Cu(II)-azide polymers with various molar equivalents of blocking diamine ligands: synthesis, structures, magnetic properties with DFT studies

Four new neutral copper-azido polymers [Cu(4)(N(3))(8)(Me-hmpz)(2)](n) (1), [Cu(4)(N(3))(8)(men)(2)](n) (2), [Cu(5)(N(3))(10)(N,N-dmen)(2)](n) (3) and [Cu(5)(N(3))(10)(N,N'-dmen)(5)](n) (4) [Me-hmpz = 1-methylhomopiperazine; men = N-methylethylenediamine; N, N-dmen = N, N-dimethylethylenediamine and N, N'-dmen = N, N'-dimethylethylenediamine] have been synthesized by using various molar equivalents of the chelating diamine ligands with Cu(NO(3))(2)center dot 3H(2)O and an excess of NaN(3). Single-crystal X-ray structures show that the basic asymmetric units of 1 and 2 are very similar, but the overall 1D structures were found to be quite different. Complex 3 with a different composition was found to be 2D in nature, while the 1D complex 4 with 1 : 1 metal to diamine ratio presented several new structural features. Cryomagnetic susceptibility measurements over a wide range of temperature were corroborated with density functional theory calculations (B3LYP functional) performed on the complexes 1-3 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Studies of phosphazenes .11. syntheses and structures of bis(primary amino)hexachlorocyclotetraphosphazenes and their dimethylamino derivatives

The bis(amino)hexachlorocyclotetraphosphazenes, 2-trans-6-N4P4 (NHR)2Cl6, R [dbnd] Me, Pr n Pr i , Bu n , CH2Ph, Ph, are obtained from the reaction of N4P4Cl8 with four mol. equivalents of the appropriate amine. Isomers with 2,4-structures have been isolated for R [dbnd] Bu n , CH2Ph. The 1H and 31P NMR spectra of these bis(amino) compounds and of their dimethylamino derivatives, 2-trans-6-N4P4 (NMe2)6 (NHR)2 are discussed.

Two new 1D chains of Ni(2)Na(2) heterometallic double half-cubane building units: Synthesis, structures and variable temperature magnetic study

An equimolar mixture of Ni(NO(3))(2)center dot 6H(2)O and pyridine-2-aldehyde with two equivalents of NaN(3) in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(2)(MeOH)}center dot MeOH center dot 3H(2)O](n) (1) and [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(4)}center dot 2DMF center dot H(2)O](n) (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100 degrees C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J approximate to + 10 cm(-1) and D approximate to -2 to -7 cm(-1) for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni(2)(II) dimeric unit, results were J = + 20.65 cm(-1) and D = -3.16 cm(-1) for 1, and J = +24.56 cm(-1) and D = -4.67 cm(-1) for 2. However, considering Ni(2)(II)Na(2)(I) cubane as magnetic core the results were J = +16.35 cm(-1) (1), +19.54 cm(-1) (2); D = -3.05 cm(-1) (1), -4.25 cm(-1) (2).

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.

Spectral Element Approach to Wave Propagation in Uncertain Composite Beam Structures

This paper presents a study of the wave propagation responses in composite structures in an uncertain environment. Here, the main aim of the work is to quantify the effect of uncertainty in the wave propagation responses at high frequencies. The material properties are considered uncertain and the analysis is performed using Neumann expansion blended with Monte Carlo simulation under the environment of spectral finite element method. The material randomness is included in the conventional wave propagation analysis by different distributions (namely, the normal and the Weibul distribution) and their effect on wave propagation in a composite beam is analyzed. The numerical results presented investigates the effect of material uncertainties on different parameters, namely, wavenumber and group speed, which are relevant in the wave propagation analysis. The effect of the parameters, such as fiber orientation, lay-up sequence, number of layers, and the layer thickness on the uncertain responses due to dynamic impulse load, is thoroughly analyzed. Significant changes are observed in the high frequency responses with the variation in the above parameters, even for a small coefficient of variation. High frequency impact loads are applied and a number of interesting results are presented, which brings out the true effects of uncertainty in the high frequency responses. [DOI: 10.1115/1.4003945]

Aza-heterocyclic ligand assisted assembly of new cobalt MOFs with pcu and graphite related structures

A hydrothermal reaction of a mixture of cobalt salt, 5-nitro isophthalic acid and triazole (compound I), 3-aminotriazole (3-AT) (compound II) and 3,5-diaminotriazole (compound III) at 220 degrees C for a day resulted in the isolation of three different, but related, compounds containing cobalt clusters. The three-dimensional compounds have Co-5 (compound-I) and Co-4 (compound-II and compound-III) clusters connected through the carboxylate and triazolate forming structures with pcu net (compound-I and compound-II) and a graphite-related net (compound-III). The water molecules (coordinated and lattice) can be readily re-adsorbed by the structure of compound-I, whereas the removal of the water molecule leads to a collapse of the structures of compound-II and compound-III. The TGA studies suggest the possibility of an intermediate structure for compound-1, which was investigated using in situ single crystal to single crystal (SCSC) transformations. The identification of an intermediate structure during the dehydration/hydration cycle in compound-I is important and provides important pointers about the dynamics of the water molecules in these compounds. Compound-I was also investigated in detail using a variety of spectroscopic techniques such as IR, UV-Vis spectroscopy etc. Magnetic studies on the synthesized compounds indicate anti-ferromagnetic behavior.

Synthesis and Molecular Structures of Carboxylic Acid Group Bearing Two Ketoimines that Exist in Enaminone Form

Condensation reaction involving substituted aminobenzoic acids (2-aminobenzoic acid and 4-aminobenzoic acid) and acetylacetone results in the formation of ketoimines [CH3C(= O)CH2C(CH3)(= NAr)] (Ar = C6H4COOH-4; 1 and C6H4COOH-2 2). Compounds 1 and 2 have been characterized by spectroscopic techniques and by single crystal X-ray diffraction studies. The absorption, emission and lifetime measurement studies have also been performed for the new compounds. While compound 1 forms a linear chain type of aggregation though intermolecular hydrogen bonding, compound 2 forms a discrete dimer in the solid state.

A review of recent developments in parametric based acoustic emission techniques applied to concrete structures

This article presents a review of recent developments in parametric based acoustic emission (AE) techniques applied to concrete structures. It recapitulates the significant milestones achieved by previous researchers including various methods and models developed in AE testing of concrete structures. The aim is to provide an overview of the specific features of parametric based AE techniques of concrete structures carried out over the years. Emphasis is given to traditional parameter-based AE techniques applied to concrete structures. A significant amount of research on AE techniques applied to concrete structures has already been published and considerable attention has been given to those publications. Some recent studies such as AE energy analysis and b-value analysis used to assess damage of concrete bridge beams have also been discussed. The formation of fracture process zone and the AE energy released during the fracture process in concrete beam specimens have been summarised. A large body of experimental data on AE characteristics of concrete has accumulated over the last three decades. This review of parametric based AE techniques applied to concrete structures may be helpful to the concerned researchers and engineers to better understand the failure mechanism of concrete and evolve more useful methods and approaches for diagnostic inspection of structural elements and failure prediction/prevention of concrete structures.

The canonic linear-phase FIR lattice structures

The Linear phase(LP) Finite Impulse Response(FIR) filters are widely used in many signal processing systems which are sensitive to phase distortion. In this article, we obtain a canonic lattice structure of an LP-FIR filter with a complex impulse response. This lattice structure is based on some novel lattice stages obtained from some properties of symmetric polynomials.This canonic lattice structure exploits the redundancy in the zeros of an LP-FIR filter.

Optimization of vibrating structures to reduce radiated noise

In this work, we propose an approach for reducing radiated noise from `light' fluid-loaded structures, such as, for example, vibrating structures in air. In this approach, we optimize the structure so as to minimize the dynamic compliance (defined as the input power) of the structure. We show that minimizing the dynamic compliance results in substantial reductions in the radiated sound power from the structure. The main advantage of this approach is that the redesign to minimize the dynamic compliance moves the natural frequencies of the structure away from the driving frequency thereby reducing the vibration levels of the structure, which in turn results in a reduction in the radiated sound power as an indirect benefit. Thus, the need for an acoustic and the associated sensitivity analysis is completely bypassed (although, in this work, we do carry out an acoustic analysis to demonstrate the reduction in sound power levels), making the strategy efficient compared to existing strategies in the literature which try to minimize some measure of noise directly. We show the effectiveness of the proposed approach by means of several examples involving both topology and stiffener optimization, for vibrating beam, plate and shell-type structures.

Studies on Field Dependent Domain Structures in Multi-Grained 0.85PbMg(1/3)Nb(2/3)O3-0.15PbTiO(3) Thin Films by Scanning Force Microscopy

0.85PbMg(1/3)Nb(2/3)O(3)-0.15PbTiO(3) (0.85PMN-0.15PT) ferroelectric relaxor thin films have been deposited on La0.5Sr0.5CoO3/(111) Pt/TiO2/SiO2/Si by pulsed laser ablation by varying the oxygen partial pressures from 50 mTorr to 400 mTorr. The X-ray diffraction pattern reveals a pyrochlore free polycrystalline film. The grain morphology of the deposited films was studied using scanning electron microscopy and was found to be affected by oxygen pressure. By employing dynamic contact-electrostatic force microscopy we found that the distribution of polar nanoregions is majorly affected by oxygen pressure. Finally, the electric field induced switching in these films is discussed in terms of domain wall pinning.

Network properties of protein-decoy structures

Convergence of the vast sequence space of proteins into a highly restricted fold/conformational space suggests a simple yet unique underlying mechanism of protein folding that has been the subject of much debate in the last several decades. One of the major challenges related to the understanding of protein folding or in silico protein structure prediction is the discrimination of non-native structures/decoys from the native structure. Applications of knowledge-based potentials to attain this goal have been extensively reported in the literature. Also, scoring functions based on accessible surface area and amino acid neighbourhood considerations were used in discriminating the decoys from native structures. In this article, we have explored the potential of protein structure network (PSN) parameters to validate the native proteins against a large number of decoy structures generated by diverse methods. We are guided by two principles: (a) the PSNs capture the local properties from a global perspective and (b) inclusion of non-covalent interactions, at all-atom level, including the side-chain atoms, in the network construction accommodates the sequence dependent features. Several network parameters such as the size of the largest cluster, community size, clustering coefficient are evaluated and scored on the basis of the rank of the native structures and the Z-scores. The network analysis of decoy structures highlights the importance of the global properties contributing to the uniqueness of native structures. The analysis also exhibits that the network parameters can be used as metrics to identify the native structures and filter out non-native structures/decoys in a large number of data-sets; thus also has a potential to be used in the protein `structure prediction' problem.