properties of strongly correlated systems within an exact diagonalization approach. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

15-deoxyspergualin hinders physical interaction between basic residues of transit peptide in PfENR and Hsp70-1

The apicoplast of Plasmodium harbors several metabolic pathways. The enzymes required to perform these reactions are all nuclearly encoded and apicoplast targeted (NEAT) proteins. Plasmodium falciparum Enoyl-ACP Reductase (PfENR) is one such NEAT protein. The NEAT proteins have a transit peptide which is required for crossing the membranes of apicoplast. We studied the importance of basic residues like Arginine and Lysine within the transit peptide. Previous studies have suggested that all basic residues are essential for apicoplast trafficking. In this study, we demonstrate that only some of these residues are essential (K44, R48, K51, and R52), whereas others are dispensable (R40, K42, and K49). On mutating these specific residues, PfENR is not imported into the apicoplast and is mislocalized to the cytoplasm. We also demonstrate that these residues are also crucial for interaction with Hsp70-1, implying that interactions of Lysine 44, Arginine 48, Lysine 51, and Arginine 52 of the transit peptide with PfHsp70-1 are required for apicoplast trafficking. 15-Deoxyspergualin, which has earlier been proposed to interact with EEVD motif of PfHsp70-1 hinders the physical interaction between these cationic residues of PfENR and Hsp70-1. Hence, we propose that in the transport competent state of NEAT proteins some specific positively charged amino acids in the transit peptide interact with PfHsp70-1, and this interaction is essential for apicoplast targeting.

Injection-molded high-density polyethylene-hydroxyapatite-aluminum oxide hybrid composites for hard-tissue replacement: Mechanical, biological, and protein adsorption behavior

In this article, we report the mechanical and biocompatibility properties of injection-molded high-density polyethylene (HDPE) composites reinforced with 40 wt % ceramic filler [hydroxyapatite (HA) and/or Al2O3] and 2 wt % titanate as a coupling agent. The mechanical property measurements revealed that a combination of a maximum tensile strength of 18.7 MPa and a maximum tensile modulus of about 855 MPa could be achieved with the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. For the same composite composition, the maximum compression strength was determined to be 71.6 MPa and the compression modulus was about 660 MPa. The fractrography study revealed the uniform distribution of ceramic fillers in the semicrystalline HDPE matrix. The cytocompatibility study with osteoblast-like SaOS2 cells confirmed extensive cell adhesion and proliferation on the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites. The cell viability analysis with the 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay revealed a statistically significant difference between the injection-molded HDPE20 wt % HA20 wt % Al2O3 composites and sintered HA for various culture durations of upto 7 days. The difference in cytocompatibility properties among the biocomposites is explained in terms of the difference in the protein absorption behavior. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Evaluation of physico-mechanical properties and in vitro biocompatibility of compression molded HDPE based biocomposites with HA/Al2O3 ceramic fillers and titanate coupling agents

The present article demonstrates how the stiffness, hardness as well as the cellular response of bioinert high-density polyethylene (HDPE) can be significantly improved with combined addition of both bioinert and bioactive ceramic fillers. For this purpose, different amounts of hydroxyapatite and alumina, limited to a total of 40 wt %, have been incorporated in HDPE matrix. An important step in composite fabrication was to select appropriate solvent and optimal addition of coupling agent (CA). In case of chemically coupled composites, 2% Titanium IV, 2-propanolato, tris iso-octadecanoato-O was used as a CA. All the hybrid composites, except monolithic HDPE, were fabricated under optimized compression molding condition (140 degrees C, 0.75 h, 10 MPa pressure). The compression molded composites were characterized, using X-ray diffraction, Fourier transformed infrared spectroscopy, and scanning electron microscopy. Importantly, in vitro cell culture and cell viability study (MTT) using L929 fibroblast and SaOS2 osteoblast-like cells confirmed good cytocompatibility properties of the developed hybrid composites. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

A Refined Methodology for Durability-Based Service Life Estimation of Reinforced Concrete Structural Elements Considering Fuzzy and Random Uncertainties

A reliable method for service life estimation of the structural element is a prerequisite for service life design. A new methodology for durability-based service life estimation of reinforced concrete flexural elements with respect to chloride-induced corrosion of reinforcement is proposed. The methodology takes into consideration the fuzzy and random uncertainties associated with the variables involved in service life estimation by using a hybrid method combining the vertex method of fuzzy set theory with Monte Carlo simulation technique. It is also shown how to determine the bounds for characteristic value of failure probability from the resulting fuzzy set for failure probability with minimal computational effort. Using the methodology, the bounds for the characteristic value of failure probability for a reinforced concrete T-beam bridge girder has been determined. The service life of the structural element is determined by comparing the upper bound of characteristic value of failure probability with the target failure probability. The methodology will be useful for durability-based service life design and also for making decisions regarding in-service inspections.

Triclabendazole: An Intriguing Case of Co-existence of Conformational and Tautomeric Polymorphism

The crystal polymorphism of the anthelmintic drug, triclabendazole (TCB), is described. Two anhydrates (Forms I and II), three solvates, and an amorphous form have been previously mentioned. This study reports the crystal structures of Forms I (1) and II (2). These structures illustrate the uncommon phenomenon of tautomeric polymorphism. TCB exists as two tautomers A and B. Form I (Z'=2) is composed of two molecules of tautomer A while Form II (Z'=1) contains a 1:1 mixture of A and B. The polymorphs are also characterized by using other solid-state techniques (differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), PXRD, FT-IR, and NMR spectroscopy). Form I is the higher melting form (m.p.: 177 degrees C, Delta Hf=approximate to 105 +/- 4 Jg-1) and is the more stable form at room temperature. Form II is the lower melting polymorph (m.p.: 166 degrees C, Delta Hf=approximate to 86 +/- 3 Jg-1) and shows high kinetic stability on storage in comparison to the amorphous form but it transforms readily into Form I in a solution-mediated process. Crystal structure analysis of co-crystals 3-11 further confirms the existence of tautomeric polymorphism in TCB. In 3 and 11, tautomer A is present whereas in 4-10 the TCB molecule exists wholly as tautomer B. The DFT calculations suggest that the optimized tautomers A and B have nearly the same energies. Single point energy calculations reveal that tautomer A (in Form I) exists in two low-energy conformations, whereas in Form II both tautomers A and B exist in an unfavorable high-energy conformation, stabilized by a five-point dimer synthon. The structural and thermodynamic features of 1-11 are discussed in detail. Triclabendazole is an intriguing case in which tautomeric and conformational variations co-exist in the polymorphs.

Structures of new crystal forms of Mycobacterium tuberculosis peptidyl-tRNA hydrolase and functionally important plasticity of the molecule

The X-ray structures of new crystal forms of peptidyl-tRNA hydrolase from M.similar to tuberculosis reported here and the results of previous X-ray studies of the enzyme from different sources provide a picture of the functionally relevant plasticity of the protein molecule. The new X-ray results confirm the connection deduced previously between the closure of the lid at the peptide-binding site and the opening of the gate that separates the peptide-binding and tRNA-binding sites. The plasticity of the molecule indicated by X-ray structures is in general agreement with that deduced from the available solution NMR results. The correlation between the lid and the gate movements is not, however, observed in the NMR structure.

Timing and broad-band spectroscopy of 1A 1118-61 with Suzaku

We present a timing and broad-band pulse-phase-resolved spectral analysis of the transient Be X-ray binary pulsar 1A 1118-61 observed during its outburst in 2009 January using Suzaku observations. The Suzaku observations were made twice, once at the peak of the outburst, and the other 13 d later at its declining phase. Pulse profiles from both observations exhibit strong energy dependence with several peaks at low energies and a single peak above similar to 10 keV. A weak, narrow peak is detected at the main dip of the pulse profiles from both observations in the energy bands below 3 keV, indicating the presence of a phase-dependent soft excess in the source continuum. The broad-band energy spectrum of the pulsar could be fitted well with a partial covering cut-off power-law model and a narrow iron fluorescence line. We also detect a broad cyclotron feature at similar to 50 keV from both observations which is a feature common for accretion-powered pulsars with high magnetic field strength. The pulse-phase-resolved spectral analysis shows an increase in the absorption column density of the partial covering component, as well as variation in the covering fraction at the dips of the pulse profiles, which naturally explains energy dependence of the same. The cyclotron line parameters also show significant variation with pulse phase with an similar to 10 keV variation in the cyclotron line energy and a variation in depth by a factor of 3. This can be explained either as the effect of different viewing angles of the dipole field at different pulse phases, or due to a more complex underlying magnetic field geometry.

Gallium and indium co-doped ZnO thin films for white light emitting diodes

Ga and In co-doped ZnO (GIZO) thin films together with ZnO, In-doped ZnO (IZO), Ga-doped ZnO (GZO), and IZO/GZO multilayer for comparison, were grown on corning glass and boron doped Si substrates by PLD. The photoluminescence spectra of GIZO showed a strong white light emission and the current-voltage characteristics showed relatively lower turn-on voltage and larger forward current. The CIE coordinates for GIZO were observed to be (0.31, 0.33) with a correlated colour temperature of 6650 K, indicating a cool white light, and establishing a possibility of white light emitting diodes. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Analysis of oxide and vanadate supports for catalytic hydrogen combustion: Kinetic and mechanistic investigations

Combustion synthesized oxide and vanadate compounds (CeO2, Fe2O3, CeVO4, and FeVO4) were tested for catalytic hydrogen combustion. The compounds were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. All the four compounds showed good activity and stability for catalytic hydrogen combustion and more than 95% conversion was observed over all the compounds within 500 degrees C. The mechanisms for the reaction over the different classes of compounds (cerium-based and iron-based compounds) were proposed on the basis of spectroscopic observations. The main difference in the mechanisms was in the nature of adsorption of H2 over the sites. The elementary processes for the reaction were proposed, corresponding rate expressions were derived, and the rate parameters for the reaction were estimated using nonlinear regression. Langmuir-Hinshelwood and Eley-Rideal mechanisms were also tested for the reaction and the proposed mechanism was compared with these mechanisms. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012